Uniform Chain Length Research Articles

Discrete Cyclic Polymers with Uniform Chain Length

Discrete Cyclic Polymers with Uniform Chain Length

Stabilizing hexagonally close-packed phase in single-component block copolymers through rational symmetry breaking

Despite being predicted to be a thermodynamically equilibrium structure, the absence of direct experimental evidence of hexagonally close-packed spherical phase in single-component block copolymers raises uncomfortable concerns regarding the existing fundamental phase principles. This work presents a robust approach to regulate the phase behavior of linear block copolymers by deliberately breaking molecular symmetry, and the hexagonally close-packed lattice is captured in a rigorous single-component system. A collection of discrete A1BA2 triblock copolymers is designed and prepared through an iterative growth method. The precise chemical composition and uniform chain length eliminates inherent size distribution and other molecular defects. Simply by tuning the relative chain length of two end A blocks, a rich array of ordered nanostructures, including Frank−Kasper A15 and σ phases, are fabricated without changing the overall chemistry or composition. More interestingly, hexagonally close-packed spherical phase becomes thermodynamically stable and experimentally accessible attributed to the synergistic contribution of the two end blocks. The shorter A blocks are pulled out from the core domain into the matrix to release packing frustration, while the longer ones stabilize the ordered spherical phase against composition fluctuation that tends to disrupt the lattice. This study adds a missing puzzle piece to the block copolymer phase diagram and provides a robust approach for rational structural engineering.

Discrete Miktoarm Star Block Copolymers with Tailored Molecular Architecture.

Molecular architecture is a critical factor in regulating phase behaviors of the block copolymer and prompting the formation of unconventional nanostructures. This work meticulously designed a library of isomeric miktoarm star polymers with an architectural evolution from the linear-branched block copolymer to the miktoarm star block copolymer and to the star-like block copolymer (i.e., 3AB → 3(AB1)B2 → 3(AB)). All of the polymers have precise chemical composition and uniform chain length, eliminating inherent molecular uncertainties such as chain length distribution or architectural defects. The self-assembly behaviors were systematically studied and compared. Gradually increasing the relative length of the branched B1 block regulates the ratio between the bridge and loop configuration and effectively releases packing frustration in the formation of the spherical or cylindrical structures, leading to a substantial deflection of phase boundaries. Complex structures, such as Frank-Kasper phases, were captured at a surprisingly higher volume fraction. Rationally regulating the molecular architecture offers rich possibilities to tune the packing symmetry of block copolymers.

Facile engineering strategy to control polymer chain structure for enhanced dispersion, electrical and sensing properties of nanocomposites

Preventing the aggregation of nanofillers and inducing uniform filler dispersion are key parameters for improving the electrical conductivity and sensing sensitivity of nanocomposites. Although the viscosity and flow index which are determined by the polymer chain structure can significantly influence the nanofiller dispersion, few systematic structural and physical analyses have been reported. In this study, a facile engineering strategy to control the polymer chain structure was designed and applied using quad-screw extrusion (QSE) capable of transferring high shear stresses. According to the increase in rotation speed of the QSE, low molecular weight polymer chains with relatively uniform chain length were prepared, enabling the fabrication of a nanocomposite with uniform dispersion. Compared to the controls, when the optimized matrix (2000 rpm) was applied to the nanocomposite with 1 wt% multi-walled carbon nanotubes, the improved strain sensor sensitivity of 798.3% were achieved owing to the improved filler dispersion and electrical conductivity.

Self-assembly immobilization of a universal catalytic microreactor for glycosyltransferases

Hyaluronic acid (HA) and chondroitin sulfate (CS) are polydisperse glycosaminoglycans (GAGs),which have important applications as health care products and drugs in skin beauty and arthritis prevention. Enzymatic synthesis is a significant strategy to obtain oligosaccharides and polysaccharides with uniform chain length and well-defined structure. However, the limitations of glycosyltransferase, such as low expression, poor stability, and difficulty in reuse, greatly restrict its application in large-scale commercial production. In this study, we constructed the expression system for hyaluronic acid synthase PmHAS and chondroitin synthase KfoC to obtain the enzyme with high expression level and good water solubility. Subsequently, we screened and optimized several highly biocompatible metal-organic frameworks (MOFs) to immobilize two glycosyltransferases efficiently. The resulting enzyme@MOF composite can catalyze the synthesis of hyaluronic acid and chondroitin oligosaccharides/polysaccharides in quantitative yield. Meanwhile, the supramolecular interactions between enzyme and hydrophilic MOFs confer satisfactory stability, durability, and reusability on immobilized PmHAS and KfoC.

