Near-Field Drives Long-Lived Shallow Trapping of Polymeric C3N4 for Efficient Photocatalytic Hydrogen Evolution

Undesired photoelectronic dormancy through active species decay is adverse to photoactivity enhancement. An insufficient extrinsic driving force leads to ultrafast deep charge trapping and photoactive species depopulation in carbon nitride (g-C₃N₄). Excitation of shallow trapping in g-C₃N₄ with long-lived excited states opens up the possibility of pursuing high-efficiency photocatalysis. Herein, a near-field-assisted model is constructed consisting of an In₂O₃-cube/g-C₃N₄ heterojunction associated with ultrafast photodynamic coupling. This In₂O₃-cube-induced near-field assistance system provides catalytic “hot areas”, efficiently enhances the lifetimes of excited states and shallow trapping in g-C₃N₄ and this favors an increased active species density. Optical simulations combined with time-resolved transient absorption spectroscopy shows there is a built-in charge transfer and the active species lifetimes are longer in the In₂O₃-cube/g-C₃N₄ hybrid. Besides these properties, the estimated overpotential and interfacial kinetics of the In₂O₃-cube/g-C₃N₄ hybrid co-promotes the liquid phase reaction and also helps in boosting the photocatalytic performance. The photocatalytic results exhibit a tremendous improvement (34-fold) for visible-light-driven hydrogen production. Near-field-assisted long-lived active species and the influences of trap states is a novel finding for enhancing (g-C₃N₄)-based photocatalytic performance.     

Laboratory-scale liquefiers for natural gas: A design and assessment study

Exact knowledge of natural gas composition is essential in custody transfer to determine the energy content of the delivery. However, for liquefied natural gas (LNG), a reliable composition determination is difficult. Here, we describe the design of a laboratory-scale reference liquefier that enables the validation and calibration of optical spectroscopy sensors by providing them with a sample of metrologically traceable composition. Hence, it is crucial to avoid fractionation of the sample during liquefaction. This is realized by supercritical liquefaction of a reference gas mixture in conjunction with a special vapor–liquid-equilibrium (VLE) cell. As this is a demanding high-pressure application, low-pressure condensation as liquefaction method was also assessed. Through experimental investigations and VLE calculations, preservation of the composition of the produced liquid sample during condensation was studied. We conclude that under optimized conditions, validation, and calibration measurements of optical sensors can be performed on condensed liquids, which, however, needs further confirmation.     

Investigation of the interaction between hydrogen and irradiation defects in titanium by using positron annihilation spectroscopy

The formation of mono-vacancy, vacancy clusters and hydrogen-vacancy complexes with 30 keV H ion-irradiated pure titanium at different doses and temperatures was measured using by Positron annihilation spectroscopy (PAS). Results show a large number of H_mV_n clusters and vacancy-like defects in the samples irradiated at for room temperature, and that the formation of H_mV_n (m > n) at the sample irradiated at a high dose inhibits the increase of the S parameter. At increased irradiation temperature, the shrinkage of vacancy clusters and the effective open volume of defects decrease the S parameters. The high-temperature irradiation results in decreased vacancy-type defect concentration, and some hydrogen atoms diffuse from the cascade region to the track region, forming a large number of hydrogen-vacancy complexes in the track region. The coincidence Doppler broadening spectroscopy, an element analysis method, used to detect hydrogen in the ion-irradiated pure titanium sample, and results show hydrogen-related peaks in the high-momentum region, which may be due to the information of positron annihilation in the covalent bond formed by the H and the Ti elements. The increased radiation dose and temperature contribute to the formation of the hydrogen vacancy-complex, and the positron annihilation in high-momentum regions easily obtain hydrogen-related information.     

In situ monitoring of the biocatalysed partial hydrolysis of cocoa butter and palm oil fraction

Partial glycerides are widely used ingredients in confectionery products that can be produced from natural fats. In a biocatalytic partial hydrolysis of cocoa butter and palm oil fractions, a product mixture containing 1.5% monoglycerides and 5.5% diglycerides intended for the use in confectionery products was created. This study is a proof of principle that shows the feasibility of monitoring the biocatalytic partial hydrolysis of these two natural fats in situ with ATR-FTIR spectroscopy. An economic approach was utilised for calibration since partial glyceride calibration standards are costly and poorly available. The released compounds were quantified by means of chemometric modelling, and the model was validated with gas chromatography. Resulting root mean square errors were in the low per cent range. Additionally, the results indicate that distinction of the released free fatty acids is possible with ATR-FTIR spectroscopy.     

