Discrete DNA-gold nanoparticle conjugates with DNA lengths as short as 15 bases for both 5 and 20 nm gold particles have been purified by anion-exchange HPLC. Conjugates comprising short DNA (<40 bases) and large gold particles (> or =20 nm) are difficult to purify by other means and are potential substrates for plasmon coupling experiments. Conjugate purity is demonstrated by hybridizing complementary conjugates to form discrete structures, which are visualized by TEM.
We briefly review the existing database of supernova spectropolarimetry, concentrating on recent data and on results from our group's research. Spectropolarimetry provides the only direct known probe of early-time supernova geometry. To obtain reliable conclusions, however, it is very important to correctly account for interstellar polarization. We find that Type IIn supernovae (SNe IIn) tend to be highly polarized, perhaps in part because of the interaction of the ejecta with an asymmetric circumstellar medium. In contrast, SNe II-P are not polarized much, at least shortly after the explosion. At later times, however, there is evidence for increasing polarization, as one views deeper into the expanding ejecta. Moreover, core-collapse SNe that have lost part (SN IIb) or all (SN Ib) of their hydrogen (or even helium; SN Ic) layers prior to the explosion tend to show substantial polarization; thus, the deeper we probe into core-collapse events, the greater the asphericity. There is now conclusive evidence that at least some SNe Ia are intrinsically polarized, although only by a small amount. Finally, SN spectropolarimetry provides the opportunity to study the fundamental properties of the interstellar dust in external galaxies. For example, we have found evidence for extremely high polarization efficiency for the dust along the line-of-sight to SN 1999gi in NGC 3184.
In this chapter the authors discuss the Pd-catalyzed reactions of aryl, alkenyl, benzyl, alkyl, and acyl electrophiles with metal nucleophiles leading to carbon-metal bond formation. The Sonogashira and related Heck-type alkyne hydrogen substitution reactions are presented. Genuine examples of the Pd-catalyzed cross-coupling reactions of preformed alkynylmetals with organic halides and the conjugate substitution reactions are outlined. The chapter also includes special discussion of the following classes of compounds: heteroaromatics; chiral compounds and their asymmetric synthesis; conjugated oligomers of biological significance; conjugated oligomers and polymers of materials chemical interest and natural products.
An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.
Our aim is to perturb the input so that an algorithm designed under the hypothesis of input non-degeneracy can execute on arbitrary instances. The deterministic scheme of [EmCa] was the first efficient method and was applied to two important predicates. Here it is extended in a consistent manner to another two common predicates, thus making it valid for most algorithms in computational geometry. It is shown that this scheme incurs no extra algebraic complexity over the original algorithm while it increases the bit complexity by a factor roughly proportional to the dimension of the geometric space. The second contribution of this paper is a variant scheme for a restricted class of algorithms that is asymptotically optimal with respect to the algebraic as well as the bit complexity. Both methods are simple to implement and require no symbolic computation. They also conform to certain criteria ensuring that the solution to the original input can be restored from the output on the perturbed input. This is immediate when the input to solution mapping obeys a continuity property and requires some case-specific work otherwise. Finally we discuss extensions and limitations to our approach.
This work presents a multiphysics model simulating membrane-electrode assemblies for CO<sub>2</sub> reduction.
In the plane-strain theory of the finite deformation of a hyperelastic solid that has a thin elastic coating on all or part of its boundary, the properties of the Hessian matrix of the coating energy, regarded as a function of the boundary stretch and a curvature-like variable, have been shown recently to play an important role in connection with the analysis of stability. Here it is proved that the Hessian is positive semidefinite in an energy-minimizing configuration. The proof is given for the case in which the bulk material to which the coating is bonded is not subject to any internal kinematic constraints and is then extended to allow for the constraint of incompressibility.
A modular synthetic strategy for the construction of cofacial porphyrin architectures bearing hydrogen-bond synthons on a xanthene platform is presented. The convergent approach is based on a xanthene aldehyde-ester building block that is easily obtainable on a multigram scale with minimal purification. Treatment of this xanthene derivative with a variety of aryl aldehydes and pyrrole under standard Lindsey conditions affords a family of meso-substituted porphyrins bearing a single functionalized xanthene spacer. Direct modification of the hydrogen-bond synthon after macrocyclization proceeds smoothly to furnish porphyrin systems with a variety of cofacial functionalities (e.g., carboxylic acid, ester, amide). Porphyrins bearing two trans-functionalized xanthene spacers are prepared by the MacDonald [2 + 2] condensation of the xanthene aldehyde-ester with readily available 5-aryl-substituted dipyrromethanes such as 5-mesityldipyrromethane to afford the pure alpha,alpha- and alpha,beta-porphyrin atropisomers after chromatographic separation. The versatility of this synthetic method offers intriguing opportunities for the use of these and related templates for the study of proton-coupled activation of small molecules.
Chiral dienes represent an important class of ligands for several asymmetric transition-metal-catalyzed transformations. Due to this fact the development of efficient and reliable protocols for the preparation of these ligands is an essential objective. In this communication, the authors present an enantioselective synthesis of C 2 and C 1 dienes based on their initial work in the field of stepwise C-H functionalization of alkenes using cobalt dinitrosoalkane complexes (J. Am. Chem. Soc. 2008, 130, 3777). The accessible products 5 can be considered as potentially interesting precursors of new chiral diene ligands.
Abstract The divergent dendronization of an ϵ‐caprolactone‐based polymer has been performed to provide access to dendronized polymers with sufficient biocompatibility and degradability for use as drug‐delivery scaffolds. The synthesis was performed through the tin(II) 2‐ethylhexanoate‐catalyzed polymerization of a γ‐functionalized ϵ‐caprolactone monomer, followed by the divergent growth of pendant polyester dendrons at each repeat unit. The resulting dendronized polymers were obtained up to the fourth generation with molecular weights as high as 80,000 Da and with polydispersities between 1.11 and 1.22. The fourth‐generation hydroxyl‐terminated dendronized polymer was degradable under a variety of aqueous conditions. A comparison of the dendronization approach with a procedure involving the ring‐opening polymerization of a second‐generation dendritic macromonomer reveals that the former procedure is best suited for the preparation of this family of dendronized polyesters because it requires shorter reaction times and affords materials with higher degrees of polymerization. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3563–3578, 2004
