Characteristic infrared spectroscopic patterns in the protein bands of human breast cancer tissue

Infrared (IR) spectra of normal, hyperplasia, fibroadenoma and carcinoma tissues of human breast obtained from 96 patients have been determined and analyzed statistically. Several spectral differences were detected in the frequency regions of N-H stretching, amide I, II and III bands: (1) the bands in the region 3000-3600cm-1 shifted to lower frequencies for the carcinomatous tissue; (2) the A(3300)/A(3075) absorbance ratio was significantly higher for the fibroadenoma than for the other types of tissues; (3) the frequency of the a-helix amide I band decreased for the malignant tissue, while the corresponding beta -sheet amide I band frequency increased; (4) the A(1657)/A(1635) and A(1553)/A(1540) absorbance ratios were the highest for fibroadenoma and carcinoma tissues; (5) the A(1680)/A(1657) absorbance ratio decreased significantly in the order of normal > hyperplasia > fibroadenoma > carcinoma; (6) the A(1651)/A(1545) absorbance ratio increased slightly for the fibroadenoma and the carcinoma tissues; (7) the bands at 1204 and 1278 cm(-1), assigned to the vibrational modes of the collagen, did not appear in the original spectra as resolved peaks and were distinctly stronger in the deconvoluted spectra of the carcinoma tissue and (8) the A(1657)/A(1204) and A(1657)/A(1278) absorbance ratios, both yielding information on the relative content of collagen, increased in the order of normal < hyperplasia < carcinoma < fibroadenoma. The said differences imply that the information is useful for the diagnosis of breast cancer and malignant breast abnormalities, and may serve as a basis for further studies on conformational changes in tissue proteins during carcinogenesis. (C) 2001 Elsevier Science B.V. All rights reserved.

Spectral Reflectance Characteristics of Kimberlite Indicator Minerals and Other Selected Mineral Grains

High chromium content in kimberlite indicator minerals such as pyrope garnet and diopside is often correlated with the presence of diamonds. In this study, kimberlite indicator minerals were examined using visible light reflectance spectroscopy to determine if chromium content can be correlated with spectral absorption features. The depth of absorption features in the visible spectral region were correlated with the molecular percentage of chromium and other first series transition metal elements obtained by electron microprobe data. In the visible part of the spectrum, chromium is evident by 3 absorption features in the pyrope reflectance spectrum; one isolated and narrow feature at the wavelength 689 nm was used to correlate with the chromium mol %. The isolation of this feature in the pyrope spectra is advantageous since it is not directly affected by other proximal absorption bands that could be caused by other transition metals. Analysis of the feature indicates that as grain volume increases the depth of the absorption feature will also increase. Clustering grain volumes into fractions yields better correlation between absorption depth and mol % chromium. Other types of garnet (almandine, grossular, spessartine) and kimberlite indicator minerals (olivine, diopside, chromite, ilmenite) were analyzed to determine if other absorption features could be used to predict the proportion of specific transition metal elements. Diopside in particular illustrates the same isolated chromium absorption feature as pyrope and may indicate mol percent but needs further study with larger sample sets.

Effect of annealing on the spectral and nonlinear optical characteristics of thin films of nano-ZnO

The annealing effect on the spectral and nonlinear optical NLO characteristics of ZnO thin films deposited on quartz substrates by sol-gel process is investigated. As the annealing temperature increases from 300–1050 °C, there is a decrease in the band gap, which indicates the changes of the interface of ZnO. ZnO is reported to show two emission bands, an ultraviolet UV emission band and another in the green region. The intensity of the UV peak remains the same while the intensity of the visible peak increases with increase in annealing temperature. The role of oxygen in ZnO thin films during the annealing process is important to the change in optical properties. The mechanism of the luminescence suggests that UV luminescence of ZnO thin films is related to the transition from conduction band edge to valence band, and green luminescence is caused by the transition from deep donor level to valence band due to oxygen vacancies. The NLO response of these samples is studied using nanosecond laser pulses at off-resonance wavelengths. The nonlinear absorption coefficient increases from 2.9 ×10−6 to 1.0 ×10−4 m/W when the annealing temperature is increased from 300 to 1050 °C, mainly due to the enhancement of interfacial state and exciton oscillator strength. The third order optical susceptibility x(3) increases with increase in annealing temperature (T) within the range of our investigations. In the weak confinement regime, T2.4 dependence of x(3) is obtained for ZnO thin films. The role of annealing temperature on the optical limiting response is also studied.

