Hydroxyl Research Articles

Depiction of new flavonoids from Nyctanthus arbor-tristis, their antimicrobial activity and drug-likeness prediction.

Bioactive compounds derived from medicinal plants, such as alkaloids, tannins and flavonoids, possess significant medicinal properties. These compounds have a broad and versatile impact on human nutrition and physiology, contributing to the treatment and management of various diseases. The isolation, structure elucidation and inhibition studies of two novel flavonoids against specific microorganisms, from the leaves of Nyctanthus arbor-tristis are reported in this study. It has been observed for the first time that the presence of an acyl aliphatic moiety, along with the O- glycoside unit at C-7, and the hydroxyl group at C-5, C-4' position in apigenin significantly enhanced antimicrobial activity. Moreover, bioactivity was also investigated through 'Molinspiration' on various parameters followed by the 'rule of five'. This study can be used to highlight the need for the potential development of natural therapeutic products with fewer side effects.

Anti-plasticizing effect of water on prilocaine and lidocaine - the role of the hydrogen bonding pattern.

It is generally accepted that water, as an effective plasticizer, decreases the glass transition temperatures (Tgs) of amorphous drugs, potentially resulting in physical instabilities. However, recent studies suggest that water can also increase the Tgs of the amorphous forms of the drugs prilocaine (PRL) and lidocaine (LID), thus acting as an anti-plasticizer. To further understand the nature of the anti-plasticizing effect of water, interactions with different solvents and the resulting structural features of PRL and LID were investigated by Fourier transform infrared spectroscopy (FTIR) and quantum chemical simulations. Heavy water (deuterium oxides) was chosen as a solvent, as the deuterium and hydrogen atoms are electronically identical. It was found that substituting hydrogen with deuterium showed a minimal impact on the anti-plasticization of water on PRL. Ethanol and ethylene glycol were chosen as solvents to compare the hydrogen bonding patterns occurring between the hydroxyl groups of the solvents and PRL and LID. Comparison of the various Tgs showed a weaker anti-plasticizing potential of these two solvents on PRL and LID. The frequency shifts of the amide CO groups of PRL and LID due to the interactions with water, heavy water, ethanol, and ethylene glycol as observed in the FTIR spectra showed a correlation with the binding energies calculated by quantum chemical simulations. Overall, this study showed that the combination of weak hydrogen bonding and strong electrostatic contributions in hydrated PRL and LID could play an important role in inducing the anti-plasticizing effect of water on those drugs.

Monitoring Ti3C2Tx MXene Degradation Pathways Using Raman Spectroscopy.

Extending applications of Ti3C2Tx MXene in nanocomposites and across fields of electronics, energy storage, energy conversion, and sensor technologies necessitates simple and efficient analytical methods. Raman spectroscopy is a critical tool for assessing MXene composites; however, high laser powers and temperatures can lead to the materials' deterioration during the analysis. Therefore, an in-depth understanding of MXene photothermal degradation and changes in its oxidation state is required, but no systematic studies have been reported. The primary aim of this study was to investigate the degradation of the MXene lattice through Raman spectroscopic analysis. Distinct spectral markers were related to structural alterations within the Ti3C2Tx material after subjecting it to thermal- and laser-induced degradation. During the degradation processes, spectral markers were revealed for several specific steps: a decrease in the number of interlayer water molecules, a decrease in the number of -OH groups, formation of C-C bonds, oxidation of the lattice, and formation of TiO2 nanoparticles (first anatase, followed by rutile). By tracking of position shifts and intensity changes for Ti3C2Tx, the spectral markers that signify the initiation of each step were found. This spectroscopic approach enhances our understanding of the degradation pathways of MXene, and facilitating enhanced and dependable integration of these materials into devices for diverse applications, from energy storage to sensors.

Aqueous Developable and CO2-Sourced Chemical Amplification Photoresist with High Performance.

