Liquid crystalline phases, microtwinning in crystals and helical chirality transformations in a main-chain chiral liquid crystalline polyester

A main-chain nonracemic chiral liquid crystalline polymer was synthesized from (R)-(-)4'-{w-[2-(p-hydroxy-o-nitrophenyloxy)-1-propyloxy]-1-decyloxyl-4-biphenylcarboxylic acid. This polymer contained 10 methylene units in each chemical repeating unit and was abbreviated PET(R*-10). On the basis of differential scanning calorimetry, wide-angle X-ray diffraction, and polarized light microscopy experiments, chiral smectic C (S-C*) and chiral smectic A (S-A*) phases were identified. Both flat-elongated and helical lamellar crystal morphologies were observed in transmission electron microscopy. Of particular interest was the flat-elongated lamellar crystals were constructed via microtwinning of an orthorhombic cell with dimensions of a = 1.42 nm, b = 1.28 nm, and c = 3.04 nm. On the other hand, the helical lamellar crystals were exclusively left-handed, which was opposite to the right-handed helical crystals grown in PET(R*-9) and PET(R*-11) (having 9 and 11 methylene units, respectively). Note that these three polymers had identical right-handed chiral centers (R*-). Therefore, a single methylene unit difference on the polymer backbones on an atomic length scale substantially changed the chirality of the crystals in the micrometer length scale. Furthermore, aggregates of these helical crystals in PET(R*-10) did not generate banded spherulites in polarized light microscopy. Possible reasons for this change and loss of helical senses (handedness) on different length scales in chirality transferring processes were discussed.

Helix-sense-selective polymerization of N,N-diphenyl (meth)acrylamide by anionic catalysts

In this paper, the helix-sense-selective polymerization of N,N-diphenyl acrylamide (DPAA) and N,N-diplienyl methacrylamide(DPMAA) were studied with living helix prepolymer as anionic initiator, and the chiral optical properties of the obtained polymers were investigated too. It was shown that optically active polymers of DPAA and DPMAA could be obtained under the experimental condition, and exhibited the same screw sense as that of the prepolymer.

Dehydrophenylalanine zippers: strong helix-helix clamping through a network of weak interactions

A decapeptide Boc-L-Ala-(DeltaPhe)(4)-L-Ala-(DeltaPhe)(3)-Gly-OMe (Peptide I) was synthesized to study the preferred screw sense of consecutive alpha,beta-dehydrophenylalanine (DeltaPhe) residues. Crystallographic and CD studies suggest that, despite the presence of two L-Ala residues in the sequence, the decapeptide does not have a preferred screw sense. The peptide crystallizes with two conformers per asymmetric unit, one of them a slightly distorted right-handed 3(10)-helix (X) and the other a left-handed 3(10)-helix (Y) with X and Y being antiparallel to each other. An unanticipated and interesting observation is that in the solid state, the two shape-complement molecules self-assemble and interact with an extensive network of C-H...O hydrogen bonds and pi-pi interactions, directed laterally to the helix axis with amazing regularity. Here, we present an atomic resolution picture of the weak interaction mediated mutual recognition of two secondary structural elements and its possible implication in understanding the specific folding of the hydrophobic core of globular proteins and exploitation in future work on de novo design.

Microstructure of GaN films grown on Si(111) substrates by metalorganic chemical vapor deposition

We report the transmission electron microscopy (TEM) study of the microstructure of wurtzitic GaN films grown on Si(I I I) substrates with AlN buffer layers by metalorganic chemical vapor deposition (MOCVD) method. An amorphous layer was formed at the interface between Si and AlN when thick GaN film was grown. We propose the amorphous layer was induced by the large stress at the interface when thick GaN was grown. The In0.1Ga0.9N/GaN multiple quantum well (MQW) reduced the dislocation density by obstructing the mixed and screw dislocations from passing through the MQW. But no evident reduction of the edge dislocations by the MQW was observed. It was found that dislocations located at the boundaries of grains slightly in-plane misoriented have screw component. Inversion domain is also observed. (C) 2003 Elsevier B.V. All rights reserved.

HELIX-INDUCED ASYMMETRIC POLYMERIZATION

Asymmetric polymerization could be induced by an already formed optically active living prepolymer with one-handed screw sense helix conformation. The usually formed anionic active centre on the prepolymer could be changed to cationic, radical and even of Ziegler-Natta type. These living prepolymers with various kinds of active centre were all effective to induce a consequent asymmetric polymerization of a monomer which may be other than that in the prepolymer, to afford an optically active helical chain with the same screw sense as that of the prepolymer. Eight monomers have been used in the work. Optical rotation, circular dichroism and gelpermeation chromatography have been taken to prove the helix-induced asymmetric polymerization.

