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Increases in complexity attainable in molecular self-assembly necessitates both advanced molecular design as well as microenvironmental control. Such control is offered by microfluidics, where precise chemical compositions and gradients can be readily established. A droplet microfluidic platform combining upstream step emulsification with downstream hydrodynamic microtraps has been designed to facilitate molecular self-assembly. The step emulsification rapidly generates uniform droplets which act as reaction chambers. The hydrodynamic microtraps hold droplets against the flow ensuring they are exposed to a continuous supply of fresh fluid for constant reagent extraction and/or delivery. Additionally, the droplet immobilization permits real-time droplet characterization and reaction monitoring. Subsequently, droplets can be released from the traps through flow reversal, allowing post-process characterization. The microfluidic system was demonstrated by the phase separation of lyotropic droplets. Ethanol/water droplets were created in a continuous ambient squalene/monoolein microflow, causing the continuous extraction of ethanol from the droplets and delivery of monoolein from the ambient microflow. Unlike conventional bulk techniques and continuous microfluidics, where finite microchannel lengths necessarily impose limits to the extent to which slow processes can proceed, this approach allows extended duration reactions whilst enabling real time process monitoring.

Dynamic, kinetically-controlled, self-assembly processes are commonly observed in nature and are capable of creating intricate, functional architectures from simple precursors. However, notably, much of the research into molecular self-assembly has been performed using conventional bulk techniques where the resultant species are dictated by thermodynamic stability to yield relatively simple assemblies. Whereas, the environmental control offered by microfluidic systems offers methods to achieve non-equilibrium reaction conditions capable of increasingly sophisticated self-assembled structures. Alterations to the immediate microenvironment during the assembly of the molecules is possible, providing the basis for kinetically-controlled assembly. This review examines the key mechanism offered by microfluidic systems and the architectures required to access them. The mechanisms include diffusion-led mixing, shear gradient alignment, spatial and temporal confinement, and structural templates in multiphase systems. The works are selected and categorised in terms of the microfluidic approaches taken rather than the chemical constructs which are formed.

High-throughput and rapid serology assays to detect the antibody response specific to severe acute respiratory syndrome-coronavirus-2 (SARS-CoV-2) in human blood samples are urgently required to improve our understanding of the effects of COVID-19 across the world. Short-term applications include rapid case identification and contact tracing to limit viral spread, while population screening to determine the extent of viral infection across communities is a longer-term need. Assays developed to address these needs should match the ASSURED criteria. We have identified agglutination tests based on the commonly employed blood typing methods as a viable option. These blood typing tests are employed in hospitals worldwide, are high-throughput, fast (10–30 min), and automated in most cases. Herein, we describe the application of agglutination assays to SARS-CoV-2 serology testing by combining column agglutination testing with peptide–antibody bioconjugates, which facilitate red cell cross-linking only in the presence of plasma containing antibodies against SARS-CoV-2. This simple, rapid, and easily scalable approach has immediate application in SARS-CoV-2 serological testing and is a useful platform for assay development beyond the COVID-19 pandemic.

As an information-bearing biomacromolecule, DNA is encoded in base-4, where each residue site can be occupied by any one of four nucleobases. Mimicking the information dense, sequence-selective hybridization of DNA, we demonstrate two orthogonal dynamic covalent interactions to effect the selective assembly of molecular ladders and grids from base-4-encoded oligo(peptoid)s.

Dynamic covalent self-assembly processes often exhibit poor capacities for error-correction owing to the relatively low connectivity rearrangement rates of dynamic covalent interactions and the common use of reaction conditions where the equilibrium state remains fixed. Here, we report a dynamic covalent self-assembly technique employing temperature, a conventional, externally-applied stimulus, to mediate the hybridization of peptoid oligomers bearing maleimide- and furan-based pendant groups to afford molecular ladders incorporating Diels–Alder adduct-based rungs. By raising or lowing the reaction temperature, this system enables the equilibrium state to be readily varied without altering reagent concentrations. Both triethylamine and the Lewis acidic scandium triflate were examined as candidate reaction catalysts; however, only scandium triflate increased the rate of single strand conversion. As the Diels–Alder cycloaddition reaction does not liberate a small molecule, a registry-dependent mass change was effected by employing a base-catalyzed thiol-Michael addition reaction between any un-reacted maleimide pendant groups and a low molecular weight thiol to enable the number of Diels–Alder adduct rungs to be readily determined by mass spectrometry. Finally, by employing a slow temperature ramp from high to low temperature, approximating the thermal cycle employed for nucleic acid hybridization, sequence-selective hybridization between model, tetra-functional precursor strands was demonstrated.

Conventional photolithographic rapid prototyping approaches typically achieve reaction confinement in depth through patterned irradiation of a photopolymerizable resin at a wavelength where the resin strongly absorbs, such that only a very thin layer of material is solidified. Consequently, three-dimensional objects are fabricated by progressive, two-dimensional addition of material, curtailing fabrication rates and necessitating the incorporation of support structures to ensure the integrity of overhanging features. Here, we examine butyl nitrite as a UV-active photoinhibitor of blue light-induced photopolymerizations and explore its utilization to confine in depth the region polymerized in a volume of resin. By employing two perpendicular irradiation patterns at blue and near-UV wavelengths to independently effect either polymerization initiation or inhibition, respectively, we enable three-dimensional photopolymerization patterning in bulk resin, thereby complementing emergent approaches to volumetric 3D printing.

