Lim Stephanie I, Zhong Chuan-Jian
Department of Chemistry, State University of New York at Binghamton, Binghamton, New York 13902, USA.
Acc Chem Res. 2009 Jun 16;42(6):798-808. doi: 10.1021/ar8002688.
The harnessing of the nanoscale properties of nanoparticles in most technological applications requires the abilities of controlled processing and assembly, which has been an important challenge because of the difficulty in manipulating interparticle properties. Molecularly mediated processing and assembly of nanoparticles have emerged as an important strategy for addressing this challenge. The capability of this strategy in manipulating size, shape, composition, and interparticle properties has significant implications for designing sensing, biosensing, nanoprobing, and many other functional nanostructures. This Account highlights some of the important findings in investigating both interparticle and collective properties as a forum for discussing new opportunities in exploiting nanoparticle-based designs and applications. The concept of mediator-template assembly of nanoparticles explores the combination of the forces from a mediator and a templating molecule for designing and controlling the interparticle interactions. The manipulation of the interparticle interaction properties and the detection of the molecular signatures are two of the key elements in this concept. A series of well-defined molecular mediators ranging from inorganic, organic, supramolecular, to biological molecules have been explored to ascertain how these two elements can be achieved in nanoparticle assemblies. The emphasis is the fundamental understanding of interparticle molecular interactions, such as covalent, electrostatic, hydrogen bonding, multidentate coordination, pi-pi interactions, etc. Each of these molecular interactions has been examined using specific molecules, such as multifunctional ligands, tunable sizes, shapes, or charges, well-defined molecular rigidity and chirality, or spectroscopic signatures, such as fluorescence and Raman scattering. Examples included thiols, thioethers, carboxylic acids, fullerenes, dyes, homocysteines, cysteines, glutathiones, proteins, and DNAs as molecular mediators for the assembly of gold, alloy, and magnetic nanoparticles. The understanding of these systems provided insights into how the unique electrical, optical, magnetic, and spectroscopic properties of the nanoparticle assemblies can be exploited for potential applications. This Account also highlights a few examples in chemical sensing and bioprobing to illustrate the importance of interparticle interactions and structures in exploiting these properties. One example involves thin-film assemblies of metal nanoparticles as biomimetic ion channels or chemiresistor sensing arrays by exploiting the nanostructured ligand framework interactions. Other examples explore the surface-enhanced Raman scattering signature as nanoprobes for the detection of protein binding or the enzyme-based cutting of interparticle DNAs. The detailed understanding of the design and control parameters in these and other systems should have a profound impact on the exploration of nanoparticles in a wide range of technological applications.
在大多数技术应用中，利用纳米颗粒的纳米级特性需要具备可控加工和组装的能力，而由于难以操控颗粒间的性质，这一直是一项重大挑战。纳米颗粒的分子介导加工和组装已成为应对这一挑战的重要策略。该策略在操控尺寸、形状、组成和颗粒间性质方面的能力，对于设计传感、生物传感、纳米探测及许多其他功能性纳米结构具有重要意义。本综述重点介绍了在研究颗粒间和集体性质方面的一些重要发现，作为讨论利用基于纳米颗粒的设计和应用新机遇的一个论坛。纳米颗粒的介导模板组装概念探索了来自介导物和模板分子的力的组合，用于设计和控制颗粒间相互作用。操控颗粒间相互作用性质和检测分子特征是这一概念的两个关键要素。已探索了一系列定义明确的分子介导物，从无机、有机、超分子到生物分子，以确定如何在纳米颗粒组装中实现这两个要素。重点是对颗粒间分子相互作用的基本理解，如共价、静电、氢键、多齿配位、π-π相互作用等。已使用特定分子对这些分子相互作用中的每一种进行了研究，例如多功能配体、可调尺寸、形状或电荷、定义明确的分子刚性和手性，或光谱特征，如荧光和拉曼散射。示例包括硫醇、硫醚、羧酸、富勒烯、染料、同型半胱氨酸、半胱氨酸、谷胱甘肽、蛋白质和DNA作为组装金、合金和磁性纳米颗粒的分子介导物。对这些系统的理解为如何利用纳米颗粒组装体独特的电学、光学、磁性和光谱性质用于潜在应用提供了见解。本综述还重点介绍了化学传感和生物探测中的一些示例，以说明颗粒间相互作用和结构在利用这些性质方面的重要性。一个示例涉及通过利用纳米结构配体框架相互作用，将金属纳米颗粒制成仿生离子通道或化学电阻传感阵列的薄膜组装体。其他示例探索了表面增强拉曼散射特征作为纳米探针，用于检测蛋白质结合或基于酶的颗粒间DNA切割。对这些及其他系统中设计和控制参数的详细理解，应对广泛技术应用中纳米颗粒的探索产生深远影响。
