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Atomic-force microscopy coupled with infrared spectroscopy (AFM-IR) deciphers surface morphology of thin-film polymer blends and composites by simultaneously mapping physical topography and chemical composition.

The facile oxidation of PS-b-P4VP and PS-b-P2VP leads to PS-b-P4VPNO and PS-b-P2VPNO copolymers with high block incompatibility (high-χ BCPs). Well-ordered, thermally-stable sub-10 nm nanostructures are obtained.

Conventional wisdom suggests that cations play a minimal role in the assembly of cationic amphiphiles. Here, we show that at liquid/liquid (L/L) interfaces, specific cation effects can modulate the assemblies of hydrophobic tails in an oil phase despite being attached to cationic headgroups in the aqueous phase. We used oligo-dimethylsiloxane (ODMS) methyl imidazolium amphiphiles to identify these specific interactions at hexadecane/aqueous interfaces. Small cations, such as Li

Direct β-arylation of thiophene derivatives with bromide as directing group is disclosed. The reaction is conducted with PdCl2/(p-tolyl)3P as catalyst, silver carbonate as additive, and aryl iodide as coupling partner, affording brominated biaryl compounds as product. Control experiments indicated that the presence of bromide group enhances the reactivity of the C–H bond, enabling β-arylation. Furthermore, the C–Br bond can be easily converted into many useful functional groups through a wide range of methodologies. The mechanistic study suggests that silver salt plays a key role in the C–H bond-activation step.

The optoelectronic properties of a given conjugated polymer depend on the chain rigidity and more importantly local chain planarity. The local backbone planarity determines the conjugation length as large twists result in break of conjugation.

Molecular orientation plays a pivotal role in defining the functionality and chemistry of interfaces, yet accurate measurements probing this important feature are few, due, in part, to technical and analytical limitations in extracting information from molecular monolayers. For example, buried liquid/liquid interfaces, where a complex and poorly understood balance of inter- and intramolecular interactions impart structural constraints that facilitate the formation of supramolecular assemblies capable of new functions, are difficult to probe experimentally. Here, we use vibrational sum-frequency generation spectroscopy, numerical polarization analysis, and atomistic molecular dynamics simulations to probe molecular orientations at buried oil/aqueous interfaces decorated with amphiphilic oligomers. We show that the orientation of self-assembled oligomers changes upon the addition of salts in the aqueous phase. The evolution of these structures can be described by competitive ion effects in the aqueous phase altering the orientations of the tails extending into the oil phase. These specific anionic effects occur via interfacial ion pairing and associated changes in interfacial solvation and hydrogen-bonding networks. These findings provide more quantitative insight into orientational changes encountered during self-assembly and pave the way for the design of functional interfaces for chemical separations, neuromorphic computing applications, and related biomimetic systems.

Liquid/liquid interfaces play a central role in scientific fields ranging from nanomaterial synthesis and soft matter electronics to nuclear waste remediation and chemical separations. This diversity of functions arises from an interface's ability to respond to changing conditions in its neighboring bulk phases. Understanding what drives this interfacial flexibility can provide novel avenues for designing new functional interfaces. However, limiting this progress is an inadequate understanding of the subtle intermolecular and interphase interactions taking place at the molecular level. Here, we use surface-specific vibrational sum frequency generation spectroscopy combined with atomistic molecular dynamics simulations to investigate the self-assembly and structure of model ionic oligomers consisting of an oligodimethylsiloxane (ODMS) tail covalently attached to a positively charged methyl imidazolium (MIM+) head group at buried oil/aqueous interfaces. We show how the presence of seemingly innocuous salts can impart dramatic changes to the ODMS tail conformations in the oil phase via specific ion effects and ion-pairing interactions taking place in the aqueous phase. These specific ion interactions are shown to drive enhanced amphiphile adsorption, induce morphological changes, and disrupt emergent hydrogen-bonding structures at the interface. Tuning these interactions allows for independent control over the oligomer structure in the oil phase versus interfacial population changes and represents key mechanistic insight that is needed to control chemical reactions at liquid/liquid interfaces.

