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Inductively coupled plasma-mass spectrometry (ICP-MS) with elemental labeling is a promising strategy for multiplex microRNA (miRNA) analysis. However, it is still challenging for specific analysis of multiple miRNAs with high homology, and the development of multiplex assays is always limited by the complexity of the sequence design. Herein, a simple and direct ICP-MS-based assay was developed for the simultaneous detection of three miRNAs by combining the lanthanide labeling strategy with entropy-driven catalytic (EDC) amplification. Owing to the specificity of EDC for nucleic acid recognition, it is able to differentiate miRNAs with single-base mutation in each EDC circuit. A universal biotin-labeled DNA strand was designed to hybridize with the DNA substrates for three EDC circuits, targeting miRNA-21, miRNA-155, and miRNA-10b, respectively. All the substrates were loaded on the surface of streptavidin magnetic beads. In the presence of target miRNA, the EDC reaction was initiated, and EDC substrates were dissociated, continuously releasing reporter strands that were labeled with lanthanides (Tb/Ho/Lu). After magnetic separation, the supernatant containing the released reporter strands was introduced into an ICP-MS system for simultaneous detection of

A highly sensitive and simple method based on rolling circle amplification (RCA) and single particle inductively coupled plasma mass spectrometry (spICP-MS) was proposed for the homogeneous detection of hepatitis B virus (HBV) deoxyribonucleic acid (DNA). In the presence of target DNA, long ssDNA possessing a large number of repeating sequence units was generated by RCA. DNA-labeled AuNP probes assembled into long chains based on complementary base pairing, further aggregating into large particles. Small Au NPs hardly produced pulse signals in spICP-MS; obvious pulse signals appeared in spICP-MS after the agglomeration of Au NPs caused by the addition of RCA products and spermidine. On the basis of this, the homogeneous detection of target DNA was realized by spICP-MS with high sensitivity. Under optimal conditions, the proposed method exhibited a good linear relationship between the frequency of the pulse signal of Au in spICP-MS and the concentration of target HBV DNA in the range of 10-2000 fmol L

High-throughput single-cell analysis is critical to elucidate the cell heterogeneity. Recently, droplet microchips using oil/gas phases to generate single-cell encapsulated droplets have been combined with inductively coupled plasma-mass spectrometry (ICP-MS) for determination of trace elements in single cells with a throughput of dozens of cells per min. To improve the sample throughput and avoid the oil phase introduced into ICP-MS, herein, a negative magnetophoresis focusing microchip was established and online-coupled to ICP-MS for single-cell analysis. MCF-7 cells in the paramagnetic salt solution were introduced into the designed focusing microchannel, in which they were focused into a single stream under both the magnetic repulsion force and inertial lift force, and then were introduced into ICP-MS for online single-cell analysis. The important parameters including the chip design, the concentration of the paramagnetic salt solution, flow rate, cell density, and dwell time were optimized. Under the optimal conditions, a high sample throughput of 1390 cells min

This work reported a simple and ultrasensitive label-free method for the detection of hepatitis B virus (HBV) DNA by combining hyperbranched rolling circle amplification (HRCA) with dual-mode detection by inductively coupled plasma mass spectrometry (ICP-MS) and fluorescence using ruthenium complex [Ru(bpy)2dppz]2+ (bpy = 2,2'-bipyridine, dppz = dipyrido [3,2-a:2',3'-c] phenazine) as a dual functional probe. An HBV DNA-initiated HRCA system was designed to realize the highly efficient amplification of HBV DNA with the generation of a mass of dsDNA. Also, the [Ru(bpy)2dppz]2+ probe was then added to intercalate into the dsDNA products, resulting in strong fluorescence recovery of the probe for fluorescence detection. Meanwhile, using a biotin-modified primer in HRCA, the dsDNA-[Ru(bpy)2dppz]2+ complexes could be captured by the avidin-coated 96-well plates, and the captured [Ru(bpy)2dppz]2+ probe was later desorbed by acid for ICP-MS detection. The linear range of the proposed method was 3.5-200 amol L-1 and the limit of detection (LOD) was 1 amol L-1 for ICP-MS detection, while the linear range was 20-500 amol L-1 and the LOD was 9.6 amol L-1 for fluorescence detection. The developed method was applied to human serum sample analysis, and the analytical results coincided very well with those obtained by the real-time polymerase chain reaction (PCR) method. The developed dual-mode label-free detection method was ultrasensitive, simple, and accurate, showing great potential for therapeutic monitoring of HBV infection.

