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181.
Lipkowitz KB D'Hue CA Sakamoto T Stack JN 《Journal of the American Chemical Society》2002,124(47):14255-14267
A hypothesis concerning asymmetric induction by chiral catalysts is posited, tested, and found to be valid. The hypothesis states that chiral catalysts that are efficient at inducing asymmetry will have their region of maximum stereoinduction spatially congruent with the site of chemistry but inefficient catalysts will not. A simple mapping strategy (stereocartography) is used to assess where the region of maximum stereoinduction is located around a given catalyst. The protocol compares interaction energies between mirror image probes at each point in space around the catalyst being considered. The probes are models of the actual transition states of the reaction being catalyzed by a particular catalyst. The hypothesis was tested on three Diels-Alder reactions. Seventeen of the eighteen catalysts conform to the hypothesis. The idea of using this as a catalyst design tool is presented. 相似文献
182.
Cedric J. Stress Basilius Sauter Lukas A. Schneider Timothy Sharpe Dennis Gillingham 《Angewandte Chemie (International ed. in English)》2019,58(28):9570-9574
Here we show a seven‐step chemical synthesis of a DNA‐encoded macrocycle library (DEML) on DNA. Inspired by polyketide and mixed peptide‐polyketide natural products, the library was designed to incorporate rich backbone diversity. Achieving this diversity, however, comes at the cost of the custom synthesis of bifunctional building block libraries. This study outlines the importance of careful retrosynthetic design in DNA‐encoded libraries, while revealing areas where new DNA synthetic methods are needed. 相似文献
183.
184.
Summary From polyglycerol samples, pure standards of tri and tetraglycerol were obtained using a column chromatographic technique.
Polyglycerols were derivatised to trimethyl silyl derivatives to obtain gas chromatographic identification of all linear,
branched and cyclic diglycerol isomers and all linear and branched triglycerols. Moreover, quantitative gas chromatographic
analysis of the di-, tri- and tetraglycerol content of a polyglycerol sample was developed.
Finally a method to characterise, on a quantitative basis, the polyglycerol content of polyglycerol fatty acid esters was
developed. It consisted of saponifying the esters, without affecting the degree of polymerisation of the polyglycerols, followed
by gas chromatographic analysis of the isolated polyglycerol fraction. 相似文献
185.
Luisa Pellegrino Franca Marangoni Giovanna Muscogiuri Paolo DIncecco Guillaume T. Duval Cedric Annweiler Annamaria Colao 《Molecules (Basel, Switzerland)》2021,26(17)
Vitamin D is essential in assuring bone health at all stages of life, but its non-skeletal effects are also essential: This vitamin impacts the physiology of the immune system, skeletal muscles and adipose tissue, glucose metabolism, skin, cardiovascular and reproductive systems, neuro-cognitive functions and cell division. The incidence of vitamin D deficiency is widespread worldwide, at any age, in young and healthy subjects, as well as in pregnant women and the elderly population, due to several factors, including inadequate sunlight exposure, skin pigmentation and coverage, adiposity, lifestyle and low dietary intakes. To overcome this problem, the fortification of foods that are consumed on a daily basis, such as milk, is strongly advisable. This opinion paper aims to discuss, in a multidisciplinary way, the current evidence supporting the importance of vitamin D in health and disease and the role of milk as an optimal carrier of this vitamin, to promote adequate intakes, highlighting its unique physico-chemical characteristics linked to both fat globule membrane and casein micelle structure. Moreover, it addresses the impact of industrial processing and storage of consumption milk on the stability of these structures, thus in determining vitamin D bioavailability and the achievement of adequate intakes. 相似文献
186.
Volcke C Simonis P Durant F Thiry PA Lambin P Culot C Humbert C 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(14):4185-4190
The influence of chemical modification of scanning tunnelling microscopy tips on image contrast is studied. This technique is applied to the identification of an ester functional group, hardly visible otherwise. Self-assembled overlayers of wax esters [CH3-(CH2)14-CO-O-(CH2)15-CH3], adsorbed at the interface between highly oriented pyrolitic graphite and a solution of phenyloctane, are imaged. The gold tips used are chemically modified by 4-mercaptobenzoic acid and 4-mercaptotoluene. The stability of the ordered overlayers formed facilitates the reproducible set of images with submolecular resolution. This allows the identification of the layer regular structure and of other features within molecules, which can be unambiguously related to the fingerprints of the COO bond. Moreover, we are interested in finding evidence of molecular motions observed at domain boundaries. 相似文献
187.
