A way to synthesize a Mn2+‐ coordinated polymer precursor ligated by sulfur atoms with acetate counter ions (Mn‐DTOGA) is proposed, which is achieved by an imine formation reaction between ...dithiooxamide and glutaraldehyde in the presence of manganese (II) acetate. MnS/MnO decorated N, S‐doped carbon nanoparticles (MnS/O‐SNC) are then prepared by calcination of the Mn ion‐coordinated polymer for the practical applications of catalytic reactions. The Mn‐DTOGA and MnS/O‐SNC structures prepared at different temperatures (700, 800, and 900 °C) are characterized using various physical and electrochemical and chemical analyses. The nanoparticles prepared at 900 °C reveal the best performance for the catalytic oxidation of Hydrogen peroxide (H2O2) and bisphenol A. The decomposition potentials of H2O2 (1.0 mm) and bisphenol A (100.0 µm) on the catalyst modified electrode are observed to be +0.40 and +0.15 V (versus Ag/AgCl), respectively. It is observed that the catalytic performances to the oxidation reactions are mainly related to MnO decorated outside the SNC particles compared to MnS formed inside the particles. The electrode reveals a wide dynamic range with the low detection limits for H2O2 (0.08 (±0.02) µm) and bisphenol A (0.17 (±0.04) µm). This study will provide essential clues for the future catalyst design.
A new synthesis method of Mn ion coordinated polymer precursor (Mn‐DTOGA) by an imine formation reaction between dithiooxamide and glutaraldehyde is demonstrated. The MnO/MnS decorated S, N doped‐carbon nanoparticles (MnS/O‐SNC) as an oxidation catalyst is prepared by calcination of Mn‐DTOGA precursor. It will pave the way to find the optimal carbon complex architecture for specific catalytic processes.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SBCE, SBMB, UL, UM, UPUK
The template‐free synthesis and the characterization of an active electrocatalyst are performed for both the hydrogen evolution and oxygen reduction reactions in acidic media. In this work, the ...unique chelation mode of benzene‐1,4‐dithiocarboxamide (BDCA) is first used to synthesize a novel palladium‐BDCA coordination polymer (PdBDCA) as a precursor of palladium sulfide nanoparticles‐decorated nitrogen and sulfur doped carbon (Pd4S‐SNC). The newly synthesized PdBDCA and Pd4S‐SNC nanoparticles are characterized using chemical, electrochemical, and surface analysis methods. Notably, the nanoparticles obtained at 700 °C exhibit the remarkable catalytic property for the hydrogen evolution reaction in 0.5 m H2SO4, showing the overpotential of 32 mV (vs reversible hydrogen electrode (RHE)) and Tafel slope of 52 mV dec−1, which are comparable to that of Pt/C. The catalyst also shows a high oxygen reduction activity, offering the half‐wave and onset potentials of 0.92 and 0.77 V (vs RHE) in 0.5 m H2SO4, with improved methanol tolerance and long‐term stability compared with Pt/C. The present study gives a way for the design of excellent electrocatalyst for the energy conversion devices in the corrosive acidic environment.
A chelation of a benzene‐1,4‐dithiocarboxamide monomer with Pd (II) ion forms a coordination polymer as a precursor of Pd4S‐decorated N and S doped carbon. The synergy effect between Pd4S and heteroatoms doped carbon matrix reveals the excellent electrocatalytic performance for hydrogen evolution and oxygen reduction reactions in acidic media.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SBCE, SBMB, UL, UM, UPUK
A novel iron-coordinated conducting polymer is synthesized, followed by the preparation of Fe3N nanoparticle-embedded sulfur and nitrogen-doped carbon (Fe3N/SNC) nanostructures via a one-step polymer ...pyrolysis strategy, which can exceptionally catalyze the oxygen reduction reaction (ORR) in both alkaline and acidic media, and the oxidation of catecholamines. To synthesize the metal coordinated polymer, FeCl3 is used as an oxidant and metal source for the polymerization of 3′,4′-diamino-terthiophene (DAT) to form poly-FeDAT. It is subsequently pyrolyzed at 900 °C to attain the Fe3N/SNC catalyst. The Fe3N/SNC electrocatalyst exhibit a more positive onset (0.985 V vs RHE), half-wave potentials (0.848 V), a higher limiting current density (5.47 mAcm−2), alcohol resistance and durability than the benchmark Pt/C in 0.1 M KOH, and it is comparable to Pt/C in 0.1 M HClO4. It also displays exceptional performance for the catalytic oxidation of catecholamines and AP, which results in simultaneous detection of DA and AP in trace amounts (the detection limits were 110 nM and 270 nM (S/N = 3) for each species, respectively). The unique catalytic activity is ascribable to the presence of pyridinic-N, graphitic-N, and Fe–N along with thiophene-S in the carbon, resulting in catalytically enhanced electron transfer from Fe3N to N, S doped carbon.
