Thermoresponsive Polymer Research Articles

Green Synthesis of Silver Nanoparticles and Its Combination with Pyropia columbina (Rhodophyta) Extracts for a Cosmeceutical Application.

We report the green synthesis of silver nanoparticles (AgNPs) by using daisy petals (Bellis perennis), leek (Allium porrum) and garlic skin (Allium sativum) as reducing agents and water as solvent. AgNPs are obtained with high monodispersity, spherical shapes and size ranging from 5 to 35 nm and characterized by UV-Vis and TEM techniques. The obtained yields in AgNPs are in concordance with the total phenolic content of each plant. We also study the incorporation of AgNPs in combination with the red algae Pyropia columbina extracts (PCE) into cosmetic formulations and analyze their combined effect as photoprotective agents. Moreover, we carry out the inclusion of the PCE containing mycosporine-like amino acids (MAAs), which are strong UV-absorbing and antioxidant compounds, into β-cyclodextrin (βCD) and pNIPAM nanoparticles and analyze stability and release. The thermoresponsive polymer is grown by free radical polymerization using N-isopropylacrylamide (NIPAM) as the monomer, N,N'-methylenebisacrylamide (BIS) as the cross-linker, and 2,2'-azobis(2-methylpropionamidene) (V50) as the initiator, while βCD complex is prepared by heating in water. We evaluate the nanoparticle and βCD complex formation by UV-Vis and FT-IR, and NMR spectroscopies, respectively, and the nanoparticles' morphology, including particle size, by TEM. The cosmetic formulations are subsequently subjected to accelerated stability tests and photoprotective analyses: a synergistic effect in the combination of AgNPs and PCE in photoprotection was found. It is not related to a UV screen effect but to the antioxidant activity, having potential against photoaging.

Thermoresponsive Shape-Memory Biobased Photopolymers of Tetrahydrofurfuryl Acrylate and Tridecyl Methacrylate.

A series of thermoresponsive shape-memory photopolymers have been synthesized from the mixtures of two biobased monomers, tetrahydrofurfuryl acrylate and tridecyl methacrylate, with the addition of a small amount of 1,3-benzendithiol (molar ratio of monomers 0-10:0.5:0.03, respectively). Ethyl (2,4,6 trimethylbenzoyl) phenylphosphinate was used as photoinitiator. The calculated biorenewable carbon content of these photopolymers was in the range of (63.7-74.9)%. The increase in tetrahydrofurfuryl acrylate content in the photocurable resins resulted in a higher rate of photocuring, increased rigidity, as well as mechanical and thermal characteristics of the obtained polymers. All photopolymer samples showed thermoresponsive shape-memory behavior when reaching their glass transition temperature. The developed biobased photopolymers can replace petroleum-derived thermoresponsive shape-memory polymer analogues in a wide range of applications.

Nasal administration of a temozolomide-loaded thermoresponsive nanoemulsion reduces tumor growth in a preclinical glioblastoma model.

Glioblastoma (GB) is the worst and most common primary brain tumor. Temozolomide (TMZ), an alkylating agent, is widely used for treating primary and recurrent high-grade gliomas. However, at least 50% of TMZ treated patients do not respond to TMZ and the development of chemoresistance is a major problem. Here, we designed a lipid nanoemulsion containing a thermoresponsive polymer (poloxamer 407) aiming to improve TMZ release into the brain via nasal delivery. Increasing amounts of poloxamer 407 were added to preformed nanoemulsions (250nm-range) obtained by spontaneous emulsification. The influence of the polymer concentration (from 2.5% to 12.5%) and temperature on viscosity was clearly evidenced. Such effect was also noticed on the mucoadhesiveness of formulations, as well as TMZ release rate and retention/permeation through nasal porcine mucosa using Franz-type diffusion cells. From these results, a formulation containing 10% of poloxamer (NTMZ-P10) was selected for further experiments by nasal route. A significantly higher TMZ amount was observed in the brain of rats from NTMZ-P10 in comparison with controls. Finally, our results show that formulation reduced significantly tumor growth by three-fold: 103.88±43.67mm3 (for NTMZ-P10) and 303.28±95.27mm3 (control). Overall, these results suggest the potential of the thermoresponsive formulation, administered by the non-invasive nasal route, as a future effective glioblastoma treatment.

