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Energy and molecules from photochemical/photocatalytic reactions. An overview.

ABSTRACT: Photocatalytic reactions have been defined as those processes that require both a (not consumed) catalyst and light. A previous definition was whether such reactions brought a system towards or away from the (thermal) equilibrium. This consideration brings in the question whether a part of the photon energy is incorporated into the photochemical reaction products. Data are provided for representative organic reactions involving or not molecular catalysts and show that energy storage occurs only when a heavily strained structure is generated, and in that case only a minor part of photon energy is actually stored (?G up to 25 kcal·mol-1). The green role of photochemistry/photocatalysis is rather that of forming highly reactive intermediates under mild conditions.

SUBMITTER: Ravelli D

PROVIDER: S-EPMC6272209 | biostudies-literature | 2015 Jan

REPOSITORIES: biostudies-literature

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Energy and molecules from photochemical/photocatalytic reactions. An overview.

Ravelli Davide D Protti Stefano S Albini Angelo A

Molecules (Basel, Switzerland) 20150116 1

Photocatalytic reactions have been defined as those processes that require both a (not consumed) catalyst and light. A previous definition was whether such reactions brought a system towards or away from the (thermal) equilibrium. This consideration brings in the question whether a part of the photon energy is incorporated into the photochemical reaction products. Data are provided for representative organic reactions involving or not molecular catalysts and show that energy storage occurs only ...[more]

PMID: 25603499

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Project description:In Photosystem I (PS I) long-wavelength chlorophylls (LWC) of the core antenna are known to extend the spectral region up to 750 nm for absorbance of light that drives photochemistry. Here we present clear evidence that even far-red light with wavelengths beyond 800 nm, clearly outside the LWC absorption bands, can still induce photochemical charge separation in PS I throughout the full temperature range from 295 to 5 K. At room temperature, the photoaccumulation of P700(+•) was followed by the absorbance increase at 826 nm. At low temperatures (T < 100 K), the formation of P700(+•)FA/B(-•) was monitored by the characteristic EPR signals of P700(+•) and FA/B(-•) and by the characteristic light-minus-dark absorbance difference spectrum in the QY region. P700 oxidation was observed upon selective excitation at 754, 785, and 808 nm, using monomeric and trimeric PS I core complexes of Thermosynechococcus elongatus and Arthrospira platensis, which differ in the amount of LWC. The results show that the LWC cannot be responsible for the long-wavelength excitation-induced charge separation at low temperatures, where thermal uphill energy transfer is frozen out. Direct energy conversion of the excitation energy from the LWC to the primary radical pair, e.g., via a superexchange mechanism, is excluded, because no dependence on the content of LWC was observed. Therefore, it is concluded that electron transfer through PS I is induced by direct excitation of a proposed charge transfer (CT) state in the reaction center. A direct signature of this CT state is seen in absorbance spectra of concentrated PS I samples, which reveal a weak and featureless absorbance band extending beyond 800 nm, in addition to the well-known bands of LWC (C708, C719 and C740) in the range between 700 and 750 nm. The present findings suggest that nature can exploit CT states for extending the long wavelength limit in PSI even beyond that of LWC. Similar mechanisms may work in other photosynthetic systems and in chemical systems capable of photoinduced electron transfer processes in general.

Dataset Information

Energy and molecules from photochemical/photocatalytic reactions. An overview.

Publications

Energy and molecules from photochemical/photocatalytic reactions. An overview.

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