Inversion of the Supramolecular Chirality of Nanofibrous Structures through Co‐Assembly with Achiral Molecules

To understand the behavior of chiral nanostructures, it is of critical importance to study how achiral molecules regulate the chirality of such nanostructures and what the main driving forces for the regulation processes are. In this work, the supramolecular chirality of helical nanofibers consisting of phenylalanine‐based enantiomers is inverted by achiral bis(pyridinyl) derivatives through co‐assembly. This inversion is mainly mediated by intermolecular hydrogen bonding interactions between the achiral additives and the chiral molecules, which may induce stereoselective interactions and different reorientations for the assembled molecules, as confirmed by calculations. This work not only exemplifies a feasible method to invert the helicity of chiral nanostructures by the addition of achiral molecules, but also provides a method to explore their functions in environments where chiral and achiral molecules are in close proximity.     

Design, synthesis, and characterization of novel nanowire structures for photovoltaics and intracellular probes

Semiconductor nanowires (NWs) represent a unique system for exploring phenomena at the nanoscale and are expected to play a critical role in future electronic, optoelectronic, and miniaturized biomedical devices. Modulation of the composition and geometry of nanostructures during growth could encode information or function, and realize novel applications beyond the conventional lithographical limits. This review focuses on the fundamental science aspects of the bottom-up paradigm, which are synthesis and physical property characterization of semiconductor NWs and NW heterostructures, as well as proof-of-concept device concept demonstrations, including solar energy conversion and intracellular probes. A new NW materials synthesis is discussed and, in particular, a new "nanotectonic" approach is introduced that provides iterative control over the NW nucleation and growth for constructing 2D kinked NW superstructures. The use of radial and axial p-type/intrinsic/n-type (p-i-n) silicon NW (Si-NW) building blocks for solar cells and nanoscale power source applications is then discussed. The critical benefits of such structures and recent results are described and critically analyzed, together with some of the diverse challenges and opportunities in the near future. Finally, results are presented on several new directions, which have recently been exploited in interfacing biological systems with NW devices.     

One-dimensional nanostructures of metals: large-scale synthesis and some potential applications

We review recent developments in our group regarding the solution-phase synthesis of one-dimensional nanostructures of metals. The synthetic approaches include solution-liquid-solid growth for nanowires of low-melting-point metals such as Pb; seed-directed growth for Ag nanowires, nanobeams, and nanobelts; kinetically controlled growth for Pt nanorods, nanowires, and multipods; and galvanic replacement for nanotubes of Au, Pt, and Pd. Both characterization and mechanistic studies are presented for each nanostructure. Finally, we highlight the electrical and plasmonic properties of these metal nanostructures and discuss their potential applications in nanoscale devices.     

Carbon nanotubes with small and tunable diameters from poly(ferrocenylsilane)-block-polysiloxane diblock copolymers

Iron-containing nanostructures produced from various self-assembled poly(ferrocenylsilane)-block-polysiloxane thin films are catalytically active for the initiation and growth of high density, small diameter carbon nanotubes (CNTs). Moreover, the tube diameter and density can be tuned by adjusting the chain lengths of the block copolymer. Iron-containing nanostructures from poly(ferrocenylmethylethylsilane)-b-poly(methylvinylsiloxane) polymer with 25 repeat units of an iron-containing segment and 265 repeat units of a non-iron-containing segment are able to produce CNTs with diameters around or less than 1 nm. Lithographically selective growth of CNTs across a large surface area has been demonstrated using this polymer system. Under the same growth condition, it has been found that the yield of defect-free CNTs varies with the size of the catalytically active nanostructures, which are dictated by the chain lengths of the two blocks. This result indicates that, for a specific-sized catalyst nanocluster, a unique set of growth conditions is required for synthesizing high yield, defect-free CNTs. This finding further addresses the importance of using uniform-sized catalyst-containing nanostructures for consistently achieving high-yield and high-quality CNTs with a minimum number of defects and amount of amorphous carbon.     

The increasing importance of carbon nanotubes and nanostructured conducting polymers in biosensors

The growing need for analytical devices requiring smaller sample volumes, decreased power consumption and improved performance have been driving forces behind the rapid growth in nanomaterials research. Due to their dimensions, nanostructured materials display unique properties not traditionally observed in bulk materials. Characteristics such as increased surface area along with enhanced electrical/optical properties make them suitable for numerous applications such as nanoelectronics, photovoltaics and chemical/biological sensing. In this review we examine the potential that exists to use nanostructured materials for biosensor devices. By incorporating nanomaterials, it is possible to achieve enhanced sensitivity, improved response time and smaller size. Here we report some of the success that has been achieved in this area. Many nanoparticle and nanofibre geometries are particularly relevant, but in this paper we specifically focus on organic nanostructures, reviewing conducting polymer nanostructures and carbon nanotubes.     