Cooling-induced, localized release of cytotoxic peptides from engineered polymer nanoparticles in living mice for cancer therapy.

Temperature-responsive polymers are often characterized by an abrupt change in the degree of swelling brought about by small changes in temperature. Polymers with a lower critical solution temperature (LCST) in particular, are important as drug and gene delivery vehicles. Drug molecules are taken up by the polymer in their solvent swollen state below their LCST. Increasing the temperature above the LCST, typically physiological temperatures, results in desolvation of polymer chains and microstructure collapse. The trapped drug is released slowly by passive diffusion through the collapsed polymer network. Since diffusion is dependent on many variables, localizing and control of the drug delivery rate can be challenging. Here, we report a fundamentally different approach for the rapid (seconds) tumor-specific delivery of a biomacromolecular drug. A copolymer nanoparticle (NP) was engineered with affinity for melittin, a peptide with potent anti-cancer activity, at physiological temperature. Intravenous injection of the NP-melittin complex results in its accumulation in organs and at the tumor. We demonstrate that by local cooling of the tumor the melittin is rapidly released from the NP-melittin complex. The release occurs only at the cooled tumor site. Importantly, tumor growth was significantly suppressed using this technique demonstrating therapeutically useful quantities of the drug can be delivered. This work reports the first example of an in vivo site-specific release of a macromolecular drug by local cooling for cancer therapy. In view of the increasing number of cryotherapeutic devices for in vivo applications, this work has the potential to stimulate cryotherapy for in vivo drug delivery.

Intestine-inspired wrinkled MXene microneedle dressings for smart wound management.

Composite MXene-based materials are prone to crack propagation, thus limiting their tensile properties. Numerous efforts have been devoted to removing material constraints and fabricating unitary MXene elastic films. Here, for the first time, inspired by the intestinal wrinkles and villi structure, we presented a ductile, biologically friendly, and highly conductive MXene-based microneedle (MMN) dressing composed of stacked MXene film and superfine microneedle arrays through a simple stretching and laser engraving strategy for wound healing. By utilizing photothermal responsive MXene, periodic porous structures, and a temperature-responsive polymer to construct the MMN dressing, the system can act as an effective route for facilitating controllable drug delivery controlled by near-infrared (NIR) irradiation. In addition, superior conductivity imparts them with the capacity to realize continuous and steady monitoring of motion sensing. The practical performance further demonstrated that the versatile MMN dressing showed obvious therapeutic efficacy in vivo animal wound models. Thus, it is believed that MMN dressings with biomimetic structures, controllable drug release, and conductive pathways will open a new chapter for wound management and widen other practical applications in biomedical fields, such as artificial tendons and soft robotics. STATEMENT OF SIGNIFICANCE: MXene-based materials have been demonstrated as critical tools in advancing our understanding of wound healing. However, the rapid crack propagation is a constraint on their tensile properties. Here, inspired by the intestinal wrinkles and villi structure, a single-step method has also been discussed to present a MXene-based microneedle dressing composed of unitary MXene elastic film and superfine microneedle arrays. At the same time, the dressing with biomimetic structures, controllable drug release, and conductive pathways has prospects in intelligent wound management and varieties of related biomedical fields.

In vitro and in vivo applications of a universal and synthetic thermo-responsive drug delivery hydrogel platform

