Hydroxyl Research Articles

Enhanced emulsion capacity and gel properties of bighead carp myofibrillar protein through interaction with fresh maize bran arabinoxylan extracted by complex enzymes

SummaryBighead carp has the largest production amount among freshwater fish in China, but its physicochemical properties change rapidly with the denaturation of their myofibril protein (MP). The protein–polysaccharide complexes have shown interesting physicochemical properties as stabilisers and emulsifiers. In this study, arabinoxylans (AXs) were prepared and mixed with bighead carp MP to form a composite gel. The effect of AXs on the thermal stability, emulsification and emulsion stability of the composite gel was investigated. The results showed that fraction precipitated by 60% ethanol (F60) and by 90% (F90) improved the denaturation temperature of bighead carp MP from 65.99 °C to 67.39 °C and 68.22 °C, respectively. The emulsifying capacity of F60 (0.54 m2 g−1) was similar to that of sucrose (0.52 m2 g−1). The effect of F90 on the emulsion stability of bighead carp MP was better than that of F60. The elasticity of bighead carp MP was improved by F60 and F90. The hydroxyl group interactions, hydrophobic interactions and electrostatic forces exist between the macromolecules. AXs of fresh maize bran could prevent protein denaturation and improve the emulsion capacity and gel properties of bighead carp MP.

A Facile and Rapid Immobilization Method of Titanium Dioxide-Alginate Composite for The Photocatalytic Removal of Reactive Black-5

A facile and rapid approach to immobilize nano-sized titanium dioxide (TiO2) using a renewable biopolymer (i.e. alginate) has been successfully demonstrated. TiO2 exhibits a positively charged surface in acidic environment due to the presence of hydroxyl groups. Meanwhile, alginate polymer is negatively charged at any pH due to the presence of carboxylic group in the polymer chain. The negatively charged alginate polymer and positively charged TiO2 formed composite instantaneously when the alginate polymer was introduced into the TiO2 nanoparticles suspension. The TiO2-alginate (TiO2-A) composite photocatalyst was characterized using thermogravimetric analysis (TGA), field emission-scanning electron microscopy (FE-SEM) coupled with energy dispersive X-ray (EDX) analysis and Fourier Transform Infrared (FTIR). Thermogravimetric analysis indicated that incorporating TiO2 into sodium alginate increases its decomposition temperature due to the stability of TiO2 at elevated temperatures, with the TiO2 content estimated in the composite being 55.6%, lower than the theoretical calculation of 62.8%. FTIR analysis revealed a shift in the peak of the carboxylic group of sodium alginate, suggesting composite formation through electrostatic interactions with TiO2 nanoparticles, while FESEM analysis showed that the TiO2-A composite surface exhibited more pores compared to protonated alginate. The TiO2-A composite was able to remove 90% of the Reactive Black 5 (RB5) in less than 200 min under Ultra-violet (UV) illumination. The optimal pH to remove RB5 was found to be pH 2 due strong electrostatic attraction of negatively charged RB5 on the positive surface of TiO2 nanoparticles. The photocatalyst can be recovered by simple separation method, i.e. gravitational settling, and reused for 10 consecutive cycles with efficiency greater than 90% consistently. The TiO2-A composite is a promising immobilized photocatalyst for practical application in wastewater treatment. Copyright © 2024 by Authors, Published by BCREC Publishing Group. This is an open access article under the CC BY-SA License (https://creativecommons.org/licenses/by-sa/4.0).

Synthesis of Multifunctional Organic Molecules via Michael Addition Reaction to Manage Perovskite Crystallization and Defect.

Additive engineering plays a pivotal role in achieving high-quality light-absorbing layers for high-performance and stable perovskite solar cells (PSCs). Various functional groups within the additives exert distinct regulatory effects on the perovskite layer. However, few additive molecules can synergistically fulfill the dual functions of regulating crystallization and passivating defects. Here, we custom-synthesized 2-ureido-4-pyrimidone (UPy) organic small molecules with diverse functional groups as additives to modulate crystallization and defects in perovskite films via the Michael addition reaction. Theoretical and experimental investigations demonstrate that the -OH groups in UPy exhibit significant effects in fixing uncoordinated Pb2+ ions, passivation of lead-iodide antisite defects, alleviating hysteresis, and reducing non-radiative recombination. Furthermore, the enhanced C=O and -NH2 motifs interact with the A-site cation via hydrogen bonding, which relieves residual strain and adjusts crystal orientation. This strategy effectively controls perovskite crystallization and passivates defects, ultimately enhancing the quality of perovskite films. Consequently, the open-circuit voltage of the UPy-based p-i-n PSCs reaches 1.20 V, and the fill factor surpasses 84%. The champion device delivers a power conversion efficiency of 25.75%. Remarkably, the unencapsulated device maintained 96.9% and 94.5% of its initial efficiency following 3,360 hours of dark storage and 1,866 hours of 1-sun illumination, respectively.