Spectral studies of naphthalocyanine (Nc) and rare earth phthalocyanine (RePc) molecules in an inorganic glassy borate matrix

Optical absorption and emission spectral studies of free and metal naphthalocyanine doped borate glass matrix are reported for the first time. Absorption spectra recorded in the UV- VIS-NIR region show the characteristic absorption bands, namely, the B-band and Q-band of the naphthalocyanine (Nc) molecule. Some of the important spectral parameters, namely, the optical absorption coefficient (α), molar extinction coefficient (ε) and absorption cross section (σa) of the principal absorption transitions are determined. Optical band gap (Eg) of the materials evaluated from the functional dependence of absorption coefficient on photon energy lies in the range 1.6 eV≤Eg≤2.1 eV. All fluorescence spectra except that of EuNc consist of an intense band in the 765 nm region corresponding to the excitation of Q-band. In EuNc the maximum fluorescence intensity band is observed at 824 nm. The intensity of the principal fluorescence band is maximum in ZnNc, whereas it is minimum in H2Nc. Radiative parameters of the principal fluorescence transitions corresponding to the Q-band excitation are also reported for the naphthalocyanine and phthalocyanine based matrices.

Raman and infrared spectral analysis of thallium niobyl phosphates: Tl2NbO2PO4, Tl3NaNb4O9(PO4)2 and TlNbOP2O7

Raman and infrared spectra of Tl2NbO2PO4, Tl3NaNb4O9(PO4)2 and TlNbOP2O7 are reported. The observed bands are assigned in terms of vibrations of NbO6 octahedra and PO4 tetrahedra in the first two compounds and in terms of NbO6 octahedra and P2O7 4− anion in the third compound. The NbO6 octahedra in all the title compounds are found to be corner-shared and distorted. The higher wavenumber values of the ν1 (NbO6) mode and other stretching modes indicate that the NbO6 octahedra in them are distorted in the order TlNbOP2O7 > Tl2NbO2PO4 > Tl3NaNb4O9(PO4)2. The splitting of the ν3 (PO4) mode indicates that PO4 tetrahedra is distorted more in Tl2NbO2PO4 than in Tl3NaNb4O9(PO4)2. The symmetry of P2O7 4− anion in TlNbOP2O7 is lowered. Bands indicate that the P–O–P bridge in the above compound has a bent P–O–P bridge configuration

Temporal-envelope constancy of speech in rooms and the perceptual weighting of frequency bands

Three experiments measured constancy in speech perception, using natural-speech messages or noise-band vocoder versions of them. The eight vocoder-bands had equally log-spaced center-frequencies and the shapes of corresponding “auditory” filters. Consequently, the bands had the temporal envelopes that arise in these auditory filters when the speech is played. The “sir” or “stir” test-words were distinguished by degrees of amplitude modulation, and played in the context; “next you’ll get _ to click on.” Listeners identified test-words appropriately, even in the vocoder conditions where the speech had a “noise-like” quality. Constancy was assessed by comparing the identification of test-words with low or high levels of room reflections across conditions where the context had either a low or a high level of reflections. Constancy was obtained with both the natural and the vocoded speech, indicating that the effect arises through temporal-envelope processing. Two further experiments assessed perceptual weighting of the different bands, both in the test word and in the context. The resulting weighting functions both increase monotonically with frequency, following the spectral characteristics of the test-word’s [s]. It is suggested that these two weighting functions are similar because they both come about through the perceptual grouping of the test-word’s bands.

Intensities and self-broadening coefficients of the strongest water vapour lines in the 2.7 and 6.25μm absorption bands

Intensities and self-broadening coefficients are presented for about 460 of the strongest water vapour lines in the spectral regions 1400–1840 cm−1 and 3440–3970 cm−1 at room temperature, obtained from rather unique measurements using a 5-mm-path-length cell. The retrieved spectral line parameters are compared with those in the HITRAN database ver. 2008 and 2012 and with recent ab-initio calculations. Both the retrieved intensities and half-widths are on average in reasonable agreement with those in HITRAN-2012. Maximum systematic differences do not exceed 4% for intensities (1600 cm−1 band) and 7% for self-broadening coefficients (3600 cm−1 band). For many lines however significant disagreements were detected with the HITRAN-2012 data, exceeding the average uncertainty of the retrieval. In addition, water vapour line parameters for 5300 cm−1 (1.9 μm) band reported by us in 2005 were also compared with HITRAN-2012, and show average differences of 4–5% for both intensities and half-widths.

