3-巯基丙酸修饰的CdSe/ZnS量子点的合成及测定牛血清白蛋白的研究

以3-巯基丙酸作为修饰剂,在水溶液中合成了稳定的CdSe/ZnS量子点(QDs),透射电镜观察所合成量子点的形貌近似球形,粒径约为25 nm.吸收光谱与荧光光谱的研究表明,CdSe QDs在410 nm处有最大吸收峰,而CdSe/ZnS QDs的最大吸收峰在470 nm处,CdSe/ZnS QDs的荧光强度是CdSe QDs的11倍.考察了缓冲溶液的体积、pH值、反应温度、反应时间对体系荧光的影响.在最佳实验条件下,体系的荧光强度与BSA的浓度呈线性关系,线性响应范围为0.746×10-7～4.48×10-7 mol/L,检出限为3.846×10-10 mol/L.并且CdSe/ZnS QDs荧光强度基本保持稳定,可达两个多月.该方法应用于合成样品的测定,结果满意.     

Forming water-soluble CdSe/ZnS QDs using amphiphilic polymers, stearyl methacrylate/methylacrylate copolymers with different hydrophobic moiety ratios and their optical properties and stability

The amphiphilic stearyl methacrylate/methylacrylic acid copolymers (PSMs) were used as phase transfer reagents to convert CdSe/ZnS core-shell quantum dots (QDs) in chloroform to water-soluble PSMs-coated quantum dots (PSM-QDs). The optical properties and stability of PSM-QDs were influenced by the hydrophobic moiety ratios of PSMs, the PSM/QDs mass/volume ratio and the reaction time. The resulting PSM-QDs on optimum reaction conditions retained 60% of the photoluminescence value of the original CdSe/ZnS QDs in chloroform. The carboxylate-based PSM-QDs survived UV irradiation in air for at least 15 days. Upon UV irradiation, the PSM-QDs became about 2 times brighter than the original CdSe/ZnS QDs in chloroform, and the UV-brightened PL can retain the brightness for at least several months. Experimental results further confirmed the stability of PSM-QDs against strong acid, photochemical and thermal treatments. In addition to good performance of PSM-QDs, the synthesis of PSM and the corresponding water-soluble QDs is relatively simple.     

Chemical and optical properties of CdSe and CdSe/ZnS nanocrystals investigated using high-performance liquid chromatography

We apply a variety of characterization tools, including dynamic light scattering (DLS), transmission electron microscopy (TEM), high-resolution size-exclusion chromatography (HRSEC), and X-ray fluorescence (XRF), to study CdSe and CdSe/ZnS semiconductor nanocrystals of various sizes. We compare the size monodispersity, composition, and optical properties such as absorbance, photoluminescence (PL), and photoluminescence excitation of samples synthesized by high-temperature organometallic decomposition methods to CdSe clusters synthesized in our laboratory using a room-temperature metathesis from ionic precursors in coordinating solvents. DLS revealed considerable aggregation in all the conventionally synthesized samples, while TEM showed significant size and shape polydispersity in the core/shell CdSe/ZnS nanoparticles. We demonstrate how HRSEC can be used to explore size and shape polydispersity in semiconductor nanocrystals by measurement of the spectral homogeneity of the PL and PLE of spectra obtained within cluster elution peaks observed by HRSEC. Using HRSEC, we show that size fractionation by solvent/nonsolvent precipitation is only partially effective in size selection and that discrete size populations are present in each fraction. HRSEC shows that our synthesis yields a single-size, blue-emitting, homogeneous population whose absorbance and PL correspond to those of the smallest-size fraction made by conventional synthesis. This suggests that especially stable discrete sizes are favored in both synthetic methods.     

(CdSe/ZnS QDs)-ionic liquid-based headspace single drop microextraction for the fluorimetric determination of trimethylamine in fish

Here, we propose the use of ionic liquid-modified QDs for the combination of ionic liquid-based headspace single drop microextraction technique (IL-HS-SDME) and QD-based fluorimetric detection. In that way, we exploit the advantages of ILs as extractant solvent and the use of QDs as fluorescence detection probe. After in situ generation of volatile trimethylamine (TMA) from fish samples, the analyte was extracted and preconcentrated directly onto a (QD)IL microdrop by HS-SDME. Then, TMA was quantified through the enhancing effect produced on the initial fluorescence of the (QD)IL dispersion. The working conditions for the (QD)IL-HS-SDME procedure were: 20 μL microdrop of (QD)IL exposed for 2 min to the headspace of a 5 mL aqueous sample (0.2 g of fish in 10 M NaOH) placed in a 10 mL vial with stirring and thermostatted at 50-60 °C. For the detection, the microdrop was transferred to a microcuvette with 300 μL of acetonitrile and the fluorescence was recorded (λ(em) = 570 nm, λ(exc) = 400 nm). Under the selected conditions, the analytical response was linear over the range from 0.05 to 0.25 mg L(-1) (R(2) = 0.997) with a detection limit of 0.014 mg L(-1) (0.35 μg TMA per gram of fish) and the relative standard deviation was 3.5% (n = 5). The proposed method was applied to the determination of TMA in hake fish samples with satisfactory results.     

