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Microgel suspensions have garnered significant interest in fundamental research due to their phase transition between liquid-like to paste-like behaviors stemming from tunable interparticle and particle-solvent interactions. Particularly, stimuli-responsive microgels undergo faster volume changes in response to external stimuli in comparison to their bulk counterparts, while maintaining their structural integrity. Here, concentrated and diluted suspensions of poly(N-isopropylacrylamide) (PNIPAm) microgels are dispersed to different packing fractions in water for the characterizations of temperature-responsive rheological responses. In the intrinsic volume phase transition (VPT), polymer chains collapse, and microgels shrink to smaller sizes. Additionally, the intermicrogel and microgel-solvent interactions vary in VPT, which results in microgel clusters that significantly affect the linear shear moduli of suspensions. The effect of the temperature ramp rate of PNIPAm microgel suspensions on rheological responses is characterized. Moreover, the effect of the mass fraction of microgels on the relative viscosity of dilute microgel suspensions is investigated. These results shed light on understanding the heating and cooling rate-dependent temperature responsiveness of PNIPAm microgel suspensions, establishing pathways to regulate the rheological characteristics in temperature-responsive microgel-based platforms. Therefore, this work envisions technological advancements in different fields such as drug delivery, tissue engineering, and diagnostic tools.

Hydrogels, composed of hydrophilic homopolymer or copolymer networks, have structures similar to natural living tissues, making them ideal for applications in drug delivery, tissue engineering, and biosensors. Since Wichterle and Lim first synthesized hydrogels in 1960, extensive research has led to various types with unique features. Responsive hydrogels, which undergo reversible structural changes when exposed to stimuli like temperature, pH, or specific molecules, are particularly promising. Temperature-sensitive hydrogels, which mimic biological processes, are the most studied, with poly(N-isopropylacrylamide) (PNIPAm) being prominent due to its lower critical solution temperature of around 32 °C. Additionally, pH-responsive hydrogels, composed of polyelectrolytes, change their structure in response to pH variations. Despite their potential, conventional hydrogels often lack mechanical strength. The double-network (DN) hydrogel approach, introduced by Gong in 2003, significantly enhanced mechanical properties, leading to innovations like shape-deformable DN hydrogels, organic/inorganic composites, and flexible display devices. These advancements highlight the potential of hydrogels in diverse fields requiring precise and adaptable material performance. In this review, we focus on advancements in the field of responsive acrylamide-based hydrogels with IPN structures, emphasizing the recent research on DN hydrogels. [ABSTRACT FROM AUTHOR]

Microcapsules are small particles that can effectively protect a core material from degradation. Microcapsules with double capsule walls can improve stability and reduce breakage due to the fact that the physical and chemical properties of double-walled materials can complement each other, thus enhancing the quality and applicability of a microcapsule. Microcapsules can achieve controlled release of core materials by using a temperature-sensitive wall material. In this research, gelatin was used as the inner wall material for these double-walled microcapsules. The outer wall material was a composite material prepared by the reaction of a hydroxyl group in gum arabic with an amino group in N-isopropylacrylamide (NIPAM) in the presence of N, N'-methylene bisacrylamide (BIS), while lavender fragrance oil served as the core material. A complex coalescence method was used for the preparation of microcapsules with double capsule walls. The effects of different proportions of gum arabic to NIPAM on the core loading, microcapsule yield and thermal stability of microcapsules were studied in detail. Additionally, the stability of these fragrance microcapsules with double capsule walls in different solvents and pH values was evaluated. The sustained release properties and mechanism of cotton fabrics treated with prepared fragrance microcapsules were investigated. The results show that the microcapsules prepared with a 10:1 ratio of NIPAM to gum arabic have good temperature responsiveness. Therefore, clothing treated with microcapsules with temperature-sensitive wall materials can ensure that the human body has a fresh and pleasant smell in the case of perspiring in summer. [ABSTRACT FROM AUTHOR]

