钛硅分子筛TS-1的合成、表征及催化性能

钛硅分子筛TS-1自Taramasso等［1］首次报道合成以来,由于其优异的选择氧化催化 性能及其催化的反应具有对环境污染轻,反应条件温和等优点而备受关注. 钛硅分子筛的制 备及应用研究是分子筛催化领域中的热点之一. 在经典的合成体系中,四丙基氢氧化铵(TPAO H)常被用作模板剂［2］,这是钛硅分子筛价格较为昂贵的主要原因之一. 国内外学者 都致力于廉价合成体系的开发,Müller等［3］报道了以四丙基溴化铵(TPABr)作模板 剂合成钛硅分子筛. 对于钛源和硅源,人们往往都采用水解趋势较为缓和的钛酯和硅酯,以达 到钛源和硅源的匹配;在合成过程中,要预先将钛酯加入到乙酰丙酮或异丙醇溶剂中进行稀释 ,并对胶液进行蒸醇处理［2,3］. 这使得钛硅分子筛的合成过程更加复杂,并提高了 其合成费用. 本文以钛酸四丁酯(TBOT)和四氯化钛混合原料作钛源,成功地合成出对丙烯环 氧化具有优异催化性能的钛硅分子筛TS-1,避免了上述的复杂步骤,并降低了钛硅分子筛的成本.     

Highly efficient and mild copper-catalyzed N- and C-arylations with aryl bromides and iodides

Mild, efficient, copper-catalyzed N-arylation procedures for nitrogen heterocycles, amides, carbamates, and C-arylation procedures for malonic acid derivatives have been developed that afford high yields of arylated products with excellent selectivity. The N-arylation of imidazole with aryl bromides or iodides was found to be greatly accelerated by inexpensive, air-stable catalyst systems, combining catalytic copper salts or oxides with a set of structurally simple chelating ligands. The reaction was shown to be compatible with a broad range of aryl halides, encompassing sterically hindered, electron-poor, and electron-rich ones, providing the arylated products under particularly mild conditions (50-82 degrees C). The lower limit in ligand and catalyst loading and the scope of Ullmann-type condensations catalyzed by complexes bearing those ligands with respect to the nucleophile class have also been investigated. Chelating Schiff base Chxn-Py-Al (1c) generates a remarkably general copper catalyst for N-arylation of pyrrole, indole, 1,2,4-triazole, amides, and carbamates; and C-arylation of diethyl malonate, ethyl cyanoacetate, and malononitrile with aryl iodides under mild conditions (50-82 degrees C). The new method reported here is the most successful to date with regard to Ullmann-type arylation of some of these nucleophiles.     

Kinetics and mechanisms of chlorine dioxide and chlorite oxidations of cysteine and glutathione

Chlorine dioxide oxidation of cysteine (CSH) is investigated under pseudo-first-order conditions (with excess CSH) in buffered aqueous solutions, p[H+] 2.7-9.5 at 25.0 degrees C. The rates of chlorine dioxide decay are first order in both ClO2 and CSH concentrations and increase rapidly as the pH increases. The proposed mechanism is an electron transfer from CS- to ClO2 (1.03 x 10(8) M(-1) s(-1)) with a subsequent rapid reaction of the CS* radical and a second ClO2 to form a cysteinyl-ClO2 adduct (CSOClO). This highly reactive adduct decays via two pathways. In acidic solutions, it hydrolyzes to give CSO(2)H (sulfinic acid) and HOCl, which in turn rapidly react to form CSO3H (cysteic acid) and Cl-. As the pH increases, the (CSOClO) adduct reacts with CS- by a second pathway to form cystine (CSSC) and chlorite ion (ClO2-). The reaction stoichiometry changes from 6 ClO2:5 CSH at low pH to 2 ClO2:10 CSH at high pH. The ClO2 oxidation of glutathione anion (GS-) is also rapid with a second-order rate constant of 1.40 x 10(8) M(-1) s(-1). The reaction of ClO2 with CSSC is 7 orders of magnitude slower than the corresponding reaction with cysteinyl anion (CS-) at pH 6.7. Chlorite ion reacts with CSH; however, at p[H+] 6.7, the observed rate of this reaction is slower than the ClO2/CSH reaction by 6 orders of magnitude. Chlorite ion oxidizes CSH while being reduced to HOCl, which in turn reacts rapidly with CSH to form Cl-. The reaction products are CSSC and CSO3H with a pH-dependent distribution similar to the ClO2/CSH system.     

