Conformational and self-assembly studies of helix forming hexapeptides containing two alpha-amino isobutyric acids

Single crystal X-ray diffraction studies reveal that three hexapeptides with general formula Boc-Ile-Aib-Xx-Ile-Aib-Yy-OMe, where Xx and Yy are Leu in peptide I, Len and Phe in peptide II, and Phe and Leu in peptide III, respectively, adopt equivalent conformations that can be described as mixed 3(10)/alpha-helice with two 4 -> 1 and two 5 -> 1 intramolecular N-H center dot center dot center dot O=C H-bonds. The peptides do not generate any helixterminating Schellman motif despite having Aib at the penultimate position from C-terminus. In the crystalline state, the helices are packed in head-to-tail fashion through intermolecular hydrogen bonds to create supramolecular helical structures. The CD Studies of the three hexapeptides in acetonitrile indicate that they are folded in well-developed 3(10)-helical structures. NMR studies of peptide I in CDCl3 also suggest the formation of a homogeneous 3 m-helical structure. The field emission scanning electron microscopic (FE-SEM) images of peptide 11 in the solid state reveal a non-twisted ribbon-like morphology, which is formed through lateral association of non-twisted filaments. (c) 2007 Elsevier Ltd. All rights reserved.

Design of a turn-linker-turn foldamer by incorporating meta-amino benzoic acid in the middle of a helix forming hexapeptide sequence: A helix breaking approach

Single crystal X-ray diffraction studies reveal that the incorporation of meta-amino benzoic acid in the middle of a helix forming hexapeptide sequence such as in peptide I Boc-Ile(1)-Aib(2)-Val(3)-m-ABA(4)-Ile(5)-Aib(6)-Leu(7)-OMe (Aib: alpha-amino isobutyric acid: m-ABA: meta-amino benzoic acid) breaks the helix propagation to produce a turn-linker-turn (T-L-T) foldamer in the solid state. In the crystalline state two conformational isomers of peptide I self-assemble in antiparallel fashion through intermolecular hydrogen bonds and aromatic pi-pi interactions to form a molecular duplex. The duplexes are further interconnected through intermolecular hydrogen bonds to form a layer of peptides. The layers are stacked one on top of the other through van der Waals interactions to form hydrophilic channels filled with solvent methanol. (C) 2009 Elsevier B.V. All rights reserved.

Design of supramolecular beta-sheet forming beta-turns containing aromatic rings and non-coded alpha-aminoisobutyric acid and the formation of flat fibrillar structures through self-assembly

Single crystal X-ray diffraction studies show that the three designed tripeptides Boc-Leu-Aib-m-NA-NO2 (I), Boc-Phe-Aib-m-NA-NO2 (II) and Boc-Pro-Aib-m-ABA-OMe (III) (Aib, -aminoisobutyric acid; m-NA, m-nitroaniline; m-ABA, m-aminobenzoic acid; Boc, t-butyloxycarbonyl) containing aromatic rings in the backbones adopt -turn structures that are self-assembled through intermolecular hydrogen bonds and van der Waals interactions to create layers of -sheets. Solvent-dependent NMR titration and CD studies show that the -turn structures of the peptides also exist in the solution phase. The field emission scanning electron microscopic and transmission electron microscopic images of the peptides in the solid state reveal fibrillar structures of flat morphology that are formed through -sheet mediated self-assembly of the preorganised -turn building blocks.

Self-assembly of beta-turn forming synthetic tripeptides into supramolecular beta-sheets and amyloid-like fibrils in the solid state

We have described here the self-assembling properties of the synthetic tripeptides Boc-Ala(1)-Aib(2) -Val (3)-OMe 1, BocAla(l)-Aib(2)-Ile(3)-OMe 2 and Boc-Ala(l)-Gly(2)-Val(3)-OMe 3 (Aib=alpha-arnino isobutyric acid, beta-Ala=beta-alanine) which have distorted beta-turn conformations in their respective crystals. These turn-forming tripeptides self-assemble to form supramolecular beta-sheet structures through intermolecular hydrogen bonding and other noncovalent interactions. The scanning electron micrographs of these peptides revealed that these compounds form amyloid-like fibrils, the causative factor for many neurodegenerative diseases including Alzheimer's disease, Huntington's disease and Prion-related encephalopathies. (C) 2004 Elsevier Ltd. All rights reserved.

