Surface-Initiated PET-RAFT via the Z-Group Approach.

Surface-initiated reversible addition-fragmentation chain transfer (SI-RAFT) is a user-friendly and versatile approach for polymer brush engineering. For SI-RAFT, synthetic strategies follow either surface-anchoring of radical initiators (e.g., azo compounds) or anchoring RAFT chain transfer agents (CTAs) onto a substrate. The latter can be performed via the R-group or Z-group of the CTA, with the previous scientific focus in literature skewed heavily toward work on the R-group approach. This contribution investigates the alternative: a Z-group approach toward light-mediated SI photoinduced electron transfer RAFT (SI-PET-RAFT) polymerization. An appropriate RAFT CTA is synthesized, immobilized onto SiO2, and its ability to control the growth (and chain extension) of polymer brushes in both organic and aqueous environments is investigated with different acrylamide and methacrylate monomers. O2 tolerance allows Z-group SI-PET-RAFT to be performed under ambient conditions, and patterning surfaces through photolithography is illustrated. Polymer brushes are characterized via X-ray photoelectron spectroscopy (XPS), ellipsometry, and water contact angle measurements. An examination of polymer brush grafting density showed variation from 0.01 to 0.16 chains nm-2. Notably, in contrast to the R-group SI-RAFT approach, this chemical approach allows the growth of intermittent layers of polymer brushes underneath the top layer without changing the properties of the outermost surface.

On the Importance of Mental Health in STEM.

From homework to exams to proposal deadlines, STEM academia bears many stressors for students, faculty, and administrators. The increasing prevalence of burnout as an occupational phenomenon, along with anxiety, depression, and other mental illnesses in the STEM community is an alarming sign that help is needed. We describe common mental illnesses, identify risk factors, and outline symptoms. We intend to provide guidance on how some people can cope with stressors while also giving advice for those who wish to help their suffering friends, colleagues, or peers. We hope to spark more conversation about this important topic that may affect us all-while also encouraging those who suffer (or have suffered) to share their stories and serve as role models for those who feel they cannot speak.

Elucidating Interfacial Chain Conformation of Superhydrophilic Polymer Brushes by Vibrational Sum Frequency Generation Spectroscopy.

Surface-tethered macromolecules (polymer brushes) are a potent means to modify surfaces with stimuli-responsive properties while avoiding delamination problems. This vibrational sum frequency generation spectroscopy study describes how the conformation of hydrophilic polymer brushes changes in response to environmental conditions, that is, changes in humidity (in air) and upon exposure to liquid water. Three hydrophilic brushes were prepared on silicon oxide surfaces by surface-initiated reversible deactivation radical polymerization of cationic (quaternary ammonium), anionic (sulfonate), and zwitterionic (containing both) monomers. The average tilt angle of methyl groups was analyzed and used to deduce the chain conformations of the polymer brushes. In air, the brush films absorb water and swell with increasing humidity. This is accompanied by the rotation of interfacial polymer chains. The degree of water uptake and chain conformation vary with the nature of the charged hydrophilic moieties. The hydrophilic polymer brush surfaces appear to remain relatively dry except in near-condensation conditions. In water, the quaternary ammonium groups of cationic and zwitterionic brushes are aligned nearly parallel to the surface. The anionic brush chains appear to assume nearly random conformations in water.

Oxygen Tolerance in Surface-Initiated Reversible Deactivation Radical Polymerizations: Are Polymer Brushes Turning into Technology?

Over the past three decades, the development of reversible deactivation radical polymerizations (RDRP), and advancements toward more user-friendly and accessible experimental setups have opened the door for nonexperts to design complex macromolecules with well-defined properties. External mediation, improved tolerance to oxygen, and increased reaction volumes for higher synthetic output are some of the many noteworthy technical improvements. The development of RDRPs in solution was paralleled by their application on solid substrates to synthesize surface-grafted "polymer brushes" via surface-initiated RDRP (SI-RDRP). This Viewpoint paper provides a current perspective on recent developments in SI-RDRP methods that are tolerant to oxygen, especially highlighting those that could potentially enable scaling up of the synthesis of brushes for the functionalization of technologically relevant materials.

Estimating Internal Stress of an Alteration Layer Formed on Corroded Boroaluminosilicate Glass through Spectroscopic Ellipsometry Analysis.