Vibrational dynamics and stability of the high-pressure chain and ring phases in S and Se

The high-pressure phases of group-VI elements sulfur and selenium in their spiral chain and ring structures are examined by in situ Raman and x-ray diffraction techniques combined with first principles electronic structure calculations. The S-II, S-III, Se-I, and Se-VII having spiral chain structures and S-VI with a molecular six-member ring structure are studied in a wide P-T range. The square spiral chain structure of S-III and Se-VII is characterized by seven Raman modes that harden with increasing pressure. The calculations reproduce the observed frequencies and allow the authors to make the mode assignment. The "p-S" and "hplt" phases of sulfur reported by previous Raman studies are identified as S-II and S-III with the triangular and square spiral chain structures, respectively. The phase relations obtained by the x-ray and Raman measurements show that the high-pressure high-temperature phases of sulfur, observed by x-ray, can be induced by laser illumination at room temperature.     

Thermodynamic and kinetic characterization of host-guest association between bolaform surfactants and alpha- and beta-cyclodextrins

The thermodynamics and kinetics of formation of host-guest complexes between a series of bolaform surfactants of type C n Me 6 (2+)2Br (-) ( n = 8, 10, and 12) and alpha-cyclodextrin and beta-cyclodextrin were studied with the aid of isothermal titration calorimetry (ITC) at 298.15 and 308.20 K. The association constant, the enthalpy, and the entropy of formation were determined. The obtained thermodynamic parameters are compared with parameters for the micelle formation of a related cationic surfactant. The difference in magnitude and sign between the parameters of the alpha-CD and beta-CD complexes is discussed based on the curvature of the cavity of the CD. We suggest that the water molecules inside the alpha-CD cavity are not able to maintain their hydrogen bond network. Upon complex formation these water molecules are expelled and reform their hydrogen bond network. The situation is different in the larger beta-CD cavity where water has the possibility of a more extensive hydrogen bonding. The kinetics for alpha-CD is slow, associated with high activation energies for both association and dissociation of the complex. The rates increased with a decrease in the number of methylene groups in the hydrocarbon chain. The slow kinetics is argued to originate from the fact that the charged headgroup needs to be pushed through a relative nonpolar cavity. A comparison is made with the Born energy.     

Quantum-chemical study of the structure and reactivity of pyrazol-5-ones and their thio and seleno analogs: X. 1-methylpyrazol-5-one and its thio and seleno analogs in H-complex formation reactions in the gas phase and in solutions

The effects of specific solvation and self-association of chalcogenpyrazol-5-ones are assessed using nonempirical quantum-chemical, density functional theory (DFT), and MP2 second-order perturbation theory methods. The formation of H-complexes with water, methanol, and DMSO stabilizes all tautomeric forms, the NH tautomers of all hetero analogs being the most affected. The NH tautomers form with water 1:2 complexes which reveal cooperativity. The complexes of chalcogenpyrazolones with DMSO are more stable than the respective complexes with water, and, therewith, the extra stabilization in continuum is less pronounced than in the case of hydration. Quantitatively, the effects of tautomer self-association compare with the effects of interaction of chalcogenpyrazolones with proton-donor solvents.     

Adsorption and Mobility of Water and Benzene Molecules in Carbon and Polymer Adsorbents

The correlation between the adsorption and the mobility of adsorbed molecules was analyzed. The peculiarities of molecular mobility in microporous adsorbents with relatively rigid (active carbons) and non-rigid (polymer super-crosslinked and methacrylate sorbents) structure were studied using pulsed nuclear magnetic resonance (NMR) techniques. It was shown that the translational behavior of water and benzene in pores are connected with the specific adsorption mechanism. The NMR data allowed analyzing the changes of molecular state in the processes of adsorption. Diffusional properties of water molecules in the super-crosslinked polystyrenes and active carbons with relatively rigid framework are similar and differ from that in methacrylate polymer sorbents. Moreover, the results of NM relaxation measurements allowed analyzing the porous structure over the scale of pore sizes, while the scale of the self-diffusion measurements comprises the areas of different porosity. The NMR data agree well with the data of adsorption measurements and complement them. Dedication: This work is devoted to memory of the professor W. Schirmer.     

