Analysis of organic compounds in environmental samples by headspace solid phase microextraction

The analysis of samples contaminated by organic compounds is an important aspect of environmental monitoring. Because of the complex nature of these samples, isolating target organic compounds from their matrices is a major challenge. A new isolation technique, solid phase microextraction, or SPME, has recently been developed in our laboratory. This technique combines the extraction and concentration processes into one step; a fused silica fiber coated with a polymer is used to extract analytes and transfer them into a GC injector for thermal desorption and analysis. It is simple, rapid, inexpensive, completely solvent-free, and easily automated. To minimize matrix interferences in environmental samples, SPME can be used to extract analytes from the headspace above the sample. The combination of headspace sampling with SPME separates volatile and semi-volatile analytes from non-volatile compounds, thus greatly reducing the interferences from non-target compounds. This paper reports the use of headspace SPME to isolate volatile organic compounds from various matrices such as water, sand, clay, and sludge. By use of the technique, benzene, toluene, ethyl-benzene, and xylene isomers (commonly known as BTEX), and volatile chlorinated compounds can be efficiently isolated from various matrices with good precision and low limits of detection. This study has found that the sensitivity of the method can be greatly improved by the addition of salt to water samples, water to soil samples, or by heating. Headspace SPME can also be used to sample semi-volatile compounds, such as PAHs, from complex matrices.     

Preparation of water‐soluble,syndiotacticity‐rich,low molecular weight poly(vinyl alcohol) microfibrils in high yields with the low‐temperature polymerization of vinyl pivalate in tetrahydrofuran and saponification

To prepare water‐soluble, syndiotacticity‐rich poly(vinyl alcohol) (PVA) microfibrils for various industrial applications, we synthesized syndiotacticity‐rich, low molecular weight PVA by the solution polymerization of vinyl pivalate (VPi) in tetrahydrofuran (THF) at low temperatures with 2,2′‐azobis(2,4‐dimethylvaleronitrile) (ADMVN) as an initiator and successive saponification of poly(vinyl pivalate) (PVPi). Effects of the initiator and monomer concentrations and the polymerization temperature were investigated in terms of the polymerization behaviors and molecular structures of PVPi and the corresponding syndiotacticity‐rich PVA. The polymerization rate of VPi in THF was proportional to the 0.91 power of the ADMVN concentration, indicating the heterogeneous nature of THF polymerization. The low‐temperature solution polymerization of VPi in THF with ADMVN proved to be successful in obtaining water‐soluble PVA with a number‐average degree of polymerization (P_n) of 300–900, a syndiotactic dyad content of 60–63%, and an ultimate conversion of VPi into PVPi of over 75%. Despite the low molecular weight of PVA with P_n = 800, water‐soluble PVA microfibrillar fibers were prepared because of the high level of syndiotacticity. In contrast, for PVA with P_n = 330, shapeless and globular morphologies were observed, indicating that molecular weight has an important role in the in situ fibrillation of syndiotacticity‐rich PVA. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1103–1111, 2002     

Electrospun Aspirin/Eudragit/Lipid Hybrid Nanofibers for Colon-targeted Delivery Using an Energy-saving Process

Both electrospinning apparatus and their commercial pro-ducts are extending their applications in a wide variety of fields. However, very limited reports can be found about how to implement an energy-saving process and in turn to reduce the production cost. In this paper, a brand-new type of coaxial spinneret with a solid core and its electrospinning methods are developed. A novel sort of medicated Eudragit/lipid hybrid nanofibers are gene-rated for providing a colon-targeted sustained release of aspirin. A series of characterizations demonstrates that the as-prepared hybrid nanofibers have a fine linear morphology with the aspirin/lipid separated from the matrix Eudragit to form many tiny islands. In vitro dissolution tests exhibit that the hybrid nanofibers are able to effectively prevent the release of aspirin under an acid condition (8.7%±3.4% for the first two hours), whereas prolong the drug release time period under a neutral condition(99.7±4.2% at the se-venth hour). The energy-saving mechanism is discussed in detail. The prepared aspirin-loaded hybrid nanofibers can be further transferred into an oral dosage form for potential application in counte-ring COVID-19 in the future.     

