Synthetically attractive chiral cyclopentenone building blocks conjugated with tetrahydro- and 2-oxotetrahydrofurans

Synthetically useful chiral building blocks (3aS,6aR)-1,3,3a,6atetrahydro-4H-cyclopenta[c]furan-4-one and (3aS,6aR)- 3a,6a-dihydro-1H-cyclopenta[c]furan-1,4(3H)-dione have been synthesized via a key allylsilane–allyl alcohol fragmentation pathway using (3aS,6S,6aR)-6-(trimethylsilyl)-3,3a,6,6a-tetrahydro-1H-cyclopenta[c]furan-1-one as an illustrative example.

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Thermodynamics and kinetics of initial gas phase reactions in chemical vapor deposition of titanium nitride. Theoretical study of TiCl4 ammonolysis

Thermodynamic equilibrium and kinetics of the gas‐phase reaction between TiCl₄ and NH₃ have been studied computationally using results from recent quantum mechanical calculations of titanium tetrachloride ammonolysis. 1 These calculations were based upon the transition state theory for the direct reactions and RRKM theory for the reactions proceeding via intermediate complex. Rate constants for the barrierless reactions were expressed through the thermodynamic characteristics of the reagents and products using a semiempirical variational method. The kinetic simulation of the gas‐phase steps of CVD was performed within a model of a well‐stirred reactor at temperatures 300–1200 K and residence times between 0.1–2 s. At temperatures below 450 K formation of donor–acceptor complexes between TiCl₄ and NH₃ is the dominating process. At higher temperatures sequential direct ammonolysis takes place. At typical LPCVD conditions the only product of the first step of ammonolysis, TiCl₃NH₂, is formed in substantial amount. © 2001 John Wiley & Sons, Inc. J Comput Chem 22: 1366–1376, 2001     

Majorization for Products of Measurable Operators

A new equality for a faithful normal semifinitetrace on a von Neumann algebra is proved. We conjecturea strengthening of the result.     

Differences of idempotents in <Emphasis Type="Italic">C</Emphasis>*-algebras

Suppose that P and Q are idempotents on a Hilbert space H, while Q = Q* and I is the identity operator in H. If U = P ? Q is an isometry then U = U* is unitary and Q = I ? P. We establish a double inequality for the infimum and the supremum of P and Q in H and P ? Q. Applications of this inequality are obtained to the characterization of a trace and ideal F-pseudonorms on a W*-algebra. Let φ be a trace on the unital C*-algebra A and let tripotents P and Q belong to A. If P ? Q belongs to the domain of definition of φ then φ(P ? Q) is a real number. The commutativity of some operators is established.     

On <Emphasis Type="Italic">τ</Emphasis>-Compactness of Products of <Emphasis Type="Italic">τ</Emphasis>-Measurable Operators

Let \(\mathcal {M}\) be a von Neumann algebra of operators on a Hilbert space \(\mathcal {H}\), τ be a faithful normal semifinite trace on \(\mathcal {M}\). We obtain some new inequalities for rearrangements of τ-measurable operators products. We also establish some sufficient τ-compactness conditions for products of selfadjoint τ-measurable operators. Next we obtain a τ-compactness criterion for product of a nonnegative τ-measurable operator with an arbitrary τ-measurable operator. We construct an example that shows importance of nonnegativity for one of the factors. The similar results are obtained also for elementary operators from \(\mathcal {M}\). We apply our results to symmetric spaces on \((\mathcal {M}, \tau )\). The results are new even for the *-algebra \(\mathcal {B}(\mathcal {H})\) of all linear bounded operators on \(\mathcal {H}\) endowed with the canonical trace τ = tr.     

Femtosecond Optical and Magneto-Optical Spectroscopy Study of Magnetic and Electronic Inhomogeneities in a Pd0.94Fe0.06 Thin Film

The results of a femtosecond optical and magneto-optical spectroscopy study of a thin epitaxial film of a low-temperature magnetically soft Pd_0.94Fe_0.06 alloy on a ({dy001})-MgO substrate are reported. The photoinduced demagnetization and magnetization recovery times are determined. The latter increases critically at approaching the ferromagnetic ordering temperature T_C = 190 K from below. It is shown that the reflectivity dynamics after a photoexcitation pulse evolves from a two-exponential in the paramagnetic phase to a four-component at 80 K < T < T_C, simplifying to a three-component at T < 50 K. According to our interpretation, such an evolution, along with the manifestation of an additional increasing component in the magnetic response at 80 K < T < T_C, indicates a magnetic and electronic inhomogeneity of the film associated with the distribution of local iron concentrations. The fraction of small-scale inclusions of the paramagnetic phase is estimated as ≈10 vol %.

     

Advances in the Study of Gas Hydrates by Dielectric Spectroscopy

The influence of kinetic hydrate inhibitors on the process of natural gas hydrate nucleation was studied using the method of dielectric spectroscopy. The processes of gas hydrate formation and decomposition were monitored using the temperature dependence of the real component of the dielectric constant ε′(T). Analysis of the relaxation times τ and activation energy ΔE of the dielectric relaxation process revealed the inhibitor was involved in hydrogen bonding and the disruption of the local structures of water molecules.