靶面激光光斑尺寸原位测量的研究

提供了一种简便易行的靶面激光光斑尺寸原位测量的方法。从高斯光束的横向光强分布特性出发,建立了激光烧蚀斑半径与辐照激光能量、光斑尺寸、烧蚀阈值间的关系式,模拟分析发现辐照激光光斑尺寸对烧蚀斑半径随辐照能量变化曲线有较大影响。对于脉宽为2 ms,波长为1064 nm的激光,实验测量了不同能量激光辐照下相纸烧蚀斑半径,并用推导出的关系式拟合测量数据,获得了靶面处光斑尺寸和样品烧蚀阈值。同时,也测量了不同位置处的光斑尺寸和样品烧蚀阈值,对高斯光束束腰位置和样品烧蚀阈值的光斑尺寸效应进行了验证。研究结果表明该技术结果可靠,简单高效。该技术可以为高能激光与固体物质相互作用的基础研究和激光加工等应用领域中实现简单方便地测量靶面光斑尺寸提供帮助。     

煤直接液化油中混合酚的分离研究

利用分子筛择形特点，对煤直接液化油中的混合酚实施高效分离。本研究选取间甲酚和对甲酚作为分离煤直接液化油馏分段混合酚的模型化合物，采用化学液相沉积法对HZSM-5吸附剂的孔口结构进行改变，分析分子筛硅铝比及颗粒粒径对模型化合物间甲酚和对甲酚吸附分离性能的影响，以获得高性能固相吸附剂，并将其应用于180-190℃馏分段混合酚分离。结果表明，当分子筛硅铝比为25、粒径为3-5 μm时，分子筛的孔口结构调节效果最优；当正硅酸乙酯的最小用量为0.2 mL/g时，固相吸附剂的吸附量为0.03 g/g，对甲酚选择性高于95%。由于外表面沉积物对吸附剂的孔口结构变化，导致对甲酚选择性的提高。进一步采用HZSM-5（1）吸附剂对真实煤直接液化油混合酚的分离中发现，苯酚和对甲酚的选择性均达到100%。     

Identification of metabolites of rupestonic acid in rat urine by liquid chromatography combined with electrospray ionization quadrupole time‐of‐flight tandem mass spectrometry

Rupestonic acid, a potential anti‐influenza agent, is an important and characteristic compound in Artemisia rupestris L., a well‐known traditional Uighur medicine for the treatment of colds. In the present study, high‐performance liquid chromatography combined with electrospray ionization quadrupole time‐of‐flight tandem mass spectrometry was used to detect and identify the metabolites in rat urine after oral administration of rupestonic acid. A total of 10 metabolites were identified or partially characterized. The structure elucidations of the metabolites were performed by comparing the changes in accurate molecular masses and fragment ions with those of the parent compound. The results showed that the main metabolites of rupestonic acid in rat urine were formed by oxidation, hydrogenation and glucuronidation. A metabolism pathway was proposed for the first time based on the characterized structures. This metabolism study can provide essential information for drug discovery, design and clinical application of rupestonic acid. Copyright © 2014 John Wiley & Sons, Ltd.     

Rational Designs for Lithium-Sulfur Batteries with Low Electrolyte/Sulfur Ratio

Lithium-sulfur batteries (LSBs) are considered a promising next-generation energy storage device owing to their high theoretical energy density. However, their overall performance is limited by several critical issues such as lithium polysulfide (PS) shuttles, low sulfur utilization, and unstable Li metal anodes. Despite recent huge progress, the electrolyte/sulfur ratio (E/S) used is usually very high (≥20 µL mg⁻¹), which greatly reduces the practical energy density of devices. To push forward LSBs from the lab to the industry, considerable attention is devoted to reducing E/S while ensuring the electrochemical performance. To date, however, few reviews have comprehensively elucidated the possible strategies to achieve that purpose. In this review, recent advances in low E/S cathodes and anodes based on the issues resulting from low E/S and the corresponding solutions are summarized. These will be beneficial for a systematic understanding of the rational design ideas and research trends of low E/S LSBs. In particular, three strategies are proposed for cathodes: preventing PS formation/aggregation to avoid inadequate dissolution, designing multifunctional macroporous networks to address incomplete infiltration, and utilizing an imprison strategy to relieve the adsorption dependence on specific surface area. Finally, the challenges and future prospects for low E/S LSBs are discussed.     

TiO2/MXene-Assisted LDI-MS for Urine Metabolic Profiling in Urinary Disease

Cancer remains an intractable medical problem. Rapid diagnosis and identification of cancer are critical to differentiate it from nonmalignant diseases. High-throughput biofluid metabolic analysis has potential for cancer diagnosis. Nevertheless, the present metabolite analysis method does not meet the demand for high-throughput screening of diseases. Herein, a high-throughput, cost-effective, and noninvasive urine metabolic profiling method based on TiO₂/MXene-assisted laser desorption/ionization mass spectrometry (LDI-MS) is presented for the efficient screening of bladder cancer (BC) and nonmalignant urinary disease. Combined with machine learning, TiO₂/MXene-assisted LDI-MS enables high diagnostic accuracy (96.8%) for the classification of patient groups (including 47 BC and 46 ureteral calculus (UC) patients) from healthy controls (113 cases). In addition, BC patients can also be identified from noncancerous UC individuals with an accuracy of 88.3% in the independent test cohort. Furthermore, metabolite variations between BC and UC individuals are investigated based on relative quantification, and related pathways are also discussed. These results suggest that this method, based on urine metabolic patterns, provides a potential tool for rapidly distinguishing urinary diseases and it may pave the way for precision medicine.     

