基于蛋壳膜固定酶和纳米银膜光度法对葡萄糖的检测

利用蛋壳膜固定酶和静电作用组装纳米银膜,建立了一种新型的光度法检测微量葡萄糖.采用共价交联法在蛋壳膜上固定葡萄糖氧化酶.酶促反应产生的H_2O_2氧化纳米银导致纳米银膜吸光度减小,日光强度的变化值与葡萄糖浓度有关,据此实现了对葡萄糖的检测.该方法检测快速,线性范围为6.0×10~(-5)～66.0×10~(-5)mol/L(r=0.999 7,n=11),检出限(S/N=3)为1.8×10~(-5) mol/L.方法成功用于临床血清样品中葡萄糖含量的检测.     

聚合物对还原法合成Pt纳米粒子过程的影响

用H_2还原K_2PtCl_4溶液的方法在常温下合成了Pt纳米粒子，考察了poly(N- isopropylacrylamide)(PNIPA), poly(N-vinylacetamide)(PNVA)和poly (vinylalcohol)(PVA)等三种可溶于水的聚合物对Pt纳米粒子大小和溶胶稳定性的 影响。TEM和溶胶中加入KCl电解质溶液后溶胶稳定性测定结果表明，以PNIPA为稳 定剂可获得粒径最小的Pt粒子，且溶胶最为稳定。较高的PNIPA/Pt~(2+)摩尔比对 合成小颗粒的Pt纳米粒子有利，而聚合物的分子量对粒子影响不大。Pt晶粒在H_2 气氛下生长过程较为缓慢，停止通入还原气体H_26h后，晶粒生长才基本完成，但 溶胶在6个月后仍保持良好的稳定性。     

Ultrasound-responsive Homopolymer Nanoparticles

Nonin vasive ultraso und is a more effective strategy for on-demand drug delivery of polymeric nano particles than many other stimuli.However,the preparation of ultrasound-responsive homopolymer nanoparticles is still very challenging.In this study,we disclose the regulating factors of ultrasound responsiveness of homopolymer nanoparticles and the disaggregation behavior of homopolymer nanoparticle aggregates.Homopolymer nanoparticles such as vesicles and large compound micelles(LCMs)are self-assembled from poly(methoxyethyl methacrylate)(PMEMA)and poly(amic acid)(PAA),respectively.The ultrasound responsiveness of PAA vesicles at metastable state could be regulated by tuning the self-assembly temperature(7^),and was optimized when Ts is around the glass transition temperature(7g)of PAA.However,the PMEMA LCMs did not respond to ultrasound as they are at stable state.On the other hand,poly(2-(2-ethoxyethoxy)ethyl acrylate)(PEEA)could self-assemble into vesicle aggregates or complex micelle aggregates,which were dissociated upon sonication.Overall,the above findings provide us with a fresh in sight for designing ultrasound-responsive polymeric nanoparticles.     

以聚电解质多层膜为纳米反应器制备Au@Pt核壳纳米粒子

以聚二烯丙基二甲基氯化铵和聚苯乙烯磺酸钠为构筑单元,通过静电层层自组装制备了多层膜,利用薄膜中存在的抗衡阴离子,选择AuCl-4和PtCl2-6作为Au和Pt的前驱体,通过连续的阴离子交换/还原,原位制备了Au-Pt双金属纳米粒子。 紫外-可见分光光度法、透射电子显微镜和能量色散X射线能谱数据表明,在聚电解质多层薄膜中成功地制备了具有核壳结构的Au@Pt双金属纳米粒子。 这种纳米粒子在电化学催化、燃料电池方面具有潜在的应用价值。     

Dendronized scorpionate complexes of molybdenum in low and high oxidation states

Tridentate (L(3)) and bidentate (L(2)) poly(pyrazolyl)methane ligands (Gn-dend)OCH(2)C(pz)(3) (1-4) and (Gn-dend)CH(3,5-Me(2)pz)(2) (pz = pyrazol-1-yl) have been used to synthesize the molybdenum(0) complexes [Mo(CO)(3)(L(3))] (G0-G3, 5-8), [Mo(CO)(4)(L(2))] (G0-G1, 13-14), and [Mo(CO)(3)(NCMe)(L(2))] (G0, 15), and the molybdenum(VI) complexes [MoCl(2)O(2)(L(2))] (9-12). The G0-G3 prefixes represent the generation of poly(aryl ether) dendrons in which the metal complexes are embedded. The molecular structures of compounds 13 and 15 have been determined by X-ray diffraction studies and the hydrodynamic radii of tricarbonyl complexes 5-8 calculated by diffusion-ordered NMR spectroscopy (DOSY). Molybdenum(VI) compounds 9-12 have also been evaluated as catalysts for olefin epoxidation, showing comparable but inferior performances than ligand-free MoCl(2)O(2), probably because of the labile coordination of L(2).     

