Die Konstitutionsabhängigkeit und die benzolinduzierten Effekte der chemischen Verschiebungen der Methoxyprotonen einiger Carbonsäuremethylester

The Chemical shifts of the methoxyprotons in about 60 methyl esters of carboxylic acids were obtained in CCl₄ and C₆D₆, and their dependence on constitution and solvent are discussed. It was shown that the values of a certain molecule could be assumed to be composed additively of a number of parameters which characterise the substituents.     

Study of potassium O,O'-Dibutyldithiophosphate combining DFT, 31P CP/MAS NMR and infrared spectroscopy

Dithiophosphates are used in many different industrial applications. To explain their functions and properties in these applications, a fundamental understanding on a molecular level is needed. Potassium O, O'-Dibutyldithiophosphate and its anion have been investigated by means of a combination of DFT and (31)P CP/MAS NMR and infrared spectroscopy. Several low-energy conformations were studied by DFT. Three different conformations with significantly different torsion angles of the O-C bond relative to the O-P-O plane were selected for further studies of infrared frequencies and (31)P NMR chemical-shift tensors. A good agreement between theoretical and experimental results was obtained, especially when the IR spectra or (31)P chemical shift tensor parameters of all three conformations were added, indicating that, because of the low energy difference between the conformations, the molecules are rapidly fluctuating between them.     

Dynamics of cellulose-water interfaces: NMR spin-lattice relaxation times calculated from atomistic computer simulations

Solid-state nuclear magnetic resonance (CP/MAS 13C NMR) spectroscopy has often been used to study cellulose structure, but some features of the cellulose NMR spectrum are not yet fully understood. One such feature is a doublet around 84 ppm, a signal that has been proposed to originate from C4 atoms at cellulose fibril surfaces. The two peaks yield different T1, differing by approximately a factor of 2 at 75 MHz. In this study, we calculate T1 from C4-H4 vector dynamics obtained from molecular dynamics computer simulations of cellulose I beta-water interfacial systems. Calculated and experimentally obtained T1 values for C4 atoms in surface chains fell within the same order of magnitude, 3-20 s. This means that the applied force field reproduces relevant surface dynamics for the cellulose-water interface sufficiently well. Furthermore, a difference in T1 of about a factor of 2 in the range of Larmor frequencies 25-150 MHz was found for C4 atoms in chains located on top of two different crystallographic planes, namely, (110) and (10). A previously proposed explanation that the C4 peak doublet could derive from surfaces parallel to different crystallographic planes is herewith strengthened by computationally obtained evidence. Another suggested basis for this difference is that the doublet originates from C4 atoms located in surface anhydro-glucose units with hydroxymethyl groups pointing either inward or outward. This was also tested within this study but was found to yield no difference in calculated T1.     

Dissociative recombination of water cluster ions with free electrons: cross sections and branching ratios

Dissociative recombination (DR) of water cluster ions H(+)(H(2)O)(n) (n=4-6) with free electrons has been studied at the heavy-ion storage ring CRYRING (Manne Siegbahn Laboratory, Stockholm University). For the first time, branching ratios have been determined for the dominating product channels and absolute DR cross sections have been measured in the energy range from 0.001 to 0.7 eV. Dissociative recombination is concluded to result in extensive fragmentation for all three cluster ions, and a maximum number of heavy oxygen-containing fragments is produced with a probability close to unity. The branching ratio results agree with earlier DR studies of smaller water cluster ions where the channel nH(2)O+H has been observed to dominate and where energy transfer to internal degrees of freedom has been concluded to be highly efficient. The absolute DR cross sections for H(+)(H(2)O)(n) (n=4-6) decrease monotonically with increasing energy with an energy dependence close to E(-1) in the lower part of the energy range and a faster falloff at higher energies, in agreement with the behavior of other studied heavy ions. The cross section data have been used to calculate DR rate coefficients in the temperature range of 10-2000 K. The results from storage ring experiments with water cluster ions are concluded to partly confirm the earlier results from afterglow experiments. The DR rate coefficients for H(+)(H(2)O)(n) (n=1-6) are in general somewhat lower than reported from afterglow experiments. The rate coefficient tends to increase with increasing cluster size, but not in the monotonic way that has been reported from afterglow experiments. The needs for further experimental studies and for theoretical models that can be used to predict the DR rate of polyatomic ions are discussed.     

