Development and application of chemometric-assisted dispersive liquid-liquid microextraction for the determination of suspected fragrance allergens in water samples

A simple and green method based on dispersive liquid-liquid microextraction, mated to chemometrics and followed by mass spectrometric detection for the determination of suspected fragrance allergens in water samples is developed and assessed in this work. Volume of extraction and disperser solvent, pH, ionic strength, extraction time, sample volume, as well as centrifugation time were initially optimized in a fractional factorial design. The obtained significant factors were optimized by using a central composite design and the quadratic model between the dependent and the independent variables was built. The obtained optimal conditions were: aqueous sample of 3.8 mL, 100 μL chloroform, 1.40 mL acetone, 4 min centrifugation time, natural pH containing 5% (w/v) NaCl, and centrifugation speed 4000 rpm. Method proved to be linear over a wide range of concentration for all analytes with R(2) between 0.9807 and 0.9959. The repeatability and reproducibility of the proposed method, expressed as relative standard deviation, varied between 3-13% and 4-16%, respectively. The limits of detection ranged from 0.007 to 1.0 μg L(-1) . The recommended method was applied to water samples including baby bath as well as swimming pool water samples and was compared with a previously reported method.     

Joint spectrogram segmentation and ridge-extraction method for separating multimodal guided waves in long bones

Ultrasonic guided waves (GWs) can be used to evaluate long bones effectively because of the ability to provide the information of the whole bone. In this study, a joint spectrogram segmentation and ridge-extraction (JSSRE) method was proposed to separate multiple modes in long bones. First, the Gabor time-frequency transform was applied to obtain the spectrogram of multimodal signals. Then, a multi-class image segmentation algorithm was used to find the corresponding region of each mode in the spectrogram, including an improved watershed transform and a region growing procedure. Finally, the ridges were extracted and the time domain signals representing individual modes were reconstructed from these ridges in each region. The validations of this method were discussed by simulated multimodal signals with different signal-to-noise ratios (SNR). The correlation coefficients between the original signals without noise and the reconstructed signals were calculated to analyze the results quantitatively. The results showed that the extracted ridges were in good agreement with generated theoretical dispersion curves, and the reconstructed signals were highly related to the original signals, even under the SNR=3 dB situation.     

Cyanobiphenyl-based liquid crystal dimers and the twist-bend nematic phase

ABSTRACT

The synthesis and characterisation of several members of the 1,ω-bis(4-cyanobiphenyl-4′-yl) alkane (CBnCB) and the 1-(4-cyanobiphenyl-4′-yloxy)-ω-(4-cyanobiphenyl-4′-yl) alkane (CBnOCB) homologous series are reported. The new odd members described CB5CB, CB13CB, CB4OCB, CB8OCB and CB10OCB all exhibit twist-bend nematic and nematic phases. The members of these series already reported in literature, CB7CB, CB9CB, CB11CB and CB6OCB, were also prepared in order to allow for a direct comparison of their transitional properties. The properties of these dimers are also compared to those of the corresponding members of the 1,ω-bis(4-cyanobiphenyl-4,-yloxy) alkanes (CBOnOCB). For any given total spacer length, for odd members of these series, the nematic–isotropic transition temperatures and associated entropy changes are greatest for the CBOnOCB dimer and lowest for the CBnCB dimer. These trends are understood in terms of molecular shape. For short spacer lengths, the twist-bend nematic–nematic transition temperature (T_NTBN) is higher for the CBnOCB series than for the CBnCB series but this is reversed as the spacer length increases. Of the CBOnOCB dimers, a virtual value of T_NTBN was estimated for CBO3OCB and T_NTBN was measured for CBO5OCB. These values are considerably lower than those observed for the corresponding members of the CBnCB or CBnOCB series. The dependence of T_NTBN on molecular structure is discussed not only in terms of the molecular curvature but also in the ability of the molecules to pack efficiently. As the temperature range of the preceding nematic phase increases, so the twist-bend nematic–nematic transition entropy change decreases and the transition approaches second order for the longer spacers. For comparative purposes, the transitional behaviour of the even-membered dimers CB6CB, CB5OCB and CBO4OCB is reported and differences accounted for in terms of molecular shape.     

Structural characteristics of different types of nanoparticles synthesised in mesomorphic metal alkanoates

The class of thermotropic ionic liquid crystals (LCs) of the metal alkanoates possesses a number of unique properties, such as intrinsic ionic conductivity, high dissolving ability and ability to form time-stable mesomorphic glasses. These ionic LCs can be used as nanoreactors for the synthesis and stabilisation of different types of nanoparticles (NPs). Thus, some semiconductors, metals and core/shell NPs were chemically synthesised in the thermotropic ionic liquid crystalline phase (smectic A) of the cadmium octanoate (CdC₈) and of the cobalt octanoate (CoC₈). By applying the scanning electron microscopy, the cadmium and cobalt octanoate composites containing CdS, Au, Ag and core/shell Au/CdS NPs have been studied. NPs’ sizes and dispersion distribution of the NPs’ size in the nanocomposites have been obtained.     

