Anisotropic Nano Research Articles

Task-Specific Janus Materials in Heterogeneous Catalysis.

Janus materials are anisotropic nano- and microarchitectures with two different faces consisting of distinguishable or opposite physicochemical properties. In parallel with the discovery of new methods for the fabrication of these materials, decisive progress has been made in their application, for example, in biological science, catalysis, pharmaceuticals, and, more recently, in battery technology. This Minireview systematically covers recent and significant achievements in the application of task-specific Janus nanomaterials as heterogeneous catalysts in various types of chemical reactions, including reduction, oxidative desulfurization and dye degradation, asymmetric catalysis, biomass transformation, cascade reactions, oxidation, transition-metal-catalyzed cross-coupling reactions, electro- and photocatalytic reactions, as well as gas-phase reactions. Finally, an outlook on possible future applications is given.

Anisotropic Particle Fabrication Using Thermal Scanning Probe Lithography

Size, shape, and chemical properties of nanoparticles are powerful tools to modulate the optical and physicochemical properties of a particle suspension. Despite having many methods to synthesize anisotropic nanoparticles, often there are challenges in terms of controlling the polydispersity, shape, size, or composition of anisotropic nanoparticles. This work has been inspired by the potential for developing a unique pathway to make different shaped monodispersed anisotropic nano- and microparticles with large flexibility in material choice. Compared to existing methods, this state-of-the-art nanolithographic method is fast, easy to prototype, and much simple in terms of its mechanical requirement. We show that this technique has been efficiently used to make a variety of anisotropic nano- and microparticles of different shapes, such as triangular prisms, ovals, disks, flowers, and stairs following the same pathway, at the same time showing the potential of being flexible with respect to the composition of the particles. The thermal scanning probe lithographic method in combination with dry reactive ion etching was used to make two-dimensional and three-dimensional templates for the fabrication of anisotropic nano- and microparticles. Deposition of different metal/metal oxides by the electron-beam evaporation method onto these templates allowed us to fabricate a range of nanomaterials according to the required functionality in potential applications. The particles were characterized by atomic force microscopy, He-ion microscopy, scanning electron microscopy, and dynamic light scattering to ensure that the developed method is reproducible, flexible, and robust in choosing the shapes for making monodispersed anisotropic nanoparticles with great control over shape and size.

Facet‐Dependent Surface Charge and Hydration of Semiconducting Nanoparticles at Variable pH (Adv. Mater. 52/2021)

SrTiO3 Nanoparticles The surface properties of different facets of SrTiO3 nanoparticles are investigated by atomic force microscopy by Frieder Mugele and co-workers in article number 2106229. Facet-specific forces, atomic-level surface structure, defects, and charges are characterized in a liquid environment. Their measurements reveal substantial differences in isoelectric points and hydration between adjacent facets. These insights are important for the performance of anisotropic nano particles in (photoelectron-) catalysis and for their colloidal self-assembly.

Interfacial Assembly of Nanowire Arrays toward Carbonaceous Mesoporous Nanorods and Superstructures

AbstractSynthesis of anisotropic carbonaceous nano‐ and micro‐materials with well‐ordered mesoporous structures has attracted increasing attention for a broad scope of applications. Although hard‐templating method has been widely employed, overcoming the viscous forces to prepare anisotropic mesoporous materials is particularly challenging via the universal soft‐templating method, especially from sustainable biomass as a carbon resource. Herein, the synthesis of biomass‐derived nanowire‐arrays based mesoporous nanorods and teeth‐like superstructures is reported, through a simple and straightforward polyelectrolyte assisted soft‐templating hydrothermal carbonization (HTC) approach. A surface energy induced interfacial assembly mechanism with the synergetic interactions between micelles, nanowire, nanorods, and polyelectrolyte is proposed. The polyelectrolyte acts not only as a stabilizer to decrease the surface energy of cylindrical micelles, nanowires and nanorods, but also as a structure‐directing agent to regulate the oriented attachment and anisotropic assembly of micelles, nanowires, and nanorods. After a calcination treatment, the carbon nanorod and teeth‐like superstructure are successfully coupled with Ru to directly produce supported catalysts for the hydrogen evolution reaction, exhibiting much better performance than the isotropic nanospheres based catalyst. This HTC approach will open up new avenues for the synthesis of anisotropic materials with various morphologies and dimensions, expanding the palette of materials selection for many applications.

