Electrospinning preparation and photophysical properties of one-dimensional (1D) composite nanofibers doped with erbium(III) complexes

1D composite nanofibers of poly(vinylpyrrolidone) (PVP, M_W≈60,000) doped with three Er(III) complexes were prepared by electrospinning. They demonstrated strong near-infrared (NIR) photoluminescence (PL) at 1535 nm and ternary Er(TTA)₃Phen (denoted as Er2, where TTA=2-thenoyltrifluoroacetonate; Phen=1,10-phenanthroline) fibers (Er2/PVP) exhibited maximum PL intensity. The crystal structure of Er2 complex has been determined by X-ray diffraction measurements. Er2 doped in fibers exhibited better thermal stability of NIR PL than the pure Er2 complex. These luminescent composite fibers have potential application in optical amplifiers.     

有机电致发光器件中Rubrene掺杂剂的荧光光谱性质

通过改变黄色荧光染料5,6,11,12-tetraphenylnaphthacene(Rubrene)的溶液浓度,研究了溶液的浓度改变对荧光小分子染料的发光光谱的影响.采用测试不同浓度Rubrene溶液光致发光(PL)的光谱强度手段,确定了溶液中染料的最佳浓度,即最大程度避免或减弱浓度效应(浓度猝灭)且光致发光强度最大时的溶液浓度.首先确定极限浓度的范围,然后通过测试范围内的不同浓度的PL光谱强度判断精确的极限浓度位置.结果表明,在Rubrene浓度为2×10-3 mol·L-1时,PL光谱强度最大,并且随着溶液浓度的继续增加,PL光谱强度的降低仅为11%,进而确定Rubrene分子的极限浓度应该在2×10-3 mol.L-1左右.通过对比不同掺杂比例的Rubrene:N,N'-Bis(naphthalen-l-y)-N,N'-bis(phenyl)benzidine(NPB)在溶液中的混合体系的PL光谱发现,NPB与Rubrene分子之间存在小完全的能鞋传递过程,有利于实现NPB分子和Rubrene分子共同的蓝光和黄光发射,从而得到色纯度较高的白色荧光.     

ZnS：Mn/SiO2量子点的表面聚乙烯吡咯烷酮修饰及其应用于海水中铅离子检测

制备了二氧化硅壳层修饰的ZnS：Mn量子点,基于聚乙烯吡咯烷酮（PVP）与二氧化硅表面硅羟基的作用,在纳米复合微粒表面进行了PVP的修饰,得到了在海水中荧光性能及胶体稳定性良好的ZnS：Mn/SiO₂/PVP 量子点。在Pb²⁺对所制备纳米微粒具有荧光猝灭效应的基础上,建立了用ZnS：Mn/SiO₂/PVP 量子点作为荧光探针检测海水中微量铅离子的新方法。研究表明,量子点浓度为10^-3 mol/L时,海水中离子浓度在10~100 μmol/L范围内与ZnS：Mn/SiO₂/PVP量子点荧光猝灭强度呈良好的线性关系,相关系数为0.994 6,检出限为8×10^-7 mol/L。     

Preparation and photoluminescent properties of Ni-doped ZrO2 fibers

Ni²⁺-doped ZrO₂ precursor fibers were prepared via sol-gel technique by dry-spinning method and then heat-treated at different temperatures. The surface of the fibers is smooth with uniform diameter and no cracks have been observed by scanning electron microscopy (SEM). The emission intensity reaches a maximum value at 1 mol% Ni²⁺ because of the concentration quenching. The photoluminescence (PL) relative intensity is apparently intensifying with increasing temperature before 700 °C due to the crystallinity of the ZrO₂ lattice improvement. The PL results show that the typical emission center is at 510 nm excited at 315 nm.     

