Effect of Confinement on the Physicochemical Properties of Chromophoric Dyes/Drugs with Cucurbit[<i>n</i>]uril: Prospective Applications

Mohanty, Jyotirmayee; Barooah, Nilotpal; Bhasikuttan, Achikanath C.

doi:10.1002/9781119683353.ch19

Cited by 3 publications

(3 citation statements)

References 70 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The effect of supramolecular encapsulation on the singlet excited state dynamics of several dyes and photosensitizers has been very well documented. − In general, for a 1:1 stoichiometry of the dye–macrocycle complex, restriction of bond rotations and vibrations decreases nonradiative deactivation pathways, thus enhancing fluorescence emission.…”

Section: Introductionmentioning

confidence: 99%

Extraordinary Control of Photosensitized Singlet Oxygen Generation by Acyclic Cucurbituril-like Containers

et al. 2023

View full text Add to dashboard Cite

Supramolecular control of singlet oxygen generation is incredibly valuable for several fields with broad applications and thus still challenging. However, macrocyclic inclusion complexes inherently restrict the interaction of photosensitizers with surrounding oxygen in the media. To circumvent this issue, we turned our attention in this work to acyclic cucurbituril-like containers and uncover their properties as supramolecular hosts for photosensitizers with extraordinary control of their photophysics, including singlet oxygen generation. Thermodynamic and photophysical studies were carried out showing that these acyclic containers compare very favorably to benchmark macrocycles such as cucurbiturils and cyclodextrins in terms of their binding affinities and supramolecular control of singlet oxygen generation. Acyclic container with terminal naphthalene walls offers a similar cavity to cucurbit[7]uril and the same carbonyl-lined portals for a tight binding of phenothiazinium dye methylene blue and stabilizing its singlet and triplet excited states. Thus, generation of singlet oxygen for this container is higher than for other macrocycles and even higher than the free photosensitizer. While the acyclic container with smaller terminal benzene walls, stacks over the dye through sulfur−π and π–π interactions deactivating the singlet and triplet excited states, thus showing the lowest generation of singlet oxygen out of all of the studied systems. Due to the great water solubility and biocompatibility of these systems, they possess great potential for novel applications in photocatalysis, synthesis, and biomedical fields, among others.

show abstract

Section: Introductionmentioning

confidence: 99%

Extraordinary Control of Photosensitized Singlet Oxygen Generation by Acyclic Cucurbituril-like Containers

et al. 2023

View full text Add to dashboard Cite

show abstract

“…Recent research has focused on the phenomenon of supramolecular pK shift, which involves a significant shift in the pK value of nitrogenous compounds by forming supramolecular complexes with macrocyclic molecules such as cucurbiturils [ 7 , 8 , 14 , 59 , 64 , 95 ]. This phenomenon is crucial for designing and optimizing supramolecular systems, with far-reaching implications in materials science [ 92 , 98 ], catalysis [ 3 , 28 , 77 ] and the development of drugs and their delivery methods [ 26 , 31 , 37 , 49 , 75 ].…”

Section: Introductionmentioning

confidence: 99%

Reliable and accurate prediction of basic pK$$_a$$ values in nitrogen compounds: the pK$$_a$$ shift in supramolecular systems as a case study

Alcázar,

Misad Saide,

Campodónico

2023

J Cheminform

View full text Add to dashboard Cite

This article presents a quantitative structure–activity relationship (QSAR) approach for predicting the acid dissociation constant (pK$$_a$$ a ) of nitrogenous compounds, including those within supramolecular complexes based on cucurbiturils. The model combines low-cost quantum mechanical calculations with QSAR methodology and linear regressions to achieve accurate predictions for a broad range of nitrogen-containing compounds. The model was developed using a diverse dataset of 130 nitrogenous compounds and exhibits excellent predictive performance, with a high coefficient of determination (R$$^2$$ 2 ) of 0.9905, low standard error (s) of 0.3066, and high Fisher statistic (F) of 2142. The model outperforms existing methods, such as Chemaxon software and previous studies, in terms of accuracy and its ability to handle heterogeneous datasets. External validation on pharmaceutical ingredients, dyes, and supramolecular complexes based on cucurbiturils confirms the reliability of the model. To enhance usability, a script-like tool has been developed, providing a streamlined process for users to access the model. This study represents a significant advancement in pK$$_a$$ a prediction, offering valuable insights for drug design and supramolecular system optimization. Graphical Abstract

show abstract

“…Recent research has focused on the phenomenon of supramolecular pK a shift, which involves a significant shift in the pK a value of nitrogenous compounds by forming supramolecular complexes with macrocyclic molecules such as cucurbiturils [7,8,14,59,64,95]. This phenomenon is crucial for designing and optimizing supramolecular systems, with far-reaching implications in materials science [92,98], catalysis [3,28,77] and the development of drugs and their delivery methods [26,31,37,49,75].…”

Section: Introductionmentioning

confidence: 99%

Reliable and accurate prediction of basic pKa values in nitrogen compounds: The pKa shift in supramolecular systems as a case study

Alcázar,

Saide,

Campodónico

2023

Preprint

View full text Add to dashboard Cite

This article presents a Quantitative Structure-Activity Relationship (QSAR) approach for predicting the acid dissociation constant (pK $_a$ ) of nitrogenous compounds, including those within supramolecular complexes based on cucurbiturils. The model combines low-cost quantum mechanical calculations with QSAR methodology and linear regressions to achieve accurate predictions for a broad range of nitrogen-containing compounds. The model was developed using a diverse dataset of 130 nitrogenous compounds and exhibits excellent predictive performance, with a high coefficient of determination (R $^2$ ) of 0.9905, low standard error (s) of 0.3066, and high Fisher statistic (F) of 2142. The model outperforms existing methods, such as Chemaxon software and previous studies, in terms of accuracy and its ability to handle heterogeneous datasets. External validation on pharmaceutical ingredients, dyes, and supramolecular complexes based on cucurbiturils confirms the reliability of the model. To enhance usability, a script-like tool has been developed, providing a streamlined process for users to access the model. This study represents a significant advancement in pK$_a$ prediction, offering valuable insights for drug design and supramolecular system optimization.

show abstract

Effect of Confinement on the Physicochemical Properties of Chromophoric Dyes/Drugs with Cucurbit[n]uril: Prospective Applications

Cited by 3 publications

References 70 publications

Extraordinary Control of Photosensitized Singlet Oxygen Generation by Acyclic Cucurbituril-like Containers

Extraordinary Control of Photosensitized Singlet Oxygen Generation by Acyclic Cucurbituril-like Containers

Reliable and accurate prediction of basic pK$$_a$$ values in nitrogen compounds: the pK$$_a$$ shift in supramolecular systems as a case study

Reliable and accurate prediction of basic pKa values in nitrogen compounds: The pKa shift in supramolecular systems as a case study

Contact Info

Product

Resources

About