The Influence of Nitrate Salts and Complex Metal Ion to Regio-Selective Synthesis of 2-Nitro-5,10,15,20-Tetra-(4-Methoxyphenyl)Porphyrinato 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(Ⅲ) 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.     

Nitridation of chromium powder in ammonia atmosphere

CrN powder was synthesized by nitriding Cr metal in ammonia gas flow, and its chemical reaction mechanism and nitridation process were studied. Through thermodynamic calculations, the Cr-N-O predominance diagrams were constructed for different temperatures. Chromium nitride formed at 7002-1200℃ under relatively higher nitrogen and lower oxygen partial pressures. Phases in the products were then investigated using X-ray diffraction (XRD), and the Cr₂N content varied with reaction temperature and holding time. The results indicate that the Cr metal powder nitridation process can be explained by a diffusion model. Further, Cr₂N formed as an intermediate product because of an incomplete reaction, which was observed by high-resolution transmission electron microscopy (HRTEM). After nitriding at 1000℃ for 20 h, CrN powder with an average grain size of 63 nm was obtained, and the obtained sample was analyzed by using a scanning electron microscope (SEM).     

Molybdenite alkali fusion and leaching:reactions and mechanism

<正>The production of MoO_3 from Sarcheshmeh molybdenite concentrate via a pyro-hydrometallurgical process was studied.The molybdenite concentrate and sodium carbonate were premixed and fused under air atmosphere.Then the fused products were leached in water and the dissolved molybdenum was recovered as ammonium molybdate.The ammonium molybdate was then calcined to produce mo-lybdic oxide.At the fusion stage,the effect of the mass ratio of carbonate to sulfide on the reaction products and the solubility of the products was investigated.The results show that during the fusion,sodium molybdate and sodium sulfate are the final reaction products and sodium sulfide is detected as an intermediate reaction product.By melting at 850℃with 5wt%excess carbonate,the maximum solubility of the products is obtained.The molybdenum is recovered from the solutions as ammonium molybdate.     

Molybdenite alkali fusion and leaching: reactions and mechanism

The production of MoO₃ from Sarcheshmeh molybdenite concentrate via a pyro-hydrometallurgical process was studied. The molybdenite concentrate and sodium carbonate were premixed and fused under air atmosphere. Then the fused products were leached in water and the dissolved molybdenum was recovered as ammonium molybdate. The ammonium molybdate was then calcined to produce molybdic oxide. At the fusion stage, the effect of the mass ratio of carbonate to sulfide on the reaction products and the solubility of the products was investigated. The results show that during the fusion, sodium molybdate and sodium sulfate are the final reaction products and sodium sulfide is detected as an intermediate reaction product. By melting at 850℃ with 5wt% excess carbonate, the maximum solubility of the products is obtained. The molybdenum is recovered from the solutions as ammonium molybdate.     

Effects of PSMA and experimental conditions on the morphologies of BaCO3 whiskers

BaCO3 whiskers exhibiting different morphologies were fabricated by a simple precipitation reaction of barium chloride with sodium carbonate in the absence and presence of poly-（styrene-alt-maleic acid） （PSMA） as a crystal growth modifier at room temperature. The as-prepared products were characterized by scanning electron microscopy （SEM）, transmission electron microscopy （TEM）, and X-ray diffraction （XRD）. The influences of experimental parameters on the size and morphology of BaCO3 whiskers were investigated and discussed. It was found that the as-prepared BaCO3 whiskers are single crystals with diameter ranging from 100 to 300 nm, and grow along the crystallographic a-axis or [ 100] direction. BaCO3 whiskers with different morphologies, such as branching and dendritic structure, can be obtained depending on the experimental conditions. With increasing PSMA concentration, the diameter of BaCO3 whiskers decreases.     

Preparation and Characterization of Ester from Rosin Acrylic Acid Adduct and Hydroxyethyl Methacrylate

1 Results Rosin is a sort of important renewable resources,which is a foremost product of our country forestry. It has very important meaning to modify the rosin based on its molecule structure and active group, to develop some deep processing products, and to endure with rosin new characteristic[1]. This work uses the rosin and acrylic acid to form rosin adduct, and then reacted with 2-hydroxyethyl methacrylate (HEMA) to form ester under the different condition. The effect of different ratios with the adduct and HEMA, catalyst types and levels on the esterification was investigated. The molecular structure of the adduct and the ester was characterized with IR spectrum. Their thermal stabilities were conducted with thermal analyzer. Experiment results show that the rosin ester was prepared successful, the best esterification condition was found out. The thermal stability of the rosin ester from acrylic acid rosin and HEMA was improved. The rosin ester may be used as negative photoresist[2].     

