Analysis of 28 insecticides in curry leaves (Murraya koenigii L.) by gas chromatography and gas chromatography–mass spectrometry

A simple and efficient method was developed for analysis of 28 insecticides (organochlorines, organophosphates and synthetic pyrethroids) in curry leaves (Murraya koenigii L.). The extraction of the analytes was carried out with acidified acetonitrile and purification with magnesium sulphate, primary secondary amine along with graphitised carbon black to remove excess chlorophyll content in curry leaves. Acetonitrile extracts were changed into hexane + acetone (9 + 1) and hexane + toluene (9 + 1) in the final step. In another method ethyl acetate was used for extraction and purification was carried out as above. The analytes in the samples were determined by gas chromatography (GC) and confirmed by gas chromatography–mass spectrometry (GC–MS). Use of ethyl acetate increased the recovery of the analytes, but co-extractive interference led to higher GC maintenance. Acidified acetonitrile was found to be a better extraction solvent compared with ethyl acetate. The use of hexane:toluene (9:1) as exchange solvent increased the recovery of organochlorine insecticides compared with hexane:acetone (9:1). The limit of quantification (LOQ) of the method was 0.01 mg kg^?1 for organochlorine insecticides and 0.05 mg kg^?1 for organophosphates and synthetic pyrethroids. The recoveries of organochlorines were within 70.36–82.45%; organophosphates, 82.54–90.93% and synthetic pyrethroids, 88.45–90.71% at the LOQ level. The method developed was found suitable for analysis of real samples of curry leaves. The pesticides detected in curry leaves collected from the retail market were mainly organophosphates and synthetic pyrethroids.     

Application of programmable temperature vaporisation injection with resistive heating-gas chromatography flame photometric detection for the determination of organophosphorus pesticides

The combination of a programmable temperature vaporisation (PTV) injector with resistive heating GC (RH-GC), a form of fast GC, has been applied to the analysis of organophosphorus (OP) pesticides. The PTV injector was optimised in the 'at-once' solvent vent mode for the injection of ethyl acetate (10-40 microL) or ACN (10 microL). The short RH-GC column (5 m x 0.25 mm ID) with fast temperature ramps (up to 153 degrees C/ min) allowed the separation of a total of 20 OP pesticides in less than 6 min. Average recoveries between 67 and 119% were obtained for pesticides spiked at 0.01 mg/kg into apple and pear matrix. Extraction of orange juice with ACN provided higher recoveries (92-104%) for methamidophos, acephate and omethoate compared to ethyl acetate (62-73%). Results for analysis of OP pesticides in samples containing incurred residues were in good agreement with those obtained using GC-MS. The overall method was rapid, allowing 20 samples to be analysed in 4 h.     

Liquid-liquid equilibrium in the toluene-methyl ethyl ketone-water system

For the toluene-methyl ethyl ketone-water system the liquid-liquid equilibrium tie-line data have been determined at 40 and 0°C and the binodal curve for this system has been determined at 40, 0 and −10°C. The tie-line data at 40 and 0°C could be correlated with good accuracy using NRTL and UNIQUAC model equations.     

Determination of polar organophosphorus pesticides in vegetables and fruits using liquid chromatography with tandem mass spectrometry: selection of extraction solvent

A method based on liquid chromatography (LC)-mass spectrometry (MS)/MS was developed for sensitive determination of a number of less gas chromatography (GC)-amenable organophosphorus pesticides (OPs; acephate, methamidophos, monocrotophos, omethoate, oxydemeton-methyl and vamidothion) in cabbage and grapes. For extraction, several solvents were evaluated with respect to the possibility of direct injection, matrix-induced suppression or enhancement of response, and extraction efficiency. Overall, ethyl acetate was the most favourable solvent for extraction, although a solvent switch was required. For some pesticide/matrix combinations, reconstitution of the residue after evaporation required special attention. Extracts were analysed on a C18 column with polar endcapping. The pesticides were ionised using atmospheric pressure chemical ionisation on a tandem mass spectrometer in multiple reaction monitoring mode. The final method is straightforward and involves extraction with ethyl acetate and a solvent switch to 0.1% acetic acid/water without further cleanup. The method was validated at the 0.01 and 0.5 mg/kg level, for both cabbage and grapes. Recoveries were between 80 and 101% with R.S.D. < 11% (n = 5). The limit of quantification was 0.01 mg/kg and limits of detection were between 0.001 and 0.004 mg/kg.     

