An investigation of the corrosion behavior of zinc-coated stainless steel orthodontic wires: the effect of physical vapor deposition method.

BACKGROUND: Releasing of metal ions might implicate in allergic reaction as a negative subsequent of the corrosion of Stainless Steel (SS304) orthodontic wires. The aim of this study was to evaluate the corrosion resistance of zinc-coated (Zn-coated) SS orthodontic wires. METHODS: Zinc coating was applied on SS wires by PVD method. Electrochemical impedance spectroscopy (EIS), Potentiodynamic polarization tests and Tafel analysis methods were used to predict the corrosion behavior of Zn-coated and uncoated SS wires in both neutral and acidic environments. RESULTS: The values of Ecorr ,icorr and Rct ,which were the electrochemical corrosion characteristics, reported better corrosion behavior of Zn-coated SS wires against uncoated ones in both artificial saliva and fluoride-containing environments. Experimental results of the Tafel plot analyses were consistent with that of electrochemical impedance spectroscopy analyses for both biological solutions. CONCLUSION: Applying Zn coating on bare SS orthodontic wire by PVD method might increase the corrosion resistance of the underlying stainless-steel substrate.

Polymeric membrane potentiometric sensors based on template-removal-free imprinted receptors for determination of antibiotics.

Currently, Nernstian-response-based polymeric membrane potentiometric sensors using molecularly imprinted polymers (MIPs) as receptors have been successfully developed for determination of organic ionic species. However, the preparation of these MIP receptors usually involves tedious and time-consuming template-removal procedures. Herein, a template-removal-free MIP is proposed and used as a receptor for fabrication of a potentiometric sensor. The proposed methodology not only significantly shortens the preparation time of MIP-based potentiometric sensors but also improves the batch-to-batch reproducibility of these sensors. By using antibiotic vancomycin as a model, the new concept offers a linear concentration range of 1.0 × 10-7 to 1.0 × 10-4 mol L-1 with a detection limit of 2.51 × 10-8 mol L-1. It can be expected that the template-removal-free MIP-based sensing strategy could lay the foundation for simple fabrication of electrochemical sensors without the need for template removal such as potentiometric and capacitive sensors and ion-sensitive field-effect transistors.

Functionalized orthopaedic implant as pH electrochemical sensing tool for smart diagnosis of hardware infection.

In the orthopaedic surgery field, the use of medical implants to treat a patient's bone fracture is nowadays a common practice, nevertheless, it is associated with possible cases of infection. The consequent hardware infection can lead to implant failure and systemic infections, with prolonged hospitalization, time-consuming rehabilitation treatments, and extended antibiotic therapy. Hardware infections are strictly related to bacterial adhesion to the implant, leading to infection occurrence and consequent pH decreasing from physiological level to acid pH. Here, we demonstrate the new strategy to use an orthopaedic implant functionalized with iridium oxide film as the working electrode for the potentiometric monitoring of pH in hardware infection diagnosis. A functional investigation was focused on selecting the implant material, namely titanium, titanium alloy, and stainless steel, and the component, namely screws and implants. After selecting the titanium-based implant as the working electrode and a silver wire as the reference electrode in the final configuration of the smart sensing orthopaedic implant, a calibration curve was performed in standard solutions. An equation equal to y = (0.76 ± 0.02) - (0.068 ± 0.002) x, R2 = 0.996, was obtained in the pH range of 4-8. Subsequently, hysteresis, interference, matrix effect, recovery study, and storage stability were investigated to test the overall performance of the sensing device, demonstrating the tremendous potential of electrochemical sensors to deliver the next generation of smart orthopaedic implants.

Wireless wearable potentiometric sensor for simultaneous determination of pH, sodium and potassium in human sweat.

