Combinational Hydrogel and Xerogel Actuators Showing NIR Manipulating Complex Actions.

Near-infrared (NIR)-driven shape memory hydrogels are synthesized with a one-pot polymerization of N,N-dimethylacrylamide in the inorganic clay and graphene oxide (GO) suspension. The hydrogel consists of only a physically crosslinked network, which is partially thermoreversible. With the efficient photothermal energy transformation of GO in the hydrogels, the shape recovery from the temporal shape is achieved by NIR irradiation. The optimal shape fixing percentage and recovery rate are found at moderate monomer and crosslinker contents. Meanwhile, the xerogel dried from the hydrogel also shows a fast NIR response shape change. The NIR manipulating combinational hydrogel-xerogel actuators are prepared by combining the wet and soft hydrogel and its dry and rigid xerogel together. The actuators achieve complex actions of turning and lifting under sequential NIR irradiation to carry an object up- and downward and around obstacles, or to transfer an object to a target position. This work provides a new idea for designing combinational actuators to fulfil complex actions.

On the development of a VIPARnd radiotherapy 3D polymer gel dosimeter.

This work presents an improvement of the VIPARnd ('nd' stands for 'normoxic, double', or VIP) polymer gel dosimeter. The gel composition was altered by increasing the concentration of the monomeric components, N-vinylpyrrolidone (NVP) and N,N'-methylenebisacrylamide (MBA), in co-solvent solutions. The optimal composition (VIPARCT, where 'CT' stands for computed tomography, or VIC) comprised: 17% NVP, 8% MBA, 12% t-BuOH, 7.5% gelatine, 0.007% ascorbic acid, 0.0008% CuSO4 × 5H2O and 0.02% hydroquinone. The following characteristics of VIC were achieved: (i) linear dose range of 0.9_30 Gy, (ii) saturation for radiation doses of over 50 Gy, (iii) threshold dose of about 0.5 Gy, (iv) dose sensitivity of 0.171 Gy-1 s-1, which is roughly 2.2 times higher than that of VIP (for nuclear magnetic resonance measurements). It was also found that VIC is dose- rate-independent, and its dose response does not alter if the radiation source is changed from electrons to photons for external beam radiotherapy. The gel responded similarly to irradiation with small changes in radiation energy but was sensitive to larger energy changes. The VIC gel retained temporal stability from 20 h until at least 10 d after irradiation, whereas spatial stability was retained from 20 h until at least 6 d after irradiation. The scheme adopted for VIC manufacturing yields repeatable gels in terms of radiation dose response. The VIC was also shown to perform better than VIP using x-ray computed tomography as a readout method; the dose sensitivity of VIC (0.397 HU Gy-1) was 1.5 times higher than that of VIP. Also, the dose resolution of VIC was better than that of VIP in the whole dose range examined.

Highly robust hydrogels via a fast, simple and cytocompatible dual crosslinking-based process.

A highly robust hydrogel device made from a single biopolymer formulation is reported. Owing to the presence of covalent and non-covalent crosslinks, these engineered systems were able to (i) sustain a compressive strength of ca. 20 MPa, (ii) quickly recover upon unloading, and (iii) encapsulate cells with high viability rates.

Visible light induced radical cyclization of o-iodophenylacrylamides: a concise synthesis of indolin-2-one.

A [Ir(ppy)2(dtb-bpy)]PF6-catalyzed intramolecular radical cyclization of o-iodophenylacrylamides affording indolin-2-ones in moderate to excellent yields via 5-exo-trig radical cyclization under visible light is presented. This method provides new access to the synthesis of indolin-2-ones under mild reaction conditions.

Fast self-healing of graphene oxide-hectorite clay-poly(N,N-dimethylacrylamide) hybrid hydrogels realized by near-infrared irradiation.

Self-healing hydrogels were proposed to be used as biomaterials, because of the capability of spontaneously healing injury, but most of the reported self-healing hydrogels do not possess high mechanical strength and fast self-healing at the same time. Herein, we prepared graphene oxide (GO)-hectorite clay-poly(N,N-dimethylacrylamide) (PDMAA) hybrid hydrogels with enhanced mechanical properties and fast self-healing capability realized by near-infrared (NIR) irradiation. The physical cross-linking between clay sheets and PDMAA chains provided the hydrogel with mechanical strength to maintain its stability in shape and architecture. GO sheets in the hybrid hydrogels acted as not only a collaborative cross-linking agent but also as a NIR absorber to absorb the NIR irradiation energy and transform it to thermal energy rapidly and efficiently, resulting in a rapid temperature increase of the GO containing gels. The chain mutual diffusion and the reformation of physical cross-linking occurred more quickly at higher temperature; consequently, the damaged hydrogel was almost completely recovered in a few minutes upon irradiation. We also demonstrated a potential application of the hybrid hydrogel as a self-healing surgical dressing.

