两嵌段共聚高分子链通过薄膜上纳米孑孔隙输运的研究

针对两嵌段高分子链的跨膜输运过程,分别给出与不同输运次序相对戍的高分子链的自由能,进而通过求解Fokker-Planck方程并在不同条件下对平均首次通过时间进行了数值计算.计算结果表明,当共聚高分子链由良溶剂区向不良溶剂区输运时,不能发生线团一链滴转变的链首先输运总是有利于整个高分子链的输运.而在给定输运次序的情况下,化学势、线团一链滴转变、共聚链的组成以及输运速率等因素对输运时间可产生显著影响.相关研究结果可为调控实际生物高分子链的输运时间提供可能的理论线索.     

Mapping a homopolymer onto a model fluid

We describe a linear homopolymer using a grand canonical ensemble formalism, a statistical representation that is very convenient for formal manipulations. We investigate the properties of a system where only next neighbor interactions and an external, confining, field are present and then show how a general pair interaction can be introduced perturbatively, making use of a Mayer expansion. Through a diagrammatic analysis, we shall show how constitutive equations derived for the polymeric system are equivalent to the Ornstein-Zernike and Percus-Yevick equations for a simple fluid and find the implications of such a mapping for the simple situation of Van der Waals mean field model for the fluid.     

Formation of a tris-capsule and a tris-carceplex from a cyclic six-bowl assembly

A macrocycle composed of six cavitands was assembled into a tris-capsule and a tris-carceplex, each of which encapsulates three guest molecules.     

Synthesis of a tetraazacyclotetradecadiene and a pentaazacyclotetradecatriene

Useful procedures for preparing a novel tetraazacyclotetradecadiene and a pentaazacyclotetradecatriene are reported. J. Heterocyclic Chem., 14, 1097 (1977)     

Wetting of a drop on a sphere

In this work, the equilibrium morphology of a drop on a sphere is analyzed as a function of the contact angle and drop volume experimentally and with analytical effective interfacial energy calculations. Experimentally, a drop on a sphere geometry is realized in an oil bath by placing a water drop on a sphere coated with a dielectric, of which the radii of curvature are comparable with that of the drop. Electrowetting (EW) is used to change the contact angle of the water drop on the sphere. To validate the applicability of EW and the Lippman-Young equation on nonflat surfaces, we systematically investigate the response of the contact angle to the applied voltage (EW response) for various drop volumes and compared the results with the case of a planar surface. The effective interfacial energy of two competing morphologies, namely, the spherically symmetric "completely engulfing" and "partially engulfing" morphologies are calculated analytically. The analytical calculations are then compared to the experimental results to confirm which morphology is energetically more favored for a given contact angle and drop volume. Our findings indicate that the "partially engulfing" morphology is always the energetically more favorable morphology.     

Constructing a multidimensional free energy surface like a spider weaving a web

Complete free energy surface in the collective variable space provides important information of the reaction mechanisms of the molecules. But, sufficient sampling in the collective variable space is not easy. The space expands quickly with the number of the collective variables. To solve the problem, many methods utilize artificial biasing potentials to flatten out the original free energy surface of the molecule in the simulation. Their performances are sensitive to the definitions of the biasing potentials. Fast‐growing biasing potential accelerates the sampling speed but decreases the accuracy of the free energy result. Slow‐growing biasing potential gives an optimized result but needs more simulation time. In this article, we propose an alternative method. It adds the biasing potential to a representative point of the molecule in the collective variable space to improve the conformational sampling. And the free energy surface is calculated from the free energy gradient in the constrained simulation, not given by the negative of the biasing potential as previous methods. So the presented method does not require the biasing potential to remove all the barriers and basins on the free energy surface exactly. Practical applications show that the method in this work is able to produce the accurate free energy surfaces for different molecules in a short time period. The free energy errors are small in the cases of various biasing potentials. © 2017 Wiley Periodicals, Inc.     