A synthetic and thermo-responsive polymer, poly(N-isopropylacrylamide)-co-(polylactide/2-hydroxy methacrylate)-co-(oligo (ethylene glycol)), is used to formulate a universal carrier platform for sustained drug release. The enabling carrier, denoted as TP, is prepared by dissolving the polymer in an aqueous solution at a relatively neutral pH. A wide range of therapeutic moieties can be incorporated without the need for the addition of surfactants, organic solvents, and other reagents to the carrier system. The resulting solution is flowable through fine gauge needle, allowing accurate administration of TP to the target site. After injection, TP carrier undergoes a coil to globe phase transition to form a hydrogel matrix at the site. The benign nature of the polymer carrier and its physical gelation process are essential to preserve the biological activity of the encapsulated compounds while the adhesive hydrogel nature of the matrix allows sustained elusion and controlled delivery of the incorporated therapeutics. The TP carrier system has been shown to be non-toxic and elicits a minimal inflammatory response in multiple in vitro studies. These findings suggest the suitability of TP as an enabling carrier of therapeutics for localized and sustained drug delivery. To confirm this hypothesis, the capabilities of TP to encapsulate and effectively deliver multiple therapeutics of different physicochemical characteristics was evaluated. Specifically, a broad range of compounds were tested, including ciprofloxacin HCl, tumor necrosis factor-alpha (TNF-α), transforming growth factor beta 1 (TGF-β1), and recombinant human bone morphogenetic protein 2 (BMP2). In vitro studies confirmed that TP carrier is able to control the release of the encapsulated drugs over an extended period of time and mitigate their burst release regardless of the compounds’ physiochemical properties for the majority of the loaded therapeutics. Importantly, in vitro and in vivo animal studies showed that the released drugs from the TP hydrogel matrix remained potent and bioactive, confirming the high potential of the TP polymer system as an enabling carrier.

Implementation of thermo-responsive polymer coatings for an early warning against critical temperature states of thermo-sensitive electronic devices with metal oxide (MOx) gas sensors

Thermo-sensitive electronic devices such as Li-ion battery systems have reached a tremendous importance over the past years, in particular due to the increased pace of technology developments in the sector of e-mobility. In the present study, thermo-responsive functional coatings which release volatile cleavage products at well-defined temperatures were developed towards their use for indirect detection of critical temperatures by metal oxide (MOx) sensors. 1,1′-Azobis(cyclohexanecarbonitrile) (ABCN) and 2,2′-azodi(isobutyronitrile) (AIBN) were implemented as additives with a concentration of 4.7 wt% in polyurethane coating formulations. The thermolysis of the blowing agents and release of tracer gases were studied by differential scanning calorimetry, thermogravimetric analysis and evolved gas analysis coupled with mass spectrometry, showing comparable peak temperatures of gas release and no significant impact of the polyurethane matrix on gas release. In addition, the released gases could be successfully monitored by implementing MOx gas sensors in combination with effective algorithms to compute a warning signal in real-time with high robustness against false positives. This work therefore paves the way towards functional coatings, which have the ability to trace critical temperatures and hot spots of sensitive electronic-based systems on large and non-conformal surfaces by indirect measurements through low-cost MOx gas sensors.

Injectable Thermosensitive Nanocomposites Based on Poly(N-vinylcaprolactam) and Silica Particles for Localized Release of Hydrophilic and Hydrophobic Drugs.

The systemic delivery of drugs employed by conventional methods has shown to be less effective than a localized delivery system. Many drugs have the effectiveness reduced by fast clearance, increasing the amount required for an efficient treatment. One way to overcome this drawback is through the use of thermoresponsive polymers that undergo a sol-gel transition at physiological temperature, allowing their injection directly in the desired site. In this work, thermosensitive nanocomposites based on poly(N-vinylcaprolactam) and silica particles with 80 and 330 nm were synthesized to be employed as delivery systems for hydrophobic (naringin) and hydrophilic (doxorubicin hydrochloride) drugs. The insertion of SiO2 increased the rheological properties of the nanocomposite at 37 °C, which helps to prevent its diffusion away from the site of injection. The synthesized materials were also able to control the drug release for a period of 7 days under physiological conditions. Due to its higher hydrophobicity and better interaction with the PNVCL matrix, naringin presented a more controlled release. The Korsmeyer-Peppas model indicated different release mechanisms for each drug. At last, a preliminary in vitro study of DOX-loaded nanocomposites cultured with L929 and MB49 cells showed negligible toxic effects on healthy cells and better efficient inhibition of carcinoma cells.

A Thermo-Responsive Polymer Micelle with a Liquid Crystalline Core.

