2-Amino-6-[(2,6-dichloro­phen­yl)imino]-3-oxocyclo­hexa-1,4-dienecarbaldehyde

The title compound, C13H8Cl2N2O2, was obtained by the oxidation of diclofenac {systematic name: 2-[2-(2,6-dichloro­phenyl­amino)­phen­yl]acetic acid}, an anti-inflammatory drug, with hydrogen peroxide catalysed by chlorido[5,10,15,20-tetra­kis­(2,6-dichloro­phen­yl)porphyrinato]manganese(III), using ammonium acetate as co-catalyst. The asymmetric unit contains two crystallographically independent mol­ecules of the title compound (Z′ = 2). The close packing of individual mol­ecules is mediated by a series of strong and rather directional N—H⋯Cl and N—H⋯O hydrogen bonds, plus weak π–π [distance between the individual double bonds of symmetry-related imino­quinone rings = 3.7604 (13) Å] and Cl⋯O inter­actions [3.0287 (18) Å]

Unrevealing the interactive effects of climate change and oil contamination on lab-simulated estuarine benthic communities

There is growing concern that modifications to the global environment such as ocean acidification and increased ultraviolet radiation may interact with anthropogenic pollutants to adversely affect the future marine environment. Despite this, little is known about the nature of the potential risks posed by such interactions. Here, we performed a multifactorial microcosm experiment to assess the impact of ocean acidification, ultraviolet radiation B (UV-B) and oil hydrocarbon contamination on sediment chemistry, the microbial community (composition and function) and biochemical marker response of selected indicator species. We found that increased ocean acidification and oil contamination in the absence of UV-B will significantly alter bacterial composition by, among other changes, greatly reducing the relative abundance of Desulfobacterales, known to be important oil hydrocarbon degraders. Along with changes in bacterial composition, we identified concomitant shifts in the composition of aromatic hydrocarbons in the sediment and an increase in oxidative stress effects on our indicator species. Interestingly, our study identifies UV-B as a critical component in the interaction between these factors, since its presence alleviates harmful effects caused by the combination of reduced pH and oil pollution. The model system used here shows that the interactive effect of reduced pH and oil contamination can adversely affect the structure and functioning of sediment benthic communities, with the potential to exacerbate the toxicity of oil hydrocarbons in marine ecosystems

Recent Synthetic Advances on the Use of Diazo Compounds Catalyzed by Metalloporphyrins

Diazo compounds are organic substances that are often used as precursors in organic synthesis like cyclization reactions, olefinations, cyclopropanations, cyclopropenations, rearrangements, and carbene or metallocarbene insertions into C−H, N−H, O−H, S−H, and Si−H bonds. Typically, reactions from diazo compounds are catalyzed by transition metals with various ligands that modulate the capacity and selectivity of the catalyst. These ligands can modify and enhance chemoselectivity in the substrate, regioselectivity and enantioselectivity by reflecting these preferences in the products. Porphyrins have been used as catalysts in several important reactions for organic synthesis and also in several medicinal applications. In the chemistry of diazo compounds, porphyrins are very efficient as catalysts when complexed with low-cost metals (e.g., Fe and Co) and, therefore, in recent years, this has been the subject of significant research. This review will summarize the advances in the studies involving the field of diazo compounds catalyzed by metalloporphyrins (M−Porph, M = Fe, Ru, Os, Co, Rh, Ir) in the last five years to provide a clear overview and possible opportunities for future applications. Also, at the end of this review, the properties of artificial metalloenzymes and hemoproteins as biocatalysts for a broad range of applications, namely those concerning carbene-transfer reactions, will be considered

Solketal Production via Solvent-Free Acetalization of Glycerol over Triphosphonic-Lanthanide Coordination Polymers

Biodiesel is one of the most significant and valuable alternatives to fossil fuels. In the process of transesterification to produce biodiesel from various feedstocks, glycerol is one of the side products obtained, in a high glycerol: biodiesel weight ratio (1:10). Therefore, the growing world demand for biodiesel prompted a glycerol surplus. It is, thus, of interest to find new and added-value paths for the transformation of this abundant chemical. One of the most auspicious glycerol applications is the production of fuel additives, namely cyclic acetals and ketals, from aldehydes and ketones, respectively. In this work, coordination polymers based on nitrile (trimethylphosphonic acid) and Ln3+/Eu3+ are used as catalysts for the acetalization of the bio-renewable glycerol into oxygenated fuel additives. Solketal is the major product obtained from the reaction of glycerol with acetone. This product improves the cold flow properties, lowering the viscosity of biodiesel, improving combustion, and boosting the octane number. The stability of the materials is studied as well as their recovery and reuse

Influence of Ethanol Parametrization on Diffusion Coefficients Using OPLS-AA Force Field

Molecular dynamics simulations employing the all-atom optimized potential for liquid simulations (OPLS-AA) force field were performed for determining self-diffusion coefficients (D11) of ethanol and tracer diffusion coefficients (D12) of solutes in ethanol at several temperature and pressure conditions. For simulations employing the original OPLS-AA diameter of ethanol’s oxygen atom (σOH), calculated and experimental diffusivities of protic solutes differed by more than 25%. To correct this behavior, the σOH was reoptimized using the experimental D12 of quercetin and of gallic acid in liquid ethanol as benchmarks. A substantial improvement of the calculated diffusivities was found by changing σOH from its original value (0.312 nm) to 0.306 nm, with average absolute relative deviations (AARD) of 3.71% and 4.59% for quercetin and gallic acid, respectively. The new σOH value was further tested by computing D12 of ibuprofen and butan-1-ol in liquid ethanol with AARDs of 1.55% and 4.81%, respectively. A significant improvement was also obtained for the D11 of ethanol with AARD = 3.51%. It was also demonstrated that in the case of diffusion coefficients of non-polar solutes in ethanol, the original σOH=0.312 nm should be used for better agreement with experiment. If equilibrium properties such as enthalpy of vaporization and density are estimated, the original diameter should be once again adopted

