Boosting the hydrogenation activity of dibenzyltoluene catalyzed by Mg-based metal hydrides

Hydrogenation of dibenzyltoluene (DBT) is of great significance for the application in liquid organic hydrogen carriers (LOHCs). We successfully develop Mg-based metal hydrides (Mg₂NiH₄, MgH₂, and LaH₃) reactive ball-milling for the hydrogenation of DBT. Mg-based metal hydrides milled with 500 min exhibit the best catalytic activity, the hydrogen uptake of DBT can reach 4.63 wt% at the first 4 h and finally achieve 5.70 wt% through 20 h, which is the first time to use hydrogen storage material as a catalyst for the hydrogenation of DBT. The excellent catalytic hydrogenation performance of Mg-based metal hydrides mostly originates from numerous catalytic activity centers formed at the surfaces of Mg₂NiH₄ nanoparticles in the MgH₂ matrix. Inspired by this mechanism, more general metal hydrides can be explored for catalyzing the hydrogenation of LOHCs. The new application of Mg-based metal hydrides is beneficial to developing efficient LOHC based hydrogen storage systems and offers novel insights to hydride-based catalysts.     

Porous CoNiOOH nanosheets derived from the well-mixed MOFs as stable and highly efficient electrocatalysts for water oxidation

The development of efficient and stable electrocatalysts is of great significance for improving water splitting. Among them, transition metal oxyhydroxides show excellent performance in oxygen evolution reactions (OER), but there are certain difficulties in direct preparation. Recently, Metal–organic frameworks (MOFs) as precatalysts or precursors have shown promising catalytic performance in OER and can be decomposed under alkaline conditions. Therefore, using a mild and controllable way to convert MOFs into oxyhydroxides and retaining the original structural advantages is crucial for improving the catalytic activity. Herein, a rapid electrochemical strategy is used to activate well-mixed MOFs to prepare Co/Ni oxyhydroxide nanosheets for efficient OER catalysts, and the structural transformation in this process was investigated in detail by using scanning electron microscope, X-ray diffraction, Raman, X-ray photoelectron spectroscopy and electrochemical methods. It is discovered that electrochemical activation can promote ligand substitution of well-mixed MOFs to form porous oxyhydroxide nanosheets and tune the electronic structure of the metal (Co and Ni), which can lead to more active site exposure and accelerate charge transfer. In addition, the change of structure also improves hydrophilicity, as well as benefiting from the strong synergistic effect between multiple species, the optimal a-MCoNi–MOF/NF has excellent OER performance and long-term stability. More obviously, the porous CoNiOOH nanosheets are formed in situ during electrochemical activation process through structural transformation and acts as the active centers. This work provides new insights for mild synthesis of MOFs derivatives and also provides ideas for the preparation of highly efficient catalysts.     

Diluted chemical bath deposition of CdZnS as prospective buffer layer in CIGS solar cell

In this study, dilute chemical bath deposition technique has been used to deposit CdZnS thin films on soda-lime glass substrates. The structural, morphological, optoelectronic properties of as-grown films have been investigated as a function of different Zn²⁺ precursor concentrations. The X-ray diffractogram of CdS thin-film reveals a peak corresponding to (002) plane with wurtzite structure, and the peak shift has been observed with the increase of the Zn²⁺ concentration upon formation of CdZnS thin film. From morphological studies, it has been revealed that the diluted chemical bath deposition technique provides homogeneous distribution of film on the substrate even at a lower concentration of Zn²⁺. Optical characterization has shown that the transparency of the film is influenced by Zn²⁺ concentration and when the Zn²⁺ concentration is varied from 0 M to 0.0256 M, bandgap values of resulting films range from 2.42 eV to 3.90 eV while. Furthermore, electrical properties have shown that with increasing zinc concentration the resistivity of the film increases. Finally, numerical simulation validates and suggests that CdZnS buffer layer with composition of 0.0032 M Zn²⁺ concentration would be a promising candidate in CIGS solar cell.     

