PERMEABILITY MEASUREMENTS OF BRAZILIAN PINUS ELLIOTTII

The liquid and gas phase permeability, of Brazilian Pinus elliotii was studied with a custom built gas and liquid flow rate analysis chamber. The longitudinal gas phase permeability is shown to be six times greater than the radial permeability. There is no statistically significant difference between the longitudinal permeability of water versus wood preservative. Scanning Electron Microscopy (SEM) images confirm that the reported permeability properties arc due to the wood itself rather than to blocked pores or other artifacts of the sample cutting process. Wood composition analysis shows that the samples of Pinus elliotii grown in Brazil are similar to other species of Pinus grown in tropical climates. Specifically, the Pinus elliotti in this study is composed of 17% extractives, 0,27% ashes, 21% hemicellulose, 45% cellulose and 30% lignin. Results arc discussed in the context of the continued search for effective wood preservatives for use in tropical climates.

Treatment of Aqueous Effluents Containing Phenol by the O(3), O(3)-UV, and O(3)-H(2)O(2) Processes: Experimental Study and Neural Network Modeling

In this work, the oxidation of the model pollutant phenol has been studied by means of the O(3), O(3)-UV, and O(3)-H(2)O(2) processes. Experiments were carried out in a fed-batch system to investigate the effects of initial dissolved organic carbon concentration, initial, ozone concentration in the gas phase, the presence or absence of UVC radiation, and initial hydrogen peroxide concentration. Experimental results were used in the modeling of the degradation processes by neural networks in order to simulate DOC-time profiles and evaluate the relative importance of process variables.

Application of high-resolution electrospray mass spectrometry for the elucidation of the disproportionation reaction of iodobenzene diacetate

Disproportionation reactions take place in solution of (diacetoxyiodo)benzene (DIB) in acetonitrile in the presence of water, giving iodine(V) and iodine(l) species. This redox reaction is accelerated by the presence of water and by increasing the temperature. Several species of the solution of DIB were identified by high-resolution ESI-MS/MS, which allowed the elucidation of the mechanisms of disproportionation for DIB in gas phase and in solution. Key species in the process are the dimers [PhI(CH)OlPh](+) at m/z 440.8864, [PhI(OAc)OlPh](+) at m/z 482.8947, and [PhI(O)(OAc)OlPh](+) at m/z 498.8887. (C) 2008 Elsevier B.V. All rights reserved.

Re-examination of the anion derivatives of isoflavones by radical fragmentation in negative electrospray ionization tandem mass spectrometry: experimental and computational studies

This paper reports theoretical and experimental studies of gas-phase fragmentation reactions of four naturally occurring isoflavones. The samples were analyzed in negative ion mode by direct infusion in ESI-QqQ, ESI-QqTOF and ESI-Orbitrap systems. The MS/MS and MS(n) spectra are in agreement with the fragmentation proposals and high-resolution analyses have confirmed the formulae for each ion observed. As expected, compounds with methoxyl aromatic substitution have showed a radical elimination of center dot CH(3) as the main fragmentation pathway. A second radical loss (center dot H) occurs as previously observed for compounds which exhibit a previous homolytic center dot CH(3) cleavage (radical anion) and involves radical resonance to stabilize the anion formed. However, in this study we suggest another mechanism for the formation of the main ions, on the basis of the enthalpies for each species. Compounds without methoxy substituent dissociate at the highest energies and exhibit the deprotonated molecule as the most intense ion. Finally, energy-resolved experiments were carried out to give more details about the gas-phase dissociation reaction of the isoflavones and the results are in agreement with the theoretical approaches. Copyright (C) 2011 John Wiley & Sons, Ltd.

