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      Supramolecular Control of Singlet Oxygen Generation

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          Abstract

          Singlet oxygen ( 1O 2) is the excited state electronic isomer and a reactive form of molecular oxygen, which is most efficiently produced through the photosensitized excitation of ambient triplet oxygen. Photochemical singlet oxygen generation (SOG) has received tremendous attention historically, both for its practical application as well as for the fundamental aspects of its reactivity. Applications of singlet oxygen in medicine, wastewater treatment, microbial disinfection, and synthetic chemistry are the direct results of active past research into this reaction. Such advancements were achieved through design factors focused predominantly on the photosensitizer (PS), whose photoactivity is relegated to self-regulated structure and energetics in ground and excited states. However, the relatively new supramolecular approach of dictating molecular structure through non-bonding interactions has allowed photochemists to render otherwise inactive or less effective PSs as efficient 1O 2 generators. This concise and first of its kind review aims to compile progress in SOG research achieved through supramolecular photochemistry in an effort to serve as a reference for future research in this direction. The aim of this review is to highlight the value in the supramolecular photochemistry approach to tapping the unexploited technological potential within this historic reaction.

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          Most cited references74

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          Photodynamic therapy of cancer: An update

          Photodynamic therapy (PDT) is a clinically approved, minimally invasive therapeutic procedure that can exert a selective cytotoxic activity toward malignant cells. The procedure involves administration of a photosensitizing agent followed by irradiation at a wavelength corresponding to an absorbance band of the sensitizer. In the presence of oxygen, a series of events lead to direct tumor cell death, damage to the microvasculature, and induction of a local inflammatory reaction. Clinical studies revealed that PDT can be curative, particularly in early stage tumors. It can prolong survival in patients with inoperable cancers and significantly improve quality of life. Minimal normal tissue toxicity, negligible systemic effects, greatly reduced long-term morbidity, lack of intrinsic or acquired resistance mechanisms, and excellent cosmetic as well as organ function-sparing effects of this treatment make it a valuable therapeutic option for combination treatments. With a number of recent technological improvements, PDT has the potential to become integrated into the mainstream of cancer treatment.
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            BODIPY dyes in photodynamic therapy.

            BODIPY dyes tend to be highly fluorescent, but their emissions can be attenuated by adding substituents with appropriate oxidation potentials. Substituents like these have electrons to feed into photoexcited BODIPYs, quenching their fluorescence, thereby generating relatively long-lived triplet states. Singlet oxygen is formed when these triplet states interact with (3)O(2). In tissues, this causes cell damage in regions that are illuminated, and this is the basis of photodynamic therapy (PDT). The PDT agents that are currently approved for clinical use do not feature BODIPYs, but there are many reasons to believe that this situation will change. This review summarizes the attributes of BODIPY dyes for PDT, and in some related areas.
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              Singlet oxygen: there is indeed something new under the sun.

              Singlet oxygen, O(2)(a(1)Delta(g)), the lowest excited electronic state of molecular oxygen, has been known to the scientific community for approximately 80 years. It has a characteristic chemistry that sets it apart from the triplet ground state of molecular oxygen, O(2)(X(3)Sigma), and is important in fields that range from atmospheric chemistry and materials science to biology and medicine. For such a "mature citizen", singlet oxygen nevertheless remains at the cutting-edge of modern science. In this critical review, recent work on singlet oxygen is summarized, focusing primarily on systems that involve light. It is clear that there is indeed still something new under the sun (243 references).
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                Author and article information

                Contributors
                Role: Academic Editor
                Journal
                Molecules
                Molecules
                molecules
                Molecules
                MDPI
                1420-3049
                02 May 2021
                May 2021
                : 26
                : 9
                : 2673
                Affiliations
                [1 ]Department of Chemistry, University of Nebraska Kearney, Kearney, NE 68849, USA; akskashyap65@ 123456gmail.com
                [2 ]Department of Chemistry and Biochemistry, The University of Texas at Arlington, Arlington, TX 76019, USA; elamparuthi.ramasamy@ 123456uta.edu
                [3 ]Department of Biology and Chemistry, SUNY Polytechnic Institute, Utica, NY 13502, USA; ramaliv@ 123456sunypoly.edu
                Author notes
                [* ]Correspondence: pattabiramm2@ 123456unk.edu
                Article
                molecules-26-02673
                10.3390/molecules26092673
                8124681
                13d445d1-685d-4fde-b3a7-d23a69b37256
                © 2021 by the authors.

                Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license ( https://creativecommons.org/licenses/by/4.0/).

                History
                : 17 March 2021
                : 27 April 2021
                Categories
                Review

                singlet oxygen,supramolecular chemistry,cavitands,cucurbituril,cyclodextrin,calixarene,singlet oxygen generation (sog),photosensitizer (ps),oxidation,photodynamic therapy (pdt),near ir (nir)

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