A Biomimetic Textile with Self-Assembled Hierarchical Porous Fibers for Thermal Insulation

Natural biomaterials with a porous structure inspired smart textiles for personal thermal management. Inspired by the hierarchically fibrous structure of hides, self-assembled hierarchical fibers with cross-scale porous networks are fabricated by the facile wet-spinning method. The biomimetic textile (abbreviated as “T”) woven by such fibers exhibits a low thermal conductivity (0.07 W/mK) comparable to that of cowhide. It also shows a high mechanical strength of up to 10 MPa as well as good flexibility (fracture strain exceeds 300%) and hydrophobicity. The heat conduction mechanism of the hierarchical structure is analyzed via finite element simulation. When immersed with the phase-change material, the textile (named as “P”) works like an adipose layer. Integration of the layers of T and P effectively slows down the heat conduction and decreases the surface temperature, resembling an animal insulation system. The study paves the way to mass production of high-performance biomimetic materials with hierarchical cellular microstructures for application in thermal insulation

Improved Model for Calculating Physical Properties of Confined Fluid by Considering Adsorption Film Theory Based on the SWCF-VR Equation of State

An improved model for calculating physical properties and phase behavior of confined fluids (oil and gas resources in shale reservoirs) by considering adsorption film theory was developed based on the square-well chain-like fluid with variable well-width range (SWCF-VR) equation of state. The accuracy of the improved model is greatly increased via comparing the experimental data of argon in cylindrical pores at 87.3 K. The physical properties of pure component hydrocarbons, mixture hydrocarbons, and real Bakken oils in nanopores were predicted and analyzed. The results show that the properties of confined fluids are very different from those of bulk-phase fluids, where confinement decreases the gas–liquid phase equilibrium constant (K-value), bubble point pressure, and interfacial tension of the fluid. The presence of the adsorption film further decreases the K-value and bubble point and increases the capillary pressure, and these properties change more significantly in pore radius with only a few nanometers. The results demonstrate the importance of improving the accuracy in calculating the properties and phase behaviors of confined fluids and also draw the necessity of considering the adsorption film theory

An Effective Osmium Precatalyst for Practical Synthesis of Diarylketones: Preparation, Reactivity, and Catalytic Application of [OsH-<i>cis</i>-(CO)₂-<i>mer</i>-{κ³‑<i>P</i>,<i>B</i>,<i>P</i>′‑B(NCH₂PPh₂)₂‑<i>o</i>‑C₆H₄}]

Developing new approaches for efficient synthesis of diarylketones from commercially available inexpensive substrates via practical procedures is highly desirable. In this work, an effective catalytic system for the synthesis of diarylketones was developed based on a newly synthesized Os PBP pincer complex [OsH-cis-(CO)2-mer-{κ3-P,B,P′-B­(NCH2PPh2)2-o-C6H4}] (1). Complex 1 proved to be very stable against many reagents at room temperature; CS2 can only react with 1 at elevated temperatures to produce [Os­(κ2-S,S’-S2CH)­(CO)-mer-{κ3-P,B,P′-B­(NCH2PPh2)2-o-C6H4}] (2). Complex 1 was found to be an efficient precatalyst for the coupling reactions between arylboronic acids and aryl aldehydes. The reactions are tolerant of many functional groups and proceed smoothly in toluene in the presence of K3PO4 and H2O at 100 °C under an air atmosphere to give diaryl ketones in good to excellent yields. It was demonstrated that the reactions were catalyzed by in situ generated osmium nanoparticles. This work would open an avenue of heterogeneous transition metal catalyst system for the synthesis of diarylketones via the coupling reactions between arylboronic acids and aryl aldehydes, which has never been reported before

Water Radiocatalysis for Selective Aqueous-Phase Methane Carboxylation with Carbon Dioxide into Acetic Acid at Room Temperature

