Optimization of extraction and quantification technique for phenolics content of garlic (Allium sativum): An application for comparative phytochemical evaluation based on cultivar origin

A range of conventional, i.e. maceration, percolation, ultrasonic assisted, Soxhlet and Soxtec extraction (STE), to advanced extraction techniques of accelerated solvent extraction (ASE) was utilized for the first time in order to optimize the extract yield and recovery of phenolics—gallic acid (GA), rutin (RT) and quercetin (QT)—quantified via ultra-high performance liquid chromatography with diode array detector (UHPLC–DAD). The effect of solvents (n-hexane, dichloromethane and methanol) and temperature (60, 80 and 100°C) upon extraction yield, phenolic content and antioxidant activity (DPPH, ABTS and DPPH) was studied, and the method was validated in commercial food samples from Saudi Arabia, China and India. A high extract yield with percentage recovery was observed for STE (1221.10 mg/5 g; 24.42%) and ASE techniques (91.50 mg/1 g; 9.15%) in methanol at 100°C. UHPLC–DAD showed retention times (min) of 0.67, 1.93 and 1.90 for GA, RT and QT, respectively in the shortest runtime of 3 min. The yield for phenolics was higher for STE/ASE (ppm): 15.27/15.29 (GA), 85.24/37.56 (RT) and 52.20/33.40 (QT), respectively. In terms of antioxidant activities, low IC₅₀ values (μg/ml) of 1.09/1.18 (DPPH), 2.11/5.32 (ABTS) and 4.35/7.88 (phenazine methosulfate–nicotinamide adenine dinucleotide) were observed for STE and ASE, respectively. Multivariate analysis for STE showed a significant (P = 0.000) correlation for extraction type vs. extract yield and phenolics content; however, there was no significance for antioxidant activities vs. extraction type. ASE showed a positive correlation for solvent vs. extraction yield, phenolics and antioxidant activity; however, there was no correlation for extraction yield and DPPH activity. Principal component analysis for STE showed a major variability (52.02%) for extraction yield and phenolics in PC1 followed by PC2 (38.30%) for antioxidant activities. For ASE, PC1 (48.68%) showed a positive correlation for solvent vs. extraction yield and phenolics while PC2 (33.12%) showed a positive correlation for temperature and antioxidant activities. STE and ASE were the optimized extraction techniques for the garlic food sample while a significant effect of solvent and temperature was observed upon extraction yield, phenolics and antioxidant activity.     

Thermal cross-link between 2,5-furandicarboxylic acid-based polyimides and bismaleimide via Diels–Alder reaction

A series of cross-linked polyimides (PIs) were prepared via two-step solution polycondensation from 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride (BPADA) and 2,5-furandicarboxylic acid-based diamines, N,N′-bis(4-amino-2-(trifluoromethyl)phenyl)furan-2,5-dicarboxamide (TFFDA) and N,N′-bis(4-aminophenyl)furan-2,5-dicarboxamide (p-FDDA), followed by thermal crosslinking reaction with bismaleimide. The thermal crosslinking reaction and its mechanism were studied by FTIR spectra and model reaction analysis, which showed Diels–Alder reaction between furan group and maleimide group played a main role in the thermal treatment. The properties of cross-linked PIs were characterized using dynamic mechanical thermal analysis, thermogravimetric analyses, tensile testing, ultraviolet-visible spectra, and wide-angle X-ray diffraction. The cross-linked polyimide film showed improved solvent-resistance, thermal and mechanical properties with T_g values of 234–306^oC, tensile strengths of 82–98 MPa and moduli of 2.3–3.0 GPa.     

Nonmetal Doping as a Robust Route for Boosting the Hydrogen Evolution of Metal-Based Electrocatalysts

Recently, nonmetal doping has exhibited its great potential for boosting the hydrogen evolution reaction (HER) of transition-metal (TM)-based electrocatalysts. To this end, this work overviews the recent achievements made on the design and development of the nonmetal-doped TM-based electrocatalysts and their performance for the HER. It is also shown that by rationally doping nonmetal elements, the electronic structures of TM-based electrocatalysts can be effectively tuned and in turn the Gibbs free energy of the TM for adsorption of H* intermediates (ΔG_H*) optimized, consequently enhancing the intrinsic activity of TM-based electrocatalysts. Notably, we highlight that concurrently doping two nonmetal elements can continuously and precisely regulate the electronic structures of the TM, thereby maximizing the activity for HER. Moreover, nonmetal doping also accounts for enhancing the physical properties of the TM (i.e. surface area). Therefore, nonmetal doping is a robust strategy for simultaneous regulation of the chemical and physical features of the TM.     

Photo-recycling the Sacrificial Electron Donor: Towards Sustainable Hydrogen Evolution in a Biphasic System

H₂ may be evolved biphasically using a polarised liquid|liquid interface, acting as a “proton pump”, in combination with organic soluble metallocenes as electron donors. Sustainable H₂ production requires methodologies to recycle the oxidised donor. Herein, the photo-recycling of decamethylferrocenium cations (DcMFc⁺) using aqueous core-shell semiconductor CdSe@CdS nanoparticles is presented. Negative polarisation of the liquid|liquid interface is required to extract DcMFc⁺ to the aqueous phase. This facilitates the efficient capture of electrons by DcMFc⁺ on the surface of the photo-excited CdSe@CdS nanoparticles, with hydrophobic DcMFc subsequently partitioning back to the organic phase and resetting the system. TiO₂ (P25) and CdSe semiconductor nanoparticles failed to recycle DcMFc⁺ due to their lower conduction band energy levels. During photo-recycling, CdS (on CdSe) may be self-oxidised and photo-corrode, instead of water acting as the hole scavenger.     

