Linear Superstructures Research Articles

Oriented Linear Self-Assembly of Colloidal Nanocrystals through Regioselective Formation of Hydrogen-Bonded Supramolecular Bridges.

The linear assembly of nanocrystals (NCs) with orientational order presents a significant challenge in the field of colloidal assembly. This study presents an efficient strategy for assembling oleic acid (OAH)-capped, faceted rare earth NCs─such as nanorods, nanoplates, and nanodumbbells─into flexible chain-like superstructures. Remarkably, these NC chains exhibit a high degree of particle orientation even with an interparticle distance reaching up to 15 nm. Central to this oriented assembly method is the facet-selective adsorption of low-molecular-weight polyethylene glycol (PEG), such as PEG-400 (Mn = 400), onto specific facets of NCs. This regioselectivity is achieved by exploiting the lower binding affinity of OAH ligands on the (100) facets of rare earth NCs, enabling facet-specific ligand displacement and subsequent PEG attachment. By adjusting the solvent polarity, the linear assembly of NCs is induced by the solvophobic effect, which simultaneously promotes the formation of hydrogen-bonded PEG supramolecular bridges. These supramolecular bridges effectively connect NCs and exhibit sufficient robustness to maintain the structural integrity of the chains, despite the large interparticle spacing. Notably, even when coassembling different types of NCs, the resulting multicomponent chains still feature highly selective facet-to-facet connections. This work not only introduces a versatile method for fabricating well-aligned linear superstructures but also provides valuable insights into the fundamental principles governing the facet-selective assembly of NCs in solution.

A Response Spectrum Method for Base-Isolated Structures with Equivalent Base Excitations

Base isolation is an effective seismic design strategy that has received considerable attention in recent decades. This research is dedicated to developing a response spectrum method (RSM) for analysis of base-isolated structures under seismic excitation. A novel analytical model consisting of a linear superstructure under equivalent base excitations is proposed in the present study. To determine the response spectra corresponding to the base excitations, termed as the base response spectra, a sufficient number of samples of base excitations comprising base responses need to be obtained through time-history analysis of the nonlinear base-isolated structure in conjunction with the Monte Carlo simulation (MCS). To improve the efficiency for each sample analysis, the recently proposed explicit time-domain method (ETDM) is utilized for fast analysis of the base acceleration and velocity responses with a dimension-reduced iteration scheme. Once the base response spectra are obtained, the mean peak values (MPVs) of structural responses of the linear superstructure can be conveniently evaluated through the complete quadratic combination (CQC) rule. A 4-story nonlinear base-isolated frame structure was analyzed to validate the effectiveness of the proposed analytical model and the feasibility of the present approach for seismic response analysis of nonlinear base-isolated structures.

Modeling and model updating of a full-scale experimental base-isolated building

Large-scale seismic structural tests are crucial to validating both structural design methodologies and the effectiveness of seismic isolation devices. However, considering the significant costs of such tests, it is essential to leverage data from completed tests by taking advantage of numerical models of the tested structures, updated using data collected from the experiments, to complete additional studies that may be difficult, unsafe or impossible to test physically. However, updating complex numerical models poses its own challenges. The first contribution of this paper is to develop a multi-stage model updating method suitable for high-order models of base-isolated structures, which is motivated and evaluated through modeling and model updating of a full-scale four-story base-isolated reinforced-concrete frame building that was tested in 2013 at the NIED E-Defense laboratory in Japan. In most studies involving model updating, all to-be-updated parameters are typically updated simultaneously; however, given the observation that the superstructure in this study predominantly moves as a rigid body in low-frequency modes and the isolation layer plays a minor role in all other modes, this study proposes updating parameters in stages: first, the linear superstructure parameters are updated so that its natural frequencies and mode shapes match those identified via a subspace system identification of the experimental building responses to low-level random excitations; then, the isolation-layer device linear parameters are updated so that the natural frequencies, damping ratios and mode shapes of the three isolation modes match. These two stages break a large-scale linear model updating problem into two smaller problems, thereby reducing the search space for the to-be-updated parameters, which generally reduces computational costs regardless of what optimization algorithm is adopted. Due to the limited instrumentation, the identified modes constitute only a subset of all modes; to match each identified mode with a FEM mode, the second contribution is a procedure proposed to compare each identified mode with a candidate set of FEM modes and to select the best match. Further, nonlinear isolation-layer device models are proposed, updated and validated with experimental data. Finally, combining the isolation-layer devices’ nonlinear models with the updated superstructure linear FEM, the final result is a data-calibrated nonlinear numerical model that will be used for further studies of controllable damping and validation of new design methodologies, and is being made available for use by the research community, alleviating the dearth of experimentally-calibrated numerical models of full-scale base-isolated buildings with lateral–torsional coupling effects.

