Singlet Molecular Oxygen Reactions with Nucleic Acids, Lipids, and Proteins

Chemical Reviews, Год журнала: 2019, Номер 119(3), С. 2043 - 2086

Опубликована: Фев. 5, 2019

Singlet oxygen (1O2) is a biologically relevant reactive species capable of efficiently reacting with cellular constituents. The resulting oxidatively generated damage to nucleic acids, membrane unsaturated lipids, and protein components has been shown be implicated in several diseases, including arthritis, cataracts, skin cancer. may endogenously produced, among various possibilities, by myeloperoxidase, an enzyme inflammation processes, also the UVA component solar radiation through photosensitization reactions. Emphasis placed this Review on description main oxidation reactions initiated 1O2 modifications within key targets, guanine for targeted amino acids. Most these give rise peroxides dioxetanes, whose formation rationalized terms [4+2] cycloaddition 1,2-cycloaddition dienes + olefins, respectively. use [18O]-labeled thermolabile endoperoxides as source applied study mechanistic aspects preferential targets biological systems. A major topic deals search molecular signature biomolecules cells. It anticipated that labeled association sensitive mass spectrometric methods should constitute powerful tools purpose.

Язык: Английский

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Chemiluminescence for bioimaging and therapeutics: recent advances and challenges

Chemical Society Reviews, Год журнала: 2020, Номер 49(19), С. 6800 - 6815

Опубликована: Янв. 1, 2020

The current progress, design principles in bioimaging and therapeutic applications, future perspectives of various chemiluminescent platforms are reviewed.

Язык: Английский

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Machine Learning for Electronically Excited States of Molecules

Chemical Reviews, Год журнала: 2020, Номер 121(16), С. 9873 - 9926

Опубликована: Ноя. 19, 2020

Electronically excited states of molecules are at the heart photochemistry, photophysics, as well photobiology and also play a role in material science. Their theoretical description requires highly accurate quantum chemical calculations, which computationally expensive. In this review, we focus on not only how machine learning is employed to speed up such excited-state simulations but branch artificial intelligence can be used advance exciting research field all its aspects. Discussed applications for include dynamics simulations, static calculations absorption spectra, many others. order put these studies into context, discuss promises pitfalls involved techniques. Since latter mostly based chemistry provide short introduction electronic structure methods approaches nonadiabatic describe tricks problems when using them molecules.

Язык: Английский

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TheoDORE: A toolbox for a detailed and automated analysis of electronic excited state computations

The Journal of Chemical Physics, Год журнала: 2020, Номер 152(8)

Опубликована: Фев. 26, 2020

The advent of ever more powerful excited-state electronic structure methods has led to a tremendous increase in the predictive power computation, but it also rendered analysis these computations much challenging and time-consuming. TheoDORE tackles this problem through providing tools for post-processing computations, which automate repetitive tasks provide rigorous reproducible descriptors. Interfaces are available ten different quantum chemistry codes range implemented therein. This article provides an overview three popular functionalities within TheoDORE, fragment-based assigning state character, computation exciton sizes measuring charge transfer, natural transition orbitals used not only visualization quantifying multiconfigurational character. Using examples organic push–pull chromophore metal complex, is shown how can be automated assignment In case conjugated polymer, we venture beyond limits traditional molecular orbital picture uncover spatial correlation effects using electron–hole plots conditional densities.

Язык: Английский

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Do Diradicals Behave Like Radicals?

Chemical Reviews, Год журнала: 2019, Номер 119(21), С. 11291 - 11351

Опубликована: Окт. 8, 2019

This review sets out to understand the reactivity of diradicals and how that may differ from monoradicals. In first part review, we delineate electronic structure a diradical with its two degenerate or nearly molecular orbitals, occupied by electrons. A classification based on whether not SOMOs can be located different sites molecule is useful in determining ground state spin. Important delocalized localized orbital transformation interchanges "closed-shell" "open-shell" descriptions. The resulting duality understanding dual singlet diradicals. second examine, consistent level theory, activation energies prototypical radical reactions (dimerization, hydrogen abstraction, addition ethylene) for representative organic diradicaloids their lowest spin states. Differences similarities vs monoradicals, either view, whichever suitable, are then discussed. last this begins an extensive, comparative, critical survey available measures character ends analysis consequences selected diradicaloids.

