高稳定性黑米碳点的绿色合成及其细胞成像应用

以绿色廉价的黑米为碳源,采用简单的水热法一步合成了碳点(carbon dots,CDs)。所合成的CDs不仅对pH、NaCl溶液和温度变化不敏感,并且不受多种金属离子的影响,表现出优异的稳定性。同时,CDs在较短波长范围(410~470 nm)表现出激发不依赖的发射行为,在较长波长范围(470~510 nm)又表现出弱激发依赖的发射行为。由于其优异的荧光特性、稳定性和低毒性,我们将其应用于人口腔角质形成细胞(Hok)、宫颈癌细胞(Hela)和骨髓间充质干细胞(MC3T3)的体外成像。     

荧光碳点的合成及其在绿麦隆检测中的应用研究

提出了一种以草木炭为碳源,采用一步水热法合成荧光碳点(CDs)的方法,并将所合成的CDs应用于农田水中绿麦隆的检测。探究了草木炭添加量、过氧化氢浓度、反应p H值、水热温度、水热时间等因素对合成CDs的影响。所合成的CDs最大激发和发射波长分别为340 nm和450 nm,发射光谱随激发波长的增大基本无红移。傅立叶红外光谱结果表明:CDs表面存在大量羟基(—OH)和羧基(—COOH)基团。绿麦隆对合成的CDs表现出选择性荧光猝灭,可应用于绿麦隆的检测。该方法对绿麦隆测定的线性范围为0. 15~3. 15mg·L~(-1),相关系数(r~2)为0. 999 3,检出限为0. 05 mg·L~(-1)。方法用于实际样品分析,加标回收率为93. 3%~112%,相对标准偏差(RSD)不大于4. 9%。实验考察了与绿麦隆结构相似的农药和常见阴阳离子对CDs荧光强度的影响,并对绿麦隆对碳点的猝灭机理进行了探讨。     

葡萄糖酸碳量子点的合成及其光学性能的研究

以葡萄糖酸为碳源,采用微波法、热解法和水热溶液法合成了水溶性较好的蓝色荧光碳量子点。用透射电镜(TEM)观察其形貌,荧光光谱(FL)和紫外可见光谱(UV)探究其激发和发射光谱,用时间分辨光谱(TRF)测其荧光寿命值。微波和热解法制备的碳量子点粒径在2.5~7.5 nm之间,激发波长为360 nm,发射波长为450 nm,荧光发射依赖激发波长,有三个荧光寿命,表面状态不均一。水热法制备的碳量子点,粒径在3.0~8.5 nm之间,激发波长为350 nm,发射波长为430 nm,荧光发射不依赖激发波长,只有一个荧光寿命值,表面状态均一。水热法合成的碳量子点荧光量子产率高为6.01%,为进一步研究葡萄糖酸制备碳量子点提供参考。     

碳量子点激发依赖荧光特性的机理、调控及应用

碳量子点（carbon dots,CDs）是一种具有强荧光、荧光波长可调、无光漂白等特性的新型荧光纳米粒子,其制备简单、成本低,而且具有良好的生物相容性和低毒性,在光电器件、生物传感及药物载体等领域展现出广阔的应用前景。其具有的独特激发依赖荧光特性是指随着激发波长的改变,其发射波长将随之改变,所以,通过调节激发波长即可实现CDs的连续全色发射,可为其在多色成像生物领域提供可能性。此外,在长波长激发下,CDs发射波长甚至可以延续到近红外区域,展现出在活体成像领域的应用前景。因此,探索CDs激发依赖荧光特性的机理是非常重要的,这将为实现CDs的激发依赖荧光特性提供理论指导。本文就近年来人们对于CDs激发依赖荧光特性的研究进行了综述,重点概述了CDs激发依赖荧光特性的机理、调控实现CDs激发依赖荧光特性的方法及CDs激发依赖荧光特性的应用。目前,CDs激发依赖荧光特性的机理主要包括：不同表面态的分布、宽的尺寸分布、碳核结构的存在及周围慢的溶剂弛豫;实现CDs激发依赖荧光特性的方法主要有：对表面态的控制、尺寸分布的控制及碳核结构的控制;CDs激发依赖荧光特性的应用主要表现在细胞成像和光电器件。最后,对这一特性研究中尚存在的问题进行了总结并且展望了其发展前景。     

