A double signal amplification-based homogeneous electrochemical sensor built on catalytic hairpin assembly and bisferrocene markers.

A facile, sensitive and unmodified Hg2+ homogeneous electrochemical sensor based on bisferrocene signal markers and catalytic hairpin self-assembly (CHA) was built on a gold disk electrode. Three hairpin probes were designed, in which thiol was labeled at both ends of the hairpin probe 1(HP1), while bisferrocene, a redox signal marker, was labeled at both ends of the hairpin probe 2(HP2) and hairpin probe 3(HP3). Due to the Hg2+ mediated thymine-Hg (II)-thymine (T-Hg2+-T) structure, when Hg2+ is introduced, the T-Hg2+-T that occurred between the probe DNA and helper DNA could open the hairpin structure of probe DNA and form a rigid DNA triangles structure by CHA. Simultaneously, four bisferrocene signal markers also reached the surface of the electrode and built potential-assisted Au-S self-assembly to achieve signal amplification. Under the optimized condition, the sensor can achieve good electrochemical response Hg2+detection, and the detection limit is as low as 0.6 pM. furthermore, this sensor has high selectivity for Hg2+ detection.

An electrochemical Hg2+ sensor based on signal amplification strategy of target recycling.

In this work, an unmodified homogeneous electrochemical sensor based on electrochemical bonding and catalytic hairpin assembly (CHA) was first constructed for the high sensitivity detection of Hg2+. Herein, tetraferrocene, a synthesized compound, was used as a signal marker that modified both ends of the hairpin probe to amplify the electrochemical signal. The interaction of T-Hg2+-T could induce the catalytic self-assembly of hairpins by means of auxiliary DNA. The rigid DNA triangle that was formed easily reaches the electrode and induced Au-S self-assembly assisted by potential, allowing tetraferrocene to reach the electrode surface and generate a sensitive electrochemical signal. CHA and tetraferrocene signal markers accomplished dual signal amplification, and the limit of detection was 0.12 pM. Differential pulse voltammetry experiments in the presence of tetraferrocene redox indicator show that the linear response range of electrochemical biosensors to mercury ions is 0.2-2000 pM, This technology offers good selectivity and high recognition efficiency for the detection of mercury ions and has broad application prospects in actual sample detection.

An electrochemical DNA sensor without electrode pre-modification.

We present a non-modification electrochemical DNA sensing strategy, which used Potential-Assisted Au-S Deposition and a clamp-like DNA probe. The dual-hairpin probe DNA was tagged with a methylene blue (MB) at the 3' terminal and a thiol at the 5' terminal., Without being hybridized with target DNA, the loop of probe prevented the thiol from reaching the bare gold electrode surface with an applied potential., After hybridization with the target DNA, the probe' s loop-stem structure opened through two distinct and sequential events, which led to the formation of a triplex DNA structure. Then the thiol easily contacted with electrode and resulted in potential-assisted Au-S self-assembly. Electrochemical signals of MB were measured by differential pulse voltammetry (DPV) and used for target quantitative detection. This strategy offered a detection limit down to 2.3pM. and an inherently high specificity for detecting even single mismatch.

An electrochemical DNA sensor for sequence-specific DNA recognization in a homogeneous solution.

In this work, a sensitive electrochemical DNA sensor based on an avidin modified electrode and a DNA-functionalized Au nanoparticle (DFNP) was developed. The DNA-functionalized Au nanoparticle contained two kinds of DNA, one is hairpin probe DNA with a biotin at the 3' terminal and a thiol at the 5' terminal, the other is methylene blue (MB)-labeled linear signal DNA. Without hybridizing with the target DNA, the loop of the hairpin impeded biotin linked with avidin on electrode. However, after target hybridization, the hairpin was opened and biotin was recognized by avidin which resulted in a DNA-functionalized Au nanoparticle brought on the electrode surface. Electrochemical signals of MB bound to signal DNA were measured by differential pulse voltammetry (DPV). Taking advantage of amplification effects of the AuNP and binding specificity of the hairpin probe, this DNA biosensor greatly simplified the electrochemical DNA detection method and displayed high specificity in DNA detection. By using this new method, we demonstrate that this prototype sensor has been able to detect as low as picomolar DNA targets with excellent differentiation ability even for a single mismatch.

A powerful synergistic effect for highly efficient diastereo- and enantioselective phase-transfer catalyzed conjugate additions.

An efficient, catalytic, diastereo- and enantioselective conjugate addition of N-(diphenylmethylene)glycine tert-butyl ester to ß-aryl substituted enones was realized in the presence of 1 mol% of newly desired dinuclear N-spiro-ammonium salts, affording functionalized α-amino acid derivatives in 57-98% yields with high diastereoselectivity (up to 99:1 dr) and enantioselectivity (up to 96.5:3.5 er).

Catalytic stereoselective synthesis of highly substituted indanones via tandem Nazarov cyclization and electrophilic fluorination trapping.

A new catalytic stereoselective tandem transformation via Nazarov cyclization/electrophilic fluorination has been accomplished. This sequence is efficiently catalyzed by a Cu(II) complex to afford fluorine-containing 1-indanone derivatives with two new stereocenters with high diastereoselectivity (trans/cis up to 49/1). Three examples of catalytic enantioselective tandem transformation are presented.

Stereoselective construction of fluorinated indanone derivatives via a triple cascade Lewis acid-catalyzed reaction.

A one-pot three-component cascade reaction proceeds by way of a Lewis acid-catalyzed Knoevenagel condensation/Nazarov cyclization/electrophilic fluorination sequence to afford fluorinated 1-indanone derivatives in moderate to good yields with high diastereoselectivities.

Highly enantioselective Michael addition of aromatic ketones to nitroolefins promoted by chiral bifunctional primary amine-thiourea catalysts based on saccharides.

[reaction: see text] A new class of thiourea catalysts have been developed which integrate saccharide and primary amine moieties into one small organic molecule. These simple catalysts are shown to be highly enantioselective for direct Michael addition of aromatic ketones to a range of nitroolefins (up to 98% ee).