Sequential functionalization of pyrazole 1-oxides via regioselective metalation: synthesis of 3,4,5-trisubstituted 1-hydroxypyrazoles

A range of 3,5-diarylated and 3,4,5-triarylated 2-(4-methoxybenzyl)pyrazole 1-oxides have been prepared by regioselective deprotonation at C-5 or bromine-magnesium exchange at C-3 or C-4 followed by transmetalation with ZnCl(2) and palladium(0)-catalyzed cross-coupling. Furthermore, the metalated pyrazole 1-oxides could be trapped with electrophiles. The sequential metalation/functionalization of the pyrazole 1-oxides may follow the order C-5, C-3, C-4, or alternatively the order C-3, C-5, C-4. The 4-methoxybenzyl group of the functionalized 2-(4-methoxybenzyl)pyrazole 1-oxides could be removed by treatment with TFA and i-Pr(3)SiH in CH(2)Cl(2), providing the corresponding functionalized 1-hydroxypyrazoles.     

Long-range electron transfer in porphyrin-containing [2]-rotaxanes: tuning the rate by metal cation coordination

A series of [2]-rotaxanes has been synthesized in which two Zn(II)-porphyrins (ZnP) electron donors were attached as stoppers on the rod. A macrocycle attached to a Au(III)-porphyrin (AuP+) acceptor was threaded on the rod. By selective excitation of either porphyrin, we could induce an electron transfer from the ZnP to the AuP+ unit that generated the same ZnP*+-AuP* charge-transfer state irrespective of which porphyrin was excited. Although the reactants were linked only by mechanical or coordination bonds, electron-transfer rate constants up to 1.2x10(10) x s(-1) were obtained over a 15-17 A edge-to-edge distance between the porphyrins. The resulting charge-transfer state had a relatively long lifetime of 10-40 ns and was formed in high yield (>80%) in most cases. By a simple variation of the link between the reactants, viz. a coordination of the phenanthroline units on the rotaxane rod and ring by either Ag+ or Cu+, we could enhance the electron-transfer rate from the ZnP to the excited 3AuP+. We interpret our data in terms of an enhanced superexchange mechanism with Ag+ and a change to a stepwise hopping mechanism with Cu+, involving the oxidized Cu(phen)22+ unit as a real intermediate. When the ZnP unit was excited instead, electron transfer from the excited 1ZnP to AuP+ was not affected, or even slowed, by Ag+ or Cu+. We discuss this asymmetry in terms of the different orbitals involved in mediating the reaction in an electron- and a hole-transfer mechanism. Our results show the possibility to tune the rates of electron transfer between noncovalently linked reactants by a convenient modification of the link. The different effect of Ag+ and Cu+ on the rate with ZnP and AuP+ excitation shows an additional possibility to control the electron-transfer reactions by selective excitation. We also found that coordination of the Cu+ introduced an energy-transfer reaction from 1ZnP to Cu(phen)2+ (k = 5.1x10(9) x s(-1)) that proceeded in competition with electron transfer to AuP+ and was followed by a quantitative energy transfer to give the 3ZnP state (k = 1.5x10(9) x s(-1)).     

The pressure equation for fluid flow in a stochastic medium

An equation modelling the pressurep(x) =p(x, w) atx ∈D ⊂R ^d of an incompressible fluid in a heterogeneous, isotropic medium with a stochastic permeabilityk(x, w) ≥ 0 is the stochastic partial differential equation

The automorphism group of the irrational rotation C*-algebra

The structure of the automorphism group of a simple C^*-algebra of real rank zero which is an inductive limit of circle algebras is described. In particular, it is proved that the automorphism group of the irrational rotation C^*-algebra,A , for any irrational number , is an extension of a topologically simple group by GL₂().Dedicated to Huzihiro Araki     

Effective synthesis of negatively charged cyclodextrins. Selective access to phosphate cyclodextrins

We report the selective preparation of α- and β-cyclodextrins bearing one and two phosphate moieties on the primary rim. These compounds were prepared by selective O-debenzylation of fully protected derivatives, followed by phosphorylation and deprotection. The synthesis of an α-cyclodextrin with both, a carboxylic group and a phosphate moiety on primary positions is also described. Title compounds are examples of negatively charged cyclodextrins that might be of interest in studying the complexation of cationic guests.     

