短程有机电子给体-受体体系的合成

设计合成了一类以蒽为电子给体,带不同吸电子取代基的苯为电子受体的新型短程有机电子给体-受体体系。光谱实验研究发现,该短程给体-受体体系内存在非常强的荧光淬灭现象。实验结果分析表明强荧光淬灭的本质在于体系分子内快速的电子转移,同时表明缩短电子给体-受体之间的距离将加快电子转移过程。     

聚苯乙烯微球中荧光共振能量转移的研究

采用分散共聚合法制备了单分散的负载有1,8-萘酰亚胺染料的荧光微球。利用供体和受体染料间的荧光共振能量转移,荧光微球在激发供体染料时同时实现了供体和受体染料的双重荧光发射信号。结果表明:当微球中染料的浓度相对较低(质量分数小于0.2%)时,荧光共振能量就可以有效地发生转移。聚合过程中增加供体或受体染料的浓度都会提高能量转移效率,这是浓度增加使得染料分子间距离缩短造成的。通过调整微球中染料浓度可以获得不同能量转移效率、具有荧光编码信号的系列荧光微球。这类粒径均一的荧光微球在多元生物分析中有潜在的应用价值。     

基于稀土复合纳米粒子的新型荧光共振能量移体系的建立及研究

采用简便的超声合成方法,成功的制备了稀土复合纳米粒子Tb/acety acetone(acac)/Polyacrylamide(PAM).该复合纳米粒子具有较高的稳定性,良好的分散性.基于该稀土复合纳米粒子为供体,罗丹明B为受体,建立了一种新型高效的荧光共振能量转移(FRET)体系.实验结果表明该供体-受体对之间具有较高的能量转移效率.     

一类供体-受体双嵌段丙烯酸酯聚合物的合成及性能

利用原子转移自由基聚合（ATRP）法合成了一种新的供体-受体双嵌段聚合物聚对（二苯胺基）苯乙烯-聚（2-（2-蒽醌甲酰氧基）甲基丙烯酸乙酯（P1-b-P2）。供体段是富电子的三苯胺段,受体段是缺电子的蒽醌段。该双嵌段聚合物的单体结构通过核磁（NMR）加以表征,聚合物通过凝胶渗透色谱（GPC）、差示扫描量热法(DSC)、紫外光谱（UV-vis）、荧光光谱（PL）和循环伏安（CV）法加以表征。GPC和紫外吸收测试表明聚合物数均分子量约为7600,最大吸收波长为305nm,CV测试计算发现受体段比供体段长,与GPC测试结果一致,表现出更好的受体性能。     

含有喹啉和香豆素的蓝色发光材料的合成及性能

合成了一种含有喹啉和香豆素基团且发射蓝光的发光材料(QCC),通过紫外-可见吸收光谱和荧光发射光谱对QCC的光物理性质进行了测试.结果表明QCC的最大吸收峰为330 nm,且在360~540 nm内具有强的荧光发射带.随着溶剂极性的增加,QCC的荧光发射峰出现明显的红移.通过荧光猝灭技术分别观察了QCC与电子给体(DMA)和电子受体(DMTP)之间的相互作用,结果表明QCC具有优良的电子转移性能.进一步研究了QCC与碳70(C₇₀)和碳纳米管(CNTs)的相互作用.利用高斯(Gaussian)09软件计算了QCC的电子能级分布情况,所得理论计算结果与电化学循环伏安法测得的结果基本一致.此外,QCC展示了良好的热稳定性,其热分解温度(t_d)为270 ℃.上述所得结果表明,QCC可作为潜在的蓝色有机发光二极管器件的发光材料.     

基于密度泛函理论对咔咯-吩噻嗪二元体激发态电荷转移的研究

采用密度泛函理论(DFT)对咔咯与吩噻嗪形成的F10C-PTZ供体-受体体系进行了计算,包括几何结构、前线分子轨道、电子-空穴分析、吸收光谱等基态和激发态性质;探讨了二元体间隔基和取代基位置对电荷转移激发态的影响.结果表明:F10C-PTZ二元体存在供体-受体间的电荷转移激发态;间隔基的C—C键会阻碍供体-受体的电荷转移,而间隔基的C—C键可增强体系的共轭性,有利于供体-受体的电荷转移;当供体取代位置与五氟苯基相邻时,咔咯上五氟苯基的拉电子效应使得供体-受体激发的电荷转移更易于发生.     

Ru/AC催化剂上不同取代苯液相加氢活性的比较研究

采用自制的Ru/AC催化剂,以异丙苯作反应物系统考察了反应条件:时间、温度、氢压、催化剂用量、底物浓度等对苯环加氢反应的影响,并与不同供电子与吸电子基团的取代苯加氢反应活性进行了比较.用XRD和XPS对催化剂进行了表征.结果表明:相同的实验条件下,带供电子基团的取代苯的加氢活性高于带吸电子基团取代苯.带供电子基团取代苯的加氢活性顺序如下:叔丁基苯>异丙苯>乙苯>甲苯>苯,间二甲苯>对二甲苯>邻二甲苯.带吸电子基团取代苯的加氢活性顺序为:苯酚>对氯苯胺>氯苯>硝基苯.该催化剂呈微晶状态,粒度很小,经氢气还原后表面上钌主要为Ru0,它们对供电子基团取代苯有很高的芳环加氢活性.     

