Novel biocompatible N-rich AIE fluorescent probe for live cell imaging and visual onsite detection of uranium.

A sensitive and biocompatible N-rich probe for rapid visual uranium detection was constructed by grafting two trianiline groups to 2,6-bis(aminomethyl)pyridine. Possessing excellent aggregation-induced emission (AIE) property and the advantages to form multidentate chelate with U selectively, the probe has been applied successfully to visualize uranium in complex environmental water samples and living cells, demonstrating outstanding anti-interference ability against large equivalent of different ions over a wide effective pH range. A large linear range (1.0 × 10-7-9.0 × 10-7 mol/L) and low detection limit (72.6 nmol/L, 17.28 ppb) were achieved for the visual determination of uranium. The recognition mechanism, photophysical properties, analytical performance and cytotoxicity were systematically investigated, demonstrating high potential for fast risk assessment of uranium pollution in field and in vivo.

"Two-in-one" dual-function luminescent MOF hydrogel for onsite ultra-sensitive detection and efficient enrichment of radioactive uranium in water.

In consideration of the severe hazards of radioactive uranium pollution and the growing demand of uranium resources, the novel sensor/adsorbent composite was creatively developed to integrate the dual functions for on-site detection of uranium contamination and efficient recovery of uranium resources. By hybridizing the luminescent 3D terbium (III) metal-organic framework (Tb-MOF) with sodium alginate (SA) gel using terbium (III) as cross-linker, the Tb-MOF/Tb-AG was fabricated with multi-luminescence centers and sufficient binding sites for uranium. Notably, the ultra-high sensitivity with detection limit as low as 1.2 ppt was achieved, which was 4 orders of magnitude lower than the uranium contamination standard in drinking water (USEPA) and even comparable to the sensitivity of the ICP-MS. Furthermore, the very wide quantification range (1.0 ×10-9-5.0 ×10-4 mol/L), remarkable adsorption capacity (549.0 mg/g) and outstanding anti-interference ability have been achieved without sophisticated sample preparation procedures. Applied in complex natural water samples from Uranium Tailings and the Pearl River, this method has shown good detection accuracy. The ultra high sensitivity and great adsorption capacity for uranium could be ascribed to the synergistic coordination, hydrogen bonding and ion exchange between uranium and Tb-MOF/Tb-AG. The mechanisms were explored by infrared spectroscopy, batch experiments, X-ray photoelectron studies and energy dispersive spectroscopic studies. In addition, the Tb-MOF/Tb-AG can be reused for uranium adsorption.

Novel biocompatible and sensitive visual sensor based on aggregation-induced emission for on-site detection of radioactive uranium in water and live cell imaging.

In consideration of the severe hazards of radioactive uranium pollution, the rapid assessment of uranium in field and in vivo are urgently needed. In this work a novel biocompatible and sensitive visual fluorescent sensor based on aggregation-induced emission (AIE) was designed for onsite detection of UO22+ in complex environmental samples, including wastewater from Uranium Plant, river water and living cell. The AIE-active sensor (named as TPA-SP) was prepared with a "bottom-up" strategy by introducing a trianiline group (TPA) with a single-bond rotatable helix structure into the salicylaldehyde Schiff-base molecule. The photophysical properties, cytotoxicity test, recognition mechanism and the analytical performance for the detection of UO22+ in actual water samples and cell imaging were systematically investigated. TPA-SP exhibited high sensitivity and selectivity toward UO22+ as well as outstanding anti-interference ability against large equivalent of different ions in a wide effective pH range. A good linear relationship in the UO22+ concentration range of 0.05-1 µM was obtained with a low limit of detection (LOD) of 39.4 nM (9.38 ppb) for uranium detection. The prepared visual sensor showed great potential for fast risk assessment of uranium pollution in environmental systems. In addition, our results also indicated that the TPA-SP exhibited very low cytotoxicity in cells and demonstrated great potential for uranium detection in vivo.

