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.

Effect of solvent on the adsorption behavior and on the surface properties of Sterculia striata polysaccharide

Characterization of Sterculia striate polysaccharide (SSP) films adsorbed onto Si wafers from solutions prepared in ethyl methyl imidazolium acetate (EmimAc), water or NaOH 0.01 mol/L was systematically studied by means of ellipsometry, atomic force microscopy and contact angle measurements. SSP adsorbed from EmimAc onto Si wafer as homogeneous monolayers (similar to 0.5 nm thick), while from water or NaOH 0.01 mol/L SSP formed layers of similar to 4.0 nm and similar to 1.5 nm thick, respectively. Surface energy values found for SSP adsorbed from EmimAc or water were 68 +/- 2 mJ/m(2) and 65 +/- 2 mJ/m(2), respectively, whereas from NaOH it amounted to 57 +/- 3 mJ/m(2). The immobilization of lysozyme (LYS) onto SSP films was also investigated. The mean thickness of LYS (d(LYS)) immobilized onto SSP films adsorbed from each solvent tended to increase with the decrease of gamma(P)(S) and gamma(total)(S). However, the enzymatic activity of LYS molecules was higher when they were immobilized onto SSP films with higher gamma(P)(S) and gamma(total)(S) values. (C) 2010 Elsevier Ltd. All rights reserved.

Surface modification of siloxane containing polyurethane polymer by dielectric barrier discharge at atmospheric pressure

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

Treatment of PVC using an alternative low energy ion bombardment procedure

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

Effect of amino-terminated substrates onto surface properties of cellulose esters and their interaction with lectins

Films of cellulose acetate butyrate (CAB) and carboxymethylcellulose acetate butyrate (CMCAB) were deposited from ethyl acetate solutions onto bare silicon wafers (Si/SiO2) or amino-terminated surfaces (APS) by means of equilibrium adsorption. All surfaces were characterized by means of ellipsometry, atomic force microscopy (AFM) and contact angle measurements. The presence of amino groups on the support surface favored the adsorption of CAB and CMCAB, inducing the orientation almost polar groups to the surface and the exposition of alkyl group to the air. Such molecular orientation caused increase of the dispersive component of surface energy (gamma(d)(s)) and decrease of the polar component of surface energy (gamma(p)(s)) of cellulose esters in comparison to those values determined for films deposited onto bare Si/SiO2 wafers. Adsorption behavior of jacalin or concanavalin A onto CAB and CMCAB films was also investigated. The adsorbed amounts of lectins were more pronounced on cellulose esters with high (gamma(p)(s)) and total surface energy (gamma(t)(s)) values. (C) 2011 Elsevier B.V. All rights reserved.

Advanced schemes for surface plasmon resonance and plasmon-enhanced fluorescence biosensors

Advanced optical biosensor platforms exploiting long range surface plasmons (LRSPs) and responsive N-isopropylacrylamide (NIPAAm) hydrogel binding matrix for the detection of protein and bacterial pathogen analytes were carried out. LRSPs are optical waves that originate from coupling of surface plasmons on the opposite sites of a thin metallic film embedded between two dielectrics with similar refractive indices. LRSPs exhibit orders of magnitude lower damping and more extended profile of field compared to regular surface plasmons (SPs). Their excitation is accompanied with narrow resonance and provides stronger enhancement of electromagnetic field intensity that can advance the sensitivity of surface plasmon resonance (SPR) and surface plasmon-enhanced fluorescence spectroscopy (SPFS) biosensors. Firstly, we investigated thin gold layers deposited on fluoropolymer surface for the excitation of LRSPs. The study indicates that the morphological, optical and electrical properties of gold film can be changed by the surface energy of fluoropolymer and affect the performance of a SPFS biosensor. A photo-crosslinkable NIPAAm hydrogel was grafted to the sensor surface in order to serve as a binding matrix. It was modified with bio-recognition elements (BREs) via amine coupling chemistry and offered the advantage of large binding capacity, stimuli responsive properties and good biocompatibility. Through experimental observations supported by numerical simulations describing diffusion mass transfer and affinity binding of target molecules in the hydrogel, the hydrogel binding matrix thickness, concentration of BREs and the profile of the probing evanescent field was optimized. Hydrogel with a up to micrometer thickness was shown to support additional hydrogel optical waveguide (HOW) mode which was employed for probing affinity binding events in the gel by means of refractometric and fluorescence measurements. These schemes allow to reach limits of detection (LODs) at picomolar and femtomolar levels, respectively. Besides hydrogel based experiments for detection of molecular analytes, long range surface plasmon-enhanced fluorescence spectroscopy (LRSP-FS) was employed for detection of bacterial pathogens. The influence of capture efficiency of bacteria on surfaces and the profile of the probing field on sensor response were investigated. The potential of LRSP-FS with extended evanescent field is demonstrated for detection of pathogenic E. coli O157:H7 on sandwich immunoassays . LOD as low as 6 cfu mL-1 with a detection time of 40 minutes was achieved.rn

