Segmental dynamics of polystyrene near polymer-polymer interfaces.

This study investigated the segmental dynamics of polymers near polymer-polymer interfaces by probing the rotation of polymer-tethered fluorescent molecules using imaging rotational fluorescence correlation microscopy. Multilayered films were utilized to provide spatial selectivity relative to different polymer-polymer interfaces. In the experimental setup, for the overlayer polymer, polystyrene (PS) was employed and a 15 nm-thick probe-containing layer was placed ≈25 nm apart from different underlayer polymers with glass transition temperatures (Tg) either lower or higher than that of PS. The underlayer of poly-n-butyl methacrylate had 72 K lower Tg than that of PS, whereas polymethyl methacrylate and polysulfone had 22 and 81 K higher Tg, respectively, than that of PS. Two key dynamic features of the glass transition, the non-Arrhenius temperature dependence and stretched relaxation, were examined to study the influence of soft and hard confinements on the segmental dynamics of the overlayer polymer near the polymer-polymer interfaces. Although complications exist in the probing location owing to the diffusion of the polymer-tethered probe during the annealing protocol to consolidate the multilayers, the results suggest that either the segmental dynamics of the polymer near the polymer-polymer interface do not change owing to the soft and hard confinements or the interfacial perturbation is very short ranged.

Rational Process Design for Facile Fabrication of Dual Functional Hybrid Membrane of MOF and Electrospun Nanofiber towards High Removal Efficiency of PM2.5 and Toxic Gases.

The application of nanofiber (NF) and porous metal-organic framework (MOF) has increasingly attracted attention for the protection of public health. This composite platform provides the physical sieving of particulate matters (PMs) and capturing gases, serving as an outstanding filtering medium with lightweight and multifunctionality. Herein, process design and optimization are performed to produce a multifunctional membrane comprised NFs and MOF particles. Electrospinning/electrospray techniques are used to fabricate a hybrid membrane of poly(vinyl alcohol) NF and Fe-BTC as an adsorptive MOF on a macroporous nonwoven (NW). Three types of filters are prepared by varying the order of processing steps, that is, MOF/NF/NW, MOF+NF/NW, and NF/MOF/NW, to elucidate the effect of the fabrication process in the filtration of air pollutant. The optimal filtration performance is achieved in MOF+NF/NW system: the highest filtration efficiency (97%) and outstanding gas capturing efficiencies (≈60% and ≈35% decreases from initial NH3 and H2 S concentrations, respectively). However, when air permeability and filtration efficiency are considered, the most desirable configuration for personal protection equipment (PPE) is NF/MOF/NW system, which effectively enabled comfortable breathing without compromising the lightweight and multifunctional performance.

In Situ Vapor-Phase Halide Exchange of Patterned Perovskite Thin Films.

Metal halide perovskites (MHPs) exhibit optoelectronic properties that are dependent on their ionic composition, and the feasible exploitation of these properties for device applications requires the ability to control the ionic composition integrated with the patterning process. Herein, the halide exchange process of MHP thin films directly combined with the patterning process via a vapor transport method is demonstrated. Specifically, the patterned arrays of CH3 NH3 PbBr3 (MAPbBr3 ) are obtained by stepwise conversion from polymer-templated PbI2 thin films to CH3 NH3 PbI3 (MAPbI3 ), followed by halide exchange via precursor switching from CH3 NH3 I to CH3 NH3 Br. It is confirmed that the phase transformation from MAPbI3 patterns to MAPbBr3 shows time- and position-dependences on the substrate during halide exchange following the solid-solution model with Avrami kinetics. The photodetectors fabricated from the completely exchanged MAPbBr3 patterns display exceptional air stability and reversible detectivity from "apparent death" upon removing the adsorbed impurities, thereby suggesting the superior structural stability of perovskite patterns prepared through vapor-phase halide exchange. The results demonstrate the potential of chemical vapor deposition patterning of MHP materials in multicomponent optoelectronic device systems.

Photoinduced Modulation of Polymeric Interfacial Behavior Controlling Thin-Film Block Copolymer Wetting.