Synthesis and application of novel N, Si-carbon dots for the ratiometric fluorescent monitoring of the antibiotic balofloxacin in tablets and serum.

A ratiometric fluorescent probe with blue-emission fluorescence based on N, Si-doped carbon dots (N, Si-CDs) for the detection of balofloxacin (BLFX) was synthesized by simple one-pot hydrothermal carbonization using methotrexate and 3-aminopropyltriethoxysilane (APTES) as carbon materials. The obtained N, Si-CDs showed dual-emission band fluorescence characterization at 374 nm and 466 nm. Furthermore, the synthesized N, Si-CD probe exhibited evidence of ratiometric fluorescence emission characteristics (F 466/F 374) toward BLFX along with a decrease in fluorescence intensity at 374 nm and an increase in fluorescence intensity at 466 nm. Based on this probe, a highly sensitive and fast detection method for the analysis of BLFX has been established with a linear range of 1-60 µM and a low detection limit of 0.1874 µM, as well as a rapid response time of 5.0 s. The developed assay has also been successfully applied for the detection of BLFX in tablets and rat serum.

A Ratiometric Fiber Optic Sensor Based on CdTe QDs Functionalized with Glutathione and Mercaptopropionic Acid for On-Site Monitoring of Antibiotic Ciprofloxacin in Aquaculture Water.

A ratiometric fluorescence fiber-optical sensor system (RFFS) merging a Y-type optical fiber spectrometer and CdTe QDs composite functionalized with glutathione and mercaptopropionic acid (GMPA@CdTe-QDs) for highly selective and on-site detection of ciprofloxacin (CIP) in environmental water samples was designed. Our preliminary results suggested that the red fluorescence of the synthesized GMPA@CdTe-QDs was effectively quenched by CIP. Based on this, the RFFS/GMPA@CdTe-QDs system was successfully fabricated and used for highly selective and rapid detection of CIP on site in the concentration range from 0 to 45 µM with the detection limit of 0.90 µM. The established method exhibited good interference resistance to the analogues of CIP and provided a great potential platform for real-time detection of CIP residues in environmental water. In addition, the fluorescence quenching mechanism of GMPA@CdTe-QDs by CIP was also investigated by means of temperature effect, fluorescence lifetime, ultraviolet (UV) visible absorption, and fluorescent spectra. Our results suggested clearly that the red fluorescence of GMPA@CdTe-QDs was quenched by CIP via the photoinduced electron-transfer (PET) mode.

A novel fluorescence ratio probe based on dual-emission carbon dots for highly selective and sensitive detection of chlortetracycline and cell imaging.

The novel dual-emission carbon dots (DECDs) for highly selective and sensitive recognition of chlortetracycline (CTC) and cell imaging were synthesized successfully by one-step synthesis. The obtained DECDs possessed two fluorescence peaks (345 nm and 450 nm) and showed specific response to CTC, resulting in a decrease in fluorescence intensity at 345 nm, a blue shift, and an increase in fluorescence intensity at 450 nm. The obtained DECDs exhibited highly selective response to CTC and not to its analogues, such as tetracycline, doxycycline, and oxytetracycline. Thus, an excellent ratiometric probe for the detection of CTC was fabricated successfully and used for the detection of CTC in real samples with the detection limit (LOD) of 16.45 nM. More importantly, the DECDs were used for quantitative detection of CTC in living cells, which demonstrated excellent biocompatibility and broad prospects in biomedicine application. Finally, the excellent selectivity of DECDs toward CTC was attributed to the FRET mechanism and the formation of complexes.

A novel carbon dot/polyacrylamide composite hydrogel film for reversible detection of the antibacterial drug ornidazole.

A carbon dot/polyacrylamide (CDs/PAM) composite hydrogel film with stable fluorescence performance was fabricated by merging a hydrogel film and carbon dots (CDs) with blue fluorescence, which were prepared by hydrothermal synthesis using anhydrous citric acid and acrylamide as carbon sources. The obtained CDs/PAM composite hydrogel film exhibited a good fluorescence quenching effect on ornidazole (ONZ), and can be used for the quantitative detection of ONZ. In the ONZ concentration range of 5-60 µM, a good linear relationship between the fluorescence quenching efficiency of the CDs/PAM composite hydrogel film and the concentration of ONZ solution was obtained with a low detection limit of 2.35 µM. In addition, the detection system has good selectivity and strong anti-interference capacity, and can be used in repeated cycles for detection.

