Systematic studies on 3d-3d and 3d-4f multimetallic complexes with interesting magnetic and/or luminescent properties

324 p.

Pose Refinement of Active Models using Forces in 3D

A new algorithm is described for refining the pose of a model of a rigid object, to conform more accurately to the image structure. Elemental 3D forces are considered to act on the model. These are derived from directional derivatives of the image local to the projected model features. The convergence properties of the algorithm is investigated and compared to a previous technique. Its use in a video sequence of a cluttered outdoor traffic scene is also illustrated and assessed.

A Newton method for pose refinement of 3D models

Different optimization methods can be employed to optimize a numerical estimate for the match between an instantiated object model and an image. In order to take advantage of gradient-based optimization methods, perspective inversion must be used in this context. We show that convergence can be very fast by extrapolating to maximum goodness-of-fit with Newton's method. This approach is related to methods which either maximize a similar goodness-of-fit measure without use of gradient information, or else minimize distances between projected model lines and image features. Newton's method combines the accuracy of the former approach with the speed of convergence of the latter.

Cue combination for 3D location judgements

Cue combination rules have often been applied to the perception of surface shape but not to judgements of object location. Here, we used immersive virtual reality to explore the relationship between different cues to distance. Participants viewed a virtual scene and judged the change in distance of an object presented in two intervals, where the scene changed in size between intervals (by a factor of between 0.25 and 4). We measured thresholds for detecting a change in object distance when there were only 'physical' (stereo and motion parallax) or 'texture-based' cues (independent of the scale of the scene) and used these to predict biases in a distance matching task. Under a range of conditions, in which the viewing distance and position of the tarte relative to other objects was varied, the ration of 'physical' to 'texture-based' thresholds was a good predictor of biases in the distance matching task. The cue combination approach, which successfully accounts for our data, relies on quite different principles from those underlying geometric reconstruction.

The point-source method for 3D reconstructions for the Helmholtz and Maxwell equations

We use the point-source method (PSM) to reconstruct a scattered field from its associated far field pattern. The reconstruction scheme is described and numerical results are presented for three-dimensional acoustic and electromagnetic scattering problems. We give new proofs of the algorithms, based on the Green and Stratton-Chu formulae, which are more general than with the former use of the reciprocity relation. This allows us to handle the case of limited aperture data and arbitrary incident fields. Both for 3D acoustics and electromagnetics, numerical reconstructions of the field for different settings and with noisy data are shown. For shape reconstruction in acoustics, we develop an appropriate strategy to identify areas with good reconstruction quality and combine different such regions into one joint function. Then, we show how shapes of unknown sound-soft scatterers are found as level curves of the total reconstructed field.

A 3D stochastic cloud model for investigating the radiative properties of inhomogeneous cirrus clouds

(From author). Comments: First 3D stochastic/fractal model of cirrus; first detailed analysis & explanation of power spectra of ice water content, including first observations of 50-km scale break and mixing-induced steepening of spectrum; first demonstration of the potential effect of wind shear on radiative fluxes by changing fall-streak orientation. Has spawned work on the effect of 3D photon transport on the radiative effects of cirrus clouds.

African climate change: Taking the shorter route

Numerous factors are associated with poverty and underdevelopment in Africa, including climate variability. Rainfall, and climate more generally, are implicated directly in the United Nations “Millennium Development Goals” to eradicate extreme poverty and hunger, and reduce child mortality and incidence of diseases such as malaria by the target date of 2015. But, Africa is not currently on target to meet these goals. We pose a number of questions from a climate science perspective aimed at understanding this background: Is there a common origin to factors that currently constrain climate science? Why is it that in a continent where human activity is so closely linked to interannual rainfall variability has climate science received little of the benefit that saw commercialization driving meteorology in the developed world? What might be suggested as an effective way for the continent to approach future climate variability and change? We make the case that a route to addressing the challenges of climate change in Africa rests with the improved management of climate variability. We start by discussing the constraints on climate science and how they might be overcome. We explain why the optimal management of activities directly influenced by interannual climate variability (which include the development of scientific capacity) has the potential to serve as a forerunner to engagement in the wider issue of climate change. We show this both from the perspective of the climate system and the institutions that engage with climate issues. We end with a thought experiment that tests the benefits of linking climate variability and climate change in the setting of smallholder farmers in Limpopo Province, South Africa.

Stereo and motion parallax cues in human 3D vision: can they vanish without a trace?

In an immersive virtual reality environment, subjects fail to notice when a scene expands or contracts around them, despite correct and consistent information from binocular stereopsis and motion parallax, resulting in gross failures of size constancy (A. Glennerster, L. Tcheang, S. J. Gilson, A. W. Fitzgibbon, & A. J. Parker, 2006). We determined whether the integration of stereopsis/motion parallax cues with texture-based cues could be modified through feedback. Subjects compared the size of two objects, each visible when the room was of a different size. As the subject walked, the room expanded or contracted, although subjects failed to notice any change. Subjects were given feedback about the accuracy of their size judgments, where the “correct” size setting was defined either by texture-based cues or (in a separate experiment) by stereo/motion parallax cues. Because of feedback, observers were able to adjust responses such that fewer errors were made. For texture-based feedback, the pattern of responses was consistent with observers weighting texture cues more heavily. However, for stereo/motion parallax feedback, performance in many conditions became worse such that, paradoxically, biases moved away from the point reinforced by the feedback. This can be explained by assuming that subjects remap the relationship between stereo/motion parallax cues and perceived size or that they develop strategies to change their criterion for a size match on different trials. In either case, subjects appear not to have direct access to stereo/motion parallax cues.

