Hexametaphosphate‐Capped Silica Mesoporous Nanoparticles Containing CuII Complexes for the Selective and Sensitive Optical Detection of Hydrogen Sulfide in Water

Cu^II‐macrocycle functionalized hexametaphosphate‐capped silica mesoporous nanoparticles have been prepared and used for the selective and sensitive detection of hydrogen sulfide in aqueous environments. The possibility of using different metal complexes combined with different capping anions and choice of different dyes or other sensing molecules as indicators makes this new protocol highly appealing for the preparation of new sensing systems for sulfide detection in different environments.     

Chebyshev spectral variational integrator and applications

The Chebyshev spectral variational integrator(CSVI) is presented in this paper. Spectral methods have aroused great interest in approximating numerically a smooth problem for their attractive geometric convergence rates. The geometric numerical methods are praised for their excellent long-time geometric structure-preserving properties.According to the generalized Galerkin framework, we combine two methods together to construct a variational integrator, which captures the merits of both methods. Since the interpolating points of the variational integrator are chosen as the Chebyshev points,the integration of Lagrangian can be approximated by the Clenshaw-Curtis quadrature rule, and the barycentric Lagrange interpolation is presented to substitute for the classic Lagrange interpolation in the approximation of configuration variables and the corresponding derivatives. The numerical float errors of the first-order spectral differentiation matrix can be alleviated by using a trigonometric identity especially when the number of Chebyshev points is large. Furthermore, the spectral variational integrator(SVI) constructed by the Gauss-Legendre quadrature rule and the multi-interval spectral method are carried out to compare with the CSVI, and the interesting kink phenomena for the Clenshaw-Curtis quadrature rule are discovered. The numerical results reveal that the CSVI has an advantage on the computing time over the whole progress and a higher accuracy than the SVI before the kink position. The effectiveness of the proposed method is demonstrated and verified perfectly through the numerical simulations for several classical mechanics examples and the orbital propagation for the planet systems and the Solar system.     

Enzyme‐Responsive Silica Mesoporous Supports Capped with Azopyridinium Salts for Controlled Delivery Applications

The preparation of a new capped silica mesoporous material, Rh‐Azo‐S , for on‐command delivery applications in the presence of target enzymes is described. The material consists of nanometric mesoporous MCM‐41‐like supports loaded with Rhodamine B and capped with an azopyridine derivative. The material was designed to show “zero delivery” and to display a cargo release in the presence of reductases and esterases, which are usually present in the colon, mainly due to intestinal microflora. The opening and cargo release of Rh‐Azo‐S in vitro studies were assessed and seen to occur in the presence of these enzymes, whereas no delivery was noted in the presence of pepsine. Moreover, Rh‐Azo‐S nanoparticles were used to study controlled Rhodamine B dye delivery in intracellular media. HeLa cells were employed for testing the “non”‐toxicity of nanoparticles. Moreover, delivery of the dye in these cells, through internalization and enzyme‐mediated gate opening, was confirmed by confocal microscopy. Furthermore, the nanoparticles capped with the Azo group and loaded with a cytotoxic camptothecin ( CPT ) were also prepared (solid CPT‐Azo‐S ) and used as delivery nanodevices in HeLa cells. When this solid was employed, the cell viability decreased significantly due to internalization of the nanoparticles and delivery of the cytotoxic agent.     

马尿酸分子印迹电化学传感器的制备及应用

采用超声法制备g-C3N4/NiO复合催化材料,将其滴涂在玻碳电极(GCE)表面构建g-C3N4/NiO/GCE催化电极。采用电聚合方法,以马尿酸为模板分子,邻苯二胺为功能单体构建M IP/g-C3N4/NiO/GCE传感器。采用时间-电流法对传感器制备条件优化。结果表明,复合催化材料对H2O2具有良好的催化效果。分子印迹传感器对马尿酸具有良好的选择性。在优化条件下,马尿酸质量浓度在0.05~2 mg/L范围内,电极电流响应与浓度呈良好的线性关系,检出限为7.1μg/L。将电极用于尿液中马尿酸的检测,回收率在87.3%~95.3%之间。     

供应和需求不确定条件下物流服务供应链能力协调研究

为解决物流能力供应和需求不确定环境下,物流服务集成商和供应商能力采购和投资的协调问题,建立了Stackelberg主从博弈下物流服务集成商和供应商的决策模型,提出了基于收益共享的能力采购费用补偿协调机制,给出了实现供应链协同以及帕雷托改进的合约参数设计和取值区间.数值分析进一步验证了该协调机制的有效性,以及供应和需求波动对决策双方行为的影响.研究结果表明,物流服务集成商通过调节合约参数取值能有效协调供应和需求随机环境下物流服务供应链的采购和投资风险.     

