The thermal isomerization of 6-difluoromethylenebicyclo[3.2.0]hept-2-ene

The thermal isomerization of 6-difluoromethylenebicyclo[3.2.0]hept-2-ene proceeds via two competing 1,3-sigmatropic processes, with an E_a nearly identical to that of the hydrocarbon.     

Charge accumulation kinetics in multi-redox molecular catalysts immobilised on TiO2

Multi-redox catalysis requires the accumulation of more than one charge carrier and is crucial for solar energy conversion into fuels and valuable chemicals. In photo(electro)chemical systems, however, the necessary accumulation of multiple, long-lived charges is challenged by recombination with their counterparts. Herein, we investigate charge accumulation in two model multi-redox molecular catalysts for proton and CO₂ reduction attached onto mesoporous TiO₂ electrodes. Transient absorption spectroscopy and spectroelectrochemical techniques have been employed to study the kinetics of photoinduced electron transfer from the TiO₂ to the molecular catalysts in acetonitrile, with triethanolamine as the hole scavenger. At high light intensities, we detect charge accumulation in the millisecond timescale in the form of multi-reduced species. The redox potentials of the catalysts and the capacity of TiO₂ to accumulate electrons play an essential role in the charge accumulation process at the molecular catalyst. Recombination of reduced species with valence band holes in TiO₂ is observed to be faster than microseconds, while electron transfer from multi-reduced species to the conduction band or the electrolyte occurs in the millisecond timescale. Finally, under light irradiation, we show how charge accumulation on the catalyst is regulated as a function of the applied bias and the excitation light intensity.

Using transient spectroelectrochemical techniques, we investigate multiply reduced states of molecular catalysts on titania photoelectrodes as a function of the applied bias and the light intensity.     

Thermal elimination of diethyldithiocarbamates and application in the synthesis of (+/-)-ferrugine

Dithiocarbamate-substituted lactams, prepared through group-transfer cyclization reactions of carbamoyl radicals, undergo a Chugaev-like thermal elimination of the dithiocarbamate group in refluxing diphenyl ether to form alpha,beta- and/or beta,gamma-unsaturated amides, depending on the structure of the starting material. This reaction sequence was used to prepare an unsaturated [3.2.2] bridged bicyclic amide, which was converted in a one-pot procedure to the 8-azabicyclo[3.2.1]octane ring system of the tropane alkaloid ferrugine by treatment with phenyllithium followed by aqueous sodium hydroxide.     

Variable Selection Towards Classification of Digital Images: Identification of Altered Glucose Levels in Serum

Identification of altered glucose levels in serum is the main indicator for diabetes, where control levels are classed as <100?mg/dL, and altered levels are classified as pre-diabetic (100–125?mg/dL) or diabetic (>125?mg/dL). Herein, we propose a method to identify control, pre-diabetic, or diabetic simulated and real-world samples based on their glucose levels using classification-based variable selection algorithms [successive projections algorithm (SPA) or genetic algorithm (GA)] coupled to linear discriminant analysis (SPA-LDA and GA-LDA) towards analyzing red–green–blue digital images. Images were recorded after glucose enzymatic reaction, whereby 250?μL of reactant content of samples were captured by using a common cell phone camera. Processing was applied to the images at a pixel level, where 72.2% of the pixels were correctly classified as control, 79.2% as pre-diabetic, and 90.9% as diabetic using SPA-LDA algorithm; and 76.8% as control, 81.4% as pre-diabetic, and 91.7% as diabetic using GA-LDA algorithm in the validation set containing nine simulated samples. Eight real-world samples were measured as an external test set, where the accuracy using GA-LDA was found to be 92%, with sensitivities ranging from 70% to 100 and specificities ranging from 90% to 99%. This method shows the potential of variable selection techniques coupled with digital image analysis towards blood glucose monitoring.     

