Development of a Coumarin-derived Fluorescent Probe for Detection of HOCl and its Application in Cells and Zebrafish.

We have prepared a simple, universal and efficient coumarin-derived fluorescent probe (XDS1) to detecting HOCl. The experimental findings revealed that the introduction of HOCl produced an obvious quenching effect on the probe with high selectivity and sensitivity. The calculated limit of detection (LOD) was as low as 0.02 µM. Furthermore, an impressive response time of less than 10 s was observed when XDS1 detecting HOCl. Importantly, the probe XDS1 exhibited negligible cytotoxicity, thereby facilitating its application for imaging HOCl within biological environment. The probe XDS1 had been successfully used for specific detection in cells.

Naphthalimide-based fluorescent probe for Hg2+ detection and imaging in living cells and zebrafish.

A simple naphthalimide-based fluorescent probe was designed and synthesized for the determination of mercury ion (Hg2+ ). The probe showed a noticeable fluorescence quenching response for Hg2+ . When added with Hg2+ , the fluorescence intensity of the probe at 560 nm was remarkably decreased with the color changed from yellow to colorless under ultraviolet (UV) light. The probe had a notable selectivity and sensitivity for Hg2+ and displayed an excellent sensing performance when detecting Hg2+ at low concentration (19.5 nM). The binding phenomenon between the probe and Hg2+ was identified by Job's method and high-resolution mass spectrometry (HRMS). Moreover, the probe was not only utilized to identify Hg2+ in real samples with satisfactory results (92.00%-110.00%) but also was successfully used for bioimaging in cells and zebrafish. The recognition mechanism has been verified by transmission electron microscopy (TEM) for the first time. All the results showed that the probe could be used as a potent useful tool for detection of Hg2+ .

Rhodamine-based Fluorescent Probe With Quick Response and High Selectivity for Imaging Labile Ferrous Iron in Living Cells and Zebrafish.

The transition between its various oxidation states of Iron plays a crucial part in various chemical transformation of cells. Misregulation of iron can give rise to the iron-catalyzed reactive oxygen species disorder which have been linked to a variety of diseases, so it is crucial to monitor the labile iron pool in vivo for clinical diagnosis. According to iron autoxidation and hydrogen abstraction reaction, we reported a novel "off-on" fluorescent probe to response to ferrous (Fe2+) both in solutions and biological systems. The probe responds to Fe2+ with good selectivity toward competing metal ions. What's more, the probe presents significant fluorescent enhancement to Fe2+ in less than 1 min, making real-time sensing in biological system possible. The applications of the probe in bioimaging revealed the changes in labile iron pool by iron autoxidation or diverse stimuli.

Improved LC-MS/MS method for the simultaneous quantification of tacrolimus and cyclosporine A in human blood and application to therapeutic drug monitoring.

In order to facilitate therapeutic drug monitoring of tacrolimus and cyclosporine A in clinical practice, a simple, rapid, robust, sensitive and specific LC-MS/MS assay was developed and validated for the simultaneous determination of tacrolimus and cyclosporine A in human whole blood. Erythrocytes were destroyed using internal standard solution with 10% (w/v) zinc sulfate in water. The analytes were extracted from 100 µl of whole blood by protein precipitation with acetonitrile. Chromatographic separation was conducted on a Kinetex PFP column (60°C) by a gradient elution with a flow rate of 0.450 ml/min in 2.5 min. Quantitative analysis was performed using electrospray ionization and multiple reaction monitoring in positive ionization mode. The method was fully validated as per current guidelines on bioanalytical methodologies of the US Food and Drug Administration and European Medicines Agency. The method developed was applied successfully in analyzing clinical samples from patients administered tacrolimus or cyclosporine A. The sample treatment procedure was rationalized and improved to fulfill the complete target extraction. The chromatography conditions were optimized to achieve rapid and accurate quantification of both analytes. This method may be beneficial as a constructive input for the therapeutic drug monitoring of tacrolimus and cyclosporine A in obtaining individualized therapy.

The ratiometric fluorescent sensor based on the mixture of CdTe quantum dots and graphene quantum dots for quantitative analysis of silver in drinks.

