Effect of Different Binders on the Combustion Properties of Lignite. Part II. Effect on kinetics

In this research kinetic analysis of the Tuncbilek lignite and its mixture with different binders (molasses, CMC, sulphide liquor, heavy crude oil, sodium silicate,cornstarch, lime, peridur, bentonite, cement and poly(vinyl-acetate)) were analysed by thermogravimetric (TG/DTG) methods. Two different kinetic models (Arrhenius and Coats–Redfern) were used to determine the activation energies of the samples studied. The concept of weighed mean activation energy was applied to determine the overall reactivity of the samples. It was observed that molasses, CMC, heavy crude oil, peridur, bentonite and poly(acetate) decreased the activation energy of the coal sample, whereas, all other binders increased the activation energy of the coal sample. This revised version was published online in July 2006 with corrections to the Cover Date.     

Lichens and mosses for correlation between trace elements and 210Po in the areas near coal-fired power plant at Yatağan, Turkey

The lichensRhizoplaca melanophthalma, Cladonia convoluta, Cladonia pyxidata and the mossesGrimmia pulvinata, Hypnum cupressiforme were analyzed for Pb, Cr, Cd, Co, Ni, Mn, Cu, Zn and Fe using atomic absorption spectrophotometry over a wide area around a coal-fired power plant located in Yataan. The results were compared with the ²¹⁰Po concentrations previously measured in the same samples. Correlations between ²¹⁰Po and trace elements for different moss and lichen species of the same localization and for different localizations for the same species were also studied. In general trace element concentrations do not show significant differences from site to site for all species except Mn in Hypnum cupressiforme and ²¹⁰Po in Grimmia pulvinata. To discuss the ²¹⁰Pb level and sources in indicator plants analyzed, also radium contents of surface soil at each sampling station was measured and compared with the average values for similar soil types in the literature.     

Photophysical and Analyte Sensing Properties of Cyclometalated Ir(III) Complexes

The synthesis of some heteroleptic, cyclometalated iridium(III) complexes is described. The utility of these [Ir(ppy)₂(N-N)]Cl (ppy = 2-phenylpyridine and N-N = substituted bipyridine, biquinoline, or phenanthroline) complexes as luminescence-based sensors is assessed. The emission intensity of an Ir(III) complex featuring the 3,3′-H_ndcbpy ligand (H_ndcbpy = dicarboxylic acid-2,2′-bipyridine; n = 0,1,2 to indicate deprotonated, mono- and diprotonated species, respectively) is seen to increase in the presence of Pb(II). Insight into the structure and analyte-sensing capability is achieved by X-ray crystallography in conjunction with computational modeling. Complexes incorporating carboxylic acid-functionalized bipyridine and biquinoline as the polypyridyl ligand show pH sensitivity while similar phenanthroline complexes do not.     

Early contrast enhancement of the liver: exact description of subphases using MRI

Purpose

The purpose of this study was to describe the subphases of early post-contrast enhancement of the liver, using vessel enhancement patterns, and correlate these findings with enhancement patterns of abdominal organs.

Materials and Methods

A total of 114 patients who underwent gadolinium-enhanced abdominal magnetic resonance imaging examinations constituted the final study group, of which 56 were women (age range, 3–94 years; mean, 50 years) and 58 were men (age range, 6–85 years; mean, 54 years). Early post-contrast sequences in all patients were evaluated retrospectively by two reviewers for the determination of the presence of contrast enhancement in predetermined major vessels of the abdomen and qualitative and quantitative extent of enhancement of the renal cortex, spleen, pancreas and liver. Based on the overall findings, subphases of early contrast enhancement of the liver were described and quantitative extent of enhancement of organs was correlated with subphases of early contrast enhancement of the liver. Mann–Whitney U test and one-way unbalanced analysis of variance tests were used for the comparisons.

