Solvent Effects on Nonradiative Relaxation Dynamics of Low-Energy Ligand-Field Excited States: A CuCl<sub>4</sub><sup>2–</sup> Complex

Mereshchenko, Andrey S.; Myasnikova, Olesya S.; Panov, Maxim S.; Kochemirovsky, Vladimir A.; Skripkin, M. Yu.; Budkina, Darya S.; Tarnovsky, Alexander N.

doi:10.1021/acs.jpcb.7b02015

Cited by 5 publications

(3 citation statements)

References 49 publications

(97 reference statements)

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“…Acetonitrile as an anhydrous solvent is important to study the phototoxicity of NPX. Conducting experiments in anhydrous solvents can eliminate the hydrogen-bond effect, proton-transfer process in ground and/or excited states . For the physiological concerns, acetonitrile as solvent can simulate the anhydrous environments in human body, as sometimes drugs will be delivered to the hydrophobic environment …”

Section: Resultsmentioning

confidence: 99%

Unveiling the Photophysical and Photochemical Reaction Process of Naproxen via Ultrafast Femtosecond to Nanosecond Laser Flash Photolysis

Liang

Sun

Huang

et al. 2019

Chem. Res. Toxicol.

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Naproxen is a nonsteroidal anti-inflammatory drug that exhibits phototoxic side effects in humans, but its mechanism of phototoxicity is ambiguous. To uncover photophysical and photochemical reaction processes of naproxen, femtosecond to nanosecond transient absorption spectroscopies were employed to directly detect excited and transient states of naproxen upon UV irradiation in pure acetonitrile, acetonitrile:water 1:1, and acetonitrile:PBS 1:1 solutions. The transient absorption data together with time-dependent density functional theory analysis-predicted absorption spectra of selected intermediates were integrated to elucidate photochemical mechanisms for reactions of naproxen in different solutions. Femtosecond transient absorption results demonstrated that naproxen has two different photochemical pathways at the early delay time before the formation of final products in various solutions. In a pure acetonitrile solvent, naproxen undergoes charge transfer to solvent to generate a radical cation intermediate, which decarboxylates to generate a radical 2B intermediate. While in an acetonitrile:PBS 1:1 solution, naproxen predominantly deprotonates first and is promoted to the singlet exited state (1NPX–), which undergoes intersystem crossing to give rise to the lowest-lying triplet states (T1). T1 then undergoes decarboxylation reaction and produces a radical 2B species. Kinetic characterization of these processes reveals that the decarboxylation reaction in an acetonitrile:PBS 1:1 solution is faster than that in a pure acetonitrile solvent. Deep studies on photophysical and photochemical processes of NPX will aid us to better understand the toxicology mechanisms associated with NPX in different conditions.

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Section: Resultsmentioning

confidence: 99%

Unveiling the Photophysical and Photochemical Reaction Process of Naproxen via Ultrafast Femtosecond to Nanosecond Laser Flash Photolysis

Liang

Sun

Huang

et al. 2019

Chem. Res. Toxicol.

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“…To avoid proton transfer, the solvent must be anhydrous and aprotic. Physiologically, MeCN can be used as a solvent to simulate the anhydrous microenvironment in the human body. , In fact, drugs are sometimes delivered to hydrophobic environments to be released and utilized . In a deoxygenated pure MeCN solvent, CP is first excited to the first singlet excited state (S 1 ) upon 300 nm pump beam and then S 1 rapidly undergoes the solvent rearrangement (SR) (see the detailed assignment below).…”

Section: Resultsmentioning

confidence: 99%

Revealing the Photophysical and Photochemical Reaction Processes of Carprofen in Different Solutions via Ultrafast Femtosecond to Nanosecond Transient Absorption

Liu

Yin

et al. 2021

Chem. Res. Toxicol.

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Carprofen (CP), one kind of a nonsteroidal antiinflammatory drug, exhibits phototoxic side effects in physiology, while its phototoxic mechanism is ambiguous. To uncover CP's photophysical and photochemical reaction processes, femtosecond to nanosecond transient absorption spectroscopies were employed to directly detect excited states and transient intermediates of CP upon UV irradiation in pure acetonitrile (MeCN), MeCN/water 1:1, and acid/alkaline buffer solutions. The transient absorption data together with DFT calculations were integrated to elucidate mechanisms for photochemical reactions of CP in different solutions. The associated photophysical and photochemical reaction pathways are dependent on various solution environments. In a pure MeCN solvent, CP is excited to a singlet state (S 1 ) and rapidly interacts with the solvent to proceed solvent rearrangement (SR). It then undergoes vibrational cooling (VC) and proceeds intersystem crossing (ISC) to produce the lowest triplet state ( 3 CP). 3 CP finally decays to the ground state. While in a MeCN/water 1:1 solution, deprotonated S 1 of CP experiences SR and VC processes, and then it is promoted to a deprotonated triplet state ( 3 CP − ). 3 CP − undergoes the parallel reactions: dechlorination to a phenyl radical ( 2 CP − ) and decarboxylation to a T 1 anion ( 3 CP − (de-CO 2 )). Finally, both intermediates produce the radical anion species 2 CP − (de-CO 2 ). In a pH = 7.4 (MeCN/PBS 1:1) solution, 3 CP − can be converted into 2 CP − (de-CO 2 ) more quickly. Interestingly, we found that the dechlorination step can be promoted in an alkaline solution. Phenyl and chlorine radicals produced in an aqueous solution may be the root cause of the drug's harmful side effects on the human body. This may be useful to guide the design of related CP drugs with minimal phototoxicity in the pharmaceutical process.

