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Special Issue "25th Anniversary of Molecules—Recent Advances in Inorganic Chemistry"

A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Inorganic Chemistry".

Deadline for manuscript submissions: closed (31 December 2020).

Special Issue Editors

Dr. Burgert Blom
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Guest Editor
Maastricht Science Programme, Assistant Professor of Inorganic Chemistry and Catalysis, Maastricht University, Kapoenstraat 2, P.O. Box 616, 6200 MD Maastricht, The Netherlands
Interests: Main Group organometallics; d-Block and f-block Organometallic Chemistry and the use of these Complexes in Catalysis and as possible drugs in cancer therapy
Special Issues and Collections in MDPI journals
Dr. Erika Ferrari
E-Mail Website
Guest Editor
Department of Chemical and Geological Sciences, University of Modena and Reggio Emilia, via Campi, 103-41125 Modena, Italy
Interests: curcumin; metal-based drugs; PET-radiotracers; gallium-68; curcuminoids; NMR spectroscopy
Special Issues and Collections in MDPI journals
Prof. Dr. Vassilis Tangoulis
E-Mail Website
Guest Editor
Department of Chemistry, University of Patras, Patra, Greece
Interests: hybrid carbon based nano-materials; encapsulation/decoration of functionalized multi-wall nanotubes with Single Molecule Magnets (SMMs) and the study of their magnetic behaviour; application of hybrid materials in the area of spintronics or medicine (MRI agents)
Special Issues and Collections in MDPI journals
Prof. Dr. Cédric R Mayer
E-Mail Website
Guest Editor
Department of Chemistry, UFR of Science, Versailles, France
Interests: hybrid organic-inorganic materials; design of composites and nanocomposites; polyoxometalate; Ru(II) and Ir(III) coordination chemistry and photophysical applications
Special Issues and Collections in MDPI journals
Prof. Dr. Axel Klein
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Guest Editor
Department für Chemie, Institut für Anorganische Chemie, Universität zu Köln, Greinstraße 6, 50939 Köln, Germany
Interests: transition metal complexes (including organometallic); platinum, palladium, nickel; synthesis; electrochemistry; photophysics; spectroscopy; modelling of catalytic processes
Prof. Dr. Constantinos C. Stoumpos
grade E-Mail Website
Guest Editor
Department of Chemistry, Northwestern University, Evanston, IL 60208, USA
Interests: synthetic inorganic chemistry; solid state chemistry; coordination chemistry; structure-property relationships; semiconductors; hybrid halide perovskites

Special Issue Information

Dear Colleagues,

In 2020, we are celebrating the 25th anniversary of our journal Molecules. To date, the journal has published more than 20,000 papers, and the journal website attracts 115,000 monthly visits and more than 395,000 monthly page-views. Our sincerest thanks go to our readers, innumerable authors, anonymous peer reviewers, editors, and all the people working in some way for the journal who have joined efforts for years. Without your help, we would never have achieved this.

To mark this important milestone, a Special Issue entitled “Recent Advances in Inorganic Chemistry” is being launched. This Special Issue collects communications, full papers, and high-quality review papers in the inorganic chemistry research fields. We kindly encourage all research groups covering various inorganic areas to make contributions to this Special Issue.

Dr. Burgert Blom
Dr. Erika Ferrari
Prof. Dr. Vassilis Tangoulis
Prof. Dr. Cédric R Mayer
Prof. Dr. Axel Klein
Prof. Dr. Constantinos C. Stoumpos
Guest Editors

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All papers will be peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Molecules is an international peer-reviewed open access semimonthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2000 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Published Papers (12 papers)

