新型磺酸功能化吡啶盐酸盐离子液体催化剂用于六氢喹啉合成(英文)

Sulfonic acid functionalized pyridinium chloride [pyridine-SO3 H]Cl has been synthesized as a novel Brnsted acidic ionic liquid and characterized on the basis of its FT-IR,1H and 13C NMR,MS,ther-mogravimetry,and derivative thermogravimetry data.The material has also been used as a highly efficient,homogeneous,and reusable catalyst for the preparation of hexahydroquinolines according to the one-pot multi-component condensation of arylaldehydes,dimedone(5,5-dimethylcyclohexane-1,3-dione),β-ketoesters,and ammonium acetate under solvent-free conditions.     

Synthesis and inhibition properties of conformational probes for the mutase-catalyzed UDP-galactopyranose/furanose interconversion

UDP-galactose mutase is a flavoenzyme that catalyzes the isomerization of UDP-galactopyranose into UDP-galactofuranose, a key step in the biosynthesis of important bacterial oligosaccharides. Several mechanisms for this unique ring-contraction have been proposed, one of them involving a putative 1,4-anhydrogalactopyranose as an intermediate in the reaction. The purpose of this study was to probe the mutase binding site with conformationally restricted analogues of its substrate. Thus, we describe the straightforward synthesis of two C-glycosidic UDP-galactose derivatives: analogue 1, presenting a galactose moiety locked in a bicyclic (1,4)B boat conformation, and UDP-C-Galf 2, where the galactose residue is locked in the conformation of the mutase substrate. The two molecules were found to be inhibitors of UDP-galactose mutase at levels depending on the redox state of the enzyme. Strong inhibition of the native enzyme, but a low one of the reduced mutase, were observed with UDP-C-Galf 2, whereas 1 displayed intermediate inhibition levels under both native and reducing conditions. These data provide evidence of a significant conformational difference of the mutase binding pocket in the reduced enzyme and in the native one, the enzyme switching from a low Galf-affinity state (reduced enzyme) to a very strong one (native enzyme). It is remarkable that the mutase binds the boat-locked analogue 1 with similar affinities in both its conformational states. These results support a mechanism involving the formation of 1,4-anhydrogalactopyranose as a low-energy intermediate. An alternative explanation would be that the distortion of the galactose moiety during the cycle contraction transiently brings the carbohydrate into a conformation close to a (1,4)B boat.     

Application of benzyl protecting groups in the synthesis of prenylated aromatic compounds

Benzyl ethers have proven to be useful protecting groups for synthesis of phenols bearing isoprenoid chains because the benzyl groups can tolerate the conditions of halogen-metal exchange used to introduce the side chains yet are cleaved in good yields upon treatment with sodium s-butanol.     

Preparation and reductive lithiation of 2-deoxy-D-glucopyranosyl phenylsulfones: A highly stereoselective route to C-glycosides

2-Deoxy-D-glucopyranosyl phenylsulfones 3a–c have been synthesized in 75–83% yield from commercial tri-O-acetyl-D-glucal 1. Their reductive desulfonylation by lithium naphthalenide and reaction of the intermediate glycosyl-lithium 5 with aldehydes leads to α-D-C-glucopyranosides with high stereoselectivity.     

1‐Methoxyhexane‐3‐thiol,a Powerful Odorant of Clary Sage (Salvia sclarea L.)

The peculiar and highly diffusive odor signal of flowering clary‐sage plants (Salvia sclarea L.) was identified to derive from trace amounts of 1‐methoxyhexane‐3‐thiol ( 1 ) by mass‐spectrometry analysis and confirmed by comparison with synthetic racemic thiol (±)‐ 1 . The enantiomers (S)‐ and (R)‐ 1 were prepared by enantioselective synthesis, and the absolute configuration of (S)‐ 1 was fully corroborated by X‐ray‐diffraction analysis of the crystalline thioester (1′S,1S)‐ 2 . Compound (S)‐ 1 is one of the most powerful odorants known, with a detection threshold of 0.04⋅10⁻³ ng/l air, and is, with its herbaceous‐green, alliaceous, and perspiration profile, key to the fragrance of clary‐sage flowers and of the freshly distilled essential oil. As a consequence of its unique odor, 1 was also suspected to be part of the volatiles of a Ruta species where it was subsequently identified together with its homologue, 1‐methoxyheptane‐3‐thiol ( 3 ), 1‐methoxy‐4‐methylpentane‐3‐thiol ( 4 ), and the known 4‐methoxy‐2‐methylbutane‐2‐thiol ( 5 ). The syntheses of (±)‐ 3 and (±)‐ 4 as well as of the enantiomer (R)‐ 4 are described. In both natural fractions, the ratio (S)‐ 1 /(R)‐ 1 was slightly in favor of the (S)‐enantiomer. Natural 4 has (R)‐configuration.     

