Smart Polymers and Coatings Obtained by Ionizing Radiation: Synthesis and Biomedical Applications

Gamma radiation has been shown particularly useful for the functionalization of surfaces with stimuli-responsive polymers. This method involves the formation of active sites (free radicals) onto the polymeric backbone as a result of the exposition to high-energy radiation, in which a proper microenvironment for the reaction among monomer and/or polymer and the active sites takes place, thus leading to propagation which forms side chain grafts. The modification of polymers using high-energy irradiation may be performed by the following methods: direct or simultaneous, pre-irradiation oxidative and pre-irradiation. The most frequent ones correspond to the pre-irradiation oxidative method and the direct one. Radiation-grafting has many advantages over conventional methods considering that it does not require catalyst nor additives to initiate the reaction, and in general, no changes on the mechanical properties with respect to the pristine polymeric matrix are observed. This chapter focused on the synthesis of smart polymers and coatings obtained by the use of gamma radiation. In addition, diverse applications of these materials in the biomedical field are also reported.

Emission or scattering?Discriminating the origin of responsiveness in AIEgen-doped smart polymers using the TPE dye

Aggregation-induced emission(AIE)luminogens are attractive dyes to probe poly-mer properties that depend on changes in chain mobility and free volume.When embedded in polymers the restriction of intramolecular motion(RIM)can lead to their photoluminescence quantum yield(PLQY)strong enhancement if local microviscosity increases(lowering of chain mobility and free volume).Nonethe-less,measuring PLQY during stimuli,i.e.heat or mechanical stress,is technically challenging;thus,emission intensity is commonly used instead,assuming its direct correlation with the PLQY.Here,by usingfluorescence lifetime as an absolutefluorescence parameter,it is demonstrated that this assumption can be invalid in many commonly encountered conditions.To this aim,different poly-mers are loaded with tetraphenylenethylene(TPE)and characterized during the application of thermal and mechanical stress and physical aging.Under these con-ditions,polymer matrix transparency variation is observed,possibly due to local changes in refractive index and to the formation of microfractures.By combin-ing different characterization techniques,it is proved that scattering can affect the apparent emission intensity,while lifetime measurements can be used to ascertain whether the observed phenomenon is due to modifications of the photophysi-cal properties of AIE dyes(RIM effect)or to alterations in the matrix optical properties.

Smart polymers for the controlled delivery of drugs–a concise overview

Smart polymers have enormous potential in various applications.In particular,smart polymeric drug delivery systems have been explored as“intelligent”delivery systems able to release,at the appropriate time and site of action,entrapped drugs in response to specific physiological triggers.These polymers exhibit a non-linear response to a small stimulus leading to a macroscopic alteration in their structure/properties.The responses vary widely from swelling/contraction to disintegration.Synthesis of new polymers and crosslinkers with greater biocompatibility and better biodegradability would increase and enhance current applications.The most fascinating features of the smart polymers arise from their versatility and tunable sensitivity.The most significant weakness of all these external stimuli-sensitive polymers is slow response time.The versatility of polymer sources and their combinatorial synthesis make it possible to tune polymer sensitivity to a given stimulus within a narrow range.Development of smart polymer systems may lead to more accurate and programmable drug delivery.In this review,we discuss various mechanisms by which polymer systems are assembled in situ to form implanted devices for sustained release of therapeutic macromolecules,and we highlight various applications in the field of advanced drug delivery.

