ACS polymers Au最新文献

This work aimed to decrease the water permeability (P_H2O) while simultaneously maintaining low oxygen permeability (P_O2) in ethylene vinyl alcohol (EVOH)-based copolymers by introducing high levels of backbone regioregularity and stereoregularity. Both regioregular atactic and isotactic EVOH samples with 75 mol % ethylene were prepared by a ring-opening metathesis polymerization (ROMP)-hydrogenation-deprotection approach and then compared to commercial EVOH(44) (containing 44 mol % ethylene) as a low P_O2 standard with poor water barrier characteristics (i.e., high P_H2O). The high levels of regioregularity and stereoregularity in these copolymers increased the melting temperature (T_m), degree of crystallinity (χ_c), and glass-transition temperature (T_g) compared to less regular structures. EVOH(44) demonstrated the highest T_m but lower χ_c and T_g values as compared to that of the isotactic polymer. Wide-angle X-ray scattering showed that semicrystalline EVOH(44) exhibited a monoclinic structure characteristic of commercial materials, while ROMP-derived polymers displayed an intermediate structure between monoclinic and orthorhombic. Tensile testing showed that isotacticity resulted in brittle mechanical behavior, while the atactic and commercial EVOH(44) samples had higher tensile toughness values. Although EVOH(44) had the lowest P_O2 of the samples explored, the atactic and tough ROMP-derived polymer approached this value of P_O2 while having a P_H2O over 3 times lower than that of commercial EVOH(44).

The precise sequence of a protein’s primary structure is essential in determining its folding pathways. To emulate the complexity of these biomolecules, functional block copolymers consisting of segmented triblocks with distinct functionalities positioned in a sequence-specific manner are designed to control the polymer chain compaction. Triblock polymers P-b-C-b-F and P-b-F-b-C and random diblock copolymer P-b-C-r-F consist of a hydrophilic poly(ethylene oxide) (PEO) block and a hydrophobic block with coumarin (C) and ferrocene (F) moieties that are grafted in a sequence-specific or random manner onto the hydrophilic block. External stimuli such as UV_B light, redox, and chemical cues influence the functional hydrophobic block to alter the packing parameters that are monitored with spectroscopic and scattering techniques. Interestingly, the positioning of the stimuli-responsive moiety within the hydrophobic block of P-b-C-b-F, P-b-F-b-C, and P-b-C-r-F affects the extent of the hydrophobic–hydrophilic balance in block copolymers that renders orthogonal control in stimuli-responsive transformation of self-assembled vesicles to micelles.

A microwave-assisted esterification reaction to prepare hyaluronan–curcumin derivatives by employing a solvent-free process was developed. In particular, a solid-state strategy to react two molecules characterized by totally different solubility profiles was developed. Hyaluronic acid, a highly hydrosoluble polysaccharide, was reacted with hydrophobic and even water-unstable curcumin. Microwave (MW) irradiation was employed to activate the reaction between the two solid compounds through the direct interaction with them and to preserve the integrity of the sensitive curcumin species. This new protocol can be considered efficient, fast, and also eco-friendly, avoiding the employment of toxic organic bases and solvents. A cytotoxicity test suggested that the developed hyaluronan–curcumin conjugate (HA-CUR) could be considered a candidate for its implementation as a new material. In addition, preliminary studies revealed promising anti-inflammatory activity and open future perspectives of further investigation.

Polyanions can internalize into cells via endocytosis without any cell disruption and are therefore interesting materials for biomedical applications. In this study, amino-acid-derived polyanions with different alkyl side-chains are synthesized via postpolymerization modification of poly(pentafluorophenyl acrylate), which is synthesized via reversible addition–fragmentation chain-transfer (RAFT) polymerization, to obtain polyanions with tailored hydrophobicity and alkyl branching. The success of the reaction is verified by size-exclusion chromatography, NMR spectroscopy, and infrared spectroscopy. The hydrophobicity, surface charge, and pH dependence are investigated in detail by titrations, high-performance liquid chromatography, and partition coefficient measurements. Remarkably, the determined pK_a-values for all synthesized polyanions are very similar to those of poly(acrylic acid) (pK_a = 4.5), despite detectable differences in hydrophobicity. Interactions between amino-acid-derived polyanions with L929 fibroblasts reveal very slow cell association as well as accumulation of polymers in the cell membrane. Notably, the more hydrophobic amino-acid-derived polyanions show higher cell association. Our results emphasize the importance of macromolecular engineering toward ideal charge and hydrophobicity for polymer association with cell membranes and internalization. This study further highlights the potential of amino-acid-derived polymers and the diversity they provide for tailoring properties toward drug delivery applications.

