Hydrogelation and self-assembly of Fmoc-tripeptides: unexpected influence of sequence on self-assembled fibril structure, and hydrogel modulus and anisotropy

The self-assembly and hydrogelation properties of two Fmoc-tripeptides [Fmoc = N-(fluorenyl-9-methoxycarbonyl)] are investigated, in borate buffer and other basic solutions. A remarkable difference in self-assembly properties is observed comparing Fmoc-VLK(Boc) with Fmoc-K(Boc)LV, both containing K protected by N(epsilon)-tert-butyloxycarbonate (Boc). In borate buffer, the former peptide forms highly anisotropic fibrils which show local alignment, and the hydrogels show flow-aligning properties. In contrast, Fmoc-K(Boc)LV forms highly branched fibrils that produce isotropic hydrogels with a much higher modulus (G' > 10(4) Pa), and lower concentration for hydrogel formation. The distinct self-assembled structures are ascribed to conformational differences, as revealed by secondary structure probes (CD, FTIR, Raman spectroscopy) and X-ray diffraction. Fmoc-VLK(Boc) forms well-defined beta-sheets with a cross-beta X-ray diffraction pattern, whereas Fmoc-KLV(Boc) forms unoriented assemblies with multiple stacked sheets. Interchange of the K and V residues when inverting the tripeptide sequence thus leads to substantial differences in self-assembled structures, suggesting a promising approach to control hydrogel properties.

Filtering techniques in self-tuning

In the last few years a state-space formulation has been introduced into self-tuning control. This has not only allowed for a wider choice of possible control actions, but has also provided an insight into the theory underlying—and hidden by—that used in the polynomial description. This paper considers many of the self-tuning algorithms, both state-space and polynomial, presently in use, and by starting from first principles develops the observers which are, effectively, used in each case. At any specific time instant the state estimator can be regarded as taking one of two forms. In the first case the most recently available output measurement is excluded, and here an optimal and conditionally stable observer is obtained. In the second case the present output signal is included, and here it is shown that although the observer is once again conditionally stable, it is no longer optimal. This result is of significance, as many of the popular self-tuning controllers lie in the second, rather than first, category.

Water vapour self-continuum and water dimers: 1. Analysis of recent work

Recent laboratory observations and advances in theoretical quantum chemistry allow a reappraisal of the fundamental mechanisms that determine the water vapour self-continuum absorption throughout the infrared and millimetre wave spectral regions. By starting from a framework that partitions bimolecular interactions between water molecules into free-pair states, true bound and quasi-bound dimers, we present a critical review of recent observations, continuum models and theoretical predictions. In the near-infrared bands of the water monomer, we propose that spectral features in recent laboratory-derived self-continuum can be well explained as being due to a combination of true bound and quasi-bound dimers, when the spectrum of quasi-bound dimers is approximated as being double the broadened spectrum of the water monomer. Such a representation can explain both the wavenumber variation and the temperature dependence. Recent observations of the self-continuum absorption in the windows between these near-infrared bands indicate that widely used continuum models can underestimate the true strength by around an order of magnitude. An existing far-wing model does not appear able to explain the discrepancy, and although a dimer explanation is possible, currently available observations do not allow a compelling case to be made. In the 8–12 micron window, recent observations indicate that the modern continuum models either do not properly represent the temperature dependence, the wavelength variation, or both. The temperature dependence is suggestive of a transition from the dominance of true bound dimers at lower temperatures to quasibound dimers at higher temperatures. In the mid- and far-infrared spectral region, recent theoretical calculations indicate that true bound dimers may explain at least between 20% and 40% of the observed self-continuum. The possibility that quasi-bound dimers could cause an additional contribution of the same size is discussed. Most recent theoretical considerations agree that water dimers are likely to be the dominant contributor to the self-continuum in the mm-wave spectral range.

Knowledge transfer: the facilitating attributes in supply-chain partnerships

This article examines the operational characteristics of supply-chain partnerships and identifies the relational attributes that cultivate knowledge transfer in such partnerships. A set of theoretical propositions are developed. A case study of a computer manufacturer's supply chain was conducted to examine their validity. The findings support the view that trust, commitment, interdependence, shared meaning, and balanced power facilitate knowledge transfer in supply-chain partnerships, and that knowledge transfer should be treated as a dynamic multistage process.

Validation of three new measure-correlate-predict models for the long-term prospection of the wind resource

The estimation of the long-term wind resource at a prospective site based on a relatively short on-site measurement campaign is an indispensable task in the development of a commercial wind farm. The typical industry approach is based on the measure-correlate-predict �MCP� method where a relational model between the site wind velocity data and the data obtained from a suitable reference site is built from concurrent records. In a subsequent step, a long-term prediction for the prospective site is obtained from a combination of the relational model and the historic reference data. In the present paper, a systematic study is presented where three new MCP models, together with two published reference models �a simple linear regression and the variance ratio method�, have been evaluated based on concurrent synthetic wind speed time series for two sites, simulating the prospective and the reference site. The synthetic method has the advantage of generating time series with the desired statistical properties, including Weibull scale and shape factors, required to evaluate the five methods under all plausible conditions. In this work, first a systematic discussion of the statistical fundamentals behind MCP methods is provided and three new models, one based on a nonlinear regression and two �termed kernel methods� derived from the use of conditional probability density functions, are proposed. All models are evaluated by using five metrics under a wide range of values of the correlation coefficient, the Weibull scale, and the Weibull shape factor. Only one of all models, a kernel method based on bivariate Weibull probability functions, is capable of accurately predicting all performance metrics studied.

