The reaction of acenaphthene with nitrobenzene

The reaction of acenaphthene with nitrobenzene was investigated in the presence of AlCl₃. The results showed that the reaction proceeded via carboncation-electrophilic substitution reaction and free radical substitution reaction pathway. The products of acenaphthenyl phenylamine and biacenaphthyl could be synthesized by this reaction. The influence of the amount of AlCl₃ and the temperature on the components of products were also studied in this reaction. Foundation item: Supported by the National Nature Science Foundation of China (No. 29676045) Biography: Wu Lin (1965-), male, Postdictor, research direction: PAHs catalytic conversion and its biologic toxicity.     

3,4-dichlorotoluene ammoxidation to 3,4-dichlorobenzonitrile over VPO/SiO<Subscript>2</Subscript> catalyst

Ammoxidation of 3,4-dichlorotoluene (DCT) to prepare 3,4-dichlorobenzonitrile (DCBN) over silica supported vanadium phosphorus oxide catalysts has been studied. On the VPO/SiO₂ catalyst, the influence of the reaction temperature, the molar ratio of air/DCT, the molar ratio of NH₃/DCT in the feed gas and the space velocity (v ₁) on the conversion, yield and selectivity was observed. The most appropriate reaction condition is: reactionT=673 K,n(DCT):n(NH₃):n(air)=1:7:30 andv ₁=250 h⁻¹. At this optimum reaction condition, the conversion of DCT is 97.8%; the molar yield of DCBN is 67.4%. It was found that the addition of element phosphorus can improve the yield of DCBN compared with VO/SiO₂ catalyst. Foundation item: Supported by Youth Chen-Guang Project of the Committee of Science and Technology of Wuhan (20015005042) Biography: Huang Chi(1972-), male, Ph D, Lecture, research direction: ammoxidation.     

Novel Substitution Reactions of 5-（4-Nitrophenyl）-10,15,20-TriphenylPorphyrin with Nucleophilic Reagents

Substitution reactions of 5-（4-nitrophenyl）-10, 15,20-triphenylporphyrin （NO2 TPP） and its metal complexes with different nucleophilic reagents were studied for preparing asymmetric porphyrin. The reaction products are different with the nucleophilic reagents changing, and three different products were found. The first obtaining product was diporphyrin when NO2 TPP reacted with sodium phenoxide or diphenoxide in DMF solution; The second was reduced product 5-（4-aminophenyl）-10, 15, 20-triphenylporphrin-M （Ⅱ） when the metal （Ni,Zn） complex of NO2 TPP reacted with above nucleophilic reagents, as well as NO2 TPP reacted with lithium mercaptoethanolate or lithium thiophenolate; The third product CNTPP was achieved with the substitution of nitro group by cyanic anion when NO2 TPP reacted with radium cyanide. Above results were explained with reduction and single electron transfer reaction respectively.     

Measurement of GaAs start duration in different solution concentration using infrared images

This paper proposes a new infrared method to measure the start duration of GaAs substrate in chemical etching. When etching starts, the temperature of liquid-film will change because of heat release in the chemical reaction. As a result, the start duration of GaAs can be tested by collecting real-time in-frared thermal images in the course of temperature variation. Both theoretical analysis and experi-mental results show that the line shape liquid film of a 2-mm width is a good monitoring subject. By making use of the grey distribution change of a certain cross section of the line shape liquid film, the start duration of reaction between GaAs and H2SO4-H202-H20 is obtained. The start durations of reac-tion between GaAs substrate and H2SO4： H202： H20 （=5：1：50 and 15：3：50） solution are about 0.2 s and 0.3-0.4 s, respectively. This result and relative method will impulse the research of wet chemical etching technology of GaAs and so on.     

Synthesis of novel polymer-bonded water-soluble metal porphyrins

The reaction of 5, 10, 15, 20-tetra-(4-pyridyl) porphyrin 1 with triruthenium dodecacarbonyl [Ru₃(CO)₁₂], zinc(II) acetate, copper(II) acetate, cobalt(II) acetate afforded complexes 2a−2d respectively. Treatment of 2a−2d with Merrifield’s peptide resin obtained 3a−3d. The compounds 3a−3d reacted with methyl iodide respectively gave 4a−4d. New complexes 4a−4d have been identified by IR, UV-visible spectra, and AES. Foundation item: Supported by the Natural Science Foundation of Hubei Province Biography: LI Zao-ying (1949-), female, Associate professor.     