Self-assembly of a mesoporous ZnS/mediating interface/CdS heterostructure with enhanced visible-light hydrogen-production activity and excellent stability

We designed and successfully fabricated a ZnS/CdS 3D mesoporous heterostructure with a mediating Zn_1–xCd_xS interface that serves as a charge carrier transport channel for the first time. The H₂-production rate and the stability of the heterostructure involving two sulfides were dramatically and simultaneously improved by the careful modification of the interface state via a simple post-annealing method. The sample prepared with the optimal parameters exhibited an excellent H₂-production rate of 106.5 mmol h^–1 g^–1 under visible light, which was 152 and 966 times higher than CdS prepared using ethylenediamine and deionized water as the solvent, respectively. This excellent H₂-production rate corresponded to the highest value among the CdS-based photocatalysts. Moreover, this heterostructure showed excellent photocatalytic stability over 60 h.     

Enhancing the device performance of a blue light‐emitting copolymer using CdSe/ZnS quantum dots

An alternating triarylamine‐functionalized fluorene‐based copolymer synthesized using a Suzuki–Miyaura cross‐coupling procedure is used as blue emitting layer in polymer light‐emitting diodes (PLEDs). Subsequently, the effects of CdSe/ZnS quantum dots (QDs) on the optoelectronic properties of the copolymer are investigated. Therefore, CdSe/ZnS QDs are embedded into the copolymer matrix and hybrid PLEDs are fabricated. The devices comprised of CdSe/ZnS QDs reveal enhanced performances, yielding about 3.4 times more luminous efficiency than that of the device without QDs. Further enhancement is achieved by using electron transport layer; the luminous efficiency rose from 0.065 to 1.740 cd A^?1 for the hybrid PLEDs, corresponding to a superb 27‐fold intensification of the efficiency. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 147–156     

Extending N-heterocyclic carbene ligands into the third dimension: a new type of hybrid phosphazane/NHC system

A simple, “click” synthetic approach to a new type of hybrid phosph(III)azane/NHC system is described. The presence of the phosphazane P₂N₂ ring unit, with P atoms flanking the NCN fragment and with this ring perpendicular to the binding site of the NHC, provides unique opportunities for modifying the electronic and steric character of these carbenes.     

A rapid and universal bacteria-counting approach using CdSe/ZnS/SiO2 composite nanoparticles as fluorescence probe

In this paper, a rapid, simple, and sensitive method was described for detection of the total bacterial count using SiO₂-coated CdSe/ZnS quantum dots (QDs) as a fluorescence marker that covalently coupled with bacteria using glutaraldehyde as the crosslinker. Highly luminescent CdSe/ZnS were prepared by applying cadmium oxide and zinc stearate as precursors instead of pyrophoric organometallic precursors. A reverse-microemulsion technique was used to synthesize CdSe/ZnS/SiO₂ composite nanoparticles with a SiO₂ surface coating. Our results showed that CdSe/ZnS/SiO₂ composite nanoparticles prepared with this method possessed highly luminescent, biologically functional, and monodispersive characteristics, and could successfully be covalently conjugated with the bacteria. As a demonstration, it was found that the method had higher sensitivity and could count bacteria in 3 × 10² CFU/mL, lower than the conventional plate counting and organic dye-based method. A linear relationship of the fluorescence peak intensity (Y) and the total bacterial count (X) was established in the range of 3 × 10²–10⁷ CFU/mL using the equation Y = 374.82X − 938.27 (R = 0.99574). The results of the determination for the total count of bacteria in seven real samples were identical with the conventional plate count method, and the standard deviation was satisfactory.     

A pH-activatable and aniline-substituted photosensitizer for near-infrared cancer theranostics

This work reports a newly designed pH-activatable and aniline-substituted aza-boron-dipyrromethene as a trifunctional photosensitizer to achieve highly selective tumor imaging, efficient photodynamic therapy (PDT) and therapeutic self-monitoring through encapsulation in a cRGD-functionalized nanomicelle. The diethylaminophenyl is introduced in to the structure for pH-activatable near-infrared fluorescence and singlet oxygen (¹O₂) generation, and bromophenyl is imported to increase the ¹O₂ generation efficiency upon pH activation by virtue of its heavy atom effect. After encapsulation, the nanoprobe can target α_vβ₃ integrin-rich tumor cells via cRGD and is activated by physiologically acidic pH for cancer discrimination and PDT. The fascinating advantage of the nanoprobe is near-infrared implementation beyond 800 nm, which significantly improves the imaging sensitivity and increases the penetration depth of the PDT. By monitoring the fluorescence decrease in the tumor region after PDT, the therapeutic efficacy is demonstrated in situ and in real time, which provides a valuable and convenient self-feedback function for PDT efficacy tracking. Therefore, this rationally designed and carefully engineered nanoprobe offers a new paradigm for precise tumor theranostics and may provide novel opportunities for future clinical cancer treatment.     

