Study on the reaction of carbon disulfide with hydroxyl radical in aqueous solution

Carbon disulfide is an important sulfur-containing compound in the environment, and its oxidation produces about 30% of the atmospheric COS[1]. In situ measure- ments show that CS2 is widespread in the sea surface wa- ters[2―4], and more recently, the continental water seems to be especially rich sources of CS2 due to industrial waste- water effluents. It is generally accepted that the ocean is an important source for atm. CS2, and Xie et al.[5] found that marine photochemical reaction of…     

Investigation of the cross-reaction mechanism of C<Subscript>6</Subscript>H<Subscript>5</Subscript>F-HNO<Subscript>2</Subscript> aqueous solution irradiated at 355 nm by transient absorbance spectrum technique

The transient absorption spectrum technique was employed to investigate the cross-reaction mechanism of C6H5F-HNO2 aqueous solution irradiated at 355 nm. The characteristic and the kinetic parameters of transient species were also detected. Hydroxyl radical derived from the photolysis of HNO2 was added to monofluorobenzene with a second-order rate constant of （5.83±0.17）×10^9 L·mol^-1·s^-1 to form an adduct, C6H5F…OH, which was able to react with HNO2 as the main reaction pathway with a rate constant of （8.3±0.1）×10^7 L·mol^-1·s^-1. The C6F6…OH adduct can also be decayed by elimination of H2O to yield monofluorophenyl radical C6H4F-. By GC-MS technique, the final products were identified to be monofluorophenol, nitro-monofluorobenzene, nitro-monofluorophenol and para-fluorobiphenyl.     

3种苏铁属植物总黄酮、总多糖含量及抗氧化活性研究

为探究锈毛苏铁(Cycas ferruginea)、叉孢苏铁(C.segmentifida)和石山苏铁(C.sexseminifera) 3种苏铁属(Cycas)植物的总黄酮、总多糖含量以及抗氧化活性,本研究采用超声波辅助法对其根、叶柄、叶、雄球花、茎干的总黄酮及总多糖含量进行提取,以DPPH自由基(DPPH·)、羟自由基(·OH)、超氧阴离子自由基(O^-₂·)清除率评价其抗氧化活性,并采用Pearson相关性分析法分析相关性。结果表明：锈毛苏铁、叉孢苏铁和石山苏铁叶的总黄酮含量较高,大小依次为锈毛苏铁(8.61 mg·100 mg^-1)>叉孢苏铁(7.82 mg·100 mg^-1)>石山苏铁(1.04 mg·100 mg^-1);茎干中总多糖含量最高,大小依次为叉孢苏铁(28.32 mg·100 mg^-1)>石山苏铁(24.43 mg·100 mg^-1)>锈毛苏铁(16.59 mg·100 mg^-1<...     

pH effect of· OH radical induced oxidation of phosphoryl- methionine in aqueous solution

Conclusion The results of pulse radiolytical research on the · OH radical-induced oxidation of NDM in aqueous solution demonstrate that pH value has a great influence on the radiolytical mechanism of NDM. At low pH value, the product is mainly stabilization of the oxidizing sulfur centre in the three-electron-bonded cation radical NDM₂ ·⁺ [S]; with the increase of pH value, NDM₂ ·⁺ [S] gradually decays to become the reducing α-amino radical which was verified by the chemical method and whose yield was also calculated. Compared with Met₂ ·⁺ [S] produced by the · OH radical-induced oxidation in aqueous solution [1], the stability of NDM₂·⁺ [S] increases and the yield of α-amino radical decreases. This suggests that the introduction of phosphoryl group has a coordinating effect on the radioprotection of methionine to biological systems, and provides the essentially theoretical foundation for the thorough clarification of the reversible phosphorylation of proteins.     

Effect of CH3OOH on the atmospheric concentration of OH radicals

Methyl hydroperoxide (CH₃OOH, MHP) is known to be a significant sink and reservoir of HO_x and RO_x radicals in the atmosphere. In order to investigate the impact of MHP on the concentration of atmospheric OH radicals, two key gas-phase reactions of MHP, i.e. the reactions with OH radicals and with UV photolysis, have been simulated at temperature of 293±2 K and total pressure of 1.01×10⁵ Pa, using the long path Fourier transform infrared (LP-FTIR) spectrometry. OH radicals are generated by the photolysis of O₃ in the presence of water vapor. Combined with the relative rate method, the reaction rate constant of MHP with OH radicals is determined to be (3.99±0.15)×10^-12 cm³?molecule^-1?s^-1, and thus the atmospheric lifetime of MHP is estimated at 2.9 days. Furthermore, from detailed analysis of the UV photolysis of MHP, the yield of OH radicals is obtained to be 0.91±0.04. Based on the MHP atmospheric lifetime and the yield of OH radicals, it is concluded that MHP plays an essential role in the redistribution of OH radicals in the troposphere.     

