Synthesis, electrochemistry and luminescence of [Pt{4'-(R)trpy}(CN)](+) (R = Ph, o-CH(3)C(6)H(4), o-ClC(6)H(4) or o-CF(3)C(6)H(4); trpy = 2,2':6',2'-terpyridine): crystal structure of [Pt{4'-(Ph)trpy}(CN)]BF(4) x CH(3)CN

The synthesis and characterization of [Pt{4'-(R)trpy}(CN)]X (R = Ph, X = BF(4) or SbF(6); R = o-CH(3)C(6)H(4), X = SbF(6); R = o-ClC(6)H(4), X = SbF(6); or R = o-CF(3)C(6)H(4), X = SbF(6)) are described where trpy = 2,2':6',2'-terpyridine. Single crystals of [Pt{4'-(Ph)trpy}(CN)]BF(4).CH(3)CN were grown by vapour diffusion of diethyl ether into an acetonitrile solution of [Pt{4'-(Ph)trpy}(CN)]BF(4). An X-ray crystal structure determination of the solvated complex confirms the near linear coordination of the cyanide ligand to the platinum centre. The cation is almost planar as evidenced by a twist of only 1.9 degrees of the phenyl group out of the plane of the terpyridyl moiety. Cyclic voltammograms were recorded in DMF/0.1 M TBAH for the [Pt{4'-(R)trpy}(CN)](+) cations. Two quasi-reversible one-electron reduction (cathodic) waves are observed with E(1/2) values that show the trend expected for an increasingly lower energy of the trpy-based LUMO of the complex i.e., [Pt{4'-(Ph)trpy}(CN)](+) approximately [Pt{4'-(o-CH(3)C(6)H(4))trpy}(CN)](+) < [Pt{4'-(o-ClC(6)H(4))trpy}(CN)](+) < [Pt{4'-(o-CF(3)C(6)H(4))trpy}(CN)](+). All the [Pt(4'-(R)trpy}(CN)](+) cations are photoluminescent in dichloromethane. Emission by [Pt{4'-(Ph)trpy}(CN)](+) is from an excited state with largely (3)MLCT orbital parentage, but with some intraligand (3)pi-pi* character mixed-in (tau = 0.1 micros). In contrast, the other three cations display emission that appears exclusively intraligand (3)pi-pi* in origin (tau approximately 0.8 micros). Emission spectra have been recorded in a low concentration frozen DME {1 : 5 : 5 (v/v) DMF-MeOH-EtOH} glass. For the R = o-CH(3)C(6)H(4), o-ClC(6)H(4) and o-CF(3)C(6)H(4) cations the envelope of vibronic structure and energies of the vibrational components are essentially the same as that recorded in dichloromethane. However, for the [Pt{4'-(Ph)trpy}(CN)](+) cation, there is a blue-shift in the energies of the vibrational components as compared to that recorded in dichloromethane, as well as a change in the envelope of vibronic structure to a more "domed" pattern; this has been interpreted in terms of a higher percentage of intraligand (3)pi-pi* character in the emitting state for the glass. Increasing the concentration of the glass invariably leads to aggregation of the cations and the consequent development of new low energy bands, such that at 0.200 mM broad peaks centred at ca. 650 and 700 nm dominate the spectrum; these bands are assigned to excimeric (3)pi-pi* and (3)MMLCT emission, respectively.     

Macroscopic arrays of magnetic nanostructures from self-assembled nanosphere templates

We have extended the widely used technique of nanosphere lithography to produce nanosphere templates with significantly improved long-range order. Single, ordered domains stretching over areas greater than 1 cm2 have been achieved by assembling spheres with the correct surface chemistry on a water/air interface. Self-assembly over macroscopic areas is facilitated by a combination of electrostatic and capillary forces. The presented technique is easily implemented, and the assembled monolayers can be transferred onto almost any surface, thus making the procedure applicable to a broad range of nanoscale research. We demonstrate this through the fabrication of hexagonally ordered, macroscopic arrays of magnetic nanostructures with modified magnetic properties.     

The effect of elevated reactant temperatures on soot nanostructures in a coflow diffusion ethylene flame

The relationship between soot surface growth, soot nanostructure and reactant temperature (T_r) in a coflow diffusion ethylene flame was investigated with multiple experimental techniques. The T_r was raised by heating the coflow air. Three cases, with 300K, 473K, and 673K T_r, respectively, were studied. Laser-induced Incandescence revealed that increasing T_r promotes soot formation. Although soot primary particle diameter (d_p) also increases with T_r, the increase in d_p slows down after 473K T_r, suggesting that there is a deceleration in soot surface growth. Transmission Electron Microscopy (TEM) imaging showed that increased T_r promotes soot aggregation and yields larger and more mature primary particles. The assessment of the Selected Area Electron Diffraction (SAED) patterns indicated that, at 673K T_r, there is a growth of lattice planes. Raman spectroscopy revealed further structural details. By assessing the band intensity ratios, soot for the T_r of 673K has more curved nanostructures. The deceleration of soot surface growth may be explained by surface aging, which is characterized by an increase in curved nanostructures.     

