Correction of the interference by mixing the reagents in the bioluminescent determination of ATP in environmental samples by an interfaced PC photometer and a robust regression procedure

 An automated procedure for correcting the interference due to mixing the reagents in the determination of ATP by a bioluminescent technique is described. The measurements were performed by an in-house interfaced PC photometer. An automated procedure based on a robust regression method and outliers detection was applied to exclude the time of the mixing of the reagents from the global time of reaction. In fact the mixing of the reagents is responsible of the poor analytical precision (RSD%>25) and low sensitivity (limit of detection≈2×10^-8 mol/l). By this procedure, the precision (RSD%<7) and sensitivity (limit of detection≈8×10^-10 mol/l) were improved. The method was applied to the determination of ATP in marine sediments and good recovery within 90–108% was obtained. For non-polluted samples the measurement can be carried out by direct comparison with standard solutions. The standard addition procedure is recommended for polluted samples. Received: 25 April 1996/Revised: 28 June 1996/Accepted: 3 July 1996     

Structure of the 18-Crown-6 Complex with Ammonium Hexafluorosilicate and Water

The crystalline host–guest type complex [(18-crown-6NH₄)₂][SiF₆]4H₂Ohas been obtained as the result of the interaction of SiF₄2NH₃ with 18-crown-6 (18C6) in an aqueous medium. Crystal data: monoclinic, space groupC 2 c, a=26.541(2), b=8.363(2), c=20.469(2) Å, = 122.43(1)°and Z=4. The final R-value is 0.070 for 3253 reflections with I 2(I).The crystals consist of the complex [NH₄18C6]⁺ cations, [SiF₆]^2-anions and water molecules. The ammonium cation is hydrogen bonded by three of its H-atoms to the crown ether oxygen atoms with N(1) O separations2.923(5)–2.940(5) Å and by the fourth H-atom to the fluorine atom of thehexafluorosilicate anion, the N(1)F(4) distance being 2.797(6) Å.The conformation of the macrocycle and the hydrogen-bond geometry in thecomplex cation closely resemble those in related adducts between 18-crown-6and ammonium salts. All crystal components are connected via a system of hydrogen bonds into a ribbon along the b axis in the unit cell.     

Aromatic substitution in the complexes formed upon addition of gaseous arenium ions to proelectrophiles. A FT-ICR study

Experiments based on FT-ICR mass spectrometry provide conclusive evidence for the operation of an alternative mechanism of electrophilic aromatic substitution occurring within the complex formed upon addition of gaseous arenium ions to a variety of proelectrophiles, including alkyl halides, alcohols, epoxides, esters and diazoalkanes. The factors affecting the efficiency of the unconventional substitution are examined in the light of the kinetic results of the FT-ICR experiments.     

Molecular structures of acetylene derivatives of tin: Part IV. Gas-phase electron-diffraction study of tetraethynyltin,Sn(CCH)4, and triethynyltin iodide,ISn(CCH)3

The geometrical parameters of tetraethynyltin and triethynyltin iodide have been determined by gas-phase electron diffraction. Triethynyltin iodide was present as an admixture in both the tetraethynyltin samples studied. Because the samples differed significantly in percentage of the iodide (17.4 ± 4.0 and 47.1 ± 3.5 mol %, in samples A and B, respectively), it was possible to determine the structures of both molecules to a sufficient degree of accuracy.The r_α, structures were solved by the least-squares treatment of the molecular intensities, using mean amplitudes and shrinkage corrections calculated from the force fields of a number of tin derivatives.The T_d-symmetry model of Sn(CCH)₄ was refined to give the following parameters: Sn-C, 2.068(5); CC, 1.228(8); CH, 1.079(51). The structural parameters for ISn(CCH)₃ (on the basis of the C_3v model with linear Sn-CC-H fragments) are as follows: Sn-I, 2.646(4); Sn-C, 2.062(17); CC, 1.226(6); ∠ISnC 108.0(2.8). (The thermal average bond distances, r_g, are given in Å, and the valence angle, rα, in degrees; the values in paren- theses are three times the standard deviations, 3σ.)The Sn-C bonds in Sn(CCH)₄, and ISn(CCH)₃ are shorter than the corresponding bonds in the monoethynyltin derivatives, Me₃SnCCH and Me₃SnCCSnMe₃. The SnI bond in ISn(CCH)₃ is noticeably shorter than those in stannane iodide and trimethylstannane iodide.     

