Wellenmechanische Absolutrechnungen an Molekülen und Atomsystemen mit der SCF?MO?LC(LCGO) Methode. IV. Das Äthylen (C2H4)

The C₂H₄ was investigated ab initio for the equilibrium distance of the centers, taking all 16 electrons into account, using the Allgemeines Programmsystem/SCF ? MO ? LC (LCGO ) Methode. A total energy of ?76.77 a.u. and an ionization energy of 10.55 eV were found.     

Quantum chemical investigations of the latent image formation

Having studied free silver clusters by quantum chemical calculations we now present a method to take into account the influence of a silver halide surface on adsorbed silver clusters. The model for the surface will be a silver halide cluster as frozen crystal section. The interactions are discussed in detail; a new bromide pseudopotential may be of special interest. Results with this method will be given in subsequent papers.     

Time spectroscopy in theA 1∑ u + state of Li2

We have determined effective cross-sections for resonant transfer of excitation energy from state-selected Li₂ molecules to ground state Li atoms $$Li_2 A\left( {\upsilon ',J'} \right) + Li2S \to Li_2 X\left( {\upsilon '',J''} \right) + Li2P$$ with two different experimental techniques. Absolute cross-sections were derived from lifetime measurements of 114 rotational levels of theA-state subject to resonant collisions which belong to vibrational statesv′=4, 5, 6, 7 and 11 of⁶Li₂ and⁷Li₂. Cross-sections amount to several thousand Ų dropping off sharply with a resonance half-width of about 16 cm^?1. The resonance behaviour of the collision cross-section inferred from lifetime data could be confirmed by a double resonance technique probing the number of excited atoms with a second laser while the first laser was scanned over the Li₂ X?A absorption band. Due to their high reliability our data prove a good basis for the test of theoretical models. In contrast to earlier investigations significant deviations were found to exist between the measured cross-sections and those predicted by the first-order dipole-dipole scattering theory.     

Wellenmechanische Absolutrechnungen an Molekülen und Atomsystemen mit der SCF?MO?LC(LCGO) Methode. VIII. Das System (Li2H)+

The (Li₂H)⁺ has been investigated ab initio in the linear configuration, with the H atom in the middle of the system, for five different distances R_LiH, taking all six electrons into account, using the Allgemeines Programmsystem/SCF? MO? LC(LCGO) Verfahren. A bond distance R_LiH of 3.14 a.u., a total energy of ?15.289 a.u., and an ionization energy of 15.1 eV were found. Comparing the results of SCF investigations, the formation energy of (Li₂H)⁺ from LiH and Li⁺ was computed to be 59.7 kcal/mole (2.58 eV). Using the energy curve near the minimum, a force constant for the symmetric vibration of k = 0.13777 × 10⁶ dyn/cm and a frequency ω = 577.9 cm^?1 were found.     

In situ tissue pathology from spatially encoded mass spectrometry classifiers visualized in real time through augmented reality

Integration between a hand-held mass spectrometry desorption probe based on picosecond infrared laser technology (PIRL-MS) and an optical surgical tracking system demonstrates in situ tissue pathology from point-sampled mass spectrometry data. Spatially encoded pathology classifications are displayed at the site of laser sampling as color-coded pixels in an augmented reality video feed of the surgical field of view. This is enabled by two-way communication between surgical navigation and mass spectrometry data analysis platforms through a custom-built interface. Performance of the system was evaluated using murine models of human cancers sampled in situ in the presence of body fluids with a technical pixel error of 1.0 ± 0.2 mm, suggesting a 84% or 92% (excluding one outlier) cancer type classification rate across different molecular models that distinguish cell-lines of each class of breast, brain, head and neck murine models. Further, through end-point immunohistochemical staining for DNA damage, cell death and neuronal viability, spatially encoded PIRL-MS sampling is shown to produce classifiable mass spectral data from living murine brain tissue, with levels of neuronal damage that are comparable to those induced by a surgical scalpel. This highlights the potential of spatially encoded PIRL-MS analysis for in vivo use during neurosurgical applications of cancer type determination or point-sampling in vivo tissue during tumor bed examination to assess cancer removal. The interface developed herein for the analysis and the display of spatially encoded PIRL-MS data can be adapted to other hand-held mass spectrometry analysis probes currently available.

