Thin films of carbohydrate based surfactants and carboxymethylcellulose acetate butyrate mixtures: Morphology and thermal behavior

Thin films of mixtures containing carboxymethylcellulose acetate butyrate (CMCAB) and carbohydrate based surfactant, namely, sorbitan monopalmitate (Span 40) or poly(oxyethylene) sorbitan monopalmitate (Tween 40) were spin-coated onto silicon wafers. The effect of surfactant concentration on resulting film morphology and surface toughness Was Studied by atomic force microscopy (AFM). Upon increasing the concentration of Span 40 in the mixture, films became rougher and more heterogeneous, indicating surface enrichment by Span 40 molecules. In the case of mixtures composed by CMCAB and Tween 40, the increase of Tween 40 in the mixture led to smoother and more homogeneous films, indicating compatibility between both components. Differential scanning calorimetry (DSC) revealed that Span 40 and Tween 40 act as plasticizers for CMCAB, leading to dramatic reduction of glass transition temperature of CMCAB, namely, Delta T(g) = -158 degrees C and Delta T(g)=-179 degrees C. respectively. (C) 2008 Elsevier B.V. All rights reserved.

Effect of surfactants and polyethylene glycol on the activity and stability of a lipase from oilseeds of Pachira aquatica

Lipases from oilseeds have a great potential for commercial exploration as industrial enzymes. Lipases are used mixed with surfactants in cleaning and other formulated products, and accordingly, both components must be compatible with each other. This work presents the results of the effects of anionic, cationic and nonionic surfactants, polyethylene glycol and urea on the activity and stability of a lipase extracted of oilseeds from Pachira aquatica. The enzyme was purified and the spectrophotometric assays were done using p-nitrophenyl acetate (p-NPA) as substrate pH 7.5 and 25 degrees C. The activity was significantly enhanced by the cationic surfactant CTAB. Bile salts increased the lipase activity in the tested concentration range, whereas anionic and nonionic surfactants showed an inhibitory effect. Aqueous solutions of PEG activated the lipase and maximum activation (161%) occurred in PEG 12,000. This effect on lipase that can be due to exposition of some hydrophobic residues located in the vicinity of the active site or aggregation.

Photochemical determination of the interactions between surfactants and polyelectrolytes

The interaction of polyelectrolytes with oppositely charged ionic surfactants was studied at low surfactant concentrations using photochemical bound and free probes. Free probes migrate to initially formed pre-aggregates in systems with high charge- density polyelectrolytes, giving rise to excimer emission. For these systems the initial aggregation process seems to be due to electrostatic interactions. For larger surfactants or copolymers containing larger proportions of neutral monomer that interactions are of hydrophobic nature.

The mechanism of dephosphorylation of bis(2,4-dinitrophenyl) phosphate in mixed micelles of cationic surfactants and lauryl hydroxamic acid

(Figure Presented) Mixed micelles of cetyltrimethylammonium bromide (CTABr) or dodecyltrimethylammonium bromide (DTABr) and the α-nucleophile, lauryl hydroxamic acid (LHA) accelerate dephosphorylation of bis(2,4-dinitrophenyl) phosphate (BDNPP) over the pH range 4-10. With a 0.1 mole fraction of LHA in DTABr or CTABr, dephosphorylation of BDNPP is approximately 10 4-fold faster than its spontaneous hydrolysis, and monoanionic LHA - is the reactive species. The results are consistent with a mechanism involving concurrent nucleophilic attack by hydroxamate ion (i) on the aromatic carbon, giving an intermediate that decomposes to undecylamine and 2,4-dinitrophenol, and (ii) at phosphorus, giving an unstable intermediate that undergoes a Lossen rearrangement yielding a series of derivatives including N,N-dialkylurea, undecylamine, undecyl isocyanate, and carbamyl hydroxamate. © 2009 American Chemical Society.

Modulation of the activity and selectivity of the immobilized lipases by surfactants and solvents

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

Studies on the interaction of surfactants and neutral cyclodextrins by capillary electrophoresis. Application to chiral analysis