Silver nanoparticles can be used in antibacterial packaging or disinfection. Research has shown that sugary fluid induces the leaching of silver nanoparticles into water, which may be harmful to humans. Single wavelength fluorescence analysis has been used for quantitative analysis of silver nanoparticles but suffers from low specificity and poor anti-interference ability. In this paper, a ratiometric fluorescence sensor system (GCS) was used for the detection of Ag+, which realized both visual detection and quantitative analysis of silver in drinks. The color changes of GCS with different concentrations of Ag+ are distinguishable and easy to analyze. There is also a good linear relationship between the concentrations of Ag+ and varieties of F424 nm/F570 nm, and the lowest detection limit reached 0.2266 nmol/L. This GCS shows good selectivity and recovery and could be used for the detection of Ag+ in drink samples.

An Ethyl-Thioglycolate-Functionalized Fe3O4@ZnS Magnetic Fluorescent Nanoprobe for the Detection of Ag+ and Its Applications in Real Water Solutions.

Ethyl-thioglycolate-modified Fe3O4@ZnS nanoparticles (Fe3O4@ZnS-SH) were successfully prepared using a simple chemical precipitation method. The introduction of ethyl thioglycolate better regulated the surface distribution of ZnS, which can act as a recognition group and can cause a considerable quenching of the fluorescence intensity of the magnetic fluorescent nanoprobe, Fe3O4@ZnS-SH. Benefiting from stable fluorescence emission, the magnetic fluorescent nanoprobe showed a highly selective fluorescent response to Ag+ in the range of 0-400 µM, with a low detection limit of 0.20 µM. The magnetic fluorescent nanoprobe was used to determine the content of Ag+ in real samples. A simple and environmentally friendly approach was proposed to simultaneously achieve the enrichment, detection, and separation of Ag+ and the magnetic fluorescent nanoprobe from an aqueous solution. These results may lead to a wider range of application prospects of Fe3O4 nanomaterials as base materials for fluorescence detection in the environment.

Synthesis and Application of Ion-Exchange Magnetic Microspheres for Deep Removal of Trace Acetic Acid from DMAC Waste Liquid.

In order to develop a deep method for removing trace acetic acid from industrial solvents, a type of quaternary ammonium-salt-modified magnetic microspheres was developed as a potential nanoadsorbent for low-concentration acetic-acid-enhanced removal from DMAC aqueous solution. The ion-exchange magnetic microspheres (Fe3O4@SiO2@N(CH3)3+) have been prepared by a two-step sol-gel method with N-trimethoxysilylpropyl-N, N, N-trimethylammonium chloride as functional monomer, tetraethyl orthosilicate as a cross-linking agent, Fe3O4@SiO2 as a matrix. The nanocomposite is characterized by SEM, FI-IR, XRD, VSM, and XPS. Moreover, the optimization of adsorption experiments shows that the maximum adsorption capacity of nanoadsorbent is 7.25 mg/g at a concentration = 30 mg/L, adsorbent dosage = 10 mg, V = 10 mL, and room temperature. Furthermore, the saturated Fe3O4@SiO2@N(CH3)3+ achieved an efficient regeneration using a simple desorption method and demonstrated a good regeneration performance after five adsorption/desorption cycles. In addition, Fe3O4@SiO2@N(CH3)3+ was used to remove acetic acid in DMAC waste liquid; the adsorption effect is consistent with that of a nanoadsorbent of acetic acid in an aqueous solution. These results indicate that Fe3O4@SiO2@N(CH3)3+ can efficiently treat acetic acid that is difficult to remove from DMAC waste liquid.

Genome-wide characterization of the tomato GASA family identifies SlGASA1 as a repressor of fruit ripening.

