Iron Self-Boosting Polymer Nanoenzyme for Low-Temperature Photothermal-Enhanced Ferrotherapy.

In this work, an iron self-boosting polymer nanoenzyme was prepared by using pyrrole-3-carboxylic acid as a monomer and iron as an oxidizing agent via a simple and one-step method [hereafter referred to as FePPy nanoparticles (NPs)]. In fact, researchers previously paid negligible attention on the iron element during the polymerization reaction of polypyrrole, thus the intrinsically catalytic functions and enzymatic activities of the high iron content (wt %: 21.11%) are ignored and not fully explored. As expected, results demonstrate that the as-synthesized FePPy NPs can decompose H2O2 to generate hydroxyl radicals (•OH) which exhibit enzyme characteristics, further inducing a nonapoptotic ferroptosis pathway. Moreover, the nanoenzyme shows impressive photothermal properties which can accelerate the Fenton reactions to enhance ferroptosis. The combined photothermal and ferroptosis therapy of FePPy NPs was found to have high efficacy. With the properties of easy synthesis, high efficacy, and good biocompatibility, the FePPy NPs are considered as potential agents for cancer treatments.

Reconciliation of pH, conductivity, total organic carbon with carboxylic acids detected by ion chromatography in solution after contact with multilayer films after γ-irradiation.

The impact of γ-irradiation on polymers in multilayer films was studied by means of the study of the diffusion and release (spontaneous migration of the molecules from the container into the product) of chemical species in aqueous solution. A series of different measurements have been performed: pH, conductivity, total organic carbon (TOC) and ion chromatography (IC). Their evolution according to γ-irradiation dose was studied. More several rinsings made over several months allowed to quantify well the impact of the irradiation on these polymers. The samples are irradiated at several γ-doses, up to 270 kGy, and compared with a non-irradiated sample used as reference. It shows that quantity of generated carboxylic acids depends on the film material (PE/EVOH/PE and EVA/EVOH/EVA) and increases with γ-dose.

Synthesis and Biological Evaluation of Ru(II) and Pt(II) Complexes Bearing Carboxyl Groups as Potential Anticancer Targeted Drugs.

The synthesis and characterization of Pt(II) (1 and 2) and Ru(II) arene (3 and 4) or polypyridine (5 and 6) complexes is described. With the aim of having a functional group to form bioconjugates, one uncoordinated carboxyl group has been introduced in all complexes. Some of the complexes were selected for their potential in photodynamic therapy (PDT). The molecular structures of complexes 2 and 5, as well as that of the sodium salt of the 4'-(4-carboxyphenyl)-2,2':6',2″-terpyridine ligand (cptpy), were determined by X-ray diffraction. Different techniques were used to evaluate the binding capacity to model DNA molecules, and MTT cytotoxicity assays were performed against four cell lines. Compounds 3, 4, and 5 showed little tendency to bind to DNA and exhibited poor biological activity. Compound 2 behaves as bonded to DNA probably through a covalent interaction, although its cytotoxicity was very low. Compound 1 and possibly 6, both of which contain a cptpy ligand, were able to intercalate with DNA, but toxicity was not observed for 6. However, compound 1 was active in all cell lines tested. Clonogenic assays and apoptosis induction studies were also performed on the PC-3 line for 1. The photodynamic behavior for complexes 1, 5, and 6 indicated that their nuclease activity was enhanced after irradiation at λ = 447 nm. The cell viability was significantly reduced only in the case of 5. The different behavior in the absence or presence of light makes complex 5 a potential prodrug of interest in PDT. Molecular docking studies followed by molecular dynamics simulations for 1 and the counterpart without the carboxyl group confirmed the experimental data that pointed to an intercalation mechanism. The cytotoxicity of 1 and the potential of 5 in PDT make them good candidates for subsequent conjugation, through the carboxyl group, to "selected peptides" which could facilitate the selective vectorization of the complex toward receptors that are overexpressed in neoplastic cell lines.

Directed γ-C(sp3)-H Alkylation of Carboxylic Acid Derivatives through Visible Light Photoredox Catalysis.

