Universal Covalent Grafting Strategy of an Aptamer on a Carbon Fiber Microelectrode for Selective Determination of Dopamine In Vivo.

The chemical information on brain science provided by electrochemical sensors is critical for understanding brain chemistry during physiological and pathological processes. A major challenge is the selectivity of electrochemical sensors in vivo. This work developed a universal covalent grafting strategy of an aptamer on a carbon fiber microelectrode (CFE) for selective determination of dopamine in vivo. The universal strategy was proposed by oxidizing poly(tannic acid) (pTA) to form an oxidized state (pTAox) and then coupling a nucleophilic sulfhydryl molecule of the dopamine-binding mercapto-aptamer with the o-quinone moiety of pTAox based on click chemistry for the interfacial functionalization of the CFE surface. It was found that the universal strategy proposed could efficiently graft the aptamer on a glassy carbon electrode, which was verified by using electroactive 6-(ferrocenyl) hexanethiol as a redox reporter. The amperometric method using a fabricated aptasensor for the determination of dopamine was developed. The linear range of the aptasensor for the determination of dopamine was 0.2-20 µM with a sensitivity of 0.09 nA/µM and a limit of detection of 88 nM (S/N = 3). The developed method has high selectivity originating from the specific recognition of the aptamer in concert with the cation-selective action of pTA and could be easily applicable to probe dopamine dynamics in the brain. Furthermore, complex vesicle fusion modes were first observed at the animal level. This work demonstrated that the covalently grafted immobilization strategy proposed is promising and could be extended to the in vivo analysis of other neurochemicals.

Understanding the different effects of fouling mechanisms on working and reference electrodes in fast-scan cyclic voltammetry for neurotransmitter detection.

Fast-scan cyclic voltammetry (FSCV) is a widely used technique for detecting neurotransmitters. However, electrode fouling can negatively impact its accuracy and sensitivity. Fouling refers to the accumulation of unwanted materials on the electrode surface, which can alter its electrochemical properties and reduce its sensitivity and selectivity. Fouling mechanisms can be broad and may include biofouling, the accumulation of biomolecules on the electrode surface, and chemical fouling, the deposition of unwanted chemical species. Despite individual studies discussing fouling effects on either the working electrode or the reference electrode, no comprehensive study has been conducted to compare the overall fouling effects on both electrodes in the context of FSCV. Here, we examined the effects of biofouling and chemical fouling on the carbon fiber micro-electrode (CFME) as the working electrode and the Ag/AgCl reference electrode with FSCV. Both fouling mechanisms significantly decreased the sensitivity and caused peak voltage shifts in the FSCV signal with the CFME, but not with the Ag/AgCl reference electrode. Interestingly, previous studies have reported peak voltage shifts in FSCV signals due to the fouling of Ag/AgCl electrodes after implantation in the brain. We noticed in a previous study that energy-dispersive spectroscopy (EDS) spectra showed increased sulfide ion concentration after implantation. We hypothesized that sulfide ions may be responsible for the peak voltage shift. To test this hypothesis, we added sulfide ions to the buffer solution, which decreased the open circuit potential of the Ag/AgCl electrode and caused a peak voltage shift in the FSCV voltammograms. Also, EDS analysis showed that sulfide ion concentration increased on the surface of the Ag/AgCl electrodes after 3 weeks of chronic implantation, necessitating consideration of sulfide ions as the fouling agent for the reference electrodes. Overall, our study provides important insights into the mechanisms of electrode fouling and its impact on FSCV measurements. These findings could inform the design of FSCV experiments, with the development of new strategies for improving the accuracy and reliability of FSCV measurements in vivo.

Newly graphene/polypyrrole (rGO/PPy) modified carbon felt as bio-cathode in bio-electrochemical systems (BESs) achieving complete denitrification.

