The core of zero-dimensional monomial ideals

The core of an ideal is the intersection of all its reductions. We describe the core of a zero-dimensional monomial ideal I as the largest monomial ideal contained in a general reduction of I. This provides a new interpretation of the core in the monomial case as well as an efficient algorithm for computing it. We relate the core to adjoints and first coefficient ideals, and in dimension two and three we give explicit formulas.     

Photopolymers for Rapid Prototyping of Soluble Mold Materials and Molding of Cellular Biomaterials

To substitute cross-linked photopolymers in rapid prototyping of mold materials and therefore extend the range of materials which can be casted, organo-soluble photopolymers were developed. Branched bisalkylacrylamides were suitable as base component for such formulations, due to their high reactivity, good mechanical properties, and excellent solubility of the formed polymers. These molding materials were used to prepare cellular biocompatible materials which could be used as bone replacement materials. Biocompatible crosslinkers based on methacrylates from hydrolyzed gelatine or lactic acid ethyleneglycol blockcopolymers and commercially available reactive diluents are the base components of such a formulation. Biocompatibility was investigated by osteoblast-like cells. Cellular biocompatible parts were obtained by thermal polymerization in soluble mould materials prepared by 3D-photoshaping.     

Influence of thermal and thermo-mechanical treatment

Two lipids with similar melting ranges but of different composition were analyzed using differential scanning calorimetry and X-ray diffraction. The lipids were processed via extrusion or were tempered at different temperatures; they were analyzed directly after extrusion and after storage at 40°C. Precirol ATO 5® showed high sensitivity to storage time and varied temperature exposure. Extrusion showed only marginal influences on the solid state. Melting peaks were narrower and shifted to higher temperatures in comparison to the untreated powder. Dynasan 114® was more robust, changes in the solid state could only be shown for samples treated above the melting range. Thus, Dynasan 114® is more appropriate for solid lipid extrusion of pharmaceutical products.     

An Ag-Atom in the 6-6 Subunit of a Zeolite: Model Calculations

Self-sensitisation of photo-oxygen evolution occurs in aqueous dispersions of silver zeolites. In presence of Cl^?, chlorine is the photoproduct in acidic medium, and the same type of self-sensitisation occurs. Self-sensitisation means that systems which are first insensitive to light of a certain wavelength become photo-active after they have been illuminated by light of higher energy. For a better understanding of silver zeolites, we have carried out EH-MO calculations on the 6–6 subunit (SBU) of a zeolite, on the 6–6 SBU with an Ag-atom in the center, on the 6–6 SBU with one Ag-atom in the center and one outside on top of the hexagon, and finally on another with one Ag-atom in the center and two Ag-atoms outside, each on top of a hexagon. The Ag⁰ in the cage of the 6–6 SBU is significantly polarized by the 6–6 SBU environment. The energy barrier to escape the 6–6 SBU is 0.8 eV for Ag⁰ and 0.5 eV for Ag⁺. The HOMO of the Ag(6–6 SBU) is a totally symmetric 5s* orbital and the LUMO is a 5p_z* type. 5p_z*←5s* electronic excitation reduces the energy barrier and allows an (Ag⁰)* to exit the 6–6 SBU, provided the excited-state lifetime is long enough. The MO picture predicts low-energy charge-transfer transitions from the zeolite framework to the 5s* orbital. The highest occupied orbitals of the zeolite framework are localized on the O-atoms. Interactions between an Ag-atom in the 6–6 SBU and one or two external Ag-atoms are discussed.     

Evaluation of a purge-and-trap injection system for capillary gas chromatography-microwave induced plasma-atomic emission spectrometry for the determination of volatile selenium compounds in water

A method is presented for the selective determination of the volatile selenium species dimethylselenide and dimethyldiselenide, using a commercially available purge-and-trap injection system coupled to capillary gas chromatography-microwave induced plasma-atomic emission spectrometry. The efficiency of the purging step was evaluated and the parameters affecting the purge and trap processes were optimized. The method was applied to the determination of volatile selenium compounds in lake water. Relative detection limits of 2ng/l for dimethylselenide and dimethyldiselenide, corresponding to an absolute detection limit of 10 pg, were achieved.     