Visible light photoredox catalysis enables direct γ- C(sp3)-H alkylation of saturated aliphatic carbonyl compounds. Electron-deficient alkenes are used as the coupling partners in this reaction. Distinguished site selectivity is controlled by the predominant 1,5-hydrogen atom transfer of an amidyl radical generated in situ.

Synthesis of carbonylated heteroaromatic compounds via visible-light-driven intramolecular decarboxylative cyclization of o-alkynylated carboxylic acids.

An efficient strategy for the easy access to carbonylated heteroaromatic compounds has been developed via a visible-light-promoted intramolecular decarboxylative cyclization reaction of o-alkynylated carboxylic acids. This method is characterized by its benign conditions and the tolerance to a wide range of functionalities.

Application of UV-irradiated Fe(III)-nitrilotriacetic acid (UV-Fe(III)NTA) and UV-NTA-Fenton systems to degrade model and natural occurring naphthenic acids.

Naphthenic acids (NAs) are a highly complex mixture of organic compounds naturally present in bitumen and identified as the primary toxic constituent of oil sands process-affected water (OSPW). This work investigated the degradation of cyclohexanoic acid (CHA), a model NA compound, and natural occurring NAs during the UV photolysis of Fe(III)-nitrilotriacetic acid (UV-Fe(III)NTA) and UV-NTA-Fenton processes. The results indicated that in the UV-Fe(III)NTA process at pH 8, the CHA removal increased with increasing NTA dose (0.18, 0.36 and 0.72 mM), while it was independent of the Fe(III) dose (0.09, 0.18 and 0.36 mM). Moreover, the three Fe concentrations had no influence on the photolysis of the Fe(III)NTA complex. The main responsible species for the CHA degradation was hydroxyl radical (OH), and the role of dissolved O2 in the OH generation was found to be negligible. Real OSPW was treated with the UV-Fe(III)NTA and UV-NTA-Fenton advanced oxidation processes (AOPs). The removals of classical NAs (O2-NAs), oxidized NAs with one additional oxygen atom (O3-NAs) and with two additional oxygen atoms (O4-NAs) were 44.5%, 21.3%, and 25.2% in the UV-Fe(III)NTA process, respectively, and 98.4%, 86.0%, and 81.0% in the UV-NTA-Fenton process, respectively. There was no influence of O2 on the NA removal in these two processes. The results also confirmed the high reactivity of the O2-NA species with more carbons and increasing number of rings or double bond equivalents. This work opens a new window for the possible treatment of OSPW at natural pH using these AOPs.

Comparison of classical fenton, nitrilotriacetic acid (NTA)-Fenton, UV-Fenton, UV photolysis of Fe-NTA, UV-NTA-Fenton, and UV-H2O2 for the degradation of cyclohexanoic acid.

The treatment of a naphthenic acid model compound, cyclohexanoic acid, with classical Fenton, UV-H2O2, UV-Fenton, nitrilotriacetic acid (NTA)-Fenton, UV-NTA-Fenton, and UV photolysis of Fe-NTA processes at pHs 3 and 8 was investigated. At 1.47 mM H2O2, 0.089 mM Fe, and 0.18 mM NTA, the UV-NTA-Fenton process at pH 3 exhibited the highest H2O2 decomposition (100% in 25 min), CHA removal (100% in 12 min) with a rate constant of 0.27 ± 0.025 min-1, and NTA degradation (100% in 6 min). Due to the formation of H2O2-Fe(III)NTA adduct, the total Fe concentration in the UV-NTA-Fenton system (0.063 mM at the end of the reaction) at pH 8 was much higher than that in the UV photolysis of Fe(III)NTA process (0.024 mM). The co-complexing effect of borate buffer helped to keep iron soluble; however, it imposed a negative influence on the CHA degradation in the UV-NTA-Fenton process (68% CHA removal in 60 min in the borate buffer compared to 92% in MilliQ water). The results demonstrated that the most efficient process for the CHA degradation under the experimental conditions was the UV-NTA-Fenton process at pH 3.

Fluorescent Pyrene Assisted Photodeprotection of 2-(2-nitrophenyl)Propyloxycarbonyl Groups on Self-Assembled Monolayers.

