用选择离子流动管质谱测定汽油和柴油蒸汽成分

采用选择离子流动管质谱(SIFT／MS)装置，以H30^ 、N0^ 为初始离子对汽油和柴油蒸汽进行了研究，质谱分析表明，汽油和柴油主要由C—H化合物组成，包括烷烃、环烷烃、烯烃、炔烃、二烯烃以及芳香烃。在这几种成分中，烷烃都占有最大的比例；汽油蒸汽和柴油蒸汽最大的区别是柴油蒸汽中长链大分子的挥发性C—H化合物所占的比例远远高于汽油蒸汽。文中还给出了以H30^ 、N0^ 为初始离子所得到的汽油蒸汽的质谱图，以及汽油、柴油蒸汽中各种成分的定量分析结果。     

Conducting polymer memory devices based on dynamic doping

Molecular electronic junctions consisting of a 20 nm thick layer of polypyrrole (PPy) and 10 nm of TiO2 between conducting layers of carbon and gold were investigated as potential nonvolatile memory devices. By making the polymer layer much thinner than conventional polymer electronic devices, it is possible to dynamically oxidize and reduce the polypyrrole layer by an applied bias. When the electrode in contact with the PPy is biased positive, oxidation of the PPy occurs to yield a conducting polaron state. The junctions exhibit a large increase in conductance in response to the positive bias, which is reversed by a subsequent negatively biased pulse. Switching between the conducting and nonconducting state can occur for pulses at least as short as 10 micros, and the conducting state persists after a positive bias pulse for at least 1 week. The read/write/read/erase cycle may be repeated for at least 1700 cycles, although with an error rate of approximately 3% due mainly to an incomplete "erase" step. The speed and retention of the PPy/TiO2 junctions are far superior to those of the analogous fluorene/TiO2 devices lacking the polymer, and the conductance changes are absent if SiO2 is substituted for TiO2. The observations are consistent with "dynamic doping" of the solid-state polymer layer, with the possible involvement of adventitious mobile ions. Although the speed of the current polymer/TiO2 junctions is slower than commercial dynamic random access memory, their retention is approximately 5 orders of magnitude longer.     

Direct imaging and probing of the p-n junction in a planar polymer light-emitting electrochemical cell

A vast array of semiconductor applications relies on the ability to dope the materials by the controlled introduction of impurities in order to achieve desired charge carrier concentration and conduction type. In this way, various functional metal/semiconductor or semiconductor/semiconductor junctions can be constructed for device applications. Conjugated polymers are organic semiconductors that can be electrochemically doped to form a dynamic p-n junction. The electronic structure and even the existence of such a polymer p-n junction had been the subject of intense scrutiny and debate. In this work, the formation of the world's largest frozen polymer p-n junction and its light-emission are visualized. With a pair of micromanipulated probes, we mapped the potential distribution of the p-n junction under bias across the entire interelectrode gap of over 10 mm. Site-selective current-voltage measurements reveal that the polymer junction is a graded p-n junction, with a much more conductive p region than n region.     

Theory of relaxation properties of two‐dimensional polymer networks, 2. Local dynamic characteristics

Using normal mode transformation obtained in Part 1 of this series^[1], the exact analytical expressions for the mean‐square displacements of junctions and non‐junction beads, the autocorrelation functions of the end‐to‐end chain vectors between neighboring junctions, and those of subchain vectors of a two‐dimensional regular network consisting of "bead and spring" Rouse chains are obtained. Contributions of intra‐ and interchain relaxation processes to the local dynamic characteristics considered are compared. The time behavior of dynamic quantities obtained is estimated for different scales of motions. The possibility of describing long‐time relaxation of a two‐dimensional network by a simplified coarse‐grained network model is demonstrated. It is shown that the local relaxation properties of a two‐dimensional polymer network (as well as a three‐dimensional network) on scales smaller than the average distance between cross‐links are very close to those of a single Rouse chain. The large‐scale collective relaxation of the polymer networks having a two‐dimensional connectivity differs considerably from that of the three‐dimensional networks.     

