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.     

可吸入尘中苯并（a）芘超声提取的高效液相色谱测定法

本文介绍一种简便、快速的可吸入尘中苯并(a)茈高效液相色谱测定方法.本法仅需5mL乙腈,超声处理10min即可完成提取过程.提取液离心后,上清液可直接进行HPLC分析.色谱条件:反相C18柱,用乙腈/水梯度洗脱,紫外检测器,λ=254nm.方法的最小检出量10~(-10)g.回收率95%,变异系数4、3%.此方法可用于大气可吸入尘中Bap的监测.     

The estimation of bioconcentration factors of aromatic hydrocarbons by high‐performance liquid chromatography

The determination of Bioconcentration Factors (BCF) via HPLC capacity factors (k') has been studied, including the effect of column type and mobile phase composition on the correlation between log BCF and log k’. Values of BCF correlate well with the phenylsilica column capacity factors. The phenylsilica column followed by C18 column give better correlations than either C8 or C2 column. The use of HPLC with phenylsilica as stationary phase and methanol‐water as mobile phase in the prediction of BCF can be at least as good or better than the use of n‐octanol/water partitioning system. There are no significant differences in the correlations between log k’ and log BCF with the changes of methanol concentration in the mobile phase, and it seems that a high proportion of methanol in the eluent is required to obtain good results.     

Determination of chlorothalonil residues in coffee

Coffee beans were treated with the fungicide chlorothalonil (2,4,5,6‐tetrachloro‐1,3‐benzene‐dicarbonitrile) and the residues were determined by high‐performance liquid Chromatograph (HPLC). Several techniques including Soxhlet extraction (SE), microwave‐assisted extraction (MAE) and accelerated solvent extraction (ASE) were compared for the extraction of residues. A column clean‐up procedure was developed to remove the co‐extractives in the extract before HPLC analysis. The overall mean recoveries from extracts obtained by SE, MAE and ASE were 89.2 ±3.9, 88.4 ±1.9 and 82.8 ±0.3, respectively. The results show that MAE followed by HPLC is a viable alternative to the commonly used SE and gas Chromatographic analysis for the determination of chlorothalonil in coffee.     

水中痕量亚当氏剂和二苯胺的固相微萃取方法研究

研究了固相微萃取(SPME)-高效液相色谱(HPLC)测定水样中痕量亚当氏剂和二苯胺的分析方法.对SPME的条件如萃取纤维、萃取时间、萃取温度、离子强度、解吸方式、解吸溶剂、解吸时间进行了优化,并用于地下水等实际水样的分析.SPME优化的条件为:选用60μmPDMS/DVB萃取纤维在室温25℃下直接萃取60min,磁力搅拌速度为1100r.min-1,然后萃取纤维在解吸室内静态解吸9min后进行HPLC分析.液相色谱分离条件为ZORBAXSBC18柱(4.6mmi.d.×250mm,5.0μm),流动相为甲醇-水(70:30,V/V),流速为1.0ml.min-1,二极管阵列检测器波长为280nm.方法线性范围为0.005mg.l-1—0.5mg.l-1(R>0.99),两种物质的检出限(S/N=3)分别为0.003mg.l-1和0.002mg.l-1.加标回收率分别在89.6%—100.4%和97.5%—100.1%(n=5)之间,相对平均标准偏差(RSD)分别在4.5%—6.2%和3.8%—6.7%之间.该方法快速、简便,无需使用有机溶剂,适于水样中痕量物质的分析.     

Callyspongia samarensis (Porifera) extracts exhibit anticancer activity and induce bleaching in Porites cylindrica (Scleractinia)

Marine sponges can produce allelopathic compounds with specific roles in the competition for benthic space. Here we demonstrate that extracts from Callyspongia samarensis (Phylum Porifera) accelerate bleaching in Porites cylindrica (Phylum Cnidaria, Order Scleractinia) and exhibit in vitro anticancer activity. A column chromatography fraction and HPLC fraction, purified from the crude methanol extract of C. samarensis, were incorporated into agar gel cubes at natural concentrations and tested on P. cylindrica corals in a laboratory assay. Statistical analysis of percent bleached area and maximum quantum yield showed that a significant difference existed between P. cylindrica nubbins that were exposed to C. samarensis extracts versus the control group. This suggests that C. samarensis contains allelopathic compounds that can cause bleaching in P. cylindrica, possibly leading to tissue necrosis and death. Furthermore, the aforementioned HPLC fraction exhibited significant growth inhibition of the HCT-116 (human colon cancer) cell line. Understanding the strategies by which sponges exert dominance over other organisms is important because it provides information about the ecological roles of sponge allelopathy and can result in the discovery of compounds with biomedical potential.     