Atomic-level insights into CeO2 performance: Chemical interactions in CMP explored through CeO2-SiO2 studies

This study explores the effects of atomic-level factors on the performance of CeO2 when interacting with SiO2 films. It specifically examines how different precursors, the ratio of Ce to OH, and reaction temperatures influence outcomes. Our findings reveal that smaller particles, around 5 nm in size, created using a Ce4+ precursor, are more effective at removing SiO2 films compared to larger, more crystalline particles from a Ce3+ precursor. This is due to their increased interaction with the SiO2 film during the polishing process, challenging the conventional emphasis on mechanical abrasion in chemical mechanical planarization (CMP) and highlighting the crucial role of chemical interactions. Further analysis through FT-IR and TGA-FTIR techniques showed distinct functional group profiles on the ceria surfaces. Ceria derived from Ce4+ exhibited a higher presence of OH and NO3 groups, enhancing adsorption capabilities, as verified by CHN analysis. Importantly, first-principles calculations identified these surface groups as key to improving adhesion to SiO2 films. Surfaces of amorphous CeO2, rich in -OH and -NO3 groups, showed significantly higher adhesion levels than their crystalline counterparts, connecting crystallinity to chemical functionality. This new insight leads to the possibility of designing next-generation CeO2 abrasives with increased chemical activity.

Hydration structure and dynamics of phosphoric acid and its anions-Ultrafast 2D-IR spectroscopy and abinitio molecular dynamics simulations.

The hydration shells of phosphate ions and phosphate groups of nucleotides and phospholipid membranes display markedly different structures and hydrogen-bond strengths. Understanding phosphate hydration requires insight into the spatial arrangements of water molecules around phosphates and in thermally activated structure fluctuations on ultrafast time scales. Femtosecond two-dimensional infrared spectroscopy of phosphate vibrations, particularly asymmetric stretching vibrations between 1000 and 1200cm-1, and abinitio molecular dynamics (AIMD) simulations are combined to map and characterize dynamic local hydration structures and phosphate-water interactions. Phosphoric acid H3PO4 and its anions H2PO4-, HPO42-, and PO43- are studied in aqueous environments of different pH value. The hydration shells of phosphates providing OH donor groups in hydrogen bonds with the first water layer undergo ultrafast structural fluctuations, which induce a pronounced spectral diffusion of vibrational excitations on a sub-300fs time scale. With a decreasing number of phosphate OH groups, the hydration shell becomes more ordered and rigid. The 2D-IR line shapes observed with hydrated PO43- ions display a pronounced inhomogeneous broadening, reflecting a distribution of hydration geometries without fast equilibration. The AIMD simulations allow for an in-depth characterization of the hydration geometries with different numbers of water molecules in the first hydration layer and different correlation functions of the fluctuating electric field that the water environment exerts on the vibrational phosphate oscillators.

Multifunctional biomass-based solar evaporator with enhanced sterilization performance for solar-driven clean water evaporation

Solar-driven interfacial evaporation presents an important technology in dealing with the global freshwater crisis due to its highly effective solar-to-vapor conversion, minimal environmental impact, and off-grid application. However, the high material cost, complex fabrication process, and lack of effective sterilization limit its scaled-up application. Herein, we demonstrate an efficient multi-functional, biomass-based (MBB) photothermal evaporator using CuO nanoparticle-modified, carbonized peanut shells in a low-cost and scabble way. With highly efficient solar absorption, localized heating, and water transport, the MBB photothermal evaporator achieved a ∼ 91.1 % solar-to-vapor efficiency under sunlight illumination with a clean water production rate of 1.46 kg m−2 h−1. A similar evaporation rate of 1.41 kg m−2 h−1 was obtained directly from wastewater or seawater with a wide range of pH (2–14). The experiments showed that the collected water is relatively clean with complete removal of Escherichia coli and Staphylococcus aureus by damaging bacterial cell walls. 99 % of methylene blue and rhodamine B can also be effectively removed, benefiting from the formation of chelating and hydrogen bonds with the OH groups on the surface of MBB. This research provides a new environmentally sustainable photothermal evaporator for water purification, specifically designed to benefit economically stressed communities.

