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Lipid-porphyrin conjugates are considered nowadays as promising building blocks for the conception of drug delivery systems with multifunctional properties such as photothermal therapy (PTT), photodynamic therapy (PDT), phototriggerable release, photoacoustic and fluorescence imaging. For this aim, we have recently synthesized a new lipid-porphyrin conjugate named PhLSM. This was obtained by coupling pheophorbide-a (Pheo-a), a photosensitizer derived from chlorophyll-a, to egg lyso-sphingomyelin. The pure PhLSMs were able to self-assemble into vesicle-like structures that were however not stable and formed aggregates with undefined structures due to the mismatch between the length of the alkyl chain in sn-1 position and the adjacent porphyrin. Herein, stable PhLSMs lipid bilayers were achieved by mixing PhLSMs with cholesterol which exhibits a complementary packing parameter. The interfacial behavior as well as the fine structures of their equimolar mixture was studied at the air/buffer interface by the mean of Langmuir balance and x-ray reflectomerty (XRR) respectively. Our XRR analysis unraveled the monolayer thickening and the increase in the lateral ordering of PhLSM molecules. Interestingly, we could prepare stable vesicles with this mixture that encapsulate hydrophilic fluorescent probe. The light-triggered release kinetics and the photothermal conversion were studied. Moreover, the obtained vesicles were photo-triggerable and allowed the release of an encapsulated cargo in an ON-OFF fashion., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Bacterial spores are important in food processing due to their ubiquity, resistance to high temperature and chemical inactivation. This work aims to study the effect of ultraviolet C (UVC) on the spores of Bacillus subtilis and Bacillus velezensis at a molecular and individual level to guide in deciding on the right parameters that must be applied during the processing of liquid foods. The spores were treated with UVC using phosphate buffer saline (PBS) as a suspension medium and their lethality rate was determined for each sample. Purified spore samples of B. velezensis and B. subtilis were treated under one pass in a UVC reactor to inactivate the spores. The resistance pattern of the spores to UVC treatment was determined using dipicolinic acid (Ca-DPA) band of spectral analysis obtained from Raman spectroscopy. Flow cytometry analysis was also done to determine the effect of the UVC treatment on the spore samples at the molecular level. Samples were processed for SEM and the percentage spore surface hydrophobicity was also determined using the Microbial Adhesion to Hydrocarbon (MATH) assay to predict the adhesion strength to a stainless-steel surface. The result shows the maximum lethality rate to be 6.5 for B. subtilis strain SRCM103689 (B47) and highest percentage hydrophobicity was 54.9% from the sample B. velezensis strain LPL-K103 (B44). The difference in surface hydrophobicity for all isolates was statistically significant (P < 0.05). Flow cytometry analysis of UVC treated spore suspensions clarifies them further into sub-populations unaccounted for by plate counting on growth media. The Raman spectroscopy identified B4002 as the isolate possessing the highest concentration of Ca-DPA. The study justifies the critical role of Ca-DPA in spore resistance and the possible sub-populations after UVC treatment that may affect product shelf-life and safety. UVC shows a promising application in the inactivation of resistant spores though there is a need to understand the effects at the molecular level to design the best parameters during processing., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Due to their excellent biocompatibility and biodegradability, natural hydrogels are highly demanded biomaterials for biomedical applications such as wound dressing, tissue engineering, drug delivery or three dimensional cell culture. Highly energetic electron irradiation up to 10 MeV is a powerful and fast tool to sterilize and tailor the material's properties. In this study, electron radiation treatment of agarose hydrogels was investigated to evaluate radiation effects on physical, structural and chemical properties. The viscoelastic behavior, surface hydrophilicity and swelling behavior in a range of typical sterilization doses of 0 kGy to 30 kGy was analyzed. The mechanical properties were determined by rheology measurements and decreased by more than 20% compared to the initial moduli. The number average molecular weight between crosslinks was estimated based on rubber elasticity theory to judge on the radiation degradation. In this dose range, the number average molecular weight between crosslinks increased by more than 6%. Chemical structure was investigated by FTIR spectroscopy to evaluate the radiation resistance of agarose hydrogels. With increasing electron dose, an increasing amount of carbonyl containing species was observed. In addition, irradiation was accompanied by formation of gas cavities in the hydrogels. The gas products were specified for CO 2 , CO and H 2 O. Based on the radiolytic products, a radiolysis mechanism was proposed. Electron beam treatment under high pressure conditions was found to reduce gas cavity formation in the hydrogels., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

The objective of this work was to investigate the influence of different gamma ray dosages (5, 10, and 10 kGy) on the structural, mechanical, surface and barrier properties of chitosan (Ch) based nanocomposite film. The results showed gamma irradiation caused an increase in the surface hydrophobicity, water vapor permeability and sensitivity of films to water and also, yellowness and opacity of films increased, simultaneously. By increasing the irradiation doses up to 10 kGy, the mechanical properties of Ch/BCNC film was significantly enhanced. As observed by FTIR spectra, no change occurred in the chemical functional groups of the films during irradiation. XRD studies confirmed that crystallinity of films was increased after irradiation. The nanocomposite film irradiated by 10 kGy had the highest thermal stability. In conclusion, gamma radiation can be considered as a safe method for sterilization of foods and modification of Ch/BCNC film properties., (Copyright © 2020. Published by Elsevier Ltd.)

