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 %.

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.

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.

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.

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.

Label-free fluorescence strategy for methyltransferase activity assay based on poly-thymine copper nanoclusters engineered by terminal deoxynucleotidyl transferase.

The assay of detecting DNA methyltransferase activity has been identified as one of the central challenges in cancer diagnostics as DNA methylation is closely related to the diagnosis and treatment of tumors. In this study, a label-free fluorescence probe based on poly-thymine copper nanoclusters engineered by terminal deoxynucleotidyl transferase is proposed for methyltransferase activity assay. Taking advantage of the efficient polymerization extension reaction catalyzed by terminal deoxynucleotidyl transferase and the copper nanoclusters with large Stokes shift instead of labeling fluorescent dyes, the strategy exhibits a broader linear scope from 1 to 300 U mL-1 with a detection limit of 0.176 U mL-1. The economical method is specificity for M.SssI and also provides a convenient and high-throughput platform for screening the DNA methylation inhibitors, which displays a great potential for the practical applications of the drug development and clinical cancer diagnosis in the future.

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.

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.

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.

Correction to: Effects of miR-150-5p on the growth and SOCS1 expression of rheumatoid arthritis synovial fibroblasts.

The first name of the co-author of the above article was presented incorrect in the published version. The author name "Miangliang Qiu" should read "Mingliang Qiu" as mentioned above.

Effects of miR-150-5p on the growth and SOCS1 expression of rheumatoid arthritis synovial fibroblasts.

OBJECTIVE: miR-150-5p has been implicated in the regulation and onset of immune diseases. We investigated the effects of miR-150-5p on the functions of RA synovial fibroblasts (RASFs). METHOD: The binding site between suppressor of cytokine signaling 1 (SOCS1) and miR-150-5p was analyzed using European Bioinformatics Institute database, and the 3' UTR of SOCS1 mRNA, including the binding site, was amplified and ligated to the 3'-end of LUC2 gene in the pmirGL0 dual-luciferase vector. The pmirGL0 vector and corresponding mimics were subsequently co-transfected into 293T cells to compare the relative fluorescence intensity of LUC2 between the miR-150-5p mimics and the negative control (NC) mimics groups. Further, the RASF cell line MH7A was transfected with miR-150-5p or NC mimics and subjected to flow cytometric analysis, cell counting kit-8 assay, western blot analysis, qPCR, and enzyme-linked immunosorbent (ELISA) assay 48 h after transfection. RESULTS: miR-150-5p mimics resulted in a lower cell apoptotic rate and proportion of cells in the S phase. Using a dual-luciferase reporter gene assay, we then found that SOCS1 is a potential target of miR-150-5p. Compared with NC mimics, miR-150-5p mimics significantly decreased the protein and mRNA expression levels of SOCS1. ELISA assay showed that miR-150-5p mimics increased interleukin-6 level in the cell culture medium but did not influence tumor necrosis factor-alpha levels. CONCLUSIONS: Overall, the growth-promoting effect of miR-150-5p on MH7A cells may be attributed to the miR-150-5p-induced degradation of SOCS1 mRNA, suggesting a potential therapeutic target for RA.Key Points• SOCS1 is a potential target of miR-150-5p.• miR-150-5p promoted the growth of RASF cell line MH7A.• miR-150-5p increased the secretion of IL-6 but did not significantly affect TNF-α levels in MH7A cells.

Colorimetric determination of the activity of methyltransferase based on nicking enzyme amplification and the use of gold nanoparticles conjugated to graphene oxide.

A method is described for the colorimetric determination of the activity of CpG methyltransferase (M.SssI). It is based on (a) the crosslinking effect between dsDNA-modified gold nanoparticles (AuNPs) and graphene oxide (GO), and (b) an amplification reaction with the aid of a nicking enzyme. To avoid the aggregation of AuNPs (which would produce false signals), a hairpin DNA was connected to the AuNPs. Thus, the red color of the solution (measured at 530 nm) increases linearly with the activity of M.SssI from 0.2 to 60 U·mL-1, and the limit of detection is 67 U·mL-1. This is superior to some reported strategies. The method was successfully applied to analyze spiked serum samples. Conceivably, it represents a powerful tool for use in drug development and diagnosis. Graphical abstracts A method based on the conjugated cross-linking effect between dsDNA modified Au NPs and GO coupled with an amplification reaction of nicking enzyme has been developed for colorimetric detection of the activity of CpG methyltransferase (M.SssI).