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Research

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Open AccessArticle
Reversible Diels–Alder Reactions with a Fluorescent Dye on the Surface of Magnetite Nanoparticles
Molecules 2021, 26(4), 877; https://doi.org/10.3390/molecules26040877 - 07 Feb 2021
Viewed by 446
Abstract
Diels–Alder reactions on the surface of nanoparticles allow a thermoreversible functionalization of the nanosized building blocks. We report the synthesis of well-defined magnetite nanoparticles by thermal decomposition reaction and their functionalization with maleimide groups. Attachment of these dienophiles was realized by the synthesis [...] Read more.
Diels–Alder reactions on the surface of nanoparticles allow a thermoreversible functionalization of the nanosized building blocks. We report the synthesis of well-defined magnetite nanoparticles by thermal decomposition reaction and their functionalization with maleimide groups. Attachment of these dienophiles was realized by the synthesis of organophosphonate coupling agents and a partial ligand exchange of the original carboxylic acid groups. The functionalized iron oxide particles allow a covalent surface attachment of a furfuryl-functionalized rhodamine B dye by a Diels–Alder reaction at 60 °C. The resulting particles showed the typical fluorescence of rhodamine B. The dye can be cleaved off the particle surface by a retro-Diels–Alder reaction. The study showed that organic functions can be thermoreversibly attached onto inorganic nanoparticles. Full article
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Open AccessArticle
Desymmetrizing Heteroleptic [Cu(P^P)(N^N)][PF6] Compounds: Effects on Structural and Photophysical Properties, and Solution Dynamic Behavior
Molecules 2021, 26(1), 125; https://doi.org/10.3390/molecules26010125 - 29 Dec 2020
Cited by 2 | Viewed by 455
Abstract
The preparation, characterization and electrochemical and photophysical properties of a series of desymmetrized heteroleptic [Cu(P^P)(N^N)][PF6] compounds are reported. The complexes incorporate the chelating P^P ligands bis(2-(diphenylphosphanyl)phenyl)ether (POP) and (9,9-dimethyl-9H-xanthene-4,5-diyl)bis(diphenylphosphane) (xantphos), and 6-substituted 2,2′-bipyridine (bpy) derivatives with functional groups attached [...] Read more.
The preparation, characterization and electrochemical and photophysical properties of a series of desymmetrized heteroleptic [Cu(P^P)(N^N)][PF6] compounds are reported. The complexes incorporate the chelating P^P ligands bis(2-(diphenylphosphanyl)phenyl)ether (POP) and (9,9-dimethyl-9H-xanthene-4,5-diyl)bis(diphenylphosphane) (xantphos), and 6-substituted 2,2′-bipyridine (bpy) derivatives with functional groups attached by –(CH2)n– spacers: 6-(2,2′-bipyridin-6-yl)hexanoic acid (1), 6-(5-phenylpentyl)-2,2′-bipyridine (2) and 6-[2-(4-phenyl-1H-1,2,3,triazol-1-yl)ethyl]-2,2′-bipyridine (3). [Cu(POP)(1)][PF6], [Cu(xantphos)(1)][PF6], [Cu(POP)(2)][PF6], [Cu(xantphos)(2)][PF6], and [Cu(xantphos)(3)][PF6] have been characterized in solution using multinuclear NMR spectroscopy, and the single crystal structure of [Cu(xantphos)(3)][PF6].0.5Et2O was determined. The conformation of the 6-[2-(4-phenyl-1H-1,2,3,triazol-1-yl)ethyl]-substituent in the [Cu(xantphos)(3)]+ cation is such that the α- and β-CH2 units reside in the xanthene ‘bowl’ of the xantphos ligand. The 6-substituent desymmetrizes the structure of the [Cu(P^P)(N^N)]+ cation and this has consequences for the interpretation of the solution NMR spectra of the five complexes. The NOESY spectra and EXSY cross-peaks provide insight into the dynamic processes operating in the different compounds. For powdered samples, emission maxima are in the range 542–555 nm and photoluminescence quantum yields (PLQYs) lie in the range 13–28%, and a comparison of PLQYs and decay lifetimes with those of [Cu(xantphos)(6-Mebpy)][PF6] indicate that the introduction of the 6-substituent is not detrimental in terms of the photophysical properties. Full article
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Open AccessArticle
