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31.
Villanueva J Villegas V Querol E Avilés FX Serrano L 《Journal of mass spectrometry : JMS》2002,37(9):974-984
In the post-genomic era, several projects focused on the massive experimental resolution of the three-dimensional structures of all the proteins of different organisms have been initiated. Simultaneously, significant progress has been made in the ab initio prediction of protein three-dimensional structure. One of the keys to the success of such a prediction is the use of local information (i.e. secondary structure). Here we describe a new limited proteolysis methodology, based on the use of unspecific exoproteases coupled with matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS), to map quickly secondary structure elements of a protein from both ends, the N- and C-termini. We show that the proteolytic patterns (mass spectra series) obtained can be interpreted in the light of the conformation and local stability of the analyzed proteins, a direct correlation being observed between the predicted and the experimentally derived protein secondary structure. Further, this methodology can be easily applied to check rapidly the folding state of a protein and characterize mutational effects on protein conformation and stability. Moreover, given global stability information, this methodology allows one to locate the protein regions of increased or decreased conformational stability. All of this can be done with a small fraction of the amount of protein required by most of the other methods for conformational analysis. Thus limited exoproteolysis, together with MALDI-TOF MS, can be a useful tool to achieve quickly the elucidation of protein structure and stability. 相似文献
32.
Addition and Substitution Reactions at Tetrafluoro- and Tetrachlorodiborane(4) From equimolar mixtures of B2F4 and MenN(SiMe3)3-n (n = 0–3) the mono-addition products 1–4 are formed at low temperatures. By elimination of Me3SiF the adduct 2 gives the dimeric monosubstituted diborane 8 , which slowly decomposes at room temperature to the aminoborane 6 and (BF)n. The course of the reactions was studied by means of 11B and 19F NMR spectroscopy and by measuring the vapor pressures. According to the 11B and 31P NMR spectra the reaction of B2Cl4 with PCl5 or [Me4N]Cl in liquid hydrogen chloride at 0°C does not yield [PCl4]2+[B2Cl6]2? or [Me4N]2+[B2Cl6]2? but gives [PCl4]+[BCl4]?, PCl3 and BCl3 or [Me4N]+[BCl4]? and BCl3 besides (BCl)n. 相似文献
33.
Keshtov M. L. Rusanov A. L. Keshtova S. V. Petrovskii P. V. Shchegolikhin A. A. 《Russian Chemical Bulletin》2002,51(1):117-123
A series of previously unknown unsymmetrical difluoroaromatic compounds, viz., p-fluorobenzoylphenyl(p-fluorophenyl)-substituted imidazoles, pyrazines, and quinoxalines, were synthesized according to multistep procedures with the use of chloral as the key compound. The reactivities of the resulting difluoroaromatic compounds were estimated based on 19F and 13C NMR spectral data and the results of quantum-chemical calculations. The calculated charge densities on the Cipso atoms correlate linearly with the experimental chemical shifts in the 19F and 13C NMR spectra. Difluoroaromatic compounds, which are characterized by F > –110 and C > 163 and by the charge density on the Cipso atom higher than 0.08 e, are sufficiently activated to be used for the preparation of high-molecular-weight polyethers. 相似文献
34.
New activated bis- and tetrafluoroaromatic compounds containing the bis-phenylquinoxaline fragments, viz., methylene-bis-6(7),6"(7")-{2-(p-fluoro)phenyl-3[4-(p-fluorobenzoyl)phenyl]quinoxalines}, were prepared according to multistep procedures with the use of chloral as the starting compound. The presence of the activating carbonyl groups in the para positions with respect to two fluorine atoms opens up the possibility of the use of these monomers for the synthesis of high-molecular-weight aromatic quinoxaline-containing polyether ketones. 相似文献
35.
Facile synthesis of 6(E)-geranylgeraniol-19-oic acid 1,a naturally occurring alicyclic diterpene acid, by a Horner-Wadsworth-Emmons olefination of two readily available fragments 2 and 3,is described. 相似文献
36.
Uwe Klingebiel Gerhild Wendenburg Anton Meller 《Monatshefte für Chemie / Chemical Monthly》1979,110(2):289-296
Lithium salts of hydrazines react with fluorosilanes under formation of fluorosilylhydrazines and LiF. Five membered rings are obtained in the reaction of bis(fluorosilyl)-hydrazines with lithiated amines. The mass,1H-and19F-nmr spectra of the compounds are reported. 相似文献
37.
