Nanostructured N, S, and P-Doped Elaeagnus Angustifolia Gum-Derived Porous Carbon with Electrodeposited Silver for Enhanced Electrochemical Sensing of Acetaminophen.

Acetaminophen (N-acetyl-p-aminophenol, APAP) is regularly used for antipyretic and analgesic purposes. Overdose or long-term exposure to APAP could lead to liver damage and hepatotoxicity. In this study, the approach of enhanced electrochemical detection of APAP by nanostructured biomass carbon/silver was developed. Porous biomass carbon derived from Elaeagnus Angustifolia gum was prepared by pyrolysis with co-doping of electron-rich elements of nitrogen, sulfur, and phosphorus. The electrodeposition of silver onto a glassy carbon electrode modified with porous carbon could enhance the sensing signal towards APAP. Two linear ranges from 61 nM to 500 µM were achieved with a limit of detection of 33 nM. The developed GCE sensor has good anti-interference, stability, reproducibility, and human urine sample analysis performance. The silver-enhanced biomass carbon GCE sensor extends the application of biomass carbon, and its facile preparation approach could be used in constructing disposable sensing chips in the future.

Separation and Qualitative Study of Mentha asiatica Boriss. Essential Oil Components by prep-GC, GC-QTOF-MS, NMR and Prediction of Bioactive Compounds.

In order to understand the material basis of wild Mentha asiatica Boris. in Xinjiang, the chemical constituents of essential oil extracted from aerial parts of this plant were studied. A total 52 components were detected and 45 compounds were identified. First of all, the essential oil was separated by silica gel column chromatography, and divided into several parts according to the results of thin layer chromatography. Eight fractions were obtained, and then each fragment was preliminarily screened for antibacterial activity. It was found that all eight fragments had certain antibacterial activity in different level. Then the fractions were subjected to preparative gas chromatography (prep-GC) for further isolation. Ten compounds were identified by 13 C-NMR, 1 H-NMR and gas chromatography-quadrupole time of flight-Mass spectrometry (GC-QTOF-MS). They are sabinene, limonene and ß-caryophyllene, (1R*,3S*,5R*)-sabinyl acetate, piperitone oxide, rotundifolone, thymol, piperitone, 4-hydroxypiperiditone, cedrol. After screened by bioautography, 4-hydroxypiperone and thymol were showed best antibacterial activity. The inhibitory effects of the two isolated compounds on Candida albicans and their related mechanisms were studied. The results showed that, 4-hydroxypiperone and thymol significantly reduced ergosterol content on the surface of Candida albicans cell membrane in a dose-dependent manner. This work has accumulated experience for the development and utilization of Xinjiang characteristic medicinal plant resources and new drug research and development, and provided scientific basis and support for the later research and development of Mentha asiatica Boris.

Electrochemical determination of chloramphenicol and metronidazole by using a glassy carbon electrode modified with iron, nitrogen co-doped nanoporous carbon derived from a metal-organic framework (type Fe/ZIF-8).

In this study, an iron-doped metal-organic framework (MOF) Fe/ZIF-8 was synthesized from ZIF-8 at room temperature. Direct carbonization of Fe/ZIF-8 under a nitrogen atmosphere produced nanoporous nitrogen doped carbon nanoparticles decorated with Fe component (Fe/NC). The Fe/NC exhibited a large surface area (1221.185 m2 g-1) and narrow pore-size distribution (3-5 nm). The nanoporous Fe/NC components along with Nafion were used to modify a glassy carbon electrode for the electrochemical determination of chloramphenicol and metronidazole via linear sweep voltammetry. Under optimal conditions, the reduction peak currents (observed at -0.237 V and -0.071 V vs. Ag/AgCl) of these analytes increased linearly with increasing chloramphenicol and metronidazole concentrations in the range of 0.1-100 µM and 0.5-30 µM, with the detection limits estimated to be 31 nM and 165 nM, respectively. This result was attributed to the large surface area, porous structure, high nitrogen content, and as well as the electrocatalytic effect of Fe atoms embeded in the carbon support. The proposed sensor was used for chloramphenicol and metronidazole analysis in samples, providing satisfactory results.

Hierarchically Ordered Porous Carbon with Atomically Dispersed FeN4 for Ultraefficient Oxygen Reduction Reaction in Proton-Exchange Membrane Fuel Cells.