It has been well established that the early-stage interactions of nanoparticles with cells are governed by the extracellular protein corona. However, after entering into the cells, the evolving protein corona is the key to subsequent processing of nanoparticles by cells. To identify the protein corona around intracellular nanoparticles, it is essential to maintain its original compositions during cell treatment. Herein, we develop a paraformaldehyde (PFA) cross-linking strategy to stabilize corona compositions when extracting protein coronas from cells, providing original information on protein coronas around intercellular gold nanoparticles (AuNPs). The stability of the protein corona after PFA cross-linking was carefully investigated with several characterization methods, and the results demonstrate that PFA cross-linking successfully prevents the dissociation and exchange of corona proteins. Then the recovered intracellular protein corona around AuNPs from living HepG2 cells with a PFA cross-linking strategy was subjected to nanoHPLC-MS/MS for proteomic analysis. It was found that the compositions of intracellular protein coronas are dominated by cell-derived proteins and undergo significant variation of protein species and amounts over time during internalization. Time-resolved analysis provides relevant proteins involved in nanoparticle cellular uptake and transportation, indicating that AuNPs are endocytosed mainly by a clathrin-mediated uptake mechanism and directed into an endolysosomal pathway toward their final destination. Such proteomic-based results are verified by pharmacological inhibition and TEM imaging analysis. This work provides a universal strategy to study compositions of protein corona around intercellular nanoparticles and could be a footstone to link the formation of protein corona around nanoparticles to their biological function in cells.

Quantification of multiple disease-related microRNAs (miRNAs) is of great significance for clinical diagnosis. Based on the simultaneous multiple element detection ability of inductively coupled plasma-mass spectrometry (ICP-MS) and good specificity of multicomponent nucleic acid enzymes (MNAzymes), a novel and simple method based on the MNAzyme amplification strategy and lanthanide labeling coupled with ICP-MS detection was proposed for the sensitive and simultaneous detection of three miRNAs (miRNA-21, miRNA-155, and miRNA-10b). Specifically, a probe consisting of streptavidin-modified magnetic beads (SA-MBs) and three DNA substrates labeled with lanthanide tags (159Tb/165Ho/175Lu) was constructed. In the presence of target miRNAs, three pairs of MNAzymes were assembled where each pair was hybridized with the corresponding miRNA, and then the substrates on the SA-MBs were cleaved by the activated MNAzymes, continuously releasing the fragment with lanthanide tags. The released lanthanide tags in the supernatant were collected after magnetic separation and analyzed by ICP-MS, realizing the simultaneous quantification of multiple miRNAs. The correlation of the lanthanide tag signal with the miRNA concentration fitted well in a linear model in the range of 50-1000 pmol L-1 (miRNA-21) and 50-2000 pmol L-1 (miRNA-155 and miRNA-10b). The limits of detection for three miRNAs were 11-20 pmol L-1, with the relative standard deviations of 2.2-2.7%. The recoveries of target miRNAs in the human serum and HepG-2 cells were in the range of 87.2-111% and 93.3-111%, respectively. Overall, the method is ideal for the simultaneous quantification of multiple miRNAs with advantages of low spectral interference, high sensitivity, good selectivity, and strong resistance to the complex matrix.

Because of the growing interest in bis-MPA dendrimers and hyperbranched polymers, a linear, polyester equivalent is of great importance in understanding how this commercially viable family of branc...

Therapeutic drug monitoring is central to optimize therapeutic efficacy and minimize adverse events; however, the pharmacokinetics and pharmacodynamics of most drugs differ greatly among individuals. Evaluation of the therapeutic response is in urgent need to help clinician predict the clinical dose of drug. Herein, we described an analytical assay using gold nanocluster (AuNC)-decorated metal-organic frameworks (MOFs) for targeted drug delivery and monitoring pharmacodynamics, giving attractive options for studying individualized therapy. The camptothecin (Cam) anticancer drug was caged in the NH

