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81.
    
The halogen elimination of 1,2-diiodoethane (C2H4I2) and 1,2-diiodotetrafluoroethane (C2F4I2) serves as a model reaction for investigating the influence of fluorination on reaction dynamics and solute–solvent interactions in solution-phase reactions. While the kinetics and reaction pathways of the halogen elimination reaction of C2H4I2 were reported to vary substantially depending on the solvent, the solvent effects on the photodissociation of C2F4I2 remain to be explored, as its reaction dynamics have only been studied in methanol. Here, to investigate the solvent dependence, we conducted a time-resolved X-ray liquidography (TRXL) experiment on C2F4I2 in cyclohexane. The data revealed that (ⅰ) the solvent dependence of the photoreaction of C2F4I2 is not as strong as that observed for C2H4I2, and (ⅱ) the nongeminate recombination leading to the formation of I2 is slower in cyclohexane than in methanol. We also show that the molecular structures of the relevant species determined from the structural analysis of TRXL data provide an excellent benchmark for DFT calculations, especially for investigating the relevance of exchange-correlation functionals used for the structural optimization of haloalkanes. This study demonstrates that TRXL is a powerful technique to study solvent dependence in the solution phase.  相似文献   
82.
Phase behavior in liquid crystallization was studied for a series of liquid crystalline (LC) diblock copolymers consisting of rubbery amorphous and side-chain liquid crystalline components, poly(n-butyl acrylate) (PBA) and poly[11-(4′-cyanophenyl-4″-phenoxy)undecyl acrylate] (PLC), respectively, using a time-resolved small-angle X-ray scattering (SAXS) techniques, DSC and polarized optical microscopy (POM). The block copolymers used had three kinds of copolymer compositions, 44, 20 and 15 wt% of PLC compositions (BLC44, BLC20 and BLC15, respectively). BLC44 showed a smectic liquid crystalline structure. In the process of liquid crystallization for BLC44, the SAXS peak due to the microphase separation structure existing before liquid crystallization was changed continuously to be at a smaller angular side, and at almost the same time, a new peak appeared at a further smaller angular side and developed. The former peak disappeared with the development of liquid crystallization. The behavior of these SAXS peaks suggests that the microphase separation structure was changed discretely at the transition from isotropic to smectic and that two phases coexist in the early stage of the liquid crystallization. The coexistence of two peaks in the early stage of the liquid crystallization corresponded to the POM observation. In the isotropization process, coexistence of two phases was not observed. For BLC20 exhibiting a cylindrical structure in both isotropic and liquid crystalline states, the liquid crystalline structure was not smectic but probably nematic, and the spacing was changed continuously in liquid crystallization. No liquid crystallization was observed in SAXS, POM and DSC for BLC15. The orientation of smectic layers within lamellar domains was investigated using 2D-SAXS images. The smectic layer was aligned perpendicularly to the lamellar interface.  相似文献   
83.
Polypeptide hydrogels were prepared by cross-linking of hydrophobically-modified poly[N5-(2-hydroxyethyl) l-glutamine] having alkyl side chains –CnH2n+1. Chain length of the alkyl group was n = 8, 16, and 18, and their mole fractions in the polypeptide were varied in the range of 0.05–0.16. Shape memory ability of the prepared polypeptide hydrogels was investigated. After deformation at 60 °C, the hydrogel was cooled in order to fix the temporary deformed shape. It was found that crystallization of the alkyl side chains did not occur, and the fixation ability of the hydrogel at 0 °C was low. In the subsequent heating process, the deformed temporary shape spontaneously recovered to the original shape gradually with increasing temperature, in other words, the shape recovery ratio varied with depending on the recovery temperature. From these observations, it was proposed that the shape fixation of the polypeptide hydrogel was achieved by strong segregation of the hydrophobic alkyl chains at low temperature, and the shape recovery of the deformed hydrogel was accompanied by the gradual decrease of the segregation strength with the temperature increase.  相似文献   
84.
