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21.
The interaction between POCl(3) or POBr(3) and pyridine or DMAP has been reinvestigated to clarify the discrepancies between previously published results concerning the Lewis acidity of phosphoryl halides and their behavior toward pyridine bases. The obtained results show that POCl(3) virtually does not react with pyridine, while it does with 4-(dimethylamino)pyridine (DMAP), even in SO(2) solution, to yield an ionic compound [(DMAP)(2)PO(2)]Cl.3SO(2) (1.3SO(2)). Its recrystallization from acetonitrile gives [(DMAP)(2)PO(2)]Cl.CH(3)CN (1.CH(3)CN). The POBr(3) reacts readily with both DMAP and pyridine forming the analogous tribromides, [(DMAP)(2)PO(2)]Br(3) (2) and [(py)(2)PO(2)]Br(3) (3), respectively. Treatment of 3 with Me(3)SiOSO(2)CF(3) in acetonitrile solution led to [(py)(2)PO(2)][CF(3)SO(3)].CH(3)CN (4), while the reaction between 1.CH(3)CN and Me(3)SiOPOF(2) gave [(DMAP)(2)PO(2)][PO(2)F(2)] (5). The crystal structures of 1.CH(3)CN, 1.3SO(2), 2, and 4 revealed that all four compounds are ionic containing the distorted tetrahedral cations [(DMAP)(2)PO(2)](+) and [(py)(2)PO(2)](+). Both ions represent a donor-stabilized form of the so far unknown cation [PO(2)](+). The geometry of [(DMAP)(2)PO(2)](+), optimized by density functional calculations at the B3LYP/6-31G(d,p) level, is in good agreement with X-ray structural data. The NBO analysis of natural atomic charges shows an extensive delocalization of the [PO(2)](+) intrinsic positive charge and indicates a contribution of the electrostatic attraction to the formation of N-P donor-acceptor bonds. According to a (31)P NMR study, the reactions of both phosphoryl halides with DMAP proceed via successive formation of the intermediates [(DMAP)POX(2)](+) and (DMAP)PO(2)X to give an equimolar mixture of [(DMAP)(2)PO(2)](+) and PX(5) (X = Cl, Br) as the end products. The NMR spectroscopic identification of the cations [(DMAP)POX(2)](+) and [(DMAP)(2)PO(2)](+) was supported by ab initio calculations of their chemical shifts. 相似文献
22.
Families of complex superlattice structures, consisting of combinations of basic hexagonal or square patterns, are found in a photosensitive reaction-diffusion system. The structures are induced by simple illumination patterns whose wavelengths are appropriately related to that of the system's intrinsic Turing pattern. Computer simulations agree with the structures and their stability. The technique offers a general approach to generating superlattices for use in information storage and other applications. 相似文献
23.
Violeta D. Mitic Snezana D. Nikolic Vesna P. Stankov-Jovanovic 《Central European Journal of Chemistry》2010,8(3):559-565
A kinetic spectrophotometric method for hydrazine determination in the range of 9.36×10−7 to 4.37×10−5 mol dm−3, based on the inhibitory effect of hydrazine on the oxidation of Victoria Blue 4- R by KBrO3, was developed and validated. Kinetic parameters are reported for both the indicating and the inhibiting reaction. The detection
limit was established as 9.98×10−8 mol dm−3. The selectivity of the proposed method was tested considering the influence of different ions that may be present in real
samples. The method was successfully applied for hydrazine determination in various samples (very pure water from the water-steam
system of a power plant and Isoniazid tablets, a pharmaceutical product).
相似文献
24.
Ivana M. Savic G. S. Nikolic Ivan M. Savic M. D. Cakic 《Russian Journal of Physical Chemistry A, Focus on Chemistry》2010,84(13):2306-2313
Bioactive copper complexes with oligosaccharides, pullulan or dextran, are the objective of the present study, because of
their possible biomedical applications. The alkaline and acid hydrolysis of the Cu(II) complexes with reduced low-molar pullulan
or dextran were carried out by conductometric method. The influence of ligand constitutions on the stability of the complexes
was examined on the basis of ligand property. The complexes degradation during alkaline and acid hydrolysis were carried out
in sodium hydroxide and hydrochloric acid solutions of 0.1, 0.5, and 1.0 mol dm−3, at different temperature (25, 40, and 60°C, respectively). According to the obtained results by the conductivity investigation
during forced degradation studies, it could be concluded that the Cu(II) complexes show the small pharmaceutical stability
to both hydrolysis. 相似文献
25.
