Добірка наукової літератури з теми "Macromolecular Building Blocks - Nanoscale Dimensions"

Nanotechnology, a much abused term, refers to the fabrication and assembly of functional objects of nanometer dimensions. In this article, we will refer only to specific aspects of chemical nanotechnology, meaning by this the production of structures of nanometer dimensions by chemical means. In particular, we will center the discussion on the use of metal nanoparticles as chemical building blocks.

ABSTRACTHigh-index materials such as silicon and III-V compounds have recently gained a lot of interest as a promising material platform for efficient photonic nanostructures. Because of the high refractive index, nanoparticles of such materials support Mie resonances and enable efficient light control and its confinement at the nanoscale. Here we propose a design of nanostructure with multipole resonances where optical nanoantennas are made out of transition metal dichalcogenide, in particular, tungsten disulfide WS2. Transition metal dichalcogenide (TMDCs) possess a high refractive index and strong optical anisotropy because of their layered structure and are promising building blocks for next-generation photonic devices. Strong anisotropic response results in different components of TMDC permittivity and the possibility of tailoring nanostructure optical properties by choosing different axes and adjusting dimensions in design. The proposed periodic array of TMDC nanoantennas can be used for controlling optical resonances in the visible and near-infrared spectral ranges and engineering efficient ultra-thin optical components with nanoscale light confinement.

Molecules provide versatile building blocks, with a vast palette of functionalities and an ability to assemble via supramolecular and covalent bonding to generate remarkably diverse macromolecular systems. This is abundantly displayed by natural systems that have evolved on Earth, which exploit both supramolecular and covalent protocols to create the machinery of life. Importantly, these molecular assemblies deliver functions that are reproducible, adaptable, finessed and responsive. There is now a real need to translate complex molecular systems to surfaces and interfaces in order to engineer 21st century nanotechnology. ‘Top-down’ and ‘bottom-up’ approaches, and utilisation of supramolecular and covalent assembly, are currently being used to create a range of molecular architectures and functionalities at surfaces. In parallel, advanced tools developed for interrogating surfaces and interfaces have been deployed to capture the complexities of molecular behaviour at interfaces from the nanoscale to the macroscale, while advances in theoretical modelling are delivering insights into the balance of interactions that determine system behaviour. A few examples are provided here that outline molecular behaviour at surfaces, and the level of complexity that is inherent in such systems.

One-dimensional (1D) nanostructures are ideal systems for investigating the dependence of electrical transport, optical properties and mechanical properties on size and dimensionality. They are expected to play an important role as both interconnects and functional components in the fabrication of nanoscale electronic and optoelectronic devices. This article presents an overview of current research activities that center on nanowires whose lateral dimensions fall anywhere in the range of 1–200 nm. It is organized into three parts: The first part discusses various methods that have been developed for generating nanowires with tightly controlled dimensions, orientations, and well-defined properties. The second part highlights a number of strategies that are being developed for the hierarchical assembly of nanowire building blocks. The third part surveys some of the novel physical properties (e.g., optical, electrical, and mechanical) of these nanostructures. Finally, we conclude with some personal perspectives on the future research directions in this field.

Systems with nanoscale dimensions have attracted great attention for many decades since they manifest interesting size-dependent behavior and have many possible technological applications. While significant progress has been made toward the experimental and theoretical understanding of various phenomena at nanoscale, much is yet is to be explored in fully comprehending how the interplay of several parameters such as shape, size and dimensionality affects the resulting properties. In this work, we study the nature of the interaction in a nanosystem consisting of a charged nanoplate and a charged nanowire. The two constituent nanostructures of this nanosystem represent important building blocks for bottom-up assembly processes. We consider a specific orientation of the two nanostructures and calculate exactly their interaction energy as a function of shape, size and relative distance. With help from suitable though nontrivial mathematical transformations, we are able to derive a closed form exact expression for such an interaction energy. It is shown that the interaction energy of this configuration is very sensitive to shape and depends in a nontrivial way on size and separation distance.

