胶体水相法制备高量子产率及高稳定性的水溶性ZnSe量子点

采用简便的胶体水相法制备了高荧光强度且稳定性良好的ZnSe量子点(ZnSe QDs),克服了以往水相合成法稳定性差、量子产率低等缺陷。优化后的最佳合成条件为：以还原型L-谷胱甘肽作为稳定剂,L-谷胱甘肽∶Se2-∶Zn2+摩尔比为5∶1∶5,介质pH 10.5,反应温度在90～100 ℃之间。且合成后不需要采取任何光照后处理,ZnSe QDs的量子产率(QYs) 即可高达50.1%,放置3个月后荧光强度基本不变,水溶性优良。用紫外-可见分光光度法(UV-Vis)、荧光分光光度法(FL)、透射电子显微镜(TEM)等分析检测手段,对得到的ZnSe QDs的性能进行表征。合成的量子点在300 nm激发下发蓝紫色荧光(370 nm),其优良的光化学特性将有利于其在光热器件的制造及化学生物领域的应用。     

量子点的荧光特性在生物探针方面的应用

量子点具有传统有机荧光染料无可比拟的光学魅力,在生物医学及材料领域已引起广泛的兴趣,许多科学工作者在量子点用于生物学领域方面已经取得一定进展。目前,量子点最有前途的应用领域是在生物体系中作为荧光标记物。通过观察量子点标记分子与靶分子相互作用的部位,及其在活细胞内的运行轨迹,可能为信号传递的分子机制提供线索,从而为阐明细胞生长发育的调控及癌变规律提供直观依据。文章介绍了量子点研究生物大分子之间的相互作用、生物大分子荧光标记、细胞及生物组织的荧光标记与成像以及活体成像等方面的应用。并概述了纳米量子点作为生物荧光探针的应用前景以及亟待解决的问题。     

Enhancement of Intracellular Delivery of CdTe Quantum Dots (QDs) to Living Cells by Tat Conjugation

Quantum dots (QDs), as novel fluorescence probes, have shown a great potential for bio-molecular labeling and cellular imaging. To stain cellular targets, the sufficient intracellular delivery of QDs is required. In this work the tat, a typical membrane-permeable carrier peptide, was conjugated with thiol-capped CdTe QDs to form CdTe Tat-QDs, and the intracellular deliveries of CdTe QDs or CdTe Tat-QDs were compared in human hepatocellular carcinoma (QGY) cells and human breast cancer (MCF7) cells in vitro by means of confocal laser scanning microscopy. Added into the cell dishes, both QDs and Tat-QDs adhered to the outer leaflet of the plasma membrane of cells within a few minutes, but the binding amount of Tat-QDs was obviously higher than that of QDs. Then both QDs and Tat-QDs can penetrate into cells, and their cellular contents increased with incubation time but both saturated after 3 hours incubation. However the cellular levels of Tat-QDs were higher than those of QDs, with the ratio of 2.1 (±0.3) times in QGY cells and 1.5 (±0.2) times in MCF7 cells, demonstrating the enhancing effect of Tat conjugation on the intracellular delivery of QDs.     

功能性CdTe量子点荧光增敏法测定对苯二胺

以CdT e量子点作为荧光探针,基于荧光增敏法对对苯二胺进行了定量检测,考察了缓冲溶液体系、量子点浓度、反应时间等多种因素的影响。实验结果表明,在pH 7.6的0.2m ol/LN a2HPO4-N aH2PO4缓冲液中,反应时间为15m in,对苯二胺浓度为6.0×10-6—1.8×10-5m ol/L范围时,其线性回归方程为ΔF=75.64＋7.95C（10-6m ol/L）,相关系数和检出限分别为0.9989和2.1×10-8m ol/L。该方法检出限低,灵敏度高,为对苯二胺的测定提供了新的选择。     

平均探测时间:研究单个量子点荧光现象的另一种思路

Due to photoluminescence intermittency of single colloidal quantum dots (QDs), the traditional exponential fluorescence lifetime analysis is not perfect to characterize QDs'' fluorescent emission behavior. In this work we used the time-tagged time-resolved (TTTR) mode to record the fluorescent photons from single QDs. We showed that this method is compatible with the traditional lifetime analysis. In addition, by constructing the trajectory over time and the distribution of average arrival time (AAT) of the fluorescent photons, more details about the emission behavior of QDs were revealed.     

