Electron binding motifs of (H2O)n- clusters

It is has been established that the excess electrons in small (i.e., n < or = 7) (H2O)n- clusters are bound in the dipole field of the neutral cluster and, thus, exist as surface states. However, the motifs for the binding of an excess electron to larger water clusters remain the subject of considerable debate. The prevailing view is that electrostatic interactions with the "free" OH bonds of the cluster dominate the binding of the excess electron in both small and large clusters. In the present study, a quantum Drude model is used to study selected (H2O)n- clusters in the n = 12-24 size range with the goal of elucidating different possible binding motifs. In addition to the known surface and cavity states, we identify a new binding motif, where the excess electron permeates the hydrogen-bonding network. It is found that electrostatic interactions dominate the binding of the excess electron only for isomers with large dipole moments, whereas in isomers without large dipole moments polarization and correlation effects dominate. Remarkably, for the network-permeating states, the excess electron binds even in the absence of electrostatic interactions.     

Application of the Lattice-Boltzmann Method for Particle-laden Flows: Point-particles and Fully Resolved Particles

The Lattice-Boltzmann-Method (LBM) is a powerful and robust approach for calculating fluid flows over or through complex geometries. This method was further developed for allowing the calculation of several problems relevant to dispersed particle-laden flows. For that purpose two approaches have been developed. The first approach concerns the coupling of the LBM with a classical Lagrangian procedure where the particles are considered as point-masses and hence the particles and the flow around them are numerically not resolved. As an example of use, the flow through a single pore representing a single element of a filter medium was considered and the deposition of nano-scale particles was simulated. The temporal evolution of the deposit structures is visualised and both the filtration efficiency and the pressure drop are simulated and compared with measurements. In the second developed LBM-approach, the particles are fully resolved by the numerical grid whereby the flow around particles is also captured and it is possible to effectively calculate forces on complex particles from the bounce-back boundary condition. As a case study the flow around spherical agglomerates consisting of poly-sized spherical primary particles with sintering contact is examined. Using local grid refinement and curved wall boundary condition, accurate simulations of the drag coefficient of such complex particles were performed. Especially the effect of porosity on the drag was analysed. Moreover, the flow about very porous fractal flocks, generated by a random process, was simulated for different flock size and fractal dimension. The drag coefficients resulting from LBM simulations were compared to theoretical results for Stokes flow. Finally, scenarios with moving particles were considered. First, the sedimentation of a single particle towards a plane wall was simulated and compared with measurements for validation. Secondly, the temporal sedimentation of a cluster of 13 particles was studied. Here, the primary particles were allowed to stick together and form agglomerates. This research will be the basis for further analysing agglomerate formation in laminar and turbulent flows.     

New Generation of Phase-Doppler Instruments for particle velocity,size and concentration measurements

Phase-Doppler anemometry (PDA) is applied for particle size, velocity and concentration measurements in two-phase or multi-phase flows of ever increasing complexity. For accurate measurements the experimenter must be provided with software and hardware which permit an optimal layout of the PDA optics for a given application, reliable detection of signals over a wide particle diameter range, accurate determination of particle concentration and precise discrimination between particles of different composition. Recent work at LSTM, Erlangen, has been directed to developing a complete PDA package for the above purposes. Progress in this direction is summarized in this paper.     

Resonance states of atomic Di-anions

Metastable states of O (2-), S (2-), B (2-), and Al (2-) are studied in the framework of the complex absorbing potential method using highly correlated multireference configuration interaction wave functions. The first row species O (2-) and B (2-) are found to be broad resonances showing widths of roughly 1.7 eV, whereas the second row systems S (2-) and Al (2-) possess widths clearly smaller than 1 eV. The identified resonance states are compared to the fundamental H (2-) resonance, and the relationship with recent electron scattering experiments is discussed.     

Al(CN)6(3-) and Al(NC)6(3-) trianions

At this time the smallest trianions observed in the gas phase are fluorinated fullerenes and large organic ring systems with attached sulfonic acid groups. Considerably smaller trianions have been predicted to be sufficiently stable for observation in mass spectrometers, but have not yet been detected. Here two isomers of the aluminium cyanide trianion, Al(CN)(6)(3-) and Al(NC)(6)(3-), are studied using ab initio methods. These two isomers are predicted to be electronically stable and to show substantial barriers with respect to dissociation of CN(-) units. Thus, the investigated trianions hit a sweat-spot regarding the possibility of detection, as they are by far more robust with respect to dissociation than alkali halide trianions, while at the same time materials from which these trianions can at least in principle be formed are much more readily available than those needed for producing small covalently bound trianions.     

Downstream processing of antibodies: Single-stage versus multi-stage aqueous two-phase extraction

Single-stage and multi-stage strategies have been evaluated and compared for the purification of human antibodies using liquid–liquid extraction in aqueous two-phase systems (ATPSs) composed of polyethylene glycol 3350 (PEG 3350), dextran, and triethylene glycol diglutaric acid (TEG-COOH). The performance of single-stage extraction systems was firstly investigated by studying the effect of pH, TEG-COOH concentration and volume ratio on the partitioning of the different components of a Chinese hamster ovary (CHO) cells supernatant. It was observed that lower pH values and high TEG-COOH concentrations favoured the selective extraction of human immunoglobulin G (IgG) to the PEG-rich phase. Higher recovery yields, purities and percentage of contaminants removal were always achieved in the presence of the ligand, TEG-COOH. The extraction of IgG could be enhanced using higher volume ratios, however with a significant decrease in both purity and percentage of contaminants removal. The best single-stage extraction conditions were achieved for an ATPS containing 1.3% (w/w) TEG-COOH with a volume ratio of 2.2, which allowed the recovery of 96% of IgG in the PEG-rich phase with a final IgG concentration of 0.21 mg/mL, a protein purity of 87% and a total purity of 43%. In order to enhance simultaneously both recovery yield and purity, a four stage cross-current operation was simulated and the corresponding liquid–liquid equilibrium (LLE) data determined. A predicted optimised scheme of a counter-current multi-stage aqueous two-phase extraction was hence described. IgG can be purified in the PEG-rich top phase with a final recovery yield of 95%, a final concentration of 1.04 mg/mL and a protein purity of 93%, if a PEG/dextran ATPS containing 1.3% (w/w) TEG-COOH, 5 stages and volume ratio of 0.4 are used. Moreover, according to the LLE data of all CHO cells supernatant components, it was possible to observe that most of the cells supernatant contaminants can be removed during this extraction step leading to a final total purity of about 85%.     

Quantum Drude oscillator model for describing the interaction of excess electrons with water clusters: an application to (H2O)13(-)

Cluster anions for which the excess electron occupies an extended nonvalence orbital can be described by use of a model Hamiltonian employing quantum Drude oscillators to represent the polarizable charge distributions of the monomers. In this work, a Drude model for water cluster anions is described and used to investigate the (H2O)13(-) cluster. Several low-energy isomers are characterized, and the finite-temperature properties of the cluster are investigated by means of parallel tempering Monte Carlo simulations. Two structural motifs, one with double-acceptor water monomers and the other with four-membered rings of double-acceptor single-donor monomers with four free OH groups pointed in the same direction, are found to lead to large (approximately > eV) electron binding energies. The distributions of the computed vertical detachment energies qualitatively reproduce the experimentally measured photoelectron spectrum, and our simulations indicate that both of the main peaks in the measured spectrum derive from several isomers.     

ChemInform Abstract: Instability of the Al42‐ “All‐Metal Aromatic” Ion and Its Implications.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.