Reactive scattering of a supersonic oxygen atom beam O + I2

Reactive scattering of O atoms with I₂ molecules has been studied at an initial translational energy E = 43 kJ mol^-1 using a supersonic beam of O atoms seeded in He and E = 18 kJ mol^-1 using O atoms seeded in Ne. Velocity distributions of OI product were measured by cross-correlation time-of-flight analysis. Full contour maps of the differential reaction cross section were obtained which show predominantly rebound scattering at both initial translational energies. Scattering in the forward direction has a product translational energy distribution similar to that predicted for a long-lived collision complex but scattering in the backward direction has a much higher product translational energy. The greater predominance of rebound scattering observed for O + I₂ compared with O + Br₂ may be attributed to the greater exoergicity of the O + I₂ reaction. However, comparison with the O + IBr reaction which exhibits a long-lived collision complex mechanism indicates that the predominance of backward scattering for O + I₂ also arises from diminished forward scattering from larger impact parameter collisions.     

Reactive scattering of alkali dimers: Product K atoms from K2+Br2, IBr,BrCN, SnCl4

Approximate angular distribution measurements of reactively scattered K atoms from a potassium dimer K₂ beam by cross beam molecules Br₂, IBr, BrCN, SnCl₄ are reported. Forward peaking in the centre of mass differential cross section for K₂+Br₂, IBr, BrCN unambiguously confirms that the reaction path at large impact parameters yields K + KX + Y products. Differential cross sections at wide angles for K compared with KX products, suggest that the reaction path yielding KX + KY products becomes important at small impact parameters. Comparison of the reactive K atom scattering with the KX scattering lends further support to a schematic mechanism of the reaction dynamics suggested previously. The K₂ + SnCl₄ reaction does not yield reactively scattered K atoms.     

Reactive scattering of oxygen atoms: O+I2, ICl,Br2

Angular and velocity distribution measurements of IO reactive scattering from crossed beams of O atoms and halogen molecules I₂, ICl are reported. Angular distribution measurements are reported for BrO from O + Br₂. The O atom beam was generated at ～350 K from a microwave discharge source and the halogen molecule beam from a supersonic nozzle source at ～380 K. The product time-of-flight distribution was recorded at each laboratory scattering angle by a mini-computer. The scattering data are found to be in excellent agreement with the RRKM-AM model of reactive scattering via a long-lived collision complex. The observation of IO product from O + ICl identifies the complex with a bound O-I-Cl triplet state, previously observed for O-Cl-Cl in matrix isolation studies, as proposed by Herschbach. The maximum centrifugal barrier B _m′ for dissociation of the long-lived complex can be accurately determined, particularly for O + I₂. The B _m′ values indicate that both the entrance and exit valleys of the potential energy surface are governed by centrifugal barriers in the region of long-range van der Waals potentials. The comparatively small reaction cross section (e.g. Q ～ 2 Ų for O + Br₂ from discharge flow measurements) is attributed primarily to an orientation requirement for reaction. The RRKM-AM model indicates a ‘tight linear’ transition state for dissociation of the O-I-I complex, corresponding to significant long-range IO orienting forces in the exit valley of the potential energy surface.     

Reactive scattering of alkali dimers K2 + I2, CH2I2, CHI3, CBr4

Angular distribution measurements of KX reactive scattering of a potassium dimer K₂ beam by I₂ and by a series of halomethane molecules are reported. The K₂ + I₂ reactive scattering is similar to that previously observed for K₂ + Br₂. The predominant reaction path yields K + KI + I with the K and KI product recoiling in the forward direction. However, the forward peak of the KI differential cross section is lower than that for K from K₂ + I₂ and is broader than that observed for KBr from K₂ + Br₂. This is attributed to slow dissociation of the I ₂ ^- ion formed in the electron jump mechanism previously proposed for K₂ + Br₂. In the halomethane reactions, both alkali atoms of the K₂ dimer become bound alkali halide molecules in all reactive collisions, despite the direct dynamics of the corresponding supersonic K atom reactions. Thus, these reactions provide compelling evidence for a second electron jump mechanism, previously proposed for the reactions of K₂ dimers with polyhalide molecules. The differential cross sections for the K₂ dimer plus halomethane reactions indicate an osculating collision complex with a lifetime at least comparable to its rotational period, perhaps much longer. This reaction complex is identified with the doubly ionic state formed by the second electron jump transition.     

Dative Bonding between Group 13 Elements Using a Boron‐Centered Lewis Base

An electron‐rich monovalent boron compound is used as a Lewis base to prepare adducts with Group 13 Lewis acids using both its boron and nitrogen sites. The hard Lewis acid AlCl₃ binds through a nitrogen atom of the Lewis base, while softer Lewis acids GaX₃ (Cl, Br, I) bind at the boron atom. The latter are the first noncluster Lewis adducts between a boron‐centered Lewis base and a main‐group Lewis acid.     