A water-soluble fluorescence resonance energy transfer probe for hypochlorous acid and its application to cell imaging

A water-soluble fluorescence resonance energy transfer (FRET) probe for hypochlorous acid (HOCl), dansyl rhodamine B piperazinoacetohydrazide, was designed, synthesized and characterized. The dansyl moiety in the probe acted as a FRET donor and the rhodamine moiety acted as a FRET acceptor. The two moieties were connected by a HOCl-cleavable active bond, and cleavage of this linker decreased the FRET efficiency and increased the fluorescence intensity of the donor at 501 nm. The water solubility of the prob...     

以甲酚红和钙黄绿素为变色剂的有机可逆热色性材料

合成了以甲酚红和钙黄绿素作为电子给予体 ,以 8 羟基喹啉作为电子接受体的有机可逆热色性材料 ,并对材料进行了DSC测定     

Structural Changes of Water Molecules Upon the Reduction of Quinones in The Reaction Center from Rhodobactery Sphaeroides

1 Results The photosynthetic bacterial reaction center (RC) is a membrane protein complex.The RC is composed of three protein subunits and redox components such as bacteriochlorophylls, bacteriopheophytins,and quinones.The RC performs the photochemical electron transfer from the bacteriochlorophyll dimer through a series of electron donor and acceptor molecules to a secondary quinone,QB.QB accepts electrons from a primary quinone,QA,in two sequential electron transfer reactions.The second electron trans...     

聚苯撑乙炔共轭聚合物的合成及光电性能

利用钯催化剂Pd(PPh3)2Cl2和相转移催化剂PTC,采用Heck交叉偶联缩聚反应合成了(苯撑乙炔-氰基乙烯苯撑)共聚物(C12-PPE-DCNTB),比较了聚合物的紫外吸收光谱和荧光光谱特征及热稳定性。以ITO为阳极,Ba/Al为阴极,制备了构型为ITO/PEDOT-PSS/MEH-PPV C12-PPE-DCNTB(1/1,m/m)/Ba/Al的本体异质结器件,初步讨论了活性层的光物理特征及器件的光伏性能。     

Synthesis and Characterization of Fluorene-based Polymers Containing Electron-withdrawing Thiazolo Thiazole Unit

1 Results Low bandgap polymers can be used for pure red light emitting materials or solar cell materials.To make low bandgap polymers,we designed conjugated polymers with alternating sequences of the appropriate donor/acceptor units in the main chain.3-hexyl thiophene was used as a electron donating unit.For the electron accepting unit,we selected thiazolothiazole and bithiazole units having electron withdrawing property.Polyfluorene(PF) is the preferred conjugated polymer in light-emitting applications...     

Gating charge displacement in voltage-gated ion channels involves limited transmembrane movement

Voltage-gated ion channels are responsible for generating electrical impulses in nerves and other excitable cells. The fourth transmembrane helix (S4) in voltage-gated channels is the primary voltage-sensing unit that mediates the response to a changing membrane electric field. The molecular mechanism of voltage sensing, particularly with respect to the magnitude of the transmembrane movement of S4, remains controversial. To determine the extent of this transmembrane movement, we use fluorescent resonance energy transfer between the S4 domain and a reference point in the lipid bilayer. The lipophilic ion dipicrylamine distributes on either side of the lipid bilayer depending on the membrane potential, and is used here as a resonance-energy-transfer acceptor from donor molecules attached to several positions in the Shaker K+ channel. A voltage-driven transmembrane movement of the donor should produce a transient fluorescence change because the acceptor also translocates as a function of voltage. In Shaker K+ channels no such transient fluorescence is observed, indicating that the S4 segment does not translocate across the lipid bilayer. Based on these observations, we propose a molecular model of voltage gating that can account for the observed 13e gating charge with limited transmembrane S4 movement.     

Direct measurement of electrical transport through DNA molecules

Attempts to infer DNA electron transfer from fluorescence quenching measurements on DNA strands doped with donor and acceptor molecules have spurred intense debate over the question of whether or not this important biomolecule is able to conduct electrical charges. More recently, first electrical transport measurements on micrometre-long DNA 'ropes', and also on large numbers of DNA molecules in films, have indicated that DNA behaves as a good linear conductor. Here we present measurements of electrical transport through individual 10.4-nm-long, double-stranded poly(G)-poly(C) DNA molecules connected to two metal nanoelectrodes, that indicate, by contrast, large-bandgap semiconducting behaviour. We obtain nonlinear current-voltage curves that exhibit a voltage gap at low applied bias. This is observed in air as well as in vacuum down to cryogenic temperatures. The voltage dependence of the differential conductance exhibits a peak structure, which is suggestive of the charge carrier transport being mediated by the molecular energy bands of DNA.     

