Band-selective recoupling of homonuclear double-quantum dipolar interaction with a generalized composite 0 degrees pulse: application to 13C aliphatic region-selective magnetization transfer in solids

Recoupling of homonuclear double quantum (DQ)-dipolar interactions is a useful technique for the structural analysis of molecules in solids. We have designed a series of elemental 0 degrees pulses for the recoupling sequences with the rf phase rotation about the z-axis, known as CN. The proposed 0 degrees pulses whose total flip angle >/=360 degrees provide spin rotation vectors in the xy-plane. Thus, the residual spin rotation can be canceled by rf phase rotation about the z-axis. An analysis by the coherent averaging theory showed that effective bandwidths of the recoupling sequences are limited not by the reduction in the dipolar scaling factor but by the increase in the residual spin rotation due to offset. A CN sequence with these elemental pulses provides an effective bandwidth of DQ-dipolar recoupling from ca. 0.5nu(R) to 4nu(R) for numerical simulations. Here, nu(R) is the sample spinning frequency. The 0 degrees pulses were applied to band-selective recoupling for the magnetization transfer in uniformly 13C-labeled molecules. Narrow-band recoupling enhances the magnetization transfer between spins within the effective range by decoupling the dipolar interactions between spins one of which is outside the range. The narrow band operation reduces rf field strength, which improves the CH decoupling. Increases in signal intensities by the use of the proposed 0 degrees pulses are experimentally shown for 13C-labeled amino acids.     

Iodine atom transfer [3 + 2] cycloaddition reaction with electron-rich alkenes using N-tosyliodoaziridine derivatives as novel azahomoallyl radical precursors

Treatment of N-tosyliodoaziridine derivatives with Et(3)B efficiently produces various azahomoallyl radical (2-akenylamidyl radical) species which give oxygen-functionalized pyrrolidine derivatives through iodine atom transfer [3 + 2] cycloaddition with electron-rich alkenes such as enol ethers and ketene acetal. The present cycloaddition reaction proceeds regioselectively via C-N bond cleavage of an aziridinylalkyl radical intermediate and addition of the resulting azahomoallyl radicals to the terminal carbon of an alkene. The reaction of alkenes with the cyclohexenylamidyl radical generated from an optically active bicyclic iodoaziridine [(1S,2S,6S)-2-iodo-7-(p-toluenesulfonyl)-7-azabicyclo[4.1.0]heptane, 94% ee] also proceeds to give optically active octahydroindole derivatives (84-93% ee).     

Long rod-like array of bis(imidazolyl)porphyrinatocobalt(III) by successive complementary coordination

Simple bis(imidazolyl)porphyrin cobalt(III) complex was found to form a long polymeric array by complementary coordination of imidazole to cobalt ion. Formation of higher ordered assemblies was also observed.     

A commutativity criterion for certain algebras of invariant differential operators on nilpotent homogeneous spaces

Let G be a connected, simply connected real nilpotent Lie group with Lie algebra , H a connected closed subgroup of G with Lie algebra and f a linear form on satisfying f([, ]) = {0} Let _f be the unitary character of H with differential at the origin. Let _f be the unitary representation of G induced from the character _f of H. We consider the algebra (, , f) of differential operators invariant under the action of G on the bundle with basis G/H associated to these data. We show that (, , f) is commutative if and only if _f is of finite multiplicities. This proves a conjecture of Corwin-Greenleaf and Duflo. Mathematics Subject Classification (1991):43A80, 43A85, 22E25, 22E27, 22E30UMR n 7539 du CNRS, Analyse, Géométrie et Applications.UMR n 7586 du CNRS, Théorie des Groupes, Représentations, Applications.     

Measurement of the resonant d(mu)t molecular formation rate in solid HD

Measurements of muon-catalyzed dt fusion ( d(mu)t-->4He + n + mu(-)) in solid HD have been performed. The theory describing the energy dependent resonant molecular formation rate for the reaction (mu)t + HD-->[(d(mu)t)pee](*) is compared to experimental results in a pure solid HD target. Constraints on the rates are inferred through the use of a Monte Carlo model developed specifically for the experiment. From the time-of-flight analysis of fusion events in 16 and 37 microg x cm(-2) targets, an average formation rate consistent with 0.897+/-(0.046)(stat)+/-(0.166)(syst) times the theoretical prediction was obtained.     

