Search

Both afterglow-catalysis and photoluminescence (PL) self-reporting of pollutant degradation are achieved by persistent luminescent ethylenediaminetetraacetic acid disodium (EDTA)-etched Cr3+-doped ...

Surface-enhanced Raman scattering (SERS) has been widely investigated in recent years. The subtle design and synthesis of SERS substrates, including the semiconductor–metal composites, are the key ...

The authors proposed a novel template-free strategy, urease-mediated interfacial growth of NH

Traps, size and aqueous-dispersibility are the most important parameters that affect the features and applications of persistent luminescent nanoparticles (PLNPs). However, simultaneous controlling of these parameters is rather difficult and has not been reported yet. We present the first exploration on adjusting the traps, size and aqueous-dispersibility of PLNPs via simple ethylenediaminetetraacetate (EDTA) etching. Cr0.0043+:ZnGa2O4 (ZGO) was used as the PLNP model. EDTA etching of the sintered ZGO results in effective reduction of the size and great improvement in the aqueous-dispersibility. In addition, EDTA etching alters the density of mediate traps and generates new deep traps, thus achieving the massive production of (ultra)small ZGO–EDTA with fine aqueous-dispersibility, suitable mediate/deep traps and superlong bright afterglows (51 days). As EDTA can interact with most metals, this simple EDTA etching strategy is prospectively amenable to other PLNPs, and the resulting PLNPs–EDTA have wide applications in both biological field and information storage.

Selectively capturing nanosized titanium dioxide (nano-TiO2) from complex mixtures is a very significant but very formidable task both for enriching the analytical methodology and removing/recycling of nano-TiO2. We presented a novel sustainable strategy for such a task by using the bisphosphonate-functionalized Fe3O4 (BP-Fe3O4) nanoparticles as the highly selective adsorbents toward nano-TiO2. The BP-Fe3O4 exhibited high equilibrium adsorption capacity (Qe) toward nano-TiO2 (2.45 g g–1 for 60 nm anatase TiO2) but negligible Qe toward nano-SiO2 (0.01 g g–1 for 15 nm SiO2). The BP-Fe3O4 also had good adsorption capability toward nano-TiO2 in complex liquid media, or in the solid mixtures containing 10−500 times of coexisting nano-SiO2. This capturing strategy enables the green pretreatment for quantitative analysis of nano-TiO2 in complex real samples with the spike recoveries of 69.9–99.0% and low detection limit of 0.02 ppm. Furthermore, this strategy offers great convenience for identification of the cr...

We presented the first exploration of the easily prepared nickel-decorated magnetic Fe3O4 nanoparticles as recyclable nanosized magnetic self-stirring catalysts for microdroplet reactions. The cross-linked polymer poly(cyclotriphosphazene-co-4,4′-sulfonyldiphenol) (PZS) was used as the intermediary to link Fe3O4 and anchored nickel nanodots. On the basis of the charming magnetic feathers of Fe3O4 and the fine catalysis activity of Ni, the Fe3O4@PZS-Ni nanoparticles could not only self-stir or make the reactants move along the tiny channels with the help of the external rotating magnetic field but also exhibit high catalysis activity and convenient recyclability. The Fe3O4@PZS-Ni nanoparticles have the merits of small size, good suspension, easy fabrication, and most importantly, superior flexibility and adaptability to any shape of the microreactors or nanoreactors; thus, they may bring new inspiration for self-stirring catalytic reactions in micro/nanochips or micro/nanobiological tubules or tissues.

EDTA etching, the first strategy that simply generates deep traps while reducing the size and improving the aqueous-dispersibility, is presented., Traps, size and aqueous-dispersibility are the most important parameters that affect the features and applications of persistent luminescent nanoparticles (PLNPs). However, simultaneous controlling of these parameters is rather difficult and has not been reported yet. We present the first exploration on adjusting the traps, size and aqueous-dispersibility of PLNPs via simple ethylenediaminetetraacetate (EDTA) etching. Cr0.0043+:ZnGa2O4 (ZGO) was used as the PLNP model. EDTA etching of the sintered ZGO results in effective reduction of the size and great improvement in the aqueous-dispersibility. In addition, EDTA etching alters the density of mediate traps and generates new deep traps, thus achieving the massive production of (ultra)small ZGO–EDTA with fine aqueous-dispersibility, suitable mediate/deep traps and superlong bright afterglows (51 days). As EDTA can interact with most metals, this simple EDTA etching strategy is prospectively amenable to other PLNPs, and the resulting PLNPs–EDTA have wide applications in both biological field and information storage.

Traditional photoluminescence resonance energy transfer (PRET)-based sensors are widely applied, but still suffer from the severe background interference from in situ excitation. The afterglow nature of the persistent luminescence nanoparticles (PLNPs) allows optosensing after the stoppage of in situ illumination, and thus subtly overcomes that interference. We proposed a simple strategy for functionalizing PLNPs for bioanalytical applications and the new afterglow resonance energy transfer (ARET)-based assay for quantitative determination and imaging of fibroblast activation protein-alpha (FAPα) in live cells using Au-decorated Cr3+0.004:ZnGa2O4 as donor and Cy5.5-KGPNQC-SH as acceptor. The ARET between the donor and acceptor quenches the afterglow of the donor, and the cleavage of peptide KGPNQC by FAPα inhibits the ARET and restores the afterglow of the donor. The ARET-based assay of FAPα, with the linear range of 0.1–2.0 mg·L–1 (1.2–22.9 nM), LOD of 11 μg·L–1 (115 pM), and RSD of 3.9% (for 0.5 mg·L–1 ...