3-甲基噻吩和3-氯噻吩的电化学共聚

3-甲基噻吩和3-氯噻吩首次三氟化硼乙醚溶液中实现了电化学共聚。共聚物的分子结构通过电化学分析、红外和拉曼光谱得到了证实。实验结果表明：单体投料比对共聚物的结构和电化学性质有很大的影响;共聚物比3-甲基噻吩和3-氯噻吩的均聚物具有更大的充放电电容和更可逆的氧化还原性质。     

聚乳酸接枝改性纳米生物玻璃/PLGA复合材料的制备、表面性质及生物活性

以丙交酯开环聚合原位接枝改性的纳米生物玻璃(PLLA-g-BG)与聚丙交酯-乙交酯(PLGA)复合材料为研究对象, 采用TGA, ESEM和EDX分析其接枝率, 粒子分散性和表面元素分布, 通过将兔成骨细胞种植于材料膜表面进行体外培养, 采用荧光染色法、NIH Image J图像分析软件、MTT法和流式细胞术等手段检测细胞在材料表面的平均黏附数量、扩展面积比、增殖能力和细胞周期的变化, 综合评价新型改性纳米复合材料的生物相容性和生物活性. 结果表明, 聚乳酸表面接枝改性可明显改善纳米生物玻璃粒子的团聚; PLGA中掺入一定比例的改性PLLA-g-BG可明显促进兔成骨细胞的黏附、扩展与增殖; 改性纳米生物玻璃的应用可提高生物可降解聚酯材料的生物相容性和生物活性.     

Persistent interactions between hydroxylated nanoballs and atactic poly(2-hydroxyethyl methacrylate)(PHEMA)

The incorporation of self-assembled nanoparticles, a.k.a. hydroxylated nanoballs, into poly(2-hydroxyethyl methacrylate)(PHEMA) gives rise to a cross-linked network/hydrogel with enhanced interfacial interaction, whereas its inclusion in poly(methyl methacrylate)(PMMA) results in plasticization.     

Morphology of gold nanoparticles synthesized by filamentous cyanobacteria from gold(I)-thiosulfate and gold(III)--chloride complexes

Plectonema boryanum UTEX 485, a filamentous cyanobacterium, has been reacted with aqueous Au(S(2)O(3))(2)(3)(-) and AuCl(4)(-) solutions ( approximately 400-550 mg/L Au) at 25-100 degrees C for up to 1 month and at 200 degrees C for 1 day. The interaction of cyanobacteria with aqueous Au(S(2)O(3))(2)(3)(-) promoted the precipitation of cubic (100) gold nanoparticles (<10-25 nm) at membrane vesicles and admixed with gold sulfide within cells and encrusted on the cyanobacteria, whereas reaction with AuCl(4)(-) resulted in the precipitation of octahedral (111) gold platelets ( approximately 1-10 microm) in solutions and nanoparticles of gold (<10 nm) within bacterial cells. Functional groups imaged by negative ion TOF-SIMS on (111) faces of the octahedral platelets were predominantly Cl and CN, with smaller amounts of C(2)H and CNO.     

Interaction of 2- and 4-mercaptopyridine with pentacyanoferrates and gold nanoparticles

2-Mercapto- and 4-mercaptopyridine (2- and 4MPy) react with the [Fe(CN)(5)(H(2)O)](3-) complex, forming the S-coordinated [Fe(CN)(5)(2MPy)](3-) and the N-coordinated [Fe(CN)(5)(4MPy)](3-) complexes. The rates of formation and dissociation of the [Fe(II)(CN)(5)(2MPy)](3-) complex were determined as k(f) = 294 dm(3) mol(-1) s(-1) and k(d) = 0.019 s(-1) by means of stopped-flow technique. The equilibrium constants for the iron(II) and -(III) species were calculated as K(f)(II) = 1.5 x 10(4) mol(-1) dm(3) and K(f)(III) = 1.3 x 10(6) mol(-1) dm(3), in comparison with 2.6 x 10(5) and 3.4 x 10(4) mol(-1) dm(3), respectively, for the 4MPy isomer. In the presence of gold nanoparticles, both 2- and 4MPy can displace the stabilizing citrate species, leading to substantial aggregation in aqueous solution, as deduced from the surface-enhanced Raman spectroscopy effect and from the decay of the 520-nm plasmon band accompanied by the rise of the characteristic exciton band at 650 nm. The [Fe(CN)(5)(4MPy)](3-) complex promotes strong stabilization of the gold nanoparticles by interacting through the S atom. On the other hand, the labile [Fe(CN)(5)(2MPy)](3-) complex induces aggregation, delivering the 2MPy ligand to the gold nanoparticles.     