Effect of storage temperature on degradation of methidathion in fortified orange and peach juices

The effect of storage temperature on methidathion degradation in orange and peach juices was studied. The insecticide was aseptically added to packed orange and peach juices, which were stored at 40, 15, and 0 degrees C. Samples were taken at regular intervals and examined for residues of methidathion. Residues were determined with a simple gas chromatographic method; recoveries of methidathion from orange and peach juices ranged from 88.1 to 110% for both juices, and the limits of determination were 0.004 and 0.003 mg/kg, respectively. The experimental data were used to evaluate rate constants, half-lives, and times required to reach legal maximum residue limits, and activation energies for the decomposition of methidathion in orange and peach juices. Storage of fruit juices in refrigerated rooms greatly extended the half-life of methidathion beyond that of methidathion in samples stored at higher temperatures. Half-life values for methidathion in orange and peach juices, respectively, were 4.1 and 3.8 days for storage at 40 degrees C, 115 and 113 days for storage at 15 degrees C, and 330 and 385 days for storage at 0 degrees C. Activation energies for methidathion degradation in orange and peach juices were 22.6 and 21.7 kcal/mol, respectively.     

Multiresidue analysis of 83 pesticides and 12 dioxin-like polychlorinated biphenyls in wine by gas chromatography–time-of-flight mass spectrometry

A multiresidue method is described for simultaneous estimation of 83 pesticides and 12 dioxin-like polychlorinated biphenyls (PCBs) in red and white wines. The samples (20 mL wine, acidified with 20 mL 1% HCl) were extracted with 10 mL ethyl acetate (+20 g sodium sulphate) and cleaned by dispersive solid-phase extraction (DSPE) with anhydrous calcium chloride and Florisil successively. The final extract (5 mL) was solvent exchanged to 1 mL of cyclohexane:ethyl acetate (9:1), further cleaned by DSPE with 25 mg primary secondary amine sorbent and analyzed by gas chromatography–time-of-flight mass spectrometry (GC–TOF-MS) within 31 min run time. The limits of quantification of most analytes were ≤10–20 μg/L. Acidification of wine prior to extraction prevented hydrolysis of organophosphorous pesticides as well as dicofol, whereas treatment with CaCl₂ minimized the fatty acid co-extractives significantly. Solvent exchange to cyclohexane:ethyl acetate (9:1) further minimized the co-extractives. Recoveries at 5, 10 and 20 ng/mL were >80% for most analytes except cyprodinil, buprofezin and iprodione. The expanded uncertainties at 10 ng/mL were <20% for most analytes. Intra-laboratory precision in terms of Horwitz ratio of all the analytes was below 0.5, suggesting ruggedness of the method. Effectively, the method detection limit for most analytes was as low as up to 1 ng/mL in both red and white wine, except for cyfluthrin and cypermethrin.     

Solubility of methane in cellulose acetate — conditioning effect of carbon dioxide

The solubility of CH₄ and CO₂ in cellulose 2.4-acetate membranes was measured at temperatures between —10° and 30°C, and at pressures of up to 40 atm. Pre-exposure of the membrane samples to high-pressure CO₂ caused an increase in the solubility of CH₄, as well as of CO₂ [2]. In contrast, pre-exposure of the samples to high-pressure CH₄ did not alter the solubility of either CH₄ or CO₂. A similar “conditioning effect” by high-pressure CO₂ was also observed with other glassy polymers by Paul et al. [9-11], who reasonably attributed it to the non-equilibrium nature of the glassy state. The solubility isotherms for CH₄ and CO₂ in cellulose 2.4-acetate can be fitted to the “dual-mode” sorption model [1], but a consideration of the heats of solution suggests that a “two Langmuir sites” model [16] may offer a more satisfactory representation of the data. The cellulose acetate samples employed in this study were prepared by drying reverse osmosis membranes and are believed to have contained a large amount of free volume.     

气相色谱法测定茶叶中的噻嗪酮、甲胺磷、乙酰甲胺磷及三唑磷残留

建立了同时测定茶叶中噻嗪酮、甲胺磷、乙酰甲胺磷和三唑磷4种农药残留量的测定方法。在45 ℃加温条件下,用乙酸乙酯-正己烷混合溶剂提取及活性炭色谱柱净化,用不同配比的乙酸乙酯-正己烷混合液梯度洗脱待测组分,以DB-210毛细管色谱柱分离、氮磷检测器测定。结果表明,上述4种农药在10 min内能很好地分离;样品加标回收率(n=3)为73.4%~96.9%。方法的变异系数为2.49%~3.35%,茶叶（干重）中4种农药的定量检测下限为7.0~12.0 μg/kg。     

Determination of chlorpyrifos and acephate in tropical soils and application in dissipation studies