The breakdown of the polymeric component of contemporary composite dental restorative materials compromises their longevity, while leachable compounds from these materials have cellular consequences. Thus, a new generation of composite materials needed to be designed to have a longer service life and ensure that any leachable compounds are not harmful to appropriate cell lines. To accomplish this, we have developed concurrent thiol-ene-based polymerization and allyl sulfide–based addition-fragmentation chain transfer chemistries to afford cross-linked polymeric resins that demonstrate low shrinkage and low shrinkage stress. In the past, the filler used in dental composites mainly consisted of glass, which is biologically inert. In several of our prototype composites, we introduced fluorapatite (FA) crystals, which resemble enamel crystals and are bioactive. These novel prototype composites were benchmarked against similarly filled methacrylate-based bisphenol A diglycidyl ether dimethacrylate / triethylene glycol dimethacrylate (bisGMA/TEGDMA) composite for their cytotoxicity, mechanical properties, biofilm formation, and fluoride release. The leachables at pH 7 from all the composites were nontoxic to dental pulp stem cells. There was a trend toward an increase in total toughness of the glass-only-filled prototype composites as compared with the similarly filled bisGMA/TEGDMA composite. Other mechanical properties of the glass-only-filled prototype composites were comparable to the similarly filled bisGMA/TEGDMA composite. Incorporation of the FA reduced the mechanical properties of the prototype and bisGMA/TEGDMA composite. Biofilm mass and colony-forming units per milliliter were reduced on the glass-only-filled prototype composites as compared with the glass-only-filled bisGMA/TEGDMA composite and were significantly reduced by the addition of FA to all composites. Fluoride release at pH 7 was greatest after 24 h for the bisGMA/TEGDMA glass + FA composite as compared with the similarly filled prototypes, but overall the F- release was marginal and not at a concentration to affect bacterial metabolism.

The intrinsic healing of covalently cross-linked polymer networks is commonly effected via the utilization of backbone-borne functional groups able to reversibly cleave or rearrange, thereby enabling mixing and coreaction of network strands that bridge contacted interfaces; however, such materials often exhibit slow healing rates and are susceptible to creep under load. To address these deficiencies, we incorporated hexaarylbiimidazole (HABI) functionalities, groups that are homolytically cleavable, to yield relatively low reactivity lophyl radicals under UV or visible light irradiation and which, in the absence of light, spontaneously recombine without significantly participating in deleterious side reactions, into the backbone of poly(ethylene glycol)-based polymeric gels. Whereas the network connectivity of these HABI-incorporating gels was stable in the dark, they exhibited significant creep upon irradiation. The influence of swelling solvent on the reaction kinetics of backbone-borne HABI photolysis ...

Despite the prevalence of polymers in modern everyday life, there is little introduction to the topic in science education throughout primary or secondary schooling in the United States. Of the few states that do include polymer education, this is only found at the high school level, primarily in biology or chemistry. Over the past year, we have developed a graduate-student-run outreach initiative aimed at providing young students with an understanding and appreciation of this class of materials through the interactive teaching of polymer science with audience-appropriate language. Our lessons are developed to align with the Michigan State Education Standards (Michigan is an NGSS Lead State Partner), such that each lesson can be adapted to the vocabulary of the classroom, even across different grade levels and school curricula. Most importantly, each of our lessons has multiple hands-on activities to reiterate and reinforce the concepts taught through active learning. In teaching our graduate student volu...

This protocol presents the use of Lewis acidic multi-role reagents to circumvent kinetic trapping observed during the self-assembly of information-encoded oligomeric strands mediated by paired dynamic covalent interactions in a manner mimicking the thermal cycling commonly employed for the self-assembly of complementary nucleic acid sequences. Primary amine monomers bearing aldehyde and amine pendant moieties are functionalized with orthogonal protecting groups for use as dynamic covalent reactant pairs. Using a modified automated peptide synthesizer, the primary amine monomers are encoded into oligo(peptoid) strands through solid-phase submonomer synthesis. Upon purification by high-performance liquid chromatography (HPLC) and characterization by electrospray ionization mass spectrometry (ESI-MS), sequence-specific oligomers are subjected to high-loading of a Lewis acidic rare-earth metal triflate which both deprotects the aldehyde moieties and affects the reactant pair equilibrium such that strands completely dissociate. Subsequently, a fraction of the Lewis acid is extracted, enabling annealing of complementary sequence-specific strands to form information-encoded molecular ladders characterized by matrix assisted laser desorption/ionization mass spectrometry (MALDI-MS). The simple procedure outlined in this report circumvents kinetic traps commonly experienced in the field of dynamic covalent assembly and serves as a platform for the future design of robust, complex architectures.

Utilization of constituent molecular precursors bearing covalently coreactive functional groups for self-assembly risks premature reaction, impeding synthetic and purification efforts. To prevent premature amine-aldehyde condensation for oligomers bearing both groups, we employ a dual-role Lewis acid catalyst for both in situ acetal deprotection and subsequent imine exchange, effecting oligomer assembly.