An effective novel reaction system for the photo-degradation of aqueous organic pollutants

A novel reaction system consisted of a supported TiO₂ film electrode, a Ru−Ti oxide film electrode and air (oxygen) electrode is reported. The air (oxygen) electrode can provide H₂O₂ continuously for homogeneous photochemical oxidation reaction on the spot. In this reactor, degradation reaction of aniline occur from interface of TiO₂ film to all solution which is irradiated by ultraviolet ray. The degradation rate of aniline was characterized by measuring the change of chemical oxygen demand (COD) in solution under different conditions. It was found that the degradation rate of aniline in the novel system increased apparently as compared with single heterogeneous photocatalysis and homogeneous photochemistry system. It can be explained in terms of combining acts of heterogeneous photocatalysis and homogeneous photochemistry. Foundation item: Supported by the National Natural Science Foundation of China (10791033) Biography: CAI Nai-cai (1946-), male, Associate professor, Research direction: electrochemical catalysis and photocatalysis.     

Photodegradation of 17α-Ethynylestradiol in Aqueous Solution with Nitzschia hantzschiana or Chlorella vulgaris and Fe^3＋

0　IntroductionTherehasbeenincreasingconcernabouttheenvironmentaleffectsofoestrogensandxenoestrogens[1 ] .17α ethynylestradiol(EE2 ) (Fig .1)isasyntheticestrogenicsteroidthathastherapeuticuses (e.g .Oralcontraception) .Syntheticestrogensaregenerallymorestableinwaterthannaturalestrogensandhavegreaterpotency.Theyaredifficulttobeabsolutelyremovedfromwastewatersbyprimaryandsecondarytreatment.Thedegradationchemistryofthiscom poundhasnotbeenextensivelystudied .Therearefewpublishedarticlesstudying…     

The influence of nitrate salts and complex metal ion to regio-selective synthesis of 2-nitro-5, 10, 15, 20-tetra-(4-Methoxyphenyl) prophyrinato metal

A series of 2-nitro-5, 10, 15, 20-tetra (4-methoxyphenyl) porphyrinato metals were regioselectively synthesized with nitrate salts as nitrating reagent in acetic acid/acetic anhydride for preparation of 2-substituted porphyrin. The influence of nitrate salts and complex metal ion to the reaction were investigated. The extent of 2-nitration increased with the electronegativity of the central metal. When Cu(NO₃)₂×3H₂O was used as nitrating reagent, almost quantitative yields of 2-nitro porphyrin were obtained in the case of Cu (II) or Ni (II) chelates, while Zn(II) or Mn(II) chelates gave 50% and 30% yields respectively. If Zn(NO₃)₂×10H₂O was used as nitrating agent, no product was found for Cu(II) or Ni(II) chelates, 12% was found for Zn(II) chelates. The other metal ion and nitrate salts were also found in quite different influence. Foundation item: Supported by the National Natural Science Foundation of China (29872033) Biography: Chen Zhang-ping (1946-), male, Professor, research direction, porphyrin.     

Chemiluminescence determination of tetracycline and oxytetracycline in pharmaceutical preparations using Ru (bipy)3 2+-cerium (IV) system

A new chemiluminescence (CL) method for the determination of tetracycline and oxytetracycline is developed, based on the CL reaction of tetracycline and oxytetracycline with Ru (bipy)₃ ²⁺ and Ce (IV). In sulfuric acid medium, the CL emission is generated upon continuous oxidtion of Ru(bipy)₃ ²⁺ by cerium (IV). The emission intensity is greatly enhanced when tetracycline and oxytetracycline are introduced into the reaction system after acid degradation. Under the optimum conditions, the calibration curves are linear over the range of 8.0×10⁻⁸∼4.0×10⁻⁶ mol/L for tetracycline and of 2.0×10⁻⁷∼4.0×10⁻⁵ mol/L for oxytetracycline, with the detection limits are 4.2×10⁻⁸ mol/L for tetracycline and 1.5×10⁻⁷ mol/L for oxytetracycline, respectively. The proposed method was used for the determination of tetracycline and oxytetracycline in pharmaceutical formulations with good results. Foundation item: Supported by the National Natural Science Foundation of China and the Natural Science Foundation of Hubei Province. Biography: HAH He-you (1962), male, Associate profeddor, Ph.D graduate candidate. Present address, Department of Chemistry, Huainan Teacher's College, Huainan.     