Nitrate reduction in bio-electrochemical systems (BESs) has attracted wide attention due to its low sludge yields and cost-efficiency advantages. However, the high resistance of traditional electrodes is considered to limit the denitrification performance of BESs. Herein, a new graphene/polypyrrole (rGO/PPy) modified electrode is fabricated via one-step electrodeposition and used as cathode in BES for improving nitrate removal from wastewater. The formation and morphological results support the successful formation of rGO/PPy nanohybrids and confirm the part covalent bonding of Py into GO honeycomb lattices to form a three-dimensional cross-linked spatial structure. The electrochemical tests indicate that the rGO/PPy electrode outperforms the unmodified electrode due to the 3.9-fold increase in electrochemical active surface area and 6.9-fold decrease in the charge transfer resistance (Rct). Batch denitrification activity tests demonstrate that the BES equipped with modified rGO/PPy biocathode could not only achieve the full denitrification efficiency of 100% with energy recovery (15.9 × 10-2 ± 0.14 A/m2), but also favor microbial attach and growth with improved biocompatible surface. This work provides a feasible electrochemical route to fabricate and design a high-performance bioelectrode to enhance denitrification in BESs.

Activated carbon fiber as an efficient co-catalyst toward accelerating Fe2+/Fe3+ cycling for improved removal of antibiotic cefaclor via electro-Fenton process using a gas diffusion electrode.

The electro-Fenton (EF) based on gas-diffusion electrodes (GDEs) reveals promising application prospective towards recalcitrant organics degradation because such GDEs often yields superior H2O2 generation efficiency and selectivity. However, the low efficiency of Fe2+/Fe3+ cycle with GDEs is always considered to be the limiting step for the EF process. In this study, activated carbon fiber (ACF) was firstly employed as co-catalyst to facilitate the performance of antibiotic cefaclor (CEC) decomposition in EF process. It was found that the addition of ACF co-catalyst achieved a rapid Fe2+/Fe3+ cycling, which significantly enhanced Fenton's reaction and hydroxyl radicals (•OH) generation. X-ray photoelectron spectroscopy (XPS) results indicated that the functional groups on ACF surface are related to the conversion of Fe3+ into Fe2+. Moreover, DMSO probing experiment confirmed the enhanced •OH production in EF + ACF system compared to conventional EF system. When inactive BDD and Ti4O7/Ti anodes were paired to EF system, the addition of ACF could significantly improve mineralization degree. However, a large amount of toxic byproducts, including chlorate (ClO3-) and perchlorate (ClO4-), were generated in these EF processes, especially for BDD anode, due to their robust oxidation capacity. Higher mineralization efficiency and less toxic ClO4- generation were obtained in the EF + ACF process with Ti4O7/Ti anode. This presents a novel alternative for efficient chloride-containing organic removal during wastewater remediation.

Controlled synthesized of ternary Cu-Co-Ni-S sulfides nanoporous network structure on carbon fiber paper: a superior catalytic electrode for highly-sensitive glucose sensing.

BACKGROUND: Efficient monitoring of glucose concentration in the human body necessitates the utilization of electrochemically active sensing materials in nonenzymatic glucose sensors. However, prevailing limitations such as intricate fabrication processes, lower sensitivity, and instability impede their practical application. Herein, ternary Cu-Co-Ni-S sulfides nanoporous network structure was synthesized on carbon fiber paper (CP) by an ultrafast, facile, and controllable technique through on-step cyclic voltammetry, serving as a superior self-supporting catalytic electrode for the high-performance glucose sensor. RESULTS: The direct growth of free-standing Cu-Co-Ni-S on the interconnected three-dimensional (3D) network of CP boosted the active site of the composites, improved ion diffusion kinetics, and significantly promoted the electron transfer rate. The multiple oxidation states and synergistic effects among Co, Ni, Cu, and S further promoted glucose electrooxidation. The well-architected Cu-Co-Ni-S/CP presented exceptional electrocatalytic properties for glucose with satisfied linearity of a broad range from 0.3 to 16,000 µM and high sensitivity of 6829 µA mM- 1 cm- 2. Furthermore, the novel sensor demonstrated excellent selectivity and storage stability, which could successfully evaluate the glucose levels in human serum. Notably, the novel Cu-Co-Ni-S/CP showed favorable biocompatibility, proving its potential for in vivo glucose monitoring. CONCLUSION: The proposed 3D hierarchical morphology self-supported electrode sensor, which demonstrates appealing analysis behavior for glucose electrooxidation, holds great promise for the next generation of high-performance glucose sensors.