Electrospray MS-based characterization of beta-carbolines - mutagenic constituents of thermally processed meat

The beta-carbolines 1-methyl-9H-pyrido [3,4-b]indole and 9H-pyrido[3,4b]indole have been implicated as having causative roles in a number of human diseases, such as Parkinson`s disease and cancer. As they can be formed during the heating of protein-rich food, a number of analytical methodologies have been proposed for their detection and quantification in foodstuff For this purpose, LC-MS and LC-MS/MS have emerged as the most specific analytical methods, and the quantification is based on the occurrence of unusual ions, such as [M+H-(H(center dot))](+) and [M + H-2H](+). In this study, we have investigated the formation of these ions by accurate-mass electrospray MS/MS and demonstrated that these ions are formed from gas-phase ion-molecule reactions between water vapor present in the collision cell and the protonated molecule of 1-methyl-9H-pyrido [3,4-b]indole and 9H-pyrido[3,4b]indole. Although this reaction has been previously described for heterocyclic amine ions, it has been overlooked in the most of recent LC-MS and LC-MS/MS studies, and no complete data of the fragmentation are reported. Our results demonstrate that additional attention should be given with respect to eliminating water vapor residues in the mass spectrometer when analysis of beta-carbolines is performed, as this residue may affect the reliability in the results of quantification.

HPLC separation, NMR and QTOF/MS/MS structure elucidation of a prominent nitric oxide donor agent based on an isomeric composition of a nitrosyl ruthenium complex

A new and promising nitrosyl ruthenium complex, [Ru(NO)(bdqi-COOH)(terpy)](PF(6))(3), bdqi-COOH is 3,4-diiminebenzoic acid and terpy is 2,2`-terpyridine, has been synthesized as a NO donor agent. The procedure used for [Ru(NO)(bdqi-COOH)(terpy)](PF(6))(3) synthesis has, apparently, yielded the formation of two isomers in which the ligand bdqi-COOH appears to be coordinated in its reduced form (bdcat-COOH), which could have differences in their pharmacological properties. Therefore, it was intended to separate the two possible isomers by high-performance liquid chromatography (HPLC) and to characterize them by high resolution mass spectrometry (QTOF MS) and by magnetic nuclear resonance spectroscopy (NMR). The results obtained by MS showed that the ESI-MS mass spectra of both HPLC column fractions, e.g. peak 1 and peak 2, are essentially equal, showing that both isomers display nearly identical gas-phase behavior with clusters of isotopologue ions centered at m/z 573, m/z 543 and m/z 513. Regarding the NMR analysis, the results showed that the positional isomerism is located in the bdqi-COOH ligand. From the observed results it can be concluded that the synthesis procedure that has been used results in the formation of two [Ru(terpy)(bdqi-COOH)NO](PF(6))(3) isomers. (c) 2009 Elsevier B.V. All rights reserved.

Fragmentation studies and electrospray ionization mass spectrometry of lapachol: protonated, deprotonated and cationized species

Electrospray ionization mass spectrometric analysis of lapachol (2-hydroxy-3-(3-methy1-2-butenyl)-1,4-naphthoquinone) was accomplished in order to elucidate the gas-phase dissociation reactions of this important biologically active natural product. The occurrence of protonated and cationized species in the positive mode and of deprotonated species in the negative mode was explored by means of collision-induced dissociation (CID) experiments. For the protonated molecule, the H(2)O and C(4)H(8) losses occur by two competitive channels. For the deprotonated molecule, the even-electron rule is not conserved, and the radicalar species are eliminated by formation of distonic anions. The fragmentation mechanism for each ion was suggested on the basis of computational thermochemistry. Atomic charges, relative energies, and frontier orbitals were employed aiming at a better understanding of the gas-phase reactivity of lapachol. Potential energy surfaces for fragmentation reactions were obtained by the B3LYP/6-31+G(d,p) model. Copyright (C) 2010 John Wiley & Sons, Ltd.

VOC removal: Comparison of MCM-41 with hydrophobic zeolites and activated carbon

The recently discovered mesoporous molecular sieve MCM-41 was tested as an adsorbent for VOC removal. Its adsorption/desorption properties were evaluated and compared with other hydrophobic zeolites (silicalite-1 and zeolite Y) and a commercial activated carbon, BPL. The adsorption isotherms of some typical VOCs (benzene, carbon tetrachloride, and n-hexane) on MCM-41 are of type IV according to the IUPAC classification, drastically different from the other microporous adsorbents, indicating that VOCs, in the gas phase, have to be at high partial pressures in order to make the most of the new mesoporous material as an adsorbent for VOC removal. However, a proper modification of the pore openings of MCM-41 can change the isotherm types from type IV to type I without remarkable loss of the accessible pare volumes and, therefore, significantly enhance the adsorption performance at low partial pressures. Adsorption isotherms of water on these adsorbents are all of type V, demonstrating that they possess a similar hydrophobicity. Desorption of VOCs from MCM-41 could be achieved at lower temperatures (50-60 degrees C), while this had to be conducted at higher temperatures (100-120 degrees C) for microporous adsorbents, zeolites, and activated carbons.

