Adjustable chromatographic performance of silica-based mixed-mode stationary phase through the control of co-grafting amounts of imidazole and C18 chain.

In this paper, three imidazole- and C18- bifunctional silica stationary phases (Sil-Im-C18) were prepared by adjusting introduction interval of octadecyltrichlorosilane (ODS) and 3-imidazol-1-ylpropyl(trimethoxy)silane (TMPImS), which can be used for reversed-phase liquid chromatography (RPLC) and ion exchange chromatography (IEC) with adjustable performance. The successful preparation of Sil-Im-C18 were confirmed by the characterizations of elemental analysis, infrared spectroscopy (FTIR) and contact angle (CA). Chromatographic performance of Sil-Im-C18 were evaluated by the separation of Tanaka test mixture, alkylbenzenes, linear PAHs and a set of analytes with different properties (uracil, phenol, 1,2-dinitrobenzene and naphthalene), and compared with commonly used C18 column. It was found that the chromatographic performance of Sil-Im-C18 changed significantly with the difference in bonding amount of imidazole and C18. Sil-Im-C18 demonstrated the excellent separation performance towards polycyclic aromatic hydrocarbons (PAHs), phenylesters, phenylamines, phenols and inorganic anions, and notably, nucleobases and nucleosides can be separated using pure water as mobile phases. The van Deemter plot showed that the column efficiency of Sil-Im-C18-3 was 64,933 plate·m-1 for naphthalene, indicated that Sil-Im-C18 was reasonably chromatographic columns. The RSD values of retention time were 0.22 %-0.61 % for 10 needles alkylbenzenes injected continuously at 50 °C to investigate thermal stability and repeatability, all the fluctuations of k of naphthalene were less than 2.3 % for Sil-Im-C18-1 during flushing 24 h with the mobile phase at different pH values (pH = 3 and 8), the retention time of alkylbenzenes were almost same for Sil-Im-C18-1 at different time, the RSD values of retention time of alkylbenzenes were 0.45 %-2.28 % for two batches Sil-Im-C18-1, revealing the excellent repeatability, thermal stability, durability and reproducibility of Sil-Im-C18, and implying a commercial prospect.

A C4-modified bipyridinium multi-mode stationary phase for reversed phase, hydrophilic interaction and ion exchange chromatography.

A novel C4-modified bipyridinium stationary phase (Sil-DPC4) was prepared and characterized by elemental analysis (EA) and Fourier transform infrared spectrometry (FT-IR) and further investigated for multi-mode liquid chromatography. The chromatographic performances of Sil-DPC4 were evaluated by reversed-phase chromatography using polycyclic aromatic hydrocarbons (PAHs), phenylamines and phenols, hydrophilic interaction chromatography using nucleosides and nucleobases, and ion exchange chromatography using inorganic ions and organic ions. The effects of the acetonitrile content, salt concentration and pH value of the mobile phase on the retention of Sil-DPC4 were also investigated. Sil-DPC4 showed multiple retention mechanisms including π-π, hydrophobic and electrostatic interactions for PAHs, phenylamines and phenols compared with a dipyridine modified silica stationary phase (Sil-DP) and C18 in RPLC, faster separation for nucleosides and nucleobases compared with Sil-DP, and higher hydrophilicity than HILIC in HILIC, and stronger retention and better separation ability for inorganic ions and organic ions in comparison to Sil-DP in IEC. Besides, Sil-DPC4 was used successfully to detect iodide in artificial seawater and had the potential to analyze radionuclide iodine-131 in seawater. In conclusion, multiple retention mechanisms of Sil-DPC4 could make it have potential applications in complex samples.

Grafting of Tetraphenylethylene on Silica Surface, Characterizations, and Their Chromatographic Performance as Reversed-Phase Stationary Phases.

