金纳米线阵列制备及其光谱特性

利用电化学沉积方法在重离子径迹模板中制备出直径从45 nm到200 nm, 长径比达700的金纳米线阵列, 利用扫描电子显微镜(SEM)和X射线衍射(XRD)对所制备金纳米线的形貌及晶体结构进行分析, 结果表明, 在1.5 V(无参比电极)沉积电压下所制备出的直径为200 nm金纳米线沿[100]晶向具有较好择优取向. 利用紫外-可见光谱(UV-Vis)对镶嵌在透明模板中平行排列的金纳米线阵列光学特性进行研究, 发现金纳米线直径为45 nm时, 其紫外可见光谱在539 nm处有强烈吸收峰, 随着金纳米线直径增加, 吸收峰红移, 当金纳米线直径达到200 nm时, 其吸收峰峰位移至700 nm. 结合金纳米颗粒相关表面等离子体共振吸收效应对实验结果进行了讨论.     

利用聚合物自组装实现绿色荧光蛋白生色团的荧光增强

根据绿色荧光蛋白的发光原理,采用聚乙二醇与聚甲基丙烯酸甲酯的两亲性两嵌段聚合物通过自组装包覆生色团的方式,模拟了绿色荧光蛋白发光,考察了组装行为对光学性能的影响,并将其用于细胞成像.通过核磁共振、高分辨质谱、傅里叶变换红外光谱、凝胶渗透色谱、紫外-可见吸收光谱及荧光光谱等表征了生色团分子和聚合物的结构及性能.生色团紫外最大吸收在371 nm,荧光最大发射峰在428 nm.聚合物和生色团进行组装后,其紫外吸收消失,而最大荧光发射峰强度大大增强,且发生了约70 nm的红移,这是因为组装使得生色团的自由旋转受到了限制,且生色团共平面性增加.动态光散射(DLS)和透射电镜(TEM)证明了纳米粒子的结构和尺寸.由于尺寸适合且具有较好的荧光性能,纳米粒子成功应用于细胞成像.这种绿色荧光蛋白生色团的简单自组装方式在生物成像领域具有良好应用前景.     

模仿绿色荧光蛋白的荧光聚合物的合成和光学性质研究

受绿色荧光蛋白(GFP)荧光增强原理启发,采用开环聚合制备了两亲性聚乙二醇-生色团-聚己内酯(PEG-c-PCL)嵌段聚合物.通过核磁共振氢谱和碳谱(1H-,13C-NMR)、傅立叶变换红外光谱(FTIR)、凝胶渗透色谱(GPC)和紫外可见吸收光谱(UV-Vis)等证明其结构和性质.生色团和聚合物有相似的紫外吸收光谱,且最大吸收峰都在371 nm.荧光发射光谱表明,生色团的发射峰在427 nm,但聚合物的荧光发射峰出现了6 nm的红移,这是高分子化引起的结果.透射电镜(TEM)和动态光散射(DLS)证明了该两亲性嵌段聚合物能够组装成为纳米粒子.当聚合物组装成纳米粒子后,荧光强度增大了55倍,并且荧光发射峰出现了14 nm的红移,这些现象可归结于荧光生色团自由旋转的限制和组装导致的相互作用增强.     

枝状纳米结构氧化锆的合成和表征

以PEG200为结构诱导剂,用诱导-陈化方法合成了枝状纳米结构氧化锆。电导率的测定表明,PEG200对特殊形貌氧化锆的形成具有诱导和调控作用。用SEM、XRD、UV等对所得氧化锆的形貌、结构和紫外吸收特性等的表征表明,合成的枝状氧化锆以四方相结构为主。产物除了在235nm处有较强的吸收外,在300nm附近还可观察到多重的吸收。     