The self-assembly of long-sequence, peptoid-based molecular ladders with up to 16 rungs was demonstrated via the dimerization of oligomeric precursors bearing dynamic covalent pendant groups, with delineation of three potential mechanisms. These include a ‘molecular zipper’, whereby hybridization starts at one end followed by a series of imine condensation reactions to zip up complementary strands, or a ‘molecular hand-shake line’ or ‘toehold displacement’, whereby the molecular ladder formation would occur by shuffling or exchanging through bond rearrangement via cooperative transimination and imine metathesis reactions. MALDI mass spectrometry was used to determine the hybridization registry mechanism, with distance measurements using Forster resonance energy transfer (FRET) further confirming the registry mechanism, indicating that two complementary strands initially interact and bind by rapidly ‘zipping-up’ at any point generating molecular ladders with an arbitrary number of rungs, followed by slowly shuffling through a ‘molecular hand-shake line’ until these ladders come into registry.

The immobilization of antimicrobial peptides (AMPs) to surfaces, enabling their utilization in biosensor and antibacterial/antifouling coating applications, is typically performed using rigid, solid support materials such as glass or gold and may require lengthy, temperamental protocols. Here, we employ a hydrogel immobilization platform to afford facile fabrication and surface functionalization while offering improved biocompatibility for evaluating the influence of linker length, surface density, and AMP conjugation site on retained peptide activity. Rapid, interfacial photo-polymerization using the radical-mediated thiol-ene addition mechanism was used to generate cross-linked, polymeric coatings bearing residual thiol moieties on prefabricated poly(ethylene glycol) (PEG)-based hydrogel supports. The photo-polymerized coatings were 60 μm thick and contained 0.55 nmol of unreacted free thiols, corresponding to a concentration of 410 μM, for use as cecropin A (CPA) immobilization handles via thiol-maleimide conjugation, where the CPA-bound maleimide moiety was localized at either the carboxyl terminus or midsequence between Ala

Covalent organic frameworks, cross-linked crystalline polymers constructed from rigid organic precursors connected by covalent interactions, have emerged as a promising class of nanoporous materials owing to their highly desirable combination of attributes, including facile chemical tunability, structural diversity, and excellent stability. Despite the distinct advantages offered by three-dimensional covalent organic frameworks, research efforts have predominantly focused on the more synthetically-accessible, two-dimensional variants. Here we present an overview of synthetic approaches to yield three-dimensional covalent organic frameworks, identify synthetic obstacles that have hindered progress in the field and recently-employed methods to address them, and propose alternative techniques to circumvent these synthetic challenges. Three-dimensional covalent organic frameworks are attractive functional materials, although there are fewer examples than their two-dimensional counterparts. Here, the authors review the synthetic approaches yielding these compounds, and highlight key challenges facing researchers in the field.

Photopatterning polymerization inhibition volumes by two-color irradiation enables exceptional 3D printing speed and functionality., Contemporary, layer-wise additive manufacturing approaches afford sluggish object fabrication rates and often yield parts with ridged surfaces; in contrast, continuous stereolithographic printing overcomes the layer-wise operation of conventional devices, greatly increasing achievable print speeds and generating objects with smooth surfaces. We demonstrate a novel method for rapid and continuous stereolithographic additive manufacturing by using two-color irradiation of (meth)acrylate resin formulations containing complementary photoinitiator and photoinhibitor species. In this approach, photopatterned polymerization inhibition volumes generated by irradiation at one wavelength spatially confine the region photopolymerized by a second concurrent irradiation wavelength. Moreover, the inhibition volumes created using this method enable localized control of the polymerized region thickness to effect single-exposure, topographical patterning.

Dynamic covalent chemistry, in conjunction with template-directed assembly, enables the fabrication of extended nanostructures that are both precise and tough. Here we demonstrate the dynamic covalent assembly of peptoid-based molecular ladders with up to 12 rungs via scandium(III)-catalyzed imine metathesis by employing the principle of Vernier templating, where small precursor units with mismatched numbers of complementary functional groups are coreacted to yield larger structures with sizes determined by the respective precursor functionalities. Owing to their monomer diversity and synthetic accessibility, sequence-specific oligopeptoids bearing dynamic covalent pendant groups were employed as precursors for molecular ladder fabrication. The generated structures were characterized using matrix-assisted laser desorption/ionization mass spectrometry and gel permeation chromatography, confirming successful molecular ladder fabrication.

Analogous to the thiol-ene and phosphane-ene polymerizations, radical-mediated iodo-ene reactions are described here that proceed via alternating propagation and chain transfer (i.e., APT) reactions between perfluoroiodide- and vinyl-bearing monomers. The thermal polymerization of a diiodo/tetraene formulation yielded a cross-linked, homogeneous polymer that was approximately seven times as radiopaque as aluminum owing to its high iodine content. Visible-light photopolymerizations of model iodo-ene monomers were monitored using mid-IR spectroscopy, revealing that the perfluoroiodide functional group consumption exceeded that of the vinyl, a discrepancy that decreased with increasing irradiation intensities and hence polymerization rates. The functional group conversions in resin formulations with a large initial perfluoroiodide excess exacerbated secondary side reactions that led to off-stoichiometric functional group consumption; nevertheless, photopolymerization of resin formulations with excess vinyl stoichiometry proceeded according to the ideal APT mechanism.

