Self‐Assembled Monolayers on Gold for the Fabrication of Radioactive Stents

An innovative and easily applicable method for the fabrication of radioactive stents, to be used for the treatment of restenosis, is presented. By incorporating the β‐emitting radioisotopes ¹⁸⁶Re, ¹⁸⁸Re, ⁹⁰Y, or ³²P into sulfur‐containing adsorbates, it becomes possible to cover a gold surface with a radioactive self‐assembled monolayer (SAM). Two methods have been investigated. In the first, SAMs consisting of potentially radioactive rhenium‐, yttrium‐, and phosphorus‐containing adsorbates have been assembled on 2D gold substrates, after which they have been studied by wettability measurements, electrochemistry, and X‐ray photoelectron spectroscopy (XPS). The stability of these SAMs under simulated physiological conditions (phosphate buffered saline, PBS solution) for periods up to two months has been demonstrated. Alternatively, potentially radioactive monolayers have been prepared by exposure of SAMs of mono‐, bi‐, and tridentate ligands to a solution containing a radiometal (rhenium) in order to bind the metal to the monolayer. The polydentate ligands exhibit excellent binding capacity, leading to SAMs containing over 10^–10 mol/cm² of the radiometal, which is more than sufficient to make this system viable for the delivery of therapeutical dosages of radiation.     

Nanoscale Refractive Index Tuning of Siloxane‐Based Self‐Assembled Electro‐Optic Superlattices

The refractive indices of self‐assembled organic electro‐optic superlattices can be tuned by intercalating high‐Z optically transparent group 13 metal oxide sheets into the structures during the self‐assembly process. Microstructurally regular acentricity and sizable electro‐optic responses are retained in this straightforward synthetic procedure. This “one‐pot” all wet‐chemistry approach involves: i) layer‐by‐layer covalent self‐assembly of intrinsically acentric multilayers of high‐hyperpolarizability chromophores on inorganic oxide substrates, ii) protecting group cleavage to generate a large density of reactive surface hydroxyl sites, iii) self‐limiting capping of each chromophore layer with octachlorotrisiloxane, iv) deposition of metal oxide sheets derived from THF solutions of Ga(OⁱC₃H₇)₃ or In(OⁱC₃H₇)₃, and v) covalent capping of the resulting superlattices.     

Liquid‐Crystal Composites Composed of Photopolymerized Self‐Assembled Fibers and Aligned Smectic Molecules

A new liquid‐crystal composite, composed of photopolymerizable self‐assembled fibers and a smectic liquid crystal, and its photopolymerized composite have been prepared. The fibers oriented along the smectic layers are obtained by self‐assembly of an amino acid derivative with terminal methacryloyl groups in the smectic liquid crystal. The oriented fibrous structures are fixed by photopolymerization, resulting in the formation of microgrooves on the substrate surfaces. The aligned direction of the liquid‐crystalline molecules is changed to the direction along the fibers after thermal annealing. The patterning of liquid‐crystal alignment is achieved for these liquid‐crystal composites by patterned photopolymerization.     

Fabrication of Multicomponent Microsystems by Directed Three‐Dimensional Self‐Assembly

We have developed a directed self‐assembly process for the fabrication of three‐dimensional (3D) microsystems that contain non‐identical parts and a statistical model that relates the process yield to the process parameters. The self‐assembly process uses geometric‐shape recognition to identify different components, and surface tension between liquid solder and metal‐coated areas to form mechanical and electrical connections. The concept is used to realize self‐packaging microsystems that contain non‐identical subunits. To enable the realization of microsystems that contain more than two non‐identical subunits, sequential self‐assembly is introduced, a process that is similar to the formation of heterodimers, heterotrimers, and higher aggregates found in nature, chemistry, and chemical biology. The self‐assembly of three‐component assemblies is demonstrated by sequentially adding device segments to the assembly solution including two hundred micrometer‐sized light‐emitting diodes (LEDs) and complementary metal oxide semiconductor (CMOS) integrated circuits. Six hundred AlGaInP/GaAs LED segments self‐assembled onto device carriers in two minutes, without defects, and encapsulation units self‐assembled onto the LED‐carrier assemblies to form a 3D circuit path to operate the final device. The self‐assembly process is a well‐defined statistical process. The process follows a first‐order, non‐linear differential equation. The presented model relates the progression of the self‐assembly and yield with the process parameters—component population and capture probability—that are defined by the agitation and the component design.     

