Palladium-catalyzed asymmetric synthesis of axially chiral allenylsilanes and their application to SE2' chirality transfer reactions

Stepwise application of the Pd-catalyzed S(N)2' reaction and the desilylative S(E)2' reaction to the ambivalent 2-bromo-1-silyl-1,3-dienes provides a novel route to the highly enantioselective construction of tertiary and quaternary propargylic stereogenic centers via axially chiral allenylsilanes.     

A microelectrochemical sensing system for the determination of Epstein–Barr virus antibodies

An electrochemical method for the detection of Epstein–Barr virus (EBV) infections is described. The method relies on an immunoassay with electrochemical read-outs based on recombinant antigens. The antigens are immobilised on an Au electrode surface and used to complementarily bind antibodies from serum samples found during different stages of infection with EBV. Thiol chemistry under formation of self-assembled monolayers functions as a means to immobilise the antigens at the Au electrodes. A reporter system consisting of a secondary antibody labelled with alkaline phosphatase is used for electrochemical detection. The feasibility of the assay design is demonstrated and the assay performance is tested against the current gold standard in EBV detection. Close correlation is obtained for the results found for the developed electrochemical immunoassay and a standard line assay. Moreover, the electrochemical immunoassay is combined with a nanoporous electrode system allowing signal amplification by means of redox recycling. An amplification factor of 24 could be achieved.     

Measuring hidden Higgs and strongly-interacting Higgs scenarios

Higgs couplings can be affected by physics beyond the Standard Model. We study modifications through interactions with a hidden sector and in specific composite Higgs models accessible at the LHC. Both scenarios give rise to congruent patterns of universal, or partially universal, shifts. In addition, Higgs decays to the hidden sector may lead to invisible decay modes which we also exploit. Experimental bounds on such potential modifications will measure the concordance of an observed Higgs boson with the Standard Model.     

Characterisation of FXTAS related isolated intranuclear protein inclusions using laser tweezers Raman spectroscopy

We report the analysis of the vibrational modes of intranuclear protein inclusions isolated from the brain of human subjects with the Fragile X‐associated tremor/ataxia syndrome (FXTAS). In this preliminary study, Raman spectra of optically trapped inclusions were measured and analysed to determine protein composition and structure. Our main findings are as follows: (1) The spectra of protein inclusions are characteristic of H2A and H2B histones, which correlate with previous mass spectrometry (MS) studies; (2) Tyrosine is present in its OH form and exposed at the protein surface; (3) Zn and to a lesser extent Cu bound to histidine side chains are detected in the inclusions; (4) The tryptophan side‐chain torsion angle is calculated to be 102°; (5) Several potential spectroscopic markers for the inclusions of FXTAS are identified. These results show the capability of using laser tweezers Raman spectroscopy to identify protein inclusions in a non‐perturbative way and to gain further insight into the pathogenesis and progression of FXTAS in human subjects and in experimental models of this disorder. Copyright © 2009 John Wiley & Sons, Ltd.     

Analysis of self‐repair mechanisms of Phaseolus vulgaris var. saxa using near‐infrared surface‐enhanced Raman spectroscopy

We used surface‐enhanced Raman spectroscopy (SERS) to investigate ultrastructural changes in cell‐wall composition during the self‐repair of lacerated hypocotyls of Phaseolus vulgaris var. saxa. A detailed study of self‐repair mechanisms requires localized information about cell‐wall structure and morphology in addition to the chemical cell‐wall composition. Characteristic Raman and SER spectra yielded two‐dimensional maps of cross sections of P. vulgaris var. saxa visualizing chemical compositions in the walls of different cell types and during various repair phases. SERS substrate particles were produced by the reduction of gold chloride on the plant tissue surface and characterized with absorption spectroscopy, scanning electron microscopy and energy‐dispersive X‐ray spectroscopy. The SERS results were compared with stained cross sections of the same plant using dark‐field microscopy with focus on lignin and suberin contents in repairing cells. In addition, SERS measurements revealed Au cyanide compounds on the cell surface, indicating the formation of hydrogen cyanide during the self‐repair phase. Copyright © 2009 John Wiley & Sons, Ltd.     

Size-dependent word frequencies and translational invariance of books

It is shown that a real novel shares many characteristic features with a null model in which the words are randomly distributed throughout the text. Such a common feature is a certain translational invariance of the text. Another is that the functional form of the word-frequency distribution of a novel depends on the length of the text in the same way as the null model. This means that an approximate power-law tail ascribed to the data will have an exponent which changes with the size of the text-section which is analyzed. A further consequence is that a novel cannot be described by text-evolution models such as the Simon model. The size-transformation of a novel is found to be well described by a specific Random Book Transformation. This size transformation in addition enables a more precise determination of the functional form of the word-frequency distribution. The implications of the results are discussed.