三价铕荧光络合物与聚乙烯吡咯烷酮复合物研究

为研究稀土荧光络合物与高分子形成的复合物的结构与发光性能间的关系,利用α-噻吩甲酰三氟丙酮（TTA）和三苯基氧化膦（TPPO）与氯化铕（EuCl₃）分别制备了Eu(TTA)₃·2H₂O和Eu(TTA)₃·(TPPO)₂络合物,及其与聚乙烯吡咯烷酮（PVP）的复合物。采用荧光光谱,红外光谱和透射电镜等方法对复合物进行了表征。荧光光谱测定结果表明Eu(TTA)₃·2H₂O与PVP K30结构单元摩尔比为1∶35的PVP/Eu(TTA)₃·2H₂O复合物的612　nm发射峰的荧光强度较Eu(TTA)₃·2H₂O络合物有显著提高。红外光谱研究表明络合物的Eu3+与PVP分子的羰基之间存在着明显的配位作用,并且存在多种配位方式。透射电镜观察结果表明复合物具有微相分离结构,其中的稀土络合物为无定形结构,这进一步表明PVP与络合物分子间存在相互作用。     

新型汞离子CQDs-CuNCs比率荧光探针的构建及在螃蟹中的应用

汞是一种典型的低剂量高毒性物质,广泛存在于环境和水体中,可通过食物链传递并累积,从而对人体造成危害。因此,准确快速的监测食品中汞离子（Hg2+）含量对于保障食品安全具有重要意义。目前,常用的Hg2+检测方法包括液相色谱-原子荧光光谱法（LC-AFS）、电感耦合等离子质谱法（ICP-MS）、电化学法和荧光分析法。比率型荧光探针具有双发射荧光特性,其中内置校准功能可降低因探针浓度和各种环境因素产生的检测误差,可以有效的克服单发射荧光探针的不足。本研究提出了基于碳量子点（CQDs）和铜纳米簇（CuNCs）的新型比率型荧光探针用于螃蟹中Hg2+的快速检测。主要研究内容和结果如下：（1）CQDs-CuNCs复合体系的制备。以蔗糖为碳源,聚乙二醇为钝化剂,通过微波介导法合成CQDs;以抗坏血酸为还原剂和稳定剂通过水热法合成CuNCs,后通过自组装制成CQDs-CuNCs复合体系。（2）CQDs-CuNCs复合体系的表征。利用高倍透射电子显微镜（HRTEM）、紫外-可见吸收光谱（UV-Vis）、荧光光谱（FL）和傅里叶变换红外光谱（FTIR）对CQDs-CuNCs复合体系表征,结果显示,该研究成功合成了具有双发射特性的CQDs-CuNCs比率型荧光探针。（3）CQDs-CuNCs复合体系的稳定性测试。将CQDs-CuNCs比率型探针与传统的单通道CuNCs探针的稳定性进行对比。结果表明,当探针浓度漂移和测量温度波动时,CQDs-CuNCs比率型探针比单发射的CuNCs抗干扰能力更强,稳定性更高。（4）CQDs-CuNCs复合体系对Hg2+的检测。当Hg2+存在时,复合体系中的CuNCs发生团聚,而CQDs基本不受影响,导致443 nm处的CuNCs荧光猝灭而545 nm处的CQDs荧光强度几乎不变。依据荧光强度的比值（I_{443 nm}/I_{545 nm}）与Hg2+浓度的关系实现定量检测。在对标准Hg2+检测时,CQDs-CuNCs复合体系的I_{443 nm}/I_{545 nm}和单发射CuNCs的猝灭率与Hg2+浓度（0.1～12 μmol·L-1）均呈现良好的线性关系,相关系数分别达到0.994 7和0.991 6,检测限（3σ/S）分别为2.83和3.62 nmol·L-1。在螃蟹样品检测中,CQDs-CuNCs比率型探针和单发射的CuNCs得到回收率分别为102.5%~105.4%和104.2%~112.5%,说明CQDs-CuNCs复合体系比单发射CuNCs对Hg2+具有更高的灵敏性和稳定性。以上结果表明,本研究所构建的CQDs-CuNCs比率型荧光探针能够用于食品中Hg2+的快速、准确检测。     

水溶性CdTe/CdS纳米晶表面SiO2壳层的反相胶束法包覆

"提出了一种水相中制备CdTe/CdS核壳结构纳米粒子的方法.用Te粉作为碲源,用Na2S作为硫源,在50 ℃下制备了CdTe/CdS核壳结构纳米粒子. 用紫外可见吸收光谱和荧光光谱分析了CdS壳层对CdTe核的影响. 随CdS壳层厚度的增加,紫外可见吸收光谱和荧光光谱均发生了红移. CdS壳层厚度较薄时,CdTe/CdS纳米晶的荧光强度较CdTe纳米粒子有显著提高;而CdS壳层厚度较厚时,CdTe/CdS纳米晶的荧光强度会逐渐降低. 用反相胶束法在CdTe/CdS核壳结构纳米粒子的表面包被一层SiO2,     

