共查询到20条相似文献,搜索用时 31 毫秒
1.
《Physics and Chemistry of Liquids》2012,50(1):13-23
Experimental refractive indices and molar refractions for the binary mixtures of each of the isomers of chlorobutane with each of the isomers of butanol are given at 298.15?K. From these data the refractive index deviations were calculated. The experimental refractive index results were compared with those predicted by several mixing rules: Lorentz–Lorenz, Gladstone–Dale, Arago–Biot, Wiener and Heller. 相似文献
2.
Summary Using achiral stationary phases of different polarity in capillary gas chromatography it is demonstrated that the hydration of 1,2–5,6-dibenzocycloocta-1,5-diene yields five isomers of the tricyclo[10.4.0.04,9]hexadecanes. With highly polar stationary phases all isomers of the tricyclic hexadecanes and the semihydrated products in the mixture were also separated from each other. The chiral isomers were separated on cyclodextrin stationary phase. Moreover, with columns of achiral and chiral phases coupled in series, in a double oven gas chromatograph, it was possible to estimate the configuration of the isomers. The separation of diastereomers on chiral stationary phases is a useful means for structural assignment of isomeric compounds.Dedicated to Professor Leslie S. Ettre on the occasion of his 70th birthday. 相似文献
3.
A pair of isomeric cyclic triads containing three quadruply bonded [Mo2] units, [Mo2(cis-DAniF)2]2+ (DAniF = N,N'-di-p-anisylformamidinate), bridged by six fluoride anions, has been synthesized and crystallographically characterized. For the alpha isomer, the three [Mo2] units are oriented in two orthogonal directions. Two of them are structurally equivalent and parallel to each other, but oriented perpendicular to the third one. The beta isomer is a triangle with three geometrically identical [Mo2] units, parallel to each other, as the vertices. Thus, the beta isomer possesses idealized D3h symmetry while the alpha isomer only has C2v symmetry. These two isomers do not interconvert in boiling THF or toluene or under irradiation with ultraviolet light, but oxidation of the alpha isomer first generates an alpha+ species that changes to beta+. The two isomers have very similar electrochemical behavior, both showing three reversible one-electron redox processes for the [Mo2] centers and similar potential separations (DeltaE(1/2)). The first and second redox couples are well separated (ca. 390-410 mV), while the second and third ones are separated by only about 150 mV. 相似文献
4.
Zhao L Yang W Luo Y Zhai T Zhang G Yao J 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(12):3773-3778
Organic nanotubes of various diameters were fabricated from the isomeric molecule dibenzoylmethane (DBM) by using an immersing technique with ordered porous alumina membrane as the template. The ratio of the enol isomers of DBM increased as the diameters of the nanotubes decreased. In addition, although almost no fluorescence could be detected for the DBM monomer, a striking enhancement in the fluorescence emission intensity of the nanotubes was observed as the diameters decreased. This is due to the increased ratio of the enol isomers. 相似文献
5.
《Electrochemistry communications》2003,5(4):334-336
Polarographic current–voltage curves enabled distinguishing between the degree of covalent hydration of iso-, tere-, and orthophthalaldehydes. Hydration, which is negligible for isophthalaldehyde, strong for terephthalaldehyde and very strong for orthophthalaldehyde, together with acid–base reactions, affect the electrolysis of each of the three isomers differently. In solutions of orthophthalaldehyde polarography enables simultaneous following of concentrations of the unhydrated, acyclic monohydrated, cyclic hemiacetal forms. Each of these forms react with amino acids by a different rate. 相似文献
6.
A. K. Sircar 《Journal of Thermal Analysis and Calorimetry》1997,49(1):293-301
Many of the isomers of polybutadiene and polyisoprene elastomers can be characterized by thermal analysis.T g is sensitive to side chain units (1,2 or 3,4 structure) for both polymers. Crystallinity measurements can characterizecis andtrans isomers. DMA and DEA master curves provide an idea of the heterogeneity of the chain units from the width of the loss factor curves in theT g region. Thermal and thermooxidative degradation, as followed by DSC and DTG, can differentiate specific natural and synthetic isomers of polyisoprenes in raw and vulcanized states. 相似文献
7.