Metabolic Glycoengineering in hMSC-TERT as a Model for Skeletal Precursors by Using Modified Azide/Alkyne Monosaccharides

Metabolic glycoengineering enables a directed modification of cell surfaces by introducing target molecules to surface proteins displaying new features. Biochemical pathways involving glycans differ in dependence on the cell type; therefore, this technique should be tailored for the best results. We characterized metabolic glycoengineering in telomerase-immortalized human mesenchymal stromal cells (hMSC-TERT) as a model for primary hMSC, to investigate its applicability in TERT-modified cell lines. The metabolic incorporation of N-azidoacetylmannosamine (Ac₄ManNAz) and N-alkyneacetylmannosamine (Ac₄ManNAl) into the glycocalyx as a first step in the glycoengineering process revealed no adverse effects on cell viability or gene expression, and the in vitro multipotency (osteogenic and adipogenic differentiation potential) was maintained under these adapted culture conditions. In the second step, glycoengineered cells were modified with fluorescent dyes using Cu-mediated click chemistry. In these analyses, the two mannose derivatives showed superior incorporation efficiencies compared to glucose and galactose isomers. In time-dependent experiments, the incorporation of Ac₄ManNAz was detectable for up to six days while Ac₄ManNAl-derived metabolites were absent after two days. Taken together, these findings demonstrate the successful metabolic glycoengineering of immortalized hMSC resulting in transient cell surface modifications, and thus present a useful model to address different scientific questions regarding glycosylation processes in skeletal precursors.     

Piezoelectricity of the Transmembrane Protein ba3 Cytochrome c Oxidase

Controlling the electromechanical response of piezoelectric biological structures including tissues, peptides, and amino acids provides new applications for biocompatible, sustainable materials in electronics and medicine. Here, the piezoelectric effect is revealed in another class of biological materials, with robust longitudinal and shear piezoelectricity measured in single crystals of the transmembrane protein ba₃ cytochrome c oxidase from Thermus thermophilus. The experimental findings from piezoresponse force microscopy are substantiated using a range of control measurements and molecular models. The observed longitudinal and shear piezoelectric responses of ≈ 2 and 8 pm V⁻¹, respectively, are comparable to or exceed the performance of commonly used inorganic piezoelectric materials including quartz, aluminum nitride, and zinc oxide. This suggests that transmembrane proteins may provide, in addition to physiological energy transduction, technologically useful piezoelectric material derived entirely from nature. Membrane proteins could extend the range of rationally designed biopiezoelectric materials far beyond the minimalistic peptide motifs currently used in miniaturized energy harvesters, and the finding of robust piezoelectric response in a transmembrane protein also raises fundamental questions regarding the molecular evolution, activation, and role of regulatory proteins in the cellular nanomachinery, indicating that piezoelectricity might be important for fundamental physiological processes.     

Photomemory and Pulse Monitoring Featured Solution-Processed Near-Infrared Graphene/Organic Phototransistor with Detectivity of 2.4 × 1013 Jones

Emerging graphene/organic phototransistors are eye-catching technologies owing to their unique merits including easy/low-cost fabrication, temperature independent, and achieving various functions. However, their development in the near-infrared (NIR) region is experiencing a bottleneck of inferior sensitivity due to low exciton dissociation efficiency and inefficient charge extraction rate. Here, a novel-design solution-processed graphene/organic NIR phototransistor is reported, that is, creatively introducing electron extraction layer of ZnO on graphene channel and employing organic ternary bulk heterojunction as photosensitive layer, successfully breaking that bottleneck. The phototransistor exhibits a high responsivity of 6.1 × 10⁶ A W⁻¹, a superior detectivity of 2.4 × 10¹³ Jones, and a remarkable minimum detection power of 1.75 nW cm⁻² under 850 nm radiation. Considering its excellent NIR detection performance, a noncontact transmission-type pulse monitoring is carried out with no external circuit support, from which human pulse signal and heart rate can be displayed in real time. The phototransistor, interestingly, can be switched into a photomemory function with a retention time of 1000 s in the atmosphere through a gate voltage of −20 V. The design takes the characteristics of graphene/organic phototransistors to a higher level, beyond the limit of sensitivity, and opens up a novel approach for developing multifunction devices.     

Achieving High Electroluminescence Efficiency and High Color Rendering Index for All-Fluorescent White OLEDs Based on an Out-of-Phase Sensitizing System

Sensitizing conventional fluorescence (CF) dopants with thermally activated delayed fluorescence (TADF) materials has achieved considerable progress, by which the advantages of TADF materials and CF dopants can be fully harnessed. However, the usually used co-phase configuration of CF dopant-engaged sensitizing systems often encounters exciton loss due to Dexter energy transfer (DET). Herein, an effective out-of-phase configuration is proposed to sensitize CF dopants in the fabrication of white organic light-emitting diodes (WOLEDs). Based on a new efficient sky-blue TADF luminogen DCP-BP-DPAC which has an electroluminescence (EL) peak at 486 nm and an EL efficiency of 26.6%, a green TADF material BDMAC-XT, and a red CF dopant DBP sensitized by BDMAC-XT through an out-of-phase configuration without interlayer, efficient WOLEDs are successfully fabricated. By further adopting orange TBRB or 4CzTPNBu as intermediate sensitizers, more efficient energy transfer to DBP is achieved via Förster energy transfer. Through step-by-step energy transfer and elimination of excess DET process, high-performance all-fluorescent WOLEDs are achieved, providing excellent EL efficiencies over 23.0%, and highly stable white light with a high color rendering index of 87. The outstanding EL performance and high-quality emission color demonstrate the great potential of the proposed out-of-phase design for sensitizing systems of WOLEDs.     

