基于上转换发光共振能量转移的CRISPR/Cas12a生物传感系统用于HPV16 DNA双信号检测

传统的纯核结构的上转换纳米材料用于生物传感时, 存在表面猝灭效应或者因发光共振能量转移(LRET)效率不高导致灵敏度低等缺点, 对目标物的灵敏检测有一定的局限性. 本文通过多步高温共沉淀, 介导壳层外延成长法, 合成了NaYF₄∶Yb³⁺,Er³⁺(C-UCNPs)核层发光和NaYF₄@NaYF₄∶Yb³⁺,Er³⁺@NaYF₄(CSS-UCNPs)内壳层发光能量限域型上转换纳米材料, 并表征了材料的晶型、 形貌、 表面配体、 元素组成和发光共振能量转移效率. 结果表明, 该材料具有表面猝灭效应低、 发光共振转移效率较高的优势, 随后将其与成簇规律间隔的短回文重复序列及其相关蛋白(CRISPR/Cas)12a-纳米金系统结合, 实现了人乳头瘤病毒DNA(HPV16 DNA)的比色定性和上转换发光定量分析, 检出限为69.8 pmol/L, 双信号检测有效提高了检测结果的准确性. 此外, 本方法不仅特异性强, 还能识别单碱基错配的HPV16 DNA, 提高了DNA片段的容错率.     

Studies on Upconversion Mechanism of ZrO2 ： Er^3＋, Yb^3＋ Nanocrystals Under Excitation at 488 and 980 nm

Erbium, Ytterbium-codoped ZrO2 nanoparticles(ZrO2:Er^3 ,Yb^3 ) were prepared by the sol-emulsiongel technique. The purpose of the present study is the application of upconversion phosphor in the biological label. In order to make out the mechanism of upconversion under 980 nm excitation the 488 nm pump was used. The influence of temperature on the crystallite phase was studied. The results confirm the upconverted mechanism in ZrO2:Er^3 ,Yb^3 nanocrystals is due to an energy transfer upconversion(ETU).     

La_(2.4)Mo_(1.6)O_8∶Yb~(3+),Er~(3+)材料的制备及其上转换发光性质

采用高温固相法制备了La_(2.4)Mo_(1.6)O_8∶Yb~(3+),Er~(3+)荧光粉。通过X射线衍射(XRD)和上转换发射光谱对样品进行了相结构和发光性质表征。XRD实验结果表明:合成的样品为面心立方萤石结构(Fm-3m)的La_(2.4)Mo_(1.6)O_8相。在980 nm红外光激发下,La_(2.4)Mo_(1.6)O_8∶Yb~(3+),Er~(3+)荧光粉发出分别来自Er~(3+)离子的~2H1_(1/2)→~4I_(15/2)、~4S_(3/2)→~4I_(15/2)跃迁的绿光(主峰为548和529 nm)和~4F_(9/2)→~4I_(15/2)跃迁的红光(主峰为670 nm)。进一步地,对样品中可能的上转换发光机制进行了讨论。     

氟离子浓度对稀土掺杂上转换发光纳米材料形貌及荧光寿命的影响

利用溶剂热法制备了Yb³⁺、Er³⁺共掺的NaYF₄上转换发光纳米材料。实验结果表明,不同F^-离子对纳米晶的晶型和粒径尺寸起着重要的作用。低F^-离子浓度下,NaYF₄纳米材料的粒径尺寸随F^-离子浓度的增加逐渐变小且趋于均一;高F^-离子浓度下,六方晶相的形成受到抑制,上转换纳米晶出现团聚现象。在一定浓度范围内,F^-离子的浓度有利于促进荧光发射。同时F^-离子浓度对荧光寿命也有显著的影响。     

上转换荧光响应性复合纳米凝胶的制备及荧光能量传递行为

采用水热法合成NaYF₄∶Yb³⁺,Er³⁺稀土纳米晶, 再经3-苄基三硫代碳酸酯基丙酸(BSPA)修饰, 制得功能化纳米晶体; 以罗丹明6G(R6G)为母体荧光染料, 经一系列反应合成了乙烯基功能化单体罗丹明6G酰基邻羧基苯甲肼腙(R6GHA); 将功能化纳米晶体与R6GHA构成荧光共振能量传递(FRET)的“给体/受体”对, 通过可逆加成断裂链转移(RAFT)聚合和“点击化学”反应, 合成具有多重响应性复合荧光纳米凝胶NaYF₄∶Yb³⁺,Er³⁺/PNIPAm-co-R6GHA. 采用TEM, XRD, FTIR和DSC对产物的微观结构进行了表征; 采用上转换荧光光谱(PL)研究了该复合纳米凝胶对pH值、 环境温度和不同金属离子的荧光响应行为, 并对相关机理进行了探讨. 结果表明, 环境温度变化对复合纳米凝胶的荧光发射具有显著影响, 且该复合纳米凝胶对Hg²⁺具有选择性荧光响应; 在H⁺或Hg²⁺作用下, 复合纳米凝胶中纳米晶和R6GHA之间会发生荧光共振能量传递; 通过纳米凝胶中纳米晶与R6GHA特征荧光发射峰比率的变化, 实现对Hg²⁺的检测.     