Biomimetic oxidation of carbamazepine with hydrogen peroxide catalyzed by a manganese porphyrin

This laboratory project is planned for an undergraduate chemistry laboratory in which students prepare a manganese porphyrin able to mimic the oxidative metabolism of carbamazepine, one of the most frequently prescribed drugs in the treatment of epilepsy. The in vitro oxidation of carbamazepine results in the formation of the corresponding 10,11-epoxide, the main in vivo metabolite. The reaction is catalyzed by manganese porphyrin in the presence of H2O2, an environmentally-friendly oxidant. Through this project students will develop their skills in organic synthesis, coordination chemistry, chromatographic techniques such as TLC and HPLC, UV-visible spectrophotometry, and NMR spectroscopy

Vine Waste Valorisation: Integrated Approach for the Prospection of Bioactive Lipophilic Phytochemicals

Substantial amounts of vine wastes are produced during vineyard management, and the chemical profiling of high-value lipophilic phytochemicals is becoming crucial in order to find a complementary route towards their integrated valorisation. The prospection of bioactive phytochemicals from unripe grape, vine shoot, vine cane, stalk and leaf dichloromethane extracts was carried out by gas chromatography–mass spectrometry (GC–MS), analysing samples from a mixture of four red Vitis vinifera L. varieties (Baga, Aragonez, Água Santa and Shiraz), collected at Bairrada Appellation, as a representative case study of typical multi-variety Portuguese vineyards. Vine wastes showed distinct amounts of lipophilic extract, ranging from 0.68% (vine canes) to 13.35% (vine leaves) at dry weight (dw). Thirty-three components were identified, including fatty acids and alcohols, sterols and triterpenoids accounting for amounts from 118.9 mg/100 g dw to 1512.0 mg/100 g dw. The integrated study revealed that unripe grape, stalk and leaf dichloromethane extracts stood out as possible sources of triterpenic compounds (103.2 to 653.5 mg/100 g dw), with lupeol, ursolic and oleanolic acids prevailing. Leaf extract is also reported as an undervalued source of α-tocopherol, as the major component detected in this matrix (300.5 mg/100 g dw). These exploratory results are a relevant contribution for the exploitation of undervalued vine residues as a source of health-promoting components with the potential to be used as supplements or nutraceutical ingredients

Biomimetic Oxidation of Benzofurans with Hydrogen Peroxide Catalyzed by Mn(III) Porphyrins

The modelling of metabolic activation of the benzofuran nucleus is important to obtain eco-sustainable degradation methods and to understand the related mechanisms. The present work reports the catalytic oxidation of benzofuran, 2-methylbenzofuran, and 3-methylbenzofuran by hydrogen peroxide, at room temperature, in the presence of different Mn(III) porphyrins as models of cytochrome P450 enzymes. Conversions above 95% were attained for all the substrates. The key step is the formation of epoxides, which undergo different reaction pathways depending on factors, such as the position of the methyl group and the reaction and work-up conditions used

Halophyte plant colonization as a driver of the composition of bacterial communities in salt marshes chronically exposed to oil hydrocarbons

In this study, two molecular techniques [denaturing gradient gel electrophoresis (DGGE) and barcoded pyrosequencing] were used to evaluate the composition of bacterial communities in salt marsh microhabitats [bulk sediment and sediment surrounding the roots (rhizosphere) of Halimione portulacoides and Sarcocornia perennis ssp. perennis] that have been differentially affected by oil hydrocarbon (OH) pollution. Both DGGE and pyrosequencing revealed that bacterial composition is structured by microhabitat. Rhizosphere sediment from both plant species revealed enrichment of operational taxonomic units closely related to Acidimicrobiales, Myxococcales and Sphingomonadales. The in silico metagenome analyses suggest that homologous genes related to OH degradation appeared to be more frequent in both plant rhizospheres than in bulk sediment. In summary, this study suggests that halophyte plant colonization is an important driver of hydrocarbonoclastic bacterial community composition in estuarine environments, which can be exploited for in situ phytoremediation of OH in salt marsh environments

Photocatalytic degradation of methyl orange mediated by a silica coated nanomagnet porphyrin hybrid

The photocatalytic activity of a silica coated nanomagnet porphyrin hybrid (NPH) and of the corresponding porphyrin precursors (H2P and ZnP) was evaluated in the degradation of the methyl orange dye (MO) under visible light irradiation. The catalytic degradation of MO was performed under air, in the absence and in the presence of aqueous hydrogen peroxide. The results show that the hybrid NPH was the most effective photocatalyst causing the total degradation of MO after 270 min of white light irradiation (150 mW cm−2 ) in the presence of hydrogen peroxide. The remarkable photocatalytic activity of this NPH, associated with the possibility of its reuse, makes this material a promising photocatalyst.publishe