Functional micro/nanostructures: simple synthesis and application in sensors, fuel cells, and gene delivery

In order to develop new, high technology devices for a variety of applications, researchers would like to better control the structure and function of micro/nanomaterials through an understanding of the role of size, shape, architecture, composition, hybridization, molecular engineering, assembly, and microstructure. However, researchers continue to face great challenges in the construction of well-defined micro/nanomaterials with diverse morphologies. At the same time, the research interface where micro/nanomaterials meet electrochemistry, analytical chemistry, biomedicine, and other fields provides rich opportunities to reveal new chemical, physical, and biological properties of micro/nanomaterials and to uncover many new functions and applications of these materials. In this Account, we describe our recent progress in the construction of novel inorganic and polymer nanostructures formed through different simple strategies. Our synthetic strategies include wet-chemical and electrochemical methods for the controlled production of inorganic and polymer nanomaterials with well-defined morphologies. These methods are both facile and reliable, allowing us to produce high-quality micro/nanostructures, such as nanoplates, micro/nanoflowers, monodisperse micro/nanoparticles, nanowires, nanobelts, and polyhedron and even diverse hybrid structures. We implemented a series of approaches to address the challenges in the preparation of new functional micro/nanomaterials for a variety of important applications This Account also highlights new or enhanced applications of certain micro/nanomaterials in sensing applications. We singled out analytical techniques that take advantage of particular properties of micro/nanomaterials. Then by rationally tailoring experimental parameters, we readily and selectively obtained different types of micro/nanomaterials with novel morphologies with high performance in applications such as electrochemical sensors, electrochemiluminescent sensors, gene delivery agents, and fuel cell catalysts. We expect that micro/nanomaterials with unique structural characteristics, properties, and functions will attract increasing research interest and will lead to new opportunities in various fields of research.     

Aggregate nanostructures of organic molecular materials

Conjugated organic molecules are interesting materials because of their structures and their electronic, electrical, magnetic, optical, biological, and chemical properties. However, researchers continue to face great challenges in the construction of well-defined organic compounds that aggregate into larger molecular materials such as nanowires, tubes, rods, particles, walls, films, and other structural arrays. Such nanoscale materials could serve as direct device components. In this Account, we describe our recent progress in the construction of nanostructures formed through the aggregation of organic conjugated molecules and in the investigation of the optical, electrical, and electronic properties that depend on the size or morphology of these nanostructures. We have designed and synthesized functional conjugated organic molecules with structural features that favor assembly into aggregate nanostructures via weak intermolecular interactions. These large-area ordered molecular aggregate nanostructures are based on a variety of simpler structures such as fullerenes, perylenes, anthracenes, porphyrins, polydiacetylenes, and their derivatives. We have developed new methods to construct these larger structures including organic vapor-solid phase reaction, natural growth, association via self-polymerization and self-organization, and a combination of self-assembly and electrochemical growth. These methods are both facile and reliable, allowing us to produce ordered and aligned aggregate nanostructures, such as large-area arrays of nanowires, nanorods, and nanotubes. In addition, we can synthesize nanoscale materials with controlled properties. Large-area ordered aggregate nanostructures exhibit interesting electrical, optical, and optoelectronic properties. We also describe the preparation of large-area aggregate nanostructures of charge transfer (CT) complexes using an organic solid-phase reaction technique. By this process, we can finely control the morphologies and sizes of the organic nanostructures on wires, tubes, and rods. Through field emission studies, we demonstrate that the films made from arrays of CT complexes are a new kind of cathode materials, and we systematically investigate the effects of size and morphology on electrical properties. Low-dimension organic/inorganic hybrid nanostructures can be used to produce new classes of organic/inorganic solid materials with properties that are not observed in either the individual nanosize components or the larger bulk materials. We developed the combined self-assembly and templating technique to construct various nanostructured arrays of organic and inorganic semiconductors. The combination of hybrid aggregate nanostructures displays distinct optical and electrical properties compared with their individual components. Such hybrid structures show promise for applications in electronics, optics, photovoltaic cells, and biology. In this Account, we aim to provide an intuition for understanding the structure-function relationships in organic molecular materials. Such principles could lead to new design concepts for the development of new nonhazardous, high-performance molecular materials on aggregate nanostructures.     