Dental implant and abutment in PEEK: stress assessment in single crown retainers on anterior region.

OBJECTIVE: Stress distribution assessment by finite elements analysis in poly(etheretherketone) (PEEK) implant and abutment as retainers of single crowns in the anterior region. MATERIALS AND METHODS: Five 3D models were created, varying implant/abutment manufacturing materials: titanium (Ti), zirconia (Zr), pure PEEK (PEEKp), carbon fiber-reinforced PEEK (PEEKc), glass fiber-reinforced PEEK (PEEKg). A 50 N load was applied 30o off-axis at the incisal edge of the upper central incisor. The Von Mises stress (σvM) was evaluated on abutment, implant/screw, and minimum principal stress (σmin) and maximum shear stress (τmax) for cortical and cancellous bone. RESULTS: The abutment σvM lowest stress was observed in PEEKp group, being 70% lower than Ti and 74% than Zr. On the implant, PEEKp reduced 68% compared to Ti and a 71% to Zr. In the abutment screws, an increase of at least 33% was found in PEEKc compared to Ti, and of at least 81% to Zr. For cortical bone, the highest τmax values were in the PEEKp group, and a slight increase in stress was observed compared to all PEEK groups with Ti and Zr. For σmin, the highest stress was found in the PEEKc. Stress increased at least 7% in cancellous bone for all PEEK groups. CONCLUSION: Abutments and implants made by PEEKc concentrate less σvM stress, transmitting greater stress to the cortical and medullary bone. CLINICAL RELEVANCE: The best stress distribution in PEEKc components may contribute to decreased stress shielding; in vitro and in vivo research is recommended to investigate this.

Preparation of CF/PEEK Composites with High Mechanical Performance Using PEEK Derivatives as the Sizing Agent.

Owing to their excellent physical and chemical properties, the carbon fibre reinforced poly(ether-ether-ketone) composites (CF/PEEK) are widely used in aerospace applications such as rockets, missiles, and high-speed vehicles. However, both carbon fibre (CF) and poly(ether-ether-ketone) (PEEK) have inert molecular chain structures, which seriously affect the interfacial properties of CF/PEEK composites. In this study, to improve the properties of CF/PEEK composites, carboxylated PEEK (PEEK-COOH) with different carboxylation degrees is synthesized as the sizing agent by a "two-step" method. Then, the activated CF surface is coated by PEEK-COOH sizing layers with different functionalization degrees to prepare the CF/PEEK composites. The results show that the interfacial properties of CF/PEEK composites are improved after applying the sizing agent. When the carboxylation degree of PEEK-COOH is 19.61%, the flexural strength, flexural modulus, and interlaminar shear strength (ILSS) of CF/PEEK composites reach 489.34 MPa, 25.387 GPa, and 81.3 MPa, respectively. In addition, the use of PEEK-COOH sizing agents can form an excellent transition layer between CF and PEEK, creating an efficient stress transfer system and facilitating an even stress distribution between CF and PEEK. Furthermore, the main mechanism of material fracture changes from CF debonding to CF and resin fracture.

Carbon-fiber-reinforced polyetheretherketone orthopedic implants in musculoskeletal and spinal tumors: imaging and clinical features.

Carbon-fiber-reinforced polyetheretherketone (CFR-PEEK) orthopedic implants are gaining popularity in oncologic applications as they offer many potential advantages over traditional metallic implants. From an imaging perspective, this instrumentation allows for improved evaluation of adjacent anatomic structures during radiography, computed tomography (CT), and magnetic resonance imaging (MRI). This results in improved postoperative surveillance imaging quality as well as easier visualization of anatomy for potential image-guided percutaneous interventions (e.g., pain palliation injections, or ablative procedures for local disease control). CFR-PEEK devices are also advantageous in radiation oncology treatment due to their decreased imaging artifact during treatment planning imaging and decreased dose perturbation during radiotherapy delivery. As manufacturing processes for CFR-PEEK materials continue to evolve and improve, potential orthopedic applications in the spine and appendicular skeleton increase. An understanding of the unique properties of CFR-PEEK devices and their impact on imaging is valuable to radiologists delivering care to orthopedic oncology patients in both the diagnostic and interventional settings. This multidisciplinary review aims to provide a comprehensive insight into the radiologic, surgical, and radiation oncology impact of these innovative devices.