水热法促进EuVO_4@YVO_4核壳结构纳米颗粒中Eu~(3+)的扩散及其对发光性能的影响

采用共沉淀法制备了EuVO4@YVO4核壳结构纳米颗粒,然后用聚电解质聚苯乙烯磺酸钠对其进行包覆和保护,并在200?C下对样品水热处理0—48 h.在水热处理48 h后,样品的发光强度增强了约5倍,平均发光寿命由0.410 ms延长至0.579 ms.对样品的发光衰减曲线的拟合、分析为Eu3+的扩散提供了有力的证据.这种自内而外的扩散降低了样品核心中Eu3+的局域浓度,削弱了浓度猝灭效应,同时又能够避免表面猝灭效应的发生,从而使得样品的发光寿命变长、发光效率迅速提升.     

Polystyrene Microspheres in Tissue-Simulating Phantoms Can Collisionally Quench Fluorescence

Tissue-simulating phantoms that replicate intrinsic optical properties in a controlled manner are useful for quantitative studies of photon transport in turbid biological media. In such phantoms, polystyrene microspheres are often used to simulate tissue optical scattering. Here, we report that using polystyrene microspheres in fluorescent tissue-simulating phantoms can reduce fluorophore quantum yield via collisional quenching. Fluorescence lifetime spectroscopy was employed to characterize quenching in phantoms consisting of a fluorescein dye and polystyrene microspheres (scattering coefficients _s 100-600cm^–1). For this range of tissue-simulating phantoms, analysis using the Stern-Volmer equation revealed that collisional quenching by polystyrene microspheres accounted for a decrease in fluorescence intensity of 6-17% relative to the intrinsic intensity value when no microspheres (quenchers) were present. The intensity decrease from quenching is independent of additional, anticipated losses arising from optical scattering associated with the microspheres. These results suggest that quantitative fluorescence measurements in studies employing such phantoms may be influenced by collisional quenching.     

Fluorescence Quenching Reaction of Polyvinylpyrrolidone-Eosin Y System for the Determination of Polyvinylpyrrolidone

In pH 1.8 ∼ 2.8 weak acid medium, polyvinylpyrrolidone (PVP) and Eosin Y reacted to form complex that could result in Eosin Y (EY) fluorescence quenching. The maximum quenching wavelength was at 542 nm. The fluorescence quenching (ΔF) was proportional to the concentration of polyvinylpyrrolidone in a certain range. The linear range, the correlation coefficient and the detection limit were 0.33 ∼ 2.0 μg•mL⁻¹, 0.9994 and 99.6 ng•mL⁻¹, respectively. The influences of the coexistence substances were tested and the results showed that the method had good selectivity. Therefore, a new method based on fluorescence quenching of eosin Y by PVP for the determination of trace PVP was developed. The method was sensitive, simple and rapid, which was applied to the determination of trace PVP in the beer with satisfactory results. The reaction mechanism was also discussed.     

Temperature and concentration dependences of the photoluminescence of MEH-PPV polymer composite films with ZnO nanoparticles

The absorption and photoluminescence (PL) spectra of MEH-PPV: ZnO composite films have been investigated at different concentrations of ZnO nanoparticles and at different temperatures (in the case of PL). It has been shown that, at 297 K, with increasing concentration of ZnO nanoparticles in the composite, the intensity of the PL lines of MEH-PPV decreases, whereas the intensity of the PL lines of ZnO increases. At a relatively low concentration of ZnO nanoparticles, a decrease in the temperature leads to an increase in the intensity of PL lines associated with MEH-PPV and ZnO, whereas at higher concentrations of ZnO nanoparticles, the intensity of these lines decreases. This is accompanied by a slight shift in the maximum of the PL toward the infrared (IR) region and a narrowing of the PL line of MEH-PPV with a decrease in the temperature and with an increase in the ZnO concentration. The mechanism of energy transfer in composite systems consisting of a polymer and inorganic nanoparticles that can be responsible for the observed effects has been discussed.     