Loss of Pendimethalin in Surface Runoff from Plots Untilled and Tilled with Tobacco

Abstract

The loss of pendimethalin (N-(ethylpropyl)-2,6-dinitro-3,4-xylidine), a selective herbicide in runoff water was determined on sandy-clay-loam soil plots cultivated with tobacco in relation with the use of ammonium nitrate limestone as fertelizer, for a period of two years, 1990 and 1991. The surface slope of plots was 11% and the use of fertilizer decreased the soil erosion from a value 617 g/m²to 320 g/m². The runoff of surface waters were between 16-24% of the rainfall amounts. Reduction in pendimethalin in waterways results from water loss by infiltration, sediment loss, and by attachment adsorption on vegetative and organic matter. Surface runoff levels were highest for the first runoff event after herbicide application, 1.5 g/10 m² and initial concentrations were related to the time lapse between herbicide application and the date of the first run-off event. Maximum concentrations were 5.95 and 8.54 μg/L in 1990 and 1991 respectively. Persistence studies showed that pendimethalin concentration in runoff of 0.5 cm soil layer decreased by 88.2%, from 2.46 to 0.29 μg/g within 233 days, in 1990 and by 87.6%, from 2.42 to 0.30 μg/g within 235 days in 1991. After 310 day the concentration of pendimethalin was only 0.1 μg/g.     

松质骨超声背散射信号的谱信息熵判断方法

在松质骨超声背散射评价的实际应用中,如何快速准确地判断接收到的信号中是否包含有效背散射信号是一个重要问题。提出一种基于谱信息熵的背散射信号判断方法。对在体采集的984例成人跟骨处临床数据,采用该方法判断背散射信号的有效性,将判断结果与经验判断结果进行对照分析,并分析该方法中的信号区间长度和谱信息熵分段数对判断结果的影响。结果表明,当信号区间长度为13μs,谱信息熵分段数为15~20时,该方法可以获得最佳的判断结果(准确度〉95%,灵敏度〉99%,特异度〉87%),并且计算时间极短(1.5 ms)。因此采用谱信息熵方法判断背散射信号的有效性,可以满足超声骨质评价中对准确性和实时性的要求。     

超声诊断骨质疏松症中松质骨的模型

骨质疏松症(OP)是老龄化社会中影响健康的一个重要问题，超声技术已成为诊断骨质疏松症的一种常用方法。文中综述了近年来用超声诊断骨质疏松症中松质骨模型研究的进展，对棒状模型、流体多孔介质模型(Biot理论)和层状模型(schoenberg理论)进行了分析和讨论，指出了各理论模型存在的缺陷，对下一步的研究工作提出了建议。     

Determination of the pesticides considered as endocrine-disrupting compounds (EDCs) by solid-phase extraction followed by gas chromatography with electron capture and mass spectrometric detection

An SPE method followed by GC-electron capture detection (ECD) with confirmation by MS for the trace determination of four pesticides considered as endocrine-disrupting compounds (EDCs) in natural waters and sediments has been developed. Target analytes, fenarimol, fenvalerate, pendimethalin, and vinclozolin, belong to different chemical groups and are used mainly in agriculture. In the present study, analysis employs an offline SPE step for the extraction of the target analytes from natural waters. Sonication and subsequent SPE clean-up was used for extraction and purification of the sediment samples which were finally treated with activated copper powder. The type of SPE disk, eluents as well as solution parameters including pH value, and concentrations of salts and humic substances were examined for the efficiency of the method. The recoveries of all pesticides were in relatively high levels, ranging from 75 to 97% for waters and 71 to 84% for sediment samples. Both methods were applied to real water and sediment samples and the presence of the tested compounds was investigated.     

Aqueous phototransformation of zinc pyrithione Degradation kinetics and byproduct identification by liquid chromatography--atmospheric pressure chemical ionisation mass spectrometry

The photochemical behavior of the antifouling agent zinc pyrithione (ZnPT) was studied in aqueous media of different composition under simulated solar irradiation using a xenon light source. The influence of important constituents of natural water (dissolved organic matter and nitrate) was also examined using a multivariate kinetic model. It was found that photodegradation proceeds via a pseudo first-order reaction. Kinetic experiments were monitored by LC-MS and photolytic half-lives ranging between 9.2 and 15.1 min have been observed. The increasing concentration of dissolved organic matter (DOM) accelerates the photolysis reaction, while the effect of nitrate ions was also positive since it increased the degradation rate, but to a lesser extent. Irradiation of the aqueous ZnPT solutions gave rise to several transformation products that were isolated by means of solid-phase extraction using poly(styrene-divinylbenzene) extraction disks. These byproducts were identified using liquid chromatography-atmospheric pressure chemical ionisation mass spectrometry. Besides 2-pyridinesulfonic-acid, other degradation products formed included pyridine-N-oxide, 2-mercaptopyridine, 2,2'-dithiobis(pyridine-N-oxide), 2,2-dipyridyl disulfide and the pyridine/pyrithione mixed disulfide, 2,2'-dithiobispyridine mono-N-oxide (PPMD).     

骨小梁中超声背散射信号的频率分析及其微结构的估计

骨质疏松症是一种骨强度下降的全身性骨骼疾病,骨强度的下降是骨量减少和骨微结构退化的共同结果。相比于传统的超声透射方法,超声背散射法可提供更多的骨微结构信息,而对于松质骨结构的建模能有助于结构信息的获取。本文将骨小梁简化为单圆柱模型(圆柱状的单根骨小梁浸于骨髓中),并基于此模型对超声背散射与频率的关系进行分析。用铝线代替骨小梁做仿体实验,通过实验与理论结果的比较来验证单圆柱模型的可行性。