Methyl Ether Research Articles

Phytochemical and pharmacological investigation of the non-volatile compounds of Lepidium cartilagineum (J. C. Mayer) Thell. and determination of the essential oil composition of its flowers and fruits

Eighteen compounds, among them phenylpropanoids (1–2), neolignans (3–9), a megastigmane (10), a phenyl glucoside (11), flavonoids (12–14), and N-containing compounds (15–18) were isolated from the methanolic extract of the whole plant of L. cartilagineum. The structures of the compounds were determined by NMR and MS measurements. The composition of the essential oils prepared from the flowers and fruits of L. cartilagineum was investigated using GC and GC–MS measurements. The essential oils were rich in aliphatic aldehydes and hydrocarbons, but low in sulfur-containing compounds, e.g., isothiocyanates. The extracts prepared from the aerial parts and roots of the plant, the essential oil, and the isolated compounds (1–9) were tested for antiproliferative activity against COLO 205 and COLO 320 cell lines and antibacterial activity on Lactobacillus rhamnosus. Dehydrodiconiferyl alcohol γ’-methyl ether (5) possessed marked antiproliferative activity against both human tumor cell lines. Neither the extracts nor the compounds affected the growth of the bacteria and did not influence the biofilm formation of L. rhamnosus. Based on the results, it can be concluded that L. cartilagineum is non-toxic to the human gut microbiome forming L. rhamnosus.

Модификация твердофазной полимерной поверхности путём прививки акриловых мономеров

Graft copolymerization onto a solid polymer surface is an effective tool for its modification. A large number of works have been published and require systematization. A search and review of English-language scientific literature devoted to the graft copolymerization of acrylic monomers onto a polymeric solid-phase surface have been carried out. Grafting onto plates and films, as well as fibers and colloidal particles, is considered. It has been revealed that the most popular substrates for graft copolymerization are, besides polyethylene, propylene and polyethylene terephthalate; polyurethanes, polyfluoroethylenes, rubbers, etc. Graft polymerization mainly proceeds on amorphous areas of the substrate and does not destroy the crystalline phase. It is possible to use the methods of controlled radical polymerization (ATRP, RAFT). Of the acrylic monomers, acrylic and methacrylic acids, glycidyl acrylate and glycidyl methacrylate, and others have been used, while the main method has been UV photopolymerization with an initiator–benzophenone. Of the three aliphatic ketones (acetone, methyl ethyl ketone and methyl propyl ketone), acetone has been the best solvent. Cophotoinitiators have been also used (a synergistic effect was observed), corona discharge, gamma radiation (60Co), ozone and plasma treatment, and a supercritical CO2 medium. The degree of grafting has been controlled by changing the soaking time in the monomer, pressure, concentration of monomer and initiator in the liquid phase, reaction temperature and reaction time. A new technology of graft polymerization with photopatterning has also been proposed. Problems of graft polymerization in terms of surface modification of polymer materials (hydrophilization of the surface, improving paintability and wettability, enhancing adhesion to certain surfaces, biocompatibility) are touched upon, and possible areas of their application are outlined.

Abiotic Production of Dimethyl Sulfide, Carbonyl Sulfide, and Other Organosulfur Gases via Photochemistry: Implications for Biosignatures and Metabolic Potential

Among the atmospheric gases that have been proposed as possible biosignatures in exoplanetary atmospheres, organosulfur gases are currently considered one of the more robust indicators of extant life. These gases include dimethyl sulfide (DMS; CH3SCH3), carbonyl sulfide (OCS), and carbon disulfide (CS2), which are predominantly secondary metabolic products of living organisms on Earth. Here we present results that challenge this interpretation and provide constraints on the robustness of organosulfur gases as biosignatures. Through laboratory photochemical experiments, we show the abiotic production of organosulfur gases, including DMS, OCS, methane thiol (CH3SH), ethane thiol (C2H5SH), CS2, and ethyl methyl sulfide (CH3CH2SCH3) via photochemistry in analog atmospheres. Gas-phase products of H2S/CH4/N2 haze photochemistry, with or without CO2, were collected and analyzed using gas chromatography equipped with sulfur chemiluminescence detection. Depending on the starting conditions, we estimate that DMS, OCS, CH3SH, CH3CH2SH, CS2, and CH3CH2SCH3 are produced in mixing ratios >10−1 ppmv. We further demonstrate that as the mixing ratio of CO2 increases, so does the relative importance of OCS compared to DMS. Although our results constrain the robustness of common organosulfur gases as biosignatures, the presence of these compounds may serve as an indicator of metabolic potential on exoplanets.