The tunable surface-wetting properties of photosensitive random copolymer mats were used to spatially control the orientations of thin-film block copolymer (BCP) structures. A photosensitive mat was produced via thermal treatment on spin-coated random copolymers of poly(styrene-ran-2-nitrobenzyl methacrylate-ran-glycidyl methacrylate), synthesized via reversible-deactivation radical polymerization. The degree of UV-induced deprotection of the nitrobenzyl esters in the mat was precisely controlled through the amount of UV-irradiation energy imparted to the mat. The resulting polarity switching of the constituents collectively altered the interfacial wetting properties of the mat, and the tunability allowed lamellar or cylinder-forming poly(styrene-b-methyl methacrylate) BCP thin films, applied over the mat, to change the domain orientation from perpendicular to parallel at proper UV exposures. UV irradiation passing through a photomask was capable of generating defined regions of BCP domains with targeted orientations.

Segmental dynamics of polymer by rotational fluorescence correlation microscopy.

The segmental dynamics of polymers is known to be closely related to the glass transition where the glass transition is the single most important parameter in its application. In this study, we designed an efficient and reliable experimental method to study the ensemble segmental dynamics of polymers by probing rotation of fluorescent molecules in the polymer matrix using a home-built microscope setup. The rotational dynamics of fluorescent molecules was analyzed using a fluorescence correlation method that extracts information through orthogonally polarized fluorescence images. From fluorescence intensities, autocorrelation functions (ACFs) were obtained in many areas simultaneously and by averaging several ACFs, well-defined ACF and precise experimental values were obtained from a single measurement movie. The robustness of the method and optimal experimental conditions were investigated by performing experiments with various probe concentrations, frame rates, and measurement lengths. By employing a home-built vacuum chamber, a wide temperature range was achieved, and we demonstrate the versatility and efficiency of imaging rotational FCM (fluorescence correlation microscopy) by probing segmental dynamics of different polymeric systems with glass transition temperature that differ by ≈100 K and with fragility ranging from 49 to 131. The imaging rotational FCM covers dynamics up to 4 orders of magnitude near the glass transition, and it was found that the rapidity of the stretching exponent ß variation with temperature correlates with the fragility of polymers.

Orientation of a monolayer of dipolar molecules on graphene from X-ray absorption spectroscopy.

Recently, single-walled carbon nanotubes as well as graphene functionalized with azobenzene chromophores have drawn attention for applications in optoelectronics due to their ability to undergo cis-trans isomerization when exposed to light. The electronic properties of the nanocarbon materials at these unconventional interfaces can be tailored by gaining structural insight into the organic monolayers at the molecular level. In this work, we use polarization-dependent X-ray absorption spectroscopy to probe the orientation of three chromophores on graphene, all identical except for their terminal groups. All three terminal groups (methyl, nitro, and nitrile) are well-oriented, with a tilt angle of about 30° from the substrate for the shared azobenzene group. Density functional theory calculations are in good agreement with experimental results and give two similar, stable configurations for the orientation of these molecules on graphene.

Chemical Structure-Physicochemical Property Relationships of Copolymers Utilizable for Negative-Tone Photoimaging via Chemical Amplification.

We demonstrate an understanding of different physicochemical properties of copolymers induced by systematic changes in their structural parameters, i.e., the chemical structure of the comonomer unit, composition, molecular weight, and dispersity. The terpolymers were designed to be implemented in a chemically amplified resist (CAR) to form negative-tone patterns. With two basic repeating units of 4-hydroxystyrene and 2-ethyl-2-methacryloxyadamantane as monomers for conventional CARs, the pendant group of the third methacrylate comonomer was varied from aromatic, aliphatic lactone to lactone rings to modulate the interaction capability of the copolymer chains with n-butyl acetate, which is a negative-tone developer. Along with these structures, the monomer composition, molecular weight, and dispersity were also controlled. Physicochemical properties of the synthesized copolymers having controlled structures, i.e., dissolution behaviors and quantified Hansen solubility parameters, surface wetting characteristics, and surface roughness, which can be important properties affecting patterning capability in high-resolution lithography, were explored. Furthermore, the feasibility to use experimentally determined Hansen solubility parameters of the copolymers for the prediction of pattern formation using a coarse-grained model was assessed. Our comprehensive studies on the correlation of the structural parameters of the copolymers with final properties offer fundamental avenues to attain effective designs of the complex CAR system toward the lithographic process to achieve a sub-10 nm dimension, which is close to a single-chain dimension.

