Reaction Of Singlet Oxygen Research Articles

Membrane reactors accelerate polymer photosensitizer-based singlet oxygen reactions

Polymer photosensitizers have gained a growing interest as singlet oxygen (1O2) generators. Although they provide a route to sustainable chemistry, their efficiency in bulk reactions is restricted by a limited oxygen supply and a short lifetime. Herein, we report membrane reactors that support a range of organic reactions using 1O2 generated from polymer photosensitizers. The porous nature of the membrane support, a nylon fabric membrane functionalized with poly(fluorenthiophen thiadiazothiophen) (PFOTTzT), allows highly efficient trapping of a thin membrane of reagents that is in close proximity to the 1O2 source. We demonstrate that oxidation reactions are accelerated by 10 – 100 folds, and polymerization reactions are rapidly initiated and accelerated and reach a nearly 2-fold increase in the degree of polymerization. The method is compatible with a range of solvents upon protection of the polymeric photosensitizers with a porous layer of polytetrafluoroethylene (PTFE) fabric that prevents solvent transport but allows 1O2 diffusion through. Summarizing, our membrane reactors are sustainable, low-cost, robust-in-use and overcome current limitations in reactions involving 1O2 from polymer photosensitizers and show strong potential for green industrial use.

Construction of dual active sites on diatomic metal (FeCo−N/C-x) catalysts for enhanced Fenton-like catalysis

High metal loading of single-atom catalysts enables excellent catalytic activity, but possibly causes serious aggregation problem. Herein, a series of diatomic FeCo−N/C-x (x represents metal content) were skillfully designed and applied to improve the catalytic activity for peroxymonosulfate (PMS) activation toward degrading organic micropollutants. The unprecedented dual active sites, referring to Fe(N3)−Co(N3) moiety and FeCo alloy, are constructed on the obtained FeCo−N/C-x, thereby exhibiting significantly greater performance toward degrading aqueous phenol (e.g., 0.316 min−1 for FeCo−N/C-3) via PMS activation, compared with those of traditional single-atom Co−N/C (0.011 min−1) and Fe−N/C (0.018 min−1). Combined experimental and theoretical calculations demonstrate the independent functions of dual active sites, in which Fe(N3)−Co(N3) and FeCo alloy can decrease the energy barrier of O−O bond cleaving resulting in the formation of high-valent FeCoO reactive species and singlet oxygen, respectively. This study opens up a new platform toward constructing dual active sites for enhanced Fenton-like catalytic activity.

Self-Rectifiable and Hypoxia-Assisted Chemo-Photodynamic Nanoinhibitor for Synergistic Cancer Therapy.

Photodynamic therapy (PDT) can eradicate cancer cells under light irradiation, mainly because of reactive singlet oxygen (1O2) being transformed from intratumoral oxygen. Nonetheless, the consumption of oxygen during PDT results in serious hypoxic conditions and an elevated hypoxia-inducing factor-1α (HIF-1α) level that hamper further photodynamic efficacy and induce tumor metastasis. To address this problem, we developed hypoxia-assisted NP-co-encapsulating Ce6 (photosensitizer) and YC-1 (HIF-1α inhibitor) as a self-rectifiable nanoinhibitor for synergistic antitumor treatment. PDT-aggravated intracellular hypoxic stress facilitated NP dissociation to release the drug (YC-1), which achieved tumor killing and HIF-1α inhibition to further enhance the therapeutic effect of PDT and prevent tumor metastasis. Besides, in vivo studies revealed that the HC/PI@YC-1 NPs afforded synergistic anticancer efficacy with minimal toxicity. Therefore, this study provides a prospective approach against PDT drawbacks and combination cancer therapy.

