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991.
Chihiro Kachi‐Terajima Dr. Takamasa Akatsuka Masa‐aki Kohbara Satoshi Takamizawa Dr. 《化学:亚洲杂志》2007,2(1):40-50
The crystalline one‐dimensional compound, [RhII2(bza)4(pyz)]n ( 1 ) (bza=benzoate, pyz=pyrazine) demonstrates gas adsorbency for N2, NO, NO2, and SO2. These gas‐inclusion crystal structures were characterized by single‐crystal X‐ray crystallography as 1 ?1.5 N2 (298 K), 1 ?2.5 N2 (90 K), and 1 ?1.95 NO (90 K) under forcible adsorption conditions and 1 ?2 NO2 (90 K) and 1 ?3 SO2 (90 K) under ambient pressure. Crystal‐phase transition to the P space group that correlates with gas adsorption was observed under N2, NO, and SO2 conditions. The C2/c space group was observed under NO2 conditions without phase transition. All adsorbed gases were stabilized by the host lattice. In the N2, NO, and SO2 inclusion crystals at 90 K, short interatomic distances within van der Waals contacts were found among the neighboring guest molecules along the channel. The adsorbed NO molecules generated the trans‐NO???NO associated dimer with short intermolecular contacts but without the conventional chemical bond. The magnetic susceptibility of the NO inclusion crystal indicated antiferromagnetic interaction between the NO molecules and paramagnetism arising from the NO monomer. The NO2 inclusion crystal structure revealed that the gas molecules were adsorbed in the crystal in dimeric form, N2O4. 相似文献
992.
In order to explore the transfer mechanism of chromium(III) in mammals, a novel complex [Cr(ASA)(en)2]Cl· 2H2O, bis(ethylenediamine‐ κ 2 N,N′)(4‐aminosalicylic acid‐ κ 2 O,O′) chromium(III) monochloride dihydrate was synthesized (4‐aminosalicylic acid=H2ASA, ethylenediamine=en). The crystal structure belongs to orthorhombic system with the space group P212121 by means of X‐ray diffraction. The characteristic for transfer of Cr3+ from the compound to the low‐molecular‐mass chelator EDTA and the iron‐binding protein apoovotransferrin (apoOTf) was followed by UV‐visible (UV‐Vis) and fluorescence spectra in 0.01 mol·L?1 Hepes at pH 7.4. The second order rate constants were calculated. Those spectra in conjunction were used to obtain more accurate information about the interaction of chromium complex with apoOTf. The experimental results indicate that Cr3+ can be transferred from the complex to apoOTf with the retention of the 4‐aminosalicylic acid acting as a synergistic anion. 相似文献
993.
Stability constant for mercury binding by commercial and natural humic acids (HA) were determined using a new potentiometric mercury(II) sensor based on dithiosalicylic acid modified carbon paste electrode. The sensor present a high selective and sensitive response to mercury(II) ions, and a low detection limit of 1.8×10?8 M. The potentiometric titrations curves of humic acids against mercury(II) ions were modeled. For 1.00×10?7 to 3.00×10?4 M mercury(II) ion concentration levels the results are consistent with the presence of two different binding sites in the humic acid macromolecule. The strongest binding sites (log K1 ranging from 10.1 to 6.8) are probably due to interaction with carboxylic acid and amine groups in the molecule, whereas weakest binding sites (log K2 ranging from 8.8 to 4.5) can be associated to phenolic groups. 相似文献
994.
Xiu Hui Lu Hai Bin Yu Wei Rong Wu Yue Hua Xu 《International journal of quantum chemistry》2007,107(2):451-457
Mechanisms of the cycloaddition reaction between singlet difluoromethylene carbene and acetone have been investigated with the second‐order Møller–Plesset (MP2)/6‐31G* method, including geometry optimization and vibrational analysis. Energies for the involved stationary points on the potential energy surface (PES) are corrected by zero‐point energy (ZPE) and CCSD(T)/6‐31G* single‐point calculations. From the PES obtained with the CCSD(T)//MP2/6‐31G* method for the cycloaddition reaction between singlet difluoromethylene carbene and acetone, it can be predicted that path B of reactions 2 and 3 should be two competitive leading channels of the cycloaddition reaction between difluoromethylene carbene and acetone. The former consists of two steps: (i) the two reactants first form a four‐membered ring intermediate, INT2, which is a barrier‐free exothermic reaction of 97.8 kJ/mol; (ii) the intermediate INT2 isomerizes to a four‐membered product P2b via a transition state TS2b with an energy barrier of 24.9 kJ/mol, which results from the methyl group transfer. The latter proceeds in three steps: (i) the two reactants first form an intermediate, INT1c, through a barrier‐free exothermic reaction of 199.4 kJ/mol; (ii) the intermediate INT1c further reacts with acetone to form a polycyclic intermediate, INT3, which is also a barrier‐free exothermic reaction of 27.4 kJ/mol; and (iii) INT3 isomerizes to a polycyclic product P3 via a transition state TS3 with an energy barrier of 25.8 kJ/mol. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007 相似文献
995.
