Generation of zero-valent sulfur from dissimilatory sulfate reduction in sulfate-reducing microorganisms.

Dissimilatory sulfate reduction (DSR) mediated by sulfate-reducing microorganisms (SRMs) plays a pivotal role in global sulfur, carbon, oxygen, and iron cycles since at least 3.5 billion y ago. The canonical DSR pathway is believed to be sulfate reduction to sulfide. Herein, we report a DSR pathway in phylogenetically diverse SRMs through which zero-valent sulfur (ZVS) is directly generated. We identified that approximately 9% of sulfate reduction was directed toward ZVS with S8 as a predominant product, and the ratio of sulfate-to-ZVS could be changed with SRMs' growth conditions, particularly the medium salinity. Further coculturing experiments and metadata analyses revealed that DSR-derived ZVS supported the growth of various ZVS-metabolizing microorganisms, highlighting this pathway as an essential component of the sulfur biogeochemical cycle.

Renewable biomass-based aerogels: from structural design to functional regulation.

Global population growth and industrialization have exacerbated the nonrenewable energy crises and environmental issues, thereby stimulating an enormous demand for producing environmentally friendly materials. Typically, biomass-based aerogels (BAs), which are mainly composed of biomass materials, show great application prospects in various fields because of their exceptional properties such as biocompatibility, degradability, and renewability. To improve the performance of BAs to meet the usage requirements of different scenarios, a large number of innovative works in the past few decades have emphasized the importance of micro-structural design in regulating macroscopic functions. Inspired by the ubiquitous random or regularly arranged structures of materials in nature ranging from micro to meso and macro scales, constructing different microstructures often corresponds to completely different functions even with similar biomolecular compositions. This review focuses on the preparation process, design concepts, regulation methods, and the synergistic combination of chemical compositions and microstructures of BAs with different porous structures from the perspective of gel skeleton and pore structure. It not only comprehensively introduces the effect of various microstructures on the physical properties of BAs, but also analyzes their potential applications in the corresponding fields of thermal management, water treatment, atmospheric water harvesting, CO2 absorption, energy storage and conversion, electromagnetic interference (EMI) shielding, biological applications, etc. Finally, we provide our perspectives regarding the challenges and future opportunities of BAs. Overall, our goal is to provide researchers with a thorough understanding of the relationship between the microstructures and properties of BAs, supported by a comprehensive analysis of the available data.

Identification and validation of cuproptosis-related molecular clusters in non-alcoholic fatty liver disease.

Non-alcoholic fatty liver disease (NAFLD) is a major chronic liver disease worldwide. Cuproptosis has recently been reported as a form of cell death that appears to drive the progression of a variety of diseases. This study aimed to explore cuproptosis-related molecular clusters and construct a prediction model. The gene expression profiles were obtained from the Gene Expression Omnibus (GEO) database. The associations between molecular clusters of cuproptosis-related genes and immune cell infiltration were investigated using 50 NAFLD samples. Furthermore, cluster-specific differentially expressed genes were identified by the WGCNA algorithm. External datasets were used to verify and screen feature genes, and nomograms, calibration curves and decision curve analysis (DCA) were performed to verify the performance of the prediction model. Finally, a NAFLD-diet mouse model was constructed to further verify the predictive analysis, thus providing new insights into the prediction of NAFLD clusters and risks. The role of cuproptosis in the development of non-alcoholic fatty liver disease and immune cell infiltration was explored. Non-alcoholic fatty liver disease was divided into two cuproptosis-related molecular clusters by unsupervised clustering. Three characteristic genes (ENO3, SLC16A1 and LEPR) were selected by machine learning and external data set validation. In addition, the accuracy of the nomogram, calibration curve and decision curve analysis in predicting NAFLD clusters was also verified. Further animal and cell experiments confirmed the difference in their expression in the NAFLD mouse model and Mouse hepatocyte cell line. The present study explored the relationship between non-alcoholic fatty liver disease and cuproptosis, providing new ideas and targets for individual treatment of the disease.

The role of endoplasmic reticulum stress-related genes in the diagnosis and subtyping of non-alcoholic fatty liver disease.

