Rapid liquid chromatographic analysis of Metoclopramide in pharmaceutical preparations

A sensitive, accurate and reproducible method for the analysis of metoclopramide, a gastrointestinal drug, has been described. An isocratic HPLC elution method was employed which requires about 10 minutes to be performed. The concentration of metoclopramide hydrochloride preparations was found to be 95.1 ±0.3% and 94.21 ±0.25% in tablet and injection formulations, respectively.     

Rapid liquid chromatographic analysis of flurazepam in pharmaceutical preparation

An accurate and reproducible method for the analysis of flurazepam hydrochloride in pharmaceutical preparations has been described. A simple and rapid isocratic HPLC elution method was employed which requires about 15 minutes to be performed. The percentage mean recovery of flurazepam hydrochloride in Dalmane capsules was found to be 100.67% + 1.23% of the declared amount     

高效液相色谱法测定天然水体中微囊藻毒素方法优化

以3种微囊藻毒素Microcystin-RR(MC-RR)、Microcystin-YR(MC-YR)和Microcystin-LR(MC-LR)为研究对象,对前处理及高效液相色谱分析测定方法进行优化,使3种目标物均可检测.进一步对天然水体样本的采集与储存条件进行探讨.研究结果显示,聚乙烯塑料瓶和棕色玻璃瓶对于样品保存不存在明显差异;-20℃条件下保存45 d内样品变化不存在明显差异,可作为样品储存条件.     

Green chemistry approach to analysis of formic acid and acetic acid in aquatic environment by headspace water-based liquid-phase microextraction and high-performance liquid chromatography

A simple and totally organic-free (green) method, viz. headspace water-based liquid-phase microextraction combined with high-performance liquid chromatography-ultraviolet detection has been successfully developed for analysis of formic acid and acetic acid in environmental water samples. A microdrop of an aqueous solution of sodium hydroxide was suspended from the tip of a microsyringe needle over the headspace of the stirred sample solution containing the analytes at pH 1.0 for a given time. The microdrop was then retracted into the microsyringe, diluted with HPLC mobile phase, and injected to HPLC. Optimum efficiency has been achieved for: 3.0 µL NaOH microdrop (0.1 mol L^?1) exposed for 15 min over the headspace of an aqueous sample of 6.5 mL at 55 °C, containing 15% w/v of Na₂SO₄, adjusted to pH = 1.0 and stirred at 750 rpm. Under these conditions, enrichment factors of 162 and 187, limits of detection of 0.3 and 0.1 µg L^?1 (S/N = 3) with dynamic linear ranges of 1–500 and 0.5–500 µg L^?1 were obtained for formic acid and acetic acid, respectively. A reasonable repeatability (5.8% ≤ RSD ≤ 8.8%, n = 6) and satisfactory linearity (r² ≥ 0.997) illustrated the performance of the method.     

改进的QuEChERS-高效液相色谱法测定水产品中16种多环芳烃

采用改进的QuEChERS,对水产样品进行提取、净化,用高效液相色谱仪-荧光/紫外检测器串联检测,建立了同时测定水产品中16种多环芳烃的高效液相色谱分析方法.样品经乙腈提取,Florisil+C18小柱净化,Waters PAH色谱柱分离,以乙腈-水为流动相进行梯度洗脱,外标法定量.本方法中,16种多环芳烃在各自相应浓度范围内线性关系良好,相关系数不低于0.999,检出限为0.1—3.6μg·kg-1.采用该方法在鲤鱼、对虾和牡蛎中进行加标回收实验,回收率在75.0%—118.2%范围内,相对标准偏差(RSD)为2.6%—13.7%.应用本方法对环渤海湾的水产样品进行了调查分析,发现部分样品中含有PAHs,含量为2.11—147μg·kg-1,为下一步开展相关风险评估工作打下了良好工作基础.     

Cadmium accumulation by green algae Cladophora glomerata (L.) Kutz. (Chlorophyta) in presence of Nile tilapia Oreochromis niloticus (L.)

