Solvent Water Research Articles

Oxidative Amidation of Ferrocenyl Aldehydes with Amines Catalyzed by Chalcogenised Fe3Se2(CO)9 Cluster: Direct Transformation of Aldehyde to Amides.

With the interest and knowing the importance of ferrocenyl conjugates, a direct amidation of ferrocenyl aldehyde has been developed under feasible conditions. Varieties of amines has been oxidatively coupled with ferrocene aldehyde in the presence of highly economical and robustly stable iron chalcogenide ironcarbonyl clusters [Fe3E2(CO)9, E= S, Se, and Te] and TBHP. The reaction worked in greener solvent water at a moderate temperature of 70 °C and the ferrocenyl-amides in just 30 minutes. All the varieties of amines were found to be well tolerated for the present method, and due to the high medicinal importance of ferrocenyl-amides, sole focus of this report was concentrates on the synthesis of various new ferrocenyl-amides in good to excellent amounts.

Balancing Brightness and Photobasicity: Modulating Excited-State Proton Transfer Pathways in Push-Pull Fluorophores for Biological Two-Photon Imaging.

Push-pull fluorophores with donor-π-acceptor architectures are attractive scaffolds for the design of probes and labels for two-photon microscopy. Such fluorophores undergo a significant charge-delocalization in the excited state, which is essential for achieving a large two-photon absorption cross-section and brightness. The polarized excited state may, however, also facilitate excited-state proton transfer (ESPT) pathways that can interfere with the probe response. Herein, we employed steady-state and time-resolved spectroscopic studies to elucidate whether ESPT is responsible for the pH-dependent emission response of the Zn(II)-selective fluorescent probe chromis-1. Composed of a push-pull architecture with a pyridine ring as the acceptor, the chromis-1 fluorophore core acts as a photobase that promotes ESPT upon acidification. Although the pKa of the pyridine acceptor increases more than six orders of magnitude upon excitation, the photobasicity is not sufficient to deprotonate solvent water molecules under neutral conditions. Rather, the pH-dependent emission response is caused by the pendant bis-isonicotinic acid chelating group which upon protonation facilitates an excited-state intramolecular proton transfer to the pyridine acceptor. A simple permutation of the core pyridine nitrogen from the para- to the ortho-position relative to the thiazole substituent was sufficient to reduce the excited-state basicity by two orders of magnitude without compromising the two-photon excited brightness. These results highlight the importance of choosing the appropriate fluorophore core and chelating moiety for minimizing pH-dependent responses in the design of fluorescent probes for biological imaging.

Palladium Single Atom-supported Covalent Organic Frameworks for Aqueous-phase Hydrogenative Hydrogenolysis of Aromatic Aldehydes via Hydrogen Heterolysis.

Developing a method for the tandem hydrogenative hydrogenolysis of bio-based furfuryl aldehydes to methylfurans is crucial for synthesizing sustainable biofuels and chemicals; however, it poses a challenge due to the easy hydrogenation of the C=C bond and difficult cleavage of the C-O bond. Herein, a palladium (Pd) single-atom-supported covalent organic framework was fabricated and showed a unique 2,5-dimethylfuran yield of up to 98.2% when reacted with 5-methyl furfuryl aldehyde in an unprecedented water solvent at 30°C. Furthermore, it exhibited excellent catalytic universality while converting various furfuryl-, benzyl-, and heterocyclic aldehydes at room temperature. The analysis of the catalytic mechanism confirmed that H2 was heterolytically activated on the Pd-N pair and triggered the keto-enol tautomerism of the covalent organic frameworks (COFs) host, resulting in H--Pd∙∙∙O-H+ sites. These sites served as novel asymmetric hydrogenation sites for the C=O group and hydrogenolysis sites for the C-OH group through a scarce SN2 mechanism. This study demonstrated remarkable bifunctional catalysis through the H2-induced keto-enol tautomerism of COF catalysts for the atypical preparation of methyl aromatics in a water solvent at room temperature.