Factors required for the uridylylation of the foot-and-mouth disease virus 3B1, 3B2, and 3B3 peptides by the RNA-dependent RNA polymerase (3D(pol)) in vitro

The 5' terminus of picornavirus genomic RNA is covalently linked to the virus-encoded peptide 313 (VTg). Foot-and-mouth disease virus (FMDV) is unique in encoding and using 3 distinct forms of this peptide. These peptides each act as primers for RNA synthesis by the virus-encoded RNA polymerase 3D(pol). To act as the primer for positive-strand RNA synthesis, the 3B peptides have to be uridylylated to form VPgpU(pU). For certain picornaviruses, it has been shown that this reaction is achieved by the 3D(pol) in the presence of the 3CD precursor plus an internal RNA sequence termed a cis-acting replication element (cre). The FMDV ere has been identified previously to be within the 5' untranslated region, whereas all other picornavirus cre structures are within the viral coding region. The requirements for the in vitro uridylylation of each of the FMDV 313 peptides has now been determined, and the role of the FMDV ere (also known as the 3B-uridylylation site, or bus) in this reaction has been analyzed. The poly(A) tail does not act as a significant template for FMDV 3B uridylylation.

Cycloadditions of chiral carbonyl ylides with imine dipolarophiles as a route to enantiomerically pure alpha-amino-beta-hydroxy acids

The preparation of enantiomerically pure threo-beta-amino-alpha-hydroxy acids via 1,3-dipolar cycloadditions of imine dipolarophiles with the chiral isomunchnone derived from (5R)-5-phenylmorpholin-3-one 1 is described. The cycloadducts were obtained with excellent diastereofacial- and exo-selectivity. Subsequent hydrolysis and chemoselective exocyclic amide cleavage afforded the threo-beta-amino-alpha-hydroxy acids with recovery of the initial chiral auxiliary. (C) 2009 Published by Elsevier Ltd.

Syntheses of two new 1D and 3D networks of Cu(II) and Co(II) using malonate and urotropine as bridging ligands: Crystal structures and magnetic studies

Two new metal-organic based polymeric complexes, [Cu-4(O2CCH2CO2)(4)(L)].7H(2)O (1) and [CO2(O2CCH2CO2)(2)(L)].2H(2)O (2) [L = hexamethylenetetramine (urotropine)], have been synthesized and characterized by X-ray crystal structure determination and magnetic studies. Complex 1 is a 1D coordination polymer comprising a carboxylato, bridged Cu-4 moiety linked by a tetradentate bridging urotropine. Complex 2 is a 3D coordination polymer made of pseudo-two-dimensional layers of Co(II) ions linked by malonate anions in syn-anticonformation which are bridged by bidentate urotropine in trans fashion, Complex 1 crystallizes in the orthothombic system, space group Pmmn, with a = 14,80(2) Angstrom, b = 14.54(2) Angstrom, c = 7.325(10) Angstrom, beta = 90degrees, and Z = 4. Complex 2 crystallizes in the orthorhombic system, space group Imm2, a = 7.584(11) Angstrom, b = 15.80(2) Angstrom, c = 6.939(13) Angstrom, beta = 90.10degrees(1), and Z = 4. Variable temperature (300-2 K) magnetic behavior reveals the existence of ferro- and antiferromagnetic interactions in 1 and only antiferromagnetic interactions in 2. The best fitted parameters for complex 1 are J = 13.5 cm(-1), J = -18.1 cm(-1), and g = 2.14 considering only intra-Cu-4 interactions through carboxylate and urotropine pathways. In case of complex 2, the fit of the magnetic data considering intralayer interaction through carboxylate pathway as well as interlayer interaction via urotropine pathway gave no satisfactory result at this moment using any model known due to considerable orbital contribution of Co(II) ions to the magnetic moment and its complicated structure. Assuming isolated Co(II) ions (without any coupling, J = 0) the shape of the chi(M)T curve fits well with experimental data except at very low temperatures.

A new route to furanoeremophilane sesquiterpenoids. Synthesis of Senecio metabolites (+/-)-6-hydroxyeuryopsin, (+/-)-1,10-epoxy-6-hydroxyeuryopsin, (+/-)-toluccanolide A and (+/-)-toluccanolide C

A new strategy for the synthesis of sesquiterpenoids of the furanoeremophilane family was developed in which the tricyclic nucleus was assembled in an A + C -> A - C -> A - B - C sequence. The A - C connection was made via coupling of a cyclohexenylmethyl bromide with a stannylfuran under "ligandless" Stille conditions, and the key cyclization which closed ring B was accomplished with complete stereocontrol by intramolecular formylation of a 2-silylfuran in the presence of trimethylsilyl triflate. This route was used to complete the first total syntheses of the furanoeremophilane 6-hydroxyeuryopsin and the eremophilenolides toluccanolide A and toluccanolide C, as well as a formal synthesis of 1,10-epoxy-6-hydroxyeuryopsin.