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1.
Hanni M Lantto P Runeberg N Jokisaari J Vaara J 《The Journal of chemical physics》2004,121(12):5908-5919
Quantum chemical calculations of the nuclear shielding tensor, the nuclear quadrupole coupling tensor, and the spin-rotation tensor are reported for the Xe dimer using ab initio quantum chemical methods. The binary chemical shift delta, the anisotropy of the shielding tensor Delta sigma, the nuclear quadrupole coupling tensor component along the internuclear axis chi( parallel ), and the spin-rotation constant C( perpendicular ) are presented as a function of internuclear distance. The basis set superposition error is approximately corrected for by using the counterpoise correction (CP) method. Electron correlation effects are systematically studied via the Hartree-Fock, complete active space self-consistent field, second-order M?ller-Plesset many-body perturbation, and coupled-cluster singles and doubles (CCSD) theories, the last one without and with noniterative triples, at the nonrelativistic all-electron level. We also report a high-quality theoretical interatomic potential for the Xe dimer, gained using the relativistic effective potential/core polarization potential scheme. These calculations used valence basis set of cc-pVQZ quality supplemented with a set of midbond functions. The second virial coefficient of Xe nuclear shielding, which is probably the experimentally best-characterized intermolecular interaction effect in nuclear magnetic resonance spectroscopy, is computed as a function of temperature, and compared to experiment and earlier theoretical results. The best results for the second virial coefficient, obtained using the CCSD(CP) binary chemical shift curve and either our best theoretical potential or the empirical potentials from the literature, are in good agreement with experiment. Zero-point vibrational corrections of delta, Delta sigma, chi (parallel), and C (perpendicular) in the nu=0, J=0 rovibrational ground state of the xenon dimer are also reported. 相似文献
2.
Khalid Ibrahim Katariina Yliheikkilä Barbro Löfgren Markku Leskelä Jukka Seppälä 《European Polymer Journal》2004,40(6):1095-1104
Four tetradentate nitrogen ligands, viz. dichloro{[N,N′-diphenyl-N,N′-di(quinoline-2-methyl)]-1,2-ethylene diamine} (1), {[N,N′-dioctyl-N,N′-di(quinoline-2-methyl)]-1,2-ethylene diamine} (2), {[N,N′-dibenzyl-N,N′-di(quinoline-2-methyl)]-1,2-ethylene diamine} (3), and (1R,2R)-(−)-N,N′-di(quinoline-2-methyl) di-iminocyclohexane (4), were investigated as novel complexing ligands in iron-mediated atom transfer radical polymerization (ATRP) of methyl methacrylate where ethyl-2-bromoisobutyrate was the initiator in o-xylene at 90 °C. With ligands 1 and 2 the experimental molecular weights increased gradually with monomer conversion. High to moderate conversions (87%, 43%) were obtained in relatively short times (90 min for 1 and 30 min for 2), which indicates an efficient catalyst system, but after these times a dramatic increase in viscosity of the polymerization medium led to loss of control. It is noteworthy that polymerization proceeded in a controlled manner with ligand 1, which has two rather bulky substituents on the N-atom. Such bulky ligands did not work for a copper-based system, where they led to excessive terminations or other side reactions. When the bulkiness of the substituents was significantly increased, as in ligand 3, a decrease in polymerization rate and loss of control occurred. Ligand 4 was less efficient than the other ligands, probably because the ethylene bridge was replaced by cyclohexane bridge. 相似文献
3.
Mikael Mohtaschemi Anni Sorvari Antti Puisto Markus Nuopponen Jukka Seppälä Mikko J. Alava 《Cellulose (London, England)》2014,21(6):3913-3925
We conduct rheological characterization of nanofibrillated cellulose (NFC) suspensions, a highly non-Newtonian complex fluid, at several concentrations. Special care is taken to cope with the prevalent problems of time scale issues, wall depletion and confinement effects. We do this by combining the wide-gap vane geometry, extremely long measurement times, and modeling. We take into account the wide-gap related stress heterogeneity by extending upon mainstream methods and apply a gap correction. Furthermore, we rationalize the experimental data through a simple viscous structural model. With these tools we find that, owing to the small size of the particles subjected to Brownian motion, the NFC suspensions exhibit a critical shear rate, where the flow curve experiences a turning point. This makes the steady state of these suspensions at low shear rates non-unique. To optimize various mixing and pumping applications, such history dependent tendency of NFC suspensions to shear band needs to be taken into account. 相似文献
4.
