http://www.mdpi.com/journal/molecules Latest open access articles published in Molecules at http://www.mdpi.com/journal/molecules Molecules 1420-3049 http://www.mdpi.com/1420-3049/15/3/1513 The thermal [4+2] cycloadditions of 3-acetyl-, 3-carbamoyl, and 3-ethoxycarbonylcoumarins with 2,3-dimethyl-1,3-butadiene under solvent free conditions are reported, as well as the epoxidation reactions of some adducts. Discussion is focused on the structural features of the Diels-Alder adducts and their epoxides, based upon NMR, X-ray, and mass spectral data, and supported by ab initio theoretical calculations. http://www.mdpi.com/1420-3049/15/3/1513 Mon, 08 Mar 2010 23:00:01 GMT Molecules 2010-03-09 15 3 Article 1513 1530 1420-3049 Thermal [4 + 2] Cycloadditions of 3-Acetyl-, 3-Carbamoyl-, and 3-Ethoxycarbonyl-Coumarins with 2,3-Dimethyl-1,3-butadiene under Solventless Conditions: A Structural Study 2010-03-09 doi:10.3390/molecules15031513 Irma Y. Flores-Larios Lizbeth López-Garrido Francisco J. Martínez-Martínez Jorge González Efrén V. García-Báez Alejandro Cruz Itzia I. Padilla-Martínez http://www.mdpi.com/1420-3049/15/3/1501 The synthesis of a new chiral pyrrolidine has been performed using 2,3-O-isopropylidene-D-erythronolactol as a suitable starting material. http://www.mdpi.com/1420-3049/15/3/1501 Mon, 08 Mar 2010 23:00:01 GMT Molecules 2010-03-09 15 3 Article 1501 1512 1420-3049 Synthesis of a New Chiral Pyrrolidine 2010-03-09 doi:10.3390/molecules15031501 Mari Fe. Flores Marta G. Núñez Rosalina F. Moro Narciso M. Garrido Isidro S. Marcos Enrique F. Iglesias Pilar García David Díez http://www.mdpi.com/1420-3049/15/3/1487 The direct aerobic coupling reaction of arenes with olefins was successfully achieved by the use of Pd(OAc)2/molybdovanadophosphoric acid (HPMoV) as a key catalyst under 1 atm of dioxygen. This catalytic system could be extended to the coupling reaction of various substituted benzenes with olefins such as acrylates, aclrolein, and ethylene through the direct aromatic C-H bond activation. http://www.mdpi.com/1420-3049/15/3/1487 Mon, 08 Mar 2010 23:00:01 GMT Molecules 2010-03-09 15 3 Article 1487 1500 1420-3049 Pd(II)/HPMoV-Catalyzed Direct Oxidative Coupling Reaction of Benzenes with Olefins 2010-03-09 doi:10.3390/molecules15031487 Yasushi Obora Yasutaka Ishii http://www.mdpi.com/1420-3049/15/3/1473 Coprinus comatus, also called chicken drumstick mushroom, is currently commercially available in China. Hot water and ethanolic extracts were prepared from cap and stipe of C. comatus fruit bodies and their antioxidant properties were studied. Ethanolic extract from stipe showed high antioxidant activity (80.6%) at 1 mg/mL. Reducing power of hot water extracts from cap was 1.653 at 10 mg/mL. Extracts from cap showed better scavenging ability on DPPH (57.9% at 1 mg/mL) than stipe ones. Ethanolic extracts were more effective in scavenging ability on hydroxyl radicals (57.4–61.3% at 5 mg/mL) than hot water extracts. Ethanolic extracts showed moderate scavenging ability on superoxide radicals (46.3–47.0% at 20 mg/mL). Naturally occurring antioxidant components including total phenols (3.60–20.00 mg/g), tocopherols (0.58–11.93 mg/g), flavonoids (0.19–3.52 mg/g) and polysaccharides (58.52–547.86 mg/g) were found in the extracts. Overall, extracts from cap were more effective for the antioxidant properties assayed. http://www.mdpi.com/1420-3049/15/3/1473 Mon, 08 Mar 2010 23:00:01 GMT Molecules 2010-03-09 15 3 Article 1473 1486 1420-3049 Antioxidant Properties of Cap and Stipe from Coprinus comatus 2010-03-09 doi:10.3390/molecules15031473 Bo Li Fei Lu Xiaomin Suo Haijuan Nan Bin Li http://www.mdpi.com/1420-3049/15/3/1466 The oxidation of 1-unsubstituted or 1-phenyl-1H-isotellurochromenes with m-chloroperbenzoic acid (mCPBA) in CHCl3 resulted in a ring opening reaction to produce as the sole products the corresponding o-formyl or benzoyl distyryl ditellurides, which were also produced by the hydrolysis of the 2-benzotelluropyrylium salts readily prepared from the parent isotellurochromene. http://www.mdpi.com/1420-3049/15/3/1466 Mon, 08 Mar 2010 23:00:01 GMT Molecules 2010-03-09 15 3 Article 1466 1472 1420-3049 Novel Oxidative Ring Opening Reaction of 1H-Isotelluro-chromenes to Bis(o-formylstyryl) Ditellurides 2010-03-09 doi:10.3390/molecules15031466 Haruki Sashida Hirohito Satoh Kazuo Ohyanagi Mamoru Kaname http://www.mdpi.com/1420-3049/15/3/1453 Nephelium lappaceum is a tropical fruit whose peel possesses antioxidant properties. Experiments on the isolation and identification of the active constituents were conducted, and on their antioxidant activity using a lipid peroxidation inhibition assay. The methanolic extract of N. lappaceum peels exhibited strong antioxidant properties. Sephadex LH-20 chromatography was utilized in the isolation of each constituent and the antioxidant properties of each was studied. The isolated compounds were identified as ellagic acid (EA) (1), corilagin (2) and geraniin (3). These compounds accounted for 69.3% of methanolic extract, with geraniin (56.8%) as the major component, and exhibited much greater antioxidant activities than BHT in both lipid peroxidation (77-186 fold) and DPPH• (42-87 fold) assays. The results suggest that the isolated ellagitannins, as the principal components of rambutan peels, could be further utilized as both a medicine and in the food industry. http://www.mdpi.com/1420-3049/15/3/1453 Mon, 08 Mar 2010 23:00:01 GMT Molecules 2010-03-09 15 3 Article 1453 1465 1420-3049 Identification of Major Phenolic Compounds from Nephelium lappaceum L. and Their Antioxidant Activities 2010-03-09 doi:10.3390/molecules15031453 Nont Thitilertdecha Aphiwat Teerawutgulrag Jeremy D. Kilburn Nuansri Rakariyatham http://www.mdpi.com/1420-3049/15/3/1442 A novel chiral macrocyclic ligand incorporating a chiral salen moiety into a framework containing two biphenyl units was synthesized. Structural properties and conformational aspects of the free ligand and an UO2 complex were studied by using NMR spectroscopy in solution and MM calculations. The Mn(III) complex was tested as catalyst in enantioselective oxidation of prochiral unfunctionalized olefins to the corresponding optically active epoxides under very mild conditions. http://www.mdpi.com/1420-3049/15/3/1442 Mon, 08 Mar 2010 23:00:01 GMT Molecules 2010-03-09 15 3 Article 1442 1452 1420-3049 Synthesis and Conformational Study of a Novel Macrocyclic Chiral(Salen) ligand and its Uranyl and Mn Complexes 2010-03-09 doi:10.3390/molecules15031442 Maria E. Amato Francesco P. Ballistreri Andrea Pappalardo Gaetano A. Tomaselli Rosa M. Toscano http://www.mdpi.com/1420-3049/15/3/1433 SrCl2·6H2O has been shown to act as an efficient catalyst for the conversion of aldehydes or ketones into the corresponding gem-dihydroperoxides (DHPs) by treatment with aqueous H2O2 (30%) in acetonitrile. The reactions proceed under mild and neutral conditions at room temperature to afford good to excellent yields of product. http://www.mdpi.com/1420-3049/15/3/1433 Sun, 07 Mar 2010 23:00:01 GMT Molecules 2010-03-08 15 3 Article 1433 1441 1420-3049 Mild and Efficient Strontium Chloride Hexahydrate-Catalyzed Conversion of Ketones and Aldehydes into Corresponding gem- Dihydroperoxides by Aqueous H2O2 2010-03-08 doi:10.3390/molecules15031433 Davood Azarifar Kaveh Khosravi Fatemeh Soleimanei http://www.mdpi.com/1420-3049/15/3/1425 New organotin substituted α-anilinomethylphosphonates were prepared and were characterized by FT-IR, 1H- and 13C-NMR spectroscopy and elemental microanalysis. http://www.mdpi.com/1420-3049/15/3/1425 Sun, 07 Mar 2010 23:00:01 GMT Molecules 2010-03-08 15 3 Article 1425 1432 1420-3049 Synthesis and Characterization of Novel Organotin-Phosphorous Compounds II 2010-03-08 doi:10.3390/molecules15031425 Salem S. Al-Deyab Mohamed H. El-Newehy http://www.mdpi.com/1420-3049/15/3/1408 Development of effective and environmentally friendly disinfectants, or virucidal agents, should help prevent the spread of infectious diseases through human contact with contaminated surfaces. These agents may also be used, if non-toxic to cells and tissues, as chemotherapeutic agents against infectious diseases. We have shown that arginine has a synergistic effect with a variety of virucidal conditions, namely acidic pH and high temperature, on virus inactivation. All of these treatments are effective, however, at the expense of toxicity. The ability of arginine to lower the effective threshold of these parameters may reduce the occurrence of potential toxic side effects. While it is clear that arginine can be safely used, the mechanism of its virus inactivation has not yet been elucidated. Here we examine the damages that viruses suffer from various physical and chemical stresses and their relations to virus inactivation and aggregation. Based on the relationship between the stress-induced structural damages and the infectivity of a virus, we will propose several plausible mechanisms describing the effects of arginine on virus inactivation using the current knowledge of aqueous arginine solution properties. http://www.mdpi.com/1420-3049/15/3/1408 Sun, 07 Mar 2010 23:00:01 GMT Molecules 2010-03-08 15 3 Review 1408 1424 1420-3049 Arginine as a Synergistic Virucidal Agent 2010-03-08 doi:10.3390/molecules15031408 Satoshi Ohtake Tsutomu Arakawa A. Hajime Koyama http://www.mdpi.com/1420-3049/15/3/1398 The cationic ring-opening polymerization reaction of tetrahydrofuran at 20 ºC was catalyzed by H3PW12O40·13H2O as solid acid catalyst. The effect of the proportions of acetic anhydride and catalyst, reaction time and support on the polymerization reaction was investigated. It has been found that the yield and the viscosity of the polymer depend on the proportion of acetic anhydride, the presence of the latter in the reactant mixture being required for the ring-opening. The catalytic activity of the alumina-supported heteropolyacid results showed that Brønsted acid sites are more effective than Lewis ones for the cationic ring-opening polymerization. http://www.mdpi.com/1420-3049/15/3/1398 Sun, 07 Mar 2010 23:00:01 GMT Molecules 2010-03-08 15 3 Article 1398 1407 1420-3049 The Cationic Ring-Opening Polymerization of Tetrahydrofuran with 12-Tungstophosphoric Acid 2010-03-08 doi:10.3390/molecules15031398 Ahmed Aouissi Salem S. Al-Deyab Hassan Al-Shahri http://www.mdpi.com/1420-3049/15/3/1378 Artemisinins have become essential antimalarial drugs for increasingly widespread drug-resistant malaria strains. Although tremendous efforts have been devoted to decipher how this class of molecules works, their exact antimalarial mechanism is still an enigma. Several hypotheses have been proposed to explain their actions, including alkylation of heme by carbon-centered free radicals, interference with proteins such as the sarcoplasmic/endoplasmic calcium ATPase (SERCA), as well as damaging of normal mitochondrial functions. Besides artemisinins, other endoperoxides with various backbones have also been synthesized, some of which showed comparable or even higher antimalarial effects. It is noteworthy that among these artemisinin derivatives, some enantiomers displayed similar in vitro malaria killing efficacy. In this article, the proposed mechanisms of action of artemisinins are reviewed in light of medicinal chemistry findings characterized by efficacy-structure studies, with the hope of gaining more insight into how these potent drugs work. http://www.mdpi.com/1420-3049/15/3/1378 Sun, 07 Mar 2010 23:00:01 GMT Molecules 2010-03-08 15 3 Review 1378 1397 1420-3049 Biological Actions of Artemisinin: Insights from Medicinal Chemistry Studies 2010-03-08 doi:10.3390/molecules15031378 Jian Li Bing Zhou http://www.mdpi.com/1420-3049/15/3/1354 New synthetic methods for the preparation of biologically active phospholipids and lysophospholipids (LPLs) are very important in solving problems of membrane–chemistry and biochemistry. Traditionally considered just as second-messenger molecules regulating intracellular signalling pathways, LPLs have recently shown to be involved in many physiological and pathological processes such as inflammation, reproduction, angiogenesis, tumorogenesis, atherosclerosis and nervous system regulation. Elucidation of the mechanistic details involved in the enzymological, cell-biological and membrane-biophysical roles of LPLs relies obviously on the availability of structurally diverse compounds. A variety of chemical and enzymatic routes have been reported in the literature for the synthesis of LPLs: the enzymatic transformation of natural glycerophospholipids (GPLs) using regiospecific enzymes such as phospholipases A1 (PLA1), A2 (PLA2) phospholipase D (PLD) and different lipases, the coupling of enzymatic processes with chemical transformations, the complete chemical synthesis of LPLs starting from glycerol or derivatives. In this review, chemo-enzymatic procedures leading to 1- and 2-LPLs will be described. http://www.mdpi.com/1420-3049/15/3/1354 Sun, 07 Mar 2010 23:00:01 GMT Molecules 2010-03-08 15 3 Review 1354 1377 1420-3049 Synthesis of Lysophospholipids 2010-03-08 doi:10.3390/molecules15031354 Paola D’Arrigo Stefano Servi http://www.mdpi.com/1420-3049/15/3/1340 A novel method for the conversion of unprotected and unmodified aldoses to aldo-imidazoles has been developed. Using iodine as a catalyst in acetic acid solution, a series of mono- and oligosaccharides, including those containing carboxyl and acetamido groups, undergo an oxidative condensation reaction with aromatic vicinal diamines at room temperature to give the corresponding aldo-imidazole products in high yields. No cleavage of the glycosidic bond occurs under the mild reaction conditions. The compositional analysis of saccharides is commonly realized by capillary electropheresis of the corresponding aldo-imidazole derivatives, which are easily synthesized by the reported iodine-promoted oxidative condensation. In addition, a series of aldo-imidazoles were determined by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI–TOF MS) to analyze molecular weight and ion intensity. The diamine-labeled saccharides showed enhanced signals in MALDI–TOF MS. The combined use of aldoimidazole derivatization and mass spectrometric analysis thus provides a rapid method for identification of saccharides, even when less than 1 pmol of saccharide is present in the sample. These results can be further applied to facilitate the isolation and analysis of novel saccharides. http://www.mdpi.com/1420-3049/15/3/1340 Thu, 04 Mar 2010 