Microwave-assisted-demulsification dispersive liquid-liquid microextraction for the determination of triazole fungicides in water by gas chromatography with mass spectrometry.

A novel microwave-assisted-demulsification dispersive liquid-liquid microextraction technique was established for determination of three triazole fungicides in environmental water samples by gas chromatography with mass spectrometry. Importantly, microwave irradiation has been applied in demulsification to achieve the phase separation and enrichment of triazole fungicides in water samples successfully with low-density toluene as extractant. The experimental variables, including microwave power, microwave time, ultrasonic time, type and volume of extraction solvent, and effect of salting out were investigated. Under the optimized conditions, the method showed good linearity for myclobutanil, tebuconazole, and difenoconazole in the range of 1-100 µg/L. The limits of detection and the limits of quantification were within the range of 0.14-0.27 and 0.47-0.90 µg/L, respectively. The suitable enrichment factors for three triazole pesticides were in the range of 425-636. The recoveries were between 89.3 and 108.7%, and the relative standard deviations were from 5.4 to 8.6%. Finally, environmental water samples were used to verify the applicability of the proposed method for analysis of triazole fungicides targets. It can be concluded that the developed microwave-assisted-demulsification dispersive liquid-liquid microextraction gas chromatography with mass spectrometry method was a rapid, efficient, reliable, and environmental friendly way for analysis of triazole fungicides in water.

Simultaneous determination of sulfonamides and metabolites in manure samples by one-step ultrasound/microwave-assisted solid-liquid-solid dispersive extraction and liquid chromatography-mass spectrometry.

An in-line matrix cleanup method was used for the simultaneous extraction of 15 sulfonamides and two metabolites from manure samples. The ultrasound/microwave-assisted extraction (UMAE) combined with solid-liquid-solid dispersive extraction (SLSDE) procedure provides a simple sample preparation approach for the processing of manure samples, in which the extraction and cleanup are integrated into one step. Ultrasonic irradiation power, extraction temperature, extraction time, and extraction solvent, which could influence the UMAE efficiency, were investigated. C18 was used as the adsorbent to reduce the effects of interfering components during the extraction procedure. The extracts were concentrated, and the analytes were analyzed by liquid chromatography-tandem mass spectrometry (LC-MS/MS) without any further cleanup. The isotopically labeled compounds sulfamethoxazole-d 4, sulfamethazine-d 4, sulfamonomethoxine-d 4, and sulfadimethoxine-d 6 were selected as internal standards to minimize the matrix effect in this method. The recoveries of the antibiotics tested ranged from 71 to 118 % at the three spiking levels examined (20, 200, and 500 µg · kg(-1)). The limits of detections were 1.2-3.6 µg · kg(-1) and the limits of quantification were 4.0-12.3 µg · kg(-1) for the sulfonamides and their metabolites. The applicability of the method was demonstrated by analyzing 30 commercial manure samples. The results indicated that UMAE-SLSDE combined with LC-MS/MS is a simple, rapid, and environmentally friendly method for the analysis of sulfonamides and their metabolites in manure, and it could provide the basis for a risk assessment of the antibiotics in agricultural environments.

Effect of acupuncture on hippocampal Ref-1 expression in cerebral multi-infarction rats.

Redox effector factor (Ref-1) is a sensitive marker for oxidative cellular injury. The aim of this study was to investigate the effects of acupuncture on hippocampal Ref-1 expression in cerebral multi-infarction rats. The rats with reference memory impairment were randomly allocated to three groups: impaired group, acupuncture group and placebo acupuncture group. Moreover, normal group and sham-operated group were set as control groups. Morris water maze test showed that cerebral multi-infarction rats did not present significant changes in spatial working memory performance. Further investigation by immunohistochemistry revealed that acupunctural treatment significantly increased the expression of Ref-1 in the hippocampus of the impaired rats. These findings suggested that the spatial working memory was unaffected in the cerebral multi-infarction rats although spatial reference memory deficits were detected in our previous study; in addition, acupuncture could increase the Ref-1 expression, consequently exerting the anti-oxidant effects.

[Study on the mechanism of liesegang pattern development during carbonating of traditional sticky rice-lime mortar].

Liesegang patterns in traditional sticky rice-lime mortar undergoing carbonation were investigated by means of FTIR, XRD and SEM. Results indicate that well-developed Liesegang patterns only occur in the mortar prepared with aged lime and sticky rice. The smaller Ca(OH)2 particle size in aged lime and the control of the sticky rice for the crystallization of calcium carbonate lead to the small pores in this mortar. These small pores can make Ca2+ and CO3(2-) highly supersaturated, which explains the reason why Liesegang pattern developed in the sticky rice-aged lime mortar. The formed metastable aragonite proves that Liesegang pattern could be explained based on the post-nucleation theory.