Acid–Base Titration: Analysis of Phosphoric Acid Anodizing Solutions. A Problem-Based Learning Approach

Phosphoric acid anodizing solutions are routinely titrated to monitor their concentrations; however, after successive anodizations of aluminum metal, increasing amounts of dissolved aluminum interfere with the neutralization titration. The true concentration of phosphoric acid is determined by a correction factor based on the concentration of the dissolved aluminum, which is determined industrially by flame atomic absorption spectrometry. The academic determination of a correction factor for aluminum as well as copper can be designed as a traditional or a problem-based learning exercise.     

Crystal structure of supramolecular complexes formed by 18-crown-6 andcis-anti-cis-dicyclohexano-18-crown-6 (host) with 3,4-diaminofurazane (guest)

An X-ray—diffraction study is reported for two molecular complexes containing 3,4-diamino-1,2,5-oxadiazole as guest (G) with 18-crown-6 (18-C-6) andcis-anti-cis-dicyclohexano-18-crown-6 (DCH-6B) as host. Both complexes are of the polymeric-chain structure with the guest molecule bridging two crown neighbours. ComplexI: [18-C-6*G*H₂O], 111, monoclinic,P2₁/n,a=8.171(1),b=15.042(2),c=16.209(6) Å, =101.15(2)°, finalR-factor 0.068. ComplexII: [DCH-6B*G], 11, monoclinicC2/c,a=21.212(4),b=9.380(2),c=13.049(3) Å, =108.61(3)°, finalR 0.047.     

Delphinidin–Aluminum(III) Complexes in Aqueous and Non-Aqueous Media: Spectroscopic Characterization and Theoretical Study

Summary. The study of delphinidin complexation with trivalent aluminum in acidic aqueous buffered (pH 3.0 and 3.8) and methanolic solutions was performed utilizing electronic absorption spectroscopy and quantum chemical calculations. In its structure delphinidin possesses several chelating sites in competition towards aluminum(III). Molar ratio plots denoted the formation of only one aluminum(III):delphinidin complex of stoichiometry of 1:1 in both investigated media. Semiempirical calculations, performed at the restricted HF AM1 level, enabled the determination of the structural features of free delphinidin and structural modifications caused by chelation of aluminum(III). Considering the pigment molecular structure and the results of the theoretical calculations it is possible to equally implicate C3′–C4′ and C4′–C5′ hydroxyl groups as those with the predominant chelating power.     

Coordination modes between copper(II) and N-acetylneuraminic (sialic) acid from a 2D-simulation analysis of EPR spectra. Implications for copper mediation of sialoglycoconjugate chemistry relevant to human biology