Enhanced peroxymonosulfate activation by Cu-doped LaFeO3 with rich oxygen vacancies: Compound-specific mechanisms

The degradation reaction mechanisms of organic pollutants by peroxymonosulfate (PMS) activation processes remain controversial. In this study, Cu-doped LaFeO3 samples were prepared and used as heterogeneous catalysts of PMS for the degradation of pharmaceuticals. Compared to LaFeO3 (LFO), the increased catalytic activity of LaFe1-xCuxO3 (LFCO) samples was observed, among which LFCO-7.5 exhibited the best performance. The enhanced catalytic activity of LFCO-7.5 was attributable to the generation of abundant oxygen vacancies. Hydroxyl radicals, sulfate radicals, superoxide and singlet oxygen were detected in the LFCO-7.5/PMS system. However, selective effects of radical scavengers on the degradation of different pharmaceuticals and selective reactivity of singlet oxygen toward different pharmaceuticals indicate the existence of compound-specific degradation mechanisms in the LFCO-7.5/PMS system. Furthermore, possible degradation pathways of SDZ and the toxicity evolution were investigated during sulfadiazine (SDZ) degradation. This study further enhances our knowledge on the degradation reaction mechanisms of organic pollutants in PMS activation processes.

Reactivity of Singlet Oxygen with DNA, an Update.

The reactivity of singlet oxygen with DNA constituents and in particular with the guanine base has been studied during more than four decades but the exact mechanisms by which such a reactive oxygen species reacts with DNA is still a matter of debate. In this review article, a summary of the data that were obtained from several laboratories and using complementary experimental and theoretical approaches are presented. Reaction mechanisms of 1 O2 with guanine and its oxidation product 8-oxo7,8-dihydroguanine are presented both at the nucleoside level and when the base is inserted into DNA since significant differences have been observed. Efforts have been made to propose tentative mechanisms to explain the conflicting results that were sometimes reported and hypotheses have been put forward to tentatively explain still contradictory observations.

Photoinactivation of bacteriophage MS2, Tulane virus and Vibrio parahaemolyticus in oysters by microencapsulated rose bengal

Abstract Bivalve molluscan shellfish such as oysters are important vectors for the transmission of foodborne pathogens including both viruses and bacteria. Photoinactivation provides a cold-sterilization option against the contamination as excited photosensitizers could transfer electronic energy to oxygen molecules producing reactive oxygen species such as singlet oxygen, leading to oxidative damage and death of the pathogens. However, the efficacy of photoinactivation is very often compromised by the presence of food matrix due to the nonselective reactions of short-lived singlet oxygen with organic matter other than the target pathogens. In order to address this issue, we encapsulated a food-grade photosensitizer rose bengal (RB) in alginate microbeads. An extra coating of chitosan effectively prevented the release of RB from the microbeads in seawater, and more importantly, enhanced the selectivity of the photoinactivation via the electrostatic interactions between cationic chitosan and anionic charge of the virus particles (bacteriophage MS2 and Tulane virus) and the Gram-negative bacteria Vibrio parahaemolyticus (V. parahaemolyticus). The treatment of oysters with microencapsulated RB resulted in significantly higher reductions of MS2 phage, Tulane virus and V. parahaemolyticus than free RB and non-RB carrying microbeads (P<0.05) tested with both in vitro and in vivo experimental set-ups. This study demonstrated a new strategy in delivering comprehensively formulated biochemical sanitizers in bivalve shellfish through their natural filter-feeding activity and thereby enhancing the mitigation efficiency of foodborne pathogen contamination.

Electronic couplings for singlet oxygen photosensitization and its molecular orbital overlap description

The reaction of triplet fusion, also named triplet-triplet annihilation, has attracted a lot of research interests because of its wide applications in photocatalytic, solar cells, and bioimaging. As for the singlet oxygen photosensitization, the reactive singlet oxygen species are generated through the energy transfers from photosensitizer (PS) to ground triplet oxygen molecule. In this work, we computed the electronic coupling for singlet oxygen photosensitization using the nonadiabatic coupling from the quantum chemical calculation. Then we utilized the molecular orbital (MO) overlaps to approximate it, where the MOs were computed from isolated single molecules. As demonstrated with quantitative results, this approach well describes the distribution of the coupling strength as the function of the intermolecular distance between the sensitizer and O2, providing us a simple but effective way to predict the coupling of triplet fusion reactions.