Palladium Single Atom‐supported Covalent Organic Frameworks for Aqueous‐phase Hydrogenative Hydrogenolysis of Aromatic Aldehydes via Hydrogen Heterolysis

Developing a method for the tandem hydrogenative hydrogenolysis of bio‐based furfuryl aldehydes to methylfurans is crucial for synthesizing sustainable biofuels and chemicals; however, it poses a challenge due to the easy hydrogenation of the C=C bond and difficult cleavage of the C–O bond. Herein, a palladium (Pd) single‐atom‐supported covalent organic framework was fabricated and showed a unique 2,5‐dimethylfuran yield of up to 98.2% when reacted with 5‐methyl furfuryl aldehyde in an unprecedented water solvent at 30°C. Furthermore, it exhibited excellent catalytic universality while converting various furfuryl‐, benzyl‐, and heterocyclic aldehydes at room temperature. The analysis of the catalytic mechanism confirmed that H2 was heterolytically activated on the Pd–N pair and triggered the keto‐enol tautomerism of the covalent organic frameworks (COFs) host, resulting in H––Pd∙∙∙O–H+ sites. These sites served as novel asymmetric hydrogenation sites for the C=O group and hydrogenolysis sites for the C–OH group through a scarce SN2 mechanism. This study demonstrated remarkable bifunctional catalysis through the H2‐induced keto‐enol tautomerism of COF catalysts for the atypical preparation of methyl aromatics in a water solvent at room temperature.

Reduction of 4‐Nitrophenol Catalyzed by Gold Nanoclusters with Aggregation‐induced‐emission: Emission Intensity Correlated Activity and Mechanistic Exploration

Thiolate‐protected Au nanoclusters (NCs) has developed as a promising class of model catalysts to achieve fundamental understanding of metal nano‐catalysis. In this work, using glutathione (GSH) protected Au NCs (Au@GSH NCs) with aggregation‐induced‐emission (AIE) characteristics as model catalyst for the hydrogenation of 4‐nitrophenol (4‐NP), photoluminescence (PL) intensity correlated catalytic activity of Au@GSH NCs was successfully mediated by the addition of Ag+ in the preparation or poor solvent in the reaction medium, showing a relationship of ‘as one falls, another rises.’ Au NCs with intense PL implied a dense packing of peripheral ligand which hampered the accessibility of active site and thus exhibited slowest catalytic reaction kinetics of the reduction of 4‐NP and vice versa. Based on this methodology, a case study of the effect of salt additives on the catalytic activity is carried out, different mechanisms are distinguished by the change in the PL intensity, and with the combination of diagnostic deuterium isotope experiments, it has been demonstrated that the proton from water solvent is involved in the reaction and that the proton transfer process is the rate‐determining step, the contribution of ionic additives to the hydrogen bonding network determines their effect on the reaction kinetics.

Antioxidant characterization of fruits of the Family Cactaceae: Hylocereus undatus, Selenicereus megalanthus, and Hylocereus polyrhizus

In this study, the antioxidant capacity of the peel and pulp of three Pitaya species was investigated: Hylocereus undatus, Selenicereus megalanthus, and Hylocereus polyrhizus. The methods used include the 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical scavenging method, the thiobarbituric acid reactivity assay (TBARS) for inhibition of lipid peroxidation, and the Folin-Ciocalteau method for determination of total phenolic content. Regarding the TBARS results, the peel sample of 20% H. polyrhizus showed the highest antioxidant capacity in both solvents (water and alcohol) analyzed. Regarding the pulp, the H. undatus sample in the aqueous extract was the sample with the highest antioxidant potential (12.5%). In the ethanolic extract, the sample of H. polyrhizus pulp (25%) showed the highest antioxidant potential, as did the peel at a concentration of 20%. Using the DPPH method, the peel sample of the 5% aqueous extract of H. undatus can be highlighted with a greater antioxidant capacity. Regarding the pulp, the sample with the highest potential was the 20% H. undatus in the aqueous extract. In the ethanolic extract, the H. undatus samples from the peel and pulp showed the highest antioxidant potential with 25 and 50%, respectively. In terms of phenolic content, no significant difference was found between the peel samples, but among the pulp samples, H. undatus had the lowest concentration. It can be concluded that the different pitaya species exhibited significant antioxidant capacity, suggesting that pitaya consumption could potentially provide benefits to human health due to its bioactive compounds.

