Mg-catalyzed one-pot preparation of benzimidazoles and spirooxindoles by an immobilized chlorophyll b on magnetic nanoparticles

Chlorophyll b was extracted from Heliotropium europaeum plant, then immobilized on magnetic nanoparticles (Fe₃O₄@SiO₂@Chl-Mg) and found as an efficient and green catalyst for the preparation of a variety of benzimidazoles and spirooxindoles in mild conditions. The catalyst was fully characterized by Fourier-transform infrared (FTIR), ultraviolet–visible (UV–vis) spectroscopy, X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy (EDX), thermogravimetric (TGA), vibrating sample magnetometer (VSM), transmission electron microscopy (TEM), and dynamic light scattering (DLS) analyses. To prove the catalytic influence of Mg over the reactions, the catalytic activity of the demetalated chlorophyll b as well as some other control experiments was investigated. High to excellent yields were achieved for all entries, whether benzimidazole or spirooxindole derivatives at short reaction times. The catalyst could be recovered and reused for several consecutive runs by a simple external magnetic field without any considerable reactivity loss. The properties of the recovered catalyst were investigated by various analyses. Finally, the reasonable mechanisms were proposed for the reactions based on the literature.     

Study on the mechanism of catalytic synthesis of dimethyldichlorosilane by AlCl3/MIL‐53(Al)@γ‐Al2O3

Dimethyldichlorosilane, one of the most consumed organosilicon monomers in the industry, can be prepared in a highly efficient and environmentally friendly synthesis method of disproportionating methylchlorosilanes. However, the internal mechanism of the reaction remains unclear. In this paper, the mechanism catalyzed by AlCl₃/MIL‐53(Al) and AlCl₃/MIL‐53(Al)@γ‐Al₂O₃ catalysts was calculated at B3LYP/6‐311++G(3df, 2pd) level by using the density functional theory (DFT). The results showed that although the two catalysts had similar active structures, the catalytic effects were significantly different. The Lewis acid center on the surface of γ‐Al₂O₃ in the core‐shell catalyst is complementary to the classic Lewis acid AlCl₃ through the spatial superposition effect, which greatly improves the Lewis acid catalytic activity of AlCl₃/MIL‐53(Al)@γ‐Al₂O₃.     

铟镓共掺杂对n-ZnO纳米棒/p-GaN异质结生长行为和光电性能的影响

利用低温水热法在p-GaN薄膜上生长了铟(In)和镓(Ga)共掺杂的ZnO纳米棒。X射线衍射(XRD)、X射线光电子能谱(XPS)和X射线能量色谱仪(EDS)结果表明,In和Ga已固溶到ZnO晶格中。扫描电子显微镜(SEM)结果表明, ZnO纳米棒具有良好的c轴取向性,随着In和Ga共掺杂浓度的增加,纳米棒的直径减小,密度增加。XRD结果表明,In和Ga共掺杂引起ZnO晶格常数增大,导致(002)衍射峰向低角度方向偏移。同时,ZnO的光学性质受到In和Ga共掺杂的影响。与纯ZnO相比, 共掺杂ZnO纳米棒的紫外发射峰都出现轻微红移,这是表面共振和带隙重整效应综合作用的结果。I-V特性曲线表明,随着In和Ga共掺杂浓度的增加,n-ZnO纳米棒/p-GaN异质结具有更好的导电性。     

High-throughput lipidomics analysis to discover lipid biomarkers and profiles as potential targets for evaluating efficacy of Kai-Xin-San against APP/PS1 transgenic mice based on UPLC–Q/TOF–MS

Lipid metabolism has a significant function in the central nervous system and Alzheimer's disease (AD) is an age-related senile disease characterized by central nerve degeneration. The pathological development of AD is closely related to lipid metabolism disorders. To reveal the influence of Kai-Xin-San (KXS) on lipid metabolism in APP/PSI transgenic mice and potential therapeutic targets for treating AD, brain tissue samples were collected and analyzed by high-throughput lipidomics based on UPLC–Q/TOF-MS. The collected raw data were processed by multivariate data analysis to discover the potential biomarkers and lipid metabolic profiles. Compared with the control wild-type mouse group, nine potential lipid biomarkers were found in the AD model group, of which seven were up-regulated and two were down-regulated. Orally administrated KXS can reverse the changes in these potential biomarkers. Compared with the model group, a total of six differential metabolites showed a recovery trend and may be potential targets for KXS to treat AD. This study showed that high-throughput lipidomics can be used to discover the perturbed pathways and lipid biomarkers as potential targets to reveal the therapeutic effects of KXS.     

Assessing the nucleophilic character of 2-amino-4-arylthiazoles through coupling with 4,6-dinitrobenzofuroxan: Experimental and theoretical approaches based on structure-reactivity relationships

A kinetic study of the reactions of potentially bioactive 2-amino-4-arylthiazoles with highly reactive 4,6-dinitrobenzofuroxan (DNBF) is reported herein in acetonitrile solution. The complexation reaction was followed by recording the UV–vis spectra with time at λ_max = 482 nm. Electronic effects of substituents influencing the rate of reaction have been studied using structure-reactivity relationships. It is shown that the Hammett plot relative to the reaction of DNBF with 2-amino-4-(4-chlorophenyl)thiazole exhibit positive deviation from the log k₁ versus σ correlation, while it showed excellent linear correlation in terms of Yukawa–Tsuno equation. It has be noticed that the nonlinear Hammett plot observed for 2-amino-4-(4-chlorophenyl) thiazole is not attributed to a change in rate-determining step but is due to nature of electronic effect of substituent caused by the resonance of stabilization of substrates. The second-order rate constant (k₁) relating to the bond C–C and C-N forming step of the complexation processes of DNBF with 4-substituted-aminothiazoles and 2-amino-5-methyl-4-phenylthiazole, respectively, is fit into the linear relationship log k = s_N (N + E), thereby permitting the assessment of the nucleophilicity parameter (N) of the 2-amino-4-arylthiazoles of the range (4.90 < N < 6.85). 2-amino-4-arylthiazoles is subsequently ranked by positioning its reactivity on the general nucleophilicity scale developed recently by Mayr and coworkers (2003) leading an interesting and a direct comparison over a large domain of π-, σ -, and n-nucleophiles. The global electrophilicity/nucleophilicity reactivity indexes of the 2-amino-4-arylthiazoles have been investigated by means of a density functional theory (DFT) method. .     

