超分子组装体系中基于三重态-三重态湮灭的上转换发光

超分子组装实质上是对分子的精密组织和调控,结合三重态-三重态湮灭上转换发光,能够调控分子激发态能量的转移,提高上转换效率。本文综述了超分子组装体系中上转换发光的研究进展,包括基于有机凝胶、亲疏溶剂组装的超分子膜、纳米颗粒、聚合物薄膜以及主-客体配位超分子等体系。这些超分子体系为上转换发光提供了良好的基质,取代了传统三重态-三重态湮灭上转换发光的溶液体系,既解决了由于染料溶解性导致的聚集荧光猝灭,又有效地阻隔了氧气,同时,将上转换发光体系固体化而便于集成到器件等各个应用领域。值得注意的是,不同的超分子组装体系中的上转换发光,有着温度响应,可逆开/关效应,甚至是将光能转化为机械能的特性。     

荧光超分子聚合物研究进展

超分子聚合物是单体通过非共价键有序组装形成的一种新型聚合物。非共价相互作用赋予了超分子聚合物动态可逆性、刺激响应性及自适性。荧光超分子聚合物是将荧光团引入到超分子聚合物中,从而赋予超分子聚合物特殊的光学性能。因此,荧光超分子聚合物固有的发光性质及动态可逆性使得超分子聚合物被广泛应用于荧光传感器、探针、显影剂及发光二极管等领域。本文根据发光颜色不同的荧光超分子聚合物的设计及应用进行分类,并对荧光超分子聚合物的未来发展进行展望。     

双光子激发的超分子聚合物纳米颗粒生物成像研究

将具有双-2-脲基-4[1H]-嘧啶酮（bisUPy）的β-二羰基氟硼类衍生物（BF₂-bisUPy）及卟啉衍生物（Por（Pt）-bisUPy）通过四重氢键作用组装成超分子聚合物,通过微乳液法制备成在水中均匀分散的超分子聚合物纳米颗粒（SPNP）。扫描电子显微镜形貌表征表明获得的纳米颗粒粒径约为60 nm。紫外-可见吸收光谱、荧光发射光谱及寿命衰减实验均证明纳米颗粒内BF₂-bisUPy与Por（Pt）-bisUPy可发生高效的能量传递。具有双光子吸收的BF₂-bisUPy作为能量供体,可通过荧光共振能量传递（FRET）增强双光子激发下Por（Pt）-bisUPy的发光。双光子激发荧光强度与激光功率测试表明所制备的超分子聚合物纳米颗粒具有强烈的双光子激发下的荧光及磷光双发射,这种纳米材料可进入细胞,具有优秀的生物相容性,并在双光子激发时表现出强烈的荧光和磷光双发射生物成像。     

曙红与卟啉分子间和分子内的光致相互作用

合成了以半刚性链(一CH_2phCH_2—)和柔性链(—(CH_2)_4—)连接的曙红-卟啉二元化合物及其模型化合物.通过吸收光谱、荧光光谱、激发光谱及荧光寿命研究了模型化合物分子间的相互作用和二元化合物分子内的光致电子转移和能量传递.结果表明:二元化合物的模型化合物曙红乙酯和卟啉易形成基态复合物 在二元化合物分子内激发曙红时,曙红能将其单重态能量传递给卟啉,并能引发分子内的电子转移;激发卟啉时,能发生曙红向卟啉的电子转移.分析了分子构型和溶剂极性对2种过程的影响.     

热诱导组装Ta2O5空心微球

在有机体系中电化学溶解钽得到有机前驱体钽醇盐,在30 mL电解液中加入6 mL H2O2和0.6 g阳离子表面活性剂十六烷基三甲基溴化铵(CTAB),150℃溶剂热反应24 h,产物经过高温热处理后得到Ta2O5空心微球.研究表明:溶剂热反应得到无定型Ta2O5纳米颗粒,600 ℃热处理后得到由纳米颗粒组装成的无定型T2O5半球结构.经过进一步的900℃高温热处理导致这些相邻半球结构进一步组装为斜方晶系的Ta2O5微米级空心球(直径约2 μm),球壁厚度在150 nm左右,空心部分直径约为1.5μm,球壁是由更小的Ta2O5纳米空心球组成;而在相同条件下,采用油酸代替CTAB,得到粒径减小的Ta2O5纳米颗粒.同时探讨了高温热诱导组装多孔Ta2O5微米空心球的可能形成机理.     