In recent years, the coupling of structurally and functionally controllable polymers with biologically active protein materials to obtain polymer–protein conjugates with excellent overall properties and good biocompatibility has been important research in the field of polymers. In this study, the hyperbranched polymer hP(DEGMA-co-OEGMA) was first prepared by combining self-condensation vinyl polymerization (SCVP) with photo-induced metal-free atom transfer radical polymerization (ATRP), with 2-(2-bromo-2-methylpropanoyloxy) ethyl methacrylate (BMA) as inimer, and Di (ethylene glycol) methyl ether methacrylate (DEGMA) and (oligoethylene glycol) methacrylate (OEGMA, Mn = 300) as the copolymer monomer. Then, hP(DEGMA-co-OEGMA) was used as a macroinitiator to continue the polymerization of a segment of pyridyl disulfide ethyl methacrylate (DSMA) monomer to obtain the hyperbranched multiarm copolymers hP(DEGMA-co-OEGMA)-star-PDSMA. Finally, the lysozyme with sulfhydryl groups was affixed to the hyperbranched multiarm copolymers by the exchange reaction between sulfhydryl groups and disulfide bonds to obtain the copolymer protein conjugates hP(DEGMA-co-OEGMA)-star-PLZ. Three hyperbranched multiarm copolymers with relatively close molecular weights but different degrees of branching were prepared, and all three conjugates could self-assemble to form nanoscale vesicle assemblies with narrow dispersion. The biological activity and secondary structure of lysozyme on the assemblies remained essentially unchanged. [ABSTRACT FROM AUTHOR]

Cholesteric liquid crystal oligomers and polymers are promising materials for creating materials and devices with stimuli-responsive structural color, and the cholesteric to smectic pre-transition effect is of particular interest as it leads to a strong redshift in the reflected color upon cooling. Cholesteric polymers can be stabilized by the formation of semi-interpenetrating networks to obtain more robust photonic materials, but this tends to strongly suppress the pre-transition effect. Here, we show that the pre-transition effect in semi-interpenetrating networks based on main-chain cholesteric oligomers can be amplified by incorporating a smectic monomer and by increasing the degree of polymerization of the oligomers. This amplification counteracts the suppressing effect of the semi-interpenetrating network, and the resulting materials still show a significant band shift upon cooling. Presumably, both methods lead to the formation of more smectic domains in the cholesteric helix, which causes an amplified pre-transitional effect. The results bring us closer to the use of cholesteric semi-interpenetrating cholesteric networks for applications in smart sensing, healthcare, and safety devices.

Summary: Halogen bonding (XB) opens avenues to supramolecular assemblies. Here, we report XB-driven supramolecular assemblies of quaternary ammonium iodide (QAI)-containing polymers in three (solution, surface, and solid) phases. In the solution, QAI-containing block copolymers form unique self-assembly structures such as micrometer-sized giant vesicles (up to 5-μm diameter) and a 1-dimensional (1D) structure with multiple inter-vesicular linkages via XB. Exploiting the temperature dependence of XB strength, external molecules are successfully loaded and unloaded. On the surface, reversible XB crosslinking and decrosslinking of QAI-containing polymer brushes are achieved. The wettability of the polymer brush is finely tuned by the XB crosslinking density. In solid phase, QAI-containing monomers are co-crystalized (assembled) via XB. A polymer sheet is obtained via the solid-phase polymerization of the monomer co-crystal; the sheet enables capture and release of halogen-containing (XB-coordinating) guest molecules and thereby serves as an innovative host material.

