Metal- and ligand-directed one-pot syntheses,crystal structures,and properties of novel oxo-centered tetra- and hexametallic clusters

Starting from closely related metal-ligand combinations, completely different oligomeric metal clusters are synthesized. Whereas, picoline-tetrazolylamide HL(1) (1) and zinc or nickel acetate afforded [2x2] grids [M(4)(L(1))(8)] (2), slightly different N-(2-methylthiazole-5-yl)-thiazole-2-carboxamide HL(2) (5 a) and nickel acetate yielded the monometallic complex [Ni(L(2))(2)(OH(2))(2)] (6). In contrast, reaction of 5 a with zinc acetate produced the tetrametallic zinc cluster [Zn(4)O(L(2))(4)(OAc)(2)] (7). Even more surprising, when 3-methyl-substituted HL(3) (5 b) instead of 2-methyl-substituted HL(2) (5 a) was allowed to react under identical conditions with zinc acetate, the cluster [Zn(4)O(L(3))(4)Cl(2)] (8) crystallized from dichloromethane. Clusters 7 and 8 are isostructural. As for 7, in 8 two of the edges of the tetrahedron of zinc ions are doubly bridged, two are singly bridged, and the other two are nonbridged. On the other hand, when iron(II) acetate under aerobic conditions was allowed to react with 5 a, the unprecedented complex [[Fe(3)O(L(2))(2)(OAc)(4)](2)O] (9) was isolated. Cluster 9 is composed of two trimetallic, triangular mu(3)-O(2-)-centered [Fe(3)O(L(2))(2)(OAc)(4)](+) modules, linked by an almost linear mu(2)-O(2-) bridge. The M?ssbauer spectrum together with cyclic voltammetric and square-wave voltammetric measurements of 9 are reported, and 6-9 were characterized unequivocally by single-crystal X-ray structure analyses.     

Synthese neuer Aminofluorsilane,sowie Alkoxylierung von Bis (trimethylsilyl)-amino-fluorsilanen

The reaction of aminofluorsilanes of the type (R=H,F) (Me ₃Si)₂N?SiF₂R with two moles of ammonia, or of a mono- or dialkylamine, yields the corresponding amino-compounds, e.g. (Me ₃Si)₂N?Si(F)R?NH₂, (Me ₃Si)₂N?Si(F)R?NHR′ and (Me ₃Si)₂N?Si(F)R?NR₂′ (R′=Me, Et). Analogous products are obtained by reaction of the aminofluorosilanes with lithium salts of amines with bulky organic substituents in a 1 : 1 molar ratio. Alkoxy- and aryloxyaminofluorosilanes are prepared by the reaction of sodium alcoholates and sodium phenolate with (Me ₃Si)₂N?Si(F₂)R (R=H, C₂H₃, C₂H₅, C₆H₅). The i.r.-, mass-,¹H- and¹⁹F-NMR spectra of the above compounds are reported.     

ROTATIONAL DIFFUSION OF RHODAMINE 6G IN HUMAN BLOOD SERUM

Abstract —The time-dependent rotational relaxation of Rhodamine 6G in fresh and dried human blood serum was investigated using picosecond phasefluorometry. Measurements were also carried out in aqueous solutions of amino acids, glucose, urea, and bovine serum albumin to evaluate our model for the interactions. It is shown that the distribution of Rhodamine 6G between the aqueous and the protein phase of the blood serum strongly depends on protein concentration and temperature.     

Development of a chemical vapor sensor using piezoelectric quartz crystals with coated unusual lipids

Piezoelectric quartz crystal sensors were developed using lipids with various properties for highly sensitive detection of chemical vapors. Lipids with varying lengths of alkyl chains were coated onto 10 MHz AT-cut quartz crystal resonators and the response of these modified crystals to chemical vapors were measured. It was shown that hydrophilic compounds, such as ethanol and methanol, could be recognized efficiently by lipids having shorter alkyl chains, whereas lipids with longer alkyl chains showed affinity to more hydrophobic vapors, such as toluene, hexane and cyclohexane. Frequency changes caused by adsorption of alcohols could be enhanced when cholesterol was co-immobilized in the lipid layer. To confirm the assumption that the sensor-response might be affected by the properties of lipids derived from acyl chains, we have examined the effects of two types of newly synthesized unusual lipids on sensor response. When lipids having one triple bond each at different positions on their alkyl chains were coated onto quartz crystals separately, lower responses were observed compared to responses obtained for a sensor with immobilized, saturated phosphatidylcholine. Lipids containing -branched acyl chains, however, showed good affinity for organic vapors, and sensor responses improved 4–5-fold. Moreover, these sensors were shown to have sensitivity of the same order as the humans' sense of smell (10⁻⁵–10⁻⁶ w/w in liquid paraffin) when measured using standard odorants (isovaleric acid, skatole, etc.) for an olfactometry established in Japan.     

