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51.
Transitions of tethered polymer chains: a simulation study with the bond fluctuation lattice model 总被引:1,自引:0,他引:1
A polymer chain tethered to a surface may be compact or extended, adsorbed or desorbed, depending on interactions with the surface and the surrounding solvent. This leads to a rich phase diagram with a variety of transitions. To investigate these transitions we have performed Monte Carlo simulations of a bond fluctuation model with Wang-Landau and umbrella sampling algorithms in a two-dimensional state space. The simulations' density-of-states results have been evaluated for interaction parameters spanning the range from good- to poor-solvent conditions and from repulsive to strongly attractive surfaces. In this work, we describe the simulation method and present results for the overall phase behavior and for some of the transitions. For adsorption in good solvent, we compare with Metropolis Monte Carlo data for the same model and find good agreement between the results. For the collapse transition, which occurs when the solvent quality changes from good to poor, we consider two situations corresponding to three-dimensional (hard surface) and two-dimensional (very attractive surface) chain conformations, respectively. For the hard surface, we compare tethered chains with free chains and find very similar behavior for both types of chains. For the very attractive surface, we find the two-dimensional chain collapse to be a two-step transition with the same sequence of transitions that is observed for three-dimensional chains: a coil-globule transition that changes the overall chain size is followed by a local rearrangement of chain segments. 相似文献
52.
Huber K Witte T Hollmann J Keuker-Baumann S 《Journal of the American Chemical Society》2007,129(5):1089-1094
A new tool is presented to control formation of Ag nanoparticles. Small amounts of silver ions were added to dilute solutions of long-chain sodium polyacrylates (NaPA). Four NaPA samples covering a molar mass regime of 97 kD < or = Mw < or = 650 kD have been used. With amounts of added Ag(+) as low as 1-2% of the COO(-) groups of the polyanionic chains, significant changes could already be induced in the NaPA coils with 650 kD. If the NaPA concentration was kept below 0.1 g/L, the coils with 650 kD exhibited a significant coil shrinking in stable solutions. At larger NaPA concentrations, addition of Ag+ initiates an aggregation of the polyacrylate coils toward compact structures. Coil shrinking and aggregation was revealed by means of time-resolved static light scattering. If exposed to UV-radiation, small Ag particles formed within the shrunken anionic polyacrylate coils. The Ag nanoparticles were identified by means of an enhanced light scattering and a characteristic plasmon absorption band around 410 nm. No such Ag particle formation could be observed even at 5 times larger concentrations of Ag(+) and NaPA if the two smallest polyacrylate samples have been used under otherwise equal conditions. This molar mass sensitive response of NaPA to Ag(+)-addition suggests an interesting phenomenon: if the coil size of the NaPa chains, which act as Ag(+) collectors, is large enough, local Ag(+) concentration in these coil-shaped Ag(+) containers exceeds a critical value, and irradiation with UV generates Ag nanoparticles. 相似文献
53.
H.A. Di Rado P.A. Beneyto J.L. Mroginski A.M. Awruch 《Mathematical and Computer Modelling》2009,49(5-6):1058-1070
The main scope of this paper is to present a fully coupled numerical model for isothermal soil consolidation analysis based on a combination of different stress states. Being originally a non-symmetric problem, it may be straightforward reduced to a symmetric one, and general guidelines for the conditions in which this reduction may be carried out, are addressed. Non-linear saturation–suction and permeability-suction functions were incorporated into a Galerkin approach of the non-saturated soil consolidation problem, which was solved using the finite element method.In order to validate the model, various examples, for which previous solutions are known, were solved. The use of either a strongly non-linear and non-symmetric formulation or a simple symmetric formulation with accurate prediction in deformation and pore-pressures is extremely dependent on the soil characteristic curves and their derivatives and this aspect is taken into account in the present mathematical approach. The emergent coupling effects may be easily uncoupled in the computer model by merely recasting some coefficients of the discrete equation system. 相似文献
54.
Fekete A Frommberger M Ping G Lahaniatis MR Lintelman J Fekete J Gebefugi I Malik AK Kettrup A Schmitt-Kopplin P 《Electrophoresis》2006,27(5-6):1237-1247
A method for the determination of low-molecular-weight amines from indoor and ambient air was developed using a concentration device followed by CE coupled with indirect spectrophotometric and mass spectrometric detection that enables a reliable, rapid-response and easy-to-operate method. In indirect detection method, the selected amines were separated from interfering metal ions and amino alcohols present in the samples with an imidazole-based buffer with ethanol and EDTA as modifier. By replacing imidazole with ammonium, the final buffer was applicable for MS detection for the analytes with m/z higher than 50. A novel monolithic polymer material based on poly(methacrylate-acrylate) copolymer was developed for sampling short-chain amines from the gaseous phase. The selected analysis conditions were applied to quantify the selected short-chain amines with detection limits for the whole procedure determined between 1 and 2 microg/filter when 40 L air was sampled with 1 L/min velocity. Improved linearity and precision were obtained when the raw, time-scaled electropherogram data were transformed into mobility-scale applied for the determination of the performance characteristics of the methods. The applicability of the process of data transformation into the mobility scale was demonstrated by studying the matrix effect of water-miscible metal working fluid (stable water-oil emulsion) and of ambient air as real samples. CE-indirect UV and CE-MS, combined with the possibility of rapid air sampling, can be useful for the estimation of short-term exposure of the selected biogenic amines. 相似文献
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Ruud Peters Ingrid Elbers Anna Undas Eelco Sijtsma Sophie Briffa Pauline Carnell-Morris Agnieszka Siupa Tae-Hyun Yoon Loïc Burr David Schmid Jutta Tentschert Yves Hachenberger Harald Jungnickel Andreas Luch Florian Meier Jovana Kocic Jaeseok Kim Byong Chon Park Barry Hardy Colin Johnston Kerstin Jurkschat Jrg Radnik Vasile-Dan Hodoroaba Iseult Lynch Eugenia Valsami-Jones 《Molecules (Basel, Switzerland)》2022,27(15)
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