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61.
Vermonden T Jena SS Barriet D Censi R van der Gucht J Hennink WE Siegel RA 《Macromolecules》2010,43(2):782-789
Hydrogel formation triggered by a change in temperature is an attractive mechanism for in situ gelling biomaterials for pharmaceutical applications such as the delivery of therapeutic proteins. In this study, hydrogels were prepared from ABA triblock polymers having thermosensitive poly(N-(2-hydroxypropyl) methacrylamide lactate) flanking A-blocks and hydrophilic poly(ethylene glycol) B-blocks. Polymers with fixed length A blocks (~22 kDA) but differing PEG-midblock lengths (2, 4 and 10 kDa) were synthesized and dissolved in water with dilute fluorescein isothiocyanate (FITC)-labeled dextrans (70 and 500 kDA). Hydrogels encapsulating the dextrans were formed by raising the temperature. Fluorescence recovery after photobleaching (FRAP) studies showed that diffusion coefficients and mobile fractions of the dextran dyes decreased upon elevating temperatures above 25 °C. Confocal laser scanning microscopy and cryo-SEM demonstrated that hydrogel structure depended on PEG block length. Phase separation into polymer-rich and water-rich domains occurred to a larger extent for polymers with small PEG blocks compared to polymers with a larger PEG block. By changing the PEG block length and thereby the hydrogel structure, mobility of FITC-dextran could be tailored. At physiological pH the hydrogels degraded over time by ester hydrolysis, resulting in increased mobility of the encapsulated dye. Since diffusion can be controlled according to polymer design and concentration, plus temperature, these biocompatible hydrogels are attractive as potential in situ gelling biodegradable materials for macromolecular drug delivery. 相似文献
62.
David Siegel Karsten Andrae Matthias Proske Cindy Kochan Matthias Koch Marcus Weber Irene Nehls 《Journal of chromatography. A》2010,1217(15):2206-2215
A novel, cost-efficient method for the analytical extraction of the Fusarium mycotoxin zearalenone (ZON) from edible oils by dynamic covalent hydrazine chemistry (DCHC) was developed and validated for its application with high performance liquid chromatography-fluorescence detection (HPLC-FLD). ZON is extracted from the edible oil by hydrazone formation on a polymer resin functionalised with hydrazine groups and subsequently released by hydrolysis. Specifity and precision of this approach are superior to liquid partitioning or gel permeation chromatography (GPC). DCHC also extracts zearalanone (ZAN) but not α-/β-zearalenol or -zearalanol. The hydrodynamic properties of ZON, which were estimated using molecular simulation data, indicate that the compound is unaffected by nanofiltration through the resin pores and thus selectively extracted. The method's levels of detection and quantification are 10 and 30 μg/kg, using 0.2 g of sample. Linearity is given in the range of 10–20,000 μg/kg, the average recovery being 89%. Bias and relative standard deviations do not exceed 7%. In a sample survey of 44 commercial edible oils based on various agricultural commodities (maize, olives, nuts, seeds, etc.) ZON was detected in four maize oil samples, the average content in the positive samples being 99 μg/kg. The HPLC-FLD results were confirmed by HPLC–tandem mass spectrometry and compared to those obtained by a liquid partitioning based sample preparation procedure. 相似文献
63.
The Toolkit for Accurate Scientific Software (TASS) is a suite of integrated tools for the formal verification of programs
used in computational science, including numerically-intensive message-passing-based parallel programs. While TASS can verify
a number of standard safety properties (such as absence of deadlocks and out-of-bound array indexing), its most powerful feature
is the ability to establish that two programs are functionally equivalent. These properties are verified by performing an
explicit state enumeration of a model of the program(s). In this model, symbolic expressions are used to represent the inputs
and the values of variables. TASS uses novel techniques to simplify the symbolic representation of the state and to reduce
the number of states explored and saved. The TASS front-end supports a large subset of C, including (multi-dimensional) arrays,
structs, dynamically allocated data, pointers and pointer arithmetic, functions and recursion, and other commonly used language
constructs. A number of experiments on small but realistic numerical programs show that TASS can scale to reasonably large
configurations and process counts. TASS is open source software distributed under the GNU Public License. The Java source
code, examples, experimental results, and reference materials are all available at . 相似文献
64.