Polymers in Drug Delivery

Polymers are being used extensively in drug delivery due to their surface and bulk properties. They are being used in drug formulations and in drug delivery devices. These drug delivery devices may be in the form of implants for controlled drug delivery. Polymers used in colloidal drug carrier systems, consisting of small particles, show great advantage in drug delivery systems because of optimized drug loading and releasing property. Polymeric nano particulate systems are available in wide variety and have established chemistry. Non toxic, biodegradable and biocompatible polymers are available. Some nano particulate polymeric systems possess ability to cross blood brain barrier. They offer protection against chemical degradation. Smart polymers are responsive to atmospheric stimulus like change in temperature;pressure, pH etc. thus are extremely beneficial for targeted drug delivery. Some polymeric systems conjugated with antibodies/specific biomarkers help in detecting molecular targets specifically in cancers. Surface coating with thiolated PEG, Silica-PEG improves water solubility and photo stability. Surface modification of drug carriers e.g. attachment with PEG or dextran to the lipid bilayer increases their blood circulation time. Polymer drug conjugates such as Zoladex, Lupron Depot, On Caspar PEG intron are used in treatment of prostate cancer and lymphoblastic leukemia. Polymeric Drug Delivery systems are being utilized for controlled drug delivery assuring patient compliance.

A salt-induced viscosifying smart polymer for fracturing inter-salt shale oil reservoirs

Inter-salt shale oil reservoirs located between two salt layers are always accompanied by high temperature and high salinity. However, the present commonly used water-soluble polymers in fracturing fluids su er from poor tolerance to high temperature and high salinity. Thermoviscosifying polymers(TVP) whose aqueous solution shows viscosity increase upon increasing temperature and salt concentration have received considerable attention recently, which is promising for utilization in fracturing fluids to overcome these problems. In this work, both the salt-induced viscosifying property and mechanism of a TVP solution were investigated and the performance of TVP used as fracturing fluid based on the conditions of the Jianghan inter-salt shale oil reservoir in China was evaluated. It is found that the salt-induced viscosifying property of the TVP solution decreases with temperature and shear rate, but increases with polymer concentration. The number of intermolecular hydrophobic domains increases with the salt concentration contributing to the strengthening of a 3D network structure, which results in an increase in viscosity. In addition, the TVP fracturing fluid formulated with saturated brine exhibits excellent temperature and shear resistance, sand-suspending performance, and gel-breaking performance. Its viscosity remains above50 m Pa s after being sheared for 1 h even at a high temperature of 140 °C and the sand-suspending stability can be maintained for more than 1 week at 100 °C. Furthermore, the fracturing fluid can be easily broken down within 12h using 0.2 wt%–0.3 wt% potassium persulfate without residue.

Effect of CF and RPP on the Mechanical and Electrical Properties of Smart Aggregate

By using redispersible polymer powder（RPP） and carbon fiber（CF） to adjust the flexibility and electrical properties of the smart aggregate, a new kind of smart aggregate with Z type structure was proposed. The study shows that Z type aggregate is more sensitive to the feedback of external force than the prism aggregate in the same loading environment, and it indicates that Z type aggregate is more suitable for the research and application of concrete health monitoring. Although the incorporation of RPP would cause the compressive strength of the aggregates and the elastic modulus of hardened cement mortar to reduce slightly within the dosage of RPP by 2.25% because of the polymer film formed in the internal system, this would improve the deformability of the aggregates. In the early loading stage（in the first 60 seconds）, the intelligent concrete specimens implanted with Z type smart aggregate do not show higher sensitivity as expected, although the resistance change rate changes a little bit more, the overall of it is still in balance. Adding RPP could improve the flexibility of smart aggregates exactly, and it plays an active role in prolonging the life of the smart aggregates. By implanting Z type aggregates the damage and failure of the concrete structure could be predicted accurately in this study. The results of this paper will help to promote further research and application of intelligent concrete.

Smart aggregation-induced emission polymers:Preparation,properties and bio-applications

Owing to the outstanding photophysical properties,organic luminescent materials featuring aggregation-induced emission(AIE)characteristics have attracted wide attention in various fields.Numerous researches focused on low-mass AIE luminogens,and relatively less attention has been paid on AIE polymers and the related applications,in spite of the fact that AIE polymers exhibit excellent advantages of processability,multifunctional integration and synergistic effects.In this review,we briefly summarize and discuss the superiorities of AIE polymers in preparation,properties and bio-applications,and the considerable progress in these aspects are introduced as well.Finally,the structure-property relationship,challenges and opportunities are also discussed.Hopefully,this review will be a trigger for smart AIE polymer research and further broaden their applications.

