Search Results (189)

The synthesis of cannabigerol—a cannabinoid with significant pharmaceutical potential—is described. The synthesis involves four stages. In the first step, (E)-non-3-en-2-one reacts with dimethyl malonate to yield a cyclic enone, which is subsequently oxidized with bromine to produce the olivetol ester. This ester then undergoes an alumina-catalyzed coupling reaction with geraniol, followed by ester hydrolysis to obtain cannabigerol. By modifying the chain length of the enone in the initial step and employing allylic alcohols other than geraniol, a range of cannabigerol derivatives can be synthesized, including the natural product cannabigerovarin. Full article

The efficient synthetic routes and evaluates cytotoxic profiles of denitroaristolochic acids II–V (DAA-II–V) were demonstrated in this study. Based on retrosynthetic analysis, a modular synthetic strategy was developed through Suzuki–Miyaura coupling, Wittig reaction, and bismuth triflate-catalyzed intramolecular Friedel–Crafts cyclization to efficiently construct the phenanthrene core. Process optimization significantly improved yields: aryl bromide intermediate A reached 50.8% yield via bromination refinement, while arylboronic ester intermediate B overcame selectivity limitations. Combining Darzens condensation with Wittig reaction enhanced throughput, achieving 88.4% yield in the key cyclization. Structures were confirmed by NMR and mass spectra. CCK-8 cytotoxicity assays in human renal proximal tubular epithelial cells revealed distinct toxicological profiles: DAA-III and DAA-IV exhibited IC₅₀ values of 371 μM and 515 μM, respectively, significantly higher than the nitro-containing prototype AA-I (270 μM), indicating that the absence of nitro group attenuates but does not eliminate toxicity, potentially via altered metabolic activation. DAA-II and DAA-V showed no detectable cytotoxicity within assay limits, suggesting reduced toxicological impact. Structure–activity analysis exhibited that the nitro group is not essential for cytotoxicity, with methoxy substituents exerting limited influence on potency. This challenges the conventional DNA adduct-dependent toxicity paradigm, implying alternative mechanisms like oxidative stress or mitochondrial dysfunction may mediate damage in denitro derivatives. These systematic findings provide new perspectives for AA analog research and a foundation for the rational use and safety assessment of Aristolochiaceae plants. Full article

Government regulations have required consumer products—electrical and electronic components, toys, furniture, clothing, and cars— to meet ever-increasing flame resistance standards, and industry has met these norms by adding brominated fire retardants. However, end-of-life treatment and up-cycling of these plastics is challenging as the brominated compounds are endocrine disruptors, bioaccumulators, and persist in the environment. Pyrolysis, catalytic cracking, or combustion, to recover its fuel value, produces toxic brominated dibenzodioxins and dibenzofurans Here, we demonstrated the efficacy of a solvothermal treatment that extracts up to 99% of the bromine from high-impact polystyrene (HIPS) and polystyrene (PS) in electrical and electronic waste (e-waste). The process operated between 160 °C and 230 °C with ethylene glycol or triethylene glycol as the solvent and NaOH or KOH as the extraction agent (0.5 M to 2 M). The reaction rates depended on the particle size: 60 mm plastic chunks took up to between 4 and 24 h to react while fibers 3 mm in diameter reacted in less than 5 min. Full article

Unlike the wide number of natural biflavonoids, natural bichalcones are a rare and even less studied class. Nevertheless, some of them have proved their interest in the fight against cancer through their cytotoxic activity against human tumor cell lines. The aim of this study was to synthesize a novel bichalcone: 3′,3‴,4,4′,4″,4‴,5′,5‴-octamethoxy-2,3″-bichalcone 1. The most efficient synthetic pathway was the Suzuki–Miyaura reaction between a boronated chalcone and a brominated one. Full article