Background: Treating a titanium or titanium alloy implant with ultraviolet (UV) light is known to improve its associated cell growth and osseointegration. However, little is known about the effect of UV irradiation on hydroxyapatite (HA), which is also used frequently in orthopaedic and dental surgery. Here we examined the effect of UV irradiation on the hydrophilicity of HA, and on its osteoconduction ability in rats., Methods: HA implants of low and high porosity were treated with UV light, and photofunctionalisation was assessed by the contact angle of a water drop on the surface. HA implants were also inserted into rat femurs, and the rats were killed 2 or 4 weeks later. The bone volume and bone area ratio were calculated from microcomputed tomography and histological data., Results: The contact angle of a water drop on HA implants of both porosities was significantly reduced after UV irradiation. In the rat femurs, there was no significant difference in the bone volume between the UV light-treated and control implants at 2 or 4 weeks. The bone area ratio for the UV light-treated versus control implants was significantly increased at 2 weeks, but there was no significant difference at 4 weeks., Conclusions: The surface of UV-irradiated HA disks was hydrophilic, in contrast to that of non-irradiated HA disks. Photofunctionalisation accelerated the increase in the bone area ratio in the early healing stage. This technology can be applied to surgical cases requiring the early fusion of bone and HA.

γS-crystallin, a crucial structural lens protein, plays an important role in maintaining lens transparency through its solubility and stability. The S39C mutation, a proven pathogenic mutation involved in congenital cataract, resulted in progressive cataract in adolescents. In this study, using biophysical methods, we thoroughly investigated the effects of the S39C mutation on the γS-crystallin structure, stability and propensity for aggregations. The data from spectroscopy analyses did not reveal an effect of the S39C mutation on the native structure of monomeric γS-crystallin. However, when faced with oxidative conditions, the S39C mutation prevented γS-crystallin from forming stable disulfide-linked dimers and remarkably increased hydrophobicity and the propensity to aggregate and precipitate. Under UV irradiation, heat shock, and GdnHCl-induced denaturation, the S39C mutant tended to aggregate and was prone to form more deleterious aggregates than the wild type protein. Therefore, the S39C mutation significantly increased the sensitivity of γS-crystallin to environmental stress. However, the addition of αA-crystallin and lanosterol did not change the tendency of the mutant to aggregate. According to molecular dynamic (MD) simulations, the S39C mutation had little effect on the secondary or tertiary structures of monomeric γS-crystallin but disrupted the disulfide-linked structure of the γS-crystallin dimer. The cleavage of this bond might largely reduce the structural stability of γS-crystallin. The significant decrease in the structural stability along with the increasing aggregation tendency under environmental stress might be the major causes of progressive juvenile onset cataracts induced by the S39C mutation., Competing Interests: Declaration of competing interest No benefits in any form have been received or will be received from a commercial party related directly or indirectly to the subject of this article. All authors declare no conflict of interest., (Copyright © 2020 Elsevier Inc. All rights reserved.)

Soluble microneedles (MNs) of four different hydrophilic polymers namely sodium carboxymethyl cellulose ( CMC), polyvinylpyrrolidone (PVP) K30, PVP K90 and sodium hyaluronate (HU) were fabricated by mold casting technique. When exposed to gamma radiation, a dose of 25 kilogray (kGy) was found to render the microneedle (MN) sterile. However, CMC was found to form MNs with poor mechanical properties, whereas PVP K30 MNs were drastically deformed upon exposure to applied dose as observed in bright field microscopy. Scanning electron microscopy (SEM) revealed that morphology of PVP K90 and HU MNs were not significantly affected at the applied dose. The appearances of characteristic peaks of irradiated MNs of PVP K90 and HU in Fourier-transform infrared spectra suggested structural integrity of the polymers on irradiation. Differential scanning calorimetry (DSC) indicated gamma irradiation failed to alter the glass transition temperature and thus mechanical properties of PVP K90 MNs. However, DSC and Powder X-ray Diffraction (PXRD) conclusively indicated that the degree in crystallinity of HU was substantially reduced on irradiation. In vitro dissolution profiles of sterile PVP K90 and HU MNs were similar to un-irradiated MNs with a similarity factor ( f 2 ) of 64 and 54, respectively. In vivo dissolution studies in human subjects indicated that sterile MNs of PVP K90 and HU exhibited dissolution of 78.45 ± 1.09 and 78.57 ± 0.70%, respectively, after 20 min. The studies suggested that PVP K90 and HU could be suitable polymers to fabricate soluble MNs as the structural, morphological, microstructural and dissolution properties remained unaltered post γ sterilization.