In Vitro Antifungal Activity and Mechanism of Ag3PW12O40 Composites against Candida Species
Molecules 2020, 25(24), 6012; https://doi.org/10.3390/molecules25246012 - 18 Dec 2020
Viewed by 461
Abstract
Fungal infections pose a serious threat to human health. Polyoxometalates (POMs) are metal–oxygen clusters with potential application in the control of microbial infections. Herein, the Ag3PW12O40 composites have been synthesized and verified by Fourier transform infrared (FT-IR) spectrum, [...] Read more.
Fungal infections pose a serious threat to human health. Polyoxometalates (POMs) are metal–oxygen clusters with potential application in the control of microbial infections. Herein, the Ag3PW12O40 composites have been synthesized and verified by Fourier transform infrared (FT-IR) spectrum, transmission electron microscopy (TEM), scanning electron microscope (SEM), elemental analysis, and X-ray diffraction (XRD). The antifungal activities of Ag3PW12O40 were screened in 19 Candida species strains through the determination of minimum inhibitory concentration (MIC) by the microdilution checkerboard technique. The minimum inhibitory concentration (MIC50) values of Ag3PW12O40 are 2~32 μg/mL to the Candida species. The MIC80 value of Ag3PW12O40 to resistant clinical isolates C. albicans HL963 is 8 μg/mL, which is lower than the positive control, fluconazole (FLC). The mechanism against C. albicans HL963 results show that Ag3PW12O40 can decrease the ergosterol content. The expressions of ERG1, ERG7, and ERG11, which impact on the synthesis of ergosterol, are all prominently upregulated by Ag3PW12O40. It indicates that Ag3PW12O40 is a candidate in the development of new antifungal agents. Full article
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Open AccessArticle
Mechanochemical P-derivatization of 1,3,5-Triaza-7-Phosphaadamantane (PTA) and Silver-Based Coordination Polymers Obtained from the Resulting Phosphabetaines
Molecules 2020, 25(22), 5352; https://doi.org/10.3390/molecules25225352 - 16 Nov 2020
Viewed by 421
Abstract
We have described earlier that in aqueous solutions, the reaction of 1,3,5-triaza-7-phosphaadamantane (PTA) with maleic acid yielded a phosphonium-alkanoate zwitterion. The same reaction with 2-methylmaleic acid (citraconic acid) proceeded much slower. It is reported here, that in the case of glutaconic and itaconic [...] Read more.
We have described earlier that in aqueous solutions, the reaction of 1,3,5-triaza-7-phosphaadamantane (PTA) with maleic acid yielded a phosphonium-alkanoate zwitterion. The same reaction with 2-methylmaleic acid (citraconic acid) proceeded much slower. It is reported here, that in the case of glutaconic and itaconic acids (constitutional isomers of citraconic acid), formation of the corresponding phosphabetaines requires significantly shorter reaction times. The new phosphabetaines were isolated and characterized by elemental analysis, multinuclear NMR spectroscopy and ESI-MS spectrometry. Furthermore, their molecular structures in the solid state were determined by single crystal X-ray diffraction (SC-XRD). Synthesis of the phosphabetaines from PTA and unsaturated dicarboxylic acids was also carried out mechanochemically with the use of a planetary ball mill, and the characteristics of the syntheses in solvent and under solvent-free conditions were compared. In aqueous solutions, the reaction of the new phosphabetaines with Ag(CF3SO3) yielded Ag(I)-based coordination polymers. According to the SC-XRD results, in these polymers the Ag(I)-ion coordinates to the N and O donor atoms of the ligands; however, Ag(I)-Ag(I) interactions were also identified. The Ag(I)-based coordination polymer (CP1.2) formed with the glutaconyl derivative of PTA (1) showed considerable antimicrobial activity against both Gram-negative and Gram-positive bacteria and yeast strains Full article
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Open AccessCommunication
Controlling the Size and Pattern Pitch of Ni(OH)2 Nanoclusters Using Dip-Pen Nanolithography to Improve Water Oxidation
Molecules 2020, 25(12), 2937; https://doi.org/10.3390/molecules25122937 - 26 Jun 2020
Viewed by 654
