Field emission tip as a nanometer source of free electron femtosecond pulses

We report a source of free electron pulses based on a field emission tip irradiated by a low-power femtosecond laser. The electron pulses are shorter than 70 fs and originate from a tip with an emission area diameter down to 2 nm. Depending on the operating regime we observe either photofield emission or optical field emission with up to 200 electrons per pulse at a repetition rate of 1 GHz. This pulsed electron emitter, triggered by a femtosecond oscillator, could serve as an efficient source for time-resolved electron interferometry, for time-resolved nanometric imaging and for synchrotrons.     

Enantioselectivity of monolithic silica stationary phases immobilized with different concentrations cellulose tris (3,5-dimethylphenylcarbamate), analyzed with different mobile phases in capillary electrochromatography

The 3,5-dimethylphenylcarbamate derivatives of cellulose bearing 3-(triethoxysilyl)propyl residues were immobilized in a capillary format onto a monolithic silica support by intermolecular polycondensation of the triethoxysilyl groups. The resulting columns were used for chiral separations using capillary electrochromatography. The effects of the synthesizing solvent, the selector coating procedure, the chiral selector concentration onto the silica monolith and the mobile phase pH value, on the separation of enantiomers were studied. The column-to-column reproducibility and stability also were evaluated. A test set of 14 chiral substances, including acidic, neutral, bifunctional and basic compounds, was used to investigate the effects of the factors mentioned above. Twelve pairs of enantiomers showed enantioselectivity at some of the different conditions tested. The column-to-column repeatability was satisfactory, and the prepared columns were stable under the adopted analysis conditions.     

Synthesis of 2,3-anti-3,4-anti and 2,3-anti-3,4-syn propionate motifs: a diastereoselective tandem sequence of Mukaiyama and free-radical-based hydrogen transfer reactions

[reaction: see text] Reported herein is a strategy employing a Mukaiyama reaction in tandem with a hydrogen transfer reaction for the elaboration of 2,3-anti-3,4-anti and 2,3-anti-3,4-syn propionate motifs. The mode of complexation is controlled through monodentate or chelate pathways for the Mukaiyama reaction to give access to either syn or anti aldol products, precursors of the free-radical reduction reaction. Boron Lewis acid is used to control the free-radical reaction through the exocyclic pathway.     

Intrinsic and Intramolecular Lipophilicity Effects in O-Glucuronides

In this study, we compared the lipophilicity of O-glucuronides and their aglycones. Distribution coefficients (log D) and P values of neutral species (log P) were determined by centrifugal partition chromatography (CPC) in octanol/buffer systems. Two-phase potentiometry was also used to measure the log P value of some lipophilic solutes. The experimentally determined global influence of glucuronidation on lipophilicity, obtained as the difference (decrement) log P_{(glucuronide)} ? log P_(aglycone), was found to be ?1.30 ± 0.16 (n = 4) for glucuronides of alcohols (methyl, menthyl, neomenthyl, and chloramphenicol O-glucuronide). The mean decrement was ?2.06 ± 0.31 (n = 9) for glucuronides of phenols (phenyl, p-nitrophenyl, 1-naphthyl, 6-bromo-2-naphthyl, 4-methylumbelliferyl, 3-coumarinyl, phenolphthalein, 4′-benzophenonyl O-glucuronide, and diflunisal phenolic glucuronide). For the acylglucuronide of diflunisal and its rearrangement isomers, the mean decrement was ?1.80 ± 0.08 (n = 4; range ?1.7 to ?1.9). Differences in through-bond proximity effects as parametrized in the CLOGP algorithm seem to account for much of this difference. Conformational factors may also play a role, although it appears modest and unassessable for the glucuronides investigated here. The results imply that in vivo glucuronidation should have a stronger influence on the excretion of phenols than on that of alcohols.     

Influence of peak measurement parameters on the quality of chiral electrophoretic separations

The effect of nine peak measurement/analysis parameters on chiral capillary electrophoresis (CE), followed by UV detection, was studied. The parameters pertained UV-detection (detection wavelength, reference wavelength, and wavelength bandwidths), signal processing (data acquisition rate, type and amount of filtering) and peak detection (detection threshold and peak width). The influence of these factors on the chiral separation of dimethindene enantiomers was studied at two different concentrations (i.e., at high and low signal-to-noise (S/N) ratio) by the means of experimental designs. The electropherogram characteristics considered were the resolution between the two enantiomers, the peak areas, and the S/N ratio. A D-optimal design was first used as screening design to identify the most critical parameters. Afterwards, a modelling of the different responses as a function of these critical parameters was performed based on the results of a face-centered central composite design. The results showed that the signal-processing parameters should be carefully selected when developing a CE separation since very important variations in the separation, the S/N ratio and the peak area of the substances can occur by setting these parameters at different levels. The detection wavelength should also be carefully chosen for optimal peak area measurement. The role of these parameters becomes more important with decreasing concentration of the analytes (i.e., low S/N ratio). This study showed that the peak measurement/analysis parameters should be optimized as the chemical and physical parameters of a method. They also should always be well specified in order to allow a good transfer of a method from one instrument to another.     

Access to New Endoperoxide Derivatives by Electrochemical Oxidation of Substituted 3‐Azabicyclo[4.1.0]hept‐4‐enes

A series of substituted 3‐azabicyclo[4.1.0]hept‐4‐ene derivatives were prepared and analysed by cyclic voltammetry. Preparative aerobic electrochemical oxidation reactions were then carried out. Three original endoperoxides were isolated, characterised and subjected to antimalarial and cytotoxicity activity assays.     

