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Owing to the natural abundance, variety of structural features, and highly specific functions, natural monomers render themselves as potential candidates for production of high ...performance functional polymers. The emerging concept of the biorefinery and development of new biosynthetic routes to synthesize a versatile and broad spectrum of natural monomers and polymers continues to gain momentum. The production of high quality polymers from renewable feedstocks requires innovative chemical modifications and catalytic transformations to achieve higher yields in an efficient manner. A fresh look into monomers available from natural resources such as terpenes, rosin, glycerol, furans, tannins, suberin, their derivatives and miscellaneous monomers may inspire future applications with impactful biobased materials. There are also many areas that require urgent discussion and review pertaining to recent developments in the field; this includes monomer sources that give molecules having special structural features. In particular, cardanol, a naturally occurring low-molecular-weight compound is unique as it contains a phenolic head group and a hydrocarbon chain with different degrees of unsaturation. This molecule possesses functional groups that are amenable for classical chemical modification, which is instrumental in developing a wide range of functional monomers and polymers. A large number of soft and hard materials have been developed from cardanol-based monomers. During the past, a large number of industrial grade materials have been developed from plant-based monomers, including development from microbial and fermentation processes (i.e. lactic acid). This review provides a comprehensive study and survey on recent developments on monomers and polymers derived from urushiol and cardanol based monomers and polymers, vegetable oil-based monomers and polymers, microbially produced monomers and polymers. These all represent emerging fronts giving a vast scope while highlighting important potential material and reagent opportunities.
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•The functional polymers-coated Cu hollow microspheres catalyst is prepared.•This catalyst makes Zn–CO2 battery an impressive capability of CO2 conversion.•The high energy density CH4 ...product can be obtained.•The primary Zn–CO2 battery exhibits a high power density of 1.36 mW cm−2.•A homemade in-situ Raman device displays the evolution of the CO2RR intermediates.
Zn–CO2 batteries are attracting much attention because the CO2 reduction reaction (CO2RR) to hydrocarbon products takes place during the discharge process. However, the CO2RR products in Zn–CO2 batteries are almost exclusively C1 products (CO and HCOOH) without exploring high energy density products. Therefore, in this work, the functional polymers-coated Cu hollow microspheres are prepared as the cathodic catalysts in the primary Zn–CO2 batteries with the aim of obtaining the high energy density product of CH4. Functional polymers composed of polyethyleneimine (PEI) and perfluorinated sulfonic acid (PFSA) are orderly coated on the Cu hollow microspheres prepared by using the colloidal self-assembly technique to form a Cu/PEI/PFSA cathodic catalyst. According to the results of the finite element analysis, PFSA enables CO2 diffusion length to reach more than 200 nm, while the PEI gives rise to a high steady-state CO2 concentration of 0.726 mol m−3 on the Cu surface. Hence, as compared to the Cu nanoparticles and bare Cu hollow microspheres catalysts, the Cu/PEI/PFSA-based primary Zn–CO2 battery exhibits a maximum power density of 1.36 mW cm−2 and a high Faraday efficiency of 42.78 % towards CH4 at 5 sccm of CO2 flow rate and 1.25 mA cm−2 of current density. In addition, a homemade in-situ Raman device displays the evolution of the CO2RR intermediates during the operation of the primary Zn–CO2 batteries, revealing the direction of CO2 conversion to hydrocarbon products.
•Many studies were done to purify wastewater and to preserve fresh water sources.•Here, the synthesis/fabrication of polymeric-clay membranes for water treatment are described.•The ...antifouling/antimicrobial/antifungal properties of the membranes are assessed broadly.•Overall, we describe the field of water conservation based on functional polymer-clay composites.
Water is essential for every living being. Increasing population, mismanagement of water sources, urbanization, industrialization, globalization, and global warming have all contributed to the scarcity of fresh water sources and the growing demand of such resources. Securing and allocating sufficient water resources has thus become one of the current major global challenges. Membrane technology has dominated the field of water purification due to its ease of usage and fabrication with high efficiency. The development of novel membrane materials can hence play a central role in advancing the field of membrane technology. It is noted that polymer-clay nanocomposites have been used widely for treatment of waste water. Nonetheless, not much efforts have been put to functionalize their membranes to be selective for specific targets. This review was organized to offer better insights into various types of functional polymer and clays composite membranes developed for efficient treatment and purification of water/wastewater. Our discussion was extended further to evaluate the efficacy of membrane techniques employed in the water industry against major chemical (e.g., heavy metal, dye, and phenol) and biological contaminants (e.g., biofouling).