三氟乙酸对无金属卟啉-茈酰亚胺分子阵列激发态衰变过程的影响

用紫外-可见吸收光谱和荧光光谱研究了CF3COOH浓度变化对CHCl3溶液中N-[P-5′-(m-10′，15′，20′-三苯基卟啉)基]-N′-正十二烷基-3，4:9，10-四羧基茈二酰亚胺分子阵列(TrPP-MDPTCDI)的光致激发态衰变机理的影响，发现无论激发无金属卟啉还是苝酰亚胺基元，分子阵列均表现出质子化无金属卟啉生色团的特征荧光发射.对电子结构的分析说明质子化使[H2^2 TrPP^ -MDPTCDI]成为各种激发态中相对稳定的物种，因此，未质子化前占主导的从卟啉到茈酰亚胺基元的光致电子转移衰变途径在质子化后受到有效抑制，激发卟啉生色团(λ=439nm)直接得到[H2^2 TrPP^ -MDPTCDI]，并以辐射衰变方式回到基态；激发苝酰亚胺生色团(λ=491nm)得到的[H2^2 TrPP-MDPTCDI^ ]通过电荷分离态迅速弛豫到[H2^2 TrPP^ -MDPTCDI]，并辐射荧光，同时伴随少量的从茈酰亚胺到质子化无金属卟啉生色团的能量转移.     

9-戊基咔唑-3,6-双-(炔苯基-4-甲酸乙酯)的合成与双光子特性研究

采用钯催化的碳碳偶合反应合成了9-戊基咔唑-3,6-双-(炔苯基-4-甲酸乙酯)(I).进一步研究了化合物I在四氢呋喃和40%四氢呋喃水溶液中的光物理性质,结果显示,化合物I在40%四氢呋喃水溶液中的紫外吸收峰位置与其四氢呋喃溶液相比没有发生明显移动,它在40%四氢呋喃水溶液中的单光子荧光发射峰出现在453 nm,较其在四氢呋喃溶液的发射有42 nm红移,其荧光量子效率为0.44.用波长为660 nm飞秒激光激发时,化合物I在40%四氢呋喃水溶液中的双光子荧光发射最大峰红移至489 nm,其双光子吸收截面值为251GM,比其在四氢呋喃溶液中的截面(151 GM)增强了60%.     

溶液pH值对光响应性偶氮聚电解质H-聚集的影响

研究了溶液pH值变化对水溶性侧链偶氮聚电解质的生色团H 聚集行为的影响规律 .研究发现 ,偶氮聚电解质溶液中生色团的存在状态与聚合物链上羧基的电离度有着密切的关系 .调节溶液pH值可使生色团发生聚集和解聚集的转变 ,从而导致对应的紫外吸收光谱发生明显变化 .在羧酸的部分电离区内 ,侧链偶氮苯H 聚集体随pH升高而部份解聚 ,导致特征吸收峰红移 ,其相应的光响应速率加快和光致反 顺异构效率提高     

偶氮聚电解质的聚集和纳米聚集体

研究了两种具有不同化学结构的阴离子型偶氮聚电解质在四氢呋喃 /水混合溶剂中的聚集行为 .利用紫外 可见光谱和透射电镜等研究了偶氮聚电解质的聚集过程以及相应聚集体的形貌以及介质pH对聚集的影响 .结果表明 ,在四氢呋喃 /水混合溶剂中 ,随着水含量的增加 ,偶氮生色团逐渐聚集 ,其紫外光谱上最大吸收峰位置逐渐蓝移 ,而强度逐渐下降 .在较高浓度条件下 ,形成的聚集体可以用透射电镜直接观察到 ,呈现直径为 80nm左右的球形超分子结构 .与相应的偶氮两亲性小分子相比 ,这两种偶氮聚电解质形成的聚集体具有更高的稳定性 .由于羧酸基团和偶氮生色团相互连接的方式不同 ,溶液pH对这两种聚集体具有完全相反的影响 .偶氮生色团的聚集会严重影响偶氮生色团反式至顺式的异构化效率 .     

