Chemical Methods Research Articles

Enhancing the combustion of nAl with AlF3 coating: gas-solid reaction mechanism for reducing combustion agglomeration of Al powder.

The combustion agglomeration of nano-aluminum (nAl) powder leads to incomplete combustion, which seriously hinders its application as metal fuel. In this work, nAl@AlF3 composites were produced by coating nAl with AlF3via a facile chemical deposition method. TEM and SEM analyses indicated that the AlF3 layer was evenly coated on the surface of nAl with a thickness of 4.6-9.1 nm, thereby varying the quantity of AlF3 applied. Experimental results from combustion indicated that the prepared nAl@AlF3 composites exhibit superior combustion efficiency, a higher combustion rate, and reduced combustion agglomeration as compared to raw nAl. Contrary to the widely accepted explanation that volatilization of AlF3 hinders Al combustion agglomeration, we proved that the gas-solid reaction between nAl and AlF3 plays an important role in inhibiting the sintering of nAl particles produced. The gaseous intermediate (i.e., AlOF and HF) released from the hydrolysis of AlF3 could reduce the diffusion barrier of Al2O3 to facilitate the reaction of Al core, which enhances the combustion reaction kinetics. More importantly, these gaseous products actively participate in the reaction cycle to continuously exert their catalytic effects.

The potential toxicity of chemically fabricated silver nanomaterials based on accumulation and histological changes in fish (Cyprinus carpio).

The bio-reductive fabrication of nanomaterials is a developing arena of study that seeks to fabricate nanoparticles (NPs) using microorganisms, plants, and animal blood. However, the chemical approach of AgNPs fulfills the need of abundant need of NPs. In contrast, chemically fabricated AgNPs are more toxic than biological AgNPs. Therefore, the current study aimed to assess and evaluate the chemically fabricated silver nanoparticles (AgNPs) for their possible toxicity in Common carp fish (Cyprinus carpio). The chemically synthesized silver nanoparticles were purchased from the market and applied for their possible toxicity. The chemically fabricated AgNPs were used against the Cyprinus carpio for bioaccumulation in different organs and histological alterations in the intestine and muscles. The results revealed that the AgNPs were mostly accumulated in the intestines followed by the gills, liver, and muscles (p < .05). The accumulated AgNPs caused histological alterations in gills and intestines at the highest concentration (0.08 mg/L). However, no alterations were observed by the middle and lowest concentration of AgNPs, particularly, in the intestine. In conclusion, more extensive research is required to establish the hazards related to the use of nanoparticles to disclose their negative effects on fish and the aquatic environment. REASEARCH HIGHLIGHTS: The chemical method fabricates a large amount of AgNPs Additionally, considered more toxic than the bio-reductive method AgNPs have excellent and diverse applications AgNPs deposited in various organs and cause histological changes.

Chemical Potential Analysis as an Alternative to the van't Hoff Method: Hypothetical Limits of Solar Thermochemical Hydrogen.

The van't Hoff method is a standard approach for determining reaction enthalpies and entropies, e.g., in the thermochemical reduction of oxides, which is an important process for solar thermochemical fuels and numerous other applications. However, by analyzing the oxygen partial pressure pO2, e.g., as measured by thermogravimetric analysis (TGA), this method convolutes the properties of the probe gas with the solid-state properties of the examined oxides, which define their suitability for specific applications. The "chemical potential method" is here proposed as an alternative. Using the oxygen chemical potential ΔμO instead of pO2 for the analysis, this method does not only decouple gas-phase and solid-state contributions but also affords a simple and transparent approach to extracting the temperature dependence of the reduction enthalpy and entropy, which carries important information about the defect mechanism. For demonstration of the approach, this work considers three model systems; (1) a generic oxide with noninteracting, charge-neutral oxygen vacancy defects, (2) Sr0.86Ce0.14MnO3(1-δ) alloys with interacting vacancies, and (3) a model for charged vacancy formation in CeO2, which reproduces the extensive experimental TGA data available in the literature. The reduction behavior of these model systems obtained from the chemical potential method is correlated with simulated results for the thermochemical water splitting cycle, highlighting the exceptional behavior of CeO2, which originates from defect ionization. The theoretical performance limits for solar thermochemical hydrogen within the charged defect mechanism are assessed by considering hypothetical materials described by a variation of the CeO2 model parameters within a plausible range.

