Path to achieving molecular dispersion in a dense reactive mixture

A uniform dispersion of reactants is necessary to achieve a complete reaction involving multicomponents. In this study, we have examined the role of plasticizer in the reaction of two seemingly unlikely reactants: a highly crystalline hexamethylenetetramine (HMTA) and a strongly hydrogen bonded phenol formaldehyde resin. By combining information from NMR, infrared spectroscopy and differential scanning calorimetry, we were able to determine the role of specific intermolecular interactions necessary for the plasticizer to dissolve the highly crystalline HMTA and to plasticize the phenol formaldehyde resin in this crosslinking reaction. The presence of the plasticizer increased the segmental mobility, disrupted the hydrogen bonded matrix, and freed the hydroxyl units, which further increased the solubility of the HMTA. Both the endothermic and exothermic transitions are accounted for in the calorimetric data obtained. For the first time, it is possible to obtain the effective molar ratio of each component needed to complete the crosslinking reaction efficiently. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1519–1526     

Surface of room temperature ionic liquid [bmim][PF6] studied by polarization- and experimental configuration-dependent sum frequency generation vibrational spectroscopy

Understanding and control of the surface properties such as molecular orientations are of great importance in numerous applications of ionic liquids. However, there remain discrepancies among the previous experimental and theoretical studies on the surface orientation and structures of room temperature ionic liquids(RTIL) systems. In this article, the orientation of 1-butyl-3-methylimidazolium([bmin]) cation at the air/liquid interface of a characteristic RTIL, 1-butyl-3-methylimidazolium hexafluorophosphate([bmim][PF6]), was investigated by the sum frequency generation vibrational spectroscopy(SFG-VS). Detailed polarization and experimental configuration analyses of the SFG-VS spectra showed the possibility of a small spectral splitting in the CH3 symmetric stretching region, which can be further attributed to the probable existence of multiple orientations for the interfacial [bmim] cations. In addition, the(N)–CH3 vibrations were absent, ruling out the prediction by several recent molecular dynamics simulations which state that portions of the [bmim] cations orient with a standing-up(N)–CH3 group at the ionic liquid surface. Hence, new realistic theoretical models have to be developed to reflect the complex nature of the ionic liquid surface.     

Two homosecoiridoids from the fl ower buds of Lonicera japonica

Two new homosecoiridoids, named loniaceticiridoside (1) and lonimalondialiridoside (2), were isolated from an aqueous extract of the flower buds of Lonicera japonica. Their structures including the absolute configuration were determined by extensive spectroscopic studies, especially by 2D NMR and CD data analysis. A proposed biosynthetic pathway and preliminary investigations of the biological activity of compounds 1 and 2 are also discussed.     

Gravitational wave imprint of new symmetry breaking

It is believed that there are more fundamental gauge symmetries beyond those described by the Standard Model of particle physics. The scales of these new gauge symmetries are usually too high to be reachable by particle colliders. Considering that the phase transition (PT) relating to the spontaneous breaking of new gauge symmetries to the electroweak symmetry might be strongly first order, we propose considering the stochastic gravitational waves (GW) arising from this phase transition as an indirect way of detecting these new fundamental gauge symmetries. As an illustration, we explore the possibility of detecting the stochastic GW generated from the PT of \begin{document}$ {\bf{B}}-{\bf{L}}$\end{document} in the space-based interferometer detectors. Our study demonstrates that the GW energy spectrum is reachable by the LISA, Tianqin, Taiji, BBO, and DECIGO experiments only for the case where the spontaneous breaking of \begin{document}$ {\bf{B}}-{\bf{L}}$\end{document} is triggered by at least two electroweak singlet scalars.     

Highly Selective Copper‐Catalyzed Asymmetric [3+2] Cycloaddition of Azomethine Ylides with Acyclic 1,3‐Dienes

The first examples of the catalytic asymmetric 1,3‐dipolar cycloaddition of azomethine ylides with acyclic activated 1,3‐dienes (and 1,3‐enynes) are described. Under copper catalysis, a selective cycloaddition at the terminal γ,δ‐C?C bond is observed. In addition, depending on the ligand used, either the exo or the endo adduct can be obtained with high selectivity. Under appropriate reaction conditions, the acyclic 1,6‐addition product is detected, suggesting a stepwise mechanism. The resulting C4‐alkenyl‐substituted pyrrolidines are suitable substrates for further access to polycyclic systems, as highlighted by the preparation of hexahydrochromeno[4,3‐b]pyrrole and the tetracyclic core of the alkaloid gracilamine.     

原位液相透射电子显微镜及其在 纳米粒子表征方面的应用

近年来,基于透射电子显微技术、微纳加工技术和薄膜制造技术的发展,原位液相透射电子显微技术产生,为构建多种纳米级分辨率尺度下的微实验平台,发展新型纳米表征技术和众多领域的相关研究提供了途径.本文首先介绍了应用于原位液相透射电子显微技术的液体腔设计要求,然后介绍了液体腔的发展和典型的制备工艺,最后综述了近年来液体腔透射电子显微镜在纳米粒子成核和生长方面的应用研究,并探讨了该技术前沿发展面临的机遇和挑战.本文将为提高我国先进纳米表征技术和原子精准构筑技术提供相关讨论和支持.     

Sensitive chemically amplified electrochemical detection of ruthenium tris-(2,2′-bipyridine) on tin-doped indium oxide electrode

Optimized combination of chemical agents was selected for sensitive electrochemical detection of dissolved ruthenium tris-(2,2′-bipyridine) (Ru-bipy). The detection was based on the chemical amplification mechanism, in which the anodic current of a redox-active analyte was amplified by a sacrificial electron donor in solution. On indium-doped tin oxide (ITO) electrodes, electrochemical reaction of the analyte was reversible, but that of the electron donor was greatly suppressed. Several transition metal complexes, such as ferrocene and tris-(2,2′-bipyridine) complexes of osmium, iron and ruthenium, were evaluated as model analyte. A correlation between the amplified current and the standard potential of the complex was observed, and Ru-bipy generated the largest current. A variety of organic bases, acids and zwitterions were assessed as potential electron donor. Sodium oxalate was found to produce the largest amplification factor. With Ru-bipy as the model analyte and oxalate as the electron donor, the analyte concentration curve was linear up to 50 μM, with a lower detection limit of approximately 50 nM. Preliminary work was presented in which a Ru-bipy derivative was attached to bovine serum albumin and detected electrochemically. Although the combination of Ru-bipy, oxalate and ITO electrode has been used before for electrochemiluminescent detection of Ru-bipy and oxalate, as well as electrochemical detection of oxalate, its utility in amplified voltammetric detection of Ru-bipy as a potential electrochemical label has not been reported previously.     

完全非相干白光一维光生伏打暗空间孤子

使用白炽灯作光源在LiNbO₃∶Fe晶体内实验观察到一维白光光生伏打暗空间孤 子. 由奇数 和偶数初始条件分别产生了灰孤子和灰孤子对，它们所感应的波导能导向白光和相干光. 用 相干光清楚地探测到它们内部的多模结构. 该实验证明了白光光生伏打暗空间孤子的存在， 并指出了用完全非相干的白光暗孤子控制和导向相干光的可能性. 关键词： 光生伏打效应 自陷 完全非相干孤子 波导