Oxalate films and red stains on Carrara marble

The analytical studies carried out during two different diagnostic surveys, respectively in 1983 and 2003, offered the opportunity to control decay phenomena development on stones facing Certosa of Pavia (Italy). Calcium oxalate films and red stains, present on Carrara marble surface, have been particularly focused; these are the only decay phenomena which apparently have remained unchanged during a period of twenty years. More sensitive and in-depth analytical studies (FTIR equipped with diamond cell, GC-MS, SEM-EDS and optical microscopy) achieved a better knowledge about their composition. Results allowed a critical evaluation of the role of oxalate films on the external marble surface and to suggest new hypotheses about the formation of red stains.     

Liquid chromatographic analysis of vitamin B6 in reconstituted infant formula: collaborative study

A liquid chromatographic (LC) method was validated for the determination of total vitamin B6 in infant formula. Total vitamin B6 was quantified by converting the phosphorylated and free vitamers into pyridoxine. Pyridoxine was determined by ion pair reversed-phase LC with fluorescence detection. The method was subjected to an AOAC collaborative study involving a factory-manufactured, milk- and soy-based infant formula. Each was spiked at 3 concentrations in the range of 0-1 microg/g and sent as blind duplicate to participant laboratories. Nine laboratories returned valid data which were statistically analyzed for outliers and precision parameters. The repeatability relative standard deviation (RSD(r)) ranges were 2.0-4.0 and 3.5-5.9% for fortified milk- and soy-based formulas, respectively. The reproducibility relative standard deviation (RSD(R)) ranges were 8.2-8.4 and 6.7-11.2% for fortified milk- and soy-based formulas, respectively. HORRAT values ranged from 0.42 to 0.53, indicating that the precision of the method is acceptable. The mean RSD(r):RSD(R) values were 0.60 and 0.55 for milk- and soy-based formulas, respectively. As expected, RSDs for the unfortified samples were higher, but their HORRAT values (0.81 and 2.06) helped define a realistic limit of quantitation as 0.05 microg/g. Recovery data were quantitative and varied between 81.4 and 98.0% (mean = 89.8%) for each of 6 spiked materials.     

Correlation of the Solubilizing Abilities of 1-Butyl-1-methyl-pyrrolidinium Tris(pentafluoroethyl)trifluorophosphate, 1-Butyl-1-methylpyrrolidinium Triflate and 1-Methoxyethyl-1-methylmorpholinium Tris(pentafluoroethyl)trifluorophosphate

Chromatographic retention data were measured for a wide range of organic solutes on 1-butyl-1-methylpyrolidinium tris(pentafluoroethyl)trifluorophosphate ([BMPyrr]⁺[FAP]^?), 1-butyl-1-methylpyrrolidinium triflate, ([BMPyrr]⁺[Trif]^?), and 1-methoxyethyl-1-methylmorpholinium tris(pentafluoroethyl)trifluorophosphate, ([MeoeMMorp]⁺[FAP]^?), stationary phases at (323, 353 and 383) K. The measured retention factors were combined with published infinite dilution activity coefficient and gas-to-water partition coefficient data to yield gas-to-anhydrous ionic liquid (IL) and water-to-anhydrous IL partition coefficients. The three sets of partition coefficients were analyzed using the Abraham model. The derived Abraham model correlations describe the observed gas-to-IL (log₁₀ K) and water-to-IL (log₁₀ P) partition coefficient data to within average standard deviations of about 0.11 and 0.15 log₁₀ units, respectively.     

Thermal studies for preparation of Nb10Hf1Ti Alloy

The aim of this work is to evaluate the feasibility of preparation of Nb10Hf1Ti alloy by magnesiothermic reduction of its oxides. DTA studies were conducted to identify the reduction temperature for co reduction of the mixed oxides of Nb₂O₅, HfO₂, and TiO₂ by magnesium under reducing atmosphere. Based on DTA analysis, experiments were carried out to prepare Nb10Hf1Ti alloy by magnesiothermic reduction of their oxides at 750 °C. The reduced product was analyzed for its phases by X-ray diffraction. The excess Mg was leached out, the alloy mixture was vacuum dried, pelletized, sintered, and electron beam melted to get a consolidated alloy of the required composition. The alloy was characterized using different techniques such as optical microscopy, scanning electron microscopy, and chemical analysis. Microstructural observations revealed the formation of coarse grain structure in the consolidated alloy. The alloy product was also evaluated for its micro hardness.     

