Photooxidation Responsive Elastin-Like Polypeptide Conjugates for Photodynamic Therapy Application.

Stimuli-responsive recombinant elastin-like polypeptides (ELPs) are artificial protein polymers derived from the hydrophobic domain of tropoelastin that have attracted significant interest for drug delivery and tissue engineering applications. In the present study, we have conjugated a photosensitizer (PS) to a hydrophobic methionine-containing ELP scaffold, which upon reaction with singlet oxygen (1O2) is transformed into a hydrophilic sulfoxide derivative facilitating the disassembly of photosensitizer-delivery particles during the photodynamic therapy (PDT) process. A peripherally substituted carboxy-Zn(II)-phthalocyanine derivative (TT1) bearing a carboxyl group directly linked to the Pc-ring, and presenting an absorption maximum around 680 nm, was selected as PS which simultaneously acted as a photooxidation catalyst. A TT1-ELP[M1V3-40] conjugate was prepared from ELP[M1V3-40] modified with an alkyne group at the N-terminal chain end, and from TT1-amide-C3-azide by copper(I)-catalyzed alkyne-azide cycloaddition (CuAAC) reaction. This innovative model photooxidation sensitive PS delivery technology offers promising attributes in terms of temperature-controlled particle formation and oxidation-triggered release, narrow molar mass distribution, reproducibility, scalability, non-immunogenicity, biocompatibility, and biodegradability for pharmaceutical applications in an effort to improve the clinical effectiveness of PDT treatments.

Light-Induced Histidine Adducts to an IgG1 Molecule Via Oxidized Histidine Residue and the Potential Impact of Polysorbate-20 Concentration.

PURPOSE: Histidine (His) undergoes light-induced reactions such as oxidation, crosslinking and addition. These reactions are initiated by singlet oxygen (1O2) to generate His photo-oxidation products, which are subject to nucleophilic attack by a non-oxidized His residue from another protein or by nucleophilic buffer components such as Tris and His. This report aims to identify light-induced His-adducts to a monoclonal antibody (mAb-1) due to the reaction of His molecules in the buffer with the photooxidized His residues under ICH light conditions. Since polysorbate-20 (PS-20) is a commonly used excipient in biotherapeutics formulation, it is also important to study the impact of PS-20 concentration on protein photostability. RESULTS: We identified and characterized light-induced His-adducts of mAb-1 by LC-MS/MS. We showed that the levels of light-induced His-adducts generally correlate with the solvent accessibility of His residues in the protein. In addition, the presence of PS-20 at concentrations commonly used in protein drug formulations can significantly increase the levels of light-induced His-adducts. CONCLUSIONS: Since His residues are present in a conserved region in the Fc domain, and may be present in the complementarity-determining region (CDR), the impact on the biological functions of the His-adducts observed here should be further studied to evaluate the risk of their presence.

Chitosan Nanocomposite Coatings Containing Chemically Resistant ZnO-SnOx Core-shell Nanoparticles for Photocatalytic Antifouling.

Functional nanocomposites with biopolymers and zinc oxide (ZnO) nanoparticles is an emerging application of photocatalysis in antifouling coatings. The reduced chemical stability of ZnO in the acidic media in which chitosan is soluble affects the performance of chitosan nanocomposites in antifouling applications. In this study, a thin shell of amorphous tin dioxide (SnOx) was grown on the surface of ZnO to form ZnO-SnOx core-shell nanoparticles that improved the chemical stability of the photocatalyst nanoparticles, as examined at pH 3 and 6. The photocatalytic activity of ZnO-SnOx in the degradation of methylene blue (MB) dye under visible light showed a higher efficiency than that of ZnO nanoparticles due to the passivation of electronic defects. Chitosan-based antifouling coatings with varying percentages of ZnO or ZnO-SnOx nanoparticles, with or without the glutaraldehyde (GA) crosslinking of chitosan, were developed and studied. The incorporation of photocatalysts into the chitosan matrix enhanced the thermal stability of the coatings. Through a mesocosm study using running natural seawater, it was found that chitosan/ZnO-SnOx/GA coatings enabled better inhibition of bacterial growth compared to chitosan coatings alone. This study demonstrates the antifouling potential of chitosan nanocomposite coatings containing core-shell nanoparticles as an effective solution for the prevention of biofouling.

Synthesis of Xanthones, Thioxanthones and Acridones by a Metal-Free Photocatalytic Oxidation Using Visible Light and Molecular Oxygen.

