Eu3+-functionalized covalent organic framework for ratiometric fluorescence detection and adsorption of tetracycline and information steganography.

Functional materials with organic/inorganic composites as the main matrix and rare earth ion complexes as the guest have shown a very broad application prospect for antibiotic sensors. However, Eu3+-complex often relies on a single fluorescence response signal, which is susceptible to changes in the detection environment and cannot simultaneously detect and remove tetracycline (TC). Herein, green fluorescent covalent two-dimensional organic framework (COF-TD) is synthesized, followed by modification of Eu3+ to synthesize COF-TD@Eu3+. In the ratiometric sensor, Eu3+ serves as the recognition site and specific response probe for TC, while COF-TD is the fluorescence reference and carrier for Eu3+. Due to the antenna effect, TC enhances the red fluorescence of Eu3+, while the green fluorescence of COF-TD remains almost stable. Based on the change of fluorescence intensity and fluorescence color from green to red, the efficient ratiometric sensing can be finished in 1 min. The developed method shows high sensitivity with a detection limit of 0.3 µM and high selectivity to TC which makes the method applicable to detect TC in traditional Chinese medicine preparations. In addition, due to the high specific surface area of COFs and specific adsorption sites, COF-TD@Eu3+ also shows good performance for TC removal. The findings show that the maximum adsorption capacity is 137.3 mg g-1 and the adsorption equilibrium is reached in 30 min. Smartphone assisted COF-TD@Eu3+ for both ratiometric fluorescence detection and detecting the absorption of TC is proposed for the first time. The molecular cryptosteganography that transforms the selective response of COF-TD@Eu3+ to binary strings is anticipated to advance utilization of nanomaterials in logic sensing and information safety.

A novel fluorescent nanoprobe based on potassium permanganate-functionalized Ti3C2 QDs for the unique "turn-on" dual detection of Cr3+ and Hg2+ ions.

Titanium carbide quantum dots (Ti3C2 QDs) were synthesized by ammonia-assisted hydrothermal method. We also synthesized potassium permanganate (KMnO4)-functionalized Ti3C2 QDs (Mn-QDs) by modifying Ti3C2 nanosheets with KMnO4 and then cutting the functional nanosheets into Mn-QDs. The Ti3C2 QDs and Mn-QDs were characterized by fluorescence spectroscopy (FL), Fourier transform infrared spectroscopy (FTIR), UV-vis spectrophotometry (UV-vis), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM). Furthermore, the modified Mn-QDs have strong luminescence ability and good dispersion stability, which can be used for Cr3+ and Hg2+ double ion detection with enhanced fluorescence specificity. Cr3+/Hg2+ and negatively charged Mn-QDs are bound together by electrostatic interactions. Meanwhile, the surface of Mn-QDs is rich in functional groups, which interacts with Cr3+/Hg2+ to modify the surface traps, leading to defect passivation and exhibiting photoluminescence enhancement. For the dynamic quenching produced by the interaction of Mn-QDs with Hg2+ within 50 µM, it may be caused by the complex formation of Hg2+ trapped by the amino group on the surface of Mn-QDs. The detection limits for Cr3+ and Hg2+ were 0.80 µM and 0.16 µM, respectively. The recoveries of Cr3+ and Hg2+ ions in real water samples were 93.79-105.10% and 93.91-102.05%, respectively, by standard addition recovery test. In this work, the application of Mn-QDs in Cr3+ and Hg2+ ion detection was researched, which opens a new way for its application in the field of detecting heavy metal ions.

A light-up "G-quadruplex nanostring" for label-free and selective detection of miRNA via duplex-specific nuclease mediated tandem rolling circle amplification.

MicroRNA (miRNA) has emerged as a promising genetic marker for cancer diagnosis and therapy because its expression level is closely related to the progression of malignant diseases. Herein, a label-free and selective fluorescence platform was proposed for miRNA based on light-up "G-quadruplex nanostring" via duplex-specific nuclease (DSN) mediated tandem rolling circle amplification (RCA). First, a long DNA generated from upstream RCA was designed with the antisense sequences for miR-21 and downstream RCA primer. Upon recognizing miR-21, the resulting DNA-RNA permitted DSN digestion and triggered downstream two-way RCA, and generation of abundant "G-quadruplex nanostring" binding with ZnPPIX for label-free fluorescent responses. In our strategy, the strong preference of DSN for perfectly matched DNA/RNA ensures its excellent selectivity. The developed method generated wide linear response with LOD of 1.019 fM. Additionally, the miR-21 levels in cell extracts have been evaluated, revealing the utility of this tool for biomedical research and clinical diagnosis.

