Chemical Methods Research Articles

Using Adiabatic Energy Splitting To Compute Dexter Energy Transfer Couplings.

Dexter energy transfer and transport (DET) are of broad interest in energy science, and DET rates depend on electronic couplings between donor and acceptor species. DET couplings are challenging to compute since they originate from both one- and two-particle interactions, and the strength of this interaction drops approximately exponentially with donor-acceptor distances. Using adiabatic energy splitting to compute DET couplings has advantages because adiabatic states can be calculated directly using conventional quantum chemical methods. We describe a minimum energy splitting method to compute the DET coupling by altering molecular geometries to drive the systems into a T1/T2 energy quasi-degenerate-activated DA complex. We explore the accuracy of various quantum chemical approaches to calculate the Dexter couplings.

Electrocatalytic hydrogen evolution coupled with dye hydrogenation reactions for sustainable wastewater treatment using transition-metal (Fe, Co, Ni, Cu) nanoparticles with ZnO nanowire supports

A water electrolysis coupled with chemical reduction strategy is proposed to realize sustainable wastewater treatment. Correspondingly, a series of transition-metal (e.g., iron, cobalt, nickel and copper) nanoparticles anchored on zinc oxide nanowire array (ZnO NA) with bifunctional catalytic activity for hydrogen evolution reaction together with dye hydrogenation reaction (HER/DHR) are developed, while their catalytic activity are comparatively investigated at the same time. This renewable strategy with environmental and economic benefits exhibits high-efficiency treatment capability towards various dye wastewaters. For example, a typical system based on nickel nanoparticles with ZnO NA supports, which exhibits higher catalytic activity towards the HER/DHR than those of other three counterparts under the same conditions, can transform waste 4-nitrophenol into valuable 4-aminophenol with an apparent rate constant of 36.95 × 10-3 min−1 and a conversion rate of 98.32 %, thereby achieving dye decolorization and resource regeneration simultaneously. Its efficiency is significantly superior to that of chemical method dependent on traditional reducing agents and commercial nickel materials, demonstrating its stronger competitiveness. It is mainly benefited from the interface synergistic effect of nickel nanoparticles and zinc oxide nanowires. This novel system is expected to replace conventional sewage remediation technologies for efficient, inexpensive, and eco-friendly dye degradation, and thus is very important for energy and environmental sustainability.

Oleanane-type saponins from Lysimachia laxa Baudo and their anti-bacterial activities.

Seven new oleanane-type triterpene saponins, lysimaponins A-G, were isolated from aerial parts of Lysimachia laxa Baudo. Their chemical structures have been elucidated by analysis of spectroscopic and chemical methods. All compounds were evaluated for their anti-bacterial effects against Microcystis aeruginosa, Vibrio parahaemolyticus, V. harveyi, V. vulinificus, V. cholerae, and V. alginolyticus. All compounds showed potent anti-bacterial activities against the cyanobacteria M. aeruginosa with IC50 values ranging from 14.4 ± 1.2 to 35.3 ± 2.2 µg/mL. Compounds 1, 2, 4-7 inhibited V. parahaemolyticus with MIC values ranging from 64 to 256 µg/mL. The results suggested that saponins from L. laxa could be potential anti-cyanobacteria agents.

In vitro study on the anticancer effects of oxalipalladium against PC3 human prostate carcinoma cells

Prostate cancer is a common type of cancer in men with high incidence and mortality. Our aim was to investigate the effects of oxalipalladium (ox-Pd) on metastatic human prostate cancer PC3 cells and compare them with the effects of oxaliplatin (ox-Pt) (as an approved cancer drug). We synthesized ox-Pd through a new chemical method and used FT-IR, 1H NMR, 13C NMR, and MS analyzes to characterize it. The effects of ox-Pd on PC3 cells viability, apoptosis, cell cycle, migration, and gene expression were examined. Inhibition of topoisomerase IIα activity was investigated by pHOT1 plasmid relaxation and kDNA decatenation assays. Chemical tests showed ox-Pd with the correct composition and structure. For the first time, the exact fragmentation pathway of ox-Pd and its difference with ox-Pt was obtained by MS analysis. Ox-Pd significantly decreased PC3 cell viability with less/no toxicity effect on MHFB-1 normal skin fibroblasts. Wound scratch assay confirmed the strong anti-migratory activity of ox-Pd. According to flow cytometry analysis, this drug increased the number of PC3 cells in late apoptosis and decreased DNA replication and mitosis. Furthermore, pHOT1 plasmid relaxation and kDNA decatenation assays showed that ox-Pd strongly inhibited the catalytic activity of topoisomerase IIα. The expression of topoisomerase IIα, Bcl-2, P21, and survivin was decreased while the expression of Bax and p53 was increased under ox-Pd treatment. We provide the first evidence that ox-Pd exhibits more selective anticancer effects on PC3 cells compared to ox-Pt. Taken together, these data strongly suggest a therapeutic window for ox-Pd in cancer.

