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991.
基于半导体光放大器进行光标签提取的性能分析   总被引:5,自引:2,他引:3  
牛长流  张民  叶培大 《光子学报》2006,35(2):274-276
利用半导体光放大器增益饱和数学模型,第一次分析了基于单个半导体放大器进行光标签提取的节点性能.通过对半导体光放大器的参量分析和优化,仿真显示,对于标签速率2.5 Gb/ s 、净荷速率40 Gb/s 的光分组包,提取的标签消光比可达到13 dB.  相似文献   
992.
光突发交换网络中最长队列优先调度组装机制   总被引:5,自引:5,他引:0  
吕召彪  王洪波  张民  叶培大 《光子学报》2006,35(9):1374-1378
提出了光突发交换网络中的最长队列优先调度(LQF-SA)机制,将边缘节点的突发组装和突发调度两种技术紧密结合在一起.在现实网络中,业务通常是非均匀分布的,即在某些源宿对之间存在更大的业务流量.仿真结果表明,LQF-SA机制可以很好地完成非均匀分布业务流的组装.即使在均匀分布业务流输入下,LQF-SA机制在突发大小分布、组装效率和突发丢失率等方面也优于已提出的轮询调度组装(RR-SA)机制.  相似文献   
993.
Alkali-activated materials (AAMs) are considered to be alternative cementitious materials for civil infrastructures. Nowadays, efforts have been made in developing AAMs with self-compacting ability. The obtained self-compacting AAMs (SCAAMs) accomplish superior passing and filling properties as well as excellent mechanical and environmental advantages. This work critically revisits recent progresses in SCAAMs including mixture proportions, fresh properties, mechanical strength, microstructure, acid and sulfate resistance, high temperature behaviors, impact resistance and interface shear strength. To facilitate direct comparison and interpretation of data from different publications, mixture proportions were normalized in terms of the content of key reactive components from precursors and activators, and correlation with mechanical behaviors was made. Moreover, special attention was paid to current research challenges and perspectives to promote further investigation and field application of SCAAMs as advanced construction material.  相似文献   
994.
Prasiola japonica possesses several biological activities. However, reports on the anti-inflammatory activities and molecular mechanisms of its different solvent fractions remain limited. In this study, we investigated the potential anti-inflammatory activities of P. japonica ethanol extract (Pj-EE) and four solvent fractions of Pj-EE made with hexane (Pj-EE-HF), chloroform (Pj-EE-CF), butanol (Pj-EE-BF), or water (Pj-EE-WF) in both in vitro (LPS-induced macrophage-like RAW264.7 cells) and in vivo (carrageenan-induced acute paw edema mouse models) experiments. The most active solvent fraction was selected for further analysis. Various in vitro and in vivo assessments, including nitric oxide (NO), cytokines, luciferase assays, real-time polymerase chain reactions, and immunoblotting analyses were performed to evaluate the underlying mechanisms. In addition, the phytochemical constituents were characterized by Liquid chromatography-tandem mass spectrometry. In in vitro studies, the highest inhibition of NO production was observed in Pj-EE-CF. Further examination revealed that Pj-EE-CF decreased the expression of inflammation-related cytokines in LPS-induced RAW264.7 cells and suppressed subsequent AP-1-luciferase activity by inhibition of phosphorylation events in the AP-1 signaling pathway. Pj-EE-CF treatment also demonstrated the strongest reduction in thickness and volume of carrageenan-induced paw edema, while Pj-EE-BF showed the lowest activity. Furthermore, Pj-EE-CF also reduced gene expression and cytokines production in tissue lysates of carrageenan-induced paw edema. These findings support and validate the evidence that Pj-EE, and especially Pj-EE-CF, could be a good natural source for an anti-inflammatory agent that targets the AP1 pathway.  相似文献   
995.
The application of chitosan (CS) and whey protein (WP) alone or in combination in 3D/4D printing has been well considered in previous studies. Although several excellent reviews on additive manufacturing discussed the properties and biomedical applications of CS and WP, there is a lack of a systemic review about CS and WP bio-inks for 3D/4D printing applications. Easily modified bio-ink with optimal printability is a key for additive manufacturing. CS, WP, and WP–CS complex hydrogel possess great potential in making bio-ink that can be broadly used for future 3D/4D printing, because CS is a functional polysaccharide with good biodegradability, biocompatibility, non-immunogenicity, and non-carcinogenicity, while CS–WP complex hydrogel has better printability and drug-delivery effectivity than WP hydrogel. The review summarizes the current advances of bio-ink preparation employing CS and/or WP to satisfy the requirements of 3D/4D printing and post-treatment of materials. The applications of CS/WP bio-ink mainly focus on 3D food printing with a few applications in cosmetics. The review also highlights the trends of CS/WP bio-inks as potential candidates in 4D printing. Some promising strategies for developing novel bio-inks based on CS and/or WP are introduced, aiming to provide new insights into the value-added development and commercial CS and WP utilization.  相似文献   
996.