Gibberellins (GAs) play crucial roles in a wide range of developmental processes and stress responses in plants. However, the roles of GA-responsive genes in tomato (Solanum lycopersicum) fruit development remain largely unknown. Here, we identify 17 GASA (Gibberellic Acid-Stimulated Arabidopsis) family genes in tomato. These genes encode proteins with a cleavable signal peptide at their N terminus and a conserved GASA domain at their C terminus. The expression levels of all tomato GASA family genes were responsive to exogenous GA treatment, but adding ethylene eliminated this effect. Comprehensive expression profiling of SlGASA family genes showed that SlGASA1 follows a ripening-associated expression pattern, with low expression levels during fruit ripening, suggesting it plays a negative role in regulating ripening. Overexpressing SlGASA1 using a ripening-specific promoter delayed the onset of fruit ripening, whereas SlGASA1-knockdown fruits displayed accelerated ripening. Consistent with their delayed ripening, SlGASA1-overexpressing fruits showed significantly reduced ethylene production and carotenoid contents compared to the wild type. Moreover, ripening-related genes were downregulated in SlGASA1-overexpressing fruits but upregulated in SlGASA1-knockdown fruits compared to the wild type. Yeast two-hybrid, co-immunoprecipitation, transactivation, and DNA pull-down assays indicated that SlGASA1 interacts with the key ripening regulator FRUITFULL1 and represses its activation of the ethylene biosynthesis genes ACS2 and ACO1. Our findings shed new light on the role and mode of action of a GA-responsive gene in tomato fruit ripening.

Controllable Preparation of Superparamagnetic Fe3O4@La(OH)3 Inorganic Polymer for Rapid Adsorption and Separation of Phosphate.

Superparamagnetic Fe3O4 particles have been synthesized by solvothermal method, and a layer of dense silica sol polymer is coated on the surface prepared by sol-gel technique; then La(OH)3 covered the surface of silica sol polymer in an irregular shape by controlled in situ growth technology. These magnetic materials are characterized by TEM, FT-IR, XRD, SEM, EDS and VSM; the results show that La(OH)3 nanoparticles have successfully modified on Fe3O4 surface. The prepared Fe3O4@La(OH)3 inorganic polymer has been used as adsorbent to remove phosphate efficiently. The effects of solution pH, adsorbent dosage and co-existing ions on phosphate removal are investigated. Moreover, the adsorption kinetic equation and isothermal model are used to describe the adsorption performance of Fe3O4@La(OH)3. It was observed that Fe3O4@La(OH)3 exhibits a fast equilibrium time of 20 min, high phosphate removal rate (>95.7%), high sorption capacity of 63.72 mgP/g, excellent selectivity for phosphate in the presence of competing ions, under the conditions of phosphate concentration 30 mgP/L, pH = 7, adsorbent dose 0.6 g/L and room temperature. The phosphate adsorption process by Fe3O4@La(OH)3 is best described by the pseudo-second-order equation and Langmuir isotherm model. Furthermore, the real samples and reusability experiment indicate that Fe3O4@La(OH)3 could be regenerated after desorption, and 92.78% phosphate removing remained after five cycles. Therefore, La(OH)3 nanoparticles deposited on the surface of monodisperse Fe3O4 microspheres have been synthesized for the first time by a controlled in-situ growth method. Experiments have proved that Fe3O4@La(OH)3 particles with fast separability, large adsorption capacity and easy reusability can be used as a promising material in the treatment of phosphate wastewater or organic pollutants containing phosphoric acid functional group.

A novel mitochondria-targetable NIR fluorescent probe for monitoring intracellular hypobromous acid levels.

The development of ultrasensitive in situ detection techniques for monitoring hypobromous acid (HBrO) levels in the biological systems is of great significance to reveal its complex pathological and physiological effects. A simple mitochondria-targetable hydrazine-based near-infrared (NIR) fluorescent probe (Mito-NIR) for detecting HBrO in the mitochondria of live cells is presented in this paper. Probe Mito-NIR displays the ultrafast (< 5 s) response for HBrO. It can detect HBrO with high sensitivity. Additionally, it shows high selectivity towards HBrO over other biologically important substances. Finally, it can monitor the changes of endogenous/exogenous HBrO levels in the mitochondria of live cells. A simple mitochondria-targetable NIR fluorescent probe with picomolar sensitivity for HBrO was developed to specifically track mitochondrial HBrO.

The Development of a 4-aminonaphthalimide-based Highly Selective Fluorescent Probe for Rapid Detection of HOCl.