Understanding the dynamics of soft colloids, such as star polymers, dendrimers, and microgels, is of scientific and practical importance. It is known that the excluded volume effect plays a key role in colloidal dynamics. Here, we propose a condition of compressibility equivalence that provides a simple method to experimentally evaluate the excluded volume of soft colloids from a thermodynamic view. We apply this condition to survey the dynamics of a series of star polymer dispersions. It is found that as the concentration increases, the slowing of the long-time self-diffusivity of the star polymer, normalized by the short-time self-diffusivity, can be mapped onto the hard-sphere behavior. This phenomenon reveals the dynamic equivalence between soft colloids and hard spheres, despite the apparent complexity of the interparticle interaction of the soft colloids. The methods for measuring the osmotic compressibility and the self-diffusivities of soft colloidal dispersions are also presented., 18 pages, 4 figures

Using the electrostatic complex of G4 poly(amidoamine) (PAMAM) dendrimer with an amphiphilic surfactant as a model system, contrast variation small angle neutron scattering (SANS) is implemented to resolve the key structural characteristics of dendrimer-based guest–host system. Quantifications of the radial distributions of the scattering length density and the hydration level within the complex molecule reveal that the surfactant is embedded in the peripheral region of dendrimer and the steric crowding in this region increases the backfolding of the dendritic segments, thereby reducing the hydration level throughout the complex molecule. The insights into the spatial location of the guest molecules as well as the perturbations of dendrimer conformation and hydration level deduced here are crucial for the delicate design of dendrimer-based guest–host system for biomedical applications.

The synthesis and characterization of well-defined polyacid based block copolymers containing polyisoprene (PI) are reported. The challenge of maintaining the integrity of the polydiene while producing polyacid from the

Structural evolution from poly(lactide) (PLA) macromonomer to resultant PLA molecular bottlebrush during ring opening metathesis polymerization (ROMP) was investigated for the first time by combining size exclusion chromatography (SEC), small-angle neutron scattering (SANS), and coarse-grained molecular dynamics (CG-MD) simulations. Multiple aliquots were collected at various reaction times during ROMP and subsequently analyzed by SEC and SANS. These complementary techniques enable the understanding of systematic changes in conversion, molecular weight and dispersity as well as structural details of PLA molecular bottlebrushes. CG-MD simulation not only predicts the experimental observations, but it also provides further insight into the analysis and interpretation of data obtained in SEC and SANS experiments. We find that PLA molecular bottlebrushes undergo three conformational transitions with increasing conversion (i.e., increasing the backbone length): (1) from an elongated to a globular shape due to longer side chain at low conversion, (2) from a globular to an elongated shape at intermediate conversion caused by excluded volume of PLA side chain, and (3) the saturation of contour length at high conversion due to chain transfer reactions.

We have used neutron scattering to investigate the influence of concentration on the conformation of a star polymer. By varying the contrast between the solvent and the isotopically labeled stars, we obtain the distributions of polymer and solvent within a star polymer from analysis of scattering data. A correlation between the local desolvation and the inward folding of star branches is discovered. From the perspective of thermodynamics, we find an analogy between the mechanism of polymer localization driven by solvent depletion and that of the hydrophobic collapse of polymers in solutions.

Structural studies of wormlike micelles have so far mostly focused on the conformational properties of surfactant aggregates. The diffuse ionic atmosphere, which has a profound influence on various micellization phenomena such as thermodynamic stability and structural polymorphism, remains largely unexplored experimentally. In this report a strategy of contrast variation small-angle neutron scattering for this crucial structural study is outlined. Underlined by a general criterion established for unbiasedly identifying the length scale relevant to charge association from the spectral evolution, our analytical framework can provide a quantitative description of counterion distribution in a mathematically tractable manner. Our method can be conveniently extended to facilitate structural studies of complex multicomponent systems using contrast variation neutron scattering.

We outline a machine learning strategy for quantitively determining the conformation of AB-type diblock copolymers with excluded volume effects using small angle scattering. Complemented by computer simulations, a correlation matrix connecting conformations of different copolymers according to their scattering features is established on the mathematical framework of a Gaussian process, a multivariate extension of the familiar univariate Gaussian distribution. We show that the relevant conformational characteristics of copolymers can be probabilistically inferred from their coherent scattering cross sections without any restriction imposed by model assumptions. This work not only facilitates the quantitative structural analysis of copolymer solutions but also provides the reliable benchmarking for the related theoretical development of scattering functions.

Deuterium, a stable hydrogen isotope, has been playing important roles in many scientific areas, including polymer science. The developments of deuteration science and polymer science have been int...

This study demonstrates how the large concentration fluctuations of polymeric liquids under deformation and flow can be quantitatively studied by applying the spherical harmonic expansion technique...

