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21.
Jacob Aboudi 《International Journal of Solids and Structures》2012,49(22):3113-3128
The temperature field generated by the sudden application of a far-field mechanical loading of a periodically layered composite with an interfacial crack or with a cracked layer parallel to the interfaces is determined. As a result of the crack’s existence, the periodicities of the structure and the thermoelastic field are lost. The complexity of the resulting problem is resolved by the combined application of the representative cell method and the full (two-way) dynamic thermomechanical equations. In the former analysis, due to the loss of periodicity the dynamic thermoelastic Green’s functions are generated, in conjunction with the double finite discrete Fourier transform. In the latter one, the transformed displacements and temperature are expressed by second-order expansions and the strong-form of the elastodynamic and energy equations together with the various interfacial and the so called Born–von Karman boundary conditions are imposed in the average sense (in the transform domain). The results exhibit the induced temperature field at any point in the plane of the crack. The generated temperature fields show the cooling and heating zones in both Mode I and Mode II deformations. In addition, the adiabatic assumption (according to which the heat conduction is a priori ignored) is assessed by comparing the computed temperature field with the corresponding one based on the full thermomechanical coupling. 相似文献
22.
Liane K. Soares Renata G. LaraRaquel G. Jacob Eder J. LenardãoDiego Alves Gelson Perin 《Tetrahedron letters》2014
We present herein our results on the nucleophilic addition of imidazole to a range of arylselanylalkynes by simple heating in DMF without any additives to give (Z)-1-(1-organyl-(2-arylselanyl)vinyl)-1H-imidazoles. The reactions were performed under mild conditions with a range of arylselanylalkynes in good yields and with high regio- and stereoselectivity to give the respective (Z)-arylselanyl alkene as the only isomer. 相似文献
23.
pH‐controlled reaction divergence of decarboxylation versus fragmentation in reactions of dihydroxyfumarate with glyoxylate and formaldehyde: parallels to biological pathways 下载免费PDF全文
Christopher J. Butch Jing Wang Jiande Gu Rebeca Vindas Jacob Crowe Pamela Pollet Leslie Gelbaum Jerzy Leszczynski Ramanarayanan Krishnamurthy Charles L. Liotta 《Journal of Physical Organic Chemistry》2016,29(7):352-360
The reactions of dihydroxyfumarate with glyoxylate and formaldehyde exhibit a unique pH‐controlled mechanistic divergence leading to different product suites by two distinct pathways. The divergent reactions proceed via a central intermediate (2,3‐dihydroxy‐oxalosuccinate, 3 , in the reaction with glyoxylate and 2‐hydroxy‐2‐hydroxymethyl‐3‐oxosuccinate, 14 , in the reaction with formaldehyde). At pH 7–8, products ( 7 , 8 , and 15 ) exclusively from a decarboxylation of the intermediate are observed, while at pH 13–14, products ( 9 , 10 , and 16 ) solely derived from a hydroxide‐promoted fragmentation of the intermediate are formed. The decarboxylative and fragmentation pathways are mutually exclusive and do not appear to coexist under the range of pH (7–14) conditions investigated. Herein, we employ a combination of quantitative 13C NMR measurements and density functional theory calculations to provide a rationale for this pH‐driven reaction divergence. These rationalizations also hold true for the reactions of dihydroxyfumarate produced in situ by the catalytic cyanide‐mediated dimerization of glyoxylate. In addition, the non‐enzymatic decarboxylation and fragmentation transformations of these central intermediates ( 3 and 14 ) appear to have intriguing parallels to the enzymatic reactions of oxalosuccinate and formation of glyceric acid derivatives in extant metabolism – the high and low pH mimicking the precise control exerted by the enzymes over reaction pathways. Copyright © 2016 John Wiley & Sons, Ltd. 相似文献
24.
Jacob RE Laicher G Minard KR 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2007,188(2):357-366
In (3)He magnetic resonance images of pulmonary air spaces, the confining architecture of the parenchymal tissue results in a non-Gaussian distribution of signal phase that non-exponentially attenuates image intensity as diffusion weighting is increased. Here, two approaches previously used for the analysis of non-Gaussian effects in the lung are compared and related using diffusion-weighted (3)He MR images of mechanically ventilated rats. One approach is model-based and was presented by Yablonskiy et al., while the other approach utilizes the second order decay contribution that is predicted from the cumulant expansion theorem. Total lung coverage is achieved using a hybrid 3D pulse sequence that combines conventional phase encoding with sparse radial sampling for efficient gas usage. This enables the acquisition of nine 3D images using a total of only approximately 1 L of hyperpolarized (3)He gas. Diffusion weighting ranges from 0 s/cm(2) to 40 s/cm(2). Results show that the non-Gaussian effects of (3)He gas diffusion in healthy rat lungs are directly attributed to the anisotropic geometry of lung microstructure as predicted by the Yablonskiy model, and that quantitative analysis over the entire lung can be reliably repeated in time-course studies of the same animal. 相似文献
25.
26.