Nanocrystal cellulose from diverse biological sources: Application and innovations

Cellulose is the most abundant renewable polymer on Earth which is extensively distributed in diverse ecosystems. It is present in higher plants, marine organisms, and also produced through microbial processes in organisms like algae, fungi, and bacteria. From an industrial perspective, the semicrystalline nature of cellulose present in different plant and microbial sources enables the fabrication of various types of nanocellulose, such as nanofibre and nanocrystals, through mechanical disintegration and chemical methods, respectively. Nanocellulose distinguishes itself as a sustainable, nonharmful, and biodegradable polymer. It will enable sustainable development for responsible consumption and production. Possessing a range of excellent properties, it can be seamlessly integrated into various materials. Research on nanocellulose is gaining momentum in response to current issues related to fossil fuels, including concerns about CO2 emissions, plastic pollution, and the need for renewable energy sources. This review addresses nanocrystals production method from cellulose found in agricultural, microbial sources, and its applications in fields such as materials science, electronics, medicine, and environmental science.

Sonication protocols and their contributions to the microbiological diagnosis of implant-associated infections: a review of the current scenario

Addressing the existing problem in the microbiological diagnosis of infections associated with implants and the current debate about the real power of precision of sonicated fluid culture (SFC), the objective of this review is to describe the methodology and analyze and compare the results obtained in current studies on the subject. Furthermore, the present study also discusses and suggests the best parameters for performing sonication. A search was carried out for recent studies in the literature (2019-2023) that addressed this research topic. As a result, different sonication protocols were adopted in the studies analyzed, as expected, and consequently, there was significant variability between the results obtained regarding the sensitivity and specificity of the technique in relation to the traditional culture method (periprosthetic tissue culture – PTC). Coagulase-negative Staphylococcus (CoNS) and Staphylococcus aureus were identified as the main etiological agents by SFC and PTC, with SFC being important for the identification of pathogens of low virulence that are difficult to detect. Compared to chemical biofilm displacement methods, EDTA and DTT, SFC also produced variable results. In this context, this review provided an overview of the most current scenarios on the topic and theoretical support to improve sonication performance, especially with regard to sensitivity and specificity, by scoring the best parameters from various aspects, including sample collection, storage conditions, cultivation methods, microorganism identification techniques (both phenotypic and molecular) and the cutoff point for colony forming unit (CFU) counts. This study demonstrated the need for standardization of the technique and provided a theoretical basis for a sonication protocol that aims to achieve the highest levels of sensitivity and specificity for the reliable microbiological diagnosis of infections associated with implants and prosthetic devices, such as prosthetic joint infections (PJIs). However, practical application and additional complementary studies are still needed.

Use of diffusive gradients in thin-film technique to predict the mobility and transfer of nutrients and toxic elements from agricultural soil to crops-an overview of recent studies.

The purpose of this review was to survey the recent applications of the diffusive gradients in thin films (DGT) technique in the assessment of mobility and bioavailability of nutrients and potentially toxic elements (PTEs) in agricultural soil. Many studies compared the capabilities of the DGT technique with those of classical soil chemical extractants used in single or sequential procedures to predict nutrients and PTE bioavailability to crops. In most of the published works, the DGT technique was reported to be superior to the conventional chemical extraction and fractionation methods in obtaining significant correlations with the metals and metalloids accumulated in crops. In the domain of nutrient bioavailability assessment, DGT-based studies focused mainly on phosphorous and selenium labile fraction measurement, but potassium, manganese, and nitrogen were also studied using the DGT tool. Different DGT configurations are reported, using binding and diffusive layers specific for certain analytes (Hg, P, and Se) or gels with wider applicability, such as Chelex-based binding gels for metal cations and ferrihydrite-based hydrogels for oxyanions. Overall, the literature demonstrates that the DGT technique is relevant for the evaluation of metal and nutrient bioavailability to crops, due to its capacity to mimic the plant root uptake process, which justifies future improvement efforts.

