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21.
Aiming at a synthesis of spiro[2.4]hepta-4,6-dienes with a carbon substituent at C-4, we investigated solvolysis reactions of the thiatricycle 2, obtained from spiro[2.4]hepta-4,6-diene (1) and thiophosgene by [4 + 2] cycloaddition. With methanol or ethanol a mixture of the esters 7 and 8 was formed. Desulfurization of the thionoesters 8 gave methyl and ethyl spiro[2.4]hepta-4,6-diene-4-carboxylate (10a,b). The corresponding alcohol (11) was prepared from 10b by LiAlH(4) reduction. Ethenetetracarbonitrile combined with the 4-substituted spiro[2.4]hepta-4,6-dienes to give the [4 + 2] cycloadducts 12a-c. Diels-Alder reaction between 11 and 2-chloroacrylonitrile afforded the spiro(bicyclo[2.2.1]hept-5-ene-7,1'-cyclopropane) derivative 14a that was transformed in three steps to rac-10-hydroxycamphor (17). This synthesis of a bornane derivative opens opportunity for variations and thus may find further applications. 相似文献
22.
A HPLC method was developed for the analysis of secoisolariciresinol diglucoside (SDG) and hydroxycinnamic acid glucosides in milled defatted flaxseed flour. Direct extraction by 1 M NaOH for 1 h at 20 degrees C resulted in a higher yield than that obtained by hydrolysis of alcoholic extracts. An internal standard, o-coumaric acid, was used and the method was found to be easy, fast, and with good repeatability. On dry matter basis, different samples of flaxseeds varied considerably in their content of (+)-SDG (11.9-25.9 mg/g), (-)-SDG (2.2-5.0 mg/g), p-coumaric acid glucoside (1.2-8.5 mg/g), and ferulic acid glucoside (1.6-5.0 mg/g). 相似文献
23.
Renato Fedele Dušan Jovanovi? Bengt Eliasson Padma K. Shukla 《Physics letters. A》2010,374(5):788-795
The possibility of the decomposition of the three-dimensional (3D) Gross-Pitaevskii equation (GPE) into a pair of coupled Schrödinger-type equations, is investigated. It is shown that, under suitable mathematical conditions, it is possible to construct the exact controlled solutions of the 3D GPE from the solutions of a linear 2D Schrödinger equation coupled with a 1D nonlinear Schrödinger equation (the transverse and longitudinal components of the GPE, respectively). The coupling between these two equations is the functional of the transverse and the longitudinal profiles. The applied method of nonlinear decomposition, called the controlling potential method (CPM), yields the full 3D solution in the form of the product of the solutions of the transverse and longitudinal components of the GPE. It is shown that the CPM constitutes a variational principle and sets up a condition on the controlling potential well. Its physical interpretation is given in terms of the minimization of the (energy) effects introduced by the control. The method is applied to the case of a parabolic external potential to construct analytically an exact BEC state in the form of a bright soliton, for which the quantitative comparison between the external and controlling potentials is presented. 相似文献
24.
[reaction: see text] Olefination of aliphatic dithioacetals with Grignard reagents is catalyzed by Ni(acac)(2) in the presence of an appropriate trialkylphosphine ligand. 相似文献
25.
Baldur Föhlisch Robert Flogaus Jutta Oexle Angelika Schädel 《Tetrahedron letters》1984,25(17):1773-1776
1,1-Dichloro- and 1,3-dichloro-2-alkanones react with 2-methylfuran in the presence of lithium perchlorate/triethylamine to form 2-chloro-1-methyl-8-oxabicyclo [3.2.1]oct-6-ene-3-ones predominantly. 相似文献
26.
J. Silverio E. Svensson Ann-Charlotte Eliasson G. Olofsson 《Journal of Thermal Analysis and Calorimetry》1996,47(5):1179-1200
In the present study, isothermal microcalorimetry was introduced as a tool to investigate properties of starch retrogradation during the first 24 h. The study was made on purified amylose and amylopectin from corn, as well as on native starches, such as wheat, potato, maize, waxy maize and amylomaize, differing in their amylose content. The results were obtained in the form ofP-t traces (thermal powervs. time), and integration of these traces gave a net exothermic enthalpy of reaction, caused by the crystallization of amylose and amylopectin. TheP-t traces reflected the quantities of amylose and amylopectin in the starch studied. Depending on the amylose content and the botanical source of the starch, the rate of crystallization of amylose was high and predominated over that of amylopectin during the first 5–10 h. The contribution from amylose crystallization to the measured exothermic enthalpy was very substantial during this period. After 10 h, amylose crystallized at a lower constant rate. During the first 24 h, amylopectin crystallized at a low steady rate. The exothermic enthalpies obtained by the isothermal microcalorimetric investigations during the first 24 h of retrogradation were generally low in relation to the endothermic melting enthalpies observed by differential scanning calorimetry (DSC) measurements after 24 h of storage. The discrepancies in enthalpy values between the two methods are discussed in relation to phase separation and the endothermic effects owing to the decrease in polymer-water interactions when polymer-rich regions in the starch gel separate. Besides the exothermic enthalpies obtained, theP-t traces also made it possible to study the initial gelation properties of amylose from different botanical sources. The present study further demonstrated that isothermal microcalorimetry can provide a possible way to investigate the antistaling effect of certain polar lipids, such as sodium dodecylsulphate (SDS) and 1-monolauroyl-rac-glycerol (GML), when added to starches of different botanical origin. The net exothermic heat of reaction for starch retrogradation during the first 24 h was decreased when GML or SDS was added to the starch gels. The recordedP-t traces also showed how the effect of the added lipid influenced different periods during the first 24 h of starch retrogradation, and that the effect depended mainly on the amylose content, the botanical source of the starch, and the type of lipid used. When GML or SDS was added to waxy maize, the isothermal microcalorimetric studies clearly indicated some interaction between amylopectin and the polar lipids. These results concerning the action of anti-staling agents are further discussed in relation to the helical inclusion complexes formed between amylose-polar lipid and amylopectin-polar lipid.The authors thank Eva Qvarnström at the Dept. of Thermochemistry and Eva Tjerneld at the Dept. of Food Technology for valuable practical assistance. Financial support was obtained from the Swedish Council for Forestry and Agricultural Research (SJFR) and the Swedish Farmer's Foundation for Agricultural Research (Stiftelsen Lantbruksforskning). 相似文献
27.
