Asymmetric Total Syntheses,Stereostructures, and Cytotoxicities of Marine Bromotriterpenoids Aplysiol B (Laurenmariannol) and Saiyacenol A

There are marine cytotoxic bromotriterpenoids, named the thyrsiferol family that are structurally characterized by some tetrahydropyran (THP) and tetrahydrofuran (THF) rings. The thyrsiferol family belongs to natural products that are often difficult to determine their stereostructures even by the current, highly advanced spectroscopic methods, especially in acyclic systems including stereogenic tetrasubstituted carbon centers. In such cases, it is effective to predict and synthesize the possible stereostructures. Herein, to elucidate ambiguous stereostructures and unassigned absolute configurations of aplysiol B, laurenmariannol, and saiyacenol A, members of the thyrsiferol family, we carried out their asymmetric chemical syntheses featuring 6-exo and 5-exo oxacyclizations of epoxy alcohol precursors and 6-endo bromoetherification of a bishomoallylic alcohol. In this paper, we report total assignments of their stereostructures through their asymmetric chemical syntheses and also their preliminary cytotoxic activities against some tumor cells. These results could not have been achieved without depending on asymmetric total synthesis.     

对比实验法在无机及分析化学实验教学中的应用——以银量法测定氯含量实验为例

介绍莫尔法和荧光黄法测定生理盐水中氯化钠含量的实验原理和操作步骤，针对无机及分析化学实验教学中测定氯含量实验的原理、指示剂、标准溶液、滴定条件及适用范围等内容进行比较和分析，阐明了不同实验方法与操作步骤之间的对应关系。学生根据预习实验，结合具体实验操作、实验现象和实验结果的对比，可以充分直观地理解实验内容，掌握无机及分析化学实验的学习方法，提高学生的发现问题和解决问题的能力。     

Fabrication of Nano Flower‐shaped Platinum on Glassy Carbon Electrode as a Sensitive Sensor for Lead Electrochemical Analysis

Platinum nanoflowers modified glassy carbon electrodes (PtNFs/GCE) was fabricated simply for lead determination in water samples. The modified electrodes were prepared by electrodeposition in hexachloroplatinic acid solution at constant potential. The influence of deposition time and potential on surface morphology, chemical composition, electrochemical properties of electrode were investigated. At ?0.2 V of potential and 150 s of deposition duration, platinum developed as nanoflower shape and scattered densely all over the glassy carbon surface, producing the largest electrochemically active surface areas. The highest differential pulse stripping voltammetry (DPSV) signal of lead was obtained by using the prepared electrode. Under optimized experimental condition of electrolyte, accumulation potential and time, the peak current was found to be linear proportion to lead concentration in range of 1 to 100 μg L^?1 (slope=0.371) with a limit of detection of 0.398 μg L^?1. The method has good repeatability and reproducibility with relative standard deviations of 1.47 % and 4.83 %, respectively. The modified PtNFs/GCE also demonstrated an excellent long‐term stability with only 9 % decrease in Pb peak current over 30 days. Moreover, the performance of the modified PtNFs/GCE in determination of Pb(II) in two industrial wastewaters was good agreement with data obtained by a graphite furnace atomic absorption spectrometry (GFAAS) method.     

Crystal Growth and Structure Determination of Pigment Orange 82

The crystal structure of the important industrial orange pigment PO82, major part of the BASF Colors & Effects^® product Sicopal^® Orange K/L 2430, was solved from combined X‐ray single crystal, X‐ray and neutron powder diffraction, ¹¹⁹Sn Mössbauer spectroscopy, transmission electron microscopy, electron diffraction, and chemical analyses. The structure contains Keggin type clusters composed of four [M₃O₁₃] trimers consisting each of three MO₆ octahedra that share edges and one common oxygen atom connecting the trimers to the central ZnO₄ tetrahedron. The octahedrally coordinated metal atom position is mixed occupied by Ti⁴⁺, Sn⁴⁺, and Zn²⁺. Adjacent Keggin clusters share vertices and are further interconnected to four ZnO₄ tetrahedra. This framework of interconnected MO₆ octahedra and ZnO₄ tetrahedra contains channels along [110], in which the Sn²⁺ cations are located.     

Magnetic solid‐phase extraction based on carbon nanosphere@Fe3O4 for enantioselective determination of eight triazole fungicides in water samples

In this work, a carbon nanosphere decorated by Fe₃O₄ nanoparticles was prepared, characterized and used as the magnetic adsorbent. Eight commonly used chiral triazole fungicides, including penconazole, uniconazole, paclobutrazol, triazolone, tebuconazole, hexaconazole, triticonazole and epoxiconazole were extracted from two environmental water samples (river water and lake water) by magnetic solid‐phase extraction, followed by the enantiomeric analysis on a Chiralpark IC column coupled with a triple quadrupole mass spectrometry to evaluate their possible stereoselective degradation occurring in the water samples. The possible factors affecting the extraction performance, such as amount of used adsorbents, pH and ionic strength of water solution, types and volumes of desorption solvents were systematically investigated. Under the optimum conditions, extraction yields of eight triazole fungicides were above 80% and the concentration factors were as high as 1000. Method detection and quantification limits for the enantiomers of eight triazole fungicides were in the range of 0.56–6.95 ng/L. Satisfactory accuracy (relative recovery 77.8–93.5%), good intraday precision (RSD 4.3–9.8%) and interday precision (RSD 3.1–7.9%) were also obtained. The developed method provided the simplicity of operation, rapidity and high enrichment factor, which can be used to monitor and evaluate the behavior of the individual enantiomer of chiral triazole fungicides.     

