在离子液体中合成有机磷农药通用半抗原

以离子液体[Bmim] Br为溶剂和催化剂,O,O-二烷基二硫代磷酸铵盐(1a,1b)与氯乙酸于45℃反应40min,合成了有机磷农药半抗原S-羧甲基-O,O-二乙基二硫代磷酸酯和S-羧甲基-O,O-二甲基二硫代磷酸酯,产率分别为97.9％和98.4％.1a和1b低温(＜5℃)酸化后与丙烯酸在[Bmim] Br中于室温反应60 min,合成了两个有机磷农药半抗原S-羧乙基-O,O-二乙基二硫代磷酸酯和S-羧乙基-O,O-二甲基二硫代磷酸酯,产率分别为93.7％和94.2％.[Bmim] Br重复使用4次后依然保持较高的催化活性.     

生物素-亲和素放大酶联免疫吸附法测定双酚A

建立了可用于快速、灵敏地检测双酚A的生物素-亲和素放大酶联免疫吸附测定法,测得最佳实验条件为包被抗原浓度为13.8mg/L、抗体稀释为2.4×105倍,生物素化二抗和酶标亲和素的最佳稀释倍数分别为2000倍和500倍。在优化条件下,方法的线性范围0.2~1000μg/L;最低检出限0.05μg/L。所建立的方法用于食品和唾液中双酚A含量的测定,样品处理简单,结果满意。     

生物素-亲和素放大酶联免疫吸附法测定氯胺酮

建立了检测氯胺酮的生物素-亲和素放大酶联免疫吸附测定法(BA-ELISA)。实验最佳测定条件:抗原包被浓度为2.0mg/L、氯胺酮单克隆抗体浓度为10.2mg/L,生物素化羊抗小鼠IgG(Biotin-IgG)和酶标链霉亲和素(SA-HRP)的最佳反应浓度分别为0.29和1.0mg/L。在此优化条件下,方法的线性范围为0.1～1000μg/L;检出限为0.03μg/L。氯胺酮生物样品的加标回收率为94%～102%。与酶标二抗体系ELISA法相比,BA-ELISA具有更高的灵敏度,适于低浓度氯胺酮的检测。     

气相色谱法测定不对称催化合成反应液中手性1,1-二苯基-2-丙醇含量

(S)-(+)-1,1-二苯基-2-丙醇是一种很有用的医药中间体,用它可以合成生物素,此物质广泛应用于医学各领域。近年来大量研究证实,生物素-亲和素(BAS)系统几乎可与目前研究成功的各种标记物结合。在生物素-亲和素(BAS)系统中,借助所形成的生物素-亲和素-酶复合物,追踪生物素标记的抗原或抗体,通过酶催化底物显色,可检出相应的抗体或抗原。由于抗原或抗体分子可偶联多个生物素,     

基于碳纳米管载体的丙烯酰胺免疫亲和吸附剂的研究

自从在油炸及烧烤的淀粉类食品中检测到具有潜在致癌风险的丙烯酰胺副产物后,发展简单实用的丙烯酰胺检测方法的研究备受重视~([1]).以N-羟基琥珀酰亚胺丙烯酸酯(NAS)为半抗原,成功制备了对丙烯酰胺具有特异性识别和结合作用的多克隆抗体,建立了能够对淀粉类食品中丙烯酰胺进行快速检测的生物素-亲和素酶联免疫分析方法~([2]).     

链亲和素-磁性微粒的制备及其应用

通过物理吸附和共价作用机制, 制备两种链亲和素-磁性微粒, 即链亲和素-金磁微粒和链亲和素-氨基磁粒, 并对其在不同缓冲液中的稳定性进行研究; 采用酶抑制法测定两种链亲和素-磁性微粒对游离生物素的结合能力; 分别以紫外吸收和固相核酸杂交方法, 测定两种链亲和素-磁性微粒对生物素标记寡核苷酸探针的固定化容量及活性, 并与Dynabeads®M-270 Streptavidin进行比较. 结果表明: 通过物理吸附作用制备的链亲和素-金磁微粒, 适用于核酸杂交与检测常用的STE (Tris-NaCl-EDTA) 缓冲系统, 通过共价作用形成的链亲和素-氨基磁粒, 适用于STE和磷酸盐(PBS)缓冲系统; 1 mg链亲和素-金磁微粒和链亲和素-氨基磁粒对游离生物素的最大结合容量分别为4950和5115 pmol; 对生物素标记寡核苷酸探针(24 mer) 的结合容量分别为2839和2978 pmol, 测定结果均是Dynabeads®M-270 Streptavidin的6~7倍; 与FITC-标记互补寡核苷酸的杂交结果表明, 固定于链亲和素-磁性微粒表面的寡核苷酸探针保持了较好的生物学活性.     

