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111.
Hong-Tao Fan Yan Lu Ai-Juan Liu Bing Jiang Hua Shen Cong-Cong Huang Wen-Xiu Li 《Analytica chimica acta》2015
A diffusive gradients in thin films (DGT) device for the analysis of free Cd(II) species, based on Cd(II) ion-imprinted sorbent (IIS) as the binding agents and commercial polyethersulfone membrane (PES) as diffusion layer, was developed (PES/IIS-DGT). DGT time-series experiments showed that the mass of free Cd(II) species accumulated by PES/IIS-DGT was linear vs. time (R2 = 0.9953) and the concentration of free Cd(II) species by PES/IIS-DGT was in good agreement with the total dissolved concentrations of free Cd(II) species in simple synthetic solutions where free ionic species dominated. PES/IIS-DGT performance was independent in the range of pH 4.5–7.5 and ionic strength range from 1.0 × 10−3 to 0.7 mol L−1. The measurement of free Cd(II) species in synthetic solution containing different concentrations of ligands by PES/IIS-DGT showed an excellent agreement with the value measured by Cd(II) ion selective electrodes (Cd-ISE), indicating that PES/IIS-DGT method is more suitable than Cd-ISE for the measurement of low concentration of free Cd(II) species due to the enrichment of IIS for the analytes. 相似文献
112.
在磁共振脉冲优化领域,优化脉冲普遍存在幅值过大的问题,这极大地限制了优化脉冲的使用范围。为了限制优化脉冲的幅值,扩大其应用范围,提出了一种基于L-BFGS-B数值算法的脉冲优化设计方法。首先基于Liouville-von Neuman方程,使用最优控制思想构建优化模型;然后使用L-BFGS-B算法,在限制幅值的条件下对优化模型进行数值迭代求解;最后以脉冲的激发效率以及激发轮廓的均匀性作为衡量优化脉冲优劣的标准对该方法进行仿真和实验验证。结果表明,采用该方法获得的优化脉冲在幅值被限制的前提下,仍能获得较传统磁共振脉冲更好的共振激发效果,进而增强信号的灵敏度,提高图像的质量。 相似文献
113.
For the first time, a diffusive gradients in thin films (DGT) device using molecularly imprinted polymer (MIP) as the binding agent and nylon membrane (NM) as the diffusive layer (NM-MIP-DGT) has been developed for sampling 4-chlorophenol (4-CP) in water. The MIP was prepared by precipitation polymerization with methacrylic acid as monomer and ethyleneglycoldimethacrylate as cross-linker. The diffusion coefficient of 4-CP through NM was obtained to be 0.788 ± 0.040 μ cm2 s−1 by diffusion cell method. The ratio was 1.01 ± 0.05 (mean ± standard deviation) for the concentration of 4-CP sampled by NM-MIP-DGT and analyzed by HPLC method to the total concentration of 4-CP in the synthetic solution where free 4-CP species dominated. The results showed that NM-MIP-DGT could sample 4-CP in synthetic solution accurately. The performance of NM-MIP-DGT for sampling 4-CP was independent of pH in the range of 3–7 and ionic strength in the range of 0.0001–0.1 mol L−1 NaCl solution. The concentration of free form of 4-CP sampled by NM-MIP-DGT decreased with the increasing concentration of dissolved organic carbon in different water samples due to the electrostatic interaction of natural organic compounds with 4-CP. 1.8 mg L−1 of the free form of 4-CP was determined by HPLC which was sampled by NM-MIP-DGT in an intermediate untreated industrial effluent. The NM-MIP-DGT can be a potential passive tool for sampling the free form of 4-CP in water. 相似文献
114.
Yong-Hyun Kim Ki-Hyun Kim Jan E. Szulejko Min-Suk Bae Richard J.C. Brown 《Analytica chimica acta》2014
For the quantitative analysis of ‘compounds lacking authentic standards or surrogates’ (CLASS) in environmental media, we previously introduced an effective carbon number (ECN) approach to develop an empirical equation for the prediction of their response factor (RF). In this research, a series of laboratory experiments were carried out to benchmark the reliability of an ECN approach for sorbent tube/thermal desorption/gas chromatography (GC)/mass spectrometry (MS) applications. First, the ECN values were determined using external calibration data from 25 reference volatile organic compounds (VOCs) using two MS dectectors (quadrupole (Q) and time-of-flight (TOF)). Then, a certified standard mixture of 54 VOCs was analyzed by each system as a simulated unknown sample. The analytical bias, assessed in terms of percentage difference (PD) between the certified and ECN-predicted mass values, averaged 19.2 ± 16.1% (TOF-MS) and 28.2 ± 27.6% (Q-MS). The bias using a more simplified carbon number (CN)-based prediction increased considerably, yielding 53.4 ± 53.3% (TOF-MS) and 61.7 ± 81.3% (Q-MS). However, the bias obtained using the ECN-based prediction decreased significantly to yield average PD values of 9.84 ± 7.28% (TOF-MS) and 16.8 ± 8.35% (Q-MS), if the comparison was limited to 26 (out of 54) VOCs with CN ≥ 4 (i.e., 25 aromatics and hexachlorobutadiene). 相似文献
115.