Accumulation of metals by aquatic organisms is mostly affected by other biological components in environments. In this study, cadmium (Cd) accumulation in green algae, Cladophora glomerata (L.) Kutz., exposed to 0.1 and 1.0 mg L^?1 of Cd for 15 and 30 days was examined in laboratory conditions in the presence of Nile tilapia Oreochromis niloticus (L.). The green algae C. glomerata accumulated Cd concentrations as 690 ± 70 and 3430 ± 470 mg kg^?1 on day 15, and 1130 ± 180 and 6830 ± 1540 mg kg^?1 on day 30. There were significant increases (p < 0.05) in metal accumulation by green algae as the exposure time and metal concentration increased. The results also indicated that the presence of Nile tilapia in the medium led to a significant Cd accumulation in the green algae compared to control (p < 0.05).     

A new approach to graphical and numerical analysis of links between plant chemotaxonomy and secondary metabolism from HPLC data smoothed by a simplex mixture design

Summary. HPLC analysis of secondary metabolites represents an efficient tool for the studying of plant chemical diversity under different aspects: chemotaxonomy, metabolomics, adaptative responses to ecological factors, etc. Statistical analyses of HPLC databases, e.g. correlation analysis between HPLC peaks, can reliably provide information on the similarity/dissimilarity degrees between the chemical compounds. The similarities, corresponding to positive correlations, can be interpreted in terms of analogies between chemical structures, synchronic metabolisms or co-evolution of two compounds under certain environment conditions, etc. . In terms of metabolism, positive correlations can translate precursor-product relationships between compounds; negative correlations can be indicative of competitive processes between two compounds for a common precursor(s), enzyme(s) or substrate(s). Furthermore, the correlation analysis under a metabolic aspect can help to understand the biochemical origins of an observed polymorphism in a plant species. With the aim of showing this, we present a new approach based on a simplex mixture design, Scheffé matrix, which provides a correlation network making it possible to graphically visualise and to numerically model the metabolic trends between HPLC peaks. The principle of the approach consisted in mixing individual HPLC profiles representative of different phenotypes, then from a complete mixture set, a series of average profiles were calculated to provide a new database with a small variability. Several iterations of the mixture design provided a smoothed final database from which the relationships between the secondary metabolites were graphically and numerically analysed. These relationships were scale-dependent, namely either deterministic or systematic: the first consisted of a monotonic global trend covering the whole variation field of each metabolites’ pair; the second consisted of repetitive monotonic variations which gradually attenuated or intensified along a global trend. This new metabolomic approach was illustrated from 404 individual plants of Astragalus caprinus (Leguminoseae), belonging to four chemical phenotypes (chemotypes) on the basis of flavonoids analysed in their leaves. After smoothing, the relationships between flavonoids were numerically fitted using linear or polynomial models; therefore the co-response coefficients were easily interpreted in terms of metabolic affinities or competitions between flavonoids which would be responsible of the observed chemical polymorphism (the four chemotypes). The statistical validation of the approach was carried out by comparing Pearson correlations to Spearman correlations calculated from the smoothed and the crude HPLC database, respectively. Moreover, the signs of the smoothed relationships were finely supported by analogies and differences between the chemical structures of flavonoids, leading to fluent interpretation in relation to the pathway architecture.     

邻苯二甲酸二丁酯(DBP)对斜生栅藻的致毒效应研究

为了评估邻苯二甲酸二丁酯(DBP)对水生生物的毒性效应,采用室内培养的方法,研究了DBP对斜生栅藻(Scenedesmus obliquus)的急性毒性效应.实验设置5个暴露组(5、10、20、50、100mg·L-1)和1个对照组(0mg·L-1),暴露96h后分别测定DBP对斜生栅藻生长量、光合色素含量、超氧化物歧化酶(SOD)活性、丙二醛(MDA)含量等生理生化指标的影响.结果表明,各暴露组DBP对斜生栅藻的生长均有抑制作用,随DBP暴露浓度的增大,藻细胞密度逐渐降低,显示出明显的剂量-效应关系.DBP对斜生栅藻的24、48、72、96h的EC50值分别为3.31、15.49、1.95、2.21mg·L-1.叶绿素a、b及类胡萝卜素含量随着DBP暴露浓度的增大呈现相同的变化趋势,均为低浓度(5～10mg·L-1)上升,高浓度(10～100mg·L-1)下降.随DBP暴露浓度的增大,斜生栅藻SOD活性表现为先激活后抑制,在20mg·L-1时SOD活性达到最大值(与对照比较,p<0.05);当DBP暴露浓度≥10mg·L-1时,MDA含量随DBP浓度的增大显著增加(与对照比较,p<0.05,p<0.01).     