In the present study, mixed systems composed of SDS in the presence of neutral cyclodextrins were considered. Firstly, the effect of the CDs on the CMC of the surfactant was evaluated by CE experiments. Furthermore, a new CE approach based on electric current measurement was developed for the estimation of the stoichiometry as well as of the binding constants of SDS-CDs complexes. The results of these investigations were compared to those obtained with a different technique, electronic paramagnetic resonance (EPR). The obtained results suggested that methylated CDs, in particular (2,6-di-O-methyl)-beta-cyclodextrin (DM-beta-CD), strongly affect the micellization of SDS in comparison to the other studied CDs. This effect also paralleled the chiral CD-MEKC performance, as indicated by the enantioresolution of (+/-)-Catechin, which was firstly selected as a model compound representative of important chiral phytomarkers. Then a CD-MEKC system, composed of sodium dodecyl sulfate as surfactant (90 mM) and hydroxypropyl-beta-cyclodextrin (25 mM) as chiral selector, under acidic conditions (25 mM borate – phosphate buffer, pH 2.5) was applied to study the thermal epimerisation of epi-structured catechins, (-)-Epicatechin and (-)-Epigallocatechin, to non epi-structured (-)-Catechin and (-)-Gallocatechin. The latter compounds, being non-native molecules, were for the first time regarded as useful phytomarkers of tea sample degradation. The proposed method was applied to the analysis of more than twenty tea samples of different geographical origins (China, Japan, Ceylon), having undergone different storage conditions and manufacturing processes.

Surfactants and their aerobic degradation products

Die Ziele der vorliegenden Arbeit waren 1) die Entwicklung und Validierung von sensitiven und substanz-spezifischen Methoden für die quantitative Bestimmung von anionischen, nichtionischen und amphoteren Tensiden und deren Metaboliten in wässrigen Umweltproben unter Einsatz leistungsfähiger, massenspektrometrischer Analysengeräte,2) die Gewinnung von aeroben, polaren Abbauprodukten aus Tensiden in einem die realen Umweltbedingungen simulierenden Labor-Festbettbioreaktor (FBBR), dessen Biozönose oberflächenwasserbürtig war,3) zur Aufklärung des Abbaumechanismus von Tensiden neue, in 2) gewonnene Metabolite zu identifizieren und massenspektrometrisch zu charakterisieren ebenso wie den Primärabbau und den weiteren Abbau zu verfolgen,4) durch quantitative Untersuchungen von Tensiden und deren Abbauprodukten in Abwasser und Oberflächenwasser Informationen zu ihrem Eintrag und Verhalten bei unterschiedlichen hydrologischen und klimatischen Bedingungen zu erhalten,5) das Verhalten von persistenten Tensidmetaboliten in Wasserwerken, die belastetes Oberflächenwasser aufbereiten, zu untersuchen und deren Vorkommen im Trinkwasser zu bestimmen,6) mögliche Schadwirkungen von neu entdeckten Metabolite mittels ökotoxikologischer Biotests abzuschätzen,7) durch Vergleich der Felddaten mit den Ergebnissen der Laborversuche die Umweltrelevanz der Abbaustudien zu belegen. Die Auswahl der untersuchten Verbindungen erfolgte unter Berücksichtigung ihres Produktionsvolumens und der Neuheit auf dem Tensidmarkt. Sie umfasste die Waschmittelinhaltsstoffe lineare Alkylbenzol-sulfonate (LAS), welches das Tensid mit der höchsten Produktionsmenge darstellte, die beiden nichtionischen Tenside Alkylglucamide (AG) und Alkylpolyglucoside (APG), ebenso wie das amphotere Tensid Cocamidopropylbetain (CAPB). Außerdem wurde der polymere Farbübertragungsinhibitor Polyvinylpyrrolidon (PVP) untersucht.

Local pain and spreading hyperalgesia induced by intramuscular injection of nerve growth factor are not reduced by local anesthesia of the muscle

Injections with local anesthesia for therapeutic and diagnostic purposes are common clinical practice. This double-blind placebo controlled study explores the rational of local anesthetic blocks for the detection of muscle pain as the primary generator in spreading hyperalgesic conditions.

Wetting and spreading of a surfactant film on solid particles: influence of sharp edges and surface irregularities

