Synthesis, structural analysis, and magnetic behaviour of three fumarate bridged coordination polymers: five-fold interpenetrated diamond-like net of Ni-II, sheets of Ni-II and Co-II

The hydrothermal reactions of Ni(NO3)(2).6H(2)O, disodium fumarate (fum) and 1,2-bis(4-pyridyl)ethane (bpe)/1,3-bis(4-pyridyl) propane (bpp) in aqueous-methanol medium yield one 3-D and one 2-D metal-organic hybrid material, [Ni(fum)(bpe)] (1) and [Ni(fum)(bpp)(H2O)] (2), respectively. Complex 1 possesses a novel unprecedented structure, the first example of an "unusual mode" of a five-fold distorted interpenetrated network with metal-ligand linkages where the four six-membered windows in each adamantane-type cage are different. The structural characterization of complex 2 evidences a buckled sheet where nickel ions are in a distorted octahedral geometry, with two carboxylic groups, one acting as a bis-chelate, the other as a bis-monodentate ligand. The metal ion completes the coordination sphere through one water molecule and two bpp nitrogens in cis position. Variable-temperature magnetic measurements of complexes 1 and 2 reveal the existence of very weak antiferromagnetic intramolecular interactions and/or the presence of single-ion zero field splitting (D) of isolated Ni-II ions in both the compounds. Experimentally, both the J parameters are close, comparable and very small. Considering zero-field splitting of Ni-II, the calculated D values are in agreement with values reported in the literature for Ni-II ions. Complex 3, [{Co(phen)}(2)(fum)(2)] (phen=1,10-phenanthroline) is obtained by diffusing methanolic solution of 1,10-phenanthroline on an aqueous layer of disodium fumarate and Co(NO3)(2).6H(2)O. It consists of dimeric Co-II(phen) units, doubly bridged by carboxylate groups in a distorted syn-syn fashion. These fumarate anions act as bis-chelates to form corrugated sheets. The 2D layer has a (4,4) topology, with the nodes represented by the centres of the dimers. The magnetic data were fitted ignoring the very weak coupling through the fumarate pathway and using a dimer model.

Discrepancy between parental reports of infants' receptive vocabulary and infants' behaviour in a preferential looking task

Two experiments are described which explore the relationship between parental reports of infants' receptive vocabularies at 1; 6 (Experiment 1a) or 1-3, 1;6 and 1;9 (Experiment 1b) and the comprehension infants demonstrated in a preferential looking task. The instrument used was the Oxford CD1, a British English adaptation of the MacArthur-Bates CD1 (Words & Gestures). Infants were shown pairs of images of familiar objects, either both name-known or both name-unknown according to their parent's responses on the CD1. At all ages, and on both name-known and name-unknown trials, preference for the target image increased significantly from baseline when infants heard the target's label. This discrepancy suggests that parental report underestimates infants' word knowledge.

Rheological and thermal behaviour of poly(N-isopropylacrylamide)/alginate smart polymeric networks

Interpenetrating polymeric networks based on sodium alginate and poly(N-isopropylacrylamide) (PNIPAAm) covalently crosslinked with N,N′-methylenebisacrylamide have been investigated using rheology, thermogravimetry, differential scanning calorimetry, X-ray diffraction measurements and scanning electron microscopy (SEM). An improved elastic response of the samples with a higher PNIPAAm content and increased amount of crosslinking agent was found. The temperature-responsive behaviour of the hydrogel samples was evidenced by viscoelastic measurements performed at various temperatures. It is shown that the properties of these gels can be tuned according to composition, amount of crosslinking agent and temperature changes. X-ray scattering analysis revealed that the hydrophobic groups are locally segregated even in the swollen state whilst cryo-SEM showed the highly heterogeneous nature of the gels.

Synthesis and phase behaviour of a homologous series of polymethacrylate-based side-chain liquid crystal polymers

The homologous series of side chain liquid crystal polymers, the poly[x-(4-methoxyazobenzene- 40-oxy)alkyl methacrylate]s, has been prepared in which the length of the flexible alkyl spacer has been varied from 3 to 11 methylene units. All the polymers exhibit liquid crystalline behaviour. The propyl and butyl members show exclusively nematic behaviour. The pentyl, hexyl, octyl and decyl members show a nematic and a smectic A phase while the heptyl, nonyl and undecyl homologues exhibit only a smectic A phase. The smectic A phase has been studied using X-ray diffraction and assigned as a smectic A1 phase in which the side chains are fully overlapped and the backbones are confined to lie between the smectic layers. For the nonyl member an incommensurate smectic phase is observed. The dependence of the transition temperatures on the length of the flexible spacer is understood in terms of the average shapes of the side chains.

