A microspectroscopic study of the electronic homogeneity of ordered and disordered Sr2FeMoO6

Disordered Sr₂FeMoO₆ shows a drastic reduction in saturation magnetization compared to highly ordered samples, moreover magnetization as a function of the temperature for different disordered samples shows qualitatively different behaviours. We investigate the origin of such diversity by performing spatially resolved photoemission spectroscopy on various disordered samples. Our results establish that e_xtensive electronic inhomogeneity, arising most probably from an underlying chemical inhomogeneity in disordered samples, is responsible for the observed magnetic inhomogeneity. It is further pointed out that these inhomogeneities are connected with composition fluctuations of the type Sr₂Fe_1+x Mo_1-x O₆ with Fe-rich (x > 0) and Mo-rich (x < 0) regions. Dedicated to Prof J Gopalakrishnan on his 62nd birthday.     

Characterisation of the Kratos Axis Ultra with spherical mirror analyser for XPS imaging

The imaging performance of an XPS instrument employing a spherical mirror electron energy analyser has been characterised by measuring the peak position, full width at half maximum (FWHM), and lineshape, at every pixel in the image, for different modes of operation. Changes in these parameters have been identified and recommendations made for quantification of, and chemical state determination from, spectrum image data sets. Copyright © 2006 John Wiley & Sons, Ltd.     

Study of optical response of spinel oxide by utilizing IR-THz spectromicroscopy

We performed a spectromicroscopic measurement on LiV₂O₄ in IR-THz (25 meV–1.5 eV) from 6–300 K under high pressures up to 20 GPa by using a DAC at the spectromicroscopy station (BL43IR) at SPring-8. At 40 K, a clear metal–insulator change was observed above 6 GPa in the optical conductivity spectra. The newly developed peak structure around 1 eV reflects the pseudo-gap forming under pressure at 40 K.     

Aerosol damage to a microchannel plate analysed by X‐ray photoelectron spectromicroscopy

Localised corrosion on a microchannel plate has been studied using X‐ray photoelectron spectromicroscopy. Curve fitting to the spectra at each pixel in the image data set reveals the presence of sodium and carbonate species at the corrosion sites, which optical microscopy suggests originated as droplets. It is proposed that aerosol contamination of the alkali enriched microchannel plate during removal of particulate material using a stream of compressed gas was responsible for the initiation of corrosion. Copyright © 2006 John Wiley & Sons, Ltd.     

Deciphering the Structure and Chemical Composition of Drug Nanocarriers: From Bulk Approaches to Individual Nanoparticle Characterization

Drug nanocarriers (NCs) with sizes usually below 200 nm are gaining increasing interest in the treatment of severe diseases such as cancer and infections. Characterization methods to investigate the morphology and physicochemical properties of multifunctional NCs are key in their optimization and in the study of their in vitro and in vivo fate. Whereas a variety of methods has been developed to characterize “bulk” NCs in suspension, the scope of this review is to describe the different approaches for the NC characterization on an individual basis, for which fewer techniques are available. The accent is put on methods devoid of labelling, which could lead to artefacts. For each characterization method, the principles and approaches to analyze the data are presented in an accessible manner. Aspects related to sample preparation to avoid artefacts are indicated, and emphasis is put on examples of applications. NC characterization on an individual basis allows gaining invaluable information in terms of quality control, on: i) NC localization and fate in biological samples; ii) NC morphology and crystallinity; iii) distribution of the NC components (drugs, shells), and iv) quantification of NCs’ chemical composition. The individual characterization approaches are expected to gain increasing interest in the near future.     

A synchrotron FTIR microspectroscopy investigation of fungal hyphae grown under optimal and stressed conditions

Synchrotron FTIR can provide high spatial resolution (<10 μm pixel size) in situ biochemical analyses of intact biotissues, an area of increasing importance in the post-genomic era, as gene functions and gene networks are coming under direct scrutiny. With this technique, we can simultaneously assess multiple aspects of cell biochemistry and cytoplasmic composition. In this paper, we report the first results of our synchrotron FTIR examination of hyphae of three important fungal model systems, each with sequenced genomes and a wealth of research: Aspergillus, Neurospora, and Rhizopus. We have analyzed the FTIR maps of Aspergillus nidulans cells containing the hypA1 allele, a well-characterized single-gene temperature-sensitive morphogenetic mutation. The hypA1 cells resemble wildtype at 28 °C but have growth defects at 42 °C. We have also investigated Neurospora and Rhizopus cultures grown in media with optimal or elevated pH. Significant differences between the spectra of the three fungi are likely related to differences in composition and structure. In addition, high spatial resolution synchrotron FTIR spectroscopy provides an outstanding method for monitoring subtle subcellular changes that accompany environmental stress. Figure Photomicrographs and FTIR spectra acquired along Rhizopus hyphae grown at pH 6.5 (a) and pH 8.5 (b). Scale bars 50 μm     

