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41.
对于NO分子轨道的能级次序现有两种不同的说法,不少人根据NO与O_2~+是等电子体,由O_2~+分子的能级次序确定NO分子组态。本文用NO和O_2~(+)从头计算结果以及NO的紫外光电子能谱相结合的方法说明NO的5σ轨道是弱成键轨道,5σ的轨道能稍高于1π轨道能,也就是说NO的能级次序是与N_2分子相同的;NO与O_2~+虽是等电子体,但是能级次序并不相同,因此由O_2~+的能级次序确定NO分子的电子组态是不妥的。 相似文献
42.
A series of hydrogels based on N-isopropylacrylamide, sodium acrylate, and N-tert-butylacrylamide were synthesized by free radical polymerization in a mixture of dioxane and water with tetra(ethylene glycol) diacrylate as the crosslinker and benzoyl peroxide as the initiator. The swelling behavior including the swelling rate of the crosslinked gels in water was studied with gravimetric method. The swelling ratio of the gel (0.1 mol% crosslinking) can reach 420 g/g at 20 °C and such a gel can release 96% of the water absorbed at 40 °C. The lower critical swelling temperature (LCST) of the copolymers can be adjusted by changing the chemical composition of the polymers. Such crosslinked gels can be potentially used as thermosensitive superabsorbent because of their high water uptake and thermal sensitivity. 相似文献
43.
A unique flow injection chemiluminescence (CL) method for the determination of calcium dobesilate in pharmaceutical preparations and human urine is presented in this paper. The analytical reagents involved in the CL reaction, luminol and ferricyanide, were both immobilized on an anion-exchange column in an FI system. The CL signal produced by the reaction of luminol with ferricyanide (the reagents had been eluted from the column through sodium phosphate injection) decreased in the presence of dobesilate. The decreased CL intensity was linear to the dobesilate concentration in the range 0.2100.0ngmL–1. At a flow rate of 2.0mLmin–1, one analytical cycle can be completed in 1.5min, including sampling and washing, resulting in a throughput of 40 cycles per hour. The proposed method was applied successfully to the determination of dobesilate in pharmaceutical preparations and human urine without any pre-treatment. It was found that, after oral administration, the dobesilate concentration reached its maximum after three hours, and the dobesilate metabolism ratio in 24 hours was 57.1% in the bodies of volunteers.Received September 14, 2002; accepted March 11, 2003
Published online July 16, 2003 相似文献
44.
CrystalStructuresofLanthanumComplexeswithNitrobenzoicAcids¥MaJian-Fang;JinZhong-Sheng;NiJia-Zuan(LaboratoryofRareEarthChemist... 相似文献
45.
A novel method of synthesizing protein chiral stationary phase (protein-CSP) is proposed with 2,4,6-trichloro-1,3,5-triazine as the activator. The bovine serum albumin (BSA) based chiral columns (150 x 4.6 mm I.D.) were prepared successfully within 8 h. With tryptophan as the probe solute, it was observed that the BSA immobilized by this method had a better ability to distinguish enantiomers than that activated by glutaric dialdehyde. This may be due to the well-maintained BSA conformation and the larger amount of BSA immobilized on the silica gel. The BSA-CSP prepared by this method was relatively stable under experimental conditions, and the resolution of 13 chiral compounds was achieved. The coupling reaction in this method is mild, reliable and reproducible; it is also suitable for the immobilization of various biopolymers in the preparation of bioreactor, biosensor and affinity chromatography columns. 相似文献
46.
Self-association system of(R)-1,3-butanediol in dilute carbon tetrachloride(CCl4)solution is studied as a model of molecular association mixture.Analysis methods including FSMWEFA(fixed-size moving window evolving factor analysis)combined with PCA(principal component analysis),SIMPLISMA (simple-to-use interactive self-modeling mixture analysis),and ITTFA(iterative target transformation factor analysis)are adopted to resolve infrared spectra of(R)-1,3-butanediol solution.Association number and equilibrium constant are computed.(R)-1,3-butanediol in dilute inert solution is determined as a monomer-trimer equilibrium system.Theoretical investigation of trimer structures is carried out with DFT(density functional theory),and structural factors are analyzed. 相似文献
47.
