Enabling the Selective Detection of Endocrine-Disrupting Chemicals via Molecularly Surface-Imprinted "Coffee Rings".

Molecularly imprinted polymers (MIPs) represent an intriguing class of synthetic materials that can selectively recognize and bind chemical or biological molecules in a variety of value-added applications in sensors, catalysis, drug delivery, antibodies, and receptors. In this context, many advanced methods of implementing functional MIP materials have been actively studied. Herein, we report a robust strategy to produce highly ordered arrays of surface-imprinted polymer patterns with unprecedented regularity for MIP-based sensor platform, which involves the controlled evaporative self-assembly process of MIP precursor solution in a confined geometry consisting of a spherical lens on a flat Si substrate (i.e., sphere-on-flat geometry) to synergistically utilize the "coffee-ring" effect and repetitive stick-slip motions of the three-phase contact line simply by solvent evaporation. Highly ordered arrays of the ring-patterned MIP films are then polymerized under UV irradiation to achieve semi-interpenetrating polymer networks. The extraction of templated target molecules from the surface-imprinted ring-patterned MIP films leaves behind copious cavities for the recognizable specific "memory sites" to efficiently detect small molecules. As a result, the elaborated surface structuring effect, sensitivity, and specific selectivity of the coffee-ring-based MIP sensors are scrutinized by capitalizing on an endocrine-disrupting chemical, 2,4-dichlorophenoxyacetic acid (2,4-D), as an example. Clearly, the evaporative self-assembly of nonvolatile solutes in a confined geometry renders the creation of familiar yet ordered coffee-ring-like patterns for a wide range of applications, including sensors, scaffolds for cell motility, templates, substrates for neuron guidance, etc., thereby dispensing with the need of multistep lithography techniques and external fields.

A Facile and Highly Efficient Route to Amphiphilic Star-Like Rod-Coil Block Copolymer via a Combination of Atom Transfer Radical Polymerization with Thiol-Ene Click Chemistry.

With a combination of atom transfer radical polymerization (ATRP), quasi-living Grignard metathesis method, and thiol-ene click reaction, an amphiphilic star-like rod-coil diblock copolymer poly(acrylic acid)-block-poly(3-hexylthiophene) comprising 21-arm inner coil-like PAA blocks and outer rod-like conjugated polymer poly(3-hexylthiophene) (P3HT) blocks with well-defined molecular structures and narrow molecular weight distribution is synthesized. First, the bromide end-groups of 21-arm star-like ATRP coil polymers PtBA-Br are converted successfully into reactive thioacetate end groups by post-functionalization using potassium thioacetate. Subsequently, 21-arm star-like coil polymers PtBA-SCOCH3 react with rod-like vinyl-functionalized P3HT to yield functional star-like rod-coil diblock copolymers PtBA-b-P3HT via thiol-ene click reaction, followed by selective hydrolysis of inner PtBA block into PAA block. The present synthetic approach enables the construction of well-defined star-like conformation with few structural limitations in a facile and highly efficient manner due to the robust and orthogonal nature of the thiol-ene click reaction. It may be extended to produce block copolymers with other topologies, such as cylindrical, hyperbranched, and dendritic structures.

Immobilization of Pt Nanoparticles via Rapid and Reusable Electropolymerization of Dopamine on TiO2 Nanotube Arrays for Reversible SERS Substrates and Nonenzymatic Glucose Sensors.

Inspired by mussel-adhesion phenomena in nature, polydopamine (PDA) coatings are a promising route to multifunctional platforms for decorating various materials. The typical self-polymerization process of dopamine is time-consuming and the coatings of PDA are not reusable. Herein, a reusable and time-saving strategy for the electrochemical polymerization of dopamine (EPD) is reported. The PDA layer is deposited on vertically aligned TiO2 nanotube arrays (NTAs). Owing to the abundant catechol and amine groups in the PDA layer, uniform Pt nanoparticles (NPs) are deposited onto the TiO2 NTAs and can effectively prevent the recombination of electron-hole pairs generated from photo-electrocatalysis and transfer the captured electrons to participate in the photo-electrocatalytic reaction process. Compared with pristine TiO2 NTAs, the as-prepared Pt@TiO2 NTA composites exhibit surface-enhanced Raman scattering sensitivity for detecting rhodamine 6G and display excellent UV-assisted self-cleaning ability, and also show promise as a nonenzymatic glucose biosensor. Furthermore, the mussel-inspired electropolymerization strategy and the fast EPD-reduced nanoparticle decorating process presented herein can be readily extended to various functional substrates, such as conductive glass, metallic oxides, and semiconductors. It is the adaptation of the established PDA system for a selective, robust, and generalizable sensing system that is the emphasis of this work.

Precisely Size-Tunable Monodisperse Hairy Plasmonic Nanoparticles via Amphiphilic Star-Like Block Copolymers.