Overcoming Chemical Dissociation Processes: Electrochemical Modulation of High‐Affinity Binding Sites for Rapid Uranium Extraction from Seawater

AbstractCurrently reported adsorption (hydroxyl or amidoxime) groups must dissociate hydrogen ions to form ─O− units for the coordination with uranyl ions. However, this process suffers a high energy barrier for bond dissociation, leading to the sluggish uptake speed and low adsorption capacity for uranium extraction from natural seawater. Herein, this study proposes a strategy for electrochemical modulation of adsorption sites, which overcomes the chemical dissociation processes of hydrogen ions. Poly‐2,5‐dihydroxy‐1,4‐benzoquinone containing redox carbonyl groups is intercalated into the channels of a covalent organic framework (COF) through in situ cross‐linking of 2,5‐dihydroxy‐1,4‐benzoquinone. Under electrochemical modulation, the C═O groups are transformed into adjacent phenol–oxygen anions to cooperate with the coordination atoms (O and N) on the COF channel for rapid binding of uranyl ions, which gave an absorption rate of 4.2 mg g−1 d−1 (≈3.3 ppb of uranium in natural seawater). Notably, the COF‐based electrodes delivered an average capacity of ≈20.8 mg‐U per g for uranyl ion adsorption during 5 days of extraction, ≈3000 times larger than that of classical tannin‐based adsorbents. The proposed method for preparing electrochemically modulated binding sites is expected to provide guidance for designing high‐efficiency adsorbents in the future.

Hydrophilic and Insulative Interface Strategy Against Side Reactions for Dendrite‐Free Zinc Metal Anodes

AbstractThe zinc dendrite growth and the parasitic hydrogen evolution reactions (HER) hinder the commercialization of zinc batteries. To address this, a hydroxyl‐rich Boehmite coating (HR‐BC) strategy is developed that combines excellent electrical insulation and high zinc ion conductivity. The hydrophilic hydroxyl groups facilitate hydrogen bond formation with the hydrated zinc ions, accelerating the de‐solvation process and suppressing the HER. Additionally, the electrically insulative nature of Boehmite prevents the reduction of zinc ions within HR‐BC and results in preferential Zn deposition underneath it, leading to a dendrite‐free “sandwich structure” of HR‐BC//Zn deposition//Zn foil. Symmetric cells using HR‐BC‐Zn electrodes obtain an ultralong and stable cycling lifetime of 1700 h at 5 mA cm−2, along with a high cumulative plating capacity of 4250 mAh cm−2. When paired with a V2O5 cathode, the HR‐BC‐Zn anode demonstrates a high capacitance retention of 90% and an average Coulombic efficiency (CE) of 99.8% after 4000 cycles. Furthermore, when combined with a heteroatoms‐doped carbon (HDC) cathode, the HR–BC–Zn//HDC pouch‐type cell exhibits superior lifetime performance with nearly 100% average CE after 15000 cycles at 3.0 A g−1. This work highlights the effectiveness of hydrophilic and insulative coating strategies in fostering the progression of long‐lasting zinc‐based energy storage systems.

Monte Carlo QM/MM simulation studies of the Cannizzaro reaction in ionic liquids for improved biofuel production.

The conversion of biomass to 5-hydroxymethylfurfural (HMF) holds substantial promise as a renewable energy source. Notably, HMF can be transformed into 2,5-bis(hydroxymethyl)furan (BHMF), a crucial reactant in biofuel production, but requires harsh operating conditions, H2, and precious metal catalysts. A recently reported Cannizzaro reaction of HMF to BHMF, characterized by its efficiency, mild conditions, and eco-friendliness, instead employed ionic liquids (ILs) to achieve high yields. In this study, combined quantum mechanical and molecular mechanical (QM/MM) simulations in conjunction with Metropolis Monte Carlo statistical mechanics and free-energy perturbation theory utilized M06-2X/6-31+G(d), PDDG/PM3, and the OPLS-VSIL force field to uncover important solute-solvent interactions present in the HMF to BHMF reaction pathway. The Cannizzaro reaction was examined in water and in five ILs composed of the 1-butyl-3-methylimidazolium [BMIM] cation coupled to hexafluorophosphate, tetrafluoroborate, thiocyanate, chloride, and bromide. Energetic and structural analysis of the rate-determining hydride transfer between HMF and the hydride-donor anion HMFOH- attributed the enhanced reactivity to highly organized solvent interactions featuring (1) hydrogen bonding between the ring protons of [BMIM] and the negatively charged carbonyl oxygen atoms on the transition structure, (2) favorable electrostatic interactions between the IL anions and solute hydroxyl groups, and (3) beneficial π-π stacking interactions between [BMIM] and the two aromatic rings present in HMF and HMFOH-.

