Bifunctional Smart Hydrogel Dressing with Strain Sensitivity and NIR-Responsive Performance.

Smart response hydrogel has a broad application prospect in human health real-time monitoring due to its responses to a variety of stimuli. In this study, we developed a novel smart hydrogel dressing based on conductive MXene nanosheets and a temperature-sensitive PNIPAm polymer. γ-Methacryloxypropyltrimethoxysilane (KH570) was selected to functionalize the surface of MXene further to improve the interface compatibility between MXene and PNIPAm. Our prepared K-M/PNIPAm hydrogel was found to have a strain-sensitive property, as well as a respond to NIR phase change and volume change. When applied as a strain flexible sensor, this K-M/PNIPAm hydrogel exhibited a high strain sensitivity with a gauge factor (GF) of 4.491, a broad working strain range of ≈250%, a fast response of ∼160 ms, and good cycle stability (i.e., 3000 s at 20% strain). Besides, this K-M/PNIPAm hydrogel can be used as an efficient NIR light-controlled drug release carrier to achieve on-demand drug release. This work paved the way for the application of smart response hydrogel in human health real-time monitoring and NIR-controlled drug release functions.

3D printing fluorescent material with tunable optical properties.

The 3D printing of fluorescent materials could help develop, validate, and translate imaging technologies, including systems for fluorescence-guided surgery. Despite advances in 3D printing techniques for optical targets, no comprehensive method has been demonstrated for the simultaneous incorporation of fluorophores and fine-tuning of absorption and scattering properties. Here, we introduce a photopolymer-based 3D printing method for manufacturing fluorescent material with tunable optical properties. The results demonstrate the ability to 3D print various individual fluorophores at reasonably high fluorescence yields, including IR-125, quantum dots, methylene blue, and rhodamine 590. Furthermore, tuning of the absorption and reduced scattering coefficients is demonstrated within the relevant mamalian soft tissue coefficient ranges of 0.005-0.05 mm-1 and 0.2-1.5 mm-1, respectively. Fabrication of fluorophore-doped biomimicking and complex geometric structures validated the ability to print feature sizes less than 200 µm. The presented methods and optical characterization techniques provide the foundation for the manufacturing of solid 3D printed fluorescent structures, with direct relevance to biomedical optics and the broad adoption of fast manufacturing methods in fluorescence imaging.

A Near-Infrared-Triggered Dynamic Wrinkling Biointerface for Noninvasive Harvesting of Practical Cell Sheets.

Cell sheet engineering represents a new era of precise and efficient regenerative medicine, but its efficacy is limited by the elaborative preparation and the weak mechanics. Herein, a near-infrared (NIR)-triggered dynamic wrinkling biointerface was designed for rapid acquisition of practical cell sheets. The biocompatible NIR can initiate the photothermal-mechanical linkage cascade to efficiently dissolve the collagen supporting layer and release the high-quality cell sheets. The interfacial shear force generates with the dynamic wrinkling, playing an active role in accelerating the cell sheet release. High-quality and self-supporting cell sheets can be harvested within a few minutes, demonstrating a new paradigm of photothermal-mechanical manipulation. The transplantable cell sheets with outstanding physiological and mechanical performances were proven to promote wound healing in skin regeneration. This method may open a completely new front in thermal and mechanical responsive cascade to harvest cell sheets, facilitating their wide applications in regenerative medicine.

Spatio-temporal control over destabilization of Pickering emulsions stabilized by light-sensitive dextran-based nanoparticles.

