An original traceless linker strategy for solid-phase synthesis of N,N',N'-substituted guanidines

An original sequence for solution- and solid-phase synthesis of N,N',N"-trisubstituted guanidines is described. The sequence involves as key intermediate a bis-electrophilic chlorothioformamidine that is stable, easy to prepare and also easy to handle. Supported chlorothioformamidine, prepared in two steps from Merrifield resin, undergoes smooth nucleophilic addition of a primary amine to afford the corresponding supported isothiourea. The guanidine is obtained in satisfactory yield and good purity through a functionalizing-release process by heating the supported isothiourea in the presence of a primary amine in toluene at 100 degrees C. Compatibility of this sequence with several functional groups is demonstrated.     

Fracture and second-order phase transitions

Using the global fiber bundle model as a tractable scheme of progressive fracture in heterogeneous materials, we define the branching ratio in avalanches as a suitable order parameter to clarify the order of the phase transition occurring at the collapse of the system. The model is analyzed using a probabilistic approach suited to smooth fluctuations. The branching ratio shows a behavior analogous to the magnetization in known magnetic systems with second-order phase transitions. We obtain a universal critical exponent beta approximately = 0.5 independent of the probability distribution used to assign the strengths of individual fibers.     

Crystal blocking measurements of the time delay of fission induced by 32S, 48Ti, and 58Ni bombardment of W

The time delay in fission induced by bombardment of W with 180 MeV 32S, 240-255 MeV 48Ti, and 315-375 MeV 58Ni has been measured by observation of crystal blocking. There is a clear narrowing and a small increase in the minimum yield of the angular dips for fission compared with scaled dips for elastically scattered ions. This is interpreted as a fission delay of about 2 as, only weakly dependent on energy and atomic number. The delay is longer by 1 to 2 orders of magnitude than obtained from standard interpretations of measurements of prescission neutrons and giant-dipole-resonance gamma rays and from calculations of the nuclear dynamics in heavy-ion reactions.     

Analogue of cosmological particle creation in an ion trap

We study phonons in a dynamical chain of ions confined by a trap with a time-dependent (axial) potential strength and demonstrate that they behave in the same way as quantum fields in an expanding or contracting Universe. Based on this analogy, we present a scheme for the detection of the analogue of cosmological particle creation which should be feasible with present day technology. In order to test the quantum nature of the particle creation mechanism and to distinguish it from classical effects such as heating, we propose to measure the two-phonon amplitude via the 2nd red sideband transition and to compare it with the one-phonon amplitude (1st red sideband).     

Deeply virtual compton scattering off the neutron

The present experiment exploits the interference between the deeply virtual Compton scattering (DVCS) and the Bethe-Heitler processes to extract the imaginary part of DVCS amplitudes on the neutron and on the deuteron from the helicity-dependent D(e,e'gamma)X cross section measured at Q2=1.9 GeV2 and xB=0.36. We extract a linear combination of generalized parton distributions (GPDs) particularly sensitive to E_{q}, the least constrained GPD. A model dependent constraint on the contribution of the up and down quarks to the nucleon spin is deduced.     

Copper(II) complexes with new polypodal ligands presenting axial-equatorial phenoxo bridges {2-[(bis(2-pyridylmethyl)amino)methyl]-4-methylphenol, 2-[(bis(2-pyridylmethyl)amino)methyl]-4-methyl-6-(methylthio)phenol}: examples of ferromagnetically coupled bi- and trinuclear copper(II) complexes

Two new ligands, 2-[(bis(2-pyridylmethyl)amino)methyl]-4-methylphenol (HL) and 2-[(bis(2-pyridylmethyl)amino)methyl]-4-methyl-6-(methylthio)phenol (HSL), were synthesized and were used to prepare the trinuclear copper(II) complex {[CuSL(Cl)]2Cu}(PF6)2.H2O (1) and the corresponding binuclear complexes [Cu2(SL)2](PF6)2 (2) and [Cu2L2](PF6)2 (3). The crystal structure of 1 shows two different coordination environments: two square base pyramidal centers (Cu1 and Cu1a, related by a C2 axes), acting as ligands of a distorted square planar copper center (Cu2) by means of the sulfur atom of the SCH3 substituent and the bridging phenoxo oxygen atom of the ligand (Cu2-S = 2.294 A). Compounds 2 and 3 show two equivalent distorted square base pyramidal copper(II) centers, bridged in an axial-equatorial fashion by two phenoxo groups, thus defining an asymmetric Cu2O2 core. A long copper-sulfur distance measured in 2 (2.9261(18) A) suggests a weak bonding interaction. This interaction induces a torsion angle between the methylthio group and the phenoxo plane resulting in a dihedral angle of 41.4(5) degrees. A still larger distortion is observed in 1 with a dihedral angle of 74.0(6) degrees. DFT calculations for 1 gave a ferromagnetic exchange between first neighbors interaction, the calculated J value for this interaction being +11.7 cm-1. In addition, an antiferromagnetic exchange for 1 was obtained for the second neighbor interaction with a J value of -0.05 cm-1. The Bleaney-Bowers equation was used to fit the experimental magnetic susceptibility data for 2 and 3; the best fit was obtained with J values of +3.4 and -16.7 cm-1, respectively. DFT calculations for 2 and 3 confirm the nature and the values of the J constants obtained by the fit of the experimental data. ESR and magnetic studies on the reported compounds show a weak exchange interaction between the copper(II) centers. The low values obtained for the coupling constants can be explained in terms of a poor overlap between the magnetic orbitals, due to the axial-equatorial phenoxo bridging mode observed in these complexes.     