共同装载吴茱萸碱和Fe3O4纳米粒子的磁性药物载体的制备

以单甲醚-聚乙二醇-聚（丙交酯-乙交酯）（mPEG-PLGA）作为载体,采用溶液透析的方法共同装载抗癌药物吴茱萸碱和Fe₃O₄ 磁性纳米粒子. 通过透射电子显微镜、红外光谱、紫外-可见光谱及体外释放实验、普鲁士蓝染色、体外毒性实验和磁靶向研究,综合评价了磁性纳米药物载体的性能. 结果表明,磁性药物载体胶束分散性良好,粒径均一,有较高的载药量和包封率,能够实现药物缓释,具有磁靶向特性.     

以聚合物乳胶为模板经表面引发原子转移自由基聚合制备空心二氧化硅纳米微球

均匀的空心纳米及微米球因具有可裁剪结构及良好的光学性能和表面性能,而具有非常广泛的应用前景,空心胶囊是一类重要的材料,它是通过不同的化学和物理方法,直接除去壳-核粒子的内核而获得的,目前主要是通过控制表面沉积。或利用静电相互作用层层组装。制备空心胶囊,但前者易于产生独立的无机粒子沉淀,后者的步骤太过繁琐。     

非共价键自组装制备聚对苯撑乙炔/聚丙烯酸水溶性荧光纳米粒子及其光物理行为研究

通过功能化聚对苯撑乙炔(含羟基与氨基)和聚丙烯酸之间的非共价键自组装制备了一系列含共轭聚合物的水溶性荧光纳米粒子, 并进行了相关结构和光学性质表征. 研究表明, 纳米粒子的大小和聚丙烯酸/聚对苯撑乙炔质量比直接相关. 光物理性质研究表明, 形成水溶性纳米粒子后, 疏水的聚苯撑乙炔链在纳米粒子中易于形成π-链间聚集, 其光物理性质与其在薄膜态时相似.     

Probing the electronic structure and chemical bonding of the "staple" motifs of thiolate gold nanoparticles: Au(SCH3)2- and Au2(SCH3)3-

Thiolate-protected gold nanoparticles have been found recently to be coordinated by the so-called "staple" bonding motifs, consisting of quasi-linear [RS-Au-SR] and V-shaped [RS-Au-(SR)-Au-SR] units, which carry a negative charge formally. Using photoelectron spectroscopy (PES) in conjunction with ab initio calculations, we have investigated the electronic structure and chemical bonding of the simplest staples with R = CH(3): Au(SCH(3))(2)(-) and Au(2)(SCH(3))(3)(-), which were produced by electrospray ionization. PES data of the two Au-thiolate complexes are obtained both at room temperature (RT) and 20 K. The temperature-dependent study reveals significant spectral broadening at RT, in agreement with theoretical predictions of multiple conformations due to the different orientations of the -SCH(3) groups. The Au-S bonds in Au(n)(SCH(3))(n+1)(-) (n = 1, 2) are shown to be covalent via a variety of chemical bonding analyses. The strong Au-thiolate bonding and the stability of the Au-thiolate complexes are consistent with their ubiquity as staples for gold nanoparticles and on gold surfaces.     

Stimuli responsive poly(1-[11-acryloylundecyl]-3-methyl-imidazolium bromide): dewetting and nanoparticle condensation phenomena

A stimuli-responsive homopolymer poly(ILBr) is fabricated via a "two-phase" atom transfer radical polymerization (ATRP) process, where ILBr stands for the reactive ionic liquid surfactant, 1-[11-acryloylundecyl]-3-methyl-imidazolium bromide. An extraordinarily wide molecular weight distribution (PDI = 6.0) was obtained by introducing the initiator (4-bromomethyl methyl benzoate) in a heterogeneous two-phase process. The molecular weight distribution of poly(ILBr) was characterized by size-exclusion chromatography (SEC). The resulting homopolymer was found to be surface active and stimuli responsive. Poly(ILBr) films coated on quartz exhibit stimuli-responsive dewetting after ion exchange of Br(-) by PF(6)(-). This dewetting phenomenon can be understood in chain segmental terms as a stimuli-induced structural relaxation and appears to be the first such reported stimuli-responsive polymeric dewetting. Titrating aqueous poly(ILBr) with aqueous bis(2-ethylhexyl)sulfosuccinate induces nanophase separation and results in the condensation of nanoparticles 30-60 nm in diameter.     

