Synthesis and Characterization of New Multifunctional Self-Boosted Filters for UV Protection: ZnO Complex with Dihydroxyphenyl Benzimidazole Carboxylic Acid.

The incidence of skin cancer is increasing both because of climate change and the increase in pollution than people's incorrect habits of sun exposure. In these regards, sunscreen and photoprotection are essential tools in consenting the benefits induced by safe solar light exposition and skin cancer prevention. In this work, a new class of sunscreen filter was synthesized by chemical combination of a physical filter (ZnO) and Oxisol (dihydroxyphenyl benzimidazole carboxylic acid), an antioxidant molecule with booster effect. In this work, a new class of filters with new properties was achieved by direct functionalization of particles surface. A full characterization of this multifunctional ingredient (ZnO-Ox) was conducted: Compared with the simple mixture, the new filter acts as a multifunctional molecule showing a higher Sun Protection Factor (SPF), a better cytotoxic profile (MTT and NRU assay), and anti-acne activity. A strong reduction of photocatalytic activity of ZnO was observed, also improving the safety profile.

Confined-Melting-Assisted Synthesis of Bismuth Silicate Glass-Ceramic Nanoparticles: Formation and Optical Thermometry Investigation.

Bismuth-based (nano)materials have been attracting increasing interest due to appealing properties such as high refractive indexes, intrinsic opacity, and structural distortions due to the stereochemistry of 6s2 lone pair electrons of Bi3+. However, the control over specific phases and strategies able to stabilize uniform bismuth-based (nano)materials is still a challenge. In this study, we employed the ability of bismuth to lower the melting point of silica to introduce a new synthetic approach able to confine the growth of bismuth-oxide-based materials into nanostructures. Combining in situ temperature-dependent synchrotron radiation X-ray powder diffraction (XRPD) with high-resolution transmission electron microscopy (HR-TEM) analyses, we demonstrate the evolution of a confined Bi2O3-SiO2 nanosystem from Bi2SiO5 to Bi4Si3O12 through a melting process. The silica shell acts as both a nanoreactor and a silicon source for the stabilization of bismuth silicate glass-ceramic nanocrystals keeping the original spherical shape. The exciton peak of Bi2SiO5 is measured for the first time allowing the estimation of its real energy gap. Moreover, based on a detailed spectroscopic investigation, we discuss the potential and the limitations of Nd3+-activated bismuth silicate systems as ratiometric thermometers. The synthetic strategy introduced here could be further explored to stabilize other bismuth-oxide-based materials, opening the way toward the growth of well-defined glass-ceramic nanoparticles.

A New Approach to UV Protection by Direct Surface Functionalization of TiO2 with the Antioxidant Polyphenol Dihydroxyphenyl Benzimidazole Carboxylic Acid.

Skin cancer is the most common malignant cancer with an incidence of 1 million cases/year. It is well known that exposure to UV radiation from sunlight leads the most frequent risk factors for several skin disorders including skin cancer. Sunscreen filters represent a valid protection against dangerous effects derived from UV radiation, and they can be divided in organic and inorganic UV filters. Adding, at the product formulation, molecules with booster effect, or also substances that can increase the protecting effectiveness via synergic mechanisms, can further enhance their protection activity. Moreover, this approach leads to develop formulations with high SPF (Sun Protection Factor) with a reduced content of UV filters, this is in line with the recent decisions of yet a few countries (Palau, Thailand, Philippines, and Hawaii) to ban some sunscreen filters to preserve marine environments (i.e., reef). In this work, a new class of sunscreen UV filters has been synthesized, by means the combination of physical filter and Oxisol, an antioxidant molecule with booster effect. In this study, the synthesis of new physical multifunctional ingredients is reported, by means the direct surface functionalization of inorganic filters (in particular TiO2) with Oxisol. In this study, the full characterization of these multifunctional ingredients is also reported, in addition to the cytotoxicity tests, the photocatalytic activity and the rheological properties involved on skin application.

Validation of a protocol based on Raman and infrared spectroscopies to nondestructively estimate the oxidative degradation of UHMWPE used in total joint arthroplasty.