Surface cloud radiative forcing from broadband radiation measurements on the Antarctic plateau

Surface based measurements systems play a key role in defining the ground truth for climate modeling and satellite product validation. The Italian-French station of Concordia is operative year round since 2005 at Dome C (75°S, 123°E, 3230 m) on the East Antarctic Plateau. A Baseline Surface Radiation Network (BSRN) site was deployed and became operational since January 2006 to measure downwelling components of the radiation budget, and successively was expanded in April 2007 to measure upwelling radiation. Hence, almost a decade of measurement is now available and suitable to define a statistically significant climatology for the radiation budget of Concordia including eventual trends, by specifically assessing the effects of clouds and water vapor on SW and LW net radiation. A well known and robust clear sky-id algorithm (Long and Ackerman, 2000) has been operationally applied on downwelling SW components to identify cloud free events and to fit a parametric equation to determine clear-sky reference along the Antarctic daylight periods (September to April). A new model for surface broadband albedo has been developed in order to better describe the features the area. Then, a novel clear-sky LW parametrization, based on a-priori assumption about inversion layer structure, combined with daily and annual oscillations of the surface temperature, have been adopted and validated. The longwave based method is successively exploited to extend cloud radiative forcing studies to nighttime period (winter). Results indicated inter-annual and intra-annual warming behaviour, i.e. 13.70 W/m2 on the average, specifically approaching neutral effect in summer, when SW CRF compensates LW CRF, and warming along the rest of the year due prevalentely to CRF induced on the LW component.

Liquid–Vapor Interface of Formic Acid Solutions in Salt Water: A Comparison of Macroscopic Surface Tension and Microscopic in Situ X-ray Photoelectron Spectroscopy Measurements

The liquid–vapor interface is difficult to access experimentally but is of interest from a theoretical and applied point of view and has particular importance in atmospheric aerosol chemistry. Here we examine the liquid–vapor interface for mixtures of water, sodium chloride, and formic acid, an abundant chemical in the atmosphere. We compare the results of surface tension and X-ray photoelectron spectroscopy (XPS) measurements over a wide range of formic acid concentrations. Surface tension measurements provide a macroscopic characterization of solutions ranging from 0 to 3 M sodium chloride and from 0 to over 0.5 mole fraction formic acid. Sodium chloride was found to be a weak salting out agent for formic acid with surface excess depending only slightly on salt concentration. In situ XPS provides a complementary molecular level description about the liquid–vapor interface. XPS measurements over an experimental probe depth of 51 Å gave the C 1s to O 1s ratio for both total oxygen and oxygen from water. XPS also provides detailed electronic structure information that is inaccessible by surface tension. Density functional theory calculations were performed to understand the observed shift in C 1s binding energies to lower values with increasing formic acid concentration. Part of the experimental −0.2 eV shift can be assigned to the solution composition changing from predominantly monomers of formic acid to a combination of monomers and dimers; however, the lack of an appropriate reference to calibrate the absolute BE scale at high formic acid mole fraction complicates the interpretation. Our data are consistent with surface tension measurements yielding a significantly more surface sensitive measurement than XPS due to the relatively weak propensity of formic acid for the interface. A simple model allowed us to replicate the XPS results under the assumption that the surface excess was contained in the top four angstroms of solution.

Basic and other measurements of radiation from the Baseline Surface Radiation Network (BSRN) Station Ny-Ålesund in the years 1992 to 2013, reference list of 253 datasets

At Ny-Ålesund (78.9° N), Svalbard, surface radiation measurements of up- and downward short- and longwave radiation are operated since August 1992 in the frame of the Baseline Surface Radiation Network (BSRN), complemented with surface and upper air meteorology since August 1993. The long-term observations are the base for a climatological presentation of the surface radiation data. Over the 21-year observation period, ongoing changes in the Arctic climate system are reflected. Particularly, the observations indicate a strong seasonality of surface warming and related changes in different radiation parameters. The annual mean temperature at Ny-Ålesund has risen by +1.3 ± 0.7 K per decade, with a maximum seasonal increase during the winter months of +3.1 ± 2.6 K per decade. At the same time, winter is also the season with the largest long-term changes in radiation, featuring an increase of +15.6 ± 11.6 W/m**2 per decade in the downward longwave radiation. Furthermore, changes in the reflected solar radiation during the months of snow melt indicate an earlier onset of the warm season by about 1 week compared to the beginning of the observations. The online available dataset of Ny-Ålesund surface radiation measurements provides a valuable data source for the validation of satellite instruments and climate models.

