DSC study of the effect of irradiation upon the glass transition temperature (T g) of polyethylene

The glass transition of an irradiated, ultra-high molecular weight, linear polyethylene was investigated by means of the Perkin-Elmer DSC-2 differential scanning calorimeter. The experimental specific heat data were compared with those of the nonirradiated sample, obtained by DSC and adiabatic calorimetry.     

(Z)-3-p-tolylsulfinylacrylonitrile as a chiral dienophile: diels-alder reactions with furan and acyclic dienes

The behavior of (Z)-3-p-tolylsulfinylacrylonitrile (1) as a chiral dienophile has been evaluated from its reactions with furan and acyclic dienes. Electrostatic interactions of the cyano group with the sulfinyl one restrict the conformational mobility around the C-S bond, thus controlling the pi-facial selectivity, which is almost complete in all cases, the approach of the diene from the less-hindered face of the dienophile (that bearing the lone electron pair) in the predominant rotamer being the favored one. The regioselectivity is also completely controlled by the cyano group. Additionally, the reactivity of compound 1 as well as its endo-selectivity are both higher than those observed for the corresponding (Z)-3-sulfinylacrylates, thus proving the potential of sulfinylnitriles as chiral dienophiles.     

Infinitesimal Stability of the Equilibrium States of?an?Incompressible, Isotropic Elastic Tube Under?Pressure

The infinitesimal stability of the equilibrium states of an arbitrary incompressible, isotropic and homogeneous elastic cylindrical shell in a pure radial expansion under a constant inflation pressure is studied for both thick- and thin-walled shells. The classical criterion of infinitesimal stability yields a general stability theorem relating the frequency and pressure response and reveals that points at which the pressure is stationary define the domain of unstable or neutrally stable states. All results are expressed in terms of a general shear response function, and specific results are provided for the Mooney-Rivlin, Gent and Ogden models, the second having limited extensibility, the last including experimental data. Every static state of a Mooney-Rivlin tube is stable so long as the pressure is less than an asymptotic limit that increases with the thickness. Otherwise, only the Ogden model exhibits static states of instability for all long cylindrical tubes of thickness less than a transitional value above which all static states are infinitesimally stable. A long cylindrical cavity in all three unbounded models is stable for all pressures. All results are illustrated graphically.     

Effect of the sixth axial ligand in CS-ligated iron(II)octaethylporphyrinates: structural and Mössbauer studies

The effect of a sixth ligand in a series of low-spin thiocarbonyl-ligated iron(II)octaethylporphyrinates has been investigated. Six-coordinate complexes have been synthesized and characterized by M?ssbauer and infrared spectroscopy and single-crystal X-ray structure determinations. The results are compared with the five-coordinate parent complex. The crystal structures of [Fe(OEP)(CS)(1-MeIm)] and [Fe(OEP)(CS)(Py)] are reported and discussed. The 1-methylimidazole and pyridine derivatives exhibit Fe-C(CS) bond distances of 1.703(4) and 1.706(2) A that are significantly longer than the 1.662(3) A reported for five-coordinate [Fe(OEP)(CS)] (Scheidt, W. R.; Geiger, D. K. Inorg. Chem. 1982, 21, 1208). The trans Fe-N(ligand) distances of 2.112(3) and 2.1550(15) A observed for the 1-methylimidazole and pyridine complex are approximately 0.13 A longer than those observed for analogous bis-ligated complexes and are consistent with a significant structural trans effect for the CS ligand. M?ssbauer investigations carried out for five- and six-coordinate thiocarbonyl derivatives with several different sixth axial ligands reveal interesting features. All derivatives exhibit very small isomer shift values, consistent with a very strong interaction between iron and CS. The five-coordinate derivative has delta(Fe) = 0.08 mm/s, and the six-coordinate complexes exhibit delta(Fe) = 0.14 to 0.19 mm/s at 4.2 K. The five-coordinate complex shows a large quadrupole splitting (DeltaE(q) = 1.93 mm/s at 4.2 K) which is reduced on coordination of the sixth ligand (DeltaE(q) = 0.42-0.80 mm/s at 4.2 K). Addition of a sixth ligand also leads to a small decrease in the value of nu(CS). Correlations in structural, IR, and M?ssbauer results suggest that the sixth ligand effect is primarily induced by changes in sigma-bonding. The structure of [Fe(OEP)(CS)(CH(3)OH)] is briefly reported. Crystal data: [Fe(OEP)(CS)(1-MeIm)] crystallizes in the monoclinic system, space group P2(1)/n, Z = 4, a = 9.5906(5) A, b = 16.704(4) A, c = 23.1417(6) A, beta = 100.453(7) degrees. [Fe(OEP)(CS)(Py)] crystallizes in the triclinic system, space group P1, Z = 5, a = 13.9073(6) A, b = 16.2624(7) A, c = 22.0709(9) A, alpha = 70.586(1) degrees, beta = 77.242(1) degrees, gamma = 77.959(1) degrees. [Fe(OEP)(CS)(CH(3)OH)] crystallizes in the triclinic system, space group P1, Z = 1, a = 9.0599(5) A, b = 9.4389(5) A, c = 11.0676(6) A, alpha = 90.261(1) degrees, beta = 100.362(1) degrees, gamma = 114.664(1) degrees.     