SimRNAweb v2.0: a web server for RNA folding simulations and 3D structure modeling, with optional restraints and enhanced analysis of folding trajectories.

Research on ribonucleic acid (RNA) structures and functions benefits from easy-to-use tools for computational prediction and analyses of RNA three-dimensional (3D) structure. The SimRNAweb server version 2.0 offers an enhanced, user-friendly platform for RNA 3D structure prediction and analysis of RNA folding trajectories based on the SimRNA method. SimRNA employs a coarse-grained model, Monte Carlo sampling and statistical potentials to explore RNA conformational space, optionally guided by spatial restraints. Recognized for its accuracy in RNA 3D structure prediction in RNA-Puzzles and CASP competitions, SimRNA is particularly useful for incorporating restraints based on experimental data. The new server version introduces performance optimizations and extends user control over simulations and the processing of results. It allows the application of various hard and soft restraints, accommodating alternative structures involving canonical and noncanonical base pairs and unpaired residues, while also integrating data from chemical probing methods. Enhanced features include an improved analysis of folding trajectories, offering advanced clustering options and multiple analyses of the generated trajectories. These updates provide comprehensive tools for detailed RNA structure analysis. SimRNAweb v2.0 significantly broadens the scope of RNA modeling, emphasizing flexibility and user-defined parameter control. The web server is available at https://genesilico.pl/SimRNAweb.

Estimation of Time of Death through Observation of Microbiota Changes in the Oral Cavity

Abstract: Various methods for estimating post-mortem (PMI) have been investigated such as rigor mortis, livor mortis, molecular, chemical, and forensic entomology (insect) methods. However, these methods have weaknesses, therefore researchers are looking for more accurate methods in determining the time of death of a person. Molecular methods are unreliable due to the degradation of DNA, RNA, and proteins in corpses over time. In different parts of the body, the amount of diversity of microbes will be different. The oral cavity is the most abundant microbial area among other parts of the body due to its continuous exposure to the respiratory and digestive systems. This area has great potential in estimating time intervals of death because of its ease of access and the types of microbiomes that predominate at any given time. Therefore, this narrative review was conducted to describe studies that used oral microbiota communities to estimate post-mortem intervals. Proteobacteria, Firmicutes, Actinobacteria, and Bacteroidetes are the dominant microbial types found in corpses. Firmicutes became one of the dominant bacterial phyla in the early stages of decomposition. Actinobacteria were found to decrease as PMI increased. Studies have shown that the oral microbiome has excellent potential as a parameter to determine the post-mortem interval. However, further research is needed with more complex environmental conditions such as different humidity and temperature. In addition, further research requires more samples of human remains to obtain more valid results. Keywords: oral microbiome; post-mortem interval; human identification; forensic odontology

Modificación química de almidón procedente de semillas de frutos: Métodos, propiedades y aplicaciones

The fruit seeds, commonly regarded as waste after consuming the fresh pulp, emerge as a source of unconventional starch with innovative potential. This study focuses on highlighting the significance of these seeds by exploring chemical modification methods in this starch source that add value by transforming their properties. The review emphasizes the influence of key factors such as the type of chemical reagent, its concentration, reaction parameters (pH, temperature, time), and the botanical source of the seed on the degree of modification and the resulting morphological and functional properties of the starch. The importance of specific conditioning during the chemical modification process is underscored, as it significantly contributes to enhancing the properties of the modified starch derived from fruit seed. In this regard, new perspectives are opened to efficiently harness fruit seeds, turning them into a valuable source of starch with diverse applications in both the food and non-food industries.

Crystalline-Amorphous Heterophase PdMoCrW Tetrametallene: Highly Efficient Oxygen Reduction Electrocatalysts for a Long-Term Zn-Air Battery.