Identification of new minor metabolites of penicillin G in human serum by multiple-stage tandem mass spectrometry.

Liquid chromatography/mass spectrometry (LC/MS) and liquid chromatography/tandem mass spectrometry (LC/MS/MS) were applied to characterize drug metabolites. Although these two methods have overcome the identification and structural characterization of metabolites analysis, they remain time-consuming processes. In this study, a novel multiple-stage tandem mass spectrometric method (MS(n) ) was evaluated for identification and characterization of new minor metabolism profiling of penicillin G, one of the ß-lactam antibiotics, in human serum. Seven minor metabolites including five phase I metabolites and two phase II metabolites of penicillin G were identified by using data-dependent LC/MS(n) screening in one chromatographic run. The accuracy masses of seven identified metabolites of penicillin G were also confirmed by mass spectral calibration software (MassWorks™). The proposed data-dependent LC/MS(n) method is a powerful tool to provide large amounts of the necessary structural information to characterize minor metabolite in metabolism profiling.

Microwave-assisted Natural Deep Eutectic Solvents Pretreatment Followed by Hydrodistillation Coupled with GC-MS for Analysis of Essential Oil from Turmeric (Curcuma longa L.).

In the past decade, natural deep eutectic solvents (NADESs) as green and sustainable extraction solvents with great potential for the efficient extraction of bioactive compounds from the plants are emerging. In this study, a microwave-assisted technology is used to prepare natural deep eutectic solvents. And natural deep eutectic solvents as pretreatment solvents coupled with microwave-assisted hydrodistillation (MAHD) for isolating essential oil (EO) derived from turmeric (Curcuma longa L.) is investigated. To improve the essential oil yield of turmeric (Curcuma longa L.) as a target, various factors affecting extraction efficiency including the type and amount of natural deep eutectic solvents, pretreatment time, pretreatment temperature and hydrodistillation (HD) time are discussed and optimized through central composite design (CCD) of the response surface methodology (RSM). The optimal conditions are as follows: natural deep eutectic solvent composed of choline chloride and oxalic acid (molar ratio with 1:1) as a pretreatment solvent, an amount of 60 g, a pretreatment time of 5 min, a pretreatment temperature of 84 ºC, a hydrodistillation time of 76 min. Under the optimum conditions, the highest essential oil yield of 0.85% is achieved. Additionally, the essential oil is analyzed by using gas chromatography-mass spectrometry (GC-MS), with a total of 49 compounds being identified. Through combining natural deep eutectic solvents with a microwave-assisted hydrodistillation technique, this work provides an eco-friendly extraction way of isolating essential oil, which boosts development in the monitoring other spice quality field.

Dispersive Liquid-Liquid Microextraction Combined with Microwave Demulsification for Determination of FAME Residuals in Biodiesel Wastewater.

Biodiesel consists of various fatty acid methyl esters (FAMEs) that are mainly produced through transesterification of plant oil or animal fat. It is essential for biodiesel to be purified utmostly to meet its product standard before being traded, while the universal purification method has been water washing. However, water washing inevitably causes the residual of FAMEs in wastewater, which represents a loss of industrial profits. For the purpose of determination and monitoring of the FAME profile in wastewater, there is a necessity to develop a fast and reliable approach with small volume of sample in need. Hence, in this study, a combination of dispersive liquid-liquid microextraction (DLLME) and microwave demulsification is applied for the enrichment of residual FAMEs in water, followed by qualitative and quantitative analyses using gas chromatography-mass spectrometry. The results indicate that the optimal extractant in DLLME approach is toluene. And the optimal parameters are 20 mL of water sample, 80 µL of toluene as the extractant, 60 s of ultrasonic irradiation duration, 200 W of microwave power and 2 min of microwave irradiation duration. The standard curves and linear equations obtained with these conditions are used for the quantitative analysis of biodiesel wastewater, which reveals that there was 50.35 mg·L-1 of the total FAME residuals in wastewater. To the best of our knowledge, it is for the first time that the combined technique of DLLME and microwave demulsification is applied in determination of residual FAMEs in water samples. The proposed method corresponds to small volumes of sample and extractant and short analytical period. It also has the potential to be extended to the analysis of other water pollutants.