Yb ion as a sensitizer for the upconversion luminescence in nanocrystalline Gd3Ga5O12:Ho

The effect of Yb³⁺ co-doping on the upconversion luminescence in nanocrystalline Gd₃Ga₅O₁₂:Ho³⁺ was examined. Strong and efficient NIR to green anti-Stokes luminescence was noted in nanocrystalline Gd₃Ga₅O₁₂:Ho³⁺, Yb³⁺ after excitation into the ²F_5/2 level of Yb³⁺ with 978 nm radiation. Weaker blue, red and NIR anti-Stokes luminescence was also observed after 978 nm excitation. An enhancement of the red ⁵F₅ → ⁵I₈ luminescence was observed in the anti-Stokes spectrum compared to the Stokes emission spectrum. This enhancement was attributed to two distinct energy transfer upconversion (ETU) mechanisms which preferentially populate the (⁵F₄, ⁵S₂) and ⁵F₅ levels.     

1.54 and 1.75 μm infrared luminescence of Y2O3:Er

A new 1.75 μm infrared emission transition of Y₂O₃:Er³⁺ is assigned to the ⁴S_3/2 → ⁴I_9/2 transition of Er³⁺ ions situated at the C₂ sites of cubic RE₂O₃ (RE = Y, Gd, Lu). The intensities of features in the 1.54 μm ⁴I_15/2–⁴I_13/2 absorption transition due to Er³⁺ at S₆ and C₂ sites are consistent with the site occupation ratio and the relative magnetic dipole–electric dipole intensity contributions of Er³⁺ at the different sites. The 1.54 μm emission lines are predominantly from Er³⁺ ions at C₂ sites. The different behaviours of the emission intensities 1.75 and 1.54 μm groups with change in Er³⁺ dopant ion concentration, preparation technique, Yb³⁺ co-doping, temperature change and different excitation line are rationalized.     

NaYF4:Nd3+,Yb3+纳米粒子用于生物体系温度测量

采用溶剂热法制备了Nd³⁺敏化Yb³⁺的近红外纳米探针NaYF₄:Nd³⁺,Yb³⁺,观察到材料在980与865 nm两处发光峰的强度比值随温度的升高而降低。通过对探针中Nd³⁺/Yb³⁺比例的调节,综合考虑材料的发光强度与温敏效率,确定了NaYF4:2%Nd, 20%Yb为所测条件下适用于测量生物体系温度的较优组成。材料转水相前后温敏效率均随着Yb³⁺离子掺杂增加而提高,环己烷中最高可达1.9%·K^-1,水相中最高为0.46%·K^-1。通过盖肉片模拟及激光加热活体成像实验,研究了温敏材料在生物环境中发光随温度的变化情况,以及组织遮挡前后荧光比值未发生明显变化的结果,初步验证了使用该探针测量生物体系温度的可行性。     

Effect of Zn2+ Ions on Upconversion Emission of Er3+ in Zn/Er:LiNbO3 Crystal

The effect of Zn2+ ions codoped on the upconversion emission of Er3+ ions in Er:LiNbO3 crystal under different excitation wavelength was reported.The upconversion emission spectra of Zn/Er:LiNbO3 follo...     

锌-稀土矩形纳米簇的构筑及近红外发光性能

本文设计了一个新型含苯-甲基-苯骨架的席夫碱配体,构筑了两个具有矩形结构的锌-稀土纳米簇[Ln₂Zn₂L₂(OAc)₆] (Ln = Yb (1)和Er (2))。该席夫碱配体以“伸展型”配位模式与稀土离子进行配位,使这些锌-稀土纳米簇表现出较大的分子尺寸结构(0.7 nm × 1.1 nm × 2.2 nm)。荧光性质研究表明,由Zn/L组成的发色基团能有效敏化1和2中Yb³⁺和Er³⁺离子的近红外发光。通过对荧光量子产率及寿命进行分析发现,Zn/L对Yb³⁺离子的传能效率要高于Er³⁺离子。     