Guide for Nonequilibrium Molecular Dynamics Simulations of Organic Solvent Transport in Nanopores: The Case of 2D MXene Membranes.

Organic solvent nanofiltration (OSN) stands out as an energy-efficient and low-carbon footprint technology, currently reliant on polymeric membranes. With their exceptional chemical stability and tunable sieving properties, two-dimensional (2D) nanolaminate membranes present distinct advantages over conventional polymer-based membranes, attracting tremendous interest in the OSN community. Computational approaches for designing innovative 2D nanolaminates exhibit significant potential for the future of OSN technology. Imitating the pressure gradient in filtration processes by applying an external force to atoms within a predefined slab, boundary-driven nonequilibrium molecular dynamics ((BD)-NEMD) is a state-of-the-art simulation method with a proven track record in investigating the water transport in nanopores. Nevertheless, implementation of (BD)-NEMD for a broad range of solvents poses a challenge in estimating the OSN performance of theoretical membranes. In this work, we developed a (BD)-NEMD protocol that elucidates the effects of several computational details often overlooked in water simulations but are crucial for bulky solvent systems. We employed a MXene (Ti3C2O2) nanochannel as a model membrane and examined the transport of nine solvents (methanol, ethanol, acetone, n-hexane, n-heptane, toluene, ethyl acetate, dichloromethane, and water) having different properties. First, the impact of ensemble type, thermostatting, channel wall model, and restraining force constant was elaborated. After optimizing the thermostatting approach, we demonstrated that the location of the force slab particularly affects the flux of bulky solvents by changing the density distribution in the feed and permeate sides. Similarly, the uniformity of intramolecular force distribution in bulky solvents and resulting flux are shown to be prone to manipulation by slab boundaries. Next, the magnitudes of the external force generating a linear relation between the pressure gradient and solvent flux were identified for each solvent to ensure that calculated fluxes could be extrapolated to experimentally related pressures. This linear relation was also validated for a mixture system containing 50% ethanol and 50% water. We then correlated the calculated solvent permeances with various solvent properties, such as viscosity, Hansen solubility parameters, kinetic diameter, and interaction energy. Remarkably, we observed a linear correlation with an R2 value of 0.96 between permeance and the combined parameter of viscosity and interaction energy. Finally, the solvent permeances calculated with our proposed methodology closely align with the experimentally reported data. Overall, our work aims to serve as a practical guide and bridge the gap in established simulation methods that are suited for a broad range of solvents and membrane materials.

Cluster aggregation of water-based deep eutectic solvents in water and evaluation of their cytotoxicity

Deep Eutectic Solvents (DESs) are emerging in the recent literature as promising environmentally friendly liquids in different topics, finding fruitful applications as substitutes to common volatile organic solvents.In this work a study of cluster formation of water-based DESs in water dilutions is presented. The three analysed mixtures are: glycolic acid/water (GA/H2O); betaine/water (TMG/H2O), choline chloride/water (ChCl/H2O). Ionic conductivity, viscosity, ultrasound spectroscopy and NMR techniques showed the presence of aggregates of aquoDESs in water dilutions. These aggregates are present in the solutions until values about 50% w/w of added water, showing the presence of water-in-water structured systems. Moreover, taking into account the convenient disposal as water dilution of a DES, the cytotoxicity of these dilutions was evaluated on Caco2 model cells, showing the effect to be related only to the non-water components of these liquids. The water dilutions of water-based DESs have a great relevance for their applications, because their physical properties can be modulated as needed preserving their DESs’ identities.

