Elastic modulus of the crystalline regions of polyimide derived from poly(amic acid)–biphtalic dianhydride and p-phenylene diamine

The elastic modulus E_l of the crystalline regions in the direction parallel to the chain axis was measured by X-ray diffraction for polyimide derived from polyamic acid (biphthalic dianhydride and p-phenylene diamine). These specimens were cured by two different routes: curing at 200 °C, and at 400 °C for 1 h, respectively (2STEPS), and curing from 80 °C to 400 °C stepwise (nine steps) for 1 h at each step (STEPWISE). The E_l values of 54–169 GPa were obtained for the STEPWISE specimen and 80–178 GPa for the 2STEPS specimen, depending on the meridional reflection employed for measurement of the E_l value. A linear relationship between the E_l value and the fiber identity period was obtained from each meridional diffraction, such that the E_l value increased with an increase in the fiber identity period. The E_l value of the fully extended structure was estimated to be 210 GPa. These are considered to be due to the coexistence of polymorphs with different skeletal structures. The crystalline regions of the 2STEPS specimen seems to consist of a more extended skeleton than those of the STEPWISE specimen. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 3294–3301, 1999     

Decisive role of electronic polarization of the protein environment in determining the absorption maximum of halorhodopsin

It is known that the absorption maximum of halorhodopsin is red shifted by 10 nm with the uptake of a chloride ion Cl(-). According to the X-ray structure, the ion is located at the position of the counterion of the chromophore, protonated retinal Schiff base. Thus, the direction of the observed spectral change is opposite to that expected from the pi-electron redistribution (an increase in the bond alternation) induced by the counterion. The physical origin of this abnormal shift is never explained in terms of any simple chemical analogues. We successfully explain this phenomenon by a QM/MM type of excitation energy calculation. The three-dimensional structure of the protein is explicitly taken into account using the X-ray structure. We reveal that the electronic polarization of the protein environment plays an essential role in tuning the absorption maximum of halorhodopsin.     

Facially Dispersed Polyhydride Cu9 and Cu16 Clusters Comprising Apex‐Truncated Supertetrahedral and Square‐Face‐Capped Cuboctahedral Copper Frameworks

By using a linear tetraphosphine, meso‐bis[(diphenylphosphinomethyl)phenylphosphino]methane (dpmppm), nona‐ and hexadecanuclear copper hydride clusters, [Cu₉H₇(μ‐dpmppm)₃]X₂ (X=Cl ( 1 a ), Br ( 1 b ), I ( 1 c ), PF₆ ( 1 d )) and [Cu₁₆H₁₄(μ‐dpmppm)₄]X₂ (X₂=I₂ ( 2 c ), (4/3) PF₆?(2/3) OH ( 2 d )) were synthesized and characterized. They form copper‐hydride cages of apex‐truncated supertetrahedral {Cu₉H₇}²⁺ and square‐face‐capped cuboctahedral {Cu₁₆H₁₄}²⁺ structures. The hydride positions were estimated by DFT calculations to be facially dispersed around the copper frameworks. A kinetically controlled synthesis gave an unsymmetrical Cu₈H₆ cluster, [Cu₈H₆(μ‐dpmppm)₃]²⁺ ( 3 ), which readily reacted with CO₂ to afford linear Cu₄ complexes with formate bridges, leading to an unprecedented hydrogenation of CO₂ into formate catalyzed by {Cu₄(μ‐dpmppm)₂} platform. The results demonstrate that new motifs of copper hydride clusters could be established by the tetraphosphine ligands, and the structures influence their reactivity.     

Monomolecular film and absorption behavior of polymers having carboxyl groups

π-A isotherms of monolayers of various copolymers containing carboxyl groups derived from acrylic acid (AA) were measured. The conformation of polymer adsorbed on the water surface and interaction forces between polymer and water surface (considered to be a model for the surface of inorganic powders) owing to AA groups is discussed based on the π-A isotherms.

Polyacrylic esters having a small amount of AA groups formed the expanded type of monolayer. AA groups cause an increase in the interaction force between the polymer and water surface. Polymethyl methacrylate having a small amount of AA groups formed condensed-type monolayers, while with a large amount of AA groups it showed two types of monolayer collapse. Though polystyrene could not spread as a mono-layer, poly (styrene-acrylic acid) [p(St-AA)] copolymer formed a monolayer when the AA content was over 4 mol %. The adsorbance of P(St-AA) on water, calculated from π-A isotherm, is the same as that obtained on α-Fe₂O₃ independently. This means the conformation of the polymer on the solid surface and the interaction force can be discussed by using the π-A isotherm.     

Flow and heat transfer over a backward-facing step with a cylinder mounted near its top corner

A study was made to see if it is possible to enhance the heat transfer in the downstream region of a backward-facing step, where heat transfer is normally deteriorated, by the insertion of a cylinder near the top corner of the step. Cylinder size and streamwise position of the cylinder were kept constant but the cross-stream position of the cylinder was changed in three steps. Results of the heat transfer experiment, flow visualization, and measurement of the averaged and fluctuating flow fields were reported. When the cylinder was mounted at a position, a little higher than the top surface of the step, a jet-like flow pattern emerged in the averaged velocity profile beneath the cylinder and the recirculating flow was intensified. Therefore, the velocity of recirculating flow near the wall is increased at some streamwise positions. Additionally, the velocity fluctuation was intensified not only in the shear layer between the jet-like flow and the recirculating flow regions but also in the near wall region, resulting in the effective augmentation of heat transfer in this case. Therefore, it is concluded that the mounting of a cylinder is effective in the enhancement of deteriorated heat transfer in the recirculating flow region, if its is mounted in a proper position.     

Intrinsic low temperature paramagnetism in B-DNA

We present an experimental study of magnetization in lambda-DNA in conjunction with structural measurements. The results show the surprising interplay between the molecular structures and their magnetic property. In the B-DNA state, lambda-DNA exhibits paramagnetic behavior below 20 K that is nonlinear in an applied magnetic field whereas, in the A-DNA state, it remains diamagnetic down to 2 K. We propose orbital paramagnetism as the origin of the observed phenomena and discuss its relation to the existence of long range coherent transport in B-DNA at low temperature.     

Gold and Silver Chains Supported by Linear Hexaphosphine Ligands

A new linear hexaphosphine, rac‐cis,cis,trans‐ bis{[(diphenylphosphinomethyl)phenylphosphinomethyl]phenylphosphino}methane ( P₆ ), was synthesized and isolated as a pure isomer, confirmed by transforming to the corresponding phosphine sulfide. The methylene‐bridged linear hexaphosphine readily organized flexible gold(I) and silver(I) hexanuclear chains, [M₆(μ‐ P₆ )₂]X₆ (X₆=(OTf)₆, M=Au ( 1 ), Ag ( 2 ); X₆=Cl₂(PF₆)₄, M=Au ( 3 )). The hexaphosphine also supported a tetrasilver(I) complex [Ag₄(μ‐ P₆ )₂](OTf)₄ ( 4 ), which was readily transformed by treatment with AgOTf into 3 , revealing a drastic alternation of the two P₆ arrangement. The hexagold(I) chains exhibited a considerably red‐shifted absorption (～410 nm) and emission (540–580 nm) to ¹[5d_σ*→6p_σ] and from ³[5d_σ*→6p_σ] excited states of the metal centers, respectively. The new linear hexaphosphine could be a useful tool to construct linear metal clusters as subnano building blocks.