AbstractThe emergence of micro- and nanoscale science and engineering has provided new avenues for engineering materials with macromolecular and even molecular-scale precision, leading to diagnostic and therapeutic technologies that will revolutionize the way healthcare is administered. Biomaterials have evolved from off-the-shelf products to materials designed with molecular precision to exhibit the desired properties for a specific application, often mimicking biological systems. Controlling interactions at the level of natural building blocks, from proteins to cells, facilitates the novel exploration, manipulation, and application of living systems and biological phenomena. In addition, polymer networks with precisely engineered binding sites have been created via molecular imprinting, where functional monomers are preassembled with a target molecule and then the structure is locked with network formation. Nanoscale science and engineering have accelerated the development of novel drug delivery systems and led to enhanced control over how a given pharmaceutical is administered, helping biological potential to be transformed into medical reality. Micro- and nanoscale devices have been fabricated using integrated-circuit processing techniques, enabling strict temporal control over drug release. The advantages of these microdevices include simple release mechanisms, very accurate dosing, the capability of complex release patterns, the potential for local delivery, and possible biological drug stability enhancement by means of storage in a microvolume that can be precisely controlled. In particular, the development of polymer systems that are able to interact with their environment in a thermodynamically responsive manner has led to novel intelligent biomaterials and applications. Intelligent biomedical materials can be used for the delivery of drugs, peptides, and proteins; as targeting agents for site-specific delivery; or as components for the preparation of protein or drug conjugates. These intelligent materials are attractive options as functional components in micro- and nanodevices because of the ease with which recognition and actuation properties can be precisely tailored. Recent developments in intelligent materials and nano- or microdevices for drug delivery systems are the emphasis of this review, which addresses the use of intelligent biomedical materials as carriers for the development of novel pharmaceutical formulations.

ABSTRACTTo realize applications based on nanowires, the development of methods that allow the organization of nanostructures into integrated arrangements is crucial. While many different methods exist, the direct synthesis of complex nanowire structures is one of the most suitable approaches to efficiently connect numerous nanostructures to the macroscopic world. The fabrication of various 3D nanowire assemblies including arrays, networks, and hierarchical structures by combining specifically designed template materials with electrochemical deposition is demonstrated. The ion track template method is extended to create more complex structures by changing template production and electrodeposition parameters. In contrast to current synthesis routes, it is possible to independently control many of the parameters defining both (i) characteristics of individual nanowires (including dimensions and composition) and (ii) the arrangement of the nanoscale building blocks into nanowire assemblies determined by nanowire orientation and integration level. Results that highlight the benefits arising from the design of advanced 3D nanowire architectures are presented.

AbstractSince the development of the light microscope in the 16th century, optical device size and performance have been limited by diffraction. Optoelectronic devices of today are much bigger than the smallest electronic devices for this reason. Achieving control of light—material interactions for photonic device applications at the nanoscale requires structures that guide electromagnetic energy with subwavelength-scale mode confinement. By converting the optical mode into nonradiating surface plasmons, electromagnetic energy can be guided in structures with lateral dimensions of less than 10% of the free-space wavelength. A variety of methods—including electron-beam lithography and self-assembly—have been used to construct both particle and planar plasmon waveguides. Recent experimental studies have confirmed the strongly coupled collective plasmonic modes of metallic nanostructures. In plasmon waveguides consisting of closely spaced silver rods, electromagnetic energy transport over distances of 0.5 m has been observed. Moreover, numerical simulations suggest the possibility of multi-centimeter plasmon propagation in thin metallic stripes. Thus, there appears to be no fundamental scaling limit to the size and density of photonic devices, and ongoing work is aimed at identifying important device performance criteria in the subwavelength size regime. Ultimately, it may be possible to design an entire class of subwavelength-scale optoelectronic components (waveguides, sources, detectors, modulators) that could form the building blocks of an optical device technology—a technology scalable to molecular dimensions, with potential imaging, spectroscopy, and interconnection applications in computing, communications, and chemical/biological detection.