An amphiphilic diblock copolymer (PChM-PNIPAM), composed of poly(cholesteryl 6-methacryloyloxy hexanoate) (PChM) and poly(N-isopropyl acrylamide) (PNIPAM) blocks, was prepared via reversible addition-fragmentation chain transfer radical polymerization. The PChM and PNIPAM blocks exhibited liquid crystalline behavior and a lower critical solution temperature (LCST), respectively. PChM-PNIPAM formed water-soluble polymer micelles in water below the LCST because of hydrophobic interactions of the PChM blocks. The PChM and PNIPAM blocks formed the core and hydrophilic shell of the micelles, respectively. With increasing temperature, the molecular motion of the pendant cholesteryl groups increased, and a liquid crystalline phase transition occurred from an amorphous state in the core. With further increases in temperature, the PNIPAM block in the shell exhibited the LCST and dehydrated. Hydrophobic interactions of the PNIPAM shells resulted in inter-micellar aggregation above the LCST.

Thermoresponsive bio-affinity interfaces for temperature-modulated selective capture and release of targeted exosomes.

The existing methods for exosome isolation, such as ultracentrifugation, size exclusion, and affinity separation, suffer from some limitations. Herein, we aimed to develop temperature-modulated exosome-capturing materials using thermoresponsive polymers and peptides with affinity for exosomes. Poly(2-hydroxyethyl methacrylate-co-propargyl acrylate)-b-poly(N-isopropylacrylamide) (P(HEMA-co-PgA)-b-PNIPAAm) was grafted on silica beads via a two-step process of activator regenerated by electron transfer atom transfer radical polymerization. Peptides with affinity for exosomes were conjugated to the propargyl group of the bottom P(HEMA-co-PgA) segment of the copolymer via a click reaction. The prepared copolymer-grafted beads were characterized by elemental analysis, X-ray photoelectron spectroscopy, scanning electron microscopy, transmission electron microscopy, gel permeation chromatography, and the turbidity of the polymer solution. Results indicated that the copolymer and peptide were successfully modified on the silica beads. Exosomes from SK-BR-3​cells, a human breast cancer cell line, were selectively captured on the prepared beads at 37​°C, as the upper PNIPAAm segment shrank and the affinity between the peptide and exosome was enhanced. Upon lowering the temperature to 4​°C, the captured exosomes were released from the copolymer brush because of the extension of the PNIPAAm segment that reduced the affinity between peptides and exosomes. These findings demonstrated that the prepared copolymer brush-grafted silica beads can capture and release targeted exosomes via temperature modulation. Taken together, the developed copolymer brush-grafted silica beads would be useful for the separation of exosomes using simple procedures such as temperature modulation.

Design, Characterization and Pharmacokinetic-Pharmacodynamic Evaluation of Poloxamer and Kappa-Carrageenan-Based Dual-Responsive In Situ Gel of Nebivolol for Treatment of Open-Angle Glaucoma.

This study developed a dual-responsive in situ gel of nebivolol (NEB), a selective β-adrenergic antagonist. The gel could achieve sustained concentrations in the aqueous humor to effectively treat glaucoma. The gel was prepared using a combination of poloxamers (Poloxamer-407 (P407) and Poloxamer-188 (P188)) and kappa-carrageenan (κCRG) as thermo-responsive and ion-sensitive polymers, respectively. Box-Behnken design (BBD) was used to optimize the effect of three critical formulation factors (concentration of P407, P188 and κCRG) on two critical response variables (sol-to-gel transition temperature of 33-35 °C and minimum solution state viscosity) of the in situ gel. A desirability function was employed to find the optimal concentrations of P407, P188 and κCRG that yielded a gel with the desired sol-to-gel transition temperature and solution state viscosity. An NEB-loaded gel was prepared using the optimized conditions and evaluated for in vitro drug release properties and ex vivo ocular irritation studies. Furthermore, ocular pharmacokinetic and pharmacodynamics studies were conducted in rabbits for the optimized formulation. The optimized NEB-loaded gel containing P407, P188 and κCRG had a sol-to-gel transition temperature of 34 °C and exhibited minimum viscosity (212 ± 2 cP at 25 °C). The optimized NEB-loaded gel sustained drug release with 86% drug release at the end of 24 h. The optimized formulation was well tolerated in the eye. Ocular pharmacokinetic studies revealed that the optimized in situ gel resulted in higher concentrations of NEB in aqueous humor compared to the NEB suspension. The aqueous humor Cmax of the optimized in situ gel (35.14 ± 2.25 ng/mL) was 1.2 fold higher than that of the NEB suspension (28.2 ± 3.1 ng/mL), while the AUC0-∞ of the optimized in situ gel (381.8 ± 18.32 ng/mL*h) was 2 fold higher than that of the NEB suspension (194.9 ± 12.17 ng/mL*h). The systemic exposure of NEB was significantly reduced for the optimized in situ gel, with a 2.7-fold reduction in the plasma Cmax and a 4.1-fold reduction in the plasma AUC0-∞ compared with the NEB suspension. The optimized gel produced a higher and sustained reduction in the intra-ocular pressure compared with the NEB suspension. The optimized gel was more effective in treating glaucoma than the NEB suspension due to its mucoadhesive properties, sustained drug release and reduced drug loss. Lower systemic exposure of the optimized gel indicates that the systemic side effects can be significantly reduced compared to the NEB suspension, particularly in the long-term management of glaucoma.

