Pimprinols A–C,from the terrestrial actinomycete,Streptomyces sp.

A Streptomyces sp. Lv3-13, isolated from the rhizosphere soil of the plant Mespilus germanica, has yielded three new pimprinine derivatives, named pimprinols A–C (1–3) and the unknown (2-aminophenyl)(2-ethyloxazol-5-yl) methanone (4) along with the known compounds 2-ethyl oxazole pimprinine and 2-propyl oxazole pimprinine. The structures of the compounds were elucidated based on spectroscopic methods including UV, HR-ESIMS and 1D, 2D NMR data. Compounds 1–4 were screened for antimicrobial and cytotoxic activities.     

Macrocycle-Derived Functional Xanthenes and Progress Towards Concurrent Detection of Glucose and Fructose

The detection of saccharides in biological media is of great current importance for the monitoring of disease states. We have previously reported that solutions of boronic acid-functionalized macrocycles form acyclic oligomeric materials in situ. The oligomers contain fluorescent xanthene moieties. Current efforts are aimed at modulating the spectroscopic responses of these materials for the analysis of specific sugars. We describe conditions whereby the xanthene boronic acids exhibit high colorimetric fructose selectivity. In contrast, at physiological levels selective glucose monitoring can be achieved via fluorescence. Additionally, we describe a method which exhibits promise for detecting both glucose and fructose at dual wavelengths in the UV-Vis region. Mechanistic rationale for each of these findings is presented.     

On the reactivity of isoindolo[2,1-a]quinazoline-5-ones

Base- and acid-catalyzed nucleophilic addition of 11H-isoindolo[2,1-a]quinazoline-5-one to aromatic aldehydes and maleimides was investigated. The aldol adducts and condensation products were obtained stereoselectively. Main diastereomers of the Michael adducts were isolated in 74-89% yield, and converted by N-methylation to new stable α-substituted isoindole derivatives, for which 6-methylisoindolo[2,1-a]]quinazoline-5-one stands as the unsubstituted reference. The stability of the latter was monitored in moist aerated CDCl₃ solution, and one of the oxidative hydrolysis product was characterized by X-ray diffraction analysis as the corresponding N-arylphthalimide. The reactivity of the unsubstituted 6-methylisoindolo[2,1-a]]quinazoline-5-one was also investigated with acetylenic Michael acceptors. Fully conjugated isoindole derivatives possessing an original pull-push-pull structure were obtained. The conformations and molecular orbitals of the dibenzoylacetylene adduct were studied at the DFT level of theory. Its static quadratic hyperpolarizabilty β₀ was also calculated at the ZINDO level.     

Vortex lattice matching effects in a washboard pinning potential induced by Co nanostripe arrays

An advanced mask-less nanofabrication technique, focused electron beam-induced deposition (FEBID), has been employed on epitaxial Nb thin films to prepare ferromagnetic decorations in the form of an array of Co stripes. These substantially modify the non-patterned films’ superconducting properties, providing a washboard-like pinning potential landscape for the vortex motion. At small magnetic fields B ? 0.1 T, vortex lattice matching effects have been investigated by magneto-transport measurements. Step-like drops in the field dependencies of the films resistivity ρ(B) have been observed in particular for the vortex motion perpendicular to the Co stripes. The field values, corresponding to the middle points of these drops in ρ(B), meet the vortex lattice parameter matching the pinning structure’s period. These disagree with the results of Jaque et al. (2002) [11], who observed matching effects corresponding to the stripe width in Nb films grown on periodically distributed submicrometric lines of Ni.     

Desynchronization transitions in nonlinearly coupled phase oscillators

We consider the nonlinear extension of the Kuramoto model of globally coupled phase oscillators where the phase shift in the coupling function depends on the order parameter. A bifurcation analysis of the transition from fully synchronous state to partial synchrony is performed. We demonstrate that for small ensembles it is typically mediated by stable cluster states, that disappear with creation of heteroclinic cycles, while for a larger number of oscillators a direct transition from full synchrony to a periodic or a quasiperiodic regime occurs.     

Spectrum of an electron spin coupled to an unpolarized bath of nuclear spins

The main source of decoherence for an electron spin confined to a quantum dot is the hyperfine interaction with nuclear spins. To analyze this process theoretically we diagonalize the central spin Hamiltonian in the high magnetic B-field limit. Then we project the eigenstates onto an unpolarized state of the nuclear bath and find that the resulting density of states has Gaussian tails. The level spacing of the nuclear sublevels is exponentially small in the middle of each of the two electron Zeeman levels but increases superexponentially away from the center. This suggests to select states from the wings of the distribution when the system is projected on a single eigenstate by a measurement to reduce the noise of the nuclear spin bath. This theory is valid when the external magnetic field is larger than a typical Overhauser field at high nuclear spin temperature.     

Visual detection of cysteine and homocysteine

The determination of cysteine and homocysteine levels is of great current interest for the monitoring of desease states. A new colorimetric method for the simultaneous detection of l-cysteine and l-homocysteine has been developed. A fluorescein derivative reacts with the above amino acids, producing their respective thiazolidines resulting in color changes. Interference from other amino acids and proteins is minimal.     

3-Fluoroalkyl (CF3, CHF2, CH2F) Cyclobutane-Derived Building Blocks for Medicinal Chemistry: Synthesis and Physicochemical Properties

Synthesis and physicochemical characterization of all possible cis- and trans-1,3-disubstituted cyclobutane-derived amines and carboxylic acids bearing mono-, di- and trifluoromethyl groups at the C-3 position is disclosed. Tetramethylammonium fluoride (TMAF)- or morpholinosulfur trifluoride (Morph-DAST)-mediated nucleophilic fluorination of appropriate cis- and trans-diastereomeric substrates was used as the key step for the preparation of CH₂F- and CHF₂-substituted derivatives. To obtain the corresponding cis- and trans-isomeric CF₃-substituted derivatives, resolution of known 3-(trifluoromethyl)cyclobutanecarboxylic acid (obtained as a mixture of diastereomers) was applied. The proposed procedures were suitable for the preparation of corresponding fluoroalkyl-substituted cyclobutane-derived amines and carboxylic acids on up to 50 g scale. All 12 building blocks obtained were characterized by measuring dissociation constants (pK_a) and lipophilicities (LogP, for model derivatives) to evaluate the effect of the fluoroalkyl substituents on their physicochemical properties relevant to further drug discovery applications.     

Estimation Problems for Periodically Correlated Isotropic Random Fields

Spectral theory of isotropic random fields in Euclidean space developed by M. I. Yadrenko is exploited to find a solution to the problem of optimal linear estimation of the functional

$$ A\zeta ={\sum\limits_{t=0}^{\infty}}\,\,\,{\int_{S_n}} \,\,a(t,x)\zeta (t,x)\,m_n(dx) $$

which depends on unknown values of a periodically correlated (cyclostationary with period T) with respect to time isotropic on the sphere S _n in Euclidean space E ⁿ random field ζ(t, x), t?∈?Z, x?∈?S _n . Estimates are based on observations of the field ζ(t, x)?+?θ(t, x) at points (t, x), t?=???1,???2, ..., x?∈?S _n , where θ(t, x) is an uncorrelated with ζ(t, x) periodically correlated with respect to time isotropic on the sphere S _n random field. Formulas for computing the value of the mean-square error and the spectral characteristic of the optimal linear estimate of the functional Aζ are obtained. The least favourable spectral densities and the minimax (robust) spectral characteristics of the optimal estimates of the functional Aζ are determined for some special classes of spectral densities.