Anion directed template synthesis of Cu(II) complexes of a N,N,O donor mono-condensed Schiff base ligand: A molecular scaffold forming highly ordered H-bonded rectangular grids

Anion directed, template syntheses of two dinuclear copper(II) complexes of mono-condensed Schiff base ligand Hdipn (4-[(3-aminopentylimino)-methyl]-benzene-1,3-diol) involving 2,4- dihydroxybenzaldehyde and 1,3-diaminopentane were realized in the presence of bridging azide and acetate anions. Both complexes, [Cu-2(dipn)(2)(N-3)(2)] (1) and [Cu-2(dip(n))(2)(OAc)(2)] (2) have been characterized by X-ray crystallography. The two mononuclear units are joined together by basal-apical, double end-on azido bridges in complex 1 and by basal-apical, double mono-atomic acetate oxygen-bridges in 2. Both complexes form rectangular grid-like supramolecular structures via H-bonds connecting the azide or acetate anion and the p-hydroxy group of 2,4- dihydroxybenzaldehyde. Variable-temperature (300-2 K) magnetic susceptibility measurements reveal that complex 1 has antiferromagnetic coupling (J = -2.10 cm (1)) through the azide bridge while 2 has intra-dimer ferromagnetic coupling through the acetate bridge and inter-dimer antiferromagnetic coupling through H-bonds (J = 2.85 cm (1), J' = -1.08 cm (1)). (C) 2009 Elsevier B. V. All rights reserved.

Effect of Stretching on the Structure of Cylinder- and Sphere-Forming Styrene-Isoprene-Styrene Block Copolymers

Two styrene-isoprene-styrene block copolymers Vector 4111 and 4113, exhibiting cylindrical (18 wt % PS) and spherical (16 wt % PS) morphology, respectively, have been examined under uniaxial elongation up to 200% strain. On the basis of stress-strain data, mechanical properties are compared for isotropic and oriented polystyrene domains. The structure at various stages of deformation has been determined from SAXS patterns in three planes and two principal deformation directions with respect to orientation. Samples showed a very high degree of hexagonal packing, resulting in an X-ray pattern taken parallel to the cylinder alignment approaching single crystal ordering. Cylinders were aligned with the closest packed planes parallel to film surface. Particular attention has been paid to a lattice deformation process occurring during the first stretching and relaxation cycle. For a copolymer with oriented cylindrical morphology the deformation was affine up to 120% strain. The microdomain spacing was calculated parallel and perpendicular to the stretching direction. The cylindrical microstructure orientation, quantified by Hermans' orientation factor reduced during elongation of oriented polymer, while the elongation of isotropic sample caused an increase of orientation. Deformation of all studied morphologies was reversible.

Film-forming polymers containing in the main-chain dibenzo crown ethers with aliphatic (C-10-C-16), aliphatic-aromatic, or oxyindole spacers

Novel, linear, soluble, high-molecular-weight, film-forming polymers and copolymers in which main-chain crown ether units alternate with aliphatic (C-10-C-16) units have been obtained for the first time from aromatic electrophilic substitution reactions of crown ethers by aliphatic dicarboxylic acids followed by reduction of the carbonyl groups. The crown ether unit is dibenzo-18-crown-6, dibenzo-21-crown-7, dibenzo-24-crown-8, or dibenzo-30-crown-10; the aliphatic spacer is derived from a dicarboxylic acid (sebacic, 1,12-dodecanedicarboxylic, hexadecanedioic or 1,4-phenylenediacetic acids). The reactions were performed at 35 degrees C in a mixture of methanesulfonic acid (MSA) with phosphorus pentoxide, 12:1 (w/w), (Eaton's reagent). The carbonyl groups in the polyketones obtained were completely reduced to methylene linkages by treatment at room temperature with triethylsilane in a mixture of trifluoroacetic acid and dichloromethane. Polymers containing in the main chain crown ethers alternating with oxyindole fragments were prepared by one-pot condensation of crown ethers with isatin in a medium of Eaton's reagent. A possible reaction mechanism is suggested. According to IR and NMR analyses, the polyacylation reactions lead to the formation of isomeric (syn/anti-substituted) crown ether units in the main chain. The polymers obtained were soluble in the common organic solvents, and flexible transparent films could be cast from the solutions. DSC and X-ray studies of the polymers with "symmetrical" crown ethers reveal the presence of the endotherms corresponding to the supramolecular assemblies.

