Photothermal displacement spectroscopy: An optical probe for solids and surfaces

We present a sensitive technique for determining the optical and thermal properties of solids, surfaces and thin films. This technique, photothermal displacement Spectroscopy, is based on the detection of the thermal expansion of a sample upon absorption of electromagnetic radiation. The technique is well suited for in situ ultrahigh vacuum studies and for experiments where wide temperature ranges are required. We show that surface and bulk optical absorption can be distinguished and that surface absorptions of αL=10^?6/W of incident power can be measured. The theoretical basis of the signal generation is given, and excellent experimental and theoretical agreement is demonstrated. The implications of our findings to imaging and microscopy are discussed.     

On the Uniqueness for the Spatially Homogeneous Boltzmann Equation with a Strong Angular Singularity

We prove an inequality on the Wasserstein distance with quadratic cost between two solutions of the spatially homogeneous Boltzmann equation without angular cutoff, from which we deduce some uniqueness results. In particular, we obtain a local (in time) well-posedness result in the case of (possibly very) soft potentials. A global well-posedness result is shown for all regularized hard and soft potentials without angular cutoff. Our uniqueness result seems to be the first one applying to a strong angular singularity, except in the special case of Maxwell molecules. Our proof relies on the ideas of Tanaka (Z. Wahrscheinlichkeitstheor. Verwandte. Geb. 46(1):67–105, [1978]) we give a probabilistic interpretation of the Boltzmann equation in terms of a stochastic process. Then we show how to couple two such processes started with two different initial conditions, in such a way that they almost surely remain close to each other.     

Thermosensitive and Switchable Terpyridine‐Functionalized Metallo‐Supramolecular Poly(N‐isopropylacrylamide)

Metallo‐supramolecular polymers offer attractive possibilities to combine the properties of polymers with the characteristics offered by the metal–ligand coordination. Here we present for the first time the combination of metal‐bis(terpyridine) complexes and lower critical solution temperature (LCST) polymers that can be switched by addressing either the thermosensitive polymer or the metal complex. We describe a new strategy for the synthesis of poly(N‐isopropylacrylamide) (PNIPAM) end functionalized with a terpyridine moiety, which is further used for the preparation of Fe^II and Zn^II‐bis(terpyridine PNIPAM). The comparison of the LCST behavior of the uncomplexed ligands and their metal complexes that bear different counter ions is included. Furthermore, the switchability of the synthesized Fe^II system is demonstrated by a decomplexation reaction followed by the characterization of the uncomplexed ligand.

     

Zn7Cu6: a magic cluster of brass?

Density functional theory was applied to a series of 13-atom Zn–Cu alloy clusters. We did a thorough search for the low-energy isomers by global optimization, plus explicit optimization of all homotops of the icosahedron. Structures of copper rich clusters tend to be compact, often icosahedra, whereas zinc rich clusters ( ${{\rm Zn}_8{\rm Cu}_{5}^{+}}$ , Zn₉Cu₄, Zn₁₁Cu₂) have compact copper cores surrounded by an incomplete shell of solvating Zn atoms. The icosahedral structure, low total energy, and large hardness of Zn₇Cu₆ indicate that it has special stability among Zn _x Cu _y clusters. However, Zn₇Cu₆ has many low lying isomers and a small cohesive energy compared to brass, which suggest that it is not stable in a broader sense.     

Effectiveness of the suzuki-miyaura cross-coupling reaction for solid-phase peptide modification

The Suzuki-Miyaura (SM) cross-coupling reaction has recently become one of the most efficient methods for C-C bond construction opening a wide range of opportunities in organic synthesis. This study focused on the evaluation of the use of the SM reaction to modify peptides using a solid-phase synthesis approach, an avenue that was still not investigated intensively. We used as a peptide model [Ala (1,2,3), Leu (8)]Enk linked to a polystyrene support on which it was previously assembled. The aromatic residues Tyr (4) and Phe (7) of [Ala (1,2,3), Leu (8)]Enk were respectively substituted with p-iodo-Phe, and an SM-related strategy was developed. Results indicated that the reaction conditions involving K 3PO 4 or Na 2CO 3 (base), DMF (solvent), Pd(PPh 3) 4 (catalyst), and temperatures ranging from 50 to 80 degrees C during 20 h were found as optimal. Finally applying those optimal conditions, a series of [Ala (1,2,3), Leu (8)]Enk analogs modified at Tyr (4) or Phe (7) positions was synthesized using diverse boronic acid derivatives.     