Anju Midha Rajender D. Verma K. Brown R. V. Parish 《Monatshefte für Chemie / Chemical Monthly》1983,114(6-7):661-667
Mixed dialkytin(IV) trifluoroacetates,Me EtSn(O2CCF3)2,Et Pr
n
Sn(O2CCF3)2 andPr
n
Bu
n
Sn(O2CCF3)2 have been prepared by metathetical reactions of the corresponding dialkyltin(IV) chlorides with silver trifluoroacetate in CH2Cl2. They are monomeric in benzene and nonconducting inMeNO2 andMeCN. Bidentate trifluoroacetate groups are indicated by their IR spectra.Mössbauer spectra confirmtrans-arrangement of theR-Sn-R moiety.1H,19F NMR and mass spectra are also discussed.
Gemischte Dialkylzinn(IV)-trifluoracetate
Zusammenfassung Die gemischten Dialkylzinn(IV)-trifluoroacetateMe EtSn(O2CCF3)2,Et Pr n Sn(O2CCF3)2 undPr n Bu n Sn(O2CCF3)2 wurden über Metathese-Reaktionen der entsprechenden Dialkylzinn(IV)-chloride mit Silbertrifluoracetat in CH2Cl2 dargestellt. Sie sind monomer in Benzol und nichtleitend inMeNO2 undMeCN. Die IR-Spektren zeigen zweizähnige Trifluoracetat-Gruppen an. DieMössbauer-Spektren bestätigen dietrans-Anordnung derR-Sn-R-Einheit. Die1H-,19F-NMR und die Massenspektren werden ebenfalls diskutiert.相似文献
38.
Gelebe AC Kaye PT Klein R Sewry JD Soper AG 《Magnetic resonance in chemistry : MRC》2005,43(11):952-955
The influence of substituents and structure on the 13C NMR spectra of four series of benzoxathiepine derivatives has been investigated. Signal assignments in the 13C NMR spectra have been facilitated by the use of several predictive methods, permitting comparison of their relative efficacy. 相似文献
39.
毛茛科植物贡嘎乌头 ( Aconitum liljestrandii)具有镇痛、镇静、祛风湿等功效 ,产于我国西藏东部及四川西部 [1] .我们从其块根中分得 1 8个单体 ,其中 1 6个为已知生物碱 [2 ,3] ,2个为新生物碱 [3] .本文报道新的 C19-二萜生物碱贡乌生 ( Liljestrandisine) 1的结构 .1 实验部分1 .1 仪器与试剂 Boetius微量熔点测定仪 ;Nicolet FTIR2 0 0 SXV型红外光谱仪 ,KBr压片 ;BrukerAC- E2 0 0和 Varian Unity INOVA40 0 /5 4核磁共振仪 ,溶剂为 CDCl3,TMS为内标 ;VG Autospec30 0 0型和 VG70 A型质谱仪 ;Pekin Polarimete… 相似文献
40.
Least squares estimations have been used extensively in many applications, e.g. system identification and signal prediction. When the stochastic process is stationary, the least squares estimators can be found by solving a Toeplitz or near-Toeplitz matrix system depending on the knowledge of the data statistics. In this paper, we employ the preconditioned conjugate gradient method with circulant preconditioners to solve such systems. Our proposed circulant preconditioners are derived from the spectral property of the given stationary process. In the case where the spectral density functions() of the process is known, we prove that ifs() is a positive continuous function, then the spectrum of the preconditioned system will be clustered around 1 and the method converges superlinearly. However, if the statistics of the process is unknown, then we prove that with probability 1, the spectrum of the preconditioned system is still clustered around 1 provided that large data samples are taken. For finite impulse response (FIR) system identification problems, our numerical results show that annth order least squares estimator can usually be obtained inO(n logn) operations whenO(n) data samples are used. Finally, we remark that our algorithm can be modified to suit the applications of recursive least squares computations with the proper use of sliding window method arising in signal processing applications.Research supported in part by HKRGC grant no. 221600070, ONR contract no. N00014-90-J-1695 and DOE grant no. DE-FG03-87ER25037. 相似文献