Atom transfer radical-polymerized cationic shells on gold nanoparticles for near infrared-triggered photodynamic therapy of tumor-bearing animals.

Gold nanoparticles (AuNPs) were surface-engineered with a cationic corona to enhance the incorporation of photosensitizers for photodynamic therapy (PDT). The cationic corona composed of poly(2-(dimethylamino)ethyl methacrylate) was atom transfer radical-polymerized on the surface of the AuNPs. The cationic corona of the engineered surface was characterized by dynamic light scattering, electron microscopy, Raman spectroscopy, and mass spectroscopy. Chlorin-e6 (Ce6) incorporated onto the surface-engineered AuNPs exhibited higher cell incorporation efficiency than bare AuNPs. Ce6-incorporated AuNPs were confirmed to release singlet oxygen upon NIR irradiation. Compared to Ce6, Ce6-incorporated AuNPs exhibited higher cellular uptake and cytotoxicity against cancer cells in an irradiation time-dependent manner. Near-infrared-irradiated animals administered Ce6-incorporated AuNPs exhibited higher levels of tumor suppression without noticeable body weight loss. This result was attributed to the higher localization of Ce6 at the tumor sites to induce cancer cell apoptosis. Thus, we envision that engineered AuNPs with cationic corona can be tailored to effectively deliver photosensitizers to tumor sites for photodynamic therapy.

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.

Long-term microwaving of denture base materials: effects on dimensional, color and translucency stability.

INTRODUCTION: While the combined effect of microwave irradiation with cleansing solutions on denture base materials has been investigated, the effects of only using microwave irradiation and, more importantly, in a long-term basis, was not studied yet. OBJECTIVE: The purpose of this study was to evaluate the effect of a long-term repeated microwaving on the dimensional, color and translucency stability of acrylic and polyamide denture base materials. MATERIAL AND METHODS: Thirty two specimens (32 mm x 10 mm x 2.5 mm) from polyamide (Valplast) and PMMA (Vertex Rapid Simplified) denture base materials were made. Eight specimens from each material were immersed in distilled water (control) and 8 were subjected to microwave exposure at 450 W for 3 minutes for a period simulating 224 days of daily disinfection. Linear dimension, color change (ΔE*) and translucency parameter (TP) were measured at baseline and after certain intervals up to 224 cycles of immersion, using a digital calliper and a portable colorimeter. The results were analysed using two-way repeated measures ANOVA to estimate possible differences among predetermined cycles and material type. Regression analysis was also performed to estimate the trend of changes with time. Statistical evaluations performed at a significance level of 5%. RESULTS: Data analysis showed significant changes in length at baseline with an increasing number of cycles (p<0.05) and a significant interaction of cycle-material (p<0.001). The ΔΕ* parameter was significantly higher with a higher number of cycles (p<0.001), but it did not vary between materials (p>0.05). TP decreased similarly in both materials following microwave action but in a significantly higher level for Valplast (p<0.001). CONCLUSIONS: The results indicated that long-term repeated microwaving affects linear dimensional, color and translucency changes of both materials. Differences between PMMA and polyamide material were noted only in dimension and translucency changes.

Long-term microwaving of denture base materials: effects on dimensional, color and translucency stability

Abstract While the combined effect of microwave irradiation with cleansing solutions on denture base materials has been investigated, the effects of only using microwave irradiation and, more importantly, in a long-term basis, was not studied yet. Objective The purpose of this study was to evaluate the effect of a long-term repeated microwaving on the dimensional, color and translucency stability of acrylic and polyamide denture base materials. Material and Methods Thirty two specimens (32 mm x 10 mm x 2.5 mm) from polyamide (Valplast) and PMMA (Vertex Rapid Simplified) denture base materials were made. Eight specimens from each material were immersed in distilled water (control) and 8 were subjected to microwave exposure at 450 W for 3 minutes for a period simulating 224 days of daily disinfection. Linear dimension, color change (ΔE*) and translucency parameter (TP) were measured at baseline and after certain intervals up to 224 cycles of immersion, using a digital calliper and a portable colorimeter. The results were analysed using two-way repeated measures ANOVA to estimate possible differences among predetermined cycles and material type. Regression analysis was also performed to estimate the trend of changes with time. Statistical evaluations performed at a significance level of 5%. Results Data analysis showed significant changes in length at baseline with an increasing number of cycles (p<0.05) and a significant interaction of cycle-material (p<0.001). The ΔΕ* parameter was significantly higher with a higher number of cycles (p<0.001), but it did not vary between materials (p>0.05). TP decreased similarly in both materials following microwave action but in a significantly higher level for Valplast (p<0.001). Conclusions The results indicated that long-term repeated microwaving affects linear dimensional, color and translucency changes of both materials. Differences between PMMA and polyamide material were noted only in dimension and translucency changes.

