金纳米簇化学发光体外生物检测应用研究进展

金纳米簇是一种制备工艺简单、具有分子级尺寸和量子效应的新型发光材料,近年来在化学发光检测中得到了广泛应用,特别是较多应用于体外生物检测.本文综述了金纳米簇化学发光(含电化学发光)体系在体外生物检测中的应用进展.首先,阐释了金纳米簇的合成方法、结构、性质及其化学发光基本原理;其次,总结了国内外近年来基于该体系的体外生物检...     

密排纳米团簇薄膜应变传感器的响应特性及其与团簇覆盖率的相关性

本文通过在PET薄膜上的叉指电极间沉积Pd纳米团簇制备了柔性应变传感器件.传感器通过测量纳米团簇薄膜的电导随PET薄膜形变的变化而产生对应变的响应,不仅具有高的仪表因子,而且具有宽的量程.实验发现,由于密排纳米团簇阵列的电子输运具有渗流特征,造成应变传感器的响应特性与纳米团簇的覆盖率紧密相关.通过控制纳米团簇的沉积过程,制备了由覆盖率接近有效渗流阈值的纳米团簇点阵构成的应变传感器.从最低应变探测限到0.3%应变之间,传感器件具有线性响应且仪表因子高达55.在更高的应变时,仪表因子进一步达到200.纳米团簇薄膜甚至还可以对达到8%应变的巨大形变产生响应,对应的应变因子达到惊人的3500.     

组氨酸、谷胱甘肽混合修饰金纳米团簇的光稳定性研究

金纳米团簇(简称金簇)由几到几百个金原子及修饰试剂组成,由于其尺寸接近于电子费米波长,表现出良好的发光特性及生物相容性,是一类新型纳米标记探针。目前,金纳米团簇在生物检测、细胞成像、癌症诊断及治疗等领域受到研究者的广泛关注。然而,对于光照条件下金簇的稳定性还不清楚。在合成组氨酸、谷胱甘肽混合修饰金簇的基础上,系统研究了光照条件下金簇在不同pH(5.0,7.4和9.0)的荧光变化规律,结果表明,在氙灯强光照射下,金纳米团簇的荧光会随着照射时间的增加逐渐降低,在pH 9.0条件下比pH 5.0及7.4时降低更快,说明金簇在pH 5.0及7.4时光稳定性更好。在此基础上,采用紫外-可见吸收光谱、红外光谱等手段研究了光照前后金簇表面基团的变化规律,发现光照后金簇的紫外可见吸收光谱及红外光谱均发生了明显的变化,说明光照导致金簇表面修饰基团发生了变化。当向体系中通入氮气后,金簇最大发射波长处荧光强度随照射时间的变化明显变慢,说明金簇表面基团与溶液中溶解氧发生了反应,导致金簇表面电荷及修饰试剂状态发生变化,从而导致金簇荧光产生猝灭。相关研究结果对于金纳米团簇在生命科学及分析化学等领域的进一步应用具有一定的参考价值。     

密排纳米团簇薄膜应变传感器的响应特性及共与团簇覆盖率的相关性（英文）

本文通过在PET薄膜上的叉指电极间沉积Pd纳米团簇制备了柔性应变传感器件.传感器通过测量纳米团簇薄膜的电导随PET薄膜形变的变化而产生对应变的响应,不仅具有高的仪表因子,而且具有宽的量程.实验发现,由于密排纳米团簇阵列的电子输运具有渗流特征,造成应变传感器的响应特性与纳米团簇的覆盖率紧密相关.通过控制纳米团簇的沉积过程,制备了由覆盖率接近有效渗流阈值的纳米团簇点阵构成的应变传感器.从最低应变探测限到0.3%应变之间,传感器件具有线性响应且仪表因子高达55.在更高的应变时,仪表因子进一步达到200.纳米团簇薄膜甚至还可以对达到8%应变的巨大形变产生响应,对应的应变因子达到惊人的3500.     