Effects of vertical component of near-field ground motions on seismic responses of asymmetric structures supported on TCFP bearings

The effects of vertical component of earthquakes on torsional amplification due to mass eccentricity in seismic responses of base-isolated structures subjected to near-field ground motions are studied in this paper. 3-, 6- and 9-story superstructures and aspect ratios of 1, 2 and 3 have been modeled as steel special moment frames mounted on Triple Concave Friction Pendulum (TCFP) bearings considering different period and damping ratios. Three-dimensional linear superstructures resting on nonlinear isolators are subjected to both 2 and 3 component near-field ground motions. Effects of mass eccentricity and vertical component of 25 near-field earthquakes on the seismic responses including maximum isolator displacement and base shear as well as peak superstructure acceleration are studied. The results indicate that the effect of vertical component on the responses of asymmetric structures, especially on the base shear is significant. Therefore, it can be claimed that in the absence of the vertical component, mass eccentricity has a little effect on the base shear increase. Additionally, the impact of this component on acceleration is remarkable so the roof acceleration of a nine-story structure has been increased 1.67 times, compared to the case that the structure is subjected to only horizontal components of earthquakes.

Seismic responses of asymmetric steel structures isolated with the TCFP subjected to mathematical near-fault pulse models

In this paper, the effects of mass eccentricity of superstructure as well as stiffness eccentricity of isolators on the amplification of seismic responses of base-isolated structures are investigated by using mathematical near-fault pulse models. Superstructures with 3, 6 and 9 stories and aspect ratios equal to 1, 2 and 3 are mounted on a reasonable variety of Triple Concave Friction Pendulum (TCFP) bearings considering different period and damping ratio. Three-dimensional linear superstructure mounted on nonlinear isolators are subjected to simplified pulses including fling step and forward directivity while various pulse period (Tp) and Peak Ground Velocity (PGV) amounts as two crucial parameters of these pulses are scrutinized. Maximum isolator displacement and base shear as well as peak superstructure acceleration and drift are selected as the main engineering demand parameters. The results indicate that the torsional intensification of different demand parameters caused by superstructure mass eccentricity is more significant than isolator stiffness eccentricity. The torsion due to mass eccentricity has intensified the base shear of asymmetric 6-story model 2.55 times comparing to symmetric one. In similar circumstances, the isolator displacement and roof acceleration are increased 49 and 116 percent respectively in the presence of mass eccentricity. Furthermore, it is demonstrated that torsional effects of mass eccentricity can force the drift to reach the allowable limit of ASCE 7 standard in the presence of forward directivity pulses.

Seismic Responses of Isolated Structures with Mass Asymmetry Mounted on TCFP Subjected to Near-Fault Ground Motions

This study is devoted to investigate the effects of mass eccentricity on seismic responses of base-isolated structures subjected to near-field ground motions. Superstructures with 3, 6 and 9 stories with aspect ratios equal to 1, 2 and 3 have been idealized as steel special moment frames resting on a reasonable variety of triple concave friction pendulum bearings considering different period and damping ratios for the isolators. Three-dimensional linear superstructures mounted on nonlinear isolators have been subjected to three components of near-field ground motions. Under 25 near-field ground motions, effects of mass eccentricity on the main parameters of the systems have been studied. These parameters have been selected as the main engineering demands including maximum isolator displacement and base shear as well as peak superstructure acceleration. The results indicate that the mass eccentricities do not have a remarkable effect on isolator displacement. In contrary to displacement, torsional effect of mass eccentricity has raised the base shear up to 1.75 times in a three-story superstructure. Additionally, mass eccentricity can amplify the roof acceleration of a nine-story model approximately 3 times in comparison with a symmetric one. It is also concluded that eccentricity in the direction of the subjected earthquake has the most impact on the base shear, while the isolator displacement and roof acceleration are mostly influenced by the eccentricity perpendicular to the earthquake path.

