Efficient Syntheses of Traumatic Lactone and Rhizobialide

Herein, we report the total synthesis of traumatic lactone and rhizobialide by utilizing allenoic acid to construct the lactone ring. The key starting materials, allenoic acids, could be prepared by the ATA (allenation of terminal alkynes) of a terminal alkyne with an aldehyde that contained a protected hydroxyl group followed by hydrolysis. Importantly, the asymmetric synthesis could be realized just by replacing racemic diphenylprinol with (R)- or (S)-diphenylprinol to deliver the optically active allenoate.     

Isobutane Dehydrogenation Assisted by CO2 over Silicalite‐1‐Supported ZnO Catalysts: Influence of Support Crystallite Size

The ZnO catalysts supported on Silicalite‐1 zeolites with different crystallite sizes (0.08, 0.35, 1 and 1.7 μm, respectively) and 5% Zn were synthesized via an incipient wetness method. The catalysts were characterized by XRD, N₂ adsorption, SEM, TEM‐EDX, DRIFT spectra and NH₃‐TPD, and their catalytic performance in isobutane dehydrogenation assisted by CO₂ was investigated. The catalytic activity is strongly dependent on the crystallite size of Silicalite‐1 support. The ZnO/S‐1‐0.35 catalyst with ca. 0.35 μm crystallite size displays the highest activity, affording an initial isobutane conversion of 51.0% and 74.5% isobutene selectivity. This can be attributed to a higher amount of acid sites present on this catalyst as well as the largest amount of nest silanols possessed by the S‐1‐0.35 support.     

Carbazoles from the [4C+2C] Reaction of 2,3‐Allenols with Indoles

A mild and efficient method using readily available 1‐aryl‐2,3‐allenols and unprotected‐N indoles, Au⁺‐catalyzed cyclization, and aromatization to afford the final [4C+2C] products, carbazoles 4, with an excellent selectivity, is reported. The reaction demonstrates excellent regioselectivity and allows the N?H unit to undergo reactivity unprotected. A mechanism involving a spiropolycyclic intermediate has been proposed and synthetic application is also demonstrated.     

A facile synthesis of β-allenyl furanimines via Pd-catalyzed cyclization of 2,3-allenamides with propargylic carbonates

The Pd(OAc)₂/TFP-catalyzed cyclization reaction of 2,3-allenamides in the presence of propargylic carbonates provides an efficient route to β-allenyl furanimine derivatives. Preliminary mechanistic study showed that this reaction was probably initiated by Pd(0) species.     

鞘氨醇与DPPC, DPPE单层膜的热力学特性及形态观察

鞘氨醇(sphingosine)是生物体内合成鞘脂的母体化合物, 是生物膜中的重要组分之一. 通过分析表面压力和平均分子面积(π-A)等温线数据分别研究了鞘氨醇与二棕榈酰基磷脂酰胆碱(DPPC)和二棕榈酰基磷脂酰乙醇胺(DPPE)二元组分单层膜的热力学特性, 并在恒定膜压下制备不同摩尔比例的混合脂膜用原子力显微镜进行观测. 实验结果表明: (1)鞘氨醇与DPPC组成的系统中, XD-Sph＝0.2, 0.4, 0.6时, 过量分子面积与过量吉布斯自由能在所研究的表面压力下表现为负值, 而当XD-Sph＝0.8时, 表现为正值; (2)鞘氨醇与DPPE组成的系统中, 当表面压力 π＜25 mN•m－1时, 过量分子面积与过量吉布斯自由能在所研究的组分比例下表现为负值, 当π≥25 mN•m－1时为正值. 混合单层膜的分子面积与表面吉布斯自由能决定了分子间的相互作用, 当为负值时分子间相互作用表现为吸引力, 出现凝聚现象; 为正值时分子间相互作用表现为排斥力, 促使单层膜出现相分离现象. 过量吉布斯自由能值越小, 单层膜的热稳定性越高. 弹性系数曲线分析和AFM图片观测进一步验证了理论分析的结果.     

Ultrasensitive amperometric determination of PSA based on a signal amplification strategy using nanoflowers composed of single-strand DNA modified fullerene and Methylene Blue,and an improved surface-initiated enzymatic polymerization

The authors describe a signal amplification strategy for highly sensitive detection of the prostate-specific antigen (PSA). This is accomplished by a combination of two methods, viz. (a) improved surface-initiated enzymatic polymerization (SIEP), and (b) the use of nanoflowers prepared from C₆₀ fullerene and Methylene Blue (C₆₀/MB) modified with a long single-strand DNA. C₆₀/MB acts as a novel electrochemical indicator. The C₆₀/MB nanoflowers improve the load of MB and promote the electron transfer. The integration of the SIEP technique and the C₆₀/MB nanomaterial also results in improved loading of MB on the nucleic acid. Ultimately, dual cascade signal amplification is accomplished. The biosensor was constructed as follows: (a) Gold nanospheres were modified with antibody 2 (Ab₂) and a thiolated oligonucleotide (referred to as S₀). (2) S₀ is then extended by the SIEP reaction. (3) The redox indicator C₆₀/MB is then connected to the extended guanine-rich ssDNA which then yields the amperometric signal. (4) A sandwich immunoassay is performed by capturing the nanoprobe oy type Ab₂-Au-S₀ on the gold electrode modified with multi-walled carbon nanotubes (MWCNTs) and protein A. Current is measured by using differential pulse voltammetry (DPV). The synergic effect of the biofunctional nanomaterial and the signal amplification strategy greatly improves the performance of this immunoassay. Under optimized conditions and at a working voltage of typically ?0.18 V (vs Ag/AgCl), the assay has a linear range that extends from 15 pg·mL^?1 to 8 ng·mL^?1 of PSA. The detection limit is as low as 1.7 pg·mL^?1 (at an S/N ratio of 3). In our perception, this dual amplification scheme has a wide scope in that it may become applicable to numerous other immunoassays.

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Graphical abstract C₆₀/Methylene blue nanoflowers, a novel electrochemical indicator, connect with the long single-stranded DNA (ssDNA) extended by the improved surface-initiated enzymatic polymerization method. This amplification strategy is utilized to construct a sandwich prostate-specific antigen (PSA) immunosensor.

     

基于内置电光晶体F P标准具的扫描滤波方法

基于内置电光晶体的F-P标准具,利用F-P多光束干涉原理和晶体的线性电光效应,提出了一种能有效提高啁啾脉冲信噪比的扫描滤波方法。给出了电光晶体加载电压的时变函数表达式,分析了影响信噪比提升效果的主要因素,并重点讨论了电光晶体的电压控制参数对信噪比提升效果和滤波器透过率的影响。研究结果表明,利用该扫描滤波方法可将啁啾脉冲激光信噪比提升约2个量级。