Thermoresponsive Polymers under Pressure with a Focus on Poly(N-isopropylacrylamide) (PNIPAM).

Pressure is a key variable in the phase behavior of responsive polymers, both for applications and from a fundamental point of view. In this feature article, we review recent developments, particularly applications of neutron techniques such as small-angle neutron scattering (SANS) and quasi-elastic neutron scattering (QENS), across the temperature-pressure phase diagram. These are complemented by kinetic SANS experiments following pressure jumps. In the prototype system poly(N-isopropylacrylamide) (PNIPAM), QENS revealed the pressure-dependent characteristics of hydration water around the lower critical solution temperature transition. The size, water content, and inner structure of the mesoglobules formed in the two-phase region depend strongly on pressure, as shown by SANS. Beside these changes at the phase transition, the mesoglobule formation at low pressure is determined by kinetic factors, namely the formation of a polymer-rich, rigid shell, which hampers further growth by coalescence. At high pressure, in contrast, the growth proceeds by diffusion-limited coalescence without any kinetic hindrance. The disintegration of the mesoglobules evolves either via chain release from their surface or via swelling, depending on the osmotic pressure of the water. Moreover, we report on the profound influence of pressure on the cononsolvency effect. In the temperature-pressure frame, the one-phase region is hugely expanded upon the addition of the cosolvent methanol. SANS experiments unveil the enthalpic and entropic contributions to the effective Flory-Huggins interaction parameter between the segments and the solvent mixture. QENS experiments demonstrate an increase in polymer associated water with pressure, whereas methanol is released. Correspondingly, the solvent phase becomes enriched in methanol, providing a mechanism for the breakdown of cononsolvency at a high pressure. Finally, we outline future opportunities for high-pressure studies of thermoresponsive polymers, with a focus on neutron methods.

Dynamic Behavior of Poly(N-isopropylmethacrylamide) in Neat Water and in Water/Methanol Mixtures.

We investigate the collective dynamics of thermoresponsive polymer poly(N-isopropylmethacrylamide) (PNIPMAM) in aqueous solution and in water/methanol mixtures in the one-phase region. In neat water, the polymer concentration c is varied in a wide range around the overlap concentration c*, that is estimated at 23 g L-1. Using dynamic light scattering (DLS), two decays ("modes") are consistently observed in the intensity autocorrelation functions for c = 2-150 g L-1 with relaxation rates which are proportional to the square of the momentum transfer. Below c*, these are attributed to the diffusion of single chains and to clusters from PNIPMAM that are formed due to hydrophobic interactions. Above c*, they are assigned to the diffusion of the chain segments between overlap points and to long-range concentration fluctuations. From the temperature-dependent behavior of the overall scattering intensities and the dynamic correlation lengths of the fast mode, the critical temperatures and the scaling exponents are determined. The latter are significantly lower than the static values predicted by mean-field theory, which may be related to the presence of the large-scale inhomogeneities. The effect of the cosolvent methanol on the dynamics is investigated for polymer solutions having c = 30 g L-1 and methanol volume fractions in the solvent mixtures of up to 60 vol %. The phase diagram was established by differential scanning calorimetry. The slow mode detected by DLS becomes significantly weaker as methanol is added, i.e., the solutions become more homogeneous. Beyond the minimum of the coexistence line, which is located at 40-50 vol % of methanol, the dynamics is qualitatively different from the one at lower methanol contents. Thus, going from the water-rich to the methanol-rich side of the miscibility gap, the change of interaction of the PNIPMAM chains with the two solvents has a severe effect on the collective dynamics.

PNIPAM Mesoglobules in Dependence on Pressure.

Poly(N-isopropylacrylamide) (PNIPAM) in aqueous solution forms mesoglobules above its cloud point temperature Tcp. While these are small and compact at atmospheric pressure, they are large and water-rich at high pressure. To identify the transition between these states, we employed optical microscopy and carried out isothermal pressure scans. Using very small angle neutron scattering, we determined the size and water content of the mesoglobules in pressure scans at different temperatures above Tcp. We observe a distinct transition at pressures of 35-55 MPa with the transition pressure depending on temperature. While the transition is smooth at high temperatures, i.e., far away from the coexistence line, it is abrupt at low temperatures, i.e., close to the coexistence line. Hence, at high temperatures, the swelling of the mesoglobules dominates, whereas at low temperatures, the coalescence of mesoglobules prevails. Subsequently decreasing the pressure results in a gradual deswelling of the mesoglobules at high temperature. In contrast, at low temperatures, small and compact mesoglobules form, but the large aggregates persist. We conclude that, on the time scale of the experiment, the disintegration of the large swollen aggregates into small and compact mesoglobules is only partially possible. Erasing the history by cooling the sample at the maximum pressure into the one-phase state does not result in qualitative changes for the behavior with the only difference that Fewer mesoglobules are formed when the pressure is decreased again. The newly identified transition line separates the low-pressure from the high-pressure regime.