Light-responsive microgels are interesting colloidal systems with potential applications in the biotechnology and medicine. However, synthesis of light-responsive microgels with high loading of photoswitchable molecules is still very challenging. Herein we developed a new method to synthesize light and temperature dual-responsive spiropyran-modified poly(N -vinylcaprolactam) microgels. The novel and straightforward microgels synthesis route involved: a) synthesis of poly(N -vinylcaprolactam- co -vinylformamide) copolymers via RAFT polymerization followed by the hydrolysis to obtain primary amine groups, b) attachment of carboxyl-modified spiropyran molecules to polymer chains via coupling, and c) crosslinking of spiropyran-modified polymer chains in W/O miniemulsion to form microgels. Via this method, we successfully synthesized poly(N -vinylcaprolactam) microgels containing more than 10 mol% spiropyran. The reversible light responsiveness of the spiropyran-modified copolymers and microgels in aqueous solution, which originates from the spiropyran photoisomerization under irradiation with different wavelengths, was demonstrated by UV–Vis spectroscopy. Spiropyran-modified copolymers demonstrate shift of the lower critical solution temperature (LCST) due to the polarity change of spiropyran molecules under dark, UV and visible light. Surprisingly, dynamic light scattering (DLS) results show that the microgels based on the same copolymers are less affected by UV irradiation. Microgels are swollen in darkness when spiropyran molecules are in the polar, merocyanine form, and collapse after irradiation with visible light, due to the transformation of spiropyran to the relatively nonpolar, closed spirocyclic form. In addition, the spiropyran-modified microgels exhibit reversible temperature responsiveness by presenting a volume phase transition in water from a swollen state to a collapsed state with increasing temperature and the transition temperature decreased compared to the pristine microgels due to the hydrophobicity of spiropyran units. [ABSTRACT FROM AUTHOR]

A softer natural Pickering nanostabilizer, S -ovalbumin (S -OVA) was reported in this work, based on our previous researches about soft globular protein nanoparticles. Compared with native OVA, S -OVA has higher surface hydrophobicity, greater conformational flexibility and thinner tightly-bond water layer, which make it be unfolded more highly at the oil–water interface. However, S -OVA also possesses higher zeta-potential and thicker closely-surrounding water layer, offering it stronger electrostatic repulsion and steric hindrance between molecules and increased intramolecular cohesion. The improvements guarantee S -OVA undisintegrated particle structure and independent state on the interface and high refolding off the interface. The more flexible interior and firmer exterior together endow a higher softness to S -OVA. The HIPPE gels solely stabilized by S -OVA were fabricated using one-step shearing. These HIPPE gels own steady network structure mainly supported by bridging flocculation, strong self-supporting ability and moldability. The high storage stability and ability to inhibiting lipid oxidization provide the HIPPE gels an enormous potential in encapsulating and protecting volatile, easily-oxidized or dangerous organic liquids, during the storage and transportation. The attractive temperature responsiveness offers a high convenience to re-obtaining the organic liquids. And a re-encapsulation can be easily achieved via a re-shearing. The heat-enhanced gel intensity and moldability mean the HIPPE gels can be applied to produce dualistic gels or porous scaffolds with latent applications. These findings are helpful to explore more new Pickering stabilizers from the nature and extend the applications of HIPPEs in highly-demanded and high-tech industries. [ABSTRACT FROM AUTHOR]

Traces of certain heavy metals are crucial for the metabolism of living beings, but poisoning occurs when their concentration increases. On the other hand, heavy metals such as lead, mercury, and cadmium lack functionality in higher organisms, resulting in considerable toxicity. Their long-term persistence is an environmental issue, being adsorption an alternative for the removal of metal pollutants, for example in wastewater. Adsorption has many advantages, such as high efficiency, simple design, low toxicity and reusable materials. Among the adsorbents, hydrogels feature improved resistance and high levels of swelling, comparable in costs to other common materials. In this work, we synthesized a copolymer of N,N -dimethylacrylamide (DMAa) and 2-hydroxyethyl methacrylate (HEMA) and evaluated its lead (II) adsorption capacity. The copolymer poly(HEMA-co-DMAa) was synthesized by a free-radical type bulk copolymerization of equal volumes of each monomer. The copolymer was characterized by 1 H and 13 C NMR, and Raman spectroscopies, and by the temperature and pH dependant-swelling effect of the hydrogel. Quantification of the removed Pb 2+ from probe solutions was performed by a UV spectrophotometric method as proposed by Krzek et al. Results suggest that at equilibrium, the amount of sorbed Pb(II) increased as the probe solution also increased (gradually from 10 to 200 ppm). Raman and 13 C spectroscopies confirmed effective copolymerization between HEMA and DMAa. The p(HEMA-co-DMAa) copolymer featured a swelling capacity up to 3.6 times their weight of water and exhibited a LCST in the range of 308–340 K with its geometric center around 313 K. In conclusion, a thermo-and-pH-responsive copolymer was obtained from the HEMA and DMAa monomers with LCST at 313 K and pH critical point at pH = 8, featuring efficient Pb(II) adsorption capabilities. The synthesized p(HEMA-co-DMAa) is promising for applications in heavy metals adsorption in aqueous systems with a broad range of pH and temperature, featuring resistance on adsorption and desorption cycles without mechanical degradation. [ABSTRACT FROM AUTHOR]

