New chiral phosphine-phosphite ligands in the enantioselective palladium-catalyzed allylic alkylation

A series of chiral phosphine-phosphite ligands 1-6 have been synthesized and used in the enantioselective palladium-catalyzed reaction of rac-1,3-diphenyl-2-propenyl acetate with dimethyl malonate as nucleophile. Ligands 1a, 2, 3, 5a, 6a, and 6b have been synthesized starting from racemic tert-butylphenylphosphinoborane. The use of dynamically resolved Li phosphide (-)-sparteine provided the optically pure ligands. Crystals of the allylpalladium (6a) complex were obtained, suitable for X-ray crystal structure determination. The X-ray crystal structure of the allylpalladium (6a) complex revealed a longer palladium-carbon bond distance trans to the phosphine moiety indicating that the attack of the nucleophile takes place at the carbon trans to the phosphine moiety. This was confirmed by the fact that the phosphine moiety did not affect the enantioselectivity directly. Under mild reaction conditions, enantioselectivities up to 83% were obtained (25 degrees C) with ligand 1e. Systematic variation of the ligand bridge and the phosphite moiety showed that the configuration of the product is controlled by the atropisomerism of the biphenyl substituent at the phosphite moiety. The conformation of the biphenyl group, in turn, is controlled by the substituent at the chiral carbon in the bridge. Ligands with large bite angles yielded higher enantioselectivities.     

Intercalation of Benzamide into Kaolinite

Well-crystallized kaolinite (K) was initially reacted at 60 degrees C with a water/dimethylsulfoxide (DMSO) mixture and the resulting intercalation derivative (K-DMSO) was characterized by powder X-ray diffractometry (PXRD), thermal analysis (simultaneous TG and DSC), and Fourier-transformed infrared spectroscopy (FTIR). Benzamide crystals were then melted with the K-DMSO derivative at 140 degrees C for 4 days, when a gradual displacement of DMSO by benzamide was observed within the interlayer spacing of the modified kaolinite. The resulting material, after extensive washing with acetone, was characterized and compared to the results obtained previously for the K-DMSO composite. Benzamide intercalation proceeded by gradual displacement of DMSO molecules until completion. The structural stabilization of the K-BZ derivative was explained through the establishment of hydrogen bonds between the carbonyl oxygen atoms of the intercalated benzamide and aluminol groups present at the surface of the kaolinite layer. The interlamellar spacing of K-BZ was shown to be possibly occupied by benzamide molecules that were located at a 68 degrees orientation in relation to the layer surface. Unlike most intercalation molecules such as DMSO, variations in the interplanar spacing of kaolinite were consistent with the nonkeying of any other part of the molecule between the aluminosilicate interlayers. Copyright 2000 Academic Press.     

Chimera states and synchronization in magnetically driven SQUID metamaterials

One-dimensional arrays of Superconducting QUantum Interference Devices (SQUIDs) form magnetic metamaterials exhibiting extraordinary properties, including tunability, dynamic multistability, negative magnetic permeability, and broadband transparency. The SQUIDs in a metamaterial interact through non-local, magnetic dipole-dipole forces, that makes it possible for multiheaded chimera states and coexisting patterns, including solitary states, to appear. The spontaneous emergence of chimera states and the role of multistability is demonstrated numerically for a SQUID metamaterial driven by an alternating magnetic field. The spatial synchronization and temporal complexity are discussed and the parameter space for the global synchronization reveals the areas of coherence-incoherence transition. Given that both one- and two-dimensional SQUID metamaterials have been already fabricated and investigated in the lab, the presence of a chimera state could in principle be detected with presently available experimental set-ups.     

Discrete breathers in nonlinear magnetic metamaterials

Magnetic metamaterials composed of split-ring resonators or U-type elements may exhibit discreteness effects in THz and optical frequencies due to weak coupling. We consider a model one-dimensional metamaterial formed by a discrete array of nonlinear split-ring resonators where each ring interacts with its nearest neighbors. On-site nonlinearity and weak coupling among the individual array elements result in the appearance of discrete breather excitations or intrinsic localized modes, both in the energy-conserved and the dissipative system. We analyze discrete single and multibreather excitations, as well as a special breather configuration forming a magnetization domain wall and investigate their mobility and the magnetic properties their presence induces in the system.     

Driven linear modes: Analytical solutions for finite discrete systems

We have obtained exact analytical expressions in closed form, for the linear modes excited in finite and discrete systems that are driven by a spatially homogeneous alternating field. Those modes are extended for frequencies within the linear frequency band while they are either end-localized or end-avoided for frequencies outside the linear frequency band. The analytical solutions are resonant at particular frequencies, which compose the frequency dispersion relation of the finite system.     

\mathcal{PT}-symmetric nonlinear metamaterials and zero-dimensional systems

A one dimensional, parity-time ( $\mathcal{PT}$ )-symmetric magnetic metamaterial comprising split-ring resonators having both gain and loss is investigated. In the linear regime, the transition from the exact to the broken $\mathcal{PT}$ -phase is determined through the calculation of the eigenfrequency spectrum for two different configurations; the one with equidistant split-rings and the other with the split-rings forming a binary pattern ( $\mathcal{PT}$ dimer chain). The latter system features a two-band, gapped spectrum with its shape determined by the gain/loss coefficient as well as the interelement coupling. In the presence of nonlinearity, the $\mathcal{PT}$ dimer chain configuration with balanced gain and loss supports nonlinear localized modes in the form of a novel type of discrete breathers below the lower branch of the linear spectrum. These breathers that can be excited from a weak applied magnetic field by frequency chirping, can be subsequently driven solely by the gain for very long times. The effect of a small imbalance between gain and loss is also considered. Fundamental gain-driven breathers occupy both sites of a dimer, while their energy is almost equally partitioned between the two split-rings, the one with gain and the other with loss. We also introduce a model equation for the investigation of classical $\mathcal{PT}$ symmetry in zero dimensions, realized by a simple harmonic oscillator with matched time-dependent gain and loss that exhibits a transition from oscillatory to diverging motion. This behavior is similar to a transition from the exact to the broken $\mathcal{PT}$ phase in higher-dimensional $\mathcal{PT}$ -symmetric systems. A stability condition relating the parameters of the problem is obtained in the case of a piece-wise constant gain/loss function that allows the construction of a phase diagram with alternating stable and unstable regions.     

The assessment of user-perceived web quality: Application of a satisfaction benchmarking approach

The assessment of website quality is considered as a problem of measuring user satisfaction, in order to analyse user perceptions and preferences. The presented pilot user satisfaction survey concerns the major cellular phone service providers in Greece. The analysis is based on a multicriteria preference disaggregation approach for satisfaction benchmarking analysis and consists of the following parts: (1) the user satisfaction analysis, which concerns the identification of customer preferences and includes the estimation of the relative importance and the demanding level of the different user satisfaction dimensions, and (2) the satisfaction benchmarking analysis, which is mainly focused on the performance evaluation of the competitive organisations against the satisfaction criteria, as well as the identification of the competitive advantages of each company. The results presented in this paper demonstrate how business organisations may locate their position against competition, pinpoint their weak points and determine which website characteristics will improve their global performance.