Shadowgraphy investigation of laser-induced forward transfer: Front side and back side ablation of the triazene polymer sacrificial layer

Thin films of a photodecomposible triazene polymer are used as sacrificial layer for the micro-deposition of sensitive materials by laser-induced forward transfer. To understand the ablation process of this sacrificial layer, the ultraviolet laser ablation of triazene films was investigated by time-resolved shadowgraphy. Irradiation from the film side shows a complete decomposition into gaseous fragments, while ablation through the substrate causes ejection of a solid flyer of polymer. The occurence of the flyer depends on the film thickness as well as on the applied fluence, and a compact flyer is obtaind when these two parameters are optimized.     

Laser ablation of energetic polymer solutions: effect of viscosity and fluence on the splashing behavior

Laser plasma thrusters are a new kind of propulsion system for small satellites, and work with the thrust created by the laser ablation of a target. Liquid polymer solutions are very promising fuels for such systems, provided that no splashing of the target occurs, because ejection of droplets strongly decreases the performances of the system. We have investigated the nanosecond infrared laser ablation of glycidyl azide polymer solutions containing carbon nanoparticles as absorber. Shadowgraphy imaging revealed two cases, namely splashing regime and solid-like behavior. The transition between both regimes depends on the viscosity of the solution and on the laser fluence, and is explained by the recoil force acting on the target. Appropriate conditions to avoid splashing were identified, showing that this liquid polymer solution is a suitable fuel for laser plasma thrusters.     

Facile Synthesis of Diastereoisomerically and Optically Pure 2‐Substituted Hexahydro‐1H‐pyrrolizin‐3‐ones

We report a short synthetic route that provides optically active 2‐substituted hexahydro‐1H‐pyrrolizin‐3‐ones in four steps from commercially available Boc (tert‐but(oxy)carbonyl))‐protected proline. Diastereoisomers (−)‐ 11 and (−)‐ 12 were assembled from the proline‐derived aldehyde (−)‐ 8 and ylide 9 via a Wittig reaction and subsequent catalytic hydrogenation (Scheme 3). Cleavage of the Boc protecting group under acidic conditions, followed by intramolecular cyclization, afforded the desired hexahydro‐1H‐pyrrolizinones (−)‐ 1 and (+)‐ 13 . Applying the same protocol to ylide 19 afforded hexahydro‐1H‐pyrrolizinones (−)‐ 25 and (−)‐ 26 (Scheme 5). The absolute configuration of the target compounds was determined by a combination of NMR studies (Figs. 1 and 2) and X‐ray crystallographic analysis (Fig. 3).     

Captured and cross-linked palladium nanoparticles

Polystyrene-poly(ethylene glycol) resin-captured cross-linked palladium nanopaticles were prepared via a straightforward route, and their heterogeneous behavior was truly confirmed by various tests. They were applied to aqueous Suzuki cross-coupling reactions with various aryl bromides and recycled up to six times without loss of activity.     

Fe(0)-mediated synthesis of tri- and tetra-substituted olefins from carbonyls: an environmentally friendly alternative to Cr(II)

Fe(0) was investigated as a cost-effective, environmentally friendly alternative to Cr(II) for the olefination of carbonyls by activated polyhalides. In many instances, Fe(0) was equivalent or superior to Cr(II). Notably, Fe(0), but not Cr(II), proved compatible with a wide range of functionality, inter alia, unprotected phenol, aryl nitro, carboxylic acid, and alkyl nitrile. A surprising reversal of stereoselectivity for aldehydes versus ketones was observed using both metals. The resultant alpha-halo-alpha,beta-unsaturated or alpha,beta-unsaturated carboxylic acids, esters, and nitriles are common structural elements in numerous compounds of interest as well as key intermediates in the preparation of other functionality.     

Compression-induced stiffness in the buckling of a one fiber composite

We study the buckling of a one fiber composite whose matrix stiffness is slightly dependent on the compressive force. We show that the equilibrium curves of the system exhibit a limit load when the induced stiffness parameter gets bigger than a threshold. This limit load increases when the stiffness parameter is increasing and it is related to a possible localized path in the post-buckling domain. Such a change in the maximum load may be very desirable from a structural stand point.     

Morphology of MgO smoke crystallites upon etching in wet environment

The etching of MgO smoke in wet conditions – an archetype for aqueous dissolution of oxide crystals – is explored on the basis of transmission electron microscope (TEM) analyses. In pure water with neutral pH, in acid solutions and in moist air, the MgO cubic crystallites show first (1 1 0) truncations of the 〈1 1 0〉 edges and then (1 1 1) cuts at the corners. Criteria are given to characterize (1 1 0) and (1 1 1) cuts on the TEM images. It is shown that (1 1 0) truncations appear independently of the formation of the (1 1 1) cuts and are associated with a stationary state. The picture is fully consistent with the previous suggestion of a “constrained Wulff profile” [9] which explains the formation of (1 1 0) cuts by excluding (1 1 1) facets.     

Tracy–Widom at High Temperature

We investigate the marginal distribution of the bottom eigenvalues of the stochastic Airy operator when the inverse temperature \(\beta \) tends to \(0\) . We prove that the minimal eigenvalue, whose fluctuations are governed by the Tracy–Widom \(\beta \) law, converges weakly, when properly centered and scaled, to the Gumbel distribution. More generally we obtain the convergence in law of the marginal distribution of any eigenvalue with given index \(k\) . Those convergences are obtained after a careful analysis of the explosion times process of the Riccati diffusion associated to the stochastic Airy operator. We show that the empirical measure of the explosion times converges weakly to a Poisson point process using estimates proved in Dumaz and Virág (Ann Inst H Poincaré Probab Statist 49(4):915–933, 2013). We further compute the empirical eigenvalue density of the stochastic Airy ensemble on the macroscopic scale when \(\beta \rightarrow 0\) . As an application, we investigate the maximal eigenvalues statistics of \(\beta _N\) -ensembles when the repulsion parameter \(\beta _N\rightarrow 0\) when \(N\rightarrow +\infty \) . We study the double scaling limit \(N\rightarrow +\infty , \beta _N \rightarrow 0\) and argue with heuristic and numerical arguments that the statistics of the marginal distributions can be deduced following the ideas of Edelman and Sutton (J Stat Phys 127(6):1121–1165, 2007) and Ramírez et al. (J Am Math Soc 24:919–944, 2011) from our later study of the stochastic Airy operator.     

How Can a Hydrophobic MOF be Water‐Unstable? Insight into the Hydration Mechanism of IRMOFs

We report an ab initio molecular dynamics study of the hydration process in a model IRMOF material. At low water content (one molecule per unit cell), water physisorption is observed on the zinc cation but the free?bound equilibrium strongly favors the free state. This is consistent with the hydrophobic nature of the host matrix and its type‐V isotherm observed in a classical Monte Carlo simulation. At higher loading, a water cluster can be formed at the Zn₄O site and this is shown to stabilize the water‐bound state. This structure rapidly transforms into a linker‐displaced state, where water has fully displaced one arm of a linker and which corresponds to the loss of the material’s fully ordered structure. Thus an overall hydrophobic MOF material can also become water unstable, a feature that has not been fully understood until now.