Cycloaddition reaction of quadricyclane and fluoroolefins

Reaction of quadricyclane (1) with fluoroolefins of different structure results in stereoselective formation of polyfluorinated exo-tricyclo[4.2.1.0^2,5]non-7-enes. The reaction of a mixture of trans/cis CF₃CFCFCF₃ with 1 is stereoselective and the resulting cycloadducts 7a, b preserve the original alkene stereochemistry. The relative rate constants of cycloaddition of a series of fluoroolefins to 1 under pseudo first-order conditions measured by kinetic NMR at 109 °C provide a kinetic scale of reactivities of the fluoroolefins in this reaction.These relative rate constants correlate well with the number of fluoroalkyl groups connected to the double bond, reaching a maximum for the tri-substituted olefin: CF₃CFCF₂:CF₃CFCFCF₃:(CF₃)₂CC(CF₃)₂:(CF₃)₂CCFC₂F₅ = 1:1.2-1.9:4:138.     

Mass transfer due to cavitation microstreaming

In this paper the influence of the microstreaming, which occurs when a gas bubble vibrates in a viscous liquid, on the mass transfer across the liquid-gas interface, is considered. A systematic theory is developed using results obtained by Davidson and Riley for steady streaming. Particular attention is devoted to two special cases.     

In-beam study of 144Gd

A level scheme of ¹⁴⁴Gd has been established using the ¹⁴⁴Sm(α, 4nγ) reaction and in-beam spectroscopy methods. Excitation functions, γ-ray angular distributions, γ-γ coincidence spectra, γ-spectra time related to the cyclotron beam bursts and conversion coefficients for the delayed transitions have been measured.The level scheme comprises 11 levels with spins up to I = 12. Two isomers, a 13 ± 2 ns, 7^? state at 2471.4 keV and a 145 ± 30 ns, 10⁺ state at 3433.0 keV have been observed. The former has similar excitation energy as the 7^? isomers in ¹⁴²Sm, ¹⁴⁰Nd and ¹³⁸Ce and it may arise from the $\text{{ν}\text{d}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}{}^{\mathrm{?1}}\text{× ν}\text{h}{}_{\mathrm{<mtext>11</mtext><mtext>2</mtext>}}{}^{\mathrm{?1}}\text{}}$ configuration although its lifetime seems to indicate some degree of collectivity. The 10⁺ state has a similar excitation energy as the 10⁺ isomer found in ¹³⁸Ce and it may arise from the dominant $\text{ν}\text{h}{}_{\mathrm{<mtext>11</mtext><mtext>2</mtext>}}{}^{\mathrm{?2}}$ configuration. Below the 10⁺ isomer in ¹⁴⁴Gd only two excited states have positive parity; the hitherto known first 2⁺ and 4⁺ states. The 11⁺ and 12⁺ states must include four-particle configurations or they have to be of collective nature. The latter possibility is supported by the considerable E2/M1 mixture (≈ 20 %) observed for the 11⁺ to 10⁺ transition. An analysis of the systematics of ground band levels in the N = 80 isotones shows the same gradual behavior between the two VMI solutions previously found for the Te isotopes.     

"Nanocasting": using SBA-15 silicas as hard templates to obtain ultrasmall monodispersed gamma-Fe2O3 nanoparticles

This work describes the use of mesoporous SBA-15 silicas as hard templates for the size-controlled synthesis of oxide nanoparticles, with the pores acting as nanoscale reactors. This fundamental work is mainly aimed at understanding unresolved issues concerning the occurrence and size dependence of phase transitions in oxide nanocrystals. Aqueous solutions of Fe(NO3)3*9H2O are deposited inside the pores of SBA-15 silicas with mesopore diameters of 4.3, 6.6, and 9.5 nm. By calcination, the nitrate salt transforms into FeOx oxides. The XRD peaks of nanocrystals are broad and overlapping, resulting in ambiguities attributed to a given allotropic variety of Fe2O3 (alpha, epsilon, or gamma) or Fe3O4. The association of XRD, SAED, and Raman information is necessary to solve these ambiguities. The metastable gamma-Fe2O3 variety is selectively formed at low Fe/Si atomic ratio (ca. 0.20) and when a low calcination temperature is used (773 or 873 K followed by quenching to room temperature once the targeted temperature is reached). The small size dispersion of the patterned nanoparticles, suggested on a local scale by TEM, is confirmed statistically by magnetic measurements. The nanoparticles have a superparamagnetic behavior around room temperature. Their magnetic moments (from 220 to 370 mB), their sizes (from 4.0 to 4.8 nm), and their blocking temperatures (from 36 to 58 K) increase with the silica template mesopore diameter. Their magnetic properties are compared to those of standard gamma-Fe2O3 nanoparticles of similar size, obtained by coprecipitation in water and stabilized by a citrate coating.     

A high power hybrid mid-IR laser source

An efficient hybrid mid-IR laser system comprising a thulium fibre laser, Ho:YAG solid state laser and a zinc germanium phosphide optical parametric oscillator is presented. A 790 nm diode pumped 1908 nm thulium fibre laser operating at 30 W pumps an RTP q-switched Ho:YAG laser emitting 17 W at 40 kHz and 2090 nm. The zinc germanium phosphide optical parametric oscillator efficiently converts this into the 3-5 μm region producing 10.1 W with 59% optical conversion efficiency and an M² = 1.5.     

Decay of quantum correlations in atom optics billiards with chaotic and mixed dynamics

We perform echo spectroscopy on ultracold atoms in atom-optics billiards to study their quantum dynamics. The detuning of the trapping laser is used to change the "perturbation", which causes a decay in the echo coherence. Two different regimes are observed: first, a perturbative regime in which the decay of echo coherence is nonmonotonic and partial revivals of coherence are observed in contrast with the predictions of random matrix theory. These revivals are more pronounced in traps with mixed dynamics as compared to traps where the dynamics is fully chaotic. Next, for stronger perturbations, the decay becomes monotonic and independent of the strength of the perturbation. In this regime no clear distinction can be made between chaotic traps and traps with mixed dynamics.