舒巴坦钠合成工艺研究

以6-氨基青霉烷酸为起始原料，经重氮化、合成；溴化、氧化、还原、整个过程反应条件温成盐制备β-内酰胺酶抑制剂舒巴坦钠，精选出合适的工艺条件，提高了成品的收率，使总收率达72．4％；和，操作简单，适合大生产的要求。     

L-3-（1-萘基）-丙氨酸的LC—MS分析

L-3-（1-萘基）-丙氨酸（L-3-（1-Naphthyl）-alanine）是合成药物和多肽的中间体。目前国内不同厂家生产的L-3-（1-萘基）-丙氨酸的比例各不相同,造成产品的纯度有明显的差异,从而影响其合成产品的优劣和临床疗效,因此测定L-3-（1-萘基）-丙氨酸所占的比例对控制产品质量、保证临床疗效非常重要。文献已报道其含量测定方法为薄层色谱法和液相色谱法,均无法同时进行定性分析,该文建立的LC—MS法,为L-3-（1-萘基）-丙氨酸提供一种能同时定性和定量分析的新方法。     

γ-缩水甘油醚氧丙基三甲氧基硅烷合成工艺研究

评价了氯铂酸-异丙醇、氯铂酸-四氢呋喃体系在烯丙基缩水甘油醚和三甲氧基硅烷硅氢加成反应中的催化性能;重点进行了氯铂酸-异丙醇体系催化合成γ-缩水甘油醚氧丙基三甲氧基硅烷的工艺研究.其最佳工艺条件是催化剂:三甲氧基硅烷:烯丙基缩水甘油醚为1.42×10-5:1:1(物质的量),反应温度约85℃,反应时间60min,产物收率约72.58%.用傅立叶红外光谱对化合物进行了表征.     

生物可降解聚酯酰胺共聚物的设计、制备及表征

以直接熔融缩聚方法成功地制备了L-乳酸和α-丙氨酸聚酯酰胺共聚物,采用红外光谱、核磁共振、凝胶色谱、示差扫描量热仪和X射线衍射等方法对共聚物结构进行了分析表征,重点考察了投料比对产物组成、分子量及其热性能和结晶性能的影响,并对共聚物的降解性能进行了初步试验。随着α-丙氨酸含量的增加,相应共聚物的分子量明显下降,结晶性能下降直至变成无定形态。降解速率受共聚组分α-丙氨酸含量的控制,随之增加而加快,结果表明所制备的L-乳酸和α-丙氨酸聚酯酰胺共聚物具有良好的降解性能,是一种良好的药物缓释载体材料。     

钛氧酞菁的合成工艺研究

以钛酸四丁酯和1,3-二亚氨基异吲哚啉为原料,高收率地合成了钛氧酞菁(TiOPc).分别考察了原料处理方法、反应介质、反应物配比、酞酸四丁酯投料温度及反应时间对产物收率的影响,适宜的合成条件是粗品1,3-二亚氨基异吲哚啉经过w(NaOH)=0.5%的碱性溶液处理,以蒸馏干燥过的邻二氯苯为溶剂,投料比n(1,3-二亚氨基异吲哚啉):n(钛酸四丁酯)=3:1,回流反应3h,收率达到91.26%.     

环烷氧锡引发L-丙交酯的开环聚合

以环烷氧锡化合物引发L-丙交酯开环聚合制备高分子量聚L-乳酸。考察了单体引发剂配比、聚合温度和聚合时间等聚合条件对聚合产物特性黏度的影响。用1H-NMR、13C-NMR分析聚合产物微观结构表明,环烷氧锡引发L-丙交酯开环聚合是基于酰氧键断裂开环聚合的“配位-插入”机理。DSC、TGA、XRD等测试结果表明,所得聚L-乳酸具有较高的结晶度和立构规整度。     

替考拉宁手性膜拆分对羟基苯甘氨酸的研究

以聚砜膜为基膜,大环抗生素替考拉宁作为手性选择剂,1,6-己二异腈酸酯为交联剂,采用界面聚合法,制备具有手性选择性的替考拉宁-异腈酸酯聚砜复合膜。研究优化了单体摩尔比、聚合反应时间等制膜条件,渗析分离了D,L-对羟基苯甘氨酸.当D,L-对羟基苯甘氨酸的料液浓度为0.1mg/mL时,其对映体过剩值(e.e.)可达90.5%.     