气体团簇离子束装置的设计及其在表面平坦化、自组装纳米结构中的应用

根据超声膨胀原理,n(10-10^4)个气体原子可以绝热冷却后凝聚在一起形成团簇,经过离化后,形成带一个电荷量的团簇离子,比如Arn^+.当团簇离子与固体材料相互作用时,由于平均每个原子携带的能量(~eV)较低,仅作用于材料浅表面区域,因此,气体团簇离子束是材料表面改性的优良选择.本文介绍了一台由武汉大学加速器实验室自主研制的气体团簇离子束装置,包括整体构造、工作原理及实验应用.中性团簇束由金属锥形喷嘴(F=65-135μm,q=14°)形成,平均尺寸为3000 atoms/cluster,经离化后,其离子束流达到了50μA.Ar团簇离子因其反应活性较低,本文运用Ar团簇离子(平均尺寸为1000 atoms/cluster)进行了平坦化和自组装纳米结构的研究.单晶硅片经Ar团簇离子束处理后,均方根粗糙度由初始的1.92 nm降低到0.5 nm,同时观察到了束流的清洁效应.利用Ar团簇离子束的倾斜(30°-60°)轰击,在宽大平坦的单晶ZnO基片上形成了纳米波纹,而在ZnO纳米棒表面则形成了有序的纳米台阶,同时,利用二维功率谱密度函数分析了纳米结构在基片上的表面形貌和特征分布,并计算了纳米波纹的尺寸和数量.     

基于钯/碳纳米粒子复合薄膜的双氧水电化学传感性能研究

本文采用团簇束流沉积方法制备了一种复合纳米粒子电化学催化剂,在碳纳米粒子支撑层上沉积钯纳米粒子薄膜,发现其在双氧水电化学传感中具有较高的灵敏度.碳纳米粒子的覆盖率对钯纳米粒子薄膜的双氧水电化学催化活性有明显的影响.当碳纳米粒子覆盖满一个单层的时候,钯/碳纳米粒子复合薄膜对双氧水的检测灵敏度达到了最高值,是没有碳纳米粒子支撑层时的两倍之多.     

Au/TiN复合薄膜制备及其表面增强拉曼光谱研究

表面增强拉曼散射光谱(SERS)已用于环境监测、生物医药、食品卫生等领域,而高活性SERS基底是表面增强拉曼散射光谱技术应用的关键。TiN作为新型等离子材料具有较强的SERS性能,同时化学稳定性及生物相容性较好,但其SERS性能不如贵金属金强。该研究采用氨气还原氮化法和电化学沉积法,在TiN薄膜表面沉积贵金属Au纳米颗粒制备出Au/TiN复合薄膜。在Au/TiN复合薄膜中单质Au和TiN两种物相共存;随着电化学沉积时间延长,TiN薄膜表面单质金纳米颗粒数量逐渐增多,金纳米颗粒尺寸增大,颗粒间距减小。由于金与TiN两者的本征表面等离子共振耦合作用,Au/TiN复合薄膜的共振吸收峰发生了偏移。利用罗丹明6G为拉曼探针分子,对Au/TiN复合薄膜进行SERS性能分析,发现Au/TiN复合薄膜上的R6G探针分子的拉曼峰信号强度随沉积时间延长呈现先增大后减小的规律;当电化学沉积时间为5 min时,R6G拉曼信号峰较高,复合薄膜样品的SERS活性最大。将Au/TiN复合薄膜和Au薄膜分别浸泡在10-3,10-5,10-7,10-8及10-9 mol·L-1 R6G溶液5 min,进行检测限分析,发现Au/TiN复合薄膜检测极限达10-8 mol·L-1,增强因子达到8.82×105,与Au薄膜和TiN薄膜相比,Au/TiN复合薄膜上对R6G探针分子SERS活性最高。这得益于Au/TiN复合膜中表面等离子体产生的耦合效应,使得局域电磁场强度增强,从而引起R6G探针分子拉曼信号增强。通过2D-FDTD模拟电场分布发现Au/TiN,Au及TiN薄膜具有电场增强作用,其中Au/TiN复合薄膜的增强作用尤为显著,这也证实了氮化钛与金纳米颗粒之间存在耦合效应。另外发现TiN与Au之间可能存在电荷转移,促进了4-氨基苯硫酚氧化反应,进而证实了TiN与Au薄膜的协同作用。此外,Au/TiN复合薄膜均匀性较好,相对平均偏差仅为7.58%。由此可见,采用电化学沉积制备的Au/TiN复合薄膜具有作为SERS基底材料的应用潜力。     

基于钯/碳纳米粒子复合薄膜的双氧水电化学传感性能研究（英文）

本文采用团簇束流沉积方法制备了一种复合纳米粒子电化学催化剂,在碳纳米粒子支撑层上沉积钯纳米粒子薄膜,发现其在双氧水电化学传感中具有较高的灵敏度.碳纳米粒子的覆盖率对钯纳米粒子薄膜的双氧水电化学催化活性有明显的影响.当碳纳米粒子覆盖满一个单层的时候,钯/碳纳米粒子复合薄膜对双氧水的检测灵敏度达到了最高值,是没有碳纳米粒子支撑层时的两倍之多.     

