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1.
Kento Nishikibe Keisuke Nishikawa Momochika Kumagai Matsumi Doe Yoshiki Morimoto 《化学:亚洲杂志》2022,17(1):e202101137
There are marine cytotoxic bromotriterpenoids, named the thyrsiferol family that are structurally characterized by some tetrahydropyran (THP) and tetrahydrofuran (THF) rings. The thyrsiferol family belongs to natural products that are often difficult to determine their stereostructures even by the current, highly advanced spectroscopic methods, especially in acyclic systems including stereogenic tetrasubstituted carbon centers. In such cases, it is effective to predict and synthesize the possible stereostructures. Herein, to elucidate ambiguous stereostructures and unassigned absolute configurations of aplysiol B, laurenmariannol, and saiyacenol A, members of the thyrsiferol family, we carried out their asymmetric chemical syntheses featuring 6-exo and 5-exo oxacyclizations of epoxy alcohol precursors and 6-endo bromoetherification of a bishomoallylic alcohol. In this paper, we report total assignments of their stereostructures through their asymmetric chemical syntheses and also their preliminary cytotoxic activities against some tumor cells. These results could not have been achieved without depending on asymmetric total synthesis. 相似文献
2.
System scan of the multiplicity correlation between forward and backward rapidities in relativistic heavy-ion collisions using a multi-phase transport model 下载免费PDF全文
A systematic study on forward–backward (FB) multiplicity correlations from large systems to small ones through a multi-phase transport model (AMPT) has been performed and the phenomenon that correlation strength increases with centrality can be explained by taking the distribution of events as the superposition of a series of Gaussian distributions. It is also found that correlations in the \begin{document}$ \eta -\phi $\end{document} ![]()
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plane can imply the shape of the event. Furthermore, long-range correlations originate from the fluctuations associated with the source information. FB correlations allow us to decouple long-range correlations from short-range correlations, and may provide a chance to investigate the α-clustering structure in initial colliding light nuclei as well. It seems the tetrahedron 16O + 16O collision gives a more uniform and symmetrical fireball, that emits the final particles more isotropically or independently in the longitudinal direction, indicating that the forward–backward multiplicity correlation could be used to identify the pattern of α-clustered 16O in future experiments. 相似文献
3.
A Hjelmslev quadrilateral is a quadrilateral with two right angles at opposite vertices. Using mutual distances as coordinates, we show that any four-body central configuration forming a Hjelmslev quadrilateral must be a right kite configuration. 相似文献
4.
目前,悬链线在竖向集中力和均布荷载共同作用下的构形分析和受力计算的理论仍不完善。针对这一问题,通过引入悬链线的几何约束方程、力平衡方程和超越方程,建立了竖向集中力与均布荷载共同作用下的非线性方程组。采用牛顿迭代法求解方程组,得到了悬链线的构形和受力情况。为了验证理论计算的正确性,进行了算例和试验验证。结果表明,算例的计算结果与文献结论保持一致,试验测得的构形和水平张力大小与理论计算的构形和水平张力大小吻合较好。本文的理论计算可以更加简单精确地计算出悬链线在竖向集中力和均布荷载共同作用下的构形和受力情况,为实际工程提供重要的理论指导。 相似文献
5.
Mixed Polymer‐Coated Magnetic Nanoparticles as Forward Osmosis Draw Agents of Tuned Hydrophilicity 下载免费PDF全文
Dr. Priyanka Dey Dr. Emad L. Izake 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(32):11253-11260
We recently reported a polymer‐coated magnetic nanoparticle (MNP) draw agent for the forward osmosis (FO) water desalination process. The water flux was found to increase when the polymer poly(sodium acrylate) (PSA) was anchored to the MNP surface as compared to the polymer (or polyelectrolyte solution) alone, due to the polymer chains being stretched out and most of the hydrophilic groups on the polymer contributing to water flux. We herein report the use of a secondary polymer poly(N‐isopropylacrylamide) PNIPAM to manipulate the PSA polymer conformation and influence inter‐ and intrachain interactions to enhance the efficiency of the FO draw agent. These PSA–PNIPAM‐coated MNPs generated a much higher water flux of ~11.66 LMH when compared to the 100 % PSA‐coated MNPs featuring a value of ~5.32 LMH under identical FO conditions. The osmotic pressure and water flux driven by the mixed polymer‐coated MNPs were found to be a strong function of the net polymer coverage on MNPs, that is, net available hydrophilic groups. Our new draw agent demonstrates potential for use in the water industry due to its improved efficiency and cost effectiveness as it uses only ~0.062 % (w/v) of the draw agent solution. 相似文献
6.