We have previously described the photoactivated depot (PAD) approach for the light-stimulated release of therapeutic proteins such as insulin. The aim of this method is to release insulin from a shallow dermal depot in response to blood glucose information, using transcutaneous irradiation. Our first approach utilized a photocleavable group that linked insulin to an insoluble but injectable polymer bead. The bead conferred insolubility, ensuring that the injected material stayed at the site of injection, until light cleaved the link, and allowed insulin to be absorbed systemically. While this proved to be effective, the use of a polymer to ensure insolubility introduces two major design problems: (1) low concentration of insulin, as a majority of the material is composed of polymer, and (2) upon release of the insulin, the polymer has to be cleared from the system. To address these two problems, in this work, we have pursued "hydrophobic tags", photocleavable small nonpolar molecules that confer insolubility to the modified insulin prior to irradiation without the bulk or need for biodegradation required of polymers. We developed a combined solid- and solution-phase synthetic approach that allowed us to incorporate a range of small nonpolar moieties, including peptides, into the final depot materials. The resulting materials are >90% w/w insulin and have sharply decreased solubilities relative to unmodified insulin (≤1000 × lower). We demonstrated that they can be milled into low micron-sized particles that can be readily injected through a 31G needle. These suspensions can be prepared at an effective concentration of 20 mM insulin, a concentration at which 120 μL contains 7 days of insulin for a typical adult. Finally, upon photolysis, the insoluble particles release soluble, native insulin in a predictable fashion. These combined properties make these new modified insulins nearly ideal as candidates for PAD materials.

Background: Ovalbumin (OVA), a protein with excellent nutritional and processing properties, is the major allergen of hen egg white. High-intensity ultrasound treatment increases the immunoglobulin (Ig)G and IgE binding abilities by unfolding the conformational structure of OVA. This may allow a modification of the IgG and IgE binding of OVA by combining high-intensity ultrasound with other methods, such as glycation, thus representing a promising method for the improvement of protein properties., Results: Glycation with mannose (M) after ultrasound pretreatment at 0-600 W significantly reduced the IgG and IgE binding abilities and dramatically enhanced the antioxidant activity of OVA-M conjugates, with the lowest values of IgG and IgE binding and highest values of antioxidant capacity observed at 600 W. Polyacrylamide gel electrophoresis showed that the molecular weight of OVA-M conjugates with ultrasound pretreatment increased more than non-pretreatment sample, implying that ultrasound pretreatment promoted glycation. The α-helix content and ultraviolet absorption of OVA were observably increased, whereas β-sheet content, intrinsic fluorescence and surface hydrophobicity were notably decreased, indicating that the tertiary and secondary structures of OVA were markedly changed., Conclusion: High-intensity ultrasound pretreatment can be conducive to reducing the binding abilities of IgG and IgE and enhancing the antioxidant activity of OVA-M conjugates. Therefore, glycation combined with high-intensity ultrasound pretreatment might be a promising method for producing hypo-allergenic and high-antioxidant OVA products. © 2018 Society of Chemical Industry., (© 2018 Society of Chemical Industry.)

Objective: This study aimed to investigate the physical relation and mechanism of bactericidal activity on pathogenic E. coli by ultrasonic field with whey protein isolate (WPI)., Methods: Ultrasound treatment was performed under the conditions of intensity at 65 W/cm 2 , pulse duty ratio at 0.5 for 0-15 min with WPI concentration ranged from 0 to 10%. Viscosity, granularity, surface hydrophobicity, free radical scavenging activity, and thermal denaturation were assessed by rotational viscometer, Malvern Mastersizer 2000 particle size analyzer, fluorescent probe ANS method, DPPH method, and differential scanning calorimetry, respectively., Results: The thermal denaturation of WPI was not altered by ultrasound field, but the viscosity of WPI was increased upon 10 min treatment. Additionally, its ability to scavenge free radicals and hydrophobicity were increased. The result also showed that the bacteria viability was improved by WPI during ultrasound treatment. However, the WPI protection was decreased by the prolonged treatment., Conclusion: Ultrasound treatment resulted in the increasing of the viscosity, free radicals scavenging activity and hydrophobicity of WPI which led to reduced bactericidal activity on E. coil, while WPI protection was disintegrated by prolonged treatment., (Copyright © 2018. Published by Elsevier Ltd.)

Background: In order to investigate the influence of non-thermal effects of microwaves on the flavour of fish and meat products, the G-actin of grass carp in ice baths was exposed to different microwave powers (0, 100, 300 or 500 W); the surface hydrophobicity, sulfhydryl contents, secondary structures and adsorption capacity of G-actin to ketones were determined., Results: As microwave power increased from 0 to 300 W, the surface hydrophobicity, total and reactive sulfhydryls increased; α-helix, β-sheet and random coil fractions turned into β-turn fractions. As microwave power increased from 300 to 500 W, however, hydrophobicity and sulfhydryl contents decreased; β-turn and random coil fractions turned into α-helix and β-sheet fractions. The tendencies of adsorbed capacity of ketones were similar to hydrophobicity and sulfhydryl contents., Conclusion: The increased adsorbing of ketones could be attributed to the unfolding of secondary structures by revealing new binding sites, including thiol groups and hydrophobic binding sites. The decreased binding capacity was related to the refolding and aggregation of protein. The results suggested that microwave powers had obvious effects on the flavour retention and proteins structures in muscle foods. © 2017 Society of Chemical Industry., (© 2017 Society of Chemical Industry.)

The research investigates the mechanism of microwave radiation effects on biological characteristics and structural-dynamic parameters of a sensor bioluminescence system. The research objects are a sterile growth medium (fish meal hydrolisate) and a bacterial culture. It has been established that irradiation causes changes of the growth medium spectral properties within the range of 200-350nm. Changes take place in the intensity and character of luminescence, as well as in relaxation parameters of nuclear magnetic resonance, growth characteristics of the bacterial culture, its cellular morphology and surface topology. The research results enabled us to establish the mechanisms of primary molecular processes that occur when the bacterial culture is exposed to microwave radiation. Transformation of the dynamic-structural state of adsorbed water phases on biopolymer surfaces has been found to be the key factor in the mechanism of microwave effects on living and water-containing objects., (Copyright © 2017 Elsevier B.V. All rights reserved.)