In situ precision synthesis of monodisperse hairy plasmonic nanoparticles with tailored dimensions and compositions by capitalizing on amphiphilic star-like diblock copolymers as nanoreactors are reported. Such hairy plasmonic nanoparticles comprise uniform noble metal nanoparticles intimately and perpetually capped by hydrophobic polymer chains (i.e., "hairs") with even length. Interestingly, amphiphilic star-like diblock copolymer nanoreactors retain the spherical shape under reaction conditions, and the diameter of the resulting plasmonic nanoparticles and the thickness of polymer chains situated on the surface of the nanoparticle can be readily and precisely tailored. These hairy nanoparticles can be regarded as hard/soft core/shell nanoparticles. Notably, the polymer "hairs" are directly and permanently tethered to the noble metal nanoparticle surface, thereby preventing the aggregation of nanoparticles and rendering their dissolution in nonpolar solvents and the homogeneous distribution in polymer matrices with long-term stability. This amphiphilic star-like block copolymer nanoreactor-based strategy is viable and robust and conceptually enables the design and synthesis of a rich variety of hairy functional nanoparticles with new horizons for fundamental research on self-assembly and technological applications in plasmonics, catalysis, energy conversion and storage, bioimaging, and biosensors.

Flow-enabled self-assembly of large-scale aligned nanowires.

One-dimensional nanowires enable the realization of optical and electronic nanodevices that may find applications in energy conversion and storage systems. Herein, large-scale aligned DNA nanowires were crafted by flow-enabled self-assembly (FESA). The highly oriented and continuous DNA nanowires were then capitalized on either as a template to form metallic nanowires by exposing DNA nanowires that had been preloaded with metal salts to an oxygen plasma or as a scaffold to direct the positioning and alignment of metal nanoparticles and nanorods. The FESA strategy is simple and easy to implement and thus a promising new method for the low-cost synthesis of large-scale one-dimensional nanostructures for nanodevices.

An unconventional route to high-efficiency dye-sensitized solar cells via embedding graphitic thin films into TiO2 nanoparticle photoanode.

Graphitic thin films embedded with highly dispersed titanium dioxide (TiO(2)) nanoparticles were incorporated for the first time into the conventional dye-sensitized solar cells (DSSCs), resulting in a remarkably improved cell efficiency due to its superior electron conductivity. Massively ordered arrays of TiO(2) dots embedded in carbon matrix were fabricated via UV-stabilization of polystyrene-block-poly(4-vinylpyridine) films containing TiO(2) precursors followed by direct carbonization. For dye-sensitized TiO(2) based solar cells containing carbon/TiO(2) thin layers at both sides of pristine TiO(2) layer, an increase of 62.3% [corrected] in overall power conversion efficiency was achieved compared with neat TiO(2)-based DSSCs. Such a remarkably improved cell efficiency was ascribed to the superior electron conductivity and extended electron lifetime elucidated by cyclic voltammetry and impedance spectroscopy.

Large-scale hierarchically structured conjugated polymer assemblies with enhanced electrical conductivity.

Stripes on a plane: A set of highly ordered microscopic stripes (purple; see scheme) were produced over a large area by using controlled evaporative self-assembly in a cylinder-on-Si geometry of conjugated homopolymers or all-conjugated diblock copolymer (P3BHT). The crystallinity of the as-prepared assemblies of P3BHT was greatly improved following chloroform vapor annealing, resulting in a fourfold increase in electrical conductivity.

Learning from "coffee rings": ordered structures enabled by controlled evaporative self-assembly.

Research into the evaporation of solutions is not only aimed at a better understanding the physics of evaporation, but increasingly at capitalizing on the extremely simple method it offers to assemble diverse nonvolatile solutes into complex ordered structures on the submicron and longer length scales. This Review highlights recent advances in evaporative assembly of confined solutions, focusing especially on recently developed approaches that provide structures with unprecedented regularity composed of polymers, nanoparticles, and biomaterials, by controlled evaporation-driven, flow-aided self-assembly. A broad range of variables that can control the deposition are explored and the future directions of this rich field are presented.

A simple route to hierarchically assembled micelles and inorganic nanoparticles.

Earning their stripes: A hierarchical assembly of micelles composed of an amphiphilic diblock copolymer, poly(styrene)-block-poly(4-vinylpyridine) (PS-b-P4VP), were made by combining controlled evaporative self-assembly of the confined PS-b-P4VP toluene solution in a cylinder-on-Si geometry with spontaneous self-assembly of micelles. This method gave microscopic stripes of nanometer-sized PS-b-P4VP micelles within the stripes (see pictures).

pH-controlled assembly and properties of LbL membranes from branched conjugated poly(alkoxythiophene sulfonate) and various polycations.

