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991.
Excursion to the World of Heptacyclic Compounds Made of Azulenes and Acetylenedicarboxylates 下载免费PDF全文
Yi Chen Erja Lehto Peter Uebelhart Anthony Linden Hans‐Jürgen Hansen 《Helvetica chimica acta》2015,98(7):913-937
Azulenes and acetylenedicarboxylates react under acid catalysis (Brønsted or Lewis) and form (2aRS,8aSR)‐2a,8a‐dihydrocyclopenta[cd]azulene‐1,2‐dicarboxylates as intermediate products, which then dimerize by central bond‐formation between C(2a1) and C(2′a1) and various peripheral C,C′‐atoms of the dihydroazulene fragments, depending on the substituents present. The reactions are often accompanied by the formation of side‐products, such as 2‐(azulen‐1‐yl)fumarates and ‐maleates and others caused by H‐shifts of the primary intermediates. H‐Shifts between the two tetrahydrocyclopenta[cd]azulene parts of the heptacyclic structures were also found. 相似文献
992.
Two 2,6‐Dioxabicyclo[3.3.1]nonan‐3‐ones from Phragmanthera capitata (Spreng.) Balle (Loranthaceae) 下载免费PDF全文
Bruno N. Lenta Joél T. Ateba Jean R. Chouna Makoah N. Aminake Flore Nardella Gabriele Pradel Beate Neumann Hans Georg Stammler Catherine Vonthron‐Sénécheau Silvère Ngouela Norbert Sewald 《Helvetica chimica acta》2015,98(7):945-952
Phytochemical investigation of the leaves of Phragmanthera capitata collected on Cassia spectabilis tree led to the isolation of two natural lactones, rel‐(1R,5S,7S)‐7‐[2‐(4‐hydroxyphenyl)ethyl]‐2,6‐dioxabicyclo[3.3.1]nonan‐3‐one ( 1 ) and 4‐{2‐[rel‐(1R,3R,5S)‐7‐oxo‐2,6‐dioxabicyclo[3.3.1]non‐3‐yl]ethyl}phenyl 3,4,5‐trihydroxybenzoate ( 2 ) together with the known compounds betulinic acid ( 3 ), dodoneine ( 4 ), quercetin 3‐O‐α‐L ‐rhamnopyranoside ( 5 ), quercetin 3‐O‐α‐L ‐arabinofuranoside ( 6 ), quercetin ( 7 ), betulin ( 8 ), lupeol ( 9 ), and sitosterol ( 10 ). Their structures were established by means of modern spectroscopic techniques, and the relative configuration of compound 1 was confirmed by X‐ray analysis. Compounds 1 and 2 were tested in vitro for their antiplasmodial activity against the Plasmodium falciparum chloroquine sensitive‐strains NF54 and 3D7. Compound 2 exhibited good antiplasmodial activity against both strains with IC50 of 2.4 and 4.9 μM , respectively, while compound 1 was inactive. 相似文献
993.
Dr. Graeme J. Stasiuk Dr. Florencia Minuzzi Dr. Myra Sae‐Heng Charlotte Rivas Dr. Hans‐Paul Juretschke Dr. Lorenzo Piemonti Dr. Peter R. Allegrini Dr. Didier Laurent Andrew R. Duckworth Prof. Andrew Beeby Prof. Guy A. Rutter Prof. Nicholas J. Long 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(13):5023-5033
Despite the contribution of changes in pancreatic β‐cell mass to the development of all forms of diabetes mellitus, few robust approaches currently exist to monitor these changes prospectively in vivo. Although magnetic‐resonance imaging (MRI) provides a potentially useful technique, targeting MRI‐active probes to the β cell has proved challenging. Zinc ions are highly concentrated in the secretory granule, but they are relatively less abundant in the exocrine pancreas and in other tissues. We have therefore developed functional dual‐modal probes based on transition‐metal chelates capable of binding zinc. The first of these, Gd ?1 , binds ZnII directly by means of an amidoquinoline moiety (AQA), thus causing a large ratiometric Stokes shift in the fluorescence from λem=410 to 500 nm with an increase in relaxivity from r1=4.2 up to 4.9 mM ?1 s?1. The probe is efficiently accumulated into secretory granules in β‐cell‐derived lines and isolated islets, but more poorly by non‐endocrine cells, and leads to a reduction in T1 in human islets. In vivo murine studies of Gd ?1 have shown accumulation of the probe in the pancreas with increased signal intensity over 140 minutes. 相似文献
994.
Probing the Diastereoselectivity of Staudinger Reactions Catalyzed by N‐Heterocyclic Carbenes 下载免费PDF全文
Morgan Hans Prof. Johan Wouters Prof. Albert Demonceau Prof. Lionel Delaude 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(30):10870-10877
The reaction of ethylphenylketene with 1,3‐dimesitylimidazol‐2‐ylidene (IMes) or 1,3‐dimesitylimidazolin‐2‐ylidene (SIMes) afforded the corresponding azolium enolates in high yields. The two zwitterions were fully characterized by various analytical techniques. Their thermal stabilities were monitored by thermogravimetric analysis and the molecular structure of SIMes ? EtPhC?C?O was determined by means of X‐ray crystallography. A mechanism was proposed to account for the trans‐diastereoselectivity observed in the [2+2] cycloaddition of ketenes and N‐protected imines catalyzed by N‐heterocyclic carbenes and an extensive catalytic screening was performed to test its validity. The steric bulk of the NHC catalyst markedly affected the cis/trans ratio of the model β‐lactam product. The nature of the solvent used to carry out the Staudinger reaction also significantly influenced its diastereoselectivity. Conversely, the nature of the substituent on the N‐sulfonated imine reagent and the reaction temperature were less critical parameters. 相似文献
995.