Colloidal interactions in a homeotropic nematic cell with different elastic constants.

We propose a theoretical description of the interaction mediated by a nematic-liquid-crystal host with different Frank elastic constants. A general expression for the energy of such an interaction between colloidal particles of arbitrary size and shape suspended in a homeotropic cell is obtained. In the cells of large thickness, the presented potential converges to that found previously for small particles in the nematic bulk. In general, our results confirm the validity of the one-constant approximation for weakly elastically anisotropic nematic liquid crystals. For nematics with a high splay-to-bend ratio we predict a larger range of the interaction. Using the dependence of this range on the elastic constants, we show that there exists a qualitative similarity between the interactions in a nematic and in a smectic-A phase. It manifests itself, in particular, in a decrease of the angle between a chain of quadrupole particles and the uniform far-field director across a nematic-smectic-A phase transition. We also demonstrate that the anisotropy of the elastic constants can lead to the formation of thermodynamically stable linear superstructures of asymmetric particles (elastic monopoles) with large, compared to usual dipole chains, interparticle distances.

Water-Mediated Assembly of Gold Nanoparticles into Aligned One-Dimensional Superstructures.

This Article shows that water in ethanol colloids of gold nanoparticles enhances the formation of linear clusters and, more important for applications in electronics, determines their assembly on surfaces. We show by dynamic light scattering that ethanol colloids contain mainly monomers and dimers and that wormlike superstructures are mostly absent, despite UV-vis evidence of aggregation. Water added to the colloid as a cosolvent was found to enhance the number of clusters as well as their average size, confirming its role in linear self-assembly, on the scale of a few particles. Water adsorbed from the atmosphere during coating was also found to be a powerful lever to tune self-assembly on surfaces. By varying the relative humidity, a sharp transition from branched to linear superstructures was observed, showing the importance of water as a cosolvent in the formation of cluster superstructures. We show that one-dimensional superstructures may form due to long-range mobility of precursor clusters on wet surfaces, allowing their rearrangement. The understanding of the phenomenon allows us to statistically align both clusters and resulting superstructures on patterned substrates, opening the way to rapid screening in molecular electronics.

Self-assembly and fibrillization of a Fmoc-functionalized polyphenolic amino acid

Self-assembly of Fmoc-L-DOPA leads to the formation of twisted fibers at pH 2. Temperature dependent circular dichroism (CD) reveals the formation of a linear superstructure via π–π stacking. SAXS experiments together with TEM imaging confirm the existence of semi-flexible twisted-multistranded fibers. The self-assembly is found to be pH-dependent, with no aggregation at pH 5 and 7.

Effect of DNA hairpin loops on the twist of planar DNA origami tiles.

The development of scaffolded DNA origami, a technique in which a long single-stranded viral genome is folded into arbitrary shapes by hundreds of short synthetic oligonucleotides, represents an important milestone in DNA nanotechnology. Recent findings have revealed that two-dimensional (2D) DNA origami structures based on the original design parameters adopt a global twist with respect to the tile plane, which may be because the conformation of the constituent DNA (10.67 bp/turn) deviates from the natural B-type helical twist (10.4 bp/turn). Here we aim to characterize the effects of DNA hairpin loops on the overall curvature of the tile and explore their ability to control, and ultimately eliminate any unwanted curvature. A series of dumbbell-shaped DNA loops were selectively displayed on the surface of DNA origami tiles with the expectation that repulsive interactions among the neighboring dumbbell loops and between the loops and the DNA origami tile would influence the structural features of the underlying tiles. A systematic, atomic force microscopy (AFM) study of how the number and position of the DNA loops influenced the global twist of the structure was performed, and several structural models to explain the results were proposed. The observations unambiguously revealed that the first generation of rectangular shaped origami tiles adopt a conformation in which the upper right (corner 2) and bottom left (corner 4) corners bend upward out of the plane, causing linear superstructures attached by these corners to form twisted ribbons. Our experimental observations are consistent with the twist model predicted by the DNA mechanical property simulation software CanDo. Through the systematic design and organization of various numbers of dumbbell loops on both surfaces of the tile, a nearly planar rectangular origami tile was achieved.

