Synthesis, properties, and optical applications of noble metal nanoparticle-biomolecule conjugates

Noble metal nanoparticles, such as gold or silver nanoparticles and nanorods, exhibit unique photonic, electronic and catalytic properties. Functionalization of noble metal nanoparticles with biomolecules (e.g., protein and DNA) produces systems that possess numerous applications in catalysis, delivery, therapy, imaging, sensing, constructing nanostructures and controlling the structure of biomolecules. In this paper, the recent development of noble metal nanoparticle-biomolecule conjugates is reviewed from the following three aspects: (1) synthesis of noble metal nanoparticle-biomolecule systems by electrostatic adsorption, direct chemisorption of thiol derivatives, covalent binding through bifunctional linkers and specific affinity interactions; (2) the photonic properties and bioactivation of noble metal nanoparticle-biomolecule conjugates; and (3) the optical applications of such systems in biosensors, and medical imaging, diagnosis, and therapy. The conjugation of Au and Ag nanoparticles with biomolecules and the most recent optical applications of the resulting systems have been focused on.     

贵金属纳米粒子的制备、结构和应用

贵金属纳米粒子因其特有的光学以及化学和催化性能，正引起科技界越来越浓厚的兴趣。通常这些特性决定于这些金属粒子的粒径和形态。由于非球形粒子比各向同性的球形粒子具有更优越的性能，它们已经成为研究的焦点，人们正在努力寻找粒子形状如何影响粒子理化性能的答案。贵金属纳米粒子的形状可控合成技术已经取得了明显进展。本文就贵金属纳米粒子的形状可控合成及其应用研究的当前进展进行综合评述。     

生物法合成纳米金的研究进展

纳米金以它独特的光学、电学和催化性质受到人们越来越多的关注.目前,生物合成的纳米金具有经济、无毒、环境友好等特点而成为研究热点.综述了利用细菌、真菌、放线菌、酵母菌以及各种植物材料合成纳米金的方法,并将各种方法进行了比较,讨论了每种方法的特点、尺寸和形貌的控制以及合成机理.最后,展望了生物合成纳米金的应用以及未来的发展方向.     

Surface modifications of Pt-based atomically ordered nanoparticles to improve catalytic performances for oxygen reduction reaction

Bimetallic platinum-cobalt (Pt–Co) nanostructure catalysts represent superior catalytic performances for oxygen reduction reaction (ORR). In a variety of Pt–Co catalyst structures, atomically ordered structure catalysts show excellent catalytic performances in the ORR. In this work, for promoting their catalytic performances, atomically ordered PtCo nanoparticles (PtCo/C) with carbon supported were successfully prepared by an improved impregnation method and annealing. Then, the ordered PtCo/C catalysts have been significantly improved by doped with ultralow amount of Au and Cr transition metal. The physical and electrochemical test results demonstrate the Cr–PtCo/C and Au–PtCo/C catalysts have superior catalytic performances including mass activity and stability compared to commercialized Johnson Matthey (JM) Pt/C, which was the result of the modified electronic properties of Pt surface and atomically ordered structure. The presence of Au and Cr enhances the stability of PtCo/C catalysts. This work represents a simple way to promote the catalytic performances of the atomically ordered catalysts.     

金属-染料包覆共掺杂复合物的制备与热学特性

提出了一种基于包覆共掺杂结构金属纳米粒子偶氮染料复合物(MNPADC) 合成的新方法,可使偶氮染料甲基橙定向吸附于球形金属银纳米粒子表面形成染料对纳米粒子的包覆结构,再将具有该结构的掺杂剂掺于聚合物基质聚乙烯醇中,制备出MNPADC复合材料薄膜.紫外可见吸收光谱表明,该材料在波长为400~450 nm的波段具有良好的光吸收特性.热质量分析发现,其热学特性更适合于光存储的要求.实验结果表明,该材料的设计方法为改善有机光存储介质材料的热学性能提供了简便而有效的途径.     

