以萘酰亚胺衍生物基荧光高分子为载体和指示剂的 相分离免疫分析方法

以4-甲氧基-N-(2-N’,N’-二甲基氨基乙基-N’-烯丙基)萘二甲酰亚胺氯化铵(DMNAA)为荧光单体, 合成了一种pH敏感荧光高分子聚N-异丙基丙烯酰胺-4-甲氧基-N-(2-N’,N’-二甲基氨基乙基-N’-烯丙基)萘二甲酰亚胺氯化铵-N,N-二甲基氨丙基甲基丙烯酰胺[P(NIP-DMAPM-DMNAA)]. 采用共聚法将日本血吸虫抗原(SjAg)固定在P(NIP-DMAPM-DMNAA)上, 制备P(NIP-DMAPM-DMNAA)-SjAg连接物, 与日本血吸虫抗体(待测, SjAb)发生免疫反应后, 调节pH值, 使荧光高分子相变分离高分子-免疫组分连接物, 最后, 利用蛋白A对抗体的亲和性捕获P(NIP-DMAPM-DMNAA)-SjAg-SjAb, 通过测定高分子自身的荧光信号来定量 SjAb. 该新型高分子具有良好的荧光特性, 对pH响应快速, 37 ℃下相转变pH值为7.2, 分离免疫复合物时造成的损害低. 与传统相分离免疫分析比较, 新方法通过高分子相变分离和蛋白A捕获双重分离作用, 消除了非特异性组分和未反应的特异性免疫成分等的干扰; 利用高分子自身的荧光信号检测, 无须另外的标记物, 大大提高了免疫分析的简便性. 以日本血吸虫抗体为分析对象, 测得线性范围为1～1500 ng/mL, 抗体检出限为1.3 ng/mL, 相对标准偏差为3.6% (n＝10), 结果令人满意.     

穿心莲内酯硫酸酯化反应体系中四个新的衍生物的分离与表征

通过色谱方法, 从复杂的穿心莲内酯硫酸酯化反应体系中分离获得4个新的穿心莲内酯衍生物, 应用谱学方法进行了表征. 主要利用1H NMR, 13C NMR, DEPT, 1H-1H COSY, HSQC, HMBC及NOSEY等1D和2D NMR技术, 并通过与母体化合物NMR数据的对比分析, 鉴定这4个化合物分别为3,19-二羟基-8,11,13-赖百当三烯-15,16-内酯(1), 3-羟基-8,11,13-赖百当三烯-15,16-内酯-19-硫酸酯(2), 8,11,13-赖百当三烯-15,16-内酯-3,19-二硫酸酯(3), 3-羟基- 8(R)-12(S)-8(12)-环氧-13-赖百当烯-15,16-内酯-19-硫酸酯(4).     

Two-photon spectroscopic behaviors and photodynamic effect on the BEL-7402 cancer cells of the new chlorophyll photosensitizer

The spectroscopic properties of a new chlorophyll derivate photosensitizer(CDP) are studied under the excitation wavelengths at 800 and 400 nm using femtosecond pulses from a Ti:sapphire laser.The damaging effect of CDP on the BEL-7402 cancer cells is also investigated upon two-photon illumination at 800 nm.The normalized fluorescence spectra of CDP in tetrahydrofuran(THF) show that two-photon and one-photon spectra have the same distributions and the same emission bands(675 nm).The life-times of two-and one-photon induced fluorescence of this molecule are of the order of 5.0 ns.By comparing the data it is shown that there is some difference between the two lifetimes,but the differ-ence is less than one nanosecond.The two-photon absorption cross section of the molecule is also measured at 800 nm and estimated as about σ′2 ≈ 31.5×10-50 cm4·s·photon-1.The results of two-photon photodynamic therapy(TPPDT) tests show that CDP can kill all of the tested cancer cells according to the usual Eosine assessment.Our results indicate that the two-photon-induced photophysical,photo-chemical and photosensitizing processes of CDP may be basically similar to those of one-photon ex-citation.These behaviors of the sample suggest that one may find other possible methods to estimate some photosensitizers' effects in details such as their distribution in cells and the reactive targets of the sub-cellular parts of some tumor cells via two-photon excitation techniques.     