Finely controlled size-selective precipitation and separation of CdSe/ZnS semiconductor nanocrystals using CO2-gas-expanded liquids

A technique was developed to size-selectively separate polydisperse dispersions of CdSe/ZnS nanocrystals into distinct color fractions using only the tunable solvent properties of CO2-expanded hexane. This size-selective precipitation of semiconductor nanoparticles is achieved by finely tuning the solvent strength of the CO2/hexane medium by simply adjusting the applied CO2 pressure. These subtle changes affect the balance between osmotic repulsive and van der Waals attractive forces, thereby allowing fractionation of the nanocrystals into multiple narrow size populations.     

Characterizing mixed phosphonic acid ligand capping on CdSe/ZnS quantum dots using ligand exchange and NMR spectroscopy

The ligand capping of phosphonic acid functionalized CdSe/ZnS core–shell quantum dots (QDs) was investigated with a combination of solution and solid‐state ³¹P nuclear magnetic resonance (NMR) spectroscopy. Two phosphonic acid ligands were used in the synthesis of the QDs, tetradecylphosphonic acid and ethylphosphonic acid. Both alkyl phosphonic acids showed broad liquid and solid‐state ³¹P NMR resonances for the bound ligands, indicative of heterogeneous binding to the QD surface. In order to quantify the two ligand populations on the surface, ligand exchange facilitated by phenylphosphonic acid resulted in the displacement of the ethylphosphonic acid and tetradecylphosphonic acid and allowed for quantification of the free ligands using ³¹P liquid‐state NMR. After washing away the free ligand, two broad resonances were observed in the liquids' ³¹P NMR corresponding to the alkyl and aromatic phosphonic acids. The washed samples were analyzed via solid‐state ³¹P NMR, which confirmed the ligand populations on the surface following the ligand exchange process. Copyright © 2015 John Wiley & Sons, Ltd.     

In situ activation and monitoring of the evolution of the intracellular caspase family

The evolution of the intracellular caspase family is crucial in cell apoptosis. To evaluate this process, a universal platform of in situ activation and monitoring of the evolution of intracellular caspase is designed. Using well-known gold nanostructure as a model of both nanocarrier and matter inducing the cell apoptosis for photothermal therapy, a nanoprobe is prepared by assembly of two kinds of dye-labelled peptides specific to upstream caspase-9 and downstream caspase-3 as the signal switch, and folic acid as a targeting moiety. The energy transfer from dyes to the gold nanocarrier at two surface plasmon resonance absorption wavelengths leads to their fluorescence quenching. Upon endocytosis of the nanoprobe to perform the therapy against cancer cells, the peptides are successively cleaved by intracellular caspase activation with the evolution from upstream to downstream, which lights up the fluorescence of the dyes sequentially, and can be used to quantify both caspase-9 and caspase-3 activities in cancer cells and to monitor their evolution in living mice. The recovered fluorescence could also be used to assess therapeutic efficiency. This work provides a novel powerful tool for studying the evolution of the intracellular caspase family and elucidating the biological roles of caspases in cancer cell apoptosis.     

Iridium-complex modified CdSe/ZnS quantum dots; a conceptual design for bi-functionality toward imaging and photosensitization

We report the design and synthesis of Ir-complex functionalized CdSe/ZnS quantum dots (QDs), in which the QD plays a key role in imaging, while the Ir-complex acts as a sensitizer to produce singlet oxygen; this conceptual design presents a novel scheme in both bio-imaging and photodynamic therapy.     

Laser Assisted Catalytic Growth of ZnS/CdSe Core‐Shell and Wire‐Coil Nanowire Heterostructures

ZnS/CdSe core‐shell and wire‐coil nanowire heterostructures have been synthesized by chemical vapor deposition assisted with pulsed laser ablation. Measurements from high‐resolution transmission electron microscopy and selected area electron diffraction have revealed that both ZnS/CdSe core‐shell and wire‐coil nanowires are of single‐crystalline hexagonal wurtzite structures and grow along the [0001] direction. While the lattice parameters of ZnS and CdSe in the core‐shell nanowires are nearly equal to those of bulk ZnS and CdSe, change of the lattice parameters in the CdSe‐coil is attributed to the doping of Zn into CdSe, resulting in the relaxation of compressive strain at the interface between CdSe‐coil and ZnS‐wire. Composition variation across the interfacial regions in the ZnS/CdSe nanowire heterostructures ranges only 10–15 nm despite the pronounced lattice mismatch between ZnS and CdSe by ?11%. Growth mechanisms of the ZnS/CdSe nanowire heterostructures are discussed.     

