1-甲基环氧乙烷-1-丙炔醚的结构测定及其核磁图谱

以¹H-NMR谱和¹³C双自旋回波的APT脉冲序列测定文献中尚未曾发表的化合物HC≡C-CH₂-O-C^CH₃-_O-CH₂文中计算了峰强度与脉冲间隔时间的关系,讨论了各谱线的相位并区分出-CH₃、-CH₂、-CH和季碳。     

原伊鲁烷型倍半萜醇芳香酸酯的碳谱研究

作者自人工发酵得到的蜜环菌Armillaria mellea (Vahl.ex Fr.) Quel.菌丝体中分离出十七个原伊鲁烷型倍半萜醇芳香酸翻,在研究这些化合物的化学结构中,对其全去偶碳谱,偏共振谱或INEPT谱,C-H COSY谱和远程C-H COSY谱进行比较仔细地分析,指定了每个化合物各碳的归属,讨论了其碳谱的特征,并指出¹³C NMR谱是对新的该类型化合物结构测定的有效方法.     

13C NMR spectra of azolopyridines and their quaternary salts

¹³ C NMR spectra of some azole series have been investigated: 2-pyridylbenzimidazoles, 2-pyridylimidazo [4,5-b]-pyridines, 2-pyridylimidazo[4,5-c]-pyridines, analogous oxazole compounds, as well as their mono- and bisquaternary salts. Some problems, related to the structure of these compounds in solution, have been discussed.V. I. Vernadskii Institute of Geochemistry and Analytical Chemistry, Russian Academy of Sciences, Moscow 117975. Torino University, Italy. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 4, pp. 866–872, April, 1992.     

Azine bridged silver coordination polymers: Powder X-ray diffraction route to crystal structure determination of silver benzotriazole

In continuation of our interest in solid-state structures of silver complexes of photographic importance, the structure for silver benzotriazole (AgBZT), has now been obtained. The preferred method for solving crystal structures is via single-crystal X-ray diffraction (XRD). However, for some materials, growing single crystals of appropriate size and quality is often difficult or even impossible. AgBZT is an example of such a silver complex with poor solubility. The usual routes to preparing single crystals using recrystallization from a cooperating solvent resulted in polycrystalline powder samples. We propose a crystal structure for AgBZT, solved from synchrotron X-ray powder diffraction data, using a direct-space Monte Carlo simulated annealing approach. AgBZT crystals are monoclinic, (P2₁/c), with unit cell dimensions, a=14.8052(3) Å, b=3.7498(4) Å, c=12.3495(12) Å, and β=114.200(6)°. The AgBZT complex is constructed from all three of the Benzotriazole (BZT) nitrogens bonding to a separate silver atom. As a consequence of this bonding mode, the structure is a highly cross-linked, coordination polymer.     

Difference in micellar properties of sodium dodecyl sulfonate from sodium 4-decyl naphthalene sulfonate in D2O solution studied by 1H NMR relaxation and 2D NOESY

¹H chemical shift changes of sodium 4-decyl naphthalene sulfonate (SDNS) at 313 K show that its critical micellar concentration lies between 0.82 and 0.92 mmol/dm³, which is in the same range as that of the previous study at 298 K. The spin–lattice relaxation time, spin–spin relaxation time and two-dimensional nuclear Overhauser enhancement spectroscopy experiments give information about the structure of the SDNS micelle and the dynamics of the molecules in the micelle. The size of the SDNS micelle remains almost unchanged in the temperature range from 298 to 313 K as deduced by analyzing the self-diffusion coefficient. Special arrangement of the naphthyl rings of SDNS in the micelles affects the packing of these hydrophobic chains. The methylene groups of the alkyl chain nearest the naphthalene groups penetrate into the aromatic region, which results in a more tightly packed hydrophobic micellar core than that of sodium dodecyl sulfonate.     