HPLC determination of ascorbic acid using luminol-Cu (II) chemiluminescence-application to the analysis of Juice beverage

The chemiluminescence (CL) of luminol-Cu (II) was applied to HPLC determination of ascorbic acid, which was separated by a C₁₈ reverse-phase column with a mobile phase of 0.25 mol/L HAc. The eluted ascorbic acid was mixed with 0.3 mmol/L luminol and 0.05 mol/L CuSO₄. The light emission from the reaction of Cu(II) oxidized ascorbic acid and luminol was detected by a modified luminometer. The detection limit was 3.6×10⁻⁶ mol/L for ascorbic acid at aS/N ratio of 3, and the linear calibration range was 2×10⁻⁴–2×10⁻³ mol/L. The relative standard deviation for 5 replicate injections of 1×10⁻³ mol/L ascorbic acid was calculated as 4.3%. The method was successfully applied to determination of ascorbic acid in juice beverage. Foundation item: National Natural Science Foundation of China (29605001) Biography: Wu Feng-wu(1963-), male, research direction: analytical chemistry.     

盐胁迫和铝胁迫对加拿大一枝黄花种子萌发的影响

为探究加拿大一枝黄花(Solidago canadensis)在不同浓度下对盐胁迫和铝胁迫的耐受性,以加拿大一枝黄花为材料,采用室内生物测定的方法,利用 0、200、400、800、1600、3200 mg/L 不同浓度 Na Cl 和 AlCl₃ 溶液处理加拿大一枝黄花种子,并对其萌发特性进行比较研究。结果表明：(1)加拿大一枝黄花种子的发芽率随着Na Cl 浓度的增加而降低,与对照相比,800 mg/L 浓度的 Na Cl 溶液对其发芽率和发芽势产生显著抑制作用(P <0.05),当浓度为 1600 ～ 3200mg/L 时,发芽率和发芽势极显著降低(P < 0.01),当浓度为 800 ～ 3200 mg/L 时,加拿大一枝黄花发芽指数极显著降低(P < 0.01);(2)加拿大一枝黄花种子发芽率随着 AlCl₃ 浓度的增加而降低,与对照相比,200 ～ 3200mg/L 的 AlCl₃ 溶液对其发芽率、发芽势及发芽指数受到极显著抑制作用(P < 0.01)。(3)加拿大一枝黄花种子对盐胁迫...     

Solid-phase preparation and characterization of Chitosan

0　IntroductionChitosanhasbeenwidelyusedinpharmaceu tical,agriculturalandindustrialfieldbe causeofitsintriguing properties[1 ] .Chemicalmethodstopreparechitosanfromchitinhavebeenbroadlystudiedincludingsolutionmethod ,meltedalkalinemethod,microwavesemi drymethod ,improvedLinelbergmethod ,dissolution precipita tionmethodandsoon ,inwhichalkalinewasallusedasthecatalyst[2 ] .Biologicalmethodwasapromisingwayinthatitproducedlittleenviron mentalpollutionanditsreactionconditionsweremild .However,thism…     

Quantum chemical and topological study on the insertion reaction of dichlorcarbene with acetaldehyde

The insertion reaction mechanisms of siglet and striglet CCI2 with CH3CHO have been studied by using the DFT, NBO, CCSD（T） and AIM method. The geometries of reactions, transition state and products were completely optimized by B3LYP/6-31G（d）. All the energy of the species was obtained at the CCSD（T）/6-31G（d,p） level. The calculated results indicated that all the major pathways of the reaction were obtained on the singlet potential energy surface. The singlet CCl2 can not only insert the Cα--H （reaction I） but also can react with Cβ--H （reaction ll）. There are three main existing pathways and the products are P1 （CH3COHCCl2）, P2 （CH2COHCHCl2） and P4[CHCl2CHCHOH] respectively. Reaction II happens more easily according to the energy changes and the barrier in rate-controlling step. In addition, the important geometries in domain pathways have been studied by AIM theory. And also, the energy changes of H in the inserted C--H bond have been investigated.     

The discharge and charge behavior of the Pb-Birnessite in LiOH aqueous solution

0　IntroductionManganeseoxideshavebeenwidelystudiedasbatterycathodesbecauseofitslowcostandlowtoxicity .Muchefforthasbeenfocusedonthespinelphase ,γ MnO2 andse verallayeredmanganeseoxidesinaqueousandnon aqueous .Sothereismuchinterestinmanganeseoxidesforuseascathodematerialsforadvancedlithiumbatteriestoreplacetheexpensivelithiumcobaltornickelsystem .ButthespinelLixMn2 O4hasthelowerratecapabilityandlowertheoreti calcapacityandγ MnO2 hasunsatisfactoryreversibilityinaqueous,thereby ,theiradvant…     

Studies of several systems with air electrode electro-synthesizing H<Subscript>2</Subscript>O<Subscript>2</Subscript> on the spot for degrading aniline in aqueous

