Double addition of H2 to transition metal-borane complexes: a 'hydride shuttle' process between boron and transition metal centres

The addition of H(2) across a transition metal-borane bond is reported for the first time providing a mechanism for recharging borane functional groups to borohydride.     

Special issue of FOA10 in honor of our colleagues in Japan and New Zealand

Tribute

Special issue of FOA10 in honor of our colleagues in Japan and New Zealand     

Synthesis of glycerol carbonate from glycerol and urea with gold-based catalysts

The reaction of glycerol with urea to form glycerol carbonate is mostly reported in the patent literature and to date there have been very few fundamental studies of the reaction mechanism. Furthermore, most previous studies have involved homogeneous catalysts whereas the identification of heterogeneous catalysts for this reaction would be highly beneficial. This is a very attractive reaction that utilises two inexpensive and readily available raw materials in a chemical cycle that overall, results in the chemical fixation of CO(2). This reaction also provides a route to up-grade waste glycerol produced in large quantities during the production of biodiesel. Previous reports are largely based on the utilisation of high concentrations of metal sulfates or oxides, which suffer from low intrinsic activity and selectivity. We have identified heterogeneous catalysts based on gallium, zinc, and gold supported on a range of oxides and the zeolite ZSM-5, which facilitate this reaction. The addition of each component to ZSM-5 leads to an increase in the reaction yield towards glycerol carbonate, but supported gold catalysts display the highest activity. For gold-based catalysts, MgO is the support of choice. Catalysts have been characterised by XRD, TEM, STEM and XPS, and the reaction has been studied with time-on-line analysis of products via a combination of FT-IR spectroscopy, HPLC, (13)C NMR and GC-MS analysis to evaluate the reaction pathway. Our proposed mechanism suggests that glycerol carbonate forms via the cyclization of a 2,3-dihydroxypropyl carbamate and that a subsequent reaction of glycerol carbonate with urea yields the carbamate of glycerol carbonate. Stability and reactivity studies indicate that consecutive reactions of glycerol carbonate can limit the selectivity achieved and reaction conditions can be selected to avoid this. The effect of the catalyst in the proposed mechanism is discussed.     

Determination of pesticide residues in honey by single-drop microextraction and gas chromatography

A novel, simple, and rapid single-drop microextraction (SDME) procedure combined with GC has been developed, validated, and applied for the determination of multiclass pesticide residues in honey samples. The SDME was optimized using a Plackett-Burman screening design considering all parameters that may influence an SDME procedure and a consequent central composite design to control the parameters that were found to significantly influence the pesticide determination. The developed analytical method required minimal volumes of organic solvents and exhibited good analytical characteristics with enrichment factors ranging from 3 for alpha-endosulfan to 10 for lindane, procymidone, and captan and method quantification limits ranging from 0.03 microg/kg for phosalone to 10.6 microg/kg for diazinon. The relative recoveries obtained ranged from 70.8% for captan to 120% for fenarimol, and the precision (RSD) ranged from 3 to 15%. The proposed SDME procedure followed by GC with an electron capture detector for quantification and GC/MS for identification was applied with success to the analysis of 17 honey samples. Monitoring results indicated a low level of honey contamination by diazinon, chlorpyrifos-ethyl, procymidone, bromopropylate, and endosulfan (alpha-, beta-, and endosulfan sulfate) residues that were far below the maximum residue limit values specified by the European Union for endosulfan (10 microg/kg) and bromopropylate (100 microg/kg) in honey samples.     

Self‐Assembling Nanomaterials using Magnetic Nanoparticles Modified with Polystyrene Brushes

Magnetic nanomaterials have been studied in order to generate novel nanocomposites that display both the magnetic properties of the nanoparticles and the ability to self‐assemble of the amorphous block copolymer matrix. Towards this goal, iron oxide magnetic nanoparticles have been modified with PS brushes by ATRP in order to improve both the dispersion and the affinity of the nanoparticles with one of the blocks of a polystyrene‐block‐polybutadiene‐block‐polystyrene block copolymer. This method of preparation of nanocomposites opens new strategies for the generation of magnetic nanomaterials. The samples are characterized using DSC and atomic and magnetic force microscopies.

     

Polyoxomolybdenum(V/VI)-sulfite compounds: synthesis, structural, and physical studies