A simple strategy for in situ fabrication of a smart hydrogel microvalve within microchannels for thermostatic control.

Self-regulation of temperature in microchip systems is crucial for their applications in biomedical fields such as cell culture and biomolecule synthesis as well as those cases that require constant temperature conditions. Here we report on a simple and versatile approach for in situ fabrication of a smart hydrogel microvalve within a microchip for thermostatic control. The thermo-responsive hydrogel microvalve enables the "on-off" switch by sensing temperature fluctuations to control the fluid flux as well as the fluid heat exchange for self-regulation of the temperature at a constant range. Such temperature self-regulation is demonstrated by integrating the microvalve-incorporated microchip into the flow circulation loop of a micro-heat-exchanging system for thermostatic control. Moreover, the microvalve-incorporated microchip is employed for culturing cells under temperature self-regulation. The smart microvalve shows great potential as a temperature controller for applications that require thermostatic conditions. This approach offers a facile and flexible strategy for in situ fabricating hydrogel microvalves within microchips as chemostats and microreactors for biomedical applications.

N-isopropylacrylamide gel dosimeter to evaluate clinical photon beam characteristics.

The introduction of beam intensity control concept in current radiotherapy techniques has increased treatment planning complexity. Thus, small-field dose measurement has become increasingly vital. Polymer gel dosimetry method is widely studied. It is the only dose measurement tool that provides 3D dose distribution. This study aims to use an N-isopropylacrylamide (NIPAM) gel dosimeter to conduct beam performance measurements of percentage depth dose (PDD), beam flatness, and symmetry for photon beams with field sizes of 3×3 and 4×4 cm(2). Computed tomography scans were used to readout the gel dosimeters. In the PDD measurement, the NIPAM gel dosimeter and Gafchromic™ EBT3 radiochromic film displayed high consistency in the region deeper than the build-up region. The gel dosimeter dose profile had 3% lower flatness and symmetry measurement at 5 cm depth for different fields compared with that of the Gafchromic™ EBT3 film. During gamma evaluation under 3%/3 mm dose difference/distance-to-agreement standard, the pass rates of the polymer gel dosimeter to the TPS and EBT3 film were both higher than 96%. Given that the gel is tissue equivalent, it did not exhibit the energy dependence problems of radiochromic films. Therefore, the practical use of NIPAM polymer gel dosimeters is enhanced in clinical dose verification.

Retrieval of rat aortic smooth muscle cells as intact cell sheet for regenerative medicine: a cost effective approach using photo polymerization.

Cell-based therapeutics are promising routes for the regeneration of damaged cells and organs. The recovery of cells cultured in vitro for such applications requires the use of proteolytic enzymes which deteriorate its property by disruption of cell-cell and cell-matrix interactions. Intact cell sheets can be retrieved with the use of thermo responsive polymer grafted on to the culture plates. Our study presents the use of photo-polymerization as a simple and inexpensive way to create thermo-responsive culture surfaces for the detachment of intact cell sheet. Poly (N-isopropyl acrylamide) (PNIPAAm) was synthesized by photo-polymerization and characterized by NMR spectroscopy, differential scanning calorimetry and gel permeation chromatography. Thermo-responsive culture dishes were prepared by the coating method and characterized for its thermo-responsive efficacy using FTIR spectroscopy and water contact angle measurements. Atomic force microscopy depicted the thin coating achieved with this method is similar to the conventional grafting method. Suitability for cell culture and cell sheet retrieval was assessed by culturing rat aortic smooth muscle cells in the PNIPAAm coated tissue culture plates. The cells remained viable as evident from the live dead assay and the cell sheet was detached by low temperature treatment. The results demonstrate a versatile method for creating thermo responsive culture surfaces while eliminating the use of expensive radiation sources for the conventional grafting method.

Nanozeolites doped photopolymer layers with reduced shrinkage.

An acrylamide based photopolymer doped with pure silica MFI-type zeolite (silicalite-1) nanoparticles has been characterized for holographic recording purposes. The concentrations of the silicalite-1 nanoparticles in the photopolymer layers were 1, 2.5, 5 and 7.5 wt. %. The inclusion of silicalite-1 nanoparticle in the photopolymer has resulted in an increase of the diffraction efficiency by up to 40%, and decrease of the shrinkage from 1.32% to 0.57%. The best results were obtained in layers doped with 5 wt. % silicalite-1 nanoparticles.

Evaluation of thermosensitive microspheres as potential components for sun-protectors.