A reversed-phase liquid chromatographic (RPLC) method has been developed for determination of arabinosylcytosin (Ara-C) and
its metabolite 1-β-D-arabinofuranosyluracil (Ara-U) on a 250 mm × 4.6 mm i.d., 5 μm particle, Diamonsil C18 column. The mobile phase was a mixture of 5% methanol and 95% 10 mmol L−1 phosphate buffer adjusted to pH 5.5. The flow-rate was 1.0 mL min−1 and the injection volume 20 μL. Eluting compounds were detected at 270 nm by use of an ultraviolet detector. Under these
LC conditions cyclophosphamide (CTX) and pirarubicin (THP), two other medicines given with Ara-C in clinical treatment, do
not interfere with measurement of Ara-C and Ara-U. Individual calibration plots of peak area against concentration generated
from analysis of standard solutions were used to calculate the concentrations of Ara-C and Ara-U in sample solutions. The
calibration plot was linear in the range 2.5–100 μg mL−1, the average recovery of Ara-C and Ara-U was more than 98% (RSD < 2.5%), and between-day and within-day precision, expressed as relative standard deviation (RSD), were below 4.0%. LOQ for both Ara-C and Ara-U was 2 μg mL−1. The method is rapid, simple, accurate and reproducible, and especially useful for application to patient samples. 相似文献
996.
三齿单核三(3,5-二甲基-1-吡唑)硼氢钼配合物Tp*Mo(O)Cl2 (1)(Tp*=三(3,5-二甲基-1-吡唑)硼氢HB(C3H(Me2)N2)3)与含硫族元素碳硼烷的锂盐[(THF)2LiE2C2B10H10(THF)]< 相似文献
997.
本文报道了一种新型三维亚磷酸锌[HO(CH2)2NH3]2•[Zn3(HPO3)4]的合成和晶体结构。在它的结构中,ZnO4和HPO3严格按照顶点连接的方式交替相连。骨架结构存在两个沿着不同方向无限延伸的由ZnO4和HPO3组成的四元环链,在[0 1 0]、[0 4 15]和[0 -4 15]三个方向形成了三个交叉8元环孔道,有机胺阳离子起着平衡电荷和稳定骨架的结构。它的晶体数据为:[HO(CH2)2NH3]2•[Zn3(HPO3)4],M=640.21, 正交晶系, Fdd2空间群, a=2.8528, b=0.8426, c=1.6159nm, Z=8, V=3.884nm3, R1=0.0219, wR2=0.0544。 相似文献
998.
The molecular orientation distribution function of a stable radical 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl in magnetic-field oriented 4-cyano-4’-n-pentylbiphenyl was determined from the angular dependence of the ESR spectra. The preferred molecular orientation of radical species in the liquid crystal matrix was determined. The temperature evolution of the orientation distribution function was studied.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 190–195, January, 2005. 相似文献
999.
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
1000.
Polychlorinated biphenyls (PCBs) and chlorobenzenes (CBzs) are two classes of dioxin precursors formed in municipal solid waste incinerators (MSWIs); they produce negative health effects similar to those of dioxins. Reducing the analytical time required for determining the concentrations of these compounds in MSWIs is important for quickly evaluating their importance and assessing associated health risks. In the present study, water is used as a safe and environmentally friendly solvent in microwave-assisted extraction (MAE) for PCB and CBz analyses. MAE is compared with traditional Soxhlet extraction (SE) to determine the extraction efficiencies. The evaluation of extraction efficiencies shows that MAE has a high extraction efficiency compared with that of SE when water content is lower than 60%. Furthermore, the extraction time and organic solvent consumption are reduced with MAE compared with SE. 相似文献