Improved analytical methods for the metabolomic profiling of tissue samples are constantly needed.Currently,conventional sample preparation methods often involve tissue biopsy and/or homogenization,which disrupts the ...Improved analytical methods for the metabolomic profiling of tissue samples are constantly needed.Currently,conventional sample preparation methods often involve tissue biopsy and/or homogenization,which disrupts the endogenous metabolome.In this study,solid-phase microextraction(SPME)fibers were used to monitor changes in endogenous compounds in homogenized and intact ovine lung tissue.Following SPME,a Biocrates AbsoluteIDQ assay was applied to make a downstream targeted metabolomics analysis and confirm the advantages of in vivo SPME metabolomics.The AbsoluteIDQ kit enabled the targeted analysis of over 100 metabolites via solid-liquid extraction and SPME.Statistical analysis revealed significant differences between conventional liquid extractions from homogenized tissue and SPME results for both homogenized and intact tissue samples.In addition,principal component analysis revealed separated clustering among all the three sample groups,indicating changes in the metabolome due to tissue homogenization and the chosen sample preparation method.Furthermore,clear differences in free metabolites were observed when extractions were performed on the intact and homogenized tissue using identical SPME procedures.Specifically,a direct comparison showed that 47 statistically distinct metabolites were detected between the homogenized and intact lung tissue samples(P<0.05)using mixed-mode SPME fibers.These changes were probably due to the disruptive homogenization of the tissue.This study's findings highlight both the importance of sample preparation in tissue-based metabolomics studies and SPME's unique ability to perform minimally invasive extractions without tissue biopsy or homogenization while providing broad metabolite coverage.展开更多
The direct coupling of solid-phase microextraction(SPME)to mass spectrometry(MS)(SPME-MS)has proven to be an effective method for the fast screening and quantitative analysis of compounds in complex matrices such as b...The direct coupling of solid-phase microextraction(SPME)to mass spectrometry(MS)(SPME-MS)has proven to be an effective method for the fast screening and quantitative analysis of compounds in complex matrices such as blood and plasma.In recent years,our lab has developed three novel SPME-MS techniques:SPME-microfluidic open interface-MS(SPME-MOI-MS),coated blade spray-MS(CBS-MS),and SPME-probe electrospray ionization-MS(SPME-PESI-MS).The fast and high-throughput nature of these SPME-MS technologies makes them attractive options for point-of-care analysis and anti-doping testing.However,all these three techniques utilize different SPME geometries and were tested with different MS instruments.Lack of comparative data makes it difficult to determine which of these methodologies is the best option for any given application.This work fills this gap by making a comprehensive comparison of these three technologies with different SPME devices including SPME fibers,CBS blades,and SPME-PESI probes and SPME-liquid chromatography-MS(SPME-LC-MS)for the analysis of drugs of abuse using the same MS instrument.Furthermore,for the first time,we developed different desorption chambers for MOI-MS for coupling with SPME fibers,CBS blades,and SPME-PESI probes,thus illustrating the universality of this approach.In total,eight analytical methods were developed,with the experimental data showing that all the SPME-based methods provided good analytical performance with R^(2)of linearities larger than 0.9925,accuracies between 81%and 118%,and good precision with an RSD%≤13%.展开更多
Volatile constituents in fully mature fruits of apricot (Prunus armeniaca L.) cultivar Xinshiji were extracted using headspace solid-phase microextraction (HS-SPME) and simultaneous steam distillation extraction ...Volatile constituents in fully mature fruits of apricot (Prunus armeniaca L.) cultivar Xinshiji were extracted using headspace solid-phase microextraction (HS-SPME) and simultaneous steam distillation extraction (SSDE) and then analyzed using capillary gas chromatography and gas chromatography-mass spectrometry. A total of 70 components were identified by HSSPME, including 20 esters, 19 hydrocarbons, 5 alcohols, 5 ketones, 4 acids, 4 lactones, 3 aldehydes, and 10 miscellaneous components, with the esters being the dominant constituent. On the basis of the odor unit values, it is believed that the following compounds probably contributed to the fresh apricot odor: hexyl acetate, β-ionone, butyl acetate, (E)-2-hexenal, linalool, limonene, γ-decalactone, and hexanal. A total of 49 components were also detected by SSDE, including 13 hydrocarbons, 9 alcohols, 7 aldehydes, 9 esters, 4 ketones, 4 lactones, 2 acids, and 1 miscellaneous component, of which the monoterpene alcohols were the dominant constituents. It could be judged from the odor unit values that the following compounds were the major contributors to boiled apricot aroma: β-ionone, linalool, hexyl acetate, γ-dodecalactone, γ- decalactone, (E)-2-hexenal, hexanal, γ-octalactone, phenylacetaldehyde, butyl acetate, limonene, α-terpineol, and δ-decalactone. The results show that HS-SPME is a simple, rapid, and solvent-free method, which is an alternative to the classical SSDE.展开更多
This paper describes the electrodeposition of polyphosphate-doped polypyrrole/nanosilica nano-composite coating on steel wire for direct solid-phase microextraction of bisphenol A and five phthalates. We optimized inf...This paper describes the electrodeposition of polyphosphate-doped polypyrrole/nanosilica nano-composite coating on steel wire for direct solid-phase microextraction of bisphenol A and five phthalates. We optimized influencing parameters on the extraction efficiency and morphology of the nanocomposite such as deposition potential, concentration of pyrrole and polyphosphate, deposition time and the nanosilica amount. Under the optimized conditions, characterization of the nanocomposite was inves-tigated by scanning electron microscopy and Fourier transform infra-red spectroscopy. Also, the factors related to the solid-phase microextraction method including desorption temperature and time, extrac-tion temperature and time, ionic strength and pH were studied in detail. Subsequently, the proposed method was validated by gas chromatography-mass spectrometry by thermal desorption and acceptable figures of merit were obtained. The linearity of the calibration curves was between 0.01 and 50 ng/mL with acceptable correlation coefficients (0.9956-0.9987) and limits of detection were in the range 0.002-0.01 ng/mL. Relative standard deviations in terms of intra-day and inter-day by five replicate analyses from aqueous solutions containing 0.1 ng/mL of target analytes were in the range 3.3%-5.4% and 5%-7.1%, respectively. Fiber-to-fiber reproducibilities were measured for three different fibers prepared in the same conditions and the results were between 7.3% and 9.8%. Also, extraction recoveries at two different concentrations were ≥96%. Finally, the suitability of the proposed method was demonstrated through its application to the analysis of some eye drops and injection solutions.展开更多