Lion CJ Vasselin DA Schwalbe CH Matthews CS Stevens MF Westwell AD 《Organic & biomolecular chemistry》2005,3(21):3996-4001
Novel reaction pathways for the hypervalent iodine-mediated oxidation of bioactive phenols containing extended conjugated pi-systems are described. Oxidation of 4-hydroxystilbenes in methanol using a hypervalent iodine-based oxidant led to the formal 1,2-addition of methoxy groups across the central stilbene double bond. Treatment of the structurally related 4-hydroxyisoflavone with di(trifluoroacetoxy)iodobenzene leads to the surprising formation of 2,4'-dihydroxybenzil. Potential mechanisms for these new reaction pathways are discussed, and the X-ray crystal structure of 2,4'-dihydroxybenzil is presented. In contrast, oxidation of the corresponding 3-hydroxystilbenes and 3-hydroxyisoflavone led to conventional dienone oxidation products. The antitumour implications of these oxidation processes are briefly highlighted; the novel 4-substituted phenolic oxidation products were found to be inactive in terms of in vitro antitumour cellular activity, whereas the 3-substituted phenol products gave novel agents with potent and enhanced antitumour activity in the HCT 116 cancer cell line. 相似文献
188.
As a consequence of an initiative of the local authorities of the city of Antwerp (Belgium), dioxin levels were determined in eggs from free range hens owned by private owners in the Northern districts of Antwerp. The reasons for this survey stem from some fears that free range eggs could be contaminated by local environmental sources (e.g. soil, grass, earthworms) as a result of the presence in this area of intensive industrial and domestic activities. The analyses revealed high levels of PCDD/F in the home-produced eggs (average = 9.9 pg WHO-TEQ per g of fat; n = 15). An evaluation of the available results has been carried out by the Scientific Committee of the Belgian Federal Agency for the Safety of the Food Chain. From this evaluation, it appeared that the analysis of congener profiles was of limited use because all profiles were dominated by the OCDD congener, independently of the level of contamination. There were not enough indications allowing a causal link to be established between high dioxin levels in eggs and soil contamination and, on the other hand, it was assumed that other factors such as feeding habits, physiological state and egg laying rhythm of the hens could not be ruled out as potential causes of aggravation. A quick risk assessment led to the conclusion that the impact of this contamination is highly relevant for the consumer’s health due to the important contribution of such home-produced eggs in the estimations of total body burden. 相似文献
189.
Verleyen T Verhe R Garcia L Dewettinck K Huyghebaert A De Greyt W 《Journal of chromatography. A》2001,921(2):277-285
Because of its complex nature, the analysis of deodorizer distillate is a challenging problem. Deodorizer distillate obtained from the deodorization process of vegetable oils consists of many components including free fatty acids, tocopherols, sterols, squalene and neutral oil. A gas chromatographic method for the analysis of deodorizer distillate without saponification of the sample is described. After a concise sample preparation including derivatization and silylation, distillate samples were injected on column at 60 degrees C followed by a gradual increase of the oven temperature towards 340 degrees C. The temperature profile of the oven was optimized in order to obtain a baseline separation of the different distillate components including free fatty acids, tocopherols, sterols, squalene and neutral oil. Good recoveries for delta-tocopherol, alpha-tocopherol, stigmasterol and cholesteryl palmitate of 97, 94.4, 95.6 and 92%, respectively were obtained. Repeatability of the described gas chromatographic method was evaluated by analyzing five replicates of a soybean distillate. Tocopherols and sterols had low relative standard deviations ranging between 1.67 and 2.25%. Squalene, mono- and diacylglycerides had higher relative standard deviations ranging between 3.33 and 4.12%. Several industrial deodorizer distillates obtained from chemical and physical refining of corn, canola, sunflower and soybean have been analyzed for their composition. 相似文献
190.
Let G be a connected reductive group defined over a finite fieldwith q elements and let F: G G be the corresponding Frobeniusendomorphism. We prove that the Mackey formula for Lusztig inductionand restriction holds in GF if all the simple components ofG are of type A. Our result holds for every Frobenius endomorphism(split or non-split) and for every q. 1991 Mathematics SubjectClassification: 20G05, 20G40. 相似文献