Acid-catalyzed rearrangement of 3-(β-2-aminostyryl)quinoxalin-2(1H)ones—a new and efficient method for the synthesis of 2-benzimidazol-2-ylquinolines

A highly efficient, one-step, versatile method for the synthesis of 2-benzimidazol-2-ylquinolines has been developed on the basis of an acid-catalyzed rearrangement proceeding via a novel ring contraction of 3-(β-2-aminostyryl)quinoxalin-2(1H)ones.     

Comparison of essential oil components and in vitro anticancer activity in wild and cultivated Salvia verbenaca

The objectives of our research were to study the chemical composition and the in vitro anticancer effect of the essential oil of Salvia verbenaca growing in natural sites in comparison with those of cultivated (Sc) plants. The oil from wild (Sw) S. verbenaca presented hexadecanoic acid (23.1%) as the main constituent, while the oil from Sc plants contained high quantities of hexahydrofarnesyl acetone (9.7%), scarce in the natural oil (0.7%). The growth-inhibitory and proapoptotic effects of the essential oils from Sw and Sc S. verbenaca were evaluated in the human melanoma cell line M14, testing cell vitality, cell membrane integrity, genomic DNA fragmentation and caspase-3 activity. Both the essential oils were able to inhibit the growth of the cancer cells examined inducing also apoptotic cell death, but the essential oil from cultivated samples exhibited the major effects.     

Tensor method for optimal control problems constrained by fractional three-dimensional elliptic operator with variable coefficients

We introduce the tensor numerical method for solving optimal control problems that are constrained by fractional two- (2D) and three-dimensional (3D) elliptic operators with variable coefficients. We solve the governing equation for the control function which includes a sum of the fractional operator and its inverse, both discretized over large 3D $n\times n\times n$ spacial grids. Using the diagonalization of the arising matrix-valued functions in the eigenbasis of the one-dimensional Sturm–Liouville operators, we construct the rank-structured tensor approximation with controllable precision for the discretized fractional elliptic operators and the respective preconditioner. The right-hand side in the constraining equation (the optimal design function) is supposed to be represented in a form of a low-rank canonical tensor. Then the equation for the control function is solved in a tensor structured format by using preconditioned CG iteration with the adaptive rank truncation procedure that also ensures the accuracy of calculations, given an $\epsilon$-threshold. This method reduces the numerical cost for solving the control problem to $O(n\log n)$ (plus the quadratic term $O(n^2)$ with a small weight), which outperforms traditional approaches with $O(n^3\log n)$ complexity in the 3D case. The storage for the representation of all 3D nonlocal operators and functions involved is also estimated by $O(n\log n)$. This essentially outperforms the traditional methods operating with fully populated $n^3\times n^3$ matrices and vectors in ${?}^{n^3}$. Numerical tests for 2D/3D control problems indicate the almost linear complexity scaling of the rank truncated preconditioned conjugate gradient iteration in the univariate grid size n.     

XPS and AFM characterization of the enzyme glucose oxidase immobilized on SiO(2) surfaces

A process to immobilize the enzyme glucose oxidase on SiO2 surfaces for the realization of integrated microbiosensors was developed. The sample characterization was performed by monitoring, step by step, oxide activation, silanization, linker molecule (glutaraldehyde) deposition, and enzyme immobilization by means of XPS, AFM, and contact angle measurements. The control of the environment during the procedure, to prevent silane polymerization, and the use of oxide activation to obtain a uniform enzyme layer are issues of crucial importance. The correct protocol application gives a uniform layer of the linker molecule and the maximum sample surface coverage. This result is fundamental for maximizing the enzyme bonding sites on the sample surface and achieving the maximum surface coverage. Thin SiO2 layers thermally grown on a Si substrate were used. The XPS Si 2p signal of the substrate was monitored during immobilization. Such a signal is not completely shielded by the thin oxide layer and it is fully suppressed after the completion of the whole protocol. A power spectral density analysis on the AFM measurements showed the crucial role of both the oxide activation and the intermediate steps (silanization and linker molecule deposition) to obtain uniform immobilized enzyme coverage. Finally, enzymatic activity measurements confirmed the suitability of the optimized protocol.     