Conjugated polymer (CP) materials that are considered as an attractive choice for various electronic and optoelectronic applications possess highly heterogeneous complex structures that can span several orders of magnitude in length scale. This is due to the intricate coupling effects of weak secondary interactions and entropic forces that determine molecular organization in bulk polymer materials. Understanding the influence of molecular interactions on the emergence and evolution of nano- and microscale structures is of paramount importance to the guided design and development of condensed CP materials. Such understanding is even more critical for the rational design of hierarchical systems away from equilibrium, where weak molecular interactions can guide the system along competing kinetic pathways toward local energy minima and metastable architectures. In this work, we studied a promising concept for accessing various kinetically stabilized semi-crystalline CP nanostructures that are formed in the process of controlled chain-growth Kumada catalyst-transfer polymerization initiated by a small-molecule catalytic species which can exist in equilibrium between free and aggregated states. Specifically, we chose a small-molecule perylenedicarboximide (PDCI) polymerization catalytic initiator which has a strong tendency toward reversible supramolecular assembly–disassembly that can be controlled by temperature. Addition of a thiophene monomer to a solution of the PDCI initiator starts the chain-growth polymerization process, which produces distinct nanoscale semi-crystalline polythiophene structures formed under predominant kinetic control. We demonstrated that, depending on the reaction temperature (which affects the fine balance between the position of PDCI assembly–disassembly equilibrium, rate of polymerization, and solvent–solute interactions for the growing polythiophene chains), a range of kinetically trapped hierarchically organized semi-crystalline CP systems with substantially varying optoelectronic properties could be obtained. In addition to spectroscopic and electron microscopic studies, in order to better reveal the structural aspects of the generated polymer nanoscale systems, we carried out a series of X-ray diffraction and neutron scattering experiments which indicated complex hierarchical organization in these kinetically stabilized CP assembled materials. We expect that this in situ polymerization-based approach can lead to a general way to expand access to various semi-crystalline CP nanostructured materials with broadly tunable electronic and optical properties.

The adsorption of monoclonal antibodies (mAbs) on hydrophobic surfaces is known to cause protein aggregation and degradation. Therefore, surfactants, such as Poloxamer 188, are widely used in therapeutic formulations to stabilize mAbs and protect mAbs from interacting with liquid-solid interfaces. Here, the adsorption of Poloxamer 188, one mAb and their competitive adsorption on a model hydrophobic siliconized surface is investigated with neutron scattering coupled with contrast variation to determine the molecular structure of adsorbed layers for each case. Small angle neutron scattering measurements of the affinity of Poloxamer 188 to this mAb indicate that there is negligible binding at these solution conditions. Neutron reflectometry measurements of the mAb show irreversible adsorption on the siliconized surface, which cannot be washed off with neat buffer. Poloxamer 188 can be adsorbed on the surface already occupied by mAb, which enables partial removal of some adsorbed mAb by washing with buffer. The adsorption of the surfactant introduces significant conformational changes for mAb molecules that remain on the surface. In contrast, if the siliconized surface is first saturated with the surfactant, no adsorption of mAb is observed. Competitive adsorption of mAb and Poloxamer 188 from solution leads to a surface dominantly occupied with surfactant molecules, whereas only a minor amount of mAb absorbs. These findings clearly indicate that Poloxamer 188 can protect against mAb adsorption as well as modify the adsorbed conformation of previously adsorbed mAb.

Flexible alkyl side chain in conjugate polymers (CPs) improves the solubility and promotes solution processability, in addition, it affects interchain packing and charge mobilities. Despite the well‐known charge mobility and morphology correlation for these semi‐crystalline polymers, there is a lack of fundamental understanding of the impact of side chain on their crystallization kinetics. In the present work, isothermal crystallization of five poly(3‐alkylthiophene‐2,5‐diyl) (P3ATs) with different side‐chain structures were systematically investigated. To suppress the extremely fast crystallization and trap the sample into amorphous glass, an advanced fast scanning chip calorimetry technique, which is able to quench the sample with few to tens thousands of K/s, was applied. Results show that the crystallization of P3ATs was greatly inhibited after incorporation of branched side chains, as indicated by a dramatic up to six orders of magnitude decrease in the crystallization rate. The suppressed crystallization of P3ATs were correlated with an increased π–π stacking distance due to unfavorable side‐chain steric interaction. This work provides a pathway to use side‐chain engineering to control the crystallization behavior for CPs, thus to control device performance.

