Recent progress on cyclic polymers: Synthesis,bioproperties, and biomedical applications

Polymer topologies exert a significant effect on its properties, and polymer nanostructures with advanced architectures, such as cyclic polymers, star‐shaped polymers, and hyperbranched polymers, are a promising class of materials with advantages over conventional linear counterparts. Cyclic polymers, due to the lack of polymer chain ends, have displayed intriguing physical and chemical properties. Such uniqueness has drawn considerable attention over the past decade. The current review focuses on the recent progress in the design and development of cyclic polymer with an emphasis on its synthesis and bio‐related properties and applications. Two primary synthetic strategies towards cyclic polymers, that is, ring‐expansion polymerization and ring‐closure reaction are summarized. The bioproperties and biomedical applications of cyclic polymers are then highlighted. In the end, the future directions of this rapidly developing research field are discussed. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1447–1458     

Malolactonate polymers and copolymers for biomedical applications

A new class of malolactonate polymers and copolymers with a wide range of lateral chain structures were synthesized by anionic ring opening polymerization of alkyl malolactonate monomers. The monomers were prepared in good yields according to established procedures. Final macromolecular and thermal characteristics were in agreement with the designed monomer structures. Molecular weights in the range 4-20 kD were attained, as a result of chain transfer reactions. Representative polymeric compounds displayed stability up to 200 °C. Many of the obtained poly(alkyl malolactonate)s were able to sustain and promote with 3T3 murine fibroblasts adhesion and proliferation onto their surface.     

Cyclic Polymers by Ring‐Closure Strategies

The preparation of cyclic macromolecules has always represented a challenging task for polymer science, mainly because of difficulties in connecting chain extremities together. Initiated by the pioneering studies of Jacobson and Stockmayer, preparative pathways to cyclic polymers have been considerably improved within the last two decades thanks to the advent of both controlled polymerizations and efficient coupling reactions in organic chemistry. This Review aims to provide a critical up‐to‐date overview and illustrate the considerable efforts that have been made in the past few years to improve the availability of macrocycles for industrial and academic investigations through the use of the ring‐closure approach. Particular attention is paid to methods for the preparation of monocycles over more complex architectures, since the latter are usually derived from the former.     

Functional and highly porous scaffolds for biomedical applications

Highly porous functional scaffolds were obtained from linear and cross-linked multifunctional poly(ε-caprolactone) and poly(L-lactide). The polymers were synthesized by ring-opening polymerization of ε-caprolactone and L-lactide using poly(but-2-ene-1,4-diyl malonate) (PBM) as macroinitiator and stannous 2-ethylhexanoate. The presence of a double bond in each repeating unit of PBM enabled cross-linking of both scaffolds and films. Soft and flexible scaffolds were created from cross-linked PBM. The mechanical properties of scaffolds and films were evaluated under cyclic conditions, with a focus on the compositions and molecular weights. It was obvious that PBM in the polymers and its cross-linking ability resulted in tunable material characteristics, including an increased ability to recover after repeated loading.     

金纳米粒子的合成、特性及其在生物医学检测中的应用研究进展

近年来,纳米技术越来越广泛的应用到各个领域,金纳米粒子因其具有许多优良的物理、化学及生物学性质而引起了人们特别的关注。本文综述了金纳米粒子几种经典的合成方法,以及基于金纳米粒子独特的理化性质在病原体、核酸蛋白质检测方面的最新研究进展。     

Cyclic polymers: Synthetic strategies and physical properties

Syntheses of cyclic polymers including cyclic homopolymers, cyclic block copolymers, sun‐shaped polymers, and tadpole polymers are discussed on the basis of a differentiation between synthetic methods and synthetic strategies (e.g., polycondensation, ring–ring equilibration, or ring‐expansion polymerization). Furthermore, all synthetic methods are classified as kinetically or thermodynamically controlled reactions. Characteristic properties of cyclic polymers such as smaller hydrodynamic volume, lower melt viscosities, and higher thermostabilities are compared to the properties of their linear counterparts. Furthermore, the nanophase separation of cyclic diblock copolymers is discussed. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 251–284, 2010     