Engineering Increased Stability into Self‐Assembled Protein Fibers

Two stages in the rational redesign of a peptide‐based, self‐assembling fiber (SAF) are described. The SAF system comprises two peptides designed to form an offset α‐helical coiled‐coil heterodimer. The “sticky‐ends” are complementary and promote longitudinal assembly. Alone, the two peptides are unstructured, but co‐assemble upon mixing to form α‐helical fibrils, which bundle to form fibers 40–50 nm wide and tens of micrometers long. Assembly is controllable and occurs at pH 7 in water, making SAFs a potential scaffold for 3D cell culture. The purposes of the redesigns were 1) to investigate the fiber‐thickening process, and 2) to increase fiber stability for potential biological and biomedical applications. First, mutations were made to the original peptide designs to increase fibril–fibril interactions and so produce thicker and more‐stable fibers. The second iteration aimed to increase the primary peptide–peptide interactions by increasing the overlap in the offset dimer and so promote the initial step in fiber formation. As judged by circular dichroism spectroscopy and transmission electron microscopy, both iterations improved fiber assembly and stability: the critical peptide concentration for assembly improved from 60 μM to 4 μM ; the midpoint of thermal unfolding increased from 22 °C to 65 °C; and the salt tolerance improved from 75 mM to greater than 250 mM KCl. These improvements bring closer applications of the SAF system under physiological conditions, for example as a biocompatible material for 3D cell culture. In addition, ordered surface features were observed in the second‐ and third‐generation fibers compared with the original design. This indicates improved internal order in the redesigned fibers. In turn, this suggests a molecular mechanism for the improved stability and sheds light on the fiber‐assembly process.     

Oriented Growth of Self‐Assembled Polyaniline Nanowire Arrays Using a Novel Method

A novel method for fabrication of highly oriented polyaniline (PANI) nanowires without removal of the template was developed by combining self‐assembly and template synthesis techniques. By using a self‐assembly process under inhibition conditions, oriented arrays of PANI nanowires growing out of the nanoporous template were obtained, with nanowire diameters ranging from 110 to 190 nm and lengths of several micrometers. The lengths of these wires can be roughly controlled by the polymerization time.     

Engineering of Self‐Assembled Domain Architectures with Ultra‐high Piezoelectric Response in Epitaxial Ferroelectric Films

Substrate clamping and inter‐domain pinning limit movement of non‐180° domain walls in ferroelectric epitaxial films thereby reducing the resulting piezoelectric response of ferroelectric layers. Our theoretical calculations and experimental studies of the epitaxial PbZr_xTi_1–xO₃ films grown on single crystal SrTiO₃ demonstrate that for film compositions near the morphotropic phase boundary it is possible to obtain mobile two‐domain architectures by selecting the appropriate substrate orientation. Transmission electron microscopy, X‐ray diffraction analysis, and piezoelectric force microscopy revealed that the PbZr_0.52Ti_0.48O₃ films grown on (101) SrTiO₃ substrates feature self‐assembled two‐domain structures, consisting of two tetragonal domain variants. For these films, the low‐field piezoelectric coefficient measured in the direction normal to the film surface (d₃₃) is 200 pm V^–1, which agrees well with the theoretical predictions. Under external AC electric fields of about 30 kV cm^–1, the (101) films exhibit reversible longitudinal strains as high as 0.35 %, which correspond to the effective piezoelectric coefficients in the order of 1000 pm V^–1 and can be explained by elastic softening of the PbZr_xTi_1–xO₃ ferroelectrics near the morphotropic phase boundary.     

Self‐Assembled Robust Dipeptide Nanotubes and Fabrication of Dipeptide‐Capped Gold Nanoparticles on the Surface of these Nanotubes

Three water‐soluble dipeptides containing N‐terminally located β‐alanine residue and C‐terminally located α‐amino acid residues (β‐Ala‐L ‐Xaa, Xaa = Val/Ile/Phe) form robust crystalline nanotubes. These dipeptide nanotubes contain a common motif, a hybrid of β,α‐amino acids, which are stable against heat up to 80 °C, a wide range of pH (2–10), and proteolytic degradation. These robust crystalline dipeptide nanotubes are used as a template for fabricating dipeptide‐capped gold nanoparticles on their outer surfaces. This is an easy way to develop nanotube/nanoparticle hybrid materials under mild conditions.     