超声萃取/气相色谱-串联质谱法同时测定纺织品中6种禁用有机磷阻燃剂

以丙酮为萃取溶剂,建立了超声萃取/气相色谱-串联质谱同时测定纺织品中6种禁用有机磷阻燃剂的分析方法.6种禁用有机磷阻燃剂三-(1-氮杂环丙基)氧化膦( TEPA)、三-(2-氯乙基)磷酸酯(TCEP)、三-(2,3-二氯丙基)磷酸酯(TDCP)、二-(2,3-二溴丙基)磷酸酯(DDBPP)、三-(邻甲苯基)磷酸酯(TO...     

微悬臂生物传感器检测生物素-亲和素相互作用

将生物素共价键合到微悬臂的硅表面, 利用微悬臂传感技术在流动注样条件下研究了生物素-亲和素的动态作用过程, 同时利用原子力显微镜(AFM)力刻蚀技术验证了生物素化硅表面结合亲和素的有效性. 结果显示亲和素与生物素作用产生较大的表面应力驱动微悬臂偏转, 悬臂偏转的程度和速率与亲和素的浓度相关, 亲和素浓度越大, 微悬臂偏转程度也越大, 同时反应速率也更快. 这项工作为开发新型的无标记检测技术, 研究生物分子之间相互作用提供了有益的探索.     

基于生物素-亲和素系统的压电免疫传感器检测相思子毒素研究

利用生物素-亲和素系统的放大作用和纳米金质量扩增效应,建立了压电免疫传感器检测相思子毒素的新方法.首先在石英晶体的金电极上依次组装二巯基丙酸、EDC和NHS进行表面修饰,然后通过亲和素固定生物素标记相思子毒素多抗来制备敏感膜,利用纳米金的质量扩增效应设计了一种"毒素-纳米金标记单抗"复合物,成功实现了对相思子毒素的检测,提高了传感器灵敏度和重现性.本传感器对相思子毒素响应的线性范围为0.05～5 mg/L; 回归方程为Δf＝50.81CAbrin+67.11(r=0.9903,n＝10,P<0.0001); 检测灵敏度为50.81 Hz · L/mg.     

基于磁性纳米颗粒和金纳米粒子构建DNA电化学生物传感技术

本文构建了一种基于纳米粒子、茎环DNA和丝网印刷电极(SPCE)的电化学生物传感技术用于乳腺癌基因的快速、灵敏检测。该传感技术中,探针DNA的两端分别标记了巯基和生物素,巯基用于与金纳米粒子(AuNPs)作用,生物素用于与磁性纳米颗粒(MNPs)表面修饰的链酶亲和素作用以达到富集的目的,之后利用SPCE进行电化学检测。无目标DNA存在时,双标记DNA保持茎环结构,使得生物素分子很难和MNPs上的亲和素接触。一旦加入目标DNA,茎环结构打开,生物素得以与MNPs上的链霉亲和素发生特异性结合,形成的复合物(MNPs-DNA-AuNPs)通过磁性富集到SPCE表面,从而获得AuNPs的电化学信号。该DNA电化学生物传感对单碱基错配有良好的分辨能力,完全互补DNA的检出限为8.0×10-13 mol/L。     

Physico-chemical properties of Chitosan films

Chitosan films obtained by dry phase inversion were prepared from an aqueous solution of chitosan in acetic acid. The films, of thickness less than 20 μm, were transparent, very flexible and had smooth surfaces. Increasing the film thickness induced an increase of the internal tensions and the consequent formation of a rough surface. Structural investigations by X-ray diffraction and Fourier transform IR analysis, showed that the chitosan films, as prepared, are amorphous. Further annealing to evaporate acetic acid and water traces, changed the amorphous phase into a more ordered phase, characterized by diffraction peaks at 2θ values of 9, 17, 20 and 23 degrees. Thermal investigations by TG, DTG, and DTA revealed that the decomposition of the chitosan films as prepared proceeds in two stages, starting from 180°C and 540°C.     

Pyrazoles as molecular probes to study the properties of co-crystals by solid state NMR spectroscopy

Equimolar mixtures of 3,5-dimethylpyrazole (1) with four NH-imidazoles (2–5) have been studied by¹³C and ¹⁵N CPMAS NMR and by DSC. In three cases, the solid mixture behaves as the sum of the individual components [imidazole (2), 2-methylimidazole (3) and 2,4(5)-dimethylimidazole (5)]. In one case [4,5-dimethylimidazole (4)], the mixture corresponds to a new species in which the dynamic behavior of1 no longer exists.     

Aqueous p-nitrotoluene oxidation induced with direct glow discharge plasma

A plasma induced degradation process has been studied to treat 4-nitrotoluene (4-NT) present as an aqueous pollutant. The plasma was locally generated from a glow discharge around a tip of a platinum anode in an electrolytic solution. The influence of initial pH and Fe²⁺ on the degradation was examined. Major intermediates resulting from the degradation process were identified. Amongst the aromatic intermediates, p-hydroxybenzoic acid was the predominant degradation product. The formation of oxalic acid, malic acid was also observed. The final products of degradation were NH ₄ ⁺ , NO ₃ ⁻ and CO₂. Based on the analysis of intermediates and the kinetic considerations, the degradation was shown to follow a pseudo-first order reaction hence, a possible reaction pathway was proposed.     