The copper transporter, SLC31A1, transcriptionally activated by ELF3, imbalances copper homeostasis to exacerbate cisplatin-induced acute kidney injury through mitochondrial dysfunction.

Acute kidney injury (AKI) is a common complication of cisplatin chemotherapy, which greatly limits its clinical effect and application. This study explored the function of solute Carrier Family 31 Member 1 (SLC31A1) in cisplatin-induced AKI and its possible mechanism. Mice and HK-2 cells were exposed to cisplatin to establish the in vivo and in vitro AKI models. Cell viability was detected by CCK-8. Mitochondrial and oxidative damage was determined by Mito-Tracker Green staining, mtROS level, ATP production, mitochondrial membrane potential, MDA content and CAT activity. AKI was evaluated by renal function and histopathological changes. Apoptosis was detected by TUNEL and caspase-3 expression. Molecule expression was measured by RT-qPCR, Western blotting, and immunohistochemistry. Molecular mechanism was studied by luciferase reporter assay and ChIP. SLC31A1 level was predominantly increased by cisplatin exposure in AKI models. Notably, copper ion (Cu+) level was enhanced by cisplatin challenge. Moreover, Cu+ supplementation intensified cisplatin-induced cell death, mitochondrial dysfunction, and oxidative stress in HK-2 cells, indicating the involvement of cuproptosis in cisplatin-induced AKI, whereas these changes were partially counteracted by SLC31A1 knockdown. E74 like ETS transcription factor 3 (ELF3) could directly bind to SLC31A1 promoter and promote its transcription. ELF3 was up-regulated and positively correlated with SLC31A1 expression upon cisplatin-induced AKI. SLC31A1 silencing restored renal function, alleviated mitochondrial dysfunction, and apoptosis in cisplatin-induced AKI mice. ELF3 transcriptionally activated SLC31A1 to trigger cuproptosis that drove cisplatin-induced AKI through mitochondrial dysfunction, indicating that SLC31A1 might be a promising therapeutic target to mitigate AKI during cisplatin chemotherapy.

Based on Fe and Ni prepared organic colloidal materials as efficient oxide nanozymes for chemiluminescence detection of GSH and Hg(II) ions.

Metal-organic gels (MOGs) are a type of metal-organic colloid material with a large specific surface area, loose porous structure, and open metal active sites. In this work, FeNi-MOGs were synthesized by the simple one-step static method, using Fe(III) and Ni(II) as the central metal ions and terephthalic acid as the organic ligand. The prepared FeNi-MOGs could effectively catalyze the chemiluminescence of luminol without the involvement of H2O2, which exhibited good catalytic activity. Then, the multifunctional detected platform was constructed for the detection of GSH and Hg2+, based on the antioxidant capacity of GSH, and the strong affinity between mercury ion (Hg2+) and GSH which inactivated the antioxidant capacity of GSH. The experimental limits of detection (LOD) for GSH and Hg2+ were 76 nM and 210 nM, and the detection ranges were 2-100 µM and 8-4000 µM, respectively. The as-proposed sensor had good performance in both detection limit and detection range of GSH and Hg2+, which fully met the needs of daily life. Surprisingly, the sensor had low detection limits and an extremely wide detection range for Hg2+, spanning five orders of magnitude. Furthermore, the detection of mercury ions in actual lake water and GSH in human serum showed good results, with recovery rates ranging from 90.10 % to 105.37 %, which proved that the method was accurate and reliable. The as-proposed sensor had great potential as the platform for GSH and Hg2+ detection applications.

Facile preparation of bimetallic Au-Cu nanoclusters as fluorescent nanoprobes for sensitive detection of Cr3+ and S2O82- ions.

