Synthesis and Photophysical Properties of a Series of Cyclopenta[<i>b</i>]naphthalene Solvatochromic Fluorophores

Benedetti, Erica; Kocsis, Laura S.; Brummond, Kay M.

doi:10.1021/ja3055029

Cited by 126 publications

(96 citation statements)

References 26 publications

(32 reference statements)

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“…A MW-assisted intramolecular didehydrogenative Diels-Alder reaction of styrene-ynes (92) was reported to furnish fluorophores 93 (Scheme 2.66) [102,103]. (95) featuring close structural similarity to bioactive molecules were obtained by the intramolecular hetero Diels-Alder cycloaddition of alkyne triazines (94) under MW conditions in good yields (Scheme 2.67) [104].…”

Section: Diels-alder Cycloadditionsmentioning

confidence: 99%

Microwave-Assisted Syntheses in Organic Chemistry

Kiss

Bálint²,

Keglevich

2016

SpringerBriefs in Molecular Science

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The second part focuses on the summary of typical organic chemical reactions selected, such as coupling reactions (C-C bond formation reactions, carbon-heteroatom bond formations), condensations (aldol-type-, Claisen-, Knoevenagel reaction), multicomponent reactions (Mannich-, Biginelli-, Hantzsch-, Bucherer-Bergs-, Strecker-, Gewald-, Kabachnik-Fields-, Kindler-, Passerini-, Ugi-and domino reactions), cycloadditions (including Diels-Alder reactions). The authors tried to compile fashionable reactions that have been reviewed less in the past years.

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Section: Diels-alder Cycloadditionsmentioning

confidence: 99%

Microwave-Assisted Syntheses in Organic Chemistry

Kiss

Bálint²,

Keglevich

2016

SpringerBriefs in Molecular Science

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“…Donor groups including a pyrrolidyl 35, piperidine 37, morpholine 38, benzylamine 39, aniline 40, and paramethoxyaniline 41 were all installed via the Buchwald−Hartwig cross-coupling reaction, while different acceptor groups, such as aldehydes 36 and 42 and ester 43 were incorporated during synthesis of the IMDDA precursor. 27 Absorption and emission maxima along with quantum yields (not shown) for these dyes were measured in CH 2 Cl 2 ( Figure 1). The tertiary cyclic amino ketone series of compounds 35, 37, and 38 ranged in absorption maxima from 355 to 390 nm, with the pyrrolidylsubstituted dye 35 having the most red-shifted absorption maxima extending close to the visible region.…”

Section: Accounts Of Chemical Researchmentioning

confidence: 99%

Intramolecular Didehydro-Diels–Alder Reaction and Its Impact on the Structure–Function Properties of Environmentally Sensitive Fluorophores.

Brummond

Kocsis

2015

Acc. Chem. Res.

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Reaction discovery plays a vital role in accessing new chemical entities and materials possessing important function.1 In this Account, we delineate our reaction discovery program regarding the [4 + 2] cycloaddition reaction of styrene-ynes. In particular, we highlight our studies that lead to the realization of the diverging reaction mechanisms of the intramolecular didehydro-Diels-Alder (IMDDA) reaction to afford dihydronaphthalene and naphthalene products. Formation of the former involves an intermolecular hydrogen atom abstraction and isomerization, whereas the latter is formed via an unexpected elimination of H2. Forming aromatic compounds by a unimolecular elimination of H2 offers an environmentally benign alternative to typical oxidation protocols. We also include in this Account ongoing work focused on expanding the scope of this reaction, mainly its application to the preparation of cyclopenta[b]naphthalenes. Finally, we showcase the synthetic utility of the IMDDA reaction by preparing novel environmentally sensitive fluorophores. The choice to follow this path was largely influenced by the impact this reaction could have on our understanding of the structure-function relationships of these molecular sensors by taking advantage of a de novo construction and functionalization of the aromatic portion of these compounds. We were also inspired by the fact that, despite the advances that have been made in the construction of small molecule fluorophores, access to rationally designed fluorescent probes or sensors possessing varied and tuned photophysical, spectral, and chemical properties are still needed. To this end, we report our studies to correlate fluorophore structure with photophysical property relationships for a series of solvatochromic PRODAN analogs and viscosity-sensitive cyanoacrylate analogs. The versatility of this de novo strategy for fluorophore synthesis was demonstrated by showing that a number of functional groups could be installed at various locations, including handles for eventual biomolecule attachment or water-solubilizing groups. Further, biothiol sensors were designed, and we expect these to be of general utility for the study of lipid dynamics in cellular membranes and for the detection of protein-binding interactions, ideal applications for these relatively hydrophobic fluorophores. Future studies will be directed toward expanding this chemistry-driven approach to the rational preparation of fluorophores with enhanced photophysical and chemical properties for application in biological systems.