Passive urban ventilation by combined buoyancy-driven slope flow and wall flow: Parametric CFD studies on idealized city models

This paper reports the results of a parametric CFD study on idealized city models to investigate the potential of slope flow in ventilating a city located in a mountainous region when the background synoptic wind is absent. Examples of such a city include Tokyo in Japan, Los Angeles and Phoenix in the US, and Hong Kong. Two types of buoyancy-driven flow are considered, i.e., slope flow from the mountain slope (katabatic wind at night and anabatic wind in the daytime), and wall flow due to heated/cooled urban surfaces. The combined buoyancy-driven flow system can serve the purpose of dispersing the accumulated urban air pollutants when the background wind is weak or absent. The microscopic picture of ventilation performance within the urban structures was evaluated in terms of air change rate (ACH) and age of air. The simulation results reveal that the slope flow plays an important role in ventilating the urban area, especially in calm conditions. Katabatic flow at night is conducive to mitigating the nocturnal urban heat island. In the present parametric study, the mountain slope angle and mountain height are assumed to be constant, and the changing variables are heating/cooling intensity and building height. For a typical mountain of 500 m inclined at an angle of 20° to the horizontal level, the interactive structure is very much dependent on the ratio of heating/cooling intensity as well as building height. When the building is lower than 60 m, the slope wind dominates. When the building is as high as 100 m, the contribution from the urban wall flow cannot be ignored. It is found that katabatic wind can be very beneficial to the thermal environment as well as air quality at the pedestrian level. The air change rate for the pedestrian volume can be as high as 300 ACH.

Comparative study of the performance of the M-cycle counter-flow and cross-flow heat exchangers for indirect evaporative cooling - paving the path towards sustainable cooling of buildings

This paper provides a comparative study of the performance of cross-flow and counter-flow M-cycle heat exchangers for dew point cooling. It is recognised that evaporative cooling systems offer a low energy alternative to conventional air conditioning units. Recently emerged dew point cooling, as the renovated evaporative cooling configuration, is claimed to have much higher cooling output over the conventional evaporative modes owing to use of the M-cycle heat exchangers. Cross-flow and counter-flow heat exchangers, as the available structures for M-cycle dew point cooling processing, were theoretically and experimentally investigated to identify the difference in cooling effectiveness of both under the parallel structural/operational conditions, optimise the geometrical sizes of the exchangers and suggest their favourite operational conditions. Through development of a dedicated computer model and case-by-case experimental testing and validation, a parametric study of the cooling performance of the counter-flow and cross-flow heat exchangers was carried out. The results showed the counter-flow exchanger offered greater (around 20% higher) cooling capacity, as well as greater (15%–23% higher) dew-point and wet-bulb effectiveness when equal in physical size and under the same operating conditions. The cross-flow system, however, had a greater (10% higher) Energy Efficiency (COP). As the increased cooling effectiveness will lead to reduced air volume flow rate, smaller system size and lower cost, whilst the size and cost are the inherent barriers for use of dew point cooling as the alternation of the conventional cooling systems, the counter-flow system is considered to offer practical advantages over the cross-flow system that would aid the uptake of this low energy cooling alternative. In line with increased global demand for energy in cooling of building, largely by economic booming of emerging developing nations and recognised global warming, the research results will be of significant importance in terms of promoting deployment of the low energy dew point cooling system, helping reduction of energy use in cooling of buildings and cut of the associated carbon emission.

Complexes of NiX2 (X=Cl− and NO3−) with a NNO donor Schiff base: anion dependent structural variations and spectroscopic behaviour

Two new nickel(11) complexes, [NiLL'(H2O)(2)Cl] (1) and [{NiLL'(H2O)](2)(mu-H)]NO3·H2O(2), have been synthesized using a tridentate Schiff base ligand, HL, 2-[(2-dimethylamino-ethylimino)-methyl]-phenol, along with Cl- or NO3(-) as an anionic co-ligand or counter anion (where L'H = salicylaldehyde). Both complexes have been characterized by X-ray crystallography. The structural analyses reveal that complex 1 is mononuclear whereas 2 is a hydrogen-bridged dinuclear complex. The Ni(II) ions possess a distorted octahedral geometry in both structures. Both complexes show negative solvatochromic behaviour with increasing donor number (DN) of the solvent. In more coordinating solvents, like DMSO or methanol, the colour of the solutions is green, whereas in less coordinating solvents, like dichloromethane (DCM) or acetonitrile, it is red.

