The effects of the specific adsorption of anion on the reactivity of the Ru(0001) surface towards CO adsorption and oxidation: in situ FTIRS studies

The dynamics of adsorption and oxidation of CO on Ru(0001) electrode in sulfuric acid solution have been studied using in situ FTIR spectroscopy under potential control and at open circuit, the latter at 20 and 55 degrees C. The in situ IR data show clearly that the bisulfate anion adsorbs on the Ru(0001) surface over the potential range from -200 mV to 350 mV (vs. Ag/AgCl) at 20 degrees C in the absence and presence of adsorbed CO; however, increasing the temperature to 55 degrees C and/ or increasing the concentration of dissolved O-2 reduces the bisulfate adsorption. The formation of surface (hydro-) oxide at higher potentials replaces the bisulfate adsorbates. Both linear (COL) and three-fold hollow bonded CO (COH) adsorbates were produced following CO adsorption at Ru(0001) in H2SO4, as was observed in our previous studies in HClO4. However, the amount of adsorbed CO observed in H2SO4 was ca. 10% less than that in HClO4; in addition, the COL and COH frequencies were higher in H2SO4, and the onset potential for COads oxidation 25 mV lower. These new results are interpreted in terms of a model in which the adsorbed bisulfate weakens the CO adlayer, allowing the active Ru oxide layer to form at lower potentials. Significantly different results were observed at open circuit in H2SO4 compared both to the data under potential control and to our earlier data in HClO4, and these observations were rationalized in terms of the adsorbed HSO4- anions (pre-adsorbed at -200 mV) inhibiting the oxidation of the surface at open circuit (after stepping from the initial potential of -200 mV), as the latter was no longer driven by the imposed electrochemical potential but via chemical oxidation by trace dissolved O-2. Results from experiments at open circuit at 55 degrees C and using oxygen-saturated H2SO4 supported this model. The difference in Ru surface chemistry between imposed electrochemical control and chemical control has potential implications with respect to fuel cell electrocatalysis.

Interaction of water, hydrogen and their mixtures with SnO2 based materials: the role of surface hydroxyl groups in detection mechanisms

DRIFTS, TGA and resistance measurements have been used to study the mechanism of water and hydrogen interaction accompanied by a resistance change (sensor signal) of blank and Pd doped SnO2. It was found that a highly hydroxylated surface of blank SnO2 reacts with gases through bridging hydroxyl groups, whereas the Pd doped materials interact with hydrogen and water through bridging oxygen. In the case of blank SnO2 the sensor signal maximum towards H-2 in dry air (R-0/R-g) is observed at similar to 345 degrees C, and towards water, at similar to 180 degrees C, which results in high selectivity to hydrogen in the presence of water vapors (minor humidity effect). In contrast, on doping with Pd the response to hydrogen in dry air and to water occurred in the same temperature region (ca. 140 degrees C) leading to low selectivity with a high effect of humidity. An increase in water concentration in the gas phase changes the hydrogen interaction mechanism of Pd doped materials, while that of blank SnO2 is unchanged. The interaction of hydrogen with the catalyst doped SnO2 occurs predominantly through hydroxyl groups when the volumetric concentration of water in the gas phase is higher than that of H-2 by a factor of 1000.

Rapid Surface Plasmon Resonance Immunoassay for the Determination of Deoxynivalenol in Wheat, Wheat Products, and Maize-Based Baby Food

A rapid screening assay (9 min/sample) has been developed and validated for the detection of deoxynivalenol in durum wheat, wheat products, and maize-based baby foods using an SPA biosensor. Through a single laboratory validation, the limits of detection (LOD) for wheat, wheat-based breakfast cereal, and maize-based baby food were 57, 9, and 6 mu g/kg, respectively. Intra-assay and interassay precisions were calculated for each matrix at the maximum and half-maximum European Union regulatory limits and expressed as the coefficient of variation (CV). All CVs fell below 10% with the exception of the between-run CV for breakfast cereal. Recoveries at the concentrations tested ranged from 92 to 115% for all matrices. Action limits of 161, 348, and 1378 mu g/kg were calculated for baby food, wheat-based breakfast cereal, and wheat, respectively, and the linear range of the assay was determined as 250-2000 mu g/kg.