2,6-二乙酰氨基吡嗪-1-氧化物硝化反应研究

研究了2,6-二乙酰氨基吡嗪-1-氧化物在硝硫混酸和发烟硝酸/酸性离子液体中的硝化反应。在混酸硝化体系中,考察了混酸硝化剂类型对产物2,6-二氨基-3,5-二硝基吡嗪-1-氧化物(LLM-105)收率和纯度的影响。在发烟硝酸/N,N,N-三甲基-N-丙磺酸基-硫酸氢铵(TMPSHSO4)硝化体系中,考察了在酸性离子液体催化条件下酸性离子液体使用量、硝解反应温度、酸性离子液体重复使用次数对LLM-105收率和纯度的影响。结果表明:混酸硝化体系中,2,6-二乙酰氨基吡嗪-1-氧化物的最佳硝化剂为KNO3和质量分数20%发烟硫酸,LLM-105的收率为72.5%,质量分数为98.6%。发烟硝酸/酸性离子液体硝化体系中,最佳反应条件为:TMPSHSO4与2,6-二乙酰氨基吡嗪-1-氧化物的物质的量的比为0.051.00,硝解温度为75℃,LLM-105收率为64.8%,质量分数为98.5%,TMPSHSO4经回收可重复使用3次。相对而言,以发烟硝酸/TMPSHSO4为硝化剂合成LLM-105更具优势。用1H NMR、IR和MS对LLM-105的结构进行了表征。     

甲基(γ-氯丙基)二氯硅烷的合成研究

以磷配体对氯铂酸硅氢加成催化剂进行改性,以γ-氯丙烯和甲基二氯氢硅为原料合成甲基(γ-氯丙基)二氯硅烷.探讨了该催化剂对硅氢加成反应的催化活性,较系统地研究了催化剂用量、配体与氯铂酸摩尔比、温度控制等因素对产品收率的影响.实验表明:氯铂酸-磷配体催化剂是合成甲基(γ-氯丙基)二氯硅烷的良好催化剂,在n(氯铂酸):n(磷配体)=1:3,催化剂用量为反应物料总摩尔数的1.5×10-5,一次投料方式,反应时间3.0h的优化条件下,甲基(γ-氯丙基)二氯硅烷的产率可达77.9%.     

L-丙交酯和聚L-乳酸的制备与性能

从左旋L-乳酸经高温催化反应得到低聚L-乳酸，再经高温裂解减压蒸馏制得单体L-丙交酯（LLA），理论收率高达80%以上。LLA经纯化，再以辛酸亚锡为催化剂开环聚合得到聚L-丙交酯（聚L-乳酸，PLLA），其粘均分子量可达到40万。     

Electrochemiluminescence of tris(8-hydroxyquinoline-5-sulfonic acid)aluminum(III) in aqueous solution

The electrochemiluminescence (ECL) of tris(8-hydroxyquinoline-5-sulfonic acid)aluminum(III) in aqueous solution is reported. ECL is generated by complexing aluminum ions with the chelating agent 8-hydroxyquinoline-5-sulfonic acid (HQS) to form Al(HQS)3, followed by oxidation in the presence of tri-n-propylamine (TPrA). The ECL intensity peaks a potential corresponding to oxidation of both TPrA and Al(HQS)3, and the ECL emission spectrum (lambda(max) = 499 nm) matches the photoluminescence emission spectrum, indicating that the emission is from a Al(HQS)3* excited state. ECL efficiencies (phi(ecl), photons generated per redox event) of 0.002 using Ru(bpy)3(2+) (phi(ecl) = 1) as relative standard. Conditions for ECL emission were optimized and used to generate a calibration curve that was linear over the 7 x 10(-6)-4 x 10(-4) M (5-281 mg/L (ppm)) range with a theoretical limit of detection of 1 ppm. The ECL of several metal ions other than aluminum with HQS and effects on Al(HQS)3 ECL were also examined.     

Stabilization of single-wall carbon nanotubes in fully sulfonated polyaniline

The interaction of single wall carbon nanotubes (SWNT) with an aqueous solution of the fully sulfonated polyaniline poly(2-methoxyaniline-5-sulfonic acid) (PMAS) and (+)-1-phenylethylamine (PhEA) has been investigated using spectroscopic methods. UV-vis spectral measurements show that the PMAS backbone undergoes conformational changes upon interaction with both SWNT and PhEA. Partial intercalation of PMAS into SWNTbundles was confirmed by Raman spectroscopy and electron microscopy.     

Facile electrosynthsis of poly (pyrene-1-sulfonic acid sodium salt) film: A good candidate for blue light-emitting diodes applications

Pyrene-1-sulfonic acid sodium salt (PyS) was chemically synthesized, and its polymer film, poly (pyrene-1-sulfonic acid sodium salt) (PPyS), was successfully electropolymerized by direct anodic oxidation both in aqueous and boron trifluoride diethyl etherate (BFEE) systems. The PPyS films showed good redox activity and structural stability even in SA. The impedance spectra of PPyS films indicated that the electron transfer resistance was about 23 Ω. The fluorescent result exhibited that the emission band of PPyS was red-shifed at least 76 nm in comparison with the monomer. Both the impedance and the fluorescent spectra demonstrated that the PPyS films were good semiconducting polymer and excellent blue-light-emitting materials, respectively.     

