Innovative Bio-Based Organic UV-A and Blue Light Filters from Meldrum's Acid.

Faced with the ban of some organic UV filters such as octinoxate or avobenzone, especially in Hawaii, it became essential to offer new alternatives that are both renewable and safe for humans and the environment. In this context, a class of bio-based molecules displaying interesting UV filter properties and great (photo)stability has been developed from Meldrum's acid and bio-based and synthetic p-hydroxycinnamic acids, furans and pyrroles. Moreover, p-hydroxycinnamic acid-based Meldrum's derivatives possess valuable secondary activities sought by the cosmetic industry such as antioxidant and anti-tyrosinase properties. The evaluation of the properties of mixture of judiciously chosen Meldrum's acid derivatives highlighted the possibility to modulate secondary activity while maintaining excellent UV protection. Meldrum's acid derivatives are not only competitive when benchmarked against organic filters currently on the market (i.e., avobenzone), but they also do not exhibit any endocrine disruption activity.

Novel osteoinductive photo-cross-linkable chitosan-lactide-fibrinogen hydrogels enhance bone regeneration in critical size segmental bone defects.

The purpose of this study was to develop and characterize a novel photo-cross-linkable chitosan-lactide-fibrinogen (CLF) hydrogel and evaluate the efficacy of bone morphogenetic protein-2 (BMP-2) containing a CLF hydrogel for osteogenesis in vitro and in vivo. We synthesized the CLF hydrogels and characterized their chemical structure, degradation rate, compressive modulus and in vitro BMP-2 release kinetics. We evaluated bioactivities of the BMP-2 containing CLF hydrogels (0, 50, 100 and 500ngml(-1)) in vitro using W-20-17 preosteoblast mouse bone marrow stromal cells and C2C12 mouse myoblast cells. The effect of BMP-2 containing CLF gels (0, 0.5, 1, 2 and 5µg) on bone formation was evaluated using rat critical size segmental bone defects for 4weeks. Fourier transform infrared spectroscopy spectra and scanning electron microscopy images showed chemical and structural changes by the addition of fibrinogen into the chitosan-lactide copolymer. The incorporation of fibrinogen molecules significantly increased the compressive modulus of the hydrogels. The in vitro BMP-2 release study showed initial burst releases from the CLF hydrogels followed by sustained releases, regardless of the concentration of the BMP-2 over 4weeks. Cells in all groups were viable in the presence of the hydrogels regardless of BMP-2 doses, indicating non-cytotoxicity of hydrogels. Alkaline phosphate activity and mineralization of cells exhibited dose dependence on BMP-2 containing CLF hydrogels. Radiography, microcomputed tomography and histology confirmed that the BMP-2 containing CLF hydrogels prompted neo-osteogenesis and accelerated healing of the defects in a dose-dependent manner. Thus the CLF hydrogel is a promising delivery system of growth factors for bone regeneration.

Electrospinning and crosslinking of low-molecular-weight poly(trimethylene carbonate-co-(L)-lactide) as an elastomeric scaffold for vascular engineering.

The growth of suitable tissue to replace natural blood vessels requires a degradable scaffold material that is processable into porous structures with appropriate mechanical and cell growth properties. This study investigates the fabrication of degradable, crosslinkable prepolymers of l-lactide-co-trimethylene carbonate into porous scaffolds by electrospinning. After crosslinking by γ-radiation, dimensionally stable scaffolds were obtained with up to 56% trimethylene carbonate incorporation. The fibrous mats showed Young's moduli closely matching human arteries (0.4-0.8MPa). Repeated cyclic extension yielded negligible change in mechanical properties, demonstrating the potential for use under dynamic physiological conditions. The scaffolds remained elastic and resilient at 30% strain after 84days of degradation in phosphate buffer, while the modulus and ultimate stress and strain progressively decreased. The electrospun mats are mechanically superior to solid films of the same materials. In vitro, human mesenchymal stem cells adhered to and readily proliferated on the three-dimensional fiber network, demonstrating that these polymers may find use in growing artificial blood vessels in vivo.

Degradation of 1,4-dioxane using advanced oxidation processes.

INTRODUCTION: In the nuclear industry 1,4-dioxane is used as a solvent in liquid scintillation technique for measuring low-energy beta-emitters such as ³H or C¹4 in aqueous media. Improper disposal of 1,4-dioxane can contaminate the ground and surface waters. Conventional wastewater treatment processes like chemical treatment, air stripping, carbon adsorption, and biological treatment are ineffective for the degradation of 1,4-dioxane. METHODS: In the present study, the kinetics of degradation of 1,4-dioxane using advanced oxidation processes viz., H2O2 alone, Fe(II) + H2O2, UV (15 W) + H2O2, UV (15 W) + Fe(II) + H2O2, US (130 KHz) + Fe(II) + H2O2, and sunlight + Fe(II) + H2O2 at pH 3.0 was investigated. The optimization of Fe (II) for the processes using Fe (II) + H2O2 was carried out. CONCLUSIONS: The kinetics of degradation using sunlight + Fe (II) + H2O2 was found to be fastest when compared to the other processes. The degradation was found to follow first-order kinetics. Formation of acidic intermediates was suspected from the observed pH changes during the degradation processes.