Objectives The aim of this study is to determine if hexaarylbiimidazoles (HABIs) are efficient, visible light-active photoinitiators for thiol–ene systems. We hypothesize that, owing to the reactivity of lophyl radicals with thiols and the necessarily high concentration of thiol in thiol–ene formulations, HABIs will effectively initiate thiol–ene polymerization upon visible light irradiation. Methods UV–vis absorption spectra of photoinitiator solutions were obtained using UV–vis spectroscopy, while EPR spectroscopy was used to confirm radical species generation upon HABI photolysis. Functional group conversions during photopolymerization were monitored using FTIR spectroscopy, and thermomechanical properties were determined using dynamic mechanical analysis. Results The HABI derivatives investigated exhibit less absorptivity than camphorquinone at 469 nm; however, they afford increased sensitivity at this wavelength when compared with bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide. Photolysis of the investigated HABIs affords lophyl radicals. Affixing hydroxyhexyl functional groups to the HABI core significantly improved solubility. Thiol–ene resins formulated with HABI photoinitiators polymerized rapidly upon irradiation with 469 nm. The glass transition temperatures of the thiol–ene resin formulated with a bis(hydroxyhexyl)-functionalized HABI and photopolymerized at room and body temperature were 49.5 ± 0.5 °C and 52.2 ± 0.1 °C, respectively. Significance Although thiol–enes show promise as continuous phases for composite dental restorative materials, they show poor reactivity with the conventional camphorquinone/tertiary amine photoinitiation system. Conversely, despite their relatively low visible light absorptivity, HABI photoinitiators afford rapid thiol–ene photopolymerization rates. Moreover, minor structural modifications suggest pathways for improved HABI solubility and visible light absorption.

The recombination of lophyl radicals generated by the photodissociation of hexaarylbiimidazole (HABI) compounds has been previously reported to proceed as either first-, 3/2-, or second-order reactions. Here, we re-examine the recombination of HABI-derived lophyl radicals to resolve these disparate reported recombination reaction orders. EPR spectroscopy was used to monitor the radical concentration for two HABI-based compounds in solution both during irradiation until steady state was achieved, then in the dark, where only the radical recombination reaction proceeded. Over short dark periods, lophyl radical recombination could be adequately described by second-order reaction kinetics. To better evaluate these reactions, UV–vis spectrophotometry measurements were performed over longer dark recombination periods. The molar absorptivities of the lophyl radical species were determined and used to express UV–vis absorbance data as radical concentrations. Analysis of these radical concentration curves over ext...

Despite originating only a little more than a decade ago, click chemistry has become one of the most powerful paradigms in materials science, synthesis, and modification. By developing and implementing simple, robust chemistries that do not require difficult separations or harsh conditions, the ability to form, modify, and control the structure of materials on various length scales has become more broadly available to those in the materials science community. As such, click chemistry has seen broad implementation in polymer functionalization, surface modification, block copolymer and dendrimer synthesis, biomaterials fabrication, biofunctionalization, and in many other areas of materials science. Here, the basic reactions, approaches, and applications of click chemistry in materials science are highlighted, and a brief look is taken into the future enabling developments in this field.

A pyrrolopyrazine-thione derived from oltipraz, a compound that has been investigated as a chemopreventive agent, affords radicals in the presence of thiols and oxygen via a redox cycle, an attribute that suggests its suitability as an initiator for oxygen-mediated polymerization. Here, we explore the utilization of this pyrrolopyrazine-thione, generated in situ from a precursor, as an initiator for the radical-mediated thiol-ene polymerization. While the pyrrolopyrazine-thione was shown to be capable of generating radicals in the presence of atmospheric oxygen and thiol groups, the reaction extents achievable were lower than desired owing to the presence of unwanted side reactions that would quench radical production and, subsequently, suppress polymerization. Moreover, we found that complex interactions between the pyrrolopyrazine-thione, its precursor, oxygen, and thiol groups determine whether or not the quenching reaction dominates over those favorable to polymerization.

The ability of vascular-targeted drug carriers (VTCs) to localize and bind to a targeted, diseased endothelium determines their overall clinical utility. Here, we investigate how particle modulus and size determine adhesion of VTCs to the vascular wall under physiological blood flow conditions. In general, deformable microparticles (MPs) outperformed nanoparticles (NPs) in all experimental conditions tested. Our results indicate that MP modulus enhances particle adhesion in a shear-dependent manner. In low shear human blood flow profiles in vitro, low modulus particles showed favorable adhesion, while at high shear, rigid particles showed superior adhesion. This was confirmed in vivo by studying particle adhesion under venous shear profiles in a mouse model of mesenteric inflammation, where MP adhesion was 127% greater (p < 0.0001) for low modulus particles compared to more rigid ones. Mechanistically, we establish that particle collisions with leukocytes drive these trends, rather than differences in particle deformation, localization, or detachment. Overall, this work demonstrates the importance of VTC modulus as a design parameter for enhanced VTC interaction with vascular walls, and thus, contributes important knowledge for development of successful clinical theranostics with applications for many diseases.

A new diepoxide monomer (ADTDE) containing an allylic dithioether moiety has been synthesized to extend the suite of monomers that form networks exhibiting radical-mediated photoplasticity. These cross-linked polymers show permanent shape change under load and stress relax only when under the stimulus of visible or UV radiation. The Lewis base-catalyzed reaction of the epoxide groups in ADTDE with tri- and tetrafunctional thiols was monitored by differential scanning calorimetry and infrared spectroscopy. These curing systems were found to be more efficient than anionic, cationic, or anhydride polymerizations. The dynamic mechanical thermal analysis of ADTDE with the tetrathiol showed that the network was rubbery at room temperature which is considered ideal for the demonstration of photoplasticity. The photoinduced creep behavior was shown to be controlled by the presence of active free radicals in the matrix—on cessation of irradiation, the creep was terminated. The stress relaxation of the stretched ne...