Polymeric nanofibers are finding increasing number of applications and hold the potential to revolutionize diverse fields such as tissue engineering, smart textiles, sensors, and actuators. Aligning and producing long smooth, uniform and defect-free fibers with control on fiber dimensions at the submicron and nanoscale has been challenging due to fragility of polymeric materials. Besides fabrication, the other challenge lies in the ability to characterize these fibers for mechanical properties, as they are widely believed to have improved properties than bulk due to minimization of defects. In this study we present an overall strategy for fabrication and mechanical characterization of polymeric fibers with diameters ranging from sub-50 nm to sub-microns. In the proposed fabrication strategy, polymeric solution is continuously pumped through a glass micropipette which is collected in the form of aligned fiber arrays on a rotating substrate. Polymer molecular weight and polymer solution concentration play dominant roles in controlling the fiber dimensions, which can be used to deposit fibers of different diameters in the same layer or successively built up multi-layer structures. Using this approach, we demonstrate single and multi-layer architectures of several polymeric systems such as Polystyrene (PS), Poly(methyl methacrylate) (PMMA), Poly lactic acid (PLA), and poly(lactic-co-glycolic acid) (PLGA). Further, we demonstrate the ability to manufacture PMMA fixed-free boundary condition cantilevers by breaking the fixed-fixed boundary condition PMMA fibers using Atomic Force Microscope (AFM) in the lateral mode. An integrated approach for mechanical characterization of polymeric fibers is developed. In this approach, the fibers are first deposited on commercially available Transmission Electron Microscopy (TEM) grids in aligned configurations and are mapped for accurate locations under the TEM. Subsequently, the fibers are carefully placed under the AFM and mechanically characterized for flexural modulus using lateral force microscopy (LFM). Finally, accurate fiber dimensions are determined under the Scanning Electron Microscope (SEM). The unique advantage of this approach lies in the ability to deposit a large number of fibers with tunable diameters in aligned configurations with fixed-fixed boundary conditions and requires no external manipulation. Finally, we present a novel methodology to study the resonance characteristics of fixed-fixed boundary condition suspended fibers using a commercially available Laser Doppler Vibrometer (LDV) for sensor applications. The methods developed in this study will greatly aid in increasing our fundamental knowledge of polymeric materials at reduced lengthscales and allow integration of these one-dimensional building blocks in bottom-up assembly environments.

Here we focus on recent advances in understanding the deformation and fracture behavior of collagen, Nature’s most abundant protein material and the basis for many biological composites including bone, dentin or cornea. We show that it is due to the basis of the collagen structure that leads to its high strength and ability to sustain large deformation, as relevant to its physiological role in tissues such as bone and muscle. Experiment has shown that collagen isolated from different sources of tissues universally displays a design that consists of tropocollagen molecules with lengths of approximately 300 nanometers. Using a combination of theoretical analyses and multi-scale modeling, we have discovered that the characteristic structure and characteristic dimensions of the collagen nanostructure is the key to the ability to take advantage of the nanoscale properties of individual tropocollagen molecules at larger scales, leading to a tough material at the micro- and mesoscale. This is achieved by arranging tropocollagen molecules into a staggered assembly at a specific optimal molecular length scale. During bone formation, nanoscale mineral particles precipitate at highly specific locations in the collagen structure. These mineralized collagen fibrils are highly conserved, nanostructural primary building blocks of bone. By direct molecular simulation of the bone’s nanostructure, we show that it is due to the characteristic nanostructure of mineralized collagen fibrils that leads to its high strength and ability to sustain large deformation, as relevant to its physiological role, creating a strong and tough material. We present a thorough analysis of the molecular mechanisms of protein and mineral phases in deformation, and report discovery of a new fibrillar toughening mechanism that has major implications on the fracture mechanics of bone. Our studies of collagen and bone illustrate how hierarchical multi-scale modeling linking quantum chemistry with continuum fracture mechanics approaches can be used to develop predictive models of hierarchical protein materials. We conclude with a discussion of the significance of hierarchical multi-scale structures for the material properties and illustrate how these structures enable one to overcome some of the limitations of conventional materials design, combining disparate material properties such as strength and robustness.