Non-alcoholic fatty liver disease (NAFLD) is the most prevalent liver disease worldwide. Chronic activation of endoplasmic reticulum stress (ERS) in hepatocytes may promote the development of NAFLD, yet endoplasmic reticulum stress-related genes (ERSGs) have not been studied in NAFLD. Our aim is to study the relationship between ERSGs and the immune microenvironment of NAFLD patients and to construct predictive models. We screened 48 endoplasmic reticulum stress-related differentially expressed genes (ERSR-DEGs) using data from two GEO datasets and the GeneCards database. Enrichment analysis revealed that ERSR-DEGs are closely associated with immune-related pathways and functions. The immune infiltration profile of NAFLD was obtained by single sample gene set enrichment analysis (ssGSEA). There were significant differences in immune cell infiltration and immune function between NAFLD group and control group. Using 113 NAFLD samples, we explored two molecular clusters based on ERSR-DEGs. A five-gene SVM model was selected as the best machine learning model, and a nomogram based on five-gene SVM model showed good predictive efficiency. The mRNA expression levels of POR, PPP1R15A, FOS and FAS were significantly different between NAFLD mice and healthy mice. In conclusion, ERS is closely associated with the development of NAFLD. We established a promising and SVM-based predictive model to assess the risk of disease in patients with ERS subtypes and NAFLD.

Circularly Polarized Room Temperature Phosphorescence through Twisting-Induced Helical Structures from Polyvinyl Alcohol-Based Fibers Containing Hydrogen-Bonded Dyes.

Room temperature phosphorescence (RTP) materials have garnered significant attention owing to its distinctive optical characteristics and broad range of potential applications. However, the challenge remains in producing RTP materials with more simplicity, versatility, and practicality on a large scale, particularly in achieving chiral signals within a single system. Herein, we show that a straightforward and effective combination of wet spinning and twisting technique enables continuously fabricating RTP fibers with twisting-induced helical chirality. By leveraging the hydrogen bonding interactions between polyvinyl alcohol (PVA) and quinoline derivatives, along with the rigid microenvironment provided by PVA chains, typically, Q-NH2@PVA fiber demonstrates outstanding phosphorescent characteristics with RTP lifetime of 1.08 s and phosphorescence quantum yield of 24.6 %, and the improved tensile strength being 1.7 times than pure PVA fiber (172±5.82 vs 100±5.65 MPa). Impressively, the transformation from RTP to circularly polarized room temperature phosphorescence (CP-RTP) is readily achieved by imparting left- or right-hand helical structure through simply twisting, enabling large-scale production of chiral Q-NH2@PVA fiber with dissymmetry factor of 10-2. Besides, an array of displays and encryption patterns are crafted by weaving or seaming to exemplify the promising applications of these PVA-based fibers with outstanding adaptivity in cutting-edge anti-counterfeiting technology.

1+1>2: Fiber Synergy in Aggregation-Induced Emission.

Mesoscopic aggregate is important to transfer or even amplify the molecular information in macroscopic materials. As an important branch of aggregate science, aggregation-induced emissive luminogens (AIEgens) often show slight or even no emission in solutions but exhibit bright emission when they aggregate, which open a new avenue for the practical applications. Due to the flexible and rotor structure of AIEgens, the aggregate structure of AIEgens is highly sensitive to the surrounding microenvironment, resulting in adjustable optical properties. Fibers integrated of a multiplicity of functional components are ideal carriers to control the aggregation processes, further assembly of fibers produces large-scale fabrics with amplified functions and practical values. In this Concept article, we focus on the latest advances on the synergy between "AIE+Fiber" for the boosted performance that beyond AIE, and their applications are presented and abstracted out to stimulate new ideas for developing "AIE+Fiber" systems.

Removal of contamination in helium for precise SF6 -based Δ36 S measurements.