Light modulation and coupling and rugby‐shaped resonators based on polymer fiber waveguide junctions

We report a systematic study of the dependence of the output efficiency and scattering efficiency on crossing angle, guided wavelength, and junction size in polymer nanofiber waveguide junctions. The junctions were assembled by using poly(trimethylene terephthalate) nanofibers (PNFs) with diameters of 200–800 nm under an optical microscope with the assistant of micromanipulators. A Chinese character and an SU pattern based the PNF junction technique have been demonstrated, moreover, the junction technique has also been expanded to various elastic substrates instead of glass substrate with high robustness. To further demonstrate the ability of modulating light of using the junction technique, we fabricated rugby‐shaped microresonators based on the polymer fiber junction, which exhibited high Q factor up to 10⁵. Furthermore, the microresonators can incorporate dyes or quantum dots into them, acting as active devices. We believe that the polymer fiber junction technique would provide a versatile platform for investigating light modulation or light matter interaction in various cavities with different configuration. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 833–840     

EPR spin probe study of polymer associative systems

Molecular dynamics of polyacrylamide gels, polymeric micelles and hydrogel of polyacrylic acid and macrodiisocyanate was investigated by the ESR spectroscopy of spin probes. The local mobility in network junction of polyacrylamide gels is found to be essentially slower than that in the micelles created by the low molecular weight detergents and does not depend on the amount and length of hydrophobic groups (C9 or C12) in the polymer chain. The immersion of 10-30 mol.% of ionic monomers into the polymer chain (sodium acrylate) influences insufficiently on the local mobility of network junctions. In aqueous solutions, polystyrene-block-poly-(N-ethyl-4-vinylpyridinium bromide) block copolymers create polymeric micelles. The local mobility in the polystyrene core of the micelles is about twice as much as that in the solid polystyrene. Partially swellable polymer network in aqueous solutions was synthesized from polyacrylic acid and macrodiisocyanate. The local mobility in hydrophobic regions of the gel is substantially lower than that in the hydrophilic regions. It was concluded that the hydrophobic and hydrophilic regions and the local dynamics of them dictate practical application of the polymer associative systems.     

Self-assembly of organic-inorganic hybrid materials constructed from eight-connected coordination polymer hosts with nanotube channels and polyoxometalate guests as templates

Two polyoxometalate-templated organic-inorganic hybrid porous frameworks, namely, [Cu2(H2O)2(bpp)2Cl][PM12O40].approximately 20H2O (for 1, M = W; for 2, M = Mo; bpp = 1,3-bis(4-pyridyl)propane), were self-assembly obtained and structurally determined by elemental analyses, inductively coupled plasma analyses, infrared spectroscopy, and single-crystal X-ray diffraction analyses. Single-crystal X-ray analysis of these crystals revealed that both of the structures are constructed from eight-connected three-dimensional coordination polymer hosts [Cu2(H2O)2(bpp)2Cl]n(3n+) and ball-shaped Keggin-type guests [PM12O40]n(3n-) as templates. The polymer hosts resulted from a bcc-type framework with nanotubes, and the nanotubes can be regarded as a tetra-stranded helix structure. Furthermore, compounds 1 and 2 exhibit photoluminescent properties at ambient temperature, and the compound 2 bulk-modified carbon paste electrode ( 2-CPE) displays good electrocatalytic activity toward the reduction of nitrite.     

A chiral self-catenated dual-ligand coordination polymer constructed from three distinct interwoven helical motifs interconnected by one-dimensional chains

Hydrothermal synthesis has afforded [Co3(oba)3(bpmp)2]n [oba = oxybis(benzoate), bpmp = bis(4-pyridylmethyl)piperazine], a chiral coordination polymer possessing an aesthetic self-catenated three-dimensional structure with an unprecedented 8-connected uninodal 4(4)5(17)6(7) topology. The network is formed by the junction of {Co3O2} clusters into three different homochiral interlocked helical motifs, linked by one type of "infinite" chain pattern. Antiferromagnetic exchange is observed within the {Co3O2} clusters.     

Electronic absorption spectra of the protonated polyacetylenes H2CnH+ (n = 4, 6, 8) in neon matrixes

Electronic absorption spectra of the protonated polyacetylenic chains H2CnH+ (n = 4, 6, 8) and the neutral H2C8H have been observed in 6 K neon matrixes after mass selection. The wavelength of the H2CnH+ electronic transitions depends quasi-linearly on n, typical of carbon chains. The origin band is at 286.0, 378.6, and 467.6 nm for n = 4, 6, and 8, respectively. Two ground-state vibrations of H2C4H+ in the IR absorption spectrum were also detected. On the basis of the spectroscopic trends and the assignment of the vibrational frequencies in the ground and excited electronic states, it is concluded that the H2CnH+ species are C(2v) linear carbon chains with one H atom on one end and two on the other.     

