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41.
A. Shaira 《Journal of Coordination Chemistry》2015,68(17-18):3013-3031
A series of dinuclear Pt(II) complexes bridged with polyethyleneglycol ether of the type [ClPt(tpy)O(CH2CH2O)n(tpy)PtCl]Cl2 where n = 1 (Ptdteg), 2 (Ptdtdeg), 3 (Ptdtteg), 4 (Ptdttteg), and linker-free complex, (Ptdt) (where tpy = 2,2′:6′,2″-terpyridine), were synthesized and characterized to investigate the role of bridging polyethyleneglycol ether linker on the substitution reactivity of dinuclear Pt(II) complexes. Substitution reactions were studied using thiourea nucleophiles, viz. thiourea (TU), 1,3-dimethyl-2-thiourea (DMTU), 1,1,3,3-tetramethyl-2-thiourea (TMTU) under pseudo-first-order conditions as a function of concentration and temperature by conventional stopped-flow reaction analyzer. The reactions gave single exponential fits following the rate law kobs = k2[Nu]. Introduction of polyethyleneglycol ether linker decreases the electrophilicity of the platinum center and the whole complex. The results obtained indicate that the rate of substitution is controlled by both electronic and steric hindrance which increases with the length of the linker. Experimental results are supported by density functional theory calculations and structures obtained at B3LYP/LANL2DZ level. The order of the reactivity of the nucleophiles is TU > DMTU > TMTU. The magnitude and the size of the enthalpy of activation and entropy of activation support an associative mode of mechanism, where bond formation in the transition state is favored. 相似文献
42.
Teemu Näykki Timo Sara-Aho Tero Väisänen Ivo Leito 《International journal of environmental analytical chemistry》2015,95(1):1-15
A novel tool for the investigation of stability of total mercury in water samples is presented. The study focuses on the application of enriched 196Hg stable isotopic reagent for the stability studies. Natural abundance of 196Hg in water samples is only 0.15%. Thus, the use of the 196Hg isotope spike represents a major advantage, when it can be assumed that all the measured isotope is the same as is accurately added by the analyst, and the change in its mass concentration can be followed simply and reliably. Tests were carried out with industrial waste water and two type of the natural water. Cold vapour (CV) inductively coupled plasma mass spectrometer (ICP-MS) technique was applied for the mercury measurements. Monitoring was continued for approximately 100 days. It is commonly advised that the measurement for total mercury in water samples should be carried out within 14 days. In this study the samples were observed to be stable for more than three months, if they were stored at a temperature of 4–6°C. The results of this stability study were in line with the guidance presented in EPA standard 1631. However, the samples were noticed to be stable for a much longer time than is presented in the standard method ISO 17852. 相似文献
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44.
针对水力压裂过程中采用的人工应力遮挡控制缝高技术,通过室内物理模拟实验,在转向剂浓度一定的条件下考虑携带液与地层压差、渗流量、时间等因素,采用电测法对人工岩芯表面应变进行了测试;利用非线性有限元方法对裂缝尖端应力进行计算,研究了转向剂形成人工应力遮挡的作用效果。结果表明采用转向剂可以建立3~4MPa的人工应力遮档,对采用转向剂的压裂设计和施工参数提出了建议。 相似文献
45.
建筑物内火灾烟羽流和顶蓬射流诱发的空气运动盐水模拟实验研究 总被引:3,自引:0,他引:3
盐水在清水中的扩散与火灾烟气在空气中的蔓延相似,因而可用盐水的扩散来模拟火灾烟气的蔓延;同样地,由于盐水的扩散而导致的环境清水的运动也可用来模拟烟气蔓延诱发的空气运动。基于这一原理,本文用实验的方法,研究了建筑物内初起火灾产生的烟羽流和顶蓬射流所诱发的空气运动,并对走廊空气层生长规律和运动特性进行了初步的测量和分析。所得结果基本合理,对建筑物通风排烟及疏散通道设计有帮助,从而为建筑火灾环境空气的运动的实验研究开辟了新的思路,也为火灾区域模拟提供了实验依据 相似文献
46.