Laine研究小组直接用二氧化硅和乙二醇在无机碱的作用下,合成了五配位硅化合物:Laine研究的意义在于他开创了低温合成配位有机硅化合物的先河,这种方法有四个优点,(1)能耗小;(2)原料来源丰富,价格低廉,二氧化硅占地壳的1/4,乙二醇也很便宜;(3)污染小;(4)制得的五配位硅化合物反应活性非常高。但Laine在聚合物方面做的工作较少,过去只是把这个方法应用于高性能陶瓷玻璃的制备以及离子导电聚合物的研究中J,主要是解决不了五配位硅钾化合物的水解可逆性问题。  相似文献   
997.
We study the Leibniz n-algebra Un(∑),whose multiplication is defined viathe bracket of a Leibniz algebra ∑ as[x1,...,xn]=[x1,[...,[xn-2,[xn-1,xn]]...]].Weshow that Un(∑) is simple if and only if ∑ is a simple Lie algebra.An analog of Levi'stheorem for Leibniz algebras in Un(Lb) is established and it is proven that the Leibnizn-kernel of Un(Σ) for any semisimple Leibniz algebra Σ is the n-algebra Un(Σ).  相似文献   
998.
二氧化碳共聚SalenMX催化剂   总被引:1,自引:0,他引:1  
  相似文献   
999.
植物样品中各元素的含量,是评价土壤质量及健康的重要指标。为满足测定大批量生态地球化学植物样品中多金属元素分析要求,建立了交互模式-电感耦合等离子体质谱(ICP-MS)法测定植物样品中7种痕量金属元素的定量分析方法。讨论了ICP-MS的STD、KED(He)、交互模式3种方法测定植物样品中7种金属元素结果。结果表明,利用工作曲线法配制Hg标准溶液,更改82Se在线校正方程系数为1.83,在ICP-MS的交互模式下测定植物样品中82Se、63Cu、60Ni、66Zn、111Cd、75As、202Hg可以得到准确可靠的结果,克服了植物样品中Se和Hg元素测定的难题。基于所建方法各元素校准曲线系数>0.999,方法检出限为0.000 4~0.08 mg/kg,加标回收率在96.2%~107%,测定GBW10010a(大米)、GBW10012(玉米)、GBW10021(豆角)3种标准物质,结果均在参考值范围内,相对标...  相似文献   
1000.
The use of hydrazine-catalyzed ring-closing carbonyl–olefin metathesis (RCCOM) to synthesize polycyclic heteroaromatic (PHA) compounds is described. In particular, substrates bearing Lewis basic functionalities such as pyridine rings and amines, which strongly inhibit acid catalyzed RCCOM reactions, are shown to be compatible with this reaction. Using 5 mol% catalyst loadings, a variety of PHA structures can be synthesized from biaryl alkenyl aldehydes, which themselves are readily prepared by cross-coupling.

Hydrazine catalysis enables the ring-closing carbonyl–olefin metathesis (RCCOM) to form polycyclic heteroaromatics, especially those with basic functionality.