三维荧光与紫外光谱联合表征样品中猝灭剂赋存状态:以胡敏酸与Fe(Ⅲ)相互作用为例

利用三维荧光-紫外光谱表征了荧光猝灭剂的赋存状态,当样品体系中存在Fe(Ⅲ)的情况下,胡敏酸会发生荧光猝灭现象,而其紫外光谱基本不受影响。考察了胡敏酸荧光强度I值(Ex/Em=300 nm/510nm)和紫外吸光度A值(UV300)的变化,I/A比值越小,说明水样中猝灭剂Fe(Ⅲ)浓度越高。当胡敏酸为10,15和20 mg·L~(-1)时,根据Stern-Volmer公式I/I_0=1-f_c×K_c×[c]/(1+K_c×[c])以及拟合函数I/A=f×[k/(CFe~(3+)+c)+b],拟合得到荧光猝灭常数K_c=1.08~1.15,比例系数f_c=1.10~1.14之间,胡敏酸荧光强度值与吸光度比值(I/A)及铁离子浓度(C_(Fe~(3+))相关曲线系数f=0.83~1.19,k=587.19~612.19,c=0.87~0.92,b=-87.09~-46.36,拟合曲线相关性R~2均为0.99。Stern-Volmer公式描述了Fe(Ⅲ)对胡敏酸荧光的猝灭作用,但实际样品测定时难以获得无猝灭剂时的荧光强度I_0。基于荧光强度I_0与紫外吸光度A之间的内在联系,两者比值I/A与Fe(Ⅲ)浓度c的拟合函数亦可以反映Fe(Ⅲ)对胡敏酸荧光的影响。利用拟合公式预测城市污水厂及纳污河流样品的树脂分离富集液中铁离子浓度,与电感耦合等离子体发射光谱仪实际测量值相比,铁离子浓度较高的情况下(铁离子浓度大于0.4 mg·L~(-1)时)预测结果较好,可以判断猝灭剂的存在及相应浓度。     

含油岩屑固体粉末荧光的研究

通过对含油岩屑固体粉末荧光的研究,指出了在固体粉末中含油浓度在一定范围内时,其粉末荧光强度与含油的浓度成线性关系,对二者关系进行线性拟合,其相关系数R=0．9936。当样品中的含油的浓度达到一定程度时,其荧光强度保持一个恒定的值。同时,研究了固体粉末荧光猝灭现象以及猝灭机制。指出含油岩屑粉末的荧光猝灭,主要是生荧团分子之间形成络合物以及由于激发光谱和发射光谱重叠所引起的交叉弛豫所致。最后比较了固体粉末中荧光浓度猝灭与溶液中浓度猝灭。这些对于研究和开发对含油岩屑直接进行荧光检测的录井技术具有重要的指导意义。     

荧光猝灭法对头孢羟氨苄和头孢拉定荷移反应研究

研究了头孢羟氨苄和头孢拉定对荧光素的荧光猝灭反应及相互作用机理。因形成荷移络合物,头孢羟氨苄和头孢拉定对荧光素的荧光强度有很强的猝灭作用。采用紫外-可见光谱、红外光谱结合量子化学计算分析了荷移反应过程,揭示了头孢菌素类药物的成键规律和反应机理。在此基础上建立了测定头孢羟氨苄和头孢拉定含量的荧光光谱法。络合物的激发波长和发射波长分别为483, 517和519 nm,头孢羟氨苄和头孢拉定浓度分别在0.3～13.5 mg·L-1和0.1～1.2 mg·L-1范围内为线性关系,相关系数分别是r=0.999 7和r=0.999 3。应用该方法测定了头孢羟氨苄和头孢拉定药物制剂含量, 回收率分别在99.63%～99.91%和99.71%～100.08%之间。测定结果与文献值基本吻合。     

Photoluminescence study on Eu-implanted GaN

The photoluminescence (PL) properties of Eu-implanted GaN thin films are studied. The experimental results show that the PL intensity is seriously affected by ion implantation conditions. The PL efficiency increases exponentially with annealing temperature increasing up to a maximum temperature of 1050℃. Moreover, the PL intensity for the sample implanted along the channelling direction is nearly twice more than that observed from the sample implanted along the random direction. The thermal quenching of PL intensity from 10K to 300K for sample annealed at 1050℃ is only 42.7%.     