The past decade has witnessed tremendous advances in the synthesis of polymers that contain elements from the main groups beyond those found in typical organic polymers. Unique properties that arise ...from dramatic differences in bonding and molecular geometry, electronic structure, and chemical reactivity, are exploited in diverse application fields. Herein we highlight recent advances in inorganic backbone polymers, discuss how Lewis acid/base functionalization of polymers results in unprecedented reactivity, and survey conjugated hybrids with unique electronic structures for sensor and device applications.
Polymers go main group! This Review shows how the incorporation of the full range of available main‐group elements into polymers leads to new functional hybrid materials with potential use in diverse application fields ranging from advanced elastomers, responsive gels, biodegradable materials, to organic electronics, imaging agents, sensors, and supported catalysts.
Effective utilization of carbon dioxide as a C1 feedstock is an ongoing challenge for chemists. The catalytic reaction of epoxides and carbon dioxide to produce cyclic or polycarbonates has become an ...important reaction that continues to be dominated by metal-based catalysts. Metal-free catalysts have shown promise as an alternative for these transformations, but this area remains quite underdeveloped. In this work, we show that arylboranes, BPh3 and B(C6F5)3, can be used as catalysts, in the presence of a suitable cocatalyst or as a preformed Lewis acid/base adduct, to prepare either the cyclic organic carbonate e.g., a turnover number (TON) of 2960 was obtained for propylene oxide to propylene carbonate or polycarbonate product (e.g., copolymerization of vinylcyclohexene oxide gave a polycarbonate with 99+% carbonate linkages, M n 6270 g mol–1, Đ 1.03). Selectivity toward cyclic or polymer product is dependent on the substrate used. Lower activity was observed using B(C6F5)3 due to its increased Lewis acidity. Kinetic studies of this “metal-free” reaction reveal a process that is first-order in all reagents with the surprising exception of carbon dioxide, for which an inverse dependence was discovered. This means reactions can be performed at atmospheric pressure (TON 3960 for glycidyl chloride to cyclic carbonate at P CO2 1 atm). In terms of polycarbonate formation, when a bicyclic epoxide containing a vinyl functional group was employed as a substrate, the vinyl functionality could be cross-linked (both intra- and intermolecularly) or part of a functional monomer, leading to polycarbonates with T g values of 184 and 122 °C, respectively. These data highlight that a wide range of sustainable, organic carbonate materials can be produced at modest pressures using arylborane catalysts, the reactivity of which can be modified by adjustment of electronics and potentially sterics.
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Magnetic resonance imaging (MRI) is recognized as the most powerful clinical imaging modality due to its ability to generate detailed three-dimensional anatomical images with high ...spatial resolution in a non-invasive manner without requiring harmful ionizing radiation. Conventionally, exogenous paramagnetic transition metal ion chelates or iron oxide nanoparticles are used as contrast agents (CAs) to enhance the image contrast of anatomical features. However, despite the wide use of these metal-based CAs, safety concerns have been raised regarding their potential toxic effects resulting from long-term in vivo accumulation. This has driven the development of organic metal-free CAs in various forms for use in MRI. Importantly, functional polymers capable of MRI via different mechanisms represent one of the most promising alternatives to current metal-based MRI CAs due to appealing features such as low toxicity, improved pharmacokinetics and biodistribution profile, and tailored structures and functionalities. Such structural and functional flexibility can enable a myriad of biomedical applications. In this review, we will highlight advances in the development of functional polymers as organic metal-free macromolecular MRI CAs based on different mechanisms including polymeric nitroxide-based 1H MRI CAs, polymeric chemical exchange saturation transfer (CEST) MRI CAs, and polymeric heteronuclei-based MRI CAs. In addition, the review will address the challenges and future opportunities for these promising classes of metal-free polymeric MRI CAs.
Although mortality continues to decline over the past two decades, cancer is still a pervasive healthcare problem worldwide due to the increase in the number of cases, multidrug resistance (MDR) and ...metastasis. As a consequence of multidrug resistance, cancer treatment must rely on a host of chemotherapeutic agents and chemosensitizers to achieve remission. To overcome these problems, a series of biodegradable triblock copolymers of PEG, guanidinium-functionalized polycarbonate and polylactide (PEG-PGCx-PDLAy) is designed as chemotherapeutic agents. These copolymers self-assemble into micellar nanoparticles, and are highly effective against various cancer cell lines including human breast cancer (BCap37), liver cancer (HepG2), lung cancer (A549) and epidermoid carcinoma (A431) cell lines as well as MDR Bats-72 and Bads-200 cancer cells that were developed from BCap37. Multiple treatments with the polymers at sub-lethal doses do not induce resistance. The polymers kill cancer cells by a non-apoptotic mechanism with significant vacuolization and subsequent membrane disruption. In vivo antitumor efficacy is evaluated in a metastatic 4T1 subcutaneous tumor model. Treatment with stereocomplexes of PEG-PGC43-PLLA19 and PEG-PGC43-PDLA20 at a dose of 20 mg/kg of mouse body weight suppresses tumor growth and inhibits tumor metastasis in vivo. These polymers show promise in the treatment of cancer without the onset of resistance.
