Gold-Nanoshell-Functionalized Polymer Nanoswimmer for Photomechanical Poration of Single-Cell Membrane.

We report an ultrasound-driven gold-nanoshell-functionalized polymer multilayer tubular nanoswimmer that can photomechanically perforate the membrane of a cancer cell by assistance of near-infrared (NIR) light. The nanoswimmers were constructed by a template-assisted layer-by-layer technique and subsequent functionalization of Au nanoshells inside the big opening. The nanoswimmers exhibit efficient and controllable movement toward target cells through the manipulation of the acoustic field. Next, the nanoswimmers with end-on attachment onto the HeLa cells achieve the poration of the cell membrane within 0.1 s under the irradiation of NIR light. The experimental and theoretical results suggest that the instantaneous photothermal effect provides enough photomechanical force to open the cell membrane. Such NIR-light-assisted nanoswimmers-enabled cell membrane poration possesses various advantages including active targeting, short time, and precision in single cells that conventional chemical and physical cell poration techniques could not achieve and, thus, provides considerable promise in a variety of biomedical applications such as gene delivery and artificial insemination.

Effect of light aging on silicone-resin bond strength in maxillofacial prostheses.

PURPOSE: The aim of this study was to investigate the effect of accelerated light aging on bond strength of a silicone elastomer to three types of denture resin. MATERIALS AND METHODS: A total of 60 single lap joint specimens were fabricated with auto-, heat-, and photopolymerized (n = 20) resins. An addition-type silicone elastomer (Episil-E) was bonded to resins treated with the same primer (A330-G). Thirty specimens served as controls and were tested after 24 hours, and the remaining were aged under accelerated exposure to daylight for 546 hours (irradiance 765 W/m(2) ). Lap shear joint tests were performed to evaluate bond strength at 50 mm/min crosshead speed. Two-way ANOVA and Tukey's test were carried out to detect statistical significance (p < 0.05). RESULTS: ANOVA showed that the main effect of light aging was the most important factor determining the shear bond strength. The mean bond strength values ranged from 0.096 to 0.136 MPa. The highest values were recorded for auto- (0.131 MPa) and photopolymerized (0.136 MPa) resins after aging. CONCLUSIONS: Accelerated light aging for 546 hours affects the bond strength of an addition-type silicone elastomer to three different denture resins. The bond strength significantly increased after aging for photo- and autopolymerized resins. All the bonds failed adhesively.

Biodegradable elastomeric networks: highly efficient cross-linking of poly(trimethylene carbonate) by gamma irradiation in the presence of pentaerythritol triacrylate.

Biodegradable elastomeric poly(trimethylene carbonate) (PTMC) networks were efficiently formed by gamma irradiating the linear polymer in the presence of pentaerythritol triacrylate (PETA). The properties of networks formed upon irradiation of PTMC films containing (0, 1, 5 wt %) PETA as a cross-linking aid were evaluated. The gel contents and network densities increased with increasing PETA contents, irradiation dose, and initial polymer molecular weights. At a dose of 25 kGy, networks with gel fractions up to 0.96 could be obtained. The networks were noncytotoxic, had elastic moduli below 10.7 MPa and high tensile strengths of up to 37.7 MPa. The incorporation of PETA also improved the resistance to creep and to tear propagation significantly, resulting in permanent set values that were as low as 0.9% strain and tear strengths up to 9.3 ± 2.0 N/mm. Furthermore, the enzymatic erosion rates of the networks could be decreased from 12.0 ± 2.9 to 3.0 ± 1.6 µm/day. These biodegradable elastomeric PTMC networks may be utilized in a broad range of medical applications.

Synchrotron radiation-based analysis of fatigue in dental restorative materials.

Few studies performed a microstructural analysis of dental restorations to evaluate fatigue impact under various tensions, because of a lack of analytical equipment. In this study, the fatigue of restorative materials was evaluated using the force tester's fatigue method at 0.30, 0.3, 0.40, and 0.45 N. The fatigue effect analysis of tooth restorations was performed with each sample by randomly dividing the sequence into grades 0-4 and the evaluators were blinded to the test results. The evaluation methods involved visual and stereoscopic approaches, and used synchrotron radiation (SR). The evaluation facilitated the observation of microscopic cracks in the material using SR. The initiation of cracks was attributed to air bubbles, invisible to the naked eye or under the microscope. The fatigue effect analysis using SR enabled closer observations compared with other types of evaluation. We expect that this strategy will provide a basis for the study of physical and mechanical properties of dental materials.

Nanomechanical characterization of time-dependent deformation/recovery on human dentin caused by radiation-induced glycation.