Teachers as researchers and teachers as software developers: how use-case analysis helps build better educational software

A series of government initiatives has raised both the profile of ICT in the curriculum and the expectation that high quality teaching and learning resources will be accessible across electronic networks. In order for e-learning resources such as websites to have the maximum educational impact, teachers need to be involved in their design and development. Use-case analysis provides a means of defining user requirements and other constraints in such a way that software developers can produce e-learning resources which reflect teachers' professional knowledge and support their classroom practice. It has some features in common with the participatory action research used to develop other aspects of classroom practice. Two case-studies are presented: one involves the development of an on-line resource centred on transcripts of original historical documents; the other describes how 'Learning how to Learn', a major, distributed research project funded under the ESRC Teaching and Learning Research Programme is using use-case analysis to develop web resources and services.

Primary teachers as readers

In the context of the continued pressure and politicisation of the teaching of reading in England, the United Kingdom Literacy Association (UKLA) sought to ascertain patterns in primary teachers' reading, both personally and professionally. The project, undertaken in 11 Local Authorities in England, explored 1200 primary teachers' personal reading habits and preferences, investigated their knowledge of children's literature, and documented their reported use of texts in the classroom through a questionnaire. In addition, it sought to establish the extent of the teachers' involvement with and use of local area/school library services. This paper reports on the findings with reference to the teachers' personal reading, the frequency of this reading and the sources they use to select their reading material. It also considers the teachers' favourite childhood texts and the books they identified as highly significant to them, as well as their perceptions of the importance of literature. Connections are made to the data gathered about their knowledge of children's literature, and how primary teachers decide which literature to work with in the classroom.

Exploring teachers' knowledge of children's literature

In the context of the current debate about teaching reading, research to ascertain primary teachers' personal and professional reading practices was undertaken. The study explored teachers' reading habits and preferences, investigated their knowledge of children's literature, and documented their reported use of such texts and involvement with library services. Questionnaire responses were gathered from 1200 teachers. The data were analysed and connections made between the teachers' own reading habits and preferences, their knowledge of children's literature, their accessing practices and pedagogic use of literature in school. This paper reports on part of the dataset and focuses on teachers' knowledge of children's literature; it reveals that primary professionals lean on a narrow repertoire of authors, poets and picture fiction creators. It also discusses teachers' personal reading preferences and considers divergences and connections between these as well as the implications of the teachers' limited repertoires on the reading development of young learners.

Student-teachers' perspectives on positive and negative social processes in schools

In recent years, the Standards for Qualified Teacher Status in England have placed new emphasis on student-teachers' ability to become integrated into the 'corporate life of the school' and to work with other professionals. Little research, however, has been carried out into how student-teachers perceive the social processes and interactions that are central to such integration during their initial teacher education school placements. This study aims to shed light on these perceptions. The data, gathered from 23 student-teachers through interviews and reflective writing, illustrate the extent to which the participants perceived such social processes as supporting or obstructing their development as teachers. Signals of inclusion, the degree of match or mismatch in students' and school colleagues' role expectations, and the social awareness of both school and student-teacher emerged as crucial factors in this respect. The student-teachers' accounts show their social interactions with school staff to be meaningful in developing their 'teacher self' and to be profoundly emotionally charged. The implications for mentor and student-teacher role preparation are discussed in this article.

Teachers' networks in and out of school

A 'mapping task' was used to explore the networks available to head teachers, school coordinators and local authority staff. Beginning from an ego-centred perspective on networks, we illustrate a number of key analytic categories, including brokerage, formality, and strength and weakness of links with reference to a single UK primary school. We describe how teachers differentiate between the strength of network links and their value, which is characteristically related to their potential impact on classroom practice.

Teachers' views on the nature of models

A semi-structured interview was used in Brazil to enquire into the 'notion of model' held by a total sample of 39 science teachers who were: employed in 'fundamental' (6-14 years) and 'medium' (15-17 years) schools; student science teachers currently doing their practicum; and university science teachers. Seven 'aspects' of their notions of a model were identified: the nature of a model, the use to which it can be put, the entities of which it consists, its relative uniqueness, the time span over which it is used, its status in the making of predictions, and the basis for the accreditation of its existence and use. Categories of meaning were identified for each of these aspects. The profiles of teachers' notions of 'model' in terms of the aspects and categories were complex, providing no support for the notion of 'Levels' in understanding. Teachers with degrees in chemistry or physics had different views about the notion of 'model' to those with degrees in biology or with teacher training certificates.