Sample records for benzoin

  1. Recent advances in N-heterocyclic carbene (NHC-catalysed benzoin reactions

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    Rajeev S. Menon


    Full Text Available N-Heterocyclic carbenes (NHCs have emerged as a powerful class of organocatalysts that mediate a variety of organic transformations. The Benzoin reaction constitutes one of the earliest known carbon–carbon bond-forming reactions catalysed by NHCs. The rapid growth of NHC catalysis in general has resulted in the development of a variety of benzoin and benzoin-type reactions. An overview of such NHC-catalysed benzoin reactions is presented.

  2. Identification of benzoin obtained from calli of Styrax officinalis by HPLC


    DEMİRAY, Hatice; DEREBOYLU, Aylin EŞİZ; YAZICI, Zekiye Işın; Karabey, Fatih


    The stem tissue of Styrax officinalis L. distributed in West Anatolia was induced with agents such as boric acid and cocarboxylase (thiamine diphosphate), extensive stimulators of resin channels, in order to increase the amount of benzoin volatile oil. While the benzoin content was 120% in the induction medium to which excess boron and niacin were added, it increased to 231% when cocarboxylase (thiamine diphosphate) was added to the medium. Benzoin content of Styrax from petiole calli was 166...

  3. Propagation of Valuable North Sumatera Benzoin Trees (Styrax Sp) Using Macrocutting Technique (United States)

    Susilowati, A.; Hartini, K. S.; Rachmat, H. H.; Alvaroby, M.


    Kemenyan known as Sumatran benzoin is North Sumatera local species that produce high valuable rosin and prospective export comodities. However, sustainability of Sumatran benzoin production has many constraints such as instability of resin production, lack information of propagation technique and traditional management system. Until now, comprehensive information for Sumatran benzoin propagation system still not determined yet. The objectives of this research were (1) to get information about propagation technique of Sumatran benzoin and its suitable growing medium and 2) to get information on adventitious root formation in Sumatran benzoin cuttings. Cutting materials (Toba benzoin and Durame benzoin) were originated from 1 year old seedling propagated by seed. Media used were combination of sand : rice husk (1:0 v/v; 1/1 v/v). Results showed that interaction between media and benzoin species significantly affected primer and secondary root lenght. While planting medium significantly improved secondary root length and number. Benzoin species significantly affected primary and secondary root lenght, and secondary root number.

  4. Kultur Daun Pucuk Tanaman Kemenyan (Styrax benzoin Dryander) Pada Media Ms Dengan Pemberian Atonik Dan BAP


    Tarigan, Rico Pranata


    The research about “The Leaf Tissue Culture Of Benzoin (Styrax Benzoin Dryander) In MS Media With Atonik And BAP” has been done in Plant Tissue Culture Laboratory of Biology Department at Faculty of Mathematics and Natural Science, University of Sumatera Utara from Januari 2010 until May 2010. The aim of the research was to obtain the effect of combination Atonik and BAP to the growth of the leaf tissue culture of benzoin (Styrax benzoin Dryander) using Complete Randomized Design and two fact...

  5. Antibacterial, anti-biofilm and anticancer potentials of green synthesized silver nanoparticles using benzoin gum (Styrax benzoin) extract. (United States)

    Du, Juan; Singh, Hina; Yi, Tae-Hoo


    This study described a simple and green approach for the synthesis of silver nanoparticles (AgNPs) employing benzoin gum water extract as a reducing and capping agent and their applications. The AgNPs were characterized by ultraviolet-visible spectrophotometer, X-ray diffraction pattern, field emission transmission electron microscopy, dynamic light scattering, zeta potential and fourier transform infrared spectroscopy. The AgNPs showed promising antimicrobial activity against various pathogens (Gram-negative, Gram-positive and fungus) and possessed high free radical scavenging activity (104.5 ± 7.21 % at 1 mg/ml). In addition, the AgNPs exhibited strong cytotoxicity towards human cervical cancer and human lung cancer cells as compared to the normal mouse macrophage cells. Moreover, the AgNPs possessed anti-biofilm activity against Escherichia coli, and compatibility to human keratinocyte HaCaT cells, which suggests the use of dressing with the AgNPs in chronic wound treatment. Therefore, AgNPs synthesized by benzoin gum extract are comparatively green and may have broad spectrum potential application in biomedicine.

  6. An investigation of the catalytic potential of potassium cyanide and imidazolium salts for ultrasound-assisted synthesis of benzoin derivatives


    Javad Safari; Zohre Zarnegar; Masoume Ahmadi; Susan Seyyedi


    A rapid, highly efficient and mild green synthesis of benzoin was performed using substituted benzaldehyde catalyzed by KCN and imidazolium salts in EtOH/H2O under ultrasonic activation. The products were obtained in good yields within short reaction times with N,N′-dialkylimidazolium salts, which were found to be more effective pre-catalysts at room temperature for benzoin condensation in comparison to corresponding cyanide ion in heating method. This simple method affords benzoin derivative...

  7. An investigation of the catalytic potential of potassium cyanide and imidazolium salts for ultrasound-assisted synthesis of benzoin derivatives

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    Javad Safari


    Full Text Available A rapid, highly efficient and mild green synthesis of benzoin was performed using substituted benzaldehyde catalyzed by KCN and imidazolium salts in EtOH/H2O under ultrasonic activation. The products were obtained in good yields within short reaction times with N,N′-dialkylimidazolium salts, which were found to be more effective pre-catalysts at room temperature for benzoin condensation in comparison to corresponding cyanide ion in heating method. This simple method affords benzoin derivatives at room temperature in short reaction times with high yield and purity.

  8. A tailor-made chimeric thiamine diphosphate dependent enzyme for the direct asymmetric synthesis of (S)-benzoins. (United States)

    Westphal, Robert; Vogel, Constantin; Schmitz, Carlo; Pleiss, Jürgen; Müller, Michael; Pohl, Martina; Rother, Dörte


    Thiamine diphosphate dependent enzymes are well known for catalyzing the asymmetric synthesis of chiral α-hydroxy ketones from simple prochiral substrates. The steric and chemical properties of the enzyme active site define the product spectrum. Enzymes catalyzing the carboligation of aromatic aldehydes to (S)-benzoins have not so far been identified. We were able to close this gap by constructing a chimeric enzyme, which catalyzes the synthesis of various (S)-benzoins with excellent enantiomeric excess (>99%) and very good conversion.

  9. Ceratocystis larium sp. nov., a new species from Styrax benzoin wounds associated with incense harvesting in Indonesia

    NARCIS (Netherlands)

    Wyk, van M.; Wingfield, B.D.; Clegg, P.A.; Wingfield, M.J.


    Styrax benzoin trees, native to the island Sumatra, Indonesia are wounded to produce resin that is collected and burned as incense. These wounds on trees commonly develop into expanding cankers that lead to tree death. The aim of this study was to consider whether Ophiostomatoid fungi, typically ass

  10. (±)Methanodibenzodiazocine tethered [C-H]+ functional site: Study towards benzoin condensation and Baylis-Hillman reactions

    Indian Academy of Sciences (India)

    Arruri Sathyanarayana; Ganesan Prabusankar


    New heterocyclic ring systems consisting of (±) methanodibenzodiazocine and imidazolium/benzimidazolium salts were synthesized in very good yield. Subsequently, these halide salts were subjected to the anion exchange reaction with KPF6 to yield the corresponding azolium salts in excellent yield. The possible applications of these newly prepared salts were investigated in homogeneous catalysis. Remarkable changes in the catalytic activity were observed by varying the bulkiness of N-substituent at imidazole. Catalytic activity of these newly prepared salts was tested for the benzoin condensation reaction. Exclusive formation of benzoin products were observed in good yield. Similarly, the dimerization of cyclohexen-1-one to Baylis-Hillman type product, 2-(3-oxocyclohexyl)-2-cyclohexen-1-one was studied.

  11. Alumina and Silica Oxides as Catalysts for the Oxidation of Benzoins to Benzils under Solvent-free Conditions

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    A. H. Dabbagh


    Full Text Available Alumina or silica gel are used as catalysts for a solvent-free oxidation of benzoins to the corresponding benzils. These catalysts are easily recovered after completion of the reactions, which are carried out either by heating in a sand bath or using microwave irradiation. Comparison of the results obtained with both catalysts indicates that all the reactants examined were oxidized faster on alumina than on silica under these conditions.

  12. Feasibility of gas/solid carboligation: conversion of benzaldehyde to benzoin using thiamine diphosphate-dependent enzymes. (United States)

    Mikolajek, R; Spiess, A C; Büchs, J


    A carboligation was investigated for the first time as an enzymatic gas phase reaction, where benzaldehyde was converted to benzoin using thiamine diphosphate (ThDP)-dependent enzymes, namely benzaldehyde lyase (BAL) and benzoylformate decarboxylase (BFD). The biocatalyst was immobilized per deposition on non-porous support. Some limitations of the gas/solid biocatalysis are discussed based on this carboligation and it is also demonstrated that the solid/gas system is an interesting tool for more volatile products.

  13. Ceratocystis larium sp. nov., a new species from Styrax benzoin wounds associated with incense harvesting in Indonesia. (United States)

    van Wyk, M; Wingfield, B D; Clegg, P A; Wingfield, M J


    Styrax benzoin trees, native to the island Sumatra, Indonesia are wounded to produce resin that is collected and burned as incense. These wounds on trees commonly develop into expanding cankers that lead to tree death. The aim of this study was to consider whether Ophiostomatoid fungi, typically associated with wounds on trees might be associated with resin harvesting on S. benzoin. Samples were collected from the edges of artificially induced wounds, and particularly where cankers and staining of the vascular tissue was evident. Tissue samples were incubated in moist chambers and carrot baiting was also used to detect the presence of Ceratocystis spp. Fruiting structures with morphology typical of species in the C. fimbriata s.l. species complex and species in the anamorph genus Thielaviopsis were found, on both the incubated wood and the carrot baits. DNA sequences were generated for the Internal Transcribed Spacer regions 1 and 2 including the 5.8S rRNA gene, part of the beta-tubulin and the Transcription Elongation Factor 1-alpha gene regions. These data were compared with those of other species in the C. fimbriata s.l. species complex and Thielaviopsis using phylogenetic analysis. Morphology of the isolates in culture as well as phylogenetic inference showed that the Thielaviopsis sp. present on the wounds was T. basicola. The Ceratocystis sp. from S. benzoin represents a new taxon in the C. fimbriata s.l. complex described here as C. larium sp. nov.

  14. Expedient synthesis of C-aryl carbohydrates by consecutive biocatalytic benzoin and aldol reactions. (United States)

    Hernández, Karel; Parella, Teodor; Joglar, Jesús; Bujons, Jordi; Pohl, Martina; Clapés, Pere


    The introduction of aromatic residues connected by a C-C bond into the non-reducing end of carbohydrates is highly significant for the development of innovative structures with improved binding affinity and selectivity (e.g., C-aril-sLex). In this work, an expedient asymmetric "de novo" synthetic route to new aryl carbohydrate derivatives based on two sequential stereoselectively biocatalytic carboligation reactions is presented. First, the benzoin reaction of aromatic aldehydes to dimethoxyacetaldehyde is conducted, catalyzed by benzaldehyde lyase from Pseudomonas fluorescens biovar I. Then, the α-hydroxyketones formed are reduced by using NaBH4 yielding the anti diol. After acetal hydrolysis, the aldol addition of dihydroxyacetone, hydroxyacetone, or glycolaldehyde catalyzed by the stereocomplementary D-fructose-6-phosphate aldolase and L-rhamnulose-1-phosphate aldolase is performed. Both aldolases accept unphosphorylated donor substrates, avoiding the need of handling the phosphate group that the dihydroxyacetone phosphate-dependent aldolases require. In this way, 6-C-aryl-L-sorbose, 6-C-aryl-L-fructose, 6-C-aryl-L-tagatose, and 5-C-aryl-L-xylose derivatives are prepared by using this methodology.


