Aptamer-Based Fluorescent Biosensing of Adenosine Triphosphate and Cytochrome c via Aggregation-Induced Emission Enhancement on Novel Label-Free DNA-Capped Silver Nanoclusters/Graphene Oxide Nanohybrids.

Four fluorescent DNA-stabilized fluorescent silver nanoclusters (DNA-AgNCs) were designed and synthesized with differences in lengths of cytosine-rich DNA strand (as the stabilizing agent) and target-specific strand DNA aptamers for adenosine triphosphate (ATP) and cytochrome c (Cyt c). After their nanohybrid formation with graphene oxide (GO), it was unexpectedly found that, depending on the composition of the base and length of the strand DNA aptamer, the fluorescence intensity of three of the nanohybrids significantly enhanced. Our experimental observations and quantum mechanical calculations provided an insight into the mechanisms underlying the behavior of DNA-AgNCs/GO nanohybrids. The enhanced fluorescence was found to be attributed to the aggregation-induced emission enhancement (AIE) characteristic of the DNA-AgNCs adsorbed on the GO surface, as confirmed evidently by both fluorescence and transmission electron microscopies. The AIE is a result of hardness and oxidation properties of GO, which lead to enhanced argenophilic interaction and thus to increased Ag(I)-DNA complex shell aggregation. Consequently, two of the DNA-AgNCs/GO nanohybrids were successfully extended to construct highly selective, sensitive, label-free, and simple aptasensors for biosensing of ATP (LOD = 0.42 nM) and Cyt c (LOD = 2.3 nM) in lysed Escherichia coli DH5 α cells and mouse embryonic stem cells, respectively. These fundamental findings are expected to significantly influence the designing and engineering of new AgNCs/GO-based AIE biosensors.

A highly selective semiconducting polymer dots-based "off-on" fluorescent nanoprobe for iron, copper and histidine detection and imaging in living cells.

Semiconducting polymer dots (PDs) hold a great promise as fluorescence nanoprobes, due to their photostability, biocompatibility, and high quantum yield. Herein, the synthesis and characterization of highly fluorescent PDs for selective and sensitive detection of Fe3+,Cu2+, and histidine (His) have been reported. First, carboxyl functionalized poly[(9,9-dioctylfluorenyl-2,7-diyl)-alt-co-(1,4-benzo-(2,1',3)-thiadiazole)] (PFBT) PDs were synthesized through a nano-precipitation technique, and then they were functionalized by -COOH groups using 9-anthracenecarboxylic acid. The formation of PDs was proved using transmission electron microscopy, dynamic light scattering, and Fourier transform infrared (FTIR) spectroscopy analyses. The PDs exhibited a yellow fluorescence with a peak centered at 540 nm (photo-excited at 460 nm) with a quantum yield of 25%. The fluorescence of PDs significantly quenched in the presence of Cu2+ ion, and then selectively recovered upon addition of His, providing the possibility of constructing a sensitive Cu2+-His off-on fluorescent nanoprobe. The PDs exhibited a linear dynamic range for Cu2+ from 0.1 to 630 µmol L-1 with a limit of detection of 61.7 nmol L-1, and for Fe3+ from 0.1 to 720 µmol L-1 with a limit of detection of 58.1 nmol L-1. In addition, the PDs/Cu2+ probe showed a linear dynamic range for His from 0.1 to 920 µmol L-1 with a limit of detection of 79.6 nmol L-1. Besides, the prepared PDs/Cu2+ probe exhibited a promising potential for selective and sensitive sensing of His in blood serum and for intracellular imaging.

Functionalized layered double hydroxide with nitrogen and sulfur co-decorated carbondots for highly selective and efficient removal of soft Hg2+ and Ag+ ions.

A facile composite was fabricated via direct assembly of nitrogen and sulfur co-decorated carbon dots with abundant oxygen-containing functional groups on the surface of the positively charged layered double hydroxide (N,S-CDs-LDH). The novel N,S-CDs-LDH demonstrates highly selective bindings (M-S) and an extremely efficient removal capacity for soft metal ions such as Ag+ and Hg2+ ions. N,S-CDs-LDH displayed a selectivity order of Ag+> Hg2+ >> Cu2+ >>> Pb2+ > Zn2+ > Cd2+ for their adsorption. The enormous capacities for Hg2+ (625.0 mg g-1) and Ag+ (714.3 mg g-1) and very high distribution coefficients (Kd) of 9.9 × 106 mL g-1 (C0 = 20 mg L-1) and 2.0 × 107 mL g-1 (C0 = 20 mg L-1) for Hg2+ and Ag+, respectively, place the N,S-CDs-LDH at the top of LDH based materials known for such removal. The adsorption kinetic curves for Hg2+ and Ag+ fitted well with the pseudo-second order model. For Hg2+ and Ag+, an exceptionally rapid capture with removal ∼100% within 80 min was observed (Cions = 30 mg L-1 and V/m ratio of 1000). The adsorption isotherms were well described using Langmuir isotherm. The N,S-CDs-LDH was successfully applied to highly efficient removal of Hg2+ and Ag+ from aqueous solutions.

