Development of a novel high volume band compression injector for the analysis of complex samples like toxaphene pesticide

A new type of injector has been developed for gas chromatographic analysis. The injector has high volume and band compression (HVBC) capabilities useful for the analysis of complex samples. The injector consists essentially of a packed liner operated at room temperature while a narrow heated zone is used to axially scan the liner selectively desorbing the compounds of interest. The scanning speed, distance and temperature of the zone are precisely controlled. The liner is connected to an interface which can vent the solvent or any undesirable compounds, and transfer the analytes to an analytical column for separation and quantification. The injector is designed to be compatible with injection volumes from 1 to more than 250microL. At a low sample volume of 1microL, the injector has competitive performances compared to those of the "on-column" and "split/splitless" injectors for the fatty acid methyl esters and toxaphene compounds tested. For higher volumes, the system produces a linear response according to the injected volume. In this explorative study, the maximum volume injected seems to be limited by the saturation of the chromatographic system instead of being defined by the design of the injector. The HVBC injector can also be used to conduct "in situ" pretreatment of the sample before its transfer to the analytical column. For instance, a toxaphene sample was successively fractionated, using the HVBC injector, in six sub-fractions characterized by simpler chromatograms than the chromatogram of the original mixture. Finally, the ability of the HVBC injector to "freeze" the separation in time allowing the analyst to complete the analysis at a later time is also discussed.     

Are Allenes with Zwitterionic Character Still Allenes? Of Course!

The true ground state of 1 is a matter of debate, but for clarity and convenience the allene resonance form 1 a , is the most appropriate. The arguments for aromaticity made by Christl and Engels are shown to be incorrect.

     

Synthesis and characterization of epoxy functionalized cooligomers based on chlorotrifluoroethylene and allyl glycidyl ether

The synthesis of functionalized fluorocooligomers based on chlorotrifluoroethylene (CTFE) and allyl glycidyl ether (AGE) under radical copolymerization is presented. The compositions of comonomers in the cooligomers were determined by three different analyses viz: from ¹H and ¹⁹F NMR spectroscopy by using 1,3‐bis(trifluoromethyl) benzene as the external standard, epoxy equivalent weight value, and elemental analyses. The compositions determined by three methods were matching reasonably well and showed that the resulting poly(CTFE‐co‐AGE) cooligomers exhibit a tendency for alternation. The distribution of the monomers in the cooligomers was proposed based on the assessment of the reactivity ratios, r_i, of both comonomers. These values were determined from the kinetics of radical copolymerization of CTFE with AGE from Fineman‐Ross, Kelen‐Tudos, and extended Kelen‐Tudos methods which led to the assessment of the average reactivity ratios as: r_CTFE = 0.20 ± 0.03 and r_AGE = 0.15 ± 0.08 at 74 °C. The lower M_n values substantiated the formation of cooligomers rather than copolymers. The formation of cooligomers was attributed to the chain transfer to AGE (by hydrogen abstraction from AGE) from the allylic transfer. The poly(CTFE‐co‐AGE) cooligomers were soluble in most of the common organic polar solvents. An optimization of cooligomer yields was investigated by using ethyl vinyl ether as a third comonomer and from different initiators. The thermal stabilities of the cooligomers, obtained by thermal gravimetric analysis, showed a 5% weight loss at temperatures over 225 °C under air. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3587–3595, 2010     

Recent progress in homogeneous supported asymmetric catalysis: example of the BINAP and the BOX ligands

Industrial developments of asymmetric catalysis are slowed down by cost and toxicity of the soluble transition metal complexes which are used as catalysts. This problem could be solved by using homogeneous supported catalysis among other technologies. The article analyzes recent results obtained in the fields of catalysis using transition metal complexes grafted on organic or inorganic materials. Two types of ligand are considered: BINAP and BOX. In these two cases several approaches are still under investigations and some of them appear to give a higher performance, such as the polymer with ligand in the main chain and with rigid spacer in case of the BINAP and the ligand grafted on silica particles in the case of BOX.     

