Preparation and properties of insoluble films of cyclodextrin condensation polymers

The preparation and properties of smooth and stable films of cyclodextrin polymers are described. The commercially available water soluble prepolymers of-, -, and-cyclodextrin of low molecular masses were crosslinked with glutaric dialdehyde. Side-chain unreacted aldehyde groups were reduced with sodium borohydride. For the-cyclodextrin polymer, optimum film performance was found for a 1:10 mass ratio of glutaric dialdehyde to prepolymer, which corresponds to a molar ratio of glutaric dialdehyde to cyclodextrin units of about 1.75: 1. Such films, of thickness 2.4 µm, were prepared on metallic or glassy-carbon substrates for characterization by scanning-electron microscopy, and for studies with the electrochemical quartz-crystal microbalance.     

Über eine zum Kreisproblem verwandte Summe

An equivalent form of the classical circle problem is the unproved conjecture (3) . In this note the corresponding conjecture with _k (.) (the 1-periodic Bernoulli polynomials of orderk2) instead of ₁(.) is settled in an affirmative way (even with =0). Moreover, a generalized sum (6) is estimated by means of an analogue to a classical result due tovan der Corput.     

High-performance flow atomic spectrometry: New nebulization techniques,on-line speciation and on-line sample pretreatment

An interface-free combination of HPLC separation techniques and methods for element determination by atomic spectrometry can be achieved by hydraulic high-pressure nebulization (HHPN). With high-temperature HHPN (300 ( degrees )C) super heated liquids can be nebulized providing aerosol yields of up to 90% in flame AAS. This new nebulization method combines the advantages of HHPN and thermospray techniques (very small aerosol droplets, high aerosol yield, nebulization of saturated salt solutions).     

Photoelectron spectroscopy of isolated multiply negatively charged oligonucleotides

Ultraviolet photoelectron spectroscopy in an ion beam was used to investigate the electronic properties of isolated DNA oligonucleotides [dA(5)-4H](4-) and [dT(5)-4H](4-), carrying four excess negative charges. We find the fourth adiabatic electron affinity to be slightly negative for [dA(5)-4H](4-), while it is positive for [dT(5)-4H](4-). This implies a significant influence of the base composition on energetics, which is in turn relevant for analytic applications and also for charge transport properties.     

Thermal synthesis of the optical pure pentapeptide derivative Z-(L)-Ala-(L)-Phe-Gly-(L)-Phe-Gly-OMe

The pentapeptide Z-(L)-Ala-(L)-Phe-Gly-(L)-Phe-Gly-OMe was obtained by reacting the activated dipeptide derivative Z-(L)-Ala-(L)-Phe-OPcp with the amino peptide derivative TFA·H-Gly-(L)-Phe-Gly-OMe at 100–105°C under reduced pressure (10^?2-10-^?3 Torr) without using solvents. The product obtained by bulk condensation showed no racemization, whereas the product obtained by a matrix mediated condensation contained 5,5 % diastereomer Z-(L)-Ala-(D)-Phe-Gly-(L)-Phe-Gly-OMe. Separation of diastereomers was achieved by HPLC on a silicagel column.     

Synthesis,Reactivity, and Structural Characterization of Dioxovanadium(V) Complexes with Tridentate Schiff Base Ligand: Vanadium Complexes in Supramolecular Networks

The synthesis, characterization and crystal structure analysis of the ammonium salt of the dioxovanadium(V) complex NH₄[VO₂(salhyph)] with the tridentate Schiff base ligand derived from salicylaldehyde and benzoic acid hydrazide (H₂salhyph) is reported. NH₄[VO₂(salhyph)] crystallizes in the monoclinic space group Pn with a = 708.8(2), b = 1444.3(3), c = 717.1(2) pm and β = 101.09(2)°. The vanadium atom of the dioxovanadium(V) moiety has a distorted square‐pyramidal coordination geometry. Extensive hydrogen bonding is observed between the ammonium cation and the oxygen atoms coordinated to the vanadium atom yielding to a two‐dimensional network, where the complex anions are arranged in a bilayer. Additional crystal packing within the bilayer appears to be controlled mostly by π stacking between the aromatic rings of the ligand. The reactions of NH₄[VO₂(salhyph)] with several proton acidic compounds including water, methanol, and proton acids lead to neutral monooxovanadium(V) and dioxovanadium(V) complexes ([VO₂(Hsalhyph)], [V₂O₃(salhyph)₂] and [VO(OMe)(salhyph)(HOMe)]).     

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.