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排序方式: 共有208条查询结果,搜索用时 15 毫秒
91.
We present molecular dynamics simulations of planar Poiseuille flow of a Lennard-Jones fluid at various temperatures and body forces. Local thermostatting is used close to the walls to reach steady-state up to a limit body force. Macroscopic fields are obtained from microscopic data by time- and space-averaging and smoothing the data with a self-consistent coarse-graining method based on kernel interpolation. Two phenomena make the system interesting: (i) strongly confined fluids show layering, i.e., strong oscillations in density near the walls, and (ii) the stress deviates from the Newtonian fluid assumption, not only in the layered regime, but also much further away from the walls. Various scalar, vectorial, and tensorial fields are analyzed and related to each other in order to understand better the effects of both the inhomogeneous density and the anisotropy on the flow behavior and rheology. The eigenvalues and eigendirections of the stress tensor are used to quantify the anisotropy in stress and form the basis of a newly proposed objective, inherently anisotropic constitutive model that allows for non-collinear stress and strain gradient by construction. 相似文献
92.
Pinheiro JP Moura L Fokkink R Farinha JP 《Langmuir : the ACS journal of surfaces and colloids》2012,28(13):5802-5809
We prepared anionic multistimuli responsive core-shell polymer nanoparticles with very low size dispersity. By using either acrylic acid (AA) or methacrylic acid (MA) as a comonomer in the poly(N-isopropyl acrylamide) (PNIPAM) shell, we are able to change the distribution of negative charges in the nanoparticle shell. The particle size, volume phase transition temperature, and aggregation state can be modulated using temperature, pH, or ionic strength, providing a very versatile platform for applications in sensors, medical diagnostics, environmental remediation, etc. The nanoparticles have a glassy poly(methyl methacrylate) (PMMA) core of ca. 40 nm radius and a cross-linked PNIPAM anionic shell with either AA or MA comonomers. The particles, p(N-AA) and p(MA-N), respectively, have the same total charge but different charge distributions. While the p(MA-N) particles have the negative charges preferentially distributed toward the inner shell, in the case of the p(N-AA) particles the charge extends more to the particle outer shell. The volume phase transition temperature (T(VPT)) of the particles is affected by the charge distribution and can be fine-tuned by controlling the electrostatic repulsion on the particle shell (using pH and ionic strength). By suppressing the particle charge we can also induce temperature-driven particle aggregation. 相似文献
93.
Flow visualisation is essential when trying to understand hydrodynamic equilibrium in continuous counter-current extraction (CCCE) (also known as dual-flow counter-current chromatography). The technique allows two immiscible liquid phases to be pumped through the spinning coil simultaneously in opposite directions. When this process was described previously it was assumed that the phases were evenly distributed throughout the coil. Visualisation studies by van den Heuvel and Sutherland in 2007 showed that this was not the case. A special centrifuge, where the coil is cantilevered so that the coil and the fluids inside the coil can be visualised, was used to study the distribution of the phases. Factorial experimental design was used to systematically study the effect of the starting conditions inside the coil on the phase distribution at equilibrium. For each experiment the eluted volumes and the volume of upper phase in the coil at the end of the experiment (at equilibrium) were recorded. In addition, two photographs were taken when the phases in the coil had reached equilibrium. One of these photographs was taken during the experiment when the phases were still being pumped through and one when the flow was stopped. The systematic experiments showed that the initial phase inside the coil has no effect on the phase distribution achieved at equilibrium. Statistical analysis also showed that the lower phase flow rate has double the effect on the phase distribution compared to the upper phase flow rate. From these visualisation studies, it can be concluded that the balance of the phases flowing through the coil at equilibrium is complex. The volumes of upper and lower phase and how they are distributed does influence the separation. It is important therefore to understand the relationship between respective flow rates and the phase distribution if peak elution is to be accurately predicted. 相似文献
94.
Havenith RW De Proft F Jenneskens LW Fowler PW 《Physical chemistry chemical physics : PCCP》2012,14(28):9897-9905
Ring currents calculated in the ipsocentric CTOCD-DZ formalism are presented for four representative metallabenzenes, compounds in which a benzene CH group is formally replaced by a transition metal atom with ligands. Aromaticity is probed using ring currents computed using non-relativistic and relativistic orbitals (derived with relativistic effective core potentials or ZORA). Maps computed at different levels of relativistic theory turn out to be similar, showing that orbital nodal character is the main determinant of ring current. Diatropic/paratropic global ring currents in these compounds, and also circulations localised on the metal centre, are interpreted in terms of contributions of localised π-type orbitals and metal d-orbitals, respectively. All four considered metallabenzenes should be regarded as 6π electron species, despite the fact that three support diatropic ('aromatic') ring currents and one a paratropic ('anti-aromatic') current. The current-density maps determine the correct way to count electrons in these species: differential occupation of d-orbitals of formal π-symmetry contributes to circulation on the metal centre, but not around the benzenoid ring. The overall trend from strongly diatropic to weakly paratropic ring currents along the series 1 to 4 is explained by the increasing strength of interaction between formally non-bonding orbitals on the metal centre and C(5)H(5) moiety, which together make up the six-membered ring. 相似文献
95.
96.
Elgersma RC Meijneke T de Jong R Brouwer AJ Posthuma G Rijkers DT Liskamp RM 《Organic & biomolecular chemistry》2006,4(19):3587-3597
The incorporation of a single beta-aminoethane sulfonyl amide moiety in a highly amyloidogenic peptide sequence resulted in a complete loss of amyloid fibril formation. Instead, supramolecular folding morphologies were observed. Subsequent chemoselective N-alkylation of the sulfonamide resulted in amphiphilic peptide-based hydrogelators. It was found that variation of merely the alkyl chain induced a dramatic variation in aggregation motifs such as helical ribbons and tapes, ribbons progressing to closed tubes, twisted lamellar sheets and entangled/branched fibers. 相似文献
97.
98.
99.
Sander?Dommers Cristian?Giardinà Remco?van?der?Hofstad 《Journal of statistical physics》2010,141(4):638-660
We study a ferromagnetic Ising model on random graphs with a power-law degree distribution and compute the thermodynamic limit
of the pressure when the mean degree is finite (degree exponent τ>2), for which the random graph has a tree-like structure. For this, we closely follow the analysis by Dembo and Montanari
(Ann. Appl. Probab. 20(2):565–592, 2010) which assumes finite variance degrees (τ>3), adapting it when necessary and also simplifying it when possible. Our results also apply in cases where the degree distribution
does not obey a power law. 相似文献
100.