Deep‐UV Photochemistry and Patterning of (Aminoethylaminomethyl)phenethylsiloxane Self‐Assembled Monolayers

The 193 nm photochemistry of (aminoethylaminomethyl)phenethylsiloxane (PEDA) self‐assembled monolayers (SAMs) under ambient conditions is described. The primary photodegradation pathways at low exposure doses (< 100 mJ cm^–2) are benzylic C–N bond cleavage (ca. 68 %), with oxidation of the benzyl C to the aldehyde, and Si–C bond cleavage (ca. 32 %). Amine‐containing photoproducts released from the SAM during exposure remain physisorbed on the surface, where they undergo secondary photolysis leading to their complete degradation and removal after ca. 1200 mJ cm^–2. NaCl(aq) post‐exposure rinsing removes the physisorbed materials, showing that degradation of the original PEDA species (leaving Si–OH) is substantially complete after ca. 450 mJ cm^–2. Consequently, patterned, rinsed PEDA SAMs function as efficient templates for fabrication of high‐resolution, negative‐tone, electroless metal and DNA features with good selectivity at low dose (i.e., ca. 400 mJ cm^–2) via materials grafting to the intact amines remaining in the unirradiated PEDA SAM regions.     

The Effect of Hydrogen Bonding on Self‐Assembled Polyaniline Nanostructures

Polyaniline (PANI) nanotubes with an outer diameter of 165–240 nm and an inner diameter of 10–70 nm were prepared by a self‐assembly process in the presence of six different carboxylic acids—propionic acid (PA), lactic acid (LA), succinic acid (SA), malic acid (MA), tartaric acid (TA), and citric acid (CA)—as the dopants. These nanotubes aggregated to form nanotube dendrites when the carboxylic acids contain an OH group. Moreover, the number of OH and COOH groups of the carboxylic acids affected the size, aggregated dendrite morphology, and thermal and electrical properties of the nanotubes. It was proposed that the micelle formed by the carboxylic acids acts as a template in the formation of the nanotubes, while the hydrogen bonds between the polymer chain of PANI and the OH group of the carboxylic acids supply a driving force to form the aggregated nanotube dendrites.     

Control of Specular and Diffuse Reflection of Light Using Particle Self‐Assembly at the Polymer and Metal Interface

We present a novel method of controlling the specular and diffuse reflection of light by the electrostatic deposition of a spherical particle monolayer followed by electroless plating. Charged polystyrene colloidal particles, ranging in size from 100 nm to 5 μm, were adsorbed from solution onto oppositely charged polyelectrolyte multilayers (PEM). The monodisperse particle monolayers were coated with nickel in a two‐step electroless plating process using palladium catalysts. These surfaces can be used as diffusive metal reflectors with a uniformly controlled surface roughness due to the uniform size of deposited particles. In addition, the self‐assembled particles at the polymer and metal interface deflected the internal stresses that build‐up at the interface while the metal was being deposited. This allowed a thicker metal film to be deposited before delamination occurred. A UV‐VIS spectrometer with movable fiber optic cables was employed to characterize the optical properties of the reflectors. The optical fibers permit versatile and precise measurements of specular and diffuse reflectance. By measuring the angular dependent reflectance, we demonstrate how to estimate the distribution of reflected light from the nickel coated surface and how to calculate the ratio of specular and diffuse reflection in the total reflected light. Optical measurements of our nickel samples showed that this approach could be used to control the portion of diffuse reflection from 8.25 to 59.97 %. Additionally, a quartz crystal microbalance was employed to study the electroless nickel plating rate on PEM. Our proposed method is simple, cost‐effective and convenient for mass production because the process consists of a series of simple immersion steps without vacuum technology or special equipment.     

The Effect of Nanoscale Confinement on the Collective Electron Transport Behavior in Au Nanoparticles Self‐Assembled in a Nanostructured Polystyrene‐block‐poly(4‐vinylpyridine) Diblock Copolymer Ultra‐thin Film

This study involves the collective electron transport behavior of sequestered Au nanoparticles in a nanostructured polystyrene‐block‐poly(4‐vinylpyridine). The monolayer thin films (ca. 30 nm) consisting of Au nanoparticles self‐assembled in the 30‐nm spherical poly(4‐vinylpyridine) domains of an polystyrene‐block‐poly(4‐vinylpyridine) diblock copolymer were prepared. From the current‐voltage characteristics of these thin films, the collective electron transport behavior of Au nanoparticles sequestered in the spherical poly(4‐vinylpyridine) nanodomains was found to be dictated by Coulomb blockade and was quasi one‐dimensional, as opposed to the three‐dimensional behavior displayed by Au nanoparticles that had been dispersed randomly in homo‐poly(4‐vinylpyridine). The threshold voltage of these composite increased linearly upon increasing the inter‐nanoparticle distance. The electron tunneling rate constant in the case of Au nanoparticles confined in poly(4‐vinylpyridine) nanodomains is eight times larger than that in the randomly distributed case and it increases upon increasing the amount of Au nanoparticles. This phenomenon indicates that manipulating the spatial arrangement of metal nanoparticles by diblock copolymer can potentially create electronic devices with higher performance.     

