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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 [micro]M. 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 chemesensors for chemo/biedetection. 10.1021/ac102531z

This paper reports a surface molecular self-assembly strategy for molecular imprinting in electropolymerized polyaminothiophenol (PATP) membranes at the surface of gold nanoparticles (AuNPs) modified glassy carbon (gc) electrode for the electrochemical detection of pesticide chlorpyrifos (CPF). Electropolmedzable p-aminothiophenol (ATP) was first assembled on the AuNPs at the gc electrode surface by the formation of Au--S bonds, and subsequently, the CPF template was further assembled onto the monolayer of ATP through the hydrogen-bonding interaction between amino group and CPF. A conductive hybrid membrane was fabricated at the assembled gc electrode by the electropolymerization in a mixing solution containing additional ATP and CPF templates, and meanwhile, the CPF was spontaneously imprinted into the PATP/AuNP film. The amount of imprinted sites at the PATP/AuNP film was significantly increased due to the additional replenishment of CPF templates. The cyclic voltammetric response of the imprinted PATP-AuNP-gc sensor to CPF is about 3.2-fold as compared with the imprinted PATP-Au sensor, and the detection limit for CPF is about 2 orders of magnitude lower than that by the imprinted PATP-Au sensor. An excellent electrochemical selectivity for CPF over other pesticides was also achieved. The combination of surface molecular self-ssembly with electropolymerized molecular imprinting on a larger surface area of a AuNP-medified electrode produces a high ratio of imprinted sites and, thus, provides an ultrasensitive electrochemical detection of organophosphate pesticide. 10.1021/ac901860t

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 ~ 1 nM TNT with the use of only 10 [micro]L of solution (~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.

[Mn.sup.2+]-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 [Mn.sup.2+] 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 [Mn.sup.2+] 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 ~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-acceptlng 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.

This paper reports the molecular imprinting at the walls of highly uniform silica nanotubes for the recognition of 2,4,6-trinitrotoluene (TNT). It has been demonstrated that TNT templates were efficiently imprinted into the matrix of silica through the strong acid-base pairing interaction between TNT and 3-aminopropyltriethoxysilane (APTS). TNT-imprinted silica nanotubes were synthesized by the gelation reaction between APTS and tetraethylorthosilicate (TEOS), selectively occurring at the porous walls of APTS-modified alumina membranes. The removal of the original TNT templates leaves the imprinted cavities with covalently anchored amine groups at the cavity walls. A high density of recognition sites with molecular selectivity to the TNT analyte was created at the wall of silica nanotubes. Furthermore, most of these recognition sites are situated at the inside and outside surfaces of tubular walls and in the proximity of the two surfaces due to the ultrathin wall thickness of only 15 nm, providing a better site accessibility and lower mass-transfer resistance. Therefore, greater capacity and faster kinetics of uptaking target species were achieved. The silica nanotube reported herein is an ideal form of material for imprinting various organic or biological molecules toward applications in chemical/biological sensors and bioassay.

This paper reports the finding of an investigation of a surface molecular self-assembly strategy for molecular imprinting of polymer nanowires/nanotubes. It has been demonstrated that 2,4,6-trinitrotoluene (TNT) templates were spontaneously assembled onto aminopropyl group-modified alumina pore walls by a strong charge-transfer complexing interaction between amino groups and electron-deficient nitroaromatics, forming a novel basis of surface molecular imprinting. While an additional amount of TNT templates was further replenished into a precursor mixture, a stepwise progressive polymerization was designed toward the controllable preparation of TNT-imprinted polymer nanowire/nanotube arrays in an alumina membrane. The imprinted nanowires/nanotubes with a high density of surface-imprinted sites and regular interior sites exhibit the high capacity of binding TNT molecules, which is nearly 2.5-3.0-fold that of normal imprinted particles. Moreover, the imprinted nanotubes and nanowires have ~6- and 4-fold increase in the rate of binding TNT molecules, respectively. The combination of surface molecular assembly with nanostructures in the imprinting technique can create more effective recognition sites than the only use of porogens in traditional approaches. This novel, facile strategy reported herein can be further expected to fabricate various molecular recognition nanoarrays for sensing or analytic applications.

