Preparation of organic–inorganic hybrid silica monolith with octyl and sulfonic acid groups for capillary electrochromatograhpy and application in determination of theophylline and caffeine in beverage

An organic–inorganic hybrid silica monolithic column with octyl and sulfonic acid groups has been prepared by sol–gel technique for capillary electrochromatograhpy. The structure of hybrid monolith was optimized by changing the composition of tetraethoxysilane (TEOS), octyltriethoxysilane (C₈-TEOS) and 3-mercaptopropyltrimethoxysilane (MPTMS) in the mixture of precursors. Then, the obtained hybrid monolith was oxidized using hydrogen peroxide (30%, w/w) to yield sulfonic acid groups. The sulfonic acid group, which served as strong cation-exchanger, dominated the charge on the surface of the capillary column and generated stable electroosmotic flow (EOF) in a wide range of pH. The monolithic column was characterized by scanning electron microscopy (SEM), Fourier transform infrared (FT-IR) spectroscopy and elemental analysis (EA), and the performance of column was evaluated in detail by separating different kinds of compounds with column efficiency up to 155,000 plates/m for thiourea. In addition, this monolithic column was also applied in the analysis of theophylline (TP) and caffeine (CA) in beverages. The detection limits were 0.39 and 0.48 μg/mL for theophylline and caffeine, respectively. The method reproducibility was tested by evaluating the intra- and inter-day precisions, and relative standard deviations of less than 3.9 and 8.4%, respectively, were obtained. Recoveries of compounds from spiked beverage samples ranged from 87.2 to 105.2%.     

液晶性9-苯亚甲基取代芴-苯共聚物的设计合成及催化剂对聚合物链立构规整性、液晶性和光学性质的影响

为了制备适于制造有机发光场效应管的高分子材料, 通过Suzuki偶联反应, 采用不同Pd催化剂, 合成了一种侧基横挂偶极基团的液晶9-苯亚甲基取代芴-苯共聚物. 考察了不同催化剂对合成的聚合物的分子量、聚合物链中单体单元的结构排列及液晶性质和光学性质的影响. 结果表明, 2种不同的Pd催化剂对合成的聚合物的分子量影响不大, 但对聚合物链的立构规整性以及聚合物的液晶态温度范围有较大的影响. Pd(PPh3)4作催化剂合成的聚合物(PA)中单体单元的结构排列较单一, 立构规整性好, 有较宽的液晶态温度范围. Pd(OAc)2为催化剂合成的聚合物(PB)链中单体单元的结构排列相对复杂, 液晶态温度范围较窄. 聚合物链的立构规整性对其光学性质影响很大. PA具有较高的溶液及固体膜的紫外最大吸收峰值和溶液荧光效率, 其退火膜的激发和发射光谱的半峰宽均比PB的窄, 并且光学性质不随加热条件的变化而变化.     

新型白桦脂酸糖苷化衍生物的合成及体外抗A549活性

为改善白桦脂酸的水溶性和稳定性,以白桦脂酸苷元为起始原料,对其28-COOH进行甲基化修饰后制得白桦脂酸-28-羧甲酯(1)。分别以D-半乳糖、D-氨基葡萄糖等为起始原料,通过对糖羟基保护与去保护,得到一系列单糖、二糖片段。通过三氯乙酰亚胺酸酯途径合成的糖片段对1的3-位羟基进行修饰,合成了3种白桦脂酸糖苷化衍生物2~4,其结构经¹H NMR、¹³C NMR和MS（ESI）表征。采用MTT法测试了2~4对人肺癌细胞(A549)的体外抑制活性。结果表明：化合物2~4在不同浓度下对A549细胞均有一定抑制作用,其中化合物4在浓度1×10^-3 mmol·L^-1时抑制率最高,达到(91.07±0.18)%。      

动基座激光束定向偏差测量新方法

提出了将二维摆镜和象限探测器相结合的动基座激光束定向偏差测量新方法.以摆镜作为快速调整激光发射主光轴方向的元件,利用象限探测器测量从目标返回激光主光轴的动态变化量,并从中分离光轴稳定平台运动对摆镜的耦合作用,得到激光主光轴相对目标视线的偏角,进而操控激光发射主光轴稳定瞄准目标.该方法具有较好的实时性,适用于运动目标的跟踪及时间为秒级的机载激光制导武器.     