Graphene-Fiber Microelectrodes for Ultrasensitive Neurochemical Detection.

Here, we have synthesized and characterized graphene-fiber microelectrodes (GFME's) for subsecond detection of neurochemicals with fast-scan cyclic voltammetry (FSCV) for the first time. GFME's exhibited extraordinary properties including faster electron transfer kinetics, significantly improved sensitivity, and ease of tunability that we anticipate will have major impacts on neurochemical detection for years to come. GF's have been used in the literature for various applications; however, scaling their size down to microelectrodes and implementing them as neurochemical microsensors is significantly less developed. The GF's developed in this paper were on average 20-30 µm in diameter and both graphene oxide (GO) and reduced graphene oxide (rGO) fibers were characterized with FSCV. Neat GF's were synthesized using a one-step dimension-confined hydrothermal strategy. FSCV detection has traditionally used carbon-fiber microelectrodes (CFME's) and more recently carbon nanotube fiber electrodes; however, uniform functionalization and direct control of the 3D surface structure of these materials remain limited. The expansion to GFME's will certainly open new avenues for fine-tuning the electrode surface for specific electrochemical detection. When comparing to traditional CFME's, our GFME's exhibited significant increases in electron transfer, redox cycling, fouling resistance, higher sensitivity, and frequency independent behavior which demonstrates their incredible utility as biological sensors.

Nanostructured carbon-fiber surfaces for improved neurochemical detection.

Fundamental insight into the extent to which the nanostructured surface and geometry impacts neurochemical interactions at electrode surfaces could provide significant advances in our ability to design and fabricate ultrasensitive neurochemical detection probes. Here, we investigate the extent to which the nanostructure of the carbon-fiber surface impacts detection of catecholamines and purines with fast-scan cyclic voltammetry (FSCV). Carbon-fibers were treated with argon (Ar) plasma to induce variations in the nano- and micro-structure without changing the functionalization of the surface. We tested variations in topology by measuring the extent to which the flow rate, RF power, and treatment time affect the surface roughness. Flow rates from 50-100 sccm, plasma power from 20-100 W, and treatment times from 30 s to 5 min were compared. Two Ar-treatments were chosen from the optimization studies for comparison, and the surface roughness was evaluated using atomic force microscopy (AFM). To ensure no changes in chemical composition, fibers were analyzed with X-ray photoelectron spectroscopy (XPS). On average, at the optimized Ar-plasma treatment procedure, oxidative current for adenosine and ATP increased by 3.5 ± 1.4-fold and 3.2 ± 0.6-fold, and guanosine and GTP by 1.7 ± 0.3-fold and 1.8 ± 0.3-fold, respectively (n = 9). Dopamine increased by 1.7 ± 0.3-fold. The extent to which changes in the electrode structure impact adsorption, sensitivity, and electron transfer rates were measured. A COMSOL Multiphysics simulation was developed to enable the modeling of mass transport of electroactive species at varying electrode geometries. Overall, this study provides critical insight into the extent to which the nanostructure of the surface impacts the electrochemical detection of neurochemicals.

Design and Evaluation of a Lactate Microbiosensor: Toward Multianalyte Monitoring of Neurometabolic Markers In Vivo in the Brain.