A novel near-infrared-responsive (NIR-responsive) photothermal therapy (PTT) agent based on perylene-diimide-encapsulated (PDI-encapsulated) PEGylated silica nanocapsules (SNCs) is developed. Dicyclohexylamino-PDI (DCAPDI) with electron-donating cyclohexylamino substitutes at bay positions aggregates into J-aggregation in the core of SNCs, and their electronic coupling interactions are strengthened because of the spatial confinement of SNCs, resulting in strong NIR absorption but negligible fluorescence emission which is crucial for NIR-responsive PTT. Based on our knowledge, this is the first example of generating NIR photothermal conversion by means of molecular aggregation derived from spatial confinement. Unprecedented photostability is achieved with the DCAPDI-encapsulated SNCs in response to more than 60 runs of cyclic NIR exposure with each run exposed to the 808 nm, 1 W cm

N-doped magnetic porous carbon (N-MPC) is an emerging adsorbent for water pollution control. However, high cost and multisteps procedure make the direct fabrication of N-MPCs difficult until now. Herein, highly dispersed N-MPCs were synthesized by a facial one-pot solid-state pyrolysis strategy. Heating the mixture of ZnO, Co(OH)2, and 2-methylimidazole (HmIm), Zn/Co bimetallic ZIFs formed at the initial stages, being the primary self-template to produce N-MPCs during subsequent high-temperature treatment. By altering the pyrolysis temperature and the molar ratio of ZnO/Co(OH)2 in the precursor, the magnetism, nitrogen content, and surface areas of N-MPCs can be easily controlled. Due to its high special surface areas and the decoration of abundant nitrogen functional groups (pyrrole-N and pyridinic-N), the optimized N-MPC-700-7/3 exhibited a superior adsorption performance for Hg2+ uptake (489 mg g–1). Moreover, the N-MPCs exhibited fast dynamics in adsorption (K2 = 0.47 g mg–1 min–1) and good chemical s...

Magnetic metal–organic framework composites (MFCs) were prepared in water at room temperature through a simple, low-cost and green strategy only by employing organic salts as anionic linker sources. Amino-functionalized MFCs (MFC-N) with different amino group contents were successfully prepared by varying the ratio of disodium of 2-aminoterephthalic (NH2-Na2BDC)/terephthalic acid (Na2BDC). The prepared nanoscale MFC-N-X (X represents the percentage of NH2-Na2BDC, i.e., X = 0, 50, and 100) showed high surface area, large pore volume, excellent magnetic response, and good water and thermal stability. Among these prepared MFC-N-X, MFC-N-100 exhibited the highest adsorption capacity of 358 mg g–1 for methylene blue (MB) and 71 mg g–1 for As(V) due to its porous structure and abundant amino groups. The prepared MFC-N-100 was successfully applied to remove MB and As(V) from different water samples (tap water, lake water, and domestic sewage) with a high removal efficiency and a rapid separation of the sorbent f...

Development of multimodal detection technologies for accurate diagnosis of cancer at early stages is in great demand. In this work, we report a novel approach using an aptamer-based dual-functional probe for rapid, sensitive, and specific counting and visualization of MCF-7 cells by inductively coupled plasma–mass spectrometry (ICP-MS) and fluorescence imaging. The probe consists of a recognition unit of aptamer to catch cancer cells specifically, a fluorescent dye (FAM) moiety for fluorescence resonance energy transfer (FRET)-based “off-on” fluorescence imaging as well as gold nanoparticles (Au NPs) tag for both ICP-MS quantification and fluorescence quenching. Due to the signal amplification effect and low spectral interference of Au NPs in ICP-MS, an excellent linearity and sensitivity were achieved. Accordingly, a limit of detection of 81 MCF-7 cells and a relative standard deviation of 5.6% (800 cells, n = 7) were obtained. The dynamic linear range was 2 × 102 to 1.2 × 104 cells, and the recoveries i...

Magnetic porous organic polymers (MOPs) with abundant thiol groups were synthesized successfully in high yield through a template-free and catalyst-free diazo-coupling reaction. The reaction was conducted under mild conditions in aqueous solution, in which the introduction of magnetism and thiol-functionalization was realized simultaneously, avoiding the use of environment-unfriendly organic solvents. The magnetic nanoparticles (MNPs) were embedded into hierarchical porous network structures of porous organic polymers (POPs) physically and the magnetism of thiol-functionalized MOPs (MOP-SH) was easily controlled by varying the amount of spiked MNPs. The obtained MOP-SH exhibited high thermal stability and chemical stability within a wide pH range (2–13), and good adsorption performance for Hg(II) over a wide pH range due to the abundant thiols in its hierarchical structure. After the adsorption process by using MOP-SH, the concentration of Hg in the spiked domestic sewage reached 1.1 μg L–1, which is even...