Facile preparation and characterization of new green emitting carbon dots for sensitive and selective off/on detection of Fe3+ ion and ascorbic acid in water and urine samples and intracellular imaging in living cells.

Carbon dots (CDs) have gained great attention as multifunctional materials because of their interesting properties and general applicability. However, there are some reports for the preparation of highly luminescent green-emitting CDs (G-CDs), although these reports seem not to be extensible. Herein, new G-CDs (quantum yield: 27.2%) were synthesized from a facile hydrothermal treatment of p-aminosalicylic acid and ethylene glycol dimethacrylate as both carbon and nitrogen source and cross-linking agent, respectively. The chemical composition and optical properties of the as-prepared G-CDs were successfully investigated using transmission electron microscopy, atomic force microscopy, dynamic light scattering, X-ray diffraction, energy dispersive X-ray spectroscopy, Fourier transform infrared spectroscopy and fluorescence and UV-vis spectroscopies. Interestingly, the fluorescence intensity of G-CDs was selectivity quenched by Fe3+ in the range of 0.05-10.0 µmol L-1, with a detection limit of 13.7 nmol L-1. Meanwhile, ascorbic acid found to reduce Fe3+ to Fe2+, thereby causing restoration of the fluorescence of G-CDs. The detection limit for ascorbic acid detection was estimated as 82.0 nmol L-1 over a linear range from 0.2 to 11.0 µmol L-1. Furthermore, the designed sensing platform was successfully utilized to the detection of Fe3+ and ascorbic acid in water and urine samples and to intracellular imaging without surface modification.

SiO2-coated magnetic graphene oxide modified with polypyrrole-polythiophene: A novel and efficient nanocomposite for solid phase extraction of trace amounts of heavy metals.

The synthesis of a novel nanocomposite comprised of SiO2-coated magnetic graphene oxide modified with a pyrrole-thiophene (mGO/SiO2@coPPy-Th) copolymer is reported in the present work. The nanocomposite was applied for the fast magnetic solid phase extraction (MSPE) of trace levels of copper, lead, chromium, zinc and cadmium from water and agricultural samples. The nanocomposite was prepared in three steps: (1) decoration of graphene oxide sheets with magnetite nanoparticles thorough a facile one-step chemical reaction strategy; (2) chemical grafting by a silica layer to obtain high stability in acidic solutions; and (3) surface modification by coPPy-Th via simultaneous oxidation polymerization of pyrrole and thiophene in the presence of mGO/SiO2 composite. The nanocomposite was subsequently characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR), X-ray powder diffraction (XRD) and vibrating sample magnetometry (VSM) techniques. Several important experimental variables that could affect MSPE performance, including the pH of the sample, sorption time, sorbent dosage, eluent type and its concentration, eluent volume and elution time, were investigated and optimized. Under optimal conditions, the limits of detection for the target heavy metals ranged from 0.15 to 0.65µgL-1. The maximum sorption capacity of the mGO/SiO2@coPPy-Th nanocomposite was 201, 230, 125, 98 and 80mgg-1 for Cu(II), Pb(II), Zn(II), Cr(III) and Cd(II), respectively. Finally, the feasibility of the proposed method was investigated for the extraction and determination of the target metals from real matrices.

Magnetic molecularly imprinted composite for the selective solid-phase extraction of p-aminosalicylic acid followed by high-performance liquid chromatography with ultraviolet detection.

