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Controlling thermal reactivity with different colors of light.

ABSTRACT: The ability to switch between thermally and photochemically activated reaction channels with an external stimulus constitutes a key frontier within the realm of chemical reaction control. Here, we demonstrate that the reactivity of triazolinediones, powerful coupling agents in biomedical and polymer research, can be effectively modulated by an external photonic field. Specifically, we show that their visible light-induced photopolymerization leads to a quantitative photodeactivation, thereby providing a well-defined off-switch of their thermal reactivity. Based on this photodeactivation, we pioneer a reaction manifold using light as a gate to switch between a UV-induced Diels-Alder reaction with photocaged dienes and a thermal addition reaction with alkenes. Critically, the modulation of the reactivity by light is reversible and the individually addressable reaction pathways can be repeatedly accessed. Our approach thus enables a step change in photochemically controlled reactivity, not only in small molecule ligations, yet importantly in controlled surface and photoresist design.

SUBMITTER: Houck HA

PROVIDER: S-EPMC5707371 | biostudies-literature | 2017 Nov

REPOSITORIES: biostudies-literature

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Controlling thermal reactivity with different colors of light.

Houck Hannes A HA Du Prez Filip E FE Barner-Kowollik Christopher C

Nature communications 20171130 1

The ability to switch between thermally and photochemically activated reaction channels with an external stimulus constitutes a key frontier within the realm of chemical reaction control. Here, we demonstrate that the reactivity of triazolinediones, powerful coupling agents in biomedical and polymer research, can be effectively modulated by an external photonic field. Specifically, we show that their visible light-induced photopolymerization leads to a quantitative photodeactivation, thereby pro ...[more]

PMID: 29187733

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Project description:Light colors may affect poultry behaviors, well-being and performance. However, preferences of layer pullets for light colors are not fully understood. This study was conducted to investigate the pullet preferences for four light-emitting diode colors, including white, red, green and blue, in a lighting preference test system. The system contained four identical compartments each provided with a respective light color. The pullets were able to move freely between the adjacent compartments. A total of three groups of 20 Chinese domestic Jingfen layer pullets (54 to 82 days of age) were used for the test. Pullet behaviors were continuously recorded and summarized for each light color/compartment into daily time spent (DTS), daily percentage of time spent (DPTS), daily times of visit (DTV), duration per visit, daily feed intake (DFI), daily feeding time (DFT), feeding rate (FR), distribution of pullet occupancy and hourly time spent. The results showed that the DTS (h/pullet·per day) were 3.9±0.4 under white, 1.4±0.3 under red, 2.2±0.3 under green and 4.5±0.4 under blue light, respectively. The DTS corresponded to 11.7% to 37.6% DPTS in 12-h lighting periods. The DTV (times/pullet·per day) were 84±5 under white, 48±10 under red, 88±10 under green and 94±8 under blue light. Each visit lasted 1.5 to 3.2 min. The DFI (g/pullet·per day) were 27.6±1.7 under white, 7.1±1.6 under red, 15.1±1.1 under green and 23.1±2.0 under blue light. The DFT was 0.18 to 0.65 h/pullet·per day and the FR was 0.57 to 0.75 g/min. For most of the time during the lighting periods, six to 10 birds stayed under white, and one to five birds stayed under red, green and blue light. Pullets preferred to stay under blue light when the light was on and under white light 4 h before the light off. Overall, pullets preferred blue light the most and red light the least. These findings substantiate the preferences of layer pullets for light colors, providing insights for use in the management of light-emitting diode colors to meet pullet needs.

Project description:Hemoglobin I (HbI) from the clam Lucina pectinata is an intriguing hemeprotein that binds and transports H(2)S to sulfide-oxidizing chemoautotrophic bacteria to maintain a symbiotic relationship and to protect the mollusk from H(2)S toxicity. Single point mutations at E7, B10, and E11 were introduced into the HbI heme pocket to define the reactivity of sulfide with hemeproteins. The functional and structural properties of mutant and wild-type recombinant proteins were first evaluated using the well-known ferrous CO and O(2) derivatives. The effects of these mutations on the ferric environment were then studied in the metaquo and hydrogen sulfide derivatives. The results obtained with the ferrous HbI mutants show that all the E7 substitutions and the PheB10Tyr mutation influence directly CO and O(2) binding and stability while the B10 and E11 substitutions induce distal structural rearrangements that affect ligand entry and escape indirectly. For the metaquo-GlnE7His, -PheB10Val, -PheB10Leu, and -E11 variants, two individual distal structures are suggested, one of which is associated with H-bonding interactions between the E7 residues and the bound water. Similar H-bonding interactions are invoked for these HbI-H(2)S mutant derivatives and the rHbI, altering in turn sulfide reactivity within these protein samples. This is evident in the resonance Raman spectra of these HbI-H(2)S complexes, which show reduction of heme iron as judged by the appearance of the nu(4) oxidation state marker at 1356 cm(-1), indicative of heme-Fe(II) species. This reduction process depends strongly on distal mutations showing faster reduction for those HbI mutants exhibiting the strongest H-bonding interactions. Overall, the results presented here show that (a) H(2)S association is regulated by external kinetic barriers, (b) H(2)S release is controlled by two competing reactions involving simple sulfide dissociation and heme reduction, (c) at high H(2)S concentrations, reduction of the ferric center dominates, and (d) reduction of the heme is also enhanced in those HbI mutants having polar distal environments.

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Controlling thermal reactivity with different colors of light.

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Controlling thermal reactivity with different colors of light.

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