七-(2,6-二-O-甲基)-β-环糊精对1,1 -联萘酚对映体手性识别的电喷雾质谱研究

利用电喷雾质谱研究了β-环糊精、七-(2,6-二-O-甲基)-β-环糊精作为手性识别试剂对1,1'-联萘酚对映体的手性识别效应.实验结果表明,在气相中,β-环糊精与七-(2,6-二-O-甲基)-β-环糊精都可以与联萘酚形成非共价复合物.对形成的复合物的串联质谱研究表明,β-环糊精不能识别联萘酚对映体,而七-(2,6-二-O-甲基)-β-环糊精对联萘酚对映体有较强的手性识别效应.进一步研究表明七-(2,6-二-O-甲基)-β-环糊精与联萘酚对映体混合比例以及CID能量对于手性识别并无影响.

Phase transition behavior and structure of the thermotropic liquid crystal 6-{[(4 '-{[(undecyl)carbonyl]oxy}biphenyl-4yl)carbonyl]oxy}-1-hexyne

The phase transition behaviors and corresponding structures of 6-{[(4'-([(undecyl)carbonyl]oxy)biphenyl-4yl)carbonyl]oxyl-l-hexyne (A4EE11) were investigated using differential scanning calorimetry (DSC), polarizing optical microscopy (POM) and wide angle X-ray diffraction (WAXD). In comparison with the published homologues, 5- [(4'-heptoxy-biphenyl-4-yl)carbonyl]oxyl-1-pentyne (A3EO7) which shows a monotropic smectic A (SmA) phase and a metastable monotropic smectic C (SmC) phase; 5-{ [(4'-heptoxybiphenyl-4-yl)oxy]carbonyl)- I-pentyne (A3E'O7) that exhibits three enantiotropic stable liquid crystalline (LC) phases, SmA phase, SmC phase and smectic X (SmX) phase; 5-{[(4'-heptoxy-biphenyl-4-yl)carbonyl]oxy}-1-undecyne (A9EO7) which has a monotropic SmA phase and a metastable crystal phase, A4EE11 integrates the enantiotropy, monotropy and metastability of the LC phases of those three compounds. Upon cooling from isotropic state to room temperature, in the temperature range of 62.0 to 58.5 degrees C, A4EE11 shows an enantiotropic smectic A (SmA) phase with a layer spacing d=32.69 angstrom.

(E)-6-fluoropyridine-2-carbaldehyde oxime

The title compound, C6H5FN2O, exists as the E isomer. The crystal structure is stabilized by O-(HN)-N-... hydrogen bonding.

6,7,8,9-Tetrahydro-5H-pyrido[2,3-b]azepine-5,8-dione: a hydrogen-bonded dimer structure

In the title compound, C9H8N2O2, two crystallographically independent molecules form a dimer structure, in which two N-H center dot center dot center dot N hydrogen bonds generate an intermolecular R-2(2)( 8) ring.

七-(2,6-二-O-甲基)-β-环糊精对薄荷醇对映体手性识别的电喷雾质谱研究

利用电喷雾质谱研究了七-(2,6-二-O-甲基)-β-环糊精(DM-β-CD)作为手性识别试剂对薄荷醇对映体的手性识别效应。实验结果表明,在气相条件下,DM-β-CD可以与薄荷醇形成特异性结合复合物,化学计量比为1∶1。对复合物的串联质谱研究表明,DM-β-CD对薄荷醇对映体有较强的手性识别能力,手性识别率为Rchiral=1.81。DM-β-CD与(-)-薄荷醇形成的复合物比与(+)-薄荷醇形成的复合物稳定。

用核磁共振方法表征6(8)氨基-3H苯[1,2]氧嗪-1,4-二酮

用一维1HNMR、13CNMR方法研究了6(8)氨基-3H苯[1,2]氧嗪-1,4二-酮的结构,并通过二维1H-1H同核相关谱(COSY)、13C-1H异核相关谱(HMQC)及13C-1H异核远程相关谱(HMBC)进一步确定了该类化合物的1H谱和13C谱中各谱峰的归属,为研究同类化合物表征提供了依据。

Systematic study of the transfer of amino acids across the water/1,2-dichloroethane interface facilitated by dibenzo-18-crown-6

Facilitated ion transfer reactions of 20 amino acids with di.benzo-18-crown-6 (DB18C6) at the water/1,2-dichloroethane (W/DCE) interfaces supported at the tips of micro- and nano-pipets were investigated systematically using cyclic voltammetry. It was found that there were only 10 amino acids, that is, Leu, Val, Ile, Phe, Trp, Met, Ala, Gly, Cys, Gln (in brief), whose protonated forms as cations can give well-defined facilitated ion transfer voltammograms within the potential window, and the reaction pathway was proven to be consistent with the transfer by interfacial complexation/dissociation (TIC/TID) mechanisms. The association constants of DB 18C6 with different amino acids in the DCE (beta(0)), and the kinetic parameters of reaction were evaluated based on the steady-state voltammetry of micro- or nano-pipets, respectively The experimental results demonstrated that the selectivity of complexation of protonated amino acid by DB18C6 compared with that of alkali metal cations was low, which can be attributed to the vicinal effect arising from steric hindrance introduced by their side group and the steric bulk effect by lipophilic stabilization.