An increase in non-enzymatic collagen matrix cross-links, such as advanced glycation end-products (AGEs), is known to be a major complication in human mineralized tissues, often causing abnormal fractures. However, degradation of mechanical properties in relation to AGEs has not been fully elucidated at the material level. Here, we report nanoscale time-dependent deformation and dimensional recovery of human tooth dentin that has undergone glycation induced by x-ray irradiation. The reduction in enzymatic collagen cross-linking and the increased level of AGEs with concomitant growth of disordered collagen matrix diminished creep deformation recovery in the lower mineralized target region. However, the elevated AGEs level alone did not cause a reduction in time-dependent deformation and its recovery in the higher mineralized target region. In addition to the elevated AGEs level, the degradation of the mechanical properties of mineralized tissues should be assessed with care in respect to multiple parameters in the collagen matrix at the molecular level.

Setting characteristics of a resin infiltration system for incipient caries treatment.

OBJECTIVES: This study investigated the curing efficiency, the extent of atmospheric oxygen inhibition to the polymerization reaction and the mechanical properties of a new resin-infiltration system for caries treatment. METHODS: The curing efficiency was estimated by measuring the percentage degree of cure (%DC) of thin resin films (h: 150µm, Ø: 5mm, n=3), 10min after 40s exposure to a quartz halogen bulb (750mW/cm2) light curing unit (Optilux 501, Demetron/Kerr, USA), in the absence of O2, by micro ATR-FTIR spectroscopy. The extent of O2 inhibition on resin film setting (width in µm) was assessed by transmission optical microscopy on thin films (h: 150µm, Ø: ∼7mm, n=5) placed between two transparent cover slips and exposed to air from lateral sites. For each sample the extent of inhibition was measured at 5 different locations. The mechanical properties were tested employing Instrumented Indentation Testing according to ISO 14577:2002. Resin specimens (h: 2mm, Ø: 10mm, n=5) were prepared employing cylindrical teflon moulds enclosed in transparent matrix strips and glass slides as before. The measurements were performed employing a Vickers indenter attached to a universal hardness testing machine (ZHU2.5/Z2.5 plus test Xpert software, Zwick/Roell, Ulm, Germany). The parameters tested were Martens Hardness (MH), Vickers Hardness (VHN), Indentation Elastic Modulus (EIT) and elastic to total ratio of indentation work (ηIT). For all these tests, specimens of a conventional light-curing bonding resin (HB-Heliobond, Ivoclar-Vivadent, FL) prepared as above were used as control. Student t-test was used to identify statistically significant differences between the two materials in the parameters tested (a: 0.05). RESULTS: The results of the materials tested were: (a) [% DC]; IC: 57.4±1.5, HB: 59.8±2.4, (b) [Width of O2 inhibition/µm]; IC: 33.1±6.5, HB: 23.6±4.4, (c) [MH/N/mm(2)] IC; 116±16, HB: 261±35, (d) [VHN]; IC; 15.4±2.5, HB: 22.1±1.8, (e) [EIT/(GPa)]; IC; 2.3±0.4, HB: 7.5±0.5, and (g) [ηIT (%)] IC; 50.3±3.4, HB: 35.1±1.9. The IC presented no significant difference in terms of % DC, higher thickness of the inhibited layer, lower MH, VHN, EIT and greater ηIT values than HB. CONCLUSIONS AND CLINICAL SIGNIFICANT: The resin-infiltrating system for incipient caries treatment demonstrated the same curing efficiency with a conventional unfilled bonding resin, but exhibited higher extent of oxygen inhibition, lower hardness, lower elastic modulus and higher plastic to elastic indentation energy.

Photocrosslinked nanocomposite hydrogels from PEG and silica nanospheres: structural, mechanical and cell adhesion characteristics.

Photopolymerized hydrogels are extensively investigated for various tissue engineering applications, primarily due to their ability to form hydrogels in a minimally invasive manner. Although photocrosslinkable hydrogels provide necessary biological and chemical characteristics to mimic cellular microenvironments, they often lack sufficient mechanical properties. Recently, nanocomposite approaches have demonstrated potential to overcome these deficits by reinforcing the hydrogel network with. In this study, we investigate some physical, chemical, and biological properties of photocrosslinked poly(ethylene glycol) (PEG)-silica hydrogels. The addition of silica nanospheres significantly suppresses the hydration degree of the PEG hydrogels, indicating surface interactions between the silica nanospheres and the polymer chains. No significant change in hydrogel microstructure or average pore size due to the addition of silica nanospheres was observed. However, addition of silica nanospheres significantly increases both the mechanical strength and the toughness of the hydrogel networks. The biological properties of these nanocomposite hydrogels were evaluated by seeding fibroblast cells on the hydrogel surface. While the PEG hydrogels showed minimum cell adhesion, spreading and proliferation, the addition of silica nanospheres enhanced initial cell adhesion, promoted cell spreading and increased the metabolic activity of the cells. Overall, results indicate that the addition of silica nanospheres improves the mechanical stiffness and cell adhesion properties of PEG hydrogels and can be used for biomedical applications that required controlled cell adhesion.

