A theoretical study of filter cake washing

A problem on filter cake washing assuming a geometrical model of the pore spaces, in which axial dispersion occurs in the flow channel and mass transfer through a resistance is taking place from the cross channels to the flow channel, is solved by deriving the differential equations and the auxiliary conditions corresponding to the geometrical model and solving the mathematical problem utilizing the Laplace transform and a method for its numerical inversion that utilizes positive values of the transform variable. The numerical results are checked by comparison with asymptotic expansions and by recalculating the results utilizing other values of the transform variable. The results are presented both numerically with four significant figures and graphically.     

Nitrogen quadrupole coupling in ethylisocyanate (CH3CH2NCO)

We measured and analyses the nitrogen hyperfine structure in the rotational spectrum of ethylisocyanate by MWFT-spectroscopy.     

Determination of binding geometry of DNA-adduct systems through induced circular dichroism

Many molecules (adducts) bound to DNA are postulated to intercalate between successive DNA base pairs. Linear dichroism (LD) has been used to yield information about the angular orientation of the adduct relative to the helix axis, but cannot probe the orientation within the plane perpendicular to this axis. A model is presented in this paper which predicts that the degree of alignment relative to a DNA fixed axis in this plane may be directly probed through the sign of the circular dichroism (CD) induced in an adduct transition of known polarization. Comparison with experimental data suggests that the method can complement LD studies in giving detailed information about the binding geometry.     

Determination of the neutron electric form factor from the reaction 3 He(e,e'n) at medium momentum transfer

The electric form factor of the neutron G_En has been determined in double polarized exclusive ³ He(e,e'n) scattering in quasi–elastic kinematics by measuring asymmetries A _⊥, A _∥ of the cross section with respect to helicity reversal of the electron, with the nuclear spin being oriented perpendicular to the momentum transfer q in case of A_⊥ and parallel in case of A_∥. The experiment was performed at the 855 MeV c. w. microtron MAMI at Mainz. The degree of polarization of the electron beam and of the gaseous ³ He target were each about 50%. Scattered electrons and neutrons were detected in coincidence by detector arrays covering large solid angles. Quasi–elastic scattering events were reconstructed from the measured electron scattering angles ϑ_e, φ_e and the neutron momentum vector p _n ^′ in the plane wave impulse approximation. We obtain the result <G _En>_{(0.27 < Q2c2/GeV2 < 0.5)}= 0.0334 ± 0.0033_stat± 0.0028_syst which is averaged over the indicated range of Q ², the squared momentum transfer. This G _En value is significantly smaller than measured from the D(e,e'n) reaction under similar kinematical conditions. To what extent final state interactions in ³He quench the G _En result is subject of calculations currently in progress elsewhere. Received: 29 April 1999     

Spectral properties and orientation of voltage-sensitive dyes in lipid membranes

Voltage-sensitive dyes are frequently used for probing variations in the electric potential across cell membranes. The dyes respond by changing their spectral properties: measured as shifts of wavelength of absorption or emission maxima or as changes of absorption or fluorescence intensity. Although such probes have been studied and used for decades, the mechanism behind their voltage sensitivity is still obscure. We ask whether the voltage response is due to electrochromism as a result of direct field interaction on the chromophore or to solvatochromism, which is the focus of this study, as result of changed environment or molecular alignment in the membrane. The spectral properties of three styryl dyes, di-4-ANEPPS, di-8-ANEPPS, and RH421, were investigated in solvents of varying polarity and in model membranes using spectroscopy. Using quantum mechanical calculations, the spectral dependence of monomer and dimer ANEPPS on solvent properties was modeled. Also, the kinetics of binding to lipid membranes and the binding geometry of the probe molecules were found relevant to address. The spectral properties of all three probes were found to be highly sensitive to the local environment, and the probes are oriented nearly parallel with the membrane normal. Slow binding kinetics and scattering in absorption spectra indicate, especially for di-8-ANEPPS, involvement of aggregation. On the basis of the experimental spectra and time-dependent density functional theory calculations, we find that aggregate formation may contribute to the blue-shifts seen for the dyes in decanol and when bound to membrane models. In conclusion, solvatochromic and other intermolecular interactions effects also need to be included when considering electrochromic response voltage-sensitive dyes.     

