Protein disulphide isomerase-assisted functionalization of proteinaceous substrates

Protein disulphide isomerase (PDI) is an enzyme that catalyzes thiol-disulphide exchange reactions among a broad spectrum of substrates, including proteins and low-molecular thiols and disulphides. As the first protein-folding catalyst reported, the study of PDI has mainly involved the correct folding of several cysteine-containing proteins. Its application on the functionalization of protein-based materials has not been extensively reported. Herein, we review the applications of PDI on the modification of proteinaceous substrates and discuss its future potential. The mechanism involved in PDI functionalization of fibrous protein substrates is discussed in detail. These approaches allow innovative applications in textile dyeing and finishing, medical textiles, controlled drug delivery systems and hair or skin care products.We thank to FCT 'Fundacao para a Ciencia e Tecnologia' (scholarship SFRH/BD/38363/2007) for providing Margarida Fernandes the grant for PhD studies

Biology of human hair: Know your hair to control it

Hair can be engineered at different levels—its structure and surface—through modification of its constituent molecules, in particular proteins, but also the hair follicle (HF) can be genetically altered, in particular with the advent of siRNA-based applications. General aspects of hair biology are reviewed, as well as the most recent contributions to understanding hair pigmentation and the regulation of hair development. Focus will also be placed on the techniques developed specifically for delivering compounds of varying chemical nature to the HF, indicating methods for genetic/biochemical modulation of HF components for the treatment of hair diseases. Finally, hair fiber structure and chemical characteristics will be discussed as targets for keratin surface functionalization

Formation of singlet oxygen from solutions of vitamin E

Vitamin E offers protection against oxidative stress and is an efficient quencher of singlet oxygen. A recent report suggests that photo-excitation of vitamin E results in the formation of a triplet state (Naqvi et al. Photochem Photobiol Sci 2, 381 (2003)). This leads to the possibility of the triplet state of vitamin E being able to sensitize singlet oxygen and if this is the case it would be counter productive in terms of the biological protective function of vitamin E. We report the production of singlet oxygen, detected by 1270 nm luminescence, from pulsed laser excitation (308 nm) of vitamin E and an analogue, 2,2,5,7,8-pentamethyl-6-hydroxy-chroman (PMHC), with quantum yields between ~0.1 and 0.2. The luminescence was identified as singlet oxygen from self-quenching by vitamin E with solvent-dependent rate constants similar to published values. Whilst the beneficial antioxidant aspects of vitamin E are well established, these results indicate that vitamin E when directly excited can sensitize singlet oxygen formation and may, therefore, be capable of inducing biochemical and biological damage. The results are discussed in relation to recent reports on the deleterious effects of vitamin E dietary supplementation and pro-oxidant effects of vitamin E

Long-lived connection between southern Siberia and northern Laurentia in the Proterozoic

Precambrian supercontinents Nuna-Columbia (1.7 to 1.3 billion years ago) and Rodinia (1.1 to 0.7 billion years ago) have been proposed. However, the arrangements of crustal blocks within these supercontinents are poorly known. Huge, dominantly basaltic magmatic outpourings and intrusions, covering up to millions of square kilometres, termed Large Igneous Provinces, typically accompany (super) continent breakup, or attempted breakup and offer an important tool for reconstructing supercontinents. Here we focus on the Large Igneous Province record for Siberia and Laurentia, whose relative position in Nuna-Columbia and Rodinia reconstructions is highly controversial. We present precise geochronology—nine U–Pb and six Ar–Ar ages—on dolerite dykes and sills, along with existing dates from the literature, that constrain the timing of emplacement of Large Igneous Province magmatism in southern Siberia and northern Laurentia between 1,900 and 720 million years ago. We identify four robust age matches between the continents 1,870, 1,750, 1,350 and 720 million years ago, as well as several additional approximate age correlations that indicate southern Siberia and northern Laurentia were probably near neighbours for this 1.2-billion-year interval. Our reconstructions provide a framework for evaluating the shared geological, tectonic and metallogenic histories of these continental blocks