Synthesis of high-modulus thermoset PUs of PCL-PTMG/CNW biomaterials with different soft domain architecture and composition for high shape memory performance

Cellulose - In this research work, a series of thermoset polyurethane (tPU) nanocomposites and a thermoplastic PU (TPPU) were synthesized using semi-crystalline polyols. Poly(ε-caprolactone)...     

On the sensitivity of ASL MRI in detecting regional differences in cerebral blood flow

Arterial-spin-labeling (ASL) magnetic resonance imaging (MRI) provides a noninvasive tool to measure cerebral blood flow (CBF) and is increasingly used as a surrogate for baseline neural activity. However, the power of ASL MRI in detecting CBF differences between patient and control subjects is hampered by inter-subject variations in global CBF, which are associated with non-neural factors and may contribute to the noise in the across-group comparison. Here, we investigated the sensitivity of this technique and proposed a normalization strategy to better detect such a difference. A “model” situation was employed in which two visual stimuli (i.e. cross fixation and flashing checkerboard) were presented to two groups of subjects to mimic “control” and “patient” groups (N=7 for each group), respectively. It was found that absolute CBF (aCBF) in the occipital lobe in the checkerboard group was 26.0% greater compared to the fixation group, but the level of significance was modest (P=.03). In contrast, when normalizing the CBF with whole-brain CBF or CBF in a reference region [termed relative CBF (rCBF)], the statistical significance was improved considerably (P<.003). For voxel-based analysis, the rCBF indices correctly detected CBF differences in the occipital lobe in the across-group comparison, while aCBF failed to detect any significant cluster using the same statistical threshold. We also performed Monte Carlo simulation to confirm the experimental findings and found that the power improvement was most pronounced when signal-to-noise-ratio is moderate and the underlying CBF difference was small. The simulation also showed that, with the proposed normalization, a detection power of 80% can be achieved using a sample size of about 20. In summary, rCBF is a more sensitive index to detect small differences in CBF, rather than the much-sought-after aCBF, since it reduces data noise caused by inter-subject variations in global CBF.     

The effect of wavy leading edges on aerofoil–gust interaction noise

High-order accurate numerical simulations are performed to investigate the effects of wavy leading edges (WLEs) on aerofoil–gust interaction (AGI) noise. The present study is based on periodic velocity disturbances predominantly in streamwise and vertical directions that are mainly responsible for the surface pressure fluctuation of an aerofoil. In general, the present results show that WLEs lead to reduced AGI noise. It is found that the ratio of the wavy leading-edge peak-to-peak amplitude (LEA) to the longitudinal wavelength of the incident gust (_λg${\lambda }_g$) is the most important factor for the reduction of AGI noise. It is observed that there exists a tendency that the reduction of AGI noise increases with LEA/_λg$\mathrm{LEA}/{\lambda }_g$ and the noise reduction is significant for LEA/_λg≥0.3$\mathrm{LEA}/{\lambda }_g\ge 0.3$. The present results also suggest that any two different cases with the same LEA/_λg$\mathrm{LEA}/{\lambda }_g$ lead to a strong similarity in their profiles of noise reduction relative to the straight leading-edge case. The wavelength of wavy leading edges (LEW), however, shows minor influence on the reduction of AGI noise under the present gust profiles used. Nevertheless, the present results show that a meaningful improvement in noise reduction may be achieved when 1.0≤LEW/_λg≤1.5$1.0\le \mathrm{LEW}/{\lambda }_g\le 1.5$. In addition, it is found that the beneficial effects of WLEs are maintained for various flow incidence angles and aerofoil thicknesses. Also, the WLEs remain effective for gust profiles containing multiple frequency components. It is discovered in this paper that WLEs result in incoherent response time to the incident gust across the span, which results in a decreased level of surface pressure fluctuations, hence a reduced level of AGI noise.     

MCD-finite Domains and Ascent of IDF Property in Polynomial Extensions

An integral domain is said to have the IDF property when every non-zero element of it has only a finite number of non-associate irreducible divisors. A counterexample has already been found showing that the IDF property does not necessarily ascend in polynomial extensions. In this paper, we introduce a new class of integral domains, called MCD-finite domains, and show that for any domain D, D[X] is an IDF domain if and only if D is both IDF and MCD-finite. This result entails all the previously known sufficient conditions for the ascent of the IDF property. Our new characterization of polynomial domains with the IDF property enables us to use a different construction and build another counterexample which strengthen the previously known result on this matter.     

Microbundles, manifolds and metrisability

The notion of a microbundle was introduced in the 1960s but the theory came to an abrupt halt when it was shown that for a metrisable manifold, microbundles are equivalent to fibre bundles. In this paper we consider microbundles over non-metrisable manifolds. In some cases microbundles are equivalent to fibre bundles but in others they are not. In particular, we show that a manifold is metrisable if and only if its tangent microbundle is equivalent to a fibre bundle. We also illustrate that for some non-metrisable manifolds every trivial microbundle contains a trivial fibre bundle whereas other manifolds may support a trivial microbundle not containing a trivial fibre bundle.