Self‐Assembled Complexes of Horseradish Peroxidase with Magnetic Nanoparticles Showing Enhanced Peroxidase Activity

Bio‐nanocatalysts (BNCs) consisting of horseradish peroxidase (HRP) self‐assembled with magnetic nanoparticles (MNPs) enhance enzymatic activity due to the faster turnover and lower inhibition of the enzyme. The size and magnetization of the MNPs affect the formation of the BNCs, and ultimately control the activity of the bound enzymes. Smaller MNPs form small clusters with a low affinity for the HRP. While the turnover for the bound fraction is drastically increased, there is no difference in the H₂O₂ inhibitory concentration. Larger MNPs with a higher magnetization aggregate in larger clusters and have a higher affinity for the enzyme and a lower substrate inhibition. All of the BNCs are more active than the free enzyme or the MNPs (BNCs > HRP ? MNPs). Since the BNCs show surprising resilience in various reaction conditions, they may pave the way towards new hybrid biocatalysts with increased activities and unique catalytic properties for magnetosensitive enzymatic reactions.     

Kirigami‐Inspired Self‐Assembly of 3D Structures

Self‐assembly of 3D structures presents an attractive and scalable route to realize reconfigurable and functionally capable mesoscale devices without human intervention. A common approach for achieving this is to utilize stimuli‐responsive folding of hinged structures, which requires the integration of different materials and/or geometric arrangements along the hinges. It is demonstrated that the inclusion of Kirigami cuts in planar, hingeless bilayer thin sheets can be used to produce complex 3D shapes in an on‐demand manner. Nonlinear finite element models are developed to elucidate the mechanics of shape morphing in bilayer thin sheets and verify the predictions through swelling experiments of planar, millimeter‐scaled PDMS (polydimethylsiloxane) bilayers in organic solvents. Building upon the mechanistic understandings, The transformation of Kirigami‐cut simple bilayers into 3D shapes such as letters from the Roman alphabet (to make “ADVANCED FUNCTIONAL MATERIALS”) and open/closed polyhedral architectures is experimentally demonstrated. A possible application of the bilayers as tether‐less optical metamaterials with dynamically tunable light transmission and reflection behaviors is also shown. As the proposed mechanistic design principles could be applied to a variety of materials, this research broadly contributes toward the development of smart, tetherless, and reconfigurable multifunctional systems.     

Non‐Close‐Packed Crystals from Self‐Assembled Polystyrene Spheres by Isotropic Plasma Etching: Adding Flexibility to Colloid Lithography

Hexagonally ordered arrays of non‐close‐packed nanoscaled spherical polystyrene (PS) particles are prepared exhibiting precisely controlled diameters and interparticle distances. For this purpose, a newly developed isotropic plasma etching process is applied to extended monolayers of PS colloids (starting diameters <300 nm) deposited onto hydrophilic silicon. Accurate size, shape, and smoothness control of such particles is accomplished by etching at low temperatures (?150 °C) with small rates not usually available in standard reactive ion etching equipment. The applicability of such PS arrays as masks for subsequent pattern transfer is demonstrated by fabricating arrays of cylindrical nanopores into Si.     

Seed‐Assisted Synthesis of BaCrO4 Nanoparticles and Nanostructures in Water‐in‐Oil Microemulsions

Isooctane dispersions of discrete isometric BaCrO₄ nanoparticles or self‐assembled linear chains of prismatic BaCrO₄ nanoparticles were added as surfactant‐coated seed crystals/nanostructures to Na₂CrO₄/NaAOT/Ba(AOT)₂/isooctane microemulsion reaction solutions prepared at w = 10 with molar ratios favoring the de novo synthesis of either nanoparticle chains ([Ba²⁺]/ [CrO₄^2–] = 1:1) or isolated nanoparticles ([Ba²⁺]/[CrO₄^2–] = 1:5.5). Addition of BaCrO₄ nanoparticles or chains under particle‐ or chain‐producing conditions, respectively, resulted in preferential growth of the seeds with retention of particle morphology and nanostructure architecture. In contrast, addition of linear chains to microemulsion reaction solutions under particle‐producing conditions resulted in disruption of the seed nanostructure and overgrowth of the released prismatic nanoparticles to produce discrete oval‐shaped or cuboidal nanocrystals depending on the seed concentration used. Discrete faceted nanoparticles were also produced by seed‐assisted synthesis when isometric nanoparticles were added at relatively high concentrations to chain‐producing microemulsion reaction solutions; however, decreasing the seed population resulted in intact self‐assembled linear chains and superlattices that consisted of interlinked prismatic nanoparticles with end‐capped pseudo‐hexagonal morphology. Growth of the seeds and their assembly/disassembly was consistent with a model of coupled synthesis and self‐organization based on the strength of electrostatic interactions at the surfactant‐crystal interface. The results suggest that microemulsion‐based processes could be of general importance for controlling the secondary growth of pre‐organized nanoparticle‐based superstructures, as well as the morphological refinement of their constituent building blocks.     