Covalent organic nanospheres(CONs)were explored as a fiber coating for solid-phase microextraction of genotoxic impurities(GTIs)from active ingredients(AIs).CONs were synthesized by an easy solutionphase procedure at...Covalent organic nanospheres(CONs)were explored as a fiber coating for solid-phase microextraction of genotoxic impurities(GTIs)from active ingredients(AIs).CONs were synthesized by an easy solutionphase procedure at 25℃.The obtained nanospheres exhibited a high specific surface area,good thermostability,high acid and alkali resistance,and favorable crystallinity and porosity.Two types of GTIs,alkyl halides(1-iodooctane,1-chlorobenzene,1-bromododecane,1,2-dichlorobenzene,1-bromooctane,1-chlorohexane,and 1,8-dibromooctane)and sulfonate esters(methyl p-toluenesulfonate and ethyl ptoluenesulfonate),were chosen as target molecules for assessing the performance of the coating.The prepared coating achieved high enhancement factors(5097-9799)for the selected GTIs.The strong affinity between CONs and GTIs was tentatively attributed to π-π and hydrophobicity interactions,large surface area of the CONs,and size-matching of the materials.Combined with gas chromatography-mass spectrometry(GC-MS),the established analytical method detected the GTIs in capecitabine and imatinib mesylate samples over a wide linear range(0.2-200 ng/g)with a low detection limit(0.04-2.0 ng/g),satisfactory recovery(80.03%-109.5%),and high repeatability(6.20%-14.8%)and reproducibility(6.20%-14.1%).Therefore,the CON-coated fibers are promising alternatives for the sensitive detection of GTIs in AI samples.展开更多
We have investigated the use of flash evaporation, headspace solid-phase microextraction (HS-SPME) and steam distillation (SD) as sample concentration and preparation techniques for the analysis of volatile constituen...We have investigated the use of flash evaporation, headspace solid-phase microextraction (HS-SPME) and steam distillation (SD) as sample concentration and preparation techniques for the analysis of volatile constituents present in Houttuynia cordata Thunb. The samples were analyzed by gas chromatography (GC) and identified by mass spectrometry (MS). Comparison studies were performed. It was found that the results obtained between Headspace solid-phase microextraction HS-SPME and SD techniques were in good agreement. Seventy-nine compounds in Houttuynia cordata Thunb were identified by MS. In flash evaporation, thirty-nine compounds were identified. Discrimination in the response for many constituents studied was not observed, which can be clearly observed in SD and HS-SPME techniques. As a conclusion, HS-SPME is a powerful tool for determining the volatile constitutes present in the Houttuynia cordata.展开更多
Headspace solid-phase microextraction(HS-SPME) with sol-gel calix[6]arene-containing fiber followed by gas chromatography with a flame ionization detector was used to examine the composition and distribution of seve...Headspace solid-phase microextraction(HS-SPME) with sol-gel calix[6]arene-containing fiber followed by gas chromatography with a flame ionization detector was used to examine the composition and distribution of seven polycyclic aromatic hydrocarbons(PAHs) in water. The novel SPME fiber exhibited higher extraction efficiency to PAHs compared with poly(dimethylsiloxane) and other calixarene-containing fibers. Extraction/retention mechanism based on the interactions between calixarenes and PAHs was discussed. Owing to the good selectivity and high extraction capability of this calixarene fiber, low detection limits were obtained in a range of 0.34―6.50 ng/L and the relative standard deviation values were ≤12.3% for all of the analytes. The linear ranges of the proposed method were five orders of magnitude for the tested compounds, with linear correlation coefficients(r) greater than 0.998. The method was applied to the determination of polycyclic aromatic hydrocarbons in nine water sources in Wuhan City, China. Standard addition method was selected for the quantification and the recovery values were in a satisfactory range. Total PAHs concentrations in the nine surface water samples were found to vary between undetectable and 8.840 μg/L with two- and three-ring PAHs predominating.展开更多
5, 11, 17, 23-tetra-tert-butyl-25, 27-diethoxy-26, 28-dihydroxycalix \ arene /hydroxy-terminated silicone oil coated fiber was first prepared and applied for solid-phase microextraction with sol-gel technology. The pr...5, 11, 17, 23-tetra-tert-butyl-25, 27-diethoxy-26, 28-dihydroxycalix \ arene /hydroxy-terminated silicone oil coated fiber was first prepared and applied for solid-phase microextraction with sol-gel technology. The properties of the new coating were investigated by analysis of benzene derivatives, polycyclic aromatic hydrocarbons and aromatic amines. The fiber is characterized by good sensitivity and selectivity to these aromatics. The fiber has stable performance at a high temperature of 380℃ and after a long solvent immersing, thus its lifetime is very long. It shows good fiber-to-fiber and batch-to-batch reproducibility. Furthermore, broad linear ranges and low detection limits are also its characteristics.展开更多
The sol-gel technology is applied for the preparation of solid-phase microextraction (SPME) fiber. The fiber demonstrates high thermal stability, efficient extraction rate and the selectivity for non-polar or low-pol...The sol-gel technology is applied for the preparation of solid-phase microextraction (SPME) fiber. The fiber demonstrates high thermal stability, efficient extraction rate and the selectivity for non-polar or low-polar analytes. Efficient SPME-GC-FID analyses of benzene- toluene-ethylbenzene-xylenes (BTEXs) and low-polar halocarbon were achieved by the sol-gel coated DSDA-DDBT-TiO2 fiber. Some parameters of the SPME fiber for the determination of halocarbon in aqueous sample were investigated.展开更多
The solid-phase microextraction technique quantifies analytes without considerably affecting the sample composition.Herein,a proof-of-concept study was conducted to demonstrate the use of coated probe electrospray ion...The solid-phase microextraction technique quantifies analytes without considerably affecting the sample composition.Herein,a proof-of-concept study was conducted to demonstrate the use of coated probe electrospray ionization(coated-PESI)and coated blade spray(CBS)as ambient mass spectrometry approaches for monitoring drug biotransformation.The ability of these methods was investigated for monitoring the dephosphorylation of a prodrug,combretastatin A4 phosphate(CA4P),into its active form,combretastatin A4(CA4),in a cell culture medium supplemented with fetal bovine serum.The CBS spot analysis was modified to achieve the same extraction efficiency as protein precipitation and obtained results in 7 min.Because coated-PESI performs extraction without consuming any samples,it is the preferred technique in the case of a limited sample volume.Although coated-PESI only extracts small quantities of analytes,it uses the desorption solvent volume of 5-10 pL,resulting in high sensitivity,thus allowing the detection of compounds after only 1 min of extraction.The biotransformation of CA4P into CA4 via phosphatases occurs within the simple matrix,and the proposed sample preparation techniques are suitable for monitoring the biotransformation.展开更多