A rapid and accurate method for the extraction and determination of the two organophosphorus insecticides, chlorpyrifos and acephate in top- and subsoil materials of three tropical clayey soils from Sarawak has been developed. Soil samples were extracted with ethyl acetate and the pesticides were determined by GC-FPD. High recoveries of 76–102% and 76–100% were obtained for acephate and chlorpyrifos respectively, at fortification levels of 0.01, 0.1 and 1 mg kg^?1 with standard deviations below 9.0%. The addition of water prior to the extraction was important for obtaining high and reproducible recoveries. The method did not require clean-up of the extracts prior to GC analysis and could be detected down to 0.01 mg kg^?1. A field study was conducted using the modified method to measure the degradation kinetics and migration of acephate and chlorpyrifos in one of the soils over a period of 84 days. The degradation of acephate and chlorpyrifos were rapid with half-lives of 3.3 and 8.7 days, respectively. Both pesticides were detected in subsoils 2 h after application at the deepest (50 cm) soil layers examined and at concentrations up to 5.42 mg kg^?1. Subsoil concentrations of acephate were higher than for chlorpyrifos, and subsoil concentrations of acephate peaked after it had started to degrade in the top soil. The subsoil concentrations of the pesticides were attributed to transport with soil particles (chlorpyrifos) and via solution (acephate) through pores and cracks present in the soil profiles. The study demonstrates the high mobility of even strongly retained and fast degrading pesticides under tropical humid conditions.     

Methoxy-mercuration of methacrylic and cinnamic esters and cinnamaldehyde

The methoxymercuration of methyl and ethyl methacrylates, ethyl cinnamate and cinnamaldehyde has been kinetecally studied in the temperature range 35°–50°. Second-order kinetics has been observed for the over-all reaction. In all the cases, the reaction is appreciably accelerated by acetic acid and strongly retarded by sodium acetated and nitrogen bases. The results indicate an ionic mechanism involving a reactive carbonium ion as an intermediate formed by interaction between the unsaturated compound and undissociated mercuric acetate.     

A study of large-volume on-column injection GC-ECD for the ultratrace analysis of organochlorine pesticides in water

In this work, a large-volume on-column injection method for the analysis of 21 organochlorine pesticides, including HCH isomers, DDT derivatives and cyclodiene derivatives, was optimized. The solvent selected to carry out the study was ethyl acetate and the injection volume was 100 μl. Some factors were introduced in a Plackett-Burman design to determine their influence in the vaporization efficiency. The significant factors were then studied by a univariate procedure and sorted according to their importance on the response. The effect of the injection conditions on the peak resolution was also noted. The conditions selected according to sensitivity and resolution were: initial oven temperature 75 °C, injection speed 20 μl s⁻¹, solvent vapor exit (SVE) valve closure time 60 s, initial pressure 100 kPa and isothermal oven time 1 min. Analytical characteristics expressed in terms of precision, linear range, and limit of detection have been determined and compared with those obtained by splitless injection. The degradation of endrin and p,p′-DDT thermolabile pesticides was evaluated for both injection techniques. Finally the developed method was successfully applied to the ultratrace analysis of pesticides in natural waters. With this purpose a micro liquid-liquid extraction method using 2 ml of ethyl acetate to extract 10 ml of water sample was proposed. Recoveries between 69 and 107% were obtained with a very good precision (0.2-1.3%) for the studied pesticides, except for p,p′-DDD. Detection limits between 0.3 and 25 ng l⁻¹, which fulfill the limits established by the new water directive 2008/105/EC, were achieved. The MLLE method was compared with the SPE method by the analysis of some water samples using both procedures, and good concordance was obtained.     

Multiresidue analysis of pesticides in vegetables and fruits using a high capacity absorbent polymer for water

A single extraction and a single clean-up procedure was developed for multi-residue analysis of pesticides in non-fatty vegetables and fruits. The method involves the use of a high capacity absorbent polymer for water as a drying agent in extraction from wet food samples and of a graphitized carbon column for clean-up. A homogeneously chopped food sample (20 g) and polymer (3 g) were mixed to absorb water from the sample and then 10 min later the mixture was vigorously extracted with ethyl acetate (100 ml). The extract (50 ml), separated by filtration, was loaded on a graphitized carbon column without concentration. Additional ethyl acetate (50 ml) was also eluted and both eluates were concentrated to 5 ml for analysis. The procedure for sample preparation was completed within 2 h. In a recovery test, 107 pesticides were spiked and average recoveries were more than 80% from asparagus, orange, potato and strawberry. Most pesticides were recovered in the range 70-120% with usually less than a 10% RSD for six experiments. The results indicated that a single extraction with ethyl acetate in the presence of polymer can be applied to the monitoring of pesticide residues in foods.     

