"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 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.

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.

Molecularly imprinted microspheres and nanospheres for di(2-ethylhexyl)phthalate prepared by precipitation polymerization.

Molecularly imprinted microspheres (MIMs, >3 microm) and nanospheres (MINs, approximately 450 nm) for the environmental endocrine disruptor di(2-ethylhexyl)phthalate (DEHP) were prepared by a precipitation polymerization (PP) procedure. The effect of the dispersive solvents acetonitrile (ACN) and cyclohexane (CH), the cross-linkers ethylene glycol dimethacrylate (EDMA) and trimethylpropane trimethacrylate (TRIM), and the template on particle size and morphology of polymers was investigated in detail by scanning electron microscopy (SEM) and BET adsorption isotherm determination. When used as HPLC stationary phase, the microspheres exhibited strong affinity for the template DEHP with an imprint factor (IF) higher than 8.0 in ACN/water (60:40, v/v) as mobile phase. Furthermore, baseline separation of DEHP from benzyl butyl phthalate (BBP) and dibutyl phthalate (DBP) could be achieved. In contrast, no or only poor separation could be observed with non-imprinted polymeric polymers (NIPs) or imprinted bulk polymers (MIB), respectively. Similarly, the obtained MINs exhibited an imprinting effect in pure ACN, i.e. the bond amount of DEHP was significantly higher compared to NIPs, as was shown in rebinding experiments. Besides their use as an HPLC stationary phase, MIMs might further be applicable for SPE sample cleanup, while MINs could be used as a recognition layer on sensor surfaces.

Identification and characterization of major flavonoids and caffeoylquinic acids in three Compositae plants by LC/DAD-APCI/MS.

In this study, a liquid chromatography/diode array detector-atmospheric pressure chemical ionization/mass spectrometry (LC/DAD-APCI/MS) was successfully developed to identify and characterize the main flavonoids and caffeoylquinic acids (CQAs) of three common Compositae plants (Chrysanthemum morifolium Raman, Artemisia annua, and Chrysanthemum coronarium) which have been used as herbal medicine. Identifications were performed by comparing the retention time, UV and mass spectra of samples with standards or/and earlier publications. The crude methanolic extracts of these plants were assayed directly using LC/MS without any further pretreatment. The proposed method is rapid and reproducible and is useful for characterization and evaluation of different plant flavonoids and CQAs. A total of 41 different flavonoids and 6 CQAs were identified and confirmed by APCI-MS. The main components of three Compositae plants were also compared. Although there exist some similarities in the flavonoidic content of the leaf and flower of C. morifolium, significant variations in their varieties and concentrations were observed. Artemisia annua processes substantial amount of alkylated derivatives of flavones and Chrysanthemum coronarium contains only CQAs. These findings suggest that although all the plants studied are from the same Compositae family, their flavonoids and phenolic compositions are markedly different. The proposed method is useful for further chromatographic fingerprinting of plant flavonoids.

Separation and determination of astaxanthin from microalgal and yeast samples by molecularly imprinted microspheres.

In this work, molecularly imprinted microspheres (MIMs) were synthesized by aqueous microsuspension polymerization using astaxanthin (3,3'-dihydroxy-beta,beta'-carotene-4,4'-dione) as imprinting molecule. The MIMs obtained were subsequently packed into the stainless steel column and the chromatographic characterization of the column was investigated. The effects of pH and composition of the mobile phase on the retention factor (k') were investigated in detail. The mixture of methanol and dichloromethane (DCM) (8:2, v/v) was used as mobile phase A while the mixture of methanol and water (5:5, v/v) as mobile phase B. The separation of astaxanthin and zeaxanthin (3,3'-dihydroxyl-beta-carotene) was obtained when the concentration of mobile phase B was higher than 30% (v/v) due to their strong lipophilicity. The method developed was successfully applied to separate astaxanthin in the saponified samples of the microalga Haematococcus pluvialis and the yeast Phaffia rhodozyma. The recovery of adding 40 mg astaxanthin to 1.0 g microalgal sample was 95.5% with an R.S.D. (n =5) of 5.3%. The results of determination of astaxanthin in the microalga and the yeast were 3.7% (R.S.D (n = 1.5%, n = 9) and 0.041% (R.S.D n= 7.3%, n = 9), respectively.