甲烷催化燃烧催化剂的研究进展

甲烷催化燃烧的目的是通过催化作用降低其起燃温度(T_(10))和完全转化温度(T_(90)),加深其氧化程度,从而提高燃料的利用率。简述了甲烷催化燃烧反应的机理,从种类、制备方法以及催化性能等方面详细介绍了甲烷催化燃烧催化剂的最新进展。贵金属催化剂的催化性能优越,但高成本以及热稳定性差等因素极大地限制了其应用;非贵金属催化剂尤其是复合金属氧化物催化剂(例如钙钛矿型复合金属氧化物催化剂和六铝酸盐系列催化剂等)拥有较高的催化活性,因其成本低,有更好的发展前景。提高非贵金属催化剂的低温催化活性和高温热稳定性是今后甲烷催化燃烧催化剂的主要研究方向。     

CeO2/CNTs纳米复合粒子的制备及其催化性能

 采用液相化学沉积法制备CeO2/CNTs纳米复合粒子,考查了表面活性剂对产物形貌的影响,采用TEM、XRD、FT-IR等手段对产物的形貌和晶相结构进行表征。结果表明,在一定条件下,表面活性剂的“桥接”作用有效地改善了活性组分的负载,以十二烷基苯磺酸钠为表面活性剂,以自制碳纳米管（CNTs）为载体,可以制备出负载均匀的CeO2/CNTs纳米复合粒子。探讨了活性组分CeO2在CNTs表面的负载机制,并在此基础上研究了所得样品在风化煤硝酸氧解制备腐植酸中的催化性能。催化结果表明,CeO2/CNTs纳米复合粒子的催化性能明显优于单纯的CeO2和CNTs的催化性能,能显著提高腐植酸的产率。     

Synthesis, characterization and antibacterial activity of copper, nickel and bimetallic Cu– Ni nanoparticles for potential use in dental materials

The antibacterial effect is a desirable property in dental materials.Development of simple methods for the preparation of nanosized metal particles has attracted significant attention because of their future applications due to unusual size-dependent antibacterial properties.Copper(Cu),Nickel(Ni) and bimetallic Cu–Ni nanoparticles were prepared by a simple chemical method and their antibacterial activity was tested against the widely used standard human pathogens Staphylococcus aureus(gram-negative) and Escherichia coli(gram-positive).Additionally,these nanoparticles were tested against the dental pathogen Streptococcus mutans.Our results are promising for potential use in dental materials science.     

Effect of ZnO nanoparticles on anti-aging properties of polyurethane coating

Polyurethane nano-coatings were prepared by adding nano-concentrates with nanometer zinc oxide （nano-ZnO） to polyurethane coating. The dispersion state of nanoparticles was observed by TEM images. SEM observation and FT-IR analysis indicate that the nano-coating with 1% ZnO nanoparticles can retain better morphological structure than the nano-coating with 5% ZnO nanoparticles after 500 h accelerated aging. It is known from XPS analysis that the anti-oxidation properties of polyurethane coating are enhanced by 1% ZnO nanoparticles through the nano-network and destroyed by 5% ZnO nanoparticles due to the strong light catalysis. A small change in capacitances of nano-coatings with 1% ZnO nanoparticles before and after accelerated aging indicates that 1% ZnO nanoparticles improve the corrosion resistance of coating, while a large increase in capacitances of nano-coating with 5% ZnO nanoparticles before and after accelerated aging demonstrates that 5% ZnO nanoparticles damage the corrosion resistance of coating.     

化学镀法制备多壁碳纳米管负载非晶态镍-磷纳米粒子催化剂的性能及其苯加氢催化活性研究

通过化学镀工艺,采用以次磷酸钠为还原剂的镀液将镍-磷（Ni-P）纳米粒子负载于多壁碳纳米管（MWCNTs）表面。通过场发射扫描电子显微镜（FE-SEM）、高分辨透射电镜（HR-TEM）、X射线衍射仪（XRD）、选区电子衍射仪（SAED）、电感耦合等离子体质谱（ICP-MS）、傅里叶变换红外光谱仪（FT-IR）、差示热分析仪（DTA）、X射线光电子能谱仪（XPS）等测试手段对催化剂的物理化学性能进行了表征,分析结果表明：Ni-P纳米粒子化学组成为Ni_73.8P_26.2,为非晶态结构实心圆球体,均匀分散负载于MWCNTs外壁,平均尺寸约100 nm,粒度分布窄,镍元素与磷元素之间无明显电子转移,催化剂在350℃以下结构和热稳定性较强。通过催化剂对于苯加氢反应的研究评价了其催化性能,结果表明在Ni-P/MWCNTs催化剂作用下,苯全部选择性地转化为环己烷,催化剂显示出较好的催化活性（71.2%）和高选择性（100%）。     

Chaperonin-mediated stabilization and ATP-triggered release of semiconductor nanoparticles