Study of metal-assisted chemical etching of silicon as an alternative to dry etching for the development of vertical comb-drives

Metal-assisted chemical etching (MaCEtch) has recently emerged as a promising technique to etch anisotropic nano- and microstructures in silicon by metal catalysts. It is an economical wet chemical etching method, which can be a good alternative to deep-reactive ion etching (DRIE) process in terms of verticality and etch depth. In the present study, gold is used as a metal catalyst and deposited using physical vapour deposition. It has already been demonstrated that (100) p-type Si wafer can be etched with vertical and smooth side walls. Effects of varying concentrations of etchant constituents and various other parameters, that is, porosity of deposited Au, surface contaminants, oxide formation, metal catalyst, etching time, role of surface tension of additives on the etch depth and surface defects are studied and discussed in detail. By increasing the hydrofluoric acid (HF) concentration from 7.5 M to 10 M, lateral etching is reduced and the microstructure’s width is increased from 17 µm to 18 µm. Porous defects are suppressed by decreasing the hydrogen peroxide (H2O2) concentration from 1.5 M to 1 M. On increasing the etching time from 30 min to 60 min, the microstructures are over-etched laterally. Smoother side walls are fabricated by using the low-surface-tension additive ethanol. The maximum etch depth of 2.6 µm is achieved for Au catalyst in 30 min. The results are encouraging and useful for the development of vertical comb-drives and Micro-Electro-Mechanical Systems (MEMS).

Ellipsoidal inhomogeneity with anisotropic incoherent interface. Multipole series solution and application to micromechanics

The ellipsoidal inhomogeneity with transversely isotropic incoherent interface is considered in the conductivity and elasticity context. The general imperfect interface is modeled by the first order approximation of thin transversely isotropic interphase layer. This model expands the Gurtin et al. (1998) theory of curved deformable interfaces in solids with a nanometer-scale microstructure to the incoherent interfaces between the dissimilar elastic materials and provides a certain insight into the interface moduli. The rigorous analytical solution to the conductivity and elasticity problems has been obtained by the multipole expansion method in terms of ellipsoidal solid harmonics. An accurate fulfillment of the imperfect interface conditions reduces the model boundary value problem to the linear algebraic system for multipole strengths. These results apply equally to the inhomogeneities with anisotropic interphases and nano level incoherent interfaces. The obtained solutions are valid for the non-uniform far loading and are readily incorporated in the many-particle (finite cluster or representative unit cell) model of heterogeneous solid with anisotropic incoherent interface. The tensors of effective conductivity and elastic stiffness of composite with ellipsoidal inhomogeneities are evaluated using Maxwell homogenization scheme. The obtained accurate numerical data indicate that the effective properties of composite may vary widely due to shape of inhomogeneities and the interface anisotropy ratio. Taking the incoherency of interface into account may increase reliability of predicting the behavior of nanostructured solids.

Influence of cap weight on the motion of a Janus particle very near a wall.

The dynamics of anisotropic nano- to micro scale colloidal particles in confined environments, either near neighboring particles or boundaries, is relevant to a wide range of applications. We utilized Brownian dynamics simulations to predict the translational and rotational fluctuations of a Janus sphere with a cap of nonmatching density near a boundary. The presence of the cap significantly impacted the rotational dynamics of the particle as a consequence of gravitational torque at experimentally relevant conditions. Gravitational torque dominated stochastic torque for a particle >1 μm in diameter and with a 20-nm-thick gold cap. Janus particles at these conditions sampled mostly cap-down or "quenched" orientations. Although the results summarized herein showed that particles of smaller diameter (<1 μm) with a thin gold coating (<5 nm) behave similarly to an isotropic particle, small increases in either particle diameter or coating thickness quenched the polar rotation of the particle. Histogram landscapes of the separation distance from the boundary and orientation observations of particles with larger diameters or thicker gold coatings were mostly populated with quenched configurations. Finally, the histogram landscapes were inverted to obtain the potential energy landscapes, providing a road map for experimental data to be interpreted.

Anisotropic Nano-/Microparticles from Diversified Copolymers by Solvent-Mediated Self-Assembly.