Ni 掺杂ZnO纳米线的电子结构与磁性

采用自旋极化密度泛函理论系统研究了Ni掺杂ZnO纳米线的电子结构、磁学和光学性质.磁学性质计算结果显示六种Ni掺杂ZnO纳米线的磁性耦合体系出现了铁磁(FM)、反铁磁(AFM)和顺磁(PM)二种不同的耦合状态.能量计算结果表明Ni原子在纳米线外表面沿[0001]方向替代Zn原子时能量最低,体系的AFM耦合相对稳定,AFM体系表现出金属性.态密度计算结果显示FM耦合在费米能级附近出现了明显的自旋极化现象,发生了强烈的Ni 3d和O 2p杂化效应,掺杂产生的磁矩主要来源于Ni 3d未成对轨道电子和部分O 2p轨道电子的贡献,FM耦合表现出半金属性.另外,光学性质计算结果显示Ni掺杂ZnO纳米线的远紫外吸收峰发生了红移现象,而380 nm附近的近紫外吸收峰发生了明显的蓝移现象,在整个紫外区都表现出了优异的发光性能.以上结果表明Ni掺杂ZnO纳米线是一种很有前途的磁光电子材料.     

帽状锌纳米结构的制备及其表面等离子体共振特性

利用真空热蒸发法在二氧化硅纳米粒子单层膜上沉积锌薄膜制备了帽状锌纳米结构. 采用透射电镜(TEM)、扫描电镜(SEM)、X射线衍射(XRD)和紫外-可见吸收光谱(UV-Vis)对样品的形貌、结构和光学特性进行了表征和研究. SEM照片表明所得到的复合纳米粒子为不完全包裹的帽状结构, 且其表面较粗糙. XRD分析结果显示在二氧化硅纳米粒子上沉积的锌膜呈多晶六角密堆结构. 吸收光谱研究表明, 帽状锌纳米结构在570～760 nm范围内具有明显的由纵向双极子表面等离子体共振引起的吸收峰, 且随着锌帽层厚度的增加或二氧化硅内核粒径的增大, 该吸收峰逐渐红移; 当内核粒径增大到500 nm时, 帽状锌纳米结构在412 nm附近还出现了一个四极子共振峰.     

DNA‐Based Oligochromophores as Light‐Harvesting Systems

The chromophores ethynyl pyrene as blue, ethynyl perylene as green and ethynyl Nile red as red emitter were conjugated to the 5‐position of 2′‐deoxyuridine via an acetylene bridge. Using phosphoramidite chemistry on solid phase labelled DNA duplexes were prepared that bear single chromophore modifications, and binary and ternary combinations of these chromophore modifications. The steady‐state and time‐resolved fluorescence spectra of all three chromophores were studied in these modified DNA duplexes. An energy‐transfer cascade occurs from ethynyl pyrene over ethynyl perylene to ethynyl Nile red and subsequently an electron‐transfer cascade in the opposite direction (from ethynyl Nile red to ethynyl perylene or ethynyl pyrene, but not from ethynyl perylene to ethynyl pyrene). The electron‐transfer processes finally provide charge separation. The efficiencies by these energy and electron‐transfer processes can be tuned by the distances between the chromophores and the sequences. Most importantly, excitation at any wavelength between 350 and 700 nm finally leads to charge separated states which make these DNA samples promising candidates for light‐harvesting systems.     

Formation and Characterization of Europium Bisphthalocyanine Organic Nanowires by Electrochemical Deposition

Europium bisphthalocyanine (EuPc2) nanowires were prepared by electrochemicaldeposition method. Scanning electron microscopy (SEM) images show the evolution of themorphologies of nanowires obtained under different deposition time (Td). The optical properties ofeuropium bisphthalocyanine films were studied by UV-Vis absorption spectra. The morphology of EuPc2 nanowires could be controlled by changing deposition conditions, which provides a usefulmethod to make organic nanowires.     