Polymersomes frequently appear in the literature as promising candidates for a wide range of applications from targeted drug delivery to nanoreactors. From a cell mimetic point of view, it is important to understand the size and shape changes of the vesicles in the physiological environment since that can influence the drug delivery mechanism. In this work we studied the structural features of polymersomes consisting of poly(ethylene glycol)-poly(dimethylsiloxane)-poly(ethylene glycol) at the nanoscopic length scale in the presence of NaCl, which is a very common molecule in the biotic aqueous environment. We used dynamic light scattering (DLS), cryo-TEM, small angle neutron scattering (SANS) and small angle X-ray scattering (SAXS). We observed transformation of polymersomes from spherical to elongated vesicles at low salt concentration and into multivesicular structures at high salt concentration. Model fitting analysis of SANS data indicated a reduction of vesicle radius up to 47% and from the SAXS data we observed an increase in membrane thickness up to 8% and an increase of the PDMS hydrophobic segment up to 11% indicating stretching of the membrane due to osmotic imbalance. Also, from the increase in the interlamellar repeat distance up to 98% under high salt concentrations, we concluded that the shape and structural changes observed in the polymersomes are a combined result of osmotic pressure change and ion-membrane interactions.

We use broad-band dielectric spectroscopy (BDS) and small-angle X-ray scattering (SAXS) to investigate the impact of architectural asymmetry in the miktoarm star copolymer on the dielectric polymer...

Although considerable progress has been made to optimize the optoelectronic properties of conjugated polymers (CPs), the rational design of CPs with tailored physical properties for end-use applica...

Bioinspired membrane molecules with improved physical properties and enhanced stability can serve as functional models for conventional lipid or amphiphilic species. Importantly, these molecules can also provide new insights into emergent phenomena that manifest during self-assembly at interfaces. Here, we elucidate the structural response and mechanistic steps underlying the self-assembly of the amphiphilic, charged oligodimethylsiloxane imidazolium cation (ODMS-MIM

Poly(ethylene oxide) (PEO)-based electrolytes have gained increasing attention in both the rechargeable battery industry and fundamental research, but any influence of the ions on the polymer confo...

Solid-state narrow-band light emitters are on-demand for quantum optoelectronics. Current approaches based on defect engineering in low-dimensional materials usually introduce a broad range of emission centers. Here, we report narrow-band light emission from covalent heterostructures fused to the edges of graphene nanoribbons (GNRs) by controllable on-surface reactions from molecular precursors. Two types of heterojunction (HJ) states are realized by sequentially synthesizing GNRs and graphene nanodots (GNDs) and then coupling them together. HJs between armchair GNDs and armchair edges of the GNR are coherent and give rise to narrow-band photoluminescence. In contrast, HJs between the armchair GNDs and the zigzag ends of GNRs are defective and give rise to nonradiative states near the Fermi level. At low temperatures, sharp photoluminescence emissions with peak energy range from 2.03 to 2.08 eV and line widths of 2-5 meV are observed. The radiative HJ states are uniform, and the optical transition energy is controlled by the band gaps of GNRs and GNDs. As these HJs can be synthesized in a large quantity with atomic precision, this finding highlights a route to programmable and deterministic creation of quantum light emitters.

Thermomechanical properties of conjugated polymers (CPs) are greatly influenced by both their microstructures and backbone dynamics. In the present work, to investigate the effect of the side-chain branch position on the backbone's mobility and molecular packing structure, four poly (3-alkylthiophene-2,5-diyl) derivatives (P3ATs) with different side chains, either branched or linear, were synthesized by a quasi-living Kumada catalyst transfer polymerization (KCTP) method. The side-chain branch position greatly influences the glass transition temperature (Tg) of the backbone of P3ATs as well as the melting temperature (Tm), as measured by dynamic mechanical analysis (DMA) and differential scanning calorimetry (DSC) respectively. Placing the branching point closer to the conjugated backbone leads to increased backbone Tg and Tm. Also, according to grazing incidence wide-angle X-ray scattering (GIWAXS) results, branching closer to the backbone causes tighter packing in the side-chain direction. The tighter packing along the side-chain direction coresponds with the higher Tm, which decreases the free volume of the polymer system and subsequently increases the Tg at the same time. This work provides the first in-depth understanding of branch point influences on the thermal properties of poly(3-alkylthiophenes). It would provide guidance to the future development of side-chain engineering on next-generation CPs with desirable thermomechnical properties for stretchable and wearable electronics.