Methane (CH4) carboxylation with carbon dioxide (CO2) into acetic acid (CH3COOH) is an ideal chemical reaction to utilize both greenhouse gases with 100% atom efficiency but remains a great challenge under mild conditions. Herein, we introduce a concept of water (H2O) radiocatalysis for efficient and selective aqueous-phase CH4 carboxylation with CO2 into CH3COOH at room temperature. H2O radiolysis occurs under γ-ray radiation to produce ·OH radicals and hydrated electrons that efficiently react with CH4 and CO2, respectively, to produce ·CH3 radicals and ·CO2– species facilely coupling to produce CH3COOH. CH3COOH selectivity as high as 96.9 and 96.6% calculated respectively from CH4 and CO2 and a CH3COOH production rate of as high as 121.9 μmol·h–1 are acquired. The water radiocatalysis driven by γ-rays is also applicable to selectively produce organic acids from other hydrocarbons and CO2

Role of Water in Methanol Photochemistry on TiO₂ Nanocrystals: An In Situ DRIFTS Study

Effects of adsorbed water on methanol photochemistry on TiO2 surfaces is an interesting and important issue. In this paper, we have studied coadsorption and photochemistry of water and methanol on TiO2 nanocrystals with different predominantly exposed facets using in situ diffuse-reflectance infrared spectroscopy and an isotope labeling technique. Preadsorbed water on TiO2 exerts versatile influences on methanol photochemistry. Water competes with methanol for surface sites on TiO2; meanwhile, surface OH groups are capable of assisting methanol decomposition to methoxy species. Surface OH groups can trap photoexcited electrons, which open up photocatalytic reactions of adsorbed methanol species in the absence of O2; moreover, the acquiring surface •OH radicals can directly participate in photocatalytic conversions of adsorbed methanol species. In the presence of O2, water influences photocatalytic oxidation of adsorbed methanol species on TiO2 NCs mainly by affecting methanol and O2 adsorption. All these effects vary sensitively with exposed facets and surface structures of TiO2 nanocrystals. These results unveil the complex nature of influences of adsorbed water on methanol photochemistry on TiO2 surfaces

Capillary Zone Electrophoresis-Tandem Mass Spectrometry for Top-Down Proteomics of Mouse Brain Integral Membrane Proteins

Mass spectrometry (MS)-based top-down characterization of integral membrane proteins (IMPs) is crucial for understanding their functions in biological processes. However, it is technically challenging due to their low solubility in typical MS-compatible buffers. In this work, for the first time, we developed an efficient capillary zone electrophoresis (CZE)-tandem MS (MS/MS) method for the top-down proteomics (TDP) of IMPs enriched from mouse brains. Our technique employs a sample buffer containing 30% (v/v) formic acid and 60% (v/v) methanol for solubilizing IMPs and utilizes a separation buffer of 30% (v/v) acetic acid and 30% (v/v) methanol for maintaining the solubility of IMPs during CZE separation. Single-shot CZE-MS/MS identified 51 IMP proteoforms from the mouse brain sample. Coupling size exclusion chromatography (SEC) to CZE-MS/MS enabled the identification of 276 IMP proteoforms from the mouse brain sample containing 1–4 transmembrane domains. This proof-of-concept work demonstrates the high potential of CZE-MS/MS for the large-scale TDP of IMPs

Capillary Zone Electrophoresis-Tandem Mass Spectrometry for Top-Down Proteomics of Mouse Brain Integral Membrane Proteins