Motion of a drop on a solid surface due to a wettability gradient

The hydrodynamic force experienced by a spherical-cap drop moving on a solid surface is obtained from two approximate analytical solutions and used to predict the quasi-steady speed of the drop in a wettability gradient. One solution is based on approximation of the shape of the drop as a collection of wedges, and the other is based on lubrication theory. Also, asymptotic results from both approximations for small contact angles, as well as an asymptotic result from lubrication theory that is good when the length scale of the drop is large compared with the slip length, are given. The results for the hydrodynamic force also can be used to predict the quasi-steady speed of a drop sliding down an incline.     

Hydrodynamic force on a microparticle approaching a wall in a nanoparticle dispersion: observation of a separation-dependent effective viscosity

Colloid probe atomic force microscopy was used to measure the hydrodynamic force exerted on a 30-μm-diameter silica particle being moved toward or away from a silica plate in aqueous dispersions of 22-nm-diameter silica nanoparticles (6 or 8 vol %). Upon comparing the measured force to predictions made using the well-known expression of Cox and Brenner (Cox, R. G.; Brenner, H. Chem. Eng. Sci.1967, 22, 1753-1777) assuming a constant viscosity equal to that of the bulk dispersion, the measured drag force was found to become significantly less than that predicted at smaller particle-plate separation distances (e.g., <500 nm). A recent theoretical paper by Bhattacharya and Blawzdziewicz (Bhattacharya, S.; Blawzdziewicz, J. J. Chem. Phys.2008, 128, 214704) predicted that in a solution of dispersed nanoparticles the effective viscosity characterizing the hydrodynamic force on the particle should vary from that of the solvent at contact to that of the bulk dispersion at large separations. By adjusting the viscosity in the Cox and Brenner expression to make the predicted hydrodynamic force match that measured (i.e., the effective viscosity), a curve showing these exact characteristics was obtained. The effective viscosity profile was not a function of particle speed, and changes in the effective viscosity extended to separation distances of as large as 2 μm (nearly 100 times the hard diameter of the nanoparticles). These results suggest that in the range of typical colloidal forces (on the order of 100 nm), the dynamics of particle motion in such systems are determined by the viscosity of the solvent and not that of the bulk dispersion.     

Impedance of a passive iron electrode in a solution containing a reducing agent

Frequency dependences of impedance of a passive iron electrode in 0.5 M Na₂SO₄ solutions with and without 0.01 M K₄[Fe(CN)₆] are obtained by a pulsed method and the Fourier transform. At 1–1000 Hz, the results in 0.5 M Na₂SO₄ satisfactorily agree with our previous results obtained by a lock-in method. With the [Fe(CN)₆]^4- ions present, the impedance decreases faster at lower frequencies. The impedance of the oxide film/solution interface relaxes longer the film impedance. These conclusions are similar to those obtained earlier.Translated from Elektrokhimiya, Vol. 41, No. 1, 2005, pp. 97–101.Original Russian Text Copyright © 2005 by Klyuev, Rotenberg, Batrakov.To the Centennial of B.N. Kabanov.     

Taming Mars with a tent and a tunnel: creation of a biosphere-city

An unconventional site-specific outdoor utility sculpture, used as a Strait of Gibraltar stopper, may soon store unwanted Earth-atmosphere derived wastes (mineralized CO2 and CFCs) for hundreds of years. Such a Land Art processing facility, an anti-global warming/cooling antidote, is an appropriate macro-engineering response to allegedly impending human survival macro-problems.     

Preparation of a lipid a derivative that contains a 27-hydroxyoctacosanoic acid moiety

[structure: see text] A general synthetic strategy for long-chain omega-1 hydroxy fatty acids has been developed, which employs as a key reaction step a cross metathesis between omega-unsaturated ester and 3-butene-2-ol. The resulting lipids were used for the preparation of lipid A derivatives of Rhizobium sin-1, which have the ability to inhibit the E. coli LPS-dependent synthesis of tumor necrosis factor by human monocytes.     

