The position dependent 15N enrichment of nitrous oxide in the stratosphere.

The position dependent 15N fractionation of nitrous oxide (N2O), which cannot be obtained from mass spectrometric analysis on molecular N2O itself, can be determined with high precision using isotope ratio mass spectrometry on the NO+ fragment that is formed on electron impact in the source of an isotope ratio mass spectrometer. Laboratory UV photolysis experiments show that strong position dependent 15N fractionations occur in the photolysis of N2O in the stratosphere, its major atmospheric sink. Measurements on the isotopic composition of stratospheric N2O indeed confirm the presence of strong isotope enrichments, in particular the difference in the fractionation constants for 15N14NO and 14N15NO. The absolute magnitudes of the fractionation constants found in the stratosphere are much smaller, however, than those found in the lab experiments, demonstrating the importance of dynamical and also additional chemical processes like the reaction of N2O with O(1D).     

A generally covariant formulation of classical electrodynamics for charges of finite extension

A generally covariant formulation of classical electrodynamics for charges of finite extension has been developed. The charges are required to maintain a prescribed “rigid” shape throughout the course of their motion. An action principle is formulated for the coupled system consisting of the charges plus electromagnetic and gravitational fields. The action principle yields a complicated set of coupled integro-differential equations for the motion and fields. A perturbation expansion in powers of the size of the charge distribution is obtained. In the limit that the size of the charge tends to zero, only a few kinematical features survive in the equations of motion. The resulting equations of motion have the DeWitt-Brehme [Ann. Phys.9 (1969), 220] form, but with additional curvature-coupling terms which were omitted by them owing to an algebraic error.     

Self-assembled palladium(II) "click" cages: synthesis, structural modification and stability

Readily synthesised and functionalised di-1,2,3-triazole "click" ligands are shown to self-assemble into coordinatively saturated, quadruply stranded helical [Pd(2)L(4)](BF(4))(4) cages with Pd(II) ions. The cages have been fully characterised by elemental analysis, HR-ESMS, IR, (1)H, (13)C and DOSY NMR, DFT calculations, and in one case by X-ray crystallography. By exploiting the CuAAC "click" reaction we were able to rapidly generate a small family of di-1,2,3-triazole ligands with different core spacer units and peripheral substituents and examine how these structural modifications affected the formation of the [Pd(2)L(4)](BF(4))(4) cages. The use of both flexible (1,3-propyl) and rigid (1,3-phenyl) core spacer units led to the formation of discrete [Pd(2)L(4)](BF(4))(4) cage complexes. However, when the spacer unit of the di-1,2,3-triazole ligand was a 1,4-substituted-phenyl group steric interactions led to the formation of an oligomeric/polymeric species. By keeping the 1,3-phenyl core spacer constant the effect of altering the "click" ligands' peripheral substituents was also examined. It was shown that ligands with alkyl, phenyl, electron-rich and electron-poor benzyl substituents all quantitatively formed [Pd(2)L(4)](BF(4))(4) cage complexes. The results suggest that a wide range of functionalised palladium(II) "click" cages could be rapidly generated. These novel molecules may potentially find uses in catalysis, molecular recognition and drug delivery.     

Synergistic Brønsted/Lewis acid catalyzed aromatic alkylation with unactivated tertiary alcohols or di-tert-butylperoxide to synthesize quaternary carbon centers

Dual Brønsted/Lewis acid catalysis involving environmentally benign, readily accessible protic acid and iron promotes site-selective tert-butylation of electron-rich arenes using di-tert-butylperoxide. This transformation inspired the development of a synergistic Brønsted/Lewis acid catalyzed aromatic alkylation that fills a gap in the Friedel–Crafts reaction literature by employing unactivated tertiary alcohols as alkylating agents, leading to new quaternary carbon centers. Corroborated by DFT calculations, the Lewis acid serves a role in enhancing the acidity of the Brønsted acid. The use of non-allylic, non-benzylic, and non-propargylic tertiary alcohols represents an underexplored area in Friedel–Crafts reactivity.