Zinc-halogen batteries are usually based on two-electron transfer reactions from X⁻ to X₂. However, the halogen is capable of being further oxidized to higher valence states, thereby achieving the higher capacity of zinc- halogen batteries. Here, a six-electron reaction based on I⁻/I⁺ and Br⁻/Br⁰ is activated successfully by introducing KI into the electrolyte. ZIF-8-derived porous carbon (ZPC), serving as the host of halogen, effectively suppresses polybromide/polyiodide shuttle owing to the chemisorption/physical adsorption. Additionally, the adsorption of I⁻ on the surface of the zinc anode effectively inhibits the growth of dendrites and the formation of by-products. Consequently, zinc-bromine batteries exhibit outstanding electrochemical performance, including a specific capacity of 345 mAh g⁻¹ at 1 A g⁻¹ and an excellent capacity retention of 80% after 3000 cycles at 2 A g⁻¹. This strategy provides a novel way for enhancing the electrochemical performance of zinc-halogen batteries. Full article

In previous quests to synthesize fragments of tumor-associated carbohydrate antigens (TACAs), we determined that bromoalkyl β glycosides of N-acetylglucosamine were labile and incompatible with some of the synthetic conditions required for the preparation of oligosaccharides. While N-acetylglucosamine chloroalkyl β glycosides are common intermediates for oligosaccharide synthesis, they exhibit poor yields upon subsequent reactions used to introduce the oxyamine required for further conjugation. Thus, we looked to synthesize these TACAs using chloroalkyl β glycosides and substitute the chlorine for bromine at a later synthetic stage. Upon substitution of the bromine for chlorine using sodium bromide in a dibromomethane (DBM) dimethylformamide (DMF) mixture, we observed the unexpected anomerization of the N-acetylglucosamine β glycosides, yielding up to 90% of the α glycosides. We describe our studies of this unexpected anomerization and report on how the anomeric ratios can be controlled experimentally. Interestingly, we also report the anomerization of alkyl β glycosides of N-acetylglucosamine in a mixture of DBM and DMF without sodium bromide. Further studies are being conducted to determine the mechanism of this anomerization and the scope of this reaction. Full article

Demand and prices for antimony have increased over the last few years. Recycling supplied 15% of domestic consumption in the US, while the remaining 85% was imported. Hydrometallurgical processes have long used alkaline sulfide systems and hydrochloric acid, closing doors on new approaches. Bromine compounds have been recently used to recover PGMs and REEs successfully; thus, antimony leaching with bromine compounds is theoretically feasible. This research was conducted to develop a viable technology for hydrobromic acid between 50 °C and 70 °C as a leaching reagent on dross through single- and two-stage leaching using design of experiment (DoE) and adding sustainability to current industrial processes while minimizing waste products in recycling processes. The preliminary results showed that bromine, specifically hydrobromic acid, can be used as a leaching reagent for antimony dissolution. By decreasing the lead content in the solids and increasing the concentration, temperature, and reaction time, antimony leaching from the dross was increased from 20% to 50%. The findings, coupled with acid regeneration, can be implemented as an alternative to other reagents in industrial plants. Full article

Dissolved organic carbon (DOC) is a critical parameter in water quality management due to its interaction with disinfectants, leading to the formation of disinfection byproducts (DBPs) during water treatment. Forest ecosystems are key contributors of DOC to surface waters, stemming from soil leachate. This study is the first to use DOC solutions directly extracted from soil to examine the formation of trihalomethanes (THMs) during chlorination and chloramination under varying environmental conditions. For this purpose, soil samples from a densely forested upland Cedar Lake watershed in Illinois were processed to extract DOC, which was then subjected to controlled disinfection experiments under varying pH, temperature, disinfectant dose, and reaction time. The results demonstrate that chlorination produces significantly higher levels of THMs compared to chloramination, with THM concentrations ranging from 31.996 μg/L to 62.563 μg/L for chlorination and 0.508 μg/L to 0.865 μg/L for chloramination. The yields of DBPs determined by chloramination increased approximately 4, 5, and 10 times with a higher DOC concentration, disinfectant concentration, and reaction time, respectively. For chlorination, these increases were approximately 5, 8, and 3 times, respectively. The presence of bromide in the DOC solutions influenced the concentration of brominated THMs (Br-THMs). The results indicate that a high formation of THMs, during both disinfection processes, occurred in the pH range of 7–8 and temperature range of 20–25 degrees Celsius. Furthermore, all tested water quality indicators (DOC, total dissolved solids, turbidity, and UV254), except for pH and Specific Ultraviolet Absorbance (SUVA), exhibited a strong positive correlation with THM levels during chlorination. In contrast, these parameters displayed a moderate to weak correlation with THM levels in the chloramination process. These findings highlight the critical role of DOC characteristics and disinfection conditions in controlling THM formation, providing valuable insights for optimizing water treatment processes. Full article