Synthesis of fluorinated hyperbranched polymers capable as highly hydrophobic and oleophobic coating materials

A series of coating materials were prepared from two classes of hyperbranched polymers containing short fluorocarbon chains (HPEFs/HPUFs). The obtained hyperbranched polymers were characterized by FT-IR, ¹H NMR, ¹³C NMR, ¹⁹F NMR, GPC and TG analyses. HPEFs/HPUFs exhibited very low surface free energies (13.67-24.49 mJ/m²) which almost are independent of their internal backbone but dependent on the terminal fluorocarbon chains. Highly hydrophobic and/or oleophobic surfaces of cotton woven fabric can be achieved from these polymers by solution-immersion coating method. The static and dynamic wettabilities of the HPEFs/HPUFs treated fabrics have been investigated. The static contact angles reached to 146°, 122° and 102° for water, hexadecane and decane, respectively. The lowest contact angle hysteresis reached to 5.9°.     

小型高分辨电子轰击离子源反射式飞行时间质谱仪的研制

常用的气体分析质谱仪使用四极杆质谱作为分析器,分辨率一般低于300,无法解决同质量数离子带来的干扰问题.本实验自行研制了一种小型高分辨气体分析质谱仪,它采用电子轰击离子源反射式飞行时间质量分析器.仪器腔体总长45 cm,在m/z 28的位置,质量分辨率达到3000(Full width at half maximum,FWHM),实现了CO和N2的半峰谷分离;在m/z 69的位置,仪器分辨率达到5000(FWHM).在直接大气压进样条件下,可以检测到空气中136Xe(含量7.8 μ g/m3)和80Kr(含量2.8 μg/m3).使用ADC采集时,仪器的动态范围为1 06.该仪器将作为高端气体质谱仪,应用于过程监测在线分析、环境有机挥发物研究、热分析质谱及催化反应监测等领域.     

Crystal structures and thermal decomposition kinetics of lanthanide complexes with 3,4,5-trimethoxybenzoic acid and 1,10-phenanthroline

A series of lanthanide complexes with the 3,4,5-trimethoxybenzoic acid(3,4,5-tmoba) and 1,10-phenanthroline(phen),[Ln(3,4,5-tmoba) 3 phen] 2(Ln = Pr(1),Nd(2) and Ho(3)),have been synthesized and characterized by a series of techniques including elemental analysis,IR spectra,X-ray crystallography and TG/DSC-FTIR technology.The three complexes have two kinds of coordination modes,in which the Pr 3+ and Nd 3+ cations are nine-coordinated and the Ho 3+ cation is eight-coordinated.The three-dimensional IR accumulation spectra of gaseous products for complexes 1-3 were analyzed and the gaseous products were identified by the typical IR spectra obtained from the 3D surface graphs.Meanwhile,we obtained the activation energy E of the first steps of complexes 1-3 by the integral isoconversional non-linear(NL-INT) method and discussed the non-isothermal kinetics of complexes 1-3 using the Malek method.Finally,SB(m,n) was defined as the kinetic method of the first-step thermal decomposition.The thermodynamic parameters △G≠,△H≠ and △S≠ of activation at the peak temperature were also calculated.     

