Characterizing Pressure‐Induced Uranium C?H Agostic Bonds

The diuranium(III) compound [UN′′₂]₂(μ‐η⁶:η⁶‐C₆H₆) (N′′=N(SiMe₃)₂) has been studied using variable, high‐pressure single‐crystal X‐ray crystallography, and density functional theory . In this compound, the low‐coordinate metal cations are coupled through π‐ and δ‐symmetric arene overlap and show close metal CH contacts with the flexible methyl CH groups of the sterically encumbered amido ligands. The metal–metal separation decreases with increasing pressure, but the most significant structural changes are to the close contacts between ligand CH bonds and the U centers. Although the interatomic distances are suggestive of agostic‐type interactions between the U and ligand peripheral CH groups, QTAIM (quantum theory of atoms‐in‐molecules) computational analysis suggests that there is no such interaction at ambient pressure. However, QTAIM and NBO analyses indicate that the interaction becomes agostic at 3.2 GPa.     

Group I cation templated formation of luminescent mono- and bis-substituted thionaphthol heterobimetallic complexes of Pr, Nd, Eu and Tb

Metathesis of lanthanide tris di-tert-butyl beta-diketonates ([Ln(thd)3] Ln=Pr, Nd, Eu, Tb) with one or two equivalents of group 1 salts of the sulfur bridged binaphtholate dianion [1,1'-S(2-OC10H4But(2)-3,6)2]2-, [M2L], M=K, Li affords luminescent mono- and bis-ligand substituted complexes ML[LnL(thd)2].L; M=K, Ln=Pr , Nd , Eu and Tb (L=thf, diethyl ether or toluene) and M(thf)2[LnL2(thd)]; M=Li, Ln=Pr , Nd , Eu , Tb . The potassium salt [K2L] affords mono-L substituted complexes most cleanly, while the lithium salt [Li2L] yields the bis-L substituted complexes most cleanly. The L ligands function as antenna for the sensitised lanthanide-centred emission in Eu3+ and Tb3+ complexes. The X-ray single-crystal structures of mono- and bis-L lanthanide complexes of Nd3+ are presented.     

Enantioselective N-heterocyclic carbene catalyzed formal [3+2] cycloaddition using α-aroyloxyaldehydes and oxaziridines

An enantioselective N-heterocyclic carbene catalysed formal [3+2] cycloaddition has been developed for the synthesis of oxazolindin-4-one products. The reaction of oxaziridines and α-aroyloxyaldehydes under N-heterocyclic carbene catalysis provides the formal cycloaddition products with excellent control of the diastereo- and enantioselectivity (12 examples, up to >95:5 dr, >99:1 er). A matched-mismatched effect between the enantiomer of the catalyst and oxaziridine was identified, and preliminary mechanistic studies have allowed the proposal of a model to explain these observations.     

Mechanistic insight into the lanthanide(III) salt catalysed monoacylation of symmetrical diols from structural models

Model studies are presented that suggest the mechanism of the lanthanide(III) salt catalysed mono acylation of symmetrical diols proceeds via chelation of the diol and the anhydride to the lanthanide salt, followed by an 'intramolecular' acyl transfer.     

Certification of fat-soluble vitamins,carotenoids, and cholesterol in human serum: Standard reference material 968b

In Standard Reference Material 968b, fat-soluble vitamins and cholesterol in human serum, certified values are provided for cholesterol, retinol, retinyl palmitate, -tocopherol, trans--carotene, total -carotene (trans plus cis isomers), total -carotene, and lutein. Non-certified values are also reported for -tocopherol (includes -tocopherol), -tocopherol, zeaxanthin, -cryptoxanthin, trans-lycopene, trans-lycopene, trans--carotene, total lycopene, 9-cis-carotene, 13- plus 15-cis--carotene, and 15-cis--carotene. Both certified and non-certified values are based on the agreement among results from three different liquid chromatographic analytical procedures developed at NIST and from an interlaboratory comparison exercise among institutions that participate in a NIST-managed Micronutrients Measurement Quality Assurance Program. Cholesterol is certified in this material using the NIST isotope dilution/mass spectrometric definitive method.     

Uranyl complexation by a schiff-base, polypyrrolic macrocycle

Mononuclear uranyl (UO(2)(2+)) complexes supported by the polypyrrolic macrocycle L have been synthesized and exhibit hinged macrocyclic structures with an expanded cavity and enforced pi-stacking and hydrogen bonding motifs.     

Measurement of the positive muon anomalous magnetic moment to 0.7 ppm

A higher precision measurement of the anomalous g value, a(mu)=(g-2)/2, for the positive muon has been made at the Brookhaven Alternating Gradient Synchrotron, based on data collected in the year 2000. The result a(mu(+))=11 659 204(7)(5)x10(-10) (0.7 ppm) is in good agreement with previous measurements and has an error about one-half that of the combined previous data. The present world average experimental value is a(mu)(expt)=11 659 203(8)x10(-10) (0.7 ppm).     

Hopf bifurcation and analysis of equilibrium for a third-order differential equation in a model of competition

1. IntroductionOne of the more challenging aspects of mathematical biology is competition modelling.Although the mathematical idea is simple[1], this type of modelling is so difficult to carryout in any generality since there are so maily ways for a population to compete.The simplest form of competition is called eXPloitative competition. This occurs whenone or more populations compete for the same resources such as a common food supplyor a growth-limiting nutriellt. A simple example of this…     

Precise Measurement of Muon Capture on the Proton

The aim of the μCap experiment is a 1% measurement of the singlet capture rate Λ _S for the basic electro-weak reaction μ + p → n + ν_μ. This observable is sensitive to the weak form-factors of the nucleon, in particular to the induced pseudoscalar coupling constant g _P . It will provide a rigorous test of theoretical predictions based on the Standard Model and effective theories of QCD. The present method is based on high precision lifetime measurements of μ⁻ in hydrogen gas and the comparison with the free μ⁺ lifetime. The μ⁻ experiment will be performed in ultra-clean, deuterium-depleted H₂ gas at 10 bar. Low density compared to liquid H₂ is chosen to avoid uncertainties due to ppμ formation. A time projection chamber acts as a pure hydrogen active target. It defines the muon stop position in 3D and detects rare background reactions. Decay electrons are tracked in cylindrical wire-chambers and a scintillator array covering 75% of 4π. This revised version was published online in August 2006 with corrections to the Cover Date.