Direct in vivo measurements of neurometabolic markers in the brain with high spatio-temporal resolution, sensitivity, and selectivity is highly important to understand neurometabolism. Electrochemical biosensors based on microelectrodes are very attractive analytical tools for continuous monitoring of neurometabolic markers, such as lactate and glucose in the brain extracellular space at resting and following neuronal activation. Here, we assess the merits of a platinized carbon fiber microelectrode (CFM/Pt) as a sensing platform for developing enzyme oxidase-based microbiosensors to measure extracellular lactate in the brain. Lactate oxidase was immobilized on the CFM/Pt surface by crosslinking with glutaraldehyde. The CFM/Pt-based lactate microbiosensor exhibited high sensitivity and selectivity, good operational stability, and low dependence on oxygen, temperature, and pH. An array consisting of a glucose and lactate microbiosensors, including a null sensor, was used for concurrent measurement of both neurometabolic substrates in vivo in the anesthetized rat brain. Rapid changes of lactate and glucose were observed in the cortex and hippocampus in response to local glucose and lactate application and upon insulin-induced fluctuations of systemic glucose. Overall, these results indicate that microbiosensors are a valuable tool to investigate neurometabolism and to better understand the role of major neurometabolic markers, such as lactate and glucose.

Measurement of Neuropeptide Y Using Aptamer-Modified Microelectrodes by Electrochemical Impedance Spectroscopy.

Aptamer-modified microelectrodes for Neuropeptide Y measurement by electrochemical impedance spectroscopy was described here. The advantages of using carbon fiber or platinum microelectrodes are because they are promising materials with high electrical conductivity, chemical stability, and high surface area that can be easily modified on their surface. The immobilization and biofouling were studied and compared using EIS. Moreover, the adsorption of NPY to the aptamer-modified microelectrodes was also demonstrated by EIS. Changes of -ω*Zimag, an impedance factor that gives information of the capacitance, is directly correlated with concentrations. A widely linear range was obtained from 10 to 1000 ng/mL of NPY. This method was able to detect NPY without performing a redox reaction by adsorption at the surface of the microelectrodes, with the specificity provided by aptamer functionalization of the microelectrode surface.

Activated Carbon Fiber Cloth/Biomimetic Apatite: A Dual Drug Delivery System.

A biomaterial that is both bioactive and capable of controlled drug release is highly attractive for bone regeneration. In previous works, we demonstrated the possibility of combining activated carbon fiber cloth (ACC) and biomimetic apatite (such as calcium-deficient hydroxyapatite (CDA)) to develop an efficient material for bone regeneration. The aim to use the adsorption properties of an activated carbon/biomimetic apatite composite to synthetize a biomaterial to be used as a controlled drug release system after implantation. The adsorption and desorption of tetracycline and aspirin were first investigated in the ACC and CDA components and then on ACC/CDA composite. The results showed that drug adsorption and release are dependent on the adsorbent material and the drug polarity/hydrophilicity, leading to two distinct modes of drug adsorption and release. Consequently, a double adsorption approach was successfully performed, leading to a multifunctional and innovative ACC-aspirin/CDA-tetracycline implantable biomaterial. In a second step, in vitro tests emphasized a better affinity of the drug (tetracycline or aspirin)-loaded ACC/CDA materials towards human primary osteoblast viability and proliferation. Then, in vivo experiments on a large cortical bone defect in rats was carried out to test biocompatibility and bone regeneration ability. Data clearly highlighted a significant acceleration of bone reconstruction in the presence of the ACC/CDA patch. The ability of the aspirin-loaded ACC/CDA material to release the drug in situ for improving bone healing was also underlined, as a proof of concept. This work highlights the possibility of bone patches with controlled (multi)drug release features being used for bone tissue repair.

Mesoporous Carbon Fibers with Tunable Mesoporosity for Electrode Materials in Energy Devices.

To improve the properties of mesoporous carbon (MC), used as a catalyst support within electrodes, MC fibers (MCFs) were successfully synthesized by combining organic-organic self-assembly and electrospinning deposition and optimizing heat treatment conditions. The pore structure was controlled by varying the experimental conditions. Among MCFs, MCF-A, which was made in the most acidic condition, resulted in the largest pore diameter (4-5 nm), and the porous structure and carbonization degree were further optimized by adjusting heat treatment conditions. Then, since the fiber structure is expected to have an advantage when MCFs are applied to devices, MCF-A layers were prepared by spray printing. For the resistance to compression, MCF-A layers showed higher resistance (5.5% change in thickness) than the bulk MC layer (12.8% change in thickness). The through-plane resistance was lower when the fiber structure remained more within the thin layer, for example, +8 mΩ for 450 rpm milled MCF-A and +12 mΩ for 800 rpm milled MCF-A against the gas diffusion layer (GDL) 25BC carbon paper without a carbon layer coating. The additional advantages of MCF-A compared with bulk MC demonstrate that MCF-A has the potential to be used as a catalyst support within electrodes in energy devices.