Surface-Enhanced Raman Evidence of Protonation, Reorientation, and Ag+ Complexation of Deoxyadenosine and Deoxyadenosine-5 '-Monophosphate (dAMP) on Ag and Au Surfaces

Surface-enhanced Raman (SERS) spectra of deoxyadenosine and 5'-dAMP on Ag and Au surfaces showed the protonation of both compounds in the N1 position, their orientation geometry on metal surfaces, and the formation of Ag+ complexes at alkaline pH on hydroxylamine-reduced Ag colloids. Interestingly, substitution at the N9 position caused dramatic changes in the relative band intensities within the spectra of both deoxyadenosine and 5'-dAMP compared to that of simple adenine, although they continued to be dominated by adenine vibrations. Concentration-dependent spectra of 5'-dAMP were observed, which matched that of adenine at high concentrations and that of deoxyadenosine at lower concentration (

Time-Resolved DRIFTS, MS, and Resistance Study of SnO2 Materials: The Role of Surface Hydroxyl Groups in Formation of Donor States

Time-resolved DRIFTS, MS, and resistance measurements were used to study the interaction of undoped and Pd-doped SnO2 with H-2 in air and argon at 300 degrees C. Using first-order kinetics, we compare the time constants for the resistance drop and its partial recovery with those of the surface hydroxyl evolution and water formation in the gas phase upon exposure to hydrogen. In the case of the undoped oxide, resistance and bridging hydroxyls (BOHs) evolve similarly, manifesting a fast main drop followed by recovery at a similar rate. The rate of water formation for this material was found to be much slower than that of the main drop in both the resistance and BOHs. In contrast, the resistance change for SnO2-Pd appeared to be similar to that of water formation, and no correlation was found between the evolution of resistance and surface OHs. Isotopic exchange on both materials revealed that water formation occurs via fast and slow hydrogen transfer to surface oxygen species. While the former originates from just-adsorbed hydrogen, the latter appears to proceed from the preadsorbed OHs. Both surfaces exhibit close interaction between chemisorbed oxygen and existing bridging OH groups, indicating that the latter is an intermediate in the hydrogen oxidation and generation of donor states on the surface.

Analysis of Biological Interactions and Recognitions by Surface Plasmon Resonance

This chapter contains sections titled:

•Introduction to Surface Plasmon Resonance Technology

•Working Principle of SPR

•Sensor Surface Chemistry and Its Fabrications

•Important Factors Impacting on the Performance of SPR-Based Analyses of Biological Interactions on the Nonbiological Transducer Surface

•Localized SPR of Inorganic Nanoparticles for Analyses of Biological Interaction

•References

Preaggregated Ag Nanoparticles in Dry Swellable Gel Films for Off-the-Shelf Surface-Enhanced Raman Spectroscopy

Large, thin (50 mu m) dry polymer sheets containing numerous surface-enhanced Raman spectroscopy (SERS) active Ag nanopartide aggregates have been prepared by drying aqueous mixtures of hydroxyethylcelloulose (HEC) and preaggregated Ag colloid in 10 x 10 cm molds. In these dry films, the particle aggregates are protected from the environment during storage and are easy to handle; for example, they can be cut to size with scissors. When in use, the highly swellable HEC polymer allowed the films to rapidly absorb aqueous analyte solutions while simultaneously releasing the Ag nanoparticle aggregates to interact with the analyte and generate large SERS signals. Either the films could be immersed in the analyte solution or 5 mu L droplets were applied to the surface; in the latter method, the local swelling caused the active area to dome upward, but the swollen film remained physically robust and could be handled as required. Importantly, encapsulation and release did not significantly compromise the SERS performance of the colloid; the signals given by the swollen films were similar to the very high signals obtained from the parent citrate-reduced colloid and were an order of magnitude larger than a commercially available nanoparticle substrate. These "Poly-SERS" films retained 70% of their SERS activity after being stored for 1 year in air. The films were sufficiently homogeneous to give a standard deviation of 3.2% in the absolute signal levels obtained from a test analyte, primarily due to the films' ability to suppress "coffee ring" drying marks, which meant that quantitative analysis without an internal standard was possible. The majority of the work used aqueous thiophenol as the test analyte; however, preliminary studies showed that the Poly-SERS films could also be used with nonaqueous solvents and for a range of other analytes including theophylline, a therapeutic drug, at a concentration as low as 1.0 x 10(-5) mol dm(-3) (1.8 mg/dm(3)), well below the sensitivity required for theophylline monitoring where the target range is 10-20 mg/dm(3).