Rigid-to-Flexible Transition in a Molecular Brush in a Good Solvent at a Semidilute Concentration.

The structures of a molecular brush in a good solvent are investigated using synchrotron small-angle X-ray scattering in a wide range of concentrations. The brush under study, PiPOx239-g-PnPrOx14, features a relatively long poly(2-isopropenyl-2-oxazoline) (PiPOx) backbone and short poly(2-n-propyl-2-oxazoline) (PnPrOx) side chains. As a solvent, ethanol is used. By model fitting, the overall size and the persistence length as well as the interaction length and interaction strength are determined. At this, the interplay between form and structure factor is taken into account. The conformation of the molecular brush is traced upon increasing the solution concentration, and a rigid-to-flexible transition is found near the overlap concentration. Finally, the results of computer simulations of the molecular brush solutions confirm the experimental results.

Poly(sulfobetaine)-Based Diblock Copolymer Thin Films in Water/Acetone Atmosphere: Modulation of Water Hydration and Co-nonsolvency-Triggered Film Contraction.

The water swelling and subsequent solvent exchange including co-nonsolvency behavior of thin films of a doubly thermo-responsive diblock copolymer (DBC) are studied via spectral reflectance, time-of-flight neutron reflectometry, and Fourier transform infrared spectroscopy. The DBC consists of a thermo-responsive zwitterionic (poly(4-((3-methacrylamidopropyl) dimethylammonio) butane-1-sulfonate)) (PSBP) block, featuring an upper critical solution temperature transition in aqueous media but being insoluble in acetone, and a nonionic poly(N-isopropylmethacrylamide) (PNIPMAM) block, featuring a lower critical solution temperature transition in water, while being soluble in acetone. Homogeneous DBC films of 50-100 nm thickness are first swollen in saturated water vapor (H2O or D2O), before they are subjected to a contraction process by exposure to mixed saturated water/acetone vapor (H2O or D2O/acetone-d6 = 9:1 v/v). The affinity of the DBC film toward H2O is stronger than for D2O, as inferred from the higher film thickness in the swollen state and the higher absorbed water content, thus revealing a pronounced isotope sensitivity. During the co-solvent-induced switching by mixed water/acetone vapor, a two-step film contraction is observed, which is attributed to the delayed expulsion of water molecules and uptake of acetone molecules. The swelling kinetics are compared for both mixed vapors (H2O/acetone-d6 and D2O/acetone-d6) and with those of the related homopolymer films. Moreover, the concomitant variations of the local environment around the hydrophilic groups located in the PSBP and PNIPMAM blocks are followed. The first contraction step turns out to be dominated by the behavior of the PSBP block, whereas the second one is dominated by the PNIPMAM block. The unusual swelling and contraction behavior of the latter block is attributed to its co-nonsolvency behavior. Furthermore, we observe cooperative hydration effects in the DBC films, that is, both polymer blocks influence each other's solvation behavior.

Cononsolvency of thermoresponsive polymers: where we are now and where we are going.

Cononsolvency is an intriguing phenomenon where a polymer collapses in a mixture of good solvents. This cosolvent-induced modulation of the polymer solubility has been observed in solutions of several polymers and biomacromolecules, and finds application in areas such as hydrogel actuators, drug delivery, compound detection and catalysis. In the past decade, there has been a renewed interest in understanding the molecular mechanisms which drive cononsolvency with a predominant emphasis on its connection to the preferential adsorption of the cosolvent. Significant efforts have also been made to understand cononsolvency in complex systems such as micelles, block copolymers and thin films. In this review, we will discuss some of the recent developments from the experimental, simulation and theoretical fronts, and provide an outlook on the problems and challenges which are yet to be addressed.

Salt-Dependent Phase Transition Behavior of Doubly Thermoresponsive Poly(sulfobetaine)-Based Diblock Copolymer Thin Films.

