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A Raman spectroscopic investigation of the disulfide conformation in oxytocin and lysine vasopressin.

The conformation of the CCSSCC moiety in oxytocin and lysine vasopressin is investigated using laser Raman spectroscopy. The Raman spectra of solutions of these hormones in water and in dimethyl sulfoxide show an intense band at 508 cm-1 which is assigned to the S-S stretching mode. The presence of shoulders on this band between 490 and 525 cm-1 shows that there is an equilibrium among several conformations for the disulfide unit of these hormones in solution. Most of the CS-SC dihedral angles are within 30 degrees of +/-90 degrees, but some of the molecules have CS-SC dihedral angles strained away from this value by more than 30 degrees. The previously published circular dichroism spectra of these hormones are reinterpreted, and it is shown that the circular dichroism spectra indicate the presence of more than one conformation for the disulfide unit, in agreement with the Raman results.

Cystine↗

Estimation of residual stress in dental porcelain by laser-Raman spectroscopy.

Residual stress in the surface of dental porcelain was estimated using laser Raman spectroscopy. Sixteen different magnitudes of residual stress were generated in commercial porcelain disks by tempering, ion exchange, and slow cooling. The specimens were analyzed using a laser-Raman spectrometer with an Ar+ laser. The Raman shift of the largest peak near 500 cm-1 originating from silica was used as an indicator of the level of residual stress. For comparison, the residual stress in the specimen was estimated by the indentation micro-fracture method. The Raman shift of the porcelain increased with increasing residual stress at 3.7 x 10(-2) cm-1/MPa (R2 = 0.89). The increase in the Raman shift corresponded to the increase in compressive stress. In addition, the value of full width at half maximum on the peak corresponded to the residual stress (-1.57 x 10(-1) cm-1/MPa: R2 = 0.82). These results revealed that the increase of residual stress in porcelain clearly appears on the Raman spectrum as an increase in the Raman shift. It is thus feasible to estimate residual stress in porcelain by laser-Raman spectroscopy.

Aluminum Silicates↗

Comparison of depth of dentin etching and resin infiltration with single-step adhesive systems.

OBJECTIVES: Adhesion of resin composites to dentin is currently believed to result from impregnation of adhesive resin into superficially demineralized dentin. The purpose of this study was to use micro-Raman spectroscopy and scanning electron microscopy (SEM) to investigate the extent of resin penetration into etched dentin with single-step adhesive systems. METHODS: Adhesive systems used were One-Up Bond F (Tokuyama Dental) and Reactmer Bond (Shofu, Inc.). A self-etching primer system Mac Bond II (Tokuyama Dental) was employed as a control. Resin composites were bonded to bovine dentin with the adhesive systems, and specimens were sectioned parallel to dentinal tubules. Raman spectra were successively recorded along a line perpendicular to the dentin-adhesive interface in steps of 0.2 microm and the spectra were obtained. SEM observations of the resin-dentin interface were also conducted. RESULTS: The dentin-resin interface of single-step adhesive systems showed a gradual transition in the relative amount of adhesive from the resin side to dentin side. The widths of resin penetration into demineralized dentin detected by Raman microscopy were greater than those obtained by the morphological analysis using SEM. CONCLUSIONS: From the results of this study, a gradual variation in the composition of the dentin-resin interface was detected, and the degree of resin impregnation observed with SEM observation was less than that detected with the Raman microscopy.

Animals↗

In situ spectral monitoring of mRNA translation in embryonic stem cells during differentiation in vitro.

Raman microspectroscopy was used to determine biochemical markers during the differentiation of embryonic murine stem cells (mES) in vitro. Such markers are useful to determine the differentiation status of ES cells cultured on biomaterials. Raman spectra of mES cells as undifferentiated, spontaneously differentiated (4 days), and differentiated cells via formation of embryoid bodies (16, 20 days) were analyzed. Unsupervised hierarchical cluster analysis and principal component analysis were used to determine biochemical differences between mES cells in various states of differentiation. The undifferentiated cells were characterized by high scores of the first principal component (PC1, 49% variance). Similarity between the PC1 loading and the Raman spectrum of RNA indicated a high concentration of RNA in mES cells compared to differentiated cells. The ratio between the peak areas of RNA and proteins was used as a measure of mRNA translation. Using the same peak area ratio, it was possible to differentiate even between mES as undifferentiated and in early stages of differentiation (4 days). These findings were correlated with biological studies reporting high levels of nontranslated mRNA during early embryonic development. Therefore, the RNA translation obtained from the Raman spectra can be used as marker of differentiation state of mES cells.

Animals↗

Characterization of polymorphic forms of fluconazole using Fourier transform Raman spectroscopy.

Detailed Fourier transform Raman spectra of fluconazole have been recorded and the main spectral features of fluconazole have been assigned to its vibrational modes. Two different polymorphic forms of fluoconazole were identified in two spectral regions, 150-1700 cm-1 and 2700-3200 cm-1, respectively. The FT-Raman results agree well with those of differential scanning calorimetry and X-ray powder diffractometry. The combination of definiteness with easy sample handling makes FT-Raman spectroscopy a valuable technique for the analysis of polymorphs.

Calorimetry, Differential Scanning↗

Raman spectroscopy.

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Arteriosclerosis↗