疏水上转换纳米晶的均相体系聚合物包覆及在发光检测中的应用

选用水解的十八碳烯-马来酸酐共聚物(PMAO)为表面修饰分子,发展了一种以疏水纳米粒子吸附表面活性剂十二烷基磺酸钠(Na YF_4-SDS)为中间体的均一液相聚合物包覆纳米粒子方法.该方法解决了油溶性纳米晶与弱极性聚合物分子难以在单一体系下均匀分散的问题,实现了在均一液相体系下对疏水纳米晶的单分散包覆以及表面羧酸官能团修饰.红外光谱与表面Zeta电位测试结果表明纳米晶已被聚合物包覆,粒子表面为强电负性的羧酸基团.电镜结果表明聚合物包覆的上转换纳米晶粒径无明显的变化,具有良好的单分散性.发射光谱表明聚合物包覆前后粒子的发射谱带无显著变化,保持了原油相粒子的发光性能.进一步的特异性识别荧光显微成像实验证实聚合物包覆后的粒子(Na YF_4-PMAO)可用于生物学检测.     

2-脲基-4[1氢]-嘧啶酮四氢键萘-蒽超分子组装体系:"通过键"机制的单重态能量传递

设计合成了基于2-脉基-4[1氢]-嘧啶酮AADD四氢键萘-葱超分子组装体系UPNa·UPAn.稳态和时间分辨荧光光谱研究表明UPNa·UPAn四氢键组装体可以发生从茶到葱的高效、快速的单重态能量传递过程.体系内光诱导单重态能量传递的速度和效率远大于通过F(o)rster机制的单重态能量传递速率,表明组装体系UPNa·...     

不同表面活性剂反胶束对纳米AgCl性能的影响

在反胶束中研究了直径10～14nm的AgCl微粒子与曙红间的作用,比较了阴离子型和非离子型表面活性剂组成的反胶束微环境效应.考察了AgCl粒子对曙红吸收光谱、荧光光谱及荧光寿命的影响.讨论了AgCl粒子对曙红荧光猝灭的机制,初步研究了稳定剂苯基巯基四氮唑及四氮茚对曙红-AgCl粒子反胶束体系的影响.     

β-NaYF4：Yb,Er纳米晶与四甲基异氰酸罗丹明染料分子间的发光共振能量转移研究

Yb^3＋和Er^3＋离子掺杂的NaYF4纳米晶在近红外光（980nm）激发下可产生中心位于539和655nm的上转换发光,其中位于539nm的发光与四甲基异氰酸罗丹明（tetrametrylrhodarnine isothiocyante,TRITC）染料分子的吸收光谱部分重叠.本文基于上述光谱重叠特性,构筑了以β-NaYF4：Yb,Er为能量给体、TRITC为能量受体的发光共振能量转移（LRET）体系.TRITC分子通过静电作用紧密吸附于纳米晶表面,其较近距离的相互作用利于提高LRET效率和体系的稳定性.在980nm近红外光激发下,LRET过程使NaYF4：Yb,Er位于539nm的上转换发光减弱,同时可观察到TRITC染料分子的发光.对发光寿命的研究也证实了β-NaYF4：Yb,Er到TRITC的能量传递.     

高耐光/耐化学性的核壳型荧光纳米微球的制备

选取不溶于水的、光/热稳定性优良的荧光溶剂染料, 采用改进的细乳液(Miniemulsion)聚合反应, 将染料分子以分散状态牢固地嵌入交联的纳米聚合物基质中, 然后结合种子聚合反应技术构建生物相容性壳层, 制备出发射橙、黄、绿和青色光的系列核壳型荧光纳米微球. 获得的核壳型荧光纳米微球的平均粒径小于40 nm, 粒度较均一, 其水胶体具有优异的储存稳定性, 较高的光/化学稳定性和发光效率; 纳米微球的交联壳层表面富含与蛋白质、核酸等相容的羧基. 该制备方法简便可控, 原材料易得, 成本低廉, 也可选用含氨基、巯基和羟基等化学修饰基团的壳层单体来构建多样化的纳米微球壳层.     

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%.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.