Backbone-Photodegradable Polymers by Incorporating Acylsilane Monomers via Ring-Opening Metathesis Polymerization.

Materials capable of degradation upon exposure to light hold promise in a diverse range of applications including biomedical devices and smart coatings. Despite the rapid access to macromolecules with diverse compositions and architectures enabled by ring-opening metathesis polymerization (ROMP), a general strategy to introduce facile photodegradability into these polymers is lacking. Here, we report copolymers synthesized via ROMP that can be degraded by cleaving the backbone in both solution and solid states under irradiation with a 52 W, 390 nm Kessil LED to generate heterotelechelic low-molecular-weight fragments. To the best of our knowledge, this work represents the first instance of the incorporation of acylsilanes into a polymer backbone. Mechanistic investigation of the degradation process supports the intermediacy of an α-siloxy carbene, formed via a 1,2-photo Brook rearrangement, which undergoes insertion into water followed by cleavage of the resulting hemiacetal.

Bio-inspired photonic crystals for naked eye quantification of nucleic acids.

Herein, a chip imitating the desert beetle shell was presented for naked eye nucleic acid quantification. The hydrophobic photonic crystal substrate treated by ultraviolet local irradiation could effectively disperse the sample into hundreds of droplets for digital loop-mediated isothermal amplification (dLAMP). Pyrophosphate (PPI), a by-product of the LAMP reaction, combined with magnesium ions to form a poorly soluble precipitate. It could be fixed on a silica substrate due to complexation, resulting in the disappearance of the structural color of the photonic crystals. The number of points without structural color contains the information of the copy number of nucleic acids in the sample. This chip could achieve the naked eye quantitative detection of Salmonella DNA without fluorescence or other chromogenic reagents. Thus, the chip designed in this study can help the development of digital nucleic acid detection under limited resource settings (LRS) and can be suitable for POCT (point of care test) standards.

Gamma-Irradiation Induced Functionalization of Graphene Oxide with Organosilanes.

Gamma-ray radiation was used as a clean and easy method for turning the physicochemical properties of graphene oxide (GO) in this study. Silane functionalized-GO were synthesized by chemically grafting 3-aminopropyltriethoxysilane (APTES) and 3-glycidyloxypropyltrimethoxysilane (GPTES) onto GO surface using gamma-ray irradiation. This established non-contact process is used to create a reductive medium which is deemed simpler, purer and less harmful compared conventional chemical reduction. The resulting functionalized-GO were characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), thermogravimetric analysis (TGA), and Raman spectroscopy. The chemical interaction of silane with the GO surface was confirmed by FT-IR. X-ray diffraction reveals the change in the crystalline phases was due to surface functionalization. Surface defects of the GO due to the introduction of silane mioties was revealed by Raman spectroscopy. Thermogravimetric analysis of the functionalized-GO exhibits a multiple peaks in the temperature range of 200-650 °C which corresponds to the degradation of chemically grafted silane on the GO surface.

Effect of the addition of silanated silica on the mechanical properties of microwave heat-cured acrylic resin.

OBJECTIVES: The purpose of this study was to evaluate the flexural strength and Vickers hardness of a microwave energy heat-cured acrylic resin by adding different concentrations of silane surface-treated nanoparticle silica. METHODS: Acrylic resin specimens with dimensions of 65 × 10 × 2.5 mm were formed and divided into five experimental groups (n = 10) according to the silica concentration added to the acrylic resin mass (weight %) prior to polymerisation : G1, without silica; G2, 0.1% silica; G3, 0.5% silica; G4, 1.0% silica; and G5, 5.0% silica. The specimens were submitted to a three-point flexural strength test and to the Vickers hardness test (HVN). The data obtained were statistically analysed by anova and the Tukey test (α = 0.05). RESULTS: Regarding flexural strength, G5 differed from the other experimental groups (G1, G2, G3 and G4) presenting the lowest mean, while G4 presented a significantly higher mean, with the exception of group G3. Regarding Vickers hardness, a decrease in values was observed, in which G1 presented the highest hardness compared with the other experimental groups. CONCLUSION: Incorporating surface-treated silica resulted in direct benefits in the flexural strength of the acrylic resin activated by microwave energy; however, similar results were not achieved for hardness.

The effects of primer precuring on the shear bond strength between gold alloy surfaces and metal brackets.

