Organic polymer/inorganic heterostructure coupled with efficient allosteric bicycle strand displacement for photochemical sensing.

In this work, a high-performance conjugated microporous polymer (CMP) decorated with BiOBr (Tr(PhXOD)3-CMP/BiOBr) is synthesized to application in construction of ultrasensitive photoelectrochemical (PEC) biosensor for sensing miRNA-122, by firstly coupling with efficient clip toehold-mediated allosteric bicycle strand displacement (ABSD). Notably, the Tr(PhXOD)3-CMP/BiOBr not only owns self-enhanced D-A-D structure that extremely shortens migration distance of photo-generated electron, but also forms Z-type heterostructure for accelerating electron-hole separation, thereby significantly enhancing the photocurrent with 10-fold higher than commonly used methods. Meanwhile, the clip toehold-mediated ABSD based on ternary linkage structure transformation avoids the attrition of invading strand, endowing the conservation of high concentration for undergoing rapid reaction with high-efficiency DNA amplification, which dramatically improves reaction time and superior target conversion. The experimental results indicate that proposed PEC biosensor had a high sensitivity to miRNA-122 with a detection limit of 0.49 fM, which provides a newly organic/inorganic photosensitive nanomaterials and efficient DNA strand displacement in bioanalytical and early clinical disease diagnosis.

Long-Wavelength Illumination-Induced Photocurrent Enhancement of a ZnPc Photocathodic Material for Bioanalytical Applications.

Herein, a novel photocathodic nanocomposite poly{4,8-bis[5-(2-ethylhexyl)-thiophen-2-yl] benzo[1,2-b:4,5-b']dithiophene-2,6-diyl-alt-3-fluoro-2-[(2-ethylhexyl)-carbonyl]thieno[3,4-b]thiophene-4,6-diyl}/phthalocyanine zinc (PTB7-Th/ZnPc) with high photoelectric conversion efficiency under long-wavelength illumination was prepared to construct an ultrasensitive biosensor for the detection of microRNA-21 (miRNA-21), accompanied by a prominent anti-interference capability toward reductive substances. Impressively, the new heterojunction PTB7-Th/ZnPc nanocomposite could not only generate a strong cathodic photocurrent to improve the detection sensitivity under long-wavelength illumination (660 nm) but also effectively avoid the high damage of biological activity caused by short-wavelength light stimulation. Accordingly, by coupling with rolling circle amplification (RCA)-triggered DNA amplification to form functional biquencher nanospheres, a PEC biosensor was fabricated to realize the ultrasensitive analysis of miRNA-21 in the concentration range of 0.1 fM to 10 nM with a detection limit as low as 32 aM. This strategy provided a novel long-wavelength illumination-induced photocurrent enhancement photoactive material for a sensitive and low-damage anti-interference bioassay and early clinical disease diagnosis.

Highly efficient photocathodic cascade material for constructing sensitive photoelectrochemical biosensor.

Photocathodic biosensor possesses excellent anti-interference capability in bioanalysis, which however suffers from high electron-hole recombination rate with low photocurrent. Herein, a high-performance inorganic organic P3HT@C60@ZnO nanosphere with cascade energy band arrangement was synthesized as photoactive signal probe, which inherited the advantages of inorganic strong optical absorptivity and organic high mobility for photo-generated holes. Specifically, the well-matched band gap endowed not only the improved life for light generated carrier and promoted separation of electron-hole pairs, but also the expansion of charge-depletion layer, significantly improving the photoelectric conversion efficiency for acquiring an extremely high photocathodic signal that increased by 30 times compared with individual materials. Accordingly, by integrating with the efficient amplification of DNA nanonet derived from clamped hybrid chain reaction (C-HCR), a sensitive P3HT@C60@ZnO nanosphere based photocathodic biosensor was proposed for accurate detection of p53. The experimental results showed that the biosensor had a wide detection range from 0.1 fM to 10 nM and a low detection limit of 0.37 fM toward p53, offering a new avenue to construct sensitive PEC platform with superior anti-interference ability and hold a prospective application in early disease diagnosis and biological analysis.