Study of Competitive Chelating Reaction between Lanthanum and Tribromoarsenazo in the Medium of Weak Acid by Capillary Zone Electrophoresis

Two kinds of metal chelates of rare earth elements reacted with tribrimoarsenazo formed under the condition of critic acid were observed by simultaneous technique of capillary electrophoresis-photothermal interference spectrometry. The tendency of the conversion between these chelates as functions of the mole ratio of the reagent and the metal, pH value and the elapsing time was investigated. Kinetic equation of competitive chelating reaction between the TBA-La (Ⅲ) and La (Ⅲ) -critic acid were established. It was found that the competitive chelating reaction follows second-order kinetics, for this second-order reaction, k = 5. 55 L·mol-1·S-1 .     

Glycyrrhetinic acid-modified nanoparticles for drug delivery: Preparation and characterization

In this work, glycyrrhetinic acid-modified chitosan （mGA-suc-CTS） used as liver targeted carrier for drug delivery, was prepared via hemisuccinate as a bridged group. The structure of the product was confirmed by IR and NMR methods and the degree of substitution （DS） of glycyrrhetinic acid groups was estimated via elemental analysis. Nanoparticles were formed by ionic gelation methold. The drug-loading and release behavior of the nanoparticles were investigated using BSA as the model drug. The results indicated that the carrier with a highest DS of 5.19% could be got and the DS was controlled by changing reaction temperature or feed ratio. BSA could be entrapped into the nanoparticles with the drug-loading ratio of 26.3% and the encapsulation efficiency of 81.5%. A sustained release over an 11-day period was observed in pH 7.4 in vitro.     

Reaction of diaminoglyoxime and cyclic azine compounds in high temperature and pressure water

Diaminoglyoxime was reacted in water at 150-400℃ and at 27.5 MPa pressure in metal Ti tubing reactor. Experimental results indicate that, diaminoglyoxime can be converted into NH-3 and CO-2, either through direct hydrolysis or through pyrolysis and polymerization, and then further hydrolysis. The possible reaction mechanism is nucleophilic addition of water.     

In vitro study of poly(ethylene carbonate) as a drug-eluting stent coating

An in vitro feasibility study of the use of poly(ethylene carbonate) (PEC) as a biodegradable coating material for drug-eluting stents is reported, and the performance of PEC is compared with that of poly(lactic-co-glycolic acid) (PLGA). Scanning electron microscopy (SEM) images of PEC and PLGA discs after treatment with an alkaline KO2 solution as a superoxide source showed that the PEC maintained its integrity whereas holes and small particles appeared during the treatment of PLGA. Sirolimus and paclitaxel were loaded into PEC and PLGA in order to study drug release performance. Attenuated total reflectance–infrared (ATR– FTIR) spectroscopy of sirolimus, PEC and the sirolimus-loaded PEC coating showed that no chemical reaction occurred between sirolimus and PEC. The results of atomic force microscopy (AFM) revealed that the mean roughness (Ra) values of the bare metal stent (BMS) and the drugeluting stent (DES) were 2.3 nm and 1.0 nm, respectively. After balloon expansion experiments, no delamination or destruction of the PEC coating was observed. The drug release profile of sirolimus was different from that of paclitaxel when PEC was employed as the drug carrier, and the release curves of sirolimus were different when PEC and PLGA were used as drug carriers. All the experimental results demonstrated that PEC was one of the best potential stent-coating materials.     

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.     

Photocatalytic Oxidation of NOx with Porous TiO2 Nanometer Thin Film

A new kind of porous nano-TiO2 composite films was prepared on the glass substrate with the water glass as hinders and the sodium fluorosilicate as solidifying reagent. The morphologies of the films were studied by scanning electron microscope(SEM). The UV-Vis spectrophotometer was also used to investigate the absorption of the films. The gasphase photocatalytic oxidation of nitrogen oxides on the composite film was carried out in TiO2 UV system, and some important factors affecting the photocatalytic oxidation were also studied such as the catalyst concentration, vapor pressure and the presence of oxygen. The results showed the conversion of NOx reached 97.5% after 2 h UV-irradiation. The final product of photo-oxidation was detected to be HNO3 hy FT-IR. The way of photocatalytic oxidation of NOx was possibly useful in the practical application.     

Preparation of (R)- and (S)-2-Allyl-1, 3, 2-dinaphtho (α, β) [d.f] dioxaborepin and their reactions with aldehydes

(R)- and(S)-2-Allyl-1,3,2-dinaphtho (α,β) [d.f] dioxaborepin ((R)-2 and(S)-2) have been first prepared by the reaction of(R)-(+)- or(S)-(−)-1, 1′-bi-2-naphthol and triallylborane in THF at room temperature, respectively.(S)-2 and(R)-2 are sensitive to moisture and oxygen in air and disproportionate easily to triallylborane and 1,1′-bi-2 naphthyl bis (1,1′-bi-2-naphtholborate) at ambient temperature. However, THF is a stabilizer for them. The reactions of(R)-2 or(S)-2 and some aliphetic or aromatic aldehydes in CH₂Cl₂ at −78°C for several hours afforded β-alkylenyl alcohols in up to 84.8%ee. Among them, optically active 1-(3, 5-dichlorophenyl)-3-butenol and 1-(2-methoxyphenyl)-3-butenol were first prepared Foundation item: Supported by the National Natural Science Foundation of China (29972033) Biography: Liu Dejun (1973), male, Ph. D, research direction: asymmetric synthesis     