Direct and Indirect Chemiluminescence: Reactions, Mechanisms and Challenges.

Emission of light by matter can occur through a variety of mechanisms. When it results from an electronically excited state of a species produced by a chemical reaction, it is called chemiluminescence (CL). The phenomenon can take place both in natural and artificial chemical systems and it has been utilized in a variety of applications. In this review, we aim to revisit some of the latest CL applications based on direct and indirect production modes. The characteristics of the chemical reactions and the underpinning CL mechanisms are thoroughly discussed in view of studies from the very recent bibliography. Different methodologies aiming at higher CL efficiencies are summarized and presented in detail, including CL type and scaffolds used in each study. The CL role in the development of efficient therapeutic platforms is also discussed in relation to the Reactive Oxygen Species (ROS) and singlet oxygen (1O2) produced, as final products. Moreover, recent research results from our team are included regarding the behavior of commonly used photosensitizers upon chemical activation under CL conditions. The CL prospects in imaging, biomimetic organic and radical chemistry, and therapeutics are critically presented in respect to the persisting challenges and limitations of the existing strategies to date.

Merging of a Perylene Moiety Enables a RuII Photosensitizer with Long-Lived Excited States and the Efficient Production of Singlet Oxygen.

Multichromophoric systems based on a RuII polypyridine moiety containing an additional organic chromophore are of increasing interest with respect to different light‐driven applications. Here, we present the synthesis and detailed characterization of a novel RuII photosensitizer, namely [(tbbpy)2Ru((2‐(perylen‐3‐yl)‐1H‐imidazo[4,5‐f][1,10]‐phenanthrolline))](PF6)2 RuipPer, that includes a merged perylene dye in the back of the ip ligand. This complex features two emissive excited states as well as a long‐lived (8 μs) dark state in acetonitrile solution. Compared to prototype [(bpy)3Ru]2+‐like complexes, a strongly altered absorption (ϵ=50.3×103 M−1 cm−1 at 467 nm) and emission behavior caused by the introduction of the perylene unit is found. A combination of spectro‐electrochemistry and time‐resolved spectroscopy was used to elucidate the nature of the excited states. Finally, this photosensitizer was successfully used for the efficient formation of reactive singlet oxygen.

Synthesis of Some Substituted Furans and Endoperoxides Via Singlet Oxygen Reactions

Cinnamaldehyde was used to condense with substituted acetophenone then with acetone to form substituted 2,4- diene -1- pentanone (1- 4), after two moles of cinnamaldehyde condense with one mole of acetone to form 1, 5- diphenyl nona- 8- tetraene -5 – one (5), for these reactions, sodium hydroxide was used as a catalyst, the resulted compounds reduced by Luche (specific reduction agent use cerium chloride as a catalyst with sodium borohydride to protect double bond) reaction to form 2,4- diene-1- methoxy pentane (6-9) and -5- methoxy nona- 1,3,6,8 – tetraene – 1,9 - diyl dibenzene (10), the resulted dienes compound converted to endoperoxides (11- 15) via singlet oxygen reaction in the present of Rose Bengal as a catalyst with light in chlorinated solvent and finally by appling of Appel reaction condition these compounds converted to furans (16- 20). All mechanisms of the reaction were listed. These compounds were identified by thin layer chromatography TLC, and by their physical properties in addition, the IR spectroscopy and 1HNMR.

Visualising UV-A light-induced damage to plasma membranes of eye lens.