Accelerating the photodeprotection rate of photolabile protecting group is conducive to a light-directed chemical reaction, especially for the in situ synthesis of a biochip. Herein, a photosensitizer pyrene was applied to the photodeprotection of 2-(2-nitrophenyl)propyloxycarbony (NPPOC) groups on self-assembled monolayers (SAMs). It was found that the addition of pyrene could largely improve photodeprotection rate, and effectively prevent molecule damage that are often encountered by the photosensitizer 2-isopropyl thioxanthone (ITX). The most likely explanation for this result is that the whole photodeprotection process involves three joint actions, including ultraviolet light irradiation, triplet energy transfer by pyrene, and singlet fluorescence irradiation from pyrene. The joint actions enable the transfer of over-absorbed energy from pyrene to protecting groups in terms of fluorescence rather than free radicals produced by ITX that are detrimental to the molecules modified on glass substrates. Pyrene dissolved in an optimized combination of mixed solvent of dimethylacetamide (DMAC), ethanol, and dioxane with a volume ratio of 1:1:1 was tested to produce a complete photodeprotection of NPPOC groups within 6 min under 365 nm ultraviolet with an intensity of 10.8 mW/cm2. Meanwhile, tens to hundreds of cycles of photodeprotection could be conducted at a high efficiency. This research will shed light on the deprotection of photolabile groups with weak ultraviolet using a fluorescent sensitizer.

Meteorite-catalyzed syntheses of nucleosides and of other prebiotic compounds from formamide under proton irradiation.

Liquid formamide has been irradiated by high-energy proton beams in the presence of powdered meteorites, and the products of the catalyzed resulting syntheses were analyzed by mass spectrometry. Relative to the controls (no radiation, or no formamide, or no catalyst), an extremely rich, variegate, and prebiotically relevant panel of compounds was observed. The meteorites tested were representative of the four major classes: iron, stony iron, chondrites, and achondrites. The products obtained were amino acids, carboxylic acids, nucleobases, sugars, and, most notably, four nucleosides: cytidine, uridine, adenosine, and thymidine. In accordance with theoretical studies, the detection of HCN oligomers suggests the occurrence of mechanisms based on the generation of radical cyanide species (CN·) for the synthesis of nucleobases. Given that many of the compounds obtained are key components of extant organisms, these observations contribute to outline plausible exogenous high-energy-based prebiotic scenarios and their possible boundary conditions, as discussed.

[Effects of UV radiation on the aggregation performance of small molecular organic acids].

This study systematically investigated the effects of UV radiation on the aggregation of small molecular aliphatic carboxylic acids and phenolic acids by jar test. Experimental results show that solution pH has little effect on the coagulation of small molecular aliphatic carboxylic acids including citric acid, oxalic acid, tartaric acid, and succinic acid. For the solutions pretreated with UV light, the removal rates of the selected aliphatic carboxylic acids in coagulation are higher than that without UV radiation. Further study shows that photochemical reactions occur during UV radiation which decreases the negative charge in aliphatic carboxylic acids, and thereby increases their aggregation properties. Different from aliphatic carboxylic acids, phenol, salicylic acid, and benzoic acid have poor coagulation properties, and UV radiation does not have notable effects on their aggregation in the coagulation process. The coagulation performance of tannic acid is better than the other phenolic acids. At pH = 6, its removal rate is above 90%, which may be contributed to the aliphatic carboxylic acid structure in its molecular. Meanwhile, the large molecular of tannic acid is also easier to be adsorbed by the hydrolysis products of PAC1.

Derivative mechanisms of organic acids in microwave oxidation of landfill leachate.

This study compared formation and degradation behaviors of organic acids in landfill leachate under microwave oxidation process (MOP) and under conventional heating oxidation (CHO) and explored derivative mechanisms of organic acids in MOP. The results showed that formation and degradation behaviors of oxalic acid were very similar under CHO and MOP, in which its concentrations decreased in the temperature-raising period, then increased due to decomposition of TOC from 10 to 70 min, decreased due to persulfate oxidation from 70 to 130 min, and stayed the same afterwards. The pH values of the leachate solution dropped 0.51 and 0.65 pH units after MOP and CHO treatment, respectively. Oxalic acid was the dominant organic acid formed in MOP. The derivative mechanisms of organic acids were developed using the experimental results. Lactic acid was generated from decomposition of malic acid, and oxalic acid was formed from oxidation of its precursors. Acetic acid was formed and soon decomposed. Lactic acid had its maximum concentration with a persulfate dose of 0.5M, while lower or higher persulfate doses yielded few or no lactic acid in MOP.