9H-Xanthenes, 9H-thioxanthenes and 9,10-dihydroacridines can be easily oxidized to the corresponding xanthones, thioxanthones and acridones, respectively, by a simple photo-oxidation procedure carried out using molecular oxygen as oxidant under the irradiation of visible blue light and in the presence of riboflavin tetraacetate as a metal-free photocatalyst. The obtained yields are high or quantitative.

Oxidative Photocyclization of Aromatic Schiff Bases in Synthesis of Phenanthridines and Other Aza-PAHs.

The oxidative photocyclization of aromatic Schiff bases was investigated as a potential method for synthesis of phenanthridine derivatives, biologically active compounds with medical applications. Although it is possible to prepare the desired phenanthridines using such an approach, the reaction has to be performed in the presence of acid and TEMPO to increase reaction rate and yield. The reaction kinetics was studied on a series of substituted imines covering the range from electron-withdrawing to electron-donating substituents. It was found that imines with electron-withdrawing substituents react one order of magnitude faster than imines bearing electron-donating groups. The 1H NMR monitoring of the reaction course showed that a significant part of the Z isomer in the reaction is transformed into E isomer which is more prone to photocyclization. The portion of the Z isomer transformed showed a linear correlation to the Hammett substituent constants. The reaction scope was expanded towards synthesis of larger aromatic systems, namely to the synthesis of strained aromatic systems, e.g., helicenes. In this respect, it was found that the scope of oxidative photocyclization of aromatic imines is limited to the formation of no more than five ortho-fused aromatic rings.

Novel magnetically separable of Fe3O4/Ag3PO4@WO3 nanocomposites for enhanced photocatalytic and antibacterial activity against Staphylococcus aureus (S. aureus).

BACKGROUND: Iron oxide nanocomposites have received a great attention for their application in various fields like physics, medicine, biology, and material science etc., due to their unique properties, such as magnetism, electrical properties, small size, biocompatibility and low toxicity. METHODS: Fe3O4/Ag3PO4@WO3 nanocomposites with different weight percent of Ag3PO4 were successfully prepared through fabricated Ag3PO4/Fe3O4 with WO3 via in situ fabrication method, electrospinning involved precursor solution preparation and spinning to enhance photocatalyst performance under simulated sunlight for the degradation of methylene blue (MB) and antibacterial activity against Staphylococcus aureus (S. aureus). RESULTS: The photocatalytic degradation of methylene blue (MB) under simulated light irradiation indicated that the nanocomposite with 0.25 mg of Ag3PO4 has the best activity. An additional advantage of these photocatalysts is magnetic recoverability, using external magnetic field and photocatalytic stability of the nanocomposites was evaluated for three cycles. In addition, using different scavengers, holes (h+) and superoxide radical (O 2 ·-) radicals and hydroxide radical (·OH) were identified the main oxidative species in the degradation reaction of methylene blue. CONCLUSIONS: The results reveal that Fe3O4/Ag3PO4@WO3-0.25 nanocomposites have photocatalytic and antibacterial activity against S. aureus. The photocatalyst and mechanism based on the enhancement of electron transfer processes between Ag3PO4 and WO3 nanoparticles.

DNA Oxidation Photoinduced by Norharmane Rhenium(I) Polypyridyl Complexes: Effect of the Bidentate N,N'-Ligands on the Damage Profile.

ReI -polypyridyl complexes have interesting and distinctive photochemical and photosensitizing properties. This work describes the capability to induce (or photoinduce) DNA damage of three ReI -complexes with a naturally occurring alkaloid called norharmane (nHo) as ligand: [Re(CO)3 (nHo)(L)]CF3 SO3 where L=2,2'-bipyridine (ReBpy), phenanthroline (RePhen) or dipyrido[3,2-a:2',3'-c]phenazine (ReDppz). The interaction of the complexes with DNA was investigated by steady-state and time-resolved spectroscopy. Data show that the mode and strength of interaction depend on the chemical structure of the bidentate ligand. The complexes show a major static contribution to the overall interaction, giving rise to the formation of noncovalent adducts with DNA, and the particular trend observed was RePhen>ReDppz>ReBpy. Photo-oxidation at the purine bases represents the major DNA damaging mechanism. RePhen also induces single-strand breaks in a yield similar to that of base damage, suggesting an additional photosensitizing pathway. We also performed the Ames test to evaluate the cytotoxic and mutagenic properties of both non-irradiated and photoexcited complexes. RePhen, but not the other complexes, turned out to be both toxic and phototoxic for the bacteria.

Ozone in the food industry: Principles of ozone treatment, mechanisms of action, and applications: An overview.

