KF-Al2O3催化合成2-甲基-1-苄基苯并咪唑

苯并咪唑类杂环化合物具有杀菌、消炎、抗癌、抗氧化的活性,广泛用于食品的防虫和防腐,用于动、植物病毒的防治,人体疾病和肿瘤的防治[1-3],本文用KF Al2O3作催化剂,用DMF为溶剂,利用2 甲基苯并咪唑与苄基溴反应合成2 甲基 1 苄基苯并咪唑的新型方法,考察了诸因素对产率的影响,找出了最佳的反应条件。合成路线如下:1　实验部分1 1　仪器与试剂Brurer AM 500超导核磁共振波谱仪(溶剂CDCl3);CarloErbal1106型元素分析仪,NicoletIm pact410型红外光谱仪,KBr压片,HP1100型和Finnigan FTMS 2000型质谱仪(以上均由华东理工大学分析…     

A new approach to the synthesis of α-chlorocycloalkanones

α-Chlorocycloalkanones(Ⅳ) were synthesized from cycloalkanones via potassiumα-oxocycloalkylsulfonates(Ⅱ).A two-step mechanism was proposed to explain the formation ofⅣfromⅡ.     

含氰基基团的以C为中心的不对称阴离子离子液体的合成、表征及应用

首次通过不对称阴离子的钠盐/钾盐和不同的季胺化的咪唑,吡咯溴盐/氯盐进行离子交换,合成了一系列含氰基官能团的不对称阴离子功能化离子液体。通过红外、核磁共振、质谱和元素分析对离子液体的结构进行表征;通过TGA对离子液体的热稳定性进行测定,结果发现不对称功能化离子液体具有良好的热稳定性,其分解温度在219-319℃范围内。将功能化离子液体[Bmim][C(CN)2COCH3]作为弱配体应用于模型的Suzuki偶联反应,发现在反应中加入功能化离子液体[Bmim][C(CN)2COCH3]可以使反应收率提高10-15%。     

四（对羟基苯基）卟啉—硅胶固定相的合成及在核苷酸分析中的应用

以大孔微硅胶作基体，经γ－氨丙基三乙氧基硅烷活化与间隔臂氯代环内烷反应后，再与预先合成的四（对羟基苯基）卟啉配体键合，构成电荷转移型亲和色谱固定相。以ＰＨ＝７．０的磷酸盐缓冲溶液作流动相，成功实现对一些核苷酸的高效液相亲和色谱分离。     

Efficient reduction of graphene oxide catalyzed by copper

We report that copper thin films deposited on top of graphene oxide (GO) serve as an effective catalyst to reduce GO sheets in a diluted hydrogen environment at high temperature. The reduced GO (rGO) sheets exhibit higher effective field-effect hole mobility, up to 80 cm(2) V(-1) s(-1), and lower sheet resistance (13 kΩ □(-1)) compared with those reduced by reported methods such as hydrazine and thermal annealing. Raman and XPS characterizations are addressed to study the reduction mechanism on graphene oxide underneath copper thin films. The level of reduction in rGO sheets is examined by Raman spectroscopy and it is well correlated with hole mobility values. The conductivity enhancement is attributed to the growth of the graphitic domain size. This method is not only suitable for reduction of single GO sheets but also applicable to lower the sheet resistance of Langmuir-Blodgett assembled GO films.     

Palladium-catalyzed C–H glycosylation and retro Diels–Alder tandem reaction via structurally modified norbornadienes (smNBDs)

This report describes palladium-catalyzed C–H glycosylation and retro Diels–Alder tandem reaction via structurally modified norbornadienes (smNBDs). smNBDs were proposed to regulate the reactivity of the aryl-norbornadiene-palladacycle (ANP), including its high chemoselectivity and regioselectivity, which were the key to constructing C2 and C3 unsubstituted C4-glycosidic indoles. The scope of this substrate is extensive; the halogenated six-membered and five-membered glycosides were applied to the reaction smoothly, and N-alkyl (primary, secondary and tertiary) C4-glycosidic indoles can also be obtained by this method. In terms of mechanism, the key ANP intermediates characterized by X-ray single-crystal diffraction and further controlled experiments proved that the migration-insertion of smNBDs with phenylpalladium intermediate endows them with high chemo- and regioselectivity. Finally, density functional theory (DFT) calculation further verified the rationality of the mechanism.

