Mono- and binuclear bipyridyl derivatives of the Mo(eta(3)-C3H5)(CO)(2) fragment: structural studies and fluxionality in solution

New mono- and binuclear complexes of the Mo(eta(3)-C3H5)(CO)(2) fragment, containing bipyridyl ligands (2,2'-bpy, 4,4'-Me-2-2,2'-bpy) as chelates, and mono- (4-CNpy, 4-Mepy, NCMe, Br) or bidentate nitrogen ligands (4,4'-bpy, bipyridylethylene, pyrazine) as terminal or bridging ligands, respectively, were prepared. The binuclear complex [{Mo(eta(3)-C3H5)(CO)(2)(2,2'-bpy)}(2)(mu-4,4'-bpy)][PF6](2) (2) was shown by X-ray diffraction to assemble in the crystal forming large channels with a rectangular section. A longer bridge, such as bipyridylethylene, led to a different structure (3). 4-CNpy behaved as monodentate ligand (4), coordinating through the pyridine nitrogen as a terminal ligand. NMR spectroscopy studies showed that the complexes exhibited a fluxional behavior in solution, the endo and exo forms of the more symmetrical equatorial isomers being usually present and interconverting in solution. The solid state structures of the complexes revealed a preference for the more symmetrical equatorial isomer, with the two chelate ligands in trans positions in the binuclear species. The rings tended to become parallel in the organized crystal. (C) 2003 Elsevier B.V. All rights reserved.

Syntheses and crystal structures of two new coordination polymers of Cd(II) using organic spacer and inorganic-bridging ligands

Two new cadmium (II) complexes [Cd(hmt)(dca)(2)] (n) (1) and [Cd-3(hmt)(2)(SeCN)(6)(H2O)(2)] (n) (2) (hmt=hexamethylenetetramine, dca=dicyanamide) have been synthesized and characterized by X-ray single-crystal analysis. The complex 1 is a 2D rectangular grid of octahedral cadmium (II) with CdN6 chromophore where cadmium centers are doubly bridged by dicyanamide and hmt along a-axis, which are interlinked by dicyanamide running along c-axis. Whereas, complex 2 is a 1D chain of octahedral cadmium (II) with a three-leg ladder topology running along a-axis. The Cd(II) centers are doubly bridged through SeCN (infinite rail) along a-axis and singly bridged by hmt (two-step rung) along c-axis, having cadmium centers with CdSe2N3O and CdSe2N4 chromophores. The adjacent chains through H-bonding between coordinated water and hmt, and (SeSe)-Se-... interaction are extended to 2D supramolecular architecture.

Investigation of the fracture mode for hard and soft wheat endosperm using the loading-unloading bending test

Investigation of the fracture mode for hard and soft wheat endosperm was aimed at gaining a better understanding of the fragmentation process. Fracture mechanical characterization was based on the three-point bending test which enables stable crack propagation to take place in small rectangular pieces of wheat endosperm. The crack length can be measured in situ by using an optical microscope with light illumination from the side of the specimen or from the back of the specimen. Two new techniques were developed and used to estimate the fracture toughness of wheat endosperm, a geometric approach and a compliance method. The geometric approach gave average fracture toughness values of 53.10 and 27.0 J m(-2) for hard and soft endosperm, respectively. Fracture toughness estimated using the compliance method gave values of 49.9 and 29.7 J m(-2) for hard and soft endosperm, respectively. Compressive properties of the endosperm in three mutually perpendicular axes revealed that the hard and soft endosperms are isotropic composites. Scanning electron microscopy (SEM) observation of the fracture surfaces and the energy-time curves of loading-unloading cycles revealed that there was a plastic flow during crack propagation for both the hard and soft endosperms, and confirmed that the fracture mode is significantly related to the adhesion level between starch granules and the protein matrix.