Effect of CH3OOH on the atmospheric concentration of OH radicals

Methyl hydroperoxide (CH₃OOH, MHP) is known to be a significant sink and reservoir of HO_x and RO_x radicals in the atmosphere. In order to investigate the impact of MHP on the concentration of atmospheric OH radicals, two key gas-phase reactions of MHP, i.e. the reactions with OH radicals and with UV photolysis, have been simulated at temperature of 293±2 K and total pressure of 1.01×10⁵ Pa, using the long path Fourier transform infrared (LP-FTIR) spectrometry. OH radicals are generated by the photolysis of O₃ in the presence of water vapor. Combined with the relative rate method, the reaction rate constant of MHP with OH radicals is determined to be (3.99±0.15)×10^-12 cm³?molecule^-1?s^-1, and thus the atmospheric lifetime of MHP is estimated at 2.9 days. Furthermore, from detailed analysis of the UV photolysis of MHP, the yield of OH radicals is obtained to be 0.91±0.04. Based on the MHP atmospheric lifetime and the yield of OH radicals, it is concluded that MHP plays an essential role in the redistribution of OH radicals in the troposphere.     

Preparation and photocatalytic properties of ilmenite NiTiO<Subscript>3</Subscript> powders for degradation of humic acid in water

The powders of ilmenite structure NiTiO₃ were prepared by a modified Pechini process using tetrabutyl titanate and nickel acetate as raw materials, and using citric acid and ethanol as a chelating agent and a solvent respectively. The powder samples were characterized by thermogravimetric and differential thermal analysis (TG-DTA) and X-ray diffraction (XRD). The photocatalytic activity of NiTiO₃ under the irradiation of ultraviolet rays (UV) light was evaluated by degrading humic acid (HA) in water as a probe reaction. The possible photodegradation mechanism was studied by the examination of active species ·OH, ·O₂⁻, and holes (h⁺) through adding scavengers. The TG-DTA and XRD results indicated that the good crystal structure of ilmenite phase NiTiO₃ could be obtained when the Ni-Ti citrate complex was calcined at 600°C. The photocatalytic activity experiments indicated that NiTiO₃ had favourable photocatalytic activity under the irradiation of UV light, and the photocatalytic degradation rate of HA reached 95.3% after a 2.5 h reaction with the photocatalyst calcined at 600°C and a photocatalyst dosage of 0.4 g/L. The possible photocatalytic mechanism was deduced that holes (h⁺) and ·OH radicals are the major reactive active species in the photocatalytic reaction, and dissolved oxygen plays a weak role in the degradation of HA.     

Synthesis of layered LiMnO2 byin situ oxidation-intercalation and a study of the reaction mechanism and electrochemical performance

Using Mn(OH)₂ as precursor, LiOH as lithiating agent and (NH₄)₂S₂O₈ as oxidant, layeredo-LiMnO₂ was obtained by a novel method—in situ oxidation-intercalation under mild conditions (80 °C). The product was characterized by XRD, ICP, TEM and⁷Li-NMR. The results reveal that orthorhombic LiMnO₂ with high purity and good crystallinity can be obtained by this method. During electrochemical tests, a LiMnO₂/Li cell shows an initial reversible capacity of 208 mAh · g⁻¹ and a reversible capacity of 180 mAh · g⁻¹ after 30 cycles at room temperature.     

转SOD基因烟草的光合特性初探

 以转基因Fe-SOD,Mn-SOD高表达、转基因Mn-SOD反义低表达烟草及非转基因品系为供试材料,比较CO₂光强对烟草光合作用和蒸腾作用的影响及不同叶位叶片的光合差异.在相同条件下,Mn-SOD高表达烟草CO₂补偿点最高(105μmol·mol^-1),Mn-SOD低表达烟草最低(78μmol·mol^-1),CO₂浓度对非转基因烟草蒸腾作用的影响比对其他三个转基因品系的影响要强.Mn-SOD低表达烟草的光补偿点最高(45μmol·m^-2·s^-1),而Mn-SOD高表达烟草最低(25μmol·m^-2·s^-1),并且强光对非转基因烟草的光合作用抑制大,转基因品系对强光具有较强的耐受力.同一叶位叶片,转基因烟草的光合速率、蒸腾速率更强.但转基因SOD高表达烟草在整体上并没有表现出明显的光合作用优势.     

