Photoinduced intramolecular tryptophan oxidation and excited-state behavior of [Re(L-AA)(CO)3(α-diimine)](+) (L = pyridine or imidazole, AA = tryptophan, tyrosine, phenylalanine)

Re(I) carbonyl-diimine complexes [Re(L-AA)(CO)(3)(N,N)](+) (N,N = bpy, phen) containing an aromatic amino acid (AA), phenylalanine (Phe), tyrosine (Tyr), or tryptophan (Trp), linked to Re by a pyridine-amido or imidazole-amido ligand L have been synthesized and their excited-state properties investigated by nanosecond time-resolved IR (TRIR) and emission spectroscopy. Near-UV optical excitation populates a Re(I)(CO)(3)→N,N (3)MLCT excited state *[Re(II)(L-AA)(CO)(3)(N,N(?-))](+). Decay to the ground state (50-300 ns lifetime) is the only excited-state deactivation process observed in the case of Phe and Tyr complexes, whereas the Trp-containing species undergo a Trp(indole)→*Re(II) electron transfer (ET) producing a charge-separated (CS) state, [Re(I)(L-Trp(?+))(CO)(3)(N,N(?-))](+). The ET occurs with a 8-40 ns lifetime depending on L, N,N, and the solvent. The CS state is characterized by ν(CO) IR bands shifted to lower wavenumbers from their respective ground-state positions and two bands at 1278 and 1497 cm(-1) tentatively attributed to Trp(?+). The amido bridge is affected by both the MLCT excitation and the subsequent ET, manifested by the shifts and intensity changes of the amide-I IR band at about 1680 cm(-1). The CS state decays to the ground state by a N,N(?-)→Trp(?+) back-ET the rates of which are comparable to those of the forward ET, 30-60 ns. This study independently demonstrates that Trp can act as an electron-hopping intermediate in photodriven ET systems based on Re-labeled proteins and supramolecules. Photoinduced ET in Trp-containing Re complexes also can be used to generate Trp(?+) and investigate its spectral properties and reactivity.     

A novel monochromator for experiments with ultrashort X‐ray pulses

Aiming at advancing storage‐ring‐based ultrafast X‐ray science, over the past few years many upgrades have been undertaken to continue improving beamline performance and photon flux at the Femtoslicing facility at BESSY II. In this article the particular design upgrade of one of the key optical components, the zone‐plate monochromator (ZPM) beamline, is reported. The beamline is devoted to optical pump/soft X‐ray probe applications with 100 fs (FWHM) X‐ray pulses in the soft X‐ray range at variable polarization. A novel approach consisting of an array of nine off‐axis reflection zone plates is used for a gapless coverage of the spectral range between 410 and 1333 eV at a designed resolution of E/ΔE = 500 and a pulse elongation of only 30 fs. With the upgrade of the ZPM the following was achieved: a smaller focus, an improved spectral resolution and bandwidth as well as excellent long‐term stability. The beamline will enable a new class of ultrafast applications with variable optical excitation wavelength and variable polarization.     

Rook Poset Equivalence of Ferrers Boards

A natural construction due to K. Ding yields Schubert varieties from Ferrers boards. The poset structure of the Schubert cells in these varieties is equal to the poset of maximal rook placements on the Ferrers board under the Bruhat order. We determine when two Ferrers boards have isomorphic rook posets. Equivalently, we give an exact categorization of when two Ding Schubert varieties have identical Schubert cell structures. This also produces a complete classification of isomorphism types of lower intervals of 312-avoiding permutations in the Bruhat order.     

A new dendrimer scaffold for preparing dimers or tetramers of biologically active molecules

Synthesis of a new scaffold derived from iminodipropionic acid for the preparation of peptide dimers and tetramers is described.     

A Fair Allocation of County Cricket Opponents

Each team in the English County Cricket Championship plays against some other teams twice a year, and others only once. This paper describes a case study whose aim was to overcome this inherent unfairness by producing a four-year schedule of opponents which was as fair as possible, and could be easily seen to be fair, while still allowing for traditional rivalries. The schedule also needed to be satisfactory in regard to several other constraints and objectives. Various simple heuristics were used; these are described in some detail. Of particular interest is the effectiveness of a ‘local non-worsening’ approach when the objective is to find any feasible solution. This is equivalent to simulated annealing at a constant temperature of absolute zero.     

An efficient synthesis of 1,6- and 1,7-dibromo-3-aminoisoquinolines: versatile templates for the preparation of functionalized isoquinolines

An efficient synthetic route to 1,6- and 1,7-dibromo-3-aminoisoquinoline was devised. These intermediates served as ideal templates for the preparation of 3-aminoisoquinoline analogues functionalized at C(6) or C(7).     

The minimal free resolution of a Borel ideal

We consider the Eliahou–Kervaire minimal free resolution of a 0-Borel ideal and its applications.     

Fabrication of a metal nanoparticles and polymer nanofibers composite material by an in situ chemical synthetic route

This work demonstrated a facile route for the synthesis of poly(3,5-dimethyl aniline) nanofibers by polymerization of 3,5-dimethyl aniline using Pd-acetate as the oxidant. The reduction of Pd ion is accompanied by oxidative polymerization of 3,5-dimethyl aniline, leading to a metal-polymer composite material. Palladium nanoparticles (approximately 2 nm) are uniformly distributed throughout the polymer that makes the composite material a unique morphology. The resultant composite material was characterized by means of different techniques. IR and Raman spectra provide the information on the chemical structure of the polymer. TEM images show the morphology of the polymer and size of the metal particles.     

Affinity capillary electrophoresis applied to the studies of interactions of a member of heat shock protein family with an immunosuppressant

The bioaffinity of receptor-ligand interactions is investigated by determining the binding constant (association constant or dissociation constant) of the resulting complex utilizing affinity capillary electrophoresis (ACE). The ACE binding assay was established with a potent immunosuppressant, deoxyspergualin (DSG), that binds specifically to Hsc70, a constitutive or cognate member of heat shock protein 70 (Hsp70) family. Quantitative determination of binding constants under different running buffer systems provide comparative results. The association constants for the interaction between Hsc70 protein and DSG were found to be 5.7·10⁴ M⁻¹ in a buffer with pH 6.95 and 6.3·10⁴ M⁻¹ in a buffer with pH 5.30 (or corresponding dissociation constants, 18 and 16 μM, respectively) based on Scatchard analyses. Binding of DSG to a synthetic peptide, SINPDEAVAYGAAV-QAAILSGDK, one of the DSG-binding fragments found from tryptic digest of Hsc70 protein, provides further detailed information for the understanding of Hsc70 binding domain. The applicability of using coated capillaries was also evaluated for probing Hsc70-DSG interaction.