An eye lens is constantly exposed to the solar UV radiation, which is considered the most important external source of age-related changes to eye lens constituents. The accumulation of modifications of proteins and lipids with age can eventually lead to the development of progressive lens opacifications, such as cataracts. Though the impact of solar UV radiation on the structure and function of proteins is actively studied, little is known about the effect of photodamage on plasma membranes of lens cells. In this work we exploit Fluorescence Lifetime Imaging Microscopy (FLIM), together with viscosity-sensitive fluorophores termed molecular rotors, to study the changes in viscosity of plasma membranes of porcine eye lens resulting from two different types of photodamage: Type I (electron transfer) and Type II (singlet oxygen) reactions. We demonstrate that these two types of photodamage result in clearly distinct changes in viscosity - a decrease in the case of Type I damage and an increase in the case of Type II processes. Finally, to simulate age-related changes that occur in vivo, we expose an intact eye lens to UV-A light under anaerobic conditions. The observed decrease in viscosity within plasma membranes is consistent with the ability of eye lens constituents to sensitize Type I photodamage under natural irradiation conditions. These changes are likely to alter the transport of metabolites and predispose the whole tissue to the development of pathological processes such as cataracts.

The Reactive Oxygen Species Singlet Oxygen, Hydroxy Radicals, and the Superoxide Radical Anion—Examples of Their Roles in Biology and Medicine

Reactive oxygen species comprise oxygen-based free radicals and non-radical species such as peroxynitrite and electronically excited (singlet) oxygen. These reactive species often have short lifetimes, and much of our understanding of their formation and reactivity in biological and especially medical environments has come from complimentary fast reaction methods involving pulsed lasers and high-energy radiation techniques. These and related methods, such as EPR, are discussed with particular reference to singlet oxygen, hydroxy radicals, the superoxide radical anion, and their roles in medical aspects, such as cancer, vision and skin disorders, and especially pro- and anti-oxidative processes.

Iron-Based Dual Active Site-Mediated Peroxymonosulfate Activation for the Degradation of Emerging Organic Pollutants.

It is still a challenge to synthesize highly efficient and stable catalysts for the Fenton-like reaction. In this study, we constructed an integrated catalyst with highly dispersed iron-based dual active sites, in which Fe2N and single-atom Fe (SA-Fe) were embedded into nitrogen- and oxygen-co-doped graphitic carbon (Fe-N-O-GC-350). Extended X-ray absorption fine structure (EXAFS) confirmed the coordination structure of iron, and line combination fitting (LCF) demonstrated the coexistence of Fe2N and SA-Fe with percentages of 75 and 25%, respectively. Iron-based dual active sites endowed Fe-N-O-GC-350 with superior catalytic activity to activate peroxymonosulfate (PMS) as evidenced by the fast degradation rate of sulfamethoxazole (SMX) (0.24 min-1) in the presence of 0.4 mM PMS and 0.1 g/L Fe-N-O-GC-350. Unlike the reported singlet oxygen and high-valent iron oxo-mediated degradation induced by the SA-Fe catalyst, both surface-bound reactive species and singlet oxygen contributed to SMX degradation, while surface-bound reactive species dominated. Density functional theory (DFT) simulation indicated that Fe2N and SA-Fe enhanced the adsorption of PMS, which played a key role in PMS activation. The Fe-N-O-GC-350/PMS system had resistance to the interference of common inorganic anions and high oxidation capacity to recalcitrant organic contaminants. This study elucidated the important role of Fe2N in PMS activation and provide a clue to design rationally catalysts with iron-based dual active sites to activate PMS for the degradation of emerging organic pollutants.

Suppressing Singlet Oxygen Formation during the Charge Process of Li-O2 Batteries with a Co3O4 Solid Catalyst Revealed by Operando Electron Paramagnetic Resonance.

Aprotic lithium-oxygen (Li-O2) batteries promise high energy, but the cycle life has been plagued by two major obstacles, the insulating products and highly reactive singlet oxygen (1O2), which cause higher overpotential and parasitic reactions, respectively. A solid-state catalyst is known to reduce overpotential; however, it is unclear whether it affects 1O2 generation. Herein, Co3O4 was employed as the representative catalyst in Li-O2 batteries, and 1O2 generation was investigated by ex-situ and operando electron paramagnetic resonance (EPR) spectroscopy. By comparing a carbon nanotube (CNT) cathode with a Co3O4/CNT cathode, we find that 1O2 generation in the charge process can be suppressed by the Co3O4 catalyst. After carefully studying the discharge products on the two electrodes and the corresponding decomposition processes, we conclude that a LiO2-like species is responsible for the 1O2 generation during the early charge stage. The Co3O4 catalyst reduces the amount of LiO2-like species in discharge products, and thus the 1O2 formation is suppressed.