A volatolomic approach using cerumen as biofluid to diagnose bovine intoxication by Stryphnodendron rotundifolium

An innovative volatolomic approach employs the detection of biomarkers present in cerumen (earwax) to identify cattle intoxication by Stryphnodendron rotundifolium Mart., Fabaceae (popularly known as barbatimão). S. rotundifolium is a poisonous plant with the toxic compound undefined and widely distributed throughout the Brazilian territory. Cerumen samples from cattle of two local Brazilian breeds (‘Curraleiro Pé-Duro’ and ‘Pantaneiro’) were collected during an experimental intoxication protocol and analyzed using headspace (HS)/GC–MS followed by multivariate analysis (genetic algorithm for a partial least squares, cluster analysis, and classification and regression trees). A total of 106 volatile organic metabolites were identified in the cerumen samples of bovines. The intoxication by S. rotundifolium influenced the cerumen volatolomic profile of the bovines throughout the intoxication protocol. In this way, it was possible to detect biomarkers for cattle intoxication. Among the biomarkers, 2-octyldecanol and 9-tetradecen-1-ol were able to discriminate all samples between intoxicated and nonintoxicated bovines. The cattle intoxication diagnosis by S. rotundifolium was accomplished by applying the cerumen analysis using HS/GC–MS, in an easy, accurate, and noninvasive way. Thus, the proposed bioanalytical chromatography protocol is a useful tool in veterinary applications to determine this kind of intoxication.     

An improved LC–MS/MS method for determination of docetaxel and its application to population pharmacokinetic study in Chinese cancer patients

Because of its unpredictable side effects and efficacy, the anticancer drug docetaxel (DTX) requires improved characterisation of its pharmacokinetic profiles through population pharmacokinetic studies. A sensitive and rugged LC–MS/MS method for the detection of DTX in human plasma was developed and optimised using paclitaxel as an internal standard (IS). The plasma samples underwent rapid extraction using hybrid solid-phase extraction-protein precipitation. The analyte and IS were separated with an isocratic system on a Zorbax Eclipse Plus C₁₈ column using water containing 0.05% acetic acid along with 20 μM of sodium acetate and methanol (30/70, v/v) as the mobile phase. Quantification was performed using a triple quadrupole mass spectrometer through multiple reaction monitoring in positive mode, using the m/z 830.3 → 548.8 and m/z 876.3 → 307.7 transitions for DTX and paclitaxel, respectively. The range of the calibration curve was 1–500 ng/mL for DTX, and the linear correlation coefficient was >0.99. The accuracies ranged from −4.6 to 4.2%, and the precision was no higher than 7.0% for the analytes. No significant matrix effect was observed. Both DTX and the IS showed considerable recovery. This method was finally applied to the establishment of a population pharmacokinetic model to optimise the clinical use of DTX.     

A dried blood spot assay with HPLC–MS/MS for the determination of larotrectinib in mouse blood and its application to a pharmacokinetic study

Larotrectinib is a first-generation tropomyosin kinase inhibitor, approved for the treatment of solid tumors. In this paper, we present a validated dried blood spot (DBS) method for the quantitation of larotrectinib from mouse blood using HPLC–MS/MS, which was operated under multiple reaction monitoring mode. To the DBS disc cards, acidified methanol enriched with internal standard (IS; enasidenib) was added and extracted using tert-butyl methyl ether as an extraction solvent with sonication. Chromatographic separation of larotrectinib and the IS was achieved on an Atlantis dC₁₈ column using 10 mm ammonium formate–acetonitrile (30:70, v/v) delivered at a flow-rate of 0.80 ml/min. Under these optimized conditions, the retention times of larotrectinib and the IS were ~0.93 and 1.37 min, respectively. The total run time was 2.50 min. Larotrectinib and the IS were analyzed using positive ion scan mode and parent–daughter mass to charge ion (m/z) transitions of 429.1 → 342.1 and 474.1 → 267.1, respectively, were used for the quantitation. The calibration range was 1.06–5,080 ng/ml. No matrix effect or carryover was observed. Hematocrit did not influence DBS larotrectinib concentrations. All of the validation parameters met the acceptance criteria. The applicability of the validated method was shown in a mouse pharmacokinetic study.     

Time-dependent Ginzburg–Landau equations for multi-gap superconductors

We numerically solve the time-dependent Ginzburg–Landau equations for two-gap superconductors using the finite-element technique. The real-time simulation shows that at low magnetic field, the vortices in small-size samples tend to form clusters or other disorder structures. When the sample size is large, stripes appear in the pattern. These results are in good agreement with the previous experimental observations of the intriguing anomalous vortex pattern, providing a reliable theoretical basis for the future applications of multi-gap superconductors.     

Definition and detection of data-based uniqueness in evaluating bilinear (two-way) chemical measurements

Multivariate curve resolution methods, frequently used in analyzing bilinear data sets, result in ambiguous decomposition in general. Implementing the adequate constraints may lead to reduce the so-called rotational ambiguity drastically, and in the most favorable cases to the unique solution. However, in some special cases, non-negativity constraint as minimal information of the system is a sufficient condition to resolve profiles uniquely. Although, several studies on exploring the uniqueness of the bilinear non-negatively constrained multivariate curve resolution methods have been made in the literature, it has still remained a mysterious question. In 1995, Manne published his profile-based theorems giving the necessary and sufficient conditions of the unique resolution. In this study, a new term, i.e., data-based uniqueness is defined and investigated in details, and a general procedure is suggested for detection of uniquely recovered profile(s) on the basis of data set structure in the abstract space. Close inspection of Borgen plots of these data sets leads to realize the comprehensive information of local rank, and these argumentations furnish a basis for data-based uniqueness theorem. The reported phenomenon and its exploration is a new stage (it can be said fundament) in understanding and describing the bilinear (matrix-type) chemical data in general.