高效液相色谱-串联质谱法同时检测水体中26种药物及个人护理品

通过优化固相萃取条件和高效液相色谱-串联质谱参数,建立了可以同时检测地表水和地下水中26种典型药物及个人护理品(pharmaceuticals and personal care products,PPCPs),包括磺胺类、大环内酯类、喹诺酮类、酰胺醇类、精神类、消炎止痛类以及个人护理品的检测方法.通过将水样pH值调节...     

Selective separation and preconcentration studies of chromium(VI) with Alamine 336 supported liquid membrane

Chromium compounds have received considerable attention because these are used extensively in such industrial applications as electroplating, steelmaking, tanning of leather goods, and corrosion inhibition. The use of supported liquid membranes (SLMs) to remove metals from wastewaters has actively been pursued by the scientific and industrial community. In the present work, the selective separation and preconcentration of Cr(VI) ions has been studied by using a commercial amine as the membrane liquid on the porous polypropylene support. Permeation experiments were conducted on a laboratory scale batch reactor made up of perspex, with a memberane fixed amid the two chambers. The flux of Cr(VI) ions was found to be maximum (3.15?×?10^?5?mol?cm^?2?s^?1) around pH 1. Above and below this pH the flux decreases. Distribution studies show that an increase in the amine concentration leads to higher distribution coefficients at fixed pH values. At pH around unity, the distribution of Cr(VI) ions into the organic phase was found to be maximum, of the order of 56.3. The Cr(VI) transport through the membrane increases with rise in temperature. In order to check the long-term efficiency of the flat sheet SLM, an experiment was conducted with higher Cr(VI) concentration (5000?ppm) for 24?h, at optimised parameters. It was observed that in 24?h, about 1/5th of the feed Cr(VI) is left over while the rest is transported. However, minute organic droplets were also seen in the feed and strip compartments, after 1 day. This observation suggested the loss of membrane liquid. The feasibility of preconcentration of Cr(VI) by using the proposed SLM parameters, was also studied by using the hollow fibre (HF) system. Highest enrichment factor (E.F) value was obtained for 50?mg?L^?1 whereby all of the metal was transported to the stripping phase and the resulting Cr concentration was 688?mg?L^?1 (E.F?=?13.8). It was observed that while treating more diluted solutions, the enrichment factor decreases. The values of E.F equal to 8.9 and 11.3 were found for initial Cr concentration of 10 and 30?mg?L^?1.     

应用物种敏感性分布评估多环芳烃对淡水生物的生态风险（Assessing Ecological Risks of Polycyclic Aromatic Hydrocarbons（PAHs）to Freshwater Organisms by Species Sensitivity Distributions）

阐述了利用物种敏感性分布进行生态风险评价的原理与方法,构建了淡水生物对8种常见多环芳烃(蒽、芘、苯并[a]芘、荧蒽、菲、芴、苊、萘)的物种敏感性分布;在此基础上,计算了这8种多环芳烃对不同类别生物的HC5(Hazardous Concentration for5%of the species)阈值,预测了不同浓度多环芳烃对生物的潜在影响比例PAF(Potentialaffected fraction),比较了不同类别生物对多环芳烃的敏感性,以及多环芳烃对淡水生物的生态风险,并对以红枫湖、黄河、白洋淀为代表的中国典型水体中的多环芳烃进行了联合生态风险评价.结果表明:1)当污染物浓度达到10μg·L-1时,半数多环芳烃的风险超过了5%的阈值;当浓度上升到100μg·L-1时,只有萘和苊没有显著生态风险.2)对于芴和荧蒽,无脊椎动物更为敏感;而对于萘,则脊椎动物更敏感.3)通过HC5值比较和SSD曲线图比较,可得出污染物对所有物种的生态风险大小依次为:蒽>芘>苯并[a]芘>荧蒽>菲>芴>苊>萘;对脊椎动物风险大小为:荧蒽>苊>萘;对无脊椎动物:蒽>芘>荧蒽>菲>芴>苊>萘.4)多环芳烃在红枫湖、黄河、小白洋淀的生态风险均较低,急性联合msPAF(multisubstance PAF)值小于1%.     