A two-dimensional molybdenum (V) phosphate with covalently bonded transition metal coordination complexes: hydrothermal synthesis and structure characterization of Na-2[{Mn(phen)(2)(H2O)}{Mn(phen)(2)}(3){Mn (Mo12O24)-O-V (HPO4)(6)(PO4)(2)(OH)(6)}] center dot 4H(2)O (phen=1,10-phenanthroline)

An organic-inorganic hybrid molybdenum phosphate, Na-2[{Mn(phen)(2)(H2O)} {Mn(phen)(2)}(3){(MnMo12O24)-O-v (HPO4)(6)(PO4)(2) (OH)(6)}] . 4H(2)O (phen=1,10-phenanthroline), involving molybdenum present in V oxidation state and covalently bonded transition metal coordination complexes, has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction. Deep brown-red crystals are formed in the triclinic system, space group P (1) over bar, a=16.581(l)Angstrom, b=18.354(1)Angstrom, c=24.485(2)Angstrom, alpha=80.589(l)degrees, beta=71.279(1)degrees, gamma=67.084(1)degrees, V=6493.8(8)Angstrom(3), Z=2, lambda(MoKalpha)=0.71073Angstrom (R(F)=0.0686 for 29,053 reflections). Data were collected on a Bruker Smart Apex CCD diffractometer at 293 K in the range of 1.76 < theta < 28.06degrees using omega-2theta scans technique. The structure of the title compound may be considered to be based on {Mo6O12(HPO4)(3)(PO4)(OH)(3)} units bonded together with {Mn(phen)(2)} subunits into a two-dimensional network. Two types of tunnels are observed in the solid of the title compound.

Compatibilization of polyamide-6/syndiotactic polystyrene blends using styrene/glycidyl methacrylate copolymers

Blends of polyamide-6 (PA6) with syndiotactic polystyrene (sPS) were prepared using a series of styrene/glycidyl methacrylate (SG) copolymers as compatibilizers. These copolymers are miscible with sPS, and the epoxide units in SG are capable of reacting with PA6 end groups. These copolymers thus have the potential to form SG-g-PA6 graft copolymers at the PA6/sPS interface during melt processing. This study focuses on the effects of functionality and concentration of the compatibilizer on the morphological, mechanical and crystallization behaviors of the blends.. In general, SG copolymers are effective in reducing the sPS domain size and improving the interfacial adhesion. About 5 wt% glycidyl methacrylate (GMA) is the optimum content in SG copolymer that produces the best compatibilization. Both the strength and modulus of the blend have been improved on addition of the SG copolymers, accompanying a loss in toughness when higher concentration copolymer is added. Incorporation of SG compatibilizers to PA6/sPS blend has little influence on the crystallization behavior of PA6 component but resulted in a steady reduction in intensity of crystallinity peak of sPS and simultaneous crystallization of sPS with PA6 is observed.

高功率镍氢电池La_(1-x)Mg_x(NiCoAl)_(3.6)金属氢化物电极的电化学性能研究

MH-Ni电池具有电化学比能量高、耐过充/放电性能好、无记忆效应和环境友好等优点而得到广泛应用.金属氢化物电极是MH-Ni电池的核心材料,其研究工作主要集中在稀土AB_5系、钛系、锆系和镁基等合金作为MH-Ni电池金属氢化物电极方面.但这些体系合金的电化学容量低,活化

Reactive compatibilization of polyamide 6 with isocyanate functionalized ethylene-propylene copolymer

Reactive compatibilization of ethylene-propylene copolymer functionalized with allyl (3-isocyanato-4-tolyl) carbamate (TAI) isocyanate (EPM-g-TAI) and polyamide 6 (PA6) was investigated in this paper, FTIR analysis revealed the evidence of a chemical reaction between the end groups of PA6 and EPM-g-TAI. Thermal, rheological, morphological, and mechanical properties of the resultant system were examined, DSC analysis indicated that the crystallization of PA6 in Pa6/EPM-g-TAI blends was inhibited, due to the chemical reaction that occurs at the interface of PA6 and EPM-g-TAI. Rheological measurement showed that complex viscosity and storage modulus of PA6/EPM-g-TAI were both dramatically enhanced compared to those of PA6/EPM at the same blending composition. After examining the morphology of both blending systems, smaller particile sizes, more homogeneous distribution of domains and improved interfacial adhesion between matrix and domains were observed in the compatibilized system. Mechanical properties such as tensile strength. Young's modulus, flexural strength and modulus, as well as notched and un-notched impact strength of PA6/EPM-g-TAI blends were also found to improve gradually with increasing the content of grafted TAI.