π-Conjugated cyanostilbene derivatives: a unique self-assembly motif for molecular nanostructures with enhanced emission and transport

π-Conjugated organic molecules represent an attractive platform for the design and fabrication of a wide range of nano- and microstructures for use in organic optoelectronics. The desirable optical and electrical properties of π-conjugated molecules for these applications depend on their primary molecular structure and their intermolecular interactions such as molecular packing or ordering in the condensed states. Because of the difficulty in satisfying these rigorous structural requirements for photoluminescence and charge transport, the development of novel high-performance π-conjugated systems for nano-optoelectronics has remained a challenge. This Account describes our recent discovery of a novel class of self-assembling π-conjugated organic molecules with a built-in molecular elastic twist. These molecules consist of a cyano-substituted stilbenic π-conjugated backbone and various terminal functional groups, and they offer excellent optical, electrical, and self-assembly properties for use in various nano-optoelectronic devices. The characteristic "twist elasticity" behavior of these molecules occurs in response to molecular interactions. These large torsional or conformational changes in the cyanostilbene backbone play an important role in achieving favorable intermolecular interactions that lead to both high photoluminescence and good charge carrier mobility in self-assembled nanostructures. Conventional π-conjugated molecules in the solid state typically show concentration (aggregation) fluorescence quenching. Initially, we describe the unique photoluminescence properties, aggregation-induced enhanced emission (AIEE), of these new cyanostilbene derivatives that elegantly circumvent these problems. These elastic twist π-conjugated backbones serve as versatile scaffolds for the preparation of well-defined patterned nanosized architectures through facile self-assembly processes. We discuss in particular detail the preparation of 1D nanowire structures through programmed self-assembly. This Account describes the importance of utilizing AIEE effects to explore optical device applications, such as organic semiconducting lasers (OSLs), optical memory, and sensors. We demonstrate the rich electronic properties, including the electrical conductivity, field-effect carrier mobility, and electroluminescence of highly crystalline 1D nanowire and coaxial donor-acceptor nanocable structures composed of elastic twist π-conjugated molecules. The electronic properties were measured using various techniques, including current-voltage (I-V), conducting-probe atomic force microscopy (CP-AFM), and space-charge-limited-current (SCLC) measurements. We prepared and characterized several electronic device structures, including organic field-effect transistors (OFETs) and organic light-emitting field-effect transistors (OLETs).     

3D Conformal Surface Engineering of Continuous Fibers with Porous Microstructures for 1D Advanced Functional Materials

One-dimensional (1D) continuous advanced functional materials and devices with inherent flexibility for complex deformations facilitate a broad range of applications in wearable technology. This communication presents a new electrostatic self-assembly strategy for controllable assembly of nanomaterials to fabricate 1D continuous materials with customizable functions based on a kind of continuous fiber fully surface-engineered with 3D conformal porous microstructures (F@3CPMs) by a unique self-assembly approach of breath figure using water microdroplet arrays. Through gently rubbing the modified fibers with suitable triboelectric materials, either positively or negatively charged F@3CPMs can be rationally prepared with adjustable triboelectric charge intensity. Besides showing superiority in incorporating desired components, such kind of F@3CPMs are demonstrated to have general applicability and enhanced performance in controllable self-assembly of polymeric, metal, and carbon nanomaterials for customizable functionalizations. Moreover, taking advantages of continuous fibers that can deform largely, functional F@3CPMs are further applied for development of 1D flexible motion sensing devices by twisting directly, which can be either used as 1D freestanding devices for straightforward integration with conventional fabrics or woven as a fabric structure integrity for a kind of self-powered interactive textiles without additional battery as power resources to detect and monitor the body motions of human beings.     

Biomimetic peptide nanosensors

The development of a miniaturized sensing platform tailored for sensitive and selective detection of a variety of biochemical analytes could offer transformative fundamental and technological opportunities. Due to their high surface-to-volume ratios, nanoscale materials are extremely sensitive sensors. Likewise, peptides represent robust substrates for selective recognition due to the potential for broad chemical diversity within their relatively compact size. Here we explore the possibilities of linking peptides to nanosensors for the selective detection of biochemical targets. Such systems raise a number of interesting fundamental challenges: What are the peptide sequences, and how can rational design be used to derive selective binders? What nanomaterials should be used, and what are some strategies for assembling hybrid nanosensors? What role does molecular modeling play in elucidating response mechanisms? What is the resulting performance of these sensors, in terms of sensitivity, selectivity, and response time? What are some potential applications? This Account will highlight our early attempts to address these research challenges. Specifically, we use natural peptide sequences or sequences identified from phage display as capture elements. The sensors are based on a variety of nanomaterials including nanowires, graphene, and carbon nanotubes. We couple peptides to the nanomaterial surfaces via traditional surface functionalization methods or self-assembly. Molecular modeling provides detailed insights into the hybrid nanostructure, as well as the sensor detection mechanisms. The peptide nanosensors can distinguish chemically camouflaged mixtures of vapors and detect chemical warfare agents with sensitivities as low as parts-per-billion levels. Finally, we anticipate future uses of this technology in biomedicine: for example, devices based on these sensors could detect disease from the molecular components in human breath. Overall, these results provide a novel platform for the development of highly sensitive and selective "nanoelectronic noses".     