A comparative metabolomics analysis of Açaí (Euterpe oleracea Mart.) fruit, food powder, and botanical dietary supplement extracts.

Euterpe oleracea Mart. (açaí) is a botanical of interest to many who seek functional foods that provide antioxidant and anti-inflammatory properties. Cancer patients are increasingly taking botanical dietary supplements containing açaí to complement their conventional therapeutics, which may lead to serious adverse events. Before testing our açaí extracts in vitro for botanical-drug interactions, the goal is to chemically characterize our extracts for compounds whose biological activity in açaí is unknown. The objective of this work was to develop a chemical fingerprinting method for untargeted characterization of açaí samples from a variety of sources, including food products and botanical dietary supplement capsules, made with multiple extraction solvents. An optimized LC-MS method was generated for in-depth untargeted fingerprinting of chemical constituents in açaí extracts. Statistical analysis models were used to describe relationships between the açaí extracts based on molecular features found in both positive and negative mode ESI. In an attempt to elucidate the differences in metabolites among açaí extracts from different cultivars, we identified or tentatively identified 173 metabolites from the 16 extracts made from 6 different sources. Of these compounds, there are 138 reported in açaí for the first time. Statistical models showed similar yet distinct differences between the extracts tested based on the polarity of compounds present and the origin of the source material. A high-resolution mass spectrometry method was generated that allowed us to greatly characterize 16 complex extracts made from different sources of açaí with different extraction solvent polarities.

Electrochemical activity of self-supporting nitrogen-doped graphene for the degradation and in-situ determination of methylene blue

Environmentally friendly wastewater treatment and online pollution monitoring systems, important for water quality control, are yet to be developed. Electrochemical strategies combining the electrocatalytic degradation and electroanalysis of organic pollutants are expected to achieve this key technology. This study employed a chemical vapor deposition method using N₂ gas as the nitrogen source and applying an alternating electric field to prepare self-supporting nitrogen-doped graphene (NG) tubes with a wall thickness of up to 480 μm comprising few-layer NG nanosheets. The correlation between the properties of these materials and the electrocatalytic activity for methylene blue (MB) was investigated. The feasibility of the electrochemical strategy for online wastewater treatment and detection was validated using a combination of UV–visible spectroscopy and differential pulse voltammetry. The NG tube with the N-C bond distribution regulated by adjusting the methane flow rate and growth time exhibited high electrocatalytic activity, rapidly degrading 50 mg L⁻¹ of MB within 36 min and tracking changes in MB concentration. The NG tubes were assembled in an electrocatalytic meter pen for water treatment, achieving a degradation efficiency of 99.4 % and a detection limit of 0.3 mg L−1 for the MB solution, quite satisfactory for emerging simultaneous degradation and monitoring processes. The developed self-supporting NG tubes are promising materials for electrocatalytic degradation anodes and sensing electrodes in water treatment. Dual-functional electrocatalytic systems have potential applications in water quality monitoring and improvement.