在线紫外-可见光谱研究ITO导电玻璃电极上苯胺与对苯二胺的电化学共聚及其产物的表征

本文用在线紫外-可见光谱电化学的方法较详细地研究了在0.5M硫酸水溶液中苯胺、对苯二胺以及苯胺与对苯二胺混合体系在ITO导电玻璃电极上的电化学聚合和共聚合的过程。苯胺与对苯二胺在ITO导电玻璃上发生了电化学共聚合,在0.5M硫酸水溶液的纯苯胺和苯胺与对苯二胺共聚时的循环伏安曲线以及其对应的在线紫外-可见光谱表明对苯二胺的加入除了发生共聚外,也使聚合的速率明显加快;而且纯苯胺在循环伏安电化学聚合时在430nm处出现的吸收带因对苯二胺的加入而消失,说明对苯二胺的加入使聚合的机理与纯苯胺的聚合机理有明显不同,主要原因是苯胺产生的反应中间体可能很快与对苯二胺的阳离子自由基反应聚合。在导电玻璃ITO上的聚合物膜的反射傅立叶红外光谱表明,对苯二胺的加入可能产生了具有1,2取代模式结构,这说明了对苯二胺结合进入到聚合物中。这种共聚使得产物的表面形貌也发生了变化,聚合物扫描电镜图表明对笨二胺的加入有利于纤维状的表面形貌产生,纤维的直径可达到50nm粗细;同时用在线紫外-可见光谱研究了纯聚苯胺和共聚物随电位变化的电变色性质,结果表明在0v-0.6v之间共聚物与纯聚苯胺的在线紫外-可见光谱有明显的不同,且共聚物的电变色可逆性比纯聚苯胺好;同时SEM图也表明在0.8v电位下聚苯胺和共聚物表面形貌发生了团聚。     

An Isoindigo‐Based “Double‐Cable” Conjugated Polymer for Single‐ Component Polymer Solar Cells

An isoindigo‐based “double‐cable” conjugated polymer bearing perylene bisimide side units was developed via Stille polymerization for application in single‐component polymer solar cells, in which a power conversion efficiency of 1% with broad photo‐response from 300 nm to 800 nm was achieved. There is no evidence of large phase separation confirmed by AFM images and photoluminescence (PL) spectra. The space charge limit current measurements and light intensity dependence measurements indicate that the low electron mobility and the significant recombination of photogenerated charge carriers in active layer mainly account for the low performance of our solar cells. Our results suggest that these “double‐cable” are promising candidates for use in single‐component polymer solar cells with NIR photoresponse.     

Shape-controlled synthesis of ternary chalcogenide ZnIn2S4 and CuIn(S,Se)2 nano-/microstructures via facile solution route

We demonstrated in this paper the shape-controlled synthesis of ZnIn2S4, CuInS2, and CuInSe2 nano- and microstructures through a facile solution-based route. One-dimensional ZnIn2S4 nanotubes and nanoribbons were synthesized by a solvothermal method with pyridine as the solvent, while ZnIn2S4 solid or hollow microspheres were hydrothermally prepared in the presence of a surfactant such as cetyltrimethylammonium bromide (CTAB) or poly(ethylene glycol) (PEG). The mechanisms related to the phase formation and morphology control of ZnIn2S4 are proposed and discussed. The UV-vis absorption spectra show that the as-prepared nano- and micromaterials have strong absorption in a wide range from UV to visible light and that their band gaps are somewhat relevant to the size and morphology. The photoluminescence measurements of the ZnIn2S4 microspheres at room temperature reveal intense excitation at approximately 575 nm and red emission at approximately 784 nm. Furthermore, CuInS2 and CuInSe2 with different morphologies such as spheres, platelets, rods, and fishbone-like shapes were also obtained by similar hydrothermal and solvothermal synthesis.     

