Two-photon absorption of metal-organic DNA-probes

We report remarkable multiphoton absorption properties of DNA intercalating ruthenium complexes: (1) [Ru(phen)(2)dppz](2+); (2) [(11,11'-bidppz)(phen)(4)Ru(2)](4+); (3) [11,11'-bipb(phen)(4)Ru(2)](4+). Two-photon spectra in the range from 460 to 1100 nm were measured using the Z-scan technique. In particular, complex 2 was found to exhibit very strong two- and three-photon absorption properties, which could be an effect of symmetric charge transfer from the ends towards the middle of the conjugated dimeric orbital system. We propose that these molecules could provide a new generation of DNA binding nonlinear chromophores for wide applications in biology and material science. The combination of a large two-photon cross section and strong luminescence quantum yields for the molecules when intercalated makes the compounds uniquely bright and photo-stable probes for two-photon luminescence imaging and also promising as enhanced photosensitizers in two-photon sensitizing applications.     

Adsorption and spontaneous rupture of vesicles composed of two types of lipids

To analyze the adsorption of single vesicles composed of two types of lipids (e.g., zwitterionic and positively charged lipids or zwitterionic and negatively charged lipids), we propose a statistical model taking into account lipid-surface interactions, lipid-lipid lateral interactions, and vesicle bending energy. Our treatment specifies how these parameters govern vesicle adsorption, shows how the radius of the vesicle-surface contact area may depend on the vesicle composition, and clarifies the conditions for vesicle rupture.     

A promiscuous glutathione transferase transformed into a selective thiolester hydrolase

Human glutathione transferase A1-1 (hGST A1-1) can be reengineered by rational design into a catalyst for thiolester hydrolysis with a catalytic proficiency of 1.4 x 10(7) M(-1). The thiolester hydrolase, A216H that was obtained by the introduction of a single histidine residue at position 216 catalyzed the hydrolysis of a substrate termed GSB, a thiolester of glutathione and benzoic acid. Here we investigate the substrate requirements of this designed enzyme by screening a thiolester library. We found that only two thiolesters out of 18 were substrates for A216H. The A216H-catalyzed hydrolysis of GS-2 (thiolester of glutathione and naphthalenecarboxylic acid) exhibits a k(cat) of 0.0032 min(-1) and a KM of 41 microM. The previously reported catalysis of GSB has a k(cat) of 0.00078 min(-1) and KM of 5 microM. The k(cat) for A216H-catalyzed hydrolysis of GS-2 is thus 4.1 times higher than for GSB. The catalytic proficiency (k(cat)/KM)/k(uncat) for GS-2 is 3 x 10(6) M(-1). The promiscuous feature of the wt protein towards a range of different substrates has not been conserved in A216H but we have obtained a selective enzyme with high demands on the substrate.     

A simple model for the water o-H2 complex

The infrared spectrum of the complex between o-H2 and H2O, D2O, or HDO, isolated in a matrix of solid p-H2, has been studied between 20 and 4500 cm(-1). In addition the infrared spectrum of the complex between p-D2 and H2O in solid o-D2 has been studied. The spectral shifts are interpreted as the result of the quadrupole-dipole interaction between hydrogen and water.     

Parallel searching on m rays

We investigate parallel searching on m concurrent rays. We assume that a target t is located somewhere on one of the rays; we are given a group of m point robots each of which has to reach t. Furthermore, we assume that the robots have no way of communicating over distance. Given a strategy S we are interested in the competitive ratio defined as the ratio of the time needed by the robots to reach t using S and the time needed to reach t if the location of t is known in advance.

If a lower bound on the distance to the target is known, then there is a simple strategy which achieves a competitive ratio of 9—independent of m. We show that 9 is a lower bound on the competitive ratio for two large classes of strategies if m2.