Poly(methyl methacrylate-co-ethyl acrylate) latex particles with poly(ethylene glycol) grafts: structure and film formation

Water-based copolymer dispersions were prepared using methyl methacrylate (MMA), ethyl acrylate (EA) (MMA/EA = 1:2), and a series of nonionic polymerizable surfactants, i.e., "surfmers" based on poly(ethylene glycol)-(meth)acrylates. The latexes were compared with the behavior of a conventionally stabilized (nonionic nonylphenol ethoxylate, NP100 with 84 ethylene oxide units) dispersion with the same MMA-EA composition (PMMAEA). A number of techniques were employed in order to characterize structure, dynamics, and film formation properties: solution/solid-state NMR, dynamic/static light scattering (DLS/SLS), differential scanning calorimetry (DSC), tensile/shear mode dynamic mechanical thermal analysis (DMTA), and atomic force microscopy (AFM). The surfmers were found to be miscible with the MMA-EA copolymer at room temperature, with 46-85 mol % of the reacted surfmer detected at the particle surfaces, and the remaining part buried in the particle bulk. In contrast, the NP100 surfactant formed a separate interphase between the copolymer particles with no mixing detected at room temperature or at 90 degrees C. For a 4.0% dry weight concentration, NP100 phase separated and further crystallized at room temperature over a period of several months. Composition fluctuations related to a limited blockiness on a length scale above approximately 2 nm were detected for PMMAEA particles, whereas the surfmer particles were found to be homogeneous also below this limit. On a particle-particle level, the dispersions tended to form colloidal crystals unless hindered by a broadened particle size distribution or, in the case of PMMAEA, by the action of NP100. Finally, a surface roughness (Rq) master plot was constructed for data above the glass transition temperature (Tg) from Tg + 11 degrees C to Tg + 57 degrees C and compared with the complex shear modulus over 11 frequency decades. Shift factors from the 2 methods obeyed the same Williams-Landel-Ferry (WLF) temperature dependence, thus connecting the long-time surface flattening process to the rheological behavior of the copolymer.     

Dissociative recombination study of N(3) (+): cross section and branching fraction measurements

We report an investigation into the dissociative recombination of the azide radical cation, N(3) (+). The reaction rate constant has been measured to be 6.47 x 10(-7) cm(3) s(-1) at room temperature. This value is smaller than those reported earlier for the ion-electron neutralization of N(3) (+) at nitrogen atmospheric pressure. A strong propensity to dissociate through the N(2)+N channel has been observed.     

Plasmid purification using non-porous anion-exchange silica fibres

A new type of fibre-based anion-exchange material for plasmid purification was developed. The basic material consisted of non-porous silica fibres with a mean diameter of 1.5 microm and a surface area of 2.4m(2)g(-1). The fibre surface was provided with several types of ligands, either by adsorption of polymers (chitosan or poly(ethyleneimine)) or by polymerization of amine-containing acrylic monomers onto a propyl methacrylate-silanized surface. The resulting polymer layers contained primary, tertiary or quaternary amines as ion-exchange groups. The packing density could be varied considerably, 9-34% (v/v). The loose packing structure provided excellent flow properties suitable for high-speed operations. The best overall performance was shown by silica fibres provided with tertiary amine polymers, having a plasmid-binding capacity of 0.9 mg ml(-1) (pre-purified plasmid) and a plasmid recovery of 62% (performance data remained stable though several adsorption cycles). The high flow rates possible with the fibre material made it especially useful when large volumes of cleared lysate were processed. The columns could be operated with retention of their adsorption properties at speeds of up to 1800 cm h(-1), equivalent to 0.5 column volumes per minute. The binding capacity was found to be lower than anticipated from the design of the fibres. Fluorescence imaging showing individual plasmid molecules indicated the fibre population to be heterogeneous with respect to plasmid adsorption, some fibres displaying poor binding properties. Possible reasons for this heterogeneity are discussed.     

Large acoustic transients induced by nonthermal melting of InSb

We have observed large-amplitude strain waves following a rapid change in density of InSb due to nonthermal melting. The strain has been measured in real time via time-resolved x-ray diffraction, with a temporal resolution better than 2 ps. The change from the solid to liquid density of the surface layer launches a high-amplitude strain wave into the crystalline material below. This induces an effective plane rotation in the asymmetrically cut crystal leading to deflection of the diffracted beam. The uniform strain in the layer below the molten layer is 2.0(+/-0.2)%. A strain of this magnitude develops within 5 ps of the incident pulse showing that the liquid has reached the equilibrium density within this time frame. Both the strain amplitude and the depth of the strained material in the solid can be explained by assuming a reduction in the speed of sound in the nonequilibrium liquid compared to measured equilibrium values.