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991.
Young‐Kyu Han 《Journal of computational chemistry》2001,22(16):2010-2017
We have compared the performance of widely used hybrid functionals for calculating the bond lengths and harmonic vibrational frequencies of AnF6 (An=U, Np, and Pu) and UF6?nCln (n=1–6) molecules using “small‐core” relativistic effective core potentials and extended basis sets. The calculated spectroscopic constants compare favorably with experimental data for the bond lengths (average error ≤ 0.01 Å) and vibrational frequencies (average error ≤ 7 cm?1) of the AnF6 molecules. The experimental vibrational frequencies of the stretching modes were available for most of the UF6?nCln (n=1–6) molecules. The calculated vibrational frequencies are in good agreement with the experimental data to within 4.6 cm?1 and 7.6 cm?1 for selected Becke1 and Lee, Yang, Parr (B1LYP), and Becke3 and Perdew, Wang (B3PW91) functionals, respectively. We conclude that one can predict reliable geometries and vibrational frequencies for the unknown related systems using hybrid density functional calculations with the RECPs. The geometries and vibrational frequencies of the UF6?nCln (n=1–6) molecules that have not been determined experimentally are also presented and discussed. © 2001 John Wiley & Sons, Inc. J Comput Chem 22: 2010–2017, 2001 相似文献
992.
The synthesis of 6‐amino‐4,5‐dihydro‐8H‐1‐(2‐phosphonylmethoxyethyl)imidazo[4,5‐e][1,3]diazepine‐4,8‐dione (7), a novel ring‐expanded (“fat”) acyclic nucleotide analogue of phosphonomethoxyethylguanine (PMEG), has been reported. It was prepared in 4 steps in 51% overall yield starting from dimethyl imida‐zole‐4,5‐dicarboxylate. 相似文献
993.
Daniel A. Vega John M. Sebastian Yueh‐Lin Loo Richard A. Register 《Journal of Polymer Science.Polymer Physics》2001,39(18):2183-2197
Triblock copolymers in midblock‐selective solvents can form physical gels. However, at low triblock contents (near the percolation threshold), the bridging of chains between micelles can lead to macrophase separation. Adding a styrene–isoprene diblock to a styrene–isoprene–styrene triblock copolymer in squalane can eliminate macrophase separation, yielding a wide range of stable, single‐phase gels with a disordered arrangement of micelles. The plateau modulus of these triblock gels scales with the 2.2 power of polymer content, indicating the importance of entanglements in dictating the modulus. Comparing gels made from the midblock‐saturated derivative of the same polymer [styrene‐(ethylene‐alt‐propylene)‐styrene] in squalane reveals that the modulus differences in the gels are a direct consequence of the difference in the entanglement molecular weight of the midblock homopolymer in bulk. Finally, the broad relaxation spectrum of these triblocks is well‐described by a recent theory for the dynamics of entangled star polymers, with the breadth of the relaxation spectrum dictated by the number of entanglements per midblock in the gel. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2183–2197, 2001 相似文献
994.
Loon‐Seng Tan Sharon R. Simko Shih Jung Bai Richard A. Vaia Barney E. Taylor Marlene D. Houtz Max D. Alexander Robert J. Spry 《Journal of Polymer Science.Polymer Physics》2001,39(20):2539-2548
As an alternative method for processing polyaniline (PANI) from its conducting (protonated) state, vacuum casting of PANI from a methanesulfonic acid (MSA) solution provided films with electrical conductivity values of about 130–150 S/cm. In addition, we similarly prepared blended films of PANI · MSA and poly(p‐phenylene benzobisthiazole) (PBZT). This process eliminated the need for a subsequent protonation step and had the additional advantage that the conjugated PBZT may provide alternative conducting pathways. Conductivity values of the composite films ranged from 100 pS/cm to 124 S/cm, and the films displayed critical concentration behavior with a PANI threshold concentration of 2.75% and a critical exponent of 4. Transmission electron micrographs displayed phase‐separated regions with PANI forming a continuous network at high concentrations. Thermogravimetric analysis results demonstrated the thermal and thermooxidative stability advantage of the blends due to the PBZT component. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2539–2548, 2001 相似文献
995.
Ping Yin Xian‐Yang Chen Chong‐De Li Xin‐Quan Xin 《International journal of quantum chemistry》2001,82(6):293-298
Ab initio calculations have been carried out to study the structures and relative stabilities of the planar eight‐membered ring B4N4H4 and its isoelectronic species C8H4 at the HF/6‐31G*, MP2/6‐31G*, MP2/6‐311G**, and MP4SDQ/6‐31G* levels. The analyses of Milliken population, vibration frequencies, π‐molecular orbital components, and orbital energy levels were used to evaluate the relative stabilities of these two similar systems. The homodesmotic reactions were also taken to be a useful index of relative stability for X4Y4H4 (XY=CC, BN) and gave the resonance energies with MP4SDQ/6‐31G* of C8H4 (?37.2 kcal/mol) < B4N4H4 (?29.2 kcal/mol). Furthermore, we calculated the thermodynamic functions of these reactions to discuss the influence of temperature. It is concluded that B4N4H4 may exist in theory and could be a little more stable than C8H4. © 2001 John Wiley & Sons, Inc. Int J Quant Chem 82: 293–298, 2001 相似文献
996.