Detection of <Emphasis Type="Italic">Staphylococcus aureus</Emphasis> Carrying the Gene for Toxic Shock Syndrome Toxin 1 by Quantum-Dot-Probe Complexes

In this study, a high-sensitive and high-specific method to detect the toxic shock syndrome toxin-1 (TSST-1)-producing Staphylococcus aureus was developed based on quantum dot (QD) and oligonucleotide probe complexes. S. aureus carrying tst gene which is responsible for the production of TSST-1 were detected based on fluorescence resonance energy transfer (FRET) occurring between CdSe/ZnS QD donors and black hole quencher (BHQ) acceptors. QD-DNA probe was prepared by conjugating the carboxyl-modified QD and the amino-modified DNA with the EDC. Photoluminescence (PL) quenching was achieved through FRET after the addition of BHQ-DNA which was attached to tst gene probe by match sequence hybridization. The PL recovery was detected in the presence of target DNA by BHQ-DNA detached from QD-DNA probe because of the different affinities. In contrast, mismatch oligonucleotides and DNAs of other bacteria did not contribute to fluorescence intensity recovery, which exhibits the higher selectivity of the biosensor. The experimental results showed clearly that the intensity of recovered QD PL is linear to the concentration of target DNA within the range of 0.2–1.2 μM and the detection limit was 0.2 μM.     

高压条件下酪氨酸在线荧光光谱研究

在Cu2+与酪氨酸摩尔浓度比为0至40范围内,考察了压力对酪氨酸荧光光谱的影响,结果表明:在无Cu2+情况下,压力对酪氨酸荧光强度具有增敏作用,压力越高,增敏效果越显著,当压力为60 MPa时,荧光强度增加了约9%.Cu2+对酪氨酸荧光有猝灭作用,Cu2+浓度越高,猝灭越强;在Cu2+存在的情况下,压力对酪氨酸荧光的影...     

掺饵氢化非晶氧化硅1.54μm发光性质的研究

采用等离子体增强化学汽相沉积技术生长不同氧含量的氢化非晶氧化硅薄膜(a-SiO_{x∶H),离子注入铒及退火后在室温观察到很强的光致发光.当材料中氧硅含量比约为1和 1.76时,分别对应77Ｋ和室温测量时最强的1.54μm光致发光.从15到250Ｋ的变温实验显示 出三个不同的强度与温度变化关系,表明氢化非晶氧化硅中铒离子的能量激发和发光是一个 复杂的过程.提出氢化非晶氧化硅薄膜中发光铒离子来自于富氧区,并对实验现象进行了解 释.氢化非晶氧化硅中铒发光的温度淬灭效应很弱.从15到250Ｋ,光致发光强度减弱约1/2. 关键词： 铒 光致发光 氧含量}     

Fluorescence modulation of single CdSe nanowires by charge injection through the tip of an atomic-force microscope

We demonstrate a direct correlation between the charge state and photoluminescence (PL) intensity of individual CdSe nanowires by actively charging them and performing electrostatic force microscopy and PL measurements simultaneously. While the injection of positive charges leads to an immediate PL quenching, a small amount of injected electrons can lead to an increase of the PL intensity. We directly observed the migration of excess charges into the substrate, which leads to a recovery of the PL. Further, we show that the PL of individual NWs can be actively switched between on and off states by charging with the atomic-force microscope tip. We propose a model based on charge trapping and migration into the substrate to explain our results.     

较高掺杂浓度下CdSe/ZnS量子点光纤光致荧光光谱

制备了一种较高浓度掺杂的CdSe/ZnS量子点掺杂光纤.测量了不同掺杂浓度和不同光纤长度下的量子点光纤光致荧光光谱,得剑了荧光峰值增益最大时的量子点掺杂浓度和光纤长度.与低浓度掺杂光纤相比,较高掺杂浓度光纤中的荧光峰值光强明显提高.荧光峰值光强随光纤长度的变化在短距离内(L<1 cm)急剧上升,之后缓慢均匀下降.波长473 nm激励光强随光纤}乏度的变化呈指数形式衰减,消光系数为0.26～1.02 cm-1.在给定激励光强和激励波长的条件下,光纤中可达到最大荧光辐射的晕子点总数为一恒量.光纤中的荧光峰值波长存在红移,红移大小约8～15 nm,红移量与掺杂浓度以及光纤长度有关.这些实验结果可为今后量子点光纤放大器的研制提供参考.