3-thiophene Boronic Acid Research Articles

Photoelectrochemical pathogenic bacteria sensing platform integrated with sterilization function based on the g-C3N4 nanosheets decorated with AuNPs and Poly(3-thiophene boronic acid)

The integration of sterilization capabilities into sensing platforms is a crucial step in mitigating the significant health risks associated with the persistence of pathogenic bacteria. In this study, we developed a photoelectrochemical (PEC) pathogenic bacteria sensing platform integrated with sterilization function. The platform was based on the g-C3N4 nanosheets decorated with AuNPs and Poly(3-thiophene boronic acid) (PTBA). The incorporation of AuNPs and PTBA proved highly beneficial for enhancing the PEC and photocatalytic performance of bulk g-C3N4. Leveraging the boronic acid group of PTBA, we achieved the selective capture of pathogenic bacteria on the surface of the electrode. The platform showed a high detection sensitivity towards Escherichia coli (E. coli) with a low limit detection (30.5 cfu/mL). Furthermore, the sensing platform demonstrated an exceptional antibacterial rate (99.9 %) resulting from the photoelectrocatalytic effect of PTBA/AuNPs/g-C3N4. This research presents a potential application of the platform as a self-cleaning biosensor for pathogenic diagnosis.

3-Thiopheneboronic acid: an effective additive for regulation on electrode/electrolyte interphase of lithium metal battery with high-loading cathode

Lithium metal has been considered as a potential replacement for the commercialized graphite anode to further boost the energy density of Li-ion batteries. However, Li dendrite growth during Li plating/stripping causes safety concern and poor lifespan of Li metal batteries (LMBs). In addition, the deploy of Ni-rich high-loading LiNixCoyMn1-x-yO2 (NCM, 0.6 ≤ x ≤ 0.95) is also an efficient way for boosting energy density. However, the dissolution of transition metal ion and structure evolution during cell operation can leave an adverse effect on cell performances. Herein, dual-functional 3-thiopheneboronic acid (TB) additive is used to form a lithium borate-rich solid electrolyte interphase (SEI) on Li anode and an improved cathode electrolyte interphase (CEI) on Ni-rich cathode. The TB-induced SEI layer is conductive and stable, and thus beneficial to improving kinetic limitation of Li nucleation and obtain a uniform morphology of Li deposition. When the TB-protected Li metal anode matches the high-loading LiNi0.6Co0.2Mn0.2O2 (NMC622) cathode (13.65 mg cm−2), high initial capacities of 163.78 mAh g−1 (2.23 mAh cm−2) at 0.2 C and 164.82 mAh g−1 (2.25 mAh cm−2) at 0.5 C after activation are obtained, attributing to the effective SEI and stable CEI induced by TB. This strategy of introducing additives into LMB system with Ni-rich high-loading NMC cathode affords an emerging energy storage system to demonstrates the material engineering of batteries with very high energy density.

Using boronic acid functionalization to simultaneously enhance electrical conductivity and thermoelectric performance of free-standing polythiophene film

Poly(3-thiophene boronic acid) (PTBA) as a boronic acid functionalized conducting polymer has been developed in sensors and electrochromics due to the characteristic feature of boronic acid groups, however, the previously reported PTBA had a very low electrical conductivity of 2.0 × 10−9 S cm−1, and up to day there are no researches on PTBA used as thermoelectric materials. In this study, a free-standing PTBA film with high-quality was firstly electrosynthesized in acetonitrile containing boron trifluoride diethyl etherate (1:1 by volume). SEM, FT-IR, UV–vis and TG were conducted to investigate morphologies, structures and thermal stability of PTBA films. Notably, the introduction of boronic acid groups in polythiophene significantly increases the Seebeck coefficient from 72.5 to 125.0 μV K−1, electrical conductivity from 0.014 to 0.027 S cm−1, and power factor from 0.0074 to 0.0422 μW m−1 K−2. Free-standing PTBA film will be a promising material in the field of thermoelectric.

A Nonenzymatic Glucose Sensor Platform Based on Specific Recognition and Conductive Polymer-Decorated CuCo2O4 Carbon Nanofibers.