Trace heavy metals have great impact on biological system; therefore, it is essential to develop suitable analytical methods for the determination of trace heavy metals in biological samples to elucidate their biochemical and physiological functions in organisms. Herein, we presented a chip-based array monolithic microextraction system and combined it with inductively coupled plasma mass spectrometry (ICPMS) for online analysis of trace Hg, Pb, and Bi in real-world biological samples. Six ethylenediamine modified poly(glycidyl methacrylate-co-ethylene glycol dimethacrylate) (poly(GMA-co-EDMA-NH2)) capillary monolithic columns were embedded parallelly in microchannels of a microfluidic chip for array monolithic microextraction. Various parameters affecting the chip-based array monolithic microextraction of target metals were investigated. The sample throughput of the proposed method was 16 h–1, with the limits of detection for Hg, Pb, and Bi of 23, 12, and 13 ng L–1, respectively. The developed method was ...

Single cell analysis is a significant research field in recent years reflecting the heterogeneity of cells in a biological system. In this work, a facile droplet chip was fabricated and online combined with time-resolved inductively coupled plasma mass spectrometry (ICPMS) via a microflow nebulizer for the determination of zinc in single HepG2 cells. On the focusing geometric designed PDMS microfluidic chip, the aqueous cell suspension was ejected and divided by hexanol to generate droplets. The droplets encapsulated single cells remain intact during the transportation into ICP for subsequent detection. Under the optimized conditions, the frequency of droplet generation is 3-6 × 106 min-1, and the injected cell number is 2500 min-1, which can ensure the single cell encapsulation. ZnO nanoparticles (NPs) were used for the quantification of zinc in single cells, and the accuracy was validated by conventional acid digestion-ICPMS method. The ZnO NPs incubated HepG2 cells were analyzed as model samples, and the results exhibit the heterogeneity of HepG2 cells in the uptake/adsorption of ZnO NPs. The developed online droplet-chip-ICPMS analysis system achieves stable single cell encapsulation and has high throughput for single cell analysis. It has the potential in monitoring the content as well as distribution of trace elements/NPs at the single cell level.

We report a sensitive, selective, simple, and reliable magnetic immunoassay protocol for detection and imaging of HepG2 cells. After being captured by Cs-doped multicore magnetic nanoparticles (MMNPs), HepG2 cells were labeled by CdSe/ZnS quantum dots (QDs), which could be visualized by fluorescence imaging using the photoluminescence property of QDs, and subsequently, they can be counted by inductively coupled plasma mass spectrometry (ICP-MS) with Cd/Cs as elemental tag. Because of the superior photoluminescence properties and the large quantities of detectable Cd atoms contained in the QDs core, QDs play a dual function role in this assay, making the method easier and more comprehensive than other similar approaches. Under the optimal conditions, the limit of detection of 61 HepG2 cells and the relative standard deviation of 5.4% (800 HepG2 cells, n = 7) were obtained. The linear range was 200-30 000 cells, and the recoveries in human whole blood were in the range of 86-104%. The proposed method enables us not only to count but also to see the cancer cells with the same labeling process, opening a promising avenue for research and clinical application.

Hydrophilic magnetic N-doped porous carbon composites (MNPCs) with high special surface areas and rich nitrogen content was prepared via simple one-step carbonization of zinc oxide nanoparticles (ZnO NPs), 2-methylimidazole (HmIm), and Fe3O4@SiO2 magnetic nanoparticles (MNPs) mixture directly. During the carbonization process, ZnO NPs directly reacts with HmIm to yield porous ZIF-8 while the MNPs are incorporated into the frameworks to generate magnetic metal–organic frameworks (MFCs), and the MFCs acts as a self-sacrificing template to prepare MNPC. The obtained MNPCs via simple one-step carbonization strategy display higher adsorption capacity (429 mg g–1) for Hg2+ ions than MNPC-T700-M3-T (382 mg g–1) which was obtained by two-step synthesis strategy for comparison. It also exhibits very fast adsorption dynamics (adsorption rate constant (K2) = 2.45 g mg–1 min–1) for Hg2+ and could efficiently remove 95% Hg2+ in 2 min for 20 mg L–1 Hg2+ solution. Furthermore, the prepared MNPC exhibits good chemical st...

