The light-independent recovery of the photosynthetic apparatus from photoinhibition was monitored upon a transition of irradiance-stressed Dunaliella salina Teod. to darkness. Upon dark incubation, the chlorophyll (Chl) a /Chl b ratio of the cells decreased promptly with a half-time of 2.5 h from about 12:1 to about 5:1. In contrast, dark incubation of control cells resulted in only a negligible change of the Chl a /Chl b ratio. During dark incubation of irradiance-stressed cells, the level of the Chl a and b light-harvesting proteins of photosystem II (PSII) increased, a change accompanied by alterations in the composition of these light-harvesting proteins. The amount of photodamaged PSII, measured from the relative amount of a 160 kDa protein complex which contains the photodamaged D1 reaction center protein, decreased during dark incubation after an initial lag period. Concomitantly, the amount of functional PSII, measured from the 32 kDa form of D1, increased slightly in the dark. The results show that, in the dark, photodamaged D1 is slowly removed upon degradation from the thylakoid membrane and replaced by a de novo synthesized D1 protein. The amount of reaction center proteins and number of photochemically active PSI centers increased in the dark. These results suggest that thylakoid membranes of irradiance-stressed D. salina exist in a state of dynamic flux. We conclude that several aspects of the D. salina recovery from photoinhibition are light independent.
The suspension copolymerization of several t-butoxycarbonyl (t-BOC) protected 4-vinyl phenols with divinylbenzene has been studied to produce high porosity 10 μm bead materials with surface areas of 200–300 m2/g for use as separation media. The choice and amount of porogen is critical for the control of porosity and surface area while particle size and size distribution is controlled by other reaction variables. The t-BOC protecting groups of the polymers are easily removed by thermolysis and the deprotected beads are useful in the separation of amines. The relationship between polymer structure and separation ability in h.p.l.c. has been explored and the effect of alkyl substituents located ortho to the phenolic groups is discussed.
The synthesis of novel dendrimers functionalized with laser dyes both at the periphery and at the core, along with all relevant model compounds necessary for accurate photophysical studies, is described. The utilized synthetic strategy involves a modular approach in which a variety of peripheral and core moieties can be placed on a dendritic structure bearing electrophilic peripheral groups and a nucleophilic core. Specifically, the target macromolecules required functionalization with the laser dyes coumarin 2 (periphery) and coumarin 343 (core) due to the possibility of energy transfer from the former to the latter dye. In addition, the preparation of a novel, highly soluble and reactive hypermonomer utilized in the rapid and efficient synthesis of high-generation dye-labeled dendrimers and model compounds is outlined.
Glassy carbon electrodes were modified by electrochemical reduction of a diazonium molecule ((i)Pr3SiOCH2C6H4N2(+)BF4(-)) featuring a triisopropylsilyl-protected benzylic hydroxyl group. This electrochemical process introduced a monolayer of (i)Pr3SiOCH2C6H4- groups onto the surface of the electrode. The bulky -Si(i)Pr3 protecting group not only prevents the uncontrolled growth of structurally ill-defined and electronically blocking polyphenylene multilayers, but also separates the phenyl groups in the monolayer. Thus, the void spaces between these aryl units should allow a better accommodation of sizable molecules. Removal of the -Si(i)Pr3 protecting groups by (n)Bu4NF exposed the reactive benzylic hydroxyl functionalities that can undergo further transformations to anchor functional molecules. As an example, redox-active ferrocene molecules were grafted onto the modified electrode via a sequence of mesylation, azidation, and copper-catalyzed [3 + 2] cycloaddition reactions. The presence of ferrocenyl groups on the surface was confirmed by X-ray photoelectron spectroscopic and electrochemical studies. The resulting ferrocene-modified glassy carbon electrode exhibits cyclic voltammograms typical of surface-bound redox active species and remarkable electrochemical stability in an acidic aqueous environment.
A novel approach based on the reaction of multifunctional star polymers with chromophore-labelled linear polymers is presented for evaluating the extent of termination by chain–chain coupling during living free-radical polymerizations. A mixed initiating system consisting of an unlabelled, multifunctional initiator and an excess of a monofunctional alkoxyamine initiator containing a chromophore, such as pyrene, is used to initiate the living polymerization of vinyl monomers leading to a mixture of star and linear polymers. The occurrence of chain–chain coupling is readily identified and quantified by isolating the star polymer that is obtained and elucidating the level of incorporation of pyrene units by UV/vis spectroscopy. This allows the level of chain–chain coupling to be determined since the inclusion of pyrene into the star structure is a direct result of termination by radical coupling.
Dicobalt(II) cofacial bisporphyrins anchored by dibenzofuran (DPD) and xanthene (DPX) are efficient electrocatalysts for the four-electron reduction of oxygen to water despite their ca. 4 Å difference in metal–metal distances, suggesting that the considerable longitudinal Pac-Man flexibility of the pillared platforms is the origin for the similar catalytic reactivity of these structurally disparate systems.
