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A study published in the British Journal of Dermatology suggests that there may be a link between psoriasis and cardiovascular risk through elevated plasma triglycerides. The study found that individuals with high plasma triglyceride levels had a higher probability of developing psoriasis compared to those with lower levels. The researchers also identified genetic variants associated with triglyceride metabolism that could potentially be targeted for treatment. Further research is needed to explore the impact of lowering triglyceride levels on psoriasis severity and the development of related conditions. [Extracted from the article]

Background: Psoriasis (PSO) is a skin disorder with systemic inflammation and high coronary artery disease risk. A distinct lipid phenotype occurs in psoriasis, which is characterized by high plasma triglycerides (TGs) with typically normal or even low LDL-C. The extent to which cholesterol on LDL subfractions, such as small dense LDL-C (sdLDL-C), are associated with vulnerable coronary plaque characteristics in PSO remains elusive. Methods: A recently developed equation for estimating sdLDL-C from the standard lipid panel was utilized in a PSO cohort (n = 200) with 4-year follow-up of 75 subjects. Coronary plaque burden was assessed by quantitative coronary computed tomography angiography (CCTA). Multivariate regression analyses were used for establishing associations and prognostic value of estimated sdLDL-C. Results: Estimated sdLDL-C was positively associated with non-calcified burden (NCB) and fibro-fatty burden (FFB), which remained significant after multivariate adjustment for NCB (β = 0.37; P = 0.050) and LDL-C adjustment for FFB (β = 0.29; P < 0.0001). Of note, total LDL-C calculated by the Friedewald equation was not able to capture these associations in the study cohort. Moreover, in the regression modelling estimated sdLDL-C was significantly predicting necrotic burden progression over 4 years follow-up (P = 0.015), whereas LDL-C did not. Finally, small LDL particles (S-LDLP) and small HDL particles (S-HDLP), along with large and medium TG-rich lipoproteins (TRLPs) had the most significant positive correlation with estimated sdLDL-C. Conclusions: Estimated sdLDL-C has a stronger association than LDL-C with high-risk features of coronary atherosclerotic plaques in psoriasis patients. Clinical trial registration: URL: https://www.clinicaltrials.gov. Unique identifiers: NCT01778569 [ABSTRACT FROM AUTHOR]

[Display omitted] • Stable surface layers of water-soluble dimethyl sulfoxide (DMSO) on water. • Poorly soluble multilayer films of DMSO on substrates. • Gibbs layers of DMSO compressed and transferred. • A new robust method and device for forming DMSO spread layers. Dimethyl sulfoxide (DMSO) is sometimes used as a solvent in the preparation of Langmuir-Blodgett (LB) films. By analogy with standard volatile solvents, it is often assumed that DMSO has no further effect once the solute molecules are distributed over the subphase surface. We hypothesized that this is not always the case and that DMSO may play an important role by remaining on the surface after spreading, contributing to the isotherms, influencing the formation of the LB film, and being incorporated into the resulting film. We studied the spreading of pure DMSO and the properties of Langmuir (spread) and Gibbs (adsorbed) layers of DMSO on water, proposed a robust approach to form the spread layers, and used the LB method to fabricate multilayer films on solid substrates. DMSO, which is completely miscible with water, can itself form a spreading surface layer very similar to the Langmuir layers of insoluble amphiphiles. When transferred repeatedly to a substrate, this layer forms a remarkably stable, poorly soluble multilayer film. [ABSTRACT FROM AUTHOR]

