The partial molar volumes, V°2 and partial molar heat capacities, C°p ,2 , at infinite dilution have been determined for the tripeptides of sequence glycyl-X-glycine, where X is one of the amino acids glycine, tyrosine, glutamine, proline, and cysteine, in aqueous solution at 25°C. Using these results, the partial molar heat capacities and volumes of the amino acid side chains were derived. The side chain heat capacities and volumes were compared with those obtained using other model compounds.

Clear-coated boards have not been recommended for use in exterior conditions since irradiation with visible and UV radiation darkens them and photodegrades the lignin in the wooden surface beneath the coating, leading to delamination and subsequent catastrophic coating failure due to the continued action of sun, rain, and biological factors. Many approaches to rectify this problem have been explored. Chemical modification of the surface with hexavalent chromium, reaction with various anhydrides, grafting of UV absorbers, and esterification are among the methods attempted. A second approach has been via the clear coating itself where UV absorbers, antioxidants, and ultrafine titanium and iron oxides have been added. However, these have had limited or no success in stopping photodegradation processes. Since the main cause of photodegradation is photooxidation of lignin in the wooden surface as a consequence of free radical reactions initiated by UV irradiation, the approach taken in the present study, in an attempt to enhance the weathering performance of clear-coated boards outdoors, was to delignify the surfaces of wooden boards and then apply clear coatings to try and retard possible photodegradation. Two different pretreatments were used. Firstly, chemical surface delignification with a peracetic acid treatment created a partial delignification to a depth of 2-3 mm while still retaining the structural integrity of the surface. Secondly, a preweathering treatment, which resulted in a 100-lmdeep delignification zone, was compared. The coatings applied to the exposure surface of the pretreated boards were either polyurethane or an acrylic varnish. The clear-coated boards were exposed to exterior and accelerated weathering regimes for 3 years or 3000 h, respectively. Pretreated coated boards did not darken and yellow on exposure but untreated coated boards did. However, despite apparently arresting photodegradative processes on board surfaces, there were no significant gains in the performance ratings of coated pretreated boards over those of coated untreated control boards. Explanations for this involve the effectiveness of design factors incorporated into boards for exposure trials. These factors were the fungicidal dipping of boards before coating, precoating the exposure surface with a reactive primer, and applying a full polyurethane system to the back side and edges of boards. Both pretreatments resulted in clear-coated board surfaces that performed very similarly on exposure outperforming systems reported previously. It was surprising to observe that the preweathering treatment, which resulted in a 100-lm-deep delignification zone, performed as effectively as the chemically pretreated boards with 2-to 3-mm treatment zone. However, preweathered surfaces had lost all lignin in the middle lamella and there was cell separation, whereas in peracetic acid-treated boards, there was more or less complete lignin removal from the cell corner middle lamella only and partial lignin removal from other cell wall regions. ...

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The aim of this work was to produce a less photodegradation-prone substrate for clear coating by partially delignifying the surface cells of Pinus radiata boards to a depth of 2-3 mm while maintaining the integrity of the wood surface tissues in the delignified zone. To achieve this, several surface oxidative delignification treatments were trialled in the method development process and peracetic acid was chosen as the method for refinement and deployment. The treatment method was optimized to yield a significant degree of delignification compatible with the aim of producing a photostabilized yet intact wooden surface. A preweathering technique was also used as a second delignification method for producing photostabilized boards. Microscopic and chemical techniques were used to characterize the effects of chemical and preweathering treatments, which produced delignified surface envelopes 2-3 mm and 100 lm deep, respectively. Acetyl bromide lignin analyses, infrared spectroscopic analyses, and density changes of 30-lm-thick sections of peracetic-acid-treated samples, as a function of depth from the wood surface, suggested that a partial delignification had occurred that diminished with depth. Light and transmission electron microscopy provided evidence of delignification at the cellular level. In the surface layers of peracetic-acid-treated boards, all cell wall regions were delignified, with the middle lamella being the most severely affected. Lignin appeared to be completely removed from the cell corner middle lamella regions, but tracheids were still joined in other parts of the middle lamella. The S 1 , S 2 , and S 3 walls were also delignified. In subsurface layers, cell walls were only partially delignified and the tissues held their integrity. In contrast, in the preweathered boards, cell walls in the outermost layers were completely separated at the middle lamella from photodegradation. Preferential lignin removal over that of hemicelluloses was achieved via oxidative treatment of solid wood. The outcome of this was the successful fulfillment of our aim to produce partially delignified wooden surfaces that retained sufficient strength and aesthetic appearance and were suitable for application in wooden structures, provided that the necessary protection measures were carried out. Due to the narrow surface zone produced, machining of such surfaces would not be recommended as the most delignified zone would be removed first. In Part 2 of this series, the photostability of treated boards, which had been clear coated and weathered, will be considered.