Reaction of layered sodium disilicate SKS-6 with calcium chloride solution as revealed by solid state NMR spectroscopy: exploring the calcium ion extracting mechanism of SKS-6

Solid-state 1H, 29Si NMR and 23Na MQMAS NMR spectroscopy combined with X-ray powder diffraction (XRD) technique was used to study the reaction between layered sodium disilicate SKS-6 and calcium chloride solution with different concentrations. Based on the experimental results the calcium ion extracting mechanism of SKS-6 was demonstrated to be via ion replacement, during which calcium ions replace sodium ions and combine with the non-bridging oxygen in SKS-6 for charge compensation, and simultaneously sodium ions leave the interlayer. This ion-replacement process was greatly influenced by the substitution of sodium ions by protons as well as the calcium ions concentration. Increasing calcium ions concentration favors the replacement of sodium ions by calcium ions, but prevents sodium ions from being substituted by protons.     

New Bithiazole‐Based Sensitizers for Efficient and Stable Dye‐Sensitized Solar Cells

A series of new push–pull organic dyes ( BT‐I – VI ), incorporating electron‐withdrawing bithiazole with a thiophene, furan, benzene, or cyano moiety, as π spacer have been synthesized, characterized, and used as the sensitizers for dye‐sensitized solar cells (DSSCs). In comparison with the model compound T1 , these dyes containing a thiophene moiety between triphenylamine and bithiazole display enhanced spectral responses in the red portion of the solar spectrum. Electrochemical measurement data indicate that the HOMO and LUMO energy levels can be tuned by introducing different π spacers between the bithiazole moiety and cyanoacrylic acid acceptor. The incorporation of bithiazole substituted with two hexyl groups is highly beneficial to prevent close π–π aggregation, thus favorably suppressing charge recombination and intermolecular interaction. The overall conversion efficiencies of DSSCs based on bithiazole dyes are in the range of 3.58 to 7.51 %, in which BT‐I ‐based DSSCs showed the best photovoltaic performance: a maximum monochromatic incident photon‐to‐current conversion efficiency (IPCE) of 81.1 %, a short‐circuit photocurrent density (J_sc) of 15.69 mA cm^?2, an open‐circuit photovoltage (V_oc) of 778 mV, and a fill factor (ff) of 0.61, which correspond to an overall conversion efficiency of 7.51 % under standard global AM 1.5 solar light conditions. Most importantly, long‐term stability of the BT‐I – III ‐based DSSCs with ionic‐liquid electrolytes under 1000 h of light soaking was demonstrated and BT‐II with a furan moiety exhibited better photovoltaic performance of up to 5.75 % power conversion efficiency.     

Characterization of Zn‐Containing Metal–Organic Frameworks by Solid‐State 67Zn NMR Spectroscopy and Computational Modeling

Metal–organic frameworks (MOFs) are an extremely important class of porous materials with many applications. The metal centers in many important MOFs are zinc cations. However, their Zn environments have not been characterized directly by ⁶⁷Zn solid‐state NMR (SSNMR) spectroscopy. This is because ⁶⁷Zn (I=5/2) is unreceptive with many unfavorable NMR characteristics, leading to very low sensitivity. In this work, we report, for the first time, a ⁶⁷Zn natural abundance SSNMR spectroscopic study of several representative zeolitic imidazolate frameworks (ZIFs) and MOFs at an ultrahigh magnetic field of 21.1 T. Our work demonstrates that ⁶⁷Zn magic‐angle spinning (MAS) NMR spectra are highly sensitive to the local Zn environment and can differentiate non‐equivalent Zn sites. The ⁶⁷Zn NMR parameters can be predicted by theoretical calculations. Through the study of MOF‐5 desolvation, we show that with the aid of computational modeling, ⁶⁷Zn NMR spectroscopy can provide valuable structural information on the MOF systems with structures that are not well described. Using ZIF‐8 as an example, we further demonstrate that ⁶⁷Zn NMR spectroscopy is highly sensitive to the guest molecules present inside the cavities. Our work also shows that a combination of ⁶⁷Zn NMR data and molecular dynamics simulation can reveal detailed information on the distribution and the dynamics of the guest species. The present work establishes ⁶⁷Zn SSNMR spectroscopy as a new tool complementary to X‐ray diffraction for solving outstanding structural problems and for determining the structures of many new MOFs yet to come.     

Thermoelastic free vibration of clampe circular plate

An analysis was given for the free vibration of clamped circular plate when temperature and stress fields were coupled. A nonlinear differential equation about time was obtained by using Galerkin’s method. The numerical results of vibration amplitude vs time were compared with the uncoupled case. It is found that if the given initial displacement is small, the effect of thermoelastical coupling will make the natural frequency increase; if the given initial displacement is large, it will be the opposite case. Effects of some different vibration factors are also discussed.     