Sea surface fugacity of carbon dioxide measurements in the Indian and Southern Oceans obtained during MINERVE-29/ANTARES-II cruise

The sub-Antarctic zone (SAZ) lies between the subtropical convergence (STC) and the sub-Antarctic front (SAF), and is considered one of the strongest oceanic sinks of atmospheric CO2. The strong sink results from high winds and seasonally low sea surface fugacities of CO2 (fCO2), relative to atmospheric fCO2. The region of the SAZ, and immediately south, is also subject to mode and intermediate water formation, yielding a penetration of anthropogenic CO2 below the mixed layer. A detailed analysis of continuous measurements made during the same season and year, February - March 1993, shows a coherent pattern of fCO2 distributions at the eastern (WOCE/SR3 at about 145°E) and western edges (WOCE/I6 at 30°E) of the Indian sector of the Southern Ocean. A strong CO2 sink develops in the Austral summer (delta fCO2 < - 50 µatm) in both the eastern (110°-150°E) and western regions (20°-90°E). The strong CO2 sink in summer is due to the formation of a shallow seasonal mixed-layer (about 100 m). The CO2 drawdown in the surface water is consistent with biologically mediated drawdown of carbon over summer. In austral winter, surface fCO2 is close to equilibrium with the atmosphere (delta fCO2 ± 5 µatm), and the net CO2 exchange is small compared to summer. The near-equilibrium values in winter are associated with the formation of deep winter mixed-layers (up to 700 m). For years 1992-95, the annual CO2 uptake for the Indian Ocean sector of the sub Antarctic Zone (40°-50°S, 20°-150°E) is estimated to be about 0.4 GtC/yr. Extrapolating this estimate to the entire sub-Antarctic zone suggests the uptake in the circumpolar SAZ is approaching 1 GtC/yr.

Atmospheric energy for subsurface life on Mars?

The location and density of biologically useful energy sources on Mars will limit the biomass, spatial distribution, and organism size of any biota. Subsurface Martian organisms could be supplied with a large energy flux from the oxidation of photochemically produced atmospheric H2 and CO diffusing into the regolith. However, surface abundance measurements of these gases demonstrate that no more than a few percent of this available flux is actually being consumed, suggesting that biological activity driven by atmospheric H2 and CO is limited in the top few hundred meters of the subsurface. This is significant because the available but unused energy is extremely large: for organisms at 30-m depth, it is 2,000 times previous estimates of hydrothermal and chemical weathering energy and far exceeds the energy derivable from other atmospheric gases. This also implies that the apparent scarcity of life on Mars is not attributable to lack of energy. Instead, the availability of liquid water may be a more important factor limiting biological activity because the photochemical energy flux can only penetrate to 100- to 1,000-m depth, where most H2O is probably frozen. Because both atmospheric and Viking lander soil data provide little evidence for biological activity, the detection of short-lived trace gases will probably be a better indicator of any extant Martian life.

Anisotropic surface chemistry of aspirin crystals

The wettability of the (001), (100), and (011) crystallographic facets of macroscopic aspirin crystals has been experimentally investigated using a sessile drop contact angle (θ) method. θ for a nonpolar liquid was very similar for all three facets, though significant θ differences were observed for three polar probe liquids. The observed hydrophobicity of the (001) and (100) facets is ascribed to a reduced hydrogen bonding potential at these surfaces, whilst the observed hydrophilicity of facet (011) may be attributed to presence of surface carboxylic functionalities as confirmed by X-ray photoelectron spectroscopy (XPS). The dispersive component of the surface free energy (γ) was similar for all three facets (35 ± 2 mJ/m). The total surface energy, γs varied between 46 and 60 mJ/m due to significant variations in the polar/acid-base components of γ for all facets. Surface polarity as determined by γ measurements and XPS data were in good agreement, linking the variations in wettability to the concentration of oxygen containing surface functional groups. In conclusion, the wettability and the surface energy of a crystalline organic solid, such as aspirin, was found to be anisotropic and facet dependant, and in this case, related to the presence of surface carboxylic functionalities. © 2007 Wiley-Liss, Inc. and the American Pharmacists Association.