The low catalytic activity and poor mass transport capacity of platinum group metal free (PGM-free) catalysts seriously restrict the application of proton-exchange membrane fuel cells (PEMFCs). Catalysts derived from Fe-doped ZIF-8 could in theory be as active as Pt/C thanks to the high intrinsic activity of FeN4 ; however, the micropores fail to meet rapid mass transfer. Herein, an ordered hierarchical porous structure is introduced into Fe-doped ZIF-8 single crystals, which were subsequently carbonized to obtain an FeN4 -doped hierarchical ordered porous carbon (FeN4 /HOPC) skeleton. The optimal catalyst FeN4 /HOPC-c-1000 shows excellent performance with a half-wave potential of 0.80 V in 0.5 m H2 SO4 solution, only 20 mV lower than that of commercial Pt/C (0.82 V). In a real PEMFC, FeN4 /HOPC-c-1000 exhibits significantly enhanced current density and power density relative to FeN4 /C, which does not have an optimized pore structure, implying an efficient utilization of the active sites and enhanced mass transfer to promote the oxygen reduction reaction (ORR).

Rational Design of Hierarchical, Porous, Co-Supported, N-Doped Carbon Architectures as Electrocatalyst for Oxygen Reduction.

Developing highly active nonprecious-metal catalysts for the oxygen reduction reaction (ORR) is of great significance for reducing the cost of fuel cells. 3D-ordered porous structures could substantially improve the performance of the catalysts because of their excellent mass-diffusion properties and high specific surface areas. Herein, ordered porous ZIF-67 was prepared by forced molding of a polystyrene template, and Co-supported, N-doped, 3D-ordered porous carbon (Co-NOPC) was obtained after further carbonization. Co-NOPC exhibited excellent performance for the ORR in an alkaline medium with a half-wave potential of 0.86 V vs. reversible hydrogen electrode (RHE), which is higher than that of the state-of-the-art Pt/C (0.85 V vs. RHE). Moreover, the substantially improved catalytic performance of Co-NOPC compared with Co-supported, N-doped carbon revealed the key role of its hierarchical porosity in boosting the ORR. Co-NOPC also exhibited a close-to-ideal four-electron transfer path, long-term durability, and resistance to methanol penetration, which make it promising for large-scale application.

Soft-templated mesoporous carbon-modified glassy carbon electrode for sensitive and selective detection of aristolochic acids.

In this study, ordered mesoporous carbon (OMC) was synthesized by applying a soft template method, and its mesoporous structure was characterized by scanning electron microscopy, transmission electron microscopy, and nitrogen adsorption-desorption techniques. X-ray diffraction and Raman spectroscopic analyses were conducted to demonstrate the high graphitization and topological defects at the sample surface. An electrochemical sensor based on an OMC-modified glassy carbon electrode (OMC/GCE) was constructed to detect aristolochic acids (AAs) using cyclic voltammetry and linear sweep voltammetry. The dependence of the experimental parameters including solution pH, scan rate, and accumulation time were examined and optimized. Under the optimal conditions, the response of OMC/GCE was linear over wide concentration ranges of AAs (0.6-10 µM and 10-50 µM), with sensitivities of -1.77 and -0.31 µA/µM, respectively. The limit of detection was calculated to be 0.186 µM (at S/N = 3). Furthermore, the proposed OMC/GCE was applied to detect AAs in Asarum sieboldini and the content of AAs was calculated to be 8.9 µg/g with high accuracy and precision. In addition, the modified electrode also exhibited good selectivity, reproducibility, and stability. Therefore, the OMC/GCE can be used as a platform for the determination of AAs.

Double-shelled yolk-shell Si@C microspheres based electrochemical sensor for determination of cadmium and lead ions.