The food contamination issue requires continuous control of food at each step of the production process. High quality and safety of products are equally important factors in the food industry. They may be achieved with several, more or less technologically advanced methodologies. In this work, we review the role, contribution, importance, and impact of ozone as a decontaminating agent used to control and eliminate the presence of microorganisms in food products as well as to extend their shelf-life and remove undesirable odors. Several researchers have been focusing on the ozone's properties and applications, proving that ozone treatment technology can be applied to all types of foods, from fruits, vegetables, spices, meat, and seafood products to beverages. A compilation of those works, presented in this review, can be a useful tool for establishing appropriate ozone treatment conditions, and factors affecting the improved quality and safety of food products. A critical evaluation of the advantages and disadvantages of ozone in the context of its application in the food industry is presented as well.

Inosine Can Increase DNA's Susceptibility to Photo-oxidation by a RuII Complex due to Structural Change in the Minor Groove.

Key to the development of DNA-targeting phototherapeutic drugs is determining the interplay between the photoactivity of the drug and its binding preference for a target sequence. For the photo-oxidising lambda-[Ru(TAP)2 (dppz)]2+ (Λ-1) (dppz=dipyridophenazine) complex bound to either d{T1 C2 G3 G4 C5 G6 C7 C8 G9 A10 }2 (G9) or d{TCGGCGCCIA}2 (I9), the X-ray crystal structures show the dppz intercalated at the terminal T1 C2 ;G9 A10 step or T1 C2 ;I9 A10 step. Thus substitution of the G9 nucleobase by inosine does not affect intercalation in the solid state although with I9 the dppz is more deeply inserted. In solution it is found that the extent of guanine photo-oxidation, and the rate of back electron-transfer, as determined by pico- and nanosecond time-resolved infrared and transient visible absorption spectroscopy, is enhanced in I9, despite it containing the less oxidisable inosine. This is attributed to the nature of the binding in the minor groove due to the absence of an NH2 group. Similar behaviour and the same binding site in the crystal are found for d{TTGGCGCCAA}2 (A9). In solution, we propose that intercalation occurs at the C2 G3 ;C8 I9 or T2 G3 ;C8 A9 steps, respectively, with G3 the likely target for photo-oxidation. This demonstrates how changes in the minor groove (in this case removal of an NH2 group) can facilitate binding of RuII dppz complexes and hence influence any sensitised reactions occurring at these sites. No similar enhancement of photooxidation on binding to I9 is found for the delta enantiomer.

Reversing the Regioselectivity of Halofunctionalization Reactions through Cooperative Photoredox and Copper Catalysis.

Halofunctionalization of alkenes is a classical method for olefin difunctionalization. It gives rise to adducts which are found in many natural products and biologically active molecules, and offers a synthetic handle for further manipulation. Classically, this reaction is performed with an electrophilic halogen source and leads to regioselective formation of the halofunctionalized adducts. Herein, we demonstrate a reversal of the native regioselectivity for alkene halofunctionalization through the use of an acridinium photooxidant in conjunction with a copper cocatalyst.

Production of Metal-Free Composites Composed of Graphite Oxide and Oxidized Carbon Nitride Nanodots and Their Enhanced Photocatalytic Performances.

A novel metal-free composite (GN) composed of two types of carbon-based nanomaterials, graphite oxide (GO) and 2D oxidized carbon nitride (OCN) nanodots was produced. Chemical and morphological characterizations reveal that GN contains a main component of GO with well-dispersed 2D OCN nanodots. GN shows enhanced photocatalytic performance for degrading an organic pollutant, Rhodamine B, under visible light.

Photocatalytic Oxygenation of Substrates by Dioxygen with Protonated Manganese(III) Corrolazine.

