Determination of sulpiride in human urine using excitation-emission matrix fluorescence coupled with second-order calibration.

This paper proposes a new and effective approach for the quantitative analysis of sulpiride, a significant antipsychotic drug, in human urine samples by the incorporation of excitation-emission matrix (EEM) fluorescence and second-order calibration methodologies based on the alternating fitting residue (AFR) and self-weighted alternating trilinear decomposition (SWATLD) algorithms. With the application of a second-order advantage, the proposed strategy could be utilized for a direct concentration determination of sulpiride with a simple pretreatment step, even in the presence of serious natural fluorescent interferences. The average recoveries of sulpiride in complex urine samples by using AFR and SWATLD with an estimated component number of three were 101.2 +/- 2.1 and 94.4 +/- 0.7%, respectively. Moreover, the accuracy of the two algorithms was also evaluated through elliptical joint confidence region (EJCR) tests as well as the figures of merit, such as sensitivity (SEN), selectivity (SEL) and limit of detection (LOD). The experimental results demonstrated that both algorithms, as promising quantitative alternatives, have been satisfactorily applied to the determination of sulpiride in human urine, but the performance of AFR was slightly better than that of SWATLD.     

带干扰的多险种风险模型的破产概率

将多险种风险模型推广到带干扰项的一种新模型,讨论了收益过程的性质,并利用鞅的方法得出了破产概率所满足的Lundberg不等式及其一般公式.     

气液色谱法测定双-(4,6-二异丙基水杨酸)合铜(Ⅱ)与脂肪胺和醇加合反应的热力学性质

用气液色谱法,在不同的温度下,测定了以α-甲基萘作为固定液时,路易斯碱脂肪胺和醇的溶解平衡常数K_R~0,以及它们与作为路易斯酸的过渡金属配合物双-(4,6-二异丙基水杨酸)合铜(Ⅱ)相互作用的表观分配常数K_R和加合反应的平衡常数K_1。再根据热力学公式: 进一步求出了加合反应的焓变ΔH和熵变ΔS。     

硅酸铋(BSO)晶体闪烁性能研究

报道对BSO晶体闪烁性能研究的若干结果. 包括晶体的激发光谱和荧光光谱、光产额、发光衰减时间和抗辐照能力等特性.     

Low-frequency modulation of distortion product otoacoustic emissions in humans

Low-frequency modulation of distortion product otoacoustic emissions (DPOAEs) was measured from the human ears. In the frequency domain, increasing the bias tone level resulted in a suppression of the cubic difference tone (CDT) and an increase in the magnitudes of the modulation sidebands. Higher-frequency bias tones were more efficient in producing the suppression and modulation. Quasi-static modulation patterns were derived from measuring the CDT amplitude at the peaks and troughs of bias tones with various amplitudes. The asymmetric bell-shaped pattern resembled the absolute value of the third derivative of a nonlinear cochlear transducer function. Temporal modulation patterns were obtained from inverse FFT of the spectral contents around the DPOAE. The period modulation pattern, averaged over multiple bias tone cycles, showed two CDT peaks each correlated with the zero-crossings of the bias tone. The typical period modulation pattern varied and the two CDT peaks emerged with the reduction in bias tone level. The present study replicated the previous experimental results in gerbils. This noninvasive technique is capable of revealing the static position and dynamic motion of the cochlear partition. Moreover, the results of the present study suggest that this technique could potentially be applied in the differential diagnosis of cochlear pathologies.     

弱粘结的斜交铺设层合圆柱壳的柱形弯曲

导出了两端简文的具有弱粘结界面的任意斜交铺设层合圆柱壳柱形弯曲问题的一个精确弹性理论解。分析中采用线性弹簧模型来表征界面的弱粘结特性。引进新的物理量改写了基本方程,导出了对应的状态空间列式,并利用变量替换技术将该状态方程转换成常系数状态方程,从而方便求解。最后给出了数值算例,并讨论了弱界面的影响。     

Systematic chemical profiling of a multicomponent Chinese herbal formula Huo Luo Xiao Ling Dan by ultra high performance liquid chromatography coupled with electrospray ionization quadrupoletime‐of‐flight mass spectrometry

Huo Luo Xiao Ling Dan, a Chinese herbal formula consisting of 11 different herbs, has been used in folk medicine for the treatment of arthritis and other chronic inflammatory diseases. However, the chemical compositions of Huo Luo Xiao Ling Dan are not completely characterized. In the present study, an ultra high performance liquid chromatography coupled with electrospray ionization quadrupole time‐of‐flight mass spectrometry method in positive and negative ion modes was employed to identify biochemical constitutes in Huo Luo Xiao Ling Dan. As a result, a total of 76 compounds including alkaloids, monoterpene glycosides, iridoids, phenolic acids, and tanshinones, coumarins, lactones, flavones, and their glycosides, triterpenes, and triterpene saponins were characterized by comparing the retention time and mass spectrometry data with reference standards within 5 ppm error or by reference to the reference literature. These results would provide the basis for a further in vivo study of Huo Luo Xiao Ling Dan and information for potential new drug candidates for treating arthritis and other chronic inflammatory diseases.     