Mass spectrometry (MS)-based top-down characterization of integral membrane proteins (IMPs) is crucial for understanding their functions in biological processes. However, it is technically challenging due to their low solubility in typical MS-compatible buffers. In this work, for the first time, we developed an efficient capillary zone electrophoresis (CZE)-tandem MS (MS/MS) method for the top-down proteomics (TDP) of IMPs enriched from mouse brains. Our technique employs a sample buffer containing 30% (v/v) formic acid and 60% (v/v) methanol for solubilizing IMPs and utilizes a separation buffer of 30% (v/v) acetic acid and 30% (v/v) methanol for maintaining the solubility of IMPs during CZE separation. Single-shot CZE-MS/MS identified 51 IMP proteoforms from the mouse brain sample. Coupling size exclusion chromatography (SEC) to CZE-MS/MS enabled the identification of 276 IMP proteoforms from the mouse brain sample containing 1–4 transmembrane domains. This proof-of-concept work demonstrates the high potential of CZE-MS/MS for the large-scale TDP of IMPs

Pilot Evaluation of the Long-Term Reproducibility of Capillary Zone Electrophoresis–Tandem Mass Spectrometry for Top-Down Proteomics of a Complex Proteome Sample

Mass spectrometry (MS)-based top-down proteomics (TDP) has revolutionized biological research by measuring intact proteoforms in cells, tissues, and biofluids. Capillary zone electrophoresis–tandem MS (CZE-MS/MS) is a valuable technique for TDP, offering a high peak capacity and sensitivity for proteoform separation and detection. However, the long-term reproducibility of CZE-MS/MS in TDP remains unstudied, which is a crucial aspect for large-scale studies. This work investigated the long-term qualitative and quantitative reproducibility of CZE-MS/MS for TDP for the first time, focusing on a yeast cell lysate. Over 1000 proteoforms were identified per run across 62 runs using one linear polyacrylamide (LPA)-coated separation capillary, highlighting the robustness of the CZE-MS/MS technique. However, substantial decreases in proteoform intensity and identification were observed after some initial runs due to proteoform adsorption onto the capillary inner wall. To address this issue, we developed an efficient capillary cleanup procedure using diluted ammonium hydroxide, achieving high qualitative and quantitative reproducibility for the yeast sample across at least 23 runs. The data underscore the capability of CZE-MS/MS for large-scale quantitative TDP of complex samples, signaling its readiness for deployment in broad biological applications. The MS RAW files were deposited in ProteomeXchange Consortium with the data set identifier of PXD046651

Modulating Hysteresis of Perovskite Solar Cells by a Poling Voltage

Perovskite solar cells have a puzzling phenomenon of current hysteresis. Here, we modulate the hysteresis by applying a poling voltage. Charge accumulations are detected in the perovskite solar cells. Two interacting capacitors are identified through dynamic voltage measurement. We elucidate that the current hysteresis originates mainly from the polarization and depolarization of electric dipoles of CH₃NH₃⁺ under an external electric field due to the intrinsic ferroelectric properties of perovskite. The polarization leads to charge accumulation at the surface of perovskite, which establishes a polarization-induced electric field. The polarization-induced electric field affects the charge transport inside the solar cells, resulting in the current hysteresis. The polarization of electric dipoles can be modified by the poling and sweeping voltage, which makes the hysteresis exhibit a history-dependent effect

In-Depth Proteome Coverage by Improving Efficiency for Membrane Proteome Analysis

Although great achievement has been made in the mapping of human proteome, the efficiency of sample preparation still needs to be improved, especially for membrane proteins. Herein, we presented a novel method to deepen proteome coverage by the sequential extraction of proteins using urea and 1-dodecyl-3- methylimidazolium chloride (C12Im-Cl). With such a strategy, the commonly lost hydrophobic proteins by 8 M urea extraction could be further recovered by C12Im-Cl, as well as the suppression effect of high abundance soluble proteins could be decreased. Followed by the in situ sample preparation and separation with different stationary phases, more than 9810 gene products could be identified, covering 8 orders of magnitude in abundance, which was, to the best of our knowledge, the largest data set of HeLa cell proteome. Compared with previous work, not only the number of proteins identified was obviously increased, but also the analysis time was shortened to a few days. Therefore, we expect that such a strategy has great potential applications to achieve unprecedented coverage for proteome analysis