23:00:01 GMT Molecules 2010-03-05 15 3 Article 1340 1353 1420-3049 I2-Catalyzed Oxidative Condensation of Aldoses with Diamines: Synthesis of Aldo-Naphthimidazoles for Carbohydrate Analysis 2010-03-05 doi:10.3390/molecules15031340 Chunchi Lin Wei-Ting Hung Chien-Yuan Kuo Kuo-Shiang Liao Yin-Chen Liu Wen-Bin Yang http://www.mdpi.com/1420-3049/15/3/1324 A series of Ru(II) and Os(II) tris-chelate complexes with new bidentate 2-pyridylquinoline ligands have been synthesized and fully characterized by EA,1H-NMR and FAB-MS techniques. The new ligands are: L1 = 4-p-methoxyphenyl-6-bromo-2-(2′- pyridyl)quinoline (mphbr-pq) and L2 = 4-p-hydroxyphenyl-6-bromo-2-(2′-pyridyl)-quinoline (hphbr-pq). The complexes studied are: [Ru(bpy)2L1](PF6)2 (C1), [Ru(bpy)2L2](PF6)2 (C2), [Os(bpy)2L1](PF6)2 (C3), [Os(bpy)2L2](PF6)2 (C4) (bpy = 2,2′-bipyridine), [Ru(dmbpy)2L1](PF6)2 (C5), [Ru(dmbpy)2L2](PF6)2 (C6), [Os(dmbpy)2L1](PF6)2 (C7), and [Os(dmbpy)2L2](PF6)2 (C8) (dmbpy = 4,4′-dimethyl-2,2′-bipyridine). Moreover, new functionalized complexes C9-C12 were obtained by the basecatalyzed direct alkylation of C2, C4, C6, and C8 with 6-bromo-1-hexene. The complete assignment of the 1H-NMR spectra for the two new ligands (L1 and L2), and their Ru(II) or Os(II) complexes has been accomplished using a combination of one- and two-dimensional NMR techniques. The JH,H values have been determined for the majority of the resonances. http://www.mdpi.com/1420-3049/15/3/1324 Thu, 04 Mar 2010 23:00:01 GMT Molecules 2010-03-05 15 3 Article 1324 1339 1420-3049 Asymmetric Ruthenium(II) and Osmium(II) Complexes with New Bidentate Polyquinoline Ligands. Synthesis and NMR Characterization 2010-03-05 doi:10.3390/molecules15031324 Antonino Mamo Alessandro Aureliano Antonino Recca http://www.mdpi.com/1420-3049/15/3/1309 Since its identification in the early 1970s, artemisinin, as well as semi-synthetic derivatives and synthetic trioxanes, have been used in malaria therapy. Reduction of artemisinin by NaBH4 produced dihydroartemisinin (DHA), and yielded a new stereochemically labile centre at C-10, which, in turn, provided two interconverting lactol hemiacetal epimers (namely a and b), whose rate of interconversion depends on buffer, pH, and solvent polarity. Since interconversion of the two epimers occurred on a chromatographic time-scale, this prompted a thorough investigation of the phenomenon as a crucial requisite of any analytical method aimed at quantitating this family of drugs. In this critical review we discuss the current importance of the on-column epimerization of DHA in the development of analytical methods aimed at quantifying the drug, with the purpose of identifying the optimal conditions to minimize on-column epimerization while achieving the best selectivity and efficiency of the overall separation. http://www.mdpi.com/1420-3049/15/3/1309 Thu, 04 Mar 2010 23:00:01 GMT Molecules 2010-03-05 15 3 Review 1309 1323 1420-3049 Stereodynamic Investigation of Labile Stereogenic Centres in Dihydroartemisinin 2010-03-05 doi:10.3390/molecules15031309 Ilaria D’Acquarica Francesco Gasparrini Dorina Kotoni Marco Pierini Claudio Villani Walter Cabri Michela Di Mattia Fabrizio Giorgi http://www.mdpi.com/1420-3049/15/3/1302 The palladium-catalyzed hydroarylation of N-methyl-substituted tricyclic imides was studied in order to find a new stereoselective access to a series of new exo-aryl(hetaryl)-substituted tricyclic N-methylimides. http://www.mdpi.com/1420-3049/15/3/1302 Wed, 03 Mar 2010 23:00:01 GMT Molecules 2010-03-04 15 3 Article 1302 1308 1420-3049 Reductive Heck Reactions of N-Methyl-substituted Tricyclic Imides 2010-03-04 doi:10.3390/molecules15031303 Gokce Goksu Nuket Ocal Dieter E. Kaufmann http://www.mdpi.com/1420-3049/15/3/1291 The reduction of γ-N-benzylamino-β-ketophosphonates 6 and 10, readily available from L-proline and L-serine, respectively, can be carried out in high diastereoselectivity with catecholborane (CB) in THF at -78 ºC to produce the syn-γ-N-benzylamino-β-hydroxyphosphonates 11 and 13 as a single detectable diastereoisomer, under non-chelation or Felkin-Anh model control. http://www.mdpi.com/1420-3049/15/3/1291 Wed, 03 Mar 2010 23:00:01 GMT Molecules 2010-03-04 15 3 Article 1291 1301 1420-3049 Synthesis of syn-γ-Amino-β-hydroxyphosphonates by Reduction of β-Ketophosphonates Derived from L-Proline and L-Serine 2010-03-04 doi:10.3390/molecules15031291 Mario Ordóñez Selene Lagunas-Rivera Emanuel Hernández-Núñez Victoria Labastida-Galván http://www.mdpi.com/1420-3049/15/3/1280 A catalytic asymmetric nitro-Mannich (aza-Henry) reaction with rare earth metal/alkali metal heterobimetallic catalysts is described. A Yb/K heterobimetallic catalyst assembled by an amide-based ligand promoted the asymmetric nitro-Mannich reaction to afford enantioenriched anti-b-nitroamines in up to 86% ee. Facile reduction of the nitro functionality allowed for efficient access to optically active 1,2-diamines. http://www.mdpi.com/1420-3049/15/3/1280 Wed, 03 Mar 2010 23:00:01 GMT Molecules 2010-03-04 15 3 Article 1280 1290 1420-3049 Catalytic Asymmetric Nitro-Mannich Reactions with a Yb/K Heterobimetallic Catalyst 2010-03-04 doi:10.3390/molecules15031280 Tatsuya Nitabaru Naoya Kumagai Masakatsu Shibasaki http://www.mdpi.com/1420-3049/15/3/1270 Both bifidobacteria and clostridia are part of the natural gut microflora and while clostridia may be responsible for severe intestinal infections, bifidobacteria are probiotic microorganisms belonging to the most important prospective bacteria in the bowel. The antimicrobial activity of biochanin A was tested in vitro against six Bifidobacterium spp., and eight Clostridium spp. using the broth microdilution method. Biochanin A showed an inhibition against all clostridia in the range of minimum inhibitory concentrations (MIC) from 64 μg/mL (for Cl. clostridioforme, strains DSM 933 and I3) to 1,024 μg/mL (for Cl. perfringens, DSM 11778). No bifidobacteria were suppressed at four-fold higher concentration (MICs > 4,096) than MIC of Cl. perfringens. These results indicate selective growth inhibition of biochanin A and its potential use in antimicrobial prevention and/or protection. http://www.mdpi.com/1420-3049/15/3/1270 Tue, 02 Mar 2010 23:00:01 GMT Molecules 2010-03-03 15 3 Communication 1270 1279 1420-3049 Selective Growth Inhibitory Effect of Biochanin A Against Intestinal Tract Colonizing Bacteria 2010-03-03 doi:10.3390/molecules15031270 Olga Sklenickova Jaroslav Flesar Ladislav Kokoska Eva Vlkova Katerina Halamova Jan Malik http://www.mdpi.com/1420-3049/15/3/1265 Lithium, used in conjunction with sodium metal, produces a high yield of biphenyl when reacted with dibenzothiophene, dibenzothiophene sulfoxide or dibenzothiophene sulfone. http://www.mdpi.com/1420-3049/15/3/1265 Tue, 02 Mar 2010 23:00:01 GMT Molecules 2010-03-03 15 3 Article 1265 1269 1420-3049 Desulfurization of Dibenzothiophene and Oxidized Dibenzothiophene Ring Systems 2010-03-03 doi:10.3390/molecules15031265 Diego P. Morales Alexander S. Taylor Steven C. Farmer http://www.mdpi.com/1420-3049/15/3/1242 Reduced glutathione (GSH) is the most abundant non-protein thiol in mammalian cells and the preferred substrate for several enzymes in xenobiotic metabolism and antioxidant defense. It plays an important role in many cellular processes, such as cell differentiation, proliferation and apoptosis. GSH deficiency has been observed in aging and in a wide range of pathologies, including neurodegenerative disorders and cystic fibrosis (CF), as well as in several viral infections. Use of GSH as a therapeutic agent is limited because of its unfavorable biochemical and pharmacokinetic properties. Several reports have provided evidence for the use of GSH prodrugs able to replenish intracellular GSH levels. This review discusses different strategies for increasing GSH levels by supplying reversible bioconjugates able to cross the cellular membrane more easily than GSH and to provide a source of thiols for GSH synthesis. http://www.mdpi.com/1420-3049/15/3/1242 Tue, 02 Mar 2010 23:00:01 GMT Molecules 2010-03-03 15 3 Review 1242 1264 1420-3049 Prodrug Approach for Increasing Cellular Glutathione Levels 2010-03-03 doi:10.3390/molecules15031242 Ivana Cacciatore Catia Cornacchia Francesco Pinnen Adriano Mollica Antonio Di Stefano http://www.mdpi.com/1420-3049/15/3/1232 Research over the past decade has indicated that melanocortin peptides are potent inhibitors of inflammation and a promising source of new anti-inflammatory and cytoprotective therapies. The purpose of the present paper is to compare protective effects of α-, β-, and γ-melanocyte stimulating hormone on acetaminophen induced liver lesions in male CBA mice. Acetaminophen was applied intragastrically in a dose of 150 mg/kg, and tested substances were applied intraperitoneally 1 hour before acetaminophen. Mice were sacrificed after 24 hours and intensity of liver injury was estimated by measurement of plasma transaminase activity (AST and ALT) and histopathological grading of lesions. It was found that α-, β-, and γ-MSH decrease intensity of lesions by both criteria in a dose-dependent manner. http://www.mdpi.com/1420-3049/15/3/1232 Tue, 02 Mar 2010 23:00:01 GMT Molecules 2010-03-03 15 3 Article 1232 1241 1420-3049 The Influence of α-, β-, and γ-Melanocyte Stimulating Hormone on Acetaminophen Induced Liver Lesions in Male CBA Mice 2010-03-03 doi:10.3390/molecules15031232 Vladimir Blagaić Karlo Houra Petra Turčić Nikola Štambuk Paško Konjevoda Alenka Boban-Blagaić Tomislav Kelava Marina Kos Gorana Aralica Filip Čulo http://www.mdpi.com/1420-3049/15/3/1223 The in vitro antiradical activity of Schisandra chinensis lignans was investigated using DPPH, ABTS+, Fenton reaction inhibition and tyrosine-nitration inhibition assays, as were the in vivo antidiabetic activities of selected lignans in an animal model of alloxan-induced diabetes. Different degrees of antiradical activity were found, depending upon the structural parameters of the tested compounds. Unfortunately, the compounds showed no antidiabetic activity in concentration range tested. http://www.mdpi.com/1420-3049/15/3/1223 Tue, 02 Mar 2010 23:00:01 GMT Molecules 2010-03-03 15 3 Article 1223 1231 1420-3049 Evaluation of the Antiradical Activity of Schisandra Chinensis Lignans Using Different Experimental Models 2010-03-03 doi:10.3390/molecules15031223 Karel Šmejkal Tereza Šlapetová Pavel Krmenčík Renata Kubínová Pavel Suchý Stefano Dall´Acqua Gabbriella Innocenti Ján Vančo Karolína Kalvarová Margita Dvorská Jiří Slanina Eva Kramářová Jan Muselík Milan Žemlička http://www.mdpi.com/1420-3049/15/3/1213 The association constants Kb of three hosts I–III designed to have both enhanced hydrogen bonding donor strength and conformational preorganization with biotin analogues 1–5 are reported. 1H-NMR titrations under two different concentration conditions have been employed to determine the association constants Kb. A statistical analysis using a presence absence matrix has been applied to calculate the different contributions. Hydrogen bond interactions make naphthyridine derivatives II and III potent binders and effective receptors for (+)-biotin methyl ester (1), due to the complex stabilization by additional hydrogen bonds. http://www.mdpi.com/1420-3049/15/3/1213 Tue, 02 Mar 2010 23:00:01 GMT Molecules 2010-03-03 15 3 Article 1213 1222 1420-3049 Molecular Recognition Studies on Naphthyridine Derivatives 2010-03-03 doi:10.3390/molecules15031213 José Carlos Iglesias-Sánchez Dolores Santa María Rosa M. Claramunt José Elguero http://www.mdpi.com/1420-3049/15/3/1196 Epidemiological evidence indicates that nutritionally-derived polyphenols such as resveratrol (RES) have neuroprotective properties. Administration of RES to culture media protects a wide variety of neuronal cell types from stress-induced death. Dietary supplementation of RES can ameliorate neuronal damage and death resulting from both acute and chronic stresses in rodents. The specific molecular mechanisms by which RES acts at the cellular level remain incompletely understood. However, many experimental data indicate that RES reduces or prevents the occurrence of oxidative damage. Here we discuss possible mechanisms by which RES might exert protection against oxidative damage and cell death. Evidence suggesting that RES’s chemical antioxidant potential is not sufficient explanation for its effects is discussed. Putative biological activities, including interactions with estrogen receptors and sirtuins are critically discussed. We provide a synthesis of how RES’s phytoestrogenic properties might mediate the neuronal stress resistance underlying its observed neuroprotective properties. http://www.mdpi.com/1420-3049/15/3/1196 Tue, 02 Mar 2010 23:00:01 GMT Molecules 2010-03-03 15 3 Review 1196 1212 1420-3049 trans-Resveratrol as A Neuroprotectant 2010-03-03 doi:10.3390/molecules15031196 Ellen L. Robb Jeffrey A. Stuart http://www.mdpi.com/1420-3049/15/3/1168 Both acute and chronic degenerative diseases of the nervous system reduce the viability and function of neurons through changes in intracellular calcium signaling. In particular, pathological increases in the intracellular calcium concentration promote such pathogenesis. Disease involvement of numerous regulators of intracellular calcium signaling located on the plasma membrane and intracellular organelles has been documented. Diverse groups of chemical compounds targeting ion channels, G-protein coupled receptors, pumps and enzymes have been identified as potential neuroprotectants. The present review summarizes the discovery, mechanisms and biological activity of neuroprotective molecules targeting proteins that control intracellular calcium signaling to preserve or restore structure and function of the nervous system. Disease relevance, clinical applications and new technologies for the identification of such molecules are being discussed. http://www.mdpi.com/1420-3049/15/3/1168 Tue, 02 Mar 2010 23:00:01 GMT Molecules 2010-03-03 15 3 Review 1168 1195 1420-3049 Control of Intracellular Calcium Signaling as a Neuroprotective Strategy 2010-03-03 doi:10.3390/molecules15031168 R. Scott Duncan Daryl L. Goad Michael A. Grillo Simon Kaja Andrew J. Payne Peter Koulen http://www.mdpi.com/1420-3049/15/3/1161 A new geldanamycin analogue was isolated from Streptomyces hygroscopicus A070101. The structure was elucidated as 11-methoxy-17-formyl-17-demethoxy-18-O-21-O-dihydrogeldanamycin (1) on the basis of extensive 1D and 2D NMR as well as HRESI-MS spectroscopic data analysis. Compound 