有机半导体荧光传感材料及危险化学品检测应用

荧光传感材料作为有机半导体光电功能材料的重要组成之一,以其灵敏度高、选择性强、响应速度快等优势,成为当前化学传感领域的一个研究热点,近年来在反恐、禁毒等领域有着广泛的应用.然而目前,对荧光敏感材料各项性能参数的设计与优化,依然存在着经验性问题,需要基于构效结合思维,从待测物质的分子层次的物性认知出发,更有针对性地设计相应的传感材料.本文基于国内外前沿工作,结合本课题组多年在危险化学品荧光传感方向的经验,以爆炸物、神经毒剂和合成毒品的检测为例,对荧光敏感材料的设计原则和传感的分子级微观作用机制进行了系统论述.     

基于发光材料的温度探测新机制探索

温度是最基本的物理量之一,它的准确测量在科学研究和技术应用等领域具有十分重要的意义。基于物质光学响应特性的温度探测是一种新型的测温技术,可以克服传统温度计内在的不足,满足非接触式、高分辨率、快速响应等探测需求。围绕着可用于温度传感的固体发光材料展开,从基于荧光强度、荧光强度比和荧光寿命这三类不同的温度探测方式出发,详细介绍了关于温度探测的工作所取得的成果和进展,讨论了它们作为测温材料的温度区间以及相对灵敏度,归纳总结了各自的优缺点,并对其发展前景进行了展望。     

SrAl2O4:Eu2+,Dy3+长余辉材料发光性能与温度依赖研究

对SrAl2O4:Eu2+,Dy3+长余辉材料在100～500 K温度之间的发光性能进行研究.实验结果表明,材料的荧光及余辉强度在特定温度区间内呈线性变化,在热释峰所在温度范围具有较好的发光性能.其变化规律表明SrAl2O4:Eu2+,Dy3+长余辉材料内部陷阱中电子的释放包括瞬时释放和延时释放两种类型,其中电子瞬时释放进而跃迁发光是荧光的组成部分,延时释放产生的跃迁则导致余辉发光.陷阱和电子的复合与陷阱中电子释放过程均随温度升高而增强,但温度过高时会发生热猝灭.材料荧光强度与余辉强度在特定温度区间内随温度呈线性变化关系表明其可以作为一种光纤温度传感材料.     

有机荧光温度传感体系研究进展

温度是最常见的物理量之一,对温度的精确测量无论在科学研究还是在生产生活中均具有重要意义.荧光温度传感是一种新型半侵入式温度测量方法,具有高灵敏度、快速响应、可视化效果好等优点.有机荧光分子是最早用于荧光温度传感的材料,近年来有机荧光温度传感体系研究取得显著进展.主要对近五年有机荧光温度传感的重要研究成果进行综述,并对其未来发展进行展望.     

X射线荧光光谱法对聚变靶丸保气半寿命的测量

建立了非破坏性测量单个聚变靶丸保气半寿命的方法,测量的相对不确定度约为10%.利用X射线荧光(XRF)光谱仪测量不同时刻靶丸内气体的相对含量,根据气体泄漏规律计算其漏率,从而计算出靶丸的保气半寿命.由于110 ℃时的靶丸保氩半寿命与常温下靶丸保氘半寿命相关,因此分别测量了塑料聚变靶丸在常温及100 ℃时对氩气的保气半寿命;常温下塑料靶丸的保氩半寿命达数千小时,而100 ℃时塑料靶丸的保氩半寿命仅数十小时.考察了仪器的稳定性以及样品纵向位置z对谱线强度的影响.由于采用了样品位置精确定位技术,因此测量不确定度主要来源于仪器的稳定性.该技术因其无损、快速和简单而作为靶丸质量控制工具,用以淘汰漏率快于建立的标准设定值.XRF光谱法为惯性约束聚变实验用靶提供了一一对应的保气半寿命参数,使聚变实验结果得到明显改善.     