Catalytic air oxidation of manganese in synthetic waters

An attempt was made to study the oxidation of manganese by air in synthetic waters. A series of batch experments were performed at differnet values of concentration, temperature and pH. Unoxidized manganese in the solution was determined by formaldoxime spectrometric method. Results of these studies indicated that the air oxidation of manganese soluble in water can be effectively performed in basic media and that oxidation yield increasedwith an increase in pH and concentration. The yield was very high in the presence of manganese dioxide, sepiolite or clinoptilolite in solution and, the oxidation was almost completed especially at high values of pH and concentration. The reaction was found to be first order with respect to Mn²⁺ with a very low activation energy. A yield of 62% was obtained for the air oxidation of wastewater taken from the treatment plant of Corum Municipality.     

Zur Kenntnis der Reaktionsfähigkeit des Thiomorpholins und alkylsubstituierter Thiomorpholine, 4. Mitt.

Thiomorpholine as well as alkyl substituted thiomorpholines and their Sdioxides, respectively, are transformed into the corresponding N-Aminothiomorpholines by nitrosation (1–5) followed by the reduction with zinc in acetic acid/acetic acid anhydride under simultaneous formation of the corresponding N-acetyl derivates, and hydrolysis by hydrochloric acid (6–9). Examples of this method are described. 4-Aminothiomorpholines and their Sdioxides react with aldehydes or ketones to give azomethines (10–31). Acylation with mono-and dicarbonic acid chlorides leads to the N-acyl derivatives32–44.Mannich condensation is also possible. By oxidation with yellow mercury oxide tetracenes are formed (46–47).

Teil der DissertationM. Schmitz, Techn. Hochschule Aachen, 1975.     

Beiträge zur Chemie der Pyrrolpigmente, 39. Mitt.: Ein Kraftfeldmodell zur konformationsanalytischen Untersuchung von Gallenfarbstoffen

A force field model was designed with respect to the special needs of bile pigments. It is parametrized and tested using partial structures of bile pigments as well as an integral pigment; the solution structures of the molecules were previously deduced using independent experimental methods.

38. Mitt::Falk, H., Schlederer, T., Wolshann, P., Mh. Chem.112, 199 (1981).     

Präparation und röntgenographische Untersuchung eines neuen Kupfer-Oxoaluminats: Cu2Al4O7

Solid state reaction of CuO and Al₂O₃ with a flux of PbO about 930°C and reaction time of 8d gives the new compound Cu₂Al₄O₇. The red single crystals were examined by energydispersive microanalysis and X-ray diffraction methods. Cu₂Al₄O₇ has cubic symmetry, space group ,a=908.0 pm. The typical coordination of Cu⁺ (CN=6 and CN=12) and the interstitial arrangement of the AlO₄-tetrahedra are discussed with respect to related compounds.

     

Hydrazyl,Nitronyl-, and imino-nitroxides: Synthesis,properties and reaction with nitric oxide and nitrogen dioxide

Ten novel and stable free radicals of nitronyl-, imino-nitroxide and hydrazyl type compounds were synthesized and their physico-chemical properties investigated. UV-Vis and ESR spectroscopic data, as well as the lipophilicities and specific hydrophobic areas of the compounds are compiled. The reaction of these radical compounds with nitric oxide and nitrogen dioxide was also investigated. The radicals synthesized, show selectivity in their reaction with these nitric oxides, depending on their structure (nitronyl-nitroxide radicals react with NO, while hydrazyl radicals react with NO₂). The processes are easily monitored by UV-Vis or ESR spectroscopy.     

Neue Synthesemethoden, 4. Mitt.: Milde einphasenoxidation von Sulfiden und Sulfoxiden zu Sulfonen

The mild oxidation of sulfides and sulfoxides to sulfones with benzyltriethylammoniumpermanganate in organic solvents is described.

1Scholz, D., in Vorbereitung.     

A kinetic method for <Emphasis Type="Italic">para</Emphasis>-nitrophenol determination based on its inhibitory effect on the catalatic reaction of catalase

The inhibitory effect of para-nitrophenol on the catalytic reaction of catalase was investigated. Michaelis-Menten kinetic parameters were determined from Lineweaver-Burk plots obtained in the absence or in the presence of the inhibitor. The inhibitor pattern, revealed by the Lineweaver-Burk plots, suggested a fully mixed inhibition mechanism. Spectrophotometric monitoring of the indicator reaction: in conjunction with initial rate measurements was employed for the kinetic determination of the inhibitor. Calibration plots of initial rate vs. para-nitrophenol concentration were linear in the concentration range 0.9·10⁻⁵–2.5·10⁻⁵ mol/L and the detection limit was 3·10⁻⁶ mol/L (417 μg/L) para-nitrophenol. Interferences from other phenolic compounds like orto-cresole, meta-and orto-nitrophenol were observed.