Inthis work, a general strategy was proposed for fine manipulatingintrinsic growth of water-soluble salts belonging to different crystalsystems. Various hollow microsphere hierarchical architectures assembledwith hopperlike single crystal blocks of cubic KBr, orthorhombic (NH4)2SO4, or hexagonal Na2SO3have been designed and prepared via microemulsions. Intrinsicgrowth manipulations of different water-soluble salts has been successfullyachieved by preventing growth of the outside surface of each singlecrystal block via a diffusion-limit effect of the interfaces betweenthe oil phase and aqueous droplets. As a result, hopperlike singlecrystals of water-soluble salts belonging to different crystal systemswere formed. Furthermore, octahedral NaCl hopperlike single crystal,rather than their typical cubic shape, has also been fabricated bymanipulating their growth rates along different lattice directionsin combination with urea as additives. The large amount of fine manipulationof intrinsic growth of water-soluble salts will provide us with adeep understanding of crystallography of inorganic salts, as wellas facilitate design and production of water-soluble salts architectureswith corresponding shapes, according to the different requirements. [ABSTRACT FROM AUTHOR]

This paper reports the finding of an investigation of a surface molecular self-assembly strategy for molecular imprinting of polymer nanowires/nanotubes. It has been demonstrated that 2,4,6-trinitrotoluene (TNT) templates were spontaneously assembled onto aminopropyl group-modified alumina pore walls by a strong charge-transfer complexing interaction between amino groups and electron-deficient nitroaromatics, forming a novel basis of surface molecular imprinting. While an additional amount of TNT templates was further replenished into a precursor mixture, a stepwise progressive polymerization was designed toward the controllable preparation of TNT-imprinted polymer nanowire/nanotube arrays in an alumina membrane. The imprinted nanowires/nanotubes with a high density of surface-imprinted sites and regular interior sites exhibit the high capacity of binding TNT molecules, which is nearly 2.5-3.0-fold that of normal imprinted particles. Moreover, the imprinted nanotubes and nanowires have ~6- and 4-fold increase in the rate of binding TNT molecules, respectively. The combination of surface molecular assembly with nanostructures in the imprinting technique can create more effective recognition sites than the only use of porogens in traditional approaches. This novel, facile strategy reported herein can be further expected to fabricate various molecular recognition nanoarrays for sensing or analytic applications. [ABSTRACT FROM AUTHOR]

In this paper, we report a simple polypeptide-directed strategy for fabricating large spherical assembly of CaCO3 nanoparticles. Stepwise growth and assembly of a large number of nanoparticles have been observed, from the formation of an amorphous liquidlike CaCO3-polypeptide precursor, to the crystallization and stabilization of polypeptide-capped nanoparticles, and eventually, the spherical assembly of nanoparticles. The "soft" poly(aspartate)-capping layer binding on a nanoparticle surface resulted in the unusual soft nature of nanoparticle assembly, providing a reservoir of primary nanoparticles with a moderate mobility, which is the basis of a new strategy for reconstructing nanoparticle assembly into complex nanoparticle architectures. Moreover, the findings of the secondary assembly of nanoparticle microspheres and the morphology transformation of nanoparticle assembly demonstrate a flexible and controllable pathway for manipulating the shapes and structures of nanoparticle assembly. In addition, the combination of the polypeptide with a double hydrophilic block copolymer (DHBC) allows it to possibly further control the shape and complexity of the nanoparticle assembly. A clear perspective is shown here that more complex nanoparticle materials could be created by using "soft" biological proteins or peptides as a mediating template at the organic−inorganic interface. [ABSTRACT FROM AUTHOR]

Diagnostic and monitoring for drug-induced liver injury (DILI) predominantly rely on serum aminotransferases. However, owing to their widespread expression across multiple organs, a significant challenge emerges from the absence of reliable biomarkers for DILI diagnosis. Herein, we introduce a concept for DILI detection, circumventing the nonspecific elevation and delayed release of aminotransferases and then straightforwardly focusing on the core feature of DILI, abnormal gene expression caused by drug overdose. The developed full-scale platform integrates the properties of spherical nucleic acids with elaborately designed fluorescence in situ hybridization sequences, enabling the sensitive and specific profiling of drug-overdosed miR-122 expression alterations across molecular, cellular, organismal, and clinical scales and effectively bypassing the phenotypic features of disease. Furthermore, the diagnostic efficacies of serum and total RNA extracted from both mouse and human blood samples for DILI diagnosis were analyzed using the receiver operating characteristic curve and principal component analysis. We anticipate that this universal platform holds potential in facilitating DILI diagnosis, therapeutic evaluation, and prognosis.

