氨青霉素降解产物在汞膜电极上的伏安法研究

考察了氨苄青霉素在酸、碱条件下的降解产物于玻碳汞膜电极上的伏安行为,降解产物在醋酸缓冲溶液（pH5.5)的底液中均产生了灵敏的阴极还原峰,以碱降解条件为好。已将方法应用于模拟样品的分析。     

麦草碱木素及其热化学降解产物相对分子质量分布的测定

以pH=10的0．1mol/L NaNO3溶液为流动相，在Ultrahydrogel柱上测定麦草碱木素及其热化学降解产物的相对分子质量分布，测定碱木素降解产物所用洗脱液宜用pH10的0．1mol/LNaNO3水溶液，比较了由于样品结构特性和物理性质差异而造成的流动行为的差异，并确定两种样品各自的色谱条件。     

头孢环己烯降解产物荧光性质的研究及分析应用

本文详细研究了头孢环己烯（先锋Ⅵ）在酸、碱介质中的降解反应，通过降解产生的荧光产物建立了酸、碱降解荧光分析法。方法检出限分别是０．７６ｎｇ／ｍｌ（酸降解）和１／１ｎｇ／ｍｌ（碱降解），线性范围皆为０￣０．１０μｇ／ｍｌ，精密度和准确度是酸降解荧光分析优于碱降解。酸降解荧光分析应用于血清和尿样中头孢环己烯测定，结果令人满意。     

青蒿素及其一类物的结构和合成 XXIII: 脱氧青蒿素碱降解产物内酯构型的测定

本文根据具有双氢青蒿乙素这类结构的化合物,其内酯构型和内酯羰基α-位氢的化学位移间存在的经验性规律,推定了脱氧青蒿素碱降解产物的内酯构型应为β-顺式内酯构型2,并通过合成此降解产物加以证实。同时讨论了降解产物形成的机理。     

青蒿素及其一类物的结构和合成 XXIII: 脱氧青蒿素碱降解产物内酯构型的测定

本文根据具有双氢青蒿乙素这类结构的化合物, 其内酯构型和内酯羰基α-位氢的化学位移间存在的经验性规律, 推定了脱氧青蒿素碱降解产物的内酯构型应为β-顺式内酯构型2, 并通过合成此降解产物加以证实, 同时讨论了降解产物形成的机理。     

液相色谱-质谱法研究附子生物碱的煎煮减毒机理

建立了基于液相色谱-质谱分析的附子中生物碱指纹分析方法,并将其应用于附子煎煮减毒的机理研究。基于质谱特征鉴定了生物碱标准品在加热回流过程中产生的6种降解产物,确定了双酯型生物碱的煎煮条件降解规律。在此基础上研究了附子饮片煎煮不同时间条件下生物碱的指纹变化,结果表明,长时间煎煮可明显降低双酯型生物碱和生物脂碱的浓度,为附子的安全用药提供了科学依据。     

LC-ESI-MS分析两性霉素B降解产物

两性霉素B(amphotericinB)是一种常用的抗真菌抗生素,属于多烯大环内酯类化合物,化学性质不稳定,在生产和储存过程中容易发生多种降解反应,产生无活性甚至有毒性的降解物,直接影响产品质量和临床用药的安全,因此,研究该抗生素降解物和降解途径,对防止产品降解、保证产品质量非常必要。已有不少有关两性霉素B各种剂型稳定性的研究报道,ThomaK等研究报道了多烯类抗生素光稳定性结果,然而有关两性霉素B在酸、碱、加热、氧化和光照等条件下降解途径研究未见报道。由于直接分离鉴定各降解产物比较困难,本实验采用LC-MS在线分析手段,直接分析检测降解产物。实验表明,通过检测各种加速实验样品的降解物,可以确立降解途径和降解物,本文对控制降解反应发生、提高产品质量以及稳定性研究具有重要意义。     

