Thermally reversible light scattering films based on the melting/crystallization of organic crystals dispersed in an epoxy matrix

Films that can be reversibly switched from opaque to transparent states by varying temperature (TRLS films), have potential applications in thermal sensors, optical devices, recording media, etc. A dispersion of organic crystals in a thermoset may be used for these purposes provided that at temperatures higher than the melting point there is a matching of refractive indices of both phases. A model system consisting on a dispersion of diphenyl (DP) crystals in an epoxy matrix based on diglycidyl ether of bisphenol A and m-xylylenediamine, was analyzed as a possible TRLS film encapsulated between transparent covers to avoid sublimation of DP. To obtain a uniform dispersion of DP-rich domains in the epoxy matrix by polymerization-induced phase separation, it was necessary to add 5 wt% of polystyrene (PS) to the initial formulation. Phase separation induced by polymerization at 80 °C led to a dispersion of PS/DP domains in the epoxy matrix due to the low compatibility of PS with the epoxy and its high compatibility with DP. Crystallization and melting processes were confined to the interior of dispersed domains leading to an excellent reproducibility of the optical properties of TRLS films in the course of successive heating-cooling cycles.     

飞行时间质谱中的空间电荷效应研究

在分子多光子电离实验中, 发现母体离子的飞行时间(TOF)质谱峰随激光强度的提高而展宽, 此现象归因于离子团内离子间库仑排斥作用的空间电荷效应. 为从理论上解释此现象, 尝试了从一个简单的理论模型进行推演, 得到飞行时间质谱峰的半高全宽(FWHM)与激光能量、样品气体的分压比、电极板的总电压、离子质量及所采用的透镜聚焦焦距之间关系的解析表达式, 所得的结果能够很好地说明实验现象.     

Debye screening for two-dimensional Coulomb systems at high temperatures

The grand canonical ensemble of a two-dimensional Coulomb system with±1 charges is proved to have screening phenomena in its high-temperature region. The Coulomb potential in a finite region is assumed to be (–)^–1, where is the Laplacian with zero boundary conditions on. The hard-core condition is not assumed. The model is set up by separating (–)^–1 into a shortrange part and a long-range part depending on a parameter. The self-energies are subtracted only for the short-range part and therefore a choice of is a choice of subtraction of self-energies. The method of proof is in general the same as that of Brydges-Federbush Debye screening, except that here a modification for the short-range part of the potentials is needed.     

A rigorous control of logarithmic corrections in four-dimensional ϕ4 spin systems

Using Gawedzki and Kupiainen's rigorous block spin transformation method, we study critical phenomena in ⁴ spin systems in four dimensions. In Part I of this work we investigate in detail the renormalization group trajectory of the system not exactly at the critical point.     

Collapse transition and asymptotic scaling behavior of lattice animals: Low-temperature expansion

A low-temperature expansion for the free energy density of lattice animals is derived. Analysis of the series yields a collapse transition temperature ofT _c - 0.54, in close agreement with previous estimates. It is demonstrated that _p,k, the number ofp-particle,p-bond animals, obeys the asymptotic scaling law log _p,k pg(k/p) + o(p). The low-temperature series and numerical data are used to estimate the scaling function.     

Michael and ring expansion reactions of 6-carboethoxy-3,5-diaryl-2-cyclohexen-1-ones

When -keto-ester1 a was reacted with dimethyl acetylenedicarboxylate ring expansion occurred to give substituted cyclooctadienones.Michael reactions of the title compounds1 with unsaturated ketones gave adducts, some of which underwent further cyclization reactions. A new route to -tetralone ring system10 via cyclization of the intermediateMichael adduct9 is described.

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Michael- und Ringerweiterungsreaktionen von 6-Carboethoxy-3,5-diaryl-2-cyclohexen-1-onen

Zusammenfassung Bei der Reaktion von -Keto-ester1 a mit Dimethyl-acetylendicarboxylat wurden unter Ringerweiterung substituierte Cyclooctadienone erhalten. DieMichael-Reaktion der Titelverbindung1 mit ungesättigten Ketonen ergab Addukte, von denen einige weitere Cyclisierungsreaktionen eingingen. Es wird ein neuer Weg zum -Tetralonsystem10 über die Cyclisierung des intermediärenMichael-Addukts9 beschrieben.

     

Broadband and band-selective IMPRESS-gHMBC: compensation of refocusing inefficiency with synchronized inversion sweep

Compensation of refocusing inefficiency in a gHMBC experiment by replacing the rectangular pi pulse with a pair of adiabatic pulses with synchronized inversion sweep (CRISIS) significantly improves the performance of the gHMBC experiment. The CRISIS-gHMBC experiment retains the pure absorptive shapes in F1 and hence results in better lineshape and higher resolution than the current versions of magnitude mode gHMBC spectra. When used as a broadband experiment, CRISIS-gHMBC, owing to better refocusing efficiency of the adiabatic pulse pairs, gives improved performance across the 13C spectral width. Moreover, it is shown that CRISIS-gHMBC is a robust and improved alternative and when used along with the IMPRESS (Improved Resolution using Symmetrically Shifted pulses) technique further increases the sensitivity and resolution without additional experimental time. The IMPRESS-CRISIS combination is demonstrated for broadband gHMBC and band-selective gHMBC experiments. The ICbs-gHMBC [IMPRESS-CRISIS-band-selective gHMBC] experiment is an attractive and better alternative to individual band-selective gHMBC.     

Modeling high-pressure densities at wide temperature range with volume scaling: Cyclohexane + n-hexadecane mixtures

High-pressure density data for cyclohexane + n-hexadecane mixtures at a wide temperature range was modeled with several classical equations of state (EOS) and correlative models. A modification for softening the co-volume and another for a volume scaling of the Peng–Robinson EOS (VS-PR) were proposed. The VS-PR model is able to correlate the pure component experimental data employing only five adjustable parameters, with root-mean-square deviation (RMSD) between calculated and experimental densities essentially within the experimental error. This result is superior to widely used approaches, i.e., a six parameter Tait model and six parameter volume translations (temperature and pressure dependent) for Peng–Robinson and Patel–Teja EOS. The VS-PR model also represents well the isobaric thermal expansion and the isothermal compressibility coefficients of the pure cyclohexane, a small naphthenic substance as well as a long chain n-alkane hydrocarbon, n-hexadecane. When modeling the mixture data, the use of VS-PR model of pure components along with the Redlich–Kister expansion, truncated at the first term, the density was correlated within a RMSD only 60% greater than the experimental error. The proposed model is able to accurately represent all the tested mixture data with a relatively small number of parameters.     

Multipole expansion of diatomic overlap

A systematic extension of Ruedenberg's expansion formula is applied to evaluate two-electron integrals occurring in calculations on molecular structure. Minimum STO basis sets are used for all SCF-calculations within the framework of the MEDO-method (Multipole Expansion of Diatomic Overlap). The errors due to this approximation scheme are almost negligible compared to those introduced by the truncated basis set: LiH, Li₂ and N₂ are chosen as examples.