Non-invasive Near Infrared Fluorescence Imaging of CdHgTe Quantum Dots in Mouse Model

Near infrared CdHgTe quantum dots (QDs) acted as biomarker for in vivo imaging were synthesized in aqueous solution. The size and the fluorescence wavelength of the synthesized quantum dots can be arbitrary manipulated by using different refluxing time. In particular, the fluorescence wavelength was extended to near infrared range (700∼900 nm), which make the in vivo imaging possible. Meanwhile, the characteristics, such as morphology, size, spectra, stability and toxicity were investigated. The dynamic bio-distribution, clearance from blood, liver and intestine in living animal were in vivo monitored by a NIR imaging system. The circulation of CdHgTe QDs in living mice was addressed semi-quantitatively according to the changes of fluorescence intensity. The high stability as well as high fluorescence intensity makes QDs particular interested candidates for in vivo imaging studies.     

CdTe量子点荧光猝灭法测定微量铅

以CdTe量子点作为荧光探针,基于荧光猝灭法对铅进行了定量检测,考察了缓冲溶液体系、量子点浓度、反应时间等多种因素的影响。实验结果表明,在pH 7.5的0.2mol/L Na2HPO4-NaH2PO4缓冲液中,反应时间为10min,铅浓度为2.0×10-6—3.5×10-5mol/L范围时,其线性回归方程为ΔF=26.35+11.47C(×10-6mol/L),相关系数和检出限分别为0.9991和1.8×10-8mol/L。该方法灵敏度高,为铅的测定提供了新的方法。     

New Design for Quantum Dots Cellular Automata to obtain Fault Tolerant Logic Gates

In this paper, we analyze fault tolerance properties of the Majority Gate, as the main logic gate for implementation with Quantum dots Cellular Automata (QCA), in terms of fabrication defect. Our results demonstrate the poor fault tolerance properties of the conventional design of Majority Gate and thus the difficulty in its practical application. We propose a new approach to the design of QCA-based Majority Gate by considering two-dimensional arrays of QCA cells rather than a single cell for the design of such a gate. We analyze fault tolerance properties of such Block Majority Gates in terms of inputs misalignment and irregularity and defect (missing cells) in assembly of the array. We present simulation results based on semiconductor implementation of QCA with an intermediate dimensional dot of about 5 nm in size as opposed to magnetic dots of greater than 100 nm or molecular dots of 2–5Å. Our results clearly demonstrate the superior fault tolerance properties of the Block Majority Gate and its greater potential for a practical realization. We also show the possibility of designing fault tolerant QCA circuits by using Block Majority Gates.     

L-半胱氨酸修饰CdS量子点检测银离子

室温一步合成了L-半胱氨酸修饰的CdS量子点,具有水溶性和生物相溶性。在0．0050mol／L磷酸缓冲溶液中,于L-半胱氨酸存在下,银离子对CdS量子点荧光发射有显著的增敏作用,CdS量子点荧光发射峰位置逐渐由545nm向558nm红移,CdS量子点荧光强度与银离子的浓度成线性关系,方法的线性响应范围为2．0×10^-7-1．0×10^-6mol／L,检出限为2．1×10^-8mol／L。是一种简单,迅速,灵敏且可操作的检测银离子的新方法。     