Optimization of apodization functions in terahertz transient spectrometry

A quadratic programming optimization procedure for designing asymmetric apodization windows tailored to the shape of time-domain sample waveforms recorded using a terahertz transient spectrometer is proposed. By artificially degrading the waveforms, the performance of the designed window in both the time and the frequency domains is compared with that of conventional rectangular, triangular (Mertz), and Hamming windows. Examples of window optimization assuming Gaussian functions as the building elements of the apodization window are provided. The formulation is sufficiently general to accommodate other basis functions. (C) 2007 Optical Society of America

Measurement of propagation constant in waveguides with wideband coherent terahertz spectroscopy

A quasi-optical technique for characterizing micromachined waveguides is demonstrated with wideband time-resolved terahertz spectroscopy. A transfer-function representation is adopted for the description of the relation between the signals in the input and output port of the waveguides. The time-domain responses were discretized, and the waveguide transfer function was obtained through a parametric approach in the z domain after describing the system with an autoregressive with exogenous input model. The a priori assumption of the number of modes propagating in the structure was inferred from comparisons of the theoretical with the measured characteristic impedance as well as with parsimony arguments. Measurements for a precision WR-8 waveguide-adjustable short as well as for G-band reduced-height micromachined waveguides are presented. (C) 2003 Optical Society of America.

Generalized honeycomb torus is Hamiltonian

Generalized honeycomb torus is a candidate for interconnection network architectures, which includes honeycomb torus, honeycomb rectangular torus, and honeycomb parallelogramic torus as special cases. Existence of Hamiltonian cycle is a basic requirement for interconnection networks since it helps map a "token ring" parallel algorithm onto the associated network in an efficient way. Cho and Hsu [Inform. Process. Lett. 86 (4) (2003) 185-190] speculated that every generalized honeycomb torus is Hamiltonian. In this paper, we have proved this conjecture. (C) 2004 Elsevier B.V. All rights reserved.

Baroclinic stationary waves in aquaplanet models

An aquaplanet model is used to study the nature of the highly persistent low-frequency waves that have been observed in models forced by zonally symmetric boundary conditions. Using the Hayashi spectral analysis of the extratropical waves, the authors find that a quasi-stationary wave 5 belongs to a wave packet obeying a well-defined dispersion relation with eastward group velocity. The components of the dispersion relation with k ≥ 5 baroclinically convert eddy available potential energy into eddy kinetic energy, whereas those with k < 5 are baroclinically neutral. In agreement with Green’s model of baroclinic instability, wave 5 is weakly unstable, and the inverse energy cascade, which had been previously proposed as a main forcing for this type of wave, only acts as a positive feedback on its predominantly baroclinic energetics. The quasi-stationary wave is reinforced by a phase lock to an analogous pattern in the tropical convection, which provides further amplification to the wave. It is also found that the Pedlosky bounds on the phase speed of unstable waves provide guidance in explaining the latitudinal structure of the energy conversion, which is shown to be more enhanced where the zonal westerly surface wind is weaker. The wave’s energy is then trapped in the waveguide created by the upper tropospheric jet stream. In agreement with Green’s theory, as the equator-to-pole SST difference is reduced, the stationary marginally stable component shifts toward higher wavenumbers, while wave 5 becomes neutral and westward propagating. Some properties of the aquaplanet quasi-stationary waves are found to be in interesting agreement with a low frequency wave observed by Salby during December–February in the Southern Hemisphere so that this perspective on low frequency variability, apart from its value in terms of basic geophysical fluid dynamics, might be of specific interest for studying the earth’s atmosphere.

Random orthogonal matrix simulation

This paper introduces a method for simulating multivariate samples that have exact means, covariances, skewness and kurtosis. We introduce a new class of rectangular orthogonal matrix which is fundamental to the methodology and we call these matrices L matrices. They may be deterministic, parametric or data specific in nature. The target moments determine the L matrix then infinitely many random samples with the same exact moments may be generated by multiplying the L matrix by arbitrary random orthogonal matrices. This methodology is thus termed “ROM simulation”. Considering certain elementary types of random orthogonal matrices we demonstrate that they generate samples with different characteristics. ROM simulation has applications to many problems that are resolved using standard Monte Carlo methods. But no parametric assumptions are required (unless parametric L matrices are used) so there is no sampling error caused by the discrete approximation of a continuous distribution, which is a major source of error in standard Monte Carlo simulations. For illustration, we apply ROM simulation to determine the value-at-risk of a stock portfolio.