NMR and GPC Analysis of Alkyd Resins: Influence of Synthesis Method, Vegetable Oil and Polyol Content.

Alkyd resins are oil-based polymers that have been widely used for generations in the surface coating industry and beyond. Characterization of these resins is of high importance to understand the influence of its components on its behavior, compatibility with other resins, and final quality to ensure high durability. Here, NMR spectroscopy and GPC were used for characterizing differences in the chemical structure, molecular distribution, and dispersity between oil-based and fatty acid-based alkyd polymers made from sacha inchi and linseed oils. Sancha inchi (Plukentia volubilis L.) is a fruit-bearing plant native to South America and the Caribbean, and has a rich unsaturated fatty acid content. The effect of vegetable oil and polyol selection on the synthesis of alkyd resins for coating applications was analyzed. The influence of two different synthesis methods, monoglyceride and fatty acid processes, was also compared. Important structural differences were observed using NMR: one-dimensional spectra revealed the degree of unsaturated fatty acid chains along the polyester backbone, whereas, 2D NMR experiments facilitated chemical shift assignments of all signals. GPC analysis suggested that alkyd resins with homogeneous and high molecular weights can be obtained with the fatty acid process, and that resins containing pentaerythritol may have uniform chain lengths.

True self-reinforced composites enabled by tuning of molecular structure for lightweight structural materials in future mobility

The development of vehicle bodies based on lightweight structural composites is urgently required to upgrade electric cars and to commercialize urban air mobility. Self-reinforced composites (SRCs) are attracting attention due to their advantages in terms of price, lightness, disposal and recycling compared to carbon fiber-reinforced polymers (CFRPs). In this study, a new concept for 100% polypropylene (PP) SRC was proposed to simultaneously improve the adhesive, tensile and impact properties of SRCs without undermining the advantages of SRCs. For this implementation, a facile engineering strategy using quad screw extrusion (QSE) capable of generating high shear stress was employed to modify the melting temperature and impregnation properties of the PP matrix via controlling polymer chain structure. As the screw rotation speed of QSE increased, low molecular weight polymer chains with uniform chain lengths were prepared, which led to a decrease in the melting temperature of the PP matrix and an increase in the flowability and impregnation property of the matrix. Using this strategy, the adhesive strength, tensile strength and impact resistance of the optimized SRC improved by 333%, 228%, and 2700%, respectively. Racing drone flight experiments with the SRC and CFRP frames illustrated the advantages of the SRC frame such as the increase of the flight time due to low density of the SRC, the excellent impact resistant characteristics (which improves user safety), and the superior electrical insulation properties suitable for frequency transmission and reception. Therefore, the proposed SRC can be an ideal choice as a lightweight structural material for future mobility.

Local Chain Feature Mandated Self-Assembly of Block Copolymers

This work demonstrates an effective and robust approach to regulate phase behaviors of a block copolymer by programming local features into otherwise homogeneous linear chains. A library of sequence-defined, isomeric block copolymers with globally the same composition but locally different side chain patterns were elaborately designed and prepared through an iterative convergent growth method. The precise chemical structure and uniform chain length rule out all inherent molecular defects associated with statistical distribution. The local features are found to exert surprisingly pronounced impacts on the self-assembly process, which have yet to be well recognized. While other molecular parameters remain essentially the same, simply rearranging a few methylene units among the alkyl side chains leads to strikingly different phase behaviors, bringing about (i) a rich diversity of nanostructures across hexagonally packed cylinders, Frank-Kasper A15 phase, Frank-Kasper σ phase, dodecagonal quasicrystals, and disordered state; (ii) a significant change of lattice dimension; and (iii) a substantial shift of order-to-disorder transition temperature (up to 40 °C). Different from the commonly observed enthalpy-dominated cases, the frustration due to the divergence between the native molecular geometry originating from side chain distribution and the local packing environment mandated by lattice symmetry is believed to play a pivotal role. Engineering the local chain feature introduces another level of structural complexity, opening up a new and effective pathway for modulating phase transition without changing the chemistry or composition.