气相色谱-质谱联用研究抗坏血酸在注射液中的降解产物

抗坏血酸是一种常用药物,化学性质不稳定,有关其降解产物,已见许多报道,仅在Mikova,Kamila所作综述中,就包括了C_1—C_(10)48种降解产物。本文作者根据前报气相色谱—质谱联用分离鉴定抗坏血酸及降解产物的分析方法,以25％抗坏血酸注射液为对象,研究了注射液安瓿中抗坏血酸在中性条件下的无氧降解产物,确定了在该条件下抗坏血酸降解有丙三醇、丁四     

高效液相色谱-电喷雾串联质谱法对氧化条件下缬草素降解产物的结构及氧化动力学研究

建立了评价缬草素在氧化条件下稳定性的系统方法。采用高效液相色谱-电喷雾串联质谱(HPLC-ESI MS/MS)法对缬草素在氧化条件下(H2O2)的降解产物进行分离,并对主要降解产物进行结构鉴定,样品经Agilent Extend-C18分离,以乙腈-0.25%乙酸水溶液为流动相,梯度洗脱,质谱条件为电喷雾离子源(ESI),正离子模式检测。在上述条件下,共鉴定出4个主要降解产物,其中1个由标准品对照而得,4个化合物的结构母核均为缬草醛类成分。利用HPLC测定缬草素在H2O2中不同时间点的含量变化,经计算缬草素在H2O2中的变化符合一级动力学方程,10%的原型产物发生降解的时间为0.5 h。实验从定性和定量两方面揭示了缬草素的降解机制和降解规律,可为缬草素或含有缬草素的中药制剂的进一步研究与应用提供依据。     

溶液pH值对二嗪磷紫外光降解产物及降解途径的影响

在低压汞灯(253.7 nm)光照条件下, 研究了溶液pH值对农药二嗪磷光降解产物及降解途径的影响. 结果表明: 不同溶液pH值条件下二嗪磷的光降解均符合一级反应动力学, 其在中性(pH=7.0, k=0.0234 min^-1)和碱性(pH=10.0, k=0.0236 min^-1)条件下的光降解速率基本相同, 且略高于酸性(pH=4.0, k=0.0193 min^-1)时的光降解速率. 通过UPLC-ESI-MS/MS对降解产物测定分析发现: 溶液pH值显著地影响了二嗪磷光降解产物的种类及生成量. 溶液pH=4.0、7.0和10.0的二嗪磷溶液分别UV光照60 min时分别检出了五种、八种和六种主要的光降解产物, 且同一产物在不同pH值条件下的生成量存在显著差异. 结合MS和MS/MS质谱图信息, 推导出了二嗪磷主要光降解产物的分子结构, 并根据光降解产物种类及生成量随光照时间的变化关系提出了不同溶液pH值时二嗪磷的可能降解途径.     

Indirect determination of ampicillin sodium with sodium nitrate-ammonium thiocyanate-water system by extraction-flotation of cuprous thiocyanate

A novel method for indirect determination of ampicillin sodium by the extraction-flotation is proposed in this paper. It is indicated that the degradation of ampicillin sodium took place in the presence of 0.30 M sodium hydroxide in boiling water for 20 min. At pH 4.0, in the presence of ammonium thiocyanate, the thiol group of the degradation product of ampicillin sodium could reduce copper(II) to copper(I) due to the formation of the emulsion cuprous thiocyanate precipitation. By determining the residual amount of copper(II) in the solution and calculating the flotation yield of cuprous thiocyanate, the indirect determination of ampicillin sodium can be performed. When the concentration of cooper(II) was 5.0 μg/mL, a good linear relationship was obtained between the flotation yield of cuprous thiocyanate and the amount of ampicillin sodium in the range of 0.40～9.6 μg/mL. The linear equation is E = 4.1469 + 3.7949c with the correlation coefficient r = 0.9992, and the detection limit (3σ/K) of 0.37 μg/mL. Each parameter has been optimized and the reaction mechanism has been studied. The method has been successfully applied to the determination of ampicillin sodium in pharmaceutical, human plasma and urine samples. Analytical results obtained are satisfactory.     