Surface modification is an effective way to functionalize the materials so as to get some special properties. Tetraphenylethylene (TPE) has been widely investigated as a well-known reagent which has the nature of aggregation-induced emission (AIE), but has never been reported in the liquid chromatography stationary phase. In this work, TPE-grafted silica (Sil-TPE) was obtained successfully using the derivative of 1-(4-hydroxyphenyl)-1,2,2-triphenylethylene as a ligand, and then characterized by elemental analysis, Fourier transform infrared spectra, thermogravimetric analysis, and so forth. Laser scanning confocal microscopy images reflected the AIE phenomenon of grafted TPE because the internal vibration and rotation of TPE molecules were restrained in the confined silica space. The contact angle test showed superhydrophobic properties of Sil-TPE. In order to understand thoroughly the mechanism of chromatographic performance and retention behavior for Sil-TPE, Tanaka test mixture, alkylbenzenes, polycyclic aromatic hydrocarbons (PAHs), and phenols were separated. This reveals that Sil-TPE has strong aromaticity and certain shape selectivity, especially, has excellent separation performance for PAHs and phenols. The thermodynamic properties and repeatability of Sil-TPE were further studied, which showed the stability of Sil-TPE. This work shows that TPE can be successfully grafted on silica surface and it has the potential to be a new kind of promising stationary phases in the future.

Correction: A novel electrochemical sensor based on microporous polymeric nanospheres for measuring peroxynitrite anion released by living cells and studying the synergistic effect of antioxidants.

Correction for 'A novel electrochemical sensor based on microporous polymeric nanospheres for measuring peroxynitrite anion released by living cells and studying the synergistic effect of antioxidants' by Fuxin Liu et al., Analyst, 2019, 144, 6905-6913, https://doi.org/10.1039/C9AN01693G.

Construction of a novel electrochemical sensing platform to investigate the effect of temperature on superoxide anions from cells and superoxide dismutase enzyme activity.

It is of great significance to realize the detection of trace amounts of superoxide anions (O2•-) in biological systems due to the connection between the concentration of O2•- and some diseases. Here, we present a novel method to fabricate a non-enzymatic electrochemical sensor for measuring O2•- from biological systems. The sensor was fabricated by nanocomposites (PAMAM-Au) synthesized by using (PAMAM-G4.0) dendrimers as template/stabilizers for gold nanoparticles (AuNPs) growth. Transmission electron microscopy (TEM) investigations indicate that AuNPs were encapsulated in PAMAM with average diameter about 8 nm. The electrochemical technique confirmed that PAMAM-Au possessed extraordinary electrochemical response to superoxide anions. As an analytical and sensing platform, apart from excellent sensitivity, wide liner range (from 3.69 × 10-5 - 37.2 µM), ultra-low detection limit (0.0123 nM), our sensor also presented satisfying performance for monitoring changes of O2•- levels upon different stimuli. Furthermore, we investigated the effect of temperature on superoxide anions released from living cells and enzyme activity through an electrochemical method for the first time. Most importantly, the simulated electrochemical study in vitro further confirmed that temperature has a crucial influence on both the ability of living cells to resist external stimulation and the antioxidant capacity of superoxide dismutase. As expected, the study may provide researchers with potential value for understanding the temperature effects on organisms and the treatment of diseases caused by oxidative stress.

Photothermometric analysis of bismuth ions using aggregation-induced nanozyme system with a target-triggered surface cleaning effect.

