Separation of molecular tracers sorbed onto atmospheric particulate matter by flash chromatography

In to order increase sensitivity and to reduce the background induced by matrix effects, a method was developed that uses flash chromatography to separate various compounds present in atmospheric aerosol samples prior to their analysis with different analytical techniques (GC–MS, GC–FID, HPLC). For this purpose, flash chromatography using a 4 g silica gel column crossed by eluent at a flow rate of 20 mL min⁻¹ was used. An eluent with enhanced polarity is needed to separate nonpolar (linear and branched alkanes), semipolar (PAH, nitro-PAH and cholesterol) and polar (methoxyphenols, alkanoic acids, and levoglucosan) compounds. Three combinations of solvents were used: hexane for the nonpolar fraction (F1), toluene/hexane for the semipolar fraction (F2) and dimethylformamide for the polar fraction (F3). The use of different eluents for each fraction allows separation of the sample to be accomplished with good repeatability and satisfying yields [85 ± 5% for F1, 81 ± 8% (PAHs), 89 ± 6% (nitro-PAHs) and 74 ± 7% (cholesterol) for F2 and 79 ± 7% (n-alkanoic acids), 40 ± 11% (methoxyphenols) and 77 ± 6% (levoglucosan) for F3]. The methoxyphenol yields were low due to losses during the concentration/evaporation step. This method was then applied to analyse the organic composition of particles collected at an urban site in Strasbourg (France).     

Heck arylations of pent-4-enoates or allylmalonate using a palladium/tetraphosphine catalyst

The Heck reaction of aryl halides with functionalised alk-1-enes should be a powerful method for the synthesis of functionalised (E)-1-arylalk-1-ene derivatives. The major problem of this reaction is the palladium-catalysed migration of the carbon-carbon double bond along the alkyl chain when there are no substituents on the C3 carbon of the alk-1-enes. We observed that for the arylation of ethyl pent-4-enoate, ethyl 2-methylpent-4-enoate or dimethyl allylmalonate this migration could be partially or completely controlled using appropriate reaction conditions. The ramification on the alkyl chain and the substituents on the aryl halide have also an important influence on this migration. Moreover, the cis,cis,cis-1,2,3,4-tetrakis(diphenylphosphinomethyl)cyclopentane/1/2[PdCl(C₃H₅)]₂ system catalyses this reaction with a wide range of aryl bromides using very high ratio substrate/catalyst in good yields.     

Trapping of the highly strained [5](2,4)quinolinophane system

The highly strained [5](2,4)quinolinophane system can be generated as an intermediate (2b), which is extremely susceptible towards the attack of both nucleophilic and electrophilic species. Addition of water at the carbon bridgehead C2 occurs rapidly and is followed by rearrangements to give a strain free product 10. An unusual carbene addition at the N1C2 bond of 2b is proposed to explain the formation of the strained ‘anti-Bredt’ type olefin 11.     

Slice imaging of the quantum state-to-state cross section for photodissociation of state-selected rovibrational bending states of OCS (v2=0,1,2/JlM)+hnu-->CO(J)+S(1D2)

Using hexapole quantum state-selection of OCS (v(2)=0,1,2/JlM) and high-resolution slice imaging of quantum state-selected CO(J), the state-to-state cross section OCS (v(2)=0,1,2/JlM)+hnu-->CO(J)+S((1)D(2)) was measured for bending states up to v(2)=2. The population density of the state-selected OCS (v(2)=0,1,2 /JlM) in the molecular beam was obtained by resonantly enhanced multiphoton ionization of OCS and comparison with room temperature bulk gas. A strong increase of the cross section with increasing bending state is observed for CO(J) in the high J region, J=60-67. Integrating over all J states the authors find sigma(v(2)=0):sigma(v(2)=1):sigma(v(2)=2)=1.0:7.0:15.0. A quantitative comparison is made with the dependence of the transition dipole moment function on the bending angle.     

Analysis of trace levels of pesticides in rainwater by SPME and GC-tandem mass spectrometry after derivatisation with PFFBr

Solid-phase microextraction (SPME) was used for the analysis of some pesticides (bromoxynil, chlorotoluron, diuron, isoproturon, 2,4-MCPA, MCPP and 2,4-D) in rainwater after derivatisation with PFBBr and gas chromatography-ion trap mass spectrometry. The derivatisation procedure was optimized by testing different methods: direct derivatisation in the aqueous phase followed by SPME extraction, on-fibre derivatisation and derivatisation in the injector. The best result was obtained by headspace coating the PDMS/DVB fibre with PFBBr for 10 min followed by direct SPME extraction for 60 min at 68 °C (pH 2 and 75% NaCl). Good detection limits were obtained for all the compounds: these ranged between 10 and 1,000 ng L⁻¹ with a relatively high uncertainty due to the combination of derivatisation and SPME extraction steps. The optimized procedure was applied to the analysis of pesticides in rainwater and results obtained shows that this method is a fast and simple technique to assess the spatial and temporal variations of concentrations of pesticides in rainwater.     

