Relations between 77Se NMR chemical shifts of (phenylseleno)-benzenes and their molecular structures derived from nine X-ray crystal structures

An extensive library of 77Se chemical shifts have been generated from the NMR measurements on substituted (phenylseleno)benzenes, including 33 new compounds. The variation in chemical shifts cover 265 ppm ranging from 446 to 181 ppm. Crystal structures have been determined for nine selected representatives of the substituted (phenylseleno)-benzenes. The analysis of the crystal structures supported that through-space interactions between selenium and the ortho-substituent observed in the crystal structures also are likely to be present in solution. The variation in the 77Se NMR chemical shifts can be rationalised from the intramolecular interactions with the substituent in the ortho-position. Furthermore it appears that these ortho-effects are roughly additive, and that it is the actual interactions and not the resulting conformational constraints that are responsible for the variations in the 77Se NMR chemical shifts.     

Dinitrogen chemistry from trigonally coordinated iron and cobalt platforms

This report establishes that trigonally coordinated "[PhBPiPr3]M" platforms (M = Fe, Co) will support both pi-acidic (N2) and pi-basic (NR) ligands at a fourth binding site. The N2 complexes of iron that are described are the first thoroughly characterized examples to exhibit a 4-coordinate geometry. Methylation of monomeric {Fe0(N2)-} and {Co0(N2)-} species successfully derivatizes the beta-N atom of the coordinated N2 ligand and affords the diazenido products {FeII(N2Me)} and {CoII(N2Me)}, respectively. One-electron oxidation of the mononuclear M0(N2)- species produces dinuclear and synthetically versatile MI(N2)MI complexes. These latter species provide clean access to the chemistry of the "[PhBPiPr3]MI" subunit. For example, addition of RN3 to MI(N2)MI results in oxidative nitrene transfer to generate [PhBPiPr3]MNR with concomitant N2 release.     

Dissociative cycloelimination,a new selenium based pericyclic reaction

The stereospecific oxidation of hydrazine into cis-diimide and the catalytic disproportionation of hydrogen peroxide effected by selenoxides are suggested to involve a dissociative cycloelimination from an intermediary selenurane.     

A generalization of a theorem on biseparating maps

In J. Math. Anal. Appl. 12 (1995) 258–265, Araujo et al. proved that for any linear biseparating map  from C(X) onto C(Y), where X and Y are completely regular, there exist ω in C(Y) and an homeomorphism h from the realcompactification vX of X onto vY, such that

The compact version of this result was proved before by Jarosz in Bull. Canad. Math. Soc. 33 (1990) 139–144. In Contemp. Math., Vol. 253, 2000, pp. 125–144, Henriksen and Smith asked to what extent the result above can be generalized to a larger class of algebras. In the present paper, we give an answer to that question as follows. Let A and B be uniformly closed Φ-algebras. We first prove that every order bounded linear biseparating map from A onto B is automatically a weighted isomorphism, that is, there exist ω in B and a lattice and algebra isomorphism ψ between A and B such that

(a)=ωψ(a) for all aA.

We then assume that every universally σ-complete projection band in A is essentially one-dimensional. Under this extra condition and according to a result from Mem. Amer. Math. Soc. 143 (2000) 679 by Abramovich and Kitover, any linear biseparating map from A onto B is automatically order bounded and, by the above, a weighted isomorphism. It turns out that, indeed, the latter result is a generalization of the aforementioned theorem by Araujo et al. since we also prove that every universally σ-complete projection band in the uniformly closed Φ-algebra C(X) is essentially one-dimensional.     

Investigation of endoglucanase selectivity on carboxymethyl cellulose by mass spectrometric techniques

The benefits of applying cellulose selective enzymes as analytical tools for chemical structure characterization of cellulose derivatives have been frequently addressed over the years. In a recent study the high selectivity of cellulase Cel45A from Trichoderma reesei (Tr Cel45A) was utilized for relating the chemical structure to the flow properties of carboxymethyl cellulose (CMC). However, in order to take full advantage of the enzymatic hydrolysis the enzyme selectivity on the cellulose substrate must be further investigated. Therefore, the selectivity of Tr Cel45A on CMC was studied by chemical sample preparation of the enzyme products followed by mass spectrometric chemical structure characterization. The results strongly suggest that, in accordance with recent studies, also this highly selective endoglucanase is able to catalyze hydrolysis of glucosidic bonds adjacent to mono-substituted anhydroglucose units (AGUs). Furthermore, the results also indicate that substituents on the nearby AGUs will affect the hydrolysis.     

Asymmetric equilibria in dynamic two-sided matching markets with independent preferences

A fundamental fact in two-sided matching is that if a market allows several stable outcomes, then one is optimal for all men in the sense that no man would prefer another stable outcome. We study a related phenomenon of asymmetric equilibria in a dynamic market where agents enter and search for a mate for at most n rounds before exiting again. Assuming independent preferences, we find that this game has multiple equilibria, some of which are highly asymmetric between sexes. We also investigate how the set of equilibria depends on a sex difference in the outside option of not being mated at all.     

The effect of sample salt additives on capillary electrophoresis analysis of intact proteins using surface modified capillaries

The effect of adding alkali salts to protein samples for capillary electrophoretic (CE) analysis of intact proteins was studied. A high degree of peak stacking, even for large proteins, was found to occur when alkali salts were added to the sample. The addition of salt to the protein sample promotes a strong improvement in the peak efficiency of individual proteins giving up to 2.1 × 10⁶ apparent plates/m. The concentration of salt required in the sample to reach optimal peak efficiency show dependency on both the molecular weight and molar concentration of the protein. However, adding salt will, at a sufficiently high concentration, cause a mixture of proteins to co-migrate to one very sharp peak. The observed sample stacking effect was obtained with a number of different surface modified silica capillaries indicating a general phenomenon and not surface coating specific.     

Optical study of the formation of pyrrolo[2,3-d]pyrimidine-based fluorescent nanoaggregates

Pyrrolo[2,3-d]pyrimidine derivatives possessing different sterically-hindered end-groups at position 7 of the heterocycle were studied and compared with respect to nanoaggregate formation ability by the reprecipitation method in aqueous solutions. The emergence of nanoaggregates with an increasing water fraction in THF/water mixture was traced by observing sudden changes in spectral and transient fluorescence dynamics accompanied by fluorescence efficiency turn-on. The aggregation induced emission with a maximal 20-fold emission efficiency enhancement was obtained. Tuning of the nanoaggregates sizes from about 50 nm to 600 nm by increasing the THF/water ratio was revealed by electron microscopy. Almost perfect spherical shapes of the nanoaggregates and their structureless fluorescence bands similar to those of their neat amorphous films suggested an amorphous-like nature of the pyrrolo[2,3-d]pyrimidine-based nanoparticles.     

Hopf structures on ambiskew polynomial rings

We derive necessary and sufficient conditions for an ambiskew polynomial ring to have a Hopf algebra structure of a certain type. This construction generalizes many known Hopf algebras, for example U(sl₂), U_q(sl₂) and the enveloping algebra of the three-dimensional Heisenberg Lie algebra. In a torsion-free case we describe the finite-dimensional simple modules, in particular their dimensions, and prove a Clebsch-Gordan decomposition theorem for the tensor product of two simple modules. We construct a Casimir type operator and prove that any finite-dimensional weight module is semisimple.