Superior photostability, minimal phototoxicity, red-shifted absorption/emission wavelengths, high brightness, and an enlarged Stokes shift are essential characteristics of top-tier organic fluorophores, particularly for long-lasting super-resolution imaging in live cells (e.g., via stimulated emission depletion (STED) nanoscopy). However, few existing fluorophores possess all of these properties. In this study, we demonstrate a general approach for simultaneously enhancing these parameters through the introduction of 9,9-dimethyl-9,10-dihydroacridine (DMA) as an electron-donating auxochrome. DMA not only induces red shifts in emission wavelengths but also suppresses photooxidative reactions and prevents the formation of triplet states in DMA-based fluorophores, greatly improving photostability and remarkably minimizing phototoxicity. Moreover, the DMA group enhances the fluorophores' brightness and enlarges the Stokes shift. Importantly, the "universal" benefits of attaching the DMA auxochrome have been exemplified in various fluorophores including rhodamines, difluoride-boron complexes, and coumarin derivatives. The resulting fluorophores successfully enabled the STED imaging of organelles and HaloTag-labeled membrane proteins.

Online analysis of industrial chemicals is extremely important for managing product quality and performance. The chlorine (Cl) content is one of the most important technical metrics for chlorinated paraffins (CPs), and the conventional approaches to estimate Cl contents require transforming the Cl element to chloride followed by quantitative analysis with either titration or instrumentation, which are normally tedious and time-consuming and cannot simultaneously guide the industrial production. Here, we developed a rapid, real-time, and online approach to determine the Cl content of CPs with facile Raman spectroscopy. The chlorination of paraffins generated two new Raman peaks at 610-618 and 668-690 cm -1 , which are associated with the vibrational modes of the S HH and S HC conformations of the C-Cl bond in CPs, respectively. More importantly, the corresponding peak of the S HH conformation decreased and that of the S HC conformation increased with the enhancement of the chlorination degree of CPs. The ratiometric calculation of the two respective Raman peak areas leads to a quantitative analysis of the Cl content of CPs. The developed approach can online provide the Cl contents of CPs within seconds accurately but without the tedious sample treatment required by conventional approaches. The strategy of integrating Raman analysis with the industrial pipeline will help in managing the production and quality control of industrial chemicals., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

Endoplasmic reticulum (ER) is an important organelle of a membranous tubule network in cells for the synthesis, assembly, and modification of peptides, proteins, and enzymes. Autophagy and destruction of ER commonly occur during normal cellular activities. These processes have been studied extensively, but the spontaneous ER regeneration process is poorly understood because of the lack of molecular tools capable of distinguishing the intact, damaged, autophagic, and regenerative ER in live cells. Herein, we report a dual-localizing, environment-responsive, and lifetime-sensitive fluorescent probe for real-time monitoring ER autophagy and regeneration in live cells. Using this tool, the fluorescence lifetime imaging can quantitatively determine the degrees of ER destruction and spontaneous recovery. Significantly, we show that triglycerides supplied in lipid droplets can efficiently repair ER via the two critical pathways: (i) supplying materials for ER repair by converting triglycerides into fatty acids and diglycerides and (ii) partially inhibiting autophagy for stressed ER.

Histones are the alkali proteins in eukaryotic somatic chromatin cells which constitute the nucleosome structure together with DNA. Their abnormality is often associated with multiple tumorigenesis and other human diseases. Nevertheless, a simple and efficient super-resolution method to visualize histone distribution at the subcellular level is still unavailable. Herein, a Zn(II) terpyridine complex with rich-electronic azide units, namely, TpZnA-His, was designed and synthesized. The initial in vitro and in silico studies suggested that this complex is able to detect histones rapidly and selectively via charge-charge interactions with the histone H3 subunit. Its live cell nuclear localization, red-emission tail, and large Stokes shift allowed super-resolution evaluation of histone distributions with a clear distinction against nuclear DNA. We were able to quantitatively conclude three histone morphology alternations in live cells including condensation, aggregation, and cavity during activating histone acetylation. This work offers a better understanding as well as a versatile tool to study histone-involved gene transcription, signal transduction, and differentiation in cells.

Intracellular lipid metabolism occurs in lipid droplets (LDs), which is critical to the survival of cells. Imaging LDs is an intuitive way to understand their physiology in live cells. However, this is limited by the availability of specific probes that can properly visualize LDs in vivo. Here, an LDs-specific red-emitting probe is proposed to address this need, which is not merely with an ultrahigh signal-to-noise (S/N) ratio and a large Stokes shift (up to 214 nm) but also with superior resistance to photobleaching. The probe has been successfully applied to real-time tracking of intracellular LDs behaviors, including fusion, migration, and lipophagy processes. We deem that the proposed probe here offers a new possibility for deeper understanding of LDs-associated behaviors, elucidation of their roles and mechanisms in cellular metabolism, and determination of the transition between adaptive lipid storage and lipotoxicity as well.