In this paper, we present a disposable inkjet dispenser platform technology and demonstrate the Lab-on-a-Printer concept, an extension of the ubiquitous Lab-on-a-Chip concept, whereby microfluidic modules are directly integrated into the printhead. The concept is demonstrated here through the integration of an inkjet dispenser and a microfluidic mixer enabling control over droplet composition from a single nozzle in real-time during printing. The inkjet dispenser is based on a modular design platform that enables the low-cost microfluidic component and the more expensive actuation unit to be easily separated, allowing for the optional disposal of the former and reuse of the latter. To limit satellite droplet formation, a hydrophobic-coated and tapered micronozzle was microfabricated and integrated with the fluidics to realize the dispenser. The microfabricated devices generated droplets with diameters ranging from 150-220 μm, depending mainly on the orifice diameter, with printing rates up to 8000 droplets per second. The inkjet dispenser is capable of dispensing materials with a viscosity up to ∼19 mPa s. As a demonstration of the inkjet dispenser function and application, we have printed type I collagen seeded with human liver carcinoma cells (cell line HepG2), to form patterned biological structures.

Temperature-responsive oxazoline-based polymer brushes have gained increased attention as biocompatible surfaces. In aqueous environment, they can be tuned between hydrophilic and hydrophobic behavior triggered by a temperature stimulus. This transition is connected with changes in molecule-solvent interactions and results in a switching of the brushes between swollen and collapsed states. This work studies the temperature-dependent interactions between poly(2-oxazoline) brushes and water. In detail, thermoresponsive poly(2-cyclopropyl-2-oxazoline), nonresponsive hydrophilic poly(2-methyl-2-oxazoline), as well as a copolymer of the two were investigated with in situ infrared ellipsometry. Focus was put on interactions of the brushes' carbonyl groups with water molecules. Different polymer-water interactions could be observed and assigned to hydrogen bonding between C=O groups and water molecules. The switching behavior of the brushes in the range of 20-45 °C was identified by frequency shifts and intensity changes of the amide I band.

The applications of hierarchical micro/nano-structures, which possess properties of two-scale roughness, have been studied in various fields. In this study, hierarchical periodic micro/nano-structures were fabricated on nitinol, an equiatomic Ni-Ti alloy, using a femtosecond laser for the surface modification of intravascular stents. By controlling the laser fluence, two types of surfaces were developed: periodic nano- and micro/nano-structures. Evaluation of water contact angles indicated that the nano-surface was hydrophilic and the micro/nano-surface was hydrophobic. Endothelial cells aligned along the nano-structures on both surfaces, whereas platelets failed to adhere to the micro/nano-surface. Decorrelation between the responses of the two cell types and the results of water contact angle analysis were a result of the pinning effect. This is the first study to show the applicability of hierarchical periodic micro/nano-structures for surface modification of nitinol., (Copyright © 2015. Published by Elsevier B.V.)

AtTDX, a thioredoxin-like plant-specific protein present in Arabidopsis is a thermo-stable and multi-functional enzyme. This enzyme is known to act as a thioredoxin and as a molecular chaperone depending upon its oligomeric status. The present study examines the effects of γ-irradiation on the structural and functional changes of AtTDX. Holdase chaperone activity of AtTDX was increased and reached a maximum at 10 kGy of γ-irradiation and declined subsequently in a dose-dependent manner, together with no effect on foldase chaperone activity. However, thioredoxin activity decreased gradually with increasing irradiation. Electrophoresis and size exclusion chromatography analysis showed that AtTDX had a tendency to form high molecular weight (HMW) complexes after γ-irradiation and γ-ray-induced HMW complexes were tightly associated with a holdase chaperone activity. The hydrophobicity of AtTDX increased with an increase in irradiation dose till 20 kGy and thereafter decreased further. Analysis of the secondary structures of AtTDX using far UV-circular dichroism spectra revealed that the irradiation remarkably increased the exposure of β-sheets and random coils with a dramatic decrease in α-helices and turn elements in a dose-dependent manner. The data of the present study suggest that γ-irradiation may be a useful tool for increasing holdase chaperone activity without adversely affecting foldase chaperone activity of thioredoxin-like proteins.

Ultraviolet (UV) light treatment of implant surfaces has been demonstrated to enhance their bioactivity significantly. This study examined the effect of UV treatment of different zirconia surfaces on the response of primary human alveolar bone-derived osteoblasts (PhABO). Disks of two zirconia-based materials with two different surface topographies (smooth, roughened) were exposed to UV light. Qualitative and quantitative assessment of PhABO on zirconia surfaces, by means of immunofluorescence, scanning electron microscopy and DNA quantification at 4 and 24 h revealed a higher number of initially attached osteoblasts on UV-treated surfaces. Cell area and perimeter were significantly larger on all UV-treated surfaces (p<0.05). The proliferation activity was significantly higher on both roughened UV-treated surfaces than on untreated samples at day 3 of culture (p<0.05). The expression levels of collagen I, osteopontin and osteocalcin at day 14 and alkaline phosphatase activity at day 7 and 14 of culture period were similar among UV-treated and untreated surfaces. Alizarin-Red-Staining at day 21 demonstrated significantly more mineralised nodules on UV-treated samples than on untreated samples. Contact angle measurements and X-ray photoelectron spectroscopy showed that UV light transformed zirconia surfaces from hydrophobic to (super-) hydrophilic (p<0.05) and significantly reduced the atomic percentage of surface carbon. The results showed that UV light pre-treatment of zirconia surfaces changes their physicochemical properties and improves their attractiveness against PhABO, primarily demonstrated by an augmented cell attachment and spreading. This may result in faster healing and better bone-to-implant contact of zirconia implants in vivo following such a pre-treatment.

