X‐ray photoelectron spectroscopic chemical state quantification of mixed nickel metal,oxide and hydroxide systems

Quantitative chemical state X‐ray photoelectron spectroscopic analysis of mixed nickel metal, oxide, hydroxide and oxyhydroxide systems is challenging due to the complexity of the Ni 2p peak shapes resulting from multiplet splitting, shake‐up and plasmon loss structures. Quantification of mixed nickel chemical states and the qualitative determination of low concentrations of Ni(III) species are demonstrated via an approach based on standard spectra from quality reference samples (Ni, NiO, Ni(OH)₂, NiOOH), subtraction of these spectra, and data analysis that integrates information from the Ni 2p spectrum and the O 1s spectra. Quantification of a commercial nickel powder and a thin nickel oxide film grown at 1‐Torr O₂ and 300 °C for 20 min is demonstrated. The effect of uncertain relative sensitivity factors (e.g. Ni 2.67 ± 0.54) is discussed, as is the depth of measurement for thin film analysis based on calculated inelastic mean free paths. Copyright © 2009 John Wiley & Sons, Ltd.     

Flashlamp-pumped laser performance of LiCaAIF6:Cr3+

The results of flashlamp pumping of the LiCaAIF₆:Cr³⁺ (Cr:LiCAF) laser crystal are reported. We have so far obtained slope efficiencies as high as 1.55% in a close-coupled, diffusely reflecting cavity. Based on the measured insertion loss of the presently available material, we predict that an efficiency of about 4% will be obtained when low-loss material becomes available. This extrapolated efficiency is comparable with the performance of a high-quality alexandrite laser rod in the same apparatus.     

Total synthesis and antimalarial activity of symplostatin 4

The first total synthesis of symplostatin 4, a marine cyanobacterium-derived natural product, is described. Notable features of the route include the efficient preparation of three key fragments and final assembly to the natural product via sequential imide and amide couplings. Symplostatin 4 was also demonstrated to possess significant antimalarial activity (ED(50) of 74 nM against Plasmodium falciparum, strain 3D7).     

N,N′‐Diethyl‐4‐nitrobenzene‐1,3‐diamine, 2,6‐bis(ethylamino)‐3‐nitrobenzonitrile and bis(4‐ethylamino‐3‐nitrophenyl) sulfone

N,N′‐Diethyl‐4‐nitrobenzene‐1,3‐diamine, C₁₀H₁₅N₃O₂, (I), crystallizes with two independent molecules in the asymmetric unit, both of which are nearly planar. The molecules differ in the conformation of the ethylamine group trans to the nitro group. Both molecules contain intramolecular N—H...O hydrogen bonds between the adjacent amine and nitro groups and are linked into one‐dimensional chains by intermolecular N—H...O hydrogen bonds. The chains are organized in layers parallel to (101) with separations of ca 3.4 Å between adjacent sheets. The packing is quite different from what was observed in isomeric 1,3‐bis(ethylamino)‐2‐nitrobenzene. 2,6‐Bis(ethylamino)‐3‐nitrobenzonitrile, C₁₁H₁₄N₄O₂, (II), differs from (I) only in the presence of the nitrile functionality between the two ethylamine groups. Compound (II) crystallizes with one unique molecule in the asymmetric unit. In contrast with (I), one of the ethylamine groups, which is disordered over two sites with occupancies of 0.75 and 0.25, is positioned so that the methyl group is directed out of the plane of the ring by approximately 85°. This ethylamine group forms an intramolecular N—H...O hydrogen bond with the adjacent nitro group. The packing in (II) is very different from that in (I). Molecules of (II) are linked by both intermolecular amine–nitro N—H...O and amine–nitrile N—H...N hydrogen bonds into a two‐dimensional network in the (10) plane. Alternating molecules are approximately orthogonal to one another, indicating that π–π interactions are not a significant factor in the packing. Bis(4‐ethylamino‐3‐nitrophenyl) sulfone, C₁₆H₁₈N₄O₆S, (III), contains the same ortho nitro/ethylamine pairing as in (I), with the position para to the nitro group occupied by the sulfone instead of a second ethylamine group. Each 4‐ethylamino‐3‐nitrobenzene moiety is nearly planar and contains the typical intramolecular N—H...O hydrogen bond. Due to the tetrahedral geometry about the S atom, the molecules of (III) adopt an overall V shape. There are no intermolecular amine–nitro hydrogen bonds. Rather, each amine H atom has a long (H...O ca 2.8 Å) interaction with one of the sulfone O atoms. Molecules of (III) are thus linked by amine–sulfone N—H...O hydrogen bonds into zigzag double chains running along [001]. Taken together, these structures demonstrate that small changes in the functionalization of ethylamine–nitroarenes cause significant differences in the intermolecular interactions and packing.     

