Design, Synthesis of Chiral Ketone and Application in Asymmetric Epoxidation

A class of chiral ketone was synthesized for asymmetric epoxidation. High ee values have been obtained for a number of cis olefin and trans olefin. The epoxidation was stereospecific with no isomerizatiom observed in the epoxidation of acyclic system. Encourageingly high ee value has also been obtained for a number of terminal olefins. Mechanistic studies show that electronic interactions play an important role in the stereodifferentiation. O O O O O O NBoc O O t-BuO2CH2CN O O O …     

相位共轭皮秒光脉冲的直接观察和记录

利用条纹照相机直接观察和记录了由全息相位共轭技术产生的相位共轭的皮秒光脉冲。实验结果与理论相符合。 关键词：     

脱氢姜黄烯及其类似物的合成

利用苯乙酮及苯乙酮衍生物,经过傅-克乙酰化反应、偶联反应、Wittig烯化反应,合成了脱氢姜黄烯及其类似物.再经选择性催化氢化反应,可分别得到α-姜黄烯、黄根醇甲醚及姜黄氢醌甲醚.     

高强度聚乙烯醇/聚苯胺/聚吡咯/TiO2导电杂化水凝胶的制备与性能

本文以聚乙烯醇(PVA)、苯胺(ANI)、吡咯(Py)及钛酸丁酯(TBOT)为原料,通过溶胶-凝胶法、原位氧化聚合法及冷冻-融溶法一步得到聚乙烯醇/聚苯胺/聚吡咯/TiO 2(PVA/PANI/PPy/TiO 2)杂化水凝胶。结果表明,该杂化水凝胶具有优异的力学性能和导电性能。当n(ANI)∶[KG-*3/5]n(Py)=8∶[KG-*3/5]2(TBOT体积为100μL)时,其压缩强度高达2.45 MPa。同时,在外加电源的作用下,该凝胶能够使灯泡发光。当n(ANI)∶[KG-*3/5]n(Py)=2∶[KG-*3/5]8(TBOT体积为150μL)时,杂化水凝胶的电导率(0.25 S/m)最好。该杂化水凝胶有望广泛地应用在柔性可穿戴电子器件、安全离子电池、传感器和生物器件等领域。     

A Novel Approach to Synthesis of Tricyclic Diterpenoid

A novel approach has been found and the first total synthesis of (±)-Salvirecognine was accomplished by using it. In which intramolecular cyclization and Friedel-Crafts alkylation took place simultaneously to afford key intermediates for synthesis of aromatic tricyclic diterpenoids OMe PPA O O O OMe 1 2 Scheme 1 As shown in Scheme 1 intramolecular cyclization and Friedel-Crafts alkylation took place simultaneously when compound 1 was treated by PPA at 125 ℃. In which the i-pr…     

3-苯基-1-丁炔-3-醇质谱碎裂中[C8H7]^+的结构及分子内质子迁移反应

报道了3-苯基-1-丁炔-3-醇的常规电子轰击质谱(EIMS)。利用碰撞诱导解离(CID)技术研究了质谱碎裂过程中产生的[C8H7]^+的气相离子结构。同时, 氘代同位素交换、亚稳(MI)和CID实验进一步证实了m/z 103离子的形成并不是分子离子的质谱碎裂中顺次失去甲基自由基和中性CO分子的直接氢迁移的协同反应, 而是在失去CO分子前后发生了二次质子迁移反应的逐步过程。在此基础上提出了一种独特的双分子质子键合复合物中间体的碎裂机理。     

甘蓝夜蛾信息素类似物的设计合成及初步活性研究

甘蓝夜蛾隶属鳞翅目夜蛾科,主要危害甘蓝、西兰花、萝卜等十字花科蔬菜。与传统的化学农药防治相比,昆虫信息素防治具有专一性强、灵敏度高、绿色环保、同时不会误伤天敌等优点。但天然信息素易降解、持效期短,长期单一使用会诱导昆虫产生抗性等问题。针对这些问题,本文设计并合成了4种结构新颖的信息素类似物:反-11-十六碳烯-3-氯丙酸酯(G1)、反-11-十六碳烯-2-溴丙酸酯(G2)、11,12-二氟十六烷基-1-醇(G3)、11,12-二氟十六烷基乙酸酯(G4),并表征了其结构。通过触角电生理试验(EAG)初步测试了G1~G4的室内生物活性。     