Neuronal nuclei (NeuN) protein is a key RNA-associated protein to guide the transcription of RNA and regulate mRNA splicing in neurons. However, the lack of effective labeling and tracking method has hindered the elucidation of the biological mechanism of NeuN operation in living neurons to understand correlated central nervous system disorders. Here, we report a molecular probe that can be inserted into a neighboring hydrophobic-hydrophilic region in NeuN, which upon binding becomes capable of emitting light in red region. The NeuN specificity enables the probe imaging neuronal cells in primary brain regions including hippocampus, cerebellum, midbrain, and cingulate gyrus. The probes' optical properties are such to enable stimulated emission depletion imaging showing for the first time the 3D structure of RNA tangling into NeuN in a living neuron with tens of nanometer resolution.

Distinguishing tumor cells from normal cells holds the key to precision diagnosis and effective intervention of cancers. The fundamental difficulties, however, are the heterogeneity of tumor cells and the lack of truly specific and ideally universal cancer biomarkers. Here, we report a concept of tumor cell detection, bypassing the specific genotypic and phenotypic features of different tumor cell types and directly going toward the hallmark of cancer, uncontrollable growth. Combining spherical nucleic acids (SNAs) with exquisitely engineered molecular beacons (SNA beacons, dubbed SNAB technology) is capable of identifying tumor cells from normal cells based on the molecular phenotype of telomerase activity, largely bypassing the heterogeneity problem of cancers. Owing to the cell-entry capability of SNAs, the SNAB probe readily achieves tumor cell detection across multiple platforms, ranging from solution-based assay, to single cell imaging and in vivo solid tumor imaging (unlike PCR that is restricted to cell lysates). We envision the SNAB technology will impact cancer diagnosis, therapeutic response assessment, and image-guided surgery.

Precise identification and detection of cancer cells using nanoparticle probes are critically important for early cancer diagnosis and subsequent therapy. We herein develop novel folate receptor (FR)-targeted surface-enhanced Raman scattering (SERS) nanoprobes for cancer cell imaging based on a click coupling strategy. A Raman-active derivative (5,5'-dithiobis(2-nitrobenzoic acid)-N 3 (DNBA-N 3 )) is designed with a disulfide bond for covalently anchoring to the surface of hollow gold nanoparticles (HAuNPs) and a terminal azide group for facilitating highly efficient conjugation with the bioligand. Modification of HAuNPs with DNBA-N 3 yields monolayer coverage of Raman labels absorbed on the nanoparticle surface (HAuNP-DNBA-N 3 ) and strong SERS signals. HAuNP-DNBA-N 3 can be simply and effectively conjugated with folate bicyclo[6.1.0]nonyne derivatives via a copper-free click reaction. The synthesized nanoprobes (HAuNP-DNBA-folic acid (FA)) exhibit excellent targeted capacities to FR-positive cancer cells relative to FR-negative cells through SERS mappings. The receptor-mediated delivery behaviors are confirmed by comparison with the uptake of HAuNP-DNBA-N 3 and free FA competition experiments. In addition to its good stability and benign biocompatibility, the developed SERS nanoprobes have great potential for applications in targeted tumor imaging.

A two-photon fluorescent probe (J1) that selectively stains intracellular nucleolar RNA was screened from three water-soluble terpyridine derivatives (J1-J3) with quaternary ammonium groups. The photophysical properties of J1-J3 were systemically investigated both experimentally and theoretically, revealing that J1-J3 possess large Stokes shifts and the two-photon absorption action cross sections range from 38 to 97 GM in the near-infrared region. This indicates that J1 could specifically stain nucleoli by targeting the nucleolar rRNA from the recognition experiments in vitro, the two-photon imaging experiments, and the stimulated emission depletion in vivo. The mechanism of action in which J1 binds to the nucleolar rRNA was researched via both experiments and molecular modeling. The high binding selectivity of J1 to nucleolar RNA over cytosolic RNA made this probe a potential candidate to visualize rRNA probe in the living cells.