Solution 1H and 13C NMR of new chiral 1,4‐oxazepinium heterocycles and their intermediates from the reaction of 2,4‐pentanedione with α‐L‐amino acids and (R)‐(—)‐2‐phenylglycinol

The reaction of 2,4‐pentanedione ( 1 ) with (R)‐(—)‐2‐phenylglycine methyl ester ( 2 ), (R)‐(—)‐2‐phenylglycinol ( 3 ) and the proteinogenic amino acids (2S,3R)‐(—)‐2‐amino‐3‐hydroxybutyric acid (L ‐threonine) ( 4 ) and (R)‐(—)‐2‐amino‐3‐mercaptopropionic acid (L ‐cysteine) ( 5 ) methyl esters was investigated. The corresponding enamines 6 , 7 and 8 were isolated and characterized spectroscopically whereas 9 , which is unstable, was transformed in situ into 13 . Treatment of 7 , 8 and 9 with boron trifluoride etherate afforded the new [1,4]oxazepines 10 , 11 and [1,4]thiazepine ( 12 ) as their BF₃O^? salts. The structures of the enamines and their corresponding seven‐membered heterocycles were assessed by 1D and 2D NMR spectroscopy. Variable‐temperature experiments revealed different molecular mobility behavior among these heterocycles. Copyright © 2003 John Wiley & Sons, Ltd.     

Mössbauer Studies and Magnetic Properties of Y3−x Ce x Fe5O12

It is shown that in-situ ^166mHo (I = 7) in a spherical single crystal of HoF₃ can be used as sensitive internal thermometer to thermally detect NMR (NMR-TDNO) from the 100% abundant stable ¹⁶⁵Ho (I = 7/2) nuclei. In addition, new ^166mHo NMRON results are reported. Both the ^166mHo NMRON and ¹⁶⁵Ho NMR-TDNO spectra show three distinct quadrupolar split sub-resonances, in zero applied field. The data is used to make estimates of the Ho magnetic moments and quadrupole parameters for the ^166mHo and ^166mHo sites.     

Crystalline structure of polyamide 12 as revealed by solid‐state 13C NMR and synchrotron WAXS and SAXS

The crystalline structure of polyamide‐12 (PA12) was studied by solid‐state ¹³C nuclear magnetic resonance (NMR) as well as by synchrotron wide‐ and small‐angle X‐ray scattering (WAXS and SAXS). Isotropic and oriented PA12 showed different NMR spectra ascribed to γ‐ and γ′‐crystalline modifications, respectively. On the basis of the position of the first diffraction peak, the isotropic γ‐form and the oriented γ′‐form were shown to be with hexagonal crystalline lattice at room temperature. When heated, the two PA12 polymorphs demonstrated different behaviors. Above 140 °C, the isotropic γ‐PA12 partially transformed into α‐modification. No such transition was observed with the oriented γ′‐PA12 phase even after annealing at temperatures close to melting. A γ′–γ transition was observed here only after isotropization by melting point. Various structural parameters were extracted from the WAXS and SAXS patterns and analyzed as a function of temperature and orientation: the degree of crystallinity, the d‐spacings, the Bragg's long spacings, the average thicknesses of the crystalline (l_c) and amorphous (l_a) phases, and the linear crystallinity x_cl within the lamellar stacks. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 3720–3733, 2005     

高压下某些导电高分子色散关系的研究

利用晶格动力学方法,研究在高压下几种导电高分子具有不同晶格链时的色散关系及其曲线的变化.链间耦合作用的减弱使横波与纵波的ω差值相应增大,且在BZ边界处拉开一个间隙,这是维度作用的结果.     

Influence of the H/F replacement on the homoaromaticity of homotropylium ion: a GIAO/DFT theoretical study

The problem of homoaromaticity in mono-, di- and polyfluorinated- homotropylium cations is addressed by the B3LYP/6-311++G** DFT method. The energetic, structural and magnetic criteria are used for this purpose. They convincingly show that the ground state equilibrium species are aromatic, or in other words that the homoaromaticity is preserved by the (poly)fluorination. In contrast, a considerable decrease in the aromatic stabilization is observed in the transition structures (TS). According to the NICS(0) index, they vary form strongly antiaromatic, via weakly and non-aromatic to slightly aromatic transition states. However, the hierarchy of the aromaticity in fluorinated homotropylium ions predicted by NICS(0) is completely unrelated to that obtained by using the energy criterion assuming a kinetic definition of aromaticity. On the other hand the latter is closely related to geometric parameters of the equilibrium and transition structures.