Ultrasensitive thermal lens spectroscopy of water

A recently developed dual-beam configuration that optimizes the thermal lens technique has been used to obtain the absorption spectrum of pure water from 350 to 528 nm. Our results indicate the minimum linear absorption coefficient smaller than 2 X 10(-5) cm(-1) between 360 and 400 nm. This value is lower than previous literature data, and it is blueshifted. Absorption coefficients as small as 2 X 10(-7) cm(-1) can be measured for water using 1 W of excitation power. A detection limit of similar to 6 X 10(-9) cm(-1) (P=1 W) for CCl(4) was estimated, which represents, to the best of our knowledge, the highest sensitivity obtained in small absorption measurements in liquids. (C) 2009 Optical Society of America

Lower Bounds on the Exchange-Correlation Energy in Reduced Dimensions

Bounds on the exchange-correlation energy of many-electron systems are derived and tested. By using universal scaling properties of the electron-electron interaction, we obtain the exponent of the bounds in three, two, one, and quasione dimensions. From the properties of the electron gas in the dilute regime, the tightest estimate to date is given for the numerical prefactor of the bound, which is crucial in practical applications. Numerical tests on various low-dimensional systems are in line with the bounds obtained and give evidence of an interesting dimensional crossover between two and one dimensions.

Physical signatures of discontinuities of the time-dependent exchange-correlation potential

The exact exchange-correlation (XC) potential in time-dependent density-functional theory (TDDFT) is known to develop steps and discontinuities upon change of the particle number in spatially confined regions or isolated subsystems. We demonstrate that the self-interaction corrected adiabatic local-density approximation for the XC potential has this property, using the example of electron loss of a model quantum well system. We then study the influence of the XC potential discontinuity in a real-time simulation of a dissociation process of an asymmetric double quantum well system, and show that it dramatically affects the population of the resulting isolated single quantum wells. This indicates the importance of a proper account of the discontinuities in TDDFT descriptions of ionization, dissociation or charge transfer processes.

Electronic structure of In(2)O(3) and Sn-doped In(2)O(3) by hard x-ray photoemission spectroscopy

The valence and core levels of In(2)O(3) and Sn-doped In(2)O(3) have been studied by hard x-ray photoemission spectroscopy (hv = 6000 eV) and by conventional Al K alpha (hv = 1486.6 eV) x-ray photoemission spectroscopy. The experimental spectra are compared with density-functional theory calculations. It is shown that structure deriving from electronic levels with significant In or Sn 5s character is selectively enhanced under 6000 eV excitation. This allows us to infer that conduction band states in Sn-doped samples and states at the bottom of the valence band both contain a pronounced In 5s contribution. The In 3d core line measured at hv = 1486.6 eV for both undoped and Sn-doped In(2)O(3) display an asymmetric lineshape, and may be fitted with two components associated with screened and unscreened final states. The In 3d core line spectra excited at hv = 6000 eV for the Sn-doped samples display pronounced shoulders and demand a fit with two components. The In 3d core line spectrum for the undoped sample can also be fitted with two components, although the relative intensity of the component associated with the screened final state is low, compared to excitation at 1486.6 eV. These results are consistent with a high concentration of carriers confined close to the surface of nominally undoped In(2)O(3). This conclusion is in accord with the fact that a conduction band feature observed for undoped In(2)O(3) in Al K alpha x-ray photoemission is much weaker than expected in hard x-ray photoemission.

gamma Cassiopeiae: an X-ray Be star with personality

An exciting unsolved problem in the study of high energy processes of early type stars concerns the physical mechanism for producing X-rays near the Be star gamma Cassiopeiae. By now we know that this source and several ""gamma Cas analogs"" exhibit an unusual hard thermal X-ray spectrum, compared both to normal massive stars and the non-thermal emission of known Be/X-ray binaries. Also, its light curve is variable on almost all conceivable timescales. In this study we reanalyze a high dispersion spectrum obtained by Chandra in 2001 and combine it with the analysis of a new (2004) spectrum and light curve obtained by XMM-Newton. We find that both spectra can be fit well with 3-4 optically thin, thermal components consisting of a hot component having a temperature kT(Q) similar to 12-14 keV, perhaps one with a value of similar to 2.4 keV, and two with well defined values near 0.6 keV and 0.11 keV. We argue that these components arise in discrete (almost monothermal) plasmas. Moreover, they cannot be produced within an integral gas structure or by the cooling of a dominant hot process. Consistent with earlier findings, we also find that the Fe abundance arising from K-shell ions is significantly subsolar and less than the Fe abundance from L-shell ions. We also find novel properties not present in the earlier Chandra spectrum, including a dramatic decrease in the local photoelectric absorption of soft X-rays, a decrease in the strength of the Fe and possibly of the Si K fluorescence features, underpredicted lines in two ions each of Ne and N (suggesting abundances that are similar to 1.5-3x and similar to 4x solar, respectively), and broadening of the strong NeXLy alpha and OVIII Ly alpha lines. In addition, we note certain traits in the gamma Cas spectrum that are different from those of the fairly well studied analog HD110432 - in this sense the stars have different ""personalities."" In particular, for gamma Cas the hot X-ray component remains nearly constant in temperature, and the photoelectric absorption of the X-ray plasmas can change dramatically. As found by previous investigators of gamma Cas, changes in flux, whether occurring slowly or in rapidly evolving flares, are only seldomly accompanied by variations in hardness. Moreover, the light curve can show a ""periodicity"" that is due to the presence of flux minima that recur semiregularly over a few hours, and which can appear again at different epochs.