Highly efficient metal‐free organic catalysts to design new Environmentally‐friendly starch‐based blends

A one‐step process is reported to directly synthesize blends of poly(trimethylene carbonate) (PTMC) with a modified granular starch. Trimethylene Carbonate (TMC) ring‐opening polymerization is performed in the presence of native starch particles in bulk conditions at 150 °C and the efficiency of metal‐free organic catalysts (TBD and phosphazene superbases P1‐t‐Oct, P2‐t‐bu, and P4‐t‐bu) are investigated to replace the organo‐metallic stannous octanoate initiator. TMC monomer is successively converted into PTMC and the robustness of organic catalysts is highlighted with significant activities at very low concentrations (<100 ppm), where stannous octanoate is inefficient. Reactivity of starch toward TMC ROP is deeply investigated by NMR techniques and a starch‐graft‐PTMC is indirectly evidenced. Starch substitution degree reaches 0.9% indicating that PTMC grafting only occurs at the surface of swollen granular starch. PTMC graft length from the starch surface remained low in the range 2–12 and model ROP reactions highlight the role of TMC hydrolysis on PTMC graft length. Despite low PTMC grafts, a fine dispersion of intact starch particles into the PTMC matrix is evidenced. Consequently, metal‐free organic catalysts at low concentrations are promising candidates for synthesizing blends of PTMC with high loadings of surface‐modified starch (32% by weight) in 2 min within a one‐step process. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 493–503     

In situ single‐crystal to single‐crystal (SCSC) transformation of the one‐dimensional polymer catena‐poly[[diaqua(sulfato)copper(II)]‐μ2‐glycine] into the two‐dimensional polymer poly[μ2‐glycine‐μ4‐sulfato‐copper(II)]

The one‐dimensional coordination polymer catena‐poly[diaqua(sulfato‐κO)copper(II)]‐μ₂‐glycine‐κ²O:O′], [Cu(SO₄)(C₂H₅NO₂)(H₂O)₂]_n, (I), was synthesized by slow evaporation under vacuum of a saturated aqueous equimolar mixture of copper(II) sulfate and glycine. On heating the same blue crystal of this complex to 435 K in an oven, its aspect changed to a very pale blue and crystal structure analysis indicated that it had transformed into the two‐dimensional coordination polymer poly[(μ₂‐glycine‐κ²O:O′)(μ₄‐sulfato‐κ⁴O:O′:O′′:O′′)copper(II)], [Cu(SO₄)(C₂H₅NO₂)]_n, (II). In (I), the Cu^II cation has a pentacoordinate square‐pyramidal coordination environment. It is coordinated by two water molecules and two O atoms of bridging glycine carboxylate groups in the basal plane, and by a sulfate O atom in the apical position. In complex (II), the Cu^II cation has an octahedral coordination environment. It is coordinated by four sulfate O atoms, one of which bridges two Cu^II cations, and two O atoms of bridging glycine carboxylate groups. In the crystal structure of (I), the one‐dimensional polymers, extending along [001], are linked via N—H...O, O—H...O and bifurcated N—H...O,O hydrogen bonds, forming a three‐dimensional framework. In the crystal structure of (II), the two‐dimensional networks are linked via bifurcated N—H...O,O hydrogen bonds involving the sulfate O atoms, forming a three‐dimensional framework. In the crystal structures of both compounds, there are C—H...O hydrogen bonds present, which reinforce the three‐dimensional frameworks.     

Improved variable reduction in partial least squares modelling based on predictive-property-ranked variables and adaptation of partial least squares complexity

The calibration performance of partial least squares for one response variable (PLS1) can be improved by elimination of uninformative variables. Many methods are based on so-called predictive variable properties, which are functions of various PLS-model parameters, and which may change during the variable reduction process. In these methods variable reduction is made on the variables ranked in descending order for a given variable property. The methods start with full spectrum modelling. Iteratively, until a specified number of remaining variables is reached, the variable with the smallest property value is eliminated; a new PLS model is calculated, followed by a renewed ranking of the variables. The Stepwise Variable Reduction methods using Predictive-Property-Ranked Variables are denoted as SVR-PPRV. In the existing SVR-PPRV methods the PLS model complexity is kept constant during the variable reduction process. In this study, three new SVR-PPRV methods are proposed, in which a possibility for decreasing the PLS model complexity during the variable reduction process is build in. Therefore we denote our methods as PPRVR-CAM methods (Predictive-Property-Ranked Variable Reduction with Complexity Adapted Models). The selective and predictive abilities of the new methods are investigated and tested, using the absolute PLS regression coefficients as predictive property. They were compared with two modifications of existing SVR-PPRV methods (with constant PLS model complexity) and with two reference methods: uninformative variable elimination followed by either a genetic algorithm for PLS (UVE-GA-PLS) or an interval PLS (UVE-iPLS). The performance of the methods is investigated in conjunction with two data sets from near-infrared sources (NIR) and one simulated set. The selective and predictive performances of the variable reduction methods are compared statistically using the Wilcoxon signed rank test. The three newly developed PPRVR-CAM methods were able to retain significantly smaller numbers of informative variables than the existing SVR-PPRV, UVE-GA-PLS and UVE-iPLS methods without loss of prediction ability. Contrary to UVE-GA-PLS and UVE-iPLS, there is no variability in the number of retained variables in each PPRV(R) method. Renewed variable ranking, after deletion of a variable, followed by remodelling, combined with the possibility to decrease the PLS model complexity, is beneficial. A preferred PPRVR-CAM method is proposed.