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911.
在280~320K的温度范围内考察了30%十六烷基三甲基溴化铵水溶液的红外光谱随温度的变化。结果表明该体系的凝聚胶-液晶相转变温度为300K。在300K以下的凝聚胶相,分子的极性头部基团处于高度“固定”的状态,分子的碳氢链以有序的相互平行方式排列,极性头与碳氢链之间有一定的倾斜角。在300K以上的液晶相,极性头内部CH_3-(N~+)基团以及整个极性头与碳氢链之间发生了旋转,碳氢链变为以六方亚晶胞填充形式存在,旦扭曲式构象异构体数量显著增多,极性头与碳氢链之间已不存在倾斜角,分子的亲水极性头和疏水碳氢链部分都处于“融化”状态。 相似文献
912.
NMR spectroscopy plays an important part in the determination of the structures of organic compounds. The parameters of importance here are the chemical shifts of the 1H and 13C nuclei and the spin-spin interactions both between 1H nuclei and between 1H and 13C nuclei. Couplings between 13C nuclei were almost completely neglected until a few years ago, since they were extremely difficult to observe because of the low natural abundance of 13C. However, it is these couplings which afford information directly on the carbon-carbon connectivities in the molecule. It is now possible to use a special NMR pulse sequence to make these couplings more readily visible: the result of using this sequence is a 13C-NMR spectrum from which the carbon skeleton concerned can be directly read off. Two-dimensional spectra in particular are very easy to evaluate. The pulse sequence involved, which bears the somewhat puzzling name INADEQUATE, produces double-quantum coherences from which the NMR signals of the coupled carbon nuclei can be obtained. In this article the principle of double-quantum coherence is described and a number of examples for the application of the INADEQUATE pulse sequences to problems in synthetic organic chemistry, biosynthesis and natural products chemistry are presented; in addition, the possibility of applying the INADEQUATE method to other nuclei is considered. 相似文献
913.
Chandra S Kumar R 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2005,62(4-5):1050-1057
Reaction of divalent cobalt(II) and trivalent ruthenium(III) salts (NO3, SCN and SO4) with macrocyclic ligands L1, L2 and L3 having N2S2, N4 and N5 core, have been designed and carry out. All these three macrocyclic ligands and their complexes were obtained in pure form. Their structures were investigated by using microanalytical analyses, IR, mass, magnetic moments, electronic and EPR spectral studies. The redox properties of the complexes were also examined by cyclic voltammetry. An interesting feature of complexes is that the relatively large rings of macrocyclic ligands prevent the macrocyclic rings from approaching the metal center as closely as they would, if they were not constrained. So the Ru-N distances are longer than expected due to ring size. Electrochemical studies show that the macrocyclic ligand L1 is more effective electron donors to ruthenium than of L2 and L3. Electronic spectral properties also show that the sulphur donor atom of L1 weakens the ligand field with respect to ligand-to-metal charge-transfer band. However it is expected that second-row transition metal-ligand bonds tend to be weaker than third-row transition metal-ligand bonds. There are well-established examples of reactions in which decreased of reactivity down a triad of transition metals is not observed. These novelties are usually attributed to pi-bonding effects for ligands such as carbon monoxide, solvent effects, or a change in mechanism. 相似文献
914.
Gas hydrates are non-stoichiometric crystalline compounds of water with gas at a certain temperature and pressure. Compared to the thermodynamics of hydrate formation, our knowledge on the kinetics aspect is rather immature. It is well known that the kinetics of hydrate formation/dissociation plays an important role in many industrial cases, such as the exploitation of methane hydrate underground, the storage and transportation of natural gas in solid hydrate state, the inhibition of hydrate i… 相似文献
915.