Two more pieces of the colibactin genotoxin puzzle from Escherichia coli show incorporation of an unusual 1-aminocyclopropanecarboxylic acid moiety

Colibactin represents a structurally undefined class of bacterial genotoxin inducing DNA damage and genomic instability in mammalian cells, thus promoting tumour development and exacerbating lymphopenia in animal models. The colibactin biosynthetic gene cluster (clb) has been known for ten years and it encodes a hybrid nonribosomal peptide synthetase (NRPS)/polyketide synthase (PKS) assembly line. Nevertheless, the final chemical product(s) remain unknown. Previously, we and others reported several colibactin pathway-related metabolites including N-myristoyl-d-asparagine (1) as part of a prodrug precursor that is cleaved from the putative precolibactin to form active colibactin by the peptidase ClbP. Herein, we report two new colibactin pathway-related metabolites (2 and 3) isolated from a clbP mutant of the probiotic E. coli Nissle 1917 strain. Their structures were established by HRMS and NMR. Compound 2 shows an additional 4-aminopenatanoic acid moiety with respect to 1, while 3 is characterized by the presence of an unusual 7-methyl-4-azaspiro[2.4]hept-6-en-5-one residue. Moreover, we propose the biosynthetic pathway towards both intermediates on the basis of extensive gene inactivation and feeding experiments. The identification of 2 and 3 provides further insight into colibactin biosynthesis including the involvement and formation of a rare 1-aminocyclopropanecarboxylic acid unit. Thus, our work establishes additional steps of the pathway forming the bacterial genotoxin colibactin.     

Bulk derivatization and cation exchange restricted access media-based trap-and-elute liquid chromatography–mass spectrometry method for determination of trace estrogens in serum

Estrone (E1), estradiols (α/β-E2), and estriol (E3) are four major metabolically active estrogens exerting strong biological activities at very low circulating concentrations. This paper reports a sensitive and efficient method with automated, on-line clean-up and detection to determine trace estrogens in a small volume of serum samples using liquid chromatography–electrospray ionization–tandem mass spectrometry directly, without off-line liquid–liquid or solid-phase extraction pretreatments. Serum aliquots (charcoal stripped fetal bovine serum, 100 μL) were spiked with four estrogen standards and their corresponding isotope-labeled internal standards, then bulk derivatized with 2-fluoro-1-methyl-pyridium p-toluenesulfonate (2-FMP) to establish the calibration curves and perform method validation. Calibration was established in the concentration ranges of 5–1000 pg mL⁻¹, and demonstrated good linearity of R² from 0.9944 to 0.9997 for the four derivatized estrogens. The lower detection limits obtained were 3–7 pg mL⁻¹. Good accuracy and precision in the range of 86–112% and 2.3–11.9%, respectively, were observed for the quality control (QC) samples at low, medium, and high concentration levels. The stability tests showed that the derivatized serum samples were stable 8 h after derivatization at room temperature and at least to 48 h if stored at −20 °C. The method was applied to measure trace estrogens in real human and bovine serum samples, and three of four estrogen compounds studied were observed and quantified.     

The stereocomplex formation and phase separation of PLLA/PDLA blends with different optical purities and molecular weights

In this study, the poly(L-lactide)/poly(D-lactide)(PLLA/PDLA) blends with different optical purities of PLLA and various molecular weights of PDLA are prepared by solution mixing, and the stereocomplex formation and phase separation behaviors of these blends are investigated. Results reveal that optical purity and molecular weight do not vary the crystal structure of PLA stereocomplex(sc) and homochiral crystallites(hc). As the optical purity increasing in the blends, the melting temperature of sc(Tsc) and the content of sc(ΔHsc) increased, while the melting temperature of hc(Thm) hardly changes, although the content of hc(ΔHhm) decreased gradually. The Tsc and ΔHsc are also enhanced as the molecular weight of PDLA reduces, and the ΔHhm reduces rapidly even though the Thm does not vary apparently. With lower optical purities of PLLA and higher molecular weights of PDLA, three types of crystals form in the blends, i.e., PLA sc, PLLA hc and PDLA hc. As molecular weight decreases and optical purity enhances, the crystal phase decreases to two(sc and PDLA hc), and one(sc) finally. This investigation indicates that the phase separation behavior between PLLA and PDLA in the PLLA/PDLA blends not only depends on molecular weights, but also relies on the optical purities of polymers.