Trust and relational embeddedness: exploring a paradox of trust pattern development in key supplier relationships

This paper explores the role of trust as an enabler and constraint between buyers and suppliers engaged in long-term relationships. According to the relational view, cooperative strategies require trust-based mutual commitments to co-create value. However, complete pictures of the positive and negative outcomes from trust development have yet to be fully developed. In particular, trust as an originator of path dependent constraints resulting from over embeddedness is yet to be integrated into the relational view. We use a case-based methodology to explore whether trust is an optimizing phenomenon in key supplier relationships. Two cases where trust development processes demonstrate a paradox of trust-building behaviors cultivate different outcomes constraining value co-creation.

Terrorist transgressions: gendered representations of the terrorist in visual culture

The aim of Terrorist Transgressions is to analyse the myths inscribed in images of the terrorist and identify how agency is attributed to representation through invocations and inversions of gender stereotypes. In modern discourses on the terrorist the horror experienced in Western societies was the appearance of a new sense of the vulnerability of the body politic, and therefore of the modern self with its direct dependency on security and property. The terrorist has been constructed as the epitome of transgression against economic resources and moral, physical and political boundaries. Although terrorism has been the focus of intense academic activity, cultural representations of the terrorist have received less attention. Yet terrorism is dependent on spectacle and the topic is subject to forceful exposure in popular media. While the terrorist is predominantly aligned with masculinity, women have been active in terrorist organisations since the late 19th century and in suicidal terrorist attacks since the 1980s. Such attacks have confounded constructions of femininity and masculinity, with profound implications for the gendering of violence and horror. The publication arises from an AHRC networking grant, 2011-12, with Birkbeck, and includes collaboration with the army at Sandhurst RMA. The project relates to a wider investigation into feminism, violence and contemporary art.

Self-construals, Symbolic and Hedonic Preferences, and Actual Purchase Behavior

The study explores the influence of the independent and interdependent self-construals on actual purchase behavior and the mediating role of consumer preferences for symbolic and hedonic meanings. Data were collected through a survey of about 1,000 respondents. Results indicate that independent consumers draw on the self/hedonic- and status-symbolic resources of clothing in the construction and expression of their identities. Regarding the interdependent consumers, they show no interest in clothing affiliation and status symbolism. The degree of preference for status-symbolic meaning mediates all effects of the independent and interdependent self-construals on actual purchase behavior; self-expressive/hedonic preferences mediate two of the three effects of the independent self on actual purchase behavior when accounting for suppression effects, whereas the expected mediation of preference for affiliation meaning is not supported.

Self-assembly of a dual functional bioactive peptide amphiphile incorporating both matrix metalloprotease substrate and cell adhesion motifs

We describe a bioactive lipopeptide that combines the capacity to promote the adhesion and subsequent self-detachment of live cells, using template-cell-environment feedback interactions. This self-assembling peptide amphiphile comprises a diene-containing hexadecyl lipid chain (C16e) linked to a matrix metalloprotease-cleavable sequence, Thr-Pro-Gly-Pro-Gln-Gly-Ile-Ala-Gly-Gln, and contiguous with a cell-attachment and signalling motif, Arg-Gly-Asp-Ser. Biophysical characterisation revealed that the PA self-assembles into 3 nm diameter spherical micelles above a critical aggregation concentration (cac). In addition, when used in solution at 5–150 nM (well below the cac), the PA is capable of forming film coatings that provide a stable surface for human corneal fibroblasts to attach and grow. Furthermore, these coatings were demonstrated to be sensitive to metalloproteases expressed endogenously by the attached cells, and consequently to elicit the controlled detachment of cells without compromising their viability. As such, this material constitutes a novel class of multi-functional coating for both fundamental and clinical applications in tissue engineering.

Training and the commitment of outsourced information technologies' workers: psychological contract fulfillment as a mediator

Outsourced workers in information technologies (IT) generally have high skills and a high value on the job market. Their IT outsourcing organizations are likely to provide them with training, in the first place for skill development, but perhaps also as a way to bind the workers to them. This can be understood along the role of the psychological contract. Outsourced IT workers may see training as a fulfillment of their psychological contract. Accordingly, we hypothesize that psychological contract fulfillment mediates the relationship between training and affective commitment to the IT outsourcer. This was tested in a sample of 158 Portuguese outsourced IT workers. The results showed that employees who considered that they were receiving good training opportunities felt a greater affective commitment to their IT outsourcers. This relationship was mediated by the fulfillment of the relational psychological contract.