A rapid and convenient method for preparative separation of three indissolvable polyphenols from Euphorbia pekinensis by the flexible application of solvent extraction combined with counter‐current chromatography

A rapid and convenient method was established to preparatively isolate the three ellagic acid types of compounds, which were the main polyphenols in Euphorbia pekinensis, by flexibly applying solvent extraction combined with counter‐current chromatography (CCC). The total extract (extracted using 95% ethanol) of E. pekinensis was pretreated by two simple steps before CCC isolation, following the procedure: the total extract was extracted by classical solvent extraction using petroleum ether and ethyl acetate, respectively, and then the ethyl acetate extract was suspended using 95% ethanol, after being allowed to stand overnight, the sediment was obtained. Partial sediment (100 mg) was then directly separated by CCC with a two‐phase solvent system composed of chloroform‐95% ethanol‐water‐85% formic acid (50:50:50:5, v/v/v/v). About 22 mg of 3,3′‐dimethoxy ellagic acid (1), 12 mg of 3,3′‐di‐O‐methyl‐4‐O‐(β‐d ‐xylopyranosyl)ellagic acid (2), and 35 mg of ellagic acid (3) with purities of 96.0, 95.2, and 95.4% were obtained respectively in one step within 4 h. After being purified by washing with methanol, the purities of the three compounds obtained were all above 98%. The purities were determined by HPLC and their chemical structures were further identified by ¹H and ¹³C NMR spectroscopy. The recoveries were calculated as 84.6, 85.7, and 89.5%, respectively. The result demonstrated that the present isolation method was rapid, economical and efficient for the preparative separation of polyphenols from E. pekinensis.     

S‐Alkylation of Soft Scorpionates

The alkylation reactions of soft scorpionates are reported. The hydrotris(S‐alkyl‐methimazolyl)borate dications (alkyl=methyl, allyl, benzyl), which were prepared by the reaction of Tm^Me anion and primary alkyl halides, have been isolated and structurally characterised. The reaction is, however, not universally successful. DFT analysis of these alkylation reactions (C?S versus B? H alkylation) indicates that the observed outcome is driven by kinetic factors. Extending the study to incorporate alternative imine thiones (mercaptobenzothiazole, bz; thiazoline, tz) led to the structural characterisation of di[aquo‐μ‐aquohydrotris(mercaptobenzothiazolyl)boratosodium], which contains sodium atoms in the κ³‐S,S,S coordination mode. Alkylation of Na[Tbz] and Na[tzTtz] leads to decomposition resulting in the formation of the simple S‐alkylated heterocycles. The analysis of the species involved in these reactions shows an inherent weakness in the B? N bond in soft scorpionates, which has implications for their use in more advanced chemistry.     

Dynamic Effects in Intramolecular Schmidt Reactions: Entropy,Electrostatic Drag,and Selectivity Prediction

Electrostatic drag in the intramolecular Schmidt reactions of azidopropylcyclohexanones is characterized using density functional theory (DFT) calculations and direct dynamics simulations. Despite resulting from enthalpically favorable interactions, electrostatic drag slows down N₂ loss during formation of bridged lactam products, an effect with implications for controlling product selectivity.     

Development of a Mild and Versatile Directed Cycloaddition Approach to Pyridines

The aza‐Diels–Alder cycloaddition of 1,2,4‐triazines with alkynes offers a rapid and convenient method for the synthesis of highly substituted pyridines, but often requires harsh conditions and long reaction times. The present study offers a solution to these limitations by use of a temporary tether established by a Lewis acid–base complexation of in situ generated alkynylboranes and triazines bearing a Lewis basic donor. The cycloaddition reactions take place within 20 min at 40 °C and provide direct access to a broad range of pyridines with complete and predictable regiocontrol. The carbon?boron bond can be further functionalised by cross‐coupling allowing further functionality to be introduced after cycloaddition.     

Protein Allostery at Atomic Resolution

Protein allostery is a phenomenon involving the long range coupling between two distal sites in a protein. In order to elucidate allostery at atomic resoluion on the ligand-binding WW domain of the enzyme Pin1, multistate structures were calculated from exact nuclear Overhauser effect (eNOE). In its free form, the protein undergoes a microsecond exchange between two states, one of which is predisposed to interact with its parent catalytic domain. In presence of the positive allosteric ligand, the equilibrium between the two states is shifted towards domain–domain interaction, suggesting a population shift model. In contrast, the allostery-suppressing ligand decouples the side-chain arrangement at the inter-domain interface thereby reducing the inter-domain interaction. As such, this mechanism is an example of dynamic allostery. The presented distinct modes of action highlight the power of the interplay between dynamics and function in the biological activity of proteins.     