共掺稀土离子对Er~(3+)激活中红外激光晶体光谱性能的影响

Er3+掺杂的晶体能够产生2.7~3.0μm波段中红外激光,在激光医疗、光通讯、环境探测和光电对抗等领域具有重要的应用。基于本课题组近年来开展的Er3+激活中红外激光晶体的相关工作,本文综述了共掺稀土离子对Er3+激活晶体光谱性能的影响:包括敏化离子Cr3+、Yb3+等的敏化作用增强了Er3+的特征吸收峰;退激活离子Pr3+、Ho3+等的退激活效应抑制了自终态瓶颈效应;以及共掺Nd3+所起的敏化和退激活双重作用,并对中红外激光的研究趋势和前景进行了展望。     

上转换纳米粒子结合DNA链式扩增技术在阿霉素光控释放中的应用

纳米技术的发展使得纳米材料可以通过不同的表面包覆和修饰而在生物医药中发挥应用。 构建简单、经济、药物释放可控的生物相容性纳米药物仍是纳米生物化学领域的重点。 我们构建的纳米载药体系(DDS)以NaYF₄：Yb/Tm上转换纳米粒子为载体,在其表面通过光致断键型小分子4,5-二甲氧基-2-硝基苯基乙酮(DMNPE)连接一段短单链DNA,利用DNA链式扩增技术(HCR)来调节纳米粒子最终修饰的双链DNA的总量,从而控制对抗癌药物阿霉素(Dox)的担载量,在980 nm激光照射下上转换纳米粒子发射可切断DMNPE连接的近紫外光,协同胞内DNA酶的作用达到对药物的可控释放。 由于近红外光照对生物组织具有较好的穿透能力,此体系能够对病灶位置有更好的光靶向性从而减少药物的毒副作用。     

Fabricating UCNPs-AuNPs Fluorescent Probe for Sensitive Sensing Thiamphenicol

Anovel fluorescent probe has been constructed based on fluorescence resonance energy transfer(FRET) between upconversion nanomaterials(UCNPs) NaYF₄:Yb,Er and gold nanoparticles(AuNPs). The fluorescent "off-on" switching was formed for the detection of thiamphenicol(TAP) in egg samples. The fluorescence of UCNPs can be quenched to a certain degree by AuNPs. After adding TAP, the AuNPs generated aggregation and the fluorescence of UCNPs was recovered. The synthesized amination UCNPs and AuNPs were characterized by Fourier transform infrared spectroscopy(FTIR), UV-Vis, X-ray diffraction(XRD), energy dispersive spectrometer(EDS), and transmission electron microscope(TEM) techniques for observation and confirmation. As a model target, the detection of TAP has two linear ranges in the buffer solution within 0.01-0.1 μmol/L and 0.1-1 μmol/L using this fluorescent probe. The detection limit was obtained to be 0.003 μmol/L(S/N=3), which is favorable for trace analysis. The recovery of TAP from 98.2% to 105.3% was obtained, and the relative standard deviation(RSD) was from 2.5% to 4.3%. Furthermore, the method established in this study based on the UCNPs auto-low background fluorescence has high selectivity and strong ability to eliminate interference, which is beneficial to analyzing complex samples.     

Tm3+掺杂的NaYF4微米颗粒中强烈的单带下转换荧光发射

采用柠檬酸钠辅助的水热方法合成了一系列具有不同长径比的Tm³⁺掺杂的β-NaYF₄ (NaYF:Tm³⁺)微米棒(盘).通过X射线衍射(XRD),扫描电子显微镜(SEM),能量色散X射线荧光光谱(EDX),傅里叶变换红外(FTIR)光谱和激光光谱学等手段对所制备的系列β-NaYF₄微米棒(盘)进行了表征. XRD和SEM分析表明β-NaYF₄微米棒(盘)的长径比依赖于前驱液的pH值,随着前驱液的pH值的增加,从长棒逐渐过渡到六角盘.光谱测量结果表明:一系列NaYF₄:Tm³⁺微米晶体在656 nm脉冲激光选择激发下,均获得了强烈的单带近红外下转换荧光发射.系统研究了激发波长、环境温度和颗粒长径比对NaYF₄:Tm³⁺微米晶体中单带近红外荧光强度的调控.结果表明:颗粒长径比越大,荧光强度越强.进一步探索了颗粒长径比调控的荧光增强机理,并提出了基于长径比控制的缺陷空位机理.     