Synthesis of Temperature- and pH-Sensitive Graft Copolymer Containing 2-(Diethylamino)ethyl Methacrylate and N-Vinylcaprolactam onto Silicone Rubber

Silicone rubber films were modified by the consecutive grafting of 2-(diethylamino)ethyl methacrylate (DEAEMA) and N-vinylcaprolactam (NVCL) using direct method on two steps with gamma-rays. The effect of absorbed dose and monomer concentration on grafting degree was determined. The grafted samples were verified by FTIR-ATR spectroscopy and swelling;thermal properties were analyzed by DSC and TGA. The stimuli-responsive behavior was studied by swelling and/or DSC. Thermo- and pH-sensitive films of (PP-g-DEAEMA)-g-NVCL presented a pH critical at 3.2 and LCST around 63.5℃.

A Disulfide-Based Poly(ether-b-amide)Copolymer with Rapid Self-healing Ability under Moderate Conditions

Comprehensive Summary A disulfide-based poly(ether-b-amide)copolymer with rapid self-healing capability under moderate conditions was synthesized from 4,4’-dithiodibutyric acid(DTDBA),isophorondiamine(IPDA)and poly(tetramethylene oxide)(PTMO)based on a two-step method.The incorporation of IPDA with asymmetric structure and substantial steric hindrance not only effectively decreased the number of regular H-bonds,but also inhibited the crystallization of polyamide segments,imparting the synthesized poly(ether-b-amide)copolymer with an amorphous structural feature.Based on the coordination of segmental diffusion and recombination of disulfide bonds and hydrogen bonds,the scratches and damaged mechanical properties of PEBADS-I611 could be completely self-healed after healing at 40°C for only 11 min and 3 h,respectively.

New approach for chiral separation: from polysaccharide-based materials to chirality-responsive polymers

Chiral separation that is closely related to daily life is a meaningful research. Polysaccharide-(e.g., cellulose, amylose derivatives) based chiral packing materials afford powerful chiral stationary phases(CSPs) toward a broad range of racemic compounds. However, considering the explosive growth of specific chiral drugs, the separation efficiencies of these CSPs need further improvement, which calls for new approaches and strategies. Smart polymers can change their physical or chemical properties dynamically and reversibly according to the external stimuli(e.g., thermo-, pH, solvent, ion, light, critical parameters for chromatographic separation) exerted on them, subsequently resulting in tunable changes in the macroscopic properties of materials. In addition to their excellent controllability, the introduction of chiral characteristics into the backbones or side-chains of smart polymers provides a promising route to realize reversibly conformational transition in response to the chiral analytes. This dramatic transition may significantly improve the performance of materials in chiral separation through modulating the enantioselective interactions between materials and analytes. With the help of chirality-responsive polymers, intelligent and switchable CSPs could be developed and applied in column-liquid chromatography. In these systems, the elution order or enantioselectivity of chiral drugs can be precisely modulated, which will help to solve many challenging problems that involve complicated enantiomers. In this paper we introduce some typical examples of smart polymers that serve as the basis for a discussion of emerging developments of CPSs, and then briefly outline the recent CSPs based on natural and certain synthetic polymers.

Controlling the gelation temperature of biomimetic polyisocyanides

Thermosensitive polymers show an entropy-driven transition from a well-solvated to a poorly solvated polymer chain, resulting in a more compact globular conformation. The transition at the lower critical solution temperature（LCST） is often sharp, which allows for a wide range of smart material applications.At the LCST, oligo（ethylene glycol）-substituted polyisocyanides（PICs） form soft hydrogels, composed of polymer bundles similar to biological gels, such as actin, fibrin and intermediate filaments. Here, we show that the LCST of PICs strongly depends linearly on the length of the ethylene glycol（EG） tails; every EG group increases the LCSTand thus the gelation temperature by nearly 30 ℃. Using a copolymerisation approach, we demonstrate that we can precisely tailor the gelation temperature between 10 ℃ and 60 ℃and, consequently, tune the mechanical properties of the PIC gels.