The water vapor-induced swelling, as well as subsequent phase-transition kinetics, of thin films of a diblock copolymer (DBC) loaded with different amounts of the salt NaBr, is investigated in situ. In dilute aqueous solution, the DBC features an orthogonally thermoresponsive behavior. It consists of a zwitterionic poly(sulfobetaine) block, namely, poly(4-(N-(3'-methacrylamidopropyl)-N,N-dimethylammonio) butane-1-sulfonate) (PSBP), showing an upper critical solution temperature, and a nonionic block, namely, poly(N-isopropylmethacrylamide) (PNIPMAM), exhibiting a lower critical solution temperature. The swelling kinetics in D2O vapor at 15 °C and the phase transition kinetics upon heating the swollen film to 60 °C and cooling back to 15 °C are followed with simultaneous time-of-flight neutron reflectometry and spectral reflectance measurements. These are complemented by Fourier transform infrared spectroscopy. The collapse temperature of PNIPMAM and the swelling temperature of PSBP are found at lower temperatures than in aqueous solution, which is attributed to the high polymer concentration in the thin-film geometry. Upon inclusion of sub-stoichiometric amounts (relative to the monomer units) of NaBr in the films, the water incorporation is significantly increased. This increase is mainly attributed to a salting-in effect on the zwitterionic PSBP block. Whereas the addition of NaBr notably shifts the swelling temperature of PSBP to lower temperatures, the collapse temperature of PNIPMAM remains unaffected by the presence of salt in the films.

Co-nonsolvency in concentrated aqueous solutions of PNIPAM: effect of methanol on the collective and the chain dynamics.

The polymer dynamics in concentrated solutions of poly(N-isopropyl acrylamide) (PNIPAM) in D2O/CD3OD mixtures is investigated in the one-phase region. Two polymer concentrations (9 and 25 wt%) and CD3OD contents in the solvent mixture of 0, 10 and 15 vol% are chosen. Temperature-resolved dynamic light scattering (DLS) reveals the collective dynamics. Two modes are observed, namely the fast relaxation of polymer segments within the blobs and the slow collective relaxation of the blobs. As the cloud point is approached, the correlation length related to the fast mode increases with CD3OD content. It features critical scaling behavior, which is consistent with mean-field behavior for the 9 wt% PNIPAM solution in pure D2O and with 3D Ising behavior for all other solutions. While the slow mode is not very strong in the 9 wt% PNIPAM solution in pure D2O, it is significantly more prominent as CD3OD is added and at all CD3OD contents in the 25 wt% solution, which may be attributed to enhanced interaction between the polymers. Neutron spin-echo spectroscopy (NSE) reveals a decay in the intermediate structure factor which indicates a diffusive process. For the polymer concentration of 9 wt%, the diffusion coefficients from NSE are similar to the ones from the fast relaxation observed in DLS. In contrast, they are significantly lower for the solutions having a polymer concentration of 25 wt%, which is attributed to the influence of the dominant large-scale dynamic heterogeneities. To summarize, addition of cosolvent leads to enhanced large-scale heterogeneities, which are reflected in the dynamic behavior at small length scales.

Solvent Vapor Annealing of a Diblock Copolymer Thin Film with a Nonselective and a Selective Solvent: Importance of Pathway for the Morphological Changes.

Diblock copolymer thin films of polystyrene-block-poly(dimethyl siloxane) (PS-b-PDMS) featuring PDMS cylinders in a PS matrix are investigated during solvent vapor annealing with mixtures of n-heptane (which is strongly selective for PDMS) and toluene (which is close to nonselective for both blocks). Swelling in the vapor of one of the pure solvents and exchanging it stepwise by the vapor of the other solvent is compared to swelling in a given binary solvent vapor mixture for a prolonged time. The resulting structural changes, such as ordering of the cylinders on a hexagonal lattice and their transition into lamellae, are followed using in situ, real-time grazing-incidence small-angle X-ray scattering (GISAXS). In three runs, the sequence of solvent vapor swelling and vapor exchange is varied. Compiling the resulting morphologies in a diagram of states in dependence on the solvent content in the film and in the minority nanodomains allows insight into the role of the glass transition of the PS matrix for the ordering processes and their time scales. Based on these findings, a protocol is suggested to efficiently obtain an order-to-order transition from the cylindrical morphology with random domain orientation to the oriented lamellar state.

Switch It Inside-Out: "Schizophrenic" Behavior of All Thermoresponsive UCST-LCST Diblock Copolymers.

