Predicting reactivity with a general-purpose reactivity indicator

Barrera, Yoshio; Anderson, James S.

doi:10.1016/b978-0-32-390259-5.00012-3

Cited by 2 publications

(2 citation statements)

References 61 publications

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“…Density Functional Theory offers a computationally efficient approach to addressing these challenges. Specifically, Conceptual DFT (CDFT) [ 63 , 98 ], a subfield that focuses on linking DFT quantities to chemical reactivity, has emerged as a powerful tool [ 99 , 100 , 101 , 102 , 103 ]. In this methodology, we detail the development of a model for predicting the reactivity of thiophene derivatives based on their structure and the conceptual DFT principles involved.…”

Section: Methodsmentioning

confidence: 99%

Thiophene Stability in Photodynamic Therapy: A Mathematical Model Approach

Alcázar

2024

IJMS

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Thiophene-containing photosensitizers are gaining recognition for their role in photodynamic therapy (PDT). However, the inherent reactivity of the thiophene moiety toward singlet oxygen threatens the stability and efficiency of these photosensitizers. This study presents a novel mathematical model capable of predicting the reactivity of thiophene toward singlet oxygen in PDT, using Conceptual Density Functional Theory (CDFT) and genetic programming. The research combines advanced computational methods, including various DFT techniques and symbolic regression, and is validated with experimental data. The findings underscore the capacity of the model to classify photosensitizers based on their photodynamic efficiency and safety, particularly noting that photosensitizers with a constant rate 1000 times lower than that of unmodified thiophene retain their photodynamic performance without substantial singlet oxygen quenching. Additionally, the research offers insights into the impact of electronic effects on thiophene reactivity. Finally, this study significantly advances thiophene-based photosensitizer design, paving the way for therapeutic agents that achieve a desirable balance between efficiency and safety in PDT.

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Section: Methodsmentioning

confidence: 99%

Thiophene Stability in Photodynamic Therapy: A Mathematical Model Approach

Alcázar

2024

IJMS

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“…[32][33][34][35][36][37] The original GPRI was formulated to model where a molecule is likely to be attacked by a nucleophile or electrophile, though it has been applied to discern the quality of leaving groups as well. 37 The derivation of the GPRI relies on modeling the interaction energy between the molecule of interest and the attacking molecule considering the changes in the number of electrons and the external potential 38 and is related to a few models found in the literature. [39][40][41][42][43] The new model proposed by Barrera and Anderson has been shown to be accurate in predicting the correct product for different radical reactions comparing with the radical Fukui function outcomes.…”

Section: Introductionmentioning

confidence: 99%

Does the radical GPRI strongly depend on the population scheme? A comparative study to predict radical attack on unsaturated molecules with the radical general‐purpose reactivity indicator

Barrera,

Anderson

2024

J Comput Chem

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The reactivity of 22 unsaturated molecules undergoing attack by a methyl radical (⋅CH3) have been elucidated using the condensed radical general‐purpose reactivity indicator (condensed radical GPRI) appropriate for relatively nucleophilic or electrophilic molecules. Using the appropriate radical GPRI equation for electrophilic attack or nucleophilic radical attack, seven different population schemes were used to assign the most reactive atoms in each of the 22 molecules. The results show that the condensed radical GPRI is sensitive to the population scheme chosen, but less sensitive than the radical Fukui function. Therefore, the reliability of these methods depends on the population scheme. Our investigation indicates that the condensed radical GPRI is most accurate in predicting the dominant products of the methyl radical addition reactions on a variety of unsaturated molecules when the Hirshfeld, Merz–Singh–Kollman, or Voronoi deformation density population schemes are used. Furthermore, for all populations schemes in the majority of instances where the radical Fukui function failed the radical GPRI was able to identify the most reactive atom under certain reactivity conditions.

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Predicting reactivity with a general-purpose reactivity indicator

Cited by 2 publications

References 61 publications

Thiophene Stability in Photodynamic Therapy: A Mathematical Model Approach

Thiophene Stability in Photodynamic Therapy: A Mathematical Model Approach

Does the radical GPRI strongly depend on the population scheme? A comparative study to predict radical attack on unsaturated molecules with the radical general‐purpose reactivity indicator

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