常规液相色谱柱测定早熟素Ⅱ的方法探讨

通过使用市售的常规C18液相色谱柱(规格:150mm×4.6mm,5 μm),探讨了早熟素Ⅱ的分析方法并对其进行了可行性论证.以V(甲醇):V(水)=80:20为流动相,流量1 mL·min~(-1),检测波长为224nm,柱温35℃.得出早熟素Ⅱ在8～108μg·mL~(-1)的范围内呈良好的线性关系(相关系数,为0.99997),最低检出限为1.0379μg·mL~(-1)(信噪比为3),加标回收率为93.3%～104.98%,变异系数为0.12%～4.41%.与使用非常规色谱柱分析早熟索Ⅱ的方法相比,该方法采用了市售常规柱,能够更大限度地满足实验条件,通用性更强.     

Spectrophotometric and HPLC method for quantification of Loratadine on swabs for cleaning validation

Cleaning validation is a major challenge in multi-product pharmaceutical industries. UV spectrophotometric and HPLC methods have been developed and validated for determination of residual amount of Loratadine. Both methods were validated for linearity, range, accuracy, precision, and robustness. The limit of quantification was 1 mg L^?1 by UV spectrophotometric method and 0.5 mg L^?1 by HPLC method. A spike recovery study was done on a stainless steel (316 grade) plate and specific residual cleaning level (SRCL) was down to 6 μg 25.8 cm^?2. Recovery was found to be more than 70%. Both methods were simple, highly sensitive, precise, and accurate, and have potential of being useful for routine quality control.     

Cleanup by solid‐phase extraction and HPLC of organochlorine insecticides and PCBS in various nonfatty and fatty samples

An accurate, simple and cheap extraction and cleanup procedure for capillary GC analysis of organo‐chlorine insecticides (OCs) in vegetables (cabbage and carrots) at the ng/g level, and for soil at the μg/g level is presented. The cleanup is carried out on solid‐phase extraction (SPE) cartridges, filled with 500 mg silica, 1 g of deactivated Florisil (10% w/w water), and 100 mg of anhydrous sodium sulphate. Recoveries >90% are obtained. The cleanup of OCs in fatty samples on an HPLC LiChrosorb Si 100 column is evaluated for subsequent capillary GC analysis. Fractionation of OCs and Aroclor 1254 and 1260 on an HPLC Nucleosil 100 column appears to be satisfactory.     

Biodegradation of carbofuran in sequencing batch reactor augmented with immobilised Burkholderia cepacia PCL3 on corncob

The performance of sequencing batch reactors (SBRs) augmented with immobilised Burkholderia cepacia PCL3 on corncob for biodegradation of carbofuran in basal salt medium (BSM) was studied. A 2.0-L SBR with a working volume of 1.5 L was operated for a total cycle of 48 h, consisting of 1.0 h fill phase, 46 h react phase and 1.0 h decant phase. The initial pH of the feed medium was 7.0. Air was fed into the reactor at a controlled flow rate of 600 mL·min ^?1. The effect of hydraulic retention time (HRT) (14 to 6 days) on carbofuran-degradation efficiency was investigated at a carbofuran concentration in the feed medium of 20 mg·L ^?1. The shortest HRT resulting in complete degradation of carbofuran was 8 days. At 75% of the optimum HRT (6 days), the effects of biostimulation using organic amendments, i.e. molasses, cassava pulp, rice bran and spent yeast, and the effect of carbofuran concentration in the feed medium (20–80 mg·L ^?1) were investigated. The optimum conditions for SBRs were an initial carbofuran concentration of 40 mg·L ^?1 and 0.1 g·L ^?1 of rice bran as a biostimulated amendment. Complete degradation of carbofuran with a first-order kinetic constant (k ₁) of 0.044 h^?1 was achieved under these optimum conditions.     

水中杀菌剂叶青双及其降解物的反相液相色谱测定

本文用反相液相色谱法测定水中叶青双及其降解物2-氨基5-巯基-1,3,4-噻二唑。平均回收率分别为91％和94％;对水样的最低检测浓度分别为2ppb和0.8ppb;叶青双与2-氨基-5-巯基-1,3,4-噻二唑的分离度为2.5。本法在柱效和灵敏度上比硅胶柱液相色谱法有明显的提高。     

快速液相色谱-串联质谱法测定环境空气中的全氟化合物

不同研究报道的空气中离子型全氟化合物(PFCs)的分析方法各不相同,本文的目的在于对比和优化不同分析条件。通过对比不同流动相(甲醇和乙腈)、不同色谱柱(C8和C18)、不同梯度洗脱条件下目标化合物的分离效果,确定了以甲醇为流动相、C18色谱柱为分离柱和最佳梯度淋洗液分离的仪器分析条件。比较了甲醇和正已烷/丙酮混合溶剂萃取气相(PUF)和颗粒相(GFF)样品的效果,确定以甲醇为萃取溶剂。建立了空气中PFCs的LC-MS/MS优化分析方法,方法线性范围在0.1~50 ng·m L~(-1)之间,PUF与GFF样品方法检出限分别为0.02~0.35 pg·m~(-3)和0.02~0.26 pg·m~(-3)。同时将方法用于大气实际样品分析。     

