Showing papers on "Polymer published in 2020"

MXene and MXene-based composites: synthesis, properties and environment-related applications

Abstract: In recent years, a new large family of two dimensional transition metal carbides, carbonitrides, and nitrides, so-called MXenes, have grabbed considerable attention, owing to their many fascinating physical and chemical properties that are closely related to the rich diversity of their elemental compositions and surface terminations. In particular, it is easy for MXenes to form composites with other materials such as polymers, oxides, and carbon nanotubes, which further provides an effective way to tune the properties of MXenes for various applications. Not only have MXenes and MXene-based composites come into prominence as electrode materials in the energy storage field as is widely known, but they have also shown great potential in environment-related applications including electro/photocatalytic water splitting, photocatalytic reduction of carbon dioxide, water purification and sensors, thanks to their high conductivity, reducibility and biocompatibility. In this review, we summarize the synthesis and properties of MXenes and MXene-based composites and highlight their recent advances in environment-related applications. Challenges and perspectives for future research are also outlined.

Polyamide nanofiltration membrane with highly uniform sub-nanometre pores for sub-1 Å precision separation.

Abstract: Separating molecules or ions with sub-Angstrom scale precision is important but technically challenging. Achieving such a precise separation using membranes requires Angstrom scale pores with a high level of pore size uniformity. Herein, we demonstrate that precise solute-solute separation can be achieved using polyamide membranes formed via surfactant-assembly regulated interfacial polymerization (SARIP). The dynamic, self-assembled network of surfactants facilitates faster and more homogeneous diffusion of amine monomers across the water/hexane interface during interfacial polymerization, thereby forming a polyamide active layer with more uniform sub-nanometre pores compared to those formed via conventional interfacial polymerization. The polyamide membrane formed by SARIP exhibits highly size-dependent sieving of solutes, yielding a step-wise transition from low rejection to near-perfect rejection over a solute size range smaller than half Angstrom. SARIP represents an approach for the scalable fabrication of ultra-selective membranes with uniform nanopores for precise separation of ions and small solutes. Separating molecules or ions with sub-Angstrom scale precision is important but technically challenging. Here, the authors demonstrate that precise solute-solute separation can be achieved using polyamide membranes formed via surfactant-assembly regulated interfacial polymerization.

Microbial and Enzymatic Degradation of Synthetic Plastics

Abstract: Synthetic plastics are pivotal in our current lifestyle and therefore, its accumulation is a major concern for environment and human health. Petroleum-derived (petro-)polymers such as polyethylene (PE), polyethylene terephthalate (PET), polyurethane (PU), polystyrene (PS), polypropylene (PP), and polyvinyl chloride (PVC) are extremely recalcitrant to natural biodegradation pathways. Some microorganisms with the ability to degrade petro-polymers under in vitro conditions have been isolated and characterized. In some cases, the enzymes expressed by these microbes have been cloned and sequenced. The rate of polymer biodegradation depends on several factors including chemical structures, molecular weights, and degrees of crystallinity. Polymers are large molecules having both regular crystals (crystalline region) and irregular groups (amorphous region), where the latter provides polymers with flexibility. Highly crystalline polymers like polyethylene (95%), are rigid with a low capacity to resist impacts. PET-based plastics possess a high degree of crystallinity (30-50%), which is one of the principal reasons for their low rate of microbial degradation, which is projected to take more than 50 years for complete degraded in the natural environment, and hundreds of years if discarded into the oceans, due to their lower temperature and oxygen availability. The enzymatic degradation occurs in two stages: adsorption of enzymes on the polymer surface, followed by hydro-peroxidation/hydrolysis of the bonds. The sources of plastic-degrading enzymes can be found in microorganisms from various environments as well as digestive intestine of some invertebrates. Microbial and enzymatic degradation of waste petro-plastics is a promising strategy for depolymerization of waste petro-plastics into polymer monomers for recycling, or to covert waste plastics into higher value bioproducts, such as biodegradable polymers via mineralization. The objective of this review is to outline the advances made in the microbial degradation of synthetic plastics and, overview the enzymes involved in biodegradation.

