Reactivity of 2-ethoxy-5-alkyl-3,4-dihydro-2H-pyrans towards aluminum alkyls : a facile synthesis of cyclobutylmethanols

2-Ethoxy-5-alkyl-3,4-dihydro-2H-pyrans react with Albuⁱ₃ and through a regioselective hydride addition provide substituted cyclobutylmethanols in very good yields.     

Alloy contribution to phonon softening in ultra-heavily doped Si:As

Experimentally observed phonon softening of the 520 cm^-1 Raman line in ultra-heavily doped n-Si is attributed to the electron-phonon self-energy effects as well as change in lattice force constants of the alloy system.     

Direct evidence for As as a Zn-site impurity in ZnO

Arsenic has been reported in the literature as one of the few p-type dopants in the technologically promising II-VI semiconductor ZnO. However, there is an ongoing debate whether the p-type character is due to As simply replacing O atoms or to the formation of more complicated defect complexes, possibly involving As on Zn sites. We have determined the lattice location of implanted As in ZnO by means of conversion-electron emission channeling from radioactive (73)As. In contrast to what one might expect from its nature as a group V element, we find that As does not occupy substitutional O sites but in its large majority substitutional Zn sites. Arsenic in ZnO (and probably also in GaN) is thus an interesting example for an impurity in a semiconductor where the major impurity lattice site is determined by atomic size and electronegativity rather than its position in the periodic system.     

The impact of metrological traceability on the validity of creatinine measurement as an index of renal function

When the calibration of a routine measurement procedure is traced back to metrological higher order, a significant discrepancy can occur between the analytical conditions of the routine measurement and the analytical conditions that were used in the clinical studies upon which the decision-making criteria are based. This can lead to serious interpretation errors with possible dramatic consequences for patients. The calibration of the creatinine Jaffé method is an excellent example of the importance of medical traceability. The compensated Jaffé method correlated accurately with the reference method and the compensated Jaffé creatinine clearance (CrCl), Cockroft and Gault and MDRD with the ⁵¹Cr EDTA clearance. The Schwartz estimate based upon the compensated Jaffé and enzymatic method overestimated, while uncompensated Jaffé slightly underestimated glomerular filtration rate (GFR). The situation in children is complex since serum creatinine concentrations are much lower in infants, rendering tubular secretion relatively more important. Low-molecular weight proteins have been suggested to replace serum creatinine as a marker for GFR. -trace protein, cystatin C, and ₂-microglobulin showed good correlation with GFR. However, care should be taken in patients presenting with some malignant tumors, since significant increases of cystatin C in patients with metastatic melanoma or colorectal cancer has been reported.Presented at the 9th Conference on Quality in the Spotlight, 18-19 March 2004, Antwerp, Belgium     

Experimental and theoretical characterization of arsenite in water: insights into the coordination environment of As-O

Long-term exposure to arsenic in drinking water has been linked to cancer of the bladder, lungs, skin, kidney, nasal passages, liver, and prostate in humans. It is therefore important to understand the structural aspects of arsenic in water, as hydrated arsenic is most likely the initial form of the metalloid absorbed by cells. We present a detailed experimental and theoretical characterization of the coordination environment of hydrated arsenite. XANES analysis confirms As(III) is a stable redox form of the metalloid in solution. EXAFS analysis indicate, at neutral pH, arsenite has a nearest-neighbor coordination geometry of approximately 3 As-O bonds at an average bond length of 1.77 A, while at basic pH the nearest-neighbor coordination geometry shifts to a single short As-O bond at 1.69 A and two longer As-O bonds at 1.82 A. Long-range ligand scattering is present in all EXAFS samples; however, these data could not be fit with any degree of certainty. There is no XAS detectable interaction between As and antimony, suggesting they are not imported into cells as a multinuclear complex. XAS results were compared to a structural database of arsenite compounds to confirm that a 3 coordinate As-O complex for hydrated arsenite is the predominate species in solution. Finally, quantum chemical studies indicate arsenite in solution is solvated by 3 water molecules. These results indicate As(OH)3 as the most stable structure existing in solution at neutral pH; thus, ionic As transport does not appear to be involved in the cellular uptake process.     

Preparation of a novel diphosphine-palladium macrocyclic complex possessing a molecular recognition site. Oxidative addition studies

A disphosphine-palladium(0) complex capable of recognising barbiturates has been prepared. Oxidative addition studies with a barbitiurate:aryl iodide conjugate provided new Pd(ii) complexes where the positioning of the Pd-bound aryl group is controlled by the molecular recognition event.     

A metal-centered hydrophobic pocket recognizing pyridine over piperidine

Two external spaces of an inorganic tennis ball are a novel type of metal-centered hydrophobic pocket where two hydrophobic trans-(+/-)-1,2-diaminocyclohexane groups stand perpendicularly to and around the metal coordination plane. The space recognizes pyridine over piperidine, and a novel supramolecule was obtained using such pyridine recognition properties.