Single-walled carbon nanohorns immobilized on a microporous hollow polypropylene fiber as a sorbent for the extraction of volatile organic compounds from water samples

We have evaluated the behavior of single-walled carbon nanohorns as a sorbent for headspace and direct immersion (micro)solid phase extraction using volatile organic compounds (VOCs) as model analytes. The conical carbon nanohorns were first oxidized in order to increase their solubility in water and organic solvents. A microporous hollow polypropylene fiber served as a mechanical support that provides a high surface area for nanoparticle retention. The extraction unit was directly placed in the liquid sample or the headspace of an aqueous standard or a water sample to extract and preconcentrate the VOCs. The variables affecting extraction have been optimized. The VOCs were then identified and quantified by GC/MS. We conclude that direct immersion of the fiber is the most adequate method for the extraction of VOCs from both liquid samples and headspace. Detection limits range from 3.5 to 4.3 ng L^?1 (excepted for toluene with 25 ng L^?1), and the precision (expressed as relative standard deviation) is between 3.9 and 9.6 %. The method was applied to the determination of toluene, ethylbenzene, various xylene isomers and styrene in bottled, river and tap waters, and the respective average recoveries of spiked samples are 95.6, 98.2 and 86.0 %.

Templating Ag on DNA/polymer hybrid nanowires: Control of the metal growth morphology using functional monomers

Ag nanowires and nanoparticles have been formed on hybrid λ-DNA/conducting polymer templates. The strong, but non-covalent, interaction of the conducting polymer with the double helix allowed us to incorporate chemical functionalities (alkynyl) into the DNA/conducting polymer strands by synthesis of functional monomers. Oxidative polymerisation of alkynyl-thienylpyrrole in the presence of λ-DNA produced conductive nanowires bearing alkyne groups; we show, using a combination of AFM, cAFM and EFM phase measurements that the alkyne functionality strong influences the subsequent templating reaction of Tollens’ reagent to produce uniform conductive nanowires comprised of many connected Ag clusters.     

Pt supported on carbon nanofibers as electrocatalyst for low temperature polymer electrolyte membrane fuel cells

Carbon nanofibers synthesized via the thermo catalytic decomposition of methane were investigated for the first time as an electrocatalyst support in PEMFC cathodes. Their textural and physical properties make them a highly efficient catalyst support for cathodic oxygen reduction in low temperature PEMFC. Tests performed in MEAs showed that Pt supported on carbon nanofibers exhibited an enhancement of ca. 94% in power density at 0.600 V, in comparison with a commercial catalyst supported on conventional carbon black, Pt/Vulcan XC-72R.     

Structural Analysis of Zincocenes with Substituted Cyclopentadienyl Rings

New zincocenes [ZnCp′₂] ( 2 – 5 ) with substituted cyclopentadienyl ligands C₅Me₄H, C₅Me₄tBu, C₅Me₄SiMe₂tBu and C₅Me₄SiMe₃, respectively, have been prepared by the reaction of ZnCl₂ with the appropriate Cp′‐transfer reagent. For a comparative structural study, the known [Zn(C₅H₄SiMe₃)₂] ( 1 ), has also been investigated, along with the mixed‐ring zincocenes [Zn(C₅Me₅)(C₅Me₄SiMe₃)] ( 6 ) and [Zn(C₅Me₅)(C₅H₄SiMe₃)] ( 7 ), the last two obtained by conproportionation of [Zn(C₅Me₅)₂] with 5 or 1 , as appropriate. All new compounds were characterised by NMR spectroscopy, and by X‐ray methods, with the exception of 7 , which yields a side‐product ( C ) upon attempted crystallisation. Compounds 5 and 6 were also investigated by ¹³C CPMAS NMR spectroscopy. Zincocenes 1 and 2 have infinite chain structures with bridging Cp′ ligands, while 3 and 4 exhibit slipped‐sandwich geometries. Compounds 5 and 6 have rigid, η⁵/η¹(σ) structures, in which the monohapto C₅Me₄SiMe₃ ligand is bound to zinc through the silyl‐bearing carbon atom, forming a Zn? C bond of comparable strength to the Zn? Me bond in ZnMe₂. Zincocene 5 has dynamic behaviour in solution, but a rigid η⁵/η¹(σ) structure in the solid state, as revealed by ¹³C CPMAS NMR studies, whereas for 6 the different nature of the Cp′ ligands and of the ring substituents of the η¹‐Cp′ group (Me and SiMe₃) have permitted observation for the first time of the rigid η⁵/η¹ solution structure. Iminoacyl compounds of composition [Zn(η⁵‐C₅Me₄R)(η¹‐C(NXyl)C₅Me₄R)] resulting from the reactions of some of the above zincocenes and CNXyl (Xyl=2,6‐dimethylphenylisocyanide) have also been obtained and characterised.     