The implementation of light-sensitive Pickering emulsions with spatio-temporal responsiveness in advanced applications like drug-delivery, colloidal or reaction engineering would open new avenues. However, curiously, light-sensitive Pickering emulsions are barely studied in the literature and their biocompatibility and/or degradability scarcely addressed. Thus, their development remains a major challenge. As an original strategy, we synthesized light-sensitive nanoparticles based on biocompatible Poly(NitroBenzylAcrylate) grafted dextran (Dex-g-PNBA) to stabilize O/W Pickering emulsions. The produced emulsions were stable in time and could undergo time and space-controlled destabilization under light stimulus. Irradiation time and alkaline pH-control of the aqueous phase were proved to be the actual key drivers of destabilization. As the nanoparticles themselves were photolyzed under light stimulus, possible harmful effects linked to accumulation of nanomaterials should be avoided. In addition to UV light (365 nm), visible light (405 nm) was successfully used for the spatio-temporal destabilization of the emulsions, offering perspectives for life science applications.

Cellulose nanocrystals reinforced highly stretchable thermal-sensitive hydrogel with ultra-high drug loading.

Hydrogels often have poor mechanical properties which limit their application in load-bearing tissues such as muscle and cartilage. In this work, a near-infrared light-triggered stretchable thermal-sensitive hydrogel with ultra-high drug loading was developed by a combination of natural polymeric nanocrystals, a network of synthetic thermo-responsive polymer, and magnetic Fe3O4 nanoparticles. The hydrogels comprise cellulose nanocrystals (CNCs) decorated with Fe3O4 nanoparticles (Fe3O4/CNCs) dispersed homogeneously in poly(N-isopropylacrylamide) (PNIPAm) networks. The composite hydrogels exhibit an extensibility of 2200%. Drug loading of vancomycin (VCM) reached a high value of 10.18 g g-1 due to the dispersion of Fe3O4/CNCs and the interactions between the CNCs and the PNIPAm network. Importantly, the hydrogels demonstrated a thermo-response triggered by NIR, with the temperature increasing from 26 to 41 °C within 60 s. The hydrogels have high biocompatibility evidenced by cell proliferation tests, illustrating that these hydrogels are promising as dressings for wound closure, and wound healing.

Spatiotemporal patterning of photoresponsive DNA-based hydrogels to tune local cell responses.

Understanding the spatiotemporal effects of surface topographies and modulated stiffness and anisotropic stresses of hydrogels on cell growth remains a biophysical challenge. Here we introduce the photolithographic patterning or two-photon laser scanning confocal microscopy patterning of a series of o-nitrobenzylphosphate ester nucleic acid-based polyacrylamide hydrogel films generating periodically-spaced circular patterned domains surrounded by continuous hydrogel matrices. The patterning processes lead to guided modulated stiffness differences between the patterned domains and the surrounding hydrogel matrices, and to the selective functionalization of sub-regions of the films with nucleic acid anchoring tethers. HeLa cells are deposited on the circularly-shaped domains functionalized with the MUC-1 aptamers. Initiation of the hybridization chain reaction by nucleic acid tethers associated with the continuous hydrogel matrix results in stress-induced ordered orthogonal shape-changes on the patterned domains, leading to ordered shapes of cell aggregates bound to the patterns.

Performance optimization of CdS precipitated graphene oxide/polyacrylic acid composite for efficient photodegradation of chlortetracycline.

Here a CdS embedded poly acrylic acid (PAA)/graphene oxide (GO) polymeric composite was prepared for the efficient degradation of chlortetracycline (CTC) driven by visible light irradiation. The structure-activity relationship of GO/PAA-CdS was confirmed through the photocatalytic evaluation of a series of samples prepared by varying GO concentration, molar ratio of Cd:S and the amount of crosslinking agent. Through the composition, morphology, photoelectrochemical characterizations and degradation kinetic studies, it could be confirmed that the enhanced photocatalytic activity is attributed to the controlled growth of CdS nanoparticles by polymer net structure and effective electron transfer along GO nanosheets. The photodegradation of CTC was confirmed to be mainly governed by O2- and OH radicals generated from GO/PAA-CdS. The degradation intermediates of CTC were confirmed by LC-MS, and possible degradation pathways were proposed based on the prediction of radical attacking sites according to Fukui function values obtained through Density Functional Theory (DFT). Moreover, it was found that the catalytic activity of the photocatalyst was maintained after several cycles confirming the enhanced anti-photocorrosion of GO/PAA-CdS. This research provided an efficient approach by a novel photocatalyst for the removal of CTC from wastewater.

