Self-assembled arrays of silica particles on the patterns reflecting the phase-separated structures of mixed Langmuir–Blodgett films

In this study, we constructed self-assembled arrays of silica particles on the micro- and nanopatterns of functionalized templates fabricated from phase-separated mixed Langmuir–Blodgett (LB) films. Electrostatic interaction between the carboxylic groups of silica particles and amino groups on the functionalized templates results in the formation of the self-assembled arrays of silica particles. The patterns of the silica particle arrays can be designed by controlling the phase-separated structures of the original mixed LB films.     

Adsorbed surfactants as templates for the synthesis of morphologically controlled polyaniline and polypyrrole nanostructures on flat surfaces: from spheres to wires to flat films

Nanostructures of polyaniline (PAni) and polypyrrole (PPy) with controlled morphologies have been synthesized on atomically flat surfaces using adsorbed surfactant molecules as templates. Atomic force microscopy (AFM) has been used to investigate polymer film formation on highly oriented pyrolytic graphite (HOPG) and chemically modified HOPG. Morphological control over the resulting polymer film is possible by the addition of coadsorbing molecules, manipulation of the length of the surfactant hydrophobe, or by changing the surface chemistry of the adsorbing substrate. Phase transitions between spheres, cylinders/wires, and featureless films have been observed which exactly parallel transitions between spheres, cylinders, and flat layers in the adsorbed surfactant. Parallel arrays of PAni nanowires can be synthesized with alignment evident over large areas in a simple self-assembly technique in which fabrication and arrangement take place simultaneously. Such a technique in which one can engineer sub-100-nm-ordered nanoscale pi-conjugated polymer structures of a desired shape by a simple self-assembly process presents potential as templates, sensors, and microelectronic devices.     

Acid red 88 dye doped polyaniline framed by soft template method: A potential candidate for dye-sensitized solar cells

The metal-like band structure and the tripping transfer of electrons between bipolarons and polarons found in polyaniline make it for elevated scientific validity. Through a soft template in situ oriented oxidative polymerization, self-assembled nano tubular structures of Acid red (AR88) dye-doped Polyaniline in the presence of hydrochloric acid medium (AR88/PAni/HCl) were prepared and characterized well using different analytical tools. The AR88 (5x10^-4 M) doped PAni prepared in the presence of 1 M HCl shows higher conductivity (2.2679 Scm^?1) and seized its eminent electrical properties. The presence of sulfonic acid group-containing AR88 provides a better environment to give higher conductivity than the PAni-HCl. Due to its better optical transparency, the as-synthesized samples were used for photovoltaic applications. The AR88/PAni/HCl was used as a photosensitizer in dye-sensitized solar cells which shows photoconversion efficiency of around 1.58 %.     

Facile synthesis of the structural hierarchy in chrysanthemum–snowball-like self-organized polyaniline

A facile synthesis of the “chrysanthemum–snowball”-shaped polyaniline (PAni) has been prepared by using self-assembly polymerization of the host–guest monomeric inclusion complex of β-cyclodextrin (β-CD) with aniline. The amount of the monomer complex plays a role as a structural regulator during fabrication of the inclusion polymer as chrysanthemum–snowball structure/nanorods via intermolecular interactions such as: hydrogen bonding between β-CD and PAni, π–π interactions and cooperative interaction between PAni with FeCl₃ in an aqueous medium. The microstructure and morphology of the resulting materials were investigated by using various analytical techniques such as Fourier transform infrared, wide-angle X-ray diffraction, small-angle X-ray scattering, field emission scanning electron microscopy and transmission electron microscopy. After observing the growth process, a tentative mechanism is proposed to elucidate the formation of the PAni hierarchical structures.     