Rapid prototyping of poly(methyl methacrylate) microfluidic systems using solvent imprinting and bonding

We have developed a method for rapid prototyping of hard polymer microfluidic systems using solvent imprinting and bonding. We investigated the applicability of patterned SU-8 photoresist on glass as an easily fabricated template for solvent imprinting. Poly(methyl methacrylate) (PMMA) exposed to acetonitrile for 2 min then had an SU-8 template pressed into the surface for 10 min, which provided appropriately imprinted channels and a suitable surface for bonding. After a PMMA cover plate had also been exposed to acetonitrile for 2 min, the imprinted and top PMMA pieces could be bonded together at room temperature with appropriate pressure. The total fabrication time was less than 15 min. Under the optimized fabrication conditions, nearly 30 PMMA chips could be replicated using a single patterned SU-8 master with high chip-to-chip reproducibility. Relative standard deviations were 2.3% and 5.4% for the widths and depths of the replicated channels, respectively. Fluorescently labeled amino acid and peptide mixtures were baseline separated using these PMMA microchips in <15s. Theoretical plate numbers in excess of 5000 were obtained for a approximately 3 cm separation distance, and the migration time relative standard deviation for an amino acid peak was 1.5% for intra-day and 2.2% for inter-day analysis. This new solvent imprinting and bonding approach significantly simplifies the process for fabricating microfluidic structures in hard polymers such as PMMA.     

Comparison of proton conduction in KTaO3 and SrZrO3

In the present paper, the authors focus on proton conduction pathways in a cubic perovskite KTaO(3) and an orthorhombic perovskite SrZrO(3). Density functional theory with a generalized gradient approximation is used to find proton binding sites. The nudged elastic band method is used to find transition states between minima. With this potential energy map of binding and transition states, adjacency matrices and their analogs identify four types of conduction paths in KTaO(3). Distortions from these paths are seen in SrZrO(3). In both cases, the lowest energy path has an intraoctahedral transfer rate-limiting barrier. A Fourier analysis of the OH stretch in ab initio molecular dynamics simulations revealed a strongly redshifted OH stretch in SrZrO(3) relative to KTaO(3). Hence, an orthorhombic system with a lowest energy conduction path limited by an intraoctahedral barrier can exhibit a redshifted OH stretch.     

Thio- and seleno-ether complexes with Group 4 tetrahalides and tin tetrachloride: preparation and use in CVD for metal chalcogenide films

Reaction of TiCl(4) or ZrI(4) with the soft, neutral o-C(6)H(4)(CH(2)EMe)(2) (E = S or Se) in anhydrous CH(2)Cl(2) (or toluene) yields the distorted octahedral chelate complexes [MX(4){o-C(6)H(4)(CH(2)EMe)(2)}]. Using Et(2)Se gives [MX(4)(Et(2)Se)(2)] (M = Zr, X = Cl or I; M = Hf, X = I). The Sn(IV) analogues, [SnCl(4){o-C(6)H(4)(CH(2)EMe)(2)}] and [SnCl(4)(Et(2)Se)(2)] were obtained similarly. These complexes have been characterised spectroscopically and analytically, and crystal structures of trans-[SnCl(4)(Et(2)Se)(2)] and some selenonium salts derived as minor by-products from the parent Group 4 complexes are described. The neutral chalcogenoether complexes have been evaluated as single source precursors to ME(2)/ME thin films via LPCVD. [TiCl(4){o-C(6)H(4)(CH(2)EMe)(2)}] leads to the deposition of air and moisture stable TiE(2) films (with no residual Cl). Coverage of the substrate is uniform with platelet growth perpendicular to the surface. The heavier Zr(IV) species do not lead to significant ZrE(2) deposition. On the other hand, LPCVD of [SnCl(4){o-C(6)H(4)(CH(2)SMe)(2)}] leads to deposition of SnS(2) at lower temperatures and SnS at higher temperatures, while [SnCl(4){o-C(6)H(4)(CH(2)SeMe)(2)}] gives rather uneven coatings of SnSe(2). The Et(2)Se derivative, [SnCl(4)(Et(2)Se)(2)] leads to uniform deposition of SnSe(2) with growth perpendicular to the substrate surface. The SnE(2)/SnE films are stable indefinitely to air and moisture. The generation of TiS(2), SnS(2) and SnS in this way are very rare examples of metal sulfide deposition from C-S bond fission within a thioether complex.     

Monotone traveling wavefronts of the KPP-Fisher delayed equation

In the early 2000's, Gourley (2000), Wu et al. (2001), Ashwin et al. (2002) initiated the study of the positive wavefronts in the delayed Kolmogorov-Petrovskii-Piskunov-Fisher equation

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