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    Full Text Available Bilirubin is the degradation product of heme, thebulk of which is derived from hemoglobin of senescenterythrocytes and hepatic hemoproteins. Bilirubin ispotentially toxic, but is normally rendered harmless bybinding to plasma albumin, and efficient hepatic clearance.Jaundice, (also known as icterus is a yellowishpigmentation of the skin, the conjunctival membranes overthe sclerae (whites of the eyes, and other mucousmembranes caused by hyperbilirubinemia (increased levelsof bilirubin in the blood. Complications of jaundiceinclude sepsis especially cholangitis, biliary cirrhosis,pancreatitis, coagulopathy, renal and liver failure.Treatment of rats with Phenylhydrazine 5 mg/ kg bodyweight for five days resulted in the development ofjaundice as BR level was found to be higher than 2 mg/dL.Bilirubin lowering potential of Benzoin ethyl alcoholextract was evaluated in temporarily jaundiced adultwistar rats. Treatment of these rats with Benzoin extractfor seven days reduced the BR level significantly to thenormal value. Whereas smaller dose (10mg/kg bodyweight resulted in the reduction in BR level from 2.51 ±0.02 to 0.90 ± 0.01 mg/dL, higher doses of 20 and 40mg/kg body weight were found to be more effective inreducing the bilirubin level from 2.54 ± 0.01 to 0.82 ±0.01 mg/dL and from 2.49±0.02 to 0.66±0.01 mg/dL,respectively. Therefore, Benzoin ethyl alcohol extract canbe used to reduce bilirubin concentration to a normal levelin jaundiced subjects.

  16. Electron-transfer-initiated benzoin- and Stetter-like reactions in packed-bed reactors for process intensification

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    Anna Zaghi


    Full Text Available A convenient heterogeneous continuous-flow procedure for the polarity reversal of aromatic α-diketones is presented. Propaedeutic batch experiments have been initially performed to select the optimal supported base capable to initiate the two electron-transfer process from the carbamoyl anion of the N,N-dimethylformamide (DMF solvent to the α-diketone and generate the corresponding enediolate active species. After having identified the 2-tert-butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diazaphosphorine on polystyrene (PS-BEMP as the suitable base, packed-bed microreactors (pressure-resistant stainless-steel columns have been fabricated and operated to accomplish the chemoselective synthesis of aroylated α-hydroxy ketones and 2-benzoyl-1,4-diones (benzoin- and Stetter-like products, respectively with a good level of efficiency and with a long-term stability of the packing material (up to five days.

  17. Electron-transfer-initiated benzoin- and Stetter-like reactions in packed-bed reactors for process intensification (United States)

    Zaghi, Anna; Ragno, Daniele; Di Carmine, Graziano; De Risi, Carmela; Bortolini, Olga; Giovannini, Pier Paolo; Fantin, Giancarlo


    A convenient heterogeneous continuous-flow procedure for the polarity reversal of aromatic α-diketones is presented. Propaedeutic batch experiments have been initially performed to select the optimal supported base capable to initiate the two electron-transfer process from the carbamoyl anion of the N,N-dimethylformamide (DMF) solvent to the α-diketone and generate the corresponding enediolate active species. After having identified the 2-tert-butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diazaphosphorine on polystyrene (PS-BEMP) as the suitable base, packed-bed microreactors (pressure-resistant stainless-steel columns) have been fabricated and operated to accomplish the chemoselective synthesis of aroylated α-hydroxy ketones and 2-benzoyl-1,4-diones (benzoin- and Stetter-like products, respectively) with a good level of efficiency and with a long-term stability of the packing material (up to five days). PMID:28144342


    Institute of Scientific and Technical Information of China (English)

    文瑞明; 丁亮中; 罗新湘; 俞善信


    @@ INTRODUCTION Benzil is an important photosensitive initiator of organic synthesis intermediates, medicinal intermediates and ultraviolet solidified resin(UV resin), and is usually prepared by oxidizing benzoin. The oxidizers and methods reported are mainly: (PhCH2Et3N)+Br-/(PhCO)2O2/MeCN[1], DMSO/(COCl)2/CH2Cl2[2], CrO3*CH3NH2*HCl/Al2O3[3], the metallorganic compound[4], microwave radiation[5],etc.

  19. 吸电子基取代苯偶姻的实用合成%Practical Synthesis of Benzoins Substituted by Electron-withdrawing Groups

    Institute of Scientific and Technical Information of China (English)

    杨文领; 杨云刚; 方丽; 张万顺


    The Benzoins condensation reaction by the way of the classical Vitamin B1 is substituted under the protection of inert gases and adds aqueous Na2 S2 O3 and zinc dust after its completion to inhibit product disintegration to make thiamin derivate which is replaced by electron-withdrawing groups depended upon KCN hyper toxic catalyst synthesis.It is supposed that the classical way of Vitamin B1 segregated nothing and electron-deficient benzoins could not be prepared by classical Vitamin B1 -promoted ones might be owing to the synergy between silica gel /alumina and decomposed Vitamin B1 during column chromatography,which could be inhibited by Zn-Na2 S2 O3 .%将经典维生素 B1法安息香缩合反应改进在惰性气体保护下进行,且在反应完成后加入硫代硫酸钠和锌粉抑制产物分解,可制备过去主要依赖 KCN 等剧毒催化剂合成的吸电子基团取代的苯偶姻衍生物。推测经典维生素 B1法分离不到产物,可能是由于柱层析时硅胶或氧化铝与维生素 B1分解产物的共同作用导致贫电子苯偶姻产物的分解,而 Zn-Na2 S2 O3溶液可以抑制这种作用。

  20. Dual-mesoporous ZSM-5 zeolite with highly b-axis-oriented large mesopore channels for the production of benzoin ethyl ether. (United States)

    Zhou, Xiaoxia; Chen, Hangrong; Zhu, Yan; Song, Yudian; Chen, Yu; Wang, Yongxia; Gong, Yun; Zhang, Guobin; Shu, Zhu; Cui, Xiangzhi; Zhao, Jinjin; Shi, Jianlin


    Dual-mesoporous ZSM-5 zeolite with highly b axis oriented large mesopores was synthesized by using nonionic copolymer F127 and cationic surfactant CTAB as co-templates. The product contains two types of mesopores--smaller wormlike ones of 3.3 nm in size and highly oriented larger ones of 30-50 nm in diameter along the b axis--and both of them interpenetrate throughout the zeolite crystals and interconnect with zeolite microporosity. The dual-mesoporous zeolite exhibits excellent catalytic performance in the condensation of benzaldehyde with ethanol and greater than 99 % selectivity for benzoin ethyl ether at room temperature, which can be ascribed to the zeolite lattice structure offering catalytically active sites and the hierarchical and oriented mesoporous structure providing fast access of reactants to these sites in the catalytic reaction. The excellent recyclability and high catalytic stability of the catalyst suggest prospective applications of such unique mesoporous zeolites in the chemical industry.

  1. Simultaneous spectrophotometric determination of trace amounts of uranium, thorium, and zirconium using the partial least squares method after their preconcentration by alpha-benzoin oxime modified Amberlite XAD-2000 resin. (United States)

    Ghasemi, Jahan B; Zolfonoun, E


    A new solid phase extraction method for separation and preconcentration of trace amounts of uranium, thorium, and zirconium in water samples is proposed. The procedure is based on the adsorption of U(VI), Th(IV) and Zr(IV) ions on a column of Amberlite XAD-2000 resin loaded with alpha-benzoin oxime prior to their simultaneous spectrophotometric determination with Arsenazo III using orthogonal signal correction partial least squares method. The enrichment factor for preconcentration of uranium, thorium, and zirconium was found to be 100. The detection limits for U(VI), Th(IV) and Zr(IV) were 0.50, 0.54, and 0.48microgL(-1), respectively. The precision of the method, evaluated as the relative standard deviation obtained by analyzing a series of 10 replicates, was below 4% for all elements. The practical applicability of the developed sorbent was examined using synthetic seawater, natural waters and ceramic samples.

  2. Determination of borax in flour and its products by benzoin fluorescence method%安息香荧光法测定面粉及其制品中硼砂根

    Institute of Scientific and Technical Information of China (English)

    王莎莎; 薛岭; 田益玲


    目的:建立一种安息香荧光衍生法测定面粉及其制品中硼砂根的含量。方法安息香与硼离子形成复合物,在甘氨酸做缓冲溶液条件下,通过荧光分光光度法测定复合物中的硼,进而建立一种快速检测食品中的硼砂含量的方法。结果在该条件下硼砂根为10-7~10-5 mol/L范围内回归系数达到0.9999。利用该条件建立的测定面制品中硼砂的含量回收率为83%~102%,其中面粉中的回收率在100%左右。结论本研究证明使用该方法测定面粉及其制品中的硼酸根较为准确、可靠,为方便快速地测定食品中的硼砂提供了技术支持。%Objectvie To develop a benzoin fluorescence method for the determination of borax in flour and its products. Methods Benzoin and boron ions formed complexes in glycine buffer solution and then de-termined by fluorescence spectrophotometry, thereby establishing a method for rapid detection of food borax content. Results Under the described conditions, the proposed method was applicable over the concentration range ( 10-7~10-5 mol/L), the borate concentration was linear with the fluorescence intensity (regression coef-ficient: 0.9999), with recoveries for borax in flour and related products were almost 100and 83~102 respec-tively. Conclusion The established method for determination of borax in flour and its products is accurate and validated, which provides efficient technical support for rapidly detecting the borax in food.