Colloidal chemical approaches to inorganic micro- and nanostructures with controlled morphologies and patterns

The controlled synthesis of inorganic micro- and nanostructures with tailored morphologies and patterns has attracted intensive interest because the properties and performances of micro- and nanostructured materials are largely dependent on the shape and structure of the primary building blocks and the way in which the building blocks are assembled or integrated. This review summarizes the recent advances on the solution-phase synthesis of inorganic micro- and nanostructures with controlled morphologies and patterns via three typical colloidal chemical routes, i.e., synthesis based on catanionic micelles, reactive templates, and colloidal crystal templates, with focus on the approaches developed in our lab. Firstly, catanionic micelles formed by mixed cationic/anionic surfactants are used as effective reaction media for the shape-controlled synthesis of inorganic nanocrystals and the solution growth of hierarchical superstructures assembled by one-dimensional (1D) nanostructures. Secondly, reactive template-directed chemical transformation strategy provides a simple and versatile route to fabricate both hollow structures and 1D nanostructures. Thirdly, colloidal crystals are employed as very effective templates for the facile solution-phase synthesis of novel inorganic structures with controlled patterns, such as three-dimensionally (3D) ordered macroporous materials and two-dimensionally (2D) patterned nanoarrays and nanonets. Finally, a brief outlook on the future development in this area is presented.     

Solution-based synthetic strategies for 1-D nanostructures

One-dimensional (1-D) nanostructures of materials have received great research attention because of their unique photochemistry, photophysical, and electron-transport properties different from those of bulky or nanoparticle materials. One of the main challenges in this field is how to precisely control the sizes, dimensionalities, compositions, and crystal structures of materials in nanoscale. This review summarizes the recent progress in the solution-based routes to prepare 1-D nanostructures, highlighting the contribution from this laboratory. Crystal structure as one of the inherent factors that may determine the growth behavior of the nanocrystals is emphasized in this paper. Particularly compounds with layered structures or anistropic crystal structures are given special attention in the controlled growth of 1-D nanostructures. This review aims to present a relatively general understanding of the correlation between the crystal structure and growth behavior of materials under solution-based conditions and show how to choose appropriate conditions for the growth of 1-D nanostructures.     

Formation of two-dimensional structures by tuning the driving force of chemical reactions: an interpretation of kinetic control

Understanding shape control during wet chemical synthesis is important for rational synthesis of nanostructures. Here, we show that two-dimensional metal structures can be obtained from metal salts by reducing the driving force of the reduction reaction that directly translates to the growth of the metal taking place by the two-dimensional nucleation (layer-by-layer growth) mechanism. Experimental evidence is provided for Au, Ag, Pt and Pd systems by choosing appropriate reaction conditions without using any external surfactant. The results are analyzed in terms of the calculations of driving force under different conditions. The results show that surfactants may not be important for producing shape control for the case of 2-D structures while they are required to obtain size control. It is shown that the regime of low driving force is also one where the kinetics of the process is slow and thus a new interpretation of the kinetic control hypothesis is provided.     

One-dimensional inorganic nanostructures: synthesis, field-emission and photodetection

One-dimensional inorganic nanostructures have drawn prime attention due to their potential for understanding fundamental physical concepts and constructing nanoscale electronic and optoelectronic devices. This critical review mainly focuses on our recent research progresses in 1D inorganic nanostructures, including their rational synthesis and potential applications, with an emphasis on field-emitter and photodetector applications. Firstly, we will discuss the rational design of synthetic strategies and the synthesis of 1D nanostructures via a vapour phase approach. Secondly, we will present our recent progresses with respect to several kinds of important inorganic nanostructures and their field-emission and photoconductivity characteristics. Finally, we conclude this review with some perspectives/outlook and future research in these fields (212 references).     

Recent advancements in DNA nanotechnology-enabled extracellular vesicles detection and diagnosis: A mini review

Extracellular vesicles (EVs) are cell-derived nanosized vesicles widely recognized for their critical roles in various pathophysiological processes. Molecular analysis of EVs is currently being considered an emerging tool for diseases diagnosis. However, the small size and heterogeneity of EVs has staggered the EVs research for diseases diagnosis. DNA nanotechnology enables self-assembly of versatile DNA nanostructures and has shown enormous potential in assisting EVs biosensing. In this review, we briefly introduce the recent advances in DNA nanotechnology approaches for EVs detection. The approaches were categorized based on the dimension of DNA nanostructures. We provide critical evaluation of these approaches, and summarize the pros and cons of specific methods. Further, we discuss the challenges and future perspectives in this field.     