以花生碳量子点为探针基于其荧光猝灭-恢复测定多巴胺的研究

碳量子点(CQDs)是一种新型的荧光碳纳米功能材料,其良好的生物相容性和优异的光学性能引起了人们的广泛关注。选用富含蛋白质、脂肪和碳水化合物的花生仁(Peanut,PN)及水为原料,无需添加任何其他试剂,在水热反应釜中于190℃反应20 h,可一步合成绿色发光CQDs。透射电镜(TEM)结果显示,所制备的花生碳量子点(PN-CQDs)的粒径大约在10 nm左右,分布较为均匀;X射线衍射谱(XRD)和傅里叶变换红外光谱(FTIR)显示PN-CQDs晶型为无定型碳,表面富含-OH、-COOH、含氮官能团等亲水性基团,具有良好的水溶性。紫外-可见光谱(UV-Vis)和荧光发射光谱(FL)表明, PN-CQDs在275 nm处有一明显的吸收峰,为CQDs紫外特征吸收峰;该PN-CQDs具有激发波长依赖性,荧光发射峰的位置随激发波长的变化而移动;当激发波长λex为326 nm时,发射波长λem为408 nm处的荧光强度最大, PN-CQDs发出蓝色的荧光。以硫酸奎宁为参照物,利用参比法测得PN-CQDs的荧光量子产率φ为5.0%。基于该PN-CQDs良好的发光特性,以其为探针,构建了"关-开"型荧光体系用于多巴胺(Dopamine,DA)的高灵敏度检测。研究表明,在pH 3.80的HAc-NaAc缓冲介质中, Ce(Ⅳ)存在下, PN-CQDs与Ce(Ⅳ)之间的电子转移反应和Ce(Ⅳ)与该PN-CQDs表面基团结合使PN-CQDs发生的聚集作用共同导致PN-CQDs在λex/λem=326 nm/408 nm处的荧光发生猝灭,荧光信号"关闭";当加入DA后, DA与结合于PN-CQDs表面的强氧化性Ce(Ⅳ)发生反应,从而将Ce(Ⅳ)从PN-CQDs表面移除, PN-CQDs的荧光得以恢复,荧光信号重新"打开"。在优化的实验条件下, DA浓度与PN-CQDs在λex/λem=326/408 nm处的荧光恢复值ΔF呈良好线性关系,线性范围为2.5×10-7~1.0×10-5mol·L^-1,决定系数R2为0.997 6,检出限为9.0×10-8mol·L^-1。探讨了体系的荧光"猝灭-恢复"机理,对PN-CQDs和PN-CQDs-Ce(Ⅳ)体系进行了荧光寿命拟合,其加权平均荧光寿命分别为6.02与5.15 ns, Ce(Ⅳ)对PN-CQDs荧光猝灭类型为动态猝灭;反应中生成的Ce(Ⅲ)于λex/λem=251/350 nm处的荧光对DA的测定无影响。该方法灵敏、简便、快速,应用于实际样品中DA的测定,加标回收率(平均值±SD)在97.5%±1.3%~103%±1.5%之间,结果满意。该研究提供了一种新的DA荧光检测方法,实现了对DA的准确测定。     

The Influence of Surface Trapping and Dark States on the Fluorescence Emission Efficiency and Lifetime of CdSe and CdSe/ZnS Quantum Dots

To investigate the influence of surface trapping and dark states on CdSe and CdSe/ZnS quantum dots (QDs), we studied the absorption, fluorescence intensity and lifetime by using one-and two-photon excitation, respectively. Experimental results show that both one- and two-photon fluorescence emission efficiencies of the QDs enhance greatly and the lifetime increase after capping CdSe with ZnS due to the effective surface passivation. The lifetime of one-photon fluorescence of CdSe and CdSe/ZnS QDs increase with increasing emission wavelength in a supralinear way, which is attributed to the energy transfer of dark excitons. On the contrary, the lifetime of two-photon fluorescence of bare and core-shell QDs decrease with increasing emission wavelength, and this indicates that the surface trapping is the dominant decay mechanism in this case.     

量子点光谱成像技术与重建仿真

为满足机载星载平台对光谱成像系统紧凑型和轻量化的需求,克服当前光谱成像技术分光系统结构复杂、成本高的不足,提出了基于量子点材料的光谱成像技术方案。将条带状的量子点阵列片放置于前置镜焦面前,利用量子点材料对光谱的吸收特性对探测目标的入射光谱进行调制,使用最小二乘法建立探测目标的光谱重建模型,采用推扫的方式获取数据并进行光谱重建可以获得目标光谱和空间信息。量子点光谱成像技术具有光谱分辨率高、能量利用率高、体积小、光谱范围宽和成本低等优势。分析了不同光谱谱段间隔和噪声等因素对重建光谱分辨率的影响,以及对重建光谱准确性或者失真度的影响。分析得出谱段间隔越低,光谱分辨率越高;重建的准确性和分辨率随着噪声水平的增大而降低;适当的提高谱段间隔,可以提高重建的准确性。将已知数据立方体和它的仿真结果进行对比,可以看出还原得到的量子点光谱图像质量较好,验证了该技术的可行性。量子点材料为光谱成像技术提供了新的途径,在航空航天等小型化光谱遥感领域具有极大的应用潜力。     