Oligonucleotide Analogues with Integrated Bases and Backbones. Part 23

The sulfone 2 , and the sulfoxides (S)‐ 3 and (R)‐ 3 were obtained by oxidation of the thiomethylene‐linked A*[s ]U dinucleoside 1 . Conformational analysis and association studies of 2 , (S)‐ 3 , and (R)‐ 3 reveal a strong influence of the configuration on the conformation of the linking unit and on the self‐association of the dinucleosides.     

Self assembly of anastomosis-like superstructures in fatty acid/guanidine hydrochloride aqueous dispersions

A mixture between 1% sodium myristate and guanidine hydrochloride at a molar ratio of 1 in water forms a gel of membranes below a phase transition of ca. 21 °C and a viscous limpid and isotropic solution above. As observed by both TEM and AFM, we report the formation of interconnected superstructures in that latter phase. Those assemblies exhibit a size of ca. 4–40 nm width and several tens of μm length with unexpected disconnections and re-connections between them having the appearance of an anastomosis-like superstructure.     

Magnetic N-doped carbon nanotubes: A versatile and efficient material for the determination of polycyclic aromatic hydrocarbons in environmental water samples

This paper describes a new, efficient and versatile method for the sampling and preconcentration of PAH in environmental water matrices using special hybrid magnetic carbon nanotubes. These N-doped amphiphilic CNT can be easily dispersed in any aqueous matrix due to the N containing hydrophilic part and at the same time show high efficiency for the adsorption of different PAH contaminants due to the very hydrophobic surface. After adsorption, the CNT can be easily removed from the medium by a simple magnetic separation. GC/MS analyses showed that the CNT method is more efficient than the use of polydimethylsiloxane (PDMS) with much lower solvent consumption, technical simplicity and time, showing good linearity (range 0.18–80.00 μg L⁻¹) and determination coefficient (R² > 0.9810). The limit of detection ranged from 0.05 to 0.42 μg L⁻¹ with limit of quantification from 0.18 to 1.40 μg L⁻¹. Recovery (n = 9) ranged from 80.50 ± 10 to 105.40 ± 12%. Intraday precision (RSD, n = 9) ranged from 1.91 to 9.01%, whereas inter day precision (RSD, n = 9) ranged from 7.02 to 17.94%. The method was applied to the analyses of PAH in four lake water samples collected in Belo Horizonte City, Brazil.     

On‐Site Determination of Carbendazim,Cathecol and Hydroquinone in Tap Water Using a Homemade Batch Injection Analysis Cell for Screen Printed Electrodes

In this work, we present a simple homemade batch‐injection analysis cell for screen‐printed electrodes (BIA‐SPE). The potential of the proposed system for on‐site analysis was demonstrated by the determination of carbendazim, catechol, and hydroquinone in tap water. The system provided reduced injection volume (30 µL), high analytical frequency (≈200 h^?1) and low detection limits (nanomolar level). Moreover, the BIA‐SPE cell presented better stability (RSD≈0.4 %) than a conventional flow injection cell for SPE (RSD≈5.0 %) in organic media. The proposed homemade BIA‐SPE cell is very simple, inexpensive and can be easily constructed in any laboratory.     

Enantiospecific C?H Activation Using Ruthenium Nanocatalysts

The activation of C H bonds has revolutionized modern synthetic chemistry. However, no general strategy for enantiospecific C H activation has been developed to date. We herein report an enantiospecific C H activation reaction followed by deuterium incorporation at stereogenic centers. Mechanistic studies suggest that the selectivity for the α‐position of the directing heteroatom results from a four‐membered dimetallacycle as the key intermediate. This work paves the way to novel molecular chemistry on nanoparticles.     

One‐Pot Preparation of Inert Well‐Defined Polymers by RAFT Polymerization and In Situ End Group Transformation

A one‐pot procedure that straightforwardly combines reversible addition‐fragmentation chain transfer (RAFT) polymerization and end group transformation to remove the RAFT end groups is developed for the synthesis of well‐defined poly(meth)acrylates and polyacrylamides with inert end groups. This procedure only requires the addition of an amine at the end of the standard RAFT polymerization procedure, which avoids the separation and purification of the intermediate polymers and, hence, extremely reduces the working time and utilized amount of solvents. Upon addition of the amine, a thiol group is formed by aminolysis of the thiocarbonylthio group, which subsequently undergoes Michael addition with unreacted monomer leading to an inert thioether functionalized polymer.