In this work, we report double-shelled yolk-shell Si@C structure as a high-performance electrochemical sensing material for heavy metal ions. A SiO2-assisted polybenzoxazine (PB) coating strategy is used to synthesize highly monodispersed Si@C microspheres. After thermal carbonization of PB layers and selective removal of the SiO2 layers, Si@C microspheres were prepared. The resultant Si@C microspheres exhibit uniform spherical morphology and clearly double-shelled yolk-shell structures. The obtained Si@C microspheres are employed to prepare the chemically modified electrode for the sensitive determination of Cd(II) and Pb(II). By the method of anodic stripping voltammetry, the Si@C-based electrode shows a very wide linear dynamic range for target ions (e.g., 0.5-400 µg L-1 for Cd(II) and Pb(II)) and low limit of detections (e.g., 0.068 µg L-1 for Cd(II) and for 0.105 µg L-1 Pb(II)). The remarkable results, such as excellent resistance to interference ions, good repeatability, and reproducibility were also obtained. Furthermore, compared with those Cd(II) and Pb(II) sensors known in the literature, the analytical performance of Si@C-based electrode is better. Finally, when further used to determine Cd(II) and Pb(II) in tap water and lake water, the results of fabricated electrode successfully achieve good consistency with the data obtained from inductively coupled plasma-mass spectrometry (ICP-MS).

Taraxacum-like Mg-Al-Si@porous carbon nanoclusters for electrochemical rutin detection.

The authors describe a method for synthesis of a nanomaterial consisting of porous carbon encapsulated Mg-Al-Si alloy (denoted as Mg-Al-Si@PC) nanocluster. The nanocluster was synthesis by a solvothermal reaction, followed by high-temperature annealing. The nanoclusters were used as a novel immobilization platform for electrochemical sensing of rutin. The electrochemical behavior of rutin at a modified electrode was investigated by cyclic voltammetry and differential pulse voltammetry. The modified electrode demonstrates a high electrocatalytic activity toward rutin oxidation at a relatively low working potential (0.6 vs. Ag/AgCl). Under optimal conditions, the sensor has a linear response in the 1-10 µM rutin concentration range, and a 0.01 µM lower detection limit (at an S/N ratio of 3). It was successfully applied to the quantification of rutin in pharmaceutical tablets, and satisfactory results were obtained. Furthermore, the results correspond with those with the standard method and with the amounts indicated by the producer, respectively. Graphical abstract Schematic diagram of the Mg-Al-Si@PC nanocluster preparation process and electroanalysis mechanism.

Differential pulse voltammetry detection of Pb(ii) using nitrogen-doped activated nanoporous carbon from almond shells.

Almond shell-based charcoal was prepared by carbonizing almond shells in a nitrogen atmosphere. Nanoporous carbon (NPC) was formed via activating the obtained charcoal using potassium hydroxide as an activating agent, followed by the synthesis of nitrogen-doped nanoporous carbon (N-NPC) via a hydrothermal reaction using urea as the nitrogen source. The obtained N-NPC possessed a large surface area (1075 m2 g-1), narrow pore-size distribution (1-2 nm) and nitrogen content reaching 2.23 wt%. Using N-NPC with Nafion to modify a glassy carbon electrode, a highly sensitive electrochemical sensor was fabricated for the determination of Pb(ii) in aqueous solutions with differential pulse anodic stripping voltammetry (DPASV). The peak current of Pb(ii) showed linearity over concentrations from 2.0 to 120 µg L-1 and the detection limit (S/N = 3) was estimated to be 0.7 µg L-1 for Pb(ii), which was 15-fold lower than the guideline value of drinking water given by the World Health Organization (WHO). The experimental data indicated that this easy and low-cost method is an accurate and fast method for the detection of trace Pb(ii).

Synthesis of an iron-nitrogen co-doped ordered mesoporous carbon-silicon nanocomposite as an enhanced electrochemical sensor for sensitive and selective determination of chloramphenicol.

In this study, we developed a sensitive electrochemical sensor for the detection of chloramphenicol (CAP). An iron-nitrogen co-doped ordered mesoporous carbon-silicon nanocomposite (Si-Fe/NOMC) was prepared as follows. First, an SBA-15 surface was treated with an iron and nitrogen co-doped carbon framework obtained from the polymerization of ethylenediamine and carbon tetrachloride via the hard templating method. The mixture was then carbonized at a high temperature (900℃). Finally, the Si-Fe/NOMC modified electrode was fabricated, and employed as a high-performance electrochemical sensor to trace the CAP in drug samples using the large surface area of the hetero-atoms iron, nitrogen and silicon co-doped in the porous structure. Cyclic voltammetry and differential pulse voltammetry tests were determine to assess the efficiency of the sensor. Under optimized conditions, the sensor exhibited rapid current response for CAP in a phosphate buffer solution PBS with pH 7.5. The linear concentration of CAP ranged from 1 µM to 500 µM, with a limit of detection of 0.03 µM (S/N = 3). Furthermore, the electrochemical sensor was used to detect CAP in eye drop samples with satisfactory results.