Effect of acupuncture treatment on spastic states of stroke patients.

PURPOSES: The control of spasticity is often a significant problem in the management of patients with stroke. The aim of this study was to evaluate the effect of acupuncture treatment on the spastic states of stroke patients. SETTING: An outpatient Acupuncture Department in the First Teaching Hospital of Tianjin University of Traditional Chinese Medicine. PARTICIPANTS: One hundred and thirty-one patients, mean (SD) age of 59 (12) years, with spastic hemiplegia were included at mean (SD) month of 17 (7) months after stroke. INTERVENTION: Participants received two 30-day treatment regimens: combined stimulating surface projection zone of decussation of pyramid and traditional acupuncture treatment, and traditional acupuncture treatment only. MAIN OUTCOME MEASURES: Differences in the modified Ashworth scale (MAS), Fugl-Meyer Assessment (FMA), Barthel Index (BI), and the electromyographic activity of the affected extremity between arms. RESULTS: The average (+/-SD) upper extremity Ashworth score significantly decreased, from 3.08+/-0.77 before treatment to 1.82+/-0.65 after acupuncture intervention (wrist joint, P<0.05), and from 2.72+/-0.59 to 1.32+/-0.71 (elbow joint, P<0.05) for treatment group. There were significant differences noted between the treatment group and control group after administration. Lower extremity treatment responses were similar to upper extremity responses. However, both groups showed similar improvement in FMA (upper extremity) and FMA (lower extremity). However, the improvements of FMA (total), BI, and F/M ratio were better in treatment group than in control group. CONCLUSIONS: These results suggested that acupuncturing surface projection zone of decussation of pyramid was effective in reducing spastically increased muscle tone and motor neuron excitability in spastic hemiplegia, and could improve spastic states of stroke patients, thus providing a safe and economical method for treating stroke patients.

Quantitative structure-property relationship studies on amino acid conjugates of jasmonic acid as defense signaling molecules.

Jasmonates and related compounds, including amino acid conjugates of jasmonic acid, have regulatory functions in the signaling pathway for plant developmental processes and responses to the complex equilibrium of biotic and abiotic stress. But the molecular details of the signaling mechanism are still poorly understood. Statistically significant quantitative structure-property relationship models (r(2) > 0.990) constructed by genetic function approximation and molecular field analysis were generated for the purpose of deriving structural requirements for lipophilicity of amino acid conjugates of jasmonic acid. The best models derived in the present study provide some valuable academic information in terms of the 2/3D-descriptors influencing the lipophilicity, which may contribute to further understanding the mechanism of exogenous application of jasmonates in their signaling pathway and designing novel analogs of jasmonic acid as ecological pesticides.

Attraction of Culex pipiens pallens (Diptera: Culicidae) to Floret Volatiles and Synthetic Blends of Its Nectar Host Plant Abelia chinensis (Rubiales: Caprifoliaceae).

Abelia chinensis R. Br. (Dipsacales: Caprifoliaceae) is one of the preferred nectar host plants for Culex pipiens pallens Coquillett (Diptera: Culicidae). However, the volatile compounds of its flowers that might be involved in directing mosquitoes' orientation to its nectaries remain unknown. In the present study, the volatile compounds released by A. chinensis florets were collected by solid phase microextraction fiber and analyzed by gas chromatography-mass spectrometry system. Based on the major component species in the volatile profile, a synthetic phytochemical blend (Blend B, composed of six compounds at their most attractive concentrations) was formulated, and its attractiveness was tested against the pentane extract of A. chinensis florets at most attractive concentration (Blend A) and a formerly developed synthetic phytochemical blend (Blend C) in the olfactometer, respectively. The results revealed that the volatile profile of A. chinensis florets was mainly composed of aromatic compounds, most of which had been reported to be attractive to other mosquito species. The synthetic Blend B was as attractive as Blend A (10-1-fold of the crude pentane extract) in the olfactometer bioassays, but they were not as attractive as the formerly developed Blend C. The present study indicated that quantitative and qualitative differences in the constituents of phytochemical blends could significantly affect their attractiveness to Cx. pipiens pallens, and the capture efficiency of phytochemical attractants deserves further research before being applied in the field.

Quantitative structure-activity relationship studies on 1-aryl-tetrahydroisoquinoline analogs as active anti-HIV agents.