新型荧光双重敏感响应性壳聚糖衍生物的合成及其发光性能研究

为了开发新型多功能天然高分子荧光材料,合成出一种新型含有环氧丙氧基荧光素(EPF)基团的水溶性壳聚糖衍生物GCS-EPF, 并用IR,1H NMR,UV光谱和荧光光谱等手段进行结构和发光性能的研究. 结果表明, 修饰后水溶性壳聚糖(GCS)的水溶液、 固体粉末和薄膜在520 nm附近具有较强的荧光发射, 其荧光强度不仅在0-60 ℃时对度有较快敏感响应, 同时在pH=0-13.5时对pH也有较快敏感响应, 具有双重敏感响应, 因此可将其作为温度荧光探针和pH荧光探针的高分子材料.     

透明导电玻璃(ITO)基材自加热传感静态芯片聚合酶链反应(PCR)

利用商品化ITO玻璃导电层的温阻效应, 无需任何微加工手段, 实现了自加热和传感的芯片温度自动程序控制, 最大程度地减小了传感滞后对温度控制稳定性的影响, 温度控制的稳定性达到了0.2 ℃, 升温速度最快可达20 ℃/s以上, 在冷却风扇辅助下降温速度最快达到了8 ℃/s. 芯片温控单元的引线从传统的两对(一对用于传感, 一对用于加热)减少为一对. 通过在该芯片上直接构建多个开放微池反应器的方法成功地实现了λDNA 157 bp片段的并行扩增. 将该芯片置于倒置荧光显微镜样品台上, 以蓝色(575 nm)发光二极管为光源, 以光电倍增管为检测手段检测了dsDNA和SYBR Green Ⅰ嵌合物的荧光强度随温度的实时变化曲线.     

用正电子研究CuCl2在NaY上的扩散

用正电子湮没谱学研究了机械混合CuCl₂与NaY中CuCl₂在NaY沸石中的扩散.分别测量了不同质量比的CuCl₂-NaY(0～0.03)沸石分子筛经140℃烘烤1h;CuCl₂-NaY(0～0.05)经450℃烘烤4h;CuCl₂-NaY(0.01)经不同温度烘烤1h以及经300℃下烘烤烘不同时间后的正电子寿命谱.所有谱中都出现了5(或4)个寿命分量,其第3,4,5寿命分量分别与β笼、超笼及沸石微粒界面空间的大小和数量相关.实验表明,正电子湮没谱学可敏感地探测出少量CuCl₂在NaY沸石中的扩散变化.而对于只含少量氯化铜(0.01)的情况,虽经高温长时间烘烤,但仍有相当数量的氯化铜存在于NaY外表面.     

氮掺杂碳量子点的制备及在细胞温度传感中的应用

该研究以生物质西红柿为碳源和氮源,通过微波法制备了氮自掺杂碳量子点（N-CQDs）。通过场发射透射电子显微镜（TEM）、X射线光电子能谱仪（XPS）和荧光光度计等对其形貌、结构、稳定性、光电性能、温敏性及细胞毒性进行考察,并用于活细胞温度传感研究。实验结果表明,所制备的N-CQDs稳定性强,光电性能优异,对温度具有较强的敏感性。在25～65℃范围内,N-CQDs的荧光强度随着温度的升高而降低,两者呈良好的线性关系。N-CQDs能穿透4T1细胞的细胞膜,显示出低毒性和生物相容性,在4T1细胞中具有良好的温度传感性能。该N-CQDs在活细胞荧光温度传感领域具有较大的应用潜能,有望作为温敏型纳米荧光探针在细胞研究等生物医学领域得到广泛应用。     

荧光传感方法检测爆炸物的研究进展

爆炸物检测是当前国际安全中迫切关注的问题之一。在过去的几十年中,大量的荧光传感材料用于荧光传感检测气态、液态和固态爆炸物见诸于报道。近年来,为了实现爆炸物的快速响应、高灵敏和高选择性的检测,研究工作者大力开发了各种新型荧光材料。这篇综述总结了近年来用于爆炸物检测的先进荧光材料,详尽、系统、重点地介绍了共轭聚合物、荧光小分子、超分子体系、具有聚集诱导发光效应的活性材料及静电纺丝纳米材料等各种荧光材料在爆炸物检测中的应用,展望了荧光传感方法在爆炸物检测领域的应用前景。     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

Selective syntheses of 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones via temperature-dependent Rh(II)-carbenoid-mediated 2H-azirine-ring expansion