Polycyclic heteroaromatic (PHA) structures comprise the core framework of many valuable compounds with a diverse range of applications (Fig. 1A).1 For example, polycyclic azines (e.g. quinolines) are embedded in many alkaloid natural products, including diplamine2 and eupolauramine3 to name just a few. These types of structures are also of interest for their biological activity, such as with the inhibitor of the Src-SH3 protein–protein interaction shown in Fig. 1A.4 Many nitrogenous PHAs are also useful as ligands for transition metal catalysis, as exemplified by the widely used ligand 1,10-phenanthroline.5 Meanwhile, chalcogenoarenes6 such as dinaphthofuran7 and benzodithiophene8 have attracted high interest for both their medicinal properties9 and especially for their potential use as organic light-emitting diodes (OLEDs), organic photovoltaics (OPVs), and organic field-effect transistors (OFETs).10 These and numerous other examples have inspired the development of a wide variety of strategies to construct PHAs.1,11–14 Although these approaches are as varied as the structures they target, the wide range of molecular configurations within PHA chemical space and the challenges inherent in exerting control over heteroatom position and global structure make novel syntheses of these structures a topic of continuing interest.Open in a separate windowFig. 1(A) Examples of PHAs. (B) RCCOM strategy for PHA synthesis. (C) Lewis base inhibition for Lewis acid vs. hydrazine catalyzed RCCOM. (D) Hydrazine-catalyzed RCCOM for PHA synthesis.One potentially advantageous strategy for PHA synthesis is the use of ring-closing carbonyl–olefin metathesis15 (RCCOM) to forge one of the PHA rings, starting from a suitably disposed alkenyl aldehyde precursor 2 that can be easily assembled by cross-coupling (Fig. 1B). In related work, the application of RCCOM to form polycyclic aromatic hydrocarbons (PAHs) was reported by Schindler in 2017.16 In this case, 5 mol% FeCl3 catalyzed the metathesis of substrates to form phenanthrenes and related compounds in high yields at room temperature. This method was highly attractive for its efficiency, its use of an earth-abundant metal catalyst, and the production of benign acetone as the only by-product. Nevertheless, one obvious drawback to the use of Lewis acid activation is that the presence of any functionality that is significantly more Lewis basic than the carbonyl group can be expected to strongly inhibit these reactions (Fig. 1C). Such a limitation thus renders this method incompatible with a wide swath of complex molecules, especially PHAs comprised of azine rings. This logic argues for a mechanistically orthogonal RCCOM approach that allows for the synthesis of PHA products with a broader range of ring systems and functional groups.We have developed an alternative approach to catalytic carbonyl–olefin metathesis that makes use of the condensation of 1,2-dialkylhydrazines 5 with aldehydes to form hydrazonium ions 6 as the key catalyst–substrate association step.17–19 This interaction has a much broader chemoorthogonality profile than Lewis acid–base interactions and should thus be much less prone to substrate inhibition than acid-catalyzed approaches. In this Communication, we demonstrate that hydrazine-catalyzed RCCOM enables the rapid assembly of PHAs bearing basic functionality (Fig. 1D).For our optimization studies, we chose biaryl pyridine aldehyde 7 as the substrate (20 salt 11 was also productive (entry 2), albeit somewhat less so. Notably, iron(iii) chloride generated no conversion at either ambient or elevated temperatures (entries 3 and 4). Trifluoroacetic acid (TFA) was similarly ineffective (entry 5). Meanwhile, a screen of various solvents revealed that, while the transformation could occur in a range of media (entries 6–9), THF was optimal. Finally, by raising the temperature to 90 °C (entry 10) or 100 °C (entry 11), up to 96% NMR yield (85% isolated yield) of adduct 8 could be obtained in the same time period.Optimization studiesa
EntryCatalystSolventTemp. (°C)8 yield (%)
110THF8067
211THF8053
3FeCl3DCErt0
4FeCl3DCE800
5TFATHF800b
610i-PrOH8031
710CH3CN8028
810EtOAc8026
910Toluene8024
1010THF9087
1110THF10096c
Open in a separate windowaConditions: substrate 8 (0.2 mmol) and 5 mol% catalyst in 0.4 mL of solvent (0.5 M) in a 5 mL sealed tube were heated to the temperature indicated for 15 h. Yields were determined by 1H NMR using CH2Br2 as an internal standard.b2 equiv. of TFA was used.c85% isolated yield.Using the optimized conditions, we explored the synthesis of various PHAs (Fig. 2). In addition to benzo[h]isoquinoline (8), products 12 and 13 with fluorine substitution at various positions could be generated in good yields. Similarly, benzoisoquinolines 14 and 15 bearing electron-donating methoxy groups and the dioxole-fused product 16 were also accessed efficiently. Furthermore, a phenolic ether product 17 with a potentially acid-labile N-Boc group was generated in modest yield. We found that an even more electron-donating dimethylamino group was also compatible with this chemistry, allowing for the production of 18 in 68% yield. On the other hand, adduct 19 bearing a strongly electron-withdrawing trifluoromethyl group was isolated in only modest yield. The naphtho-fused isoquinoline 20 could be generated as well; however, 20 mol% catalyst was required to realize a 35% yield. The thiophene-fused product 21 was furnished in much better yield, also with the higher catalyst loading. Although not a heterocyclic system, we found that the reaction to form phenanthrene (22) was well-behaved, providing that compound in 83% yield. In addition, an amino-substituted phenanthrene 23 was also formed in good yield. Other thiophene-containing PAHs such as 24–26 were produced efficiently. On the other hand, adduct 27 was generated only in low yield. Naphthofuran (28), which is known to have antitumor and oestrogenic properties,21 was synthesized in good yield. Finally, pharmaceutically important structures such as benzocarbazole2229 and naphthoimidazole2330 could be accessed in moderate yields with increased catalyst loading.Open in a separate windowFig. 