This feature article reviews our recent advancements on the synthesis, phase behavior, and micellar structures of diblock copolymers consisting of oppositely thermoresponsive blocks in aqueous environments. These copolymers combine a nonionic block, which shows lower critical solution temperature (LCST) behavior, with a zwitterionic block that exhibits an upper critical solution temperature (UCST). The transition temperature of the latter class of polymers is strongly controlled by its molar mass and by the salt concentration, in contrast to the rather invariant transition of nonionic polymers with type II LCST behavior such as poly(N-isopropylacrylamide) or poly(N-isopropyl methacrylamide). This allows for implementing the sequence of the UCST and LCST transitions of the polymers at will by adjusting either molecular or, alternatively, physical parameters. Depending on the location of the transition temperatures of both blocks, different switching scenarios are realized from micelles to inverse micelles, namely via the molecularly dissolved state, the aggregated state, or directly. In addition to studies of (semi)dilute aqueous solutions, highly concentrated systems have also been explored, namely water-swollen thin films. Concerning applications, we discuss the possible use of the diblock copolymers as "smart" nanocarriers.

Hydration and Dehydration Kinetics: Comparison between Poly( N-isopropyl methacrylamide) and Poly(methoxy diethylene glycol acrylate) Films.

Thermoresponsive films of poly( N-isopropyl methacrylamide) (PNIPMAM) and poly(methoxy diethylene glycol acrylate) (PMDEGA) are compared with respect to their hydration and dehydration kinetics using in situ neutron reflectivity. Both as-prepared films present a homogeneous single-layer structure and have similar transition temperatures of the lower critical solution temperature type (TT, PNIPMAM 38 °C and PMDEGA 41 °C). After hydration in unsaturated D2O vapor at 23 °C, a D2O enrichment layer is observed in PNIPMAM films adjacent to the Si substrate. In contrast, two enrichment layers are present in PMDEGA films (close to the vapor interface and the Si substrate). PNIPMAM films exhibit a higher hydration capability, ascribed to having both donor (N-H) and acceptor (C═O) units for hydrogen bonds. While the swelling of the PMDEGA films is mainly caused by the increase of the enrichment layers, the thickness of the entire PNIPMAM films increases with time. The observed longer relaxation time for swelling of PNIPMAM films is attributed to the much higher glass transition temperature of PNIPMAM. When dehydrating both films by increasing the temperature above the TT, they react with a complex response consisting of three stages (shrinkage, rearrangement, and reswelling). PNIPMAM films respond faster than PMDEGA films. After dehydration, both films still contain a large amount of D2O, and no completely dry film state is reached for a temperature above their TTs.

All-In-One "Schizophrenic" Self-Assembly of Orthogonally Tuned Thermoresponsive Diblock Copolymers.

Smart, fully orthogonal switching was realized in a highly biocompatible diblock copolymer system with variable trigger-induced aqueous self-assembly. The polymers are composed of nonionic and zwitterionic blocks featuring lower and upper critical solution temperatures (LCSTs and UCSTs). In the system investigated, diblock copolymers from poly( N-isopropyl methacrylamide) (PNIPMAM) and a poly(sulfobetaine methacrylamide), systematic variation of the molar mass of the latter block allowed for shifting the UCST of the latter above the LCST of the PNIPMAM block in a salt-free condition. Thus, successive thermal switching results in "schizophrenic" micellization, in which the roles of the hydrophobic core block and the hydrophilic shell block are interchanged depending on the temperature. Furthermore, by virtue of the strong electrolyte-sensitivity of the zwitterionic polysulfobetaine block, we succeeded to shift its UCST below the LCST of the PNIPMAM block by adding small amounts of an electrolyte, thus inverting the pathway of switching. This superimposed orthogonal switching by electrolyte addition enabled us to control the switching scenarios between the two types of micelles (i) via an insoluble state, if the LCST-type cloud point is below the UCST-type cloud point, which is the case at low salt concentrations or (ii) via a molecularly dissolved state, if the LCST-type cloud point is above the UCST-type cloud point, which is the case at high salt concentrations. Systematic variation of the block lengths allowed for verifying the anticipated behavior and identifying the molecular architecture needed. The versatile and tunable self-assembly offers manifold opportunities, for example, for smart emulsifiers or for sophisticated carrier systems.

Binding of HSA to Macromolecular pHPMA Based Nanoparticles for Drug Delivery: An Investigation Using Fluorescence Methods.