The development of nanozyme-based photothermometric sensing for point-of-care testing (POCT) heavy metal ions is of great significance for disease diagnosis and health management. Considering the low catalytic activity of most nanozymes at physiological pH, we found bismuth ions (Bi3+) could effectively enhance the peroxidase (POX)-like activity of cetyltrimethylammonium bromide and citrate-capped octahedral gold nanoparticle (CTAB/Cit-AuNP) nanozymes. It is mainly based on Bi3+ ions being able to trigger the surface cleaning effect of CTAB/Cit-AuNPs. Because the more active Bi3+ ions could effectively bind with citrate on the gold surface and competitively destroy the electrostatic interaction between citrate and CTAB, resulting in the removal of CTAB ligands from the gold surface. Without the ligand protection, CTAB/Cit-AuNPs aggregated immediately, and further resulted in a significant activation of the POX-like activity of AuNP nanozymes. Based on this principle, we introduced the enzyme substrate 3,3',5,5'-tetramethylbenzidine (TMB) into this aggregation-induced nanozyme system, and rationally designed a photothermometric platform to quickly and sensitively detect Bi3+ ions by using the good photothermal effect of the oxidation product of TMB (oxTMB). The developed photothermometric method only using a common thermometer has a limit of detection (LOD) as low as 45.7 nM for POCT analysis of Bi3+ ions. This study not only provides a more accurate understanding of the aggregation-induced nanozymes based on the surface cleaning principle, but also shows the potential applications of aggregation-induced nanozymes in the POCT field.

A Fenton-like reaction system with analyte-activated catfish effect as an enhanced colorimetric and photothermal dopamine bioassay.

Fenton-like reaction systems have been proven to be efficient as powerful promoters in advanced oxidation processes (AOPs) due to their generated reactive oxygen species (ROS), such as ˙OH and ˙O2-, which can further oxidize a specific chromogenic substrate like 3,3',5,5'-tetramethylbenzidine (TMB) to generate sensitive color readout and thereby demonstrate more potential in the colorimetric analysis field. However, the inherent drawback of the low rate-limiting step of Fe3+/Fe2+ conversion in the Fenton-like reaction and its resultant inefficiency for H2O2 decomposition hinder its practical applications. We herein communicate an analyte-activated catfish effect based catalysis strategy to promote the Fenton-like reaction, in which dopamine, like a catfish, was added to activate the Fenton-like reaction. By definition, the conversion rate of Fe3+ to Fe2+ in the proposed Fenton-like reaction can be significantly accelerated through a specific DA-mediated electron transfer process which further promotes the reaction activity in the Fenton-like reaction to generate more ˙OH and ˙O2- radicals. As a result, the produced ˙OH and ˙O2- radicals in such a reaction system can significantly oxidize TMB indicator into its oxidation product (TMBox) and therefore indicate the corresponding target-dependent color and photothermal signal readout, enabling the successful fabrication of a more sensitive and stable colorimetric and photothermometric DA sensor. More significantly, this strategy can greatly advance the practical application of Fenton-like reactions in the fields of colorimetric and photothermometric bioassays.

Highly Selective Separation of Rare Earth Elements by Zn-BTC Metal-Organic Framework/Nanoporous Graphene via In Situ Green Synthesis.

Rare earth elements (REEs) are used widely in devices of many fields, but it is still a troublesome task to achieve their selective separation and purification. Metal-organic frameworks (MOFs) as an emerging porous crystalline material have been used for selective separation of REEs using the size-selective crystallization properties. However, so far, almost all MOFs cannot be used directly for selective separation of REEs in strong acid via solid-state adsorption. Herein, a zinc-trimesic acid (Zn-BTC) MOF is grown by solid synthesis in situ on ZnO nanoparticles covering nanoporous graphene for preparing Zn-BTC MOF/nanoporous graphene composites with strong acid resistance. The adsorption capacity of the resulting composites to REEs is highly sensitive to the ionic radius, which may be attributed to the fact that the REE ions coordinate with O to form a stable structure. The selectivity of Ce/Lu is ≈10,000, and it is extremely important that the selectivity between adjacent REEs (e.g., Nd/Pr) is as high as ≈9.8, so the composite exhibits the best separation performance so far. This work provides a green, facile, scale, and effective synthesis strategy of Zn-BTC MOF/nanoporous graphene, which is hopefully applied directly in the separation industries of REEs.

Simply translating mercury detection into a temperature measurement: using an aggregation-activated oxidase-like activity of gold nanoparticles.

A novel Hg2+-responsive thermometer system for translating mercury detection into temperature monitoring was developed based on an aggregation-activated oxidase-like activity of gold nanoparticles.