Equipping Uridine with Three Dipeptide Motifs for the Inhibition of Radical-Induced DNA Oxidation.

We report the discovery and characterization of antioxidative effects of uridine linked with three dipeptide motifs against DNA oxidation induced by peroxyl radicals. First, the dipeptide motifs are constructed by using the Ugi four-component reaction (Ugi 4CR), in which caffeic, ferulic, sinapic, and syringic acids are used as the carboxylic acid resources, vanillin, benzaldehyde, and p-hydroxybenzaldehyde are used as the aldehyde resources, tyramine- and dopamine-related isocyanides as well as ethyl isocyanoacetate are used as the isocyanide resources, and 2-(p-aminophenyl)ethanol is used as the amine component. We found that the antioxidative effects of the Ugi 4CR products are 1.3-2.8 times higher than those of caffeic, ferulic, sinapic, and syringic acids in the protection of DNA against peroxyl radical-induced oxidation. Moreover, when three Ugi 4CR products are linked with three hydroxyl groups of uridine by using three succinic anhydrides as the linkage, the inhibitory effects of the afforded uridine-dipeptide hybrids against the DNA oxidation increase 4.4-8.9 times (>3 times) compared to that of the Ugi 4CR product. This is due to the hybrid structure consisting of uridine and three motifs of the Ugi 4CR product enabling binding with the DNA strand more efficiently and quenching free radicals more rapidly. Therefore, the hybrid structure constructed by the nucleoside with antioxidative dipeptides offers an additional advantage for protecting DNA against radical-induced oxidation.

Functionalization of MXene using iota-carrageenan, maleic anhydride, and N,N′-methylene bis-acrylamide for high-performance removal of thorium (IV), uranium (IV), sulfamethoxazole, and levofloxacin

An increasing quantity of pollutants has been discharged into the aquatic media, posing a serious hazard to public health. To address this issue, a new sorbent material, MXene@i.Carr@MaMb, was developed through the functionalization of the MXene surface using iota-carrageenan (i.Carr), maleic anhydride, and N, N′-methylene bis-acrylamide. This sorbent material was designed to remove thorium (Th (IV)) effectively, uranium (U (IV)), sulfamethoxazole (SMX), and levofloxacin (LEV) from wastewater. The MXene@i.Carr@MaMb composite incorporated significant functional groups, including OH, F, and O from MXene, oxygen and ester sulfate groups from iota-carrageenan (i.Carr), and OH, NH, and CO groups from N, N′-methylene bis-acrylamide, and maleic anhydride, which interacted with the UV (IV), Th (IV), SMX, and LEV pollutants through electrostatic interaction, complexation, and hydrogen bonding. MXene@i.Carr@MaMb composite exhibited excellent sorption capacities for Th (IV) (3.6 ± 0.03 mmol g−1), U (IV) (3.7 ± 0.09 mmol g−1), SMX (5.8 ± 0.03 mmol g−1), and LEV (5.9 ± 0.05 mmol g−1) at 323.15 K. The sorption kinetics and isotherms of radioactive metals and antibiotics can be well-described using pseudo-first-order kinetic models and Langmuir and Sips isothermal equations. This study presented a novel sorbent material for efficiently removing radioactive metals and antibiotics from wastewater.