Amphiphilic poly( N-(2-hydroxypropyl)methacrylamide) copolymers ( pHPMA) bearing cholesterol side groups in phosphate buffer saline self-assemble into nanoparticles (NPs) which can be used as tumor-targeted drug carriers. It was previously shown by us that human serum albumin (HSA) interacts weakly with the NPs. However, the mechanism of this binding could not be resolved due to overlapping of signals from the complex system. Here, we use fluorescence labeling to distinguish the components and to characterize the binding: On the one hand, a fluorescent dye was attached to pHPMA, so that the diffusion behavior of the NPs could be studied in the presence of HSA using fluorescence lifetime correlation spectroscopy. On the other hand, quenching of the intrinsic fluorescence of HSA revealed the origin of the binding, which is mainly the complexation between HSA and cholesterol side groups. Furthermore, a binding constant was obtained.

Superhydrophobic Silicon Nanocrystal-Silica Aerogel Hybrid Materials: Synthesis, Properties, and Sensing Application.

Silicon nanocrystals (SiNCs) are abundant and exhibit exquisitely tailorable optoelectronic properties. The incorporation of SiNCs into highly porous and lightweight substrates such as aerogels leads to hybrid materials possessing the attractive features of both materials. This study describes the covalent deposition of SiNCs on and intercalation into silica aerogels, explores the properties, and demonstrates a prototype sensing application of the composite material. SiNCs of different sizes were functionalized with triethoxyvinylsilane (TEVS) via a radical grafting approach and subsequently used for the synthesis of photoluminescent silica hybrids. The resulting SiNC-containing aerogels possess high porosities, SiNC-based size-dependent photoluminescence, transparency, and a superhydrophobic macroscopic surface. The materials were used to examine the photoluminescence response toward low concentrations of 3-nitrotoluene (270 µM), demonstrating their potential as a sensing platform for high-energy materials.

Macromolecular pHPMA-Based Nanoparticles with Cholesterol for Solid Tumor Targeting: Behavior in HSA Protein Environment.

Nanoparticles (NPs) that form by self-assembly of amphiphilic poly(N-(2-hydroxypropyl)-methacrylamide) (pHPMA) copolymers bearing cholesterol side groups are potential drug carriers for solid tumor treatment. Here, we investigate their behavior in solutions of human serum albumin (HSA) in phosphate buffered saline. Mixed solutions of NPs, from polymer conjugates with or without the anticancer drug doxorubicin (Dox) bound to them, and HSA at concentrations up to the physiological value are characterized by synchrotron small-angle X-ray scattering and isothermal titration calorimetry. When Dox is absent, a small amount of HSA molecules bind to the cholesterol groups that form the core of the NPs by diffusing through the loose pHPMA shell or get caught in meshes formed by the pHPMA chains. These interactions are strongly hindered by the presence of Dox, which is distributed in the pHPMA shell, meaning that the delivery of Dox by the NPs in the human body is not affected by the presence of HSA.

Effect of chain architecture on the swelling and thermal response of star-shaped thermo-responsive (poly(methoxy diethylene glycol acrylate)-block-polystyrene)3 block copolymer films.

The effect of chain architecture on the swelling and thermal response of thin films obtained from an amphiphilic three-arm star-shaped thermo-responsive block copolymer poly(methoxy diethylene glycol acrylate)-block-polystyrene ((PMDEGA-b-PS)3) is investigated by in situ neutron reflectivity (NR) measurements. The PMDEGA and PS blocks are micro-phase separated with randomly distributed PS nanodomains. The (PMDEGA-b-PS)3 films show a transition temperature (TT) at 33 °C in white light interferometry. The swelling capability of the (PMDEGA-b-PS)3 films in a D2O vapor atmosphere is better than that of films from linear PS-b-PMDEGA-b-PS triblock copolymers, which can be attributed to the hydrophilic end groups and limited size of the PS blocks in (PMDEGA-b-PS)3. However, the swelling kinetics of the as-prepared (PMDEGA-b-PS)3 films and the response of the swollen film to a temperature change above the TT are significantly slower than that in the PS-b-PMDEGA-b-PS films, which may be related to the conformation restriction by the star-shape. Unlike in the PS-b-PMDEGA-b-PS films, the amount of residual D2O in the collapsed (PMDEGA-b-PS)3 films depends on the final temperature. It decreases from (9.7 ± 0.3)% to (7.0 ± 0.3)% or (6.0 ± 0.3)% when the final temperatures are set to 35 °C, 45 °C and 50 °C, respectively. This temperature-dependent reduction of embedded D2O originates from the hindrance of chain conformation from the star-shaped chain architecture.

Dynamic glass transition of the rigid amorphous fraction in polyurethane-urea/SiO2 nanocomposites.