[Display omitted] • Metal phthalocyanine complexes are the catalysts for oxidation and other reactions. • μ-Nitrido diiron complexes feature a particular structure and catalytic properties. • Mild oxidation of methane. • Oxidative defluorination of heavily fluorinated aromatic compounds. • Flexibility of binuclear macrocyclic platform. For a long time biomimetic oxidation catalysis was mainly associated with metal porphyrin complexes. Phthalocyanine complexes, also belonging to large family of macrocyclic complexes have been under-investigated as catalysts until recently. In this review, we present the development of phthalocyanine catalytic chemistry at IRCELYON with a topical focus on contributions from our group during last 20 years and discuss recent research directions from personal perspective. Catalytic chemistry of phthalocyanine complexes is a rapidly growing field including not only oxidations but also many other reactions. Recent discovery of remarkable catalytic properties of μ-nitrido diiron phthalocyanines will give a new impetus and should even accelerate this development. These binuclear N-bridged complexes emerge as promising bio-inspired catalysts, in particular, for challenging reactions such as a low temperature oxidation of methane and oxidative defluorination of heavily fluorinated aromatic compounds. The scope of their catalytic applications is constantly increasing. The bimetallic construction is flexible and has a significant potential for further development including implementation of different ligands, metals and bridging groups. Consequently, the properties of this scaffold can be fine-tuned by platform architecture thus providing novel tools for catalysis. [ABSTRACT FROM AUTHOR]

Anti-inflammatory therapy with tumour necrosis factor alpha inhibitors improves high-density lipoprotein cholesterol antioxidative capacity in rheumatoid arthritis patients. This editorial refers to 'TNF induces endothelial dysfunction in rheumatoid arthritis via LOX-1 and arginase 2: reversal by monoclonal TNF antibodies' by A. Akhmedov I et al. i , pp. 254-266. [Extracted from the article]

This is a comment on the paper "Hovsgol earthquake 5 December 2014, MW = 4.9 seismic and acoustic effects" by Dobrynina, A.A., Sankov, V.A., Tcydypova, L.R., German, V.I., Chechelnitsky, V.V., and Munkhuu U. (JOSE, 2018, 22, 377–389). The model of infrasonic wave generation from the Mw = 4.9 Hovsgol earthquake of 5 December 2014 suggested by Dobrynina et al. was based on an incorrect traveltime which led to an error in the location of the infrasound source and to misinterpretation of its type. [ABSTRACT FROM AUTHOR]

The current coronavirus disease 2019 (COVID‐19) pandemic presents a global challenge for managing acutely ill patients and complications from viral infection. Systemic inflammation accompanied by a "cytokine storm," hemostasis alterations and severe vasculitis have all been reported to occur with COVID‐19, and emerging evidence suggests that dysregulation of lipid transport may contribute to some of these complications. Here, we aim to summarize the current understanding of the potential mechanisms related to COVID‐19 dyslipidemia and propose possible adjunctive type therapeutic approaches that modulate lipids and lipoproteins. Specifically, we hypothesize that changes in the quantity and composition of high‐density lipoprotein (HDL) that occurs with COVID‐19 can significantly decrease the anti‐inflammatory and anti‐oxidative functions of HDL and could contribute to pulmonary inflammation. Furthermore, we propose that lipoproteins with oxidized phospholipids and fatty acids could lead to virus‐associated organ damage via overactivation of innate immune scavenger receptors. Restoring lipoprotein function with ApoA‐I raising agents or blocking relevant scavenger receptors with neutralizing antibodies could, therefore, be of value in the treatment of COVID‐19. Finally, we discuss the role of omega‐3 fatty acids transported by lipoproteins in generating specialized proresolving mediators and how together with anti‐inflammatory drugs, they could decrease inflammation and thrombotic complications associated with COVID‐19. [ABSTRACT FROM AUTHOR]

Methane hydroxylation by metal-oxo oxidants is one of the Holy Grails in biomimetic and biotechnological chemistry. The only enzymes known to perform this reaction in Nature are iron-containing soluble methane monooxygenase and copper-containing particulate methane monooxygenase. Furthermore, few biomimetic iron-containing oxidants have been designed that can hydroxylate methane efficiently. Recent studies reported that μ-nitrido-bridged diiron(IV)-oxo porphyrin and phthalocyanine complexes hydroxylate methane to methanol efficiently. To find out whether the reaction rates are enhanced by replacing iron by ruthenium, we performed a detailed computational study. Our work shows that the μ-nitrido-bridged diruthenium(IV)-oxo reacts with methane via hydrogen atom abstraction barriers that are considerably lower in energy (by about 5 kcal mol‒1) as compared to the analogous diiron(IV)-oxo complex. An analysis of the electronic structure implicates similar spin and charge distributions for the diiron(IV)-oxo and diruthenium(IV)-oxo complexes, but the strength of the O‒H bond formed during the reaction is much stronger for the latter. As such a larger hydrogen atom abstraction driving force for the Ru complex than for the Fe complex is found, which should result in higher reactivity in the oxidation of methane. [ABSTRACT FROM AUTHOR]