某些分析化学实验教材中均相沉淀概念的误区

目前，均相沉淀法在大学分析化学实验中已很少采用。高锰酸钾间接滴定法测定钙含量是大学分析化学实验中的经典实验之一，历史上存在均相沉淀法和传统沉淀法2种不同的沉淀操作。虽然我国现有大学分析化学实验中已不采用均相沉淀法进行该实验，但在某些分析化学实验教材中，却存在概念混乱的现象，即把传统沉淀法称作均相沉淀法。对这种现象进行了探讨和总结。     

Simultaneous determination of 75 abuse drugs including amphetamines,benzodiazepines, cocaine,opioids, piperazines,zolpidem and metabolites in human hair samples using liquid chromatography–tandem mass spectrometry

A liquid chromatography–tandem mass spectrometric method for the simultaneous determination of 75 abuse drugs and metabolites, including 19 benzodiazepines, 19 amphetamines, two opiates, eight opioids, cocaine, lysergic acid diethylamide, zolpidem, three piperazines and 21 metabolites in human hair samples, was developed and validated. Ten‐milligram hair samples were decontaminated, pulverized using a ball mill, extracted with 1 mL of methanol spiked with 28 deuterated internal standards in an ultrasonic bath for 60 min at 50°C, and purified with Q‐sep dispersive solid‐phase extraction tubes. The purified extracts were evaporated to dryness and the residue was dissolved in 0.1 mL of 10% methanol. The 75 analytes were analyzed on an Acquity HSS T3 column using gradient elution of methanol and 0.1% formic acid and quantified in multiple reaction monitoring mode with positive electrospray ionization. Calibration curves were linear (r ≥ 0.9951) from the lower limit of quantitation (2–200 pg/mg depending on the drug) to 2000 pg/mg. The coefficients of variation and accuracy for intra‐ and inter‐assay analysis at three QC levels were 4.3–12.9% and 89.2–109.1%, respectively. The overall mean recovery ranged from 87.1 to 105.3%. This method was successfully applied to the analysis of 11 forensic hair samples obtained from drug abusers.     

Synthesis and Structure Determination of SCM-15: A 3D Large Pore Zeolite with Interconnected Straight 12×12×10-Ring Channels

A new germanosilicate zeolite named SCM-15 (Sinopec Composite Material No. 15), the first zeolite containing a 3-dimensional (3D) channel system with interconnected 12-, 12-, and 10-ring channels (pore sizes: 6.1×7.2, 6.1×7.4, and 5.2×5.9 Å), has been synthesized using neutral 4-pyrrolidinopyridine as organic structure-directing agents (OSDAs). Its structure has been determined by combining single-crystal electron diffraction (SCED) and synchrotron powder X-ray diffraction (SPXD) data. The unique open framework structure of SCM-15 is related to that of FOS-5 ( BEC ), ITQ-7 ( ISV ), PKU-16 ( POS ), ITQ-26 ( IWS ), ITQ-21, Beta polymorph B, and SU-78B, since all these framework structures can be constructed from similar chains which are connected through shared 4-ring or double 4-ring (d4r) units. Based on this relation, six topologically reasonable 3D large or extra-large pore hypothetical zeolites are predicted.     

Structure determination of KScS2, RbScS2 and KLnS2 (Ln = Nd,Sm, Tb,Dy, Ho,Er, Tm and Yb) and crystal–chemical discussion

The title structures of KScS₂ (potassium scandium sulfide), RbScS₂ (rubidium scandium sulfide) and KLnS₂ [Ln = Nd (potassium neodymium sufide), Sm (potassium samarium sulfide), Tb (potassium terbium sulfide), Dy (potassium dysprosium sulfide), Ho (potassium holmium sulfide), Er (potassium erbium sulfide), Tm (potassium thulium sulfide) and Yb (potassium ytterbium sulfide)] are either newly determined (KScS₂, RbScS₂ and KTbS₂) or redetermined. All of them belong to the α‐NaFeO₂ structure type in agreement with the ratio of the ionic radii r³⁺/r⁺. KScS₂, the member of this structural family with the smallest trivalent cation, is an extreme representative of these structures with rare earth trivalent cations. The title structures are compared with isostructural alkali rare earth sulfides in plots showing the dependence of several relevant parameters on the trivalent cation crystal radius; the parameters thus compared are c, a and c/a, the thicknesses of the S—S layers which contain the respective constituent cations, the sulfur fractional coordinates z(S²⁻) and the bond‐valence sums.     

Large‐Scale Synthesis of Enantiopure Molecular Cages: Chiroptical and Recognition Properties

A convenient and efficient gram‐scale synthesis for enantiopure hemicryptophane–tren (tren=tris(2‐aminoethyl)amine) derivatives has been developed. The four‐step synthesis is based on the optical resolution of a key intermediate, cyclotriveratrylene, for which the energy barrier for racemization has been measured to ensure that no racemization occurs during the two last steps of the synthetic pathway. The assignments of the absolute configurations have been performed by electronic circular dichroism and the enantiopurity was determined by NMR spectroscopy in the presence of enantiopure camphor sulfonic acid. To highlight the interest of such compounds, the recognition of norephedrine neurotransmitter was investigated and showed a remarkable enantioselectivity towards the C₃ symmetrical hosts. Finally, this highly modular synthetic pathway was used to provide eight enantiopure hemicryptophanes with different sizes, shapes, and functionalities. These results underline the high potential of this approach, which could lead to many applications in chiral recognition or asymmetric supramolecular catalysis.