Shape control of nanostructured TiO2 using a Schiff base ligand via sol–gel hydrothermal method

Employing a Schiff base ligand in a hydrothermal sol–gel method for preparation of TiO₂ nanostructures was studied. The as-prepared products were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectrum, electron dispersive X-ray spectroscopy and ultraviolet–visible spectroscopy. It is shown that in the controlled reaction conditions, a Schiff base ligand containing hard atoms is capable of driving the growth mechanism in a way that anisotropic shapes of TiO₂ nanostructures are formed. Considering the structure of the Schiff base ligand, the possible growth mechanism of TiO₂ nanostructures is proposed. The optical studied as well as calculated molecular orbital structure of ligand by density functional theory is done.     

Phthalocyanines: An Old Dog Can Still Have New (Photo)Tricks!

Phthalocyanines have enjoyed throughout the years the benefits of being exquisite compounds with many favorable properties arising from the straightforward and diverse possibilities of their structural modulation. Last decades appreciated a steady growth in applications for phthalocyanines, particularly those dependent on their great photophysical properties, now used in several cutting-edge technologies, particularly in photonic applications. Judging by the vivid reports currently provided by many researchers around the world, the spotlight remains assured. This review deals with the use of phthalocyanine molecules in innovative materials in photo-applications. Beyond a comprehensive view on the recent discoveries, a critical review of the most acclaimed/considered reports is the driving force, providing a brief and direct insight on the latest milestones in phthalocyanine photonic-based science.     

Cesium Lead Halide Perovskite Nanostructures: Tunable Morphology and Halide Composition

Inorganic halide perovskite (CsPbX₃) nanostructures have gained considerable interest in recent years owing to their enhanced stability and optoelectronic applications. Recent developments in the synthesis of nanostructures are reviewed. The impact of the precursor and ligand nature, temperature and growth time on the morphology and shape tuning of CsPbX₃ nanostructures is described in relation to their optical properties. The presynthetic and postsynthetic anion exchange strategies to retain pre‐existing crystal phase and shape are discussed in this minireview.     

Shape‐Controlled Growth of Carbon Nanostructures: Yield and Mechanism

Carbon nanostructures with precisely controlled shapes are difficult materials to synthesize. A facet‐selective‐catalytic process was thus proposed to synthesize polymer‐linked carbon nanostructures with different shapes, covering straight carbon nanofiber, carbon nano Y‐junction, carbon nano‐hexapus, and carbon nano‐octopus. A thermal chemical vapor deposition process was applied to grow these multi‐branched carbon nanostructures at temperatures lower than 350 °C. Cu nanoparticles were utilized as the catalyst and acetylene as the reaction gas. The growth of those multi‐branched nanostructures was realized through the selective growth of polymer‐like sheets on certain indexed facets of Cu catalyst. The vapor–facet–solid (VFS) mechanism, a new growth mode, has been proposed to interpret such a growth in the steps of formation, diffusion, and coupling of carbon‐containing oligomers, as well as their final precipitation to form nanostructures on the selective Cu facets.     

Low-temperature polymer-assisted synthesis of shape-tunable zinc oxide nanostructures dispersible in both aqueous and non-aqueous media

We report the shape-controlled synthesis of zinc oxide (ZnO) nanostructures by a poly(vinyl methyl ether) (PVME)-assisted alkaline hydrolysis of zinc acetate at low temperature (20 °C). In this method, ZnO nanostructures of various morphologies including dumbbells, lances and triangles have been successfully prepared via a simple variation of different reaction parameters such as polymer concentration, pH of the reaction mixture and precursor concentration. However, without PVME, ZnO of such structurally uniform morphologies were not formed; rather ZnO of a mixture of defined and undefined morphologies were obtained indicating PVME-assisted the growth of such regular shaped ZnO nanostructures. HRTEM analysis of lance- and triangle-shaped samples as well as SAED patterns of all kinds of samples (dumbbell, lance and triangle) revealed that the ZnO nanostrcutures are single crystalline in nature and might form through oriented growth. XRD analysis also revealed the formation of well crystalline ZnO with a hexagonal structure. FTIR spectroscopy and TGA analysis confirmed the adsorption of PVME on the surface of ZnO nanostructures. Being a solvent adaptable polymer, the adsorbed PVME makes these shaped ZnO nanostructures highly dispersible in both polar and non-polar organic solvents including water. The extent of dispersibility in different solvents was studied by spectroscopic and microscopic techniques. Such solvent adoptability of PVME-coated ZnO nanostructures increases its ease of applications in device fabrication as well as in biological systems.     

