Molecular Ordering of Layer-by-Layer Polyelectrolyte Films Studied by Sum-Frequency Vibrational Spectroscopy

The molecular arrangement in organic thin films is crucial for their increasing technological applications. Here, we use vibrational spectroscopy by sum-frequency generation (SFG) to study the ordering of polyelectrolyte layers adsorbed on silica for all steps of layer-by-layer (LbL) self-assembly. In situ measurements during adsorption and rinsing showed that the adsorbed polymer has a disordered conformation and confirmed surface charge overcompensation upon polyelectrolyte adsorption by probing the interfacial electric field. In dry films, the polymer chains acquired a net orientational ordering, which was affected, however, by the adsorption of subsequent layers. Such a detailed characterization may allow the control of LbL film structure and functionality with unprecedented power.

Solution behavior and surface properties of carboxymethylcellulose acetate butyrate

Solution behavior of carboxymethylcellulose acetate butyrate (CMCAB) in acetone and ethyl acetate has been investigated by small-angle X-ray scattering (SAXS) and capillary viscometry and correlated with the characteristics of CMCAB films. Viscosity and SAXS measurements showed that ethyl acetate is a better solvent than acetone for CMCAB. Thin films of CMCAB were deposited onto silicon wafers (Si/SiO(2)) by spin coating. AFM images revealed that CMCAB spin coated films from solutions prepared in ethyl acetate were homogeneous and flat. However, films obtained from solutions in acetone were very rough. Contact angle measurements with polar and apolar test liquids characterized CMCAB surfaces as hydrophobic and allowed estimating the surface energy of CMCAB. Sum frequency generation vibrational spectroscopy was used to understand the role played by solvents and to gain insight about molecular orientation at Si/SiO(2)/CMCAB interface.

Cholesterol Mediates Chitosan Activity on Phospholipid Monolayers and Langmuir-Blodgett Films

The polysaccharide chitosan has been largely used in many biological applications as a fat and cholesterol reducer, bactericide agent, and wound healing material. While the efficacy for some of such uses is proven, little is known about the molecular-level interactions involved in these applications. In this study, we employ mixed Langmuir and Langmuir-Blodgett (LB) films of negatively charged dimyristoyl phosphatidic acid (DMPA) anti cholesterol as cell membrane models to investigate the role of cholesterol in the molecular-level action of chitosan. Chitosan does not remove cholesterol froth the monolayer. The interaction with chitosan tends to expand the DMPA monolayer due to its interpenetration within the film. On the other hand, cholesterol induces condensation of the DMPA monolayer. The competing effects cause the surface pressure isotherms of mixed DMPA-cholesterol films on a chitosan subphase to be unaffected by the cholesterol mole fraction, due to distinct degrees of chitosan penetration into the film in the presence of cholesterol. By combining polarization-modulated infrared reflection absorption spectroscopy (PM-IRRAS) and sum-frequency generation spectroscopy (SFG), we showed that chitosan induces order into negatively charged phospholipid layers, whereas the opposite occurs for cholesterol. In conclusion, chitosan has its penetration in the film modulated by cholesterol, and electrostatic interactions with negatively charged phospholipids, such as DMPA, are crucial for the action of chitosan.

Stability and interface properties of thin cellulose ester films adsorbed from acetone and ethyl acetate solutions

Stability and interface properties of cellulose acetate propionate (CAP) and cellulose acetate butyrate (CAB) films adsorbed from acetone or ethyl acetate onto Si wafers have been investigated by means of contact angle measurements and atomic force microscopy (AFM). Surface energy (gamma(total)(S)) values determined for CAP adsorbed from acetone are larger than those from ethyl acetate. In the case of CAB films adsorbed from ethyl acetate and acetone were similar. Dewetting was observed by AFM only for CAP films prepared from ethyl acetate. Positive values of effective Hamaker constant (A(eff)) were found only for CAP prepared from ethyl acetate, corroborating with dewetting phenomena observed by AFM. Oil the contrary, negative values of A(eff) were determined for CAP and CAB prepared from acetone and for CAB prepared from ethyl acetate, Corroborating with experimental observations. Sum frequency generation (SFG) vibrational spectra indicated that CAP and CAB films prepared from ethyl acetate present more alkyl groups oriented perpendicularly to the polymer-air interface than those films prepared from acetone. Such preferential orientation corroborates with macroscopic contact angle measurements. Moreover, SFG spectra showed that acetone hinds strongly to Si wafers, creating a new surface for CAP and CAB films. (C) 2008 Elsevier Inc. All rights reserved.

