Hydrogenolysis of [PhBP3]Fe[triple bond]N-p-tolyl: probing the reactivity of an iron imide with H2

This paper describes the reductive hydrogenolysis of a low-spin (S = 1/2) iron(III) imide. Pseudotetrahedral [PhBP3]FeIIIN-p-tolyl is reduced by hydrogen at ambient temperature and pressure in benzene solution. The reduction appears to proceed in a stepwise fashion. An intermediate S = 2 iron(II) anilide, [PhBP3]Fe(N(H)-p-tolyl), is observed and has been independently generated and structurally characterized. Prolonged hydrogenolysis in benzene results in the complete hydrogenolysis of the Fe-N linkage to release H2N-p-tolyl. The major iron-containing product formed from this step is the diamagnetic cyclohexadienyl complex, [PhBP3]Fe(eta5-cyclohexadienyl), which has also been independently prepared and structurally characterized. Evidence is presented to suggest that the final [PhBP3]Fe(eta5-cyclohexadienyl) product is formed via benzene insertion into a reactive [PhBP3]FeII-H intermediate.     

Optical tweezers applied to a microfluidic system

We will demonstrate how optical tweezers can be combined with a microfluidic system to create a versatile microlaboratory. Cells are moved between reservoirs filled with different media by means of optical tweezers. We show that the cells, on a timescale of a few seconds, can be moved from one reservoir to another without the media being dragged along with them. The system is demonstrated with an experiment where we expose E. coli bacteria to different fluorescent markers. We will also discuss how the system can be used as an advanced cell sorter. It can favorably be used to sort out a small fraction of cells from a large population, in particular when advanced microscopic techniques are required to distinguish various cells. Patterns of channels and reservoirs were generated in a computer and transferred to a mask using either a sophisticated electron beam technique or a standard laser printer. Lithographic methods were applied to create microchannels in rubber silicon (PDMS). Media were transported in the channels using electroosmotic flow. The optical system consisted of a combined confocal and epi-fluorescence microscope, dual optical tweezers and a laser scalpel.     

Multiwavelength pulse generator using time-lens compression

We demonstrate a novel method of generating a multiwavelength pulse train by use of time-lens compression. In addition to pulse compression, this time lens simultaneously displaces the pulses according to their center wavelengths, resulting in a temporally evenly spaced multiwavelength pulse train. We further demonstrate a new aberration-correction technique based on the temporal analog of a spatial correction lens to improve the quality of the compressed pulses. Through the use of cw distributed-feedback lasers and electro-optic phase modulators, the all-fiber system allows complete tunability of temporal spacing, spectral profile, and repetition rate.     

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.     

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.