Fast tensor method for summation of long‐range potentials on 3D lattices with defects

In this paper, we present a method for fast summation of long‐range potentials on 3D lattices with multiple defects and having non‐rectangular geometries, based on rank‐structured tensor representations. This is a significant generalization of our recent technique for the grid‐based summation of electrostatic potentials on the rectangular L × L × L lattices by using the canonical tensor decompositions and yielding the O(L) computational complexity instead of O(L³) by traditional approaches. The resulting lattice sum is calculated as a Tucker or canonical representation whose directional vectors are assembled by the 1D summation of the generating vectors for the shifted reference tensor, once precomputed on large N × N × N representation grid in a 3D bounding box. The tensor numerical treatment of defects is performed in an algebraic way by simple summation of tensors in the canonical or Tucker formats. To diminish the considerable increase in the tensor rank of the resulting potential sum, the ?‐rank reduction procedure is applied based on the generalized reduced higher‐order SVD scheme. For the reduced higher‐order SVD approximation to a sum of canonical/Tucker tensors, we prove the stable error bounds in the relative norm in terms of discarded singular values of the side matrices. The required storage scales linearly in the 1D grid‐size, O(N), while the numerical cost is estimated by O(NL). The approach applies to a general class of kernel functions including those for the Newton, Slater, Yukawa, Lennard‐Jones, and dipole‐dipole interactions. Numerical tests confirm the efficiency of the presented tensor summation method; we demonstrate that a sum of millions of Newton kernels on a 3D lattice with defects/impurities can be computed in seconds in Matlab implementation. The tensor approach is advantageous in further functional calculus with the lattice potential sums represented on a 3D grid, like integration or differentiation, using tensor arithmetics of 1D complexity. Copyright © 2015 John Wiley & Sons, Ltd.     

Chemical composition and biological activity of Salvia verbenaca essential oil

Salvia verbenaca L. (syn. S. minore) is a perennial herb known in the traditional medicine of Sicily as "spaccapetri" and is used to resolve cases of kidney stones, chewing the fresh leaves or in decoction. The chemical composition of the essential oil obtained from aerial parts of S. verbenaca collected in Piano Battaglia (Sicily) on July 2009, was analyzed by GC and GC-MS. The oil was strongly characterized by fatty acids (39.5%) and carbonylic compounds (21.2%), with hexadecanoic acid (23.1%), (Z)-9-octadecenoic acid (11.1%) and benzaldehyde (7.3%) as the main constituents. The in vitro activity of the essential oil against some microorganisms in comparison with chloramphenicol by the broth dilution method was determined. The oil exhibited a good activity as inhibitor of growth of Gram + bacteria.     

A Multifunctional Bichromophoric Nanoaggregate for Fluorescence Imaging and Simultaneous Photogeneration of RNOS and ROS

We report the design, preparation, and properties of a nanoaggregate formed in phosphate buffer solution by a porphyrin–β‐cyclodextrin (β‐CD) conjugate and a nitric oxide photodonor tailored to fit the β‐CD cavity. The small nanoassembly with a diameter of about 13 nm exhibits the typical red fluorescence of the porphyrin chromophore. The empty cavity of the β‐CD unit in the nanoaggregate is able to accommodate the NO photodonor, thereby forming a supramolecular bichromophoric aggregate with diameter of about 16 nm. This nanoconstruct preserves the fluorescence of the porphyrin core and is able to generate nitric oxide and singlet oxygen under illumination with visible light. The nanoassembly internalizes in melanoma cells, can be mapped therein by fluorescence microscopy, and induces a significant level of cell mortality, probably due to the combined action of reactive nitrogen oxide species (RNOS) and reactive oxygen species (ROS).     

Pyridinyloxazolidines: versatile scaffolds for chiral catalyst construction

Pyridinyloxazolidines are structurally versatile chiral ligand frameworks that are easily made and coordinated to Pd(II); the resulting complexes, which show significant steric and electronic differences from their oxazoline counterparts, as well as intermolecular H-bonding in the solid state, can be isolated in diastereomerically pure form and are remarkably resistant to hydrolysis.