Fabrication of Chitosan-Based Intumescent Flame Retardant Coating for Improving Flame Retardancy of Polyacrylonitrile Fabric.

In order to improve the flame retardancy of polyacrylonitrile (PAN) fabrics, glycidyl methacrylate (GMA) was first grafted onto the surface of PAN fabric (PAN-g-GMA) by means of UV-induced photo grafting polymerization process. Then, PAN-g-GMA was chemically grafted with chitosan to obtain a bigrafted PAN fabric (PAN-g-GMA-g-CS). Finally, the flame-retardant PAN fabric (FR-PAN) was prepared by phosphorylation. The structure and elemental analysis of the samples were characterized by Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). The thermal degradation properties and combustion characteristics of the fabrics were accessed by thermogravimetric analysis (TG), differential scanning calorimetry (DSC), and cone calorimeter (CC). The results show that the onset thermal decomposition temperature of FR-PAN fabric is lower than that of the control sample due to the degradation of the grafting groups. The combustion test indicates that the FR-PAN fabric has an excellent flame-retardant property and the combustion rate is significantly reduced. In addition, the char residue of the burned FR-PAN fabric is over 97%, indicating excellent char-forming ability.

Synchrotron FTIR Micro-spectroscopy Studies Demonstrate the Release of Ceramide Molecules from a Ceramide-containing UV-curable Acrylic Adhesive Resin.

A recent study has shown that the addition of ceramide to adhesive materials of medical sheets or tapes improves or maintains skin barrier functions despite the irritation and damage caused by the repeated removal of the sheet or tape. This fact may imply that ceramide molecules are released from the adhesive material and penetrate the skin. In this study, we investigated whether ceramide molecules are released from a UV-curable acrylic adhesive resin (acResin®) sheet containing ceramide molecules attached to a cultured skin sample by estimating the local ceramide concentration from the data obtained by synchrotron Fourier transform infrared micro-spectroscopy analysis. Since section samples of uniform thickness could not be prepared, the intensity data of the amide I peak originating from ceramide were normalized by using the intensity data of the ester peak originating from the resin matrix. This analysis enabled the quantification of the change in local ceramide concentrations in the sheet samples. This result indicates that ceramide molecules were released from the acResin® sheet attached to the cultured skin sheet.

Preparation of polyacrylic acid-grafted-acryloyl/hemicellulose (PAA-g-AH) hybrid films with high oxygen barrier performance.

Developing high-performance oxygen barrier films using biomass-based materials is crucial for the development of green and sustainable society. Herein, we develop a strategy to synthesize polyacrylic acid-grafted-acryloyl/hemicellulose composites (PAA-g-AH) as film materials with excellent oxygen barrier property. The as-synthesized films were extensively characterized by Fourier transform infrared (FT-IR), scanning electron microscopy (SEM), gel permeation chromatography (GPC), 1H nuclear magnetic resonance (1H NMR), mechanical test, light transmittance and oxygen transmission rate (OTR) measurement. All these testing results showed that the optimum film exhibit great oxygen barrier property with a low OTR value of 0.25 ± 0.01 cm3* µm/(m2*d*kPa), which was much lower than that of pure PAA film. Moreover, the hybrid films possess well mechanical strength, light transmittance and recycle usage properties. Experimental results indicated that the as-synthesized films have great potential applications in several fields as packaging materials, such as drug, food and electronic products.

Hollow Capsules with Multiresponsive Valves for Controlled Enzymatic Reactions.