Gold nanozyme as an excellent co-catalyst for enhancing the performance of a colorimetric and photothermal bioassay.

Advanced oxidation processes (AOPs) have recently proposed for advancing colorimetric sensing applications, owing to their excellent performance of sensitive color readout that generated from the oxidation of chromogenic substrates like 3,3',5,5'-tetramethylbenzidine (TMB) by reactive oxygen species (ROS) of AOPs such as ·OH and ·O2- radicals. However, the efficiency of ROS generation and the related H2O2 decomposition in most AOPs is quite low especially at neutral pH, which greatly hampered the practical sensing applications of the AOPs. We herein communicated that ß-cyclodextrin (ß-CD)-capped gold nanoparticles (ß-CD@AuNPs) can promote catalysis at neutral pH for AOP as an excellent co-catalyst. In this strategy, inorganic pyrophosphate (PPi) ions was first used to coordinate with Cu2+ and form Cu2+-PPi complex. In the presence of hydrogen peroxide, target inorganic pyrophosphatase (PPase) can hydrolyze PPi into inorganic phosphate (Pi) and release free Cu2+ simultaneously, resulting in a Cu2+-triggered Fenton-like AOP reaction. The introduced ß-CD@AuNPs acts as a co-catalyst, analogous to mediators in the most co-catalyzed system, to enhance the rate-limiting step of Cu2+/Cu+ conversion in Cu2+/H2O2 Fenton-like AOP and resulting in an efficient generation of ·OH and ·O2- radicals, which further producing an intense blue color by oxidizing TMB into its oxidation product (TMBox) within a short time. Finally, this reaction system was used to simply detecting target PPase with the colorimetric and photothermal readout based on the in-situ generated TMBox indicator. More significantly, we successfully demonstrated nanozyme can serve as a co-catalyst to promote the AOP catalysis at neutral pH, and inspire other strategies to overcome the pH limitation in the AOP catalysis and expand its colorimetric and photothermometric application.

Photothermal and colorimetric dual mode detection of nanomolar ferric ions in environmental sample based on in situ generation of prussian blue nanoparticles.

Iron ions play a key role in many physiological processes, which can provide feedback for the evaluation of biological systems and environmental processes. New strategies for portable determination of Fe3+ therefore are still in urgent need. Here, through an in situ generation of prussian blue nanoparticles (PB NPs) in aqueous solution, we developed a bimodal method for photothermal and colorimetric detection of Fe3+. The sensing mechanism is based on the effective oxidation etching of Au-Cu core-shell nanocubes induced by Fe3+, accompanied by the in situ generation of PB NPs. It can be attributed to the specific reaction between ferrous ions (Fe2+) from the reduction of Fe3+ and potassium ferricyanide (K3[Fe(CN)6]) in the reaction solution. The in situ produced PB NPs show distinct bare-eye-detectable readouts with highly sensitive colorimetric and photothermal responses and thus can be used for Fe3+ determination. Such colorimetric change signals of characteristic absorbance at 740 nm in the UV-vis spectra showed a sensitive response to Fe3+ with a LOD of 210 nM. Moreover, as a sensitive photothermal probe, PB NPs generated in our Fe3+-enabled reaction system also exhibited a sensitive response to Fe3+ with a LOD of 70 nM. In addition, the standard addition experiments demonstrate our photothermal and colorimetric probe has good applicability for Fe3+ detection in the river water sample. What's more, the proposed strategy opens a new horizon for affordable detection of metal ions using a common thermometer, and therefore has a great potential for analytical chemistry and some important applications such as environmental monitoring, disease diagnostics and food analysis.

Enhanced Thermometric Sensor for Arsenate Analysis Based on Dual Temperature Readout Signaling Strategy.