Phenyl bonded mesoporous silica (C6H5-MCM-41) was applied as the fiber coating of solid-phase microextraction (SPME). The performance of the fiber coating was discussed coupling to HPLC. Applicability of mesoporous fi...Phenyl bonded mesoporous silica (C6H5-MCM-41) was applied as the fiber coating of solid-phase microextraction (SPME). The performance of the fiber coating was discussed coupling to HPLC. Applicability of mesoporous fiber coating was examined for the determination of benzo[a]pyrene (B[a]P) in water samples. The limit of detection (LOD) is 0.28μg·L-1. Good recovery and relative standard deviation (RSD) were obtained.展开更多
This research examined the typical flavor compounds in the commonest type of Khat called Harari Khat grown in the region of Ethiopia.Twenty-eight compounds, which includes 1,2-Propanedione,1-Phenyl,Hexanol,Hexanal com...This research examined the typical flavor compounds in the commonest type of Khat called Harari Khat grown in the region of Ethiopia.Twenty-eight compounds, which includes 1,2-Propanedione,1-Phenyl,Hexanol,Hexanal compounds,Limonene, Benzaldehyde with other flavors, were extracted by polydimethylsiloxane at room temperature for 30min from Khat samples,and identified by solid-phase microextraction-gas chromatography-mass spectrometry (SPME-GC-MS).This method needs no organic solvents and required minimal sample.展开更多
The chlorination process is one of the water treatment method used for the disinfection of water. The disinfection by products are trihalomethanes such as chloroform, dichloromethane, dibromochloromethane and bromofor...The chlorination process is one of the water treatment method used for the disinfection of water. The disinfection by products are trihalomethanes such as chloroform, dichloromethane, dibromochloromethane and bromoform. A headspace solid-phase microextraction method has been developed for determination oftrihalomethanes in water samples. The experimental parameters such as the stirring rate, extraction time, extraction temperature and desorption time were investigated. The linearity, detection limits and percentage recovery were evaluated. The optimum conditions were stirring rate 800 rpm/min, extraction time 6 min, extraction temperature 20 ~C, desorption time 2.5 min and desorption temperature 220 ~C. The detection limits were 0.01 ~g/L and the recoveries were in the range of 86-110 %, The proposed method was successfully applied to determination of THM4 in tap water samples. The THM4 contents were varied depending on the sample sites and the season. The total THM4 contents in cool, summer and rainy season were in the range of 27.58-41.89, 32.06-60.73 and 46.26-69.87 p.g/L, respectively. Confirmation of the detected compounds in water samples were performed by gas chromatograph-mass spectrometer. The mass spectra of the target compounds in water samples is in good agreement with trihalomethanes standard spectra.展开更多
[Objectives]This study aimed to determine the volatile components in Santalum album Linn and gradually clarify the aroma composition of S.album Linn.[Methods]Solid-phase microextraction method was used to obtain the v...[Objectives]This study aimed to determine the volatile components in Santalum album Linn and gradually clarify the aroma composition of S.album Linn.[Methods]Solid-phase microextraction method was used to obtain the volatile components of S.album Linn.The aroma components were analyzed by gas chromatography-mass spectrometry and their relative contents were calculated using the area normalization method.[Results]In a dry state at room temperature,39 chemical components were identified from S.album Linn,mainly olefins(91.15%),alkanes(3.00%),alcohols(2.56%),esters(2.19%),ketones(0.55%),aldehydes(0.41%)and heterocyclics(0.14%).[Conclusions]This method has the advantages of low sample consumption,easy operation,rapid identification of aroma components and high sensitivity,and can effectively separate and determine volatile components in S.album Linn,realizing the rapid identification of different S.album Linn varieties and providing technical support for further research on Chinese medicinal materials.展开更多
In vivo lung perfusion(IVLP)is a novel isolated lung technique developed to enable the local,in situ administration of high-dose chemotherapy to treat metastatic lung cancer.Combination therapy using folinic acid(FOL)...In vivo lung perfusion(IVLP)is a novel isolated lung technique developed to enable the local,in situ administration of high-dose chemotherapy to treat metastatic lung cancer.Combination therapy using folinic acid(FOL),5-fluorouracil(F),and oxaliplatin(OX)(FOLFOX)is routinely employed to treat several types of solid tumours in various tissues.However,F is characterized by large interpatient variability with respect to plasma concentration,which necessitates close monitoring during treatments using of this compound.Since plasma drug concentrations often do not reflect tissue drug concentrations,it is essential to utilize sample-preparation methods specifically suited to monitoring drug levels in target organs.In this work,in vivo solid-phase microextraction(in vivo SPME)is proposed as an effective tool for quantitative therapeutic drug monitoring of FOLFOX in porcine lungs during pre-clinical IVLP and intravenous(IV)trials.The concomitant extraction of other endogenous and exogenous small molecules from the lung and their detection via liquid chromatography coupled to high resolution mass spectrometry(LC-HRMS)enabled an assessment of FOLFOX's impact on the metabolomic profile of the lung and revealed the metabolic pathways associated with the route of administration(IVLP vs.IV)and the therapy itself.This study also shows that the immediate instrumental analysis of metabolomic samples is ideal,as long-term storage at80℃ results in changes in the metabolite content in the sample extracts.展开更多