硅胶基质高效液相色谱填料研究进展

高效液相色谱(HPLC)不仅是一种有效的分析分离手段,也是一种重要的高效制备分离技术。色谱柱是HPLC系统的核心,不同性能的填料是HPLC广泛应用的基础。硅胶是开发最早、研究最为深入、应用最为广泛的HPLC固定相基质,其制备方法主要有喷雾干燥法、溶胶-凝胶法、聚合诱导胶体凝聚法及模板法等。近年来,亚2μm小粒径硅胶、核-壳型硅胶、双孔径硅胶、介孔性硅胶、有机杂化硅胶等新型硅胶应用于HPLC并取得了色谱分离技术的飞速发展,例如基于亚2μm填料的超高压液相色谱技术、基于核-壳型填料的快速分离技术、基于杂化硅胶填料的高温液相色谱技术等。硅胶经表面化学键合、聚合物包覆等有机改性可制得先进的大分子限进填料、温敏性填料、手性填料等,大大扩展了HPLC的应用范围。本文对液相色谱用硅胶的制备方法、改性与修饰方法以及硅胶基质固定相的评价方法加以系统综述,概述了新型硅胶在HPLC中的应用进展,并对硅胶基质填料的发展方向与应用前景进行了展望。     

LaGaO3基固体氧化物燃料电池阳极材料Ce1-xTmxO2-δ（Tm=Cu,Mn,Fe）研究

以研究与Sr,Mg掺杂LaGaO3(LSGM)电解质匹配的阳极材料为出发点,系统研究了Ce1-xTmxO2-δ(Tm=Cu,Mn,Fe)固溶体的晶体结构、热化学稳定性、电化学性能和单电池发电实验。柠檬酸法合成的Ce1-xTmxO2-δ化合物在x<0.2时均为单相材料,与LSGM电解质有良好的热化学相容性。采用交流阻抗法研究了阳极材料的电化学性能,金属元素掺杂可以显著地改善CeO2电化学性能,Fe元素掺杂阳极材料极化电阻最小,随着元素掺杂量的增加以及氢气增湿,极化电阻减小。采用电解质支撑结构单电池进行发电实验,在800℃时,以Ce0.8Fe0.2O2-δ作为阳极的单电池最高功率密度可达98 mW.cm-2,表明该材料作为IT-SOFC的阳极材料具有一定的可行性,有望成为适合LSGM电解质的阳极材料。     

Mg-Ni-Nd非晶电极合金充放电过程中的组织结构变化及对其放电容量的影响

采用熔体快淬法制备了(Mg70.6 Ni29.4)90Nd10的非晶贮氢合金带,用X射线衍射仪和高分辨电镜对该合金在充放电循环过程中的组织结构演变进行了动态跟踪.结果表明:(Mg70.6Ni29.4)90Nd10贮氢合金在充放电循环过程中由非晶态慢慢晶化为纳米晶,初生相NdMg2 Ni9在循环过程中逐渐转化为Mg2 Ni,α-Mg和Nd2H5相.电化学性能测试表明,由于微观结构的变化对其放电容量的影响过程分为3个阶段:首先是前两个循环的活化过程,在第3个循环达到放电容量最高值(580.5 mAh·g-1);接下来是放电容量显著降低的4～10个循环阶段;最后是放电容量保持稳定的11 ～20个循环.研究发现NdMg2 Ni9相的存在和保持合金的非晶结构是提高镁基电极合金循环稳定性的重要因素.     

碳纳米管表面修饰程度对其载Pd纳米粒子的电催化氧化水合肼性能的影响

比较了未氧化处理与经浓硝酸或混酸(浓硫酸与浓硝酸体积比为1∶1)处理后的不同多壁碳纳米管(MWNTs)为载体的Pd催化剂(Pd/MWNTs)对水合肼氧化的电催化性能. 光谱表征和电化学测试结果表明, MWNTs表面不修饰或修饰程度过大都不利于金属Pd纳米粒子的沉积. 浓硝酸处理使MWNTs表面修饰的含氧基团适中, 能够促进负载的Pd纳米粒子均一分布, 因此提高Pd/MWNTs催化剂对水合肼的电催化性能. 相反, 混酸处理使MWNTs表面产生的含氧基团过多, 导致金属Pd纳米粒子部分聚集, 从而降低Pd/MWNTs催化剂对水合肼的电催化性能.