In this study thermosensitive polymeric microspheres obtained in former research were evaluated in vitro for their photoprotective activity. The UVA/UVB ratio was assessed at so called shelf temperature, i.e., at 25 degrees C, and at elevated temperature of 45 degrees C. The evaluated polymers absorb higher levels of UV radiation, when heated from 25 degrees C to 45 degrees C. The MS1 polymer may be defined as polymer with high efficiency in the terms of gaining protection against UVA radiation, when heated. The MS2 absorbs both UVA and UVB radiation, and may be considered, as most protective, when heated to 45 degrees C. The equalized and less strong activity has the polymer MS3 when heated, with lipophilic radical implemented during synthesis.

Polymer gels for in-phantom dose imaging in radiotherapy.

Normoxic polymer gel dosimeters are studied, with the aim of achieving a valid and advantageous method for in-phantom 3D dose determinations. Developments were carried out in the application of such dosimetric material to the method based on dosimeter gel layers that has shown good reliability for absorbed dose imaging in radiotherapy. The technique has been improved, in particular taking care of minimizing the oxygen infiltration into the gel matrix in order to suitably avoid its effect of inhibiting the polymerization process after exposure. A suitable choice of the material of dosimeter walls has brought to achieve good steadiness in time of dosimeter sensitivity and satisfactory results in dose imaging and depth-dose profiling.

Photopolymerization of methacrylated chitosan/PNIPAAm hybrid dual-sensitive hydrogels as carrier for drug delivery.

A series of hybrid hydrogels based on glycidyl methacrylated chitosan (CS-GMA) and N-isopropylacrylamide (NIPAAm) were designed and prepared via photopolymerization technology. The hydrogels were characterized by Fourier transform infrared (FT-IR), differential scanning calorimetry (DSC) and optical transmittance. The interior morphology of hydrogels was investigated by scanning electron microscopy (SEM). The swelling experiment results revealed that hybrid hydrogel exhibited combined pH and temperature sensitivities. Acid orange 8 (AO8) and 5-flurouracil (5-Fu) were selected as model drugs for examining their release from hydrogels. The results suggested that hydrogel composition and pH value of buffer solution had great influences on release profiles.

Molecularly imprinted poly (methacrylamide-co-methacrylic acid) composite membranes for recognition of curcumin.

In this study, molecularly imprinted poly (methacrylamide-co-methacrylic acid) composite membranes with different ratio of methacrylamide (MAM) versus methacrylic acid (MAA) were prepared via UV initiated photo-copolymerization on the commercial filter paper. Curcumin was chosen as the template molecule. Infra-red (IR) spectroscopy was used to study the binding mechanism between the imprinted sites and the templates. The morphology of the resultant membranes was visualized by scanning electron microscopy (SEM). Static equilibrium binding and recognition properties of the imprinted composite membranes to curcumin (cur-I) and its analogues demethoxycurcumin (cur-II) or bisdemethoxycurcumin (cur-III) were tested. The results showed that curcumin-imprinted membranes had the best recognition ability to curcumin compared to its analogues. From the results, the biggest selectivity factor of alpha(cur-I/cur-II) and alpha(cur-I/cur-III) were 1.50 and 5.94, and they were obtained from the composite membranes in which MAM/MAA were 1:4 and 0:1, respectively. The results of this study implied that the molecularly imprinted composite membranes could be used as separation membranes for curcumin enrichment.

Removal of bovine serum albumin using solid-phase extraction with in-situ polymerized stationary phase in a microfluidic device.

Serum albumin, one of the most abundant serum proteins, blocks the expression of other important biomarkers. The objective of this study is to remove serum albumin effectively by using solid-phase extraction (SPE) in microfluidic devices. Photo-polymerized adsorbent as a stationary phase of SPE was used to remove bovine serum albumin (BSA). The adsorption capacity was examined with the effect of pH and concentration in BSA solution, and adjustment of monomer concentration such as hydrophilic 2-acrylamido-2-methyl-1-propanesulfonic acid and acrylamide in the adsorbent. The effect of hydrophobic butyl methacylate on BSA adsorption was also studied. Selective removal in a bicomponent with BSA and bovine gamma-globulin was performed by adjusting the pH as required.

A kind of novel biodegradable hydrogel made from copolymerization of gelatin with polypseudorotaxanes based on alpha-CDs.

A kind of novel biodegradable supramolecular hydrogel was synthesized via copolymerization of gelatin methacrylamide with photocurable and biodegradable polypseudorotaxanes under UV irradiation. These polypseudorotaxanes were prepared by supramolecular self-assemblies of alpha-cyclodextrins threaded onto amphiphilic LA-PEG-LA copolymers end-capped with methacryloyl groups. The hydrogels are injectable, and their structure was characterized in detail with FTIR, (1)H NMR, XRD, TG and DSC techniques. Their swelling behaviour and morphologies were also examined. The analytical results demonstrated that the channel-type crystalline structure of the polypseudorotaxanes remains in the as-obtained hydrogels. Moreover, the SEM pictures showed that the hydrogels having gelatin methacrylamide are more suitable for cell seeding and proliferation than those without gelatin added.

