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Nanoscale Jul 2016As clinical nanomedicine has emerged over the past two decades, phototherapeutic advancements using nanotechnology have also evolved and impacted disease management.... (Review)
Review
As clinical nanomedicine has emerged over the past two decades, phototherapeutic advancements using nanotechnology have also evolved and impacted disease management. Because of unique features attributable to the light activation process of molecules, photonanomedicine (PNM) holds significant promise as a personalized, image-guided therapeutic approach for cancer and non-cancer pathologies. The convergence of advanced photochemical therapies such as photodynamic therapy (PDT) and imaging modalities with sophisticated nanotechnologies is enabling the ongoing evolution of fundamental PNM formulations, such as Visudyne®, into progressive forward-looking platforms that integrate theranostics (therapeutics and diagnostics), molecular selectivity, the spatiotemporally controlled release of synergistic therapeutics, along with regulated, sustained drug dosing. Considering that the envisioned goal of these integrated platforms is proving to be realistic, this review will discuss how PNM has evolved over the years as a preclinical and clinical amalgamation of nanotechnology with PDT. The encouraging investigations that emphasize the potent synergy between photochemistry and nanotherapeutics, in addition to the growing realization of the value of these multi-faceted theranostic nanoplatforms, will assist in driving PNM formulations into mainstream oncological clinical practice as a necessary tool in the medical armamentarium.
Topics: Nanomedicine; Neoplasms; Photochemistry; Photochemotherapy; Theranostic Nanomedicine
PubMed: 27328309
DOI: 10.1039/c5nr08691d -
Molecules (Basel, Switzerland) Aug 2021Atmospheric organic aerosols play a major role in climate, demanding a better understanding of their formation mechanisms by contributing multiphase chemical reactions... (Review)
Review
Atmospheric organic aerosols play a major role in climate, demanding a better understanding of their formation mechanisms by contributing multiphase chemical reactions with the participation of water. The sunlight driven aqueous photochemistry of small 2-oxocarboxylic acids is a potential major source of organic aerosol, which prompted the investigations into the mechanisms of glyoxylic acid and pyruvic acid photochemistry reviewed here. While 2-oxocarboxylic acids can be contained or directly created in the particles, the majorities of these abundant and available molecules are in the gas phase and must first undergo the surface uptake process to react in, and on the surface, of aqueous particles. Thus, the work also reviews the acid-base reaction that occurs when gaseous pyruvic acid meets the interface of aqueous microdroplets, which is contrasted with the same process for acetic acid. This work classifies relevant information needed to understand the photochemistry of aqueous pyruvic acid and glyoxylic acid and motivates future studies based on reports that use novel strategies and methodologies to advance this field.
PubMed: 34500711
DOI: 10.3390/molecules26175278 -
International Journal of Molecular... Aug 2015Photodynamic therapy (PDT) is a clinical modality used to treat cancer and infectious diseases. The main agent is the photosensitizer (PS), which is excited by light and... (Review)
Review
Photodynamic therapy (PDT) is a clinical modality used to treat cancer and infectious diseases. The main agent is the photosensitizer (PS), which is excited by light and converted to a triplet excited state. This latter species leads to the formation of singlet oxygen and radicals that oxidize biomolecules. The main motivation for this review is to suggest alternatives for achieving high-efficiency PDT protocols, by taking advantage of knowledge on the chemical and biological processes taking place during and after photosensitization. We defend that in order to obtain specific mechanisms of cell death and maximize PDT efficiency, PSes should oxidize specific molecular targets. We consider the role of subcellular localization, how PS photochemistry and photophysics can change according to its nanoenvironment, and how can all these trigger specific cell death mechanisms. We propose that in order to develop PSes that will cause a breakthrough enhancement in the efficiency of PDT, researchers should first consider tissue and intracellular localization, instead of trying to maximize singlet oxygen quantum yields in in vitro tests. In addition to this, we also indicate many open questions and challenges remaining in this field, hoping to encourage future research.
Topics: Animals; Cell Death; Humans; Oxidation-Reduction; Photochemistry; Photochemotherapy; Photosensitizing Agents
PubMed: 26334268
DOI: 10.3390/ijms160920523 -
Nature Oct 2021Metal-catalysed cross-couplings are a mainstay of organic synthesis and are widely used for the formation of C-C bonds, particularly in the production of unsaturated...
