Die Berechnung von Einelektronen-Integralen in der SCF-Xα-SW-Methode: I. Die Normierung

A normalization of the wave functions by means of the theoretical exact Multiple-Scattering-(MS)-formalism is discussed within the framework of the SCF-X-SW-method. For the atomic and extramolecular regions the integrals of normalization can be easily determined and the results can be described by the corresponding electronic charges. The calculation of the integral of the interatomic region is problematic. The needful volume integration is only necessary to theGreen's functions of the wave functions and can be solved by means of the residual theory. The further analytical calculation of the surface integrals leads to a complicated formalism which can be numerically evaluated.

     

Polymeric Catalysts

The present-day position in the field of polymeric catalysts is outlined. The following selected groups of polymeric catalysts are discussed: synthetic hydrolases, immobilized enzymes, phase-transfer catalysts, nucleophilically active bases, polymers with conjugated π-systems, photosensitizers, polymers as carriers for catalytically active metals or ions, and immobilized homogeneous catalysts. Polymeric catalysts have the following valuable properties: insoluble polymeric catalysts are readily separable from reaction solutions and can often be re-used without loss of activity; a hydrophobic matrix protects the organometallic active center from deactivation by oxygen and water; by fixation of finely divided metals on an ion exchanger, multistage reactions may be effected successively in one reactor. Polymeric carriers may influence the catalytic properties; for example, in the case of immobilized enzymes on polyionic carriers the pH of the activity maximum may be shifted.     

Copper(II) Complexes of ω‐Hydroxy‐Functionalized N‐Salicylidenehydrazides show pH‐Controlled Switching between Dicationic Dimers and Neutral One‐Dimensional Coordination Polymers

New copper(II) complexes of the hydrazone ligands H₂salhyhb, H₂salhyhp, and H₂salhyhh, derived from salicylaldehyde and ω‐hydroxy carbonic acid hydrazides, have been synthesized and physically characterized. Two fundamental structures were found in solid state depending on the pH‐value of the reaction solution. Acidic conditions lead to the formation of the di‐μ‐phenoxo‐bridged dicationic complex dimers [{Cu(Hsalhyhb)}₂]²⁺ ( 1a ), [{Cu(Hsalhyhp)}₂]²⁺ ( 2a ), and [{Cu(Hsalhyhh)}₂]²⁺ ( 3a ), isolated as perchlorate salts. The dimeric complexes show strong antiferromagnetic coupling with J = ?399 ( 1a ), ?410 ( 2a ), and ?311 cm^?1 ( 3a ). Higher pH‐values resulted in the aggregation of neutral copper ligand fragments to the one‐dimensional coordination polymers [{Cu(salhyhb)}_n] ( 1b ), [{Cu(salhyhp)}_n] ( 2b ), and [{Cu(salhyhh)}_n] ( 3b ). 3b has been examined by means of X‐ray crystallography and represents the first example of a structurally characterized neutral copper(II) N‐salicylidenehydrazide complex without additional ligands. The magnetic interactions in the polymers are also antiferromagnetic with J = ?125 ( 1b ), ?136 ( 2b ), and ?148 cm^?1 ( 3b ), but strongly reduced compared to the corresponding dimeric complexes. The two basic structure types can be reversibly interconverted simply by pH‐control.     

Channel activity of a viral transmembrane peptide in micro-BLMs: Vpu(1-32) from HIV-1

We report for the first time on pore-suspending lipid bilayers, which we call micro-black lipid membranes (micro-BLMs), based on a highly ordered macroporous silicon array. Micro-BLMs were established by first functionalizing the backside porous silicon surface with gold and then chemisorbing 1,2-dipalmitoyl-sn-glycero-3-phosphothioethanol followed by spreading 1,2-diphytanoyl-sn-glycero-3-phosphocholine dissolved in n-decane. Impedance spectroscopy revealed the formation of single lipid bilayers confirmed by a mean specific capacitance of 0.6 +/- 0.2 microF/cm2. Membrane resistances were in the G omega-regime and beyond. The potential of the system for single channel recordings was demonstrated by inserting the transmembrane domain of the HIV-1 accessory peptide Vpu(1-32), which forms helix bundles with characteristic opening states. We elucidated different amilorides as potential drugs to inhibit channel activity of Vpu.     