Objective(s)Physiological changes in the body may be utilized as potential triggers for controlled drug delivery. Based on these mechanisms, stimulus–responsive drug delivery has been developed.Materials and MethodsIn this study, a kind of poly (N-isopropylacrylamide-acrylamide) membrane was prepared by radical copolymerization. Changes in swelling ratios and diameters of the membrane were investigated in terms of temperature. On-off regulation of drug permeation through the membrane was then studied at temperatures below and above the phase transition temperature of the membrane. Two drugs, vitamin B12 and acetaminophen were chosen as models of high and low molecular weights here, respectively. ResultsIt was indicated that at temperatures below the phase transition temperature of the membrane, copolymer was in a swollen state. Above the phase transition temperature, water was partially expelled from the functional groups of the copolymer. Permeation of high molecular weight drug models such as vitamin B12 was shown to be much more distinct at temperatures below the phase transition temperature when the copolymer was in a swollen state. At higher temperatures when the copolymer was shrunken, drug permeation through the membrane was substantially decreased. However for acetaminophen, such a big change in drug permeation around the phase transition temperature of the membrane was not observed. ConclusionAccording to the pore mechanism of drug transport through hydrogels, permeability of solutes decreased with increasing molecular size. As a result, the relative permeability, around the phase transition temperature of the copolymer, was higher for solutes of high molecular weight.

Abstract: Silver (Ag) nanoparticles loading temperature responsive hybrid microgels were readily prepared by in situ reduction of Ag+ ions coordinated into poly(N-isopropylacrylamide) microgels. The weight percentage content of the entrapped Ag nanoparticles measured by thermogravity analysis tops 25%, and their average particle sizes determined by transmission electron microscopy are within the range from 8 to 11nm. The results obtained by X-ray diffraction exhibit that the Ag nanoparticles are of face-centered cubic single crystal structure. The particle sizes of the hybrid microgels decrease sharply with environmental temperature increasing from 30 to 35°C, and their surface plasmon resonance absorption wavelengths are pronouncedly red-shifted within the same temperature range. The catalytic reactivity of the Ag nanoparticles loading hybrid microgels can be tunable with four stages of change versus temperature from 20 to 45°C. [Copyright &y& Elsevier]

Objective(s) Physiological changes in the body may be utilized as potential triggers for controlled drug delivery. Based on these mechanisms, stimulus-responsive drug delivery has been developed. Materials and Methods In this study, a kind of poly (N-isopropylacrylamide-acrylamide) membrane was prepared by radical copolymerization. Changes in swelling ratios and diameters of the membrane were investigated in terms of temperature. On-off regulation of drug permeation through the membrane was then studied at temperatures below and above the phase transition temperature of the membrane. Two drugs, vitamin B12 and acetaminophen were chosen as models of high and low molecular weights here, respectively. Results It was indicated that at temperatures below the phase transition temperature of the membrane, copolymer was in a swollen state. Above the phase transition temperature, water was partially expelled from the functional groups of the copolymer. Permeation of high molecular weight drug models such as vitamin B12 was shown to be much more distinct at temperatures below the phase transition temperature when the copolymer was in a swollen state. At higher temperatures when the copolymer was shrunken, drug permeation through the membrane was substantially decreased. However for acetaminophen, such a big change in drug permeation around the phase transition temperature of the membrane was not observed. Conclusion According to the pore mechanism of drug transport through hydrogels, permeability of solutes decreased with increasing molecular size. As a result, the relative permeability, around the phase transition temperature of the copolymer, was higher for solutes of high molecular weight. [ABSTRACT FROM AUTHOR]