A convenient two-step synthesis of 6-methylenesubstituted-4-trichloromethyl-2-methylsulfanyl pyrimidines

This work reports a two-step synthetic strategy to obtain a series of 6-methylenesubstituted-4-trichloromethyl-2-methylsulfanylpyrimidines from the cyclization of 5-bromo-4-methoxy-1,1,1-trichloro-pent-3-en-2-ones with 2-methyl-2-pseudothiourea sulfate, followed by nucleophilic substitution of 6-bromomethyl-4-trichloromethyl-2-methylsulfanylpyrimidine with a series of nucleophiles. Alternative strategies to obtain 6-halomethyl-4-trichloro[fluoro]methyl-2-methylsulfanyl pyrimidines have been addressed.     

Rapid field screening test for determination of 2,4,6-trinitrotoluene in water and soil with immunofiltration

A rapid field screening test for 2,4,6-trinitrotoluene (TNT) in water and soil is described. The immunofiltration assay is based on a simplified enzymelinked immunosorbent assay (ELISA) performed in a pre-packed portable device. Performance of the test was assayed in spiked water, methanolic soil extracts (dilution 1: 10) and natural water samples. A quantitative colour response to concentrations of TNT in the range of 1 to 30 g/l in water and 50 to 1000 g/kg in soil is demonstrated. The relative average standard deviations are 11.9% and 14.1%, respectively. High correlations between immunofiltration, ELISA and gas chromatography have been demonstrated. The cross reactivities of the antibody are comparable in both techniques.Dedicated to Professor Dr. Dieter Klockow on the occasion of his 60th birthday     

Kinetic studies of some substituted hexarhodium carbonyl clusters

Reactions of the halides X- (X- = chloride, bromide or iodide) with the substituted cluster Rh6(CO)15(PPh3) in oxygen-free chloroform lead to [Rh5(CO)14(PPh3)]-, Rh(CO)2(PPh3)2X and [Rh(CO)2X2]- in the molar ratios 2:1: approximately 13. Oxidation by the solvent is assumed to lead to most of the Rh(I) product, and the stoichiometry for reactions with I- can be defined as 4Rh6(CO)15(PPh3) + 27I- + 12CHCl3 --> 2[Rh5(CO)14(PPh3)]- + Rh(CO)2(PPh3)2I + 13[Rh(CO)2I2]- + 6C2H2Cl4 + 4CO + 12Cl-. This can be rationalized quite simply with the aid of a few generally justifiable assumptions. Rate constants for reactions with bromide increase to a limiting value with increasing [Br-] in a way that shows that breaking of one Rh-Rh bond, with an unusual closo to nido structural change, is rate determining. This opening of the cluster might be spontaneous or solvent induced. To complete the reaction, the bromide has to compete with the reverse nido to closo change. The same closo to nido change is also a major rate determining step for reactions with P(OPh)3 in oxygen-free solutions, and for reactions with bromide in oxygenated solutions in the presence of trifluoroacetic and some other acids. The limiting rates increase slightly with increasing basicity of the ligands P(p-XC6H4)3 along the series X = F3C, Cl, F, H and MeO. Activation parameters for these reactions are reported.     

Preparative and electrochemical investigations on the electron sponge behavior of cobalt telluride clusters: CO substitution in [Co11Te7(CO)10]n- ions (n=1, 2) by PMe2Ph and crystal structure of [Co11Te7(CO)5(PMe2Ph)5

The reaction of the cluster salts [Cp(2*) Nb(CO)(2)](n)[Co(11)Te(7)(CO)(10)] (Cp*=C(5)Me(5); n=1, 2) with excess PMe(2)Ph gave the neutral, dark brown clusters [Co(11)Te(7)(CO)(6)(PMe(2)Ph)(4)] (5) and [Co(11)Te(7)(CO)(5)(PMe(2)Ph)(5)] (6) with 147 metal valence electrons. The new compounds were characterized by IR spectroscopy, elemental analyses, and mass spectrometry. The molecular structure of 6 was determined by X-ray crystallography. Like its precursor anion, it consists of a pentagonal-prismatic [Co(11)Te(7)] core, but with a ligand sphere composed of five CO and five PMe(2)Ph ligands. Detailed electrochemical studies of both reactions reveal that a stepwise substitution of CO ligands in the initial cluster anions takes place leading to intermediate [Co(11)Te(7)(CO)(10-m)(PMe(2)Ph)(m)](n-) ions (m=1-5; n=1, 2). Each of these intermediates is distinguished by at least one oxidation and two reduction waves, giving rise to a total of 21 redox couples and 27 electroactive species. The electron sponge character of the new compounds is particularly pronounced in 5, which exhibits charges n between +1 and -4 corresponding to metal valence electron counts of between 146 and 151.