Graphical abstract Highlights • Structural and electronic properties of homoleptic and heteroleptic binuclear complexes are considered. • Homometallic M O M and heterometallic M O M′ complexes involving Fe, Mn, Ru, Cr, Mo, Re, Al, Si, P, B. • Covalently linked and non-covalently assembled µ-oxo dimeric structures. • Catalytic and photocatalytic applications. • Application of µ-oxo binuclear complexes in optoelectronic and medical applications. Abstract This review covers recent advances in the preparation, characterization and application of µ-oxo dimeric complexes with different metals and non-metal and macrocyclic ligands achieved during last ten years. Binuclear iron, manganese, ruthenium, chromium, molybdenum, rhenium, aluminium, silicon, phosphorus and boron oxygen-bridged complexes supported by phthalocyanine, porphyrin, porphyrazine, corrole, tetrabenzotriazacorrole, subphthalocyanine and subporphyrin ligands have been prepared and characterized demonstrating a great versatility of µ-oxo binuclear macrocyclic platform which can accommodate a myriad of homoleptic and heteroleptic combinations with the same or different metal sites. They exhibit interesting structural and electronic properties allowing their increasing use in catalysis, optoelectronic, medical and other applications. [ABSTRACT FROM AUTHOR]

Persistent skin inflammation and impaired resolution are the main contributors to psoriasis and associated cardiometabolic complications. Omega-3 polyunsaturated fatty acids (PUFAs), eicosapentaenoic acid (EPA), and docosahexaenoic acid (DHA), are known to exert beneficial effects on inflammatory response and lipid function. However, a specific role of omega-3 PUFAs in psoriasis and accompanied pathologies are still a matter of debate. Here, we carried out a direct comparison between EPA and DHA 12 weeks diet intervention treatment of psoriasis-like skin inflammation in the K14-Rac1V12 mouse model. By utilizing sensitive techniques, we targeted EPA- and DHA-derived specialized pro-resolving lipid mediators and identified tightly connected signaling pathways by RNA sequencing. Treatment with experimental diets significantly decreased circulating pro-inflammatory cytokines and bioactive lipid mediators, altered psoriasis macrophage phenotypes and genes of lipid oxidation. The superficial role of these changes was related to DHA treatment and included increased levels of resolvin D5, protectin DX and maresin 2 in the skin. EPA treated mice had less pronounced effects but demonstrated a decreased skin accumulation of prostaglandin E 2 and thromboxane B 2. These results indicate that modulating psoriasis skin inflammation with the omega-3 PUFAs may have clinical significance and DHA treatment might be considered over EPA in this specific disease. [Display omitted] [ABSTRACT FROM AUTHOR]

μ-Nitrido diiron tetrabutylphthalocyanine, (FePctBu4)2N, in combination with H2O2 can perform an efficient defluorination of heavily fluorinated aromatics via an oxidative pathway. To check whether hydroxyl radicals might be involved in this reaction we have compared catalytic activities of (FePctBu4)2N - H2O2 and FeSO4 - H2O2 systems in the transformation of five differently fluorinated benzenes, perfluoronaphthalene, pentafluoropyridine, and eight functionalized perfluorinated benzenes. In sharp contrast with (FePctBu4)2N - H2O2 system, all fluorinated benzene derivatives were completely stable in the presence of FeSO4 and H2O2 at 60 °C during 15 h. Perfluorinated aromatic compounds functionalized with electron-donating or electron-withdrawing groups as well as pentafluoropyridine exhibited very low conversions. These results unambiguously show that Fenton chemistry is not responsible for the oxidative defluorination of highly fluorinated aromatic compounds performed by the (FePctBu4)2N - H2O2 system. [ABSTRACT FROM AUTHOR]