Large‐Scale Synthesis of Enantiopure Molecular Cages: Chiroptical and Recognition Properties 下载免费PDF全文
Sara Lefevre Dawei Zhang Estelle Godart Marion Jean Dr. Nicolas Vanthuyne Jean‐Christophe Mulatier Dr. Jean‐Pierre Dutasta Dr. Laure Guy Prof. Alexandre Martinez 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(6):2068-2074
A convenient and efficient gram‐scale synthesis for enantiopure hemicryptophane–tren (tren=tris(2‐aminoethyl)amine) derivatives has been developed. The four‐step synthesis is based on the optical resolution of a key intermediate, cyclotriveratrylene, for which the energy barrier for racemization has been measured to ensure that no racemization occurs during the two last steps of the synthetic pathway. The assignments of the absolute configurations have been performed by electronic circular dichroism and the enantiopurity was determined by NMR spectroscopy in the presence of enantiopure camphor sulfonic acid. To highlight the interest of such compounds, the recognition of norephedrine neurotransmitter was investigated and showed a remarkable enantioselectivity towards the C3 symmetrical hosts. Finally, this highly modular synthetic pathway was used to provide eight enantiopure hemicryptophanes with different sizes, shapes, and functionalities. These results underline the high potential of this approach, which could lead to many applications in chiral recognition or asymmetric supramolecular catalysis. 相似文献
7.
Total Synthesis and Structure Elucidation of JBIR‐39: A Linear Hexapeptide Possessing Piperazic Acid and γ‐Hydroxypiperazic Acid Residues 下载免费PDF全文
Dr. Masahito Yoshida Naoki Sekioka Dr. Miho Izumikawa Dr. Ikuko Kozone Dr. Motoki Takagi Dr. Kazuo Shin‐ya Prof. Dr. Takayuki Doi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(7):3031-3041
The total synthesis and stereochemical structural elucidation of JBIR‐39, containing four nonproteinogenic piperazic acid (Piz) residues, is reported. The synthesis includes Sc(OTf)3‐catalyzed acylation of a Piz(γ‐OTBS) derivative with piperazic acid chloride, providing the desired Piz‐Piz(γ‐OTBS) dipeptide in high yield without epimerization. After assembling two additional Piz moieties and (S)‐isoleucic acid at the N‐terminus, amidation with the (R)‐α‐methylserine ester at the C‐terminus, and deprotection afforded the desired (2R,8S)‐hexapeptide, which is the assumed structure of JBIR‐39. Although the spectral data of the (2R,8S)‐hexapeptide was not identical to JBIR‐39, further synthesis of three stereoisomers confirmed the stereochemical structure of JBIR‐39 to be (2S,6S,8S,11R,16S,21R,26S,27S). 相似文献
8.
Bis(N‐Confused Porphyrin) as a Semirigid Receptor with a Chirality Memory: A Two‐Way Host Enantiomerization through Point‐to‐Axial Chirality Transfer 下载免费PDF全文
Prof. Piotr J. Chmielewski Dr. Marta Siczek Prof. Marcin Stępień 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(6):2547-2559
The adduct formation of protonated bis(N‐confused porphyrin) (BNCP, 3,3′‐bis(meso‐tetratolyl‐2‐aza‐21‐carbaporphyrin) with chiral anions, carboxylic acids, and alcohols was studied in solution by means of 1H NMR and circular dichroism (CD) spectroscopic analysis and DFT methods. The addition of enantiopure guests to the acidified BNCP resulted in optical activity that vanished after neutralization. Pairs of the 1H NMR‐distinguishable diastereomers were formed when enantiopure guests were applied, although a single form was observed upon the addition of the racemic mixtures in each case. Unidirectional configuration change that led to diastereomeric excess was observed in several instances. Such an excess was memorized by metalation of the adducts with AgBF4, thus resulting in optically active silver(III) complexes of BNCP with some enantiomeric excess. Absolute configurations of BNCP cations and bis(zinc) and bis(silver(III)) complexes were determined on the basis of time‐dependent (TD)‐DFT calculations of their CD spectra. It was shown that some of the chiral carboxylates induced opposite directions of enantiomerization of di‐ and tetracations or di‐/tetracation and bis(zinc) complexes. The source of the optical activity of the equimolar diastereomeric mixture of adducts is discussed. 相似文献
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