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61.
62.
Natalia N. Dioubankova 《Tetrahedron》2004,60(21):4617-4626
The synthesis of two novel fluorescent uridine-2′-carbamate phosphoramidites is described. The reagents carrying fluorescent polyaromatic hydrocarbons 1-phenylethynylpyrene (PEPy) or 9,10-bis(phenylethynyl)anthracene (BPEA) are suitable for oligonucleotide synthesis. Prepared oligonucleotide conjugates show strong dye emissions at 401 and 485 nm, but low FRET rate when located in the oligonucleotide duplex. The dyes show considerable compensation of the usual carbamate duplex destabilization. The possible explanation of both effects is binding of PEPy and BPEA to the minor groove of the DNA duplex. 相似文献
63.
A comparative study of the performance of liquid chromatography (LC)-atmospheric pressure chemical ionisation (APCI)-mass spectrometry (MS) and gas chromatography (GC)-mass spectrometry techniques for the determination of resin and fatty acids from paper mill process waters was carried out. These compounds are responsible for the high toxicity of paper mill effluents and little research has been carried out regarding their analysis using mass spectrometric techniques. To prove the usability of GC and LC-MS, 16 treated and untreated water samples of recycle, kraft and pulp paper mills were analysed and good agreement was observed as regards to compounds detected and corresponding concentrations. This paper also reports the limits of detection, recoveries, reproducibility, linearity and precision using the two methods. GC-MS presented better selectivity and lower detection limits (below 0.2 microg/l), but derivatization of the extracts and the short life of derivatives (12-24 h) made the technique tedious and prone to high variations. Although LC-APCI-MS presented coelution of the non-aromatic resin acids, it also showed good sensitivity (limits of detection <3 microg/l) and permitted the detection of resin and fatty acids at microg/l level. In addition, since samples could be directly injected to the chromatographic system, LC-APCI-MS was proven as a powerful technique for quick and unequivocal quality control during papermaking. 相似文献
64.
A novel convergent approach to dendritic macromolecules is described in which 4,6-dichloro-2-(4-methoxyphenyl)-pyrimidine is used as the building block. The nucleophilic aromatic substitution reaction at this AB2-monomer was used as the key step in the propagation of the dendrons. Different core reagents were used to form the dendrimers, including a 5,15-bis(pyrimidyl)porphyrin core. Fourth-generation dendrons and third-generation dendrimers could be synthesized. The presented dendrimers are promising candidates to be used in applications where a more rigid structure and a larger resistance towards the applied conditions is required. 相似文献
65.
G. V. Gavrilova A. A. Aleshkin V. A. Nikanorov D. P. Krut'ko V. I. Rozenberg O. A. Reutov 《Russian Chemical Bulletin》1995,44(3):502-506
A novel method for the synthesis of the oxime of 4-methyl-2,4,6-cycloheptatrien-1-one (Eschenmoser's oxime) is proposed. The method involves redox enlargement of the ring of 4-dibromomethyl-4-methyl-2,5-cyclohexadien-1-one oxime through the action of Ni(PPh3)4 in DMF (in the presence of Zn). The product is formed as a mixture ofsyn- andanti-forms readily interconverting in solutions. A similar reaction of 4-methyl-4-trichloromethyl-2,5-cyclohexadien-1-one oxime afforded the dimer of agem--centered semiquinoid carbene (1,2-bis-(1-methyl-4-oxyimino-2,5-cyclohexadienyl)-1,2-dichloroethylene), together withsyn- andanti-isomers of 4-chloro-5-methyl-2,4,6-cycloheptatrien-1-one oxime, which are readily separable but also quickly interconverting in solutions. For the latter compounds, the complete1H NMR assignment of the stereoisomeric structures has been carried out.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 519–523, March, 1995.The authors are grateful to the International Science Foundation (Grant MHW000) as well as the Russian Foundation for Basic Research (Project No. 94-03-08873) for the financial support of the work. 相似文献
66.
Alastair C. Lewis Sarah A. Askey Krystyna M. Holden Keith D. Bartle Michael J. Pilling 《Journal of separation science》1997,20(2):109-114
The composition and concentration of polycyclic aromatic compounds (PAC) in fuels. Theier combustion products and in the atmosphere remains a topic of considerable interest. Despite the wealth of literature on the identification of PAC, speciation at low concentrations remains difficult due to instrument limitation and the complexity of fuel and environmental samples. Consequently on line sample preparation procedures (SPE, SFE, LC, etc.) are becomeing an increasingly important step in the analysis procedure particularly where sample clean-up and fractionation are essential for improving analytical resolution. In this study a normal phase high pressure analytical resolution. In this study a normal phase high pressure liquid chromatography-gas chromatography (LC-GC) system has been developed to provide quantitative analysis of samples, as diverse as coal liquids, petroleum fuels, diesel exhaust particulates, and urban air particulates. Separation and identification of parent and alkylated PAH, hetercycline nitro-and oxy-PAC can be achieved by direct coupling to an atomic emission detector and a bech top mass spectrometer. For both systems the primary LC separation combined with the large sample volume transferred to GC vastly improves detection limits. Furthermore the complimentary nature of the two detectors used enables the positive indentification of many unknowns. 相似文献
67.
Ammonium acetate was found to catalyze efficiently the selective deprotection of aromatic acetates in the presence of various sensitive functionalities in aqueous methanol under neutral conditions at room temperature to yield the corresponding phenols in excellent yields. The method has been utilized for deprotection of acetates of several naturally occurring bioactive phenolic compounds and for preparation of venkatasin, a natural coumarino-lignan, from the anticancer compound cleomiscosin A. 相似文献
68.
Aromatic peptide nucleic acid analogs having an N-(2-aminobenzyl)glycine backbone (APNA 1) were previously identified as promising new leads for the design of polyaromatic DNA mimics. Structural modifications of 1, which lock the aromatic backbone into a unique conformation, while maintaining the same space distribution between the nucleobases as in 1, were investigated. The electrostatic potential of the aromatic backbone was also modified in an attempt to improve the solubility of these compounds in aqueous media and to evaluate how the quadrapole of the aromatic backbone may influence the biophysical properties of the APNA oligomers. PNA hexamers containing a single monomer insert of each new APNA monomer were used to explore the hybridization properties of these analogs with poly rA and poly dA. Preliminary results indicated that these modifications do not seriously alter the molecular recognition properties of APNAs towards DNA and RNA. 相似文献
69.
Summary The method for the contraction and expansion of graphs is used to treat the subspectrality of benzenoid hydrocarbons in relation to eigenvalues ±1. Counts of benzenoid hydrocarbons together with degeneracies of eigenvalues have been carried out for all species having h 7 hexagons. In addition, twelve homologous series are evaluated, and the closed results for the distribution of eigenvalues ± 1 and degeneracies in terms of the number of repeated units are tabulated. This method is universal and applicable to cases sharing other eigenvalues and to nonbenzenoid systems.Also known as Yuan-sun Kiang 相似文献
70.
The electron capture detector (ECD) response to numerous aromatic hydrocarbons of low electron affinity (EA) is shown to be detrimentally affected by two processes which compete with and typically overwhelm the electron capture reactions of these molecules. It is shown that the effects of these two undesired reactions can be eliminated by the permanent addition of trimethylamine and one of several alkyl monochlorides to the detector make-up gas. These modifications of the detector gas result in greatly increased sensitivity, increased linearity, and increased reproducibility of response. A kinetic model for the ECD responses of low EA resonance capture molecules is developed which appears to explain these improvements. 相似文献