Initial DNA Interactions of the Binuclear Threading Intercalator Λ,Λ‐[μ‐bidppz(bipy)4Ru2]4+: An NMR Study with [d(CGCGAATTCGCG)]2

Binuclear polypyridine ruthenium compounds have been shown to slowly intercalate into DNA, following a fast initial binding on the DNA surface. For these compounds, intercalation requires threading of a bulky substituent, containing one Ru^II, through the DNA base‐pair stack, and the accompanying DNA duplex distortions are much more severe than with intercalation of mononuclear compounds. Structural understanding of the process of intercalation may greatly gain from a characterisation of the initial interactions between binuclear Ru^II compounds and DNA. We report a structural NMR study on the binuclear Ru^II intercalator Λ,Λ‐B (Λ,Λ‐[μ‐bidppz(bipy)₄Ru₂]⁴⁺; bidppz=11,11′‐bis(dipyrido[3,2‐a:2′,3′‐c]phenazinyl, bipy = 2,2′‐bipyridine) mixed with the palindromic DNA [d(CGCGAATTCGCG)]₂. Threading of Λ,Λ‐B depends on the presence and length of AT stretches in the DNA. Therefore, the latter was selected to promote initial binding, but due to the short stretch of AT base pairs, final intercalation is prevented. Structural calculations provide a model for the interaction: Λ,Λ‐B is trapped in a well‐defined surface‐bound state consisting of an eccentric minor‐groove binding. Most of the interaction enthalpy originates from electrostatic and van der Waals contacts, whereas intermolecular hydrogen bonds may help to define a unique position of Λ,Λ‐B. Molecular dynamics simulations show that this minor‐groove binding mode is stable on a nanosecond scale. To the best of our knowledge, this is the first structural study by NMR spectroscopy on a binuclear Ru compound bound to DNA. In the calculated structure, one of the positively charged Ru²⁺ moieties is near the central AATT region; this is favourable in view of potential intercalation as observed by optical methods for DNA with longer AT stretches. Circular dichroism (CD) spectroscopy suggests that a similar binding geometry is formed in mixtures of Λ,Λ‐B with natural calf thymus DNA. The present minor‐groove binding mode is proposed to represent the initial surface interactions of binuclear Ru^II compounds prior to intercalation into AT‐rich DNA.     

Single-step kinase inhibitor screening using a peptide-modified gold nanoparticle platform

Two complementary formats for kinase inhibitor screening are presented in which peptide-modified gold nanoparticles are enzymatically phosphorylated and rapidly aggregate on a surface or in solution by action of phosphospecific antibodies. The simple and rapid colourimetric response of the assays makes them an attractive approach for drug-screening applications.     

Theoretical Efficiency Limits of Photoelectrochemical CO2 Reduction: A Route-Dependent Thermodynamic Analysis

Solar-fuel formation via photoelectrochemical (PEC) routes using water and CO₂ as feedstock has attracted much attention. Most PEC CO₂ reduction studies have been focused on the development of novel photoactive materials; however, there is still a lack of understanding of the key limiting factors of this process. In this study, the theoretical limits of Solar-to-Fuel (STF) efficiencies of single- and dual-junction photo-absorbing materials are illustrated for single-step multi-electron CO₂ reduction into fuels including HCOO⁻, CO, CH₃OH and C₂H₅OH. It is also highlighted that STF efficiency depends on the route of two-step PEC CO₂ reduction process using CH₃OH as a model fuel. Finally, it is illustrated the beneficial role of alternative strategies such as dual-junction photo-absorbing electrodes, externally applied bias and subsequent reactor chambers on the maximum theoretical efficiencies of PEC CO₂ reduction.