Trace mercury speciation in cells is critical to understand its cytotoxicity and cell protection mechanism. In this work, we fabricated a chip-based magnetic solid-phase microextraction (MSPME) system, integrating a cell lysis unit as well as a sample extraction unit, and online combined it with micro high-performance liquid chromatography (microHPLC)-inductively coupled plasma mass spectrometry (ICPMS) for the speciation of mercury in HepG2 cells. Magnetic nanoparticles with sulfhydryl functional group were synthesized and self-assembled in the microchannels for the preconcentration of mercury species in cells under an external magnetic field. The enrichment factors are ca. 10-fold, and the recoveries for the spiked samples are in the range of 98.3-106.5%. The developed method was used to analyze target mercury species in Hg(2+) or MeHg(+) incubated HepG2 cells. The results demonstrated that MeHg(+) entered into the HepG2 cells more easily than Hg(2+), and part of the MeHg(+) might demethylate into Hg(2+) in HepG2 cells. Besides, comprehensive speciation of mercury in incubated cells revealed different detoxification mechanisms of Hg(2+) and MeHg(+) in Hg(2+) or MeHg(+) incubated HepG2 cells.

In this work, a novel method of TiO2 nanoparticles (NPs) functionalized monolithic capillary microextraction (CME) online coupling with inductively coupled plasma mass spectrometry (ICPMS) was developed for the sequential determination of Gd3+ and Gd-based contrast agents in human urine samples. The monolithic capillary was prepared by embedding anatase TiO2 NPS in the poly(methacrylic acid-ethylene glycol dimethacrylate) (MAA-EDMA) framework. The Gd3+ and Gd-based contrast agents (such as gadolinium-diethylene triamine pentaacetic acid (Gd-DTPA) and Gd-DTPA-bismethylamide (Gd-DTPA-BMA)) display different adsorption behaviors on the prepared monolithic capillary which possesses the adsorption properties of both anatase TiO2 NPS and poly(MAA-EDMA) monolith. Under the optimized conditions, the limits of detection (LODs) were found to be 3.6, 3.2, and 4.5 ng L–1 for Gd3+, Gd-DTPA, and Gd-DTPA-BMA, respectively, which are the lowest up to date. The enrichment factor was 25-fold with the sample throughput of 5...

In this study, the hydrophilic polymer monolithic capillary (poly(acrylamide-vinylpyridine-methylene bis(acrylamide)), poly(AA-VP-Bis)) was prepared for the separation and enrichment of carboxyl group-containing gold nanoparticles (Au NPs) from environmental waters followed by online ICPMS determination. The extraction mechanism of the prepared poly(AA-VP-Bis) monolithic capillary for Au NPs is based on the static electrical and hydrogen bond interactions between the carboxyl group on the surface of Au NPs and pyridine/amide groups on the surface of the monolith. Under the optimal conditions, a detection limit of 24.2 fmol L(-1) and a sample throughput of 6 h(-1) were achieved for 3 nm citrate stabilized Au NPs, and the original morphology of the Au NPs could be maintained during the extraction process. The developed method was successfully applied for the analysis of carboxyl group-containing Au NPs in environmental water samples, such as tap water, the Yangtze River water, and the East Lake water, with recoveries in the range of 77-103%. Compared with the reported approaches for analysis of Au NPs, this method is an online strategy for carboxyl group-containing Au NPs determination and has the merits of low detection limit, small sample consumption, fast extraction/desorption kinetics, wide linear range, high selectivity, and high throughput.

N-Nitrosamines, probable human carcinogens, are a group of disinfection byproducts under consideration for drinking water regulation. Currently, no method can determine trace levels of alkyl and tobacco-specific nitrosamines (TSNAs) of varying physical and chemical properties in water by a single analysis. To tackle this difficulty, we developed a single solid-phase extraction (SPE) method with high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) for the determination of 14 nitrosamines of health concern with widely differing properties. We made a cartridge composed of a vinyl/divinylbenzene polymer that efficiently concentrated the 14 nitrosamines in 100 mL of water (in contrast to 500 mL in other methods). This single SPE-HPLC-MS/MS technique provided calculated method detection limits of 0.01-2.7 ng/L and recoveries of 53-93% for the 14 nitrosamines. We have successfully demonstrated that this method can determine the presence or absence of the 14 nitrosamines in drinking water systems (eight were evaluated in Canada and the U.S.), with occurrence similar to that in other surveys. N-Nitrosodimethylamine (NDMA), N-nitrosodiphenylamine, and the TSNA 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanol were identified and quantified in authentic drinking water. Formation potential (FP) tests demonstrated that NDMA and TSNA precursors were present in (1) water samples in which tobacco was leached and (2) wastewater-impacted drinking water. Our results showed that prechlorination or ozonation destroyed most of the nitrosamine precursors in water. Our new single method determination of alkylnitrosamines and TSNAs significantly reduced the time and resource demands of analysis and will enable other studies to more efficiently study precursor sources, formation mechanisms, and removal techniques. It will be useful for human exposure and health risk assessments of nitrosamines in drinking water.