Metallenes have received sustained attention owing to their unique microstructure characteristics and compelling catalytic applications, but the synthesis of multielement crystalline-amorphous metallenes remains a formidable challenge. Herein, we report a one-step wet chemical reduction method to synthesize composition-tunable crystalline-amorphous heterophase PdMoCrW tetrametallene. As-synthesized PdMoCrW tetrametallene is composed of approximately six to seven atomic layers and has flexible crimpiness, a crystalline-amorphous heterophase structure, and high-valence metal species. Time-dependent experiments show that PdMoCrW tetrametallene follows a three-step growth mechanism that includes nucleation, lateral growth, and atom diffusion, respectively. The novel ultrathin structure, optimized Pd electronic structure, and hydrophilic surface together greatly promote the activity and stability of PdMoCrW tetrametallene in the alkaline oxygen reduction reaction. Pd75.9Mo9.4Cr8.9W5.8/C exhibits excellent mass and specific activities of 2.81 A mgPd-1 and 4.05 mA cm-2, which are 20.07/14.46 and 23.42/16.20 times higher than those of commercial Pt/C and Pd/C, respectively. Furthermore, a Zn-air battery assembled using Pd75.9Mo9.4Cr8.9W5.8/C as a cathode catalyst achieves a peak power density of 156 mW cm-2 and an ultralong durability of 329 h. This study reports an effective strategy for constructing crystalline-amorphous quaternary metallenes to advance non-Pt electrocatalysts toward oxygen reduction reaction (ORR) performance and for a Zn-air battery.

A Deep Learning Approach for Chromium Detection and Characterization from Soil Hyperspectral Data

High levels of chromium (Cr) in soil pose a significant threat to both humans and the environment. Laboratory-based chemical analysis methods for Cr are time consuming and expensive; thus, there is an urgent need for a more efficient method for detecting Cr in soil. In this study, a deep neural network (DNN) approach was applied to the Land Use and Cover Area frame Survey (LUCAS) dataset to develop a hyperspectral soil Cr content prediction model with good generalizability and accuracy. The optimal DNN model was constructed by optimizing the spectral preprocessing methods and DNN hyperparameters, which achieved good predictive performance for Cr detection, with a correlation coefficient value of 0.79 on the testing set. Four important hyperspectral bands with strong Cr sensitivity (400–439, 1364–1422, 1862–1934, and 2158–2499 nm) were identified by permutation importance and local interpretable model-agnostic explanations. Soil iron oxide and clay mineral content were found to be important factors influencing soil Cr content. The findings of this study provide a feasible method for rapidly determining soil Cr content from hyperspectral data, which can be further refined and applied to large-scale Cr detection in the future.

Antireflection microstructures on ZnSe for mid- and far-IR fabricated by femtosecond laser ablation assisted with wet chemical etching

Most infrared materials used in high-power systems, such as optical parametric generators, have high values of refractive indices, which result in high Fresnel losses. The performance of conventional antireflection coatings is limited when used in high-power and ultra-broadband systems. An alternative approach is to fabricate antireflection microstructures (ARMs) that allow for a broadband increase in transmittance without reducing the damage threshold of the material. In this work, ARMs were fabricated on the surface of ZnSe crystals using the femtosecond laser ablation assisted with wet chemical etching method. This allowed to produce high aspect ratio microstructures that increase the transmittance up to 98% in the mid- and far- infrared regions.