Язык: Английский

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Molecular Probes for Autofluorescence-Free Optical Imaging

Chemical Reviews, Год журнала: 2021, Номер 121(21), С. 13086 - 13131

Опубликована: Сен. 24, 2021

Optical imaging is an indispensable tool in clinical diagnostics and fundamental biomedical research. Autofluorescence-free optical imaging, which eliminates real-time excitation to minimize background noise, enables clear visualization of biological architecture physiopathological events deep within living subjects. Molecular probes especially developed for autofluorescence-free have been proven remarkably improve the sensitivity, penetration depth, target specificity, multiplexing capability. In this Review, we focus on advancements molecular through lens particular or photophysical mechanisms that produce long-lasting luminescence after cessation light excitation. The versatile design strategies these are discussed along with a broad range applications. Finally, challenges perspectives further advance next-generation vivo vitro biosensors.

Язык: Английский

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A generic approach towards afterglow luminescent nanoparticles for ultrasensitive in vivo imaging

Nature Communications, Год журнала: 2019, Номер 10(1)

Опубликована: Май 2, 2019

Abstract Afterglow imaging with long-lasting luminescence after cessation of light excitation provides opportunities for ultrasensitive molecular imaging; however, the lack biologically compatible afterglow agents has impeded exploitation in clinical settings. This study presents a generic approach to transforming ordinary optical (including fluorescent polymers, dyes, and inorganic semiconductors) into luminescent nanoparticles (ALNPs). integrates cascade photoreaction single-particle entity, enabling ALNPs chemically store photoenergy spontaneously decay it an energy-relay process. Not only can profiles be finetuned afford emission from visible near-infrared (NIR) region, but also their intensities predicted by mathematical model. The representative NIR permit rapid detection tumors living mice signal-to-background ratio that is more than three orders magnitude higher fluorescence. biodegradability further heightens potential vivo imaging.

Язык: Английский

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Chemiluminescent carbon dots: Synthesis, properties, and applications

Nano Today, Год журнала: 2020, Номер 35, С. 100954 - 100954

Опубликована: Сен. 11, 2020

Язык: Английский

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Recent Advances and Challenges in Luminescent Imaging: Bright Outlook for Chemiluminescence of Dioxetanes in Water

ACS Central Science, Год журнала: 2019, Номер 5(6), С. 949 - 959

Опубликована: Май 29, 2019

Chemiluminescence is gradually being recognized as a powerful tool for sensing and imaging. Most known light-emitting compounds undergo chemiexcitation through spontaneous decomposition of cyclic peroxide moieties. A ground-breaking milestone in the chemistry such was achieved 30 years ago with discovery triggerable dioxetanes by Schaap's group. Our group has recently developed distinct methodology to significantly improve light emission efficiency phenoxy-dioxetane luminophores under physiological conditions. Introduction an electron-withdrawing substituent at ortho position resulted approximately 3000-fold increase chemiluminescence quantum yield aqueous media. Furthermore, we discovered that wavelength kinetics could be determined electronic nature incorporated on dioxetane luminophore. This recent development provided scientists new chemiluminophores can act single-component probes vivo vitro detection imaging various analytes enzymes. outlook describes progress toward applications synthetic suitable environments.

Язык: Английский

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Molecular Chemiluminescent Probes with a Very Long Near‐Infrared Emission Wavelength for in Vivo Imaging

Angewandte Chemie International Edition, Год журнала: 2020, Номер 60(8), С. 3999 - 4003

Опубликована: Окт. 29, 2020

Abstract Chemiluminescence imaging is imperative for diagnostics and due to its intrinsically high sensitivity. To improve in vivo detection of biomarkers, chemiluminophores that simultaneously possess near‐infrared (NIR) emission modular structures amenable construction activatable probes are highly desired; however, these rare. Herein, we report two with record long NIR (>750 nm) via integration dicyanomethylene‐4H‐benzothiopyran or dicyanomethylene‐4H‐benzoselenopyran dioxetane unit. Caging the different cleavable moieties produces chemiluminescence (NCPs) only produce signals upon reaction reactive oxygen species enzymes, example, β‐galactosidase, a tissue‐penetration depth up 2 cm. Thus, this study provides molecular scaffolds applicable turn‐on versatile biomarkers deep tissues.

Язык: Английский

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