Silvia Stumpf Gudrun Goretzki Kerstin Gloe Karsten Gloe Wilhelm Seichte Edwin Weber Jan W. Bats 《Journal of inclusion phenomena and macrocyclic chemistry》2003,45(3-4):225-233
The di- and tetra-allyl ethers of tert-butylcalix[4]arene 1 and 2 have been prepared by alkylation of tert-butylcalix[4]arene with allyl bromide and K2CO3 using different reaction times. Solution 1H NMR measurement of the di-allyl ether 1 and X-ray crystal structures of the complexes of 1 with chloroform (1a) or methanol (1b) indicate the cone conformation of 1 in which intramolecular hydrogen bonding can be maximized. The crystalline state conformers 1a and 1b are distorted in different grades depending on the solvent. While methanol is incorporated in the macrocycle, chloroform molecules do not occupy the cage. The solution 1H NMR spectra of tetra-allyl ether 2 show the co-existence of the cone and partial cone conformation. The partial cone conformer of 2 was investigated by X-ray crystallography. In this compound hydrogen bonding is not existent. The conformer distribution is likely affected by steric and template effects. 相似文献
916.
917.
Summary -Lactoglobulin A and B (-LACT) were separated by displacement chromatography (DSC) on an ionexchange column using dextran sulfate as the displacer. A LALLS photometer and a UV detector, in series, were used to determine the molecular weight (MW) of the proteins, on-line. The results indicate that both, -LACT A and B, were present as dimers in the buffer used for the mobile phase. The MWs of the proteins were about 6–8% higher than the theoretical MW of a dimer (37,000). Additional control studies have shown the presence of a high molecular weight species in both the proteins, which could possibly be an aggregate. This species was observed in the LALLS signal but was nearly absent in the UV signal. Our work has demonstrated the feasibility of interfacing LALLS with displacement chromatography for detecting impurities or aggregates which may be difficult to detect by conventional detectors used for chromatography. 相似文献
918.
O. A. Snytnikova P. S. Sherin L. V. Kopylova Yu. P. Tsentalovich 《Russian Chemical Bulletin》2007,56(4):732-738
Photochemical reactions involving kynurenines, viz., molecules present in the eye lens, can result in modifications of the lens proteins and cause a development of a cataract.
The rate constants of the reactions of photoexcited kynurenine with several amino acids and antioxidants contained in the
lens were measured. The most efficient quenchers of triplet kynurenine are amino acids tryptophan and tyrosine, as well as
antioxidant ascorbate. In all cases, the quenching reaction proceeds by the electron transfer mechanism, except for the reaction
with oxygen where transfer of the triplet energy to the oxygen molecule occurs.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 704–710, April, 2007. 相似文献
919.
Cengiz Soykan Ramazan Coskun Ali Delibas Ertan Sahin 《高分子科学》2007,(5):491-500
2-Acrylamido-2-methy1-1-propanesulfonic acid(AMPS),and maleic acid(MA)copolymerized with different feed ratios using N,N-dimethylformamide as a solvent and benzoyl peroxide(Bz_2O_2)as an initiator at 70℃.Structure and composition of copolymers for a wide range of monomer feed were determined by elemental analysis(content of N for AMPS-units).Monomer reactivity ratios for AMPS(M_1)-MA(M_2)pair were determined by the application of conventional linearization methods such as Fineman-Ross(F-R),Kelen-Tüd(?)s(KT)and Extended Kelen-Tüds(EKT)and a nonlinear error invariable model method using a computer program RREVM.The characterizations were done by Fourier transform infrared spectroscopy(FTIR),differential scanning calorimetry(DSC)thermal gravimetry analysis(TGA),and and X-ray diffraction.The antimicrobial effects of polymers were also tested on various bacteria,and yeast. 相似文献
920.
报道用催化反应热诱导激光光偏转法测定痕量尿素。发现将脲酶制成一定浓度的乙醇浓液能显著地增强激光光偏转信号强度。探讨了增强作用机理以及光偏转号强度与尿素浓度的关系,并应用于尿样中尿素含量的测定,结果满意。 相似文献