Surface-enhanced Raman scattering (SERS) by use of noble metal nanoparticles has become a powerful tool to determine a low-concentration target by unique spectral fingerprints, but it is still limited to the Raman-inactive and nonresonant biomolecules such as amine acids, proteins, and hormones. Here, we report an Ehrlich reaction based derivative strategy in combination with gold nanoparticles (Au NPs) hotspots for the selective detection of indole-like plant hormones by SERS spectroscopy. Ehrlich reaction of p-(dimethylamino)benzaldehyde (PDAB) with the indole ring chemically transformed plant hormone indole-3-butyric acid (IBA) into a Raman-active and resonant derivative with an extended π-conjugated system in the form of a cation, which produced a new absorption band at 626 nm. On the other hand, cationic IBA-PDAB highly evoked the aggregation of Au NPs with negative citrate ligands to form the effective Raman hotspots and gave rise to the new absorption ranging from 600 to 800 nm. Significantly, the spectral overlap among IBA-PDAB, aggregated Au NPs, and the exciting laser initiated the multiple optical resonances to generate the ultrahigh Raman scattering with a sensitive limit of 2.0 nM IBA. The IBA in the whole sprouts and various parts of pea, mungbean, soybean, and black bean has been identified and quantified. The reported method opens a novel avenue for the SERS detection of Raman-inactive analyte by a proper derivation.

Colloidal quantum dots can be stabilized in either a polar solvent or a nonpolar solvent depending on their surface chemistry. The former is typically achieved by charge stabilization while the latter by steric hindrance. This allows reversible tuning of their surface polarity for targeted application by engineering their ligand profile. Here we developed a hybrid stabilization approach that leveraged a combination of steric hindrance and charge stabilization simultaneously. We demonstrated this mechanism in a phase transfer process where hexane dispersed and hydrophobic CdSe/CdS core/shell quantum dots were exchanged into the hydrophilic dimethylformamide (DMF) phase. This was achieved by employing both Z-type cadmium acetate and X-type halide ligands. The results suggested only by using this hybrid stabilization strategy were we able to achieve good colloidal stability while preserving their photoluminescence quantum yield. This hybrid ligand strategy may promise new opportunities for the application of QDs in optoelectronic areas.

Classical pH test papers are widely used to measure the acid-base degree of media in a qualitative or semiquantitative manner. However, the extension of portable and inexpensive methods to a wide range of analytes so as to eliminate the tediousness of instrumental assays remains unsuccessful. Here, we report a novel kind of dual-colored carbon dot (CD) ratiometric fluorescent test paper for the semiquantitative assay of copper ions (Cu 2+ ) by a dose-sensitive color evolution. The preparation of the test paper is based on the following two interesting findings: on the one hand, residual p-phenylenediamine at the surface of as-synthesized red CDs (r-CDs) efficiently binds Cu 2+ ions to produce a strong visible absorption that overlaps the emission of blue CDs (b-CDs); on the other hand, the Cu 2+ ions render the adsorption of small b-CDs onto the surface of larger r-CDs through their dual-coordinating interactions with the surface ligands of both r-CDs and b-CDs. These two mechanisms lead to a specific spectral energy transfer to quench the fluorescence of b-CDs with a sensitive detection limit of 8.82 nM Cu 2+ , whereas the red fluorescence of r-CDs is unaffected as a stable internal standard. Ratiometric fluorescent test papers have been prepared using a mixture of r-CDs and b-CDs (1:7) as ink by jetprinting on a piece of paper. With the addition of Cu 2+ ions, the blue test paper produces a consecutive wide-colored evolution from blue to orange-red, with a dose-discerning ability as low as 25 nM.

Graphene oxide (GO) has been widely used as a fluorescence quencher, but its luminescent properties, especially tailor-made controlling emission colors, have been seldom reported due to its heterogeneous structures. Herein, we demonstrated a novel chemical oxidative strategy to tune GO emissions from brown to cyan without changing excitation wavelength. The precise tuning is simply achieved by varying reaction times of GO nanosheets in piranha solution, but there is no need for complex chromatography separation procedures. With increasing reaction times, oxygen content on the lattice of GO nanosheets increased, accompanied by the diminution of their sizes and sp(2) conjugation system, resulting in an increase of emissive carbon cluster-like states. Thereby, the luminescent colors of GO were tuned from brown to yellow, green, and cyan, and its fluorescent quantum yields were enhanced. The obtained multicolored fluorescent GO nanosheets would open plenty of novel applications in cellular imaging and multiplex encoding analysis.

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.