In this report, gas chromatography-mass spectrometry (GC-MS) based non-targeted metabolomics is used to develop appropriate headspace solid phase microextractions (HS-SPME) to enhance the understanding of volatile com...In this report, gas chromatography-mass spectrometry (GC-MS) based non-targeted metabolomics is used to develop appropriate headspace solid phase microextractions (HS-SPME) to enhance the understanding of volatile complexity of flue-cured tobacco leaves. Non-targeted metabolic profiling of GC-MS shows that the extraction condition of HS-SPME at 100?C for 30 min provides a better metabolite profile than other extraction conditions tested. GC-MS and principal component analyses (PCA) show that among five types of fibers tested, 100 μm polydimethylsiloxane (PMDS), 65 μm polydimethylsiloxane/divinylbenzene (PMDS/DVB) and 75 μm carboxen/polydimethylsiloxane (CAR/ PMS) provide a better reproducible metabolite profile. Based on an appropriate PDMS extraction condition optimized, we use GC-MS analysis and PCA to compare metabolite profiles in flue-cured leaves of tobacco plants grown in North Carolina, India and Brazil, respectively. The resulting data of PCA show that the global metabolic profiles in North Carolina samples are separated from those in Brazil and India samples, two groups of which are characterized by a partially overlapped pattern. Several peaks that were differentially accumulated in samples were annotated to known metabolites by deconvolution analysis, such as norsolanadione, solavetivone and rishtin. Norsolanadione is detected only in Brazil samples. Solavetivone is detected in samples of India and Brazil but not in those of North Carolina. Rishtin is detected in samples of North Carolina and India but not in Brazil samples. These data indicate that not only can a non-targeted metabolic profiling approach enhance the understanding of volatile complexity, but also can identify marker volatile metabolites in tobacco leaves produced in different growth regions.展开更多
For identifying and quantifying prohibited substances,solid-phase microextraction(SPME)continues to arouse interest as a sample preparation method.However,the practical implementation of this method in routine laborat...For identifying and quantifying prohibited substances,solid-phase microextraction(SPME)continues to arouse interest as a sample preparation method.However,the practical implementation of this method in routine laboratory testing is currently hindered by the limited number of coatings compatible with the ubiquitous high-performance liquid chromatography(HPLC)systems.Only octadecyl(C18)and polydimethylsiloxane/divinylbenzene ligands are currently marketed for this purpose.To address this situation,the present study evaluated 12 HPLC-compatible coatings,including several chemistries not currently used in this application.The stationary phases of SPME devices in the geometry of thin filmcoated blades were prepared by applying silica particles bonded with various functional ligands(C18,octyl,phenyl-hexyl,3-cyanopropyl,benzenesulfonic acid,and selected combinations of these),as well as unbonded silica,to a metal support.Most of these chemistries have not been previously used as microextraction coatings.The 48 most commonly misused substances were selected to assess the extraction efficacy of each coating,and eight desorption solvent compositions were used to optimize the desorption conditions.All samples were analyzed using an HPLC system coupled with triple quadrupole tandem mass spectrometry.This evaluation enables selection of the best-performing coatings for quantifying prohibited substances and investigates the relationship between extraction efficacy and the physicochemical characteristics of the analytes.Ultimately,using the most suitable coatings is essential for trace-level analysis of chemically diverse prohibited substances.展开更多
Adjuvant chemotherapy improves the survival outlook for patients undergoing operations for lung metastases caused by colorectal cancer (CRC). However, a multidisciplinary approach that evaluates several factors relate...Adjuvant chemotherapy improves the survival outlook for patients undergoing operations for lung metastases caused by colorectal cancer (CRC). However, a multidisciplinary approach that evaluates several factors related to patient and tumor characteristics is necessary for managing chemotherapy treatment in metastatic CRC patients with lung disease, as such factors dictate the timing and drug regimen, which may affect treatment response and prognosis. In this study, we explore the potential of spatial metabolomics for evaluating metabolic phenotypes and therapy outcomes during the local delivery of the anticancer drug, oxaliplatin, to the lung. 12 male Yorkshire pigs underwent a 3 h left lung in vivo lung perfusion (IVLP) with various doses of oxaliplatin (7.5, 10, 20, 40, and 80 mg/L), which were administered to the perfusion circuit reservoir as a bolus. Biocompatible solid-phase microextraction (SPME) microprobes were combined with global metabolite profiling to obtain spatiotemporal information about the activity of the drug, determine toxic doses that exceed therapeutic efficacy, and conduct a mechanistic exploration of associated lung injury. Mild and subclinical lung injury was observed at 40 mg/L of oxaliplatin, and significant compromise of the hemodynamic lung function was found at 80 mg/L. This result was associated with massive alterations in metabolic patterns of lung tissue and perfusate, resulting in a total of 139 discriminant compounds. Uncontrolled inflammatory response, abnormalities in energy metabolism, and mitochondrial dysfunction next to accelerated kynurenine and aldosterone production were recognized as distinct features of dysregulated metabolipidome. Spatial pharmacometabolomics may be a promising tool for identifying pathological responses to chemotherapy.展开更多
A fast and reliable method for the determination of trace PAHs (polynuclear aromatic hydrocarbons) in seawater by solid-phase microextraction (SPME) followed by gas chromatographic (GC) analysis has been developed. Th...A fast and reliable method for the determination of trace PAHs (polynuclear aromatic hydrocarbons) in seawater by solid-phase microextraction (SPME) followed by gas chromatographic (GC) analysis has been developed. The SPME operational parameters have been optimized, and the effects of salinity and dissolved organic matter (DOM) on PAHs recoveries have been investigated. SPME measures only the portion of PAHs which are water soluble, and can be used to quantify PAH partition coefficient between water and DOM phases. The detection limits of the overall method for the measurement of sixteen PAHs range from 0.1 to 3.5 ng/g, and the precisions of individual PAH measurements range from 4% to 23% RSD. The average recovery for PAHs is 88.2±20.4%. The method has been applied to the determination of PAHs in seawater and sediment porewater samples collected in Jiaozhou Bay and Laizhou Bay in Shandong Peninsula, China. The overall levels of PAHs in these samples reflect moderate pollution compared to seawater samples reported elsewhere. The PAH distribution pattern shows that the soluble PAHs in seawater and porewater samples are dominated by naphthalenes and 3 ring PAHs. This is in direct contrast to those of the sediment samples reported earlier, in which both light and heavy PAHs are present at comparable concentrations. The absence of heavy PAHs in soluble forms (<0.1-3.5 ng/L) is indicative of the strong binding of these PAHs to the dissolved or solid matters and their low seawater solubility.展开更多
基金supported by the Natural Sciences and Engineering Research Council of Canada,NSERC(Grant No.:IRCPJ 184412-15).
