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51.
With the aid of Riemann–Liouville fractional calculus theory,fractional order Savitzky–Golay differentiation(FOSGD) is calculated and applied to pretreat near infrared(NIR) spectra in order to improve the performance of multivariate calibrations.Similar to integral order Savitzky–Golay differentiation(IOSGD),FOSGD is obtained by fitting a spectral curve in a moving window with a polynomial function to estimate its coefficients and then carrying out the weighted average of the spectral curve in the window with the coefficients.Three NIR datasets including diesel,wheat and corn datasets were utilized to test this method.The results showed that FOSGD,which is easy to compute,is a general method to obtain Savitzky–Golay smoothing,fractional order and integral order differentiations.Fractional order differentiation computation to the NIR spectra often improves the performance of the PLS model with smaller RMSECV and RMSEP than integral order ones,especially for physical properties of interest,such as density,cetane number and hardness. 相似文献
52.
Yahui Zhang Lingwei Kong Jianbing Shi Bin Tong Junge Zhi Xiao Feng Yuping Dong 《中国化学》2015,33(7):701-704
A new type of AIE molecules based on hexaphenyl‐1,3‐butadienes was reported with respect to the synthesis and characterization. This material exhibited different maximum emission wavelength and enhanced emission intensity at different aggregate state (amorphous and crystalline state). 相似文献
53.
Tuning the Reactivity of Isocyano Group: Synthesis of Imidazoles and Imidazoliums from Propargylamines and Isonitriles in the Presence of Multiple Catalysts 下载免费PDF全文
Dr. Shuo Tong Dr. Qian Wang Prof. Dr. Mei‐Xiang Wang Prof. Dr. Jieping Zhu 《Angewandte Chemie (International ed. in English)》2015,54(4):1293-1297
The reaction of propargyl amines with tert‐butylisonitrile in the presence of a catalytic amount of both Yb(OTf)3 and AgOTf afforded imidazoles, whereas the same reaction with primary and secondary alkylisonitriles, as well as arylisonitriles, in the presence of three metal salts [Yb(OTf)3/AgOTf/KOTf] resulted in the 1,3,4,5‐tetrasubstituted imidazoliums in excellent yields. Both chiral amines and chiral isonitriles can be used to provide corresponding chiral heterocycles without racemization. In this multiple catalytic system, Yb(OTf)3 catalyzed the insertion of isonitriles to the N? H bond of amines, AgOTf catalyzed the 5‐exo‐dig cyclization of the resulting amidine nitrogen to the tethered triple bond, and KOTf promoted the salt metathesis, thus providing at the same time the counterion to the imidazolium. Against common knowledge, the isocyano group acted in these reactions as a polarized triple bond instead of conventional carbene‐like function. 相似文献
54.
Visible‐Light‐Promoted Iminyl‐Radical Formation from Acyl Oximes: A Unified Approach to Pyridines,Quinolines, and Phenanthridines 下载免费PDF全文
Heng Jiang Xiaode An Kun Tong Tianyi Zheng Prof. Dr. Yan Zhang Prof. Dr. Shouyun Yu 《Angewandte Chemie (International ed. in English)》2015,54(13):4055-4059
A unified strategy involving visible‐light‐induced iminyl‐radical formation has been established for the construction of pyridines, quinolines, and phenanthridines from acyl oximes. With fac‐[Ir(ppy)3] as a photoredox catalyst, the acyl oximes were converted by 1 e? reduction into iminyl radical intermediates, which then underwent intramolecular homolytic aromatic substitution (HAS) to give the N‐containing arenes. These reactions proceeded with a broad range of substrates at room temperature in high yield. This strategy of visible‐light‐induced iminyl‐radical formation was successfully applied to a five‐step concise synthesis of benzo[c]phenanthridine alkaloids. 相似文献
55.
Dr. Xin Fang Ying Tong Di Yu Zhang Dr. Zhi Ping Xu Prof. Yang Lu Qian Qian Chen Prof. Qi Tai Zheng Prof. Dr. Xiao Jiang Hao 《Angewandte Chemie (International ed. in English)》2015,54(19):5592-5595
Perforalactone A ( 1 ), a new 20S quassinoid with a unique cagelike 2,4‐dioxaadamantane ring system and a migrated side chain, was isolated from the plant Harrisonia perforata together with two biosynthetically related new quassinoids. The structures of these natural products were elucidated by NMR spectroscopy, X‐ray diffraction analysis, computational modeling, and the CD excitation chirality method. The compounds exhibited notable biological properties, including insecticidal activity against Aphis medicaginis Koch and antagonist activity at the nicotinic acetylcholine receptor of Drosophila melanogaster. The structural features of these compounds may be related to their promising biological characteristics. Their biosynthesis and an alternative origin of quassinoid‐type natural products are also discussed. 相似文献
56.