Smart Polymer Surfaces with Complex Wrinkled Patterns: Reversible, Non-Planar, Gradient, and Hierarchical Structures.

This review summarizes the relevant developments in preparing wrinkled structures with variable characteristics. These include the formation of smart interfaces with reversible wrinkle formation, the construction of wrinkles in non-planar supports, or, more interestingly, the development of complex hierarchically structured wrinkled patterns. Smart wrinkled surfaces obtained using light-responsive, pH-responsive, temperature-responsive, and electromagnetic-responsive polymers are thoroughly described. These systems control the formation of wrinkles in particular surface positions and the reversible construction of planar-wrinkled surfaces. This know-how of non-planar substrates has been recently extended to other structures, thus forming wrinkled patterns on solid, hollow spheres, cylinders, and cylindrical tubes. Finally, this bibliographic analysis also presents some illustrative examples of the potential of wrinkle formation to create more complex patterns, including gradient structures and hierarchically multiscale-ordered wrinkles. The orientation and the wrinkle characteristics (amplitude and period) can also be modulated according to the requested application.

Two-Level 3D Column-like Nanofilms with Hexagonally-Packed Tantalum Fabricated via Anodizing of Al/Nb and Al/Ta Layers-A Potential Nano-Optical Biosensor.

Reanodizing metal underlayers through porous anodic alumina has already been used extensively to fabricate ordered columns of different metal oxides. Here, we present similar 3D multilayered nanostructures with unprecedented complexity. Two-level 3D column-like nanofilms have been synthesized by anodizing an Al/Nb metal layer in aqueous oxalic acid for forming the first level, and an Al/Ta layer in aqueous tartaric acid for forming the second level of the structure. Both levels were then reanodized in aqueous boric acid. The Ta layer deposited on partially dissolved porous anodic alumina of the first level, with protruding tops of niobia columns, acquired a unique hexagonally-packed structure. The morphology of the first and second levels was determined using scanning electron microscopy. Prolonged etching for 24 h in a 50%wt aqueous phosphoric acid was used to remove the porous anodic alumina. The formation mechanism of aluminum phosphates on the second-level columns in the process of long-time cold etching is considered. The model for the growth of columns on a Ta hexagonally-packed structure of the second level is proposed and described. The described approach can be applied to create 3D two- or three-level column-like systems from various valve metals (Ta, Nb, W, Hf, V, Ti), their combinations and alloys, with adjustable column sizes and scaling. The results of optical simulation show a high sensitivity of two-level column-like 3D nanofilms to biomedical objects and liquids. Among potential applications of these two-level column-like 3D nanofilms are photonic crystals for full-color displays, chemical sensors and biosensor, solar cells and thermoresponsive shape memory polymers.