Responsive nanostructures from aqueous assembly of rigid-flexible block molecules

During the past decade, supramolecular nanostructures produced via self-assembly processes have received considerable attention because these structures can lead to dynamic materials. Among these diverse self-assembly systems, the aqueous assemblies that result from the sophisticated design of molecular building blocks offer many potential applications for producing biocompatible materials that can be used for tissue regeneration, drug delivery, and ion channel regulation. Along this line, researchers have synthesized self-assembling molecules based on ethylene oxide chains and peptide building blocks to exploit water-soluble supramolecular structures. Another important issue in the development of systems that self-assemble is the introduction of stimuli-responsive functions into the nanostructures. Recently, major efforts have been undertaken to develop responsive nanostructures that respond to applied stimuli and dynamically undergo defined changes, thereby producing switchable properties. As a result, this introduction of stimuli-responsive functions into aqueous self-assembly provides an attractive approach for the creation of novel nanomaterials that are capable of responding to environmental changes. This Account describes recent work in our group to develop responsive nanostructures via the self-assembly of small block molecules based on rigid-flexible building blocks in aqueous solution. Because the rigid-flexible molecules self-assemble into nanoscale aggregates through subtle anisometric interactions, the small variations in local environments trigger rapid transformation of the equilibrium features. First, we briefly describe the general self-assembly of the rod amphiphiles based on a rigid-flexible molecular architecture in aqueous solution. We then highlight the structural changes and the optical/macroscopic switching that occurs in the aqueous assemblies in response to the external signals. For example, the aqueous nanofibers formed through the self-assembly of the rod amphiphiles respond to external triggers by changing their shape into nanostructures such as hollow capsules, planar sheets, helical coils, and 3D networks. When an external trigger is applied, supramolecular rings laterally associate and merge to form 2D networks and porous capsules with gated lateral pores. We expect that the combination of self-assembly principles and responsive properties will lead to a new class of responsive nanomaterials with many applications.     

Solution-phase synthesis of metal and/or semiconductor homojunction/heterojunction nanomaterials

The design and architecture of programmable metal-semiconductor nanostructures with excellent optoelectronic properties from metal and semiconductor building blocks with nanoscale dimensions have been a key aim of material scientists due to their central roles in the fabrication of electronic, optical, and optoelectronic nanodevices. This review focuses on the latest advances in the solution-phase synthesis of metal and/or semiconductor homojunction/heterojunction nanomaterials. It begins with the simplest construction of metal/metal and semiconductor/semiconductor homojunctions, and then highlights the synthetic design of metal/metal and semiconductor/semiconductor heterojunction nanostructures with different building blocks. Special emphasis is placed on metal/semiconductor heterojunction nanomaterials, which are the most challenging and promising nanomaterials for future applications in optoelectronic nanodevices. Finally, this review concludes with personal perspectives on the directions for future research in this field.     

Optical excitations in organic dendrimers investigated by time-resolved and nonlinear optical spectroscopy

Our research is concerned with the optical properties of covalently bound branched multichromophore systems. The presence of strong intramolecular interactions in dendrimers and other branched macromolecules has stimulated new approaches toward improved energy transfer and light-emitting and enhanced nonlinear optical materials, as well as the possibility of delocalized (exciton) excitations in molecular aggregates. This Account summarizes some of our investigations, which combine the use of different time-resolved techniques to examine the dynamics in organic (conjugated) branched structures and provide important structure-function correlations necessary for applications.     

One-Dimensional Nanostructures and Devices of II–V Group Semiconductors

The II–V group semiconductors, with narrow band gaps, are important materials with many applications in infrared detectors, lasers, solar cells, ultrasonic multipliers, and Hall generators. Since the first report on trumpet-like Zn₃P₂ nanowires, one-dimensional (1-D) nanostructures of II–V group semiconductors have attracted great research attention recently because these special 1-D nanostructures may find applications in fabricating new electronic and optoelectronic nanoscale devices. This article covers the 1-D II–V semiconducting nanostructures that have been synthesized till now, focusing on nanotubes, nanowires, nanobelts, and special nanostructures like heterostructured nanowires. Novel electronic and optoelectronic devices built on 1-D II–V semiconducting nanostructures will also be discussed, which include metal–insulator-semiconductor field-effect transistors, metal-semiconductor field-effect transistors, and p–n heterojunction photodiode. We intent to provide the readers a brief account of these exciting research activities.     

