Comparative decay characteristics of the light generated free radical in chromatophores and chloroplasts

Abstract— Chromatophores of Rhodospirillum rubrum when illuminated exhibit a free radical which ordinarily shows a biphasic decay. When chromatophores are dehydrated at room temperature the time course of the appearance of the light-induced free radical is unaffected, but the decay pattern has been altered. Only the fast component remains, the slow component is no longer evident. Scanning the magnetic field reveals the presence of a dark signal which is stable as long as the preparation remains dehydrated. This signal has the same peak-to-peak line width of ? 10 G and the same g factor as the signal evident in the light. The amplitude of this signal is equal to the amplitude of the slow decay component seen in aqueous chromatophore suspensions. Chromatophores frozen in an aqueous medium at —150°C exhibit a behavior identical with dehydrated preparations. The effects produced by lyophilization or by freezing at low temperatures are entirely reversible. When a lyophilized preparation is re-hydrated, the stabilized portion of the signal now decays in the dark; the same is observed when preparations frozen at —150°C are thawed. When such thawed or re-hydrated preparations are illuminated again, they exhibit the usual light-induced ESR signal showing a biphasic dark decay. A comparison was made between the behavior of the light-induced ESR signal of chromatophores and that of system I of chloroplasts. This comparison revealed that there is a greater similarity in some of the decay characteristics of these signals than had been recognized previously. In chloroplasts, temperature insensitive, non-enzymatic back-reactions of the light-induced free radical appear to be nil, and in chromatophores a distinct portion of the light-induced free radicals exhibit the same characteristics. Another portion of the chromatophore free radicals must be able to back-react by electron tunneling, a mechanism which appears to be absent in the chloroplast system.     

FLASH PHOTOLYSIS-ELECTRON SPIN RESONANCE STUDIES OF THE INTERACTION OF PHENAZINE METHOSULFATE WITH REACTION-CENTER PREPARATIONS FROM THE R-26 MUTANT OF RHODOPSEUDOMONAS SPHEROIDES*

Abstract— Using the technique of flash photolysis-electron spin resonance, we have shown, by means of a kinetic analysis, that phenazine methosulfate (PMS) interacts with reaction-center preparations from the blue-green mutant R26 of Rhodopseudomonas spheroides. At intermediate concentrations of PMS, biphasic decay kinetics of the P870⁺ ESR signal are observed demonstrating that the PMS radical interacts with reaction centers by a specific binding mechanism. With PMS bound to reaction centers, the P870⁺ ESR signal decays in ˜ 1 ms; whereas, in unbound reaction centers the decay is ˜ 120 ms. A model is proposed involving the interaction of PMS on the donor side of P870.     

FLASH PHOTOLYSIS-ELECTRON SPIN RESONANCE: A KINETIC STUDY OF ENDOGENOUS LIGHT-INDUCED FREE RADICALS IN REACTION CENTER PREPARATIONS FROM RHODOPSEUDOMONAS SPHEROIDES*

Abstract— Using the technique of flash photolysis-electron spin resonance, we have detected, by means of a kinetic analysis, a rapidly decaying signal in reaction center preparations from the R26 blue-green mutant of Rhodopseudomonas spheroides. This signal, which we designate Signal B3, is essentially the same as that seen previously in iron-free preparations. Signal B3 decays at 20°C with a 1/ e time of ˜ 3 ms and exhibits an activation energy of 5 ± 1 kcal mol^-1 over the temperature range 0–30°C. Extraction with isooctane completely eliminates Signal B3, whereas readdition of exogenous ubiquinone-30 completely restores the signal. o -Phenanthroline has no effect on Signal B3. We discuss these results in terms of a model in which the primary acceptor is an iron-ubiquinone complex with excess ubiquinone serving as a secondary electron acceptor pool.     

Dynamic response of blast loaded prestressed flat plates

A finite difference method was used to study the effect of inplane loads on the dynamic response of a square flat plate subjected to a transverse blast load. The method can be easily programmed for rapid evaluation on a digital computer. A modal superposition method of analysis and a shock spectrum for the load are used. It is shown that inplane tension loads significantly influence the stiffness and subsequent dynamic response of flat plates.     

Convergent Versus Divergent Three-Step Synthesis of the First (4-Aminophenoxy)alkanoic Acid–Based Tripodal Melamines

Starting from N-(4-hydroxyphenyl)acetamide (Paracetamol, convergent approach) or from cyanuric chloride in reaction with 4-aminophenol (divergent approach), two synthetic routes toward novel tripodal N-substituted melamines as s-triazine derivatives of (4-aminophenoxy)acetic acid or of 4-(4-aminophenoxy)butyric acid are comparatively defined. The key steps consist of Williamson etherification of N-masked forms of 4-aminophenol and acidic hydrolysis of the N- and/or O-protected (4-aminophenoxy)alkanoic segments.