By coupling two equivalents of N,N-diethyldithiocarbamoylmethylbenzoic acid succinimidyl ester with cystamine dihydrochloride, a disulfide-carrying compound (Cys-BDC) was prepared and used as iniferter (a compound which pursues initiation, chain transfer, and termination) in the telomerization of N,N-dimethylacrylamide and 3-acrylamidophenylboronic acid. The telomerization was carried out in the presence of N,N,N′,N′-tetraethylthiuram disulfide under photoirradiation at 365 nm. An aqueous solution of the telomer obtained showed responsiveness to both temperature and sugars as confirmed by the turbidity measurements. The telomer formed a self-assembled monolayer (SAM) on a gold surface as confirmed by both cyclic voltammetry (CV) and ellipsometry. The recognition of sugar residues by the telomer SAM constructed on the gold electrode was detected by the CV measurements. The usefulness of the iniferter to prepare various telomer-carrying SAMs with bio-related functions was strongly suggested. [Copyright &y& Elsevier]

A series of multi-stimuli responsive water-soluble copolymers with higher porphyrin content were synthesized. [Display omitted] • A series of water-soluble copolymers with higher porphyrin content were synthesized. • The obtained porphyrin copolymers aqueous solution showed responsive behavior to temperature, ionic strength and pH. • The photo-thermal conversion efficiency of porphyrin copolymer aqueous solutionat can achieve 25.34%. Water-soluble porphyrins have played an important role and showed potential application value in photodynamic therapy, sensor and aqueous photocatalysis. Most of the reported water-soluble porphyrin polymers have low porphyrin content, which is difficult to give full play to the role of porphyrin. To improve the content of porphyrin in polymers, we introduced the hydrophilic chain into the porphyrin molecule to obtain the hydrophilic porphyrin monomer, and then copolymerized with the hydrophilic monomer N-isopropylacrylamide to obtain the water-soluble copolymers with higher porphyrin content. The prepared porphyrin copolymers aqueous solution also showed responsive behavior to temperature, ionic strength and pH. Firstly, temperature affects the solvability and photophysical properties of copolymers. When heating the temperature above their cloud point, the copolymers chain aggregated, leading to the decreased light transmittance and enhanced emission intensity. Secondly, the copolymer aqueous solution showed responsive behavior to ionic strength. After adding different sodium salts into the copolymer aqueous solution, the changes order of cloud point was completely consistent with the Hofmeister series, and their emission intensity also varied. Finally, the copolymer aqueous solution showed responsive behavior to pH. When the pH of copolymer aqueous solution decreased, the inner nitrogen atoms in porphyrin ring were protonated, resulting in an increase in the cloud point of their aqueous solution. At the same time, the maximum absorption peak gradually red-shifted, and the emission intensity also decreased. Therefore, based on the decrease in fluorescence, the protonated copolymer could be used as photo-thermal conversion materials. The measured photo-thermal conversion efficiency (PCE) of the copolymer in the pH = 1.0 aqueous solution was 25.34%. [ABSTRACT FROM AUTHOR]

• GA-based composite with temperature responsiveness were synthesized. • The composite can adaptively switch absorbing frequency band as temperature change. • The composite exhibits recyclable thermal and electric properties. Smart microwave absorption (MA) materials with responsiveness to environment are highly desired in modern communication systems, while designing and fabricating high-performance microwave absorbers with adaptivity to working in dynamic service environment is still a challenge. Here we report a temperature-responsive composite composing covalently bonded poly(N-isopropylacrylamide) (PNIPAAm) and graphene aerogel (GA)for adaptive MA. The dynamic change of hydrogen bonds actuate the conformation change of PNIPAAm chains when the temperature varies below and above the critical transition temperature of 34.8℃, which drives the reduced graphene oxide sheets in GA to delaminate and restacking simultaneously. As a result, the electrical, dielectric and thermal properties of the composite become adaptively switchable. More important, the composite is capable of achieving an effective MA within quite different frequency bands under stimuli of temperature changes. Typically, at 20℃, the effective absorbing band (below −10 dB) ranges from 8.5 to 17.5 GHz, and the minimum reflection loss (RL min) reaches −32 dB, while when the temperature increases to 50℃, the effective absorbing band shifts to 4.5 ~ 14.0 GHz with the same RL min. This temperature-responsive composite has great potential of being used as smart devices, especially the advanced electromagnetic protection equipment in the modern communication systems. [ABSTRACT FROM AUTHOR]

