Neutron diffraction data with high real-space resolution are reported for an extensive series of cesium germanate glasses with 2, 5, 10, 15, 18, 21, 25, and 30 mol % Cs(2)O, and also for pure GeO(2) in its vitreous, quartz, and rutile forms. The results for pure GeO(2) show that neutron diffraction can clearly identify an increase in the Ge-O coordination number above the tetrahedral value of four. The results for cesium germanate glasses give strong evidence that the Ge-O coordination number rises to a maximum of 4.36 +/- 0.03 for 18 mol % Cs(2)O and then declines. This behavior may be associated with the germanate anomaly in the thermophysical properties. A model is developed for the composition-dependence of the Ge-O coordination number, and according to this model the rise in the coordination number involves the formation of mostly GeO(5) units, rather than GeO(6) units. Our results also show that the low alkali anomaly is a longer range phenomenon, and is not associated with a preference for the formation of nonbridging oxygens for very low alkali oxide content.

An expanding body of literature suggests Raman spectroscopy is a promising tool for skin cancer diagnosis and in-vivo tumor border demarcation. The development of an in-vivo diagnostic tool is, however, hampered by the fact that construction of fiber optic probes suitable for Raman spectroscopy in the so-called fingerprint region is complicated. In contrast, the use of the high wave-number region allows for fiber optic probes with a very simple design. We investigate whether high wave-number Raman spectroscopy (2800 to 3125 cm(-1)) is able to provide sufficient information for noninvasive discrimination between basal cell carcinoma (BCC) and noninvolved skin. Using a simple fiber optic probe, Raman spectra are obtained from 19 BCC biopsy specimens and 9 biopsy specimens of perilesional skin. A linear discriminant analysis (LDA)-based tissue classification model is developed, which discriminates between BCC and noninvolved skin with high accuracy. This is a crucial step in the development of clinical dermatological applications based on fiber optic Raman spectroscopy.

Raman spectroscopy is a powerful diagnostic tool, enabling tissue identification and classification. Mostly, the so-called fingerprint (approximately 400-1800 cm(-1)) spectral region is used. In vivo application often requires small flexible fiber-optic probes, and is hindered by the intense Raman signal that is generated in the fused silica core of the fiber. This necessitates filtering of laser light, which is guided to the tissue, and of the scattered light collected from the tissue, leading to complex and expensive designs. Fused silica has no Raman signal in the high wave number region (2400-3800 cm(-1)). This enables the use of a single unfiltered fiber to guide laser light to the tissue and to collect scattered light in this spectral region. We show, by means of a comparison of in vitro Raman microspectroscopic maps of thin tissue sections (brain tumors, bladder), measured both in the high wave number region and in the fingerprint region, that essentially the same diagnostic information is obtained in the two wave number regions. This suggests that for many clinical applications the technological hurdle of designing and constructing suitable fiber-optic probes may be eliminated by using the high wave number region and a simple piece of standard optical fiber.

In vivo Raman spectroscopy, using fiber-optic probes is hindered by the intense background signal, which is generated in the fused-silica fibers, in the fingerprint region of the Raman spectrum (approximately 0-2000 cm(-1)). Optical filtering is necessary to obtain tissue spectra of sufficient quality. The complexity of fiber-optic probes for fingerprint Raman spectroscopy, in combination with size constraints and flexibility requirements for in vivo use have been a major obstacle in the development of in vivo diagnostic tools based on Raman spectroscopy. A setup for remote Raman spectroscopic tissue characterization in the high-wavenumber region ( approximately 2400-3800 cm(-1)) is presented. It makes use of a single, unfiltered, optical fiber for guiding laser light to the sample and for collecting scattered light and guiding it back to a spectrometer. Such a simple configuration is possible because the fused-silica core and cladding of the fiber present almost no Raman background signal at these wavenumbers. Several commercially available optical fibers were tested with respect to Raman signal background, to determine their suitability for in vivo Raman spectroscopy measurements in the high-wavenumber region. Different fiber core, cladding, and coating materials were tested. Silica core-silica clad fibers, with an acrylate coating and a black nylon jacket, proved to be one of the best candidates. In vitro measurements on brain tissue of a 6-month-old pig were obtained with a remote high-wavenumber Raman setup. They illustrate the low background signal generated in the setup and the signal quality obtained with a collection time of 1 s.

No abstract