A kinetic and mechanistic study of dinuclear Pt(II) 2,2′:6′,2″-terpyridine compounds bridged with polyethyleneglycol ether flexible linkers

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 k_obs = 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.     

N-支套索冠醚异羟肟酸的合成及其钴(II)配合物的氧加合性能

由乙二胺四乙酸二酐和多缩乙二醇出发,合成了一系列具有N-支套索冠醚结构的二异羟肟酸配体(L1H2~L4H2)及其钴(II)配合物(Co L1~Co L4),以IR,1H NMR,MS和元素分析进行结构表征。测定在不同温度下Co L1~Co L4的氧加合常数In KO2和热力学参数ΔH0、ΔS0,研究了氮杂冠醚环的大小对配合物氧加合性能的影响。     

甲氧基多溴联苯醚色谱相对保留时间的QSRR研究

基于有机化合物定量结构与色谱相对保留时间的关系,对26个甲氧基多溴联苯醚化合物进行了B3LYP/6-31G*水平上的结构优化,并在优化结构基础上进行了分子连接性指数和量子化学结构参数的提取。应用SPSS统计软件对甲氧基多溴联苯醚化合物的色谱相对保留时间与分子连接性指数进行了多元线性回归(MLR)。结果表明,三阶类分子连接性指数可以很好地表达甲氧基多溴联苯醚化合物色谱相对保留时间与结构描述符之间的定量关系。用外部测试集的方法对模型预测能力进行了验证,结果表明:所建立的QSRR模型具有较强的稳健性和预测能力。     

Design of TiO2@graphene nanosheets with rough surface and its reinforcement to polyarylene ether nitriles

The interfacial interaction is extremely important when dealing with filler‐reinforced polymer materials. Herein, in order to improve the interfacial interaction with the polyarylene ether nitriles (PEN) matrix, a three‐dimensional rough structure was designed. First, needle‐like TiO₂ nanocrystals were grown on each surface of the graphene. Morphology analysis proved that rough TiO₂ nanocrystals were coated on the graphene nanosheets. Then, TiO₂@graphene/PEN composites were fabricated to investigate the filler–matrix interaction. Thereafter, the different polymer chains could be interlocked by the TiO₂ “needles” when the rough TiO₂@graphene was embedded into the polymer resin. The surrounding PEN polymer chains (work as ropes) could tie to the “needles” (work as wood pile). That is to say, the effective polymer chain length was greatly lengthened, resulting in the improvement of interfacial interactions and mechanical properties. Most importantly, the morphology, mechanical and rheological tests of the composites also proved the improvement of interfacial interactions and mechanical properties. Copyright © 2015 John Wiley & Sons, Ltd.     

Fabrication of thermo-responsive polymer nanocomposites for smart window applications

Abstract

Thermo-responsive polymers have attracted much attention in recent years because they can provide a variety of applications for smart devices, but the lack of sufficient mechanical properties and late response rate of the polymers limit their applications. In the current work, we fabricated polymer nanocomposites made from poly(vinyl methyl ether) and nanofillers with photothermal conversion property such as graphene oxide, antimony tin oxide nanoparticles, and silver nanoplates. The prepared nanocomposites showed rapidly reversible and reliable transparent-opaque transitions during the repeated heating and cooling processes, suggesting that they can be applied to smart window applications.     

Diffusion Limitations and Translocation Barriers in Atomically Thin Biomimetic Pores

Ionic transport in nano- to sub-nano-scale pores is highly dependent on translocation barriers and potential wells. These features in the free-energy landscape are primarily the result of ion dehydration and electrostatic interactions. For pores in atomically thin membranes, such as graphene, other factors come into play. Ion dynamics both inside and outside the geometric volume of the pore can be critical in determining the transport properties of the channel due to several commensurate length scales, such as the effective membrane thickness, radii of the first and the second hydration layers, pore radius, and Debye length. In particular, for biomimetic pores, such as the graphene crown ether we examine here, there are regimes where transport is highly sensitive to the pore size due to the interplay of dehydration and interaction with pore charge. Picometer changes in the size, e.g., due to a minute strain, can lead to a large change in conductance. Outside of these regimes, the small pore size itself gives a large resistance, even when electrostatic factors and dehydration compensate each other to give a relatively flat—e.g., near barrierless—free energy landscape. The permeability, though, can still be large and ions will translocate rapidly after they arrive within the capture radius of the pore. This, in turn, leads to diffusion and drift effects dominating the conductance. The current thus plateaus and becomes effectively independent of pore-free energy characteristics. Measurement of this effect will give an estimate of the magnitude of kinetically limiting features, and experimentally constrain the local electromechanical conditions.     