Preparation of well-defined poly(ether-ester) macromers: photogelation and biodegradability.

Two series of poly(ether-ester)-based bis-functional macromers terminated with acrylate groups and a well-defined number of ester bonds were synthesized. One series had a chain of 1, 3 or 5 ester bonds at both ends of the central poly(ethylene glycol) block (molecular weight, about 1000), while the other had an alternating structure of oligo(ethylene glycol) each of them linked to two ester bonds, in which 6 or 10 ester bonds were incorporated equally in the macromer molecules and the total molecular weight was adjusted by about 1000. Irradiation of all poly(ether-ester) macromers mixed with camphorquinone resulted in the formation of gels. Gel yield increased and hydrophilic properties of the gels produced decreased with irradiation time. The elastic modulus of the gels decreased with the number of ester bonds. Upon incubation in a PBS solution (pH 8.04), all gels were gradually degraded with time. At 3 weeks of incubation, the degradation ratio increased linearly with the number of ester bonds per unit of molecular weight of the macromers. The order of in vivo degradation rates determined from weight loss was similar to that of the in vitro study. Thus, these poly(ether-ester) macromers may be useful for biodegradable biomaterials or tissue engineering scaffolds.

Flexural strength of experimentally filled resins made of electron beam irradiated silica fillers.

This study investigated the influence of different silica fillers on the flexural strength of experimentally filled resins. Hydrophilic (non-silanated) silica, hydrophobic silica modified by organofunctional silane, and silica modified by organofunctional silane that additionally contains polymerizable carbon double bonds were assigned into further subgroups: the first subgroup was electron beam irradiated with 10 kGy (dose rate) and the second with 30 kGy, whereas the third constituted the non-irradiated control group. In total, nine experimentally filled resin blends were mixed. Rectangular specimens were constructed, and a flexural strength test was performed. Regardless of the type of silica, specimens constructed of blends containing non-irradiated fillers showed the lowest flexural strength in comparison to their corresponding irradiated groups. With increasing dose rates from 10 to 30 kGy, filler irradiation prior to blend mixing resulted in slightly increased flexural strength values for hydrophilic as well as for organofunctional silanated silica. Specimens constructed of blends with fillers that were not only modified by silane containing polymerizable carbon double bonds but were additionally irradiated showed the highest flexural strength. The results of this study indicate that the flexural strength of filled resins could be enhanced by advance preparation of silica fillers with silane coupling agents followed by electron beam irradiation.

Photo-crosslinked poly(epsilon-caprolactone fumarate) networks for guided peripheral nerve regeneration: material properties and preliminary biological evaluations.

In an effort to achieve suitable biomaterials for peripheral nerve regeneration, we present a material design strategy of combining a crystallite-based physical network and a crosslink-based chemical network. Biodegradable polymer disks and conduits have been fabricated by photo-crosslinking three poly(epsilon-caprolactone fumarate)s (PCLF530, PCLF1250, and PCLF2000), which were synthesized from the precursor poly(epsilon-caprolactone) (PCL) diols with nominal molecular weights of 530, 1250, and 2000 g mol(-1), respectively. Thermal properties such as glass transition temperature (T(g)), melting temperature (T(m)), and crystallinity of photo-crosslinked PCLFs were examined and correlated with their rheological and mechanical properties. Furthermore, in vitro degradation of uncrosslinked and crosslinked PCLFs in PBS crosslinked PCLFs in 1 N NaOH aqueous solution at 37 degrees C was studied. In vitro cytocompatibility, attachment, and proliferation of Schwann cell precursor line SPL201 cells on three PCLF networks were investigated. Crosslinked PCLF2000 with the highest crystallinity and mechanical properties was found to best support cell attachment and proliferation. Using a new photo-crosslinking method, single-lumen crosslinked PCLF nerve conduits without defects were fabricated in a glass mold. Crosslinked PCLF2000 nerve conduits were selected for evaluation in a 1cm gap rat sciatic nerve model. Histological evaluation demonstrated that the material was biocompatible with sufficient strength to hold sutures in place after 6 and 17 weeks of implantation. Nerve cable with myelinated axons was found in the crosslinked PCLF2000 nerve conduit.