Conformation Analysis of GalNAc‐Appended Sugar Amino Acid Foldamers as Glycopeptide Mimics

Sugar amino acid (SAA)‐based foldamers with well‐defined secondary structures were appended with N‐acetylgalactosamine (GalNAc) sugars to access sequence‐defined, multidentate glycoconjugates with full control over number, spacing and position. Conformation analysis of these glycopeptides by extensive NMR spectroscopic studies revealed that the appended GalNAc units had a profound influence on the native conformational behaviour of the SAA foldamers. Whereas the 2,5‐cis glycoconjugate showed a helical structure in water, comprising of two consecutive 16‐membered hydrogen bonds, its 2,5‐trans congener displayed an unprecedented 16/10‐mixed turn structure not seen before in any glycopeptide foldamer.     

Insights into Protein Stability in Cell Lysate by 19F NMR Spectroscopy

In living organisms, protein folding and function take place in an inhomogeneous, highly crowded environment possessing a concentration of diverse macromolecules of up to 400 g/L. It has been shown that the intracellular environment has a pronounced effect on the stability, dynamics and function of the protein under study, and has for this reason to be considered. However, most protein studies neglect the presence of these macromolecules. Consequently, we probe here the overall thermodynamic stability of cold shock protein B from Bacillus subtilis (BsCspB) in cell lysate. We found that an increase in cell lysate concentration causes a monotonic increase in the thermodynamic stability of BsCspB. This result strongly underlines the importance of considering the biological environment when inherent protein parameters are quantitatively determined. Moreover, we demonstrate that targeted application of ¹⁹F NMR spectroscopy operates as an ideal tool for protein studies performed in complex cellular surroundings.     

La2O3对SiO2-CaO-Al2O3-MgO熔体黏度和结构的影响

使用分析纯物质模拟微晶玻璃熔体，分别采用柱体旋转法和拉曼光谱技术研究了La2O3含量对SiO2-CaO-Al2O3-MgO熔体黏度和结构的影响规律。结果表明：熔体黏度和黏流活化能随着La2O3含量的增加而降低；拉曼光谱表明La2O3能破坏硅酸盐结构（Qn），随着La2O3含量的增加，Q1、Q2的百分含量增加，Q3的百分含量减小，Q0的百分含量基本不变，表明熔体中非桥氧数量增加，熔体聚合度降低。La2O3在熔体中起网络修饰体的作用。     

Online monitoring of the curing of adhesives with a miniaturised interdigital sensor using impedance spectroscopy

Monitoring adhesives during manufacturing and their lifetime has become increasingly important due to the variety of materials and applications. Impedance spectroscopy is a suitable method for online monitoring of the curing process. We present a miniaturised interdigital structure to monitor the curing process of the adhesives using impedance spectroscopy. Compared to other sensors, our sensor is ultrathin, so that it disappears in the adhesive joint. Therefore, it can remain in the joint and be used for lifetime monitoring. In addition it is suitable for thin adhesive layers due to its fine grid. We demonstrate that the impedance of the sensor embedded in the adhesive gives insight into the curing mechanisms. Therefore monitoring of a dispersion and an epoxy is shown. In addition, the curing cycles can be reliably controlled using this monitoring method. The permittivity of the adhesives is extracted from the impedance measurements, applying analytical models of the electrical field of the interdigital structure.     

Influence of the chemical structure of additives poly(ethylene-co-vinyl acetate)-based on the pour point of crude oils

One of the methods to prevent wax precipitation, during petroleum production, transport, and refining, is the use of polymer additives that can reduce the oil pour point. However, no single additive work for all types of crude oil and this relation is not yet well known. In this study, a family of polymers based on poly(ethylene-co-vinyl acetate), containing hydroxyl groups and long pendant hydrocarbon chains (from C6 to C18), were synthesized and characterized by H¹ nuclear magnetic resonance and solubility test. Four crude oil samples containing different amounts and size distribution of the wax were used. The additive's action is favored by higher contents of iso + cycloalkanes and lower contents of n-paraffins with larger chain sizes. The presence of the CH₃COO group in the copolymers promoted the lowering of the pour point, supported by a low OH concentration and the presence of a long pendant hydrocarbon chain: the best results were obtained with C10 and C12 chain lengths. © 2020 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48969.