Maolei Zhu Brad Bendiak Brian Clowers Herbert H. Hill Jr 《Analytical and bioanalytical chemistry》2009,394(7):1853-1867
The rapid separation of isomeric precursor ions of oligosaccharides prior to their analysis by mass spectrometry to the nth power (MS
n
) was demonstrated using an ambient pressure ion mobility spectrometer (IMS) interfaced with a quadrupole ion trap. Separations
were not limited to specific types of isomers; representative isomers differing solely in the stereochemistry of sugars, in
their anomeric configurations, and in their overall branching patterns and linkage positions could be resolved in the millisecond
time frame. Physical separation of precursor ions permitted independent mass spectra of individual oligosaccharide isomers
to be acquired to at least MS3, the number of stages of dissociation limited only practically by the abundance of specific product ions. IMS–MS
n
analysis was particularly valuable in the evaluation of isomeric oligosaccharides that yielded identical sets of product
ions in tandem mass spectrometry experiments, revealing pairs of isomers that would otherwise not be known to be present in
a mixture if evaluated solely by MS dissociation methods alone. A practical example of IMS–MSn analysis of a set of isomers included within a single high-performance liquid chromatography fraction of oligosaccharides
released from bovine submaxillary mucin is described. 相似文献
8.
Summary Mixed ligand complexes of Cr(III), Co(II), Cu(II) and Zn(II) with the p-diethylaminoanil of phenylglyoxal and either thiourea or ammonia, isolated as binary mixtures of isomers, were separated on thin layers of alumina or silica gel and on paper strips. Separation of mixtures in bulk was by column chromatography whereas quantitative analysis including determination of isomeric compositions of isolates was by TLC. Resolved isomers were identified using correlations of their RF with spectral properties. 相似文献
9.
Milanowska J Polit A Wasylewski Z Gruszecki WI 《Journal of photochemistry and photobiology. B, Biology》2003,72(1-3):1-9
Two-component monomolecular layers were formed with DPPC and two stereoisomers of zeaxanthin 9-cis and 13-cis at the argon-water interface. Very distinct over-additivity which represents affection of a lipid arrangement in the membrane has been observed in the case of zeaxanthin 9-cis (maximum at 20 mol%) but not in the case of zeaxanthin 13-cis. The differences in the organization of the isomers of zeaxanthin-DPPC monolayers are interpreted in terms of the different orientation of both xanthophylls at the interface observed at relatively high surface pressures (>25 mN/m) comparable to the surface pressures of biomembranes. The results are consistent with the model according to which zeaxanthin 9-cis adopts a vertical orientation at the polar-nonpolar interface in contrast to zeaxanthin 13-cis, which is oriented horizontally owing to the fact that it interacts by two hydroxyl groups with the same hydrophobic-hydrophilic interface in the monolayer. The findings are discussed in comparison with the behavior of zeaxanthin in the conformation all-trans in the same system. Zeaxanthin all-trans forms efficiently molecular aggregates in the mixed monolayers in contrast to cis isomers. Circular dichroism measurements show the formation of molecular structures by zeaxanthin 13-cis that are interpreted as dimers. FTIR measurements show that these dimers are stabilized by van der Waals interactions unlike aggregated structures formed by all-trans zeaxanthin that are stabilized by hydrogen bonding. Physiological importance of the differences in aggregation and orientation of stereoisomers of zeaxanthin in lipid environment is discussed. 相似文献
10.
A specific, sensitive and precise capillary gas chromatographic method using electron-capture detection was developed for the determination of four isomeric vasodilating organic mononitrates, viz. L-isoidide mononitrate (L-IIMN), isosorbide-2-mononitrate (IS-2-MN), isomannide mononitrate (IMMN) and isosorbide-5-mononitrate (IS-5-MN), in rat plasma. With a sample size of 100 microliters of rat plasma, the detection limits were found to be between 0.5 and 2 ng/ml for these mononitrates, and the absolute recovery was found to range from 83 to 90%. The within-day coefficients of variation for the assay of the four isomers were less than 5%, while the between-day coefficients of variation were less than 10%. Because of the short retention times of these isomers in this assay, routine analyses of about sixty plasma samples per day can be carried out. The possibility of in vivo interconversion among these four isomers in rats was investigated after individual administration of each isomer. No interconversion was found based on examination of plasma samples. The gas chromatographic method was applied to the pharmacokinetic studies of these four isomers in rats; at an intravenous dose of 2 mg/kg, the biological half-lives of L-IIMN, IMMN, IS-2-MN and IS-5-MN were found to be 13.2, 25.2, 54.6 and 112 min, respectively. 相似文献
11.
