Substituent effects on the basicity of 3,7-diazabicyclo[3.3.1]nonanes

Basicity constants for a series of 3,7-diazabicyclo[3.3.1]nonane derivatives in acetonitrile with a variation over 13 orders of magnitude have been determined using a spectrophotometric titration technique. An excellent correlation between basicity and calculated proton affinities obtained at PCM-B3LYP/6-31+G(d)//B3LYP/6-31G(d) level was found. The results are discussed in terms of substituent effects and compared to (15)N NMR chemical shifts.     

Pentakis(trifluoromethyl)phenyl, a sterically crowded and electron-withdrawing group: synthesis and acidity of pentakis(trifluoromethyl)benzene, -toluene, -phenol, and -aniline

A general route to functionalized pentakis(trifluoromethyl)phenyl (C6(CF3)5) derivatives, promising building blocks for designing novel stable carbenes, radical species, superacids, weakly coordinating anions and other practically and theoretically useful species, is presented. This pertrifluoromethylation route proceeds via conveniently pregenerated (trifluoromethyl)copper (CF3Cu) species in DMF, stabilized by addition of 1,3-dimethyl-2-imidazolidinone (DMI). These species react with hexaiodobenzene at ambient temperature to give the potassium pentakis(trifluoromethyl)phenoxide along with hexakis(trifluoromethyl)benzene and pentakis(trifluoromethyl)benzene in a combined yield of 80%. A possible reaction pathway explaining the formation of pentakis(trifluoromethyl)phenoxide is proposed. Pentakis(trifluoromethyl)phenol gives rise to easily functionalized pentakis(trifluoromethyl)chlorobenzene and pentakis(trifluoromethyl)aniline. Pertrifluoromethylation of pentaiodochlorobenzene and pentaiodotoluene allows straightforward access to pentakis(trifluoromethyl)chlorobenzene and pentakis(trifluoromethyl)toluene, respectively. XRD structures of several C6(CF3)5 derivatives were determined and compared with the calculated structures. Due to the steric crowding the aromatic rings in all C6(CF3)5 derivatives are significantly distorted. The gas-phase acidities (Delta Gacid) and pKa values in different solvents (acetonitrile (AN), DMSO, water) for the title compounds and a number of related compounds have been measured. The origin of the acidifying effect of the C6(CF3)5 group has been explored using the isodesmic reactions approach.     

The molecular approach to heterogeneous nucleation

A molecular approach to heterogeneous nucleation has been developed. The expressions for the equilibrium cluster distribution, the reversible work of the cluster formation, and the nucleation rate have been derived. Two separate statements for the work of formation were formulated. If the equilibrium cluster distribution is normalized on the monomer concentration near the substrate surface, the reversible work of formation is expressed by DeltaG(het) (I) = (F(n) (het)-F(n) (hom))-(F(1) (het)-F(1) (hom)) + DeltaG(hom) where F(n) (het) and F(n) (hom) are the Helmholtz free energies of a cluster interacting with a substrate and a cluster not interacting with the substrate, respectively. If the equilibrium cluster distribution is normalized on the monomer concentration far from the substrate surface, the work of cluster formation is given by DeltaG(het) (II) = (F(n) (het)-F(n) (hom)) + DeltaG(hom). The former expression corresponds to the approach of the classical heterogeneous nucleation theory. The cluster partition function appears to be dependent on the location of a virtual plane, which separates the volume, where the interaction of the clusters with the substrate is effective from the one where interaction is negligible. Our Monte Carlo simulations have shown that the dependence is rather weak and thus the location of the plane is not very important. According to the simulations the variation of the plane position in the range from 20 to 50 Angstroms does not lead to a considerable change of the heterogeneous nucleation rate.     

Proof of Harary's conjecture on the reconstruction of trees

We prove that a tree with at least three cutvertices is reconstructible from its cutvertex- deleted subgraphs. This answers in the affirmative a question raised by Professor Harary at the Seventh British Combinatorial Conference in 1979.     

Atomic layer deposition of PbZrO3 thin films

In this paper, we report on the preparation of lead zirconate films for the first time using atomic layer deposition in an attempt to investigate some of the film properties and also to evaluate possible use of the precursor combination to prepare more complex lead titanate zirconate. In the depositions tetraphenyl lead (Ph₄Pb) was used as the lead and zirconium 2,2,6,6-tetramethyl-3,5-heptadionato (Zr(thd)₄) as the zirconium precursor, while ozone was used as the oxygen source. Film growth, stoichiometry and quality were studied using different pulsing ratios at deposition temperatures of 275 and 300 °C. According to X-ray diffraction, the crystalline perovskite phase was observed when films deposited on SrTiO₃(1 0 0) were annealed at 600 °C. Surface roughness was reduced for lead deficient films as well as in annealed samples.     

