LaF_3∶Yb~(3+),Er~(3+)纳米晶:溶剂热法合成及上转换发光性质

利用溶剂热合成方法,分别以油酸和油胺为表面有机配体,合成了具有六角结构,颗粒尺寸分别为19和23nm单分散的LaF3:Yb3+,Er3+纳米晶。在980nm红外激光照射下,LaF3:Yb3+,Er3+纳米晶发射出肉眼可观察的绿色和红色上转换荧光,而且其发光过程均符合双光子过程。结合红外光谱与上转换光谱分析了表面有机配体对LaF3:Yb3+,Er3+纳米晶上转换发光的影响,结果显示,以油酸分子为表面配体的纳米晶具有较高的上转换发射强度,但以油胺为表面配体的纳米晶的红光发射相对增强。     

β-Ga2O3∶Cr3+近红外长余辉纳米颗粒的制备及发光性能

以三乙二醇为表面配体, 利用沉淀法制备了β-Ga₂O₃∶Cr³⁺近红外(NIR)长余辉纳米颗粒. 考察了反应条件对β-Ga₂O₃∶Cr³⁺的发光性能和晶体结构的影响, 并初步探讨了其NIR余辉发光机理. 结果表明, 当溶液的pH值为7, 煅烧温度为700 ℃时, 可获得高纯度的β-Ga₂O₃∶Cr³⁺纳米颗粒, 其平均粒径为30 nm, 最大余辉发射波长可调控为750 nm, NIR余辉发光时间长于384 h. 本方法得到的β-Ga₂O₃∶Cr³⁺长余辉纳米颗粒不仅尺寸小, 而且NIR余辉时间长, 发射波长可调控, 在低背景噪音的深组织活体成像中具有潜在的应用前景.     

Cr,In共掺杂MgGa2O4小尺寸近红外长余辉纳米颗粒的制备及发光性能

采用乙二醇辅助共沉淀法制备了小尺寸Cr,In共掺杂MgGa₂O₄(MGO∶Cr, In)近红外长余辉发光纳米粒子(Persistent luminescence nanoparticles, PLNPs), 并考察了Cr, In共掺杂及煅烧温度对MGO晶体结构、 余辉发光性质和尺寸的影响. 结果表明, 最优Cr, In共掺杂浓度分别为0.3%和0.02%, MGO∶Cr, In晶体属于Fd3m空间群, Cr, In共掺杂对纳米颗粒的结构无影响, 平均粒径为(8.61±2.23) nm, 分散性良好, 最佳煅烧温度为700 ℃. 并且, In掺杂可有效延长其余辉发光寿命, 平均发光寿命(τ_av)从49.33 s增大至52.89 s; 荧光量子产率增高至44.9%; 活化能E_a为(0.36±0.04) eV, 具有良好的热稳定性; 陷阱深度为0.696 eV. 此外, 该PLNPs分别在260 nm、410 nm和600 nm处有激发峰, 表明UV光、 蓝绿光以及红光皆可实现对其的激发, 发射波长皆位于705 nm处, 属于Cr³⁺的²E(²G)→⁴A₂(⁴F)跃迁. 该PLNPs在红色LED灯、 光学储器件以及生物医学等领域具有巨大潜在应用价值.     

稀土上转换发光材料标记抗体的制备及在免疫组化中的应用

采用微波辐射法合成了具有上转换发光特性的六方相纳米粒子NaGdF₄: Yb³⁺,Er³⁺(UCNPs), 其晶粒大小约为65 nm, 且粒子在980 nm的激发光下显示绿光(550 nm). 进一步在NaGdF₄: Yb³⁺,Er³⁺纳米晶的表面包覆了一层二氧化硅层, 进行氨基功能化后获得了表面共价结合氨基基团的粒径为70 nm的上转换发光纳米微球NaGdF₄: Yb³⁺,Er³⁺@SiO₂-NH₂(UCNPs@SiO₂-NH₂). 通过共价键将UCNPs@SiO₂-NH₂与多克隆抗体免疫球蛋白联接, 将标记后的多克隆抗体应用于传统的免疫组化检测子宫内膜腺细胞中基质金属蛋白酶组织抑制剂-4(TIMP-4)蛋白的表达. 结果表明, 微波合成的稀土上转换发光纳米材料形貌规则且粒径均一, 包覆硅壳后材料具有良好的分散性和水溶性, 荧光强度高且稳定, 在980 nm激发光下对生物组织无背景荧光, 可以很好地检测组织中蛋白质的表达.     

