Magnetically separable Pd-iron-oxides composites as highly efficient and recyclable catalysts for ultra-rapid degradation and debromination of polybrominated diphenyl ethers.

When precious nano-metals are used as environmental catalysts, it is important to tune the particle sizes and the reusability of the nano-metals for achieving their highly efficient catalytic performance at a low cost. In the present work, magnetic iron oxides (FeOx-Y) nanoparticles were pre-prepared as supports of nano-metals, where Y represented the mole percentage of Fe(III) in the total iron (Y ≥ 50 %). FeOx-Y (support), PdCl42- (Pd source) and NaBH4 (reducing agent) were added into the organic pollutant solution containing 2,2',4,4'-tetrabromodiphenyl ether (BDE47). After the NaBH4 was added, the followed reaction realized not only the rapid in-situ preparation of a Pd-loaded FeOx-Y composite catalyst (Pd-FeOx-Y), but also the ultra-fast and complete debromination of BDE47 within 30 s. Comparing the case without adding FeOx-Y, the debromination efficiency of BDE47 was much promoted in the presence of FeOx-Y. The support-induced enhancing effect on the catalytic ability of Pd nanoparticles was improved by increasing the Fe(III) content in the support, being attributed to the much more hydroxyl groups on the support surface. Considering both the catalytic and recovery abilities of Pd-FeOx-Y, Pd-FeOx-75 was the optimal choice because it could be magnetically recovered and re-used for multiple cycles with high catalytic activities. The presently developed "catalyst preparation-pollutant degradation" one-pot system could be applied to conduct complete debromination of all the PBDEs.

Ultrasensitive electrochemical detection of miRNA based on polymerization signal amplification.

The detection of trace tumor-related serum miRNA biomarkers is in great demand for the early diagnosis of cancer. Herein, for the first time, an electrochemical sensing platform based on atom transfer radical polymerization (ATRP) signal amplification strategy for ultrasensitive determination of the breast and prostate cancer marker miRNA-141 has been developed. The hairpin DNAs were immobilized on the benzoic acid modified electrode to capture the target miRNA-141, the recognition of miRNA-141 released thiol groups on the end of probes, followed by the association of ATRP initiators modified gold nanoparticles with thiol groups, and then triggered the polymerization on electrode surface, causing a great number of ferrocene (Fc) signal molecules grafted on the sensor interface. As a result, the electrochemical signal intensity of signal molecule has been greatly increased. The proposed biosensor has a linear range from 10 pM to 10 aM with a detection limit of 3.23 aM for miRNA-141, opening a new and promising path for ultrasensitive analysis of tumor-related miRNAs.

Electrochemical CYFRA21-1 DNA sensor with PCR-like sensitivity based on AgNPs and cascade polymerization.

In this work, a new method of CYFRA21-1 DNA (tDNA) detection based on electrochemically mediated atom transfer radical polymerization (e-ATRP) and surface-initiated reversible addition-fragmentation chain transfer polymerization (SI-RAFT) cascade polymerization and AgNP deposition is proposed. Firstly, the peptide nucleic acid (PNA) probe is captured on a gold electrode by Au-S bonds for specific recognition of tDNA. After hybridization, PNA/DNA strands provide high-density phosphate groups for the subsequent ATRP initiator by the identified carboxylate-Zr4+-phosphate chemistry. Then, a large number of monomers are successfully grafted from the DNA through the e-ATRP reaction. After that, the chain transfer agent of SI-RAFT and methacrylic acid (MAA) are connected by recognized carboxylate-Zr4+-carboxylate chemistry. Subsequently, through SI-RAFT, the resulting polymer introduces numerous aldehyde groups, which could deposit many AgNPs on tDNA through silver mirror reaction, causing significant amplification of the electrochemical signal. Under optimal conditions, this designed method exhibits a low detection limit of 0.487 aM. Moreover, the method enables us to detect DNA at the level of PCR-like and shows high selectivity and strong anti-interference ability in the presence of serum. It suggests that this new sensing signal amplification technology exhibits excellent potential of application in the early diagnosis of non-small cell lung cancer (NSCLC). Graphical abstract Electrochemical detection principle for CYFRA21-1 DNA based on e-ATRP and SI-RAFT signal amplification technology.

