Effects of the architecture and environment on polymeric molecular assemblies of novel amphiphilic diblock copolynorbornenes with narrow polydispersity via living ring‐opening metathesis polymerization

Diblock copolymers of 5‐(methylphthalimide)bicyclo[2.2.1]hept‐2‐ene (NBMPI) and 1,5‐cyclooctadiene were synthesized by living ring‐opening metathesis polymerization with a well‐defined catalyst {RuCl₂(CHPh)[P(C₆H₁₁)₃]₂}. Unhydrogenated diblock copolymers showed two glass transitions due to poly(NBMPI) and polybutadiene segments, such as two glass‐transition temperatures at ?86.5 and 115.3 °C for poly 1a and ?87.2 and 115.3 °C for poly 1b . However, only one melting temperature could be observed for hydrogenated copolymers, such as 119.8 °C for poly 2a and 121.7 °C for poly 2b . The unhydrogenated diblock copolymer with the longer poly(NBMPI) chain (poly 1a ; temperature at 10% mass loss = 400 °C) exhibited better thermal stability than the one with the shorter poly(NBMPI) chain (poly 1b ; temperature at 10% mass loss = 385 °C). Two kinds of hydrogenated diblock copolymers, poly 2a and poly 2b , exhibited relatively poor solubility but better thermal stability than unhydrogenated diblock copolymers because of the polyethylene segments. Poly[(hydrochloride quaternized 2‐norbornene‐5‐methyleneamine)‐b‐butadiene]‐1 (poly 3a ) was obtained after the hydrolysis and quaternization of poly 1a . Dynamic light scattering measurements indicated that the hydrodynamic diameters of the cationic copolymer (poly 3a ) in water (hydrodynamic diameter = 1580 nm without salt), methanol/water (4/96 v/v; hydrodynamic diameter = 1500 nm without salt), and tetrahydrofuran/water (4/96 v/v; hydrodynamic diameter = 1200 nm without salt) decreased with increasing salt (NaCl) concentration. The effect of temperature on the hydrodynamic diameter of hydrophobically modified poly 3a was also studied. The inflection point of the hydrodynamic diameter of poly 3a was observed at various polymer concentrations around 30 °C. The critical micelle concentration of hydrophobically modified poly 3a was observed at 0.018 g dL^?1. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2901–2911, 2006     

同位素稀释-火花源质谱法分析人参样品中微量元素

本文采用同位素稀释-火花源质谱法定量分析了吉林野山参,园参及高丽参中30多种微量元素的含量。测定下限2μg/g,相对标准偏差在5～28％以内。     

磷脂液相二次离子质谱分析中的分子离子簇

对3种极性头不同的磷脂DMPG、DMPC、DMPE的液相二次离子质谱分析中出现 的分子离子簇现象进行了系统的研究。结果表明，虽然分子离子簇的形成与许多因素有关， 如PH值、离子强度等，但起决定作用的是样品在底物中的浓度，浓度增大有利于分子离子簇 的形成。研究还发现，由不同种类磷脂分子形成的分子离子簇峰明显高于由同种磷脂分子所 形成的分子离子簇峰，指出异种磷脂分子间的簇离子形成能力高于同种磷脂分子。此外还讨 论了磷脂分子在离子源条件下的稳定性、裂解规律及相互作用等。结果表明，本实验所选用 的磷脂分子在LSIMS条件下是稳定的，均能得到较强的分子离子峰，其主要碎片峰是磷酰键断裂而产生的碎片离子峰。     

Synthesis of novel tetracyclic chromenes through carbanion chemistry of 4-methyl coumarins

Various substituents were introduced onto the methyl group in 4-methyl coumarins through lithiation, followed by reactions with a wide range of electrophiles. The presence of an alkoxy group on 6′-phenyl ring was found to be pivotal for the success of this reaction. This procedure provided a convenient synthetic pathway to elaborate the methyl group of 4-methylcoumarins. Application of this methodology was showcased with the synthesis of biologically important novel tetracyclic chromene ring systems (n = 1-3).     

Dinuclear iron(II)-cyanocarbonyl complexes linked by two/three bridging ethylthiolates: relevance to the active site of [Fe] hydrogenases

Dinuclear iron(II)-cyanocarbonyl complex [PPN](2)[Fe(CN)(2)(CO)(2)(mu-SEt)](2) (1) was prepared by the reaction of [PPN][FeBr(CN)(2)(CO)(3)] and [Na][SEt] in THF at ambient temperature. Reaction of complex 1 with [PPN][SEt] produced the triply thiolate-bridged dinuclear Fe(II) complex [PPN][(CN)(CO)(2)Fe(mu-SEt)(3)Fe(CO)(2)(CN)] (2) with the torsion angle of two CN(-) groups (C(5)N(2) and C(3)N(1)) being 126.9 degrees. The extrusion of two sigma-donor CN(-) ligands from Fe(II)Fe(II) centers of complex 1 as a result of the reaction of complex 1 and [PPN][SEt] reflects the electron-rich character of the dinuclear iron(II) when ligated by the third bridging ethylthiolate. The Fe-S distances (2.338(2) and 2.320(3) A for complexes 1 and 2, respectively) do not change significantly, but the Fe(II)-Fe(II) distance contracts from 3.505 A in complex 1 to 3.073 A in complex 2. The considerably longer Fe(II)-Fe(II) distance of 3.073 A in complex 2, compared to the reported Fe-Fe distances of 2.6/2.62 A in DdHase and CpHase, was attributed to the presence of the third bridging ethylthiolate, instead of pi-accepting CO-bridged ligand as observed in [Fe] hydrogenases. Additionally, in a compound of unusual composition ([Na.(5)/(2)H(2)O][(CN)(CO)(2)Fe(mu-SEt)(3)Fe(CO)(2)(CN)])(n)((1)/(2)O(Et)(2))(n) (3), the Na(+) cations and H(2)O molecules combining with dinuclear [(CN)(CO)(2)Fe(mu-SEt)(3)Fe(CO)(2)(CN)](-) anions create a polymeric framework wherein two CN(-) ligands are coordinated via CN(-)-Na(+)/CN(-)-(Na(+))(2) linkages, respectively.     