Background: Poly-ether-ether-ketone (PEEK) has biomechanical and chemical properties that are excellent for biomedical applications; however, PEEK adhesion to bone or chondral tissue proceeds slowly due to poor hydrophilicity and other surface characteristics., Objective: We investigated the structural change, hydrophilicity, and cytocompatibility of a PEEK surface after 172-nm xenon excimer UV-irradiation., Methods: The surface characteristics before and after irradiation were evaluated by contact angle and ATR-FTIR measurements. Mouse osteoblast-like cells (MC3T3-E1) were cultured on PEEK plates and collected after 6, 12 and 24 h for cell adhesion analysis by crystal violet staining (CVS) and scanning electron microscopy (SEM)., Results: UV-irradiation improved PEEK surface hydrophilicity, as indicated by a significant drop in water contact angle (p<0.05). Irradiated PEEK showed additional peaks around 3370 cm-1 and 1720 cm-1, highlighting the generation of hydroxyl and carbonyl groups. CVS and SEM revealed improved adhesion to the PEEK surface after UV-irradiation., Conclusion: Our results suggest that 172-nm UV-irradiated PEEK may be used in biomedical applications that require good cell adhesion.

Purpose: The new technology of photofunctionalization with ultraviolet (UV) light for titanium implants has earned considerable attention. We hypothesized that UV light treatment would enhance bone formation on titanium mesh., Materials and Methods: We implemented in vitro and in vivo experiments to examine the effectiveness of UV treatment for bone formation on titanium mesh surfaces. Titanium mesh for medical use was prepared as samples, which were autoclaved and stored under dark ambient conditions for 4 weeks. UV treatment was performed for 12 minutes. Carbon contamination, hydrophilicity, and protein adhesion of the titanium mesh surface were examined in an in vitro model. Bone tissue formation around the titanium mesh was observed in a rat femur bone model. The Mann-Whitney U test was used to examine differences between the untreated and UV-treated groups. P values of < .05 were considered significant., Results: UV-mediated photofunctionalization reduced carbon contamination rates on the untreated titanium mesh surfaces. The hydrophobic surface of the untreated titanium mesh became superhydrophilic after UV-mediated photofunctionalization (P < .01). The amount of protein adsorbed onto the titanium was 1.5 to 3 times greater on the photofunctionalized titanium mesh surfaces than on the untreated titanium mesh surfaces (P < .01). In the animal experiment, the newly formed bone on the UV-treated titanium mesh was approximately 2.5 times greater than that on the untreated mesh (P < .05)., Conclusions: UV-mediated photofunctionalization is effective, as demonstrated by the enhanced bone tissue formation on the titanium mesh. Future studies will focus on bone augmentation using an UV-mediated photofunctionalized titanium implant and mesh., (Copyright © 2014 American Association of Oral and Maxillofacial Surgeons. Published by Elsevier Inc. All rights reserved.)

Peanut protein isolate (PPI) was glycated with glucomannan through classical heating or ultrasound treatment in this work. The physicochemical properties of PPI-glucomannan conjugates prepared by ultrasound treatment were compared to those prepared by classical heating. Compared with classical heating, ultrasound treatment could accelerate the graft reaction between PPI and glucomannan and improve the concentration of available free amino groups of PPI. Solubility and emulsifying properties of the conjugates obtained by ultrasound treatment were both improved as compared to those obtained by classical heating and native PPI. Decreases of lysine and arginine contents during the graft reaction indicated that these two amino acid residues attended the covalent linkage between PPI and glucomannan. Structural feature analyses suggested that conjugates obtained by ultrasound treatment had less α-helix, more β-structures and random coil, higher surface hydrophobicity and less compact tertiary structure as compared to those obtained by classical heating and native PPI., (Copyright © 2014 Elsevier B.V. All rights reserved.)

Self-healing of the superhydrophobic cotton fabric (SCF) obtained by the radiation-induced graft polymerization of lauryl methacrylate (LMA) and n-hexyl methacrylate (HMA), can be achieved by ironing. Through the steam ironing process, the superhydrophobicity of the SCFs will be regenerated even after the yarns are ruptured during the abrasion test under a load pressure of 44.8 kPa. SCFs made from LMA grafted cotton fabric can ultimately withstand at least 24,000 cycles of abrasion with periodic steam ironing. The FT-IR microscope results show that the migration of the polymethacrylates graft chains from the interior to the surface is responsible for the self-healing effect.

