A Novel Enhanced-Fluorescent Probe Based on DHLA-Stabilized Red-Emitting Copper Nanoclusters for Methimazole Detection Via Aggregation-Induced Emission Effect.

Herein, an aqueous phase synthesis approach was presented for the fabrication of copper nanoclusters (Cu NCs) with aggregation-induced emission (AIE) property, utilizing lipoic acid and NaBH4 as ligands and reducing agent, respectively. The as-synthesized Cu NCs exhibit an average size of 3.0 ± 0.2 nm and demonstrate strong solid-state fluorescence upon excitation with UV light. However, when dissolved in water, no observable fluorescent emission is detected in the aqueous solution of Cu NCs. Remarkably, the addition of Methimazole induced a significant red fluorescence from the aqueous solution of Cu NCs. This unexpected phenomenon can be ascribed to the aggregation of negatively charged Cu NCs caused by electrostatic interaction with positively charged imidazole groups in Methimazole, resulting in enhanced fluorescence through AIE mechanism. Therefore, there exists an excellent linear correlation between the fluorescent intensities of Cu NCs aqueous solution and the concentration of Methimazole within a range of 0.1-1.5 mM with a low limit of detection of 82.2 µM. Importantly, the designed enhanced-fluorescent nanoprobe based on Cu NCs exhibits satisfactory performance in assaying commercially available Methimazole tablets, demonstrating its exceptional sensitivity, reliability, and accuracy.

ZnS QDs Stabilized Concurrently with Glutathione and L-cysteine for Highly Sensitive Determining Adriamycin Based on the Fluorescence Enhancement Mechanism.

In this work, a facile and fast aqueous-phase synthetic method is proposed to prepare water-soluble ZnS quantum dots stabilized simultaneously with glutathione and L-cysteine (ZnS QDs-GSH/L-Cys). As-synthesized ZnS QDs-GSH/L-Cys were monodispersed spherical nanocrystals with a mean diameter of 5.0 ± 0.7 nm. Besides, the obtained ZnS QDs-GSH/L-Cys emitted more intensive blue fluorescence and exhibited an improved stability in aqueous solution compared with ZnS quantum dots merely stabilized with GSH (ZnS QDs-GSH). Interestingly, Adriamycin, a representative anticancer drug, was added into the solution of ZnS QDs-GSH/L-Cys, the blue fluorescence of ZnS QDs-GSH/L-Cys was greatly enhanced instead of being quenched, which indicated that ZnS QDs-GSH/L-Cys can be used as an enhanced-fluorescence nanoprobe for determining Adriamycin. The observed fluorescent enhancement could be attributed to the blocking of photoinduced electron transfer (PET) in ZnS QDs-GSH/L-Cys due to the electrostatic interaction between the -COO- groups on the surface of quantum dots and the -NH3+ groups in Adriamycin, followed by the coordination interaction among ZnS QDs-GSH/L-Cys and Adriamycin. The fluorescence intensity of ZnS QDs-GSH/L-Cys presented a good linear response with the concentration of Adriamycin ranging from 2.0 to 20 µg•mL-1. The proposed fluorescent nanoprobe exhibited an excellent sensitivity with the LOD of 0.1 µg•mL-1 and a good accuracy for detecting Adriamycin.

Rapid biosynthesis of fluorescent CdSe QDs in Bacillus licheniformis and correlative bacterial antibiotic change assess during the process.

Cadmium selenide (CdSe) quantum dots (QDs) were biosynthesized rapidly in 18 h in Bacillus licheniformis ATCC 11946 (B. licheniformis); this process benefited from the cellular machinery of bacteria metal metabolism, in which inorganic Na2 SeO3 and CdCl2 were chosen as raw materials to produce high quality CdSe QDs by a designed two-step protocol. Research outcomes demonstrated that the purified CdSe QDs possessed maximum fluorescence intensities at weak alkalinity solutions and had good fluorescence stabilities at 4°C as well as at room temperature after standing for 1 week. Glutathione (GSH) concentration and superoxide dismutase (SOD) content, both of which were reported to be greatly related to biosynthetic activities in some bacterial matrices, were monitored during the biosynthetic process in B. licheniformis. Bacterial resistance research further showed that the change in rates in bacterial inhibition zone diameter to seven different antibiotics was less than 9% after B. licheniformis was used to manufacture CdSe QDs, showing a relative lower environmental risk in short-term heavy metal exposure.