Seeking high-performance photoresist is an important item for semiconductor industry due to the continuous miniaturization and intelligentization of integrated circuits. Polymer resin containing carbonate group has many desirable properties, such as high transmittance, acid sensitivity and chemical formulation, thus serving as potential photoresist material. In this work, a series of aqueous developable CO2-sourced polycarbonate (CO2-PC) were produced via alternating copolymerization of CO2 and epoxides bearing acid-cleavable cyclic acetal groups in the presence of tetranuclear organoborane catalyst. The produced CO2-PCs were investigated as chemical amplification resists in deep ultraviolet (DUV) lithography. Under the catalysis of photoacid, the acetal (ketal) groups in CO2-PC were hydrolysed into two equivalents of hydroxyl groups, which changes the exposed areas from hydrophobicity to hydrophilicity, thus enabling the exposed regions to be developed in water. Through normalized remaining thickness analysis, the optimal CO2-derived resist achieved a remarkable sensitivity of 1.9 mJ/cm2, a contrast of 7.9, a favorable resolution (750 nm, half pitch), and etching resistance (38% higher than poly(tert-butyl acrylate)). Such performances outperforming commercial KrF and ArF chemical amplification resists (i.e., polyhydroxystyrene-derived and polymethacrylate-based resists), which endows broad application prospects in the field of DUV (248 nm and 193 nm) and extreme ultraviolet (EUV) lithography and nanomanufacturing.

Construction of highly robust amino orange peel cellulose for Cu2+ adsorption study

ABSTRACT In this paper, a kind of cellulose aerogel (HRCNFs) with high mechanical robustness and durability was prepared by using orange peel cellulose and polyethylenimine, and it was used for high-efficiency adsorption of Cu (II). Fourier analysed the structure and morphology of HRCNFs transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM), and the pore structure characteristics of the materials were evaluated by BET. The adsorption capacity of HRCNFs as adsorbent to remove Cu (II) ions from aqueous solution was further studied. The maximum adsorption capacity was 167.21 mg/g. Adsorption is mainly a single-layer chemisorption process. Based on FTIR and BET analysis, the adsorption mechanism is the strong surface complexation of amino, carboxyl, and hydroxyl groups with Cu (II). Through many cycles, HRCNFs retain their integrity and high mechanical robustness. Therefore, the synthesised HRCNFs material can be considered a promising adsorbent for the removal of Cu (II) ions from polluted water bodies.

Syntheses of α(2,8) Sialosides Containing NeuAc and NeuGc by Using Double Carbonyl-Protected N-Acyl Sialyl Donors.

We report on the syntheses of NeuAc and NeuGc-containing glycosides via the use of double carbonyl-protected N-acetyl sialyl donors. The 7-O,9-O-carbonyl protection of an N-acyl-5-N,4-O-carbonyl-protected sialyl donor markedly increased the α-selectivity during glycosylation, particularly when glycosylating the C-8 hydroxyl group of sialic acids. The N-acyl carbamates were selectively opened with ethanethiol under basic conditions to provide N-acyl amines. It is noteworthy that N-glycolyl carbamate was more reactive to nucleophiles by comparison with the N-acetyl carbamate due to the electron-withdrawing oxygen in the N-acyl group and however, allowed selective opening of the carbamates without the loss of N-glycolyl groups. To demonstrate the utility of the approach, we began by synthesizing α(2,3) and α(2,6) sialyl galactosides. Glycosylation of the hydroxy groups of galactosides at the C-6 position with the NeuAc and NeuGc donors provided the corresponding sialyl galactoses in good yields with excellent α-selectivity. However, glycosylation of the 2,3-diol galactosyl acceptor selectively provided Siaα(2,2)Gal. Next, we prepared a series of α(2,8) disialosides composed of NeuAc and NeuGc. Glycosylation of NeuGc and NeuAc acceptors at the C-8 hydroxyl group with NeuGc and NeuAc sialyl donors provided the corresponding α(2,8) disialosides, and no significant differences were detected in the reactivities of these acceptors.

Nanoarchitectonics of an acetogenin-enriched nanosystem mediated by an aqueous extract ofAnnona cherimolaMill with anti-inflammatory and proapoptotic activity against HepG2 cell line.