纳米晶LaAlO3掺Eu3+的复合沉淀法制备及发光性质

以NH₃·H₂O-NH₄HCO₃混合溶液为复合沉淀剂,制备了LaAlO₃:Eu³⁺纳米晶体.通过X射线衍射、扫描电镜和透射电镜对产物进行了表征,用荧光光度计测试了样品的三维荧光光谱、激发光谱和发射光谱.结果表明:前驱沉淀物经800℃焙烧处理2h,制备出球型形貌,颗粒分散性好、尺寸约为40nm的立方相LaAlO₃纳米晶.由三维荧光光谱确定了LaAlO₃:Eu³⁺的最佳监测波长和激发波长,在395nm波长光的激发下观察到纳米LaAlO₃中Eu³⁺的591nm(⁵D₀-⁷F₁)和613nm(⁵D₀-⁷F₂)特征发射谱,磁偶极跃迁⁵D₀-⁷F₁的发射峰强度要比电偶极跃迁⁵D₀-⁷F₂更强,而且这种趋势随着焙烧温度的升高明显增强,说明由该法制备的纳米LaAlO₃中Eu³⁺离子占据的位置具有高的对称性.     

氟离子浓度对稀土掺杂上转换发光纳米材料形貌及荧光寿命的影响

利用溶剂热法制备了Yb³⁺、Er³⁺共掺的NaYF₄上转换发光纳米材料。实验结果表明,不同F^-离子对纳米晶的晶型和粒径尺寸起着重要的作用。低F^-离子浓度下,NaYF₄纳米材料的粒径尺寸随F^-离子浓度的增加逐渐变小且趋于均一;高F^-离子浓度下,六方晶相的形成受到抑制,上转换纳米晶出现团聚现象。在一定浓度范围内,F^-离子的浓度有利于促进荧光发射。同时F^-离子浓度对荧光寿命也有显著的影响。     

水热法合成AgGd0.9Eu0.1(WO4)2及其发光性能

利用水热法制备了不同形貌的AgGd_0.9Eu_0.1(WO₄)₂ 红色发光材料, 通过X射线衍射(XRD)、扫描电镜(SEM)、X射线能谱分析(EDS)、透射电镜(TEM)及荧光光谱(PL)对不同条件下制备样品的物相、形貌和荧光性质进行了表征, 探讨了初始溶液的pH值和表面活性剂的种类对产物形貌和颗粒尺寸的影响. 结果表明: 本文所述条件下所得样品均属于单斜晶系|初始溶液的pH值和表面活性剂的种类对产物的形貌起关键作用. 通过调整初始溶液的pH值和表面活性剂的种类, 可以得到不同粒径的球形、棒状和空心球形颗粒|AgGd_0.9Eu_0.1(WO₄)₂的发射光谱表现为Eu^3＋离子的特征发射, 样品颗粒的形貌以及颗粒尺寸对发射光谱的强度有一定影响.     

基于DNA电化学发光传感器研究金纳米颗粒对量子点的电化学发光影响

纳米金颗粒具有高的消光系数和良好的表面等离子体共振特性, 其等离子体共振特性受纳米金颗粒的尺寸和周围环境等因素的影响. 本文基于半导体纳米晶电化学发光信号对金纳米颗粒的距离依赖性制备了DNA电化学发光传感器. 首先利用循环伏安法(CV)在玻碳电极(GCE)表面原位沉积金纳米颗粒(AuNPs), 巯基丙酸包裹的CdS量子点(QDs)与氨基修饰的双链DNA (dsDNA)通过酰胺键缩合, 形成量子点修饰的双链DNA(QDs-dsDNA). 最后将QDs-dsDNA 通过dsDNA 另一端的巯基组装到纳米金表面, 得到CdS QDs-DNA/AuNPs/GCE电化学发光传感器. 在优化电极表面QDs-dsDNA密度、金纳米颗粒沉积方法等实验条件的基础上, 对不同传感器的表面性质进行了表征, 如形貌和电化学阻抗等. 进一步通过控制纳米金和CdS QDs之间的DNA研究了纳米金对CdS QDs发光信号的影响作用. 结果显示DNA链的长度和类型对发光信号有着重要的影响. 最后将此传感器用于环境污染物的DNA损伤检测, 显示出很好的灵敏响应.     