Evaluation of the migration of chemicals from baby bottles under standardised and duration testing conditions.

After the prohibition of bisphenol-A-containing polycarbonate baby bottles in the European Union (EU), alternative materials, such as polypropylene, polyethersulphone, Tritan™ copolyester, etc., have appeared on the market. Based on an initial screening and in vitro toxicity assessment, the most toxic migrating compounds were selected to be monitored and quantified using validated GC- and LC-QqQ-MS methods. The effect of several 'real-life-use conditions', such as microwave, sterilisation and dishwasher, on the migration of different contaminants was evaluated by means of duration tests. These results were compared with a reference treatment (filling five times with pre-heated simulant at 40°C) and with the legal EU 'repetitive-use conditions' (three migrations, 2 h at 70°C). Analysis of the third migration step of the EU repetitive-use conditions (which has to comply with the EU legislative migration limits) showed that several non-authorised compounds were observed in some baby bottles exceeding 10 µg kg(-1). However, all authorised compounds were detected well below their respective specific migration limits (SMLs). The reference experiment confirmed the migration of some of the compounds previously detected in the EU repetitive-use experiment, though at lower concentrations. Analysis of extracts from the microwave and dishwasher experiments showed a reduction in the migration during the duration tests. In general, the concentrations found were low and comparable with the reference experiment. Similar observations were made for the two sterilisation types: steam and cooking sterilisation. However, steam sterilisation seems to be more recommended for daily use of baby bottles, since it resulted in a lower release of substances afterwards. Repeated use of baby bottles under 'real-life' conditions showed no increase in the migration of investigated compounds and, after some time, the migration of these compounds even became negligible.

Light-triggered chemical amplification to accelerate degradation and release from polymeric particles.

We describe a means of chemical amplification to accelerate triggered degradation of a polymer and particles composed thereof. We designed a light-degradable copolymer containing carboxylic acids masked by photolabile groups and ketals. Photolysis allows the unmasked acidic groups in the polymer backbone to accelerate ketal hydrolysis even at neutral pH.

UV/thermally driven rewritable wettability patterns on TiO2-PDMS composite films.

Composite films of TiO2 and polydimethylsiloxane (PDMS) are prepared by a sol-gel method, cured with UV irradiation, and then treated in hot water to crystallize the TiO2 in the film. The presence of anatase TiO2 contributes to the photoinduced superhydrophilicity of the film under UV irradiation. Contact angle studies reveal that the TiO2-PDMS composite film recovers its original hydrophobic state. Hydrophobic-superhydrophilic patterns are successfully formed on the films. The wettability patterns can be erased by UV irradiation and thermal treatment. New wettability patterns can be reconstructed, demonstrating that the film exhibits rewritable wettability without the need for organic chemicals.

Removal of acidic indigo carmine textile dye from aqueous solutions using radiation induced cationic hydrogels.

This study examined the removal of acidic indigo carmine dyes from aqueous solutions using cationic hydrogels. Irradiated hydrogels were investigated as a new sorbent for dye removal from aqueous solution. Poly(N,N-Diethylamino ethyl methacrylate) [poly(DEAEMA)] hydrogels were prepared by radiation polymerisation of N,N-diethylamino ethyl methacrylate [DEAEMA] monomer in the presence of cross-linking agent, ethylene glycol dimethacrylate [EGDMA], and used for the removal of acidic indigo carmine textile dye. The adsorption of dyes was examined using a batch sorption technique. The effects of pH, time and initial dye concentration on the adsorption capacity of hydrogels were investigated. Maximum gelation ratio was 98.2% at irradiation dose of 5.3 kGy. Maximum equilibrium volume swelling, V/V(0), value was 21.3 at pH 2.8. Maximum amount of adsorbed indigo carmine onto hydrogels was 96.7 mg dye/g gel at pH 2.8, 21 h of adsorption time and 120 mg/L initial dye solution. Swelling and adsorption capacity increased with decreasing of pH. Compared with Congo red, amounts of adsorbed indigo carmine are much higher than those of Congo red. Langmuir isotherm model was the best fit for these poly(DEAEMA) hydrogels-indigo carmine systems.

Radiolysis products and sensory properties of electron-beam-irradiated high-barrier food-packaging films containing a buried layer of recycled low-density polyethylene.