2Substrate scope studies for hydrazine 1-catalyzed RCCOM synthesis of polycyclic heteroaromatics. a Conditions: substrate and catalyst 1·(TFA)2 (5 mol%) in THF (0.5 M) were heated to 100 °C in a 5 mL sealed tube for 15 h. Yields were determined on purified products. b 20 mol% catalyst.We also examined the scope of the olefin substitution pattern (
EntrySubstrateTime (h)Yield (%)
1 1596
2 485
3b 4827
4 4854
5 4864
Open in a separate windowaConditions: 5 mol% 10 in THF (0.5 M) in a 5 mL sealed tube were heated to the temperature indicated for 15–48 h. Conversions and yields were determined by 1H NMR using CH2Br2 as an internal standard.bMixture of E/Z (2 : 1) isomers.The vinyl substrate 31 led to very little desired product (entry 2), while the propenyl substrate 32 (2 : 1 mixture of E and Z isomers) was somewhat improved but still low-yielding (entry 3). Finally, styrenyl substrates 33 and 34 (entries 4 and 5) led to improved yields relative to 31 and 32, with the cis isomer 34 being slightly more efficient (entry 5).In order to better understand the facile nature of this RCCOM reaction, we conducted DFT calculations for each step of the proposed reaction pathway (Fig. 3A). Condensation of the substrate 7 with [2.2.1]-hydrazinium 10 to afford the hydrazonium Z-35 was found to be exergonic by −13 kcal mol−1. Isomerization of Z-35 to E-35 comes at a cost of ∼3 kcal mol−1, but the total activation energy for cycloaddition (cf.36), taking into account this isomerization, was still relatively modest at only +21.0 kcal mol−1 with an overall exergonicity of −11.1 kcal mol−1. The energetic change for proton transfer in the conversion of cycloadduct 37a to the cycloreversion precursor 37b was negligible (+1.2 kcal mol−1). Interestingly, including the proton migration step, the cumulative energy barrier for cycloreversion 38 was found to be only +21.7 kcal mol−1, nearly the same as for the cycloaddition. Undoubtedly, the formation of an aromatic ring greatly facilitates this step relative to other types of substrates. Unsurprisingly, the cycloreversion to produce benzoisoquinoline 8 along with hydrazonium 39 was calculated to be strongly exergonic. Finally, the hydrolysis of 39 to regenerate hydrazinium catalyst 10 (and acetone) required an energy input approximately equal to that gained from the condensation with the substrate to form 35.Open in a separate windowFig. 3(A) Computational study of hydrazine 10-catalyzed RCCOM of biaryl aldehyde 7. Calculations were performed at the PCM(THF)-M06-2X/6-311+G(d,p)//6-31G(d) level of theory.24,25 All energies are given in units of kcal mol−1. (B) 1H NMR spectroscopy of the RCCOM reaction of 7 catalyzed by 10 at 60 °C in THF-d8 with mesitylene as internal standard for 5 hours. (C) Plot of the data showing conversion vs. time. SM = starting material 7; CA = cycloadduct 37; Prd = product 8.Given the low activation energy barriers of both the cycloaddition and cycloreversion steps, we reasoned it should be possible for the reaction to proceed at a relatively low temperature. In fact, we observed 82% conversion of biaryl aldehyde 7 to cycloadduct 37 (72%) and benzoisoquinoline 8 (10%) at 40 °C over 6 hours. Attempts to isolate the cycloadduct 37 resulted in complete conversion to 8 during column chromatography. Meanwhile, at 60 °C over approximately 4 hours, 95% of the starting material 7, via the intermediate cycloadduct 37, was converted to benzoisoquinoline product 8 (Fig. 3B and C). The rate of consumption of the cycloadduct was consistent with first-order behavior, and upon fitting, revealed the rate constant for cycloreversion as kCR = 2.14 × 10−4 s−1, with a half-life of 54 minutes. These observations corroborate the computational results, in particular showing that the cycloreversion step is quite facile with these types of substrates compared to other hydrazine-catalyzed COM reactions we have investigated17 and that cycloaddition and cycloreversion have energetically similar activation energies.In conclusion, the development of catalytic carbonyl–olefin metathesis reactions has opened new possibilities for the rapid construction of complex molecules. The current work demonstrates this strategy as a means to rapidly access polycyclic heteroaromatics, which often require lengthy sequences that can be complicated by the presence of basic functionality. The ability of the hydrazine catalysis platform to accommodate such functional groups provides a novel approach to polycyclic heteroaromatic synthesis and greatly expands the landscape of structures accessible by RCCOM.  相似文献   
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