Synthesis and amphiphilic properties of S-alkylthiopentonolactones and their pentitol derivatives

The amphiphilic properties of S-alkylthiopentono-1,4-lactones (D-ribono-, D-arabinono-, D-xylono-) and corresponding pentitol derivatives with the general formula Su-SR (R=CnH2n+1) are studied. It was shown that CMC, surface area, CPP, and pC20 are influenced by the following structural parameters: alkyl chain length, the number of free hydroxyls, cyclic or acyclic Su structure, and alditol configuration.     

饱和烷烃分子C_nH_(2n+2)(n=4-6)的电子动量光谱(英文)

使用B3LYP/TZVP//B3LYP/aug-cc-pVTZ方法系统研究了饱和烷烃分子CnH2n+2(n=4-6)的轨道电子动量光谱,比较了同分异构体CnH2n+2(n=4-6)对轨道动量分布的影响.结合二维空间分析方法对电子在坐标空间中的密度分布进行了系统的研究.计算结果表明,最内价壳层电荷分布主要由s电子贡献,第二近邻芯价壳层则主要由p电子贡献,而其余的价壳层则为sp杂化.最内价轨道表现出最大的谱线强度并且远大于其它轨道的谱线强度,而且正烷烃的谱线强度要大于异烷烃等同分异构体的谱线强度,表现出了明显的与甲基移动的个数有关的性质.     

Effects of added surfactants on thermoreversible gelation of associating polymer solutions

The influence of added surfactants on physical properties of associating polymer solutions was examined by a new statistical‐mechanical theory of associating polymer solutions with multiple junctions and by computer simulation. The sol–gel transition line, the spinodal line, and the number of elastically effective chains in the mixed networks were calculated as functions of the concentration of added surfactants. All of them exhibited nonmonotonic behavior as a result of the following two competing mechanisms. One was the formation of new mixed micelles by binding surfactants onto the polymer associative groups. These micelles serve as crosslink junctions and promote gelation. The other was the replacement of polymer associative groups in the already formed network junctions by added surfactants. Such replacement lowers connectivity of junctions and destroys networks. The critical micelle concentration was also calculated. The results are compared with the reported experimental data on poly(ethylene oxide)‐based associating polymers and hydrophobically modified cellulose derivatives. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 733–751, 2004     

Topological polymer chemistry by dynamic selection from electrostatic polymer self-assembly

A collection of recent developments in topological polymer chemistry is presented. First, topological isomerism occurring on randomly coiled, flexible polymer molecules having cyclic and linear structures is discussed. Second, an electrostatic self-assembly and covalent fixation strategy has been developed for the synthesis of polymeric topological isomers. These isomers have double cyclic, manacle-, and theta-shaped constructions, and are prepared by using either linear or star telechelic polymer precursors having moderately strained cyclic ammonium salt groups, which carry multifunctional carboxylate counteranions. A technique of reversed-phase chromatography (RPC) is demonstrated as an effective means to separate polymers with different topologies, especially polymeric topological isomers. A further extension of topological polymer chemistry has been observed by dynamic selection from electrostatic polymer self-assembly to enable the effective formation of tadpole-shaped, cyclic-linear hybrid topologies.     

Molecular rectification in a metal-insulator-metal junction based on self-assembled monolayers

An electrical junction formed by mechanical contact between two self-assembled monolayers (SAMs)--a SAM formed from an dialkyl disulfide with a covalently linked tetracyanoquinodimethane group that is supported by silver (or gold) and a SAM formed from an alkanethiolate SAM that is supported by mercury-rectifies current. The precursor to the SAM on silver (or gold) was bis(20-(2-((2,5-cyclohexadiene-1,4-diylidene)dimalonitrile))decyl)) disulfide and that for the SAM on mercury was HS(CH(2))(n-1)CH(3) (n = 14, 16, 18). The electrical properties of the junctions were characterized by current-voltage measurements. The ratio of the conductivity of the junction in the forward bias (Hg cathodic) to that in the reverse bias (Hg anodic), at a potential of 1 V, was 9 +/- 2 when the SAM on mercury was derived from HS(CH(2))(15)CH(3). The ratio of the conductivity in the forward bias to that in the reverse bias increased with decreasing chain length of the alkanethiol used to form the SAM on mercury. These results demonstrate that a single redox center asymmetrically placed in a metal-insulator-metal junction can cause the rectification of current and indicate that a fixed dipole in the insulating region of a metal-insulator-metal junction is not required for rectification.     