Separation and determination of the antitumor drug piritrexim by molecularly imprinted microspheres in high-performance liquid chromatography.

Molecularly imprinted microspheres were synthesised using the antitumor drug piritrexim (PTX) as a template molecule by aqueous microsuspension polymerisation and were used as a high-performance liquid chromatographic stationary phase. The molecularly imprinted column exhibited strong retention behaviour to the template molecule. The influences of pH of the buffer and the ratio of methanol to buffer on the retention behaviour were investigated in detail. Results indicated that the baseline separation of PTX, trimetrexate (TMX), trimethoprim (TMP) and sulfamethazine (SMZ) was achieved when the pH value of the acetate buffer was above pH 3.5 and the ratio of methanol to the buffer was 6:4 (v/v). A gradient elution programme was employed to enhance the separation, which led to an improvement in sensitivity and a reduction in determination errors. The method developed was used to analyse urine samples supplemented with PTX. The recoveries of 5 microg mL(-1) PTX in the urine sample were 99.1+/-3.0% and 93.3+/-2.8% at the beginning and 24 h later, respectively.

Preparative separation and determination of matrine from the Chinese medicinal plant Sophora flavescens Ait by molecularly imprinted solid-phase extraction.

Molecularly imprinted microspheres (MIMs) were synthesized by micro-suspension polymerization using matrine (MT) as template. The MIMs were employed for solid-phase extraction (SPE) and as chromatographic stationary phase for the determination of MT from the Chinese medicinal plant Sophora flavescens. The effects of the various eluents, their concentrations and volumes on the retention behavior were investigated. The selectivity and capacity of the imprinted microspheres against MT was also discussed. The results showed that the MIMs exhibited stronger specific affinity to MT than to oxymatrine (OMT). Methanol-water (3:7, v/v) was used for washing impurities from the MIMs-SPE cartridge loaded with the herb extracts, while methanol-glacial acetic acid (9:1, v/v) was used for eluting MT. The maximum load of MT and the recovery of MIMs cartridge towards MT were 38.7 microg g(-1) and 71.4%, respectively. The method developed might be used to separate and extract effective constituents from Chinese medicinal plants on a large scale.

Chromatographic characterization of molecularly imprinted microspheres for the separation and determination of trimethoprim in aqueous buffers.

Molecularly imprinted microspheres (MIMs) against trimethoprim (TMP), prepared by aqueous microsuspension polymerization, bound strongly to TMP, by electrostatic and other non-covalent interactions. The effects of pH, kind and ionic strength (I) of buffer on capacity factors (k') have been discussed in detail. The capacity factors for TMP increased with increasing pH of both acetate and phosphate buffers. The effects of ionic strength on capacity factors were very substantial and the linear relationship between logk' and logI was described by the equation logk'=0.3162-0.4420logI with R=-0.9995. The results showed that pH 3.5 acetate buffer (0.05 mol L(-1)) containing 0.1 mol L(-1) sodium chloride and a 1:9 ratio of buffer to methanol were the optimum conditions for separation and determination of TMP. The calibration plot of peak area against concentration was linear with R=0.9979.

Preparative isolation and purification of salvianolic acid B from the Chinese medicinal plant Salvia miltiorrhiza by high-speed counter-current chromatography.

High-speed counter-current chromatography was applied to the isolation and purification of salvianolic acid B from the Chinese medicinal plant Salvia miltiorrhiza Bunge. The crude salvianolic acid B was obtained by extraction with ethanol-water from S. miltiorrhiza Bunge. Preparative high-speed counter-current chromatography with a two-phase solvent system composed of n-hexane-ethyl acetate-ethanol-water (3:7:1:9, v/v) was successfully performed yielding 342 mg salvianolic acid B at 98% purity from 500 mg of the crude extract in a one-step separation.