Determination of aldehydes in water samples by coupling magnetism-reinforced molecular imprinting monolith microextraction and non-aqueous capillary electrophoresis.

Excess 2, 4-dinitrophenylhydrazine (2, 4-DNPH) is often applied for the derivatization of aldehyde prior to the chromatographic analysis. However, the residual 2, 4-DNPH may cause background interference and limit the enrichment efficiency of trace aldehydes. To overcome the above bottle-neck problems, improve the extraction efficiency and omit the manipulation for changing the polarity of solvent for the hydrophobic analytes separation, a new method combining magnetism-reinforced in-tube solid phase microextraction (IT-SPME) technique with non-aqueous capillary electrophoresis (NACE) was developed. The monolithic extraction cartridge was prepared in situ inside a capillary and doped with magnetic molecular imprinting polymers (mMIPs). The selective and efficient extraction of the derived analytes with simultaneous removal of the superfluous derivatization agent was achieved owing to the combined effect of molecular imprinting and magnetism reinforcement. By coupling with NACE, the highly hydrophobic effluent can be analyzed directly. The LODs of the method are between 0.0032~0.0049 mg L-1 and the recoveries are between 87.3~99.8% for the tested aldehydes. The developed approach is sensitive enough for detection of surface (drinking) water. The aldehydes in real water samples have been detected by this method, showing results that are in good agreement with the standard SPE-HPLC method.

Visual test for the presence of the illegal additive ethyl anthranilate by using a photonic crystal test strip.

A test strip has been developed for the rapid detection of the illegal additive ethyl anthranilate (EA) in wine. The detection scheme is based on a combination of photonic crystal based detection and molecular imprinting based recognition. The resulting molecularly imprinted photonic crystal (MIPC) undergoes a gradual color change from green to yellow to red upon binding of EA. A semi-quantitative colorimetric card can be used to estimate the content of EA, either visually or by making use of an optical fiber spectrometer. A linear relationship was found between the Bragg diffraction peak shift and the concentration of EA in the range from 0.1 mM to 10 mM. The detection limit is 10 µM. The test has been successfully used to screening for the presence of EA in grape wine. The test strip is selective, and can be re-used after re-activation. Graphical abstract Schematic representation of the fabrication and application of the molecularly imprinted photonic crystal (MIPC) based test trip. The resulting MIPC undergoes a gradual color change from green to yellow to red upon binding of the illegal wine additive ethyl anthranilate (EA).

[Determination of carbonyls in ambient PM2.5 by coupling dummy template imprinting technology and high performance liquid chromatography].

The determination of ambient carbonyls by the derivative method inevitably leads to the introduction of extra 2,4-dinitrophenylhydrazine (2,4-DNPH) into the sample solution. Traditional solid phase extraction (SPE) materials cannot remove this interference. To address this issue, a selective molecularly imprinted solid phase extraction (MISPE) column was prepared. With 2,4-dinitroaniline (2,4-DNAN) as the dummy template, MISPE could eliminate the excessive derivative agent (2,4-DNPH) in the air samples. Consequently, the sample could be concentrated effectively while the sensitivity increased greatly. By coupling MISPE and high performance liquid chromatography (HPLC), the developed method was used to study the concentration and source of 14 carbonyls of PM2.5 during spring in Guangzhou Higher Education Mega Center. Results showed that the total concentration of carbonyls increased with the level of air pollution. Particularly, the content of isovaleraldehyde increased sharply to account for 21% of the 14 total carbonyls in the haze days. Moreover, a high positive correlation between isovaleraldehyde and propionaldehyde was found either in normal days or haze days. From the correlation analysis, it was shown that anthropogenic emissions together with photochemical reaction had contributed to the abnormally high levels of carbonyls in ambient PM2.5 in the haze days. This aspect should be further investigated.