Super Sensitization: Grand Charge (Hole/Electron) Separation in ATC Dye Sensitized CdSe,CdSe/ZnS Type‐I,and CdSe/CdTe Type‐II Core–Shell Quantum Dots

Ultrafast charge‐transfer dynamics has been demonstrated in CdSe quantum dots (QD), CdSe/ZnS type‐I core–shell, and CdSe/CdTe type‐II core–shell nanocrystals after sensitizing the QD materials by aurin tricarboxylic acid (ATC), in which CdSe QD and ATC form a charge‐transfer complex. Energy level diagrams suggest that the conduction and valence band of CdSe lies below the LUMO and the HOMO level of ATC, respectively, thus signifying that the photoexcited hole in CdSe can be transferred to ATC and that photoexcited ATC can inject electrons into CdSe QD, which has been confirmed by steady state and time‐resolved luminescence studies and also by femtosecond time‐resolved absorption measurements. The effect of shell materials (for both type‐I and type‐II) on charge‐transfer processes has been demonstrated. Electron injection in all the systems were measured to be <150 fs. However, the hole transfer time varied from 900 fs to 6 ps depending on the type of materials. The hole‐transfer process was found to be most efficient in CdSe QD. On the other hand, it has been found to be facilitated in CdSe/CdTe type‐II and retarded in CdSe/ZnS type‐I core–shell materials. Interestingly, electron injection from photoexcited ATC to both CdSe/CdTe type‐II and CdSe/ZnS type‐I core–shell has been found to be more efficient as compared to pure CdSe QD. Our observation suggests the potential of quantum dot core–shell super sensitizers for developing more efficient quantum dot solar cells.     

Concentration-dependent rhombitrihexagonal tiling patterns at the liquid/solid interface

We report STM investigations on a linear oligophenyleneethylene (OPE)-based self-assembling Pd(ii) complex 1 that forms highly-ordered concentration dependent patterns on HOPG. At high concentration, 2D lamellar structures are observed whereas the dilution of the system below a critical concentration leads to the formation of visually attractive rhombitrihexagonal Archimedean tiling arrangements featuring three different kinds of polygons: triangles, hexagons and rhombi. The key participation of the Cl ligands attached to the Pd(ii) centre in multiple C–H···Cl interactions was demonstrated by comparing the patterns of 1 with those of an analogous non-metallic system 2.     

G-quadruplex DNA and ligand interaction in living cells using NMR spectroscopy

Gathering structural information from biologically relevant molecules inside living cells has always been a challenging task. In this work, we have used multidimensional NMR spectroscopy to probe DNA G-quadruplexes inside living Xenopus laevis oocytes. Some of these structures can be found in key regions of chromosomes. G-quadruplexes are considered potential anticancer therapeutic targets and several lines of evidence indirectly point out roles in key biological processes, such as cell proliferation, genomic instability or replication initiation. However, direct demonstrations of the existence of G-quadruplexes in vivo are scarce. Using SOFAST-HMQC type spectra, we probed a tetramolecular G-quadruplex model made of d(TG₄T)₄ inside living Xenopus laevis oocytes. Our observations lead us to conclude that the quadruplex structure is formed within the cell and that the intracellular environment preferentially selects a conformation that most resembles the one found in vitro under KCl conditions. We also show for the first time that specific ligands targeting G-quadruplexes can be studied using high resolution NMR directly inside living cells, opening new avenues to study ligand binding discrimination under physiologically relevant conditions with atomic detail.     

A supramolecular nanovehicle toward systematic,targeted cancer and tumor therapy

A supramolecular nanovehicle (denoted as SNV) was fabricated by encapsulating zinc phthalocyanine (ZnPc) and doxorubicin (DOX) into a copolymer (PVP-b-PAA-g-FA), so as to achieve systematic and synergistic chemotherapy-photodynamic therapy (PDT), targeted tumor imaging and therapy. The sophisticated copolymer designed in this work can load the PDT photosensitizer (ZnPc) and chemotherapy drug (DOX) simultaneously, which exhibits an excellent performance in chemotherapy-PDT targeted cancer and tumor therapy for both in vitro studies performed with HepG2 cells and in vivo tests with mice. This work provides a new drug formulation with a chemotherapy-PDT synergistic effect by virtue of the supramolecular material design, which possesses the advantages of an ultra-low drug dosage and highly-efficient in vivo targeted tumor imaging/therapy.