Fluorescence-based peptide labeling and fractionation strategies for analysis of cysteine-containing peptides

This study demonstrates that 1,5-I-AEDANS (5-({2-[(iodoacetyl)amino]ethyl}amino)naphthalene-1-sulfonic acid) can be used as a versatile fluorescence-based peptide quantification tool and provides readily interpretable tandem mass spectra for de novo peptide sequencing. Two AEDANS-cysteinyl-peptide fractionation strategies were evaluated. One AEDANS-cysteinyl-peptide fractionation strategy employs immobilized metal affinity chromatography (IMAC) to recover AEDANS-labeled peptides and reduce the complexity of peptide mixtures. In an alternate solid-phase approach, 1,5-I-AEDANS was coupled to an o-nitrobenzyl-based photocleavable resin to produce a resin that can label and isolate thiols and cysteine-containing peptides with a modified-AEDANS label (mAEDANS: 5-((4-amino-4-oxobutanoyl){2-[(iodoacetyl)amino]ethyl}amino)naphthalene-1-sulfonic acid). This fractionation protocol enriches cysteine-containing peptides more specifically than the IMAC strategy. Using micro-LC-ESI-MS with an on-line fluorescence detector and a Q-TOF mass spectrometer, we generated fluorescence-based elution profiles and corresponding positive ion mass spectra of AEDANS-labeled peptides. This study demonstrates that AEDANS-peptides produce positive ion ESI-MS mass spectra with detection limits comparable to those of the unlabeled peptide. Collision-induced dissociation (CID) of fluorescent AEDANS-peptides revealed readily interpretable product ion spectra with the label intact. Similar to the AEDANS-labeled peptide, an mAEDANS-labeled thiol is fluorescent and CID of a mAEDANS-labeled peptide also reveals an interpretable product ion spectrum with the label intact.     

Structural and ionization effects on the adsorption behaviors of some anilinic compounds from aqueous solution onto high-area carbon-cloth

The adsorption of anilinic compounds; aniline, p-toluidine, 1-napthylamine and sodium salt of diphenylamine-4-sulfonic acid from solutions in H₂O, in 1 M H₂SO₄ or in 0.1 M NaOH onto activated carbon-cloth was studied by in situ UV spectroscopy. A specially designed adsorption cell was used for this purpose. The adsorption processes were found to follow first-order kinetics and the rate constants were determined. The pH at the point of zero charge of the carbon-cloth surface was measured as 7.4. The highest rates and extents of adsorption were observed from H₂O solutions for aniline, p-toluidine and 1-napthylamine and from solution in 1 M H₂SO₄ for the sodium salt of diphenylamine-4-sulfonic acid. The adsorption behaviors of these four anilinic compounds in the three solutions (in H₂O, in 0.1 M NaOH and in 1 M H₂SO₄) were explained in terms of electrostatic and dispersion interactions between carbon-cloth surface and the anilinic species. The adsorption isotherm data for the anilinic compounds were derived at 30 °C and treated according to Langmuir and Freundlich models. The Freundlich model was found to represent the experimental isotherm data better than Langmuir model.     

Synthesis and characterization of processable multi-walled carbon nanotubes-sulfonated polydiphenylamine graft copolymers

Water soluble and processable nanocomposites composed of multi-walled carbon nanotubes (MWNTs) and poly(diphenylamine sulfonic acid) (PDPASA) are synthesized and characterized. Two types of methodologies are adopted. MWNTs are covalently functionalized with 2,5-diaminobenzene sulfonic acid (DABSA) and further in situ polymerized with diphenylamine-4-sulfonic acid (DPASA). This results in the formation of nanocomposites, MWNT(DABSA)-g-PDPASA, in which PDPASA is presented as the graft chains onto MWNTs. In another approach, DPASA is in situ polymerized in presence of unfunctionalized MWNTs, results in a nanocomposite in which MWNTs are present as entrapped mass in PDPASA matrix. Both nanocomposites are found to be water soluble and can form free standing films. The conductivity of MWNT(DABSA)-g-PDPASA and MWNT/PDPASA is found to be 1.25 mS x cm(-1) and 0.65 mS x cm(-1), respectively, which is higher than that of pristine PDPASA (0.25 x 10(-5) S x cm(-1)). The nanocomposites are characterized for their structure, morphology, optical and thermal properties.     