The structure and dynamics of lipid membranes in the presence of extracellular macromolecules are critical for cell membrane functions and many pharmaceutical applications. The pathogen virulence-suppressing end-phosphorylated polyethylene glycol (PEG) triblock copolymer (Pi-ABAPEG) markedly changes the interactions with lipid vesicle membranes and prevents PEG-induced vesicle phase separation in contrast to the unphosphorylated copolymer (ABAPEG). Pi-ABAPEG weakly absorbs on the surface of lipid vesicle membranes and slightly changes the structure of 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) unilamellar vesicles at 37 °C, as evidenced by small angle neutron scattering. X-ray reflectivity measurements confirm the weak adsorption of Pi-ABAPEG on DMPC monolayer, resulting in a more compact DMPC monolayer structure. Neutron spin-echo results show that the adsorption of Pi-ABAPEG on DMPC vesicle membranes increases the membrane bending modulus κ.

We performed multiscale molecular dynamics (MD) simulations of bottlebrush polymers with fluorinated side chains to investigate the influence of the bottlebrush architecture on the spatial distribu...

Thermomechanical properties of polymers highly depend on their glass transition temperature (T g). Differential scanning calorimetry (DSC) is commonly used to measure T g of polymers. However, many conjugated polymers (CPs), especially donor–acceptor CPs (D–A CPs), do not show a clear glass transition when measured by conventional DSC using simple heat and cool scan. In this work, we discuss the origin of the difficulty for measuring T g in such type of polymers. The changes in specific heat capacity (Δc ₚ) at T g were accurately probed for a series of CPs by DSC. The results showed a significant decrease in Δc ₚ from flexible polymer (0.28 J g⁻¹ K⁻¹ for polystyrene) to rigid CPs (10⁻³ J g⁻¹ K⁻¹ for a naphthalene diimide‐based D–A CP). When a conjugation breaker unit (flexible unit) is added to the D–A CPs, we observed restoration of the Δc ₚ at T g by a factor of 10, confirming that backbone rigidity reduces the Δc ₚ. Additionally, an increase in the crystalline fraction of the CPs further reduces Δc ₚ. We conclude that the difficulties of determining T g for CPs using DSC are mainly due to rigid backbone and semicrystalline nature. We also demonstrate that physical aging can be used on DSC to help locate and confirm the glass transition for D‐A CPs with weak transition signals. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019, 57, 1635–1644

We put forth a simple and yet practical theoretical model generalized from Raoult’s law and Henry’s law and show that it can be reduced to these two laws under limiting conditions. The model entertains a hybrid parameter h_B with activity coefficient bundled into it, which smoothly bridges the p_B^* and K_B coefficients in Raoult’s law and Henry’s law. The value of h_B falls in the interval of [K_B, p_B^*] or [p_B^*, K_B] in the case of negative or positive deviation from Raoult’s law, respectively. We uncover an overlapping rule for the ranges of h_A and h_B, which binary mixtures must obey to form azeotropes. We also provide straightforward ways to analyze the characteristic mole fraction and pressure for azeotropes and to understand the relative positions of vapor composition curves with respect to the liquid counterparts. We rely heavily on experimental data available in the literature for representative binary mixtures with both negative and positive deviations from Raoult’s law to illustrate the algebraic derivations. The knowledge gained is useful in the analysis of experimental data from vapor-liquid equilibrium measurements and possess pedagogical merit in various relevant fields.

