A ring-closing metathesis route to 7-membered aza-heteroannulated sugars

Azepane rings have been constructed diastereoselectively upon a carbohydrate derivative utilising reductive amination and RCM. The stereochemistry of the ring junctions was confirmed by X-ray crystallography and NMR. Diastereoselective dihydroxylation has also been employed to afford a tetrahydroxylated azepane carbohydrate derivative with potential biological activity.     

Ideals and solutions of nonlinear field equations

Families of horizontal ideals of contact manifolds of finite order are studied. Each horizontal ideal is shown to admit ann-dimensional module of Cauchy characteristic vectors that is also a module of annihilators (in the sense of Cartan) of the contact ideal. Since horizontal ideals are generated by 1-forms, any completely integrable horizontal ideal in the family leads to a foliation of the contact manifold by submanifolds of dimensionn on which the horizontal ideal vanishes. Explicit conditions are obtained under which an open subset of a leaf of this foliation is the graph of a solution map of the fundamental ideal that characterizes a given system of partial differential equations of finite order withn independent variables. The solution maps are obtained by sequential integration of systems of autonomous ordinary differential equations that are determined by the Cauchy characteristic vector fields for the problem. We show that every smooth solution map can be obtained in this manner. Let {_Vi¦1in} be a basis for the module of Cauchy characteristic vector fields that are in Jacobi normal form. If a subsidiary balance ideal admits each of then vector fieldsV _i as a smooth isovector field, then certain leaves of the foliation generated by the corresponding closed horizontal ideal are shown to be graphs of solution maps of the fundamental ideal. A subclass of these constructions agree with those of the Cartan-Kähler theorem. Conditions are also obtained under which every leaf of the foliation is the graph of a solution map. Solving a given system ofr partial differential equations withn independent variables on a first-order contact manifold is shown to be equivalent to the problem of constructing a complete system of independent first integrals. Properties of systems of first integrals are analyzed by studying the collection ISO[A _ij ] of all isovectors of the horizontal ideal. We show that ISO[A _ij ] admits the direct sum decomposition ^*[A _ij ]W[A _ij ] as a vector space, where ^*[A _ij ] is the module of Cauchy characteristics of the horizontal ideal. ISO[A _ij ] also forms a Lie algebra under the standard Lie product,^*[A _ij ] andW[A _ij ] are Lie subalgebras of ISO[A _ij ], and [A _ij ] is an ideal. A change of coordinates that resolves (straightens out) the canonical basis for ^*[A _ij ] is constructed. This change of coordinates is used to reduce the problem of solving the given system of PDE to the problem of root extraction of a system ofr functions ofn variables, and to establish the existence of solutions to a second-order system of overdetermined PDE that generate the subspaceW[A _ij ]. Similar results are obtained for second-order contact manifolds. Extended canonical transformations are studied. They are shown to provide algorithms for calculating large classes of closed horizontal ideals and a partial analog of classical Hamilton-Jacobi theory.     

Solid supports for micro analytical systems

The development of micro analytical systems requires that fluids are able to interact with the surface of the microfluidic chip in order to perform analysis such as chromatography, solid phase extraction, and enzymatic digestion. These types of analyses are more efficient if there are solid supports within the microfluidic channels. In addition, solid supports within microfluidic chips are useful in producing devices with multiple functionalities. In recent years there have been many approaches introduced for incorporating solid supports within chips. This review will explore several state of the art methods and applications of introducing solid supports into chips. These include packing chips with beads, incorporating membranes into chips, creating supports using microfabrication, and fabricating gels and polymer monoliths within microfluidic channels.     

Observation of a quadrupole plasmon mode for a colloidal solution of gold nanoprisms

The synthesis and optical properties of single crystalline gold nanoprisms have been investigated. A three-step mediated seed growth process in an aqueous solution generated gold nanoprisms with a relatively homogeneous size distribution. The purity of these nanostructures has allowed us to observe a weak quadrupole resonance in addition to a strong dipole resonance associated with these novel structures. The experimental optical spectra agree with discrete dipole approximation calculations that have been modeled from the dimensions of gold nanoprisms produced in this synthesis.     

A DFT study of the ground state multiplicities of linear vs angular polyheteroacenes

Unrestricted density functional calculations in combination with the broken-symmetry approach and spin-projection methods have been employed to study a series of formally 4n pi antiaromatic linear and angular polyheteroacenes. Calculations show that the linear polyheteroacene molecules have either stable singlet zwitterionic 6-9 or singlet diradical 5 ground states because they sacrifice the aromaticity of the central arene to form two independent cyanines. The corresponding angular compounds 10-14 have robust triplet states, since they cannot create independent cyanines to escape their overall antiaromaticity. An analysis based on the SOMO-SOMO energy splittings, their spatial distributions, and the spin density populations for the triplet states is presented to clarify the factors that determine their ground state multiplicities.     

Solution-phase, triangular ag nanotriangles fabricated by nanosphere lithography

A novel method to produce solution-phase triangular silver nanoparticles is presented. Ag nanoparticles are prepared by nanosphere lithography and are subsequently released into solution. The resulting nanoparticles are asymmetrically functionalized to produce either single isolated nanoparticles or dimer pairs. The structural and optical properties of Ag nanoparticles have been characterized. Mie theory and the Discrete Dipole Approximation method (DDA) have been used to model and interpret the optical properties of the released Ag nanoparticles.     

Angular momentum decoupling approximations in the quantum dynamics of reactive systems

Two methods for implementing angular momentum decoupling approximations in quantum mechanical reactive scattering examined. Applications of both reactive and nonreactive H + H₂ collisions indicate that for the most intense individual reactive transitions and for all degeneracy-averaged ones, these decoupling methods (especially the “proper” decoupling method) yield results in good agreement with those of fully-coupled calculations. However, for the less intense reactive transitions and all individual nonreactive transitions, very large errors can result from use of these approximate methods.