Persistent luminescence nanoparticles (PLNPs) are unique optical materials emitting long-lasting luminescence after ceasing excitation. Such a unique optical feature allows luminescence detection without constant external illumination to avoid the interferences of autofluorescence and scattering light from biological fluids and tissues. Besides, near-infrared (NIR) PLNPs have advantages of deep penetration and the reactivation of the persistent luminescence (PL) by red or NIR light. These features make the application of NIR-emitting PLNPs in long-term bioimaging no longer limited by the lifetime of PL. To take full advantage of PLNPs for biological applications, the versatile strategies for bridging PLNPs and biological system become increasingly significant for the design of PLNPs-based nanoprobes. In this Account, we summarize our systematic achievements in the biological applications of PLNPs from biosensing/bioimaging to theranostics with emphasizing the engineering strategies for fabricating specific PLNPs-based nanoprobes. We take surface engineering and manipulating energy transfer as the major principles to design various PLNPs-based nanoprobes based on the nature of interactions between nanoprobes and targets. We have developed target-induced formation or interruption of fluorescence resonance energy transfer systems for autofluorescence-free biosensing and imaging of cancer biomarkers. We have decorated single or dual targeting ligands on PLNPs for tumor-targeted imaging, and integrated other modal imaging agents into PLNPs for multimodal imaging. We have also employed specific functionalization for various biomedical applications including chemotherapy, photodynamic therapy, photothermal therapy, stem cells tracking and PL imaging-guided gene therapy. Besides, we have modified PLNPs with multiple functional units to achieve challenging metastatic tumor theranostics. The proposed design principle and comprehensive strategies show great potential in guiding the design of PLNPs nanoprobes and promoting further development of PLNPs in the fields of biological science and medicine. We conclude this Account by outlining the future directions to further promote the practical application of PLNPs. The novel protocols for the synthesis of small-size, monodisperse, and water-soluble PLNPs with high NIR PL intensity and superlong afterglow are the vibrant directions for the biomedical applications of PLNPs. In-depth theories and evidence on luminescence mechanism of PLNPs are highly desired for further improvement of their luminescence performance. Furthermore, other irradiations without tissue penetrating depth limit, such as X-ray, are encouraged for use in energy storage and re-excitation of PLNPs, enabling imaging in deep tissue in vivo and integrating other X-ray sensitized theranostic techniques such as computed tomography imaging and radiotherapy. Last but not least, PLNPs-based nanoprobes and the brand new hybrids of PLNPs with other nanomaterials show a bright prospect for accurate diagnosis and efficient treatment of diseases besides tumors.

Smart drug carriers with intrinsic photoluminescence (PL) tracking of controllably released drugs are of great significance to indicate in real-time where, when and how the drug was released. Herein, we present a novel multifunctional poly(N-isopropylacrylamide)–Mn–ZnS (PMZS) nanocomposite for thermo- and pH-controlled release of doxorubicin (Dox) and real-time tracking of the released Dox in a PL-enhanced manner. The simple coupling of Mn–ZnS quantum dots and poly(N-isopropylacrylamide) resulted in the unique thermo- and pH-responsive PL of PMZS. There was a much higher PL intensity at 37 °C than 25 °C and a much higher PL intensity at weakly acidic pH than at neutral pH, which is promising for PL imaging in tumor microenvironments. The PL of the PMZS composite was greatly quenched upon loading of Dox (the loading content and encapsulation efficiency of PMZS composites toward Dox were 15.2% and 84.1%, respectively), but was gradually restored with the controllable release of Dox, and the restored PL intensity was proportional to the cumulative amount of Dox released. The versatility of the PMZS composite as an effective Dox carrier and real-time PL-enhanced tracking of the controllably released Dox were further proved by cell viability assays and in vitro cell imaging experiments. The simple PMZS nanocomposite was easily-synthesized, biocompatible, and promising for PL tracking of when, where and how Dox was released.

One step synthesis of ε-caprolactam from cyclohexanone and hydroxylamine used acidic ionic liquids [HSO3-b-N(CH3)HSO4 as reaction medium and catalyst were investigated. Reaction conditions were investigated to obtain the optimum conditions. The results indicate that the yield of CPO is 35.9% and the yield of CPL is 20.4% under optimal reaction conditions.

A novel strategy was presented to construct the enhanced molecularly imprinted polymer (MIP)-based room temperature phosphorescence (RTP) probe by combining the RTP of Mn-doped ZnS quantum dots (Mn-ZnS QDs) and two-fragment imprinting. Two fragments or structurally similar parts of the target analytes were used as the dummy templates. Polyethyleneimine capped Mn-ZnS (PEI-Mn-ZnS) QDs, offering the binding sites to interact with the carboxyl groups of templates, were imbedded into MIPs by the hydrolysis of tetraethoxysilane. The rebinding of the target analytes to their fragments' cavities (recognition sites) modulated the selective aggregation of Mn-ZnS QDs in QDs-MIPs and resulted in the RTP enhancement. This new method was suitable for the selective enhanced RTP detection of nonphosphorescent analytes without any derivatization and inducers. The proposed methodology was applied to construct the high selective enhanced MIP-based RTP probe for domoic acid (DA) detection. The RTP enhancement of two-fragment imprinting silica was about 2 times of one-fragment imprinting silica and 4 times of the nonimprinting silica. The two-fragment imprinting silica exhibited the linear RTP enhancement to DA in the range of 0.25-3.5 μM in buffer and 0.25-1.5 μM in shellfish sample. The precision for 11 replicate detections of 1.25 μM DA was 0.65% (RSD), and the limit of detection was 67 nM in buffer and 2.0 μg g(-1) wet weight (w/w) in shellfish sample.

