Low-energy impact response of composite and sandwich composite plates with piezoelectric sensory layers

An efficient model reduction based methodology is presented for predicting the global (impact force, plate deflection and electric potential) and through-thickness local (interfacial strains and stresses) dynamic response of pristine simply-supported cross-ply composite and sandwich composite plates with piezoelectric sensory layers subjected to low-energy impact. The through-thickness response of the laminate is modelled using coupled higher-order layerwise displacement-based piezoelectric laminate theories. Linearized contact laws are implemented for simulating the impactor–target interaction during impact. The stiffness, mass, piezoelectric and permittivity matrices of the plate are formulated from ply to structural level and reduced by applying a Guyan reduction technique to yield the structural system in state space. This reduction technique enables the formulation of a plate–impactor structural system of minimum size (1 term per vibration mode for composite plates – 2 terms for sandwich plates) and reduces computational cost, thus facilitating applicability for real-time impact and vibration control.     

Dendritic Metalloporphyrin-Fullerene Conjugates: Changing the Microenvironment around Redox-Active Centers and its Impact on Charge-Transfer Reactions

Photophysical investigations on a series of (2,4,6)-tris-substituted metalloporphyrin-fullerene conjugates revealed the effects of an electron-rich microenvironment surrounding the electron-donating porphyrin as a function of the metal center. On one hand, for all conjugates-water-soluble and non-water-soluble-ultrafast charge separation was observed upon photoexcitation. On the other hand, when examining the charge recombination dynamics for the non-water-soluble conjugates it becomes obvious that the (2,4,6)-tris-substitution stabilizes the radical-ion-pair state relative to the mono-substitution in the ortho-, meta-, and para-position. The more efficient protection of the electron-donating porphyrin from solvation is thought to be the major cause for this impact. Nevertheless, the situation is slightly different for the water-soluble conjugates. At first glance, the radical-ion-pair state lifetimes are, also in the case of the (2,4,6)-tris-substitution, longer than for the mono-substituted ortho-, meta- and para-conjugates. Upon closer inspection, they fail, however, to exhibit any metal dependence. Competing with the protection from solvation of the dendrons, dipole-charge interactions impact the stabilization in the polar aqueous environment and, in turn, become the dominant force governing the electron-transfer dynamics.     

A charge-transfer challenge: combining fullerenes and metalloporphyrins in aqueous environments

A series of truly water-soluble C(60)/porphyrin electron donor-acceptor conjugates has been synthesized to serve as powerful mimics of photosynthetic reaction centers. To this end, the overall water-solubility of the conjugates was achieved by adding hydrophilic dendrimers of different generations to the porphyrin moiety. An important variable is the metal center of the porphyrin; we examined zinc(II), copper(II), cobalt(II), nickel(II), iron(III), and manganese(III). The first insights into electronic communication between the electron donors and the electron acceptors came from electrochemical assays, which clearly indicate that the redox processes centered either on C(60) or the porphyrins are mutually affected. Absorption measurements, however, revealed that the electronic communication in terms of, for example, charge-transfer features, remains spectroscopically invisible. The polar environment that water provides is likely to be a cause of the lack of detection. Despite this, transient absorption measurements confirm that intramolecular charge separation processes in the excited state lead to rapid deactivation of the excited states and, in turn, afford the formation of radical ion pair states in all of the investigated cases. Most importantly, the lifetimes of the radical ion pairs were found to depend strongly on several aspects. The nature of the coordinated metal center and the type of dendrimer have a profound impact on the lifetime. It has been revealed that the nature/electronic configuration of the metal centers is decisive in powering a charge recombination that either reinstates the ground state or any given multiplet excited state. Conversely, the equilibrium of two opposing forces in the dendrimers, that is, the interactions between their hydrophilic regions and the solvent and the electronic communication between their hydrophobic regions and the porphyrin and/or fullerene, is the key to tuning the lifetimes.     

Explicit propagators for a random walker and unidirectionality on linear chains

Explicit propagators are given for a diffusing particle (motor) moving on a linear chain of either infinity or finite length with reflecting ends. Each chain contains a number of thermally accessible barriers and/or potential wells (active sites). All particle interactions with its environment are considered to be short-range and are described by repulsive/attractive delta function potentials. By employing perturbation expansion, closed analytical expressions for the spatio-temporal evolution of the probability density function of the motor are derived, and are valid up to second order with respect to the expansion parameter u, which denotes the strength of interaction between motor and active sites. The mean displacement for two different chains is calculated indicating in both cases that the organization of the motion is done through the interplay of interaction intensities and their positions.     