Efficacy of Melia azedarach leaf extract in different solvents against Heterotermes indicola Wasmann (Blattodea: Rhinotermitidae) using non-durable wooden blocks under laboratory and field conditions

Hetertermes indicola Wasman (Blattodea: Rhinotermitidae) is a highly wood-destructive termite species in the urban settings of Pakistan. This study evaluated the biocidal action of Melia azedarach leaf extract in different solvents on H. indicola by conducting choice and no-choice feeding deterrence assays using impregnated palatable wood under field and laboratory conditions. Dose-dependent and time-dependent trends were observed in the leaf extracts of M. azedarach at different concentrations (500, 1000, and 1500 ppm) using solvent water and methanol with 80–100 % termite mortality after 6 days of exposure. A key outcome was the higher termiticidal efficacy of methanolic extract compared to aqueous extract under both field and laboratory conditions. The LC50 values of 358 ppm for methanol and 466 ppm for aqueous extract after 15 days in a laboratory no-choice experiment exhibit a quantitative measure of chinaberry leaf extract toxicity. A significant reduction in mean percent weight loss (8.26 %) of treated wood with 1500 ppm of M. azedarach leaf extract in methanol was observed under field conditions. In conclusion, triterpenoids and phytol present in methanolic leaf extract demonstrated higher efficacy in both lab and field conditions making a solid foundation for the further development of natural wood preservatives. Since they induced rapid lethargic conditions in termites and digestive toxicity which leads to minimum loss of treated wood.

A very simple synthesis of defect-rich PdAg nanosponges for highly selective hydrogenation of furfural

Furfuryl alcohol (FA) is an important chemical and has extensive applications in varied fields. To realize the highly selective hydrogenation of furfural (FF) to produce FA, the key is the preparation of the catalysts with excellent performance. Herein, a very simple wet chemical method is developed for the one-step preparation of PdAg nanosponges (NSs). Specifically, with Pd(OAc)2 and AgNO3 as precursors, and ethylene glycol (EG) as both solvent and reducing agent, PdAg NSs can be grown and assembled at mild temperature of 40 °C. Throughout the reaction, no any surfactants and additional reducing agents are applied. The as-prepared PdAg NSs possess 3D self-supported alloy structures, “clean” surface, abundant pores, high specific surface area and rich defects. In the FF hydrogenation reaction at 60 °C under 1.5 MPa H2 pressure in the mixed solvent of ethanol and water (1 : 4 in volume ratio), the self-supported PdAg-1 NSs (1 : 1 in Pd/Ag molar ratio) exhibit superior catalytic performance than other PdAg NSs, pure Pd sample and commercial Pd/C (10%). With PdAg-1 NSs as catalyst in the absence of support, 100% FF can be converted and the selectivity toward FA is as high as 97.1% at 36.0 h of reaction. After 4 cycles, PdAg-1 NSs still maintain the high catalytic activity in FF hydrogenation and high selectivity toward FA, which may originate from the 3D self-supported structures, high specific surface area, “clean” surface, rich defects and electronic synergistic effect between Pd and Ag. This simple fabrication of PdAg NSs introduces new ideas for the synthesis of other nanostructured bi- and multi-metallic catalysts for highly selective FF hydrogenation to FA and other advanced applications.