Local DNA microviscosity converts ruthenium polypyridyl complexes to ultrasensitive photosensitizers

In this manuscript, we have reported how DNA binding of ruthenium polypyridyl complexes (RPCs) make them more efficient photosensitizer. The DNA binding of RPCs results in a significant enhancement of their emission intensity and excited-state lifetime. As a result, upon visible-light irradiation, these complexes generate reactive singlet oxygen, which causes selective DNA damage and kills cancer cells. This investigation also demonstrates the effect of light-driven RPCs on bacterial growth arrest through DNA nicking and differential localization in cancer and non-cancer cells. The local DNA microviscosity suppresses the non-radiative pathways which causes a large enhancement in the emission intensity and the excited state lifetime. The visible-light-triggered singlet-oxygen efficiently produces nick in DNA and inhibits bacterial growth. RPCs also localize inside the cancer cell nucleus and in the vicinity of the nuclear membrane of non-cancerous cells, confirmed by live-cell confocal microscopy. The results provide a facile platform for the novel antibiotic intended discovery combined with cancer therapy.

Graphene Oxide and Graphene Quantum Dots as Delivery Systems of Cationic Porphyrins: Photo-Antiproliferative Activity Evaluation towards T24 Human Bladder Cancer Cells.

The development of new photodynamic therapy (PDT) agents designed for bladder cancer (BC) treatments is of utmost importance to prevent its recurrence and progression towards more invasive forms. Here, three different porphyrinic photosensitizers (PS) (TMPyP, Zn-TMPyP, and P1-C5) were non-covalently loaded onto graphene oxide (GO) or graphene quantum dots (GQDs) in a one-step process. The cytotoxic effects of the free PS and of the corresponding hybrids were compared upon blue (BL) and red-light (RL) exposure on T24 human BC cells. In addition, intracellular reactive oxygen species (ROS) and singlet oxygen generation were measured. TMPyP and Zn-TMPyP showed higher efficiency under BL (IC50: 0.42 and 0.22 μm, respectively), while P1-C5 was more active under RL (IC50: 0.14 μm). In general, these PS could induce apoptotic cell death through lysosomes damage. The in vitro photosensitizing activity of the PS was not compromised after their immobilization onto graphene-based nanomaterials, with Zn-TMPyP@GQDs being the most promising hybrid system under RL (IC50: 0.37 μg/mL). Overall, our data confirm that GO and GQDs may represent valid platforms for PS delivery, without altering their performance for PDT on BC cells.

Quantification of Hydroperoxides by Gas Chromatography with Flame Ionisation Detection

Hydroperoxides are of great importance in the fields of atmospheric and biological chemistry. However, there are several analytical challenges in their analysis: unknown and usually low UV absorption coefficients, high reactivity, thermal instability, and a lack of available reference standards. To overcome these limitations, we propose a GC-FID approach involving pre-column silylation and quantification via the effective carbon number approach. Four hydroperoxides of α-pinene were synthesized in the liquid phase with singlet oxygen and identified using literature data on isomer yield distribution, MS spectra, estimated boiling temperatures of each isomer (retention time), their thermal stability and derivatisation rate. The developed procedure was used for the determination of hydroperoxides in bottled and autooxidised turpentine. We anticipate that this method could also be applied in atmospheric chemistry, where the reactivity of singlet oxygen could help explain the high formation rates of secondary organic aerosols.