In addition to particle size and surface chemistry, the shape of particles plays an important role in their wetting and displacement by the surfactant film in the lung. The role of particle shape was the subject of our investigations using a model system consisting of a modified Langmuir-Wilhelmy surface balance. We measured the influence of sharp edges (lines) and other highly curved surfaces, including sharp corners or spikes, of different particles on the spreading of a dipalmitoylphosphatidyl (DPPC) film. The edges of cylindrical sapphire plates (circular curved edges, 1.65 mm radius) were wetted at a surface tension of 10.7 mJ/m2 (standard error (SE) = 0.45, n = 20) compared with that of 13.8 mJ/m2 (SE = 0.20, n = 20) for cubic sapphire plates (straight linear edges, edge length 3 mm) (p < 0.05). The top surfaces of the sapphire plates (cubic and cylindrical) were wetted at 8.4 mJ/m2 (SE = 0.54, n = 20) and 9.1 mJ/m2 (SE = 0.50, n = 20), respectively, but the difference was not significant (p > 0.05). The surfaces of the plates showed significantly higher resistance to spreading compared to that of the edges, as substantially lower surface tensions were required to initiate wetting (p < 0.05). Similar results were found for talc particles, were the edges of macro- and microcrystalline particles were wetted at 7.2 mJ/m2 (SE = 0.52, n = 20) and 8.2 mJ/m2 (SE = 0.30, n = 20) (p > 0.05), respectively, whereas the surfaces were wetted at 3.8 mJ/m2 (SE = 0.89, n = 20) and 5.8 mJ/m2 (SE = 0.52, n = 20) (p < 0.05), respectively. Further experiments with pollen of malvaceae and maize (spiky and fine knobbly surfaces) were wetted at 10.0 mJ/m2 (SE = 0.52, n = 10) and 22.75 mJ/m2 (SE = 0.81, n = 10), respectively (p < 0.05). These results show that resistance to spreading of a DPPC film on various surfaces is dependent on the extent these surfaces are curved. This is seen with cubic sapphire plates which have at their corners a radius of curvature of about 0.75 microm, spiky malvaceae pollen with an even smaller radius on top of their spikes, or talc with various highly curved surfaces. These highly curved surfaces resisted wetting by the DPPC film to a higher degree than more moderately curved surfaces such as those of cylindrical sapphire plates, maize pollens, or polystyrene spheres, which have a surface free energy similar to that of talc but a smooth surface. The macroscopic plane surfaces of the particles demonstrated the greatest resistance to spreading. This was explained by the extremely fine grooves in the nanometer range, as revealed by electron microscopy. In summary, to understand the effects of airborne particles retained on the surfaces of the respiratory tract, and ultimately their pathological potential, not only the particle size and surface chemistry but also the particle shape should be taken in consideration.

Na–H Exchange Acts Downstream of RhoA to Regulate Integrin-induced Cell Adhesion and Spreading

The ubiquitously expressed Na–H exchanger NHE1 functions in regulating intracellular pH and cell volume. NHE1 activity is stimulated by hormones, growth factors, and activation of integrin receptors. We recently determined that NHE1 activity is also stimulated by activation of the low molecular weight GTPase RhoA and that increases in NHE1 activity are necessary for RhoA-induced formation of actin stress fibers. We now show that NHE1 acts downstream of RhoA to modulate initial steps in integrin signaling for the assembly of focal adhesions. Adhesion of CCL39 fibroblasts on fibronectin was markedly delayed in the presence of the NHE inhibitor ethylisopropylamiloride. In mutant PS120 cells, derived from CCL39 fibroblasts but lacking NHE1, adhesion was also delayed but was rescued in PS120 cells stably expressing NHE1. In the absence of NHE1 activity, cell spreading was inhibited, and the accumulation of integrins, paxillin, and vinculin at focal contacts was impaired. Additionally, tyrosine phosphorylation of p125FAK induced by integrin clustering was also impaired. Inactivation of RhoA with C3 transferase and inhibition of the Rho-kinase p160ROCK with the pyridine derivative Y-27632 completely abolished activation of NHE1 by integrins but not by platelet-derived growth factor. These findings indicate that NHE1 acts downstream of RhoA to contribute a previously unrecognized critical signal to proximal events in integrin-induced cytoskeletal reorganization.

pH foliar e deposição de gotas de pulverização em plantas daninhas aquáticas: Brachiaria mutica, Brachiaria subquadripara e Panicum repens

A diversidade morfológica da superfície foliar existente entre as espécies de plantas e a presença de estruturas foliares, como tricomas, estômatos, cutícula e ceras, podem exercer grande influência na aderência e deposição das gotas de pulverização, assim como na absorção do herbicida. Dessa forma, o objetivo do presente trabalho foi estudar, em plantas daninhas aquáticas emersas (Brachiaria mutica, Brachiaria subquadripara e Panicum repens), o pH foliar, bem como a área de molhamento de gotas de pulverização na superfície foliar adaxial e abaxial. O experimento foi conduzido no Núcleo de Pesquisas Avançadas em Matologia - NUPAM, pertencente à Faculdade de Ciências Agronômicas de Botucatu/SP - UNESP. As plantas foram cultivadas em caixas d'água no campo, quando elas atingiram seu pleno desenvolvimento (antes do florescimento), foram feitas as avaliações de pH foliar e da área de molhamento de gotas de pulverização. As tensões superficiais das gotas depositadas (0,5 µL), apresentadas pelas soluções de glyphosate aplicado isoladamente (5,0% v v-1, Rodeo 480g L-1 e.a. - produto comercial), glyphosate + Aterbane BR (5,0% + 0,5% v v-1), glyphosate + Silwet L-77 (5,0% + 0,05% v v-1), além das soluções com os adjuvantes isolados, Aterbane BR (0,5% v v-1) e Silwet L-77 (0,05% v v-1), foram respectivamente de 72,1; 28,7; 23,3; 37,3; e 22,1 mN m-1. As médias obtidas de pH foliar variaram entre 5,71 e 6,03, destacando-se a espécie B. mutica, com valores de 5,72 e 6,03 para as faces adaxial e abaxial, respectivamente. Contudo, mais estudos devem ser realizados para verificar a influência do pH foliar na absorção de herbicidas por espécies daninhas aquáticas. Das plantas daninhas aquáticas avaliadas, B. subquadripara foi a espécie que obteve as maiores médias de área de molhamento nas faces adaxial e abaxial da folha, proporcionadas pelas soluções de glyphosate + Aterbane BR, glyphosate + Silwet L-77 e Silwet L-77, com valores de 6,44 - 4,36; 7,77 - 10,59; e 10,94 - 10,28 mm², respectivamente.

