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91.
Anand VG Venkatraman S Rath H Chandrashekar TK Teng W Ruhlandt-Senge K 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(10):2282-2290
Modified octaphyrins with 34pi electrons have been synthesized and characterized following a simple synthetic methodology. An acid-catalyzed alpha,alpha coupling of tetrapyrranes containing furan, thiophene and selenophene rings resulted in the formation of the respective octaphyrins in relatively good yield. Solution studies by (1)H NMR and 2D NMR methods and single crystal Xray structural characterization reveal an almost flat structure with two heterocyclic rings inverted. Specifically, in 14 two selenophene rings (one on each biselenophene unit) are inverted while in 15 two furan rings (one on each bifuran unit) are inverted when the meso substituent are mesityl groups. On changing the mesityl substituent to m-xylyl group as in 19, the location of ring inversion shifts to pyrrole rings (one on each bipyrrole unit) indicating the dependence of structure on the meso substituents. UV/Vis studies, both in freebase and protonated forms reveal typical porphyrinic character and the aromatic nature of the octaphyrins. The Deltadelta values evaluated by (1)H NMR spectroscopy also support their aromatic nature. The protonated forms of octaphyrins bind TFA anion in a 1:2 ratio. The TFA anions are located one above and below the plane of the octaphyrin macrocycle and they are held by weak electrostatic NH-O interactions similar to that observed for protonated rubyrins. However, in the present case, there is an additional non-electrostatic CH-O interaction involving beta-CH of the inverted heterocyclic ring and the carbonyl oxygen of the TFA. Furthermore, inter molecular interactions between the Cbond;H of the meso-mesityl group and the fluorine of CF(3) group of bound TFA leads to the formation of one-dimensional supramolecular arrays with interplanar distance of 13 A between two octaphyrins. 相似文献
92.
A Setaram C-80 calorimeter has been modified in order to measure the heat flow of energetic materials at pressures up to 69 MPa. A manifold and sample cells capable of operating at high pressure were designed, constructed and evaluated. This paper will describe, in detail, the high pressure manifold construction, safety assessment and calibration. As well, the results for initial trials with ammonium nitrate (AN), and pentaerythritol tetranitrate (PETN) at various pressures and heating rates will be discussed. 相似文献
93.
《Electroanalysis》2003,15(18):1453-1459
A novel method for fabricating a micro gas sensor film on an indium tin oxide (ITO) electrode patterned using micro‐machining technology was developed. A micromanipulation system equipped with a counter electrode (Au; Ø10 μm) and a microsyringe, which was connected to a microinjection system, was first constructed. With this system, micro gas sensor arrays could be successfully prepared on ITO electrodes. Two kinds of micro gas sensor films were prepared, based on polythiophene (PTh) and poly(3‐n‐dodecylthiophene) (PD). The response behavior of conventional PTh and micro‐PTh films against NH3 at three different operating temperatures (25, 40 and 60 °C) was investigated by measuring the resistance of the film. With the micro‐PTh film, a reversible response was observed against NH3 when measured at 40 and 60 °C. In addition, the responsive characteristics of the microsensor films against different testing gases were examined at the three operating temperatures. The resistance of the microsensor films of PTh and PD changed considerably, depending on the type of testing gas, allowing these sensor films to be used for the detection of various gases. Furthermore, the microsensor films had a high stability compared with conventional films prepared from the same polymer. 相似文献
94.
Summary The effects of concentration, separation and spectral similarity as factors influencing the accuracy of iterative target testing
factor analysis (ITT-FA) are investigated for three component systems by the application of analysis of variance (ANOVAR).
ANOVAR is applied over a range of peak separations to map the changing effects of the three factors with increasing overlap.
Two error responses were measured and analysed, (a) Relative cluster error (RCE) a measure of the error over all peaks in
a cluster and (b) Relative peak error (RPE) the error of an individual peak. Multicomponent analysis (MCA) a method requiringa priori spectral information, is used as a referee method for ITT-FA. 相似文献
95.
