Enzyme-like acceleration for the hydrolysis of a DNA model promoted by a dinuclear Zn(II) catalyst in dilute aqueous ethanol

The rates and products of cleavage of methyl (2-chloro-4-nitrophenyl) phosphate (2) promoted by a dinuclear Zn(II) complex (3) of 1,3-bis-N,N'(1,5,9-triazacyclododecyl)propane along with 1 equiv of ethoxide were investigated in ethanol solution containing small amounts of water (8 mM or=1.6 x 10(17) times relative to the background hydroxide reaction, suggesting that complex 3 promotes the hydrolysis at least 1000 times more effectively than ethanolysis.     

Bistability of quantum magnetotransport in a multilayer Ge/p-Ge1−x Six heterostructure with wide potential wells

Two metastable states of a multilayer Ge/p-Ge_1−x Si_x heterosystem with wide (∼ 35 nm) potential wells (Ge) are observed in strong magnetic fields B at low temperatures. In the first state, the Hall resistivity exhibits an inflection near the value ρ_xy=h/e ² scaled to one Ge layer. The longitudinal magnetoresistivity ρ_xx(B) possesses a minimum in the range of fields where this inflection occurs. The temperature evolution of the inflection in ρ_xy(B), the minimum of ρ _xx(B), and the value of ρ_xy at the inflection indicates a weakly expressed state of the quantum Hall effect with a uniform current distribution over the layers. In the second metastable state, an unusually wide plateau near h/2e ² with a very weak field dependence is observed in ρ_xy(B). Estimates show that in these samples the Fermi level lies below but close to the top of the inflection in the bottom of the well. For this reason, the second state can be explained by separation of a hole gas in the Ge layers into two sublayers, and the saturation of ρ_xy(B) near h/2e ² can be explained by the formation of a quantum Hall insulator state. Pis’ma Zh. éksp. Teor. Fiz. 70, No. 4, 290–297 (25 August 1999)     

Catalysis of the methanolysis of activated amides by divalent and trivalent metal ions. The effect of Zn(2+), Co(2+), and La(3+) on the methanolysis of acetylimidazole and its (NH(3))(5)Co(III) complex.

The metal ions Zn(2+), Co(2+), and La(3+) strongly catalyze the methanolysis of the activated amides acetylimidazole (1) and its ligand-exchange-inert Co(III) complex, (NH(3))(5)Co(III)-AcIm (2). Studies of the kinetics of methanolysis are performed with pH measurement and control, and the metal ions are soluble in the medium throughout the pH regions where ionization of the M(x+)(CH(3)OH)(y) occurs. Zn(2+) and Co(2+) act as Lewis acids toward 1, catalyzing attack of external methoxide on a 1:M(2+) complex at values only 100-fold lower than the diffusion limit, the k(OR) values being 5.6 x 10(7) M(-1) s(-1) and 2.5 x 10(7) M(-1) s(-1), while that for CH(3)O(-) attack on 2 is 4.69 x 10(7) M(-1) s(-1). Since neither Zn(2+) nor Co(2+) promotes the methanolysis of 2, these metals appear to be acting through transient binding to the distal N of 1, which activates the C=O of the complex to external CH(3)O(-) attack. La(3+) catalyzes the methanolysis of both 1 and 2, which occurs by a mechanism that is fundamentally different from that exhibited by Zn(2+) and Co(2+) in that the active species appears to be a bis-methoxy-bridged dimer (La(3+))(2)(CH(3)O(-))(2)(CH(3)OH)(x)() that interacts directly with the C=O unit of the substrate.     

Quantum Oscillations of Magnetoresistance in HgCdTe/HgTe/HgCdTe Heterostructures with Inverted Band Spectrum

Physics of the Solid State - The effects observed in the Shubnikov–de Haas oscillation regime in the HgCdTe/HgTe/HgCdTe heterostructure with a wide (20.3 nm) HgTe quantum well with an...     

Phase Diagram of the Two-Orbital Model for Iron-Based HTSC: Variational Cluster Approximation

JETP Letters - The phase diagram of the two-dimensional two-orbital Hubbard model, which is widely used to describe high-temperature iron-based superconductors, is calculated in the electron doping...     