New methods for portable detection of arsenate are still in urgent need. Herein, we explored a simple but sensitive thermometric strategy for arsenate determination without complex instruments and skilled technicians. Cobalt oxyhydroxide (CoOOH) nanoflakes, can ingeniously decompose hydrogen peroxide into oxygen in a sealed reaction vessel, accompanied by marked pressure and significant temperature increase due to the exothermic reaction effect (ΔH = -98.2 kJ/mol). The increased pressure then compelled a certain amount of H2O overflowing from the drainage device into another vessel, leading to a significant temperature decrease due to the preloaded ammonium nitrate (NH4NO3) and its good dissolution endothermic effect (ΔH = 25.4 kJ/mol). In the presence of arsenate, the catalytic activity of CoOOH nanoflakes for H2O2 decomposition was inhibited dramatically, resulting in an obvious decrease of the pressure, weighting water and temperature response. The two temperature responses with increasing and decreasing feature were easily measured through a common thermometer, and exhibited an effective signaling amplification via coupling both "signal-on" and "signal-off" temperature readout elements. The obtained dual superimposing temperature readout exhibits a good linear with the concentration of arsenate with a lower detection limit (51 nM, 3.8 ppb). Compared to the inductively coupled plasma mass spectrometry, this enhanced thermometric strategy provides a simple, rapid, convenient, low cost, and portable platform for sensing arsenate in real environmental water.

Target-mediated surface chemistry of gold nanorods for breaking the low color resolution limitation of monocolorimetric sensor.

A long-term limitation of low color resolution in the monocolorimetric sensors seriously restricts its extending application, especially for the traditional organic dyes-based monocolorimetric sensors. Herein, we explore a simple target-mediated surface chemistry-based modulation for regulating the surface of gold nanorods (AuNRs), resulting in a successful multicolorimetric sensor for inorganic pyrophosphatase (PPase) activity. It operates on the principle that PPase modulates the release of Fe3+ free from the ferric-pyrophosphate complex (Fe3+-PPi) through a specific target-catalyzed hydrolysis process, leading to a better mediation for the unique chemical redox reaction between Fe3+ and I-. Subsequently, I- is oxidized into I2, which as a moderate oxidant further regulates the surface of AuNRs due to the rapidly etching reaction between I2 and AuNRs. As a result, the resultant AuNRs surface change further leads to a blue-shift longitudinal LSPR effect of AuNRs, along with a naked-eye-detectable rainbow-like multicolor signal readout. Under optimal conditions, the proposed multicolorimetric sensor exhibits an affordable sensing performance for PPase activity in the range from 1.5 U L-1 to 9 U L-1 with a detection limit of 0.8 U L-1 (S/N = 3). To this point, our strategy not only provides a promising way for breaking the low color resolution limitation of the traditional monocolorimetric sensors, but also broadens the applicability of AuNRs etching-based multicolorimetric sensors.

Molecule-gated surface chemistry of Pt nanoparticles for constructing activity-controllable nanozymes and a three-in-one sensor.

Herein, a simple strategy for constructing activity-controllable nanozymes is proposed based on the glutathione (GSH)-gated surface chemistry of citrate-capped Pt nanoparticles (PtNPs). PtNPs have been shown to have oxidase-like activity that can effectively catalyze the oxidation of 3,3',5,5'-tertamethylbenzidine (TMB) by O2, resulting in a typical color reaction from colorless to blue. We found that GSH can inhibit the oxidase-like activity of PtNPs as a molecule-gated surface chemistry element, resulting in a dramatic decrease of the oxidation of TMB. The addition of copper ions (Cu2+) could oxidize GSH into glutathione disulfide (GSSG), resulting in the distinct suppression of GSH-modulated PtNP surface chemistry and oxidase-like activity inhibition, which further results in a significant acceleration of TMB oxidation and the obvious recovery of intense blue color. Furthermore, the color-based detection signal associated with the redox of TMB indicator here was found to show good fluorescence and a photothermal effect and exhibit sensitive and selective response toward the proposed molecule-gated surface chemistry and Cu2+ target. On the basis of this phenomenon, we successfully constructed a three-in-one sensor for Cu2+ with a triple signal readout, colorimetric, photothermal (temperature), and fluorescence, depending on the proposed in situ modulation method for PtNP catalysis. The applicability of the three-in-one sensor was also demonstrated by measuring Cu2+ in human serum with a standard addition method, and the results are of satisfactory accuracy as confirmed by ICP-MS measurements.