Mesoionic pyridopyrimidinylium and pyridooxazinylium olates and non-mesoionic pyridopyrimidinones. Structures in the solid state, solution, and matrices

X-Ray crystal structures, C-13 NMR spectra and theoretical calculations (B3LYP/6-31G*) are reported for the mesoionic (zwitterionic) pyridopyrimidinylium- and pyridooxazinyliumolates 2a, 3a and 5a,b as well as the enol ether 11b and the enamine 11c. The 1-NH compounds like 1a, 2a and 3a exist in the mesoionic form in the crystal and in solution, but the OH tautomers such as 1b and 2b dominate in the gas phase as revealed by the Ar matrix IR spectra in conjunction with DFT calculations. All data indicate that the mesoionic compounds can be regarded as intramolecular pyridine-ketene zwitterions (cf. 16 --> 17) with a high degree of positive charge on the pyridinium nitrogen, a long pyridinium N-CO bond (ca. 1.44-1.49 Angstrom), and normal C=O double bonds (ca. 1.22 Angstrom). All mesoionic compounds exhibit a pronounced tilting of the olate C=O groups (the C=O groups formally derived from a ketene) towards the pyridinium nitrogen, giving NCO angles of 110-118 degrees. Calculations reveal a hydrogen bond with 6-CH, analogous to what is found in ketene-pyridine zwitterions and the C3O2-pyridine complex. The 2-OH tautomers of type 1b, 2b, and 11 also show a high degree of zwitterionic character as indicated by the canonical structures 11 12.

Similitude applied to centrifugal scaling of unsaturated flow

Centrifuge experiments modeling single-phase flow in prototype porous media typically use the same porous medium and permeant. Then, well-known scaling laws are used to transfer the results to the prototype. More general scaling laws that relax these restrictions are presented. For permeants that are immiscible with an accompanying gas phase, model-prototype (i.e., centrifuge model experiment-target system) scaling is demonstrated. Scaling is shown to be feasible for Miller-similar (or geometrically similar) media. Scalings are presented for a more, general class, Lisle-similar media, based on the equivalence mapping of Richards' equation onto itself. Whereas model-prototype scaling of Miller-similar media can be realized easily for arbitrary boundary conditions, Lisle-similarity in a finite length medium generally, but not always, involves a mapping to a moving boundary problem. An exception occurs for redistribution in Lisle-similar porous media, which is shown to map to spatially fixed boundary conditions. Complete model-prototype scalings for this example are derived.

The use of electrospray ionization tandem mass spectrometry on the structural characterization of novel asymmetric metallo-organic supermolecules, based on pentafluorophenylporphyrins and ruthenium complexes

The novel asymmetric metallo-organic triads cis- and trans-[B(4-py)BPFPH(2){Ru(3)O(Ac)(6)(py)(2)}(Ru(bpy)(2)Cl}](PF(6))(2) (5a,b) for which cis- and trans-B(4-py)BPFPH(2)=5,10-bis(pentafluorophenyl)-15,20-bis(4-pyridyl)porphyrin and 5,15-bis(pentafluorophenyl)-10,20-bis(4-pyridyl)porphyrin, respectively; Ac = acetate; py = pyridine and bpy = 2,2`-bipyridine, as well as their corresponding monosubstituted dyads cis- and trans-[B(4-py)BPFPH(2){Ru(3)O(Ac)(6)(py)(2)}]PF(6) (4a,b) have been structurally characterized via electrospray ionization mass spectrometry (ESI-MS and ESI-MS/MS). The ESI-MS of dyads 4a,b display two characteristic Ru-multicomponent clusters of isotopologue ions corresponding to singly charged ions 4a,b(+) of m/z 1629 and doubly charged ions [4a,b+H](2+) of m/z 815 and the triads 5a,b are detected by ESI-MS as the intact doubly charged cluster of isotopologue ions of m/z 1039 [5a,b](2+). The ESI-MS/MS of 4a,b(+), [4a,b+H](2+) and [5a,b](2+) reveal characteristic dissociation pathways, which confirm the structural assignments providing additional information on the intrinsic binding strengths of the gaseous ions. Although the gas-phase behavior of each pair of isomers was rather similar, the less symmetric dyads 4a,b are distinguished via the (1)H NMR spectral profile of the pyrrolic signals. Exploratory photophysical assays have shown that both modifying motifs alter the porphyrinic core emission profile, opening the possibility to use these asymmetric systems as photophysical devices. (C) 2008 Elsevier Ltd. All rights reserved.