In this study, a modified synthetic method for labeling a lignin dimer (guaiacylglycerol-β-guaiacyl ether-[α-¹³C]) was developed. The chemical structure of the target compound was analyzed using ¹H-NMR, ¹³C-NMR, and other analytical techniques. Then, the ¹³C-labeled phenolic lignin model compound was subjected to kraft pulping in the presence of xylose. Finally, the resulting reaction products were fractionated using acid precipitation and ethyl acetate extraction, and each fraction was analyzed by carbon-13 nuclear magnetic resonance (¹³C-NMR) and two-dimensional heteronuclear multiple quantum coherence (HMQC) spectroscopy. This aimed to investigate the occurrence of lignin–carbohydrate complexes (LCCs) during the conventional kraft pulping process. Employing ethanol as the reaction medium facilitated the bromination of 4-acetylguaiacol-[α-¹³C], resulting in a homogeneous reaction and significantly improving the yield of the brominated product to over 90%. Additionally, kraft pulping of the phenolic lignin model compound in the presence of xylose led to the occurrence of minor quantities of benzyl ether-type lignin–carbohydrate complex (LCC) structures, which were predominantly detected in the ethyl acetate extractive. Full article

We describe an approach towards the synthesis of previously unknown 3-benzoyl-1′,3′,6-trimethyl-2′H,3H,4H-spiro[furo[3,2-c]pyran-2,5′-pyrimidine]-2′,4,4′,6′(1′H,3′H)-tetraone. The presented method is based on the cyclization of 5-(1-(4-hydroxy-6-methyl-2-oxo-2H-pyran-3-yl)-2-oxo-2-phenylethyl)-1,3-dimethylpyrimidine-2,4,6(1H,3H,5H)-trione. It was shown that the presented reaction proceeds through the stage of bromination of the starting compound followed by O-nucleophilic attack. The structures of the obtained compound were established by ¹H, ¹³C NMR and IR spectroscopy, and high-resolution mass spectrometry. Full article

The presented work discusses the highly efficient esterification of poly (γ-glutamic acid) (γ-PGA) with alkyl halides at room temperature. The esterification reaction was completed within 3 h, and the prepared γ-PGA esters were obtained with excellent yields (98.6%) when 1,1,3,3-tetramethylguanidine (TMG) was used as a promoter. The influence of the amount of TMG, solvent, reaction conditions, and alkyl halides on the esterification reaction was examined. It was found that polar aprotic solvents, such as N-Methylpyrrolidone (NMP) and 1,3-Dimethyl-2-imidazolidinone (DMI), were favorable for the esterification. Non-polar or weakly polar solvents (i.e., dichloroethane, acetonitrile) were not favorable for the esterification. Water as a solvent had a negative effect on esterification. The reactivity of bromine halogenated compounds was higher than that of chlorine halogenated compounds but lower than that of iodine halogenated compounds. The structures of the prepared γ-PGA ester were confirmed by ¹H NMR and FT-IR spectroscopy. Thermal stability and hydrophobic properties of the resulting product were tested. The results showed that the prepared γ-PGA propyl ester had high thermal stability (up to 267 °C) and showed good hydrophobicity (contact angle 118.7°). Full article