A double arity hierarchy theorem for transitive closure logic

In this paper we prove that thek-ary fragment of transitive closure logic is not contained in the extension of the (k–1)-ary fragment of partial fixed point logic by all (2k–1)-ary generalized quantifiers. As a consequence, the arity hierarchies of all the familiar forms of fixed point logic are strict simultaneously with respect to the arity of the induction predicates and the arity of generalized quantifiers.Although it is known that our theorem cannot be extended to the sublogic deterministic transitive closure logic, we show that an extension is possible when we close this logic under congruence.Supported by a grant from the University of Helsinki. This research was initiated while he was a Junior Researcher at the Academy of FinlandThis article was processed by the author using the LATEX style filepljourlm from Springer-Verlag.     

An NMR-Based Approach to the Measurement of High Log K HL Values at Low Ionic Strength. 31P NMR Study of 1,2-Diaminoethane-N,N,N′,N′-tetra(methylenephosphonic Acid) Protonation Equilibrium at pH > 12

A sequential NMR based approach is proposed for measurements of high log K values at low ionic strength. [³¹P] NMR technique is used to determine the protonation constants of 1,2-diaminoethane-N,N,N,N-tetra(methylenephosphonic acid) (EDTPH, H₈L) at 25°C in 0.1 mol-dm^–3 KNO₃ and at 37°C in 0.15 mol-dm^–3 NaCl at pH 11–14. For equilibrium L + H HL log K are found to be 13.3 (0.1) and 12.9 (0.1), respectively.     

Transient bimodality in interacting particle systems

We consider a system of spins which have values ±1 and evolve according to a jump Markov process whose generator is the sum of two generators, one describing a spin-flipGlauber process, the other aKawasaki (stirring) evolution. It was proven elsewhere that if the Kawasaki dynamics is speeded up by a factor ^–2, then, in the limit 0 (continuum limit), propagation of chaos holds and the local magnetization solves a reaction-diffusion equation. We choose the parameters of the Glauber interaction so that the potential of the reaction term in the reaction-diffusion equation is a double-well potential with quartic maximum at the origin. We assume further that for each the system is in a finite interval ofZ with ^–1 sites and periodic boundary conditions. We specify the initial measure as the product measure with 0 spin average, thus obtaining, in the continuum limit, a constant magnetic profile equal to 0, which is a stationary unstable solution to the reaction-diffusion equation. We prove that at times of the order ^–1/2 propagation of chaos does not hold any more and, in the limit as 0, the state becomes a nontrivial superposition of Bernoulli measures with parameters corresponding to the minima of the reaction potential. The coefficients of such a superposition depend on time (on the scale ^–1/2) and at large times (on this scale) the coefficient of the term corresponding to the initial magnetization vanishes (transient bimodality). This differs from what was observed by De Masi, Presutti, and Vares, who considered a reaction potential with quadratic maximum and no bimodal effect was seen, as predicted by Broggi, Lugiato, and Colombo.     

Synthesis of Amphiphilic Amino Alcohols

An efficient and general approach for the synthesis of amphiphilic 1,2-amino alcohols is reported. The use of N-benzyl protecting groups is essential for obtaining good yields when opening a long-chain terminal epoxide with an amine.     

Mixing Properties for Mechanical Motion¶of a Charged Particle in a Random Medium

We study a one-dimensional semi-infinite system of particles driven by a constant positive force F which acts only on the leftmost particle of mass M, called the heavy particle (the h.p.), and all other particles are mechanically identical and have the same mass m < M. Particles interact through elastic collisions. At initial time all neutral particles are at rest, and the initial measure is such that the interparticle distances ξ _i are i.i.d. r.v. Under conditions on the distribution of ξ which imply that the minimal velocity obtained by each neutral particle after the first interaction with the h.p. is bigger than the drift of an associated Markovian dynamics (in which each neutral particle is annihilated after the first collision) we prove that the dynamics has a strong cluster property, and as a consequence, we prove existence of the discrete time limit distribution for the system as seen from the first particle, a ψ-mixing property, a drift velocity, as well as the central limit theorem for the tracer particle. Received: 22 March 2000 / Accepted: 8 December 2000