A pH-Responsive Hydrogel for the Oral Delivery of Ursolic Acid: A Pentacyclic Triterpenoid Phytochemical.

In this study, poly(HEMA-PEGxMEM-IA) hydrogels were prepared by radical copolymerization of poly(ethylene glycol) methyl ether methacrylate (PEGxMEM), 2-hydroxyethyl methacrylate (HEMA), and itaconic acid (IA). The reaction was carried out in ethanolic solution using N,N'-methylenebisacrylamide (MBA) as a crosslinking agent and 1-hydroxycyclohexyl phenyl ketone (HCPK) as a photo-initiator. The poly(HEMA-PEGxMEM-IA) hydrogels (HGx) were evaluated as a delivery system for ursolic acid (UA), a phytochemical extracted from the plant Clinopodium revolutum, "flor de arena". The hydrogels were characterized by Fourier-transform infrared spectroscopy (FTIR-ATR), Raman spectroscopy, X-Ray diffraction (XRD), thermogravimetric analysis (TGA), and scanning electron microscopy (SEM). The swelling behavior was studied in buffer solutions from pH 2 to 10, specifically at pH 2.2 (gastric environment) and 7.4 (intestinal environment). It was found that the hydrogels studied showed sensitivity to pH. At pH 2.2, the degree of swelling for HG5 and HG9 hydrogels was 0.45 and 0.93 (g water/g hydrogel), respectively. At pH 7.4, the degree of swelling for HG5 and HG9 hydrogels was 1.97 and 2.64 (g water/g hydrogel), respectively. The SEM images show the variation in pore size as a function of pH, and the UA crystals in the pores of the hydrogels can also be observed. The in vitro UA release data best fit the Korsmeyer-Peppas kinetic model and the diffusion exponent indicates that the release mechanism is governed by Fickian diffusion.

Comparative Study of n-C5 Bond Dissociation Energies and H-Atom Abstraction via H for Alkane, Alcohol, Methyl Ether, Nitroso, Nitro, Nitrite, and Nitrate.

Energetic materials have a wide range of applications, for many of which new materials are constantly developed. For understanding how energetic materials are chemically converted, it is essential to systematically understand how relevant functional groups affect the stability and properties of such materials. Here, the impact of nitroso, nitro, nitrite, and nitrate functional groups on a pentyl moiety is studied theoretically, focusing on bond dissociation energies and H atom abstraction via Ḣ. The nitroso group is found to imply the strongest effects, while the nitro group appears to exert a stabilizing effect on the pentyl moiety. Importantly, the nitrogenated functional groups generally stabilize the pentyl moiety, in contrast to alcohol and methyl ether functional groups. Therefore, it is concluded that using analogies to the chemistries of the latter two functional groups for chemical kinetic modeling of nitrogenated functional groups is not adequate. Based on the presented bond dissociation energies and rate coefficients, it is to be expected that unimolecular bond fissions at the nitrogenated functional groups will dominate over a wide temperature range. Building on the provided data, future detailed chemical kinetic modeling efforts for nitroso, nitro, nitrite, and nitrate compounds can be aided or initiated.

Leveraging Ion Pairing and Transport in Localized High-Concentration Electrolytes for Reversible Lithium Metal Anodes at Low Temperatures.

Coulombic efficiency of over 99% is rarely achieved for Li metal anode below -40°C, hindering the practical application of high-energy-density Li metal batteries under extreme conditions. Herein, limiting factors for Li metal reversibility are investigated utilizing ether-based localized high-concentration electrolytes of different solvent-diluent combinations. We find that along with the desolvation barrier, bulk ion transport properties including ionic conductivity, transference number, and diffusivity are also crucial factors for low-temperature Li deposition behavior. Superior Li metal reversibility was observed within the combination of the solvent with moderately weak solvating power and the diluent with minimal viscosity, highlighting the role of ion transport and the necessity for a trade-off with desolvation. The optimized electrolyte composed of lithium bis(fluorosulfonyl)imide, methyl n-propyl ether, and 1,1,2,2-tetrafluoroethyl methyl ether delivers exceptional Coulombic efficiency of 99.34% at -40°C and 98.96% at -60°C under a current density of 0.5 mA cm-2. Furthermore, Li||LiCoO2 (2.7 mAh cm-2) cells demonstrate impressive reversible capacity and cycling stability at these temperatures. This work sheds light on the less-recognized relevance of bulk ion transport to low-temperature performance and provides guidelines for the electrolyte design of Li metal batteries operating in cold environments.

