Energy‐resolved technique for discovery and identification of malonyl‐triterpene saponins in Caulophyllum robustum by UHPLC‐electrospray Fourier transform mass spectrometry

Malonyl‐triterpene saponins (MTSs) attract scientific attentions because of their structural diversities and valuable bioactivities. However, its thermal instability brings a huge amount of challenges for isolation and purification of this class of compounds. To our best knowledge, there has been no report on isolation and analysis of MTSs from genus Caulophyllum. In this study, a strategy combining data acquisition using an energy‐resolved technique and the narrow widow extracted ion chromatograms as data mining method was developed for discovery and identification of MTSs in Caulophyllum robustum hair roots by ultra high liquid chromatography coupled to electrospray ionization Fourier transform mass spectrometry. The method was performed at an independent MS full scan using our bottom‐up energies by in‐source collision induced dissociations with 0, 25, 50 and 100 eV in both positive and negative modes. Precursor ion as well as fragment ion information was simultaneously collected from four energy‐resolved MS spectra in a single run of 18 min. The fragmentation pathways of intact deprotonated, protonated and sodium ions of MTSs were proposed for the structural elucidation of Caulophyllum MTSs. A flowchart involving a stepwise procedure based on key fragments from ESI^?/ESI⁺‐FT‐MS^{(1, 1)} to MS^{(1, 4)} spectra was constructed for the identification of structural elements in the MTSs. As a result, a total of 23 MTSs were discovered and tentatively identified, which had not been reported from Caulophyllum species before. All of these were potentially new compounds. This study provides an excellent example for discovery and identification of MTSs in herb medicines. Copyright © 2016 John Wiley & Sons, Ltd.     

计算烷烃异构体生成焓的新方法

基于作者提出的诱导极性叠加原理,设计了包括与诱导极性叠加总量要关的能量项的烷烃异构体的标准生成焓估算的新方法。与前人方法比较,它具有较高的计算精度,较少的参数,各参数物理意义明确,而且理论上可以推广到含多种杂原子的衍生物的标准生成焓的计算。     

钌联吡啶单配体双取代基效应

对钌联吡啶配合物及其单配体的4,4′ 双取代衍生物, 用量子化学密度泛函(DFT)方法在B3LYP/LanL2DZ水平上进行计算.探讨一些强的推电子基团(如－OCH3)和强的拉电子基团(如－NO2)的取代基效应对配合物的电子结构与相关性质,如配位键长、光谱性质等的影响规律,为该类配合物的合成,光、电、催化和生化作用机理分析提供理论参考.     

固相萃取-高效液相色谱/串联质谱法测定食醋中的3种甜味剂

建立了食醋中3种甜味剂的固相萃取-高效液相色谱/串联质谱分析方法。样品经酸性水稀释,弱阴离子固相萃取柱净化,Pursuit C18色谱柱分离,10 mmol/L醋酸铵(含0.1%氨水)和乙腈为流动相梯度洗脱,电喷雾负离子模式下多反应监测(MRM)模式检测。糖精钠、安赛蜜、甜蜜素的定量限分别为10、5、5 μg/kg,回收率为72.1%～96.8%,相对标准偏差小于15%。该方法准确、灵敏度高,可用于食醋中甜味剂的定性定量检验。     

瞬态荧光方法研究溶剂诱导的三苯胺衍生物的对称性破缺电荷转移动力学

在缺乏特征红外振动的情况下追踪具有四极或八极对称性分子的激发态对称性破缺电荷转移通常是很困难的.本文以一种具有八极对称性的三苯胺衍生物为研究对象,利用飞秒时间分辨瞬态荧光光谱方法获得发光跃迁偶极矩的演化动力学,进而实时表征了其溶剂诱导对称性破缺电荷转移的动力学过程.当该分子处于弱极性甲苯溶液中时,在激发态弛豫过程中其发射偶极矩变化较小;当处于较强极性的四氢呋喃溶液中时,其发射偶极矩在数皮秒内快速减小.在对比单体偶极分子的荧光动力学后,推断八极分子的发光态在强极性溶剂中经历溶剂诱导的结构变化,由激子耦合的八极对称性降低至激发定域的偶极对称性;而在较弱极性的溶剂中,其八极对称性在溶剂化稳定中得以较大程度的保持.     

羊八井50m2RPC实验及初步测试结果

介绍了羊八井50m²电阻板室(RPC)地毯实验的结构、安装和对其性能的初步测试.测试的结果表明RPC完全能够很好地在海拔4300m,气压594mbar的羊八井宇宙线观测站正常地运行.     

Security analysis of a spatiotemporal-chaos-based cryptosystem

An S-box modified one-way coupled map lattice is applied as a chaotic cryptograph. The security of the system is evaluated from various attacks currently used, including those based on error function analysis, statistical property analysis, and known-plaintext and chosen-ciphertext analytical computations. It is found that none of the above attacks can be better than the brute force attack of which the cost is exhaustively quantitated by the key number in the key space. Also, the system has fairly fast encryption (decryption) speed, and has extremely long period for finite-precision computer realization of chaos. It is thus argued that this chaotic cryptosystem can be a hopeful candidate for realistic service of secure communications.     

Towards Dynamic Control of Wettability by Using Functionalized Altitudinal Molecular Motors on Solid Surfaces

We report the synthesis of altitudinal molecular motors that contain functional groups in their rotor part. In an approach to achieve dynamic control over the properties of solid surfaces, a hydrophobic perfluorobutyl chain and a relatively hydrophilic cyano group were introduced to the rotor part of the motors. Molecular motors were attached to quartz surfaces by using interfacial 1,3‐dipolar cycloadditions. To test the effect of the functional groups on the rotary motion, photochemical and thermal isomerization studies of the motors were performed both in solution and when attached to the surface. We found that the substituents have no significant effect on the thermal and photochemical processes, and the functionalized motors preserved their rotary function both in solution and on a quartz surface. Preliminary results on the influence of the functional groups on surface wettability are also described.     

Polymorphism of Amino Acid‐Based Dendrons: From Organogels to Microcrystals

There is a delicate balance for a low‐weight molecule to behave as a gelator or crystal. The synthesis of two novel amino acid‐based naphthalene‐dendrons, Nap ‐ G1 and Nap ‐ G2 is described. Both dendrons display polymorphic properties in organic solvents. Nap ‐ G1 developed a fibrous network with β‐sheet architecture in cyclohexane but exhibited a spherulitic network in mixed solvents (chloroform/petroleum ether 1:5, v/v). On the other hand, Nap ‐ G2 acted as an efficient organogelator in chloroform but formed crystalline fibers in relatively high polarity solvents (such as acetone and methanol). Combinations of characterizations have been employed to study the polymorphism.     

Ionic liquids for the convenient synthesis of functional nanoparticles and other inorganic nanostructures

Ionic liquids are a new class of organic solvents with high polarity and a preorganized solvent structure. Very polar reactions can be carried out in these liquid in the absence of or with a controlled amount of water, and crystalline nanoparticles can be synthesized conveniently at ambient temperatures. The pronounced self-organization of the solvent is used in the synthesis of self-assembled, highly organized hybrid nanostructures with unparalleled quality. The extraordinary potential of ionic liquids in materials synthesis is described in this minireview and a physicochemical explanation is given.