Seawater is a long-standing remedy against a number of skin or rheumatic conditions since ancient times, now popular in many countries, where spa, thalassotherapy and seawater pools have considerably boomed. Exposure to seawater and sunlight is an essential component of thalassotherapy, defined by any controlled interaction with marine environments and their natural elements, even in the absence of skin applications of algae, sands or muds. Seawater pools therefore offer the opportunity of thalassotherapy to patients unable to go the beach or during the winter months. The evidence from various studies seems to converge on combined exposure to solar radiation and seawater as a more effective approach than irradiation alone or bathing in freshwater followed by irradiation to reduce symptoms of inflammatory skin diseases or rheumatic conditions. An unwanted consequence of chlorine-based treatment of seawater is the formation of disinfection-by-products (DBPs) due to reactions of disinfectants with organic matter of anthropogenic origin released by bathers. Whilst chlorination of freshwater predominantly generates chlorinated DBPs, the prevailing species produced by chlorination of seawater pools are brominated DBPs, reportedly more genotoxic. However, despite greater toxicity of brominated DBPs, there is evidence that DBPs concentration in freshwater pools is significantly higher (probably due to the larger number of users) compared to seawater pools. Containing the number of bathers could therefore reduce the risk of exposure to DBPs in both types of pool. The outdoor location of pools can further contribute to reducing the risk of genotoxicity thanks to volatilization, airborne dispersion and photodegradation of some DBPs. Full article

Electrodialysis (ED) has already been applied to recover nickel in galvanizing processes, allowing nickel recovery and the production of a treated effluent with demineralized water quality. However, the growth in ED use is still limited by the production and commercialization of ion-selective membranes, currently limited to a few large companies. Therefore, this paper presents the development of homogeneous cationic and anionic membranes made from poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) for ED use. Cationic membranes were prepared by the sulfonation reaction of PPO under different experimental conditions (PPO:H₂SO₄ molar ratio and reaction time). Anionic membranes were prepared by the bromination reaction of PPO, followed by the amination reaction. The membranes were characterized for their chemical and electrochemical properties, including ion exchange capacity, conductivity, thermal stability, and surface morphology. The optimal conditions for cationic membrane sulfonation were achieved with a 1:4.4 PPO:H₂SO₄ molar ratio, and a reaction time of 0.5 h. For anionic membranes, the best results were obtained with bromination, with a PPO:NBS (N-Bromosuccinimide) molar ratio of 1:0.5, followed by 14 days of amination. Overall, 91.8% chloride, 90.9% sulfate, and 85.5% nickel ion extraction was achieved, highlighting PPO as a promising polymer for the development of anionic and cationic ion-selective membranes for ED. Full article

Photoredox-catalyzed phosphonylation of bromo-substituted 1,10-phenanthrolines under visible light irradiation was studied. The reaction was shown to proceed under mild conditions with Eosin Y as a photocatalyst in DMSO under blue light irradiation. It is transition-metal-free and affords the target phosphonate-substituted 1,10-phenanthrolines in moderate yields (26–51%) in 22 to 40 h. The rate and selectivity of the reaction depend largely on the position of the bromine atom, as well as on the nature and position of other substituents in the 1,10-phenanthroline core. Full article

Leishmaniasis, a protozoan disease affecting humans, exposes significant shortcomings in current treatments. In continuation to our previous findings on amidoxime-based antileishmanial compounds bearing a 4,5-dihydrofuran scaffold, twelve new amidoxime derivatives substituted at position 3 with an amide bearing a nitrogen heterocycle were synthesized. This series was designed to replace the sulfone and aryl group on a previously reported HIT. The synthesis of these compounds involved the following three-step pathway: manganese (III) acetate-based cyclization of a β-ketoester, followed by amidation with LiHMDS and a final reaction with hydroxylamine. Three of them, containing either bromine, chlorine, or methyl substitutions and featuring a pyridine moiety, showed an interesting toxicity–activity relationship in vitro. They exhibited IC₅₀ values of 15.0 µM, 16.0 µM, and 17.0 µM against the promastigote form of the parasite and IC₅₀ values of 0.5 µM, 0.6 µM, and 0.3 µM against the intracellular amastigote form, respectively. A selectivity index (SI) greater than 300 was established between the cytotoxic concentrations (in murine macrophages) and the effective concentrations (against the intracellular form of Leishmania amazonensis). This SI is at least seventy times higher than that observed for Pentamidine and twenty-five times higher than that observed for the reference HIT, as previously reported. Full article