Solvent annealing produces ordered assemblies in thin films of block copolymers and, in contrast to uniform thermal annealing, can be used to tune the self-assembled morphology, control the domain orientation with respect to the substrate, and, as demonstrated here, reduce the defect density. The two-dimensional network topology of lamellae self-assembled by polystyrene-block-poly(methyl methacrylate) block copolymers in thin films was compared when processed by solvent and thermal annealing techniques. The mixed solvent annealing method described here reduced the overall defect density (e.g., dislocations with PMMA or PS cores) and thus the connectivity of the lamellar domains compared to thermal annealing; however, the long-range continuity of the networks was maintained and depended primarily on the copolymer composition. In addition, the persistence length of the lamellar domains for solvent annealed films was found to be 2–3 times that of the corresponding thermally annealed systems.
One key route for controlling reaction selectivity in heterogeneous catalysis is to prepare catalysts that exhibit only specific types of sites required for desired product formation. Here we show that alkanethiolate self-assembled monolayers with varying surface densities can be used to tune selectivity to desired hydrogenation and hydrodeoxygenation products during the reaction of furfural on supported palladium catalysts. Vibrational spectroscopic studies demonstrate that the selectivity improvement is achieved by controlling the availability of specific sites for the hydrogenation of furfural on supported palladium catalysts through the selection of an appropriate alkanethiolate. Increasing self-assembled monolayer density by controlling the steric bulk of the organic tail ligand restricts adsorption on terrace sites and dramatically increases selectivity to desired products furfuryl alcohol and methylfuran. This technique of active-site selection simultaneously serves both to enhance selectivity and provide insight into the reaction mechanism.
This groundbreaking work of the Weimer and Musgrave groups was highlighted in a news article.
Solar thermal water-splitting (STWS) cycles have long been recognized as a desirable means of generating hydrogen gas (H2) from water and sunlight. Two-step, metal oxide–based STWS cycles generate H2 by sequential high-temperature reduction and water reoxidation of a metal oxide. The temperature swings between reduction and oxidation steps long thought necessary for STWS have stifled STWS’s overall efficiency because of thermal and time losses that occur during the frequent heating and cooling of the metal oxide. We show that these temperature swings are unnecessary and that isothermal water splitting (ITWS) at 1350°C using the “hercynite cycle” exhibits H2 production capacity >3 and >12 times that of hercynite and ceria, respectively, per mass of active material when reduced at 1350°C and reoxidized at 1000°C.
This work was highlighted as a JACS Spotlight, JACS135, 5475−5476 (2013).
Aptamer-ligand binding events, involving small molecule targets, at a surfactant-laden aqueous/liquid crystal (LC) interface were found to trigger a LC reorientation that can be observed in real-time using polarized light. The response was both sensitive and selective: reorientation was observed at target concentrations on the order of the aptamer dissociation constant, but no response was observed in control experiments with target analogues. Circular dichroism and resonance energy transfer experiments suggested that the LC reorientation was due to a conformational change of the aptamer upon target binding. Specifically, under conditions where aptamer-ligand binding induced a conformational change from a relaxed random coil to more intricate secondary structures (e.g., double helix, G-quadruplex), a transition from planar to homeotropic LC orientation was observed. These observations suggest the potential for a label-free LC-based detection system that can simultaneously respond to the presence of both small molecules and nucleic acids.
We present an integrated theory and simulation study of polydisperse polymer grafted nanoparticles in a polymer matrix to demonstrate the effect of polydispersity in graft length on the potential of mean force between the grafted nanoparticles. In dense polymer solutions, increasing polydispersity in graft length reduces the strength of repulsion at contact and weakens the attractive well at intermediate interparticle distances, completely eliminating the latter at high polydispersity index. The reduction in contact repulsion is attributable to polydispersity relieving monomer crowding near the particle surface, especially at high grafting densities. The elimination of the midrange attractive well is attributable to the longer grafts in the polydisperse graft length distribution that introduce longer range steric repulsion and alter the wetting of the grafted layer by matrix chains. Dispersion of the grafted particles is stabilized by increased penetration or wetting of the polydisperse grafted layer by the matrix chains. This work demonstrates that at high grafting densities, polydispersity in graft length can be used to stabilize dispersions of grafted nanoparticles in a polymer matrix at conditions where monodisperse grafts would cause aggregation.
