A transfer map for singular fibrations

Using a new group of singular chains on polyhedra, a transfer map is defined on the chain level for fibrations with singularities. These include usual transfer on homology as well as Oliver transfer and other cases.     

Combinatorial criteria for uniqueness of Gibbs measures

We generalize previously known conditions for uniqueness of the Gibbs measure in statistical physics models by presenting conditions of any finite size for models on any underlying graph. We give two dual conditions, one requiring that the total influence on a site is small, and the other that the total influence of a site is small. Our proofs are combinatorial in nature and use tools from the analysis of discrete Markov chains, in particular the path coupling method. The implications of our conditions for the mixing time of natural Markov chains associated with the models are discussed as well. We also present some examples of models for which the conditions hold. © 2005 Wiley Periodicals, Inc. Random Struct. Alg., 2005     

Fine Tuning of Chlorophyll Spectra by Protein‐Induced Ring Deformation

The ability to tune the light‐absorption properties of chlorophylls by their protein environment is the key to the robustness and high efficiency of photosynthetic light‐harvesting proteins. Unfortunately, the intricacy of the natural complexes makes it very difficult to identify and isolate specific protein–pigment interactions that underlie the spectral‐tuning mechanisms. Herein we identify and demonstrate the tuning mechanism of chlorophyll spectra in type II water‐soluble chlorophyll binding proteins from Brassicaceae (WSCPs). By comparing the molecular structures of two natural WSCPs we correlate a shift in the chlorophyll red absorption band with deformation of its tetrapyrrole macrocycle that is induced by changing the position of a nearby tryptophan residue. We show by a set of reciprocal point mutations that this change accounts for up to 2/3 of the observed spectral shift between the two natural variants.     

Eight-membered-ring solid-state conformational interconversion via the atom-flip mechanism, a CPMAS 13C NMR and crystallographic stereochemical study

Nefopam methohalide (chloride, bromide, and iodide) medium-ring quaternary ammonium salts of the non-narcotic analgesic tertiary amine drug give crystals belonging to the identical monoclinic P2(1)/c space group, and all of these pseudopolymorphs exhibit the same packing motif. A singular boat-boat (BB) more compact conformation is observed in the nefopam methochloride crystal. Larger halide anions (bromide and iodide) increase the void distance between the 2(1)-screw axis related adjacent ammonium cations to accommodate void-size dependent equilibrium quantities of the twist-chair-chair (TCC) more extended conformation. The BB:TCC occupancy factors are 0.961(5):0.039(5) [193 K], 0.780(5):0.220(5) [293 K], and 0.755(6):0.245(6) [343 K] for the methobromide crystal, while values of 0.657(5):0.343(5) [193 K] and 0.592(7):0.408(7) [293 K] were measured for the methiodide. Above a minimum of ca. 2.53 A, the occupancy factors were found to be linearly correlated to the intermolecular (TCC)Me(eq)-H...H-Me(ax)(TCC) distance between abutting methyl group protons in 2(1)-screw axis related neighbors. Temperature-dependent occupancy factors for the two conformers are interpreted in terms of a medium ring atom-flip facile interconversion between the two low energy conformations in crystals containing the appropriate size intercation void. A BB/TCC atom-flip interconversion in the methochloride unit cell would result in van der Waals interactions due to an estimated 2.31 A close intermolecular (TCC)Me(eq)-H...H-Me(ax)(TCC) distance between adjacent 2(1)-screw symmetry ammonium cations. The 203 K low-temperature CPMAS 13C NMR spectrum of the methiodide salt showed two slow exchange limit (SEL) delta 57.91 [BB] and delta 63.10 [TCC] OCH2CH2N peaks. A variable low-temperature CPMAS NMR investigation of the solid methiodide showed complex dynamic behavior that cannot be interpreted solely on the basis of an atom-flip conformational interconversion. Local magnetic fields from the gem-dimethyl rapidly rotating proton magnetic dipoles provide a distance-dependent T1 relaxation mechanism for neighboring carbons in the solid-state.     

Use of metallic and dielectric films for hollow fibers

The problem of transmission of CO₂ laser radiation through hollow fibers and waveguides was studied theoretically and confirmed experimentally. The transmission of the laser radiation through metal and metal-dielectric tubes was measured and compared with the theoretical data based on a ray model solution. This makes possible the investigation of the transmission of the CO₂ radiation through waveguides when the internal wall is covered with a metal or a metal- dielectric film. It was shown theoretically and proved experimentally that the transmission of the CO₂ radiation is possible even through bent waveguides.     

Cash flow optimization in delivery scheduling

The paper examines the inventory routing problem from the perspective of the present value of the cash flow associated with the distribution of a commodity such as propane. We analyze this problem for both deterministic and stochastic customer demands and validate our results on data from a real life distribution operation of propane. The analysis based on the present value of the cash flow indicates that optimization of propane deliveries based on efficiency/cost criteria alone will generate inferior solutions and it would be more advantageous for the company to set deliveries for a large percentage of the customers based on the present value of cash flow. In addition, in the case of stochastic demands, deliveries based on the cash flow consideration will tend to reduce the number of stockouts (i.e. improve both profit and service).     

Collision broadening model for the biexciton resonance in CuCl

It is shown that the cage model of the spectral broadening of the biexciton resonance in CuCl due to collisions is in agreement with experimental results.