Kinetics and mechanisms of hydrolysis and aminolysis of thioxocephalosporins

The effect of replacing the beta-lactam carbonyl oxygen in cephalosporins by sulfur on their reactivity has been investigated. The second-order rate constant for alkaline hydrolysis of the sulfur analogue is 2-fold less than that for the natural cephalosporin. The thioxo derivative of cephalexin, with an amino group in the C7 side chain, undergoes beta-lactam ring opening with intramolecular aminolysis by a reaction similar to that for cephalexin itself. However, the rate of intramolecular aminolysis for the S-analogue is 3 orders of magnitude greater than that for cephalexin. Furthermore, unlike cephalexin, intramolecular aminolysis in the S-analogue occurs up to pH 14 with no competitive hydrolysis. The rate of intermolecular aminolysis of natural cephalosporins is dominated by a second-order dependence on amine concentration, whereas that for thioxocephalosporins shows only a first-order term in amine. The Bronsted beta(nuc) for the aminolysis of thioxo-cephalosporin is +0.39, indicative of rate-limiting formation of the tetrahedral intermediate with an early transition state with relatively little C-N bond formation.     

Recovery and stabilization of heavy metal sludge (Cu and Ni) from etching and electroplating plants by electrolysis and sintering

This work dealt with the recovery and stabilization of the sludge with heavy metals (Cu and Ni) produced from etching and electroplating plants. The heavy metals in the sludge were deprived of by acid leaching, followed by precipitation with 28% NH₄OH, and finally by electrolysis. In the electrolysis, the recovery percentage and purity were investigated at different electronic currency and temperature. The metal-deprived sludge was stabilized by mixing with glass powder and clay, followed by sintering at high temperature. How the ratio of glass powder to metal-deprived sludge affected final products (sludge bricks) was explored, in terms of specific gravity, absorption capacity, unconfined compressive strength, morphology, the volume shrinkage ratio and burn-up ratio. The volume shrinkage ratio and burn-up ratio of sludge bricks increased with metal-deprived sludge contents. The heavy metal remaining in sludge bricks was assessed through TCLP (toxicity characteristic leaching procedure) and by the analysis of SEM and EDX. The results from TCLP showed that the contents of leached metals were all below the regulatory criteria. This fact approved the feasibility of our method.     

Electron beam modification and crosslinking: Influence of nitrile and carboxyl contents and level of unsaturation on structure and properties of nitrile rubber

The structural changes of nitrile rubber with varying nitrile contents, hydrogenated nitrile rubber and carboxylated nitrile rubber in the presence and absence of a polyfunctional monomer, namely trimethylolpropane triacrylate, at different doses of electron beam irradiation, were investigated with the help of FTIR spectroscopy (in the attenuated total reflectance mode), dynamic mechanical thermal analysis and sol–gel analysis. Solid-state NMR with gated high power decoupling technique was used to understand the mechanism of crosslinking of the irradiated samples. The allylic radicals generated in the butadiene chains react to form intermolecular crosslinkages. There was a significant decrease in the concentration of olefinic groups for the nitrile rubber on irradiation. This was also affirmed by the increase in the carbon resonances due to C–C linkages from the NMR technique, indicating more crosslinkages. The spectroscopic crosslink densities were determined and the results were compared with the swelling measurements. The variation in the crosslink clustering for rubbers with different acrylonitrile contents was explained using the NMR technique. The increase in crosslinking was also revealed by the increase in the percent gel content and dynamic storage moduli with radiation doses. The lifetime of spurs formed and the critical dose, an important criterion for overlapping of spurs, were determined for both the grafted and the ungrafted nitrile rubbers of different grades and compared using a mathematical model. The ratio of scissioning to crosslinking for nitrile rubber was determined using Charlesby–Pinner equation. The mechanical properties had also been studied for both the modified and the unmodified systems.     

Liquid chromatographic assay of phenothiazine, thioxanthene and butyrophenone neuroleptics and antihistamines in blood and plasma with conventional and radial compression columns and UV and electrochemical detection

An assay strategy for determining a wide range of phenothiazine, thioxanthene and butyrophenone neuroleptics and antihistamines both alone and in combination in blood and plasma is described. The general method employs liquid chromatography with both conventional and radial compression nitrile bonded columns. Detection is by ultraviolet absorption spectrophotometry or by amperometry depending on the concentrations to be measured. Ultraviolet absorption is suitable down to 10 ng/ml. Below this level amperometry is preferable. The various compounds are used as internal standards for each other. The lower limit of detection is approximately 0.1 ng ml-1 with 10-ml sample. The with-run coefficient of variation is a maximum of 7.3%.     

meso-tetraalkyltetrabenzoporphyrins and their zinc complexes. Synthesis and properties

A number of meso-tetraalkyltetrabenzoporphyrin zinc complexes having alkyl substituents with different lengths were synthesized by reaction of excess phthalimide with zinc salts of aliphatic carboxylic acids. The corresponding free bases were obtained by treatment of the complexes with sulfuric acid. The spectral properties of the complexes and ligands and thermal stability of the former were studied.     