Tailored growth of high-quality CsPbI3 nanobelts

Nanobelts with a representative rectangular cross section have attracted much interest, owing to their unique applications for exploring novel and efficient optoelectronic nanodevices. In this work, we report the mass production of high-quality single-crystalline CsPbI₃ nanobelts by a one-step template-free process using a solvothermal method. The as-prepared nanobelts are typically sized in 170–305 nm in width, 50–170 nm in height, and several microns in length, respectively. Accordingly, their width-to-height ratio of the cross section could be tailored from 1 to 6.35 by adjusting the amount of Cs₂CO₃ within the raw materials, representing the formation of CsPbI₃ nanobelts in a tailored manner. The nanobelt growth was attributed mainly to a surfactant-assisted, seed-mediated anisotropic growth mechanism.     

功能树枝状大分子的研究进展

树枝状分子是一类有较大潜力的新型高分子纳米材料。目前为止,树枝状大分子的研究已经涉及生物、化学、物理学、机械学、纳米学等领域。综述了最新报道的几类功能树枝状分子在非线性光学材料、光电材料、药物化学和自组装化学方面的最新应用进展。     

CuO纳米材料的制备及应用研究进展

CuO是一种重要的p型半导体材料,已经被广泛的应用于超导材料、催化剂、磁存储材料、气体传感器、生物医学和锂离子电池等领域。各种形貌的CuO纳米材料,如纳米线、纳米棒、纳米带、纳米花等,已经通过铜的热氧化法、水热合成法和湿化学法等制备出来。CuO纳米材料因其广泛的应用越来越受到人们的关注,与此同时,目前制备方面存在的问题也应该进行相应的改进。     

One-dimensional organic-inorganic hybrid nanomaterials

This feature article presents the current research activities that concentrate on one-dimensional (1D) organic-inorganic hybrid nanostructures such as nanowires, nanorods, and nanotubes. The combination of organic and inorganic components in a 1D manner has been an increasingly expanding research field because the synergistic behavior of organic-inorganic materials is bound directly to the charming characteristics of 1D nanomaterials. These are responsible for the many novel optical and electrical properties, hierarchical superstructures, functions, and versatile applications that have been achieved. In this article, after justifying the interest in developing 1D organic-inorganic hybrid nanomaterials, we classify 1D hybrid nanostructures and review construction strategies that have been adopted, with a special focus on template-directed synthesis. In summary, we provide our personal perspectives on the future emphasis of the research on 1D organic-inorganic hybrid nanostructures.     

一维纳米硼酸盐研究进展：从基础热力学到工程实践

纳米线/棒/管/带/晶须等纳米材料由于其独特的一维（1D）结构及在电子、光学、催化、能源、环境和医药等领域的广泛应用前景而成为研究的热点之一,而硼酸盐则由于其多变的组成及其在众多领域内的独特性能及应用受到了广泛关注。重点围绕碱/碱土金属硼酸盐,从基础热力学、控制合成、应用开发、工程实践等方面对1D纳米硼酸盐材料的最新研究成果进行了综述。此外,对1D纳米硼酸镁的熔融盐（MSS）、化学气相沉积（CVD）等传统高温工艺及本课题组多年来所致力的水热-热转化（HTC）法制备进行了客观比较,结果表明,HTC法在形貌控制合成乃至中试放大等方面具有一定优势。最后以硼酸镁纳米晶须为例,从前述4个方面对目前1D纳米硼酸盐研究中所存在的问题、尤其是针对腐蚀性技术瓶颈的绿色水热合成及其工程实践对策进行了分析和展望。     

Anion-controlled morphologies and spectral features of cyanine-based nanoGUMBOS--an improved photosensitizer

The ability to control the morphologies and spectral properties of organic low-dimensional nanomaterials is of paramount importance. The research reported herein demonstrates a template-free approach to tailored morphological and optical properties for a novel class of pseudoisocyanine (PIC)-based fluorescent organic nanoparticles derived from a group of uniform materials based on organic salts (GUMBOS). The synthesized nanoscale PIC-based particles (termed nanoGUMBOS), [PIC][NTf(2)] and [PIC][BETI], exhibit interesting adaptability as a function of the associated anion. The diamond-shaped nanostructures of [PIC][NTf(2)] and [PIC][BETI] nanorods exhibit enhanced fluorescence quantum yields relative to the parent compound, [PIC][I]. As supported by fluorescence lifetime measurements, these enhanced spectral properties can be attributed to differences in molecular self-assembly ordering (e.g., H- vs. J-aggregation) and restricted molecular rotation leading to reduced twisted intramolecular charge transfer in the nanoGUMBOS. The electrochemical properties of the PIC-based GUMBOS suggest their potential use in dye-sensitized solar cells.     