Fabrication,characterization and X-band microwave absorption properties of PAni/Fe3O4/PVA nanofiber composites materials

This work presents a study of microwave absorption properties of PAni/Fe₃O₄/PVA nanofiber composites with different ratio of Fe₃O₄ nanoparticles. The morphology of the composites nanofibers study by Field Emission Scanning Electron Microscopes (FESEM) and Transmission Electron Microscope (TEM) showed that the low content of Fe₃O₄ nanoparticles presence in the composites nanofibers indicates very much uniform surface, in the composites nanofiber without many bends, but some bends develop at higher content of Fe₃O₄ nanoparticles as indicated in the TEM image. Image-J software was used to further investigate the diameter of the composites nanofiber and found to be in the range of 152 to 195 nm. The nanofiber composites show excellent electric and magnetic properties and therefore vary with the addition of Fe₃O₄ nanoparticles in the composites nanofiber. In addition the PAni/Fe₃O₄/PVA composites nanofibers were further characterized by X-ray diffraction spectra (XRD) and Four Transformation infrared spectra (FTIR). The XRD pattern shows the presence of PAni nanotubes containing Fe₃O₄ nanoparticles by indicating peaks at 23.4⁰ and 35.43⁰ which was further supported by FTIR analysis. Microwave vector network analyzers (MVNA) were used to estimate the microwave absorption properties of the composites nanofibers. The absorption parameters was found to be −6.4 dB at 12.9 GHz within the range of X-band microwave absorption frequency, this reflection loss is attributed to the multiple absorption mechanisms as a result of the improved of impedance matching between dielectric and magnetic loss of the absorbent materials demonstrating that these materials can be used as protective material for electromagnetic radiation.     

Thin films of Ag nanoparticles prepared from the reduction of AgI nanoparticles in self-assembled films

A novel method for the preparation of thin films of Ag nanoparticles is reported. Using mercaptoacetic acid as the stabilizing agent, AgI nanoparticles were prepared in aqueous solution. And based on electrostatic interactions, the thiol-passivated AgI nanoparticles were assembled in a self-assembled film by alternative deposition with a cationic polyelectrolyte. Then the AgI nanoparticles in the composite film were reduced by NaBH(4), which resulted in the formation of a thin film of Ag nanoparticles. UV-visible spectra and X-ray photoelectron spectroscopy data confirmed the transformation from AgI to Ag. Atomic force microscopy (AFM) showed that the formed Ag nanoparticles distributed on the film homogeneously. Surface-enhanced Raman spectroscopy (SERS) measurement indicated that the prepared thin films could be used as effective SERS substrates. The reduction process was also carried out by UV light at selective surface regions, which resulted in the formation of patterned nanoparticle arrays.     

Electrochemical polymerization of aniline monomers infiltrated into well-ordered truncated eggshell structures of polyelectrolyte multilayers

The use of nanosphere lithography to construct two-dimensional arrays of polystyrene (PS) particles coated with multilayered polyelectrolyte (PE) shells and truncated eggshell structures composed of PE thin layers is reported. The truncated eggshell PE structures were produced by extraction of the PS particle cores with toluene. The core-extraction process ruptures the apex of the PE coating and causes a slight expansion of the PE thin layers. Aniline hydrochloride was infiltrated into the PE shells and subsequently electropolymerized to yield an array of a composite containing polyaniline (PAni) and PE thin shells. Voltammetric, quartz crystal microbalance, and reflectance Fourier transform infrared spectroscopic measurements indicate that aniline monomers were confined within the thin PE shells and the electropolymerization occurred in the interior of the PE shell. The PE thickness governs the amount of infiltrated monomer and the ultimate loading of the PAni in the truncated eggshell structure. Surface-structure imaging by atomic force microscopy and scanning electron microscopy, carried out after each step of the fabrication process, shows the influence of the PE thickness on the organization and dimensions of the arrays. Thus, the PE thin shells composed of different layers can function as nanometer-sized vessels for the entrapment of charged species for further construction of composite materials and surface modifications. This approach affords a new avenue for the synthesis of new materials that combine the unique properties of conductive polymers and the controllability of template-directed surface reactions.     