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“…It was found that isomers of Prodan with different positioning of the donor and acceptor group in the naphthalene core exhibit much stronger solvatochromic properties (Benedetti et al 2012). Its naphthalene core was also substituted with aromatic hydrocarbons possessing increased electronic conjugation.…”

Section: The Environment-sensitive (Solvatochromic) Dyesmentioning

confidence: 99%

Molecular-Size Fluorescence Emitters

Demchenko

2015

Introduction to Fluorescence Sensing

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A variety of fluorescent and luminescent materials in the form of molecules, their complexes and nanoparticles are available for implementation as response units into sensing and imaging technologies and we discuss their general properties that are essential for these applications. Organic dyes were the first and remain to be the most popular emitters used with these purposes. Their labeling and responsive properties are overviewed. Natural fluorescent proteins and their engineered analogues incorporate organic fluorophores that are synthesized spontaneously from the polypeptide chain inside the living cells without the need of their intrusion, as the gene products. They resulted in revolutionary advancement in cell imaging and show good prospects in sensing and reporting on cellular processes. Organic heterocyclic compounds can incorporate metal ions generating long-living luminescence. Moreover, noble metal particles of a very small size exhibit unique light-absorbing and fluorescent emission properties. In this Chapter we focus on these types of fluorophores that possess subnanometer dimensions and display single type of absorption-emission cycle. The more complex nanostructures and nanocomposites will be overviewed in Chaps. 5 and 6 that follow. Fluorophores and Their Characteristics General Properties of Fluorescent DyesIn view of tremendous diversity of structures, chemical reactivities and spectroscopic properties, one needs certain practically useful criteria for the dye selection for the purpose of sensing and imaging. They can be formulated in the form of spectroscopic parameters that have to be optimized. It is the parameter describing the ability of molecule to absorb light at a particular wavelength. The absorbance E measured at any wavelength on spectrophotometer is proportional to the dye concentration c (in mol/l) and the light path length in a sample l (in cm). In this relation, ε plays the role of coefficient of proportionality, so that E = εcl. The value of molar absorbance is obtained by purifying and drying the dye, dissolving it at low concentration and measuring E on a spectrophotometer. The broadly used term extinction includes absorbance and light scattering. Absorbance is a unique characteristic of a molecule under certain environmental conditions. In general, the bigger the fluorophore size, the greater is the probability that the photon will be absorbed.The value of ε max at the maximum of absorption band is the common characteristic of the light-absorbing power of the dye. The dye 'brightness' that determines the absolute sensitivity of fluorescence detection (Wetzl et al. 2003) is the product of molar absorbance and quantum yield, Φ. The absorbance is related to optical cross-section and for organic dyes, ε max varies from ca. 10 3 l mol −1 cm −1 for small dyes, such as coumarins to ca. 10 5 l mol −1 cm −1 for larger fluorophores such as cyanines and phthalocyanines (Lavis and Raines 2008). It should be selected as high as possible, but the limiting factor is the fluorophore size. Us...

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Synthesis and Photophysical Properties of a Series of Cyclopenta[b]naphthalene Solvatochromic Fluorophores

Cited by 126 publications

References 26 publications

Microwave-Assisted Syntheses in Organic Chemistry

Microwave-Assisted Syntheses in Organic Chemistry

Intramolecular Didehydro-Diels–Alder Reaction and Its Impact on the Structure–Function Properties of Environmentally Sensitive Fluorophores.

Molecular-Size Fluorescence Emitters

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