Surface-Enhanced Raman Scattering (SERS) on transition metal and semiconductor nanostructures

Surface-Enhanced Raman Scattering (SERS) spectroscopy has experienced a rapid growth over the past 30 years, and has become a valuable tool in various research areas. In conjunction with recent explosive development of nanoscience and nanotechnology, the SERS-active substrates have also expanded from traditional Group 11 metals (Au, Ag, Cu) to non-Group 11 nanostructures. This paper gives an overview of historical advances in the use of non-Group 11 nanostructures as substrates for SERS. Several possible mechanisms and important factors for SERS from non-Group 11 nanostructures are discussed in detail. The SERS from non-Group 11 nanostructures provides many significant applications in surface, interface analysis and biochemical detection. It is reasonable to believe that the advancement in the non-Group 11 nanostructures-based SERS-active substrates will lead to a more promising future for the SERS technology in surface science, spectroscopy and biomedicine.     

Step-by-Step Design of New Theranostic Nanoformulations: Multifunctional Nanovectors for Radio-Chemo-Hyperthermic Therapy under Physical Targeting

While investigating the possible synergistic effect of the conventional anticancer therapies, which, taken individually, are often ineffective against critical tumors, such as central nervous system (CNS) ones, the design of a theranostic nanovector able to carry and deliver chemotherapy drugs and magnetic hyperthermic agents to the target radiosensitizers (oxygen) was pursued. Alongside the original formulation of polymeric biodegradable oxygen-loaded nanostructures, their properties were fine-tuned to optimize their ability to conjugate therapeutic doses of drugs (doxorubicin) or antitumoral natural substances (curcumin). Oxygen-loaded nanostructures (diameter = 251 ± 13 nm, ζ potential = −29 ± 5 mV) were finally decorated with superparamagnetic iron oxide nanoparticles (SPIONs, diameter = 18 ± 3 nm, ζ potential = 14 ± 4 mV), producing stable, effective and non-agglomerating magnetic nanovectors (diameter = 279 ± 17 nm, ζ potential = −18 ± 7 mV), which could potentially target the tumoral tissues under magnetic driving and are monitorable either by US or MRI imaging.     

Growth and characterization of highly branched nanostructures of magnetic nanoparticles

Magnetite nanoparticles of Fe(3)O(4) have been found to grow into large highly branched nanostructures including nanochains and highly branched nanotrees in the solid state through a postannealing process. By varying the preparation conditions such as annealing time and temperature, the nanostructures could be easily manipulated. Changing the starting concentration of the magnetic nanoparticle solution also caused significant changes of the nanoarchitectures. When the magnetic nanoparticle concentration is low, the nanoparticles formed straight rods mainly with an average diameter of 80 nm and a length of several microns. With increasing concentration of the nanoparticles, treelike structures began to form. With further increase of the concentration, well-ordered nanostructures with the appearance of snowflakes were generated. The driving force for the formation of the highly ordered nanostructures includes interaction between the nanoparticles and interaction through surface-capping molecules. This experiment demonstrates that novel nanostructures can be generated by self-assembly of magnetic nanoparticles under the solid state.     

Recent progress in functionalized layered double hydroxides and their application in efficient electrocatalytic water oxidation

Layered double hydroxides(LDHs), a class of anionic clays consisting of brucite-like host layers and interlayer anions, have been widely investigated in the last decade due to their promising applications in many areas such as catalysis, ion separation and adsorption. Owing to the highly tunable composition and uniform distribution of metal cations in the brucite-like layers, as well as the facile exchangeability of intercalated anions, LDHs can be modified and functionalized to form various nanostructures/composites through versatile processes such as anion intercalation and exfoliation, decoration of nanoparticles, selfassembly with other two-dimensional(2D) materials, and controlled growth on conductive supports(e.g.,nanowire arrays, nanotubes, 3D foams). In this article, we briefly review the recent advances on both the LDH nanostructures and functionalized composites toward the applications in energy conversion, especially for water oxidation.     

Recycling Nanowire Templates for Multiplex Templating Synthesis: A Green and Sustainable Strategy

Template‐directed synthesis of nanostructures has been emerging as one of the most important synthetic methodologies. A pristine nanotemplate is usually chemically transformed into other compounds and sacrificed after templating or only acts as an inert physical template to support the new components. If a nanotemplate is costly or toxic as waste, to recycle such a nanotemplate becomes highly desirable. Recently, ultrathin tellurium nanowires (TeNWs) have been demonstrated as versatile chemical or physical templates for the synthesis of a diverse family of uniform 1D nanostructures. However, ultrathin TeNWs as template are usually costly and are discarded as toxic waste in ionic species after chemical reactions or erosion. To solve the above problem, we conceptually demonstrate that such a nanotemplate can be economically recycled from waste solutions and repeatedly used as template.