Improving the ferroelectric properties of Lu doped Hf0.5Zr0.5O2 thin films by capping a CeO x layer

Lu doped Hf0.5Zr0.5O2 (HZO) ferroelectric films were prepared on Pt/TiN/SiO2/Si substrate by chemical solution deposition method, and an interfacial engineering strategy for improving the ferroelectric property was explored by capping the Lu doped HZO films with a cerium oxide layer. Compared with the Lu doped HZO film without the CeO x coating layer, the Lu doped HZO film with the CeO x coating layer has a larger remanent polarization (2P r = 34.72 µC cm−2) and presents weaker wake-up behavior, which result from the higher orthogonal phase ratio and the lower oxygen vacancy of the CeO x coated Lu doped HZO film. In addition, the CeO x coating can remarkably improve the fatigue resistance and retention performance of the Lu doped HZO films. It is hoped that the results can provide an effective approach for the realization of high-performance and highly reliable hafnium oxide based ferroelectric thin films.

Numerical Investigation on Thermal Conductivity of Graphene Foam Composite for Thermal Management Applications.

Graphene foam prepared by the chemical vapor deposition method is a promising thermal interfacial material. However, the thermal properties of graphene foam highly depend on the experimental fabrication conditions during the chemical vapor deposition process. Aiming to reveal how to prepare the appropriate graphene foam for the various thermal management scenarios, the influence of experimental conditions on thermal properties of graphene foam was investigated. Furthermore, the contribution of thermal conductivity and thermal radiation to the effective thermal coefficient of graphene foam was carried out for comparison. The research results showed that the porosity and the cross-section shape of the struts of the growth template were two critical factors affecting the thermal transport of graphene foam, especially with the increase of temperature. In addition, the deposition time of graphene determined the wall thickness and affected the thermal conductivity directly. The thermal radiation contributed more than thermal conductivity when the temperature climbed continuously. Comparatively, the effective thermal coefficient of graphene foam composite with high porosity and circular-shape struts was much superior to that of others at high temperature. The research findings provide important guidance for graphene foam fabrication and its applications in the field of thermal management.

Optimization of keratin hydrolysis from sheep wool waste for enhanced crop performance: A sustainable approach in agriculture

Protein hydrolysates have emerged as potent enhancers of agricultural productivity, attributed to their nitrogen and amino acid richness. This study focuses on extracting keratin from sheep wool waste via water-based hydrolysis, aiming for eco-friendly alternatives to chemical methods. To refine this process, a novel response surface methodology integrating a Box-Behnken design (RSM-BBD) was devised, centering on temperature and hydrolysis time as pivotal factors affecting yield. Optimization yielded an impressive 99% w/v hydrolysis yield, with a fixed solid-liquid ratio (15:100 w/v) yielding 18.72 g/l of total nitrogen extraction. Analysis revealed a dominant presence of phenylalanine, noted for its role in plant water conservation. Agricultural trials demonstrated the hydrolysate's efficacy in enhancing maize crop physiology, evidenced by increased leaf surface area and fresh and dry plant weights across varied application rates. These results underscore the value of this innovative valorization process in agriculture. By harnessing keratin from sheep wool waste through water-based hydrolysis, the study proposes a sustainable alternative to traditional chemical techniques. The optimization of key parameters and subsequent positive impacts on maize crop physiology illustrate the potential of this approach to foster sustainable agricultural practices.

Anti-Resistant Strategies: Icotinib Derivatives as Promising Non-Small Cell Lung Cancer Therapeutics.

Non-small cell lung cancer (NSCLC) patients often benefit from EGFR inhibitors like gefitinib. However, drug resistance remains a significant challenge in treatment. The unique properties of 1,2,3-triazole, a nitrogen-based compound, hold promise as potential solutions due to its versatile structural attributes and diverse biological effects, including anticancer properties. Our synthesis process involved the huisgen cycloaddition chemical method, which generated diverse icotinib derivatives. We evaluated the anticancer capabilities of these derivatives against various cancer cell lines, with a specific focus on NSCLC cells that exhibit drug resistance. Additionally, we investigated the binding affinity of selected compounds, including 3l, towards wild-type EGFR using surface plasmon resonance (SPR) experiments. Notably, icotinib derivatives such as derivative 3l demonstrated significant efficacy against different cancer cell lines, including those resistant to conventional therapies. Compound 3l exhibited potent activity with IC50 values below 10 μM against drug-resistant cells. SPR experiments revealed that 3l exhibited enhanced affinity towards wild-type EGFR compared to icotinib. Our research findings suggest that 3l acts as a compelling antagonist for the protein tyrosine kinase of EGFR (EGFR-PTK). Icotinib derivative 3l, featuring a 1,2,3-triazole ring, demonstrates potent anticancer effects against drug-resistant NSCLC cells. Its enhanced binding affinity to EGFR and modulation of the EGFR-RAS-RAF-MAPK pathway position 3l as a promising candidate for the future development of anticancer drugs.