A single-component inimer containing cross-linkable ultrathin polymer coating for dense polymer brush growth.

We have developed a highly versatile universal approach to grow polymer brushes from a variety of substrates with high grafting density by using a single-component system. We describe a random copolymer which consists of an inimer, p-(2-bromoisobutyloylmethyl)styrene (BiBMS), copolymerized with glycidyl methacrylate (GMA) synthesized by reversible addition-fragmentation chain-transfer (RAFT) polymerization. Thermal cross-linking created a mat that was stable during long exposure in organic solvent even with sonication or during Soxhlet extraction. The absolute bromine density was determined via X-ray photoelectron spectroscopy (XPS) to be 1.86 ± 0.12 Br atoms/nm(3). The ratio of experimental density to calculated absolute initiator density suggests that ~25% of the bromine is lost during cross-linking. Surface-initiated ATRP (SI-ATRP) was used to grow PMMA brushes on the substrate with sacrificial initiator in solution. The brushes were characterized by ellipsometry, XPS, and atomic force microscopy (AFM) to determine thickness, composition, and homogeneity. By correlating the molecular weight of polymer grown in solution with the brush layer thickness, a high grafting density of 0.80 ± 0.06 chains/nm(2) was calculated. By synthesizing the copolymer before cross-linking on the substrate, this single-component approach avoids any issues with blend miscibility as might be present for a multicomponent curable mixture, while resulting in high chain density on a range of substrates.

A dual functional layer for block copolymer self-assembly and the growth of nanopatterned polymer brushes.

We present a versatile method for fabricating nanopatterned polymer brushes using a cross-linked thin film made from a random copolymer consisting of an inimer (p-(2-bromoisobutyloylmethyl)styrene), styrene, and glycidyl methacrylate (GMA). The amount of inimer was held constant at 20 or 30% while the relative amount of styrene to GMA was varied to induce perpendicular domain orientation in an overlying P(S-b-MMA) block copolymer (BCP) film for lamellar and cylindrical morphologies. A cylinder forming BCP blend with PMMA homopolymer was assembled to create a perpendicular hexagonal array of cylinders, which allowed access to a nanoporous template without the loss of initiator functionality. Surface-initiated ATRP of 2-hydroxyethyl methacrylate was conducted through the pores to generate a dense array of nanopatterned brushes. Alternatively, gold was deposited into the nanopores, and brushes were grown around the dots after removal of the template. This is the first example of combining the chemistry of nonpreferential surfaces with surface-initiated growth of polymer chains.

Light-driven reversible modulation of doping in graphene.

We report a route to noncovalently latch dipolar molecules on graphene to create stable chromophore/graphene hybrids where molecular transformation can be used as an additional handle to reversibly modulate doping while retaining high mobilities. A light switchable azobenzene chromophore was tethered to the surface of graphene via π-π interactions, leading to p-doping of graphene with an hole concentration of ~5 × 10(12) cm(-2). As the molecules switch reversibly from trans to cis form the dipole moment changes, and hence the extent of doping, resulting in the modulation of hole concentration up to ~18% by alternative illumination of UV and white light. Light-driven conductance modulation and control experiments under vacuum clearly attribute the doping modulation to molecular transformations in the organic molecules. With improved sensitivities these "light-gated" transistors open up new ways to enable optical interconnects.

Polymer segmental dynamics near the interface of silica particles in the particle/polymer composites.

We demonstrate an approach to examine the local segmental dynamics of a polymer near the interface of an inorganic filler by observing the rotational dynamics of the fluorescent probe at the chain ends of polymer brushes grafted onto the surface of the filler particles. Localization of the fluorescent probe was realized by designing and synthesizing fluorophore-tethered polystyrene (PS) brushes anchored on the surface of silica particles of controlled sizes. Fluorophore-functionalized telechelic PS with an azide functionality at the other chain end was achieved via a combination of atom transfer radical polymerization and post-polymerization modification. The azide-bearing PS chains were tethered to alkyne-functionalized particles via copper-catalyzed cycloaddition reaction. The molecular weight of the grafted polymer chains was controlled to be less than the critical entanglement molecular weight, and the chain density was controlled to be low enough so that the observed dynamics was not perturbed by the polymer brush conformation and brush-matrix polymer entanglement. The polymer dynamics near the surface of the particles at low concentrations was closely examined in the bulk film geometry by employing imaging rotational fluorescence correlation microscopy (irFCM). The observed polymer dynamics near the interface were not altered in the inorganic/polymer composite geometry when the surface did not have favorable interaction with the matrix polymer. The presented rational design of the chemical route and examination of local dynamics highlight a feasible approach to construct material systems with high complexities towards a deeper understanding of composite materials.