A Prospective Follow-up Study of 44 Mandibular Immediately Loaded Implants Using Resonance Frequency Analysis: Preliminary 1-Year Results

Purpose: This clinical study aimed to evaluate initial, 4-months, and 1-year stability of immediately loaded dental implants inserted according to a protocol of lower rehabilitation with prefabricated bars. Materials and Methods: The sample was composed of 11 edentulous patients. In each patient, 4 interforaminal implants were inserted. Immediately after implant installation, resonance frequency analysis (RFA) for each fixation was registered as well as after 4 months and 1 year with the prosthetic bar removed as it is a screwed system. Results: The clinical implant survival rate was 100%. The RFA showed an increase in stability after 4 months from 64.09 +/- 648 to 64.31 +/- 4.96 and I year, 67.11 +/- 4.37. The analysis of variance showed a statistically significant result (P = 0.015) among implant stability quotient values for the different periods evaluated. Tukey test results showed statistically significant differences between 1-year results and the initial periods but there was no statistically significant difference between initial and 4-month results (P > 0.05). Conclusion: These preliminary 1-year results indicate that immediate loading of mandibular dental implants using the studied prefabricated bars protocol is a reliable treatment as it is in accordance with the results described in the literature for other similar techniques. (Implant Dent 2009; 18:530-538)

Performance of the Quantitative Food Frequency Questionnaire Used in the Brazilian Center of the Prospective Study Natural History of Human Papillomavirus Infection in Men: The HIM Study

The Natural History of Human Papillomavirus (HPV) Infection in Men: The HIM Study is a prospective multi-center cohort study that, among other factors, analyzes participants` diet. A parallel cross-sectional study was designed to evaluate the validity and reproducibility of the quantitative food frequency questionnaire (QFFQ) used in the Brazilian center from the HIM Study. For this, a convenience subsample of 98 men aged 18 to 70 years from the HIM Study in Brazil answered three 54-item QFFQ and three 24-hour recall interviews, with 6-month intervals between them (data collection January to September 2007). A Bland-Altman analysis indicated that the difference between instruments was dependent on the magnitude of the intake for energy and most nutrients included in the validity analysis, with the exception of carbohydrates, fiber, polyunsaturated fat, vitamin C, and vitamin E. The correlation between the QFFQ and the 24-hour recall for the deattenuated and energy-adjusted data ranged from 0.05 (total fat) to 0.57 (calcium). For the energy and nutrients consumption included in the validity analysis, 33.5% of participants on average were correctly classified into quartiles, and the average value of 0.26 for weighted kappa shows a reasonable agreement. The intraclass correlation coefficients for all nutrients were greater than 0.40 in the reproducibility analysis. The QFFQ demonstrated good reproducibility and acceptable validity. The results support the use of this instrument in the HIM Study. J Am Diet Assoc. 2011;111:1045-1051.

Validation of a food frequency questionnaire for women with osteoporosis

The importance of nutrient intakes in osteoporosis prevention in treatment is widely recognized. The objective of the present study was to develop and validate a FFQ for women with osteoporosis. The questionnaire was composed of 60 items, separated into 10 groups. The relative validation was accomplished through comparison of the 3-Day Food Record (3DR) with the FFQ. The 3DR was applied to 30 elderly women with confirmed osteoporosis, and after 45 days the FFQ was administrated. Statistical analysis comprised the Kolmogorov-Smirnov, Student T test and Pearson correlation coefficient. The agreement between two methods was evaluated by the frequency of similar classification into quartiles, and by the Bland-Altman method. No significant differences between methods were observed for the mean evaluated nutrients, except for carbohydrate and magnesium. Pearson correlation coefficients were positive and statistically significant for all nutrients. The overall proportion of subjects classified in the same quartile by the two methods was on average 50.01% and in the opposite quartile 0.47%. For calcium intake, only 3% of subjects were classified in opposite extreme quartiles by the two methods. The Bland-Altman analysis demonstrated that the differences obtained by the two methods in each subject were well distributed around the mean of the difference, and the disagreement increases as the mean intake increases. These results indicates that the FFQ for elderly women with osteoporosis presented here is highly acceptable and is an accurate method that can be used in large-scale or clinical studies for evaluation of nutrient intakes in a similar population.