Au nano-flower/organic polymer heterojunction-based cathode photochemical biosensor with reduction-accelerated quenching effect of porphyrin manganese.

In this work, a novel reduction-accelerated quenching of manganese porphyrin (MnPP) based signal-off cathode photochemical (PEC) biosensor by using Au nano-flower/organic polymer (PTB7-Th) heterojunction as platform was proposed for ultrasensitive detection of Hg2+. Firstly, the photoactive PTB7-Th with Au nano-flower on electrode could form a typical Mott-Schottky heterojunction for acquiring an extremely high cathode signal. Meanwhile, the presence of target Hg2+ could bring in the formation of T-Hg2+-T based scissor-like DNA walker, which thus activated efficient Mg2+-specific DNAzyme based cleavage recycling to shear hairpin H2 on electrode to exposure abundant trigger sites of hybridization chain reaction (HCR) for in-situ decoration of quencher MnPP. Here, besides the steric hinderance and light competition effect of MnPP decorated DNA nanowires attributing to signal decrease, we for the first time testified the MnPP reduction-accelerated quenching that constantly consumed the photo-generated electron by using cyclic voltammetry (CV). As a result, the proposed biosensor had excellent sensitivity and selectivity to Hg2+ in the range of 1 fM-10 nM with a detection limit of 0.48 fM. The actual sample analysis showed that the biosensor could reliably and quantitatively identify Hg2+, indicating an excellent application prospect in routine detection.

P3HT-PbS nanocomposites with mimicking enzyme as bi-enhancer for ultrasensitive photocathodic biosensor.

Photocathodic biosensor has great capability in anti-interference from reductive substances, however, the low signal intensity of photoactive species with inferior detection sensitivity restricts its wide application. In this work, the P3HT-PbS nanocomposites were synthesized as signal tags, by integrating with target-trigger generated hemin/G-quadruplex nanotail as bi-enhancer to significantly apmplify the photocurrent, an ultrasensitive photocathodic biosensor was proposed for detection of ß2-microglobulin (ß2-MG). Impressively, P3HT with cathode signal is an attractive polymer consisted of substantial thiophene groups with high absorption coefficient and mobility of photo-generated holes, which could anchor with the PbS dots as sensitizer, providing a high charge mobility and strong photosensitivity. More importantly, target-trigger generated hemin/G-quadruplexes could accept the electron from illuminated photoactive species through the conversion of Fe(III)/Fe(II) in hemin, effectively reducing charge recombination rate as well as accelerating the generation of electron acceptor O2 in the assistant of H2O2. Moreover, hemin/G-quadruplexes inherited the HRP mimicking catalytic capability that further improved the produce of plentiful O2. As a result, PEC cathode signal was significantly enhanced for sensitive analysis of ß2-MG protein with a good detection range of 0.1 pg/mL to 100 ng/mL. It would provide a path for establishing PEC platform with excellent anti-interference ability and extend the application of photoelectrochemical (PEC) biosensor in bioanalysis and early disease diagnosis.

A novel self-enhanced carbon nitride platform coupled with highly effective dual-recycle strand displacement amplifying strategy for sensitive photoelectrochemical assay.

In this work, a novel self-enhanced photoelectric active material, Na+, K+-codoped carbon nitride (NaKCN), was synthesized for constructing sensitive photoelectrochemical (PEC) biosensor to detect target miRNA-182-5p. Ingeniously, the NaKCN displayed glucose oxidase (GOx)-mimicking photocatalytic property, which catalyzed glucose to in situ generate high levels of H2O2 as its own electron donor for enhancing photocurrent. Moreover, the Na+, K+ co-doping could reduce energy gap of carbon nitride material, effectively improving the optical absorptivity and photocatalytic efficiency. Additionally, a novel highly effective dual-recycle TSD amplifying strategy was constructed to convert a small amount of target into plentiful two types of output DNAs labeling with sensitizer MB to enhance photocurrent of NaKCN. As a result, this PEC biosensor achieved a high sensitivity with low detection limit of 3.3 fM, which provided a new avenue for improving sensitivity of bioanalysis and diagnosis of diseases.

In Situ Formation of Multifunctional DNA Nanospheres for a Sensitive and Accurate Dual-Mode Biosensor for Photoelectrochemical and Electrochemical Assay.