1 showed considerable cytotoxicity (SRB) against human cancer cell lines (breast cancer MCF-7, skin melanoma SK-MEL-2 and lung carcinoma COR-L23). http://www.mdpi.com/1420-3049/15/3/1161 Tue, 02 Mar 2010 23:00:01 GMT Molecules 2010-03-03 15 3 Communication 1161 1167 1420-3049 A New Geldanamycin Analogue from Streptomyces hygroscopicus 2010-03-03 doi:10.3390/molecules15031161 Hao Zhang Guang-Zhi Sun Xiang Li Hong-Yu Pan Yan-Sheng Zhang http://www.mdpi.com/1420-3049/15/3/1154 (S)-N-methylpyrrolidine-2-carboxylate, a derivative of natural L-proline, was found to be an efficient ligand for the copper-catalyzed Goldberg-type N-arylation of amides with aryl halides under mild conditions. A variety of N-arylamides were synthesized in good to high yields. http://www.mdpi.com/1420-3049/15/3/1154 Mon, 01 Mar 2010 23:00:01 GMT Molecules 2010-03-02 15 3 Article 1154 1160 1420-3049 Copper-Catalyzed N-Arylation of Amides Using (S)-N-Methylpyrrolidine-2-carboxylate as the Ligand 2010-03-02 doi:10.3390/molecules15031154 Chaoyu Wang Lijuan Liu Wei Wang Dong-Sheng Ma Hua Zhang http://www.mdpi.com/1420-3049/15/3/1141 Yan73 is a “teinturier” red wine variety cultivated in China and used in winemaking to strengthen red wine color. Here, the anthocyanin profile in both the skin and pulp of this grape variety was analyzed by HPLC-MS. The results showed that 18 anthocyanins were detected in both the skin and the pulp, and pelargonidin-3-O-glucoside, an anthocyanin compound hardly detected in most other Vitis viniferaberries, was found. However, the contents of individual anthocyanins in the skin and the pulp were significantly different. Compared with the skin, the pulp exhibited much lower ratio of 3’,5’-substituted to 3’-substituted anthocyanins and much higher ratio of methoxylation of anthocyanin B-ring to non methoxylation, and with regard to the aromatic acylated and aliphatic acylated anthocyanins, both their contents in the skin are higher than in the pulp. The findings will provide some new insight for the tissue-specific expression and regulation of the genes involving in anthocyanin biosynthesis in grape berries. http://www.mdpi.com/1420-3049/15/3/1141 Mon, 01 Mar 2010 23:00:01 GMT Molecules 2010-03-02 15 3 Article 1141 1153 1420-3049 Different Anthocyanin Profiles of the Skin and the Pulp of Yan73 (Muscat Hamburg × Alicante Bouschet) Grape Berries 2010-03-02 doi:10.3390/molecules15031141 Jian-Jun He Yan-Xia Liu Qiu-Hong Pan Xiang-Yun Cui Chang-Qing Duan http://www.mdpi.com/1420-3049/15/3/1127 We have selected aptamers binding to lysozyme from a DNA library using capillary electrophoresis-systematic evolution of ligands by exponential enrichment. During the selection process the dissociation constant of the ssDNA pool decreased from the micromolar to the low nanomolar range within five rounds of selection. The final aptamer had a dissociation constant of 2.8 ± 0.3 nM, 6.1 ± 0.5 nM, and 52.9 ± 9.1 nM as determined by fluorescence anisotropy, surface plasmon resonance and affinity capillary electrophoresis respectively. The aptamers were successfully challenged for specificity against other egg white proteins. The high affinity aptamers open up possibilities for the development of aptamer based food and medical diagnostics. http://www.mdpi.com/1420-3049/15/3/1127 Mon, 01 Mar 2010 23:00:01 GMT Molecules 2010-03-02 15 3 Article 1127 1140 1420-3049 Selection and Characterization of DNA Aptamers for Egg White Lysozyme 2010-03-02 doi:10.3390/molecules15031127 Dinh T. Tran Kris P. F. Janssen Jeroen Pollet Elke Lammertyn Jozef Anné Ann Van Schepdael Jeroen Lammertyn http://www.mdpi.com/1420-3049/15/3/1113 The course of reaction of aryl and heteroaryl sulfonamides with diphenylcarbonate (DPC) and 4-dimethylaminopyridine (DMAP) was found to depend on the pKa of the sulfonamide used. Aryl sulfonamides with pKa ~ 10 gave 4-dimethylamino-pyridinium arylsulfonyl-carbamoylides, while the more acidic heteroaryl sulfonamides (pKa ~ 8) furnished 4-dimethylaminopyridinium heteroarylsulfonyl carbamates. Both the carbamoylides and carbamate salts reacted with aliphatic and aromatic amines with the formation of appropriate aryl(heteroaryl)sulfonyl ureas, and therefore, can be regarded as safe and stable substitutes of the hazardous and difficult to handle aryl(heteroaryl)sulfonyl isocyanates. http://www.mdpi.com/1420-3049/15/3/1113 Thu, 25 Feb 2010 23:00:01 GMT Molecules 2010-02-26 15 3 Article 1113 1126 1420-3049 Synthesis of Novel Aryl(heteroaryl)sulfonyl Ureas of Possible Biological Interest 2010-02-26 doi:10.3390/molecules15031113 Franciszek Sączewski Anna Kuchnio Monika Samsel Marta Łobocka Agnieszka Kiedrowska Karolina Lisewska Jarosław Sączewski Maria Gdaniec Patrick J. Bednarski http://www.mdpi.com/1420-3049/15/3/1103 Compoundswith two phenolic OH groups like curcumin possess efficient antioxidant and anti-inflammatory activity. We synthesized p-cresol dimer (2,2'-dihydroxy-5,5'-dimethylbiphenol, 2a) and p-methoxyphenol dimer (2,2'-dihydroxy-5,5'-dimethoxybiphenol, 2b) by ortho-ortho coupling reactions of the parent monomers, p-cresol (1a) and p-methoxyphenol (1b), respectively. Their antioxidant activity was determined using the induction period method, and their cytotoxicity towards RAW 264.7 cells was also investigated using a cell counting kit. The stoichiometric factors n (number of free radicals trapped by one mole of antioxidant moiety) for 2a and 2b were 3 and 2.8, respectively, being greater than those for 1a and 1b. The ratio of the rate constant of inhibition to that of propagation (kinh/kp) for 2a and 2b was similar to that for 2-t-butyl-4-methoxyphenol (BHA), a conventional food antioxidant. The 50% inhibitory dose (ID50) declined in the order 1b > 1a >> 2b > 2a > BHA. The cytotoxicity for 2a and 2b was significantly greater than that for the parent monomers (p < 0.001), but smaller than that for BHA (p < 0.01). Compounds 2a and 2b may be useful as food antioxidants. http://www.mdpi.com/1420-3049/15/3/1103 Thu, 25 Feb 2010 23:00:01 GMT Molecules 2010-02-26 15 3 Article 1103 1112 1420-3049 Radical-Scavenging Activity and Cytotoxicity of p-Methoxyphenol and p-Cresol Dimers 2010-02-26 doi:10.3390/molecules15031103 Yoshinori Kadoma Yukio Murakami Takako Ogiwara Mamoru Machino Ichiro Yokoe Seiichiro Fujisawa http://www.mdpi.com/1420-3049/15/3/1097 A new flavone, named crotoncaudatin (1), was isolated from the stems of Croton caudatus Geisel. var. tomentosus Hook., together with nine known analogues: 3,5,6,7,8,3′,4′-heptamethoxyflavone (2), tangeretin (3), nobiletin (4), 5,6,7,4′-tetramethoxy-flavone (5), sinensetin (6), kaempferol (7), tiliroside (8), kaempferol-3-O-rutinoside (9) and rutin (10). The structures of the above compounds were established by a combination of spectroscopic methods, including HR-ESI-MS, 1H-NMR, 13C-NMR, HMQC and HMBC spectra. All compounds were isolated from and identified in this species for the first time and compounds 1-6 are new for the genus Croton. http://www.mdpi.com/1420-3049/15/3/1097 Thu, 25 Feb 2010 23:00:01 GMT Molecules 2010-02-26 15 3 Article 1097 1102 1420-3049 Flavonoids from the Stems of Croton caudatus Geisel. var. tomentosus Hook 2010-02-26 doi:10.3390/molecules15031097 Guo-An Zou Zhi-Heng Su Hong-Wu Zhang Yuan Wang Jun-Shan Yang Zhong-Mei Zou http://www.mdpi.com/1420-3049/15/2/1089 Two new polyynes, named oplopantriol A (5) and oplopantriol B (6), were isolated from the root bark of Oplopanax horridus (Smith) Miq, an ethnic medicinal plant of North America, along with four known polyynes: (3S,8S)-falcarindiol (1), oplopandiol (2), (11S,16S,9Z)-9,17-octadecadiene-12,14-diyne-1,11,16-triol, 1-acetate (3) and oplopandiol acetate (4). The structures of the new compounds were elucidated by detailed spectroscopic analyses, including 1D and 2D NMR techniques and chemical methods. The absolute configurations of the new compounds 5 and 6 were determined by comparing their optical rotation values with the hydrolysis products of the known compounds 3 and 4, respectively, derived from the same plant. On the basis of an analysis of their physical and chemical properties we show that the alkaline hydrolysis of 3 and 4 afforded the new compounds 5 and 6, respectively. http://www.mdpi.com/1420-3049/15/2/1089 Mon, 22 Feb 2010 23:00:01 GMT Molecules 2010-02-23 15 2 Article 1089 1096 1420-3049 Isolation and Identification of Two New Polyynes from a North American Ethnic Medicinal Plant--Oplopanax horridus (Smith) Miq. 2010-02-23 doi:10.3390/molecules15021089 Wei-Hua Huang Qing-Wen Zhang Chong-Zhi Wang Chun-Su Yuan Shao-Ping Li http://www.mdpi.com/1420-3049/15/2/1082 Because of their interesting biological properties various methods for the synthesis of substituted pyrroles are described in the literature. However, synthesis of pyrroles fused with a β-lactam ring has not been reported. Our group has demonstrated synthesis and biological evaluation of various β-lactams as anticancer agents. The anticancer activities of these compounds have prompted us to study the synthesis of pyrroles bound to the β-lactams. We have identified an expeditious synthetic method for the preparation of pyrroles fused with β-lactams by reacting 3-amino β-lactams with acetonylacetone in the presence of catalytic amounts (5 mol%) of molecular iodine at room temperature. It has also been discovered that the reaction gives products under domestic and automated microwave oven irradiation. To our knowledge, there are no other prior reports that describe the synthesis of pyrrole-substituted β-lactams. http://www.mdpi.com/1420-3049/15/2/1082 Mon, 22 Feb 2010 23:00:01 GMT Molecules 2010-02-23 15 2 Communication 1082 1088 1420-3049 Remarkable Iodine-Catalyzed Synthesis of Novel Pyrrole- Bearing N-Polyaromatic β-Lactams 2010-02-23 doi:10.3390/molecules15021082 Debasish Bandyopadhyay Gildardo Rivera Isabel Salinas Hector Aguilar Bimal K. Banik http://www.mdpi.com/1420-3049/15/2/1074 Ten novel 4-(4,6-dimethoxypyrimidin-2-yloxy)phenoxy acetates and 4-(4,6-dimethylpyrimidin-2-yloxy)phenoxy acetates were synthesized with hydroquinone, 2-methylsulfonyl-4,6-disubstituted-pyrimidine and chloroacetic ester as starting materials. The products were characterized by IR, 1H-NMR, MS spectra and elemental analyses. Preliminary bioassay indicates that the target compounds possess high herbicidal activity against monocotyledonous plants such as Digitaria sanguinalis L. at concentrations of 100 mg/L and 50 mg/L. http://www.mdpi.com/1420-3049/15/2/1074 Mon, 22 Feb 2010 23:00:01 GMT Molecules 2010-02-23 15 2 Article 1074 1081 1420-3049 Synthesis and Biological activity of 4-(4,6-Disubstituted-pyrimidin-2-yloxy)phenoxy Acetates 2010-02-23 doi:10.3390/molecules15021074 Lin Jiang Hao Wang Maorong Wang Xinhuan Teng http://www.mdpi.com/1420-3049/15/2/1041 An overview of the synthesis and applications of chiral 2,3-epoxy alcohols containing unsaturated chains is presented. One of the fundamental synthetic routes to these compounds is Sharpless asymmetric epoxidation, which is reliable, highly chemoselective and enables easy prediction of the product enantioselectivity. Thus, unsaturated epoxy alcohols are readily obtained by selective oxidation of the allylic double bond in the presence of other carbon-carbon double or triple bonds. The wide availability of epoxy alcohols with unsaturated chains, the versatility of the epoxy alcohol functionality (e.g. regio- and stereo-selective ring opening; oxidation; and reduction), and the arsenal of established alkene chemistries, make unsaturated epoxy alcohols powerful starting materials for the synthesis of complex targets such as biologically active molecules. The popularization of ring-closing metathesis has further increased their value, making them excellent precursors to cyclic compounds. http://www.mdpi.com/1420-3049/15/2/1041 Mon, 22 Feb 2010 23:00:01 GMT Molecules 2010-02-23 15 2 Review 1041 1073 1420-3049 Synthetic Applications of Chiral Unsaturated Epoxy Alcohols Prepared by Sharpless Asymmetric Epoxidation 2010-02-23 doi:10.3390/molecules15021041 Antoni Riera María Moreno http://www.mdpi.com/1420-3049/15/2/1028 Novel Ru(II) complex-based hybrid inorganic-organic materials immobilized via a diamine co-ligand site instead of the conventional diphosphine ligand have been prepared. The complexes were prepared by two different methods: sol-gel and surface modification techniques. The structures of the desired materials were deduced by several available physical measurements like elemental analyses, infrared, FAB-MS and 1H-, 13C- and 31P-NMR spectroscopy. Due to a lack of solubility the structures of xerogel 3 and modified 4 were studied by solid state 13C-, 29Si- and 31P-NMR spectroscopy, infrared spectroscopy and EXAFS. These materials were stable enough to serve as hydrogenation catalysts. Selective hydrogenation of functionalized carbonyls in a,b-unsaturated compounds was successfully carried out under mild conditions in a basic medium using these complexes as catalysts. http://www.mdpi.com/1420-3049/15/2/1028 Mon, 22 Feb 2010 23:00:01 GMT Molecules 2010-02-23 15 2 Article 1028 1040 1420-3049 Synthesis and Characterization of Novel Inorganic-Organic Hybrid Ru(II) Complexes and Their Application in Selective Hydrogenation 2010-02-23 doi:10.3390/molecules15021028 Ismail Warad Zeid Al-Othman Saud Al-Resayes Salem S. Al-Deyab El-Refaie Kenawy http://www.mdpi.com/1420-3049/15/2/1007 Medical-grade polyvinyl chloride was coated by polysaccharides through a novel physicochemical approach. An initial surface activation was performed foremost via diffuse coplanar surface barrier discharge plasma in air at ambient temperature and pressure. Then, radical graft copolymerization of acrylic acid through grafting-from pathway was directed to render a well-defined brush of high density, and finally a chitosan monolayer and chitosan/pectin alternating multilayer were bound onto the functionalized surfaces. Surface characteristics were systematically investigated using several probe techniques. In vitro bacterial adhesion and biofilm formation assays indicated that a single chitosan layer was incapable of hindering the adhesion of a Staphylococcus aureus bacterial strain, while up to 30% reduction was achieved by the chitosan/pectin layered assembly. On the other hand, chitosan and chitosan/pectin multilayer could retard Escherichia coli adhesion by 50% and 20%, respectively. Furthermore, plasma treated and graft copolymerized samples were also found effective to diminish the degree of adherence of Escherichia