Ran Cui

Ultrasmall Near-Infrared Ag2Se Quantum Dots with Tunable Fluorescence for in Vivo Imaging

A strategy is presented that involes coupling Na(2)SeO(3) reduction with the binding of silver ions and alanine in a quasi-biosystem to obtain ultrasmall, near-infrared Ag(2)Se quantum dots (QDs) with tunable fluorescence at 90 °C in aqueous solution. This strategy avoids high temperatures, high pressures, and organic solvents so that water-dispersible sub-3 nm Ag(2)Se QDs can be directly obtained. The photoluminescence of the Ag(2)Se QDs was size-dependent over a wavelength range from 700 to 820 nm, corresponding to sizes from 1.5 ± 0.4 to 2.4 ± 0.5 nm, with good monodispersity. The Ag(2)Se QDs are less cytotoxic than other nanomaterials used for similar applications. Furthermore, the NIR fluorescence of the Ag(2)Se QDs could penetrate through the abdominal cavity of a living nude mouse and could be detected on its back side, demonstrating the potential applications of these less toxic NIR Ag(2)Se QDs in bioimaging.

Near-Infrared Electrogenerated Chemiluminescence of Ultrasmall Ag2Se Quantum Dots for the Detection of Dopamine

The near-infrared (NIR) electrogenerated chemiluminescence (ECL) of water-dispersed Ag(2)Se quantum dots (QDs) with ultrasmall size was presented for the first time. The Ag(2)Se QDs have shown a strong and efficient cathodic ECL signal with K(2)S(2)O(8) as coreactant on the glassy carbon electrode (GCE) in aqueous solution. The ECL spectrum exhibited a peak at 695 nm, consistent with the peak in photoluminescence (PL) spectrum of the Ag(2)Se QDs solution, indicating that the Ag(2)Se QDs had no deep surface traps. Dopamine was chosen as a model analyte to study the potential of Ag(2)Se QDs in the ECL analytical application. The ECL signal of Ag(2)Se QDs can also be used for the detection of the dopamine concentration in the practical drug (dopamine hydrochloride injection) containing several adjuvants such as edetate disodium, sodium bisulfite, sodium chloride and so on. The Ag(2)Se QDs could be a promising candidate emitter of ECL biosensors in the future due to their fantastic features, such as ultrasmall size, low toxicity, good water solubility, and near infrared (NIR) fluorescent emission.

Uniform fluorescent nanobioprobes for pathogen detection.

Manipulating biochemical reactions in living cells to synthesize nanomaterials is an attractive strategy to realize their synthesis that cannot take place in nature. Yeast cells have been skillfully utilized to produce desired nanoparticles through spatiotemporal coupling of intracellular nonrelated biochemical reaction pathways for formation of fluorescent CdSe quantum dots. Here, we have successfully transformed Staphylococcus aureus cells into cellular beacons (fluorescing cells), all of which are highly fluorescent and photostable with perfect uniformity. Importantly, on the basis of such cells, we efficiently fabricated fluorescent nanobioprobes by a specific interaction between the protein A expressed on the S. aureus surface and the Fc fragment domain of antibodies, avoiding the use of other common methods for cell surface modifications, such as molecular covalent connection or more difficult genetic and metabolic engineering. Coupled with immunomagnetic beads, the resulting fluorescent-biotargeting bifunctional cells, i.e., biotargeting cellular beacons, can be employed as nanobioprobes for detection of viruses, bacteria, and tumor cells. With this method, H9N2 AIV can be detected specifically with a limit of 8.94 ng/mL (based on protein content). Furthermore, diverse probes for detection of different pathogens or for other biomedical applications can be easily obtained by simply changing the antibody conjugated to the cell surface.

Ionic liquids improved reversed-phase HPLC on-line coupled with ICP-MS for selenium speciation

Room-temperature ionic liquids (RTILs) improved reversed-phase high performance liquid chromatography (RP-HPLC) on-line combined with inductively coupled plasma mass spectrometry (ICP-MS) was developed for selenium speciation. The different parameters affecting the retention behaviors of six target selenium species especially the effect of RTILs as mobile phase additives have been studied, it was found that the mobile phase consisting of 0.4% (v/v) 1-butyl-3-methylimidazolium chloride ([BMIM]Cl), 0.4% (v/v) 1-butyl-2,3-dimethylimidazolium tetrafluroborate ([BMMIM]BF(4)) and 99.2% (v/v) water has effectively improved the peak profile and six target selenium species including Na(2)SeO(3) (Se(IV)), Na(2)SeO(4) (Se(VI)), L-selenocystine (SeCys(2)), D,L-selenomethionine (SeMet), Se-methylseleno-l-cysteine (MeSeCys), seleno-D,L-ethionine (SeEt) were separated in 8 min. In order to validate the accuracy of the method, a Certified Reference Material of SELM-1 yeast sample was analyzed and the results obtained were in good agreement with the certified values. The developed method was also successfully applied to the speciation of selenium in Se-enriched yeasts and clover. For fresh Se-enriched yeast cells, it was found that the spiked SeCys(2) in living yeast cells could be transformed into SeMet. Compared with other ion-pair RP-HPLC-ICP-MS approaches for selenium speciation, the proposed method possessed the advantages including ability to regulate the retention time of the target selenium species by selecting the suitable RTILs and their concentration, simplicity, rapidness and low injection volume, thus providing wide potential applications for elemental speciation in biological systems.