Herein a photoelectrochemical (PEC) and electrochemical (EC) dual-mode biosensor with cationic N,N-bis(2-(trimethylammonium iodide)propylene)perylene-3,4,9,10-tetracarboxydiimide (PDA+)-decorated multifunctional DNA spheres in situ generated on an electrode was proposed for sensitive and accurate detection of miRNA-141. By employing a target-related ternary "Y" structure cleavage cycling reaction, the target DNA was converted into massive output DNA anchored on a TiO2 substrate, and hence triggering the rolling circle amplification (RCA) reaction. Upon addition of magnesium ions and PDA+, the long DNA tails of the RCA product were condensed in situ to form multifunctional DNA spheres. Notably, the distance between DNA spheres and TiO2 substrate was short, thus forming an effective PDA+-TiO2 sensitization structure with fast electron transfer for acquiring an extremely enhanced PEC signal with assistance of ascorbic acid (AA). Meanwhile, cationic PDA+ with a large planar π-π skeleton enabled favorable redox-activity and substantial loading on DNA spheres, directly producing an obviously well-defined cathodic peak for implementing EC biodetection on the same sensing platform. This approach not only avoided difficult assembly of diverse signal indicators but also significantly improved the sensitivity by utilizing cleavage cycling amplification and RCA strategies. Moreover, the distinct dual-response signals from two different transduction mechanisms and independent signal transduction can mutually support accuracy improvement. As a result, detection ranges of 0.1 fM to 1 nM for PEC and 2 fM to 500 pM for EC were obtained for miRNA-141, providing a universal and efficient biosensing method with promising applications in bioanalysis and early disease diagnosis.

Electrochemical lead(II) biosensor by using an ion-dependent split DNAzyme and a template-free DNA extension reaction for signal amplification.

A voltammetric biosensor for lead(II) (Pb2+) is described that is based on signal amplification by using an ion-dependent split DNAzyme and template-free DNA extension reaction. The Pb2+-dependent split DNAzyme was assembled on gold nanoparticles (Au@Fe3O4), and this nanoprobe then was exposed to Pb2+ which causes the split-off of DNAzymes to release primers containing 3'-OH groups (S1 and S2). The template-free DNA extension reaction triggers the generation of long ssDNA nanotails, which then can bind the free redox probe N,N'-bis(2-(trimethylammonium iodide)propylene)perylene-3,4,9,10-tetracarboxyldiimide (PDA+) via electrostatic adsorption. Hence, the concentration of PDA+ in solution is reduced. Therefore, less free PDA+ can be immobilized on a glassy carbon electrode modified with electrodeposited gold nanoparticles (depAu) to produce an electrochemical signal, typically measured at ∼0.38 V (vs. SCE) for quantitation of Pb2+. The use of a Pb2+-dependent split DNAzyme avoids the usage of a proteinic enzyme. It also increases the sensitivity of the sensor which has a lower detection limit of 30 pM of Pb2+. Graphical abstract Novel electrochemical biosensor based on the amplification of ion-dependent split DNAzyme and template-free DNA extension reaction for trace detection of Pb2+.

Novel D-A-D-Type Supramolecular Aggregates with High Photoelectric Activity for Construction of Ultrasensitive Photoelectrochemical Biosensor.

In this work, hydrazine-functionalized perylene diimide derivative supramolecular (HPDS), a novel self-enhanced donor-acceptor-donor (D-A-D) type aggregates with excellent photoelectric activity, was synthesized by a facile one-pot green route and further applied in construction of coreactant-free photoelectrochemical (PEC) biosensor for ultrasensitive DNA assay. Impressively, the HPDS formed by D-A-D units not only possessed effectively shorted electron-transfer path between donor and acceptor, but also presented a desiring aggregate state via the π-π stacking of perylene core and hydrogen bonding of the terminal moiety, thereby acquiring a high density electron flow for generating the extremely high PEC signal. Experimental data showed that the well film-formed HPDS aggregate could produce an exciting photocurrent intensity about 6-fold stronger than that of precursor perylene dianhydride with donor N2H4 in detection buffer and even 12-fold than that of perylene dianhydride only. In this respect, the resultant HPDS aggregate as a novel self-enhanced PEC signal tag was adopted to fabricate the coreactant-free PEC biosensor with the help of target dual-recycling-induced bipedal DNA walker cascade amplification strategy for ultrasensitive DNA (a fragment of TP53 gene) assay. The proposed biosensor showed a high sensitivity with a low detection limit down to femtomole level, providing a new avenue for sensitive bioanalysis and clinical diagnosis.