We report here that tobacco-specific nitrosamines (TSNAs) are produced from specific tobacco alkaloids during water chloramination. To identify the specific precursors for the formation of specific TSNAs in drinking water, we have developed a solid-phase extraction-liquid chromatography-tandem mass spectrometry (SPE-LC-MS/MS) method for simultaneous determination of five TSNAs and three tobacco alkaloids. Using this method, we detected nicotine (NIC) at 15.1 ng/L in a source water. Chloramination of this source water resulted in the formation of 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone (NNK) (0.05 ng/L) and 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanol (NNAL) (0.2 ng/L) along with the reduction of NIC to 1.1 ng/L, suggesting that NNK and NNAL were formed from NIC. To confirm that tobacco alkaloids are the precursors of TSNAs, we chloraminated water-leaching samples of tobacco from three brands of cigarettes and found that the formation of TSNAs coincides with the reduction of the alkaloids. Chloramination of individual alkaloids confirms that NNK and NNAL are produced from NIC, N-nitrosonornicotine (NNN) from nornicotine (NOR), and N-nitrosoanabasine (NAB) from anabasine (ANA). Furthermore, we have identified specific intermediates of these reactions and proposed potential pathways of formation of TSNAs from specific alkaloids. These results confirm that NNK and NNAL are the disinfection byproducts (DBPs) resulting from NIC in raw water.

Surface-initiated atom transfer radical polymerization (SI-ATRP) has emerged as a powerful tool to synthesize polymer-tethered particles (here called particle brushes) that can self-assemble into hybrid materials with well-defined microstructure, morphology, and enhanced mechanical properties or optical transparency, as compared to binary particle/polymer nanocomposite materials. However, side reactions—such as the thermal self-initiation (TSI) of some monomers, such as styrene, during the polymerization—can result in the formation of varying amounts of homopolystyrene, in addition to particle brushes. The presence of homopolystyrene impurity reduces the predictability of properties and impedes the interpretation of structure–property relations in particle brush materials. This contribution presents a systematic evaluation of the formation of TSI homopolystyrene and its implications on the properties of polystyrene-tethered silica based particle brush materials. Kinetic and molecular weight studies reveal...

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.

CdTe quantum dots (QDs) are prepared on TiO(2) nanotubes (TiO(2) NTs), for the first time, with pulse electrodeposition. A novel single-drop optical sensor is prepared with the CdTe QDs-modified TiO(2) NTs, and applied for the detection of polycyclic aromatic hydrocarbons (PAHs) based on fluorescence resonance energy transfer (FRET). Excited at 270 nm, the sensor shows fluorescence emission at around 370 nm. As PAHs are with absorption/fluorescence emission at around 364/410 nm, FRET happens between the CdTe QDs and PAHs with the CdTe QDs as donors and PAHs as receptors. The sensitivity is dependent on the number of rings of the PAHs, with the highest sensitivity observed in the response to benzo(a)pyrene (BaP). Using FRET, the sensitivity to BaP is enhanced by about 2 orders with respect to the direct fluorescent spectrometry. The proposed sensor shows a linear response to the logarithm of BaP concentration in the range of 400 nM to 40 pM, with a detection limit of 15 pM, which is much close to the quality criteria (15.1 pM) in drinking water set by U.S. Environment Protection, suggesting that the proposed sensor can be used for quick scanning of PAHs. The achieved sensitivity is much higher than that of the published sensor-based methods. As PAHs are quantified based on the relative fluorescence intensity at 410-370 nm, the sensor need no calibration with a standard sensor, avoiding the influence from the sensor-to-sensor difference. The practicability of the sensor is tested by analyzing PAHs in Xiangjiang River water, the PAHs contents ranges from 0.045 to 2.847 ng/L based on the sampling spots.