Air pollutant contamination and acidification of surface waters in the North York Moors, UK: Multi-proxy evidence from the sediments of a moorland pool

Despite the extensive geographical range of palaeolimnological studies designed to assess the extent of surface water acidification in the United Kingdom during the 1980s, little attention was paid to the status of surface waters in the North York Moors (NYM). In this paper, we present sediment core data from a moorland pool in the NYM that provide a record of air pollution contamination and surface water acidification. The 41-cm-long core was divided into three lithostratigraphic units. The lower two comprise peaty soils and peats, respectively, that date to between approximately 8080 and 6740 cal. BP. The uppermost unit comprises peaty lake muds dating from between approximately ad 1790 and the present day (ad 2006). The lower two units contain pollen dominated by forest taxa, whereas the uppermost unit contains pollen indicative of open landscape conditions similar to those of the present. Heavy metal, spheroidal carbonaceous particle, mineral magnetics and stable isotope analysis of the upper sediments show clear evidence of contamination by air pollutants derived from fossil-fuel combustion over the last c. 150years, and diatom analysis indicates that the naturally acidic pool became more acidic during the 20th century. We conclude that the exceptionally acidic surface waters of the pool at present (pH=c. 4.1) are the result of a long history of air pollution and not because of naturally acidic local conditions. We argue that the highly acidic surface waters elsewhere in the NYM are similarly acidified and that the lack of evidence of significant recovery from acidification, despite major reductions in the emissions of acidic gases that have taken place over the last c. 30years, indicates the continuing influence of pollutant sulphur stored in catchment peats, a legacy of over 150years of acid deposition.

Surface electron properties and catalytic activity of cerium-zirconium mixed oxides

The electron donating properties, surface acidity/ basicity and catalytic activity of cerium - zirconium mixed oxides at various compositions have been reported at an activation temperature of 500 degree C. The catalytic activity for the esterification of acetic acid with n-butanol has heen correlated with electron donating properties and surface acidity/basicity of the oxides.

Ground- and excited-state properties of M-center oxygen vacancy aggregates in the bulk and the surface of MgO

Aggregates of oxygen vacancies (F centers) represent a particular form of point defects in ionic crystals. In this study we have considered the combination of two oxygen vacancies, the M center, in the bulk and on the surface of MgO by means of cluster model calculations. Both neutral and charged forms of the defect M and M+ have been taken into account. The ground state of the M center is characterized by the presence of two doubly occupied impurity levels in the gap of the material; in M+ centers the highest level is singly occupied. For the ground-state properties we used a gradient corrected density functional theory approach. The dipole-allowed singlet-to-singlet and doublet-to-doublet electronic transitions have been determined by means of explicitly correlated multireference second-order perturbation theory calculations. These have been compared with optical transitions determined with the time-dependent density functional theory formalism. The results show that bulk M and M+ centers give rise to intense absorptions at about 4.4 and 4.0 eV, respectively. Another less intense transition at 1.3 eV has also been found for the M+ center. On the surface the transitions occur at 1.6 eV (M+) and 2 eV (M). The results are compared with recently reported electron energy loss spectroscopy spectra on MgO thin films.

Surface structure and stability of PdZn and PtZn alloys: Density-functional slab model studies

Geometric parameters of binary (1:1) PdZn and PtZn alloys with CuAu-L10 structure were calculated with a density functional method. Based on the total energies, the alloys are predicted to feature equal formation energies. Calculated surface energies of PdZn and PtZn alloys show that (111) and (100) surfaces exposing stoichiometric layers are more stable than (001) and (110) surfaces comprising alternating Pd (Pt) and Zn layers. The surface energy values of alloys lie between the surface energies of the individual components, but they differ from their composition weighted averages. Compared with the pure metals, the valence d-band widths and the Pd or Pt partial densities of states at the Fermi level are dramatically reduced in PdZn and PtZn alloys. The local valence d-band density of states of Pd and Pt in the alloys resemble that of metallic Cu, suggesting that a similar catalytic performance of these systems can be related to this similarity in the local electronic structures.