coli. http://www.mdpi.com/1420-3049/15/2/1007 Mon, 22 Feb 2010 23:00:01 GMT Molecules 2010-02-23 15 2 Article 1007 1027 1420-3049 Polysaccharides Coatings on Medical-Grade PVC: A Probe into Surface Characteristics and the Extent of Bacterial Adhesion 2010-02-23 doi:10.3390/molecules15021007 Ahmad Asadinezhad Igor Novák Marián Lehocký František Bílek Alenka Vesel Ita Junkar Petr Sáha Anton Popelka http://www.mdpi.com/1420-3049/15/2/997 The title compounds, (4-trifluoromethoxyphenyl)-2,5-dimethyl-3-(2-R-thiazol-4-yl)-1H-pyrroles, were prepared in four steps starting from commercially available 4-trifluoromethoxyaniline. The pyrrole (second ring) was added in one step using the Paal-Knorr method. The thiazole (third ring) was added in three steps using chloroacylation with chloroacetonitrile followed by heterocyclization with thioamides/thioureas. http://www.mdpi.com/1420-3049/15/2/997 Mon, 22 Feb 2010 23:00:01 GMT Molecules 2010-02-23 15 2 Article 997 1006 1420-3049 Synthesis of 1-(4-Trifluoromethoxyphenyl)-2,5-dimethyl-3-(2-R-thiazol-4-yl)-1H-pyrroles via Chain Heterocyclization 2010-02-23 doi:10.3390/molecules15020997 Mykhaylo V. Vovk Oleksandr M. Pinchuk Andrij O. Tolmachov Andrei A. Gakh http://www.mdpi.com/1420-3049/15/2/988 Thiosemicarbazone analogs of papaveraldine and related compounds 1–6 were synthesized and evaluated for cytotoxic and antimalarial activities. The cytotoxic activity was tested against HuCCA-1, HepG2, A549 and MOLT-3 human cancer cell lines. Thiosemicarbazones 1–5 displayed cytotoxicity toward all the tested cell lines, while compounds 2–5 selectively showed potent activity against the MOLT-3 cell lines. Significantly, N(4)-phenyl-2-benzoylpyridine thiosemicarbazone 4 exhibited the most potent activity against HuCCA-1, HepG2, A549 and MOLT-3 cell lines with IC50 values of 0.03, 4.75, 0.04 and 0.004 µg/mL, respectively. In addition, 2-benzoylpyridine thio-semicarbazones 3 and 4 showed antimalarial activity against Plasmodium falciparum with IC50 of 10-7 to < 10-6 M. The study demonstrates the quite promising activity of analog 4 as a lead molecule for further development. http://www.mdpi.com/1420-3049/15/2/988 Mon, 22 Feb 2010 23:00:01 GMT Molecules 2010-02-23 15 2 Article 988 996 1420-3049 Synthesis, Cytotoxic and Antimalarial Activities of Benzoyl Thiosemicarbazone Analogs of Isoquinoline and Related Compounds 2010-02-23 doi:10.3390/molecules15020988 Ratchanok Pingaew Supaluk Prachayasittikul Somsak Ruchirawat http://www.mdpi.com/1420-3049/15/2/959 By-products derived from food processing are attractive source for their valuable bioactive components and color pigments. These by-products are useful for development as functional foods, nutraceuticals, food ingredients, additives, and also as cosmetic products. Lycopene is a bioactive red colored pigment naturally occurring in plants. Industrial by-products obtained from the plants are the good sources of lycopene. Interest in lycopene is increasing due to increasing evidence proving its preventive properties toward numerous diseases. In vitro, in vivo and ex vivo studies have demonstrated that lycopene-rich foods are inversely associated to diseases such as cancers, cardiovascular diseases, diabetes, and others. This paper also reviews the properties, absorption, transportation, and distribution of lycopene and its by-products in human body. The mechanism of action and interaction of lycopene with other bioactive compounds are also discussed, because these are the crucial features for beneficial role of lycopene. However, information on the effect of food processing on lycopene stability and availability was discussed for better understanding of its characteristics. http://www.mdpi.com/1420-3049/15/2/959 Mon, 22 Feb 2010 23:00:01 GMT Molecules 2010-02-23 15 2 Review 959 987 1420-3049 Revealing the Power of the Natural Red Pigment Lycopene 2010-02-23 doi:10.3390/molecules15020959 Kin-Weng Kong Hock-Eng Khoo K. Nagendra Prasad Amin Ismail Chin-Ping Tan Nor Fadilah Rajab http://www.mdpi.com/1420-3049/15/2/917 Organocatalytic asymmetric α-oxidation and amination reactions of carbonyl compounds are highly useful synthetic methodologies, especially in generating chiral building blocks that previously have not been easily accessible by traditional methods. The concept is relatively new and therefore the list of new catalysts, oxidizing and aminating reagents, as well as new substrates, are expanding at an amazing rate. The scope of this review includes new reactions and catalysts, mechanistic aspects and synthetic applications of α-oxidation, hydroxylation, aminoxylation, amination, hydrazination, hydroxyamination and related α-heteroatom functionalization of aldehydes, ketones and related active methylene compounds published during 2005–2009. http://www.mdpi.com/1420-3049/15/2/917 Wed, 10 Feb 2010 23:00:01 GMT Molecules 2010-02-11 15 2 Review 917 958 1420-3049 Organocatalyzed Asymmetric α-Oxidation, α-Aminoxylation and α-Amination of Carbonyl Compounds 2010-02-11 doi:10.3390/molecules15020917 Tirayut Vilaivan Worawan Bhanthumnavin http://www.mdpi.com/1420-3049/15/2/878 Huntington’s disease (HD) is an inheritable autosomal-dominant disorder whose causal mechanisms remain unknown. Experimental models have begun to uncover these pathways, thus helping to understand the mechanisms implicated and allowing for the characterization of potential targets for new therapeutic strategies. 3-Nitropropionic acid is known to produce in animals behavioural, biochemical and morphologic changes similar to those occurring in HD. For this reason, this phenotypic model is gaining attention as a valuable tool to mimick this disorder and further developing new therapies. In this review, we will focus on the past and present research of this molecule, to finally bring a perspective on what will be next in this promising field of study. http://www.mdpi.com/1420-3049/15/2/878 Tue, 09 Feb 2010 23:00:01 GMT Molecules 2010-02-10 15 2 Review 878 916 1420-3049 3-Nitropropionic Acid as a Tool to Study the Mechanisms Involved in Huntington’s Disease: Past, Present and Future 2010-02-10 doi:10.3390/molecules15020878 Isaac Túnez Inmaculada Tasset Verónica Pérez-De La Cruz Abel Santamaría http://www.mdpi.com/1420-3049/15/2/871 A new 1,4-diazepine, callysponine (1), was isolated from a South China Sea Callyspongia sp. marine sponge, together with four known proline-based diketopiperazines: cyclo-(S-Pro-R-Leu) (2), cyclo-(S-Pro-R-Val) (3), cyclo-(S-Pro-R-Ala) (4), andcyclo-(S-Pro-R-Tyr) (5). The new structure was determined on the basis of NMR and MS analysis, and the absolute stereochemistry was defined by NOESY spectroscopy and optical rotation. The structures of the known compounds were identified by comparison of their spectroscopic data with those reported in the literature. Callysponine (1) did not inhibit the growth of HepG2 (hepatoma carcinoma cell), A549 (lung carcinoma cell), and HeLa (cervical cancer cell) cell lines. http://www.mdpi.com/1420-3049/15/2/871 Tue, 09 Feb 2010 23:00:01 GMT Molecules 2010-02-10 15 2 Article 871 877 1420-3049 A New 1,4-Diazepine from South China Sea Marine Sponge Callyspongia Species 2010-02-10 doi:10.3390/molecules15020871 Ri-Ming Huang Wei Ma Jun-De Dong Xue-Feng Zhou Tunhai Xu Kyung Jin Lee Xianwen Yang Shi-Hai Xu Yonghong Liu http://www.mdpi.com/1420-3049/15/2/857 P-glycoprotein (P-gp) is one of the ABC transporters responsible for the resistance of several tumours to successful chemotherapy. Numerous agents are capable of interfering with the P-gp-mediated export of drugs but unfortunately most of them produce serious side effects. Some plant polyphenols, including the flavonol quercetin (Q), manifest anti-neoplastic activity mainly due to their influence on cell cycle control and apoptosis. Reports are also available which show that Q may intensify action of cytostatic drugs and suppress the multidrug resistance (MDR) phenomenon. The study aimed at determination if Q sensitizes cells resistant to daunorubicin (DB) through its effect on P-gp expression and action. The experiments were conducted on two cell lines of human pancreatic carcinoma, resistant to DB EPP85-181RDB and sensitive EPP85-181P as a comparison. Cells of both lines were exposed to selected concentrations of Q and DB, and then membranous expression of P-gp and its transport function were examined. The influence on expression of gene for P-gp (ABCB1) was also investigated. Results of the studies confirmed that Q affects expression and function of P-gp in a concentration-dependent manner. Moreover it decreased expression of ABCB1. Thus, Q may be considered as a potential modulator of P-gp. http://www.mdpi.com/1420-3049/15/2/857 Mon, 08 Feb 2010 23:00:01 GMT Molecules 2010-02-09 15 2 Article 857 870 1420-3049 Quercetin as a Potential Modulator of P-Glycoprotein Expression and Function in Cells of Human Pancreatic Carcinoma Line Resistant to Daunorubicin 2010-02-09 doi:10.3390/molecules15020857 Sylwia Borska Miroslaw Sopel Magdalena Chmielewska Maciej Zabel Piotr Dziegiel http://www.mdpi.com/1420-3049/15/2/842 Oligo(ε-caprolactone) and oligolactide were synthesized via ring-opening polymerization of cyclic esters in the presence of creatinine as initiators. Thus obtained oligomers were successfully used in the synthesis of novel polyurethane conjugates of norfloxacin. The structures of the polymers and conjugates were elucidated by means of MALDI-TOF MS, NMR and IR studies. http://www.mdpi.com/1420-3049/15/2/842 Thu, 04 Feb 2010 23:00:01 GMT Molecules 2010-02-05 15 2 Article 842 856 1420-3049 Seeking Polymeric Prodrugs of Norfloxacin. Part 2. Synthesis and Structural Analysis of Polyurethane Conjugates 2010-02-05 doi:10.3390/molecules15020842 Marcin Sobczak Katarzyna Nurzyńska Waclaw Kolodziejski http://www.mdpi.com/1420-3049/15/2/834 A new scalarane sesterterpene, phyllofolactone M (1), and a new sterol, (24E)-5α,6α-epoxystigmasta-7,24(28)-dien-3β-ol (3), together with a known sesterterpene, phyllofolactone B (2), were isolated from the South China Sea sponge Phyllospongia foliascens. Their structures were elucidated by spectroscopic analysis and comparison with known compounds. In addition, previous NMR data assignments for the known sesterterpene phyllofolactone B (2) were revised. http://www.mdpi.com/1420-3049/15/2/834 Thu, 04 Feb 2010 23:00:01 GMT Molecules 2010-02-05 15 2 Article 834 841 1420-3049 Sesterterpenes and a New Sterol from the Marine Sponge Phyllospongia foliascens 2010-02-05 doi:10.3390/molecules15020834 Hong-Jun Zhang Yang-Hua Yi Fan Yang Wan-Sheng Chen Hou-Wen Lin http://www.mdpi.com/1420-3049/15/2/824 Ceramides play a crucial role in the barrier function of the skin as well as in transmembrane signaling. In this study long aliphatic chain tartaric acid diamides able to replace ceramides in an in vitro model of the stratum corneum lipid matrix due to their similar physico-chemical properties were synthesized from diacetoxysuccinic anhydride in four steps. Their pro-apoptotic effect on fibroblast cells was also investigated. http://www.mdpi.com/1420-3049/15/2/824 Thu, 04 Feb 2010 23:00:01 GMT Molecules 2010-02-05 15 2 Article 824 833 1420-3049 Synthesis and Characterization of Long-Chain Tartaric Acid Diamides as Novel Ceramide-Like Compounds 2010-02-05 doi:10.3390/molecules15020824 Bálint Sinkó Melinda Pálfi Szabolcs Béni József Kökösi Krisztina Takács-Novák http://www.mdpi.com/1420-3049/15/2/813 A sustainable Knoevenagel condensation of a series of aldehydes with malononitrile and ethyl cyanoacetate is described. The process is based on the combination of microwave activation and hydroxyapatite catalysis under solvent-free conditions. Products are obtained in and high yields after short reaction times. The effects of the specific surface of porous calcium hydroxyapatite and microwave activation are discussed. http://www.mdpi.com/1420-3049/15/2/813 Wed, 03 Feb 2010 23:00:01 GMT Molecules 2010-02-04 15 2 Article 813 823 1420-3049 Microwave-Assisted and Efficient Solvent-free Knoevenagel Condensation. A Sustainable Protocol Using Porous Calcium Hydroxyapatite as Catalyst 2010-02-04 doi:10.3390/molecules15020813 Siham Mallouk Khalid Bougrin Abdelaziz Laghzizil Rachid Benhida http://www.mdpi.com/1420-3049/15/2/804 Ancient Chinese herbal texts as far back as the 4th Century Zhou hou bei ji fang describe methods for the use of Qing Hao (Artemisia annua) for the treatment of intermittent fevers. Today, the A. annua constituent artemisinin is an important antimalarial drug and the herb itself is being grown and used locally for malaria treatment although this practice is controversial. Here we show that the ancient Chinese methods that involved either soaking, (followed by wringing) or pounding, (followed by squeezing) the fresh herb are more effective in producing artemisinin-rich extracts than the usual current method of preparing herbal teas from the dried herb. The concentrations of artemisinin in the extracts was up to 20-fold higher than that in a herbal tea prepared from the dried herb, but the amount of total artemisinin extracted by the Chinese methods was much less than that removed in the herbal tea. While both extracts exhibited potent in vitro activities against Plasmodium falciparum, only the pounded juice contained sufficient artemisinin to suppress parasitaemia in P. berghei infected mice. The implications of these results are discussed in the context of malaria treatment using A. annua infusions. http://www.mdpi.com/1420-3049/15/2/804 Wed, 03 Feb 2010 23:00:01 GMT Molecules 2010-02-04 15 2 Article 804 812 1420-3049 Ancient Chinese Methods Are Remarkably Effective for the Preparation of Artemisinin-Rich Extracts of Qing Hao with Potent Antimalarial Activity 2010-02-04 doi:10.3390/molecules15020804 Colin W. Wright Peter A. Linley Reto Brun Sergio Wittlin Elisabeth Hsu http://www.mdpi.com/1420-3049/15/2/793 We report on the solubility of hen lysozyme (HEWL) in aqueous ethylammonium nitrate (EAN) as a function of water content. We find the solubility behavior to be complex, exhibiting both a maximum (400 mg/mL) at very high EAN content) and a minimum at intermediate EAN content. We exploit this solubility profile in a novel approach to generating crystals of hydrophilic proteins, based on rehydration of a high concentration protein solution. We describe the production of crystals of X-ray diffraction quality. Two related ionic liquid solvent systems, with the same solubility profiles but different effective pH characteristics, are identified for future evaluation. http://www.mdpi.com/1420-3049/15/2/793 