Imaging the dynamics of gas phase reactions

Ion imaging methods are making ever greater impact on studies of gas phase molecular reaction dynamics. This article traces the evolution of the technique, highlights some of the more important breakthroughs with regards to improving image resolution and in image processing and analysis methods, and then proceeds to illustrate some of the many applications to which the technique is now being applied--most notably in studies of molecular photodissociation and of bimolecular reaction dynamics.     

Interaction of the glycoalkaloid tomatine with DMPC and sterol monolayers studied by surface pressure measurements and Brewster angle microscopy

The interaction of the glycoalkaloid tomatine with monolayers of dimyristoylphosphatidylcholine (DMPC) and cholesterol, as well as other selected sterols, has been investigated using surface pressure measurements at constant area and Brewster angle microscopy (BAM). The interaction of tomatine with sterol monolayers is found to vary with the structure of the sterol. The interaction of tomatine with cholesterol-containing monolayers results in a surface pressure increase accompanied by the appearance of a mottled texture. Morphological changes are observed that suggest the formation of tomatine-cholesterol complexes that aggregate at the water-air interface. No morphology change observable by BAM is observed for monolayers containing epicholesterol, suggesting that the stereochemistry of hydrogen bonding between the sterol and the sugar units on tomatine is of particular significance. Strong interactions are observed with cholestanol- and coprostanol-containing monolayers, and BAM reveals formation of spiked aggregates upon interaction with 7:3 mole ratio DMPC/coprostanol mixed monolayers. More modest surface pressure changes are observed for cholestenone- and epicoprostanol-containing monolayers. A much smaller surface pressure increase is observed when tomatine is injected beneath a pure DMPC monolayer.     

Nematic Liquid Crystals with a Trifluoromethyl Group

Abstract

We have synthesised a new class of compounds incorporating a trifluoromethyl group in the terminal alkoxy or alkenyloxy chain. Compounds containing several aromatic rings were synthesised with a view to producing compounds of high birefringence. This also included the synthesis of compounds containing a carbon-carbon triple bond. Compounds with three 1,4-disubstituted rings were synthesised in order to produce materials with a high nematic clearing point and as low a melting point as possible. Laterally fluoro-substituted compounds were prepared to generate a high positive value of the dielectric anisotropy, a low melting point and no smectic mesophases. Substances containing a cyclohexyl ring, which tend to induce a lower viscosity and compounds incorporating a bicyclo[2.2.2]octane ring were also synthesised in order to produce a high nematic clearing point and to influence the elastic constants. The (E)-trifluorobut-2-enyloxy-compounds were prepared in attempts to produce compounds with appropriate elastic constants and a high birefringence.     

Generic pole assignability,structurally constrained controllers and unimodular completion

In this paper we assume dynamical systems are represented by linear differential-algebraic equations (DAEs) of order possibly higher than one. We consider a structured system of DAEs for both the to-be-controlled plant and the controller. We model the structure of the plant and the controller as an undirected and bipartite graph and formulate necessary and sufficient conditions on this graph for the structured controller to generically achieve arbitrary pole placement. A special case of this problem also gives new equivalent conditions for structural controllability of a plant. Use of results in matching theory, and in particular, ‘admissibility’ of edges and ‘elementary bipartite graphs’, make the problem and the solution very intuitive. Further, our approach requires standard graph algorithms to check the required conditions for generic arbitrary pole placement, thus helping in easily obtaining running time estimates for checking this. When applied to the state space case, for which the literature has running time estimates, our algorithm is faster for sparse state space systems and comparable for general state space systems.     

On the vanishing of subspaces of alternating bilinear forms

Given a field F and integer n≥3, we introduce an invariant s_n (F) which is defined by examining the vanishing of subspaces of alternating bilinear forms on 2-dimensional subspaces of vector spaces. This invariant arises when we calculate the largest dimension of a subspace of n?×?n skew-symmetric matrices over F which contains no elements of rank 2. We show how to calculate s_n (F) for various families of field F, including finite fields. We also prove the existence of large subgroups of the commutator subgroup of certain p-groups of class 2 which contain no non-identity commutators.     

The extended QUALIFLEX method for multiple criteria decision analysis based on interval type-2 fuzzy sets and applications to medical decision making

QUALIFLEX, a generalization of Jacquet-Lagreze’s permutation method, is a useful outranking method in decision analysis because of its flexibility with respect to cardinal and ordinal information. This paper develops an extended QUALIFLEX method for handling multiple criteria decision-making problems in the context of interval type-2 fuzzy sets. Interval type-2 fuzzy sets contain membership values that are crisp intervals, which are the most widely used of the higher order fuzzy sets because of their relative simplicity. Using the linguistic rating system converted into interval type-2 trapezoidal fuzzy numbers, the extended QUALIFLEX method investigates all possible permutations of the alternatives with respect to the level of concordance of the complete preference order. Based on a signed distance-based approach, this paper proposes the concordance/discordance index, the weighted concordance/discordance index, and the comprehensive concordance/discordance index as evaluative criteria of the chosen hypothesis for ranking the alternatives. The feasibility and applicability of the proposed methods are illustrated by a medical decision-making problem concerning acute inflammatory demyelinating disease, and a comparative analysis with another outranking approach is conducted to validate the effectiveness of the proposed methodology.     

