In situ hydrodynamic lateral force calibration of AFM colloidal probes

Lateral force microscopy (LFM) is an application of atomic force microscopy (AFM) to sense lateral forces applied to the AFM probe tip. Recent advances in tissue engineering and functional biomaterials have shown a need for the surface characterization of their material and biochemical properties under the application of lateral forces. LFM equipped with colloidal probes of well-defined tip geometries has been a natural fit to address these needs but has remained limited to provide primarily qualitative results. For quantitative measurements, LFM requires the successful determination of the lateral force or torque conversion factor of the probe. Usually, force calibration results obtained in air are used for force measurements in liquids, but refractive index differences between air and liquids induce changes in the conversion factor. Furthermore, in the case of biochemically functionalized tips, damage can occur during calibration because tip-surface contact is inevitable in most calibration methods. Therefore, a nondestructive in situ lateral force calibration is desirable for LFM applications in liquids. Here we present an in situ hydrodynamic lateral force calibration method for AFM colloidal probes. In this method, the laterally scanned substrate surface generated a creeping Couette flow, which deformed the probe under torsion. The spherical geometry of the tip enabled the calculation of tip drag forces, and the lateral torque conversion factor was calibrated from the lateral voltage change and estimated torque. Comparisons with lateral force calibrations performed in air show that the hydrodynamic lateral force calibration method enables quantitative lateral force measurements in liquid using colloidal probes.     

Design of cross-linked semicrystalline poly(ε-caprolactone)-based networks with one-way and two-way shape-memory properties through Diels-Alder reactions

Cross‐linked poly(ε‐caprolactone) (PCL)‐based polyesterurethane (PUR) systems have been synthesized through Diels–Alder reactions by reactive extrusion. The Diels–Alder and retro‐Diels–Alder reactions proved to be useful for enhancing the molecular motion of PCL‐based systems, and therefore their crystallization ability, in the design of cross‐linked semicrystalline polymers with one‐way and two‐way shape‐memory properties. Successive reactions between α,ω‐diol PCL (PCL₂), furfuryl alcohol, and methylene diphenyl 4,4′‐diisocyanate straightforwardly afforded the α,ω‐furfuryl PCL‐based PUR systems, and subsequent Diels–Alder reactions with N,N‐phenylenedimaleimide afforded the thermoreversible cycloadducts. The cross‐linking density could be modulated by partially replacing PCL‐diol with PCL‐tetraol. Interestingly, the resulting PUR systems proved to be semicrystalline cross‐linked polymers, the melting temperature of which (close to 45 °C) represented the switching temperature for their shape‐memory properties. Qualitative and quantitative measurements demonstrated that these PUR systems exhibited one‐way and two‐way shape‐memory properties depending on their cross‐linking density.     

Polyethylenes bearing a terminal porphyrin group

An α-[Cu(II)-porphyrin]-polyethylene was synthesized for the first time using copper catalyzed 1,3-dipolar azide-alkyne Huisgen cycloaddition yielding highly colored moiety-substituted polyethylene.     

Statistical properties of derivatives: A journey in term structures

This article presents an empirical study of 13 derivative markets for commodities and financial assets. The study goes beyond statistical analysis by including the maturity as a variable for the daily returns of futures contracts from 1998 to 2010, and for delivery dates up to 120 months. We observe that the mean and variance of the commodities follow a scaling behavior in the maturity dimension with an exponent characteristic of the Samuelson effect. The comparison between the tails of the probability distribution according to the expiration dates shows that there is a segmentation in the fat tails exponent term structure above the Lévy stable region. Finally, we compute the average tail exponent for each maturity, and we observe two regimes of extreme events for derivative markets, reminiscent of a phase diagram with a sharp transition at the 18th delivery month.     

The Charging of Micellar Nanoparticles in Electrospray Ionization

Charging of nanoparticles through electrospray has scarcely been explored. Spherical nanometer‐sized amphiphilic block copolymer nanoparticles with diameters ranging from ～65 to ～150 nm were electrosprayed and analysed by charge detection spectrometry. Herein, we explore the charging of these micellar nano‐objects by conducting a thorough study in different solvents, including pure water, and upon the addition of “supercharging” agents. The charge (z) of micellar nanoparticles electrosprayed from water solution is compared to the Rayleigh’s limiting charge (z_R) of a charged water droplet of the same dimensions. An average ratio (z/z_R) of 0.6–0.65 is observed for the micellar macro‐ions, supporting the charge residue mechanism, where the number of charges available to the micellar macro‐ion is limited by the number of charges on the nanodroplet, which is a function of the surface tension of the solvent. Also we show the possibility of increasing the charging of micellar nanoparticles in the negative mode by adding organic bases (in particular piperidine) to water/methanol solutions.     