Retrievals of a size parameter for phytoplankton and spectral light absorption by colored detrital matter from water-leaving radiances at SeaWiFS channels in a continental shelf region off Brazil

Many efforts are currently oriented toward extracting more information from ocean color than the chlorophyll a concentration. Among biological parameters potentially accessible from space, estimates of phytoplankton cell size and light absorption by colored detrital matter (CDM) would lead to an indirect assessment of major components of the organic carbon pool in the ocean, which would benefit oceanic carbon budget models. We present here 2 procedures to retrieve simultaneously from ocean color measurements in a limited number of bands, magnitudes, and spectral shapes for both light absorption by CDM and phytoplankton, along with a size parameter for phytoplankton. The performance of the 2 procedures was evaluated using different data sets that correspond to increasing uncertainties: ( 1) measured absorption coefficients of phytoplankton, particulate detritus, and colored dissolved organic matter ( CDOM) and measured chlorophyll a concentrations and ( 2) SeaWiFS upwelling radiance measurements and chlorophyll a concentrations estimated from global algorithms. In situ data were acquired during 3 cruises, differing by their relative proportions in CDM and phytoplankton, over a continental shelf off Brazil. No local information was introduced in either procedure, to make them more generally applicable. Over the study area, the absorption coefficient of CDM at 443 nm was retrieved from SeaWiFS radiances with a relative root mean square error (RMSE) of 33%, and phytoplankton light absorption coefficients in SeaWiFS bands ( from 412 to 510 nm) were retrieved with RMSEs between 28% and 33%. These results are comparable to or better than those obtained by 3 published models. In addition, a size parameter of phytoplankton and the spectral slope of CDM absorption were retrieved with RMSEs of 17% and 22%, respectively. If these methods are applied at a regional scale, the performances could be substantially improved by locally tuning some empirical relationships.

Nanostructured hybrid films containing nanophosphor: Fabrication and electronic spectral properties

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Alteration of soil properties through a weathering sequence as evaluated by spectral reflectance

In the study of physical, chemical, and mineralogical data related to the weathering of soils and the quantification of their properties, remote sensing constitutes an important technique that, in addition to conventional analyses, can contribute to soil survey. The objectives of this research were to characterize and differentiate soils developed from basaltic rocks that occur in the Parana state, Brazil and to quantify soil properties based on their spectral reflectance. These observations were used to verify the relationship between the soils and reflectance with regard to weathering, organic matter (OM), and forms of Fe. From the least to the most weathered soil, we used a Typic Argiudoll (Reddish Brunizem), Rhodudalf (Terra Roxa Estruturada), and Rhodic Hapludox (Very Dark Red Latosol). The spectral reflectances between 400 and 2500 nm were obtained in the laboratory from soil samples collected at two depth increments, 0- to 20- and 40- to 60-cm, using an Infra Red Intelligent Spectroradiometer (IRIS). Correlation, regression, and discriminant estimates were used in analyzing the soil and spectral data. Results of this study indicated that soils could be separated at the soil-type level based on reflectance intensity in various absorption bands. Soil collected in the 40- to 60-cm depth appeared to have higher reflectance intensities than those from the 0- to 20-cm depth. Removal of OM from soil samples promoted higher reflectance intensity in the entire spectrum. Amorphous and crystalline Fe influenced reflectance differently. Weathering of basaltic soils was correlated with alterations in the reflectance intensities and absorption features of the spectral curves. Multivariate analysis demonstrated that this technique was efficient in the estimation of clay, silt, kaolinite, crystalline Fe, amorphous Fe, and Mg through the use of reflected energy of the soils.

Early autonomic dysfunction in patients with diabetes mellitus assessed by spectral analysis of heart rate and blood pressure variability

Patients with diabetes mellitus (DM) often have alterations of the autonomic nervous system (ANS), even early in their disease course. Previous research has not evaluated whether these changes may have consequences on adaptation mechanisms in DM, e.g. to mental stress. We therefore evaluated whether patients with DM who already had early alterations of the ANS reacted with an abnormal regulatory pattern to mental stress. We used the spectral analysis technique, known to be valuable and reliable in the investigation of disturbances of the ANS. We investigated 34 patients with DM without clinical evidence of ANS dysfunction (e.g. orthostatic hypotension) and 44 normal control subjects (NC group). No patients on medication known to alter ANS responses were accepted. The investigation consisted of a resting state evaluation and a mental stress task (BonnDet). In basal values, only the 21 patients with type 2 DM were different in respect to body mass index and systolic blood pressure. In the study parameters we found significantly lower values in resting and mental stress spectral power of mid-frequency band (known to represent predominantly sympathetic influences) and of high-frequency and respiration bands (known to represent parasympathetic influences) in patients with DM (types 1 and 2) compared with NC group (5.3 +/- 1.2 ms2 vs. 6.1 +/- 1.3 ms2, and 5.5 +/- 1.6 ms2 vs. 6.2 +/- 1.5 ms2, and 4.6 +/- 1.7 ms2 vs. 6.2 +/- 1.5 ms2, for resting values respectively; 4.7 +/- 1.4 ms2 vs. 5.9 +/- 1.2 ms2, and 4.6 +/- 1.9 ms2 vs. 5.6 +/- 1.7 ms2, and 3.7 +/- 2.1 ms2 vs. 5.6 +/- 1.7 ms2, for stress values respectively; M/F ratio 6/26 vs. 30/14). These differences remained significant even when controlled for age, sex, and body weight. However, patients with DM type 2 (and significantly higher body weight) showed only significant values in mental stress modulus values. There were no specific group effects in the patients with DM in adaptation mechanisms to mental stress compared with the NC group. These findings demonstrate that power spectral examinations at rest are sufficiently reliable to diagnose early alterations in ANS in patients with DM. The spectral analysis technique is sensitive and reliable in investigation of ANS in patients with DM without clinically symptomatic autonomic dysfunction.