Dual Brønsted/Lewis acid catalysis involving environmentally benign, readily accessible protic acid and iron promotes site-selective tert-alkylation of arenes using di-tert-butylperoxide and tertiary alcohols.     

Measurements of emission spectra from hot,dense germanium plasma in short pulse laser experiments

Heating of thin foil targets by an high power laser at intensities of 10¹⁷–10¹⁹ W/cm² has been studied as a method for producing high temperature, high density samples to investigate X-ray opacity and equation of state. The targets were plastic (parylene-N) foils with a microdot made of a mixture of germanium and titanium buried at depth of 1.5 μm. The L-shell spectra from the germanium and the K-shell spectra from the titanium were taken using crystal spectrometers recording onto film and an ultra fast X-ray streak camera coupled to a conical focussing crystal with a time resolution of 1 ps. The conditions in the microdot were inferred by comparing the measured spectra to synthetic spectra produced by the time-dependent collisional–radiative (CR) models FLY and FLYCHK. The data were also compared to simulated spectra from a number of opacity codes assuming local thermodynamic equilibrium (LTE). Temperature and density gradients were taken into account in the comparisons. The sample conditions were inferred from the CR modelling using FLYCHK to be 800 ± 100 eV and 1.5 ± 0.5 g/cc. The best fit to the LTE models was at a temperature 20% lower than with the CR model. Though the sample departs from LTE significantly useful spectral comparisons can still be made. The results and comparisons are discussed along with improvements to the experimental technique to achieve conditions closer to LTE.     

Evolution of multimodal particle size distribution in vinyl acetate/butyl acrylate emulsion copolymerizations

This article presents a study on the engineering of multimodal distributions in semibatch emulsion polymerizations with nonionic surfactants. Various methods of producing multimodal distributions are demonstrated, and the sensitivity of the process to the properties of the reagents are analyzed. A test‐bed emulsion polymerization system, equipped with instrumentation to measure particle size distribution (capillary hydrodynamic fractionator) and monomer conversion (densitometer and flow meters), is used for this purpose. The process is monitored and controlled with an industrial distributed control system, which enables the automated operation of the process through sequential or logic controllers operating over lower level proportional integral derivative controllers. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2232–2249, 2003     

Highly-functionalised difluorinated cyclohexane polyols via the Diels-Alder reaction: regiochemical control via the phenylsulfonyl group

A difluorinated dienophile underwent cycloaddition reactions with a range of furans to afford cycloadducts which could be processed regio- and stereoselectively via episulfonium ions, generated by the reaction between their alkenyl groups and phenylsulfenyl chloride. The oxabicyclic products were oxidised to the phenylsulfonyl level and ring opened via E1(C)B or reductive desulfonative pathways to afford, ultimately, difluorinated cyclohexene or cyclohexane polyols.     

Supramolecular Recognition: Use of Cofacially Disposed Bis‐terpyridyl Square‐Planar Complexes in Self‐Assembly and Molecular Recognition

A molecular receptor consisting of a molecular spacer that constrains two terpyridyl‐palladium(II) complexes to be disposed in a parallel cofacial geometry has been prepared. The separation between the two terpyridyl‐palladium units is enforced to be ca. 7 Å, a distance sufficient to incarcerate aromatic molecules and square‐planar complexes. A number of molecules are shown to associate with this spacer‐chelator complex. In particular, 9‐methylanthracene (9‐MA) is found to form a 1 : 2 host‐guest complex. A crystal structure of this complex shows one 9‐MA in the molecular cleft formed by the two terpyridyl‐palladium units and the other 9‐MA molecule to lie above one of the terpyridyl‐palladium units. Nuclear Overhauser effects on analogous molecules that contain two anthracene guests tethered intramolecularly indicate that the structure found in the solid is similar to that in solution. Low‐temperature ¹H‐NMR studies indicate rapid exchange between the two binding sites. The spacer‐chelator complexes, when combined with appropriate molecular linkers, readily form molecular rectangles, trigonal prisms, and tetragonal prisms. One molecular rectangle is shown to associate with up to five 9‐MA molecules.