  3. 无水苯甲酸锂的合成、结构表征及热化学研究%Synthesis, Structure Characterization and Thermochemistry of Anhydrous Lithium Benzoinate

    Institute of Scientific and Technical Information of China (English)

    何东华; 邸友莹; 杨伟伟; 孔玉霞; 淡文彦; 谭志诚


    用分析纯苯甲酸和一水氢氧化锂作为反应物, 采用水热合成法制得苯甲酸锂. 利用X射线粉末衍射、 FTIR、 元素分析及化学分析等方法对样品进行组成和结构表征. 采用精密自动绝热热量计测量了其在80~400 K范围内的摩尔热容, 利用最小二乘法将此温区热容实验值对折合温度进行拟合, 得到热容随温度变化的多项式方程. 通过设计合理的热化学循环, 选用0.1 mol/L HCl溶液作为量热溶剂, 利用等温环境溶解-反应热量计分别测定合成反应的反应物和产物在所选溶剂中的溶解焓, 得到反应焓Δ_rH~φ -_m=-(9.75±0.27) kJ/mol. 利用Hess定律计算出苯甲酸锂的标准摩尔生成焓Δ_fH~φ-_m(C6H5COOLi, s)=-(307.82±0.57) kJ/mol.%Benzoic acid and lithium hydroxide with the analytical grade were chosen as the reactants, and the lithium benzoinate was synthesized by means of hydrothermal synthesis. XRD,FTIR and elementary and chemical analyses were applied to characterize its composition and structure. Low-temperature heat capacities of the compound were measured via a precision automated adiabatic calorimeter over the temperature range from 80-400 K. A polynomial equation of the heat capacities as a function of the temperature was fitted by the least square method. A reasonable thermochemical cycle was designed on the basis of the preparation reaction of the substance, 0.1 mol/L of HC1 solution was chosen as the calorimetric solvent, and the standard molar enthalpies of dissolution for the reactants and products of the hydrothermal reaction in the selected solvents were measured by an isoperibol solution-reaction calorimeter, respectively. The enthalpy change of the preparation reaction was determined as △_rH_m~θ =-(9.75±0.27) kJ/mol from the standard molar enthalpies of dissolution. Eventually, the standard molar enthalpy of formation of anhydrous lithium benzoinate was derived to be △_rH_m~θ =-(307.82±0.57) kJ/mol by

  4. 二氧化硅负载镍铝水滑石的制备及其催化合成安息香乙醚的研究%NiAl-LDHs/SiO2 Composite: Preparation and Application in Benzoin Ethyl Ether Synthesis

    Institute of Scientific and Technical Information of China (English)

    王国强; 谢鲜梅; 高成云; 吴旭; 安霞; 程淑艳


    采用共沉淀法制备了以二氧化硅为载体,表面包覆镍铝水滑石的NiA1-LDHs/SiO2复合物,借助XRD、IR及N2吸附-脱附等手段对合成物进行了表征,并将其应用于苯甲醛与乙醇反应生成安息香乙醚反应中进行活性评价.结果表明,复合物中镍铝水滑石与二氧化硅以稳定的Si-O-Al和Si-O-Ni键结合,镍铝水滑石均匀分布于二氧化硅表面,且生成的复合物比表面积较大;当镍铝水滑石负载量为20%时,在反应温度为70℃、反应时间为60 min条件下,NiAl-LDHs/SiO2催化苯甲醛与乙醇反应的苯甲醛转化率为61.8%,安息香乙醚选择性接近100%,其催化效果明显优于单一的NiAl-LDHs.%A surface-covered NiAl-LDHs composite NiAl-LDHs/SiO2 was prepared by coprecipitation method using silicon dioxide as supporter. The composite was characterized using X-ray diffraction (XRD), Fourier transform infrared (FTIR) and N2-adsorption/desorption measurement, and its catalytic performance was evaluated in terms of benzoin ethyl ether synthesis by reaction between benzaldehyde and methanol. The results show that the NiAl-LDHs and SiO2 are combined each other through the stable chemical bond of Si-O-Al and Si-O-Ni in the composite. NiAl-LDHs is distributed uniformly on the surface of SiO2, and the composite has high specific surface area. Additionally, the synthesis of benzoin ethyl ether was performed with NiAl-LDHs/SiO2 of 20% LDHs loadings as the catalyst at 70 ℃ for 60 min. The results show that conversion rate of benzaldehyde could reach 61,8% with the selectivity of benzoin ethyl ether nearly 100% and that NiAl-LDHs/SiO2 has higher catalytic activity than single NiAl-LDHs.

  5. Benzoin Condensation: Monitoring a Chemical Reaction by High-Pressure Liquid Chromatography (United States)

    Bhattacharya, Apurba; Purohit, Vikram C.; Bellar, Nicholas R.


    High-pressure liquid chromatography (HPLC) is the preferred method of separating a variety of materials in complex mixtures such as pharmaceuticals, polymers, soils, food products and biological fluids and is also considered to be a powerful analytical tool in both academia and industry. The use of HPLC analysis as a means of monitoring and…

  6. Drug: D03091 [KEGG MEDICUS

    Lifescience Database Archive (English)

    Full Text Available rapeutic category: 7150 7319 Styracaceae (storax family) Styrax benzoin resin Maj...ion D03091 Benzoin; Benzoin tincture; Anxixang Crude drugs [BR:br08305] Dicot plants: asterids Styracaceae (storax family) D03091 Benzoin PubChem: 17397246 ...

  7. Insights into the Competing Mechanisms and Origin of Enantioselectivity for N-Heterocyclic Carbene-Catalyzed Reaction of Aldehyde with Enamide (United States)

    Qiao, Yan; Chen, Xinhuan; Wei, Donghui; Chang, Junbiao


    Hydroacylation reactions and aza-benzoin reactions have attracted considerable attention from experimental chemists. Recently, Wang et al. reported an interesting reaction of N-heterocyclic carbene (NHC)-catalyzed addition of aldehyde to enamide, in which both hydroacylation and aza-benzoin reactions may be involved. Thus, understanding the competing relationship between them is of great interest. Now, density functional theory (DFT) investigation was performed to elucidate this issue. Our results reveal that enamide can tautomerize to its imine isomer with the assistance of HCO3‑. The addition of NHC to aldehydes formed Breslow intermediate, which can go through cross-coupling with enamide via hydroacylation reaction or its imine isomer via aza-benzoin reaction. The aza-benzoin reaction requires relatively lower free energy barrier than the hydroacylation reaction. The more polar characteristic of C=N group in the imine isomers, and the more advantageous stereoelectronic effect in the carbon-carbon bond forming transition states in aza-benzoin pathway were identified to determine that the imine isomer can react with the Breslow intermediate more easily. Furthermore, the origin of enantioselectivities for the reaction was explored and reasonably explained by structural analyses on key transition states. The work should provide valuable insights for rational design of switchable NHC-catalyzed hydroacylation and aza-benzoin reactions with high stereoselectivity.

  8. Catalytic activation of carbohydrates as formaldehyde equivalents for Stetter reaction with enones. (United States)

    Zhang, Junmin; Xing, Chong; Tiwari, Bhoopendra; Chi, Yonggui Robin


    We disclose the first catalytic activation of carbohydrates as formaldehyde equivalents to generate acyl anions as one-carbon nucleophilic units for a Stetter reaction. The activation involves N-heterocyclic carbene (NHC)-catalyzed C-C bond cleavage of carbohydrates via a retro-benzoin-type process to generate the acyl anion intermediates. This Stetter reaction constitutes the first success in generating formal formaldehyde-derived acyl anions as one-carbon nucleophiles for non-self-benzoin processes. The renewable nature of carbohydrates, accessible from biomass, further highlights the practical potential of this fundamentally interesting catalytic activation.

  9. Aqueous Media Oxidation of Alcohols with Ammonium Persulfate

    Institute of Scientific and Technical Information of China (English)

    IMANZADEH, Gholam Hassan; ZAMANLOO, Mohammad R.; MANSOORI, Yaghoob; KHODAYARI, Ali


    Oxidation of series of various primary and secondary alcohols to corresponding carbonyl compounds with ammonium persulfate in aqueous media was described. No over oxidation of primary alcohols to carboxylic acids and secondary alcohols to esters was observed. Under such conditions benzoin was converted to benzoic acid.

  10. Ceric ammonium nitrate catalysed three component one-pot efficient synthesis of 2,4,5-triaryl-1H-imidazoles

    Indian Academy of Sciences (India)

    Jaiprakash N Sangshetti; Nagnnath D Kokare; Sandeep A Kotharkara; Devanand B Shinde


    Ceric ammonium nitrate (CAN) is used as an efficient catalyst for the synthesis of 2,4,5-triaryl-1H-imidazoles via condensation of benzoin/benzil, ammonium acetate, and aromatic aldehydes. The easy work-up, higher yields and shorter reaction time are the advantages of the method presented here.

  11. The Prehistory of the Proposed Clayton Lake Area, Southeast Oklahoma. Phase I Investigations. (United States)


    Wild lettuce) Lepidium virginianwn ( Pepper grass) Lindera benzoin (Spice bush) Liquidambar styraoiflua (Sweetgum) Inner bark Shoots, leaves...established tree ring calibration curves has not significantly helped in reducing these discrepancies (Ralph, Michael, and Han 1973; Damon, Ferguson ...below in a summary form. Corrected dates, obtained by following Ralph, Michael, and Han (1973) and Damon, Ferguson , Long, and Wallick (1974) are also

  12. Solar thermochemical reactions Ⅲ: A convenient one-pot synthesis of 1,2,4,5-tetrasubstituted imidazoles catalyzed by high surface area SiO2 and induced by solar thermal energy

    Institute of Scientific and Technical Information of China (English)

    Ramadan A. Mekheimer; Afaf M. Abdel Hameed; Seham A.A. Mansour; Kamal Usef Sadek


    A simple, convenient and efficient method for the synthesis of 1,2,4,5-tetrasubstituted imidazole derivatives using benzoin, an aromatic aldehyde, an aromatic amine in the presence of ammonium acetate catalyzed by high surface area SiO2 and induced by free solar thermal energy was reported.

  13. N,N-Dimethylbenzimidazolium iodide as a green catalyst for cross-coupling of aromatic aldehydeswith unactivated imines

    Directory of Open Access Journals (Sweden)

    Viwat Hahnvajana wong


    Full Text Available Cross-coupling of aromatic aldehydes with unactivated iminescatalyzed by N,N-dimethylbenzimidazolium iodide in ethanolic sodium hydroxide solution gave α-amino ketonesin satisfactory yields. Benzoin condensation and further oxidation of the resulted aroins also occurred as side reactions.

  14. Tannic acid Catalyzed an Efficient Synthesis of 2,4,5-Triaryl-1H-Imidazole

    Directory of Open Access Journals (Sweden)

    Shitole Nana Vikram


    Full Text Available Tannic acid (C76H52O46 has been found to be an efficient catalyst for one-pot synthesis of 2,4,5-triaryl substituted imidazoles by the reaction of an arylaldehyde, benzyl/benzoin and an ammonium acetate. The short reaction time and excellent yields making this protocol practical and economically attractive.

  15. Preparation of azidoaryl- and azidoalkyloxazoles for click chemistry. (United States)

    Loner, Catherine M; Luzzio, Frederick A; Demuth, Donald R


    A series of azidoaryl- and azidoalkyl(diphenyl)oxazole scaffolds were warranted for biofilm inhibition studies. Cyclization of azidoaryl- or azidoalkyl esters of benzoin with ammonium acetate in acetic acid gives 2-azidoaryl- or 2-azidoalkyl-4,5-diphenyloxazoles. The azidoaryl esters are prepared from the corresponding azidocarboxylic acids/acid chlorides while the azidoalkyl esters are prepared from the corresponding haloalkyl esters.

  16. The Catalytic Asymmetric Intramolecular Stetter Reaction. (United States)

    de Alaniz, Javier Read; Rovis, Tomislav


    This account chronicles our efforts at the development of a catalytic asymmetric Stetter reaction using chiral triazolium salts as small molecule organic catalysts. Advances in the mechanistically related azolium-catalyzed asymmetric benzoin reaction are discussed, particularly as they apply to catalyst design. A chronological treatise of reaction discovery, catalyst optimization and reactivity extension follows.

  17. Cyclotetrabenzoin: Facile Synthesis of a Shape-Persistent Molecular Square and Its Assembly into Hydrogen-Bonded Nanotubes. (United States)

    Ji, Qing; Le, Ha T M; Wang, Xiqu; Chen, Yu-Sheng; Makarenko, Tatyana; Jacobson, Allan J; Miljanić, Ognjen Š


    Cyanide-catalyzed benzoin condensation of terephthaldehyde produces a cyclic tetramer, which we propose to name cyclotetrabenzoin. Cyclotetrabenzoin is a square-shaped macrocycle ornamented with four α-hydroxyketone functionalities pointing away from the central cavity, the dimensions of which are 6.9×6.9 Å. In the solid state, these functional groups extensively hydrogen bond, resulting in a microporous three-dimensional organic framework with one-dimensional nanotube channels. This material exhibits permanent-albeit low-porosity, with a Langmuir surface area of 52 m(2)  g(-1) . Cyclotetrabenzoin's easy and inexpensive synthesis and purification may inspire the creation of other shape-persistent macrocycles and porous molecular crystals by benzoin condensation.