Abstract
We use dip-pen nanolithography to accurately pattern Ni(OH)2 nanoclusters on a metachemical surface with an exceptionally large surface area. The distance between the nanoclusters can be manipulated to control the oxygen-evolution reaction current and overpotential, thereby improving the efficiency of the water-splitting [...] Read more.
We use dip-pen nanolithography to accurately pattern Ni(OH)2 nanoclusters on a metachemical surface with an exceptionally large surface area. The distance between the nanoclusters can be manipulated to control the oxygen-evolution reaction current and overpotential, thereby improving the efficiency of the water-splitting process while using minute amounts of the catalyst. Full article
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Open AccessFeature PaperArticle
Synthesis, Spectroscopy, Electrochemistry and DFT of Electron-Rich Ferrocenylsubphthalocyanines
Molecules 2020, 25(11), 2575; https://doi.org/10.3390/molecules25112575 - 01 Jun 2020
Cited by 1 | Viewed by 594
Abstract
A series of novel ferrocenylsubphthalocyanine dyads Y-BSubPc(H)12 with ferrocenyl-carboxylic acids Y-H = (FcCH2CO2-H), (Fc(CH2)3CO2-H) or (FcCO(CH2)2CO2-H) in the axial position were synthesized from the parent Cl-BSubPc(H) [...] Read more.
A series of novel ferrocenylsubphthalocyanine dyads Y-BSubPc(H)12 with ferrocenyl-carboxylic acids Y-H = (FcCH2CO2-H), (Fc(CH2)3CO2-H) or (FcCO(CH2)2CO2-H) in the axial position were synthesized from the parent Cl-BSubPc(H)12 via an activated triflate-SubPc intermediate. UV/Vis data revealed that the axial ferrocenyl-containing ligand did not influence the Q-band maxima compared to Cl-BSubPc(H)12. A combined electrochemical and density functional theory (DFT) study showed that Fe group of the ferrocenyl-containing axial ligand is involved in the first reversible oxidation process, followed by a second oxidation localized on the macrocycle of the subphthalocyanine. Both observed reductions were ring-based. It was found that the novel Fc(CH2)3CO2BSubPc(H)12 exhibited the lowest first macrocycle-based reduction potential (−1.871 V vs. Fc/Fc+) reported for SubPcs till date. The oxidation and reduction values of Fc(CH2)nCO2BSubPc(H)12 (n = 0–3), FcCO(CH2)2CO2BSubPc(H)12, and Cl-BSubPc(H)12 illustrated the electronic influence of the carboxyl group, the different alkyl chains and the ferrocenyl group in the axial ligand on the ring-based oxidation and reduction values of the SubPcs. Full article
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Open AccessArticle
Oxidative Dehydrogenation of Propane over Vanadium-Containing Faujasite Zeolite
Molecules 2020, 25(8), 1961; https://doi.org/10.3390/molecules25081961 - 23 Apr 2020
Cited by 3 | Viewed by 740
Abstract
Oxidative dehydrogenation (ODH) of light alkanes to olefins—in particular, using vanadium-based catalysts—is a promising alternative to the dehydrogenation process. Here, we investigate how the activity of the vanadium phase in ODH is related to its dispersion in porous matrices. An attempt was made [...] Read more.
Oxidative dehydrogenation (ODH) of light alkanes to olefins—in particular, using vanadium-based catalysts—is a promising alternative to the dehydrogenation process. Here, we investigate how the activity of the vanadium phase in ODH is related to its dispersion in porous matrices. An attempt was made to synthesize catalysts in which vanadium was deposited on a microporous faujasite zeolite (FAU) with the hierarchical (desilicated) FAU as supports. These yielded different catalysts with varying amounts and types of vanadium phase and the porosity of the support. The phase composition of the catalysts was confirmed by X-ray diffraction (XRD); low temperature nitrogen sorption experiments resulted in their surface area and pore volumes, and reducibility was measured with a temperature-programmed reduction with a hydrogen (H2-TPR) method. The character of vanadium was studied by UV-VIS spectroscopy. The obtained samples were subjected to catalytic tests in the oxidative dehydrogenation of propane in a fixed-bed gas flow reactor with a gas chromatograph to detect subtract and reaction products at a temperature range from 400–500 °C, with varying contact times. The sample containing 6 wt% of vanadium deposited on the desilicated FAU appeared the most active. The activity was ascribed to the presence of the dispersed vanadium ions in the tetragonal coordination environment and support mesoporosity. Full article