小尺寸铝纳米团簇的相变行为

采用分子动力学方法模拟了半径从0.3–1.3 nm变化的小尺寸铝纳米团簇的熔化、凝固行为. 基于势能-温度曲线、热容-温度曲线分析, 获得了熔点、凝固点与尺寸的依变关系, 并利用表面能理论、小尺寸效应开展了现象分析.研究表明, 铝团簇原子数小于80时, 熔点和凝固点的尺寸依赖性出现无规律的异常变化; 而大于该原子数, 熔、凝固点则随着团簇尺寸的减小而单调下降; 当原子数为27时, 团簇熔点高于块材熔点近40 K. 同时, 铝纳米团簇呈现出凝固滞后现象, 即凝固点低于熔点. 关键词： 纳米团簇 熔点 凝固点 分子动力学     

单斜结构纳米CePO4的控制合成与发光性能研究

利用水热法,调节反应体系中PO3-4/Ce3+摩尔比,低温控制合成了单斜结构CePO4纳米棒及花状纳米团簇.用XRD,FE-SEM,DSC-TG和荧光光谱分析了产物的相结构、晶粒尺寸、形貌及发光性能.结果显示,随PO3-4/Ce3+摩尔比的增加,单斜结构CePO4的合成温度降低,其形貌由棒状演变为花状纳米团簇.当PO3-4/Ce3+摩尔比较低时,得到CePO4纳米棒;当PO3-4/Ce3+摩尔比较高时,得到花状纳米团簇.产物的荧光光谱分析显示一维纳米棒的光致发光性能优于花状纳米团簇.原料H3PO4可重复利用,降低了合成CePO4的成本.     

Study of electrical field distribution of gold-capped nanoparticle for excitation of localized surface plasmon resonance

The specific optical characteristics which can be observed from noble metal nanostructured materials such as nanoparticles and nanoislands have wide variety of applications such as biosensors, solar cells, and optical circuit. Because, these noble metal nanostructures induce the increment of light absorption efficiency by the enhancing effect of electrical field from localized surface plasmon resonance (LSPR) excitation. However, the enhancing effects of electrical field from LSPR using simple structured noble metal nanostructures for several applications are not satisfactory. To realize the more effective light absorption efficiency by the enhancing effect of electrical field, quite different noble metal nanostructures have been desired for applying to several applications using LSPR. In this study, to obtain the more effective enhancing effect of electrical field, conditions for LSPR excitation using a gold-capped nanoparticle layer substrate are computationally analyzed using finite-difference time-domain (FDTD) method. From the previous research, LSPR excitation using such gold-capped nanoparticle layer substrates has a great potential for application to high-sensitive label-free monitoring of biomolecular interactions. For understanding of detailed LSPR excitation mechanism, LSPR excitation conditions were investigated by analyzing the electrical field distribution using simulation software and comparing the results obtained with experimental results. As a result of computational analysis, LSPR excitation was found to depend on the particle alignment, interparticle distance, and excitation wavelength. Furthermore, the LSPR optical characteristics obtained from the simulation analysis were consistent with experimentally approximated LSPR optical characteristics. Using this gold-capped nanoparticle layer substrate, LSPR can be excited easily more than conventional noble metal nanoparticle-based LSPR excitation without noble metal nanoparticle synthesis. Hence, this structure is detectable a small change of refractive index such as biomolecular interactions for biosensing applications.     

Self‐Assembly of Ag6 Clusters into Nanowires for Nonenzymatic Electrochemical Sensing of Glucose

Self‐assembly of metal nanoclusters into 3D ordered superstructures and the exploration of their electrochemical properties are highly significant for fundamental research and practical application. In this study, atomically precise Ag₆(NALC)₅ nanoclusters are successfully synthesized and their structure is determined carefully. It is interesting that the prepared Ag₆(NALC)₅ nanoclusters can be self‐assembled into ultrafine nanowires, long ribbons, and finally 3D porous network in the mixed solution of water and ethanol, which can be attributed to the solvent polarity, static electricity interaction between ligands, and the possible Van der Waals attractions. Such assembly phenomenon lays a foundation for the future fabrication of silver clusters‐based nanodevices. In addition, the synthesized silver nanoclusters can be used for electrochemical sensing of glucose with high detection sensitivity, selectivity, and low limit of detection. This work is expected to be helpful for the synthesis of atomically precise metal nanoclusters and their applications in fabrication of nanodevices for chemical sensors.     

