The Role of Radical Bridges in Polynuclear Single-Molecule Magnets

Employing radical bridges between anisotropic metal ions has been a viable route to achieve high-performance single-molecule magnets (SMMs). While the bridges have been mainly considered for their ability to promote exchange interactions, the crystal-field effect arising from them has not been taken into account explicitly. This lack of consideration may distort the understanding and limit the development of the entire family. To shed light on this aspect, herein we report a theoretical investigation of a series of N -radical-bridged diterbium complexes. It is found that while promoting strong exchange coupling between the terbium ions, the N -radical induces a crystal field that interferes destructively with that of the outer ligands, and thus reduces the overall SMM behavior. Based on the theoretical results, we conclude that the SMM behavior in this series could be further maximized if the crystal field of the outer ligands is designed to be collinear with that of the radical bridge. This conclusion can be generalized to all exchange-coupled SMMs.     

Influence of exciton-exciton interaction with spin paired charge carriers and exciton-lattice interaction on the surface properties of crystalline solids

Applying tight-binding approximation and spin pairing of like charge carriers in a pair of excitons created in a lattice, the possibility of forming a bound exciton-exciton state is studied. It is found that, provided there exists strong exciton-lattice interaction, such a bound state may be formed and its energy may lie within the valence band deforming the material into a crystalline solid with no energy gap. Lowering of the energy is calculated in naphthalene and anthracene crystals where some experimental results are known. The excess energy released after the formation of such bound state can be adequate, depending on the material, to desorb neutral atoms or eject of electrons from surfaces.     

Minimal entropy and collapsing with curvature bounded from below

We show that if a closed manifold M admits an ℱ-structure (not necessarily polarized, possibly of rank zero) then its minimal entropy vanishes. In particular, this is the case if M admits a non-trivial S ¹-action. As a corollary we obtain that the simplicial volume of a manifold admitting an ℱ-structure is zero.?We also show that if M admits an ℱ-structure then it collapses with curvature bounded from below. This in turn implies that M collapses with bounded scalar curvature or, equivalently, its Yamabe invariant is non-negative.?We show that ℱ-structures of rank zero appear rather frequently: every compact complex elliptic surface admits one as well as any simply connected closed 5-manifold.?We use these results to study the minimal entropy problem. We show the following two theorems: suppose that M is a closed manifold obtained by taking connected sums of copies of S ⁴, ℂP ², ²,S ²×S ²and the K3 surface. Then M has zero minimal entropy. Moreover, M admits a smooth Riemannian metric with zero topological entropy if and only if M is diffeomorphic to S ⁴,ℂP ²,S ²×S ²,ℂP ²#  ² or ℂP ²# ℂP ². Finally, suppose that M is a closed simply connected 5-manifold. Then M has zero minimal entropy. Moreover, M admits a smooth Riemannian metric with zero topological entropy if and only if M is diffeomorphic to S ⁵,S ³×S ², then on trivial S ³-bundle over S ² or the Wu-manifold SU(3)/SO(3). Oblatum 13-III-2002 & 12-VIII-2002?Published online: 8 November 2002 G.P. Paternain was partially supported by CIMAT, Guanajuato, México.?J. Petean is supported by grant 37558-E of CONACYT.     

A simple and general method for the synthesis of multicomponent Na2V6O16.3H2O single-crystal nanobelts

Multicomponent Na2V6O16.3H2O (barnesite) single-crystalline nanobelts were synthesized by a direct reaction-crystallization growth of bulk V2O5 and NaF powders under hydrothermal treatment without using any templates or catalysts. This new strategy could be extended to prepare other one-dimensional multicomponent nanomaterials including ammonium, alkali-metal or alkali-earth metal vanadium oxide bronzes and other transition metal oxyfluorides. This is an efficient and mild solution method with clear advantages over the traditional high-temperature approach for the large-scale production of 1D multicomponent nanomaterials. The applicability of this approach toward the preparation of other inorganic systems, such as tungstates and molybdates, will be explored.     

Microwave-assisted synthesis and in-situ self-assembly of coaxial Ag/C nanocables

We have successfully developed a new one-pot solution-phase route, namely microwave-assisted hydrothermal reduction/carbonization (MAHRC), for a rapid synthesis of coaxial Ag/C nanocables. The nanocables can self-assemble in situ in an end-to-end fashion into interconnected chains.     

syn-2,3-Disubstituted-2,3-dihydro-1,4-benzoxathiin rings: preparation from quinone ketals and 2-mercaptoethanols

A general method for the preparation of syn-2,3-disubstituted-2,3-dihydro-1,4-benzoxathiin rings from 2-mercaptoethanols and quinone ketals is presented. This ring system is produced by Michael addition of a 2-mercaptoethanol to a quinone ketal, followed by cyclization of the initial Michael adduct, and subsequent aromatization to afford a syn-2,3-disubstituted-1,4-benzoxathiin in fair to good chemical yield. Several chiral syn-2,3-disubstituted-2,3-dihydro-1,4-benzoxathiin rings were prepared with this method from enantioenriched 2-mercaptoethanols. No loss of enantiopurity was observed.     

An alternative sampling algorithm for use in liquid chromatography/tandem mass spectrometry experiments

In liquid chromatography/tandem mass spectrometry (LC/MS/MS) analyses of complex peptide mixtures, dynamic exclusion functions are used to minimize repeat selections of identical precursors for collision induced dissociation (CID). We describe a new algorithm for the dynamic exclusion of m/z values during LC/MS/MS. Full-scan based peak exclusion (Fulspec) uses a simplified model of chromatographic peak formation to detect and exclude contaminants present throughout the run or that lead to broad peaks. Therefore, instead of excluding peptides from fragment analysis according to a rigidly predefined time window, the chromatographic properties of the detected analytes are used. The algorithm was tested on two datasets derived from previously published experiments. Fulspec achieves a distribution of CID spectra with minimal tailing on the retention time axis, without resorting to rigid exclusion of m/z values. The procedure further excludes intensities with a bias towards low-quality CID spectra. This combination frees up valuable analytical capacity. The underlying intensity vs. quality analyses challenge the assumption that abundant precursors automatically give the best identifications. Further validation of the algorithm will require its incorporation by equipment manufacturers into the instrument control programs.     

A mesoporous Pt/TiO2 nanoarchitecture with catalytic and photocatalytic functions

A novel metal/semiconductor nanocomposite with catalytic and photocatalytic functions has been prepared. The new material consists of highly dispersed platinum (Pt) nanoparticles embedded in a cubic mesoporous nanocrystalline anatase (meso-nc-TiO2) thin film. The porous thin film possesses a narrow pore-size distribution and a large surface area. The diameter of the Pt cluster can be controlled to below 5 nm, and the high dispersion of these clusters gives rise to catalytic activity for the oxidation of carbon monoxide, an important reaction for automobile exhaust treatment. This novel ordered mesoporous Pt/TiO2 nanoarchitecture is also a promising photochemical material, as demonstrated by the photo-driven killing of Micrococcus lylae cells on the film.