We present herein a new single probe, polyethyleneimine (PEI)/MnZnS nanocomposite, for two-color imaging and three-dimensional sensing. The PEI/MnZnS nanocomposite possesses unique, individually excited, two-color, photoluminescence (PL) emissions at λ=495 and 585 nm; this allows two-color imaging of the same space just by changing the excitation wavelength in situ. Moreover, the two PL bands of the nanocomposite are orthogonal, which allows the discrimination of eight proteins just by recording the three-channel optical signals of the single probe. The two PL bands of the PEI/MnZnS composite are capable of distinguishing eight proteins at 0.5 μM, whereas the three-channel signals (two PL bands and light scattering) can discriminate these proteins at no less than 0.25 μM.

We presented a novel fluorescence anisotropy (FA) method for the noninvasive, effective, simple, and convenient discrimination of the symmetric and asymmetric distribution of the ligands on Mn-doped ZnS quantum dots (QDs). The symmetric or asymmetric distribution of mercaptopropionic acid (MPA) and NH2-polyethylene glycol-CH3 (PEG-m, MW 2000) was controlled by the condensation reaction of the carboxyl of MPA and the amino of PEG-m with or without the masking by the amino-functionalized silica nanoparticles. The ligand-asymmetric Janus-QDs were obtained with the masking, whereas the ligand-symmetric PEG-QDs were gained without masking. The FA values of the QDs could not only distinguish the ligand symmetric PEG-QDs from the ligand asymmetric Janus-QDs but also discriminate the QDs with a different PEG-m amount. Besides, the FA assay also has superiority over the dynamic light scattering (DLS) and photoluminescence (PL) methods in discriminating the interaction of Janus-QDs or PEG-QDs with protamine (the se...

Neodymium (Nd(3+)) doped nanomaterials exhibited the unique near infrared (NIR) luminescence properties. However, the application of Nd-doped nanomaterials to chemosensors was rarely explored. Herein, the water-soluble 2-aminoethyl dihydrogen phosphate stabilized Nd-doped LaF(3) (ADP-Nd-LaF(3)) nanoparticles were explored as the NIR probe for chemosensors. The NIR emission intensity at 1061 nm of ADP-Nd-LaF(3) nanoparticles kept stable in the aqueous solution of various pH and coexisting of most common metal ions except copper ion, consequently, the ADP-Nd-LaF(3) nanoparticles were developed as a high selective NIR probe for Cu(II). The NIR emission of ADP-Nd-LaF(3) exhibits a linear quenching response to Cu(II) in the range 5-100 μM, with a detection limit of 0.8 μM. The precision of eleven replicate detections of 5 μM Cu(II) was 0.5% (RSD). The recovery of spiked Cu(II) in human urine and waste water samples ranged from 102 to 109%. The possible mechanism of Cu(II)-induced fluorescence quenching of ADP-Nd-LaF(3) nanoparticles was also discussed.

The outstanding properties such as large surface area, diverse structure, and accessible tunnels and cages make metal organic frameworks (MOFs) attractive as novel separation media in separation sciences. However, the utilization of MOFs in EKC has not been reported before. Here we show the exploration of zeolitic imidazolate framework-8 (ZIF-8), one of famous MOFs, as the pseudostationary phase (PSP) in EKC. ZIF-8 nanocrystals were used as the PSP through dispersing in the running buffer (20 mM phosphate solution containing a 1% v/v methanol (pH 9.2)) to enhance the separation of the phenolic isomers (p-benzenediol, m-benzenediol, o-benzenediol, m-nitrophenol, p-nitrophenol, and o-nitrophenol). ZIF-8 nanocrystals in the running buffer were negatively charged, and interacted with the phenolic hydroxyl groups of the analytes, and thus greatly improved the separation of the phenolic isomers. Inclusion of 200 mg L-(1) ZIF-8 in the running buffer as the background electrolyte gave a baseline separation of the phenolic isomers within 4 min. The relative standard deviations for five replicate separations of the phenolic isomers were 0.2-1.1% for migration time and 4.5-9.7% for peak area. The limits of detection varied from 0.44 to 2.0 mg L-(1) . The results show that nanosized MOFs are promising for application in EKC.

Lab-on-a-nanoparticle: the triple-channel optical properties of Mn-doped ZnS quantum dots (fluorescence, phosphorescence, and light scattering) are explored to develop a multidimensional sensing device for the discrimination of proteins in a lab-on-a-nanoparticle approach.

As volatile organic compounds (VOCs) are a major group of air pollutants, development of materials for efficient adsorption and removal of VOCs is of great significance in both environmental and analytical sciences. Here we report metal-organic frameworks (MOFs) MIL-101 for the effective adsorption of VOCs at atmospheric pressure. A simple device was designed for quartz crystal microbalance (QCM), and six VOCs with various functional groups and polarities, i.e., n-hexane, toluene, methanol, butanone, dichloromethane, and n-butylamine, were chosen as targets to probe the adsorption properties of MIL-101. The developed device allows measurement of the adsorption isotherms and monitoring of the dynamic process for the adsorption of VOCs on MOFs, and also provides a useful tool for characterization of MOFs. The adsorption isotherms of the VOCs on MIL-101 followed the Dubinin-Astakhov equation with the characteristic energy from 5.70 (methanol) to 9.13 kJ mol(-1) (n-butylamine), Astakhov exponent from 0.50 (n-butylamine) to 3.03 (n-hexane), and the limiting adsorption capacity from 0.08 (n-hexane) to 12.8 (n-butylamine) mmol g(-1). MIL-101 exhibited the strongest affinity to n-butylamine, but the weakest affinity to n-hexane. The determined Astakhov exponents and the isosteric heats of adsorption revealed the energetic heterogeneity of MIL-101. MIL-101 showed the most energetically homogeneous for n-hexane, but the most energetically heterogeneous for n-butylamine. The dynamic process of adsorption monitored by the QCM system demonstrated the distribution of the sorption sites within MIL-101. The metal sites within the MIL-101 were vital in adsorption process. MIL-101 gave much higher affinity and bigger adsorption capacity to VOCs than activated carbon, offering great potential for real applications in the adsorption and removal of VOCs.