Six vinyl-based, imidazolium room-temperature ionic liquid (RTIL) monomers were synthesized and photopolymerized to form dense poly(RTIL) membranes. The effect of polymer backbone (i.e., poly(ethylene), poly(styrene), and poly(acrylate)) and functional cationic substituent (e.g., alkyl, fluoroalkyl, oligo(ethylene glycol), and disiloxane) on ideal CO2/N2 and CO2/CH4 membrane separation performance was investigated. The vinyl-based poly(RTIL)s were found to be generally less CO2-selective compared to analogous styrene- and acrylate-based poly(RTIL)s. The CO2 permeability of n-hexyl- (69 barrers) and disiloxane- (130 barrers) substituted vinyl-based poly(RTIL)s were found to be exceptionally larger than that of previously studied styrene and acrylate poly(RTIL)s. The CO2 selectivity of oligo(ethylene glycol)-functionalized vinyl poly(RTIL)s was enhanced, and the CO2 permeability was reduced when compared to the n-hexyl-substituted vinyl-based poly(RTIL). Nominal improvement in CO2/CH4 selectivity was observed upon fluorination of the n-hexyl vinyl-based poly(RTIL), with no observed change in CO2 permeability. However, rather dramatic improvements in both CO2 permeability and selectivity were observed upon blending 20 mol % RTIL (emim Tf2N) into the n-hexyl- and disiloxane-functionalized vinyl poly(RTIL)s to form solid–liquid composite films.
Polymerized room-temperature ionic liquids (poly(RTIL)s) have garnered attention as new and interesting membrane materials for CO2/light gas separations because they combine the high CO2 affinity and thermal and chemical stability of RTILs, with the physical and mechanical properties of polymeric materials. Our group recently synthesized a new type of block copolymer (BCP) combining an imidazolium-based poly(RTIL) and an alkyl non-ionic polymer. These alkyl-b-ionic BCPs phase-separate into ordered nanostructures. Prior work investigating gas transport through phase-separated BCPs is very limited, and none has included RTIL-based BCP systems. However it has been shown that nanoscale phase-separation could facilitate gas transport via nanostructure orientation control or phase connectivity improvement. We have successfully made defect-free, thin-film composite membranes with these novel alkyl-imidazolium BCPs as a 3–20μm thick top layer, and determined their CO2/N2 separation properties via single-gas permeability measurements and selectivity calculations. These new BCP materials were found to have distinct advantages over the analogous physical blends of the parent homopolymers with respect to membrane fabrication. The composition of the BCP top layer, which is directly connected to the type of nanostructure formed, was found to have a significant effect on CO2 permeability (i.e., it can increase CO2 permeability by two orders of magnitude up to an observed value of 9300barrer). This improvement is mainly due to a large increase in the diffusion coefficient in the ordered nanostructures compared to amorphous BCP materials.
Reversible biomolecular patterning in hydrogels can direct cell function in a user-defined manner. In their communication on page 1816 ff., K. S. Anseth and C. A DeForest report 4D spatiotemporal control over the presentation of bioligands by using a thiol–ene photoconjugation reaction, which is initiated by visible light, combined with the photocleavage of an o-nitrobenzyl ether, which is controlled by UV light. This method allows cell functions to be probed dynamically.
Garment materials that provide protection against exposure to toxic chemical warfare agents (CWAs) not only require the ability to block the passage of these toxic compounds in vapor form but also the ability to transport water vapor to allow cooling for the wearer. Only a very limited number of examples of such “breathable” CWA barrier materials are known. A new type of reactive organic/inorganic composite film material is presented that has a very high water vapor transport rate (>1800 g m^–2 day^–1 for a 220-μm-thick film) and the ability to completely block penetration of the mustard agent simulant, 2-chloroethyl ethyl sulfide (CEES), after 22 h of continuous exposure. This new composite material is based on two components: (1) a cross-linked, diol-functionalized room-temperature ionic liquid polymer that serves as a dense, flexible hydrophilic matrix, and (2) a basic zeolite (sodium zeolite-Y (NaY)) that serves as an inexpensive, nucleophilic additive that chemically degrades the CEES as it enters the film. Preliminary FT-IR studies on this new reactive barrier material suggest that the OH groups on the ionic polymer not only facilitates water vapor transport but may also help activate mustard-type vapors for reaction with the imbedded NaY.