For the first time, this study shows the nanoarchitectonic process to obtain an acetogenin-enriched nanosystem (AuNPs-Ac) using an aqueous extract from Annona cherimola Mill (ACM) composed of gold nanoparticles embedded in an organic matrix that acts as stabilizing agent and presents anti-inflammatory activity and cytotoxical effect against HepG2 cell line, promoting apoptosis. The synthesis of AuNPs-Ac was confirmed by X-ray diffraction analysis, showing metallic gold as the only phase, and the scanning transmission microscope showed an organic cap covering the AuNPs-Ac. Fourier-transformed infrared suggests that the organic cap comprises a combination of different annonaceous acetogenins, alkaloids, and phenols by the presence of bands corresponding to aromatic rings and hydroxyl groups. High-Performance Liquid Chromatography has demonstrated the presence of annonacin, a potent acetogenin, in the extract of ACM. An in vitro anti-inflammatory activity of the extract of ACM and the AuNPs-Ac was performed using the albumin denaturation method, showing a nonlinear response, which is better than sodium diclofenac salt in a wide range of concentrations that goes from 200 to 400 µg/mL with both samples. The viability assay was studied using trypan blue, treating IMR90 and HepG2 at different concentrations of AuNPs-Ac. The results defined a median lethal dose of 800 µg/mL against HepG2 through apoptosis according to the ratio of caspase-cleaved 9/alpha-tubulin evaluated. It was also demonstrated that the nanosystem presents a higher cytotoxic effect on the HepG2 cell line than in IMR90, suggesting a targeted mechanism. In addition, the nanosystem performs better than using only the extract of ACM in the anti-inflammatory or antiproliferative test, attributed to their higher surface area.

Dehydrogenative synthesis of N-functionalized 2-aminophenols from cyclohexanones and amines: Molecular complexities via one-shot assembly.

Polyfunctionalized arenes are privileged structural motifs in both academic and industrial chemistry. Conventional methods for accessing this class of chemicals usually involve stepwise modification of phenyl rings, often necessitating expensive noble metal catalysts and suffering from low reactivity and selectivity when introducing multiple functionalities. We herein report dehydrogenative synthesis of N-functionalized 2-aminophenols from cyclohexanones and amines. The developed reaction system enables incorporating amino and hydroxyl groups into aromatic rings in a one-shot fashion, which simplifies polyfunctionalized 2-aminophenol synthesis by circumventing issues associated with traditional arene modifications. The wide substrate scope and excellent functional group tolerance are exemplified by late-stage modification of complex natural products and pharmaceuticals that are unattainable by existing methods. This dehydrogenative protocol benefits from using 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO) as oxidant that offers interesting chemo- and regio-selective oxidation processes. More notably, the essential role of in situ generated water is disclosed, which protects aliphatic amine moieties from overoxidation via hydrogen bond-enabled interaction.

Changes in the Glucose Concentration Affect the Formation of Humic-like Substances in Polyphenol–Maillard Reactions Involving Gibbsite

The polyphenol–Maillard reaction is considered one of the important pathways in the formation of humic-like substances (HLSs). Glucose serves as a microbial energy source that drives the humification process. However, the effects of changes in glucose, particularly its concentration, on abiotic pathways remain unclear. Given that the polyphenol–Maillard reaction requires high precursor concentrations and elevated temperatures (which are not present in soil), gibbsite was used as a catalyst to overcome energetic barriers. Catechol and glycine were introduced in fixed concentrations into a phosphate-buffered solution containing gibbsite using the liquid shake-flask incubation method, while the concentration of glucose was controlled in a sterile incubation system. The supernatant fluid and HLS components were dynamically extracted over a period of 360 h for analysis, thus revealing the influence of different glucose concentrations on abiotic humification pathways. The results showed the following: (1) The addition of glucose led to a higher degree of aromatic condensation in the supernatant fluid. In contrast, the supernatant fluid without glucose (Glu0) and the control group without any Maillard precursor (CK control group) exhibited lower degrees of aromatic condensation. Although the total organic C (TOC) content in the supernatant fluid decreased in all treatments during the incubation period, the addition of Maillard precursors effectively mitigated the decreasing trend of TOC content. (2) While the C content of humic-like acid (CHLA) and the CHLA/CFLA ratio (the ratio of humic-like acid to fulvic-like acid) showed varying increases after incubation, the addition of Maillard precursors resulted in a more noticeable increase in CHLA content and the CHLA/CFLA ratio compared to the CK control group. This indicated that more FLA was converted into HLA, which exhibited a higher degree of condensation and humification, thus improving the quality of HLS. The addition of glycine and catechol without glucose or with a glucose concentration of 0.06 mol/L was particularly beneficial in enhancing the degree of HLA humification. Furthermore, the presence of glycine and catechol, as well as higher concentrations of glucose, promoted the production of N-containing compounds in HLA. (3) The presence of Maillard precursors enhanced the stretching vibration of the hydroxyl group (–OH) of HLA. After the polyphenol–Maillard reaction of glycine and catechol with glucose concentrations of 0, 0.03, 0.06, 0.12, or 0.24 mol/L, the aromatic C structure in HLA products increased, while the carboxyl group decreased. The presence of Maillard precursors facilitated the accumulation of polysaccharides in HLA with higher glucose concentrations, ultimately promoting the formation of Al–O bonds. However, the quantities of phenolic groups and phenols in HLA decreased to varying extents.