Results

Early hepatic arterial phase was observed in 14/114 patients, mid-hepatic arterial phase in 23/114 patients, late hepatic arterial phase in 33/114 patients, splenic vein only hepatic arterial dominant phase in 20/114 patients and hepatic arterial dominant phase in 24/114 patients. There was an overall association between the subphases of enhancement and the quantitative extent of enhancement for all studied organs (P<.0001).

Conclusion

The evaluation of vessel and organ enhancement patterns has allowed the characterization of five different subphases in early post-contrast enhancement of the liver. The quantitative extent of enhancement of abdominal organs also demonstrated significant correlation with these five subphases.     

Combined quantum mechanical/molecular mechanical study on the pentacoordinated ferric and ferrous cytochrome P450cam complexes

The pentacoordinated ferric and ferrous cytochrome P450(cam) complexes have been investigated by combined quantum mechanical/molecular mechanical (QM/MM) calculations in the presence of a protein/solvent environment and by QM calculations on the isolated QM regions with use of density functional theory. The B3LYP functional has been found more reliable than the BLYP and BHLYP functionals for estimating the relative state energies. The B3LYP/CHARMM calculations with an all-electron basis set for iron give high-spin ground states for the title complexes, in agreement with experiment. The comparison of the B3LYP/CHARMM results of the entire protein system with the B3LYP calculations on the naked QM regions shows that the amount of stabilization by the protein environment is largest for the intermediate-spin states, followed by the high-spin states of the complexes. The calculation of M?ssbauer parameters in the presence of the enzyme environment confirms the double occupation of the d(xz) orbital in the quintet spin state of the ferrous complex, consistent with the computed QM/MM energies in the enzyme environment, while the d(x)2(-)(y)2 orbital is doubly occupied in the gas-phase quintet state.     

Spectral tuning in visual pigments: an ONIOM(QM:MM) study on bovine rhodopsin and its mutants

We have investigated geometries and excitation energies of bovine rhodopsin and some of its mutants by hybrid quantum mechanical/molecular mechanical (QM/MM) calculations in ONIOM scheme, employing B3LYP and BLYP density functionals as well as DFTB method for the QM part and AMBER force field for the MM part. QM/MM geometries of the protonated Schiff-base 11- cis-retinal with B3LYP and DFTB are very similar to each other. TD-B3LYP/MM excitation energy calculations reproduce the experimental absorption maximum of 500 nm in the presence of native rhodopsin environment and predict spectral shifts due to mutations within 10 nm, whereas TD-BLYP/MM excitation energies have red-shift error of at least 50 nm. In the wild-type rhodopsin, Glu113 shifts the first excitation energy to blue and accounts for most of the shift found. Other amino acids individually contribute to the first excitation energy but their net effect is small. The electronic polarization effect is essential for reproducing experimental bond length alternation along the polyene chain in protonated Schiff-base retinal, which correlates with the computed first excitation energy. It also corrects the excitation energies and spectral shifts in mutants, more effectively for deprotonated Schiff-base retinal than for the protonated form. The protonation state and conformation of mutated residues affect electronic spectrum significantly. The present QM/MM calculations estimate not only the experimental excitation energies but also the source of spectral shifts in mutants.     

Trace Elemental Analysis of Allium Species by Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) with Multivariate Chemometrics

Aerial parts and roots of the 12 Allium species collected from five localities of Turkey were studied for trace elements (Ag, As, Cd, Co, Cr, Cu, Ni, Pb, Se, Tl, V, and Zn) using inductively coupled plasma mass spectrometry (ICP-MS). A tomato leaves certified reference material was used to characterize the accuracy and precision of the analysis. Each Allium species contained Se (315–2740?µg/kg), Tl (2.75–71?µg/kg), V (77–6790?µg/kg), and Zn (3.73–26.6?mg/kg) which can meet the necessary daily intake of these minerals. In addition, chemometric analyses were performed using correlation analysis, principal component analysis, and hierarchical cluster analysis to determine the association of 12 trace elements in the Allium species. Using chemometrics, the distribution of elements between aerial parts and roots, and geographic collection localities of Allium species were also examined. This study is important the consumers because of the wide consumption of Allium species. This report is the first detailed characterization of the metal content of Allium species.     