磷酸三苯酯(TPP)和磷酸三(2-氯异丙基)酯(TCPP)诱导人胚肾细胞HEK293凋亡的机制研究

磷系阻燃剂对人体的潜在毒性作用引起了国内外研究者的广泛关注。肾脏是机体重要的排毒器官,若肾脏细胞受损,可能影响肾脏功能的正常发挥。本研究以人胚肾细胞HEK293为研究对象,结合传统毒理学实验,筛选出磷酸三苯酯(TPP)及磷酸三(2-氯异丙基)酯(TCPP)诱导人胚肾细胞HEK293凋亡的关键靶标基因p53。在此基础上采用分子对接模拟和光谱法分析发现,TPP和TCPP分别以嵌插方式和沟槽方式结合p53-DNA,改变基因片段的框架结构,启动分子起始事件,通过影响相关基因(Bax、Hrk、Bcl-2和Bad)的表达量,导致线粒体途径释放cyt c,最终激活Caspase 7实现细胞凋亡。研究结果阐明了此类污染物诱导凋亡的作用机制,为毒害化学品的污染防控提供理论依据。     

Perfluorocarboxylic acids (PFCAs) and perfluoroalkyl sulfonates (PFASs) in surface and tap water around Lake Taihu in China

Perfluorinated compounds (PFCs) are ubiquitously distributed in the environment mainly as perfluoro-carboxylic acids (PFCAs) and perfluoroalkyl sulfonates (PFASs). In this paper, six PFCAs and two PFASs were quantified in surface and tap water samples from 12 sites around Lake Taihu near Shanghai City in East China. Predominant PFCs were perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS), of which the concentration ranges were 6.8–206 and 1.2–45 ng·L⁻¹, the geometric means were 35.3 and 9.4 ng·L⁻¹, and the median (quartile range) values were 31.4 (34.4) and 10.4 (10.7) ng·L⁻¹, respectively. Other PFCs were also detected but in much lower concentrations than PFOA. The sources of the PFCs were expected to be direct industrial discharges in the Lake Taihu area, and this area was also a possible source of PFCs contaminations in Shanghai district in the downstream. PFCs distributions were found different in the upstream, downstream and north part of Lake Taihu. Occurrences of PFCs in the tap water in Lake Taihu area indicated their exposure to the local people. A brief estimation of the environmental risks by PFCs implied no acute or immediate risks from PFCs to local human health, but chronic risks from PFOA in the tap water should be considered in the downstream regions.     

全氟辛烷磺酸(PFOS)和多壁碳纳米管(MWCNTs)复合对斑马鱼外周血红细胞DNA的损伤

为了评价全氟辛烷磺酸(PFOS)和多壁碳纳米管(MWCNTs)对水环境及鱼类的影响,以斑马鱼为模式生物,研究了PFOS和MWCNTs复合对斑马鱼外周血红细胞的DNA损伤。将成年斑马鱼暴露于PFOS(0.2、0.4、0.8、1.6 mg·L-1)、MWCNTs(50 mg·L-1)、PFOS+MWCNTs(0.2+50、0.4+50、0.8+50、1.6+50 mg·L-1)和对照溶液中30 d后,断尾取血进行微核试验和彗星试验。结果表明:PFOS和MWCNTs均可造成斑马鱼外周血红细胞的DNA损伤。1.6 mg·L-1PFOS处理组的微核率、Olive尾矩及尾长分别为(36.3±0.25)‰、(87.91±14.90)μm和(250.49±34.71)μm。PFOS与MWCNTs复合后,斑马鱼外周血红细胞的DNA损伤效应明显降低。复合处理组斑马鱼外周血红细胞的微核率、Olive尾矩及尾长均低于PFOS单独处理相。1.6 mg·L-1复合处理组的微核率、Olive尾矩及尾长比PFOS单独处理组分别降低了24.7%、68.9%、52.4%。因此,在实验浓度范围内,MWCNTs可以降低PFOS对斑马鱼外周血红细胞的DNA损伤。     

