Urinary metabolomic study of non‐small cell lung carcinoma based on ultra high performance liquid chromatography coupled with quadrupole time‐of‐flight mass spectrometry

Metabolic profiles from human urine reveal the significant difference of carnitine and acylcarnitines levels between non‐small cell lung carcinoma patients and healthy controls. Urine samples from cancer patients and healthy individuals were assayed in this metabolomic study using ultra high performance liquid chromatography coupled to quadrupole time‐of‐flight mass spectrometry. The data were normalized by the sum of all intensities and creatinine calibration, respectively, before orthogonal partial least squares discriminant analysis. Twenty differential metabolites were identified based on standard compounds or tandem mass spectrometry fragments. Among them, some medium‐/long‐chain acylcarnitines, for example, cis‐3,4‐methylene heptanoylcarnitine, were found to be downregulated while carnitine was upregulated in urine samples from the cancer group compared to the control group. Receiver operating characteristic analysis of the two groups showed that the area under curve for the combination of carnitine and 11 selected acylcarnitines was 0.958. This study suggests that the developed carnitine and acylcarnitines profiling method has the potential to be used for screening non‐small cell lung carcinoma.     

One‐step strategy for the synthesis of a derivatized cyclodextrin‐based monolithic column

Derivatized β‐cyclodextrin (β‐CD) functionalized monolithic columns were prepared by a “one‐step” strategy using click chemistry. First, the intended derivatized β‐CD monomers were synthesized by a click reaction between propargyl methacrylate and mono‐6‐azido‐β‐CD and then sulfonation or methylation was carried out. Finally, monolithic columns were prepared through a one‐step in situ copolymerization of the derivatized β‐CD monomer and ethylene glycol dimethacrylate. The sulfated β‐CD‐based monolith was successfully applied to the hydrophilic interaction liquid chromatography separation of nucleosides and small peptides, while the methylated β‐CD‐functionalized monolith was useful for the separation of nonpolar compounds and drug enantiomers in capillary reversed‐phase liquid chromatography. The structures of the monomers were characterized by Fourier transform infrared spectroscopy and mass spectrometry. The physicochemical properties and column performance of monoliths were evaluated by scanning electron microscopy and micro high performance liquid chromatography. This strategy has considerable prospects for the preparation of other derivatized CD‐functionalized methacrylate monoliths.     

Evaluation of a series of prolylamidepyridines as the chiral derivatization reagents for enantioseparation of carboxylic acids by LC–ESI–MS/MS and the application to human saliva

Mass spectrometry has become a popular analytical tool because of its high sensitivity and specificity. The use of a chiral derivatization reagent for the mass spectrometry (MS) detection seems to be efficient for the enantiomeric separation of racemates. However, the number of chiral reagents for the liquid chromatography (LC)–MS/MS analysis is very limited. According to these observations, we are currently in the process of developing novel labeling reagents for chiral molecules in MS/MS analysis. The derivatization reagent that is effective for enhancing not only the electrospray ionization–MS/MS sensitivity but also the reversed-phase LC resolution of carboxylic acid enantiomers should have a highly proton-affinitive moiety and an asymmetric structure near the reactive functional group. Furthermore, the resulting derivative has to provide a characteristic product ion suitable for the selected reaction monitoring. Based upon these considerations, a series of prolylamidepyridines ((S)-N-pyrrolidine-2-carboxylic acid N-(pyridine-2-yl)amide (PCP2), (S)-N-pyrrolidine-2-carboxylic acid N-(pyridine-3-yl)amide, and (S)-N-pyrrolidine-2-carboxylic acid N-(pyridine-4-yl)amide) was synthesized as ideal labeling reagents for the enantioseparation of chiral carboxylic acids and evaluated in terms of separation efficiency and detection sensitivity by ultra-performance LC (UPLC)–MS/MS. Among the synthesized reagents, PCP2 was the most efficient chiral derivatization reagent for the enantioseparation of carboxylic acid. The Rs values and the detection limits of the derivatives of non-steroidal anti-inflammatory drugs, which were selected as the representative carboxylic acids, were in the range of 2.52–6.07 and 49–260 amol, respectively. The sensitive detection of biological carboxylic acids (detection limits, 32–520 amol) was also carried out by the proposed method using PCP2 and UPLC–MS/MS. The PCP2 was applied to the determination of carboxylic acids in human saliva. Several biological carboxylic acids, such as lactic acid (LA), 3-hydroxybutylic acid, maric acid, succinic acid, α-ketoglutalic acid, and citric acid, were clearly identified in the saliva of healthy persons and diabetic patients. Furthermore, the ratio of d-LA in diabetic patients was higher than that in normal subjects. Judging from these results, PCP2 seems to be a useful chiral derivatization reagent for the determination not only of chiral, but also achiral, carboxylic acids in real samples.