Modulating Benzothiadiazole‐Based Covalent Organic Frameworks via Halogenation for Enhanced Photocatalytic Water Splitting

Abstract: Two-dimensional covalent organic frameworks (2D COFs), an emerging class of crystalline porous polymers, have been recognized as a new platform for efficient solar-to-hydrogen energy conversion owing to their pre-designable structures and tailor-made functions. Herein, we demonstrate that slight modulation of the chemical structure of a typical photoactive 2D COF (Py-HTP-BT-COF) via chlorination (Py-ClTP-BT-COF) and fluorination (Py-FTP-BT-COF) can lead to dramatically enhanced photocatalytic H2 evolution rates (HER=177.50 μmol h-1 with a high apparent quantum efficiency (AQE) of 8.45 % for Py-ClTP-BT-COF). Halogen modulation at the photoactive benzothiadiazole moiety can efficiently suppress charge recombination and significantly reduce the energy barrier associated with the formation of H intermediate species (H*) on polymer surface. Our findings provide new prospects toward design and synthesis of highly active organic photocatalysts toward solar-to-chemical energy conversion.

Vitrimers: directing chemical reactivity to control material properties

Abstract: The development of more sustainable materials with a prolonged useful lifetime is a key requirement for a transition towards a more circular economy. However, polymer materials that are long-lasting and highly durable also tend to have a limited application potential for re-use. This is because such materials derive their durable properties from a high degree of chemical connectivity, resulting in rigid meshes or networks of polymer chains with a high intrinsic resistance to deformation. Once such polymers are fully synthesised, thermal (re)processing becomes hard (or impossible) to achieve without damaging the degree of chemical connectivity, and most recycling options quickly lead to a drop or even loss of material properties. In this context, both academic and industrial researchers have taken a keen interest in materials design that combines high degrees of chemical connectivity with an improved thermal (re)processability, mediated through a dynamic exchange reaction of covalent bonds. In particular vitrimer materials offer a promising concept because they completely maintain their degree of chemical connectivity at all times, yet can show a clear thermally driven plasticity and liquid behavior, enabled through rapid bond rearrangement reactions within the network. In the past decade, many suitable dynamic covalent chemistries were developed to create vitrimer materials, and are now applicable to a wide range of polymer matrices. The material properties of vitrimers, however, do not solely rely on the chemical structure of the polymer matrix, but also on the chemical reactivity of the dynamic bonds. Thus, chemical reactivity considerations become an integral part of material design, which has to take into account for example catalytic and cross-reactivity effects. This mini-review will aim to provide an overview of recent efforts aimed at understanding and controlling dynamic cross-linking reactions within vitrimers, and how directing this chemical reactivity can be used as a handle to steer material properties. Hence, it is shown how a focus on a fundamental chemical understanding can pave the way towards new sustainable materials and applications.

Porous organic polymers: a promising platform for efficient photocatalysis

Abstract: Porous organic polymers (POPs) are a class of multi-dimensional porous network materials, which are built via strong covalent linkages between various organic building blocks with different geometries and topologies, and have recently become a rising research field in porous materials. POPs can be generally divided into two categories based on their degree of long-range order, including amorphous (e.g., CMPs, HCPs, PIMs, and PAFs) and crystalline (e.g., COFs). Owning to their advantages of light-weight, superior inherent porosity, excellent stability, pre-designable and tunable structures and functions, POPs have received increasing attention and research interest for their tremendous potential applications in gas storage/separation, heterogeneous catalysis, photoelectric conversion, chemical- and bio-sensing, energy storage and conversion, etc. Their porous structure, pore size, specific surface areas and functions can be directly designed and facilely tuned by introducing specific functional building blocks. In this review article, we summarize the latest representative advances in the field of POPs, focusing on their design and synthetic strategies, with emphasis on their specific applications in photocatalysis, including photocatalytic chemical transformation, photodetoxification of contaminants from water, and water splitting.