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…     

Preparation by a rheological phase reaction method and thermal decomposition reaction mechanism of nickelous salicylate tetrahydrate

0　IntroductionInrecentyears,studiesonBinghamfluid ,suchasElec trorheologicalfluid ,areactivelypursued[1 6] .Rheologicaltechniqueshavebeenplayinganimportantroleinsyntheticchem istry .Therheologicalphasereactionmethodisthe processofpreparingcompoundsormaterialsfromasolid liquidrheologicalmixture.Thatis,thesolidreactantsarefullymixedinapropermolarratio ,andmadeupbyaproperamountofwaterorothersolventstoaBinghambodyinwhichthesolidparticlesandliquidsubstanceareuniformlydistributed ,sothattheprodu…     

Spectrofluorimetric determination of magnesium (II) with 7-(8-Hydroxy-3, 6-disulfonaphthylazo)-8-hydroxyquinoline-5-sulfonic acid

A new fluorescent reagent, 7-(8-hydroxy-3, 6-disulfonaphthylazo)-8-hydroxyquinoline-5-sulfonic acid (HDNHQ) for the determination of magnesium has been developed. It reacted with magnesium to form a 1∶1 fluorescent complex withλ _ex/λ _em immediately at room temperature in ammonia-ammonium chloride buffer (pH 10.7). A linear relationship was obtained in the magnesium concentration range of 0–160 ng·mL⁻¹ with the detection limit of 0.04 ng·mL⁻¹. The proposed method was simple, rapid and sensitive. It has been successfully applied to the determination of trace magnesium in blood serum with recoveries of 103.75% and 98.16%, respectively. Foundation item: Supported by the Zi-Qiang Foundation of Wuhan University Biography: Zhang Xian (1975-), female, Ph. D candidant, research direction: organic reagent synthesis and analysis.     

乙醇萃取法制备低Na;K高纯氯化锂

基于碱金属氯化物在乙醇中的溶解度差异,首次提出了乙醇萃取法制备低Na,K高纯氯化锂的工艺方法·除Ca实验表明,当草酸锂的加入量为0·6%时,Ca质量分数可控制在10×10-6~15×10-6以下;除Na,K实验表明,当液固比为8·5,过滤次数为2次时,Na质量分数可降到40×10-6以下,K质量分数可降到5×10-6以下·说明乙醇萃取法很好地解决了氯化锂制备中很难深度除去Na,K的技术难题     

Synthesis of Novel Covalent-linked Linear Porphyrin-Thiophene Copolymers

0　IntroductionTheconstructionofmacro molecularsystemcontainingmul tipleredoxcentersorphotosensitizersisanimportantsub jectinthedesignofmolecularelectronicdevices[1 ,2 ] .Forsuchobjectives,systematizationofdonor (redoxcenter) acceptortriadmoleculesintolargemolecularsystemsisoneofthemostfeasibleapproaches,becausetheexquisiteincorporationofthephotosensi tizersandsuitableelectrondonorsand /oracceptorsintoapoly mericchainisusefulforvariousmolecularsystembasedonphoto inducedelectrontransfer[3 ,4] …     

4-羟基苯基卟吩的合成和分离方法改进

对单羟基苯基卟吩[ 5- ( 4- 羟基苯基) - 10, 15, 20- 三苯基- 21H, 23H- 卟吩( H2TPPOH) ] 和多羟基苯基卟吩[ 5, 10- 二( 4- 羟基苯基) - 15, 20- 二苯基- 21H, 23H- 卟吩(H²TPP( OH) ₂) 、 5- 苯基- 10, 15, 20- 三( 4- 羟基苯基) - 21H,23H- 卟吩( H₂TPP( OH) ₃) ] 的分离方法作了改进.实验表明, 分离各种羟基苯基卟吩, 产物纯度高,分离效果好,并可节省大量洗脱剂,缩短了柱分离时间
同时,还考察了配料比, 吡咯溶液的滴加速度和操作方式对合成各种羟基苯基卟吩产率的影响采用3:1.05:4( 苯甲醛:对羟基苯甲醛: 吡咯,摩尔比) , 3 min 滴完吡咯溶液,强烈的电动搅拌, 可提高H₂TPPOH 的收率.     

Optical Properties of Ru（bipy）2 （dppx）^2＋ in Different Environments

The emission spectra of Ru（bipy）2 （dppx）^2＋ in different environments has been studied. It was found that the solvent polarity and the ability of donating and transferring proton are the important factors in predicting luminescence intensity in different systems. The increasing content of water in the organic solutions of Ru（bipy）2 （dppx）^2＋ leads to de crease in emission intensity that follows the Perrin sphere of quenching model. The effect of base content of DNA on the fluorescence spectra of Ru （bipy）2 （dppx）^2＋ has also been studied.