Hydrogen bonding affects the [NiFe] active site of Desulfovibrio vulgaris Miyazaki F hydrogenase: a hyperfine sublevel correlation spectroscopy and density functional theory study

Pulse electron paramagnetic resonance and hyperfine sublevel correlation spectroscopy have been used to investigate nitrogen coordination of the active site of [NiFe] hydrogenase of Desulfovibrio vulgaris Miyazaki F in its oxidized "ready" state. The obtained (14)N hyperfine (A = [+1.32, +1.32, +2.07] MHz) and nuclear quadrupole (e(2)qQ/h = -1.9 MHz, eta = 0.37) coupling constants were assigned to the N(epsilon) of a highly conserved histidine (His88) by studying a hydrogenase preparation in which the histidines were (15)N labeled. The histidine is hydrogen-bonded via its N(epsilon)-H to the nickel-coordinating sulfur of a cysteine (Cys549) that carries an appreciable amount of spin density. Through the hydrogen bond a small fraction of the spin density ( approximately 1%) is delocalized onto the histidine ring giving rise to an isotropic (14)N hyperfine coupling constant of about 1.6 MHz. These conclusions are supported by density functional calculations. The measured (14)N quadrupole coupling constants are related to the polarization of the N(epsilon)-H bond, and the respective hydrogen bond can be classified as being weak.     

para‐Sulfonated Calixarenes Used as Synthetic Receptors for Complexing Photolabile Cholinergic Ligand

The water‐soluble tetra‐, hexa‐ and octasulfonated calix[4]arenes, calix[6]arenes, and calix[8]arenes 1 – 3 , respectively, were investigated as potential synthetic receptors for photolabile cholinergic ligand A , a photolytic precursor of choline. Ligand A is a bifunctional molecule carrying a photolabile 2‐nitrobenzyl group at one end and a choline moiety at the other end. Results from NMR studies have shown that calixarenes 1 – 3 form stable 1 : 1 complexes with A , having similar binding potential to that observed with the cholinergic enzymes acetylcholinesterase and butyrylcholinesterase. Further studies have suggested that calix[8]arene forms a ditopic complex by binding concomitantly to both the cationic choline moiety and the aromatic photolabile group of A , whereas calix[4]arene and calix[6]arene form monotopic complexes with A . The ditopic complex between calix[8]arene and A results from mutually induced fitting process, while the monotopic complexes between calix[4]arene and A can be regulated by pH: at neutral pH, calix[4]arene specifically binds the cationic choline moiety, while, at acidic pH, it complexes unselectively both the cationic choline moiety and the aromatic group of A . Our results show that para‐sulfonated calixarenes are versatile artificial receptors which bind in various ways to the bifunctional photolabile cholinergic ligand A , depending on their size, geometry, and state of protonation.     

Quantitative analysis of backbone dynamics in a crystalline protein from nitrogen-15 spin-lattice relaxation

A detailed analysis of nitrogen-15 longitudinal relaxation times in microcrystalline proteins is presented. A theoretical model to quantitatively interpret relaxation times is developed in terms of motional amplitude and characteristic time scale. Different averaging schemes are examined in order to propose an analysis of relaxation curves that takes into account the specificity of MAS experiments. In particular, it is shown that magic angle spinning averages the relaxation rate experienced by a single spin over one rotor period, resulting in individual relaxation curves that are dependent on the orientation of their corresponding carousel with respect to the rotor axis. Powder averaging thus leads to a nonexponential behavior in the observed decay curves. We extract dynamic information from experimental decay curves, using a diffusion in a cone model. We apply this study to the analysis of spin-lattice relaxation rates of the microcrystalline protein Crh at two different fields and determine differential dynamic parameters for several residues in the protein.     

A New Approach to the {\ast} -Genvalue Equation

We show that the eigenvalues and eigenfunctions of the star-genvalue equation can be completely expressed in terms of the corresponding eigenvalue problem for the quantum Hamiltonian. Our methods make use of a Weyl-type representation of the star-product and of the properties of the cross-Wigner transform, which appears as an intertwining operator.     

Rheological properties of fresh and cryopreserved human arteries tested in vitro

Cryopreservation is widely used to preserve blood vessels for a while but is controversially suspected to affect the mechanical behavior of these allografts. The aim of this study was to determine whether differences in the three-dimensional mechanical behavior exist or not between fresh and cryopreserved arteries. Using a previously developed experimental system, in vitro inflation tests were performed on twenty segments of human fresh and cryopreserved arteries, in static conditions. Opening angles were also measured from images of rings in zero-stress state. The initial reference state was chosen as the unloaded state and tests were performed on specimens stretched at natural “in vivo” length. Mechanical measures calculated are “natural” (Hencky) strains (finite deformations), “true” (Cauchy) stresses in radial, circumferential, and longitudinal directions as well as strain energy per unit volume. Tangent moduli are derived from radial and circumferential stress-strain characteristics using non-linear curve fitting. Values of incremental and pressure-strain elastic parameters, wall stiffness, and compliance per unit length are also calculated. Results are presented in terms of characteristics of stresses and strains in the three directions, axial force, tangent moduli vs strains or stresses, and energy per unit volume, for both types of artery, with reference to transmural pressure. Detailed numerical results are given at mean transmural pressure or in the physiological range. Significant differences are indicated by statistic Student T-tests. Results obtained show that significant differences exist between rheological properties of fresh and cryopreserved segments of human artery. Strains, stresses, axial force, strain energy, and wall stiffness values highlight those differences whereas elastic parameters, compliance, and opening angle do not. The usefulness of some parameters to compare the mechanical behavior existing between fresh and cryopreserved arteries is therefore underlined. Received: 3 January 2000 Revision received: 12 April 2000 Accepted: 8 May 2000