Efficiency of intermolecular chemiluminescence systems lacks significant solvent cavity effect in binary toluene/diphenylmethane mixtures

Khalid, Muhammad; Oliveira, M. A.; Souza, Sérgio Pereira de; Ciscato, Luiz Francisco Monteiro Leite; Bartoloni, Fernando Heering; Baader, W. J.

doi:10.1016/j.jphotochem.2015.06.031

Cited by 18 publications

(16 citation statements)

References 41 publications

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“…The solvent viscosity dependence of the singlet quantum yields ( Φ s ) in CL transformations has been rationalized using models described before in the literature, the free‐volume and the collisional model . The correlations of the quantum yields obtained in both systems studied according to these models show, in a first glance, a better correlation for both systems with the free‐volume model (Figs.…”

Section: Discussionmentioning

confidence: 78%

“…). The observed rate constants ( k obs ) were obtained by monoexponential fitting and the chemiluminescence quantum yields ( Φ CL ) and singlet chemiexcitation quantum yields ( Φ S ) by integration of the emission intensity time curves using appropriate intensity calibration, as described before (Table ) .…”

Section: Resultsmentioning

confidence: 99%

“…In addition, our group recently provided experimental results on the catalyzed decomposition of diphenoyl peroxide and a relatively stable 1,2‐dioxetanone derivative, spiro ‐adamantyl‐1,2‐dioxetanone ( 2 ) first synthesized by the W. Adam research group . Using toluene/diphenyl ether as well as toluene/diphenylmethane mixtures, it was shown that intermolecular CIEEL systems can be less sensitive to solvent‐cavity effects than the intramolecular ones, like the induced decomposition of 1,2‐dioxetanes .…”

Section: Discussionmentioning

confidence: 99%

“…Recently, the solvent‐cavity effect on CIEEL systems was investigated using the solvent systems toluene/diphenyl ether and toluene/diphenylmethane, in which the mixtures have different viscosities, whereas other parameters are similar . It was shown in both cases that quantum yields for intermolecular CIEEL systems have a small dependence on solvent viscosity, whereas the intramolecular induced decomposition of 1,2‐dioxetanes has a significantly higher one.…”

Section: Introductionmentioning

confidence: 99%

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Chemiexcitation Efficiency of Intermolecular Electron‐transfer Catalyzed Peroxide Decomposition Shows Low Sensitivity to Solvent‐cavity Effects

Khalid

Souza

Bartoloni

et al. 2016

Photochem & Photobiology

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Intermolecular chemically initiated electron exchange luminescence (CIEEL) systems are known to possess low chemiluminescence efficiency; whereas, the corresponding intramolecular transformations are highly efficient. As the reasons for this discrepancy are not known, we report in this work our studies of the solvent-cavity effect on the efficiency of two intermolecular CIEEL systems, the catalyzed decomposition of diphenoyl peroxide and of a relatively stable 1,2-dioxetanone derivative, spiro-adamantyl-1,2-dioxetanone. The results indicate a very low medium viscosity effect on the quantum yields of these systems, a priori not compatible with these bimolecular transformations, showing also that their low efficiency cannot be due to solvent-cavity escape of intermediate radical ion pairs. In addition, the solvent-cage effect on the CIEEL efficiency, after the occurrence of the initial electron transfer, proved also to be very low, indicating the intrinsic low viscosity effect on the chemiexcitation step. Therefore, it is concluded that the low efficiency of these systems is intrinsic to the chemiexcitation step and cannot be improved by medium viscosity effects, being possibly due to sterical hindrance on charge-transfer complex formation in the initial step of the CIEEL.