CuCo2O4 decoration carbon nanofibers (CNFs) as an enzyme-free glucose sensor were fabricated via electrospinning technology and carbonization treatment. The CNFs with advantages of abundant nitrogen amounts, porosity, large surface area, and superior electrical conductivity were used as an ideal matrix for CuCo2O4 decoration. The resultant CuCo2O4–CNF hybrids possessed favorable properties of unique three-dimensional architecture and good crystallinity, accompanied by the CuCo2O4 nanoparticles uniformly growing on the CNF skeleton. To further enhance the selective molecular recognition capacity of the developed sensor, a conductive film was synthesized through the electropolymerization of thiophene and thiophene-3-boronic acid (TBA). Based on the synergistic effects of the performances of CNFs, CuCo2O4 nanoparticles, and boronic acid-decorated polythiophene layer, the obtained poly(thiophene-3-boronic acid) (PTBA)/CuCo2O4–CNF-modified electrodes (PTBA/CuCo2O4–CNFs/glassy carbon electrode (GCE)) displayed prominent electrocatalytic activity toward electro-oxidation of glucose. The fabricated sensor presented an outstanding performance in the two linear ranges of 0.01–0.5 mM and 0.5–1.5 mM, with high selectivity of 2932 and 708 μA·mM−1·cm−2, respectively. The composite nanofibers also possessed good stability, repeatability, and excellent anti-interference selectivity toward the common interferences. All these results demonstrate that the proposed composite nanofibers hold great potential in the application of constructing an enzyme-free glucose sensing platform.

High-performance electrochromic device based on polythiothene/poly(3-thiophene boronic acid) bilayer film

Abstract In this article, electrochromic polymer bilayer film on indium tin oxide (ITO) coated glass is built as electrode to facilitate the diffusion and migration of ions in electrochromic devices (ECDs). We investigate the performance of device based on the bilayer film using polythiothene (PT) and poly(3-thiophene boronic acid) (P3TBA) as model polymers. Notably, the incorporation of thin P3TBA layer (P3TBA has a high polarity) can change the surface morphology of PT film (rough and uncompacted), and increase the surface area of PT/P3TBA film, which will benefit the diffusion and migration of ions in ECD based on PT/P3TBA bilayer film on ITO glass (PT/P3TBA/ITO). As a result, the performance of ECD based on PT/P3TBA/ITO is significantly improved, which exhibits a highly optical contrast (48%), coloration efficiency (298 cm2/C), short response time (the coloration time and bleaching time are 5.27 and 0.48 s), and stable cycling. Compared with ECD based on PT film on ITO glass (PT/ITO), the optical contrast of ECD based on PT/P3TBA/ITO increases 200% (16% → 48%), and its coloration efficiency increases 54% (193 → 298 cm2/C). This study suggests that rational design of bilayer film micromorphology on electrode level might be a useful strategy for fabricating high performance polymer ECDs.

Conductive imprinted electrochemical sensor for epinephrine sensitive detection and double recognition

Epinephrine (EP), an important derivative of a neurotransmitter in the mammalian central nervous system and monitoring the concentration of EP is significant in biological and chemical researches. In this work, a molecularly imprinted polymer (MIP)/gold nanoparticles (AuNPs) composite (MIP/AuNPs) was modified on glassy carbon electrode (GCE) surface to fabricate a novel electrochemical sensor for EP detection. The modified AuNPs increased the surface area of the electrode and improved the sensitivity of the sensor. 3-thiophene boronic acid (3-TBA), as a monomer of conductive polymer, was employed to electropolymerize MIP in the presence of EP. Scanning electron microscope, cyclic voltammetry, and electrochemical impedance spectroscopy characterization results demonstrated that the prepared sensor possessed sensitive detection and selective recognition abilities toward EP. Unlike the other MIP based electrochemical sensors, conductive poly(3-TBA) matrix, as well as the conductive AuNPs can enhance the sensitivity of the sensor. Under the optimal conditions, the sensor can sensitively detect EP with a linear range and limit of detection of 9.0×10−8–1.0×10−4mol/L and 7.6×10−8mol/L, respectively. And the sensor showed double recognition ability to EP due to the following reasons: first, size and shape complementarity between the formed imprinted sites and the template molecules; second, the reversible covalent interaction between boronic acid of 3-TBA and cis-diol of EP. Thus, the sensor can recognize EP from its analogues. And the sensor has been applied to analyze EP in injection samples with satisfactory results.

Electro-optical properties of the perfect reflector material: Poly(3-thiophene boronic acid) semiconducting polymer

Based on first principles density functional theory, structural, electronic, and optical properties of poly (3-thiophene boronic acid) organic polymer have been calculated. It consist of positively charged pending boronic acid and negatively charged polymerized thiophene backbone which have anionic polymerization as in the type of vinyl polymerization. Electro-optical properties of the polymer indicates that it is not only an extrinsic (p-type) semiconductor with the electronic band gap, Eg = 1.35 eV, but also a perfect reflector polymer in the red band from 1.66 eV (∼747 nm) to 1.91 eV (∼650 nm). However, its refractive index diminishes at around 1.91 eV (∼650 nm) interestingly. These results suggest that, it will be a very promising multi-functional polymer for both academia and industries of electronic and optical device technologies. POLYM. ENG. SCI., 2016. © 2016 Society of Plastics Engineers

