Mesoporous zinc germanium oxynitride for CO2 photoreduction under visible light

Mesoporous zinc germanium oxynitride was synthesized by a template-free method at high temperature. Through optimizing redox potentials as well as improving crystallinity, this material showed enhanced activity in CO(2) photoreduction.     

New caged coumarin fluorophores with extraordinary uncaging cross sections suitable for biological imaging applications

Photocaged fluorescent molecules are important research tools for tracking molecular dynamics with high spatiotemporal resolution in biological systems. We have designed and synthesized a new class of caged coumarin fluorophores. These coumarin cages displayed more than 200-fold fluorescence enhancement after UV photolysis. Remarkably, the uncaging cross section of a 1-(2-nitrophenyl)ethyl (NPE)-caged coumarin is 6600 at wavelength of 365 nm, about 2 orders of magnitude higher than previously described caged fluorophores. Product analysis of the photolytic reaction showed clean conversion of NPE-caged coumarin to 2-nitrosoacetophenone and the parent coumarin, suggesting that the mechanism of the photolysis follows the known photochemical reaction pathway of the 2-nitrobenzyl group. We have also measured the two-photon uncaging cross sections of NPE-caged coumarins 2a and 5 at 740 nm to be near 1 Goeppert-Mayer (GM). The mechanistic study, together with the two-photon uncaging data, suggested that the coumarin moiety serves as an antenna to enhance the light harvesting efficiency of the coumarin cage and that the photonic energy absorbed by coumarin was utilized efficiently to photolyze the NPE group. Future explorations of this type of "substrate-assisted photolysis" may yield other cages of high uncaging cross sections. For cellular imaging applications, we prepared a cell permeable and caged coumarin fluorophore, NPE-HCCC2/AM (10), which can be loaded into fully intact cells to high concentrations. Initial tests of this probe in a number of cultured mammalian cells showed desired properties for the in vivo imaging applications. The combined advantages of robust fluorescence contrast enhancement, remarkably high uncaging cross sections, noninvasive cellular delivery, and flexible chemistry for bioconjugations should generate broad applications of these caged coumarins in biochemical and biological research.     

Oxime as a general photocage for the design of visible light photo-activatable fluorophores

Photoactivatable fluorophores have been widely used for tracking molecular and cellular dynamics with subdiffraction resolution. In this work, we have prepared a series of photoactivatable probes using the oxime moiety as a new class of photolabile caging group in which the photoactivation process is mediated by a highly efficient photodeoximation reaction. Incorporation of the oxime caging group into fluorophores results in loss of fluorescence. Upon light irradiation in the presence of air, the oxime-caged fluorophores are oxidized to their carbonyl derivatives, restoring strong fluorophore fluorescence. To demonstrate the utility of these oxime-caged fluorophores, we have created probes that target different organelles for live-cell confocal imaging. We also carried out photoactivated localization microscopy (PALM) imaging under physiological conditions using low-power light activation in the absence of cytotoxic additives. Our studies show that oximes represent a new class of visible-light photocages that can be widely used for cellular imaging, sensing, and photo-controlled molecular release.

Photoactivatable fluorophores have been widely used for tracking molecular and cellular dynamics with subdiffraction resolution.     

Site-specific prodrug release using visible light

Using a photosensitization-singlet oxygenation-dioxetane cleavage strategy, a photodynamic prodrug system has been developed, whereby drugs bearing carbonyl groups can first be attached to a photosensitizer to give a photosensitizer-drug complex and then released from the complex upon visible light irradiation. Visible light, which has good penetration through tissue, generates singlet oxygen via the photosensitizer, which then releases the prodrug when and where required. With this system, drug mimics and methyl esters of NSAIDs have been successfully incorporated with photosensitizers related to verteporfin and then released by visible light illumination in high to quantitative yields within minutes.     

Hemicyanine-linked pyrimidine mimics as solvatochromic fluorophores with visible excitation wavelengths

The design of solvatochromic fluorescent nucleosides with visible excitation wavelengths is a goal towards the generation of modified oligonucleotides for fluorimetry-based molecular imaging. Herein, two hemicyanine-linked C5-2′-deoxyuridine nucleosides (PyI-dU and APPy-dU) have been synthesized by first generating hemicyanine-alkyne precursors that were attached via the alkyne moiety to 5-iodo-2′-deoxyuridine (5-I-dU) by Sonogashira coupling. The photophysical properties of the hemicyanine-linked dU probes have been characterized and compared to the corresponding properties of the hemicyanine-alkyne precursors. The nucleoside probe PyI-dU exhibits optical features that mimic the properties of the free hemicyanine-alkyne precursor, while the APPy-dU probe displays more favorable optical properties (longer excitation wavelength, brighter emission in water) than its precursor that is ascribed to π-stacking interactions between the hemicyanine dye with the dU nucleobase. Overall, probe APPy-dU is a superior solvatochromic fluorophore than PyI-dU suggesting its greater utility for fluorescent imaging applications.     