Characterization of the Chemical Profile of Euphorbia Species from Turkey by Gas Chromatography–Mass Spectrometry (GC-MS), Liquid Chromatography–Tandem Mass Spectrometry (LC-MS/MS), and Liquid Chromatography–Ion Trap–Time-of-Flight–Mass Spectrometry (LC-IT-TOF-MS) and Chemometric Analysis†

The Euphorbiaceae family comprises of about 300 genera and 5000 species primarily distributed in America and tropical Africa. The Euphorbia genus is represented by 105 species and locally named as “Sütle?en” and “Xa?îl” in Turkey. The present study aimed to determine the chemical constituents of E. aleppica, E. eriophora, E. macroclada, E. grisophylla, E. seguieriana subsp. seguieriana, E. craspedia, E. denticulata, E. falcata, and E. fistulosa, and classify them by utilizing the chemometric techniques of principal component analysis (PCA) and hierarchical cluster analysis (HCA). Linoleic acid, 17-tetratriacontane, palmitic acid, and hexatriacontane were the major fatty acids from the gas chromatography–mass spectrometry (GC/MS) analyses. Characterization of 268 constituents of the studied species was achieved by liquid chromatography–ion trap–time-of-flight–mass spectrometry (LC-IT-TOF-MS). Furthermore, a new liquid chromatography–tandem mass spectrometry (LC-MS/MS) method was developed and validated for the simultaneous quantitative determination of 11 compounds (quinic acid, protocatechuic acid, rutin, hesperidin, eugenol, p-coumaric acid, piceatannol, scopoletin, dl-kavain, chrysophanic acid, and resiniferatoxin) in these species. The developed method was validated for the linearity, limit of detection, limit of quantification, repeatability, and recovery.     

Computational thermochemistry of glycolaldehyde

We use a variant of the focal point analysis to refine estimates of the relative energies of the four low‐energy torsional conformers of glycolaldehyde. The most stable form is the cis‐cis structure which enjoys a degree of H‐bonding from hydroxyl H to carbonyl O; here dihedral angles τ₁ (O?C? C? O) and τ₂ (C? C? O? H) both are zero. We optimized structures in both CCSD(T)/aug‐cc‐pVDZ and aug‐cc‐pVTZ; the structures agree within 0.01 Å for bond lengths and 1.0 degrees for valence angles, but the larger basis brings the rotational constants closer to experimental values. According to our extrapolation of CCSD(T) energies evaluated in basis sets ranging to aug‐cc‐pVQZ the trans‐trans form (180°, 180°) has a relative energy of 12.6 kJ/mol. The trans‐gauche conformer (160°, ±75°) is situated at 13.9 kJ/mol and the cis‐trans form (0°, 180°) at 18.9 kJ/mol. Values are corrected for zero point vibrational energy by MP2/aug‐cc‐pVTZ frequencies. Modeling the vibrational spectra is best accomplished by MP2/aug‐cc‐pVTZ with anharmonic corrections. We compute the Watsonian parameters that define the theoretical vibrational‐rotational spectra for the four stable conformers, to assist the search for these species in the interstellar medium. Six transition states are located by G4 and CBS‐QB3 methods as well as extrapolation using energies for structures optimized in CCSD(T)/aug‐cc‐pVDZ structures. We use two isodesmic reactions with two well‐established thermochemical computational schemes G4 and CBS‐QB3 to estimate energy enthalpy and Gibbs energy of formation as well as the entropy of the gas phase system. Our extrapolated electronic energies of species appearing in the isodesmic reactions produce independent values of thermodynamic quantities consistent with G4 and CBS‐QB3. © 2013 Wiley Periodicals, Inc.