Wavelength distinguishable signal quenching and enhancing toward photoactive material 3,4,9,10-perylenetetracarboxylic dianhydride for simultaneous assay of dual metal ions.

Photoelectrochemical (PEC) assay with low background, simple instrumentation and high sensitivity has deemed as one of the most potential strategies to simultaneous multi-component detection. How to distinguish photocurrent changes caused by various targets on a single sensing platform thus becomes the key issue to be resolved. Herein, we innovatively proposed a multiplex PEC biosensor based on wavelength distinguishable signal quenching and enhancing toward photoactive material 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA) for simultaneous assay of dual metal ions. Briefly, S1 and S2 ssDNA containing sensitizer methylene blue and quencher ferrocene (termed as MB-S1 and Fc-S2), respectively, were first generated through target Pb2+ and Mg2+-induced DNAzyme-assisted target recycling, which thereafter were modified on PTCDA sensing platform specifically via host-guest recognition with ß-cyclodextrin (ß-CD). Interestingly, the sensitizer MB could enhance photocurrent of PTCDA under the excitation wavelength of 623 nm and 590 nm, respectively, while the quencher Fc just quencher the photocurrent of PTCDA under the excitation wavelength of 590 nm, thereby achieving wavelength distinguishable signal quenching and enhancing toward photoactive material PTCDA for simultaneous assay of dual metal ions. As a result, the conceived biosensor for Mg2+ and Pb2+ detection realized high sensitivity with detection limit of 0.3 pM and 0.3 nM, respectively. The proposed strategy not only for the first time achieved the discrimination of varied PEC signal caused by two targets with usage of sole photoelectric material, but also realized the simultaneous multiplex assay on a single sensing platform, providing a new way for constructing effective and sensitive PEC biosensor for multi-component detection.

Dependent signal quenching and enhancing triggered by bipedal DNA walker for ultrasensitive photoelectrochemical biosensor.

Herein, by utilizing bipedal DNA walker as booster to adjust the distance of quencher ferrocene (Fc) and sensitizer methylene blue (MB) to photoactive material perylene-3,4,9,10-tetracarboxylic acid (PTCA), a novel "on-off-super on" photoelectrochemical (PEC) biosensor was proposed for ultrasensitive detection of thrombin (TB). Firstly, the PTCA matrix on electrode could provide a high initial PEC signal assisted by depAu. Upon the Fc labeled on hairpin DNA 1 (H1-Fc) proximate to PTCA, the PEC signal could obviously decrease to reduce the background signal. Interestingly, the target TB-related bipedal DNA walker implemented the opening of H1-Fc for the departure of Fc toward PTCA, which achieved the recovery of PEC signal and exposed the prelocked toehold domain for the hybridization with hairpin DNA 2 labeled with MB (H2-MB), thereby making the MB approach to PTCA for achieving the "super on" signal. As a result, this proposed strategy showed a wide linear range from 0.5 fM to 100 nM with a low detection limit down to 0.17 fM for TB detection, providing an efficient and available avenue for sensitive detection of biomolecules in bioanalysis and disease diagnosis.

C60@C3N4 nanocomposites as quencher for signal-off photoelectrochemical aptasensor with Au nanoparticle decorated perylene tetracarboxylic acid as platform.