Metallic nanoclusters (NCs) have attracted special attention from researchers due to their interesting optical properties. In this experiment, we proposed a facile one-step method for the synthesis of bimetallic gold-copper nanoclusters (AuCuNCs). The prepared AuCuNCs were characterized by fluorescence spectroscopy (FL), UV-vis absorption spectrum, transmission electron microscopy (TEM), etc. The emission peak of the prepared AuCuNCs was located at 455 nm and showed blue luminescence under the excitation of 365 nm UV light. Furthermore, after the addition of Cr3+ and S2O82- ions, the FL emission intensity of AuCuNCs was significantly reduced at 455 nm and there was a color change of diminished blue luminescence under UV lamp. The AuCuNCs exhibited excellent linearity and sensitivity for the detection of Cr3+ and S2O82- ions. The limits of detection (LOD) for the Cr3+ and S2O82- ions were calculated to be 1.5 and 0.037 µM, respectively. Finally, the recoveries of Cr3+ and S2O82- ions in Runxi Lake and tap water were measured by standard addition recovery test and were 96.66 âˆ¼ 116.29 %, 95.75 âˆ¼ 119.4 %.

Eu doped Ti3C2 quantum dots to form a ratiometric fluorescence platform for visual and quantitative point-of-care testing of tetracycline derivatives.

Antibiotic residues have become a public health issues, the fast detection of tetracycline (Tc) in the environment is urgently required. In this work, Ti3C2 quantum dots (Ti3C2 QDs) and Europium ions jointly constructed a ratiometric fluorescence (FL) platform for the detection of Tc, based on synergistic impact of the Foster Resonance Energy Transfer (FRET) from Ti3C2 QDs to Eu3+ ions and the Antenna Effect (AE) between Tc and Eu3+ ions. And we proposed a ratiometric FL platform for detecting Tc with good linear response range (100-1000 uM) and low detection limit (48.79 nM). Meanwhile, we applied this platform to detect a serious of ß-diketone ligands of Eu3+ ions, demonstrating the platform's versatility for this category of chemical. Furthermore, based on the color changes of QDs@Eu3+ from blue to red at 365 nm ultraviolet light, an intelligent detection smart device was built for the visual semi-quantitative detection of Tc in actual samples. We proved the applicability of the device in complicated samples and the potential for rapid, sensitive, intuitive and point-of-care detection in the field of environment, food, pharmaceutical and agriculture.

Utilizing dual carriers assisted by enzyme digestion chemiluminescence signal enhancement strategy simultaneously detect tumor markers CEA and AFP.

To measure two tumor biomarkers, alpha-fetoprotein (AFP) and carcinoembryonic antigen (CEA), a dual-carrier CL sensor with restriction enzyme digestion (Exo I) and aptamer technology utilizing gold nanoparticles (hydroxylamine amplification) and horseradish peroxidase (HRP) as the CL signal enhancement in the sensing strategy was formed. These nanoparticles and nano-enzyme were precisely detected and tagged to the appropriate position attributable to the particular recognition of biotin and streptavidin. In this sensing strategy, target markers were further enriched and recognized sensitively by CL following enrichment, and matching strong chemical signals were collected under luminol catalysis, allowing for marker identification. For CEA (0.1-80 ng/mL) and AFP (2-500 ng/mL), the proposed method has a large linear range, with detection limits of 36.6 pg/mL and 0.94 ng/mL, respectively.

Chemiluminescence "signal-on-off" dual signals ratio biosensor based on single-stranded DNA functions as guy wires to detect EcoR V.