Jukka J. Remes Ahmed Abou Elseoud Esa Ollila Marianne Haapea Tuomo Starck Juha Nikkinen Osmo Tervonen Olli Silven 《Magnetic resonance imaging》2013,31(8):1338-1348
Subject-level resting-state fMRI (RS-fMRI) spatial independent component analysis (sICA) may provide new ways to analyze the data when performed in the sliding time window. However, whether principal component analysis (PCA) and voxel-wise variance normalization (VN) are applicable pre-processing procedures in the sliding-window context, as they are for regular sICA, has not been addressed so far. Also model order selection requires further studies concerning sliding-window sICA. In this paper we have addressed these concerns. First, we compared PCA-retained subspaces concerning overlapping parts of consecutive temporal windows to answer whether in-window PCA and VN can confound comparisons between sICA analyses in consecutive windows. Second, we compared the PCA subspaces between windowed and full data to assess expected comparability between windowed and full-data sICA results. Third, temporal evolution of dimensionality estimates in RS-fMRI data sets was monitored to identify potential challenges in model order selection in a sliding-window sICA context. Our results illustrate that in-window VN can be safely used, in-window PCA is applicable with most window widths and that comparisons between windowed and full data should not be performed from a subspace similarity point of view. In addition, our studies on dimensionality estimates demonstrated that there are sustained, periodic and very case-specific changes in signal-to-noise ratio within RS-fMRI data sets. Consequently, dimensionality estimation is needed for well-founded model order determination in the sliding-window case. The observed periodic changes correspond to a frequency band of ≤ 0.1 Hz, which is commonly associated with brain activity in RS-fMRI and become on average most pronounced at window widths of 80 and 60 time points (144 and 108 s, respectively). Wider windows provided only slightly better comparability between consecutive windows, and 60 time point or shorter windows also provided the best comparability with full-data results. Further studies are needed to determine the cause for dimensionality variations. 相似文献
5.
6.
Nikolaos Pahimanolis Arto Salminen Paavo A. Penttilä Juuso T. Korhonen Leena-Sisko Johansson Janne Ruokolainen Ritva Serimaa Jukka Seppälä 《Cellulose (London, England)》2013,20(3):1459-1468
In this paper, nanofibrillated cellulose/carboxymethyl cellulose (CMC) composite films were prepared using tape casting. The obtained transparent films showed shear induced partial alignment of fibrils along the casting direction, resulting in birefringence in cross polarized light. The carboxyl groups of CMC could be further utilized to create ionic crosslinking by treatment with glycidyl trimethyl ammonium chloride (GTMA). The GTMA treated composite films had improved mechanical properties both in wet and dry state. The chemical composition and morphologies of composites were analyzed with X-ray photoelectron spectroscopy, elemental analysis, scanning electron microscopy and wide-angle X-ray scattering. 相似文献
7.
Colette Lebrun Dr. Matthieu Starck Vicky Gathu Yves Chenavier Dr. Pascale Delangle 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(50):16566-16573
Peptides are interesting tools to rationalize uranyl–protein interactions, which are relevant to uranium toxicity in vivo. Structured cyclic peptide scaffolds were chosen as promising candidates to coordinate uranyl thanks to four amino acid side chains pre‐oriented towards the dioxo cation equatorial plane. The binding of uranyl by a series of decapeptides has been investigated with complementary analytical and spectroscopic methods to determine the key parameters for the formation of stable uranyl–peptide complexes. The molar ellipticity of the uranyl complex at 195 nm is directly correlated to its stability, which demonstrates that the β‐sheet structure is optimal for high stability in the peptide series. Cyclodecapeptides with four glutamate residues exhibit the highest affinities for uranyl with log KC=8.0–8.4 and, therefore, appear as good starting points for the design of high‐affinity uranyl‐chelating peptides. 相似文献
8.
We point out the need for Behavioral Operational Research (BOR) in advancing the practice of OR. So far, in OR behavioral phenomena have been acknowledged only in behavioral decision theory but behavioral issues are always present when supporting human problem solving by modeling. Behavioral effects can relate to the group interaction and communication when facilitating with OR models as well as to the possibility of procedural mistakes and cognitive biases. As an illustrative example we use well known system dynamics studies related to the understanding of accumulation. We show that one gets completely opposite results depending on the way the phenomenon is described and how the questions are phrased and graphs used. The results suggest that OR processes are highly sensitive to various behavioral effects. As a result, we need to pay attention to the way we communicate about models as they are being increasingly used in addressing important problems like climate change. 相似文献
9.
New statistical methods have recently been developed to reconstruct and analyze dark matter mass maps from weak lensing observations. The field of weak lensing is motivated by the observations made in the last decades showing that the visible matter represents only about 4-5% of the Universe, the rest being dark. The Universe is now thought to be mostly composed of an invisible, pressureless matter, potentially a relic from higher energy theories, called "dark matter" (20-21%) and by an even more mysterious term, described in Einstein equations as a vacuum energy density, called "dark energy" (70%). This "dark" Universe is not well described or even understood, so this point could be the next breakthrough in cosmology. 相似文献
10.
Kowalewski J Effemey M Jokisaari J 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2002,157(2):171-177
Multiple-field (4.7, 9.4, 14.1 T) carbon-13 relaxation data are reported for hexamethylenetetramine (HMTA) in the cryosolvent D(2)O/DMSO at 243 K. Under these conditions, the reorientational motion of HMTA is outside of the extreme narrowing range and the relaxation data can be subjected to a quantitative interpretation. Because of the high symmetry of the HMTA molecule, the reorientation must be isotropic. Treating the reorientation as a small-step rotational diffusion of a rigid body, we obtain a rotational correlation time of 1.0 ns and a carbon-proton dipole-dipole coupling constant corresponding to an effective internuclear distance of 114. 2 pm. The harmonic vibrational correction to the dipole-dipole coupling constant, based on a known force field, yields an NMR estimate of the r(alpha) distance of 110.8 +/- 0.3 pm. 相似文献