Synthesis and characterization of thiazolothiazole‐based polymers and their applications in polymer solar cells

A novel series of thiazolothiazole (Tz)‐based copolymers, poly[9,9‐didecylfluorene‐2,7‐diyl‐alt‐2,5‐bis‐(3‐hexylthiophene‐2‐yl)thiazolo[5,4‐d]thiazole] (P1), poly[9,9‐dioctyldibenzosilole‐2,7‐diyl‐alt‐2,5‐bis‐(3‐hexylthiophene‐2‐yl)thiazolo[5,4‐d]thiazole] (P2), and poly[4,4′‐bis(2‐ethylhexyl)‐dithieno[3,2‐b:2′,3′‐d]silole‐alt‐2,5‐bis‐(3‐hexylthiophene‐2‐yl)thiazolo[5,4‐d]thiazole] (P3), were synthesized for the use as donor materials in polymer solar cells (PSCs). The field‐effect carrier mobilities and the optical, electrochemical, and photovoltaic properties of the copolymers were investigated. The results suggest that the donor units in the copolymers significantly influenced the band gap, electronic energy levels, carrier mobilities, and photovoltaic properties of the copolymers. The band gaps of the copolymers were in the range of 1.80–2.14 eV. Under optimized conditions, the Tz‐based polymers showed power conversion efficiencies (PCEs) for the PSCs in the range of 2.23–2.75% under AM 1.5 illumination (100 mW/cm²). Among the three copolymers, P1, which contained a fluorene donor unit, showed a PCE of 2.75% with a short‐circuit current of 8.12 mA/cm², open circuit voltage of 0.86 V, and a fill factor (FF) of 0.39, under AM 1.5 illumination (100 mW/cm²). © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Advanced Developments in Cyclic Polymers: Synthesis,Applications, and Perspectives

Due to the topological effect, cyclic polymers demonstrate different and unique physical and biological properties in comparison with linear counterparts having the same molecular-weight range. With advanced synthetic and analytic technologies, cyclic polymers with different topologies, e.g. multicyclic polymers, have been reported and well characterized. For example, various cyclic DNA and related structures, such as cyclic duplexes, have been prepared conveniently by click chemistry. These types of DNA have increased resistance to enzymatic degradation and have high thermodynamic stability, and thus, have potential therapeutic applications. In addition, cyclic polymers have also been used to prepare organic–inorganic hybrids for applications in catalysis, e.g. catalyst supports. Due to developments in synthetic technology, highly pure cyclic polymers could now be produced in large scale. Therefore, we anticipate discovering more applications in the near future. Despite their promise, cyclic polymers are still less explored than linear polymers like polyolefins and polycarbonates, which are widely used in daily life. Some critical issues, including controlling the molecular weight and finding suitable applications, remain big challenges in the cyclic-polymer field. This review briefly summarizes the commonly used synthetic methodologies and focuses more on the attractive functional materials and their biological properties and potential applications.     

Synthesis of eight- and star-shaped poly(epsilon-caprolactone)s and their amphiphilic derivatives

Spirocyclic tin dialkoxides are unique initiators for the ring-expansion polymerization of lactones leading to complex, but well-defined macromolecular architectures. In a first example, epsilon-caprolactone (epsilon CL) was polymerized, followed by the resumption of polymerization of a mixture of epsilon CL and epsilon CL alpha-substituted by a chloride (alpha Cl epsilon CL), so leading to "living" eight-shaped chains. Upon hydrolysis of the alkoxides, a four-arm star-shaped copolyester was formed, whose each arm was grafted by conversion of the chloride units into azides, followed by the Huisgen's [3+2] cycloaddition of alkyne end-capped poly(ethylene oxide) (PEO) onto the azide substituents. The complexity of this novel amphiphilic architecture was increased further by substituting the four-arm interconnecting PCL by an eight-shaped PCL. In a preliminary step, epsilon CL was polymerized followed by a few units of epsilon CL alpha-substituted by an acrylate. The intramolecular photo-crosslinking of the acrylates adjacent to the tin dialkoxides was effective in stabilizing the eight-shaped polyester while preserving the chain growth sites. This quite unusual tetrafunctional macroinitiator was used to copolymerize epsilon CL and alpha Cl epsilon CL, followed by hydrolysis of the alkoxides, conversion of the chloride units into azides and grafting of the four arms by PEO (see above). This architecture reported for the very first time is nothing but a symmetrical four-tail eight-shaped copolyester macromolecule.     