This paper reports on the development of a flexible-wearable potentiometric sensor for real-time monitoring of sodium ion (Na+), potassium ion (K+), and pH in human sweat. Na0.44MnO2, polyaniline, and K2Co[Fe(CN)6] were used as sensing materials for Na+, H+ and K+ monitoring, respectively. The simultaneous potentiometric Na+, K+, and pH sensing were carried out by the developed sensor, which enables signal collection and transmission in real-time to the smartphone via a Wi-Fi access point. Then, the potentiometric responses were evaluated by a designed android application. Na+, K+, and pH sensors illustrated high sensitivity (59.7 ± 0.8 mV/decade for Na+, 57.8 ± 0.9 mV/decade for K+, and 54.7 ± 0.6 mV/pH for pH), excellent stability, and good batch-to-batch reproducibility. The results of on-body experiments demonstrated that the proposed platform is capable of real-time monitoring of the investigated ions.

The Role of the Unbinding Cycle on the Coordination Abilities of the Bi-Cyclopeptides toward Cu(II) Ions.

Bicyclic peptides have attracted the interest of pharmaceutical companies because of their remarkable properties, putting them on a new path in medicine. Their conformational rigidity improves proteolytic stability and leads to rapid penetration into tissues via any possible route of administration. Moreover, elimination of renal metabolism is of great importance, for example, for people with a history of liver diseases. In addition, each ring can function independently, making bicyclic peptides extremely versatile molecules for further optimization. In this paper, we compared the potentiometric and spectroscopic properties studied by UV-vis, MCD, and EPR of four synthetic analogues of the bi-cyclic peptide c(PKKHP-c(CFWKTC)-PKKH) (BCL). In particular, we correlated the structural and spectral properties of complexes with coordinating abilities toward Cu(II) ions of MCL1 (Ac-PKKHPc(CFWKTC)PKKH-NH2) that contains the unbinding cycle and N- and C-terminal linear parts with two histidine residues, one per part; two monocyclic ligands containing one histidine residue, both in the N-terminal position, i.e., MCL2 (Ac-PKKHPc(CFWKTC)PKKS-NH2) and in the C-terminal position, i.e., MCL3 (Ac-PKKSPc(CFWKTC)PKKH-NH2), respectively; and the linear structure LNL (Ac-PKKHPSFWKTSPKKH-NH2). Potentiometric results have shown that the bicyclic structure promotes the involvement of the side chain imidazole donors in Cu(II) binding. On the other hand, the results obtained for the mono-cyclic analogues lead to the conclusion that the coordination of the histidine moiety as an anchoring group is promoted by its location in the peptide sequence further from the nonbinding cycle, strongly influencing the involvement of the amide donors in Cu(II) coordination.

A novel potentiometric screen-printed electrode based on crown ethers/nano manganese oxide/Nafion composite for trace level determination of copper ion in biological fluids.

Copper levels in biological fluids are associated with Wilson's, Alzheimer's, Menke's, and Parkinson's diseases, making them good biochemical markers for these diseases. This study introduces a miniaturized screen-printed electrode (SPE) for the potentiometric determination of copper(II) in some biological fluids. Manganese(III) oxide nanoparticles (Mn2O3-NPs), dispersed in Nafion, are drop-casted onto a graphite/PET substrate, serving as the ion-to-electron transducer material. The solid-contact material is then covered by a selective polyvinyl chloride (PVC) membrane incorporated with 18-crown-6 as a neutral ion carrier for the selective determination of copper(II) ions. The proposed electrode exhibits a Nernstian response with a slope of 30.2 ± 0.3 mV/decade (R2 = 0.999) over the linear concentration range 5.2 × 10-9 - 6.2 × 10-3 mol/l and a detection limit of 1.1 × 10-9 mol/l (69.9 ng/l). Short-term potential stability is evaluated using constant current chronopotentiometry (CP) and electrochemical impedance spectroscopy (EIS). A significant improvement in the electrode capacitance (91.5 µF) is displayed due to the use of Mn2O3-NPs as a solid contact. The presence of Nafion, with its high hydrophobicity properties, eliminates the formation of the thin water layer, facilitating the ion-to-electron transduction between the sensing membrane and the conducting substrate. Additionally, it enhances the adhesion of the polymeric sensing membrane to the solid-contact material, preventing membrane delamination and increasing the electrode's lifespan. The high selectivity, sensitivity, and potential stability of the proposed miniaturized electrode suggests its use for the determination of copper(II) ions in human blood serum and milk samples. The results obtained agree fairly well with data obtained by flameless atomic absorption spectrometry.