中药碳点的合成及其在生物成像和医学治疗方面的应用

碳点(Carbon dots, CDs)作为一类粒径小于10 nm新型零维光致发光纳米材料,具备可调荧光发射和激发波长,良好的光稳定性、水溶性和生物相容性、低毒性等显著优势,近年来得到了学者们广泛关注。以富含多种活性成分并可发挥多种药效作用的中药(Traditional Chinese Medicines, TCM)为碳源,制备出具有一些特殊功能的中药CDs(TCM-CDs),进而有望发挥出更大的药用价值。本文详细介绍了中药CDs的合成方法及每种合成方法的优缺点,全面综述了中药碳点在生物成像和医学治疗方面的最新研究进展,并对中药CDs研究的重要性及面临的主要问题及挑战和未来的发展方向进行了展望。     

硝酸辅助合成水溶性绿光碳点及其在pH测量与Fe~(3+)检测中的应用（英文）

以柠檬酸、甲酰胺与浓硝酸为原料合成了绿色荧光碳点(CDs),对其物相、形貌及荧光性能进行了表征,并研究了其在离子检测及荧光标记方面的应用。结果表明:所合成的CDs呈现良好的水溶性;当以360～460 nm波长的光激发时,该CDs发出明亮的绿色荧光,并且发射峰的位置不随激发光波长而改变,其量子产率高达44.2%;同时,该绿光CDs对pH敏感,体系pH值在4.5～8.5范围内时,其归一化荧光强度与pH间有较好的线性关系;此外,该绿光CDs对Fe~(3+)有较好的选择性响应,在0～1 000μmol·L~(-1)范围内,体系的荧光淬灭效率(I0/I)与Fe~(3+)浓度有良好的线性关系,检出限为9.8μmol·L~(-1)。     

自组装水热合成碳点-中空氧化硅纳米粒复合材料

利用反相微乳液体系制备出粒径均一的中空氧化硅纳米粒(SHN),以此为基础,再利用水热法通过自组装合成了碳点-中空氧化硅纳米粒复合材料(CD-SHN)。 采用高分辨透射电子显微镜(HRTEM)和场发射扫描电子显微镜(FESEM)对其结构进行了表征,结果显示SHN尺寸为30~40 nm,壳厚约为10 nm,在此基础上合成出具有和海葵类似结构的CD-SHN,尺寸约为1 μm,并且,在水相中具有良好的分散性。 海葵状CD-SHN既具有激发波长依赖的多色荧光发射性能,又具有良好的光稳定性,其最大激发及发射波长分别位于360和435 nm附近,经40 W白炽灯照射60 min,其荧光强度仍可保持97%。 该材料的制备过程条件温和,其原材料生物相容性良好,在生物造影方面具有潜在的优势。     

红枣碳量子点荧光探针的制备及对食品中赖氨酸的检测

以红枣为原料,采用热解法制备了荧光碳量子点(CDs),加入表面活性剂增加了CDs的稳定性。用荧光表征CDs的光学性质,透射电镜观察了CDs的外貌特征。结果表明:荧光激发和发射波长分别为335nm/435nm,荧光量子产率为0. 81,碳点平均直径为3. 1nm,由于赖氨酸对碳量子点的荧光具有增敏作用,可以用于食品中L赖氨酸(L-lys)的分析检测。在p H大于7. 6、25℃条件下,L-lys的加入量与(CDs)荧光强度的增加成正比,其线性回归方程为△F=104. 8C-23. 1(C:μmol·L-1)线性范围为10～0. 4μmol·L-1,r=0. 9959,标准偏差为1. 36,检出限3. 9×10-8mol·L-1,该方法简单、准确、选择性好,适用于食品中L-Lys的检测。     