The interfacial dilational properties of hydrophobically modified associating polyacrylamide studied by the interfacial tension relaxation method at an oil-water interface

The interfacial dilational viscoelastic properties of hydrophobically associating block copolymer composed of acrylamide (AM) and a low amount of 2-phenoxylethyl acrylate (POEA) (<1.0 mol%) at the octane-water interfaces were studied by means of the interfacial tension relaxation method. The dependencies of interfacial dilational elasticity and viscous component on the dilational frequency were investigated. The interaction of hydrophobically associating block copolymer [P(AM/POEA)] with sodium dodecyl sulfate (SDS) has been explored. The results show that at lower frequency, the dilational elasticity for different concentration copolymer is close to zero; at higher frequency, the dilational elasticity shows no change with increased frequency; At moderate frequency (10(-3)-1 Hz), the dilational elasticity decreased with a decrease in the dilational frequency. The results show that the hydrophobic groups of [P(AM/POEA)] chains can be associated by inter- or intrachain liaisons in water solution. The dilational viscous component for P(AM/POEA) comes forth a different maximum value at different frequencies when the polymer concentration is different. It is generally believed that the dilational viscous component reflects the summation of the various microscopic relaxation processes at and near the interface and different relaxation processes have different characteristic frequencies. The spectrum of dilational viscous component may appear more than once maximum values at different frequencies. The influence of SDS on the limiting dilational elasticity and viscous component for polymer solution was elucidated. For 5000 ppm polymer solution, the limiting dilational elasticity decreased with an increase in SDS concentration. The dilational viscous component passed through a maximum value with a rise in the dilational frequency, which appeared at different frequency when SDS concentration is different; and the higher is the concentration, the lower is the dilational frequency. It can be explained that macromolecules may be substituted by SDS molecules in the interface and the interaction of molecules decrease, which makes the limiting dilational elasticity decrease. For 200 ppm polymer solution, the limiting dilational elasticity increased firstly and then decreased with SDS concentration increasing. This may be explained that the interfacial polymer concentration is so low that SDS molecules absorbed in the interface dominate dilational properties of the interfacial film even at very low SDS concentration. However, SDS molecules can gradually substitute the polymer molecules in the interface with a rise in SDS concentration, which results in the decrease in the limiting dilational elasticity.     

A Minor New Flavone from Scutellaria baicalensis Georgi

A new flavone,6,2′-dihydroxy-5,7,8,6′-tetramethoxyflavone,was isolated from the roots of Scutellaria baicalensis. Its structure was established on the basis of spectral evidences.     

羟基取代烷基苯磺酸盐界面扩张粘弹性质

研究了2-羟基-3,5-二癸基苯磺酸钠(C10C10OHphSO3Na)表面和正癸烷-水界面上的扩张粘弹性质, 考察了平衡时间对界面性质的影响. 研究结果表明, 羟基取代烷基苯磺酸钠具有十分特异的界面性质, 其扩张模量比一般表面活性剂大一个数量级, 达到平衡的时间较长, 形成的界面膜弹性较大. 界面张力弛豫测定结果表明, 平衡时界面上存在特征时间长达103 s的慢过程. 上述实验结果可能是由于羟基间形成氢键造成的.     

漆树漆酶的催化氧化作用——Ⅳ.二茂铁及其衍生物的酶促氧化

In phosphate buffer-diethylene glycol monobutyl ether(DGBE), the oxidations of ferrocene and 15 derivatives were investigated in the presence of Rhus vernicifera laccase. The results showed that ferrocene and 11 derivatives can be oxidized. The mechanism of Laccase catalyzed oxidation of ferrocene was put forward.     

Analytical pyrolysis of carbohydrates: I. Chemical interpretation of matrix influences on pyrolysis-mass spectra of amylose using pyrolysis-gas chromatography-mass spectrometry

Inorganic additives, viz. Na₂CO₃, NaOH, HCl, ZnC₂, NaH₂PO₄, Na₂HPO₄, NaCl. MgSO₄ and sea salt, to the pyrolysis matrix change the pyrolysis-mass spectrum of amylose significantly. Carbonyl compounds, acids and their lactones, furans, pyranones anhydrosugars and aromatic substances are found in different ratios under the various conditions, as determined by pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS).Carbonyl compounds, acids and lactones are released from alkaline and neutral matrices. Furans and anhydrohexoses are particularly formed under neutral and acidic conditions. Pyranones are specific for phosphate matrices. Unsaturated hydrocarbons and aromatic substances arise from strongly alkaline or dehydrating matrices. Degradation pathways are proposed for various compound categories.The results of pyrolysis-mass spectrometry and Py-GC-MS are highly compatible.