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1.
上转换发光是一种将长波长的激发光转化为短波长发射的反斯托克斯发光现象,三线态-三线态湮灭上转换(TTA-UC)能够在较低密度能量下被激发,且上转换量子产率高,因此获得研究者们广泛关注。关于敏化剂分子结构与上转换发光性能相关性的研究一直是TTA-UC研究领域的重要热点,选择两种代表性的卟啉钯光敏剂[PdOEP-八乙基卟啉钯(Ⅱ)和PdBrTPP-四溴苯基卟啉钯(Ⅱ)]与蒽衍生物9,10-(4-羟甲基)苯基蒽p-DHMPA发光剂组合上转换体系作为研究模型,通过一系列合成工作获得材料分子后,进一步比较两种敏化剂的光谱性质与体系最终上转换性能之间关系。通过细致研究敏化剂和发光剂的荧光发射和寿命等光谱性质对敏化剂系间窜越,三线态-三线态能量转移及三线态-三线态湮灭等能量传递过程的影响后,发现在532 nm处的摩尔吸光系数PdBrTPP (10.8 cm-1·mmol-1)大于PdOEP (3.0 cm-1·mmol-1);三线态寿命PdBrTPP (173.13 μs)大于PdOEP (109.21 μs)。但与p-DHMPA配对时光敏剂与发光剂的三线态能级差ΔETT,PdOEP (0.140 eV)却高于PdBrTPP (0.062 eV),通过Stern-Volmer方程得到Stern-Volmer猝灭常数KSV和双分子猝灭常数kq值也是PdOEP略高,最终表现出上转换阈值PdOEP/p-DHMPA (22.40 mW·cm-2)小于PdBrTPP/p-DHMPA (29.78 mW·cm-2),上转换发光效率ΦUC,PdOEP/p-DHMPA (28.3%)大于PdBrTPP/p-DHMPA (26.8%)。因此,卟啉钯敏化剂的构效对三重态湮灭上转换发光效率影响最为重要的决定因素是敏化剂三线态高低。对于不同的敏化剂,在分子主体结构、摩尔吸光系数与三线态寿命等光谱参数差别不大的情况下,敏化剂的三线态能级越高,就将会具有更大的上转换发光效率。然而如果以总上转换能力指标来评价,PdBrTPP的共轭结构能够提升其在激发波长处吸收更多光子的能力,具有比PdOEP更高的摩尔吸光系数,造成其总上转换能力η比PdOEP高3.4倍。因此从上转换总效能指标来评价,通过敏化剂分子设计调控其在激发光波长处的摩尔吸光系数也不失为一种简单易行的方法。  相似文献   
2.
The aim of this work was to evaluate the influence of US on the properties of the fluconazole emulsions prepared using imidazolium-based ILs ([Cn C1im]Br). The effects of the preparation method (mechanical stirring or US), US amplitude, alkyl chain length (of [C12C1im]Br or [C16C1im]Br), and IL concentration on the physicochemical properties were evaluated. Properties such as droplet size, span index, morphology, viscosity encapsulation efficiency, and drug release profile were determined. The results showed that US-prepared emulsions had a smaller droplet size and smaller polydispersity (Span) than those prepared by mechanical stirring. Additionally, the results showed that emulsions prepared with [C16C1im]Br and US had spherical shapes and increased stability compared to emulsions prepared by MS, and also depended on the IL concentration. The emulsion prepared by US at 40% amplitude had increased encapsulation efficiency. US provided a decrease in the viscosity of emulsions containing [C12C1im]Br; however, in general, all emulsions had viscosity close to that of water. Emulsions containing [C16C1im]Br had the lowest viscosities of all the emulsions. The emulsions containing the IL [C16C1im]Br had more controlled release and a lower cumulative percentage of drug release. The IL concentration required to prepare these emulsions was lower than the amount of conventional surfactant required, which highlights the potential synergic effects of ILs and US in preparing emulsions of hydrophobic drugs.  相似文献   
3.
In the past decade, big data has become increasingly prevalent in a large number of applications. As a result, datasets suffering from noise and redundancy issues have necessitated the use of feature selection across multiple domains. However, a common concern in feature selection is that different approaches can give very different results when applied to similar datasets. Aggregating the results of different selection methods helps to resolve this concern and control the diversity of selected feature subsets. In this work, we implemented a general framework for the ensemble of multiple feature selection methods. Based on diversified datasets generated from the original set of observations, we aggregated the importance scores generated by multiple feature selection techniques using two methods: the Within Aggregation Method (WAM), which refers to aggregating importance scores within a single feature selection; and the Between Aggregation Method (BAM), which refers to aggregating importance scores between multiple feature selection methods. We applied the proposed framework on 13 real datasets with diverse performances and characteristics. The experimental evaluation showed that WAM provides an effective tool for determining the best feature selection method for a given dataset. WAM has also shown greater stability than BAM in terms of identifying important features. The computational demands of the two methods appeared to be comparable. The results of this work suggest that by applying both WAM and BAM, practitioners can gain a deeper understanding of the feature selection process.  相似文献   
4.
