Multiple pathways to the reaction centre

2007 ◽  
pp. 75-106
Keyword(s):  
Reaction Centre

Structural analysis of the photosynthetic membrane from Ectothiorhodospira halochloris

1983 ◽  
Vol 41 ◽  
pp. 740-741
Author(s):  
H. Engelhardt ◽  
R. Guckenberger ◽  
W. Baumeister
Keyword(s):  
Lattice Structure ◽  
Bacterial Species ◽  
Hexagonal Lattice ◽  
Reaction Centre ◽  
Photosynthetic Membrane ◽  
Rhodopseudomonas Viridis ◽  
Photosynthetic Membranes ◽  
Ectothiorhodospira Halochloris ◽  
Main Components

Bacterial photosynthetic membranes contain, apart from lipids and electron transport components, reaction centre (RC) and light harvesting (LH) polypeptides as the main components. The RC-LH complexes in Rhodopseudomonas viridis membranes are known since quite seme time to form a hexagonal lattice structure in vivo; hence this membrane attracted the particular attention of electron microscopists. Contrary to previous claims in the literature we found, however, that 2-D periodically organized photosynthetic membranes are not a unique feature of Rhodopseudomonas viridis. At least five bacterial species, all bacteriophyll b - containing, possess membranes with the RC-LH complexes regularly arrayed. All these membranes appear to have a similar lattice structure and fine-morphology. The lattice spacings of the Ectothiorhodospira haloohloris, Ectothiorhodospira abdelmalekii and Rhodopseudomonas viridis membranes are close to 13 nm, those of Thiocapsa pfennigii and Rhodopseudomonas sulfoviridis are slightly smaller (∼12.5 nm).

Full Kinetics and a Mechanism Investigation for the Generation of 4- Substituted 1, 4-Dihydropyridine Derivatives in the Presence of Green Catalyst and Aqueous Medium: Experimental Procedure

2020 ◽  
Vol 17 ◽  
Author(s):  
Sayyed Mostafa Habibi-Khorassani ◽  
Mehdi Shahraki ◽  
Sadegh Talaiefar
Keyword(s):  
Reaction Mechanism ◽  
Reaction Centre ◽  
Green Catalyst ◽  
Experimental Procedure ◽  
Dominant Mechanism ◽  
Rate Determining Step ◽  
12 Steps ◽  
Reaction Constant ◽  
Substituted 1 ◽  
Dihydropyridine Derivatives

Aims and Objective: The main objective of the kinetic investigation of the reaction among ethyl acetoacetate 1, ammoniumacetat 2, dimedone 3 and diverse substitutions of benzaldehyde 4-X, (X= H, NO2, CN, CF3, Cl, CH (CH3)2, CH3, OCH3, OCH3, and OH) for the generation of 4-substituted 1, 4-dihydropyridine derivatives (product 5) was the recognition of the most realistic reaction mechanism. The layout of the reaction mechanism studied kinetically by means of the UV-visible spectrophotometry approach. Materials and Methods: Among the various mechanisms, only mechanism1 (path1) involving 12 steps was recognized as a dominant mechanism (path1). Herein, the reaction between reactants 1 and 2 (kobs= 814.04 M-1 .min-1 ) and also compound 3 and 4-H (kobs= 151.18 M-1 .min-1 ) were the logical possibilities for the first and second fast steps (step1 and step2, respectively). Amongst the remaining steps, only step9 of the dominant mechanism (path1) had substituent groups (X) near the reaction centre that could be directly resonated with it. Results and Discussion: Para electron-withdrawing or donating groups on the compound 4-X increases the rate of the reaction 4 times more or decreases 8.7 times less than the benzaldehyde alone. So, this step is sensitive for monitoring any small or huge changes in the reaction rate. For this reason, step9 is the rate-determining step of the reaction mechanism (path1). Conclusion: The recent result is the agreement with the Hammett description with an excellent dual substituent factor (r = 0.990) and positive value of reaction constant (ρ = +0.9502) which confirmed both the resonance and inductive effects “altogether” contributed on the reaction centre of step9 in the dominant mechanism (path1).

Chemometric Analysis of Substituent Effects. VIII. Alternative Interpretation of Substituent Effects (AISE)

1995 ◽  
Vol 60 (9) ◽  
pp. 1502-1528 ◽  
Author(s):  
Oldřich Pytela
Keyword(s):  
Multiple Bond ◽  
Substituent Effects ◽  
Alternative Interpretation ◽  
Class I ◽  
Reaction Centre ◽  
Correlation Equations ◽  
Class Iii ◽  
Substituent Constant ◽  
Chemical Models ◽  
The Individual

