Bianhua Liu

Amine-Capped ZnS−Mn2+ Nanocrystals for Fluorescence Detection of Trace TNT Explosive

Mn2+-doped ZnS nanocrystals with an amine-capping layer have been synthesized and used for the fluorescence detection of ultratrace 2,4,6-trinitrotoluene (TNT) by quenching the strong orange Mn2+ photoluminescence. The organic amine-capped nanocrystals can bind TNT species from solution and atmosphere by the acid-base pairing interaction between electron-rich amino ligands and electron-deficient aromatic rings. The resultant TNT anions bound onto the amino monolayer can efficiently quench the Mn2+ photoluminescence through the electron transfer from the conductive band of ZnS to the lowest unoccupied molecular orbital (LUMO) of TNT anions. The amino ligands provide an amplified response to the binding events of nitroaromatic compounds by the 2- to approximately 5-fold increase in quenching constants. Moreover, a large difference in quenching efficiency was observed for different types of nitroaromatic analytes, dependent on the affinity of nitro analytes to the amino monolayer and their electron-accepting abilities. The amine-capped nanocrystals can sensitively detect down to 1 nM TNT in solution or several parts-per-billion of TNT vapor in atmosphere. The ion-doped nanocrystal sensors reported here show a remarkable air/solution stability, high quantum yield, and strong analyte affinity and, therefore, are well-suited for detecting the ultratrace TNT and distinguishing different nitro compounds.

Resonance Energy Transfer-Amplifying Fluorescence Quenching at the Surface of Silica Nanoparticles toward Ultrasensitive Detection of TNT

This paper reports a resonance energy transfer-amplifying fluorescence quenching at the surface of silica nanoparticles for the ultrasensitive detection of 2,4,6-trinitrotoluene (TNT) in solution and vapor environments. Fluorescence dye and organic amine were covalently modified onto the surface of silica nanoparticles to form a hybrid monolayer of dye fluorophores and amine ligands. The fluorescent silica particles can specifically bind TNT species by the charge-transfer complexing interaction between electron-rich amine ligands and electron-deficient aromatic rings. The resultant TNT-amine complexes bound at the silica surface can strongly suppress the fluorescence emission of the chosen dye by the fluorescence resonance energy transfer (FRET) from dye donor to the irradiative TNT-amine acceptor through intermolecular polar-polar interactions at spatial proximity. The quenching efficiency of the hybrid nanoparticles with TNT is greatly amplified by at least 10-fold that of the corresponding pure dye. The nanoparticle-assembled arrays on silicon wafer can sensitively detect down to approximately 1 nM TNT with the use of only 10 microL of solution (approximately 2 pg TNT) and several ppb of TNT vapor in air. The simple FRET-based nanoparticle sensors reported here exhibit a high and stable fluorescence brightness, strong analyte affinity, and good assembly flexibility and can thus find many applications in the detection of ultratrace analytes.

A simple, reliable and sensitive colorimetric visualization of melamine in milk by unmodified gold nanoparticles

In this paper, we report a simple, reliable and sensitive colourimetric visualization of melamine in milk products using citrate-stabilized gold nanoparticles (Au NPs). Upon exposure to ppb-level melamine, gold nanoparticle solution exhibits a highly sensitive colour change from red to blue and rapid aggregation kinetics within the initial 5 min, which can directly be seen with the naked eye and monitored by UV-vis absorbance spectra. As confirmed by the comparison with six other typical amino compounds, the melamine molecule itself contains multiple strong-binding sites to the surface of Au NPs and thus plays a role of molecular linker to efficiently crosslink Au NPs. Further evidence is that the sensitivity is significantly improved when NaHSO(4) is added to promote the ligand exchange between citrate and melamine at the surface of Au NPs. The NaHSO(4)-optimized Au NPs system provides a rapid colourimetric assay for the rapid detection of melamine down to approximately 25 ppb in real milk products.

Ligand Replacement-Induced Fluorescence Switch of Quantum Dots for Ultrasensitive Detection of Organophosphorothioate Pesticides

The development of a simple and on-site assay for the detection of organophosphorus pesticed residues is very important for food safety and exosystem protection. This paper reports the surface coordination-originated fluorescence resonance energy transfer (FRET) of CdTe quantum dots (QDs) and a simple ligand-replacement turn-on mechanism for the highly sensitive and selective detection of organophosphorothioate pesticides. It has been demonstrated that coordination of dithizone at the surface of CdTe QDs in basic media can strongly quench the green emission of CdTe QDs by a FRET mechanism. Upon the addition of organophosphorothioate pesticides, the dithizone ligands at the CdTe QD surface are replaced by the hydrolyzate of the organophosphorothioate, and hence the fluorescence is turned on. The fluorescence turn on is immediate, and the limit of detection for chlorpyrifos is as low as ∼0.1 nM. Two consecutive linear ranges allow a wide determination of chlorpyrifos concentrations from 0.1 nM to 10 μM. Importantly, the fluorescence turn-on chemosensor can directly detect chlorpyrifos residues in apples at a limit of 5.5 ppb, which is under the maximum residue limit allowed by the U.S. Environmental Protection Agency. The very simple strategy reported here should facilitate the development of fluorescence turn-on chemosensors for chemo/biodetection.