Miriam R. B. Porzberg Laust Moesgaard Catrine Johansson Udo Oppermann Jacob Kongsted Jasmin Mecinovi 《Molecules (Basel, Switzerland)》2022,27(3)
Epigenetic readout of the combinatorial posttranslational modification comprised of trimethyllysine and asymmetric dimethylarginine (H3K4me3R8me2a) takes place via biomolecular recognition of tandem Tudor-domain-containing protein Spindlin1. Through comparative thermodynamic data and molecular dynamics simulations, we sought to explore the binding scope of asymmetric dimethylarginine mimics by Spindlin1. Herein, we provide evidence that the biomolecular recognition of H3K4me2R8me2a is not significantly affected when R8me2a is replaced by dimethylarginine analogues, implying that the binding of K4me3 provides the major binding contribution. High-energy water molecules inside both aromatic cages of the ligand binding sites contribute to the reader–histone association upon displacement by histone peptide, with the K4me3 hydration site being lower in free energy due to a flip of Trp151. 相似文献
27.
Alyssa B. Sanders Jacob T. Zangaro Nakoa K. Webber Ryan P. Calhoun Elizabeth A. Richards Samuel L. Ricci Hannah M. Work Daniel D. Yang Kaitlyn R. Casey Joseph C. Iovine Gabriela Baker Taylor V. Douglas Sierra B. Dutko Thomas J. Fasano Sarah A. Lofland Ashley A. Rajan Mihaela A. Vasile Benjamin R. Carone Nathaniel V. Nucci 《Molecules (Basel, Switzerland)》2022,27(5)
Despite considerable advances in recent years, challenges in delivery and storage of biological drugs persist and may delay or prohibit their clinical application. Though nanoparticle-based approaches for small molecule drug encapsulation are mature, encapsulation of proteins remains problematic due to destabilization of the protein. Reverse micelles composed of decylmonoacyl glycerol (10MAG) and lauryldimethylamino-N-oxide (LDAO) in low-viscosity alkanes have been shown to preserve the structure and stability of a wide range of biological macromolecules. Here, we present a first step on developing this system as a future platform for storage and delivery of biological drugs by replacing the non-biocompatible alkane solvent with solvents currently used in small molecule delivery systems. Using a novel screening approach, we performed a comprehensive evaluation of the 10MAG/LDAO system using two preparation methods across seven biocompatible solvents with analysis of toxicity and encapsulation efficiency for each solvent. By using an inexpensive hydrophilic small molecule to test a wide range of conditions, we identify optimal solvent properties for further development. We validate the predictions from this screen with preliminary protein encapsulation tests. The insight provided lays the foundation for further development of this system toward long-term room-temperature storage of biologics or toward water-in-oil-in-water biologic delivery systems. 相似文献
28.
Shrinkage microporosity in cast aluminum was characterized utilizing the frequency dependence of ultrasonic attenuation caused by scattering from the pores. Measurements were made with the plate specimen immersed in water, and, by using a focused transducer, spatial resolution of about 2 mm was obtained. An accurate measure of attenuation was obtained by comparing the specimen’s ultrasonic signal with that from a pore-free reference specimen. Although the attenuation could be fitted using a single spherical pore size, better fits were obtained by assuming a lognormal distribution of spheres. Pore volume fraction inferred from the lognormal fits overestimates the actual volume fraction, determined from density measurements, by the same factor for all volume fractions. The actual volume fraction is overestimated by more than 100%, due to the complicated, nonspherical pore shapes, and must be taken into account to obtain accurate values of porosity. The strong correlation (r2=0.97) between ultrasonic and density-derived volume fractions permits reliable, nondestructive laboratory measurements of porosity. 相似文献
29.
Auger-Electron-Spectroscopy (AES) and Direct-Recoils-Spectrometry (DRS) were applied to study the interaction of O2 with a polycrystalline gadolinium surface, in the temperature range 300–670 K and oxygen pressure up to 2 × 10? 6 Torr. It has been found that initial uptake of oxygen, at coverage measurable by the techniques used here, results in rapid oxide island formation. The subsurface is believed to be a mixture of oxide particles and oxygen dissolved in the Gd metal, the latter being the mobile species, even at relatively low temperatures.Enhanced inward diffusion of oxygen starts as early as 420 K and dictates the surface oxygen concentration and effective thickness of the forming oxide. The oxygen accumulation rate at the near-surface region, as measured by the O(KLL) AES signal intensity, goes through a maximum as a function of temperature at 420 K. This is a result of the combination of still efficient oxygen chemisorption that increases surface occupation and slow inward diffusion. The thickest oxide, ~ 1.7 nm, is formed at 300 K and its effective thickness was found to decrease with increasing temperature (due to oxygen dissolution into the metal bulk).Diffusion coefficients of the oxygen dissolution into the bulk were evaluated for various temperatures utilizing models for infinitely thin oxide layer and thick oxide layer, respectively. The best fit under our experimental procedure was obtained by the thick layer model, and the coefficients that were calculated are D0 = 2.2 × 10? 16m2s? 1 and Ea = 46kJ/mol. 相似文献
30.
Eapen J Williams WC Buongiorno J Hu LW Yip S Rusconi R Piazza R 《Physical review letters》2007,99(9):095901
Transient hot-wire data on thermal conductivity of suspensions of silica and perfluorinated particles show agreement with the mean-field theory of Maxwell but not with the recently postulated microconvection mechanism. The influence of interfacial thermal resistance, convective effects at microscales, and the possibility of thermal conductivity enhancements beyond the Maxwell limit are discussed. 相似文献