Numerical analysis of saltwater intrusion using B-spline boundary elements

Continuity of the derivatives of the main variable is an important feature to obtain an accurate representation of moving boundaries with discrete numerical methods, since the value and direction of the velocity are normally used to relocate the nodal points in a time-marching scheme. A recently developed formulation of the boundary element method using cubic B-splines provides up to C² continuity between adjacent elements. This formulation is applied in this work to saltwater intrusion problems in confined, leaky and unconfined aquifers.     

Enthalpy of formation of the cyclopentadienyl radical: photoacoustic calorimetry and ab initio studies

The gas-phase C-H bond dissociation enthalpy (BDE) in 1,3-cyclopentadiene has been determined by time-resolved photoacoustic calorimetry (TR-PAC) as 358 +/- 7 kJ mol(-1). Theoretical results from ab initio complete basis-set approaches, including the composite CBS-Q and CBS-QB3 procedures, and basis-set extrapolated coupled-cluster calculations (CCSD(T)) are reported. The CCSD(T) prediction for the C-H BDE of 1,3-cyclopentadiene (353.3 kJ mol(-1)) is in good agreement with the TR-PAC result. On the basis of the experimental and the theoretical values obtained, we recommend 355 +/- 8 kJ mol(-1) for the C-H BDE of 1,3-cyclopentadiene and 271 +/- 8 kJ mol(-1) for the enthalpy of formation of cyclopentadienyl radical.     

An all-atom force field for metallocenes

A new all-atom force field, for the molecular modeling of metallocenes was constructed. Quantum chemical calculations were performed to obtain several force field terms not yet defined in the literature. The remainder were transferred from the OPLS-AA/AMBER framework. The parametrization work included the obtention of geometrical parameters, torsion energy profiles, and distributions of atomic charges that blend smoothly with the OPLS-AA specification for a variety of organic molecular fragments. Validation was carried out by comparing simulated and experimental data for five different ferrocene derivatives in the crystalline phase. The present model can be regarded as a step toward a general force field for metallocenes, built in a systematic way, easily integrated with OPLS-AA, and transferable between different metal-ligand combinations.     

Energetics of C-F, C-Cl, C-Br, and C-I bonds in 2-haloethanols. enthalpies of formation of XCH(2)CH(2)OH (X = F, Cl, Br, I) compounds and of the 2-hydroxyethyl radical

The energetics of the C-F, C-Cl, C-Br, and C-I bonds in 2-haloethanols was investigated by using a combination of experimental and theoretical methods. The standard molar enthalpies of formation of 2-chloro-, 2-bromo-, and 2-iodoethanol, at 298.15 K, were determined as Delta(f)H(degree)m(CH2CH2OH, l) = -315.5 +/- 0.7 kJ.mol-1, Delta(f)H(degree)mBrCH2CH2OH, l) = -275.8 +/- 0.6 kJ.mol-1, Delta(f)H(degree)m(ICH2CH2OH, l) = -207.3 +/- 0.7 kJ.mol-1, by rotating-bomb combustion calorimetry. The corresponding standard molar enthalpies of vaporization, Delta(vap)H(degree)m(ClCH2CH2OH) = 48.32 +/- 0.37 kJ.mol-1, Delta(vap)H(degree)m(BrCH2CH2OH) = 54.08 +/- 0.40 kJ.mol-1, and Delta(vap)H(degree)m(ICH2CH2OH) = 57.03 +/- 0.20 kJ.mol-1 were also obtained by Calvet-drop microcalorimetry. The condensed phase and vaporization enthalpy data lead to Delta(f)H(degree)m(ClCH2CH2OH, g) = -267.2 +/- 0.8 kJ.mol-1, Delta(f)H(degree)m(BrCH2CH2OH, g) = -221.7 +/- 0.7 kJ.mol-1, and Delta(f)H(degree)m(ICH2CH2OH, g) = -150.3 +/- 0.7 kJ.mol-1. These values, together with the enthalpy of selected isodesmic and isogyric gas-phase reactions predicted by density functional theory (B3LYP/cc-pVTZ) and CBS-QB3 calculations were used to derive the enthalpies of formation of gaseous 2-fluoroethanol, Delta(f)H(degree)m(FCH2CH2OH, g) = -423.6 +/- 5.0 kJ.mol-1, and of the 2-hydroxyethyl radical, Delta(f)H(degree)m(CH2CH2OH, g) = -28.7 +/- 8.0 kJ.mol-1. The obtained thermochemical data led to the following carbon-halogen bond dissociation enthalpies: DHo(X-CH2CH2OH) = 474.4 +/- 9.4 kJ.mol-1 (X = F), 359.9 +/- 8.0 kJ.mol-1 (X = Cl), 305.0 +/- 8.0 kJ.mol-1 (X = Br), 228.7 +/- 8.1 kJ.mol-1 (X = I). These values were compared with the corresponding C-X bond dissociation enthalpies in XCH2COOH, XCH3, XC2H5, XCH=CH2, and XC6H5. In view of this comparison the computational methods mentioned above were also used to obtain Delta(f)H(degree)m-594.0 +/- 5.0 kJ.mol-1 from which DHo(F-CH2COOH) = 435.4 +/- 5.4 kJ.mol-1. The order DHo(C-F) > DHo(C-Cl) > DHo(C-Br) > DHo(C-I) is observed for the haloalcohols and all other RX compounds. It is finally concluded that the major qualitative trends exhibited by the C-X bond dissociation enthalpies for the series of compounds studied in this work can be predicted by Pauling's electrostatic-covalent model.     

