Optical studies of pulsed-laser fragmentation of biliary calculi

The fragmentation of gallstones and kidney stones using pulsed visible laser radiation has recently been demonstrated; however, the fragmentation mechanism is not well understood. The temporal and spectral characteristics of the bright flash of light accompanying fragmentation of gallstones were studied using 0.8 and 360-s-long, 690-nm-wavelength, dye-laser pulses. Time-resolved visible emission spectra show a broad continuum upon which line spectra are superimposed. The continuum emission is due to free-free and free-bound electron transitions indicative of a plasma and the line spectra are due to neutral and ionized calcium. Initiation of this plasma is fluence rather than intensity dependent. A model is proposed in which laser energy is coupled to the plasma, which then impulsively expands, generating intense acoustic transients which fracture the stone.     

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     

X-ray structure and variable temperature NMR spectra of [meso-triarylcorrolato]copper(III)

The diamagnetic square planar d(8) complexes [meso-arylcorrolato]copper(III) become paramagnetic upon warming, indicative of the equilibrium between the [corrolato]copper(III) and the [corrolato](+)* copper(II) forms of the complex. [meso-Triphenylcorrolato]copper(III) was structurally characterized and found to be saddled.     

Réductions chimique et électrochimique de 5H-benzopyranno[4,3-d]pyrimidines

The chemical reduction of 5H-[1]benzopyranno[4,3-d]pyrimidines with lithium aluminum hydrrde leads to 3,4-dihydro derivations. The electro-chemical reducation in acidic medium shows two monoelectronic cathodic waves. In netural or basic medium, substituted compounds in 2 position show a single bielectronic wave while two bielectronic waves are observed for unsubstituted compounds In all cases, preparative electrolysis lead to a hydrodimer in the 4,4′-positiom.     

Use of solid-phase microextraction-capillary-gas chromatography (SPME-CGC) for the varietal characterization of wines by means of chemometrical methods

The extraction of wine aroma compounds was studied by direct-SPME (DI/SPME), headspace-SPME (HS/SPME) and multiple-headspace-extraction-SPME (MHE/SPME). The aromagrams obtained by HS/SPME-CGC were evaluated with chemometrical methods for the varietal classification of wines. Received: 25 July 1997 / Revised: 24 September 1997 / Accepted: 7 October 1997     

Speciation and biosynthetic variation in four dictyoceratid sponges and their cyanobacterial symbiont, Oscillatoria spongeliae

Four species of marine sponges (Phylum Porifera, Order Dictyoceratida), which contain the filamentous cyanobacterial symbiont Oscillatoria spongeliae, were collected from four locations in Palau. The halogenated natural products associated with the symbiont were characterized from each sample, revealing that each species contained either chlorinated peptides, brominated diphenyl ethers, or no halogenated compounds. Analysis of the host sponges and the symbionts indicated that each species of sponge contained a distinct strain of morphologically similar cyanobacteria. Although cospeciation may be present in this group, we have identified that at least one host switching event has occurred in this symbiosis. Only the strain of O. spongeliae in the sponge containing the chlorinated compounds possessed genes involved in the biosynthesis of chlorinated leucine precursors, indicating that the chemical variation observed in these animals has a genetic foundation.     

Protein-Loop Mimetics: A Diketopiperazine-Based Template to Stabilize Loop Conformations in Cyclic Peptides Containing the NPNA and RGD Motifs

We explore here an approach to mimic the structures and biological functions of protein loops in small synthetic molecules, by grafting the loop of interest onto an organic template comprising a bicyclic diketopiperazine, prepared by the formal coupling of (2S,4S)-4-aminoproline (Pro(NH₂)) and aspartic acid (Asp). The Fmoc-protected template 4 is used to prepare cyclo(-Ala¹-Asn²-Pro³-Asn⁴-Ala⁵- Ala⁶-Temp-) ( 5 ) and cyclo(-Ala¹-Arg²-Gly³-Asp⁴-Temp-) ( 6 ) (where Temp = template derived from 4 ), containing the Asn-Pro-Asn-Ala (NPNA) and Arg-Gly-Asp (RGD) motifs. The conformational properties of these molecules are studied in aqueous solution by NMR and simulated-annealing methods. The NPNA motif, an immunodominant epitope on the circumsporozoite surface protein of the malaria parasite Plasmodium falciparum, is shown to adopt a stable type-I β-turn in 5 . The template in 5 adopts a preferred conformation with Pro(NH₂)χ₁ ≈? ?35° and the Asp moiety χ₁ ≈? 70°. A different template conformation is inferred for 6 , with Pro(NH₂)χ₁ ≈? 0°, but the ARGD loop appears by NMR to undergo rapid conformational averaging. Solid-phase binding assays reveal that 6 displays modest antagonist activity towards both the integrin α_IIbβ₃ and α_vβ₃ receptors.     

Ab initio study of the binding of Trichostatin A (TSA) in the active site of histone deacetylase like protein (HDLP)

Histone deacetylase (HDAC) inhibitors have recently attracted considerable interest because of their therapeutic potential for the treatment of cell proliferative diseases. An X-ray structure of a very potent inhibitor, Trichostatin A (TSA), bound to HDLP (an HDAC analogue isolated from Aquifex aeolicus), is available. From this structure, an active site model (322 atoms), relevant for the binding of TSA and structural analogues, has been derived, and TSA has been minimized in this active site at HF 3-21G* level. The resulting conformation is in excellent accordance with the X-ray structure, and indicates a deprotonation of the hydroxamic acid in TSA by His 131. Also, a water molecule was minimized in the active site. In addition to a similar deprotonation, in accordance with a possible catalytic mechanism of HDAC as proposed by Finnin et al. (M. S. Finnin, J. R. Donigian, A. Cohen, V. M. Richon, R. A. Rifkind and P. A. Marks, Nature, 1999, 401, 188-193), a displacement of the resulting OH- ion in the active site was observed. Based on these results, the difference in energy of binding between TSA and water was calculated. The resulting value is realistic in respect to experimental binding affinities. Furthermore, the mechanism of action of the His 131-Asp 166 charge relay system was investigated. Although the Asp residue in this motif is known to substantially increase the basicity of the His residue, no proton transfer from His 131 to Asp 166 was observed on binding of TSA or water. However, in the empty protonated active site, this proton transfer does occur.     

L'acide hydroxylamine-O-sulfonique,réactif de choix pour la conversion d'aldéhydes en nitriles

Hydroxylamine-O-sulfonic acid: a convenient reagent for the conversion of aldehydes into nitriles . Hydroxylamine-O-sulfonic acid (HAS) proved to be an excellent reagent for the conversion of aliphatic, aromatic and heteroatomic aldehydes into nitriles. There, aldehydes in the form of suspension in HAS water solution, react rapidely to give the corresponding nitriles in high yield. Only with formylpyridines could the intermediate oxime-O-sulfonic acids be isolated.