Photoallylation and Photoreduction of Cyclohexylidenepropanedinitrile by Use of Allyltrimethylsilane via Photoinduced Electron Transfer:  Control of the Product Ratio Depending on pKaValues of Additives

2001 ◽  
Vol 3 (9) ◽  
pp. 1277-1280 ◽  
Author(s):  
Tomoo Hayamizu ◽  
Munehiro Ikeda ◽  
Hajime Maeda ◽  
Kazuhiko Mizuno
Keyword(s):  
Electron Transfer ◽  
Photoinduced Electron Transfer ◽  
Product Ratio

Photochemical nucleophile–olefin combination, aromatic substitution (photo-NOCAS) reaction. Part 9: methanol-2,6-dimethyl-1,6-heptadiene, and 1,4-dicyanobenzene

1995 ◽  
Vol 73 (6) ◽  
pp. 762-771 ◽  
Author(s):  
Dennis A. Connor ◽  
Donald R. Arnold ◽  
Pradip K. Bakshi ◽  
T. Stanley Cameron
Keyword(s):  
Electron Transfer ◽  
Radical Cation ◽  
Photoinduced Electron Transfer ◽  
Aromatic Substitution ◽  
Radical Ions ◽  
Double Bonds ◽  
Alkoxy Radical ◽  
Product Ratio

The photochemical nucleophile–olefin combination, aromatic substitution (photo-NOCAS) reaction of methanol, 2,6-dimethyl-1,6-heptadiene, and 1,4-dicyanobenzene yields three distinct types of 1:1:1 adducts: an acyclic product, 4-(1-methoxymethyl-1,5-dimethyl-5-hexenyl)benzonitrile (8, 5%); a cis–trans pair of cyclohexanes, 4-(3-methoxymethyl-1,3-dimethylcyclohexyl)benzonitrile (9cis (12%) and 9trans (11%)); and a cis–trans pair of cycloheptanes, 4-(4-methoxy-1,4-dimethylcycloheptyl)benzonitrile (10cis (12%) and 10trans (10%)). Variation in the concentration of the nucleophile, methanol, and codonor, biphenyl, affects the product ratio and it has been possible to establish the mechanisms for the formation of these products. The acyclic product is formed by a typical photo-NOCAS reaction, that is, addition (anti-Markovnikov) across one of the heptadiene double bonds. The cyclohexane products are formed following 1,6-endo cyclization of the intermediate β-alkoxy radical. And the cycloheptane products result from 1,7-endo,endo cyclization of the initially formed 2,6-dimethyl-1,6-heptadiene radical cation. Comparison of the relative rates of these cyclization processes can be made with those of the next smaller homolog, 2,5-dimethyl-1,5-hexadiene. Keywords: photochemistry, photoinduced electron transfer, radical ions, radicals, cyclization.

Computationally Assisted Design of High Signal-to-Noise Photoinduced Electron Transfer-Based Voltage-Sensitive Dyes

2020 ◽  
Author(s):  
Rishikesh Kulkarni ◽  
Anneliese Gest ◽  
Chun Kei Lam ◽  
Benjamin Raliski ◽  
Feroz James ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Dft Calculations ◽  
Photoinduced Electron Transfer ◽  
Density Functional ◽  
Embryonic Stem ◽  
High Sensitivity ◽  
Md Simulations ◽  
High Signal ◽  
Signal To Noise ◽  
Green Fluorescent

<p>High signal-to-noise optical voltage indicators will enable simultaneous interrogation of membrane potential in large ensembles of neurons. However, design principles for voltage sensors with high sensitivity and brightness remain elusive, limiting the applicability of voltage imaging. In this paper, we use molecular dynamics (MD) simulations and density functional theory (DFT) calculations to guide the design of a bright and sensitive green-fluorescent voltage-sensitive fluorophore, or VoltageFluor (VF dye), that uses photoinduced electron transfer (PeT) as a voltage-sensing mechanism. MD simulations predict an 11% increase in sensitivity due to membrane orientation, while DFT calculations predict an increase in fluorescence quantum yield, but a decrease in sensitivity due to a decrease in rate of PeT. We confirm these predictions by synthesizing a new VF dye and demonstrating that it displays the expected improvements by doubling the brightness and retaining similar sensitivity to prior VF dyes. Combining theoretical predictions and experimental validation has resulted in the synthesis of the highest signal-to-noise green VF dye to date. We use this new voltage indicator to monitor the electrophysiological maturation of human embryonic stem cell-derived medium spiny neurons. </p>

Photoinduced electron transfer in mechanically interlocked suit[3]ane systems

2021 ◽  
Author(s):  
Anton J Stasyuk ◽  
Olga A. Stasyuk ◽  
Miquel Solà ◽  
Alexander Voityuk
Keyword(s):  
Electron Transfer ◽  
Photoinduced Electron Transfer ◽  
New Class ◽  
Transfer Processes ◽  
Two Component ◽  
Electron Transfer Processes

Suitanes, a new class of two-component mechanically interlocked systems, have recently been developed. In this work, we report a detailed study of photoinduced electron transfer processes in the suit[3]anes consisting...

scholarly journals A quantum optics approach to photoinduced electron transfer in cavities

2021 ◽  
Vol 154 (5) ◽  
pp. 054104
Author(s):  
D. Wellnitz ◽  
G. Pupillo ◽  
J. Schachenmayer
Keyword(s):  
Electron Transfer ◽  
Quantum Optics ◽  
Photoinduced Electron Transfer
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