Light-responsive bioconjugates as novel tools for specific capture of biologicals by photoaffinity precipitation.

Light-responsive bioconjugates are synthesized by a two-step protocol calling first for cotelomerization (chain-transfer polymerization) of N-isopropylacrylamide and N-acryloxysuccinimide. The desired bioligand (biotin) is used in modified form as chain-transfer agent in this step. As a consequence, 100% of the produced bioconjugates carry this group. In a second step, the cotelomers (bioconjugates) are rendered photoresponsive by linking a chromophore ((3-aminopropyloxy)azobenzene) group to the N-acryloxysuccinimide side chains. The resulting structures show a critical solution temperature in pure water of 16 degrees C when the azo groups in the side chains are predominately in the (stable) trans state. Irradiation with UV light (330 nm) switches the azo group into the more hydrophilic cis state, and the critical solution temperature rises to 18 degrees C. Irradiation with visible light (> 440 nm) switches the group back to the trans state. Adjusting the temperature to an intermediate level, the bioconjugates are used to demonstrate the concept of photo affinity precipitation, i.e., the specific capture and recovery by light-induced precipitation of a target molecule (avidin) from a serum-containing cell-culture supernatant. The avidin was obtained in highly purified form; no nonspecific copurification of protein impurities was observable.

Dynamic swelling behavior of gamma-radiation induced polyelectrolyte poly(AAm-co-CA) hydrogels in urea solutions.

The aim of this study was to investigate the equilibrium swelling properties in urea solutions of gamma-radiation induced polyelectrolyte copolymeric hydrogels consisting of acrylamide (AAm) and crotonic acid (CA). Poly(acrylamide-co-crotonic acid), poly(AAm-co-CA) hydrogels containing different amounts of CA were obtained in the form of rods after radiation. Swelling experiments were performed in aqueous urea solutions at 25 degrees C, gravimetrically. The hydrogels showed large extents of swelling in aqueous (urea/water) media the swelling being highly dependent on the chemical composition of the hydrogels and irradiation dose. The percentage swelling of poly(AAm-co-CA) hydrogels was between 1160 and 4250%, while that of the AAm hydrogels was between 670 and 900%. The diffusional exponent values (n) are between 0.51 and 0.66, hence the diffusion of urea/water into the hydrogels is non-Fickian. Equilibrium urea/water contents of the hydrogel systems were changed between 0.870 and 0.977.

Temperature-sensitive polymer-nanoshell composites for photothermally modulated drug delivery.

Composites of thermally sensitive hydrogels and optically active nanoparticles have been developed for the purpose of photothermally modulated drug delivery. Copolymers of N-isopropylacrylamide (NIPAAm) and acrylamide (AAm) exhibit a lower critical solution temperature (LCST) that is slightly above body temperature. When the temperature of the copolymer exceeds the LCST, the hydrogel collapses, causing a burst release of any soluble material held within the hydrogel matrix. Gold-gold sulfide nanoshells, a new class of nanoparticles designed to strongly absorb near-infrared light, have been incorporated into poly(NIPAAm-co-AAm) hydrogels for the purpose of initiating a temperature change with light; light at wavelengths between 800 and 1200 nm is transmitted through tissue with relatively little attenuation, absorbed by the nanoparticles, and converted to heat. Significantly enhanced drug release from composite hydrogels has been achieved in response to irradiation by light at 1064 nm. We have investigated the release of methylene blue and proteins of varying molecular weight. Additionally, the nanoshell-composite hydrogels can release multiple bursts of protein in response to repeated near-IR irradiation.

Determination of acrylamide monomer in polyacrylamide degradation studies by high-performance liquid chromatography.

A high-performance liquid chromatography method using C18 and ion-exchange columns in series is developed for the determination of acrylamide and acrylic acid monomers in polymeric samples. The C18 column acts as a guard column, trapping surfactants and impurities and retaining the nonionic species. The ion-exchange column then separates the monomers according to their respective ionic strengths. This method has been proven in the laboratory to work successfully for all types of acrylamide/acrylic acid polymers and matrices. Detection limits for both monomers can be achieved in the parts-per-billion range. The method is used to study the possible degradation of polyacrylamide to acrylamide monomer in the presence of glyphosate (a herbicide) and sunlight. Polyacrylamide is used as a spray drift reduction aid in combination with glyphosate. In normal applications, the polymer and herbicide are in contact with each other in the presence of sunlight. The results show that the polymer does not degrade to acrylamide in the presence of glyphosate or sunlight or any combination of the two. It is also observed that glyphosate influences the solubility of polyacrylamide, and care must be used when combining the two.