Amplifying vibrational circular dichroism by manipulation of the electronic manifold

Vibrational circular dichroism is a powerful technique to study the stereochemistry of chiral molecules, but often suffers from small signal intensities. Electrochemical modulation of the energies of the electronically excited state manifold is now demonstrated to lead to an order of magnitude enhancement of the differential absorption. Quantum-chemical calculations show that increased mixing between ground and excited states is at the origin of this amplification.

CUP Intermediate Greek-English Lexicon

Document design and typeface design: A typographic specification for a new Intermediate Greek-English Lexicon by CUP, accompanied by typefaces modified for the specific typographic requirements of the text. The Lexicon is a substantial (over 1400 pages) publication for HE students and academics intended to complement Liddell-Scott (the standard reference for classical Greek since the 1850s), and has been in preparation for over a decade. The typographic appearance of such works has changed very little since the original editions, largely to the lack of suitable typefaces: early digital proofs of the Lexicon utilised directly digitised versions of historical typefaces, making the entries difficult to navigate, and the document uneven in typographic texture. Close collaboration with the editors of the Lexicon, and discussion of the historical precedents for such documents informed the design at all typographic levels to achieve a highly reader-friendly results that propose a model for this kind of typography. Uniquely for a work of this kind, typeface design decisions were integrated into the wider document design specification. A rethinking of the complex typography for Greek and English based on historical editions as well as equivalent bilingual reference works at this level (from OUP, CUP, Brill, Mondadori, and other publishers) led a redefinition of multi-script typeface pairing for the specific context, taking into account recent developments in typeface design. Specifically, the relevant weighting of elements within each entry were redefined, as well as the typographic texture of type styles across the two scripts. In details, Greek typefaces were modified to emphasise clarity and readability, particularly of diacritics, at very small sizes. The relative weights of typefaces typeset side-by-side were fine-tuned so that the visual hierarchy of the entires was unambiguous despite the dense typesetting.

An optically transparent thin-layer electrochemical cell for the study of vibrational circular dichroism of chiral redox-active molecules

An optically transparent thin-layer electrochemical (OTTLE) cell with a locally extended optical path has been developed in order to perform vibrational circular dichroism (VCD) spectroscopy on chiral molecules prepared in specific oxidation states by means of electrochemical reduction or oxidation. The new design of the electrochemical cell successfully addresses the technical challenges involved in achieving sufficient infrared absorption. The VCD-OTTLE cell proves to be a valuable tool for the investigation of chiral redox-active molecules.

Drawing from development: towards unifying theory and development of ICT4D

Within the literature, many authors have argued that the rapid growth of the field of Information and Communication Technologies for Development (ICT4D) has resulted in an emphasis on the applications rather than on theory. However, it is clear that it is not theories, rather the integration of theory and practice, that is often lacking. To address this gap, the authors begin by exploring some of the popular theoretical approaches to ICT4D with a view to identifying those theories relevant to shared impacts: development, delivery and communication. To unify practice and theory, we offer a framework to directly assess the impact of ICT4D on development.

Switchable amplification of vibrational circular dichroism as a probe of local chiral structure

A new method to detect the vibrational circular dichroism (VCD) of a localized part of a chiral molecular system is reported. A local VCD amplifier was implemented, and the distance dependence of the amplification was investigated in a series of peptides. The results indicate a characteristic distance of 2.0±0.3 bonds, which suggests that the amplification is a localized phenomenon. The amplifier can be covalently coupled to a specific part of a molecule, and can be switched ON and OFF electrochemically. By subtracting the VCD spectra obtained when the amplifier is in the ON and OFF states, the VCD of the local environment of the amplifier can be separated from the total VCD spectrum. Switchable local VCD amplification thus makes it possible to “zoom in” on a specific part of a chiral molecule.

Elucidating the structure of chiral molecules by using amplified vibrational circular dichroism: from theory to experimental realization

Recent experimental observations of enhanced vibrational circular dichroism (VCD) in molecular systems with low-lying electronically excited states suggest interesting new applications of VCD spectroscopy. The theory describing VCD enhancement through vibronic coupling schemes was derived by Nafie in 1983, but only recently experimental evidence of VCD amplification has demonstrated the extent to which this effect can be exploited as a structure elucidation tool to probe local structure. In this Concept paper, we give an overview of the physics behind vibrational circular dichroism, in particular the equations governing the VCD amplification effect, and review the latest experimental developments with a prospective view on the application of amplified VCD to locally probe biomolecular structure.

Raphael into the Baroque: drawing in the Carracci workshop

Discussion of the influence of Raphael's drawings on the practice of the workshop of Annibale Carracci in Rome.

Realising the cup product of local Tate duality

We present an explicit description, in terms of central simple algebras, of a cup product map which occurs in the statement of local Tate duality for Galois modules of prime cardinality p. Given cocycles f and g, we construct a central simple algebra of dimension p^2 whose class in the Brauer group gives the cup product f\cup g. This algebra is as small as possible.

FORCED CONVECTION TO LAMINAR FLOW OF LIQUID EGG YOLK IN CIRCULAR AND ANNULAR DUCTS

The steady-state heat transfer in laminar flow of liquid egg yolk - an important pseudoplastic fluid food - in circular and concentric annular ducts was experimentally investigated. The average convection heat transfer coefficients, determined by measuring temperatures before and after heating sections with constant temperatures at the tube wall, were used to obtain simple new empirical expressions to estimate the Nusselt numbers for fully established flows at the thermal entrance of the considered geometries. The comparisons with existing correlations for Newtonian and non-Newtonian fluids resulted in excellent agreement. The main contribution of this work is to supply practical and easily applicable correlations, which are, especially for the case of annulus, rather scarce and extensively required in the design of heat transfer operations dealing with similar shear-thinning products. In addition, the experimental results may support existing theoretical analyses.

gamma-zein secondary structure in solution by circular dichroism

The proline-rich N-terminal domain of gamma-zein has been reported in relevant process, which include its ability to cross the cell membranes. Evidences indicate that synthetic hexapeptide (PPPVHL), naturally found in N-terminal portion of gamma-zein, can adopt the polyproline II (PPII) conformation in aqueous solution. The secondary structure of gamma-zein in maize protein bodies had been analyzed by solid state Fourier transform infrared and nuclear magnetic resonance spectroscopies. However, it was not possible to measure PPII content in physiological environment since the beta-sheet and PPII signals overlap in both solid state techniques. Here, the secondary structure of gamma-zein has been analyzed by circular dichroism in SDS aqueous solution with and without ditiothreitol (DTT), and in 60% of 2-propanol and water with DTT The results show that gamma-zein has high helical content in all solutions. The PPII conformation was present at about 7% only in water/DTT solution. (c) 2007 Wiley Periodicals, Inc.