Cylindrical spike model for the formation of diamondlike thin films by ion deposition

T /n_S of n_T rearrangements and n_S atoms in the spike volume as the crucial parameter characterizing the ability of a given ion–target combination to achieve complete rearrangement of the spike volume. n_T/n_S>1 is the optimum condition for diamondlike film growth. For aC films the ion energy dependence of n_T/n_S agrees well with the measured sp³ bond fraction. For Ar⁺-ion-assisted deposition of aC we find n_T/n_S>1 above 50 eV with no pronounced ion energy dependence. Furthermore, our model predicts optimum conditions for the formation of cubic boron nitride between 50 eV and 3 keV. Accepted: 14 October 1997     

High temperature crystallization of aluminum fluoride. Course,hydrolysis, solid phases.

A study for AlF₃ crystallization from water solution was performed in the temperature range 100 to 200°C.Four solid phases were found to be precipitated, AlF₃.3H₂O (up to ca.120°C, cubic α-AlF₃.H₂O (decomposition of AlF₃.3H₂O in suspension), hexagonal β -AlF₃.H₂O (direct from solution) and the hydroxyfluoride Al(OH,F)₃.H₂O with an F/Al ratio of ca. 2.5 (hydrolysis of AlF₃). The extent of hydrolysis was established as a function of the initial AlF₃ concentration.X-ray diffraction and thermogravimetric data for the monohydrates were given and differences between the two indicated.     

Macrophage-targeting oligopeptides from Mortierella alpina

The realm of natural products of early diverging fungi such as Mortierella species is largely unexplored. Herein, the nonribosomal peptide synthetase (NRPS) MalA catalysing the biosynthesis of the surface-active biosurfactants, malpinins, has been identified and biochemically characterised. The investigation of the substrate specificity of respective adenylation (A) domains indicated a substrate-tolerant enzyme with an unusual, inactive C-terminal NRPS module. Specificity-based precursor-directed biosynthesis yielded 20 new congeners produced by a single enzyme. Moreover, MalA incorporates artificial, click-functionalised amino acids which allowed postbiosynthetic coupling to a fluorophore. The fluorescent malpinin conjugate penetrates mammalian cell membranes via an phagocytosis-mediated mechanism, suggesting Mortierella oligopeptides as carrier peptides for directed cell targeting. The current study demonstrates substrate-specificity testing as a powerful tool to identify flexible NRPS modules and highlights basal fungi as reservoir for chemically tractable compounds in pharmaceutical applications.

Specificity profiling of a nonribosomal peptide synthetase of an early diverging fungus revealed high substrate flexibility. Feeding studies with click-functionalised amino acids enabled the production of fluorescent peptides targeting macrophages.     

Gold Nanoparticles as Effective ion Traps in Poly(dimethylsiloxane) Cross-Linked by Metal-Ligand Coordination

At this time, the development of advanced elastic dielectric materials for use in organic devices, particularly in organic field-effect transistors, is of considerable interest to the scientific community. In the present work, flexible poly(dimethylsiloxane) (PDMS) specimens cross-linked by means of ZnCl₂-bipyridine coordination with an addition of 0.001 wt. %, 0.0025 wt. %, 0.005 wt. %, 0.04 wt. %, 0.2 wt. %, and 0.4 wt. % of gold nanoparticles (AuNPs) were prepared in order to understand the effect of AuNPs on the electrical properties of the composite materials formed. The broadband dielectric spectroscopy measurements revealed one order of magnitude decrease in loss tangent, compared to the coordinated system, upon an introduction of 0.001 wt. % of AuNPs into the polymeric matrix. An introduction of AuNPs causes damping of conductivity within the low-temperature range investigated. These effects can be explained as a result of trapping the Cl⁻ counter ions by the nanoparticles. The study has shown that even a very low concentration of AuNPs (0.001 wt. %) still brings about effective trapping of Cl⁻ counter anions, therefore improving the dielectric properties of the investigated systems. The modification proposed reveals new perspectives for using AuNPs in polymers cross-linked by metal-ligand coordination systems.     

Thermodynamic equilibrium between locally excited and charge-transfer states through thermally activated charge transfer in 1-(pyren-2′-yl)-o-carborane

Reversible conversion between excited-states plays an important role in many photophysical phenomena. Using 1-(pyren-2′-yl)-o-carborane as a model, we studied the photoinduced reversible charge-transfer (CT) process and the thermodynamic equilibrium between the locally-excited (LE) state and CT state, by combining steady state, time-resolved, and temperature-dependent fluorescence spectroscopy, fs- and ns-transient absorption, and DFT and LR-TDDFT calculations. Our results show that the energy gaps and energy barriers between the LE, CT, and a non-emissive ‘mixed’ state of 1-(pyren-2′-yl)-o-carborane are very small, and all three excited states are accessible at room temperature. The internal-conversion and reverse internal-conversion between LE and CT states are significantly faster than the radiative decay, and the two states have the same lifetimes and are in thermodynamic equilibrium.

Reversible conversion between excited-states is key to many photophysical phenomena. We studied the equilibrium between LE and CT states by time-resolved and temperature-dependent fluorescence, fs- and ns-transient absorption, and LR-TDDFT calculations.     

Perturbed angular correlation study of radiation-induced defects in Rh metal

Radiation-induced defects are studied in cubic rhodium metal, using the local probe technique ‘Time differential perturbed angular correlation’ (TDPAC) at liquid N₂ temperature. Isochronal annealing was done at 300, 1073 and 1473 K temperatures. The irradiated sample showed two quadrupole interaction frequencies at 1150 and 93 MHz. The low frequency disappeared at room-temperature annealing, which was assigned to In trapped at a vacancy, whereas the higher frequency remained up to high temperatures and was attributed to In trapped at Rh–C complexes in the Rh matrix.     

Electron transfer in the reflection of atoms from metal surfaces

The resonance mechanism for positive and negative ionization of an atom reflected from a metal surface is treated in the time-dependent Hartree-Fock approximation assuming that the atom moves on its classical trajectory. A simple model is parameterized to describe 30–500 eV Na atoms reflected from tungsten, and the ionization probabilities are calculated by numerical integration of the equation of motion of the time evolution operator. Significant ionization can only occur if either the ionization level, or the affinity level of the atom crosses the Fermi level beyond the range of the atom-metal hopping interaction. On clean tungsten, the former situation applies, and the probability of positive ionization is nearly unity, and of negative ionization nearly zero.     

Nonparametric Estimation of Regression Functions in Point Process Models

We prove that the empirical L ²-risk minimizing estimator over some general type of sieve classes is universally, strongly consistent for the regression function in a class of point process models of Poissonian type (random sampling processes). The universal consistency result needs weak assumptions on the underlying distributions and regression functions. It applies in particular to neural net classes and to radial basis function nets. For the estimation of the intensity functions of a Poisson process a similar technique yields consistency of the sieved maximum likelihood estimator for some general sieve classes. This revised version was published online in August 2006 with corrections to the Cover Date.