Multi-Color Fluorescent Carbon Dots: Graphitized sp2 Conjugated Domains and Surface State Energy Level Co-Modulate Band Gap Rather Than Size Effects

Four types of carbon dots (CDs) with various color (blue, green, yellow, and red) emissions have been synthesized under solvent-free conditions from citric acid and different nitrogen sources (DMF, urea, ethanamide, and formamide). By detailed characterization and comparison, it is confirmed that the graphitized sp² conjugated domain and surface functional groups such as C−O and C=N play synergetic roles in adjusting the fluorescence properties. Notably, the size effect is not the dominant mechanism to achieve multi-color fluorescence emissions in this work. The structural configuration of the carbon dots further influences the energy band structure, as demonstrated in simplified energy level diagrams. An absorption peak at approximately 560 nm appears in the visible light region for red-emitting CDs, assigned to an n→π* transition of the aromatic structure, thus introducing a new surface state energy level, resulting in a reduction in the energy of electron transition and the expansion into the visible region of the UV/Vis spectrum. Taking advantage of the diverse absorption and emission properties, different CDs/TiO₂ binary composites are obtained for photocatalytic degradation of organic dyes, and it is found that the absorption range in terms of visible light and the band gap of the carbon dots make a difference to the photocatalytic performance of the composites.     

双二芳基乙烯配体构建的Ag (Ⅰ)配合物及多色光致变色性质

采用闭环态紫外最大吸收波长不同的2个二芳基乙烯:1,2-双(2'-甲基-5'-(4"-苯腈)-3'-噻吩)全氟环戊烯(L1)和顺-1,2-二氰基-1,2-双(2',4',5'-三甲基-3'-噻吩)乙烯(L2)为配体,以Ag(Ⅰ)为金属离子、具有强配位能力的CF_3COO~-为阴离子,合成了一个新的双组分光致变色Ag(Ⅰ)配合物1。通过红外光谱、核磁共振氢谱及质谱对其进行结构表征。以直接混合的双配体体系(L1+L2)为对照,用UV-Vis光谱法研究了配合物1在四氢呋喃(THF)溶液和聚甲基丙烯酸甲酯(PMMA)薄膜中的多色态光致变色性质。结果表明,银离子配位没有抑制而是调节了 2个配体的光致变色性质,经254、405 nm和大于550 nm波长光的不同组合照射,可选择性地使1中2个配体发生分步光异构化反应,成功实现了黄色、蓝色、红色和紫色4个色态的转变。     

Ca0.8La0.2-x-yMoO4∶xTb3+,yEu3+荧光材料的水热合成及多色发光性质

采用水热法制备了Ca0.8La0.2-x-y MoO4∶xTb3+,yEu3+荧光材料,并对其结构和发光性能进行了研究。X射线衍射(XRD)分析表明,合成的样品为四方晶系的CaMoO4白钨矿结构,稀土离子La3+、Eu3+、Tb3+的引入不会改变主晶格的结构。荧光光谱表明,与CaMoO4∶Eu3+荧光粉相比,基质中掺杂La后的Ca0.8La0.15MoO4∶0.05Eu3+样品的616 nm(5D0→7F2)处的特征发射峰明显增强。在285 nm紫外光激发下,Ca0.8La0.16-y MoO4∶0.04Tb3+,yEu3+(y=0.01,0.03,0.05,0.07)系列样品在545 nm和616 nm处出现的发射峰,分别对应于Tb3+的5D4→7F5跃迁和Eu3+的5D0→7F2跃迁,并且随着Eu3+掺杂量的增加,Tb3+的发射峰逐渐减弱,Eu3+的发射峰逐渐增强,表明该荧光材料中存在着由Tb3+到Eu3+能量传递。随着Ca0.8La0.16-y MoO4∶0.04Tb3+,yEu3+(y=0.01,0.03,0.05,0.07)系列样品中激活剂Eu3+掺杂量的增加,荧光粉实现了从绿色→黄绿→黄色→红色的颜色可调。     