Biocatalysis in Non-Conventional Media: Unlocking the Potential for Sustainable Chiral Amine Synthesis.

The application of biocatalysis has become essential in both academic and industrial domains for the asymmetric synthesis of chiral amines, and it serves as an alternative tool to transition-metal catalysis and complements traditional chemical methods. It relies on the swift expansion of available processes, primarily as a result of advanced tools for enzyme discovery, combined with high-throughput laboratory evolution techniques for optimising biocatalysts. This manuscript highlights recent chemical and technological developments contributing to the sustainable applications of biocatalysis with industrial interest. Specifically, the use of non-conventional reaction media and the combination with photocatalysis can enhance production of chiral amines by allowing higher working concentrations and cascade transformations, leading to high yields and enantiomeric excesses. Furthermore, a selection of both known and modern strategies for enzyme immobilisation, along with the use of fed-batch and flow synthesis, demonstrates the potential to translate laboratory synthesis to effective scaled-up applications and improve the processing of large reaction volumes.

Synthesis and evaluation of Schiff base as corrosion inhibitor for carbon steel in 1 M HCl solution

Purpose The main purpose of the present study is to introduce new Schiff bases as corrosion inhibitor for carbon steel in 1 M HCl. The inhibitory activity of Schiff base was also assessed. Design/methodology/approach 2,2′-((1Z,1′Z)-((2,2-dimethylpropane-1,3-diyl)bis(azanylylidene))bis(methanylylidene))diphenol was synthesized and it’s performance as an inhibitor was then investigated in 1 M HCl. The inhibition of this compound was studied and evaluated by the chemical methods of electrochemical impedance spectroscopy, electrochemical potential dynamic polarization and Atomic Force microscopy (AFM) method. The thermodynamics parameters were investigated for corrosion of carbon steel in both the absence and presence of Schiff base. Findings The results of the tests showed that this compound has a good performance as an inhibitor and the percentage of inhibition on steel corrosion will increase with increasing concentration and it will reach 70% in the presence of 2 × 10−3 M of this inhibitor. Polarization tests indicated that this compound will act as a mixed inhibitor. Nyquist curves showed that the addition of this substance to the solution increased the charge transfer resistance and decreased the capacity of the double layer. The absorption of the new Schiff base on steel follows Langmuir adsorption isotherm, and the amount of free energy of adsorption indicates the spontaneous adsorption of this inhibitor. Using AFM investigations, the results of electrochemical methods were confirmed. Originality/value Incorporation of a new Schiff base into 1 M HCl is a promising approach for protecting the carbon steel against corrosive solution.

LASIS-Assisted Copper Nanoparticle Synthesis and Characterization, along with UV-Visible Spectroscopy

This study investigates the creation of copper nanoparticles (CuNPs) using chemical reduction and laser ablation in liquid (LASIS). UV-visible spectroscopy is used to examine the optical characteristics of the nanoparticles created by these techniques. The purpose of the study is to compare the stability, efficacy, and particle size of CuNPs produced using different techniques. When comparing the LASIS method to the chemical reduction process, Transmission Electron Microscopy (TEM) examination revealed that the former produced smaller and more uniform nanoparticles. This work demonstrates the effectiveness of both synthesis techniques, with LASIS clearly outperforming the other in the production of superior CuNPs with more control over particle size and dispersion. A thorough explanation of the chemical reduction method and LASIS used in the synthesis of copper nanoparticles is provided, and UV-visible spectroscopy is used to characterize the resulting particles.

Valorization of Seafood Waste for Food Packaging Development.

