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1.
The preferred conformations of the tripeptide glutathione have been investigated by performing quantum mechanical calculations using the PCILO method. A series of model compounds representing fragments of the tripeptide has been studied as well as the complete molecule. The results are compared with the available experimental data. 相似文献
2.
Density functional (BLYP, B3LYP and BHLYP) and highly correlated MP2 and CCSD(T) calculations have been performed to investigate conformers, energy barriers, intramolecular H-bond strength, gas-phase basicity and deprotonation energies of glyoxilic acid oxime (gao) and related ions in gas phase and in aqueous solution (SCRF-PCM method). BHLYP/6-311G(d,p) and B3LYP/6-31++G(d) predictions for the global minimum conformer of gao were consistent with experiment. BLYP level overestimated the H-bond and stabilized incorrectly the H-bonded conformer. The calculations in solution indicated destabilization of H-bonded conformers due to the small polarizability and weaken of the H-bond. The same global minimum structures in gas phase and aqueous solution were found for gao-neutral (ectt) and gao-dianion (e−2), whereas they were different for gao-anion because of the strong decrease of the conformational energies in solution. The global minimum structures of the neutral, anion and dianion of gao, obtained in solution, are in agreement with experiment. The gas-phase basicity (GB) and molecular electrostatic potential (MEP) calculations revealed the same sites for electrophilic attack, supported by the nature of HOMO: the carbonylic oxygen for the neutral, the carboxylic oxygen for the anion and the oxime nitrogen for the dianion. MEP results in gas phase and in solution suggested a region between the two atoms, but not on one atom in accordance with bidentate binding of gao ions to a metal. The BHLYP/6-31++G(d,p) molecular properties of gao were in best consistent with CCSD(T) results. The thermodynamical properties (GB and bond deprotonation energy) of gao were better estimated at B3LYP level. 相似文献
3.
Michael I. Bruce Mark A. Buntine Benjamin G. Ellis Paul J. Low Brian W. Skelton 《Journal of organometallic chemistry》2004,689(21):3308-3326
The preparation of several ruthenium complexes containing cyanocarbon anions is reported. Deprotonation (KOBut) of [Ru(NCCH2CN)(PPh3)2Cp]PF6 (1) gives Ru{NCCH(CN)}(PPh3)2Cp (2), which adds a second [Ru(PPh3)2Cp]+ unit to give [{Ru(PPh3)2Cp}2(μ-NCCHCN)]+ (3). Attempted deprotonation of the latter to give the μ-NCCCN complex was unsuccessful. Similar chemistry with tricyanomethanide anion gives Ru{NCC(CN)2}(PPh3)2Cp (4) and [{Ru(PPh3)2Cp}2{μ-NCC(CN)CN}]PF6 (5), and with pentacyanopropenide, Ru{NCC(CN)C(CN)C(CN)2}(PPh3)2Cp (6) and [{Ru(PPh3)2Cp}2{μ-NCC(CN)C(CN)C(CN)CN}]PF6 (7). The Ru(dppe)Cp* analogues of 6 and 7 (8 and 9) were also prepared. Thermolysis of 6 (refluxing toluene, 12 h) results in loss of PPh3 and formation of the binuclear cyclic complex {Ru(PPh3)Cp[μ-NC{C(CN)C(CN)2}CN]}2 (10). The solid-state structures of 2-4 and 8-10 have been determined and the nature of the isomers shown to be present in solutions of the binuclear cations 7 and 9 by NMR studies has been probed using Hartree-Fock and density functional theory. 相似文献
4.
Fernando Castañeda Paul Silva M. Teresa Garland Ata Shirazi Clifford A. Bunton 《Phosphorus, sulfur, and silicon and the related elements》2013,188(8):2152-2168
The phosphonium ylidic diesters, methyl and ethyl isopropyl and, methyl and ethyl t-butyl triphenylphosphoranylidene malonates, 1a,b and 2a,b , respectively, have the syn-anti conformation in solution, as in the crystal, and the bulkier alkoxy group is oriented towards phosphorus. The 1 H NMR spectra show that in 1a,b , the isopropyl group is oriented towards the face of a phenyl group, consistent with π shielding in the 1 H signals, and examination of the 1 H coupled 13 C NMR spectra allows assignment of the acyl carbon signals. Computed bond lengths and angles for isolated molecules are similar to those in the crystal, and the geometry and the NMR spectra indicate extensive ylidic resonance. Estimated partial atomic charges on the ester oxygens are more negative when they are oriented towards, rather than away from, phosphorus. 相似文献
5.