Electronic transport between Au surface and scanning tunnelling microscope tip via a multipodal cyclodextrin host–metallo‐guest supramolecular system

An elementary supramolecular conducting system was constructed using a novel (±)‐thioctic acid‐functionalized β‐cyclodextrin host deposited on a gold (Au) surface and an iridium‐bearing guest molecule with biphenyl tails to insert specifically into the cyclodextrin cavity. The resulting supramolecular system was used to investigate remote electron communication between the flat Au surface and the platinum (Pt)/iridium (Ir) tip of a scanning tunnelling microscope. The morphology of the surfaces after successive deposition of host molecules followed by guest molecules was investigated. Formation of features of 2 nm size was shown on the Au surface functionalised with the supramolecular system. I–V spectroscopic analysis of the tunnelling current through this supramolecular layer revealed the relation between the effective barrier height and tunnelling distance. Thus, in the supramolecular host–metallo‐guest system, a small increase of conductance is observed, compared to the layer without the guest. This can be attributed to the presence of the Ir‐guest, which eventually creates intermediate energy states between the Au substrate and the Pt/Ir tip. Copyright © 2011 John Wiley & Sons, Ltd.     

Submerged fermentation of the edible mushroom Pleurotus ostreatus in a batch stirred tank bioreactor as a promising alternative for the effective production of bioactive metabolites

The aim of this study was to investigate the potential of the submerged fermentation procedure in the production of bioactive metabolites of the common edible mushroom Pleurotus ostreatus. The biomass of the mushroom strain was produced by submerged fermentation in a batch stirred tank bioreactor and extracted by solvents of increasing polarity. The dichloromethane and methanol extract were fractioned by different techniques including Adsorption Chromatography and Fast Centrifugal Partition Chromatography (FCPC). The structures of pure compounds were elucidated with 1D/2D NMR-spectroscopic analyses, and chemical correlations combined with GC/MS and LC/MS experiments. Nineteen metabolites (e.g., fatty acids, phenolic metabolites, nucleotides and alkaloids) were isolated. Beyond the production of known metabolites, we report herein the production also of trans-3,4-dihydro-3,4,8-trihydroxynapthalen-1(2H)-one, indolo-3-carboxylic acid, 3-formylpyrrole and 4-hydroxybenzoic acid, that have pharmaceutical interest and are isolated for the first time from Pleurotus strains. This work indicates the great potential of the established bioprocess for the production of P. ostreatus mycelia with enhanced metabolic profile.     

Interaction-induced dipoles of hydrogen molecules colliding with helium atoms: a new ab initio dipole surface for high-temperature applications

We report new ab initio results for the interaction-induced dipole moments Δμ of hydrogen molecules colliding with helium atoms. These results are needed in order to calculate collision-induced absorption spectra at high temperatures; applications include modeling the radiative profiles of very cool white dwarf stars, with temperatures from 3500 K to 9000 K. We have evaluated the dipoles based on finite-field calculations, with coupled cluster methods in MOLPRO 2006 and aug-cc-pV5Z (spdfg) basis sets for both the H and He centers. We have obtained values of Δμ for eight H(2) bond lengths ranging from 0.942 a.u. to 2.801 a.u., for 15 intermolecular separations R ranging from 2.0 a.u. to 10.0 a.u., and for 19 different relative orientations. In general, our values agree well with earlier ab initio results, for the geometrical configurations that are treated in common, but we have determined more points on the collision-induced dipole surface by an order of magnitude. These results make it possible to calculate transition probabilities for molecules in excited vibrational states, overtones, and rotational transitions with ΔJ > 4. We have cast our results in the symmetry-adapted form needed for absorption line shape calculations, by expressing Δμ as a series in the spherical harmonics of the orientation angles of the intermolecular vector and of a unit vector along the H(2) bond axis. The expansion coefficients depend on the H(2) bond length and the intermolecular distance R. For large separations R, we show that the ab initio values of the leading coefficients converge to the predictions from perturbation theory, including both classical multipole polarization and dispersion effects.     

Practical synthesis of 1′-substituted Tubercidin C-nucleoside analogs

Several 1′-substituted analogs of Tubercidin C-nucleosides were prepared using a highly convergent synthesis. Good to high diastereoselectivity was achieved using a variety of nucleophiles targeting the 1′-position. The source for this stereoselectivity is herein proposed. It is thought to be attributed to a temperature-dependent chelation of the incoming nucleophile to either the 2′- or 3′-benzyloxy ether of the ribose core.     

On the maximum number of feasible ranking sequences in multi-criteria decision making problems

In many decision problems the focus is on ranking a set of m alternatives in terms of a number, say n, of decision criteria. Given are the performance values of the alternatives for each one of the criteria and the weights of importance of the criteria. This paper demonstrates that if one assumes that the criteria weights are changeable, then the number of all possible rankings may be significantly less than the upper limit of m!. As a matter of fact, this paper demonstrates that the number of possible rankings is a function of the number of alternatives and the number of criteria. These findings are important from a sensitivity analysis point of view or when a group decision making environment is considered.