Fluorescent Metallic Nanoclusters: Electron Dynamics,Structure, and Applications

Atomically precise Au nanoclusters (NCs) have emerged as fascinating fluorescent nanomaterials and attracted considerable research interest in both fundamental research and practical applications. Due to enhanced quantum confinement, they possess extraordinary optical, electronic, and magnetic properties and therefore are very promising for a wide range of applications, including biosensing, bioimaging, catalysis, photonics, and molecular electronics. Remarkable progress has been reported for the fundamental understanding, synthesis techniques, and applications. In this review, the updated advances are summarized in Au NCs, including synthesis techniques, optical properties, and applications. In particular, we focus on the optical properties and electron dynamic processes. In addition, the progress in other noble metallic NCs is included in this Review, such as Ag, Cu, Pt, and alloy, which have attracted much research interest recently. Finally, an outlook is presented for such fascinating nanomaterials in both aspects of future fundamental research and potential applications.     

鸡蛋蛋白孵化金纳米荧光团簇与其对污水中痕量Hg~(2+)的检测

金纳米荧光团簇作为一种新型纳米材料,毒性低,光稳定性好,斯托克位移较长。作为荧光探针,不容易由杂质造成干扰。因此,这类材料在环境监测领域引起了广泛的兴趣。然而,由于所选用的配体成本较高,反应条件复杂,目前绝大数合成金纳米荧光团簇的方法造价昂贵,不利于广泛应用。该工作建立了十分简便的方法,利用市售鸡蛋蛋清为天然蛋白质配体,价格低廉,无毒性,不需要任何复杂反应条件,在37℃的条件下孵化,水浴加热24h,得到亮度很高的红色荧光金纳米团簇,适合被普遍采纳。根据实验研究发现,所得到的金纳米团簇稳定性较好,其中激发光谱的最大峰位于470nm,而发射光谱的最大发射峰位于680nm,为典型的红色纳米荧光团簇,相应的荧光产率为8.76%。通过进一步研究发现,所得金纳米荧光团簇可设计为汞金属离子选择性探针。并根据荧光选择性淬灭现象,将其成功地应用于污水中Hg~(2+)的检测。检出限小于1ppb,满足安全饮用水的检出限要求。校准曲线的线性相关线数在99.8%以上。同时研究了实际样品中Hg~(2+)的加标回收测试。并与原子吸收法进行对比。在低浓度测试时,该方法有显著的优越性。在测定高浓度的Hg~(2+)时,两种方法的结果无明显差异,进一步说明了方法的准确性。该方法为天然水中Hg~(2+)的简便检测提供了有效而又经济实惠的手段。     

CO激光器的发展及潜在应用

本文描述CO激发器的发展及潜在应用。叙述工业用预冷气流激光器,气动激光器和外科用水冷管式激光器。概述三种类型的预电离TEA CO激光器及电子束控制CO激光器。最后介绍CO激光器选用的贵金属催化剂。     

Noble-gas nanoclusters with fivefold symmetry stabilized in superfluid helium

Macroscopic samples (volume approximately cm(3), atomic density approximately 10(19) -10(20) cm(-3)) of noble-gas nanoclusters (size approximately 5-6 nm) were produced in superfluid helium by an impurity-helium gas injection technique. X-ray diffraction measurements show that the samples consist of weakly interacting nanoclusters with fivefold symmetry, such as icosahedra and decahedra. These results open new opportunities for fundamental research of nanoclusters of noble gases and other materials in well-controlled environments using experimental techniques requiring bulk samples.     

Sensitivity enhancement of AZO-based ethanol sensor decorated by Au nano-islands

Detecting the hazardous gases for monitoring air pollution and medical diagnosis make highly sensitive gas sensors appeal to many researches. In this paper, benefiting from unique properties of noble metals, Al-doped ZnO based Ethanol sensors were fabricated and characterized in three structures including Al: ZnO thin film, Silver and Gold nano-islands on Al: ZnO thin film. The Silver and Gold thin films turn to nano-islands after a simple annealing process. The XRD analysis of the sputtered Al: ZnO layer indicates the wurtzite crystal structure of the layer with a peak at (002) plane. Moreover, the sensitivity study reveals that Nano-islands of noble metals substantially affects the sensitivity of the sensors. The decorated Gold nano-island Al: ZnO Ethanol sensor has the highest response showing an amount of 45. The response of Al: ZnO and Silver decorated Al: ZnO sensors are virtually identical to all concentrations of Ethanol, whereas the Al: ZnO gas sensor with Gold nano-islands has the substantial sensitivity for different concentrations. In addition, the response times of the sensors are 85, 70 and 90 s for Al: ZnO, Al: ZnO with Ag islands and Al: ZnO decorated by Au islands, respectively. The recovery time of Al: ZnO sensor decorated by Au islands is about 23s, while the recovery time of the Al: ZnO and Al: ZnO decorated by Silver islands are 360 and 370s, respectively. Hence, the simple annealing process on the sputtered gas sensor with a thin layer of Gold makes nano-islands on the sensor which elevates the performance of Ethanol sensing due to the high sensitivity and sensitivity of the sensor.     