Über die Reaktionen von Guanidin bzw. Harnstoff mit Cyanhydrinen

Action of guanidine or urea on cyclohexanone-, cyclopentanone-, cycloheptanone-and acetonecyanohydrine3 a?3 d generates very different products: 3 a reacts with guanidine inDMF to yield 1,3-diazaspiro[4.5]decane-2,4-diimine (5 a). Heating the components without solvent affords 7,14-diazadispiro[5.1.5.2]pentadecan-15-one(7)^15–17, the guanidine not participating in the reaction; similarly3 b is transformed by guanidine to a pentacyclic dispirocompound (possible formulae19 and20), whereas3 d reacts to give 3,3,5,5-tetramethylpiperazine-2,6-dione(21)¹⁹. In 3-pentanone guanidine-cyanide condensates itself to give 2,4-diamino-triazine (22)^{21, 22}. Action of urea on3 a?3 d yields the 4-imino-1,3-diazaspiroalkan-2-ones6 a?6 c and the 4-imino-5,5-dimethylimidazolidin-2-one6 d ^6–8 resp. If the reaction of urea and3 d is carried out inDMF, however, 5,5-dimethyl-4-ureido-3-imidazolin-2-one (28) (or the tautomeric carbamoyliminoimidazolidinone27) is produced. The structures of the compounds prepared are proved by NMR-, IR- and mass spectra.     

Simultaneous determination of capecitabine and its metabolite 5-fluorouracil by column switching and liquid chromatographic/tandem mass spectrometry

A liquid chromatographic/tandem mass spectrometric method was developed and validated for the quantitation of capecitabine and its metabolite 5-fluorouracil in human plasma. The simultaneous determination of both analytes was achieved by a column switching method using a trapping column and two analytical columns with different stationary phases. Isocratic elution was used for the separation of capecitabine on a C18 column whereas 5-fluorouracil was separated using gradient elution on an non-polar carbon phase. The calibration curves were linear for both compounds with a correlation factor (R2) > 0.9993 for 5-fluorouracil and >0.9942 for capecitabine. The assay was validated in the concentration range 5.00-1000 ng ml(-1) for both compounds. The intra-day precision was better than 10% for 5-fluorouracil and better than 11% for capecitabine whereas the inter-day precision was better than 8% for 5-fluorouracil and better than 14% for capecitabine.     

On strong summability of multiple Fourier series and smoothness properties of functions

_n —n- — ƒ()L _v (T _n ), 1f, - -. -.     

Über substituierte 1,6-Dihydro-1,3,5-triazin-2,4-diamine, 1′,5′,6′,7′-Tetrahydrospiro[cyclopentan-1,4′-cyclopentapyrimidin]-2′(3′ H)-imine und das 6-Phenyl-2,4-pyrimidindiamin

Guanidine reacts with cyclohexanone, cycloheptanone, acetone and 3-pentanone, resp., in a molar ratio 2∶1 to give the 1,3,5-triazaspiro[5.5]undeca-and [5.6]dodeca-1,3-dien-2,4-diamines3 a and3 b resp. and the 6,6-dimethylresp. diethyl-1,6-dihydro-1,3,5-triazin-2,4-diamines3 d and3 e resp. On the contrary, action of guanidine on cyclopentanone yields not3 c, but the 1′,5′,7′-tetrahydrospiro[cyclopentane-1,4′-cyclopentapyrimidine]-2′(3′H)-imines2 c, 5 c and6 c resp., which are 1∶2- and 1∶3-condensates. Phenylacetone is transformed by guanidine (1∶2) to give 6-phenyl-2,4-pyrimidindiamine (8 f). The structure of the compounds cited is proved by NMR-, IR-, and (partially) mass spectra. The different courses of the formation of3 a, b, d, e, 2 c, 5 c and6 c resp. and8 f are also discussed. The structural formulae of some additional bases, which were synthesized from guanidine and cyclopentanone, 3-pentanone and phenylacetone resp. could not be established.     

Zur Längenberechnung der Torsion äusserer Potenzen

Let R be a noetherian ring of dimension d and M a finitely generated R-module of homologic dimension less or equal to one. Assume further that M has a rank r, which equals d or (in case d>0) d?1 and that the r-th Fitting-ideal \(\vartheta _r (M)\) of M has grade ?d. Then the torsion-submodule of the d-th exterior power of M and the module \(R/\vartheta _r (M)\) are equivalent.     

A short note on Dedekind sums

We will give a new proof for the fact that the values of Dedekind sums are dense on the real line.