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1.
Reddy PN Srikanth R Swamy NS Srinivas R Sharma GV Nagendar P Krishna PR 《Journal of mass spectrometry : JMS》2005,40(11):1429-1438
Positive and negative ion electrospray ionization (ESI) tandem mass spectral study of a new series of hybrid peptides, viz, BocN-alpha,beta-peptides and BocN-beta,alpha-peptides, synthesized from C-linked carbo-beta3-amino acids [Caa (S)] and L-Ala has been carried out. The alpha,beta-peptides have been differentiated from beta,alpha-peptides by the collision-induced dissociation (CID) of [M + H]+ and [M - H]- ions in positive and negative ion ESI-MS respectively. The fragment ion [M + H - C(CH3)3 + H]+ formed from [M + H]+ ions by the loss of 2-methyl-prop-2-ene in alpha,beta-peptides with L-Ala at the N-terminus is insignificant or totally absent for beta,alpha-peptides which have the Caa (S) at N-terminus. The fragment ion [M - H-C(CH3)3OH - HNCO]- formed from [M - H]- of beta,alpha-peptide acids is totally absent for alpha,beta-peptide acids. This has been attributed to the absence of the beta-methylene group in alpha,beta-peptides, and the participation of the beta-methylene group in the loss of HNCO in beta,alpha-peptide acids is confirmed by the deuteration experiments. The CID of [M + H-Boc + H]+ ions of these peptides also produce characteristic fragmentation. In the CID spectra of alpha,beta-peptides, the b(n)+ ions and the resulting y(n)+ ions occur at a mass difference of 243 and 71 Da corresponding to the successive losses of Caa and L-Ala, whereas a mass difference of 71 and 243 Da is observed for beta,alpha-peptides. In contrast to the CID of protonated peptides, the CID of [M - H]- ions of the alpha,beta- and beta,alpha-peptide acids do not give b(n)- ions and show abundant z(n) (-) ions. Further, a pair of diastereomeric dipeptide esters and acids have been distinguished by the CID of [M + H]+ ions. The loss of 2-methyl-prop-2-ene is more pronounced for Boc-NH-Caa(R)-D-Ala-OCH3 (21) and Boc-NH-Caa(R)-D-Ala-OH (23) with Caa (R) at the N-terminus, whereas it is totally absent for Boc-NH-Caa (S)-D-Ala-OCH3 (22) and Boc-NH-Caa(S)-D-Ala-OH (24) peptides, which have Caa (S) at the N-terminus. Thus, on the basis of our previous and present studies, we propose that the CID of [M + H]+ ions provides a simple and useful method for distinguishing the configuration of Caa (S or R) at the N-terminus of BocN-carbo beta,alpha- and beta,beta-dipeptides. 相似文献
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3.
Mohamed M. Ibrahim Gaber A.M. Mersal Nagi El-Shafai Mohamed M. Youssef Hanaa Shokry 《Comptes Rendus Chimie》2014,17(10):1013-1022
A dithiolate-containing a carbamate mononuclear cobalt(II) complex namely, [Co(Boc-S)2] (1), was obtained by the reaction of a methanolic solution of cobalt(II) nitrate hexahydrate with two equimolar amounts of the deprotonated form of tert-butyl N-(2-mercaptoethyl)carbamate (Boc-SH). The cobalt(II) complex (1) was characterized in the solid state and in solution by using FT–IR, Raman, UV–visible, and EI–mass spectroscopies, as well as thermal and X-ray diffraction studies. Spectral data showed that the carbamate (Boc-SH) acts as a mono-anionic bidentate ligand coordinating the cobalt(II) ion through two imine nitrogen and two deprotonated thiolate sulfur donor atoms in a distorted tetrahedral geometry. The thermoanalytical data evidence that the complex is stable up to 165 °C and undergoes complete decomposition, resulting in CoO. TEM imaging of the oxide residue shows its nano size clusters, suggesting that the complex (1) may be used as a precursor for nano-oxides. X-ray powder diffraction patterns evidence an isomorphism among the complex. The redox behavior of the cobalt(II) complex was also investigated by cyclic voltammetry. The reaction of the dithiolate cobalt(II) complex (1) with methyl iodide appears to occur intramolecularly with the cobalt-bound dithiolate, forming the cobalt(II)-bound dithioether complex [Co(Boc–SCH3)2]I2 (2), as a dication complex with a clean second-order reaction of 13.24 × 10−2 M−1·s−1. 相似文献
4.
Nagi Reddy Vanga Anudeep Kota Ramakrishna Sistla Mallavadhani Uppuluri 《Molecular diversity》2017,21(2):273-282
5.
The first total synthesis of Pestalotioprolide C and C7-epi-Pestalotioprolide C adopting Noyori asymmetric reduction, HWE Olefination and Shiina macrolactonization as the key steps has been described. 相似文献
6.
M. C. Reddy B. P. Nagi Reddy K. R. Sridharan J. Ramakrishna 《Magnetic resonance in chemistry : MRC》1984,22(7):464-467
From consideration of 1H–1H vicinal coupling constants and 13C? 1H long-range coupling constants in a series of amino acid derivatives, the precise values of 13C component vicinal coupling constants have been calculated for the three minimum energy staggered rotamers for the C(α)H? C(β)H2 side-chains of amino acids. 相似文献
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8.
Venkatapuram Padmavathi Sanapalli Nagi Reddy Guda Dinneswara Reddy Bhumireddy Chinnachennaiahgari Venkatesh Adivireddy Padmaja 《Journal of heterocyclic chemistry》2011,48(5):1197-1201
A new class of bis heterocycles—sulfone linked pyrazolyl oxadiazoles thiadiazoles were prepared from E‐phenylsulfonylethenesulfonylacetic acid and studied their antimicrobial activities. J. Heterocyclic Chem., (2011). 相似文献
9.
In this paper, we study the calibration problem for the Merton–Vasicek default probability model [Robert Merton, On the pricing of corporate debt: the risk structure of interest rate, Journal of Finance 29 (1974) 449–470]. We derive conditions that guarantee existence and uniqueness of the solution. Using analytical properties of the model, we propose a fast calibration procedure for the conditional default probability model in the integrated market and credit risk framework. Our solution allows one to avoid numerical integration problems as well as problems related to the numerical solution of the nonlinear equations. 相似文献
10.
BINDING OF HEMATOPORPHYRIN DERIVATIVE TO HUMAN SERUM ALBUMIN 总被引:1,自引:0,他引:1
Abstract Dialysis of hematoporphyrin derivative fraction A (HpD-A) off human serum albumin at 38°C followed the Hill equation for cooperative binding with saturation at 5 to 8. 600 dalton porphyrin units. Approximately 15% of the HpD-A was free for concentrations typical of human serum in photoradiation therapy. Possible structures of the tumor-localizing and -photosensitizing component in HpD-A are considered. Of these, a folded-over, covalent dimer appears to be more consistent with the photophvsical properties. 相似文献