三苯胺类小分子的合成及其AIE性能研究

以二苯胺、碘苯、对碘甲苯以及对碘苯甲醚为原料,合成了三苯胺及其衍生物T1~T5(4-甲氧基三苯胺、4-甲基三苯胺、4-醛基三苯胺、4-乙烯基三苯胺),并对其紫外-可见吸收光谱与荧光光谱进行了检测。结果表明,连有甲氧基、甲基、乙烯基取代基的三苯胺化合物在甲醇/氯仿混合溶液中具有聚集诱导发光(AIE)性能;而醛基取代的4-醛基三苯胺表现出了聚集荧光猝灭(ACQ)现象。     

Spectrophotometric determination of titanium with tannin and thioglycollic acid and its application to titanium-treated steels and ferrous and non-ferrous alloys

A sensitive spectrophotometric method for the determination of titanium by formation of its complex with tannin and thioglycollic acid at pH 4 has been developed. The intense yellow colour is measured at 400 nm and the system obeys Beer's law over the range 0.2-5 ppm titanium in the solution measured. The method is applicable to titanium-treated steels, stainless steels, permanent magnet alloys and duralumin alloys. The interference of Co, Ni, Cr, Mn, V, Mo and W can be eliminated by prior separation of titanium by controlled addition of cupferron in the presence of thioglycollic acid (TGA). Copper can be quantitatively separated by precipitation with TGA and determined complexometrically with EDTA, with PAN as indicator. Niobium interferes even in traces.     

Chemical and physical modification and electret properties of polytetrafluoroethylene films

Composites with titanium oxide structures on the surface of a polymer matrix were prepared by preliminary plasma activation of polytetrafluoroethylene films, followed by chemical treatment with vapors of titanium tetrachloride and water. The chemical composition and structure of the modified film surface were studied by scanning electron microscopy, atomic force microscopy, and X-ray photoelectron spectroscopy. The stability of the formed surface charge increases in going from the initial film to the plasma-activated film, then to the film successively treated with vapors of titanium tetrachloride and water, and finally to the plasma-activated film treated subsequently with vapors of titanium tetrachloride and water. The modified polytetrafluoroethylene films are of interest as electrets with enhanced operation characteristics.     

Spectrophotometric kinetic and determination of quinones and barbiturates.

The kinetics of 1,3-dimethylbarbituric acid with some quinones, namely 1,4-benzoquinone, 1,4-naphthoquinone and p-chloranil in 50% methyl alcohol-water mixture have been investigated spectrophotometrically at 30-50 degrees C. The reaction follows overall second-order kinetics, first order each in reactant. From the dependence of the rate constants on temperature, activation parameters have been calculated. A plot of deltaH# versus deltaS# for the reaction gave a good straight line with an isokinetic temperature of 387.66 K. The rate of reaction increases with increasing dielectric constant of the medium. Based on this reaction, a spectrophotometric determination method of quinones is described. Beer's law was obeyed within the concentration range 2.7-61.5 microg ml(-1) quinone. The method was applied for determination of barbituric, thiobarbituric and 1,3-dimethylbarbituric acids with 1,4-naphthoquinone within a concentration range of 3.2-39.5 microg ml(-1) barbiturate. The reaction mechanism and reactivity have been discussed.     

水解交联改性的聚丙烯酰胺的吸水保肥能力研究

研究聚丙烯酰胺（PAM）的水解，并对其结构进行了表征。研究了二醛交联的聚丙烯酰胺及其水解产物对水、肥的吸收及保持能力，结果表明，聚丙烯酰胺水解交联后，部分胺基转化为羧基和羟基。由于羧基、羟基和胺基的协同作用，对水和肥的保持、吸收能力大大增强。水解4h的产物PAM-4中羧基、羟基和胺基的协同作用最好，对水和肥的保持、吸收能力最强。与乙二醛交联的PAM-4相比，戊二醛交联的PAM-4因可以有更大的网络伸展空间，水和肥的保持、吸收能力更强。戊二醛交联的PAM-4对CO（NH2）2有较大的吸收容量。     