Redox Properties of Bacillus subtilis Ferredoxin:NADP+ Oxidoreductase: Potentiometric Characteristics and Reactions with Pro-Oxidant Xenobiotics.

Bacillus subtilis ferredoxin:NADP+ oxidoreductase (BsFNR) is a thioredoxin reductase-type FNR whose redox properties and reactivity with nonphysiological electron acceptors have been scarcely characterized. On the basis of redox reactions with 3-acetylpyridine adenine dinucleotide phosphate, the two-electron reduction midpoint potential of the flavin adenine dinucleotide (FAD) cofactor was estimated to be -0.240 V. Photoreduction using 5-deazaflavin mononucleotide (5-deazaFMN) as a photosensitizer revealed that the difference in the redox potentials between the first and second single-electron transfer steps was 0.024 V. We examined the mechanisms of the reduction of several different groups of non-physiological electron acceptors catalyzed by BsFNR. The reactivity of quinones and aromatic N-oxides toward BsFNR increased when increasing their single-electron reduction midpoint redox potentials. The reactivity of nitroaromatic compounds was lower due to their lower electron self-exchange rate, but it exhibited the same trend. A mixed single- and two-electron reduction reaction was characteristic of quinones, whereas reactions involving nitroaromatics proceeded exclusively via the one-electron reduction reaction. The oxidation of FADH• to FAD is the rate-limiting step during the oxidation of fully reduced FAD. The calculated electron transfer distances in the reaction with nitroaromatics were close to those of other FNRs including the plant-type enzymes, thus demonstrating their similar active site accessibility to low-molecular-weight oxidants despite the fundamental differences in their structures.

Chronopotentiometric sensors for antimicrobial peptide-based biosensing of Staphylococcus aureus.

Charged antimicrobial peptides can be used for direct potentiometric biosensing, but have never been explored. We report here a galvanostatically-controlled potentiometric sensor for antimicrobial peptide-based biosensing. Solid-state pulsed galvanostatic sensors that showed excellent stability under continuous galvanostatic polarization were prepared by utilizing reduced graphene oxide/poly (3,4-ethylenedioxythiophene): poly (4-styrenesulfonate) (rGO/PEDOT: PSS) as a solid contact. More importantly, the chronopotentiometric sensor can be made sensitive to antimicrobial peptides with intrinsic charge on demand via a current pulse. In this study, a positively charged antimicrobial peptide that can bind to Staphylococcus aureus with high affinity and good selectivity was designed as a model. Two arginine residues with positive charges were linked to the C-terminal of the peptide sequence to increase its potentiometric responses on the electrode. The bacteria binding-induced charge or charge density change of the antimicrobial peptide enables the direct chronopotentiometric detection of the target. Under the optimized conditions, the concentration of Staphylococcus aureus can be determined in the linear range 10-1.0 × 105 CFU mL-1 with a detection limit of 10 CFU mL-1. It is anticipated that such a chronopotentiometric sensing platform is readily adaptable to detect other bacteria by choosing the peptides.

Single-cell calcium monitoring of Caco-2 cell co-cultured with intestinal microbiome through carbon fiber based potentiometric microelectrode.