Optical properties and morphologies of molecular aggregates of two similar cyanine dyes (BIC and TDBC) have been studied. The dyes have the same 5,5′,6,6′-tetrachlorobenzimidacarbocyanine chromophore part and differ just in one methyl group in alkyl chains. Due to such a similarity of the dye molecular structures, their aggregates are often supposed to have similar structure. However the difference in optical properties was reported in some publications assuming different structures of the J-aggregates. Indeed, we have found distinct morphologies for BIC and TDBC J-aggregates: spherical species for BIC J-aggregates and rod-like ones for TDBC J-aggregates. The difference in morphologies and, hence, structures is the reason of unlike optical properties of these J-aggregates. [ABSTRACT FROM AUTHOR]

Low temperature selective transformation of alkanes to useful products continues to be an important challenge in chemistry and industry. μ-Nitrido diiron phthalocyanines in combination with H 2 O 2 have been recently identified as powerful oxidation catalysts for these challenging reactions due to the formation of ultra-high valent diiron oxo species PcFe(IV)μNFe(IV) O(Pc + ). This very strong two-electron oxidizing species is generated from peroxo complex PcFe(IV)μNFe(III) O O R(Pc) (R H in the case of H 2 O 2 ) via heterolytic O O bond cleavage. Therein we show that the evolution of the peroxo diiron complex depends on the peroxide structure. Using t BuOOH we have demonstrated the formation of an one-electron oxidizing PcFe(IV)μNFe(IV) O(Pc) and t BuO radical via homolytic O O cleavage of the peroxocomplex. The reactivity of the μ-nitrido diiron tetra- t -butylphthalocyanine − t BuOOH catalytic system was investigated in the oxidation of different C H bonds in alkanes, olefins, aromatic and alkylaromatic compounds. The main products of cyclohexane oxidation were cyclohexanone and cyclohexanol whereas bicyclohexyl was formed in minor amounts even in the presence of O 2 and t BuOOH. Under optimal conditions, the turnover numbers of almost 5300 have been achieved. [ABSTRACT FROM AUTHOR]

• Irradiated austenitic steel shows intergranular fracture at (400–600)°C and channel fracture at (400–550)°C. • Portion of intergranular fracture zones increases, and channel fracture zones decreases with temperature growth. • Fracture strain is larger for notched round bars than for smooth ones at temperature above 400 °C. • Intergranular high temperature fracture criterion is developed. • Intergranular fracture modeling for smooth and notched round bars and cracked specimens is performed. The fracture mechanisms of austenitic 18Cr-9Ni steel have been investigated over the temperature range from 200° to 600 °C using the following states: (1) after neutron irradiation at temperature of 400 °C up to damage dose of 30 dpa; (2) after neutron irradiation and subsequent aging at 550 °C for 3000 h. The fracture properties and mechanisms have been determined under uniaxial tension of smooth round and notched round bars, i.e. for various stress triaxialities. Sharp decrease in the fracture strain and transition to intergranular fracture have been revealed for smooth round bars over high temperature range that indicates high temperature radiation embrittlement. Over the same temperature range the fracture strain is larger for notched round bars than for smooth round bars, moreover a portion of intergranular fracture is also larger. This finding is rather abnormal as the fracture strain usually decreases when stress triaxiality and intergranular fracture portion increase. On the basis of the obtained experimental results, for the first time, the fracture stress-controlled criterion and fracture model have been developed over temperature range of high temperature radiation embrittlement. The proposed model allows one to explain larger value of the fracture strain for notched round bars as compared with smooth round bars and also to predict fracture toughness over range of high temperature radiation embrittlement. The formulated criterion and model have been verified by comparison of the calculated and experimental values of fracture toughness for 18Cr-9Ni steel irradiated up to damage dose of (24–30) dpa. Experimental values of fracture toughness have been obtained from compact tension CT-0.5 specimens tested at 200 °C and 600 °C. [ABSTRACT FROM AUTHOR]

