Spin liquid state in the S = 1/2 triangular lattice Ba3CuSb2O9

The synthesis and characterization of Ba3CuSb2O9, which has a layered array of Cu2+ spins in a triangular lattice, are reported. The magnetic susceptibility and neutron scattering experiments of this material show no magnetic ordering down to 0.2 K with a θ(CW) = -55 K. The magnetic specific heat reveals a T-linear dependence with a γ = 43.4 mJ K(-2) mol(-1) below 1.4 K. These observations suggest that Ba3CuSb2O9 is a new quantum spin liquid candidate with a S = 1/2 triangular lattice.     

Theoretical studies on aromaticity of selected hydroxypyrones. Part 3#. Chelatoaromaticity phenomenon in metalcomplexes of hydroxypyrones

The aim of this project is to study the aromatic properties of various forms (neutral, cationic, and anionic) of selected hydroxypyrones (pyromeconic acid, maltol, and ethylmaltol) and their metalcomplexes with aluminum, gallium, and indium ions. Aromaticity of hydroxypyrone metalcomplexes is important because it can influence the stability of such complexes, which is crucial for their applications in medicinal and environmental chemistry. Results from ten different indices of aromaticity (HOMA, NICS(0), NICS(1), NICS_scan, ASE_iso, PDI, FLU, I_ring, MCI, and KMCI) show that aromaticity in hydroxypyrones decreases in the order cations > neutral molecules > anions. Performed calculations situate the aromaticities of ligands in metalcomplexes close to their respective cations. This means that complexation causes a significant increase of the aromaticity of ligands, which stabilizes formed chelatocomplexes. On the other hand, we clearly show that rings that are involved in binding metal ions are not aromatic. Copyright © 2010 John Wiley & Sons, Ltd.     

The Formation of Pd Nanocrystals from Pd2(dba)3 Microcrystals

As‐grown platelets formed from tris‐(dibenzylideneacetone) dipalladium(0) [Pd₂(dba)₃] precursor in the presence of Pd17 RNA are investigated before and after thermal annealing. Results show that as‐grown platelets are disordered crystals of Pd₂(dba)₃ containing 1?2 nm Pd clusters and platelets grown in the absence of RNA are morphologically and structurally similar to those formed with RNA. The initially formed crystals are so sensitive to environmental variables that the degree of crystallinity can not be determined accurately by electron diffraction. X‐ray crystallography on as‐grown platelets gives a crystal structure consistent with Pd₂(dba)₃, but reveals a composition of ≈Pd_1.07(dba)₃, indicating one Pd atom in Pd₂(dba)₃ is lost from the structure. Both electron beam and thermally induced decomposition of as‐grown Pd₂(dba)₃ platelets having a hexagonal habit on the micrometer scale produces elemental Pd platelets having a hexagonal habit on the nanometer scale. These hexagonal platelets are composed of a partially sparse form of Pd₂(dba)₃ that is initially crystalline but rapidly degrades due to the loss of Pd atoms from organic ligand cages. Once released, Pd atoms aggregate to form Pd clusters, which grow and transform into well‐formed Pd nanocrystals under electron‐beam irradiation or through thermal annealing.     

The Yang-Mills Heat Semigroup on Three-Manifolds with Boundary

Long time existence and uniqueness of solutions to the Yang-Mills heat equation is proven over a compact 3-manifold with smooth boundary. The initial data is taken to be a Lie algebra valued connection form in the Sobolev space H ₁. Three kinds of boundary conditions are explored, Dirichlet type, Neumann type and Marini boundary conditions. The last is a nonlinear boundary condition, specified by setting the normal component of the curvature to zero on the boundary. The Yang-Mills heat equation is a weakly parabolic nonlinear equation. We use gauge symmetry breaking to convert it to a parabolic equation and then gauge transform the solution of the parabolic equation back to a solution of the original equation. Apriori estimates are developed by first establishing a gauge invariant version of the Gaffney-Friedrichs inequality. A gauge invariant regularization procedure for solutions is also established. Uniqueness holds upon imposition of boundary conditions on only two of the three components of the connection form because of weak parabolicity. This work is motivated by possible applications to quantum field theory.     

Spatially Resolved Confocal Resonant Raman Microscopic Analysis of Anode‐Grown Geobacter sulfurreducens Biofilms

When grown on the surface of an anode electrode, Geobacter sulfurreducens forms a multi‐cell thick biofilm in which all cells appear to couple the oxidation of acetate with electron transport to the anode, which serves as the terminal metabolic electron acceptor. Just how electrons are transported through such a biofilm from cells to the underlying anode surface over distances that can exceed 20 microns remains unresolved. Current evidence suggests it may occur by electron hopping through a proposed network of redox cofactors composed of immobile outer membrane and/or extracellular multi‐heme c‐type cytochromes. In the present work, we perform a spatially resolved confocal resonant Raman (CRR) microscopic analysis to investigate anode‐grown Geobacter biofilms. The results confirm the presence of an intra‐biofilm redox gradient whereby the probability that a heme is in the reduced state increases with increasing distance from the anode surface. Such a gradient is required to drive electron transport toward the anode surface by electron hopping via cytochromes. The results also indicate that at open circuit, when electrons are expected to accumulate in redox cofactors involved in electron transport due to the inability of the anode to accept electrons, nearly all c‐type cytochrome hemes detected in the biofilm are oxidized. The same outcome occurs when a comparable potential to that measured at open circuit (?0.30 V vs. SHE) is applied to the anode, whereas nearly all hemes are reduced when an exceedingly negative potential (?0.50 V vs. SHE) is applied to the anode. These results suggest that nearly all c‐type cytochrome hemes detected in the biofilm can be electrochemically accessed by the electrode, but most have oxidation potentials too negative to transport electrons originating from acetate metabolism. The results also reveal a lateral heterogeneity (x–y dimensions) in the type of c‐type cytochromes within the biofilm that may affect electron transport to the electrode.     