Although quantum dot (QD)-based room temperature phosphorescence (RTP) probes are promising for practical applications in complex matrixes such as environmental, food and biological samples, current QD-based-RTP probes are not only quite limited but also exclusively based on the RTP quenching mechanism. Here we report an ascorbic acid (AA) induced phosphorescence enhancement of sodium tripolyphosphate-capped Mn-doped ZnS QDs, and its application for turn-on RTP detection. The chelating ability allows AA to extract the Mn and Zn from the surface of the QDs and to generate more holes which are subsequently trapped by Mn(2+), while the reducing property permits AA to reduce Mn(3+) to Mn(2+) in the excited state, thereby enhancing the excitation and orange emission of the QDs. The enhanced RTP intensity of the QDs increases linearly with the concentration of AA in the range of 0.05-0.8 μM. Thus, a QD-based RTP probe for AA is developed. The proposed QD-based turn-on RTP probe avoids tedious sample pretreatment, and offers good sensitivity and selectivity for AA in the presence of the main relevant metal ions and other molecules in biological fluids. The limit of detection (3s) of the developed method is 9 nM AA, and the relative standard deviation is 4.8 % for 11 replicate detections of 0.1 μM AA. The developed method is successfully applied to the analysis of real samples of human urine and plasma for AA with quantitative recoveries from 96 to 105 %.

Integrating various enzymes with nanomaterials provides various nanohybrids with new possibilities in biosensor applications. Furthermore, the enzymatic activity and stability are also improved due to the large surface area of nanomaterials. Here we report the conjugation of glucose oxidase (GOD) onto phosphorescent Mn-doped ZnS quantum dots (QDs) using 1-ethyl-3-(3-dimethylaminopropy)carbodiimide (EDC)/N-hydroxysuccinimide (NHS) as coupling reagents for glucose biosensing based on the effective quenching of the room temperature phosphorescence (RTP) of Mn-doped ZnS QDs by the H(2)O(2) generated from GOD-catalyzed oxidation of glucose. The obtained bioconjugate not only provided improved enzymatic performance with Michaelis-Menten constant of 0.70 mM but also favored biological applications because the phosphorescent detection mode avoided the interference from autofluorescence and scattering light from the biological matrix. In addition, the GOD-conjugated Mn-doped ZnS QDs showed better thermal stability in the temperature range of 20-80 degrees C. The GOD-Mn-doped ZnS QDs based RTP sensor for glucose gave a detection limit of 3 microM and two linear ranges from 10 microM to 0.1 mM and from 0.1 to 1 mM. The developed biosensor was successfully applied to the determination of glucose in real serum samples without the need for any complicated sample pretreatments.

Metal−organic frameworks (MOFs) with metal-containing secondary building units and organic linkers have great potential for the separation of isomers. In this work, the adsorption and separation of xylene isomers and ethylbenzene (EB) on two Zn−terephthalate MOFs (MOF-5 and MOF-monoclinic) were studied by means of pulse gas chromatography, static vapor-phase adsorption, and breakthrough adsorption. The two studied Zn−terephthalate MOFs showed different selectivity and efficiency for the separation of xylene isomers and EB. On MOF-5, EB eluted first, while other isomers eluted at the same time. MOF-monoclinic showed a preferable adsorption of p-xylene over other isomers. The adsorption and separation of xylene isomers and EB were equilibrium-constant-controlled on MOF-5 and diffusion-dominated on MOF-monoclinic. On the basis of the measured McReynolds constants, MOF-5 was characterized as a stationary phase of nonpolarity, whereas MOF-monoclinic as a stationary phase of intermediate polarity for gas chroma...

A new type of molecularly imprinted polymer (MIP)-based room-temperature phosphorescence (RTP) optosensor was developed by anchoring the MIP layer on the surface of Mn-doped ZnS quantum dots (QDs) via a surface molecular imprinting process. The synergetic combination of the RTP property of the Mn-doped ZnS QDs and the merits of the surface imprinting polymers not only improves the RTP selectivity of the Mn-doped ZnS QDs but also makes the MIP-based RTP optosensor also applicable to selective detecting of those nonphosphorescent analytes without the need for any inducers and derivatization. The new MIP-based RTP sensing protocol was applied to detect trace pentachlorophenol (PCP) in water samples without the interference of autofluorescence and scattering light of matrixes. The detection limit for PCP was 86 nM, and the precision for five replicate detections of 0.4 microM PCP was 2.8% (relative standard deviation). The recovery of spiked PCP in river water samples ranged from 93% to 106%.