A gas diffusion electrode (air electrode) with a high current efficiency of electro-synthesizing H₂O₂ using O₂ in air was prepared. The several systems with air electrode as cathode of electro-synthesizing H₂O₂ on the reaction spot for degrading aniline in aqueous—electro-Fenton system, photo-excitation electro-H₂O₂ system and photo-electro-Fenton system, were developed. The rates of decomposition of H₂O₂ and mineralization of aniline were experimentally measured respectively under different conditions, and the results indicated there has an excellent parallel relation between decomposition rate of H₂O₂ and mineralization rate of aniline. Especially, photo-electro-Fenton system, where H₂O₂ is decomposed the fastest, is the best system of oxidizing and degrading organic toxicants. Compared photo-electro-Fenton system with photo-Fenton system, important role is revealed in the interface of air electrode. In this paper, the mineralization mechanism of aniline in the photo-electro-Fenton system was also discussed. Foundation item: Supported by the National Natural Science Foundation of China (200710026) and Foundation of Environmental Sciences Academy of Jiangsu Province. Biography: Cao xiao-yu (1979-), male, Master candidate, research direction: Electrochemistry     

Synthesis and X-ray crystal structure of a new manganese 18-metallacrown-6

0　IntroductionThemetalionsinmetallamacrocylesformedbysupramolecularself assemblycantaketrigonal,square planar,andtetrahe dralconfiguration[1 ,2 ] .Metallacrownisaspecialclassofmetalla macrocyle,theyareanalogoustocrownethersinbothstructureandfunctionexceptthatthemetalionsarenowtakingthepositionsofcoordinationatomsincrownether[3,4] .Themetallacrownswithdifferentnumberof [M—N—O]repeatunithavedifferentcavitysizes,suchas 9 MC 3[5 7] ,12 MC 4 [4,8 1 4 ] and 15 MC 5 [1 5] .Thereportedazameta…     

Study on the action of sodium selenite on the mitochondria metabolism of<Emphasis Type="Italic">Carassius auratus</Emphasis> hybrid carps liver by microcalorimetry

By using an LKB-2277 bioactivity monitor and ampoule method, the fundamental thermogenesis curves of the metabolic process of liver mitochondria fromCarassius auratus hybrid carps and the toxic effect of Na₂SeO₃ on it were studied at 28°C. From the thermogenesis curves, the thermokinetic equations were established under different condition. The kinetics show that Na₂SeO₃ has toxic action on the metabolism process ofCarassius auratus hybrid carps liver mitochondria. Foundation item: Supported by the National Science Foundation of China (29973030, 30170010 and 5020310), Chenguang Project of Wuhan and National Postdoctor Foundation of China Biography: Li Xi (1968-), female, Associate pofessor, research direction: biothermochemistry and biomaterials.     

Laser cooling using anti-stokes fluorescence in Yb3+-doped fluorozirconate glasses

The fluorozirconate glasses ZBLANP (ZrF₄−BaF₂−LaF₃−NaF−PbF₂) doped with different Yb³⁺ concentration were prepared. The Raman spectra and absorption spectra are measured to substantiate the existence of phonon-assisted emission. After analyzing the normalized absorption spectra of samples with different Yb³⁺-doped concentration, we calculated the maximum cooling effect in the 3 wt% Yb³⁺-doped sample pumped at 1 012.5 nm. The corresponding cooling capability is about −4.09 °C/W and the cooling efficiency reaches 1.76%. Foundation item: Supported by the Key Science Foundation of Wuhan (9601P0223) Biography: Xu Tian-ming (1978-), female, Master candidate, research direction: information optics and nonlinear optics.     

Corrosion resistance properties and preparation of α-C3N4 thin films

Well adhered C₃N₄ films were prepared by Plasma Enhanced Chemical Vapor Deposition (PECVD) on industrial pure iron substrates using ternary Si−N−C films as buffer layer. XRD measurement showed that the C₃N₄ films belong to the α-C₃N₄ phase. Electrochemical experiments showed that the corrosive resistance of the pure iron raised by two orders of magnitude after being covered with the α-C₃N₄ coating. Foundation item: Supported by the National Natural Science Foundation of China(19875037) Biography: ZHANG Wei(1975-), male, Graduate student. Research direction: thin film.     

(异)螺甾烷型甾体皂苷元的选择性开环反应研究

利用一种全新的甾体皂苷元E/F全开环体系,即室温下,加入催化量的无水AlCl3,以CH3COCl作开环试剂、CH2Cl2作溶剂的开环体系,以良好的收率及选择性实现了甾体工业重要基础原料薯蓣皂苷元、剑麻皂苷元的E/F全开环,提出了可能的开环反应机理.开环产物具有胆甾烷的完整碳骨架并在C16,C22,C26位引入了具有良好衍生能力的多个官能团,该产物为一系列高活性甾体化合物的简捷合成提供了原料.