Transition-metal 13-atom clusters assessed with solid and surface-biased functionals

First-principles density-functional theory studies have reported open structures based on the formation of double simple-cubic (DSC) arrangements for Ru(13), Rh(13), Os(13), and Ir(13), which can be considered an unexpected result as those elements crystallize in compact bulk structures such as the face-centered cubic and hexagonal close-packed lattices. In this work, we investigated with the projected augmented wave method the dependence of the lowest-energy structure on the local and semilocal exchange-correlation (xc) energy functionals employed in density-functional theory. We found that the local-density approximation (LDA) and generalized-gradient formulations with different treatment of the electronic inhomogeneities (PBE, PBEsol, and AM05) confirm the DSC configuration as the lowest-energy structure for the studied TM(13) clusters. A good agreement in the relative total energies are obtained even for structures with small energy differences, e.g., 0.10 eV. The employed xc functionals yield the same total magnetic moment for a given structure, i.e., the differences in the bond lengths do not affect the moments, which can be attributed to the atomic character of those clusters. Thus, at least for those systems, the differences among the LDA, PBE, PBEsol, and AM05 functionals are not large enough to yield qualitatively different results.     

Two‐Photon Imaging of a Cellular Line Using Organic Fluorescent Nanoparticles Synthesized by Laser Ablation

A comparative study of the optical properties of organic fluorescent nanoparticles fabricated by laser ablation (NPs‐LA), reprecipitation (NPs‐RP), and microemulsion (NPs‐ME) methods is presented. These nanoparticles contain a fluorene‐based p‐conjugated molecule (BT2). Distinctive electronic transitions are observed in samples due to the specific way in which the molecule BT2 is assembled in each type of nanoparticles; for instance, transitions involved in absorption and emission spectra of NPs‐LA result in blueshifting with respect to the molecular solution of BT2, whereas redshifting is observed in NPs‐RP and NPs‐ME. Further, the results show that under infrared excitation, the aqueous suspensions of NPs‐LA exhibit the highest fluorescence induced by two‐photon absorption (≈790 GM at 740 nm), as well as the best photostability, compared with aqueous suspensions of NPs‐RP and NPs‐ME. The nanoparticles synthetized by the three aforementioned methods are employed as exogenous agents for the visualization of human cervical cancer cell line (HeLa) using confocal and two‐photon microscopy. Under similar experimental conditions, it is found that microscopy images of the best quality are obtained with NPs‐LA. These results show that laser ablation is a suitable technique for the fabrication of organic fluorescent nanoparticles used as contrast agents for in vitro fluorescence microscopy.     

Electrochemical study of a dendritic family at the water/1,2-dichloroethane interface

The transfer of six dendritric molecules, DMs, across the water/1,2-dichloroethane interface was investigated using cyclic voltammetry. From the variation of peak potential with pH, two different mechanisms of transfer were postulated depending on the nature of the molecules. Voltammetric parameters were employed to evaluate the hydrophilic/hydrophobic character and calculate the acid dissociation constant of these molecules. The results were explained taking into account the nature and multiplicity of functional surface groups.     

Influence of external factors on the micellization process and aggregate structure of poly(oxy)styrene-poly(oxy)ethylene block copolymers

Solutions of the polyoxystyrene-polyoxyethylene block copolymer SO(17)EO(65), where SO denotes polystyrene oxide block as the hydrophobic block and EO the polyethylene oxide block as the hydrophilic block, in mixtures of water (a selective solvent for the EO blocks) and 1,4-dioxane (a good solvent for both blocks) were studied by surface tension and light scattering measurements. Surface and micellar structural parameters have been analyzed as a function of solvent composition. The critical micelle concentration increases and the micellar aggregation number decreases, respectively, as the amount of 1,4-dioxane in the binary solvent increases as a consequence of the enhanced solubility of the SO blocks in the solvent mixture, causing the lowering of the interfacial tension between the hydrophobic blocks in the micellar core and the solvent; therefore, to achieve thermodynamic equilibrium, the micelle size decreases. In addition, static light scattering (SLS) has been proved to be a useful technique to detect the lower boundary of the transition between a dilute micellar solution (sol) to a local-ordered micellar solution (soft gel) resulting from a percolation mechanism. Comparison of the sol-soft gel boundaries obtained from SLS for copolymers SO(17)EO(65) and EO(67)SO(15)EO(67) with those previously derived by rheology is made. Finally, changes in the autocorrelation function of the solutions at the boundary obtained from dynamic light scattering are also analyzed.     

Apoptolidin A: total synthesis and partially glycosylated analogues

The total synthesis of apoptolidin A is described employing an early glycosylation strategy. Strategic disconnections were chosen between C11-C12 (cross-coupling) and C19O-C1 (macrocyclization). The cis-selective glycosylation at C9-OH was achieved with the new SIBA protective group at O2/O3 of the L-glucose residue. Auxiliary substitutents at the 2-position of the 2-deoxy sugars were applied to form selectively the glycosidic linkages of the C27 disaccharide. The cross-coupling of the glycosylated northern half with the glycosylated southern half was achieved with CuI-thiophene carboxylate. The macrocyclization of a trihydroxy carboxylic acid produced the 20-membered macrolide selectively. H2SiF6 was suitable for the final deprotection of the silyl ethers and the conversion of the C21 methylketal into the hemiketal. The synthetic flexibility of the approach was proven by the synthesis of some glycovariants.     

Micrometric single crystal germanates obtained using a double‐spherical mirror furnace

Micro‐crystals of two new compounds EuMnGe₂O₇ and SmMnGe₂O₇ were grown performing the flux method in a double‐spherical mirror furnace. One valuable advantage of this system was that the heating profile could be modified easily adjusting lamp positions and orientation as well. The micrometric crystals were observed and analyzed for chemical composition by scanning electron microscopy and energy dispersive spectroscopy. This furnace is perfectly suitable to grow at low price, low temperature and short time new materials as a single crystal for basic research or to obtain raw material. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

The bilateral birth–death chain generated by the associated Jacobi polynomials

We give a probabilistic interpretation of the associated Jacobi polynomials, which can be constructed from the three-term recurrence relation for the classical Jacobi polynomials by shifting the integer index n by a real number t. Under certain restrictions, this will give rise to a doubly infinite tridiagonal stochastic matrix, which can be interpreted as the one-step transition probability matrix of a discrete-time bilateral birth–death chain with state space on $\mathbb{Z}$. We also study the unique UL and LU stochastic factorizations of the transition probability matrix, as well as the discrete Darboux transformations and corresponding spectral matrices. Finally, we use all these results to provide an urn model on the integers for the associated Jacobi polynomials.