A Facile Electrochemical Sensor Based on PyTS⁻CNTs for Simultaneous Determination of Cadmium and Lead Ions.

A simple and easy method was implemented for the contemporary detection of cadmium (Cd2+) and lead (Pb2+) ions using 1,3,6,8-pyrenetetrasulfonic acid sodium salt-functionalized carbon nanotubes nanocomposites (PyTS⁻CNTs). The morphology and composition of the obtained PyTS⁻CNTs were characterized using scanning electron microscopy (SEM), energy dispersive spectrometry (EDS), and X-ray photoelectron spectroscopy (XPS). The experimental results confirmed that the fabricated PyTS⁻CNTs exhibited good selectivity and sensitivity for metal ion-sensing owing to the insertion of sulfonic acid groups. For Cd2+ and Pb2+, some of the electrochemical sensing parameters were evaluated by varying data such as the PyTS⁻CNT quantity loaded on the pyrolytic graphite electrode (PGE), pH of the acetate buffer, deposition time, and deposition potential. These parameters were optimized with differential pulse anodic sweeping voltammetry (DPASV). Under the optimal condition, the stripping peak current of the PyTS⁻CNTs/Nafion/PGE varies linearly with the heavy metal ion concentration, ranging from 1.0 µg L-1 to 90 µg L-1 for Cd2+ and from 1.0 µg L-1 to 110 µg L-1 for Pb2+. The limits of detection were estimated to be approximately 0.8 µg L-1 for Cd2+ and 0.02 µg L-1 for Pb2+. The proposed PyTS⁻CNTs/Nafion/PGE can be used as a rapid, simple, and controllable electrochemical sensor for the determination of toxic Cd2+ and Pb2+.

Selective voltammetric determination of Cd(II) by using N,S-codoped porous carbon nanofibers.

Porous carbon nanofibers codoped with nitrogen and sulfur (NFs) were prepared by pyrolysis of trithiocyanuric acid, silica nanospheres and polyacrylonitrile (PAN) followed by electrospinning. The NFs were used to modify a glassy carbon electrode (GCE) which then displayed highly sensitive response to traces of Cd(II). Compared to a bare GCE and a Nafion modified GCE, the GCE modified with codoped NFs shows improved sensitivity for Cd(II) in differential pulse anodic sweep voltammetry. The stripping peak current (typically measured at 0.81 V vs. Ag/AgCl) increases linearly in the 2.0-500 µg·L-1 Cd(II) concentration range. This is attributed to the large surface area (109 m2·g-1), porous structure, and high fraction of heteroatoms (19 at.% of N and 0.75 at.% of S). The method was applied to the determination of Cd(II) in (spiked) tap water where it gave recoveries that ranged between 96% and 103%. Graphical abstract Schematic of a glassy carbon electrode (GCE) modified with N- and S-codoped porous carbon nanofibers (N,S-PCNFs). This GCE has good selectivity for cadmium ion (Cd2+) which can be determined by differential pulse anodic sweeping voltammetry (DPASV) with a detection limit as low as 0.7 ng·mL-1.

Synergistic Effects between Atomically Dispersed Fe-N-C and C-S-C for the Oxygen Reduction Reaction in Acidic Media.

Various advanced catalysts based on sulfur-doped Fe/N/C materials have recently been designed for the oxygen reduction reaction (ORR); however, the enhanced activity is still controversial and usually attributed to differences in the surface area, improved conductivity, or uncertain synergistic effects. Herein, a sulfur-doped Fe/N/C catalyst (denoted as Fe/SNC) was obtained by a template-sacrificing method. The incorporated sulfur gives a thiophene-like structure (C-S-C), reduces the electron localization around the Fe centers, improves the interaction with oxygenated species, and therefore facilitates the complete 4 e- ORR in acidic solution. Owing to these synergistic effects, the Fe/SNC catalyst exhibits much better ORR activity than the sulfur-free variant (Fe/NC) in 0.5 m H2 SO4 .