Random Lasing in Self‐Assembled Dye‐Doped Latex Nanoparticles: Packing Density Effects

Efficient random lasing (RL) from self‐assembled dye‐doped latex nanoparticles (d = 50–380 nm) presenting size polydispersity is reported. This new system exhibits a very good chemical compatibility between dye (Rhodamine 6G) and polymer as well as a high refractive index contrast between nanoparticle and surroundings (air), in such a way that its emission properties surpass the ones previously reported in similar systems. Furthermore, this system allows analyzing in detail the effects of the nanoparticle size polydispersity and the packing density on the RL emission properties. It is shown that size polydispersity gives rise to non‐uniformities in the filling fraction along the sample that lead to fluctuations on the scattering length across the sample and thus to a variation on the emission properties. Finally, it is observed that the increase of the filling fraction, enabled by the use of binary mixtures of nanoparticles with different sizes, results in remarkable improvements in the RL emission properties.     

Cover Picture: Fabrication of Multicomponent Microsystems by Directed Three‐Dimensional Self‐Assembly (Adv. Funct. Mater. 5/2005)

Directed three‐dimensional self‐assembly to assemble and package integrated semiconductor devices is demonstrated by Jacobs and Zheng on p. 732. The self‐assembly process uses geometrical shape recognition to identify different components and surface‐tension between liquid solder and metal‐coated areas to form mechanical and electrical connections.The components (top left) self‐assemble in a turbulent flow (center) and form functional multi‐component microsystems (bottom right) by sequentially adding parts to the assembly solution. The technique provides, for the first time, a route to enable the realization of three‐dimensional heterogeneous microsystems that contain non‐identical parts, and connecting them electrically. We have developed a directed self‐assembly process for the fabrication of three‐dimensional (3D) microsystems that contain non‐identical parts and a statistical model that relates the process yield to the process parameters. The self‐assembly process uses geometric‐shape recognition to identify different components, and surface tension between liquid solder and metal‐coated areas to form mechanical and electrical connections. The concept is used to realize self‐packaging microsystems that contain non‐identical subunits. To enable the realization of microsystems that contain more than two non‐identical subunits, sequential self‐assembly is introduced, a process that is similar to the formation of heterodimers, heterotrimers, and higher aggregates found in nature, chemistry, and chemical biology. The self‐assembly of three‐component assemblies is demonstrated by sequentially adding device segments to the assembly solution including two hundred micrometer‐sized light‐emitting diodes (LEDs) and complementary metal oxide semiconductor (CMOS) integrated circuits. Six hundred AlGaInP/GaAs LED segments self‐assembled onto device carriers in two minutes, without defects, and encapsulation units self‐assembled onto the LED‐carrier assemblies to form a 3D circuit path to operate the final device. The self‐assembly process is a well‐defined statistical process. The process follows a first‐order, non‐linear differential equation. The presented model relates the progression of the self‐assembly and yield with the process parameters—component population and capture probability—that are defined by the agitation and the component design.     

Self‐Assembled In‐Plane Growth of Mg2SiO4 Nanowires on Si Substrates Catalyzed by Au Nanoparticles

In‐plane growth of Mg₂SiO₄ nanowires on Si substrates is achieved by using a vapor transport method with Au nanoparticles as catalyst. The self‐assembly of the as‐grown nanowires shows dependence on the substrate orientation, i.e., they are along one, two, and three particular directions on Si (110), (100), and (111) substrates, respectively. Detailed electron microscopy studies suggest that the Si substrates participate in the formation of Mg₂SiO₄, and the epitaxial growth of the nanowires is confined along the Si <110> directions. This synthesis route is quite reliable, and the dimensions of the Mg₂SiO₄ nanowires can be well controlled by the experiment parameters. Furthermore, using these nanowires, a lithography‐free method is demonstrated to fabricate nanowalls on Si substrates by controlled chemical etching. The Au nanoparticle catalyzed in‐plane epitaxial growth of the Mg₂SiO₄ nanowires hinges on the intimate interactions between substrates, nanoparticles, and nanowires, and our study may help to advance the developments of novel nanomaterials and functional nanodevices.