Signal output mode is the important part of biosensor. In general, "signal on" and "signal off" are two common output modes. The development of dual signals-based ratio analysis as a powerful diagnostic tool has attracted widespread attention in the biosensor field in recent years. Dual signals ratio sensors with "signal on" and "signal off" are more favored because of their low background signal and better sensitivity and selectivity. In this study, inspired by the idea that EcoR V can cut specific sites of DNA to produce two corresponding fragments, and by using the capturing probe as guy wires, a reliable and sensitive method for EcoR V assay is developed based on the ratio of dual chemiluminescence (CL) signals for the first time. In particular, in the existence of the objective EcoR V, the substrate DNA would be degraded into two double stranded oligonucleotides with blunt ends which include the sequence I and the sequence II, then they can separately compete with two different corresponding capture probes on magnetic beads (MBs). One of capture probe hybridized with the sequence I containing more guanine (G) bases that reacted with the phenylglyoxal (PG) to produce chemical reaction which triggered a positive CL signal output I + CL as "signal-on"; another capture probe is priority to hybridize the sequence II, which triggered the weaker reporter DNA linked with horseradish peroxidase (HRP) probe to fall off the MBs, thereby outputting a negative CL signal I-CL as "signal-off". By comparing the linear relation and the correlation coefficient, the I-CL/I + CL ratio method has better linear relation (0.01-10 U/mL) and higher sensitivity (0.0045 U/mL). In addition, this developed strategy of high selectivity which can directly detect low concentration of target EcoR V in human serum, and thus this dual ratio biosensor might offer a promising detection approach for clinical diagnostics.

One-pot label-free dual-aptasensor as a chemiluminescent tool kit simultaneously detect adenosine triphosphate and chloramphenicol in foods.

The chemiluminescence (CL) analysis based on label-free dual-aptasensor was developed for simultaneous detection of adenosine triphosphate (ATP) and chloramphenicol (CAP) in food. Magnetic microspheres and polystyrene microspheres used as separating and immobilizing carriers which immobilized the two different captured DNA, respectively. Then these carriers were put in the mixture of ATPs, CAPs, ATP-binding aptamers and CAP-binding aptamers to make one-pot label-free recognized interaction. The more ATP or CAP molecules binding their aptamers, the less aptamers left on the surface of carriers reducing the CL signals. The proposed aptasensor exhibited high selectivity and sensitivity for ATP and CAP with the limits of detection of 3.76 × 10-8 moL/L and 2.48 × 10-8 moL/L, respectively. Finally, this method is further validated by measuring the recovery of ATP/CAP spiked in three different food samples.

DNA aptamer folding on magnetic beads for sequential detection of adenosine and cocaine by substrate-resolved chemiluminescence technology.

We have developed a new aptamer-based chemiluminescence (CL) biosensing platform for the sequential detection of two small molecules as exemplified by adenosine and cocaine. Each biosensing platform comprises NH(2)-functionalized capture DNA immobilized on magnetic beads; this can hybridize with one end of the aptamer. A corresponding reporter DNA probe labeled with either digoxigenin or biotin on its 5'-terminus recognizes the other end of the aptamer. The target compounds adenosine or cocaine act as specific competitors to aptamer-reporter DNA binding, and the corresponding aptamers preferentially form target-aptamer complexes. This results in detachment of the reporter DNA probe from the magnetic beads, with more target molecules resulting in less reporter DNA probe remaining on the beads. Those left are sequentially detected by using substrate-resolved anti-digoxigenin-alkaline phosphatase and streptavidin-horseradish peroxidase. Experimental results confirm that this CL immunosensing platform has good sensitivity with detection limits of 5.2 x 10(-9) M and 3.2 x 10(-9) M for adenosine and cocaine, respectively. Because it is straightforward to adapt this strategy to detect a spectrum of small molecules by using different aptamers, this method may offer a new direction in designing high-performance CL aptasensors for sensitive and sequential determination of a limited number of small molecules.

Label-free and enzyme-free one-step rapid colorimetric detection of DNA methylation based on unmodified gold nanoparticles.

DNA methylation has been identified as one of the important causes of tumorigenesis, so it is important to develop some advanced methods for detecting and quantifying DNA methylation. In this study, a label-free and enzyme-free one-step rapid colorimetric detection of DNA methylation based on unmodified Au nanoparticles(Au NPs)has been proposed. This method can quickly, efficiently, economically and easily colorimetric detect methylated DNA only by the color change of unmodified Au NPs solution without the covalent modification of Au NPs in advance or complicated instruments for implementation with practical limitations or expensive biological enzymes or traditional organic dyes during the reaction. The strategy employed the difference in electrostatic attraction of single-stranded DNA and double-stranded DNA against salt-induced aggregation of Au NPs. The method has a DNA methylated detection limit of 8.47 nM and it is distinctly visible to detect methylated DNA with the naked eye as low as 20 nM. Furthermore, the strategy has an ability to detect methylated DNA in the presence of abundant unmethylated DNA with the detection limit of 0.13% and as low as 1% methylated DNA can be distinguished in heterogeneous samples with the naked eye. Also, the stratagem provides a convenient and rapid platform for methylated DNA detection of human serum samples in one step, which displays a huge potential for clinical diagnosis and treatment of oncological diseases.