红藻条斑紫菜R-藻红蛋白中的能量传递过程

本文通过对条斑紫菜R-PE(藻红蛋白)及其α-β-γ亚基的吸收光谱和荧光光谱进行计算机解叠,研究了R-PE内发色团之间的能量传递过程,并对R-PE及亚基内的各发色团进行了“s”和“f”型的指认。发现在亚基中为“f”型的发色团在R-pE(αβ)₆γ中起着“s”型发色团的作用,且将能量传递给最后的“f”型发色团。荧光激发偏振光谱进一步证明了R-PE内的能量转移过程与计算机解叠的结果一致。     

Cyclopalladated complexes of 4-aryl-2,1,3-benzothiadiazoles: new emitters in solution at room temperature

The cyclopalladation of the 4-aryl-2,1,3-benzothiadiazoles 1a-c with palladium acetate in acetic acid afforded the novel dimeric complexes 2a-c in good yields. These were then converted into the monomeric pyridine-, chloro-coordinated cyclometallated complexes 3a-c through reaction with lithium chloride in acetone and then pyridine in dichloromethane. All complexes were fully characterized by means of NMR, IR and elemental analysis. The X-ray structure of complex 2c revealed that it presents transoid geometry, whereas the X-ray structure of 3c shows that the pyridine ligand and the thiazole ring are mutually trans. Photophysical properties were investigated by means of UV-Vis absorption and fluorescence emission in solution. Solid-state diffuse reflectance UV-Vis spectra (DRUV) were also applied in order to better characterize the complexes photophysics in the solid state. All complexes present intense absorption at around 300 nm (λ(1)) via(1)LC transitions located in BTD ligands, and additional low energy absorption bands, higher than 450 nm (λ(2)) of (1)MLCT character. The complexes are fluorescent in solution at room temperature, where two emission bands could be observed, a high energy band (excitation @ λ(1)) ascribed to the ligand emission and an additional red shifted low intense band (excitation @ λ(2)) due to the complex emission.     

Ultrafast energy-electron transfer cascade in a multichromophoric light-harvesting molecular square

A molecular square with dimensions of about 4 nm, incorporating sixteen pyrene chromophores attached to four ditopic bay-functionalized perylene bisimide chromophores, has been synthesized by coordination to four Pt(II) phosphine corner units and fully characterized via NMR spectroscopy and ESI-FTICR mass spectrometry. Steady-state and time-resolved emission as well as femtosecond transient absorption studies reveal the presence of a highly efficient (>90%) and fast photoinduced energy transfer (k(en) approximately equal to 5.0 x 10(9) s(-1)) from the pyrene to the perylene bisimide chromophores and a very fast and efficient electron transfer (>94%, k(et) approximately equal to 5 x 10(11) up to 43 x 10(11) s(-1)). Spectrotemporal parametrization indicates upper excited-state electron-transfer processes, various energy and electron-transfer pathways, and chromophoric heterogeneity. Temperature-dependent time-resolved emission spectroscopy has shown that the acceptor emission lifetime increases with decreasing temperature from which an electron-transfer barrier is obtained. The extremely fast electron-transfer processes (substantially faster and more efficient than in the free ligand) that are normally only observed in solid materials, together with the closely packed structure of 20 chromophoric units, indicate that we can consider the molecular square as a monodisperse nanoaggregate: a molecularly defined ensemble of chromophores that partly behaves like a solid material.     

纳米银掺杂二氧化硅复合颗粒的制备及表征

0引言金属纳米颗粒因其粒子尺寸小(1￣100nm),比表面积大,表面原子数多,表面能和表面张力随粒径的下降急剧增大而具有量子尺寸效应[1]、小尺寸效应[2]、表面效应[3]及宏观量子隧道效应[4]等,从而出现了不同于常规固体的新奇特性,如:光学性质、磁性质以及电磁学性质[5],使其在催化、信息存储及非线性光学等领域展示了广阔的应用前景[6]。虽然制备金属纳米颗粒的方法有很多[6],但是由于纳米尺寸的金属颗粒具有较高的表面能,容易发生聚集,所以如何保持其稳定性依旧是比较困难的问题。随着纳米科技的发展,人们正尝试用各种方法来解决这个问题:如…