Carleman estimates for semi-discrete parabolic operators and application to the controllability of semi-linear semi-discrete parabolic equations

In arbitrary dimension, in the discrete setting of finite-differences we prove a Carleman estimate for a semi-discrete parabolic operator, in which the large parameter is connected to the mesh size. This estimate is applied for the derivation of a (relaxed) observability estimate, that yield some controlability results for semi-linear semi-discrete parabolic equations. Sub-linear and super-linear cases are considered.     

Dopant profiling in silicon nanowires measured by scanning capacitance microscopy

Silicon nanowires (SiNWs) with axial doping junctions were synthesized via the Au‐catalyzed vapor–liquid–solid growth method with the use of HCl. In this work, dopant profiling from three axially doped SiNWs with p–i, p–n and n–i–p junctions were investigated using both scanning electron microscopy (SEM) and scanning capacitance microscopy (SCM). It turns out that observed doping contrasts in SEM are also affected by the surface roughness and sample charging. In contrast, SCM allows us to delineate with sub‐10 nm resolution the electrical junctions and provides a relative value of the doping concentration in each segment of the NW. SCM clearly evidences the expected doping regions within these SiNWs thanks to the addition of HCl during the growth that strongly prevents shell overgrowth. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

A mild and efficient synthesis of new pentafluorosulfanyl-substituted electron-deficient alkenes and allylsilanes

A series of pentafluorosulfanyl-substituted acrylic esters and amides have been synthesized in moderate to good yields from 3-pentafluorosulfanyl-prop-2-enol employing a chromic oxidation and subsequent coupling reaction. New pentafluorosulfanyl-substituted allylsilanes were also obtained from a SF₅-Cl addition on allylsilanes followed by a β-elimination reaction.     

Thermotropic Luminescent Clustomesogen Showing a Nematic Phase: A Combination of Experimental and Molecular Simulation Studies

Octahedral Mo₆ nanoclusters are functionalized with two organic ligands containing cyanobiphenyl (CB) units, giving luminescent hybrid liquid crystals (LC). Although the mesogenic density around the bulky inorganic core is constant, the two hybrids show different LC properties. Interestingly, one of them shows a nematic phase, which is particularly rare for this kind of supermolecular system. This surprising result is explained by using large‐scale molecular dynamic simulations.     

Core–Shell Nanoreactors for Efficient Aqueous Biphasic Catalysis

Water‐borne phosphine‐functionalized core‐cross‐linked micelles ( CCM ) consisting of a hydrophobic core and a hydrophilic shell were obtained as stable latexes by reversible addition–fragmentation chain transfer (RAFT) in water in a one‐pot, three‐step process. Initial homogeneous aqueous‐phase copolymerization of methacrylic acid (MAA) and poly(ethylene oxide) methyl ether methacrylate (PEOMA) is followed by copolymerization of styrene (S) and 4‐diphenylphosphinostyrene (DPPS), yielding P(MAA‐co‐PEOMA)‐b‐P(S‐co‐DPPS) amphiphilic block copolymer micelles ( M ) by polymerization‐induced self‐assembly (PISA), and final micellar cross‐linking with a mixture of S and diethylene glycol dimethacrylate. The CCM were characterized by dynamic light scattering and NMR spectroscopy to evaluate size, dispersity, stability, and the swelling ability of various organic substrates. Coordination of [Rh(acac)(CO)₂] (acac=acetylacetonate) to the core‐confined phosphine groups was rapid and quantitative. The CCM and M latexes were then used, in combination with [Rh(acac)(CO)₂], to catalyze the aqueous biphasic hydroformylation of 1‐octene, in which they showed high activity, recyclability, protection of the activated Rh center by the polymer scaffold, and low Rh leaching. The CCM latex gave slightly lower catalytic activity but significantly less Rh leaching than the M latex. A control experiment conducted in the presence of the sulfoxantphos ligand pointed to the action of the CCM as catalytic nanoreactors with substrate and product transport into and out of the polymer core, rather than as a surfactant in interfacial catalysis.