Wed, 03 Feb 2010 23:00:01 GMT Molecules 2010-02-04 15 2 Communication 793 803 1420-3049 The Solubility of Hen Lysozyme in Ethylammonium Nitrate/H2O Mixtures and a Novel Approach to Protein Crystallization 2010-02-04 doi:10.3390/molecules15020793 Nolene Byrne C. Austen Angell http://www.mdpi.com/1420-3049/15/2/780 Pseudomonas aeruginosa is an opportunistic pathogen which is responsible for a wide range of infections. Production of virulence factors and biofilm formation by P. aeruginosa are partly regulated by cell-to-cell communication quorum-sensing systems. Identification of quorum-quenching reagents which block the quorum-sensing process can facilitate development of novel treatment strategies for P. aeruginosa infections. We have used molecular dynamics simulation and experimental studies to elucidate the efficiencies of two potential quorum-quenching reagents, triclosan and green tea epigallocatechin gallate (EGCG), which both function as inhibitors of the enoyl-acyl carrier protein (ACP) reductase (ENR) from the bacterial type II fatty acid synthesis pathway. Our studies suggest that EGCG has a higher binding affinity towards ENR of P. aeruginosa and is an efficient quorum-quenching reagent. EGCG treatment was further shown to be able to attenuate the production of virulence factors and biofilm formation of P. aeruginosa. http://www.mdpi.com/1420-3049/15/2/780 Tue, 02 Feb 2010 23:00:01 GMT Molecules 2010-02-03 15 2 Article 780 792 1420-3049 Evaluation of Enoyl-Acyl Carrier Protein Reductase Inhibitors as Pseudomonas aeruginosa Quorum-Quenching Reagents 2010-02-03 doi:10.3390/molecules15020780 Liang Yang Yang Liu Claus Sternberg Søren Molin http://www.mdpi.com/1420-3049/15/2/766 Some 3-(Substituted methylthio)-4-phenyl-5-(3,4,5-trimethoxyphenyl)-4H-1,2,4-triazole derivatives were synthesized in six steps starting from easily accessible gallic acid. The resulting sulfides were then catalytically oxidized to the title sulfones with H2O2. The products were obtained in high yield under mild conditions and practically devoid of any by-products. The structures were confirmed by elemental analysis, IR, 1H- and 13C-NMR spectral data. Furthermore, a detailed X-ray crystallography structural analysis of model triazole 7g was carried out. http://www.mdpi.com/1420-3049/15/2/766 Tue, 02 Feb 2010 23:00:01 GMT Molecules 2010-02-03 15 2 Article 766 779 1420-3049 Synthesis and Crystal Structure of Novel Sulfone Derivatives Containing 1,2,4-Triazole Moieties 2010-02-03 doi:10.3390/molecules15020766 Weiming Xu Baoan Song Pinaki Bhadury Yang Song Deyu Hu http://www.mdpi.com/1420-3049/15/2/747 The CeO2 nanorods (CeNR) promote the oxidation of ethylbenzene (PhEt) and cyclohexene with t-BuOOH, at temperatures as low as 55 ºC. For both substrates the saturated C-H bonds are preferentially activated over the unsaturated ones. The catalyst seems fairly stable towards leaching phenomena. The liquid-phase oxidation catalysis may be associated with the Ce3+/Ce4+ inter-conversion in the one-electron redox processes mediating the formation of tert-butyl-(per)oxy radicals. CeNR is very effective in H2O2 disproportionation. Pre-treatment of CeNR with H2O2 or t-BuOOH prior to the catalytic reaction enhances the reaction rate of PhEt with t-BuOOH in comparison to CeNR. Textural characterization and spectroscopic studies suggest that catalytic activation is associated to defect sites. http://www.mdpi.com/1420-3049/15/2/747 Mon, 01 Feb 2010 23:00:01 GMT Molecules 2010-02-02 15 2 Article 747 765 1420-3049 Catalytic Performance of Ceria Nanorods in Liquid-Phase Oxidations of Hydrocarbons with tert-Butyl Hydroperoxide 2010-02-02 doi:10.3390/molecules15020747 Andreia G. Macedo Sílvia E. M. Fernandes Anabela A. Valente Rute. A. S. Ferreira Luís D. Carlos João Rocha http://www.mdpi.com/1420-3049/15/2/735 The chemical composition of the essential oils of Salvia africana L., Salvia elegans Vahl, Salvia greggii A. Gray, Salvia mellifera Green and Salvia munzii Epling, cultivated in Eboli (Salerno, Southern Italy), was studied by means of GC and GC-MS analyses. In all, 88 compounds were identified, 54 for S. africana, accounting for 95.4% of the total oil, 55 for S. elegans (92.9%), 50 for S. greggii (96.9%), 54 for S. mellifera (90.4%) and 47 for S. munzii (97.5%), respectively. In S. africana,the amount of monoterpenoids and sesquiterpenoids is very similar. For other species, the monoterpenoid percentage is greater than the amount of sesquiterpenoids. The oils of S. elegans, S. greggii and S. munzii were active inhibitors of germination and radical elongation of Raphanus sativus L. and Lepidium sativum L. http://www.mdpi.com/1420-3049/15/2/735 Sun, 31 Jan 2010 23:00:01 GMT Molecules 2010-02-01 15 2 Article 735 746 1420-3049 Chemical Composition and Antigerminative Activity of the Essential Oils from Five Salvia Species 2010-02-01 doi:10.3390/molecules15020735 Laura De Martino Graziana Roscigno Emilia Mancini Enrica De Falco Vincenzo De Feo http://www.mdpi.com/1420-3049/15/2/709 Conscious of the importance that stereochemical issues may have on the design of efficient organocatalyts for both Morita-Baylis-Hillman and aza-Morita-Baylis-Hillman reaction we have analyzed them in this minireview. The so-called standard reactions involve “naked” enolates which therefore should lead to the syn adducts as the major products, irrespective of the E, Z stereochemistry of the enolate. Accordingly, provided the second step is rate determining step, the design of successful bifunctional or polyfunctional catalysts has to consider the geometrical requirements imposed by the transition structures of the second step of these reactions. On the other hand, MBH and aza-MBH reactions co-catalyzed by (S)-proline and a secondary or tertiary amine (co-catalyst) involve the aldol-type condensation of either a 3-amino-substituted enamine, dienamine, or both, depending on the cases. A Zimmerman-Traxler mechanism defines the stereochemical issues regarding these co-catalyzed condensations which parallel those of the well established (S)-proline catalyzed aldol-like reactions. http://www.mdpi.com/1420-3049/15/2/709 Sun, 31 Jan 2010 23:00:01 GMT Molecules 2010-02-01 15 2 Review 709 734 1420-3049 Enantioselective, Organocatalytic Morita-Baylis-Hillman and Aza-Morita-Baylis-Hillman Reactions: Stereochemical Issues 2010-02-01 doi:10.3390/molecules15020709 Javier Mansilla José M. Saá http://www.mdpi.com/1420-3049/15/2/699 Using methanesulfonic acid as a catalyst, a series of cyclododeceno[b]indene derivatives were synthesized by the cyclization of α-benzylcyclododecanones, which were prepared by the reactions of cyclododecanones with a variety of substituted benzyl chlorides or bromides using NaH as a base. Their structures were confirmed by mp, IR spectra, 1H-NMR, 13C-NMR, MS, and x-ray diffraction. The preferred conformations were analyzed by crystal structure, 1H-NMR and quantum chemistry calculations, and compared with the x-ray diffraction structure of 2,3,5,6-bis(ortho-1,10-decylidene)dihydropyrazine. The results showed that the cyclododecene moiety adopted a preferred [1ene2333] conformation, and the substituted groups at aromatic ring had no significant influence on the conformation. http://www.mdpi.com/1420-3049/15/2/699 Sun, 31 Jan 2010 23:00:01 GMT Molecules 2010-02-01 15 2 Article 699 708 1420-3049 Facile Synthesis and Preferred Conformation Analysis of Cyclododeceno[b]indene 2010-02-01 doi:10.3390/molecules15020699 Chunyan Zhang Shengyan Gong Li Zhang Daoquan Wang Mingan Wang http://www.mdpi.com/1420-3049/15/2/689 The barks of two endemic Commiphora species namely, Commiphora ornifolia (Balf.f.) Gillett and Commiphora parvifolia Engl., were collected from Soqotra Island in Yemen and their essential oils were obtained by hydrodistillation. The chemical composition of both oils was investigated by GC and GC-MS. Moreover, the essential oils were evaluated for their antimicrobial activity against two Gram-positive bacteria, two Gram-negative bacteria and one yeast species by using a broth micro-dilution assay for minimum inhibitory concentrations (MIC) and for their antioxidant activity by measuring the DPPH radical scavenging activity. A total of 45 constituents of C. ornifolia (85.6%) and 44 constituents of C. parvifolia (87.1%) were identified. The oil of C. ornifolia was characterized by a high content of oxygenated monoterpenes (56.3%), of which camphor (27.3%), α-fenchol (15.5%), fenchone (4.4%) and borneol (2.9%) were identified as the main components. High contents of oxygenated sesquiterpenes (36.1%) and aliphatic acids (22.8%) were found in C. parvifolia oil, in which caryophyllene oxide (14.2%), β-eudesmol (7.7%), bulnesol (5.7%), T-cadinol (3.7%) and hexadecanoic acid (18.4%) predominated. The results of the antimicrobial assay showed that both oils exhibited moderate to high antibacterial activity especially against Gram-positive bacteria. C. ornifolia oil was the most active. In addition, the DPPH-radical scavenging assay exhibited only weak antioxidant activities for both oils at the high concentration tested. http://www.mdpi.com/1420-3049/15/2/689 Sun, 31 Jan 2010 23:00:01 GMT Molecules 2010-02-01 15 2 Article 689 698 1420-3049 Chemical Analysis and Biological Activity of the Essential Oils of Two Endemic Soqotri Commiphora Species 2010-02-01 doi:10.3390/molecules15020689 Ramzi A. Mothana Adnan J. Al-Rehaily Wulf Schultze http://www.mdpi.com/1420-3049/15/2/680 Harvested longan (Dimocarpus longan Lour.) fruit are susceptible to decay caused by both bacterial and fungal infections. Ochratoxin A (OTA) is a kind of mycotoxin produced by a number of fungi. In this study, OTA was extracted from longan fruit pulp by 80% methanol and then loaded on C-18 solid-phase extraction columns. The extract solution was then analyzed by high-performance liquid chromatography - fluorescence detection (HPLC-FD) and an electron spray ionization-mass spectrometry (ESI-MS), respectively. The HPLC-FD analysis showed that a compound similar to OTA might exist in longan fruit pulp, but further analysis by the ESI-MS method demonstrated that OTA was not present in the longan pulp, indicating that the presence of OTA in longan fruit pulp detected by the HPLC-FD analysis needed to be confirmed by the ESI-MS method. http://www.mdpi.com/1420-3049/15/2/680 Thu, 28 Jan 2010 23:00:01 GMT Molecules 2010-01-29 15 2 Article 680 688 1420-3049 A Comparative Identification of Ochratoxin A in Longan Fruit Pulp by High Performance Liquid Chromatography-Fluorescence Detection and Electron Spray Ionization-Mass Spectrometry 2010-01-29 doi:10.3390/molecules15020680 Jing Li Haihui Xie Bao Yang Xinhong Dong Linyan Feng Feng Chen Yueming Jiang http://www.mdpi.com/1420-3049/15/2/672 A new flavone C-glycoside, isovitexin 6″-O-E-p-coumarate (1) and two known flavonoid glycosides—quercetin 3-O-β-D-glucuronopyranoside (2) and isoorientin (3)—were isolated from an ethanol extract of aerial parts of Clematis rehderiana. Their structures were determined by spectroscopic methods. The antioxidant effects of the two flavone C-glycosides were evaluated by both the MTT and DPPH assays. Compound 1 showed potent activities against H2O2-induced impairment in PC12 cells within the concentration range tested, whereas compound 3 scavenged DPPH radical strongly, with an IC50 value of 13.5 μM. http://www.mdpi.com/1420-3049/15/2/672 Thu, 28 Jan 2010 23:00:01 GMT Molecules 2010-01-29 15 2 Communication 672 679 1420-3049 A New Flavone C-Glycoside from Clematis rehderiana 2010-01-29 doi:10.3390/molecules15020672 Zhi-Zhi Du Xian-Wen Yang Hao Han Xiang-Hai Cai Xiao-Dong Luo http://www.mdpi.com/1420-3049/15/2/660 A series of eighteen azomethines has been synthesized by the reaction of appropriate primary aromatic amines with aryl and/or heteroaryl carboxaldehydes. The synthesized azomethines have been evaluated for their in vitro antileishmanial, antibacterial and antifungal activities. The results revealed some antifungal activity of most of the synthesized compounds, whereas the antileishmaniasis activity results highlighted that all synthesized azomethines inhibited parasite growth and most of them showed highly potent action towards Leishmania major promastigotes. No remarkable bactericidal activities were observed. http://www.mdpi.com/1420-3049/15/2/660 Wed, 27 Jan 2010 23:00:01 GMT Molecules 2010-01-28 15 2 Article 660 671 1420-3049 Antileishmanial, Antimicrobial and Antifungal Activities of Some New Aryl Azomethines 2010-01-28 doi:10.3390/molecules15020660 Yasser M.S.A. Al-Kahraman Hassan. M.F. Madkour Dildar Ali Masoom Yasinzai http://www.mdpi.com/1420-3049/15/2/649 An efficient and stereoselective catalytic system for the Heck cross coupling reaction using novel 1,3-dialkyl-3,4,5,6-tetrahydropyrimidinium salts (1, LHX) and Pd(OAc)2 loading has been reported. The palladium complexes derived from the salts 1a-f prepared in situ exhibit good catalytic activity in the Heck coupling reaction of aryl bromides under mild conditions. http://www.mdpi.com/1420-3049/15/2/649 Wed, 27 Jan 2010 23:00:01 GMT Molecules 2010-01-28 15 2 Article 649 659 1420-3049 Palladium-Catalyzed Heck Coupling Reaction of Aryl Bromides in Aqueous Media Using Tetrahydropyrimidinium Salts as Carbene Ligands 2010-01-28 doi:10.3390/molecules15020649 Sedat Yaşar Emine Özge Özcan Nevin Gürbüz Bekir Çetinkaya İsmail Özdemir http://www.mdpi.com/1420-3049/15/2/639 From the twigs of Miliusa mollis Pierre, three new compounds including (2S,3S)-2,3-dihydro-2-(4-methoxyphenyl)-3-methyl-5-[1(E)-propenyl]benzofuran, (7S,8S)- threo-Δ8'-4-methoxyneolignan and tyrosol-1-O-β-xylopyranosyl-(1→6)-O-β-gluco-pyranoside were isolated, along with seven known compounds. Their structures were elucidated through analysis of their spectroscopic data. http://www.mdpi.com/1420-3049/15/2/639 Wed, 27 Jan 2010 23:00:01 GMT Molecules 2010-01-28 15 2 Article 639 648 1420-3049 New Neolignans and a Phenylpropanoid Glycoside from Twigs of Miliusa mollis 2010-01-28 doi:10.3390/molecules15020639 Kanokporn Sawasdee Tanawat Chaowasku Kittisak Likhitwitayawuid http://www.mdpi.com/1420-3049/15/2/627 The essential oil of the stems and fruits of Caralluma europaea (Guss.) N.E.Br. (Apocynaceae) from Lampedusa Island has been obtained by hydrodistillation and its composition analyzed. The analyses allowed the identification and quantification of 74 volatile compounds, of which 16 were aromatic and 58 non-aromatic. Stems and fruits contained 1.4% and 2.7% of aromatic compounds respectively, while