Thermoresponsive nanocomposite hydrogels based on Gelatin/poly (N–isopropylacrylamide) (PNIPAM) for controlled drug delivery

This study is focused on developing thermoresponsive nanocomposite hydrogels based on gelatin by the incorporation of a thermoresponsive polymer, poly (N–isopropylacrylamide) (PNIPAM), that can undergo a sol–gel transition by physiological conditions with the aim of minimally invasive drug delivery. Various hybrid nanocomposite hydrogels consisting of gelatin as the matrix and acetaminophen–loaded PNIPAM nanoparticles were prepared using response surface methodology through the design of experiment software. PNIPAM nanoparticles were synthesized using the photopolymerization technique. Nanocomposite hydrogels were characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), swelling capacity, hydrolytic degradation, antibacterial and cell viability measurements, and release studies. Narrow size distribution of PNIPAM nanoparticles was observed, indicating successful polymerization and good size control by the reactor size. The system exhibited a reversible sol–gel transition around 37 °C, close to body temperature. The swelling capacity of nanocomposite hydrogel was found to decrease above the phase transition temperature. Drug–loaded gelatin–PNIPAM nanocomposite hydrogels indicated the antibacterial activity against the gram–positive and gram–negative species. Hydrogels with a lower ratio of PNIPAM to gelatin demonstrated a lower amount, more uniform, and delayed release compared to the other hydrogels, indicating good potential for drug delivery targeted purposes.

Electrochemical Cloud Point Temperature from Thermoamperometry: Real-Time Analysis for Phase Transition of Thermoresponsive Polymers.

Cloud point temperature (Tcp) is a thermal index used to define the phase transition of thermoresponsive polymers. In this study, we used electrochemical techniques to obtain an electrochemical cloud point temperature (Tecp) that exhibits the more accurate phase transition temperature and can replace Tcp. Thermoamperometry on an ultramicroelectrode was conducted with a poly(arylene ether sulfone) (PES10) as a model system to obtain a current-temperature (i-T) curve in real time; the Tecp of the PES10 was determined from the i-T curve. The i-T curve shows an unprecedented current decrease in the PES10 solution despite increasing temperature; on the other hand, the current increased linearly with increasing temperature in the solution without PES10. This phenomenon was analyzed by considering the characteristics of PES10 during phase transition, such as dynamic viscosity, temperature of the solution, and electrode impedance. It was confirmed that the current drops shown in the i-T curves were mainly due to the decrease of real electrode area. The comparison of Tecp and Tcp showed that both depended similarly on the concentrations of the thermoresponsive polymer and the supporting electrolyte. The results reveal that by adjusting the concentration of polymer and electrolyte in an organic solution, Tecp, as a new analytical method, can be used in electric circuit-based energy storage appliances such as Li-ion batteries and supercapacitors.

Folic-Acid-Conjugated Thermoresponsive Polymeric Particles for Targeted Delivery of 5-Fluorouracil to CRC Cells.

Colorectal cancer is the fourth most common cancer worldwide and the third most frequently diagnosed form of cancer associated with high mortality rates. Recently, targeted drug delivery systems have been under increasing attention owing to advantages such as high therapeutic effectiveness with a significant depletion in adverse events. In this report, we describe the biocompatible and thermoresponsive FA-conjugated PHEA-b-PNIPAAm copolymers as nanocarriers for the delivery of 5-FU. The block copolymers were obtained using RAFT (Reversible Addition-Fragmentation chain Transfer) polymerization and were characterized by methods such as SEC (Size Exclusion Chromatography), NMR (Nuclear Magnetic Resonance), UV-Vis (Ultraviolet-Visible), FT-IR (Fourier Transform Infrared) spectroscopy, and TGA (Thermogravimetric Analysis). Nanoparticles were formed from polymers with and without the drug-5-fluorouracil, which was confirmed using DLS (Dynamic Light Scattering), zeta potential measurements, and TEM (Transmission Electron Microscopy) imaging. The cloud points of the polymers were found to be close to the temperature of the human body. Eventually, polymeric carriers were tested as drug delivery systems for the safety, compatibility, and targeting of colorectal cancer cells (CRC). The biological evaluation indicated high compatibility with the representative host cells. Furthermore, it showed that proposed nanosystems might have therapeutic potential as mitigators for 5-FU-induced monocytopenia, cardiotoxicity, and other chemotherapy-associated disorders. Moreover, results show increased cytotoxicity against cancer cells compared to the drug, including a line with a drug resistance phenotype. Additionally, the ability of synthesized carriers to induce apoptosis and necrosis in treated CRC cells has been confirmed. Undoubtedly, the presented aspects of colorectal cancer therapy promise future solutions to overcome the conventional limitations of current treatment regimens for this type of cancer and to improve the quality of life of the patients.