Magnetic–fluorescent Langmuir–Blodgett films of fluorophore-labeled ferritin nanoparticles

We have covalently coupled fluorophore 4-(2-hydroxyethoxy)-7-nitro-2,1,3-benzoxadiazole (NBD) to the external ferritin shell through lysine residues. An increase in the luminescence quantum yield of the fluorescent ferritin particles and a blue shift in its emission peak compared to individual fluorophore were observed. The study of the particles by transmission electron microscopy showed that the native iron core ferritin is intact and that no degradation occurs during chemical functionalization of the protein shell. The NBD-labeled ferritin particles are water soluble, which allowed their controlled deposition by the Langmuir–Blodgett (LB) technique. Superparamagnetic and fluorescent properties of the particles are preserved within the LB film.     

Intercalation chemistry of layered vanadyl phosphate: a review

The intercalation chemistry of layered α_I modification of vanadyl phosphate and vanadyl phosphate dihydrate is reviewed. The focus is on neutral molecular guests and on metal cations used as guest species. The basic condition for the ability of the neutral molecules to be intercalated into vanadyl phosphate is a presence of an electron donor atom in them. The most commonly used guest compounds are those containing oxygen, nitrogen or sulfur as electron donor atoms. Regarding the molecules containing oxygen, various compounds were used as molecular guests starting from water to alcohols, ethers, aldehydes, ketones, carboxylic acids, lactones, and esters. An arrangement of the guest molecules in the interlayer space is discussed in connection with the data obtained by powder X-ray diffraction, thermogravimetry, IR and Raman spectroscopies, and solid-state NMR. In some cases, the local structure was suggested on the basis of quantum chemical calculations. Besides of those O-donor guests, also N-donor guests such as amines, nitriles and nitrogenous heterocycles and S-donor guests such as tetrathiafulvalene were intercalated into VOPO₄. Also intercalates of complexes like ferrocene were prepared. Intercalation of cations is accompanied by a reduction of vanadium(V) to vanadium(IV). In this kind of intercalation reactions, an iodide of the intercalated cation is often used as it serves both as a mild reduction agent and as a source of the intercalated species. Intercalates of alkali metals, hydronium and ammonium were prepared and characterized. In the case of lithium and sodium intercalates, a staging phenomenon was observed. These redox intercalated vanadyl phosphates undergo ion exchange reactions which are discussed from the point of the nature of cations involved in the exchange. Vanadyl phosphates in which a part of vanadium atom is replaced by other metals are also briefly reviewed.     

Determination of organic and inorganic mercury species in water and sediment samples by HPLC on-line coupled with ICP-MS

This paper describes a preconcentration method for Hg²⁺ and MeHg⁺ in water samples using sodium diethyldithiocarbamate immobilized in polyurethane foam (PU-NaDDC) and an extraction method for several mercury species in sediment samples, including MeHg⁺, EtHg⁺ and PhHg⁺, which is simple, rapid, and uses a single organic solvent. Separation and measurement were done by high-performance liquid chromatography on-line with inductively coupled plasma mass spectrometry (HPLC/ICP-MS). Initially, the test of recovery was applied using procedures compatible with HPLC. Under the optimum extraction conditions, recoveries of 96.7, 96.3 and 97.3% were obtained for MeHg⁺, EtHg⁺, and PhHg⁺, respectively, from n = 4 spiked sediment samples. This study also demonstrates that the combination of solid-phase extraction on PU-NaDDC with HPLC separation and ICP-MS detection is an effective preconcentration procedure for simultaneous measurement of Hg²⁺ and MeHg⁺ at ultra-trace levels in water samples. The application of the proposed procedure to the determination of mercury species in drinking water sample was investigated. The proposed method clearly gave satisfactory average recoveries between 93.7 and 101.5%.     