聚对二甲苯纳米纤维阵列的CVD液晶模板法制备及降解性能

聚对二甲苯(PPX)具有优异的生物相容性和化学稳定性, 将其构建成仿细胞外基质结构的可降解纳米纤维在生物工程领域具有重要意义. 本文采用化学气相沉积(CVD)法, 以向列型热致液晶E7为模板, 以4-羟甲基-对二甲苯二聚体(PCP-CH₂OH)为聚-(4-羟甲基-对二甲苯)(PPX-CH₂OH)的前驱体, 通过在其分子链上引入 5,6-苯并-2-亚甲基-1,3-二氧杂环庚烷(BMDO)链段制备BMDO/PPX-CH₂OH共聚物纳米纤维阵列, 探讨了共聚物纳米纤维阵列形貌的影响因素, 分析得到了制备共聚物纳米纤维阵列的最佳反应条件, 并研究了BMDO/PPX-CH₂OH共聚物纳米纤维阵列的生物降解性能. 研究表明, 在液晶模板作用下, 通过CVD法成功地使PCP-CH₂OH与BMDO共聚, 并得到了BMDO/PPX-CH₂OH共聚物纳米纤维阵列; 其形貌主要受样品台的温度和沉积速率的影响, 而单体质量比影响较小; 经优化后CVD最佳条件为: 样品台温度-10 ℃, 沉积速率约为0.01 nm/s, 单体质量比为10∶1; 共聚物在37 ℃的0.1 mol/L Na₂CO₃/0.1 mol/L NaHCO₃的缓冲溶液体系下可有效降解, 当降解时间超过23 d后, 纳米纤维阵列中的酯基可完全分解; 当降解时间超过30 d时, 纳米纤维阵列基本降解完全, 总体呈碎片状.     

Synthesis and characterization of "hairy urchin"-like polyaniline by using β-cyclodextrin as a template

A novel synthesis of "hairy urchin"-shaped polyaniline (PAni) and its surface coverage with nanospikes was achieved from a simple microemulsion polymerization technique in the presence of β-cyclodextrin (β-CD). The rodlike micelle phase was characterized, and the key factors affecting the formation of PAni nanostructures were systematically examined. Ferric chloride (FeCl(3)) has played a role as a structural directing agent to fabricate the polymer as hairy urchin-like structure/nanorods via a cooperative interaction between FeCl(3) and DoTAC in an aqueous medium. Host-guest inclusion complex of β-cyclodextrin with aniline was used as a monomer. It has been revealed that the formation of the supramolecular complexes of polyaniline with β-CD due to host-guest interaction is indispensable for the fabrication of these unique PAni nanostructures, and a suitable β-CD to aniline molar ratio is essential to their exclusive formation. Different varieties of PAni nanostructures such as hairy urchin, branched particles consisting of rodlike branches, and regular rodlike particles were obtained in the presence of FeCl(3). Also, in the absence of FeCl(3), a predominant product of regular spherical particles and wirelike aggregation exhibiting faceted surfaces were obtained. The structures of polyaniline hairy urchin-like nanorods were analyzed using transmission electron microscopy (TEM). The synthesized polymer was characterized by Fourier-transform infrared spectroscopy and X-ray diffraction technique. Additionally, the relationship between the morphology and the conductivity of the PAni nanostructures was investigated as well.     

Biomimetic antireflective hierarchical arrays

We report a simple method for the fabrication of biomimetic antireflective hierarchical arrays based on the combination of self-assembled polymer spheres and nanoimprint lithography (NIL). The hierarchical structures are fabricated by creating nanopillars on the microscale round protrusion arrays, which are similar to natural mosquito eyes consisting of combined micro- and nanostructures. The hierarchical arrays dramatically suppress the surface reflection from visible to near-infrared regions with an angle of incidence of up to 70°.     

Effect of fiber geometry on macroscale friction of ordered low-density polyethylene nanofiber arrays

Ordered low-density polyethylene (LDPE) nanofiber arrays are fabricated from silicon nanowire (SiNW) templates synthesized by a simple wet-chemical process based on metal-assisted electroless etching combined with colloidal lithography. The geometrical effect of nanofibrillar structures on their macroscale friction is investigated over a wide range of diameters and lengths under the same fiber density. The optimum geometry for contacting a smooth glass surface is presented with discussions on the compromise between fiber tip-contact area and fiber compliance. A friction design map is developed, which shows that the theoretical optimum design condition agrees well with the LDPE nanofiber geometries exhibiting high measured friction.     