Reaction of Na(2)Mo(VI)O(4) x 2H(2)O with (NH(4))(2)SO(3) in the mixed-solvent system H(2)O/CH(3)CN (pH = 5) resulted in the formation of the tetranuclear cluster (NH(4))(4)[Mo(4)(VI)SO(16)] x H(2)O (1), while the same reaction in acidic aqueous solution (pH = 5) yielded (NH(4))(4)[Mo(5)(VI)S(2)O(21)] x 3H(2)O (2). Compound {(H(2)bipy)(2)[Mo(5)(VI)S(2)O(21)] x H(2)O}(x) (3) was obtained from the reaction of aqueous acidic solution of Na(2)Mo(VI)O(4) x 2H(2)O with (NH(4))(2)SO(3) (pH = 2.5) and 4,4'-bipyridine (4,4'-bipy). The mixed metal/sulfite species (NH(4))(7)[Co(III)(Mo(2)(V)O(4))(NH(3))(SO(3))(6)] x 4H(2)O (4) was synthesized by reacting Na(2)Mo(VI)O(4) x 2H(2)O with CoCl(2) x 6H(2)O and (NH(4))(2)SO(3) with precise control of pH (5.3) through a redox reaction. The X-ray crystal structures of compounds 1, 2, and 4 were determined. The structure of compound 1 consists of a ring of four alternately face- and edge-sharing Mo(VI)O(6) octahedra capped by the trigonal pyramidal sulfite anion, while at the base of the Mo(4) ring is an oxo group which is asymmetrically shared by all four molybdenum atoms. Compound 3 is based on the Strandberg-type heteropolyion [Mo(5)(VI)S(2)O(21)](4-), and these coordinatively saturated clusters are joined by diprotonated 4,4'-H(2)bipy(2+) through strong hydrogen bonds. Compound 3 crystallizes in the chiral space group C2. The structure of compound 4 consists of a novel trinuclear [Co(III)Mo(2)(V)SO(3)(2-)] cluster. The chiral compound 3 exhibits nonlinear optical (NLO) and photoluminescence properties. The assignment of the sulfite bands in the IR spectrum of 4 has been carried out by density functional calculations. The cobalt in 4 is a d(6) octahedral low-spin metal atom as it was evidenced by magnetic susceptibility measurements, cw EPR, BVS, and DFT calculations. The IR and solid-state UV-vis spectra as well as the thermogravimetric analyses of compounds 1-4 are also reported.     

Determination of 13 synthetic food colorants in water-soluble foods by reversed-phase high-performance liquid chromatography coupled with diode-array detector

A reversed-phase high performance liquid chromatographic method for the successful separation and determination of 13 synthetic food colorants (Tartrazine E 102, Quinoline Yellow E 104, Sunset Yellow E 110, Carmoisine E 122, Amaranth E 123, Ponceau 4R E 124, Erythrosine E 127, Red 2G E 128, Allura Red AC E 129, Patent Blue V E 131, Indigo Carmine E 132, Brilliant Blue FCF E 133 and Green S E 142) was developed. A C18 stationary phase was used and the mobile phase contained an acetonitrile-methanol (20:80 v/v) mixture and a 1% (m/v) ammonium acetate buffer solution at pH 7.5. Successful separation was obtained for all the compounds using an optimized gradient elution within 29 min. The diode-array detector was used to monitor the colorants between 350 and 800 nm. The method was thoroughly validated. Detection limits for all substances varied between 1.59 (E 142) and 22.1 (E 124) μg L⁻¹. The intra-day precision (as R.S.D._r) ranged from 0.37% (E 122 in fruit flavored drink at a concentration of 100 mg L⁻¹) to 4.8% (E 142 in icing sugar at a level of 0.9 mg kg⁻¹). The inter-day precision (as R.S.D._R) was between 0.86% for E 122 in fruit flavored drink at 100 mg L⁻¹ and 10% for E142 in jam at a concentration of 9 mg kg⁻¹. Satisfactory recoveries, ranging from 94% (E 142 in jam) to 102% (E 131 in sweets), were obtained. The method was applied to the determination of colorants in various water-soluble foods, such as fruit flavoured drinks, alcoholic drinks, jams, sugar confectionery and sweets, with simple pre-treatment (dilution or water extraction).     

Simultaneous liquid chromatographic determination of metals and organic compounds in pharmaceutical and food-supplement formulations using evaporative light scattering detection

A novel method for the non-derivatization liquid chromatographic determination of metals (potassium, aluminium, calcium and magnesium) and organic compounds (ascorbate and aspartate) was developed and validated based on evaporative light scattering detection (ELSD). Separation of calcium, magnesium and aluminium was achieved by the cation exchange column Dionex CS-14 and an aqueous TFA mobile phase according to the following time program: 0-6 min TFA 0.96 mL L⁻¹, 6-7 min linear gradient from TFA 0.96-6.4 mL L⁻¹. Separation of potassium, magnesium and aspartate was achieved by the lipophilic C₁₈ Waters Spherisorb column and isocratic aqueous 0.2 mL L⁻¹ TFA mobile phase. Separation of sodium, magnesium, ascorbate and citrate was also achieved by the C₁₈ analytical column, according to the following elution program: 0-2.5 min aqueous nonafluoropentanoic acid (NFPA) 0.5 mL L⁻¹; 2.5-3.5 min linear gradient from 0.5 mL L⁻¹ NFPA to 1.0 mL L⁻¹ TFA. In all cases, evaporation temperature was 70 °C, pressure of the nebulizing gas (nitrogen) 3.5 bar, gain 11 and the flow rate 1.0 mL min⁻¹. Resolution among calcium and magnesium was 1.8, while for all other separations was ≥3.2. Double logarithmic calibration curves were obtained within various ranges from 3-24 to 34-132 μg mL⁻¹, and with good correlation (r > 0.996). Asymmetry factor ranged from 0.9 to 1.9 and limit of detection from 1.3 (magnesium) to 17 μg mL⁻¹ (ascorbate).The developed method was applied for the assay of potassium, magnesium, calcium, aluminium, aspartate and ascorbate in pharmaceuticals and food-supplements. The accuracy of the method was evaluated using spiked samples (%recovery 95-105%, %R.S.D. < 2) and the absence of constant or proportional errors was confirmed by dilution experiments.