A new chemiluminescence method for the determination of 8-hydroxyguanine based on l-histidine bound nickel nanoparticles.

A new chemiluminescence aptasensor for sensitive and efficient detection of 8-hydroxyguanine based on the synergistic interaction of Ni NPs@l-histidine@aptamer@MBs has been developed, and it has been applied in the real urine samples of cancer patients.

In situ extraction of intracellular L-asparaginase using thermoseparating aqueous two-phase systems.

The feasibility and generic applicability of directly integrating conventional discrete operations of cell disruption by high pressure homogenizer and the product capture by aqueous two-phase extraction (ATPE) system have been demonstrated for the extraction of intracellular L-asparaginase from E. coli. In a side-by-side comparison with the conventional ATPE process, including cell disruption, centrifugal clarification and following ATPE, purification of L-asparaginase via this novel in situ ATPE process yielded a product of L-asparaginase with a higher specific activity of 94.8 U/(mg protein) and a higher yield of 73.3%, both of which in the conventional ATPE process were 78.6 U/(mg protein) and 52.1%, respectively. In the purification of L-asparaginase (pI=4.9), product-debris interactions commonly diminish its recovery. It was demonstrated that immediate extraction of L-asparaginase in ATPE systems when it is released at pH 5.0 during cell disruption effectively increased its recovery in the top phase due to the reduced interaction between L-asparaginase and cell debris and the reduced degradation by contaminated protease. In addition, no clarification step and/or disruptate storage are required in this in situ ATPE, which reduced the number of unit operations and thus shortened the overall process time. This novel process has a good potential for the separation of other intracellular biological products.

Improving alachlor biodegradability by ferrate oxidation.

Alachlor can be recalcitrant when present at high concentrations in wastewater. Ferrate oxidation was used as a pretreatment to improve its biodegradability and was evaluated by monitoring alachlor elimination and removal of COD(Cr) (chemical oxygen demand determined by potassium dichromate) during the oxidation process up to a value compatible with biological treatment. Ferrate oxidation resulted in elimination of alachlor followed by degradation of its intermediates. High pH suppressed alachlor removal and COD(Cr) removal due to the low redox potential of ferrate ions. Although alachlor can be totally eliminated within 10 min under optimized conditions (alachlor, 40 mg l(-1); ferrate:alachlor molar ratio, 2; and pH 7.0), its complete mineralization cannot be achieved by ferrate oxidation alone. Alachlor solution treated by ferrate for 10 min inhibited an up-flow biotreatment with activated sludge. The biodegradability of ferrate-pretreated solution improved when the treatment was increased to 20 min, at the point of which BOD(5)/COD(Cr) ratio of the treated solution was increased to 0.87 from 0.35 after 10 min treatment. Under optimized conditions, ferrate oxidation for 20 min resulted in total elimination of alachlor, partial removal of COD(Cr) and the ferrate-treated solution could be effectively treated by the up-flow activated sludge process.

[Encapsulating hepatocytes with chitosan in physiological conditions].

Prepared from 15.3% N-acetylated chitosan (FNC), half N-acetylated chitosan (HNC) possesses a good solubility in a weak basic solution, guaranteeing the formation of microcapsules by the coacervating reaction between HNC and methacrylic acid (MAA)-hydroxyethyl methacrylate (HEMA)-methyl methacrylate (MMA) (MAA-HEMA-MMA) terpolymer under physiological conditions. When hepatocytes were encapsulated in such 3-dimensional microenvironment, as compared to monolayer culture, cell functions, including P450 activity, urea production and albumin release, were well supported. The prepared microcapsules have good mechanical stability and permeability.

A novel small Odorranalectin-bearing cubosomes: preparation, brain delivery and pharmacodynamic study on amyloid-ß25₋35-treated rats following intranasal administration.