  18. Efficient Multi-component Synthesis of Highly Substituted Imidazoles Utilizing P2O5/SiO2 as a Reusable Catalyst%Efficient Multi-component Synthesis of Highly Substituted Imidazoles Utilizing P2O5/SiO2 as a Reusable Catalyst

    Institute of Scientific and Technical Information of China (English)

    Shaterian, Hamid Reza; Ranjbar, Mohammad; Azizi, Kobra


    Phosphorus pentoxide supported on silica gel (P2O5/SiO2) has been used as an efficient and reusable catalyst for the one-pot pseudo four-component synthesis of 2,4,5-trisubstituted imidazoles from benzil or benzoin, aldehydes, and ammonium acetate. It was also used for four-component preparation of 1,2,4,5-tetrasubstituted imidazoles from benzil or benzoin, aldehydes, primary amine, and ammonium acetate under thermal solvent-free conditions. The remarkable features of this new procedure are high conversions, cleaner reaction, simple experimental and work-up procedures and also the catalyst can be easily separated from the reaction mixture and reused several times without any loss of its activity.

  19. Severe facial dermatitis as a late complication of aesthetic rhinoplasty; a case report

    Directory of Open Access Journals (Sweden)

    Sodaify Manoochehr


    Full Text Available Abstract Background Contact dermatitis, as a cutaneous complication after rhinoplasty, is of early onset, limited and transient. The cause of this dermatitis is irritant or allergic. Late onset skin complications are rare and non-inflammatory. Case presentation We are reporting an unexpected, severe allergic contact dermatitis of the face, in a young female, appearing one month following aesthetic rhinoplasty. She failed to respond to ordinary treatments for dermatitis. We did standard battery – including nitrofurazone, tincture of benzoin and hydrocortisone – patch test for the patient that showed sensitivity to benzoin and corticosteroid. Conclusions In summary we report a case of a severe allergic contact dermatitis of the face, in a 21-year-old girl who underwent corrective aesthetic rhinoplasty, appearing one month following surgical operation. We were unable to find a similar report in the medical literature.

  20. A novel polymeric catalyst for the one-pot synthesis of 2,4,5-triaryl-1H-imidazoles

    Indian Academy of Sciences (India)

    Ali Mohammadi; Hossein Keshvari; Reza Sandaroos; Hamed Rouhi; Zeinalabedin Sepehr


    An efficient synthesis of 2,4,5-trisubstituted imidazoles is achieved by three component cyclocondensation of benzil or benzoin, aldehyde and ammonium acetate by using novel polymeric catalyst [poly(AMPS-co-AA)] under solvent-free conditions. The key advantages of this process are high yields, shorter reaction times, easy work-up, purification of products by non-chromatographic method and the reusability of the catalyst.

  1. Organic chemistry experiment

    Energy Technology Data Exchange (ETDEWEB)

    Mun, Seok Sik


    This book deals with organic chemistry experiments, it is divided five chapters, which have introduction, the way to write the experiment report and safety in the laboratory, basic experiment technic like recrystallization and extraction, a lot of organic chemistry experiments such as fischer esterification, ester hydrolysis, electrophilic aromatic substitution, aldol reaction, benzoin condensation, wittig reaction grignard reaction, epoxidation reaction and selective reduction. The last chapter introduces chemistry site on the internet and way to find out reference on chemistry.

  2. Mechanism of benzaldehyde lyase studied via thiamin diphosphate-bound intermediates and kinetic isotope effects. (United States)

    Chakraborty, Sumit; Nemeria, Natalia; Yep, Alejandra; McLeish, Michael J; Kenyon, George L; Jordan, Frank


    Direct spectroscopic observation of thiamin diphosphate-bound intermediates was achieved on the enzyme benzaldehyde lyase, which carries out reversible and highly enantiospecific conversion of ( R)-benzoin to benzaldehyde. The key enamine intermediate could be observed at lambda max 393 nm in the benzoin breakdown direction and in the decarboxylase reaction starting with benzoylformate. With benzaldehyde as substrate, no intermediates could be detected, only formation of benzoin at 314 nm. To probe the rate-limiting step in the direction of ( R)-benzoin synthesis, the (1)H/ (2)H kinetic isotope effect was determined for benzaldehyde labeled at the aldehyde position and found to be small (1.14 +/- 0.03), indicating that ionization of the C2alphaH from C2alpha-hydroxybenzylthiamin diphosphate is not rate limiting. Use of the alternate substrates benzoylformic and phenylpyruvic acids (motivated by the observation that while a carboligase, benzaldehyde lyase could also catalyze the slow decarboxylation of 2-oxo acids) enabled the observation of the substrate-thiamin covalent intermediate via the 1',4'-iminopyrimidine tautomer, characteristic of all intermediates with a tetrahedral C2 substituent on ThDP. The reaction of benzaldehyde lyase with the chromophoric substrate analogue ( E)-2-oxo-4(pyridin-3-yl)-3-butenoic acid and its decarboxylated product ( E)-3-(pyridine-3-yl)acrylaldehyde enabled the detection of covalent adducts with both. Neither adduct underwent further reaction. An important finding of the studies is that all thiamin-related intermediates are in a chiral environment on benzaldehyde lyase as reflected by their circular dichroism signatures.

  3. Dressing spray enhances the adhesive strength of surgical dressing tapes

    Directory of Open Access Journals (Sweden)

    Sarifakioglu Evren


    Full Text Available Background: The use of surgical adhesive tapes after minor surgical and dermatologic operations is widespread. Their use reduces the wound tension and separation and they ultimately improve the postoperative scar. The most commonly used wound adhesives to enhance the adhesiveness of the surgical tapes, are tincture of benzoin and mastisol. Aim: The purpose of the present study is to demonstrate the role of adhesive power of dressing spray with the adhesive tape application on the skin, which is widely used in clinics after the skin closure. Methods: Fifteen volunteers who were chosen among the medical personnel of the hospital comprised the study group. The skin of the flexor aspect of the 1/3 middle forearm of the subjects was used as the procedure region. The data is collected in the first, second and eighth days of the study. At the first stage of the study, an adhesive wound closure tape was applied to the skin without any compound of adhesives (group A. In the second and third stages, a thin coat of transparent film dressing spray (group B and an adhesive compound of tincture of benzoin (group C were applied to the skin before the adhesive tape placement, respectively. Different values of weights ranging between 50-900 gm were hanged by hooking into the center of the adhesive tape. The weights that caused complete separations of the tape from the skin after exactly 20 seconds were recorded in all groups. The data was analyzed by using Friedman test in order to calculate statistical significance between groups A, B and C. Results: The difference in adhesive power between control and groups B and C was found to be highly significant ( p < 0.05. Compound tincture of benzoin was observed to have greatest adhesive strength. Transparent film dressing spray was not as efficient as tincture of benzoin, but when compared with the control group, it enhanced the tape adhesion by 2-fold. Conclusion: The results indicated that dressing spray tested has

  4. Rapid Preparation of Monolithic Columns for Capillary Electrochromatography Separation

    Institute of Scientific and Technical Information of China (English)

    Wen Jun GONG; Yi Jun ZHANG; Yu Ping ZHANG; Seong Ho CHOI


    Fritless packed silica gel columns were prepared using sol-gel technology. The part of a75 μm i.d. capillary was filled with a mixture of methacryloxypropyltrimethoxysilane, toluene and hydrochloric acid. Four different photoinitiators such as benzoin methyl ether, Irgacure 819,Irgacure 1700 and irgacure 1800 were added in the presence or absence of sodium dodecyl sulfate during the polymerization process. The above eight solutions were irradiated at 365 nm about5-10 min to prepare the porous monolithic sol-gel columns by a one-step process.

  5. Redox Switching of Orthoquinone-Containing Aromatic Compounds with Hydrogen and Oxygen Gas. (United States)

    Urakawa, Kazuki; Sumimoto, Michinori; Arisawa, Mitsuhiro; Matsuda, Masaki; Ishikawa, Hayato


    Unique redox switching of orthoquinone-containing pentacyclic aromatic compounds with molecular hydrogen and oxygen in the presence of a palladium nanoparticle catalyst (SAPd) is disclosed. These molecules were predicted by in silico screening before synthesis. Efficient protocols for the synthesis of orthoquinone-containing aromatic compounds by palladium-mediated homocoupling and the benzoin condensation reaction were developed. Clear switching between orthoquinone and aromatic hydroquinone compounds was observed on the basis of their photoluminescence properties. Furthermore, the twist strain of the orthoquinone moiety could induce dramatic changes in color and emission.

  6. 1-Azadienes as regio- and chemoselective dienophiles in aminocatalytic asymmetric Diels-Alder reaction. (United States)

    Ma, Chao; Gu, Jing; Teng, Bin; Zhou, Qing-Qing; Li, Rui; Chen, Ying-Chun


    Electron-deficient 1-aza-1,3-butadienes containing a 1,2-benzoisothiazole-1,1-dioxide or 1,2,3-benzoxathiazine-2,2-dioxide motif act as regio- and chemoselective dienophiles in normal-electron-demand Diels-Alder reactions with HOMO-raised trienamines, rather than typical 4π-participation in inverse-electron-demand versions. The enantioenriched cycloadducts could be efficiently converted to spiro or fused frameworks with high structural and stereogenic complexity by a sequential aza-benzoin reaction or other transformations.

  7. Preparation, Characterization, and Catalytical Application of MgCoAl-Hydrotalcite-Like Compounds

    Institute of Scientific and Technical Information of China (English)

    Kai Yan; Xianmei Xie; Jinping Li; Xiulan Wang; Zhizhong Wang


    MgCoAl-hydrotalcite-like compounds (MgCoAl-HTLcs) were synthesized using the copre-cipitation method of variable pH values. The effect of each factor on the preparation of HTLcs was discussed systematically, which included pH values, mole ratios of Mg2+ to Co2+, the concentrations of the solution, and the temperature and time of the hydrothermal treatment. Besides, the thermal decomposition of MgCoAl-HTLcs was discussed. X-ray diffraction, thermogravimetric analysis, and FT-IR spectroscopy were performed to characterize the MgCoAl-HTLcs samples. The results showed that when the pH = 7.6-8.5 or 5.5-6.2, atomic ratios of (Mg2++Co2+)/Al3+ = 2 and Mg2+/Co2+ ranging from 1.00 to 2.00, temperature and time of hydrothermal treatment being 110 ℃ and 6 h, unique MgCoAl-HTLcs with high crystallinity could be obtained. When the calcination temperature was up to 250 ℃, the MgO phase was detected coexisting with Al2O3 and MgAl2O4 was highly spreaded on the derived mixed oxides. The synthesis reaction of benzoin methyl ether with methanol and benzaldehyde was chosen to study the catalytic activity of MgCoAl-HTLcs. The catalyst showed high activity and high stability in the synthesis of benzoin methyl ether in the feasible condition.