Research into the manufacturing of LIB electrodes is constantly evolving with new active materials, improved binders, and improved drying techniques to more efficiently produce high-quality electrodes. However, the one constant in all these endeavors is that electrode research and manufacture still generally rely on a slurry-coating process, where large amounts of potentially toxic solvents are necessary for slurry production. As such, solvent-free, also known as dry-process (DP), electrode processing has been proposed to solve the conventional lithium-ion battery electrodes fabrication disadvantages, such as high equipment costs for solvent reclamation, currently seen in industry. Currently, the solvent-free, state-of-the-art electrodes use polytetrafluoroethylene (PTFE) as a binder and the PTFE is fibrillized and dispersed in the dry powder mixture using a jet mill. One key solvent-free electrode shortcoming is that PTFE is not electrochemically stable for the anode, traditionally resulting in initial capacity losses of greater than 30% and poor mechanical strength, effectively limiting solvent-free processing to cathodes. A second shortcoming is that solvent-free electrodes generally require the addition of fibrillization promoters or processing steps that add cost and detract from performance by limiting active material content in the final electrodes. In a recent development, Navitas and its internal partners of Cabot, Arkema, the University of Tennessee, Knoxville, and Oak Ridge National Laboratory have shown the capability to produce both solvent-free anodes and cathodes utilizing an advanced dry-electrode process (ADEP) that also enables high-throughput production of next generation battery electrodes. These electrodes have improved mechanical strength, sufficient to withstand roll-to-roll manufacturing, and the anodes demonstrate an initial capacity loss of less than 15%. The group has demonstrated roll-to-roll production of solvent-free electrodes at quasi-industry standard active material compositions (90-92%) without the reliance of previously used fibrillization promoters, even at reduced PTFE concentrations in the formulation. Navitas has recently demonstrated the large format lamination of the initially formed, or “free-standing,” electrodes after they have been produced in roll-to-roll manufacturing and the integration of solvent-free electrodes in dual-layer and multi-layer pouch cells using typical industry tooling and cell production techniques. Key words: solvent-free, dry-process, fibrillization, next generation lithium-ion batteries (NGLB), advanced dry-electrode process (ADEP), initial capacity loss, free-standing, roll-to-roll, pouch cell

Understanding the reaction mechanisms of dehydrogenative Caryl–Caryl coupling is the key to directed formation of π-extended polycyclic aromatic hydrocarbons. Here we utilize isotopic labeling to identify the exact pathway of cyclodehydrogenation reaction in the on-surface synthesis of model atomically precise graphene nanoribbons (GNRs). Using selectively deuterated molecular precursors, we grow seven-atom-wide armchair GNRs on a Au(111) surface that display a specific hydrogen/deuterium (H/D) pattern with characteristic Raman modes. A distinct hydrogen shift across the fjord of Caryl–Caryl coupling is revealed by monitoring the ratios of gas-phase by-products of H2, HD, and D2 with in situ mass spectrometry. The identified reaction pathway consists of a conrotatory electrocyclization and a distinct [1,9]-sigmatropic D shift followed by H/D eliminations, which is further substantiated by nudged elastic band simulations. Our results not only clarify the cyclodehydrogenation process in GNR synthesis but also present a rational strategy for designing on-surface reactions towards nanographene structures with precise hydrogen/deuterium isotope labeling patterns., Selective deuterations were exploited to synthesize graphene nanoribbons on Au(111) surface with a specific H/D pattern on edges, allowing the determination of cyclodehydrogenation reaction pathway within the framework of pericyclic reactions.

The spatial correlations of entangled polymer dynamics are examined by molecular dynamics simulations and neutron spin-echo spectroscopy. Due to the soft nature of topological constraints, the initial spatial decays of intermediate scattering functions of entangled chains are, to the first approximation, surprisingly similar to those of an unentangled system in the functional forms. However, entanglements reveal themselves as a long tail in the reciprocal-space correlations, implying a weak but persistent dynamic localization in real space. Comparison with a number of existing theoretical models of entangled polymers suggests that they cannot fully describe the spatial correlations revealed by simulations and experiments. In particular, the strict one-dimensional diffusion idea of the original tube model is shown to be flawed. The dynamic spatial correlation analysis demonstrated in this work provides a useful tool for interrogating the dynamics of entangled polymers. Lastly, the failure of the investigated models to even qualitatively predict the spatial correlations of collective single-chain density fluctuations points to a possible critical role of incompressibility in polymer melt dynamics.

Thermoplastic elastomers (TPEs) have found use in a wide range of applications, such as adhesives, elastomers, coatings, fibers, and in additive manufacturing techniques such as 3D printing. Despite their omnipresence, the need for advanced TPEs with adaptive properties is continuously growing. Along with a brief historical introduction, this review presents an overview of typical structure-property relationships for various TPEs and discusses the design principles of TPEs from a synthetic chemistry perspective. Recent advances in TPEs with different macromolecular architectures, including linear ABA triblock copolymers, ABC triblock terpolymers, multiblock copolymers, star copolymers, graft copolymers, bottlebrush polymers, and hyperbranched polymers are reviewed. Service temperatures and mechanical properties of the different materials are compared in each section. Incorporating various supramolecular interactions into different macromolecular architectures as a means to further extend the range of TPE applications is also discussed. Future opportunities for TPE research in both academia and industry are addressed as perspectives.

A new method, “nonvolatile solvent vapor annealing” (NVASA), has been developed to anneal block copolymers during film deposition by controlling the solvent drying process. Precise amounts of high ...