Aspirin (ASA) is known to alter the production of potent inflammatory lipid mediators, but whether it interacts with omega-3 fatty acids (FAs) from fish oil to affect atherosclerosis has not been determined. The goal was to investigate the impact of a fish oil-enriched diet alone and in combination with ASA on the production of lipid mediators and atherosclerosis. ApoE(-/-) female mice were fed for 13weeks one of the four following diets: omega-3 FA deficient (OD), omega-3 FA rich (OR) (1.8g omega-3 FAs/kg·diet per day), omega-3 FA rich plus ASA (ORA) (0.1g ASA/kg·diet per day) or an omega-3 FA deficient plus ASA (ODA) with supplement levels equivalent to human doses. Plasma lipids, atherosclerosis, markers of inflammation, hepatic gene expression and aortic lipid mediators were determined. Hepatic omega-3 FAs were markedly higher in OR (9.9-fold) and ORA (7-fold) groups. Mice in both OR and ORA groups had 40% less plasma cholesterol in very low-density lipoprotein-cholesterol and low-density lipoprotein fractions, but aortic plaque area formation was only significantly lower in the ORA group (5.5%) compared to the OD group (2.5%). Plasma PCSK9 protein levels were approximately 70% lower in the OR and ORA groups. Proinflammatory aortic lipid mediators were 50%-70% lower in the ODA group than in the OD group and more than 50% lower in the ORA group. In summary, less aortic plaque lesions and aortic proinflammatory lipid mediators were observed in mice on the fish oil diet plus ASA vs. just the fish oil diet. [ABSTRACT FROM AUTHOR]

The ultimate objective of bioinspired catalysis is the development of efficient and clean chemical processes. Cytochrome P450 and soluble methane monooxygenase enzymes efficiently catalyze many challenging reactions. Extensive research has been performed to mimic their exciting chemistry, aiming to create efficient chemical catalysts for functionalization of strong C--H bonds. Two current biomimetic approaches are based on (i) mononuclear metal porphyrin-like complexes and (ii) iron and diiron non-heme complexes. However, biomimetic catalysts capable of oxidizing CH4 are still to be created. In the search for powerful oxidizing catalysts, we have recently proposed a new bioinspired strategy using N-bridged diiron phthalocyanine and porphyrin complexes. This platform is particularly suitable for stabilization of Fe(IV)Fe(IV) complexes and can be useful to generate high-valent oxidizing active species. Indeed, the possibility of charge delocalization on two iron centers, two macrocyclic ligands, and the nitrogen bridge makes possible the activation of H2O2 and peracids. The ultrahigh-valent diiron--oxo species (L)FeIV--N--FeIV(L+•)=O (L = porphyrin or phthalocyanine) have been prepared at low temperatures and characterized by cryospray MS, UV--vis, EPR, and Mössbauer techniques. The highly electrophilic (L)FeIV--N--FeIV(L+•)=O species exhibit remarkable reactivity. In this Account, we describe the catalytic applications of μ-nitrido diiron complexes in the oxidation of methane and benzene, in the transformation of aromatic C--F bonds under oxidative conditions, in oxidative dechlorination, and in the formation of C--C bonds. Importantly, all of these reactions can be performed under mild and clean conditions with high conversions and turnover numbers. μ-Nitrido diiron species retain their binuclear structure during catalysis and show the same mechanistic features (e.g., 18O labeling, formation of benzene epoxide, and NIH shift in aromatic oxidation) as the enzymes operating via high-valent iron--oxo species. μ-Nitrido diiron complexes can react with perfluorinated aromatics under oxidative conditions, while the strongest oxidizing enzymes cannot. Advanced spectroscopic, labeling, and reactivity studies have confirmed the involvement of high-valent diiron--oxo species in these catalytic reactions. Computational studies have shed light on the origin of the remarkable catalytic properties, distinguishing the Fe--N--Fe scaffold from Fe--C--Fe and Fe--O--Fe analogues. X-ray absorption and emission spectroscopies assisted with DFT calculations allow deeper insight into the electronic structure of these particular complexes. Besides the novel chemistry involved, iron phthalocyanines are cheap and readily available in bulk quantities, suggesting high application potential. A variety of macrocyclic ligands can be used in combination with different transition metals to accommodate M--N--M platform and to tune their electronic and catalytic properties. The structural simplicity and flexibility of μ-nitrido dimers make them promising catalysts for many challenging reactions. [ABSTRACT FROM AUTHOR]