Experimental investigation of hybrid enhanced oil recovery techniques for Ugnu Heavy Oil on Alaska North Slope

The Alaska North Slope (ANS) is endowed with a substantial reservoir of heavy oil, estimated at 12–18 billion barrels, primarily concentrated within the Ugnu reservoirs. These deposits, situated at depths ranging from 2,000 to 4,000 feet, lie in close proximity to the permafrost and have undergone biodegradation, resulting in in-situ viscosities reaching thousands of centipoise. Following the success in recovering the somewhat less heavy, viscous oils through polymer injection, the deposits in Ugnu Formation are garnering significant interest. Although thermal recovery methods are commonplace for heavy oils, applying these methods on ANS is impractical, given the adjacency to continuous permafrost. Therefore, non-thermal hybrid enhanced oil recovery (cEOR) methods, such as solvent (e.g., CO2) and low salinity water (LSW) based, or LSW and polymer-based techniques, emerge as the primarily feasible options for recovering these vast heavy oil resources. This study experimentally investigates, via systematically carried out fluid property and phase behavior tests and a series of sand-pack coreflood experiments, the potential to enhance the recovery of Ugnu heavy oils. The coreflood experiments reveal the synergistic effect of combining liquid-CO2 with LSW to be the most promising approach in this study as a water alternating gas (WAG) process results in the cumulative recovery factor of 83.5%, doubling the recovery obtained by continuous low salinity waterflood. Additionally, the liquid-CO2-LSW WAG process demonstrated an additional benefit for CO2 storage, with about 25% of the pore volume of the liquid-CO2 injected being sequestered at the end of the injection process. This significant recovery improvement is attributed to a substantial reduction of oil viscosity upon contact with the liquid CO2 during the soaking period, with a reduction of up to 95% of the original oil viscosity. Meanwhile, in-situ emulsion generation was observed in the oil produced from the continuous LSW flooding. This was also evident by the increased differential pressure across the sand-pack compared to that of the liquid-CO2 alternating LSW process. The promising results of this study indicate significant potential for liquid-CO2 alternating LSW injection as an effective cEOR technique for Ugnu heavy oils.

Structural analysis and theoretical studies of 2-(2-chlorobenzylidene) malononitrile (CS) “a riot controlling agent”

In solvent methanol, malononitrile and 2-chlorobenzaldehyde were stirred in the presence of base piperidine to synthesise the target chemical 2-(2-chlorobenzylidene) malononitrile (CS). The crystal structure of the target compound C10H5ClN2 has been elucidated through X-ray crystallographic analysis. It crystallises in the monoclinic crystal system within the P21 space group, containing four molecules per asymmetric unit. The unit cell dimensions are a = 3.8825(3) Å, b = 21.0202(18) Å, c = 21.3481(18) Å, and β = 95.096(4)°. The phenyl and malononitrile groups, which make up the molecular components, are each planar but slanted towards one another at a dihedral angle of 12.7° (4). Besides this, target molecule is also stabilized by hydrogen bonding, halogen bonding and π stacking interactions. Solid-state structure has been analysed through Hirshfeld surface analysis, including the evaluation of the different energy frameworks, indicating that the molecular sheets are primarily formed by hydrogen bonds and halogen bonds and the stabilization is dominated via the electrostatic energy contribution. Fingerprint plots were carried out to study the relative contribution of noncovalent interactions in the target compound CS. Further, the density functional theory calculations were employed using B3LYP hybrid functional with 6-311++G level basic set to optimize the structural coordinates in gas phase and in different solvents (chloroform, water, and methanol). The chemically active regions of the target compound were identified by the analysis of molecular electrostatic potential surface. Further, from PASS analysis and literature reports, molecular docking of title compounds was carried out with human transient receptor potential ankyrin 1 ion channel (hTRPA1) (PDB-ID 6PQO). ΔGb (docking energy) and inhibition constant was calculated to be −7.53 kcal/mol and 3.33 μM respectively, with the target ion channel.