Single network adaptive critic aided dynamic inversion for optimal regulation and command tracking with online adaptation for enhanced robustness

To combine the advantages of both stability and optimality-based designs, a single network adaptive critic (SNAC) aided nonlinear dynamic inversion approach is presented in this paper. Here, the gains of a dynamic inversion controller are selected in such a way that the resulting controller behaves very close to a pre-synthesized SNAC controller in the output regulation sense. Because SNAC is based on optimal control theory, it makes the dynamic inversion controller operate nearly optimal. More important, it retains the two major benefits of dynamic inversion, namely (i) a closed-form expression of the controller and (ii) easy scalability to command tracking applications without knowing the reference commands a priori. An extended architecture is also presented in this paper that adapts online to system modeling and inversion errors, as well as reduced control effectiveness, thereby leading to enhanced robustness. The strengths of this hybrid method of applying SNAC to optimize an nonlinear dynamic inversion controller is demonstrated by considering a benchmark problem in robotics, that is, a two-link robotic manipulator system. Copyright (C) 2013 John Wiley & Sons, Ltd.

Making sense of an everyday science text : linguistic, visual and spatial design

In this article, we take a close look at the literacy demands of one task from the ‘Marvellous Micro-organisms Stage 3 Life and Living’ Primary Connections unit (Australian Academy of Science, 2005). One lesson from the unit, ‘Exploring Bread’, (pp 4-8) asks students to ‘use bread labels to locate ingredient information and synthesise understanding of bread ingredients’. We draw upon a framework offered by the New London Group (2000), that of linguistic, visual and spatial design, to consider in more detail three bread wrappers and from there the complex literacies that students need to interrelate to undertake the required task. Our findings are that although bread wrappers are an example of an everyday science text, their linguistic, visual and spatial designs and their interrelationship are not trivial. We conclude by reinforcing the need for teachers of science to also consider how the complex design elements of everyday science texts and their interrelated literacies are made visible through instructional practice.

Making sense of working lives and working choices : the role of satirical cartoons

This study examined the tone and content of 107 political, satirical cartoons images published in the popular culture forum of mainstream newspapers. The cartoons illustrated the reform of the industrial relations system in Australia in 2005 and 2006. The images were conveyed in a moderate tone. That is, they were more about poking fun at and questioning authority and power, rather than simply describing the issues on one hand, or demonstrating any revolutionary fervor on the other. The cartoons’ content represented many of the concerns and issues being voiced by employer groups, government, opposition, unions and the media at the time. Themes likely to evoke a strong response from the readership included the importance of a collective response in voicing opposition to the legislation and enacting change, the risks to fundamental working conditions, the stealth and dogma associated with the rollout of the changes and the increasing disparity in wealth and power between employers and workers. The images were an important part of the wider discourse and a mechanism which helped place industrial relations squarely in the minds of working Australians.

Sense and sensibility by Jane Austen

It's the fact that it's Austen mentioned here that provokes a response. The broad cultural veneration of Jane Austen means that even those who have never read her work are likely to have a strong reaction to Emerson's famou quotation. It is worth considering Emerson's accustion befor teaching an Austen novel, as many of his assertions will be amde - albeit in different terms - byt twenty-first-century students.

Making sense of the resource-based view?

The Resource Based View (RBV) of strategic management has been criticized for relying on inconsistent assumptions of rationality, and mutually inconsistent underlying hypotheses. In this paper, I outline how these critiques can be addressed by re-building RBV on a sense-making foundation. The core notions from sense-making of bounded cognition, retrospective sense-making, incrementalism, loose coupling, causal maps and organizational paradigm are introduced. These are then used to propose a re-construction of key RBV constructs, extending some conceptual discussions, and providing for a conceptually consistent formulation. Implications for the use of RBV as a theory and future research are discussed.

Making sense of Australia's war memorials

War memorials are an important part of the Australian landscape and culture. This essay suggests five possible explanations for this: a) imperial loyalty, at least initially; b) the warrior cult; c) guilt at the loss of so many young people in a seemingly senseless fashion; d) the demise of formal religion, and; e) the insecure nature of Australian nationalism.

A biomechanical study of top screw pullout in anterior scoliosis correction constructs

Study Design: Biomechanical testing of vertebral body screw pullout resistance with relevance to top screw pullout in endoscopic anterior scoliosis constructs. Objectives: To analyse the effect of screw positioning and angulation on pullout resistance of vertebral body screws, where the pullout takes place along a curved path as occurs in anterior scoliosis constructs. Summary of Background Data: Top screw pullout is a significant clinical problem in endoscopic anterior scoliosis surgery, with rates of up to 18% reported in the literature. Methods: A custom designed biomechanical test rig was used to perform pullout tests of Medtronic anterior vertebral screws where the pullout occurred along an arc of known radius. Using synthetic bone blocks, a range of pullout radii and screw angulations were tested, in order to determine an ‘optimal’ configuration. The optimal configuration was then compared with standard screw positioning using a series of tests on ovine vertebrae (n=29). Results: Screw angulation has a small but significant effect on pullout resistance, with maximum strength being achieved at 10 degree cephalad angulation. Combining 10 degree cephalad angulation with maximal spacing between the top two screws (maximum pullout radius) increased the pullout resistance by 88% compared to ‘standard’ screw positioning (screws inserted perpendicular to rod at mid-body height). Conclusions: The positioning of the top screw in anterior scoliosis constructs can significantly alter its pullout resistance.