The objective of this study was to investigate the effects of precuring of primer coated on bracket bases on the strength of bonds between metal brackets and gold alloy. Square type III gold alloy plates were sandblasted with 30 µm silicon dioxide. After silica coating, excessive particles were removed gently with air. Silane was then applied, and maxillary central incisor metal brackets were bonded to each conditioned alloy surface with Transbond XT. Half of the specimens were precured at the bracket base after primer coating and the other half was not precured before bonding to the alloy surface. After bracket positioning, samples were cured using a light emitting diode (LED) for 40 seconds. Shear bond strengths were tested and adhesive remnant index (ARI) was evaluated after 1 hour and 24 hours. The primer precuring and 24 hours group exhibited highest bond strength (12.53 MPa) and the no precuring and 1 hour group showed lowest bond strength (5.58 MPa). Precured groups showed lower ARI scores. Due to the shallow curing depth of LED light and inhibition of transillumination at the metal surface, primer precuring at the bracket base is required for secure bracket bonding on gold alloy surfaces using LED curing units.

Decatungstate (W10O32(4-))/silane: a new and promising radical source under soft light irradiation.

The use of decatungstate (W10O32(4-)) in combination with silanes to generate silyl radicals under green fluorescence bulb irradiation as well as sunlight exposure is described. The mechanisms are investigated by ESR and laser flash photolysis experiments. The high potential of this reaction is evidenced here when using a decatungstate/silane/diphenyl iodonium salt combination as an initiating system for the ring opening photopolymerization of epoxides.

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.

Photoactivation of alkyl C-H and silanization: a simple and general route to prepare high-density primary amines on inert polymer surfaces for protein immobilization.

Surface modification through implanting functional groups has been demonstrated to be extremely important to biomedical applications. The usage of organic polymer phase is often required to achieve satisfactory results. However, organic surfaces usually have poor chemical reactivity toward other reactants and target biomolecules because these surfaces usually only consist of simple alkyl (C-H) and/or alkyl ether (ROR') structures. For the first time, we here report the potential to perform silanization techniques on alkyl polymer surface, which provide a simple, fast, inexpensive, and general method to decorate versatile functional groups at the molecular level. As an example, high-density primary amines could be obtained on a model polymer, polypropylene substrate, through the reaction between amine-capped silane, 3-aminopropyltriethoxysilane (APTES) and hydroxylated polypropylene surface. A model protein, immunoglobulin (IgG), could be effectively immobilized on the surface after transforming amines to aldehydes by the aldehyde-amine condensation reaction between glutaraldehyde (GA) and amines. The routes we report here could directly make use of the benefits from well-developed silane chemistry, and hereby are capable of grafting any functionalities on inert alkyl surfaces via changing the terminal groups in silanes, which should instantly stimulate the development of many realms such as microarrays, immunoassays, biosensors, filtrations, and microseparation.

Selective protein patterning based on the micro-structured organosilane self-assembled monolayer by vacuum ultraviolet light lithography.

We have succeeded to immobilize fluorescent proteins selectively using a micro-structured organosilane self-assembled monolayer as a template. An organosilane layer with amino terminal group was formed on a thermally oxidized Si wafer by liquid-phase method and then was pattern-etched by vacuum ultraviolet light (VUV). The second organosilane layer with thiol terminal group was deposited on the etched area by chemical vapor surface modification method (CVSM). These micro-structured organosilane layer containing two reactive terminal groups were chemically modified using bi-functional linkers. Two kinds of fluorescent protein, Enhanced Cyan Fluorescent Protein (ECFP) and R-phycoerythrin were selectively immobilized on the chemically modified surface.

Effect of UV irradiation on the shear bond strength of titanium with segmented polyurethane through gamma-mercapto propyl trimethoxysilane.

The objective of this study was to investigate the effect of UV irradiation on shear bond strength between a titanium (Ti) and a segmented polyurethane (SPU) composite through gamma-mercapto propyl trimethoxysilane (gamma-MPS). To this end, the shear bond strength of Ti/SPU interface of Ti-SPU composite under varying conditions of ultraviolet ray (UV) irradiation was evaluated by a shear bond test. The glass transition temperatures of SPU with and without UV irradiation were also determined using differential scanning calorimetry. It was found that the shear bond strength of Ti/SPU interface increased with UV irradiation. However, excessive UV irradiation decreased the shear bond strength of Ti/SPU interface. Glass transition temperature was found to increase during 40-60 seconds of UV irradiation. In terms of durability after immersion in water at 37 degrees C for 30 days, shear bond strength was found to improve with UV irradiation. In conclusion, UV irradiation to a Ti-SPU composite was clearly one of the means to improve the shear bond strength of Ti/SPU interface.