Giorgi G Salvini L Ponticelli F 《Journal of the American Society for Mass Spectrometry》2002,13(11):1298-1303
Different mass spectrometry (MS) techniques have been applied to the study of modified tryptophan isomers obtained by photochemical reactions. The gas phase behavior of the molecular ions and the most abundant fragment ions produced under electron ionization has been selectively studied by MS/MS experiments. Both the fragmentation reactions occurring in the ion source, as well as those produced under collision-induced dissociation conditions have allowed to characterize and differentiate each isomer from the others. Investigation of a bisubstituted derivative has been useful in the rationalization of the gas phase behavior of this series of modified tryptophans. This study has allowed the evaluation of the role played by the substituents and their positions at the indolic ring on the gas phase decompositions that are distinctive and selective for each isomer. The occurrence of regiospecific reactions suggests that isomerization phenomena do not occur either in the molecular ions or in the main fragment ions in the gas phase. 相似文献
12.
It is shown that the bases described in a number of papers and patents as 2,6-dimethyl-, 2,6-diamino-, and 2,6-dimercaptobenzo[1,2-d:4,3-d']bisthiazoles (isomers of linear structure) are actually 2,7-dimethyl-, 2,7-diamino-, and 2,7-dimercaptobenzo [1,2-d:6,5-d']bisthiazoles (isomers of angular structure). The synthesis of the hitherto unknown 2,6-dimethylbenzo[1,2-d:4,5-d'] bisthiazoles is described. 相似文献
13.
By means of Fabry-Pérot Fourier transform microwave spectroscopy, the rotational spectrum of protonated sulfur dioxide in two distinct isomeric forms, a cis- and a trans-geometry, is reported. The search for both isomers was based on theoretical structures obtained at the CCSD(T)/cc-pwCVQZ level of theory corrected for zero-point vibrational effects. At a similarly high level of theory, the cis-isomer is calculated to be the global minimum on the potential energy surface, but the trans-isomer is predicted to lie only a few kcal/mol higher in energy. A total of seven lines, including a- and b-type transitions, has been observed for both isomers, and precise rotational constants have been derived. Because sulfur dioxide, SO(2), is a widespread and very abundant astronomical species, and because it possesses a large proton affinity, HOSO(+) is an excellent candidate for radioastronomical detection. 相似文献
14.
It is shown that the bases described in a number of papers and patents as 2,6-dimethyl-, 2,6-diamino-, and 2,6-dimercaptobenzo[1,2-d:4,3-d']bisthiazoles (isomers of linear structure) are actually 2,7-dimethyl-, 2,7-diamino-, and 2,7-dimercaptobenzo [1,2-d:6,5-d']bisthiazoles (isomers of angular structure). The synthesis of the hitherto unknown 2,6-dimethylbenzo[1,2-d:4,5-d'] bisthiazoles is described. 相似文献
15.
Electrospray ionization combined with ion trap mass spectrometry (ESI-ITMS) is a powerful tool for structural analysis of complex carbohydrates. Although its application to sulfated glycans has been limited so far, it should provide critical information, such as sulfate positions, on their structures. In this work, MS(n) spectra of nine monosulfated monosaccharides, consisting of five hexoses and four N-acetylhexosamines, were measured in negative ion mode to find basic fragmentation rules for sulfated sugars. Two pairs of positional isomers with respect to sulfation, i.e., Gal4S and Gal6S, and GalNAc4S and GalNAc6S, showed characteristic fragmentation patterns in MS(3), and could be discriminated from one another by the appearance of particular diagnostic fragment ions that characterize individual isomers. It was also demonstrated that, even if a mixture of these positional isomers was analyzed, the proportion of each species could be estimated through analysis of the abundance ratios of the diagnostic ions. However, 3-O-sulfated saccharides (Glc3S and GlcNAc3S) gave a single abundant diagnostic ion in MS(2) corresponding to the hydrogensulfate ion, [OSO(3)H](-), and this characteristic clearly differentiated them from their positional isomers. In contrast, 6-O-sulfated diastereomers consisting of two groups, Glc6S, Man6S, Gal6S, and GlcNAc6S, GalNAc6S, could not be discriminated by the types of fragment ions; however, the abundance ratios of particular fragment ions differed significantly between Glc(NAc)6S and Gal(NAc)6S. Since ESI-ITMS yielded large quantities of useful information on structures of monosulfated hexoses and N-acetylhexosamines in an extremely simple and reproducible manner, establishment of a comprehensive strategy based on ESI-ITMS(n) appears to be a promising technique for structural elucidation of sulfated complex carbohydrates. 相似文献
16.