Voltage-Gated Metal-Enhanced Fluorescence

We demonstrate the influence of electrical current on the ability of surface plasmons to amplify fluorescence signatures. An applied direct current across Silver Island Films (SIFs) of low electrical resistance perturbs the fluorescence enhancement. For a given applied current, surface plasmons in just-continuous films are sparsely available for fluorophore dipole-coupling and hence the enhanced fluorescence is gated as a function of the applied current. For thicker, low resistance films, sufficient charge carriers are now present in the metal that metal-enhanced fluorescence (MEF) is perturbed to a lesser extent, induced surface plasmons readily formed on the surface by the close-proximity dipole.     

An Interpenetrated Framework Material with Hysteretic CO2 Uptake

A new, twofold interpenetrated metal–organic framework (MOF) material has been synthesized that demonstrates dramatic steps in the adsorption and hysteresis in the desorption of CO₂. Measurement of the structure by powder X‐ray diffraction (PXRD) and pair distribution function (PDF) analysis indicates that structural changes upon CO₂ sorption most likely involve the interpenetrated frameworks moving with respect to each other.     

Rules for selecting the parameters of Oustaloup recursive approximation for the simulation of linear feedback systems containing PID controller

Oustaloup recursive approximation (ORA) is widely used to find a rational integer-order approximation for fractional-order integrators and differentiators of the form s^v, v ∈ (−1, 1). In this method the lower bound, the upper bound and the order of approximation should be determined beforehand, which is currently performed by trial and error and may be inefficient in some cases. The aim of this paper is to provide efficient rules for determining the suitable value of these parameters when a fractional-order PID controller is used in a stable linear feedback system. Two numerical examples are also presented to confirm the effectiveness of the proposed formulas.     

高阶辛算法的稳定性与数值色散性分析

利用Maxwell方程的哈密尔顿函数,导出对应的欧拉-哈密尔顿方程.利用辛积分技术与高阶交错差分技术,建立求解三维时域Maxwell方程的高阶辛算法;结合电磁场中的物理概念,借助矩阵分析和张量分析理论,获得高阶时域方法及高阶辛算法的稳定性和数值色散性的统一处理新方法.用数值结果证实方法的正确性,与FDTD算法和其它时域高阶方法相比,高阶辛算法具有较大的计算优势,为电磁计算提供了新的途径.     

基于CIC的数字正交锁相放大器的甲烷检测实验研究

针对甲烷在大气中背景气体成分复杂、检测难度大、稳定性差等问题,本文基于可调谐二极管激光吸收光谱技术和波长调制光谱技术,将积分梳状滤波器与有限脉冲响应滤波器相结合应用于数字正交锁相放大器,开展大气中甲烷气体的痕量检测实验研究。实验表明,与传统的数字正交锁相放大器相比较,改进的数字正交锁相放大器提取的二次谐波信号的信噪比从38.61 dB提高到44.95 dB;将非线性迭代最小二乘法-极限学习机算法模型应用于甲烷气体浓度反演,与经典的最小二乘法相比较,其均方根误差减小了0.907;通过16组浓度步进实验测试,该系统的实际检测下限为1 ppm;在压力为600 mbar,温度为25℃,甲烷浓度为50 ppm进行3 h的长期稳定性测试,检测的甲烷浓度变化范围为49.6~50.3 ppm,其标准差为0.0921 ppm。当积分时间达到56 s时,该系统的理论检测极限为25.6 ppb。积分梳状滤波器和非线性迭代最小二乘法-极限学习机算法模型在红外气体检测方面具有较高的优越性和实用前景。