Effects of boundaries on structure formation in low-dimensional colloid model systems near the liquid-solid-transition in equilibrium and in external fields and under shear

A brief review focusing on low-dimensional colloidal model systems is given describing both simulation studies and complementary experiments, elucidating the interplay between phase behavior, geometric structures, and transport phenomena. These studies address the response of these very soft colloidal systems to perturbations such as uniform or uniaxial compression, laser fields, randomly quenched disorder, and shear deformation caused by moving boundaries. Binary hard-disk mixtures are studied by Monte Carlo simulation, to investigate ordering on surfaces or in monolayers, modeling the effect of a substrate by an external potential. By weak external laser fields the miscibility of the mixture can be controlled, and the underlying mechanism (laser-induced demixing) is clarified. The stability of various space-filling structures is discussed only for the case where no laser fields are present.Hard spheres interacting with repulsive screened Coulomb or dipolar interaction confined in 2D and 3D narrow constrictions are investigated by Brownian Dynamics simulation. With respect to the structural behavior, it is found that layers or planes throughout the microchannel are formed. The arrangement of the particles is disturbed by diffusion, and can also be modified by an external driving force causing a density gradient along the channel. Then the number of layers or planes gets reduced, adjusting to the density gradient, and this self-organized change of order also shows up in the particle velocities. The experimental work that is reviewed here addresses dipolar colloidal particles confined by gravity on a solid substrate on which a set of pinning sites has been randomly distributed. The dynamics of the system is studied by tracking the trajectories of individual particles, and it is found that the mean square displacements of particles that are nearest neighbors of pinned particles are strongly affected by these defects. The influence of the pinning sites on the order and microscopic mechanism of phase transitions in two dimensions is investigated.     

Measurement of strong interaction parameters in antiprotonic hydrogen and deuterium

In the PS207 experiment at CERN, X-rays from antiprotonic hydrogen and deuterium have been measured at low pressure. The strong interaction shift and the broadening of the K _α transition in antiprotonic hydrogen were determined. Evidence was found for the individual hyperfine components of the protonium ground state. This revised version was published online in August 2006 with corrections to the Cover Date.     

Mean-field theory of discommensurations in ANNNI-systems

A method which allows a convenient treatment of domain walls and discommensurations (DCs) in spin lattices is used to determine the structure and the free energy of isolated discommensurations in ANNNI systems as well as their interaction energies,. Considered in detail are DCs in the antiphase structure (<2>-phase). The method makes use of an expansion of the mean field equations about the relevant (in the present case the antiphase-)fixed point. Analytical expressions are presented, exhibiting spatial oscillations of the DC-interaction which are shown to be related to the stable focus characteristics of the antiphase fixed point. As a consequence of these oscillations the transitions at the antiphase boundary are of first order everywhere except at themultiphase point.     

Determination of the ultraviolet absorbance and radioactivity of purine compounds separated by high-performance liquid chromatography. Application to metabolic flux rate analysis.

A double detection system for the determination of adenine metabolism in biological tissues using isocratic ion-pair reversed-phase chromatography is presented. Two isocratic ion-pair separations were used: (i) 10 mM NH4H2PO4, 2 mM tetrabutylammonium phosphate (PIC reagent A) and 18% acetonitrile for the determination of nucleotides and (ii) 50 mM KH2PO4, 1 mM PIC reagent A and 1% acetonitrile for the determination of monophosphorylated nucleotides, nucleosides and nucleobases. The parallel detection of ultraviolet absorbance at 254 nm and the radioactivity of separated purine compounds allows the detection of pool sizes and of the specific radioactivities in tracer kinetic experiments. The high-performance liquid chromatography methods were applied to the determination of flux rates during adenine nucleotide metabolism in suspensions of Ehrlich mouse ascites tumour cells. The pathways of adenine metabolism in cells during the proliferation and plateau phases of tumour growth were compared.     

