Present status of the Technological Laboratory at the LMU Munich

The Technological Laboratory of LMU is undergoing major changes. Most important of them is raising a DLC-Factory’s for diamond-like-carbon (DLC) foils production and a shutdown of the Hot-Lab Facility. Current Laboratory status and development plans are presented in this paper.     

Di-tert-butyldiphosphatetrahedrane as a Source of 1,2-Diphosphacyclobutadiene Ligands

Reactions of di-tert-butyldiphosphatetrahedrane ( 1 ) with cycloocta-1,5-diene- or anthracene-stabilised metalate anions of iron and cobalt consistently afford complexes of the rarely encountered 1,2-diphosphacyclobutadiene ligand, which have previously been very challenging synthetic targets. The subsequent reactivity of 1,2-diphosphacyclobutadiene cobaltates toward various electrophiles has also been investigated and is compared to reactions of related 1,3-diphosphacyclobutadiene complexes. The results highlight the distinct reactivity of such isomeric species, showing that the 1,2-isomers can act as precursors for previously unknown triphospholium ligands. The electronic structures of the new complexes were investigated by several methods, including NMR, EPR and Mößbauer spectroscopies as well as quantum chemical calculations.     

Physical boundaries within aggregates – differences between amorphous,para‐crystalline,and crystalline Structures

The structural properties of finely divided inorganic materials such as metal and metalloid oxides, silicates or carbonates of both synthetic and natural origin are compared by means of electron microscopy and tomography. The structure of the outer surfaces of various compact or compacted agglomerates may suggest some striking similarities between various amorphous silica on the one hand and crystalline titania and alumina on the other however the details of the interior fine structure are completely different. Inside of the crystalline aggregates of, for example, alumina and titania distinct grain boundaries between the inter‐grown primary crystallites exist. Also physical boundaries between different solid phases and crystalline/amorphous transitions in core/shell structures can occur. No physical grain or phase boundaries were found inside of synthetic amorphous silica or para‐crystalline carbon black thus, the aggregate is the constituent particle. Synthetic amorphous silica from different production technologies (fumed/pyrogenic, precipitated, aerogel, gel) may exhibit different macro‐morphology but distinct similarities of the amorphous silica networks. Computational studies on silica and titania underline the stability of constituent particles and aggregates as observed by means of TEM after dispersing the original materials by ultra‐sonication.     

Selector‐Induced Dynamic Deracemization of a Selectand‐Modified Tropos BIPHEPO‐Ligand: Application in the Organocatalyzed Asymmetric Double‐Aldol‐Reaction

Stereolabile interconverting catalysts open up the possibility of directing enantioselectivity in asymmetric synthesis by formation of diastereomeric complexes with chiral auxiliaries and deracemization. However, the stoichiometrically used auxilliaries can significantly limit the potential applications of such systems. We synthesized a new BIPHEPO tropos ligand containing achiral selectands in the backbone, which forms transient diastereomeric associates with amylose‐tris‐3,5‐dimethylphenyl carbamate as a selector and thus deracemizes. The enantiomerically enriched BIPHEPO obtained was successfully used in the organocatalytic asymmetric double aldol addition of substituted methyl ketones to form benzaldehyde. This strategy combines an on‐column deracemization with the high stereoinduction of chiral biarylphosphineoxides and opens up new possibilities in the field of self‐amplified asymmetric syntheses.     

Polymers with indan units

Cationic polymerisation of 1, 4-diisopropenyl benzene, 1, 4-(2-chloro-isopropyl)benzene and related compounds yields soluble polymers with repeating units of indan. High performance polymers with indan units are available via nucleophilic substitution of halogenated aromatic monomers containing a central indan element, which are synthesized from 1, 1, 3-trimethyl-3-phenylindan via Friedel-Crafts-reaction with corresponding halogenated acyl- and sulfonyl chlorides.     

Apparent diffusion coefficient of line scan diffusion image in normal prostate and prostate cancer—comparison with single-shot echo planner image

Purpose

This retrospective study was designed to evaluate the apparent diffusion coefficient (ADC) of line scan diffusion images (LSDI) in normal prostate and prostate cancer. Single-shot echo planner images (SS-EPI) were used for comparison.