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•Fe3N NPs embedded S/N doped carbon is synthesized by a facile, one step polymer pyrolysis strategy.•The catalyst possesses extraordinary catalytic activity for oxygen reduction reaction and catecholamines oxidation.•The catalyst can simultaneously detect dopamine (DA) and acetaminophen (AP) in human urine samples.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
Lactate is one of the major biomarkers to assess the physical fitness of human in clinical or sports medicine. The proper and well‐timed lactate determination can avoid some exigent conditions ...including hemorrhage, respiratory distress, sepsis, and hypoxia. Therefore, rapid, facile, selective, and reliable detection of lactate have gained appreciation lately. Among the various lactate detection methods, electrochemical method is the most rapid, convenient, and sensitive technique. Specifically, nanomaterial‐based nonenzymatic electrochemical lactate sensors are much desirable to solve the demerits and stability issues of enzymatic lactate sensors. Numerous materials including metal and metal oxide nanoparticles, metal–organic frameworks, molecularly imprinted polymers, and carbons were used as electrocatalysts to achieve highly sensitive lactate sensors. This present review mainly focuses on the recent developments of these materials for enzyme‐free lactate oxidation and the future prospective of electrode modification catalysts for lactate sensors.
This review summarizes recent trends in the development and applications of electrochemical nonenzymatic lactate sensors based on nanostructured materials including metal and metal oxide nanoparticles, metal–organic frameworks, and molecularly imprinted polymers and carbons. In addition, the analytical performance such as dynamic range, sensitivity, detection limit, and so forth is also highlighted. Detection challenges and future perspective are briefly discussed for development of the lactate sensors toward miniaturization and commercialization purpose.
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FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SBCE, SBMB, UL, UM, UPUK
A monomer precursor of polyterthiphene derivative bearing both electron donor (-NH
2
) and acceptor (–COOH) groups (3-(2,2′:5′,2″-terthiophen-3′-yl)-5-aminobenzoic acid, TABA) was newly synthesized ...and characterized. The comparison analysis was performed forpTABA with a single acceptor or donor group bearing polymer. The frontier orbital calculation for the monomer reveals the intermolecular electron movement from donor to acceptor through the backbone. The electrical study confirmed that the conductivity of the functionalized polymer increased from 0.11 S cm
−1
(with single donor group) to 0.24 S cm
−1
(with single acceptor group) through 0.19 S cm
−1
(for both donor and acceptor groups), as a result of stabilization of quinoid form on the polymer backbone. Derivative cyclic voltabsorptometry (DCVA) obtained for pTABA confirmed the formation of neutral, polaron, and bipolaron at 470 nm (at +1.07/+0.80 V), 781 nm (at +1.07/+0.80 V), and 950 nm (at +1.30/+1.19 V), respectively. The absorption bands of radical species were blue-shifted by the donor group functionalized polymer and red-shifted by the acceptor group. The electrochromic performance of polymer bearing both donor and acceptor groups achieved nine colors between orange (0.0 V) and midnightblue (1.4 V) compared with that of single functional groups displaying two or three colors.
The performance enhancement of 3D‐printed electrode comprised of polylactic acid (PLA) and graphite (Gr) doped with graphene oxide (GO) was studied to detect five heavy metal ions in trace level. The ...pretreatment of PLA/Gr/GO electrode with potential cycling in H2SO4 solution achieved the most sensitive response. The characteristics of the composite electrodes were verified using XPS, FE‐SEM, EDXS, Raman, and impedance spectroscopy. The experimental variables affecting the response current were optimized with respect to pH, deposition time, ratio of PLA/Gr/GO, and supporting electrolytes. The pretreated 3D‐PLA/Gr/GO electrode showed a wide dynamic range from 0.5 ppb to 1.0 ppm with low detection limits of 0.039–0.13 ppb. The reliability of the PLA/Gr/GO electrode was evaluated by analyzing the reference samples of European Reference Materials.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SBCE, SBMB, UL, UM, UPUK
A disposable microfluidic channel sensor printed on a plastic platform was developed to analyze heavy metal ions (HMIs) as a model target species. Precise separation and detection of multiple targets ...were established by symmetrically applying a small AC potential on the carbon channel walls to induce an electrodynamic force. The separation device was constructed by covering it with a plastic lid to achieve capillary action in the channel. The sample flow rate was regulated by the hydrophilicity of the lid plastic and electrodynamic convection by the AC field, which was characterized by the contact angle measurement and the additional electrodynamic force. The flow variables and their relevance to the capillary phenomena were demonstrated, and the analytical parameters were optimized. The working electrode was modified with poly(diamino terthiophene) anchored with nanosized graphene oxide (pDATT/GO) to enhance the detection performance. The experimental variables for separating and detecting the target species were optimized according to the AC frequency and amplitude, sample flow rate, electrolytes, pH, temperature, and applied potential for detection. The linear dynamic ranges were between 0.1 and 200.0 ppb, with detection limits of 0.04 ± 0.023, 0.29 ± 0.05, 0.07 ± 0.011, and 0.14 ± 0.06 ppb for Cu2+ Cd2+, Hg2+, and Pb2+, respectively. Finally, the reliability of the proposed method was evaluated through analysis of HMIs in real water samples. The results were matched to those obtained through parallel analysis using ICP–MS at a 95% confidence level.
