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991.
Jurriaan M Zwier Albert M Brouwer Tamás Keszthelyi Gurusamy Balakrishnan Jesper F Offersgaard Robert Wilbrandt Frédérique Barbosa Urs Buser Jér?me Amaudrut Georg Gescheidt Stephen F Nelsen Charles D Little 《Journal of the American Chemical Society》2002,124(1):159-167
The radical cation of 1,3,6,8-tetraazatricyclo [4.4.1.1(3,8)]dodecane (TTD) has been studied using magnetic resonance and optical spectroscopic methods and computational techniques. With the help of deuterated isotopomers, assignments of EPR and resonance Raman spectra could be unequivocally established. The results demonstrate that the radical cation has D(2d) symmetry, and instantaneous electron delocalization over the four equivalent nitrogen atoms occurs. This extensive delocalization in a completely saturated system is a unique feature of the TTD radical cation. The spectroscopy of TTD, in contrast to that of simpler diamines such as 1,4-diaza[2.2.2]bicyclooctane, simultaneously reveals the consequences of orbital interactions through space and through bonds. The relationship between nitrogen pyramidalization and hyperfine coupling constants in nitrogen-centered radical cations with a number of different bonding arrangements is reviewed. 相似文献
992.
Many analytical approaches are available to evaluate (bio)molecular interactions, all of which have their particular advantages and disadvantages. In recent years, two relatively new techniques have emerged that may be used by the bioanalytical community to evaluate such interactions, namely affinity capillary electrophoresis (ACE) and bioaffinity electrospray ionization-mass spectrometry (ESI-MS). In this paper, we describe and evaluate the use of both these techniques for the investigation of the interactions of glycopeptide antibiotics with peptides that mimic the bacterial cell wall binding site. We focus particularly on the effect of the sugar moieties attached to the antibiotic peptide backbone and on the noncovalent dimerization of these glycopeptide antibiotics. 相似文献
993.
Rózyło TK Siembida R Nemeth ZI Albert L Tyihak E 《Biomedical chromatography : BMC》2000,14(3):173-179
Taking into consideration the unquestionable intracellular occurrence of formaldehyde (HCHO) and its generators in cells of plant, animal and human organisms as well as in body fluids it was resolved to determine their levels in hard tissues of physiologically and pathologically changed teeth. The aim of the work was to determine the relationship between the level of HCHO and the levels of its generators in pathologically changed teeth, mainly carietic teeth as tooth caries is still a serious and commonly occurring problem. The occurrence of HCHO (captured as its dimedone adduct) and some of its potential generators was demonstrated in the hard tissues of healthy and pathological human teeth by means of OPLC, HPLC and MS analyses. It was established that the measurable level of HCHO was increased in the carietic teeth in comparison with healthy ones. In the case of paradontic tooth sample, a dramatic increase of HCHO was observed and at the same time the level of betaines was decreased considerably. The obtained results give a new insight into the pathology of hard tissues of teeth in strong correlation with the phases of stress syndrome. 相似文献
994.
Homochiral cis,cis-; cis,trans- and trans,trans-spiro[4.4]nonane-1,6-diols were prepared via diastereoselective reduction of enantiomerically pure spiro[4.4]nonane-1,6-dione (1) with the corresponding reducing agents: lithium n-butyldiisobutylaluminium hydride for cis,cis-diol (2) with 88% yield; BH3·THF for cis, trans-diol (3) with 91% yield; LiAlH4 for trans,trans-diol (4) with 15% yield. 相似文献
995.
[reaction: see text] The synthesis of several cis-2,3,6-trisubstituted piperidines has been developed employing the aza-Achmatowicz oxidation as the key reaction step. Its usage is illustrated by the facile synthesis of the piperidin-3-ol alkaloids (+/-)-deoxocassine and (+/-)-azimic acid. 相似文献
996.