二维液相色谱(2D-LC)因具有较高的峰容量,在复杂样品的分离分析中获得了广泛的关注。然而,制备型2D-LC以纯化高纯单体为目标,在方法开发和设备构成等方面与分析型2D-LC有较大的不同,目前尚未得到充分的开发,在大规模的制备纯化中应用较少。本文以一套制备液相色谱模块为分离系统,以稀释泵、切换阀和捕集柱阵列为接口,构建了新型的制备型2D-LC系统,旨在规模化纯化多个活性成分。以烟叶中可以用作医药原料的烟碱、绿原酸、芦丁和茄尼醇等组分为目标物,考察了不同类型填料对样品的捕集效率、过载条件下的色谱保留行为等,优化了制备色谱条件。进而利用在线2D-LC系统实现了烟叶提取物的纯化,通过一次运行获得了4个高纯化合物。该系统具有中压色谱纯化成本低、系统在线运行自动化程度高、稳定性好及容易放大等优点。烟叶中活性化学成分的回收利用对促进烟草行业的发展及带动地方农业经济开发具有重大的意义。 相似文献
96.
Keerakit Kaewket Pattanaphong Janphuang Peerawat Laohana Nantawat Tanapongpisit Wittawat Saenrang Kamonwad Ngamchuea 《Electroanalysis》2023,35(2):e202200200
Silver microelectrode arrays are fabricated by photolithography for a one-step analysis of H2O2 in low ionic strength samples. The effects of electrode length, width, band-to-band separation, connection height, and adhesion layer are evaluated. The developed sensor shows excellent repeatability (RSD=1.20 % (n=5)) and reproducibility (RSD=1.12 % (n=5)) with the linear range of 0.0–10.0 mM, the sensitivity of 9.84±0.34 μA mM−1, and the detection limit of 22.69 μM. The sensor has been successfully applied to detect H2O2 directly without the addition of supporting electrolyte in synthetic urine, tap water, drinking water, and milk samples. 相似文献
97.
We reported a manually operated static droplet array (SDA)-based device for the synthesis of nonspherical microparticles with different shapes. The improved SDA structure and reversible bonding between poly(dimethylsiloxane) (PDMS) were used in the device for the large-scale synthesis and rapid extraction of nonspherical microparticles. To understand the device physics, the effects of flow rate, SDA well size, and shape on droplet generation performances were explored. The results indicated that droplet generation in SDA structures was insensitive to the flow rate, and monodisperse droplets were generated by the SDA-based device through manually pushing the syringe. Finally, we integrated four kinds of SDA structures in one device and successfully realized the synthesis and extraction of nonspherical microparticles with different shapes and materials. Our SDA-based device offers numerous advantages, such as simple manual operation, low equipment cost, controllable microparticle shapes and sizes, and large-scale production. Thus, it holds the potential to be used as a flexible tool for the production of nonspherical microparticles. 相似文献
98.
99.
100.
采用模压成型方法制备了2种柔软性不同的热塑性聚氨酯/短切碳纤维/碳纳米管(TPU/SCF-CNT)复合材料复制物, 其表面上具有倒金字塔微结构阵列, 内部有SCF与CNT共同构成的导电通路. 将复合材料复制物和相应的复合材料平整片封装成柔性传感器. 结果表明, 压力作用下传感器内复制物和平整片之间的接触电阻因倒金字塔底棱的形变而显著降低. 对使用柔软性较高的复合材料封装的传感器, 虽然其相对迟滞稍大, 但压力作用下倒金字塔底棱形变量较大, 且复制物和平整片内导电通路增加量较大, 因此其在0~2.5 kPa的线性区内具有较高的灵敏度(0.32 kPa?1). 制备的2种传感器均具有快速响应特性, 且能在500 s(约1580次)的循环压缩/释放测试(峰值压力约3 kPa)中保持较稳定的电阻响应. 研究表明, 利用模压成型的表面倒金字塔结构复合材料复制物封装成的柔性压力传感器具有良好的传感性能. 相似文献