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“…UV-visible diffuse reflectance spectra show that TNS has an absorption edge near 373 nm, which enhanced to 560 nm by utilizing biphenylamine complexes on TNS. Because biphenylamine complexes possess d-d electronic transitions, an asymmetric distorted octahedral ionic sheet (framework) [41]. The symmetric copper complexes of the selected amines i.e.…”

Section: Resultsmentioning

confidence: 99%

Sensitization of TiO₂ nanosheets with Cu–biphenylamine framework to enhance photocatalytic degradation performance of toxic organic contaminants: synthesis, mechanism and kinetic studies

Khan

Mutahir²,

Wang³

et al. 2018

Nanotechnology

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TNS/Cu(X) composite materials were firstly synthesized via simple overnight stirring of TNS in the methanolic solution of Cu complexes. The developed TNS/Cu(X) composites had a well-designed nanostructure, in which the TNS and Cu complexes were closely bounded with each other. The biphenylamine complexes fixed on the TNS surface in form of nanocapsules, which were confirmed by TEM and SEM, thus improving the surface area and subsequently charge separation. Innovatively merged photocatalysts of Cu complexes with TNS were successfully verified for photocatalytic mineralization of colored and colorless organic contaminants under the visible light degradation. As compared to original TNS, TNS/Cu(BA) showed prominent improvement in the catalytic actions. Kinetics i.e. t (half-life times period), K, and R (linear regression co-efficient) were also studied. The amended materials created charge separation, by means of electrons gathering at the higher CB, and holes gathering at the lower level valence band of the Cu complex, therefore improving mineralization efficiency of the electrons and holes. TNS/Cu(BA) degrade 99%-99.6% of methyl orange (MO) and rhodamine B (RhB) dyes at 120 min, and 160 min, respectively, and 68% of phenol and 53% of TCP were destroyed in 180 min. The resilient holes can directly destroy MO, RhB, phenol, and TCP.

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Solvent Effects on Nonradiative Relaxation Dynamics of Low-Energy Ligand-Field Excited States: A CuCl₄^2– Complex

Cited by 5 publications

References 49 publications

Unveiling the Photophysical and Photochemical Reaction Process of Naproxen via Ultrafast Femtosecond to Nanosecond Laser Flash Photolysis

Unveiling the Photophysical and Photochemical Reaction Process of Naproxen via Ultrafast Femtosecond to Nanosecond Laser Flash Photolysis

Revealing the Photophysical and Photochemical Reaction Processes of Carprofen in Different Solutions via Ultrafast Femtosecond to Nanosecond Transient Absorption

Sensitization of TiO₂ nanosheets with Cu–biphenylamine framework to enhance photocatalytic degradation performance of toxic organic contaminants: synthesis, mechanism and kinetic studies

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Solvent Effects on Nonradiative Relaxation Dynamics of Low-Energy Ligand-Field Excited States: A CuCl42– Complex

Cited by 5 publications

References 49 publications

Unveiling the Photophysical and Photochemical Reaction Process of Naproxen via Ultrafast Femtosecond to Nanosecond Laser Flash Photolysis

Unveiling the Photophysical and Photochemical Reaction Process of Naproxen via Ultrafast Femtosecond to Nanosecond Laser Flash Photolysis

Revealing the Photophysical and Photochemical Reaction Processes of Carprofen in Different Solutions via Ultrafast Femtosecond to Nanosecond Transient Absorption

Sensitization of TiO2 nanosheets with Cu–biphenylamine framework to enhance photocatalytic degradation performance of toxic organic contaminants: synthesis, mechanism and kinetic studies

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Product

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Solvent Effects on Nonradiative Relaxation Dynamics of Low-Energy Ligand-Field Excited States: A CuCl₄^2– Complex

Sensitization of TiO₂ nanosheets with Cu–biphenylamine framework to enhance photocatalytic degradation performance of toxic organic contaminants: synthesis, mechanism and kinetic studies