The current challenge for polymeric nanoreactors is to precisely control the membrane permeability between permeable, impermeable, and semipermeable at defined pH. Additionally, the synthetic methods are obstructed by tedious purification processes, especially when polymer multiblocks are required in the membrane of capsules to achieve different responsiveness and functions. Here, we report a rapid one-pot synthesis of ABA-type triblock copolymer brushes on silica template via surface-initiated single electron transfer living radical polymerization (SI-SET-LRP). It is worth noting that there is no purification between the successive block formation steps, since each step is taken to full translation within 20 min. After removing the template, hollow capsules with cross-linked membrane are obtained and have been used as multiresponsive nanoreactors for enzymatic reactions. Their membrane permeability is triggered primarily by temperature and secondarily by pH to allow controlled enzymatic reactions to be reversibly addressable between "permeable", "semipermeable", and "impermeable" valve-like membrane status. These valve-like features highlight the significant potential of hollow capsules, for example, in the fields of synthetic biology and enzyme-deficient disease therapeutic applications.

Characterization of Ivoclar Vivadent Dental Restoration Material for 137CS Retrospective Radiation Dosimetry.

Retrospective dosimetry is the method of using materials on or near a person who is exposed to ionizing radiation to determine the amount of radiation received by the person. A possible candidate material for retrospective dosimetry is Ivoclar Vivadent IPS e.max® CAD ceramic dental restoration material, which exhibits radiation-induced thermoluminescence when exposed to gamma- and x-ray radiation from a Cs source. The purpose of this paper is to characterize the material and study the behavior of the thermoluminescence signal with radiation dose and with delay time between radiation exposure and thermoluminescence measurement. The first glow peak is well-modeled by a first-order glow curve deconvolution formula. The height of the first glow peak is approximately linear with dose. The fading of the signal with time is approximately described by a power law curve with cutoff. The material appears to be suitable for retrospective radiation dosimetry.

Radiation induced crosslinking of polyacrylamide incorporated low molecular weights natural polymers for possible use in the agricultural applications.

Superabsorbent hydrogels based on polyacrylamide (PAAm) and Na-alginate (Alg) or chitosan (CS) were synthesized by γ-rays. The effect of dose and copolymer composition on gel content and water absorbency of PAAm/Alg, PAAm/CS and PAAm/Alg/CS hydrogels were studied. The gel content and water absorbency follows the order PAAm/Alg>PAAm/Alg/CS>PAAm/CS. The effect of different cations, fertilizers, buffers on water absorbency of the hydrogels was investigated. Water retention capability of swollen hydrogels as a function of time was studied. PAAm/Alg hydrogel has a high water retention capability. An application of the prepared hydrogels in agricultural fields was performed using maize plants. The results showed that the presence of hydrogels had growth promotion effect on quality and quantity of maize plants. The plants treated by PAAm/Alg hydrogels showed 50% increase in the grain yield suggesting their possible use as a soil conditioner and a water reservoir for plant-soil system.

Photothermally triggered actuation of hybrid materials as a new platform for in vitro cell manipulation.

Mechanical forces in the cell's natural environment have a crucial impact on growth, differentiation and behaviour. Few areas of biology can be understood without taking into account how both individual cells and cell networks sense and transduce physical stresses. However, the field is currently held back by the limitations of the available methods to apply physiologically relevant stress profiles on cells, particularly with sub-cellular resolution, in controlled in vitro experiments. Here we report a new type of active cell culture material that allows highly localized, directional and reversible deformation of the cell growth substrate, with control at scales ranging from the entire surface to the subcellular, and response times on the order of seconds. These capabilities are not matched by any other method, and this versatile material has the potential to bridge the performance gap between the existing single cell micro-manipulation and 2D cell sheet mechanical stimulation techniques.

Synthesis and characterization of polyacrylic acid- grafted-carboxylic graphene/titanium nanotube composite for the effective removal of enrofloxacin from aqueous solutions: Adsorption and photocatalytic degradation studies.