Chemometric Analysis of Urinary Volatile Organic Compounds to Monitor the Efficacy of Pitavastatin Treatments on Mammary Tumor Progression over Time

Volatile organic compounds (VOCs) in urine are potential biomarkers of breast cancer. Previously, our group has investigated breast cancer through analysis of VOCs in mouse urine and identified a panel of VOCs with the ability to monitor tumor progression. However, an unanswered question is whether VOCs can be exploited similarly to monitor the efficacy of antitumor treatments over time. Herein, subsets of tumor-bearing mice were treated with pitavastatin at high (8 mg/kg) and low (4 mg/kg) concentrations, and urine was analyzed through solid-phase microextraction (SPME) coupled with gas chromatography-mass spectrometry (GC-MS). Previous investigations using X-ray and micro-CT analysis indicated pitavastatin administered at 8 mg/kg had a protective effect against mammary tumors, whereas 4 mg/kg treatments did not inhibit tumor-induced damage. VOCs from mice treated with pitavastatin were compared to the previously analyzed healthy controls and tumor-bearing mice using chemometric analyses, which revealed that mice treated with pitavastatin at high concentrations were significantly different than tumor-bearing untreated mice in the direction of healthy controls. Mice treated with low concentrations demonstrated significant differences relative to healthy controls and were reflective of tumor-bearing untreated mice. These results show that urinary VOCs can accurately and noninvasively predict the efficacy of pitavastatin treatments over time.     

The DI-SPME Method for Determination of Selected Narcotics and Their Metabolites,and Application to Bone Marrow and Whole Blood Analysis

The present investigation utilised the quick and easy SPME/LC-MS method to determine selected narcotic substances and their metabolites in whole blood. The study included qualitative analysis and validation of the method. Analytes were determined in the linearity range of 25–300 ng/mL. The precision during and between days (in general CV < 13.41%), and the LOD which results in between 0.36 and 11.08 ng/mL, and the LOQ between 1.20 and 36.90 ng/mL were investigated. The validation results obtained, as well as the results of subsequent in-laboratory tests, confirmed the applicability of the method in the analysis of blood samples. An attempt to apply the method to the analysis of bone marrow samples has yielded promising results; however, more detailed studies are needed in this area.     

佩兰挥发性化学成分的固相微萃取研究

采用固相微萃取-气相色谱-质谱法分析佩兰中挥发性化学成分,共分离出84个组分,并鉴定了67个组分,用归一化法测定其质量分数,占总挥发性组分峰面积的98.05%。主要成分是对-伞花烃(5.19%)、芳樟醇(3.72%)、β-石竹烯(12.35%)、α-律草烯(13.39%)、α-姜黄烯(2.11%)、(-)-石竹烯氧化物(8.25%)、. /-.-4-乙酰基-1-甲基环己烯(8.91%)。     

Chemical Approach to the Optimization of Conditions Using HS-SPME/GC–MS for Characterization of Volatile Compounds in Eugenia brasiliensis Fruit