Charge transfer in Cr adsorption and reaction at the rutile TiO2(110) surface

The rutile TiO2(110) surface has been doped with sub-monolayer metallic Cr, which oxidises and donates charge to specific surface Ti ions. X-Ray and ultra violet photoemission spectroscopy and first principles density functional theory with Hubbard U are used to assign the oxidation states of Cr and surface Ti and we find that Cr2+ forms on bridging oxygen ions and a 5-fold coordinated surface Ti atom is reduced to Ti3+ and the Cr ions readily react with oxygen (to Cr3+), which leads to depletion of surface Ti3+ 3d electrons.

Report of the 2010 assessment of the scientific assessment panel: future ozone and its impact on surface UV

SCIENTIFIC SUMMARY Globally averaged total column ozone has declined over recent decades due to the release of ozone-depleting substances (ODSs) into the atmosphere. Now, as a result of the Montreal Protocol, ozone is expected to recover from the effects of ODSs as ODS abundances decline in the coming decades. However, a number of factors in addition to ODSs have led to and will continue to lead to changes in ozone. Discriminating between the causes of past and projected ozone changes is necessary, not only to identify the progress in ozone recovery from ODSs, but also to evaluate the effectiveness of climate and ozone protection policy options. Factors Affecting Future Ozone and Surface Ultraviolet Radiation • At least for the next few decades, the decline of ODSs is expected to be the major factor affecting the anticipated increase in global total column ozone. However, several factors other than ODS will affect the future evolution of ozone in the stratosphere. These include changes in (i) stratospheric circulation and temperature due to changes in long-lived greenhouse gas (GHG) abundances, (ii) stratospheric aerosol loading, and (iii) source gases of highly reactive stratospheric hydrogen and nitrogen compounds. Factors that amplify the effects of ODSs on ozone (e.g., stratospheric aerosols) will likely decline in importance as ODSs are gradually eliminated from the atmosphere. • Increases in GHG emissions can both positively and negatively affect ozone. Carbon dioxide (CO2)-induced stratospheric cooling elevates middle and upper stratospheric ozone and decreases the time taken for ozone to return to 1980 levels, while projected GHG-induced increases in tropical upwelling decrease ozone in the tropical lower stratosphere and increase ozone in the extratropics. Increases in nitrous oxide (N2O) and methane (CH4) concentrations also directly impact ozone chemistry but the effects are different in different regions. • The Brewer-Dobson circulation (BDC) is projected to strengthen over the 21st century and thereby affect ozone amounts. Climate models consistently predict an acceleration of the BDC or, more specifically, of the upwelling mass flux in the tropical lower stratosphere of around 2% per decade as a consequence of GHG abundance increases. A stronger BDC would decrease the abundance of tropical lower stratospheric ozone, increase poleward transport of ozone, and could reduce the atmospheric lifetimes of long-lived ODSs and other trace gases. While simulations showing faster ascent in the tropical lower stratosphere to date are a robust feature of chemistry-climate models (CCMs), this has not been confirmed by observations and the responsible mechanisms remain unclear. • Substantial ozone losses could occur if stratospheric aerosol loading were to increase in the next few decades, while halogen levels are high. Stratospheric aerosol increases may be caused by sulfur contained in volcanic plumes entering the stratosphere or from human activities. The latter might include attempts to geoengineer the climate system by enhancing the stratospheric aerosol layer. The ozone losses mostly result from enhanced heterogeneous chemistry on stratospheric aerosols. Enhanced aerosol heating within the stratosphere also leads to changes in temperature and circulation that affect ozone. • Surface ultraviolet (UV) levels will not be affected solely by ozone changes but also by the effects of climate change and by air quality change in the troposphere. These tropospheric effects include changes in clouds, tropospheric aerosols, surface reflectivity, and tropospheric sulfur dioxide (SO2) and nitrogen dioxide (NO2). The uncertainties in projections of these factors are large. Projected increases in tropospheric ozone are more certain and may lead to reductions in surface erythemal (“sunburning”) irradiance of up to 10% by 2100. Changes in clouds may lead to decreases or increases in surface erythemal irradiance of up to 15% depending on latitude. Expected Future Changes in Ozone Full ozone recovery from the effects of ODSs and return of ozone to historical levels are not synonymous. In this chapter a key target date is chosen to be 1980, in part to retain the connection to previous Ozone Assessments. Noting, however, that decreases in ozone may have occurred in some regions of the atmosphere prior to 1980, 1960 return dates are also reported. The projections reported on in this chapter are taken from a recent compilation of CCM simulations. The ozone projections, which also form the basis for the UV projections, are limited in their representativeness of possible futures since they mostly come from CCM simulations based on a single GHG emissions scenario (scenario A1B of Emissions Scenarios. A Special Report of Working Group III of the Intergovernmental Panel on Climate Change, Cambridge University Press, 2000) and a single ODS emissions scenario (adjusted A1 of the previous (2006) Ozone Assessment). Throughout this century, the vertical, latitudinal, and seasonal structure of the ozone distribution will be different from what it was in 1980. For this reason, ozone changes in different regions of the atmosphere are considered separately. • The projections of changes in ozone and surface clear-sky UV are broadly consistent with those reported on in the 2006 Assessment. • The capability of making projections and attribution of future ozone changes has been improved since the 2006 Assessment. Use of CCM simulations from an increased number of models extending through the entire period of ozone depletion and recovery from ODSs (1960–2100) as well as sensitivity simulations have allowed more robust projections of long-term changes in the stratosphere and of the relative contributions of ODSs and GHGs to those changes. • Global annually averaged total column ozone is projected to return to 1980 levels before the middle of the century and earlier than when stratospheric halogen loading returns to 1980 levels. CCM projections suggest that this early return is primarily a result of GHG-induced cooling of the upper stratosphere because the effects of circulation changes on tropical and extratropical ozone largely cancel. Global (90°S–90°N) annually averaged total column ozone will likely return to 1980 levels between 2025 and 2040, well before the return of stratospheric halogens to 