Crystallography Aided by Atomic Core-Level Binding Energies: Proton Transfer versus Hydrogen Bonding in Organic Crystal Structures

Ionic bond or hydrogen bridge? Br?nsted proton transfer to nitrogen acceptors in organic crystals causes strong N1s core-level binding energy shifts. A study of 15 organic cocrystal and salt systems shows that standard X-ray photoelectron spectroscopy (XPS) can be used as a complementary method to X-ray crystallography for distinguishing proton transfer from H-bonding in organic condensed matter.     

Computation of Nielsen numbers for maps of closed surfaces

Let be a closed surface, and let be a map. We would like to determine Nielsen fixed point theory provides a lower bound for , called the Nielsen number, which is easy to define geometrically and is difficult to compute.

We improve upon an algebraic method of calculating developed by Fadell and Husseini, so that the method becomes algorithmic for orientable closed surfaces up to the distinguishing of Reidemeister orbits. Our improvement makes tractable calculations of Nielsen numbers for many maps on surfaces of negative Euler characteristic. We apply the improved method to self-maps on the connected sum of two tori including classes of examples for which no other method is known. We also include the application of this algebraic method to maps on the Klein bottle . Nielsen numbers for maps on were first calculated (geometrically) by Halpern. We include a sketch of Halpern's never published proof that for all maps on .

     

New procedure for the preparation of highly sterically hindered alkenes using a hypervalent iodine reagent

New methodology is described to construct the olefinic bond in overcrowded alkenes using a hypervalent iodine reagent, and applied in the synthesis of molecular motors.     

Membrane-introduction mass spectrometry (MIMS)

Membrane-introduction mass spectrometry (MIMS) for chemical analysis involves directly sampling analytes in gaseous, liquid and solid samples through a semi-permeable membrane coupled to a mass spectrometer, yielding selective and sensitive quantitation. Because MIMS is an on-line technique, in which samples can be continuously flowed over a membrane interface, it can yield analytical results in real time without the need for sample clean-up and chromatographic separation. This review highlights trends and developments in MIMS over the past decade and describes recent studies that pertain to its use for on-site, in-situ and in-vivo chemical analysis. We report on advancements in instrumentation, including membrane materials, interface configurations and ionization techniques that have extended the range of analytes amenable to MIMS.We summarize the progress made in the miniaturization of mass spectrometers that have resulted in field-portable systems and review recent applications of continuous mobile monitoring and on-site environmental monitoring to yield both temporally and spatially resolved quantitative and semi-quantitative data. Finally, we describe recent work involving the use of MIMS for in-vivo chemical analysis.     

Discrimination of organic acids using a three molecule array based upon cruciform fluorophores

A small array was obtained from three reactive cruciform fluorophores in six different solvents. The array discerned 10 different aromatic carboxylic acids by protonation-induced fluorescence shifts, which were recorded by digital photography. This simple array can discern acids that have closely spaced pK(a) values.     

The Synthesis of a Bis(thiosemicarbazone) Macrocyclic Ligand and the Mn(II), Co(II), Zn(II) and 68Ga(III) Complexes

A 1,4,7,10-tetraazacyclododecane (cyclen) variant bearing two thiosemicarbazone pendant groups has been prepared. The ligand forms complexes with Mn²⁺, Co²⁺ and Zn²⁺. X-ray crystallography of the Mn²⁺, Co²⁺ and Zn²⁺ complexes showed that the ligand provides a six-coordinate environment for the metal ions. The Mn²⁺ and Zn²⁺ complexes exist in the solid state as racemic mixtures of the Δ(δ,δ,δ,δ)/Λ(λ,λ,λ,λ) and Δ(λ,λ,λ,λ)/Λ(δ,δ,δ,δ) diastereomers, and the Co²⁺ complex exists as the Δ(δ,δ,δ,δ)/Λ(λ,λ,λ,λ) and Δ(λ,λ,λ,δ)/Λ(δ,δ,δ,λ) diastereomers. Density functional theory calculations indicated that the relative energies of the diastereomers are within 10 kJ mol⁻¹. Magnetic susceptibility of the complexes indicated that both the Mn²⁺ and Co²⁺ ions are high spin. The ligand was radiolabelled with gallium-68, in the interest of developing new positron emission tomography imaging agents, which produced a single species in high radiochemical purity (>95%) at 90 °C for 10 min.     

Full does not imply strong, does it?

We give a duality for the variety of bounded distributive lattices that is not full (and therefore not strong) although it is full but not strong at the finite level. While this does not give a complete solution to the “Full vs Strong” Problem, which dates back to the beginnings of natural duality theory in 1980, it does solve it at the finite level. One consequence of this result is that although there is a Duality Compactness Theorem, which says that if an alter ego of finite type yields a duality at the finite level then it yields a duality, there cannot be a corresponding Full Duality Compactness Theorem. Received October 1, 2002; accepted in final form November 10, 2004.     

A non-dualisable entropic algebra

We give an example of a five-element unary algebra which is entropic but does not admit a natural duality. Received September 26, 2000; accepted in final form April 4, 2001.     

Not every full duality is strong!

Is every full duality strong? We show that the answer is ‘no’, thereby answering a question that goes back to the earliest foundations of the theory of natural dualities. Received July 3, 2006; accepted in final form September 8, 2006.