Phenanthroline modulated self-assembly of nano/micro-scaled metal–organic frameworks

In stark contrast to the report that phenanthroline is an efficient chelate ligand for lanthanide-based metal–organic framework formation, here it is found that phenanthroline can act as a very useful regent to modulate self-assembly of nano/micro-sized yttrium benzenetricarboxylate (Y–BTC). 1D nanobelts of Y–BTC was firstly produced via a simple, mild one-step approach. Then the morphology was transformed to 3D urchin-like hierarchical architectures with the assistance of phenanthroline. Interestingly, the as-synthesized 3D urchin-like superstructures can be disassembled through simple ultrasonic treatment. Thus a large quantity of 1D nanorods was obtained. Additionally, brilliant-red light of the nanomaterials was realized by doping Eu^3 + ions.     

The ion implantation-induced properties of one-dimensional nanomaterials

Nowadays, ion implantation is an extensively used technique for material modification. Using this method, we can tailor the properties of target materials, including morphological, mechanical, electronic, and optical properties. All of these modifications impel nanomaterials to be a more useful application to fabricate more high-performance nanomaterial-based devices. Ion implantation is an accurate and controlled doping method for one-dimensional nanomaterials. In this article, we review recent research on ion implantation-induced effects in one-dimensional nanostructure, such as nanowires, nanotubes, and nanobelts. In addition, the optical property of single cadmium sulfide nanobelt implanted by N⁺ ions has been researched.     

金纳米棒的合成及应用研究进展

金纳米材料具有特殊的物理、化学性质。与其他形状的金纳米材料相比,金纳米棒同时具有化学和光学方面的备向异性,在材料科学、局域表面等离子体共振（LSPR）传感、生物医学等领域存在着巨大的应用前景。文章系统的评述了金纳米棒的合成及应用进展。具体内容包括金纳米棒的合成、金纳米棒的光学特性、金纳米棒在LSPR传感分析方面的应用以及金纳米棒在生物医学方面的应用。     

High-precision,large-domain three-dimensional manipulation of nano-materials for fabrication nanodevices

Nanoscaled materials are attractive building blocks for hierarchical assembly of functional nanodevices, which exhibit diverse performances and simultaneous functions. We innovatively fabricated semiconductor nano-probes of tapered ZnS nanowires through melting and solidifying by electro-thermal process; and then, as-prepared nano-probes can manipulate nanomaterials including semiconductor/metal nanowires and nanoparticles through sufficiently electrostatic force to the desired location without structurally and functionally damage. With some advantages of high precision and large domain, we can move and position and interconnect individual nanowires for contracting nanodevices. Interestingly, by the manipulating technique, the nanodevice made of three vertically interconnecting nanowires, i.e., diode, was realized and showed an excellent electrical property. This technique may be useful to fabricate electronic devices based on the nanowires'' moving, positioning, and interconnecting and may overcome fundamental limitations of conventional mechanical fabrication.     

STEM nanoanalysis of Au/Pt/Ti-Si3N4 interfacial defects and reactions during local stress of SiGe HBTs

Nanoscaled materials are attractive building blocks for hierarchical assembly of functional nanodevices, which exhibit diverse performances and simultaneous functions. We innovatively fabricated semiconductor nano-probes of tapered ZnS nanowires through melting and solidifying by electro-thermal process; and then, as-prepared nano-probes can manipulate nanomaterials including semiconductor/metal nanowires and nanoparticles through sufficiently electrostatic force to the desired location without structurally and functionally damage. With some advantages of high precision and large domain, we can move and position and interconnect individual nanowires for contracting nanodevices. Interestingly, by the manipulating technique, the nanodevice made of three vertically interconnecting nanowires, i.e., diode, was realized and showed an excellent electrical property. This technique may be useful to fabricate electronic devices based on the nanowires' moving, positioning, and interconnecting and may overcome fundamental limitations of conventional mechanical fabrication.