The major strategies for designing surfaces that prevent fouling due to proteins, bacteria, and marine organisms are reviewed. Biofouling is of great concern in numerous applications ranging from biosensors to biomedical implants and devices, and from food packaging to industrial and marine equipment. The two major approaches to combat surface fouling are based on either preventing biofoulants from attaching or degrading them. One of the key strategies for imparting adhesion resistance involves the functionalization of surfaces with poly(ethylene glycol) (PEG) or oligo(ethylene glycol). Several alternatives to PEG-based coatings have also been designed over the past decade. While protein-resistant coatings may also resist bacterial attachment and subsequent biofilm formation, in order to overcome the fouling-mediated risk of bacterial infection it is highly desirable to design coatings that are bactericidal. Traditional techniques involve the design of coatings that release biocidal agents, including antibiotics, quaternary ammonium salts (QAS), and silver, into the surrounding aqueous environment. However, the emergence of antibiotic- and silver-resistant pathogenic strains has necessitated the development of alternative strategies. Therefore, other techniques based on the use of polycations, enzymes, nanomaterials, and photoactive agents are being investigated. With regard to marine antifouling coatings, restrictions on the use of biocide-releasing coatings have made the generation of nontoxic antifouling surfaces more important. While considerable progress has been made in the design of antifouling coatings, ongoing research in this area should result in the development of even better antifouling materials in the future.

https://onlinelibrary.wiley.com/doi/pdf/10.1002/adma.201001215

Antifouling coatings: recent developments in the design of surfaces that prevent fouling by proteins, bacteria, and marine organisms.

Flexible pressure sensors are essential parts of an electronic skin to allow future biomedical prostheses and robots to naturally interact with humans and the environment. Mobile biomonitoring in long-term medical diagnostics is another attractive application for these sensors. Here we report the fabrication of flexible pressure-sensitive organic thin film transistors with a maximum sensitivity of 8.4 kPa(-1), a fast response time of 15,000 cycles and a low power consumption of <1 mW. The combination of a microstructured polydimethylsiloxane dielectric and the high-mobility semiconducting polyisoindigobithiophene-siloxane in a monolithic transistor design enabled us to operate the devices in the subthreshold regime, where the capacitance change upon compression of the dielectric is strongly amplified. We demonstrate that our sensors can be used for non-invasive, high fidelity, continuous radial artery pulse wave monitoring, which may lead to the use of flexible pressure sensors in mobile health monitoring and remote diagnostics in cardiovascular medicine.

/pdf/flexible-polymer-transistors-with-high-pressure-sensitivity-3nuszplute.pdf

Flexible polymer transistors with high pressure sensitivity for application in electronic skin and health monitoring

Dingcai Wu,*,† Fei Xu,† Bin Sun,† Ruowen Fu,† Hongkun He,‡ and Krzysztof Matyjaszewski*,‡ †Materials Science Institute, Key Laboratory for Polymeric Composite and Functional Materials of Ministry of Education, School of Chemistry and Chemical Engineering, Sun Yat-sen University, Guangzhou 510275, People's Republic of China ‡Department of Chemistry, Carnegie Mellon University, 4400 Fifth Avenue, Pittsburgh, Pennsylvania 15213, United States

Design and Preparation of Porous Polymers

A mean-field phase diagram for conformationally symmetric diblock melts using the standard Gaussian polymer model is presented. Our calculation, which traverses the weak- to strong-segregation regimes, is free of traditional approximations. Regions of stability are determined for disordered (DIS) melts and for ordered structures including lamellae (L), hexagonally packed cylinders (H), body-centered cubic spheres (QIm3m), close-packed spheres (CPS), and the bicontinuous cubic network with Ia3d symmetry (QIa3d). The CPS phase exists in narrow regions along the order−disorder transition for χN ≥ 17.67. Results suggest that the QIa3d phase is not stable above χN ∼ 60. Along the L/QIa3d phase boundaries, a hexagonally perforated lamellar (HPL) phase is found to be nearly stable. Our results for the bicontinuous Pn3m cubic (QPn3m) phase, known as the OBDD, indicate that it is an unstable structure in diblock melts. Earlier approximation schemes used to examine mean-field behavior are reviewed, and compa...

Unifying Weak- and Strong-Segregation Block Copolymer Theories

Small Angle Scattering of X-Rays

The grazing incidence small-angle X-ray scattering (GISAXS) from structures within a thin film on a substrate is generally a superposition of the two scatterings generated by the two X-ray beams (reflected and transmitted beams) converging on the film with a difference of twice the incidence angle (αi) of the X-ray beam in their angular directions; these two scatterings may overlap or may be distinct, depending on αi. The two scatterings are further distorted by the effects of refraction. These reflection and refraction effects mean that GISAXS is complicated to analyze. To quantitatively analyze GISAXS patterns, in this study we derived a GISAXS formula under the distorted wave Born approximation. We applied this formula to the quantitative analysis of the GISAXS patterns obtained for various compositions of polystyrene-b-polyisoprene (PS-b-PI) diblock copolymer thin films on silicon substrates with native oxide layers. This analysis showed that the diblock copolymer thin films consist of hexagonally pac...