UNLABELLED: As a matter of fact, the in vivo oxidative degradation of highly cross-linked polyethylene (HXLPE) still remains one of the limiting factors that affect the long term survivorship of joint replacements. Recent studies clearly pointed out that also the new generation of highly cross-linked and remelted polyethylene components in total hip and knee replacement underwent unexpected oxidation after 5-10years of implantation. The standard methodology to investigate the oxidation of polyethylene (PE) relies on the use of infrared spectroscopy, which, if from one hand is a reliable technique for the detection of oxidized species containing carbonyl group, on the other hand it is not capable of discriminating the fraction of carboxyl acids that is responsible for chain scission and subsequent deterioration of the mechanical properties of the polymer. In the present study we validate a new protocol based on Raman spectroscopy, which is suitable on assessing the structural degradation of polyethylene induced by oxidation. Following in vitro accelerated aging experiments, the oxidation index (OI) of different commercially available HXLPEs, as calculated by infrared spectroscopy according to ASTM standard, has been univocally correlated to the most severe variation of crystalline phase (αc), as calculated by Raman spectroscopy. In each material, locations with equal values of OI showed different degree of recrystallization induced by chain scission, confirming that infrared spectroscopy might overestimate the effective mechanical degradation of the polymer. In addition, as compared to the standards based on infrared spectroscopy, this new method of assessing oxidation enables to investigate the degradation occurring on the original surface of HXLPE components, due to the nondestructive nature of Raman spectroscopy and its high spatial resolution. STATEMENT OF SIGNIFICANCE: In the present study we validate a new protocol based on Raman spectroscopy, which is suitable on assessing the structural degradation of polyethylene induced by oxidation. In fact, the standard methodology to investigate the oxidation in polyethylene relies on the use of infrared spectroscopy, which is capable of detecting the presence of oxidized species containing carbonyl group, the main products of oxidation in polyolefins. If from one hand this technique enables quantitative analysis of oxidation, on the other hand it is not capable of discriminating the fraction of species with carbonyl groups responsible for the chain scission. In fact, esters, ketones and carboxyl acids are products of oxidation with carbonyl groups commonly formed on polyethylene at the end of the oxidative cascade initiated by the presence of free radicals, but only the latter are responsible for the chain scission and the subsequent deterioration of the mechanical properties. The oxidation index as obtained according to the ASTM standards is not univocally correlated to a certain degree of mechanical deterioration, but, in simple words, two retrievals with the same amount of carbonyl groups might have had different degradation of the mechanical properties. Recrystallization is a direct consequence of the reduction of molecular weight that occurs after chain scission. Raman spectroscopy (RS) is a viable non-destructive method to assess the fraction of crystalline phase in polyethylene and, due to its high spatial resolution, is perfectly suitable to analyze the microstructural modification at the mesoscopic scale, where the effects of oxidation manifest themselves. The aim of the present paper is twofold: i) to compare the microstructural modifications caused by in vitro oxidation on 5 different types of polyethylene currently available on the market of joint replacements; ii) to establish a protocol based on the comparative analysis of IR and RS results to obtain a phenomenological correlation capable to judge the mechanical deterioration of the material induced by the oxidative degradation.

On the molecular interaction between femoral heads and polyethylene liners in artificial hip joints: phenomenology and molecular scale phenomena.

The chemical interaction of femoral heads with polyethylene liners is an important new area of research in total hip arthroplasty (THA) as a consequence of an unabating quest for elongated artificial joint lifetimes. It is a topic that goes beyond simple mechanical behavior or wear. It seeks to describe the prosthetic device as a whole by adding chemical considerations to mechanics and abrasion. One of the poorly understood chemical interactions is oxygen affinity of the femoral heads. While oxygen unavoidably diffuses into the non-crystalline enclaves of the polyethylene liner as a result of its contact with the tribolayer, a ceramic femoral head can either attract or release oxygen due to its tribochemical interactions. In this study, changes in liner crystallinity and oxidation were observed during simple static contact with different femoral heads within a hydrothermal environment. Examinations were made using Raman microprobe spectroscopy coupled with nanometer-scale spectroscopic analyses (x-ray photoelectron spectroscopy (XPS) and cathodoluminescence (CL) spectroscopy) on different sets of ceramic and polyethylene couples exposed for increasing periods to a hydrothermal environment. Even in the absence of frictional loading, structural modifications were clearly detected, statistically validated, and correlated with the oxygen affinity of various femoral head materials. It was found that oxide (Al2O3, Al2O3/ZrO2, and m-ZrO2) and non-oxide (Si3N4) ceramic heads release or attract nascent oxygen species, respectively. This research unequivocally identified a new gap in our knowledge of THA biomaterial interactions, with future studies and material improvements undoubtedly leading to an increase in longevity for prosthetic joints.