Immobilisation of fully sulfonated polyaniline on nanostructured calcium silicate

Up to 7.4% (w/w) of the sulfonated polyaniline, poly(2-methoxyaniline-5-sulfonic acid) (PMAS) can be absorbed onto nanostructured calcium silicates. Spectroscopic and leaching studies on the novel PMAS-silicate nanocomposites obtained indicate that attachment of the PMAS occurs via electrostatic binding of PMAS sulfonate groups to Ca2+ sites on the silicates. The surface area and pore volume of the nanocomposites are comparable to those of pure silicate and increase the surface area of the PMAS polymer by several orders of magnitude. The PMAS emeraldine salt in the nanocomposites retains its chemical reactivity, being readily oxidised and reduced to its pernigraniline and leucoemeraldine forms, respectively. The conductivity of the composite is comparable to that of the pure PMAS, several orders of magnitude higher than that of dried nanostructured calcium silicate.     

Biodegradation of Direct Red 5B, a textile dye by newly isolated Comamonas sp. UVS

Soil samples collected from the vicinity of "Manpasand textile industry", located near Ichalkaranji, India were studied for screening and isolation of bacterial strains capable of degradation of textile dyes. A potential strain was selected on the basis of rapid dye degradation and later identified as Comamonas sp. UVS. Comamonas sp. UVS showed 100% decolorization of Direct Red 5B (DR5B) dye at 40 degrees C and pH 6.5. The maximum Direct Red 5B concentration decolorized was 1100mg/l in nutrient broth within 125h. A numerical simulation with the Michaelis-Menten kinetics model gives an optimal value of 16.01+/-0.36mgdye/gcell/h for maximum rate (V(max)) and 7.97+/-0.21mg/l for the Michaelis constant (K(m)). The induction in the activities of laccase and LiP was observed during decolorization. These enzymes were inhibited by the addition of sodium azide. The biodegradation was monitored by UV-vis, FTIR spectroscopy and HPLC. The GCMS analysis indicated the presence of 7-benzoylamino-3-diazenyl-4-hydroxy-naphthalene-2-sulfonic acid in degraded product of the dye. The germination of Triticum aestivum seeds was inhibited with DR5B treatment but not with the treatment of dye degradation products.     

Differential fate of metabolism of a sulfonated azo dye Remazol Orange 3R by plants Aster amellus Linn., Glandularia pulchella (Sweet) Tronc. and their consortium

Plant consortium-AG of Aster amellus Linn. and Glandularia pulchella (Sweet) Tronc. showed complete decolorization of a dye Remazol Orange 3R in 36 h, while individually A. amellus and G. pulchella took 72 and 96 h respectively. Individually A. amellus showed induction in the activities of enzymes veratryl alcohol oxidase and DCIP reductase after degradation of the dye while G. pulchella showed induction of laccase and tyrosinase, indicating their involvement in the dye metabolism. Consortium-AG showed induction in the activities of lignin peroxidase, veratryl alcohol oxidase, laccase, tyrosinase and DCIP reductase. Two different sets of induced enzymes from A. amellus and G. pulchella work together in consortium-AG resulting in faster degradation of the dye. The degradation of the dye into different metabolites was confirmed using High Performance Liquid Chromatography and Fourier Transform Infra Red Spectroscopy. Gas Chromatography Mass Spectroscopy analysis identified four metabolites of dye degradation by A. amellus as acetamide, benzene, naphthalene and 3-diazenylnaphthalene-2-sulfonic acid, four metabolites by G. pulchella as acetamide, 3-diazenyl-4-hydroxynaphthalene-2-sulfonic acid, naphthalen-1-ol and (ethylsulfonyl)benzene, while two metabolites by consortium-AG as 2-(phenylsulfonyl)ethanol and N-(naphthalen-2-yl)acetamide. The non-toxic nature of the metabolites of Remazol Orange 3R degradation was revealed by phytotoxicity studies.     

Electrolyte-doped ice as a platform for atto- to femtoliter reactor enabling zeptomol detection

Rapid freezing of an aqueous electrolyte in liquid nitrogen provides an effective way to fabricate uniform-sized liquid pores with the radius ranging from 0.15 to 3 μm (<1% rsd), corresponding to atto- to femtoliter volumes. The size of liquid pores depends on the temperature, and the concentration and type of a salt incorporated into an original aqueous solution. When the concentration of a salt is kept lower than 20 mM, liquid pores are discretely distributed in an ice matrix. Unlike usual small spaces accommodating liquid water, the pore size is tunable and continuously variable by changing the above experimental parameters. The liquid pore has been utilized as microreactors, in which the fluorescent complexation between Mg(2+) and 8-hydroxyquinoline-5-sulfonic acid (HQS) is studied. Under the optimum condition, fluorescence from Mg(2+) ions in the zeptomol level confined in a liquid pore is detected.