The absence of nitrone form in re-determined crystal structure of 2-hydroxyimino-3-methyl-4-nitro-2,5-dihydrothiophene 1,1-dioxide

Crystal and molecular structures of 2-hydroxyimino-3-methyl-4-nitro-2,5-dihydrothiophene-1,1-dioxide C₅H₆N₂O₅S (I) have been re-determined by single crystal X-ray diffraction analysis. The structure of I (space group P2₁2₁2₁, a = 6.124(1) Å, b = 9.205(2) Å, c = 14.884(3) Å, Z = 4) was solved by the direct method and refined anisotropically in the full-matrix approximation to R = 0.064 using all 1756 measured independent reflections (automated diffractometer CAD-4, λCuK_α, anomalous scattering taken into account). This study proves that the compound I contains a disordered group H-O-N=C, but not the isomeric nitrone group O←N(H)=C, as it has been concluded by the workers who pioneered single crystal X-ray diffraction study of I and erroneously took the second low-occupied oxygen position of the disordered hydroxyimine group for H at N atom.     

Calculation of the proton affinities of polyfluorobenzenes and the activation energies for 1,2-hydrogen shifts in their carbocations

Isolated polyfluorobenzene (PFB) molecules and their protonated forms are investigated by the AM1 method with full geometry optimization. The proton affinities of PFB are estimated for different protonated positions. The proton affinity of PFB averaged over all isomers is shown to decrease monotonically as the number of fluorine atoms in the molecule increases. The relative populations of different isomers of arenonium ions (AI) formed by PFB protonation are determined. From the calculated data, the value of ⁺ for the F atom in theipso-position is estimated as 1.00. The activation energies of the 1,2-hydrogen shifts in AI are calculated. The dependences of the proton affinity and the activation energies of 1,2-hydrogen shifts on the number of halogen atoms are found to have distinct characters for PFB and polychlorobenzenes. The physical reasons for these difference are discussed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 1878–1882, November, 1993.     

On the applicability of the “abt” concept

Kaiser's “abt” concept rests on the experimental establishment of a linear relation between band width at half height, b_0.5, and capacity ratio, k, according to His column specification quantity, h_real, is dependent on the square of the slope a, obtained from a linear regression analysis based on this relation. It is shown in the present paper that an improvement of the experimental conditions leading to a lower extra-column contribution to band broadening, b, introduces a tendency towards a negative curvature in the plot at low k values. The mean slope increases, and an uncritical linear regression would yield an h_real-value which is higher than before and which would be in the opposite direction to the requirements of a reliable column specification. Generally the linear regression analysis has to be moved to higher k regions in cases of curvature, especially as it is also shown that h_real is an estimation of the traditional HETP value, H∞, that would be obtained when k approaches infinity. This theoretically expected relation is a strong motivation for the use of h_real as a column specification, since the b_0.5-value associated with H∞ is expected to be practically independent of b.     

LOW DENSITY POLYETHYLENE/CLAY NANOCOMPOSITES MODIFIED BY ETHYLENE COPOLYMERS： EFFECTS OF FUNCTIONALIZED SEGMENTS ON MORPHOLOGY

Melt extrusion was used to prepare binary nanocomposites of ethylene copolymers and organoclay and trinary nanocomposites of low-density polyethylene （LDPE）, ethylene copolymer and organoclay. X-ray diffraction （XRD） and transmission electron microscopy （TEM） were used to analyze the structure of the clay phase and the morphology of the nanocomposites. Influences of the comonomer in the copolymer and the content of the copolymer on the morphology of the resulting nanocomposites were discussed. The binary and the trinary composites may form intercalated or exfoliated structures depending on the interaction between the copolymer and the clay layers and the content of the copolymer.     

Analogy between real irreducible tensor operator and molecular two-particle operator

. Molecular matrix elements of a physical operator are expanded in terms of polycentric matrix elements in the atomic basis by multiplying each by a geometrical factor. The number of terms in the expansion can be minimized by using molecular symmetry. We have shown that irreducible tensor operators can be used to imitate the actual physical operators. The matrix elements of irreducible tensor operators are easily computed by choosing rational irreducible tensor operators and irreducible bases. A set of geometrical factors generated from the expansion of the matrix elements of irreducible tensor operator can be transferred to the expansion of the matrix elements of the physical operator to compute the molecular matrix elements of the physical operator. Two scalar product operators are employed to simulate molecular two-particle operators. Thus two equivalent approaches to generating the geometrical factors are provided, where real irreducible tensor sets with real bases are used. Received: 3 September 1996 / Accepted: 19 December 1996     

成核剂含量对β晶相聚丙烯结晶与熔融行为的影响

用DSC研究了β成核剂含量对β聚丙烯在等温与非等温结晶条件下的结晶与熔融行为的影响,发现当成核剂含量为0.005％时,结晶焓△H_c、β晶的熔融焓△H_(mβ)及熔点T_(mβ)均为最大,而α晶的相对含量最小.广角X-衍射数据表明,成核剂含量高的试样的(301)衍射峰的相对强度下降,反映分子链排列的纵向有序性降低.根据聚丙烯分子在β成核剂上附生结晶的成核机理解释了上述结果.     

