Chemically Induced pH Perturbations for Analyzing Biological Barriers Using Ion-Sensitive Field-Effect Transistors.

Potentiometric pH measurements have long been used for the bioanalysis of biofluids, tissues, and cells. A glass pH electrode and ion-sensitive field-effect transistor (ISFET) can measure the time course of pH changes in a microenvironment as a result of physiological and biological activities. However, the signal interpretation of passive pH sensing is difficult because many biological activities influence the spatiotemporal distribution of pH in the microenvironment. Moreover, time course measurement suffers from stability because of gradual drifts in signaling. To address these issues, an active method of pH sensing was developed for the analysis of the cell barrier in vitro. The microenvironmental pH is temporarily perturbed by introducing a low concentration of weak acid (NH4+) or base (CH3COO-) to cells cultured on the gate insulator of ISFET using a superfusion system. Considering the pH perturbation originates from the semi-permeability of lipid bilayer plasma membranes, induced proton dynamics are used for analyzing the biomembrane barriers against ions and hydrated species following interaction with exogenous reagents. The unique feature of the method is the sensitivity to the formation of transmembrane pores as small as a proton (H+), enabling the analysis of cell-nanomaterial interactions at the molecular level. The new modality of cell analysis using ISFET is expected to be applied to nanomedicine, drug screening, and tissue engineering.

Deferoxamine B: A Natural, Excellent and Versatile Metal Chelator.

Deferoxamine B is an outstanding molecule which has been widely studied in the past decade for its ability to bind iron and many other metal ions. The versatility of this metal chelator makes it suitable for a number of medicinal and analytical applications, from the well-known iron chelation therapy to the most recent use in sensor devices. The three bidentate hydroxamic functional groups of deferoxamine B are the centerpiece of its metal binding ability, which allows the formation of stable complexes with many transition, lanthanoid and actinoid metal ions. In addition to the ferric ion, in fact, more than 20 different metal complexes of deferoxamine b have been characterized in terms of their chemical speciation in solution. In addition, the availability of a terminal amino group, most often not involved in complexation, opens the way to deferoxamine B modification and functionalization. This review aims to collect and summarize the available data concerning the complex-formation equilibria in solutions of deferoxamine B with different metal ions. A general overview of the progress of its applications over the past decade is also discussed, including the treatment of iron overload-associated diseases, its clinical use against cancer and neurodegenerative disorders and its role as a diagnostic tool.

The Influence of Plasticizers on the Response Characteristics of the Surfactant Sensor for Cationic Surfactant Determination in Disinfectants and Antiseptics.

Surfactant liquid-membrane type sensors are usually made of a PVC, ionophore and a plasticizer. Plasticizers soften the PVC. Due to their lipophilicity, they influence the ion exchange across the membrane, ionophore solubility, membrane resistance and, consequently, the analytical signal. We used the DMI-TPB as an ionophore, six different plasticizers [2-nitrophenyl-octyl-ether (P1), bis(2-ethylhexyl) phthalate (P2), bis(2-ethylhexyl) sebacate (P3), 2-nitrophenyl phenyl ether (P4), dibutyl phthalate (P5) and dibutyl sebacate (P6)] and a PVC to produce ionic surfactant sensors. Sensor formulation with P1 showed the best potentiometric response to four usually used cationic surfactant, with the lowest LOD, 7 × 10-7 M; and potentiometric titration curves with well-defined and sharp inflexion points. The sensor with P6 showed the lowest analytical performances. Surfactant sensor with P1 was selected for quantification of cationic surfactant in model solutions and commercial samples of disinfectants and antiseptics. It showed high accuracy and precision in all determinations, with recovery from 98.2 to 99.6, and good agreement with the results obtained with surfactant sensor used as a referent one, and a standard two-phase titration method. RDS values were lower than 0.5% for all determinations.

Direct Potentiometric Study of Cationic and Nonionic Surfactants in Disinfectants and Personal Care Products by New Surfactant Sensor Based on 1,3-Dihexadecyl-1H-benzo[d]imidazol-3-ium.

A novel, simple, low-cost, and user-friendly potentiometric surfactant sensor based on the new 1,3-dihexadecyl-1H-benzo[d]imidazol-3-ium-tetraphenylborate (DHBI-TPB) ion-pair for the detection of cationic surfactants in personal care products and disinfectants is presented here. The new cationic surfactant DHBI-Br was successfully synthesized and characterized by nuclear magnetic resonance (NMR), Fourier transform infrared (FTIR) spectrometry, liquid chromatography-mass spectrometry (LC-MS) and elemental analysis and was further employed for DHBI-TPB ion-pair preparation. The sensor gave excellent response characteristics for CTAB, CPC and Hyamine with a Nernstian slope (57.1 to 59.1 mV/decade) whereas the lowest limit of detection (LOD) value was measured for CTAB (0.3 × 10-6 M). The sensor exhibited a fast dynamic response to dodecyl sulfate (DDS) and TPB. High sensor performances stayed intact regardless of the employment of inorganic and organic cations and in a broad pH range (2-11). Titration of cationic and etoxylated (EO)-nonionic surfactant (NSs) (in Ba2+) mixtures with TPB revealed the first inflexion point for a cationic surfactant and the second for an EO-nonionic surfactant. The increased concentration of EO-nonionic surfactants and the number of EO groups had a negative influence on titration curves and signal change. The sensor was successfully applied for the quantification of technical-grade cationic surfactants and in 12 personal care products and disinfectants. The results showed good agreement with the measurements obtained by a commercial surfactant sensor and by a two-phase titration. A good recovery for the standard addition method (98-102%) was observed.

Wearable electrochemical biosensors in North America.

Tremendous research and commercialization efforts around the world are focused on developing novel wearable electrochemical biosensors that can noninvasively and continuously screen for biochemical markers in body fluids for the prognosis, diagnosis and management of diseases, as well as the monitoring of fitness. Researchers in North America are leading the development of innovative wearable platforms that can comfortably comply to the human body and efficiently sample fluids such as sweat, interstitial fluids, tear and saliva for the electrochemical detection of biomarkers through various sensing approaches such as potentiometric ion selective electrodes and amperometric enzymatic sensors. We start this review with a historical timeline overviewing the major milestones in the development of wearable electrochemical sensors by North American institutions. We then describe how such research efforts have led to pioneering developments and are driving the advancement and commercialization of wearable electrochemical sensors: from minimally invasive continuous glucose monitors for chronic disease management to non-invasive sweat electrolyte sensors for dehydration monitoring in fitness applications. While many countries across the globe have contributed significantly to this rapidly emerging field, their contributions are beyond the scope of this review. Furthermore, we share our perspective on the promising future of wearable electrochemical sensors in applications spanning from remote and personalized healthcare to wellness.