文摘Improved analytical methods for the metabolomic profiling of tissue samples are constantly needed.Currently,conventional sample preparation methods often involve tissue biopsy and/or homogenization,which disrupts the endogenous metabolome.In this study,solid-phase microextraction(SPME)fibers were used to monitor changes in endogenous compounds in homogenized and intact ovine lung tissue.Following SPME,a Biocrates AbsoluteIDQ assay was applied to make a downstream targeted metabolomics analysis and confirm the advantages of in vivo SPME metabolomics.The AbsoluteIDQ kit enabled the targeted analysis of over 100 metabolites via solid-liquid extraction and SPME.Statistical analysis revealed significant differences between conventional liquid extractions from homogenized tissue and SPME results for both homogenized and intact tissue samples.In addition,principal component analysis revealed separated clustering among all the three sample groups,indicating changes in the metabolome due to tissue homogenization and the chosen sample preparation method.Furthermore,clear differences in free metabolites were observed when extractions were performed on the intact and homogenized tissue using identical SPME procedures.Specifically,a direct comparison showed that 47 statistically distinct metabolites were detected between the homogenized and intact lung tissue samples(P<0.05)using mixed-mode SPME fibers.These changes were probably due to the disruptive homogenization of the tissue.This study's findings highlight both the importance of sample preparation in tissue-based metabolomics studies and SPME's unique ability to perform minimally invasive extractions without tissue biopsy or homogenization while providing broad metabolite coverage.
基金the National Science Centre,Poland(Grant No.:2020/04/X/NZ9/01281).
文摘The direct coupling of solid-phase microextraction(SPME)to mass spectrometry(MS)(SPME-MS)has proven to be an effective method for the fast screening and quantitative analysis of compounds in complex matrices such as blood and plasma.In recent years,our lab has developed three novel SPME-MS techniques:SPME-microfluidic open interface-MS(SPME-MOI-MS),coated blade spray-MS(CBS-MS),and SPME-probe electrospray ionization-MS(SPME-PESI-MS).The fast and high-throughput nature of these SPME-MS technologies makes them attractive options for point-of-care analysis and anti-doping testing.However,all these three techniques utilize different SPME geometries and were tested with different MS instruments.Lack of comparative data makes it difficult to determine which of these methodologies is the best option for any given application.This work fills this gap by making a comprehensive comparison of these three technologies with different SPME devices including SPME fibers,CBS blades,and SPME-PESI probes and SPME-liquid chromatography-MS(SPME-LC-MS)for the analysis of drugs of abuse using the same MS instrument.Furthermore,for the first time,we developed different desorption chambers for MOI-MS for coupling with SPME fibers,CBS blades,and SPME-PESI probes,thus illustrating the universality of this approach.In total,eight analytical methods were developed,with the experimental data showing that all the SPME-based methods provided good analytical performance with R^(2)of linearities larger than 0.9925,accuracies between 81%and 118%,and good precision with an RSD%≤13%.
基金The study was supported by the National Natural Science Foundation of China (30471196).
文摘Volatile constituents in fully mature fruits of apricot (Prunus armeniaca L.) cultivar Xinshiji were extracted using headspace solid-phase microextraction (HS-SPME) and simultaneous steam distillation extraction (SSDE) and then analyzed using capillary gas chromatography and gas chromatography-mass spectrometry. A total of 70 components were identified by HSSPME, including 20 esters, 19 hydrocarbons, 5 alcohols, 5 ketones, 4 acids, 4 lactones, 3 aldehydes, and 10 miscellaneous components, with the esters being the dominant constituent. On the basis of the odor unit values, it is believed that the following compounds probably contributed to the fresh apricot odor: hexyl acetate, β-ionone, butyl acetate, (E)-2-hexenal, linalool, limonene, γ-decalactone, and hexanal. A total of 49 components were also detected by SSDE, including 13 hydrocarbons, 9 alcohols, 7 aldehydes, 9 esters, 4 ketones, 4 lactones, 2 acids, and 1 miscellaneous component, of which the monoterpene alcohols were the dominant constituents. It could be judged from the odor unit values that the following compounds were the major contributors to boiled apricot aroma: β-ionone, linalool, hexyl acetate, γ-dodecalactone, γ- decalactone, (E)-2-hexenal, hexanal, γ-octalactone, phenylacetaldehyde, butyl acetate, limonene, α-terpineol, and δ-decalactone. The results show that HS-SPME is a simple, rapid, and solvent-free method, which is an alternative to the classical SSDE.
基金financial support of Department of Pharmaceutics, Faculty of Pharmacy, Kerman Medical Science University
文摘This paper describes the electrodeposition of polyphosphate-doped polypyrrole/nanosilica nano-composite coating on steel wire for direct solid-phase microextraction of bisphenol A and five phthalates. We optimized influencing parameters on the extraction efficiency and morphology of the nanocomposite such as deposition potential, concentration of pyrrole and polyphosphate, deposition time and the nanosilica amount. Under the optimized conditions, characterization of the nanocomposite was inves-tigated by scanning electron microscopy and Fourier transform infra-red spectroscopy. Also, the factors related to the solid-phase microextraction method including desorption temperature and time, extrac-tion temperature and time, ionic strength and pH were studied in detail. Subsequently, the proposed method was validated by gas chromatography-mass spectrometry by thermal desorption and acceptable figures of merit were obtained. The linearity of the calibration curves was between 0.01 and 50 ng/mL with acceptable correlation coefficients (0.9956-0.9987) and limits of detection were in the range 0.002-0.01 ng/mL. Relative standard deviations in terms of intra-day and inter-day by five replicate analyses from aqueous solutions containing 0.1 ng/mL of target analytes were in the range 3.3%-5.4% and 5%-7.1%, respectively. Fiber-to-fiber reproducibilities were measured for three different fibers prepared in the same conditions and the results were between 7.3% and 9.8%. Also, extraction recoveries at two different concentrations were ≥96%. Finally, the suitability of the proposed method was demonstrated through its application to the analysis of some eye drops and injection solutions.