Polyacrylic acid-grafted-carboxylic graphene/titanium nanotube (PAA-g-CGR/TNT) composite was synthesized. It was effectively used as adsorbent as well as photocatalyst. The composite was characterized by FTIR, XRD, SEM, TEM, Surface Area Analyzer, XPS and DRS. The photocatalytic activity of PAA-g-CGR/TNT composite was evaluated on the basis of the degradation of pollutants by using sunlight. The band gap of the prepared photocatalyst was found to be 2.6eV. The removal of the antibiotic enrofloxacin (ENR) was achieved by two step mechanism based on adsorption and photodegradation. The maximum adsorption was observed at pH 5.0. The best fitted kinetic model was found to be pseudo-second-order. The maximum adsorption was observed at 30°C. The maximum adsorption capacity was found to be 13.40mg/g. The kinetics of photodegradation of ENR onto PAA-g-CGR/TNT composite follow first-order kinetics and optimum pH was found to be 5.0. The regeneration and reuse of the adsorbent-cum-photocatalyst were also examined upto five cycles.

Microwaved bacterial cellulose-based hydrogel microparticles for the healing of partial thickness burn wounds.

Burn wound management is a complex process because the damage may extend as far as the dermis which has an acknowledged slow rate of regeneration. This study investigates the feasibility of using hydrogel microparticles composed of bacterial cellulose and polyacrylamide as a dressing material for coverage of partial-thickness burn wounds. The microparticulate carrier structure and surface morphology were investigated by Fourier transform infrared, X-ray diffraction, elemental analysis, and scanning electron microscopy. The cytotoxicity profile of the microparticles showed cytocompatibility with L929 cells. Dermal irritation test demonstrated that the hydrogel was non-irritant to the skin and had a significant effect on wound contraction compared to the untreated group. Moreover, histological examination of in vivo burn healing samples revealed that the hydrogel treatment enhanced epithelialization and accelerated fibroblast proliferation with wound repair and intact skin achieved by the end of the study. Both the in vitro and in vivo results proved the biocompatibility and efficacy of hydrogel microparticles as a wound dressing material.

LED Curing Lights and Temperature Changes in Different Tooth Sites.

Objectives. The aim of this in vitro study was to assess thermal changes on tooth tissues during light exposure using two different LED curing units. The hypothesis was that no temperature increase could be detected within the dental pulp during polymerization irrespective of the use of a composite resin or a light-curing unit. Methods. Caries-free human first molars were selected, pulp residues were removed after root resection, and four calibrated type-J thermocouples were positioned. Two LED lamps were tested; temperature measurements were made on intact teeth and on the same tooth during curing of composite restorations. The data was analyzed by one-way analysis of variance (ANOVA), Wilcoxon test, Kruskal-Wallis test, and Pearson's χ (2). After ANOVA, the Bonferroni multiple comparison test was performed. Results. Polymerization data analysis showed that in the pulp chamber temperature increase was higher than that without resin. Starlight PRO, in the same condition of Valo lamp, showed a lower temperature increase in pre- and intrapolymerization. A control group (without composite resin) was evaluated. Significance. Temperature increase during resin curing is a function of the rate of polymerization, due to the exothermic polymerization reaction, the energy from the light unit, and time of exposure.

Initial characterization of a gel patch dosimeter for in vivo dosimetry.

