Development of a Potential-Modulated Electrochemiluminescence Measurement System for Selective and Sensitive Determination of the Controlled Drug Codeine.

Codeine is a common analgesic drug that is a pro-drug of morphine. It also has a high risk of abuse as a recreational drug because of its extensive distribution as an OTC drug. Therefore, sensitive and selective screening methods for codeine are crucial in forensic analytical chemistry. To date, a commercial analytical kit has not been developed for dedicated codeine determination, and there is a need for an analytical method to quantify codeine in the field. In the present work, potential modulation was combined with electrochemiluminescence (ECL) for sensitive determination of codeine. The potential modulated technique involved applying a signal to electrodes by superimposing an AC potential on the DC potential. When tris(2,2'-bipyridine)ruthenium(II) ([Ru(bpy)3]2+) was used as an ECL emitter, ECL activity was confirmed for codeine. A detailed investigation of the electrochemical reaction mechanism suggested a characteristic ECL reaction mechanism involving electrochemical oxidation of the opioid framework. Besides the usual ECL reaction derived from the amine framework, selective detection of codeine was possible under the measurement conditions, with clear luminescence observed in an acidic solution. The sensitivity of codeine detection by potential modulated-ECL was one order of magnitude higher than that obtained with the conventional potential sweep method. The proposed method was applied to codeine determination in actual prescription medications and OTC drug samples. Codeine was selectively determined from other compounds in medications and showed good linearity with a low detection limit (150 ng mL-1).

Sensitive screening of methamphetamine stimulant using potential-modulated electrochemiluminescence.

Methamphetamine (MA) is one of the most commonly abused recreational stimulants; thus, rapid and sensitive screening methods for MA are of great importance in forensic analytical chemistry. In the present work, potential modulation was combined with electrochemiluminescence (ECL) for the sensitive determination of MA. The potential modulated (PM) technique involved applying a signal to electrodes by superimposing an alternating current potential on the direct current potential. When tris(2,2'-bipyridine)ruthenium(II) (Ru(bpy)32+) was used as an ECL emitter, the sensitivity of MA detection by PM-ECL was over 100 times that obtained with in conventional potential sweep mode. The radical on the α-carbon of the amine moiety is thought to play an important role in the ECL reaction mechanism involving amine-containing species. However, in the case of MA-type stimulants, density functional theory calculations suggest that the generated α-carbon radicals induce further intramolecular proton transfer. On the basis of the proposed ECL reaction route, we clarified the conditions under which MA could be selectively detected in the presence of the similar substance methoxyphenamine. The proposed method was applied to MA determination in a spiked human urine sample and showed good linearity with a low detection limit (100 nM, ca. 15 ng mL-1).

Imaging Single Bacterial Cells with Electro-optical Impedance Microscopy.

Impedance measurements have been an important tool for biosensor applications, including protein detection, DNA quantification, and cell study. We present here an electro-optical impedance microscopy (EIM) based on the dependence of surface optical transmission on local surface charge density for single bacteria impedance imaging. We applied a potential modulation to bacteria placed on an indium tin oxide-coated slide and simultaneously recorded a sequence of transmitted microscopy images. By performing fast Fourier transform analysis on the image sequences, we obtained the DC component (signal at 0 Hz) for cell morphology imaging and the AC component (signal at the modulation frequency) for the mapping of cell impedance responses with subcellular resolution for the first time. Using this method, we have monitored the viability of Escherichia coli bacterial cells under treatment with two different classes of antibiotics with low-frequency potential modulation. The results showed that the impedance response is sensitive to the antibiotic that targets the bacterial cell membrane as the membrane capacitance dominated at low-frequency modulation. Heterogeneous responses to the antibiotic treatment were observed at a single bacteria level. In addition to the high spatial resolution, EIM is label-free and simple and can be potentially used for the continuous mapping of single bacteria impedance changes under different conditions.

Potential-modulated electrochemiluminescence of a tris(2,2'-bipyridine)ruthenium(II) / lidocaine system under 430 kHz ultrasound irradiation.

The electrochemiluminescence (ECL) of tris(2,2'-bipyridine)ruthenium(II) (Ru(bpy)32+) in the presence of lidocaine was investigated under ultrasound (US) irradiation. The sonoelectrochemical experiments are conducted by indirect irradiation of ultrasound with a piezoelectric transducer operating at 430 kHz. In a supporting electrolyte at pH 11, the Ru(bpy)32+/lidocaine system gave weak ECL peaks around +1.2 V and +1.45 V, respectively. The ECL signal at +1.2 V was attributed to redox reactions of the oxidative intermediates of Ru(bpy)32+ and lidocaine, while the signal at +1.45 V was assumed to be caused by an advanced oxidation process due to the generation of hydroxyl radicals (OH) at the electrode surface. In this study, the potential modulation approach is employed in the study of ECL process upon US irradiations because it can suppress the noise components from sonoluminescence effectly and improve the resolution of ECL-potential profiles. It is found ECL signals were greatly enhanced upon US irradiation at the output power of 30 W, however, the relative intensity of ECL signal at +1.2 V was larger than that obtained with a rotating disk electrode even though the mass transport effect is equilvalent. The experiment results suggest that the chemical effect (i.e., generation of OH) by 430 kHz US becomes remarkable in the electrochemical process. Detailed ECL reaction routes under US are proposed in this study.