A study of the pyrolytic behavior of the butanol isomers has been made in order to establish a basis for their identification from the thermolysis pattern of each butanol. The identity of the volatile products was established by gas chromatographic analysis. Each isomer was found to decompose via degradation reactions characteristic of the structural arrangement of each alcohol molecule for which mechanisms are proposed. 相似文献
17.
Summary N-Benzoylphenylhydroxylarnine complexes of some metals have been investigated by HPLC. The green chromium complex formed by this reagent shows conclusive evidence of the presence of geometrical isomers. It is photosensitive and changes to a brown modification when irradiated with ultra violet or visible light. Elution behaviour of the complexes has been studied with different solvent mixtures. Attempts have been made to characterize the complexes from different measurements.
Untersuchung von isomeren Chrom-N-benzoylphenylhydroxylaminaten durch HPLC相似文献
18.
4‐Hydrazino‐7H‐pyrrolo[2,3‐d]pyrimidines ( 4 ) were cyclocondensed with formic acid or triethyl orthoformate to give 7H‐1,2,4‐triazolo[1,5‐c]pyrrolo[3,2‐e]pyrimidines ( 5 ) and 7H‐1,2,4‐triazolo[4,3‐c]pyrrolo‐[3,2‐e]pyrimidines ( 6 ) respectively. The [4,3‐c]‐isomers ( 6 ) were rearranged into thermodynamically more stable [1,5‐c]‐isomers ( 5 ). The identical compounds ( 5 ) were prepared using another route by reacting 3‐amino‐4‐imino‐7H‐pyrrolo[2,3‐d]pyrimidines ( 3 ) with formic acid or triethylorthoformate. Reaction of 2‐amino‐3‐cyanopyrroles ( 1 ) with triethyl orthoformate followed by hydrazinolysis afforded ( 3 ) via the formation of N‐ethoxymethylene‐2‐amino‐3‐cyanopyrroles ( 2 ). 相似文献
19.
Trace amounts of a dibenzothiophene (DBT) series in complex matrices were detected by gas chromatography with flame photometric detection (FPD) after purification and isolation by normal-phase high performance liquid chromatography. The gas chromatographic behavior of eleven methylated DBTs was studied on six common stationary phases. Complete resolution of the four monomethyl DBT isomers was only achieved on a capillary column coated with a methylphenylsilicone phase gummified in situ by heat-curing. The determination of the relative distribution of the four monomethylated isomers is proposed as a powerful method for monitoring oil pollution in marine environment. 相似文献
20.
Zhao L Northrop BH Zheng YR Yang HB Lee HJ Lee YM Park JY Chi KW Stang PJ 《The Journal of organic chemistry》2008,73(17):6580-6586
A new approach wherein steric interactions between substituents of unsymmetrical bis(4-pyridyl)acetylene ligands dictate the self-selection of single isomers of [4 + 4] self-assembled squares is presented. Each [4 + 4] self-assembly is characterized by multinuclear (31)P and (1)H NMR spectroscopies and electrospray ionization mass spectrometry. NMR spectroscopic studies are used to provide a means of evaluating the efficiency of bulky substituents at proximal or remote positions relative to the Pt-N bonding motif to direct self-selection. Molecular modeling using the MMFF force field is utilized to determine the relative energy of different isomers of each assembly, and modeling results reasonably explain the trend in self-selectivity with varying pyridyl substitution. 相似文献