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1.
Synthetic peptides are in huge demand in expansion of potential peptide mimics, which may have improved or comparable function as natural one. With these concerns, phenyl bearing aromatic amino acids and peptides has extensively explored, because phenyl residue has high probability in forming stable secondary structure, owing to the presence of an extra stabilizing factor as π–π non-covalent interactions. Apart from phenyl bearing benzenoid aromatic amino acids, a few non-benzenoid aromatic derivatives such as tropolone and related compounds are also occurred in nature, but troponyl containing amino acids and peptides are very poorly understood. Tropolonyl derivatives also contain carbonyl functional group, which may play an important role to provide stable conformation in peptide. Herein we report the synthesis, and conformational analysis of rationally designed new unnatural δ-amino acid, troponyl aminoethylglycine (Tr-aeg), which contains troponyl residue as side chain in flexible aminoethylglycine (aeg) amino acid backbone. We also demonstrate the role of troponyl carbonyl of Tr-aeg residue in hydrogen bonding with adjacent amide NH of their hybrid di/tri-peptides with NMR methods and DFT calculations. In future, Tr-aeg amino acid would be a potential building block in development of promisable peptide mimics. 相似文献
2.
Enantiopure unnatural homologated amino acids, whereby there is?>?1 carbon atom between the C- and N- termini have found great utility in a number of applications. The enantiopure syntheses of β-amino acids are well documented, as increasingly are those of γ-amino acids. δ-Amino acids on the other hand are much less well-studied despite reports of their potential utility. This review attempts to summarise strategies that have been adopted towards the enantioselective synthesis of δ-amino acids and their precursors (e.g. nitrile/nitro/azido/ester/alcohol etc) and where appropriate demonstrate their utility. Only systems which are all carbon between the two termini are considered and only those where the shortest route between any given C-termini and any given N-termini is four carbons long (i.e. lysine derivatives are not considered). 相似文献
3.
The title compounds were synthesized from the selectively protected N-acylated d-glucosamine derivatives, containing α-halo carboxylic acid moieties, via intramolecular 3-O-alkylation. It was found that if the starting compound contains asymmetric electrophilic center, isomuramic acid derivatives were mainly formed, regardless of the configuration of the electrophilic carbon atom. An explanation for the observed stereochemical results was proposed on the basis of the analysis of steric interactions in the molecules of the starting compounds, as well as using the concept of anchimeric assistance. It was shown that N-acetylation of the obtained lactam derivatives and subsequent methanolysis under mild conditions led to the selective cleavage of δ-lactam ring resulting in the formation of the corresponding ester derivatives of N-acetylmuramic acid or its analogues in high yields. 相似文献
4.
Giangiacomo Beretta Fabrizio Gelmini Fabrizio Fontana Roberta Manuela Moretti Marina Montagnani Marelli Patrizia Limonta 《Natural product research》2018,32(10):1130-1135
In this work, we report a rapid and convenient HPLC-UV-DAD method for the isolation of δ-T3 on semi-preparative scale from two different vitamin E rich processed, commercially available products obtained from the fruits of Elaeis guineensis Jacq. (oil palm) and from the seeds of Bixa orellana L. (achiote tree). Chromatography was run using reverse phase (RP) C-18 columns and HPLC-grade acetonitrile as mobile phase. The purity of the isolated δ-T3, assessed by GC–MS and 1H NMR was above 98%. The δ-T3 cytotoxic activity found in vitro against the proliferation of human A375 melanoma cells compared to that of the other δ-T3 free tocols mixture suggest its primary role in the experimental anticancer activity observed for palm oil derived products. Taken altogether, the results of this study highlight the importance of the application of suitable purification systems for the preparations of tocotrienols prior to their experimental or clinical testing. 相似文献
5.
2-Isopropylbenzimidazole and 2-methylbenzimidazole have been found to be effective bulky proton sources for stereoselective protonation of chiral enolate anions. 2-Isopropylbenzimidazole worked in the stereoselective protonation of the Birch reduction of chiral α,β-unsaturated imides. On the other hand, 2-methylbenzimidazole was found to be the best protonation reagent in the isomerization reaction of α,β-unsaturated imide into β,γ-unsaturated imide. The Birch reduction using 2-isopropylbenzimidazole realized a concise and stereoselective synthesis of δ-lactone 14, a sex pheromone of Macrocentrus grandii, while the isomerization reaction using 2-methylbenzimidazole was employed in the highly stereoselective synthesis of the γ-lactone intermediate in the synthesis of depsipeptide antibiotics. These bulky proton sources would be powerful tools to achieve a concise synthesis of natural products. 相似文献
6.