Packaging plays a crucial role in protecting food by providing excellent mechanical properties as well as effectively blocking water vapor, oxygen, oil, and other contaminants. The low degradation of widely used petroleum-based plastics leads to environmental pollution and poses health risks. This has drawn interest in renewable biopolymers as sustainable alternatives. The seafood industry generates significant waste that is rich in bioactive substances like chitin, chitosan, gelatins, and alginate, which can replace synthetic polymers in food packaging. Although biopolymers offer biodegradability, biocompatibility, and non-toxicity, their films often lack mechanical and barrier properties compared with synthetic polymer films. This comprehensive review discusses the chemical structure, characteristics, and extraction methods of biopolymers derived from seafood waste and their usage in the packaging area as reinforcement or base materials to guide researchers toward successful plastics replacement and commercialization. Our review highlights recent advancements in improving the thermal durability, mechanical strength, and barrier properties of seafood waste-derived packaging, explores the mechanisms behind these improvements, and briefly mentions the antimicrobial activities and mechanisms gained from these biopolymers. In addition, the remaining challenges and future directions for using seafood waste-derived biopolymers for packaging are discussed. This review aims to guide ongoing efforts to develop seafood waste-derived biopolymer films that can ultimately replace traditional plastic packaging.

High-Surface-Area Co-Cu-B Monolithic Self-Supported Catalyst for Efficient Sodium Borohydride Hydrolysis

Sodium borohydride (NaBH4) is a nontoxic and ideal storage material for hydrogen due to its safety and high hydrogen storage capacity. In order to improve the practicality of the sodium borohydride hydrogen production system, we deposited non-precious metal catalytic materials on readily available polymer foams using a simple chemical plating method, developing a suitable 3D catalyst. Its high specific surface area enables it to produce hydrogen at a rate of up to 3.92 L min−1 g−1. Its unique structure gives the catalyst excellent durability. In addition, an efficient NaBH4-based H2 supply system was developed using this catalyst. Co-Cu-B can facilitate stable hydrogen production from NaBH4, yielding a consistent power output ranging from 0 to 100 W. This work provides a new pathway for developing high-efficiency monolithic self-supported catalysts for industrial applications.

Chemical approaches to the sulfation of small molecules: current progress and future directions.

Sulfation is one of the most important modifications that occur to a wide range of bioactive small molecules including polysaccharides, proteins, flavonoids, and steroids. In turn, these sulfated molecules have significant biological and pharmacological roles in diverse processes including cell signalling, modulation of immune and inflammation response, anti-coagulation, anti-atherosclerosis, and anti-adhesive properties. This Essay summarises the most encountered chemical sulfation methods of small molecules. Sulfation reactions using sulfur trioxide amine/amide complexes are the most used method for alcohol and phenol groups in carbohydrates, steroids, proteins, and related scaffolds. Despite the effectiveness of these methods, they suffer from issues including multiple-purification steps, toxicity issues (e.g., pyridine contamination), purification challenges, stoichiometric excess of reagents which leads to an increase in reaction cost, and intrinsic stability issues of both the reagent and product. Recent advances including SuFEx, the in situ reagent approach, and TBSAB show the widespread appeal of novel sulfating approaches that will enable a larger exploration of the field in the years to come by simplifying the purification and isolation process to access bespoke sulfated small molecules.

MgO Modified by X2, HX, or Alkyl Halide (X = Cl, Br, or I) Catalytic Systems and Their Activity in Chemoselective Transfer Hydrogenation of Acrolein into Allyl Alcohol.

A new type of catalyst containing magnesium oxide modified with various modifiers ranging from bromine and iodine, to interhalogen compounds, hydrohalogenic acids, and alkyl halides have been prepared using chemical vapor deposition (CVD) and wet impregnation methods. The obtained systems were characterized using a number of methods: determination of the concentration of X- ions, surface area determination, powder X-ray diffraction (PXRD), surface acid-base strength measurements, TPD of probe molecules (acetonitrile, pivalonitrile, triethylamine, and n-butylamine), TPD-MS of reaction products of methyl iodide with MgO, and Fourier transform infrared spectroscopy (FTIR). The catalysts' activity and chemoselectivity during transfer hydrogenation from ethanol to acrolein to allyl alcohol was measured. A significant increase in the activity of modified MgO (up to 80% conversion) in the transfer hydrogenation of acrolein was found, while maintaining high chemoselectivity (>90%) to allyl alcohol. As a general conclusion, it was shown that the modification of MgO results in the suppression of strong basic sites of the oxide, with a simultaneous appearance of Brønsted acidic sites on its surface. Independently, extensive research on the reaction progress of thirty alkyl halides with MgO was also performed in order to determine its ability to neutralize chlorinated wastes.