Highly trans‐Selective Arylation of Achmatowicz Rearrangement Products by Reductive γ‐Deoxygenation and Heck–Matsuda Reaction: Asymmetric Total Synthesis of (−)‐Musellarins A–C and Their Analogues 下载免费PDF全文
Zhilong Li Dr. Fanny C. F. Ip Prof. Dr. Nancy Y. Ip Prof. Dr. Rongbiao Tong 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(31):11152-11157
Fully functionalized pyranuloses derived from Achmatowicz rearrangement (AR) are versatile building blocks in organic synthesis. However, access to trans‐2,6‐dihydropyrans from pyranuloses remains underexplored. Herein, we report a new two‐step trans arylation of AR products to access 2,6‐trans‐dihydropyranones. This new trans‐arylation method built on numerous plausible, but unsuccessful, direct arylation reactions, including Ferrier‐type and Tsuji–Trost‐type reactions, was finally enabled by an unprecedented, highly regioselective γ‐deoxygenation of AR products by using Zn/HOAc and a diastereoselective Heck–Matsuda coupling. The synthetic utility of the reaction was demonstrated in the first asymmetric total synthesis of (?)‐musellarins A–C and 12 analogues in 11–12 steps. The brevity and efficiency of our synthetic route permitted preparation of enantiomerically pure musellarins and analogues (>20 mg) for preliminary cytotoxicity evaluation, which led us to identify two analogues with three‐to‐six times greater potency than the musellarins as promising new leads. 相似文献
57.
A kind of new temperature sensitive molecularly imprinted polymer (MIP) with ofloxacin (OFL) as template was prepared for the coating of solid phase microextraction (SPME). Dopamine was self-polymerized on stainless steel fiber (SSF) as the SPME support followed by silanization. Then MIP was synthesized as SPME coating on the modified SSF in a capillary, with N-isopropyl acrylamide as temperature sensitive monomer and methacrylic acid as functional monomer. The synthesis could be well repeated with multiple capillaries putting in the same reaction solution. The obtained MIP fiber was evaluated in detail with different techniques and various adsorption experiments. At last the MIP fiber was used to extract the OFL in milk. Satisfied recoveries between 89.7 and 103.4% were obtained with the limit of quantification (LOQLC) of 0.04 μg mL−1 by the method of SPME coupled with high performance of liquid chromatography (HPLC). 相似文献
58.
HPLC Determination of Lansoprazole and Method Application for the Formulation Development of Enteric‐coated Lansoprazole Pellets 下载免费PDF全文
The aim of this study was to develop a validated HPLC method for the determination of lansoprazole in dissolution medium and pellets. For the formulation development, we investigated the role of 2‐hydroxypropyl‐β‐cyclodextrin (HPβCD) on the dissolution of enteric‐coated pellets of lansoprazole prepared by the solution layering technique using a fluid bed coater. Dissolution results demonstrated the coating using Acryl‐Eze protected the formulations from releasing lansoprazole in acid medium for the first 2 h, and the addition of HPβCD improved the dissolution performance by 189%, compared with the group without HPβCD. The DSC analysis displaced an absence of the endothermic peak for the lyophilized products lansoprazole and HPβCD, and FTIR analysis demonstrated the band broadening, shifting or disappearance compared to the spectra of the physical mixture, which indicated the formation of the inclusion complex between lansoprazole and HPβCD. This study has developed a validated HPLC method to measure lansoprazole in test media and pellets, which was applied successfully to the formula tion development of enteric‐coated pellets. 相似文献
59.
60.
Four Metal Complexes Based on Bulky Imidazole Ligands: Solvothermal Syntheses,Crystal Structures,and Fluorescence Properties 下载免费PDF全文
Xue Zhang Sai Li Yue‐Jiao He Tong Han Xiao‐Ling Wang Bang Chen Kang‐Yu Zou Zuo‐Xi Li 《无机化学与普通化学杂志》2015,641(11):1874-1880
In order to explore the influences of (de‐)protonation of the imidazole ring on the structural diversity of the resulting complexes, the imidazole‐based ligands 4, 5‐diphenylimidazole (Hdpi) and 1H‐phenanthro[9, 10‐d]imidazole (Hpi) were utilized as bulky building blocks to construct four complexes by solvothermal reactions, i.e. [Ag(Hdpi)2](NO3) · (H2O) ( 1 ), [Cu(dpi)]∞ ( 2 ), [Cu(Hpi)(NO3)]∞ ( 3 ), and [(H2pi)(NO3)] · H2O ( 4 ). In complex 1 , two Hdpi ligands adopt a monodentate pattern and coordinate with one AgI ion to form a mononuclear unit, which is further connected by hydrogen bonds into a 1D supramolecular helix. The deprotonated dpi ligand of 2 acts in bidentate mode, and bridges CuI ions to afford a 1D chain. In 3 , the NO3– ion, acts as a monodentate bridging ligand and joins CuI ions to generate a 1D chain. The Hpi ligand employs a monodentate mode to bond with CuI ions of the 1D chain. 4 is protonated and two H2pi nitrogen atoms are free of coordination. Interestingly, hydrogen bonds among the NO3– ion, the H2pi ligand, and the water molecule yield a macro ring R44(14). The resulting structural diversity reveals that the (de‐)protonation of imidazole ring directly steers the coordination number of ligand, and thus causes a significant effect on the structure, especially the dimensionality. Furthermore, the solid‐state fluorescence properties of the free ligands and compounds 1 – 4 were studied at room temperature. 相似文献