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81.
The dynamics of low-dimensional Brownian particles coupled to time-dependent driven anisotropic heavy particles (mesogens) in a uniform bath (solvent) have been described through the use of a variant of the stochastic Langevin equation. The rotational motion of the mesogens is assumed to follow the motion of an external driving field in the linear response limit. Reaction dynamics have also been probed using a two-state model for the Brownian particles. Analytical expressions for diffusion and reaction rates have been developed and are found to be in good agreement with numerical calculations. When the external field driving the mesogens is held at constant rotational frequency, the model for reaction dynamics predicts that the applied field frequency can be used to control the product composition. 相似文献
82.
Park MK Deng S Advincula RC 《Langmuir : the ACS journal of surfaces and colloids》2005,21(12):5272-5277
We describe the formation and permeability of polyelectrolyte multilayer hollow-shell capsules by photo-cross-linking and controlled-release (fluorescence) studies. The hollow shells were prepared by alternate layer-by-layer (LbL) adsorption of photo-cross-linkable benzophenone modified poly(allylamine hydrochloride) and poly(sodium 4-styrenesulfonate) on polystyrene particles, followed by removing the core with tetrahydrofuran. Zeta potential measurements, fourier transform infrared spectroscopy, and transmission electron microscopy were used to verify the LbL process integrity. A model drug, rhodamine B (RB), was successfully loaded into the polyelectrolyte hollow capsules. The release kinetics of RB was investigated using fluorescence spectroscopy. The permeability of RB through the hollow shells was effectively controlled based on UV irradiation time. It was shown that the release of RB molecules can be controlled by the degree of cross-linking induced in the multilayer. 相似文献
83.
The native structure of fast-folding proteins, albeit a deep local free-energy minimum, may involve a relatively small energetic penalty due to nonoptimal, though favorable, contacts between amino acid residues. The weak energetic frustration that such contacts represent varies among different proteins and may account for folding behavior not seen in unfrustrated models. Minimalist model proteins with heterogeneous contacts--as represented by lattice heteropolymers consisting of three types of monomers--also give rise to weak energetic frustration in their corresponding native structures, and the present study of their equilibrium and nonequilibrium properties reveals some of the breadth in their behavior. In order to capture this range within a detailed study of only a few proteins, four candidate protein structures (with their cognate sequences) have been selected according to a figure of merit called the winding index--a characteristic of the number of turns the protein winds about an axis. The temperature-dependent heat capacities reveal a high-temperature collapse transition, and an infrequently observed low-temperature rearrangement transition that arises because of the presence of weak energetic frustration. Simulation results motivate the definition of a new measure of folding affinity as a sequence-dependent free energy--a function of both a reduced stability gap and high accessibility to non-native structures--that correlates strongly with folding rates. 相似文献
84.
pH-Sensitive bipolar ion-permselective films of polyelectrolyte multilayers were prepared by layer-by-layer (LbL) assembly and photo-cross-linking of benzophenone-modified poly(acrylic acid) (PAA-BP) and poly(allylamine hydrochloride) (PAH-BP). The multilayer structure and ionizable group composition was finely tuned by changing the pH of the dipping solution. This structure and composition was in turn "preserved" by photo-cross-linking, forming highly stable membrane films. Since PAA-BP and PAH-BP are weak polyelectrolytes, it is possible to control the number of unbound, un-ionized -COOH or -NH2 groups in the multilayer by changing the pH. Moreover, the pH of the deposited film also plays an important role in determining selective latter permselectivity. For example, PAA-BP/PAH-BP multilayers deposited from two pH conditions, pH = 3 (PAA-BP) and pH = 6 (PAH-BP), showed pH-switchable permselectivity for both cationic (pH = 10) and anionic (pH = 3) probe molecules in a single film. The system offers advantages in film stability and introducing reversible selective ion permeability over previous multilayer film and cross-linking methods. 相似文献
85.
An increase in the rates of activated processes with the coupling to the solvent has long been predicted through the phenomenological Langevin equation in the weak coupling regime. However, its direct observation in particle-based models has been elusive because the coupling typically places the processes in the spacial-diffusion limited regime wherein rates decrease with increasing friction. In this work, the forward and backward reaction rates of the LiNC<==>LiCN isomerization reaction in a bath of argon atoms at various densities have been calculated directly using molecular dynamics trajectories. The so-called Kramers turnover in the rate with microscopic friction is clearly visible, thus providing direct and unambiguous evidence for the energy-diffusion regime in which rates increase with friction. 相似文献
86.