Mechanisms of adaptive resistance in Phytobacter sp. X4 to antimony stress under anaerobic conditions

Sb(III) oxidation by microorganisms plays a key role in the geochemical cycling of antimony and is effective for bioremediation. A previously discovered novel Sb(III)-oxidizing bacteria, Phytobacter sp. X4, was used to elucidate the response patterns of extracellular polypeptides (EPS), antioxidant system, electron transfer and functional genes to Sb(III) under anaerobic conditions. The toxicity of Sb(III) was mitigated by increasing Sb(III) oxidation capacity, and the EPS regulated the content of each component by sensing the concentration of Sb(III). High Sb(III) concentrations induced significant secretion of proteins and polysaccharides of EPS, and polysaccharides were more important. Functional groups including hydroxyl, carboxyl and amino groups on the cell surface adsorbed Sb(III) to block its entry. Hydroxyl radicals and hydrogen peroxide were involved in anaerobic Sb(III) oxidation, as revealed by changes in the antioxidant system and electron spin resonance (EPR) techniques. qPCR confirmed that proteins concerning nitrate and antimony transfer, antimony resistance and antioxidant system were regulated by Sb(III) concentration, and the synergistic cooperation of multiple proteins conferred high antimony resistance to X4. The adaptive antimony resistance mechanism of Phytobacter sp. X4 under anaerobic conditions was revealed, which also provides a reference value for bioremediation method of antimony contamination in anaerobic environment.

Preparation of fully physically crosslinked double-network gel and its fire prevention mechanism

It is important to gain an in-depth understanding of the structure of fire prevention and extinguishing materials during self-heating of coal. In this paper, an Al3+-CMC/PAM-MMT fire prevention and extinguishing gel with double-network was prepared using sodium carboxymethyl cellulose (CMC) and polyacrylamide (PAM) as raw materials, and aluminum citrate (AlCit) and sodium montmorillonite (Na-MMT) as auxiliary materials, by introducing the fully physically crosslinking effect. The optimal amounts of CMC, PAM, AlCit and MMT were determined to be 2 %, 3 %, 8 %, and 3 %, respectively, based on gelation time, stability, and resistance of the gel. The micromorphological image of the double-network gel exhibited a laminar structure of parallel-aligned fibrous networks, where the pores and channels exhibited more complex shapes and became smaller in size, highlighting the superiority of the double-network architecture. The rheological tests showed that the double-network gel had superior structural stability and viscosity under varying shear rates, making it more effective in covering the fire source, enhancing extinguishing efficiency. Additionally, its higher storage and loss moduli indicated stronger elasticity and mechanical properties compared to the single-network gel, emphasizing its advantages in energy storage and recovery. The characterization of active functional groups showed that there was an effective suppression of reactions involving hydroxyl, hydrocarbon, and carbonyl functional groups, during the spontaneous combustion process of coal, following treatment with the gel. Additionally, a proposed mechanism for the gel formation was presented. In the sealing performance test, the pressure-bearing capacity of the double-network gel was approximately twice that of the single-network gel. It indicated that the multi-level structure formed by the gel led to higher density of physical cross-linking points, which provided better sealing performance. Thermogravimetric analysis showed significant decrease in total calorific value and increase in activation energy of coal, after treatment with the gel, rendering it more difficult for spontaneous coal combustion. In the small-scale fire extinguishing performance test, the double network of Al3+-CMC/PAM-MMT gel demonstrated effective suppression of spontaneous combustion of coal and reduced the susceptibility to re-ignition. The fire prevention mechanism of the gel was further explored experimentally.

One dimensional water chain as a zipper in a new polymorph of trans [Cu(vanilin)2(H2O)2].2(H2O) crystal–A case of water induced polymorphism

A new polymorph [Cu(II)(vanillin)2(H2O)2].2(H2O) has been synthesized and characterized by single crystal X-ray structural studies. Two other crystals having same formula and coordination unit but differing supramolecular arrangement due to slightly different role played by water molecules have already been reported in the literature [B. Kozlevˇcar et al. Z. Naturforsch., B: Chem. Sci. 2005, 60, 1273][Kozlevčar et al. Acta Chim. Slov. 2005, 52, 40–43]. The current compound is another polymorph in this system which has arisen again due to a different supramolecular arrangement which is water induced. Hirshfeld surface and energy framework analysis have been employed to compare these three polymorphs by assessing the nature of intermolecular interactions. In the current compound strong OH···O hydrogen bonding interactions between coordinated water molecules and –OH group attached to vanillin ligand leads to parallel alignment of successive coordination units leading to a supramolecular ribbon topology that runs along the crystallographic a-axis. A zigzag chain of single file water chain is positioned in between successive ribbons which acts as a zipper giving rise to a 2D supramolecular arrangement of the molecular complexes. In two other reported polymorphs instead of a single file water chain a cyclic water motif has been observed. The electronic structure of the complex explored using DFT methodology. This set of three polymorphs is an interesting example of water induced polymorphism.