Improved activity of immobilized antibody by paratope orientation controller: Probing paratope orientation by electrochemical strategy and surface plasmon resonance spectroscopy

Electrochemical method and surface plasmon resonance (SPR) spectroscopic analysis are utilized herein to investigate antibody immobilization without and with orientation control for site-positioning paratopes (antigen binding site) of the antibody molecules. Biotin and its antibody were selected in current study as model. Such an approach employed thiophene-3-boronic acid (T3BA) as paratope orientation controller, (i) enabled site orientation of the antibody molecules reducing the hiding of paratopes, and (ii) maintained the activity of the captured antibodies, as confirmed by electrochemical and SPR anlysis. Anti-biotin antibody (a glycoprotein) was covalently bound to a self-assembled monolayer of T3BA modified on a nanogold-electrodeposited screen-printed electrode through boronic acid–saccharide interactions, with the boronic acid units specifically binding to the glycosylation sites of the antibody molecules. The immunosensor functioned based on competition between the analyte biotin and biotin-tagged, potassium hexacyanoferrate(II)-encapsulated liposomes. The current signal produced by the released liposomal Fe(CN)64−, measured using square wave voltammetry, yielded a sigmoidally shaped dose–response curve that was linear over eight orders of magnitude (from 10–11 to 10–3M). Furthermore this biosensing system fabricated based on T3BA approach was found to possess significantly improved sensitivity, and the limit of detection toward biotin was calculated as 0.102ngmL–1 (equivalent to 6μL of 4.19×10–10M biotin).

Glycated hemoglobin (HbA1c) affinity biosensors with ring-shaped interdigital electrodes on impedance measurement

Glycated hemoglobin (HbA1c) is one of the most important diagnostic assays for the long-term mark of glycaemic control in diabetes. This study presents an affinity biosensor for HbA1c detection which is label-free based on the impedance measurement, and it features low cost, low sample volume, and requires no additional reagent in experiments. The ring-shaped interdigital electrodes (RSIDEs) are designed to promote the distribution uniformity and immobilization efficiency of HbA1c, and are further employed to characterize the impedance change and identify various concentrations of HbA1c. The self-assembled monolayer (SAM) of thiophene-3-boronic acid (T3BA) is provided to modify the gold electrode surface. Afterwards, the esterification reaction between HbA1c and T3BA produces a relative change of electrical property on the electrode surface. The RSIDEs with SAM of T3BA exhibit a wide range from 100 to 10ng/µL producing an approximate logarithmic decrease of impedance, a low detection limit of 1ng/µL, a good selectivity and short-term stability for HbA1c determination. The remarkable advantages (miniaturization and low-cost) fill the bill of point-care diagnostics for portable sensor development.

A novel amperometric glucose biosensor based on reconstitution of glucose oxidase on thiophene-3-boronic acid polymer layer

The biosensor was constructed for determination of glucose by using glucose oxidase enzyme immobilized on poly(thiophene-3-boronic acid) (PTBA). Boronic acid functionalized polythiophene layer was obtained by electrochemical polymerization of Thiophene (Th) and thiophene-3-boronic acid (TBA) with different monomer rations. The reconstitution of the apo-glucose oxidase (apo-GOx) on a complexed flavin adenine dinucleotide (FAD) linked to polythiophene boronic acid (PTBA) monolayer yields an electrically contacted enzyme monolayer. The GOx-reconstituted enzyme electrode exhibited excellent electrocatalytic activities toward the reduction and oxidation of hydrogen peroxide as well. The PTBA/FAD/GOx biosensor shows an excellent performance for glucose at +0.4 V with a high sensitivity (2.14 μA/mM) and lower response time (∼5 s) in a wide concentration range of 0.5–18 mM (correlation coefficient of 0.9952). Furthermore, the effects of applied potential, pH, temperature, electroactive interference, stability and reusability of the biosensors were discussed.