Penicilloic acid (PA) is a degraded byproduct of penicillin and often causes fatal allergies to humans, but its rapid detection in penicillin drugs remains a challenge due to its similarity to the mother structure of penicillin. Here, we reported a ligand-replaced molecularly imprinted monolayer strategy on a surface-enhanced Raman scattering (SERS) substrate for the specific recognition and rapid detection of Raman-inactive PA in penicillin. The bis(phenylenediamine)-Cu(2+)-PA complex was first synthesized and stabilized onto the surface of silver nanoparticle film that was fabricated by a bromide ion-added silver mirror reaction. A molecularly imprinted monolayer was formed by the further modification of alkanethiol around the stabilized complex on the Ag film substrate, and the imprinted recognition site was then created by the replacement of the complex template with Raman-active probe molecule p-aminothiophenol. When PA rebound into the imprinted site in the alkanethiol monolayer, the SERS signal of p-aminothiophenol exhibited remarkable enhancement with a detection limit of 0.10 nM. The imprinted monolayer can efficiently exclude the interference of penicillin and thus provides a selective determination of 0.10‰ (w/w) PA in penicillin, which is about 1 order of magnitude lower than the prescribed residual amount of 1.0‰. The strategy reported here is simple, rapid and inexpensive compared to the traditional chromatography-based methods.

Highly green emissive gold nanoclusters (Au NCs) are synthesized using glutathione as a stabilizing agent and mercaptopropionic acid as a ligand, and the intensity of fluorescence is specifically sensitive to lead ions. We then fabricated a ratiometric fluorescence nanohybrid by covalently linking the green Au NCs to the surface of silica nanoparticles embedded with red quantum dots (QDs) for on-site visual determination of lead ions. The green fluorescence can be selectively quenched by lead ions, whereas the red fluorescence is inert to lead ions as internal reference. The different response of the two emissions results in a continuous fluorescence color change from green to yellow that can be clearly observed by the naked eyes. The nanohybrid sensor exhibits high sensitivity to lead ions with a detection limit of 3.5 nM and has been demonstrated for determination of lead ions in real water samples including tap water, mineral water, groundwater, and seawater. For practical application, we dope the Au NCs in poly(vinyl alcohol) (PVA) film and fabricate fluorescence test strips to directly detect lead ions in water. The PVA-film method has a visual detection limit of 0.1 μM, showing its promising application for on-site identification of lead ions without the need for elaborate equipment.

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.

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 dog's 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.

A new "turn on" fluorescence nanosensor for selective Hg(2+) determination is reported based on bis(dithiocarbamato)copper(II) functionalized carbon nanodots (CuDTC2-CDs). The CuDTC2 complex was conjugated to the prepared amine-coated CDs by the condensation of carbon disulfide onto the nitrogen atoms in the surface amine groups, followed by the coordination of copper(II) to the resulting dithiocarbamate groups (DTC) and finally by the additional coordination of ammonium N-(dithicarbaxy) sarcosine (DTCS) to form the CuDTC2-complexing CDs. The CuDTC2 complex at surface strongly quenched the bright-blue fluorescence of the CDs by a combination of electron transfer and energy transfer mechanism. Hg(2+) could immediately switch on the fluorescence of the CuDTC2-CDs by promptly displacing the Cu(2+) in the CuDTC2 complex and thus shutting down the energy transfer pathway, in which the sensitive limit for Hg(2+) as low as 4 ppb was reached. Moreover, a paper-based sensor has been fabricated by printing the CuDTC2-CDs probe ink on a piece of cellulose acetate paper using a commercial inkjet printer. The fluorescence "turn on" on the paper provided the most conveniently visual detection of aqueous Hg(2+) ions by the observation with naked eye. The very simple and effective strategy reported here facilitates the development of portable and reliable fluorescence nanosensors for the determination of Hg(2+) in real samples.

The chemical sensing for the convenient detection of mercuric ion (II) (Hg(2+)) have been widely explored with the use of various sensing materials and techniques. It still remains a challenge to achieve ultrasensitive but simple, rapid, and inexpensive detection to metal ions. Here we report a surface-enhanced Raman scattering (SERS) chip for the femtomolar (fM) detection of Hg(2+) by employing silver-coated gold nanoparticles (Au@Ag NPs) together with an organic ligand. 4,4'-Dipyridyl (Dpy) can control the aggregation of Au@Ag NPs via its dual interacting sites to Ag nanoshells to generate strong Raman hot spots and SERS readouts. However, the presence of Hg(2+) can inhibit the aggregation of Au@Ag NPs by the coordination with Dpy, and as a result the SERS signals of Dpy are quenched. On the basis of these findings, a SERS chip has been fabricated by the assembly of Au@Ag NPs on a piece of silicon wafer and the further modification with Dpy. The exchange of Dpy from the chip into the aqueous Hg(2+) droplet results in the quenching of Raman signals of Dpy, responding to 10 fM Hg(2+) that is about 6 orders of magnitude lower than the limit defined by the U.S. Environmental Protection Agency in drinkable water. Each test using the SERS chip only needs a droplet of 20 μL sample and is accomplished within ∼4 min. The SERS chip has also been applied to the quantification of Hg(2+) in milk, juice, and lake water.