Recognition of cyclic, acyclic, exocyclic, and spiro Acetals via structurally diagnostic ion/molecule reactions with the (CH3)(2)N-C+=O acylium ion

Reactions of the model acylium ion (CH3)(2)N-C+=O with acyclic, exocyclic, and Spiro acetals of the general formula (RO)-O-1-(CRR4)-R-3-OR2-upole mass spectrometry. Characteristic intrinsic reactivities were observed for each of these classes of acetals. The two most Characteristic intrinsic reactivities were observed for each of these classes of acetals. The two most common reactions observed were hydride and alkoxy anion [(RO-)-O-1 and (RO-)-O-2] abstraction. Other specific reactions were also observed: (a) a secondary polar [4(+) + 2] cycloaddition for acetals bearing alpha,beta-unsaturated R-3 or R-4 substituents and (b) OH- abstraction for exocyclic and spiro acetals. These structurally diagnostic reactions, in conjunction with others observed previously for cyclic acetals, are shown to reveal the class of the acetal molecule and its ring type and substituents and to permit their recognition and distinction from other classes of isomeric molecules.

Niobium to alcohol mol ratio control of the concurring esterification and etherification reactions promoted by NbCl5 and Al2O3 catalysts under microwave irradiation

Alcohols and acids can be switched to produce ethers or esters by varying the alcohol to catalyst mol ratio, in a new etherification and esterification method using NbCl5/Al2O3 catalyst under ""solvent free"" conditions and promoted by MW (microwave) irradiation. A ""two sites"" mechanism for the reaction is proposed, in an attempt to clarify the tendency of the catalyst to be dependent on the alcohol alone during the esterification process. (c) 2008 Elsevier B.V. All rights reserved.

Formation of cumulenes, triple-bonded, and related compounds by flash vacuum thermolysis of five-membered heterocycles

Flash vacuum thermolysis of a large variety of heterocyclic compounds is a useful means of production of ketenes, ketenimines, thioketenes, allenes, iminopropadienones, bis(imino)propadienes, iminopropadienethiones, carbodiimides, isothiocyanates, acetylenes, fulminic acid, nitrile imines and nitrile ylides, nitriles, cyanamides, cyanates, and other compounds, often in preparatively useful yields.

Process mineralogy of fluorosilicate minerals in OK Tedi ores

The impact of fluorine in copper flotation was relatively unknown until the introduction of skarn ores in the Ok Tedi concentrator. Fluorine in the copper concentrates reports to the gas phase during the smelting stage and forms a corrosive H2SO4-HCl-HF acid brine mixture which must be neutralised. This work was aimed at studying the mineralogy of the fluorosilicate minerals contained in the various oretypes present in the Ok Tedi porphyry copper deposit. The electron microprobe was used to analyse for fluorine and hence identify the fluorosilicate minerals in each oretype. This study revealed talc, phlogopite, biotite, clays, amphiboles, fluoroapatite and titanite to be the sources of fluorine in the orebody. Laboratory and plant investigations were conducted to study the flotation response of these minerals. Chemical assaying of the products of these tests was done to determine the bulk assay of fluorine, Using Rietveld analysis, quantitative estimates of the fluorosilicate minerals in these products were generated. Marrying of the bulk assay with the respective mineralogical assay enabled the understanding of the flotation behavior of fluorine and it's associated mineralogy. Talc and phlogopite were found to be the causes of the fluorine problem at Ok Tedi. (C) 2001 Elsevier Science Ltd. All rights reserved.