  8. Enantiomer separation by CEC——Enantiomer separation by packed-capillary electrochromatography

    Institute of Scientific and Technical Information of China (English)

    朱军; 邹汉法; 施维; 芮建中; 倪坚毅; 张玉奎


    Three chiral compounds were successfully separated in a short time with two enantiomer separation models on packed-capillary electrochromatography (CEC). (i) 75 μm I.D. capillaries were packed with 5 μm β-cyclodextrin (β-CD) chiral stationary phase (CSP). Effects of voltage, pH and concentration of organic modifier on electroosmotic flow (EOF) and chiral separations were investigated systematically. Enantiomers of a neutral compound (benzoin) and a neutral drug (mephenytoin) were separated within a short time with high efficiency. Efficiency of 32 000 theoretical plates per meter and resolution (R_s) of 1.42 were achieved for enantiomers of benzoin using a βCD packed column with 6.2 cm packed length. Efficiency of 45 000 theoretical plates per meter and R_s of 3.40 were obtained for enantiomers of mephenytoin. Especially, the enantiomer separation of mephenytion was performed in just 3.4 min with R_s of 2.60. (ⅱ) 75 μm I.D. capillary was packed with octadecylsilica particles (ODS). Chiral separat

  9. Heterofunctional Magnetic Metal-Chelate-Epoxy Supports for the Purification and Covalent Immobilization of Benzoylformate Decarboxylase From Pseudomonas Putida and Its Carboligation Reactivity. (United States)

    Tural, Servet; Tural, Bilsen; Demir, Ayhan S


    In this study, the combined use of the selectivity of metal chelate affinity chromatography with the capacity of epoxy supports to immobilize poly-His-tagged recombinant benzoylformate decarboxylase from Pseudomonas putida (BFD, E.C. via covalent attachment is shown. This was achieved by designing tailor-made magnetic chelate-epoxy supports. In order to selectively adsorb and then covalently immobilize the poly-His-tagged BFD, the epoxy groups (300 µmol epoxy groups/g support) and a very small density of Co(2+)-chelate groups (38 µmol Co(2+)/g support) was introduced onto magnetic supports. That is, it was possible to accomplish, in a simple manner, the purification and covalent immobilization of a histidine-tagged recombinant BFD. The magnetically responsive biocatalyst was tested to catalyze the carboligation reactions. The benzoin condensation reactions were performed with this simple and convenient heterogeneous biocatalyst and were comparable to that of a free-enzyme-catalyzed reaction. The enantiomeric excess (ee) of (R)-benzoin was obtained at 99 ± 2% for the free enzyme and 96 ± 3% for the immobilized enzyme. To test the stability of the covalently immobilized enzyme, the immobilized enzyme was reused in five reaction cycles for the formation of chiral 2-hydroxypropiophenone (2-HPP) from benzaldehyde and acetaldehyde, and it retained 96% of its original activity after five reaction cycles.

  10. Extended reaction scope of thiamine diphosphate dependent cyclohexane-1,2-dione hydrolase: from C-C bond cleavage to C-C bond ligation. (United States)

    Loschonsky, Sabrina; Wacker, Tobias; Waltzer, Simon; Giovannini, Pier Paolo; McLeish, Michael J; Andrade, Susana L A; Müller, Michael


    ThDP-dependent cyclohexane-1,2-dione hydrolase (CDH) catalyzes the CC bond cleavage of cyclohexane-1,2-dione to 6-oxohexanoate, and the asymmetric benzoin condensation between benzaldehyde and pyruvate. One of the two reactivities of CDH was selectively knocked down by mutation experiments. CDH-H28A is much less able to catalyze the CC bond formation, while the ability for CC bond cleavage is still intact. The double variant CDH-H28A/N484A shows the opposite behavior and catalyzes the addition of pyruvate to cyclohexane-1,2-dione, resulting in the formation of a tertiary alcohol. Several acyloins of tertiary alcohols are formed with 54-94 % enantiomeric excess. In addition to pyruvate, methyl pyruvate and butane-2,3-dione are alternative donor substrates for CC bond formation. Thus, the very rare aldehyde-ketone cross-benzoin reaction has been solved by design of an enzyme variant.

  11. Structure of the ThDP-dependent enzyme benzaldehyde lyase refined to 1.65 Å resolution

    Energy Technology Data Exchange (ETDEWEB)

    Maraite, Andy; Schmidt, Thomas; Ansörge-Schumacher, Marion B. [Department of Biotechnology, Faculty of Natural Sciences, RWTH Aachen University, Worringerweg 1, 52074 Aachen (Germany); Brzozowski, A. Marek; Grogan, Gideon, E-mail: [Structural Biology Laboratory, Department of Chemistry, University of York, Heslington, York YO10 5YW (United Kingdom); Department of Biotechnology, Faculty of Natural Sciences, RWTH Aachen University, Worringerweg 1, 52074 Aachen (Germany)


    The X-ray crystal structure of the ThDP-dependent enzyme benzaldehyde lyase has been refined to 1.65 Å. Benzaldehyde lyase (BAL; EC is a thiamine diphosphate (ThDP) dependent enzyme that catalyses the enantioselective carboligation of two molecules of benzaldehyde to form (R)-benzoin. BAL has hence aroused interest for its potential in the industrial synthesis of optically active benzoins and derivatives. The structure of BAL was previously solved to a resolution of 2.6 Å using MAD experiments on a selenomethionine derivative [Mosbacher et al. (2005 ▶), FEBS J.272, 6067–6076]. In this communication of parallel studies, BAL was crystallized in an alternative space group (P2{sub 1}2{sub 1}2{sub 1}) and its structure refined to a resolution of 1.65 Å, allowing detailed observation of the water structure, active-site interactions with ThDP and also the electron density for the co-solvent 2-methyl-2,4-pentanediol (MPD) at hydrophobic patches of the enzyme surface.

  12. Sensitive spectrophotometric determination of Co(II) using dispersive liquid-liquid micro-extraction method in soil samples. (United States)

    Hasanpour, Foroozan; Hadadzadeh, Hassan; Taei, Masoumeh; Nekouei, Mohsen; Mozafari, Elmira


    Analytical performance of conventional spectrophotometer was developed by coupling of effective dispersive liquid-liquid micro-extraction method with spectrophotometric determination for ultra-trace determination of cobalt. The method was based on the formation of Co(II)-alpha-benzoin oxime complex and its extraction using a dispersive liquid-liquid micro-extraction technique. During the present work, several important variables such as pH, ligand concentration, amount and type of dispersive, and extracting solvent were optimized. It was found that the crucial factor for the Co(II)-alpha benzoin oxime complex formation is the pH of the alkaline alcoholic medium. Under the optimized condition, the calibration graph was linear in the ranges of 1.0-110 μg L(-1) with the detection limit (S/N = 3) of 0.5 μg L(-1). The preconcentration operation of 25 mL of sample gave enhancement factor of 75. The proposed method was applied for determination of Co(II) in soil samples.

  13. Direct Electrochemical Synthesis and Crystal Structure of a New Mononuclear Copper(Ⅱ) Complex: [(bipy)2Cu(PhCOO)]ClO4·(benzil) (benzil = 1,2-Diphenyl-ethane-1,2-dione)

    Institute of Scientific and Technical Information of China (English)

    YUAN Ya-Xian; GU Ren-Ao; YAO Jian-Lin


    A new mononuclear copper(Ⅱ) complex [(bipy)2Cu(PhCOO)]ClO4·(benzil) (bipy=2,2'-bipyridine, benzil=1,2-diphenyl-ethane-1,2-dione) was synthesized by direct electrochemical oxidation of Cu electrode in an acetonitrile solution with benzoic acid, 2,2'-bipyridine and benzoin. As soon as the current flowed in the cell, benzoin was oxidized to benzil quickly. The crystal structure was determined by X-ray diffraction. It belongs to monoclinic system, space group P21/c with a=14.860(2), b=20.784(3), c=11.9150(17) (A), β=101.401(3)°, V=3607.3(9) (A)3, Z=4, Mr=806.69, Dc=1.485 g/cm3, F(000)=1660, μ=0.742 mm-1, R=0.0788 and wR=0.1519 for 6254 observed reflections (Ⅰ > 2σ(Ⅰ)). The complex contains a mononuclear [(bipy)2Cu(PhCOO)]+ cation, a solvate benzil molecule and a ClO4- anion which locates around the cation outside acting as the counter ion. The Cu(Ⅱ) ion is coordinated by two 2,2'-bipyridines and one benzoato ligand to form a distorted square-pyramid.

  14. X-ray diffraction, FTIR, UV-VIS and SEM studies on chromium (III) complexes

    Energy Technology Data Exchange (ETDEWEB)

    Mishra, Ashutosh; Dwivedi, Jagrati, E-mail:; Shukla, Kritika [School of Physics, Devi Ahilya University, Khandwa Road, Indore-452001 (India)


    Five Chromium (III) complexes have been prepared using Schiff base ligands which derived from benzoin and five different amino acids (H{sub 2}N-R). Samples were characterized by XRD, FTIR, UV-VIS and SEM method. X-Ray diffraction pattern analyzed that all chromium (III) complexes have hexagonal structure and crystalline, in nature, using Bruker D8 Advance instrument. Using VERTAX 70, FTIR spectroscopy reveals that Samples have (C=N), (C-O), (M-N) and (M-O) bonds in the range of 4000-400cm{sup −1}. UV-VIS spectroscopy give information that samples absorb the visible light which is in the range of 380-780nm. For this, Lambda 960 spectrometer used. SEM is designed for studying of the solid objects, using JEOL JSM 5600 instrument.

  15. Bactericidal Activity of Oleo-gum Resins Doped with Metal Oxides

    Directory of Open Access Journals (Sweden)

    MSc Diogo José Horst


    Full Text Available This work aimed to evaluate the bactericidal activity of vegetable oil-gum resins (Styrax benzoin, Commiphora mirrha, and Boswellia papyrifera doped with metal oxides (TiO2, P25, MoO3 e Cu2O in nanometric dimension. The in vitro susceptibility of pathogenic Gram-negative bacteria E. coli was accessed. The antibiogram essay was performed using the semi-quantitative method Kirby-Bauer (KB agar diffusion test. The materials obtained were characterized by ultraviolet visible (UV-Vis spectrophotometry, additionally; its morphology was characterized by scanning electron microscopy (SEM. The results show that in most cases the materials present bactericidal activity, thereby inhibiting both planktonic and surface associated growth of this microorganism.

  16. Efficient white light generation from 2,3-diphenyl-1,2-dihydro-quinoxaline complex (United States)

    Dwivedi, Y.; Kant, S.; Rai, R. N.; Rai, S. B.


    In this article, we report two organic materials dispersed in transparent poly (methyl methacrylate) matrix for efficient white light simulation under different optical excitations. A newly synthesized complex of benzoin and o-phenyldiamine is observed to be white on illumination with a blue LED. A new concept of white light emitting tube is also demonstrated. A mixture of 2,2″-([1,1'-biphenyl]-4,4'-diyldi-2,1-ethenediyl)-bis-benzenesulfonic acid disodium salt and complex is optimized to emit white light extended in the violet region on 355 nm laser excitation. The optical quality of the emitted white light is adjudged by the CIE coordinate, correlated color temperature and color rendition index in both the cases.