Effective synthesis of anisotropic nano-/microparticles (APs) by the copolymers is of great significance in nanomaterials and nanotechnology. However, achieving regulation of the morphology, composition, property, and particle size of anisotropic nano-/microparticles (APs) with diversified copolymers is difficult due to complex mechanism and formation conditions. In this work, a versatile one-pot solvent-mediated self-assembly (SmSa) strategy had been proposed for the facile one-pot synthesis of shape-tunable anisotropic nano-/microparticles (StAPs). In addition, the formation mechanism of StAPs was determined through numerous characterization methods related to morphology and element distribution. The results revealed that the anisotropic architectures of StAPs were closely related to the nature of poly(methylacrylic acid-methyl methacrylate-butyl acrylate) (L1) and poly(butyl acrylate-styrene) (L2) polymer chains imparted by polymer blocks of different domains. Therefore, the ordered assembly of the rigid and hydrophobic L2 polymer chains in micelles consisting of the flexible and amphiphilic L1 and solvent could be successfully carried out under the mediation of increasing solvent polarity and the strong adsorption of poly(vinylpyrrolidone) for L2. Furthermore, the developed versatile SmSa strategy and the obtained StAPs play an essential role in the development of nanoscience and nanotechnology. Particularly given its adjustable emulsifying properties at different pH values, as well as numerous sites for further modification by fluorescent or other components, it can be employed to synthesize a wide range of functional materials.

2D imprinted substrates and 3D electrospun scaffolds revolutionize biomedicine.

Momentous advances in engineering in the 1980s and 1990s reduced significantly the manufacturing cost of equipment that can produce nano to low microscale materials. This was a key milestone in the field of biomedicine, as from the early 2000s, we entered the era of nanobiomedicine. Essentially, with very low capital cost, every laboratory in the world could develop cell culture substrates and/or implantable devices with morphological features down to the nanometer scale. The rationale of using such small dimensional features derives from the fact that the extracellular space is comprised of nanoto microscale supramolecular assemblies. Further, cells employ probing filopodia extensions and contractile intracellular machinery to gather topographical, spatial, mechanical and chemical information from the extracellular environment, which consequently determines cell functionality, lineage commitment and fate. Among the various fabrication technologies, lithography constitutes the most popular 2D top-down method, while electrospinning represents the most widely used 3D bottomup method [1–7]. The produced 2D and 3D constructs have enabled the study of cell and tissue responses at previously economical and technological prohibiting small scales and the rational design thereof for a specific application/clinical indication. Key to the design tenant is that topographical features and morphological structures should promote cellular polarization and organized extracellular matrix assembly, resembling the natural conformation of tissues. Using photolithography back in 1983, microscale V-shape grooves were created to study human gingival and porcine epithelial cell response [8]. By 1997, we were in a position to fabricate substrates with feature (square) accuracy down to 14 nm (depth) to study Xenopus neurites outgrowth using electron-beam lithography [9,10]. To date, we have successfully imprinted various gratings and geometric shapes along different scales onto thermoplastic polymers to create biologically relevant topographical interfaces. Data obtained from these and other studies clearly illustrate that topographical features are powerful modulators of cell morphology and differential function [11–15]. Further, nanoand microscale arrays have been shown to be potent tools in maintaining the phenotype fidelity of permanently differentiated cells and in differentiating stem cells toward specific lineages [16,17]. Multiple topographic arrays have also been used as high-throughput systems to elucidate the cell–surface interactions and enable identification of improved surfaces for optimal/required cell response [18,19]. Specifically, topographical features have been shown to directly modulate cell–material interaction and to affect the composition, orientation and conformation of adsorbed extracellular matrix components [20,21]. Further, nanoimprinted materials have been shown to either 2D imprinted substrates and 3D electrospun scaffolds revolutionize biomedicine

Indigenous north eastern India fern mediated fabrication of spherical silver and anisotropic gold nano structured materials and their efficacy for the abatement of perilous organic compounds from waste water-A green approach

Herein, we presented a hitherto unexplored native fern of north eastern India; Diplazium esculentum mediated biogenic fabrication of spherical silver and anisotropic gold nano structured materials.

The influence of anisotropic nano- to micro-topography on in vitro and in vivo osteogenesis.

Topographically modified substrates are increasingly used in tissue engineering to enhance biomimicry. The overarching hypothesis is that topographical cues will control cellular response at the cell-substrate interface. The influence of anisotropically ordered poly(lactic-co-glycolic acid) substrates (constant groove width of ~1860 nm; constant line width of ~2220 nm; variable groove depth of ~35, 306 and 2046 nm) on in vitro and in vivo osteogenesis were assessed. We demonstrate that substrates with groove depths of approximately 306 and 2046 nm promote osteoblast alignment parallel to underlined topography in vitro. However, none of the topographies assessed promoted directional osteogenesis in vivo. 2D imprinting technologies are useful tools for in vitro cell phenotype maintenance.