基于苯并三噻吩共聚物/富勒烯衍生物的聚合物太阳能电池

以苯并三噻吩共聚物(BTT-BTz)为给体材料,具有不同能级结构的富勒烯衍生物为受体材料,通过共混方式制备光敏薄膜,并研究受体材料的能级结构对光伏器件开路电压(Voc)、短路电流(Jsc)、填充因子(FF)和电池效率(PCE)的影响.结果表明:当IC60BA为电子受体材料时,器件的Voc=1.06V,但Jsc较低,使得PCE仅为1.49%;当PC60BM和PC70BM为受体材料时,Voc分别为0.86V和0.81V,但Jsc较高,使得PCE分别为3.22%和5.06%.     

3种药物及个人护理品对斜生栅藻生长及光系统Ⅱ的影响

研究了乳糖酸红霉素(ETM)、双氯芬酸钠(DCF)及壬基酚十氧乙烯醚(NPEO10)等3种药物及个人护理品(PPCPs)对斜生栅藻(Scenedesmus obliquus)的生长及光系统Ⅱ(PS Ⅱ)的影响。结果表明:3种PPCPs对斜生栅藻的生长及其PSⅡ均有抑制作用并以ETM的毒性最大,但NPEO10在低质量浓度时(0~0.05 mg/L)对斜生栅藻的生长及PSⅡ具一定的促进作用。对叶绿素荧光快速反应曲线的分析显示,ETM同时抑制斜生栅藻PSⅡ反应中心的供体侧和受体侧,使PSⅡ反应中心失活并降低光化学反应效率等,而DCF和NPEO10主要抑制电子传递链QA后的电子传递过程。研究显示叶绿素荧光诱导动力学参数对于反映PPCPs对藻类的毒性特征具有较高的敏感性及一定的特异性,可作为PPCPs污染生态风险评价的潜在候选生物标志物。     

用DLTS和ODLTS技术研究ZnSe晶体中与Ga有关的深能级

本文应用深能级瞬态谱(DLTS)和光深能级瞬态谱(ODLTS)技术研究了掺Ga的ZnSe晶体中的深能级.发现ZnSe:Ga晶体中有一个与Ga有关的施主能级位于导带底下0.17eV处,两个与Ga有关的受主能级分别位于价带顶上0.65eV和0.72eV处.文中还对这些能级的起源进行了讨论.     

电子受体强度对基于Thieno[3,2-b]thiophene的共轭聚合物电子性质的影响

采用杂化的密度泛函方法(DFT/B3LYP),在6-31G(d)理论水平下研究了基于噻吩并[3,2-b]噻吩(Thieno[3,2-b]thiophene,TT))的D-A型共轭聚合物的几何结构、电子结构和性质.研究发现,在以TT为电子供体的D-A型共轭聚合物中,电子受体强度是影响其几何结构、电子结构和性质的重要因素.对基于TT的电子受体与电子供体交替排列的D-A型共轭聚合物,在一定范围内,电子受体强度增加,有利于减小共轭聚合物的键长交替,降低聚合物的能隙,并使其能带变宽,电子离域程度增大,载流子有效质量减小,载流子迁移能力增强.但受体强度过大,键长交替反而增大,能带和能隙均变窄,载流子迁移能力减弱.     

一种咔唑-苯并噻二唑共聚物的合成与光伏性能研究

以N-十二烷基-2,7-咔唑为给体单元、5,6-二辛氧基二噻吩苯并噻二唑为受体单元，通过Suzuki偶联反应合成了一种具有给-受体结构的共轭聚合物聚N-十二烷基-2,7-咔唑-5,6-二辛氧基-4,7-二噻吩-2-基-苯并噻二唑（PC-DODTBT），并研究了该聚合物的光物理与电化学性能。结果表明，以PC-DODTBT为电子给体，PCBM为电子受体，制得的共混体相异质结太阳能电池在AM1.5、100 mW/cm²模拟太阳光下，开路电压为0.88 V，短路电流为2.04 mA/cm²，填充因子为0.51，能量转换效率为0.92%。     

Excitation energy transfer mechanisms in allophycocyanin (I)

The mechanisms of excitation energy transfer within allophycocyanin monomer with the theory of generalized master equation (GME) and the technique of time-resobed fluorescence anisotropic spectroscopy are studied. In the case of known information of its structure and spectra, the theory applied is based on the assumption that the coupling interaction between two chromophores is fairly weak. The theory correctly predicts the experimentlly observed rate for excitation energy transfer in allophycocyanin monomer. Based on the results, the energy transfer mechanism can be described as Förster and these processes cannot take place from the high vibrational levels of donor to acceptor.