Endothermic ion molecule reactions

Endothermic ion-molecule reactions in a tandem mass spectrometer have been used for a number of years for determining thermodynamic quantities, such as heats of formation and proton affinities, for gaseous ions. Recently, the reactive, endothermic collision has been exploited as an analytical technique for the structural analysis of peptides and other biomolecules. The technique is based upon the endothermic transfer of protons associated with amide bonds to ammonia. This reaction proceeds via a long-lived collision complex. When additional beam energy is supplied, other dissociation channels are opened up, leading to the production of sequence ions for the mass-selected, protonated analyte that are normally observed in high energy collision-induced dissociation spectra. The advantage, however, is that such spectra can be produced at very low beam energies. In this article, the rationale for developing this scheme, and its roots in previous ion-molecule studies, are explored.     

Fourier analysis of the approximation power of principal shift-invariant spaces

The approximation order provided by a directed set {S _h } _h>0 of spaces, each spanned by thehZ ^d -translates of one function, is analyzed. The nearoptimal approximants of [R2] from eachs _h to the exponential functions are used to establish upper bounds on the approximation order. These approximants are also used on the Fourier transform domain to yield approximations for other smooth functions, and thereby provide lower bounds on the approximation order. As a special case, the classical Strang-Fix conditions are extended to bounded summable generating functions.The second part of the paper consists of a detailed account of various applications of these general results to spline and radial function theory. Emphasis is given to the case when the scale {s _h } is obtained froms ₁ by means other than dilation. This includes the derivation of spectral approximation orders associated with smooth positive definite generating functions.     

Synthesis of the C1-side chain of zaragozic acid D and progress towards a total synthesis

A synthesis of a 1,3-dithiane corresponding to the C1-side chain of zaragozic acid D is described. An aldol reaction using an Evans oxazolidinone is the key step in controlling stereochemistry. Metallation of the derived dithiane monosulfoxide and coupling to an aldehyde effected construction of the C1-C7 bond. Subsequent steps are also reported, including acid-mediated ketalization resulting in formation of an advanced synthetic intermediate containing the bicyclic ketal core of the natural product.     

Elimination of the diagonalization bottleneck in parallel Direct-SCF methods

Summary It is shown that the matrix diagonalization bottleneck associated with thesequential O(N _BFN ³ ) diagonalization of the fock matrix within each iteration of the Direct-SCF procedure may be eliminated, and replaced instead with a combination ofparallel O(N _BFN ^<4 ) andsequential O(N _Sub ³ ) steps. For large basis sets, the relation N_Sub N_BFN between the dimension of the expansion subspace and the number of basis functions leads to a method of wave-function optimization in which the sequential bottleneck is eliminated. As a side benefit, the second-order iterative procedure on which this method is based displays superior convergence properties, and provides greater insight into the behavior of the energy with respect to orbital variations, than the traditional first-order, fixed-point, iterative approaches. The implementation of this method may be incorporated into essentially any existing Direct-SCF program with only minimal, and localized, changes.     

A Lumped Parameter Model for Product Flow Times in Manufacturing Lines

Based upon basic drivers for the flow time, a lumped parameter model for a manufacturing line has been derived by using Kingman's approximation. The lumped parameter model for the flow time consists of a workstation and delay time. The workstation is characterized by the effective process time of the bottleneck workstation and the weighted sum of the coefficients of variation of all workstations. The delay time is determined by the sum of all effective process times of the nonbottleneck workstations. The advantage of the application of the lumped parameter model is that the variability of the total line is determined by a measurement at the operating point of the actual manufacturing line. This variability depends upon the operating point. Examples show that this dependency is not too strong for lines with a distinct bottleneck workstation in the actual line. From the derivation of the lumped parameter model it can be concluded that an improvement of the effective process time of the bottleneck workstation of the line results in an increase of the total variability of the line. This variability can be reduced by either reducing the variability of all workstations or the effective process times of the nonbottleneck workstations     

O2 and organic semiconductors: Electronic effects

Contact potential difference (CPD) measurements of the relative work functions of a range of organic semiconductor thin films show that oxygen causes effective p-type doping (with work functions increasing 0.1–0.3 eV). This doping effect is found to be reversible by exposure to high vacuum or heating in inert atmosphere. The mechanism of doping is explained by a model, based on a reversible formation of an O-substrate charge transfer state. Conductivity measurements of p-phthalocyanine films at variable temperatures support this doping model. The oxygen doping effect is consistent with filling of tail states in the gap, as shown by the increase of activation energy of hole transport with decreased O-doping, and by the good fit between experimental data and simulations of the in-gap density of states. A model hybrid solar cell configuration also shows the effect of doping by O₂ and corroborates the fact that O-doping fills the tail states in the system.     

Geometry of Thin Films

Journal of Nonlinear Science - We study ray optics in the context of double-mirror systems, in the limit as the two mirrors approach one another (thin films). This leads to a novel set of...     

Detection challenges in quantitative polymer analysis by liquid chromatography

Accurate quantification of polymer distributions is one of the main challenges in polymer analysis by liquid chromatography. The response of contemporary detectors is typically influenced by compositional features such as molecular weight, chain composition, end groups, and branching. This renders the accurate quantification of complex polymers of which there are no standards available, extremely challenging. Moreover, any (programmed) change in mobile‐phase composition may further limit the applicability of detection techniques. Current methods often rely on refractive index detection, which is not accurate when dealing with complex samples as the refractive‐index increment is often unknown. We review current and emerging detection methods in liquid chromatography with the aim of identifying detectors, which can be applied to the quantitative analysis of complex polymers.