ABSTRACT Copolymers of 1,5-dioxepan-2-one (DXO) and e-caprolactone (?-CL), δ-valerolactone (δ-VL) or L-lactide (LLA) have been synthesized and characterized. High molecular weight copolymers were obtained using stannous-2-ethyl hexanoate as catalyst in bulk. Reactivity ratios for the copolymerization of DXO and δ-VL were determined at 110°C as rVL=0.5 and rDXO=2.3. At high conversion, depolymerization of δ-VL occurred, resulting in lower molecular weight and variations in the copolymer composition. Physical properties, such as crystallinity and melting temperature of the DXO-copolymers proved to be strongly dependent on the choice of comonomer and on the molar composition of the copolymers. DXO appears to be incorporated into the poly-?-caprolactone (PCL) crystals and to some extent into the poly-δ-valerolactone (PVL) crystals, resulting in a more gradual decrease in crystallinity with increasing amount of DXO. 相似文献
7.
Four symmetrical α,α′,δ,δ′-tetramethyl-cucurbit[6]uril-based compounds have been prepared and characterised by X-ray crystallography. Their crystal structures displayed the acetate anion-selective encapsulating capability of symmetrical α,α′,δ,δ′-tetramethyl-cucurbit[6]uril. The host–guest interaction between the symmetrical α,α′,δ,δ′-tetramethyl-cucurbit[6]uril and the acetate anion in aqueous solution has also been observed by variable temperature 1H NMR spectroscopy. 相似文献
8.
Tomoyuki Tajima Yukie Yamaguchi Yo-hei Shiomoto Yutaka Takaguchi 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1):2-11
Abstract We succeeded in the synthesis of a novel poly(amidoamine) dendrimer having diphenyl diselenide at the core. Modification of the dendrimer diselenide by the reaction with glucono-δ-lactone in methanol gave a water-soluble dendrimer diselenide having chiral terminal groups. The structures of dendrimers were satisfactorily confirmed by MAIDI-TOF MS spectrometry, elemental analysis, and NMR spectroscopy. Interestingly, induced circular dichroism (ICD) of the interaction between the diphenyl diselenide core and D-gluconamide periphery of the dendrimer was observed at 300 nm. Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file. GRAPHICAL ABSTRACT 相似文献
9.
Detailed Description of Pulse Isotopic Exchange Method for Analyzing Oxygen Surface Exchange Behavior on Oxide Ion Conductors 下载免费PDF全文
A novel pulse 18O-16O isotopic exchange (PIE) technique for measurement of the rate of oxygen surface exchange of oxide ion conductors was presented. The technique employs a continuous flow packed-bed micro-reactor loaded with the oxide powder. The isothermal response to an 18O-enriched pulse passing through the reactor, thereby maintaining chemical equilibrium, is measured by on-line mass spectrometry. Evaluation of the apparent exchange rate follows from the uptake of 18O by the oxide at given reactor residence time and surface area available for exchange. The developed PIE technique is rapid, simple and highly suitable for screening and systematic studies. No rapid heating/quenching steps are required to facilitate 18O tracer anneal or analysis, as in other commonly used techniques based upon oxygen isotopic exchange. Moreover, the relative distribution of the oxygen isotopologues 18O2, 16O18O, and 16O2 in the effluent pulse provides insight into the mechanism of the oxygen exchange reaction. The PIE technique has been demonstrated by measuring the exchange rate of selected oxides with enhanced oxide ionic conductivity in the range of 350?900 oC. Analysis of the experimental data in terms of a model with two consecutive, lumped steps for the isotopic exchange reaction shows that for mixed conductors Ba0.5Sr0.5Co0.8Fe0.2O3-δ(BSCF) and La2NiO4+δ the reaction is limited by the apparent rate of dissociative adsorption of O2 molecules at the oxide surface. For yttria-stabilized zirconia (YSZ), a change-over takes place, from rate-limitations by oxygen incorporation below ∽800 oC to rate-limitations by O2 dissociative adsorption above this temperature. Good agreement is obtained with exchange rates reported for these materials in literature. 相似文献
10.
纳米α-FeOOH催化剂一段法脱除COS和H2S性能的研究 总被引:11,自引:1,他引:11
利用均相沉淀法、氨水滴定法制备纳米α-FeOOH粒子,以该粒子为活性组分制备催化剂,利用微反-色谱联用活性评价技术,在常压、空速10 000 h-1、25 ℃~60 ℃温度范围内考察了纳米α-FeOOH催化剂对COS催化水解的活性。采用热重法对纳米α-FeOOH催化剂脱除H2S的性能进行了研究。结果表明:纳米α-FeOOH催化剂对COS水解在低温度、大空速下具有高的活性,系列Ⅰ和系列Ⅱ催化剂分别在60 ℃和40 ℃~45 ℃时COS转化率达到100%。在60 ℃时各种催化剂吸附H2S的能力最强,最高饱和硫容可达到21.72w%。催化剂表面能量分布不均匀,COS催化水解在低温时存在补偿效应。 相似文献