Ultrasmall Magnetically Engineered Ag2Se Quantum Dots for Instant Efficient Labeling and Whole-Body High-Resolution Multimodal Real-Time Tracking of Cell-Derived Microvesicles.

Cell-derived microvesicles (MVs) are natural carriers that can transport biological molecules between cells, which are expected to be promising delivery vehicles for therapeutic purposes. Strategies to label MVs are very important for investigation and application of MVs. Herein, ultrasmall Mn-magnetofunctionalized Ag2Se quantum dots (Ag2Se@Mn QDs) integrated with excellent near-infrared (NIR) fluorescence and magnetic resonance (MR) imaging capabilities have been developed for instant efficient labeling of MVs for their in vivo high-resolution dual-mode tracking. The Ag2Se@Mn QDs were fabricated by controlling the reaction of Mn(2+) with the Ag2Se nanocrystals having been pretreated in 80 °C NaOH solution, with an ultrasmall size of ca. 1.8 nm, water dispersibility, high NIR fluorescence quantum yield of 13.2%, and high longitudinal relaxivity of 12.87 mM(-1) s(-1) (almost four times that of the commercial contrast agent Gd-DTPA). The ultrasmall size of the Ag2Se@Mn QDs enables them to be directly and efficiently loaded into MVs by electroporation, instantly and reliably conferring both NIR fluorescence and MR traceability on MVs. Our method for labeling MVs of different origins is universal and free of unfavorable influence on intrinsic behaviors of MVs. The complementary imaging capabilities of the Ag2Se@Mn QDs have made the long-term noninvasive whole-body high-resolution dual-mode tracking of MVs in vivo realized, by which the dynamic biodistribution of MVs has been revealed in a real-time and in situ quantitative manner. This work not only opens a new window for labeling with QDs, but also facilitates greatly the investigation and application of MVs.

Mechanism-Oriented Controllability of Intracellular Quantum Dots Formation: The Role of Glutathione Metabolic Pathway

Microbial cells have shown a great potential to biosynthesize inorganic nanoparticles within their orderly regulated intracellular environment. However, very little is known about the mechanism of nanoparticle biosynthesis. Therefore, it is difficult to control intracellular synthesis through the manipulation of biological processes. Here, we present a mechanism-oriented strategy for controlling the biosynthesis of fluorescent CdSe quantum dots (QDs) by means of metabolic engineering in yeast cells. Using genetic techniques, we demonstrated that the glutathione metabolic pathway controls the intracellular CdSe QD formation. Inspired from this mechanism, the controllability of CdSe QD yield was realized through engineering the glutathione metabolism in genetically modified yeast cells. The yeast cells were homogeneously transformed into more efficient cell-factories at the single-cell level, providing a specific way to direct the cellular metabolism toward CdSe QD formation. This work could provide the foundation for the future development of nanomaterial biosynthesis.

Dual-Responsive Gold Nanoparticles for Colorimetric Recognition and Testing of Carbohydrates with a Dispersion-Dominated Chromogenic Process.

A dispersion-dominated colorimetric approach for the recognition of carbohydrates based on biomolecule-responsive AuNPs is presented. Taking advantage of the unique dual-responsiveness of smart copolymers, the aggregation and dispersion of AuNPs can be modulated by both temperature and different kinds of carbohydrates, giving rise to a novel chromogenic mechanism for the recognition and testing of carbohydrates in aqueous media.

Synthesis of sub-5 nm Au–Ag alloy nanoparticles using bio-reducing agent in aqueous solution

Bio-reducing agent NADPH with relatively weak reducibility and favourable structure simultaneously reduced Au and Ag ions into sub-5 nm alloy nanoparticles in aqueous solution at room temperature.

Visualized investigation of yeast transformation induced with Li+ and polyethylene glycol

The effects of Li(+) and polyethylene glycol (PEG) on the genetic transformation of Saccharomyces cerevisiae were investigated by using fluorescence microscopy (FM) to visualize the binding of plasmid DNA labeled with YOYO-1 to the surface of yeast cells, scanning electron microscopy (SEM) and atomic force microscopy (AFM) to image the change in surface topography of yeast cells, coupled with transformation frequency experiments. The results showed that under the same conditions, the transformation frequencies of yeast protoplasts were much higher than those of intact yeast cells. PEG was absolutely required for the binding of DNA to the surface of intact yeast cells or yeast protoplasts, and had no effect on the surface topography of intact yeast cells or yeast protoplasts. In the presence of PEG, Li(+) could greatly enhance the binding of plasmid DNA to the surface of intact yeast cells, increase their transformation frequency, and affect their surface topography. On the other hand, no effect on the DNA binding to the surface of protoplasts and no increase in the number of transformants and no surface topography changes were found upon the treatment with Li(+) to protoplasts. In the present work, the effects of Li(+) and PEG on yeast genetic transformation were directly visualized, rather than those deduced from the results of transformation frequencies. These results indicate that cell wall might be a barrier for the uptake of plasmid DNA. Li(+) could increase the permeability of yeast cell wall, then increase the exposed sites of DNA binding on intact yeast cells. The main role of PEG was to induce DNA binding to cell surface.

Controllable synthesis of PbSe nanocubes in aqueous phase using a quasi-biosystem

By coupling two biochemical processes of reduction of Na2SeO3 with detoxification of Pb2+ in a quasi-biosystem, water-dispersed PbSe nanocubes with good monodispersity were controllably synthesized with different sizes at low temperature (90 °C) under mild conditions. The crystallization mechanism and the nature of bio-molecules influenced on the crystallization process were investigated.