6-Halogenofulvenes and allylcyclopentadiene from nickelocene

In the presence of triphenylphosphine, nickelocene reacts with tetrachloromethane to give (trichloromethyl)cyclopentadiene, which can be dehydrohalogenated to 6,6-dichlorofulvene. It reacts analogously with tetrabromomethane and (trichloromethyl)benzene. 3-Bromopropene reacts with nickelocene to give allylcyclopentadiene.     

Mechanism of horizontally aligned growth of single-wall carbon nanotubes on R-plane sapphire

As a promising one-dimensional material for building nanodevices, single-wall carbon nanotubes (SWNTs) should be organized into a rational architecture on the substrate surface. In this study, horizontally aligned SWNTs with two alignment modes were synthesized on the same R-plane sapphire wafer by chemical vapor deposition with cationized ferritins as catalysts. In the middle part of the wafer, SWNTs were aligned on the R-plane sapphire in the direction [1101]. At the edge of the wafer, SWNTs were aligned in the tangential direction to the wafer edge. The comparison of these two groups of SWNTs suggests the competition between the two alignment modes and indicates that atomic steps in high density have superior influence on the SWNTs' alignment to the crystal structure on the surface of the sapphire substrate. A "raised-head" growth mechanism model is proposed to explain why catalysts can stay active during the horizontally aligned growth of relatively long SWNTs with the strong interaction between SWNTs and the sapphire substrate.     

Characterization of a novel trace-level impurity in lisinopril using multi-stage mass spectrometry

An impurity in the bulk drug lisinopril was detected by simple reversed-phase high-performance liquid chromatography (HPLC). This trace-level impurity was rapidly identified as 2-(2-oxo-azocan-3-ylamino)-4-phenyl- butyric acid on the basis of the on-line multi-stage mass spectrometric evidence, and the proposed structure was further confirmed by multi-stage mass spectrometry of lisinopril and three related compounds.     

Single DNA molecule stretching in sudden mixed shear and elongational microflows

High-throughput stretching and monitoring of single DNA molecules in continuous elongational flow offers compelling advantages for biotechnology applications such as DNA mapping. However, the polymer dynamics in common microfluidic implementations are typically complicated by shear interactions. These effects were investigated by observation of fluorescently labeled 185 kb bacterial artificial chromosomes in sudden mixed shear and elongational microflows generated in funneled microfluidic channels. The extension of individual free DNA molecules was studied as a function of accumulated fluid strain and strain rate. Under constant or gradually changing strain rate conditions, stretching by the sudden elongational component proceeded as previously described for an ideal elongational flow (T. T. Perkins, D. E. Smith and S. Chu, Science, 1997, 276, 2016): first, increased accumulated fluid strain and increased strain rate produced higher stretching efficiencies, despite the complications of shear interactions; and second, the results were consistent with unstretched molecules predominantly in hairpin conformations. More abrupt strain rate profiles did not deliver a uniform population of highly extended molecules, highlighting the importance of balance between shear and elongational components in the microfluidic environment for DNA stretching applications. DNA sizing with up to 10% resolution was demonstrated. Overall, the device delivered 1000 stretched DNA molecules per minute in a method compatible with diffraction-limited optical sequence motif mapping and without requiring laborious chemical modifications of the DNA or the chip surface. Thus, the method is especially well suited for genetic characterization of DNA mixtures such as in pathogen fingerprinting amidst high levels of background DNA.     

Rigid linear and star-shaped pi-conjugated 2,2':6',2"-terpyridine ligands with blue emission

A series of rigid linear and star-shaped pi-conjugated 2,2':6',2"-terpyridine derivatives with the C-C single-, double-, and triple-bond linkages have been developed through the Suzuki, the Sonogashira, and the Wittig reactions. Such large rigid ligands exhibit strong blue emission in dilute solutions. [structure: see text]     

Computational study of pharmacophores: beta-lactams

The thermochemistry of bicyclic lactams (penams, penems, cephams, cephems), which are key pharmacophores in beta-lactam antibiotics, has been investigated by high-level ab initio methods. Particular attention has been paid to estimating magnitudes of amide resonance (ARE) and ring strain (RSE) in the four-member lactam ring because these quantities are difficult to measure and distinguish experimentally. The ring strain destabilization effect is greater than the stabilization arising from amide resonance. However, in cephemes the amide resonance stabilization slightly exceeds destabilization due to the beta-lactam ring strain.     

Heterochromatin and rDNA 5S and 45S sites as reliable cytogenetic markers for castor bean (Ricinus communis,Euphorbiaceae)

The increasing need for renewable energy resources has led to higher demands for biofuel, a scenario where the castor bean (Ricinus communis L.) seed oil represents a promising source of raw material. Despite that, information regarding the genome organization of R. communis is still scarce, impairing the application of modern biotechnological and breeding procedures. The present work brings the first evaluation of the mitotic chromosomes of this species, including 10 potentially interesting accessions for cultivation in semi-arid environments aiming at the biofuel production. The approach included standard staining, fluorochrome staining (CMA/DAPI), fluorescent in situ hybridization (FISH) with rDNA 5S and 45S, as well as silver impregnation. All accessions were diploid with 2n = 2x = 20, displaying mainly metacentric chromosomes, with CMA-positive bands (GC-rich) in all pairs of the complement. After silver impregnation, one to 14 nucleoli were observed, while the FISH with rDNA 45S revealed two large sites and a variety of minor dots, and the DNAr 5S hybridized in a single pair. The observed features were discussed and compared with literature data regarding pachytene bivalents.     

Eco-friendly location of small hydropower

We address the problem of locating small hydropower dams in an environmentally friendly manner. We propose the use of a multi-objective optimization model to maximize total hydropower production, while limiting negative impacts on river connectivity. Critically, we consider the so called “backwater effects” that dams have on power generation at nearby upstream sites via changes in water surface profiles. We further account for the likelihood that migratory fish and other aquatic species can successfully pass hydropower dams and other artificial/natural barriers and how this is influenced by backwater effects. Although naturally represented in nonlinear form, we manage through a series of linearization steps to formulate a mixed integer linear programing model. We illustrate the utility of our proposed framework using a case study from England and Wales. Interestingly, we show that for England and Wales, a region heavily impacted by a large number of existing river barriers, that installation of small hydropower dams fitted with even moderately effective fish passes can, in fact, create a win-win situation that results in increased hydropower and improved river connectivity.     

Determinant formula and a realization for the Lie algebra W(2,2)

In this paper, an explicit determinant formula is given for the Verma modules over the Lie algebra W(2, 2). We construct a natural realization of a certain vaccum module for the algebra W(2, 2) via the Weyl vertex algebra. We also describe several results including the irreducibility, characters and the descending filtrations of submodules for the Verma module over the algebra W(2, 2).