温度扰动下CuCl2/DMF溶液的二维相关拉曼光谱分析

溶液的光谱研究一直受到化学工作者的关注,但大多研究是以一维光谱技术为主,存在分辨率低,误差较大,重叠峰难以分辨等诸多弊端,无法清晰地给出需要的信息。二维光谱通过对外部扰动下的动态光谱进行相关分析计算,从而得到光谱强度的整体变化信息,显著提高一维光谱的分辨率以及重叠峰的分离度。在判断特定外扰下不同官能团的响应次序以及研究分子间、分子内的弱相互作用上具有独特优势。采用二维相关拉曼光谱和理论计算相结合,对溶液内微观团簇及其变化进行了研究。利用显微共焦激光拉曼光谱仪对目标溶液(纯DMF与0.84 mol·L-1的CuCl₂/DMF溶液)进行了升温实验。结果发现在C-N键伸缩振动谱带范围内,由于CuCl₂的加入,特征峰强度整体大幅下降,峰宽变大,在1 115 cm-1有新峰产生,随温度升高,伸缩振动峰强度逐渐下降,峰形变缓。为了获得C-N键振动内各特征峰随温度的变化情况,采用移动窗口二维拉曼(MW2D Raman)光谱技术,对光谱数据进行分析。结果表明溶液内不同类别的微观团簇对温度的敏锐程度不同,随温度升高,它们之间存在相互转化,且变化速度不同。为了获取溶液内各微观团簇运动的实质,以温度为外扰,采用二维拉曼(2D Raman)光谱对目标溶液进行分析,通过对二维光谱中特征峰进行归属和变化次序判断,发现金属Cu2+的加入,使得溶液体系变得更加复杂,除存在原溶剂内所含的团簇构型,还存在与Cu2+发生溶剂化的团簇构型,它们之间存在着一定的相互转化。利用密度泛函理论对溶液中可能存在的团簇构型进行结构优化和热力学计算,结果证实了Cu2+与DMF存在相互作用,且由此产生的团簇构型[Cu(DMF)_n]2+(n=1~6)的稳定性随n的增大逐渐变差,进一步验证了二维相关光谱分析的可行性与正确性。     

Study on the emulsification and oxidative stability of ovalbumin-pectin-pumpkin seed oil emulsions using ovalbumin solution prepared by ultrasound

Pumpkin seed oil (PSO), which is a valuable compound with high nutritional value used for the prevention of various chronic diseases, is prone to oxidation. In this work, small and uniform (su) ovalbumin (OVA) and pectin (PEC) were used to stabilize PSO in the form of an emulsion. The results showed that suOVA-PEC-PSO emulsion with a droplet size of 9.82 ± 0.05 μm was successfully self-assembled from PSO, PEC, and suOVA solution (with a droplet size of 230.13 ± 14.10 nm) treated with 300 W ultrasound, owing to the formation of a more stable interfacial film on the surface of droplets. The interfacial, rheological, emulsifying, and antioxidant properties of the suOVA-PES-PSO emulsions were excellent, owing to the synergistic effects between PEC and suOVA solution. Moreover, the physical stability of the suOVA-PEC-PSO emulsions to salt stress, a freeze-thaw cycle, and heat treatment was also increased and the oxidation of linolenic acid was notably delayed. These results have extended the food-related applications of OVA and PSO, and provide a promising foundation for further exploration of the self-assembly of composite emulsions by small and uniform proteins.     

Magnetism and giant magnetocaloric effect in rare-earth-based compounds R_3BWO_9(R = Gd,Dy, Ho)

The magnetism and magnetocaloric effect(MCE) of rare-earth-based tungstate compounds R_3 BWO_9(R=Gd,Dy,Ho) have been studied by magnetic susceptibility,isothermal magnetization,and specific heat measurements.No obvious long-range magnetic ordering can be found down to 2 K.The Curie-Weiss fitting and magnetic susceptibilities under different applied fields reveal the existence of weak short-range antiferromagnetic couplings at low temperature in these systems.The calculations of isothermal magnetization exhibit a giant MCE with the maximum changes of magnetic entropy being 54.80 J/kg-K at 2 K for Gd_3 BWO_9,28.5 J/kg-K at 6 K for Dy_3 BWO_9,and 29.76 J/kg-K at 4 K for Ho_3 BWO_9,respectively,under a field change of 0-7 T.Especially for Gd_3 BWO_9,the maximum value of magnetic entropy change(-ΔS_M~(max)) and adiabatic temperature change(-ΔT_(ad)~(max)) are 36.75 J/kg·K and 5.56 K for a low field change of 0-3 T,indicating a promising application for low temperature magnetic refrigeration.     

