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A series of nitrogen ligand (L)/copper complexes of the type [(CuL)-L-I](+), [(CuL)-L-II(X)](+) and [(CuL2)-L- I](+) (X = Cl-, BF4-, acac(-), CH3COO- and SO3CF3-) was studied in the gas phase by electrospray ionization mass spectrometry. The following ligands (L) were employed: 1,12-diazaperylene (dap), 1,1'-bisiso-quinoline (bis), 2,2'-bipyridine (bpy), 1,10-phenanthroline (phen), 2,11-disubstituted 1,12-diazaperylenes (dap), 3,3'- disubstituted 1,1'-bisisoquinoline (bis), 5,8-dimethoxy-substituted diazaperylene (meodap), 6,6'-dimethoxy- substituted bisisoquinoline (meobis) and 2,9-dimethyl-1,10-phenanthroline (dmphen). Collision-induced decomposition measurements were applied to evaluate the relative stabilities of the different copper complexes. The influence of the spatial arrangement of the ligands, of the type of substituents and of the counter ion of the copper salts employed for the complexation was examined. Correlations were found between the binding constants of the [ML2](+) complexes in solution and the relative stabilities of the analogous complexes in the gas phase. Furthermore, complexation with the ligands 2,11-dialkylated 1,12-diazaperylenes [alkyl = ethyl (dedap) and isopropyl (dipdap)] was studied in the solvents CH3OH and CH3CN.
Die Inline-Bestimmung von Teilchengroeßen in Emulsionen und Suspensionen stellt besondere Anforderungen an die Messtechnik, da auch bei sehr hohen Teilchenkonzentrationen im Prozess verduennungsfreie Analytik betrieben werden soll. Neben einer Klaerung der Begriffe atline, online und in-line gibt der Beitrag eine Einfuehrung in die mathematische Beschreibung von Groeßenverteilungen. Als Inline-Techniken werden Photonendichtewellen-Spektroskopie, Focused Beam Reflectance Measurement und Ultraschallextinktion-Spektroskopie diskutiert und ihre sehr unterschiedlichen physikalischen Messprinzipien erlaeutert. Auch wird kurz erklaert, wie Teilchengroeßen aus den Messresultaten erhalten werden. Die wesentlichen Charakteristika dieser drei Methoden werden abschließend im ueberblick dargestellt.
The free volume in thin films of poly(N-isopropylacrylamid) end-capped with n-butyltrio-carbonate (nbc-PNIPAM) is probed with positron annihilation lifetime spectroscopy (PALS). The PALS measurements are performed as function of energy to obtain depth profiles of the free volume of nbc-PNIPAM films. The range of nbc-PNIPAM films with thicknesses from 40 to 200 nm is focused. With decreasing film thickness the free volume increases in good agreement with an increase in the maximum swelling capability of the nbc-PNIPAM films. Thus in thin hydrogel films the sorption and swelling behavior is governed by free volume.
Oil-in-water (o/w) Pickering emulsions stabilized with silica nanoparticles were prepared. Droplets of diethyl phthalate (oil phase) act as reservoirs for 8-hydroxyquinoline (8-HQ), which is used as (a) the hydrophobizing agent for the silica particles and (b) an encapsulated corrosion inhibitor for application in active feedback coatings. The hydrophobization of silica nanoparticles with 8-HQ is determined by the amount of this agent adsorbed on the nanoparticle surface. The latter is governed by the 8-HQ concentration in the aqueous phase, which in turn depends on the degree of protonation and fir ally on the pH. We observe three ranges of 8-HQ adsorption value with respect to nanoparticle hydophobization: (I) insufficient, (2) sufficient, and (3) excessive adsorption by the formation of an 8-HQ bilayer, where only case 2 leads to the necessary nanoparticle hydrophobization. Hence emulsions stable in a narrow pH window between pH 5.5 and 4.4 follow. Here functional molecules are sufficiently charged to compensate for the charges on silica nanoparticles to make them interfacially active and thus able to stabilize an emulsion but they are still to a large extent uncharged and thereby remain in the oil phase. The emulsification is reversible upon changing the pH to a value beyond the stability region.
Homopolymers of N-acryloyl glycinamide were prepared by reversible addition-fragmentation chain transfer polymerization in water. The formed macromolecules exhibit strong polymer-polymer interactions in aqueous milieu and therefore form thermoreversible physical hydrogels in pure water, physiological buffer or cell medium.
