Analyse conformationnelle de cétones cyclopropaniques par RMN à l'aide des déplacements paramagnétiques induits par Eu(dpm)3

The lanthanide induced shifts (LIS) of the lanthanide shift reagent Eu(dpm)₃ are reported for several cyclopropyl ketones. The conformational preference of the cyclopropanoyl group is determined via LIS by comparison with two compounds: dispiro-[2.1.2.2]nonane-4-one and 4,4,5-trimethyl bicyclo[3.1.0]hexane 2-one which are respectively in s-cis and s-trans conformation.     

Detection of oligonucleotide gas-phase conformers: H/D exchange and ion mobility as complementary techniques

Gas-phase hydrogen/deuterium exchange of small oligonucleotides (dTG, dC(6) and C(6)) with CD(3)OD was performed in the second hexapole of a Fourier transform ion-cyclotron resonance (FTICR) mass spectrometer. Ion activation experiments were conducted by accelerating the ions at the entrance of the H/D exchange cell under conditions promoting exclusively collisional isomerization. These experiments allowed us to assess the presence of several conformers, and to probe the height of the isomerization barrier separating these conformers. Ion mobility experiments were also performed. Their results were consistent with the H/D exchange data. A model accounting for the competing isomerization and H/D exchange reactions is proposed. Comparing the ion acceleration experiments for H/D exchange and for ion mobility reveals that the most compact conformer displays the fastest H/D exchange. This observation shows that H/D exchange and ion mobility provide us with complementary information because hydrogen accessibility and macromolecule compactness are not univocally associated.     

Optimization of a nano‐enzymatic reactor for on‐line tryptic digestion of polypeptide conjugates by capillary electrophoresis

This work aims at studying the optimization of an on‐line capillary electrophoresis (CE)‐based tryptic digestion methodology for the analysis of therapeutic polypeptides (PP). With this methodology, a mixture of surrogate peptide fragments and amino acid were produced on‐line by trypsin cleavage (enzymatic digestion) and subsequently analyzed using the same capillary. The resulting automation of all steps such as injection, mixing, incubation, separation and detection minimizes the possible errors and saves experimental time. In this paper, we first study the differents parameters influencing PP cleavage inside the capillary (plug length, reactant concentration, incubation time, diffusion and electrophoretic plugs mixing). In a second part, the optimization of the electrophoretic separation conditions of generated hydrolysis products (nature, pH and ionic strength (I) of the background electrolyte (BGE)) is described. Using the optimized conditions, excellent repeatability was obtained in terms of separation (migration times) and proteolysis (number of products from enzymatic hydrolysis and corresponding amounts) demonstrating the robustness of the proposed methodology.     

Synthesis and supramolecular organization of amphiphilic diblock copolymers combining poly(N,N-dimethylamino-2-ethyl methacrylate) and poly(epsilon-caprolactone)

Well-defined poly(epsilon-caprolactone) (PCL)/poly(N,N-dimethylamino-2-ethyl methacrylate (PDMAEMA) diblock copolymers were synthesized, and their self-assembly was investigated as micelles both in aqueous solutions and in thin solid deposits. The synthetic approach combines controlled ring opening polymerization (ROP) of epsilon-caprolactone (CL) and atom transfer radical polymerization (ATRP) of N,N-dimethylamino-2-ethyl methacrylate (DMAEMA). Diblock copolymers were prepared by ROP of CL initiated by (Al(OiPr)3), followed by quantitative reaction of the PCL hydroxy end-groups with bromoisobutyryl bromide. The alpha-isopropyloxy omega-2-bromoisobutyrate poly(epsilon-caprolactone) (PCL-Br) obtained was used as a macroinitiator for the ATRP of DMAEMA. The molecular characterization of those diblock copolymers was performed by 1H NMR spectroscopy and gel permeation chromatography (GPC) analysis. The self-assembly of the copolymers into micellar aggregates in aqueous media was followed with dynamic light scattering (DLS), as a function of concentration and the pH. In parallel, the morphology of the solid deposits of those micelles was examined with atomic force microscopy (AFM).     

Measurement of the charge asymmetry in semileptonic Bs0 decays

We have performed the first direct measurement of the time-integrated flavor untagged charge asymmetry in semileptonic Bs0 decays ASLs,unt by comparing the decay rate of Bs0-->micro+Ds-nuX, where Ds- -->phipi- and phi-->K+K-, with the charge-conjugate Bs0 decay rate. This sample was selected from 1.3 fb-1 of data collected by the D0 experiment in run II of the Fermilab Tevatron collider. We obtain ASLs,unt=[1.23+/-0.97(stat)+/-0.17(syst)]x10(-2). Assuming that Deltam(s)/Gamma(s)>1, this result can be translated into a measurement of the CP-violating phase in Bs0 mixing: DeltaGamma(s)/Deltam(s)tanphi(s)=[2.45+/-1.93(stat)+/-0.35(syst)]x10(-2).     