Various properties of semiconductor nanoparticles, including photoluminescence and catalytic activity, make these materials attractive for a range of applications. As nanoparticles readily coagulate and so lose their size-dependent properties, shape-persistent three-dimensional stabilizers that enfold nanoparticles have been exploited. However, such wrapping approaches also make the nanoparticles insensitive to external stimuli, and so may limit their application. The chaperonin proteins GroEL (from Escherichia coli) and T.th ('T.th cpn', from Thermus thermophilus HB8) encapsulate denatured proteins inside a cylindrical cavity; after refolding, the encapsulated proteins are released by the action of ATP inducing a conformational change of the cavity. Here we report that GroEL and T.th cpn can also enfold CdS semiconductor nanoparticles, giving them high thermal and chemical stability in aqueous media. Analogous to the biological function of the chaperonins, the nanoparticles can be readily released from the protein cavities by the action of ATP. We expect that integration of such biological mechanisms into materials science will open a door to conceptually new bioresponsive devices.     

Solvent-free selective hydrogenation of o-chloronitrobenzene to o-chloroaniline over alumina supported Pt nanoparticles

A supported Pt/Al2O3 catalyst was prepared by immobilizing preformed colloidal Pt nanoparticles on Al2O3. The particle size and size distribution of Pt particles on Al2O3 remained the same as the colloidal nanoparticles. Selective hydrogenation of o-chloronitrobenzene to ochloroaniline was performed on the as-prepared Pt/Al2O3 nanocatalyst without using any solvent and 88.5% selectivity to o-chloroaniline at 98.2% conversion of o-chloronitrobenzene was achieved. Further catalytic experiments with metal cation modification showed that some metal cations could improve the activity in various degrees while maintaining the high selectivity. Especially, 99.8% selectivity to o-chloroaniline at ~100% conversion was attained with Sn4t.     

聚乙烯基吡啶复合膜的合成及表面性质

利用表面引发技术, 自组装合成新的原子转移自由基聚合(ATRP)表面引发剂, 并引发4-乙烯基吡啶(4-VP)聚合. 制备了功能性的聚4-乙烯基吡啶(PVP)膜, 同时在表面配合过渡金属Cu²⁺和Ag⁺, 用NaHB₄还原后得到表面含有金属纳米粒子的复合膜, 并利用XPS, FT-IR, AFM和接触角测试了其结构与性能. 结果表明, 聚 合物金属配合物中的金属离子已经被还原, 其纳米粒子尺寸直径约为170 nm.     

过渡元素离子表面改性锐钛型TiO2光催化活性规律探讨

试验考察第一过渡周期元素离子掺杂改性对锐钛型TiO2（A-TiO2）光催化降解水中十二烷基苯磺酸钠（DBSNa）效果的影响。结果表明，与未改性样品比较，改性后TiO2光催化活性大部分得到提高，除Cu元素掺杂外，掺杂元素电子亲和势与离子半径的比值（Ea／r）与催化活性之间存在一致性；Cu-TiO2光催化活性的降低归结于以一价形式存在。     

LLDPE/TiO2 nanocomposites produced from different crystallite sizes of TiO2 via in situ polymerization

Nano-TiO2 particles with a range of crystallite sizes were synthesized by a conventional sol-gel method,and then used as nanoparticle substrates in the synthesis of LLDPE/TiO2 nanocomposites via in situ polymerization of ethylene/1-hexene with zirconocene/MMAO catalyst.It was found that the size of the nano-TiO2 crystallite nanoparticles can influence the catalytic activity in the polymerization system.The larger nano-TiO2 crystallites provided better catalytic activity in the polymerization system due to more space for monomer attack.In addition,by thermo-gravimetric analysis,it can be seen that the larger nano-TiO2 crystallites also exhibited lower interaction with available MMAO.Consequently,the MMAO reacted more efficiently with the zirconocene catalyst during the activation process,and enhanced polymerization catalysis.All the polymer nanocomposites products did not have well defined melting temperature indicating non-crystalline polymers.This is due to the high amount of hexene incorporation(based on 13C NMR).The difference in crystallite sizes of the nano-TiO2 also affected how 1-hexene became incorporated into the polymer nanocomposites.The smaller crystallite size of nano-TiO2 allowed greater 1-hexene incorporation due to depression of the reactivity of the ethylene.The contribution of this work helps develop a better understanding of the role of nano-TiO2 in the catalytic activity of the polymerization system and in the microstructure of the polymer composite product.However,this study only considers work on the laboratory scale,so for commercial application of these results,it is necessary to scale up the polymerization process.It is only at this stage,that other physical properties,such as the mechanical properties of these materials can be sensibly determined.     

