Stark effect and generalized Bloch-Siegert shift in a strongly driven two-level system

A superconducting qubit was driven in an ultrastrong fashion by an oscillatory microwave field, which was created by coupling via the nonlinear Josephson energy. The observed Stark shifts of the "atomic" levels are so pronounced that corrections even beyond the lowest-order Bloch-Siegert shift are needed to properly explain the measurements. The quasienergies of the dressed two-level system were probed by resonant absorption via a cavity, and the results are in agreement with a calculation based on the Floquet approach.     

Insights into the Pamamycin Biosynthesis

Pamamycins are macrodiolides of polyketide origin with antibacterial activities. Their biosynthesis has been proposed to utilize succinate as a building block. However, the mechanism of succinate incorporation into a polyketide was unclear. Here, we report identification of a pamamycin biosynthesis gene cluster by aligning genomes of two pamamycin‐producing strains. This unique cluster contains polyketide synthase (PKS) genes encoding seven discrete ketosynthase (KS) enzymes and one acyl‐carrier protein (ACP)‐encoding gene. A cosmid containing the entire set of genes required for pamamycin biosynthesis was successfully expressed in a heterologous host. Genetic and biochemical studies allowed complete delineation of pamamycin biosynthesis. The pathway proceeds through 3‐oxoadipyl‐CoA, a key intermediate in the primary metabolism of the degradation of aromatic compounds. 3‐Oxoadipyl‐CoA could be used as an extender unit in polyketide assembly to facilitate the incorporation of succinate.     

Flow Structure of Swirling Turbulent Propane Flames

Flow structure of premixed propane–air swirling jet flames at various combustion regimes was studied experimentally by stereo PIV, CH* chemiluminescence imaging, and pressure probe. For the non-swirling conditions, a nonlinear feedback mechanism of the flame front interaction with ring-like vortices, developing in the jet shear layer, was found to play important role in the stabilisation of the premixed lifted flame. For the studied swirl rates (S = 0.41, 0.7, and 1.0) the determined domain of stable combustion can be divided into three main groups of flame types: attached flames, quasi-tubular flames, and lifted flames. These regimes were studied in details for the case of S = 1.0, and the difference in the flow structure of the vortex breakdown is described. For the quasi-tubular flames an increase of flow precessing above the recirculation zone was observed when increased the stoichiometric coefficient from 0.7 to 1.4. This precessing motion was supposed to be responsible for the observed increase of acoustic noise generation and could drive the transition from the quasi-tubular to the lifted flame regime.     

2,4,5,7-Tetranitrofluorescein in solutions: novel type of tautomerism in hydroxyxanthene series as detected by various spectral methods

Stepwise dissociation and tautomerism of 2,4,5,7-tetranitrofluorescein (TNF) were studied by using vis-spectroscopy in dimethylsulfoxide (DMSO), in aqueous acetone, and in cetyl-trimethylammonium chloride (CTAC) micellar solutions at ionic strength of the bulk phase 4.00M KCl. The pK(a) values in DMSO and 90 mass% (CH3)2CO as well as the 'apparent'pK(a)(a) values of the substance in micellar media were determined spectrophotometrically. The neutral (molecular) form H2R is found to be completely converted into the colorless lactone. Moreover, the lactonic structure, yellow due to 'nitrophenolate' absorption band, predominates also in the case of TNF dianion R2-. Contrary to the unsubstituted fluorescein, and like 2,4,5,7-tetrabromofluorescein (eosin), the monoanion HR- of TNF with lambda(max) 522-525 nm and E(max) approximately (60-62)x10(3) dm(3)mol(-1)cm(-1) exists mainly as a deeply and intensively colored structure with non-ionized carboxylic and ionized hydroxylic group; its fluorescence spectra in various media are registered. In 90% acetone, the Stokes shift is 1.17x10(3)cm(-1), fluorescence lifetime equals 2.3 ns. An extremely expressed trend to dianion-lactone formation of R2- ion of TNF is confirmed in the systems studied. For TNF in DMSO, in aqueous acetone, in surfactant micelles, and in trichloromethane extracts of ionic associatiates with N(n-Bu)4+ and N(n-Hept)4+, the deeply colored 'quinon-phenolate' dianion, typical for all hydroxyxanthenes, is not registered at all. The sequence of dissociation of functional groups in solution is confirmed using IR spectroscopy in DMSO.     

Molecular Structure,Thermodynamic and Spectral Characteristics of Metal-Free and Nickel Complex of Tetrakis(1,2,5-thiadiazolo)porphyrazine

The Knudsen effusion method with mass spectrometric control of the vapor composition was used to study the possibility of a congruent transition to the gas phase and to estimate the enthalpy of sublimation of metal-free tetrakis(1,2,5-thiadiazolo)porphyrazine and its nickel complex (H₂TTDPz and NiTTDPz, respectively). The geometrical and electronic structure of H₂TTDPz and NiTTDPz in ground and low-lying excited electronic states were determined by DFT calculations. The electronic structure of NiTTDPz was studied by the complete active space (CASSCF) method, following accounting dynamic correlation by multiconfigurational quasi-degenerate second-order perturbation theory (MCQDPT2). A geometrical structure of D_2h and D_4h symmetry was obtained for H₂TTDPz and NiTTDPz, respectively. According to data obtained by the MCQDPT2 method, the nickel complex possesses the ground state ¹A_1g, and the wave function of the ground state has the form of a single determinant. Electronic absorption and vibrational (IR and resonance Raman) spectra of H₂TTDPz and NiTTDPz were studied experimentally and simulated theoretically.     

A parallel solution-phase synthesis of substituted 3,7-diazabicyclo[3.3.1]nonanes

The parallel solution-phase synthesis of a series of building blocks and combinatorial libraries based on natural bispidine scaffold has been accomplished. Key reactions include catalytic hydrogenation of the (-)-cytisine heterocyclic system, followed by alkali-mediated ring cleavage. Using this approach, a series of new bispidine core building blocks for combinatorial synthesis with three points of diversity were effectively synthesized. The libraries from libraries were then obtained in good yields and purities using solution-phase acylation reactions. Obtained combinatorial libraries of 3,4,7-trisubstituted bispidines are potentially useful in the discovery of novel physiologically active compounds.     

Self-Diffusion Coefficients for Pure and Mixed Adsorbate Fluids in Narrow Pores

The equilibrium distribution and the concentration dependence of the local and average self-diffusion coefficients for pure fluid and binary mixture components in narrow slitlike pores were analyzed. The coefficients were calculated using the lattice gas model in the quasi-chemical approximation on the assumption of a spherical shape and approximately equal sizes of the components. For the pure adsorbate, these calculations were compared with molecular dynamics simulations. Both methods gave similar concentration profile changes and dynamic characteristics of interlayer particle redistributions in strong nonuniform adsorption fields for dense fluids. A satisfactory agreement was obtained for the temperature dependences of the self-diffusion coefficients along the pore axis. The influence of the molecule–wall potential and of intermolecular interaction were considered. The self-diffusion coefficients of the adsorbate were shown to strongly depend on the density of the mixture and the distance from pore walls.     

Convergence of series of dependent φ-subgaussian random variables

The almost sure convergence of weighted sums of φ-subgaussian m-acceptable random variables is investigated. As corollaries, the main results are applied to the case of negatively dependent and m-dependent subgaussian random variables. Finally, an application to random Fourier series is presented.