We report on multilayer layer-by-layer (LbL) films of the conjugated polymer sodium poly[2-(3-thienyl)ethyloxy-4-butylsulfonate] (PTH) assembled with polycations: poly(diallyldimethylammonium chloride) (PDDA), 20% quaternized poly(N-ethyl-4-vinylpyridinium bromide) (Q20), poly(ethylene imine) (PEI), and poly(allylamine hydrochloride) (PAH). These films were prepared through spin-assisted LbL assembly under various pH conditions. We demonstrated a crucial role of the deposition pH in formation of PTH/polycation films and showed that decrease in the deposition pH from 7.5 to 2.5 limits the PTH multilayer formation to Q20/PTH and PDDA/PTH films due to reduced charge density in the poly(thiophene) chains. We show that optical and surface properties of the resulting PTH/polycation films can be tuned by varying a polycation component and/or by varying the deposition pH. The fluorescence properties of the Q20/PTH, PEI/PTH, and PDDA/PTH films are pH-dependent, and the films exhibit the drastic changes in photoluminescent intensity when transferred into solutions with different pH values, which may find useful in optical sensing applications.

Friction and wear behavior of ultra-high molecular weight polyethylene as a function of polymer crystallinity.

In this study the friction, wear and surface mechanical behavior of medical-grade ultra-high molecular weight polyethylene (UHMWPE) (GUR 1050 resin) were evaluated as a function of polymer crystallinity. Crystallinity was controlled by heating UHMWPE to a temperature above its melting point and varying the hold time and cooling rates. The degree of crystallinity of the samples was evaluated using differential scanning calorimetry (DSC). A higher degree of crystallinity in the UHMWPE resulted in lower friction force and an increase in scratch resistance at the micro- and nanoscales. On the nanoscale, the lamellar structure appeared to affect the observed wear resistance. Reciprocating-wear tests performed using a microtribometer showed that an increase in crystallinity also resulted in lower wear depth and width. Nanoindentation experiments also showed an increase in hardness values with an increase in sample crystallinity.

A general and robust strategy for the synthesis of nearly monodisperse colloidal nanocrystals.

Colloidal nanocrystals exhibit a wide range of size- and shape-dependent properties and have found application in myriad fields, incuding optics, electronics, mechanics, drug delivery and catalysis, to name but a few. Synthetic protocols that enable the simple and convenient production of colloidal nanocrystals with controlled size, shape and composition are therefore of key general importance. Current strategies include organic solution-phase synthesis, thermolysis of organometallic precursors, sol-gel processes, hydrothermal reactions and biomimetic and dendrimer templating. Often, however, these procedures require stringent experimental conditions, are difficult to generalize, or necessitate tedious multistep reactions and purification. Recently, linear amphiphilic block co-polymer micelles have been used as templates to synthesize functional nanocrystals, but the thermodynamic instability of these micelles limits the scope of this approach. Here, we report a general strategy for crafting a large variety of functional nanocrystals with precisely controlled dimensions, compositions and architectures by using star-like block co-polymers as nanoreactors. This new class of co-polymers forms unimolecular micelles that are structurally stable, therefore overcoming the intrinsic instability of linear block co-polymer micelles. Our approach enables the facile synthesis of organic solvent- and water-soluble nearly monodisperse nanocrystals with desired composition and architecture, including core-shell and hollow nanostructures. We demonstrate the generality of our approach by describing, as examples, the synthesis of various sizes and architectures of metallic, ferroelectric, magnetic, semiconductor and luminescent colloidal nanocrystals.

Crafting semiconductor organic-inorganic nanocomposites via placing conjugated polymers in intimate contact with nanocrystals for hybrid solar cells.

Semiconductor organic-inorganic hybrid solar cells incorporating conjugated polymers (CPs) and nanocrystals (NCs) offer the potential to deliver efficient energy conversion with low-cost fabrication. The CP-based photovoltaic devices are complimented by an extensive set of advantageous characteristics from CPs and NCs, such as lightweight, flexibility, and solution-processability of CPs, combined with high electron mobility and size-dependent optical properties of NCs. Recent research has witnessed rapid advances in an emerging field of directly tethering CPs on the NC surface to yield an intimately contacted CP-NC nanocomposite possessing a well-defined interface that markedly promotes the dispersion of NCs within the CP matrix, facilitates the photoinduced charge transfer between these two semiconductor components, and provides an effective platform for studying the interfacial charge separation and transport. In this Review, we aim to highlight the recent developments in CP-NC nanocomposite materials, critically examine the viable preparative strategies geared to craft intimate CP-NC nanocomposites and their photovoltaic performance in hybrid solar cells, and finally provide an outlook for future directions of this extraordinarily rich field.

Synthesis of a novel photopolymerized nanocomposite hydrogel for treatment of acute mechanical damage to cartilage.