In vivo dosimetry is a greatly underutilized tool for patient safety in clinical external beam radiotherapy treatments, despite being recommended by several national and international organizations (AAPM, ICRU, IAEA, NACP). The reasons for this underutilization mostly relate to the feasibility and cost of in vivo dosimetry methods. Due to the increase in the number of beam angles and dose per fraction in modern treatments, there is a compelling need for a novel dosimeter that is robust and affordable while able to operate properly in these complex conditions. This work presents a gel patch dosimeter as a novel method of in vivo dosimetry. DEFGEL, a 6% T normoxic polyacrylamide gel, was injected into 1 cm thick acrylic molds to create 1 cm thick small cylindrical patch dosimeters. To evaluate the change in optical density due to radiation induced polymerization, dosimeters were scanned before and after irradiation using an in-house developed laser densitometer. The dose-responses of three separate batches of gel were evaluated and compared to check for linearity and repeatability. The response development time was evaluated to ensure that the patch dosimeter could be high throughput. Additionally, the potential of this system to be used as an in vivo dosimeter was tested with a clinically relevant end-to-end in vivo phantom test. All irradiations were performed with a Varian Clinac 21EX at the University of Wisconsin Medical Radiation Research Center (UWMRRC). The dose-response of all three batches of gel was found to be linear within the range of 2-20 Gy. At doses below 0.5 Gy the statistical uncertainties were prohibitively large to make quantitative assessments of the results. The three batches demonstrated good repeatability in the range of 2 Gy to up to 10 Gy, with only slight variations in response at higher doses. For low doses the dosimeter fully developed within an hour while at higher doses they fully developed within four hours. During the in vivo phantom test the predicted patch absorbed dose was 4.23 Gy while the readout dose was evaluated to be 4.37 Gy, which corresponds to a 3.2% discrepancy. The dosimeter and densitometer pairing shows promise as an in vivo dosimetry system, especially for hypofractionated or MRI-guided radiotherapy treatments where higher doses are prescribed.

Differences in the intensity of light-induced fluorescence emitted by resin composites.

BACKGROUND: The aims of this study were to compare the intensities of fluorescence emitted by different resin composites as detected using quantitative light-induced fluorescence (QLF) technology, and to compare the fluorescence intensity contrast with the color contrast between a restored composite and the adjacent region of the tooth. METHODS: Six brands of light-cured resin composites (shade A2) were investigated. The composites were used to prepare composite discs, and fill holes that had been prepared in extracted human teeth. White-light and fluorescence images of all specimens were obtained using a fluorescence camera based on QLF technology (QLF-D) and converted into 8-bit grayscale images. The fluorescence intensity of the discs as well as the fluorescence intensity contrast and the color contrast between the composite restoration and adjacent tooth region were calculated as grayscale levels. RESULTS: The grayscale levels for the composite discs differed significantly with the brand (p<0.001): DenFil (10.84±0.35, mean±SD), Filtek Z350 (58.28±1.37), Premisa (156.94±1.58), Grandio (177.20±0.81), Charisma (207.05±0.77), and Gradia direct posterior (211.52±1.66). The difference in grayscale levels between a resin restoration and the adjacent tooth was significantly greater in fluorescence images for each brand than in white-light images, except for the Filtek Z350 (p<0.05). However, the Filtek Z350 restoration was distinguishable from the adjacent tooth in a fluorescence image. CONCLUSIONS: The intensities of fluorescence detected from the resin composites varied. The differences between the composite and adjacent tooth were greater for the fluorescence intensity contrast than for the colors observed in the white-light images.

Intrapulpal Thermal Changes during Setting Reaction of Glass Carbomer® Using Thermocure Lamp.

Objectives. To measure the temperature increase induced during thermocure lamp setting reaction of glass carbomer and to compare it with those induced by visible light curing of a resin-modified glass ionomer and a polyacid-modified composite resin in primary and permanent teeth. Materials and Methods. Nonretentive class I cavities were prepared in extracted primary and permanent molars. Glass carbomer (GC) was placed in the cavity and set at 60°C for 60 sn using a special thermocure lamp. Resin-modified glass ionomer (RMGIC) and polyacid-modified composite resin (PMCR) were placed in the cavities and polymerized with an LED curing unit. Temperature increases during setting reactions were measured with a J-type thermocouple wire connected to a data logger. Data were examined using two-way analysis of variance and Tukey's honestly significant difference tests. Results. The use of GC resulted in temperature changes of 5.17 ± 0.92°C and 5.32 ± 0.90°C in primary and permanent teeth, respectively (p > 0.05). Temperature increases were greatest in the GC group, differing significantly from those in the PMCR group (p < 0.05). Conclusion. Temperature increases during polymerization and setting reactions of the materials were below the critical value in all groups. No difference was observed between primary and permanent teeth, regardless of the material used.