non-aromatic were 88.3% and 88.8%. Non-aromatic hydrocarbons were the most abundant compounds in both organs, followed by fatty acids. Data showed differences in the profiles between stems and fruits which shared only eighteen compounds; stems accounted for 38 compounds while fruits for 53. Fruits showed a higher diversity especially in aromatic compounds with twelve versus four in stems. Among the volatiles identified in stems and fruits of C. europaea 26 are present in other taxa of Apocynaceae, 52 are semiochemicals for many insects, and 21 have antimicrobial activity. The possible ecological role of the volatiles found is briefly discussed. http://www.mdpi.com/1420-3049/15/2/627 Tue, 26 Jan 2010 23:00:01 GMT Molecules 2010-01-27 15 2 Article 627 638 1420-3049 Essential Oil Composition of Stems and Fruits of Caralluma europaea N.E.Br. (Apocynaceae) 2010-01-27 doi:10.3390/molecules15020627 Pietro Zito Maurizio Sajeva Maurizio Bruno Antonella Maggio Sergio Rosselli Carmen Formisano Felice Senatore http://www.mdpi.com/1420-3049/15/2/619 In this paper we describe an isothermal rolling-circle amplification (RCA) protocol to detect gene point mutations on chips. The method is based on an allele-specific oligonucleotide circularization mediated by a special DNA ligase. The probe is circularized when perfect complementary sequences between the probe oligonucleotide and HIV cDNA gene. Mismatches around the ligation site can prevent probe circularization. The circularized probe (C-probe) can be amplified by rolling circle amplification to generate multimeric singlestranded DNA (ssDNA) under isothermal conditions. There are four sequence regions to bind respectively with fluorescent probe, RCA primer, solid probe and HIV cDNA template in the C-probe which we designed. These ssDNA products are hybridized with fluorescent probes and solid probes which are immobilized on a glass slide composing a regular microarray pattern. The fluorescence signals can be monitored by a scanner in the presence of HIV cDNA templates, whereas the probes cannot be circularized and signal of fluorescence cannot be found. The RCA array has capability of high-throughput detection of the point mutation and the single-nucleotide polymorphism (SNP).The development of C-probe-based technologies offers a promising prospect for situ detection, microarray, molecular diagnosis, single nucleotide polymorphism, and whole genome amplification. http://www.mdpi.com/1420-3049/15/2/619 Tue, 26 Jan 2010 23:00:01 GMT Molecules 2010-01-27 15 2 Article 619 626 1420-3049 Detection of HIV cDNA Point Mutations with Rolling-Circle Amplification Arrays 2010-01-27 doi:10.3390/molecules15020619 Lingwei Wu Quanjun Liu Zhongwei Wu Zuhong Lu http://www.mdpi.com/1420-3049/15/2/613 Besides two known glycosides, a new furostanol glycoside was isolated from the Fruits of Tribulus terrestris L. The structure of the new furostanol glycoside was established as 26-O-β-D-glucopyranosyl-(25S)-5α-furostane-20(22)-en-12-one-3β, 26-diol-3-O-α-L-rhamnopyranosyl-(1→2)-[β-D-glucopyranosyl-(1→4)]-β-D-galactopyranoside (1) on the basis of 1D and 2D-NMR techniques, including COSY, HMBC, and HMQC correlations. http://www.mdpi.com/1420-3049/15/2/613 Tue, 26 Jan 2010 23:00:01 GMT Molecules 2010-01-27 15 2 Communication 613 618 1420-3049 A New Furostanol Glycoside from Tribulus terrestris 2010-01-27 doi:10.3390/molecules15020613 Yajuan Xu Yonghong Liu Tunhai Xu Shengxu Xie Yunshan Si Yue Liu Haiou Zhou Tonghua Liu Dongming Xu http://www.mdpi.com/1420-3049/15/2/606 Chemical investigation of the EtOH extract of the twigs of Calophyllum inophyllum collected in Hainan Province of China resulted in the isolation of two new prenylated xanthones, caloxanthone O (1) and caloxanthone P (2). Their structures were elucidated by a study of their physical and spectral data. Compound 1 exhibited cytotoxicity against human gastric cancer cell line (SGC-7901),with an IC50 value of 22.4 μg mL-1. http://www.mdpi.com/1420-3049/15/2/606 Tue, 26 Jan 2010 23:00:01 GMT Molecules 2010-01-27 15 2 Article 606 612 1420-3049 Caloxanthones O and P: Two New Prenylated Xanthones from Calophyllum inophyllum 2010-01-27 doi:10.3390/molecules15020606 Hao-Fu Dai Yan-Bo Zeng Qi Xiao Zhuang Han You-Xing Zhao Wen-Li Mei http://www.mdpi.com/1420-3049/15/1/604 The authors wish to make the following corrections to this paper [1]: http://www.mdpi.com/1420-3049/15/1/604 Mon, 25 Jan 2010 23:00:01 GMT Molecules 2010-01-26 15 1 Correction 604 605 1420-3049 Roy et al. On Two Novel Parameters for Validation of Predictive QSAR Models. Molecules, 2009, 14, 1660-1701 2010-01-26 doi:10.3390/molecules15010604 Partha Pratim Roy Somnath Paul Indrani Mitra Kunal Roy http://www.mdpi.com/1420-3049/15/1/570 Photoresponsive block copolymers (PRBCs) containing azobenzenes and other chromophores can be easily prepared by controlled polymerization. Their photoresponsive behaviors are generally based on photoisomerization, photocrosslinking, photoalignment and photoinduced cooperative motions. When the photoactive block forms mesogenic phases upon microphase separation of PRBCs, supramolecular cooperative motion in liquid-crystalline PRBCs enables them to self-organize into hierarchical structures with photoresponsive features. This offers novel opportunities to photocontrol microphase-separated nanostructures of well-defined PRBCs and extends their diverse applications in holograms, nanotemplates, photodeformed devices and microporous films. http://www.mdpi.com/1420-3049/15/1/570 Mon, 25 Jan 2010 23:00:01 GMT Molecules 2010-01-26 15 1 Review 570 603 1420-3049 Photoresponsive Block Copolymers Containing Azobenzenes and Other Chromophores 2010-01-26 doi:10.3390/molecules15010570 Haifeng Yu Takaomi Kobayashi http://www.mdpi.com/1420-3049/15/1/554 Three new enantiopure aryl-thioureas have been synthesized, N-(4-X-phenyl)-N-[1(S)-1-phenylethyl]thiourea, X= Cl, Br, and NO2 (compounds 1-3, respectively). Large single crystals of up to 0.5 cm3 were grown from methanol/ethanol solutions. Molecular structures were derived from X-ray diffraction studies and the crystal morphology was compared to calculations employing the Bravais-Friedel, Donnay-Harker model. Molecular packing was further studied with Hirshfeld surface calculations. Semi-empirical classical model calculations of refractive indices, optical rotation and the electro-optic effect were performed with OPTACT on the basis of experimentally determined refractive indices. Compound 3 (space group P 1 (No. 1)) was estimated to possess a large electro-optic coefficient r333 of approximately 30 pm/V, whereas 1 and 2 (space Group P 21 (No. 4) exhibit much smaller effects. http://www.mdpi.com/1420-3049/15/1/554 Mon, 25 Jan 2010 23:00:01 GMT Molecules 2010-01-26 15 1 Article 554 569 1420-3049 Structure, Morphology and Optical Properties of Chiral N-(4-X-phenyl)-N-[1(S)-1-phenylethyl]thiourea, X= Cl, Br, and NO2 2010-01-26 doi:10.3390/molecules15010554 Werner Kaminsky Donald Responte Dan Daranciang Jose B. Gallegos Bao-Chau Ngoc Tran Tram-Anh Pham http://www.mdpi.com/1420-3049/15/1/545 The effect of psilostachyin, a natural sesquiterpene lactone, on the growth and viability of cultured epimastigotes of Trypanosoma cruzi (Tulahuen) is reported. The antiproliferative effect was evaluated by counting the parasites in a Neubauer chamber and measuring their viability by using the dye exclusion technique. The effect on parasite growth was irreversible at concentrations higher than 1.0 µg/mL and the addition of glutathione only partially blocked the effect of the compound. Moreover, we have studied the effects of this natural compound on parasite ultrastructure by transmission electron microscopy. Interestingly, psilostachyin induced ultrastructural alterations on the parasites at a concentration of 0.5 µg/mL, with important mitochondrial swelling and deformity of the kinetoplast. http://www.mdpi.com/1420-3049/15/1/545 Sun, 24 Jan 2010 23:00:01 GMT Molecules 2010-01-25 15 1 Article 545 553 1420-3049 Antiproliferative Effect and Ultrastructural Alterations Induced by Psilostachyin on Trypanosoma cruzi 2010-01-25 doi:10.3390/molecules15010545 Valeria Sülsen Patricia Barrera Liliana Muschietti Virginia Martino Miguel Sosa http://www.mdpi.com/1420-3049/15/1/532 Catalytic asymmetric 1,4-addition of β-keto esters to nitroalkenes is described. 2.5 mol % of a homobimetallic Lewis acid/Brønsted base bifunctional Co2-Schiff base complex smoothly promoted the reaction in excellent yield (up to 99%), diastereoselectivity, and enantioselectivity (up to >30:1 dr and 98% ee). Catalyst loading was successfully reduced to 0.1 mol %. Mechanistic studies suggested that intramolecular cooperative functions of the two Co-metal centers are important for high catalytic activity and stereoselectivity. http://www.mdpi.com/1420-3049/15/1/532 Thu, 21 Jan 2010 23:00:01 GMT Molecules 2010-01-22 15 1 Article 532 544 1420-3049 Catalytic Asymmetric 1,4-Additions of β-Keto Esters to Nitroalkenes Promoted by a Bifunctional Homobimetallic Co2-Schiff Base Complex 2010-01-22 doi:10.3390/molecules15010532 Makoto Furutachi Zhihua Chen Shigeki Matsunaga Masakatsu Shibasaki http://www.mdpi.com/1420-3049/15/1/515 Some new mono-and bis-polycyclic aromatic spiro-β-lactams and bis-non spiro-polycyclic aromatic β-lactams have been synthesized from imines derived from anthracene-9-carbaldehyde, 2-naphtaldehyde and a ketene derived from 9H-xanthene-9-carboxylic acid and phenoxyacetic acid by a [2+2] cycloaddition reaction. The cycloadducts were characterized by spectral data, including 1H-NMR, 13C-NMR, IR and elemental analyses. The configurations of some of these mono-spiro-β-lactams were established by X-ray crystal analysis. http://www.mdpi.com/1420-3049/15/1/515 Thu, 21 Jan 2010 23:00:01 GMT Molecules 2010-01-22 15 1 Article 515 531 1420-3049 Synthesis of Some New Mono- and Bis-Polycyclic Aromatic Spiro and Bis-Nonspiro-β-Lactams 2010-01-22 doi:10.3390/molecules15010515 Aliasghar Jarrahpour Edris Ebrahimi http://www.mdpi.com/1420-3049/15/1/502 New 5-(2-thienyl)-1,2,4-triazoles and 5-(2-thienyl)-1,3,4-oxadiazoles namely, N-[3-mercapto-5-(2-thienyl)-1,2,4-triazol-4-yl]-N'-arylthioureas 4a–e, 2-arylamino-5-(2-thienyl)-1,2,4-triazolo[3,4-b][1,3,4]thiadiazoles 5a–e, 3-arylaminomethyl-5-(2-thienyl)-1,3,4-oxadiazoline-2-thiones 7a–e, 3-(N-substituted anilinomethyl)-5-(2-thienyl)-1,3,4-oxadiazoline-2-thiones 8a, b and 3-(4-substituted-1-piperazinylmethyl)-5-(2-thienyl)-1,3,4-oxadiazoline-2-thiones 9a–f, were prepared. The synthesized compounds were tested for in vitro activities against certain strains of Gram-positive and Gram-negative bacteria and the yeast-like pathogenic fungus Candida albicans. Compound 9a displayed marked broad spectrum antibacterial activity, while compounds 4d, 5e, 7b, 7c, 7d, 9b, 9c and 9d were highly active against the tested Gram-positive bacteria. None of the synthesized compounds were proved to be significantly active against Candida albicans. http://www.mdpi.com/1420-3049/15/1/502 Thu, 21 Jan 2010 23:00:01 GMT Molecules 2010-01-22 15 1 Article 502 514 1420-3049 Synthesis and Antimicrobial Activity of New 5-(2-Thienyl)-1,2,4-triazoles and 5-(2-Thienyl)-1,3,4-oxadiazoles and Related Derivatives 2010-01-22 doi:10.3390/molecules15010502 Mohamed A. Al-Omar http://www.mdpi.com/1420-3049/15/1/460 The synthesis of the subgroups of acetogenins containing non-adjacent bis-THF and non-adjacent THF-THP core units is reviewed. Specifically, total syntheses of gigantecin, 4-deoxygigantecin, cis-sylvaticin, squamostatin-C, squamostatin-D, sylvaticin and mucocin are discussed. http://www.mdpi.com/1420-3049/15/1/460 Wed, 20 Jan 2010 23:00:01 GMT Molecules 2010-01-21 15 1 Review 460 501 1420-3049 Total Synthesis of Annonaceous Acetogenins Belonging to the Non-Adjacent Bis-THF and Non-Adjacent THF-THP Sub-Classes 2010-01-21 doi:10.3390/molecules15010460 Ian B. Spurr Richard C. D. Brown http://www.mdpi.com/1420-3049/15/1/442 Vitamin B6 is an intriguing molecule that is involved in a wide range of metabolic, physiological and developmental processes. Based on its water solubility and high reactivity when phosphorylated, it is a suitable co-factor for many biochemical processes. Furthermore the vitamin is a potent antioxidant, rivaling carotenoids or tocopherols in its ability to quench reactive oxygen species. It is therefore not surprising that the vitamin is essential and unquestionably important for the cellular metabolism and well-being of all living organisms. The review briefly summarizes the biosynthetic pathways of vitamin B6 in pro- and eukaryotes and its diverse roles in enzymatic reactions. Finally, because in recent years the vitamin has often been considered beneficial for human health, the review will also sum up and critically reflect on current knowledge how human health can profit from vitamin B6. http://www.mdpi.com/1420-3049/15/1/442 Tue, 19 Jan 2010 23:00:01 GMT Molecules 2010-01-20 15 1 Review 442 459 1420-3049 Vitamin B6: A Molecule for Human Health? 