Improved survival of cardiac cells on surface modified electrospun nanofibers

Polycaprolactone (PCL) is a popular synthetic polymer used in the field of cardiac tissue engineering (CTE) due to its non-toxic degraded by products and low cost manufacturing method. However, hydrophobic nature of this material limits its wide spread application in different cell interaction processes. Therefore, current study aims to chemically modify PCL made random and aligned nanofibers with collagen coating mimicking the oriented matrix of the cardiac cells. Morphological and chemical properties of the electrospun PCL nanofibers were evaluated by SEM, FTIR, XRD and water contact angle measurement. Results indicated that the anisotropic characteristics of aligned nanofibers promoted cell attachment and alignment, which closely match the requirements of native cardiac cells. Thus, aligned nanofibers could be preferred for cardiac tissue regeneration and defects over random nanofibers.     

Properties of a new 4-imidazolyl derivative of a 14-membered tetraazamacrocyclic chelating agent

A new bis-N,N'-(5-methylimidazol-4-ylmethyl) derivative of a 14-membered tetraazamacrocycle, L1, has been synthesized. The protonation constants of this compound and the stability constants of its complexes with divalent first-row transition metal ions and Fe3+ were determined at 298.2 K in aqueous 0.10 mol dm(-3) KNO3. Compound L1 exhibits high overall basicity, which is mainly conferred by the imidazolyl groups. The complexes of the divalent first row-transition metal ions of L1 follow the Irving-Williams order of stability with the maximum for Cu2+ as expected, but a steep fall of constants is verified for the Mn2+, Fe2+ and Co2+, in one side, and for the Zn2+ complexes, in the other side. Additionally, L1 shows a large affinity for Fe3+, and the relative stability constants for its Cd2+ and Pb2+ complexes indicate that L1 may be useful for the complexometric determination of these two toxic metal ions in solutions containing both metal ions. These studies together with NMR, UV-vis and EPR spectroscopic data indicated the presence of mononuclear complexes, which adopt distorted pyramidal or octahedral geometries depending on the metal centre. The X-ray crystal structure of [Cu(HL1)](PF6)2(NO3).H2O showed that the coordination sphere of the copper centre can be described as a distorted square pyramid with the basal plane defined by three nitrogen donors of the macrocycle backbone and one nitrogen atom from one imidazolyl pendant arm. The apical position is occupied by the nitrogen atom of the macrocycle trans to the pyridine ring. To achieve this coordination environment, the macrocycle is folded along the axis defined by the two N atoms contiguous to the pyridine ring. The free methylimidazolyl arm points away from the metal centre leading to an intramolecular Cu[dot dot dot]N distance of 5.155(1) A.     

Magnetoresistive chip cytometer

Although conventional state-of-the-art flow cytometry systems provide rapid and reliable analytical capacities, they are bulky, expensive and complex. To overcome these drawbacks modern flow cytometers have been developed with enhanced portability for on-site measurements. Unlike external fluorescent/optical detectors, magnetoresistive sensors are micro-fabricated, can be integrated within microfluidic channels, and can detect magnetically labelled cells. This work describes the real-time detection of single magnetically labelled cells with a magnetoresistive based cell cytometer. For Kg1-a cells magnetically labelled with 50 nm CD34 microbeads (Milteny) flowing through a 150 μm wide, 14 μm high microchannel, with speeds around 1 cm s(-1), bipolar signals with an average amplitude of 10-20 μV were observed corresponding to cell events. The number of cells counted by the spin valve cytometer has been compared with that obtained with a hemocytometer. Both methods agree within the respective error bars.     

Wood typification by Venturi easy ambient sonic spray ionization mass spectrometry: the case of the endangered Mahogany tree

Venturi easy ambient sonic spray ionization mass spectrometry in both its liquid (V(L) -EASI-MS) and solid sample modes (V(S) -EASI-MS) is shown to provide nearly immediate and secure typification of woods, as demonstrated for Mahogany, an endangered and most valuable type of tropical wood. This reddish wood displays unique phytochemical markers (phragmalin-type limonoids) which are rapidly detected from the wood surface by V(S) -EASI-MS or from a simple methanol extract of a tiny wood chip by V(L) -EASI-MS. Unique profiles were obtained for Mahogany (Swietenia macrophylla) whereas genuine samples of six other similar types of woods, which are commonly falsified by artificial coloring and commercialized as Mahogany, display also typical but dissimilar pythochemical profiles as compared to that of the authentic wood. Variable and atypical chemical profiles were observed for artificially colored woods. Secure chemical characterization via V(S) -EASI-MS or V(s) -EASI-MS fingerprints of Mahogany and other types of woods with similar appearance should help to control the illegal logging and trade of this and other endangered woods and their falsification, and to create certified standards.