离子液体中壳聚糖/AMPS共聚交联微球的制备

与线性聚合物相比,交联聚合物因其复杂的结构而具有特殊的性能[1～3].壳聚糖是甲壳素的N-脱乙酰基产物,具有良好的生物相容性、无毒性和生物可降解性等特点[4],在食品、医药及水处理等领域中广泛应用[5～7].在实际应用中,经常将各种单体接枝到聚合物表面,由于单体的均聚反应影响接     

Synthesis of Pb(OH)2/rGO Catalyst for Conversion of Sugar to Lactic Acid in Water

Conversion of sugars from biomass to platform chemicals or fuels is an attracting topic for the utilization of biomass. Pb²⁺ ion is an efficient catalyst for the degradation of sugar to lactic acid, and it will be better to fix lead on a solid catalyst to reduce the risk of exposure of Pb²⁺ to environment. Here, a simple method has been developed to prepare a composite catalyst of Pb(OH)₂/rGO, where the nanoparticles of Pb(OH)₂ in size of 2-5 nm were prepared and fixed over the as-prepared reduced graphene oxide (rGO) nanosheets. The as-obtained catalyst showed an efficient catalytic activity to degrade glucose, fructose, and cellulose in aqueous solution, and the major product is lactic acid. The yield of lactic acid reached 58.7% when fructose was used as the feedstock (433 K and 2.5 MPa N₂), and the catalyst can be recycled with high activity. Cellulose can also be directly converted into lactic acid in aqueous solution over the catalyst without extra acid or alkali, and the maximum yield of lactic acid is 31.7%.     

Development and validation of a reversed-phase ultra-performance liquid chromatographic method for assay of lacidipine and related substances

A simple isocratic, RP-ultra-performance LC method was developed and validated for the determination of lacidipine, three process impurities formed during synthesis, and three degradation products present in drug substance and the drug product. An efficient chromatographic separation was achieved on an Acquity BEH C18 column using pH 4.5 ammonium acetate-acetic acid buffer-methanol (70 + 30, v/v) mobile phase. The monitoring wavelength was 240 nm, and the flow rate 0.25 mL/min. Forced degradation studies using acid, alkali, peroxide, water, heat, and light were conducted, and all impurities were separated. The method was validated successfully for specificity, precision, linearity, accuracy, LOD, LOQ, and robustness, according to International Conference on Harmonization guidelines. The linearity of the calibration curve for lacidipine and each impurity was found to be very good (r2 > 0.999). This method is shown to be suitable for analysis of lacidipine to evaluate the quality of drug substance and a drug product.     

High-performance liquid chromatographic assay of ampicillin in plasma and broncho-alveolar lavage fluid,using fluorescence detection

Summary A high performance liquid chromatographic analysis of ampicillin in plasma and broncho-alveolar lavage fluid, using amoxicillin as internal standard, is described. The samples are deproteinated with trichloroacetic acid. For both ampicillin and amoxicillin, a fluorescent degradation product is formed in the presence of mercury(II)-chloride, after alkaline degradation and acid hydrolysis. Chromatography is done on a Spherisorb 5 ODS column using methanol-water (6040) with Pic^RB-7 (1-heptane sulphonic acid) as mobile phase and fluorescence detection (Ext 345 nm, Em 425 nm). Calibration curves for ampicillin were linear over the concentration range 1–100 g/ml in 100 l plasma samples and over the concentration range 20–2000 ng/ml in 0.5 ml samples of broncho-alveolar lavage fluid.Quantitative analyses with relative standard deviations of less than 10% are achieved.Presented at the 17th International Symposium on Chromatography, September 25–30, 1988, Vienna, Austria.     

Thermal stability and degradation mechanisms of poly(acrylic acid) and its salts: Part 3—Magnesium and calcium salts

The magnesium and calcium salts of acrylic acid have been polymerised in aqueous solution using ammonium persulphate as initiator. Both polymers were also prepared by the neutralisation of poly(acrylic acid) with metal oxide in the same medium.

