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601.
A new approach was developed to synthesize 1,4-oxazine and 1,4-oxazepine derivatives without solvent and metal. Regioselective cyclization occurred to afford exclusively the exo-dig product, and stereochemistry was studied by circular dichroism and specific optical rotation techniques. The Grignard reaction is a key synthetic step to produce high diastereomeric compounds via Cram's rule and was well supported by DFT calculations. A hydroalkoxylation mechanism was proposed and supported by DFT calculations. 相似文献
602.
Stengel F Baldwin AJ Bush MF Hilton GR Lioe H Basha E Jaya N Vierling E Benesch JL 《Chemistry & biology》2012,19(5):599-607
Small heat-shock proteins (sHSPs) are molecular chaperones that prevent irreversible aggregation through binding nonnative target proteins. Due to their heterogeneity, these sHSP:target complexes remain poorly understood. We present a nanoelectrospray mass spectrometry analysis algorithm for estimating the distribution of stoichiometries comprising a polydisperse ensemble of oligomers. We thus elucidate the organization of complexes formed between sHSPs and different target proteins. We find that binding is mass dependent, with the resultant complexes reflecting the native quaternary architecture of the target, indicating that protection happens early in the denaturation. Our data therefore explain the apparent paradox of how variable complex morphologies result from the generic mechanism of protection afforded by sHSPs. Our approach is applicable to a range of polydisperse proteins and provides a means for the automated and accurate interpretation of mass spectra derived from heterogeneous protein assemblies. 相似文献
603.
Viyannalage L Lee V Dennis RV Kapoor D Haines CD Banerjee S 《Chemical communications (Cambridge, England)》2012,48(42):5169-5171
Anisotropic Mg nanowires have been successfully prepared by electrocrystallization of Grignard's reagents thought to proceed via a modified faces, steps, and kinks (FSK) mechanism. Mg nanoparticles with roughly hexagonal shapes have also been obtained via chemical reduction of the same Grignard's reagents. 相似文献
604.
Maiti N Thomas S Jacob JA Chadha R Mukherjee T Kapoor S 《Journal of colloid and interface science》2012,374(1):141-149
Electric field-induced assembly of biological and synthetic particles has proven useful in two- and three-dimensional fabrication of composite materials, microwires, photonic crystals, artificial tissues, and more. Biological particles are typically irregularly shaped, and using non-spherical synthetic particles has the ability to expand current applications. However, there is much to be understood about the dielectrophoretic (DEP) interaction that takes place between particles of general shape. In this work, we numerically study the DEP interaction between two prolate spheroid particles suspended in an unbounded fluid. The boundary-element method (BEM) is applied to solve the coupled electric field, Stokes flow, and particle motion, and the DEP forces are obtained by integrating the Maxwell stress tensor over the particle surfaces. Effects of the initial configuration and aspect ratio are investigated. Results show that the particles go through a self-rotation process, that is, electro-orientation, while translating slowly to form a chain pair. The final formation resembles the chaining pattern observed previously in experiments using densely distributed ellipsoidal particles. Thus, the transient behavior and particle-particle interaction exhibited in the current study could be used as the fundamental mechanism to explain the phenomenon in the experiment. 相似文献
605.
Dinesh Kumar Inder Pal Singh Kapoor Gurdip Singh Nidhi Goel Udai Pratap Singh 《Journal of Thermal Analysis and Calorimetry》2012,107(1):325-334
Recent work has described the preparation and characterization of the two complexes [Fe2(C10H8N2)4O(OH2)2](NO3)4 and [Co(C10H8N2)3]2[Co(OH2)6]·7(OH2) (NO3)8 in which both the nitrogen atoms of 2,2′-bipyridine are directly bonded with the metals. Their structures were determined
by single-crystal X-ray diffraction at 296 K. Thermolysis of these complexes has been detailed by the use of TG–DTA and ignition
delay measurements. Kinetics of thermal decomposition has also been established. Model free isoconversional and model fitting
kinetic approaches have been applied to isothermal TG data for the decomposition of these complexes. 相似文献
606.
