Of chlorophyll

Chemical degradation of chlorophyll gives a number of substances including phytol The constitution of phytol is given by the name 3 7 11 15 tetramethyl 2 hexadecen 1 ol How many stereoisomers have this constitution" ... 

Willstatter s most important work for which he won the 1915 Nobel Prize in chem istry was directed toward determining the structure of chlorophyll... 

Green coloration, present in many vegetable oils, poses a particular problem in oil extracted from immature or damaged soybeans. Chlorophyll is the compound responsible for this defect. StmcturaHy, chlorophyll is composed of a porphyrin ring system, in which magnesium is the central metal atom, and a phytol side chain which imparts a hydrophobic character to the stmcture. Conventional bleaching clays are not as effective for removal of chlorophylls as for red pigments, and specialized acid-activated adsorbents or carbon are required. 

Many studies have reported a link between consumption of sunburned potatoes, ie, those exposed to the sun and having an accumulation of chlorophyll and solanine under the skin, with incidences of teratogenic effects and even death (59—61). Because sunburned potatoes in the commercial marketplace are relatively rare, and because the long-term effects of consumption of potatoes at the maximum estabUshed limits of solanine concentration are uncertain, there is equal uncertainty of the tme incidence of human toxicity (62). 

Bleaching Herbicides. Membrane-based modes of herbicidal action relevant to photosynthesis (37) include those of inhibitors of carotenoid biosynthesis, eg, norflura2on, diftmon, y -phenoxyben2amines inhibitors of chlorophyll biosynthesis, eg, oxadia2on, DTP or... 

Hydrolysis of chlorophyll using sodium hydroxide produces the moderately water-soluble sodium salts of chlorophyllin, phytol and methanol (145). The magnesium ia chlorophyllin may be replaced by copper. The sodium copper chlorophyllin salt is heat stable, and is ideal for coloring foods where heat is iavolved, such as ia canning (146). 

R. WiUstAttei and A. StoU, Investigation of Chlorophyll, tians. F. M. Scheita and A. R. Meiz, Science Piess, Lancastei, Pa., 1928. 

The substituted methylene derivative, prepared from a 2-formylpyrrole and a ma-lonic acid derivative, was used in a synthesis of chlorophyll. It is cleaved under drastic conditions (coned alkali). ... 

Chlorophyll b [519-62-0] M 907.52, sinters at 86-92 , sinters at 170 , dec at 160-170 , m 183-185 , 190-195 , [alj, -267 (Me2CO + McOH), [a] j-133 (McOH + Pyridine 95 5). See purification of chlorophyll a, and is separated from "a" by chromatography on sucrose [UV, IR Stoll and Weidemann Helv Chim Acta 42 679, 681 7959]. It forms red-black hexagonal bipyramids or four sided plates from dilute EtOH and has been recrystd from CHCl3-MeOH. It is soluble in MeOH, EtOH, EtOAc and insoluble in pet ether. [J Am Chem Soc 88 5037 1966.]... 

The interiors of rhodopseudomonad bacteria are filled with photosynthetic vesicles, which are hollow, membrane-enveloped spheres. The photosynthetic reaction centers are embedded in the membrane of these vesicles. One end of the protein complex faces the Inside of the vesicle, which is known as the periplasmic side the other end faces the cytoplasm of the cell. Around each reaction center there are about 100 small membrane proteins, the antenna pigment protein molecules, which will be described later in this chapter. Each of these contains several bound chlorophyll molecules that catch photons over a wide area and funnel them to the reaction center. By this arrangement the reaction center can utilize about 300 times more photons than those that directly strike the special pair of chlorophyll molecules at the heart of the reaction center. 

This pair of chlorophyll molecules, which as we shall see accepts photons and thereby excites electrons, is close to the membrane surface on the periplasmic side. At the other side of the membrane the symmetry axis passes through the Fe atom. The remaining pigments are symmetrically arranged on each side of the symmetry axis (Figure 12.15). Two bacteriochlorophyll molecules, the accessory chlorophylls, make hydrophobic contacts with the special pair of chlorophylls on one side and with the pheophytin molecules on the other side. Both the accessory chlorophyll molecules and the pheophytin molecules are bound between transmembrane helices from both subunits in pockets lined by hydrophobic residues from the transmembrane helices (Figure 12.16). 