UV-vis spectral titrations of a manganese(III) corrolazine complex [Mn(III)(TBP8Cz)] with HOTf in benzonitrile (PhCN) indicate mono- and diprotonation of Mn(III)(TBP8Cz) to give Mn(III)(OTf)(TBP8Cz(H)) and [Mn(III)(OTf)(H2O)(TBP8Cz(H)2)][OTf] with protonation constants of 9.0 × 10(6) and 4.7 × 10(3) M(-1), respectively. The protonated sites of Mn(III)(OTf)(TBP8Cz(H)) and [Mn(III)(OTf)(H2O)(TBP8Cz(H)2)][OTf] were identified by X-ray crystal structures of the mono- and diprotonated complexes. In the presence of HOTf, the monoprotonated manganese(III) corrolazine complex [Mn(III)(OTf)(TBP8Cz(H))] acts as an efficient photocatalytic catalyst for the oxidation of hexamethylbenzene and thioanisole by O2 to the corresponding alcohol and sulfoxide with 563 and 902 TON, respectively. Femtosecond laser flash photolysis measurements of Mn(III)(OTf)(TBP8Cz(H)) and [Mn(III)(OTf)(H2O)(TBP8Cz(H)2)][OTf] in the presence of O2 revealed the formation of a tripquintet excited state, which was rapidly converted to a tripseptet excited state. The tripseptet excited state of Mn(III)(OTf)(TBP8Cz(H)) reacted with O2 with a diffusion-limited rate constant to produce the putative Mn(IV)(O2(•-))(OTf)(TBP8Cz(H)), whereas the tripseptet excited state of [Mn(III)(OTf)(H2O)(TBP8Cz(H)2)][OTf] exhibited no reactivity toward O2. In the presence of HOTf, Mn(V)(O)(TBP8Cz) can oxidize not only HMB but also mesitylene to the corresponding alcohols, accompanied by regeneration of Mn(III)(OTf)(TBP8Cz(H)). This thermal reaction was examined for a kinetic isotope effect, and essentially no KIE (1.1) was observed for the oxidation of mesitylene-d12, suggesting a proton-coupled electron transfer (PCET) mechanism is operative in this case. Thus, the monoprotonated manganese(III) corrolazine complex, Mn(III)(OTf)(TBP8Cz(H)), acts as an efficient photocatalyst for the oxidation of HMB by O2 to the alcohol.

Anoxic photochemical oxidation of siderite generates molecular hydrogen and iron oxides.

Photochemical reactions of minerals are underappreciated processes that can make or break chemical bonds. We report the photooxidation of siderite (FeCO3) by UV radiation to produce hydrogen gas and iron oxides via a two-photon reaction. The calculated quantum yield for the reaction suggests photooxidation of siderite would have been a significant source of molecular hydrogen for the first half of Earth's history. Further, experimental results indicate this abiotic, photochemical process may have led to the formation of iron oxides under anoxic conditions. The reaction would have continued through the Archean to at least the early phases of the Great Oxidation Event, and provided a mechanism for oxidizing the atmosphere through the loss of hydrogen to space, while simultaneously providing a key reductant for microbial metabolism. We propose that the photochemistry of Earth-abundant minerals with wide band gaps would have potentially played a critical role in shaping the biogeochemical evolution of early Earth.

Ultrafast photodriven intramolecular electron transfer from an iridium-based water-oxidation catalyst to perylene diimide derivatives.

Photodriving the activity of water-oxidation catalysts is a critical step toward generating fuel from sunlight. The design of a system with optimal energetics and kinetics requires a mechanistic understanding of the single-electron transfer events in catalyst activation. To this end, we report here the synthesis and photophysical characterization of two covalently bound chromophore-catalyst electron transfer dyads, in which the dyes are derivatives of the strong photooxidant perylene-3,4:9,10-bis(dicarboximide) (PDI) and the molecular catalyst is the Cp*Ir(ppy)Cl metal complex, where ppy = 2-phenylpyridine. Photoexcitation of the PDI in each dyad results in reduction of the chromophore to PDI(•-) in less than 10 ps, a process that outcompetes any generation of (3*)PDI by spin-orbit-induced intersystem crossing. Biexponential charge recombination largely to the PDI-Ir(III) ground state is suggestive of multiple populations of the PDI(•-)-Ir(IV) ion-pair, whose relative abundance varies with solvent polarity. Electrochemical studies of the dyads show strong irreversible oxidation current similar to that seen for model catalysts, indicating that the catalytic integrity of the metal complex is maintained upon attachment to the high molecular weight photosensitizer.

Adsorption of SOx and NOx in activated viscose fibers.

SOx and NOx are emissions resulting from combustion processes and are the main agents that contribute to the formation of acid rain, which causes harm to humans and the environment. Several techniques for removing these pollutants are applied in i.e. oil refineries, thermoelectric that use petroleum oils and vehicular pollution. Among these, highlight the adsorption of contaminants by the usage of activated carbon fibers and activated carbon, which are characterized by high surface area and uniform distribution of pores, providing appropriate conditions for application in processes of removing environmental contaminants. In the present work, activated viscose fibers (AVF) were prepared and applied in adsorption experiments of NO and SO2. The materials produced showed high values of surface area, with a predominance of micro pores with diameters in the range of 1.0 nm. The AVF had satisfactory performance in the removal of contaminants and are compatible with other synthetic fibers. Thus, the formation of active sites of carbon provides contaminants adsorption, demonstrating that carbon fibers cloth can be applied for the removal of pollutants.