The signature of ENSO in the Northern Hemisphere midlatitude seasonal mean flow and high-frequency intraseasonal variability

The impact of pronounced positive and negative sea surface temperature (STT) anomalies in the tropical Pacific associated with the El Niño/Southern Oscillation (ENSO) phenomenon on the atmospheric circulation in the Northern Hemisphere extratropics during the boreal winter season is investigated. This includes both the impact on the seasonal mean flow and on the intraseasonal variability on synoptic time scales. Moreover, the interaction between the transient fluctuations on these times scales and the mean circulation is examined. Both data from an ensemble of five simulations with the ECHAM3 atmospheric general circulation model at a horizontal resolution of T42 each covering the period from 1979 through 1992 and operational analyses from ECMWF for the corresponding period are examined. In each of the simulations observed SSTs for the period of investigation are given as lower boundary forcing, but different atmospheric initial conditions are prescribed. The simulations with ECHAM3 reveal a distinct impact of the pronounced SST-anomalies in the tropical Pacific on the atmospheric circulation in the Northern Hemisphere extratropics during El Niño as well as during La Niña events. These changes in the atmospheric circulation, which are found to be highly significant in the Pacific/North American as well as in the Atlantic/European region, are consistent with the essential results obtained from the analyses. The pronounced SST-anomalies in the tropical Pacific lead to changes in the mean circulation, which are characterized by typical circulation patterns. These changes in the mean circulation are accompanied by marked variations of the activity of the transient fluctuations on synoptic time scales, that are changes in both the kinetic energy on these time scales and the atmospheric transports of momentum and heat accomplished by the short baroclinic waves. The synoptic disturbances, on the other hand, play also an important role in controlling the changes in the mean circulation associated with the ENSO phenomenon. They maintain these typical circulation patterns via barotropic, but counteract them via baroclinic processes. The hypothesis of an impact of the ENSO phenomenon in the Atlantic/European region can be supported. As the determining factor the intensification (reduction) of the Aleutian low and the simultaneous reduction (intensification) of the Icelandic low during El Niño and during La Niña events respectively, is identified. The changes in the intensity of the Aleutian low during the ENSO-events are accompanied by an alteration of the transport of momentum caused by the short baroclinic waves over the North American continent in such a way that the changes in the intensity of the Icelandic low during El Niño as well as during La Niña events are maintained.

A time-invariant visco-elastic windkessel model relating blood flow and blood volume

The difference between the rate of change of cerebral blood volume (CBV) and cerebral blood flow (CBF) following stimulation is thought to be due to circumferential stress relaxation in veins (Mandeville, J.B., Marota, J.J.A., Ayata, C., Zaharchuk, G., Moskowitz, M.A., Rosen, B.R., Weisskoff, R.M., 1999. Evidence of a cerebrovascular postarteriole windkessel with delayed compliance. J. Cereb. Blood Flow Metab. 19, 679–689). In this paper we explore the visco-elastic properties of blood vessels, and present a dynamic model relating changes in CBF to changes in CBV. We refer to this model as the visco-elastic windkessel (VW) model. A novel feature of this model is that the parameter characterising the pressure–volume relationship of blood vessels is treated as a state variable dependent on the rate of change of CBV, producing hysteresis in the pressure–volume space during vessel dilation and contraction. The VW model is nonlinear time-invariant, and is able to predict the observed differences between the time series of CBV and that of CBF measurements following changes in neural activity. Like the windkessel model derived by Mandeville, J.B., Marota, J.J.A., Ayata, C., Zaharchuk, G., Moskowitz, M.A., Rosen, B.R., Weisskoff, R.M., 1999. Evidence of a cerebrovascular postarteriole windkessel with delayed compliance. J. Cereb. Blood Flow Metab. 19, 679–689, the VW model is primarily a model of haemodynamic changes in the venous compartment. The VW model is demonstrated to have the following characteristics typical of visco-elastic materials: (1) hysteresis, (2) creep, and (3) stress relaxation, hence it provides a unified model of the visco-elastic properties of the vasculature. The model will not only contribute to the interpretation of the Blood Oxygen Level Dependent (BOLD) signals from functional Magnetic Resonance Imaging (fMRI) experiments, but also find applications in the study and modelling of the brain vasculature and the haemodynamics of circulatory and cardiovascular systems.

Model estimation of cerebral hemodynamics between blood flow and volume changes: A data-based modeling approach

It is well known that there is a dynamic relationship between cerebral blood flow (CBF) and cerebral blood volume (CBV). With increasing applications of functional MRI, where the blood oxygen-level-dependent signals are recorded, the understanding and accurate modeling of the hemodynamic relationship between CBF and CBV becomes increasingly important. This study presents an empirical and data-based modeling framework for model identification from CBF and CBV experimental data. It is shown that the relationship between the changes in CBF and CBV can be described using a parsimonious autoregressive with exogenous input model structure. It is observed that neither the ordinary least-squares (LS) method nor the classical total least-squares (TLS) method can produce accurate estimates from the original noisy CBF and CBV data. A regularized total least-squares (RTLS) method is thus introduced and extended to solve such an error-in-the-variables problem. Quantitative results show that the RTLS method works very well on the noisy CBF and CBV data. Finally, a combination of RTLS with a filtering method can lead to a parsimonious but very effective model that can characterize the relationship between the changes in CBF and CBV.