CyClick Chemistry for the Synthesis of Cyclic Peptides

Here, we report a novel “CyClick” strategy for the macrocyclization of peptides that works in an exclusively intramolecular fashion thereby precluding the formation of dimers and oligomers via intermolecular reactions. The CyClick chemistry is highly chemoselective for the N‐terminus of the peptide with a C‐terminal aldehyde. In this protocol, the peptide conformation internally directs activation of the backbone amide bond and thereby facilitates formation of a stable 4‐imidazolidinone‐fused cyclic peptide with high diastereoselectivity (>99 %). This method is tolerant to a variety of peptide aldehydes and has been applied for the synthesis of 12‐ to 23‐membered rings with varying amino acid compositions in one pot under mild reaction conditions. The reaction generated peptide macrocycles featuring a 4‐imidazolidinone in their scaffolds, which acts as an endocyclic control element that promotes intramolecular hydrogen bonding and leads to macrocycles with conformationally rigid turn structures.     

Molecular level comparison of water extractives of maple and oak with negative and positive ion ESI FT‐ICR mass spectrometry

Soluble extractives in wood function to protect living trees from destructive agents and also contribute to wood color and fragrance. Some extractive components have biological activities with medical applications. They also play important roles in wood processing and related applications. To increase the knowledge of wood chemistry, maple and oak were extracted by water. Ultraviolet/visible (UV/vis) spectroscopy indicated the presence of a phenolic compound, resorcinol, in maple extractives having higher molecular mass and more aromatic components than oak extractives. Negative and positive electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT‐ICR‐MS) identified thousands of formulas in the two samples in the m/z range of 200 to 800. They mainly fall into the lignin‐like, carbohydrate‐like, and tannin‐like compound categories. The top 25 peaks (ie, formulas) with the highest relative magnitude in negative ESI represented nearly 50% of the summed total spectral magnitude of all formulas assigned in the maple and oak extractives. Furthermore, the base peak (ie, most abundant peak) accounted for about 14% of the total abundance in each wood sample. Literature comparisons identified 17 of 20 formulas in the top five peaks of the four spectra as specific bioactive compounds in trees and other plants, implying the potential to explore utilization of maple and oak extractives for functional and medicinal applications. The various profiling of the top 25 peaks from the two samples also suggested the possible application of FT‐ICR‐MS for detecting chemical markers useful in profiling and identification of wood types and sources.     

Charged condensation

We consider Bose–Einstein condensation of massive electrically charged scalars in a uniform background of charged fermions. We focus on the case when the scalar condensate screens the background charge, while the net charge of the system resides on its boundary surface. A distinctive signature of this substance is that the photon acquires a Lorentz-violating mass in the bulk of the condensate. Due to this mass, the transverse and longitudinal gauge modes propagate with different group velocities. We give qualitative arguments that at high enough densities and low temperatures a charged system of electrons and helium-4 nuclei, if held together by laboratory devices or by force of gravity, can form such a substance. We briefly discuss possible manifestations of the charged condensate in compact astrophysical objects.     

Encapsulated Neutral Ruthenium Catalyst for Substrate-Selective Oxidation of Alcohols

The neutral complex dichloro-{diethyl[(5-phenyl-1,3,4-oxadiazol-2-ylamino)-(4-trifluoro-methylphenyl)methyl]phosphonate} (p-cymene)-ruthenium(II) was encapsulated inside a self-assembled hexameric host obtained upon reaction of 2,8,14,20-tetra-undecyl-resorcin[4]arene and water. The formation of an inclusion complex was inferred from a combination of spectral measurements (MS, UV/Vis spectroscopy, ¹H and DOSY NMR). The ³¹P and ¹⁹F NMR spectra are consistent with motions of the ruthenium complex inside the self-assembled capsule. Molecular dynamics simulations carried out on the inclusion complex confirmed these intra-cavity movements and highlighted possible supramolecular interactions between the ruthenium first coordination sphere ligands and the inner part (aromatic rings) of the capsule. The embedded ruthenium complex was assessed in the catalytic oxidation (using NaIO₄ as oxidant) of mixtures of three arylmethyl alcohols into the corresponding aldehydes. The reaction kinetics were shown to vary as a function of the substrates’ size, with the oxidation rate varying in the order benzylalcohol >4-phenyl-benzylalcohol >9-anthracenemethanol. Control experiments realized in the absence of hexameric capsule did not allow any discrimination between the substrates.