Twisting and planarization in push-pull ethylenes

As determined by X-ray crystallography, Meldrum's acid derivatives 8–19 feature dihedral angles around the central CC double bonds between 3 and 83°. Hydrogen bonds between substituents RHN and the carbonyl groups favour near-planarity. Sterically demanding substituents favour large dihedral angles and zwitterionic structures as in formula 20. AM1 calculations of the structures are in excellent agreement with the experimental X-ray data, provided a dielectric field is incorporated (?= 40). This can be ascribed to the highly polar (zwitterionic) nature of the molecules. It is further predicted that all these molecules, including those that are stabilised in a planar form by intramolecular hydrogen bonds, undergo rapid rotation about the central CC bonds at room temperature. DFT calculations incorporating a dielectric field model (PCM) are in excellent agreement with the near-perpendicular arrangement of the alkene moiety in 19.

A theoretical study of the origin of rotational barriers in push-pull ethylenes

Using the B3LYP/6-31G* ab initio method, we have studied the rotation about the C=C bonds in 15 push-pull ethylenes of the general formula (X,Y)C=C(CHO)(2) [X, Y = NH2, NHCH3, N(CH3)(2), OCH3, SCH3] in the gas phase. Two stationary points (minimum and transition state) were located for all compounds. The geometry, dipole moments, natural bond orbital atomic charges, as well as the rotational barriers were examined. The torsion angle 0 depends essentially on the presence or absence of intramolecular hydrogen bonds, and the barrier is a function of the torsion angle. (C) 2002 Elsevier Science B.V. All rights reserved.

The role of colour in signalling and male choice in the agamid lizard Ctenophorus ornatus

Bright coloration and complex visual displays are frequent and well described in many lizard families. Reflectance spectrometry which extends into the ultraviolet (UV) allows measurement of such coloration independent of our visual system. We examined the role of colour in signalling and mate choice in the agamid lizard Ctenophorus ornatus. We found that throat reflectance strongly contrasted against the granite background of the lizards' habitat. The throat may act as a signal via the head-bobbing and push-up displays of C. ornatus. Dorsal coloration provided camouflage against the granite background, particularly in females. C. ornatus was sexually dichromatic for all traits examined including throat UV reflectance which is beyond human visual perception. Female throats were highly variable in spectral reflectance and males preferred females with higher throat chroma between 370 and 400 nm. However, female throat UV chroma is strongly correlated to both throat brightness and chest UV chroma and males may choose females on a combination of these colour variables. There was no evidence that female throat or chest coloration was an indicator of female quality. However, female brightness significantly predicted a female's laying date and, thus, may signal receptivity. One function of visual display in this species appears to be intersexual signalling, resulting in male choice of females.

Globalization and women in southeast Asian higher education management

This paper draws on data from a group case study of women in higher education management in Hong Kong, Singapore, Malaysia, and Thailand. I investigate culture-specific dimensions of what the Western literature has conceptualized as glass ceiling impediments to women's career advancement in higher education. I frame my argument within recent debates about globalization and glocalization to show how the push-pull and disjunctive dynamics of globalization are experienced in local sites by social actors who traverse global flows and yet remain tethered to local discourses, values, and practices. All of the women in this study were trained in Western universities and are fluent English speakers, world-class experts in their fields, well versed with equity discourses, and globally connected on international nongovernment organization (NGO) and academic circuits. They are indeed global cosmopolitans. And yet their testimonies indicate that so-called Asian values and religious-cultural ideologies demand the enactment of a specific construct of Asian femininity that militates against meritocratic equality and academic career aspirations to senior management levels. Despite the global nature of the University and increasing global flows of academics, students, and knowledge, the politics of academic glass ceilings are not universal but always locally inflected with cultural values and norms. As such, the politics of disadvantage for women in higher education require local and situated analyses in the context of global patterns of the educational status Of women and the changing nature of higher education.