Nitrogen-rich covalent organic frameworks with multiple carbonyls for high-performance sodium batteries.

Abstract: Covalent organic frameworks with designable periodic skeletons and ordered nanopores have attracted increasing attention as promising cathode materials for rechargeable batteries. However, the reported cathodes are plagued by limited capacity and unsatisfying rate performance. Here we report a honeycomb-like nitrogen-rich covalent organic framework with multiple carbonyls. The sodium storage ability of pyrazines and carbonyls and the up-to twelve sodium-ion redox chemistry mechanism for each repetitive unit have been demonstrated by in/ex-situ Fourier transform infrared spectra and density functional theory calculations. The insoluble electrode exhibits a remarkably high specific capacity of 452.0 mAh g−1, excellent cycling stability (~96% capacity retention after 1000 cycles) and high rate performance (134.3 mAh g−1 at 10.0 A g−1). Furthermore, a pouch-type battery is assembled, displaying the gravimetric and volumetric energy density of 101.1 Wh kg−1cell and 78.5 Wh L−1cell, respectively, indicating potentially practical applications of conjugated polymers in rechargeable batteries. Covalent organic frameworks are receiving increasing attention as promising cathode materials for rechargeable batteries. Here the authors report a honeycomb-like nitrogen-rich COF design in which the pyrazines and carbonyls enable favorable redox chemistry and remarkable Na-ion storage performance.

Fundamental Concepts of Hydrogels: Synthesis, Properties, and Their Applications

Abstract: In the present review, we focused on the fundamental concepts of hydrogels-classification, the polymers involved, synthesis methods, types of hydrogels, properties, and applications of the hydrogel. Hydrogels can be synthesized from natural polymers, synthetic polymers, polymerizable synthetic monomers, and a combination of natural and synthetic polymers. Synthesis of hydrogels involves physical, chemical, and hybrid bonding. The bonding is formed via different routes, such as solution casting, solution mixing, bulk polymerization, free radical mechanism, radiation method, and interpenetrating network formation. The synthesized hydrogels have significant properties, such as mechanical strength, biocompatibility, biodegradability, swellability, and stimuli sensitivity. These properties are substantial for electrochemical and biomedical applications. Furthermore, this review emphasizes flexible and self-healable hydrogels as electrolytes for energy storage and energy conversion applications. Insufficient adhesiveness (less interfacial interaction) between electrodes and electrolytes and mechanical strength pose serious challenges, such as delamination of the supercapacitors, batteries, and solar cells. Owing to smart and aqueous hydrogels, robust mechanical strength, adhesiveness, stretchability, strain sensitivity, and self-healability are the critical factors that can identify the reliability and robustness of the energy storage and conversion devices. These devices are highly efficient and convenient for smart, light-weight, foldable electronics and modern pollution-free transportation in the current decade.

Polymer/molecular semiconductor all-organic composites for high-temperature dielectric energy storage.

Abstract: Dielectric polymers for electrostatic energy storage suffer from low energy density and poor efficiency at elevated temperatures, which constrains their use in the harsh-environment electronic devices, circuits, and systems. Although incorporating insulating, inorganic nanostructures into dielectric polymers promotes the temperature capability, scalable fabrication of high-quality nanocomposite films remains a formidable challenge. Here, we report an all-organic composite comprising dielectric polymers blended with high-electron-affinity molecular semiconductors that exhibits concurrent high energy density (3.0 J cm−3) and high discharge efficiency (90%) up to 200 °C, far outperforming the existing dielectric polymers and polymer nanocomposites. We demonstrate that molecular semiconductors immobilize free electrons via strong electrostatic attraction and impede electric charge injection and transport in dielectric polymers, which leads to the substantial performance improvements. The all-organic composites can be fabricated into large-area and high-quality films with uniform dielectric and capacitive performance, which is crucially important for their successful commercialization and practical application in high-temperature electronics and energy storage devices. Dielectric polymers are widely used in electrostatic energy storage but suffer from low energy density and efficiency at elevated temperatures. Here, the authors show that all-organic composites containing high-electron-affinity molecular semiconductors exhibit excellent capacitive performance at 200 °C.