Correlation between MMPs and their inhibitors in breast cancer tumor tissue specimens and in cell lines with different metastatic potential

Background: The metastatic disease rather than the primary tumor itself is responsible for death in most solid tumors, including breast cancer. The role of matrix metalloproteinases ( MMPs), tissue inhibitors of MMPs (TIMPs) and Reversion-inducing cysteine-rich protein with Kazal motifs ( RECK) in the metastatic process has previously been established. However, in all published studies only a limited number of MMPs/MMP inhibitors was analyzed in a limited number of cell lines. Here, we propose a more comprehensive approach by analyzing the expression levels of several MMPs (MMP-2, MMP-9 and MMP-14) and MMP inhibitors (TIMP-1, TIMP-2 and RECK) in different models ( five human breast cancer cell lines, 72 primary breast tumors and 30 adjacent normal tissues). Methods: We analyzed the expression levels of MMP-2, MMP-9 and MMP-14 and their inhibitors (TIMP-1, TIMP-2 and RECK) by quantitative RT-PCR (qRT-PCR) in five human breast cancer cell lines presenting increased invasiveness and metastatic potential, 72 primary breast tumors and 30 adjacent normal tissues. Moreover, the role of cell-extracellular matrix elements interactions in the regulation of expression and activity of MMPs and their inhibitors was analyzed by culturing these cell lines on plastic or on artificial ECM (Matrigel). Results: The results demonstrated that MMPs mRNA expression levels displayed a positive and statistically significant correlation with the transcriptional expression levels of their inhibitors both in the cell line models and in the tumor tissue samples. Furthermore, the expression of all MMP inhibitors was modulated by cell-Matrigel contact only in highly invasive and metastatic cell lines. The enzyme/inhibitor balance at the transcriptional level significantly favors the enzyme which is more evident in tumor than in adjacent non-tumor tissue samples. Conclusion: Our results suggest that the expression of MMPs and their inhibitors, at least at the transcriptional level, might be regulated by common factors and signaling pathways. Therefore, the multi-factorial analysis of these molecules could provide new and independent prognostic information contributing to the determination of more adequate therapy strategies for each patient.`

Application of electron paramagnetic resonance Spectroscopy for validation of the novel (AN plus DN) solvent polarity scale

Based on solvation studies of polymers, the sum (1: 1) of the electron acceptor (AN) and electron donor (DN) values of solvents has been proposed as an alternative polarity scale. To test this, the electron paramagnetic resonance isotropic hyperfine splitting constant, a parameter known to be dependent on the polarity/proticity of the medium, was correlated with the (AN+DN) term using three paramagnetic probes. The linear regression coefficient calculated for 15 different solvents was approximately 0.9, quite similar to those of other well-known polarity parameters, attesting to the validity of the (AN+DN) term as a novel ""two-parameter"" solvent polarity scale.

Low-frequency Raman spectra and fragility of imidazolium ionic liquids

Raman spectra within the 5-200 cm(-1) range have been recorded as a function of temperature for different ionic liquids based on imidazolium cations. A correlation has been found between fragility and the temperature dependence of the strength of fast relaxational motions. Understanding quasielastic scattering as the relaxational contribution to ionic mean-squared displacement elucidates some effects on ionic liquids' fragility resulting from modifications in the chemical structure. (C) 2010 American Institute of Physics. [doi:10.1063/1.3462962]

High performance gold nanorods and silver nanocubes in surface-enhanced Raman spectroscopy of pesticides

The behavior of Au nanorods and Ag nanocubes as analytical sensors was evaluated for three different classes of herbicides. The use of such anisotropic nanoparticles in surface-enhanced Raman scattering (SERS) experiments allows the one to obtain the spectrum of crystal violet dye in the single molecule regime, as well as the pesticides dichlorophenoxyacetic acid (2,4-D), trichlorfon and ametryn. Such metallic substrates show high SERS performance at low analyte concentrations making them adequate for use as analytical sensors. Density functional theory (DFT) calculations of the geometries and vibrational wavenumbers of the adsorbates in the presence of silver or gold atoms were used to elucidate the nature of adsorbate-nanostructure bonding in each case and support the enhancement patterns observed in each SERS spectrum.