Preliminary phytochemical screening and in vitro anti-helicobacter pylori activity of extracts of the stem bark of Bridelia micrantha (Hochst., Baill., Euphorbiaceae)

Helicobacter pylori is a major risk factor for gastritis, ulcers and gastric cancer. This study was aimed to determine the antimicrobial activity of the stem bark of Bridelia. micrantha on H. pylori isolated in South Africa. Extracts and clarithromycin were tested against 31 clinical strains, including a standard strain (NCTC 11638) of H. pylori, by measuring the diameters of the corresponding inhibition zones, followed by determination of the Minimum Inhibitory Concentration (MIC) (using metronidazole, and amoxicillin as control antibiotics) and the rate of kill. Preliminary phytochemical screening was also done. Inhibition zone diameters which ranged from 0-23 mm were observed for all five of the extracts and 0-35 mm for clarithromycin. Marked susceptibility of strains (100%) was noted for the acetone extract (P < 0.05), followed by ethyl acetate extract (93.5%). The MIC?? values ranged from 0.0048 to 0.156 mg/mL for the ethyl acetate extract and 0.0048 to 0.313 mg/mL for the acetone extract. The MIC?? values ranged from 0.0048 to 2.5 mg/mL for the ethyl acetate extract and 0.078 to > 0.625 mg/mL for the acetone extract, respectively. Insignificant statistical difference in potency was observed when comparing the crude ethyl acetate extract to metronidazole and amoxicillin (P > 0.05). Complete killing of strain PE430C by the ethyl acetate extract was observed at 0.1 mg/mL (2 × MIC) and 0.2 mg/mL (4 × MIC) at 66 and 72 h. For strain PE369C, 100% killing was observed at 0.1 mg/mL (2 × MIC) in 66 and 72 h. The ethyl acetate extract could thus be a potential source of lead molecules for the design of new anti-Helicobacter pylori therapies as this study further confirmed the presence of phytochemicals including alkaloids, flavonoids, steroids, tannins and saponins.     

分散固相萃取/高效液相色谱-串联质谱法检测大葱中虫酰肼、涕灭威及其衍生物的农药残留

采用分散固相萃取法净化(DSPE),高效液相色谱-串联质谱法(HPLC-MS/MS)在分时段多反应监测模式下对大葱中的虫酰肼、涕灭威及其衍生物进行测定,外标法定量,并对比了乙酸乙酯和乙腈作为提取剂的提取效果.结果表明,采用乙腈为提取剂时,4种农药在10～120μg/L范围内线性关系良好,且方法的定量下限(LOQ)均低于...     

1,3,6,8-Tetraethynylpyrene and 1,3,6,8-tetrakis (trimethylsilylethynyl) pyrene: Photophysical properties in homogeneous media

The photophysical properties of two new tetra substituted derivatives of pyrene: 1,3,6,8-tetraethynylpyrene (TEP) and 1,3,6,8-tetrakis(trimethylsilylethynyl)pyrene (TEP-TMS) have been studied. Studies were done with respect to mirror image symmetry in the absorption and emission spectra and permissive or forbidden nature of S₀–S₁ transition, solvent sensitivity of the first and third vibronic bands and fluorescence anisotropy. Both the derivatives exhibited a strongly allowed S₀–S₁ transition, high fluorescence quantum yield, shorter fluorescence lifetime compared to pyrene and invariance of the vibronic band intensity ratio to solvent polarity. The behavior of the two pyrene derivatives validates the hypothesis “solvent polarity mediates vibronic coupling and therefore the emission band intensities, for forbidden S₀–S₁ transitions”. The trimethylsilyl derivative (TEP-TMS) was characterized by a strong fluorescence in solid state. The tetraethynyl derivative (TEP) showed high fluorescence anisotropy comparable to the well-known anisotropy probe DPH in glycerol at 0 °C. The fluorescence intensities of TEP and TEP-TMS did not show any significant change in the temperature ranger 0–40 °C for a low viscous solvent like ethanol and in the range 0–60 °C in glycerol. Unlike pyrene, no excimer emission was observed even up to 10⁻³ M for TEP and TEP-TMS.     