Three-dimensional cell growth on structures fabricated from ORMOCER by two-photon polymerization technique.

Two-photon polymerization technique was applied to generate three-dimensional (3D) scaffold-like structures using the photosensitive organic-inorganic hybrid polymer ORMOCER. The structures were studied with respect to potential applications as scaffold for tissue engineering. Cell counting and comet assay, respectively, demonstrated that doubling time and DNA strand breaks of CHO cells, GFSHR-17 granulosa cells, GM-7373 endothelial cells, and SH-SY5Y neuroblastoma cells were not affected by ORMOCER. ORMOCER related alteration of formation of tissue specific cell-to-cell adhesions like gap junctions was ruled out by double whole-cell patch-clamp technique. Additionally, growth of cells on the vertical surfaces of 3D structures composed of ORMOCER is shown.

Low shrinkage light curable nanocomposite for dental restorative material.

OBJECTIVES: The aim of this study was to develop a low shrinkage visible light curable nanocomposite dental restorative material without sacrificing the other properties of conventional materials. This nanocomposite was developed by using an epoxy resin 3,4-epoxycyclohexylmethyl-(3,4-epoxy)cyclohexane carboxylate (ERL4221) matrix with 55% wt of 70-100 nm nanosilica fillers through ring-opening polymerization. GPS (gamma-glycidoxypropyl trimethoxysilane) was used to modify the surfaces of silica nanoparticles. RESULTS: The nanocomposite was shown to exhibit low polymerization shrinkage strain, which is only a quarter of currently used methacrylate-based composites. It also exhibited a low thermal expansion coefficient of 49.8 microm/m degrees C which is comparable to that of the methacrylate based composites (51.2 microm/m degrees C). The strong interfacial interactions between the resin and fillers at nanoscales were demonstrated by an observed high strength and high thermal stability of the nanocomposite. A microhardness of 62 KHN and a tensile strength of 47 MPa were reached. A high degree of conversion ( approximately 70%) can be obtained after less than 60 s of irradiation upon the nanocomposite. A transmission electron microscope (TEM) study of the nanocomposite showed no aggregation of fillers. Comparable results to the methacrylate based composites were obtained from the one day MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl-2H-tetrazolium bromide) cytotoxicity test. SIGNIFICANCE: The developed epoxy resin based nanocomposite demonstrated low shrinkage and high strength and is suitable for dental restorative material applications.

Interphase structure-property relationships in thermoset dimethacrylate nanocomposites.

OBJECTIVES: The aim of this research was to better understand the relationships between interphase composition and the resultant mechanical properties of thermoset methacrylate nanocomposites, ultimately for the purpose of improving the properties of dental restorative materials through manipulation of the interphase. METHODS: Silica nanoparticles were silanized with three different silanes and blends of those silanes to generate six different interphase compositions. The silanes varied in their relative polarity, flexibility, and reactivity towards photo-polymerization. Composites containing 60% by mass of the silanized fillers were prepared and analyzed for uncured paste handling characteristics, vinyl conversion, biaxial flexure strength (BFS), modulus, and Knoop hardness. RESULTS: Dual silanization of the fillers improved the handling characteristics of the uncured composite pastes compared to those containing fillers silanized with 3-methacryloxypropyltrimethoxysilane. To obtain high BFS, functional groups reactive in free radical polymerization were needed in the composite interphase, but a high concentration of those groups was not necessary. Moduli were highest for composites with interphases that contained styrylethyltrimethoxysilane, a reactive aromatic silane. The hardness values of the composites with reactive interphases were all comparable. Methacrylate conversion was only modestly influenced by silane interphase composition. SIGNIFICANCE: This study suggests that dual silanization is a practical method for improving the handling characteristics of uncured dental restorative nanocomposites while maintaining or improving the mechanical properties of the cured composites.

Use of a DNA film on a self-assembled monolayer for investigating the physical process of DNA damage induced by core electron ionization.