Desorption/ionization on porous silicon mass spectrometry (DIOS) of model cationized fatty acids

Desorption/ionization on porous silicon (DIOS) is a very useful technique in the case of small molecular weight compounds, compared to the matrix-assisted laser desorption ionization (MALDI). This is because MALDI generates matrix-related ions that overlap with the mass range of interest. The aim of our work was to investigate the suitability of the DIOS technique in the case of fatty acids in negative ion mode. The analysis of the chosen fatty acid models, nonadecanoic acid (C(19)H(38)O(2)) and heneicosanoic acid (C(21)H(42)O(2)), gave rise to the observation of the deprotonated monomeric species and selective cationized multimeric species. This cation selectivity was further elucidated by complementary studies based on the addition of various metals such as Ag(I), Zn(II), Fe(II), and also Cu(II). Specific behavior, depending upon the introduced metal, was highlighted by different redox reaction processes and also metastable decompositions (in PSD mode).     

Synthesis and characterization of poly(4‐alkyl‐4‐methyl‐2‐azetidinone)s

Poly‐β‐amides (nylons 3) were synthesized via the anionic polymerization of a series of 4‐alkyl‐4‐methyl‐2‐azetidinones where the alkyl group is a methyl, ethyl, propyl, butyl, or pentyl. The “non‐assisted” polymerization was conducted under vacuum, in the bulk, at 160°C, using potassium 2‐pyrrolidonate as catalyst, whereas the “assisted” polymerization was carried in dimethylsulfoxide, at room temperature, using N‐acetylpyrrolidinone‐2 as activator but it gave no polymer with a propyl or bulkier side group. Side reactions occur in all cases. X‐ray spectra showed that poly(4‐alkyl‐4‐methyl‐2‐azetidinone)s are amorphous with propyl, butyl, and pentyl groups, and semi‐crystalline with methyl or ethyl substituents. Both semi‐crystalline polyamides exhibit an extended planar zigzag conformation, with a fiber identity period along the c axis of 4.9 Å. Glass transition temperatures, melting temperatures, and/or decomposition temperatures are also reported. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 761–769, 1999     

Majorants andL p norms

It is shown that ifG is an infinite compact abelian group, thenL ^p (G) has the upper majorant property only ifp is even orp=∞. The research for this paper was partially supported by National Research Council of Canada Operating Grant A-4822.     

Backlighter development at the National Ignition Facility (NIF): Zinc to zirconium

K-shell X-ray emission from laser-irradiated planar Zn, Ge, Br, and Zr foils was measured at the National Ignition Facility for laser irradiances in the range of 0.6–9.5 × 10¹⁵ W/cm². The incident laser power had a pre-pulse to enhance the laser-to-X-ray conversion efficiency (CE) of a 2–5 ns constant-intensity pulse used as the main laser drive. The measured CE into the 8–16 keV energy band ranged from 0.43% to 2%, while the measured CE into the He-like resonance 1s2–1s2p(1P) and intercombination 1s2–1s2p(3P) transitions, as well as from their 1s2(2s,2p)l–1s2p(2s,2p)l satellite transitions for l = 1, 2, 3, corresponding to the Li-, Be-, and B-like resonances, respectively, ranged from 0.3% to 1.5%. Absolute and relative CE measurements are consistent with X-ray energy scaling of (hν)^?3 to (hν)^?5, where hν is the X-ray energy. The temporal evolution of the broadband X-ray power was similar to the main laser drive for ablation plasmas having a critical density surface.