Anionic Solvation Transition at Low Temperatures for Reversible Anodes in Lithium-Oxygen Batteries.

Li-O2 batteries provide a novel technology for electric energy storage due to their high energy density. However, the strong solvent coordination with Li+ at low temperatures impacts their performance and triggers irreversible interfacial reactions on the Li anode. Herein, cyclopentyl methyl ether (CME) is incorporated in a dimethoxyethane (DME)-based electrolyte to realize an anionic solvation transition at low temperatures in Li-O2 batteries. CME featuring a single O coordination site substitutes highly solvating DME in the first solvation sheath, and it induces more anion coordination to Li+ across the room- and low-temperature ranges. The low residence time of CME (66 ps at 25 °C, 382 ps at -40 °C.) in the solvation structures leads to the fast exchange of coordinated CME molecules with Li+ in comparison with DME and facilitates Li+ desolvation at low temperatures. The simultaneously generated inorganic-rich solid electrolyte interphase promotes Li+ transport to improve Li deposition and suppress Li dendrite formation. These enable the Li-O2 battery to present a good cycling stability of 110 cycles with a fixed capacity of 1000 mA h g-1 at -40 °C. This work paves the way for designing novel electrolytes in low-temperature batteries.

Loss of OsMATE6 Function Enhances Drought Resistance Without Yield Penalty by Regulating Stomatal Closure in Rice.

Drought is one of the most severe environmental factors limiting plant growth and crop yield, necessitating the identification of genes that enhance drought resistance for crop improvement. Through screening an ethyl methyl sulfonate-mutagenized rice mutant library, we isolated the PEG tolerance mutant 97-1 (ptm97-1), which displays enhanced resistance to osmotic and drought stress, and increased yield under drought conditions. A point mutation in OsMATE6 was identified as being associated with the drought-resistant phenotype of ptm97-1. The role of OsMATE6 in conferring drought resistance was confirmed by additional OsMATE6 knockout mutants. OsMATE6 is expressed in guard cells, shoots and roots and the OsMATE6-GFP fusion protein predominantly localizes to the plasma membrane. Our ABA efflux assays suggest that OsMATE6 functions as an ABA efflux transporter; mutant protoplasts exhibited a slower ABA release rate compared to the wild type. We hypothesize that OsMATE6 regulates ABA levels in guard cells, influencing stomatal closure and enhancing drought resistance. Notably, OsMATE6 knockout mutants demonstrated greater yields under field drought conditions compared to wild-type plants, highlighting OsMATE6 as a promising candidate for improving crop drought resistance.

Insights into the Mechanisms of Single-Photon and Two-Photon Excited Surface Enhanced Fluorescence by Submicrometer Silver Particles.

Surface enhanced fluorescence (SEF) based on noble metal nanoparticles is an effective means to achieve high sensitivity in fluorescence detection. Currently, the physical mechanism behind enhanced fluorescence is not fully understood. This paper measures the fluorescence signals of Dihydroporphyrin f methyl ether (CPD4) under both single-photon and two-photon excitation based on submicrometer silver particles with rough morphologies, achieving enhancement factors of 34 and 45 times, respectively. On this basis, by combining the radiative field characteristics produced by the silver particles, a stimulated radiation model of molecules is established to elucidate the changes in the molecular photophysical process when influenced by silver particles. Moreover, the fluorescence lifetime of the molecules was measured, showing that the presence of silver particles induces an increase in the molecular radiative decay rate, causing the fluorescence lifetime to decay from 3.8 ns to 3 ns. The results indicate that the fluorescence enhancement primarily originates from the submicrometer silver particles' enhancement effect on the excitation light. Additionally, the fluorescence signal emitted by the molecules couples with the silver particles, causing the local surface plasmon resonances generated by the silver particles to also emit light signals of the same frequency. Under the combined effect, the fluorescence of the molecules is significantly enhanced. The findings provide a theoretical foundation for understanding the fluorescence enhancement mechanism of silver particles, adjusting the enhancement effect, and developing enhanced fluorescence detection devices based on submicrometer silver particles, holding significant practical importance.