In this study, poly(methylmethacrylate) (PMMA)-based hybrid materials were prepared from reactive silica nanoparticles. These nanoparticles were obtained by the reaction of 2-(methacryloyloxy)ethyl isocyanate with colloidal silica dispersed in ethyl acetate, and they were copolymerized in various ratios with methyl methacrylate. Dynamic mechanical analysis (DMA), thermogravimetric analysis (TGA) and visible spectrometry were performed to evaluate the physical properties of the resulting hybrid materials. The PMMA-silica hybrid copolymers maintained high transparency, and their storage elastic modulus and surface hardness increased with increasing silica content. Moreover, in comparison with PMMA, the hybrid copolymers had greater heat resistance and lower volume contraction.  相似文献   
85.
影响啤酒酵母菌吸附铅离子条件的研究   总被引:1,自引:0,他引:1  
采用啤酒酵母自制生物吸附剂用于吸附金属铅离子,考察了pH值、反应时间、酵母浓度及金属离子浓度对啤酒酵母吸附Pb2 的影响.单因素实验结果表明,当pH值为5.0、溶液初始Pb2 浓度为80 mg·L-1、啤酒酵母的浓度为1.0 g·L-1、反应时间为0.5 h时,吸附效果最佳.通过正交实验,确定初始Pb2 浓度为反应过程中的显著因素.  相似文献   
86.
The improvement in the surface cleanliness of electroplated nickel by rinsing in alkaline electrolyzed water (AEW) was determined. When the nickel plated sample was rinsed with the AEW, it was found that the amount of residual sulfate ion on the surface of a sample decreased approximately by half compared to one rinsed only with de-ionized pure water. Because nanosize hydrogen bubbles are present in the AEW, and the zeta-potential has a negative value, we then surmised that the mechanism of rinsing was as follows: The sulfate ions are selectively absorbed on the nanosize colloidal hydrogen bubbles, or substituted for anions absorbed on the hydrogen bubbles. The sulfate ions absorbed on the nickel surface then become detached. The detached sulfate ions are absorbed on the surface of the hydrogen bubbles, and negatively charge the hydrogen bubbles. It can be considered that any detached sulfate ions do not re-adhere due to the electrical repulsion force of the negatively charged nickel surface. Thus the sample is efficiently rinsed.  相似文献   
87.
This paper describes a self-aligned fabrication process for diamond gated field emitter array (FEA). Utilizing the non-conformal coverage sputtering conditions of silicon oxide, an interesting “sphere on cone” structure is formed on diamond nano tip array, which is the key point of gate hole opening process. This structure causes shadowing at certain regions of side-wall during Ti / Au gate metal deposition. Removal of “sphere” by wet etching leads to the successful fabrication of a single crystalline diamond gated FEA. Scanning electron microscope observations reveal the fabrication of a uniform emitter array with tip radius of curvature (20 nm) and gate hole (1.4 μm). We also confirmed that no noticeable physical damage exists on tip. In field emission characteristics of the fabricated single crystal diamond gated FEA, gate voltage control of field emission current is realized.  相似文献   
88.
Molecular architectures built of inorganic cyanometalate building blocks provide variegated host structures with several organic guest molecules. The strategies to derive novel structures are presented briefly. The formation of a charge-transfer (CT) complex as the guest inside the cavity and the photochemistry of the CT complexes are discussed. The chemical pressure that the guest experiences inside the cavity is also discussed based on the vibrational spectroscopic results.  相似文献   
89.
The infrared chemiluminescence spectra of CO2 formed during steady-state CO+NO reaction over Pd(110) indicated that the temperature of the bending vibrational mode was much higher than that of the antisymmetric one at higher surface temperatures such as 800–850 K. Especially, in the high temperature range, more vibrationally excited CO2 was formed from CO+NO reaction than CO+O2 reaction. On the basis of the result, we propose the model structure of reaction intermediates for CO2 formation in CO+NO reaction, which is different from that in CO+O2 reaction.  相似文献   
90.
Rates of formation of gases, oils, asphaltenes and preasphaltenes during non-solvent liquefaction of coal over molten tin catalyst have been measured. A probable reaction scheme and the rate constants for the pathways comprising the scheme have been presented. The results show that the catalyst greatly accelerates the conversion of preasphaltenes to asphaltenes. It also accelerates two other reactions, i.e., coal to preasphaltenes and coal to asphaltenes. By contrast, the catalyst does little to promote gasification and formation of oils.  相似文献   
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