Jiwen Cai Xiaopeng Hu Cai‐Hong Chen Liang‐Nian Ji 《Acta Crystallographica. Section C, Structural Chemistry》2001,57(4):394-396
The racemic title compound, trans‐[N,N‐bis(2‐aminoethyl)‐1,2‐ethanediamine‐κ4N](dl ‐isoleucinato‐N,O)cobalt(III) diperchlorate, [Co(C6H18N4)(C6H12NO2)](ClO4)2, crystallizes in the enantiomorphous space group P212121 with Z = 12 (Z′ = 3). Each of the three cations in the asymmetric unit represents a different chirality of the isoleucine ligand; two of them are R (or d ) and the third is the S (or l ) enantiomer. The mixture crystallizes in a so‐called unbalanced crystallization, in which the cations adopt a chiral array of composition RRS or SSR, depending on the crystal selected for data collection. 相似文献
997.
998.
Miao Du Zhi‐Hui Zhang Yan‐Ping You 《Acta Crystallographica. Section C, Structural Chemistry》2005,61(9):o574-o576
Co‐crystallization of hemimellitic acid (benzene‐1,2,3‐tricarboxylic acid) dihydrate (H3HMA·2H2O) with 4,4′‐bipyridine (4,4′‐bpy) affords the 1:1 co‐crystal benzene‐1,2,3‐tricarboxylic acid–4,4′‐bipyridine (1/1), H3HMA·4,4′‐bpy or C9H6O6·C10H8N2. Strong O—H⋯O hydrogen bonds connect the acid molecules to form a one‐dimensional zigzag chain, around which the 4,4′‐bpy components are fixed as arms via O—H⋯N interactions, resulting in a ladder motif. Through weak C—H⋯O non‐covalent forces, the resulting acid layers are extended into a three‐dimensional pillar‐layered architecture supported by rod‐like 4,4′‐bpy components. The influence on hydrogen‐bonding models is also discussed, with the discovery of an unexpected interaction motif that does not follow the routine hydrogen‐bonded hierarchical rule in the construction of an acid–base co‐crystal. 相似文献
999.
Jordi de Mier‐Vinu ngel M. Montaa Virtudes Moreno María J. Prieto 《无机化学与普通化学杂志》2005,631(11):2054-2061
Two 1,4‐diamine ligands were synthesized having 1,2‐bis(aminomethyl)‐cyclohexane and 1,2‐bis(aminomethyl)‐benzene structures. The two ligands have different electron density in the six‐membered ring: a cyclohexane versus a phenyl ring. The organic synthesis of the ligands was carried out by synthetic pathways of seven and four steps, respectively, starting from 1,2,3,6‐tetrahydrophthalic anhydride and diethyl phthalate. The coordination of platinum to these ligands afforded platinum(II) complexes which are analogue to the clinical drug cisplatin but form a seven‐membered chelate ring. The interaction of the platinum compounds with DNA was studied in order to know the relationship between the electron density of ligands and their capability to chelate DNA, by using three techniques: Circular Dichroism, Agarose Gel Electrophoresis and Atomic Force Microscopy. The degree of interaction of both compounds with DNA was slightly different, but both complexes showed a cisplatin‐like behaviour and are promising candidates to follow an extensive study of their cytotoxic activity. 相似文献
1000.
Novel synthesis of (1H)‐pyridin‐2‐one, pyrazolo[1,5‐a]pyrimidine and isoxazole derivatives incorporating N‐methylphthalimide moiety are reported. Reaction of enaminone 2 with malononitrile affords 4. Condensation of 2 with cyanothioacetamide or benzoylacetonitrile affords compounds 6 and 7 respectively. Reaction of 2 with hydrazine hydrate afford 2,3‐dihydrophthalazine‐1,4‐dione ( 10 ). Condensation of 2 with hydroxylamine and 3‐aminopyrazole derivatives affords compounds 12 and 15a,b respectively. Antimicrobial and antifungal activity were determined for representative compounds and most of them showed moderate activity as antimicrobial agents, while compounds 2 and 7 show strong activity against Aspergillus niger. The structure of the newly synthesized compounds was elucidated by elemental analyses and 1H nmr spectra and some cases by 13C nmr investigation. 相似文献