Colton D. Payne Bastian Franke Mark F. Fisher Fatemeh Hajiaghaalipour Courtney E. McAleese Angela Song Carl Eliasson Jingjing Zhang Achala S. Jayasena Grishma Vadlamani Richard J. Clark Rodney F. Minchin Joshua S. Mylne K. Johan Rosengren 《Chemical science》2021,12(19):6670
Head-to-tail cyclized peptides are intriguing natural products with unusual properties. The PawS-Derived Peptides (PDPs) are ribosomally synthesized as part of precursors for seed storage albumins in species of the daisy family, and are post-translationally excised and cyclized during proteolytic processing. Here we report a PDP twice the typical size and with two disulfide bonds, identified from seeds of Zinnia elegans. In water, synthetic PDP-23 forms a unique dimeric structure in which two monomers containing two β-hairpins cross-clasp and enclose a hydrophobic core, creating a square prism. This dimer can be split by addition of micelles or organic solvent and in monomeric form PDP-23 adopts open or closed V-shapes, exposing different levels of hydrophobicity dependent on conditions. This chameleonic character is unusual for disulfide-rich peptides and engenders PDP-23 with potential for cell delivery and accessing novel targets. We demonstrate this by conjugating a rhodamine dye to PDP-23, creating a stable, cell-penetrating inhibitor of the P-glycoprotein drug efflux pump.The cyclic peptide PDP-23 adopts a different structure depending on conditions. In water it forms a dimer, but can unfold allowing its hydrophobic core to interact with membranes. PDP-23 shows promise as a cell penetrating scaffold for drug delivery. 相似文献
28.
Starch-Enhanced Synthesis of Oxygenates from Methane and Carbon Dioxide Using Dielectric-Barrier Discharges 总被引:3,自引:0,他引:3
Ji-Jun Zou Yue-ping Zhang Chang-Jun Liu Yang Li Baldur Eliasson 《Plasma Chemistry and Plasma Processing》2003,23(1):69-82
In this work, starch has been used to enhance the oxygenate formation directly from methane and carbon dioxide using dielectric-barrier discharges (DBDs). The use of starch inhibits the formation of liquid hydrocarbons and significantly increases the selectivity of oxygenates. Oxygenates produced include primarily formaldehyde, methanol, ethanol, formic acid, and acetic acid. The total selectivity is about 10–40% with conversion of methane and carbon dioxide of about 20%. Lower methane feed concentration favors the production of oxygenates, and higher feed flow rate leads to higher selectivity of oxygenates in the presence of starch. 相似文献
29.
8-Oxabicyclo[3.2.1]oct-6-en-3-ones (5), easily available by [4+3]cycloaddition, were epoxidised at the CC double bond. The 3,9-dioxatricyclo[3.3.1.02,4]nonan-7-ones (6) thus obtained are rearranged on treatment with sodium ethoxide in ethanol to form 3-hydroxybenzaldehydes (8a-d) and 3-hydroxy-2,4,5-trimethylacetophenone (8e) in good yields. As intermediates of these rearrangements, 8-hydroxy-6-oxatricyclo [3.2.1.02,7]octan-3-ones are postulated ; the trimethyl derivative 7g and the 6-carba-derivatives 4a,b could be isolated. 相似文献
30.
The 1H and 13C NMR chemical shifts of dibenzo[b, f]pentalene and its 5,10-dimethyl derivative are presented and compared with those of the corresponding dilithium dianions. As probed by the relative 13C NMR chemical shifts, the charge distribution within the dianion system is clearly dependent on the actual ion pair state. This condition is demonstrated by varying the solvent and temperature. The polarization of charge towards the pentalene carbons, i.e. the preferred cation positions, is observed on going to tight ion pair conditions. Further support for this model is gained from 7Li NMR. The limitations of the use of 1H and 13C NMR chemical shifts to measure charge distributions within anion systems are discussed. 相似文献