A bio-based soy wood adhesive modified by dual-crosslinking strategy with excellent mechanical strength and water-resistance

Soy-based adhesives have garnered significant attention owing to their distinctive environmentally sustainable characteristics and low cost. However, they exhibit inadequate bonding strength and water-resistance, which can be attributed to the presence of polar groups in soy flours. Herein, a simple and eco-friendly dual-crosslinking strategy was proposed to manufacture a soy-based adhesive (SF/IO4/CA adhesive) with excellent mechanical properties and good water-resistance. Specifically, soy flours were treated with sodium periodate (NaIO4) for oxidization, which facilitated the soy flours' self-crosslinking process by converting carbohydrates into components having the cross-linking action (internal cross-linking agents). Then, incorporating the citric acid (CA) would promote to the carboxyl groups (-COOH) of CA to react with the hydrophilic hydroxyl groups (-OH) present in soy flours by esterification reaction. The findings demonstrated that a high-performance plywood using SF/IO4/CA adhesive was successfully produced, which shear strength of cold-water (20 °C for 24 h), hot-water (63 °C for 3 h), and boiling-water (93 °C for 3 h) reached 1.69 MPa, 1.68 MPa, 1.72 MPa, and 1.47 MPa, respectively. The soy-based adhesive has excellent mechanical strength and water-resistance due to its dual-crosslinking network system, which has significant promise for application use in the wood-based panels industry.

Self-healing injectable hydrogels incorporating hyaluronic acid and phytic acid: Rheological insights and implications for regenerative medicine

Eying the increasing impact of hyaluronic acid (HA) and its multifaceted applications, this study employs a non-toxic, one-pot strategy to develop injectable, self-healing hydrogels for biomedical applications. Phytic acid (PA), a plant-derived organic acid with high biocompatibility and numerous hydroxyl groups, can act as a cross-linking agent to form hydrogen-bonded networks with the HA chains. The study examined the optimal mass ratio of HA to PA to achieve superior hydrogel performance. Fourier transform infrared spectroscopy, rheological studies, and thermal analysis confirmed the successful formation of the hydrogels, which exhibited injectability, rapid self-healing, malleability, and elasticity. The investigation of different compositions revealed a sensitive influence of PA on the self-assembly phenomena of HA during flow. SEM cross-section images of the freeze-dried gels revealed a porous surface in the form of an interconnected network of microchannels. In addition, the hydrogel exhibits good tissue adhesion properties and promotes cell proliferation in biocompatibility tests on human gingival fibroblasts. The significance of this study lies in the ability of the proposed materials to be injected, to conform to the complex 3D structure of host tissues as well as their ability to recover after damage, indicating significant potential as scaffolds for wound healing.

Synthesis, Spectroscopic Characterization, DFT, Molecular Docking, Catechol Oxidase Activity, and Anti-SARS-CoV-2 of Acylhydrazone Derivatives

In the present work, five pyrazole-hydrazone biomolecule ligands (L1–L5) were synthesized by condensation between 1H-pyrazole-3-carbohydrazide (2) and aromatic benzaldehydes. Their corresponding structures were elucidated employing NMR and FT-IR spectra and ESI-MS data. Li-Cu(II) complexes (i = 1–5) were evaluated for catecholase activity in situ at standard conditions. The findings disclose that the catecholase oxidation rate varies with the substituted functional groups in ligand and the anion type in the copper (II) salt. Catecholase activity results showed that the L(i = 1–5) -Cu(II)SO4 complexes exhibited efficient catalytic activity, and a maximum activity of 105 ± 42 µM.min−1 is obtained with L5-Cu(II)SO4. DFT and NBO calculations have been carried out to identify the global reactivity and the strength of interaction bonds between the donors and acceptors in L1–L5. The optimized structure of L1–L3 and L5 were found planar, while that of L4 is out of the molecular plan and forms a torsion angle of 18 degrees due to the presence of methoxy and hydroxyl group at meta and para. In L4, the 5-methyl-1H-pyrazole moiety. NBO findings show that the strongest interactions in L1–L5 are those involved in the electronic transition from π-bonding → π*-antibonding and LP → π*- antibonding molecular orbitals. Further, the anti-SARS-CoV-2 of L1–L5 are investigated by estimating their binding affinities into its binding. The docking results reveal that L1–L5 may act as SARS-CoV-2 main protease inhibitors with estimated binding energies in the −6.00 to −8.0 kcal.mol−1 range.