A Frequency-Selective pH-Responsive paraCEST Agent

Paramagnetic chemical exchange saturation transfer (paraCEST) agents are well-suited for imaging tissue pH because the basis of CEST, chemical exchange, is inherently sensitive to pH. Several previous pH-sensitive paraCEST agents were based on an exchanging Ln³⁺-bound water molecule as the CEST antenna but this design often added additional line-broadening to the bulk water signal due to T₂ exchange. We report herein a pH-sensitive paraCEST agent that lacks an inner-sphere water molecule but contains one Ln-bound −OH group for CEST activation. The Yb³⁺ complex, Yb( 1 ), displayed a single, highly shifted CEST peak originating from the exchangeable Yb-OH proton, the frequency of which changed over the biologically relevant pH range. CEST images of phantoms ranging in pH from 6 to 8 demonstrate the potential of this agent for imaging pH. Initial rodent imaging studies showed that Gd( 1 ) remains in the vascular system much longer than anticipated but is cleared slowly via renal filtration.     

Exploiting the Potential of Meroterpenoid Cyclases to Expand the Chemical Space of Fungal Meroterpenoids

Fungal meroterpenoids are a diverse group of hybrid natural products with impressive structural complexity and high potential as drug candidates. In this work, we evaluate the promiscuity of the early structure diversity-generating step in fungal meroterpenoid biosynthetic pathways: the multibond-forming polyene cyclizations catalyzed by the yet poorly understood family of fungal meroterpenoid cyclases. In total, 12 unnatural meroterpenoids were accessed chemoenzymatically using synthetic substrates. Their complex structures were determined by 2D NMR studies as well as crystalline-sponge-based X-ray diffraction analyses. The results obtained revealed a high degree of enzyme promiscuity and experimental results which together with quantum chemical calculations provided a deeper insight into the catalytic activity of this new family of non-canonical, terpene cyclases. The knowledge obtained paves the way to design and engineer artificial pathways towards second generation meroterpenoids with valuable bioactivities based on combinatorial biosynthetic strategies.     

双中心全息记录的矢量分析与记录方向优化

对描述双掺杂晶体非挥发性全息记录动力学过程的Kukhtarev方程进行了矢量分析,分析中考虑了体光生伏特效应和外加电场的作用。在小信号近似的基础上给出了双中心全息记录中记录与固定阶段空间电荷场的矢量解析解。在综合考虑空间电荷场的各向异性以及晶体有效电光系数的各向异性后,给出了双中心全息记录的优化记录方向。结果表明,对(Fe,Mn)∶LiNbO3晶体633nm寻常光记录,优化记录方向主要由有效电光系数决定,光栅波矢与光轴夹角为22°,方位角为30°;对(Fe,Mn)∶LiNbO3晶体633nm非寻常光记录,优化记录方向主要由固定空间电荷场决定,光栅波矢与光轴夹角为44°,方位角为90°。     

基于联合变换相关器的Dempster-Shafer理论计算

提出了用联合变换相关器(JTC)来实现证据理论概率分配函数正交和的光学计算,在理论上对于如何用联合变像相关器实现证据理论分配函数正交和作了详细的讨论,并作了相应的仿真测试,结果显示该方法是可行的。与John Caulfield提出的用声光器件矢量外积实现的正交和计算相比,在该结构中由于采用二进制编码的数值计算,因此其计算精度得到了提高,同时对联合变换相关器输入端二进制编码的数值空间位置的适当调整可以直接得到所需要的证据理论正交和矢量,在处理步骤上得到了简化。     

敏化光波长对(Fe,Ni):LiNbO3晶体全息记录性能的影响

分别采用514 nm绿光、488 nm蓝光和390 nm紫外光作为敏化光,633 nm红光作为记录光,详细研究了敏化光波长对氧化(Fe,Ni):LiNbO3晶体全息记录性能的影响.结果表明:随着敏化光波长的逐渐减小,氧化(Fe,Ni):LiNbO3晶体的非挥发全息记录性能逐渐优化,390 nm紫外光是这三种敏化光中最优的敏化光.考虑敏化光的吸收,为了在双中心全息记录中获得最优的性能,应当选择合适波长的敏化光:一方面短波长敏化光能有效地敏化深中心;另一方面短波长敏化光的吸收太强(如对光折变效应无用的基质吸收),不能沿厚度方向有效地敏化晶体,所以实际上需折衷考虑,并从理论上给予了解释.