Evaluation of tubular poly(trimethylene carbonate) tissue engineering scaffolds in a circulating pulsatile flow system.

Tubular scaffolds (internal diameter approximately 3 mm and wall thickness approximately 0.8 mm) with a porosity of approximately 83% and an average pore size of 116 µm were prepared from flexible poly(trimethylene carbonate) (PTMC) polymer by dip-coating and particulate leaching methods. PTMC is a flexible and biocompatible polymer that crosslinks upon irradiation; porous network structures were obtained by irradiating the specimens in vacuum at 25 kGy before leaching soluble salt particles. To assess the suitability of these scaffolds in dynamic cell culturing for cardiovascular tissue engineering, the scaffolds were coated with a thin (0.1 to 0.2 mm) non-porous PTMC layer and its performance was evaluated in a closed pulsatile flow system (PFS). For this, the PFS was operated at physiological conditions at liquid flows of 1.56 ml/s with pressures varying from 80-120 mmHg at a frequency of 70 pulsations per minute. The mechanical properties of these coated porous PTMC scaffolds were not significantly different than non-coated scaffolds. Typical tensile strengths in the radial direction were 0.15 MPa, initial stiffness values were close to 1.4 MPa. Their creep resistance in cyclic deformation experiments was excellent. In the pulsatile flow setup, the distention rates of these flexible and elastic scaffolds were approximately 0.10% per mmHg, which is comparable to that of a porcine carotid artery (0.11% per mmHg). The compliance and stiffness index values were close to those of natural arteries.?In long-term deformation studies, where the scaffolds were subjected to physiological pulsatile pressures for one week, the morphology and mechanical properties of the PTMC scaffolds did not change. This suggests their suitability for application in a dynamic cell culture bioreactor.

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.

Combined and sequential delivery of bioactive VEGF165 and HGF from poly(trimethylene carbonate) based photo-cross-linked elastomers.

The ability of trimethylene carbonate (TMC) based elastomers to release bioactive vascular endothelial growth factor (VEGF(165)) and hepatocyte growth factor (HGF) separately and in combined and sequential fashions using an osmotic release mechanism was investigated. A TMC-based elastomer was chosen since TMC degrades without producing potentially harmful acidic degradation products, and its mechanical properties can be tailored by copolymerizing with D,L-lactide (DLLA) and epsilon-caprolactone (epsilon-CL) and by controlling the cross-link density. The bioactivities of released VEGF(165) and HGF were assessed using the proliferation of human aortic endothelial (HAEC) and CCL 208 monkey lung epithelial cell lines. VEGF(165) and HGF were lyophilized separately or together with trehalose, rat serum albumin (RSA) and NaCl. No significant elastomer degradation occurred over the initial 8 weeks, during which the bulk of the embedded growth factors were released. The presence of a low concentration of NaCl in the release media did not affect the viability of HAEC and CCL 208 cells. The TMC-based elastomer was able to provide a sustained release of highly bioactive VEGF(165) and HGF for more than 10 days. When released in combination from the same device, VEGF(165) and HGF were released at similar rates. By preparing a dual-layered cylinder, in which VEGF(165) was in the outer layer and HGF in the inner layer, a constant release of VEGF alone was first obtained, followed by overlapping and constant release of the two growth factors after a period of 4days. This study demonstrates the potential of TMC-based elastomers combined with an osmotic mechanism to release acid-sensitive growth factors in bioactive form alone and in combination, in controlled rates and sequences.

Macrophage-mediated erosion of gamma irradiated poly(trimethylene carbonate) films.

A macrophage culture model was used to investigate the erosion of gamma irradiated poly(trimethylene carbonate) (PTMC) films. When the PTMC films were incubated in the culture medium, but physically separated from the cells by a membrane, no erosion occurred. In contrast, when the J774A macrophages were directly cultured on PTMC films, they adhered to the films and were found to have eroded the polymer surface. Macrophages adhered to gamma irradiated poly(epsilon-caprolactone) (PCL) controls as well, but to a lesser extent than to the PTMC films. In this case, no signs of erosion were observed. Human skin fibroblasts cultured on PTMC and PCL films as controls also adhered to the films but did not erode the surfaces. The effect of enzymes and reactive oxygen species that can be secreted by macrophages on the erosion process was assessed using aqueous solutions of cholesterol esterase, lipoprotein lipase, esterase, potassium superoxide, and hydrogen peroxide. The PTMC films eroded in aqueous enzyme solutions as well as in aqueous superoxide solutions. Cholesterol esterase and superoxide anion radicals seem to be most involved in the macrophage-mediated erosion of PTMC. This macrophage culture model is useful in assessing the influence of macrophages on the in vivo biodegradability of polymers and in elucidating the biodegradation mechanisms involved.