Optimized active layer morphology toward efficient and polymer batch insensitive organic solar cells.

Abstract: Morphology control in laboratory and industry setting remains as a major challenge for organic solar cells (OSCs) due to the difference in film-drying kinetics between spin coating and the printing process. A two-step sequential deposition method is developed to control the active layer morphology. A conjugated polymer that self-assembles into a well-defined fibril structure is used as the first layer, and then a non-fullerene acceptor is introduced into the fibril mesh as the second layer to form an optimal morphology. A benefit of the combined fibril network morphology and non-fullerene acceptor properties was that a high efficiency of 16.5% (certified as 16.1%) was achieved. The preformed fibril network layer and the sequentially deposited non-fullerene acceptor form a robust morphology that is insensitive to the polymer batches, solving a notorious issue in OSCs. Such progress demonstrates that the utilization of polymer fibril networks in a sequential deposition process is a promising approach towards the fabrication of high-efficiency OSCs. Reliably controlling the morphology in organic solar cells is desired for up-scaling. Here Weng et al. combine the advantages of the fibril network donor and the state of the art Y6 acceptor in a two-step approach to deliver a high efficiency of 16% without batch-to-batch variation.

Random terpolymer based on thiophene-thiazolothiazole unit enabling efficient non-fullerene organic solar cells.

Abstract: Developing a high-performance donor polymer is critical for achieving efficient non-fullerene organic solar cells (OSCs). Currently, most high-efficiency OSCs are based on a donor polymer named PM6, unfortunately, whose performance is highly sensitive to its molecular weight and thus has significant batch-to-batch variations. Here we report a donor polymer (named PM1) based on a random ternary polymerization strategy that enables highly efficient non-fullerene OSCs with efficiencies reaching 17.6%. Importantly, the PM1 polymer exhibits excellent batch-to-batch reproducibility. By including 20% of a weak electron-withdrawing thiophene-thiazolothiazole (TTz) into the PM6 polymer backbone, the resulting polymer (PM1) can maintain the positive effects (such as downshifted energy level and reduced miscibility) while minimize the negative ones (including reduced temperature-dependent aggregation property). With higher performance and greater synthesis reproducibility, the PM1 polymer has the promise to become the work-horse material for the non-fullerene OSC community. The batch reproducibility of polymer donor materials limits the performance of polymer solar cells. Here Wu et al. develop a polymer donor PM1 by random terpolymerization strategy with a high efficiency of 17.6% in the device and excellent batch-to-batch reproducibility.

Protein-Based Nanoparticles as Drug Delivery Systems.

Abstract: Nanoparticles have been extensively used as carriers for the delivery of chemicals and biomolecular drugs, such as anticancer drugs and therapeutic proteins Natural biomolecules, such as proteins, are an attractive alternative to synthetic polymers commonly used in nanoparticle formulation because of their safety In general, protein nanoparticles offer many advantages, such as biocompatibility and biodegradability Moreover, the preparation of protein nanoparticles and the corresponding encapsulation process involved mild conditions without the use of toxic chemicals or organic solvents Protein nanoparticles can be generated using proteins, such as fibroins, albumin, gelatin, gliadine, legumin, 30Kc19, lipoprotein, and ferritin proteins, and are prepared through emulsion, electrospray, and desolvation methods This review introduces the proteins used and methods used in generating protein nanoparticles and compares the corresponding advantages and disadvantages of each

Two compatible polymer donors contribute synergistically for ternary organic solar cells with 17.53% efficiency