Light-activated polymers can undergo complex deformation in response to the combination of mechanical and optical stimuli. These materials are attractive for remote actuation and sensing applications. However, the behavior of such materials subjected to photomechanical patterning is not well understood. In this paper we consider a polymer that operates by photoactivated stress relaxation; at the molecular level, photoinitiation of residual initiator molecules generate free radicals that break and then reform in-chain functionalities of stretched chains in an elastomeric network, which results in macroscopic stress relaxation. We carry out experiments and finite element calculations that demonstrate the sequence of deformation events culminating in the formation of a buckled spot as a result of biaxially stretching the elastomeric film then irradiating a circular region followed by releasing the mechanical constraint. In order to better understand the photomechanics, we analyze a simpler model problem wherein a linear elastic, stress relaxing disk is subjected to (i) radial extension, (ii) irradiation of a concentric circular region, and (iii) release of the applied displacements in (i), which results in deformation and stress redistribution. In the final step, the deformation may transition from planar to buckling out of the plane depending on system parameters. Companion finite element calculations are performed against which our analytical results are in good agreement. Although not directly comparable, the analytic model qualitatively agrees with the experiments. The results of this work provide a useful foundation from which to explore more interesting behavior of periodically photo-mechanically patterned films and other more challenging actuation problems.

Light-activated polymers are an exciting class of modern materials that respond mechanically when irradiated by light at particular wavelengths. While details of the mechanisms that connect the optical excitation to mechanical behavior are complex and differ from material to material, there is sufficient commonality among them to permit the development of a generalized modeling framework to describe the photomechanics. The features shared by light-activated polymers involve light interacting with the material, which triggers photochemical reactions that alter the structure of the crosslinked polymer network. Many such structural alterations result in an evolution of the polymer network, and subsequent macroscopic deformation. When this process is appropriately executed it can enable a photomechanical shape-memory effect. In this paper, we develop a three-dimensional finite-deformation modeling framework to describe the photomechanical response of light-activated polymer systems. This framework integrates four coupled phenomena that contribute to macroscopic photomechanical behavior: photophysics, photochemistry, chemomechanical coupling, and mechanical deformation. The chemomechanical coupling consists of chemically induced structural alterations of the crosslinked network that result in subsequent deformation. We describe this behavior through a decomposition of the crosslinked network into two components consisting of an original network and a photochemically altered network; both evolve during photomechanical deformation. The modeling framework presented in this paper is sufficiently general that it is applicable to light-activated polymer systems that operate with various mechanisms in each of the four areas. Using this modeling approach, we develop constitutive models for two recently developed light-activated polymer systems [Lendlein, A., Hongyan, J., Junger, O., Langer, R., 2005. Light-induced shape-memory polymers. Nature 434 (7035) 879; Scott, T.F., Schneider, A.D., Cook, W.D., Bowman, C.N., 2005. Photoinduced plasticity in crosslinked polymers. Science 308 (5728) 1615]. For the material developed by Scott and his co-workers we validate our model by measuring and numerically simulating photo-induced stress relaxation and bending deformation and obtain good agreement between measurements and predictions. Finally, we use the model to study the effects of photomechanical parameters (applied strain magnitude, irradiation time and intensity, and photoabsorber concentration) and the behavior of the network evolution rule on the material response.

Subwavelength Patterning Microscopists have recently achieved fluorescence imaging at subwavelength resolution by focusing one beam of light in a halo around another beam, thereby quenching the glow of fluorescent dyes in all but the very center of the illuminated spot. Three studies have now adapted this approach to photolithography (see the Perspective by Perry ). Andrew et al. (p. 917 , published online 9 April) coated a photo-resist with molecules that, upon absorbing the ultraviolet etching beam, isomerized to a transparent layer but returned to the initially opaque form upon absorption of visible light. Applying an interference pattern with ultraviolet peaks superimposed on visible nodes restricted etching to narrow regions in the center of these nodes, yielding lines of subwavelength width. Scott et al. (p. 913 , published online 9 April) used a central beam to activate polymerization initiators, while using a halo-shaped surrounding beam to trigger inhibitors that would halt polymerization. Li et al. (p. 910 , published online 9 April) found that use of a different initiator molecule allowed both beams to share the same wavelength (800 nanometers), with a relatively weak quenching beam lagging a highly intense initiating beam slightly in time. Both the latter techniques produced three-dimensional features honed to subwavelength dimensions.

Allyl sulfide addition-fragmentation chain transfer was employed concurrently with the radical-mediated formation of a thiol-ene network to enable network adaptation and mitigation of polymerization-induced shrinkage stress. This result represents the first demonstration of simultaneous polymerization and network adaptation in covalently crosslinked networks with significant implications for the fabrication of low stress polymer networks. For comparison, analogous networks incorporating propyl sulfide moieties, incapable of addition-fragmentation, were synthesized and evaluated in parallel. At the highest irradiation intensity, the allyl sulfide-containing material demonstrated a more than 75% reduction in the final stress when compared with the propyl sulfide-containing material. Analysis of the conversion evolution revealed that allyl sulfide addition-fragmentation decreased the polymerization rate owing to thiyl radical sequestration. Slow consumption of the allyl sulfide functional group suggests that intramolecular homolytic substitution occurs by a step-wise, rather than concerted, mechanism. Simultaneous stress and conversion measurements demonstrated that the initial stress evolution was identical for both the allyl and propyl sulfide-containing materials but diverged after gelation. While addition-fragmentation chain transfer was found to occur throughout the polymerization, its effect on the stress evolution was concentrated towards the end of polymerization when network rearrangement becomes the dominant mechanism for stress relaxation. Even after the polymerization reaction was completed, the polymerization-induced shrinkage stress in the allyl sulfide-containing material continued to decrease, exhibiting a maximum in the stress evolution and demonstrating the potential for continuing, longer term stress relaxation.