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Section: Discussionmentioning

confidence: 78%

Section: Resultsmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Chemiexcitation Efficiency of Intermolecular Electron‐transfer Catalyzed Peroxide Decomposition Shows Low Sensitivity to Solvent‐cavity Effects

Khalid

Souza

Bartoloni

et al. 2016

Photochem & Photobiology

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“…7,12 Composto orgânicos cíclicos que possuem ligação peroxídica, como dioxetanos, 1,2-dioxetanonas (ou -peroxilactonas), peróxido de difenoíla e a 1,2dioxetanodiona são espécies que, sob determinadas condições reacionais, geram estados excitados e estão envolvidos na elucidação do mecanismo de diversos sistemas quimi e bioluminescentes, através de estudos cinéticos envolvendo suas decomposições, catalisadas ou não, e seus valores rendimento quântico. 7,[13][14][15][16][17][18] 20…”

Section: Princípios Básicos De Quimiluminescênciaunclassified

Estudo mecanístico do sistema peroxioxalato com diferentes catalisadores

Souza¹

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Agradeço, primeiramente, aos meus pais por todo amor, atenção, dedicação e cuidado. Por terem me proporcionado uma boa educação e me ajudado a chegar até aqui. Muito obrigada ao Willi por todo apoio, pelo conhecimento compartilhado, por todas as discussões de resultados, entre outras coisas que contribuíram para a minha formação. Agradeço também a Paulete, que juntamente ao Willi, sempre abriram as portas de sua casa para nossas confraternizações de grupo anuais. Agradeço todos os meus colegas de laboratório, com os quais tive o prazer de conviver ao longo de todos esses anos, especialmente a Ana P. Fileno e o Sandro, por terem me orientado durante minha IC com tanta dedicação, me auxiliando nos primeiros passos da minha carreira científica. Aos nossos técnicos, Luiz Carlos e Suzana, por todos os momentos de descontração e risadas com as piadas prontas. Aos amigos do IQ: Luiza, Vinícius, Thuany, Biff, André, Aninha, Amanda e a Karina. E todas as amizades conquistadas durante esses 10 anos de IQ-USP. Sem vocês tudo teria sido mais difícil. À Shirley, ao Cezar, ao Paulinho, ao Edgar e à Dani, vocês são incríveis, me diverti infinitamente na companhia de vocês! Ao pessoal da secretaria de pós-graduação, em especial a Cibele, o Milton e o Marcelo, por toda a ajuda com os prazos, documentações, prestação de contas e certificados do PAE. Ao CNPq pela bolsa concedida.

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Anticancer activity and morphological analysis of Pt (II) complexes: Their DFT approach, docking simulation, and ADME‐Tox profiling

Rossi,

Stagno,

Piperno

et al. 2024

Applied Organom Chemis

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A consistent series of Pt (II) polypyridyl complexes (i.e., LDP‐10–25), previously obtained and characterized by our research group, underwent extensive biological investigations to verify their activity profile as target‐based anticancer agents. Preliminary in vitro screening at 10 μM against three tumor cell lines known to overexpress DNA G‐4 (MDA‐MB 231, U87, and U2‐OS) pointed out that four of them, namely, LDP‐15, LDP‐16, LDP‐24, and LDP‐25, had promising cytotoxic activity compared with cisplatin. Therefore, these four compounds were selected for continuous assays against the same three cell lines and morphological analyses on U2‐OS cells that showed IC50 values in the micromolar range and remarkable changes in nuclei shape and cytoskeleton integrity, respectively. Docking studies supported the idea that the antiproliferative activity of the complexes could be attributed to their interaction via a hybrid binding mode with the intended molecular target, DNA G‐4. In addition, in silico ADME‐Tox profiling studies showed no risk of tumorigenic, irritant, or reproductive effects for the title compounds. DFT calculations were used to verify the structural characteristics of the four selected compounds and to investigate their electronic behavior. Overall, the results obtained, both experimentally and theoretically, indicate that LDP‐15, LDP‐16, LDP‐24, and LDP‐25 complexes could be useful for further study as potential therapeutic agents.

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Efficiency of intermolecular chemiluminescence systems lacks significant solvent cavity effect in binary toluene/diphenylmethane mixtures

Cited by 18 publications

References 41 publications

Chemiexcitation Efficiency of Intermolecular Electron‐transfer Catalyzed Peroxide Decomposition Shows Low Sensitivity to Solvent‐cavity Effects

Chemiexcitation Efficiency of Intermolecular Electron‐transfer Catalyzed Peroxide Decomposition Shows Low Sensitivity to Solvent‐cavity Effects

Estudo mecanístico do sistema peroxioxalato com diferentes catalisadores

Anticancer activity and morphological analysis of Pt (II) complexes: Their DFT approach, docking simulation, and ADME‐Tox profiling

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