The visual detection of anesthetics in fish based on an inverse opal photonic crystal sensor.

A novel smart sensor for the rapid and label-free detection of benzocaine has been developed based on the combination of photonic crystal (PC) and molecular imprinting polymer (MIP) techniques. A molecularly imprinted photonic crystal (MIPC) hydrogel film was prepared via a non-covalent, self-assembly approach with a PC mould. With a highly ordered inverse opal structure, the resulting benzocaine MIPC exhibited high sensitivity, smart specificity, quick response times and good regeneration abilities. It can give rise to a readable optical signal and color change upon binding with benzocaine, with a detection limit of 16.5 µg mL-1. The sensor has been successfully used to visually estimate benzocaine concentrations in fish samples. In comparison with HPLC, the developed MIPC sensor has shown satisfactory accuracy in terms of results. It has great potential for on-site screening and the visual detection of trace benzocaine in real samples.

A novel and fast responsive turn-on fluorescent probe for the highly selective detection of Cd2+ based on photo-induced electron transfer.

A novel, highly sensitive and fast responsive turn-on fluorescence probe, 2,2'-((1E,1'E)-((1,10-phenanthroline-2,9-diyl)bis(methanylylidene)) bis(azanylylidene)) diphenol (ADMPA), for Cd2+ was successfully developed based on 2,9-dimethyl-1,10-phenanthroline and o-aminophenol. ADMPA showed a remarkable fluorescence enhancement toward Cd2+ against other competing cations, owing to the suppression of the photo-induced electron transfer (PET) and CH[double bond, length as m-dash]N isomerization. A good linear relationship (R 2 = 0.9960) was obtained between the emission intensity of ADMPA and the concentration of Cd2+ (0.25-2.5 µM) with a detection limit of 29.3 nM, which was much lower than that reported in literature. The binding stoichiometry between ADMPA and Cd2+ was 2 : 1 as confirmed by the Job's Plot method, which was further confirmed by a 1H NMR titration experiment. Moreover, the ADMPA probe was successfully applied to detect Cd2+ in real water samples with a quick response time of only 6.6 s, which was about 3-40 times faster than the reported cadmium ion probe.

Determination of carbonyl pollutants adsorbed on ambient particulate matter of type PM2.5 by using magnetic molecularly imprinted microspheres for sample pretreatment and capillary electrophoresis for separation and quantitation.

The authors describe a method for the determination of carbonyl pollutants adsorbed on ambient particulate matter (diameter < 2.5 µm; PM2.5). 2,4-Dinitrophenylhydrazine (DNPH) was used to derivatize carbonyl compounds. Magnetic molecularly imprinted polymers (MMIPs) selective for 2,4-DNPH were synthesized to remove excess of the derivatization reagent 2,4-DNPH. Micellar electrokinetic chromatography (MEKC) was then applied to the separation of DNPH-derivatized carbonyl compounds. The increased sensitivity of MEKC with UV detection and the sample cleanup resulted in drastically reduced sampling times (15 min) with detection limits ranging from 0.005-0.068 µg·m-3 for different carbonyls. The method was applied to continuous monitoring of carbonyl compounds on ambient PM 2.5 for two consecutive months. The concentrations and gas-to-particle ratios of carbonyls were determined, and a statistical method was used to evaluate the correlation among different carbonyls. It was observed that the total concentration of carbonyls, especially of multi-carbon carbonyls, increases with the level of air pollution. The level of isovaleraldehyde rises sharply and accounts for 37% of total carbonyls on days with extremely humid haze. The ratio of acetaldehyde to propionaldehyde (C2/C3) decreases with the duration and heaviness of haze conditions. Results indicate that anthropogenic emissions and the characteristics of the atmosphere (e.g. temperature, sunlight, and relative humidity) are the main factors that lead to abnormally high levels of isovaleraldehyde and other carbonyls in ambient PM 2.5. Graphical abstract Schematic of a method for the determination of carbonyl pollutants adsorbed on ambient fine particle of type PM2.5. Magnetic molecularly imprinted polymers (MMIPs) were synthesized to remove the excess derivatization reagent (2,4-DNPH) in air sample prior to CE separation.