The aim was to study the effect of electron-beam irradiation on the production of radiolysis products and sensory changes in experimental high-barrier packaging films composed of polyamide (PA), ethylene-vinyl alcohol (EVOH) and low-density polyethylene (LDPE). Films contained a middle buried layer of recycled LDPE, while films containing 100% virgin LDPE as the middle buried layer were taken as controls. Irradiation doses ranged between zero and 60 kGy. Generally, a large number of radiolysis products were produced during electron-beam irradiation, even at the lower absorbed doses of 5 and 10 kGy (approved doses for food 'cold pasteurization'). The quantity of radiolysis products increased with irradiation dose. There were no significant differences in radiolysis products identified between samples containing a recycled layer of LDPE and those containing virgin LDPE (all absorbed doses), indicating the 'functional barrier' properties of external virgin polymer layers. Sensory properties (mainly taste) of potable water were affected after contact with irradiated as low as 5 kGy packaging films. This effect increased with increasing irradiation dose.

The effect of artificial accelerated weathering on the mechanical properties of maxillofacial polymers PDMS and CPE.

The effect of UVA-UVB irradiation on the mechanical properties of three different industrial types of polydimethylsiloxane and chlorinated polyethylene samples, used in maxillofacial prostheses, was investigated in this study. Mechanical properties and thermal analysis are commonly used to determine the structural changes and mechanical strength. An aging chamber was used in order to simulate the solar radiation and assess natural aging. Compression and tensile tests were conducted on a Zwick testing machine. Durometer Shore A hardness measurements were carried out in a CV digital Shore A durometer according to ASTM D 2240. Glass transition temperature was evaluated with a differential scanning calorimeter. Simple mathematical models were developed to correlate the measured properties with irradiation time. The effect of UVA-UVB irradiation on compressive behavior affected model parameters. Significant deterioration seems to occur due to irradiation in samples.

Formation of superhydrophobic poly(dimethysiloxane) by ultrafast laser-induced surface modification.

The formation of hemispherical nanostructures and microscaled papilla by ultrafast laser irradiation was found to be a potential method to generate superhydrophbic surface of synthetic polymers. Irradiation of femtosecond laser creates roughened poly(dimethylsiloxane) (PDMS) surface in nano- and microscales, of which topography fairly well imitate a Lotus leaf in nature. The modified surface showed superhydrophobicity with a contact angle higher than 170 degrees as well as sliding angle less than 3 degrees. We further demonstrated that negative replica of the processed PDMS surface exhibit large contact angle hysteresis with a sliding angle of 90 degrees while the positive replica maintains superhydrophobicity.

Cell interactions with laser-modified polymer surfaces.

The performance of a polymeric biomaterial depends on the bulk and surface properties. Often, however, the suitability of the surface properties is compromised in favour of the bulk properties. Altering the surface properties of these materials will have a profound effect on how cells and proteins interact with them. Here, we have used an excimer laser to modify the surface wettability of nylon 12. The surface treatment is rapid, cost-effective and can cause reproducible changes in the surface structure of the polymers. Polymers were treated with short wavelength ( < 200 nm) UV light. These wavelengths have sufficient photon energy (6.4eV) to cause bond scission at the material surface. This results in a surface reorganisation with incorporation of oxygen. Surface wettability changes were confirmed using contact angle measurements. Cell interactions with the surfaces were examined using 3T3 fibroblast and HUVEC cells. Cells morphology was examined using a confocal laser scanning microscope (CLSM). Cell activity and cell number on the treated nylon were assessed using biochemical assays for up to seven days. Both fibroblasts and endothelial cells initially proliferated better on treated compared with untreated samples. However, over seven days activity decreased for both cell types on the control samples and endothelial cell activity and cell number also decreased on the treated polymer.

The effect of solar irradiation on the fading of nylon and polyester fabrics dyed with selected disperse dyestuffs on radiant energy basis.

Solar total, UVA and UVB irradiances were measured separately using three kinds of wavelength band detectors in Tokyo, Japan in November 1999. Characteristics of diurnal variations were examined: Total irradiance reached a maximum value of about 600 W m(-2) at around noon. The variation pattern of UVA irradiance was observed to be similar to the total irradiance. The energy level was about 4.65% of total irradiance. Diurnal variation of UVB was in the form of a steeper bell curve due to the absorption in the air mass. UVB energy to solar total irradiance was about 0.07%. Photodegradation characteristics of two disperse dyestuffs were investigated on the basis of solar radiant energy. A UVA fluorescent lamp was applied to examine the fading characteristics to find the wavelength dependency. As a result, nylon dyeings were less lightfast by a factor of about 6 and 13 for C I Disperse Blue 27 and C I Disperse Blue 165, respectively, compared with polyester on the radiant energy basis. Visible light, as well as UVA, radiation contribute to fading of C I Disperse Blue 165 whereas UVA mostly cause the fading of C I Disperse Blue 27.

Permittivity measurement of thermoplastic composites at elevated temperature.

