scholarly journals Persistent Radical Pairs Between N-Substituted Naphthalimide and Carbanion Exhibit pKa-Dependent UV-vis Absorption

Author(s):  
Xiancheng Nie ◽  
Tao Wang ◽  
Xiaoyu Chen ◽  
Wenhuan Huang ◽  
Linkun Huang ◽  
...  

A new strategy is constructed for estimating and screening pK<sub>a</sub> values among different carbon acids under ambient conditions via the UV-vis absorption spectrum of persistent radical pair originating from an <i>N</i>-substituted naphthalimide (NNI) derivative in the presence of various carbanions in organic solutions

2019 ◽  
Author(s):  
Xiancheng Nie ◽  
Tao Wang ◽  
Xiaoyu Chen ◽  
Wenhuan Huang ◽  
Linkun Huang ◽  
...  

A new strategy is constructed for estimating and screening pK<sub>a</sub> values among different carbon acids under ambient conditions via the UV-vis absorption spectrum of persistent radical pair originating from an <i>N</i>-substituted naphthalimide (NNI) derivative in the presence of various carbanions in organic solutions


2019 ◽  
Author(s):  
Xiancheng Nie ◽  
Tao Wang ◽  
Xiaoyu Chen ◽  
Wenhuan Huang ◽  
Linkun Huang ◽  
...  

A new strategy is constructed for estimating and screening pK<sub>a</sub> values among different carbon acids under ambient conditions via the UV-vis absorption spectrum of persistent radical pair originating from an <i>N</i>-substituted naphthalimide (NNI) derivative in the presence of various carbanions in organic solutions


2020 ◽  
Author(s):  
Jordan Smith ◽  
Hadi Zadeh Haghighi ◽  
Christoph Simon

ABSTRACTUnderstanding the mechanisms underlying anesthesia would be a key step towards understanding consciousness. The process of xenon-induced general anesthesia has been shown to involve electron transfer, and the potency of xenon as a general anesthetic exhibits isotopic dependence. We propose that these observations can be explained by a mechanism in which the xenon nuclear spin influences the recombination dynamics of a naturally occurring radical pair of electrons. We develop a simple model inspired by the body of work on the radical-pair mechanism in cryptochrome in the context of avian magnetoreception, and we show that our model can reproduce the observed isotopic dependence of the general anesthetic potency of xenon in mice. Our results are consistent with the idea that radical pairs of electrons with entangled spins could be important for consciousness.


2009 ◽  
Vol 7 (suppl_2) ◽  
Author(s):  
Erin Hill ◽  
Thorsten Ritz

A proposed mechanism for magnetic compasses in animals is that systems of radical pairs transduce magnetic field information to the nervous system. One can show that perfectly ordered arrays of radical pairs are sensitive to the direction of the external magnetic field and can thus operate, in principle, as a magnetic compass. Here, we investigate how disorder, inherent in biological cells, affects the ability of radical pair systems to provide directional information. We consider biologically inspired geometrical arrangements of ensembles of radical pairs with increasing amounts of disorder and calculate the effect of changing the direction of the external magnetic field on the rate of chemical signal production by radical pair systems. Using a previously established signal transduction model, we estimate the minimum number of receptors necessary to allow for detection of the change in chemical signal owing to changes in magnetic field direction. We quantify the required increase in the number of receptors to compensate for the signal attenuation through increased disorder. We find radical-pair-based compass systems to be relatively robust against disorder, suggesting several scenarios as to how a compass structure can be realized in a biological cell.


2006 ◽  
Vol 78 (1) ◽  
pp. 31-44 ◽  
Author(s):  
Jinqi Xu ◽  
Mathew George ◽  
Richard G. Weiss

Both the regio- and stereo-chemistries of the photoreactions of 1-naphthyl (R)-2-phenylpropanoate have been investigated in poly(vinyl acetate) films in their glassy (at 5ºC) and melted (at 50ºC) states and in ethyl acetate. These results are compared with those from irradiations in polyethylene films and in n-hexane. The regioselectivity of the intermediate 1-naphthoxy/(R)-2-phenylpropanoyl radical pair combinations is much higher in both the melt and glassy states of poly(vinyl acetate) films than that in the melt state of completely amorphous polyethylene films, but the stereoselectivity of intermediate prochiral 1-naphthoxy/1-phenylethyl radical pair combinations is much lower in poly(vinyl acetate). The results emphasize the need to control the ratio between the rates of radical tumbling and translation, as well as the ratio between the rates of in-cage motions and cage-escape, if high stereo- and regio-selectivities of combination products are to be achieved. A mechanistic picture of how the radicals of the intermediate pairs are affected by and interact with the various media is advanced.