基金supported by the Key Research and Development Program of Shandong Province(Grant No.:2019GSF111001)the National Natural Science Foundation of China(Grant No.:21906096)+2 种基金the Youth Science Funds of the Shandong Academy of Sciences(Grant No.:2019QN009)the Youth Ph.D.Cooperation Funds of Qilu University of Technology(Shandong Academy of Sciences,Grant No.:2018BSHZ0029)the Program for Taishan Scholars of Shandong Province(Grant No.:tsqn202103099).
文摘Covalent organic nanospheres(CONs)were explored as a fiber coating for solid-phase microextraction of genotoxic impurities(GTIs)from active ingredients(AIs).CONs were synthesized by an easy solutionphase procedure at 25℃.The obtained nanospheres exhibited a high specific surface area,good thermostability,high acid and alkali resistance,and favorable crystallinity and porosity.Two types of GTIs,alkyl halides(1-iodooctane,1-chlorobenzene,1-bromododecane,1,2-dichlorobenzene,1-bromooctane,1-chlorohexane,and 1,8-dibromooctane)and sulfonate esters(methyl p-toluenesulfonate and ethyl ptoluenesulfonate),were chosen as target molecules for assessing the performance of the coating.The prepared coating achieved high enhancement factors(5097-9799)for the selected GTIs.The strong affinity between CONs and GTIs was tentatively attributed to π-π and hydrophobicity interactions,large surface area of the CONs,and size-matching of the materials.Combined with gas chromatography-mass spectrometry(GC-MS),the established analytical method detected the GTIs in capecitabine and imatinib mesylate samples over a wide linear range(0.2-200 ng/g)with a low detection limit(0.04-2.0 ng/g),satisfactory recovery(80.03%-109.5%),and high repeatability(6.20%-14.8%)and reproducibility(6.20%-14.1%).Therefore,the CON-coated fibers are promising alternatives for the sensitive detection of GTIs in AI samples.
文摘We have investigated the use of flash evaporation, headspace solid-phase microextraction (HS-SPME) and steam distillation (SD) as sample concentration and preparation techniques for the analysis of volatile constituents present in Houttuynia cordata Thunb. The samples were analyzed by gas chromatography (GC) and identified by mass spectrometry (MS). Comparison studies were performed. It was found that the results obtained between Headspace solid-phase microextraction HS-SPME and SD techniques were in good agreement. Seventy-nine compounds in Houttuynia cordata Thunb were identified by MS. In flash evaporation, thirty-nine compounds were identified. Discrimination in the response for many constituents studied was not observed, which can be clearly observed in SD and HS-SPME techniques. As a conclusion, HS-SPME is a powerful tool for determining the volatile constitutes present in the Houttuynia cordata.
基金Supported by the National Natural Science Foundation of China(No.30901007)the Fund of the Ministry of Education of China(No.081025)
文摘Headspace solid-phase microextraction(HS-SPME) with sol-gel calix[6]arene-containing fiber followed by gas chromatography with a flame ionization detector was used to examine the composition and distribution of seven polycyclic aromatic hydrocarbons(PAHs) in water. The novel SPME fiber exhibited higher extraction efficiency to PAHs compared with poly(dimethylsiloxane) and other calixarene-containing fibers. Extraction/retention mechanism based on the interactions between calixarenes and PAHs was discussed. Owing to the good selectivity and high extraction capability of this calixarene fiber, low detection limits were obtained in a range of 0.34―6.50 ng/L and the relative standard deviation values were ≤12.3% for all of the analytes. The linear ranges of the proposed method were five orders of magnitude for the tested compounds, with linear correlation coefficients(r) greater than 0.998. The method was applied to the determination of polycyclic aromatic hydrocarbons in nine water sources in Wuhan City, China. Standard addition method was selected for the quantification and the recovery values were in a satisfactory range. Total PAHs concentrations in the nine surface water samples were found to vary between undetectable and 8.840 μg/L with two- and three-ring PAHs predominating.
文摘5, 11, 17, 23-tetra-tert-butyl-25, 27-diethoxy-26, 28-dihydroxycalix \ arene /hydroxy-terminated silicone oil coated fiber was first prepared and applied for solid-phase microextraction with sol-gel technology. The properties of the new coating were investigated by analysis of benzene derivatives, polycyclic aromatic hydrocarbons and aromatic amines. The fiber is characterized by good sensitivity and selectivity to these aromatics. The fiber has stable performance at a high temperature of 380℃ and after a long solvent immersing, thus its lifetime is very long. It shows good fiber-to-fiber and batch-to-batch reproducibility. Furthermore, broad linear ranges and low detection limits are also its characteristics.
文摘The sol-gel technology is applied for the preparation of solid-phase microextraction (SPME) fiber. The fiber demonstrates high thermal stability, efficient extraction rate and the selectivity for non-polar or low-polar analytes. Efficient SPME-GC-FID analyses of benzene- toluene-ethylbenzene-xylenes (BTEXs) and low-polar halocarbon were achieved by the sol-gel coated DSDA-DDBT-TiO2 fiber. Some parameters of the SPME fiber for the determination of halocarbon in aqueous sample were investigated.