Predictive quantitative structure-activity relationship analysis was developed for a diverse series of recently synthesized 1-aryl-tetrahydroisoquinoline analogs with anti-HIV activities in this study. The conventional 2D-QSAR models were developed by genetic function approximation (GFA) and stepwise multiple linear regression (MLR) with acceptable explanation of 94.9% and 95.5% and good predicted power of 91.7% and 91.7%, respectively. The results of the 2D-QSAR models were further compared with 3D-QSAR model generated by molecular field analysis (MFA), investigating the substitutional requirements for the favorable receptor-drug interaction and quantitatively indicating the important regions of molecules for their activities. The results obtained by combining these methodologies give insights into the key features for designing more potent analogs against HIV.

Solvent-enhanced microwave-assisted derivatization following solid-phase extraction combined with gas chromatography-mass spectrometry for determination of amphetamines in urine.

An approach using microwave-assisted derivatization (MAD) following solid-phase extraction (SPE) combined with gas chromatography-mass spectrometry (GC-MS) was developed to determine amphetamines in urine samples. The parameters affecting the derivatization efficiency - including microwave power and irradiation time - were investigated. Besides, solvent is thought critically important to MAD. Derivatization performance was studied using various solvents and compared with the performance obtained without solvent. Derivatization efficiency was clearly found to be enhanced by the presence of solvent. The highest derivatization efficiencies were obtained in ethyl acetate (EA) under microwave power of 250W for 1min. Calibration curves for all amphetamines were linear over a range from 1 to 1000ng/mL, with correlation coefficients above 0.9992. The intra-day and inter-day precision were less than 15%. The applicability of the method was tested by analyzing amphetamine-abusing subjects urine samples. Accordingly, the solvent-enhanced MAD-GC-MS method appears to be adequate for determining amphetamines in urine.

l-Glutamic acid hydro-chloride at 153 K.

THE TITLE COMPOUND [SYSTEMATIC NAME: (S)-1,3-dicarboxy-propanaminium chloride], C(5)H(10)NO(4) (+)·Cl(-), has been investigated previously by Dawson [Acta Cryst. (1953). 6, 81-83], with R = 0.106 and without the location of H atoms, and then by Sequeira, Rajagopal & Chidambaram [Acta Cryst. (1972). B28, 2514-2519] using neutron diffraction with R = 0.043. The present determination at 153 K has R = 0.017 and all the H atoms are located. There are obvious differences in some C-C bond lengths between the present and previous studies. In the present structure, l-glutamic acid is protonated and is linked to the Cl(-) anion by an O-H⋯Cl hydrogen bond. The crystal structure is established by a three-dimensional network of O-H⋯O, N-H⋯O and N-H⋯Cl hydrogen bonds.

Transesterification of soybean oil by using the synergistic microwave-ultrasonic irradiation.

Microwave and ultrasound have been demonstrated to be outstanding process intensification techniques for transesterification of oil. According to their mechanisms, simultaneous effects can surely bring about better enhancement than sole microwave or ultrasound. Therefore, this study aimed to investigate the important factors and their suitable levels in the KOH-catalyzed transesterification of soybean oil with methanol by using synergistic assistance of microwave-ultrasound (CAMU). The feasibility of application of CAMU in transesterification of oil was demonstrated. When the dosage of methanol, soybean oil and KOH were 15.4g, 34.7g (with methanol-to-oil molar ratio of 12:1) and 1g, respectively, and the microwave power, ultrasonic power, ultrasonic mode, reaction temperature and reaction time were 700W, 800W, 1:0, 65°C and 6min, respectively, the transesterification reached 98.0% of yield, being the highest yield among all the results obtained; while by using 600W of microwave plus stirring instead of CAMU, only 57.4% of yield could be obtained. Compared with other reaction techniques, the transesterification by applying novel CAMU was found to have remarkable advantages. Furthermore, by monitoring the variation of real-time temperature and microwave power during transesterification reactions with different microwave operation time and by taking comparison of the corresponding yield, it was demonstrated that the main reason for the acceleration of microwave-assisted transesterification was the polarization and further activation of reactants caused by microwave irradiation, but not the factor of fast heating.

Microwave-Assisted Simplified Simultaneous Distillation Coupled with Ionic Liquid Pretreatment for the Analysis of Essential Oil in Schisandra sphenanthera.