The Caco-2 cells were used as intestinal epithelial cell model to illustrate the hyperuricemia (HUA) mechanism under the co-culture of the imbalanced intestinal microbiome in this work. The uric acid (UA) concentration in the HUA process was monitored, and could be up to 425 µmol/L at 8 h co-cultured with the imbalanced intestinal microbiome. Single-cell potentiometry based on ion-selective microelectrode was used to study extracellular calcium change, which is hypothesized to play an important role in the UA excretion. The potential signal of the calcium in the extremely limited microenvironment around single Caco-2 cell was recorded through the single-cell analysis platform. The potential signal of sharp decrease and slow increase followed within a few seconds indicates the sudden uptake and gradually excretion process of calcium through the cell membrane. Moreover, the value of the potential decrease increases with the increase of the time co-cultured with the imbalanced intestinal microbiome ranging from 0 to 8 h. The Ca2+ concentration around the cell membrane could decrease from 1.3 mM to 0.4 mM according to the potential decrease of 27.0 mV at the co-culture time of 8 h. The apoptosis ratio of the Caco-2 cells also exhibits time dependent with the co-culture of the imbalanced intestinal microbiome, and was 39.1 ± 3.6 % at the co-culture time of 8 h, which is much higher than the Caco-2 cells without any treatment (3.9 ± 2.9 %). These results firstly provide the links between the UA excretion with the apoptosis of the intestinal epithelial cell under the interaction of the imbalanced intestinal microbiome. Moreover, the apoptosis could be triggered by the calcium signaling.

Potentiometric sensing of ibuprofen over ferric oxide doped chitosan grafted polypyrrole-based electrode.

The present work demonstrates the correlation between structure, properties, and self-sensing protocols of in situ prepared ferric oxide doped grafted copolymer composite, comprised of ferric oxide, chitosan, and polypyrrole (α-Fe2O3-en-CHIT-g-PPy) for residual ibuprofen present in natural and artificial samples. The chemical structure, morphology, functionality, and physio-mechanical properties of the composite were determined by Fourier transform infrared spectrometer (FT-IR), Raman spectra, X-ray diffraction (XRD), Scanning electron microscope (SEM), X-ray photoelectron spectroscopy (XPS), Two probe method, and standard ASTM techniques to explore sensing nature. The results confirm the evolution of axially aligned structure against 110 planes of α-Fe2O3 and chemically functionalized expanded polymer matrix during in-situ chemical polymerization of pyrrole, with better porosity, interactivity, and improved electrical conductivity i.e. 7.32 × 10-3 S cm-1. Further, a thin film of prepared composite coated on an ITO glass plate was explored for potentiometric sensing of ibuprofen (IBU) present in artificial and natural samples without the use of any additional energy sources. The observed sensing parameters are the sensing ranging 0.5 µM to 100.0 µM, sensitivity 2.5081 mV µM-1 cm-2, response time 50 s, recovery time 10 s, and stability for 60 days. The sensing mechanism of the IBU sensor and effective charge transfer in the electrode was also discussed based on changes in IR spectra of the electrode recorded before and after sensing due to surface oxidation of IBU due to the presence of iron and doping effect of iron oxide in the composite.

The influence of charge on the translation of the sandwich ELISA approach to electronic biosensors.

The sandwich approach, whereby an antigen is captured by a primary antibody and detected by a secondary antibody, is commonly used to improve the selectivity and sensitivity of enzyme-linked immunosorbent assays (ELISA). This work details the experimental factors that impact the reliable translation of this sandwich approach to two commonly used electronic biosensors, namely potentiometric and impedimetric biosensors. Previous studies have demonstrated the Debye screening limitations associated with potentiometric biosensors. However, the correlation between the ionic strength of the measurement buffer and the impedimetric biosensing response has not been studied. Potentiometric biosensors were able to successfully detect the primary antibody and the target antigen by decreasing the ionic strength of the phosphate buffered saline (PBS) measurement buffer from 1x PBS to 0.01x PBS. However, the secondary antibody used for the selective signal amplification was not reliably detected. Therefore, the sandwich approach is not viable for potentiometric sensing at biologically relevant ionic strengths, due to the Debye screening effect. Alternatively, decreasing the ionic strength of the measurement buffer allowed for the successful translation of the sandwich approach to impedimetric biosensors. Impedimetric biosensing literature typically attributes a measured increase in the charge transfer resistance to an increase in the thickness of the immobilized biolayer. However, this work highlights the influence that both the charge and thickness of the biolayer have on the transport of the redox couple. Decreasing the ionic strength of the measurement buffer lowers the molecular charge screening effect. This permits the transport of a positively charged redox probe through a negatively charged immobilized biolayer via migration and diffusion. The results demonstrate that the use of a buffer at a lower, yet biologically relevant ionic strength allows for the successful translation of the sandwich approach to impedimetric biosensors.