Low temperature selective transformation of light alkanes of natural gas to useful products continues to be an important challenge in chemistry and industry. μ-Nitrido diiron phthalocyanines were recently identified as powerful oxidation catalysts capable of oxidizing methane, benzene and transforming poly- and perfluorinated aromatic compounds under oxidative conditions. Herein, we have supported two μ-nitrido diiron complexes onto silica, graphite or nafion and their catalytic performance has been evaluated in the heterogeneous oxidation of ethane in water. Acetic acid was obtained with selectivity up to 71%. Turnover number up to 58 and 50–65 % product yields can be achieved. The cleavage of C–C bond also occurred and formic acid was formed as side product. In contrast to methane oxidation, no strong influence of 75 mM acid was observed in ethane oxidation. The reactivities of C–H bonds in methane, ethane and propane were very similar when the reaction was performed in water. In contrast, in diluted acidic solution, the μ-nitrido diiron phthalocyanine – H 2 O 2 system exhibits 5 times higher activity in the oxidation of the methane C–H bond compared to the ethane C–H bond. [ABSTRACT FROM AUTHOR]

A physical-and-mechanical model of ductile fracture has been developed to predict fracture toughness and fracture strain of irradiated austenitic stainless steels taking into account stress-state triaxiality and radiation swelling. The model is based on criterion of plastic collapse of a material unit cell and takes into account deformation voids nucleation, growth of deformation and vacancy voids, and their coalescence controlled by strain hardening of a material. For justification of the model experimental data on fracture strain and fracture toughness of austenitic stainless steel 18Cr–10Ni–Ti grade irradiated up to 46–49 dpa with various swelling were used. Experimental data on fracture strain and fracture toughness are compared with the results predicted by the model. It has been shown that for prediction of the swelling effect on fracture toughness the dependence of process zone size on swelling should be taken into account. [ABSTRACT FROM AUTHOR]

The supercritical water-cooled reactors (SWCR) belong to Generation IV of reactors. These reactors have a number of advantages over currently operating WWERs and PWRs. These advantages include higher thermal efficiency, a more simplified unit design, and the possibility of incorporating it into a closed fuel cycle. It is therefore necessary to identify candidate materials for the SWCR and validate the safety and effectiveness of their use. 12Cr ferritic-martensitic (F/M) stainless steel is considered a candidate material for SWCR internals. Radiation embrittlement and corrosion cracking in the primary circuit coolant environment are the main mechanisms of F/M steels degradation during SWCR operation. Here, the stress corrosion cracking (SCC) in supercritical water at 390 and 550 °C of 12Cr F/M steel irradiated by neutrons to 12 dpa is investigated. Autoclave tests of specially designed disk specimens in supercritical water were performed. The tests were carried out under different constant load (CL), temperature 450 °C, and pressure in autoclave 25 MPa. The threshold stress, below which the SCC initiation of irradiated 12Cr F/M steel does not occur, was determined. [ABSTRACT FROM AUTHOR]

A drastic decrease in the ultimate tensile strength of irradiated austenitic steels with high swelling values is considered. The physical-mechanical model proposed in Part 1 of the present paper is applied for the prediction of a drastic decrease in ultimate tensile strength. The mechanism called by the authors the "running collapse mechanism" is used for modeling the material ductile fracture when stresses are less than the yield strength. This ductile mechanism is similar to brittle fracture when crack propagates unstable manner. Running collapse mechanism occurs due to evolution of vacancy voids resulting in irradiation swelling. Nanoscale of vacancy voids (void sizes, distance between voids) results in the possibility of ductile fracture in very small zones whose size is considerably smaller than the grain size. [ABSTRACT FROM AUTHOR]

A physical-and-mechanical model of ductile fracture has been developed to predict fracture toughness and fracture strain of irradiated austenitic steels taking into account stress-state triaxiality and radiation swelling. The model is based on criterion of plastic collapse of a material unit cell controlled by strain hardening of a material and criterion of voids coalescence due to channel shearing of voids. The model takes into account deformation voids nucleation and growth of deformation and vacancy voids. For justification of the model experimental data on fracture strain and fracture toughness of austenitic steel 18Cr-10Ni-Ti grade irradiated up to maximal dose 150dpa with various swelling were used. Experimental data on fracture strain and fracture toughness were compared with the results predicted by the model. It has been shown that for prediction of the swelling effect on fracture toughness the dependence of process zone size on swelling should be taken into account. [ABSTRACT FROM AUTHOR]

The article provides an overview on various aspects of the catalytic chemistry of phthalocyanine metal complexes (MPc). It describes the general synthetic methods for the preparation of metal phthalocyanines and different strategies for their immobilization. It also discusses the catalytic applications of MPc's in various reactions.