Purpose: After placement, titanium dental implants are conditioned by blood and tissue fluid. These initial processes are affected by the hydrophilicity of the implant. The hydrophilicity of titanium dioxide (TiO2) can be increased by ultraviolet (UV)-C irradiation. Anodic oxidation is an electrochemical treatment used to form TiO2 layers that are characterized by their thickness, roughness, and porosity on the surface of titanium implants. These oxide layers increase implant durability and performance. Therefore, the aim of this study was to investigate the effect of UV-C irradiation on the anodized titanium surface and the resultant tissue response., Materials and Methods: Twenty-five titanium disks and 56 screw-type implants were fabricated of commercially pure titanium and anodized. The samples were divided into a control group (anodized) and a test group (anodized and UV-C irradiated with a bactericidal UV sterilizer for 24 hours just prior to experimentation). The surface characteristics of the disks, including roughness, crystal phase of the oxide layer, chemical composition, and water contact angle, were then evaluated. Implants were placed into rabbit tibiae, and histomorphometric analysis was performed after healing periods of 4 and 12 weeks. The results were compared between groups., Results: The surface topography and phase of the oxide layer were not significantly different between test and control groups. Carbon surface impurities were noticeably decreased after UV-C irradiation, and water contact angle measurements were significantly lower (P < .001). After a healing period of 4 weeks, test implants showed higher values for both bone-to-implant contact and the amount of bone in the thread area of the implant (P < .01). No significant differences between groups were found for either histomorphometric measurement after 12 weeks., Conclusions: UV-C irradiation of an anodized titanium implant, accomplished via a bactericidal UV sterilizer, promoted an early bone response in rabbit tibiae.

There have been serious concerns about polybromodiphenyl ethers (PBDEs) in the environment because of their global distribution and bioaccumulation. Owing to strong hydrophobicity of PBDEs, the regular photocatalytic system, in which the substrate is solvated in the bulk solution, is not applicable to the removal of the PBDEs in water. In this work, the photocatalytic reduction degradation of decabromodiphenyl ether (BDE209), the most-used PBDEs, was investigated in aqueous system, by pre-adsorbing it on the surface of photocatalyst. It was found that the preloaded BDE209 underwent efficient reductive debromination in aqueous system under irradiation with wavelength larger than 360 nm in the presence of electron donors such as methanol. Our experiments further show that such a preloaded system exhibits different characteristics from that in the organic solution. The meta-debrominated intermediate is predominant in the present system, while the ortho-debrominated one is the main nona-BDE products in the organic solution. In addition, different from other photocatalytic system, the pH has little effect on the photocatalytic reaction. We propose that these differences are originated from the formation of overlayer of hydrophobic BDE209 to limit the motion of BDE209 and the access of water and H(+)/OH(-) to the TiO(2) surface., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

Photocrosslinkable methacrylated hyaluronic acid (HA) was prepared and incorporated into model conventional and silicone hydrogel contact lenses as an internal wetting agent. The molecular weight of the HA, the degree of methacrylation as well as the amount (0.25 to 1.0 wt %) incorporated were varied. The HA-containing hydrogels were analyzed using a variety of techniques including water contact angles, equilibrium water content (EWC), and lysozyme sorption. The presence of HA could be detected in the materials using X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy-attenuated total reflectance. The materials containing methacrylated HA had improved hydrophilicity and reduced lysozyme sorption. Effects of modified HA on EWC were dependent upon the materials but generally increased water uptake. Increased mobility of the HA associated with a lower molecular weight and lower degree of methacrylation was found to be more effective in improving hydrophilicity and decreasing lysozyme sorption than the less mobile HA. All results found suggest that photocrosslinkable HA has significant potential in contact lens applications., (Copyright © 2011 Wiley Periodicals, Inc.)

Nanoparticles consisting of a photoreactive polymer able to radically switch its hydrophobicity are successfully prepared by miniemulsion polymerization. Irradiation with UV light causes degradation of the particles where at complete dissolution is achieved by changing the initial hydrophobic photoresist polymer into hydrophilic poly(methacrylic acid). Incorporation of the fluorescence-sensitive Nile red serves as a solvatochromic probe to study the particle degradation. Diffusion of either Nile red out from or water into the former hard spherical nanoparticles is studied and not only renders the described material an ideal system for applications, where in situ dissolution of nanoparticles may be needed, but also bears the additional advantage of performing controlled burst release., (Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

In this study, degradation of humic acid (HA) via photoelectrocatalysis (PEC) process and corresponding disinfection byproduct formation potential (DBPFP) were investigated. Particularly, structure variation and subsequent DBPFP of HA during PEC treatment were correlated. The PEC process was found to be effective in reducing dissolved organic carbon concentration by 75.0% and UV absorbance at 254 nm by 92.0%. Furthermore, 90.3% of haloacetic acids formation potential and 89.8% of trihalomethanes formation potential were reduced within 180 min. Based on molecular weight and resin fraction results, it was demonstrated that HA with large aromatic, hydrophobic and long aliphatic chain organics were transformed into small and hydrophilic organics during PEC process. Combined with the fourier transform infrared spectra and (13)C nuclear magnetic resonance spectra analysis of HA fractions, it was concluded that phenolic hydroxyl and conjugated double bonds tended to be attacked by hydroxyl radicals during PEC process; these groups were reactive with chlorine to produce disinfection byproducts (DBP), especially trihalomethane and trichloroacetic acid. By contrast, amino, carboxyl and alcoholic hydroxyl groups were relatively difficult to be oxidized during PEC process; these groups had the potential to form dichloroacetic acid during chlorination. Results of these studies confirmed that PEC process was a safe and effective technique to decrease DBP formation significantly in water treatment plant., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