Grumixama (Eugenia brasiliensis Lam.) is a native fruit of the Brazilian Atlantic Forest, belonging to the Myrtaceae family, which designatesthe most significant number of species with food potential. It stands out due to its phytochemical characteristics because of the presence of polyphenols and volatile organic compounds. Volatile compounds are substances released by foods that give off an aroma and influence flavor. Solid-phase microextraction is a technique that allows for low-cost, fast, and solvent-free extraction, has an affinity for numerous analytes, and is easily coupled to gas chromatography. The objectives of this work were to evaluate the efficiency of different fibers of SPME (solid-phase microextraction) in the extraction of volatile organic compounds from grumixama pulp; optimize a method for extraction time, temperature, and sample weight; and to determine the characteristic volatile profile of this fruit. For the extraction of volatile compounds, three fibers of different polarities were used: polar polyacrylate (PA) fibers, divinylbenzene/carboxyne/polydimethylsiloxane (DVB/CAR/PDMS) semipolar fibers, and polydimethylsiloxane/divinylbenzene (PDMS/DVB). Fourteen volatile organic compounds (VOCs) were identified by DVB/CAR/PDMS, six by PA, and seven by PDMS/DVB through solid-phase microextraction in the headspace mode (SPME-HS). Considering the total number of compounds identified, regardless of the fiber used, and the optimization of the method, Eugenia brasiliensis presented sesquiterpene fractions (85.7%, 83.3%, and 85.7% of total VOCs) higher than the monoterpene fractions (14.3%, 16.7%, and 14.3%) for DVB/CAR/PDMS, PA, and PDMS/DVB, respectively in its composition. In addition, it was possible to verify that the fiber DVB/CAR/PDMS presented a better efficiency due to the larger chromatographic area observed when the grumixama pulp was subjected to conditions of 75 °C, 2.0 g, and an adsorption time of 20 min.     

Correlation between Irradiation Treatment and Metabolite Changes in Bactrocera dorsalis (Diptera: Tephritidae) Larvae Using Solid-Phase Microextraction (SPME) Coupled with Gas Chromatography-Mass Spectrometry (GC-MS)

The metabolites produced by the larvae of Bactrocera dorsalis (Diptera: Tephritidae) exposed to different doses of irradiation were analyzed using solid phase microextraction (SPME) and gas chromatography-mass spectrometry (GC-MS), and a metabonomic analysis method of irradiated insects based on GC-MS was established. The analysis revealed 67 peaks, of which 23 peaks were identified. The metabolites produced by larvae treated with different irradiation doses were compared by multivariate statistical analysis, and eight differential metabolites were selected. Irradiation seriously influenced the fatty acid metabolic pathway in larvae. Using the R platform combined with the method of multivariate statistical analysis, changes to metabolite production under four irradiation doses given to B. dorsalis larvae were described. Differential metabolites of B. dorsalis larvae carried chemical signatures that indicated irradiation dose, and this method is expected to provide a reference for the detection of irradiated insects.     

Short Tm3+-doped fiber lasers with watt-level output near 2 μm

High-power operation of diode-pumped fiber lasers at wavelength near 2μm are demonstrated with short length of heavily Tm3 -doped silica glass fibers. With 7-cm long fiber, a laser at near 2 μm is obtained with the threshold of 135 mW, maximum output power of 1.09 W, and slope efficiency of 9.6% with respect to the launched power from a laser diode at 790 nm. The output stability of this fiber laser is within 5%.The dependence of the performance of fiber lasers on the operation temperature and cavity configuration parameters is also investigated.     

Solvent selection in ultrasonic-assisted emulsification microextraction: Comparison between high- and low-density solvents by means of novel type of extraction vessel

There are numerous published reports about dispersive liquid phase microextraction of the wide range of substances, however, till now no broadly accepted systematic and purpose oriented selection of extraction solvent has been proposed. Most works deal with the optimization of available solvents without adequate pre-consideration of properness. In this study, it is tried to compare the performances of low- and high-density solvents at the same conditions by means of novel type of extraction vessel with head and bottom conical shape. Extraction efficiencies of seven basic pharmaceutical compounds using eighteen common organic solvents were studied in this work. It was much easier to work with high-density solvents and they mostly showed better performances. This work shows that although exact predicting the performance of the solvents is multifaceted case but the pre-consideration of initial selection of solvents with attention to the physiochemical properties of the desired analytes is feasible and promising. Finally, the practicality of the method for extraction from urine and plasma samples was investigated.