A novel electrochemical sensor based on microporous polymeric nanospheres for measuring peroxynitrite anion released by living cells and studying the synergistic effect of antioxidants.

Peroxynitrite anion (ONOO-) is a crucial reactive nitrogen species (RNS), which has aroused immense research interest in the biological and biomedical fields because aberrant expression levels of ONOO- are related to many diseases. In this work, a novel electrochemical sensor is described for the detection of peroxynitrite anion (ONOO-) released from living cells. It is constructed with a glassy carbon electrode (GCE) decorated with a nanocomposite (CTS-MPNS) synthesized from chitosan (CTS) functionalized microporous polymeric nanospheres (MPNS). The prepared CTS-MPNS/GCE sensor shows a supernormal manifestation in measuring ONOO- in a wide range of concentrations from 3.83 nM to 0.104 mM, and the detection limit is as low as 1.28 nM (S/N = 3), which makes it possible to detect trace amounts of ONOO- released from U87 cells. Significantly, the synergistic effect of different antioxidants on scavenging ONOO- in biological systems is further studied by an electrochemical method for the first time, which provides an efficient strategy for protecting cells against oxidative stress. The developed platform and the efficient strategy may pave the way for their future applications in the field of biomedicine and the treatment of cancer diseases.

Resistance and clonal selection among Allium sativum L. germplasm resources to Delia antiqua M. and its correlation with allicin content.

BACKGROUND: Garlic is the second largest allium crop after onion and is grown all over the world. The onion maggot (Delia antiqua M.) is a pest that seriously affects the yield and quality of garlic. Cultural controls and insecticides have several potential problems, including pesticide residue and development of resistance. Screening resistant varieties is an ideal alternative method. RESULTS: The resistance of 213 accessions of garlic clones against onion maggot was identified. The results showed that the pest index was between 5.56% and 91.11%, with classification into six groups by cluster analysis: HR (highly resistant), R (resistant), MR (moderately resistant), MS (moderately susceptible), S (susceptible) and HS (highly susceptible). Among these accessions, 9 and 30 were HR and R to onion maggot, respectively. Comparing the resistances of seven pairs of accessions between the original accessions and their progenies showed that single bulb clonal selection could be an effective way to improve allicin content, onion maggot resistance and most morphological traits. The relationship between allicin content and resistance was investigated, and a significant positive relationship was found. Accessions with a high content of allicin have great potential as resistant accessions. CONCLUSION: This study showed significant differences among garlic germplasm in their response to Delia antiqua M. Some accessions were highly resistant and tolerant. Utilization of these accessions will help minimize environmental pollution, preserve agro-ecosystems and biodiversity, and make management processes more economical. Furthermore, these accessions could be used in breeding programs to develop new maggot-resistant onion cultivars. © 2019 The Authors. Pest Management Science published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.

An ultrasensitive electrochemical sensor based on cotton carbon fiber composites for the determination of superoxide anion release from cells.

A sensor is described for determination of superoxide anion (O2˙-). The electrode consists of nitrogen-doped cotton carbon fiber (NCFs) modified with silver nanoparticles (AgNPs) which have excellent catalytic capability. The resulting sensor, best operated at working potentials around -0.5 V (vs. SCE), can detect O2˙- over an extraordinarily wide range that covers 10 orders of magnitude, and the detection limit is 2.32 ± 0.07 fM. The electrode enables the release of O2˙- from living cells under normal or under oxidative stress conditions to be determined. The ability to scavenge the superoxide anions of antioxidants was also investigated. In the authors' perception, the method represents a viable tool for studying diseases related to oxidative stress. Graphical abstract Schematic presentation of the construction of an electrochemical sensor based on Nitrogen-doped cotton carbon fiber and silver nanoparticles. It can be used for the direct detection of superoxide anions released from Glioma cells (U87) under normal or under oxidative stress conditions.