While most research works focus on the development of quantum dots (QDs)-based fluorescence sensors, much less attention is paid to the phosphorescence properties of QDs and their potential for phosphorescence detection. In this work, the phosphorescence property of Mn-doped ZnS QDs is explored to develop a novel room-temperature phosphorescence (RTP) method for the facile, rapid, cost-effective, sensitive, and selective detection of enoxacin in biological fluids. The Mn-doped ZnS QDs-based RTP method reported here does not need the use of deoxidants and other inducers and allows the detection of enoxacin in biological fluids without interference from autofluorescence and the scattering light of the matrix. The Mn-doped ZnS QDs offer excellent selectivity for detecting enoxacin in the presence of the main relevant metal ions in biological fluids, biomolecules, and other kinds of antibiotics. Quenching of the phosphorescence emission due to the addition of enoxacin at 1.0 microM is unaffected by 5000-fold excesses of Na (+) and 10000-fold excesses of K (+), Mg (2+), and Ca (2+). Amino acids such as tryptophan, histidine, and l-cysteine at 1000-fold concentration of enoxacin do not affect the detection of enoxacin. Glucose does not affect the detection at 10000-fold concentration of enoxacin. Typical coadministers (mainly other types of antibiotics) such as ceftezole, cefoperazone, oxacillin, and kalii dehydrographolidi succinas are permitted at 50-, 10-, 100-, and 50-fold excesses, respectively, without interference with the detection of enoxacin. The precision for 11 replicate detections of 0.4 microM enoxacin is 1.8% (RSD). The detection limit for enoxacin is 58.6 nM. The recovery of spiked enoxacin in human urine and serum samples ranges from 94 to 104%. The developed Mn-doped ZnS QDs-based RTP method is employed to monitor the time-dependent concentration of enoxacin in urine from a healthy volunteer after the oral medication of enoxacin. The investigation provides evidence that doped QDs are promising for RTP detection in further applications.

A room temperature ionic liquid (RTIL)-mediated nonhydrolytic sol-gel (NHSG) protocol was explored for the fabrication of new molecularly imprinted silica-based hybrid monoliths for chiral separation of a basic template zolmitriptan by CEC. The RTIL-mediated NHSG protocol involved free-radical copolymerization and NHSG process. Three carboxylic acids (trifluoromethyl acrylic acid, cinnamic acid, and methacrylic acid (MAA)) were examined as both the functional monomers and the catalysts for the NHSG condensation of methacryloxypropyltrimethoxysilane (MPTMS) to form silica-based framework. RTIL was incorporated to reduce gel shrinkage and also to act as the pore template. The effects of carboxylic acids and RTIL on the performance of the silica-based hybrid molecularly imprinted polymer (MIP) monoliths were investigated in detail to realize excellent chiral recognition and to give new insights into the mechanism of the RTIL-mediated NHSG strategy. Excellent chiral separation of (R)/(S)-zolmitriptan was achieved when the molar ratio of MAA to MPTMS was 1:4 and 1:2 with RTIL involved. The synergism of the free-radical copolymerization of the C=C bond of carboxylic acids and MPTMS with the NHSG condensation of MPTMS catalyzed by the carboxylic acids was demonstrated. The incorporation of RTIL increased porosity, and hence improved selectivity of the prepared hybrid monoliths.

For the widely used "off-on" fluorescence (or phosphorescence) resonance energy transfer (FRET or PRET) system, the separation of donors and acceptors species was vital for enhancing the sensitivity. To date, separation of free donors from FRET/PRET inhibition systems was somewhat not convenient, whereas separation of the target-induced far-between acceptors has hardly been reported yet. We presented here a novel magnetic separation-assistant fluorescence resonance energy transfer (MS-FRET) inhibition strategy for highly sensitive detection of nucleolin using Cy5.5-AS1411 as the donor and Fe3O4-polypyrrole core-shell (Fe3O4@PPY) nanoparticles as the NIR quenching acceptor. Due to hydrophobic interaction and π-π stacking of AS1411 and PPY, Cy5.5-AS1411 was bound onto the surface of Fe3O4@PPY, resulting in 90% of fluorescence quenching of Cy5.5-AS1411. Owing to the much stronger specific interaction of AS1411 and nucleolin, the presence of nucleolin could take Cy5.5-AS1411 apart from Fe3O4@PPY and restore the fluorescence of Cy5.5-AS1411. The superparamagnetism of Fe3O4@PPY enabled all separations and fluorescence measurements complete in the same quartz cell, and thus allowed the convenient but accurate comparison of the sensitivity and fluorescence recovery in the cases of separation or nonseparation. Compared to nonseparation FRET inhibition, the separation of free Cy5.5-AS1411 from Cy5.5-AS1411-Fe3O4@PPY solution (the first magnetic separation, MS-1) had as high as 25-fold enhancement of the sensitivity, whereas further separation of the nucleolin-inducing far-between Fe3O4@PPY from the FRET inhibition solution (the second magnetic separation, MS-2) could further enhance the sensitivity to 35-fold. Finally, the MS-FRET inhibition assay displayed the linear range of 0.625-27.5 μg L(-1) (8.1-359 pM) and detection limit of 0.04 μg L(-1) (0.05 pM) of nucleolin. The fluorescence intensity recovery (the percentage ratio of the final restoring fluorescence intensity to the quenched fluorescence intensity of Cy5.5-AS1411 solution by 0.09 g L(-1) Fe3O4@PPY) was enhanced from 36% (for nonseparation) to 56% (for two magnetic separations). This is the first accurate evaluation for the effect of separating donor/acceptor species on the FRET inhibition assay.