Mass spectrometry imaging of latent fingerprints using titanium oxide development powder as an existing matrix

Recent research has focused on increasing the evidentiary value of latent fingerprints through chemical analysis. Although researchers have optimized the use of organic and metal matrices for matrix‐assisted laser desorption/ionization‐mass spectrometry imaging (MALDI‐MSI) of latent fingerprints, the use of development powders as matrices has not been fully investigated. Carbon forensic powder (CFP), a common nonporous development technique, was shown to be an efficient one‐step matrix; however, a high‐resolution mass spectrometer was required in the low mass range due to carbon clusters. Titanium oxide (TiO₂) is another commonly used development powder, especially for dark nonporous surfaces. Here, forensic TiO₂ powder is utilized as a single‐step development and matrix technique for chemical imaging of latent fingerprints without the requirement of a high‐resolution mass spectrometer. All studied compounds were successfully detected when TiO₂ was used as the matrix in positive mode, although, generally, the overall ion signals were lower than the previously studied CFP. TiO₂ provided quality mass spectrometry (MS) images of endogenous and exogenous latent fingerprint compounds. The subsequent addition of traditional matrices on top of the TiO₂ powder was ineffective for universal detection of latent fingerprint compounds. Forensic TiO₂ development powder works as an efficient single‐step development and matrix technique for MALDI‐MSI analysis of latent fingerprints in positive mode and does not require a high‐resolution mass spectrometer for analysis.     

Statistical structure of the velocity field in cavitating flow around a 2D hydrofoil

Transformation of flow turbulence structure with cavitation occurrence, determination of the flow conditions favorable for nucleation of cavitation bubbles, influence of the statistical structure of turbulence on this process and the inverse effect of cavitation on the flow dynamics are challenging problems in modern fluid mechanics. The paper reports on the results of statistical processing of the velocity fields measured by a PIV technique in cavitating flow over a 2D symmetric hydrofoil for four flow conditions, starting from a cavitation-free regime and finishing by unsteady cloud cavitation. We analyze basic information on the statistical structure of velocity fluctuations in the form of histograms and Q-Q diagrams along with profiles of the mean velocity and turbulent kinetic energy. The research reveals that the flow turbulence pattern and distributions of turbulent fluctuations change significantly with the cavitation development. Under unsteady cloud cavitation conditions, the probability density function of the fluctuating velocity has a two-mode distribution, which indicates switching of two alternating flow conditions in a region above the hydrofoil aft part due to periodic passing of cavitation clouds. Behaviors of the mean and most probable velocities unexpectedly appear to be different with a monotonous increase of the incoming flow velocity. This finding must be caused by modification of the skewness coefficient of the fluctuating velocity.     

GaInP/GaAs/Ge三结太阳电池不同能量质子辐照损伤模拟

以GaInP/GaAs/Ge三结太阳电池为研究对象,开展了能量为0.7, 1, 3, 5, 10 MeV的质子辐照损伤模拟研究,建立了三结太阳电池结构模型和不同能量质子辐照模型,获得了不同质子辐照条件下的I-V曲线,光谱响应曲线,结合已有实验结果验证了本文模拟结果,分析了三结太阳电池短路电流、开路电压、最大功率、光谱响应随质子能量的变化规律,利用不同辐照条件下三结太阳电池最大输出功率退化结果,拟合得到了三结太阳电池最大输出功率随位移损伤剂量的退化曲线.研究结果表明,质子辐照会在三结太阳电池中引入位移损伤缺陷,使得少数载流子扩散长度退化幅度随质子能量的减小而增大,从而导致三结太阳电池相关电学参数的退化随质子能量的减小而增大.相同辐照条件下,中电池光谱响应退化幅度远大于顶电池光谱响应退化幅度,中电池抗辐照性能较差,同时中电池长波范围内光谱响应的退化幅度比短波范围更大,表明中电池相关电学参数的退化主要来源于基区损伤.     

Accurate iteration-free mixed-stabilised formulation for laminar incompressible Navier–Stokes: Applications to fluid–structure interaction

Stabilised mixed velocity–pressure formulations are one of the widely-used finite element schemes for computing the numerical solutions of laminar incompressible Navier–Stokes. In these formulations, the Newton–Raphson scheme is employed to solve the nonlinearity in the convection term. One fundamental issue with this approach is the computational cost incurred in the Newton–Raphson iterations at every load/time step. In this paper, we present an iteration-free mixed finite element formulation for incompressible Navier–Stokes that preserves second-order temporal accuracy of the generalised-alpha and related schemes for both velocity and pressure fields. First, we demonstrate the second-order temporal accuracy using numerical convergence studies for an example with a manufactured solution. Later, we assess the accuracy and the computational benefits of the proposed scheme by studying the benchmark example of flow past a fixed circular cylinder. Towards showcasing the applicability of the proposed technique in a wider context, the inf–sup stable P2–P1 pair for the formulation without stabilisation is also considered. Finally, the resulting benefits of using the proposed scheme for fluid–structure interaction problems are illustrated using two benchmark examples in fluid-flexible structure interaction.