Imprinting of Molecular Recognition Sites on Nanostructures and Its Applications in Chemosensors.

Biological receptors including enzymes, antibodies and active proteins have been widely used as the detection platform in a variety of chemo/biosensors and bioassays. However, the use of artificial host materials in chemical/biological detections has become increasingly attractive, because the synthetic recognition systems such as molecularly imprinted polymers (MIPs) usually have lower costs, higher physical/chemical stability, easier preparation and better engineering possibility than biological receptors. Molecular imprinting is one of the most efficient strategies to offer a synthetic route to artificial recognition systems by a template polymerization technique, and has attracted considerable efforts due to its importance in separation, chemo/biosensors, catalysis and biomedicine. Despite the fact that MIPs have molecular recognition ability similar to that of biological receptors, traditional bulky MIP materials usually exhibit a low binding capacity and slow binding kinetics to the target species. Moreover, the MIP materials lack the signal-output response to analyte binding events when used as recognition elements in chemo/biosensors or bioassays. Recently, various explorations have demonstrated that molecular imprinting nanotechniques may provide a potential solution to these difficulties. Many successful examples of the development of MIP-based sensors have also been reported during the past several decades. This review will begin with a brief introduction to the principle of molecular imprinting nanotechnology, and then mainly summarize various synthesis methodologies and recognition properties of MIP nanomaterials and their applications in MIP-based chemosensors. Finally, the future perspectives and efforts in MIP nanomaterials and MIP-based sensors are given.

Real-Time Discrimination and Versatile Profiling of Spontaneous Reactive Oxygen Species in Living Organisms with a Single Fluorescent Probe.

Fluorescent probes are powerful tools for the investigations of reactive oxygen species (ROS) in living organisms by visualization and imaging. However, the multiparallel assays of several ROS with multiple probes are often limited by the available number of spectrally nonoverlapping chromophores together with large invasive effects and discrepant biological locations. Meanwhile, the spontaneous ROS profilings in various living organs/tissues are also limited by the penetration capability of probes across different biological barriers and the stability in reactive in vivo environments. Here, we report a single fluorescent probe to achieve the effective discrimination and profiling of hydroxyl radicals (•OH) and hypochlorous acid (HClO) in living organisms. The probe is constructed by chemically grafting an additional five-membered heterocyclic ring and a lateral triethylene glycol chain to a fluorescein mother, which does not only turn off the fluorescence of fluorescein, but also create the dual reactive sites to ROS and the penetration capability in passing through various biological barriers. The reactions of probe with •OH and HClO simultaneously result in cyan and green emissions, respectively, providing the real-time discrimination and quantitative analysis of the two ROS in cellular mitochondria. Surprisingly, the accumulation of probes in the intestine and liver of a normal-state zebrafish and the transfer pathway from intestine-to-blood-to-organ/tissue-to-kidney-to-excretion clearly present the profiling of spontaneous •OH and HClO in these metabolic organs. In particular, the stress generation of •OH at the fresh wound of zebrafish is successfully visualized for the first time, in spite of its extremely short lifetime.

Selective Fluorescence Turn-On and Ratiometric Detection of Organophosphate Using Dual-Emitting Mn-Doped ZnS Nanocrystal Probe

Semiconductor nanocrystals (NCs) possess unique photoluminescent properties which can be used to design fluorescence probes for chemo/biosensing applications. Several have recently emerged that offer excellent turn-on or ratiometric fluorescence chemosensory protocols by sophisticated procedures, but it has been challenging to realize all of these advantages in a single construct. Herein, we develop an intrinsic dual-emitting Mn-doped ZnS nanocrystal-based probe that achieves this goal with turn-on and ratiometric fluorescence response for the determination of organophosphate (diethylphosphorothioate, DEP). The probe relies on the modification of dopamine dithiocarbamate on the surface of NCs and the modulation of dual emission through a photoinduced electron transfer process, which makes use of red fluorescence of Mn(2+) ions doped in the NCs as specific recognition for the target analyte and blue defect emission of the NCs as stable internal reference. In presence of DEP, the red emission of the probe is thus enhanced by switching off the electron transfer pathway, while the blue emission is almost unchanged. With the addition of different amounts DEP, the two emission intensity ratios gradually vary and display color changes from dark-blue to purple to red. Thus, this method generates turn-on and ratiometric fluorescence signals for quantitative and visual detection of the analyte. Significantly, the dual-emitting probe has been used to fabricate paper-based test strips for visual detection of DEP residues, which validate the method for its rapid, on-site, and visual identification.