Micelles of poly[oligo(ethylene glycol) methacrylate] as delivery vehicles for zinc phthalocyanine photosensitizers

Drug-loaded polymeric micelles have proven to be highly effective carrier systems for the efficient delivery of hydrophobic photosensitizers (PSs) in photodynamic therapy (PDT). This study introduces the micellization potential of poly(oligoethylene glycol methyl ether methacrylate) (pOEGMA) as a novel approach, utilizing the hydrophobic methacrylate segments of pOEGMA to interact with highly hydrophobic zinc phthalocyanine (ZnPc), thereby forming a potential micellar drug carrier system. The ZnPc molecule was synthesized from phthalonitrile derivatives and its fluorescence, photodegradation, and singlet oxygen quantum yields were determined in various solvents. In solvents such as tetrahydrofuran, dimethyl sulfoxide, and N,N-dimethylformamide, the ZnPc compound exhibited the requisite photophysical and photochemical properties for PDT applications. The pOEGMA homopolymer was synthesized via reversible addition-fragmentation chain-transfer polymerization, while ZnPc-loaded pOEGMA micelles were prepared using the nanoprecipitation method. Characterization of the pOEGMA, ZnPc, and micelles was conducted using FTIR,1H-NMR, dynamic light scattering, matrix-assisted laser desorption/ionization time-of-flight mass spectrometries, gel permeation chromatography, and transmission electron microscopy. The critical micelle concentration was determined to be 0.027 mg ml-1using fluorescence spectrometry. The drug loading and encapsulation efficiencies of the ZnPc-loaded micelles were calculated to be 0.67% and 0.47%, respectively. Additionally, the release performance of ZnPc from pOEGMA micelles was monitored over a period of nearly 10 d, while the lyophilized micelles exhibited stability for 3 months. Lastly, the ZnPc-loaded micelles were more biocompatible than ZnPc on L929 cell line. The results suggest that the pOEGMA homopolymer possesses the capability to micellize through its methacrylate segments when interacting with highly hydrophobic molecules, presenting a promising avenue for enhancing the delivery efficiency of hydrophobic PSs in PDT. Moreover, it was also deciphered that obtained formulations were highly biocompatible according to cytotoxicity results and could be safely employed as drug delivery systems in further applications.

Elevated blood-ethanol concentration promotes reduction of aliphatic ketones (acetone and ethyl methyl ketone) to secondary alcohols along with slower oxidation to aliphatic diols.

Many people convicted for drunken driving suffer from an alcohol use disorder and some traffic offenders consume denatured alcohol for intoxication purposes. Venous blood samples from people arrested for driving under the influence of alcohol were analyzed in triplicate by headspace gas chromatography (HS-GC) using three different stationary phases. The gas chromatograms from this analysis sometimes showed peaks with retention times corresponding to acetone, ethyl methylketone (2-butanone), 2-propanol, and 2-butanol in addition to ethanol and the internal standard (1-propanol). Further investigations showed that these drink-driving suspects had consumed an industrial alcohol (T-Red) for intoxication purposes, which contained > 90% w/v ethanol, acetone (~ 2% w/v), 2-butanone (~ 5% w/v) as well as Bitrex to impart a bitter taste. In n = 75 blood samples from drinkers of T-Red, median concentrations of ethanol, acetone, 2-butanone, 2-propanol and 2-butanol were 2050mg/L (2.05g/L), 97mg/L, 48mg/L, 26mg/L and 20mg/L, respectively. In a separate GC analysis, 2,3-butanediol (median concentration 87mg/L) was identified in blood samples containing 2-butanone. When the redox state of the liver is shifted to a more reduced potential (excess NADH), which occurs during metabolism of ethanol, this favors the reduction of low molecular ketones into secondary alcohols via the alcohol dehydrogenase (ADH) pathway. Routine toxicological analysis of blood samples from apprehended drivers gave the opportunity to study metabolism of acetone and 2-butanone without having to administer these substances to human volunteers.

Comprehensive identification of polyphenolic metabolites in aspen knotwood by combination of 2D NMR and HPLC-HRMS.