Aptamer-Based Potentiometric Sensor Enables Highly Selective and Neurocompatible Neurochemical Sensing in Rat Brain.

Selective and nondisruptive in vivo neurochemical monitoring within the central nervous system has long been a challenging endeavor. We introduce a new sensing approach that integrates neurocompatible galvanic redox potentiometry (GRP) with customizable phosphorothioate aptamers to specifically probe dopamine (DA) dynamics in live rat brains. The aptamer-functionalized GRP (aptGRP) sensor demonstrates nanomolar sensitivity and over a 10-fold selectivity for DA, even amidst physiological levels of major interfering species. Notably, conventional sensors without the aptamer modification exhibit negligible reactivity to DA concentrations exceeding 20 µM. Critically, the aptGRP sensor operates without altering neuronal activity, thereby permitting real-time, concurrent recordings of both DA flux and electrical signaling in vivo. This breakthrough establishes aptGRP as a viable and promising framework for the development of high-fidelity sensors, offering novel insights into neurotransmission dynamics in a live setting.

Chronopotentiometric Nanopore Sensor Based on a Stimulus-Responsive Molecularly Imprinted Polymer for Label-Free Dual-Biomarker Detection.

The development of sensors for detection of biomarkers exhibits an exciting potential in diagnosis of diseases. Herein, we propose a novel electrochemical sensing strategy for label-free dual-biomarker detection, which is based on the combination of stimulus-responsive molecularly imprinted polymer (MIP)-modified nanopores and a polymeric membrane chronopotentiometric sensor. The ion fluxes galvanostatically imposed on the sensing membrane surface can be blocked by the recognition reaction between the target biomarker in the sample solution and the stimulus-responsive MIP receptor in the nanopores, thus causing a potential change. By using two external stimuli (i.e., pH and temperature), the recognition abilities of the stimulus-responsive MIP receptor can be effectively modulated so that dual-biomarker label-free chronopotentiometric detection can be achieved. Using alpha fetoprotein (AFP) and prostate-specific antigen (PSA) as model biomarkers, the proposed sensor offers detection limits of 0.17 and 0.42 ng/mL for AFP and PSA, respectively.

The Catalysis Mechanism of E. coli Nitroreductase A, a Candidate for Gene-Directed Prodrug Therapy: Potentiometric and Substrate Specificity Studies.

E. coli nitroreductase A (NfsA) is a candidate for gene-directed prodrug cancer therapy using bioreductively activated nitroaromatic compounds (ArNO2). In this work, we determined the standard redox potential of FMN of NfsA to be -215 ± 5 mV at pH 7.0. FMN semiquinone was not formed during 5-deazaflavin-sensitized NfsA photoreduction. This determines the two-electron character of the reduction of ArNO2 and quinones (Q). In parallel, we characterized the oxidant specificity of NfsA with an emphasis on its structure. Except for negative outliers nitracrine and SN-36506, the reactivity of ArNO2 increases with their electron affinity (single-electron reduction potential, E17) and is unaffected by their lipophilicity and Van der Waals volume up to 386 Å. The reactivity of quinoidal oxidants is not clearly dependent on E17, but 2-hydroxy-1,4-naphthoquinones were identified as positive outliers and a number of compounds with diverse structures as negative outliers. 2-Hydroxy-1,4-naphthoquinones are characterized by the most positive reaction activation entropy and the negative outlier tetramethyl-1,4-benzoquinone by the most negative. Computer modelling data showed that the formation of H bonds with Arg15, Arg133, and Ser40, plays a major role in the binding of oxidants to reduced NfsA, while the role of the π-π interaction of their aromatic structures is less significant. Typically, the calculated hydride-transfer distances during ArNO2 reduction are smallwer than for Q. This explains the lower reactivity of quinones. Another factor that slows down the reduction is the presence of positively charged aliphatic substituents.