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A disposable amperometric biosensor with a dual monomers-based bioconjugate was developed for granzyme B (GzmB) detection and for monitoring of the cancer progression of patients before and after ...immunotherapy. The biosensor was fabricated by immobilizing a GzmB monoclonal antibody (Ab1) on a poly3’-(2-aminopyrimidyl)-2,2’:5’,2’’-terthiophene/gold nanoparticle (pPATT/AuNP) layer. The bioconjugate nanoparticles were synthesized through self-assembly of a monomer mixture of 2,2:5,2-terthiophene-3-(p-benzoic acid) (TBA) and PATT onto AuNPs, followed by chemical binding of brilliant cresyl blue (BCB) on TBA and GzmB polyclonal antibody (Ab2) on the PATT layer. Each sensing layer was investigated by surface analysis and electrochemical experiments. The sensor performance was assessed with selectivity, stability, reproducibility, detection limit, and real sample analysis. Under the optimized conditions, the dynamic range of GzmB was in two slopes from 3.0 to 50.0 pg/ml and from 50.0 to 1000.0 pg/ml with a detection limit of 1.75 ± 0.14 pg/ml (RSD ≤5.2%). GzmB monitoring was performed for the patient's serum samples, where a low level of GzmB was observed for lung cancer patients before immunotherapy (10.51 ± 0.99 pg/ml, RSD ≤6.2%), and the level was increased after therapy (17.19 ± 2.22 pg/ml, RSD ≤2.6%). Moreover, a significantly higher level was present in healthy persons (34.40 ± 3.92 pg/ml, RSD ≤1.4%). The cancer progression of patients before and after therapy was evaluated by monitoring GzmB levels in human serum using the proposed sensor.
•A new disposable amperometric biosensor was developed for granzyme B detection.•A nanobioconjugate was fabricated with two terthiophene derivatives assembled on Au nanoparticles.•The cancer progress before and after immunotherapy was monitored using the proposed sensor.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
A robust amperometric sensor was developed for the lactate detection in the extracellular matrix of cancer cells. The sensor was fabricated by separately immobilizing nicotinamide adenine ...dinucleotide (NAD+) onto a carboxylic acid group and lactate dehydrogenase (LDH) onto an amine group of bi-functionalized conducting polymer (poly 3-(((2,2':5′,2″-terthiophen)-3′-yl)-5-aminobenzoic acid (pTTABA)) composited with N, S-doped porous carbon. Morphological features of the composite layer and sensor performance were investigated using FE-SEM, XPS, and electrochemical methods. The experimental parameters were optimized to get the best results. The calibration plot showed a linear dynamic range between 0.5 μM and 4.0 mM with the detection limit of 112 ± 0.02 nM. The proposed sensor was applied to detect lactate in a non-cancerous (Vero) and two cancer (MCF-7 and HeLa) cell lines. Among these cell lines, MCF-7 was mostly affected by the administration of lactate transport inhibitor, α-cyano-4-hydroxycinnamate (αCHC), followed by HeLa and Vero, respectively. Furthermore, the effect of αCHC concentration and treatment time on the lactate level in the cell lines were demonstrated. Finally, cytotoxicity studies were also performed to evaluate the effect of αCHC on cell viability.
•NAD+ and LDH were separately immobilized on the bi-functionalized conducting polymer layer.•Lactate was selectively detected in the extracellular matrix of non-cancerous and cancerous cells.•Sensor performance was compared between N, S doped porous carbon and other carbon materials.•The effect of αCHC inhibitor concentration and treatment time on the lactate level in cell lines was analyzed.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
The self-assembly of PdX2 (X– = ClO4 – and PF6 –) with C 3-symmetric l- and d-L L = (2S,2′S,2″S)- and (2R,2′R,2″R)-benzenetricarbonyltris(azanediyl)tris(3-phenylpropane-2,1-diyl)triisonicotinate ...produces the chiral nanocube pair Pd6(l-L)8(X)12 and Pd6(d-L)8(X)12 (X– = ClO4 – and PF6 –, respectively) with an inner cavity of 12.3 × 12.3 × 12.3 Å3. These chiral nanocubes are effective for the enantiorecognition of various chiral amino acids via the square-wave-voltammetry technique. In the present study, the site of enantiorecognition was confirmed by density functional theory calculated interactions between each nanocube and the chiral amino acids, and the calculated interactions were coincident with the shifts of the electrochemical oxidation potentials.
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IJS, KILJ, NUK, PNG, UL, UM