PURPOSE: A novel two-layer sample composed of a deoxyribonucleic acid (DNA) film and self-assembled monolayer (SAM) was prepared on an inorganic surface to mimic the processes in which DNA is damaged by soft X-ray irradiation. MATERIALS AND METHODS: A mercaptopropyltrimethoxysilane (MPTS) SAM was formed on a sapphire surface, then oligonucleotide (OGN) molecules were adsorbed on the MPTS-SAM. The thicknesses and chemical states of the layers were determined by X-ray photoelectron spectroscopy (XPS) and near-edge X-ray fine structure (NEXAFS) around the phosphorus (P) and sulfur (S) K-edges. To induce the damage to the OGN molecules, the sample was irradiated with synchrotron soft X-rays. The chemical state of the OGN molecules before and after irradiation was examined by NEXAFS around the nitrogen (N) K-edge region. RESULTS: The thickness of the MPTS-OGN layer was approximately 7.7 nm. The S atom of the OGN molecules was located at the bottom of the OGN layer. The peak shape of the N K-edge NEXAFS spectra of the MPTS-OGN layers clearly changed following irradiation. CONCLUSIONS: The MPTS-OGN layer formed on the sapphire surface. The chemical states and the structure of the interface were elucidated using synchrotron soft X-rays. The OGN molecules adsorbed on the MPTS films decomposed upon exposure to soft X-ray irradiation.

Reduced irradiation time in slow-curing of resin composite using an intensity-changeable light source.

Possibility to shorten the total irradiation time in slow-curing with an intensity-changeable light source, Curetron 7 (CT-7), was investigated for four hybrid-type resin composites. Irradiation condition with CT-7 was assigned as 10 or 20 seconds at low light intensity (230 mW/cm2) and followed by 20 or 10 seconds at high intensity (600 mW/cm2) respectively (i.e., a total of 30 seconds). For a reference, irradiation was carried out for 30 seconds using a halogen lamp (900 mW/cm2). After irradiation, mechanical properties of the cured composites--in terms of microhardness and flexural strength--were evaluated. Also, cavity adaptation was examined in standardized, cylindrical dentin cavities treated with an adhesive system. Compared to the reference irradiation, slow-curing with CT-7 produced acceptable mechanical properties and better adaptation. These results suggested that total exposure time of slow-curing with CT-7 could be shortened to 30 seconds.

Effect of bifunctional comonomers on mechanical strength and water sorption of amorphous calcium phosphate- and silanized glass-filled Bis-GMA-based composites.

This study seeks to elucidate structure-property relationships in a series of unfilled dental copolymers and their composites. The copolymers/composites were derived from photo-activated binary monomer systems based on 2,2-bis[p-2'-hydroxy-3'-methacryloxypropoxy)phenyl] propane (Bis-GMA) and equimolar amounts of a bifunctional, surface-active comonomer, i.e., 2-hydroxyethyl methacrylate (HEMA), glycerol dimethacrylate (GDMA) or ethylene glycol methacrylate phosphate (PHEMA). Triethyleneglycol dimethacrylate, a widely used comonomer for Bis-GMA, was used as a control. Two types of fillers were investigated: (1) a hydrophilic, silica-modified amorphous calcium phosphate (Si-ACP) and (2) a more hydrophobic, silanized nanosized silica (n-SiO(2)). Both the unfilled copolymers and their composites were evaluated for biaxial flexure strength (BFS), both dry and wet after 30 days immersion in buffered saline, and for water sorption (WS) and their WS kinetic profiles. The Bis-GMA copolymers and composites derived from HEMA and GDMA had BFS and WS values, as well as WS kinetic profiles, similar to the controls. Copolymers and composites based on Bis-GMA/PHEMA had lower BFS and higher WS values. Si-ACP composites had significantly lower BFS values (that were further diminished on soaking) than their copolymers. WS increased as the level of this filler was increased except for Bis-GMA/PHEMA composites. With n-SiO(2) as the filler, a more moderate reduction in BFS occurred compared to the unfilled copolymers. By contrast to Si-ACP composites, the WS of all the n-SiO(2) composites decreased with increasing filler level. From this study it is evident that both the chemical structure of the polymer matrix and the type of filler system can have significant effects on the strength and water-related properties of dental composites.

Volumetric contraction and methacrylate conversion in photo-polymerized amorphous calcium phosphate/methacrylate composites.

