Nanoscale Organolanthanum Clusters: Nuclearity-Directing Role of Cyclopentadienyl and Halogenido Ligands

Tetramethylaluminato/halogenido(X) ligand exchange reactions in half-sandwich complexes [Cp^RLa(AlMe₄)₂] are feasible in non-coordinating solvents and provide access to large coordination clusters of the type [Cp^RLaX₂]_x. Incomplete exchange reactions generate the hexalanthanum clusters [Cp^R₆La₆X₈(AlMe₄)₄] (Cp^R=Cp*=C₅Me₅, X=I; Cp^R=Cp′=C₅H₄SiMe₃, X=Br, I). Treatment of [Cp*La(AlMe₄)₂] with two equivalents Me₃SiI gave the nonalanthanum cluster [Cp*LaI₂]₉, while the exhaustive reaction of [Cp′La(AlMe₄)₂] with the halogenido transfer reagents Me₃GeX and Me₃SiX (X=I, Br, Cl) produced a series of monocyclopentadienyl rare-earth-metal clusters with distinct nuclearity. Depending on the halogenido ion size the homometallic clusters [Cp′LaCl₂]₁₀ and [Cp′LaX₂]₁₂ (X=Br, I) could be isolated, whereas different crystallization techniques led to the aggregation of clusters of distinct structural motifs, including the desilylated cyclopentadienyl-bridged cluster [(μ-Cp)₂Cp′₈La₈I₁₄] and the heteroaluminato derivative [Cp′₁₀La₁₀Br₁₈(AlBr₂Me₂)₂]. The use of the Cp′ ancillary ligand facilitates cluster characterization by means of NMR spectroscopy.     

Cu-DNAzyme facilitates highly sensitive immunoassay

A simple Cu-DNAzyme system is used for signal transduction of a CuO nanoparticle-labeled immunoassay, which makes the immunoassay fast, simple, cost-effective, and sensitive, thus promising for biomedical applications and point-of-care testing.     

Raman spectroscopy based on a single-crystal sapphire fiber

We demonstrate the advantages of using a single-crystal sapphire fiber to perform Raman spectroscopy over using a standard glass fiber. The narrow Raman peaks and the low background signal of a single-crystal sapphire fiber allow for the detection of weaker Raman signals or Raman signals much closer to the incident laser wavelength than with a standard glass fiber, which has a strong broadband Raman spectrum of its own. The Raman spectra of calcite, single-walled carbon nanotubes, and aqueous sodium carbonate solution were collected using a 50 cm long, 200 μm diameter sapphire fiber, and then they were compared with the results using a 50 cm long, 100 μm diameter glass fiber. The Raman spectrum of each tested material becomes indistinguishable due to the background Raman signal of the glass fiber but can easily be seen using the sapphire fiber, which has only a few narrow Raman peaks of its own.     

A de bruijn-type formula for enumerating patterns of partitions

We develop a formula for enumerating the partitions of a set up to the action of a group. We give some special cases of this formula and illustrate its use with an example. Some comments are made relating the formula to an earlier formula.This work was supported in part by NSF Contract GP-43010.     

Gray codes in graphs of subsets

Let G(n,k) be a graph whose vertices are the k-element subsets of an n-set represented as n-tuples of “O's” and “1's” with k “1's”. Two such subsets are adjacent if one can be obtained from the other by switching a “O” and a “1” which are in adjacent positions, where the first and nth positions are also considered adjacent. The problem of finding hamiltonian cycles in G(n,k) is discussed. This may be considered a problem of finding “Gray codes” of the k-element subsets of an n-set. It is shown that no such cycle exists if n and k are both even or if k=2 and n?7 and that such a cycle does exist in all other cases where k?5.     

k-space inherited parallel acquisition (KIPA): application on dynamic magnetic resonance imaging thermometry

In this study, a novel method for dynamic parallel image acquisition and reconstruction is presented. In this method, called k-space inherited parallel acquisition (KIPA), localized reconstruction coefficients are used to achieve higher reduction factors, and lower noise and artifact levels compared to that of generalized autocalibrating partially parallel acquisition (GRAPPA) reconstruction. In KIPA, the full k-space for the first frame and the partial k-space for later frames are required to reconstruct a whole series of images. Reconstruction coefficients calculated for different segments of k-space from the first frame data set are used to estimate missing k-space lines in corresponding k-space segments of other frames. The local determination of KIPA reconstruction coefficients is essential to adjusting them according to the local signal-to-noise ratio characteristics of k-space data. The proposed algorithm is applicable to dynamic imaging with arbitrary k-space sampling trajectories. Simulations of magnetic resonance thermometry using the KIPA method with a reduction factor of 6 and using dynamic imaging studies of human subjects with reduction factors of 4 and 6 have been performed to prove the feasibility of our method and to show apparent improvement in image quality in comparison with GRAPPA for dynamic imaging.     

Unified description of 0+ states in a large class of nuclear collective models

A remarkably simple regularity in the energies of 0+ states in a broad class of collective models is discussed. A single formula for all 0+ states in flat-bottomed infinite potentials that depends only on the number of dimensions and a simpler expression applicable to all three interacting boson approximation symmetries in the large N(B) limit are presented. Finally, a connection between the energy expression for 0+ states given by the X5 model and the predictions of the interacting boson approximation near the critical point of the first order phase transition is explored.     

Divergent Synthesis of Bioactive Dithiodiketopiperazine Natural Products Based on a Double C(sp3)−H Activation Strategy

This article provides a detailed report of our efforts to synthesize the dithiodiketopiperazine (DTP) natural products (−)-epicoccin G and (−)-rostratin A using a double C(sp³)−H activation strategy. The strategy's viability was first established on a model system lacking the C8/C8’ alcohols. Then, an efficient stereoselective route including an organocatalytic epoxidation was secured to access a key bis-triflate substrate. This bis-triflate served as the functional handles for the key transformation of the synthesis: a double C(sp³)−H activation. The successful double activation opened access to a common intermediate for both natural products in high overall yield and on a multigram scale. After several unsuccessful attempts, this intermediate was efficiently converted to (−)-epicoccin G and to the more challenging (−)-rostratin A via suitable oxidation/reduction and protecting group sequences, and via a final sulfuration that occurred in good yield and high diastereoselectivity. These efforts culminated in the synthesis of (−)-epicoccin G and (−)-rostratin A in high overall yields (19.6 % over 14 steps and 12.7 % over 17 steps, respectively), with the latter being obtained on a 500 mg scale. Toxicity assessments of these natural products and several analogues (including the newly synthesized epicoccin K) in the leukemia cell line K562 confirmed the importance of the disulfide bridge for activity and identified dianhydrorostratin A as a 20x more potent analogue.