CdS纳米晶@碳点复合物膜的电致化学发光

采用热解柠檬酸法制备碳点(CDs),并将之与表面无包裹剂的CdS纳米晶(CdS NCs)超声复合制备CdS纳米晶@碳点(CdS NCs@CDs)复合物。研究了复合物膜阴极电致化学发光(ECL),探讨了CDs对CdS纳米晶膜ECL增强的机理。CDs分散性良好、尺寸在1.5~4 nm之间;与粒径约为4 nm的CdS纳米晶按体积比2∶3复合后,在360 nm光激发下复合物具有最强的荧光发射且表现为CDs的荧光。同时,复合物膜产生归属于激发态CdS纳米晶的最强的ECL发射,且ECL发光峰起置电势正移至-1.05 V。复合物膜的ECL发射是pH依赖的,在pH值为6时,复合物膜具有最大的ECL强度,为CdS纳米晶膜ECL强度的19倍。这种ECL增强源于CDs能束缚大量电子产生局域电场从而促进近邻CdS纳米晶激发态的形成与弛豫。     

铽穴状双功能螯合剂的合成及其光学性能

以四甲基-4-H(2,2)-2-甲氧基异邻苯二甲酰胺-四噻唑啉起始原料,合成了一种新型镧系元素穴状有机配体四甲基-胺基-L-赖氨酸-H(2,2)-羟基间苯二甲酰胺,与Tb~(3+)连接制备了双功能螯合剂Tb~(3+)■四甲基-胺基-L-赖氨酸-H(2,2)-羟基间苯二甲酰胺[Tb~(3+)■Lay-BH(2,2)IMA]。荧光性质研究表明:Tb~(3+)■Lay-BH(2,2)IMA的激发波长范围是325～375nm,最大激发波长为357 nm;发射波长范围为525～575nm,最大发射波长为543 nm;特征峰位于487 nm(~5D_4-~7F_5),543 nm(~5D_4-~7F_4),581～586 nm(~5D_4-~7F_3),619 nm(~5D_4-~7F_2),658 nm(~5D_4-~7F_1),斯托克斯位移为186 nm,荧光寿命1 018μs,量子产率24.7%。     

Mass production of highly fluorescent full color carbon dots from the petroleum coke

Heavy oil is treated as an undesirable raw material in traditional refining markets because of its low yield. However, its rich natural aromatic structure and heteroatomic compounds make it possible to be a precursor to large-scale production of carbon materials. Using heavy oil and three SDA products as precursors, we synthesized highly fluorescent multi-color carbon dots (CDs) by hydrothermal method, which can precisely control the photoluminescence wavelength in the range of 350?650 nm. The synthesized carbon dots have the advantages of good long-term stability and stability under extreme pH conditions and low price. Importantly, the carbon dots synthesized with asphalt as the precursor have the highest fluorescence quantum yield. X-ray photoelectron spectroscopy (XPS) is used to elucidate the effects of different precursor on emission color change and photoluminescence quantum yield (PLQY), thus providing a controlled tuning of the system for the functionalization of CDs. And we further used the CDs in macrophage labeling. This pathway gives a reliable and repeatable industry possibility and may boost the applications of CDs into reality.     

碳量子点荧光猝灭法检测药物中的异鼠李素

以L-天冬氨酸为碳源,尿素为氮源,采用微波加热法制备荧光碳量子点(CDs),得到的CDs具有球形结构和单一分散性,平均粒径约为5 nm。红外光谱、X射线光电子能谱、紫外和荧光光谱的表征结果表明,合成的CDs具有较高的荧光稳定性,良好的水溶性和对异鼠李素(ISOR)高的选择性。在优化条件下,ISOR浓度在0.22～180 nmol/L范围内时与CDs荧光猝灭程度(I_(F_0)/I_F)呈良好的线性关系,检出限(LOD)为1.32 nmol/L,回收率为90.8%～107%。结果表明,该CDs可用于ISOR的快速、高效、灵敏检测。     

Applicability Evaluation of Bright Green‐Emitting Carbon Dots in the Solid State for White Light‐Emitting Diodes

Self‐quenching‐resistant and bright green‐emitting carbon dots (CDs) in the solid state were synthesized via a facile hydrothermal method. Their structure, optical properties together with their thermal and photostabilities, as well as their applicability in white LEDs were investigated. The obtained CDs have nearly spherical shape with a size around 4–5 nm. The resulting powder CDs show excitation‐independent emission behavior, and can be excited over a broad range from 300–450 nm. Under optimal excitation at 400 nm, the resultant powder CDs yield bright and broad green emission around 505 nm with full width at half maximum (FWHM) of about 110 nm and under 360 nm excitation with lifetime of 15.8 ns. A potential application of the green‐emitting CDs was evaluated by constructing a white light‐emitting diode lamp. The fabricated white LED lamp emitted bright, warm white light with excellent color rendering properties (a color rendering index of 86.9 and a correlated color temperature of 3863 K).     