Optimizing the boron-loaded pH/temperature dual responsive polymer for controlled release of boron from wood

ABSTRACT Disodium octoborate tetrahydrate (DOT) is a well-received and eco-friendly preservative. However, it is prone to leaching from wood in humid conditions or rainy seasons, causing problems such as decreased efficiency in resisting fungi and poor surface performance in surface finishing. To obtain enhanced leaching resistance and simultaneously achieve controlled release of DOT, a pH and temperature dual responsive poly (2-hydroxyethyl methacrylate/2-(Dimethylamino) ethyl methacrylate) (PDH) was prepared and optimized for in situ construction of DOT-loaded PDH (PDHD) in wood. Results showed that PDH displayed obvious pH and temperature-responsive swelling, and when loaded with DOT, the PDHD consequently released DOT in a pH and temperature-responsive way. Fourier transform infrared spectroscopy, Solid-13C NMR analysis and Dynamic mechanical analysis confirmed the copolymerization of 2-Hydroxyethyl methacrylate (HEMA) and 2-(Dimethylamino) ethyl methacrylate (DMAEMA), as well as the presence of crosslinked structure formed from hydrogen bond between the hydroxyl group of HEMA and the N,N-dimethylamino groups of DMAEMA. After that, the PDHD was in situ constructed in wood for controlled release of boron. During the water leaching test, the modified wood exhibited a boron fixation rate of 49.05% compared with 0.72% of the neat DOT-treated wood. Besides, it presented controlled release activity in response to pH and temperature. This work provides new approaches to the fixation of boron preservatives and notably realizes responsive releasing of boron compounds for long-term wood preservation.

Environmental Stability Stretchable Organic Hydrogel Humidity Sensor for Respiratory Monitoring with Ultrahigh Sensitivity

AbstractReal‐time monitoring of respiration plays a very important role in human health assessment, especially in monitoring and analyzing respiration during exercise and sleep. However, traditional humidity sensors still have problems in flexibility, sensitivity, and durability, so there is an urgent need to develop humidity sensors with high sensitivity, stretchability, and environmental resistance as respiratory monitoring applications. Here, based on the double network hydrogel structure of polyvinyl alcohol and polyacrylamide, a highly sensitive, highly stretchable, and environmentally stable organic hydrogel humidity sensor has been manufactured by using the synergistic effect of lithium chloride and MXene. The hydrogel humidity sensor shows rapid response in the humidity range of 40–85% RH, and has a high sensitivity of −103.4%/% RH. In addition, it exhibits more than 3000% mechanical strain and excellent environmental resistance, which is attributed to the chemical cross‐linking in the hydrogel network and the synergistic effect of multiple hydroxyl groups in glycerol forming rich hydrogen bonds with water and polymer chains. The hydrogel humidity sensor is used for real‐time monitoring of breathing and sleep processes. This work provides a new strategy for preparing high‐performance, extensibility, and environmental stability hydrogel‐based sensors for respiratory monitoring.

Hydroxy-Functionalized Ionic Liquids under Pressure: The Influence on Hydrogen Bonding between Ions of Opposite and Like Charges.