基金supported by Shimadzu Scientific Instruments(Columbia,MD,USA)and Canada’s National Science and Engineering Research Council-Industrial Research Chair(NSERC-IRC)program,grant number IRCPJ 184412-15
文摘The solid-phase microextraction technique quantifies analytes without considerably affecting the sample composition.Herein,a proof-of-concept study was conducted to demonstrate the use of coated probe electrospray ionization(coated-PESI)and coated blade spray(CBS)as ambient mass spectrometry approaches for monitoring drug biotransformation.The ability of these methods was investigated for monitoring the dephosphorylation of a prodrug,combretastatin A4 phosphate(CA4P),into its active form,combretastatin A4(CA4),in a cell culture medium supplemented with fetal bovine serum.The CBS spot analysis was modified to achieve the same extraction efficiency as protein precipitation and obtained results in 7 min.Because coated-PESI performs extraction without consuming any samples,it is the preferred technique in the case of a limited sample volume.Although coated-PESI only extracts small quantities of analytes,it uses the desorption solvent volume of 5-10 pL,resulting in high sensitivity,thus allowing the detection of compounds after only 1 min of extraction.The biotransformation of CA4P into CA4 via phosphatases occurs within the simple matrix,and the proposed sample preparation techniques are suitable for monitoring the biotransformation.
基金the Key Laboratory of Polymer Materials of Gansu Province and the National Natural Science Foundation of China for financial support(No:20735031).
文摘Phenyl bonded mesoporous silica (C6H5-MCM-41) was applied as the fiber coating of solid-phase microextraction (SPME). The performance of the fiber coating was discussed coupling to HPLC. Applicability of mesoporous fiber coating was examined for the determination of benzo[a]pyrene (B[a]P) in water samples. The limit of detection (LOD) is 0.28μg·L-1. Good recovery and relative standard deviation (RSD) were obtained.
文摘This research examined the typical flavor compounds in the commonest type of Khat called Harari Khat grown in the region of Ethiopia.Twenty-eight compounds, which includes 1,2-Propanedione,1-Phenyl,Hexanol,Hexanal compounds,Limonene, Benzaldehyde with other flavors, were extracted by polydimethylsiloxane at room temperature for 30min from Khat samples,and identified by solid-phase microextraction-gas chromatography-mass spectrometry (SPME-GC-MS).This method needs no organic solvents and required minimal sample.
文摘The chlorination process is one of the water treatment method used for the disinfection of water. The disinfection by products are trihalomethanes such as chloroform, dichloromethane, dibromochloromethane and bromoform. A headspace solid-phase microextraction method has been developed for determination oftrihalomethanes in water samples. The experimental parameters such as the stirring rate, extraction time, extraction temperature and desorption time were investigated. The linearity, detection limits and percentage recovery were evaluated. The optimum conditions were stirring rate 800 rpm/min, extraction time 6 min, extraction temperature 20 ~C, desorption time 2.5 min and desorption temperature 220 ~C. The detection limits were 0.01 ~g/L and the recoveries were in the range of 86-110 %, The proposed method was successfully applied to determination of THM4 in tap water samples. The THM4 contents were varied depending on the sample sites and the season. The total THM4 contents in cool, summer and rainy season were in the range of 27.58-41.89, 32.06-60.73 and 46.26-69.87 p.g/L, respectively. Confirmation of the detected compounds in water samples were performed by gas chromatograph-mass spectrometer. The mass spectra of the target compounds in water samples is in good agreement with trihalomethanes standard spectra.
基金Nonprofit Institute Research Grant of Xinjiang Uygur Autonomous Region(KY2019056).
文摘[Objectives]This study aimed to determine the volatile components in Santalum album Linn and gradually clarify the aroma composition of S.album Linn.[Methods]Solid-phase microextraction method was used to obtain the volatile components of S.album Linn.The aroma components were analyzed by gas chromatography-mass spectrometry and their relative contents were calculated using the area normalization method.[Results]In a dry state at room temperature,39 chemical components were identified from S.album Linn,mainly olefins(91.15%),alkanes(3.00%),alcohols(2.56%),esters(2.19%),ketones(0.55%),aldehydes(0.41%)and heterocyclics(0.14%).[Conclusions]This method has the advantages of low sample consumption,easy operation,rapid identification of aroma components and high sensitivity,and can effectively separate and determine volatile components in S.album Linn,realizing the rapid identification of different S.album Linn varieties and providing technical support for further research on Chinese medicinal materials.
基金Institutes of Health Research(CIHR)-Natural Sciences and Engineering Research Council(NSERC)of the Canada Collaborative Health Research Projects program for their financial support(Grant No.:355935)the Natural Sciences and Engineering Research Council of Canada Industrial Research Chair(IRC)program。
文摘In vivo lung perfusion(IVLP)is a novel isolated lung technique developed to enable the local,in situ administration of high-dose chemotherapy to treat metastatic lung cancer.Combination therapy using folinic acid(FOL),5-fluorouracil(F),and oxaliplatin(OX)(FOLFOX)is routinely employed to treat several types of solid tumours in various tissues.However,F is characterized by large interpatient variability with respect to plasma concentration,which necessitates close monitoring during treatments using of this compound.Since plasma drug concentrations often do not reflect tissue drug concentrations,it is essential to utilize sample-preparation methods specifically suited to monitoring drug levels in target organs.In this work,in vivo solid-phase microextraction(in vivo SPME)is proposed as an effective tool for quantitative therapeutic drug monitoring of FOLFOX in porcine lungs during pre-clinical IVLP and intravenous(IV)trials.The concomitant extraction of other endogenous and exogenous small molecules from the lung and their detection via liquid chromatography coupled to high resolution mass spectrometry(LC-HRMS)enabled an assessment of FOLFOX's impact on the metabolomic profile of the lung and revealed the metabolic pathways associated with the route of administration(IVLP vs.IV)and the therapy itself.This study also shows that the immediate instrumental analysis of metabolomic samples is ideal,as long-term storage at80℃ results in changes in the metabolite content in the sample extracts.