Inverted Opal Fluorescent Film Chemosensor for the Detection of Explosive Nitroaromatic Vapors through Fluorescence Resonance Energy Transfer

This paper reports an inverted opal fluorescence chemosensor for the ultrasensitive detection of explosive nitroaromatic vapors through resonance-energy-transfer-amplified fluorescence quenching. The inverted opal silica film with amino ligands was first fabricated by the acid-base interaction between 3-aminopropyltriethoxysilane and surface sulfonic groups on polystyrene microsphere templates. The fluorescent dye was then chemically anchored onto the interconnected porous surface to form a hybrid monolayer of amino ligands and dye molecules. The amino ligands can efficiently capture vapor molecules of nitroaromatics such as 2,4,6-trinitrotoluene (TNT) through the charge-transfer complexing interaction between electron-rich amino ligands and electron-deficient aromatic rings. Meanwhile, the resultant TNT-amine complexes can strongly suppress the fluorescence emission of the chosen dye by the fluorescent resonance energy transfer (FRET) from the dye donor to the irradiative TNT-amino acceptor through intermolecular polar-polar resonance at spatial proximity. The quenching response of the highly ordered porous films with TNT is greatly amplified by at least 10-fold that of the amorphous silica films, due to the interconnected porous structure and large surface-to-volume ratio. The inverted opal film with a stable fluorescence brightness and strong analyte affinity has lead to an ultrasensitive detection of several ppb of TNT vapor in air.

Ratiometric fluorescence detection of mercuric ion based on the nanohybrid of fluorescence carbon dots and quantum dots

A novel nanohybrid ratiometric fluorescence probe comprised of carbon dots (C-dots) and hydrophilic CdSe@ZnS quantum dots (QDs) has been developed by simply mixing the blue-emission C-dots with red-emission carboxylmethyldithiocarbamate modified CdSe@ZnS QDs (GDTC-QDs). The nanohybrid ratiometric fluorescence probe exhibits dual emissions at 436 nm and 629 nm under a single excitation wavelength. Due to the strong chelating ability of GDTC on the surface of QDs to mercuric ion (Hg(2+)), the fluorescence of the GDTC-QDs in the nanohybrid system could be selectively quenched in the presence of Hg(2+) while the fluorescence of the C-dots remained constant, resulting in an obviously distinguishable fluorescence color evolution (from red to blue) of the nanohybrid system. The detection limit of this method was found to be as low as 0.1 μM. Furthermore, the recovery result for Hg(2+) in real samples including tap water and lake water by this method was satisfying, suggesting its potential application for Hg(2+) sensing.

Inkjet-Printed Silver Nanoparticle Paper Detects Airborne Species from Crystalline Explosives and Their Ultratrace Residues in Open Environment

An electronic nose can detect highly volatile chemicals in foods, drugs, and environments, but it is still very much a challenge to detect the odors from crystalline compounds (e.g., solid explosives) with a low vapor pressure using the present chemosensing techniques in such way as a dogs olfactory system can do. Here, we inkjet printed silver nanoparticles (AgNPs) on cellulose paper and established a Raman spectroscopic approach to detect the odors of explosive trinitrotoluene (TNT) crystals and residues in the open environment. The layer-by-layer printed AgNP paper was modified with p-aminobenzenethiol (PABT) for efficiently collecting airborne TNT via a charge-transfer reaction and for greatly enhancing the Raman scattering of PABT by multiple spectral resonances. Thus, a Raman switch concept by the Raman readout of PABT for the detection of TNT was proposed. The AgNPs paper at different sites exhibited a highly uniform sensitivity to TNT due to the layer-by-layer printing, and the sensitive limit could reach 1.6 × 10(-17) g/cm(2) TNT. Experimentally, upon applying a beam of near-infrared low-energy laser to slightly heat (but not destruct) TNT crystals, the resulting airborne TNT in the open environment was probed at the height of 5 cm, in which the concentration of airborne species was lower than 10 ppt by a theoretical analysis. Similarly, the odors from 1.4 ppm TNT in soil and 7.2, 2.9, and 5.7 ng/cm(2) TNT on clothing, leather, and envelope, respectively, were also quickly sensed for 2 s without destoying these inspected objects.