Aqueous corrosion of glass may result in the formation of an alteration layer in the glass surface of which chemical composition and network structure are different from those of the bulk glass. Since corrosion occurs far below the glass-transition temperature, the alteration layer cannot fully relax to the new structure with the lowest possible energy. Molecular dynamics simulations suggested that such a network will contain highly strained chemical bonds, which can be manifested as a stress in the alteration layer. Common techniques to measure stress in thin films or surface layers were found inadequate for thick monolithic glass samples corroded in water. Here, we explored the use of spectroscopic ellipsometry to test the presence of internal stress in the alteration layer formed by aqueous corrosion of glass. A procedure for analyses of spectroscopic ellipsometry data to determine birefringence in the alteration layer was developed. Findings with the established fitting procedure suggested that a stress builds up in the corroded surface layer of a boroaluminosilicate glass if there is a change in relative humidity, pH, or electrolyte concentration of the environment to which the glass surface is exposed. A similar process may occur in other types of glass, and it may affect the surface properties of corroded glass objects.

Preparation of Patterned and Multilayer Thin Films for Organic Electronics via Oxygen-Tolerant SI-PET-RAFT.

An oxygen-tolerant approach is described for preparing surface-tethered polymer films of organic semiconductors directly from electrode substrates using polymer brush photolithography. A photoinduced electron transfer-reversible addition-fragmentation chain transfer (PET-RAFT) approach was used to prepare multiblock polymer architectures with the structures of multi-layer organic light-emitting diodes (OLEDs), including electron-transport, emissive, and hole-transport layers. The preparation of thermally activated delayed fluorescence (TADF) and thermally assisted fluorescence (TAF) trilayer OLED architectures are described. By using direct photomasking as well as a digital micromirror device, we also show that the surface-initiated (SI)-PET-RAFT approach allows for enhanced control over layer thickness, and spatial resolution in polymer brush patterning at low cost.

Synthesis of Polymer Brushes Via SI-PET-RAFT for Photodynamic Inactivation of Bacteria.

Biofilms are a persistent issue in healthcare and industry. Once formed, the eradication of biofilms is challenging as the extracellular polymeric matrix provides protection against harsh environmental conditions and physically enhances resistance to antimicrobials. The fabrication of polymer brush coatings provides a versatile approach to modify the surface to resist the formation of biofilms. Herein, the authors report a facile synthetic route for the preparation of surface-tethered polymeric brushes with antifouling and visible light activated bactericidal properties using surface-initiated photoinduced electron transfer-reversible addition-fragmentation chain transfer polymerization (SI-PET-RAFT). Bactericidal property via the generation of singlet oxygen, which can be temporally and spatially controlled, is investigated against both Gram-positive and Gram-negative bacteria. In addition, the antibacterial properties of the surface can be recycled. This work paves the way for the preparation of polymer films that can resist and kill bacterial biofilms.

Benchtop Preparation of Polymer Brushes by SI-PET-RAFT: The Effect of the Polymer Composition and Structure on Inhibition of a Pseudomonas Biofilm.

We report a high-throughput method for producing surface-tethered polymeric brushes on glass substrates via surface-initiated photoinduced electron transfer-reversible addition-fragmentation chain transfer polymerization (SI-PET-RAFT). Due to its excellent oxygen tolerance, SI-PET-RAFT allows brush growth using low reagent volumes (30 µL) without prior degassing. An initial 28 homopolymer brush library was successfully prepared and screened with respect to their antifouling performance. The high-throughput approach was further exploited to expand the library to encompass statistical, gradient, and block architectures to investigate the effect of monomer composition and distribution using two monomers of disparate performance. In this manner, the degree of attachment from Gram-negative Pseudomonas aeruginosa (PA) bacterial biofilms could be tuned between the bounds set by the homopolymer brushes.

Comparison of Long-Term Stability of Initiating Monolayers in Surface-Initiated Controlled Radical Polymerizations.

The reproducibility of polymer brush synthesis via surface-initiated controlled radical polymerization is interrogated. Experiments compare the stability of initiating monolayers for surface-initiated (SI) reversible addition-fragmentation chain transfer polymerization (SI-RAFT) and SI atom transfer radical polymerization (SI-ATRP). Initiator-functionalized substrates are stored under various conditions and grafting densities of the resulting polymer brush films are determined via in situ ellipsometry. Decomposition of one of the examined SI-RAFT initiators results in limited reproducibility for polymer brush surface modification. In contrast, initiators for SI-ATRP show excellent stability and reproducibility. While both techniques bring inherent benefits and limitations, the described findings will help scientists choose the most efficient technique for their goals in chemical and topographical surface modification.