Radical-mediated thiol-yne step-growth photopolymerizations are utilized to form highly cross-linked polymer networks. This reaction mechanism is shown to be analogous to the thiol-ene photopolymerization; however, each alkyne functional group is capable of consecutive reaction with two thiol functional groups. The thiol-yne reaction involves the sequential propagation of a thiyl radical with either an alkyne or a vinyl functional group followed by chain transfer of the radical to another thiol. The rate of thiyl radical addition to the alkyne was determined to be approximately one-third of that to the vinyl. Chain-growth polymerization of alkyne and vinyl functionalities was only observed for reactions in which the alkyne was originally in excess. Analysis of initial polymerization rates demonstrated a near first-order dependence on thiol concentration, indicating that chain transfer is the rate-determining step. Further analysis revealed that the polymerization rate scaled with the initiation rate to an exponent of 0.65, deviating from classical square root dependence predicted for termination occurring exclusively by bimolecular reactions. A tetrafunctional thiol was photopolymerized with a difunctional alkyne, forming an inherently higher cross-link density than an analogous thiol-ene resin, displaying a higher glass transition temperature (48.9 vs -22.3 degrees C) and rubbery modulus (80 vs 13 MPa). Additionally, the versatile nature of this chemistry facilitates postpolymerization modification of residual reactive groups to produce materials with unique physical and chemical properties.

A network polymer, incorporating dynamic and reversible cross-links, was synthesized using the Diels−Alder reaction. Fourier transform infrared (FTIR) spectroscopy was used to characterize the reaction rate and thermodynamic equilibrium over a broad temperature range. Equilibrium conversion of the furan and maleimide varied from 74% at 85 °C to 24% at 155 °C, demonstrating significant depolymerization via the retro-Diels−Alder reaction. The gel point temperature, as determined by rheometry using the Winter−Chambon criterion, was 92 °C, corresponding to a gel-point conversion of 71%, consistent with the Flory−Stockmayer equation. The scaling exponents for the complex moduli, viscosity, and plateau modulus, in the vicinity of the gel-point, were determined and compared with experimental and theoretical literature values. Further, the material exhibited a low frequency relaxation owing to dynamic rearrangement of cross-links by the Diels−Alder and retro-Diels−Alder reactions.

BACKGROUND: Thiol–ene networks are of interest due to their facile photopolymerization and their open network structure. In this work, an allylic disulphide divinyl ether monomer is reacted with tetrathiol and divinyl ether monomers, which allows the network structure to permanently change in shape if stressed while under irradiation. We also study the photo-differential scanning calorimetry (DSC) kinetics and photorheology during cure and the dynamic mechanical properties after cure. RESULTS: The heat of polymerization is similar for the thiol–ene systems and suggests ca 80% conversion of the vinyl ether groups. An increase in the initiator concentration increases the photocure rate as expected. The activation energy for photopolymerization is 7.6 kJ mol−1. DSC and rheometry studies show that the polymerization kinetics is slowed by the addition of the allylic disulfide divinyl possibly due to the formation of less reactive radicals. However, as shown by dynamic mechanical thermal analysis, the network structure is not changed very much by addition of this monomer. If radicals are generated by irradiation of a photoinitiator in the network while a stress is being applied, the polymer will permanently deform depending on the fraction of 2-methylenepropane-1,3-di(thioethyl vinyl ether) in the network, due to a bond interchange reaction. CONCLUSION: The rate of thiol–ene reaction is slowed by the addition of the allylic disulfide divinyl ether. Photoplasticity is observed in the networks containing the allylic disulfide groups. Further work is required to optimize the extent of photoplasticity in these systems. Copyright © 2007 Society of Chemical Industry

The morphology of physical hydrogels is often difficult to examine due to the delicate nature of the system and therefore has not been studied in detail. Chitosan/GP (glycerophosphate salt) is a significant hydrogel in the biomedical and cosmetic fields as it is thermosensitive and contains less than 5% polysaccharide. The morphology of this system was examined with laser scanning confocal microscopy (LSCM) to image the gel morphology. The images indicate that the gel is quite heterogeneous, and power spectra reveal a fractal-like morphology. A study of composition found that increasing chitosan concentration increased the amount of polymer-rich phase present in the gel, and that the smallest aggregates decreased in size.

The aim of this study was to determine the ability of various poly(alpha-hydroxy esters) to support the in vitro propagation of murine embryonic stem (ES) cells in an undifferentiated state. To this end, ES cell colonization, growth and Oct-4 immunoreactivity following a 48 h culture period upon poly((D,L)-lactide), poly((L)-lactide), poly(glycolide) and poly((D,L)-lactide-co-glycolide) (PLGA) were assessed. By the analysis of live and dead cell number indices and Oct-4 immunoreactivity, ES cell colonization rate during a 48 h culture period was found to be significantly greater on PLGA compared to all the other unmodified poly(alpha-hydroxy esters) tested. Surface treatment of all polymers with 0.1m potassium hydroxide revealed a significant increase in ES cell live numbers when compared to all unmodified polymers, thus revealing a correlation between polymer content, hydrophilicity and colonization rate. These data suggest that surface treated poly(alpha-hydroxy esters) may be employed for ES cell scale up procedures and in tissue engineering applications requiring the colonization of scaffolds by ES cells in an undifferentiated state. According to such applications, once the designated scaffold has been colonized, ES cell directed differentiation into the desired and fully differentiated, functional adult tissue may then be effected.