Recently, more and more evidence indicated that intracellular HOCl plays a crucial role in the regulation of inflammation and apoptosis, while excessive HOCl has an impact on human health problems. So, the development of methods for sensitive detection of HOCl is very vital to reveal its various physiological and pathological functions. In this paper, we have described a simple fluorescent probe for selective detection of HOCl, whereas for higher concentrations of other biological important substances, the probe almost does not respond. The experimental results show that the probe can quantitatively determine the range of 0-1 µM HOCl, the detection limit is 0.05 µM. In addition, the probe reacts quickly with HOCl (< 3 s), which is helpful to monitor HOCl in biological system because HOCl is highly reactive and short-lived. The ability of the probe to HOCl enables it to be used to track the HOCl levels in living systems.

Rhodol-derived turn-on fluorescent probe for copper ions with high selectivity and sensitivity.

A new rhodol-derived fluorescent probe 1 with picolinate as the recognition receptor was designed and simply synthesized using a one-step reaction. With the concentration of added Cu2+ increases, it gradually turns pink, so the effect of naked eye detection can be achieved. The detection limit of probe 1 for Cu2+ is 42 nM, and the linear detection range was 0-2 µM. The experimental results showed that 1 was a fluorescent probe with high selectivity, good water solubility, and high sensitivity to Cu2+ . Probe 1 was successfully applied in cell imaging experiments and can detect the concentration of Cu2+ in water samples. All these indicate that probe 1 has the potential to be applied to the detection of Cu2+ concentration in the real environment.

A Near Infrared Fluorescent Probe for Sensitive Determination of Human Serum Albumin.

A fluorescent probe 1 has been successfully developed to determine human serum albumin (HSA). Probe 1 expresses a dramatic fluorescence enhancement to HSA without interference from other amino acids. Under the optimal conditions, the calibration graphs are linear over the range of 0 - 13.3 µg/mL with the limit of determination of 0.61 µg/mL. Thus, this probe shows high sensitivity and selectivity to HSA.

Fluorescence resonance energy transfer for investigation of the interaction of Para Red with serum albumins.

Para Red (PR) has been isolated from food additives, and shown to be toxic to humans. To facilitate examination of its toxicity, the interaction between PR and serum albumins (SA) was studied using fluorescence quenching and circular dichroism (CD) spectrophotometry. The experiments showed that the fluorescence intensity of serum albumins decreased with increasing concentrations of PR, which resulted from the binding of PR and SA. The binding constant, number of binding sites and thermodynamic parameters were calculated and hydrogen bond and van der Waals interactions were shown to play a key role in the binding process. Competition experiments indicated that PR mainly binds to Trp residues of SA within the site I. As the CD and three-dimensional spectra revealed, the addition of PR induced a conformational change in SA.

Fluorescence detection of adenosine triphosphate through an aptamer-molecular beacon multiple probe.

An aptamer-molecular beacon (MB) multiple fluorescent probe for adenosine triphosphate (ATP) assay is proposed in this article. The ATP aptamer was used as a molecular recognition part, and an oligonucleotide (short strand, SS) partially complementary with the aptamer and an MB was used as the other part. In the presence of ATP, the aptamer bound with it, accompanied by the hybridization of MB and SS and the fluorescence recovering. Wherever there is only very weak fluorescence can be measured in the absence of ATP. Based on the relationship of recovering fluorescence and the concentration of ATP, a method for quantifying ATP has been developed. The fluorescence intensity was proportional to the concentration of ATP in the range of 10 to 500 nM with a detection limit of 0.1 nM. Moreover, this method was able to detect ATP with high selectivity in the presence of guanosine triphosphate (GTP), cytidine triphosphate (CTP), and uridine triphosphate (UTP). This method is proved to be simple with high sensitivity, selectivity, and specificity.

A colorimetric and ratiometric fluorescent probe for quantification of bovine serum albumin.

A 4-aminonaphthalimide-based ratiometric fluorescent probe 1 employing the internal charge transfer (ICT) mechanism was designed and synthesized to detect bovine serum albumin (BSA). The interaction of 1 and BSA was investigated by fluorescence and UV-vis absorption spectroscopy. Upon treatment with BSA, the probe successfully exhibited a ratiometric fluorescent response at 540 nm and 480 nm. The fluorescent intensity ratio at 540 nm and 480 nm (F(540)/F(480)) increases linearly with BSA concentration in the range of 0-75.0 µg mL(-1) and the detection limit was about 2.4 ng mL(-1). Our strategy is expected to provide a methodology to quantify BSA either by a normal or by a ratiometric and colorimetric way with high sensitivity.