Ultrasensitive fluorescent detection of HTLV-II DNA based on magnetic nanoparticles and atom transfer radical polymerization signal amplification.

Human T-lymphotropic virus type II (HTLV-II) is a crucial retrovirus that is closely associated with a variety of human diseases. Herein, an ultrasensitive fluorescent HTLV-II DNA detection strategy was developed for the first time based on magnetic nanoparticles (MNPs) and atom transfer radical polymerization (ATRP) amplification. In this approach, hairpin DNA probes (pDNA) labelled with 5' thiol and 3' azide group terminally were immobilized on amino group modified MNPs surface through sulfo-N-succinimidyl-4-maleimidobutyrate sodium salt (sulfo-GMBS) cross-linkers. In the presence of target DNAs (tDNA), pDNA hybridized with tDNA to form double-stranded DNA, and therefore its azide group was away from the MNPs surface. Subsequently, to initiate ATRP reaction, initiators were introduced into the pDNA by a Cu (I)-catalyzed alkyne-azide cycloaddition (CuAAC). Then, large numbers of 9-anthracenylmethyl methacrylate polymer (pAMMA) were successfully labelled on the MNPs surface, resulting in significant amplification of the fluorescence signal. Under optimized conditions, the fluorescence signal was proportional to the logarithm of the concentration of tDNA over the range from 1 fM to 1 nM, with a detection limit of 0.22 fM. Moreover, this strategy was capable of discriminating mismatched bases and detecting HTLV-II DNA in human serum samples. By virtue of the high sensitivity, selectivity, simplicity and economy, this ultrasensitive biosensor demonstrates great potential for biomedical research and early clinical diagnosis.

Ultrasensitive fluorescence detection of sequence-specific DNA via labeling hairpin DNA probes for fluorescein o-acrylate polymers.

Sensitive detection of DNA is conducive to enhance the accuracy of diseases diagnosis and risk prediction. In this work, we report the use of activators generated by electron transfer for atom transfer radical polymerization (AGET ATRP) as a novel on-chip amplification strategy for the fluorescence detection of DNA. More specifically, the target DNA was captured by the on-chip immobilized hairpin DNA probes. Upon hybridization, exposed 3'-N3 of the hairpin was used to attach AGET ATRP initiators onto the silicon surface by click chemistry. Then, numerous fluorescent labeling linked to the end of the probes via the formation of long chain polymers of fluorescein o-acrylate, which in turn amplified the fluorescence signal for DNA detection. Under optimal conditions, it showed a good linear range from 100 fM to 1 µM in DNA detection, with the limit of detection as low as 4.3 fM. Moreover, this strategy showed good detection performance in complex real serum samples, the fluorescence intensity of 0.1 nM tDNA in 1% fetal bovine serum samples was 97.6% of that in Tris-EDTA buffer. Based on its high sensitivity, reduced cost and simplicity, the proposed signal amplification strategy displays translational potential in clinical application.

Ultrasensitive DNA biosensor based on electrochemical atom transfer radical polymerization.

Here we report a highly selective and ultrasensitive DNA biosensor based on electrochemical atom transfer radical polymerization (ATRP) signal amplification and "Click Chemistry". The DNA biosensor was prepared by immobilizing thiol and azide modified hairpin DNAs on gold electrode surface. In the presence of target DNAs (T-DNA), hairpin probes hybridized with T-DNAs to form a duplex DNA, and the ring of hairpin DNA was opened to make azide groups accessible at 3' ends. "Click reactions" proceeded between the azide and propargyl-2-bromoisobutyrate (PBIB) to initiate the ATRP reaction which brought a large number of ferrocenylmethyl methacrylate (FMMA) on the electrode surface. The amount of FMMA was proportional to the concentration of T-DNA and quantified by square wave voltammetry. Combining ATRP signal amplification with "Click Chemistry", the optimized DNA biosensor was capable of detecting 0.2 aM. T-DNA. The preliminary application of the developed DNA biosensor was demonstrated by detecting target DNA in spiked serum samples. The developed DNA biosensor shows great promise for the detection of gene biomarkers.