Isolation and characterization of biomass waste based bioplasticizer from Eucalyptus leaf: A suitability analysis of biofiller for polymeric composites

Plasticizers improve polymeric materials' properties and processability as additives. Currently, a variety of liquid synthetic plasticizers derived from fossil fuels are available. The environmental unsuitability of these materials could potentially lead to adverse effects on the environment. When we compare solid and liquid plasticizers, we find an infinite variety of liquid plasticizers. As a result, our work focuses on the extraction of plasticizer from plant sources. Accordingly, the plasticizer is extracted from eucalyptus leaves via solvent purification and surface catalysis. Research was conducted utilizing X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, and Ultraviolet (UV) visible spectroscopy to determine the characteristics of plasticizer. The scanning electron microscopy (SEM) and energy dispersive spectrum (EDS) analysis are used to analyze the surface morphology of the isolated plasticizer. The plasticizer's UV examination reveals active absorption at 375.21 nm. The plasticizer was determined to have a lower density of 0.941 g/cm3. The plasticizer that was extracted had a low solubility in water and organic solvents while possessing an estimated molecular weight of 340. The glass transition temperature of plasticizer was also examined using differential scanning electron microscopy analysis and found to be 64.17°C. The crystallinity index and size were found to be 34.08% and 28.57 nm, respectively. The characteristic features obtained were well-suited for use as filler in polymer composite materials.

Novel high-strength, recyclable, microbial-resistant, and freeze-thaw dual topological network hydrogel cooling media

The demand for multifunctional hydrogels, offering high mechanical strength, efficient cooling, and antimicrobial properties, is growing in food preservation. Here, a dual-network (DN) hydrogel PM@Cur, which includes curcumin, is fabricated through chemical crosslinking and hydrogen bonding interactions. The resulting hydrogels can withstand more than five freeze-thaw cycles at −80 °C, and resist brittleness after liquid nitrogen treatment. PM@Cur also exhibits surface hydrophobicity (contact angle >90°) for both water and organic solvents. These properties meet the mechanical, anti-fouling, and recyclable demands for hydrogel coolants. The antimicrobial assays in vitro confirmed that the inclusion of curcumin provided the PM@Cur with photodynamic antimicrobial capacity. Finally, the prepared PM@Cur hydrogel ice cubes have been confirmed to exhibit better anti-melting properties than traditional ice cubes, thus enabling the preservation of strawberries and shrimp. This study presents an innovative solution for producing advanced functional integrated hydrogels, offering a promising and safer option for food coolants.\\.

Piperine analogues as dual inhibitors for antibacterial and antiarthritic properties through impact of ligands optimization, docking and water solvation

The prevalence of bacterial diseases poses a significant challenge because of how they can develop resistance to antibiotics and evade the human immune system, highlighting the need for novel therapeutic approaches. Bacterial infection leads to the degradation of bone tissue and the development of arthritis. This study investigates the antibacterial and antirheumatic properties of piperine analogues. Computational analyses, including molecular docking quantum chemical studies and ADMET analysis, are performed to screen out potential inhibitory compounds. A library of 100 ligands is obtained from PubChem and subjected to virtual screening using various filters, including pharmacophore properties, molecular docking, and toxicity prediction, to identify potential candidates. Four compounds, P1-P4, are selected for further investigation using quantum chemical methods. These compounds are subjected to quantum chemical spectroscopic analysis, including UV–visible and IR spectra. The molecular geometries are fully optimized. HOMO and LUMO orbitals including their energies are calculated to estimate intermolecular charge transfer properties Molecular docking results revealed “compound P3 displayed the highest binding affinity to both proteins, with binding energies of 9.0 kcal/mol and 9.8 kcal/mol for FtsZ and Neutrophil collagenase proteins, respectively”. The analysis of 2D and 3D interactions between the selected compounds and both proteins reveals the formation of three important hydrogen bonds between ligand P3 and the FtsZ protein, as well as two hydrogen bonds between P3 and the Neutrophil collagenase protein. Additionally, ligand P4 forms three hydrogen bonds with the Neutrophil collagenase protein. The small energy gap of 3.85 eV between the HOMO and LUMO of the optimized molecule Neutrophil collagenase indicates that the compound is among the category of soft compounds and biologically more active. As new insights, for the first time, we performed a comparative analysis of the energies of the docked and optimized ligands that reveal the docked ligands always possess higher energies which might be considered as energy-penalty during the docking process. This energy penalty is found to be −24, −22, −26 and −32 kcal/mol for FtsZ and −169, −40, −35 and −39 Kcal/mol for Neutrophil collagenase P1-P4, respectively. The orbital energy gap further decreases in solvation with water and increases its chemical reactivity. Under the solvation effect of water as solvent, the quantum computational results indicated enhanced molecular solubility and stability, which are critical factors for bioavailability. The researchers suggested that the combination of increased reactivity and better solubility ensures that the drug performs more effectively in biological environments, making it a more potent inhibitor for bacterial infections and arthritis. The molecular geometries including bond lengths and bond angles of all studied compounds were also influenced in a solvent environment.