A portable NIR fluorimeter directly quantifies singlet oxygen generated by nanostructures for Photodynamic Therapy

This paper reports on the setting up and calibration of a portable NIR fluorimeter specifically developed for quantitative direct detection of the highly reactive singlet oxygen (1O2) chemical specie, of great importance in Photodynamic therapies. This quantification relies on the measurement of fluorescence emission of 1O2, which is peaked in the near-infrared (NIR) at λ=1270nm.In recent years, several nanostructures capable of generating reactive oxygen species (ROS) when activated by penetrating radiation (X-rays, NIR light) have been developed to apply Photodynamic Therapy (PDT) to tumours in deep tissue, where visible light cannot penetrate. A bottleneck in the characterization of these nanostructures is the lack of a fast and reliable technique to quantitatively assess their performances in generating ROS, and in particular 1O2. For instance, the widely used PDT “Singlet Oxygen Sensor Green” kit suffers from self-activation under X-ray irradiation.To solve this difficulty, we propose here direct detection of 1O2 by spectroscopic means, using an apparatus developed by us around a recent thermoelectrically-cooled InGaAs single photon avalanche photodiode (SPAD). The SPAD is coupled to a custom-made integrating sphere designed for use under irradiation with high-energy X-ray beams from clinical Radiotherapy sources. We determine the detection threshold for our apparatus, which turns to be ∼9·1081O2 in realistic experimental condition and for measurements extending to 1 min of integration. After calibrations on standard photosensitizers, we demonstrate the potentiality of this instrument characterizing some photosensitizing nanostructures developed by us.

Thermal and Mechanochemical Tuning of the Porphyrin Singlet-Triplet Gap for Selective Energy Transfer Processes: A Molecular Dynamics Approach.

Molecular dynamics simulations provide fundamental knowledge on the reaction mechanism of a given simulated molecular process. Nevertheless, other methodologies based on the “static” exploration of potential energy surfaces are usually employed to firmly provide the reaction coordinate directly related to the reaction mechanism, as is the case in intrinsic reaction coordinates for thermally activated reactions. Photoinduced processes in molecular systems can also be studied with these two strategies, as is the case in the triplet energy transfer process. Triplet energy transfer is a fundamental photophysical process in photochemistry and photobiology, being for instance involved in photodynamic therapy, when generating the highly reactive singlet oxygen species. Here, we study the triplet energy transfer process between porphyrin, a prototypical energy transfer donor, and different biologically relevant acceptors, including molecular oxygen, carotenoids, and rhodopsin. The results obtained by means of nanosecond time-scale molecular dynamics simulations are compared to the “static” determination of the reaction coordinate for such a thermal process, leading to the distortions determining an effective energy transfer. This knowledge was finally applied to propose porphyrin derivatives for producing the required structural modifications in order to tune their singlet-triplet energy gap, thus introducing a mechanochemical description of the mechanism.

Activation of peroxydisulfate using N-doped carbon-encapsulated Ni species for efficient degradation of tetracycline

In this study, N-doped porous carbon materials embedded with NiNx species (Ni@NC) were fabricated via the pyrolysis of Ni-doped zeolitic imidazolate frameworks-8 (ZIF-8) at the temperature of 900 °C. The obtained Ni@NC-1 catalyst exhibited excellent activity in activating the peroxydisulfate (PDS) that was used for removing tetracycline (TC). The catalytic system exhibited good stability, wide pH adaptation, and high resistance to the operational environment. It was supposed that NiNx species could attach to PDS and act as electron acceptors to receive the electrons for activating the PDS, thus generating highly reactive superoxide radicals (⋅O2−) and singlet oxygen (1O2) species for rapid degradation of TC. The electron transfer and dissolved oxygen-derived ⋅O2− were also responsible for the degradation of TC. In addition, the Ni@NC-1/PDS system exhibited high efficiency for removing oxytetracycline, ciprofloxacin, or levofloxacin. The results of this study would promote the design of other MOFs-derived carbon-encapsulated metal species for efficiently activating persulfate to remove antibiotics from the wastewater.