Convenient reading out and/or determination of ionic strength (IS) is of great significance for both scientific research and real life applications. We presented here a novel method for the rapid and sensitive IS assay based on the electrolyte-induced sensitive wavelength blueshifts of the reflection spectra of polyacrylate capped Fe3O4 magnetic photonic crystals (PA-Fe3O4-MPCs). For HCl, MgSO4 and the common electrolytes corresponding to the salinity of seawater (including NaCl, KCl, MgCl2, CaCl2, Na2SO4 and their mixtures), the PA-Fe3O4-MPCs displayed wavelength blueshifts identical to the total IS of the aqueous solutions, regardless of the kind of above-mentioned electrolytes in the solutions. Besides, the PA-Fe3O4-MPCs exhibited relatively high sensitivity (an average of 294 nm L mmol(-1) in the range of 0.05-0.30 mmol L(-1), and an even higher value of 386 nm L mmol(-1) at 0.05-0.15 mmol L(-1)) and fast response (within 8 s) to the IS of aqueous solutions. The relative standard deviation (RSD) for IS (NaCl, 0.1 mmol L(-1)) was 4.4% (n = 5). The developed method was applied to determine the salinity of seawater samples, and the determined results were validated by the traditional standard chlorinity titration and electric conductimetry method. The recoveries were in the range of 92-104%. The proposed PA-Fe3O4-MPCs based reflectometry method would have great potential for IS and salinity assays.

The racemic naproxen was selectively recognized by capillary electrochromatography (CEC) on an (S)-naproxen-imprinted monolith, which was prepared by an in situ thermal-initiated polymerization. The recognition selectivity of a selected monolith strictly relied on the CEC conditions involved. The factors that influence the imprinting selectivity as well as the electroosmotic flow (EOF), including the applied voltage, organic solvent, salt concentration and pH value of the buffer, column temperature, and surfactant modifiers were systematically studied. Once the column was prepared, the experiment results showed that the successful chiral recognition was dependent on CEC variables. For example: the recognition could be observed in acetonitrile and ethanol electrolytes, while methanol and dimethyl sulfoxide (DMSO) electrolytes had no chiral recognition ability. The buffer with pH values of 2.6 or 3.0 at a higher salt concentration had chiral recognition ability. Column temperatures of 25-35 degrees C were optimal. Three surfactants, sodium dodecyl sulfate (SDS), cetyltrimethylammonium bromide (CTAB), and polyoxyethylene sorbitan monolaurate (Tween 20), can improve the recognition. Baseline resolution was obtained under optimized conditions and the column efficiency of the later eluent (S)-naproxen was 90 000 plates/m.

Messenger RNA plays a pivotal role in regulating cellular activities. The expression dynamics of specific mRNA contains substantial information on the intracellular milieu. Unlike the imaging of stationary mRNAs, real-time intracellular imaging of the dynamics of mRNA expression is of great value for investigating mRNA biology and exploring specific cellular cascades. In addition to advanced imaging methods, timely extracellular stimulation is another key factor in regulating the mRNA expression repertoire. The integration of effective stimulation and imaging into a single robust system would significantly improve stimulation efficiency and imaging accuracy, producing fewer unwanted artifacts. In this study, we developed a multifunctional nanocomplex to enable self-activating and spatiotemporal imaging of the dynamics of mRNA sequential expression during the neural stem cell differentiation process. This nanocomplex showed improved enzymatic stability, fast recognition kinetics, and high specificity. With a mechanism regulated by endogenous cell machinery, this nanocomplex realized the successive stimulating motif release and the dynamic imaging of chronological mRNA expression during neural stem cell differentiation without the use of transgenetic manipulation. The dynamic imaging montage of mRNA expression ultimately facilitated genetic heterogeneity analysis. In vivo lateral ventricle injection of this nanocomplex enabled endogenous neural stem cell activation and labeling at their specific differentiation stages. This nanocomplex is highly amenable as an alternative tool to explore the dynamics of intricate mRNA activities in various physiological and pathological conditions.

Ultrasensitive and quantitative detection of cancer biomarkers is an unmet challenge because of their ultralow concentrations in clinical samples. Although gold nanoparticle (AuNP)-based immunoassays offer high sensitivity, they were unable to quantitatively detect targets of interest most likely due to their very narrow linear ranges. This article describes a quantitative colorimetric immunoassay based on glucose oxidase (GOx)-catalyzed growth of 5 nm AuNPs that can detect cancer biomarkers from attomolar to picomolar levels. In addition, the limit of detection (LOD) of prostate-specific antigen (PSA) of this approach (93 aM) exceeds that of commercial enzyme-linked immunosorbent assay (ELISA) (6.3 pM) by more than 4 orders of magnitude. The emergence of red or purple color based on enzyme-catalyzed growth of 5 nm AuNPs in the presence of target antigen is particularly suitable for point-of-care (POC) diagnostics in both resource-rich and resource-limited settings.

Discrimination of glycoproteins with different glycans is a significant but difficult issue. We presented here a new strategy for strengthening the discrimination of glycoproteins by introducing a new signaling channel, fluorescence polarization (FP), into a "single probe with three signaling channels" sensor array. The single probe was aminophenylboronic-acid-conjugated poly(acrylic acid)-Mn-doped ZnS quantum dots, and the three signaling channels were FP, room temperature phosphorescence and light scattering. Ten glycoproteins, including ovalbumin, fibrinogen, transferrin, horseradish peroxidase, vascular endothelial growth factor, immunoglobulin G, avidin, hyaluronidase, cellulase R-10, and glucose oxidase, were involved for evaluating the discriminating capability. The introduction of the FP signaling channel improved the discriminating power of the sensor array, so that the 10 glycoproteins at 0.15 μM could be well discriminated both in PBS buffer and in the presence of human serum sample. The identification accuracy of the unknown samples was 96.25% (77 out of 80) at the 0.15 μM level and 97.50% (78 out of 80) at the 0.2 μM level. The integration of the signaling patterns with different responsive principles was demonstrated as the promising way to enhance the discrimination power of the single-probe-based sensor arrays.