ADSORPTION OF SURFACE-ACTIVE AGENTS FROM AQUEOUS SOLUTION: HYDROPHOBIC SUBSTRATES∗

Isotherms for the adsorption of sodium dodecyl benzene sulfonate, sodium POE (4) nonyl phenol sulfate, and POE (25) nonyl phenol, on the hydrophobic crystalline herbicides atrazine and cyanazine were determined. Anionic surfactants were measured at 5°, 25°, and 50° C; the nonionic surfactant at 25° C only. Low degrees of surface coverage were observed; in only one case (atra-zine/NaDBS) was monolayer coverage approached. On the other hand, adsorption was accompanied by a significant increase in negative zeta potential. Although DLVO calculations suggest that this adsorption should lead to stable aggregates, these are of such size that gravitational effects overpower the DLVO terms.     

Synthesis of 5,10-dideazaminopterin

The synthesis of 5,10-dideazaaminopterin by two independent routes is described. Condensation of the piperidine enamine of 4-p-carbomethoxyphenylbutyraldehyde ( 4 ) with ethoxymethylenemalononitrile followed by treatment of the resultant arylethylenaminomalononitrile ( 5 ) with methanolic ammonia produced 2-amino-3-cyano-5-p-carbomethoxyphenethylpyridine ( 6 ). Cyclization of the aminocyanopyridine with guanidine afforded 4-amino-4-deoxy-5,10-dideazapteroic acid ( 8 ). Coupling of the pteroate intermediate with glutamate yielded the target 5,10-dideazaaminopterin ( 10 ). Alternatively, reduction of 2,4-diamino-6-formyl-5-deazapteridine ( 11 ) with sodium borohydride gave the 6-hydroxymethyl compound 12 . Conversion to the bromide was followed by alkylation of dimethyl homoterephthalate to afford methyl 4-amino-4-deoxy-10-carbomethoxy-5,10-dideazapteroate ( 14 ). Decarboxylation with ester cleavage (sodium cyanide in dimethyl sulfoxide at 180°) also gave the diaminopteroic acid ( 8 ). 5,10-dideazaaminopterin ( 10 ) was an effective growth inhibitorof folate dependent bacteria, S. faecium and L. casei.     

Direct Electrochemical Investigations of 17-Electron Complexes of CpM(CO)(3)(*) (M = Mo, W, and Cr)

Photolysis of complexes of the type M(2)(CO)(6)(RC(5)H(4))(2) (where M = W, Mo, Cr and R = H (Cp) or CH(3) (Cp')) leads to the production of short lived 17-electron radicals. Direct electrochemical characterization of these intermediates has been achieved using a technique known as photomodulated voltammetry (PMV). The results from PMV analysis are in excellent agreement with literature estimates for CpMo(CO)(3)(*) and CpCr(CO)(3)(*). However, CpW(CO)(3)(*) is found to be shifted oxidatively 115 mV relative to previous literature estimates. The change in the value for the tungsten complex changes previous estimates to the bond dissociation energy for tungsten metal hydrides by 3.0 +/- 0.9 kcal/mol. Lifetime information on the radicals is also reported based on the phase shift of the electrochemical signal observed by PMV under limiting current conditions.     

Prompt and delayed photoejection of hydrated electrons in the UV photolysis of aqueous solutions of copper(I) complexes

The ejection of hydrated electrons from 266-nm laser-photoexcited solutions containing Cu(NH₃)⁺₃, CuCl²⁻₃, or CuBr²⁻₃ occurs through two pathways on the nanosecond time scale: a prompt ejection (ττ>laser pulsewidth) which follows a first-order rate law. This behavior is consistent with electron ejection from two excited states: the primary CTTS state, and longer-lived triplet species consisting of an exciplex and its precursor. The quantum yields for both prompt and delayed ejection are quite high, in the 0.15–0.4 range.