Metal-catalysed cross-couplings are a mainstay of organic synthesis and are widely used for the formation of C-C bonds, particularly in the production of unsaturated scaffolds. However, alkyl cross-couplings using native sp-hybridized functional groups such as alcohols remain relatively underdeveloped. In particular, a robust and general method for the direct deoxygenative coupling of alcohols would have major implications for the field of organic synthesis. A general method for the direct deoxygenative cross-coupling of free alcohols must overcome several challenges, most notably the in situ cleavage of strong C-O bonds, but would allow access to the vast collection of commercially available, structurally diverse alcohols as coupling partners. We report herein a metallaphotoredox-based cross-coupling platform in which free alcohols are activated in situ by N-heterocyclic carbene salts for carbon-carbon bond formation with aryl halide coupling partners. This method is mild, robust, selective and most importantly, capable of accommodating a wide range of primary, secondary and tertiary alcohols as well as pharmaceutically relevant aryl and heteroaryl bromides and chlorides. The power of the transformation has been demonstrated in a number of complex settings, including the late-stage functionalization of Taxol and a modular synthesis of Januvia, an antidiabetic medication. This technology represents a general strategy for the merger of in situ alcohol activation with transition metal catalysis.
Topics: Alcohols; Bromides; Carbon; Catalysis; Chlorides; Metals; Methane; Nitrogen; Oxidation-Reduction; Oxygen; Paclitaxel; Photochemistry; Simvastatin
PubMed: 34464959
DOI: 10.1038/s41586-021-03920-6 -
Advances in Experimental Medicine and... 2018Retinaldehyde adducts (bisretinoids) accumulate in retinal pigment epithelial (RPE) cells as lipofuscin. Bisretinoids are implicated in some inherited and age-related... (Review)
Review
Retinaldehyde adducts (bisretinoids) accumulate in retinal pigment epithelial (RPE) cells as lipofuscin. Bisretinoids are implicated in some inherited and age-related forms of macular degeneration that lead to the death of RPE cells and diminished vision. By comparing albino and black-eyed mice and by rearing mice in darkness and in cyclic light, evidence indicates that bisretinoid fluorophores undergo photodegradation in the eye (Ueda et al. Proc Natl Acad Sci 113:6904-6909, 2016). Given that the photodegradation products modify and impair cellular and extracellular molecules, these processes likely impart cumulative damage to retina.
Topics: ATP-Binding Cassette Transporters; Albinism; Amines; Animals; Antioxidants; Darkness; Eye Color; Free Radical Scavengers; Light; Lipofuscin; Macular Degeneration; Melanosis; Mice; Mice, Inbred C57BL; Mice, Mutant Strains; Photochemistry; Retinal Pigment Epithelium; Retinaldehyde; Rod Cell Outer Segment; Stargardt Disease; Vitamin E
PubMed: 29721969
DOI: 10.1007/978-3-319-75402-4_49 -
International Journal of Molecular... Dec 2022In this research, the synthesis, photochemistry, and computational study of new - and -isomers of amino-thienostilbenes is performed to test the efficiency of their...
In this research, the synthesis, photochemistry, and computational study of new - and -isomers of amino-thienostilbenes is performed to test the efficiency of their production and acid resistance, and to investigate their electronic structure, photoreactivity, photophysical characteristics, and potential biological activity. The electronic structure and conformations of synthesized thienostilbene amines and their photocyclization products are examined computationally, along with molecular modeling of amines possessing two thiophene rings that showed inhibitory potential toward cholinesterases. New amino-styryl thiophenes, with favorable photophysical properties and proven acid resistance, represent model compounds for their water-soluble ammonium salts as potential styryl optical dyes. The comparison with organic dyes possessing a -aminostilbene subunit as the scaffold shows that the newly synthesized -aminostilbenes have very similar absorbance wavelengths. Furthermore, their functionalized -isomers and photocyclization products are good candidates for cholinesterase inhibitors because of the structural similarity of the molecular skeleton to some already proven bioactive derivatives.
Topics: Photochemistry; Thiophenes; Benzylamines; Models, Molecular; Coloring Agents
PubMed: 36614053
DOI: 10.3390/ijms24010610 -
Angewandte Chemie (International Ed. in... Sep 2020Photochemistry is a fascinating branch of chemistry that is concerned with molecules and light. However, the importance of simulating light-induced processes is... (Review)
Review
Photochemistry is a fascinating branch of chemistry that is concerned with molecules and light. However, the importance of simulating light-induced processes is reflected also in fields as diverse as biology, material science, and medicine. This Minireview highlights recent progress achieved in theoretical chemistry to calculate electronically excited states of molecules and simulate their photoinduced dynamics, with the aim of reaching experimental accuracy. We focus on emergent methods and give selected examples that illustrate the progress in recent years towards predicting complex electronic structures with strong correlation, calculations on large molecules, describing multichromophoric systems, and simulating non-adiabatic molecular dynamics over long time scales, for molecules in the gas phase or in complex biological environments.