基于马尔可夫随机场的改进Metropolis混凝土CT的图像分割方法

提出一种基于马尔可夫随机场改进的Metropolis模拟退火算法.该算法中阈值α的选取优化了Metropolis算法.根据Beyes理论将图像分割问题转化为最大后验概率求取问题,并给出了参量预测算法.在实验中,将本文提出的算法与ICM、传统的Metropolis和Gibbs采样模拟退火算法进行比较.结果表明改进的Metropolis算法在图像分割效率和分割准确度上都有明显的提高.通过混凝土CT图像分割实验,改进Metropolis的应用能够较完整地反映出混凝土材料的内部结构和缺陷.     

直接调制半导体激光器的脉冲驱动电路研究

研制了一种应用于直接调制半导体激光器的脉冲驱动电路.根据直接数字频率合成原理,利用现场可编程逻辑阵列产生频率可调方波去触发雪崩晶体管,以及雪崩晶体管的雪崩效应产生频率可调脉宽固定在3 ns的主体脉冲.该脉冲经过衰减器衰减得到合时的脉冲幅度.输出脉冲最高频率可到100 kHz,其输出电压幅度为9 V.     

丝素肽和β-环糊精包合作用及表面活性剂影响

在pH为2和包合时间是60min的最佳条件下,采用光谱法（荧光光谱与紫外-可见光谱）测得β-环糊精（β-CD）与丝素肽构成的包合体系包合比均是2∶1,平均包合常数是3.3×105。两种阴离子表面活性剂十二烷基硫酸钠、十二烷基苯磺酸钠对包合体系有阻抑作用,阳离子表面活性剂十六烷基三甲基溴化铵和非离子表面活性剂＂平平加O＂对包合体系没有影响。     

泉州湾滨海退化湿地红树林修复工程对土壤酶活性的影响

以泉州湾滨海退化湿地为对象，通过野外调查、采样、实验室分析，初步研究红树林修复工程对土壤酶活性的影响。结果表明，退化湿地修复前土壤磷酸酶和脲酶活性分别为8.78~17.72 μg/(g?24 h)和45.86~80.12 μg/(g?24 h)，修复后土壤磷酸酶和脲酶活性分别为10.21~14.22 μg/(g?24 h)和85.83~102.22 μg/(g?24 h)。在秋茄+桐花树+红海榄修复模式下，土壤磷酸酶和脲酶活性均明显增高；在秋茄+桐花树+白骨壤修复模式下，土壤磷酸酶活性明显降低，脲酶活性有一定增高；在秋茄+桐花树+木榄修复模式下，土壤磷酸酶和脲酶活性变化均不明显。     

Embedding Alkyldiamine into Layered α-Titanium Phosphate via Direct-Ion Exchange and its Application in EuIII Removal from Water

Diamine-pillared α-titanium phosphate (α-TiP) was prepared via direct ion exchange method. Moreover, 1,3-propanediamine, as the pillaring agent, was used to investigate the effect of pH, content and temperature on the interlayer distance of α-TiP. The structure and properties of the samples were characterized by X-ray Diffraction (XRD), Fourier Transform Infrared Spectroscopy (FT-IR), Field Emission Scanning Electron Microscopy (SEM), and Differential Thermal Analysis (TG). The results show that the interlayer distance of α-TiP was enlarged from 7.6 Å to 16.18 Å as the carbon chain of the intercalating diamine increased from (NH₂(CH₂)_nNH₂) (n = 2 to 7). The layer space structure consists of monomolecular alkyl chains with an average tilt angle of 75.6°. The uptake values for these five alkyldiamine cations were 3.780, 3.261, 2.443, 2.175, and 1.954 mmol, per gram of TiP, respectively. Also, we found that the direct ion exchange method is more effective in a weak acidic environment. The variation of interlayer distance was a consecutive process, and unaffected by temperature. The 1,3-propanediamine intercalation product (α-TiPPda) showed excellent performance towards Eu^III adsorption in water with removal efficiencies ≥ 99 %.