X-ray crystal structure, Raman spectroscopy, and Ab initio density functional theory calculations on 1,1,3,3-tetramethylguanidinium bromide

The salt 1,1,3,3-tetramethylguanidinium bromide, [((CH(3))(2)N)(2)C═NH(2)](+)Br(-) or [tmgH]Br, was found to melt at 135(5) °C, forming what may be referred to as a moderate temperature ionic liquid. The chemistry was studied and compared with the corresponding chloride compound. We present X-ray diffraction and Raman evidence to show that also the bromide salt contains dimeric ion pair "molecules" in the crystalline state and probably also in the liquid state. The structure of [tmgH]Br determined at 120(2) K was found to be monoclinic, space group P2(1)/n, with a = 7.2072(14), b = 13.335(3), c = 9.378(2) ?, β =104.31(3)°, Z = 2, based on 11769 reflections, measured from θ = 2.71-28.00° on a small colorless needle crystal. Raman and IR spectra are presented and assigned. When heated, both the chloride and the bromide salts form vapor phases. The Raman spectra of the vapors are surprisingly alike, showing, for example, a characteristic strong band at 2229 cm(-1). This band was interpreted by some of us to show that the [tmgH]Cl gas phase should consist of monomeric ion pair "molecules" held together by a single N-H(+)···Cl(-) hydrogen bond, the stretching vibration of which should be causing the band, based on ab initio molecular orbital density functional theory type calculations. It is not likely that both the bromide and chloride should have identical spectra. As explanation, the formation of 1,1-dimethylcyanamide gas is proposed, by decomposition of [tmgH]X leaving dimethylammonium halogenide (X = Cl, Br). The Raman spectra of all gas phases were quite identical and fitted the calculated spectrum of dimethylcyanamide. It is concluded that monomeric ion pair "molecules" held together by single N-H(+)···X(-) hydrogen bonds probably do not exist in the vapor phase over the solids at about 200-230 °C.     

Total synthesis of ascididemin via anionic cascade ring closure

A new and convergent synthesis of ascididemin is presented. Using an anionic cascade ring closure as the key step, this natural product is obtained in 45% overall yield in just 6 steps starting from 2'-fluoroacetophenone. This new approach was extended to the synthesis of a new isomer of ascididemin.     

Solid-state autocatalysis and oscillatory reactions in silicate glass systems

We report the first demonstration of autocatalysis and oscillatory behaviour in the solid-state where no decomposition process is involved. Our material system is solid-state silica glass impregnated with hydrogen. It is at the heart of photosensitivity in glass-based optical waveguides and devices, which have many applications including telecommunication devices, fibre lasers, and optical sensors. Consequently, the results reported here extend the engineering of chemical complexity to a previously uncharted area in materials science of particular relevance to photonic applications. Diagnosis is carried out optically, opening up a new approach to characterisation of such catalytic processes generally.     

Conditions for Equality of Hulls in the Calculus of Variations

We simplify and sharpen several results by K. Zhang concerning properties of quasiconvex hulls of sets and quasiconvex envelopes of their distance functions. The approach emphasizes the underlying geometry and in particular we show that K ^pc=K ^c implies K ^rc=K ^c if and only if min{m,n}≤ 2 thus answering a question raised in [Z2]. (Accepted January 24, 2000)?Published online August 21, 2000     

Poling effect of a charge-trapping layer in glass waveguides

Germanium-doped multi-layer waveguides containing a silicon oxy-nitride layer as a charge trapper are thermally poled in an air environment. Compared to the waveguides without the trapping layer, the induced linear electro-optic coefficient increases more than 20%. A comparable rise in the internal field is found. Our results demonstrate an optimization of the optical nonlinearity by shaping the built-in internal field with the charge-trapping layer. PACS 42.70.Ce; 42.82.Et; 42.70.Mp; 42.65.Wi     

Small molecules from spiders used as chemical probes

Spiders are important species in ecological systems and as major predators of insects they are endowed with a plethora of low-molecular-weight natural products having intriguing biological activities. The isolation and biological characterization of these entities are well established, however, only very recently have these compounds been used as templates for the design, synthesis, and biological evaluation of synthetic analogues. In contrast, the investigation of compounds responsible for chemical communication between spiders is far less developed, but recently new light has been shed onto the area of pheromones and allomones from spiders. Herein, we recapitulate these recent results, put them into perspective with previous findings, and provide an outlook for future studies of these chemotypes.