Several types of starches were oxidizedby H2O2in the presence of iron tetrasulfophthalocyaninecatalyst (FePcS)in batch mode, and the kinetics of the H2O2decompositionwas followed when varying the catalyst concentration and solid toliquid ratio of the starch and aqueous phase. Mainly, waxy corn starchwith high content of amylopectin and potato starch were used, butalso high amylose starch was studied. The COOH content was determinedfor the final oxidized starch. It was found that, with 40 mg of catalystand the starch present in a larger amount, the H2O2decomposition followed a first order kinetics with an initialdecomposition rate in the range of 0.10 mol/L·h. Significantlyless starch slowed down the decomposition rate to 0.05 mol/L·h;however, when no starch was present, the decomposition increased toa maximum of 0.14 mol/L. On the contrary, absence of catalyst resultedin a linear H2O2decomposition profile. TheFePcS catalyst concentration had a large impact on the decompositionof H2O2regardless of the starch amount or thestarch origin. When using very low starch amounts in relation to thecatalyst amount, brown solid residues were observed on the reactorwall, indicating that iron was defragmented from the catalyst. [ABSTRACT FROM AUTHOR]

Abstract: Catalytic properties of Fe-MIL-101 and Cr-MIL-101 metal–organic frameworks in the solvent-free oxidation of cyclohexene and α-pinene with molecular oxygen have been explored. Both catalysts allow alkene oxidation under mild conditions (1bar O2, 40–60°C) and afford allylic oxidation products. The nature of catalysis and the product distribution strongly depend on the nature of the transition metal. Cr-MIL-101 behaves as truly heterogeneous catalyst to give predominantly α,β-unsaturated ketones. Catalysis over Fe-MIL-101 has true heterogeneous nature only at 40°C, producing mainly 2-cyclohexene-1-ol. At 50–60°C, iron leaching into solution occurs, leading to cyclohexenyl hydroperoxide as the major product. Under optimal conditions, both catalysts can be reused several times without suffering a loss of the catalytic properties. Rate-retarding and rate-accelerating effects of inhibitors and initiators, respectively, indicate radical chain mechanism. Different pathways for transformation of hydroperoxide have been suggested to rationalize the observed differences in the reaction selectivities over Cr- and Fe-MIL-101. [Copyright &y& Elsevier]

Abstract: J-aggregates of amphi-PIC dye have been successfully formed in polymer films by layer-by-layer assembly method. Another dye embedded into J-aggregate layer has revealed itself as efficient exciton trap, which trapped about 80% of excitons. Analyzing J-aggregate luminescence quenching using modified Stern–Volmer equation it has been found that 1 DiD molecule quenches 50% luminescence of 60 amphi-PIC molecules forming the J-aggregate. That is half as much compared to the solution case. The reason for such difference discussed. [Copyright &y& Elsevier]

Diiron macrocyclic complexes have been often considered as catalytically inert. However, numerous published examples of the catalytic oxidation reactions mediated by these complexes indicate their potential in catalysis. Mechanistic background for their applications as oxidation catalysts and their relationship with enzymatic and biomimetic oxidation involving cytochrome P-450 and soluble methane monooxygenase are discussed. A special emphasis was put on the N-bridged diiron phthalocyanine complexes as an emerging class of oxidation catalysts. Their unusual Fe(μN)Fe structure has interesting catalytic properties and reactivity. In addition to oxidation of strong C-H bonds in alkanes including methane, aromatic, and alkylaromatic compounds, μ-nitrido diiron phthalocyanines catalyze the oxidative dehalogenation and the formation of C-C bonds. A clean and practical character of the catalytic systems coupled with real availability of the phthalocyanines suggests a possibility of the application of this approach in industry. Great potential for further developments by modification of the catalysts structure can be envisioned. [ABSTRACT FROM AUTHOR]