The equilibrium distribution of species formed between Cu(II) and N-acetylneuraminic (sialic) acid (I, LH) at 298 K has been determined using a two-dimensional (2D) simulation analysis of electron paramagnetic resonance (EPR) spectra. In acidic solutions (pH values < 4), the major species present are Cu(2+), [CuL]+ [logbeta = 1.64(4)], and [CuL2] [logbeta = 2.77(5)]. At intermediate pH values (4.0 < pH < 7.5), [CuL2H-1]- [logbeta = -2.72(7)] and two isomers of [CuLH-1] [logbeta (overall) = -3.37(2)] are present. At alkaline pH values (7.5 < pH < 11), the major species present is [CuL2H-2]2-, modeled as three isomers with unique giso and Aiso values [logbeta (overall) = -8.68(3)]. Two further species ([CuLH-3]2- and [CuL2H-3]3-) appear at pH values > 11. It is proposed that [CuL]+ most likely features I coordinated via the deprotonated carboxylic acid group (O1) and the endocyclic oxygen atom (OR) forming a five-membered chelate ring. Select Cu(II)-I species of the form [CuLH-1] may feature I acting as a dianionic tridentate chelate, via oxygen atoms derived from O1, OR, and one deprotonated hydroxy group (O7 or O8) from the glycerol tail. Alternatively, I may coordinate Cu(II) in a bidentate fashion as the tert-2-hydroxycarboxylato (O1,O2) dianion. Spectra predicted for Cu(II)-I complexes in which I is coordinated in either a O1,OR {I1-} or O1,O2 {I2-} bidentate fashion {e.g., [CuL]+ (O1,O R), [CuL2] (bis-O1,O R), [CuLH-1] (isomer: O1, O2), [CuL2H-1]- (O1, O R; O1, O2), and [CuL2H-2]2- (isomer: bis-O1, O2)} have "irregular" EPR spectra that are ascribed to the existence of Cu(II)-I(monomer) <==> Cu(II)-I(polymer) equilibria. The formation of polymeric Cu(II)-I species will be favored in these complexes because the glycerol-derived hydroxyl groups at the complex periphery (O, 7O, 8O9) are available for further Cu(II) binding. The presence of polymeric Cu(II)-I species is supported by EPR spectral data from solutions of Cu(II) and the homopolymer of I, colominic acid (Ipoly). Conversely, spectra predicted for Cu(II)-I complexes where I is coordinated in a {I2-} tridentate {e.g., [CuLH-1] (isomer: O1, O R, O7, or O8) and [CuL2H-2]2- (isomer: bis-O1,O R,O7, or O8)} or tetradentate fashion {I3-} {e.g., [CuLH-3]2- (O1, O R, O, 8O9)} are typical for mononuclear tetragonally elongated Cu(II) octahedra. In this latter series of complexes, the tendency toward the formation of polymeric Cu(II)-I analogues is small because the polydentate I effectively wraps up the mononuclear Cu(II) center. This work shows that Cu(II) could potentially mediate the chemistry of sialoglycoconjugate-containing proteins in human biology, such as the sialylated amyloid precursor protein of relevance to Alzheimer's disease.     

Measurement of the carbonaceous component in the Milan urban particulate matter

The carbonaceous component in the Milan urban particulate matter, i.e. the two components black carbon (BC) and organic carbon (OC), has been measured by means of a thermogravimetric analyzer combined with an infrared spectrophotometer (TGA/FT-IR). While black carbon may be considered a primary pollutant, organic carbon includes both primary emissions and secondary organic aerosols. Since carbonaceous aerosol (including a small quantity of inorganic carbon, too) makes up roughly from 25% to 50% of the average annual PM 2.5 mass concentration, a deeper understanding of this component is required. The TGA/FT-IR technique, employed for the first time to our knowledge for the quantification of the particulate matter carbonaceous component, allows, thought the results here presented are preliminary, to assess the two components BC and OC in a simple way especially if compared with the methods reported in the literature. The total carbon (TC) determinations performed by TGA/FT-IR on Milan urban particulate matter are in good agreement with the results obtained by a total organic carbon (TOC) analyzer operating directly on the solid sample.     

Electrocatalytic reduction of ROOH by iron porphyrins

Electrocatalytic reduction of a series of chemical oxidants of different power (tert-butyl hydroperoxide, potassium peroxomonosulfate, peracetic acid, and m-chloroperbenzoic acid) at iron-porphyrin-modified graphite electrodes is studied in buffered aqueous solutions by rotating disk and ring-disk voltammetry. Both ferric and ferrous porphyrins are catalytically active. Turnover of ferric catalysts is slower than that of the ferrous analogues and involves competing catalytic reduction and disproportionation. The kinetic data are consistent with reactant binding being the rate-determining step in catalysis by Fe(III). In catalysis by Fe(II), the turnover is controlled by the first electron transfer. The covalently linked proximal imidazole ligand is found to be crucial for achieving the Fe(III) catalysis.