Well-posed two-point initial-boundary value problems with arbitrary boundary conditions

We study initial-boundary value problems for linear evolution equations of arbitrary spatial order, subject to arbitrary linear boundary conditions and posed on a rectangular 1-space, 1-time domain. We give a new characterisation of the boundary conditions that specify well-posed problems using Fokas' transform method. We also give a sufficient condition guaranteeing that the solution can be represented using a series. The relevant condition, the analyticity at infinity of certain meromorphic functions within particular sectors, is significantly more concrete and easier to test than the previous criterion, based on the existence of admissible functions.

One-port de-embedding technique for the quasi-optical characterization of integrated components

We describe a one-port de-embedding technique suitable for the quasi-optical characterization of terahertz integrated components at frequencies beyond the operational range of most vector network analyzers. This technique is also suitable when the manufacturing of precision terminations to sufficiently fine tolerances for the application of a TRL de-embedding technique is not possible. The technique is based on vector reflection measurements of a series of easily realizable test pieces. A theoretical analysis is presented for the precision of the technique when implemented using a quasi-optical null-balanced bridge reflectometer. The analysis takes into account quantization effects in the linear and angular encoders associated with the balancing procedure, as well as source power and detector noise equivalent power. The precision in measuring waveguide characteristic impedance and attenuation using this de-embedding technique is further analyzed after taking into account changes in the power coupled due to axial, rotational, and lateral alignment errors between the device under test and the instruments' test port. The analysis is based on the propagation of errors after assuming imperfect coupling of two fundamental Gaussian beams. The required precision in repositioning the samples at the instruments' test-port is discussed. Quasi-optical measurements using the de-embedding process for a WR-8 adjustable precision short at 125 GHz are presented. The de-embedding methodology may be extended to allow the determination of S-parameters of arbitrary two-port junctions. The measurement technique proposed should prove most useful above 325 GHz where there is a lack of measurement standards.

Crooks' fluctuation theorem for a process on a two dimensional fluid field

We investigate the behavior of a two-dimensional inviscid and incompressible flow when pushed out of dynamical equilibrium. We use the two-dimensional vorticity equation with spectral truncation on a rectangular domain. For a sufficiently large number of degrees of freedom, the equilibrium statistics of the flow can be described through a canonical ensemble with two conserved quantities, energy and enstrophy. To perturb the system out of equilibrium, we change the shape of the domain according to a protocol, which changes the kinetic energy but leaves the enstrophy constant. We interpret this as doing work to the system. Evolving along a forward and its corresponding backward process, we find numerical evidence that the distributions of the work performed satisfy the Crooks relation. We confirm our results by proving the Crooks relation for this system rigorously.

Glimpsing regular lattice arrangements of primary rat hippocampal astrocytes on ultra-thin nodes of Parylene-C

In our seminal work, we reported how the biomaterial Parylene-C has the unique ability to coerce neurons and glial cells to migrate to and then grow in straight lines along serum coated rectangular parylene-C structures mounted on an oxidised silicon substrate. In this brief communication, we report how astrocyte cell bodies, from the dissociated postnatal rat hippocampus, can now to be successfully localised on an ultra-thin 13nm layer of parylene-C mounted on oxidised silicon (Figure 1). What is extremely interesting about this finding is that the astrocyte processes extended mainly in horizontal and vertical directions from the cell body thus creating a regular lattice network of individual cells. In addition, they comfortably extended a 50μm gap (equivalent to ~ 10 cell body diameters) to connect to adjacent astrocytes on neighbouring Parylene-C structures. This was found to occur repeatedly on circular geometries of 20μm diameter. In comparison to our previous work [1], we have decreased the thickness of the parylene-C structures by a factor of 10, to allow such technology to be able to be utilised for passive electrode design that requires extremely thin structures such as these. Thus, being able to culture astrocytes in regular lattice networks will pave the way for precise monitoring and stimulation of such ensembles via multi-electrode arrays, allowing a closer insight into their dynamic behaviour and their network properties.

