Growth of ZnO nanodisk, nanospindles and nanoflowers for gas sensor: pH dependency

Suitable morphology for fast electron transportation is a crucial requirement for the fabrication of gas sensor application. Highly oriented and well defined zinc oxide (ZnO) nano/micro-scale structures are grown on the glass substrates using aqueous chemical route. The grown nanostructures have been characterized by X-ray diffraction pattern (XRD), scanning electron microscope (SEM) and optical absorption techniques. The SEM micrographs revealed the formation of disk, rod, spindle and flower-like morphologies at different pH values ranging from 5 to 10. The grown nanostructures were employed for acetone gas-sensing measurement. It is observed that the sensors based on nanoflowers showed higher response (95%) for acetone gas at 325 °C. The high acetone gas sensitivity of ZnO nanoflowers can be attributed to the surface morphology. Moreover, nanoflower-like structure exhibits the fast response and recovery.     

Synthesis and characterization of a tetramethyl furanone functionalized diiminedioxime,a potential ligand for Cu radiopharmaceuticals,and its copper(II) and nickel(II) complexes

As part of our on-going effort to develop ⁶⁴Cu-based radiopharmaceuticals for PET (positron emission tomography) imaging of multidrug resistance in cancer, we prepared a tetramethylfuranone-functionalized diiminedioxime ligand, TMFPreH (TMFPreH = 4-[3-(4-hydroxyimino-2,2,5,5-dimethyl-dihydro-furan-3-ylideneamino)-propylimino]-2,2,5,5-tetramethyl-dihydrofuran-3(2H)-one oxime) and its Cu(II) and Ni(II) complexes. When the copper(II) complex was prepared from Cu(ClO₄)₂ in ethanol, it was isolated as a Cu(II)-bridged dimer, but when it was prepared from Cu(OAc)₂ and heated in acetone, an unusual example of an acetone adduct of the ligand is formed by reduction of one of the imine double bonds by the solvent. The Ni(II) complex is square pyramidal with the perchlorate counterion at the apex.     

分散液-液微萃取/高效液相色谱法测定水样中的痕量双酚A

建立了分散液-液微萃取与高效液相色谱联用技术测定水样中痕量双酚A(BPA)的方法. 通过对实验条件的筛选及优化, 得到最佳条件: 22.5 μL氯苯作萃取剂、0.5 mL丙酮作分散剂、0 min静止萃取时间、调节pH 3.2左右、10%离子强度及9 mL水样体积. 此条件下方法的线性范围为0.5~100 μg/L(R2=0.9941), 检出限为0.10 μg/L. 在BPA质量浓度为1 μg/L条件下, 方法回收率为87.8%~111.0%, 相对标准偏差8.3%(n=5), 富集倍数范围1905~2527. 对添加不同BPA浓度的自来水、地表水及回用中水进行分析, 回收率分别为(108±11.1)%, (107±13.2)%及(81.2±6.2)%(n=3). 在既定的色谱条件下, BPA的测定不受乙炔基雌二醇、雌二醇、雌三醇、雌酮和壬基酚等雌激素的干扰.     

Bifunctional thiophosphinamide catalyzed highly enantioselective Michael addition of acetone to (E)-2-azido β-nitrostyrenes and the subsequent reductive cyclization

We have proven that primary amine/thiophosphinamide incorporating (1R,2R)-1,2-diphenylethane-1,2-diamine is an efficient catalyst for the asymmetric Michael addition of acetone to (E)-2-azido β-nitrostyrenes. Under the optimal reaction conditions, the corresponding Michael addition products were obtained in excellent yields with almost perfect stereocontrol. Upon treatment with Et₃SiH/InCl₃, the Michael addition products could be successfully converted to the related 2-methyltetrahydroquinolines in acceptable yields with moderate to excellent diastereoselectivity and without appreciable loss in optical purity. This process provides a highly enantioselective pathway for the synthesis of biologically important 2-methyltetrahydroquinoline derivatives.     

The complexation of alkaline cations by crown ethers and cryptands in acetone

Stability constants and thermodynamic values for the complex formation of alkali ions by crown ethers, diaza crown ethers and cryptands have been measured by means of potentiometric and calorimetric titrations in acetone as solvent. The interactions between the ligands and solvent molecules play an important role for the complex formation. Cryptands form the most stable complexes with alkali ions if inclusion complexes are formed. Even in the case that the salts are not completely dissociated in acetone the presence of ion pairs does not influence the calculated values of the stability constants.     