Rapid and selective enrichment of phosphopeptides from complex biological samples is essential and challenging in phosphorylated proteomics. We present the direct growth of the ultrathin YPO4 shell on the surface of polyacrylate capped secondary Fe3O4 microspheres (PA-Fe3O4@YPO4) for the rapid and selective trapping phosphopeptides from complex samples. The prepared PA-Fe3O4@YPO4 could be rapidly harvested in the presence of an applied magnetic field and easily re-dispersed in solutions after removing the external magnet. The ultrathin YPO4 shell on super-hydrophilic PA-Fe3O4 has the advantages of fast adsorption/desorption dynamics and low non-specific adsorption, thus trapping of phosphopeptides from the tryptic digests mixture of β-casein/BSA with molar ratio of 1/300 is achieved in 20s adsorption/desorption time. Two phosphopeptides can still be detected with a signal to noise ratio (S/N) over 3 when the amount of β-casein was as low as 8 fmol.

A room-temperature phosphorescence (RTP) strategy was developed for direct, additive-free discrimination of catechol from resorcinol and hydroquinone based on sodium tripolyphosphate capped Mn-doped ZnS quantum dots (STPP-Mn-ZnS QDs). The RTP response of STPP-Mn-ZnS QDs to the three isomers was pH-dependent, and the greatest difference in the RTP response to the isomers was observed at pH 8.0: catechol enhanced the RTP intensity of the QDs, while resorcinol and hydroquinone had little effect on the RTP intensity of the QDs. The enhanced RTP intensity of 1 μM catechol was not affected by the coexistence of 30 μM resorcinol and 50 μM hydroquinone at pH 8.0. The detection limit of this RTP method was 53 nM catechol, and the precision was 3.2% (relative standard deviation) for five replicate detections of 1 μM catechol. The discrimination mechanism was ascribed to the weak bonded ligand of STPP-Mn-ZnS QDs and the different interaction between the three isomers and STPP-Mn-ZnS QDs. The strong binding of catechol to Zn resulted in the extraction of Zn from the surface of STPP-Mn-ZnS QDs and the generation of holes that were trapped by Mn(2+) to form Mn(3+). Catechol also promoted the reduction of Mn(3+) into Mn(2+) excited state, thus ultimately inducing the enhanced RTP response of STPP-Mn-ZnS QDs.

Metal–organic framework MIL-53(Al) was explored as the stationary phase for high-performance liquid chromatographic separation of position isomers using a binary and/or polar mobile phase. Baseline separations of xylene, dichlorobenzene, chlorotoluene and nitrophenol isomers were achieved on the slurry-packed MIL-53(Al) column with high resolution and good precision. The effects of mobile phase composition, injected sample mass and temperature were investigated. The separation of xylene, dichlorobenzene, chlorotoluene and nitrophenol isomers on MIL-53(Al) were controlled by entropy change.

Metal-organic frameworks (MOFs) were employed to design tandem molecular sieves as a dual platform for selective solid-phase microextraction (SPME) and high-resolution gas chromatographic (GC) separation of target analytes in complex matrixes. An elegant combination of a ZIF-8-coated fiber for SPME with a ZIF-8-coated capillary for GC allows selective extraction and separation of n-alkanes from complex matrixes such as petroleum-based fuel and biological fluids. The proposed tandem ZIF-8 molecular sieves not only offered good enhancement factors from 235 (hexane) to 1212 (nonane), but also exhibited wide linearity with 3 orders of magnitude for the tested linear alkanes. The limits of detection for the linear alkanes ranged from 0.46 ng L(-1) (nonane) to 1.06 ng L(-1)(hexane). The relative standard deviations of retention time, peak area, peak height, and half peak width for five replicate determinations of the tested n-alkanes at 30 ng L(-1) were 0.02-0.26%, 1.9-8.6%, 1.4-6.0%, and 1.3-7.2%, respectively. The developed tandem ZIF-8 molecular sieves were further used for the determination of linear alkanes in petroleum-based fuel and human serum. The large diversity in structure and pore size allows various combinations of MOFs for designing an MOF-based tandem molecular sieve platform to achieve different selectivities in extraction and chromatographic separation and to solve headache problems in complex real sample analysis.

A specific resonance light scattering bioassay for homocysteine is developed on the basis of target-involved assembly of polyethyleneimine-capped Ag-nanoclusters. The bioassay permits discriminating homocysteine from cysteine, glutathione and other amino acids, and allows sensitive and selective detection of homocysteine with a detection limit of 42 nM.

Persistent-luminescence nanoparticles (PLNPs) are promising as a new generation of photoluminescent probes for detection of biomolecules and bioimaging. Here we report a fluorescence resonance energy transfer (FRET) inhibition assay for α-fetoprotein (AFP) excreted during cancer cell growth using water-soluble functionalized PLNPs based on Eu2+- and Dy3+-doped Ca1.86Mg0.14ZnSi2O7. Polyethyleneimine-coated PLNPs were conjugated with AFP-antibody-coated gold nanoparticles as a sensitive and specific persistent photoluminescence probe for detection of AFP in serum samples and imaging of AFP excreted during cancer cell growth. Such PLNPs do not contain toxic heavy metals. Their long-lasting afterglow nature allows detection and imaging without external illumination, thereby eliminating the autofluorescence and scattering light from biological matrixes encountered under in situ excitation.