Changes of nucleotide patterns in liver, muscle and blood during the growth of Ehrlich ascites cells: application of the reversed-phase and ion-pair reversed-phase high-performance liquid chromatography with radial compression column

The pool of purine compounds was analysed in liver, skeletal muscle and blood of mice during the growth of Ehrlich ascites tumour cells. Three fast isocratic high-performance liquid chromatographic methods were used. (1) Determination of nucleotides by an isocratic ion-pair reversed-phase chromatography with a 10 mM ammonium phosphate buffer containing acetonitrile and tetrabutylammonium phosphate. (2) Separation of nucleosides and nucleobases in cell extracts by a reversed-phase system with methanol and 50 mM potassium phosphate buffer as eluent. (3) Nucleosides and nucleobases in body fluids were analysed by a reversed-phase system with 10 mM potassium phosphate containing methanol. These methods allow the rapid determination of purine compounds in small biological samples from various cell types and body fluids, with high accuracy and sensitivity. The pool of cellular nucleotides increased during the exponential phase of tumour growth. Adenosine accumulated significantly in all tissues in the stationary phase of tumour growth.     

Analysis of plant phosphatidylcholines by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

The use of matrix-assisted laser desorption/ionization (MALDI) time-of-flight (TOF) mass spectrometry (MS) for the quantitative determination of phospholipid (PL) molecular species has been problematic, due primarily to the formation of multiple signals (corresponding to the molecular ion and other adducts) for some classes of PL. For example, analysis of phosphatidylcholine (PC) yielded signals that corresponded to protonated and sodiated molecules in the MALDI spectrum. The resulting spectral overlap among various molecular species (e.g. [PC(16:0/18:2) + Na] and [PC(18:2/18:3)]) made it impossible to ascertain their relative amounts using this technique. Other spectral ambiguities existed among different structural isomers, such as PC(18:1/18:1) and PC(18:0/18:2). We determined that molecular species could be resolved by MALDI-TOFMS by first removing the polar head (e.g. phosphocholine) from the phospholipid to effect production of only the sodiated molecules of the corresponding diacylglycerols (DAGs). Analysis of the resulting spectrum allowed unequivocal determination of the molecular species profile of PC from potato tuber and soybean. Estimation of fatty acid composition based on the molecular species determined by MALDI-TOFMS analysis agreed with that from GC-FID analysis. Post-source decay (PSD) was used to resolve standard isomers of PC (e.g. 18:1/18:1 vs. 18:0/18:2). Our results indicated that PSD is a useful approach for resolving structural isomers of PL molecular species.     

Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry of lipids: ionization and prompt fragmentation patterns

Ionization and prompt fragmentation patterns of triacylglycerols, phospholipids (PLs) and galactolipids were investigated using matrix-assisted laser desorption/ionization (MALDI). Positive ions of non-nitrogen-containing lipids appeared only in the sodiated form, while nitrogen-containing lipids were detected as both sodiated and protonated adducts. Lipids containing acidic hydroxyls were detected as multiple sodium adducts or deprotonated ions in the positive and negative modes, respectively, with the exception of phosphatidylcholines. The positive MALDI spectra of triacylglycerols contained prompt fragments equivalent to the loss of RCOO(-) from the neutral molecules. Prompt fragment ions [PL-polar head](+) were observed in the positive MALDI spectra of all phospholipids except phosphatidylcholines. The phosphatidylcholines produced only a minor positive fragment corresponding to the head group itself (m/z 184). Galactolipids did not undergo prompt fragmentation. Post-source decay (PSD) was used to examine the source of prompt fragments. PSD fragment patterns indicated that the lipid prompt fragment ions did not originate from the observed molecular ions (sodiated or protonated), and suggested that the prompt fragmentation followed the formation of highly unstable, probably protonated, precursor ions. Pathways leading to the formation of prompt fragment ions are proposed.     

Phase transitions in 2-dimensional systems of migrating orientable lattice defects

Phase transitions are studied in a system consisting of reorientating and migrating point defects in a two dimensional lattice. Due to the long range (r ^–2) nature of the dominant elastic interaction, surface effects are of central importance and have to be included. After diagonalizing the elastic interaction energy for defects characterized by arbitrary elastic dipole tensors the free energy of the system is minimized with respect to the tensor defect density (which describes the defect distribution in space and over a discrete number of orientations). Different types of phase transitions are obtained depending on the magnitude of the defect anisotropy. The phase below the paraelastic one is characterized for large by an anisotropic but homogeneous distribution, for small by an anisotropic and inhomogeneous distribution with a non linear space dependence. Similarities and differences with 3d results for=0 (or small) are discussed.