A new type of magnetic molecular imprinted material combined with ß-cyclodextrin for the selective adsorption of zearalenone.

In this paper, a new magnetic molecular imprinted polymer-cyclodextrin (MMIP-CD) material was prepared by connecting ß-cyclodextrin (CD) on the surface of a magnetic molecular imprinted polymer (MMIP) and used for the rapid and specific adsorption of zearalenone (ZEN). By using warfarin as the virtual template molecule, tetraethyl orthosilicate (TEOS) as the crosslinking agent, and (3-aminopropyl) triethoxysilane (APTES) as the functional monomer, a MMIP was produced by surface imprinting technology. Sulfobutyl ether-ß-cyclodextrin attached to the surface of the MMIP under heating conditions produced a new specific adsorption material with exceptional adsorption capacity and excellent selectivity for ZEN. Scanning electron microscopy (SEM), transmission electron microscopy (TEM) and TEM-mapping results showed that the prepared MMIP-CD had a uniform particle size of about 480 nm, and the molecularly imprinted layer was successfully wrapped on the surface of the nanoparticles with a thickness of about 50 nm, whereby the cyclodextrin was effectively attached to the surface of the MMIP. The adsorption mechanism of MMIP-CD was confirmed by kinetic adsorption and thermodynamic adsorption experiments, the maximum adsorption capacity was found to be about 30 mg g-1, and the adsorption equilibrium could be reached within 20 min. The value of IF (QMMIP-CD/QMNIP) is 4.642. This showed that compared with MNIP, MMIP-CD showed a greatly improved specific adsorption capacity of ZEN. Selective experiments proved that MMIP-CD effectively combined the advantages of MMIP and CD, enhancing the adsorption capacity together with reducing the disadvantages that MMIP cannot distinguish structural analogs and CD cannot identify hydrophobic compounds effectively. In actual sample testing, the limit of quantification (LOQ) and limit of detection (LOD) were 0.1 ng kg-1 and 0.3 ng kg-1, respectively. The stability and detection precision of this method were 0.98-2.76% and 1.67-3.88%, respectively. The results proved that MMIP-CD had good development potential in the field of selective adsorption of ZEN, and laid the foundation for follow-up research.

Aggregation-Induced Emission Properties of Glutathione and L-Cysteine Capped CdS Quantum Dots and their Application as Zn(II) Probe.

Targeting to obtain better water solubility and stability and less aggregation-caused quenching effects of quantum dots, two kinds of thiol molecules, glutathione and L-cysteine, were firstly united to offer stabilizing ligands for aqueous synthesized CdS quantum dots, which exhibited sensitive aggregation-induced emission properties. Fluorescent intensity of the CdS quantum dots was enhanced about 5 folds by simple solvent exchange from water to 90 vol% PEG200. Restriction of intramolecular motions in an aggregate state was probably the main cause of the phenomenon. At the same time, fluorescent intensity of CdS quantum dots in the presence of zinc ions was able to be enhanced about 2.2 folds. Based on the researches, a handy metal enhanced fluorescent probe for detecting zinc ions was established. And the detection limit was 0.58 µmol/L. Zinc ions as a bridge among CdS quantum dots to form aggregates limited motions of CdS quantum dots to a certain extent and simultaneously enhanced their fluorescence emission intensities. Meanwhile, activation of surface states of CdS quantum dots also led to emission enhancement. Both of the two factors together contributed to the fluorescence enhancement and ultimately to the sensitivity to zinc ion sample detection.