Integration between a hand-held mass spectrometry desorption probe based on picosecond infrared laser technology (PIRL-MS) and an optical surgical tracking system demonstrates in situ tissue pathology from point-sampled mass spectrometry data.     

Energy-adjusted pseudopotentials for the rare earth elements

Nonrelativistic and quasirelativistic energy-adjusted pseudopotentials and optimized (7s6p5d)/[5s4p3d]-GTO valence basis sets for use in molecular calculations for fixed f-subconfigurations of the rare earth elements, La through Lu, have been generated. Atomic excitation and ionization energies from numerical HF, as well as SCF pseudopotential calculations using the derived basis sets, differ by less than 0.1 eV from numerical HF all-electron results. Corresponding values obtained from CI(SD), CEPA-1, as well as density functional calculations using the quasirelativistic pseudopotentials, are in reasonable agreement with experimental data.     

Pseudopotential calculations on Rb+2, Cs+2, RbH+, CsH+ and the mixed alkali dimer ions

Semi-empirical pseudopotentials are used in calculating the ground-state potentials curves for single valence-electron molecular ions. Very accurate results are obtained and a number of predictions given. The ionization energies of the neutral dimers are evaluated. A spectroscopic rule enables us to estimate the A ¹Σ⁺ state of KRb and RbCs.     

Phosphan-, Phosphit- und Phosphido-Komplexe des Vanadiums(V)

Phosphane, Phosphite, Phosphido, Complexes of Vanadium(V) Complex formation of tert-butylimidovanadium(V)trichloride ( 1 ) with phosphanes und phosphites has been studied. Syntheses of phosphidovanadium(V) compounds ^tC₄H₉N?VCp(NH^tC₄H₉)[P(SiMe₃)₂] and ^tC₄H₉N?VCp(NⁱProp₂)(PR₂) (R?SiMe₃, Ph) are described starting from the corresponding chlorovanadium(V) complexes. The reaction of 1 with silver hexafluorophosphate yields a bis(fluoro)phosphidovanadium(IV complex [(μ-PF₂)₂V₂Cl₂)(N^tC₄H₉)₂]; as primary intermediate product of the unknown redox reaction a cationic vanadium(V) complex [^tC₄H₉N?VCl₂ · PPh₃]⁺PF₆^? has been isolated. 1 reacts with an excess of diisopropylamine forming ^tC₄H₉N?V(NⁱProp₂)Cl₂ ( 16 ); in addition the following diisopropylamido-tert-butylimidovanadium(V) compounds ^tC₄H₉N?VCp(NⁱProp₂)Cl ( 3 ) and ^tC₄H₉N?V(NⁱProp₂)X₂ (X?CH₂CMe₃, O^tC₄H₉, CH₃COO) has been prepared. All compounds obtained are characterized by ¹H, ⁵¹V, ³¹P NMR spectroscopy. The X-ray diffraction analysis of 16 and 3 indicate a planar coordination sphere of the amido nitrogen atom.     

Concentration-Dependent Interactions of Amphiphilic PiB Derivative Metal Complexes with Amyloid Peptides Aβ and Amylin**

Metal chelates targeted to amyloid peptides are widely explored as diagnostic tools or therapeutic agents. The attachment of a metal complex to amyloid recognition units typically leads to a decrease in peptide affinity. We show here that by separating a macrocyclic GdL chelate and a PiB targeting unit with a long hydrophobic C10 linker, it is possible to attain nanomolar affinities for both Aβ_1-40 (K_d=4.4 nm ) and amylin (K_d=4.5 nm ), implicated, respectively in Alzheimer's disease and diabetes. The Scatchard analysis of surface plasmon resonance data obtained for a series of amphiphilic, PiB derivative GdL complexes indicate that their Aβ_1-40 or amylin binding affinity varies with their concentration, thus micellar aggregation state. The GdL chelates also affect peptide aggregation kinetics, as probed by thioflavin-T fluorescence assays. A 2D NMR study allowed identifying that the hydrophilic region of Aβ_1-40 is involved in the interaction between the monomer peptide and the Gd³⁺ complex. Finally, ex vivo biodistribution experiments were conducted in healthy mice by using ¹¹¹In labeled analogues. Their pancreatic uptake, ∼3 %ID g⁻¹, is promising to envisage amylin imaging in diabetic animals.