β-Cyclodextrin derived full-spectrum fluorescent carbon dots: The formation process investigation and biological applications

Carbon dots (CDs), a new building unit, have been revolutionizing the fields of biomedicine, bioimaging, and optoelectronics with their excellent physical, chemical, and biological properties. However, the difficulty of preparing excitation-dependent full-spectrum fluorescent CDs has seriously hindered their further research in fluorescence emission mechanisms and biomedicine. Here, we report full-spectrum fluorescent CDs that exhibit controlled emission changes from purple (380 nm) to red (613 nm) at room temperature by changing the excitation wavelength, and the excitation dependence was closely related to the regulation of sp² and sp³ hybrid carbon structures by β-cyclodextrin-related groups. In addition, by regulating the content of β-cyclodextrin, the optimal quantum yields of full-spectrum fluorescent CDs were 8.97%, 8.35%, 7.90%, 9.69% and 17.4% at the excitation wavelengths of 340, 350, 390, 410 and 540 nm, respectively. Due to their excellent biocompatibility and color tunability, full-spectrum fluorescent CDs emitted bright and steady purple, blue, green, yellow, and red fluorescence in MCF-7 cells. Moreover, we optimized the imaging conditions of CDs and mitochondrial-specific dyes; and realized the mitochondrial-targeted co-localization imaging of purple, blue and green fluorescence. After that, we also explored the effect of full-spectrum fluorescent CDs in vivo fluorescence imaging through the intratumorally, subcutaneously, and caudal vein, and found that full-spectrum fluorescent CDs had good fluorescence imaging ability in vivo.     

含异丙基及三氟甲基可溶性聚酰胺的合成及性能研究

以含异丙基和三氟甲基结构二胺单体3,3′-二异丙基-4,4′-二胺基苯基-4″-三氟甲基甲苯(PATFT)与萘-1,4-二甲酸、间苯二甲酸和4,4-二苯醚二甲酸3种二酸通过膦酰化反应制备一系列新型可溶性聚酰胺,其相对分子量在3.8×104~9.6×104之间.结果表明,该聚合物具有优异的溶解性能,常温不仅能溶解于N-甲基吡咯烷酮(NMP)、N,N-二甲基乙酰胺(DMAc)、N,N-二甲基甲酰胺(DMF)等高沸点有机溶剂,在加热条件下甚至能较好的溶解在四氢呋喃、氯仿、二氯甲烷等低沸点溶剂中;突出的光学性能,截止波长范围在322~350 nm,80%的透过率波长范围为378~403 nm;良好的热学性能,玻璃化转变温度(Tg)范围在213~220?C,氮气氛围下5%和10%热失重温度范围分别为453~458?C和470~482?C.聚合物薄膜具有优异的机械性能,拉伸强度、杨氏模量、断裂伸长率分别对应为68~97 MPa,1.9~2.9 GPa,14.8%~16.7%.广角X-射线图谱表明聚合物为无定形态结构.     

Eco friendly synthesis of fluorescent carbon dots for the sensitive detection of ferric ions and cell imaging

This study established a ferric ion (Fe³⁺) detection method as a result of the fluorescence quenching effect of Fe³⁺ on carbon dots (CDs). Specifically, we proposed, a green microwave synthesis route towards fluorescent CDs that requires only the brewer’s spent grain as starting materials. Transmission electron microscopy, X-ray diffraction, Fourier-transform infrared spectra and X-ray photoelectron spectroscopy were performed to investigate the CDs characteristic: morphology, size distribution, functional groups, and composition, respectively. The experimental results, which were run under optimal experimental conditions, indicated that the fluorescence intensity and concentration of Fe³⁺ were within the desired linear range (0.3–7 μM). The detection limit of this assay towards Fe³⁺ was 95 nM. The proposed method showed significant selectivity with respect to interfering ions. We evaluated the potential application of this method with tap water, lake water and fetal bovine serum as real samples. Additionally, the CDs could be served as superior bioimaging probes in Hela cells as a result of their excellent optical stability and good biocompatibility. In a word, the present study provides a new idea for CDs derived from the waste of agricultural products for detecting food or environmental contaminants and cell imaging.     