Sliding friction between polymer surfaces: a molecular interpretation

For two contacting rigid bodies, the friction force F is proportional to the normal load and independent of the macroscopic contact area and relative velocity V (Amonton's law). With two mutually sliding polymer samples, the surface irregularities transmit deformation to the underlying material. Energy loss along the deformation cycles is responsible for the friction force, which now appears to depend strongly on V [see, e.g., N. Maeda et al., Science 297, 379 (2002)]. We base our theoretical interpretation on the assumption that polymer chains are mainly subjected to oscillatory "reptation" along their "tubes." At high deformation frequencies-i.e., with a large sliding velocity V-the internal viscosity due to the rotational energy barriers around chain bonds hinders intramolecular mobility. As a result, energy dissipation and the correlated friction force strongly diminish at large V. Derived from a linear differential equation for chain dynamics, our results are basically consistent with the experimental data by Maeda et al. [Science 297, 379 (2002)] on modified polystyrene. Although the bulk polymer is below T(g), we regard the first few chain layers below the surface to be in the liquid state. In particular, the observed maximum of F vs V is consistent with physically reasonable values of the molecular parameters. As a general result, the ratio FV is a steadily decreasing function of V, tending to V(-2) for large velocities. We evaluate a much smaller friction for a cross-linked polymer under the assumption that the junctions are effectively immobile, also in agreement with the experimental results of Maeda et al. [Science 297, 379 (2002)].     

Viscoelasticity of crosslinked epoxy polymer in the transition region

The dynamic mechanical properties of highly crosslinked epoxyamine polymer networks with nonrandomly distributed crosslinks were investigated. The transition temperatures of these polymers can be correlated with the number of CH₂ groups between crosslink junctions in the aliphatic amine portions of the network. The steepness of the modulus-temperature curve is also a function of crosslink density. This is in contrast with the case of natural rubber crosslinked by sulfur or by electron irradiation, where the modulus-temperature curves have similar shapes although the glass transition temperature increases with the degree of crosslinking. An empirical distribution function, similar to the one used by Tobolsky for stress relaxation distributions, was used to describe the temperature dispersion of the dynamic moduli. Two parameters, h_g and h_r, are used to characterize the steepness of the dispersion curve below and above the transition temperature, respectively. It is tentatively concluded that h_g correlates with the length of the CH₂ sequences in the amine portion of the polymer. The quantity h_r may be related perhaps to the motion involving the trifunctional nitrogen junction.     

Liquid crystals of silver complexes derived from simple 1-alkylimidazoles

A homologous series of silver complexes of 1-alkylimidazoles (R-im, R = CnH(2n+1), where n= 10, 12, 14, 16 and 18) was synthesized. All the CnH(2n+1)-im ligands are non-mesomorphic. Upon complexation, all the [Ag(CnH(2n+1)-im)2]-[NO3], except for n = 10, exhibit liquid crystalline properties. The crystal structure of [Ag(C12H25-im)2][NO3] shows that the silver center is two-coordinate and adopts a U-shaped conformation with bilayer packing. The non-mesomorphic [Ag(C16H33-bim)2][NO3](bim = benzimidazole) has a three-coordinate silver ion and has a chair conformation with monolayer stacking. Non-mesomorphic [Ag(C16H33-bim)2][BF4] has a linear geometry around the silver ion and also has a chair conformation. The mesophase for the Ag-(CnH(2n+1)-im) complexes has been identified as the smectic A (SmA) phase. [Ag(C16H33-im)2]+ with four different anions, NO3-, BF4-, PF6- and CF3SO3- were compared. Of the four Ag-im complexes, only that with the CF3SO3- anion does not show liquid-crystal behavior.     

Facile fabrication of monodisperse polymer hollow spheres

This article reports the facile synthesis of monodisperse polymer hollow spheres by seeded emulsion polymerization without additional treatment. In this method, P(St-MMA-MAA) copolymer latex particles were first prepared by emulsifier-free emulsion polymerization and then used as seeds to carry out emulsion polymerization of methyl methacrylate (MMA), divinyl benzene (DVB), and 2-hydroxyethyl methacrylate (HEMA) with potassium persulfate (KPS) as initiator at 80 degrees C. The void of hollow spheres was readily adjusted by changing the monomer/seed weight ratio, and it could be enlarged while the diameters of hollow spheres changed little after etching by dimethyl formamide (DMF). The effects of synthetic parameters including the monomer composition and the properties of seeds on the morphology of hollow spheres were investigated in detail. On the basis of the experimental results, it seemed reasonable to conclude that the formation of hollow spheres was due to the "dissolution" of seeds in monomers and phase separation between the constituent polymers. As a thermodynamic factor, sodium dodecyl sulfate (SDS) would allow the preparation of solid particles depending on its level.