Xia C Fan X Locklin J Advincula RC Gies A Nonidez W 《Journal of the American Chemical Society》2004,126(28):8735-8743
We report the synthesis and characterization of dendritic thiophene derivatives with their unique supramolecular assembly into 2-D crystals, nanowires, and nanoparticle aggregates. The structure and size of the dendrons and dendrimers have been confirmed with various techniques, such as NMR, SEC, and MALDI-TOF-MS. The mass values were consistent with the mass observed by MALDI-TOF-MS, whereas SEC measurements also gave useful information on the hydrodynamic volume of the individual dendrimers. The interesting electrooptical properties were highlighted by very broad absorption spectra and narrower fluorescence consistent with their electrochemical behavior. The self-organization of the dendrimers on the solid substrate is dependent on the nature of the substrate, preparation methods, and the molecule-molecule and molecule-substrate interactions. Thus, 14T-1 and 30T both formed globular aggregates on mica surface, while 14T-1 also formed nanowires on graphite surface. On the other hand, the larger 30T was observed to form 2-D crystalline structures. By varying the alkyl chain length attached to 14T-1, we were also able to obtain 2-D crystals on graphite. This showed that the different symmetry of packing for 30T and 14T-1 is also dependent on several factors, such as the molecular shape, size, and the presence of noncovalent intermolecular interactions. The results demonstrated the unique ability of thiophene dendrimers to form nanostructures on surfaces. 相似文献
87.
88.
Pérez de Alejo R Ruiz-Cabello J Cortijo M Rodriguez I Echave I Regadera J Arrazola J Avilés P Barreiro P Gargallo D Graña M 《Magnetic resonance imaging》2003,21(8):901-912
An accurate computer-assisted method able to perform regional segmentation on 3D single modality images and measure its volume is designed using a mixture of unsupervised and supervised artificial neural networks. Firstly, an unsupervised artificial neural network is used to estimate representative textures that appear in the images. The region of interest of the resultant images is selected by means of a multi-layer perceptron after a training using a single sample slice, which contains a central portion of the 3D region of interest.The method was applied to magnetic resonance imaging data collected from an experimental acute inflammatory model (T(2) weighted) and from a clinical study of human Alzheimer's disease (T(1) weighted) to evaluate the proposed method. In the first case, a high correlation and parallelism was registered between the volumetric measurements, of the injured and healthy tissue, by the proposed method with respect to the manual measurements (r = 0.82 and p < 0.05) and to the histopathological studies (r = 0.87 and p < 0.05). The method was also applied to the clinical studies, and similar results were derived of the manual and semi-automatic volumetric measurement of both hippocampus and the corpus callosum (0.95 and 0.88). 相似文献
89.
Dr. Rigoberto Barrios‐Francisco Tania Benítez‐Páez Dr. Marcos Flores‐Alamo Dr. Alma Arévalo Prof. Dr. Juventino J. García 《化学:亚洲杂志》2011,6(3):842-849
The current work describes the synthesis and full characterization of zerovalent nickel complexes of the type [(dippe)Ni(η2‐C,C‐Fn‐alkyne)] (dippe=1,2‐bis(di‐isopropylphosphino‐ethane), Fn‐alkyne=fluorinated aromatic alkyne, n=1, 3, 5; 3a , 3b , 3c ) and [{(dippe)Ni}2(μ2‐C,C‐Fn‐alkyne)] ( 4 ). Reactions with complexes 3a , 3b , 3c , and water as the hydrogen source, yield selective semihydrogenation of the bound alkyne to the corresponding alkene, accompanied by partial hydrodefluorination of the aromatic ring. Different alkynes were tested; on using the alkyne with five fluorine atoms over the aromatic ring, partial defluorination was achieved under the mildest reaction conditions, followed in reactivity by the alkyne with three fluorine atoms. The alkyne with only one fluorine atom was barely defluorinated. The use of triethylsilane as a sacrificial hydride source resulted in an overall increase in reactivity towards defluorination. 相似文献
90.
The temperature-ramped irreversible Langevin equation [A. V. Popov and R. Hernandez, J. Chem. Phys. 134, 244506 (2007)] has been seen to describe the nonequilibrium atomic oscillations of a nanorod dragged across a surface. The nanorod and surface consist of hydroxylated α-Al(2)O(3) layers as was studied earlier by Hase and co-workers [J. Chem. Phys. 122, 094713 (2005)]. The present approach corresponds to the reduced Frenkel-Kontorova-Tomlinson model in which only one element of the vibrational chain representing a surface layer is considered explicitly. The key new concept centers on a separation of the environment into two effective reduced-dimensional baths: an equilibrium bath arising from the thermostated vibrations of the crystal lattice and a nonequilibrium bath arising from driven oscillations at the contact between the nanorod and the surface. The temperature of the latter is defined by the mean energy of a representative atomic oscillator for a given layer. The temporal temperature fluctuations and the dependence of the static part of the temperature on the sliding velocity are close to those found in the MD simulations of Hase and co-workers. 相似文献