5.
聚醚醚酮(PEEK)由于其耐热、耐腐蚀、耐辐照、抗疲劳、电绝缘性等优良性能,在许多领域可以代替金属、陶瓷等传统材料而得到广泛应用。特别是随着5G技术的发展和应用,PEEK已经成为5G热门材料。在PEEK材料实际应用中,温度的影响是一个非常重要和关键的因素。主要研究了PEEK太赫兹光谱以及温度对PEEK太赫兹光谱特性的影响。通过利用太赫兹透射光谱技术,同时结合控温装置,在温度从25~300 ℃均匀上升过程中,每间隔5 ℃测试得到PEEK片状样品的太赫兹时域光谱数据,利用光学参数提取算法可以得到PEEK的吸收系数、介电常数等光学参数,进一步得到特定频率下光学常数随温度的变化趋势,从而对材料进行表征和分析。在0.5~4 THz有效光谱范围内,实验结果表明,在常温(25 ℃)下,PEEK在3.5 THz具有一个明显的特征吸收峰。在25~300 ℃这个温度范围内,在1 THz频率下,PEEK的吸收系数、介电常数相对于室温分别有4.38%和5.0%的波动,同时PEEK在常温下在1 THz的介电损耗正切值为2.5×10-3,相比于PMMA和PE等高分子材料,PEEK的介电损耗正切值要低得多,且在升温过程保持相对稳定,表明PEEK在太赫兹频段的光谱特性具有很好的热稳定性和较低的介电损耗。研究结果表明,太赫兹光谱技术可以结合温控装置,通过材料的光学参数对高分子材料热稳定性进行研究和表征,同时还可以得到材料在不同温度下的介电性质。太赫兹光谱技术具有快速、高效、无标记、无损伤等优势,只需要压片就可以对固体样品进行测试,对于研究材料内部缺陷、稳定性以及材料的鉴别等具有很好的研究意义。同时本实验的测试数据可以为PEEK材料在不同温度下5G和6G等高频通信应用提供参考。  相似文献   
6.
Favipiravir finished dosage was approved for emergency use in many countries to treat SARS-CoV-2 patients. A specific, accurate, linear, robust, simple, and stability-indicating HPLC method was developed and validated for the determination of degradation impurities present in favipiravir film-coated tablets. The separation of all impurities was achieved from the stationary phase (Inert sustain AQ-C18, 250 × 4.6 mm, 5-μm particle) and mobile phase. Mobile phase A contained KH2PO4 buffer (pH 2.5 ± 0.05) and acetonitrile in the ratio of 98:2 (v/v), and mobile phase B contained water and acetonitrile in the ratio of 50:50 (v/v). The chromatographic conditions were optimized as follows: flow rate, 0.7 mL/min; UV detection, 210 nm; injection volume, 20 μL; and column temperature, 33°C. The proposed method was validated per the current International Conference on Harmonization Q2 (R1) guidelines. The recovery study and linearity ranges were established from the limit of quantification to 150% optimal concentrations. The method validation results were found to be between 98.6 and 106.2% for recovery and r2 = 0.9995–0.9999 for linearity of all identified impurities. The method precision results were achieved below 5% of relative standard deviation. Forced degradation studies were performed in chemical and physical stress conditions. The compound was sensitive to chemical stress conditions. During the study, the analyte degraded and converted to unknown degradation impurities, and its molecular mass was found using the LC–MS technique and established degradation pathways supported by reaction of mechanism. The developed method was found to be suitable for routine analysis of research and development and quality control.  相似文献   
7.
黄瑞琴  王胜  刘峥  唐群  魏润芝 《人工晶体学报》2022,51(11):1944-1951
将有机物2,5-二溴对苯二甲酸(H2L1)和2,2′-联吡啶(L2)作为双配体,使用溶剂热法和七水合硫酸锌(ZnSO4·7H2O)、六水合硝酸钴(Co(NO3)2·6H2O)分别反应,得到配合物[Zn(L1)(L2)(H2O)]n(1)和配合物[Co(L1)(L2)(H2O)]n(2)。采用单晶X射线衍射、元素分析、红外光谱、紫外光谱、荧光光谱、热重分析等测试方法对这两种物质进行分析研究。单晶测试结果表明配合物1是单斜晶系,以Zn2+配位连接L2-1与L2形成一维链状结构,各条链在分子间氢键和π…π共轭作用下有规律地堆叠形成三维网络结构。配合物2是三斜晶系,Co1离子和Co1i离子由H2L1上的羧酸氧原子O4和O4i连接,形成双齿螯合的配位结构单元,以Co2+配位连接 L2-1和L2形成二维网格结构,各层在O—H…O分子间氢键和范德瓦耳斯力作用下有规律的堆叠形成三维网络结构。配合物1和2均含有芳香杂环、羧基杂环和氮杂环,具有良好的荧光性质和热稳定性,最大发射波长分别为345 nm和333 nm。  相似文献   
8.