Some pharmaceutical properties of 3-hydroxypropyl- and 2,3-dihydroxypropyl-beta-cyclodextrins and their solubilizing and stabilizing abilities

3-Hydroxypropyl- and 2,3-dihydroxypropyl-beta-cyclodextrins (3-HP- and DHP-beta-CyDs) with different degrees of substitution (D.S.) were prepared and their pharmaceutical properties were investigated. The aqueous solubility of 3-HP- and DHP-beta-CyDs was much higher than that of the parent beta-CyD and the dissolution of DHP-beta-CyD in water was endothermic. The acid- and alpha-amylase-catalyzed hydrolysis rates of 3-HP- and DHP-beta-CyDs were slower than those of the parent beta-CyD. The hemolytic activity (human erythrocytes) and local irritancy (rabbit muscle) of DHP-beta-CyD were considerably less than those of natural, methylated or other hydroxyalkylated beta-CyDs, and decreased with increasing D.S. The ability of the hydroxyalkylated beta-CyDs to remove cholesterol and proteins from human erythrocytes decreased with increasing D.S., and correlated well with their hemolytic activity. 3-HP-beta-CyD was a more effective solubilizer for poorly water-soluble drugs than the parent beta-CyD, and its stabilizing effect on chemically instable drugs was higher than that of the parent beta-CyD. The above data suggest a considerable pharmaceutical potential of 3-HP- and DHP-beta-CyDs as parenteral carriers.     

Possibilities for separation and simultaneous determination of N-unsubstituted- and N-substituted nitroimidazoles and criteria for their identification

The N-unsubstituted nitroimidazoles have an imino hydrogen atom in contrast to the N-substituted derivatives, and react with hydroxide to give the yellow nitroimidazole anions. The difficulty of reducing the nitro-group in these anions, together with the shift of the absorption maximum to longer wavelengths makes it possible to analyse polarographically or spectrophotometrically a mixture of N-unsubstituted nitroimidazole with N-substituted derivatives. The presence of the N-unsubstituted nitroimidazole and the N-substituted derivatives is first established by chromatography. Other criteria are also proposed for distinguishing between these substances.     

Optically and redox-active ferroceneacetylene polymers and oligomers

The palladium-catalyzed Sonogashira reaction can be used to build optically active, oligomeric 1,2,3-substituted ferrocenes up to the tetramer, as well as polymers, by sequential coupling of optically active (ee > 98 %), planar chiral iodoferroceneacetylenes and ferroceneacetylenes. (SFC)-1-Iodoferrocene-2-carbaldehyde (1) was reduced to the alcohol and methylated to give the corresponding methyl ether, which was Sonogashira-coupled with HC(triple bond)CSiEt3, resulting in (RFc)-1-(C(triple bond)CSiEt3)-2-methoxymethylferrocene (4) (79%, three steps). Orthometalation with tBuLi followed by quenching with 1,2-diodoethane gave (RFc)-1-(C(triple bond)CSiEt3)-2-methoxymethyl-3-iodoferrocene (5). Deprotection of the acetylene with nBu4NF resulted in (RFc)-1-ethynyl-2-methoxymethyl-3-iodoferrocene (6), which was Sonogashira-coupled with itself to produce an optically active polymer. Deprotection of 4 with nBu4NF and Sonogashira coupling of the product with 5 resulted in the dinuclear ferrocene 9. Deprotection of 9 and coupling with 5, followed by deprotection of the resulting acetylene 11, gave the trinuclear ferrocene 12. Another such sequence involving 11 and 5 produced a tetranuclear ferrocene 13. To study the electronic communication in such oligomers in more detail, two symmetrical, closely interrelated, trinuclear ferrocenes 18 and 19 were synthesized. The redox potentials of all the ferrocenes and the ferroceneacetylene polymer were determined by cyclic and square-wave voltammetry. All the metallocenes were investigated by UV/Vis spectroscopy. A linear relationship was found between lambdamax and l/n (n=number of ferrocene units in the oligomer). The polymer displayed two redox waves in the cyclic voltammogram, at 0.65 and 0.795 V. The corresponding mixed-valence oligoferrocene cations were synthesized from four ferroceneacetylenes, and their metal-metal charge transfer bands were examined by UV/Vis-NIR. The resonance exchange integrals Had, calculated on the basis of spectral information from the metal - metal charge transfer (MMCT) bands, were between 290 and 552 cm-1.