Enhanced electrochemical performance of a cost-effective Sm2O3-coated spinel LiNi0.5Mn1.5O4 cathode for high-voltage lithium-ion batteries

Spinel LiNi0.5Mn1.5O4 (LNMO) has gained significant attention as a promising cathode material for lithium-ion batteries due to its high working voltage (>4.7 V) and energy density. However, challenges such as electrolyte decomposition-induced material interface erosion and transition metal dissolution under high operating voltage hinder its commercial use. In this study, a thin and uniform Sm2O3 layer has been successfully deposited on the surface of LNMO using a wet chemical method. A comprehensive investigation of surface morphology, crystal structure, and electrochemical performance of the modified LNMO is conducted. The results demonstrate that the Sm2O3 surface modification acts as a robust multifunctional protective layer, effectively shielding against hydrofluoric acid-induced chemical attack and enhancing the migration efficiency of lithium ions. Notably, the capacity retention rate of LNMO@Sm2O3 (3 wt%) remains up to 88 % after 280 cycles, significantly surpassing the uncoated counterpart. The coated material exhibits a capacity of 114 mAh g−1 even under 10 C rate conditions. Moreover, the AC impedance values and manganese dissolution of the modified material in the organic electrolyte are considerably lower than those of the uncoated counterpart. Theoretical calculations strongly support the experimental findings, revealing higher Mn vacancy formation energy and density of states at the Fermi energy level for the Sm2O3-modified electrodes. This research contributes to the field of surface modification and paves the way for further enhancements in the electrochemical performance of other high-voltage manganese-based lithium-ion batteries (LIBs).

Advances in genome sequencing and artificially induced mutation provides new avenues for cotton breeding.

Cotton production faces challenges in fluctuating environmental conditions due to limited genetic variation in cultivated cotton species. To enhance the genetic diversity crucial for this primary fiber crop, it is essential to augment current germplasm resources. High-throughput sequencing has significantly impacted cotton functional genomics, enabling the creation of diverse mutant libraries and the identification of mutant functional genes and new germplasm resources. Artificial mutation, established through physical or chemical methods, stands as a highly efficient strategy to enrich cotton germplasm resources, yielding stable and high-quality raw materials. In this paper, we discuss the good foundation laid by high-throughput sequencing of cotton genome for mutant identification and functional genome, and focus on the construction methods of mutant libraries and diverse sequencing strategies based on mutants. In addition, the important functional genes identified by the cotton mutant library have greatly enriched the germplasm resources and promoted the development of functional genomes. Finally, an innovative strategy for constructing a cotton CRISPR mutant library was proposed, and the possibility of high-throughput screening of cotton mutants based on a UAV phenotyping platform was discussed. The aim of this review was to expand cotton germplasm resources, mine functional genes, and develop adaptable materials in a variety of complex environments.

Assay of Front-Line Demonstration on Integrated Pest and Disease Management (IPDM) in Rice in the Vikarabad District of Telangana, India

Rice crop is attacked by various insects and diseases in spite of using pesticides, but relaying only on synthetic pesticides usage resulted into disrupt the natural balance between crop pests and their existed natural enemies. Integrated pest and disease management (IDPM) is a concept which is blended with all possible proven technologies like Cultural, Mechanical, Biological and Chemical methods. Front line demonstration on Integrated Pest and Disease Management in rice was taken up in farmers fields during kharif season of two consecutive years of 2021 and 2022 by DAATTC, Tandur in Vikarabad district of Telangana. Study revealed that seed treatment with Carbendazim @3gm/kg seed, seedling root dip with Pseudomonas species 10gm /lit of water, application of Carbofuran granules @160g/cent nursery, installation of pheromone traps, formation of alley ways and need based application of fertilizers and pesticides reduced the pest like Stem borer, BPH, Leaf folder and Blast disease significantly compared to farmers practice. Mean higher yield was recorded in demo field 6065 kg/ha compared to 5795 kg/ha in check, and showed 4.6 per cent yield increases in demonstration fields.