Simultaneous distillation extraction (SDE) is quite useful for the separation of volatile compounds from an analyte when their contents are quite low. In this study, a simplified SDE approach is applied for the extraction of essential oil from Schisandra sphenanthera, with microwave as heating source, [Bmim][Cl] as the medium for pretreatment, and gas chromatography-mass spectrometry as the analytical approach. Consequently, the improvement resulted from [Bmim][Cl] pretreatment is demonstrated by taking comparison with blank experiments. Totally 61 compounds have been detected in the essential oil obtained by using [Bmim][Cl] pretreatment, while without [Bmim][Cl] pretreatment, only 53 compounds can be detected. Moreover, [Bmim][Cl] pretreatment can also resulted in a higher yield of essential oil. The experimental results demonstrate that the simplified SDE coupled with ionic liquid pretreatment is a feasible approach for the extraction of essential oil from S. sphenanthera with high efficiency as 0.85% of essential oil yield has been obtained, and can be potentially extended to the extraction of essential oil or other target volatile compounds with low content.

Simultaneous analysis of antioxidants and preservatives in cosmetics by supercritical fluid extraction combined with liquid chromatography-mass spectrometry.

This study evaluated supercritical fluid extraction (SFE) combined with liquid chromatography-mass spectrometry (LC-MS) to determine trace preservatives and antioxidants including methylparaben (MP), ethylparaben (EP), propylparaben (PP), butylparaben (BP), butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT), alpha-tocopherol (alpha-t) and alpha-tocopherol acetate (alpha-ta) in cosmetic products. A supercritical fluid extraction procedure was used to isolate four paraben preservatives and four antioxidants from the cosmetic matrix before quantitative analysis. The optimum extraction condition was performed with static extraction for 5 min, then dynamic extraction for 20 min by using carbon dioxide supercritical fluid at 14,000 kPa and 65 degrees C. Methanol was used as collection solvent and the sea sand was chosen as a filling material. The analytes were separated on a C18 reversed-phase column using methanol-water as mobile phase and quantified by measuring its mass spectrometry. The linearity range is from 10 to 20,000 ng/g with RSD values below 18%. Detection limits are achieved at the level of 4.7-142 ng/g. It was successfully applied to the determination of paraben preservatives and antioxidants in cosmetics without tedious pretreatment.

[Influence of different light source on the laser Raman spectra in determination of sodium glutamic acid].

The influences of different laser source and different light power on laser Raman spectra were studied for the sodium glutamic acid. The results show that some influences existed using different wavelength and power of light source the peak shifting 6 cm(-1). As UV laser has great light power, the samples were destroyed, making the Raman spectra- reduce or disappear. The attenuation of light was needed. The linear relation existed between the Raman intensity and the power of laser light source, and the correlation coefficient was more then 0.999. The Raman intensity per light power unit was related to the wavelength, and was not related to the power of laser source.

Development of a Microextraction Method Based on Dissolved Carbon Dioxide Flotation after Emulsification for the Determination of Triazole Pesticides Residues in Water Samples by Gas Chromatography-Mass Spectrometry.

A novel dissolved carbon dioxide flotation after emulsification microextraction (DCF-EME) method was proposed for the determination of four triazole pesticides in water samples coupled with gas chromatography-mass spectrometry (GC-MS) in a home-made glass round flask. The DCF-EME method is based on a rapid and simple phase separation of low-density organic solvent (toluene) from the aqueous phase via introducing a saturated NaHCO3 solution into the acidified sample (0.1 mol L-1 HCl); then analytes were extracted in toluene. Various parameters affecting the extraction process were optimized. Under the optimal conditions, the recoveries for four pesticides ranged from 82.8 to 121.2%. Meanwhile the limits of detection were at the range of 0.14 - 1.04 µg L-1, and the preconcentration factors were varied between 342 and 473 for different triazoles. The method is simple, fast and environmentally friendly, being successfully applied for the determination of triazole pesticides in water samples.

[Determination of stability constant of glutamate zinc by indirect determination of FAAS with ZnS].

Based on indirect determination of glutamic acid by flame atomic absorption spectrometry with ZnS and the complexing action mechanism, the determination of stability constant of glutamate zinc was studied. Under the selected condition of pH 9.0, the stability constant of glutamate zinc is between 3.3 x 10(20) and 1.4 x 10(21), the average value is betaw = 1.03 x 10(21), and log betaw = 21.013.

A novel set of Wiener indices.

According to the definition of molecular connectivity and the definition of the Wiener index, a novel set of Wiener indices (mV(t)) were defined, named novel Wiener index. The potential usefulness of the novel Wiener index in QSAR/QSPR is evaluated by its correlation with a number of C(3)-C(8) alkanes and by a favorable comparison with models based on molecular connectivity index and Wiener index.