Comparative Study on Composite Electrodes for Medium Temperature PEFCs

1 Results The phenomena that affect the membranes could be found in the electrodes when they operate at medium temperature,due to the utilisation of Nafion as an ionomer in the catalytic layer.An approach to improve the mechanical properties of the ionomer in the catalytic layer was used: different inorganic compounds (zeolite,titania and zirconia),having different chemical-physical properties,were selected as inorganic fillers due to their water retention capacity and to act as mechanical reinforce by ...     

纳米SiC颗粒增强铝基复合材料的拉伸性能

用粉末冶金法制备了纳米SiC颗粒增强纯Al基复合材料(AlMMCs),对该材料的微观结构和拉伸性能进行了研究·结果表明,纳米SiC颗粒在含量很少时即对Al有明显的强化作用,此时,纳米颗粒在基体中的分散比较均匀;当含量较高时则纳米颗粒易于团聚,团聚会使SiC颗粒对Al的强化作用降低·纳米SiC颗粒含量发生变化,SiCp/AlMMCs的断裂机制也有所改变·     

高校实验室催化剂还原方法的分析与探索

催化剂的还原是催化剂具有催化活性的关键步骤。文章分析比较了在催化剂制备中不同还原剂对催化剂纳米粒度和稳定性的影响,并提出以金属整体型为还原剂进行催化剂还原的新概念。这些催化剂还原方法的分析,为实验室范围内催化剂提供了有力的指导。     

多壁碳纳米管负载镧掺杂氢氧化铁纳米胶粒修饰碳纤维簇电极对CO2的光电催化还原研究

通过溶胶法制备了氢氧化铁溶胶纳米粒子及镧掺杂氢氧化铁溶胶纳米粒子,多壁碳纳米管负载后,化学修饰在碳纤维簇电极上,制备出多壁碳纳米管负载镧掺杂氢氧化铁纳米胶粒修饰碳纤维簇电极,该电极对CO_2有光电催化还原作用。多壁碳纳米管修饰后增加了电极的表面积,氢氧化铁纳米胶粒修饰后还原电流变大增强了电催化还原功能,镧掺杂后起始电位正移增加了光催化还原功能。以MOPAC2012提供的PM7半经验分子轨道方法在设计的铁-氧-氯构成的氢氧化铁分子簇模型上进行半经验分子轨道计算,通过对计算结果的热力学,能级,分子轨道组成以及光谱分析表明,氢氧化铁溶胶纳米粒子及其镧掺杂对CO_2有光电催化还原行为。所设计的分子簇模型是具有热力学稳定的结构,镧掺杂加强了其稳定性。氢氧化铁分子簇具有较好的电子转移性,镧掺杂降低了其费米能级高度,有利于光催化,与实验结果相对应。且催化后的CO_2在键长、分子结构以及红外光谱都发生了较大变化,并具有碳酸的前体结构,实现了对CO_2分子的活化和光电化学催化还原。     

Selective oxidation with dioxygen by gold nanoparticle catalysts derived from 55-atom clusters

Supported gold nanoparticles have excited much interest owing to their unusual and somewhat unexpected catalytic properties, but the origin of the catalytic activity is still not fully understood. Experimental work on gold particles supported on a titanium dioxide (110) single-crystal surface has established a striking size threshold effect associated with a metal-to-insulator transition, with gold particles catalytically active only if their diameters fall below approximately 3.5 nm. However, the remarkable catalytic behaviour might also in part arise from strong electronic interaction between the gold and the titanium dioxide support. In the case of industrially important selective oxidation reactions, explanation of the effectiveness of gold nanoparticle catalysts is complicated by the need for additives to drive the reaction, and/or the presence of strong support interactions and incomplete understanding of their possible catalytic role. Here we show that very small gold entities ( approximately 1.4 nm) derived from 55-atom gold clusters and supported on inert materials are efficient and robust catalysts for the selective oxidation of styrene by dioxygen. We find a sharp size threshold in catalytic activity, in that particles with diameters of approximately 2 nm and above are completely inactive. Our observations suggest that catalytic activity arises from the altered electronic structure intrinsic to small gold nanoparticles, and that the use of 55-atom gold clusters may prove a viable route to the synthesis of robust gold catalysts suited to practical application.