Fluorescence Analysis with Quantum Dot Probes for Hepatoma Under One- and Two-Photon Excitation

A new class of fluorescent probe produced by conjugating semiconductor quantum dots (QDs) with protein molecule is proposed as an alternative to conventional organic labels. However the fluorescence characteristics of the QD bioconjugates are not clear while they are excitied with one- or two-photon laser pulse. We synthesized specific immunofluorescent probes by linking QDs to alpha fetoprotein (AFP) antibody for specific binding alpha-fetoprotein -an important marker for hepatocellular carcinoma cell lines, and archived specific fluorescence detection with the QDs-Anti-AFP in nude mice. Then, we have analyzed the fluorescence characteristics of QDs-Anti-AFP and original QDs both under one- and two-photon excitations. The results demonstrated that QDs-Anti-AFP's fluorescent spectral and lifetime haven't varied much from that of original QDs. Moreover, QDs-Anti-AFP have exhibited higher fluorescence efficiency than QDs under two-photon examination.     

CsPbBrI2量子点制备及其光探测器性能

采用热注入法制备空气稳定性良好的CsPbBrI2量子点,以375 nm的脉冲激光作为激发光源研究其光致发光性能.通过旋涂的方式制备相应薄膜,将其作为光敏层应用到光探测器,并对器件的光电子性能和稳定性进行详细研究.结果表明:CsPbBrI2量子点在635nm附近有强烈的荧光效应,光谱发光峰较窄,半峰宽约为35 nm.CsPbBrI2量子点禁带宽度为1.90eV,制备的探测器光检测带宽从紫外光260nm到红光650 nm,光响应度为0.26 A/W,高开/关比高达104,上升/衰减时间为3.5 ms/3.5 ms.在25℃,湿度在25%~35%大气环境下存储60天,性能与初始值相比几乎没有变化.CsPbBrI2量子点具有优异的稳定性、可制备高性能的宽带光检测和易于制造等优点,具备一定的应用前景.     

Thiol-Capped CdTe Quantum Dots with Two-Photon Excitation for Imaging High Autofluorescence Background Living Cells

To effectively image living cells with quantum dots (QDs), particularly for those cells containing high content of native fluorophores, the two-photon excitation (TPE) with a femto-second 800 nm laser was employed and compared with the single-photon excitations (SPE) of 405 nm and 488 nm in BY-2 Tobacco (BY-2-T) and human hepatocellular carcinoma (QGY) cells, respectively. The 405 nm SPE produced the bright photoluminescence (PL) signals of cellular QDs but also induced a strong autofluorescence(AF) from the native fluorophores like flavins in cells. The AF occupied about 30% and 13% of the total signals detected in QD imaging channel in the BY-2-T and QGY cells, respectively. With the excitation of 488 nm SPE, the PL signals were lower than those excited with the 405 nm SPE, although the AF signals were also reduced. The 800 nm TPE generated the best PL images of intracellular QDs with the highest signal ratio of PL to AF, because the two-photon absorption cross section of QDs is much higher than that of the native fluorophores. By means of the TPE, the reliable cellular imaging with QDs, even for the cells having the high AF background, can be achieved.     