Surface Engineering with Polymer Brush Photolithography.

Surface-tethered macromolecules, or polymer brushes, offer a unique platform for coating surfaces for a wide variety of applications. Surface-initiated polymerization (SI-P), through which polymer brushes can be grown directly from an initiator-functionalized surface, offers a facile, highly customizable approach that is synergistic with photolithography. Using a variety of photolithography devices and SI-Ps, complex polymer brush architectures can be fabricated with great spatial and temporal control. This article not only addresses techniques, advancements, applications, and possible future directions within the field of polymer brush photolithography, but it also provides resources to assist the reader in selecting the polymerization technique and photolithography device most conducive to a given endeavor.

Mixed Polymer Brushes for "Smart" Surfaces.

Mixed polymer brushes (MPBs) are composed of two or more disparate polymers covalently tethered to a substrate. The resulting phase segregated morphologies have been extensively studied as responsive "smart" materials, as they can be reversible tuned and switched by external stimuli. Both computational and experimental work has attempted to establish an understanding of the resulting nanostructures that vary as a function of many factors. This contribution highlights state-of-the-art MPBs studies, covering synthetic approaches, phase behavior, responsiveness to external stimuli as well as novel applications of MPBs. Current limitations are recognized and possible directions for future studies are identified.

Glass transition temperature from the chemical structure of conjugated polymers.

The glass transition temperature (Tg) is a key property that dictates the applicability of conjugated polymers. The Tg demarks the transition into a brittle glassy state, making its accurate prediction for conjugated polymers crucial for the design of soft, stretchable, or flexible electronics. Here we show that a single adjustable parameter can be used to build a relationship between the Tg and the molecular structure of 32 semiflexible (mostly conjugated) polymers that differ drastically in aromatic backbone and alkyl side chain chemistry. An effective mobility value, ζ, is calculated using an assigned atomic mobility value within each repeat unit. The only adjustable parameter in the calculation of ζ is the ratio of mobility between conjugated and non-conjugated atoms. We show that ζ correlates strongly to the Tg, and that this simple method predicts the Tg with a root-mean-square error of 13 °C for conjugated polymers with alkyl side chains.

SI-PET-RAFT: Surface-Initiated Photoinduced Electron Transfer-Reversible Addition-Fragmentation Chain Transfer Polymerization.

In this communication, surface-initiated photoinduced electron transfer-reversible addition-fragmentation chain transfer polymerization (SI-PET-RAFT) is introduced. SI-PET-RAFT affords functionalization of surfaces with spatiotemporal control and provides oxygen tolerance under ambient conditions. All hallmarks of controlled radical polymerization (CRP) are met, affording well-defined polymerization kinetics, and chain end retention to allow subsequent extension of active chain ends to form block copolymers. The modularity and versatility of SI-PET-RAFT is highlighted through significant flexibility with respect to the choice of monomer, light source and wavelength, and photoredox catalyst. The ability to obtain complex patterns in the presence of air is a significant contribution to help pave the way for CRP-based surface functionalization into commercial application.

Simultaneous Preparation of Multiple Polymer Brushes under Ambient Conditions using Microliter Volumes.

The fabrication of well-defined, multifunctional polymer brushes under ambient conditions is described. This facile method uses light-mediated, metal-free atom-transfer radical polymerization (ATRP) to grow polymer brushes with only microliter volumes required. Key to the success of this strategy is the dual action of N-phenylphenothiazine (PTH) as both an oxygen scavenger and polymerization catalyst. Use of simple glass cover slips results in a high degree of spatial and temporal control and allows for multiple polymer brushes to be grown simultaneously. The preparation of arbitrary 3D patterns and functional/emissive polymer brushes demonstrates the practicality and versatility of this novel strategy.

Novel Strategy for Photopatterning Emissive Polymer Brushes for Organic Light Emitting Diode Applications.

