Calculation of the anharmonic effect on the main reactions referring to ethylbenzene combustion mechanism

About 11 reactions related to ethylbenzene are studied in this paper using transition state theory. The YL method proposed by Yao and Lin is utilized to calculate the anharmonic and the harmonic rate constants in these reaction processes in the temperature range of 300–4,000 K, energy diagram and the temperature dependence of the rate coefficients are also presented. The calculations indicate that the harmonic rate constants are larger than the anharmonic rate constants in most cases. Especially, there is a temperature junction between the high and low relationship between the anharmonic and harmonic rate constants in several reactions. Furthermore, the calculated values are in good agreement with other theoretical ones within the allowable error. Finally, the kinetic parameters and the thermodynamic parameters are calculated. To sum up, it can be concluded that the anharmonic effect in these reactions is very significant and cannot be ignored.     

Hyperacmosin R,a New Decarbonyl Prenylphloroglucinol with Unusual Spiroketal Subunit from Hypericum acmosepalum

Two previously undescribed polycyclic polyprenylated acylphloroglucinols, hyperacmosins R-S (1–2), were obtained from the aerial parts of Hypericum acmosepalum. Their structures were elucidated by extensive spectroscopic analysis and electronic circular dichroism calculation (ECD). Compound 1 featured an unprecedented 5,8-spiroketal subunit as well as the loss of C-2′ carbonyl in the phloroglucinol ring. In addition, compounds 1 and 4 showed weak hepatoprotective activity against paracetamol-induced HepG2 cell damage at 10 μm. The plausible biosynthetic pathway of 1 was proposed via a retro-Clasisen reaction and decarboxylation.     

V2O5电致变色薄膜的Raman光谱

近年来,通过向过渡金属氧化物薄膜注入Ｌｉ 制作可调节光透过率的电变色器件已越来越引起广泛的重视[1、2].由于Ｖ2Ｏ5薄膜的稳定性差,限制了它在实际中的应用.因此,为了获得变色效率高、稳定性和可逆性能好的Ｖ2Ｏ5薄膜,使用了多种制备方法,如磁控溅射法[3、6]、电化学沉积法[7、8]、溶胶凝胶法[9、10]、旋涂法[11、12]、真空蒸镀法[13、14]等.但是,无论那种方法都要解决Ｖ2Ｏ5本身在Ｈ2Ｏ或醇等的电解质溶液中电致变色时的溶解问题,通常采用控制薄膜的沉积温度或者退火处理来提高薄膜的电致变色性能[3、4、11].为了探明薄膜结构与电致变色…     

New Diterpenoid Alkaloids from Delphinium Souliei Franch

Inourpreviouspapers'-',wehavereportedtheisolationandelucidationofaseriesofnewditerpenoidalkaloidsfromDelphinillnlsolllieiFranch.ContinuedphytochemcalinvestigationsontheconstituentsofthisplanthaveledtotheisolationoftwoothernewditerpenoidalkaloidssoulineE(l)andsoulineF(2).SoulineE(2.6mg)wasobtainedascolorlesscrystals,mpf77-78'C(fromethanol).[a]."8.0(c=0.05,CHCI;).itsmolecularformulaC,=H;,NO,wasderivedfromHkEIMS(M-f361.2613,cafe.361.2608).TheiHnmrspectrum(400MHz)exhibitedthefollowingsign…     

"Click" synthesis of small molecule probes for activity-based fingerprinting of matrix metalloproteases

By using "Click Chemistry", we achieved the facile synthesis of various affinity-based hydroxamate probes that enable generation of activity-based fingerprints of a variety of metalloproteases, including matrix metalloproteases (MMPs), in proteomics experiments.     

The anharmonic effect study of coupled Morse oscillators for the unimolecular reaction

The importance of anharmonic effect in dissociation of molecular systems especially clusters has been noted. In this paper, we shall study the effect of coupled anharmonic oscillator of the standard bilinear form (SBF) Morse oscillator (MO) potential on unimolecular reaction. We shall use the systematic theoretical approach, YL method, proposed by Yao and Lin (YAO L, et. al. J Phys Chem A, 2007, 111(29): 6722-6729), which can evaluate anharmonic effects on the rate constants based on the transition state theory. In treating the anharmonic effect with the Morse oscillator potential on unimolecular reactions under collision-free conditions by using the RRKM (Rice-Ramsperger-Kassel-Marcus) theory, the in-verse Laplace transformation of the partition functions was used to obtain the total amount of state and density of state by using the first-order and the second-order approximations of the saddle-point method. To demonstrate the anharmonic effect of the SBF Morse model, we choose some model systems and a real reaction as examples.     