Abstract: A ternary strategy has been demonstrated as a promising method to further boost the performance of organic solar cells (OSCs). Herein, an efficient polymer donor S3 was synthesized and incorporated into a PM6:Y6 system to fabricate ternary OSCs. S3 possesses complementary absorption spectra and good compatibility with PM6, which is beneficial to fine-tune the photon harvesting and morphology of the ternary blend films, resulting in simultaneous enhancement of the short-circuit current density (JSC) and fill factor (FF). In addition, the highest occupied molecular orbital (HOMO) energy level of S3 is slightly lower than that of PM6, which enables lower nonradiative energy loss in ternary OSCs compared with that of PM6-based binary OSCs, leading to higher open-circuit voltage (VOC). The optimized ternary OSCs with 20 wt% S3 in the donors achieve a PCE of 17.53%, which should be among the highest values of ternary OSCs. This work provides an effective approach to fabricate high-performance ternary OSCs by synergizing two well-matched polymer donors.

A Polymerization-Assisted Grain Growth Strategy for Efficient and Stable Perovskite Solar Cells

Abstract: Intrinsically, detrimental defects accumulating at the surface and grain boundaries limit both the performance and stability of perovskite solar cells. Small molecules and bulkier polymers with functional groups are utilized to passivate these ionic defects but usually suffer from volatility and precipitation issues, respectively. Here, starting from the addition of small monomers in the PbI2 precursor, a polymerization-assisted grain growth strategy is introduced in the sequential deposition method. With a polymerization process triggered during the PbI2 film annealing, the bulkier polymers formed will be adhered to the grain boundaries, retaining the previously established interactions with PbI2 . After perovskite formation, the polymers anchored on the boundaries can effectively passivate undercoordinated lead ions and reduce the defect density. As a result, a champion power conversion efficiency (PCE) of 23.0% is obtained, together with a prolonged lifetime where 85.7% and 91.8% of the initial PCE remain after 504 h continuous illumination and 2208 h shelf storage, respectively.

A Solvent-Exchange Strategy to Regulate Noncovalent Interactions for Strong and Antiswelling Hydrogels

Abstract: Physical hydrogels from existing polymers consisting of noncovalent interacting networks are highly desired due to their well-controlled compositions and environmental friendliness; and therefore, applied as adhesives, artificial tissues, and soft machines. Nevertheless, these gels have suffered from weak mechanical strength and low water resistance. Current methodologies used to fabricate these hydrogels mainly involve the freezing-thawing process (cryogels), which are complicated in preparation and short in adjustment of polymer conformation. Here, taking the merits of noncovalent bonds in adjustability and reversibility, a solvent-exchange strategy is developed to construct a class of exogels. Based on the exchange from a good solvent subsequently to a poor one, the intra- and interpolymer interactions are initially suppressed and then recovered, resulting in dissolving and cross-linking to polymers, respectively. Key to this approach is the good solvent, which favors of a stretched polymer conformation to homogenize the network, forming cross-linked hydrogel networks with remarkable stiffness, toughness, antiswelling properties, and thus underwater adhesive performance. The exogels highlight a facile but highly effective strategy of turning the solvent and consequently the noncovalent interactions to achieve the rational design of enhanced hydrogels and hydrogel-based soft materials.

Polymerization Reactions and Modifications of Polymers by Ionizing Radiation.