Molecularly imprinted microspheres synthesized by a simple, fast, and universal suspension polymerization for selective extraction of the topical anesthetic benzocaine in human serum and fish tissues.

A simple, fast, and universal suspension polymerization method was used to synthesize the molecularly imprinted microspheres (MIMs) for the topical anesthetic benzocaine (BZC). The desired diameter (10-20 µm) and uniform morphology of the MIMs were obtained easily by changing one or more of the synthesis conditions, including type and amount of surfactant, stirring rate, and ratio of organic to water phase. The MIMs obtained were used as a molecular-imprinting solid-phase-extraction (MISPE) material for extraction of BZC in human serum and fish tissues. The MISPE results revealed that the BZC in these biosamples could be enriched effectively after the MISPE operation. The recoveries of BZC on MIMs cartridges were higher than 90% (n = 3). Finally, an MISPE-HPLC method with UV detection was developed for highly selective extraction and fast detection of trace BZC in human serum and fish tissues. The developed method could also be used for the enrichment and detection of BZC in other complex biosamples.

Simultaneous determination of gaseous and particulate carbonyls in air by coupling micellar electrokinetic capillary chromatography with molecular imprinting solid-phase extraction.

A novel method coupling molecular imprinting solid-phase extraction (MISPE) and micellar electrokinetic capillary chromatography (MEKC) was developed to enable the hourly determination of low level of ambient carbonyls, and study their partition between gaseous phase and particulate phase. With 2,4-dinitroaniline (DNAN) as dummy imprinting template, the unreacted 2,4-Dinitrophenylhydrazine (DNPH) in sampling solution could be removed effectively using MISPE, and an average recovery of 97±5.3% (n=5) for the carbonyl-DNPH derivatives was achieved. Owing to the high enrichment due to sample clean-up, and the improvement of MEKC separation efficiency, many low abundant carbonyls could be detected by hourly in the field study.

Molecularly imprinted microspheres for the anticancer drug aminoglutethimide: synthesis, characterization, and solid-phase extraction applications in human urine samples.

Molecularly imprinted microspheres (MIMs) for the anticancer drug aminoglutethimide (AG) were synthesized by aqueous suspension polymerization. The expected size and diameter of MIMs are controlled easily by changing one of the surfactant types, ratio of organic-to-water phase or stirring rate during polymerization. The obtained MIMs exhibit specific affinity toward AG with imprinting factor of 3.11 evaluated with a chromatographic model. The resultant MIMs were used as the SPE materials for the extraction of AG from human urine. A molecularly imprinted SPE (MISPE) method coupled with HPLC has been developed for the extraction and detection of AG in urine. Our results showed that most impurities from urine can be removed effectively after a washing step and the AG has been enriched effectively after MISPE operation with the recovery of >90% (n = 3). The developed MISPE-HPLC method could be used for enrichment and detection of AG in human urine.

Synthesis and evaluation of molecularly imprinted polymeric microspheres for highly selective extraction of an anti-AIDS drug emtricitabine.

The molecularly imprinted polymeric microspheres (MIPMs, 3~5 µm), used as high-performance liquid chromatography (HPLC) and solid-phase extraction (SPE) packing materials for anti-AIDS drug emtricitabine (FTC), were synthesized by precipitation polymerization. The effects of ratio of chloroform to acetonitrile on the morphology and diameter of MIPMs were investigated. The prepared MIPMs were characterized by HPLC. The imprinting factor (2.26) suggests that the resultant MIPMs exhibit good recognition and affinity to FTC. In addition, the MIPMs were used in SPE as packing material for separation and enrichment of FTC. The recovery of FTC on MIPMs cartridge was 97.6 % in standard solution. Finally, the MIPMs cartridge was applied to extract the FTC in human serum samples. Impurities in sample have been mostly removed, and the average recovery of 92.5 % was obtained with a detection limit of 0.005 µg/mL and a linear range of 0.02~4.0 µg/mL. The method established can be used to monitor the FTC in human serum sample with good accuracy and selectivity.