石墨烯/锌铁氧体复合物的制备及抗菌性能

用氧化还原法和化学共沉淀法分别制备了石墨烯(GE)和石墨烯/锌铁氧体(GE/ZnFe2O4)复合物,通过现代测试技术表征了样品的物相结构、组成和微观形貌.以大肠杆菌、金黄色葡萄球菌和白色念珠菌为测试菌种,分别对样品的抗菌性能进行了研究.结果表明,样品的抗菌活性受GE/ZnFe2O4复合物中GE和ZnFe2O4质量比(mG/Z)以及菌种的影响,其中mG/Z=0.4的复合物对三种菌均有较好的抗菌效果,其最小抑菌浓度分别为25、25和12.5μg/mL;复合物对白色念珠菌的抗菌效果最好,这与菌种的结构有关.此外,对样品的抗菌机理进行了详细研究.     

Self‐Regulation in Flow‐Induced Structure Formation of Polypropylene

Flow‐induced structure formation is investigated with in situ wide‐angle X‐ray diffraction with high acquisition rate (30 Hz) using isotactic polypropylene in a piston‐driven slit flow with high wall shear rates (up to ≈900 s⁻¹). We focus on crystallization within the shear layers that form in the high shear rate regions near the walls. Remarkably, the kinetics of the crystallization process show no dependence on either flow rate or flow time; the crystallization progresses identically regardless. Stronger or longer flows only increase the thickness of the layers. A conceptual model is proposed to explain the phenomenon. Above a certain threshold, the number of shish‐kebabs formed affects the rheology such that further structure formation is halted. The critical amount is reached already within 0.1 s under the current flow conditions. The change in rheology is hypothesized to be a consequence of the “hairy” nature of shish. Our results have large implications for process modelling, since they suggest that for injection molding type flows, crystallization kinetics can be considered independent of deformation history.

     

福建沿海经济带城镇化质量测度与提升路径

城镇化质量的提升是有序推进城镇化健康发展的关键,从经济发展、社会发展、生态环境、基础设施质量和城乡一体化方面构建城镇化质量综合评价指标体系,运用熵值法MATLAB软件综合测度福建沿海城镇化质量空间分异,依据城镇化质量综合得分,采用系统聚类法将福建沿海城镇化质量划分为3大类型区域,利用ArcGIS10.2软件进行可视化。研究表明:福建沿海地区城镇化质量差异明显,厦门城镇化质量综合得分最高,属于高质量城镇化区域;福州、泉州、莆田分别排名2~4位,属于中等质量城镇化区域;漳州和宁德分别排名5~6位,属于低质量城镇化区域。     

无双线性对的无证书签密方案分析与改进

对高键鑫等人提出的一种无双线性对运算的无证书签密方案进行密码分析,指出方案的不可伪造性证明存在漏洞,致使方案不安全,并提出了一个改进的签密方案.安全性能方面,为了抵抗不诚实用户发起的公钥替换攻击,改进方案在签密运算的指数部分加入用户生成的部分公钥的哈希函数值,并在随机预言模型下证明了改进方案对自适应选择消息和身份攻击是存在性不可伪造的,改进方案没有使用计算耗时的对运算,具有较高的运算效率.     

基于惯性测量器件的无线步态分析平台

步态定量测量方法应用于许多领域,如临床医学、双足机器人控制等.采用惯性测量单元结合无线传感器网络建立了一个步态分析平台,将两个无线惯性测量单元传感器节点分别绑定在左右双侧脚踝,以同时采集双脚运动过程中的加速度和角速度信号,并将其通过无线方式发送到远程终端.通过模式识别、时间序列分析、阈值检测和零速修正等多种数据融合方法计算步态参数,并通过融合双足传感器数据得到双支撑相、双脚步行周期等重要的双足步态参数,其中双支撑相参数对人体日常动作的识别有重要意义.实验结果显示该研究具有较高的计算精度.     

偏微分方程最优控制中的变分迭代法应用

首先使用极大值原理得到偏微分方程问题的最优性条件,然后使用变分迭代法求解Hamilton-Pontryagin方程,实现了偏微分方程最优控制问题的准确快速求解。结合两个最优控制的经典实例,对模型和算法进行了仿真实验,证明了该方法的可行性和有效性。     

基于对比度补偿的立体视频舒适度评价

为给评价立体视频的舒适程度提供一种可参考的标准, 在确定人眼观看立体视频时水平视差为主要影响因素基础上, 以对比度作为其补偿因素对立体视频舒适度的影响。利用图形分割方法将前景与背景分离, 利用场景相关的显著区域提取方法得到显著区域, 提取显著区域的视差并分别提取前景和背景对比度, 结合深度感知理论和最小二乘拟合方法建立评价模型, 利用主观评价方法对模型进行评定, 由此得到对立体视频舒适度评价的一种方法。由主观评价验证可知, 该评价方法与人眼的立体视觉基本一致, 为进一步研究人眼立体舒适度提供参考。