多色分图层激光扫描自聚焦投影技术

为了突破常规激光投影仪由于单一波长的局限性造成应用场景的限制,同时实现对不同零件、不同材料、不同装配工艺的分图层投影,设计并搭建了多色分图层激光扫描自聚焦投影系统。系统采用2种波长的激光作为光源,根据二向色镜的位置不同,提出了多色共光轴和分光路2种激光扫描自聚焦投影方案,并推导了相应的光学系统数学模型。通过系统的自聚焦功能调节镜组间距,均可以实现在不同距离的投影面上聚焦出不同颜色的最小光斑。利用ZEMAX光学设计软件对2种投影光学系统进行仿真,并从系统可靠性和投影效果上对2种系统进行比较分析。实验结果表明：在3 m处的投影面上,共光轴系统各种波长的光斑直径均在0.8 mm以内,且光斑大小均匀,可以实现多色分图层的扫描自聚焦投影功能。     

基于聚乙烯醇聚合物点制备荧光纳米复合材料

近年来, 由于聚合物点(PDs)具有良好的荧光性质和光收集能力, 受到了人们广泛的关注, 应用在生物成像和检测等领域. 然而, 目前报道的聚合物点大多数是指共轭聚合物经过组装、固定形成的, 因此聚合物点保持着形成之前的共轭聚合物的相关性质, 且具有更好的稳定性和进一步功能化的能力. 本文中我们研究的聚合物点是指从非共轭线性聚合物为原料而制备的聚合物点, 这类聚合物包括聚环氧乙烯, 多糖等. 聚合物点不仅包含使其具有荧光的碳化中心, 还具有外围的聚合物链结构. 因此, 可以拓展应用聚合物点的聚合物特性. 我们利用PDs的荧光中心和外围的聚合物链双功能性质, 详细研究了基于PDs制备功能性纳米复合材料体系. 首先, 我们原位制备了聚乙烯醇/PDs纳米复合膜材料(PDs是直接通过聚乙烯醇可控碳化而产生的). 复合材料不仅保持了PDs的荧光特性, 还保持了聚乙烯醇易加工的特性, 如可以制备成纳米复合膜材料, PDs含量可以根据需要调控: 0, 20%, 40%, 60%, 80%, 100%. 纳米复合膜材料在不同激发光下具有多颜色发光性质. 进一步的, 我们验证了PDs水溶液可以和很多其他水溶性聚合物, 石墨烯量子点或半导体量子点实现共混, 从而制备双功能性纳米复合材料.     

Fabrication of Novel Polymer Nanoparticle-Based Fluorescence Resonance Energy Transfer Systems and their Tunable Fluorescence Properties

In this study, two hydrophobic fluorescent dyes, nitrobenzoxadiazolyl (NBD) and 9-(diethylamino)benzo[a]phenoxazin-5-one (NR) with different doping ratios were incorporated into polymer nanoparticles to constitute novel polymer nanoparticle-based fluorescence resonance energy transfer (FRET) systems via a facile one-step mini-emulsion polymerization. Spectroscopic characteristics demonstrate that the two fluorophores have been successfully embedded into the nanoparticles, and the fluorescence emission intensity of the two hydrophobic dyes can be greatly enhanced in aqueous media. The as-prepared fluorescent nanoparticles also display a uniform small size (ca. 55 nm), high dye load, intense fluorescence, as well as controllable amount and ratio of the two dyes. The observed FRET efficiencies (16.0–75.2%), as well as the distance (r) between NBD (donor) and NR (acceptor), is closely correlated to the doping ratio of two dyes. Moreover, by varying the doping ratio of two dyes, the fluorescent nanoparticles would exhibit multicolor through FRET upon a single wavelength excitation, and the fluorescence emission signals of the dye-doped nanoparticles could be accurately tuned. These results indicate that the as-prepared uniform FRET-mediated nanoparticles are of high interest in multiplexed bioanalysis.