Fluorescence-based Polymerase Amplification for the Sensitive Detection of DNA Methyltransferase Activity.

DNA methyltransferase (MTase) is related to transcriptional repressor activity in biological functions. It is an essential for cancer diagnosis and therapeutics to detect DNA MTase activity sensitively. Here, a fluorescent system based on polymerase amplification has been developed to detect DNA adenine MTase (Dam) activity sensitively. The amplification is triggered by the probe DNA regions a, which are the primes of a polymerase-induced replicated reaction. They come from methylation and a digestion reaction of DNA S1-S1, including a 5'-GATC-3' sequence recognized by Dam MTase and methylation sensitive restriction endonuclease Dpn I. The intensities of fluorescence are dependent on the Dam MTase activity. The method shows fine sensitivity with a detection limit of 3.2 × 10-4 U mL-1 and specificity for Dam MTase. In human serum samples, the method has been successfully applied, and it has also been used to screen the inhibitors, which means that the developed method can be a powerful and potential tool for drug development and clinical diagnosis in the future.

Amplification strategy for sensitive detection of methyltransferase activity based on surface plasma resonance techniques.

In this work, a newly developed surface plasma resonance (SPR) system for the sensitive detection of M.SssI activity has been designed based on double signal amplification with DNA chain cyclic reactions and AuNPs. In the absence of M.SssI, hairpin DNA 1 (HP1) can be cleaved into s1 fragments catalyzed by HpaII. The s1 fragments can then trigger a recycling process of hairpin DNA 2 (HP2) hybridization and subsequently release massive s2 and s3 in the solution of Nt.AlwI and HPII. AuNPs-DNA can be captured on gold film by the released s2 and s3 to produce a strong SPR signal. Whereas in the presence of M.SssI, methylated HP1 cannot be cleaved by HpaII, thus produce a weak SPR signal. The SPR signals are dependent on the M.SssI concentration in the range from 0.5 to 50 U/mL. The successful detection of M.SssI activity in clinical serum samples and inhibition of M.SssI using 5-Aza and 5-Aza-dC indicate a great potential of this strategy for building new monitoring platform in bioanalysis and clinical biomedicine.

Label-free colorimetric detection of biothiols utilizing SAM and unmodified Au nanoparticles.

Herein, a sensitive and selective sensor for biothiols based on colorimetric assay is reported. S-adenosyl-L-methionine (SAM) could induce the selective aggregation of unmodified gold nanoparticles (AuNPs) by electrostatic interaction. In the presence of biothiols, such as glutathione (GSH), homocysteine (Hcy), and cysteine (Cys), AuNPs prefer to react with thiols of biothiols rather than SAM due to the formation of Au-S bond. Thus, the AuNPs turn from the aggregation to the dispersion state, and the corresponding color variation in the process of anti-aggregation of AuNPs can be used for the quantitative screening of biothiols through UV-vis spectroscopy or by the naked eye. Under optimized conditions, a good linear relationship in the range of 0.4-1.2 µM is obtained for Cys, 0.2-0.9 µM for GSH, and 0.6-3.0 µM for Hcys. The detection limits of this assay for GSH, Cys and Hcys are 35.8 nM, 21.7 nM, and 62.4 nM, respectively. This colorimetric assay exhibits rapid operation (within 5 min), high selectivity and sensitivity towards biothiols with tunable dynamic ranges.

Label-free colorimetric assay for DNA methylation based on unmodified Au nanorods as a signal sensing probe coupled with enzyme-linkage reactions.

Using unmodified Au nanorods with enzyme-linkage reaction, a label-free colorimetric method for simple and convenient assay of DNA methylation is presented.