Characterisation of dissolving pulp using designed process variables, NIR and NMR spectroscopy, and multivariate data analysis

Two processability variables, filter clogging and alkali resistance, were measured in a series of laboratorycooked viscose pulps. The pulps were also characterised by ¹³CCP/MAS solid state nuclear magnetic resonance (NMR) and near infrared (NIR) spectroscopy. Partial least squares (PLS) regression was used to investigate the information provided by the spectroscopic methods with respect to the processability measurements. The study showed that the alkali resistance, R18, of the pulp and the filter clogging value, Kw, of the laboratoryprepared viscose can be modelled by NIR and multivariate data analysis (MVA). The alkali resistance, R18, of the pulp can also be calculated by NMR and partial least squares (PLS) regression. Analysis of the loading values in the PLS model showed that pulps with high alkali resistance have higher crystallinity than pulps with low alkali resistance. Analysis of variables of the cooking conditions showed that the chemical charge (Na₂O) and pH should be kept low to give high alkali resistance, whereas high Na₂O gives low filter clogging values.     

Excitation of radial collective modes in a quantum dot: Beyond linear response

The recent results on the linear breathing mode of the excitation spectrum of a quantum dot obtained by McDonald et. al [Phys. Rev. Lett. 111 , 256801 (2013)] are extended to the nonlinear regime. To accomplish this and analyze the results the response of five different models of two interacting electrons in a quantum dot to an external short lived radial excitation that is strong enough to excite the system well beyond the linear response regime is compared. The models considered describe the Coulomb interaction between the electrons in different ways ranging from mean‐field approaches to configuration interaction (CI) models, where the two‐electron Hamiltonian is diagonalized in a large truncated Fock space. The radially symmetric excitation is selected in order to severely put to test the different approaches to describe the interaction and correlations of an electron system in a nonequilibrium state. As can be expected for the case of only two electrons none of the mean‐field models can in full details reproduce the results obtained by the CI model. Nonetheless, some linear and nonlinear characteristics are reproduced reasonably well. All the models show activation of an increasing number of collective modes as the strength of the excitation is increased. By varying slightly the confinement potential of the dot it was observed how sensitive the properties of the excitation spectrum are to the Coulomb interaction and its correlation effects. In order to approach closer the question of nonlinearity one of the mean‐field models has been solved directly in a nonlinear fashion without resorting to iterations.     

1H and 13C NMR investigation of the influence of nonligated residue contacts on the heme electronic structure in cyanometmyoglobin complexes reconstituted with centro- and pseudocentrosymmetric hemins

The 1H and 13C chemical shifts for the heme methyls of low-spin, ferric sperm whale cyanometmyoglobin reconstituted with a variety of centrosymmetric and pseudocentrosymmetric hemins have been recorded and analyzed to shed light on the nature of heme-protein contacts, other than that of the axial His, that modulate the rhombic perturbation to the heme's in-plane electronic asymmetry. The very similar 1H dipolar shifts for heme pocket residues in all complexes yield essentially the same magnetic axes as in wild type, and the resultant dipolar shifts allow the direct determination of the heme methyl proton and 13C contact shifts in all complexes. It is demonstrated that, even when the magnetic axes and anisotropies are known, the intrinsic uncertainties in the orientational parameters lead to a sufficiently large uncertainty in dipolar shift that the methyl proton contact shifts are inherently significantly less reliable indicators of the unpaired electron spin distribution than the methyl 13C contact shifts. The pattern of the noninversion symmetry in 13C contact shifts in the centro- or pseudocentrosymmetric hemes is shown to correlate with the positions of aromatic rings of Phe43(CD1) and His97(FG3) parallel to, and in contact with, the heme. These results indicate that such pi-pi interactions significantly perturb the in-plane asymmetry of the heme pi spin distribution and cannot be ignored in a quantitative interpretation of the heme methyl 13C contact shifts in terms of the axial His orientation in b-type hemoproteins.     

Asymptotic Exactness of Magnetic Thomas—Fermi Theory at Nonzero Temperature

We consider the grand canonical pressure for Coulombic matter with nuclear charges ～Zin a magnetic field Band at nonzero temperature. We prove that its asymptotic limit as Z→∞ with B/Z ³→0 can be obtained by minimizing a Thomas–Fermi type pressure functional.