Coarse-Grained Modeling of EUV Patterning Process Reflecting Photochemical Reactions and Chain Conformations.

Enabling extreme ultraviolet lithography (EUVL) as a viable and efficient sub-10 nm patterning tool requires addressing the critical issue of reducing line edge roughness (LER). Stochastic effects from random and local variability in photon distribution and photochemical reactions have been considered the primary cause of LER. However, polymer chain conformation has recently attracted attention as an additional factor influencing LER, necessitating detailed computational studies with explicit chain representation and photon distribution to overcome the existing approach based on continuum models and random variables. We developed a coarse-grained molecular simulation model for an EUV patterning process to investigate the effect of chain conformation variation and stochastic effects via photon shot noise and acid diffusion on the roughness of the pattern. Our molecular simulation demonstrated that final LER is most sensitive to the variation in photon distributions, while material distributions and acid diffusion rate also impact LER; thus, the intrinsic limit of LER is expected even at extremely suppressed stochastic effects. Furthermore, we proposed and tested a novel approach to improve the roughness by controlling the initial polymer chain orientation.

Biodegradable Nanofiber/Metal-Organic Framework/Cotton Air Filtration Membranes Enabling Simultaneous Removal of Toxic Gases and Particulate Matter.

The typical filters that protect us from harmful components, such as toxic gases and particulate matter (PM), are made from petroleum-based materials, which need to be replaced with other environmentally friendly materials. Herein, we demonstrate a route to fabricate biodegradable and dual-functional filtration membranes that effectively remove PM and toxic gases. The membrane was integrated using two layers: (i) cellulose-based nanofibers for PM filtration and (ii) metal-organic framework (MOF)-coated cotton fabric for removal of toxic gases. Zeolitic imidazolate framework (ZIF-8) was grown from the surface of the cotton fabric by the treatment of cotton fabric with an organic precursor solution and subsequent immersion in an inorganic precursor solution. Cellulose acetate nanofibers (NFs) were deposited on the MOF-coated cotton fabric via electrospinning. At the optimal thickness of the NF layer, the quality factor of 18.8 × 10-2 Pa-1 was achieved with a filtration efficiency of 93.1%, air permeability of 19.0 cm3/cm2/s, and pressure drop of 14.2 Pa. The membrane exhibits outstanding gas adsorption efficiencies (>99%) for H2S, formaldehyde, and NH3. The resulting membrane was highly biodegradable, with a weight loss of 62.5% after 45 days under standard test conditions. The proposed strategy should provide highly sustainable material platforms for practical multifunctional membranes in personal protective equipment.

Single-Component Hydrophilic Terpolymer Thin Film Systems for Imparting Surface Chemical Versatility on Various Substrates.

We demonstrate a single-component hydrophilic photocrosslinkable copolymer system that incorporates all critical functionalities into one chain. This design allows for the creation of uniform functional organic coatings on a variety of substrates. The copolymers were composed of a poly(ethylene oxide)-containing monomer, a monomer that can release a primary amine upon UV light, and a monomer with reactive epoxide or cyclic dithiocarbonate with a primary amine. These copolymers are easily incorporated into the solution-casting process using polar solvents. Furthermore, the resulting coating can be readily stabilized through UV light-induced crosslinking, providing an advantage for controlling the surface properties of various substrates. The photocrosslinking capability further enables us to photolithographically define stable polymer domains in a desirable region. The resulting copolymer coatings were chemically versatile in immobilizing complex molecules by (i) post-crosslinking functionalization with the reactive groups on the surface and (ii) the formation of a composite coating by mixing varying amounts of a protein of interest, i.e., fish skin gelatin, which can form a uniform dual crosslinked network. The number of functionalization sites in a thin film could be controlled by tuning the composition of the copolymers. In photocrosslinking and subsequent functionalizations, we assessed the reactivity of the epoxide and cyclic dithiocarbonate with the generated primary amine. Moreover, the orthogonality of the possible reactions of the presented reactive functionalities in the crosslinked thin films with complex molecules is assessed. The resulting copolymer coatings were further utilized to define a hydrophobic surface or an active surface for the adhesion of biological objects.