Chromic materials for responsive surface-enhanced resonance Raman scattering systems: a nanometric pH sensor

The use of chromic materials for responsive surface-enhanced resonance Raman scattering (SERRS) based nanosensors is reported. The potential of nano-chromic SERRS is demonstrated with the use of the halochrome methyl yellow to fabricate an ultrasensitive pH optical sensor. Some of the challenges of the incorporation of chromic materials with metal nanostructures are addressed through the use of computational calculations and a comparison to measured SERRS and surface-enhanced Raman scattering (SERS) spectra is presented. A strong correlation between the measured SERRS and the medium's proton concentration is demonstrated for the pH range 2-6. The high sensitivity achieved by the use of resonance Raman conditions is shown through responsive SERRS measurements from only femtolitres of volume and with the concentration of the reporting molecules approaching the single molecule regime.

Intermolecular vibrations and fast relaxations in supercooled ionic liquids

Short-time dynamics of ionic liquids has been investigated by low-frequency Raman spectroscopy (4 < omega < 100 cm(-1)) within the supercooled liquid range. Raman spectra are reported for ionic liquids with the same anion, bis(trifluoromethylsulfonyl)imide, and different cations: 1-butyl-3-methylimidazolium, 1-hexyl-3-methylimidazolium, 1-butyl-1-methylpiperidinium, trimethylbutylammonium, and tributylmethylammonium. It is shown that low-frequency Raman spectroscopy provides similar results as optical Kerr effect (OKE) spectroscopy, which has been used to study intermolecular vibrations in ionic liquids. The comparison of ionic liquids containing aromatic and non-aromatic cations identifies the characteristic feature in Raman spectra usually assigned to librational motion of the imidazolium ring. The strength of the fast relaxations (quasi-elastic scattering, QES) and the intermolecular vibrational contribution (boson peak) of ionic liquids with non-aromatic cations are significantly lower than imidazolium ionic liquids. A correlation length assigned to the boson peak vibrations was estimated from the frequency of the maximum of the boson peak and experimental data of sound velocity. The correlation length related to the boson peak (similar to 19 angstrom) does not change with the length of the alkyl chain in imidazolium cations, in contrast to the position of the first-sharp diffraction peak observed in neutron and X-ray scattering measurements of ionic liquids. The rate of change of the QES intensity in the supercooled liquid range is compared with data of excess entropy, free volume, and mean-squared displacement recently reported for ionic liquids. The temperature dependence of the QES intensity in ionic liquids illustrates relationships between short-time dynamics and long-time structural relaxation that have been proposed for glass-forming liquids. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3604533]

Dynamic light scattering and optical absorption spectroscopy study of pH and temperature stabilities of the extracellular hemoglobin of Glossoscolex paulistus

The extracellular hemoglobin of Glossoscolex paulistus (HbGp) is constituted of subunits containing heme groups, monomers and trimers, and nonheme structures, called linkers, and the whole protein has a minimum molecular mass near 3.1 x 10(6) Da. This and other proteins of the same family are useful model systems for developing blood substitutes due to their extracellular nature, large size, and resistance to oxidation. HbGp samples were studied by dynamic light scattering (DLS). In the pH range 6.0-8.0, HbGp is stable and has a monodisperse size distribution with a z-average hydrodynamic diameter (D-h) of 27 +/- 1 nm. A more alkaline pH induced an irreversible dissociation process, resulting in a smaller D-h of 10 +/- 1 nm. The decrease in D-h suggests a complete hemoglobin dissociation. Gel filtration chromatography was used to show unequivocally the oligomeric dissociation observed at alkaline pH. At pH 9.0, the dissociation kinetics is slow, taking a minimum of 24 h to be completed. Dissociation rate constants progressively increase at higher pH, becoming, at pH 10.5, not detectable by DILS. Protein temperature stability was also pH-dependent. Melting curves for HbGp showed oligomeric dissociation and protein denaturation as a function of pH. Dissociation temperatures were lower at higher pH. Kinetic studies were also performed using ultraviolet-visible absorption at the Soret band. Optical absorption monitors the hemoglobin autoxidation while DLS gives information regarding particle size changes in the process of protein dissociation. Absorption was analyzed at different pH values in the range 9.0-9.8 and at two temperatures, 25 degrees C and 38 degrees C. At 25 degrees C, for pH 9.0 and 9.3, the kinetics monitored by ultraviolet-visible absorption presents a monoexponential behavior, whereas for pH 9.6 and 9.8, a biexponential behavior was observed, consistent with heme heterogeneity at more alkaline pH. The kinetics at 38 degrees C is faster than that at 25 degrees C and is biexponential in the whole pH range. DLS dissociation rates are faster than the autoxidation dissociation rates at 25 degrees C. Autoxiclation and dissociation processes are intimately related, so that oligomeric protein dissociation promotes the increase of autoxidation rate and vice versa. The effect of dissociation is to change the kinetic character of the autoxidation of hemes from monoexponential to biexponential, whereas the reverse change is not as effective. This work shows that DLS can be used to follow, quantitatively and in real time, the kinetics of changes in the oligomerization of biologic complex supramolecular systems. Such information is relevant for the development of mimetic systems to be used as blood substitutes.