RATIONALE: Quantifications of quadruple sulfur isotopic compositions (δ34 S, Δ33 S, and Δ36 S) of sulfur-bearing compounds in nature are valuable for providing new insights into the Earth's evolution such as the crust-mantle cycle, oxygenation of atmosphere and oceans, and the origin and evolution of early life. SF6 -based isotope ratio mass spectrometry is the most widely used method of quantification, but Δ36 S measurements at high precision and accuracy have always been technically difficult due to the low abundance of 36 S (~0.01%). In this paper, we identify a major source of isobaric interferences (i.e., contamination in helium carrier gas in the gas chromatography purification step) and propose a simple strategy to solve this problem. METHODS: An SF6 fluorination and purification system was built. Laboratory SF6 reference gas and international Ag2 S standard (IAEA-S1) were used as reference materials to test our method. Contamination from helium carrier gas (99.999%) was purified by a simple two-step cryogenic method to allow for accurate and precise measurements of Δ36 S using the SF6 -based isotope ratio mass spectrometry method. RESULTS: Without proper purification of helium carrier gas, large errors in Δ36 S measurements were found. Measured Δ36 S values of SF6 with trace contamination from helium were >10‰ higher than expected values. Using a newly developed purification strategy, the difference in Δ36 S values of SF6 before and after passing through the gas chromatography is less than instrumental errors (<0.2‰). Our improved method yielded an overall Δ36 S precision for IAEA-S1 of 0.12‰ (n = 6). This precision is comparable to that found by other laboratories around the world. CONCLUSION: Our simple two-step cryogenic method significantly improved the accuracy and precision of Δ36 S measurements and is therefore recommended for future determination of quadruple sulfur isotopic compositions in natural samples.

Waste toner-derived micro-materials as low-cost magnetic solid-phase extraction adsorbent for the analysis of trace Pb in environmental and biological samples.

Lead (Pb) is a toxic heavy metal and is commonly used in industrial applications. Thus, Pb poisoning is a concerning public health issue worldwide. The amounts of lead in natural water, urine, and blood can serve as significant indicators for monitoring the exposure of Pb poisoning. Waste toner has the characteristics of both "waste" and "resource," as it is a "resource in the wrong place." Here, a low-cost carboxylate-functionalized magnetic adsorbent was first synthesized from waste toner by a simple thermal treatment and served as a novel adsorbent with a flexible multidentate O-donor for pre-concentration of trace Pb. The characterization, adsorption behavior, and various factors of adsorption and desorption were adequately optimized, and prior to graphite furnace atomic absorption spectrometry (GFAAS) detection, a new magnetic solid-phase extraction method was proposed for the analysis of Pb in real environmental water and biological samples. The developed method exhibited a low detection limit (0.003 µg L-1), high enrichment factor (88.6-fold), good linearity (0.01-0.3 µg L-1), satisfactory precision with relative standard deviations of 7.9% (n = 7, CPb = 0.02 µg L-1), fast adsorption kinetics (5 min), and strong ability to overcome matrix interference. Validation was also performed by analyzing a certified standard reference material, and the method was successfully applied to real tap water, lake water, human urine, and human blood serum with satisfactory recoveries of 92.6-109%.

Enhanced laccase production by mutagenized Myrothecium verrucaria using corn stover as a carbon source and its potential in the degradation of 2-chlorophen.

Chlorophenols are widely used in industry and are known environmental pollutants. The degradation of chlorophenols is important for environmental remediation. In this study, we evaluated the biodegradation of 2-chlorophenol using crude laccase produced by Myrothecium verrucaria. Atmospheric and room temperature plasma technology was used to increase laccase production. The culture conditions of the M-6 mutant were optimized. Our results showed that corn stover could replace glucose as a carbon source and promote laccase production. The maximum laccase activity of 30.08 U/mL was achieved after optimization, which was a 19.04-fold increase. The biodegradation rate of 2-chlorophenol using crude laccase was 97.13%, a positive correlation was determined between laccase activity and degradation rate. The toxicity of 2-CP was substantially reduced after degradation by laccase solution. Our findings show the feasibility of the use of corn stover in laccase production by M. verrucaria mutant and the subsequent biodegradation of 2-chlorophenol using crude laccase.

