Progress on PPAPs cyclization: Guttiferone A as a case study

Guttiferone A and cyclized analogs are naturally occurring polycyclic polyprenylated acyl phloroglucinols possessing antiparasitic activities. Naturally occurring xanthones possess increased activity, but are either rare or difficult to synthesize. In this paper, three optimized methodologies to access natural, hydroxylated and non-natural xanthonic skeletons from guttiferone A are described. These compounds will serve as starting materials for further SAR studies.     

Vesicular exocytosis under hypotonic conditions shows two distinct populations of dense core vesicles in bovine chromaffin cells.

Several previous reports have discussed the effects of external osmolarity on vesicular exocytotic processes. However, few of these studies considered hypotonic conditions on chromaffin cells. Herein, the exocytosis of catecholamines by chromaffin cells was investigated in a medium of low osmolarity (200 mOsm) by amperometry at carbon fiber microelectrodes. It is observed that the frequency of the exocytotic events is significantly higher under hypotonic conditions than under physiological conditions (315 mOsm). This further confirms that the swelling of the polyelectrolytic matrix (which follows ionic exchanges) contained in dense core vesicles is the energetic driving force of the exocytotic phenomenon, being favored by a lower osmolarity. The mean amount of catecholamines released during secretory events also increases importantly under the hypotonic condition. This may be rationalized by the coexistence of two distinct populations of dense core vesicles with a relative content ratio of 4.7. The larger content population is favored under hypotonic conditions but plays only a side role under isotonic conditions.     

Highly efficient ruthenium catalysts for the formation of tetrasubstituted olefins via ring-closing metathesis

[reaction: see text] A series of ruthenium-based metathesis catalysts with N-heterocyclic carbene (NHC) ligands have been prepared in which the N-aryl groups have been changed from mesityl to mono-ortho-substituted phenyl (e.g., tolyl). These new catalysts offer an exceptional increase in activity for the formation of tetrasubstituted olefins via ring-closing metathesis (RCM), while maintaining high levels of activity in ring-closing metathesis (RCM) reactions that generate di- and trisubstituted olefins.     

Sequential Barium‐Catalysed N−H/H−Si Dehydrogenative Cross‐Couplings: Cyclodisilazanes versus Linear Oligosilazanes

Starting from Ph₃SiH, the barium precatalyst Ba[CH(SiMe₃)₂]₂?(THF)₃ was used to produce the disilazane Ph₃SiN(Bn)SiPh₂NHBn ( 4 ) by sequential N?H/H?Si dehydrogenative couplings with BnNH₂ and Ph₂SiH₂. Substrate scope was extended to other amines and hydrosilanes. This smooth protocol gives quantitative yields and full chemoselectivity. Compound 4 and the intermediates Ph₃SiNHBn and Ph₃SiN(Bn)SiHPh₂ were structurally characterised. Further attempts at chain extension by dehydrocoupling of Ph₂SiH₂ with 4 instead resulted in cyclisation of this compound, forming the cyclodisilazane c‐(Ph₂Si‐NBn)₂ ( 5 ) which was crystallographically authenticated. The ring‐closure mechanism leading to 5 upon release of C₆H₆ was determined by complementary experimental and theoretical (DFT) investigations. Ba[CH(SiMe₃)₂]₂?(THF)₃ and 4 react to afford the reactive Ba{N(Bn)SiPh₂N(Bn)SiPh₃}₂, which was characterised in situ by NMR spectroscopy. Next, in a stepwise process, intramolecular nucleophilic attack of the metal‐bound amide on the terminal silicon atom generates a five‐coordinate silicate. It is followed by turnover‐limiting β‐C₆H₅ transfer to barium; this releases 5 and forms a transient [Ba]?Ph species, which undergoes aminolysis to regenerate [Ba]?N(Bn)SiPh₂N(Bn)SiPh₃. DFT computations reveal that the irreversible production of 5 through such a stepwise ring‐closure mechanism is much more kinetically facile (ΔG^≠=26.2 kcal mol^?1) than an alternative σ‐metathesis pathway (ΔG^≠=48.2 kcal mol^?1).     