MBR工艺处理螺旋霉素制药废水过程中抗生素耐药菌与抗性基因的研究

抗生素废水含有大量的抗生素耐药菌(antibiotic resistant bacteria,ARB)与抗性基因(antibiotic resistance genes,ARGs),处理排放后可能增强受纳环境的微生物抗性,因此有必要深入研究抗生素废水处理过程中ARB与ARGs的削减效果及其影响因素。本研究采用膜生物反应器(membrane bioreactor,MBR)工艺处理螺旋霉素制药废水,考察了不同水力停留时间(hydraulic retention time,HRT)对ARB与ARGs削减效果的影响。结果表明,虽然在HRT=30 h时MBR对COD与氨氮的去除率略高于HRT=40 h,但HRT=40 h时,不仅总异养菌与肠球菌的去除效果更佳,出水肠球菌耐药率及携带的抗性基因检出率也更低,而且MBR对废水中erm B、erm F、erm X、mef A、ere A、mph B和转移元件ISCR 1、Tn 916/1545相对丰度的削减效果更好。这表明长HRT更有利于MBR工艺削减螺旋霉素废水的耐药菌与抗性基因。     

环介导恒温扩增技术快速检测短凯伦藻

短凯伦藻(Karenia brevis)是一种有毒赤潮微藻,所产生的短藻毒素对海洋生物乃至人类都有毒害作用,为加强对短凯伦藻赤潮的监控,建立了稳定的短凯伦藻环介导恒温扩增(LAMP)鉴定体系,在此基础上进行了特异性和灵敏性验证.特异性实验结果显示只有短凯伦藻或者含短凯伦藻的模板呈现阳性反应,其他微藻为阴性反应,从而验证了该LAMP方法的特异性;同时,对短凯伦藻的基因组DNA进行一系列10倍稀释作为敏感度实验的模板,并与常规PCR做了对比,结果表明:短凯伦藻的LAMP方法最低检测限度为50 pg,敏感度比常规PCR高10倍.LAMP产物鉴定不需要常规的胶电泳过程,直接采用肉眼观察的方法,在含有短凯伦藻的阳性反应管中会出现白色混浊,加入SYBRòGreen I染料呈现绿色,而未含有短凯伦藻的阴性管为澄清,染色后仍为原来的橙色.因此,该方法操作简便、特异性强、灵敏度高而成本低,在赤潮原因种检测监控方面具有良好的应用前景.     

加速溶剂萃取(ASE)-固相萃取(SPE)-高效液相色谱法(HPLC)测定土壤中青霉素钠

建立了一种加速溶剂萃取(ASE)-固相萃取(SPE)-高效液相色谱(HPLC)测定土壤中青霉素钠的简单、快速的方法.样品以超纯水为提取溶剂,50℃提取温度为ASE提取条件参数;HLB型固相萃取柱富集净化:6.0mL 5%甲醇淋洗、4.0mL乙腈-甲醇(1∶1)洗脱;高效液相色谱-紫外检测器(HPLC-PDA)测定,检测波长λ=191.1nm,柱温30℃,流动相为乙腈-0.1%甲酸/水(1∶1),采用等梯度洗脱程序,取得较好的检测分离效果.对0.5、2.0、8.0mg·kg-1等3个不同添加浓度水平的青霉素钠平均加标回收率范围为73.1%—89.7%,回收率相对标准偏差RSD范围为1.1%—2.9%(n=5),检出限可达235.0μg·L-1.结果表明,该方法操作简单,快速,准确度和精密度均符合质量控制要求,能够满足环境土壤样本中痕量青霉素钠检测分析的要求.     