Abstract: Ionizing radiation has become the most effective way to modify natural and synthetic polymers through crosslinking, degradation, and graft polymerization. This review will include an in-depth analysis of radiation chemistry mechanisms and the kinetics of the radiation-induced C-centered free radical, anion, and cation polymerization, and grafting. It also presents sections on radiation modifications of synthetic and natural polymers. For decades, low linear energy transfer (LLET) ionizing radiation, such as gamma rays, X-rays, and up to 10 MeV electron beams, has been the primary tool to produce many products through polymerization reactions. Photons and electrons interaction with polymers display various mechanisms. While the interactions of gamma ray and X-ray photons are mainly through the photoelectric effect, Compton scattering, and pair-production, the interactions of the high-energy electrons take place through coulombic interactions. Despite the type of radiation used on materials, photons or high energy electrons, in both cases ions and electrons are produced. The interactions between electrons and monomers takes place within less than a nanosecond. Depending on the dose rate (dose is defined as the absorbed radiation energy per unit mass), the kinetic chain length of the propagation can be controlled, hence allowing for some control over the degree of polymerization. When polymers are submitted to high-energy radiation in the bulk, contrasting behaviors are observed with a dominant effect of cross-linking or chain scission, depending on the chemical nature and physical characteristics of the material. Polymers in solution are subject to indirect effects resulting from the radiolysis of the medium. Likewise, for radiation-induced polymerization, depending on the dose rate, the free radicals generated on polymer chains can undergo various reactions, such as inter/intramolecular combination or inter/intramolecular disproportionation, b-scission. These reactions lead to structural or functional polymer modifications. In the presence of oxygen, playing on irradiation dose-rates, one can favor crosslinking reactions or promotes degradations through oxidations. The competition between the crosslinking reactions of C-centered free radicals and their reactions with oxygen is described through fundamental mechanism formalisms. The fundamentals of polymerization reactions are herein presented to meet industrial needs for various polymer materials produced or degraded by irradiation. Notably, the medical and industrial applications of polymers are endless and thus it is vital to investigate the effects of sterilization dose and dose rate on various polymers and copolymers with different molecular structures and morphologies. The presence or absence of various functional groups, degree of crystallinity, irradiation temperature, etc. all greatly affect the radiation chemistry of the irradiated polymers. Over the past decade, grafting new chemical functionalities on solid polymers by radiation-induced polymerization (also called RIG for Radiation-Induced Grafting) has been widely exploited to develop innovative materials in coherence with actual societal expectations. These novel materials respond not only to health emergencies but also to carbon-free energy needs (e.g., hydrogen fuel cells, piezoelectricity, etc.) and environmental concerns with the development of numerous specific adsorbents of chemical hazards and pollutants. The modification of polymers through RIG is durable as it covalently bonds the functional monomers. As radiation penetration depths can be varied, this technique can be used to modify polymer surface or bulk. The many parameters influencing RIG that control the yield of the grafting process are discussed in this review. These include monomer reactivity, irradiation dose, solvent, presence of inhibitor of homopolymerization, grafting temperature, etc. Today, the general knowledge of RIG can be applied to any solid polymer and may predict, to some extent, the grafting location. A special focus is on how ionizing radiation sources (ion and electron beams, UVs) may be chosen or mixed to combine both solid polymer nanostructuration and RIG. LLET ionizing radiation has also been extensively used to synthesize hydrogel and nanogel for drug delivery systems and other advanced applications. In particular, nanogels can either be produced by radiation-induced polymerization and simultaneous crosslinking of hydrophilic monomers in "nanocompartments", i.e., within the aqueous phase of inverse micelles, or by intramolecular crosslinking of suitable water-soluble polymers. The radiolytically produced oxidizing species from water, •OH radicals, can easily abstract H-atoms from the backbone of the dissolved polymers (or can add to the unsaturated bonds) leading to the formation of C-centered radicals. These C-centered free radicals can undergo two main competitive reactions; intramolecular and intermolecular crosslinking. When produced by electron beam irradiation, higher temperatures, dose rates within the pulse, and pulse repetition rates favour intramolecular crosslinking over intermolecular crosslinking, thus enabling a better control of particle size and size distribution. For other water-soluble biopolymers such as polysaccharides, proteins, DNA and RNA, the abstraction of H atoms or the addition to the unsaturation by •OH can lead to the direct scission of the backbone, double, or single strand breaks of these polymers.

Role of Polymer Structures in Catalysis by Transition Metal and Metal Oxide Nanoparticle Composites.