Preparation of magnetic molecularly imprinted polymers for the identification of zearalenone in grains.

This study was based on the specific binding ability of magnetic molecularly imprinted polymers (MMIPs) combined with a high-performance liquid chromatography-fluorescence detector (HPLC-FLD) for the rapid determination of zearalenone (ZEN) in cereals. A novel magnetic molecularly imprinted polymer was prepared by surface imprinting technology. Warfarin was used as a virtual template, 3-aminopropyl triethoxysilane (APTES) was used as the functional monomer, and tetraethyl orthosilicate (TEOS) was used as the cross-linking agent. Analysis by a vibrating sample magnetometer (VSM), Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) showed that MMIPs were prepared with a particle size about 450 nm, the imprinted molecular layer accounting for 10.7% of the total mass, and saturation magnetization of about 34.54 emu/g. The maximum adsorption capacity (Qmax) of the thermodynamic and kinetic adsorption experiments were 13.90 mg/g and 8.71 mg/g, respectively. The Langmuir model showed that the binding sites were uniformly distributed on the surface of the MMIPs. The Scatchard analysis showed that MMIPs had two types of binding sites with Qmax of 8.22 mg/g and 15.37 mg/g, respectively. In actual sample detection, the limit of detection (LOD) and limit of quantification (LOQ) were 0.4 ng/kg and 0.9 ng/kg, respectively. The sample recovery rate was 90.56-99.96%, the daytime stability was 1.35-2.87%. These results showed that MMIPs had good performance in selectively identifying ZEN and were suitable for determining ZEN in cereals.

Preparation of magnetic molecularly imprinted polymer for selective identification of patulin in juice.

A highly efficient and selective method was successfully developed by using magnetic molecularly imprinted polymers (MMIPs) combined with high performance liquid chromatography (HPLC) to quickly determine patulin (PAT) in juice. MMIPs was prepared by surface imprinting method using Fe3O4 nanoparticles as supporter, 2-oxindole as virtual template, (3-Aminopropyl) triethoxysilane (APTES) as functional monomer and tetraethyl orthosilicate (TEOS) as crosslinking agent. The structure of the product was characterized by vibrating sample magnetometer (VSM), Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), and thermogravimetric analysis (TGA). The results showed that MMIP with a particle size of about 450 nm was successfully prepared, the imprinted molecular layer accounted for about 11.6% of the total mass, and the saturation magnetization was about 6.82 emu/g. The maximum adsorption capacities (Qmax) of kinetic and thermodynamic adsorption experiments were 1.97 mg/g and 4.241 mg/g, respectively. The adsorption process was highly selective and fitted well with the pseudo-second-order model. Langmuir model demonstrated that the binding sites were evenly distributed on the surface of the MMIPs. Scatchard analysis showed that MMIPs had two types of binding sites with Qmax of 4.53 mg/g and 5.73 mg/g, respectively. In the actual sample application, the limit of detection (LOD) and the limit of quantification (LOQ) were 3 µg/kg and 10 µg/kg. And the recovery rate of the sample was 86.44-95.50%. MMIPs possessed excellent applicability with stability of 1.11-3.16% and accuracy of 0.63-1.94%. These results indicated that MMIPs had good performance in separating PAT and was suitable for determining PAT in actual samples.

The Loading of Luminescent Magnetic Nanocomposites Fe3O4@Polyaniline/Carbon Dots for Methotrexate and Its Release Behavior In Vitro.