Further developments in quantitative X‐ray photoelectron spectromicroscopy: preliminary results from the study of germanium corrosion

The moisture‐induced corrosion of an evaporated germanium film has been observed and studied using quantitative X‐ray photoelectron spectromicroscopy. The application of recently reported software for the processing of multi‐spectral image datasets (particularly noise reduction) to this real‐world problem revealed the formation of oxide islands above the continuous passive oxide layer. The software has been developed to map the thickness of these structures within the XPS sampling depth, with a spatial resolution of a few microns. This exemplifies a characterisation methodology of use in any situation where (non‐uniform) surface modification results in chemically shifted components of the same core level (or Auger peak) between the original substrate and new overlayer. Copyright © 2005 John Wiley & Sons, Ltd.     

Study by Raman spectromicroscopy of the effect of tensile deformation on the molecular structure of Bombyx mori silk

The effect of mechanical deformation on the polarized Raman spectra of a silk monofilament of the silkworm Bombyx mori has been studied in order to detect tensile stress-induced changes of the fibroin conformation and reorientation up to the breaking point. For this study, a motorized mechanical stretcher has been specifically designed to fit under the Raman microscope, thus allowing the simultaneous recording of the stress, strain and polarized Raman spectra. Due to its twin drive screw design, this stretcher allows to stretch the silk fiber symmetrically and thus to probe the same area of the fiber during the entire elongation procedure. The results obtained have allowed to clarify the assignment of some vibrational bands of silk. They also show that the intensity of some Raman bands is affected by tensile deformation. In particular, the amide III/amide I intensity ratio decreases as the strain increases and the variation is proportional to the stress applied on the fiber. These variations in intensity suggest that the alignment of the protein chains decreases with strain which might be due to the reorganization of the amorphous phase. The Raman spectra also show that several bands shift toward low wavenumbers as the strain applied increases indicating that the force constant and/or dihedral angles of the peptide bonds, in particular those involved in the β-sheets, are affected by drawing. Therefore, a local stress is directly applied on the β-sheets and the wavenumber shift observed is proportional to the stress applied on the fiber.     

In situ synchrotron far infrared micro-spectroelectrochemistry with a grazing angle objective

We demonstrate the use of a grazing angle objective attachment to carry out in situ far infrared micro-spectroelectrochemistry at a copper electrode on a nano-scale. A thin-layer spectrochemical cell made out of Teflon was used, fitted with a 20-μm thick Mylar window; the working electrode was 500 μm in diameter. Measurements were carried out in 0.1 M NaOH solution as a function of applied potential between –1.4 and 0 V vs a Hg/Hg₂SO₄ reference electrode. Spectra were obtained with excellent signal to noise ratio for the surface oxide film, formed on copper electrochemically with less than 1 nL of active solution volume. The surface film at 0 V was about 130 nm thick and consisted mainly of CuO, with possibly some Cu(OH)₂ also present. This interpretation is consistent with previous works and thermodynamic calculations. The technique should be useful in other investigations and the further development of electrochemical surface science.     

Confocal Raman spectromicroscopy for tin-core/carbon-shell nanowire heterostructure

High density heterostructures of carbon nanotubes encapsulated single crystalline tin nanowires have been characterized by Raman spectromicroscopy. The morphology, composition and structure of the synthesized nanoheterostructures were examined by using scanning electron microscopy, transmission electron microscopy. The Raman spectra obviously manifest the crystalline nano-graphite within amorphous carbon walls in the heterostructures. The Raman image reproduces the pristine heterostructures of the CNTs as seen in SEM image, which illustrate the single nanowires oriented uniformly grown on micro-graphitic fibers. It was found that the resultant heterostructures are luminescent which was attributed to crystalline nano-graphite embedded in the amorphous carbon matrix, which is a consequence of excitons localization within an increasing number of sp² rich clusters. The contrast in the Raman image reflects nonuniform distribution of the graphite cluster size which acts as the radiative centers. The luminescent property was reviewed. The enhanced Raman spectra and luminescent property by the well-defined tin nanowires inside the heterostructures was revealed.