One-step in-syringe ionic liquid-based dispersive liquid–liquid microextraction

Dispersive liquid–liquid microextraction (DLLME) has been proved to be a powerful tool for the rapid sample treatment of liquid samples providing at the same time high enrichment factors and extraction recoveries. A new, simple and easy to handle one step in-syringe set-up for DLLME is presented and critically discussed in this paper. The novel approach avoids the centrifugation step, typically off-line and time consuming, opening-up a new horizon on DLLME automation. The suitability of the proposal is evaluated by means of the determination of non-steroidal anti-inflammatory drugs in urine by liquid chromatography/ultraviolet detection. In the presented approach an ionic liquid is used as extractant. The target drugs can be determined in urine within the concentration range 0.02–10 μg mL⁻¹, allowing their determination at therapeutic and toxic levels. Limits of detection were in the range from 8.3 ng mL⁻¹ (indomethacin) to 32 ng mL⁻¹ (ketoprofen). The repeatability of the proposed method expressed as RSD (n = 5) varied between 2.5% (for ketoprofen) and 8.6% (for indomethacin).     

Development of a versatile,easy and rapid atmospheric monitor for benzene,toluene, ethylbenzene and xylenes determination in air

A new procedure for the passive sampling in air of benzene, toluene, ethylbenzene and xylene isomers (BTEX) is proposed. A low-density polyethylene layflat tube filled with a mixture of solid phases provided a high versatility tool for the sampling of volatile compounds from air. Several solid phases were assayed in order to increase the BTEX absorption in the sampler and a mixture of florisil and activated carbon provided the best results. Direct head-space-gas chromatography–mass spectrometry (HS-GC–MS) measurement of the whole deployed sampler was employed for a fast determination of BTEX. Absorption isotherms were used to develop simple mathematical models for the estimation of BTEX time-weighted average concentrations in air. The proposed samplers were used to determine BTEX in indoor air environments and results were compared with those found using two reference methodologies: triolein-containing semipermeable membrane devices (SPMDs) and diffusive Radiello samplers. In short, the developed sampling system and analytical strategy provides a versatile, easy and rapid atmospheric monitor (VERAM).     

fac-Acetato-bis(pyrazole) complexes: A systematic study on intra- and intermolecular hydrogen bonds

Acetato-bis(pyrazole) complexes [Mo(η³-methallyl)(O₂CMe)(CO)₂(pz^∗H)₂], (methallyl = CH₂C(CH₃)CH₂) and fac-[M(O₂CMe)(CO)₃(pz^∗H)₂], (pz^∗H = pyrazole or 3,5-dimethylpyrazole, dmpzH; M = Mn, Re) are obtained from [Mo(η³-methallyl)Cl(CO)₂(NCMe)₂] or fac-[MBr(CO)₃(NCMe)₂] [M = Mn (synthesized in situ), Re], 2 equiv. of pyrazole, and 1 equiv. of sodium acetate for Mo complexes, or silver acetate for Mn or Re complexes. The chlorido-complexes [Mo(η³-methallyl)Cl(CO)₂L₂] (L = pzH, dmpzH), obtained from the same starting material by substitution of MeCN by pzH or dmpzH, are also described. The crystal structures of the fac-acetato-bis(dimethylpyrazole) complexes present the same pattern of intramolecular hydrogen bonds between the acetate and the dimetylpyrazole ligands, whereas the crystal structures of the fac-acetato-bis(pyrazole) complexes show different hydrogen bonds patterns, with intermolecular interactions. NMR data indicate that these interactions are not maintained in solution.