Structural Analysis of Block Copolymer Thin Films with Grazing Incidence Small-Angle X-ray Scattering

Surfaces with physicochemical properties that can be modulated using external stimuli offer great promise for designing responsive or adaptive materials. Here, we describe biocompatible dynamic scaffolds based on thin hydrogel coatings that reversibly hide and display surface chemical patterns in response to temperature changes. At room temperature, the gel absorbs water, triggering an elastic creasing instability that sequesters functionalized regions within tight folds in the surface. Deswelling at approximately 37 degrees C causes the gel surface to unfold, thereby regenerating the biomolecular patterns. Crease positions are directed by topographic features on the underlying substrate, and are translated into two-dimensional micrometre-scale surface chemical patterns through selective deposition of biochemically functionalized polyelectrolytes. We demonstrate specific applications of these dynamic scaffolds--selective capture, sequestration and release of micrometre-sized beads, tunable activity of surface-immobilized enzymes and reversible encapsulation of adherent cells--which offer promise for incorporation within lab-on-a-chip devices or as dynamic substrates for cellular biology.

Dynamic display of biomolecular patterns through an elastic creasing instability of stimuli-responsive hydrogels

Integrated circuits that have improved functionality and speed in a smaller package and that consume less power are desired by the microelectronics industry as well as by end users, to increase device performance and reduce costs1,2,3,4. The fabrication of high-performance integrated circuits requires the availability of materials with low or ultralow dielectric constant (low-k: k ≤ 2.5; ultralow-k: k ≤ 2.0) because such dielectrics not only lower line-to-line noise in interconnect conductors, but also minimize power dissipation by reducing the capacitance between the interconnects1,2,3,4. Here we describe the preparation of low- and ultralow-k nanoporous organosilicate dielectrics from blends of polymethylsilsesquioxane (PMSSQ) precursor with globular ethyl acrylate-terminated polypropylenimine dendrimers, which act as porogens. These dendrimers are found to mix well with the PMSSQ precursor and after their sacrificial thermal decompositions result in closed, spherical pores of <2.0 nm radius with a very narrow distribution even at high loading. This pore size and distribution are the smallest and the narrowest respectively ever achieved in porous spin-on dielectrics. The method therefore successfully delivers low- and ultralow-k PMSSQ dielectric films that should prove very useful in advanced integrated circuits.

Ultralow- k nanoporous organosilicate dielectric films imprinted with dendritic spheres

We introduce a nanoporous membrane suitable for virus filtration with good dimensional stability under high pressures maintaining high selectivity. The membrane consists of a double layer: The upper layer is a nanoporous film with pore size of ∼17 nm and a thickness of ∼160 nm, which was prepared by polystyrene-block-poly(methyl methacrylate) copolymer (PS-b-PMMA) where PMMA block was removed by ultraviolet irradiation followed by rinsing with acetic acid. The nanoporous block copolymer film was combined with a conventional micro-filtration membrane to enhance mechanical strength. The membrane employed in this study did not show any damage or crack even at a pressure of 2 bar, while high selectivity was maintained for the filtration of human rhinovirus type 14 which has a diameter of ∼30 nm and is a major pathogen of the common cold in humans. Furthermore, due to crosslinked PS matrix during the UV irradiation, the nanoporous membrane showed excellent resistance to all organic solvents. This could be used under harsh filtration conditions such as high temperature and strong acidic (or basic) solution.

Virus Filtration Membranes Prepared from Nanoporous Block Copolymers with Good Dimensional Stability under High Pressures and Excellent Solvent Resistance

Thin poly(N-isopropylacrylamide) (PNIPAM) hydrogels were allowed to swell under two conditions: as freestanding layers and as substrate-attached layers. Through a combination of particle tracking and defocusing methods, the positions of beads embedded within the gels were monitored over time via fluorescence microscopy, providing a convenient method to track the kinetics of swelling for layers with thicknesses of the order 100 µm. These data are compared with the predictions of linear poroelastic theory, as specialized for polymer gels. This theory, along with a single set of material properties, accurately describes the observed swelling kinetics for both the freestanding and substrate-attached hydrogels. With the additional measurement of the substrate curvature induced by the swelling of the substrate-attached hydrogels, these experiments provide a simple route to completely characterize the material properties of the gel within the framework of linear poroelasticity, using only an optical microscope.

Jinhwan Yoon

Papers

Structural Analysis of Block Copolymer Thin Films with Grazing Incidence Small-Angle X-ray Scattering

Dynamic display of biomolecular patterns through an elastic creasing instability of stimuli-responsive hydrogels

Ultralow- k nanoporous organosilicate dielectric films imprinted with dendritic spheres

Virus Filtration Membranes Prepared from Nanoporous Block Copolymers with Good Dimensional Stability under High Pressures and Excellent Solvent Resistance

Poroelastic swelling kinetics of thin hydrogel layers: comparison of theory and experiment