This study addresses the control of the biological capabilities of titanium through specific nanosurface features and its potential modulation by UV photofunctionalization. Rat bone marrow derived osteoblasts were cultured on titanium disks with micropits alone, micropits with 100 nm nodules, micropits with 300 nm nodules, or micropits with 500 nm nodules, with or without UV treatment. After a 24 h incubation protein adsorption, as well as the attachment, retention, and spread of osteoblasts were examined in correlation with the topographical parameters of the titanium substrates. Each of the biological events was governed by a different set of multiple surface topographical factors with a distinctive pattern of regulation. For instance, without UV treatment the protein adsorption and cell attachment capability of titanium substrates increased linearly with increasing average roughness (Ra) and surface area of titanium disks, but increased polynomially with increasing nanonodule diameter. The cell retention capability increased polynomially with increasing nanonodular diameter and Ra, but increased linearly with increasing surface area. Consequently, the micropits with 300 nm nodules created the most favorable environment for this initial osteoblast behavior and response. UV treatment of the nanonodular titanium surfaces resulted in considerable enhancement of all biological events. However, the pattern of UV-mediated enhancement was disproportionate; exponential and overriding effects were observed depending upon the biological event and topographical parameter. As an example of overriding enhancement, the cell retention capability, which fluctuated with changes in various topographical parameters, became invariably high after UV treatment. The present data provide a basis for understanding how to optimize nanostructures to create titanium surfaces with increased biological capabilities and uncover a novel advantage of UV photofunctionalization of titanium substrates that synergistically increases its nanotopography enhanced biological capabilities whereby most of the initial biological events of osteoblasts were overwhelmingly enhanced beyond a simple proportional increase., (Copyright © 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.)

Recently, it was reported that ultraviolet (UV) illumination could trigger the unfolding of proteins by disrupting the buried disulfide bonds. However, the consequence of such unfolding has not been adequately evaluated. Here, we report that unfolded chicken egg white lysozyme (CEWL) triggered by UV illumination can form uniform globular aggregates as confirmed by dynamic light scattering, atomic force microscopy, and transmission electron microscopy. The assembling process of such aggregates was also monitored by several other methods, such as circular dichroism, fluorescence spectroscopy, mass spectrometry based on chymotrypsin digestion, ANS-binding assay, Ellman essay, and SDS-PAGE. Our finding is that due to the dissociation of the native disulfide bonds by UV illumination, CEWL undergoes drastic conformational changes resulting in the exposure of some hydrophobic residues and free thiols. Subsequently, these partially unfolded molecules self-assemble into small granules driven by intermolecular hydrophobic interaction. With longer UV illumination or longer incubation time, these granules can further self-assemble into larger globular aggregates. The combined effects from both the hydrophobic interaction and the formation of intermolecular disulfide bonds dominate this process. Additionally, similar aggregation behavior can also be found in other three typical disulfide-bonded proteins, that is, α-lactalbumin, RNase A, and bovine serum albumin. Thus, we propose that such aggregation behavior might be a general mechanism for some disulfide-bonded proteins under UV irradiation., (Copyright © 2011 Wiley-Liss, Inc.)

We demonstrate a strategy for using an optical stimulus to trigger the dissociation of block copolymer (BCP) vesicles in aqueous solution. The BCP, comprising hydrophilic poly(ethylene oxide) (PEO) and a block of poly(methacrylic acid) bearing a number of spiropyran methacrylate comonomer units (P(MAA-co-SPMA)), was allowed to firstly self-assemble into large vesicles in aqueous solution at pH=3 with protonated carboxylic acid groups, and then become kinetically stable at pH=8 due to the glassy vesicle membrane of P(MAA-co-SPMA). Fast dissociation of the vesicles was achieved through a cascade of events triggered by UV-induced isomerization from neutral spiropyran to charged merocyanine in the membrane., (Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A series of poly(ethylene glycol)-co-poly(lactide) diacrylate macromers was synthesized with variable PEG molecular weights (10 or 20 kDa) and lactate contents (0 or 6 lactates per end group). These macromers were polymerized to form hydrogels by free radical polymerization using either redox or photochemical initiators. The extent of polymerization was determined by monitoring the compressive modulus of the resulting hydrogels and by quantitative determination of unreacted acrylate after exhaustive hydrolysis of the gel. Polymerization efficiency was found to depend on the lactate content of the macromer, with higher lactate macromers giving more efficient polymerization. For redox-initiated polymerization using ferrous gluconate/t-butyl hydroperoxide initiator, macromers containing approximately six lactate repeats per end group required lower concentrations of initiator to reach high conversion than lactate-free macromers. Photochemical polymerization with α,α-dimethoxy-α-phenylacetophenone (Irgacure 651(®)) was found to be less efficient than redox polymerization, requiring the addition of N-vinyl-2- pyrrolidone (NVP) as a co-monomer to achieve conversions comparable with redox polymerization. When conditions were optimized to provide near complete conversion for all gels, the presence of lactate repeat units in the hydrogel was generally found to reduce swelling and increase the compressive modulus. Calculated values of molecular weight between cross-links (M(c)) and mesh size using Flory-Rehner theory showed that macromer molecular weight had the greatest impact on the network structure of the gel., (Copyright © 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.)