High molecular weight waterborne ABA block copolymers of styrene (St) and 2-ethylhexyl acrylate (2EHA) containing hard and soft domains were synthesized by means of RAFT (mini)emulsion polymerization using a bifunctional symmetric S,S-dibenzyl trithiocarbonate (DBTTC) RAFT agent. Miniemulsion polymerization was initially used for the synthesis of the A-block, which forms hard domains, followed by 2EHA pre-emulsion feeding to build the B-block soft domains. Polymerization kinetics and the evolution of the Molecular Weight Distribution (MWD) were followed during the synthesis of different ABA block copolymers. The thermal properties of the final symmetric block copolymers were studied on dried films by means of DSC. It was found that the block copolymers have two glass transitions, which indicates the presence of a two-phase system. Phase separation was investigated by means of microscopic techniques (AFM and TEM) and SAXS, both of the particles in the latex form, as well as after film formation at room temperature and after different post-treatments. Films were annealed at temperatures well above the glass transition temperature (Tg) of the hard phase to study the bulk morphology of the films after complete particle coalescence. Moreover, for comparison purposes, the films were re-dissolved in THF, and films were again cast directly from the homogeneous THF solutions. As THF is a good solvent for both blocks, such films serve as a reference for the equilibrium morphology. Finally, DMTA studies of the films annealed at different temperatures were performed to correlate the morphology changes with the mechanical properties of the block copolymers. [ABSTRACT FROM AUTHOR]

In order to improve the performance of traditional sodium alginate (SA) hydrogels cross-linked by Ca2+ ions to meet greater application demand, a strategy was designed to structure novel SA-based gels (named OP-PN gels) to achieve both stimulus responsiveness and improved mechanical strength. In this strategy, the SA chains are co-cross-linked by CaCl2 and cationic octa-ammonium polyhedral oligomeric silsesquioxane (Oa-POSS) particles as the first network, and an organically cross-linked poly(N-isopropyl acrylamide) (PNIPA) network is introduced into the gels as the second network. Several main results are obtained from the synthesis and characterization of the gels. For OP-PN gels, their properties depend on the content of both uniformly dispersed Oa-POSS and PNIPA network directly. The increased Oa-POSS and PNIPA network content significantly improves both the strength and resilience of gels. Relatively, the increased Oa-POSS is greatly beneficial to the modulus of gels, and the increased PNIPA network is more favorable to advancing the tensile deformation of gels. The gels with hydrophilic PNIPA network exhibit better swelling ability and remarkable temperature responsiveness, and their volume phase transition temperature can be adjusted by altering the content of Oa-POSS. The deswelling rate of gels increases gradually with the increase of POSS content due to the hydrophobic Si–O skeleton of POSS. Moreover, the enhanced drug loading and sustained release ability of the target drug bovine serum albumin displays great potential for this hybrid gel in the biomedical field. [ABSTRACT FROM AUTHOR]

The effect of hydration in corona layer on temperature responsiveness of polymer micelles consisting of poly(N-vinyl pyrrolidone)-block-poly(n-octadecyl acrylate) (PVP-b-PODA) was investigated. Small-angle X-ray scattering and dynamic light scattering showed two-step shape change of PVP-b-PODA micelles around 45 and 65 °C with elevating temperature, although only one-step shape change was observed at 45 °C in cooling process. In the first step, shape of PVP-b-PODA micelles was changed from disk to ellipsoidal oblate at the melting temperature (Tm) of PODA, although similar micelles consisting of another amphiphilic block copolymers containing PODA simply changed from disk to sphere at the Tm with elevating temperature. PVP-b-PODA micelles changed to spherical shape above 65 °C. Two-dimensional (2D) 1H-NMR showed the PVP chains were perfectly dehydrated above 65 °C. Therefore, it was suggested that the appearance of ellipsoidal shape between Tm of PODA and 65 °C was caused owing to shape memory effect of pseudo network of corona layer due to robust hydration of PVP chains. [ABSTRACT FROM AUTHOR]

