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41.
Wide-angle neutron scattering experiments combined with Empirical Potential Structural Refinement modelling have been used to study the detailed structure of decyltrimethylammonium bromide (C10TAB) micelles at two different temperatures; 25°C and 50°C and two concentrations; 0.4 and 0.8?M in water. At higher temperature, the micelles become smaller, and fewer counterions bind to the micelle surfaces, however, the headgroup positions are more ordered, possibly due to crowding in the smaller micelles. At higher concentration, the models suggest the micelles become elongated, although the aggregations numbers are smaller than those at the lower concentration. The smaller micelles found in 0.8?M solutions have more hydrated headgroups and lower counterion binding than the ellipsoidal micelles found in 0.4?M C10TAB solutions. 相似文献
42.
Fernandez-Martin C Edler KJ Roser SJ 《Langmuir : the ACS journal of surfaces and colloids》2004,20(24):10679-10684
Off-specular X-ray reflectivity measurements were carried out to follow the in situ development of surfactant-templated silica thin films at the air-water interface under conditions of controlled relative humidity and temperature, using an enclosed sample cell designed for this purpose. The results suggest a strong dependence of formation time and growth mechanism on ambient conditions. Thin films were synthesized at the air-water interface using cetyltrimethylammonium bromide (CTAB, 0.075 M) and a silica precursor, tetramethoxysilane (TMOS, 0.29-0.80 M) in an acidic medium. The studied humidity range was from 50 to 100%, the temperature was between 25 and 40 degrees C, and the TMOS/CTAB molar ratio was between 3.3 and 10.7. We observed that high humidity slows down the growth process due to lack of evaporation. However, increasing the temperature results in a decrease in the film-formation time. We proposed a formation mechanism for film growth as a consequence of phase separation, organic array assembly, and silica polymerization. 相似文献
43.
A new type of surfactant templated polymer film, which spontaneously forms at the air/water interface into micron-thick structures, was prepared from a water-soluble polymer and a catanionic surfactant mixture; the film is stable, highly ordered and robust, requiring no cross-linking agents to fix the structure. 相似文献
44.
Maya Singer Hobbs Dr. Emma V. Sackville Dr. Andrew J. Smith Prof. Karen J. Edler Dr. Ulrich Hintermair 《ChemCatChem》2019,11(21):5313-5321
Real-time Small Angle X-Ray Scattering (SAXS) has been used to investigate the homogeneity of a series of molecular iridium complexes during water oxidation catalysis in aqueous NaIO4 solution through a continuous flow cell. The results obtained for the unstable [Cp*Ir(OH2)3]2+ precursor forming amorphous IrOx nanoparticles (NPs) in-situ validate and complement previous Dynamic Light Scattering (DLS) studies by providing enhanced sensitivity for small particle sizes and increased temporal resolution under realistic reaction conditions. Correlating particle formation profiles with O2 evolution traces allowed homogeneous catalysis to be clearly distinguished from heterogeneous catalysis. A series of seven pyridine−alkoxide Cp*Ir complexes are shown to be fully homogeneous by SAXS, validating previous studies and confirming their catalysis to be molecular in nature throughout the reaction. 相似文献
45.
George M. Neville;Ana-Maria Dobre;Gavin J. Smith;Samantha Micciulla;Nick J. Brooks;Thomas Arnold;Tom Welton;Karen J. Edler; 《Advanced Optical Materials》2024,34(7):2306644
Mixtures between choline and geranic acid (CAGE) have previously been shown to insert into lipid bilayers. This may be useful for the transdermal delivery of larger pharmaceuticals, however, little is known about the mechanism of activity. By comparing the interactions between CAGE and lipid bilayers with those of a less-active, yet closely-related analogue, choline octanoic acid (CAOT), a chemical basis can be investigated. Overall, six systems are studied here by neutron reflectivity, where d54-1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) solid-supported phospholipid bilayers are first formed on SiO2 substrates before exposure to the deep eutectic solvent (DES). Components of the DES could be identified within the bilayer by exploiting contrast variation and selective deuteration. CAGE is shown to be a mild disruptive agent, free to insert and diffuse across the bilayer, preserving much of the bilayer integrity. Experiments identify co-mingling of geranate ions inhibits the efficient packing of lipid tails, increasing hydration across the bilayer. Conversely, CAOT is found to both exchange and remove lipid molecules to achieve incorporation, inducing swelling and the formation of solvent patches. It appears these behaviors derive from the structures of the anions and thus amphiphilicity of the DES, laying the foundations for the rational design and optimization of these candidates toward transdermal delivery. 相似文献
46.