The instant and on-site detection of trace aqueous mercuric ion still remains a challenge for environmental monitoring and protection. This work demonstrates a new analytical method and its utility for visual detection of aqueous Hg(2+) on the basis of a novel water-soluble CdSe-ZnS quantum dots (QDs) functionalized with a bidentate ligand of 2-hydroxyethyldithiocarbamate (HDTC). The fluorescence of the aqueous HDTC modified QDs (HDTC-QDs) could be selectively and efficiently quenched by Hg(2+) through a surface chelating reaction between HDTC and Hg(2+), and the detection limit was measured to be 1 ppb. Most interestingly, the orange fluorescence of the HDTC-QDs gradually changes to red upon the increasing amount of Hg(2+) added besides the decreasing of the fluorescence intensity. By taking advantage of this optical phenomenon, a paper-based sensor for aqueous Hg(2+) detection has been developed by immobilizing the HDTC-QDs on cellulose acetate paper which has low background fluorescence in the wavelength range. The paper-based sensor showed high sensitivity and selectivity for Hg(2+) visual detection. When Hg(2+) was dropped onto the paper-sensor, an obviously distinguishable fluorescence color evolution (from orange to red) could be clearly observed depending on the concentration of Hg(2+). The limit of detection of the visual method for aqueous Hg(2+) detection was as low as 0.2 ppm. The very simple and effective strategy reported here should facilitate the development of portable and reliable fluorescence chemosensors for mercuric pollution control.

To achieve selectivity in direct chemiluminescence (CL) detection is very significant and a great challenge as well. Here, we report a novel concept of developing intrinsically selective CL switching at the surface of Fe(3)O(4) nanoparticles for the sensitive detection and simultaneous determination of various pesticides. Fe(3)O(4) nanoparticles have peroxidase-like catalytic activity and catalyze the decomposition of dissolved oxygen to generate superoxide anions, so that the CL intensity of luminol was amplified by at least 20 times. The CL signals can be quenched by the addition of ethanol because ethanol readily reacts with superoxide anions as a radical scavenger. However, the quenching effect can be inhibited through the specific binding of target molecules on Fe(3)O(4) nanoparticles, leading to CL "turn-on" in the presence of ethanol. The novel CL "switching-on" concept demonstrated unique advantages in the detection of pesticide residues. Using the surface coordinative reactions, nonredox pesticide ethoprophos were sensitively detected with a detection limit of 0.1 nM and had a very wide detection range of 0.1 nM to 100 μM. More importantly, the selectivity of CL switching is tunable through the special surface modification of Fe(3)O(4) nanoparticles, and these Fe(3)O(4) nanoparticles with different surface groups can generate unique CL response pattern for the simultaneous determination of various pesticides. Meanwhile, the superparamagnetic properties of Fe(3)O(4) nanoparticles provide a simple magnetic separation approach to attain interference-free measurement for real detection. The very facile and versatile strategy reported here should open a new window to exploration of selective CL molecular switching and application of magnetic nanoparticles for chemo/biodetection.

Here, we report the shell thickness-dependent Raman enhancement of silver-coated gold nanoparticles (Au@Ag NPs) for the identification and detection of pesticide residues at various fruit peels. The Raman enhancement of Au@Ag NPs to a large family of sulfur-containing pesticides is ~2 orders of magnitude stronger than those of bare Au and Ag NPs, and there is a strong dependence of the Raman enhancement on the Ag shell thickness. It has been shown for the first time that the huge Raman enhancement is contributed by individual Au@Ag NPs rather than aggregated Au@Ag NPs with "hot spots" among the neighboring NPs. Therefore, the Au@Ag NPs with excellent individual-particle enhancement can be exploited as stand-alone-particle Raman amplifiers for the surface identification and detection of pesticide residues at various peels of fruits, such as apple, grape, mango, pear, and peach. By casting the particle sensors onto fruit peels, several types of pesticide residues (e.g., thiocarbamate and organophosphorous compounds) have been reliably/rapidly detected, for example, 1.5 nanograms of thiram per square centimeter at apple peel under the current unoptimized condition. The surface-lifting spectroscopic technique offers great practical potentials for the on-site assessment and identification of pesticide residues in agricultural products., (© 2011 American Chemical Society)