Effect of temperature on rectified diffusion during ultrasound-induced heating

Experimental observations of delayed-onset cavitation during ultrasound insonation have been suggested as being caused by a change in the size distribution of the bubble population due to rectified diffusion. To investigate this hypothesis, a single bubble model is used here to explore the effect of heating and the subsequent elevated temperatures on the rectified diffusion process. Numerical solution of the model, which includes the temperature dependences of seven relevant physical parameters, allows quantification of the change in the pressure threshold for rectified diffusion, as well as the importance of the bulk liquid saturation concentration in determining bubble evolution. Although elevated temperatures and liquid supersaturation reduce the rectified diffusion threshold, it remains coincident with the inertial cavitation thresholds at submicron bubble sizes at all temperatures. This observation suggests that changes in the nucleation environment, rather than bubble growth due to rectified diffusion, is a more likely cause of delayed-onset cavitation events.     

Double k-sets in symplectic generalized quadrangles

In classical projective geometry, a double six of lines consists of 12 lines ? ₁, ? ₂, . . . , ? ₆, m ₁, m ₂, . . . , m ₆ such that the ? _i are pairwise skew, the m _i are pairwise skew, and ? _i meets m _j if and only if i ≠ j. In the 1960s Hirschfeld studied this configuration in finite projective spaces PG(3, q) showing they exist for almost all values of q, with a couple of exceptions when q is too small. We will be considering double-k sets in the symplectic geometry W(q), which is constructed from PG(3, q) using an alternating bilinear form. This geometry is an example of a generalized quadrangle, which means it has the nice property that if we take any line ? and any point P not on ?, then there is exactly one line through P meeting ?. We will discuss all of this in detail, including all of the basic definitions needed to understand the problem, and give a result classifying which values of k and q allow us to construct a double k-set of lines in W(q).     

Highly efficient inelastic four-wave mixing using dual induced transparency and coherently prepared states

We investigate a life time broadened and coherently prepared five-state system for multi-wave mixing processes. We show that very efficient wave mixing occurs, producing an unconventional mixing wave that has the characteristics of both conventional four-wave mixing (FWM) and stimulated hyper-Raman (SHR) emission. In addition, we show interesting multiple simultaneous multi-photon interference effects at large propagation distances and demonstrate more than 10 orders of magnitude suppression of populations of the probe wave terminal state and the near three-photon resonance mixing wave generating state. These new type of multi-photon interference based induced transparency effects, which are critically dependent on two distinctive relaxation processes involving both an external supplied and an internally generated fields, are fundamentally different from the conventional three-state electromagnetically induced transparency effect which does not depend on propagation. As a consequence, both the probe and the wave-mixing field to propagate nearly free of absorption and distortions in a highly dispersive medium.     

Detection of incipient gear failures using statistical techniques

Gears are important components in most power transmission mechanisms.Failures of gears can cause heavy losses in industry. Conditionmonitoring and fault diagnosis of gears is therefore importantto improve safety and reliability of gearbox operations andreduce losses caused by gear failures. This research proposesa new diagnostic approach based on the statistical analysisof data. It investigates the use of Principal Components Analysis(PCA) to detect growing local faults in a two-stage industrialhelical gearbox. In this research, the vibration signal is usedto monitor fault conditions and a broken tooth is simulatedas a local fault. Since the early detection of faults is a challenge,small fault conditions were tested first as well as severe faultconditions. In order to examine the ability of the PCA to detectfault conditions, first the PCA-based model was created fornormal operating conditions. Any unexpected event such as afault condition causes a significant deviation from the PCAmodel, which is obtained from the normal condition data of thegearbox. The Square Prediction Error (SPE) was calculated todetect the fault conditions. When the vibration signal fromthe gearbox is representative of normal operation, the valueof the SPE shows very little fluctuation and remains under acertain threshold value. However, in the presence of the faultthe SPE fluctuates considerably beyond the threshold value.It is shown that the PCA-based statistical approach cannot onlybe used to detect severe fault conditions, but that it alsoreveals small growing fault conditions at very early stage.The technique also provides information about the state of thefault such as the location of the fault as well as its severity. Received 5 March 2001. Revised 12 December 2001. Accepted 17 January 2002.