Hydrothermal synthesis and structural characterization of a novel P-V-O layered compound [H(2)en](2)[H3O](6)[Co(H2O)(2)(VO)(8)(OH)(4)(PO4)8]

A new compound [H(2)en](2)[H3O](6)[Co(H2O)(2)(VO)(8)(OH)(4)(PO4)(8)] has been hydrothermally synthesized. Single crystal X-ray analysis indicates that this compound crystallizes in a monoclinic system, space group P2(1)/n with a=1.438 5(3) nm, b=1.012 2(2) nm, c=1.832 5(4) nm, beta=90.21degrees, V=2.668 2 (9) nm(3), Z = 2, D-c = 2.112 g/cm(3), R = 0.055, wR = 0.149 7, S = 1.037. The structure of [H(2)en](2)[H3O](6)[Co(H2O)(2)(VO)(8)(OH)(4)(PO4)(8)] is characterized by P-V-O layers constructed by [(VO)4 (OH)(2)(PO4)(4)](6-) non-symmetric units. The P-V-O layers are pillared by [Co(H2O)(2)](2+) group, resulting in the channels within which the protonated diaminoethane and H3O+ are located.

Systematic investigation of alkali metal ion transfer across the micro- and nano-water/1,2-dichloroethane interfaces facilitated by dibenzo-18-crown-6

Facilitated alkali metal ion (M+= Li+, Na+, K+, Rb+, and Cs+) transfers across the micro- and nano-water/1,2-dichloroethane (W/DCE) interfaces supported at the tips of micro- and nanopipets by dibenzo-18-crown-6 (DB18C6) have been investigated systematically using cyclic voltammetry. The theory developed by Matsuda et al. was applied to estimate the association constants of DB18C6 and M+ in the DCE phase based on the experimental voltammetric results. The kinetic measurements for alkali metal ion transfer across the W/DCE interface facilitated by DB18C6 were conducted using nanopipets or-submicropipets, and the standard rate constants (k(0)) were evaluated by analysis of the experimental voltammetric data. They increase in the following order: k(Cs+)(0) < k(Li+)(0) < k(Rb+)(0) < k(Na+)(0) < k(K+)(0), which is in accordance with their association constants except Cs+ and Li+.

A novel one-dimensional manganese phosphomolybdate with rectangular cavities: [H3N(CH2)(4)NH3] (H3O)(2){[Mn(phen)(2)](4) [(MnMo12O30)-O-v(HPO4)(6)(H2PO4)2} center dot 4H(2)O

A novel manganese phosphomolybdate, [H3N(CH2)(4)NH3](H3O)(2){[Mn(phen)(2)](4)[(MnMovO30)-O-12(HPO4)(6)(H2PO4)(2)]} . 4H(2)O 1, has been hydrothermally synthesized and structurally characterized by single crystal X-ray diffraction. The crystal data: triclinic, P (1) over bar, a = 14.172(7) Angstrom, b = 16.547(2) Angstrom, c = 16.679(3) Angstrom, alpha = 62.881(12)degrees, beta = 73.83(3)degrees, gamma = 88.81(3)degrees. X-ray crystallography shows that the [Mn(phen)(2)] fragments are covalently bonded to the [Mn(Mo6P4)(2)] dimers leading to a one-dimensional chain with rectangular cavities occupied by tetramethylene-diamine cations and water molecules. (C) 2002 Elsevier Science B.V. All rights reserved.

Synthesis, characterization and crystal structures of dibenzo-18-crown-6 sodium isopolytungstates

Two novel dibenzo-18-crown-6 sodium isopolytungstates, [(DB18C6)(CH3OH)Na](2)W(6)O(19)(.)DB18C6(.)H(2)O 1 and [(DB18C6)(DMF)(2)Na](4)W(10)O(32)(.)2DMF(.)2H(2)O 2, have been synthesized in mixed methanol and acetonitrile solvents and characterized by elemental analysis, TGA, IR and single crystal X-ray diffraction. The compound 1 crystallizes in the monoclinic space group C2/c with a = 23.182(8), b = 19.527(2), c = 18.737(3) Angstrom, beta = 115.15(2)degrees, V = 7678(3) Angstrom(3), Z = 4, and R1(wR2) = 0.0611(0.1504). The compound 2 crystallizes in the monoclinic space group P21/n with a = 16.516(2), b = 22.325(6), c = 20.425(7) Angstrom, beta = 91.78(2)degrees, V = 7528(3) Angstrom(3), Z = 2, and R1(wR2) = 0.0397(0.0773). The compound 1 exhibits a novel organic-inorganic sandwich-type structure, in which the crown ether-sodium complexes are coordinated to the terminal oxygen atoms of W6O192-. In compound 2, all Na+ ions are thoroughly enveloped into the organic moieties of crown ether and DMF molecules and are connected with the 'naked' polyanions W10O324- via the electrostatic attraction.