Dual microenvironmental parameter-responsive lysosome-targeting carbon dots for the high contrast discrimination of a broad spectrum of cancer cells

The development of new carbon dots (CDs) for fluorescence-based cancer diagnosis has recently attracted extensive attention. Diagnosis methods based on ligand-receptor fluorescence suffer from the heterogeneity of receptor expression. Changes in the microenvironments of cancer cells provide opportunities for accurate and broad-spectrum cancer diagnosis. The lysosomes in cancer cells have lower polarity and higher viscosity than normal cells. Based on these two key microenvironmental parameters, dual-responsive CDs with inherent lysosome-targeting ability were synthesized via one-step hydrothermal treatment. The CDs exhibit many advantageous properties including facile synthesis, good water solubility, pH-independent emission, excellent photostability, good biocompatibility, and wash-free imaging ability. The CDs were successfully employed in the fluorescence-based discrimination of a broad spectrum of cancer cells from normal cells with high contrast. The CDs are promising candidates for use in the field of cancer diagnosis.     

Regulation of cellular responses to macroporous inorganic films prepared by the inverse-opal method

Regenerative medicine for repairing damaged body tissues has recently become critically important. Cell culture scaffolds are required for the control of cell attachment, proliferation, and differentiation in in vitro cell cultures. A new strategy to control cell adhesion, morphology, and proliferation was developed by culturing mouse osteoblast-like MC3T3-E1 cells on novel cell culture scaffolds fabricated using ordered nanometer-sized pores (100, 300, 500, and 1000 nm). Results of this study indicate that after 72 h of incubation, the number of cells cultured on a silica film with a pore size of 1000 nm was similar to or slightly lower than that cultured on a non-porous control silica film. Films with 100-500 nm pore sizes, however, resulted in the cell growth inhibition. Morphology of the cultured cells revealed increased elongation and the formation of actin stress fibers was virtually absent on macroporous silica films with 100-500 nm pore size. Vinculin molecules expressed in cells cultured on the non-porous silica films showed many clear focal adhesions, whereas focal contacts were insufficiently formed in cells cultured on macroporous films. The influence of hydroxyapatite (HAp) and alumina scaffolds on the behavior of MC3T3-E1 cells was also evaluated. The proliferation rate of MC3T3-E1 cells cultured on HAp films with 1000 nm pore size was increased to approximately 20% above than that obtained of cells cultured on non-porous HAp films. These results demonstrate that the pore size and constituents of films play a role in controlling the morphology and proliferation rate of MC3T3-E1 cells.     

由蚕砂制备的碳量子点在不同激发、pH、金属离子、温度及极性环境下的荧光性质研究

碳量子点作为一种新兴的荧光纳米材料,具有粒径分布均匀、光稳定性好、激发-发射波长可调控、表面可修饰等优良的性质,兼具低毒性、生物相容性好等优点,在分析检测和生物成像等领域展现出广阔的应用前景。而蚕砂是家蚕的干燥粪便,简单易得。利用蚕砂作为碳量子点制备原料,采用微波合成的方法制备得到了一种平均水合粒径为4.86 nm,含氮、硫修饰的碳量子点材料,可作为针对激发波长、pH、金属离子浓度、温度及溶剂极性的变化有着显著响应特性的碳量子点型荧光探针。该探针的荧光最大发射波长随激发波长或pH的增加而红移;荧光强度随温度或pH的降低而增加;随着金属离子,特别是铜离子的加入而逐渐降低,并随着EDTA络离子的加入而逐渐回复。在多种溶剂中该探针均具有较好的溶解度,当换用不同极性的溶剂时,随着溶剂极性的增加荧光发射波长逐渐红移。荧光性质随多重环境参数变化为该碳量子点在未来的生物检测和成像领域提供了广阔的应用前景。