Molecular weight distribution effects of polyacrylamide flocculants on clay aggregate formation

This article investigates the effect of polyacrylamide dispersity (broad and narrow molecular weight distributions) on their flocculation performance in a system of kaolinite clay suspended in water. A series of uniform chain length (dispersity, Đ = 1.04 – 1.35) polyacrylamide flocculants were synthesized using reversible addition-fragmentation chain-transfer polymerization. These uniform polyacrylamides were used individually, as low dispersity flocculants, and in blends, as high dispersity flocculants. Flocculation of the kaolinite suspension was monitored using a focused beam reflectance measurement system where the chord-length distribution of the clay aggregates could be recorded in real-time. Polyacrylamide flocculants with lower dispersities made larger clay aggregates than those with lower dispersities at equal doses. In the polymer blends, the fraction of the high molecular weight component was the best indicator of aggregate size formation; the low molecular weight fraction influenced less the final aggregate size. These findings suggest that polymers with narrow molecular weight distributions can be used in lower dosages than standard high dispersity flocculants with a similar concentration of high molecular weight polymer chains.

Modulation of the Complex Spherical Packings through Rationally Doping a Discrete Homopolymer into a Discrete Block Copolymer: A Quantitative Study

The Frank–Kasper phase and quasicrystalline phase are an intriguing class of complex crystalline structures, which so far are sporadically observed only in a limited number of block copolymers. Incorporation of a homopolymer into a block copolymer has recently been demonstrated as an effective and robust approach to regulate the formation and evolution of these complex spherical phases. The experimental explorations, however, suffer from inherent chain length distribution of the blending stocks. In this study, we quantitatively assessed the phase behaviors of the block copolymer/homopolymer binary blends using discrete species with a precise chemical structure and uniform chain length, ruling out all interferences associated with chemical heterogeneities. Diverse spherical packings, including σ, A15, C15, and C14 phases, were captured by rationally tuning the chain length and loading content of the homopolymer. The short chains swell the spherical core and drive a transition toward the lattices with a lower interfacial curvature (i.e., σ → A15 → HEX), whereas the long chains localize in the center of the core and prompt the formation of the Frank–Kasper phases with the increasing particle volume asymmetry (C15 and C14). The experimental observation validates the recent theoretical advances, demonstrating that the blending strategy is a robust approach for structural engineering.

Effect of Molecular Architecture and Symmetry on Self-Assembly: A Quantitative Revisit Using Discrete ABA Triblock Copolymers.

The inherent statistical heterogeneities associated with chain length, composition, and architecture of synthetic block copolymers compromise the quantitative interpretation of their self-assembly process. This study scrutinizes the contribution of molecular architecture on phase behaviors using discrete ABA triblock copolymers with precise chemical structure and uniform chain length. A group of discrete triblock copolymers with varying composition and symmetry were modularly synthesized through a combination of iterative growth methods and efficient coupling reactions. The symmetric ABA triblock copolymers self-assemble into long-range ordered structures with expanded domain spacings and enhanced phase stability, compared with the diblock counterparts snipped at the middle point. By tuning the relative chain length of two end blocks, the molecular asymmetry reduces the packing frustration, and thus increases the order-to-disorder transition temperature and enlarges the domain sizes. This study would serve as a quantitative model system to correlate the experimental observations with the theoretical assessments and to provide quantitative understandings for the relationship between molecular architecture and self-assembly.

Solid-state cooling by elastocaloric polymer with uniform chain-lengths

Although the elastocaloric effect was found in natural rubber as early as 160 years ago, commercial elastocaloric refrigeration based on polymer elastomers has stagnated owing to their deficient elastocaloric effects and large extension ratios. Herein, we demonstrate that polymer elastomers with uniform molecular chain-lengths exhibit enormous elastocaloric effects through reversible conformational changes. An adiabatic temperature change of −15.3 K and an isothermal entropy change of 145 J kg−1 K−1, obtained from poly(styrene-b-ethylene-co-butylene-b-styrene) near room temperature, exceed those of previously reported elastocaloric polymers. A rotary-motion cooling device is tailored to high-strains characteristics of rubbers, which effectively discharges the cooling energy of polymer elastomers. Our work provides a strategy for the enhancement of elastocaloric effects and could promote the commercialization of solid-state cooling devices based on polymer elastomers.