植物体内水杨酸分析方法的探讨及其应用(Investigation and Application of Analysis Methods of Salicylic Acid in Plant Tissue)

准确测定植物中水杨酸的含量是深入研究其重要作用和抗病机理的必要前提.采用高效液相色谱(HPLC)对植物中内源水杨酸进行了分析,比较了紫外检测器和荧光检测器不同的检测结果,发现荧光监测器灵敏度更高,是紫外检测器的15倍.论文同时比较了使水杨酸与其他组分很好分离的液相色谱条件,结果表明,pH5.5的乙酸钠:甲醇(9:1,V/V)的流动相效果最好.用该方法测得的精密度的相对标准偏差为1.73%,重现性和稳定性均较好(稳定性的相对标准偏差为4.6%).论文以模式植物拟南芥(Arabidopsis thaliana)的野生型和水杨酸突变体两种类型为供试材料,对其体内水杨酸进行了提取测定,检测结果发现野生型体内的水杨酸的含量大约是水杨酸突变体的9倍,与文献报道吻合.     

Transmission distance of chemical cues from coral habitats: implications for marine larval settlement in context of reef degradation

The present study (Ishigaki Island, Japan) explored the distance of transmission of chemical cues emitted by live versus dead coral reefs (Exp. 1: High performance liquid chromatography (HPLC) analyses with water sampling station at 0, 1, and 2 km away from the reef) and the potential attraction of these chemical cues by larval fish, crustaceans, and cephalopods (Exp. 2: choice flume experiment conducted on 54 Chromis viridis larvae, 52 Palaemonidae sp larvae, and 16 Sepia latimanus larvae). In the experiment 1, HPLC analyses highlighted that the live coral reef (and not the dead coral reef) produced different and distinct molecules, and some of these molecules could be transported to a distance of at least 2 km from the reef with a reduction of concentration by 14–17-fold. In the experiment 2, C. viridis, Palaemonidae sp, and S. latimanus larvae were significantly attracted by chemical cues from a live coral reef (sampling station: 0 km), but not from a dead coral reef. However, only C. viridis larvae detected the chemical cues until 1 km away from the live coral reef. Overall, our study showed that chemical cues emitted by a live coral reef were transported farthest away in the ocean (at least 2 km) compared to those from a dead coral reef and that fish larvae could detect these cues until 1 km. These results support the assumption of a larval settlement ineffective in degraded coral reefs, which will assist conservationists and reef managers concerned with maintaining biodiversity on reefs that are becoming increasingly degraded.     

A rapid determination of histamine and 3-methylhistamine in human plasma by high performance liquid chromatography

Histamine plays an important pathophysiological role in allergy, inflammation, gastric acid secretion, microcirculation and neurotransmission. 3-Methylhistamine is a prominent metabolite of histamine. Different methods for determination of histamine in biological fluids have been developed. In the present study, a simple, simultaneous determination of histamine and 3-methylhistamine by HPLC (precolumn derivatization with fluorescamine) was developed in human plasma using fluorescence detection with 1-methylhistamine as the internal standard. Linear regression analysis of the ratios of the concentrations of histamine and 3-methylhistamine (X) against peak height ratios (Y) yielded the following: y = 0.0073x ? 0.0096 (R ² = 0.990) and y = 0.0077x ? 0.0111 (R ² = 0.989). In conclusion, it was possible to detect histamine and 3-methylhistamine below 5 ng mL^?1 in 1 mL plasma.     

硝基化合物的高效液相色谱(HPLC)分析

硝基化合物是炸药废水的主要成分,大部分硝基化合物具有较高的毒性.本文对奥克托今、黑索今、1,3,5-三硝基苯、1,3-二硝基苯、硝基苯、2,4,6-三硝基甲苯、2-氨基-4,6-二硝基甲苯、2,4-二硝基甲苯共8种硝基化合物的紫外光谱和液相色谱分离条件进行了研究,其最佳检测波长分别为228 nm、227 nm、227 nm、237 nm、272 nm、230 nm、226 nm、244 nm.本文建立了8种硝基化合物的高效液相色谱测定方法,色谱条件为:色谱柱为ZORBAX SB-C18(3.0 mm×250 mm,5μm),检测器为紫外检测器,流动相为甲醇-水(50∶50),流速为0.5 mL.min-1.水中8种硝基化合物可以在13 min内得到较好的分离,检出限均≤0.8 ng,回收率大于95%.     

