Synthesis and single enzyme activity of a clicked lipase-BSA hetero-dimer

Click chemistry is used to construct a novel lipase-BSA hetero-dimer, in which the latter protein acts as a foot enabling the anchoring of the enzyme onto the surface for single enzyme studies.     

Aminolysis of resin-bound N-nosylaziridine-2-carboxylic acids

[Structure: see text] Solid-phase synthesis is a rapidly developing area of organic chemistry, of particular importance for medicinal chemistry and chemical biology. Aziridines have previously only rarely been applied in solid-phase synthesis. In the present work, aminolysis of resin-bound, spring-loaded N-nitrobenzenesulfonyl-activated aziridine-2-carboxylic acids has been optimized and employed in the synthesis of a number of open-chain and heterocyclic scaffolds, including enantiopure products.     

Resonance fluorescence from semiconductor quantum dots: beyond the Mollow triplet

We show that the resonance fluorescence spectrum of a quantum dot excited by a strong optical pulse contains multiple peaks beyond those of the Mollow triplet. We show that as the area of the optical pulse is increased, new side peaks split off the central peak and shift in frequency. A simple analytical theory has been derived, which quantitatively accounts for the appearance and position of the peaks. This theory explains the physics responsible for the multiple peaks. By considering the time-dependent spectrum we demonstrate a time ordering of the side peaks, which is further evidence for the suggested physical explanation.     

Thermally induced mode coupling in rare-earth doped fiber amplifiers

We present a simple semianalytical model of thermally induced mode coupling in multimode rare-earth doped fiber amplifiers. The model predicts that power can be transferred from the fundamental mode to a higher-order mode when the operating power exceeds a certain threshold, and thus provides an explanation of recently reported mode instability in such fiber amplifiers under high average-power operation. We apply our model to a simple step-index fiber design, and investigate how the power threshold depends on various design parameters of the fiber.     

A finite loop space not rationally equivalent to a compact Lie group

We construct a connected finite loop space of rank 66 and dimension 1254 whose rational cohomology is not isomorphic as a graded vector space to the rational cohomology of any compact Lie group, hence providing a counterexample to a classical conjecture. Aided by machine calculation we verify that our counterexample is minimal, i.e., that any finite loop space of rank less than 66 is in fact rationally equivalent to a compact Lie group, extending the classical known bound of 5. Mathematics Subject Classification (2000) Primary: 55P35; Secondary: 55P15, 55R35     

Initial MAX IV Beamline Program Receives Funding

In early July 2011 it became clear that the initial MAX IV beamline program would receive the required funding of 400 MSEK from the Knut and Alice Wallenberg Foundation and 160 MSEK from Swedish universities. The construction program will start immediately and the beamlines are projected to be operative in late 2015.     

1H nuclear magnetic resonance study of the molecular imprinting of (-)-nicotine: template self-association, a molecular basis for cooperative ligand binding

In the present study, the interactions of components in a (-)-nicotine molecular imprinting polymerization mixture have been studied by 1H NMR spectroscopy. The dissociation constants for complexation of template by a functional monomer analogue, acetic acid, have been determined. Nicotine was shown to self-associate at concentrations comparable to those used in previous molecular imprinting studies (app K(diss) = 0.082M in CDCl3 at 298 K). The extent of self-association was enhanced by the presence of acetic acid. Previous studies on (-)-nicotine-imprinted methacrylic acid-ethylene dimethacrylate co-polymers suggested the involvement of recognition sites for template-template complexes. Collectively these results provide the first direct evidence for the presence of template-template complexes, and support the previously hypothesized basis for cooperative ligand recognition events in this polymer system.     

Conformationally controlled high-affinity targeting of RNA or DNA by novel 2'-amino-DNA/LNA mixmers and pyrenyl-functionalized 2'-amino-DNA

9-Mer DNA sequences containing 2'-N-methyl-2'-N-(pyren-1-ylmethyl)-2'-amino-DNA monomers display significantly increased affinity towards DNA complements whereas the corresponding 2'-amino-DNA monomer has a detrimental effect on duplex stability. These effects are efficiently reversed by incorporation of four LNA nucleotides inducing a B-DNA to A-DNA conformational change.     

Imido Analogues of Common Oxo Anions: A New Episode in the Chemistry of Cluster Compounds

Oxo anions of p- and d-block elements, for example, SiO(4)(4-), PO(4)(3-), SO(4)(2-), and CrO(4)(2-), are commonly encountered species. The full or partial replacement of the oxo ligands by isoelectronic imido (NR) groups generates homoleptic polyimido anions of the type [E(NR)(x)](z-) or heteroleptic imidooxo anions with the general formula [O(y)E(NR)(x-y)](z-) (where E=main group element or transition metal). The alkali metal derivatives of this new class of anions form ternary or quaternary cluster systems, respectively. The structures of these clusters can be rationalized in terms of the self-assembly of fundamental building blocks. An understanding of the factors that control this process may allow the design of functional materials with specific properties. In addition, these anions are attracting attention as multidentate ligands with unique electronic and stereochemical properties that may engender novel metal-centered chemistry.     

Molecular and electronic structure of chromium(V) nitrido complexes with azide and isothiocyanate ligands

The first use of [Cr(N)Cl4]2- as a starting material in chromium(v) nitrido chemistry is demonstrated in simple, high yield, metathesis reactions with the pseudohalogens SCN- and N3- yielding five-coordinate, labile complexes: [Cr(N)(NCS)4]2- and [Cr(N)(N3)4]2-, which have been crystallized and characterized by single-crystal X-ray diffraction. Reaction of [Cr(N)(NCS)4]2- with 1,10-phenanthroline furnishes six-coordinate [Cr(N)(NCS)3(phen)]- wherein phenanthroline coordinates to the position trans to the nitrido ligand. The trans influence of the nitrido ligand leads to a bond length difference of 0.223 A between the axial and equatorial ligators from the phenanthroline ligand. The absorption band with lowest energy in these pseudo-linear complexes is assigned as the electric dipole forbidden transition d(xy) --> d(x-y) based on intensities and its variation with the nature of the equatorial ligators. This absorption provides the spectrochemical series for the equatorial ligands, which is found to be numerically almost identical to that determined for chromium(III). DFT calculations reproduce the observed structures and corroborate the ligand field picture of the electronic structure of these complexes.