A light-mediated methodology to grow patterned, emissive polymer brushes with micron feature resolution is reported and applied to organic light emitting diode (OLED) displays. Light is used for both initiator functionalization of indium tin oxide and subsequent atom transfer radical polymerization of methacrylate-based fluorescent and phosphorescent iridium monomers. The iridium centers play key roles in photocatalyzing and mediating polymer growth while also emitting light in the final OLED structure. The scope of the presented procedure enables the synthesis of a library of polymers with emissive colors spanning the visible spectrum where the dopant incorporation, position of brush growth, and brush thickness are readily controlled. The chain-ends of the polymer brushes remain intact, affording subsequent chain extension and formation of well-defined diblock architectures. This high level of structure and function control allows for the facile preparation of random ternary copolymers and red-green-blue arrays to yield white emission.

Effects of Tailored Dispersity on the Self-Assembly of Dimethylsiloxane-Methyl Methacrylate Block Co-Oligomers.

The effect of dispersity on block polymer self-assembly was studied in the monodisperse limit using a combination of synthetic chemistry, matrix-assisted laser desorption ionization spectroscopy, and small-angle X-ray scattering. Oligo(methyl methacrylate) (oligoMMA) and oligo(dimethylsiloxane) (oligoDMS) homopolymers were synthesized by conventional polymerization techniques and purified to generate an array of discrete, semidiscrete, and disperse building blocks. Coupling reactions afforded oligo(DMS-MMA) block polymers with precisely tailored molar mass distributions spanning single molecular systems (D = 1.0) to low-dispersity mixtures (D ≈ 1.05). Discrete materials exhibit a pronounced decrease in domain spacing and sharper scattering reflections relative to disperse analogues. The order-disorder transition temperature (TODT) also decreases with increasing dispersity, suggesting stabilization of the disordered phase, presumably due to the strengthening of composition fluctuations at the low molar masses investigated.

Engineering Surfaces through Sequential Stop-Flow Photopatterning.

Solution-exchange lithography is a new modular approach to engineer surfaces via sequential photopatterning. An array of lenses reduces features on an inkjet-printed photomask and reproduces arbitrarily complex patterns onto surfaces. In situ exchange of solutions allows successive photochemical reactions without moving the substrate and affords access to hierarchically patterned substrates.

Metal-Free Removal of Polymer Chain Ends Using Light.

A light-mediated method for the facile removal of polymer end groups that are common to controlled radical polymerization techniques is presented. This metal-free strategy is general, being effective for chlorine, bromine, and thiocarbonylthio moieties as well as a number of different polymer families (styrenic, acrylic, and methacrylic). In addition to solution reactions, this process is readily translated to thin films, where light mediation allows the straightforward fabrication of hierarchically patterned polymer brushes.

Simple Benchtop Approach to Polymer Brush Nanostructures Using Visible-Light-Mediated Metal-Free Atom Transfer Radical Polymerization.

The development of an operationally simple, metal-free surface-initiated atom transfer radical polymerization (SI-ATRP) based on visible-light mediation is reported. The facile nature of this process enables the fabrication of well-defined polymer brushes from flat and curved surfaces using a "benchtop" setup that can be easily scaled to four-inch wafers. This circumvents the requirement of stringent air-free environments (i.e., glovebox), and mediation by visible light allows for spatial control on the micron scale, with complex three-dimensional patterns achieved in a single step. This robust approach leads to unprecedented access to brush architectures for nonexperts.

Cross-linking density and temperature effects on the self-assembly of SiO2-PNIPAAm core-shell particles at interfaces.

SiO2-PNIPAAm core-shell microgels (PNIPAAm=poly(N-isopropylacrylamide)) with various internal cross-linking densities and different degrees of polymerization were prepared in order to investigate the effects of stability, packing, and temperature responsiveness at polar-apolar interfaces. The effects were investigated using interfacial tensiometry, and the particles were visualized by cryo-scanning electron microscopy (SEM) and scanning force microscopy (SFM). The core-shell particles display different interfacial behaviors depending on the polymer shell thickness and degree of internal cross-linking. A thicker polymer shell and reduced internal cross-linking density are more favorable for the stabilization and packing of the particles at oil-water (o/w) interfaces. This was shown qualitatively by SFM of deposited, stabilized emulsion droplets and quantitatively by SFM of particles adsorbed onto a hydrophobic planar silicon dioxide surface, which acted as a model interface system. The temperature responsiveness, which also influences particle-interface interactions, was investigated by dynamic temperature protocols with varied heating rates. These measurements not only showed that the particles had an unusual but very regular and reversible interface stabilization behavior, but also made it possible to assess the nonlinear response of PNIPAAm microgels to external thermal stimuli.