European aspen (Populus tremula L.) knotwood contains large amounts of polyphenolic metabolites, mainly flavonoids, and can be considered as a promising industrial-scale source of valuable bioactive compounds. Valorization of knotwood extractives requires detailed information on their chemical composition and a relevant analytical methodology. This study proposes combined analytical strategy for non-targeted screening and identification of polyphenolic plant metabolites and is aimed at comprehensive characterization of knotwood extractives. Aspen knotwood acetone extract with determined antioxidant activity was an object of the study. Two-dimensional NMR spectroscopy with Structure Elucidator expert system was used for preliminary search of major components and specific structures. Liquid chromatography-high-resolution mass spectrometry (HPLC-HRMS) with data-dependent MS/MS spectra acquisition was used as a complementary technique providing molecular-level characterization and identification of the detected metabolites. Twenty-eight phenolic metabolites were found and identified. Among them, flavonoids, aromadendrin and naringenin, as well as their glycosylated derivatives (mainly O-glucosides) and methyl ethers, dominated. Taxifolin and its 7-O-glucoside were detected as minor components. Other detected compounds are represented by p-coumaric acid and its rutinoside and small amounts of glycosylated ferulic acid. Nineteen of the detected compounds were discovered in aspen knotwood for the first time. The results were confirmed by preparative isolation of individual compounds and NMR studies. The proposed analytical strategy based on 2D NMR and HPLC-HRMS can be considered a powerful tool in the analysis of plant extractives and allowed for the identification and semi-quantification of a large number of polyphenols in aspen knotwood.

Development of New N- and S-substituted-imidazolidin-4-one Analogues with Potent Anti-breast Cancer Activity: In vitro Molecular Docking Assessment

: 2-Thioxoimidazolidin-4-one derivatives 3, 4, 7, 8, and 9 have been synthesized from 3- (benzylideneamino)-2-thioxoimidazolidin-4-one (2) as a starting material. Compounds 3, 4, 7, 8, and 9 were obtained via the reaction of compound (2) with ethyl chloroacetate, methyl acrylate, and chlorophenacyl bromide, respectively. Elemental analysis and several spectroscopy techniques were used to confirm the synthesized compounds. The synthesized compounds, particularly compounds 7 and 8, exhibited significant cytotoxic influences on MCF-7 cells, surpassing staurosporine. Compounds 7 and 8 can induce apoptosis in those treated MCF-7 cells. Studying molecular docking approved that compounds 7 and 8 bind in two and three dimensions to the aromatase binding pockets. Molecular modeling indicates compounds 7 and 8 have a strong affinity for human topoisomerase II beta, establishing its promise as a multifaceted antitumor agent for breast cancer.

Vapor-Liquid Equilibrium of System Comprising Green Solvents: A Holistic Review

Abstract: The design and operation of distillation columns is based on vapor-liquid equilibrium data, which is a necessity for the chemical industry. In recent years, chemical industry has embraced green chemistry and sustainable development. Furthermore, green solvents are more environmentfriendly and cleaner than conventional solvents and thus offer a good alternative. Very limited work has been reported in the literature that focuses on the generation of isobaric/isothermal vapor-liquid equilibrium (VLE) data of systems comprising green solvents. In this paper, reported VLE data are explored for three emerging green solvents, such as cyclopentyl methyl ether (CPME), γ- valerolactone (GVL), and 2-methyltetrahydrofuran (2-MeTHF). Emerging green solvents have favorable environmental, health, and safety characteristics, making them attractive alternatives for a wide range of applications. The study focuses on two critical separations; the extraction of formic acid from Power-to-X chemical processes and purification of acetic acid from chemical synthesis or fermentation processes. Both processes are integral parts of the chemical industry's sustainable development. To facilitate these separations, accurate VLE data for these green solvents with acetic acid/formic acid systems are essential. The paper reviews literature related to VLE data for systems involving these green solvents. It provides insights into the experimental conditions, equipment, analysis methods, thermodynamic models, and error-minimizing functions used in the previous studies. The researchers can refer to this information as a useful reference prior to the VLE experimentation and modeling of systems comprising these three green solvents. Moreover, the paper presents an overview of recent research on green solvents and their applications, illustrating their versatility and potential for various industrial processes. Research efforts are needed to generate VLE data for green solvent systems and support the chemical industry in transitions towards more sustainable practices.