Recognition characteristics of molecularly imprinted microspheres for triazine herbicides using hydrogen-bond array strategy and their analytical applications for corn and soil samples.

The homogeneous molecularly imprinted microspheres (MIMs) based on a biologically inspired hydrogen-bond array were prepared using allobarbital as the novel functional monomer and divinylbenzene as the cross-linker. The host-guest binding characteristics were examined by molecular simulation and infrared spectroscopy. The resultant MIMs were evaluated using high performance liquid chromatography and solid-phase extraction. The results obtained demonstrate that the good imprinting effect and the excellent selectivity of MIMs are mainly due to the interaction involving the formation of three-point hydrogen bond between host and guest. The complete baseline separation was obtained for five triazine analogues and a metabolite on the MIM HPLC column. The MIMs were further successfully used as a specific sorbent for selective extraction of simetryne from corn and soil samples by molecularly imprinted solid phase extraction. Detection limits and recoveries were 5.8 µg/kg and 0.14 µg/kg and 87.4-105% and 94.6-101% for simetryne in corn and soil sample, respectively.

Analysis of adenosine phosphates in HepG-2 cell by a HPLC-ESI-MS system with porous graphitic carbon as stationary phase.

A high performance liquid chromatography coupled with electrospray ionization/mass spectrometry method was developed for the determination of adenosine 5'-monophosphate (AMP), adenosine 5'-diphosphate (ADP), and adenosine 5'-triphosphate (ATP) in the extract of HepG-2 cells. The chromatographic conditions were optimized by using porous graphitic carbon as the stationary phase for the retention and separation of the AMP, ADP and ATP. Negative-ion mode ESI-MS in basic mobile phase was applied to improve the method sensitivity. An external calibration method with linear ranges from 0.22 to 57.80 microM for AMP, from 0.59 to 117.37 microM for ADP, and from 0.49 to 98.81 microM for ATP was used for quantitative analysis. The levels of ATP, ADP, and AMP in HepG-2 cells treated with benzo[a]pyrene with different time periods were determined. Total adenine nucleotides and the energy charge potential were calculated for the investigation of the effect of benzo[a]pyrene on cell energy metabolism.

Nucleoside reverse transcriptase inhibitors and their phosphorylated metabolites in human immunodeficiency virus-infected human matrices.

Highly active antiretroviral therapy (HAART) is the common treatment strategy for human immunodeficiency virus (HIV)-infected patients at present. Generally, HAART regimens apply multi-therapy drugs that contain nucleoside/nucleotide reverse transcriptase inhibitors (NRTIs), non-nucleoside/nucleotide reverse transcriptase inhibitors (NNRTIs) and protease inhibitors (PIs). Unlike NNRTIs and PIs, the active form of NRTIs is not the drug itself but its triphosphorylated (TP) metabolites in intracellular medium. Analysis of both the prodrugs or NRTIs and their intracellular metabolites is needed to provide overall information in pharmacokinetic and therapeutic effects to HIV-infected patients. Numerous publications have reported the assays for NRTIs and their phosphorylated metabolites in various biological matrices. The methods involved liquid chromatography (LC) with UV detection (LC-UV), LC with tandem mass spectrometry (LC-MS/MS), capillary electrophoresis/electrochromatography (CE/CEC) with UV detection (CE/CEC-UV) or/and MS/MS detection (CE-MS/MS). Due to the extremely low concentration of NRTIs and the phosphorylated metabolites as well as the complex biological matrices, sample pretreatment methods such as protein precipitation (PP), liquid-liquid extraction (LLE) and solid-phase extraction (SPE) have played important role in the successful analytical method development.