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.     

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.     

Study of parameters and entrainment of a jet in cross-flow arrangement with transition at two low Reynolds numbers

Investigation of the mixing process is one of the main issues in chemical engineering and combustion and the configuration of a jet into a cross-flow (JCF) is often employed for this purpose. Experimental data are gained for the symmetry plane in a JCF-arrangement of an air flow using a combination of particle image velocimetry (PIV) with laser-induced fluorescence (LIF). The experimental data with thoroughly measured boundary conditions are complemented with direct numerical simulations, which are based on idealized boundary conditions. Two similar cases are studied with a fixed jet-to-cross-flow velocity ratio of 3.5 and variable cross-flow Reynolds numbers equal to 4,120 and 8,240; in both cases the jet issues from the pipe at laminar conditions. This leads to a laminar-to-turbulent transition, which depends on the Reynolds number and occurs quicker for the case with higher Reynolds number in both experiments and simulations as well. It was found that the Reynolds number only slightly affects the jet trajectory, which in the case with the higher Reynolds number is slightly deeper. It is attributed to the changed boundary layer shape of the cross-flow. Leeward streamlines bend toward the jet and are responsible for the strong entrainment of cross-flow fluid into the jet. Velocity components are compared for the two Reynolds numbers at the leeward side at positions where strongest entrainment is present and a pressure minimum near the jet trajectory is found. The numerical simulations showed that entrainment is higher for the case with the higher Reynolds number. The latter is attributed to the earlier transition in this case. Fluid entrainment of the jet in cross-flow is more than twice stronger than for a similar flow of a jet issuing into a co-flowing stream. This comparison is made along the trajectory of the two jets at a distance of 5.5 jet diameters downstream and is based on the results from the direct numerical simulations and recently published experiments of a straight jet into a co-flow. Mixing is further studied by means of second-order statistics of the passive scalar variance and the Reynolds fluxes. Windward and leeward sides of the jet exhibit different signs for the time-averaged streamwise Reynolds flux 〈v _x ′c′〉. The large coherent structures which contribute to this effect are investigated by means of timely correlated instantaneous PIV-LIF camera snapshots and their contribution to the average statistics of 〈v _x ′c′〉 are discussed. The discussion on mixing capabilities of the jet in cross-flow is supported by simulation results showing the instantaneous three-dimensional coherent structures defined in terms of the pressure fluctuations.     

Development of a Two-velocities Hybrid RANS-LES Model and its Application to a Trailing Edge Flow

The flow around a trailing edge is computed with a new hybrid method designed to more clearly separate the effects of total and sub-grid turbulent stress-modelling on the time-averaged and instantaneous velocity fields, and in turn, mean momentum and kinetic energy balances. These two velocity fields independently define Reynolds averaged and sub-grid-scale viscosities, and distinct stresses, at the same location. In particular, resolved eddies can emerge, or sweep in and out of the Reynolds averaged near wall layer, without being dampened by higher levels of the viscosity in this RANS dominated layer. The two-field hybrid model, first tested on channel flows, gives accurate predictions of mean velocities and stresses for different Reynolds numbers and coarse meshes. For the trailing edge flow the results of the hybrid model are close to the reference fine LES for mean velocity and turbulent content, whereas the DES-SST on the same coarse mesh gives too early separation.     

Solar Urea: Towards a Sustainable Fertilizer Industry

Urea, an agricultural fertilizer, nourishes humanity. The century-old Bosch–Meiser process provides the world's urea. It is multi-step, consumes enormous amounts of non-renewable energy, and has a large CO₂ footprint. Thus, developing an eco-friendly synthesis for urea is a priority. Herein we report a single-step Pd/LTA-3A catalyzed synthesis of urea from CO₂ and NH₃ under ambient conditions powered solely by solar energy. Pd nanoparticles serve the dual function of catalyzing the dissociation of NH₃ and providing the photothermal driving force for urea formation, while the absorption capacity of LTA-3A removes by-product H₂O to shift the equilibrium towards urea production. The solar urea conversion rate from NH₃ and CO₂ is 87 μmol g^?1 h^?1. This advance represents a first step towards the use of solar energy in urea production. It provides insights into green fertilizer production, and inspires the vision of sustainable, modular plants for distributed production of urea on farms.     

Reactions of p‐Substituted Phenols with Nitrous Acid in Aqueous Solution

The reaction of phenols with nitrite (nitrous acid HONO, or its conjugated base, NO₂^?) is of importance in stomach fluids (low pH) and in atmospheric hydrometeors (mild acid and basic pH). The initial reaction associated with the oxidation/nitration of 4‐substitued phenols promoted by HONO/NO₂ depends on the pH of the solution. At low pH, the initial step involves the reaction between HONO and phenol, whereas at basic conditions this involves an electron transfer from the phenoxy anion to nitrogen dioxide (NO₂) producing the nitrite anion. The rate of both processes is determined by the donor capacity of the substituent at the 4‐position of the phenol, and the data obtained at pH 2.3 follow a linear Hammett‐type correlation with a slope equal to –1.23. The partition of the gaseous intermediates (NO and NO₂) makes the rate of HONO‐mediated oxidation dependent on their gas–liquid distribution. At low pH, the main process is phenol oxidation, even in oxygen‐free conditions, and the presence of any 4‐substituted phenol decreases the rate of HONO auto‐oxidation.     

An Alternative Approach to the Electric Charge Quantization with Non-global Potentials

We present an alternative approach to justify the electric charge quantization by means of non-global electromagnetic potentials. We adopt a non-global potential whose singularity does not goes over to infinity and can be entirely embedded into an arbitrarily small closed ball.