Hydroxy functionalization of cations in ionic liquids (ILs) can lead to formation of hydrogen bonds between their OH groups, resulting in so-called (c-c) H-bonds. Thereby, the (c-c) H-bonds compete with regular H-bonds (c-a) between the OH groups and the anions. Polarizable cations, weakly interacting anions, and long alkyl chains at the cation support the propensity for the formation of (c-c) H-bonds. At low temperatures, the equilibrium between (c-c) and (c-a) H-bonds is strongly shifted in favor of the cation-cation interaction. Herein, we clarify the pressure dependence on (c-c) and (c-a) H-bond distributions in the IL 1-(2-hydroxyethyl)-3-methylimidazolium hexafluorophosphate [HOC2C1Im][PF6], in mixtures of [HOC2C1Im][PF6] with the nonhydroxy-functionalized IL 1-propyl-3-methylimidazolium hexafluorophosphate [C3C1Im][PF6] and in [HOC2C1Im][PF6] including trace amounts of water. The infrared (IR) spectra provide clear evidence that the (c-c) H-bonds diminish with increasing pressure in favor of the (c-a) H-bonds. Adding trace amounts of water results in enhanced (c-c) clustering due to cooperative effects. At ambient pressure, the water molecules are involved in the (c-c) H-bond motifs. Increasing pressure leads to squeezing them out of H-bond clusters, finally resulting in demixing of water and the IL at the microscopic level.

Deciphering the Self-Catalytic Mechanisms of Polymerization and Transesterification in Polybenzoxazine Vitrimers.

The use of internal catalysts has emerged as a pivotal design principle to facilitate dynamic exchanges within covalent adaptable networks (CANs). Polybenzoxazines, specifically, have shown considerable potential in generating vitrimers through thermally induced transesterification reactions catalyzed internally by tertiary amines. This study aims to investigate the chemical complexities of transesterification reactions within benzoxazine vitrimers. To achieve this, model molecules using various phenolic acids and amino-alcohol derivatives were synthesized as precursors. The structure of these model molecules was fully elucidated by using nuclear magnetic resonance (NMR). Differential scanning calorimetry (DSC) and rheology experiments evidenced the accelerated network formation of the precursors due to the presence of aliphatic -OH groups. Thermogravimetric analysis coupled with microcomputed gas chromatography (TGA-μGC) was used to provide evidence of transesterification reactions. The results showed that the spatial proximity between tertiary amine and hydroxyl groups significantly enhances the rate exchange, attributed to a neighboring group participation (NGP) effect. Interestingly, kinetic experiments using complementary NMR techniques revealed the thermal latency of the tertiary amine of benzoxazine toward transesterification reactions as its opening is needed to trigger the dynamic exchange. The study highlights the crucial role of steric hindrance and tertiary amine basicity in promoting the dynamic exchange in an internally catalyzed system.

Synthesis and Properties of Photocurable Polymers Derived from the Polyesters of Glycerol and Aliphatic Dicarboxylic Acids

The rapid development of 3D printing technology and the emerging applications of shape memory elastomer have greatly stimulated the research of photocurable polymers. In this work, glycerol (Gly) was polycondensed with sebacic, dodecanedioic, or tetradecanedioic acids to provide precursor polyesters with hydroxyl or carboxyl terminal groups, which were further chemically functionalized by acryloyl chloride to introduce sufficient, photocurable, and unsaturated double bonds. The chemical structures of the acrylated polyesters were characterized by FT IR and NMR spectroscopies. The photoinitiated crosslinking behavior of the acrylated polyesters under ultraviolet irradiation without the addition of any photoinitiator was investigated. The results showed that the precursor polyesters that had a greater number of terminated hydroxyls and a less branched structure obtained a relatively high acetylation degree. A longer chain of aliphatic dicarboxylic acids (ADCAs) and higher ADCA proportion lead to a relatively lower photopolymerization rate of acrylated polyesters. However, the photocured elastomers with a higher ADCA proportion or longer-chain ADCAs resulted in better mechanical properties and a lower degradation rate. The glass transition temperature (Tg) of the elastomer increased with the alkyl chain length of the ADCAs, and a higher Gly proportion resulted in a lower Tg of the elastomer due to its higher crosslinking density. Thermal gravimetric analysis (TGA) showed that the chain length of the ADCAs and the molar ratio of Gly to ADCAs had less of an effect on the thermal stability of the elastomer. As the physicochemical properties can be adjusted by choosing the alkyl chain length of the ADCAs, as well as changing the ratio of Gly:ADCA, the photocurable polyesters are expected to be applied in multiple fields.