脂质体封端CsPbX3(X=Cl,Br,I)纳米晶体的制备及在发光二极管中的应用

以脂质体充当表面封端配体修饰合成后的CsPbX₃纳米晶体.封端CsPbX₃纳米晶能保持原始形状和粒径大小,相对量子产率提升至（100±3）%,发射光谱在411~626 nm范围内可调.将其存储于空气（温度25℃,相对湿度50%）中150 d仍保持立方晶型.以DOPC-CsPbBr₃为颜色转换器可制造显色指数高达91.2的白色发光二极管,应用前景广阔.     

β-Ga_2O_3∶Cr~(3+)近红外长余辉纳米颗粒的制备及发光性能

以三乙二醇为表面配体,利用沉淀法制备了β-Ga_2O_3∶Cr~(3+)近红外(NIR)长余辉纳米颗粒.考察了反应条件对β-Ga_2O_3∶Cr~(3+)的发光性能和晶体结构的影响,并初步探讨了其NIR余辉发光机理.结果表明,当溶液的p H值为7,煅烧温度为700℃时,可获得高纯度的β-Ga_2O_3∶Cr~(3+)纳米颗粒,其平均粒径为30 nm,最大余辉发射波长可调控为750 nm,NIR余辉发光时间长于384 h.本方法得到的β-Ga_2O_3∶Cr~(3+)长余辉纳米颗粒不仅尺寸小,而且NIR余辉时间长,发射波长可调控,在低背景噪音的深组织活体成像中具有潜在的应用前景.     

多环芳二酐型聚酯亚胺膜的透气性能

多环芳二酐型聚酯亚胺膜的透气性能李悦生，丁孟贤，徐纪平（浙江大学高分子科学与工程研究所，杭州，３１００２７）（中国科学院长春应用化学研究所）关键词聚醚酰亚胺，聚酯酰亚胺，膜，透气性通常的聚酰亚胺加工性能较差，在芳环二酐的苯环间引入醚键等柔性基团后，其...     

Determination and study on residue and dissipation of benazolin-ethyl and quizalofop-p-ethyl in rape and soil

A QuEChERS (quick, easy, cheap, effective, rugged, and safe) method for the determination of benazolin-ethyl and quizalofop-p-ethyl in rape and soil by high-performance liquid chromatography-tandem mass spectrometry has been developed in this study. The residue and dissipation of benazolin-ethyl and quizalofop-p-ethyl in rape and soil were determined with the developed method. The half-lives of benazolin-ethyl in rape straw and soil were 3.7–5.1 days and 14.3–26.3 days, respectively. The half-lives of quizalofop-p-ethyl in rape straw and soil were 5.0-6.1 days and 0.3–9.7 days, respectively. The residue of benazolin-ethyl and quizalofop-p-ethyl in rapeseed and soil were below the detection limit (i.e., 0.5?mg?kg^?1, the maximum residue level of European Union for quizalofop-p-ethyl).     

微量元素与疾病诊断治疗的研究现状及展望

对国内外微量元素与疾病的关系及其诊断治疗的研究现状及研究动向进行了综述，包括：微量元素与地方病、癌肿、心血管病、糖尿病、眼病、神经系统病等。参考文献72篇。     

Conformations and steric and stacking interactions of trisubstituted ureas and thioureas with alkyl and phenyl groups

The monomeric ν(N—H) vibrations of various trisubstituted ureas of the R₂UPh type and -thioureas of the R₂TUPh type have been studied. The trans—out isomerism in the former and the trans—out—cis isomerism in the latter are discussed from the point of view of steric effect. The monomeric ν(N—H) vibrations of RPhUPh and RPhTUPh are also examined. The single band appearing in the spectrum of both ureas is characteristic of the cis form; this suggests the existence of phenyl—phenyl interaction (the stacking interaction proposed by Galabov et al. [10]). Behavior of ν(N—H) vibrations at several concentrations is shown to be clearly different in the three forms (trans, out and cis). The presence of the cis form is confirmed by solvent effect experiments.     