A Fenton-like degradation mechanism for 1,4-dioxane using zero-valent iron (Fe0) and UV light.

In this study, the degradation mechanism of 1,4-dioxane using zero-valent iron (Fe0) in the presence of UV light was investigated kinetically. The degradation of 1,4-dioxane in Fe0-only, photolysis, and combined Fe0 and UV reactions followed the kinetics of a pseudo-first-order model. The degradation rate constant (19 x 10(-4)min(-1)) in the combined reaction with UV-C (4.2 mW cm(-2)) and Fe0 (5 mg L(-1)) was significantly enhanced compared to Fe0-only (4.8 x 10(-4) min(-1)) and photolytic reactions (2.25 x 10(-4)min(-1)), respectively. The removal efficiency of 1,4-dioxane in combined reaction with Fe0 and UV within 4 h was enhanced by increasing UV intensity at UV-C region (34% at 4.2 mW cm(-2) and 89% at 16.9 mW cm(-2)) comparing with the removal in the combined reaction with Fe0 and UV-A (29% at 2.1 mW cm(-2), and 33% at 12.6 mW cm(-2)). It indicates that 1,4-dioxane was degraded mostly by OH radicals in the combined reaction. The degradation patterns in both Fe(0)-only and combined reactions were well fitted to the Langmuir-Hinshelwood model, implying that adsorption as well as the chemical reaction occurred. The transformation of Fe0 to Fe2+ and Fe3+ was observed in the Fe0-only and combined reactions, and the transformation rate of Fe0 was improved by UV irradiation. Furthermore, the reduction of Fe3+ was identified in the combined reaction, and the reduction rate was enhanced by an increase of UV energy. Our study demonstrated that the enhancement of 1,4-dioxane removal rate occurred via an increased supply of OH radicals from the Fenton-like reaction induced by the photolysis of Fe0 and H2O, and with producing less sludge.

Degradation of 1,4-dioxane in water using TiO2 based photocatalytic and H2O2/UV processes.

1,4-dioxane is a synthetic compound found in industrial effluent and subsequently contaminates water bodies due to its high solubility and high volatility. It is of concern due to its toxic and hazardous nature and has been listed as a class 2B carcinogen. This study involved optimisation of the photocatalytic and H(2)O(2)/UVC processes for 1,4-dioxane removal. Different photocatalysts and loadings were investigated for the degradation of low concentrations of 1,4-dioxane in water including a commercial P25, a synthesised magnetic photocatalyst and an immobilised sol-gel system. A commercial catalyst (Degussa P25) was the most efficient. A lifetime study of the sol-gel reactor showed that the coating was stable over the time period studied. The optimum H(2)O(2) concentration in the H(2)O(2)/UVC process was found to be 30ppm. The addition of H(2)O(2) to the photocatalytic process for 1,4-dioxane removal caused a decrease in rate for the commercial P25 photocatalyst and an increase in rate for the lab-made magnetic photocatalyst.

Surface functionalization of degradable polymers by covalent grafting.

With a new non-destructive and solvent-free photografting technique, N-vinylpyrrolidone was covalently grafted onto the surfaces of degradable polymers; poly(l-lactide), poly(epsilon-caprolactone), poly(lactide-co-glycolide), and poly(trimethylene carbonate). The modified surfaces were characterized by XPS, ATR-FTIR, SEM, and cell growth tests. The wettability was markedly improved, as static contact angles changed from about 80 degrees for the pristine substrates to around 30 degrees after 30min of grafting. Well-defined surface topographies, such as micro-patterns, are preserved in the process since the graft layers are thin. The biological response, measured as cytotoxicity, showed that the modified films provide good substrates, comparable with optimized cell culture plastics, for the adhesion and proliferation of normal human keratinocytes and skin fibroblasts.

Two-photon excitation of dioxane: time-resolved measurements of excited state complex formation with water.

We observed emission from the non-aromatic hydrocarbon 1,4-dioxane upon illumination with ps pulses at 380 nm. The emission intensity depended quadratically on incident power at 380 nm, indicating a two-photon process. In the absence of water the intensity decay was close to a single exponential, but displayed some evidence of an excited state process. In the presence of 1% water the emission spectra shifted dramatically to long wavelength. Water also resulted in wavelength-dependent intensity decays with negative pre-exponential factors on the long wavelength side of the emission, demonstrating the presence of an excited state reaction. At this water concentration the results are consistent with a two-state model due to emission from dioxane and a dioxane and a dioxane-water complex.