A series of biodegradable block copolymers are synthesized and self-assembled into micelles of distinctive anticancer mechanism. These polymers are highly effective against various cancer cell types including multidrug-resistant ones, demonstrate an excellent in vivo antitumor effect while inhibiting tumor metastasis. More importantly, repeated use does not induce resistance. These macromolecules have excellent potential for use as anticancer agents. Display omitted
The functionalization of nanoparticles has primarily been used as a means to impart stability in nanoparticle suspensions. In most cases even the most advanced nanomaterials lose their function ...should suspensions aggregate and settle, but with the capping agents designed for specific solution chemistries, functionalized nanomaterials generally remain monodisperse in order to maintain their function. The importance of this cannot be underestimated in light of the growing use of functionalized nanomaterials for wide range of applications. Advanced functionalization schemes seek to exert fine control over suspension stability with small adjustments to a single, controllable variable. This review is specific to functionalized nanoparticles and highlights the synthesis and attachment of novel functionalization schemes whose design is meant to affect controllable aggregation. Some examples of these materials include stimulus responsive polymers for functionalization which rely on a bulk solution physicochemical threshold (temperature or pH) to transition from a stable (monodisperse) to aggregated state. Also discussed herein are the primary methods for measuring the kinetics of particle aggregation and theoretical descriptions of conventional and novel models which have demonstrated the most promise for the appropriate reduction of experimental data. Also highlighted are the additional factors that control nanoparticle stability such as the core composition, surface chemistry and solution condition. For completeness, a case study of gold nanoparticles functionalized using homologous block copolymers is discussed to demonstrate fine control over the aggregation state of this type of material.
We highlight synthetic approaches to nanoparticle functionalization, and experimental methods for determining suspension stability and the kinetics of aggregation. We discuss theoretical models to study interparticle potential and colloidal stability of core–shell nanoparticles, by varying the composition of nanoparticle core, the surface chemistry and solution conditions. Display omitted
•Synthetic approaches to nanoparticle functionalization.•Experimental methods for aggregation kinetics characterization.•Theoretical frameworks for stability ratio calculation of core-shell particles.•Unified structure-property characterization for rational nanoparticle design.
Recently, one of the most important scientific issues for a better future life for humanity is achieving the ability to intelligently harvest, store, and utilize energy with good efficiency because ...we are facing critical environmental pollution and exhaustion of energy resources. Moreover, dramatic developments in advanced electronics, such as portable and wearable devices and electric vehicles, are being realized. Therefore, energy storage systems (ESSs) are very important for the operation of these advanced electronics. Among the energy storage materials, redox-active polymers are very attractive for ESSs because they have outstanding advantages compared with metal-based energy storage materials. For this reason, redox-active polymers are currently attracting much attention. In this review, we classify the redox-active organic groups of redox-active polymers. In addition, the latest advances in redox-active polymers and their promising application potential for ESSs are discussed with a specific focus on precise molecular designs, nanoarchitectonics, and other new approaches.
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Developing novel energy storage systems (ESSs) with high performance suitable for next-generation smart electronics and electric vehicles is one of the most important research issues. In addition, ESSs are also important for a better future for humanity, which is facing critical issues such as energy, the environment, climate, the food supply, and disease.
We can certainly conclude that the active materials are the key parts in ESS technologies for achieving superior electrochemical properties because their energy storage capability, cycle life, and charging rate predominantly depend on the active materials. Among active materials for ESSs, redox-active polymers have advantages in terms of cost-effectiveness, diversity, good processability, unique electrochemical properties, and precise tuning for ESSs. In addition, redox-active polymers can be easily combined and hybridized with other technologies and materials. Therefore, redox-active polymers are attractive as promising materials for future ESSs. Here, we present the latest research to highlight ESS applications based on redox-active polymers with a special focus on their precise molecular designs, nanoarchitectonics, and other newly developed approaches.
Based on a specific focus on precise molecular designs, nanoarchitectonics, and new approaches, we review the latest research of redox-active polymers to highlight energy storage system (ESS) applications. It is certain that ESSs are very important for future advanced electronics such as portable/wearable devices and electric vehicles. Redox-active polymers have advantages of organics, material design, and superior electrochemical properties. This review summarizes and introduces the most recent research progress and discusses the future redox-active polymers for ESSs.
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