产生量子点的一种新方法(英文)

我们提出并试验了一种制备量子点阵的新方法。利用二步法制备的阳极氧化铝上规则排列纳米洞为模板,以紫外脉冲激光(2 48nm)溅射方法将氧化物经过带纳米洞的模板溅射到单晶Si的衬底上。以荧光材料La0 .95Eu0 .0 5BaB9O16 为靶材,初步获得了Si衬底上荧光材料的点阵。     

高色域量子点LED及其在背光显示中的应用研究

量子点因其独特优异的光学特性而被广泛应用于发光领域,其中最突出的特点是光谱调谐方便,只需要改变材料的尺寸,就可实现发光光谱的调谐。结合实际应用的需要,选取CdSe材料作为主要研究对象,通过改进工艺,采用希莱克技术隔绝水氧,使用高温热注入法,调整原料中镉源和锌源,硒源和硫源的比例,获得了尺寸分别约为6.0和4.2 nm,发光峰分别为625和525 nm,半高宽分别为30和28 nm,荧光量子产率分别达到82%和61%的粒径均一、色纯度高且高效稳定核壳结构CdSe/ZnS红光和绿光量子点材料。然后对量子点LED在背光显示中的应用进行了研究,采用合成的红光和绿光量子点材料替代传统工艺中的荧光粉材料,通过改进封装方式,对量子点光转换层采用双层环氧树脂AB胶保护,同时引入PMMA透镜包覆,从根本上隔绝水氧。最终得到的量子点白光LED,红绿蓝光发射峰分别为630, 535和453 nm,半高宽别为20, 28和30 nm,三段光谱发射峰两侧对称性良好,有效解决了传统荧光粉白光LED在红色光谱波段缺失的问题,并同时实现了单色性好、色纯度高、色彩饱和度高等优点。在LED积分球光色电测试系统中20 mA电流条件下测试,得到了CIE色坐标为(0.329, 0.324)的白光量子点LED,这是非常接近标准白光的色坐标。其色温为5 094 K,光效达到94.72 lm·W-1,显色指数Ra可达78.6,寿命超过400 h。最后对量子点LED灯条进行封装得到背光源,根据测试获取的白光量子点LED发射光谱,可以得到sRGB颜色三角形,即色域,通过对比NTSC1931标准色域,得到了色域覆盖率可以达到109.7%的高色域量子点LED背光源。开发的LED背光由240个白光量子点LED制成,并且首次成功演示了29英寸液晶电视面板,这一结果将进一步开发量身定制的量子点,特别是在高性能显示器应用领域。     

Investigation of Novel Quantum Dots/Proteins/Cellulose Bioconjugate Using NSOM and Fluorescence

We investigated the engineered bioconjugate of cadmium selenide core/zinc sulfide shell, (CdSe)ZnS, quantum dots (QDs) with genetically modified proteins using fluorescence spectroscopy, near-field scanning optical microscopy (NSOM) and spectroscopy (NSOS). The protein polymer was allowed to self-assemble to the bacterial microcrystalline cellulose surface through the cellulosic binding domain. Results from the sample containing the QDs/protein/cellulose assemblies suggest that QDs were arrayed along the cellulose surface. The spectroscopic change of spectroscopic properties of the QDs upon bioconjugation, indicating the interaction among the immobilized QDs and between the constructed protein and QDs.     

碳量子点荧光猝灭法测定饮料中日落黄

以柠檬酸为碳源制备碳量子点(CQDs),所得碳量子点被394 nm的光激发后在484 nm处有较强的荧光发射,最大吸收波长为482 nm的日落黄能强烈猝灭碳量子点的荧光。基于该现象,发展了一种以碳量子点为荧光探针测定日落黄的分析方法,并探讨了荧光猝灭机理。在选定的实验条件下,该分析方法的线性检测范围为0.1~100μmol/L,检出限(3σ/k)为0.051μmol/L。     

温度对CdSe/znS量子点吸收光谱和光致发光谱的影响

测量了分散于正己烷溶液和甲苯溶液中的CdSe/ZnS量子点在室温到近溶液沸点温度间的吸收与光致发光光谱,比较了两种不同的CdSe/ZnS量子点的光谱特性,讨论了温度对吸收和光致发光光谱峰值波长以及相对强度的影响。结果表明:在25~100℃范围内,CdSe/ZnS量子点激子吸收峰波长有微小红移,最大约为4nm;光致发光光谱峰值波长略有红移,但最大不超过6nm。根据光致发光光谱测量的结果,确定了Varshni定律中关于CdSe/ZnS量子点禁带宽度的两个经验参数:α=(2.0±0.2)×10^-4eV/K和β=(200±30)K。温度对CdSe/ZnS量子点吸收强度影响不大,荧光发射强度与温度呈线性关系增强。