2010-01-20 doi:10.3390/molecules15010442 Hanjo Hellmann Sutton Mooney http://www.mdpi.com/1420-3049/15/1/432 In the present study, we investigate the effects of three different Mitragyna speciosa extracts, namely methanolic, aqueous and total alkaloid extracts, on glutathione transferase-specific activity in male Sprague Dawley rat liver cytosol in vitro and in vivo. In the in vitro study, the effect of Mitragyna speciosa extracts (0.01 to 750 µg/mL) against the specific activity of glutathione transferases was examined in rat liver cytosolic fraction from untreated rats. Our data show concentration dependent inhibition of cytosolic GSTs when Mitragyna speciosa extract was added into the reaction mixture. At the highest concentration used, the methanolic extract showed the highest GSTs specific activity inhibition (61%), followed by aqueous (50%) and total alkaloid extract (43%), respectively. In in vivo study, three different dosages; 50, 100 and 200 mg/kg for methanolic and aqueous extracts and 5, 10 and 20 mg/kg for total alkaloid extract were given orally for 14 days. An increase in GST specific activity was generally observed. However, only Mitragyna speciosa aqueous extract with a dosage of 100 mg/kg showed significant results: 129% compared to control. http://www.mdpi.com/1420-3049/15/1/432 Tue, 19 Jan 2010 23:00:01 GMT Molecules 2010-01-20 15 1 Article 432 441 1420-3049 In Vitro and in Vivo Effects of Three Different Mitragyna speciosa Korth Leaf Extracts on Phase II Drug Metabolizing Enzymes—Glutathione Transferases (GSTs) 2010-01-20 doi:10.3390/molecules15010432 Juzaili Azizi Sabariah Ismail Mohd Nizam Mordi Surash Ramanathan Mohd Ikram Mohd Said Sharif Mahsufi Mansor http://www.mdpi.com/1420-3049/15/1/420 The structures of condensed tannins isolated from two mangrove species, Kandelia candel and Rhizophora mangle, were characterized by 13C nuclear magnetic resonance (NMR) spectroscopy and matrix assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) analyses. Results demonstrate that large heterogeneity occurs in degree of polymerization, pattern of hydroxylation, and substitution with monosaccharides in the structures of the condensed tannins. Condensed tannin oligomers from K. candel and R. mangle were shown to be heterogeneous mixtures consisting of procyanidin and prodelphinidin structural units with the former dominating. The MALDI-TOF mass spectra contained masses corresponding to a distinct oligomeric series of glycosylated heteropolyflavan units. In addition, condensed tannins from two mangrove plants were screened for their potential antioxidant activities using 1,1-diphenyl-2-picrylhydrazyl (DPPH) and ferric reducing antioxidant power (FRAP) model systems. http://www.mdpi.com/1420-3049/15/1/420 Tue, 19 Jan 2010 23:00:01 GMT Molecules 2010-01-20 15 1 Article 420 431 1420-3049 Condensed Tannins from Mangrove Species Kandelia candel and Rhizophora mangle and Their Antioxidant Activity 2010-01-20 doi:10.3390/molecules15010420 Liang-Liang Zhang Yi-Ming Lin Hai-Chao Zhou Shu-Dong Wei Jia-Hong Chen http://www.mdpi.com/1420-3049/15/1/407 Flash vacuum pyrolysis (FVP) of 4-aryl-3-buten-2-ols [ArCH=CH-CH(CH3)OH, where Ar is phenyl, p-MeO, p-Me, p-Cl, p-NO2] gave the corresponding buta-1,3-dien-1-ylbenzene (ArCH=CH-CH=CH2, where Ar is Ph, p-MeO, p-Me, p-Cl, p-NO2) and 7-X-1,2-dihydronaphthalene derivatives (where X is H, MeO); FVP of 1-aryl-3-benzyloxy1-1-butenes and benzyl cinnamyl ethers [ArCH=CHCH(X)OCH2Ph, where Ar is phenyl, p-MeO, p-Me, p-Cl, X is H, Me, Ph] gave the corresponding but-2-en-1-ylbenzene derivatives (ArCH2CH=CH-X, where X is H, Me, Ph) together with benzaldehyde. The proposed mechanism of these pyrolytic transformations was supported by kinetic and product analysis. http://www.mdpi.com/1420-3049/15/1/407 Tue, 19 Jan 2010 23:00:01 GMT Molecules 2010-01-20 15 1 Article 407 419 1420-3049 Gas-Phase Pyrolytic Reaction of 4-Aryl-3-buten-2-ols and Allyl Benzyl Ethers: Kinetic and Mechanistic Study 2010-01-20 doi:10.3390/molecules15010407 Alya M. Al-Etaibi Nouria A. Al-Awadi Maher R. Ibrahim Yehia A. Ibrahim http://www.mdpi.com/1420-3049/15/1/399 Protopanaxatriol saponins obtained with AB-8 macroporous resin mainly consisted of ginsenosides Rg1 and Re. A novel mono-ester of ginsenoside-Rh1 (ginsenoside-ORh1) was synthesized through further enzymatic hydrolysis and octanoyl chloride modifications. A 53% yield was obtained by a facile synthetic method. The structures were identified on the basis of 1D-NMR and 2D-NMR, as well as ESI-TOF-MS mass spectroscopic analyses. The isolated and synthetic compounds were applied in an anti-tumor bioassay, in which ginsenoside ORh1 showed moderate effects on Murine H22 Hepatoma Cells. http://www.mdpi.com/1420-3049/15/1/399 Mon, 18 Jan 2010 23:00:01 GMT Molecules 2010-01-19 15 1 Article 399 406 1420-3049 Isolation, Synthesis and Structures of Ginsenoside Derivatives and Their Anti-Tumor Bioactivity 2010-01-19 doi:10.3390/molecules15010399 Mei Han Jin-Gang Hou Cheng-Ming Dong Wei Li Hao-Lun Yu Yi-Nan Zheng Li Chen http://www.mdpi.com/1420-3049/15/1/385 Luteolin (3′,4′,5,7-tetrahydroxylflavone) is a plant flavonoid and pharmacologically active agent that has been isolated from several plant species. In the present study, the effect of luteolin from the flowers of Lonicera japonica on phorbol 12-myristate 13-acetate (PMA) plus A23187-induced mast cell activation was examined. Luteolin significantly inhibited the induction of inflammatory cytokines such as tumor necrosis factor (TNF)-α, interleukin (IL)-8, IL-6 and granulocyte-macrophage colony-stimulating factor (GM-CSF) by PMA plus A23187. Moreover, luteolin attenuated cyclooxygenase (COX)-2 expression and intracellular Ca2+ levels. In activated HMC-1 cells, the phosphorylation of extra-signal response kinase (ERK 1/2) and c-jun N-terminal Kinase (JNK 1/2), but not p38 mitogen-activated protein kinase (p38 MAPK) were decreased by treatment of the cells with luteolin. Luteolin inhibited PMA plus A23187-induced nuclear factor (NF)-κB activation, IκB degradation, and luciferase activity. Furthermore, luteolin suppressed the expression of TNF-α, IL-8, IL-6, GM-CSF, and COX-2 through a decrease in the intracellular Ca2+ levels, and also showed a suppression of the ERK 1/2, JNK 1/2, and NF-κB activation. These results indicated that luteolin from the flowers of Lonicera japonica exerted a regulatory effect on mast cell-mediated inflammatory diseases, such as RA, allergy disease and IBD. http://www.mdpi.com/1420-3049/15/1/385 Sun, 17 Jan 2010 23:00:01 GMT Molecules 2010-01-18 15 1 Article 385 398 1420-3049 Luteolin Isolated from the Flowers of Lonicera japonica Suppresses Inflammatory Mediator Release by Blocking NF-κB and MAPKs Activation Pathways in HMC-1 Cells 2010-01-18 doi:10.3390/molecules15010385 Ok-Hwa Kang Jang-Gi Choi John-Hwa Lee Dong-Yeul Kwon http://www.mdpi.com/1420-3049/15/1/374 The deacylation of glucose, galactose and mannose pentaacetates, galactose and mannose penta(3-bromo)benzoates, as well as the dealkylation of 2,3,4,6-tetra-O-acetyl and 2,3,4,6-tetra-O-(3-bromo)benzoyl methyl α-D-glucopyranosides have been studied. In addition, a computational study on the deacylation of β-D-glucose pentaacetate has been carried out with density functional theory (B3LYP/6-31G*). The anomeric effect during deacetylation and dealkylation has been clearly demonstrated in both experimental and computational results. http://www.mdpi.com/1420-3049/15/1/374 Sun, 17 Jan 2010 23:00:01 GMT Molecules 2010-01-18 15 1 Article 374 384 1420-3049 A Simple Preparation of 2,3,4,6-Tetra-O-acyl-Gluco-, Galacto- and Mannopyranoses and Relevant Theoretical Study 2010-01-18 doi:10.3390/molecules15010374 Zerong Daniel Wang Yirong Mo Chiao-Lun Chiou Minghong Liu http://www.mdpi.com/1420-3049/15/1/352 Phospholipids are essential constituents of all living cell membranes. There are many analytical methods available for the quantitative and qualitative determination of phospholipids, but since these molecules lack chromophores, common absorbance based methods are of limited use. Beside mass spectrometry, some less specific approaches that are routinely used are evaporative light scattering detection or fluorescence, which exhibit sufficient sensitivity. Here, we focus on fluorescence, which remains an interesting way to quantify phospholipids. Two ways of detecting phospholipids by fluorescence are possible coupled with separation techniques such as thin layer chromatography (TLC), high performance liquid chromatography (HPLC) and capillary electrophoresis (CE): firstly, pre-column derivatization procedures and secondly, probe assisted post-column detection with suitable fluorescence reagents. In both cases, the common purpose is to increase the detection sensitivity. It is shown that, whereas pre-column derivatization is characterized by selectivity due to the chemical functionality of the analyte involved in the derivatization process, in supramolecular post-column derivatization, the selectivity only proceeds from the capacity of the lipid to involve supramolecular assemblies with a fluorescence probe. The aim of this review is to summarize available experiments concerning fluorescence detection of phospholipids. The interest and limitation of such detection approaches are discussed. http://www.mdpi.com/1420-3049/15/1/352 Sun, 17 Jan 2010 23:00:01 GMT Molecules 2010-01-18 15 1 Review 352 373 1420-3049 Interest of Fluorescence Derivatization and Fluorescence Probe Assisted Post-column Detection of Phospholipids: A Short Review 2010-01-18 doi:10.3390/molecules15010352 Hanadi Ibrahim Eric Caudron Athena Kasselouri Pratrice Prognon http://www.mdpi.com/1420-3049/15/1/341 Phthalides are important bio-active constituents in Si-Wu-Tang and Fo-Shou-San, two commonly used Traditional Chinese Medicine (TCM) combined prescriptions mainly derived from Radix Angelica and Rhizoma Chuanxiong. In this paper, the contents of eight phthalides, including Z-ligustilide, E-ligustilide, Z-butylenephthalide, E-butylene-phthalide, 3-butylphthalide, neocnidilide and senkyunolide A were determined or estimated by gas chromatography–mass spectrometry (GC-MS). The results showed GC-MS was a simple, rapid, and high sensitive method for analyzing phthalides in Si-Wu-Tang, Fo-Shou-San, Radix Angelica and Rhizoma Chuanxiong, and the extractable contents of each phthalides including Z-ligustilide, E-ligustilide, Z-butylenephthalide, etc. varied after Radix Angelica, Rhizoma Chuanxiong were combined into a formulation, such as Si-Wu-Tang and Fo-Shou-San. Furthermore, inhibition activity of essential oils from Si-Wu-Tang, Fo-Shou-San, Radix Angelica and Rhizoma Chuanxiong on uterine contraction was tested in an in vitro assay, and the results showed that the activity of the essential oil is higher as the content of the phthalides increase, which demonstrated that phthalides are possibly main active components inhibiting mice uterine contraction in vitro. All of the results suggested that comparative analysis of chemical components and pharmacological activities of each herb and formula is possibly helpful to elucidate the active components in traditional Chinese medicine, and to reveal the compatibility mechanism of TCM formulae. http://www.mdpi.com/1420-3049/15/1/341 Thu, 14 Jan 2010 23:00:01 GMT Molecules 2010-01-15 15 1 Article 341 351 1420-3049 Identification and Comparative Quantification of Bio-Active Phthalides in Essential Oils from Si-Wu-Tang, Fo-Shou-San, Radix Angelica and Rhizoma Chuanxiong 2010-01-15 doi:10.3390/molecules15010341 Yuping Tang Min Zhu Sheng Yu Yongqing Hua Jin-Ao Duan Shulan Su Xu Zhang Yin Lu Anwei Ding http://www.mdpi.com/1420-3049/15/1/331 Substituted pyrazinecarboxamides markedly influenced production of flavonolignans in Silybum marianum callus and suspension cultures. In this study the effect of two compounds, N-(3-iodo-4-methylphenyl)pyrazine-2-carboxamide (1) and N-(3-iodo-4-methylphenyl)-5-tert-butyl-pyrazine-2-carboxamide (2), as abiotic elicitors on flavono-lignan production in callus culture of S. marianum was investigated. Silymarin complex compounds have hepatoprotective, anticancer and also hypocholesterolemic activity. In vitro flavonolignan concentration in cells is very low and the elicitation is one of the methods to increase production. Elicitors were tested at three concentrations and at different culture times. In the case of elicitation with 1, the greatest increase of flavonolignan and taxifoline production was observed at concentration c1a after 6-hours of elicitation and after 24 and 72-hours at concentration c1b. However, increased production of silychristin, one of the compounds in the silymarin complex, was achieved after only 6-hours elicitation with c1a (2.95 × 10-4 mol/L). The content of silychristin was 2-times higher compared to the control sample. An increased production of silychristin was reached with compound 2 at the concentration c2 (2.53 × 10-3 mol/L) after 72 h of elicitation. The production of silychristin in this case was increased 12-times compared to control. http://www.mdpi.com/1420-3049/15/1/331 Wed, 13 Jan 2010 23:00:01 GMT Molecules 2010-01-14 15 1 Article 331 340 1420-3049 Substituted Pyrazinecarboxamides as Abiotic Elicitors of Flavolignan Production in Silybum marianum (L.) Gaertn Cultures in Vitro 2010-01-14 doi:10.3390/molecules15010331 Lenka Tůmová Jiří Tůma Klara Megušar Martin Doležal http://www.mdpi.com/1420-3049/15/1/305 A sensitive, selective and reliable liquid chromatography-mass spectrometry coupled with electrospray ionization interface method for simultaneous separation and determination of thymine, adenine, adenosine and cordycepin in Cordyceps sinensis has been established. The optimum separation for these analytes was achieved using a gradient elution system and a 2.0 × 150 mm Shimadzu VP-ODS column. 2-Chloroadenosine was used as internal standard for this assay. [M+H]+ions at m/z 127, 136, 268, 252 and 302 were chosen and selective ion monitoring (SIM) mode was used for quantitative analysis of the four main nucleosides. The regression equations were linear in the range of 1.0–117.5 μg·mL-1 for thymine, 1.8-127.0 μg·mL-1 for adenine, 0.6-114.0 μg·mL-1 for adenosine and 0.5-107.5 μg·mL-1 for cordycepin. The limits of quantitation (LOQ) and detection (LOD) were 1.0 and 0.2 μg·mL-1 for thymine, 1.8 and 0.6 μg·mL-1 for adenine, 0.6 and 0.1 μg·mL-1 for adenosine and 0.5 and 0.1 μg·mL-1 for cordycepin, respectively. The recoveries of the four nucleosides ranged from 98.47 to 99.32%. The developed method was successfully used to determine nucleosides in Cordyceps sinensis from different sources. http://www.mdpi.com/1420-3049/15/1/305 Tue, 12 Jan 2010 23:00:01 GMT Molecules 2010-01-13 15 1 Article 305 314 1420-3049 Analysis of the Main Nucleosides in Cordyceps Sinensis by LC/ESI-MS 2010-01-13 doi:10.3390/molecules15010305 Jian-Wei Xie Lan-Fang Huang Wei Hu Yun-Biao He Kin Ping Wong http://www.mdpi.com/1420-3049/15/1/315 A water-soluble and air-stable Pd(NH3)2Cl2/cationic 2,2’-bipyridyl system was found to be a highly-efficient and reusable catalyst for the coupling of aryl iodides and alkenes in neat water using Bu3N as a base. The reaction was conducted at 140 °C in a sealed tube in air with a catalyst loading as low as 0.0001 mol % for the coupling of activated aryl iodides with butyl and ethyl acrylates, providing the corresponding products in good to excellent yields with very high turnover numbers. In the case of styrene, Mizoroki-Heck coupling products were obtained in good to high yields by using a greater catalyst loading (1 mol %) and TBAB as a phase-transfer agent. After extraction, the residual aqueous solution could be reused several times with only a slight decrease in its activity, making the Mizoroki-Heck reaction “greener”. http://www.mdpi.com/1420-3049/15/1/315 Mon, 11 Jan 2010 23:00:01 GMT Molecules 2010-01-12 15 1 Article 315 330 1420-3049 Palladium(II)/Cationic 2,2’-Bipyridyl System as a Highly Efficient and Reusable Catalyst for the Mizoroki-Heck Reaction in Water 2010-01-12 