A Weed-Derived Hierarchical Porous Carbon with a Large Specific Surface Area for Efficient Dye and Antibiotic Removal.

Adsorption is an economical and efficient method for wastewater treatment, and its advantages are closely related to adsorbents. Herein, the Abutilon theophrasti medicus calyx (AC) was used as the precursor for producing the porous carbon adsorbent (PCAC). PCAC was prepared through carbonization and chemical activation. The product activated by potassium hydroxide exhibited a larger specific surface area, more mesopores, and a higher adsorption capacity than the product activated by sodium hydroxide. PCAC was used for adsorbing rhodamine B (RhB) and chloramphenicol (CAP) from water. Three adsorption kinetic models (the pseudo-first-order, pseudo-second-order, and intra-particle diffusion models), four adsorption isotherm models (the Langmuir, Freundlich, Sips, and Redlich-Peterson models), and thermodynamic equations were used to investigate adsorption processes. The pseudo-second kinetic and Sips isotherm models fit the experimental data well. The adsorption mechanism and the reusability of PCAC were also investigated. PCAC exhibited a large specific surface area. The maximum adsorption capacities (1883.3 mg g-1 for RhB and 1375.3 mg g-1 for CAP) of PCAC are higher than most adsorbents. Additionally, in the fixed bed experiments, PCAC exhibited good performance for the removal of RhB. These results indicated that PCAC was an adsorbent with the advantages of low-cost, a large specific surface area, and high performance.

Evaluation of Preparation and Detoxification of Hemicellulose Hydrolysate for Improved Xylitol Production from Quinoa Straw.

Quinoa straw is rich in hemicellulose, and it could be hydrolyzed into xylose. It is a promising energy resource alternative that acts as a potential low-cost material for producing xylitol. In this study, quinoa straw was used as a substrate subjected to the hydrolysis of dilute sulfuric acid solution. Based on the production of xylose and inhibitors during hydrolysis, the optimal conditions for the hydrolysis of hemicellulose in quinoa straw were determined. Detoxification was performed via activated carbon adsorption. The optimal detoxification conditions were determined on the basis of major inhibitor concentrations in the hydrolysate. When the addition of activated carbon was 3% at 30 °C for 40 min, the removal of formic acid, acetic acid, furfural, and 5-HMF could reach 66.52%, 64.54%, 88.31%, and 89.44%, respectively. In addition to activated carbon adsorption, vacuum evaporation was further conducted to perform two-step detoxification. Subsequently, the detoxified hydrolysate was used for xylitol fermentation. The yield of xylitol reached 0.50 g/g after 96 h of fermentation by Candida tropicalis (CICC 1779). It is 1.2-fold higher than that obtained through the sole vacuum evaporation method. This study validated the feasibility of xylitol production from quinoa straw via a biorefinery process.

Identification of a peptide binding to cancer antigen Kita-kyushu lung cancer antigen 1 from a phage-display library.

Kita-kyushu lung cancer antigen 1 (KK-LC-1) is a kind of cancer-testis antigen with anti-tumor potential for clinical application. As a class of small-molecule antigen conjugate, tumor-targeting peptides have broad application prospects in gastric cancer diagnosis, imaging, and biological treatment. Here, we screened specific cyclic nonapeptides from a phage-display library. The targeting peptide with the best affinity was selected and further verified in ex vivo tissue sections. Finally, enrichment of targeting peptides in tumor tissues was observed in vivo, and the dynamic biodistribution process was also observed with micro-positron emission tomography (micro-PET)/computed tomography (CT) imaging. Studies showed that the specific cyclic nonapeptide had a high binding capacity for KK-LC-1 protein. It has a strong affinity and specificity for KK-LC-1-expressing positive tumor cells. Targeting peptides were significantly enriched at tumor sites in vivo, with very low normal tissue background. These findings demonstrated that the KK-LC-1 targeting peptide has high clinical potential.

I2/CuCl2-Copromoted Formal [4 + 1 + 1] Cyclization of Methyl Ketones, 2-Aminobenzonitriles, and Ammonium Acetate: Direct Access to 2-Acyl-4-aminoquinazolines.