Araucaria forest dynamics in relation to fire frequency in southern Brazil based on fossil and modern pollen dataf

To elucidate the relationship between forest dynamics and fire frequency pollen percentages and charcoal amounts from a 120 cm long peat core and from samples of modern pollen rain were collected along a transect. The study site in southern Brazil is characterized by a species-rich mosaic of grassland-Araucaria forest. It is of crucial importance for management strategies for conservation to understand the development and maintenance of these vegetation mosaics including their sharp forest-grassland boundaries. During the late Holocene, considerable changes occurred in the area. From Anno Domini (AD) 1360 to 1410, the area was dominated by Campos (grassland) vegetation and fire was very common. From AD 1410 to 1500, Araucaria forest expanded and fire was less frequent. From AD 1500 to 1580, Campos grassland spread and the Araucaria forest ceased its development, apparently due to the increase of fire. From AD 1580 to 1935, after a decrease in fire frequency, Araucaria forest expanded again. From AD 1935 to the present, the Araucaria forest expanded while the Campos area decreased. Fire was very rare in this period. The results indicate a strong interaction of forest expansion, forming a mosaic of Campos and Araucaria forest, and the frequency of fire during the past 600 years. A possible collapse of the indigenous population following the post-Colombian colonization in southern Brazil after about AD 1550 may have caused a great reduction of fire frequency. The introduction of cattle (probably after AD 1780) and the resulting decrease of fire frequency might be the reason for forest expansion. Fire is probably the most important factor controlling the dynamics of the forest-grassland mosaics and the formation of sharp borders between these two vegetation types. (C) 2010 Elsevier B.V. All rights reserved.

Glucose metabolism by lymphocytes, macrophages, and tumor cells from Walker 256 tumor-bearing rats supplemented with fish oil for one generation

Here we investigated the effect of lifelong supplementation of the diet with coconut fat (CO, rich in saturated fatty acids) or fish oil (170, rich in n-3 polyunsaturated fatty acids) on tumor growth and lactate production from glucose in Walker 256 tumor cells, peritoneal macrophages, spleen, and gut-associated lymphocytes. Female Wistar rats were supplemented with CO or FO prior to mating and then throughout pregnancy and gestation and then the male offspring were supplemented from weaning until 90 days of age. Then they were inoculated subcutaneously with Walker 256 tumor cells. Tumor weight at 14 days in control rats (those fed standard chow) and CO supplemented was approximately 30 g. Supplementation of the diet with FO significantly reduced tumor growth by 76%. Lactate production (nmol h(-1) mg(-1) protein) from glucose by Walker 256 cells in the group fed regular chow (W) was 381.8 +/- 14.9. Supplementation with coconut fat (WCO) caused a significant reduction in lactate production by 1.6-fold and with fish oil (WFO) by 3.8-fold. Spleen lymphocytes obtained from W and WCO groups had markedly increased lactate production (553 +/- 70 and 635 +/- 150) when compared to non-tumor-bearing rats (similar to 260 +/- 30). FO supplementation reduced significantly the lactate production (297 +/- 50). Gut-associated lymphocytes obtained from W and WCO groups increased lactate production markedly (280 +/- 31 and 276 +/- 25) when compared to non-tumor-bearing rats (similar to 90 +/- 18). FO supplementation reduced significantly the lactate production (168 +/- 14). Lactate production by peritoneal macrophages was increased by tumor burden but there was no difference between the groups fed the various diets. Lifelong consumption of FO protects against tumor growth and modifies glucose metabolism in Walker tumor cells and lymphocytes but not in macrophages. Copyright (C) 2008 John Wiley & Sons, Ltd.

Generation of nonground-state condensates and adiabatic paradox

The problem of resonant generation of nonground-state condensates is addressed aiming at resolving the seeming paradox that arises when one resorts to the adiabatic representation. In this picture, the eigenvalues and eigenfunctions of a time-dependent Gross-Pitaevskii Hamiltonian are also functions of time. Since the level energies vary in time, no definite transition frequency can be introduced. Hence no external modulation with a fixed frequency can be made resonant. Thus, the resonant generation of adiabatic coherent modes is impossible. However, this paradox occurs only in the frame of the adiabatic picture. It is shown that no paradox exists in the properly formulated diabatic representation. The resonant generation of diabatic coherent modes is a well defined phenomenon. As an example, the equations are derived, describing the generation of diabatic coherent modes by the combined resonant modulation of the trapping potential and atomic scattering length.

Molecular Ordering in Layer-by-Layer Polyelectrolyte Films Studied by Sum-Frequency Vibrational Spectroscopy: The Effects of Drying Procedures

Sum-Frequency Vibrational Spectroscopy (SFVS) has been used to investigate the effect of nitrogen-flow drying on the molecular ordering of Layer-by-Layer (LbL) films of poly(allylamine hydrochloride) (PAH) alternated with poly(styrene sulfonate) (PSS). We find that films dried by spontaneous water evaporation are more ordered and homogeneous than films dried by nitrogen flow. The latter are quite inhomogeneous and may have regions with highly disordered polymer conformation. We propose that drying by spontaneous water evaporation reduces the effect of drag by the drying front, while during nitrogen-flow drying the fast evaporation of water ""freezes"" the disordered conformation of adsorbed polyelectrolyte molecules. These findings are important for many applications of LbL films, since device performance usually depends on film morphology and its molecular structure.