The material properties of greatest importance in microwave processing of a dielectric are the complex relative permittivity epsilon = epsilon'-jepsilon", and the loss tangent, tan delta = epsilon"/epsilon'. This paper describes two convenient laboratory based methods to obtain epsilon', epsilon" and hence tan delta of fibre-reinforced thermoplastic (FRTP) composites. One method employs a microwave network analyzer in conjunction with a waveguide transmission technique, chosen because it provides the widest possible frequency range with high accuracy. The values of the dielectric constant and dielectric loss of glass fibre reinforced (33%) low density polyethylene, LDPE/GF (33%), polystyrene, PS/GF (33%), and Nylon 66/GF (33%), were obtained. Results are compared with those obtained by another method using a high-temperature dielectric probe.

Reusing nylon membranes for radioactive hybridizations.

We describe a procedure for recycling nylon hybridization membranes, enabling their repeated use for radioactive Southern hybridization analysis of different DNA samples. Following hybridization and probe removal, nylon membranes containing covalently linked DNAs were treated with 0.55% sodium hypochlorite. This destroyed the DNA, thereby preventing it from participating in further hybridization and enabling the membranes to be used subsequently for binding new DNA samples. With this procedure, we were able to reuse a single membrane as many as 13 times, with no detectable loss in signal. This method was shown to be effective for membranes supplied by three different manufacturers.

Potential of an antibacterial ultraviolet-irradiated nylon film.

The antibacterial effectiveness of an ultraviolet-irradiated nylon 6, 6 film was investigated for potential use as a food-packaging material to reduce the surface microbial contamination of foods. The film-surface analyses showed that UV irradiation induced conversion of surface amide groups to amines. Irradiation also increased the dimensional scale of the film surface topography (depth of valleys) approximately 5-fold on the scale of nanometers. The irradiated nylon demonstrated antagonistic activity against Staphylococcus aureus 25923 and Escherichia coli TV1058 with 4.5 and 6 log reductions, respectively, of an initial population of 10(6) cfu mL(-1). The irradiated nylon was ineffective against Pseudomonas fluorescens 13525 and Enterococcus faecalis 19433 under similar conditions. The film demonstrated increased antimicrobial activity against S. aureus 25923 with increasing temperatures up to 45 degrees C, the highest temperature tested. Protein and salt inhibited the antibacterial nature of the irradiated film. Amines in solution (4.31 x 10(-8) M; the calculated equivalent of amines on the film) killed at least 1 x 10(4) cfu mL(-1) E. coli TV1058, and 4. 31 x 10(-7) M amines killed up to 1 x 10(7) cfu mL(-1) E. coli TV1058. The amines in solution required similar exposure time to the bacteria for population reduction as was observed with the irradiated film.

Argon laser suture lysis with different suture materials. An experimental study.

In an in vitro study, 10/0 nylon was found to require a significantly lower laser energy density to produce suture lysis following a single shot than either 10/0 Dacron or 10/0 prolene. Nylon and Dacron monofilament sutures ruptured at reproducible energy levels without significant observable changes at subthreshold irradiation. Prolene, however, was observed to stretch at energy levels below the lysis threshold, under the standard tension produced by a weight of 0.36 (SD 0.02) g. This feature may be of value when performing laser treatment to trabeculectomy flap sutures in the early postoperative period.

Ultraviolet shadowing nucleic acids on nylon membranes.

We describe a method for the direct visualization of nucleic acids on nylon membranes. Nylon is weakly fluorescent under short wave ultraviolet light allowing membrane-bound nucleic acids to be detected with a sensitivity of 10 ng. This procedure involves no staining or destaining of the gels prior to transfer, does not require duplicate sample lanes or blots, and does not interfere with transfer of the nucleic acid to the membrane or subsequent hybridization.

Rapid transfer of DNA from agarose gels to nylon membranes.

The unique properties of nylon membranes allow for dramatic improvement in the capillary transfer of DNA restriction fragments from agarose gels (Southern blotting). By using 0.4 M NaOH as the transfer solvent following a short pre-treatment of the gel in acid, DNA is depurinated during transfer. Fragments of all sizes are eluted and retained quantitatively by the membrane; furthermore, the alkaline solvent induces covalent fixation of DNA to the membrane. The saving in time and materials afforded by this simple modification is accompanied by a marked improvement in resolution and a ten-fold increase in sensitivity of subsequent hybridization analyses. In addition, we have found that nylon membrane completely retains native (and denatured) DNA in transfer solvents of low ionic strength (including distilled water), although quantitative elution of DNA from the gel is limited to fragments smaller than 4 Kb. This property can be utilized in the direct electrophoretic transfer of native restriction fragments from polyacrylamide gels. Exposure of DNA to ultraviolet light, either in the gel or following transfer to nylon membrane, reduces its ability to hybridize.