Porous shape memory polymers: Design and applications

Porous shape memory polymers (SMPs) exhibit geometric and volumetric shape change when actuated by an external stimulus and can be fabricated as foams, scaffolds, meshes, and other polymeric substrates that possess porous three-dimensional macrostructures. These materials have applications in multiple industries such as textiles, biomedical devices, tissue engineering, and aerospace. This review article examines recent developments in porous SMPs, with a focus on fabrication methods, methods of characterization, modes of actuation, and applications. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1300–1318     

Polymers as drugs—Advances in therapeutic applications of polymer binding agents

Polymer drugs are those in which a polymer agent has a direct therapeutic effect on the body. A major investigated area of polymer drugs is their use as binding agents, or sequestrants, which can neutralize or remove undesired components from the body. By taking advantage of the unique properties of crosslinked, insoluble polymers, new polymer drugs continue to be developed for oral use, acting in the gastrointestinal tract and excreted in the feces. Soluble polymer binders may be administered by a variety of routes and act at diverse sites of therapeutic action. This article reviews the properties of polymer drugs, particularly sequestrants, with an emphasis on recent advances in polymer properties which may enhance the utility of this class of drugs. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 3146–3157     

Some aspects of the synthesis and characterization of special polymers and oligomers by olefin metathesis

Homopolymers of 2-norbornene and 2,3-bis(trifluoromethyl)-2,5-norbornadiene and copolymers of these bicyclic olefins with 1,5-cyclooctadiene and cyclopentene were prepared via ring opening metathesis polymerization. The molecular weight distributions of the polymers were estimated by gel permeation chromatography.The polymers were degraded in a cross metathesis reaction with E-4-octene; only poly[2,3-bis(trifluoromethyl)-2,5-norbornadiene] was not degradable.All reactions were carried out with WCl₆/(CH₃)₄Sn as the catalyst system. The low molecular cyclic oligomers in the polymerization mixtures and the degradation products were analyzed by gas chromatography and identified using a gas chromatography/mass spectrometry coupling.The degradation experiments show reactivity differences for the double bonds situated in the polymer backbone. On the basis of these differences and the fact that this is the first time that a metathesis degradation of such polymers has been reported, the consequences on the ring opening metathesis copolymerization of cycloolefins are discussed in general terms, leading to some new aspects in the planning of the synthesis of special copolymers and oligomers.With reference to a lecture presented at the 4th International Symposium on Olefin Metathesis (ISOM 4), Belfast, 1–4 Sept. 1981.     

Cyclic polymers: past,present and future

Methods for characterising cyclic polymers are illustrated by reference first to dilute solution methods for cyclic poly(dimethylsiloxane) (PDMS) and then to the entrapment of cyclic polymers in networks. Preparative routes to cyclic polymers are then reviewed, including ring-chain equilibration reactions, coupling and condensation reactions and new methods using polymer-supported reagents. Some of the properties of cyclic PDMS are discussed, including differences between ring and chain polymer properties such as their melt viscosities and glass transition temperatures. Methods for preparing the first polymeric catenanes are described, using polymer-supported reagents. Future directions for cyclic polymer chemistry are indicated, including topological polymer chemistry.     

