Sensitive Voltammetric Response of p‐Nitroaniline on Single‐Wall Carbon Nanotube‐Ionic Liquid Gel Modified Glassy Carbon Electrodes

An ionic liquid (i.e., 1‐butyl‐3‐methylimidazolium hexafluorophosphate, BMIMPF₆)‐single‐walled carbon nanotube (SWNT) gel modified glassy carbon electrode (BMIMPF₆‐SWNT/GCE) is fabricated. At it the voltammetric behavior and determination of p‐nitroaniline (PNA) is explored. PNA can exhibit a sensitive cathodic peak at ?0.70 V (vs. SCE) in pH 7.0 phosphate buffer solution on the electrode, resulting from the irreversible reduction of PNA. Under the optimized conditions, the peak current is linear to PNA concentration over the range of 1.0×10^?8–7.0×10^?6 M, and the detection limit is 8.0×10^?9 M. The electrode can be regenerated by successive potential scan in a blank solution for about 5 times and exhibits good reproducibility. Meanwhile, the feasibility to determine other nitroaromatic compounds (NACs) with the modified electrode is also tested. It is found that the NACs studied (i.e., p‐nitroaniline, p‐nitrophenol, o‐nitrophenol, m‐nitrophenol, p‐nitrobenzoic acid, and nitrobenzene) can all cause sensitive cathodic peaks under the conditions, but their peak potentials and peak currents are different to some extent. Their peak currents and concentrations show linear relationships in concentration ranges with about 3 orders of magnitude. The detection limits are 8.0×10^?9 M for p‐nitroaniline, 2.0×10^?9 M for p‐nitrophenol, 5.0×10^?9 M for o‐nitrophenol, 5.0×10^?9 M for m‐nitrophenol, 2.0×10^?8 M for p‐nitrobenzoic acid and 8.0×10^?9 M for nitrobenzene respectively. The BMIMPF₆‐SWNT/GCE is applied to the determination of NACs in lake water.     

8—氮鸟嘌呤的极谱伏安行为

用循环伏安法（ＣＶ）、电流采样极诸法（ＳＣＰ，即ＴＡＳＴ）、常规脉冲极谱法（ＮＰＰ）、微分脉冲极谱法（ＤＰＰ）、线性扫描伏安法（ＬＳＶ）、Ｏｓｔｅｒｙｏｕｎｇ方波伏安法（ＯＳＷＶ）和计时库仑法（ＣＣ）等电化学技术研究了抗癌药物８－氮鸟嘌呤（８－ａｚａｇｕａｎｉｎｅ，ｇｕａｎａｚｏｌｏ，简称８－ＡＧ）的极谱伏安行为．在 ０． １ｍｏｌ／Ｌ Ｈ２ＳＯ４底液中，８－ＡＧ有一良好的还原峰，峰电位（Ｅｐ）在－０． ９５Ｖ（ｖｓ．Ａｇ／ＡｇＣｌ，下同）附近，８－ＡＧ浓度在４×１０－６～８×１０－４ｍｏｌ／Ｌ范围内．峰高与浓度有良好的线性关系，线性相关系数ｒ＝０．９９９９～０．９９１０，检出限为１× １０－６ｍｏｌ／Ｌ．实验证明了该峰具有吸附性．本文提出了电极反应机理，它包括：酸性介质中８－ＡＧ的质子化、质子化的８－ＡＧ在汞电极上吸附以及完全不可逆的两电子还原过程．同时用量子化学计算方法（全略微分重叠法即ＣＮＤＯ／２）对８－ＡＧ和鸟嘌呤的各原子的净电荷以及Ｗｉｂｅｒｇ键级进行了计算，从理论上解释了８－ＡＧ的电化学还原机理。     

Electron Paramagnetic Resonance Study of Radical Pairs and Isolated Radicals Trapped in Irradiated Long-Chain Hydrocarbons at Low Temperatures

The intrinsic characteristics of radical pairs produced in squalane and in cetane receiving high gamma-dose are extensively studied with the EPR technique at temperatures from 77°K up to 150°K. The spectra of the paired radicals occur at g=4 with a very low transition probability in contrast to that of isolated radicals which appear at g=2 A well-resolved hyperfine spectrum corresponding to the species (CH₃CH₂.CH₂CH₃) is observed in cetane. The isothermal decay rates of radical pairs in cetane below 100°K are significantly slow; however, the decay kinetics at 150°K is first order with rate constant=1.86 min^?1. A relatively slower decay rate is obtained for isolated radicals suggesting that the decay mechanism of paired radicals is through geminate recombination. The relative inter-radical distance in radical pairs is known from a decay curve as a function of temperature. The yields of radical pairs are low in both matrices, only few percents of those of isolated radicals. The formation mechanisms of paired radicals with direct radiolytic bond scission process are discussed in connection with the experimental observations.     