Next Generation Science Standards (NGSS) science and engineering practices are ways of eliciting the reasoning and applying foundational ideas in science. As research has revealed barriers to states and schools adopting the NGSS, this mixed‐methods study attempts to identify characteristics of professional development (PD) that will support NGSS adoption and to improve teacher readiness. In‐service science teachers from across the nation were targeted for the survey and responses represented 38 states. Research questions included: How motivated and prepared are in‐service 7–12 teachers to use NGSS science and engineering practices? What is the profile of 7–12 in‐service teachers who are motivated and feel prepared to use NGSS science and engineering practices? The study revealed that teachers identified engineering most frequently as a PD need to improve their NGSS readiness. High school teachers rated themselves as more prepared than middle school and all teachers who use Modeling Instruction expressed higher NGSS readiness. These findings and their specificity contribute to current knowledge, and can be utilized by districts in selecting PD to support teachers in preparing to implement the NGSS successfully. 相似文献
47.
Monika Karpierz Jan Suchanicz Krzysztof Konieczny Dorota Sitko Pascal Marchet Urszula Lewczuk 《Phase Transitions》2015,88(7):662-667
The 0.5K0.5Bi0.5TiO3–0.5PbTiO3 ceramics were prepared by following a standard solid-state method. The Raman, thermal and dielectric properties of these ceramics were investigated. The X-ray measurements showed that samples have single perovskite-type structure with tetragonal symmetry. Dielectric study revealed that the dielectric behaviour of the investigated ceramics is rather of normal ferroelectrics with large thermal hysteresis. The transition temperature observed by means of differential scanning calorimetry measurements is in good agreement with that obtained from dielectric study. 相似文献
48.
采用RNG k-ε 湍流模型对超临界CO2流体在内径为4 mm, 长度2000 mm, 节距为10 mm, 曲率为0.1的水平螺旋管内的冷却换热进行了数值模拟.研究了质量流量、热流量以及压力对换热系数的影响, 并和超临界CO2在水平直管内的冷却换热进行了对比.研究结果表明, 超临界CO2在水平螺旋管内流动产生的二次流强于水平直管内的二次流, 前者的换热系数大于后者; 换热系数随质量流量的增加而增大; 在似气体区, 换热系数随着热流量的增加而增大, 而在似液体区, 热流量对换热系数几乎没有影响; 换热系数峰值点随着压力的升高而下降, 并向高温区偏移. 相似文献
49.
增殖剂球床是聚变堆或混合堆产氚包层可选结构之一,准确把握增殖剂球床中载带气体的流动特性有助于提高对球床载氚过程的认识并优化包层设计。采用离散元程序PFC3D模拟增殖剂小球的填充行为,在球床内不同位置随机截取不同尺寸的控制体,利用布尔运算中的"差集"得到孔隙范围,建立孔隙分布的三维几何模型,进一步划分网格并用计算流体力学(CFD)方法求解,得出控制体上单位长度的压降以及单元体内的速度分布特征,计算结果发现载带气体速度分布与γ分布很类似,且只要选取恰当的控制体,通过计算流体力学方法可以较好地分析整个球床孔隙内流体的流动,有利于进一步研究载氚及相关过程。 相似文献
50.
Amit S. Nagare Arpan Manna Pramod D. Sonawane Anil Kumar 《Journal of Physical Organic Chemistry》2015,28(11):665-673
Prevailing classification of salts based on their effect in solubility and stability of proteins in aqueous solution predicts that tetraalkylammonium salts, guanidinium chloride (GnCl), LiClO4 act as salting‐in (S/I) and LiCl, NaCl act as salting‐out (S/O) in aqueous conditions. In the same context the behaviour of GnCl, LiClO4 and LiCl are contradictory in polar solvents like ethylene glycol and formamide. In these solvents, expected salt effect shows just opposite nature from their usual expectation. However, in the aqueous solution salts like tetraalkylammonium halide (R4NX, R = alkyl group, X = Br group) behave like salting‐in salts. The physicochemical origin of the salting in effect of R4NX type of salts has been discussed elaborately in the present work. The role of cations in terms of substitution of various alkyl groups on R4NX has been systematically presented here on the basis of experimental kinetic and thermodynamic studies. The abnormal behaviour of R4NX salts in aqueous solution has also been explained by the Setschenov equation (ks) and Δμsolvation values, which highlights their individual nature out of common properties of R4NX. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献