The cycloaddition reaction using visible light photoredox catalysis

In recent years, visible light photoredox catalysis has emerged as an important research area in synthesis. In this review, we describe the recent progress in the visible light induced cycloaddition reactions, including [2+2], [3+2], [4+2] and [2+2+2] cycloadditions, for the construction of four-, five- or six-membered cycles and polycycles. Furthermore, the mechanisms for these transformations are also discussed, in which the formation of the radicals is initiated by a visible light photoredox catalysis process.     

Two-photon uncaging of neurochemicals using inorganic metal complexes

Neuroactive compounds can be photoreleased by means of two-photon excitation using a new kind of transition metal-based caged compound.     

Inactivation of lymphocytes in blood products using riboflavin photochemical treatment with visible light

Abstract Immunocompetent lymphocytes present in blood products are an important cause of immune reactions following blood transfusion such as transfusion-associated graft-versus-host disease (TA-GVHD). In this study the effects of riboflavin photochemical treatment (RPT) on lymphocyte proliferation and cytokine production in vitro were measured to establish whether RPT of blood products can be used to prevent immune reactions resulting from transfused lymphocytes. Lymphocytes and riboflavin were added together in medical PVC transparent bags and then exposed to visible light. Control lymphocytes were exposed to light in the absence of riboflavin. Lymphocytes exposed to riboflavin photochemical treatment (RPT-lymphocytes) and control lymphocytes were tested for the proliferative ability and the production of several cytokines upon stimulation with antigens. Upon stimulation by phytohemagglutinin (PHA) the proliferation of RPT-lymphocytes was inhibited. Using flow cytometry it was shown that RPT-lymphocytes were unable to enter the S-phase of the cell cycle following PHA stimulation. The level of cytokines present in the supernatant of RPT-lymphocytes after stimulation by antigens was significantly lower than those present in the corresponding supernatant of control lymphocytes. RPT with visible light inactivates lymphocytes, inhibits lymphocyte proliferation and the production of cytokines. It appears to be a promising method to prevent immune reactions such as TA-GVHD.     

Hyperpigmentation induced by topical 5-aminolaevulinic acid plus visible light

Photodynamic therapy (PDT) with 5-aminolaevulinic acid (ALA) is an alternative tool for the treatment of superficial non-melanoma skin cancers. Recently ALA-PDT has been employed with encouraging results also for warts, condylomata and psoriasis. In this study the effects of topical ALA plus irradiation with visible light on intact human skin have been evaluated. Five skin areas (A, B, C, D, and E) on the inner upper part of the arms of five healthy volunteers (skin types III and IV) were treated with (A) ALA 20% in base cream without irradiation, (B) only the vehicle (base cream) without ALA, (C, D and E) ALA cream at the concentrations of 5, 10 and 20%, respectively; all treatments were applied with an occlusive dressing. Four hours after ALA or vehicle application areas B, C, D and E were irradiated with a fixed dose of 40 J/cm(2). ALA penetration through the intact skin was evaluated by in vivo fluorescence determination. The effects on healthy skin were evaluated by clinical and chromometric examinations, light microscopy, immunohistochemistry and electron microscopy. RESULTS: (1) in vivo fluorescence demonstrated that ALA is able to penetrate through the intact skin, when applied with occlusive dressing and induces a classical fluorescence peak due to Protoporphyrin IX (PpIX) formation, which is the active photosensitiser. (2) Skin areas receiving ALA plus irradiation showed erythema and swelling just after the irradiative session and hyperpigmentation 48-72 h later. (3) Colourimetric data confirmed significant skin colour changes: values a* (representing the erythematous changes) increased only on the skin areas where ALA+irradiation were applied and during the 48 h after irradiation, thereafter a* began to decrease; values L* (pigmentation) increased during the 2 weeks following treatment. (4) Histopathological, immunohistochemical (S100, HMB-45) and electron microscopic findings showed an absolute increment of the number of melanocytes, which appeared clearly activated. In conclusion the application of ALA cream followed by irradiation is able to induce a pigmentation response in healthy human skin, at least in skin types III and IV. This melanocytic activation could have a potential for the treatment of skin disorders characterised by hypopigmentation.     

Synthetic routes to 3-alkylsulfanyl-6-aryl-diketopyrrolo[3,4-c]pyrroles--a class of efficient, visible light excitable fluorophores

Sulfide derivatives of diketopyrrolo[3,4-c]pyrrole (SDPPs) were prepared in a one-pot procedure from arylpyrrolinones, isothiocyanates and alkylating agents, and their properties as fluorophores were evaluated.     