The temperature and frequency dependence of the dynamic mechanical properties in the glass transition was studied for a series of partially cured thermally reactive networks (low temperature cured epoxy and a dimethacrylate photocured with a conventional initiator) and more thermally stable networks (high temperature cured epoxy and two dimethacrylates photocured with a photoiniter1). The viscoelastic behavior in the transition region of the former networks changed during the experiment due to additional cure, whereas the thermally stable networks enabled the study of the effect of conversion on the transition region. The glass transition temperatures showed 1 : 1 relationships with the isothermal curing temperatures and were correlated with the degree of conversion. The breadth of the glass transition, as determined from the real and loss moduli, tan δ, and the loss compliance in the temperature and frequency domains, was found to be greater for the dimethacrylate networks than for the epoxy networks. The breadth of the transition for the dimethacrylates was not significantly dependent on the degree of cure. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1348–1359, 2004

A range of dimethacrylates with varying backbone flexibility were partially photocured to various conversions using p-xylylene bis-(N,N-diethyldithiocarbamate) as a photoiniferter and their glass transition region investigated by dynamic mechanical thermal analysis. For isothermally cured samples, the final degree of conversion was found to increase as the length of the spacer group in the monomer was increased or as the crosslink density in the resin was lowered due to the reduced glass transition temperature which allowed greater mobility and, hence, higher cure. Increasing the curing temperature also resulted in a higher degree of conversion as the network was able to polymerize further before vitrification occurred. For the partially photocured samples, the glass transition temperature was raised as the degree of conversion was increased. Most of the measures of the breadth of the glass transition were found to increase with increased conversion for dimethacrylates with short or stiff backbones (TETDMA and bisGMA) while the transition breadth was independent of conversion for either a more flexible dimethacrylate (NEGDMA) or a dimethacrylate network with a lower crosslink density (50 wt % bisGMA/50 wt % PGEMA). This conclusion was generally confirmed by analysis of the viscoelastic parameters in the frequency domain. It is not clear whether these behaviors resulted from differences in the range of molecular motions available in tight networks or if they were due to spatially heterogeneous regions in the network. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3753–3766, 2003

The reaction kinetics during photopolymerization of bisGMA/styrene blends were investigated using FTIR and ESR spectroscopy. Increased styrene concentration reduced the polymerization rate of both methacrylate and styrene due to an increase in the termination rate and due to the stability of the styryl radical. Raised styrene concentrations also increased the final methacrylate conversion, but the final styrene conversion decreased because styrene plasticized the network, allowing methacrylate conversion to rise at higher styrene concentrations; however, the copolymerization did not proceed far enough to achieve increased conversions of styrene. The final concentration of radicals was reduced at higher styrene concentrations because of an increase in the bimolecular termination rate for networks with low cross-link densities. The proportion of styryl radicals trapped in the vitrified matrix was found to be markedly higher than the proportion predicted from the proportion of styrene monomer in the feed res...

The photopolymerization kinetics of two commercial vinyl ester resins (VERs) and a model VER photoinitiated by the camphorquinone/amine photoinitiator system were monitored using isothermal DSC. A decrease in styrene concentration in model VERs was found to raise the rate of photopolymerization. In contrast, when the styrene was replaced by a monomethacrylate diluent, the photopolymerization rate passed through a maximum near 70 wt% diluent monomer. This difference in the variation of the rate of polymerization with decreased monomer concentration was attributed to the competition of the effects of the higher reactivity of the methacrylyl radical relative to the styryl radical and the lower termination rate for divinyl-rich systems (both of which tend to raise the maximum polymerization rate) and the effects of the reduction in the initiation efficiency and decrease in k p due to increased fraction of pendant double bonds (which lower the polymerization rate) when the concentration of diluent monomer was reduced. Subsequent dark polymerization was observed during a temperature ramp and the onset of polymerization was independent of resin composition due to vitrification effects during the isothermal photocuring stage. The kinetics during the dark polymerization stage was discussed in terms of the radical concentration and the propagation rate constant. Increases in the concentration of either diluent monomer raised the extent of isothermal cure during the isothermal polymerization because vitrification was delayed by the lower crosslink density and the plasticizing effect of the diluent. Higher levels of diluent also raised the maximally attainable conversion due to reduced topological restrictions for reaction in networks of lower crosslink density.

Bisphenol-A diglycidyl ether dimethacrylate was blended with styrene at varying concentrations and this model vinyl ester resin (VER) was compared with two commercial VERs. The VERs were characterized using gravimetry, FTIR spectroscopy, NMR spectroscopy, differential scanning calorimetry (DSC) and DMTA. NMR spectroscopy differentiated between a novolac epoxy-based multimethacrylate oligomer and the two bisphenol-A epoxy-based dimethacrylate oligomers. Reaction kinetics were studied using scanning and isothermal DSC and isothermal FTIR spectroscopy using benzoyl peroxide as the thermal initiator. The presence of oxygen was found to inhibit significantly the polymerization. Increased initiator concentration raised the rate of isothermal polymerization, but did not affect the final conversion while increased styrene concentration reduced the polymerization rate constant and increased the total conversion. This was interpreted in terms of the variations in the termination rate and the stability of the styryl radical on the cure rate and the effect of vitrification on the extent of cure. From measurements of the dynamic mechanical properties as a function of temperature, the breadth of the glass transition tan δ curve and the magnitude of the rubbery modulus was found to increase while the tan δ maximum decreased with increased crosslink density. The T g , as measured by DSC, and the temperature of the tan δ maximum, as measured by DMTA, were not significantly affected by the styrene content in the resin per se , but were dependent on the combined effects of composition and crosslink density of the network.