Pincer ligands with an all-phosphorus donor set: subtle differences between rhodium and palladium

The synthesis of a new, all-phosphorus pincer PP(NEt2)P ligand L3(NEt2), which is derived from 2-indolylphosphine and features a central N(2)P(NEt(2)) core, is described. This 'PPP' species shows coordination toward Rh as a neutral trisphosphine ligand. Tridentate diphenylphosphine-derived PP(H)P ligands L1(H) and L2(H), featuring a secondary phosphine core, show 'ambivalent' coordination, acting as persistent neutral triphosphine ligands with Rh, and as easily-formed monoanionic phosphido(bisphosphine) pincer ligands toward Pd. These subtle differences, which might be more general for group 9 and 10 metal complexes with this ligand set, are explained by comparative DFT calculations (BP86; def2-TZVP level of theory) for the Rh and Pd species involved, including those with the structurally related PN(H)P ligands. The optimized structure for complex PdCl(L2) indicates minimal overlap of available Pd d-orbitals with the lone pair of the central, deprotonated phosphorus atom (formally a phosphido fragment), suggesting that it behaves predominantly like a bulky phosphine instead of a phosphido fragment.     

High order numerical simulation of the thermal load on a lobed strut injector for scramjet applications

In this paper, the thermal load on an actively cooled lobed strut injector for scramjet (supersonic combustion ramjet) applications is investigated numerically. This requires coupled simulations of the strut internal and external flow fields together with the heat conduction in the solid injector body. In order to achieve a fast mixing, the lobed strut is positioned at the channel axis to inject hydrogen into the core of a Mach 3 air stream. There it is exposed to the extremely high temperatures of the high speed flow. While the external air and hydrogen flows are supersonic, the strut internal hydrogen flow is mainly subsonic, in some regions at very low Mach numbers. To enable a simulation of the internal flow field which ranges from very low to very high Mach numbers (approximately Mach 2.25 at the nozzle exit), a preconditioning technique is employed. The compressible finite‐volume scheme uses a spatially fourth order multi‐dimensional limiting process discretization, which is used here for a first time to simulate a geometrically and fluid mechanically highly complex problem. It will be demonstrated that besides its high accuracy the multi‐dimensional limiting process scheme is numerically stable even in case of demanding practical applications. The coupled simulation of the lobed strut injector delivers unique insight into the flow phenomena inside and outside the strut, the heat fluxes, the temperature distribution in the solid material, the required hydrogen mass flux with respect to cooling requirements and details concerning the conditions at the exit of the injector. Copyright © 2016 John Wiley & Sons, Ltd.     

Bubbly flow measurements in hydraulic jumps with small inflow Froude numbers

The transition from supercritical to subcritical open channel flow is characterised by a strong dissipative mechanism called a hydraulic jump. A hydraulic jump is turbulent and associated with the development of large-scale turbulence and air entrainment. In the present study, some new physical experiments were conducted to characterise the bubbly flow region of hydraulic jumps with relatively small Froude numbers (2.4 < Fr₁ < 5.1) and relatively large Reynolds numbers (6.6 × 10⁴ < Re < 1.3 × 10⁵). The shape of the time-averaged free-surface profiles was well defined and the longitudinal profiles were in agreement with visual observations. The turbulent free-surface fluctuation profiles exhibited a peak of maximum intensity in the first half of the hydraulic jump roller, and the fluctuations exhibited some characteristic frequencies typically below 3 Hz. The air–water flow properties showed two characteristic regions: the shear layer region in the lower part of the flow and an upper free-surface region above. The air–water shear layer region was characterised by local maxima in terms of void fraction and bubble count rate. Other air–water flow characteristics were documented including the distributions of interfacial velocity and turbulence intensity. The probability distribution functions (PDF) of bubble chord time showed that the bubble chord times exhibited a broad spectrum, with a majority of bubble chord times between 0.5 and 2 ms. An analysis of the longitudinal air–water structure highlighted a significant proportion of bubbles travelling within a cluster structure.     

Porous materials with two populations of voids under internal pressure: II. Growth and coalescence of voids

This study is devoted to the mechanical behaviour of polycrystalline materials with two populations of voids, small spherical voids located inside the grains and larger spheroidal voids located at the grain boundaries. In part I of the work, instantaneous effective stress–strain relations were derived for fixed microstructure. In this second part, the evolution of the microstructure is addressed. Differential equations governing the evolution of the microstructural parameters in terms of the applied loading are derived and their integration in time is discussed. Void growth results in a global softening of the stress–strain response of the material. A simple model for the prediction of void coalescence is proposed which can serve to predict the overall ductility of polycrystalline porous materials under the combined action of thermal dilatation and internal pressure in the voids.