Herein, a novel signal-off photoelectrochemical (PEC) aptasensor was proposed for sensitive detection of thrombin on the basis of C60@C3N4 nanocomposites as quencher and Au nanoparticles (depAu) decorated perylene tetracarboxylic acid (PTCA) as sensing platform. Owing to the excellent membrane-forming of PTCA and superior conductivity of depAu, the PTCA between two depAu layers can simply and effectively produce an extremely high initial photocurrent to afford a precondition for sensitive biodetection. Thereafter, the assembly of C60@C3N4 nanocomposites on electrode via typical sandwich reaction enabled the generation of a significantly decreased photocurrent. Here, the C3N4 with high surface area not only provided massive binding sites for C60 immobilization, but also partly competed with PTCA in light absorption for producing a significantly smaller photocurrent in the presence of electron donor ascorbic acid (AA). Additionally, both the C3N4 and C60 have the poor conductivity, which could inhibit the electron transfer to achieve a further decreased photocurrent, effectively improving the sensitivity of proposed biosensor. As a result, the PEC biosensor in a "signal-off" mode showed an extremely low detection limit down to 1.5 fM, providing a sensitive and universal strategy for protein detection.

Ultrasensitive photoelectrochemical biosensor for MiRNA-21 assay based on target-catalyzed hairpin assembly coupled with distance-controllable multiple signal amplification.

Here, with the target-catalyzed hairpin assembly generated dsDNA (HP1-HP2) to synchronously control the departure of quencher ferrocene and approach of sensitizer methylene blue, a distance-controllable multiple signal amplification based photoelectrochemical biosensor was proposed for MiRNA-21 assay.

Ultrasensitive Photoelectrochemical Detection of Multiple Metal Ions Based on Wavelength-Resolved Dual-Signal Output Triggered by Click Reaction.

In this work, a click reaction-triggered wavelength-resolved dual-signal output photoelectrochemical (PEC) biosensor with DNAzymes-assisted cleavage recycling amplification was proposed for sensitive triplex metal ions assay. Substantial DNA fragments azido-S1 and azido-S2, derived from the Pb2+ (target 1) and Mg2+ (target 2) dependent cleavage cycle of DNAzymes, respectively, were grafted efficiently on the same alkynyl-DNA (capture DNA) modified electrode via the Cu2+ (target 3) and ascorbic acid (AA) cocatalyzed click reaction, which thus could be subsequently used for immobilization of two different photoactive nanomaterials labeled with single DNA to generate distinguishing dual-signal output for simultaneously sensitive detection of Pb2+ and Mg2+. Furthermore, the control variable method was used for detecting Cu2+ by altering the concentration of Cu2+ in the click reaction. Owing to the usage of the click reaction and target-converted signal amplifying strategy, the utilization rate of cycle output DNAs was largely increased, significantly improving the detection sensitivity of the proposed approach. As a result, low detection limits down to picomolar were acquired for the detection of Pb2+, Mg2+, and Cu2+, providing a versatile, efficient, and sensitive PEC method for multiple assays of various targets such as metal ions, small molecules, and tumor markers.

Effects of adding bulking agent, inorganic nutrient and microbial inocula on biopile treatment for oil-field drilling waste.

Contamination from oil-field drilling waste is a worldwide environmental problem. This study investigated the performance of four bench-scale biopiles in treating drilling waste: 1) direct biopile (DW), 2) biopile plus oil-degrading microbial consortium (DW + M), 3) biopile plus microbial consortium and bulking agents (saw dust) (DW + M + BA), 4) biopile plus microbial consortium, bulking agents, and inorganic nutrients (Urea and K2HPO4) (DW + M + BA + N). Ninety days of biopiling removed 41.0%, 44.0%, 55.7% and 87.4% of total petroleum hydrocarbon (TPH) in the pile "DW", "DW + M", "DW + M + BA", and "DW + M + BA + N" respectively. Addition of inorganic nutrient and bulking agents resulted in a 56.9% and 26.6% increase in TPH removal efficiency respectively. In contrast, inoculation of hydrocarbon-degrading microorganisms only slightly enhanced the contaminant removal (increased 7.3%). The biopile with stronger contaminant removal also had higher pile temperature and lower pile pH (e.g., in "DW + M + BA + N"). GC-MS analysis shows that biopiling significantly reduced the total number of detected contaminants and changed the chemical composition. Overall, this study shows that biopiling is an effective remediation technology for drilling waste. Adding inorganic nutrients and bulking agents can significantly improve biopile performance while addition of microbial inocula had minimal positive impacts on contaminant removal.