  17. NHC–metal complexes based on benzimidazolium moiety for chemical transformation

    Directory of Open Access Journals (Sweden)

    Prashant Narayan Muskawar


    Full Text Available N-heterocyclic carbenes (NHC are now commonly encountered in organometallic and inorganic coordination chemistry because of its environmental friendly nature as solvent and catalyst, high activity, selectivity and easily recovered materials that were used to replace the traditional volatile organic solvents which generally suffered from environmental problems. Benzimidazole based ionic liquids (BILs offering a new possibility for developing environmentally-friendly basic catalyst with transition metal and non-transition metal (Ag, Au, Ru, Rh, Fe, Co, Cu, Cd and Pd. They are flexible, nonvolatile, noncorrosive and immiscible with many organic solvents. In this review, we wish to present an overview of the preparation and applications in various reactions like alkylation, arylation, etherification, benzoin reaction, aldol condensation and metal mediated catalyst in Suzuki, Suzuki–Miyaura, Heck cross coupling and reduction, also in electrochemical application (electrocatalyst, anion sensor, solar cell, proton conduction, malaria parasite, antimicrobial activity, etc.

  18. Curing of Epoxy Resin Induced by Femtosecond Laser Pulse

    Institute of Scientific and Technical Information of China (English)

    LI Yubin; ZHANG Zuoguang


    The possibility of curing of epoxy resin induced by femtosecond laser beam was explored through choosing different initiators . Absorption spectroscopy, infrared spectroscopy (IR), stereomicroscopy and scanning electron microscopy (SEM) were applied to analyze the structure of epoxy resin systems after irradiation with a femtosecond laser beam. The experimental results show that the epoxy resin systems containing diaryliodonium salts can be cured by irradiation of Jemtosecond laser pulse, while the systems containing benzoin can not be cured. It is found that diaryliodonium salts decompose under the irradiation of femtosecond laser pulse through multi ( two ) -photon absorption, initiating the ring-opening polymerization of epoxy resin. And the appearance of cured area has a sheet structure consisting of many tiny lamellar structures.

  19. Synthesis of Some New Benzimidazole Derivatives of Pharmaceutical Interest

    Directory of Open Access Journals (Sweden)

    Fawzia Zakaria El-Ablack


    Full Text Available Reaction of 2-(aminomethylbenzimidazole dihydrochloride (1 with ethyl acetoacetate was studied to give diazepinone-benzimidazole derivative (2, while, treatment of 1 with phenylhydrazono ethylacetoacetate afforded phenylhydrazino diazepinone derivative (3. On the other hand, reaction of 1 with acetyl acetone resulted in the formation of diazepine derivative (4. The reaction of 1 with ethyl cyanoacetate was studied to give 3-aminodiazepinone derivative (5. Also the reaction of 1 with acetophenone and/or benzophenone has been investigated to give the fused imidazolines 6 and 7 respectively, while the reaction of 1 with cyclopentanone gave benzimidazolyl derivative (8. Treatment of 1 with chloroacetyl chloride gave the fused pyrazinone (9. The treatment of 1 with benzoin gave the derivative (10. The structures of the hitherto unknown compounds have been confirmed from analytical and spectral data. The newly synthesized compounds were screened for antibacterial and antifungal activity.

  20. Catalytic scope of the thiamine-dependent multifunctional enzyme cyclohexane-1,2-dione hydrolase. (United States)

    Loschonsky, Sabrina; Waltzer, Simon; Fraas, Sonja; Wacker, Tobias; Andrade, Susana L A; Kroneck, Peter M H; Müller, Michael


    The thiamine diphosphate (ThDP)-dependent enzyme cyclohexane-1,2-dione hydrolase (CDH) was expressed in Escherichia coli and purified by affinity chromatography (Ni-NTA). Recombinant CDH showed the same C-C bond-cleavage and C-C bond-formation activities as the native enzyme. Furthermore, we have shown that CDH catalyzes the asymmetric cross-benzoin reaction of aromatic aldehydes and (decarboxylated) pyruvate (up to quantitative conversion, 92-99 % ee). CDH accepts also hydroxybenzaldehydes and nitrobenzaldehydes; these previously have not (or only in rare cases) been known as substrates of other ThDP-dependent enzymes. On a semipreparative scale, sterically demanding 4-(tert-butyl)benzaldehyde and 2-naphthaldehyde were transformed into the corresponding 2-hydroxy ketone products in high yields. Additionally, certain benzaldehydes with electron withdrawing substituents were identified as potential inhibitors of the ligase activity of CDH.

  1. Fast preparation of photopolymerized monolithic columns for capillary electrochromatography

    Institute of Scientific and Technical Information of China (English)

    GONG Wen-jun; XU Guang-ri; ZHANG Yi-jun; ZHANG Yu-ping; CHOI Seong-ho; LEE Kwang-pill


    Photopolymerized sol-gel(PSG) columns were prepared using methacryloxypropyltrimethoxysilane as the monomer,toluene as the porogen and hydrochloric acid as the catalyst. Four different photoinitiators such as benzoin methyl ether, Irgacure 819,lrgacure 1700 and Irgacure 1800 were comparatively used in the reaction solution in the presence and absence of sodium dodecylsulfate. The above eight solutions were respectively irradiated at 365 um for 5-10 min in each capillary (75 μm inside diameter) toprepare the porous monolithic sol-gel column by a one-step, in situ, process. The chromatographic behavior of the eight PSGcolumns were comparatively studied, all of which exhibit reversed-phase character. Using these columns, several neutral compounds,namely thiourea, benzene, toluene, ethyl benzene, biphenyl and naphthalene can be separated from mixtures with a largest columnefficiency of 74 470 plate/column for thiourea. Addition of sodium dodecyl sulfate in the polymerization process has a significantinfluence on the morphology and migration time.

  2. Production, properties and application to biocatalysis of a novel extracellular alkaline phenol oxidase from the thermophilic fungus Scytalidium thermophilum. (United States)

    Ogel, Z B; Yüzügüllü, Y; Mete, S; Bakir, U; Kaptan, Y; Sutay, D; Demir, A S


    Scytalidium thermophilum produces an extracellular phenol oxidase on glucose-containing medium. Certain phenolic acids, specifically gallic acid and tannic acid, induce the expression of the enzyme. Production at 45 degrees C in batch cultures is growth-associated and is enhanced in the presence of 160 microM CuSO4 x 5 H2O and 3 mM gallic acid. The highest enzyme activity is observed at pH 7.5 and 65 degrees C, on catechol. When incubated for 1 h at pH 7 and pH 8, 95% and 86% of the activity is retained. Thermostability decreases gradually from 40 degrees C to 80 degrees C. Estimated molecular mass is c. 83 kDa, and pI is acidic at c. 5.4. Substrate specificity and inhibition analysis in culture supernatants suggest that the enzyme has unique properties showing activity towards catechol; 3,4-dihydroxy-L-phenylalanine (L-DOPA); 4-amino-N, N-diethylaniline (ADA); p-hydroquinone; gallic acid; tannic acid and caffeic acid, and no activity towards L-tyrosine, guaiacol, 2,2'-azino-bis(3-ethyl-benzthiazoline-6-sulphonic acid) (ABTS) and syringaldazine. Inhibition is observed in the presence of salicyl hydroxamic acid (SHAM) and p-coumaric acid. Enzyme activity is enhanced by cetyltrimethylammonium bromide (CTAB) and polyvinylpyrrolidone (PVP), and the organic solvents dimethyl sulfoxide (DMSO) and ethanol. No inhibition is observed in the presence of carbon monoxide. Benzoin, benzoyl benzoin and hydrobenzoin are converted into benzil, and stereoselective oxidation is observed on hydrobenzoin. The reported enzyme is novel due to its catalytic properties resembling mainly catechol oxidases, but displaying some features of laccases at the same time.

  3. Metal chloride hydrates as Lewis acid catalysts in multicomponent synthesis of 2,4,5-triarylimidazoles or 2,4,5-triaryloxazoles

    Energy Technology Data Exchange (ETDEWEB)

    Marques, Marcelo V. [Departamento de Engenharia de Processos, Fundacao de Ciencia e Tecnologia, Cachoeirinha, RS (Brazil); Russowsky, Dennis, E-mail: [Laboratorio de Sinteses Organicas, Instituto de Quimica, Universidade Federal do Rio Grande do Sul, Porto Alegre-RS (Brazil); Ruthner, Marcelo M.; Fontoura, Luiz A.M. [Curso de Quimica, Universidade Luterana do Brasil, Canoas, RS (Brazil)


    A series of nine metal chloride hydrates (ZnCl{sub 2}.2H{sub 2}O, SnCl{sub 2}.2H{sub 2}O, CdCl{sub 2}.2H{sub 2}O, MnCl{sub 2}.4H{sub 2}O, CoCl{sub 2}.6H{sub 2}O, SrCl{sub 2}.6H{sub 2}O, NiCl{sub 2}.6H{sub 2}O, CrCl{sub 3}.6H{sub 2}O and CeCl{sub 3}.7H{sub 2}O) was investigated as mild and inexpensive Lewis acid catalysts to promote the multicomponent synthesis of triarylimidazoles. Reactions starting from benzil showed the best results when SnCl{sub 2}.2H{sub 2}O was used, while for benzoin as the starting material, CeCl{sub 3}.7H{sub 2}O was more efficient. All reactions were performed in EtOH as solvent. These catalysts were also successfully employed in the synthesis of triaryloxazoles. (author)

  4. Preparation of a crosslinked bioimprinted lipase for enrichment of polyunsaturated fatty acids from fish processing waste. (United States)

    Yan, Jinyong; Li, Lifan; Tang, Qianli; Jiang, Manzhou; Jiang, Shenzhou


    Geotrichum sp. lipase modified with a combined method composed of crosslinking and bioimprinting was employed to selectively hydrolyze waste fish oil for enrichment of eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA) in glycerides. Crosslinked polymerization by monomer (polyethylene glycol 400 dimethyl acrylate), crosslinker (trimethylolpropane trimethylacrylate), and photoinitiator (benzoin methyl ether) coupled to bioimprinting using palmitic acid as imprint molecule, resulted in much more effective enzyme preparation used in aqueous hydrolysis reaction. Since the crosslinked polymerization modification maintained bioimprinted property and gave good dispersion of enzyme in reaction mixture, the crosslinked bioimprinted enzyme exhibited higher hydrolysis temperature, enhanced specific activity, shorter hydrolysis time, and better operational stability compared to free lipase. Crude fish oil was treated at 45 degrees C with this crosslinked bioimprinted lipase for 8 h, and 46% hydrolysis degree resulted in the production of glycerides containing 41% of EPA and DHA (EPA+DHA), achieving 85.7% recovery of initial EPA and DHA. The results suggested that bioimprinted enzymes did not lose their induced property in aqueous environment when prepared according to the described crosslinking-bioimprinting method. It could also be seen that the crosslinked bioimprinted lipase was effective in producing glycerides that contained a higher concentration of polyunsaturated fatty acid with better yield.

  5. True and common balsams

    Directory of Open Access Journals (Sweden)

    Dayana L. Custódio


    Full Text Available Balsams have been used since ancient times, due to their therapeutic and healing properties; in the perfume industry, they are used as fixatives, and in the cosmetics industry and in cookery, they are used as preservatives and aromatizers. They are generally defined as vegetable material with highly aromatic properties that supposedly have the ability to heal diseases, not only of the body, but also of the soul. When viewed according to this concept, many substances can be considered balsams. A more modern concept is based on its chemical composition and origin: a secretion or exudate of plants that contain cinnamic and benzoic acids, and their derivatives, in their composition. The most common naturally-occurring balsams (i.e. true balsams are the Benzoins, Liquid Storaque and the Balsams of Tolu and Peru. Many other aromatic exudates, such as Copaiba Oil and Canada Balsam, are wrongly called balsam. These usually belong to other classes of natural products, such as essential oils, resins and oleoresins. Despite the understanding of some plants, many plants are still called balsams. This article presents a chemical and pharmacological review of the most common balsams.

