Molecular depth profiling of organic and biological materials

Atomic depth profiling using secondary ion mass spectrometry, SIMS, is common in the field micro-electronics; however, the generation of molecular information as a function of sample depth is difficult due to the accumulation of damage both on and beneath the sample surface. The introduction of polyatomic ion beams such as SF₅ and C₆₀ have raised the possibility of overcoming this problem as they deposit the majority of their energy in the upper surface of the sample resulting in increased sputter yields but with a complimentary reduction in sub-surface damage accumulation. In this paper we report the depth profile analysis of the bio-polymer polycaprolactone, PCL, using the polyatomic ions and and the monoatomic Au⁺. Results are compared to recent analysis of a similar sample using . depth profiling of cellulose is also demonstrated, an experiment that has been reported as unsuccessful when attempted with implications for biological analysis are discussed.     

One-Pot Synthesis of Chiral N-Arylamines by Combining Biocatalytic Aminations with Buchwald–Hartwig N-Arylation

The combination of biocatalysis and chemo-catalysis increasingly offers chemists access to more diverse chemical architectures. Here, we describe the combination of a toolbox of chiral-amine-producing biocatalysts with a Buchwald–Hartwig cross-coupling reaction, affording a variety of α-chiral aniline derivatives. The use of a surfactant allowed reactions to be performed sequentially in the same flask, preventing the palladium catalyst from being inhibited by the high concentrations of ammonia, salts, or buffers present in the aqueous media in most cases. The methodology was further extended by combining with a dual-enzyme biocatalytic hydrogen-borrowing cascade in one pot to allow for the conversion of a racemic alcohol to a chiral aniline.     

Synthesis of Polymers Containing Potassium Acyltrifluoroborates (KATs) and Post-polymerization Ligation and Conjugation

We report the synthesis of monomers for atom-transfer radical polymerization (ATRP) and a reversible addition-fragmentation chain transfer (RAFT) agent bearing trifluoroborate iminiums (TIMs), which are quantitatively converted into potassium acyltrifluoroborates (KATs) after polymerization. The resulting KAT-containing polymers are suitable for rapid amide-forming ligations for both post-polymerization modification and polymer conjugation. The polymer conjugation occurs rapidly, even under dilute (micromolar) aqueous conditions at ambient temperatures, thereby enabling the synthesis of a variety of linear and star-shaped block copolymers. In addition, we applied post-polymerization modification to the covalent linking of a photocaged cyclic antibiotic (gramicidin S) to the side chains of the KAT-containing copolymer. Cellular assays revealed that the polymer–antibiotic conjugate is biocompatible and provides efficient light-controlled release of the antibiotic on demand.     

Tate cohomology and periodic localization of polynomial functors

In this paper, we show that Goodwillie calculus, as applied to functors from stable homotopy to itself, interacts in striking ways with chromatic aspects of the stable category. Localized at a fixed prime p, let T(n) be the telescope of a v_n self map of a finite S–module of type n. The Periodicity Theorem of Hopkins and Smith implies that the Bousfield localization functor associated to T(n)_* is independent of choices. Goodwillies general theory says that to any homotopy functor F from S–modules to S–modules, there is an associated tower under F, {P_dF}, such that FP_dF is the universal arrow to a d–excisive functor. Our first main theorem says that P_dFP_d-1F always admits a homotopy section after localization with respect to T(n)_* (and so also after localization with respect to Morava K–theory K(n)_*). Thus, after periodic localization, polynomial functors split as the product of their homogeneous factors. This theorem follows from our second main theorem which is equivalent to the following: for any finite group G, the Tate spectrum is weakly contractible. This strengthens and extends previous theorems of Greenlees–Sadofsky, Hovey–Sadofsky, and Mahowald–Shick. The Periodicity Theorem is used in an essential way in our proof. The connection between the two theorems is via a reformulation of a result of McCarthy on dual calculus. Mathematics Subject Classification (2000) 55P65, 55N22, 55P60, 55P91     

Curve following in illiquid markets

In this article the problem of curve following in an illiquid market is addressed. The optimal control is characterised in terms of the solution to a coupled FBSDE involving jumps via the technique of the stochastic maximum principle. Analysing this FBSDE, we further show that there are buy and sell regions. In the case of quadratic penalty functions the FBSDE admits an explicit solution which is determined via the four step scheme. The dependence of the optimal control on the target curve is studied in detail.     

On the convergence rate of grad-div stabilized Taylor-Hood to Scott-Vogelius solutions for incompressible flow problems

It was recently proven in Case et al. (2010) [2] that, under mild restrictions, grad-div stabilized Taylor-Hood solutions of Navier-Stokes problems converge to the Scott-Vogelius solution of that same problem. However, even though the analytical rate was only shown to be (where γ is the stabilization parameter), the computational results suggest the rate may be improvable to γ−1. We prove herein the analytical rate is indeed γ−1, and extend the result to other incompressible flow problems including Leray-α and MHD. Numerical results are given that verify the theory.     

Rational approximation to harmonic functions

Padé-type approximation is the rational function analogue of Taylor’s polynomial approximation to a power series. A general method for obtaining Padé-type approximants to Fourier series expansions of harmonic functions is defined. This method is based on the Newton-Cotes and Gauss quadrature formulas. Several concrete examples are given and the convergence behavior of a sequence of such approximants is studied. This revised version was published online in June 2006 with corrections to the Cover Date.     

A variational method for the calculation of spin-rovibronic energy levels of triatomic molecules with three interacting electronic states

A general method is presented for the evaluation of the spin rovibronic energy levels of triatomic molecules with up to three interacting potential energy surfaces. The full theory is outlined in detail, both for singlet and for doublet electronic states and the method is then applied to the benchmark example of C₂H. High quality multireference configuration interaction calculations have been carried out to generate the 3-dimensional near-equilibrium adiabatic potential energy surfaces of the three lowest 1²A'(X²Σ⁺), 2²A'(A²Π), 1²A''(A²Π) electronic states of C₂H, and the pair of interacting states of A 0 symmetry have then been diabatized. Results are presented for J up to 7/2 and compared with gas-phase high resolution experimental results for energies up to 5600 cm¹.     

The diophantine equation x3 − 3xy2 − y3 = 1 and related equations

The diophantine equation of the title has been solved by Ljunggren, by indirect use of the p-adic method (use is made of intermediate algebraic extensions). It is generally accepted that an immediate application of the p-adic method for the aforementioned equation is impossible. In this paper, however, this view was overthrown by first solving x² + 3 = 4y³ and then x³ ? 3xy² ? y³ = 1 with direct application of the p-adic method, avoiding the use of intermediate algebraic extensions, fulfilling thus a desire of Professor Mordell. The method used in this paper has a general character, as it is shown in Appendix B, where three more examples are given.