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Lignin is a potential biomass feedstock from plant material, but it is particularly difficult to economically process. Inspired by recent ball-milling results, state-of-the-art quantum mechanochemistry calculations have been performed to isolate and probe the purely mechanochemical stretching effect alone upon acid-catalyzed deconstruction of lignin. Effects upon cleavage of several exemplary simple ethers are examined first, and with low stretching force they all are predicted to cleave substantially faster, allowing for use of milder acids and lower temperatures. Effects upon an experimentally known lignin fragment model (containing the ubiquitous β-O-4 linkage) are next examined; this first required a mechanism refinement (3-step indirect cleavage, 1-step side reaction) and identification of the rate-limiting step under zero-force (thermal) conditions. Mechanochemical activation using very low stretching forces improves at first only yield, by fully shutting off the ring-closure side reaction. At only somewhat larger forces, in stark contrast, a switch in mechanism is found to occur, from 3-step indirect cleavage to the direct cleavage mechanism of simple ethers, finally strongly enhancing the cleavage rate of lignin. It is concluded that mechanochemical activation of the common β-O-4 link in lignin would improve the rate of its acidolysis via a mechanism switch past a low force threshold. Relevance to ball-milling experiments is discussed.  相似文献   
2.
Dynamic photoelasticity and strain-gage techniques are employed to study wave propagation and dynamic load transfer in granular media. The granular medium is modeled as one- and two-dimensional deterministic and random arrays of circular disks of polyester material Homalite 100. The dynamic loading is achieved by explosive excitation. The experimental data are analyzed to determine the wave velocities, to identify the characteristic load transfer paths, and to quantitatively obtain the dynamic contact forces in the granular assembly. It is observed that the wave-propagation and dynamic-load-transfer phenomenon depends on the disk diameter and the obliqueness and flexibility of the load-transfer paths. The wave speed drops significantly in the first few granules after which the decay is more gradual. The load transter is characterized by the contact length and the friction between the contacting granules. The peak loads drop as the distance of the contact points from the point of explosive loading increases. For two-dimensional wave propagation, the load-transfer paths and the magnitude of contacting forces depend on the angles made by the normals of the contacting disks at the contact point.  相似文献   
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The objective of the present study was to develop and validate a rapid and simple stability indicating analytical method for estimating Ilaprazole. Ilaprazole was subjected to different stress conditions prescribed by International Conference on Harmonization (ICH) such as hydrolysis, oxidation, photolytic and dry heat degradation conditions. The drug was very susceptible to degradation under hydrolysis and photolytic conditions, less susceptible to oxidation and stable under dry heat degradation condition. An acceptable separation of drug and its degradants was achieved by using a C-18 column and mobile phase composed of ammonium acetate buffer (pH 3.2)—acetonitrile (55: 45, v/v). Flow rate was 1 mL/min and detection wavelength was set at 303 nm. Retention time of drug was found to be 6.6 min and analysis can be completed within 10 min. The method was validated with respect to linearity, precision, accuracy, robustness, LOD and LOQ as per ICH. The method was linear (R2 = 0.996) in the range of 2.5–250 μg/mL. The recovery was in the range from 99.2–100.2%.  相似文献   
4.
Various staining techniques are commonly used in biomedical research to investigate cellular morphology. By inducing absorption of light, staining dyes change the intracellular refractive index due to the Kramers-Kronig relationship. We present a method for creating 2D maps of real and imaginary refractive indices of stained biological cells using their thickness and absorptance. We validate our technique on dyed polystyrene microspheres and quantify the alteration in refractive index of stained biological cells. We reveal that specific staining of individual organelles can increase their scattering cross-section by orders of magnitudes, implying a major impact in the field of biophotonics.  相似文献   
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