Search results for "Faces"
showing 10 items of 3167 documents
Chemical Reactivity in AOT Microemulsions: Kinetics of Water Replacement in a Square-Planar Palladium(II) Aquo Complex by Monoalkylthioureas
1998
The kinetics of water replacement in the cationic palladium(II) aquo complex [Pd(Et4dien)(H2O)]2+, where Et4dien = Et2N(CH2)2NH(CH2)2NEt2, by thiourea, methylthiourea, and ethylthiourea have been studied at 25.0 °C in heptane−AOT−water microemulsion over a wide range of the molar ratio R (=[H2O]/[AOT]) at the constant surfactant concentration of 0.13 mol dm-3. The reaction rates are significantly higher in microemulsions than in bulk water and decrease rapidly as the parameter R increases. The kinetic data, interpreted quantitatively by applying the pseudophase model to the microemulsion, indicate that there is a weak partitioning of the nucleophiles between the water core and the AOT inter…
Femtosecond Transient Absorption Study of the Dynamics of Acrylodan in Solution and Attached to Human Serum Albumin
2003
The excited-state relaxation dynamics of the protein-labeling dye acrylodan in solution and attached to human serum albumin has been studied by femtosecond transient absorption spectroscopy. Time-resolved spectra and kinetics of stimulated emission and excited-state absorption in the wavelength region from 400 to 800 nm were studied in ethanol and dimethylformamide. The excited-state solvation dynamics is characterized by multiexponential behavior in both solvents. In ethanol solution, the time dependence of the transient spectra is interpreted in terms of fast solvent relaxation followed by excited-state isomerization of the dye. Acrylodan attached to the protein shows a relaxation compone…
Nonlinear hairy layer theory of electrophoretic fingerprinting applied to consecutive layer by layer polyelectrolyte adsorption onto charged polystyr…
1997
The consecutive layer-by-layer adsorption of poly(allylamine hydrochloride) (PAH) and poly(styrenesulfonate) (PSS) on colloidal charged latex particles is investigated by measuring the electrophoretic mobility as a function of pH and ionic strength over a broad range (electrophoretic fingerprinting). Meaningful interpretation of the data required the development of a nonlinear approach to hairy particle electrophoresis including dissociation, adsorption, and association. Steric and electrostatic exclusion of mobile ions from the hairy layer has been considered. Also, the surface conductivity correction is extended to the case of charged hairy layer particles. We deposited up to three polyel…
Understanding Digestive Ripening of Ligand-Stabilized, Charged Metal Nanoparticles
2017
Most syntheses of thiolate-protected metal nanoparticles (NPs) include a thermochemical step in which the as-prepared, polydisperse NPs are transformed to a narrower size distribution in a poorly understood process known as digestive ripening (DR). Previous theoretical approaches considered either surface and electrostatic contributions or surface and ligand-binding contributions. We show that the three contributions are needed to obtain theoretical predictions in agreement with experimental observations. Although statistical thermodynamics does not clarify mechanistic details, it certainly provides valuable insights on the DR process. Remarkably, a relatively simple theory with no fitting …
Paramagnetic aluminium β-diketiminate
2012
The β-diketiminate ligand framework is shown to undergo reduction to form a neutral main group radical stabilized by spiroconjugation of the unpaired electron over the group 13 element centre. The synthesized paramagnetic complex was characterized by EPR spectroscopy and computational chemistry.
Vibrational Circular Dichroism of Thiolate-Protected Au25 Clusters: Accurate Prediction of Spectra and Chirality Transfer within the Mixed Ligand She…
2019
We have prepared Au25(PET)18-2x((R)-FBI-NAS)x(PET = 2-phenylethylthiol, (R)-FBINAS = (R)-5,5',6,6',7,7',8,8'-octafluoro-[1,1'-binaphthalene]-2,2'-dithiol) mixed ligand shell clusters via ligand exchange. Two fractions with different composition of the ligand shell were separated using size-exclusion chromatography and studied by infrared (IR) spectroscopy and vibrational circular dichroism (VCD). Both IR and VCD spectra are dominated by FBINAS vibrations although PET is more abundant on the cluster. Calculated VCD spectra on a model cluster Au25(SH)16(FBINAS)1 depend on the charge state of the cluster, and the anion is in excellent agreement with the experimental spectra of the Au25(PET)18-…
Do the Intramolecular π Interactions Improve the Stability of Ionic, Pyridine-Carbene-Based Iridium(III) Complexes?
2013
Throughout the last years one of the most intensive research topics in light-emitting electrochemical cells (LECs) focused on the design of blue-emitting, ionic iridium(III) complexes. To this end, the most recent strategy is the use of carbene-based ancillary ligands. Although blue LECs have been successfully fabricated, the stability has been noted as the main drawback. To overcome this problem, Zhang et al. have recently explored the use of π interactions to enhance the strength of pyridine-carbene-based complexes. The authors suggested that the use of intramolecular π–π stacking interactions by means of pendant phenyl rings to improve the stability of LECs is not as effective as in devi…
Probing optical and magnetic properties via subtle stereoelectronic effects in mononuclear DyIII-complexes
2021
Tapping into the secondary coordination environment of mononuclear DyIII-complexes leads to drastic changes in luminescence and magnetism. Visualization of effects induced by stereoelectronics on the opto-magnetic properties was achieved through subtle modifications in the ligand framework.
Inhibitoren der Korrosion (8) Über die Abhängigkeit der Korrosionsinhibierung des Eisens in Salzsäure von der Struktur quartärer Phosphoniumsalze
1971
Bei quartaren Phosphoniumsalzen be-steht zwischen der Inhibitorwirkung im sauren Medium unter Auschlus von Luft und den polarographisch ermittelten Re-duktionspotentialen keine direkte Bezie-hung. Die sterischen Faktoren der nach Aufnahme von zwei Elektronen entste-henden und an der Eisenoberflache fixierten Fragmente sind offenbar fur die Inhibitorwirkung hauptsachlich ver-antwortlich. Bisphoniumsalze mit gesattigten oder ungesattigten Brucken sind unter den oben genannten Bedingungen hervor-ragende Inhibitoren. Am wirksamsten sind Bisphosphoniumsalze mit Ketten von 4 bis 10 Methylengruppen zwischen den Phosphoniumzentren. Der starre p-Phenylenrest ist als Verknupfungs-prinzip weniger geei…
Anwendung der Mößbauer-Spektroskopie auf die Untersuchung von Deckschichten in Naturumlaufkesseln
1978
57Fe-Mosbauer-spektroskopische Transmissions- und Reflexionsmessungen wurden zur Aufklarung der qualitativen und quantitativen Zusammensetzung von Deckschichten auf der Innenseite von Rohren aus Naturumlaufkesseln vorgenommen. Die Deckschichten waren bei 120 bis 174 atu, 320 bis 353 °C, einem pH-Wert zwischen 9,5 und 10,5 und einem Gehalt an P2O5 und SiO2 von < 10 bzw. < 4 mg/l auf den Rohrinnenflachen (Werkstoff 15 Mo 3: 0,12%C, 0,15% Si, 0,5% Mn, 0,04% P, 0,04% S, ⩽ 0,3% Cr, 0,25% Mo, Rest Fe; St. 45. 8. III: < 0,22% C, 0,1% Si, ⩾ 0,45% Mn, 0,05% P, 0,05% S, ⩽ 0,3% Cr, Rest Fe) innerhalb von maximal 127000 h entstanden. Die Mosbauer-spektroskopischen Untersuchungen, unterstutzt durch eine…