Facile hydrometalation of alkynes by nido-1,2-(CpRuH)(2)B(3)H(7) yielding novel Ru-B edge-bridging alkylidenes. Stepwise conversion of HCtbd1;CC(O)OMe into nido-1,2-(CpRuH)(2)-3-HOB-4-MeC-5-MeOC-BH(3), Cp = eta(5)-C(5)Me(5)

The reaction of the alkyne HCCC(O)OMe with 7 sep 1,2-(Cp*RuH)2B3H7 leads to hydroboration plus hydroruthenation to produce nido-1,3-mu-Me{C(O)OMe}C-1,2-(Cp*Ru)2B3H7, a compound with an exocluster ruthenium-boron mu-alkylidene that exists in two isomeric forms. Both isomers undergo rearrangement with intramolecular chelation of the carbonyl oxygen at a boron site, thereby opening the cluster and generating arachno-2,3,-mu(C)-5-eta1(O)-Me{C(O)OMe}C-1,2-(Cp*Ru)2B3H7. Further heating leads to deoxygenation of the carbonyl fragment by a boron center concurrent with insertion of the carbon atom into the metallaborane cage to give nido-1,2-(Cp*RuH)2-3-HOB-4-MeC-5-MeOC-BH3.     

Selective dye-labeling of newly synthesized proteins in bacterial cells

We describe fluorescence labeling of newly synthesized proteins in Escherichia coli cells by means of Cu(I)-catalyzed cycloaddition between alkynyl amino acid side chains and the fluorogenic dye 3-azido-7-hydroxycoumarin. The method involves co-translational labeling of proteins by the non-natural amino acids homopropargylglycine (Hpg) or ethynylphenylalanine (Eth) followed by treatment with the dye. As a demonstration, the model protein barstar was expressed and treated overnight with Cu(I) and 3-azido-7-hydroxycoumarin. Examination of treated cells by confocal microscopy revealed that strong fluorescence enhancement was observed only for alkynyl-barstar treated with Cu(I) and the reactive dye. The cellular fluorescence was punctate, and gel electrophoresis confirmed that labeled barstar was localized in inclusion bodies. Other proteins showed little fluorescence. Examination of treated cells by fluorimetry demonstrated that cultures supplemented with Eth or Hpg showed an 8- to 14-fold enhancement in fluorescence intensity after labeling. Addition of a protein synthesis inhibitor reduced the emission intensity to levels slightly above background, confirming selective labeling of newly synthesized proteins in the bacterial cell.     

Finite amplitude,free vibrations of an axisymmetric load supported by a highly elastic tubular shear spring

The finite amplitude, free vibrational characteristics of a simple mechanical system consisting of an axisymmetric rigid body supported by a highly elastic tubular shear spring subjected to axial, rotational, and coupled shearing motions are studied. Two classes of elastic tube materials are considered: a compressible material whose shear response is constant, and an incompressible material whose shear response is a quadratic function of the total amount of shear. The class of materials with constant shear response includes the incompressible Mooney-Rivlin material and certain compressible Blatz-Ko, Hadamard, and other general kinds of models. For each material class, the quasi-static elasticity problem is solved to determine the telescopic and gyratory shearing deformation functions needed to evaluate the elastic tube restoring force and torque exerted on the body. For all materials with constant shear response, the differential equations of motion are uncoupled equations typical of simple harmonic oscillators. Hence, exact solutions for the forced vibration of the system can be readily obtained; and for this class, engineering design formulae for the load-deflection relations are discussed and compared with experimental results of others'. For the quadratic material, however, the general motion of the body is characterized by a formidable, coupled system of nonlinear equations. The free, coupled shearing motion for which either the axial or the azimuthal shear deformation may be small is governed by a pair of equations of the Duffing and Hill types. On the other hand, the finite amplitude, pure axial and pure rotational motions of the load are described by the classical, nonlinear Duffing equation alone. A variety of problems are solved exactly for these separate free vibrational modes, and a number of physical results are presented throughout.     

An Average-Stretch Full-Network Model for Rubber Elasticity

Two constitutive models that are based on the classical non-Gaussian, Kuhn-Grün probability distribution function are reviewed. It is shown that all chains of a network cell structure comprised of a finite number of identical chains in an affine deformation referred to principal axes may have the same invariant stretch, if and only if the chains are oriented initially along any of eight directions forming the diagonals of a unit cube. The 4-chain tetrahedral and the 8-chain cubic cell structures are familiar admissible models having this property. An easy derivation of the constitutive equation for the Wu and van der Giessen full-network model of initially identical chains arbitrarily oriented in the undeformed state is presented. The constitutive equations for the neo-Hookean model, the 3 -chain model, and the equivalent 4- and 8-chain models are then derived from the Wu and van der Giessen equation. The squared chain stretch of an arbitrarily directed chain averaged over a unit sphere surrounding all chains radiating from a cross-link junction as its center is determined. An average-stretch, full-network constitutive equation is then derived by approximation of the Wu and van der Giessen equation. This result, though more general in that no special chain cell morphology is introduced, is the same as the constitutive equation for the 4- and 8-chain models. Some concluding remarks on extensions to amended models are presented.