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Open AccessArticle
Rapid and Scalable Wire-bar Strategy for Coating of TiO2 Thin-films: Effect of Post-Annealing Temperatures on Structures and Catalytic Dye-Degradation
Molecules 2020, 25(7), 1683; https://doi.org/10.3390/molecules25071683 - 07 Apr 2020
Cited by 2 | Viewed by 723
Abstract
Titanium dioxide (TiO2) thin films were rapidly coated on Corning glass substrates from the precursor solution using the wire-bar technique at the room temperature and then post-annealed at 400, 500 and 600 °C for 1 h under atmospheric conditions. The structural, [...] Read more.
Titanium dioxide (TiO2) thin films were rapidly coated on Corning glass substrates from the precursor solution using the wire-bar technique at the room temperature and then post-annealed at 400, 500 and 600 °C for 1 h under atmospheric conditions. The structural, morphological, optical, wettability and photocatalytic properties of the films were studied. X-ray diffraction analysis confirmed the formation of an anatase TiO2 structure irrespective of the post-annealing temperatures. The optical transparency of the films in the visible range was measured to be > 70%. A water contact angle (WCA) of ~0° was observed for TiO2 thin-film, post-annealed at 400 °C and 500 °C. However, WCA of 40.3° was observed for post-annealed at 600 °C. The photocatalytic dye-degradation using post-annealed thin-film was investigated indicating a steady improvement in the dye-degradation percentage (from 24.3 to 29.4%) with the increase of post-annealing temperature. The demonstrated TiO2 thin-films deposited by wire-bar coating technique showed promises for the manufacturing of large-area cost-effective self-cleaning window glass. Full article
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Open AccessArticle
Synthesis of Fe2SiO4-Fe7Co3 Nanocomposite Dispersed in the Mesoporous SBA-15: Application as Magnetically Separable Adsorbent
Molecules 2020, 25(4), 1016; https://doi.org/10.3390/molecules25041016 - 24 Feb 2020
Cited by 1 | Viewed by 827
Abstract
The mixture containing alloy and oxide with iron-based phases has shown interesting properties compared to the isolated species and the synergy between the phases has shown positive effect on dye adsorption. This paper describes the synthesis of Fe2SiO4-Fe7 [...] Read more.
The mixture containing alloy and oxide with iron-based phases has shown interesting properties compared to the isolated species and the synergy between the phases has shown positive effect on dye adsorption. This paper describes the synthesis of Fe2SiO4-Fe7Co3-based nanocomposite dispersed in Santa Barbara Amorphous (SBA)-15 and its application in dye adsorption followed by magnetic separation. Thus, it was studied the variation of reduction temperature and amount of hydrogen used in synthesis and the effect of these parameters on the physicochemical properties of the iron and cobalt based oxide/alloy mixture, as well as the methylene blue adsorption capacity. The XRD and Mössbauer results, along with the temperature-programmed reduction (TPR) profiles, confirmed the formation of Fe2SiO4-Fe7Co3-based nanocomposites. Low-angle XRD, N2 isotherms, and TEM images show the formation of the SBA-15 based mesoporous support with a high surface area (640 m2/g). Adsorption tests confirmed that the material reduced at 700 °C using 2% of H2 presented the highest adsorption capacity (49 mg/g). The nanocomposites can be easily separated from the dispersion by applying an external magnetic field. The interaction between the dye and the nanocomposite occurs mainly by π-π interactions and the mixture of the Fe2SiO4 and Fe7Co3 leads to a synergistic effect, which favor the adsorption. Full article
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Review