  6. Biochemical and structural characterization of recombinant short-chain NAD(H)-dependent dehydrogenase/reductase from Sulfolobus acidocaldarius highly enantioselective on diaryl diketone benzil. (United States)

    Pennacchio, Angela; Sannino, Vincenzo; Sorrentino, Giosuè; Rossi, Mosè; Raia, Carlo A; Esposito, Luciana


    The gene encoding a novel alcohol dehydrogenase that belongs to the short-chain dehydrogenases/reductases superfamily was identified in the aerobic thermoacidophilic crenarchaeon Sulfolobus acidocaldarius strain DSM 639. The saadh2 gene was heterologously overexpressed in Escherichia coli, and the resulting protein (SaADH2) was purified to homogeneity and both biochemically and structurally characterized. The crystal structure of the SaADH2 NADH-bound form reveals that the enzyme is a tetramer consisting of identical 27,024-Da subunits, each composed of 255 amino acids. The enzyme has remarkable thermophilicity and thermal stability, displaying activity at temperatures up to 80 °C and a 30-min half-inactivation temperature of ∼88 °C. It also shows good tolerance to common organic solvents and a strict requirement for NAD(H) as the coenzyme. SaADH2 displays a preference for the reduction of alicyclic, bicyclic and aromatic ketones and α-ketoesters, but is poorly active on aliphatic, cyclic and aromatic alcohols, showing no activity on aldehydes. Interestingly, the enzyme catalyses the asymmetric reduction of benzil to (R)-benzoin with both excellent conversion (98 %) and optical purity (98 %) by way of an efficient in situ NADH-recycling system involving a second thermophilic ADH. The crystal structure of the binary complex SaADH2-NADH, determined at 1.75 Å resolution, reveals details of the active site providing hints on the structural basis of the enzyme enantioselectivity.

  7. Scalability of the LEU-Modified Cintichem Process: 3-MeV Van de Graaff and 35-MeV Electron Linear Accelerator Studies

    Energy Technology Data Exchange (ETDEWEB)

    Rotsch, David A. [Argonne National Lab. (ANL), Argonne, IL (United States). Nuclear Engineering Division; Brossard, Tom [Argonne National Lab. (ANL), Argonne, IL (United States). Nuclear Engineering Division; Roussin, Ethan [Argonne National Lab. (ANL), Argonne, IL (United States). Nuclear Engineering Division; Quigley, Kevin [Argonne National Lab. (ANL), Argonne, IL (United States). Nuclear Engineering Division; Chemerisov, Sergey [Argonne National Lab. (ANL), Argonne, IL (United States). Nuclear Engineering Division; Gromov, Roman [Argonne National Lab. (ANL), Argonne, IL (United States). Nuclear Engineering Division; Jonah, Charles [Argonne National Lab. (ANL), Argonne, IL (United States). Nuclear Engineering Division; Hafenrichter, Lohman [Argonne National Lab. (ANL), Argonne, IL (United States). Nuclear Engineering Division; Tkac, Peter [Argonne National Lab. (ANL), Argonne, IL (United States). Nuclear Engineering Division; Krebs, John [Argonne National Lab. (ANL), Argonne, IL (United States). Nuclear Engineering Division; Vandegrift, George F. [Argonne National Lab. (ANL), Argonne, IL (United States). Nuclear Engineering Division


    Molybdenum-99, the mother of Tc-99m, can be produced from fission of U-235 in nuclear reactors and purified from fission products by the Cintichem process, later modified for low-enriched uranium (LEU) targets. The key step in this process is the precipitation of Mo with α-benzoin oxime (ABO). The stability of this complex to radiation has been examined. Molybdenum-ABO was irradiated with 3 MeV electrons produced by a Van de Graaff generator and 35 MeV electrons produced by a 50 MeV/25 kW electron linear accelerator. Dose equivalents of 1.7–31.2 kCi of Mo-99 were administered to freshly prepared Mo-ABO. Irradiated samples of Mo-ABO were processed according to the LEU Modified-Cintichem process. The Van de Graaff data indicated good radiation stability of the Mo-ABO complex up to ~15 kCi dose equivalents of Mo-99 and nearly complete destruction at doses >24 kCi Mo-99. The linear accelerator data indicate that even at 6.2 kCi of Mo-99 equivalence of dose, the sample lost ~20% of Mo-99. The 20% loss of Mo-99 at this low dose may be attributed to thermal decomposition of the product from the heat deposited in the sample during irradiation.

  8. 聚合物微球支载手性磺酰二胺的合成研究%Synthesis of microgels polystyrene supported chiral tosylated diamine

    Institute of Scientific and Technical Information of China (English)

    邓佳; 卢翠芬; 杨桂春; 陈祖兴


    以苯甲醛为原料,经安息香缩合、氧化、成环、还原、手性拆分、磺酰化反应制备含有双键的手性磺酰二胺分子,与苯乙烯和二乙烯基苯共聚制备聚苯乙烯支载手性磺酰二胺微球,总产率8.1%.用IR,1H NMR,13C NMR及元素分析对其结构进行表征,波谱解析结果与化合物结构相符.%A chiral tosylated diamines was synthesized by six steps using benzaldehyde as the initiating material, including benzoin condensation, oxygenization, cyclization reactions, reduction, chiral separation, sulfonylation, and then it was copolymerized with styrene and divinyl benzene to obtain microgels polystyrene supported chiral tosylated diamine in 8.1% overall yield. All the intermediate product was characterized by IR, 'H NMR,13C NMR and elemental analysis. The spectrum analytical results were consistent with the compound structure.

  9. Homogeneous liquid-liquid extraction method for the selective separation and preconcentration of ultra trace molybdenum. (United States)

    Ghiasvand, A R; Shadabi, S; Mohagheghzadeh, E; Hashemi, P


    A new simple and efficient homogeneous liquid-liquid extraction method for the selective separation and preconcentration of molybdenyl ions was developed. alpha-Benzoin oxime (ABO) was investigated as a complexing ligand, and perfluorooctanoate ion (PFOA(-)) was applied as a phase-separator agent under strongly acidic conditions. Under the optimal conditions ([ABO]=2.1x10(-3)M, [PFOA(-)]=1.8x10(-2)M, [HNO(3)]=1.7M, [acetone]=11.8% (v/v)), 10mug of molybdenum in 5ml aqueous phase could be extracted quantitatively into 40mul of the sedimented phase. The maximum concentration factor was 125-fold. Thiocyanate was applied as a chromogenic reagent for the direct spectrophotometric determination of molybdenum in the sedimented phase. The reproducibility of the proposed method is at the most 2.4%. The influence of the type and concentration of acid solution, the concentration of ABO, the type and volume of the water-miscible organic solvent, the concentration of PFOA(-), and the effect of different diverse ions on the extraction and determination of molybdenum(VI) were investigated. The proposed method was applied to the extraction and determination of molybdenum(VI) in natural water, Spinach, and Lucerne samples. A satisfactory agreement exists between the results obtained by the proposed method and those reported by GF-AAS.

  10. Probing the active center of benzaldehyde lyase with substitutions and the pseudosubstrate analogue benzoylphosphonic acid methyl ester. (United States)

    Brandt, Gabriel S; Nemeria, Natalia; Chakraborty, Sumit; McLeish, Michael J; Yep, Alejandra; Kenyon, George L; Petsko, Gregory A; Jordan, Frank; Ringe, Dagmar


    Benzaldehyde lyase (BAL) catalyzes the reversible cleavage of ( R)-benzoin to benzaldehyde utilizing thiamin diphosphate and Mg (2+) as cofactors. The enzyme is important for the chemoenzymatic synthesis of a wide range of compounds via its carboligation reaction mechanism. In addition to its principal functions, BAL can slowly decarboxylate aromatic amino acids such as benzoylformic acid. It is also intriguing mechanistically due to the paucity of acid-base residues at the active center that can participate in proton transfer steps thought to be necessary for these types of reactions. Here methyl benzoylphosphonate, an excellent electrostatic analogue of benzoylformic acid, is used to probe the mechanism of benzaldehyde lyase. The structure of benzaldehyde lyase in its covalent complex with methyl benzoylphosphonate was determined to 2.49 A (Protein Data Bank entry 3D7K ) and represents the first structure of this enzyme with a compound bound in the active site. No large structural reorganization was detected compared to the complex of the enzyme with thiamin diphosphate. The configuration of the predecarboxylation thiamin-bound intermediate was clarified by the structure. Both spectroscopic and X-ray structural studies are consistent with inhibition resulting from the binding of MBP to the thiamin diphosphate in the active centers. We also delineated the role of His29 (the sole potential acid-base catalyst in the active site other than the highly conserved Glu50) and Trp163 in cofactor activation and catalysis by benzaldehyde lyase.

  11. North American Lauraceae: terpenoid emissions, relative attraction and boring preferences of redbay ambrosia beetle, Xyleborus glabratus (coleoptera: curculionidae: scolytinae.

    Directory of Open Access Journals (Sweden)

    Paul E Kendra

    Full Text Available The invasive redbay ambrosia beetle, Xyleborus glabratus, is the primary vector of Raffaelea lauricola, a symbiotic fungus and the etiologic agent of laurel wilt. This lethal disease has caused severe mortality of redbay (Persea borbonia and swampbay (P. palustris trees in the southeastern USA, threatens avocado (P. americana production in Florida, and has potential to impact additional New World species. To date, all North American hosts of X. glabratus and suscepts of laurel wilt are members of the family Lauraceae. This comparative study combined field tests and laboratory bioassays to evaluate attraction and boring preferences of female X. glabratus using freshly-cut bolts from nine species of Lauraceae: avocado (one cultivar of each botanical race, redbay, swampbay, silkbay (Persea humilis, California bay laurel (Umbellularia californica, sassafras (Sassafras albidum, northern spicebush (Lindera benzoin, camphor tree (Cinnamomum camphora, and lancewood (Nectandra coriacea. In addition, volatile collections and gas chromatography-mass spectroscopy (GC-MS were conducted to quantify terpenoid emissions from test bolts, and electroantennography (EAG was performed to measure olfactory responses of X. glabratus to terpenoids identified by GC-MS. Significant differences were observed among treatments in both field and laboratory tests. Silkbay and camphor tree attracted the highest numbers of the beetle in the field, and lancewood and spicebush the lowest, whereas boring activity was greatest on silkbay, bay laurel, swampbay, and redbay, and lowest on lancewood, spicebush, and camphor tree. The Guatemalan cultivar of avocado was more attractive than those of the other races, but boring response among the three was equivalent. The results suggest that camphor tree may contain a chemical deterrent to boring, and that different cues are associated with host location and host acceptance. Emissions of α-cubebene, α-copaene, α-humulene, and

  12. Cintichem modified process - {sup 99}Mo precipitation step: application of statistical analysis tools over the reaction parameters

    Energy Technology Data Exchange (ETDEWEB)

    Teodoro, Rodrigo; Dias, Carla R.B.R.; Osso Junior, Joao A., E-mail: jaosso@ipen.b [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil); Fernandez Nunez, Eutimio Gustavo [Universidade de Sao Paulo (EP/USP), SP (Brazil). Escola Politecnica. Dept. de Engenharia Quimica


