SmI2-mediated radical cyclizations directed by a C-Si bond

The use of a silicon stereocontrol element in cyclobutanol and cyclopentanol-forming cyclizations mediated by SmI(2) results in excellent diastereocontrol. The C-Si bond in the products of cyclization provides a versatile handle for further manipulation. An asymmetric route to cyclization substrates involving copper-catalyzed silyl transfer has also been developed.     

Ambient mass spectrometry: bringing MS into the “real world”

Mass spectrometry has recently undergone a second contemporary revolution with the introduction of a new group of desorption/ionization (DI) techniques known collectively as ambient mass spectrometry. Performed in an open atmosphere directly on samples in their natural environments or matrices, or by using auxiliary surfaces, ambient mass spectrometry (MS) has greatly simplified and increased the speed of MS analysis. Since its debut in 2004 there has been explosive growth in the applications and variants of ambient MS, and a very comprehensive set of techniques based on different desorption and ionization mechanisms is now available. Most types of molecules with a large range of masses and polarities can be ionized with great ease and simplicity with the outstanding combination of the speed, selectivity, and sensitivity of MS detection. This review describes and compares the basis of ionization and the concepts of the most promising ambient MS techniques known to date and illustrates, via typical analytical and bioanalytical applications, how ambient MS is helping to bring MS analysis deeper than ever into the “real world” open atmosphere environment—to wherever MS is needed.     

Electric field gradient and electronic properties of crown thioether compounds

We compare published TDPAC experiments on ¹¹¹Cd in the crown thioether C₆H₁₂S₃AgCl with ab-initio electronic structure calculations performed within the framework of the Density Functional Theory using the Projector Augmented Wave method. We conclude from this comparison that the Cd atom at the very moment of the TDPAC experiment is positively charged, and we point out to a methodological difference between reproducing experimental electric-field gradients in molecules versus solid metals.     

High-K multi-quasiparticle states in No

We report results from an experiment on the decay of the high-K isomers in ²⁵⁴No. We have been able to establish the decay from the known high-lying four-quasiparticle isomer, which we assign as a Kπ=¹⁶⁺${\mathrm{K}}^{\pi }={16}^{+}$ state at an excitation energy of Ex=2.928(3) MeV${\mathrm{E}}_x=2.928(3)\text{MeV}$. The decay of this state passes through a rotational band based on a previously unobserved state at Ex=2.012(2) MeV${\mathrm{E}}_x=2.012(2)\text{MeV}$, which we suggest is based on a two-quasineutron configuration with Kπ=¹⁰⁺${\mathrm{K}}^{\pi }={10}^{+}$. This state in turn decays to a rotational band based on the known Kπ=⁸⁻${\mathrm{K}}^{\pi }=8^{-}$ isomer, which we infer must also have a two quasineutron configuration. We are able to assign many new gamma-rays associated with the decay of the Kπ=⁸⁻${\mathrm{K}}^{\pi }=8^{-}$ isomer, including the identification of a highly K-forbidden ΔK=8$\mathrm{\Delta }\mathrm{K}=8$ E1 transition to the ground-state band. These results provide valuable new information on the orbitals close to the Fermi surface, pairing correlations, deformation and rotational response, and K-conservation in nuclei of the deformed trans-fermium region.     

Single‐beam coherent anti‐Stokes Raman scattering (CARS) spectroscopy of gas‐phase CO2 via phase and polarization shaping of a broadband continuum

Coherent anti‐Stokes Raman scattering (CARS) spectroscopy of gas‐phase CO₂ is demonstrated using a single femtosecond (fs) laser beam. A shaped ultrashort laser pulse with a transform‐limited temporal width of ∼7 fs and spectral bandwidth of ∼225 nm (∼3500 cm⁻¹) is employed for simultaneous excitation of the CO₂ Fermi dyads at ∼1285 and ∼1388 cm⁻¹. CARS signal intensities for the two Raman transitions and their ratio as a function of pressure are presented. The signal‐to‐noise ratio of the single beam–generated CO₂ CARS signal is sufficient to perform concentration measurements at a rate of 1 kHz. The implications of these experiments for measuring CO₂ concentrations and rapid pressure fluctuations in hypersonic and detonation‐based chemically reacting flows are also discussed. Copyright © 2010 John Wiley & Sons, Ltd.     

ESR and fluorescence studies of Mn-doped Na2ZnP2O7 single crystal and glasses

X-band electron spin resonance (ESR) spectra and fluorescence measurements were performed on Mn-doped Na₂ZnP₂O₇ (NZPO) single crystal synthesized by the Czochralski pulling method and glasses synthesized by the quenching process. For the single crystal, ESR angular dependences were measured in both the zx and xy plans of the NZPO lattice. The fine and hyperfine structure parameters and g-factor values were determined by modelling the experimental spectra. Using the Newman superposition model, the resonating centres in the single crystal and powder (crushed from crystals) samples are assigned to Mn²⁺ ions substituting for both zinc and sodium. For the glass sample the analysis of the ESR data shows that Mn²⁺ ions substitute for the Na⁺ ions. These interpretations are confirmed by the fluorescence measurements with a unique broad red band for the glassy compound and the presence of two emission bands (green and red) in the case of the crystal sample.     

Selective Isomerization of Epoxides to Allylic Alcohols Catalyzed by TiO2‐Supported Gold Nanoparticles

ReacTiO ₂ ns for rings : Gold nanoparticles supported on TiO₂ are used as a novel heterogeneous catalyst for the isomerization of epoxides to allylic alcohols by a concerted mechanism (see scheme). The reaction proceeds in high yields and the product selectivity is often remarkable.

     

Photovoltaic activity of Ti/MCM‐41

Ti/MCM‐41 is a well‐known heterogeneous catalyst for alkene epoxidation with organic peroxides. This titanosilicate contains isolated titanium atoms forming part of a framework of mesoporous silica whose structure is formed by parallel hexagonal channels 3.2 nm in diameter. The surface area and porosity of Ti/MCM‐41 are about 880 m² g^?1 and 0.70 cm³ g^?1, respectively. These values are among the highest for any material. Herein, we show that Ti/MCM‐41 exhibits photovoltaic activity. Dye‐sensitized solar cells using mesoporous Ti/MCM‐41 (2.8–5.7 % Ti content) as active layer, black dye N3 as photosensitizer and I₃^?/I^? in methoxyacetonitrile as electrolyte exhibit a V_OC, J_SC and FF of 0.44 V, 0.045 mA cm^?2 and 0.33, respectively. These values compare well against 0.75 V, 4.1 mA cm^?2 and 0.64, respectively, measured for analogous solar cells using conventional P‐25 TiO₂. However, the specific current density (J_SC/Ti atom) for the Ti/MCM‐41 is very similar to that of P25 TiO₂.     

Near‐Infrared Emission Quantum Yield of Soluble Short Single‐Walled Carbon Nanotubes

Soluble short single‐walled carbon nanotubes in aerated D₂O emit in the near‐infrared (NIR) region (see picture) with a quantum yield of (3.9±0.5) ×10^?3 and a half‐life of 7.65 μs. This emission is quenched by electron‐ acceptor molecules.