Synthesis, Crystal Structure and Antiproliferative Activity of 2,2-Dimethyl-4-oxochroman-3-ylmorpholine-4-carbodithioate

The crystal structure of the new title compound 2,2-dimethyl-4-oxochroman-3-ylmorpholine-4-carbodithioate(C16H19NO3S2,Mr = 337.44) has been prepared and determined by single-crystal X-ray diffraction.The crystal is of triclinic,space group P1 with a = 9.5518(7),b = 9.7172(7),c = 11.0220(8),α = 67.08(1),β = 74.66(1),= 61.31(1)°,V = 822.72(10)3,Z = 2,Dc = 1.362 g/cm3,F(000) = 356,μ = 0.092 mm-1,MoKa radiation(λ = 0.71073),R = 0.0515 and wR = 0.1389 for 2623 observed reflections with I > 2(I).X-ray diffraction analysis reveals that the chroman ring adopts a half-chair conformation while the morpholine ring shows a chair conformation.Intramolecular and intermolecular C-H···S and C-H···O hydrogen bonds together with π-π interations are found in the structure.The result of MTT assay shows the title compound displays good antiproliferative activity against two human cancer cell lines.     

Aliphatic Organoimido Derivatives of Polyoxometalates Containing a Bioactive Ligand

A series of aliphatic organoimido derivatives of hexamolybdate based on amantadine, namely (nBu₄N)₂[Mo₆O₁₈(?NC₁₀H₁₅)] ( 1 ), (nBu₄N)₂ {cis‐[Mo₆O₁₇(?NC₁₀H₁₅)₂]} ( 2 ), (nBu₄N)₂{trans‐[Mo₆O₁₇(?NC₁₀H₁₅)₂]} ( 3 ), and (nBu₄N)₂[Mo₆O₁₆(?NC₁₀H₁₅)₃] ( 4 ), was synthesized in reasonable yield by dehydration with N,N′‐dicyclohexylcarbodiimide (DCC). They were characterized by IR and UV/Vis spectroscopy, elemental analysis, ESI mass spectrometry, and single‐crystal X‐ray structure analysis. The spectral and structural similarities and differences between monosubstituted, cis‐disubstituted, and trans‐disubstituted organoimido derivatives were elucidated and may provide guidance for related work on organoimido‐functionalized Lindqvist‐type polyoxometalates. In addition, trans‐disubstituted and polysubstituted derivatives containing aliphatic organoimido ligands have not yet been reported, and the crystal structure of the trans isomer may lead us to a deeper understanding of disubstituted derivatives. Furthermore, proliferation and morphology of MCF‐7 cells were studied with compound 1 . The present results show that the DCC‐dehydrating protocol could be an efficient approach to covalently graft bioactive ligands such as amantadine onto POMs and enhance their application in clinical cancer treatment.     

A method of identifying the blood contributor in mixture stains through detecting blood-specific mRNA polymorphism

In the past decades, messenger RNA (mRNA) biomarkers have been employed to identify the origin of body fluids in forensic medicine. We hypothesized that the polymorphism of mRNA could be applied to identify individuals in mixture samples composed of two body fluids. In this study, we selected five blood-specific mRNA biomarkers of venous blood (SPTB, CD3G, AMICA1, ANK1, and GYPA) that encompass 16 SNPs to identify the mixture contributor(s). Five specific gene markers for menstrual blood, semen, skin, saliva, and vaginal secretions were amplified and typed as body-fluid positive controls. We established the system of multiplex PCR and single base extension (SBE) reaction followed by CE. The amplicon size was between 90bp and 294bp. The peripheral blood specificity was examined against other human body fluids, including saliva, semen, skin, menstrual blood, and vaginal secretion. The 16 SNPs were peripheral blood specific and could be successfully typed in homemade mixtures which are composed of different body fluids with 1 ng peripheral blood mRNA added. This system showed a supersensitivity (1:100) in detecting the trace amount of peripheral blood mixed in other body fluids and a combined discrimination power (CDP) of 0.99929 in Chinese population. It was the first time to establish a method for identifying the blood donors and deconvoluting mixtures through detecting mRNA polymorphism with SNaPshot assay. This peripheral blood specific SNP typing system showed high sensitivity to the typing of blood source specific markers regardless of other body fluids in the mixture.