Occupational exposure and health risks of volatile organic compounds of hotel housekeepers: Field measurements of exposure and health risks

Hotel housekeepers represent a large, low-income, predominantly minority, and high-risk workforce. Little is known about their exposure to chemicals, including volatile organic compounds (VOCs). This study evaluates VOC exposures of housekeepers, sources and factors affecting VOC levels, and provides preliminary estimates of VOC-related health risks. We utilized indoor and personal sampling at two hotels, assessed ventilation, and characterized the VOC composition of cleaning agents. Personal sampling of hotel staff showed a total target VOC concentration of 57 ± 36 µg/m³ (mean ± SD), about twice that of indoor samples. VOCs of greatest health significance included chloroform and formaldehyde. Several workers had exposure to alkanes that could cause non-cancer effects. VOC levels were negatively correlated with estimated air change rates. The composition and concentrations of the tested products and air samples helped identify possible emission sources, which included building sources (for formaldehyde), disinfection by-products in the laundry room, and cleaning products. VOC levels and the derived health risks in this study were at the lower range found in the US buildings. The excess lifetime cancer risk (average of 4.1 × 10⁻⁵) still indicates a need to lower exposure by reducing or removing toxic constituents, especially formaldehyde, or by increasing ventilation rates.     

Real-time organic aerosol chemical speciation in the indoor environment using extractive electrospray ionization mass spectrometry

Understanding the sources and composition of organic aerosol (OA) in indoor environments requires rapid measurements, since many emissions and processes have short timescales. However, real-time molecular-level OA measurements have not been reported indoors. Here, we present quantitative measurements, at a time resolution of five seconds, of molecular ions corresponding to diverse aerosol-phase species, by applying extractive electrospray ionization mass spectrometry (EESI-MS) to indoor air analysis for the first time, as part of the highly instrumented HOMEChem field study. We demonstrate how the complex spectra of EESI-MS are screened in order to extract chemical information and investigate the possibility of interference from gas-phase semivolatile species. During experiments that simulated the Thanksgiving US holiday meal preparation, EESI-MS quantified multiple species, including fatty acids, carbohydrates, siloxanes, and phthalates. Intercomparisons with Aerosol Mass Spectrometer (AMS) and Scanning Mobility Particle Sizer suggest that EESI-MS quantified a large fraction of OA. Comparisons with FIGAERO-CIMS shows similar signal levels and good correlation, with a range of 100 for the relative sensitivities. Comparisons with SV-TAG for phthalates and with SV-TAG and AMS for total siloxanes also show strong correlation. EESI-MS observations can be used with gas-phase measurements to identify co-emitted gas- and aerosol-phase species, and this is demonstrated using complementary gas-phase PTR-MS observations.     

赤红球菌组氨酸激酶的融合表达和功能分析

对赤红球菌的组氨酸激酶基因进行密码子优化，将优化后的组氨酸激酶基因（rhks）构建重组表达质粒pGEX-4T-2-rhks。将此质粒导入到大肠杆菌BL21（DE3）中进行异源表达。在25 ℃和1 mmol/L异丙基-β-D-硫代吡喃半乳糖苷诱导条件下，组氨酸激酶融合蛋白（GST-RHK）获得成功表达，并具有催化活性。经谷胱甘肽琼脂糖亲和层析纯化，获得电泳纯的GST-RHK，其中纯化倍数为3.1，得率为19.5%。该蛋白大小约为72.75 kDa，Km、Vmax和Kcat值分别为20.92 μmol/L、0.17 μmol/（L·min）和1.4 min－1。野生型赤红球菌、组氨酸激酶基因增强株sdrhkE和组氨酸激酶基因敲减株sdrhkD在分别含有苯酚、甲苯、氯苯、异辛烷4 种有机溶剂的培养基中培养，菌株sdrhkD的生长情况都优于野生型赤红球菌，菌株sdrhkE的生长情况都低于野生型赤红球菌。本研究为进一步揭示赤红球菌SD3中组氨酸激酶涉及的信号转导途径与赤红球菌有机溶剂耐受性的关联机制提供一定参考依据。