Because of its relatively high solubility in aqueous media and its rapid transformation to hydroxyapatite, amorphous calcium phosphate (ACP) has been utilized as the filler phase of resin-based bioactive composites that have remineralization potential. The objectives of this study were to determine how various methacrylate resins and various types of ACP fillers affect acrylic vinyl conversion and polymerization shrinkage (PS). Several types of photo-crosslinkable resin systems were prepared and admixed with a mass fraction of 40% of either unhybridized, silica- or zirconia-hybridized ACP. After visible light-activated photo-polymerization ACP composites were assessed by near infrared spectroscopy for degree of vinyl conversion and by mercury dilatometry for PS. It was found for these composites that vinyl conversion was independent of filler type but strongly dependent on the type and composition of the resin phase. PS, on the other hand, showed more complex dependence both on the resin type and composition and, in some cases, on the type of ACP. In order to obtain ACP/methacrylate-based composites with maximal vinyl conversion, resin type and composition are of primary importance. However, in order to minimize volume contraction on polymerization it appears necessary to consider both the resin and filler type of these bioactive composites.

General collection efficiency in liquid iso-octane and tetramethylsilane used as sensitive media in a thimble ionization chamber.

The general collection efficiency in the dielectric liquids iso-octane (CaH18; 2-2-4 trimethylpentane) and tetramethylsilane (Si(CH3)4), used as sensitive media in a thimble liquid ionization chamber (LIC) with a liquid layer thickness of 1 mm, has been studied. Measurements were made for continuous radiation at varying dose rates using 140 keV photons from the decay of 99mTc for chamber polarizing voltages of 50, 100 and 500 V. The maximum dose rate in each measurement session was about 150 mGy min(-1). The experimental results were compared with theoretical general collection efficiencies calculated by the equation for the general collection efficiency in gases. The results show that the general collection efficiency in a thimble LIC for continuous radiation can be calculated with the equation for the general collection efficiency in gas ionization chambers, using the same chamber geometry correction factors and analogous characteristic ion recombination parameters for the dielectric liquids.

First tests of a liquid ionization chamber to monitor intensity modulated radiation beams.

First measurements with a prototype ionization chamber are described to be applied in online monitoring of modulated fields in radiation therapy. The liquids isooctane, isononane (TMP) and tetramethylsilane (TMS) are used in a high purity grade in order to realize high current signals for electronic read-out in parallel at frequencies exceeding 10 Hz. Signals of more than a factor 4 with respect to isooctane, analysis grade, are obtained. With an electrode structure of 400 pads, a uniformity in efficiency within 1.2% has been measured. The penumbra of a multileaf collimator could be resolved. Theoretical examination verifies that the free electrons in the liquids cause higher signals when the measured currents are compared with expectation for ion transport only.

Selected characteristics of an Ormocer and a conventional hybrid resin composite.

OBJECTIVES: The objective of this in vitro study was to evaluate surface roughness, hardness and wear resistance of an Ormocer (Admira), polymerized by a plasma arc system. A secondary objective was to investigate two placement technique bulk or incremental layers. METHODS: Blocks from Admira and Amelogen (a microhybrid composite) were prepared in cylinders, 3 mm in diameter, and 2 and 5 mm in thickness (bulk or incrementally placed) and polymerized by a plasma arc and a conventional light system. Surface roughness measurements were taken by a Surface Profilometer on the top of the specimens. Vickers hardness measurements, with a load of 600mN were taken on the top and bottom of 2 mm and top, intermediate and bottom of 5 mm thick specimens. For the wear test, specimes (8 mm in diameter and 2 mm in thickness) of Admira, Amelogen and amalgam were tested in a ball-on design, by circular movements of the antagonist (alumina ball; diameter 10 mm) under 10 N load. For the statistical evaluation of the results of surface roughness, microhardness and wear test; a paired samples t-test and Kruskal-Wallis analysis of variance test, were performed. RESULTS: Admira showed highest hardness values in all polymerization types at the top surface and this was statistically significant (p < 0.05). These highest hardness values were obtained with conventional polymerization (81.84 +/- 1.167 VHN). Meanwhile, the wear resistance of Admira was found to be higher than Amelogen (Wd(admira) = 0.024 +/- 0.00149 mm3; Wd(amelogen) = 0.032 +/- 0.00075 mm3). However, Admira demonstrated the highest surface roughness value compared to Amelogen, with plasma arc 5 s (0.65 +/- 0.023 microm). Amelogen was found to have the lowest surface roughness value with conventional 40 s (0.45 +/- 0.012 microm). SIGNIFICANCE: The results indicated that Ormocer, which was developed by Ormocer technology, demonstrated higher microhardness and wear resistance when compared to a hybrid composite; however, the polishability of Ormocer needs further investigation. Also the selection of visible light activated composite resins exhibited higher surface microhardness values when polymerized with conventional rather than with plasma arc.