Current methods to contain and decontaminate materials contacted by toxic chemical warfare agents (CWAs) have disadvantages with respect to ease of delivery, portability, and effectiveness on porous substrates. A portable, easy-to-use, spreadable coating that immediately acts as a barrier to contain CWA vapors on contacted substrates and also decontaminates soaked-in CWAs is highly desired. A new type of decontaminating barrier coating for sulfur mustard (i.e., blister agent) CWAs has been developed that is made of (1) a spreadable nonvolatile, fluid matrix based on a room-temperature ionic liquid (RTIL), (2) an organic gelator that acts as a solidifying agent to help the applied coating adhere to and prevent runoff from angled or vertical surfaces, and (3) a polyamine that acts as a reagent to chemically degrade and help draw out adsorbed blister agent. When applied to porous and nonporous substrates contacted with 2-chloroethyl ethyl sulfide (CEES, a mustard agent simulant), this spreadable, soft solid coating was found to act as an effective barrier, blocking 70–90% of the CEES vapor from entering the overhead space compared to uncoated samples. Furthermore, this reactive gel RTIL coating was able to remove (i.e., draw out and degrade) 70–95% of the liquid CEES soaked into porous substrates after 24 h at ambient temperature when applied as a static, single-application coating. Preliminary studies with added dyes and indicators to this coating system have shown that the decontamination process may be followed visually via color changes.
In summary, a new glycerol-based LLC monomer system has been developed that enables facile fabrication of unprecedented TFC QI membranes that have molecular sieving capabilities, high salt rejection, and good water permeability. We are currently exploring methods to reduce the thickness of the 3/glycerol layers to ≤0.3 μm and increase flux by optimizing roll-casting and support parameters, as well as by using other solution processing techniques (e.g., dip-, spray-, and spin-coating). We are also exploring methods for varying the QI pore size, such as the use of cosurfactants, different anions, and mixtures of LLC solvents.
Mechanophotopatterning on a photoresponsive elastomer was demonstrated by Bowman and coworkers, enabling for the first time the ability to precisely and simultaneously manipulate both the material’s shape and surface topography by exposure to light without the need for solvents, molding, or physical contact.
This work was featured in a Nature “News and Views” article by Prof. Huck 472 (7344) 425 (2011).
Photopatterning of a photoreversible covalent elastomeric network under mechanical strain, or mechanophotopatterning, provides a facile approach to fabricate complex topographical features using elementary irradiation schemes. A photoresponsive material is deformed in two dimensions and irradiated through a mask, resulting in a transparent material with topography that reflects the concentric rings of the mask.
The click reaction paradigm is focused on the development and implementation of reactions that are simple to perform while being robust and providing exquisite control of the reaction and its products. Arguably the most prolific and powerful of these reactions, the copper-catalysed alkyne-azide reaction (CuAAC) is highly efficient and ubiquitous in an ever increasing number of synthetic methodologies and applications, including bioconjugation, labelling, surface functionalization, dendrimer synthesis, polymer synthesis and polymer modification. Unfortunately, as the Cu(I) catalyst is typically generated by the chemical reduction of Cu(II) to Cu(I), or added as a Cu(I) salt, temporal and spatial control of the CuAAC reaction is not readily achieved. Here, we demonstrate catalysis of the CuAAC reaction via the photochemical reduction of Cu(II) to Cu(I), affording comprehensive spatial and temporal control of the CuAAC reaction using standard photolithographic techniques. Results reveal the diverse capability of this technique in small molecule synthesis, patterned material fabrication and patterned chemical modification.
Defect-free, microporous Al2O3/SAPO-34 zeolite composite membranes were prepared by coating hydrothermally grown zeolite membranes with microporous alumina using molecular layer deposition. These inorganic composite membranes are highly efficient for H2 separation: their highest H2/N2 mixture selectivity was 1040, in contrast with selectivities of 8 for SAPO-34 membranes. The composite membranes were selective for H2 for temperatures up to at least 473 K and feed pressures up to at least 1.5 MPa; at 473 K and 1.5 MPa, the H2/N2 separation selectivity was 750. The H2/CO2 separation selectivity was lower than the H2/N2 selectivity and decreased slightly with increasing pressure; the selectivity was 20 at 473 K and 1.5 MPa. The high H2 selectivity resulted either because most of the pores in the Al2O3 layer were slightly smaller than 0.36 nm (the kinetic diameter of N2) or because the Al2O3 layer slightly narrowed the SAPO-34 pore entrance. These composite membranes may represent a new class of inorganic membranes for gas separation.
