Photopolymerization studies of alkyl and aryl ester derivatives of ethyl α-hydroxymethylacrylate

Several new benzoate ester derivatives of ethyl α-hydroxymethylacrylate were synthesized using phase transfer catalysis and found to display unexpectedly rapid photopolymerization; i.e., from 2 to 8 times faster than MMA. New derivatives described here include the 4-fluoro-, 4-trifluoromethyl-, 4-methyl-, 2-hydroxy-, 4-nitro-, 4-methoxy-, 4-cyano-, and 3,4,5-trimethoxybenzoate esters along with the parent benzoate ester. Relative reactivities of these monomers in photopolymerizations were compared with those of the nonaromatic formate, acetate, hexanoate, and stearate derivatives. Reactivities of the nonaromatic ester derivatives increased with the length of the side chain while for the more reactive aromatic esters, rates increased in the order 4-methyl-, 4-fluoro- and benzoate < 4-trifluoromethyl- and 2-hydroxy- < 4-cyano- < 4-methoxy- < 3,4,5-trimethoxybenzoate. T_gs of the benzoate polymers ranged from 125°C for the 4-fluoro to 163°C for the 4-cyanobenzoate while those of the alkyl ester derivatives ranged from 15 to 78°C. Number average molecular weights of photoinitiated polymers (ca 10,000–20,000) were lower than those found for bulk and solution polymers (20,000—708,000) consistent with higher radical concentrations from photoinitiation. These materials greatly expand the number of candidates available for rapid photocure in thin film and coating applications, especially because their physical properties are those of linear rather than highly crosslinked structures formed from multifunctional systems. © 1996 John Wiley & Sons, Inc.     

Sharp bounds for decompositions of graphs into complete r-partite subgraphs

If G is a graph on n vertices and r ≥ 2, we let m_r(G) denote the minimum number of complete multipartite subgraphs, with r or fewer parts, needed to partition the edge set, E(G). In determining m_r(G), we may assume that no two vertices of G have the same neighbor set. For such reducedgraphs G, we prove that m_r(G) ≥ log₂ (n + r − 1)/r. Furthermore, for each k ≥ 0 and r ≥ 2, there is a unique reduced graph G = G(r, k) with m_r(G) = k for which equality holds. We conclude with a short proof of the known eigenvalue bound m_r(G) ≥ max{n₊ (G, n₋(G)/(r − 1)}, and show that equality holds if G = G(r, k). © 1996 John Wiley & Sons, Inc.     

Charge‐Induced Unzipping of Isolated Proteins to a Defined Secondary Structure

Here we present a combined experimental and theoretical study on the secondary structure of isolated proteins as a function of charge state. In infrared spectra of the proteins ubiquitin and cytochrome c, amide I (C=O stretch) and amide II (N–H bend) bands can be found at positions that are typical for condensed‐phase proteins. For high charge states a new band appears, substantially red‐shifted from the amide II band observed at lower charge states. The observations are interpreted in terms of Coulomb‐driven transitions in secondary structures from mostly helical to extended C₅‐type hydrogen‐bonded structures. Support for this interpretation comes from simple energy considerations as well as from quantum chemical calculations on model peptides. This transition in secondary structure is most likely universal for isolated proteins that occur in mass spectrometric experiments.     

Spontaneous macroscopic spin polarization in independent spinor Bose-Einstein condensates

We present experimental evidence for the spontaneous formation of a macroscopic spin polarization in overlapping regions of two independent Bose-Einstein condensates produced in different hyperfine states of 87Rb. The condensates are independent in the sense that we do not explicitly introduce a relative phase between them. A single "spin-tip" pulse maps the transverse spin polarization into longitudinal spin polarization, and the atomic density distributions are measured with a Stern-Gerlach imaging method. The resulting matter-wave interference patterns are anticorrelated.     

Efficient 1645-nm Er:YAG laser

We report a resonantly fiber-laser-pumped Er:YAG laser operating at the eye-safe wavelength of 1645 nm, exhibiting 43% optical efficiency and 54% incident slope efficiency and emitting 7-W average power when repetitively Q switched at 10 kHz. To our knowledge, this is the best performance (conversion efficiency and average power) obtained from a bulk solid-state Q-switched erbium laser. At a 1.1-kHz pulse repetition frequency the laser produces 3.4-mJ pulses with a corresponding peak power of 162 kW. Frequency doubling to produce 822.5-nm, 4.7-kW pulses at 10 kHz was performed to demonstrate the laser's utility.     

Imaging performance of an isotropic negative dielectric constant slab

The influence of material and thickness on the subwavelength imaging performance of a negative dielectric constant slab is studied. Resonance in the plane-wave transfer function produces a high spatial frequency ripple that could be useful in fabricating periodic structures. A cost function based on the plane-wave transfer function provides a useful metric to evaluate the planar slab lens performance, and using this, the optimal slab dielectric constant can be determined.     

Entanglement sudden death in qubit-qutrit systems

We demonstrate the existence of entanglement sudden death (ESD), the complete loss of entanglement in finite time, in qubit-qutrit systems. In particular, ESD is shown to occur in such systems initially prepared in a one-parameter class of entangled mixed states and then subjected to local dephasing noise. Together with previous results, this proves the existence of ESD for some states in all quantum systems for which rigorously defined mixed-state entanglement measures have been identified. We conjecture that ESD exists in all quantum systems prepared in appropriate bipartite states.     

Nanoscopic Porous Iridium/Iridium Dioxide Superstructures (15 nm): Synthesis and Thermal Conversion by In Situ Transmission Electron Microscopy

Porous particle superstructures of about 15 nm diameter, consisting of ultrasmall nanoparticles of iridium and iridium dioxide, are prepared through the reduction of sodium hexachloridoiridate(+IV) with sodium citrate/sodium borohydride in water. The water-dispersible porous particles contain about 20 wt % poly(N-vinylpyrrolidone) (PVP), which was added for colloidal stabilization. High-resolution transmission electron microscopy confirms the presence of both iridium and iridium dioxide primary particles (1–2 nm) in each porous superstructure. The internal porosity (≈58 vol%) is demonstrated by electron tomography. In situ transmission electron microscopy up to 1000 °C under oxygen, nitrogen, argon/hydrogen (all at 1 bar), and vacuum shows that the porous particles undergo sintering and subsequent compaction upon heating, a process that starts at around 250 °C and is completed at around 800 °C. Finally, well-crystalline iridium dioxide is obtained under all four environments. The catalytic activity of the as-prepared porous superstructures in electrochemical water splitting (oxygen evolution reaction; OER) is reduced considerably upon heating owing to sintering of the pores and loss of internal surface area.