Hairpin probes based click polymerization for label-free electrochemical detection of human T-lymphotropic virus types II.

A novel, simple, and label-free amplification electrochemical impedance method for quantitative detection of Human T-lymphotropic virus types II(HTLV-II) via click chemistry-mediated of hairpin DNA probes (hairpins) with polymers was developed. The hairpins were firstly attached to the gold electrode surface by an S-Au bond, the azido terminals of hairpins were close to the electrode surface, which make it difficult to be approached. After hybridizing with HTLV-II, the hairpins were unfolded and experienced a big configuration change, which made the azido terminals of the hairpins available to conjugate with alkynyl-containing polymer, called P(DEB-DSDA), formed by 1,4-diacetylenebenzene (DEB) and 4,4'-Diazido-2,2'-stilbenedisulfonic acid disodium salt tetrahydrate (DSDA) via Cu(I)-catalyzed azide-alkyne cycloaddition (CuAAC). With amount of P(DEB-DSDA) conjugated with the hairpin probes via click polymerization, its electrochemical signal can have a great amplification. Under optimized experimental conditions, this new probe showed a low detection limit of 0.171 pM with a good liner in the range of 1 pM-1 nM. Meanwhile, the biosensor also exhibited good selectivity and reliability in detection of real serum samples, indicating that it has great application potential in clinical DNA diagnosis and detection.

TEMPO-Functionalized Nanoporous Au Nanocomposite for the Electrochemical Detection of H2O2.

A novel nanocomposite of nanoporous gold nanoparticles (np-AuNPs) functionalized with 2,2,6,6-tetramethyl-1-piperidinyloxy radical (TEMPO) was prepared; assembled carboxyl groups on gold nanoporous nanoparticles surface were combined with TEMPO by the "bridge" of carboxylate-zirconium-carboxylate chemistry. SEM images and UV-Vis spectroscopies of np-AuNPs indicated that a safe, sustainable, and simplified one-step dealloying synthesis approach is successful. The TEMPO-np-AuNPs exhibited a good performance for the electrochemical detection of H2O2 due to its higher number of electrochemical activity sites and surface area of 7.49 m2g-1 for load bigger amount of TEMPO radicals. The TEMPO-functionalized np-AuNPs have a broad pH range and shorter response time for H2O2 catalysis verified by the response of amperometric signal under different pH and time interval. A wide linear range with a detection limit of 7.8 × 10-7 M and a higher sensitivity of 110.403 µA mM-1cm-2 were obtained for detecting H2O2 at optimal conditions.

Highly sensitive fluorometric determination of thrombin by on-chip signal amplification initiated by terminal deoxynucleotidyl transferase.

The article describes an on-chip amplification scheme initiated by a terminal deoxynucleotidyl transferase (TdT) for highly sensitive fluorometric determination of protein. Two thrombin-binding aptamers were designed to capture thrombin as they can form a sandwich structure for improved specificity. An amino-modified aptamer (TBA29) was first immobilized on a silicon chip. After capture of thrombin, a second aptamer (TBA15) was conjugated to the second binding site of thrombin. The 3'-terminal of aptamer TBA15 is exposed on the chip surface, and then fluorescein-labeled 12-dATP associates to the 3'-terminal with the help of TdT. This results in signal amplification, and eventually leads to highly sensitive detection. Under optimal conditions, fluorescence intensity is linearly related to the logarithm of thrombin concentration in the range of 100 fM - 0.1 µM, and the detection limit is as low as 2.0 fM. The assay is sensitive and selective even over potentially interfering proteins and in the presence of human serum. Graphical abstract Schematic strategy for thrombin detection. Two thrombin-binding aptamers were designed to capture thrombin to form a sandwich structure for improved specificity. The protein detection is based on TdT initiated on-chip fluorescent amplification.