Photopolymerizable (meth)acrylate networks are potentially advantageous biomaterials due to their ability to be formed in situ, their fast synthesis rates and their tailorable material properties. The objective of this study was to evaluate how immersion time in phosphate-buffered saline (PBS) affects the toughness of photopolymerizable methyl acrylate (MA)-co-methyl methacrylate-co-poly(ethylene glycol) dimethacrylate networks containing various concentrations of MA. Stress-strain behavior was determined by performing tensile strain to failure testing after soaking in PBS for different periods (1 day up to 9 months). In tandem, differential scanning calorimetry and PBS content measurements were undertaken at each time point in order to determine whether time-dependent changes in toughness were related to changes in T(g) or PBS absorption. The effect of immersion time on network toughness was shown to be dependent upon composition in a manner related to the viscoelastic state of the polymer upon initial immersion in PBS. The results demonstrate that tough acrylate-based materials may not maintain their toughness after several months in PBS. In addition, decreasing the PBS content by changing the network hydrophobicity resulted in better toughness maintenance after 9 months. The results provide a possible means to toughen various amorphous acrylate-based implant materials that are being explored for load-bearing biomedical applications, beyond the systems considered in this work., (Published by Elsevier Ltd.)

A typical 2-cysteine peroxiredoxin (2-Cys Prx) PaPrx can act alternatively as thioredoxin (Trx)-dependent peroxidase and molecular chaperone in Pseudomonas aeruginosa PAO1. In addition, the functional switch of PaPrx is regulated by its structural change which is dependently induced by stress conditions. In the present study, we examined the effect of gamma ray on structural modification related to chaperone activity of PaPrx. The structural change of PaPrx occupied with gamma ray irradiation (2 kGy) based on polyacrylamide gel electrophoresis (PAGE) analysis and the functional change also began. The enhanced chaperone activity was increased about 3-4 folds at 30 kGy gamma irradiation compared with nonirradiated PaPrx, while the peroxidase activity was significantly decreased. We also investigated the influence of the gamma ray on protein hydrophobicity as related to chaperone function. The exposure of hydrophobic domains reached a peak at 30 kGy gamma ray and then decreased dependently with increasing gamma irradiation. Our results suggest that highly enhanced chaperone activity could be adapted for use in bio-engineering systems and industrial applications such as enzyme stabilization during industrial process (inactivation protection), improvement of useful protein productivity (refolding and secretion) and industrial animal cell cultivation (stress protection).

A decline in CFU of gram-positive and gram-negative bacteria on the surface of UV illuminated TiO2 films (wavelength of 380 nm) is shown. A 29, 45, and 47% decrease in bacterial viability of Staphylococcus aureus, Staphylococcus epidermidis, and Escherichia coli, respectively, was seen following a 12-min exposition. It was first discovered that the reuse of TiO2 films to test a bacterial suspension for viability removes UV-induced bactericidal activity. However, annealing of TiO2 at a temperature above 400 degrees C restores the photoinduced bactericidal activity to its initial state.

The effects of increasing sonication time (60-150min), NaCl (2-18g/l), S(2)O(8)(2-) (2-10mg/l) and 1-butanol (200-600mg/l) concentrations on the destructions of seven polycyclic aromatic hydrocarbons (PAHs) and acute toxicity in a petrochemical industry wastewater in Izmir (Turkey) were investigated. The yields in more hydrophobic PAHs (DahA and BghiP) were as high as in less hydrophobic PAHs (CHR, PHE, PY, BbF and ANT) at 60 degrees C after 150min sonication. The removals in all PAHs increased from 72-78% to 97-99% as the NaCl administration was increased from 1.5 to 12g/l. The degradation efficiency of seven PAHs was enhanced by 36% with 6mg/l S(2)O(8)(2-) after 150min. OH(*) is the major process for complete sonodegradation of less hydrophobic PAHs while pyrolysis is the major process for complete degradation of more hydrophobic PAHs.

Surface modification of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) scaffolds with polyacrylamide was achieved with the aim to improve their hydrophilicity. PHBV scaffolds were prepared using the particle-leaching technique, with a porogen size of 100-200, 200-300, 300-400 and 400-500 mum, respectively. After UV polymerization, the modified PHBV scaffolds had interconnected pores with flaky substances partially filled inside. They had a lower porosity, ranging from 80.3 to 86.6%, and higher density, 0.22-0.25 g/cm(3), than the PHBV scaffolds. Mercury intrusion porosimetry results showed that the pore sizes at the peak volume increased with the increase of porogen sizes for the modified scaffolds. No extensive weight loss of the PHBV was found after 360 days incubation in PBS at 37 degrees C. However, the weight loss of the modified PHBV increased with time before 90 days incubation. After that period, it ranged only between 5 and 7.5%, with the maximum value at 240 days. During 360 days incubation, the pH value of degradation fluid fluctuated between 7.1 and 7.2. Sheep chondrocytes were cultured on the PHBV and modified PHBV scaffolds. Results showed that the modified PHBV scaffolds provided a better surface for chondrocyte adhesion and spread.