Complementary side chain promotes microphase separation in the membranes for alkali fuel cells

Anion exchange membranes (AEMs) play a crucial role in alkali electrolyte membrane fuel cells. Side chain grafted AEMs can undergo microphase separation and form good pathways to promote hydroxide ion transport; such AEMs typically have uniform side chain length at all repeat units of backbone, which may suffer from steric hindrance during cation aggregation and thus lead to insufficient microphase separation. In this work, we propose a complementary side chain structure, where a small amount of short side chain (C1) quaternized poly (dimethyl phenylene oxide) (qPPO-C1) is blended with long side chain AEM (qPPO-C6). Our results suggest that a blend AEM containing 5% qPPO-C1, whose IEC (ion exchange capacity) is as low as 1.45 mmol/g, exhibits an impressive conductivity of 37.5 mS/cm (30 °C) while its counterpart AEM with purely long side chains (qPPO-C6) displays an inferior conductivity (31.4 mS/cm) at a similar IEC. Its hydrogen/oxygen fuel cell yields a peak power density of 192 mW/cm2 when operating at 60 °C. Our work discloses, for the first time to our best knowledge, the advantage of complementary side chain in promoting microphase separation, in particular, at low IECs; it may offer new opportunities for further improvement of AEM performance.

Precisely Encoding Geometric Features into Discrete Linear Polymer Chains for Robust Structural Engineering.

Molecular shape is an essential parameter that regulates the self-organization and recognition process, which has not yet been well appreciated and exploited in block polymers due to the lack of precise and efficient modulation methods. This work (i) develops a robust approach to break the intrinsic symmetry of linear polymers by introducing geometric features into otherwise homogeneous chains and (ii) quantitatively highlights the critical contribution of molecular geometry/architecture to the self-assembly behaviors. Iteratively connecting homologous monomers of different side chains according to pre-designed sequences generates discrete polymers with exact chemical structure, uniform chain length, and programmable side-chain gradient along the backbone, which transcribes into diverse shapes. The precise chemistry eliminates all the defects and heterogeneities, providing a delicate platform for fundamental inquiries into the role of molecular geometry. A rich collection of unconventional complex phases, including Frank-Kasper A15 and σ phases, as well as a dodecagonal quasicrystal phase, were captured in these rigorous single-component systems. The self-assembly behaviors are strikingly sensitive to subtle variations of geometry, such that simply migrating a few methylene units among the side chains would generate substantial differences in lattice size or phase stability, or even trigger a phase transition toward distinct structures. The phenomena can be rationalized with a geometric argument that nonuniform side chain distribution leads to conformational mismatch between two immiscible blocks, resulting in varied interfacial curvatures and distinct lattice symmetries. The profound contribution demonstrates that molecular geometry is an effective and robust parameter for structural engineering.

Precise Amphiphilic Giant Polymeric Chain Based on Nanosized Monomers with Exact Regio-Configuration.

Polymeric chains made of "giant" monomers at a larger length scale provide intriguing insights into the fundamental principles of polymer science. In this study, we modularly prepared a library of discrete amphiphilic polymeric chains using molecular nanoparticles as repeat units, with exact control of composition, chain length, surface property, and regio-configuration. These giant polymeric chains self-assembled into a rich collection of highly ordered phases. The precise chemical structure and uniform chain length eliminate all the inherent molecular "defects", while the nanosized monomer amplifies minute structural differences, providing an ideal platform for a systematic scrutiny of the self-assembly behaviors at a larger length scale. The compositional and regio-configurational contribution was carefully studied. The regio-regularity is found to have a direct and profound impact on the chain conformation, leading to a distinct molecular packing scheme and therefore shifting the phase boundaries. With increasing the length of the linker, the regio-constraint gradually diminishes, and the neighboring particles would eventually be decoupled.

Supermolecular structures of recrystallized starches with amylopectin side chains modified by amylosucrase to different chain lengths

Understanding the supermolecular structures of recrystallized starches is imperative to manufacture novel starches with controllable physicochemical properties enabling novel applications. In this study, native amylopectin (AP) from maize was modified to different chain lengths using amylosucrase from Neisseria polysaccharea. Native AP granules showed well-organized lamellar structures with a periodicity of ca. 9.0 nm whereas modified starches formed heterogeneous structures with the average crystallite size ranging from 19.77 to 29.88 nm. Acidic treatments eroded amorphous domains in both native AP granules and modified starch particles, producing nanocrystals composed of double helices. A-type nanocrystals (~40 nm) from native AP granules showed quadrangular shape with an acute angle of ca. 60°, while irregular B-type nanocrystals were observed for the modified starches. Molecular characterizations suggested that the nanocrystals had relatively uniform chain lengths (DP 16.5–25.2), and the helix length (the thickness of nanocrystals) was positively correlated to the thermal stability of starches.