不同阳离子影响下小麦根吸收镉的动力学过程

生物配体模型(BLM)是基于稳定态假设的一个平衡模型,能够较准确地运用于预测重金属的毒性及其生物有效性.根据BLM模型的假设条件模拟土壤溶液,研究了Ca2+、Mg2+、Cu2+和Ni2+对小麦根吸收Cd2+动力学的影响,阐述了BLM在应用中存在的局限性.结果表明:在8h内的短期动力学吸收实验中,小麦根对Cd的吸收及吸附量呈线性增加,但未达到稳定值,这说明Cd2+在根-液界面未达到稳定平衡;并且小麦根对Cd的吸收是受溶液中Cd2+扩散速率影响的.小麦根对Cd的吸收通量与Cd2+浓度[Cd2+]和Cd与小麦根表上的配体结合浓度{Cd-Rcel}l都具有较好的线性关系,但随着Cd2+浓度的增加稳定常数KM-Rcell、渗透常数p和同化速率常数kint均呈降低趋势.Ca2+、Mg2+和Cu2+降低了小麦根对Cd2+的吸收通量,而Ni2+对Cd2+的竞争作用不显著.由于Cd与Ca、Ni有共同的吸收通道,Ca通道吸收达到饱和后可降低小麦根对Cd的吸收,但是Ca2+、Mg2+和Cu2+通过降低内化速率常数也可使小麦根对Cd的内化通量减少,因此不能完全用竞争效应解释其结果.另外,阳离子的存在会改变小麦根表的性质,Ca2+、Mg2+的存在会增加亨利系数KCd,即生物配体浓度{Rcel}l和(或)离子与生物配体结合稳定常数KCd-Rcell会增加,同时这些离子的存在还会降低渗透常数p和kint;Cu2+、Ni2+的存在会降低KCd;且p和k在低浓度Cd(0.01～0.05μM)条件下增加,在高浓度Cd条件下降低.     

胶原纤维固化黑荆树单宁吸附Cr(VI)的研究

研究了胶原纤维固化黑荆树单宁对Cr(VI)的吸附.采用不同温度、pH值等条件进行吸附研究,并进一步探讨了固化黑荆树单宁的吸附动力学和吸附柱动力学及其吸附机理.结果表明,该材料对Cr(VI)的吸附平衡符合Freundlich方程,温度对吸附平衡的影响不明显;吸附动力学可用拟二级速度方程来描述,该材料同时具有良好的柱动力学特性;Cr(VI)的吸附过程可能存在3个反应,即Cr(VI)与吸附剂之间发生氧化还原反应生成Cr(III),Cr(III)和-COOH之间发生离子交换反应,以及Cr(III)与单宁的邻位羟基发生螯合.图8表2参10     

Thallium(I) and thallium(III) induce apoptosis in isolated rat hepatocytes by alterations in mitochondrial function and generation of ROS

Environmental metal toxins, generated through diverse anthropogenic activities, constitute one of the major contaminants that have led to global dispersion of these toxic metals in the ecosystem. Thallium is one of these widely dispersed metals that produce severe adverse effects on human and biological systems. The influence of thallium(I) and thallium(III) on the early events that trigger apoptosis signaling were examined in freshly isolated rat hepatocytes. In addition, the role of oxidative stress, and mitochondria in the induction of apoptosis were also investigated. Incubation of thallium(I) and thallium(III) with isolated rat hepatocytes generated reactive oxygen species (ROS), collapse of mitochondrial membrane potential, activation of caspases cascade, and appearance of apoptosis phenotype. Mitochondrial permeability transition (MPT) pore sealing agents (cyclosporine A and carnitine) and ATP generators (L-glutamine, fructose, and xylitol) inhibited the activation of caspase-3 and apoptosis, indicating that both the cations activated apoptosis signaling via mitochondrial pathway. Pretreatment of hepatocytes with antioxidants (α-tocopherol or deferoxamine) also blocked caspase-3 activation induced by these cations, suggesting that oxidative stress may be directly involved in a mitochondrial MPT pore opening and activation of caspases cascade. These findings contribute to a better understanding of the mechanisms that mediate thallium-induced apoptosis in isolated rat hepatocytes.