This work was featured in Nature, "Sticky balls," 466, 417 (2010).
Granular flows involving liquid-coated solids are ubiquitous in nature (pollen capture, avalanches) and industry (filtration, pharmaceutical mixing). In this Letter, three-body collisions between liquid-coated spheres are investigated experimentally using a “Stokes’s cradle,” which resembles the popular desktop toy Newton’s cradle (NC). Surprisingly, previous work shows that every possible outcome was observed in the Stokes’s cradle except the traditional NC outcome. Here, we experimentally achieve NC via guidance from a theory, which revealed that controlling the liquid-bridge volume connecting two target particles is the key in attaining the NC outcome. These three-body experiments also provide direct evidence that the fluid resistance upon rebound cannot be completely neglected due to presumed cavitation; this resistance also influences two-body systems yet cannot be isolated experimentally in such systems.
Following Sharpless′ visionary characterization of several idealized reactions as click reactions, the materials science and synthetic chemistry communities have pursued numerous routes toward the identification and implementation of these click reactions. Herein, we review the radical-mediated thiol–ene reaction as one such click reaction. This reaction has all the desirable features of a click reaction, being highly efficient, simple to execute with no side products and proceeding rapidly to high yield. Further, the thiol–ene reaction is most frequently photoinitiated, particularly for photopolymerizations resulting in highly uniform polymer networks, promoting unique capabilities related to spatial and temporal control of the click reaction. The reaction mechanism and its implementation in various synthetic methodologies, biofunctionalization, surface and polymer modification, and polymerization are all reviewed.
Individual molecules of fluorophore-labeled alkanoic acids with various chain lengths, BODIPY−(CH2)n−COOH (abbreviated as fl-Cn), were observed to adsorb and move at the methylated fused silica−water interface as a function of temperature using total internal reflection fluorescence microscopy. The statistical analysis of squared-displacement distributions indicated that the molecular trajectories were consistent with a diffusive model involving two intertwined modes. The slower mode, typically responsible for <50% of the molecular diffusion time, had a diffusion coefficient of <0.005 μm2/s and could not be distinguished from the apparent motions of immobilized molecules because of the limitations of experimental resolution. The faster mode exhibited diffusion coefficients that increased with temperature for all chain lengths, permitting an Arrhenius analysis. Both the effective activation energies and kinetic prefactors associated with the fast-mode diffusion coefficients increased systematically with chain length for fl-C2 through fl-C10; however, fl-C15 did not follow this trend but instead exhibited anomalously small values of both parameters. These observations were considered in the context of hydrophobic interactions between the adsorbate molecules and the methylated surface in the presence of water. Specifically, it was hypothesized that fl-C2, fl-C4, and fl-C10 adopted primarily extended molecular conformations on the hydrophobic surface. The increases in activation energy and entropy with chain length for these molecules are consistent with a picture of the transition state in which the molecule partially detaches from the surface and exhibits greater conformational freedom. In contrast, the small activation energy and entropy for fl-C15 are consistent with a scenario in which the surface-bound molecule adopts a compact/globular conformation with limited surface contact and conformational flexibility.
A method is presented to prepare high-density, vertically aligned carbon nanotube (VA-CNT) membranes. The CNT arrays were prepared by chemical vapor deposition (CVD), and the arrays were collapsed into dense membranes by capillary-forces due to solvent evaporation. The average space between the CNTs after shrinkage was 3 nm, which is comparable to the pore size of the CNTs. Thus, the interstitial pores between CNTs were not sealed, and gas permeated through both CNTs and interstitial pores. Nanofiltration of gold nanoparticles and N2 adsorption indicated the pore diameters were approximately 3 nm. Gas permeances, based on total membrane area, were 1−4 orders of magnitude higher than VA-CNT membranes in the literature, and gas permeabilities were 4−7 orders of magnitude higher than literature values. Gas permeances were approximately 450 times those predicted for Knudsen diffusion, and ideal selectivities were similar to or higher than Knudsen selectivities. These membranes separated a larger molecule (triisopropyl orthoformate (TIPO)) from a smaller molecule (n-hexane) during pervaporation, possibly due to the preferential adsorption, which indicates separation potential for liquid mixtures.