A calculation model for X-ray diffraction by curved-graphene nanoparticles

An approximation of the positions of carbon atoms in a curved graphene sheet is suggested for calculation of X-ray diffraction (XRD) patterns of curved-graphene nanoparticles. The model is tested for carbon nanotubes and newly calculated carbon nanotoroids consisting of several hundreds of atoms. It is shown that the random distribution of carbon atoms with graphene surface-averaged density and the local graphene-like rearrangement of atoms in a curved lattice are sufficient for describing the XRD patterns of an ensemble of respective exact carbon nanoparticles of random isotropic orientation in the range of scattering wave vector's modulus q from several units to several tens of inverse nanometers. The model is of interest to a fast-routine identification of curved-graphene nanoparticles in carbonaceous materials.     

Analysis of the Accuracy of Measuring the Flux Density of All Hydrogen Isotopes from First Wall to Plasma Using the H-Alpha Diagnostics in ITER

Physics of Atomic Nuclei - The results of the analysis of the accuracy of measuring the flux density of all hydrogen isotopes from the first wall of the main vacuum chamber to the ITER tokamak...     

Electrocarboxylation of CCI<Subscript>4</Subscript> in MeCN during electrolysis with the sacrificial Zn anode

The regularities of galvanostatic electrocarboxylation of CCl₄ in Alk₄NBr/MeCN in an undivided cell with sacrificial Zn anode were studied. The major product of the electrolysis is zinc trichloroacetate, which is formed as a result of the reaction of the cathode-generated CCl₃- anion with CO₂. The further trichloroacetate reduction is prevented by cathode passivation. Therefore, small amounts of zinc dichloro- and monochloroacetates are formed due to the chemical reduction of zinc trichloroacetate with Zn⁰ rather than the cathodic reduction. Zero-valence zinc is formed in minor amounts when Zn²⁺ ions are discharged at the cathode surface because of the low solubility of ZnBr₂ in MeCN. The treatment of (Cl₃CCOO)₂Zn with H₂SO₄ in MeOH gives Cl₃CCO₂Me in 11% yield based on the starting CCl₄.     

Palladacycle-promoted solvolytic cleavage of O,O-dimethyl O-aryl phosphorothioates. Converting a phosphorane-like transition state to an observable intermediate

The mechanism of cleavage of a series of seven O,O-dimethyl O-aryl phosphorothioates (6a-g) promoted by a C,N-palladacycle, (2-[N,N-dimethylamino(methyl)phenyl]-C(1),N)(pyridine) palladium(II) triflate (5:OTf) in methanol at 25 °C was investigated with the aim of identifying catalytically important intermediates. Complete (s)(s)pH/rate profiles (in methanol) were conducted for the cleavage of 6a-g in the presence of 0.08 mM 5. The log k(obs) for the catalyzed methanolysis of 6a increases linearly with (s)(s)pH with a plateau above the (s)(s)pK(a)(1) of 11.16 for formation of 5:(-)OCH3. The profiles for 6b-g are bell-shaped, depending on the apparent ionizations of two acidic groups, with the rate constant maximum of the bell and the (s)(s)pK(a)(1) values shifting to higher (s)(s)pH values as the (s)(s)pK(a)(HOAr) of the leaving group phenol increases. A Br?nsted plot of the log k(obs)(max) (the maximum rate constants for cleavage of 6a-g) vs (s)(s)pK(a)(HOAr) exhibits a downward break at ~ (s)(s)pK(a)(HOAr) 13, with the two wings having β(lg) values of 0.01 and -0.96. A model describing the kinetically important species involves a complex series of equilibria: 5:(HOCH(3)):pyr <=> 5:((-)OCH3):pyr + H(+) <=>(6) 5:((-)OCH3):6 + pyr <=> phosphorane 7 → product, where the rate limiting steps change from formation of 5:((-)OCH3):6 to formation of thiophosphorane 7 and then to product formation as the aryloxy leaving groups of 6 get progressively worse. Kinetic experiments indicate that the reaction of 5 with 6e, having a 4-chlorophenoxy leaving group, rapidly produces a transient intermediate, postulated to be the palladacycle-bound 5-coordinate thiophosphorane (7e) that exists long enough to obtain its UV/vis spectrum by stopped-flow spectrophotometry. Detailed analysis of the data sheds light on the origins of a previously reported anomalously large β(lg) of -1.93 for the descending wing of a Br?nsted plot (J. Am. Chem. Soc. 2010, 132, 16599). Finally, energetics analysis indicates that the binding of palladacycle to the transition state comprising attack of methoxide on 6e, [MeO(-) + 6e](++), stabilizes the latter by 34.9 kcal/mol, converting that transition state into an observable intermediate.