Even though heavy and transition metals originated in the earth’s crust, the significant human exposure and environmental pollution consequences of anthropogenic activities include industrial production and waste, mining and smelting operations, and agricultural and domestic usage of metals. Because of their nonbiodegradable nature, heavy metal ions such as Cu²⁺ accumulate very quickly in plants and edible animals, ultimately ending up in the human food cycle. Therefore, to nullify the detrimental effects of Cu²⁺ ions for the sake of the environment and living organisms, we are motivated to design a sensor molecule that can not only detect Cu²⁺ ions but also remove them selectively from the water medium. To detect the Cu²⁺ ions, we synthesized a monomer (NCu) and its biodegradable caprolactone-based polymer (PNCu). It was observed that both NCu and PNCu showed higher selectivity toward Cu²⁺ ions by changing the color from colorless to yellow, with a limit of detection value of 29 nM and 0.3 μM. Furthermore, removing the Cu²⁺ ions from the water solution was also accomplished by introducing the hydrophobicity of the polymer (PNCu) through the ring-opening polymerization process. Due to increased hydrophobicity, the polymer produced a yellow color precipitate upon adding Cu²⁺ ions to the solution; thus, removal of the metal ion is possible using our designed polymer and its detection ability. We checked the removal efficiency of our polymer by using UV–vis spectroscopy and EDX analysis, which indicated that almost all of the copper is removed by our polymer. Therefore, to our knowledge, this is the first biodegradable caprolactone-based polymer for colorimetric turn-on detection and separation of the Cu²⁺ ions from the water.

For most individuals, wound healing is a highly organized, straightforward process, wherein the body transitions through different phases in a timely manner. However, there are instances where external intervention becomes necessary to support and facilitate different phases of the body’s innate healing mechanism. Furthermore, in developing countries, the cost of the intervention significantly impacts access to treatment options as affordability becomes a determining factor. This is particularly true in cases of long-term wound treatment and management, such as chronic wounds and infections. Silk fibroin (SF) and its nanocomposites have emerged as promising biomaterials with potent wound-healing activity. Driven by this motivation, this Review presents a critical overview of the recent advancements in different aspects of wound care using SF and SF-based nanocomposites. In this context, we explore various formats of hemostats and assess their suitability for different bleeding situations. The subsequent sections discuss the primary causes of nonhealing wounds, i.e., prolonged inflammation and infections. Herein, different treatment strategies to achieve immunomodulatory and antibacterial properties in a wound dressing were reviewed. Despite exhibiting excellent pro-healing properties, few silk-based products reach the market. This Review concludes by highlighting the bottlenecks in translating silk-based products into the market and the prospects for the future.

In recent times, the evolution of cationic polymerization has taken a multidirectional approach, with the development of cationic reversible addition–fragmentation chain transfer (RAFT) polymerization. In contrast to the conventional cationic polymerization methods, which were typically carried out under inert atmospheres and low temperatures, various novel polymerization techniques have been developed where the reactions are carried out in open air, operate at room temperature, are cost-effective, and are environmentally friendly. Besides, several external stimuli, such as heat, light, chemicals, electrical potential, etc. have been employed to activate and control the polymerization process. It also enables the combination of cationic polymerization with other polymerization methods in a single reaction vessel, eliminating the necessity for isolation and purification during intermediate steps. In addition, significant advancements have been made through various modifications in catalyst systems, resulting in polymers with an exceptionally high level of stereoregularity. This review article comprehensively analyses the recent developments in cationic polymerization, encompassing their applications and offering insights into future perspectives.

Bottlebrush (BB) polymers were synthesized via grafting-from-atom transfer radical polymerization (ATRP) of styrene on polypentenamer and polynorbornene macroinitiators with matched grafting density (n_g = 4) and backbone degrees of polymerization (122 ≥ N_bb ≥ 61) to produce a comparative study on their respective dilute solution properties as a function of increasing side chain degree of polymerization (116 ≥ N_sc ≥ 5). The grafting-from technique produced near quantitative grafting efficiency and narrow dispersity N_sc as evidenced by spectroscopic analysis and ring closing metathesis depolymerization of the polypentenamer BBs. The versatility of this synthetic approach permitted a comprehensive survey of power law expressions that arise from monitoring intrinsic viscosity, hydrodynamic radius, and radius of gyration as a function of increasing the molar mass of the BBs by increasing N_sc. These values were compared to a series of linear (nongrafted, N_sc = 0) macroinitiators in addition to linear grafts. This unique study allowed elucidation of the onset of bottlebrush behavior for two different types of bottlebrush backbones with identical grafting density but inherently different flexibility. In addition, grafting-from ATRP of methyl acrylate on a polypentenamer macroinitiator allowed the observation of the effects of graft chemistry in comparison to polystyrene. Differences in the observed scaling relationships in dilute solution as a function of each of these synthetic variants are discussed.

The association of ionizable polymers strongly affects their motion in solutions, where the constraints arising from clustering of the ionizable groups alter the macroscopic dynamics. The interrelation between the motion on multiple length and time scales is fundamental to a broad range of complex fluids including physical networks, gels, and polymer–nanoparticle complexes where long-lived associations control their structure and dynamics. Using neutron spin echo and fully atomistic, multimillion atom molecular dynamics (MD) simulations carried out to times comparable to that of chain segmental motion, the current study resolves the dynamics of networks formed by suflonated polystryene solutions for sulfonation fractions 0 ≤ f ≤ 0.09 across time and length scales. The experimental dynamic structure factors were measured and compared with computational ones, calculated from MD simulations, and analyzed in terms of a sum of two exponential functions, providing two distinctive time scales. These time constants capture confined motion of the network and fast dynamics of the highly solvated segments. A unique relationship between the polymer dynamics and the size and distribution of the ionic clusters was established and correlated with the number of polymer chains that participate in each cluster. The correlation of dynamics in associative complex fluids across time and length scales, enabled by combining the understanding attained from reciprocal space through neutron spin echo and real space, through large scale MD studies, addresses a fundamental long-standing challenge that underline the behavior of soft materials and affect their potential uses.