Jonas Boström Valera Veryazov Francesco Aquilante Thomas Bondo Pedersen Roland Lindh 《International journal of quantum chemistry》2014,114(5):321-327
An algorithm for computing analytical gradients of the second‐order Møller–Plesset (MP2) energy using density fitting (DF) is presented. The algorithm assumes that the underlying canonical Hartree–Fock reference is obtained with the same auxiliary basis set, which we obtain by Cholesky decomposition (CD) of atomic electron repulsion integrals. CD is also used for the negative semidefinite MP2 amplitude matrix. Test calculations on the weakly interacting dimers of the S22 test set (Jure?ka et al., Phys. Chem. Chem. Phys. 2006, 8, 1985) show that the geometry errors due to the auxiliary basis set are negligible. With double‐zeta basis sets, the error due to the DF approximation in intermolecular bond lengths is better than 0.1 pm. The computational time is typically reduced by a factor of 6–7. © 2013 Wiley Periodicals, Inc. 相似文献
116.
117.
S. Hosseini M.R. Pouryayevali 《Nonlinear Analysis: Theory, Methods & Applications》2011,74(12):3884-3895
In this paper, a notion of generalized gradient on Riemannian manifolds is considered and a subdifferential calculus related to this subdifferential is presented. A characterization of the tangent cone to a nonempty subset S of a Riemannian manifold M at a point x is obtained. Then, these results are applied to characterize epi-Lipschitz subsets of complete Riemannian manifolds. 相似文献
118.
Serge Gratton Ehouarn Simon David Titley‐Peloquin Philippe L. Toint 《Numerical Linear Algebra with Applications》2021,28(1)
We investigate the method of conjugate gradients, exploiting inaccurate matrix‐vector products, for the solution of convex quadratic optimization problems. Theoretical performance bounds are derived, and the necessary quantities occurring in the theoretical bounds estimated, leading to a practical algorithm. Numerical experiments suggest that this approach has significant potential, including in the steadily more important context of multiprecision computations. 相似文献
119.
土壤有机质是土壤肥力的物质基础,其含量的高低是评价土壤肥力的重要标志。土壤有机质组分根据其溶解性可分为胡敏素(HM)、胡敏酸(HA)、富里酸(FA),不同组分的肥力特性差异显著,因此,土壤有机质组分数据可更加全面、客观的反映土壤肥力状况。传统土壤土壤有机质及组分的测定工序繁杂,效率低下且时效性差,大量研究表明高光谱技术能有效提高土壤属性的检测效率并降低测试成本,但关于可见光-近红外、中红外光谱检测土壤有机质组分的报道鲜见。为了探索中红外光谱及可见光-近红外-中红外组合光谱对土壤有机质组分检测的可行性,并对比有机质单一光谱模型与有机质不同组分的组合光谱模型的预测精度,以南疆地区农田土壤为例,在阿克苏及和田地区共采集93个土样,进行有机质、胡敏素、胡敏酸、富里酸含量及光谱数据的测定。其次,利用可见-近红外(VNIR)、中红外(MIR)及其组合光谱(VNIR-MIR)三种光谱数据集,采用偏最小二乘(PLSR)、支持向量机(SVM)、随机森林(RF)三种建模方式对土壤有机质、胡敏素、胡敏酸、富里酸含量进行组合模型分析预测。结果表明:(1)土壤有机质及各组分均与光谱反射率有较好的相关性,土壤有机质及组分在MIR谱段的特征波段数量明显多于VNIR谱段。(2)有机质最优预测模型的模式为VNIR-MIR-RF,该模型的决定系数R2为0.90;胡敏素与胡敏酸最优预测模型的模式均为VNIR-RF模型,R2均为0.92;富里酸最优预测模型的模式为MIR-RF模型,R2为0.94。(3) 基于胡敏素、胡敏酸和富里酸的有机质组合光谱模型的预测精度明显高于有机质单一光谱模型,两种模型的R2分别为0.93和0.90。实现了土壤有机质组分的高效快速反演,且基于有机质组分的组合模型提高了土壤有机质预测精度,为南疆地区大尺度土壤肥力的鉴定与精准施肥提供重要的参考价值。 相似文献
120.
中国散裂中子源一期工程的直线加速器,共有8套数字化射频低电平控制单元,射频低电平的本地控制属于EPICS的异构系统,无法直接与EPICS客户端进行通信。通过在射频低电平本地控制上位机程序中嵌入一个C#类型的EPICS服务器程序,实现了使用EPICS客户端对射频低电平系统的远程控制, 从而把射频低电平控制系统接入基于EPICS框架的控制系统中。直线射频低电平远程控制投入在线运行以来,运行稳定可靠。 相似文献