2009 ◽  
Vol 37 (2) ◽  
pp. 358-362 ◽  
Author(s):  
Jonathan R. Woodward ◽  
Timothy J. Foster ◽  
Alex R. Jones ◽  
Adrian T. Salaoru ◽  
Nigel S. Scrutton

The effect of magnetic fields on chemical reactions through the RP (radical pair) mechanism is well established, but there are few examples, in the literature, of biological reactions that proceed through RP intermediates and show magnetic field-sensitivity. The present and future relevance of magnetic field effects in biological reactions is discussed.


2021 ◽  
Author(s):  
Hadi ZADEH-HAGHIGHI ◽  
Christoph Simon

The exact mechanism behind general anesthesia remains an open question in neuroscience. It has been proposed that anesthetics selectively prevent consciousness and memory via acting on microtubules (MTs). It is known that the magnetic field modulates MT organization. A recent study shows that a radical pair model can explain the isotope effect in xenon-induced anesthesia and predicts magnetic field effects on anesthetic potency. Further, reactive oxygen species are also implicated in MT stability and anesthesia. Based on a simple radical pair mechanism model and a simple mathematical model of MT organization, we show that magnetic fields can modulate spin dynamics of naturally occurring radical pairs in MT. We show that the spin dynamics influence a rate in the reaction cycle, which translates into a change in the MT density. We can reproduce magnetic field effects on the MT concentration that have been observed. Our model also predicts additional effects at slightly higher fields. Our model further predicts that the effect of zinc on the MT density exhibits isotopic dependence. The findings of this work make a connection between microtubule-based and radical pair-based quantum theories of consciousness.


2018 ◽  
Author(s):  
P. J. Hore

AbstractProlonged exposure to weak (~1 μT) extremely-low-frequency (ELF, 50/60 Hz) magnetic fields has been associated with an increased risk of childhood leukaemia. One of the few biophysical mechanisms that might account for this link involves short-lived chemical reaction intermediates known as radical pairs. In this report, we use spin dynamics simulations to derive an upper bound of 10 parts per million on the effect of a 1 μT ELF magnetic field on the yield of a radical pair reaction. By comparing this figure with the corresponding effects of changes in the strength of the Earth’s magnetic field, we conclude that if exposure to such weak 50/60 Hz magnetic fields has any effect on human biology, and results from a radical pair mechanism, then the risk should be no greater than travelling a few kilometres towards or away from the geomagnetic north or south pole.


1976 ◽  
Vol 31 (9-10) ◽  
pp. 575-588 ◽  
Author(s):  
G. W. Pohl

Abstract Three fluorescent dyes (a merocyanin, a cyanin and a modified umbelliferon) have been in­corporated into vesicles from three different lecithins. Their absorption spectrum, emission spectrum and fluorescence polarization in the lipid vesicles has been studied and compared with the spectral properties in homogeneous organic solutions. The reactivity of lipid bound dyes with reagents in the aqueous phase was investigated. The location use as indicators of phase transitions or membrane


2010 ◽  
Vol 8 (56) ◽  
pp. 451-456 ◽  
Author(s):  
Ming-Wei Chang ◽  
Eleanor Stride ◽  
Mohan Edirisinghe

Drug-delivery systems with a unique capability to respond to a given stimulus can improve therapeutic efficacy. However, development of such systems is currently heavily reliant on responsive polymeric materials and pursuing this singular strategy limits the potential for clinical translation. In this report, with a model system used for drug-release studies, we demonstrate a new strategy: how a temperature-responsive non-toxic, volatile liquid can be encapsulated and stored under ambient conditions and subsequently programmed for controlled drug release without relying on a smart polymer. When the stimulus temperature is reached, controlled encapsulation of different amounts of dye in the capsules is achieved and facilitates subsequent sustained release. With different ratios of the liquid (perfluorohexane): dye in the capsules, enhanced controlled release with real-time response is provided. Hence, our findings offer great potential for drug-delivery applications and provide new generic insights into the development of stimuli drug-release systems.


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