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.

Smartphone-based detection of levodopa in human sweat using 3D printed sensors.

Parkinson's disease (PD) is one of the leading neurological disorders negatively impacting health on a global scale. Patients diagnosed with PD require frequent monitoring, prescribed medications, and therapy for extended periods as symptom severity worsens. The primary pharmaceutical treatment for PD patients is levodopa (L-Dopa) which reduces many symptoms experienced by PD patients (e.g., tremors, cognitive ability, motor dysfunction, etc.) through the regulation of dopamine levels in the body. Herein, the first detection of L-Dopa in human sweat using a low-cost 3D printed sensor with a simple and rapid fabrication protocol combined with a portable potentiostat wirelessly connected to a smartphone via Bluetooth is reported. By combining saponification and electrochemical activation into a single protocol, the optimized 3D printed carbon electrodes were able to simultaneously detect uric acid and L-Dopa throughout their biologically relevant ranges. The optimized sensors provided a sensitivity of 83 ± 3 nA/µM from 24 µM to 300 nM L-Dopa. Common physiological interferents found in sweat (e.g., ascorbic acid, glucose, caffeine) showed no influence on the response for L-Dopa. Lastly, a percent recovery of L-Dopa in human sweat using a smartphone-assisted handheld potentiostat resulted in the recovery of 100 ± 8%, confirming the ability of this sensor to accurately detect L-Dopa in sweat.

Concentrating nutrients and recovering water and energy from source separated urine using osmotic microbial fuel cell.

This work presents the use of osmotic microbial fuel cell (OsMFC), for the first time, to concentrate nutrients and recover water and energy from source separated urine. Four sets of concentration of fresh urine as feed and NaCl as draw were examined: 10% fresh urine vs 0.25 M NaCl; 10% fresh urine vs 2 M NaCl; fresh urine vs 0.25 M NaCl; and fresh urine vs 2 M NaCl. A maximum water flux of 14.27 LMH was attained when 10% of fresh urine and 2 M of NaCl were used as feed and draw solutions, respectively. Additionally, OsMFC concentrates ~99% of TOC, TN, NH4+, and 100% of PO43- and NO3- from urine at the feed side. Polarization studies indicate that the power generation in OsMFC is related to the rate of change of conductivity and the initial conductivity of the anolyte. The maximum (0.12187 W m-3) and minimum power densities (5.3372 × 10-4 W m-3) were obtained for the conditions of fresh urine vs 0.25 M NaCl and 10% fresh urine vs 0.25 M NaCl, respectively. The study shows that OsMFC is an effective pretreatment process to concentrate nutrients from urine by recovering water and energy, simultaneously.

An all solid-state Li ion battery composed of low molecular weight crystalline electrolyte.

Conduction mechanisms in solid polymer electrolytes of Li ion batteries have always been a concern due to their theoretical limitation in conductivity value. In an attempt to increase the ionic conductivity of solid state electrolytes, used in lithium ion secondary batteries (LiBs), we studied the synthesis and conductive properties of a low molecular weight cyclic organoboron crystalline electrolyte. This electrolyte was expected to show better electrochemical properties than solid polymer electrolytes. The electrolyte was doped with LiTFSI salt via two different methods viz. (1) facile grinding of the crystalline sample with lithium salt under a nitrogen atmosphere and (2) a conventional method of solvent dissolution and evaporation under vacuum. The electrochemical properties were studied under specific composition of Li salt. The presence of crystallinity in the electrolyte can be considered as an important factor behind the high ionic conductivity of an all solid electrolyte of this type. Charge-discharge properties of the cell using the electrolyte were investigated in anodic half-cell configuration.

Cobalt-Based Coordination Polymer for Oxygen Reduction Reaction.

Lack of control over the structure and electrically nonconductive properties of coordination polymers (CPs) creates a major hindrance to designing an active electrocatalyst for oxygen reduction reaction (ORR). Here, we report a new semiconductive and low-optical band gap CP structure [{Co3(µ3-OH)(BTB)2(BPE)2}{Co0.5N(C5H5)}], 1, that exhibits high-performance ORR in alkaline medium. The electrical conductivity of compound 1 was measured using impedance spectroscopy and found to be 5 × 10-4 S cm-1. The Ketjenblack EC-600JD carbon used as a support for all the electrochemical methods such as cyclic voltammetry, rotating disk electrode, rotating ring-disk electrode and Koutecký-Levich analysis. The as-synthesized Co-based catalyst has the ability to reduce O2 to H2O by a nearly four-electron process. The crystal structure of 1 shows that the trimeric unit {Co3(µ3-OH)(COO)5N3} and monomeric unit {Co(COO)2(NC5H4)2}2+ are linked with BTB and BPE linkers to form a three-dimensional structure. Theoretical calculations predict that the monomeric center acts as an active catalytic site for ORR. This could be due to the efficient overlap of highest occupied molecular orbital-lowest unoccupied molecular orbital between monomer and O2 molecule. This CP, 1, shows facile 3.6-electron ORR, and it is inexpensive compared with widely used Pt catalysts. Therefore, this CP can be used as a promising cathode material for fuel cells in terms of efficiency and cost effectiveness.

Green, Seed-Mediated Synthesis of Au Nanowires and Their Efficient Electrocatalytic Activity in Oxygen Reduction Reaction.

A new, simple, green method for the synthesis of Au nanowires (average diameter 8 nm and several micrometers in length) using Au seeds prepared from bael gum (BG) is reported. The nanowires are characterized using UV-visible absorption spectroscopy, powder X-ray diffraction, transmission electron microscopy (TEM), and high-resolution-TEM. It is observed that the rate of the reduction process might be the decisive factor for the shape selectivity, as evident from the formation of nanowires at a particular concentration of seeds and NaOH. The polysaccharide present in BG is the active ingredient for the synthesis of Au nanowires, while the small molecules present in BG, when used alone, did not result in nanowire formation. The TEM images of the precursor to the Au nanowires suggested that new, nucleated particles align in a linear manner and fuse with one another, resulting in the nanowire. The linear fusion of the newly nucleated particles could be due to the lack of adequate protecting agent and the presence of Au complex adsorbed to the surface. The electrochemical activity of the nanowires for oxygen reduction reaction (ORR) is assessed and compared with that of nanotriangles and spherical nanoparticles of Au. The performance of Au nanowire is better than Au-nanomaterials (heat-treated as well as non-heat-treated), Au seeds, and clusters. The better efficiency of the nanowires when compared to that of the other reported catalysts is attributed to the presence of active (100) facets with numerous corners, edges, and surface defects.