Rational design of multi-component Fe(OH)3/Ni-NiO heterostructures bifunctional catalyst for electrochemical water splitting

Exploring economic-efficient bifunctional catalysts is critical for the production of green hydrogen through water splitting. Herein, we fabricate a novel hybrid catalyst with three-phase heterojunction (Fe(OH)3/Ni-NiO) via a simple electrodeposition and chemical precipitation method. Benefiting from the desirable amorphous-crystal interfaces, the electronic structure of Ni, NiO and Fe(OH)3 is regulated, which will optimize the adsorption of H intermediates (H*) and also reduce the kinetic barrier for the hydrogen evolution reaction (HER). The optimal Fe(OH)3–3/Ni-NiO/CC shows superior bifunctional activity with low overpotentials of 66 mV for HER and 220 mV for OER at 10 mA cm−2 in alkaline solution, respectively, as well as remarkable durability over a period of 40 h. Besides, Fe(OH)3–3/Ni-NiO/CC requires 1.52 and 1.72 V to deliver 10 and 100 mA cm−2 and shows no obvious increase in current within 40 h toward overall water splitting. Experimental and theoretical results show that the HER process is promoted by the synergistic effect of electronic redistribution between Ni, NiO and Fe(OH)3 due to the construction of three phase crystalline-amorphous heterogeneous interface. Meanwhile, Fe(OH)3 and NiO appeared reconstruction, transforming into FeOOH and NiOOH during OER process, respectively. This work offers a simple synthesis method for designing bifunctional catalysts for water splitting.

A Prospective Study of the Efficacy of Endofascial Axillary Dissection to Reduce Axillary Seroma Formation

Abstract Introduction Seroma formation is a common complication following axillary dissection. The pathogenesis of seroma is poorly understood. Various chemical and mechanical methods have been tried to reduce seroma with varying results. In this study, we look at a novel method of axillary dissection to reduce seroma and its attendant morbidity. The objective of the study is to compare endofascial axillary lymphadenectomy with routine axillary lymphadenectomy regarding axillary drain output following breast conservation surgery. Methods We did a prospective interventional study of endofascial axillary dissection in patients undergoing breast conservation surgery. Comparison was done with historical controls who underwent breast conservation surgery with routine axillary lymphadenectomy before the study period. All patients were operated by the same surgeon. Results Breast conservation surgery with endofascial axillary dissection was performed in 36 patients and compared with 36 patients who underwent routine axillary dissection before the study period. The mean total axillary drain output in the endofascial and routine groups were 796.8 and 1,259.3 mL, respectively (p = 0.001). The average day of drain removal in the endofascial and routine groups were 10.8 and 14.9 days, respectively (p = 0.001). The nodal yield of the endofascial and routine groups were 15.3 and 16.4 nodes, respectively (p = 0.449). The duration of surgery of the endofascial and routine groups were 89.3 and 85.1 minutes, respectively (p = 0.366). Conclusion Endofascial axillary dissection significantly reduced the mean total axillary drain output and resulted in early drain removal compared with routine axillary dissection. There were no significant differences in the nodal yield, operative time, seroma aspirations, and wound complications between the endofascial and routine axillary dissection groups.

The odd-number cyclo[13]carbon and its dimer, cyclo[26]carbon

Molecular rings of N carbon atoms (cyclo[ N ]carbons, or C N ) are excellent benchmarking systems for testing quantum chemical theoretical methods and valuable precursors to other carbon-rich materials. Odd- N cyclocarbons, which have been elusive to date, are predicted to be even less stable than even- N cyclocarbons. We report the on-surface synthesis of cyclo[13]carbon, C 13 , by manipulation of decachlorofluorene with a scanning probe microscope tip. We elucidated the properties of C 13 by experiment and theoretical modeling. C 13 adopts an open-shell configuration with a triplet ground state and a kinked geometry, which shows different extents of distortion and carbene localization depending on the molecular environment. Moreover, we prepared and characterized the C 13 dimer, cyclo[26]carbon, demonstrating the potential of cyclocarbons and their precursors as building blocks for carbon allotropes.

Deciphering the Glycan Kryptos by Solid-State Nanopore Single-Molecule Sensing: A Call for Integrated Advancements Across Glyco- and Nanopore Science.