Because of the immunogenicity and toxicity in vivo of large molecules such as lectins, the application of these molecules is remarkably restricted in drug delivery systems. In this study, to improve the brain drug delivery and reduce the immunogenicity of traditional lectin modified delivery system, Odorranalectin (OL, 1700 Da), a novel non-immunogenic small peptide, was selected to establish an OL-modified cubosomes (Cubs) system. The streptavidin (SA)-conjugated Cubs were prepared by incorporating maleimide-PEG-oleate and taking advantage of its thiol group binding reactivity to conjugate with 2-iminothiolane thiolated SA; mono-biotinylated OL was then coupled with the SA-modified Cubs. The OL-decorated Cubs (OL-Cubs) devised via a non-covalent SA-biotin "bridge" made it easy to conjugate OL and determine the number of ligands on the surface of the Cubs using sensitive chemiluminescent detection. Retention of the bio-recognitive activity of OL after covalent coupling was verified by hemagglutination testing. Nose-to-brain delivery characteristic of OL-Cubs was investigated by in vivo fluorescent biodistribution using coumarin-6 as a marker. The relative uptake of coumarin carried by OL-Cubs was 1.66- to 3.46-fold in brain tissues compared to that incorporated in the Cubs. Besides, Gly14-Humanin (S14G-HN) as a model peptide drug was loaded into cubosomes and evaluated for its pharmacodynamics on Alzheimer's disease (AD) rats following intranasal administration by Morris water maze test and acetylcholinesterase activity determination. The results suggested that OL functionalization enhanced the therapeutic effects of S14G-HN-loaded cubosomes on AD. Thus, OL-Cubs might offer a novel effective and noninvasive system for brain drug delivery, especially for peptides and proteins.

Feasibility of biogas production from anaerobic co-digestion of herbal-extraction residues with swine manure.

The objective of this work was to examine the feasibility of biogas production from the anaerobic co-digestion of herbal-extraction residues with swine manure. Batch and semi-continuous experiments were carried out under mesophilic anaerobic conditions. Batch experiments revealed that the highest specific biogas yield was 294 mL CH(4) g(-1) volatile solids added, obtained at 50% of herbal-extraction residues and 3.50 g volatile solids g(-1) mixed liquor suspended solids. Specific methane yield from swine manure alone was 207 mL CH(4) g(-1) volatile solid added d(-1) at 3.50 g volatile solids g(-1) mixed liquor suspended solids. Furthermore, specific methane yields were 162, 180 and 220 mL CH(4) g (-1) volatile solids added d(-1) for the reactors co-digesting mixtures with 10%, 25% and 50% herbal-extraction residues, respectively. These results suggested that biogas production could be enhanced efficiently by the anaerobic co-digestion of herbal-extraction residues with swine manure.

Label-free aptamer-based chemiluminescence detection of adenosine.

We have developed a novel sensitive chemiluminescence (CL) aptasensor for the target assay as exemplified by using adenosine as a model target. In this work, we have demonstrated the signaling mechanism to make detection based on magnetic separation and 3,4,5-trimethoxyl-phenylglyoxal (TMPG), a special CL reagent as the signaling molecule, which reacts instantaneously with guanine nucleobases (G) of adenosine-binding aptamer strands. Briefly, amino-functioned capture DNA sequences are immobilized on the surface of carboxyl-modified magnetic beads, and then hybridized with label-free G-rich (including 15 guanine nucleobases) adenosine-binding aptamer strands to form our CL aptasensor. Upon the introduction of adenosine, the aptamer on the surface of magnetic beads is triggered to make structure switching to the formation of the adenosine/aptamer complex. Consequently, G-rich aptamer strands are forced to dissociate from magnetic beads sensing interface, resulting in a decrease of CL signal. The decrement of peak signal is proportional to the amount of adenosine. The effects of the amounts of capture DNA, aptamer, magnetic beads are investigated and optimized. It was found that the CL intensity had a linear dependency on the concentration of adenosine in the range of 4x10(-7) to 1x10(-5)M. With a low detection limit of 8x10(-8)M and simplicity in CL detection, this novel technique will offer a great promise for future target/aptamer analysis.