Yellowing and IR-changes of spruce wood as result of UV-irradiation

The yellowing and IR-changes of spruce wood as a result of UV-irradiation were studied using two different types of xenon lamps (lambda>300 nm; I(o)=50 mW cm(-2) and lambda>280 nm; I(o)=17.5 mW cm(-2)). Changes in the IR spectra as well as the yellowing of the irradiated wood surfaces show the influence of UV light on the wood modules. The UV-irradiation (72 h; lambda>300 nm; I(o)=50 mW cm(-2)) decreased the lignin content on the surface by up to 20% of the original values. The colour difference of yellowing (deltaE) exhibited a systematic trend to higher values with increasing irradiation time. Our results show that the photoyellowing (UV-Vis detection) correlates very well with lignin degradation (IR detection). This result is in agreement with the quinone formation as the chromophoric reaction product of lignin decay. The degradation, yellowing, and oxidation kinetics differed only little using different light sources. The absorbed light intensity, which depends on wavelength, the intensity distribution of the light source and the absorption spectrum of lignin, influenced the degradation rate. Under the current experimental conditions, the absorption spectrum of lignin was the most important factor. Therefore, irradiation with lambda>280 nm is useful for rapidly monitoring the UV-degradation of wood     

Generation of new landomycins by combinatorial biosynthetic manipulation of the LndGT4 gene of the landomycin E cluster in S. globisporus

A 3 kb DNA fragment from the Streptomyces globisporus 1912 landomycin E (LaE) biosynthetic gene cluster (lnd) was completely sequenced. Three open reading frames were identified, lndGT4, lndZ4, and lndZ5, whose probable translation products resemble a glycosyltransferase, a reductase, and a hydroxylase, respectively. Studies of generated mutants from disruption and complementation experiments involving the lndGT4 gene allowed us to determine that LndGT4 controls the terminal L-rhodinose sugar attachment during LaE biosynthesis and that LndZ4/LndZ5 are responsible for the unique C11-hydroxylation of the landomycins. Generation of the novel landomycins F, G, and H in the course of these studies provided evidence for the flexibility of lnd glycosyltransferases toward their acceptor substrates and a basis for initial structure-activity relationships within the landomycin family of antibiotics.     

Cycloadditionsreaktionen der aminofluorsilane

Aminofluorsilanes are obtained by the reaction of fluorosilanes with the lithium salts of the corresponding amines. The reaction of aminofluorosilanes with butyllithium in a (2 + 2)cyclo addition reaction leads to the formation of fourmembered silicon-nitrogen ring compounds. The mechanism of the reaction is discussed, the mass, ¹H and ¹⁹F NMR spectra of the compounds are reported.     

Exact convergence rates for the bounded law of the iterated logarithm in Hilbert space

Summary In a previous paper we obtained upper and lower class type results refining the bounded LIL for sums of iid Hilbert space valued mean zero random variables, whose covariance operators satisfy certain regularity assumptions. We now establish precise convergence rates for the bounded LIL in the non-regular case. It turns out that the almost sure behavior in this case is entirely different from the behavior in the previous situation.Supported in part by NSF Grant DMS 90-05804     

Influence of solvents on the insertion of methacrolein into zirconacyclopropenes

The reaction of Cp₂Zr(L)(η²-Me₃SiC₂) (L = THF, py) with equimolar amounts of H₂C = CMe-CHO at room temperature depends strongly on the ligands L and the solvents that are used. With L = THF, in the THF solution the insertion product

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1 was isolated, whereas by conducting the reaction in n-hexane solution an alkyne substitution with 1,4-coordination of the methacrolein takes place and the binuclear complex [

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2 was obtained. In conttrast, with L = py (a stronger ligand) only a 1:1 ratio of 1 and 2 was observed in both THF and in n-hexane. At 50°C complex 1 was converted into 2 and the alkyne was eliminated quantitatively.

Complexes 1 and 2 were characterized by IR and NMR spectroscopical measurements and 1 by an additional X-ray structure determination.     

Fluorsilylsubstituierte N,N- und N,O-bis(trimethylsilyl)-hydroxylamine

Fluoro- und aminofluoro-silanes react with the lithium salt of N,O-bis(trimethylsilyl)hydroxylamine under LiF elimination and substitution. Alkyl- and amino-fluorosilanes give O-fluorosilyl-N,N-bis(trimethylsilyl)hydroxylamines, arylfluorosilanes give N-fluorosilyl-N,O-bis(trimethylsilyl)hydroxylamines. By the further reaction of O-difluorosilyl-N,N-bis(trimethylsilyl)hydroxylamine with the lithiated hydroxylamine, O,O′-fluoromethylsilyldi[N,N-bis(trimethylsilyl)hydroxylamine] is formed. On heating N-difluorophenylsilyl-N,O-bis(trimethylsilyl)hydroxylamine di[fluorophenylsilyl(methyl)amino]pentamethylsiloxane is formed by methyl group migration. The NMR and mass spectra of the compounds are reported.