Absence of magnetic order in dichloro [1,2-bis(diphenylphosphino)ethane] nickel~(2+) single crystal

Dichloro [1,2-bis(diphenylphosphino) ethane] nickel~(2+)(Ni Cl_2(dppe)) is an organic compound containing C_(26)H_(24)P_2(dppe) molecules and Cl-, Ni~(2+)ions. The large-size Ni Cl_2(dppe) single crystals with longest dimension of4 mm were grown by the method of slow evaporation of organic solution. Single crystal x-ray diffraction spectrum indicates that the single crystal is of high quality. Magnetization results of the Ni Cl_2(dppe) single crystals show an anisotropic paramagnetism behavior and diamagnetic background, which come from Ni~(2+) ions and benzene ring, respectively. However, according to the specific heat results with temperature down to 0.1 K and magnetic field up to 14 T, no expected field-induced quantum phase transition was observed in Ni Cl_2(dppe) single crystals.     

A novel near-infrared chemosensor for mercury ion detection based on D-A structure of triphenylamine and benzothiadiazole

A novel near infrared ratiometric fluorescent chemosensor based on triphenylamine, thiophene and benzothiadiazole has been developed. The emission wavelength of sensor DTPAT-BT-S was in the near infrared region. The wavelength changed from 656 nm to 723 nm, and got a rather long stokes shift about 170 nm. The sensor showed a very high selectivity towards Hg²⁺ ions.     

Positive solutions of the system for nth-order singular nonlocal boundary value problems

The paper deals with the existence and multiplicity of positive solutions to systems of nth-order singular nonlocal boundary value problems. The main tool used in the proof is fixed point index theory in cone. Some limit type conditions for ensuring the existence of positive solutions are given.     

Comparison of several stochastic parallel optimization algorithms for adaptive optics system without a wavefront sensor

Optimizing the system performance metric directly is an important method for correcting wavefront aberrations in an adaptive optics (AO) system where wavefront sensing methods are unavailable or ineffective. An appropriate “Deformable Mirror” control algorithm is the key to successful wavefront correction. Based on several stochastic parallel optimization control algorithms, an adaptive optics system with a 61-element Deformable Mirror (DM) is simulated. Genetic Algorithm (GA), Stochastic Parallel Gradient Descent (SPGD), Simulated Annealing (SA) and Algorithm Of Pattern Extraction (Alopex) are compared in convergence speed and correction capability. The results show that all these algorithms have the ability to correct for atmospheric turbulence. Compared with least squares fitting, they almost obtain the best correction achievable for the 61-element DM. SA is the fastest and GA is the slowest in these algorithms. The number of perturbation by GA is almost 20 times larger than that of SA, 15 times larger than SPGD and 9 times larger than Alopex.     

Effect of preheating temperatures on microstructure and optical properties of Na-doped ZnO thin films by sol–gel process

The chemical composition, crystalline structure, surface morphology and photoluminescence spectra of Na-doped ZnO thin films with different heat treatment process were investigated by X-ray photoelectron spectroscopy, X-ray diffraction, atomic force microscopy and a fluorescence spectrometer. The results show that preferred orientation, residual stress, average crystal size and surface morphology of the thin films are strongly determined by the preheating temperature. The effects of preheating temperature on microstructure and surface morphology have been discussed in detail. The photoluminescence spectra show that there are strong violet & UV emission, blue emission and green emission bands. The violet & UV emission is ascribed to the electron transition from the localized level below the conduction band to the valence band. The blue emission is attributed to the electron transition from the shallow donor level of oxygen vacancies to the valence band, and the electron transition from the shallow donor level of interstitial zinc to the valence band. The green emission is assigned to the electron transition from the level of ionized oxygen vacancies to the valence band.     

太阳过渡区紫外光谱的观测与诊断

太阳过渡区是太阳色球层顶到日冕底部的大气薄层。厚度仅几百千米,但其间太阳等离子体参数变化剧烈。过渡区的辐射多为光学薄的远紫外、极紫外发射谱线和背景连续谱线。由于地球大气的吸收,过渡区紫外光谱需通过天基观测才能实现。近几十年来,星载仪器的成功发射为太阳过渡区的研究打开了新纪元。工作回顾了太阳过渡区紫外光谱的观测历史和各类星载仪器,特别介绍了近十几年几种重要的光谱仪器。详细阐述了过渡区紫外光谱的发生率、电子密度和电子温度的诊断原理。讨论了过渡区紫外谱线的形状,并以SOHO/SUMER光谱仪为例介绍了表征谱线的几种重要参量及其物理意义。     

Existence and exponential convergence of almost periodic positive solution for Nicholson's blowflies discrete model with linear harvesting term

This paper deals with a discrete Nicholson's blowflies model with linear harvesting term. By using contraction mapping fixed point theorem, we obtain sufficient conditions for the existence of unique almost periodic positive solution. Moreover, we investigate exponential convergence of the almost periodic positive solution by Lyapunov functional. Copyright © 2013 John Wiley & Sons, Ltd.