Influence of copper crystal surface on the CVD growth of large area monolayer graphene

We study the influence of the surface structure of copper single crystals on the growth of large area monolayer graphene by chemical vapor deposition (CVD) in ultra-high vacuum (UHV). Using atomic-resolution scanning tunneling microscopy (STM), we find that graphene grows primarily in registry with the underlying copper lattice for both Cu(111) and Cu(100). The graphene has a hexagonal superstructure on Cu(111) with a significant electronic component,whereas it has a linear superstructure on Cu(100). Graphene on Cu(111) forms a microscopically uniform sheet, the quality of which is determined by the presence of grain boundaries where graphene grains with different orientations meet. Graphene grown on Cu(100) under similar conditions does not form a uniform sheet and instead displays exposed nanoscale edges. Our results indicate the importance of the copper crystal structure on the microstructure of graphene films produced by CVD.

Dynamic structure–soil–structure interaction between nearby piled buildings under seismic excitation by BEM–FEM model

The dynamic through–soil interaction between nearby pile supported structures in a viscoelastic half-space, under incident S and Rayleigh waves, is numerically studied. To this end, a three-dimensional viscoelastic BEM–FEM formulation for the dynamic analysis of piles and pile groups in the frequency domain is used, where soil is modelled by BEM and piles are simulated by one-dimensional finite elements as Bernoulli beams. This formulation has been enhanced to include the presence of linear superstructures founded on pile groups, so that structure–soil–structure interaction (SSSI) can be investigated making use of a direct methodology with an affordable number of degrees of freedom. The influence of SSSI on lateral spectral deformation, vertical and rotational response, and shear forces at pile heads, for several configurations of shear one-storey buildings, is addressed. Maximum response spectra are also presented. SSSI effects on groups of structures with similar dynamic characteristics have been found to be important. The system response can be either amplified or attenuated according to the distance between adjacent buildings, which has been related to dynamic properties of the overall system.

Active and passive states in ecological models (stabilization, adaptation, and survivability)

The biological process of individuals moving from an active state to a passive one when environmental conditions become adverse is formalized. From the mathematical point of view, this results in a universal linear superstructure to nonlinear models of ecosystems. It is found that under a certain choice of transition rates, the oscillatory instability can be stabilized and population survivability can be increased. Processes of competition, predation, and cyclic coadaptation of populations in a variable environment are studied.

Organogel Formation by a Cholesterol-Stoppered Bistable [2]Rotaxane and Its Dumbbell Precursor

The switching properties, gelation behavior, and self-organization of a cholesterol-stoppered bistable [2]rotaxane containing a cyclobis(paraquat-p-phenylene) ring and tetrathiafulvalene/1,5-dioxynaphthalene recognition units situated in the rod portion of the dumbbell component have been investigated by electrochemical, spectroscopic, and microscopic means. The cyclobis(paraquat-p-phenylene) ring in the [2]rotaxane can be switched between the tetrathiafulvalene and 1,5-dioxynaphthalene recognition units by addressing the redox properties of the tetrathiafulvalene unit. The organogels can be prepared by dissolving the [2]rotaxane and its dumbbell precursor in a CH2Cl2/MeOH (3:2) mixed solvent and liquified by adding the oxidant Fe(ClO4)3. Direct evidence for the self-organization was obtained from AFM investigations which have shown that both of the [2]rotaxane and its dumbbell precursor form linear superstructures which we propose are helical in nature.

Identifiability of linear superstructures under feedback-Taking base-isolated structures as example

The identifiability condition for substructural identification in free-vibration systems is investigated by spectral analysis and parametric methods in the framework of closed-loop systems. Substructures governed by linear and nonlinear feedback laws are both considered. The feedback law mechanism is shown to have greater influence on identifiability than does the model structure or the identification method. Copyright © 2008 John Wiley & Sons, Ltd.