Isothermal DSC was employed to monitor the photopolymerization kinetics of a commercial vinyl ester resin (VER) photoinitiated by the camphorquinone/amine photoinitiator system. The maximum rate of photopolymerization was found to increase tenfold as the isothermal cure temperature was varied from −30 to 90 °C due to faster propagation and greater initiator efficiency counterbalanced by a faster termination rate. After photopolymerization, the samples were temperature ramped in the DSC to monitor the dark polymerization reaction. The reduced polymerization rate increased with the scan temperature due to an increase in propagation rate. The summation of the isothermal and residual polymerization heats indicated that the final degree of cure after postcure was independent of the isothermal cure temperature. The onset temperatures for the recommencement of cure during the dark temperature scanning experiments were found to correspond closely with their respective isothermal cure temperatures as expected due to vitrification during the isothermal cure stage.

Materials that solidify in response to an initiation stimulus are currently utilized in several biomedical and surgical applications; however, their clinical adoption would be more widespread with improved physical properties and biocompatibility. One chemistry that is particularly promising is based on the thiol–ene addition reaction, a radical-mediated step-growth polymerization that is resistant to oxygen inhibition and thus is an excellent candidate for materials that polymerize upon exposure to aerobic conditions. Here, thiol–ene-based hydrogels are polymerized by exposing aqueous solutions of multi-functional thiol and allyl ether PEG monomers, in combination with enzymatic radical initiating systems, to air. An initiating system based on glucose oxidase, glucose, and Fe2+ is initially investigated where, in the presence of glucose, the glucose oxidase reduces oxygen to hydrogen peroxide which is then further reduced by Fe2+ to yield hydroxyl radicals capable of initiating thiol–ene polymerization. While this system is shown to effectively initiate polymerization after exposure to oxygen, the polymerization rate does not monotonically increase with raised Fe2+ concentration owing to inhibitory reactions that retard polymerization at higher Fe2+ concentrations. Conversely, replacing the Fe2+ with horseradish peroxidase affords an initiating system is that is not subject to the iron-mediated inhibitory reactions and enables increased polymerization rates to be attained.

Radical mediated addition-fragmentation chain transfer of mid-chain allyl sulfide functional groups was utilized to reduce polymerization-induced shrinkage stress in thiol-yne step-growth photopolymerization reactions. In previous studies, the addition-fragmentation of allyl sulfide during the polymerization of a step-growth thiol-ene network demonstrated reduced polymerization stress; however, the glass transition temperature of the material was well below room temperature (~ -20°C). Many applications require super-ambient glass transition temperatures, such as microelectronics and dental materials. Polymerization reactions utilizing thiol-yne functional groups have many of the advantageous attributes of the thiol-ene-based materials, such as possessing a delayed gel-point, resistant to oxygen inhibition, and fast reaction kinetics, while also possessing a high glass transition temperature. Here we incorporate allyl sulfide functional groups into a highly crosslinked thiol-yne network to reduce polymerization-induced shrinkage stress. Simultaneous shrinkage stress and functional group conversion measurements were performed during polymerization using a cantilever-type tensometer coupled with a FTIR spectrometer. The resulting networks were highly crosslinked, possessed super-ambient glass transition temperatures, and exhibited significantly reduced polymerization-induced shrinkage stress when compared with analogous propyl sulfide-containing materials that are incapable of addition-fragmentation.

Chemically cross-linked polymers are inherently limited by stresses that are introduced by post-gelation volume changes during polymerization. It is also difficult to change a cross-linked polymer's shape without a corresponding loss of material properties or substantial stress development. We demonstrate a cross-linked polymer that, upon exposure to light, exhibits stress and/or strain relaxation without any concomitant change in material properties. This result is achieved by introducing radicals via photocleavage of residual photoinitiator in the polymer matrix, which then diffuse via addition-fragmentation chain transfer of midchain functional groups. These processes lead to photoinduced plasticity, actuation, and equilibrium shape changes without residual stress. Such polymeric materials are critical to the development of microdevices, biomaterials, and polymeric coatings.

In this study we introduce the use of thiol-ene photopolymers as shape memory polymer systems. The thiol-ene polymer networks are compared to a commonly utilized acrylic shape memory polymer and shown to have significantly improved properties for two different thiol-ene based polymer formulations. Using thermomechanical and mechanical analysis, we demonstrate that thiol-ene based shape memory polymer systems have comparable thermomechanical properties while also exhibiting a number of advantageous properties due to the thiol-ene polymerization mechanism which results in the formation of a homogeneous polymer network with low shrinkage stress and negligible oxygen inhibition. The resulting thiol-ene shape memory polymer systems are tough and flexible as compared to the acrylic counterparts. The polymers evaluated in this study were engineered to have a glass transition temperature between 30 and 40 °C, exhibited free strain recovery of greater than 96% and constrained stress recovery of 100%. The thiol-ene polymers exhibited excellent shape fixity and a rapid and distinct shape memory actuation response.