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.     

Synthesis of a deca-lithium cage containing an [(RN)2As(mu-NR)As(NR)2]4- tetraanion; a homologue of group 15 trianions of the type [E(NR)3]3-

The novel, deca-lithium cage [(mtaNHLi)(As2(Nmta)5)-Li(4).2thf]2 (1) (mtaN = 5-methylthiazolyl, C4H4N2S) contains an imido-bridged tetraanion [(mtaN)2As(mu-Nmta)-As(Nmta)2]4-, which represents a new type of multi-functional imido group 15 ligand framework (homologous with group 15 anions of the type [As(NR)3]3-).     

Templating and selection in the formation of macrocycles containing [[P(micro-NtBu)(2)](micro-NH)](n) frameworks: observation of halide ion coordination

Amination of [ClP(micro-NtBu)](2) (1) using NH(3) in THF gives the cyclophospha(III)zane dimer [H(2)NP(micro-NtBu)](2) (2), in good yield. (31)P NMR spectroscopic studies of the reaction of 1 with 2 in THF/Et(3)N show that almost quantitative formation of the cyclic tetramer [[P(micro-NtBu)](2)(micro-NH)](4) (3) occurs. The remarkable selectivity of this reaction can (in part) be attributed to pre-organisation of 1 and 2, which prefer cis arrangements in the solid state and solution. The macrocycle 3 can be isolated in yields of 58-67 % using various reaction scales. The isolation of the major by-product of the reaction (ca. 0.5-1 % of samples of 3), the pentameric, host-guest complex [[P(micro-NtBu)(2)](2)(micro-NH)](5)(HCl).2 THF] (4.2 THF), gives a strong indication of the mechanism involved. In situ (31)P NMR spectroscopic studies support a stepwise condensation mechanism in which Cl(-) ions play an important role in templating and selection of 3 and 4. Amplification of the pentameric arrangement occurs in the presence of excess LiX (X=Cl, Br, I). In addition, the cyclisation reaction is solvent- and anion-dependent. The X-ray structures of 2 and 4.2 THF are reported.     

A modified internal lock-mass method for calibration of the product ions derived from sustained off-resonance irradiation collision-induced dissociation using a Fourier transform mass spectrometer

A modified internal lock-mass calibration method is introduced for improving the mass measurement accuracy of the product ion spectra derived from sustained off-resonance irradiation collision-induced dissociation (SORI-CID) Fourier transform ion cyclotron resonance (FTICR) mass spectrometry. This method involves an initial external calibration of the Fourier transform mass spectrometer to obtain the initial A- and B-terms for the equation (f(i) = A/(m/z)(i) + B). The A-term is adjusted by using an empirical relationship between the up-shift of the A-term and the pulse-gas duration, whereas the B-term is adjusted by using the mass of the unfragmented precursor ion from the SORI-CID mass spectrum of the unknown sample as internal lock-mass. These adjusted A- and B-terms are then used to provide exact mass SORI-CID calibration for the unknown sample. The modified internal lock-mass method achieved average mass measurement accuracy of approximately 3 ppm which is significantly better than that of the conventional internal lock-mass calibration ( approximately 9 ppm) and is approaching that of the internal calibration ( approximately 2 ppm) and requires no addition of internal calibrant or instrumental modifications.     

Generalized logic and the representation of rings

Following the progression towards weaker logics, a number of authors have considered the notion of a sheaf over a quantale or, equivalently, a quantale valued set. In this paper, we use ideas from enriched category theory to motivate the definition of a quantic sheaf. Given a localic subquantale of Q, a quantic sheaf over Q gives a sheaf in the usual sense. As an application, we derive a series of sheaf representations for commutative rings including the familiar Pierce representation.     

Novel alkyl-modified anionic siloxanes as pseudostationary phases for electrokinetic chromatography. III. Performance in organic-modified buffers

Anionic water-soluble siloxanes modified with different amounts of alkyl chains have been used as pseudostationary phases in electrokinetic chromatography. Ionic siloxane polymers with attached alkyl chains of C8 and C12 and having different alkyl chain densities have been employed previously to achieve selective and efficient separations with a range of electrophoretic mobilities and methylene selectivities. In this study, the performance of three alkyl-modified siloxanes is examined in different organic-modified buffers and at differing amounts of organic modifier. The organic modifiers used are acetonitrile and methanol. The siloxanes are stable in these organic solvents and show good mobility and good methylene selectivities even at high concentration of organic solvent. Siloxanes have also been used to separate a mixture of 14 polynuclear aromatic hydrocarbons in an acetonitrile-modified buffer.