1980 levels between 2045 and 2060. • Simulated changes in tropical total column ozone from 1960 to 2100 are generally small. The evolution of tropical total column ozone in models depends on the balance between upper stratospheric increases and lower stratospheric decreases. The upper stratospheric increases result from declining ODSs and a slowing of ozone destruction resulting from GHG-induced cooling. Ozone decreases in the lower stratosphere mainly result from an increase in tropical upwelling. From 1960 until around 2000, a general decline is simulated, followed by a gradual increase to values typical of 1980 by midcentury. Thereafter, although total column ozone amounts decline slightly again toward the end of the century, by 2080 they are no longer expected to be affected by ODSs. Confidence in tropical ozone projections is compromised by the fact that simulated decreases in column ozone to date are not supported by observations, suggesting that significant uncertainties remain. • Midlatitude total column ozone is simulated to evolve differently in the two hemispheres. Over northern midlatitudes, annually averaged total column ozone is projected to return to 1980 values between 2015 and 2030, while for southern midlatitudes the return to 1980 values is projected to occur between 2030 and 2040. The more rapid return to 1980 values in northern midlatitudes is linked to a more pronounced strengthening of the poleward transport of ozone due to the effects of increased GHG levels, and effects of Antarctic ozone depletion on southern midlatitudes. By 2100, midlatitude total column ozone is projected to be above 1980 values in both hemispheres. • October-mean Antarctic total column ozone is projected to return to 1980 levels after midcentury, later than in any other region, and yet earlier than when stratospheric halogen loading is projected to return to 1980 levels. The slightly earlier return of ozone to 1980 levels (2045–2060) results primarily from upper stratospheric cooling and resultant increases in ozone. The return of polar halogen loading to 1980 levels (2050–2070) in CCMs is earlier than in empirical models that exclude the effects of GHG-induced changes in circulation. Our confidence in the drivers of changes in Antarctic ozone is higher than for other regions because (i) ODSs exert a strong influence on Antarctic ozone, (ii) the effects of changes in GHG abundances are comparatively small, and (iii) projections of ODS emissions are more certain than those for GHGs. Small Antarctic ozone holes (areas of ozone <220 Dobson units, DU) could persist to the end of the 21st century. • March-mean Arctic total column ozone is projected to return to 1980 levels two to three decades before polar halogen loading returns to 1980 levels, and to exceed 1980 levels thereafter. While CCM simulations project a return to 1980 levels between 2020 and 2035, most models tend not to capture observed low temperatures and thus underestimate present-day Arctic ozone loss such that it is possible that this return date is biased early. Since the strengthening of the Brewer-Dobson circulation through the 21st century leads to increases in springtime Arctic column ozone, by 2100 Arctic ozone is projected to lie well above 1960 levels. Uncertainties in Projections • Conclusions dependent on future GHG levels are less certain than those dependent on future ODS levels since ODS emissions are controlled by the Montreal Protocol. For the six GHG scenarios considered by a few CCMs, the simulated differences in stratospheric column ozone over the second half of the 21st century are largest in the northern midlatitudes and the Arctic, with maximum differences of 20–40 DU between the six scenarios in 2100. • There remain sources of uncertainty in the CCM simulations. These include the use of prescribed ODS mixing ratios instead of emission fluxes as lower boundary conditions, the range of sea surface temperatures and sea ice concentrations, missing tropospheric chemistry, model parameterizations, and model climate sensitivity. • Geoengineering schemes for mitigating climate change by continuous injections of sulfur-containing compounds into the stratosphere, if implemented, would substantially affect stratospheric ozone, particularly in polar regions. Ozone losses observed following large volcanic eruptions support this prediction. However, sporadic volcanic eruptions provide limited analogs to the effects of continuous sulfur emissions. Preliminary model simulations reveal large uncertainties in assessing the effects of continuous sulfur injections. Expected Future Changes in Surface UV. While a number of factors, in addition to ozone, affect surface UV irradiance, the focus in this chapter is on the effects of changes in stratospheric ozone on surface UV. For this reason, clear-sky surface UV irradiance is calculated from ozone projections from CCMs. • Projected increases in midlatitude ozone abundances during the 21st century, in the absence of changes in other factors, in particular clouds, tropospheric aerosols, and air pollutants, will result in decreases in surface UV irradiance. Clear-sky erythemal irradiance is projected to return to 1980 levels on average in 2025 for the northern midlatitudes, and in 2035 for the southern midlatitudes, and to fall well below 1980 values by the second half of the century. However, actual changes in surface UV will be affected by a number of factors other than ozone. • In the absence of changes in other factors, changes in tropical surface UV will be small because changes in tropical total column ozone are projected to be small. By the middle of the 21st century, the model projections suggest surface UV to be slightly higher than in the 1960s, very close to values in 1980, and slightly lower than in 2000. The projected decrease in tropical total column ozone through the latter half of the century will likely result in clear-sky surface UV remaining above 1960 levels. Average UV irradiance is already high in the tropics due to naturally occurring low total ozone columns and high solar elevations. • The magnitude of UV changes in the polar regions is larger than elsewhere because ozone changes in polar regions are larger. For the next decades, surface clear-sky UV irradiance, particularly in the Antarctic, will continue to be higher than in 1980. Future increases in ozone and decreases in clear-sky UV will occur at slower rates than those associated with the ozone decreases and UV increases that occurred before 2000. In Antarctica, surface clear-sky UV is projected to return to 1980 levels between 2040 and 2060, while in the Arctic this is projected to occur between 2020 and 2030. By 2100, October surface clear-sky erythemal irradiance in Antarctica is likely to be between 5% below to 25% above 1960 levels, with considerable uncertainty. This is consistent with multi-model-mean October Antarctic total column ozone not returning to 1960 levels by 2100. In contrast, by 2100, surface clear-sky UV in the Arctic is projected to be 0–10% below 1960 levels.