Oxidative Crosslinking of Peptides and Proteins: Mechanisms of Formation,Detection, Characterization and Quantification

Covalent crosslinks within or between proteins play a key role in determining the structure and function of proteins. Some of these are formed intentionally by either enzymatic or molecular reactions and are critical to normal physiological function. Others are generated as a consequence of exposure to oxidants (radicals, excited states or two-electron species) and other endogenous or external stimuli, or as a result of the actions of a number of enzymes (e.g., oxidases and peroxidases). Increasing evidence indicates that the accumulation of unwanted crosslinks, as is seen in ageing and multiple pathologies, has adverse effects on biological function. In this article, we review the spectrum of crosslinks, both reducible and non-reducible, currently known to be formed on proteins; the mechanisms of their formation; and experimental approaches to the detection, identification and characterization of these species.     

Supercharged CO2 Photothermal Catalytic Methanation: High Conversion,Rate, and Selectivity

To overcome the thermodynamic and kinetic impediments of the Sabatier CO₂ methanation reaction, the process must be operated under very high temperature and pressure conditions, to obtain an industrially viable conversion, rate, and selectivity. Herein, we report that these technologically relevant performance metrics have been achieved under much milder conditions using solar rather than thermal energy, where the methanation reaction is enabled by a novel nickel-boron nitride catalyst. In this regard, an in situ generated HOB⋅⋅⋅B surface frustrated Lewis's pair is considered responsible for the high Sabatier conversion 87.68 %, reaction rate 2.03 mol g_Ni⁻¹h⁻¹, and near 100 % selectivity, realized under ambient pressure conditions. This discovery bodes well for an opto-chemical engineering strategy aimed at the development and implementation of a sustainable ‘Solar Sabatier’ methanation process.     

Inhibitory Effects of Varespladib,CP471474, and Their Potential Synergistic Activity on Bothrops asper and Crotalus durissus cumanensis Venoms

Snakebite is a neglected tropical disease that causes extensive mortality and morbidity in rural communities. Antivenim sera are the currently approved therapy for snake bites; however, they have some therapeutic limitations that have been extensively documented. Recently, small molecule toxin inhibitors have received significant attention as potential alternatives or co-adjuvant to immunoglobulin-based snakebite therapies. Thus, in this study, we evaluated the inhibitory effects of the phospholipase A₂ inhibitor varespladib and the metalloproteinase inhibitor CP471474 and their synergistic effects on the lethal, edema-forming, hemorrhagic, and myotoxic activities of Bothrops asper and Crotalus durissus cumanensis venoms from Colombia. Except for the preincubation assay of the lethal activity with B. asper venom, the mixture showed the best inhibitory activity. Nevertheless, the mix did not display statistically significant differences to varespladib and CP471474 used separately in all assays. In preincubation assays, varespladib showed the best inhibitory activity against the lethal effect induced by B. asper venom. However, in independent injection assays, the mix of the compounds partially inhibited the lethal activity of both venoms (50%). In addition, in the assays to test the inhibition of edema-forming activity, the mixture exhibited the best inhibitory activity, followed by Varespladib, but without statistically significant differences (p > 0.05). The combination also decreased the myotoxic activity of evaluated venoms. In these assays, the mix showed statistical differences regarding CP471474 (p < 0.05). The mixture also abolished the hemorrhagic activity of B. asper venom in preincubation assays, with no statistical differences to CP471474. Finally, the mixture showed inhibition in studies with independent administration in a time-dependent manner. To propose a mode of action of varespladib and CP471474, molecular docking was performed. PLA_2s and SVMPs from tested venoms were used as targets. In all cases, our molecular modeling results suggested that inhibitors may occupy the substrate-binding cleft of the enzymes, which was supported by specific interaction with amino acids from the active site, such as His48 for PLA_2s and Glu143 for the metalloproteinase. In addition, varespladib and CP471474 also showed interaction with residues from the hydrophobic channel in PLA_2s and substrate binding subsites in the SVMP. Our results suggest a synergistic action of the mixed inhibitors and show the potential of varespladib, CP471474, and their mixture to generate new treatments for snakebite envenoming with application in the field or as antivenom co-adjuvants.