Alternative interpretation of substituent effects (AISE) starts from the presumption that a substituent only possesses a single property described by a single substituent constant. This property is transmitted to the reaction centre by three different ways depending on the interaction type in the triad reaction centre - basic skeleton - substituent. For interpretation it is substantial whether or not the substituent has p electrons at the atom adjacent to the basic skeleton. If it has none, the substituent belongs to class I and operates only by its basic effect described by the mentioned single substituent constant. Substituents of class II possess a free electron pair at the atom adjacent to the basic skeleton, and those of class III have a multiple bond between the first and the second atoms which is polarized in the direction from the basic skeleton. Substituent effects in class I are described by a substituent constant identical with σI constant. Substituents in classes II and III show additional effects proportional to the same constant. Hence, a separate treatment of substituent effects in the individual classes provides three straight lines intersecting in a common point. Mathematically, the description of substituent effects in this approach is expressed by a family of lines with a single explaining variable. The point of intersection, which is referred to as the iso-effect point, is not identical with the classic standard substituent - hydrogen - but is near to CN substituent. The approach given has the advantage of adopting a single substituent constant whose scale can be adjusted relatively precisely. Its drawback (like in the case of the correlation equations derived from the principle of separation of substituent effects) lies in a more extensive set of substituents needed for a correlation. The AISE principle has been applied to 318 series of experimental data describing effects of 32 substituents in a large variety of chemical models (aliphatic, alicyclic, aromatic, heteroaromatic, with or without direct conjugation between reaction centre and substituent) in both chemical reactions and equilibria. A comparison with two other correlation relations with two and three substituent constants for interpretation of substituent effects based on the principle of separation of the individual substituent effects showed that the closeness of AISE based correlations is comparable with that of the correlation equations currently used. It was somewhat less successful in the models with direct conjugation between reaction centre and substituent but the AISE principle can be used even in these cases.

Chemometric Analysis of Substituent Effects. VII. Inductive Effect as a Basic Substituent Effect. Isoeffect Substituent Constant

1995 ◽  
Vol 60 (8) ◽  
pp. 1316-1332 ◽  
Author(s):  
Oldřich Pytela ◽  
Aleš Halama
Keyword(s):  
Inductive Effect ◽  
Chemical Shifts ◽  
Quantitative Description ◽  
Substituent Effects ◽  
Intersection Point ◽  
Chemometric Analysis ◽  
Reaction Centre ◽  
Substituent Constant ◽  
Modified Method ◽  
Substituted Benzoic Acids

The paper deals with chemometric analysis of the inductive effect. The notion of inductive effect is discussed, and unambiguous definitions are given for the notions of triad: reaction centre-basic skeleton-substituent, and the therewith connected definitions of inductive effect. For a quantitative description of inductive effect 7 types of chemical models were selected including noncyclic compounds, cyclic, and bicyclic compounds, derivatives of quinuclidine, 3-substituted benzoic acids, sulfonamides and pyridines. Altogether 139 sets of experimental data from literature have been used including altogether 1 294 points (9.3 points per set, 5 points at least) reflecting substituent effects of 34 substituents. It has been found that for a standard model the dissociation of substituted bicycloalkanecarboxylic acids only is satisfactory, all the other models reflecting also the mesomeric effects to variable extent (up to 10%). A distinctly different substitution behaviour was observed with 19F and 13C NMR chemical shifts of 4-substituted 1-fluoro- or 1-methylbicyclo[2.2.2]octanes. The earlier suggested model of substituent effects based on different way of transmission of substituent effects (3 classes) has been used for separating the inductive and mesomeric effects: it is mathematically presented as a set of straight lines with the intersection point at the so-called isoeffect substituent constant. Using the modified method of conjugated deviations a chemometric scale has been created for the inductive effect which agrees very well with the conventional scales given in literature; the only differences were observed for F and CH=O substituents (which are overestimated and underestimated, respectively, in literature). In the context given the inductive effect appears as a fundamental quantity forming a basis for quantitative description of other effects transferred by electrons.

A fifth chloroplast-encoded polypeptide is present in the photosystem II reaction centre complex

FEBS Letters ◽  
1989 ◽  
Vol 242 (2) ◽  
pp. 259-262 ◽  
Author(s):  
A.N. Webber ◽  
L. Packman ◽  
D.J. Chapman ◽  
J. Barber ◽  
J.C. Gray
Keyword(s):  
Photosystem Ii ◽  
Reaction Centre

scholarly journals On the performance of a photosystem II reaction centre-based photocell

2017 ◽  
Vol 8 (10) ◽  
pp. 6871-6880 ◽  
Author(s):  
Richard Stones ◽  
Hoda Hossein-Nejad ◽  
Rienk van Grondelle ◽  
Alexandra Olaya-Castro
Keyword(s):  
Photosystem Ii ◽  
Current Noise ◽  
Reaction Centre ◽  
Electron Counting ◽  
The Mean ◽  
Counting Statistics ◽  
Mean Current

We investigate the performance of a theoretical photosystem II reaction centre-inspired photocell device through the framework of electron counting statistics. In particular we look at the effect of a structured vibrational environment on the mean current and current noise.

scholarly journals UV-B radiation induced exchange of the D1 reaction centre subunits produced from the psbA2 and psbA3 genes in the cyanobacterium Synechocystis sp. PCC 6803

2000 ◽  
Vol 267 (9) ◽  
pp. 2640-2648 ◽  
Author(s):  
Imre Vass ◽  
Diana Kirilovsky ◽  
Irene Perewoska ◽  
Zoltán Máté ◽  
Ferenc Nagy ◽  
...  
Keyword(s):  
Reaction Centre ◽  
Radiation Induced ◽  
Synechocystis Sp ◽  
Pcc 6803
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