The Synthesis of MOFs of ZnImBImZnO through Hydrothermal and Solvothermal Methods

Metal-organic frameworks (MOFs) are a promising class of materials that have a wide range of applications, from gas storage to catalysis. The synthesis of MOFs from the ZnImBImZnO framework has been carried out using hydrothermal and solvothermal methods. By using different metal-ligand molar ratios and solvents, we have discovered that MOFs can be formed both in DMF and water solvents. The products obtained were studied using various techniques, including SEM, PSA, and FTIR, to confirm their formation Our research has shown that MOFs synthesized with different concentrations and solvents show different size distributions. This suggests that the choice of solvent and concentration can be used to control the size and morphology of the MOFs. Furthermore, we have found that the formation of the MOFs framework also directs the morphology of the Zn(II)-imidazole complex and ZnO NFs. Our results provide important insights into the synthesis and properties of MOFs. Moreover, the contact angle measurement data for the ZnImBImZnO framework indicates that it is unequivocally hydrophilic. By understanding the factors that influence the properties of MOFs, we can design new materials with specific properties tailored to different applications. This exciting research area has the potential to revolutionize many fields, from energy storage to drug delivery. Our results provide important insights into the properties of MOFs and pave the way for developing new materials with tailored properties.

Dyeing ability of C. longa L. and T. stans (L.) Juss. Ex Kunth on unmordanted and mordanted silk and cotton fabrics

The work was on the extraction of both the C. longa rhizomes and the petals of T. stans using four different solvents (ethanol, ethyl acetate, water, and n-hexane). The dyeing potential of the C. longa and T. stans extracts was evaluated on cotton and silk fabrics without or with mordants using potash alum, phosphomolybdic acid, iron (II) sulphate, and tartaric acid at varied temperatures and tested for colour fastness properties (wash and light fastness). The pH and absorbance of the dye bath before and after dyeing were studied. However, cotton, which is cellulosic, was better dyed than silk, which is proteinous, which showed a better choice for fabrics dyeing at 80 °C; hence, it had a good colour efficiency. Iron (II) sulphate exhibited complexes in the octahedral configuration of the coordination six with CH2O- of cotton and NH3+ and COO- of silk fabric. In addition, it was also observed that the higher the dyeing temperature, the greater the dyeing intensity. The spectroscopic characterization of the extracts was determined with the help of UV-Vis and FTIR. The UV-Vis and FTIR spectral analyses revealed the chromophore, auxochrome groups, and functional groups, respectively, within the extracts. Curcumin and rutin were identified as being responsible for the dyeing of the fabric.

Experimental and simulation study of reverse micelles formed by aerosol-OT and water in non-polar solvents.