Vapor phase oxidative synthesis of conjugated polymers and applications

Since their discovery, electrically conductive polymers have gained immense interest both in the fields of basic and applied research. Despite their vast potential in the fabrication of efficient, flexible, and low‐cost electronic and optoelectronic devices, they are often difficult to process by wet‐chemical methods due to their very low to poor solubility in organic solvents. The use of vapor‐based synthetic routes, in which conductive polymers can be synthesized and deposited as a thin film directly on a substrate from the vapor phase, provides many unique advantages. This article discusses oxidative vapor deposition processes, primarily vapor phase polymerization and oxidative chemical vapor deposition, of conjugated polymers and their applications. The mild operating conditions (near room temperature processing) allow conformal and functional coatings of conjugated polymers on delicate substrates. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Cyclic welding behavior of covalent adaptable network polymers

Surface welding effect of covalent adaptable network (CAN) polymers enables self‐healing, reprocessing and recycling of thermosets, but little is known about their welding behaviors during repeated welding‐peeling cycles. In this article, we study the cyclic welding effect of an epoxy based thermal‐sensitive CAN. Surface roughness is generated by rubbing the sample on sandpapers with different grid sizes. The welding‐peeling cycles are repeated on the same pair of samples for five times, with roughness amplitude and interfacial fracture energy measured in each cycle. It is shown that the roughness gradually decreases during the repeated welding cycles, especially when a long welding time or high welding pressure is applied. Even though lower roughness amplitude promotes the contact area, the interfacial fracture energy reduces due to the increased BER activation energy after long‐time heating. A multiscale constitutive model is adopted, where we incorporate an explicit expression of interfacial contact area as a function of root‐mean‐square roughness parameter. The model is able to capture the evolving interfacial fracture energy during repeated welding cycles by using the measured roughness parameter, network modulus and BER activation energy. The study provides theoretical basis for the design and applications of CANs involving cyclic welding‐peeling operations. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 402–413.     

三嗪基多孔有机材料的合成及在固相微萃取应用中的研究进展

三嗪基多孔有机材料(TPOPs)具有较大的比表面积、可调的孔道结构、较高的热和化学稳定性、丰富的π键体系等诸多优点,目前被广泛应用于气体储存、催化、能源转化和吸附等诸多领域。基于TPOPs的固相微萃取(SPME)技术近年来引起了人们的极大兴趣,成为样品前处理技术领域的研究热点之一。该文简要地综述了近年来TPOPs的合成方法及其在固相微萃取领域的应用与发展,并对该领域研究进行了展望。     

Advances in the scaffolds fabrication techniques using biocompatible polymers and their biomedical application: A technical and statistical review

With the advancement in tissue engineering, researchers are working hard on new techniques to fabricate more advanced scaffolds from biocompatible polymers with enhanced porosity, appropriate mechanical strength, diverse shapes and sizes for potential applications in biomedical field in general and tissue engineering in particular. These techniques include electrospinning, solution blow spinning, centrifugal spinning, particulate leaching (salt leaching), freeze-drying, lithography, self-assembly, phase separation, gas foaming, melt molding, 3-D printing, fiber mesh and solvent casting. In this article we have summarized the scaffold’s fabrication techniques from biocompatible polymers that are reported so far, the recent advances in these techniques, characterization of the physicochemical properties of scaffolds and their potential applications in the biomedical field and tissue engineering. The article will help both newcomers and experts working in the biomedical implant fabrication to not only find their desired information in one document but also understand the fabrication techniques and the parameters that control the success of biocompatible polymeric scaffolds. Furthermore, a static analysis of the work published in all forms on the most innovative techniques is also presented. The data is taken from Scopus, restricting the search to biomedical fields and tissue engineering.     

Scattering by cyclic polymers and copolymers at large scattering vectors

General formulae allowing the evaluation of the form factors of cyclic block copolymers are established and graphs for cyclic copolymers of the form (A-B)_N are shown. WhenN is large, the linear and the cyclic copolymer have the same behaviour. It is possible to extend at large angle an analytical expression given for linear polymers. This allows to show that, in the study of transesterification by small-angle neutron scattering, one can neglect the effect of cycles.Dedicated to Prof. Fischer on the occasion of his 65th birthday