Abstract Glycans, or complex carbohydrates, are information-rich biopolymers critical to many biological processes and with considerable importance in pharmaceutical therapeutics. Our understanding, though, is limited compared to other biomolecules such as DNA and proteins. The greater complexity of glycan structure and the limitations of conventional chemical analysis methods hinder glycan studies. Auspiciously, nanopore single-molecule sensors—commercially available for DNA sequencing—hold great promise as a tool for enabling and advancing glycan analysis. We focus on two key areas to advance nanopore glycan characterization: molecular surface coatings to enhance nanopore performance including by molecular recognition, and high-quality glycan chemical standards for training.

Enhancing the electrochemical properties of TiNb2O7 anodes with SP-CNT binary conductive agents for both liquid and solid state lithium ion batteries.

A high performance oxide composite electrode is obtained with a two-step solid state calcined titanium niobium oxide TiNb2O7 (TNO) anode and super P-carbon nanotube (SP-CNT) binary conductive agents. The solid state synthesized TNO-0.2C (the proportion of CNTs in the binary conductive agent is 20% wt) anode exhibits a high reversible discharge capacity of 278.6 mA h g-1 at 0.5C, a competitive rate capability with reported works that employed wet chemical methods at moderate rates (178.1 mA h g-1 at 10C), and an excellent capacity retention of 92.2% after 200 cycles at 1.5C/1.5C. The enhancement in electrochemical properties of the TNO-0.2C anode is mainly attributed to the combination of the short range and long range conductive agents in the SP-CNT binary conductive system, which guarantees an efficient electronic conductive network. The Li|Li1.3Al0.3Ti1.7(PO4)3 composite polymer electrolyte (LATPCPEs)|TNO-0.2C solid state batteries are also assembled, which deliver a high initial reversible discharge capacity of 241.3 mA h g-1 at 1C and a good capacity retention rate of 93% after 50 cycles. This work provides an efficient way to improve the electrochemical properties of TNO anodes in lithium ion batteries, especially for solid state batteries.

A Method for Rigorously Selective Capture and Simultaneous Fluorescent Labeling of N-Terminal Glycine Peptides.

Although chemical methods for the selective derivatization of amino acid (AA) side chains in peptides and proteins are available, selective N-terminal labeling is challenging, especially for glycine, which has no side chain at the α-carbon position. We report here a double activation at glycine's α-methylene group that allows this AA to be differentiated from the other 19 AAs. A condensation reaction of dibenzoylmethane with glycine results in the formation of an imine, and subsequent tautomerization is followed by intramolecular cyclization, leading to the formation of a fluorescent pyrrole ring. Additionally, the approach exhibits compatibility with AAs possessing reactive side chains. Further, the method allows for selective pull-down assays of N-terminal glycine peptides from mixtures without prior knowledge of the N-terminal peptide distribution.

Mine Site Restoration: The Phytoremediation of Arsenic-Contaminated Soils

Arsenic (As) is considered one of the most toxic chemicals to both human and environmental health. Mining activities represent one of the main anthropogenic sources of As; the concentration of As in mine soil can reach 9300 mg kg−1. To overcome the major issue of soil As pollution, soil restoration is required. Biological restoration approaches are generally more cost-effective and environmentally sustainable than physical and chemical methods. In particular, phytoremediation, an environmentally friendly technique based on the use of plants to uptake contaminants from soil, has been successfully implemented to restore As-contaminated soils at mine sites. However, mine soils are generally depleted in essential plant nutrients, such as nitrogen (N). Recent research suggests that phytoremediation can be combined with other techniques (physical, chemical, and biological) to enhance the N content and plant biomass. The aim of this review is to assess the current state of knowledge in the field of the restoration of arsenic-impacted mine site soils, focusing on phytoremediation. We critically assess recent work examining the potential of the co-application of amendments with phytoremediation and identify promising technologies and key research gaps. More studies are required to test the effectiveness of using various soil additives to enhance the phytoremediation of As, not only in pot-scale experiments but also in the field, to enable an improved management strategy for mine site restoration in the future.

Picometer-Scale Atomic Shifts Governing Subdisordered Structures in Diamond

Picometer-Scale Atomic Shifts Governing Subdisordered Structures in Diamond