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热化学发光过氧化物晶体。

Thermochemiluminescent peroxide crystals.

机构信息

New York University Abu Dhabi, P.O. Box 129188, Abu Dhabi, UAE.

Japan Synchrotron Radiation Research Institute, 1-1-1 Kouto, Sayo, Hyogo, 679-5198, Japan.

出版信息

Nat Commun. 2019 Mar 1;10(1):997. doi: 10.1038/s41467-019-08816-8.

Abstract

Chemiluminescence, a process of transduction of energy stored within chemical bonds of ground-state reactants into light via high-energy excited intermediates, is known in solution, but has remained undetected in macroscopic crystalline solids. By detecting thermally induced chemiluminescence from centimeter-size crystals of an organic peroxide here we demonstrate direct transduction of heat into light by thermochemiluminescence of bulk crystals. Heating of crystals of lophine hydroperoxide to ~115 °C results in detectable emission of blue-green light with maximum at 530 nm with low chemiluminescent quantum yield [(2.1 ± 0.1) × 10 E mol]. Spectral comparison of the thermochemiluminescence in the solid state and in solution revealed that the solid-state thermochemiluminescence of lophine peroxide is due to emission from deprotonated lophine. With selected 1,2-dioxetane, endoperoxide and aroyl peroxide we also establish that the thermochemiluminescence is common for crystalline peroxides, with the color of the emitted light varying from blue to green to red.

摘要

化学发光是一种能量传递过程,将基态反应物化学键中储存的能量通过高能激发中间体转化为光,这在溶液中是已知的,但在宏观晶态固体中仍然未被检测到。通过检测有机过氧化物厘米大小晶体的热诱导化学发光,我们在这里证明了通过体相晶体的热化学发光将热直接转化为光。加热洛芬过氧化物晶体至约 115°C 会导致可检测的蓝绿光发射,最大发射波长为 530nm,化学发光量子产率低 [(2.1±0.1)×10^-3]mol。固态和溶液中热化学发光的光谱比较表明,洛芬过氧化物的固态热化学发光是由于去质子化的洛芬发出的光。我们还选择了 1,2-二氧杂环乙烷、内过氧化物和酰基过氧化物,证明了热化学发光是晶体过氧化物的共同特性,发射光的颜色从蓝色到绿色到红色变化。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/13ac/6397279/c55459138cfc/41467_2019_8816_Fig1_HTML.jpg

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