Thermal and chemical nanofractal relaxation

We studied shape relaxation of nano-fractal islands, during annealing, after their growth from antimony cluster deposition on graphite surface. Annealing at 180^°C shows evidence of an increase of the fractal branch width with time followed by branch fragmentation, without changing the fractal dimension. The time evolution of the width of the arm suggests the surface self-diffusion mechanism as the main relaxation process. With Monte Carlo simulations, we confirmed the observed behavior. Comparison is done with our previous results on fragmentation of nano-fractal silver islands when impurity added to the incident cluster promotes rapid fragmentation by surface self-diffusion enhancement [1].     

Integrated microfabricated systems including a purification module and an on-chip nano electrospray ionization interface for biological analysis

We report here on an integrated microfabricated device dedicated to the preparation of biological samples prior to their on-line analysis by electrospray ionization-mass spectrometry (ESI-MS). This microfluidic device is fabricated using the negative photoresist SU-8 by microtechnology techniques. The device includes a chromatographic module plus an ESI interface for MS. The chromatographic module is dedicated to sample purification and is based on a polymer monolithic phase which includes hydrophobic moieties. The ESI interface is integrated onto the chip and is based on a capillary slot. We present here the integration of these different modules onto a single system that is fabricated via a SU-8-based microtechnology route. We present also their testing for the purification of peptide samples. This started with a partial integration step with the combination of at least two of the modules (microsystem + monolith; microsystem + nib) and their test before the fabrication and testing of fully integrated microsystems.     

Convex polynomial and spline approximation in C[−1, 1]

We prove that a convex functionf C[–1, 1] can be approximated by convex polynomialsp _n of degreen at the rate of ₃(f, 1/n). We show this by proving that the error in approximatingf by C² convex cubic splines withn knots is bounded by ₃(f, 1/n) and that such a spline approximant has anL third derivative which is bounded by n³₃(f, 1/n). Also we prove that iff C²[–1, 1], then it is approximable at the rate ofn ^–2 (f, 1/n) and the two estimates yield the desired result.Communicated by Ronald A. DeVore.     

Acetylcholinesterase complexed with bivalent ligands related to huperzine a: experimental evidence for species-dependent protein-ligand complementarity

Acetylcholinesterase (AChE) inhibitors improve the cognitive abilities of Alzheimer patients. (-)-Huperzine A [(-)-HupA], an alkaloid isolated from the club moss, Huperzia serrata, is one such inhibitor, but the search for more potent and selective drugs continues. Recently, alkylene-linked dimers of 5-amino-5,6,7,8-tetrahydroquinolinone (hupyridone, 1a), a fragment of HupA, were shown to serve as more potent inhibitors of AChE than (-)-HupA and monomeric 1a. We soaked two such dimers, (S,S)-(-)-bis(10)-hupyridone [(S,S)-(-)-2a] and (S,S)-(-)-bis(12)-hupyridone [(S,S)-(-)-2b] containing, respectively, 10 and 12 methylenes in the spacer, into trigonal TcAChE crystals, and solved the X-ray structures of the resulting complexes using the difference Fourier technique, both to 2.15 A resolution. The structures revealed one HupA-like 1a unit bound to the "anionic" subsite of the active-site, near the bottom of the active-site gorge, adjacent to Trp84, as seen for the TcAChE/(-)-HupA complex, and the second 1a unit near Trp279 in the "peripheral" anionic site at the top of the gorge, both bivalent molecules thus spanning the active-site gorge. The results confirm that the increased affinity of the dimeric HupA analogues for AChE is conferred by binding to the two "anionic" sites of the enzyme. Inhibition data show that (-)-2a binds to TcAChE approximately 6-7- and > 170-fold more tightly than (-)-2b and (-)-HupA, respectively. In contrast, previous data for rat AChE show that (-)-2b binds approximately 3- and approximately 2-fold more tightly than (-)-2a and (-)-HupA, respectively. Structural comparison of TcAChE with rat AChE, as represented by the closely related mouse AChE structure (1maa.pdb), reveals a narrower gorge for rat AChE, a perpendicular alignment of the Tyr337 ring to the gorge axis, and its conformational rigidity, as a result of hydrogen bonding between its hydroxyl group and that of Tyr341, relative to TcAChE Phe330. These structural differences in the active-site gorge explain the switch in inhibitory potency of (-)-2a and 2b and the larger dimer/(-)-HupA potency ratios observed for TcAChE relative to rat AChE. The results offer new insights into factors affecting protein-ligand complementarity within the gorge and should assist the further development of improved AChE inhibitors.     