Complementarity between micro-micro and micro-macro entanglement in a Bose–Einstein condensate with two Rydberg impurities

We theoretically study complementarity between micro-micro and micro-macro entanglement in a Bose–Einstein condensate with two Rydberg impurities. We investigate quantum dynamics of micro-micro and micro-macro entanglement in the micro-macro system. It is found that strong micro-macro entanglement between Rydberg impurities and the BEC can be generated by the use of initial micro-micro entanglement between two Rydberg impurities, which acts as the seed entanglement to create micro-macro entanglement. We demonstrate a curious complementarity relation between micro-micro and micro-macro entanglement, and find that the complementarity property can be sustained to some extent even though in the presence of the BEC decoherence.     

Analysis,design and simulation of MIM plasmonic filters with different geometries for technical parameters improvement

In this paper, four optical filter topologies based on metal–insulator–metal waveguides are proposed and the designed structures are investigated numerically using finite-difference timedomain method. Triangular-shaped adjunctions have been added to the filter structures to improve their transmission spectrum. These improved structures consist of air as the insulator and silver as the metal. The relative permittivity of metal has been described via the Drude,Drude–Lorentz, and Palik models. The first filter's transmission spectrum shows an acceptable transmittance. In the second optimized filter, the transmission spectrum has been improved. The transmittance spectrum can be tuned through adjusting the edge of the triangle in these four optimized filters. As a result, the bandwidths of resonance spectra can be adjusted. The theory of such tapered structures will be investigated by the tapered transmission line and will be solved with the transfer matrix method. This method shows a better performance and higher transmission efficiency in comparison with the basic structures. On the other hand, the final filter has been chosen as the best one because of its hexagonal resonator. The main reason for having a better result is due to a longer interaction length in comparison with the circular resonator. This in turn creates much better energy coupling and results in higher transmission.     

利用电磁法研究HMX与TATB混合钝感炸药的冲击起爆特性

为研究含有少量奥克托金(HMX)且以三氨基三硝基苯(TATB)为基的高能钝感炸药PBX-3的冲击起爆反应增长规律,采用火炮驱动蓝宝石飞片的方法和铝基组合式电磁粒子速度计技术进行了一维平面冲击实验。通过实验测量撞击表面及内部不同深度处的冲击波后粒子速度,得到PBX-3炸药的Hugoniot关系。根据冲击波示踪器所测数据绘制了炸药到爆轰的时间-距离(x-t)图,获得了反映炸药冲击起爆性能的Pop关系。将入射压力为12.964 GPa时达到爆轰的6条速度曲线修整成相同零点,通过读取6条曲线的分离点即反应区末端的C-J点,计算出化学反应区时间和宽度。     

第三族金属氧化物离子对二氧化碳转化的红外光谱研究

本文利用红外光解离光谱研究了第三族金属氧化物离子对二氧化碳分子的转化机制. 研究表明，对于[ScO(CO₂)_n]⁺体系，在n≤4时，形成了溶剂化结构；在n=5时，形成了碳酸盐结构，实现了二氧化碳的转化. 对于[YO(CO₂)_n]⁺体系，需要4个二氧化碳分子就可以实现二氧化碳的转化. 而在[YO(CO₂)_n]⁺体系中，只发现了溶剂化结构，没有观察到碳酸盐结构. 理论计算表明，[YO(CO₂)_n]⁺体系拥有最小的溶剂化结构向碳酸盐结构转化能垒，[LaO(CO₂)_n]⁺体系拥有最大的溶剂化结构向碳酸盐结构转化能垒. 本文从分子水平揭示了不同金属氧化物离子对二氧化碳分子转化的影响规律.     

Modified and environmentally friendly oxidation of phosphorane ylides to vicinal tricarbonyls using unsupported moist Oxone in dichloromethane

Abstract

Modified and eco-friendly oxidation of phosphorane ylides to the corresponding vicinal tricarbonyls (VTC) using unsupported moist Oxone in dichloromethane at room temperature is described. This green oxidation protocol is simple, mild, and highly efficient to operate, and allowing a chemoselective preparation of VTC from various phosphorane ylides without tedious workup procedures of extraction/drying process in excellent yields.     

S-O bond chemically constrained NiS2/rGO nanocomposite with enhanced Na-ion storage capacity

NiS₂ has become a research hotspot of anode materials for Na-ion batteries due to its high theoretical specific capacity. However, the volume effect, the dissolution of polysulfide intermediates and the low conductivity during the charge/discharge process lead to the low specific capacity and poor cycling stability. NiS₂/rGO nanocomposite was prepared by a facile two-step process: GO was prepared by modified Hummers method, and then NiS₂/rGO nanocomposite was synthesized by l-cys assisted hydrothermal method. NiS₂/rGO nanocomposite shows excellent cycle performance and rate performance, which could be attributed to the mesoporous structure on the graphene skeleton with high conductivity. Besides, the chemical constraint of a unique SO bond on NiS₂ could inhibit the dissolution of intermediates and the loss of irreversible capacity.