New urban forms: the crescents of Bath and Le Corbusier's plan for Rio de Janeiro

This article considers whether formal references in Le Corbusier's work may be traced to the eigtheenth century crescents of Bath and, in particular, Lansdowne Crescent. By exploring this line, it raises the possibility that in the work he produced for the Latin American context, this arch-modernist planner moved beyond the de-contextualized approach for which he is known and explored the possibility of integrating new urban forms with nature. The article also shows how Le Corbusier's plans for Rio de Janeiro allowed him to become an important formal reference point for successive generations of local architects and planners.     

Complexity via Gold-Catalyzed Molecular Gymnastics

Reactions of 1,6-enynes catalyzed by gold(I) complexes usually proceed stereospecifically through highly distorted cyclopropyl gold carbenes. Substrates with an alkoxy substituent at the propargylic position undergo stereoselective transformations through intermediates in which the OR group and the gold carbene are anti-oriented. Intramolecular attack of carbonyl groups to the cyclopropyl gold carbene is faster than the 1,5-migration of the OR groups, which itself is faster than the intramolecular cyclopropanation by a pendant alkenyl group. The intramolecular attack of carbonyl groups is the key transformation in the [2+2+2] gold-catalyzed cycloaddition, which has been applied in the total synthesis of (+)-orientalol F.     

Biochemical and chemical characterization of phenylglyoxal bis(guanylhydrazone), an aromatic analogue of mitoguazone

Since little has been known about the properties of aromatic analogues of the antineoplastic agent methylglyoxal bis(guanylhydrazone) (MGBG), an investigation was performed on phenylglyoxal bis(guanylhydrazone) (PhGBG). PhGBG competitively inhibited yeast adenosylmethionine decarboxylase (AdoMetDC) with a Ki of 65 microM. As compared to MGBG (Ki 0.23 microM), PhGBG is a much weaker inhibitor, being even weaker than the unsubstituted congener glyoxal bis(guanylhydrazone) (GBG, Ki 18 microM). PhGBG inhibited porcine kidney diamine oxidase (DAO) non-competitively, being a more potent inhibitor (Ki 0.12 microM) than GBG (Ki 0.17 microM) or MGBG (Ki 0.33 microM). Thus, PhGBG has an unfavourably high ratio of Ki(AdoMetDC)/Ki(DAO) for potential use for selectively inhibiting polyamine biosynthesis. This does not exclude the possibility that PhGBG or other aromatic congeners might have therapeutic value since the corresponding ratio of the antileukaemic congeners GBG and MGBG is also high as compared to many aliphatic non-antileukaemic analogues. The pKa1 and pKa2 values of PhGBG dication were found to be 6.39 +/- 0.02 and 8.64 +/- 0.02 respectively, their difference being distinctly larger than in the case of GBG or its C-alkylated analogues. This may result from decreased stability of the dication form, caused by the resonance effect or possibly by the inductive effect of the phenyl group. The species distribution of PhGBG (proportion of free base 5.5%, predominant species the monocation) at 37 degrees C resembles that of GBG and MGBG but is clearly different from that of non-antileukaemic C-alkylated analogues. These similarities suggest that PhGBG and its derivatives may be worth antitumour screening. Depending on the conditions used in the crystallization, three different types of crystals of PhGBG sulphate were obtained. Crystallography indicated that, in two of the types, the crystal consisted exclusively of the anti-anti isomer, i.e. the same isomer as has been observed in the case of GBG and its C-alkylated congeners. One crystal type, however, consisted of a different geometrical isomer (anti-syn), suggesting that PhGBG may isomerize more easily than its aliphatic analogues. Previous concepts on the isomerism of GBG and C-alkylated bis(guanylhydrazones) thus cannot be generalized to aromatic congeners. A theory based on resonance, inductive and hyperconjugative effects and electron transfers is presented that is capable of explaining the formation of the two geometrical isomers of PhGBG that were experimentally observed. A similar theory, based on hyperconjugation of C-F bonds, is presented that is capable of explaining the previous finding of the formation of the anti-syn isomer of trifluoromethylglyoxal bis(guanylhydrazone) (CF3GBG). Like that of CF3GBG, the anti-syn isomer of the PhGBG dication is stabilized by an internal hydrogen bond. The lack of structural rigidity may affect the biological properties of PhGBG, e.g. its ability to inhibit AdoMetDC.     

Automated sequential injection-microcolumn approach with on-line flame atomic absorption spectrometric detection for implementing metal fractionation schemes of homogeneous and nonhomogeneous solid samples of environmental interest

An automated sequential injection (SI) system incorporating a dual-conical microcolumn is proposed as a versatile approach for the accommodation of both single and sequential extraction schemes for metal fractionation of solid samples of environmental concern. Coupled to flame atomic absorption spectrometric detection and used for the determination of Cu as a model analyte, the potentials of this novel hyphenated approach are demonstrated by the ability of handling up to a 300 mg sample of a nonhomogeneous sewage amended soil (viz., CRM 483). The three steps of the endorsed Standards, Measurements, and Testing sequential extraction method have been also performed in a dynamic fashion and critically compared with the conventional batchwise protocols. The ecotoxicological relevance of the data provided by both methods with different operationally defined conditions is thoroughly discussed. As compared to traditional batch systems, the developed SI assembly offers minimal risks of sample contamination, the absence of metal re-distribution/readsorption, and dramatic saving of operational times (from 16 h to 40-80 min per partitioning step). It readily facilitates the accurate manipulation of the extracting reagents into the flow network and the minute, well-defined injection of the desired leachate volume into the detector. Moreover, highly time-resolved information on the ongoing extraction is given, which is particularly relevant for monitoring fast leaching kinetics, such as those involving strong chelating agents. On-line and off-line (for Cu, Pb, and Zn) single extraction schemes are also proven to constitute attractive alternatives for fast screening of metal pollution in solid samples and for predicting the current, rather than the potential, element bioavailability by the assessment of the readily mobilizable metal forms.     

Proportional Plus Integral Control for Set-Point Regulation of a Class of Nonlinear RLC Circuits

In this paper we identify graph-theoretic conditions which allow us to write a nonlinear RLC circuit as port-Hamiltonian with constant input matrices. We show that under additional monotonicity conditions on the network’s components, the circuit enjoys the property of relative passivity, an extended notion of classical passivity. The property of relative passivity is then used to build simple, yet robust and globally stable, proportional plus integral controllers. This work was partially supported by CONACyT, México.     

Intuitive Facial Animation Editing Based On A Generative RNN Framework

For the last decades, the concern of producing convincing facial animation has garnered great interest, that has only been accelerating with the recent explosion of 3D content in both entertainment and professional activities. The use of motion capture and retargeting has arguably become the dominant solution to address this demand. Yet, despite high level of quality and automation performance-based animation pipelines still require manual cleaning and editing to refine raw results, which is a time- and skill-demanding process. In this paper, we look to leverage machine learning to make facial animation editing faster and more accessible to non-experts. Inspired by recent image inpainting methods, we design a generative recurrent neural network that generates realistic motion into designated segments of an existing facial animation, optionally following user-provided guiding constraints. Our system handles different supervised or unsupervised editing scenarios such as motion filling during occlusions, expression corrections, semantic content modifications, and noise filtering. We demonstrate the usability of our system on several animation editing use cases.