doi:10.3390/molecules15010315 Shao-Hsien Huang Jun-Rong Chen Fu-Yu Tsai http://www.mdpi.com/1420-3049/15/1/288 In this study, a series of fourteen ring-substituted 8-hydroxyquinoline derivatives were prepared. The synthesis procedures are presented. The compounds were analyzed using RP-HPLC to determine lipophilicity. They were tested for their activity related to inhibition of photosynthetic electron transport (PET) in spinach (Spinacia oleracea L.) chloroplasts. Primary in vitro screening of the synthesized compounds was also performed against four mycobacterial strains and against eight fungal strains. Several compounds showed biological activity comparable with or higher than the standards isoniazid or fluconazole. For all the compounds, the relationships between the lipophilicity and the chemical structure of the studied compounds are discussed. http://www.mdpi.com/1420-3049/15/1/288 Mon, 11 Jan 2010 23:00:01 GMT Molecules 2010-01-12 15 1 Article 288 304 1420-3049 Investigating the Activity Spectrum for Ring-Substituted 8-Hydroxyquinolines 2010-01-12 doi:10.3390/molecules15010288 Robert Musiol Josef Jampilek Jacek E. Nycz Matus Pesko James Carroll Katarina Kralova Marcela Vejsova Jim O'Mahony Aidan Coffey Anna Mrozek Jaroslaw Polanski http://www.mdpi.com/1420-3049/15/1/270 A series of 6-halo-3-hydroxyphenylcoumarins (resveratrol-coumarins hybrid derivatives) was synthesized in good yields by a Perkin reaction followed by hydrolysis. The new compounds were evaluated for their vasorelaxant activity in intact rat aorta rings pre-contracted with phenylephrine (PE), as well as for their inhibitory effects on platelet aggregation induced by thrombin in washed human platelets. These compounds concentration-dependently relaxed vascular smooth muscle and some of them showed a platelet antiaggregatory activity that was up to thirty times higher than that shown by trans-resveratrol and some other previously synthesized derivatives. http://www.mdpi.com/1420-3049/15/1/270 Mon, 11 Jan 2010 23:00:01 GMT Molecules 2010-01-12 15 1 Article 270 279 1420-3049 Synthesis and Vasorelaxant and Platelet Antiaggregatory Activities of a New Series of 6-Halo-3-phenylcoumarins 2010-01-12 doi:10.3390/molecules15010270 Elías Quezada Giovanna Delogu Carmen Picciau Lourdes Santana Gianni Podda Fernanda Borges Verónica García-Morales Dolores Viña Francisco Orallo http://www.mdpi.com/1420-3049/15/1/258 We have investigated dissolution and surface reaction of calcite and aragonite in amino acid solutions of L-glutamic (L-glu) and L-aspartic acid (L-asp) at weak acidity of above pH 3. The surface reactions of calcite and aragonite were related with the dissolution. Calcite was dissolved in both solutions but the dissolution was limited by an adsorption of Ca-carboxylate salt. Aragonite was neither dissolved nor reacted in amino acid solutions because the crystal surface consisted of a hard to dissolve structure. http://www.mdpi.com/1420-3049/15/1/258 Sun, 10 Jan 2010 23:00:01 GMT Molecules 2010-01-11 15 1 Article 258 269 1420-3049 Comparison of Dissolution and Surface Reactions Between Calcite and Aragonite in L-Glutamic and L-Aspartic Acid Solutions 2010-01-11 doi:10.3390/molecules15010258 Miyoung Ryu Hwan Kim Mihee Lim Kwangsuk You Jiwhan Ahn http://www.mdpi.com/1420-3049/15/1/251 The antioxidant properties of two apple dihydrochalcones, namely phloretin and phloridzin, were evaluated and compared with those of α-tocopherol and butylated hydroxytoluene (BHT). The effects were studied in an oil-in-water emulsion system containing methyl linolenate (ML), methyl eicosapentaenoate (MEPA), and methyl docosahexaenoate (MDHA) in which oxidation was initiated by the peroxyl radical generator 2,2-azobis(2-amidinopropane) dihydrochloride (AAPH) and in fish oil where oxidation was initiated thermally. In the emulsion system, phloretin (1 and 5 mM) completely inhibited the oxidation of ML tested as evidenced by the thiobarbituric acid reactive substances (TBARS) assay. Under the same conditions, phloridzin was less effective than phloretin, but still more effective than α-tocopherol. Both phloretin and phloridzin molecules had a marginal inhibitory effect against oxidation of fish oil induced by heating at 70 °C for 3 hours, when compared to BHT. These results indicate that phloretin and phloridzin have the potential to suppress lipid oxidation in polyunsaturated fatty acid (PUFA) containing foods. http://www.mdpi.com/1420-3049/15/1/251 Sun, 10 Jan 2010 23:00:01 GMT Molecules 2010-01-11 15 1 Communication 251 257 1420-3049 Inhibition of Oxidation of Aqueous Emulsions of Omega-3 Fatty Acids and Fish Oil by Phloretin and Phloridzin 2010-01-11 doi:10.3390/molecules15010251 H. P. Vasantha Rupasinghe Afsana Yasmin http://www.mdpi.com/1420-3049/15/1/241 Eclipta prostrata, an aromatic plant, is known in Chinese herbal medicine for the treatment of various kidney diseases. In the present study, the volatile components were isolated from the aerial parts of this plant by hydrodistillation and analysed by GC–MS. A total of 55 compounds, which were the major part (91.7%) of the volatiles, were identified by matching mass spectra with a mass spectrum library (NIST 05.L). The main components were as follows: heptadecane (14.78%), 6,10,14-trimethyl-2-pentadecanone (12.80%), n-hexadecanoic acid (8.98%), pentadecane (8.68%), eudesma-4(14),11-diene (5.86%), phytol (3.77%), octadec-9-enoic acid (3.35%), 1,2-benzenedicarboxylic acid diisooctyl ester (2.74%), (Z,Z)-9,12-octadecadienoic acid (2.36%), (Z)-7,11-dimethyl-3-methylene-1,6,10-dodecatriene (2.08%) and (Z,Z,Z)-1,5,9,9-tetramethyl-1,4,7-cycloundecatriene (2.07%). The effects of volatile components and ethanolic extract from the aerial parts of this plant on the proliferation and differentiation of primary osteoblasts were evaluated by the MTT method and measuring the activity of alkaline phosphatase (ALP activity). Both volatile components and ethanolic extract (1 μg/mL to 100 μg/mL) significantly (p < 0.01) stimulated the proliferation and increased the ALP activity of primary osteoblasts. These results propose that E. prostrata can play an important role in osteoblastic bone formation, and may possibly lead to the development of bone-forming drugs. http://www.mdpi.com/1420-3049/15/1/241 Thu, 07 Jan 2010 23:00:01 GMT Molecules 2010-01-08 15 1 Article 241 250 1420-3049 Effects of Volatile Components and Ethanolic Extract from Eclipta prostrata on Proliferation and Differentiation of Primary Osteoblasts 2010-01-08 doi:10.3390/molecules15010241 Xiong-Hao Lin Yan-Bin Wu Shan Lin Jian-Wei Zeng Pei-Yuan Zeng Jin-Zhong Wu http://www.mdpi.com/1420-3049/15/1/233 Exhaustive hydro-distillation of Descurainia sophia (L.) Webb ex Prantl (flixweed) collected from two different locations (Cangzhou city-Sample 1 and Beijing city-Sample 2) gave in both cases yellowish colored oils in 0.31 and 0.26% yield, respectively. Detailed chemical composition of the essential oils was analyzed by GC and GC/MS, and forty and thirty-eight compounds were identified. The results indicated that the most abundant component of Sample 1were cis-β-ocimene (20.1%), menthol (11.27%), neoisomenthyl acetate (3.5%), alloaromadendrene (2.28%) and longicyclene (2.25%). Compared with the constituents of Sample 1, several chemical compounds such as 1,8-cineole, α-eudesmol, cis, trans-farnesol and β-pinene were not detected in Sample 2 although it was similarly dominated by cis-β-ocimene (17.12%), menthol (10.7%) and neoisomenthyl acetate (2.96%). Final analysis of the chemical constituents in the essential oils of the two samples showed similarity in their chemical composition, but the relative content of all shared chemical constituents in Sample 2 was lower than that in Sample 1. http://www.mdpi.com/1420-3049/15/1/233 Thu, 07 Jan 2010 23:00:01 GMT Molecules 2010-01-08 15 1 Article 233 240 1420-3049 Determination of the Volatile Composition in Essential Oil of Descurainia sophia (L.) Webb ex Prantl (Flixweed) by Gas Chromatography/Mass Spectrometry (GC/MS) 2010-01-08 doi:10.3390/molecules15010233 Jing Li Xingang Liu Fengshou Dong Jun Xu Yongquan Zheng Weili Shan http://www.mdpi.com/1420-3049/15/1/226 A new D3h symmetric triptycene derivative has been synthesized with the aim of obtaining molecules that are able to assemble into porous structures, and can be used in the development of new ligands. The synthesis involves a Diels-Alder reaction as the key step, followed by an oxidation and the formation of a maleimide ring. Triptycene trimaleimide furnished single crystals which have been analyzed by means of X-ray diffraction. http://www.mdpi.com/1420-3049/15/1/226 Wed, 06 Jan 2010 23:00:01 GMT Molecules 2010-01-07 15 1 Communication 226 232 1420-3049 Synthesis and Structure of D3h-Symmetric Triptycene Trimaleimide 2010-01-07 doi:10.3390/molecules15010226 Cristiano Zonta Ottorino De Lucchi Anthony Linden Martin Lutz http://www.mdpi.com/1420-3049/15/1/215 To obtain an aptamer with a high affinity for vascular endothelial growth factor (VEGF), we focused on the receptor-binding domain (RBD) of VEGF as a target epitope. Three rounds of screening gave Vap7, which bound to the VEGF isoforms VEGF121 and VEGF165 with KD values of 1.0 nM and 20 nM, respectively. Moreover, Vap7 showed specificity within the VEGF family. Secondary structure predictions and circular dicrhoism suggested that Vap7 folds into a G-quadruplex structure. We obtained a mutant aptamer that contains only this region of the aptamer sequence. This truncated mutant (V7t1) bound to both VEGF121 and VEGF165 with KD values of 1.1 nM and 1.4 nM, respectively. Its sequence was 5'-TGTGGGGGTGGACGGGCCGGGTAGA-3', and it appeared to form a G-quadruplex structure. We also produced an aptamer heterodimer consisting of our previously derived aptamer (del5-1), which binds to the heparin-binding domain of VEGF, linked to V7t1. The resulting heterodimer bound strongly to VEGF165 with a KD value of 4.7 × 102 pM. http://www.mdpi.com/1420-3049/15/1/215 Wed, 06 Jan 2010 23:00:01 GMT Molecules 2010-01-07 15 1 Article 215 225 1420-3049 Screening and Improvement of an Anti-VEGF DNA Aptamer 2010-01-07 doi:10.3390/molecules15010215 Yoshihiko Nonaka Koji Sode Kazunori Ikebukuro http://www.mdpi.com/1420-3049/15/1/198 Nicotinic acid, known as vitamin B3, is an effective lipid lowering drug and intense cutaneous vasodilator. This study reports the effect of 2-(1-adamantylthio)nicotinic acid (6) and its amide 7 and nitrile analog 8 on phenylephrine-induced contraction of rat thoracic aorta as well as antioxidative activity. It was found that the tested thionicotinic acid analogs 6-8 exerted maximal vasorelaxation in a dose-dependent manner, but their effects were less than acetylcholine (ACh)-induced nitric oxide (NO) vasorelaxation. The vasorelaxations were reduced, apparently, in both NG-nitro-L-arginine methyl ester (L-NAME) and indomethacin (INDO). Synergistic effects were observed in the presence of L-NAME plus INDO, leading to loss of vasorelaxation of both the ACh and the tested nicotinic acids. Complete loss of the vasorelaxation was noted under removal of endothelial cells. This infers that the vasorelaxations are mediated partially by endothelium-induced NO and prostacyclin. The thionicotinic acid analogs all exhibited antioxidant properties in both 2,2-diphenyl-1-picrylhydrazyl (DPPH) and superoxide dismutase (SOD) assays. Significantly, the thionicotinic acid 6 is the most potent vasorelaxant with ED50 of 21.3 nM and is the most potent antioxidant (as discerned from DPPH assay). Molecular modeling was also used to provide mechanistic insights into the vasorelaxant and antioxidative activities. The findings reveal that the thionicotinic acid analogs are a novel class of vasorelaxant and antioxidant compounds which have potential to be further developed as promising therapeutics. http://www.mdpi.com/1420-3049/15/1/198 Tue, 05 Jan 2010 23:00:01 GMT Molecules 2010-01-06 15 1 Article 198 214 1420-3049 Elucidating the Structure-Activity Relationships of the Vasorelaxation and Antioxidation Properties of Thionicotinic Acid Derivatives 2010-01-06 doi:10.3390/molecules15010198 Supaluk Prachayasittikul Orapin Wongsawatkul Apilak Worachartcheewan Chanin Nantasenamat Somsak Ruchirawat Virapong Prachayasittikul http://www.mdpi.com/1420-3049/15/1/178 In the last few years click chemistry reactions, and in particular coppercatalyzed cycloadditions, have been used intensively for the preparation of new bioconjugate molecules and materials applicable to biomedical and pharmaceutical areas. This review will be focused on conjugates of the tripeptide Arg-Gly-Asp formed by means of click chemistry reactions. This sequence is a well known binding motif for specific transmembrane proteins and is involved in cellular adhesion to the extracellular matrix, allowing the selective recognition of the biomolecule or polymer in which it is incorporated. http://www.mdpi.com/1420-3049/15/1/178 Tue, 05 Jan 2010 23:00:01 GMT Molecules 2010-01-06 15 1 Review 178 197 1420-3049 Click Chemistry for the Synthesis of RGD-Containing Integrin Ligands 2010-01-06 doi:10.3390/molecules15010178 Matteo Colombo Aldo Bianchi http://www.mdpi.com/1420-3049/15/1/164 Five generic haptens of pyrethoid insecticides, which were classified as three types, were designed and synthesized: the first (hapten 1) is for type I pyrethroids without a cyano group, the second (hapten 2 and XQ) for type II pyrethroids with a cyano group, and the third (hapten 4 and 5) for both types of pyrethroids with loss of the ester group. The hapten structures were confirmed by MS and 1H-NMR. Hapten 1 and 2 were conjugated with BSA respectively and haptens 1-5 were conjugated with OVA. Four polyclonal antisera were raised against BSA conjugates including a mixture conjugate, and twenty antibody/coating conjugate combinations were selected for studies of assay sensitivity and specificity for pyrethroids. The study revealed the best combination, which showed equal high sensitivities (I50 is around 0.02 μg mL-1) to both types of pyrethroids. The immunity results suggest that, with a mixture conjugates, a polyclonal antibody against a group of insecticides can be prepared for multi-residue assays. http://www.mdpi.com/1420-3049/15/1/164 Sun, 03 Jan 2010 23:00:01 GMT Molecules 2010-01-04 15 1 Article 164 177 1420-3049 Immunoassay Development for the Class-Specific Assay for Types I and II Pyrethroid Insecticides in Water Samples 2010-01-04 doi:10.3390/molecules15010164 Qi Zhang Wen Zhang Xiuping Wang Peiwu Li