In situ preparation of polyaniline coated fumed and precipitated silica fillers and their composites with nitrile rubber (Investigation on structure-property relationship)

In situ synthesis of polyaniline (PAni) coated pyrogenic or fumed silica (PCFS) and precipitated silica (PCPS) were carried out by the oxidative polymerization of aniline in presence of fumed silica (FS) and precipitated silica (PS). Both uncoated and PAni coated silica fillers were characterized through scanning electron microscope (SEM), infrared spectroscopy and thermo-gravimetric analysis (TGA) to evaluate particle morphology and physico-chemical character of coated and uncoated silica particles. Semi-conducting composites made from two different types of PAni coated silica fillers with NBR exhibit different trend in the variation of electrical properties under different temperature and pressure. These differences in electrical properties of two types of composites are mainly due to physico-chemical characteristics of filler particles as well as their distribution in the polymer matrix. This type of composites may be used as semi-conducting and ESD (electrostatic discharge) material.     

New electroanalytical applications of self-assembled monolayers

New applications of self-assembled monolayers of thiol compounds on gold electrodes are reviewed. They include: (i) exploitation of electrical control of self-assembly of thiol compounds for electrically-addressable immobilization of receptor molecules onto sensor arrays; (ii) a spreader-bar technique for formation of stable nanostructures; and, (iii) use of self-assembled monolayers as selective filters for chemical sensors.     

Formation of a polymer particle monolayer by continuous self-assembly from a colloidal solution

The preparation of two-dimensional monolayers of polymer particles over a large area was demonstrated via a facile solution process. Polymer microspheres were continuously self-assembled into a close-packed monolayer from a colloidal solution confined between two plates such that the top plate was carefully dragged at a constant velocity in the direction opposite that of the monolayer growth. In situ direct observation of the particle movement during the coating process confirmed that particle transport was directed toward the contact line of the solution meniscus by evaporation-induced convective flow. Sliding of the top plate apparently effectively counterbalanced the convective flow to provide the particles with a contact line for growth of a monolayer particle array. The influence of particle concentration, sliding speed of the top plate, and surface wettability of the bottom substrate were investigated and optimized. Monolayer particle arrays were successfully demonstrated as a template for the preparation of ZnO films with ordered hollow hemispherical structures. This approach is applicable to the fabrication of ordered structures of monodispersed particles composed of various materials over large areas.     

Gene transfection into adherent cells using electroporation on a dendrimer-modified gold electrode

Gene transfection into adherent cells from plasmid DNA (pDNA)-arrayed substrates known as gene transfection arrays appears to be a promising tool for the high-throughput analysis of gene functions and protein-protein interaction networks. We tested the ability of electric pulse-stimulated gene transfection from a substrate to overcome low expression efficiency and cross contamination between spots on arrays. We prepared the electrodes used for electric pulse-stimulated gene transfection by sequentially loading a gold thin layer, a self-assembled monolayer of a carboxylic acid-terminated alkanethiol (COOH-SAM), and poly(amidoamine) (PAMAM) dendrimers, either through electrostatic interactions or by covalent linkage to COOH-SAM and then to pDNA. When dendrimers were loaded onto the electrode using electrostatic interactions, the gene-expression efficiency of adherent cells increased as the generation numbers of the dendrimers that we used increased. Gene expression was rarely observed in adherent cells when dendrimers were covalently immobilized onto the electrode. Additionally, we successfully demonstrated site-specific gene transfer using a dendrimer-array electrode with no cross contamination between spots on the electrode.     