Hai‐Yang Liu Shi‐Jin Li Yi Zhao Wei Ni Xiao‐Jiang Hao Jun‐Zhu Li Yan Hua Bai‐Bo Xie Chen Qing Chang‐Xiang Chen 《Helvetica chimica acta》2007,90(10):2017-2023
Four new podocarpane‐type trinorditerpenenes, (5β,10α)‐12,13‐dihydroxypodocarpa‐8,11,13‐trien‐3‐one ( 1 ), (5β,10α)‐12‐hydroxy‐13‐methoxypodocarpa‐8,11,13‐trien‐3‐one ( 2 ), (5β,10α)‐13‐hydroxy‐12‐methoxypodocarpa‐8,11,13‐trien‐3‐one ( 3 ), and (3α,5β,10α)‐13‐methoxypodocarpa‐8,11,13‐triene‐3,12‐diol ( 4 ), together with four known diterpenes, 12‐hydroxy‐13‐methylpodocarpa‐8,11,13‐trien‐3‐one ( 5 ), spruceanol ( 6 ), ent‐3α‐hydroxypimara‐8(14),15‐dien‐12‐one ( 7 ), and ent‐3β,14α‐hydroxypimara‐7,9(11),15‐triene‐12‐one ( 8 ), were isolated from the twigs and leaves of Aleurites moluccana. Their structures were elucidated by means of comprehensive spectroscopic analyses, including NMR and MS. Except 8 , all compounds were evaluated for their cytotoxicity; compound 4 exhibited moderate inhibitory activity against Raji cells with an IC50 value of 4.24 μg/ml. 相似文献
48.
Sun MZ Ding L Ji YP Zhao DQ Liu SY Ni JZ 《Rapid communications in mass spectrometry : RCM》1999,13(3):150-155
Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS) was used to analyze two enzymes, phospholipase A2 and fibrinolytic enzyme isolated from Chinese Agkistrodon blomhoffii Ussurensis venom. Using sinapinic acid as the matrix, positive ion mass spectra of the enzymes were obtained. In addition to the dominant protein [M + H]+ ions, multimeric and multiply charged ions were also observed in the mass spectra. The higher the concentration of the enzymes, the more multiply charged polymer and multimeric ions were detected. Our results indicate that MALDI-TOFMS can provide a rapid and accurate method for molecular weight determination of snake venom enzymes. Mass accuracies of 0.1 and 0.3% were achieved by analysis of highly dialyzed phospholipase A2 and fibrinolytic enzyme, and these results are much better than those obtained using sodium dodecyl sulfate-polyacrylamide gel electrophoresis. MALDI-TOFMS thus provides a reliable method to determine the purity and molecular weight of these enzymes, which are of potential use as therapeutants. 相似文献
49.
The complex that forms between a boronic acid and a diol is often much more acidic than the starting boronic acid. In conditions where the solution pH is between the two pK(a) values, the boron atom will convert from a neutral trigonal form to an anionic tetrahedral form upon complexation. Such a change is likely to dramatically alter the electron density of neighboring groups. Utilizing this effect, we have designed and synthesized two nitrophenol-based boronic acid reporter compounds that change ionization states and therefore spectroscopic properties upon diol binding. Both compounds show significant UV changes upon addition of saccharides. For example, a blue shift of the absorption max from 373 to 332 nm was observed with the addition of D-fructose to 2-hydroxy-5-nitrophenylboronic acid at neutral pH. Such a reporter compound can be used as a recognition and signaling unit for the construction of polyboronic acid sensors for the selective and specific recognitions of saccharides of biological significance. 相似文献
50.
A mode of capillary electrochromatography (CEC), based on the dynamical adsorption of surfactants on the uncharged monolithic stationary phases has been developed. The monolithic stationary phase, obtained by the in situ polymerization of butyl methacrylate with ethylene dimethacrylate, was dynamically modified with an ionic surfactant such as the long-chain quaternary ammonium salt of cetyltrimethylammonium bromide (CTAB) and long-chain sodium sulfate of sodium dodecyl sulfate (SDS). The ionic surfactant was adsorbed on the surface of polymeric monolith by hydrophobic interaction, and the ionic groups used to generate the electroosmotic flow (EOF). The electroosmotic mobility through these capillary columns increased with increasing the content of ionic surfactants in the mobile phase. In this way, the synthesis of the monolithic stationary phase with binary monomers can be controlled more easily than that with ternary monomers, one of which should be an ionic monomer to generate EOF. Furthermore, it is more convenient to change the direction and magnitude of EOF by changing the concentration of cationic or anionic surfactants in this system. An efficiency of monolithic capillary columns with more than 140000 plates per meter for neutral compounds has been obtained, and the relative standard deviations observed for to and retention factors of neutral solutes were about 0.22% and less than 0.56% for ten consecutive runs, respectively. Effects of mobile phase composition on the EOF of the column and the retention values of the neutral solutes were investigated. Simultaneous separation of basic, neutral and acidic compounds has been achieved. 相似文献