To detect trace trinitrotoluene (TNT) explosives deposited on various surfaces instantly and on-site still remains a challenge for homeland security needs against terrorism. This work demonstrates a new concept and its utility for visual detection of TNT particulates on various package materials. The concept takes advantages of the superior fluorescent properties of quantum dots (QDs) for visual signal output via ratiometric fluorescence, the feasibility of surface grafting of QDs for chemical recognition of TNT, and the ease of operation of the fingerprint lifting technique. Two differently sized CdTe QDs emitting red and green fluorescences, respectively, have been hybridized by embedding the red-emitting one in silica nanoparticles and covalently linking the green-emitting one to the silica surface, respectively, to form a dual-emissive fluorescent hybrid nanoparticle. The fluorescence of red QDs in the silica nanoparticles stays constant, whereas the green QDs functionalized with polyamine can selectively bind TNT by the formation of Meisenheimer complex, leading to the green fluorescence quenching due to resonance energy transfer. The variations of the two fluorescence intensity ratios display continuous color changes from yellow-green to red upon exposure to different amounts of TNT. By immobilization of the probes on a piece of filter paper, a fingerprint lifting technique has been innovated to visualize trace TNT particulates on various surfaces by the appearance of a different color against a yellow-green background under a UV lamp. This method shows high selectivity and sensitivity with a detection limit as low as 5 ng/mm(2) on a manila envelope and the attribute of being seen with the naked eye.

This paper reports that extremely strongly coupled excitonic states were formed in H-aggregated monocrystalline nanosheets and semicrystalline nanowires of coplanar organic molecules of 2,5-bis(4-methoxybenzylidene) cyclopentanone, due to the highly regular face-to-face stacking of molecular excitons. It was demonstrated that the spectral absorption and fluorescence emission behaviors are dependent on the routes of molecular aggregation and the ordered degree of molecular arrangement in aggregated nanoparticles. In particular, the H-type aggregation of molecules through a highly ordered molecular arrangement in the monocrystalline nanosheets led to the formation of a new exciton coupling state with an energy band higher than that in normal semi-/noncrystalline H-aggregation. A strong symmetric absorption at higher energy bands was thus observed in the solution of nanosheets. Furthermore, the strongly coupled excitonic state may hold all the oscillator strength, leading to the extinction of the original intramolecular electronic transitions of individual molecules and the appearance of new strong absorption and fluorescence emissions at high-energy bands. These results show a perspective that the ability to control the molecular structure and its arrangement in aggregates holds promise for creating novel optical properties in molecular materials.

This paper reports a surface functional monomer-directing strategy for the highly dense imprinting of 2,4,6-trinitrotoluene (TNT) molecules at the surface of silica nanoparticles. It has been demonstrated that the vinyl functional monomer layer of the silica surface can not only direct the selective occurrence of imprinting polymerization at the surface of silica through the copolymerization of vinyl end groups with functional monomers, but also drive TNT templates into the formed polymer shells through the charge-transfer complexing interactions between TNT and the functional monomer layer. The two basic processes lead to the formation of uniform core-shell TNT-imprinted nanoparticles with a controllable shell thickness and a high density of effective recognition sites. The high capacity and fast kinetics to uptake TNT molecules show that the density of effective imprinted sites in the nanoshells is nearly 5 times that of traditional imprinted particles. A critical value of shell thickness for the maximum rebinding capacity was determined by testing the evolution of rebinding capacity with shell thickness, which provides new insights into the effectiveness of molecular imprinting and the form of imprinted materials. These results reported here not only can find many applications in molecularly imprinting techniques but also can form the basis of a new strategy for preparing various polymer-coating layers on silica support.

In this paper, we report a simple polypeptide-directed strategy for fabricating large spherical assembly of CaCO(3) nanoparticles. Stepwise growth and assembly of a large number of nanoparticles have been observed, from the formation of an amorphous liquidlike CaCO(3)-polypeptide precursor, to the crystallization and stabilization of polypeptide-capped nanoparticles, and eventually, the spherical assembly of nanoparticles. The "soft" poly(aspartate)-capping layer binding on a nanoparticle surface resulted in the unusual soft nature of nanoparticle assembly, providing a reservoir of primary nanoparticles with a moderate mobility, which is the basis of a new strategy for reconstructing nanoparticle assembly into complex nanoparticle architectures. Moreover, the findings of the secondary assembly of nanoparticle microspheres and the morphology transformation of nanoparticle assembly demonstrate a flexible and controllable pathway for manipulating the shapes and structures of nanoparticle assembly. In addition, the combination of the polypeptide with a double hydrophilic block copolymer (DHBC) allows it to possibly further control the shape and complexity of the nanoparticle assembly. A clear perspective is shown here that more complex nanoparticle materials could be created by using "soft" biological proteins or peptides as a mediating template at the organic-inorganic interface.