Biosensor analysis for the kinetic study of polyphenols deterioration during the forced thermal oxidation of extra-virgin olive oil

The process of artificial rancidification of extra-virgin olive oil due to heating in an oxidizing atmosphere was studied by testing an actual kinetic model of the process and monitoring the thermal oxidative degradation of the polyphenols contained in it. To this end, a series of oxidative degradation experiments were carried out on extra-virgin olive oil samples under isothermal conditions at 98, 120, 140, 160, and 180 °C using a thermostatic silicon oil bath. The experimental procedure used in this study carefully followed the recommendations regarding the study of olive oil rancidification set out in the AOM procedure. The change in polyphenol concentration with time was monitored at selected temperatures using a tyrosinase biosensor operating in an organic phase (n-hexane). The activation energy for the polyphenol degradation process determined using the MacCallum method was found to be practically constant throughout most of the process.

Furthermore, the application of the so-called “model-fitting” method to this process enabled the specific constant rates to be determined at the above-mentioned selected temperatures. In addition, a confirmation of the activation energy value was obtained by the “model-fitting” method and the algorithm of the kinetic model equation best-fitting the experimental curve representing the whole process was checked.

Finally, further very interesting observations were made, for instance, the half-life concentration values of polyphenols at selected temperatures between 98 and 180 °C.     

Thermotropic cellulose derivatives with flexible substituents. III. Temperature dependence of cholesteric pitches exhibiting a cholesteric sense inversion

For the thermotropic cholesteric mesophase of tri-o-(β-methoxyethoxy)ethyl cellulose (DP = 11), cholesteric pitches larger than 2 μm were precisely determined by microscopic observation and their temperature dependence was examined in the temperature range from 80°C to 140°C. In the initial temperature region of 80°C to 106°C, the pitch increases with increasing temperature. After the pitch diverges at 106°C, it decreases as temperature is raised further. This anomalous temperature dependence of pitch was associated with a thermally-induced inversion from right- to left-handed helicoidal structure which was first observed in this kind of cellulose derivatives.     

凝胶渗透色谱净化-气相色谱/串联质谱分析蘑菇中的36种农药残留

建立了用凝胶渗透色谱净化-气相色谱/串联质谱分析蘑菇中36种农药残留的方法。蘑菇中的待测农药组分在30 ℃条件下用乙酸乙酯提取,高速匀浆后通过凝胶渗透色谱净化;选用填料为中性多孔的聚苯乙烯二乙烯基苯微球体的S-X3玻璃柱(22 g,19 cm×2 cm)作为凝胶渗透色谱净化柱,流动相为乙酸乙酯-环己烷(体积比为1∶1)溶液,流速5 mL/min;收集第7~15 min流出的液体用气相色谱-三重四极杆串联质谱仪测定。在0.01~1.0 mg/L的质量浓度范围内,各种农药标准溶液的线性相关系数均大于0.99。在样品中添加36种农药(添加水平为0.01,0.05,0.10 mg/kg)的混合标准溶液,平均回收率为72.6%~117.1%,相对标准偏差为2.0%~10.8%(n=5),最低检出限为 0.1~0.7 μg/kg,最低定量限为 0.2~2 μg/kg。     

Structure and properties of a styrene–butadiene–styrene block copolymer

Electron-microscopic texture and physical properties of a styrene–butadiene–styrene (SBS) block copolymer obtained by casting from toluene, carbon tetrachloride, ethyl acetate, and methyl ethyl ketone are discussed. Two peaks are observed in the mechanical loss (tan delta;) curve at ?70 and 100°C which are attributed to segmental motion of polybutadiene and polystyrene, respectively. The polybutadiene peak heights are in the order of solubility in the solvent used; the polystyrene peak heights are in converse order. In addition to these peaks, a third peak is observed at 10°C for specimens cast from ethyl acetate or methyl ethyl ketone. A transition corresponding to this peak is also noticed in thermal analysis. It is proposed that aggregation of styrene blocks is relatively incomplete in specimens cast from solution in poor solvents.     

Determination of abamectin and azadirachtin residues in orange samples by liquid chromatography-electrospray tandem mass spectrometry

A rapid and sensitive LC-ESI-MS-MS method has been developed for the determination of azadirachtin and abamectin residues in orange samples. Samples were extracted with acetonitrile, in a high-speed blender. After the addition of sodium acetate, an aliquot of extract was directly injected into the LC-ESI-MS-MS system. The highest sensitivity of the method was achieved under MS-MS conditions using [M+Na]+ adducts as precursor ions. Recoveries for both compoundsfrom spiked orange samples at 0.01 and 0.1 mg/kg were above 80%, with good repeatability (<10%). Method detection limits achieved (<0.007 mg/kg) were adequate for the determination of these pesticides in this kind of sample from the regulatory point of view. The importance of the solvent used for extraction, as well as the addition of sodium acetate to the extracts and the selection of adequate chromatographic conditions are discussed.