Horseradish peroxidase-catalyzed synthesis of poly(thiophene-3-boronic acid) biocomposites for mono-/bi-enzyme immobilization and amperometric biosensing

We report here on a facile enzymatic polymerization protocol to prepare enzyme—poly(thiophene-3-boronic acid) (PTBA) polymeric biocomposites (PBCs) for high-performance mono-/bi-enzyme amperometric biosensing. Horseradish peroxidase (HRP)-catalyzed polymerization of thiophene-3-boronic acid (TBA) monomer was conducted in aqueous solution containing HRP (or plus glucose oxidase (GOx)) by either directly added or GOx-glucose generated oxidant H2O2. The mono-/bi-enzyme amperometric biosensors were prepared simply by casting the dialysis-isolated PBCs on Au-plated Au electrode (Auplate/Au), followed by coating with an outer-layer chitosan (CS) film. The boronic acid residues are capable of covalent bonding with enzyme at the glycosyl sites (boronic acid-diols interaction), which should less affect the enzymatic activity as compared with the common cases of covalent bonding at the peptide chains, and UV–vis spectrophotometric tests confirmed that the encapsulated HRP almost possesses its pristine enzymatic specific activity. The enzyme electrodes were studied by cyclic voltammetry, electrochemical impedance spectroscopy and chronoamperometry in the presence of Fe(CN)64− mediator. The CS/HRP–PTBA/Auplate/Au electrode responded linearly to H2O2 concentration from 1 to 300μM with a sensitivity of 390μAmM−1cm−2 and a limit of detection (LOD) of 0.1μM. The bienzyme CS/GOx−HRP−PTBA(H2O2)/Auplate/Au electrode responded linearly to glucose concentration from 5μM to 0.83mM with a sensitivity of 75.1μAmM−1cm−2 and a LOD of 1μM, and it is found here that the use of Fe(CN)64− that can only efficiently mediate HRP favorably avoids the “unusual amperometric responses” observed when other mediators that can efficiently turn over both HRP and GOx are used.

One-pot preparation of uricase–poly(thiophene-3-boronic acid)–Ptnano composites for high-performance amperometric biosensing of uric acid

Abstract Chemical oxidation of glycoprotein-bound thiophene-3-boronic acid (TBA) monomer by relatively mild oxidant chloroplatinate in neutral aqueous solution containing uricase yielded uricase–PTBA–Ptnano bionanocomposite with high enzymatic specific activity on a platinized (Ptplate) Au electrode, which was then covered by an outer-layer chitosan (CS) film to fabricate a CS/uricase–PTBA–Ptnano/Ptplate/Au electrode. This electrode exhibited a linear amperometric response to uric acid concentration from 5 μM to 1.2 mM with a sensitivity of 134 μA mM−1 cm−2, a limit of detection (S/N = 3) of 1 μM, and excellent operation/storage stability, which also worked well in serum samples.

Electrochemical immunoassay for subgroup J of avian leukosis viruses using a glassy carbon electrode modified with a film of poly (3-thiophene boronic acid), gold nanoparticles, graphene and immobilized antibody

We have modified a glassy carbon electrode (GCE) with a film of poly(3-thiophene boronic acid), gold nanoparticles and graphene, and an antibody (Ab) was immobilized on its surface through the covalent bond formed between the boronic acid group and the glycosyl groups of the Ab. Subgroup J of avian leukosis viruses (ALV-J) were electrochemically determined with the help of this electrode. There is a linear relationship between the electron transfer resistance (R et) and the concentration of ALV-J in the range from 527 to 3,162 TCID50⋅mL−1 (where TCID50 is the 50 % tissue culture infective dose). The detection limit is 210 TCID50⋅mL−1 (at an S/N of 3), and the correlation coefficient (R) is 0.9964. The electrochemical immunoassay showed good selectivity, stability and reproducibility.

Detection of glycated hemoglobin (HbA1c) based on impedance measurement with parallel electrodes integrated into a microfluidic device

This paper proposes a sensor for glycated hemoglobin (HbA1c) detection based on impedance measurement. The sensor contains a pair of parallel facing electrodes integrated into a microfluidic device. A pair of parallel facing electrodes is fabricated to characterize the impedance change and determine the concentration of HbA1c. A self-assembled monolayer (SAM) of thiophene-3-boronic acid (T3BA) is used for modifying the gold electrodes. Non-faradaic electrochemical detection of surface-bound HbA1c with no redox indicator added is conducted by utilizing the capacitive property as a sensing signal. The performance of the HbA1c sensor was investigated by impedance analyzer and the impedance changes approximately logarithmically with the concentration of HbA1c in the range of 10–100 ng/μL. The proposed detection method has potential for use in point-of-care diagnostics and can be used for the detection of various biomolecules.

Fabrication of Conducting Poly(3-thiophene boronic acid)-Grafted Multi-Walled Carbon Nanotubes by Oxidative Polymerization

Composite materials of multi-walled carbon nanotubes (MWNTs) and a conducting polymer, poly(3-thiophene boronic acid) (PTBA) were prepared by in-situ oxidative polymerization of TBA in the presence of MWNTs and potassium dichromate. The MWNTs which were previously surface functionalized with acid chloride groups were reacted with TBA using a simple "chemical grafting" technique. It was observed that the nanotubes were dispersed uniformly in the pi-conjugated polymer matrix and entrapped by the polymer. The conductivity of the composites was higher than that of the pure polymer from a conventional four-probe technique, which indicates that the fabrication of MWNTs into the polymer matrix significantly improves the conductivity of the polymer due to the intrinsic properties of MWNTs.