Microwave-assisted melt reaction method for the intercalation of carboxylic acid anions into layered double hydroxides.

Carboxylic acid anions intercalated layered double hydroxides are currently gaining increasing interest due to their potential applications in pharmaceutical field for controlled drug release in novel tunable drug delivery systems. In this work different aliphatic carboxylic acid anions were intercalated into the interlayers of commercial as well as synthetically prepared layered double hydroxides, through a novel microwave mediated melt reaction approach. The volumetric nature of microwave dielectric heating was exploited in order to rapidly heat the intimate mixture of the lamellar inorganic precursor and the appropriate organic acid, at the melting temperature of the particular mono- or dicarboxylic acid used, reaching the intercalation in approximately two hours treatment.

Synthesis, structure and properties of superhard nanostructured films deposited by the C60 ion beam.

In this work, we present results on study of DLC, nanocomposite and nanocrystal nanographite films synthesized utilizing mass-separated beam of C60-ions with energy in range from 2 to 6 keV (energy dispersions approximately 1 keV) and at Ts in the range of RT - 873 K. The dependence of the structure, mechanical and electrical properties from the ion energy and substrate temperature was revealed. We demonstrate a possibility to control the orientation of the base planes in the nanographite grains during the film growth. The dependence of mechanical properties of the films from the orientation of the base planes was defined. It is discussed a mechanisms of oriented growth for nanocrystal graphite. Possible applications of the textured nanocomposite and nanographite films are nanodevices, thin-filmed lithium batteries and field-emitter arrays.

Photodegradable iron(III) cross-linked alginate gels.

Biocompatible photoresponsive materials are of interest for targeted drug delivery, tissue engineering, 2D and 3D protein patterning, and other biomedical applications. We prepared light degradable hydrogels using a natural alginate polysaccharide cross-linked with iron(III) cations. The "hard" iron(III) cations used to cross-link the alginate hydrogel were found to undergo facile photoreduction to "soft" iron(II) cations in the presence of millimolar concentrations of sodium lactate. The "soft" iron(II) cations have a decreased ability to cross-link the alginate which results in dissolution of the hydrogel and the formation of a homogeneous solution. The photodegradation is done using long wave UV or visible light at neutral pH. The very mild conditions required for the photodegradation and the high rate at which it occurs suggest applications for iron(III) cross-linked alginate hydrogels as light-controlled biocompatible scaffolds.

High regioselective ultrasonic-assisted synthesis of 2,7-diaryl-4,7-dihydropyrazolo[1,5-a]pyrimidine-5-carboxylic acids.

New and high regioselective method of the synthesis of 2,7-diaryl-4,7-dihydropyrazolo[1,5-a]pyrimidine-5-carboxylic acids by reaction of 3-aryl-5-aminopyrazoles with arylidenpyruvic acid at room temperature under ultrasonication was developed and discussed.

Comparison of four advanced oxidation processes for the removal of naphthenic acids from model oil sands process water.

Four advanced oxidation processes (UV/TiO(2), UV/IO(4)(-), UV/S(2)O(8)(2-), and UV/H(2)O(2)) were tested for their ability to mineralize naphthenic acids to inorganic carbon in a model oil sands process water containing high dissolved and suspended solids at pH values ranging from 8 to 12. A medium pressure mercury (Hg) lamp was used, and a Quartz immersion well surrounded the lamp. The treatment goal of 5mg/L naphthenic acids (3.4 mg/L total organic carbon (TOC)) was achieved under four conditions: UV/S(2)O(8)(2-) (20mM) at pH 8 and 10, and UV/H(2)O(2) (50mM) at pH 8 (all with the Quartz immersion well). Values of electrical energy required to meet the treatment goal were about equal for UV/S(2)O(8)(2-) (20mM) and UV/H(2)O(2) (50mM) at pH 8, but three to four times larger for treatment by UV/S(2)O(8)(2-) (20mM) at pH 10. The treatment goal was also achieved using UV/S(2)O(8)(2-) (20mM) at pH 10 when using a Vycor filter that transmits light primarily in the mid and near UV, suggesting that that treatment of naphthenic acids by UV/S(2)O(8)(2-) using low pressure Hg lamps may be feasible.