A new method for the selective extraction of p-aminosalicylic acid from aqueous and urine samples has been developed using magnetic molecularly imprinted polymer nanoparticles before determination by high-performance liquid chromatography. The Fe3 O4 nanoparticles were first prepared through the chemical coprecipitation of Fe2+ and Fe3+ and then coated with a vinyl shell. Subsequently, a layer of molecularly imprinted polymers was grafted onto the vinyl-modified magnetic nanoparticles by precipitation polymerization. FTIR spectroscopy, scanning electron microscopy, vibrating sample magnetometry, and thermogravimetric analysis were applied to characterize the sorbent properties. Moreover, the predominant parameters affecting the magnetic solid phase extraction such as sample pH, sorption and elution times, the amount of sorbent, and composition and volume of eluent were investigated thoroughly. The maximum sorption capacity of the imprinted polymer toward p-aminosalicylic acid was 70.9 mg/g, which is 4.5 times higher than that of the magnetic nonimprinted polymer. The magnetic molecularly imprinted polymer nanoparticles were applied for the selective extraction of p-aminosalicylic acid from aqueous and urine samples and satisfactory results were achieved. The results illustrate that magnetic molecularly imprinted polymer nanoparticles have a great potential in the extraction of p-aminosalicylic acid from environmental and biological matrices.

Surfactant-assisted dispersive liquid-liquid microextraction of nitrazepam and lorazepam from plasma and urine samples followed by high-performance liquid chromatography with UV analysis.

Surfactant-assisted liquid-liquid microextraction followed by high-performance liquid chromatography with UV detection has been developed for the simultaneous preconcentration and determination of lorazepam and nitrazepam in biological fluids. In this study, an ionic surfactant (cetyltrimethyl ammonium bromide) was used as an emulsifier. The predominant parameters affecting extraction efficiency such as the type and volume of extraction solvent, the type and concentration of surfactant, sample pH, and the concentration of salt added to the sample were investigated and opted. Under the optimum conditions (extraction solvent and its volume, 1-octanol, 70 µL; surfactant and its concentration, 1 mL of ultra-pure water containing 2 mmol L-1 cetyltrimethyl ammonium bromide; sample pH = 9 and salt content of 10% NaCl w/v), the preconcentration factors were obtained in the range of 202-241 and 246-265 for nitrazepam and lorazepam, respectively. The limits of quantification for both drugs were 5 µg L-1 in water sample and 10 µg L-1 in biological fluids with R2 values higher than 0.993. The suitability of the proposed method was successfully confirmed by the extraction and determination of the target drugs in human urine and plasma samples in the range of microgram per liter.

Determination of haloperidol in biological samples using molecular imprinted polymer nanoparticles followed by HPLC-DAD detection.

In this study an extraction procedure using molecular imprinted polymer nanoparticles for the determination of haloperidol in biological samples is proposed. The haloperidol imprinted polymer nanoparticles were synthesized successfully by precipitation polymerization in a flask containing haloperidol as a template, ethyleneglycoldimethacrylate as a crosslinking agent, methacrylic acid as a functional monomer, and 2,2'-azobisisobutyronitrile as an initiator. The leached and unleached polymer nanoparticles have been characterized by infrared spectroscopy and scanning electron microscopy. The effect of different variables such as the pH of solution, uptake and elution time, type, and the least amount of eluent for elution of haloperidol from polymer was evaluated. Extraction efficiencies more than 97% were obtained by elution of the polymer with 1.5 mL of methanol-acetic acid-trifluoroacetic acid 79.9:20:0.1. Under optimal conditions maximum adsorption capacity was obtained 153.84 mg g(-1). The detection limit of the proposed procedure was between 0.2 and 0.35 µg L(-1). Finally this method was applied to the determination of haloperidol in plasma and urine samples and satisfactory results were achieved (RSD<6.9%).

Determination of haloperidol in biological samples with the aid of ultrasound-assisted emulsification microextraction followed by HPLC-DAD.

A rapid and simple quantitative method for preconcentration and determination of haloperidol in biological samples was developed using ultrasound-assisted emulsification microextraction, based on the solidification of floating organic droplet combined with HPLC-DAD. The effects of several factors were investigated. A total of 30 µL of 1-undecanol as an extraction solvent was injected slowly into a glass-centrifuge tube containing 4 mL alkaline sample solution that was located inside the ultrasonic water bath. The formed emulsion was centrifuged and the fine droplets of solvent were floated at the top of the test tube, then it was cooled in an ice bath and the solidified solvent was transferred into a conical vial, after melt, the analysis of the extract was carried out by HPLC. Under the optimal conditions, the extraction efficiencies were more than 90% and the preconcentration factors were obtained between 119-122. The LOQs were obtained between 4-8 µg/L and the calibration curves were linear within the range of 4-1000 µg/L. Finally this method was applied to the determination of haloperidol in plasma and urine samples in the range of µg/L and satisfactory results were achieved (RSDs <7%).