Synthesis of (+)-uniflorine a: a structural reassignment and a configurational assignment

The total synthesis of (+)-uniflorine A has allowed for the structural reassignment and the configurational assignment of the alkaloid (-)-uniflorine A from a 1,2,6,7,8-pentahydroxyindolizidine structure to (-)-(1 R,2 R,3 R,6 R,7 S,7a R)-1,2,6,7-tetrahydroxy-3-hydroxymethylpyrrolizidine (6- epi-casuarine).     

Arylation of a carbanion derived from a pyridazine; a route to a functionalized aren

1,4-Dichlorobenzene(cyclopentadienyl)iron(II) hexafluorophosphate reacts with the carbanion derived from 3-ethoxy-6-methylpyridazine N-oxide to give a Yanovsky-type adduct.     

Cation-pi interactions of a thiocarbonyl group and a carbonyl group with a pyridinium nucleus

Attractive interactions between a thiocarbonyl group and a pyridinium nucleus, and between a carbonyl group and a pyridinium nucleus have been proven by (1)H and (13)C NMR studies, UV-vis spectral analyses, and X-ray crystallographic analyses of nicotinic amides 1 and 3, and pyridinium salts 2 and 4. Comparison of the Deltadelta values, which are the differences in the chemical shifts with reference compounds 5 or 6, showed that the absolute Deltadelta values of 2 and 4 are much larger than those of 1 and 3. In the UV-vis spectra, the n-->pi absorption of the C=S group of 2a exhibited a significant blue shift in CHCl(3). X-ray crystallographic analysis of 1-4 clearly showed that the C=S group of 2a and the C=O group of 4 are very close to the pyridinium moiety compared to the case of 1 and 3. In addition, the X-ray crystal packing structure of 2a showed the C=S group is sandwiched between two pyridinium rings. These experimental results strongly suggested the existence of attractive (C=S)...Py(+) and (C=O)...Py(+) interactions in solution and in crystal. The optimized geometries of 1 and 2 calculated at the HF/6-311G level are in good agreement with their X-ray geometries. MP2/6-311G calculations for the model systems of pyridinium salts 2 and 4 predicted that the electrostatic and induction energies are the major source of the attractive interactions. Since the larger contribution of electrostatic and induction interactions are characteristic features of cation-pi interactions, the (C=S)...Py(+) and (C=O)...Py(+) interactions would be classified as a cation-pi interaction.     

Thermal properties of a disc-like compound benzene-hexa-n-pentanoate: a precursor of a discotic mesogen

The heat capacity of a disk-like compound, benzene-hexa-n-pentanoate (BH5), a precursor of a discotic mesogen, has been measured by adiabatic calorimetry between 13 and 390 K. BH5 showed four different crystalline phases, but no liquid crystalline phase. Molar entropy and transition entropies were determined and compared with those of other homologues (BH6, BH7, and BH8). An odd-even effect with respect to the number of carbon atoms in the alkyl chain was observed for the cumulative entropies of the phase transitions occurring in the solid state. This effect is discussed by comparing with data for the n-alkanes. The molar entropies of the crystalline state, especially below 250 K, exhibited a peculiar 'pairing effect' between BH(2m- 1) and BH(2m), where m is an integer.     

Thermal properties of a disc-like compound benzene-hexa-n-pentanoate: a precursor of a discotic mesogen

The heat capacity of a disk-like compound, benzene-hexa-n-pentanoate (BH5), a precursor of a discotic mesogen, has been measured by adiabatic calorimetry between 13 and 390 K. BH5 showed four different crystalline phases, but no liquid crystalline phase. Molar entropy and transition entropies were determined and compared with those of other homologues (BH6, BH7, and BH8). An odd-even effect with respect to the number of carbon atoms in the alkyl chain was observed for the cumulative entropies of the phase transitions occurring in the solid state. This effect is discussed by comparing with data for the n-alkanes. The molar entropies of the crystalline state, especially below 250 K, exhibited a peculiar 'pairing effect' between BH(2m- 1) and BH(2m), where m is an integer.