Comparing Cyclophellitol N‐Alkyl and N‐Acyl Cyclophellitol Aziridines as Activity‐Based Glycosidase Probes 下载免费PDF全文
Jianbing Jiang Thomas J. M. Beenakker Dr. Wouter W. Kallemeijn Prof. Dr. Gijsbert A. van der Marel Hans van den Elst Dr. Jeroen D. C. Codée Prof. Dr. Johannes M. F. G. Aerts Prof. Dr. Herman S. Overkleeft 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(30):10861-10869
The synthesis and evaluation as activity‐based probes (ABPs) of three configurationally distinct, fluorescent N‐alkyl cyclophellitol aziridine isosteres for profiling GH1 β‐glucosidase (GBA), GH27 α‐galactosidase (GLA) and GH29 α‐fucosidase (FUCA) is described. In comparison with the corresponding acyl aziridine ABPs reported previously, the alkyl aziridine ABPs are synthesized easily and are more stable in mild acidic and basic media, and are thus easier to handle. The β‐glucose‐configured alkyl aziridine ABP proves equally effective in labeling GBA as its N‐acyl counterpart, whereas the N‐acyl aziridines targeting GLA and FUCA outperform their N‐alkyl counterparts. Alkyl aziridines can therefore be an attractive alternative in retaining glycosidase ABP design, but in targeting a new retaining glycosidase both N‐alkyl and N‐acyl aziridines are best considered at the onset of a new study. 相似文献
996.
Dr. Thomas Schwarze Janine Riemer Dr. Sascha Eidner Prof. Hans‐Jürgen Holdt 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(32):11306-11310
A highly K+‐selective two‐photon fluorescent probe for the in vitro monitoring of physiological K+ levels in the range of 1–100 mM is reported. The two‐photon excited fluorescence (TPEF) probe shows a fluorescence enhancement (FE) by a factor of about three in the presence of 160 mM K+, independently of one‐photon (OP, 430 nm) or two‐photon (TP, 860 nm) excitation and comparable K+‐induced FEs in the presence of competitive Na+ ions. The estimated dissociation constant (Kd) values in Na+‐free solutions (KdOP=(28±5) mM and KdTP=(36±6) mM ) and in combined K+/Na+ solutions (KdOP=(38±8) mM and KdTP=(46±25) mM ) reflecting the high K+/Na+ selectivity of the fluorescent probe. The TP absorption cross‐section (σ2PA) of the TPEF probe+160 mM K+ is 26 GM at 860 nm. Therefore, the TPEF probe is a suitable tool for the in vitro determination of K+. 相似文献
997.
Da Wang Dr. Christian Richter Andreas Rühling Dr. Patrick Drücker Daniel Siegmund Prof. Dr. Nils Metzler‐Nolte Prof. Dr. Frank Glorius Prof. Dr. Hans‐Joachim Galla 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(43):15123-15126
A series of imidazolium salts bearing two alkyl chains in the backbone of the imidazolium core were synthesized, resembling the structure of lipids. Their antibacterial activity and cytotoxicity were evaluated using Gram‐positive and Gram‐negative bacteria and eukaryotic cell lines including tumor cells. It is shown that the length of alkyl chains in the backbone is vital for the antibiofilm activities of these lipid‐mimicking components. In addition to their biological activity, their surface activity and their membrane interactions are shown by film balance and quartz crystal microbalance (QCM) measurements. The structure–activity relationship indicates that the distinctive chemical structure contributes considerably to the biological activities of this novel class of lipids. 相似文献
998.
999.
It is known that the extension complexity of the TSP polytope for the complete graph \(K_n\) is exponential in n even if the subtour inequalities are excluded. In this article we study the polytopes formed by removing other subsets \({\mathcal {H}}\) of facet-defining inequalities of the TSP polytope. In particular, we consider the case when \({\mathcal {H}}\) is either the set of blossom inequalities or the simple comb inequalities. These inequalities are routinely used in cutting plane algorithms for the TSP. We show that the extension complexity remains exponential even if we exclude these inequalities. In addition we show that the extension complexity of polytope formed by all comb inequalities is exponential. For our proofs, we introduce a subclass of comb inequalities, called (h, t)-uniform inequalities, which may be of independent interest. 相似文献
1000.
Hans Schoutens 《代数通讯》2017,45(1):262-274
We prove Hochster’s small maximal Cohen–Macaulay conjecture for three-dimensional complete F-pure rings. We deduce this from a more general criterion, and show that only a weakening of the notion of F-purity is needed, to wit, being weakly F-split. We conjecture that any complete ring is weakly F-split. 相似文献