Abstract: Nanoparticle (NP)/polymer nanocomposites received considerable attention because of their important applications including catalysis. Metal and metal oxide NPs may impart catalytic properties to polymer nanocomposites, while polymers with a different structure, functionality, and architecture control the NP formation (size, shape, location, composition, etc.) and in this way, govern catalytic properties of nanocomposites. In this review we will discuss the influence of the polymer nanostructure (thin or grafted layers, polymer ordering, polymer nanopores), architecture (branched vs linear), functional groups (coordinating or ionic), specific properties (reducing, stimuli responsive, conductive), etc. on the formation of metal or metal oxide NPs and the catalytic behavior of the nanocomposites. The development of novel and efficient catalysts is crucial for progress in chemical sciences, and this explains a huge number of publications in this area in recent years. Taking into consideration previous review articles on NP/polymer catalysts, we limited this review to a discussion of a narrow temporal scope (2017-April 2019), while embracing a broad subject scope, i.e., considering any polymers and NPs which form catalytic nanocomposites. This gives us a unique view of the field of catalytic polymer nanocomposites and allows understanding of where the field is going.

Crosslinked fluoropolymers exhibiting superior high-temperature energy density and charge–discharge efficiency

Abstract: The electrification of transport requires dielectric materials capable of operating efficiently at high temperatures to meet the increasing demand of electrical energy storage at extreme conditions. Current high-temperature dielectric polymers rely on the incorporation of wide bandgap inorganic fillers to restrain electrical conduction and achieve high efficiencies at elevated temperatures. Here, we report a new class of all-polymer based high-temperature dielectric materials prepared from crosslinking of melt-processable fluoropolymers. The crosslinked polymers exhibit larger discharged energy densities and greater charge–discharge efficiencies along with excellent breakdown strength and cyclic stability at elevated temperatures when compared to the current dielectric polymers. The origins of the marked improvement in the high-temperature capacitive performance are traced to efficient charge-trapping by a range of the molecular trapping centers resulting from the crosslinked structures. In addition, the implementation of melt-extrudable polymers would enable scalable processing that is compatible with the current fabrication techniques used for polymer dielectrics, which is in sharp contrast to the dielectric polymer composites with inorganic fillers.

Color‐Tunable, Excitation‐Dependent, and Time‐Dependent Afterglows from Pure Organic Amorphous Polymers

Abstract: Achieving persistent room-temperature phosphorescence (p-RTP), particularly those of tunable full-colors, from pure organic amorphous polymers is attractive but challenging. Particularly, those with tunable multicolor p-RTP in response to excitation wavelength and time are highly important but both fundamentally and technically underexplored. Here, a facile and general strategy toward color-tunable p-RTP from blue to orange-red based on amidation grafting of luminophores onto sodium alginate (SA) chains, resulting in amorphous polymers with distinct p-RTP and even impressively excitation-dependent and time-dependent afterglows is reported. p-RTP is associated with the unique semi-rigidified SA chains, effective hydrogen bonding network, and oxygen barrier properties of SA, whereas excitation-dependent and time-dependent afterglows should stem from the formation of diversified p-RTP emissive species with comparable but different lifetimes. These results outline a rational strategy toward amorphous smart luminophores with colorful, excitation-dependent, and time-dependent p-RTP, excellent solution processability, and film-forming ability for versatile applications.

Organoboron Polymer for 10% Efficiency All-Polymer Solar Cells

Abstract: Optoelectronic polymers are always π-conjugated polymers consisting of C, H, N, S, and O elements. The main group element chemistry is a new tool to tune the optoelectronic properties of polymers. ...

Switchable Catalysis Improves the Properties of CO2-Derived Polymers: Poly(cyclohexene carbonate-b-ε-decalactone-b-cyclohexene carbonate) Adhesives, Elastomers, and Toughened Plastics.

