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Record W2895854224 · doi:10.1039/c8cp04963g

Theoretical rationalisation of the photophysics of a TICT excited state of cinnamoyl–coumarin derivatives in homogeneous and biological membrane models

2018· article· en· W2895854224 on OpenAlexafffund
Daniel Zúñiga‐Núñez, Ricardo A. Zamora, Pablo Barrías, Cristián Tirapegui, Horacio Poblete, Gloria Cárdenas‐Jirón, Emilio I. Alarcón, Alexis Aspée

Bibliographic record

VenuePhysical Chemistry Chemical Physics · 2018
Typearticle
Languageen
FieldChemistry
TopicPhotochemistry and Electron Transfer Studies
Canadian institutionsUniversity of Ottawa
FundersFondo Nacional de Desarrollo Científico y TecnológicoDepartamento de Investigaciones Científicas y Tecnológicas, Universidad de Santiago de ChileComisión Nacional de Investigación Científica y TecnológicaNatural Sciences and Engineering Research Council of CanadaUniversidad de Santiago de ChileMinisterio de Economía, Fomento y Turismo, ChileUniversidad de ChileCanadian Institutes of Health ResearchUniversidad de Talca
KeywordsCoumarinRationalisationChemistryExcited stateHomogeneousMembranePhotochemistryBiological membraneOrganic chemistryBiochemistryPhysics

Abstract

fetched live from OpenAlex

A new hybrid cinnamoyl-coumarin probe was synthesised to study the formation and dynamics of a twisted internal charge transfer (TICT) excited state in homogeneous and biological membrane models. This probe showed a large bathochromic shift of the fluorescence band with the solvent polarity, which is associated with the decrease in the fluorescence intensity due to fast non-radiative deactivation pathways, ascribed to TICT excited state formation in polar solvents. The calculated potential energy surfaces using density functional theory (DFT) and time dependent-DFT (TD-DFT) along with the energetic barriers calculated using the ABF methodology established the energy requirements for a rotational twisting of the cinnamoyl-coumarin bond for TICT excited state formation. This strategy has allowed estimating the role of the ground state conformation and excited state distribution that, concomitant with fluorescence lifetime measurements, describes in detail dual fluorescence emission from TICT and ICT excited states. Moreover, the high sensitivity of fluorescence lifetimes of the TICT excited state in liposomes allows us to propose the use of this type of probes as a powerful tool for the study of gel and crystalline liquid phases in lipid membrane models. The development of this new approach will allow rationalizing and understanding the photochemical behavior of fluorescent TICT-based probes in constrained biological environments.

Fetched live from OpenAlex and de-inverted. Abstracts are not stored in this database: the inverted indexes are 8.6 GB of the frame’s 9.3 GB of text, and the host has 13 GB free.

How this classification was reachedexpand

Full frame distilled prediction

Teacher imitation

Not calibrated prevalence, not ground truth. Human validation pending. Learned from the 10,348 direct Codex labels and 10,348 direct Gemma labels. Candidate is the union of thresholded teacher heads; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels or direct frontier model labels.

metaresearch head score (Codex)0.000
metaresearch head score (Gemma)0.000
Version: codex-gemma-dda1882f352aValidation status: machine_predicted_unvalidated
Candidate categoriesnone
Consensus categoriesnone
DomainCandidate signal: none · Consensus signal: none
Study designCandidate signal: Bench or experimental · Consensus signal: Bench or experimental
GenreCandidate signal: Empirical · Consensus signal: Empirical
Teacher disagreement score0.111
Threshold uncertainty score0.915

Codex and Gemma teacher scores by category

CategoryCodexGemma
Metaresearch0.0000.000
Meta-epidemiology (narrow)0.0000.000
Meta-epidemiology (broad)0.0010.000
Bibliometrics0.0000.000
Science and technology studies0.0000.002
Scholarly communication0.0000.000
Open science0.0000.000
Research integrity0.0000.000
Insufficient payload (model declined to judge)0.0000.000

Machine scores (provisional)

The two teacher heads of the student model, read on this work. A score orders the frame for review; it never asserts a category, and the validation status ships verbatim with every row.

Baseline scores from an immature model (maturity gate not passed, 7 training rounds). Scores rank; they never assert a category.

Opus teacher head0.016
GPT teacher head0.233
Teacher spread0.216 · how far apart the two teachers sit on this one work
Validation statusscore_only:v0-immature-baseline · verbatim from the scoring run: score_only means the number may rank works, and no category label ships from it

Classification

machine, unvalidated

Machine predicted; a candidate call from one teacher head, not a consensus.

The models applied no category: nothing in the taxonomy fit this work.
Study designBench or experimental
Domainnot available
GenreEmpirical

How this classification was reached, model by model and score by score, is at the end of the page under "How this classification was reached".

Quick stats

Citations19
Published2018
Admission routes2
Has abstractyes

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