Investigating the Potential of Phenolic Compounds and Carbohydrates as Acceptor Substrates for Levansucrase-Catalyzed Transfructosylation Reaction.

This study characterizes the acceptor specificity of levansucrases (LSs) from Gluconobacter oxydans (LS1), Vibrio natriegens (LS2), Novosphingobium aromaticivorans (LS3), and Paraburkholderia graminis (LS4) using sucrose as fructosyl donor and selected phenolic compounds and carbohydrates as acceptors. Overall, V. natriegens LS2 proved to be the best biocatalyst for the transfructosylation of phenolic compounds. More than one fructosyl unit could be attached to fructosylated phenolic compounds. The transfructosylation of epicatechin by P. graminis LS4 resulted in the most diversified products, with up to five fructosyl units transferred. In addition to the LS source, the acceptor specificity of LS towards phenolic compounds and their transfructosylation products were found to greatly depend on their chemical structure: the number of phenolic rings, the reactivity of hydroxyl groups and the presence of aliphatic chains or methoxy groups. Similarly, for carbohydrates, the transfructosylation yield was dependent on both the LS source and the acceptor type. The highest yield of fructosylated-trisaccharides was Erlose from the transfructosylation of maltose catalyzed by LS2, with production reaching 200 g/L. LS2 was more selective towards the transfructosylation of phenolic compounds and carbohydrates, while reactions catalyzed by LS1, LS3 and LS4 also produced fructooligosaccharides. This study shows the high potential for the application of LSs in the glycosylation of phenolic compounds and carbohydrates.

Adsorption performance and mechanism of Arsenic(III) and Arsenic(V) by using copper-manganese binary oxide

ABSTRACT Arsenic contamination threatens the safety of drinking water in many areas of the world. As(V) is less toxic and easier to remove than As(III). Hence, it is essential to oxidise As(III) to As(V). Based on the previous studies, Cu-Mn binary oxide (CMBO) (with a molar ratio of Cu/Mn = 3:1) was prepared by a two-step method. The results showed that CMBO has a large specific surface area (67.74 m2/g) and pore size (16.87 nm). Moreover, CMBO has an inconspicuous crystal structure and abundant hydroxyl groups, which are favourable for arsenic adsorption. The adsorption kinetics results indicated that As(III) was oxidised to As(V) during the adsorption process, and the adsorption rate for As(V) removal was faster than that for As(III) removal. The saturated adsorption capacities of As(III) and As(V) were calculated to be 64.17 mg/g and 84.87 mg/g via the Langmuir isotherm model, respectively. The results of the pH effect studies indicated that acidic conditions promoted the removal of both As(III) and As(V) by CMBO due to the electrostatic attraction. The spectroscopic analysis results demonstrated that Mn oxides within CMBO played a vital role in As(III) oxidation. The removal of As(III) by CMBO was attributed to the synergistic effect of As(III) oxidation by Mn oxides and As sorption by Cu oxides. Overall, CMBO is a promising sorbent with great potential for removing arsenic.