An experimental and simulation investigation regarding the effect of various CRAMPS parameters (delays interleaved with the decoupling shape, z-rotation symmetry and offset frequency) on the DUMBO decoupling performance is presented using two model compounds, glycine and tyrosine·HCl. Although the conclusions of this work may be extended to the other homonuclear-decoupling schemes, this work focuses essentially on the effect of adding interleaved delays to DUMBO decoupling during the indirect dimension using different 2D pulse-scheme architectures. While the simulations revealed an increasing loss of the spectral resolution with longer delays (from 0 to 6 μs), the experimental 2D (1)H DUMBO NMR correlation spectra revealed that the inclusion of delays, during the indirect dimension, improves the (1)H resolution whether the z-rotation symmetry was used or not. The best experimental spectra are obtained when z-rotation symmetry and windows are combined. 相似文献
65.
66.
Scientific computing poses many challenges to formal verification, including the facts that typical programs: (1) are numerically-intensive, (2) are highly-optimized (often by hand), and (3) often employ parallelism in complex ways. Another challenge is specifying correctness. One approach is to provide a very simple, sequential version of an algorithm together with the optimized (possibly parallel) version. The goal is to show the two versions are functionally equivalent, or provide useful feedback when they are not. We present a new verification suite consisting of pairs of programs of this form. The suite can be used to evaluate and compare tools that verify functional equivalence. The programs are all in C and the parallel versions use the Message Passing Interface. They are simpler than codes used in practice, but are representative of real coding patterns (e.g., manager-worker parallelism, loop tiling) and present realistic challenges to current verification tools. The suite includes solvers for the 1-d and 2-d diffusion equations, Jacobi iteration schemes, Gaussian elimination, and N-body simulation. 相似文献
67.
68.
Alan Siegel 《Elemente der Mathematik》2001,56(1):17-20
69.
In this paper we consider the evolution by surface diffusion of material voids in a linearly elastic solid, focusing on the evolution of voids with large surface energy anisotropy. It is well known that models for the time evolution of similar material surfaces can become mathematically ill-posed when the surface energy is highly anisotropic. In some cases, this ill-posedness has been associated with the formation of corners along the interface. Here the ill-posedness is removed through a regularization which incorporates higher order terms in the surface energy. Spectrally accurate numerical simulations are performed to calculate the steady-state solution branches and time-dependent evolution of voids, with a particular emphasis on inferring trends in the zero regularization (c→0) limit. For steady voids with large anisotropy we find that apparent corners form as c→0. In the presence of elastic stresses σ the limiting corner angles are most often found to differ from angles found on the (σ=0) Wulff shape. For large elastic stresses we find that steady solutions no longer exist; instead the void steadily lengthens via a filamenting instability referred to as tip streaming. 相似文献
70.
Mafra L Santos SM Siegel R Alves I Paz FA Dudenko D Spiess HW 《Journal of the American Chemical Society》2012,134(1):71-74
We present an experimental NMR, X-ray diffraction (XRD), and computational study of the supramolecular assemblies of two crystalline forms of Ciprofloxacin: one anhydrate and one hydrate forming water wormholes. The resonance assignment of up to 51 and 54 distinct (13)C and (1)H resonances for the hydrate is reported. The effect of crystal packing, identified by XRD, on the (1)H and (13)C chemical shifts including weak interionic H-bonds, is quantified; (1)H chemical shift changes up to ~-3.5 ppm for CH···π contacts and ~+2 ppm (CH···O((-))); ~+4.7 ppm (((+))NH···O((-))) for H-bonds. Water intake induces chemical shift changes up to 2 and 5 ppm for (1)H and (13)C nuclei, respectively. Such chemical shifts are found to be sensitive detectors of hydration/dehydration in highly insoluble hydrates. 相似文献