Validation of the reciprocity law for coating photodegradation

Accelerating the photodegradation of commercial polymeric materials has great practical importance in the weathering community. However, questions exist as to whether high radiant flux exposure results can be extrapolated to in-service exposure levels. Based on the reciprocity law, the photoresponse of a material is dependent only on the total energy to which the specimen is exposed, and is independent of the exposure time and the intensity of the radiation taken separately. An experiment to validate the applicability of the reciprocity law for polymeric coatings has been carried out using the NIST integrating sphere-based ultraviolet (UV) weathering device. A nonpigmented, non-UV stabilized acrylicmelamine coating was exposed to six different UV radiation intensities ranging from 36 W/m² to 322 W/m², and in the spectral region between 290 nm and 400 nm. Chemical changes in the coating due to UV exposure were measured with transmission Fourier transform infrared (FTIR) spectroscopy and UV-visible spectroscopy. Using two dose-damage models, the reciprocity law photoresponse for this polymeric system was verified for different photodegradation mechanisms, including chain scission, oxidation, and mass loss. Presented at the 82nd Annual Meeting of the Federation of Societies for Coatings Technology, October 27–29, 2004, in Chicago, IL.     

Tailoring the Mechanical Properties of 3D Microstructures Using Visible Light Post‐Manufacturing

The photochemistry of anthracene, a new class of photoresist for direct laser writing, is used to enable visible‐light‐gated control over the mechanical properties of 3D microstructures post‐manufacturing. The mechanical and viscoelastic properties (hardness, complex elastic modulus, and loss factor) of the microstructures are measured over the course of irradiation via dynamic mechanical analysis on the nanoscale. Irradiation of the microstructures leads to a strong hardening and stiffening effect due to the generation of additional crosslinks through the photodimerization of the anthracene functionalities. A relationship between the loss of fluorescence—a consequence of the photodimerization—and changes in the mechanical properties is established. The fluorescence thus serves as a proxy read‐out for the mechanical properties. These photoresponsive microstructures can potentially be used as “mechanical blank slates”: their mechanical properties can be readily adjusted using visible light to serve the demands of different applications and read out using their fluorescence.     

Changes in aliphatic ester composition of white wines during exposition to light. An HS-SPME-GC-MS study

The irradiation of four Italian white wines with a visible light comparable to that encountered in the market place showed a modification in the amount of aliphatic esters in the wines. Aliphatic esters are responsible for fruity aromas in wines. The first wine studied was the Gewürztraminer, a white wine from Alto Adige (Northern Italy). The amounts of the esters presents in the wine decreased. All the curves follow a pseudo-first-order kinetics. This behaviour can be explained assuming a photooxidation process catalysed by riboflavin. When Arneis Blangè was irradiated, ethyl acetate showed an increase after one day of irradiation; its content then decreased and after five days' irradiation its concentration reached a maximum. Conversely, the concentration of other aliphatic esters decreased after one day's irradiation and then increased progressively to reach a maximum after five days' irradiation. The same behaviour was observed with Pecorino wine. In this case, the concentration of the aliphatic esters decreased until the second day of irradiation but increased after five days' irradiation. In the case of the irradiation of Lighea Zibibbo all the esters showed an increase in concentration after one day of irradiation. The concentration decreased after two days' irradiation, and then increased to reach a maximum after seven days of irradiation. The increase in the amount of esters in some wines and, by contrast, the decrease in the same compounds in Gewürztraminer can be explained by considering that, during the irradiation, the pH of Gewürztraminer did not change, while the pH of Arneis Blangè changed following a curve similar to that showed by the concentration of esters. The pH change can be explained assuming the presence of a photocatalytic process induced by the presence of metals in the wines and influencing the amount of tartaric acid.     

Degradation of poly(L‐lactide) films under ultraviolet‐induced photografting and sterilization conditions

The degradation of polymers under ultraviolet (UV) irradiation has been a great concern for biomaterial and agricultural applications. The major objective of this research was to study the effect of UV irradiation on the representative bulk and surface properties of poly (L ‐lactide) (PLA) films. Two UV sources with different spectral outputs and intensities were chosen so that one of them could be used for surface modification and the other could be used for UV sterilization of the PLA films. The results established that the molecular weight of PLA decreased significantly during irradiation from the photografting lamp under atmospheric conditions. Irradiation through a Pyrex container was shown to minimize polymer degradation during UV exposure from the photografting lamp. The PLA films UV‐irradiated under the sterilization lamp for 12 h revealed a similar reduction in the molecular weight and no change in the surface hydrophilicity. However, significantly less photodegradation was observed under the sterilization lamp when the samples were held in a Pyrex container. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

A Photoswitchable Trivalent Cluster Mannoside to Probe the Effects of Ligand Orientation in Bacterial Adhesion

We have recently demonstrated, by employing azobenzene glycosides, that bacterial adhesion to surfaces can be switched through reversible reorientation of the carbohydrate ligands. To investigate this phenomenon further, we have turned here to more complex—that is, multivalent—azobenzene glycoclusters. We report on the synthesis of a photosensitive trivalent cluster mannoside conjugated to an azobenzene hinge at the focal point. Molecular dynamics studies suggested that this cluster mannoside, despite the conformational flexibility of the azobenzene-glycocluster linkage, offers the potential for reversibly changing the glycocluster's orientation on a surface. Next, the photoswitchable glycocluster was attached to human cells, and adhesion assays with type 1 fimbriated Escherichia coli bacteria were performed. They showed marked differences in bacterial adhesion, dependent on the light-induced reorientation of the glycocluster moiety. These results further underline the importance of orientational effects in carbohydrate recognition and likewise the value of photoswitchable glycoconjugates for their study.     

Photochemistry of 2,6‐di(4′‐azidobenzylidene)‐methylcyclohexanone in polymer matrices

2,6‐Di(4′‐azidobenzylidene)‐methylcyclohexanone (ABC) was one of the most used photoinitiators in negative photoresists industry, rendering insolubility of the resist films at short UV exposure times (several minutes). Although the photodecomposition of aromatic azides is very well established, the peculiarities of the irradiation medium impose specific reaction pathways for arylnitrenes. In this study, photoreactions of arylnitrenes resulted from ABC photolysis were applied in the photoinitiated crosslinking of 1,2‐polybutadiene (1,2‐PB), under soft monochromatic UV irradiation (365 nm). To elucidate the crosslinking mechanism, studies on a model compound were performed. 3‐Methyl‐1‐butene was chosen to simulate the monomeric unit of 1,2‐PB. As a support in photoproducts identifying and with the purpose of a deeper investigation of the ABC photochemistry alone, ABC was photolysed in a rigid matrix of poly(methyl methacrylate). © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44694.