Injectable Antioxidant and Oxygen-Releasing Lignin Composites to Promote Wound Healing.

The application of engineered biomaterials for wound healing has been pursued since the beginning of tissue engineering. Here, we attempt to apply functionalized lignin to confer antioxidation to the extracellular microenvironments of wounds and to deliver oxygen from the dissociation of calcium peroxide for enhanced vascularization and healing responses without eliciting inflammatory responses. Elemental analysis showed 17 times higher quantity of calcium in the oxygen-releasing nanoparticles. Lignin composites including the oxygen-generating nanoparticles released around 700 ppm oxygen per day at least for 7 days. By modulating the concentration of the methacrylated gelatin, we were able to maintain the injectability of lignin composite precursors and the stiffness of lignin composites suitable for wound healing after photo-cross-linking. In situ formation of lignin composites with the oxygen-releasing nanoparticles enhanced the rate of tissue granulation, the formation of blood vessels, and the infiltration of α-smooth muscle actin+ fibroblasts into the wounds over 7 days. At 28 days after surgery, the lignin composite with oxygen-generating nanoparticles remodeled the collagen architecture, resembling the basket-weave pattern of unwounded collagen with minimal scar formation. Thus, our study shows the potential of functionalized lignin for wound-healing applications requiring balanced antioxidation and controlled release of oxygen for enhanced tissue granulation, vascularization, and maturation of collagen.

Photoimageable Organic Coating Bearing Cyclic Dithiocarbonate for a Multifunctional Surface.

We report the fabrication of photocross-linkable and surface-functionalizable polymeric thin films using reactive cyclic dithiocarbonate (DTC)-containing copolymers. The chemical functionalities of these material surfaces were precisely defined with light illumination. The DTC copolymers, namely, poly(dithiocarbonate methylene methacrylate-random-alkyl methacrylate)s, were synthesized via reversible addition-fragmentation chain transfer polymerization, and the reaction kinetics was thoroughly analyzed. The copolymers were cross-linked into a coating using a bifunctional urethane cross-linker that contains a photolabile o-nitrobenzyl group and releases aniline upon exposure to light. The nucleophilic attack of the aromatic amine opens the DTC group, forming a carbamothioate bond and generating a reactive thiol group in the process. The surface concentrations of the unreacted DTC and thiol were effectively controlled by varying the amounts of the copolymer and the cross-linker. The use of methacrylate comonomers led to additional reactive surface functionality such as carboxylic acid via acid hydrolysis. The successful transformations of the resulting DTC, thiol, and carboxylic acid groups to different functionalities via sequential nucleophilic ring opening, thiol-ene, and carbodiimide coupling reactions under ambient conditions were confirmed quantitatively using X-ray photoelectron spectroscopy. The presented chemistries were readily adapted to the immobilization of complex molecules such as a fluorophore and a protein in lithographically defined regions, highlighting their potential in creating organic coatings that can have multiple functional groups under ambient conditions.

Reactive oxygen species scavenging nanofibers with chitosan-stabilized Prussian blue nanoparticles for enhanced wound healing efficacy.

Chronic inflammatory wounds pose therapeutic challenges in the biomedical field. Polymeric nanofibrous matrices provide extracellular-matrix-like structures to facilitate wound healing; however, wound infection and the subsequent accumulation of reactive oxygen species (ROS) delay healing. Therefore, we herein developed electrospun nanofibers (NFs), composed of chitosan-stabilized Prussian blue (PBChi) nanoparticles (NPs) and poly(vinyl alcohol) (PVA), with ROS scavenging activity to impart antioxidant and wound healing properties. The PBChi NPs were prepared using chitosan with different molecular weights, and their weight ratio with respect to PVA was optimized to yield PBChi-NP-coated PVA NFs with well-defined NF structures. In situ and in vitro antioxidant activity assays showed that the PBChi/PVA NFs could effectively remove ROS. Particularly, PBChi/PVA NFs with a lower chitosan molecular weight exhibited greater antioxidant activity. The hydroxyl radical scavenging activity of PBChi10k/PVA NFs was 60.4 %, approximately two-fold higher than that of PBChi100k/PVA NFs. Further, at the concentration of 10 µg/mL, they could significantly lower the in vitro ROS level by up to 50.7 %. The NFs caused no significant reduction in cell viability, owing to the excellent biocompatibility of PVA with PBChi NPs. Treatment using PBChi/PVA NFs led to faster cell proliferation in in vitro scratch wounds, reducing their size from 202 to 162 µm. The PBChi/PVA NFs possess notable antioxidant and cell proliferation properties as ROS-scavenging wound dressings.