Quantitative Evaluation of Carbon Fiber Dispersion in Amorphous Calcium Silicate Hydrate-Based Contact-Hardening Composites.

Carbon fiber dispersion has a substantial influence on the properties of amorphous calcium silicate hydrate-based contact-hardening composites. In this study, a mixture of carbon fiber and calcium silicate hydrate powder was compressed into solid composites at 40 MPa for one minute. The mechanical properties and electrical resistivity of the solid materials were measured, and the dispersion of carbon fibers was quantitatively evaluated by digital image processing technology. The Taipalu model was used to build the correlation between the electrical resistivity of the composites and the carbon fiber dispersion. The results of the electrical resistivity showed that the down threshold of carbon fiber content in the contact-hardening composites was 1.0 wt.% and the electrical resistivity was 30,000 Ω·cm. As the fiber content increased to 2.0 wt.%, the electrical resistivity dropped to 2550 Ω·cm, which was attributed to the increase in fiber dispersion uniformity in the solid composites, and the value of the fiber distribution coefficient reached a maximum value of 0.743. A subsequent decrease in the uniformity of the fiber dispersion was observed at a high fiber content. In addition, the carbon fiber content showed a slight influence on the fiber orientation in the contact-hardening composites.

Metal Organic Frameworks Derived Fe-N-C Nanostructures as High-Performance Electrodes for Sodium Ion Batteries and Electromagnetic Interference (EMI) Shielding.

Metal organic framework (MOF)-derived carbon nanostructures (MDC) synthesized by either calcinations or carbonization or pyrolysis are emerging as attractive materials for a wide range of applications like batteries, super-capacitors, sensors, water treatment, etc. But the process of transformation of MOFs into MDCs is time-consuming, with reactions requiring inert atmospheres and reaction time typically running into hours. In this manuscript, we report the transformation of 1,4-diazabicyclo[2.2.2]octane, (DABCO)-based MOFs into iron nitride nanoparticles embedded in nitrogen-doped carbon nanotubes by simple, fast and facile microwave pyrolysis. By using graphene oxide and carbon fiber as microwave susceptible surfaces, three-dimensional nitrogen-doped carbon nanotubes vertically grown on reduced graphene oxide (MDNCNT@rGO) and carbon fibers (MDCNT@CF), respectively, were obtained, whose utility as anode material in sodium-ion batteries (MDNCNT@rGO) and for EMI (electromagnetic interference) shielding material (MDCNT@CF) is reported.

Fast Detection of Single Liposomes Using a Combined Nanopore Microelectrode Sensor.

Here we report the development and characterization of a high throughput sensing device for single liposome detection. The device incorporates a quartz nanopipette positioned near a carbon-fiber microelectrode (CFE). Liposomes (∼200 nm diameter) loaded with Fe(CN)64- are driven out of the nanopipette orifice where they are sensed as a transient decrease in the measured ionic current (resistive-pulse analysis). Simultaneously, a redox signal is collected at the CFE due to the release of internalized redox molecules from translocating liposomes to the CFE surface. Interestingly, we observed that the redox signals arise coincidently with resistive-pulses, suggesting that leakage of liposome contents occurs during translocation. Further investigation suggested that liposome disruption occurs at the nanopore orifice and is not dependent on the nanopore electric field. The probability of this disruption appears to rely on the velocity of fluid flow in the nanopore as well as the nanopore geometry. The high-throughput nature of our technique may prove useful for rapid analysis of liposomal drug formulations or rapid, robust, direct measurement of neurotransmitter concentration in isolated vesicles from neurons and neuroendocrine cells.

Single-Cell On-Probe Derivatization-Noncontact Nanocarbon Fiber Ionization: Unraveling Cellular Heterogeneity of Fatty Alcohol and Sterol Metabolites.