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Open AccessReview
Inorganic Nanoparticle-Loaded Exosomes for Biomedical Applications
Molecules 2021, 26(4), 1135; https://doi.org/10.3390/molecules26041135 - 20 Feb 2021
Viewed by 401
Abstract
Exosomes are intrinsic cell-derived membrane vesicles in the size range of 40–100 nm, serving as great biomimetic nanocarriers for biomedical applications. These nanocarriers are known to bypass biological barriers, such as the blood–brain barrier, with great potential in treating brain diseases. Exosomes are [...] Read more.
Exosomes are intrinsic cell-derived membrane vesicles in the size range of 40–100 nm, serving as great biomimetic nanocarriers for biomedical applications. These nanocarriers are known to bypass biological barriers, such as the blood–brain barrier, with great potential in treating brain diseases. Exosomes are also shown to be closely associated with cancer metastasis, making them great candidates for tumor targeting. However, the clinical translation of exosomes are facing certain critical challenges, such as reproducible production and in vivo tracking of their localization, distribution, and ultimate fate. Recently, inorganic nanoparticle-loaded exosomes have been shown great benefits in addressing these issues. In this review article, we will discuss the preparation methods of inorganic nanoparticle-loaded exosomes, and their applications in bioimaging and therapy. In addition, we will briefly discuss their potentials in exosome purification. Full article
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Open AccessReview
Magnesium, Iron, Zinc, Copper and Selenium Status in Attention-Deficit/Hyperactivity Disorder (ADHD)
Molecules 2020, 25(19), 4440; https://doi.org/10.3390/molecules25194440 - 27 Sep 2020
Cited by 1 | Viewed by 1007
Abstract
In this study, we critically review the literature concerning the relation of Mg, Fe, Zn, Cu and Se and attention-deficit/hyperactivity disorder (ADHD). Elemental status is estimated using peripheral blood parameters, hair, urine, daily intake and response to supplementation. The observed associations between concentration [...] Read more.
In this study, we critically review the literature concerning the relation of Mg, Fe, Zn, Cu and Se and attention-deficit/hyperactivity disorder (ADHD). Elemental status is estimated using peripheral blood parameters, hair, urine, daily intake and response to supplementation. The observed associations between concentration levels of the elements Mg, Fe, Zn, Cu and Se and ADHD symptoms are contradictory. This is partly due to the heterogeneity and complexity of the disorder. As a trend, lower ferritin and zinc levels can be observed. However, this correlation is not causative, as illustrated by placebo-controlled trials reporting conflicting evidence on the efficacy of supplementation. Well-defined studies on changes in concentration levels of the elements in relation to ADHD symptoms before and after treatment with therapeutics it will be possible to shed more light on the significance of these elements in this behavioral disorder. The discussion on whether a change in concentration of an element is cause or consequence of ADHD is not within the scope of this article. Full article
Open AccessReview
New Horizons in Chemical Functionalization of Endohedral Metallofullerenes
Molecules 2020, 25(16), 3626; https://doi.org/10.3390/molecules25163626 - 10 Aug 2020
Cited by 1 | Viewed by 660
Abstract
This overview explains some new aspects of chemical functionalization of endohedral metallofullerenes (EMFs) that have been unveiled in recent years. After differences in chemical reactivity between EMFs and the corresponding empty fullerenes are discussed, cage-opening reactions of EMFs are examined. Then, the selective [...] Read more.
This overview explains some new aspects of chemical functionalization of endohedral metallofullerenes (EMFs) that have been unveiled in recent years. After differences in chemical reactivity between EMFs and the corresponding empty fullerenes are discussed, cage-opening reactions of EMFs are examined. Then, the selective bisfunctionalization of EMFs is explained. Finally, single-bonding derivatization of EMFs is addressed. The diversity and applicability of the chemical functionalization of endohedral metallofullerenes are presented to readers worldwide. Full article
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