Ti-V基储氢合金及其氢化物的物相结构与组分优化设计

Ti-V基储氢合金在室温、常压下即可表现出良好的储氢特性,且质量储氢容量明显高于传统AB₅型储氢合金,从而在氢气的精制和回收、运输和储存及热泵等方面有较早的应用。 此外,在混合气体分离、核反应堆中处理氢的同位素、镍氢电池及燃料电池负极材料等方面也得到了广泛的研究与关注。 基于目前Ti-V基储氢合金的研究现状,概述了该类合金的优势、限制性因素(包括成因)及改性手段。 此外,为了进一步理解Ti-V基合金储氢机理、构建合金组分与储氢特性之间的对应关系,本工作重点围绕Ti-V基储氢合金及其氢化物的结构、组分优化设计展开综述,并对其未来研究方向做出展望。     

Ferrocene and ferrocenium modified clays and their styrene and EVA composites

In this work, ferrocene- and ferrocenium-containing salts were employed to modify montmorillonite. X-ray measurements show an increase in the interlayer spacing upon clay modification, which means that the larger and more organophilic cations were inserted into the gallery space of montmorillonite. Attempts to prepare nanocomposites of polystyrene and ethylene vinyl acetate copolymers lead to immiscible systems; the morphology of these systems was elucidated with TEM, XRD and cone calorimetry. The thermal stability of the composites is greater than that of the virgin polymer.     

钒与糖代谢及糖尿病

微量元素钒作为生物体内必需元素，经证实有很重要的生理学功能，与机体糖代谢有十分密切的关系，且能降低糖尿病动物模型的高血糖，极有可能被开发为治疗糖尿病的药物。     

Synthesis and Optical and Redox Properties of Symmetric and Asymmetric BODIPYs

Herein, we present the synthetic route and the photophysical, electrochemical as well as laser properties of novel red‐emitting boron‐dipyrromethenes (BODIPYs) bearing arylethyne moieties. Such functionality is added along the main axis of the chromophore leading to single‐ and double‐substituted derivatives. The relationship between the dye structure and the lasing properties is studied in detail with the help of the photophysical and electrochemical properties as well as quantum mechanical simulations. The asymmetric substitution of the parent dye induces inhomogeneities in the charge distribution, which leads to an overall loss of the fluorescence capacity, mainly in polar media. Such non‐radiative deactivation processes can be softened by decreasing the electron‐donor ability of the substituent or even avoided by symmetrical substitution. Thus, grafting of the arylethyne moieties at the longitudinal axis of the indacene core results in an effective strategy to develop red‐edge BODIPYs with highly efficient and photostable laser emission.     

Synthesis of Tyrosol and Hydroxytyrosol Glycofuranosides and Their Biochemical and Biological Activities in Cell-Free and Cellular Assays

Tyrosol (T) and hydroxytyrosol (HOT) and their glycosides are promising candidates for applications in functional food products or in complementary therapy. A series of phenylethanoid glycofuranosides (PEGFs) were synthesized to compare some of their biochemical and biological activities with T and HOT. The optimization of glycosylation promoted by environmentally benign basic zinc carbonate was performed to prepare HOT α-L-arabino-, β-D-apio-, and β-D-ribofuranosides. T and HOT β-D-fructofuranosides, prepared by enzymatic transfructosylation of T and HOT, were also included in the comparative study. The antioxidant capacity and DNA-protective potential of T, HOT, and PEGFs on plasmid DNA were determined using cell-free assays. The DNA-damaging potential of the studied compounds for human hepatoma HepG2 cells and their DNA-protective potential on HepG2 cells against hydrogen peroxide were evaluated using the comet assay. Experiments revealed a spectrum of different activities of the studied compounds. HOT and HOT β-D-fructofuranoside appear to be the best-performing scavengers and protectants of plasmid DNA and HepG2 cells. T and T β-D-fructofuranoside display almost zero or low scavenging/antioxidant activity and protective effects on plasmid DNA or HepG2 cells. The results imply that especially HOT β-D-fructofuranoside and β-D-apiofuranoside could be considered as prospective molecules for the subsequent design of supplements with potential in food and health protection.