Site-selective assembly and reorganization of gold nanoparticles along aminosilane-covered nanolines prepared on indium-tin oxide

We have fabricated gold nanoparticle (AuNP) arrays on indium-tin oxide (ITO) substrates in a nearly one-dimensional fashion. AuNPs were site-selectively immobilized on ITO of which the surface had been patterned by a nanolithography process based on scanning probe microscopy. The fabricated nanoscale lines covered with aminosilane self-assembled monolayer served as chemisorption sites for citrate-stabilized AuNPs of 20 nm in diameter, accordingly, AuNP nanolines with a thickness of single nanoparticle diameter were spontaneously assembled on the lines. In this 1D array, the AuNPs were almost separated from each other due to the electrostatic repulsion between their negatively charged surface layers. Furthermore, a reorganization process of the immobilized AuNP arrays has been successfully demonstrated by replacing each AuNP's surface layer from citric acid to dodecanethiol. By this process, the AuNPs lost their electrostatic repulsion and became hydrophobic so as to be attracted to each other through hydrophobic interaction, resulting in reorganization of the AuNP array. By repeating the deposition and reorganization cycle, AuNPs were more densely packed. The optical absorption peak of the arrays due to their plasmonic resonance was found to shift from 526 to 590 nm in wavelength with repeating cycles, indicating that the resonance manner was changed from the single nanoparticle mode to the multiple particle mode with interparticle coupling.     

Self-organization of self-assembled tetrameric porphyrin arrays on surfaces

The incorporation of designed self-assembled supramolecular structures into devices requires deposition onto surfaces with retention of both structure and function. This remains a challenge and can present a significant barrier to developing devices using self-organizing materials. To examine the role of peripheral groups in the self-organization of self-assembled multiporphyrinic arrays on surfaces, Pd(II)-linked square and Pt(II)-linked trapezoidal tetrameric porphyrin arrays with peripheral tert-butylphenyl or dodecyloxyphenyl functionalities were investigated using various spectroscopies and atomic force microscopy. The Pd(II) assembled squares disassemble upon deposition on glass surfaces, while the Pt(II) assembled trapezoids are more robust and can be routinely cast on these surfaces. The orientation and length of the peripheral alkyl substituents influence the resultant structures on surfaces. The tert-butylphenyl-substituted porphyrin array forms discrete columnar stacks, which assemble in a vertical direction via pi-stacking interactions among the macrocycles. The tetrameric porphyrin array with dodecyloxyphenyl groups forms a continuous film via van der Waals interactions among the peripheral hydrocarbon chains. The super-molecules with liquid crystal-forming moieties also form three-dimensional crystalline structures at higher deposition concentrations. These observations clearly demonstrate that the number, position, and nature of the peripheral groups and the supramolecular structure and dynamics, as well as the energetics of interactions with the surface, are of key importance to the two-dimensional and three-dimensional self-organization of assemblies such as porphyrin arrays on surfaces.     

Sixfold self-assembled hierarchical structures synthesized by direct annealing of Zn microtips

A facile route and the related mechanism for forming sixfold core-shell hierarchical structure with well-defined anisotropic three-dimensional arrays have been described. The regularity and symmetry of hierarchical structures prepared by annealing Zn microtips are superior to the random nanostructure arrays formed in general vapor system reported in the literature. Owing to the distinct stress distribution on the topography of microtips during annealing, the mechanism for growing branched zinc oxide (ZnO) nanowhiskers is related to the relaxation of stress. In addition, the self-assembled hierarchical structures with naturally good contact results in a lowered energy barrier between Zn metal and ZnO semiconductor, which in turn gives a much better emission property.     

Optical modulation of supramolecular assembly of amphiphilic photochromic diarylethene: from nanofiber to nanosphere

A diarylethene derivative with histamines as side chains was synthesized and the morphology of self-assembled supramolecular architecture can be tuned from nanofiber to nanosphere by photo irradiation. The theoretical calculation and model of the self-assembled nanostructure are presented to illuminate the possible self-assembly mechanism.     

One-pot synthesis of dihydropyrano[2,3-c]chromenes via a three component coupling of aromatic aldehydes, malononitrile, and 3-hydroxycoumarin catalyzed by nano-structured ZnO in water: a green protocol

An efficient and green protocol for the synthesis of dihydropyrano[2,3-c]chromene derivatives by one-pot, three component coupling reaction of aromatic aldehyde, malononitrile, and 3-hydroxycoumarin has been developed using nano-structured ZnO as the catalyst. The formation of self-assembled organic nanofiber arising from low-molecular-weight molecules has also been performed. The optical properties of the nano-structured organic molecules were studied.