Near infrared spectroscopy for soil bulk density assessment

P>Soil bulk density values are needed to convert organic carbon content to mass of organic carbon per unit area. However, field sampling and measurement of soil bulk density are labour-intensive, costly and tedious. Near-infrared reflectance spectroscopy (NIRS) is a physically non-destructive, rapid, reproducible and low-cost method that characterizes materials according to their reflectance in the near-infrared spectral region. The aim of this paper was to investigate the ability of NIRS to predict soil bulk density and to compare its performance with published pedotransfer functions. The study was carried out on a dataset of 1184 soil samples originating from a reforestation area in the Brazilian Amazon basin, and conventional soil bulk density values were obtained with metallic ""core cylinders"". The results indicate that the modified partial least squares regression used on spectral data is an alternative method for soil bulk density predictions to the published pedotransfer functions tested in this study. The NIRS method presented the closest-to-zero accuracy error (-0.002 g cm-3) and the lowest prediction error (0.13 g cm-3) and the coefficient of variation of the validation sets ranged from 8.1 to 8.9% of the mean reference values. Nevertheless, further research is required to assess the limits and specificities of the NIRS method, but it may have advantages for soil bulk density predictions, especially in environments such as the Amazon forest.

Direct Solid-Phase Optical Measurements in Flow Systems: A Review

Measurements based on absorption, reflectance, or luminescence of molecular species or complex ions can be carried out directly on a solid support simultaneously to the retention of the analyte. The use of this strategy in flow-based systems is advantageous in view of the reproducible handling of solutions in retention and elution steps of the analyte. This approach can be exploited to increase sensitivity, minimize reagent consumption as well as waste generation, improve selectivity or for simultaneous determination based on selective retention or differences in sorption rates of the analytes. This review focuses on the main characteristics of direct solid-phase measurements in flow systems, including the discussion of advantages and limitations and practical guidelines to the successful implementation of this approach. Selected applications in diverse fields, such as pharmaceutical, food, and environmental analysis are discussed.

Characterizing suspended sediments from the Piracicaba River Basin by means of k(0)-INAA

The inorganic chemical characterization of suspended sediments is of utmost relevance for the knowledge of the dynamics and movement of chemical elements in the aquatic and wet ecosystems. Despite the complexity of the effective design for studying this ecological compartment, this work has tested a procedure for analyzing suspended sediments by instrumental neutron activation analysis, k(0) method (k(0)-INAA). The chemical elements As, Ba, Br, Ca, Ce, Co, Cr, Cs, Eu, Fe, Hf, Fig, K, La, Mo, Na, Ni, Rb, Sb, Sc, Se, Sm, Sr, Ta, Tb, Th, Yb and Zn were quantified in the suspended sediment compartment by means of k(0)-INAA. When compared with World Average for rivers, high mass fractions of Fe (222,900 mg/kg), Ba (4990 mg/kg), Zn (1350 mg/kg), Cr (646 mg/kg), Co (74.5 mg/kg), Br (113 mg/kg) and Mo (31.9 mg/kg) were quantified in suspended sediments from the Piracicaba River, the Piracicamirim Stream and the Marins Stream. Results of the principal component analysis for standardized chemical element mass fractions indicated an intricate correlation among chemical elements evaluated, as a response of the contribution of natural and anthropogenic sources of chemical elements for ecosystems. (C) 2010 Elsevier B.V. All rights reserved.