Apparent Molar Volume, Heat Capacity, and Conductance of Lithium Bis(trifluoromethylsulfone)imide in Glymes and Other Aprotic Solvents

Lithium bis(trifluoromethylsulfone)imide (LiTFSI) is a promising electrolyte for high-energy lithium batteries due to its high solubility in most solvents and electrochemical stability. To characterize this electrolyte in solution, its conductance and apparent molar volume and heat capacity were measured over a wide range of concentration in glymes, tetraethylsulfamide (TESA), acetonitrile, -butyrolactone, and propylene carbonate at 25°C and were compared with those of LiClO₄ in the same solvents. The glymes or n(ethylene glycol) dimethyl ethers (nEGDME), which have the chemical structure CH₃–O–(CH₂–CH₂–O) _n –CH₃ for n = 1 to 4, are particularly interesting since they are electrochemically stable, have a good redox window, and are analogs of the polyethylene oxides used in polymer-electrolyte batteries. TESA is a good plasticizer for polymer-electrolyte batteries. Whenever required, the following properties of the pure solvents were measured: compressibilities, expansibilities, temperature and pressure dependences of the dielectric constant, acceptor number, and donor number. These data were used in particular to calculate the limiting Debye-Hückel parameters for volumes and heat capacities. The infinite dilution properties of LiTFSI are quite similar to those of other lithium salts. At low concentrations, LiTFSI is strongly associated in the glymes and moderately associated in TESA. At intermediate concentrations, the thermodynamic data suggests that a stable solvate of LiTFSI in EGDME exists in the solution state. At high concentrations, the thermodynamic properties of the two lithium salts approach those of the molten salts. These salts have a reasonably high specific conductivity in most of the solvents. This suggests that the conductance of ions at high concentration in solvents of low dielectric constant is due to a charge transfer process rather than to the migration of free ions.     

NO reburning study based on species quantification obtained by coupling LIF and cavity ring-down spectroscopy

NO reburning is studied in a low pressure (15 hPa) premixed flame of CH4-O2 seeded with 1.8% of NO. Measurements were carried out by using cavity ring-down spectroscopy (CRDS) and laser induced fluorescence (LIF) techniques. The temperature profile was obtained by OH-LIF thermometry in the A-X (0-0) band. The OH profile was determined by LIF and calibrated by single pass absorption. The NO concentration profile was obtained by LIF in the A-X (0-0) band and corrected for Boltzmann fraction and quantum yield variations. The absolute concentration profile was determined in the burned gases by CRDS allowing a direct experimental determination of the NO reburning amount. Finally CH and CN mole fraction profiles were obtained by CRDS by exciting rotational transitions in the B-X (0-0) bands of CH and CN around 387 nm. We found a peak mole fraction of 29 ppm for CH and 3.3 ppm for CN. This last result is in contrast with a previous study of W. Juchmann, H. Latzel, D. L. Shin, G. Peiter, T. Dreier, H. R. Volpp, J. Wolfrum, R. P. Lindstedt and K. M. Leung, XXVIIth Symposium (International) on Combustion, The Combustion Institute, Pittsburgh, 1998, p. 469, performed in a similar flame, which reported much lower levels of CN. In that study the absolute concentration of CN was indirectly obtained by LIF calibrated by Rayleigh scattering. In a second part, experimental species profiles are compared with predictions of the GRI 3.0 mechanism. Comparison between experimental and predicted profiles shows a good agreement particularly for CN and NO species. A qualitative analysis of NO reburning is then performed.     

Polynomial approximation inL p (0<p<1)

We prove that forf∈L _p , 0<p<1, andk a positive integer, there exists an algebraic polynomialP _n of degree ≤n such that $$\left\| {f - P_n } \right\|_p \leqslant C\omega _k^\varphi \left( {f,\frac{1}{n}} \right)_p $$ whereω _k ^? (f,t)p is the Ditzian-Totik modulus of smoothness off inL _p , andC is a constant depending only onk andp. Moreover, iff is nondecreasing andk≤2, then the polynomialP _n can also be taken to be nondecreasing.     

Computer Handling of Chemical and Biological Data of Traditional Chinese Medicines

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