If the minimum distance to the target is not known in advance, we show a lower bound on the competitive ratio of 1+2(k+1)^k+1/k^k where k=logm where log is used to denote the base-2 logarithm. We also give a strategy that obtains this ratio.     

Oriented crosslinked polyethylene pipes by a novel extrusion method

Crosslinking and stretching (2.5 times along the circumferential direction) of the molten polymer during extrusion produced pipes with dominantly circumferential orientation and a lower degree of axial chain orientation. Differential scanning calorimetry (crystallinity and crystal thickness), density measurements (crystallinity), X-ray diffraction (c-axis orientation), infrared dichroism measurements (crystalline and amorphous chain orientation) and contraction measurements (molecular draw ratio) assessed the microstructure of the pipe material. The mechanical properties of the oriented material were assessed by uniaxial tensile tests. The orientation was biaxial with the main orientation in the circumferential direction and a lesser orientation in the axial direction. The maximum degree of circumferential orientation was obtained at the inner wall of the pipe. The lower degree of crosslinking of the core material allowed slippage of chains during the stretching of the molten polymer and it is suggested that this is the cause of the lower degree of orientation of the core material. The oriented pipe material exhibited a 5-10% higher degree of crystallinity and higher crystal thickness than conventionally crosslinked material. The tensile modulus and the tensile strength of the oriented, cross-linked material was greater along the axial direction than along the circumferential direction. The circumferential and axial moduli for the oriented, crosslinked pipe were greater than the corresponding moduli of the non-oriented cross-linked pipe material. Another pipe based on crosslinked PE that were first circumferentially stretched 2.5 times and later axially stretched 10 times (in the molten state) showed, despite the fact that it exhibited pronounced axial orientation almost a balanced tensile modulus (4.3±0.2 GPa) in the axial-circumferential plane. Atomistic modelling showed that the orientational dependence of the density of the amorphous phase is small.     

Numerical and experimental investigation of turbulent flow in a rectangular duct

Details of the turbulent flow in a 1:8 aspect ratio rectangular duct at a Reynolds number of approximately 5800 were investigated both numerically and experimentally. The three-dimensional mean velocity field and the normal stresses were measured at a position 50 hydraulic diameters downstream from the inlet using laser doppler velocimetry (LDV). Numerical simulations were carried out for the same flow case assuming fully developed conditions by imposing cyclic boundary conditions in the main flow direction. The numerical approach was based on the finite volume technique with a non-staggered grid arrangement and the SIMPLEC algorithm. Results have been obtained with a linear and a non-linear (Speziale) k–ε model, combined with the Lam–Bremhorst damping functions for low Reynolds numbers. The secondary flow patterns, as well as the magnitude of the main flow and overall parameters predicted by the non-linear k–ε model, show good agreement with the experimental results. However, the simulations provide less anisotropy in the normal stresses than the measurements. Also, the magnitudes of the secondary velocities close to the duct corners are underestimated. © 1998 John Wiley & Sons, Ltd.     

ESR applications to photochemical polymer reactions

ESR spectroscopy combined with spin-trapping technique is a selective and powerful method for studies of reaction mechanisms and intermediates in free radical reactions of polymer systems. The method has been applied to several problems in our research program of which three are presented in this paper. - The mechanism of photo-initiation with aromatic ketone/tert. amine and subsequent photocuring of acrylic coatings has been largely resolved. - The mechanism of photocrosslinking of ethylene-propylenediene copolymers (EPDM elastomers) studied by model compounds has been shown to involve formation of allyl radicals in the diene groups and crosslinking by allyl radical combination. - The photoinitiated crosslinking of polyethylenes (LD, LLD and HD) has been studied using model compounds. It involves formation of primary alkyl and allyl radicals which crosslink the polymer by radical combination. - The mechanism of photocrosslinking indicates a second order reaction, i.e. rate of crosslinking depends of the square of irradiation intensity which has been verified experimentally. This result is the basis for development of rapid crosslinking processes of technical and industrial interest.