The role of sky conditions on gross primary production in a mixed deciduous forest

The role of different sky conditions on diffuse PAR fraction (ϕ), air temperature (Ta), vapor pressure deficit (vpd) and GPP in a deciduous forest is investigated using eddy covariance observations of CO2 fluxes and radiometer and ceilometer observations of sky and PAR conditions on hourly and growing season timescales. Maximum GPP response occurred under moderate to high PAR and ϕ and low vpd. Light response models using a rectangular hyperbola showed a positive linear relation between ϕ and effective quantum efficiency (α = 0.023ϕ + 0.012, r2 = 0.994). Since PAR and ϕ are negatively correlated, there is a tradeoff between the greater use efficiency of diffuse light and lower vpd and the associated decrease in total PAR available for photosynthesis. To a lesser extent, light response was also modified by vpd and Ta. The net effect of these and their relation with sky conditions helped enhance light response under sky conditions that produced higher ϕ. Six sky conditions were classified from cloud frequency and ϕ data: optically thick clouds, optically thin clouds, mixed sky (partial clouds within hour), high, medium and low optical aerosol. The frequency and light responses of each sky condition for the growing season were used to predict the role of changing sky conditions on annual GPP. The net effect of increasing frequency of thick clouds is to decrease GPP, changing low aerosol conditions has negligible effect. Increases in the other sky conditions all lead to gains in GPP. Sky conditions that enhance intermediate levels of ϕ, such as thin or scattered clouds or higher aerosol concentrations from volcanic eruptions or anthropogenic emissions, will have a positive outcome on annual GPP, while an increase in cloud cover will have a negative impact. Due to the ϕ/PAR tradeoff and since GPP response to changes in individual sky conditions differ in sign and magnitude, the net response of ecosystem GPP to future sky conditions is non-linear and tends toward moderation of change.

Quantitative ventilation assessments of idealized urban canopy layers with various urban layouts and the same building packing density

This paper investigates urban canopy layers (UCL) ventilation under neutral atmospheric condition with the same building area density (λp=0.25) and frontal area density (λf=0.25) but various urban sizes, building height variations, overall urban forms and wind directions. Turbulent airflows are first predicted by CFD simulations with standard k-ε model evaluated by wind tunnel data. Then air change rates per hour (ACH) and canopy purging flow rate (PFR) are numerically analyzed to quantify the rate of air exchange and the net ventilation capacity induced by mean flows and turbulence. With a parallel approaching wind (θ=0o), the velocity ratio first decreases in the adjustment region, followed by the fully-developed region where the flow reaches a balance. Although the flow quantities macroscopically keep constant, however ACH decreases and overall UCL ventilation becomes worse if urban size rises from 390m to 5km. Theoretically if urban size is infinite, ACH may reach a minimum value depending on local roof ventilation, and it rises from 1.7 to 7.5 if the standard deviation of building height variations increases (0% to 83.3%). Overall UCL ventilation capacity (PFR) with a square overall urban form (Lx=Ly=390m) is better as θ=0o than oblique winds (θ=15o, 30o, 45o), and it exceeds that of a staggered urban form under all wind directions (θ=0o to 45o), but is less than that of a rectangular urban form (Lx=570m, Ly=270m) under most wind directions (θ=30o to 90o). Further investigations are still required to quantify the net ventilation efficiency induced by mean flows and turbulence.

In optics humidity compensation in NDIR exhaust gas measurements of NO2

NDIR is proposed for monitoring of air pollutants emitted by ship engines. Careful optical filtering overcomes the challenge of optical detection of NO2 in humid exhaust gas, despite spectroscopic overlap with the water vapour band.