THE PREPARATION AND STUDY ON THE NANO-TiO2/SILK FIBROIN COMPOSITE FILMS BY THE SOL-GEL METHOD

Based on the sol-gel technique using butyl titanate as oxide precursor, the regenerated SF (silk fibroin)/nano-TiO2 composite films were synthesized. Different amounts of butyl titanate to SF were used to verify this effect on the characteristics of the formed materials. Samples were characterized by thermogravimetric analysis, X-ray diffractometry, UV, AFM and FT-IR spectroscopy.The experimental results reveal that, compared to the pure silk fibroin films, the mechanical strength of these regenerated SF/nano-TiO2 composite films were increased and the dissolubility in water of SF/nano-TiO2 composite films in aqueous solution were decreased. The diameter of nano-TiO2 particle films was about 80nm through UV and AFM. The nano-TiO2 particles were well dispersed in the regenerated silk fibroin. It was found that the crystal structures of the composite films were transited from typical Silk Ⅰ to typical Silk Ⅱ by the XRD and FTIR. Furthermore, the crystallinity of the composite films was obviously improved. Through the TGA, it was demonstrated that the heat transition temperature of composite films was also enhanced.     

纳米氮化镁的合成

在制备高硬度、高热导、耐磨、耐腐蚀、耐高温的新兴陶瓷材料氧化硼、氮化硅的固相反应中，氮化镁是不可缺少的烧结助剂［‘，’j．同时，氮化镁还可用于制备发泡合金和回收核废料等领域．目前氮化镁的制备方法有：镁粉直接与氮气反应法［‘，‘1、镁在氮等离子流中与氮反应法＊‘、在氮气气氛下镁线圈爆炸法‘’‘和低压化学气相沉积法［’j．在上述方法中，有些方法需要复杂和昂贵的设备．有些方法得到氮化镁的产率较低．镁粉直接与氮气反应是具有工业生产价值的方法一然而，这种方法需要SOO”C到gOO”C的高温．我们曾经报道过利用温和…     

Electrochemical determination of dopamine and ascorbic acid at a novel gold nanoparticles distributed poly(4-aminothiophenol) modified electrode

A modified electrode is fabricated by embedding gold nanoparticles into a layer of electroactive polymer, poly(4-aminothiophenol) (PAT) on the surface of glassy carbon (GC) electrode. Cyclic voltammetry (CV) is performed to deposit PAT and concomitantly deposit Au nanoparticles. Field emission transmission electron microscopic image of the modified electrode, PAT-Au_nano-ME, indicates the presence of uniformly distributed Au nanoparticles having the sizes of 8-10 nm. Electrochemical behavior of the PAT-Au_nano-ME towards detection of ascorbic acid (AA) and dopamine (DA) is studied using CV. Electrocatalytic determination of DA in the presence of fixed concentration of AA and vice versa, are studied using differential pulse voltammetry (DPV). PAT-Au_nano-ME exhibits two well defined anodic peaks at the potential of 75 and 400 mV for the oxidation of AA and DA, respectively with a potential difference of 325 mV. Further, the simultaneous determination of AA and DA is studied by varying the concentration of AA and DA. PAT-Au_nano-ME exhibits selectivity and sensitivity for the simultaneous determination of AA and DA without fouling by the oxidation products of AA or DA. PAT and Au nanoparticles provide synergic influence on the accurate electrochemical determination of AA or DA from a mixture having any one of the component (AA or DA) in excess. The practical analytical utilities of the PAT-Au_nano-ME are demonstrated by the determination of DA and AA in dopamine hydrochloride injection and human blood serum samples.     

分散共聚法制备特殊形态高分子微球的研究

以聚乙二醇 (PEG)大分子单体为反应性稳定剂 ,在丙烯腈的分散共聚反应中添加少量苯乙烯以形成疏水性核 ,制备得到了亚微米级高分子微球 .透射电子显微镜研究表明 ,该高分子微球具有特异的形态结构 .同时研究了分散共聚体系中各种反应因素对微球形态和直径的影响 ,结果表明 ,苯乙烯单体的添加量、PEG大分子单体的浓度及分子量、混合溶剂的组成对微球直径和形态均有明显的影响 .X 射线光电子能谱 (XPS)研究结果表明 ,微球表面聚集有亲水性PEG链 ,核为疏水的聚 (丙烯腈 苯乙烯 ) ,即形成的特异形态的PEG接枝高分子微球亦为复合型结构