Facile synthesis of metal-organic framework films via in situ seeding of nanoparticles

A facile in situ nanoparticle seeding method is reported to prepare MIL-101(Cr) films on alumina supports. The in situ seeding of MIL-101(Cr) nanoparticles was promoted by use of dimethylacetamide (DMA). The generality of this approach is further demonstrated for Cu(3)(btc)(2) films by using a (poly)acrylate promoter.     

Pt nanoparticles@photoactive metal-organic frameworks: efficient hydrogen evolution via synergistic photoexcitation and electron injection

Pt nanoparticles of 2-3 nm and 5-6 nm in diameter were loaded into stable, porous, and phosphorescent metal-organic frameworks (MOFs 1 and 2) built from [Ir(ppy)(2)(bpy)](+)-derived dicarboxylate ligands (L(1) and L(2)) and Zr(6)(μ(3)-O)(4)(μ(3)-OH)(4)(carboxylate)(12) secondary building units, via MOF-mediated photoreduction of K(2)PtCl(4). The resulting Pt@MOF assemblies serve as effective photocatalysts for hydrogen evolution by synergistic photoexcitation of the MOF frameworks and electron injection into the Pt nanoparticles. Pt@2 gave a turnover number of 7000, approximately five times the value afforded by the homogeneous control, and could be readily recycled and reused.     

Electrochemical and photophysical properties of DNA metallo-intercalators containing the ruthenium(II) tris(1-pyrazolyl)methane unit

Three new ruthenium(II) complexes containing the tris(1-pyrazolyl)methane (tpm) ligand have been prepared: [Ru(tpm)(L)(dppn)]n+ (where n = 1; L = Cl (5), n = 2; L = MeCN (6) and pyridine (7); dppn = benzo[i]dipyrido[3,2-a:2',3'-c]phenazine). Complex 6 was structurally characterized by single-crystal X-ray diffraction. Binding parameters of these complexes with calf thymus DNA are reported and compared to those obtained for a previously reported monocation, [RuCl(tpm)(dppz)]+. Binding studies with the dications and the synthetic oligonucleotides poly(dA).poly(dT) and poly(dG).poly(dC) have also been determined. Photophysical and electrochemical properties of 5-7 have been investigated and compared with their dipyridophenazine (dppz) analogues.     

Comparison between measurements of elasticity and free amino group content of ovalbumin microcapsule membranes: discrimination of the cross-linking degree

Gold nanoparticle-doped poly(2-vinylpyridine) (P2VP) microcapsules and foam films were synthesized and assembled at the P2VP chloroform solution/HAuCl(4) aqueous solution interface at 25 °C. It was found that Au nanoparticles with the average diameter of 2.1 nm were homogeneously embedded in and adsorbed on the walls of the capsules and foams, the nanoparticles were composed of Au(0) and Au(III) with the molar ratio of about 75/25, and the mass percent of Au elements was measured to be 19.65%. The formation of the nanostructures was attributed to the self-assembly of P2VP at the liquid/liquid interface, the simultaneous reduction of AuCl(4)(-) ions by a small amount of ethanol in the chloroform and adsorption of AuCl(4)(-) ions. After irradiated by UV-light for 1h, the average diameter of the nanoparticles was found to be 2.2 nm, and the AuCl(4)(-) ions were transformed to Au(0) completely. The catalytic performance of these composite nanostructures were evaluated by using the reduction of 4-nitrophenol (4-NP) by potassium borohydride in aqueous solutions. The catalytic activity was very high in the first cycle, decreased rapidly and slightly in the second and third cycles, respectively, due to the aggregation of some nanoparticles, and stabilized after the third cycle.     

Anion exchange induced tunable catalysis properties of an uncommon butterfly-like tetranuclear copper(II) cluster and magnetic characterization

An uncommon butterfly-like tetranuclear copper(ii) cluster with the formula {[Cu(4)(μ(3)-OH)(2)(μ(4)-Cl)(H(2)O)(2)(L)(2)]·Cl(H(2)O)(7)}(n) (1) (H(2)L = 1,2-bis[3-(1,2,4-triazolyl)-4-amino-5-carboxylmethylthio]ethane) has been synthesized. Compound 1 exhibits interesting anion exchange characteristics, in which both guest and coordinated Cl(-) can be replaced by I(-) or NO(3)(-) in water. Furthermore, a high catalytic selectivity to produce poly(phenylene ether) by the oxidative coupling of 2,6-dimethylphenol in water is found to be 74% for 1 and 87% for the anion-exchanged product 1-MI(x), respectively. Additionally, the antiferromagnetic interaction among Cu ions for compound 1 is also found.