Carbon dioxide flow boiling in a single microchannel - Part II: Heat transfer

Flow boiling heat transfer coefficients of CO₂ have been measured in a single microchannel. Experiments were carried out in a horizontal stainless steel tube of 0.529 mm inner diameter, for three temperatures (−10, −5 and 0 °C), with the mass flux ranging from 200 to 1200 kg/m² s and the heat flux varying from 10 to 30 kW/m². The investigation covered qualities from zero to the dryout inception, i.e. pre-dryout conditions. Compared to larger microchannels and positive temperatures, a higher contribution of convective boiling was found, with a larger heat transfer coefficient than for pure nucleate boiling. Mainly two heat transfer regimes were found, depending on the boiling number (Bo). For Bo > 1.1 × 10⁻⁴, the heat transfer coefficient was highly dependent on the heat flux and moderately influenced by the quality and the mass flux. For Bo < 1.1 × 10⁻⁴, the heat transfer coefficient was hardly affected by the heat flux but strongly influenced by the quality and the mass flux. In addition, dryout results were reported. The effect of the mass flux on the dryout inception quality was found to be highly dependent on the heat flux and the saturation temperature.     

Highly stereocontrolled and regiocontrolled syntheses of 2,3,4-trisubstituted alkanoates and lactones

New chlorodiols (±)-3 and (±)-5 are densely functionalized and versatile synthons. They are converted in one step on a gram scale into 2-chlorolactones (±)-6 and (±)-7 and into 4-hydroxy glycidate esters (±)-9 and (±)-10. The 4-hydroxy glycidate esters (±)-9 and (±)-10 are converted stereospecifically and regiospecifically into oxazolines (±)-13 and (±)-14 and into cyclic carbamates (±)-18-(±)-20. The 4-hydroxy glycidate ester (±)-10 undergoes stereocontrolled and regiocontrolled epoxide opening by sodium azide to form the 2-azido-3,4-dihydroxy alkanoate (±)-21. Finally, chlorodiol (±)-5 reacts stereospecifically with silver triflate to form the 2,3-dihydroxyfuranone (±)-26.     

Systematic synthesis of inhibitors of the two first enzymes of the bacterial heptose biosynthetic pathway: towards antivirulence molecules targeting lipopolysaccharide biosynthesis

L-Heptoses (L-glycero-D-manno-heptopyranoses) are constituents of the inner core of lipolysaccharide (LPS), a molecule playing key roles in the mortality of many infectious diseases as well as in the virulence of many human pathogens. The inhibition of the first enzymes of the bacterial heptose biosynthetic pathway is an almost unexplored field to date although it appears to be a very novel way for the development of antivirulence drugs. We report the synthesis of a series of D-glycero-D-manno-heptopyranose 7-phosphate (H7P) analogues and their inhibition properties against the isomerase GmhA and the the kinase HldE, the two first enzymes of the bacterial heptose biosynthetic pathway. The heptose structures have been modified at the 1-, 2-, 6- and 7-positions to probe the importance of the key structural features of H7P that allow a tight binding to the target enzymes; H7P being the product of GmhA and the substrate of HldE, the second objective was to find structures that could simultaneously inhibit both enzymes. We found that GmhA and HldE were extremely sensitive to structural modifications at the 6- and 7- positions of the heptose scaffold. To our surprise, the epimeric analogue of H7P displaying a D-glucopyranose configuration was found to be the best inhibitor of both enzymes but also the only molecule of this series that could inhibit GmhA (IC(50)=34 μM) and HldE (IC(50)=9.4 μM) in the low micromolar range. Noteworthy, this study describes the first inhibitors of GmhA ever reported, and paves the way to the design of a second generation of molecules targeting the bacterial virulence.     

A ruthenium catalyst yielding crosslinked polyethylene

A ruthenium phosphane aryl sulfonate was found to be an efficient catalyst for the polymerization of ethene. Surprisingly, the resulting polyethylene is crosslinked.     

Formation and evolution of intense, post-filamentation, ionization-free low divergence beams

The mechanisms related to the formation and propagation of post-filamentation intense light channels were rigorously investigated experimentally and numerically. It was found that they originate from a hot spot formed by diffraction of the pulse energy reservoir onto the plasma. Once the hot spot was formed, a channel with intensity estimated at 0.5 TW/cm² could maintain its diameter over several tens of meters such that air was not ionized, but the self-focusing produced was sufficiently high to balance linear diffraction. This propagation regime is of high interest to propagate high intensity laser pulses with limited losses.     

Optical analogue of the spin Hall effect in a photonic cavity

We observe anisotropy in the polarization flux generated in a GaAs/AlAs photonic cavity by optical illumination, equivalent to spin currents in strongly coupled microcavities. Polarization rotation of the scattered photons around the Rayleigh ring is due to the TE-TM splitting of the cavity mode. Resolving the circular polarization components of the transmission reveals a separation of the polarization flux in momentum space. These observations constitute the optical analogue of the spin Hall effect.     

Enantiopure Isoindolinones through Viedma Ripening

Here we demonstrate that deracemization of isoindolinones using Viedma ripening is possible starting from a racemic mixture of conglomerate crystals. Crystals of the enantiopure isoindolinones lose their chiral identity upon dissolution even without the need for a catalyst. This enabled complete deracemization of the reported isoindolinones without a catalyst.     

Stereoselective Synthesis of Iminosugar-C-Glycosides through Addition of Organometallic Reagents to N-tert-Butanesulfinyl Glycosylamines: A Comprehensive Study

A comprehensive study of the preparation and reactivity of N-tert-butanesulfinyl glycosylamines with simple Grignard and organo lithium reagents in batch vs. continuous flow chemistry is reported. As they readily react as latent imine equivalents with a variety of carbon nucleophiles, these carbohydrate derivatives constitute very useful precursors for the diastereoselective synthesis of bioactive compounds such as iminosugar-C-glycosides. A hybrid protocol, involving the addition of benzylmagnesium chloride to a (S_R)-arabinofuranosylamine substrate in flow, at room temperature, combined with a cyclization protocol in batch is also described for the first time. Of note, this semi-continuous flow process shortens the synthesis of imino-C-glycoside scaffolds to a single workday.     

Production of Dihydrogen Using Ammonia Borane as Reagent and Pyrazole as Catalyst

Theoretical chemistry (DLPNO-CCSD(T)/def2-TZVP//M06-2x/aug-cc-pVDZ) was used to design a system based on ammonia boranes catalyzed by pyrazoles with the aim of producing dihydrogen, nowadays of high interest as clean fuel. The reactivity of ammonia borane and cyclotriborazane were investigated, including catalytic activation through 1H-pyrazole, 4-methoxy-1H-pyrazole, and 4-nitro-1H-pyrazole. The results point toward a catalytic cycle by which, at the same time, ammonia borane can initially store and then, through catalysis, produce dihydrogen and amino borane. Subsequently, amino borane can trimerize to form cyclotriborazane that, in presence of the same catalyst, can also produce dihydrogen. This study proposes therefore a consistent progress in using environmentally sustainable (metal free) catalysts to efficiently extract dihydrogen from small B−N bonded molecules.