Ruthenium(II)-cored supramolecular organic framework-mediated recyclable visible light photoreduction of azides to amines and cascade formation of lactams

Porous[Ru(bpy)₃]²⁺-cored supramolecular metal organic framework can efficiently catalyze visible light photoreduction of various azides to afford amines and, through cascade reactions, lactams.     

Enhanced dSTORM imaging using fluorophores interacting with cucurbituril

Advanced fluorescence microscopy including single-molecule localization-based super-resolution imaging techniques requires bright and photostable dyes or proteins as fluorophores. The photophysical properties of fluorophores have been proven to be crucial for super-resolution microscopy’s localization precision and imaging resolution. Fluorophores TAMRA and Atto Rho6G, which can interact with macrocyclic host cucurbit[7]uril (CB7) to form host-guest compounds, were found to improve the fluorescence intensity and lifetimes of these dyes. We enhanced the localization precision of direct stochastic optical reconstruction microscopy (dSTORM) by introducing CB7 into the imaging buffer, and showed that the number of photons as well as localizations of both TAMRA and Atto Rho6G increase over 2 times.     

Efficient visible/NIR light-driven uncaging of hydroxylated thiazole orange-based caged compounds in aqueous media

In photoactivation strategies with bioactive molecules, one-photon visible or two-photon near-infrared light-sensitive caged compounds are desirable tools for biological applications because they offer reduced phototoxicity and deep tissue penetration. However, visible-light-sensitive photoremovable protecting groups (PPGs) reported so far have displayed high hydrophobicity and low uncaging cross sections (εΦ < 50) in aqueous media, which can obstruct the control of bioactivity with high spatial and temporal precision. In this study, we developed hydroxylated thiazole orange (HTO) derivatives as visible-light-sensitive PPGs with high uncaging cross sections (εΦ ≈ 370) in aqueous solution. In addition, 2PE photolysis reactions of HTO-caged glutamate were achieved using a NIR laser (940 nm). Moreover, HTO-caged glutamate can activate N-methyl-d-aspartic acid receptors in Xenopus oocytes and mammalian cells with green-light illumination, thus allowing optical control of biological functions.

A hydroxylated thiazole orange (HTO)-caged glutamate efficiently releases a glutamate for temporal activation of ion channels under visible-to-NIR light in aqueous media.     

Redox-triggered hydroarylation of o-(hydroxyalkyl)arylalkynes with arylsulfonyl chlorides using visible light catalysis

A new radical-mediated method for the synthesis of 1-(2-(1,2-diarylvinyl)phenyl)ethan-1-ones by the redox hydroarylation of o-(hydroxyalkyl)arylalkynes with arylsulfonyl chlorides is described. This visible light catalysis method proceeds via a sequence of the radical addition of aryl group across the C-C triple bond, protonation and redox reaction, and represents a new redox transformation reaction directed by a neighboring hydroxyl group.     

Two-photon uncaging of bioactive compounds: Starter guide to an efficient IR light switch

Triggering physiological responses with a light switch has become a reality with the development of smart molecular probes such as photolabile protecting groups (PPGs), able to “uncage” biological ligands on demand. To make the light switch virtually harmless and confine the excitation to the single-cell level, the caged ligands can be released using two-photon (2P) absorption and 2P microscopy using red/infrared light. This exceptional level of precision however comes at the cost of a reduced photosensitivity and a poor compatibility of early PPGs with 2P excitation. This review aims to provide a tutorial guidebook to the design of 2P-sensitive PPGs suitable for optobiology by discussing challenges, strategies and progress in uncaging of bioactive compounds. To do so, we first recall the photo-physical principles governing 2P absorption, and the resulting ground rules in the design of efficient 2P absorbing organic dyes. We then detail how following these guidelines has led to tremendous progress in the development of a new generation of caged compounds, and the implications in the fields of biophotonics, from neurology to targeted therapy.     

Photoreactions of ferrocene with visible light in micellar solution

Photooxidation of ferrocene by CCl₄ and other organic oxidants is brought about by visible light in micellar solutions.     

Target-selective photodegradation of oligosaccharides by a fullerene-boronic acid hybrid upon visible light irradiation

A fullerene derivative was found to be capable of photodegrading oligosaccharides under irradiation with not only UV but also visible light. Furthermore, target-selective photodegradation of oligosaccharides (β-D-galactofuranosides) was achieved by a designed and synthesized fullerene-boronic acid hybrid upon irradiation with visible light in the absence of any additives under neutral conditions.