Synthesis of Calcium Phosphate Nanofilaments in Reverse Micelles

Reverse micelles of calcium bis(2-ethylhexyl)phosphate (Ca(DEHP)2) were used to synthesize calcium phosphate nanostructures from a reaction mixture initially containing a water-in-cyclohexane emulsion of Ca(DEHP)2, ammonium hydrogen phosphate, and triblock copolymer, P123. Bundles of DEHP-coated amorphous calcium phosphate nanofilaments, 2 nm in width and >300 μm in length were formed in the oil layer of a phase-separated reaction mixture prepared at a [Ca]:[PO4] molar ratio of 1:1 and pH of 8.2. The nanofilament bundles were stable in the reverse micelle phase up to around 5 days, after which they transformed into 5-nm-wide surfactant-coated hydroxyapatite nanorods. In contrast, similar experiments at a higher supersaturation level (pH = 9, [Ca]:[PO4] = 1.66) produced discrete nanofilaments (100−500 × 10−15 nm in size) that consisted of a linear superstructure based on the side-on stacking of surfactant-coated amorphous calcium phosphate nanorods. Possible factors giving rise to these ordered nanostructu...

Synthesis of aqueous Au core-Ag shell nanoparticles using tyrosine as a pH-dependent reducing agent and assembling phase-transferred silver nanoparticles at the air-water interface.

We demonstrate that the amino acid tyrosine is an excellent reducing agent under alkaline conditions and may be used to reduce Ag+ ions to synthesize stable silver nanoparticles in water. The tyrosine-reduced silver nanoparticles may be separated out as a powder that is readily redispersible in water. The silver ion reduction at high pH occurs due to ionization of the phenolic group in tyrosine that is then capable of reducing Ag+ ions and is in turn converted to a semi-quinone structure. These silver nanoparticles can easily be transferred to chloroform containing the cationic surfactant octadecylamine by an electrostatic complexation process. The now hydrophobic silver nanoparticles may be spread on the surface of water and assembled into highly ordered, linear superstructures that could be transferred as multilayers onto suitable supports by the versatile Langmuir-Blodgett technique. Further, tyrosine molecules bound to the surface of Au nanoparticles through amine groups in the amino acid may be used to selectively reduce silver ions at high pH on the surface of the Au nanoparticles, thus leading to a simple strategy for realizing phase-pure Au core-Ag shell nanostructures.

BaSO4 Crystals Grown at an Expanding Liquid−Liquid Interface in a Radial Hele-Shaw Cell Show Spontaneous Large-Scale Assembly into Filaments

Control over the crystallography, morphology, and spontaneous organization of ceramic crystals are important goals in advanced materials engineering with important application potential. Most studies hitherto have concentrated on static charged interfaces as templates for the controlled nucleation and growth of ceramic crystals. In this communication, we show that BaSO4 crystals grown at a steadily expanding liquid−liquid interface populated by fatty acid molecules spontaneously organize themselves into highly linear superstructures over large length-scales. This experiment is realized in a radial Hele-Shaw cell where the liquid−liquid interfacial growth rate and consequently time scales such as arrival of surfactant molecules to the interface etc. may be readily modulated. Possible reasons for the regular assembly of barite crystals are discussed.

DNA-mediated electrostatic assembly of gold nanoparticles into linear arrays by a simple drop-coating procedure

The assembly of nanoparticles in topologically predefined superstructures is an important problem in the area of nanoscale architecture. In this letter, we demonstrate the electrostatic assembly of lysine-capped colloidal gold particles on drop-coated DNA films. Electrostatic interaction between the positive charges on the gold nanoparticles and the negative charges on the phosphate groups of the DNA template molecules leads to the assembly of the gold nanoparticles in linear superstructures. The use of DNA as templates for the assembly of nanoparticles shows promise for extension to more complex geometries through rational design of the DNA base sequences as well as in the realization of nanowires by stringing together metal nanoparticles.

HREM contrast interpretation of pseudo-symmetric structure regions in nanocrystalline germanium

The atomic structure of nanocrystalline particles formed by vapour deposition and subsequent annealing of amorphous thin films of germanium is studied by high resolution electron microscopy, image processing, and image simulation. The HREM images reveal a highly varied multiply twinned structure. In some regions of adjacent twins contrast features are detected that show pseudo-symmetric linear and circular superstructures of local non-crystallographic symmetry. These contrast features are caused by an overlapping of twin lamellae as is demonstrated by contrast simulations. The simulation procedure is carried out for different models of superimposed twins.