Metallic Nano Particles Embedded in Sapphire

ABSTRACTSapphire is best known for its hardness that makes it ideal for many mechanical and optical applications, but its resistance to radiation damage and its optical properties, combined with metallic nano-particles, make it promising for future opto-electronic and plasmonic devices. In this paper, we present an overview of our work on the fabrication of metallic nano-particles embedded in synthetic sapphire by means of ion implantation, thermal annealing and high energy ion irradiation. We show that we can have control over the amount and size of the nano particles formed inside the matrix by carefully choosing the parameters during the preparation process. Furthermore, we show that anisotropic nano particles can be obtained by an adequate high energy ion irradiation of the originally spherical nano particles. We also have studied the linear and non-linear optical properties of these nano-composites and have confirmed that they are large enough for future applications.

Control of shape and size of polymer nanoparticles aggregates in a single-step microcontinuous flow process: a case of flower and spherical shapes.

Controlled aggregation of polymer nanoparticles for building anisotropic nano- and microstructures via a self-assembling bottom-up process is an important strategy. Therefore, in this work, the formation of structured poly(methyl methacrylate) (PMMA) particles with diameters between lower micrometer and submicrometer range by use of a microcontinuous flow arrangement was investigated in the presence of nonionic water-soluble polymer polyvinylpyrrolidone (PVP). The investigations show that the microreaction strategy is well applicable and allows a tuning of size and shape of nanoparticles in dependence on reactant concentrations and flow rate ratios. Larger and complex structured polymer particles have been found at lower PVP concentration, whereas more compact submicron-sized particles were formed at higher PVP concentrations. The addition of ionic surfactants modulates the generation of characteristic particle shapes. The observation of intermediate states between complex flowerlike particles and simple spheres in dependence on the applied concentration of low molecular weight surfactants supports the explanation of particle formation by a mechanism with superposition of particle growth and assembling. When mixed surfactants (PVP-SDS or PVP-CTAB) are used, the final particles shape depends on the concentration of individual concentrations of surfactants and on the competition between mobility, solvation, and micelle formations.

Transition Metal Ion-induced Anisotropic Architectures Using 4,4’-dicarboxy-2,2’-bipyridyl-silver Nanopetals

Designing anisotropic nano- and micro-structures are imperative in many technology oriented fields. Here we have reported a self templating method, where flower like microstructure of silver particles were used as template to generate several anisotropic structures such as rectangular cum dumbbell, cubes, hexagonal whiskers, and rectangular bars etc. under controlled catalytic activity of Co 2+ , Ni 2+ , Cu 2+ , and Zn 2+ respectively. The initial flower like microstructure (template) of silver particles have been prepared from silver salt using disodium salt of 4,4’-dicarboxy-2,2’-bipyridyl(Na2dcbpy) as the reducing as well as capping agent. Then this architecture was used as the initial template to generate several anisotropic structures. The straightforward anisotropic microstructure preparation procedure does not require any other external template, which avoids the subsequent complicated workup. The nucleation processes and optical properties were studied using optical absorption spectroscopy. The anisotropic structure of the as-synthesized Ag particles and the formations of various shaped microstructures have been confirmed by Scanning Electron Microscopy (SEM). A possible mechanism has been proposed explaining the role of dcbpy in the growth of silver particles and the transition metal ion induced anisotropic structures.

Self-Assembly of Segmented Anisotropic Particles: Tuning Compositional Anisotropy To Form Vertical or Horizontal Arrays

Columnar arrays of anisotropic nano- and microparticles, in which the long axes of the particles are oriented perpendicular to the substrate, are of interest for photovoltaics and other applications. Array assembly typically requires applied electric or magnetic fields and/or controlled drying, which are challenging over large areas. Here, we describe a scalable approach to self-assemble multicomponent nanowires into columnar arrays. Self-assembly of partially etched nanowires (PENs) occurred spontaneously during sedimentation from suspension, without drying or applied fields. PENs, which have segments that are either gold or "empty" (solvent-filled) surrounded by a silica shell, were produced from striped metal nanowires by first coating with silica and then removing sacrificial segments by acid etching. Electrostatic repulsion between the particles was necessary for array assembly; however, details of PEN surface chemistry were relatively unimportant. The aspect ratio and relative center of mass (COM) of the PENs were important for determining whether the PEN long axes were vertically or horizontally aligned with respect to the underlying substrate. Arrays with predominantly vertically aligned particles were achieved for PENs with a large offset in COM relative to the geometric center, while other types of PENs formed horizontal arrays. Assemblies were formed over >10 cm(2) areas, with over 60% of particles standing. We assessed array uniformity and reproducibility by imaging many positions within each sample and performing multiple assemblies of differently segmented PENs. This work demonstrates the versatility of gravity-driven PEN array assembly and provides a framework for designing other anisotropic particle systems that self-assemble into columnar arrays.