Simultaneous measurement of methyl tert‐butyl ether and tert‐butyl alcohol in human serum by headspace solid‐phase microextraction gas chromatography–mass spectrometry

The abundant production of methyl tert‐butyl ether (MTBE) and its widespread use have led to an increase in the potential for human exposure. This work described a simple, fast, sensitive, reliable and low‐cost method for the simultaneous measurement of MTBE and its metabolite, tert‐butyl alcohol (TBA) in human serum by headspace solid‐phase microextraction gas chromatography–mass spectrometry. Extraction conditions were optimized and 40 °C, 10 min, 250 rpm and 0.3 g NaCl for a 1 mL sample were the optimal conditions. This method showed good analytical performance in terms of sensitivity with limits of detection in serum (1 mL) of 0.03 µg/L for MTBE and 0.05 µg/L for TBA, accuracy (mean recovery values) from 75.8% to 85.8%, precision (relative standard deviations) <10% and sample stability (biodegradation) <10% after 28 days. A verification experiment proved the reproducibility and stability of this method as well. Finally the method was used to detect 212 specimens, and the internal dose levels for MTBE in human serum were presented in China. Copyright © 2015 John Wiley & Sons, Ltd.     

Formation of polyketone particle structure by hexafluoroisopropanol solvent evaporation and effects of plasticizer addition

Few solvents are capable of dissolving polyketones (PKs). 1,1,1,3,3,3‐Hexafluoro‐2‐propanol (hexafluoroisopropanol, HFIP) is a better solvent than trifluoroethanol and m‐cresol. When HFIP was evaporated from a PK/HFIP solution, a porous cast‐film with a microparticle structure was formed because the isotactic PKs adopted a helical conformation, and convection during evaporation of the high polarity and low‐boiling‐point HFIP caused aggregation and rolling of the polymer molecules. The addition of plasticizer suppressed particle formation, improving the surface structure and mechanical properties of the film. In particular, the dielectric properties of the film improved significantly. This will enable PKs, which are rigid insulating materials, to be used as dielectric materials, broadening their range of applications. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 887–892     

Analysis of F-53B,Gen-X,ADONA, and emerging fluoroalkylether substances in environmental and biomonitoring samples: A review

The persistent, bioaccumulative, and toxic properties of certain per- and polyfluoroalkyl substances (PFAS) raise concerns for environmental and human health. This has led to the gradual phase-out from production and commerce of some legacy PFAS. Fluoroalkylether compounds (ether-PFAS) are among the fluorinated alternative chemicals that are beginning to be reported in impacted and background environments. Extensive monitoring activities were conducted since 2015–2019 to bridge knowledge gaps on the environmental fate and effects of ether-PFAS including F-53B (6:2 chlorinated polyfluoroalkyl ether sulfonate [6:2 Cl-PFAES] and 8:2 Cl-PFAES), Gen-X (hexafluoropropylene oxide dimer acid [HFPO-DA]), and ADONA (dodecafluoro-3H-4,8-dioxanonanoate). In recent years, advances in nontarget screening using high-resolution mass spectrometry have revealed the identities of other infrequently monitored ether-PFAS. In this critical review, we provide an up-to-date inventory of the structures of ether-PFAS discovered in the recent literature. Their environmental occurrence, fate, and effects are discussed on a comparative perspective with some legacy PFAS such as perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS). Information on the methods employed for the quantitative and semi-quantitative analysis of ether-PFAS is also provided, including sample preparation and mass spectrometry analysis, analytical performance, and limitations. In particular, the compiled database of MS/MS fragment ions (n = 111) can be useful in spectrum interpretation of novel ether-PFAS. The concluding remarks open on possible research avenues and the challenges that remain to be addressed.     

Novel organometallic chalcones functionalized with a crown ether fragment as optical ion chemosensors

We previously reported the synthesis and characterization of new organometallic chalcones derived from ferrocene, cyrhetrene and cymantrene functionalized with a benzo‐15‐crown‐5 fragment. The ferrocene and cyrhetrene chalcones have been investigated as chemosensors for metal ions with optical response in acetonitrile. Several metal ions were selected considering the diameter of the cavity and the charge‐to‐radius ratio of the cation. The stoichiometry of the complexes was determined using Job's method. It was found that Na⁺ and Ca²⁺ complexes have a 1:1 stoichiometry while a 2:1 (metaloligand‐to‐cation) stoichiometry was determined for Ba²⁺ and Pb²⁺ complexes. The association constants were calculated according to the stoichiometry of the complex and the results showed that they are directly affected by the electron‐withdrawing nature of the organometallic fragment. Moreover, complexes of ferrocenyl chalcone have larger association constants than those of the cyrhetrenyl analogue. This experimental observation is consistent with the electronic properties of the ferrocenyl fragment.