Interaction of surfactants with DNA. Role of hydrophobicity and surface charge on intercalation and DNA melting

A probe, 9-(anthrylmethyl)trimethylammonium chloride, 1, was prepared. 1 binds to calf-thymus DNA or Escherichia coli genomic DNA with high affinity, as evidenced from the absorption titration. Strong hypochromism, spectral broadening and red-shifts in the absorption spectra were observed. Half-reciprocal plot constructed from this experiment gave binding constant of 5±0.5×104 M−1 in base molarity. We employed this anthryl probe-DNA complex for studying the effects of addition of various surfactant to DNA. Surfactants of different charge types and chain lengths were used in this study and the effects of surfactant addition to such probe-DNA complex were compared with that of small organic cations or salts. Addition of either salts or cationic surfactants led to structural changes in DNA and under these conditions, the probe from the DNA-bound complex appeared to get released. However, the cationic surfactants could induce such release of the probe from the probe-DNA complex at a much lower concentration than that of the small organic cations or salts. In contrast the anionic surfactants failed to promote any destabilization of such probe-DNA complexes. The effects of additives on the probe-DNA complexes were also examined by using a different technique (fluorescence spectroscopy) using a different probe ethidium bromide. The association complexes formed between the cationic surfactants and the plasmid DNA pTZ19R, were further examined under agarose gel electrophoresis and could not be visualized by ethidium bromide staining presumably due to cationic surfactant-induced condensation of DNA. Most of the DNA from such association complexes can be recovered by extraction of surfactants with phenol-chloroform. Inclusion of surfactants and other additives into the DNA generally enhanced the DNA melting temperatures by a few °C and at high [surfactant], the corresponding melting profiles got broadened.

Spreading and atomization of droplets on a vibrating surface in a standing pressure field

We report the first observation and analytical model of deformation and spreading of droplets on a vibrating surface under the influence of an ultrasonic standing pressure field. The standing wave allows the droplet to spread, and the spreading rate varies inversely with viscosity. In low viscosity droplets, the synergistic effect of radial acoustic force and the transducer surface acceleration also leads to capillary waves. These unstable capillary modes grow to cause ultimate disintegration into daughter droplets. We find that using nanosuspensions, spreading and disintegration can be prevented by suppressing the development of capillary modes and subsequent break-up. (C) 2012 American Institute of Physics. http://dx.doi.org/10.1063/1.4757567]

The effect of cationic, non-ionic and amphiphilic surfactants on the intercalation of bentonite

Surfactant-clay interactions are key for the development of new clay applications and inorganic-organic nanocomposites. Bentonite, with montmorillonite as the principal clay mineral constituent, was modified with varying concentrations of hexadecethyltrimethylammonium chloride (HDTMA), as a reference cationic surfactant, polypropylene glycol (PPG) 1200 and 2000, as non-ionic surfactants, and lecithin and Topcithin®, as amphiphilic phospholipid surfactants, according to the cation exchange capacity (CEC). The modified bentonites were characterised by X-ray diffraction, thermogravimetric analysis (TGA), Fourier transform infrared (FTIR) spectrometry, specific surface area and pore volume. Three intercalation regions have been identified depending on the surfactant. The non-ionic surfactant caused only a crystalline expansion of bentonite interlayers, while the cationic surfactant induced an osmotic intercalation. The amphiphilic lecithin derivatives intercalated more extensively with the bentonite matrix. The TGA and the FTIR spectra showed that, at lower concentrations, the PPGs and HDTMA adopted a disordered conformation that required more energy to degrade, while at higher concentrations, the surfactants were ordered in the interlayer space of the bentonite. The lecithin derivative surfactant had a greater thermal and conformation stability. The specific surface area reduced with increasing surfactant concentrations. This study highlights the effect of surfactant type on the interlayer space of montmorillonite in the perspective of developing novel clay functions. © 2013.