Highly efficient blue up-conversion of Tm in Nd–Yb–Tm co-doped ZrF4-based fluoride glass

Up-conversion luminescence and energy-transfer processes in Nd³⁺, Yb³⁺ and Tm³⁺ co-doped ZrF₄-based fluoride glasses have been studied under 800 nm light excitation. Blue up-converted emission around 478 nm which can be assigned to the Tm³⁺:¹G₄→³H₆ transition, was strongly observed. Up-conversion luminescence intensity exhibited an YbF₃-concentration dependence. Among the Nd³⁺, Yb³⁺ and Tm³⁺, Nd³⁺ and Tm³⁺ have ground state absorption bands due to the (²H_9/2,⁴F_5/2)←⁴I_9/2 and ³F₄←³H₆ transitions, respectively, which can be directly pumped by 800 nm radiation. However, no emissions were observed in Tm³⁺ singly-doped and Tm³⁺–Yb³⁺ doubly-doped glasses under 800 nm excitation. Therefore, a possible up-conversion mechanism may be proposed as follows: energy-transfer firstly occurs from Nd³⁺ to Yb³⁺ when Nd³⁺ is excited by 800 nm light, then the energy is transferred from Yb³⁺ to Tm³⁺ which is in the excited state and, finally, blue up-conversion emission of Tm³⁺ is observed through the Tm³⁺:¹G₄→³H₆ transition.     

室温下快速合成超小Fe3+掺杂BiF3纳米粒子

室温下快速合成了Fe³⁺掺杂的BiF₃超小纳米粒子,只需要反应1 min,较小的Fe³⁺离子即可替代BiF₃晶格中较大的Bi³⁺离子.随着Fe³⁺掺杂量的增加,BiF₃：Fe³⁺纳米粒子的粒径不断减小,当Fe³⁺的掺杂量达到0.119时,可以得到尺寸约为6.9 nm的Fe³⁺掺杂BiF₃超小纳米粒子.此外,Fe³⁺离子的掺杂使BiF₃：Fe³⁺-x样品的能带结构发生了显著变化.制备的Fe³⁺掺杂BiF₃超小纳米粒子在光催化剂和荧光材料方面具有潜在的应用价值.     

A Long-term and Stable Surface Modification Method for Lanthanide Doped Upconversion Nanoparticles by Oxidized Alginate

Lanthanide doped upconversion luminescent nanoparticles (UCNPs) have drawn widely attention in biomedical research. The generally synthesized oleate capped UCNPs have no aqueous dispersibility so that surface modification is required to be water dispersible. Herein, we developed an easy-going but effective approach to prepare hydrophilic UCNPs based on oxidized alginate molecule (OAlg). After surface modification treatment, the OAlg modified UCNPs (UCNPs-OAlg) shows excellent dispersibility and longer stability in aqueous solution even after 180 days. After incubation with UCNPs-OAlg, the upconversion luminescent images of living Hela cells were clearly obtained. It indicated that oxidized alginate modified UCNPs can be candidate for excellent imaging probes in future.     

氧化镥中杂质对铈掺杂硅酸镥多晶粉体光谱性质影响

氧化镥中杂质元素对其分离制备工艺、生产成本及镥基硅酸盐闪烁晶体的性能有很大影响,但杂质元素对晶体的性质影响研究较为有限,有待进一步完善。 本文采用高温固相法制备了Lu₂O₃分离过程中关键杂质元素Yb³⁺和Ca²⁺共掺杂Lu₂SiO₅∶Ce多晶粉体,研究了Yb³⁺或Ca²⁺含量对多晶粉体光谱性质的影响,结果表明:Yb³⁺或Ca²⁺共掺并未改变发射光谱的形状和位置,随着杂质元素摩尔分数的增加,光谱强度和荧光寿命逐渐降低。     

LD激发的ZnWO4:Er3+晶体上转换发光

采用Czochralski法生长出ZnWO₄:Er³⁺(Er=0.02mol)单晶,测量了吸收光谱和激发光谱。在波长966nm功率500mW的激光二极管(LD)激发下观察到上转换发光。强度最大的发射峰位于547和558nm,发射光谱分析表明,上转换激发过程与双光子步进吸收有关。     

Optical spectra of Yb and Yb–Nd interaction in Cs2NaNd0,4Yb0,6Cl6

Interaction between octahedrally coordinated Nd³⁺ and Yd³⁺ in Cs₂NaNd_0,4Yb_0,6Cl₆ reduces the Nd³⁺ luminescence lifetime by roughly two orders of magnitude with respect to that found in Cs₂NaNdCl_{6– · –} Analysis of low temperature absorption and emission spectra reveals that the nonradiative Nd³⁺–Yb³⁺ energy transfer has to be assisted by lattice phonon emission, nevertheless the rate of the transfer is high in the 4–300 K temperature region and attains 5.8×10⁵s^-1 at room temperature. A phase transition of Cs₂NaNd_0,4Yb_0,6Cl₆ between 12 and 13 K is evidenced by abrupt change of both the spectra and lifetimes of Yb³⁺. Reduction of Yb³⁺ lifetime from 5.3 ms to 150 μs is at the transition from low symmetry phase to high symmetry phase is supposed to be associated with a three ion interaction which occurs in ordered lattice and disappears in low temperature disordered structure.