Polymeric membrane potentiometric antibiotic sensors using computer-aided screening of supramolecular macrocyclic carriers.

Carrier-based polymeric membrane potentiometric sensors are an ideal tool for detecting ionic species. However, in the fabrication of these sensors, the screening of carriers still relies on empirical trial- and error-based optimization, which requires tedious and time-consuming experimental verification. In this work, computer-aided screening of carriers is applied in the preparation of polymeric membrane potentiometric sensors. Molecular docking is used to study the host-guest interactions between receptors and targets. Binding energies are employed as the standard to screen the appropriate carrier. As a proof-of-concept experiment, the antibiotic ciprofloxacin is selected as the target model. A series of supramolecular macrocyclic receptors including cyclodextrins, cucurbiturils and calixarenes are chosen as potential receptors. The proposed sensor based on the receptor calix[4]arene screened by molecular docking shows a lower detection limit of 0.5 µmol L-1 for ciprofloxacin. It can be expected that the proposed computer-aided screening technique of carriers can provide a simple but highly efficient method for the fabrication of carrier-based electrochemical and optical sensors.

Non-enzymatic paper-based analytical device for direct potentiometric detection of urine creatinine.

A paper-based analytical device (PAD) with an integrated composite electrode has been designed and fabricated for non-enzymatic creatinine sensing. Reduced graphene oxide (rGO) was employed to modify the PAD so that it could function as a solid-contact transducer. A new macrocyclic pyrido-hexapeptide derivative was made and used as a special ionophore in the creatinine membrane sensor. The synthesized PAD showed a detection limit of 1.0 µM (S/N = 3) and a potentiometric response towards creatinine throughout a log-linear range of 2.0 µM-10 mM (R2 = 0.9998). The sensor shows significant selectivity for a few related substances, including ephedrine, codeine, ketamine, caffeine, urea, urate, carbinoxamine, and dextromethorphan. It has been established that the testing method is appropriate for the direct potentiometric detection of creatinine in a variety of human urine sample types. When an indicating electrode and a reference electrode are put on the same flexible disposable, this lets applications with a small sample volume be done. For point-of-care creatinine measurement, the developed paper-based analytical equipment is a good choice because it is affordable, easily accessible, and self-pumping (especially when combined with potentiometric detection).

Label-free and highly-sensitive detection of calcium ions using a silicon-on-sapphire light-addressable potentiometric sensor.

BACKGROUND: Ionic calcium (Ca2+) plays a crucial role in maintaining normal physiological and biochemical functions within the human body. Detecting the concentration of Ca2+ is of utmost significance for various purposes, including disease screening, cellular metabolism research, and evaluating drug effectiveness. However, current detection approaches such as fluorescence and colorimetry face limitations due to complex labeling techniques and the inability to track changes in Ca2+ concentration. In recent years, extensive research has been conducted in this field to explore label-free and efficient approaches. RESULTS: In this study, a novel light-addressed potentiometric sensor (LAPS) using silicon-on-sapphire technology, has been successfully developed for Ca2+ sensing. The Ca2+-sensitive LAPS achieved a wide-range detection of Ca2+, ranging from 10-2 M to 10-7 M, with an impressive detection limit of 100 nM. These advancements are attributed to the ultra-thin silicon layer, silicon dioxide layer, and solid-state silicon rubber sensitive membrane around 6 µm. Furthermore, the sensor demonstrated the ability to dynamically monitor fluctuations in Ca2+ concentration ranging from 10-9 M to 10-2 M within a solution. Its remarkable selectivity, specificity, and long-term stability have facilitated its successful application in the detection of Ca2+ in human serum and urine. SIGNIFICANCE AND NOVELTY: This work presents a Ca2+-sensitive sensor that combines a low detection limit and a wide detection range. The development represents the emergence of a label-free and rapid Ca2+ detection tool with immense prospects in home-based health monitoring, community disease screening, as well as cellular metabolism, and drug screening evaluations.