Herein we demonstrate how the photoreaction between anthracenes and singlet oxygen (O-1(2)) is employed for applications either as photoswitch or as photoresist. Thin Films of the diaryl-alkyl anthracene 1 and the analogous oligomeric species 2 were it-radiated under photomasks to generate pattern structures composed of 1/1-O-2 and 2/2-O-2. Kelvin probe force microscopy (KPFM) provided a powerful and nondestructive method to image the pattern information. The following studies based on AFM, KPFM and contact angle measurements unfold that the two species 1 and 2 underwent different progressions after the imaging step. Degrading is observed for the monomeric compound 1 and the pattern eventually becomes recognizable in topography. In the oxidized state (1-O-2) the monomeric species remains physically stable. In consequence, the unreacted portion is removable and the remaining oxygenated form 1-O-2 is sufficiently stable to protect in underlying substrate (e.g., silver) from etching. Thus, the system 1/1-O-2 operates as photoresist. Oil the other hand, both states of the oligomier 2 remain stable. The Film is stable up to temperatures > 120 degrees C required to erase the pattern within acceptable time by cycloreversion. Anthracene 2 therefore acts as erasable and rewritable photochromic switch. The different behavior between 1 and 2 is explained by phase transitions which cause crystallization and finally ablation. Such transitions affect only the monomeric system 1/1-O-2 and not the oligomeric system 2/2-O-2. In conclusion, we designed two very similar materials based on diarylanthracenes, which can act either as a photoresist or as a rewritable photochrornic switch.
Stochastic approach to laser-induced ultrafast dynamics : the desorption of H-2/D-2 from Ru(0001)
(2010)
The desorption of molecular hydrogen and deuterium induced by femtosecond-laser pulses is studied theoretically for the so-called DIMET (Desorption Induced by Multiple Electronic Transitions) process. These investigations are based on nonadiabatic classical Monte Carlo trajectory (CMCT) simulations on a ground and an excited state potential energy surface, including up to all six adsorbate degrees of freedom. The focus is on the hot-electron mediated energy transfer from the surface to the molecule and back, and the energy partitioning between the different degrees of freedom of the desorbing molecules. We first validate for a two-mode model comprising the desorption mode and the internal vibrational coordinate, the classical Monte Carlo trajectory method by comparing with Monte Carlo wavepacket (MCWP) calculations arising from a fully quantum mechanical open-system density matrix treatment. We then proceed by extending the CMCT calculations to include all six nuclear degrees of freedom of the desorbing molecule. This allows for a detailed comparison between theory and experiment concerning isotope effects, energy partitioning (translational, vibrational, and rotational energies and their distributions), and the dependence of these properties on the laser fluence. The most important findings are as follows. (i) CMCT agrees qualitative with the MCWP scheme. (ii) The basic experimental features such as the large isotope effect, the non-linear increase of yield with laser fluence, translationally hot products (in the order of several 1000 K) and non-equipartitioning of translational and internal energies (E-trans > E- vib > E-rot) are well reproduced. (iii) Predictions concerning a strong angular dependence of translational energies at large observation angles are also made.
Olefin isomerization side reactions that occur during ADMET polymerizations were studied by preparing polyesters via ADMET and subsequently degrading these polyesters via transesterification with methanol. The resulting diesters, representing the repeating units of the previously prepared polyesters, were then analyzed by GC-MS. This strategy allowed quantification of the amount of olefin isomerization that took place during ADMET polymerization with second generation ruthenium metathesis catalysts. In a second step, it was shown that the addition of benzoquinone to the polymerization mixture prevented the olefin isomerization. Therefore, second generation ruthenium metathesis catalysts may now be used for the preparation of well-defined polymers via ADMET with very little isomerization, which was not possible before.
Lectin-bound conformations and non-covalent interactions of glycomimetic analogs of thiochitobiose
(2010)
The bound conformations of five S-glycoside analogs of N,N'-diacetylchitobiose as well as their non- covalent interactions with two lectins, Phytolacca americana lectin (PAL) and wheat germ agglutinin (WGA), are reported. The conformations of the ligands were examined by trNOESY experiments and compared with the free, solution-state conformations and molecular modeling data obtained by force field calculations. In the case of S-aryl, S-glycosides with exclusively S-glycosidic linkages, similar free and lectin-bound conformations and non-covalent interactions were found, whereas they differed for mixed glycosides and for a thiazoline derivative. In addition, STD (saturation transfer difference) NMR magnetization transfer efficiencies at three different temperatures were determined and assessed with respect to the structural differences of these pseudosaccharides. The binding epitopes of each substrate with PAL and WGA were also determined.