We report molecular dynamics in the rigid amorphous fraction (RAF) of the polymer bound at the interfaces with nanoparticles in polymer nanocomposites and calculate the glass transition temperature, Tg, for this bound layer of polymer. We follow the '3-phase-model' for semicrystalline polymers where the polymer matrix consists of the crystalline fraction (CF), the mobile amorphous fraction (MAF) and the RAF. While the amorphous polymer bound by crystallites is completely rigid, neither contributing to the glass transition, nor displaying molecular dynamics, the amorphous polymer bound at the interfaces with filler displays decelerated dynamics, as compared to the bulk polymer. Reports in the literature suggest a discrepancy between Tg values obtained by Differential Scanning Calorimetry (DSC) and by Dielectric Relaxation Spectroscopy (DRS). As a plausible explanation we suggest that DRS results in Tg values taking into account the bound polymer, whereas DSC does not. For this investigation we use semicrystalline polyurethane-urea/SiO2 nanocomposites and employ, next to DSC and DRS, SEM, SAXS and WAXS for morphological characterization. It is our intention to use DRS as a tool for investigating the RAF.

pH Responsiveness of hydrogels formed by telechelic polyampholytes.

We investigate the influence of pH on the rheological and structural properties of hydrogels formed by hydrophobic association of the sticky ends of the triblock terpolymer poly(methyl methacrylate)-b-poly(2-(diethylamino)ethyl methacrylate-co-methacrylic acid)-b-poly(methyl methacrylate) (PMMA-b-P(DEA-co-MAA)-b-PMMA). The middle block is a weak polyampholyte having a pH dependent charge density and sign, which enables tuning of the rheological and structural properties by pH variation. Small-angle neutron scattering (SANS) studies of solutions in D2O at 0.05 wt% and pH 3.0 reveal clusters of interconnected spherical micelles having PMMA cores, stabilized by repulsive ionic interactions in the middle polyampholyte block. With increasing pH, the degree of ionization of the DEA units decreases, whereas the one of the MAA units increases, resulting in a complete loss of the correlation between these micelles. At a concentration of 3 wt% at low pH values, the system forms a gel with charged fuzzy spheres from PMMA interacting via a screened Coulomb potential. With increasing pH, the gel disintegrates due to the decrease in the effective charge on the micelles. At both concentrations, the hydrophobic aggregation of micelles is observed near the isoelectric point. At pH 3.0-7.4, the autocorrelation functions measured by rotational dynamic light scattering at 3 wt% exhibit a decay steeper than single exponential, which confirms that the gels are frozen, presumably due to the glassy PMMA cores and hydrophobic interpolyelectrolyte complexes. At pH 11, the diffusion of single micelles is observed in addition to the frozen dynamics.

Bandgap-Tuning in Triple-Chalcogenophene Polymer Films by Thermal Annealing.

The authors study adjustable bandgap properties of the novel triple chalcogenophene-based polymer poly-(3-hexyl-2(3-(4-hexylthiophene-2-yl)-4,5-butylselenophene-1-yl)-5-(4,5-butyltellurophene-1-yl)thiophene) through a combination of morphological, spectroscopic, and computational techniques. The bandgap can be tuned after polymerization by means of mild temperature annealing, which will allow for a partnership with a broader range of donor/acceptor molecules, a property that makes it potentially suitable for organic photovoltaic implementation. The bandgap is modified by selection of the annealing temperatures, and the process is arguably related to the aggregation of tellurophene units, as similar effects are observed in polytellurophenes. Moreover, adequate chemistry engineering ensures easy solution processability and attainment of homogeneous films, which is also essential for applications.

Characterization of Lipid-Based Hexosomes as Versatile Vaccine Carriers.

Subunit vaccines typically show insufficient immunogenicity. To address this issue, we developed a novel self-adjuvanting particulate carrier system based upon the lipids phytantriol (Phy) and mannide monooleate (MaMo). Phy is a lipid known to form nonlamellar phases in fully hydrated systems, whereas MaMo has been found to promote immune responses in emulsion form. A bulk phase composition of Phy/MaMo (14 wt %) showed hexagonal (HII) phase behavior over a practical temperature range (including room and body temperature), and was therefore used for particle development. Hexosomes stabilized with different concentrations of either poloxamer 407, Myrj 59, or Pluronic F108 were successfully prepared. To demonstrate the versatile nature of these systems, the particles were further modified with either positively or negatively charged lipids and loaded with model antigens, while maintaining the HII structure. These hexosomes are structurally robust and amenable to customization, rendering them suitable as antigen delivery carriers.