Designing PbSe nanowires and nanorings through oriented attachment of nanoparticles

Single-crystal PbSe nanowires are synthesized in solution through oriented attachment of nanocrystal building blocks. Reaction temperatures of 190-250 degrees C and multicomponent surfactant mixtures result in a nearly defect-free crystal lattice and high uniformity of nanowire diameter along the entire length. The wires' dimensions are tuned by tailoring reaction conditions in a range from approximately 4 to approximately 20 nm in diameter with wire lengths up to approximately 30 microm. PbSe nanocrystals bind to each other on either {100}, {110}, or {111} faces, depending on the surfactant molecules present in the reaction solution. While PbSe nanocrystals have the centrosymmetric rocksalt lattice, they can lack central symmetry due to a noncentrosymmetric arrangement of Pb- and Se-terminated {111} facets and possess dipole driving one-dimensional oriented attachment of nanocrystals to form nanowires. In addition to straight nanowires, zigzag, helical, branched, and tapered nanowires as well as single-crystal nanorings can be controllably prepared in one-pot reactions by careful adjustment of the reaction conditions.     

Efficient conversion of Biginelli 3,4-dihydropyrimidin-2(1H)-one to pyrimidines via PyBroP-mediated coupling

An efficient two-step procedure is described to convert the Biginelli 3,4-dihydropyrimidin-2(1H)-one to various multifunctionalized pyrimidines via the Kappe dehydrogenation and a new mild PyBroP-mediated coupling with C, N, O, and S nucleophiles, which provides a readily accessible multifunctionalized pyrimidine template for diversity-oriented synthesis.     

Infinitely many solutions to perturbed elliptic equations

A new version of perturbation theory is developed which produces infinitely many sign-changing critical points for uneven functionals. The abstract result is applied to the following elliptic equations with a Hardy potential and a perturbation from symmetry:

     

Irreducible polynomials which are locally reducible everywhere

For any positive integer , there exist polynomials of degree which are irreducible over and reducible over for all primes if and only if is composite. In fact, this result holds over arbitrary global fields.

     

Email Surveillance Using Non-negative Matrix Factorization

In this study, we apply a non-negative matrix factorization approach for the extraction and detection of concepts or topics from electronic mail messages. For the publicly released Enron electronic mail collection, we encode sparse term-by-message matrices and use a low rank non-negative matrix factorization algorithm to preserve natural data non-negativity and avoid subtractive basis vector and encoding interactions present in techniques such as principal component analysis. Results in topic detection and message clustering are discussed in the context of published Enron business practices and activities, and benchmarks addressing the computational complexity of our approach are provided. The resulting basis vectors and matrix projections of this approach can be used to identify and monitor underlying semantic features (topics) and message clusters in a general or high-level way without the need to read individual electronic mail messages. Michael W. Berry is a Professor and Interim Department Head in the Department of Computer Science at the University of Tennessee and a faculty member in the Graduate School in Genome Science and Technology Program at the University of Tennessee and Oak Ridge National Laboratory. His research interests include information retrieval, data mining, scientific computing, computational science, and numerical linear algebra. He is a member of the Society for Industrial and Applied Mathematics (SIAM), Association for Computing Machinery (ACM), and the Computer Society of the Institute of Electrical and Electronics (IEEE). Professor Berry is on the editorial boards of “Computing in Science and Engineering” (IEEE Computer Society and the American Institute of Physics) and the SIAM Journal of Scientific Computing. Murray Browne is a Research Associate in the Department of Computer Science at the University of Tennessee. He is a member of the American Society for Information Science and Technology and has published numerous essays, book reviews, newspaper articles, and feature stories.     

Laser induced disruption of bacterial spores on a microchip

We report on the development of a laser based spore disruption method. Bacillus globigii spores were mixed with a laser light absorbing matrix and co-crystallized into 200-microm-wide and 20-microm-deep nanovials formed in a polydimethylsiloxane (PDMS) target plate. Surface tension effects were exploited to effect up to 125-fold spore enrichment. When the target zones were illuminated at atmospheric pressure with pulsed UV-laser light at fluences below 20 mJ cm(-2) a change in spore morphology was observed within seconds. Post illumination PCR analysis suggests the release of endogenous DNA indicative of spore disruption. For laser fluences above 20 mJ cm(-2), desorption of spores and fragments was also observed even without a matrix being employed. Desorbed material was collected in a PDMS flowcell attached to the target plate during laser illumination. This opens up a route towards the direct extraction of released DNA in an integrated spore disruption-PCR amplification microchip device.     

A weighted gram-schmidt method for convex quadratic programming

Range-space methods for convex quadratic programming improve in efficiency as the number of constraints active at the solution decreases. In this paper we describe a range-space method based upon updating a weighted Gram-Schmidt factorization of the constraints in the active set. The updating methods described are applicable to both primal and dual quadratic programming algorithms that use an active-set strategy. Many quadratic programming problems include simple bounds on all the variables as well as general linear constraints. A feature of the proposed method is that it is able to exploit the structure of simple bound constraints. This allows the method to retain efficiency when the number ofgeneral constraints active at the solution is small. Furthermore, the efficiency of the method improves as the number of active bound constraints increases. This research was supported by the U.S. Department of Energy Contract DE-AC03-76SF00326, PA No. DE-AT03-76ER72018; National Science Foundation Grants MCS-7926009 and ECS-8012974; the Office of Naval Research Contract N00014-75-C-0267; and the U.S. Army Research Office Contract DAAG29-79-C-0110. The work of Nicholas Gould was supported by the Science and Engineering Research Council of Great Britain.