Walsh spectrum properties of rotation symmetric boolean function

Rotation symmetric function was presented by Pieprzyk. The algebraic configuration of rotation symmetric（RotS） function is special. For a Rots n variables function f（x1, x2, …, xn） we have f（ρn^k （x1, x2, …xn））=f（x1, x2, …, xn） for k=0, 1, …, n-1. In this paper, useing probability method we find that when the parameters of RotS function is under circular translation of indices, its walsh spectrum is invariant. And we prove the result is both sufficient and necessary.     

Fluorescence Determination of Artemisinin Using Hemoglobin as Catalyst and Pyronine B as Substrate

0 IntroductionMaalnadria siusb atr ompajicosr .he aAltrthe pmrisoibnlienmi (n qtihneghtraoopsiucs,QHS,Fig.1) is a sesquiterpene endoperoxide isola-ted fromArtemisia annuaL., an ancient Chineseherbal medicine usedfor treatment of fever and ma-laria.Studies of the structure and activity relation-ship have shownthat endoperoxide groupis essentialfor anti malarial activity of QHS and absence of thismoiety lead to completely loss in activity of thedrug. Many techniques have been developed to de…     

超声波下酸化碘酸钾和亚硫酸钠反应的反应速率研究

分别测定在有超声波作用和在无超声波作用条件下 ,酸化碘酸钾 (KIO3 )和亚硫酸钠 (Na2 SO3 )反应的反应速率方程式及活化能 ,从而研究该反应的机理以及超声波在该反应中的作用 ,并确定反应的最佳条件。实验得出 ,超声波对该反应有一定的促进作用 ,但是这种促进作用只提高反应的速率常数和降低反应的活化能 ,并没有改变反应机理。在超声波功率为 30 0W时 ,反应的速率方程表示式为 :v =k·c1 0 9(KIO3 ) ·c1 0 0 (Na2 SO3 )·c1 0 8(H+ ) ,其中 :k =95 0 (mol-1·L) 2 ·s-1,活化能为 17 35kJ·mol-1。实验还得出 ,在温度为2 98K时 ,当KIO3 与Na2 SO3 的初始浓度比为 2∶5 ,H+ 的初始浓度为 0 0 4 2 8mol·L-1,超声功率为 30 0W时 ,反应速率为最快 ,即v =4 31× 10 -4mol·L-1·s-1)。     

The v-v energy transfer of highly vibrationally excited states (II)

The vibrational energy transfer from highly vibrationally excited CO to H₂O molecules is studied by time-resolved Fourier transform infrared emission spectroscopy (TR FTIR). Following the 193 nm laser photolysis of CHBr₃ and O₂ the secondary reactions generate CO(v). The infrared emission of CO(v → v−1) is detected by TR FTIR. The excitation of H₂O molecules is not observed. By the method of the spectral simulation and the differential technique, 8 rate constants for CO(v)/H₂O system are obtained: (1.7 ±0.1), (3.4 ±0.2), (6.2 ±0.4), (8.0 ±1.0), (9.0 ±2.0), (12 ±3), (16 ±4) and (18 ±7) (10¹³cm³ · molecule^-1· s^-1). At least two reasons lead to the efficient energy transfer. One is the contributions of the rotational energy to the vibational energy defect and the other is the result of the complex collision. With the SSH andab initio calculations, the quenching mechanism of CO(v) by H₂O is suggested.     

氮化硼纤维填充聚乙烯醇导热复合材料的制备

以聚乙烯醇（PVA）为基体,选用六方氮化硼纤维（BN fiber）作为导热填料,通过溶液共混的方法制备导热复合材料。结合X射线衍射仪（XRD）、扫描电子显微镜（SEM）以及导热测试结果,探究填料的微观形貌以及与基体的界面相容性对于提升复合材料导热性能的影响。结果表明：BN fiber对于提升复合材料的面内导热率有很好的效果,而且采用过氧化氢（H₂O₂）溶液进行表面改性,可以有效改善界面相容性;当经过1 400℃热处理再经过表面改性的BN fiber（BN fiber-1400-H₂O₂）的填充量为5%（质量分数）时,复合材料的面内导热率达到了1.32 W·m^-1·K^-1,为纯PVA体系的629%,相比于表面改性前提升了60%。     

High quality p-type ZnO film growth by a simple method and its properties

P-type ZnO：N films have been grown successfully by chemical vapor deposition （CVD） using Zn4（OH）2（O2CCH3）6·2H2O as the solid source material and ZnNO3 as the doping source material. XPS, Hall-effect measurement and PL spectra were employed to analyze the structural, electrical and optical properties and study the influence of substrate temperature on the film. Results showed that with a lower substrate temperature, the film exhibited p-type conduction and its resistivity decreased when the substrete temperature increased. When the substrates temperature was 400℃, p-type ZnO films were obtained with carrier concentration of ＋5.127×10^17 cm^-3, resistivity of 0.04706 Ω· cm and Hall mobility of 259 cm^2/（V·s）; they still exhibited p-type conduction after a month. When the substrate temperature was too high, the film was transformed from p-type to n-type conduction.     