The temperature responsive PEGylated polyaspartamide derivative, denoted as mPEG-PAAHP, was synthesized by the click reaction. FTIR and 1H NMR were adopted to characterize and confirm the chemical structures of the obtained mPEG-PAAHPs. The temperature responsive behavior investigated by transmittance and dynamic light scattering showed that some of the obtained mPEG-PAAHPs exhibited obvious temperature responsiveness and could be used to prepare nanoparticles by quickly heating. Drug paclitaxel can be encapsulated into mPEG-PAAHP based nanoparticles with a high encapsulation efficiency up to 99% (corresponding to a drug loading content of around 9.9%). Dynamic light scattering results showed that the PTX-loaded nanoparticles had a mean size around 80 nm (PDI<0.2) and good stability in PBS with 150 mM ionic strength. In vitro cytotoxicity results showed that mPEG-PAAHP did not show any toxicity to HeLa cells, but the PTX-loaded nanoparticles based on mPEG-PAAHP exhibited obvious anti-cancer activity. Thus, the temperature responsive PEGylated polyaspartamide derivative mPEG-PAAHP may be a promising drug delivery system. [ABSTRACT FROM AUTHOR]

Thermo-reversible supramolecular networks from polyisoprene-block-polystyrene-block-polyisoprene (ISI) triblock copolymers with short, functionalized polyisoprene (PI) blocks were investigated. Functional groups along the PI blocks were hydroxyl groups, ester groups with a carboxylic end-group (-O-CO-CH2-CH2-COOH), and urethane groups with an amine end-group—synthesized from various types of diamines—(-O-CO-NH-R-NH2). Dynamic mechanical analysis (DMA) was performed at temperatures above Tg of polystyrene (PS) to investigate the influence of the different functional groups, the molecular weight, and the composition of the triblock copolymers on the materials' properties. Furthermore, comparisons to DMA results of diblock copolymers, modified in the same way, will be presented. Arising reversible and irreversible processes observed during DMA experiments will be compared to results from temperature-dependent Fourier transform infrared (FTIR) spectroscopy. For the elaborated systems, the transition from reversible, hydrogen-bonded to permanently cross-linked networks was observed at around 150 °C. [ABSTRACT FROM AUTHOR]

The combination of controlled anionic polymerization and subsequent introduction of hydrogen bonding groups was established to form thermo-reversible, supramolecular networks. Several polyisoprene-block-polystyrene-block-polyisoprene (ISI) copolymers—with polystyrene (PS) as the main block, and consequently giving the decisive material characteristics—were synthesized. The novel modification approach to post-functionalize the polyisoprene (PI) end-blocks and to introduce different motifs, which are able to form self-complementary hydrogen bonds, was attained. In the first step, hydroxylation was accomplished using 9-borabicyclo[3.3.1]nonane. Starting from the hydroxylated polymer, esterification with succinic anhydride was implemented to form an ester group with carboxylic end-group (-O-CO-CH2-CH2-COOH). In a second approach, 1,1'-carbonyldiimidazole was used as coupling agent to introduce various types of diamines (diethylenetriamine, triethylentetramine, and 2,6-diaminopyridine) to prepare urethane groups with amine end-group (-O-CO-NH-R-NH2). 1H NMR spectroscopy was used to confirm the successful synthesis and to calculate the degree of functionalization Df. Differential scanning calorimetry (DSC) showed a difference of the glass transition temperature Tg between unfunctionalized and functionalized block copolymers, but no greater influence between the different types of modification, and thus, on the Tg of the PS block. In temperature dependent FTIR spectroscopy, reversible processes were observed. [ABSTRACT FROM AUTHOR]