Preparation and properties of zeolite coating on metal surface

Crystals of mordenite were grown on metallic Cr surface by the vapor phase method. The material of zeolite coating on metal surface has been characterized by X-ray powder diffraction and microprobe. It is shown by the results that this material possesses good catalytic properties.

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Low-potential nicotinamide adenine dinucleotide detection at a glassy carbon electrode modified with toluidine blue O functionalized multiwall carbon nanotubes.

The toluidine blue O (TBO) functionalized multiwall carbon nanotubes (MWNTs) nanomaterials (TBO-MWNTs) were prepared by assembling TBO onto the surface of a MWNTs modified glassy carbon (GC) electrode. Also TBO-MWNTs modified GC electrodes exhibiting a strong and stable electrocatalytic response toward beta-nicotinamide adenine dinucleotide (NADH) were described. Compared with a bare GC electrode, the TBO-MWNTs modified GC electrodes could decrease the oxidization overpotential of NADH by 730 mV, with a peak current at 0.0 V, since there was a positively synergistic electrocatalytic effect between the MWNTs and TBO toward NADH. Furthermore, the TBO-MWNTs modified GC electrodes had perfect performances, such as a low detection limit (down to 0.5 microM), being very stable (the current diminutions is lower than 6% in a period over 35 min), a fast response (within 3 s), and a wide linear range (from 2.0 microM to 3.5 mM). Such an ability of TBO-MWNTs to promote the NADH electron-transfer reaction suggests great promise for dehydrogenase-based amperometric biosensors.     

温度对半胱氨酸缓蚀性能影晌的实验评价与机理研究

通过实验对不同温度条件下半胱氦酸抑制盐酸对碳钢腐蚀的性能进行评价,并采用分子动力学模拟(Molecular Dynamics Simulation,简称MD)方法,从缓蚀剂膜抑制腐蚀粒子扩散的角度对其缓蚀机理进行深入研究.静态失重实验显示:随温度的升高(25～65℃),半胱氨睃缓蚀剂的缓蚀效率呈逐渐下降趋势,其数值从88.36%降至61.64%.MD模拟发现:随温度升高,半胱氨酸缓蚀剂膜的自由体积逐渐增大,且腐蚀粒子与缓蚀剂膜的相互作用也逐渐减弱,更有利于腐蚀粒子在膜中的主动扩散;同时膜内半胱氨酸分子的自扩散能力也随温度升高而增强,腐蚀粒子在缓蚀剂膜携带下被动迁移的过程也随之加剧.主动扩散和被动迁移两方面的变化表明,腐蚀粒子在缓蚀剂膜中扩散能力随温度升高而增大;也就是说,随温度升高,半胱氨酸缓蚀剂膜对腐蚀粒子的扩散抑制能力逐渐降低,腐蚀粒子更易扩散运移至金属表面,导致半胱氨酸缓蚀剂缓蚀效率的降低.     

Lower and upper solution method for the problem of elastic beam with hinged ends

We develop the method of lower and upper solutions for the fourth-order differential equation which models the stationary states of the deflection of an elastic beam, whose both ends simply supported

$$\begin{aligned}&y^{(4)}(x)+(k_1+k_2) y''(x)+k_1k_2 y(x)=f(x,y(x)), \ \ \ \ x\in (0,1),\\&y(0) = y(1) = y''(0) = y''(1) = 0\\ \end{aligned}$$

under the condition \(0<k_1<k_2<x_1^2\approx 4.11585\), where \(x_1\) is the first positive solution of the equation \(x\cos (x)+\sin (x)=0\). The main tools are Schauder fixed point theorem and the Elias inequality.

     

Study on bromocresol green-cetyltrimethylammonium-deoxyribonucleic acids system by resonance light scattering spectrum methods

An assay of deoxyribonucleic acids (DNA) determination, with the sensitivity at nanogram level, was established in the present study by using a common spectrofluorometer to detect the intensity of resonance light scattering (RLS). In hexamethylene tetramine (HMTA) buffer (pH 11.00), Bromocresol Green (BCG) and deoxyribonucleic acids (DNA) react with cetyltrimethylammonium bromide (CTMAB) to form large particles of three-component complex, which results in strong enhanced RLS signals characterized by three peaks at 336, 390, and 622 nm and at 336 nm that is the strongest of the three enhanced RLS peaks. Mechanistic studies showed that the enhanced RLS stems from the aggregation of BCG on DNA through the bridged and synergistic effect of CTMAB. Yeast DNA (yDNA), in the range of 0.05-0.90 ngml(-1), fish sperm DNA (fsDNA) in the range of 0.05-0.80 ngml(-1), and calf thymus DNA (ctDNA) in the range of 0.05-0.80 ngml(-1) can be determined if 2.0 x 10(-6) moll(-1) BCG was employed. The determination limit of yDNA was 12.7 ngml(-1). Three synthetic samples of yDNA were analyzed with good reproducibility.