Comelles J Moreno-Mañas M Pérez E Roglans A Sebastián RM Vallribera A 《The Journal of organic chemistry》2004,69(20):6834-6842
Cu(SbF6)2-AdamBox and copper(II) bis-(5-tert-butylsalicylaldehydate) catalyze the Michael addition in neutral media. Mechanistic studies, based on UV-vis, IR, and electrospray ionization mass spectrometry (ESI-MS), suggest that copper enolates of the beta-dicarbonyl formed in situ are the active nucleophilic species. 相似文献
997.
[reaction: see text] A unique reaction of 4-hydroxycoumarins with p-benzoquinone and pyridine was found, and through the reaction, six zwitterionic 4-hydroxycoumarin derivatives were synthesized. The structures of these compounds were determined by IR, MS(ESI), 1H NMR, 13C NMR, and single-crystal X-ray diffraction studies. 相似文献
998.
Garcia-Manyes S Verdaguer A Gorostiza P Sanz F 《The Journal of chemical physics》2004,120(6):2963-2971
NaCl hillocks have been grown on the NaCl(100) monocrystalline surface by simply making the tip of an atomic force microscope cantilever interact with the surface. A quantitative discussion about the hillock dissolution process as well as physical stability of these ionic surfaces has been made. Molecular dynamics simulations helped us to interpret the experimental data. An explanation for the hillock formation and dissolution phenomena is also discussed. 相似文献
999.
Artur M. S. Silva Judite S. Vieira Cristela M. Brito José A. S. Cavaleiro Tamás Patonay Albert Lévai José Elguero 《Monatshefte für Chemie / Chemical Monthly》2004,135(3):293-308
Summary. The bromination of 2-styrylchromones, bearing electron neutral substituents, with two molar equivalents of piridinium tribromide gave 2-(2-aryl-1,2-dibromoethyl)chromones and 3-bromo-2-(2-aryl-1,2-dibromoethyl)chromones. The presence of electron-donating substituents on their B ring led to a mixture of compounds due to the higher reactivity of their C(2)=C(3) and C=C double bonds, whereas the strongly electron-withdrawing group hindered the bromination. The dehydrobromination of 2-(2-aryl-1,2-dibromoethyl)chromones with triethylamine gave a diastereomeric mixture of (E)- and (Z)-2-(-bromostyryl)chromones. Some novel 4(5)-aryl-5(4)-(2-chromonyl)-1,2,3-triazoles have been obtained from the reactions of 2-(2-aryl-1,2-dibromoethyl)chromones, 2-(-bromostyryl)chromones, and 2-styrylchromones with sodium azide. The reactions of 2-styrylchromones with sodium azide are more efficient, general, and constitute a one-pot synthetic method of 4(5)-aryl-5(4)-(2-chromonyl)-1,2,3-triazoles allowing the preparation of 1,2,3-triazoles bearing either electron-donating or electron-withdrawing substituents in their aryl ring. The structure of all new compounds was established by extensive NMR spectroscopic studies. 相似文献
1000.
Wilds CJ Wawrzak Z Krishnamurthy R Eschenmoser A Egli M 《Journal of the American Chemical Society》2002,124(46):13716-13721
(L)-alpha-Threofuranosyl-(3'-->2')-oligonucleotides (TNA) containing vicinally connected phosphodiester linkages undergo informational base pairing in an antiparallel strand orientation and are capable of cross-pairing with RNA and DNA. TNA is derived from a sugar containing only four carbon atoms and is one of the simplest potentially natural nucleic acid alternatives investigated thus far in the context of a chemical etiology of nucleic acid structure. Compared to DNA and RNA that contain six covalent bonds per repeating nucleotide unit, TNA contains only five. We have determined the atomic-resolution crystal structure of the B-form DNA duplex [d(CGCGAA)Td(TCGCG)](2) containing a single (L)-alpha-threofuranosyl thymine (T) per strand. In the modified duplex base stacking interactions are practically unchanged relative to the reference DNA structure. The orientations of the backbone at the TNA incorporation sites are slightly altered in order to accommodate fewer atoms and covalent bonds. The conformation of the threose is C4'-exo with the 2'- and 3'-substituents assuming quasi-diaxial orientation. 相似文献