Remodeling arteries: studying the mechanical properties of 3D-bioprinted hybrid photoresponsive materials.

3D-printed cell models are currently in the spotlight of medical research. Whilst significant advances have been made, there are still aspects that require attention to achieve more realistic models which faithfully represent the in vivo environment. In this work we describe the production of an artery model with cyclic expansive properties, capable of mimicking the different physical forces and stress factors that cells experience in physiological conditions. The artery wall components are reproduced using 3D printing of thermoresponsive polymers with inorganic nanoparticles (NPs) representing the outer tunica adventitia, smooth muscle cells embedded in extracellular matrix representing the tunica media, and finally a monolayer of endothelial cells as the tunica intima. Cyclic expansion can be induced thanks to the inclusion of photo-responsive plasmonic NPs embedded within the thermoresponsive ink composition, resulting in changes in the thermoresponsive polymer hydration state and hence volume, in a stimulated on-off manner. By changing the thermoresponsive polymer composition, the transition temperature and pulsatility can be efficiently tuned. We show the direct effect of cyclic expansion and contraction on the overlying cell layers by analyzing transcriptional changes in mechanoresponsive mesenchymal genes associated with such microenvironmental physical cues. The technique described herein involving stimuli-responsive 3D printed tissue constructs, also described as four- dimensional (4D) printing, offers a novel approach for the production of dynamic biomodels.

Thermoresponsive star-shaped polymer with heteroarm type with methacrylates: preparation by living radical polymerization method and its topological effect

Thermoresponsive star-shaped polymer with heteroarm type with methacrylates was prepared by living radical polymerization method with ruthenium catalyst. The effect of the arm structures was also investigated.

Synthesis, Characterization and Photocatalytic Properties of Metal Phthalocyanine Modified Thermoresponsive Polymers

In this study, 3-hydroxyethoxyphenyl-9(10), 16(17), 23 (24)-decyloxy-zinc phthalocyanine (HDPcZn) was first prepared by liquid phase catalysis, and then it was esterified with Poly-(N-isopropylacrylamide) which have two carboxyl groups (TRIT-PNIPAM) at the end to obtain a linear thermoresponsive polymer (PcZn-PNIPAM-PcZn) with two phthalocyanines at the end. The polymer was characterized by FT-IR, 1H NMR, EDS and UV-vis, and the photocatalytic performance of the polymer was tested with 1,5-dihydroxynaphthalene (DHN) as a model pollutant. The results showed that PcZn-PNIPAM-PcZn exhibited excellent photocatalytic oxidation ability for DHN under visible light irradiation (2h, 78.1 %).

Modelling thermoresponsive polymer brush by mesoscale computer simulations

We consider a functional surface comprising thermoresponsive polymer chains, the material that has found numerous technological and biomedical applications. However, to achieve the required time and length scales for computer modelling of such applications, one is compelled to use coarse-grained mesoscopic modelling approaches. The model used here is based on the previous work [Soto-Figueroa et al., Soft Matter, 8, 1871 (2012)], and it mimics the principal feature of the poly(N-iso-propylacrylamide) (PNIPAM), namely, the rapid change of its hydrophilicity at the lower critical solution temperature (LCST). For the case of an isolated chain, we discuss scaling properties of the radius of gyration, end-to-end distance, various distribution functions, and the density profile of monomers below and above the LCST. For the case of the model thermoresposive brush, we search for the optimum grafting density at which the change in the brush height, upon crossing the LCST, reaches its maximum value. The interpretation of the thermoresponse, in terms of the Alexander-de Gennes blobs and the level of solvation of polymer chains in a brush, is provided.