This report describes palladium-catalyzed C–H glycosylation and retro Diels–Alder tandem reaction via structurally modified norbornadienes (smNBDs).     

Interplay between out-of-plane magnetic plasmon and lattice resonance for modified resonance lineshape and near-field enhancement in double nanoparticles array

Two-dimensional double nanoparticle （DNP） arrays are demonstrated theoretically, supporting the interaction between out-of-plane magnetic plasmons and in-plane lattice resonances, which can be achieved by tuning the nanoparticle height or the array period due to the height-dependent magnetic resonance and the periodicity-dependent lattice resonance. The interplay between the two plasmon modes can lead to a remarkable change in resonance lineshape and an improvement on magnetic field enhancement. Simultaneous electric field and magnetic field enhancement can be obtained in the gap region between neighboring particles at two resonance frequencies as the interplay occurs, which presents “open” cavities as electromagnetic field hot spots for potential applications on detection and sensing. The results not only offer an attractive way to tune the optical responses of plasmonic nanostructure, but also provide further insight into the plasmon interactions in periodic nanostructure or metamaterials comprising multiple elements.     

Fe—Silicalite—2催化剂表面CO2加氢反应性能的研究

研究了Ｆｅ／Ｓｉｌｉｃａｌｉｔｅ－２催化剂ＣＯ２加氢低碳烯烃反应性能，利用ＣＯ２－ＴＰＤ，ＣＯ２／Ｈ２－ＴＰＳＲ和ＣＯ／Ｈ２－ＴＰＳＲ表征手段，考察了铁含量及ＭｎＯ助剂对Ｆｅ／Ｓｉｌｉｃａｌｉｔｅ－２催化剂ＣＯ２吸附脱附及加氢反应性能的影响，表明随铁含量增加可提高催化剂对ＣＯ２的吸附能力，有利于提高ＣＯ２加氢反应的转化率。     

STRUCTURE OF CRYSTALLINE DOMAINS IN SEMICRYSTALLINE BLOCK COPOLYMER THIN FILMS

Thin film morphology of a symmetric semicrystalline oxyethylene/oxybutylene diblock copolymer （E76B38） on silicon was investigated by tapping mode atomic force microscopy （AFM）. It is found that the nascent thin film is composed of multiple polymer layers having mixed thicknesses of L ≈ L0 and L ≈ L0/2 （L0 is the long period of the block copolymer in bulk） besides the first layer near the substrate. This shows that the crystalline domain in the block copolymer consists of double poly（oxyethylene） layers. Annealing leads to disappearance of the polymer layers with thickness L ≈L0/2, indicating that such polymer layers are metastable.     

A Logic Fluorescent Chemosensor Based on Eu3+ Functionalized Cd-MOFs for Sensing Fe3+ and Cu2+ Synchronously

One of the most critical and yet unsolved issues is the effective monitoring of multiple heavy metal ions in complex systems through their specific function in fluorescence detection. In this work, luminescence-active cadmium base metal-organic frameworks (Cd-MOFs) based on the planar and rigid π-conjugated structure ligand benzo-(1,2;3,4;5,6)-tris (thiophene-2’-carboxylic acid) (H₃BTTC) was chosen. A series of sensing experiments demonstrated that the Cd-MOFs exhibits selective and sensitive response for Fe³⁺ and Eu³⁺ through fluorescence “turn off” and “antenna effect” respectively. In addition, the encapsulation of Eu³⁺ inside the Cd-MOFs (Eu³⁺@Cd-MOFs) led to an excellent probe with dual emission. To this end, a programmable fluorescence platform was developed to detect Fe³⁺ and Cu²⁺, in which the emission peaks of both the ligand and Eu³⁺ are completely quenched by Fe³⁺. The ratiometric detection of Cu²⁺ leads to a decrease in Eu³⁺ emission, while the ligand emission remains stable. To demonstrate the strategy, the fluorescence (Output) of Cd-MOFs, Eu³⁺@Cd-MOFs, and the analytes (Eu³⁺, Fe³⁺, and Cu²⁺, input) achieved elementary Boolean logic operations (OR, NOR, AND) and they constitute a logic fluorescent chemosensor to analyze Fe³⁺ and Cu²⁺ synchronously.