New zinc phosphates decorated by imidazole-containing ligands

Four new zinc phosphates [Zn(HPO4)(C6H9N3O2)] (1), [Zn(HPO4)(C4H6N2)].H2O (2), [Zn2(HPO4)2(C14H14N4)].2H2O (3), and [Zn(HPO4)(C14H14N4)] (4) were synthesized in the presence of d-histidine, 1-methylimidazole, 1,4-bis(imidazol-1-ylmethyl)benzene (L1), and 1,2-bis(imidazol-1-ylmethyl)benzene (L2), respectively, and their structures were determined by X-ray crystallography. The inorganic framework of compounds 1, 2, and 3 is composed of vertex-shared ZnO3N and HPO4 tetrahedra that form four rings, which, in turn, are linked to generate a one-dimensional ladder structure. In 1 and 2 the organic groups (monoimidazole ligand) are located at each side of the ladders, while in 3 the bisimidazole ligand, 1,4-bis(imidazol-1-ylmethyl)benzene, links the ladders together to form a novel 2D structure. Compound 1 is the first zinc phosphate framework to be templated by an N-bonded chiral amino acid. In 4 the zero-dimensional four rings are joined together by the linear bridging ligand, 1,2-bis(imidazol-1-ylmethyl)benzene, to generate a one-dimensional framework with a new face-to-face structural motif. The 3D structure of compound 4 is stabilized by hydrogen-bonding, pi-pi interactions, and C-H...pi interactions. The approach of incorporating multifunctional ligands into zinc phosphate frameworks and linking the inorganic zinc phosphates subunits by an organic ligand provides opportunities for the design of new inorganic-organic open frameworks.     

Ultrathin polymer film formation by collision-induced cross-linking of adsorbed organic molecules with hyperthermal protons

A new synthetic approach for the formation of ultrathin polymer films with customizable properties was developed. In this approach, the kinematic nature of proton collisions with simple organic molecules condensed on a substrate is exploited to break C-H bonds preferentially. The subsequent recombination of carbon radicals gives a cross-linked polymer thin film, and the selectivity of C-H cleavage preserves the chemical functionalities of the precursor molecules. The nature and validity of the method are exemplified with theoretical results from ab initio molecular dynamics calculations and experimental evidence from a variety of characterization techniques. Its applicability is demonstrated by the synthesis of ultrathin polymer films with precursor molecules such as dotriacontane, docosanoic acid, poly(acrylic acid) oligomer, and polyisoprene. The approach is fundamentally different from conventional chemical synthesis as it involves an unusual mix of physical and chemical processes including charge exchange, projectile penetration, kinematics, collision-induced dissociation, inelastic energy transfer, chain transfer, and chain cross-linking.     

4,4’-一氧二（苯胺灵）的合成和晶体结构

通过4,4’-一氧二（异氰酸苯酯）与异丙醇加成反应，合成标题化合物 4,4’-一氧二（苯胺灵）(Ⅰ) (C20H24N2O5, Mr=372.41)，并用X射线衍射、红外光谱、13C核磁共振、电子轰击质谱和元素分析对标题化合物进行表征. 晶体属于三斜晶系，空间群为P1晶体学参数为: a=0.85107(17), b=0.91164(18), c=1.45701(3) nm, α=80.44(3)°, β=85.25(3)°, γ=62.88(3)°, V=0.9922(3) nm3, Z=2, Dc=1.247 g•cm－3, μ(Mo Kα)=0.90 cm－1, F(000)=396.两个苯环平面之间的夹角为62.06° (0.06°). 晶体结构经全矩阵最小二乘法修正，最终偏离因子R=0.0520, wR=0.1434(对可观察点).此化合物应具有广谱的生物活性.     

One step isolation and purification of liquiritigenin and isoliquiritigenin from Glycyrrhiza uralensis Risch. using high-speed counter-current chromatography

High-speed counter-current chromatography (HSCCC) technique in semi-preparative scale has been successfully applied to the separation of bioactive flavonoid compounds, liquiritigenin and isoliquiritigenin in one step from the crude extract of Glycyrrhiza uralensis Risch. The HSCCC was performed using a two-phase solvent system composed of n-hexane-ethyl acetate-methanol-acetonitrile-water (2:2:1:0.6:2, v/v). Yields of liquiritigenin (98.9% purity) and isoliquiritigenin (98.3% purity) obtained were 0.52% and 0.32%. Chemical structures of the purified liquiritigenin and isoliquiritigenin were identified by electrospray ionization-MS (ESI-MS) and NMR analysis.     