Cr3+-doped phosphors show significant application potential in near-infrared (NIR) light-emitting diodes (LEDs). However, the development of thermally stable and efficient NIR phosphors still faces enormous challenges. Herein, NIR phosphors K2NaMF6:Cr3+ (M3+ = Al3+, Ga3+, and In3+) were synthesized by the hydrothermal method. The represented K2NaAlF6:Cr3+ phosphor can be effectively excited by blue light (~430 nm) to present broadband emission at half a maximum of 96 nm peaking at ~ 728 nm. Meanwhile, the K2NaAlF6:Cr3+ phosphor exhibits excellent internal quantum efficiency (IQE = 68.08%) and nearly zero-thermal-quenching behavior, which is able to maintain 96.5% emission intensity at 150 °C of the initial value at 25 °C. The NIR phosphor-converted LED was fabricated based on K2NaAlF6:Cr3+ phosphor and a blue LED chip, showing a NIR output power of 394.39 mW at 300 mA with a high photoelectric conversion efficiency of 10.9% at 20 mA. Using the high-power NIR LED as a lighting source, transparent and quick veins imaging as well as non-destructive testing were demonstrated, suggesting the NIR phosphor has a wide range of practical applications.  相似文献   
9.
催化裂化是石油化工的核心单元之一.从催化裂化尾气中分离出来的碳四馏分富含许多的不饱和烯烃,如1-丁烯、顺、反式-2-丁烯以及少量的1,3-丁二烯,这些不饱和烯烃可以通过后续聚合反应,生成合成橡胶和工程塑料的重要原料,具有重要的应用价值.上述工艺过程对原料中1,3-丁二烯的含量(<100~200 ppm)有严苛的要求.采用选择性加氢技术对碳四馏分中的1,3-丁二烯进行选择性加氢,将其转化为更高附加值的单烯烃是一个理想的解决方案.然而,1,3-丁二烯加氢反应得到的单烯烃可能发生深度加氢得到副产物丁烷.因此,开发高效选择性加氢催化剂对碳四资源的利用具有重要的现实意义.另一方面,1,3-丁二烯加氢反应可以作为模型反应,用来考察选择性加氢催化剂的性能.基于此,该反应无论在工业界还是学术界均受到广泛关注.尽管如此,有关1,3-丁二烯加氢催化剂研究进展方面的综述极少.仅有关于1,3-丁二烯加氢作为模型反应的综述报道.本文对过去半个世纪以来1,3-丁二烯加氢反应中不同催化剂的发展历程进行系统综述,特别是包括Pd,Pt和Au等的单一贵金属催化剂.重点介绍以下内容:(1)固体催化剂构效关系,包括活性金属尺寸效应、晶面和形貌效应以及载体效应(晶相、孔道和酸碱性);(2)高性能催化剂的设计新策略,如单原子催化剂、核壳结构催化剂、金属-离子液复合催化体系以及载体的形貌调控;(3)催化剂的反应机理和失活机理.提出了1,3-丁二烯选择性加氢高性能催化剂开发面临的挑战,并对潜在的发展方向进行了展望.本文认为随着纳米技术和金属纳米材料合成方法的快速发展,对贵金属活性组分进行原子层面上的调控(包括形貌、尺寸以及单原子配位环境等)已成为可能.这将有助于研制出一类新型高性能选择性加氢催化材料,从而实现高转化率条件下高附加值单烯烃的定向转化.此外,载体的酸碱性和孔道结构的调控有助于进一步调节催化剂的抗积炭性能,也是未来发展的一个重要方向.  相似文献   
10.
本文研究了弹性地基上梁主共振响应的时滞效应.基于Hamilton原理,建立了时滞影响下弹性地基上梁的非线性运动微分方程,采用多尺度法,求得了时滞效应下主共振响应调制方程以及稳定性条件.通过数值算例,分析了时滞和调谐参数影响下主共振响应的峰值及幅频响应特性.结果表明,地基反力中的时滞效应对主共振响应影响较大,会导致共振域偏移,在一定区间内,响应幅值随时滞变化先减小再增大,呈现出周期性,并导致幅频曲线弯曲程度增大.  相似文献   
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