The thermal degradation behaviour of magnesium and calcium polyacrylate was studied using thermogravimetry (TG), differential thermal analysis (DTA) and thermal volatilisation analysis (TVA). Degradation products were investigated by IR spectroscopy, mass spectrometry and GC-MS techniques, the volatile product fraction having first been separated by subambient TVA.

The decompositions of these materials show some similarities to the behaviour of the alkali metal salts of poly(acrylic acid) and to that of the alkaline earth metal salts of poly(methacrylic acid), but there are also important differences. Acetone and carbon dioxide are the most important volatile products and, in addition, there are various other carbonyl containing products. More carbon dioxide, resulting from side group scission, is evolved from magnesium polyacrylate than from calcium polyacrylate, because of the lower thermal stability of magnesium carbonate.     

Degradation of epoxidized polyenes in the presence of phthalic acid

Viscometry was used to follow the epoxidation of polybutadiene and styrene–butadiene triblock copolymers (SBS) with monoperoxyphthalic acid (MPPA). Long reaction periods lead to an abnormal increase and then drop in reduced viscosity. The increasing viscosity is due to repulsion between oxirane group and its ring-opening product with phthalic acid, while the viscosity drop can be correlated with a decrease of molecular weight. Long-term storage of the epoxidized polyenes in the reaction solution containing phthalic acid, which is the derived product from MPPA, also leads to the dramatic decrease in molecular weights. The occurrence of degradation was confirmed by GPC analysis of molecular weight and molecular weight distribution. Chloroform accelerated the degradation reaction, possibly through the generation of hydrochloric acid. The degraded products were isolated and analyzed by GPC and NMR. A free radical mechanism was proposed for the oxidative degradation of epoxidized polyenes after excessive reaction.     

Polyaddition reaction of biscarbodiimides. II. Synthesis of polyguanidines by polyaddition reaction of biscarbodiimides with diamines

A series of polyguanidines was prepared by the polyaddition reaction of biscarbodiimides with diamines. The polyaddition reaction was carried out in solution. The polymers thus obtained had intrinsic viscosities up to 0.84 and molecular weights up to 15000. The structure of the polymers was identified by comparison of their infrared spectra with those of model compounds, elementary analysis, and a study of the reaction conditions. Thermogravimetric study indicated that the polyguanidines decomposed over 170°C under nitrogen. The polyguanidines were highly resistant to hydrolytic degradation by strong acid or alkali. The polyguanidines had basic groups and formed stable hydrochloric salts when they were treated with hydrochloric acid.     

Radiolysis of alkyl benzene sulfonat (ABS) in aqueous solution

Degradation of alkyl benzene sulfonate (ABS) in aerated aqueous solution irradiated with gamma radiation with doses up to 1.8 kGy were studied. The degree of degradation, pH change, the effect of pH on the degradation, COD values and the degradation products were determined. The degradation of ABS increases with the increase of doses and decreases with the increase of ABS concentration. The degradation was somewhat more efficient in slightly acidic and neutral solutions than at basic pH oxalic acid was detected by HPLC as degradation product.     

对甲基苯酚电催化氧化机理

在无隔膜电解槽中, 利用线性伏安法和恒电流电解法研究了Ti/PbO2电极对于对甲基苯酚氧化的电催化活性, 通过阳极过程中对甲基苯酚及其氧化中间产物的液相色谱测定, 研究了对甲基苯酚电催化氧化降解的机理. 研究结果表明, Ti/PbO2电极能够有效地电催化氧化水溶液中的对甲基苯酚, 在25 ℃下, 初始浓度为2 mmol/L的对甲基苯酚溶液, 恒定电流密度为50 mA/cm2, 电解3 h, 对甲基苯酚的转化率为74.32%, 有机碳去除率为61.81%. 对甲基苯酚电氧化降解要经过生成对羟基苯甲醇、对羟基苯甲醛、对羟基苯甲酸、对苯二酚、对苯醌、顺丁烯二酸和草酸, 最终变成CO2的历程, 其中对苯二酚的氧化和顺丁烯二酸的氧化为反应的速控步骤.