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Marchán V Cieślak J Livengood V Beaucage SL 《Journal of the American Chemical Society》2004,126(31):9601-9610
Several nitrogen-sulfur reagents have been investigated as potential 5'-hydroxyl protecting groups for deoxyribonucleoside phosphoramidites to improve the synthesis of oligonucleotides on glass microarrays. Out of the nitrogen-sulfur-based protecting groups so far investigated, the 2,2,5,5-tetramethylpyrrolidin-3-one-1-sulfinyl group exhibited near optimal properties for 5'-hydroxyl protection by virtue of the mildness of its deprotection conditions. Specifically, the iterative cleavage of a terminal 5'-sulfamidite group in the synthesis of 5'-d(ATCCGTAGCCAAGGTCATGT) on controlled-pore glass is efficiently accomplished by treatment with iodine in the presence of an acidic salt. Hydrolysis of the oligonucleotide to its 2'-deoxyribonucleosides upon exposure to snake venom phosphodiesterase and bacterial alkaline phosphatase did not reveal the formation of any nucleobase adducts or other modifications. These findings indicate that the 2,2,5,5-tetramethylpyrrolidin-3-one-1-sulfinyl group for 5'-hydroxyl protection of phosphoramidites, such as 10a-d, may lead to the production of oligonucleotide microarrays exhibiting enhanced specificity and sensitivity in the detection of nucleic acid targets. 相似文献
4.
G. Piccitto R. Pucci N. H. March A. Grassi 《International journal of quantum chemistry》1989,36(4):525-531
The derivative of the electron–electron potential energy Uee with respect to internuclear separation R is studied for light homonuclear diatomic molecules at equilibrium. It is readily related to nuclear–nuclear potential energy Unn, the force constant K, and the electron–nuclear potential energy Uen. An approximate expression, based on the simplest form of density functional theory, is then used to eliminate dUen/dR|Re. The result thus obtained for dUee/dR|Re transcends an earlier proposal of Kryachko by including a term 2/3ReK, with K the force constant. Numerical tests at SCF–RHF level are presented for nine homonuclear diatomic molecules. 相似文献
5.
Chisvert A Salvador A Pascual-Martí MC March JG 《Fresenius' Journal of Analytical Chemistry》2001,369(7-8):684-689
Spectrophotometric determination of a widely used UV-filter, such as oxybenzone, is proposed. The method is based on the complexation reaction between oxybenzone and Ni(II) in ammoniacal medium. The stoichiometry of the reaction, established by the Job method, was 1:1. Reaction conditions were studied and the experimental parameters were optimized, for both flow injection (FI) and sequential injection (SI) determinations, with comparative purposes. Sunscreen formulations containing oxybenzone were analyzed by the proposed methods and results compared with those obtained by HPLC. Data show that both FI and SI procedures provide accurate and precise results. The ruggedness, sensitivity and LOD are adequate to the analysis requirements. The sample frequency obtained by FI is three-fold higher than that of SI analysis. SI is less reagent-consuming than FI. 相似文献
6.
Carette M Zerega Y March RE Perrier P Andre J 《Rapid communications in mass spectrometry : RCM》2000,14(11):979-986
The coupling of a Rydberg electron capture ion source with a Nermag R10-10H quadrupole mass filter is described. Details are given of the addition to this instrument of a creation cell for atoms excited in Rydberg states. Within the Nermag ion source, such atoms allow attachment of electrons of well-defined thermal energy. SF(6) was used for optimization of the main experimental parameters (gas pressures and voltages applied to the electrodes). The procedure by which Rydberg electron attachment was confirmed is described. A polychlorobiphenyl compound was used to illustrate the performance of this ionization technique. Ion formation was observed in the absence of fragmentation. 相似文献
7.
Marchán V Moreno V Pedroso E Grandas A 《Chemistry (Weinheim an der Bergstrasse, Germany)》2001,7(4):808-815
We have studied how platinum(II) complexes [Pt(dien)Cl]Cl, [Pt(en)Cl2] and cisplatin react with hybrid molecules that contain sulfur and nitrogen ligands, in particular Phac-Met-linker-p5'dG (Phac = phenylacetyl), Phac-His-linker-p5'dG, Phac-His-Met-linker-p5'dG and Phac-His-Gly-Met-linker-p5'dCATGGCT. The progress of the reactions was monitored by HPLC, and by [1H,15N]-HSQC NMR when 15N-cisplatin was used. The products were isolated and characterised by using enzymatic and chemical reactions and spectroscopic techniques (UV and/or NMR spectroscopy, electrospray or MALDI-TOF mass spectrometry). The combined use of digestion with proteases and reaction with hydrogen peroxide followed by mass spectrometric analysis indicated the platinum coordination positions on the peptide moiety of the largest hybrid. Monofunctional Pt-S adducts were transformed into Pt-N complexes in which Pt-N7 bonds were formed preferentially. Most of the chelates isolated had Pt-S bonds, and, in the case of cisplatin complexes, loss of the ammine trans to sulfur gave rise to the formation of tricoordinate species with platinum-mediated peptide-nucleotide cross-links. 1,2-Intrachain platinum GpG adducts were only obtained in very small amounts (1-4%). 相似文献
8.
Determination of selenium, zinc and cadmium in antidandruff shampoos by atomic spectrometry after microwave assisted sample digestion 总被引:1,自引:0,他引:1
Microwave assisted pre-treatments for atomic spectrometric determination (inductive coupled plasma-optical emission spectrometry, ICP-OES or flame atomic absorption spectrometry, FAAS) of metallic elements, usually present in antidandruff shampoos, are proposed. They are based on the digestion of the sample with HNO3 into a closed reactor, which is irradiated at 800 W for a few minutes. Selenium was determined by ICP-OES. The limit of detection was 0.11 mg l−1; the relative standard deviation (R.S.D.) for the selenium content in the samples was in the 0.6–3.6% range. The results obtained were in agreement with the label contents and the recovery of the proposed method was in the 100–106% range. Zinc and cadmium were determined by FAAS. The limit of detection for zinc determination was 0.078 mg l−1; the R.S.D. for zinc contents was in the 0.8–8.6% range. A limit of detection of 0.09 mg l−1 was obtained for cadmium determination; the R.S.D. for cadmium contents was in the 0.7–2.7% range. The determinations were performed after two different sample mineralization pre-treatments — dry ashing (in an electric furnace) and wet mineralization (in a microwave oven). Both methodologies provided comparable results for zinc and cadmium determination in shampoos. The proposed microwave assisted digestion procedures allow a precise and accurate determination of selenium, zinc and cadmium in commercial antidandruff shampoos, and the sample pre-treatment is less time-consuming than the classic methods. 相似文献
9.
The initial reaction rate is measured by monitoring the rate of increase of temperature of the solution with a thermistor; 0.2–2 mg l?1 copper in the final solution is determined, with very few interferences. 相似文献
10.
Croley TR Hughes RJ Metcalfe CD March RE 《Rapid communications in mass spectrometry : RCM》2000,14(16):1494-1498
The ubiquity and favorable medicinal properties of flavonoids make essential the determination of flavonoid levels in various matrices. While developing a liquid chromatography/tandem mass spectrometry method for the analysis of the flavonoid, apigenin, anionic oligomers and nitrate- and chloride-bound clusters of this compound were observed. Tandem mass spectrometry of these oligomers and cluster ions showed the cleavage of apigenin molecules from the precursor. The observation of these cluster ions shows the possibility of post-column derivatization techniques to enhance specificity in analysis. Copyright 2000 John Wiley & Sons, Ltd. 相似文献