We herein report an I2/CuCl2-copromoted diamination of C(sp3)-H bonds for the preparation of 2-acyl-4-aminoquinazolines from methyl ketones, 2-aminobenzonitriles, and ammonium acetate. This reaction features operational simplicity, commercially available substrates, mild reaction conditions, and good functional group compatibility. Mechanistic studies indicate that CuCl2 plays a pivotal role in this transformation. This study uses a methyl group as a novel input to construct 2-acyl-4-aminoquinazoline derivatives for the first time.

Employing Arylacetylene as a Diene Precursor and Dienophile: Synthesis of Quinoline via the Povarov Reaction.

A novel I2-mediated Povarov reaction of arylacetylenes and anilines for the synthesis of 2,4-substituted quinolines has been developed, in which arylacetylene first acts as both a diene precursor and dienophile. This work further develops the Povarov reaction to expand the types of diene precursors. Preliminary mechanistic studies indicate that the I2/DMSO system realized the oxidative carbonylation of C(sp)-H of arylacetylene and then undergoes a [4 + 2] cycloaddition reaction.

Iodine-Promoted Formal [3+2] Cycloaddition of Enaminone: Access to 2-Hydroxy-1,2-dihydro-pyrrol-3-ones with Quaternary Carbon Center.

A novel iodine promoted cyclization of enaminone with aryl methyl ketones has been developed as a straightforward method for constructing 2-hydroxy-pyrrol-3(2H)-ones. This strategy affords structurally diverse 2-hydroxy-pyrrol-3(2H)-ones rings in high yields. Moreover, a quarternary alcohol has been constructed efficiently in the reaction. Product purification required only washing with CH2Cl2 solvent, thereby avoiding traditional chromatography and recrystallization, making this an example of group-assisted purification chemistry.

Direct Synthesis of 4-Aryl-1,2,3-triazoles via I2-Promoted Cyclization under Metal- and Azide-Free Conditions.

We herein report an iodine-mediated formal [2 + 2 + 1] cyclization of methyl ketones, p-toluenesulfonyl hydrazines, and 1-aminopyridinium iodide for preparation of 4-aryl-NH-1,2,3-triazoles under metal- and azide-free conditions. Notably, this is achieved using p-toluenesulfonyl hydrazines and 1-aminopyridinium iodide as azide surrogates, providing a novel route toNH-1,2,3-triazoles. Furthermore, this approach provides rapid and practical access to potent inhibitors of indoleamine 2,3-dioxygenase (IDO).

Argon Enclosed Droplet Based 3D Microfluidic Device Online Coupled with Time-Resolved ICPMS for Determination of Cadmium and Zinc in Single Cells Exposed to Cadmium Ion.

Time-resolved (TRA)-ICPMS has become a booming subfield of single-cell analysis tools in recent years, while generation of single cells remains the major challenge. Microfluidic devices reveal their great capability and potential in encapsulation of single cells into water droplets. However, current strategies to pinch off droplets require a specific oil phase, which is not compatible to conventional ICPMS and makes the signal of cells in the water phase susceptible. Herein, we built a 3D water-in-gas microfluidic device (3D W/G MFD) with commercially available components, producing single cell droplet enclosed by argon gas. By simply tuning the flow rate of gas and water, the droplets were generated to encapsulate single cells, which significantly reduced the probability of the single signal coming from multiple cells by 1 or 2 orders of magnitude compared to direct injection. The developed oil-free 3D W/G MFD was more friendly to online coupling with TRA-ICPMS than water-in-oil devices. The effect of Cd2+ on HepG2 cells was studied by single cell detecting total Zn with 3D W/G MFD-TRA-ICPMS, and the variation of labile Zn was explored by flow cytometry with an N-(6-methoxy-8-quinolyl)-p-toluenesulfonamide probe. To the best of our knowledge, this work pioneered the exploration of variation in cellular metal content and speciation at the single-cell level, compensating for the deficiency of speciation analysis based on TRA-ICPMS and providing new insights into exploring the complexity of biology.

