The mechanism of photoinduced acylation of amines by N-acyl-5,7-dinitroindoline as determined by time-resolved infrared spectroscopy

[reaction: see text] The photochemistry of N-acyl-5,7-dinitroindoline (1) was studied in acetonitrile using nanosecond time-resolved infrared (TRIR) spectroscopy. Upon photolysis, two nearly but not completely overlapping sets of transient IR bands are observed that are assigned to two non-interconvertible conformers of mixed acetic nitronic anhydride 7. While syn-7 reverts rapidly to 1, anti-7 is long-lived and is able to acylate amines. Results of density functional theory calculations support conclusions based on experimental TRIR data.     

Solvothermal Synthesis, Crystal Structure, and Properties of the First Zinc Containing Thioantimonate(III) [Zn( tren)] 2Sb 4S 8·0.75 H 2O

Yellow crystals of the title compound were obtained under solvothermal conditions reacting elemental Zn, Sb, and S in a solution of tris(2-aminoethyl)amine (=tren) and water. The compound crystallises in the monoclinic space group P2₁/c with a=13.0247(7), b=22.308(2), c=12.1776(6) Å, and =105.352(6)°. In the structure of [Zn(tren)]₂Sb₄S₈·0.75 H₂O two [Zn(tren)]²⁺ cations are bound to the [Sb₄S₈]^4– anion via S atoms. The Zn²⁺ ions are in a trigonal bipyramidal environment of four N atoms of the tetradentate tren ligand and one S atom of the [Sb₄S₈]^4– anion. The anion is formed by SbS₃ and SbS₄ units which share common corners and edges. The interconnection mode yields three different non-planar Sb₂S₂ heterorings. The shortest intermolecular Sb–S distance amounts to about 3.7Å, and taking this long separation into account undulated chains running along [001] are formed with the water molecules residing in the pocket-like cavities. Upon heating the compound decomposes in one step starting at about 240°C. The final decomposition product was identified as ZnS and Sb₂S₃ by X-ray powder diffractometry. Additionally, spectroscopic data as well as synthetic procedures for [Zn(tren)]₂Sb₄S₈·0.75 H₂O are reported.     

Interparticle interactions in agglomerates of alpha-Fe2O3 nanoparticles: influence of grinding

We have chemically prepared a sample of antiferromagnetic alpha-Fe2O3 nanoparticles by a gel-sol technique. M?ssbauer spectra of the as-prepared sample showed that superparamagnetic relaxation was suppressed due to strong magnetic interparticle interactions even at room temperature. However, subsequent grinding of the sample by hand in a mortar for some minutes resulted in fast superparamagnetic relaxation of some of the particles. The effect was even more dramatic if the alpha-Fe2O3 powder was ground for a longer time or together with nonmagnetic eta-Al2O3 nanoparticles. Similar effects were found after low-energy ball milling. Thus it is found that the agglomeration of the nanoparticles during preparation under wet conditions results in strong magnetic interparticle interaction, but a relatively gentle mechanical treatment is sufficient to break up the agglomerates, resulting in much weaker interactions. We show that these effects can also be seen when a soil sample containing magnetic nanoparticles is ground.     

Serum Chloride Optical Sensors Based on Dynamic Quenching of the Fluorescence of Photo-Immobilized Lucigenin

This article describes the preparation and performance of an optical sensor for continuous measurement of chloride at extracellular (serum) levels (20–200mM). The sensor is based on dynamic quenching of the fluorescence of lucigenin which was photo-immobilized on a hydrogel. Quenching occurs via a collisional mechanism, and the decrease in fluorescence intensity on exposure to 100mM chloride typically is –60%. It allows the determination of chloride in the 1 to 200mM concentration range, with a precision of ±3mM at 120mM. Bromide, iodide and salicylate act as interferents, while the effect of pH and oxygen is negligibly small. The sensor displays strong fluorescence intensity, excellent reproducibility, long-term stability, response times in the order of 2–5min, and is used in a commercial serum and blood chloride analyzer.Received January 21, 2003; accepted April 6, 2003 Published online July 28, 2003     

Asymmetric Catalysis. Part 149 [1]. Synthesis of New Chiral Tridentate Ligands for Enantioselective Catalysis

Summary. The synthesis of new chiral tridentate ligands is reported which coordinate transition metals in a meridional way. The ligands contain a pyridine ring, an oxazoline ring, and a strongly coordinating diphenylphosphanyl group. The methionine-derived ligand forms a copper complex, which has been studied by X-ray crystallography. The new ligands were tested in models of enantioselective catalyses, such as hydrogenation of ketopantolactone, hydrosilylation of acetophenone, and transfer hydrogenation of acetophenone.X-ray structure analysesReceived March 4, 2003; accepted March 4, 2003 Published online August 18, 2003     

Percolation in strongly correlated systems: The massless Gaussian field

We derive a number of new results for correlated nearest neighbor site percolation onZ ^d. We show in particular that in three dimensions the strongly correlated massless harmonic crystal, i.e., the Gaussian random field with mean zero and covariance –, has a nontrivial percolation behavior: sites on whichS _x h percolate if and only ifh _c . with0 _c < . This provides the first rigorous example of a percolation transition in a system with infinite susceptibility.     

On a conjecture of R. E. Miles about the convex hull of random points

Denoty byp _d+i (B _d ,d+m) the probability that the convex hull ofd+m points chosen independently and uniformly from ad-dimensional ballB _d possessesd+i(i=1,...,m) vertices. We prove Mile's conjecture that, given any integerm, p _d+m (B _d ,d+m)»1 asd». This is obvious form=1 and was shown by Kingman form=2 and by Miles form=3. Further, a related result by Miles is generalized, and several consequences are deduced.Dedicated to Professor E. Halwaka on the occasion of his seventieth