The formation of reverse micelles by aerosol-OT [sodium bis(2-ethylhexyl) sulfosuccinate] in hydrocarbon solvents, and in the presence of water, is studied using a combination of atomistic molecular-dynamics simulations and small-angle neutron scattering (SANS). There have been many previous studies of aerosol-OT and its self-assembly in both water and non-aqueous solvents, but this work is focused on a combined experimental and simulation study of reverse-micelle formation. The effects of hydration (with water-to-surfactant molar ratios in the range 0-60) and solvent (cyclohexane and n-dodecane) are investigated. A force field is adapted that results in spontaneous formation of reverse micelles starting from completely randomized configurations. The computed dimensions of the reverse micelles compare very favourably with those determined in SANS experiments, providing validation of the simulation model. The kinetics of reverse-micelle formation are studied with a 50-ns, 1.7-million-atom system which contains, in the steady state, about 50 reverse micelles. The internal structures of reverse micelles are characterized with mass density profiles, and the effects of solvent, and the structural crossover from highly structured water to 'bulk' water in the core, are detailed. The corresponding changes in the molecular reorientation times of sequestered water are also determined. Overall, the combination of experiment and simulation gives a detailed picture of reverse-micelle self-assembly and structure.

Sodium Copper Chlorophyllin: A Sustainable Bioinspired Catalyst for the Aerobic Oxidative Synthesis of Nitrogen Heterocycles and the Oxidative Cyanation of Tertiary Amines

AbstractA remarkably simple and straightforward protocol has been reported showcasing sodium copper chlorophyllin (SCC) as an eco‐friendly, bioinspired catalyst for the aerobic oxidative synthesis of pharmaceutically prevalent nitrogen‐containing heterocycles, such as benzimidazoles and quinoxalines. This reaction was performed in green solvent water, using the green oxidant, molecular oxygen. SCC displayed exceptional efficiency, congruent with the prevailing metal/non‐metal‐based catalyst regime without requiring additives. The SCC catalyst exhibited excellent recyclability upto three cycles for the benzimidazole synthesis reaction. This benign strategy was successfully applied in synthesizing a bioactive quinoxaline i. e., Tyrphostin AG1296, a promising candidate for melanoma treatment. The catalytic activity of SCC was explored for the synthesis of another privileged moiety i. e., α‐aminonitriles, via the α‐cyanation of tertiary amines under oxidative conditions. This reaction progressed with a mild, easy‐to‐use, convenient cyanide source, such as ethyl cyanoformate, and a green and attractive solvent, such as methanol, precluding acidic media. SCC catalyst was efficiently recycled upto three cycles for the α‐aminonitriles synthesis. Overall, the utility of a biodegradable, robust catalyst such as SCC, eco‐friendly solvents such as water and methanol, green oxidants such as O2, and mild reaction conditions, devoid of acidic additives, renders the present work viable for academic and industrial research.

Molecular dynamics insights into the dynamical behavior of structurally modified water in aqueous deep eutectic solvents (ADES).

Recent studies have demonstrated that the presence of water in deep eutectic solvents (DESs) significantly affects their dynamics, structure, and physical properties. Although the structural changes due to the addition of water are well understood, the microscopic dynamics of these changes have been rarely studied. Here, we performed molecular dynamics simulation of 30% (v/v) (∼0.57 molar fraction) water mixture of DES containing CH3CONH2 and NaSCN/KSCN at various salt fractions to understand the microscopic structure and dynamics of water. The simulated results reveal a heterogeneous environment for water molecules in aqueous DES (ADES), which is influenced by the nature of the cation. The diffusion coefficients of water in ADESs are significantly lower than that in neat water and concentrated aqueous NaSCN/KSCN solution. When Na+ ions are replaced by K+ ions in the ADES system, the diffusion coefficient increases, which is consistent with the measured nuclear magnetic resonance data. Self-dynamic structure factor for water and other simulated dynamic quantities, such as reorientation, hydrogen-bond, and residence time correlation functions, show markedly slower dynamics inside ADES than in the neat water and aqueous salt solution. Moreover, these dynamics become faster when Na+ ions in ADES are replaced by K+ ions. The results suggest that the structural environment of water in Na+-rich ADES is rigid due to the presence of cation-bound water and geometrically constrained water. The medium becomes less rigid as the KSCN fraction increases due to the relatively weaker interaction of K+ ions with water than Na+ ions, which accelerates the dynamical processes.