George M. Neville;Ana-Maria Dobre;Gavin J. Smith;Samantha Micciulla;Nick J. Brooks;Thomas Arnold;Tom Welton;Karen J. Edler; 《Advanced Optical Materials》2024,34(6):2306644
Mixtures between choline and geranic acid (CAGE) have previously been shown to insert into lipid bilayers. This may be useful for the transdermal delivery of larger pharmaceuticals, however, little is known about the mechanism of activity. By comparing the interactions between CAGE and lipid bilayers with those of a less-active, yet closely-related analogue, choline octanoic acid (CAOT), a chemical basis can be investigated. Overall, six systems are studied here by neutron reflectivity, where d54-1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) solid-supported phospholipid bilayers are first formed on SiO2 substrates before exposure to the deep eutectic solvent (DES). Components of the DES could be identified within the bilayer by exploiting contrast variation and selective deuteration. CAGE is shown to be a mild disruptive agent, free to insert and diffuse across the bilayer, preserving much of the bilayer integrity. Experiments identify co-mingling of geranate ions inhibits the efficient packing of lipid tails, increasing hydration across the bilayer. Conversely, CAOT is found to both exchange and remove lipid molecules to achieve incorporation, inducing swelling and the formation of solvent patches. It appears these behaviors derive from the structures of the anions and thus amphiphilicity of the DES, laying the foundations for the rational design and optimization of these candidates toward transdermal delivery. 相似文献
47.
Chevallier C Richardson AD Edler MC Hamel E Harper MK Ireland CM 《Organic letters》2003,5(20):3737-3739
[structure: see text] The crude methanol extract of a marine sponge Cymbastela sp. collected in Papua New Guinea was selected for chemical investigation due to its significant cytotoxicity. Fractionation of the extract led to the isolation of jaspamide (1), hemiasterlin (2), milnamide A (3), and a new metabolite, milnamide D (4). The structure was solved by interpretation of NMR and mass spectra data. The cytotoxic and antitubulin activities of milnamide D (4) were evaluated. 相似文献
48.
Peng S Edler M Ahlmann N Hoffmann T Franzke J 《Rapid communications in mass spectrometry : RCM》2005,19(19):2789-2793
An interface to allow on-line qualitative and quantitative full-plate detection and analysis of compounds separated by thin-layer chromatography (TLC) is presented. A continuous wave diode laser is employed as a desorption source. Atmospheric pressure chemical ionization mass spectrometry ionizes and subsequently identifies the desorbed sample molecules. Besides direct laser desorption on untreated TLC plates, graphite particles were used as a matrix to couple in the laser power and improve the efficiency of desorption. 相似文献
49.
Dr. Oliver S. Hammond Ria Atri Dr. Daniel T. Bowron Prof. Karen J. Edler 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(41):e202200566
Deep eutectic systems are currently under intense investigation to replace traditional organic solvents in a range of syntheses. Here, indole in choline chloride-malic acid deep eutectic solvent (DES) was studied as a function of water content, to identify solute interactions with the DES which affect heterocycle reactivity and selectivity, and as a proxy for biomolecule solvation. Empirical Potential Structure Refinement models of neutron diffraction data showed [Cholinium]+ cations associate strongly with the indole π-system due to electrostatics, whereas malic acid is only weakly associated. Trace water is sequestered into the DES and does not interact strongly with indole. When water is added to the DES, it does not interact with the indole π-system but is exclusively in-plane with the heterocyclic rings, forming strong H-bonds with the -NH group, and also weak H-bonds and thus prominent hydrophobic hydration of the indole aromatic region, which could direct selectivity in reactions. 相似文献
50.
The durability of reinforced concrete structures is dominated by steel reinforcement corrosion and uncertain service loads, which have to be considered in the lifetime oriented structural design. The transport of corrosive substances into the structure is considerably influenced by load induced cracking. The crack width therefore is a major controlling factor for the lifetime of reinforced concrete structures. To improve the design for durability, finite element models in combination with optimization approaches for polymorphic uncertain data are presented. Here, the crack width at the reinforcement layer is used as the optimization objective to be minimized. The structural reliability is treated as a constraint of the optimization task in terms of the accepted failure probability. The concrete covers of the reinforcement layers are chosen as interval design parameters, with midpoints to be optimized and a given radius to take construction imprecision into account. The structural loading, the Young's modulus of concrete and the corresponding tensile strength are considered as stochastic a priori parameters within the optimization, which is solved by a particle swarm optimization approach in combination with an artificial neural network surrogate model. The polymorphic uncertain structural response is computed by a combination of Monte Carlo simulations and optimization‐based interval analysis to consider the stochastic and interval parameters within the optimization task, respectively. An application example demonstrates the performance of the proposed approach. 相似文献