Polymer brush patterns have a central role in established and emerging research disciplines, from microarrays and smart surfaces to tissue engineering. The properties of these patterned surfaces are dependent on monomer composition, polymer height, and brush distribution across the surface. No current lithographic method, however, is capable of adjusting each of these variables independently and with micrometer-scale resolution. Here we report a technique termed Polymer Brush Hypersurface Photolithography, which produces polymeric pixels by combining a digital micromirror device (DMD), an air-free reaction chamber, and microfluidics to independently control monomer composition and polymer height of each pixel. The printer capabilities are demonstrated by preparing patterns from combinatorial polymer and block copolymer brushes. Images from polymeric pixels are created using the light reflected from a DMD to photochemically initiate atom-transfer radical polymerization from initiators immobilized on Si/SiO 2 wafers. Patterning is combined with high-throughput analysis of grafted-from polymerization kinetics, accelerating reaction discovery, and optimization of polymer coatings.

In this work, we describe the radiolytic environment experienced by a polymer in water during liquid-cell transmission electron microscopy (LCTEM). We examined the radiolytic environment of aqueous solutions of poly(ethylene glycol) (PEG, 2400 g/mol) in the presence of sensitizing gold nanoparticles (GNPs, 100 nm) or radical scavenging isopropanol (IPA). To quantify polymer damage, we employed post-mortem analysis via matrix-assisted laser desorption/ionization imaging mass spectrometry (MALDI-IMS). This approach confirms IPA (1− 10% w/v) can significantly mitigate radiolysis-induced damage to polymers in water, while GNPs significantly enhance damage. We couple LCTEM experiments with simulations to provide a generalizable strategy for assessing radiolysis mitigation or enhancement. This study highlights the caution required for LCTEM experiments on inorganic nanoparticles where solution phase properties of surrounding organic materials or the solvent itself are under investigation. Furthermore, we anticipate an increased use of scavengers for LCTEM studies of all kinds.

Solvated soft matter, both biological and synthetic, can now be imaged in liquids using liquid-cell transmission electron microscopy (LCTEM). However, such systems are usually composed solely of organic molecules (low Z elements) producing low contrast in TEM, especially within thick liquid films. We aimed to visualize liposomes by LCTEM rather than requiring cryogenic TEM (cryoTEM). This is achieved here by imaging in the presence of aqueous metal salt solutions. The increase in scattering cross-section by the cation gives a staining effect that develops in situ, which could be captured by real space TEM and verified by in situ energy dispersive x-ray spectroscopy (EDS). We identified beam-induced staining as a time-dependent process that enhances contrast to otherwise low contrast materials. We describe the development of this imaging method and identify conditions leading to exceptionally low electron doses for morphology visualization of unilamellar vesicles before beam-induced damage propagates.

Commonly known as a skin pigment, melanin has a vital role in UV radiation protection, primarily acting as a radical scavenger. However, a lesser known natural property of melanin, observed in some melanized organisms, is its capacity to adsorb toxins, including metals and organic molecules. Inspired by this, we set out to generate a synthetic porous melanin that would pave the way to enhancing the natural adsorbent properties of melanin and melanin-like materials. Here, we developed a method for the synthesis of porous polydopamine-based melanin utilizing a mesoporous silica (MS) nanoparticle template and characterized its physical properties. Through the oxidative polymerization of dopamine, followed by the etching of silica, we generated synthetic porous melanin (SPM) with the highest measured surface area of any known polydopamine-based material. The prepared SPM was effective for the uptake of various gases and organophosphate toxins, with the material exhibiting high selectivity for CO 2 over CH 4 and high potential for ammonia capture. Given the demonstrated advantages provided by synthetic porous melanin and melanin's role as an adsorbent in nature, we anticipate the discovery of porous analogues in biological systems.

A century ago, Hermann Staudinger proposed the macromolecular theory of polymers, and now, as we enter the second century of polymer science, we face a different set of opportunities and challenges for the development of functional soft matter. Indeed, many fundamental questions remain open, relating to physical structures and mechanisms of phase transformations at the molecular and nanoscale. In this Viewpoint, we describe efforts to develop a dynamic, in situ microscopy tool suited to the study of polymeric materials at the nanoscale that allows for direct observation of discrete structures and processes in solution, as a complement to light, neutron, and X-ray scattering methods. Liquid-phase transmission electron microscopy (LPTEM) is a nascent in situ imaging technique for characterizing and examining solvated nanomaterials in real time. Though still under development, LPTEM has been shown to be capable of several modes of imaging: (1) imaging static solvated materials analogous to cryo-TEM, (2) videography of nanomaterials in motion, (3) observing solutions or nanomaterials undergoing physical and chemical transformations, including synthesis, assembly, and phase transitions, and (4) observing electron beam-induced chemical-materials processes. Herein, we describe opportunities and limitations of LPTEM for polymer science. We review the basic experimental platform of LPTEM and describe the origin of electron beam effects that go hand in hand with the imaging process. These electron beam effects cause perturbation and damage to the sample and solvent that can manifest as artefacts in images and videos. We describe sample-specific experimental guidelines and outline approaches to mitigate, characterize, and quantify beam damaging effects. Altogether, we seek to provide an overview of this nascent field in the context of its potential to contribute to the advancement of polymer science.