Patrizia Scafato Francesca Caprioli Laura Pisani Daniele Padula Fabrizio Santoro Giuseppe Mazzeo Sergio Abbate France Lebon Giovanna Longhi 《Tetrahedron》2013
Three forms of chiroptical spectroscopies, electronic circular dichroism (ECD), vibrational circular dichroism (VCD), and optical rotatory dispersion (ORD) have been employed to study the configuration and conformational properties of the three molecules: (S)-3-phenylcyclopentanone, (S)-3-phenylcyclohexanone, and (S)-3-phenylcycloheptanone (including (S)-3-phenylcyclopentanone-2,2,5,5-d4 and (S)-3-phenylcyclohexanone-2,2,6,6-d4). ECD and VCD spectra in the mid-IR for the three molecular systems are marginally dependent on fine conformational details, as interpreted in terms of standard DFT computational methods, with common spectroscopic features to the three systems clearly identified. Accounting for vibronic coupling mechanisms reproduces the structuring of ECD n→π∗ band. The ORD curves are quite similar for the three types of molecules, but their interpretation highlights a crucial role played by conformations of the cycloalkanone ring in the case of (S)-3-phenylcycloheptanone. The same conclusions are reached by considering the VCD spectra in the CH-stretching region. 相似文献
6.
A direct tetraalkylation of thiacalix[4]arenes using procedures well established in ‘classical’ calixarene chemistry usually gives the 1,3-alternate conformers as the main product (n-PrI/K2CO3/acetone) while the cone conformers are obtained only in very poor yields (n-PrI/NaH/DMF). Surprisingly, the so far almost inaccessible cone conformers can be prepared in high yields using the two-step procedure: dialkylation-dialkylation, opening the way for their further utilisation in supramolecular chemistry. 相似文献
7.
Abstract The Diels-Alder adduct of phencyclone, compound 1, with p-fluoranil, compound 3, has been prepared in refluxing toluene. The adduct, compound 2, has been examined by 1H, 13C and 19F NMR spectroscopy at 300, 75 and 282 MHz, respectively. At ambient temperature, the unsubstituted bridgehead phenyl groups in adduct 2 are found to exhibit hindered rotation, resulting in slow exchange limit (SEL) 1H NMR spectra. Full aryl proton assignments are made based on 1D and 2D (COSY45) NMR. The 19F NMR (proton coupled) reveals one of the two 19F signals to be a triplet. This resonance collapses to a singlet in the proton decoupled 19F spectrum, implying an unexpected long range 1H-19F coupling. For the 13C NMR spectrum, tentative assignments are presented. Data for compound 2 as a model compound for drugs are discussed in terms of the hindered aryl rotation and evidence of magnetic anisotrppic effects. 相似文献
8.
Dr. Zixuan Xu Zhaoyu Wang Dr. Wei Yao Yanhua Gao Yuxin Li Dr. Huifang Shi Prof. Wei Huang Prof. Zhongfu An 《Angewandte Chemie (International ed. in English)》2023,62(24):e202301564
Dynamic room temperature phosphorescence (RTP) materials have potential applications in optoelectronics, which inevitably suffer from poor processability, flexibility or stretchability. Herein, we report a concise strategy to develop supercooled liquids (SCLs) with dynamic RTP behavior using terminal hydroxyl engineering. The terminal hydroxyls effectively hinder the nucleation process of molecules for the formation of stable SCLs after thermal annealing. Impressively, the SCLs show reversible RTP emission via alternant stimulation by UV light and heat. Photoactivated SCLs have phosphorescent efficiency of 8.50 % and a lifetime of 31.54 ms under ambient conditions. Regarding the dynamic RTP behavior and stretchability of SCLs, we demonstrate the applications in erasable data encryption and patterns on flexible substrates. This finding provides a design principle for obtaining SCLs with RTP and expands the potential applications of RTP materials in flexible optoelectronics. 相似文献
9.
Juan M. Aceves-Hernández Esther Agacino-Valdés Manuel Paz 《Journal of Molecular Structure》2006,786(1):1-8
Hydrochlorothiazide was characterized in order to determine the possible structural modifications at different temperatures due to its importance as a drug to control heart diseases and a diuretic. This compound could present conformers due to the rotation of the NH2 group, which was studied by using different techniques such as Thermal Analysis, IR spectroscopy, X-Ray Diffraction and complemented by theoretical calculations. The theoretical and experimental results point to the conclusion that no polymorphic forms are present in the compound under study. The calculations confirm the apparent difference in values between theory and experiment for the vibration frequencies explained by the hydrogen bonds between near molecules. 相似文献
10.
《Comptes Rendus Chimie》2014,17(5):420-430
A series of trans- and cis-3,4-disubstituted 5-oxomorpholine-2-carboxylic acids 5 were prepared by a cyclocondensation between diglycolic anhydride 3 and arylideneamines 4. Transformations of the carboxylic group leading to a peptide bond in the side chain to the morpholinone ring were effected. The relative configurations and the preferred conformations of the substituents at the morpholinone ring in some of the newly prepared derivatives were determined by means of 1H NMR and X-ray analysis. 相似文献