Kinetic studies of the decomposition reaction of adducts of dinuclear Fe(Ⅱ)/O2

Kinetic studies of the decomposition reaction of dinuclear Fe(Ⅱ) adducts [Fe₂(N-Et-HPTB){O₂P(OPh)₂}](Cl- O₄)₂ (1) and [Fe₂(N-Et-HPTB) {O₂P(Ph)₂}] (ClO₄)₂ (2) with O₂ have been carried out at low temperature using UV-vis spectra. The decomposition reaction of Fe(Ⅱ)/O₂ adducts was first-order in the experimental conditions, and the activation parameters were obtained. ?H^¹ = 85.62 kJ·mol^-1, ?S¹ = 19.43 J·mol^-1·K^-1 for compound (1) and ?H^¹ = 97.97 kJ·mol^-1, ?S^¹ = 55.68 J·mol^-1·K^-1 for compound (2). These results are similar to those of dioxygen adducts of other metals complexes and natural enzymes such as methane mono- oxygenase (MMOH).     

Effect of KBr on the micellar properties of CTAB

The effect of KBr on the size, shape and microviscosity of CTAB micelles has been investigated by means of laser light scattering (LLS),¹H NMR measurements and fluorescence probe. The data obtained from the various techniques are quantitatively in agreement. The R_h of micelles in 0.01 rnol · L⁻¹ CTAB solution increases from 3.5 nm to 43 nm andR _g increases to 89 nm with addition of KBr salt. In this process, both the microviscosity and molecular weight of micelles M_w have noticeable increases, too. The rod-like micelles are formed at 0.1 rnol · L¹ KBr and the worm-like micelles are formed at above 0.2 rnol · L^-1 KBr.     

Photocatalytic degradation pathways and adsorption modes of H-acid in TiO2 suspensions

Effect of adsorption mode on photodegradation of H-acid in TiO2 suspension was studied using DFT calculation,UV-Vis spec-troscopy,FTIR,and ionic chromatography.At pH 2.5,H-acid was adsorbed on TiO2 surfaces by one dissociated sulfonic group.The adsorbed sulfonic group was attacked by surface ·OH,resulting in the production of SO42-and the cleavage of the naphtha-lene ring.At pH 5.0,H-acid was adsorbed on TiO2 surfaces by two sulfonic groups.The two adsorbed sulfonic groups were sim-ultaneously attacked by surface ·OH,leading to a faster initial production of SO42-and initial degradation rate of H-acid than those under pH 2.5.Microscopic adsorption structures may be more important than adsorption amount in controlling the photo-degradation pathways of organic pollutants.     

Cu2O-templated fabrication of Ni(OH)2·0.75H2O hollow tubes for electrocatalytic oxygen evolution reaction

Cu₂O is an ideal template material for the preparation of transition metal hydroxide/oxyhydroxides with oxygen evolution reaction (OER) enhanced catalytic performance. Here, inspired by Pearson's principle, Cu₂O wires were prepared and used as a sacrificial template to prepare Ni(OH)₂·0.75H₂O hollow tubes (Ni(OH)₂ HTs) with highly improved surface roughness. Benefiting from unique structural advantages, the Ni(OH)₂ HTs showed excellent catalytic activity, rapid kinetics and a long-term stability as the OER catalyst, where an overpotential of only 207 ?mV was required to drive a current density of 10 ?mA ?cm^?2, an ideal kinetics with a Tafel slope as 79.8 ?mV dec^?1 was calculated, and no obvious attenuation in chronoamperometry was discovered after operation for 24 ?h. This paper provides a novel template-assisted strategy to prepare high-performance transition metal-based OER catalysts possessing hollow and tubular structures.     

Third-order optical nonlinearities for lanthanum (III) complexes with 1, 10-phenanthroline components

The nonlinear refractive indexesn ₂ for the ethanol solutions of 1, 10-phenanthroline (2.0 × 10⁻³ mol · L⁻¹), [bis(l, 10-phenanthroline) lanthanum (III)] nitrate (1.0 × 10⁻³ mol · L⁻¹), and [nitrato-fluoracil-bis (1, 10_{-phenanthroline}) lanthanum (III) ] nitrate (1.0 × 10⁻³ mol · L⁻¹) are first measured, the third-order nonlinear optical susceptibilities χ(³) and 〈γ〉 are calculated, and the mechanisms of the third-order optical nonlinearities enhanced by lanthanum (III) are discussed preliminarily.