    Precipitation of {sup 99}Mo by {alpha}-benzoin oxime ({alpha}-Bz) is a standard precipitation method for molybdenum due the high selectivity of this agent. Nowadays, statistical analysis tools have been employed in analytical systems to prove its efficiency and feasibility. IPEN has a project aiming the production of {sup 99}Mo by the fission of {sup 235}U route. The processing uses as the first step the precipitation of {sup 99}Mo with {alpha}-Bz. This precipitation step involves many key reaction parameters. The aim of this work is based on the development of the already known acidic route to produce {sup 99}Mo as well as the optimization of the reactional parameters applying statistical tools. In order to simulate {sup 99}Mo precipitation, the study was conducted in acidic media using HNO{sub 3}, {alpha}Bz as precipitant agent and NaOH /1%H{sub 2}O{sub 2} as dissolver solution. Then, a Mo carrier, KMnO{sub 4} solutions and {sup 99}Mo tracer were added to the reaction flask. The reactional parameters ({alpha}-Bz/Mo ratio, Mo carrier, reaction time and temperature, and cooling reaction time before filtration) were evaluated under a fractional factorial design of resolution V. The best values of each reactional parameter were determined by a response surface statistical planning. The precipitation and recovery yields of {sup 99}Mo were measured using HPGe detector. Statistical analysis from experimental data suggested that the reactional parameters {alpha}-Bz/Mo ratio, reaction time and temperature have a significant impact on {sup 99}Mo precipitation. Optimization statistical planning showed that higher {alpha}Bz/Mo ratios, room temperature, and lower reaction time lead to higher {sup 99}Mo yields. (author)

  13. Synthesis, structure and theoretical investigation into a homoleptic tris(dithiolene) tungsten. (United States)

    Arifin, Khuzaimah; Minggu, Lorna Jeffery; Daud, Wan Ramli Wan; Yamin, Bohari M; Daik, Rusli; Kassim, Mohammad B


    A new homoleptic dithiolene tungsten complex, tris-{1,2-bis(3,5-dimethoxyphenyl)-1,2-ethylenodithiolene-S,S'}tungsten, was successfully synthesized via a reaction of the thiophosphate ester and sodium tungstate. The thiophosphate ester was prepared from 3,5-dimethoxybenzaldehyde via benzoin condensation to produce the intermediate 1,2-bis-(3,5-dimethoxyphenyl)-2-hydroxy-ethanone compound, followed by a reaction of the intermediate with phosphorus pentasulfide. FTIR, UV-Vis spectroscopy, 1H NMR and 13C NMR and elemental analysis confirmed the product as tris{1,2-bis-(3,5-dimethoxyphenyl)-1,2-ethylenodithiolene-S,S'}tungsten with the molecular formula of C54H54O12S6W. Crystals of the product adopted a monoclinic system with space group of P2(1)/n, where a=12.756(2) Å, b=21.560(3) Å, c=24.980(4) Å and β=103.998(3)°. Three thioester ligands were attached to the tungsten as bidentate chelates to form a distorted octahedral geometry. Density functional theory calculations were performed to investigate the molecular properties in a generalized-gradient approximation framework system using Perdew-Burke-Ernzerhof functions and a double numeric plus polarization basis set. The HOMO was concentrated on the phenyl ligands, while the LUMO was found along the W(S2C2)3 rings. The theoretical optical properties showed a slight blue shift in several low dielectric solvents. The solvatochromism effect was insignificant for high polar solvents.

  14. Eletroforese das proteínas do líqüido cefalorraquidiano na cisticercose do sistema nervoso central

    Directory of Open Access Journals (Sweden)

    A. Spina-França


    Full Text Available In order to analyse the paper strip electrophoresis contribution to the knowledge of cerebrospinal fluid (CSF proteins in cysticercosis of the central nervous system (CNS 40 patients were studied (identification data in table 1; the clinical forms and diagnostic data of 30 of them, who had CNS cysticercosis (cases 1 to 30 are summarized in the table 2; cysticercosis of the CNS might play a role in the pathologic condition presented by the remaining 10 patients. CSF protein fractions were examined in all the cases (results in tables 4 and 7 and those of blood sera in cases from 1 to 15 (results in table 5 by paper strip electrophoresis under the specifications previously reported54. A second examination of CSF protein fractions was made some time later in 4 cases (results in table 6. CSF samples were analysed also in respect to cytology, total protein content, Pandy and colloidal benzoin reactions and complement fixation tests for syphillis and cysticercosis (results in table 3. The values obtained for CSF protein fractions were compared to norma values found in 30 control subjects; these normal values were detailed in a prior publication55 and are summarized in table 8. This comparison shows that CNS cysticercosis produces changes in the electrophoretic prophiJe of CSF proteins (table 9; an increased y-globulin fraction was the main change observed, commonly associated to a low j8-globulin relative concentration. An inversion of a1/a2 quocient was found in 4 cases. The contributions to the study of CNS cysticercosis resulting from the electrophoretic analysis of CSF proteins are discussed in three groups: 1 - Informations obtained by paper electrophoresis of CSF proteins are independent from those resulting from the other laboratory aspects studied. Thus, if the protein fractions of blood sera are considered, although the changes found have mean values similar to those found to the CSF protein fractions (table 10, it was observed that there are

  15. Effect of alcohol aggregation on the retention factors of chiral solutes with an amylose-based sorbent: modeling and implications for the adsorption mechanism. (United States)

    Tsui, Hung-Wei; Franses, Elias I; Wang, Nien-Hwa Linda


    Various displacement models in the literature have been widely used for understanding the adsorption mechanisms of solutes in various chromatography systems. The models were used for describing the often-observed linear plots of the logarithms of the retention factor versus the logarithms of the polar modifier concentration CI(0). The slopes of such a plot was inferred to be equal to the number of the displaced modifier molecules upon adsorption of one solute molecule, and were generally found to be greater than 1. In this study, the retention factors of four structurally related chiral solutes, ethyl lactate (EL), methyl mandelate (MM), benzoin (B), and pantolactone (PL), were measured for the amylose tris[(S)-α-methylbenzylcarbamate] sorbent, or AS, as a function of the concentration of isopropanol (IPA) in n-hexane. With increasing IPA concentration CI(0), the slopes increase from less than 1, at a concentration range from 0.13 to 1.3M, to slightly more than 1 at higher concentrations. Such slopes cannot be explained by the conventional retention models. It was found previously for monovalent solutes that such slopes can only be explained when the aggregation of the mobile phase modifier, isopropyl alcohol, was accounted for. A new retention model is presented here, accounting for alcohol aggregation, multivalent solute adsorption, multivalent solute-alcohol complexation, alcohol adsorption, and solute intra hydrogen-bonding, which occur in these four solutes. The slope is found to be controlled by three key dimensionless groups, the fraction of the sorbent binding sites covered by IPA, the fraction of the solute molecules in complex form, and the fraction of the IPA molecules in aggregate form. The limiting slope at a very high IPA concentration is equal to the value of (x+y)/n, where x is the number of the solute-sorbent binding sites and y is the number of the alcohol molecules in the solute-alcohol complex, and n is the alcohol aggregation number. The model

  16. Group 4 Metalloporphyrin diolato Complexes and Catalytic Application of Metalloporphyrins and Related Transition Metal Complexes

    Energy Technology Data Exchange (ETDEWEB)

    Du, Guodong [Iowa State Univ., Ames, IA (United States)


    In this work, the first examples of group 4 metalloporphyrin 1,2-diolato complexes were synthesized through a number of strategies. In general, treatment of imido metalloporphyrin complexes, (TTP)M=NR, (M = Ti, Zr, Hf), with vicinal diols led to the formation of a series of diolato complexes. Alternatively, the chelating pinacolate complexes could be prepared by metathesis of (TTP)MCl2 (M = Ti, Hf) with disodium pinacolate. These complexes were found to undergo C-C cleavage reactions to produce organic carbonyl compounds. For titanium porphyrins, treatment of a titanium(II) alkyne adduct, (TTP)Ti(η2-PhC≡CPh), with aromatic aldehydes or aryl ketones resulted in reductive coupling of the carbonyl groups to produce the corresponding diolato complexes. Aliphatic aldehydes or ketones were not reactive towards (TTP)Ti(η2-PhC≡CPh). However, these carbonyl compounds could be incorporated into a diolato complex on reaction with a reactive precursor, (TTP)Ti[O(Ph)2C(Ph)2O] to provide unsymmetrical diolato complexes via cross coupling reactions. In addition, an enediolato complex (TTP)Ti(OCPhCPhO) was obtained from the reaction of (TTP)Ti(η2-PhC≡CPh) with benzoin. Titanium porphyrin diolato complexes were found to be intermediates in the (TTP)Ti=O-catalyzed cleavage reactions of vicinal diols, in which atmospheric oxygen was the oxidant. Furthermore, (TTP)Ti=O was capable of catalyzing the oxidation of benzyl alcohol and α-hydroxy ketones to benzaldehyde and α-diketones, respectively. Other high valent metalloporphyrin complexes also can catalyze the oxidative diol cleavage and the benzyl alcohol oxidation reactions with dioxygen. A comparison of Ti(IV) and Sn(IV) porphyrin chemistry was undertaken. While chelated diolato complexes were invariably obtained for titanium porphyrins on treatment with 1,2-diols, the reaction of vicinal diols with tin porphyrins gave a number of products, including mono

  17. Group 4 Metalloporphyrin diolato Complexes and Catalytic Application of Metalloporphyrins and Related Transition Metal Complexes

    Energy Technology Data Exchange (ETDEWEB)

    Guodong Du


    In this work, the first examples of group 4 metalloporphyrin 1,2-diolato complexes were synthesized through a number of strategies. In general, treatment of imido metalloporphyrin complexes, (TTP)M=NR, (M = Ti, Zr, Hf), with vicinal diols led to the formation of a series of diolato complexes. Alternatively, the chelating pinacolate complexes could be prepared by metathesis of (TTP)MCl{sub 2} (M = Ti, Hf) with disodium pinacolate. These complexes were found to undergo C-C cleavage reactions to produce organic carbonyl compounds. For titanium porphyrins, treatment of a titanium(II) alkyne adduct, (TTP)Ti({eta}{sup 2}-PhC{triple_bond}CPh), with aromatic aldehydes or aryl ketones resulted in reductive coupling of the carbonyl groups to produce the corresponding diolato complexes. Aliphatic aldehydes or ketones were not reactive towards (TTP)Ti({eta}{sup 2}-PhC{triple_bond}CPh). However, these carbonyl compounds could be incorporated into a diolato complex on reaction with a reactive precursor, (TTP)Ti[O(Ph){sub 2}C(Ph){sub 2}O] to provide unsymmetrical diolato complexes via cross coupling reactions. In addition, an enediolato complex (TTP)Ti(OCPhCPhO) was obtained from the reaction of (TTP)Ti({eta}{sup 2}-PhC{triple_bond}CPh) with benzoin. Titanium porphyrin diolato complexes were found to be intermediates in the (TTP)Ti=O-catalyzed cleavage reactions of vicinal diols, in which atmospheric oxygen was the oxidant. Furthermore, (TTP)Ti=O was capable of catalyzing the oxidation of benzyl alcohol and {alpha}-hydroxy ketones to benzaldehyde and {alpha}-diketones, respectively. Other high valent metalloporphyrin complexes also can catalyze the oxidative diol cleavage and the benzyl alcohol oxidation reactions with dioxygen. A comparison of Ti(IV) and Sn(IV) porphyrin chemistry was undertaken. While chelated diolato complexes were invariably obtained for titanium porphyrins on treatment with 1,2-diols, the reaction of vicinal diols with tin porphyrins gave a number of