Discrete Block Copolymers with Diverse Architectures: Resolving Complex Spherical Phases with One Monomer Resolution.

This work describes the first rigorous example of a single-component block copolymer system forming unconventional spherical phases. A library of discrete block polymers with uniform chain length and diverse architectures were modularly prepared through a combination of a step-growth approach and highly efficient coupling reactions. The precise chemical structure eliminates all the molecular defects associated with molar weight, dispersity, and compositional ratio. Complex spherical phases, including the Frank–Kasper phase (A15 and σ) and quasicrystalline phase, were experimentally captured by meticulously tuning the composition and architectures. A phase portrait with unprecedented accuracy was mapped out (up to one monomer resolution), unraveling intriguing details of phase behaviors that have long been compromised by inherent molecular weight distribution. This study serves as a delicate model system to bridge the existing gaps between experimental observations and theoretical assessments and to provide insights into the formation and evolution of the unconventional spherical phases in soft matter systems.

Bayesian Annealed Sequential Importance Sampling: An Unbiased Version of Transitional Markov Chain Monte Carlo

Abstract The transitional Markov chain Monte Carlo (TMCMC) is one of the efficient algorithms for performing Markov chain Monte Carlo (MCMC) in the context of Bayesian uncertainty quantification in parallel computing architectures. However, the features that are associated with its efficient sampling are also responsible for its introducing of bias in the sampling. We demonstrate that the Markov chains of each subsample in TMCMC may result in uneven chain lengths that distort the intermediate target distributions and introduce bias accumulation in each stage of the TMCMC algorithm. We remedy this drawback of TMCMC by proposing uniform chain lengths, with or without burn-in, so that the algorithm emphasizes sequential importance sampling (SIS) over MCMC. The proposed Bayesian annealed sequential importance sampling (BASIS) removes the bias of the original TMCMC and at the same time increases its parallel efficiency. We demonstrate the advantages and drawbacks of BASIS in modeling of bridge dynamics using finite elements and a disk-wall collision using discrete element methods.

Furthering Our Understanding of the Doping Mechanism in Conjugated Polymers Using Tetraaniline

Polyaniline is known for reversible acidic doping. However, despite extensive work, little experimental evidence exists for the initial doping mechanism mainly due to the difficulty of synthesizing polyaniline with a uniform chain length. In this study, we partially dope aniline tetramers in order to investigate the initial stage of doping in both solution and the solid state. In solution, we discovered a method for visualizing the doping level due to solvent density differences. The optical results in both the liquid and solid state suggest that the partially doped aniline tetramers are physical mixtures of aniline tetramer in the emeraldine base and emeraldine salt forms. Electron paramagnetic resonance confirms the formation of spinless bipolarons as the major carriers. Therefore, we postulate that the doping mechanism proceeds via a continual increase in the number of doubly doped tetraanilines.

Iterative synthesis of monodisperse pendants for making comb-like polyurethanes

Polyurethanes grafted with well-defined polar pendants were synthesized and investigated. A series of linear and dendritic poly(urea/malonamide)s with uniform chain length were first prepared from an iterative synthesis route, which is based on a dual-functional building block, 4-isocyanate-4´-(3,3-dimethyl-2,4-dioxo-azetidine)diphenyl methane (IDD). Moreover, side chain polyurethanes (SPUs) bearing azetidine-2,4-dione functional groups were prepared from one pot reaction for following post-functionalization of poly(urea/malonamide)s when IDD-diols were added to polyurethane prepolymers as chain extenders. Subsequently, the azetidine-2,4-dione functional groups on the SPUs underwent addition reactions with amino functional group containing dendritic or linear poly(urea/malonamide)s under mild condition, without the need of catalyst and protection/deprotection procedure to achieve polyurethanes grafted with well-defined pendants. Mechanical properties of these comb-like polyurethanes strongly depend on the architecture and the molecular length of poly(urea/malonamide) pendants, which could be adjusted by the grafting fractions of the dendritic or linear poly(urea/malonamide)s with various generations. These poly(urea/malonamide) pendants provided strong hydrogen bonding interactions to achieve physical crosslinking effects in the polyurethanes. Consequently, the polyurethanes with improved mechanical properties and sustained phase transition exhibit shape memory properties.