In the present study we developed novel luminescent magnetic nanocomposites termed Fe3O4@polyaniline/carbon dots. First, Fe3O4 magnetic nanoparticles were prepared by the coprecipitation method. The nanoparticles were then coated with polyaniline using the in situ growth method to form Fe3O4@polyaniline nanohybrids, which were endowed with amino functional groups on the surface and avoided the aggregation of Fe3O4 nanoparticles. The X-ray diffraction pattern demonstrated that the crystalline phase of the Fe3O4 nanoparticles was an inverse spinel structure and was not changed in the Fe3O4@polyaniline nanohybrids. The saturation magnetization and the coercive force of the as-prepared Fe3O4@polyaniline nanohybrids measured by a vibrating sample magnetizer were 63.7 emu·g-1 and zero respectively, which indicated that the Fe3O4@polyaniline nanohybrids exhibited excellent superparamagnetism. The Fe3O4@polyaniline nanohybrids were conjugated with carbon dots, prepared from orange juice, via the amide bond between the amino groups on the surface of the Fe3O4@polyaniline nanohybrids and the carboxyl groups on the surface of carbon dots. The obtained luminescent magnetic nanocomposites Fe3O4@polyaniline/carbon dots showed good photoluminescent properties, which hinted that the nanocomposites have potential in drug tracing and magnetic targeted drug delivery. Finally, the anticancer drug methotrexate was loaded into the Fe3O4@polyaniline/carbon dots nanocomposites, forming a novel magnetic targeted drug delivery system. The results confirmed that the novel drug delivery system exhibited excellent drug-loading capability for methotrexate of ca. 70%, and emits strong fluorescence at the wavelength of 360 nm. An in vitro release experiment of the drug delivery system indicated that the cumulative release percentage of methotrexate was 17.2% in the phosphate-buffered saline (pH = 7.4) within 36 h.

Aggregation-induced emission properties of hydrothermally synthesized Cu-In-S quantum dots.

Novel Cu-In-S quantum dots (CIS QDs), which exhibit interesting aggregation-induced emission (AIE) properties, were successfully prepared via a hydrothermal method. When the solvent was changed from water to 90 vol% DMSO, the photoluminescence intensity of the as-prepared CIS QDs was enhanced about 126-fold.

Assay of ceftazidime and cefepime based on fluorescence quenching of carbon quantum dots.

A novel and sensitive method for the determination of ceftazidime and cefepime in an active pharmaceutical ingredient (API) has been developed based on the fluorescence quenching of poly(ethylene glycol) (PEG)2000-capped carbon quantum dots (CQDs) prepared using a chemical oxidation method. The quenching of fluorescence intensity is proportional to the concentration of ceftazidime and cefepime over the range of 0.33-3.30 and 0.24-2.40 µg/mL, respectively. The mode of interaction between PEG2000-capped CQDs and ceftazidime/cefepime in aqueous solutions was investigated using a fluorescence, UV/Vis and Fourier transform infrared spectrometry (FTIR) at physiological pH. UV/Vis and FTIR spectra demonstrated that ground state compounds were formed through hydrophobic interaction the fluorescence quenching of CQDs caused by ceftazidime and cefepime. The quenching constants decreased with increases in temperature, which was consistent with static quenching.

The interaction of CuInS2 /ZnS/TGA quantum dots with tyrosine kinase inhibitor and its application.

The interactions between thioglycolic acid-capped-CuInS2 /ZnS quantum dots (CuInS2 /ZnS/TGA QDs) and tyrosine kinase inhibitor (TKI) were investigated using fluorescence, ultraviolet-visible spectrometry and Fourier transform infrared spectrometry. The results indicated that the fluorescence intensity of CuInS2 /ZnS/TGA could be quenched by imatinib, dasatinib, nilotinib, gefitinib and erlotinib, which hinted that CuInS2 /ZnS/TGA QDs could be used in the detection of TKI in active pharmaceutical ingredients (API). Calibration curves showed good linear correlation and low detection limits. The average recovery was between 98 and 102%. Moreover, the nature of the fluorescence quenching mechanism of CuInS2 /ZnS/TGA QDs by TKI was discussed. A ground state complex was formed by hydrogen bonding between the carboxyl group of CuInS2 /ZnS/TGA QDs and the amino group of TKI. This led to an increase in non-radiative transition and fluorescence quenching of CuInS2 /ZnS/TGA QDs.