Honeycomb-like macroporous crosslinked chitosan assisted EDTA-intercalated Ca-Mg-Al layered hydrotalcite composite foams for efficient U(VI) biosorption

The biosorption is considered to be highly efficient for the separation of radionuclide from radioactive wastewater. Herein, the crosslinked chitosan assisted EDTA intercalated Ca-Mg-Al layered double hydroxides composite foam (CS-EDTA-LDH) was synthesized by combining EDTA intercalation and freeze-drying methods. The macroporous and ultralight properties of CS-EDTA-LDH facilitates its rapid adsorption and facile recovery, and the inorganic/organic incorporation can avoid pore collapse and provide numerous adsorption sites, while the EDTA intercalation can enhance the complex capture of U(VI). The CS-EDTA-LDH presents various functional groups (carboxyl, hydroxyl and amino groups) for U(VI) adsorption, and the adsorption capacity for U(VI) reached 272.3 mg/g at pH 5.0 and 298 K. The adsorption kinetics of U(VI) conformed to PSO equation, whereas the isotherms conformed to the Freundlich model, indicating heterogeneous adsorption with diffusion process as a rate-controlling step. The thermodynamic parameters indicate that U(VI) adsorption by CS-EDTA-LDH is endothermic and spontaneous in nature. The adsorption mechanism is related to the synergic complexation by multi-functional groups, ion exchange, and possible isomeric substitution. Overall, CS-EDTA-LDH could be a promising biosorbent for the cleanup of radioactive pollution due to its high performance for U(VI) adsorption and facile recovery.

Role of solvent in selective hydrodeoxygenation of monomeric phenols

The current production of aromatic hydrocarbons, crucial in fuel and polymer production, relies heavily on fossil resources. Finding carbon-neutral alternatives is necessary to address the current environmental challenges. Lignin emerges as a promising source for bio-based aromatics. However, existing catalytic hydrodeoxygenation processes often yield mixtures of cycloalkanes and aromatics. In our study, we investigated a selective route to obtain aromatics from phenols using the keto-tautomer reaction mechanism. According to this mechanism, the initial hydrogenation of the carbonyl group while a phenol compound is in its keto form leads to the removal of the hydroxyl group while preserving the aromatic structure. Our experiments focused on p-cresol, guaiacol, and mequinol, employing Pd/C and Ru/C catalysts. Experimental results revealed that aromatic hydrocarbons were favored during the hydrodeoxygenation of p-cresol and mequinol, while steric effects from the methoxy group hindered guaiacol's conversion. Furthermore, we observed significantly higher conversion rates when using hydrocarbon solvents compared to water, with toluene yields of up to 13.5 % by mass achieved on Pd/C. Our computational simulations confirmed the feasibility of the keto-tautomer mechanism on Pd cluster surfaces, similar to those found in Pd/C catalysts.

Uncovering the roles of Ce and Mn for NH3-SCR over Mn-Ce/IM-5 with extraordinarily superior wide-temperature performance

The development of wide-temperature catalyst with glorious activity and the resistance of SO2 for NH3-SCR reaction are of great importance. However, the preparation of wide-temperature catalyst with outstanding NH3-SCR performance and the resistance of SO2 is still challenging. In this work, Mn and Ce modified IM-5 molecular sieve catalyst (MC-5) was synthesized by incipient wetness impregnation method and the relationship of structure-activity was studied. MC-5 exhibited superior NOx conversion and it was more than 87% in the temperature range of 150-500 °C and ca. 100% at 225 °C due to the high concentration of Mn4+ and chemisorbed oxygen, the excellent redox ability and the synergistic effect of Mn and Ce. Meanwhile, the redox cycle of Mn4++Ce3+↔Mn3++Ce4+ promoted the electron transfer. 27Al NMR spectra and NH3-TPD confirmed Mn ion was mainly located on the bridge hydroxyl group (Brønsted acid sites). The localization energies ΔE of (Al, Mn) for IM-5 was determined by theoretical calculation and the reaction mechanism of M-5 catalyst on Brønsted acid sites was proposed. The reaction mechanism of M-5 catalyst on Brønsted acid sites followed L-H mechanism. And interestingly enough, the NH3-SCR activity of MC-5 significantly increased in the presence of SO2 at 200 °C. One of the reasons was that Ce binded more easily to SO42- and thus protected the active site Mn from sulfation. The other reason was the generation of more acid sites.