Evidence for production of single top quarks and first direct measurement of |Vtb|

The D0 Collaboration presents first evidence for the production of single top quarks at the Fermilab Tevatron pp[over ] collider. Using a 0.9 fb(-1) dataset, we apply a multivariate analysis to separate signal from background and measure sigma(pp[over ]-->tb+X,tqb+X)=4.9+/-1.4 pb. The probability to measure a cross section at this value or higher in the absence of a signal is 0.035%, corresponding to a 3.4 standard deviation significance. We use the cross section measurement to directly determine the Cabibbo-Kobayashi-Maskawa matrix element that describes the Wtb coupling and find 0.68<|V(tb)|相似文献   

Lifetime difference and CP-violating phase in the Bs0 system

From an analysis of the decay Bs0-->J/psi phi, we obtain the width difference between the light and heavy mass eigenstates DeltaGamma identical with (GammaL-GammaH)=0.17+/-0.09(stat)+/-0.02(syst) ps-1 and the CP-violating phase phis=-0.79+/-0.56(stat)(-0.01)(+0.14)(syst). Under the hypothesis of no CP violation (phis identical with 0), we obtain 1/Gamma=tau(Bs0)=1.52+/-0.08(stat)(-0.03)(+0.01)(syst) ps and DeltaGamma=0.12(-0.10)(+0.08)(stat)+/-0.02(syst) ps-1. The data sample corresponds to an integrated luminosity of about 1.1 fb-1 accumulated with the D0 detector at the Fermilab Tevatron collider. This is the first direct measurement of the CP-violating mixing phase in the Bs0 system.     

Search for production of single top quarks via tcg and tug flavor-changing-neutral-current couplings

We search for the production of single top quarks via flavor-changing-neutral-current couplings of a gluon to the top quark and a charm (c) or up (u) quark. We analyze 230 pb{-1} of lepton+jets data from pp[over] collisions at a center of mass energy of 1.96 TeV collected by the D0 detector at the Fermilab Tevatron Collider. We observe no significant deviation from standard model predictions, and hence set upper limits on the anomalous coupling parameters kappa{g}{c}/Lambda and kappa{g}{u}/Lambda, where kappa{g} define the strength of tcg and tug couplings, and Lambda defines the scale of new physics. The limits at 95% C.L. are kappa{g}{c}/Lambda<0.15 TeV-1 and kappa{g}{u}/Lambda<0.037 TeV-1.     

Study of the decay Bs(0)-->Ds(*)Ds(*)

We report a study of the decay Bs(0)-->Ds(*)Ds(*) using a data sample corresponding to 1.3 fb(-1) of integrated luminosity collected by the D0 experiment in 2002-2006 during run II of the Fermilab Tevatron collider. One Ds(*) meson was partially reconstructed in the decay Ds-->phi mu nu, and the other Ds(*) meson was identified using the decay Ds-->phi pi where no attempt was made to distinguish Ds and Ds(*) states. For the branching fraction Br(Bs(0)-->Ds(*)Ds(*)) we obtain a 90% C.L. range [0.002,0.080] and central value 0.039(-0.017)(+0.019)(stat)(-0.015)(+0.016)(syst). This was subsequently used to make the most precise estimate of the width difference DeltaGamma(s)CP in the Bs(0)-Bs(0) system: DeltaGamma(s)CP/Gamma(s)=0.079(-0.035)(+0.038)(stat)(-0.030)(+0.031)(syst).     

Measurement of the Lambdab0 lifetime using semileptonic decays

We report a measurement of the Lambda(b)(0) lifetime using a sample corresponding to 1.3 fb(-1) of data collected by the D0 experiment in 2002-2006 during run II of the Fermilab Tevatron collider. The Lambda(b)(0) baryon is reconstructed via the decay Lambda(b)(0)-->micronuLambda(c)(+)X. Using 4437+/-329 signal candidates, we measure the Lambda(b)(0) lifetime to be tau(Lambda(b)(0))=1.290(-0.110)(+0.119)(stat)(-0.091)(+0.087)(syst) ps, which is among the most precise measurements in semileptonic Lambda(b)(0) decays. This result is in good agreement with the world average value.