In the bacterial reaction center the photons are absorbed by the special pair of chlorophyll molecules on the periplasmic side of the membrane (see Figure 12.14). Spectroscopic measurements have shown that when a photon is absorbed by the special pair of chlorophylls, an electron is moved from the special pair to one of the pheophytin molecules. The close association and the parallel orientation of the chlorophyll ring systems in the special pair facilitates the excitation of an electron so that it is easily released. This process is very fast it occurs within 2 picoseconds. From the pheophytin the electron moves to a molecule of quinone, Qa, in a slower process that takes about 200 picoseconds. The electron then passes through the protein, to the second quinone molecule, Qb. This is a comparatively slow process, taking about 100 microseconds. 

Modeling of the reaction center inside the hole of LHl shows that the primary photon acceptor—the special pair of chlorophyll molecules—is located at the same level in the membrane, about 10 A from the periplasmic side, as the 850-nm chlorophyll molecules in LH2, and by analogy the 875-nm chlorophyll molecules of LHl. Furthermore, the orientation of these chlorophyll molecules is such that very rapid energy transfer can take place within a plane parallel to the membrane surface. The position and orientation of the chlorophyll molecules in these rings are thus optimal for efficient energy transfer to the reaction center. 

The immediate electron acceptor for P700 is a special molecule of chlorophyll. This unique Chi a (Aq) rapidly passes the electron to a specialized quinone (Aj), which in turn passes the e to the first in a series of membrane-bound ferredoxins (Fd, Chapter 21). This Fd series ends with a soluble form of ferredoxin, Fd, which serves as the immediate electron donor to the fiavo-protein (Fp) that catalyzes NADP reduction, namely, ferredoxin NADP reductase. 

Although /3-oxidation is universally important, there are some instances in which it cannot operate effectively. For example, branched-chain fatty acids with alkyl branches at odd-numbered carbons are not effective substrates for /3-oxidation. For such species, a-oxidation is a useful alternative. Consider phy-tol, a breakdown product of chlorophyll that occurs in the fat of ruminant animals such as sheep and cows and also in dairy products. Ruminants oxidize phytol to phytanic acid, and digestion of phytanic acid in dairy products is thus an important dietary consideration for humans. The methyl group at C-3 will block /3-oxidation, but, as shown in Figure 24.26, phytanic acid a-hydroxylase places an —OFI group at the a-carbon, and phytanic acid a-oxidase decar-boxylates it to yield pristanie add. The CoA ester of this metabolite can undergo /3-oxidation in the normal manner. The terminal product, isobutyryl-CoA, can be sent into the TCA cycle by conversion to succinyl-CoA. 

Phytanic acid, the product of chlorophyll that causes problems for individuals with Refsum s disease, is 3,7,11,15-tetramethyl hexa-decanoic acid. Suggest a route for its oxidation that is consistent with what you have learned in this chapter. Hint The methyl group at C-3 effectively blocks hydroxylation and normal /3-oxidation. You may wish to initiate breakdown in some other way.)... 

Since Woodward s work on the synthesis of chlorophyll a (60JA3800) it is known that the intrinsic unstable thioformyl moiety can be stabilized by the delocalization effect of heterocyclic systems. Recently the synthesis of 2-amino- and 3-aminothioformylthiophenes (and furans) and the corresponding benzo derivatives (Scheme 19) has been reported (96S1185). These compounds exist as amino tautomers (91S609 96S1185). 

Methods for the synthesis of pyrroles are of importance, since the pyrrole unit is found in natural products widespread in nature. For example a pyrrole unit is the building block of the porphyrin skeleton, which in turn is the essential structural subunit of chlorophyll and hemoglobin. 

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