Photooxidation of arsenic(III) to arsenic(V) on the surface of kaolinite clay.

As one of the most toxic heavy metals, the oxidation of inorganic arsenic has drawn great attention among environmental scientists. However, little has been reported on the solar photochemical behavior of arsenic species on top-soil. In the present work, the influencing factors (pH, relative humidity (RH), humic acid (HA), trisodium citrate, and additional iron ions) and the contributions of reactive oxygen species (ROS, mainly HO and HO2/O2(-)) to photooxidation of As(III) to As(V) on kaolinite surfaces under UV irradiation (λ=365nm) were investigated. Results showed that lower pH facilitated photooxidation, and the photooxidation efficiency increased with the increase of RH and trisodium citrate. Promotion or inhibition of As(III) photooxidation by HA was observed at low or high dosages, respectively. Additional iron ions greatly promoted the photooxidation, but excessive amounts of Fe(2+) competed with As(III) for oxidation by ROS. Experiments on scavengers indicated that the HO radical was the predominant oxidant in this system. Experiments on actual soil surfaces proved the occurrence of As(III) photooxidation in real topsoil. This work demonstrates that the photooxidation process of As(III) on the soil surface should be taken into account when studying the fate of arsenic in natural soil newly polluted with acidic wastewater containing As(III).

Heterogeneous oxidation of SO2 by O3-aged black carbon and its dithiothreitol oxidative potential.

Ozone (O3) is an important atmospheric oxidant. Black carbon (BC) particles released into the atmosphere undergo an aging process via O3 oxidation. O3-aged BC particles may change their uptake ability toward trace reducing gases such as SO2 in the atmosphere, leading to different environmental and health effects. In this paper, the heterogeneous reaction process between O3-aged BC and SO2 was explored via in-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). Combined with ion chromatography (IC), DRIFTS was used to qualitatively and quantitatively analyze the sulfate product. The results showed that O3-aged BC had stronger SO2 oxidation ability than fresh BC, and the reactive species/sites generated on the surface had an important role in the oxidation of SO2. Relative humidity or 254nm UV (ultraviolet) light illumination enhanced the oxidation uptake of SO2 on O3-aged BC. The oxidation potentials of the BC particles were detected via dithiothreitol (DTT) assay. The DTT activity over BC was decreased in the process of SO2 reduction, with the consumption of oxidative active sites.

Complex pathways in folding of protein G explored by simulation and experiment.

The B1 domain of protein G has been a classic model system of folding for decades, the subject of numerous experimental and computational studies. Most of the experimental work has focused on whether the protein folds via an intermediate, but the evidence is mostly limited to relatively slow kinetic observations with a few structural probes. In this work we observe folding on the submillisecond timescale with microfluidic mixers using a variety of probes including tryptophan fluorescence, circular dichroism, and photochemical oxidation. We find that each probe yields different kinetics and compare these observations with a Markov State Model constructed from large-scale molecular dynamics simulations and find a complex network of states that yield different kinetics for different observables. We conclude that there are many folding pathways before the final folding step and that these paths do not have large free energy barriers.

Ozone-induced oxidative modification of plasma fibrin-stabilizing factor.

The plasma fibrin-stabilizing factor (pFXIII) function is to maintain a hemostasis by the fibrin clot stabilization. The conversion of pFXIII to the active form of the enzyme (FXIIIа) is a multistage process. Ozone-induced oxidation of pFXIII has been investigated at different stages of its enzyme activation. The biochemical results point to a decrease of an enzymatic activity of FXIIIа depending largely on the stage of the pFXIII conversion into FXIIIа at which oxidation was carried out. UV-, FTIR- and Raman spectroscopy demonstrated that chemical transformation of cyclic, NH, SH and S-S groups mainly determines the oxidation of amino acid residues of pFXIII polypeptide chains. Conversion of pFXIII to FXIIIa proved to increase protein sensitivity to oxidation in the order: pFXIII

Selective DNA purine base photooxidation by bis-terdentate iridium(III) polypyridyl and cyclometalated complexes.

Two bis-terdentate iridium(III) complexes with polypyridyl and cyclometalated ligands have been prepared and characterized. Their spectroscopic and electrochemical properties have been studied, and a photophysical scheme addressing their properties is proposed. Different types of excited states have been considered to account for the deactivation processes in each complex. Interestingly, in the presence of mono- or polynucleotides, a photoinduced electron-transfer process from a DNA purine base (i.e., guanine or adenine) to the excited complex is shown through luminescence quenching experiments. For the first time, this work reports evidence for selective DNA purine bases oxidation by excited iridium(III) bis-terdentate complexes.