Highly Efficient Production of Furfural from Corncob by Barley Hull Biochar-Based Solid Acid in Cyclopentyl Methyl Ether–Water System

Furfural, an important biobased compound, can be synthesized through the chemocatalytic conversion of D-xylose and hemicelluloses from lignocellulose. It has widespread applications in the production of valuable furans, additives, resins, rubbers, synthetic fibers, polymers, plastics, biofuels, and pharmaceuticals. By using barley hulls (BHs) as biobased support, a heterogeneous biochar Sn-NUS-BH catalyst was created to transform corncob into furfural in cyclopentyl methyl ether–H2O. Sn-NUS-BH had a fibrous structure with voids, a large comparative area, and a large pore volume, which resulted in more catalytic active sites. Through the characterization of the physical and chemical properties of Sn-NUS-BH, it was observed that the Sn-NUS-BH had tin dioxide (Lewis acid sites) and a sulfonic acid group (Brønsted acid sites). This chemocatalyst had good thermostability. At 170 °C for 20 min, Sn-NUS-BH (3.6 wt%) was applied to transform 75 g/L of corncob with ZnCl2 (50 mM) to generate furfural (80.5% yield) in cyclopentyl methyl ether–H2O (2:1, v/v). This sustainable catalytic process shows great promise in the transformation of lignocellulose to furfural using biochar-based chemical catalysts.

Melamine formaldehyde resin adhesive toughened with graphene oxide: Structures and properties

The melamine-formaldehyde (MF) resin adhesive was modified by graphene oxide (GO), the chemical structure, wettability, bonding performance, tensile properties, curing performance and thermal properties of the modified resin were analyzed, and the toughening mechanism was also discussed in this study. The results showed that: (1) The MF resin with a high molar ratio possessed stable methylene ether bonds, which could easily generate parallel folding in space to form a π-π stacking supramolecular self-assembly special structure, with the potential of enhancing the toughness of molecular structures. (2) GO contained a large number of oxygen-containing reactive functional groups, which could further lower the curing temperature of the MF resin. A dense cross-linked network structure improved the thermal stability of the resin. (3) The bonding strength and toughness of the resin were significantly improved when the content of GO was 0.1 wt%. However, due to the large specific surface area and the intense π-π interaction between sheets, GO was easy to agglomerate, and the properties of the resin with GO content of 0.4 wt% degraded sharply. (4) The crystallinity of the MF resin modified by GO decreased, and the surface energy and plastic deformation energy increased due to the increased fracture crack path and fracture surface of the resin, which was the macro-reason for the improvement of toughness. (5) The strong π-π interaction between GO sheets and π-π accumulation between triazine rings were like parallel “springs” in the molecular structure of the resin, which might be the internal reason for the improvement of toughness. In addition, it was also proved that this special structure could limit the activity of hydroxymethyl and the release of free formaldehyde in the resin.

A green bulk modification for imparting a green VIPS membrane with antifouling properties

BackgroundMembrane preparation and membrane modification processes have long involved the use of toxic solvents. The present work proposes to only use envrionmentally-friendly solvents for both the fabrication and the surface modification of hydrophobic microfiltration membranes. In addition, coating processes for membrane modification are essentially surface modification processes. However, spray-coating may be a suitable method for both surface and bulk modification. MethodsAfter dissolving poly(vinylidene fluoride) in dimethylsulfoxide, membranes were formed by the vapor-induced phase separation process, and then modified using an aqeous solution of an amphiphilic copolymer containing poly(ethylene glycol) methyl ether methacrylate units. Then, a variety of physicochemical techniques were employed to characterize the membrane structure and prove the effectiveness of the surface/bulk modification. Antifouling tests in static and dynamic conditions were conducted. Significant findingsIt is possible to reduce the water contact angle of the top surface of the membrane from 135° to 0° and that of the bottom surface from 126° to 0° within <10 s, indicating successful hydrophilization of the membrane on the one hand, and top-to-bottom modification, despite solely exposing the top surface to the spray, on the other hand. This conclusion was confirmed by deidcated surface chemistry analyses. Besides, the membranes maintained their original highly porous and symmetric structure with light effects on surface porosity and pore size following the spray-coating process. The drasting improvement of hydrophilicity resulted in effective mitigation of fibrinogen adsorption (reduced by 85 %) and Escherichia coli adhesion (reduced by 86 %). Fouling during cyclic filtration involving a bacterial suspension was also effectively reduced with a flux recovery ratio of 53 % (against 37 % for a commercial hydrophilic membrane) and an irreversible flux decline ratio of 47 % (against 63 % for a commercial hydrophilic membrane) in the conditions of the test.