Nanocellulose: A sustainable functional construct for the remediation of heavy metal ions from water

Heavy metals are considered to be a significant pollutant in water bodies, adversely affecting human health by causing various severe diseases after passing down the food chain. The rise in environmental problems due to the usage of non – biodegradable materials leads to the necessity of eco–friendly materials. The abundant and eco-friendly nature of the nanocellulose makes them promising substitutes for non-sustainable materials, nowadays. It is also possible to find the chemical components (cellulose, hemicellulose, and lignin) present in a source and the cellulose yield. In this context, nanocellulose has gained considerable attention among nanomaterials as a promising candidate for the adsorption of toxic heavy metal ions because of its large surface area, light weight, low cost, biocompatible nature, etc. Moreover, the numerous surface hydroxyl groups present in its surface make them suitable for the wide range of surface functionalization with different groups. They can thus be used individually or in combination with other materials for excellent adsorption towards various toxic heavy metal ions. The state of research on modified nanocellulose as an adsorbent for heavy metals is principally discussed in this review. Mainly two types of plant-based nanocelluloses; cellulose nanofibers (CNFs) and cellulose nanocrystals (CNCs), are discussed in detail in this review. The extraction of nanocellulose via a green approach was also covered. This review comprises comprehensive details on the modifications and other relevant properties of nanocellulose which would facilitate the adsorption of toxic heavy metals.

Fully bio-sourced catalyst-free covalent adaptable networks from epoxidized soybean oil and L-tartaric acid

Epoxidized vegetable oil (EVO)-based epoxy systems offer a promising avenue for replacing non-recyclable petroleum-based thermoset elastomers. Looking towards future prospects, they also hold potential to evolve into sustainable covalent adaptable networks (CANs). Typically, transesterification-based CANs require catalysts to achieve crosslinked structures that are reprocessable at relatively high temperatures (T ≥ 150 °C). In this study, epoxidized soybean oil (ESBO) was cross-linked with a eutectic hardener composed of L-tartaric acid (TAR) and ethyl lactate (in an aqueous solution), resulting in the development of a fully bio-based 3D covalent network capable of reprocessing without the need for an exogenous catalyst. In addition, it was demonstrated that the peculiar structure of L-tartaric acid, with –OH groups linked to its backbone, plays a prominent role in the reactivity of the system. These free hydroxyl functions facilitate both the ring-opening of epoxides and transesterification reactions, thus enhancing both curing and covalent exchange kinetics.

Identification of cholesterol in different media by using the FT-IR, FT-Raman and UV–visible spectra combined with DFT calculations

In this investigation, the experimental FT-IR and FT-Raman spectra of cholesterol in the solid phase and in ethanol solution have been combined with the B3LYP/6–311++G** calculations and the scaled quantum mechanical force field (SQMFF) methodology, normal internal coordinates and transferable scaling factors to obtain the complete vibrational assignments of 216 vibration modes expected. Hence, complete vibrational assignments for that steroid of greatest biological importance are reported for first time in gas phase and ethanol solution together with its scaled force constants. Changes in the positions of some bands and in force constants values are observed in the different media due to the predicted intra-molecular interactions between CH3/CH3, CH3/CH2 and CH2/CH2 groups by atoms in molecules (AIM) calculations. The 1H- and 13C NMR chemical shifts of normal and deuterated cholesterol in aqueous solution confirm that the H atom of OH group is involved in the formation of H bonds in solution. Studies of experimental electronic spectra of cholesterol in different concentrations of ethanol revealed that the positions of peaks maxima increase conform increase the solution concentration. The natural bond orbital (NBO) analyses reveal that the polar OH group and the four fused rings play important roles in the stability and properties of cholesterol than the large hydrophobic moiety. Frontier orbitals predicted low reactivity of cholesterol in ethanol probably due to its high ω value in this medium.

Pinpointing the catalytic role of water in low-temperature CO oxidation on gold catalysts at a molecular level

Water substantially promotes the low-temperature redox reactions catalyzed by gold. However, clarifying the catalytic role of water is challenging due to co-existing OH and H2O species on Au catalysts under working conditions. Here, via controlled preparation of OH and adsorbed H2O species on a NiO/Au(111) inverse model surface combined with isotope-labelling reactants, we provide unambiguous spectroscopic experimental evidence to identify adsorbed H2O species, instead of OH groups, to promote O2 activation for low-temperature CO oxidation at the NiO-Au interface. In combination with theoretical calculations, adsorbed H2O-stabilized O2 species was found to be facilely activated into reactive OOH species but OH stabilized-O2 species could not. These results further discriminate the role of adsorbed H2O species and OH group in O2 activation in gold catalysis, which significantly advances our fundamental understanding of both Au catalysis and catalytic role of H2O.