Stoffkennwerte

Rau, Hermann; Rau, Jenspeter

doi:10.1007/978-3-663-09492-0_8

Cited by 10 publications

(15 citation statements)

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“…If the constraint allows a certain amount of rotation, rotational relaxation will compete with direct de‐excitation to S 1 and this quantum yield will hardly change, as reported in ref. and .…”

Section: Discussionmentioning

confidence: 97%

“…On one hand, in all cases quantum yields become almost wavelength‐independent, showing the same results when exciting separately to S 1 (nπ*) or to S 2 (ππ*). On the other hand, using different restrictive strategies, in some cases the value obtained is the same as when excited to S 2 (ππ*) in free‐rotation systems (0.13 approximately), and in others it was equal to the value for excitation to S 1 (nπ*) in free‐rotation systems (between 0.21–0.24) . As a result, whether rotation is completely or only partially precluded is not clear …”

Section: Introductionmentioning

confidence: 93%

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Excited‐State Decay in the Photoisomerisation of Azobenzene: A New Balance between Mechanisms

2016

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Abstract:The mechanism of the photoisomerization of azobenzene has been studied by means of multiconfigurational ab initio calculations. Our results show that it is necessary to account for the dynamic electron correlation in the location of the critical points (CASPT2 optimizations) to obtain a correct description of the topography of the potential energy surfaces of the low-energy singlet excited states. Using this methodology, we have found that the state populated by the initial excitation is the S2 (ππ*) state, which decays very efficiently to the S1 (nπ*) state at a pedal-like non-rotated geometry. On the S1 state, relaxation leads to a rotated geometry where the system decays to the ground state, in which further relaxation can lead to either the trans or cis geometries. However the S1/S0 CI seam also extends to planar geometries, so this reaction path is also accessible for rotation-constrained systems. Our results explain the experimental observations satisfactorily.

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Section: Discussionmentioning

confidence: 97%

Section: Introductionmentioning

confidence: 93%

Excited‐State Decay in the Photoisomerisation of Azobenzene: A New Balance between Mechanisms

2016

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“…The change in the nature of the substituent is also reflected in red-shifting of the absorption wavelengths, which is typical of amidoABs. [29,47] AzoAP photochemistry reflects the impact of the electronic effects of amide groups, which dominate any effect introduced by intramolecular hydrogen bonds. A small increase in absorbance was observed at wavelengths greater than 480 nm, as expected for ABs bearing amide substituents.…”

Section: Photoisomerization and Thermal Relaxation In Solutionmentioning

confidence: 99%

Systematic Modulation of Hydrogen Bond Donors in Aminoazobenzene Derivatives Provides Further Evidence for the Concerted Inversion Photoisomerization Pathway

et al. 2013

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A series of aminoazobenzene derivatives structurally related to AzoAMP‐1 have been prepared and characterized by using a variety of analytical techniques. AzoAMP‐1 is based on 2,2′‐diaminoazobenzene with N‐methylpyridine groups. The new derivatives all contain a hydrogen bond between the aniline hydrogen atom and the azo group, as well as a separate pendant functional group that could contribute an additional hydrogen‐bond acceptor to an intramolecular network. A combination of photoisomerization studies and NMR spectroscopic and X‐ray crystallographic investigations suggest that AzoAMP‐1 possesses a unique structure that prevents isomerization through the concerted inversion pathway, which cannot be reproduced with other types or arrangements of substituents. Only AzoAMQ, which contains a similar quinolone heterocycle in place of the pyridine group of AzoAMP‐1, displayed somewhat similar photochemistry.

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“…Early reports demonstrated that the males of the wild silk moth Samia cynthia could locate a sex pheromone source over 2 miles away within several hours of their release (4). Studies of the silk moth Bombyx mori suggested that a single pheromone molecule was sufficient to activate olfactory neurons in the antenna (5).…”

mentioning

confidence: 99%

Snmp-1, a Novel Membrane Protein of Olfactory Neurons of the Silk Moth Antheraea polyphemus with Homology to the CD36 Family of Membrane Proteins

Rogers

Sun

Lerner

et al. 1997

Journal of Biological Chemistry

199

201

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While olfactory neurons of silk moths are well known for their exquisite sensitivity to sex pheromone odorants, molecular mechanisms underlying this sensitivity are poorly understood. In searching for proteins that might support olfactory mechanisms, we characterized the protein profile of olfactory neuron receptor membranes of the wild silk moth Antheraea polyphemus. We have purified and cloned a prominent 67-kDa protein which we have named Snmp-1 (sensory neuron membrane protein-1). Northern blot analysis suggests that Snmp-1 is uniquely expressed in antennal tissue; in situ hybridization and immunocytochemical analyses show that Snmp-1 is expressed in olfactory neurons and that the protein is localized to the cilia, dendrites, and somata but not the axons. Snmp-1 mRNA expression increases significantly 1-2 days before the end of adult development, coincident with the functional maturation of the olfactory system. Sequence analysis suggests Snmp-1 is homologous with the CD36 protein family, a phylogenetically diverse family of receptor-like membrane proteins. CD36 family proteins are characterized as having two transmembrane domains and interacting with proteinaceous ligands; Snmp-1 is the first member of this family identified in nervous tissue. These findings argue that Snmp-1 has an important role in olfaction; possible roles of Snmp-1 in odorant detection are discussed.The antennae of silk moths are well known for their exquisite sensitivity to pheremonal odorants (1-3). Early reports demonstrated that the males of the wild silk moth Samia cynthia could locate a sex pheromone source over 2 miles away within several hours of their release (4). Studies of the silk moth Bombyx mori suggested that a single pheromone molecule was sufficient to activate olfactory neurons in the antenna (5). In insects, odors are detected by sensilla, small hair-like structures arrayed along the antennae. The sensilla are hollow, fluid-filled cuticular structures that contain the receptor cilia of olfactory neurons. Small holes penetrate through the wall of a sensillum, permitting entry of odor molecules; odorant-binding proteins are then thought to transport the odor molecules through the fluid-filled lumen to receptor proteins in the receptor membranes of the olfactory neurons (3, 6 -9).In searching for proteins that might support olfactory mechanisms, we characterized the protein profile of olfactory neuron receptor membranes of the wild silk moth Antheraea polyphemus. The morphology of the A. polyphemus antenna permits the relatively easy isolation of olfactory sensilla in a manner yielding olfactory receptor cilia as the only cellular component (10). This preparation is free of other parts of the olfactory neurons as well as of nonneuronal cells of the antenna, and it was previously used to identify a pheromonebinding membrane protein using a radiolabeled photoaffinity analog of the A. polyphemus sex pheromone (10). This protein co-migrated with bovine serum albumin on SDS gels (around 67 kDa) and appeared to be uniquely exp...

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Stoffkennwerte

Cited by 10 publications

References 0 publications

Excited‐State Decay in the Photoisomerisation of Azobenzene: A New Balance between Mechanisms

Excited‐State Decay in the Photoisomerisation of Azobenzene: A New Balance between Mechanisms

Systematic Modulation of Hydrogen Bond Donors in Aminoazobenzene Derivatives Provides Further Evidence for the Concerted Inversion Photoisomerization Pathway

Snmp-1, a Novel Membrane Protein of Olfactory Neurons of the Silk Moth Antheraea polyphemus with Homology to the CD36 Family of Membrane Proteins

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