Intensified, Kilogram-Scaled, and Environment-Friendly: Chemoenzymatic Synthesis of Bio-Based Acylated Hydroxystyrenes.

Lignin-derived styrene derivatives are versatile building blocks for the manufacture of biobased polymers. As shown previously, phenol-protected hydroxystyrenes are accessible under industrially sound conditions (>100 g L-1, >95% yield) by subjecting biogenic phenolic acids to enzymatic decarboxylation and base-catalyzed acylation in nonaqueous media (wet cyclopentyl methyl ether, CPME). Herein, we demonstrate the production of 1 kg of 4-acetoxy-3-methoxy-styrene in a 10 L reactor and present practical adjustments to the up- and downstream processing that warrant a straightforward process and high isolated yields. Additionally, an environmental assessment is conducted, starting with a thorough E factor analysis to identify the sources that contribute most to the environmental burden (solvent and downstream processing). Also, the total CO2 production of the process is studied, including contributions from energy use and the treatment of generated wastes. The energy impact is evaluated through thermodynamic analysis, and the environmental footprint contributions by wastes-organic and aqueous fractions-are assessed based on CO2 emissions from solvent incineration and wastewater treatment, respectively. Overall, the holistic assessment of the process, its optimization, scale-up, product isolation, and environmental analysis indicate the feasibility of multistep chemoenzymatic reactions to deliver high-volume, low-value chemicals from biorefineries.

Insights into seed coats of nine cultivars of Australian lupin: Unravelling LC-QTOF MS-based biochemical profiles, nutritional, functional, antioxidant, and antidiabetic properties together with rationalizing antidiabetic mechanism by in silico approaches

Lupins, and other legumes, have attained international interest due to their reported remarkable health benefits. Currently, the seed coats are discarded as waste or animal feed. The research presented here summarizes the potential for incorporating the seed coats into ‘whole grain’ foods. We aimed to identify metabolites found in the seed coats of nine commercial Australian cultivars of lupin (Lupinus angustifolius and L. albus species), and to evaluate and compare their functional, nutritional, antioxidant, and antidiabetic properties, along with in silico exploration of mechanisms of action for selected identified secondary metabolites. The seed coats were found to contain 79 to 90% dietary fibers and substantial quantity of essential macrometals. LC-QTOF MS-based, untargeted bioactive metabolite profiling explored a total of 673 chemical entities, and identified 63 bioactive secondary metabolites including: biophenols, unsaturated fatty acids, triterpenoids, alkaloids, and dietary prebiotics (insoluble fibers). The seed coats from these nine cultivars show substantial antioxidant activity. The cultivars of L. angustifolius inhibit α-amylase and α-glucosidase significantly in vitro. Moreover, in silico docking and dynamic simulation along with ADME/T analysis suggest that quercetin 3-methyl ether and 8-C-methylquercetin 3-methyl ether as molecules, novel in lupin seed coats, are responsible for the α-amylase and α-glucosidase inhibition. The findings indicated that lupin seed coats might be beneficial food components, rather than be discarded as ‘mill waste’

Expeditious assembly of N-heteroaryl substituted quercetin derivatives as potent anticancer agents

The synthesis of a small library of N-heteroaryl substituted quercetin derivatives (28 compounds) at the C8 position applying Suzuki-Miyaura cross-coupling reaction between 8-iodoquercetin methyl ether and various pyridylboronic acids or quinolylboronic acids is reported. The obtained quercetin derivatives 2a-2n and 3a-3n were well characterized by the 1H NMR, 13C NMR and HRMS data. Preliminary biological evaluations showed that some of the synthesized 8-heteroarylated quercetin derivatives possessed very high anti-cancer cell proliferation activity in HCC827 cancer cell line (IC50< 5.0 µmol/L) in vitro. Among these synthesized compounds, quinolin-7-yl substituted compound 2m exhibited best activity in HCC827 (IC50 = 3.20 µmol/L), while quinolin-3-yl substituted compound 2i showed best activity in MGC-803 cells (IC50 = 14.92 µmol/L). The 3-pyridyl compound 3c with ortho-fluorine showed best activity in OVCAR-3 cells (IC50 = 10.67 µmol/L). The disclosed structure-activity relationship provides hints that large steric hindrance at the C8 position of quercetin alter the anticancer activities and also offers new examples for new application of electronic and steric modifications as versatile tools in drug discovery.