Third body modeling in fretting using the combined finite-discrete element method

A new approach was developed for modeling the effect of the third body on fretting. This was accomplished using the combined finite-discrete element method (FDEM) in which the third body is analyzed as discrete elements while the first bodies are modeled using finite elements. This approach provides a link between large scale models which treat the mass of wear debris as a single or small number of bodies and small scale models which only study a control volume. The FDEM was used to analyze the behavior of third body particles between flat sliding surfaces. When the third body mass is composed of unconnected particles, it behaves as a Newtonian fluid, but this behavior ceases when the particles are connected into platelets. The FDEM was also used to study the behavior of third body particles inside a Hertzian line contact. As the number of particles and platelet size increase the load carried by the worn slip zone grows larger in relationship to the unworn stick zone.     

Collision-induced dissociation mass spectrometry of nonionic surfactants following direct supercritical fluid injection

Direct injection from a capillary supercritical fluid chromatography system was used as an inlet technique for chemical ionization (CI) and low energy collision-induced dissociation (CID) mass spectrometry of a series of low volatility nonionic surfactant mixtures. Characteristic fragment ions produced by CID for various classes of nonionic surfactant molecules were found to depend greatly on the structure of the surfactant hydrophobe. This was the case even when the charge on the molecule appeared localized away from the hydrophobe. Numerous decomposition pathways are suggested by the fragment ions produced. The use of direct supercritical fluid injection as an inlet technique does not appear to influence adversely the ability to produce cm mass spectra. Direct supercritical fluid introduction allows CI to be compared with other ionization mechanisms more commonly used for multifunctional, low volatility samples.     

Effect of an aliphatic spacer group on the adsorption mechanism on the colloidal silver surface of L‐proline phosphonodipeptides

A comparative study of molecular structures of five L ‐proline (L ‐Pro) phosphonodipeptides: L ‐Pro‐NH‐C(Me,Me)‐PO₃H₂ (P1), L ‐Pro‐NH‐C(Me,iPr)‐PO₃H₂ (P2), L ‐Pro‐L ‐NH‐CH(iBu)‐PO₃H₂ (P3), L ‐Pro‐L ‐NH‐CH(PA)‐PO₃H₂ (P4) and L ‐Pro‐L ‐NH‐CH(BA)‐PO₃H₂ (P5) has been carried out using Raman and absorption infrared techniques of molecular spectroscopy. The interpretation of the obtained spectra has been supported by density functional theory calculations (DFT) at the B3LYP; 6–31 + + G** level using Gaussian 2003 software. The surface‐enhanced Raman scattering (SERS) on Ag‐sol in aqueous solutions of these phosphonopeptides has also been investigated. The surface geometry of these molecules on a silver colloidal surface has been determined by observing the position and relative intensity changes of the Pro ring, amide, phosphonate and so‐called spacer (−R) groups vibrations of the enhanced bands in their SERS spectra. Results show that P4 and P5 adsorb onto the silver as anionic molecules mainly via the amide bond (∼1630, ∼1533, ∼1248, ∼800 and ∼565 cm⁻¹), Pro ring (∼956, ∼907 and ∼876 cm⁻¹) and carboxylate group (∼1395 and ∼909 cm⁻¹). Coadsorption of the imine nitrogen atom and PO group with the silver surface, possibly by formation of a weaker interaction with the metal, is also suggested by the enhancement of the bands at 1158 and 1248 cm⁻¹. P1, P2 and P3 show two orientations of their main chain on the silver surface resulting from different interactions of the  C CH₃,  NH and  CONH fragments with this surface. Bonding to the Ag surface occurs mainly through the imino atom (1166 cm⁻¹) for P2, while for P1 and P3 it occurs via the methyl group(s) (1194–1208 cm⁻¹). The amide group functionality (CONH) is practically not involved in the adsorption process for P1 and P2, whereas the C_s P bonds do assist in the adsorption. Copyright © 2008 John Wiley & Sons, Ltd.     

Optical Spectroscopy as a Method for Skin Cancer Risk Assessment

Skin cancer is the most prevalent cancer, and its assessment remains a challenge for physicians. This study reports the application of an optical sensing method, elastic scattering spectroscopy (ESS), coupled with a classifier that was developed with machine learning, to assist in the discrimination of skin lesions that are concerning for malignancy. The method requires no special skin preparation, is non‐invasive, easy to administer with minimal training, and allows rapid lesion classification. This novel approach was tested for all common forms of skin cancer. ESS spectra from a total of 1307 lesions were analyzed in a multi‐center, non‐randomized clinical trial. The classification algorithm was developed on a 950‐lesion training dataset, and its diagnostic performance was evaluated against a 357‐lesion testing dataset that was independent of the training dataset. The observed sensitivity was 100% (14/14) for melanoma and 94% (105/112) for non‐melanoma skin cancer. The overall observed specificity was 36% (84/231). ESS has potential, as an adjunctive assessment tool, to assist physicians to differentiate between common benign and malignant skin lesions.