文摘In this report, gas chromatography-mass spectrometry (GC-MS) based non-targeted metabolomics is used to develop appropriate headspace solid phase microextractions (HS-SPME) to enhance the understanding of volatile complexity of flue-cured tobacco leaves. Non-targeted metabolic profiling of GC-MS shows that the extraction condition of HS-SPME at 100?C for 30 min provides a better metabolite profile than other extraction conditions tested. GC-MS and principal component analyses (PCA) show that among five types of fibers tested, 100 μm polydimethylsiloxane (PMDS), 65 μm polydimethylsiloxane/divinylbenzene (PMDS/DVB) and 75 μm carboxen/polydimethylsiloxane (CAR/ PMS) provide a better reproducible metabolite profile. Based on an appropriate PDMS extraction condition optimized, we use GC-MS analysis and PCA to compare metabolite profiles in flue-cured leaves of tobacco plants grown in North Carolina, India and Brazil, respectively. The resulting data of PCA show that the global metabolic profiles in North Carolina samples are separated from those in Brazil and India samples, two groups of which are characterized by a partially overlapped pattern. Several peaks that were differentially accumulated in samples were annotated to known metabolites by deconvolution analysis, such as norsolanadione, solavetivone and rishtin. Norsolanadione is detected only in Brazil samples. Solavetivone is detected in samples of India and Brazil but not in those of North Carolina. Rishtin is detected in samples of North Carolina and India but not in Brazil samples. These data indicate that not only can a non-targeted metabolic profiling approach enhance the understanding of volatile complexity, but also can identify marker volatile metabolites in tobacco leaves produced in different growth regions.
基金supported by the National Centre for Research and Development under the Lider IX programme(Grant No.:LIDER/44/0164/L-9/17/NCBR/2018)Permission to conduct experiments with controlled substances was issued by the local Pharmaceutical Inspector(Kujawsko-Pomorski Wojewodzki Inspektor Farmaceutyczny w BydgoszczyPermission No.:WIFBY-KK.857.2.4.2016).
文摘For identifying and quantifying prohibited substances,solid-phase microextraction(SPME)continues to arouse interest as a sample preparation method.However,the practical implementation of this method in routine laboratory testing is currently hindered by the limited number of coatings compatible with the ubiquitous high-performance liquid chromatography(HPLC)systems.Only octadecyl(C18)and polydimethylsiloxane/divinylbenzene ligands are currently marketed for this purpose.To address this situation,the present study evaluated 12 HPLC-compatible coatings,including several chemistries not currently used in this application.The stationary phases of SPME devices in the geometry of thin filmcoated blades were prepared by applying silica particles bonded with various functional ligands(C18,octyl,phenyl-hexyl,3-cyanopropyl,benzenesulfonic acid,and selected combinations of these),as well as unbonded silica,to a metal support.Most of these chemistries have not been previously used as microextraction coatings.The 48 most commonly misused substances were selected to assess the extraction efficacy of each coating,and eight desorption solvent compositions were used to optimize the desorption conditions.All samples were analyzed using an HPLC system coupled with triple quadrupole tandem mass spectrometry.This evaluation enables selection of the best-performing coatings for quantifying prohibited substances and investigates the relationship between extraction efficacy and the physicochemical characteristics of the analytes.Ultimately,using the most suitable coatings is essential for trace-level analysis of chemically diverse prohibited substances.
基金supported by the Canadian Institute of Health Research(CIHR)-Natural Sciences and Engineering Research Council(NSERC)of Canada Collaborative Health Research Projects program(Grant No.:355935)as well as by NSERC through the Industrial Research Chair(IRC)program(Program No.:#IRCPJ 184412e15).
文摘Adjuvant chemotherapy improves the survival outlook for patients undergoing operations for lung metastases caused by colorectal cancer (CRC). However, a multidisciplinary approach that evaluates several factors related to patient and tumor characteristics is necessary for managing chemotherapy treatment in metastatic CRC patients with lung disease, as such factors dictate the timing and drug regimen, which may affect treatment response and prognosis. In this study, we explore the potential of spatial metabolomics for evaluating metabolic phenotypes and therapy outcomes during the local delivery of the anticancer drug, oxaliplatin, to the lung. 12 male Yorkshire pigs underwent a 3 h left lung in vivo lung perfusion (IVLP) with various doses of oxaliplatin (7.5, 10, 20, 40, and 80 mg/L), which were administered to the perfusion circuit reservoir as a bolus. Biocompatible solid-phase microextraction (SPME) microprobes were combined with global metabolite profiling to obtain spatiotemporal information about the activity of the drug, determine toxic doses that exceed therapeutic efficacy, and conduct a mechanistic exploration of associated lung injury. Mild and subclinical lung injury was observed at 40 mg/L of oxaliplatin, and significant compromise of the hemodynamic lung function was found at 80 mg/L. This result was associated with massive alterations in metabolic patterns of lung tissue and perfusate, resulting in a total of 139 discriminant compounds. Uncontrolled inflammatory response, abnormalities in energy metabolism, and mitochondrial dysfunction next to accelerated kynurenine and aldosterone production were recognized as distinct features of dysregulated metabolipidome. Spatial pharmacometabolomics may be a promising tool for identifying pathological responses to chemotherapy.
文摘A fast and reliable method for the determination of trace PAHs (polynuclear aromatic hydrocarbons) in seawater by solid-phase microextraction (SPME) followed by gas chromatographic (GC) analysis has been developed. The SPME operational parameters have been optimized, and the effects of salinity and dissolved organic matter (DOM) on PAHs recoveries have been investigated. SPME measures only the portion of PAHs which are water soluble, and can be used to quantify PAH partition coefficient between water and DOM phases. The detection limits of the overall method for the measurement of sixteen PAHs range from 0.1 to 3.5 ng/g, and the precisions of individual PAH measurements range from 4% to 23% RSD. The average recovery for PAHs is 88.2±20.4%. The method has been applied to the determination of PAHs in seawater and sediment porewater samples collected in Jiaozhou Bay and Laizhou Bay in Shandong Peninsula, China. The overall levels of PAHs in these samples reflect moderate pollution compared to seawater samples reported elsewhere. The PAH distribution pattern shows that the soluble PAHs in seawater and porewater samples are dominated by naphthalenes and 3 ring PAHs. This is in direct contrast to those of the sediment samples reported earlier, in which both light and heavy PAHs are present at comparable concentrations. The absence of heavy PAHs in soluble forms (<0.1-3.5 ng/L) is indicative of the strong binding of these PAHs to the dissolved or solid matters and their low seawater solubility.