水合高氯酸盐+有机溶剂体系中氢氧化物电沉积的EQCM研究

采用电化学石英晶体微天平(EQCM)定量研究了含水合高氯酸盐的丙酮、DMF、DMSO、C2H5OH或CH3OH有机溶液中LiOH(或NaOH)的电沉积过程. 这种电沉积现象可归因于有机溶液中的溶解氧和共存水在负电位下电还原产生OH−, OH−与溶液中金属阳离子结合生成在非水溶剂中溶解度很小的氢氧化物而沉淀在电极表面, 从而引起压电参数的响应, 而使用四丁基溴化铵为支持电解质时这种现象不明显. 讨论了不同支持电解质、不同溶剂、支持电解质浓度和外加水浓度对氢氧化物电沉积的影响, 估算了氢氧化物沉淀的电极收集效率.     

Gas/Solid Reactions with Acetone

Gas/solid reactions of acetone vapor with neutral organic compounds, salts, or host crystals with strict exclusion of solvents are reported. This gas/solid technique largely avoids waste formation and saves resources. Starting hydrochlorides or hydrobromides are also synthesized by gas/solid techniques. Dihydrohalides of o-phenylenediamines give 1,5-benzodiazepines 3 , aromatic and aliphatic 1,2-aminothiols (o-aminothiophenol, penicillamines, cysteine) yield five-membered thiazolines and thiazolidines 7, 9, 11, 13. Virtually all carbonyl reagents of the primary amino type 14 give quantitatively the imino derivatives 15 and water. Salt formation may be helpful for increasing melting points and sometimes reactivity as in 8, 10 , and 12 if surface passivation has to be overcome. In the case of solid 14 the free bases react equally well. Acetone ( 2 ) may be quantitatively removed from exhaust gases by using hydroxylaminium phosphate with formation of free acetone oxime at high flow rates. Inclusion of acetone into various hosts ( 17-20 , but not 16 ) is more efficient by imbibition from the gas phase than by crystallization from acetone as the solvent. This advantage may be utilized for gas separations. Some further gases (vapors) coexist in imbibed clathrates whereas others do not. The mechanisms of the gas/solid reactions are elucidated using atomic force microscopy (AFM). Phase rebuildings involve anisotropic movements of molecules over large distances and the formation of characteristic features. In some cases surface hydrates catalyze the gas/solid reaction. Solid-state mechanisms for imbibition from the gas phase into host crystals with formation of clathrates are similar in nature to those of the covalent reactions. These results are correlated with known X-ray crystal structures where available.     

Application of cellulose acetate butyrate-based membrane for osmotic drug delivery

The release rate of drugs from an OROS^® is controlled by semipermeable membranes composed typically of cellulose acetate (CA) with various flux enhancers. Cellulose acetate butyrate (CAB) was identified as a viable alternative. The CAB membrane matched the CA membrane in robustness but had superior drying properties, offering particular advantages for thermolabile formulations. Studies were conducted to characterize CAB membrane properties with respect to performance of OROS^® systems. Four different membrane formulations with varying plasticizer type and concentration were investigated. The CAB based membranes exhibited superior drying characteristics and similar functionality to the CA:polyethylene glycol (PEG) membranes used as a control. A linear relationship was observed between the level of flux enhancer and release rate. The stability of the membrane was evaluated based on release profiles after system storage at various conditions. The CAB membranes appeared to have stability comparable to the standard CA membrane. A linear relationship between membrane weight and release rate as well as the time required to release 90% of a drug from the system [T₉₀] for a model formulation was observed. In conclusion, the newly identified alternative membrane composition allows for the use of thinner membranes, thereby reducing cost of goods, coating time and, most importantly, membrane drying time.     

Proline-catalyzed aldol reactions of acyl cyanides with acetone: an efficient and convenient synthesis of 1,3-diketones

The aldol-type addition of acetone towards (un)substituted benzoyl, heteroarylcarbonyl or α,β-unsaturated acyl cyanides was efficiently catalyzed by l-proline (30 mol %) to give 2-hydroxy-4-oxo-2-substituted pentanenitriles. Upon the treatment with sodium hydroxide, the adducts transformed to 1,3-diketones in good-to-excellent yield, furnishing an efficient and convenient method for the regioselective synthesis of 1,3-diketones.     

Polypyrrole/poly(methylmethacrylate) blend as selective sensor for acetone in lacquer

A film of α-naphthalene sulfonate-doped polypyrrole/poly(methylmethacrylate), PPy/α-NS⁻/PMMA, obtained from solution mixing was successfully used as sensing material for acetone vapor in lacquer with a high degree of selectivity based on electrical conductivity over acetic acid and a high degree of stability over the humidity change. Compared with pure PPy/α-NS⁻, the selectivity ratio of acetone/acetic acid response of PPy/α-NS⁻/PMMA blend with a PMMA/PPy weight ratio of 3.0 was ca. 3.9 times higher. The film was found to be insensitive to moisture unless the relative humidity (RH) was lower than 20% RH in which the selectivity ratio of acetone/acetic acid response was enhanced. The time required to reach the equilibrium for acetone exposure was found to increase slightly with increasing humidity.