Metal-organic framework derived carbon-based sensor for monitoring of the oxidative stress of living cell and assessment of antioxidant activity of food extracts.

A novel non-enzymatic superoxide anion radical (O2•-) sensor was prepared by silver nanoparticles (AgNPs) decorated organic frameworks (MOFs) compound-derived metal oxide coated carbon material. Transmission electron microscopy (TEM) was employed to characterize morphologies and structures of the as-prepared samples AgNPs/Co3O4@C. Electrochemical studies indicated that the AgNPs/Co3O4@C/GCE exhibited excellent detection ability to O2•-. It offered a linear range of 8 orders of magnitude and a super low detection limits of 0.0564 pM. The sensor was successfully adapted to detection of O2•- released from living cells. Furthermore, the capacities of scavenging O2•- of food antioxidants were also studied by electrochemical method at cellular milieu. Accordingly, this work provided tremendous potential for reduction incidence of oxidative stress by intaking food antioxidants.

A sensitively non-enzymatic amperometric sensor and its application in living cell superoxide anion radical detection.

Here, we report a nanocomposite composed of silver nanoparticles and multi-walled carbon nanotubes (AgNPs/MWNTs) utilized as an efficient electrode material for sensitive detection superoxide anion (O2•-). The procedure to synthesize AgNPs/MWNTs nanocomposites was green and facile. In the presence of functionalized multi-wall carbon nanotubes (MWNTs), silver nanoparticles (AgNPs) were in situ generated by chemical reduction of silver nitrate with glucose as a reducing and stabilizing agent to give the desired AgNPs/MWNTs nanocomposites. The nanocomposites can be easily used for the construction of an electrochemical sensor on glassy carbon electrode (GCE). The characterization of sensor and experimental parameters affecting its activity were investigated employing scanning electron microscopy (SEM), energy-dispersive X-ray spectrometer (EDS), X-ray diffraction (XRD), and cyclic voltammetry (CV). The resulted sensor exhibited favorable electrochemical performance for O2•- sensing with a low detection limit of 0.1192 nM and wide linear range of 6 orders of magnitude, which guarantees the capacity of sensitive and credible detection of O2•- released from living cells. Notably, a simulation experiment indicated the capacity to resist oxidative stress is limited in biological milieu. Thus this work has great potential for further applications in biological researches.

Construction of an ultrasensitive non-enzymatic sensor to investigate the dynamic process of superoxide anion release from living cells.

In this work, a novel non-enzymatic superoxide anion (O2•-) sensor was constructed based on Ag nanoparticles (NPs) / poly (amidoamine) (PAMAM) dendrimers and used to investigate the dynamic process of O2•- release from living cells. The AgNPs/PAMAM nanohybrids were characterized by transmission electron microscopy (TEM), cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The fabricated electrode exhibited excellent catalytic activity toward the reaction of O2•- with a super low detection limit (LOD) of 2.530 × 10-13M (S/N = 3) and wide linear range of 8 orders of magnitude. It could fulfill the requirement of real-time measurement O2•- released from living cells. Furthermore, zymosan was chosen as the stimulant to induce O2•- generation from cancer cells (rat adrenal medulla pheochromocytoma cell (PC12)). The electrochemical experiment results indicated that the levels of intracellular O2•- depended on the amount of Zymosan. A large amount of O2•- generated in the living cells by added heavy stimulant could damage cells seriously. More importantly, a vitro simulation experiment confirmed the role of superoxide dismutase (SOD) for the first time because it could maintain the O2•- concentration at a normal physiological range. These findings are of great significance for evaluating the metabolic processes of O2•- in the biological system, and this work has the tremendous potential application in clinical diagnostics to assess oxidative stress.