Exonuclease III-Powered Self-Propelled DNA Machine for Distinctly Amplified Detection of Nucleic Acid and Protein.

Herein, a new exonuclease III (Exo III)-powered self-propelled DNA machine was developed for the cascade multilevel signal amplification of nucleic acid and nucleic acid-related analytes. It could be easily and homogeneously operated with the use of an integral DNA hybrid probe as the recognition, amplification, and signaling element, and the Exo III cleavage as a driving force. The DNA hybrid probe was obtained by annealing two hairpin-like DNAs. The target recognition with the 3'-protruding domain of the DNA hybrid probe triggered Exo III cleavage, accompanied by target recycling and alternate generation of a large amount of target substitute and analogy. Simultaneously, the cascade bidirectional Exo III cleavage toward the DNA hybrid probe by the generated target substitute and analogy contributed for the exponential signal amplification toward target recognition event. It could be also extended for the application in protein detection with the thrombin as a protein example by introducing an additional hairpin-like aptamer switch. The proposed Exo III-powered self-propelled DNA amplification strategy showed a linear detection range for target DNA from 0.5 fM to 1 pM and for thrombin from 5 fM to 10 pM. The low detection limit toward target DNA and thrombin could reach about 0.1 fM and 5 fM, respectively, which were superior to most of reported methods. It also exhibited an excellent selectivity toward target detection. Therefore, the developed sensing system exhibits a new, simple and powerful means for amplified detection of nucleic acid and nucleic acid-related analytes, and may hold great potentials in bioanalysis, disease diagnosis and biomedicine.

Chemical Reactions Impede Thermal Transport Across Metal/ß-Ga2O3 Interfaces.

The impact of chemical reactions on the thermal boundary conductance (TBC) of Au/metal contact/ß-Ga2O3 layered samples as a function of contact thickness is investigated using high-throughput thermoreflectance measurements. A maximum in TBC of 530 ± 40 (260 ± 25) MW/m2 K is discovered for a Cr (Ti) contact at a thickness of 2.5 (5) nm. There is no local maximum for a Ni contact, for which the TBC saturates at 410 ± 35 MW/m2 K for thicknesses greater than 3 nm. Relative to the Au/ß-Ga2O3 interface, which has a TBC of 45 ± 7 MW/m2 K, these nanoscale contacts enhance TBC by factors of 6 to 12. The TBC maximum only exists for metals capable of forming oxides that are enthalpically favorable compared to ß-Ga2O3. The formation of Cr2O3, via oxygen removal from the ß-Ga2O3 substrate, is confirmed by TEM analysis. The reaction-formed oxide layer reduces the potential TBC and leads to the maximum, which is followed by a plateau at a lower value, as its thickness saturates due to passivation. Many advanced materials are prone to similar chemical reactions, impacting contact engineering and thermal management for a variety of applications.

3D Droplet-Based Microfluidic Device Easily Assembled from Commercially Available Modules Online Coupled with ICPMS for Determination of Silver in Single Cell.

More recently, single-cell analysis based on ICPMS has made considerable headway while a challenge remains to differentiate single cell from doublets during the analysis. One burgeoning solution is to encapsulate single cell into droplets on the platform of the microfluidic chip. However, the manufacture of the droplet-based microfluidic chip requires sophisticated fabrication and limits its potential application. In this paper, we presented an off-the-shelf three-dimensional (3D) microfluidic device by assembling commercially available parts without any proficient manufacturing process. Uniform monodisperse microdroplet was generated from the 3D microfluidic device with a size variation of 1.5%, and the innner diameter of the 3D microfluidic device was the same as the nebulizer (150 µm). The proposed 3D microfluidic device-time-resolved ICPMS system was applied to detect silver in single AgNPs (51 nm), and the result is in good agreement with conventional acid digestion method, demonstrating the accuracy of the method. Silver uptake behaviors in HepG2 cells were then studied by incubating with Ag+ or AgNPs under biocompatible conditions. The results revealed that the cell-to-cell variability in terms of the diversity of cells incubated with AgNPs was wider than those cells incubated with Ag+ from the aspect of the content distribution of silver at the single-cell level.