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.

Interaction of polysaccharide-protein complex from Agaricus blazei with Langmuir and Langmuir-Blodgett films of phospholipids

The use of natural substances in health applications may be hampered by the difficulties in establishing the mechanisms of action, especially at molecular-level. The protein-polysaccharide complex extracted from the mushroom Agaricus blazei Murill, referred to as CAb, has been considered for treating various diseases with probable interaction with cell membranes. In this study, we investigate the interaction between CAb and a cell membrane model represented by a Langmuir monolayer of dimyristoyl phosphatidic acid (DMPA). CAb affects the structural properties of DMPA monolayers causing expansion and increasing compressibility. In addition, interaction with DMPA polar heads led to neutralization of the electrical double layer, yielding a zero surface potential at large areas per molecule. CAb remained at the interface even at high surface pressures, which allowed transfer of Langmuir-Blodgett (LB) films onto solid supports with the CAb-DMPA mixture. The mass transferred, according to quartz crystal microbalance (QCM) measurements, increased linearly with the number of deposited layers. With UV-vis absorption, fluorescence and FTIR spectroscopies, we confirmed that the LB films contain polysaccharides, proteins and DMPA. Therefore, the CAb biological action must be attributed not only to polysaccharides but also to proteins in the complex. (C) 2008 Elsevier Inc. All rights reserved.