Intra-articular fractures initiate a cascade of pathobiological and pathomechanical events that culminate in post-traumatic osteoarthritis (PTOA). Hallmark features of PTOA include destruction of the cartilage matrix in combination with loss of chondrocytes and acute mechanical damage (AMD). Currently, treatment of intra-articular fractures essentially focuses completely on restoration of the macroanatomy of the joint. However, current treatment ignores AMD sustained by cartilage at the time of injury. We are exploring aggressive biomaterial-based interventions designed to treat the primary pathological components of AMD. This study describes the development of a novel injectable co-polymer solution that forms a gel at physiological temperatures that can be photocrosslinked, and can form a nanocomposite gel in situ through mineralization. The injectable co-polymer solution will allow the material to fill cracks in the cartilage after trauma. The mechanical properties of the nanocomposite are similar to those of native cartilage, as measured by compressive and shear testing. It thereby has the potential to mechanically stabilize and restore local structural integrity to acutely injured cartilage. Additionally, in situ mineralization ensures good adhesion between the biomaterial and cartilage at the interface, as measured through tensile and shear testing. Thus we have successfully developed a new injectable co-polymer which forms a nanocomposite in situ with mechanical properties similar to those of native cartilage, and which can bond well to native cartilage. This material has the potential to stabilize injured cartilage and prevent PTOA.

Friction and wear behavior of ultrahigh molecular weight polyethylene as a function of crystallinity in the presence of the phospholipid dipalmitoyl phosphatidylcholine.

In this study, the friction and wear behavior of ultrahigh molecular weight polyethylene (UHMWPE) were evaluated as a function of polymer crystallinity in the presence of the phospholipid dipalmitoyl phosphatidylcholine (DPPC) dissolved in ethanol. Samples of UHMWPE were separately heat treated to get high and low crystallinity samples. Degree of crystallinity was evaluated using differential scanning calorimetry. Quantitative friction and wear experiments were conducted using a custom-made microtribometer with commercially available spherical Si(3)N(4) probes in controlled and phospholipid-dissolved lubricants. The higher crystallinity sample exhibited slightly lower friction than the lower crystallinity in the control and decreased significantly when phospholipids were present. The higher crystallinity sample showed a higher wear resistance than the lower crystallinity sample during all reciprocating wear tests. DPPC acting as a lubricant had a marginal effect on the wear resistance of high crystallinity UHMWPE, whereas the low crystallinity sample became more prone to wear. Atomic force microscopy topography images and contact angle measurements of both samples before and after phospholipid exposure indicate that the higher crystallinity sample absorbed a greater density of DPPC. Increasing crystallinity is a way of escalating adsorption of surface active phospholipids onto UHMWPE to make it a more wear-resistant load-bearing material for total joint replacements.

Substrate- and time-dependent photoluminescence of quantum dots inside the ultrathin polymer LbL film.

The photoluminescence of CdSe/ZnS quantum dots (QDs) in different configurations at solid surfaces (glass, silicon, PDMS, and metals) is considered for three types of organization: QDs directly adsorbed on solid surfaces, separated from the solid surface by a nanoscale polymer film with different thickness, and encapsulated into a polymer film. The complete suppression of photoluminescence for QDs on conductive metal surfaces (copper, gold) indicated a strong quenching effect. The temporal variation of the photoluminescent intensity on other substrates (glass, silicon, and PDMS) can be tuned by placing the nanoscale (3-50 nm) LbL polymer film between QDs and the substrate. The photooxidation and photobleaching processes of QD nanoparticles in the vicinity of the solid surface can be tuned by proper selection of the substrate and the dielectric nanoscale polymer film placed between the substrate and QDs. Moreover, the encapsulation of QD nanoparticles into the polymer film resulted in a dramatic initial increase in the photoemission intensity due to the accelerated photooxidation process. The phenomenon of enhanced photoemission of QDs encapsulated into the ultrathin polymer film provides not only the opportunity for making flexible, ultrathin, QD-containing polymer films, transferable to any microfabricated substrate, but also improved light emitting properties.

Hierarchical structure formation and pattern replication induced by an electric field.

Several techniques based on soft lithography have emerged to replicate micrometre-sized patterns. Similar to most other lithographic methods, these techniques structure a single layer of photo resist. For many applications, however, it is desirable to control the spatial arrangement of more than one component. With traditional methods, this requires an iterative, multistep procedure, making the replication process more complex and less reliable. Here, a replication process is described where multiple materials are processed simultaneously. Using a bilayer formed by two different polymers, electrohydrodynamic instabilities at both polymer surfaces produce a hierarchic lateral structure that exhibits two independent characteristic dimensions. A lateral modulation of the electric field enables replication with a resolution down to 100 nanometres. This approach might provide a simple strategy for large-area, sub-100-nanometre lithography.