New energy terms for reduced protein models implemented in an off‐lattice force field

Parameterization and test calculations of a reduced protein model with new energy terms are presented. The new energy terms retain the steric properties and the most significant degrees of freedom of protein side chains in an efficient way using only one to three virtual atoms per amino acid residue. The energy terms are implemented in a force field containing predefined secondary structure elements as constraints, electrostatic interaction terms, and a solvent‐accessible surface area term to include the effect of solvation. In the force field the main‐chain peptide units are modeled as electric dipoles, which have constant directions in α‐helices and β‐sheets and variable conformation‐dependent directions in loops. Protein secondary structures can be readily modeled using these dipole terms. Parameters of the force field were derived using a large set of experimental protein structures and refined by minimizing RMS errors between the experimental structures and structures generated using molecular dynamics simulations. The final average RMS error was 3.7 Å for the main‐chain virtual atoms (C_α atoms) and 4.2 Å for all virtual atoms for a test set of 10 proteins with 58–294 amino acid residues. The force field was further tested with a substantially larger test set of 608 proteins yielding somewhat lower accuracy. The fold recognition capabilities of the force field were also evaluated using a set of 27,814 misfolded decoy structures. © 2001 John Wiley & Sons, Inc. J Comput Chem 22: 1229–1242, 2001     

Essential norm of the difference of weighted composition operators

We study differences of weighted composition operators between weighted Banach spaces H _ν ^∞ of analytic functions with weighted sup-norms and give an expression for the essential norm of these differences. We apply our result to estimate the essential norm of differences of composition operators acting on Bloch-type spaces. Authors’ addresses: Mikael Lindstr?m, Department of Mathematics, Abo Akademi University, FIN 20500 Abo, Finland; Elke Wolf, Mathematical Institute, University of Paderborn, D-33095 Paderborn, Germany     

Loud Speech in Realistic Environmental Noise: Phonetogram Data, Perceptual Voice Quality, Subjective Ratings, and Gender Differences in Healthy Speakers

A new method for cancelling background noise from running speech was used to study voice production during realistic environmental noise exposure. Normal subjects, 12 women and 11 men, read a text in five conditions: quiet, soft continuous noise (75 dBA to 70 dBA), day-care babble (74 dBA), disco (87 dBA), and loud continuous noise (78 dBA to 85 dBA). The noise was presented over loudspeakers and then removed from the recordings in an off-line processing operation. The voice signals were analyzed acoustically with an automatic phonetograph and perceptually by four expert listeners. Subjective data were collected after each vocal loading task. The perceptual parameters press, instability, and roughness increased significantly as an effect of speaking loudly over noise, whereas vocal fry decreased. Having to make oneself heard over noise resulted in higher SPL and F0, as expected, and in higher phonation time. The total reading time was slightly longer in continuous noise than in intermittent noise. The women had 4 dB lower voice SPL overall and increased their phonation time more in noise than did the men. Subjectively, women reported less success making themselves heard and higher effort. The results support the contention that female voices are more vulnerable to vocal loading in background noise.     

Influence of long-term aqueous exposure on surface properties of plasma sprayed oxides Al2O3, TiO2 and their mixture Al2O3-13TiO2

The surface properties of plasma sprayed Al₂O₃- and TiO₂-based coating materials were characterized in order to investigate the influence of surface strain and phase inhomogenity. The materials were water exposed up to 8 months. The bulk crystallographic structure, dissolution behaviour, effective charge (zeta potential, isoelectric point), surface compositions and oxidation states were determined. In addition, the properties of the aging solutions, such as conductivity, supernatant pH (point of zero charge), and redox potential, were monitored during aging.It was shown that the materials were stable under aging conditions, but that considerable surface rearrangements, such as dissolution-reprecipitation and surface site redistributions may occur. However, overall only minor changes in surface properties results from this restructuring process.