Determination of cadmium in water and herbal medicine by Penicillium chrysogenum immobilized on silica gel for flame atomic absorption spectroscopy

Penicillium chrysogenum was immobilized on silica to develop a simple and cost effective method for solid phase extraction of Cd(II) and determination using flame atomic absorption spectrometry (FAAS). The sorbent was characterized by Fourier transform infrared spectroscopy and packed into a column. The conditions for quantitative sorption and desorption of Cd(II) were optimized. The preconcentration factor was 100 while detection limit was 0.61 µg L^?1 with a relative standard deviation of 1.0%. The method was applied for determination of Cd in herbal medicine and tap water.     

Effects of high temperature and CO2 on intracellular DMSP in the cold-water coral Lophelia pertusa

Significant warming and acidification of the oceans is projected to occur by the end of the century. CO₂ vents, areas of upwelling and downwelling, and potential leaks from carbon capture and storage facilities may also cause localised environmental changes, enhancing or depressing the effect of global climate change. Cold-water coral ecosystems are threatened by future changes in carbonate chemistry, yet our knowledge of the response of these corals to high temperature and high CO₂ conditions is limited. Dimethylsulphoniopropionate (DMSP), and its breakdown product dimethylsulphide (DMS), are putative antioxidants that may be accumulated by invertebrates via their food or symbionts, although recent research suggests that some invertebrates may also be able to synthesise DMSP. This study provides the first information on the impact of high temperature (12 °C) and high CO₂ (817 ppm) on intracellular DMSP in the cold-water coral Lophelia pertusa from the Mingulay Reef Complex, Scotland (56°49′N, 07°23′W), where in situ environmental conditions are meditated by tidally induced downwellings. An increase in intracellular DMSP under high CO₂ conditions was observed, whilst water column particulate DMS + DMSP was reduced. In both high temperature treatments, intracellular DMSP was similar to the control treatment, whilst dissolved DMSP + DMS was not significantly different between any of the treatments. These results suggest that L. pertusa accumulates DMSP from the surrounding water column; uptake may be up-regulated under high CO₂ conditions, but mediated by high temperature. These results provide new insight into the biotic control of deep-sea biogeochemistry and may impact our understanding of the global sulphur cycle, and the survival of cold-water corals under projected global change.     

西洋参中六种农药残留量的HPLC分析

本文报道了甲基对硫磷等六种农药在西洋参中多残留的高铲液相色谱检测方法。采用乙醚超声波提取，经硅胶柱净化，紫外检测波长采用程序控制，在检测的时间内自动进行四次改变，使每一被检测的农药均在其最大紫外吸收波长处被检测。     

Ethyl carbamate in foods and beverages: a review

Food and beverages contain many toxic chemicals that raise health concerns. Ethyl carbamate (EC) or urethane is the ethyl ester of carbamic acid. It occurs at low level, from ng/L to mg/L, in many fermented foods and beverages. Ethyl carbamate is genotoxic and carcinogenic for a number of species such as mice, rats, hamsters and monkeys. It has been classified as a group 2A carcinogen, “probably carcinogenic to humans”, by the World Health Organization’s International Agency for Research on Cancer (IARC) in 2007. The benchmark dose lower limit of ethyl carbamate is 0.3 mg/kg bw per day and the mean intake of ethyl carbamate from food is approximately 15 ng/kg bw per day. Those levels were calculated for relevant foods including bread, fermented milk products and soy sauce. Alcoholic beverages were not included in this calculation. However, high levels of ethyl carbamate can be found in distillated spirits at concentrations ranging from 0.01 to 12 mg/L depending on to the origin of spirit. Alcoholic drinks should thus be considered as a source of ethyl carbamate. Ethyl carbamate is produced by several chemical mechanisms: first, from urea and various proteins like citrulline produced during the fermentation step and second from cyanide, and hydrocyanic acid, via ethyl carbamate precursors such as cyanate. A large panel of ethyl carbamate formation mechanisms is described from simple ethanolysis of urea in homogeneous liquid phase to photochemical oxidation of cyanide ion or complex heterogeneous gas/solid catalytic reactions. Determination of ethyl carbamate in foods and beverages involves various strategies according to the material, food or beverage, solid or liquid, and according to the concentration, from ng/L to mg/L. Usually, adapted extractive techniques and pre-concentration step are followed by analysis by gas chromatography coupled to mass spectrometry (GC–MS of GC–MS–MS). High performance liquid chromatography (HPLC) and semi-quantitative spectroscopic methods (infra-red) are also proposed as valuable alternatives to the classical but time-consuming GC–MS. Various preventing methods are developed and used in some cases at industrial scale to lower ethyl carbamate levels in food. Two types of preventing methods are described. First, adapted and optimised practices in all step of the chain of foods’ (or beverages) production lead in general to low ethyl carbamate level. Second, the abatement of ethyl carbamate precursors can be done by adapted enzymatic, physical chemical or chemical methods according to the natures of raw materials and conditions of their production processes.