Enhancement of catalytic activity by increasing surface area in heterogeneous catalysis

The use of nanoclusters in systems with confined void spaces such as inside mesoporous or microporous solids appears to be an efficient way of preventing aggregation of nanoclusters in their catalytic application. Zeolite-Y is considered as a suitable host providing highly ordered supercages with a diameter of 1.3 nm. Intrazeolite metal(0) nanoclusters were prepared at room temperature by ion-exchange of metal cations with the extra framework Na⁺ ions in Zeolite-Y, followed by the reduction of the metal cations in the cavities of Zeolite-Y with sodium borohydride in aqueous solution, whereby the Zeolite-Y is reloaded with Na⁺ ions. Hence, host framework remains intact as shown by using a multi-prong approach. Intrazeolite transition-metal(0) nanoclusters were isolated by suction filtration and drying in vacuum at room temperature and characterized by a combination of analytical methods. Intrazeolite metal(0) nanoclusters were tested as catalyst in the hydrolysis of sodium borohydride and ammonia-borane, both of which have been considered as a promising hydrogen storage materials. High catalytic activity and the outstandingly long lifetime of intrazeolite transition-metal(0) nanoclusters catalyst in the hydrogen generation from the hydrolysis of both sodium borohydride and ammonia-borane is demonstrated. The results are attributed to the small size of the nanoclusters within the zeolite cages as well as prevention of agglomeration of the nanoclusters.     

Electronic Properties of Metallic Nanoclusters on Semiconductor Surfaces: Implications for Nanoelectronic Device Applications

We review current research on the electronic properties of nanoscale metallic islands and clusters deposited on semiconductor substrates. Reported results for a number of nanoscale metal-semiconductor systems are summarized in terms of their fabrication and characterization. In addition to the issues faced in large-area metal-semiconductor systems, nano-systems present unique challenges in both the realization of well-controlled interfaces at the nanoscale and the ability to adequately characterize their electrical properties. Imaging by scanning tunneling microscopy as well as electrical characterization by current-voltage spectroscopy enable the study of the electrical properties of nanoclusters/semiconductor systems at the nanoscale. As an example of the low-resistance interfaces that can be realized, low-resistance nanocontacts consisting of metal nanoclusters deposited on specially designed ohmic contact structures are described. To illustrate a possible path to employing metal/semiconductor nanostructures in nanoelectronic applications, we also describe the fabrication and performance of uniform 2-D arrays of such metallic clusters on semiconductor substrates. Using self-assembly techniques involving conjugated organic tether molecules, arrays of nanoclusters have been formed in both unpatterned and patterned regions on semiconductor surfaces. Imaging and electrical characterization via scanning tunneling microscopy/spectroscopy indicate that high quality local ordering has been achieved within the arrays and that the clusters are electronically coupled to the semiconductor substrate via the low-resistance metal/semiconductor interface.     

Nanoparticle formation during laser ablation of solids in liquids

The experimental data on the generation of metal and semiconductor nanoparticles during their laser ablation in liquids is reviewed. The dependence of the morphology of noble metal nanoparticles on the liquid type and laser parameters is discussed. The data on the kinetics of the formation of alloyed Au-Ag nanoparticles under laser irradiation of a mixture of colloid solutions of individual nanoparticles are presented. The effect of femtosecond laser beam self-action during metal ablation in liquids via the second harmonic generation at Ag nanoclusters is discussed. The data on the generation of core-shell nanoparticles during laser ablation of alloys and in the presence of the chemical interaction of formed nanoparticles with surrounding liquid are presented. It was shown that laser ablation of CdS and ZnSe crystals leads to the formation of quantum dots of these semiconductors in solution. The parameters controlling the properties of nanoparticles during ablation in liquids and possible applications of the method are discussed.