The Rh(II)-catalyzed reaction of 2-carbonyl-substituted 2H-azirines with ethyl 2-cyano-2-diazoacetate or 2-diazo-3,3,3-trifluoropropionate provides an easy access to 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones. These compounds can be selectively prepared from the same starting material using temperature as the only varied parameter. The 2-azabuta-1,3-diene intermediate, a common precursor for both heterocyclic products, isomerizes into 2H-1,3-oxazine under kinetic control, while 1H-pyrrol-3(2H)-one is the sole product of the reaction at elevated temperatures. According to DFT-calculations a one-atom oxazine ring contraction involving ring-opening to a 2-azabuta-1,3-diene intermediate, followed by a 1,5- and 1,2-prototropic shift leads to the consecutive formation of imidoylketene and azomethine ylide, which then further undergo cyclization to the pyrrole derivative.     

Copper catalyzed/mediated synthetic methodology for ebselen and related isoselenazolones

Scope of the copper catalyzed/mediated selenium-nitrogen coupling reaction has been studied for the synthesis of isoselenazolones. It is noticed that the 2-chloro, 2-bromo-, and 2-iodo-aryl amides substrates can be exploited in the selenium-nitrogen coupling reaction by employing 25-100 mol % of CuI/1,10-phenanthroline (L) and potassium carbonate as a base in DMF. Furthermore, electron rich 2-chloro-arylamides also underwent selenium-nitrogen coupling reaction to give biologically important selenium-nitrogen heterocycles. Also, copper-catalyzed selenium-nitrogen coupling reaction has been meticulously applied for the synthesis of diaryl diselenides having methoxy, amine, and amide functionality from respective aryl iodides in the presence of stoichiometric amount of succinimide as an external Se-N coupling partner.     

Knoevenagel condensation catalyzed by novel Nmm-based ionic liquids in water

A series of novel N-methyl morpholine (Nmm) based ionic liquids with 1,2-propanediol group were synthesized and used as catalysts for Knoevenagel condensation at room temperature in water. Under the effect of the catalyst, various aldehydes or aliphatic ketones could react with a wide range of activated methylene compounds well, including malononitrile, alkyl cyanoacetate, cyanoacetamide, β-diketone, barbituric acid, 2-arylacetonitrile and thiazolidinedione. Furthermore, most of the products could be separated just by filtrating and washing with water. Additionally, the catalyst is recyclable and applicable for the large-scale synthesis.     

Construction of polyheterocyclic spirotetrahydrothiophene derivatives via sulfa-Michael/aldol cascade reaction

A series of polyheterocyclic spirotetrahydrothiophene derivatives were obtained in moderate to excellent yields via a catalyst-free sulfa-Michael/aldol cascade reaction of chalcones 1 and commercially available 1,4-dithiane-2,5-diol 2 under mild conditions. We also present the first asymmetric sulfa-Michael/aldol cascade reaction of chalcones 1 and commercially available 1,4-dithiane-2,5-diol 2 with moderate to good enantioselectivities catalyzed by readily available chiral phase-transfer catalysts (PTCs).     

Suzuki-Miyaura reactions of the soluble guanylate cyclase inhibitor NS2028: a non-product specific route to C-8 substituted analogues

Both soluble guanylate cyclase (sGC) inhibitors ODQ 1 and NS2028 2 are synthesized via improved protocols. In the former case treating 3,4-dihydroquinoxalin-2(1H)-one oxime 8, which can be prepared in two steps from 1,2-benzenediamine, with 1,1′-carbonyldiimidazole (CDI) gives the dihydro-ODQ 10 that in the presence of KMnO₄ oxidises to give ODQ 1 in an overall yield of 46% starting from 1,2-benzenediamine. In the latter case, the synthesis affords NS2028 2 from 2-amino-4-bromophenol 3 in three steps with an overall yield of 85% and avoids the need for chromatography. Furthermore, Suzuki-Miyaura reaction conditions are described that enable the preparation of 8-aryl and 8-heteroaryl derivatives of NS2028 directly from NS2028 2. Finally, demethylation of the 8-(methoxyphenyl) substituted analogues afforded the 8-(hydroxyphenyl) derivatives 40-42. All new products are fully characterised.