Relaxation behavior of laser-polarized (129)Xe gas: size dependency and wall effect of the T(1) relaxation time in glass and gelatin bulbs

Size dependency of the relaxation time T(1) was measured for laser-polarized (129)Xe gas encapsulated in different sized cavities made by glass bulbs or gelatin capsules. The use of laser-polarized gas enhances the sensitivity a great deal, making it possible to measure the longer (129)Xe relaxation time in quite a short time. The size dependency is analyzed on the basis of the kinetic theory of gases and a relationship is derived in which the relaxation rate is connected with the square inverse of the diameter of the cavity. Such an analysis provides a novel parameter which denotes the wall effect on the relaxation rate when a gas molecule collides with the surface once in a second. The relaxation time of (129)Xe gas is also dependent on the material which forms the cavity. This dependency is large and the relaxation study using polarized (129)Xe gas is expected to offer important information about the state of the matter of the cavity wall.     

Gamow-teller strengths of the inverse beta transition 176Yb-->176Lu for spectroscopy of proton-proton and other sub-MeV solar neutrinos

Discrete Gamow-Teller (GT) transitions 176Yb-->176Lu at low excitation energies have been measured via the ( 3He,t) reaction at 450 MeV and at 0 degrees. For 176Yb, two low-lying states are observed, setting low thresholds Q(nu) = 301 and 445 keV for neutrino ( nu) capture. Capture rates estimated from the measured GT strengths, the simple two-state excitation structure, and the low Q(nu) in Yb-Lu indicate that Yb-based nu detectors are well suited for a direct measurement of the sub-MeV solar electron-neutrino ( nu(e)) spectrum including pp neutrinos.     

Adsorption and structure of methyl mercaptoacetate on Cu(1 1 1) surface by XPS and NEXAFS spectroscopy

Methyl mercaptoacetate (MA) on Cu(1 1 1) surface was investigated using synchrotron radiation-based X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. MA adsorbs on the surface via thiolate formation and weak interaction of the carbonyl group with the surface. Two different adsorption states previously reported for methanethiolate and ethanethiolate were confirmed, besides atomic sulfur. NEXAFS measurements support gauche-type conformation of MA whose skeleton lies on the surface.     

Lactic acid‐ and carbonate‐based crosslinked polymeric micelles for drug delivery

Our objective was to synthesize and evaluate lactic acid‐ and carbonate‐based biodegradable core‐ and core‐corona crosslinkable copolymers for anticancer drug delivery. Methoxy poly(ethylene glycol)‐b‐poly(carbonate‐co‐lactide‐co‐5‐methyl‐5‐allyloxycarbonyl‐1,3‐dioxane‐2‐one) [mPEG‐b‐P(CB‐co‐LA‐co‐MAC)] and methoxy poly(ethylene glycol)‐b‐poly(acryloyl carbonate)‐b‐poly(carbonate‐co‐lactide) [mPEG‐b‐PMAC‐b‐P(CB‐co‐LA)] copolymers were synthesized by ring‐opening polymerization of LA, CB, and MAC using mPEG as an macroinitiator and 1,8‐diazabicycloundec‐7‐ene as a catalyst. These amphiphilic copolymers which exhibited low polydispersity and critical micelle concentration values (0.8–1 mg/L) were used to prepare micelles with or without drug and stabilized by crosslinking via radical polymerization of double bonds introduced in the core and interface to improve stability. mPEG₁₁₄‐b‐P(CB₈‐co‐LA₃₅‐co‐MAC_2.5) had a higher drug encapsulation efficiency (78.72% ± 0.15%) compared to mPEG₁₁₄‐b‐PMAC_2.5‐b‐P(CB₉‐co‐LA₃₉) (20.29% ± 0.11%).¹H NMR and IR spectroscopy confirmed successful crosslinking (～70%) while light scattering and transmission electron microscopy were used to determine micelle size and morphology. Crosslinked micelles demonstrated enhanced stability against extensive dilution with aqueous solvents and in the presence of physiological simulating serum concentration. Furthermore, bicalutamide‐loaded crosslinked micelles were more potent compared to non‐crosslinked micelles in inhibiting LNCaP cell proliferation irrespective of polymer type. Finally, these results suggest crosslinked micelles to be promising drug delivery vehicles for chemotherapy. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013