Yin Wu Yehia Mechref Iveta Klouckova Anoop Mayampurath Milos V. Novotny Haixu Tang 《Rapid communications in mass spectrometry : RCM》2010,24(7):965-972
Glycosylation is one of the most common posttranslational modifications (PTMs) of proteins, the characterization of which is commonly achieved through proteomic protocol, involving trypsin digestion followed by liquid chromatography/tandem mass spectrometry (LC/MS/MS). However, it is often not possible to characterize all glycopeptides in a complex sample because of the high complexity of glycoproteomic samples, and the relative lower abundances of glycopeptides in comparison to the unmodified peptides. We present here a targeted MS/MS analysis approach, which utilizes a previously developed computational tool, GlyPID, to guide multiple experiments, thus permitting a complete characterization of all N‐glycosylation sites of glycoproteins present in a complex sample. We have tested our approach using model glycoproteins analyzed by high‐resolution LTQ‐FT MS. The results demonstrate a potential use of our method for a high‐throughput characterization of complex mixtures of glycosylated proteins. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
26.
27.
J. Vucicevic M. Popovic K. Nikolic S. Filipic D. Obradovic D. Agbaba 《SAR and QSAR in environmental research》2017,28(3):235-252
For this study, 31 compounds, including 16 imidazoline/α-adrenergic receptor (IRs/α-ARs) ligands and 15 central nervous system (CNS) drugs, were characterized in terms of the retention factors (k) obtained using biopartitioning micellar and classical reversed phase chromatography (log kBMC and log kwRP, respectively). Based on the retention factor (log kwRP) and slope of the linear curve (S) the isocratic parameter (φ0) was calculated. Obtained retention factors were correlated with experimental log BB values for the group of examined compounds. High correlations were obtained between logarithm of biopartitioning micellar chromatography (BMC) retention factor and effective permeability (r(log kBMC/log BB): 0.77), while for RP-HPLC system the correlations were lower (r(log kwRP/log BB): 0.58; r(S/log BB): –0.50; r(φ0/Pe): 0.61). Based on the log kBMC retention data and calculated molecular parameters of the examined compounds, quantitative structure–permeability relationship (QSPR) models were developed using partial least squares, stepwise multiple linear regression, support vector machine and artificial neural network methodologies. A high degree of structural diversity of the analysed IRs/α-ARs ligands and CNS drugs provides wide applicability domain of the QSPR models for estimation of blood–brain barrier penetration of the related compounds. 相似文献
28.
Nikolic D Li Y Chadwick LR Pauli GF van Breemen RB 《Journal of mass spectrometry : JMS》2005,40(3):289-299
The female flowers of hops (Humulus lupulus L.) used to flavor beer contain the prenylated flavonoids xanthohumol (XN) and isoxanthohumol (IX). IX is moderately estrogenic in vitro and XN has pharmacological properties that might make it useful as a cancer chemopreventive agent. The metabolism of these dietary flavonoids was investigated in vitro using human liver microsomes. Hydroxylation of a prenyl methyl group was the primary route of oxidative metabolism forming either cis or trans hydroxylated metabolites of IX but only the trans isomer of XN. The double bond on the prenyl group of both compounds formed an epoxide which was opened by an intramolecular reaction with the neighboring hydroxyl group. The potent phytoestrogen 8-prenylnaringenin (8-PN) was detected as a demethylation product of IX. However, the analogous demethylation reaction was not observed for XN. Since XN can be converted to IX through acid-catalyzed cyclization in the stomach, XN might contribute to the in vivo levels of estrogenic 8-PN following consumption of hops extracts. 相似文献
29.
Milos Toth 《Applied Physics A: Materials Science & Processing》2014,117(4):1623-1629
Electron beam-induced etching (EBIE) has traditionally been used for top-down, direct-write, chemical dry etching, and iterative editing of materials. The present article reviews recent advances in EBIE modeling and emerging applications, with an emphasis on use cases in which the approaches that have conventionally been used to realize EBIE are instead used for material analysis, surface functionalization, or bottom-up growth of nanostructured materials. Such applications are used to highlight the shortcomings of existing quantitative EBIE models and to identify physicochemical phenomena that must be accounted for in order to enable full exploitation and predictive modeling of EBIE and related electron beam fabrication techniques. 相似文献
30.
Dimitrije Djukanovic Milos Petkovic Milena Simic Predrag Jovanovic Gordana Tasic Vladimir Savic 《Tetrahedron letters》2018,59(10):914-917
A one-pot, domino process was developed as an alternative approach for the preparation of 2-unsubstituted imidazolones. The methodology utilizes readily accessible bisamides, which upon a dehydration/cyclisation sequence produced imidazolones in good yields. The transformation relies on the compatibility of the dehydrating agent and base, and the reaction conditions tolerate various functional groups. 相似文献