A new cytotoxic diterpenoid glycoside from the leaves of Blumea lacera and its effects on apoptosis and cell cycle

A new diterpenoid glycoside, 6E,10E,14Z-(3S)-17-hydroxygeranyllinalool-17-O-β-d-glucopyranosyl-(1?→?2)-[α-l-rhamnopyranosyl-(1?→?6)]-β-d-glucopyranoside (1) together with the known diterpenoid glycoside (2) and two known flavonoid glycosides (3, 4) were isolated from the methanol extract of Blumea lacera leaves. The structures were determined by the interpretation of their spectroscopic data and comparison with the literature. All compounds were isolated for the first time from B. lacera and evaluated for their cytotoxic activity. Only the new compound (1) showed strong cytotoxic activity with the lowest IC₅₀ value (8.3 μM) being displayed against MCF-7 breast cancer cells. In apoptosis and cell cycle analysis, 1 revealed strong apoptotic activity against MCF-7 cells (45.5% AV⁺/PI^?) after 24 h, but showed no arresting of any of the cell cycle phases in MCF-7.     

Top-Down LESA Mass Spectrometry Protein Analysis of Gram-Positive and Gram-Negative Bacteria

We have previously shown that liquid extraction surface analysis (LESA) mass spectrometry (MS) is a technique suitable for the top-down analysis of proteins directly from intact colonies of the Gram-negative bacterium Escherichia coli K-12. Here we extend the application of LESA MS to Gram-negative Pseudomonas aeruginosa PS1054 and Gram-positive Staphylococcus aureus MSSA476, as well as two strains of E. coli (K-12 and BL21 mCherry) and an unknown species of Staphylococcus. Moreover, we demonstrate the discrimination between three species of Gram-positive Streptococcus (Streptococcus pneumoniae D39, and the viridans group Streptococcus oralis ATCC 35037 and Streptococcus gordonii ATCC35105), a recognized challenge for matrix-assisted laser desorption ionization time-of-flight MS. A range of the proteins detected were selected for top-down LESA MS/MS. Thirty-nine proteins were identified by top-down LESA MS/MS, including 16 proteins that have not previously been observed by any other technique. The potential of LESA MS for classification and characterization of novel species is illustrated by the de novo sequencing of a new protein from the unknown species of Staphylococcus.

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Masked Amino Trimethyl Lock (H2N-TML) Systems: New Molecular Entities for the Development of Turn-On Fluorophores and Their Application in Hydrogen Sulfide (H2S) Imaging in Human Cells

Masked trimethyl lock (TML) systems as molecular moieties enabling the bioresponsive release of compounds or dyes in a controlled temporal and spatial manner have been widely applied for the development of drug conjugates, prodrugs or molecular imaging tools. Herein, we report the development of a novel amino trimethyl lock (H₂N-TML) system as an auto-immolative molecular entity for the release of fluorophores. We designed Cou-TML-N₃ and MURh-TML-N₃ , two azide-masked turn-on fluorophores. The latter was demonstrated to selectively release fluorescent MURh in the presence of physiological concentrations of the redox-signaling molecule H₂S in vitro and was successfully applied to image H₂S in human cells     

Pressure enhanced conductivity in bis-1,2,3-thiaselenazolyl dimers

A synthetic sequence to salts of N-alkylated pyridine-bridged 1,2,3-thiaselenazolo-1,2,3-thiaselenazolylium cations [2]+ (R1 = Me, Et; R2 = H) is described. The corresponding radicals 2 (R1 = Me, Et; R2 = H) can be generated from the cations by chemical or electrochemical reduction. Crystals of the two radicals are isostructural and consist of interpenetrating pi-stacked arrays of closed-shell Se-Se sigma-bonded dimers [2]2 laced together with numerous short intermolecular Se- - -Se, Se- - -S, and Se- - -N contacts. Variable-temperature magnetic, conductivity, and near-infrared optical measurements indicate that the bulk materials behave as small band gap semiconductors with room-temperature conductivities sigma(RT) near 10(-6) S cm(-1) and thermal activation energies Ea of 0.32 eV (R1 = Me) and 0.36 eV (R1 = Et). LMTO band structure calculations on both compounds are consistent with this interpretation. The application of external pressure leads to dramatic increases in conductivity; at 4 GPa sigma(RT) reaches a value near 10(-1) S cm(-1) for R1 = Me and 10(-2) S/cm for R1 = Et. The conductivity remains activated for both compounds, but for R1 = Me the activation energy Ea is reduced to near 0.03 eV at 5 GPa, suggestive of a weakly metallic state.     

Bis-1,2,3-thiaselenazolyl radicals and their sigma-bonded dimers

Resonance stabilized bis-1,2,3-thiaselenazolyl radicals associate in the solid state to afford Se-Se sigma-bonded dimers.