Short-term spectral analysis of ODP Hole 114-704B

Short-term spectral analysis was carried out on geochemical logging data from ODP Site 704. The FFT was used to compute the amplitude spectra of short-term overlapping segments to produce depth-period-amplitude spectrograms of the logging data. The spectrograms provided a means of evaluating the significance of the observed periodic components. The periodic components that were consistently present and prominent across a given record interval were considered to be significant. Changes in the spectrogram characteristics seem to reflect changes in either lithology, sedimentation rates, or hiatuses and may therefore provide useful information to aid in stratigraphic and paleoenvironmental studies. The dominant periodicity during the late Pleistocene and Brunhes Chron (0.97 to 0.47 Ma) was determined to be > 100,000 yr whereas the upper Matuyama Chron was dominated by the 41,000-yr periodicity. These periodicities suggest that the sedimentation patterns within the upper Matuyama Chron (0.98-1.78 Ma) were influenced by the Milankovitch obliquity cycle and those within the latest Matuyama-Brunhes Chron (<0.98 Ma) by the eccentricity cycle. The Brunhes/Matuyama boundary therefore represents a major discontinuity. Periodicities observed within the lower Matuyama and the upper Gauss Chron did not correlate with any of the periodicities within the Milankovitch frequency bands.

The spectral sensitivity of long period gratings fabricated in elliptical core D-shaped optical fibre

Long period gratings (LPGs) were written into a D-shaped optical fibre that has an elliptical core with a W-shaped refractive index profile and the first detailed investigation of such LPGs is presented. The LPGs’ attenuation bands were found to be sensitive to the polarisation of the interrogating light with a spectral separation of about 15 nm between the two orthogonal polarisation states. A finite element method was successfully used to model many of the behavioural features of the LPGs. In addition, two spectrally overlapping attenuation bands corresponding to orthogonal polarisation states were observed; modelling successfully reproduced this spectral feature. The spectral sensitivity of both orthogonal states was experimentally measured with respect to temperature and bending. These LPG devices produced blue and red wavelength shifts depending upon the orientation of the bend with measured maximum sensitivities of -3.56 and +6.51 nm m, suggesting that this type of fibre LPG may be useful as a shape/bend orientation sensor with reduced errors associated with polarisation dependence. The use of neighbouring bands to discriminate between temperature and bending was also demonstrated, leading to an overall curvature error of ±0.14 m-1 and an overall temperature error of ±0.3 °C with a maximum polarisation dependence error of ±8 × 10-2 m-1 for curvature and ±5 × 10-2 °C for temperature.

The intelligibility of noise-vocoded speech:spectral information available from across-channel comparison of amplitude envelopes

Noise-vocoded (NV) speech is often regarded as conveying phonetic information primarily through temporal-envelope cues rather than spectral cues. However, listeners may infer the formant frequencies in the vocal-tract output—a key source of phonetic detail—from across-band differences in amplitude when speech is processed through a small number of channels. The potential utility of this spectral information was assessed for NV speech created by filtering sentences into six frequency bands, and using the amplitude envelope of each band (=30 Hz) to modulate a matched noise-band carrier (N). Bands were paired, corresponding to F1 (˜N1 + N2), F2 (˜N3 + N4) and the higher formants (F3' ˜ N5 + N6), such that the frequency contour of each formant was implied by variations in relative amplitude between bands within the corresponding pair. Three-formant analogues (F0 = 150 Hz) of the NV stimuli were synthesized using frame-by-frame reconstruction of the frequency and amplitude of each formant. These analogues were less intelligible than the NV stimuli or analogues created using contours extracted from spectrograms of the original sentences, but more intelligible than when the frequency contours were replaced with constant (mean) values. Across-band comparisons of amplitude envelopes in NV speech can provide phonetically important information about the frequency contours of the underlying formants.