Reactive oxygen species (ROS) are continuously generated as a by-product of normal aerobic metabolism. Elevated ROS formation leads to potential damage of biological structures and is implicated in various diseases. Astaxanthin, a xanthophyll carotenoid, is a secondary metabolite responsible for the red-orange color of a number of marine animals and microorganisms. There is mounting evidence that astaxanthin has powerful antioxidant, anti-inflammatory, and antiapoptotic activities. Hence, its consumption can result in various health benefits, with potential for therapeutic application. Astaxanthin contains both a hydroxyl and a keto group, and this unique structure plays important roles in neutralizing ROS. The molecule quenches harmful singlet oxygen, scavenges peroxyl and hydroxyl radicals and converts them into more stable compounds, prevents the formation of free radicals, and inhibits the autoxidation chain reaction. It also acts as a metal chelator and converts metal prooxidants into harmless molecules. However, like many other carotenoids, astaxanthin is affected by the environmental conditions, e.g., pH, heat, or exposure to light. It is hence susceptible to structural modification, i.e., via isomerization, aggregation, or esterification, which alters its physiochemical properties. Here, we provide a concise overview of the distribution of astaxanthin in tissues, and astaxanthin structures, and their role in tackling singlet oxygen and free radicals. We highlight the effect of structural modification of astaxanthin molecules on the bioavailability and biological activity. These studies suggested that astaxanthin would be a promising dietary supplement for health applications.
The effects of nonpolar and polar solvents on the Q, and Q, energies of bacteriochlorophyll (BChl) a and bacteriopheophytin (BPhe) a were examined by electronic absorption spectroscopy. All of the four different energies exhibited a linear dependence on R(n) = (nZ -l)/(nz + 2), where n is the refractive index of the solvent, in both nonpolar and polar solvents. The energy of each state of both pigments could be expressed as v = -dR(n) + e (in cm-I) where coefficient d was related to the dispersive interaction between the solute and the solvent molecules. A theory developed by Nagae showed that coefficient d originates from the quantum-mechanical fluctuation of the multipole moments of the solute, in terms of which the following characteristics of the observed d values were explained: (1) In all of the four cases of the Q, and Q, energies of both BChl a and BPhe a, the d values for the polar solvents were smaller than those for the nonpolar solvents. (2) In both nonpolar and polar solvents, the d value of BChl a was larger than that of BPhe a in the Q, energy, whereas the d value of BPhe a was larger than that of BChl a in the Q, energy. (3) The d value of the Q, energy was larger than that of the Q, energy for either case of BChl a or BPhe a.
The photostabilities of bacteriochlorophyll a and several of its derivatives, which are of interest as potential sensitizers in photodynamic tumor therapy, were investigated. The pigments were irradiated with light >630 nm in organic solvents (acetone, tetrahydrofuran, pyridine, methanol, ethanol, n-propanol, 2-propanol and toluene) and in aqueous detergent solutions (cetyl-trimethyl-ammonium bromide [CTAB], lauryldimethyl-aminoxide [LDAO] or sodium dodecyl-sulfate [SDS] and Triton X-100 [TX100]). Their stabilities in these different solvents were determined in the presence and absence of an external sensitizer (pyromethyl-pheophorbide a), oxygen, sodium ascorbate and inert gas (Ar) or vacuum. The photodegradation products of bacteriochlorophyll a in acetone solution were isolated, purified by HPLC and analyzed by their absorption spectra and mass spectroscopy. Besides the well-known dehydrogenation products, such as [3-acetyl]-chlorophyll a, which were obtained as by-products, the major products had low absorption in the visible-near infrared spectral range. The spectral signature of the major component of these products was characteristic of linear open-chain tetrapyrroles, but they lacked the characteristic protonation-deprotonation behavior and reactivity of bilins with Zn(++).
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