PubMed: 32052547
DOI: 10.1002/anie.201916381 -
BioTechniques Jan 2019Photo-crosslinkable hydrogels have recently attracted significant scientific interest. Their properties can be manipulated in a spatiotemporal manner through exposure to... (Review)
Review
Photo-crosslinkable hydrogels have recently attracted significant scientific interest. Their properties can be manipulated in a spatiotemporal manner through exposure to light to achieve the desirable functionality for various biomedical applications. This review article discusses the recent advances of the most common photo-crosslinkable hydrogels, including poly(ethylene glycol) diacrylate, gelatin methacryloyl and methacrylated hyaluronic acid, for various biomedical applications. We first highlight the advantages of photopolymerization and discuss diverse photosensitive systems used for the synthesis of photo-crosslinkable hydrogels. We then introduce their synthesis methods and review their latest state of development in biomedical applications, including tissue engineering and regenerative medicine, drug delivery, cancer therapies and biosensing. Lastly, the existing challenges and future perspectives of engineering photo-crosslinkable hydrogels for biomedical applications are briefly discussed.
Topics: Animals; Biosensing Techniques; Drug Delivery Systems; Gelatin; Humans; Hyaluronic Acid; Hydrogels; Neoplasms; Photochemical Processes; Photochemistry; Polyethylene Glycols; Polymerization; Tissue Engineering
PubMed: 30730212
DOI: 10.2144/btn-2018-0083 -
Topics in Current Chemistry (Cham) Nov 2018In recent years, photochemistry has been a highly active research field. This renaissance is linked to the upsurge of photoredox catalysis, a versatile platform for... (Review)
Review
In recent years, photochemistry has been a highly active research field. This renaissance is linked to the upsurge of photoredox catalysis, a versatile platform for synthetic methodologies using visible light photons as a traceless reagent. In contrast with UV, visible light constitutes almost half of the ground solar irradiance, making the use of solar light in chemistry a sustainable and viable possibility. However, the direct use of sunlight to power chemical reactions is still little explored. This can be explained by both the hurdles associated with solar radiation (e.g., its variability, irreproducibility, high IR content, etc.) and the need for a specialized photoreactor. Most of these issues can be tackled with technological solutions, and especially with the recourse to flow chemistry. Flow chemistry goes hand in hand with photochemistry thanks to the uniform irradiation it provides to the reaction. Furthermore, a continuous-flow reactor can be easily integrated with different solar collectors (including compound parabolic concentrators and luminescent solar concentrators) and constitutes the most efficient approach to solar photochemistry. After a description of the characteristics of the solar radiation relevant to chemistry, this chapter critically describes the different type of solar photoreactors and their applications in synthetic organic chemistry. Finally, an outlook on the future of solar photochemistry in flow is included.
Topics: Green Chemistry Technology; Oxidation-Reduction; Photochemical Processes; Solar Energy
PubMed: 30450506
DOI: 10.1007/s41061-018-0223-2 -
Molecules (Basel, Switzerland) Jun 2022The structure, tautomerization pathways, vibrational spectra, and photochemistry of 2-amino-4-methylthiazole (AMT) molecule were studied by matrix isolation FTIR...
The structure, tautomerization pathways, vibrational spectra, and photochemistry of 2-amino-4-methylthiazole (AMT) molecule were studied by matrix isolation FTIR spectroscopy and DFT calculations undertaken at the B3LYP/6-311++G(3df,3pd) level of theory. The most stable tautomer with the five-membered ring stabilized by two double C=C and C=N bonds, was detected in argon matrices after deposition. When the AMT/Ar matrices were exposed to 265 nm selective irradiation, three main photoproducts, N-(1-sulfanylprop-1-en-2-yl)carbodiimide (fp1), N-(1-thioxopropan-2-yl)carbodiimide (fp2) and N-(2-methylthiiran-2-yl)carbodiimide (fp3), were photoproduced by a cleavage of the CS-CN bond together with hydrogen atom migration. The minor photoreaction caused by the cleavage of the CS-CC bond and followed by hydrogen migration formed 2-methyl-1H-azirene-1-carbimidothioic acid (fp15). We have also found that cleavage of the CS-CN bond followed by disruption of the N-C bond produced cyanamide (fp11) and the C(CH3)=CH-S biradical that transformed into 2-methylthiirene (fp12) and further photoreactions produced 1-propyne-1-thiole (fp13) or methylthioketene (fp14). Cleavage of the CS-CC bond followed by disruption of the N-C bond produced propyne (fp22) and the S-C(NH)=N biradical that transformed into 3-aminethiazirene (fp23); further photoreactions produced N-sulfanylcarbodiimide (fp25). As a result of these transformations, several molecular complexes were identified as photoproducts besides new molecules in the AMT photolysis process.
Topics: Carbodiimides; Hydrogen; Models, Molecular; Photochemistry; Spectroscopy, Fourier Transform Infrared
PubMed: 35745029
DOI: 10.3390/molecules27123897