Abstract: Carbon dioxide/epoxide copolymerization is an efficient way to add value to waste CO2 and to reduce pollution in polymer manufacturing. Using this process to make low molar mass polycarbonate polyols is a commercially relevant route to new thermosets and polyurethanes. In contrast, high molar mass polycarbonates, produced from CO2, generally under-deliver in terms of properties, and one of the most widely investigated, poly(cyclohexene carbonate), is limited by its low elongation at break and high brittleness. Here, a new catalytic polymerization process is reported that selectively and efficiently yields degradable ABA-block polymers, incorporating 6-23 wt % CO2. The polymers are synthesized using a new, highly active organometallic heterodinuclear Zn(II)/Mg(II) catalyst applied in a one-pot procedure together with biobased e-decalactone, cyclohexene oxide, and carbon dioxide to make a series of poly(cyclohexene carbonate-b-decalactone-b-cyclohexene carbonate) [PCHC-PDL-PCHC]. The process is highly selective (CO2 selectivity >99% of theoretical value), allows for high monomer conversions (>90%), and yields polymers with predictable compositions, molar mass (from 38-71 kg mol-1), and forms dihydroxyl telechelic chains. These new materials improve upon the properties of poly(cyclohexene carbonate) and, specifically, they show good thermal stability (Td,5 ∼ 280 °C), high toughness (112 MJ m-3), and very high elongation at break (>900%). Materials properties are improved by precisely controlling both the quantity and location of carbon dioxide in the polymer chain. Preliminary studies show that polymers are stable in aqueous environments at room temperature over months, but they are rapidly degraded upon gentle heating in an acidic environment (60 °C, toluene, p-toluene sulfonic acid). The process is likely generally applicable to many other lactones, lactides, anhydrides, epoxides, and heterocumulenes and sets the scene for a host of new applications for CO2-derived polymers.

Well-Defined Gold Nanorod/Polymer Hybrid Coating with Inherent Antifouling and Photothermal Bactericidal Properties for Treating an Infected Hernia.

Abstract: Biomedical device-associated infection (BAI) is a great challenge in modern clinical medicine. Therefore, developing efficient antibacterial materials is significantly important and meaningful for the improvement of medical treatment and people's health. In the present work, we developed a strategy of surface functionalization for multifunctional antibacterial applications. A functionalized polyurethane (PU, a widely used biomedical material for hernia repairing) surface (PU-Au-PEG) with inherent antifouling and photothermal bactericidal properties was readily prepared based on a near-infrared (NIR)-responsive organic/inorganic hybrid coating which consists of gold nanorods (Au NRs) and polyethylene glycol (PEG). The PU-Au-PEG showed a high efficiency to resist adhesion of bacteria and exhibited effective photothermal bactericidal properties under 808 nm NIR irradiation, especially against multidrug-resistant bacteria. Furthermore, the PU-Au-PEG could inhibit biofilm formation long term. The biocompatibility of PU-Au-PEG was also proved by cytotoxicity and hemolysis tests. The in vivo photothermal antibacterial properties were first verified by a subcutaneous implantation animal model. Then, the anti-infection performance in a clinical scenario was studied with an infected hernia model. The results of animal experiment studies demonstrated excellent in vivo anti-infection performances of PU-Au-PEG. The present work provides a facile and promising approach to develop multifunctional biomedical devices.

Recent advances in natural polymer-based drug delivery systems

Abstract: Natural polymers have been extensively explored as the vehicles for encapsulation and delivery of drugs and other bioactive molecules, which have attracted tremendous attention. Their inherent advantages in marvelous biocompatibility, controlled enzyme degradation, specific interactions with some biomolecules, and easy modification endow them with versatility in drug delivery. In this perspective, the drug delivery systems (DDS) constructed by representative natural polymers, polysaccharides (chitosan and hyaluronic acid) and proteins (silk fibroin and collagen), are generally summarized. Payloads mainly involve small molecular weight drug, proteins, and DNA for the applications of tissue engineering, wound healing or anticancer therapy. Moreover, the DDS constructed by their derivatives and with other materials also have been presented focusing on the chemical and morphological modifications, the addtions of smart stimuli-triggered or targeted motifs and so on, which evidently promoted the delivery and therapy efficiency. Obviously, more intelligent and specific delivery strategies will be developed and more multifunctional natural polymers based carriers will be expended in the future. We try to seek more insights into the evolution of delivery system so as to figure out what we will truly gain in the next few decades to come.