Selective Electrochemical Sensing of Glycated Hemoglobin (HbA1c) on Thiophene-3-Boronic Acid Self-Assembled Monolayer Covered Gold Electrodes

We report a novel concept of sensing glycated hemoglobin, HbA 1c, which is now the most important index for a long-term average blood glucose level, by first selectively immobilizing it on the thiophene-3-boronic acid (T3BA) self-assembled monolayer (SAM)-covered gold electrode by a selective chemical reaction with boronic acid. HbA 1c thus immobilized is then detected by the label-free electrochemical impedance spectroscopic (EIS) measurements with a redox probe, an equimolar mixture of K 3Fe(CN) 6 and K 4Fe(CN) 6, present. The rate of charge transfer between the electrode and the redox probe is shown to be modulated by the amount of HbA 1c in the matrix hemoglobin solution due to the blocking effect caused by the binding of HbA 1c with boronic acid. Both the formation of a well-defined T3BA-SAM on the gold surface and the chemical binding of its boronic acid with HbA 1c in solution were confirmed by quartz crystal microbalance, atomic force microscopy, and EIS experiments.

Dimeric boronates derived from the reaction of schiff bases and boronic acids

The one-pot synthesis of dimeric boron complexes is reported. The compounds were obtained by reaction of Schiff bases (tridentate ligands) with trans-beta-phenylvinylboronic acid, 3-thiopheneboronic acid and methylboronic acid. Building of the dimeric structures is favored by the presence of intramolecular N-> B coordination bonds, resulting in the formation of ten-membered ring heterocycles. An X-ray crystallographic analysis for one of them confirmed the dimeric nature of these compounds.

Subsequent Hydride Substitution in (Arene)trihydridodiruthenium Complexes: Synthesis and Structure of Thiolato‐Bridged Diruthenium Cations of the Type [H2(arene)2Ru2(p‐X−C6H4−S)]+ and [H(arene)2Ru2(p‐X−C6H4−S)2]+

AbstractThe cationic complexes [HRu2(η6‐arene)2{μ2‐(p‐X−C6H4)−S}2]+ and [H2Ru2(η6‐arene)2{μ2‐(p‐X−C6H4)−S}]+ (arene = 1,2,4,5‐Me4C6H2 or C6Me6; X = Br and Me) are accessible in good yields from p‐X−C6H4−SH with [H3Ru2(1,2,4,5‐Me4C6H2)2][BF4] and [H3Ru2(C6Me6)2][BF4], respectively. The dibromo derivative [HRu2(C6Me6)2(p‐Br−C6H4−S)2]+ is found to undergo double Suzuki coupling reactions with 3‐thiophene boronic acid to give [HRu2(C6Me6)2(p‐C4H3S−C6H4−S)2]+. This dibromo complex is a potential precursor for the insertion of dinuclear hydrido organometallic entities in the main chain of conjugated molecules. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

Rhodium-catalyzed Asymmetric 1,4- Addition of 3-Thiopheneboronic Acid to a,b-Unsaturated Carbonyl Compounds

Asymmetric 1,4-addition of 3-thiopheneboronic acid to α,β-unsaturated carbonyl compounds proceeded with high enantioselectivity in the presence of 3 mol% (Rh) of [Rh(OH)((S)-binap)] 2 in dioxane/H 2 O (10/1) at 40 °C to give the corresponding optically active β-(3-thienyl) carbonyl compounds of over 94% ee.

Substitution of antibodies and receptors with molecularly imprinted polymers in enzyme-linked and fluorescent assays

A new technique for coating microtitre plates with molecularly imprinted polymers (MIP), specific for low-molecular weight analytes (epinephrine, atrazine) and proteins is presented. Oxidative polymerization was performed in the presence of template; monomers: 3-aminophenylboronic acid (APBA), 3-thiopheneboronic acid (TBA) and aniline were polymerized in water and the polymers were grafted onto the polystyrene surface of the microplates. It was found that this process results in the creation of synthetic materials with antibody-like binding properties. It was shown that the MIP-coated microplates are particularly useful for assay development. The high stability of the polymers and good reproducibility of the measurements make MIP coating an attractive alternative to conventional antibodies or receptors used in enzyme linked immunosorbent assay (ELISA).