The clean catalytic oxidation of 8-hydroxyquinoline (8-HQ) with tert-butyl hydroperoxide to quinoline-5,8-dione (QD), a molecular framework fragment of antitumor compounds, over silica-supported iron tetrasulfophthalocyanine catalysts (FePcS) is reported. The pronounced influence of the FePcS state (monomer vs.dimer) and the support (amorphous SiO2vs.mesoporous MCM-41) on the catalytic activity and selectivity is revealed. Depending on the catalyst structure, turnover frequency values determined from the initial rates of 8-HQ consumption varied from 215 to 3570 h−1.The effects of solvent, temperature, reagent concentrations and catalyst amounts on the substrate conversion and QD selectivity were studied to optimize the reaction conditions. With an optimal catalyst, the yield of the target product reached 66%. The truly heterogeneous nature of the catalysis was also demonstrated. [ABSTRACT FROM AUTHOR]

The clean catalytic oxidation of 8-hydroxyquinoline (8-HQ) with tert-butyl hydroperoxide to quinoline-5,8-dione (QD), a molecular framework fragment of antitumor compounds, over silica-supported iron tetrasulfophthalocyanine catalysts (FePcS) is reported. The pronounced influence of the FePcS state (monomer vs.dimer) and the support (amorphous SiO2vs.mesoporous MCM-41) on the catalytic activity and selectivity is revealed. Depending on the catalyst structure, turnover frequency values determined from the initial rates of 8-HQ consumption varied from 215 to 3570 h−1.The effects of solvent, temperature, reagent concentrations and catalyst amounts on the substrate conversion and QD selectivity were studied to optimize the reaction conditions. With an optimal catalyst, the yield of the target product reached 66%. The truly heterogeneous nature of the catalysis was also demonstrated. [ABSTRACT FROM AUTHOR]

Abstract: The aim of the present study was to determine differences in cortical processing of consonant–vowel syllables and acoustically matched non-speech sounds, as well as novel human and nonhuman sounds. Event-related potentials (ERPs) were recorded to vowel, vowel duration, consonant, syllable intensity, and frequency changes as well as corresponding changes in their non-speech counterparts with the multi-feature mismatch negativity (MMN) paradigm. Enhanced responses to linguistically relevant deviants were expected. Indeed, the vowel and frequency deviants elicited significantly larger MMNs in the speech than non-speech condition. Minimum-norm source localization algorithm was applied to determine hemispheric asymmetry in the responses. Language relevant deviants (vowel, duration and – to a lesser degree – frequency) showed higher activation in the left than right hemisphere to stimuli in the speech condition. Novel sounds elicited novelty P3 waves, the amplitude of which for nonhuman sounds was larger in the speech than non-speech condition. The current MMN results imply enhanced processing of linguistically relevant information at the pre-attentive stage and in this way support the domain-specific model of speech perception. [Copyright &y& Elsevier]

Abstract: The Baeyer-Villiger oxidation of cyclohexanone to caprolactone has been investigated at room temperature over AlFe-pillared clays, using oxygen as oxidant in the presence of benzaldehyde. A nearly complete conversion is observed with a selectivity into caprolactone above 80%. The observation of an induction period in the kinetics, of high activity of the non-pillared clay, and the detection of Fe traces in the reaction medium, suggest a process involving homogenous catalysis. The reaction is indeed catalysed in homogeneous phase by a few ppm of Fe. By contrast, iron phthalocyanine covalently supported on silica appears as a true heterogeneous catalyst, giving a selectivity above 95% to caprolactone at 61% conversion. [Copyright &y& Elsevier]

The article focuses on the conception of Evald Vasilevich Ilyenkov of ideal, defined as a form of subjective activity of social man that has objective meaning and significance. It says that the theoretical foundation of Ilyenkov is the concept of Karl Marx on human as a sociohistorical being, wherein he developed a concrete understanding of human social activity. Moreover, it mentions that ideal exists as man's ideal activity to fulfill his own goals.