Novel metal-organic frameworks with specific topology from new tripodal ligands: 1,3,5-tris(1-imidazolyl)benzene and 1,3-bis(1-imidazolyl)-5-(imidazol-1-ylmethyl)benzene

Reactions of two new tripodal ligands 1,3,5-tris(1-imidazolyl)benzene (4) and 1,3-bis(1-imidazolyl)-5-(imidazol-1-ylmethyl)benzene (5) with metal [Ag(I), Cu(II), Zn(II), Ni(II)] salts lead to the formation of novel two-dimensional (2D) metal-organic frameworks [Ag(2)(4)(2)][p-C(6)H(4)(COO)(2)].H(2)O (6), [Ag(4)]ClO(4) (7), [Cu(4)(2)(H(2)O)(2)](CH(3)COO)(2).2H(2)O (8), [Zn(4)(2)(H(2)O)(2)](NO(3))(2) (9), [Ni(4)(2)(N(3))(2)].2H(2)O (10), and [Ag(5)]ClO(4) (11). All the structures were established by single-crystal X-ray diffraction analysis. Crystal data for 6: monoclinic, C2/c, a = 23.766(3) A, b = 12.0475(10) A, c = 13.5160(13) A, beta = 117.827(3) degrees, Z = 4. For compound 7: orthorhombic, P2(1)2(1)2(1), a = 7.2495(4) A, b = 12.0763(7) A, c = 19.2196(13) A, Z = 4. For compound 8: monoclinic, P2(1)/n, a = 8.2969(5) A, b = 12.2834(5) A, c = 17.4667(12) A, beta = 96.5740(10) degrees, Z = 2. For compound 9: monoclinic, P2(1)/n, a =10.5699(3) A, b = 11.5037(3) A, c = 13.5194(4) A, beta = 110.2779(10) degrees, Z = 2. For compound 10: monoclinic, P2(1)/n, a = 9.8033(3) A, b = 12.1369(5) A, c = 13.5215(5) A, beta = 107.3280(10) degrees, Z = 2. For compound 11: monoclinic C2/c, a = 18.947(2) A, b = 9.7593(10) A, c = 19.761(2) A, beta = 97.967(2) degrees, Z = 8. Both complexes 6 and 7 are noninterpenetrating frameworks based on the (6, 3) nets, and 8, 9 and 10 are based on the (4, 4) nets while complex 11 has a twofold parallel interpenetrated network with 4.8(2) topology. It is interesting that, in complexes 6,7, and 11 with three-coordinated planar silver(I) atoms, each ligand 4 or 5 connects three metal atoms, while in the case of complexes 8, 9, and 10 with six-coordinated octahedral metal atoms, each ligand 4 only links two metal atoms, and another imidazole nitrogen atom of 4 did not participate in the coordination with the metal atoms in these complexes. The results show that the nature of organic ligand and geometric needs of metal atoms have great influence on the structure of metal-organic frameworks.     

Fluorescent polymer cubosomes and hexosomes with aggregation-induced emission

Fluorescent polymer cubosomes and hexosomes with aggregation-induced emission (AIE) were prepared from amphiphilic block copolymers PEG-b-PTPEMA where the hydrophobic block PTPEMA was a polymethacrylate with tetraphenylethene (TPE) as the AIE side group. Four highly asymmetric block copolymers with hydrophilic block weight ratio f_PEG ≤ 20% were synthesized. Cubosomes and hexosomes with strong fluorescence emission were obtained by nanoprecipitation of polymers with f_PEG < 9% in dioxane/water and THF/water systems. Their ordered internal structures were studied by electron microscopy (cryo-EM, SEM and TEM) and the X-ray scattering technique (SAXS). To elucidate the formation mechanisms of these inverted colloids, other parameters influencing the morphologies, like the water content during self-assembly and the organic solvent composition, were also investigated. This study not only inspires people to design novel building blocks for the preparation of functional cubosomes and hexosomes, but also presents the first AIE fluorescent polymer cubosome and hexosome with potential applications in bio-related fields.

Fluorescent Im$\bar{3}$m cubosome and P6mm hexosome with aggregation-induced emission (AIE) were reported, which were formed by amphiphilic block copolymers PEG-b-PTPEMA. The length of hydrophobic block PTPEMA was adjusted to control morphology formation.     

The first catalytic,asymmetric alpha-additions of isocyanides. Lewis-base-catalyzed,enantioselective Passerini-type reactions

The first, catalytic, enantioselective alpha-additions of isocyanides to aldehydes have been demonstrated (Passerini-type reactions). The catalytic system of silicon tetrachloride and a chiral bisphosphoramide 5a provided high yields and good to excellent enantioselectivities for the addition of tert-butyl isocyanide to a wide range of aldehydes (aromatic, olefinic, acetylenic, aliphatic). Aqueous workup afforded the alpha-hydroxy tert-butyl amides, whereas methanolic quench followed by basic workup afforded the alpha-hydroxy methyl esters.