CeO2-ZrO2包覆石墨粉增强铝基复合材料的制备与耐蚀性能

采用非均匀成核法,在机械搅拌条件下通过硝酸亚铈和氧氯化锆水解生成无定形氧化铈、氧化锆对石墨进行表面包覆,利用扫描电镜、 X射线衍射和XPS对所得样品进行了表征,通过搅拌铸造法制备了氧化铈/锆包覆石墨颗粒增强铝基复合材料,并对复合材料耐蚀性能进行了初步研究. SEM和XPS表明,氧化铈/锆在石墨表面形成了均匀、致密的纳米级包覆层,氧化铈/锆通过与铝液的反应性润湿提高了石墨颗粒与铝液的润湿性,阻止了石墨与铝发生化学反应. 测试结果表明,氧化物的包覆基本抵消了由于石墨的添加而降低复合材料的腐蚀电位,也降低了腐蚀电流(两个数量级).     

A novel redox-fluorescence switch based on a triad containing ferrocene and perylene diimide units

By taking advantage of the features of ferrocene as a redox-active electron donor unit and perylene diimide as a fluorescence unit, a new redox fluorescence switch can be constructed on the basis of this triad.     

Selective colorimetric and fluorescent detection of HSO4- with sodium(I), magnesium(II) and aluminium(III) xanthone-crown ether complexes

Xanthone-crown ether (1) reacts with NaClO(4), Mg(ClO(4))(2) and Al(ClO(4))(3) forming the one-dimensional chain dinuclear polymer [Na(2).1.(ClO(4))(2)] (2), the mononuclear complex [Mg.1.(H(2)O)(2)](ClO(4))(2) (3) and an interesting sandwich complex [Al.(1)(2).(H(2)O)(6)](ClO(4))(3) (4) with different ratios of metal-to-ligand, respectively. The anion recognition experiment results show that the magnesium complex (3) is a good colorimetric and fluorescent detector for HSO(4)(-) with high sensitivity and selectivity.     

Characterization and biological evaluation of paclitaxel-loaded poly(L-lactic acid) microparticles prepared by supercritical CO2

In this study, paclitaxel loaded poly( L-lactic acid) (PTX-PLLA) microparticles were prepared using solution enhanced dispersion by supercritical CO2(SEDS) technique. This supercritical antisolvent technique offers the advantage of negligible organic solvent residua in the drug loaded microparticles. Scanning electron microscopy (SEM) showed that microparticles exhibited rather spherical shape and small particle size with narrow particle size distribution. X-ray diffraction (XRD) and differential scanning calorimeter (DSC) indicated that PTX was amorphously dispersed in the PLLA matrix. The drug loading and encapsulation efficiency of PTX-PLLA microparticles were 14.33% and 62.68%, respectively. In vitro cytotoxicity evaluation of PTX-PLLA microparticles against nonsmall-cell lung cancer A549 and ovarian cancer SKOV3 cell lines indicated that PTX-PLLA had superior antiproliferation activity against the A549 and SKOV3 cell lines, compared with free PTX formulations. The cellular internalization of fluorescent microparticles was evidenced by fluorescence microscope and further confirmed by transmission electron microscopy (TEM). This was attributed to the efficient intracellular accumulation of PTX via cell phagocytosis and sustained release of PTX from PLLA matrix. The anticancer activity of PTX-PLLA was associated with PTX-induced cell apoptosis such as nuclear aberrations, condensation of chromatin and swelling damage in mitochondria. The cell apoptosis index detected by flow cytometry was higher in PTX-PLLA group than in free PTX. The PTX-PLLA formulation, which was obtained through micronization of PTX and encapsulation of micronized PTX into PLLA simultaneously in the SEDS process, significantly potentiated the anticancer activity of PTX.