Tailoring Physical Properties of Dual-Network Acrylamide Hydrogel Composites by Engineering Molecular Structures of the Cross-linked Network.

We demonstrate the impact of engineering molecular structures of poly(acrylamide) (PAAm) and poly(N-isopropylacrylamide) (PNIPAm) hydrogel composites on several physical properties. The network structure was systematically varied by (i) the type and the concentration of difunctional cross-linkers and (ii) the type of native or chemically modified natural polymers, including sodium alginate, methacrylate/dopamine-incorporated porcine skin gelatin and fish skin gelatin, and thiol-incorporated lignosulfonate, which are attractive biopolymers generated in pulp and food industries because of their abundance, rich chemical functionalities, and environmental friendliness. First, we added cross-linking agents of varying lengths at different concentrations to assess how the cross-linking agent modulates the mechanical properties of acrylamide-based composites with alginate. After chemically modifying gelatins from fish or porcine skin with methacrylate and/or dopamine, the acrylamide-based composites were fabricated with the chemically modified gelatins and thiolated lignosulfonate to assess the stress-strain behavior. Furthermore, swelling ratios were measured with respect to temperature change. The mechanical properties were systematically modulated by the changes in the molecular structure, that is, the length of the chemical unit between two end alkene groups in the difunctional cross-linker and the types of the additive natural polymers. Overall, PAAm hydrogel composites exhibit a significant, negative correlation between toughness and the volume fraction of the swollen state and between strain at fracture and the volume fraction of the swollen state. In contrast, PNIPAm hydrogel composites showed positive, but only moderate correlations, which is attributed to the difference in the network polymer structure.

Fabrication and characterization of large-area, semiconducting nanoperforated graphene materials.

We demonstrate the fabrication of nanoperforated graphene materials with sub-20-nm features using cylinder-forming diblock copolymer templates across >1 mm(2) areas. Hexagonal arrays of holes are etched into graphene membranes, and the remaining constrictions between holes interconnect forming a honeycomb structure. Quantum confinement, disorder, and localization effects modulate the electronic structure, opening an effective energy gap of 100 meV in the nanopatterned material. The field-effect conductivity can be modulated by 40x (200x) at room temperature (T = 105 K) as a result. A room temperature hole mobility of 1 cm(2) V(-1) s(-1) was measured in the fabricated nanoperforated graphene field effect transistors. This scalable strategy for modulating the electronic structure of graphene is expected to facilitate applications of graphene in electronics, optoelectronics, and sensing.

Coloration and Chromatic Sensing Behavior of Electrospun Cellulose Fibers with Curcumin.

The effective approach for coloration and chromatic sensing of electrospun cellulose fabrics with a natural colorant, curcumin, is demonstrated. To achieve high surface area, the morphology of fiber was controlled to have rough and porous surface through an electrospinning of a cellulose acetate (CA) solution under optimized electrospinning parameters and solvent system. The resulting CA fibers were treated with a curcumin dye/NaOH ethanol solution, in which deacetylation of the CA fiber and high-quality coloration with curcumin were simultaneously achieved. As a control, a cotton fiber with similar diameter and smooth surface morphology was treated by the same method, resulting in poor coloration quality. The difference can be attributed to high surface area as well as trapping of dye molecules inside of cellulose fiber during deacetylation. Both fibers were further utilized for a chromatic sensing application for specific toxic gases. The incorporated curcumin dye responded to hydrogen chloride and ammonia gases reversibly via keto-enol tautomerism, and, as a consequence, the color was reversibly changed between reddish-brown and yellow colors. The cellulose fiber fabricated by the electrospinning showed ten times higher and two times quicker responsiveness compared to curcumin-colored cotton fiber sample prepared with the same immersion method.