Enzymatic Galvanic Redox Potentiometry for In Vivo Biosensing.

Redox potentiometry has emerged as a new platform for in vivo sensing, with improved neuronal compatibility and strong tolerance against sensitivity variation caused by protein fouling. Although enzymes show great possibilities in the fabrication of selective redox potentiometry, the fabrication of an enzyme electrode to output open-circuit voltage (EOC) with fast response remains challenging. Herein, we report a concept of novel enzymatic galvanic redox potentiometry (GRP) with improved time response coupling the merits of the high selectivity of enzyme electrodes with the excellent biocompatibility and reliability of GRP sensors. With a glucose biosensor as an illustration, we use flavin adenine dinucleotide-dependent glucose dehydrogenase as the recognition element and carbon black as the potential relay station to improve the response time. We find that the enzymatic GRP biosensor rapidly responds to glucose with a good linear relationship between EOC and the logarithm of glucose concentration within a range from 100 µM to 2.65 mM. The GRP biosensor shows high selectivity over O2 and coexisting neurochemicals, good reversibility, and sensitivity and can in vivo monitor glucose dynamics in rat brain. We believe that this study will pave a new platform for the in vivo potentiometric biosensing of chemical events with high reliability.

A Potentiometric Dual-Channel Microsensor Reveals that Fluctuation of H2 S is Less pH-Dependent During Spreading Depolarization in the Rat Brain.

Spreading depolarization (SD) is one of the most common neuropathologic phenomena in the nervous system, relating to numerous diseases. However, real-time monitoring the rapid chemical changes during SD to probe the molecular mechanism remains a great challenge. We develop a potentiometric dual-channel microsensor for simultaneous monitoring of H2 S and pH featuring excellent selectivity and spatiotemporal resolution. Using this microsensor we first observe real time changes of H2 S and pH in the rat brain induced by SD. This changes of H2 S are completely suppressed when the rat pre-treats with aminooxyacetic acid (AOAA), a blocker to inhibit the H2 S-producing enzyme, indicating H2 S fluctuation might be related to enzyme-dependent pathway during SD and less pH-dependent. This study provides a new perspective for studying the function of H2 S and the molecular basis of SD-associated diseases.

Potentiometric detection of apomorphine in human plasma using a 3D printed sensor.

Apomorphine is a dopamine agonist that is used for the management of Parkinson's disease and has been proven to effectively decrease the off-time duration, where the symptoms recur, in Parkinson's disease patients. This paper describes the design and fabrication of the first potentiometric sensor for the determination of apomorphine in bulk and human plasma samples. The fabrication protocol involves stereolithographic 3D printing, which is a unique tool for the rapid fabrication of low-cost sensors. The solid-contact apomorphine ion-selective electrode combines a carbon-mesh/thermoplastic composite as the ion-to-electron transducer and a 3D printed ion-selective membrane, doped with the ionophore calix[6]arene. The sensor selectively measures apomorphine in the presence of other biologically present cations - sodium, potassium, magnesium, and calcium - as well as the commonly prescribed Parkinson's pharmaceutical, levodopa (L-Dopa). The sensor demonstrated a linear, Nernstian response, with a slope of 58.8 mV/decade over the range of 5.0 mM-9.8 µM, which covers the biologically (and pharmaceutically) relevant ranges, with a limit of detection of 2.51 µM. Moreover, the apomorphine sensor exhibited good stability (minimal drift of just 188 µV/hour over 10 h) and a shelf-life of almost 4 weeks. Experiments performed in the presence of albumin, the main plasma protein to which apomorphine binds, demonstrate that the sensor responds selectively to free-apomorphine (i.e., not bound or complexed forms). The utility of the sensor was confirmed through the successful determination of apomorphine in spiked human plasma samples.