Booker JE Boto A Churchill GH Green CP Ling M Meek G Prabhakaran J Sinclair D Blake AJ Pattenden G 《Organic & biomolecular chemistry》2006,4(22):4193-4205
In model studies towards the quaternary centre at the heart of diazonamide A (early structure 2; revised structure 1), cyclisations of the alkene-substituted iodoaryls 4, 13, 18 and 23, under Heck reaction conditions, were shown to lead to the corresponding benzodihydrofuran 5, benzofuranone 14 and the oxindoles 19 and 24 respectively, in 50-80% yield. Further manipulation of the benzodihydrofuran 5 then led to the intermediates 30, 33 and 39, which make up parts of the oxazole-indole heterocyclic core in diazonamide A. Attempts to perform a corresponding 13-exo-trig Heck cyclisation from the precursor 46a, prepared from 44 and 45, leading to 47 were not successful. A similar outcome was obtained during attempts to effect Heck cyclisations from the ester 57 and the related ether 59. Treatment of the chromene-substituted iodoaryl 62 with Pd(OAc)2, PPh3 and Ag2CO3 led to the spirocycle 64 as a crystalline solid. X-Ray crystal structure analysis established that the quaternary centre in 64 had the same configuration as that present in diazonamide A (1). 相似文献
607.
Jaya Casukhela Kameswarrao S. Casukhela Hussain Elalaoui-Talibi 《Journal of Theoretical Probability》2006,19(4):899-909
Consider a simple point process N on the line, and let be its compensator. We use a result of Kallenberg (1990, Probab. Theory Relat. Fields
86, 167–202) to give a new approach to estimate the total variation distance between the distributions of N and that of a Poisson process when has small jump sizes. 相似文献
608.
Mahendra P. Kapoor Masamitsu Moriwaki Katsuhiko Minoura Derek Timm Aya Abe Kento Kito 《Molecules (Basel, Switzerland)》2022,27(17)
Flavonoids are biologically active natural products of great interest for their potential applications in functional foods and pharmaceuticals. A hesperetin-7-O-glucoside inclusion complex with β-cyclodextrin (HEPT7G/βCD; SunActive® HCD) was formulated via the controlled enzymatic hydrolysis of hesperidin with naringinase enzyme. The conversion rate was nearly 98%, estimated using high-performance liquid chromatography analysis. The objective of this study was to investigate the stability, solubility, and spectroscopic features of the HEPT7G/βCD inclusion complex using Fourier-transform infrared (FTIR), Raman, ultraviolet–visible absorption (UV–vis), 1H- and 13C- nuclear magnetic resonance (NMR), differential scanning calorimetry (DSC), liquid chromatography/mass spectroscopy (LC–MS), scanning electron microscopy (SEM), and powdered X-ray diffraction (PXRD) spectroscopic techniques including zeta potential, Job’s plot, and phase solubility measurements. The effects of complexation on the profiles of supramolecular interactions in analytic features, especially the chemical shifts of β-CD protons in the presence of the HEPT7G moiety, were evaluated. The stoichiometric ratio, stability, and solubility constants (binding affinity) describe the extent of complexation of a soluble complex in 1:1 stoichiometry that exhibits a greater affinity and fits better into the β-CD inner cavity. The NMR spectroscopy results identified two different configurations of the HEPT7G moiety and revealed that the HEPT7G/βCD inclusion complex has both –2S and –2R stereoisomers of hesperetin-7-O-glucoside possibly in the –2S/–2R epimeric ratio of 1/1.43 (i.e., –2S: 41.1% and –2R: 58.9%). The study indicated that encapsulation of the HEPT7G moiety in β-CD is complete inclusion, wherein both ends of HEPT7G are included in the β-CD inner hydrophobic cavity. The results showed that the water solubility and thermal stability of HEPT7G were apparently increased in the inclusion complex with β-CD. This could potentially lead to increased bioavailability of HEPT7G and enhanced health benefits of this flavonoid. 相似文献
609.
Niranjana Jaya Prakash Supriya Sanatkumar Sarkar Balasubramanian Kandasubramanian 《Macromolecular bioscience》2023,23(6):2200573
The utilization of implantable devices beseeches highly invasive surgeries considering the adversaries in the insertion of large, impliable devices through the body channels, which necessitate the development of implantable devices using biocompatible shape memory polymers. Silk displays prodigious heterogeneity in its genetic structure and physical properties in accordance with the spinning and storage process, where proteins undergo folding and unfolding. The stimuli-responsive nature of silk can be explained with the help of the structural morphology and composition of the material, where the hydrogen bonds in β-sheet domains and amorphous region act as switch points and net points, respectively. This review provides a primary attempt to enswathe all the literature available to date on the stimuli-responsive nature of silk and silk-based materials as a natural and biodegradable alternative for commercially used synthetic shape memory materials taking their elastomeric nature and reduction in glass transition temperature into account. Further constitutive model using the continuum approach has been utilized to explain the anisotropic elasticity damping effect and plastic deformation based on the α-helix chains, β-sheets, and β-spiral structures. The practicability to develop biomedical devices such as patient-specific-injectable scaffolds, drug carriers, and artificial muscles has been encompassed in this article. 相似文献