Homo- and heteronuclear 2D NMR approaches to analyse a mixture of deuterated unlike/like stereoisomers using weakly ordering chiral liquid crystals

We describe several homo- and heteronuclear 2D NMR strategies dedicated to the analysis of anisotropic (2)H spectra of a mixture of dideuterated unlike/like stereoisomers with two remote stereogenic centers, using weakly orienting chiral liquid crystals. To this end, we propose various 2D correlation experiments, denoted "D(H)(n)D" or "D(H)(n)C" (with n=1, 2), that involve two heteronuclear polarization transfers of INEPT-type with one or two proton relays. The analytical expressions of correlation signals for four pulse sequences reported here were calculated using the product-operators formalism for spin I=1 and S=1/2. The features and advantages of each scheme are presented and discussed. The efficiency of these 2D sequences is illustrated using various deuterated model molecules, dissolved in organic solutions of polypeptides made of poly-gamma-benzyl-L-glutamate (PBLG) or poly-epsilon-carbobenzyloxy-L-lysine (PCBLL) and NMR numerical simulations.     

Families of curves with ordinary singular points on regular surfaces

Sunto Fissata una superficie algebrica liscia X sopra un campo algebricamente chiuso e di caratteristica 0, e una curva ridotta C su X, si introduce, per ogni -upla di numeri naturali m₁,..., m, uno schema W=W(C, m₁,..., m), parametrizzante le curve del sistema lineare ¦C¦ con punti multipli ordinari di molteplicità almeno m₁,..., m. Si studia W in relazione con la configurazione delie singolarità e delle componenti irriducibili di C. Si prova in particolare un teorema di «virtuale connessione», che permette di stabilire l'esistenza di curve irriducibili in alcuni di tali schemi W.

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Membro del G.N.S.A.G.A. del C.N.R.     

Facets for the cut cone I

We study facets of the cut coneC _n , i.e., the cone of dimension 1/2n(n – 1) generated by the cuts of the complete graph onn vertices. Actually, the study of the facets of the cut cone is equivalent in some sense to the study of the facets of the cut polytope. We present several operations on facets and, in particular, a lifting procedure for constructing facets ofC _n+1 from given facets of the lower dimensional coneC _n . After reviewing hypermetric valid inequalities, we describe the new class of cycle inequalities and prove the facet property for several subclasses. The new class of parachute facets is developed and other known facets and valid inequalities are presented.     

The ALTO project at IPN-Orsay

The availability of both a tandem deuteron beam and a linac electron beam, the latter converted into Bremsstrahlung, at the new ALTO facility at IPN-Orsay offers a unique opportunity to compare the performance of a laser ion guide under different regimes. The ALTO accelerator has delivered its first electron beam at the end of 2005 and a design for a gas-cell prototype is being studied.     

High-power laser with Nd:YAG single-crystal fiber grown by the micro-pulling-down technique

We present optical characterization and laser results achieved with single-crystal fibers directly grown by the micro-pulling-down technique. We investigate the spectroscopic and optical quality of the fiber, and we present the first laser results. We achieved a cw laser power of 10 W at 1064 nm for an incident pump power of 60 W at 808 nm and 360 kW peak power for 12 ns pulses at 1 kHz in the Q-switched regime. It is, to the best of our knowledge, the highest laser power ever achieved with directly grown single-crystal fibers.     

High-speed horizontal-path atmospheric turbulence correction with a large-actuator-number microelectromechanical system spatial light modulator in an interferometric phase-conjugation engine

Results of atmospheric propagation for a high-speed, large-actuator-number adaptive optics system are presented. The system uses a microelectromechanical system- (MEMS-) based spatial light modulator correction device with 1024 actuators. Tests over a 1.35-km path achieved correction speeds in excess of 800 Hz and Strehl ratios close to 0.5. The wave-front sensor was based on a quadrature interferometer that directly measures phase. This technique does not require global wave-front reconstruction, making it relatively insensitive to scintillation and phase residues. The results demonstrate the potential of large-actuator-number MEMS-based spatial light modulators to replace conventional deformable mirrors.     

Covalent Grafting of BPin functions on Carbon Nanotubes and Chan–Lam–Evans Post-Functionalization

The chemical functionalization of carbon nanotubes is often a prerequisite prior to their use in various applications. The covalent grafting of 4,4,5,5-tetramethyl-1,3,2-dioxaborolane (BPin) functional groups directly on the surface of multi- and single-walled carbon nanotubes, activated by nucleophilic addition of nBuLi, was carried out. Thermogravimetric analysis (TGA) coupled with mass spectrometry, Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ions mass spectrometry (ToF-SIMS) confirmed the efficiency of this methodology and proved the integrity and covalent grafting of the BPin functional groups. These groups were further reacted with various nucleophiles in the presence of a copper(II) source in the conditions of the aerobic Chan–Lam–Evans coupling. The resulting materials were characterized by TGA, XPS and ToF-SIMS. This route is efficient, reliable and among the scarce reactions that enable the direct grafting of heteroatoms at carbonaceous material surfaces.     

A Cucurbit[8]uril 2:2 Complex with a Negative pKa Shift

A viologen derivative carrying a benzimidazole group ( V-P-I ²⁺; viologen–phenylene–imidazole V-P-I ) can be dimerized in water using cucurbit[8]uril (CB[8]) in the form of a 2:2 complex resulting in a negative shift of the guest pK_a, by more than 1 pH unit, contrasting with the positive pK_a shift usually observed for CB-based complexes. Whereas 2:2 complex protonation is unclear by NMR, silver cations have been used for probing the accessibility of the imidazole groups of the 2:2 complexes. The protonation capacity of the buried imidazole groups is reduced, suggesting that CB[8] could trigger proton release upon 2:2 complex formation. The addition of CB[8] to a solution containing V-P- I ³⁺ indeed released protons as monitored by pH-metry and visualized by a coloured indicator. This property was used to induce a host/guest swapping, accompanied by a proton transfer, between V-P-I ³⁺ ⋅ CB[7] and a CB[8] complex of 1-methyl-4-(4-pyridyl)pyridinium. The origin of this negative pK_a shift is proposed to stand in an ideal charge state, and in the position of the two pH-responsive fragments inside the two CB[8] which, alike residues engulfed in proteins, favour the deprotonated form of the guest molecules. Such proton release triggered by a recognition event is reminiscent of several biological processes and may open new avenues toward bioinspired enzyme mimics catalyzing proton transfer or chemical reactions.