A facile strong inorganic acid-initiated methacrylate polymerization strategy was developed for fabricating monolithic columns at room temperature. The prepared monoliths were characterized by FTIR spectrometry, mercury intrusion porosimeter and SEM, while their performance was evaluated by CEC for the separation of various types of compounds including alkyl benzenes, polycyclic aromatic hydrocarbons, nonsteroidal anti-inflammatory drugs, anilines, and nitrophenol isomers. The column-to-column and batch-to-batch reproducibility for the prepared monoliths in terms of the RSD of EOF flow velocity, retention factor, and the minimum plate height of naphthalene ranged from 3.4 to 12.4%. The fabricated monoliths gave excellent performance for the separation of the test neutral compounds with the theoretical plates of 170 000–232 000 plates per meter for thiourea, and 77 400–112 300 plates per meter for naphthalene. The proposed strong inorganic acid-initiated methacrylate polymerization strategy is a promising alternative for fabricating organic polymer-based monoliths.

Metal-organic frameworks (MOFs) have received great attention due to their fascinating structures and intriguing potential applications in various fields. Herein, we report the first example of the utilization of MOFs for solid-phase microextraction (SPME). MOF-199 with unique pores and open metal sites (Lewis acid sites) was employed as the coating for SPME fiber to extract volatile and harmful benzene homologues. The SPME fiber was fabricated by in situ hydrothermal growth of thin MOF-199 films on etched stainless steel wire. The MOF-199-coated fiber not only offered large enhancement factors from 19,613 (benzene) to 110,860 (p-xylene), but also exhibited wide linearity with 3 orders of magnitude for the tested benzene homologues. The limits of detection for the benzene homologues were 8.3-23.3 ng L(-1). The relative standard deviation (RSD) for six replicate extractions using one SPME fiber ranged from 2.0% to 7.7%. The fiber-to-fiber reproducibility for three parallel prepared fibers was 3.5%-9.4% (RSD). Indoor air samples were analyzed for the benzene homologues using the SPME with the MOF-199-coated fiber in combination with gas chromatography-flame ionization detection. The recoveries for the spiked benzene homologues in the collected indoor air samples were in the range of 87%-106%. The high affinity of the MOF-199-coated fiber to benzene homologues resulted from the combined effects of the large surface area and the unique porous structure of the MOF-199, the pi-pi interactions of the aromatic rings of the analytes with the framework 1,3,5-benzenetricarboxylic acid molecules, and the pi-complexation of the electron-rich analytes to the Lewis acid sites in the pores of MOF-199.

In the title compound, C17H26O, the cyclohexyl ring adopts a chair conformation with the C-atom substituents in equatorial sites. The H atom of the O—H group is disordered over two positions of equal occupancy. In the crystal, O—H...O hydrogen bonds lead to [010] chains.

A fluorescent indicator-displacement molecular imprinting sensor array based on phenylboronic acid functionalized mesoporous silica was developed for discriminating saccharides. D-Fructose imprinted material (FruIM), D-xylose imprinted material (XylIM) together with a control blank nonimprinted material (NIM) were synthesized as the elements of the imprinting sensor array. Spectrofluorimetric titrations of the three materials with eight selected saccharides were carried out, and Stern-Volmer quenching constants (K(SV)) of NIM, FruIM, and XylIM with the eight selected saccharides were obtained to investigate the interaction of the materials with saccharides. The present approach couples molecular imprinting technique to indicator-displacement strategy with the use of one conventional saccharide receptor (phenylboronic acid) and one commercially available fluorescent dye (Alizarin Red S., ARS) as the indicator, and allows identifying two template saccharides (D-fructose and D-xylose) plus eight nontemplate saccharides (D-arabinose, D-glucose, D-galactose, D-mannose, L-sorbose, D-ribose, L-rhamnose and sucrose). The principal component analysis (PCA) plot shows a clear discrimination of the 10 tested saccharides at 100 mM and the first principal component possesses 94.8% of the variation. Besides, the developed saccharide imprinted sensor array is successfully applied to discriminating three brands of orange juice beverage.

Simple plan! Nanohybrids have been built from capped Mn-doped ZnS quantum dots and octa(3-aminopropyl)octasilsequioxane octahydrochloride (OA-POSS) by means of electrostatic self-assembly for the development of a novel room-temperature phosphorescence sensor for DNA sensing in biological fluids (see graphic).

We report an ion imprinted mesoporous silica based fluorescence turn-on sensor array for discrimination of metal ions. A novel fluorescent functional monomer containing an 8-hydroxyquinoline (8-HQ) moiety in combination with one-pot co-condensation method was employed to prepare fluorescent ion imprinted mesoporous silica. The imprinted materials for Zn(2+) and Cd(2+) as well as a control blank non-imprinted material (NIM) were synthesized. With the covalently anchored organic fluorophore in the inorganic mesoporous silica matrix, the binding of metal ions to the imprinting site was directly transformed into fluorescence signals. Both the imprinted materials displayed faster binding kinetics toward metal ions than NIM. Apparent binding constants (adsorption constants) for the materials with the metal ions in water were determined by a Langmuir-type analysis of the spectrofluorimetric titration data. The sensor array composed of the three materials allows discriminating the two template metal ions (Zn(2+) and Cd(2+)) plus three non-template metal ions (Mg(2+), Ca(2+) and Al(3+)) at two different concentrations. This work proves that using a simple fluorescent receptor can provide a pattern based fluorescent sensing system by taking advantage of the imprinting effect.