비국소 탄성 이론을 이용한 나노 판의 휨 및 자유진동해석

In this paper, we study the bending and free vibration analysis of nano plate, using a nonlocal elasticity theory of Eringen with a third-order shear deformation theory. This theory has ability to capture the both small scale effects and quadratic variation of shear strain and consequently shear stress through the plate thickness. Analytical solutions of bending and vibration of a laminated composite nano plate are presented using this theory to illustrate the effect of nonlocal theory on deflection of the nano plates. The relations between nonlocal third-order and local theories are discussed by numerical results. Further, effects of (i) nonlocal parameters, (ii) laminate schemes, (iii) directions of the fiber angle and (iv) number of layers on nondimensional deflections are investigated. In order to validate the present solutions, the reference solutions are used and discussed. The results of anisotropic nano plates using the nonlocal theory may be the benchmark test for the bending analysis.

Encoded anisotropic particles for multiplexed bioanalysis

Encoded anisotropic nano- and microparticles represent an exciting new class of detection and identification strategies for bioanalysis. These particles are synthesized in a number of different ways and can be encoded by shape, composition, topographical features, or optical properties. In this review, we explore synthetic methods for the formation of anisotropic encoded particles and evaluate these systems as multiplexed biosensing platforms. Suspension arrays using anisotropic particles have been used to detect a range of biological species including proteins, nucleic acids, spores, cells, and small molecules. Because in many cases a large number of codes should be obtainable, the potential exists for high levels of multiplexing (thousands or more). The bulk of work in this area to date has focused on initial proof of principle synthesis and identification; however, multiplexed bioassays have been demonstrated for a number of different anisotropic carrier particles and are beginning to be adopted in commercial assays.

Replication of anisotropic dispersed particulates and complex continuous templates

Anisotropic nano-, micro- and mesoscale natural and synthetic structures possess a unique combination of physical properties due to a complex balance of steric factors and intermolecular interactions at multiple length scales. Utilizing such structures as templates for conformal replication allows reproduction of their unique shapes and properties into different synthetic materials. This review is devoted to the recent progress made on anisotropic microstructures suitable as sacrificial templates as well as techniques currently used for their precise replication into various materials. We present an overview of synthetic strategies used for the replication of both dispersed particulates and continuous templates with a number of recent examples of anisotropic organic and inorganic replicas presented. Strategies for generating adequate robust replicas and their expected assembling behavior are also briefly discussed.

Physicochemical processes in polymer materials upon exposure at the MIR orbital space station

An overview of papers on the investigation of physicochemical processes occurring in polymer (polyimide, fluoropolymer, fluoropolyimide, unilaterally aluminized polyimide) films during long-term exposure at the Mir orbital space station is presented in the article dedicated to the centenary of the birthday of Professor S. Ya. Pshezhetskii. Anisotropic nano- and micro-structures oriented in the direction of motion of the station have been detected for the first time with the scanning electron microscopy and atomic force microscopy techniques on surfaces of films exposed to the effects of all factors of open space. The formation of anisotropic structures has been confirmed by the investigation of the light scattering circular diagrams and surface properties of the films. It is supposed that the formation of such structures results from collisions of a flux of oxygen atoms having an energy of ∼5 eV, with the outer surface of the films. It has been found with the use of electronic absorption and infrared spectroscopy that the changes in the surface and optical properties of the films are caused by the occurrence of oxidation processes, degradation of macromolecules, and opening of the imide cycles and aromatic rings of polyimide. Unilaterally aluminized polyimide films are the least resistant to the effects of outer space factors, what can be explained by the photoelectron mechanism of polymer destruction.

Study of one-side aluminized polyimide films exposed on the Mir orbital space station

During exposure on the Mir space station, external polyimide films aluminized on one side substantially lost mass and mechanical strength and their outer surfaces became hydrophilic. The surface tension and polar plots of brightness of the exposed films acquired an anisotropic character. Spatially-oriented nano- and microsized entities, whose size and shape depend on the time of exposure, were detected by the scanning electron and atomic-force microscopy techniques on the outer surfaces of external films. The orientation axes of drops on the surface of the films, polar plots of brightness, and spatially oriented structures coincided with the direction of the station movement. It was assumed that one of the main factors of outer space responsible for mass loss and the formation of the anisotropic nano- and microsized structures is the impact of a flux of oxygen atoms onto the surface of the external film. The efficiency of the reaction of atomic oxygen with polyimides was estimated. A possible (photoelectron) mechanism of the influence of the metal on polyimide degradation is discussed.