Currently in single-cell mass spectrometry, the analysis of low-abundance cell metabolites such as fatty alcohols and sterols remains a challenge. In most research studies, single-cell samples are analyzed directly after sampling. However, this workflow may exclude many effective sample pretreatment methods such as derivatization for the improvement of detection sensitivity for specific cell metabolites in a single-cell sample. Metabolites in low abundance in a cell may not be detected. Herein on-probe derivatization coupled with noncontact nanocarbon fiber ionization is proposed for sensitive fatty alcohol and sterol metabolite analysis at the single-cell level. Fatty alcohol and sterol metabolites were rapidly quaternized by the single-cell on-probe derivatization method. The reaction products were directly ionized with no postreaction processing. Furthermore, a new ionization source for noncontact nanocarbon fiber ionization was developed to show good compatibility with dichloromethane, a low-polarity solvent used in on-probe derivatization. The quaternized fatty alcohols and sterols exhibited evidently enhanced ionization efficiency in mass spectra. In applications of the developed method, seven kinds of even-numbered-carbon fatty alcohols (C12-C22) and five kinds of sterols were detected in single L-02 and HepG2 cells. Then the L-02 and HepG2 cells were readily discriminated through principal component analysis. Additionally, a rough quantitative analysis of the detected fatty alcohols and sterols in single cells was performed. The mass intensities of fatty alcohols show a significant difference between L-02 and HepG2 cells while those of sterols remain stable.

Dual-Response Ratiometric Electrochemical Microsensor for Effective Simultaneous Monitoring of Hypochlorous Acid and Ascorbic Acid in Human Body Fluids.

Redox homeostasis between hypochlorous acid (HClO/ClO-) and ascorbic acid (AA) significantly impacts many physiological and pathological processes. Herein, we report a new electrochemical sensor for the simultaneous determination of HClO and AA in body fluids. We first coated a carbon fiber microelectrode (CFME) with a three-dimensional nanocomposite consisting of graphene oxide (GO) and carbon nanotubes (CNTs) to fabricate the CFME/GO-CNT electrode. After the electrochemical reduction of GO (ERGO), we integrated a latent 1-(3,7-bis(dimethylamino)-10H-phenothiazin-10-yl)-2-methylpropan-1-one (MBS) electrochemical molecular recognition probe to monitor HClO and employed anthraquinone (AQ) as an internal reference. The compact CFME/ERGO-CNT/AQ + MBS sensor enabled the accurate and simultaneous measurement of HClO and AA with excellent selectivity and sensitivity. Measurements were highly reproducible, and the sensor was stable and exceptionally biocompatible. We successfully detected changes in the redox cycles of HClO and AA in human body fluids. This sensor is a significant advance for the investigation of reactions involved in cellular redox regulation. More importantly, we have devised a strategy for the design and construction of ratiometric electrochemical biosensors for the simultaneous determination of various bioactive species.

Natural Leukocyte Membrane-Masked Microelectrodes with an Enhanced Antifouling Ability and Biocompatibility for In Vivo Electrochemical Sensing.

Probing chemical information in the central nervous system is essential for understanding the molecular mechanism of brain function. Electrochemistry with tissue-implantable carbon fiber electrodes (CFEs) provides a powerful tool for monitoring the dynamics of neurochemicals in a subsecond time scale; however, the implantation of CFEs into brain tissue immediately causes the nonspecific adsorption of proteins on electrode surfaces. This process can dramatically impact the performance of the electrochemical method in terms of reduced sensitivity and accuracy. Herein, we report a strategy to minimize the electrode biofouling by masking CFEs with leukocyte membranes (LMs). We find that the LM masking endows CFEs with a highly hydrophilic surface that gains a high resistance to nonspecific protein adsorption. The electrode reactivity to target molecules decreases by a small degree due to the membrane coating, but the sensitivity loss of the LM-masked CFEs is greatly lessened even after in vivo implantation for 8 h. This study offers a new method of microelectrode modification by natural cell membranes for sustained sensing performance during long-term in vivo analysis.