Materials and Methods

Twenty prostate tumors were examined by conventional MRI in 14 patients prior to radical prostatectomy. All patients were examined with a 1.5-T MR imager (Signa CV/i ver. 9.1 GE Medical System Milwaukee, WI, USA). Diffusion-weighted MR imaging (DWI) using LSDI was performed with a pelvic phased-array coil, with b values of 5 and 800 s/mm². DWI using SS-EPI was performed with a body coil, with b values of 0 and 800 s/mm². The ADCs of each sequence for 14 normal prostate and 20 prostate cancers were histopathologically assessed. Signal-to-noise ratio (SNR) on DWI was estimated and compared for each sequence.

Results

The mean ADCs (±S.D.) of normal peripheral zones (PZ), transition zones (TZ) and cancer (in 10⁻³ mm²/s) that used LSDI were 1.42±0.12, 1.23±0.10 and 0.79±0.19, respectively. Those that used SS-EPI were 1.76±0.26, 1.38±0.20 and 1.05±0.27, respectively. Using unpaired t test (P<.05), we found a significant difference in each sequence between normal tissue (both PZ and TZ) and the cancer. Paired t test (P<.05) also registered a significant difference between LSDI and SS-EPI. Mean SNR for DWI using LSDI was 16.49±5.03, while the DWI using SS-EPI was 18.85±9.26. The difference between the SNR of each sequence was not statistically significant by paired t test.

Conclusion

We found that ADCs using LSDI and SS-EPI showed similar tendencies in the same patients. However, in all regions, LSDI ADCs had smaller standard deviations than SS-EPI ADCs.     

Peltier cooled PbSe double-heterostructure lasers for IR-gas spectroscopy

PbS−PbSe−PbS double-heterostructure lasers have been pulse-operated at about 200 K mounted on 4 stage thermoelectric coolers. Emitting at a wavelength of about 5.5 μm they could be used for NO gas spectroscopy. Operation temperatures of up to 230 K have been achieved with structures consisting ofn-type PbS substrates and epitaxial layers ofn-type PbSe and Tl dopedp-type PbS. The temperature dependence of the threshold current density and the emission wavelength of these DH-lasers was compared with PbSe-homojunction lasers. The use of a germanium etalon for a quick evaluation of the spectral quality of the emitted radiation is described.     

A study of high spin states in the transitional nucleus90Mo

The reaction⁵⁸Ni(³⁶Ar, 4p)⁹⁰Mo has been studied at a beam energy of 149 MeV. A detector array consisting of the OSIRIS spectrometer (12 Compton-suppressed Ge detectors), four charged-particleδE detectors and seven NE-213 neutron detectors at the VICKSI accelerator in Berlin has been used to measure the gamma radiation inγγ- and particle-γγ-coincidence mode. An additional Ge detector was placed at 162? to the beam direction to provide information on DCO ratios. The level scheme of⁹⁰Mo has been extended up to an excitation energy of about 12 MeV and probable spin 23?. Some 70 transitions and 40 levels have been newly identified. Spin assignments have been proposed on the basis of measured DCO ratios. Shell model calculations in a model space consisting of the proton 1f _5/2, 2p _3/2, 2p _1/2, and 1g _9/2 orbits and the neutron 2p _1/2, 1g _9/2, 1g _7/2, 2d _5/2, 2d _3/2, and 3s _1/2 orbits with some truncation were made for states above 9? and the predicted structure of these states is discussed.     

Time-of-flight studies of emission of μt from frozen hydrogen films

In recent TRIUMF experiments, a μ^- beam is stopped in a solid hydrogen film with a small fraction of T₂. The Ramsauer-Townsend (RT) mechanism allows μt to escape into vacuum with a few eV of energy. To study the emission process, an imaging system was used to determine the position of muon decays. Experimental histograms are in good agreement with a Monte Carlo simulation. This revised version was published online in August 2006 with corrections to the Cover Date.