The kinetics of photocatalytic degradation of aliphatic carboxylic acids in an UV/TiO2 suspension system.

Kinetic studies on the photocatalytic degradation of aliphatic carboxylic acids were carried out in a slurry photoreactor with in-situ monitoring, employing artificial UV light as the source of energy and nano-TiO2 powder as the catalyst. The influences on the photocatalytic degradation such as the initial concentration of reactant (C0), catalyst dosage (CTiO2), UV intensity (Ia) and pH value have been investigated. Good agreement has been obtained between the value calculated by Langmuir-Freundlich-Hinshelwood (L-F-H) model and experimental data, with coefficient of multiple determination (R2) varying from 0.880 to 0.999. The L-F-H model has been proven to be feasible in describing the kinetic characteristic of the photocatalytic degradation of aliphatic carboxylic acids. Moreover, the apparent reaction rate constant (k) of the photocatalytic degradation of dicarboxylic acids is higher than that of monocarboxylic acids with the same carbon atoms. This shows that the photocatalytic degradation rate is favoured by different chemical structure.

Silver-catalysed protodecarboxylation of carboxylic acids.

A silver-based catalyst system has been discovered that effectively promotes the protodecarboxylation of various carboxylic acids at temperatures of 80-120 degrees C--more than 50 degrees C below those of the best known copper catalysts.

Biological safety of liposome-fullerene consisting of hydrogenated lecithin, glycine soja sterols, and fullerene-C60 upon photocytotoxicity and bacterial reverse mutagenicity.

Various water-soluble derivatives of fullerene-C60 (C60) have been developed as detoxifiers for reactive oxygen species (ROS), whereas C60 incorporated in liposome (Lpsm) has not been reported yet. We prepared the liposome-fullerene (0.2% aqueous phase, Lpsm-Flln) which was composed of hydrogenated lecithin, glycine soja (soybean) sterols, and C60 in the weight ratio of 89.7:10:0.3, then examined the photocytotoxicity and bacterial reverse mutagenicity, as comparing with the Lpsm containing no C60. Photocytoxicity of Lpsm-Flln or Lpsm was examined using Balb/3T3 fibroblastic cells at graded doses of 0.49-1000 microg/mL under the condition of UVA- or sham-irradiation. The cells were irradiated with UVA (5 J/cm2, 320-400 nm, lambda max = 360 nm) at room temperature for 50 min. The resultant cell viability (% of control) did not decrease dose-dependently to 50% or less regardless of the UVA-irradiation. These results show that Lpsm-Flln or Lpsm does not possess photocytotoxicity to Balb/3T3 fibroblasts, and Lpsm-Flln may not exert a UVA-catalytic ROS-increasing action. A possibility for the reverse mutation by Lpsm-Flln or Lpsm was examined on four histidine-demanding strains of Salmonella typhimurium and a tryptophan-demanding strain of Escherichia coli. As for the dosages of Lpsm-Flln or Lpsm (313-5000 microg/plate), the dose-dependency of the number of reverse mutation colonies of each strain did not show a twice or more difference versus the negative control regardless of the metabolic activation, and, in contrast, marked differences for five positive controls (sodium azide, N-ethyl-N'-nitro-N-nitrosoguanidine, 2-nitrofluorene, 9-aminoacridine, and 2-aminoanthracene). The growth inhibition of bacterial strains and the deposition of Lpsm-Flln or Lpsm were not found. As a result, the bacterial reverse mutagenicity of Lpsm-Flln or Lpsm was judged to be negative under the conditions of this test. Thus, Lpsm-Flln and Lpsm may not give any significant biological toxic effects, such as photocytotoxicity and bacterial reverse mutagenicity.

Synthesis and characterization of thiochromone S,S-dioxides as new photolabile protecting groups.

3-Arylthiochromone derivatives were synthesized as new photolabile protecting groups, in which the photoreactivity was switchable based on oxidation of the sulfur atom (sulfide and sulfone); the protected substrates , released the corresponding alcohols, amines or carbonxylic acids almost quantitatively under UV-light in neutral condition and the photoproduct showed high fluorescence intensity.