The secret life of ion channels: Kv1.3 potassium channels and proliferation.

Kv1.3 channels are involved in the switch to proliferation of normally quiescent cells, being implicated in the control of cell cycle in many different cell types and in many different ways. They modulate membrane potential controlling K+ fluxes, sense changes in potential, and interact with many signaling molecules through their intracellular domains. From a mechanistic point of view, we can describe the role of Kv1.3 channels in proliferation with at least three different models. In the "membrane potential model," membrane hyperpolarization resulting from Kv1.3 activation provides the driving force for Ca2+ influx required to activate Ca2+-dependent transcription. This model explains most of the data obtained from several cells from the immune system. In the "voltage sensor model," Kv1.3 channels serve mainly as sensors that transduce electrical signals into biochemical cascades, independently of their effect on membrane potential. Kv1.3-dependent proliferation of vascular smooth muscle cells (VSMCs) could fit this model. Finally, in the "channelosome balance model," the master switch determining proliferation may be related to the control of the Kv1.3 to Kv1.5 ratio, as described in glial cells and also in VSMCs. Since the three mechanisms cannot function independently, these models are obviously not exclusive. Nevertheless, they could be exploited differentially in different cells and tissues. This large functional flexibility of Kv1.3 channels surely gives a new perspective on their functions beyond their elementary role as ion channels, although a conclusive picture of the mechanisms involved in Kv1.3 signaling to proliferation is yet to be reached.

Absolute Energy Level Positions in CdSe Nanostructures from Potential-Modulated Absorption Spectroscopy (EMAS).

Semiconductor nanostructures such as CdSe quantum dots and colloidal nanoplatelets exhibit remarkable optical properties, making them interesting for applications in optoelectronics and photocatalysis. For both areas of application a detailed understanding of the electronic structure is essential to achieve highly efficient devices. The electronic structure can be probed using the fact that optical properties of semiconductor nanoparticles are found to be extremely sensitive to the presence of excess charges that can for instance be generated by means of an electrochemical charge transfer via an electrode. Here we present the use of EMAS as a versatile spectroelectrochemical method to obtain absolute band edge positions of CdSe nanostructures versus a well-defined reference electrode under ambient conditions. In this, the spectral properties of the nanoparticles are monitored with respect to an applied electrochemical potential. We developed a bleaching model that yields the lowest electronic state in the conduction band of the nanostructures. A change in the band edge positions caused by quantum confinement is shown both for CdSe quantum dots and for colloidal nanoplatelets. In the case of CdSe quantum dots these findings are in good agreement with tight binding calculations. The method presented is not limited to CdSe nanostructures but can be used as a universal tool. Hence, this technique allows the determination of absolute band edge positions of a large variety of materials used in various applications.

Spectroelectrochemical Properties of Ultra-Thin Indium Tin Oxide Films under Electric Potential Modulation.

In this work, the spectroscopic properties of ultra-thin ITO films are characterized under an applied electric potential modulation. To detect minute spectroscopic features, the ultra-thin ITO film was coated over an extremely sensitive single-mode integrated optical waveguide, which provided a long pathlength with more than adequate sensitivity for optical interrogation of the ultra-thin film. Experimental configurations with broadband light and several laser lines at different modulation schemes of an applied electric potential were utilized to elucidate the nature of intrinsic changes. The imaginary component of the refractive index (absorption coefficient) of the ultra-thin ITO film is unequivocally shown to have a dependence on the applied potential and the profile of this dependence changes substantially even for wavelengths inside a small spectral window (500-600 nm). The characterization technique and the data reported here can be crucial to several applications of the ITO material as a transparent conductive electrode, as for example in spectroelectrochemical investigations of surface-confined redox species.

Fractal-like correlations of the fluctuating inter-spike membrane potential of a Helix aspersa pacemaker neuron.

We analyzed the voltage fluctuations of the membrane potential manifested along the inter-spike segment of a pacemaker neuron. Time series of intracellular inter-spike voltage fluctuations were obtained in the current-clamp configuration from the F1 neuron of 12 Helix aspersa specimens. To assess the dynamic or stochastic nature of the voltage fluctuations these series were analyzed by Detrended Fluctuation Analysis (DFA), providing the scaling exponent α. The median α result obtained for the inter-spike segments was 0.971 ([0.963, 0.995] lower and upper quartiles). Our results indicate a critical-like dynamic behavior in the inter-spike membrane potential that, far from being random, shows long-term correlations probably linked to the dynamics of the mechanisms involved in the regulation of the membrane potential, thereby endorsing the occurrence of critical-like phenomena at a single-neuron level.