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Mesoscale ionic diodes, which can rectify ionic current at conditions at which their pore size is larger than 100 nm and thus over 100 times larger than the Debye length, have been recently discovered with potential applications in ionic circuits as well as osmotic power generation. Compared with the conventional nanoscale ionic diodes, the mesoscale ionic diodes can offer much higher conductance, ionic current resolution, and power generated. However, the thermal response, which has been proven playing a crucial role in nanofluidic devices, of the mesoscale ionic diode remains significantly unexplored. Here, we report the thermal dependence of the mesoscale ionic diode comprising a conical pore with a tip opening diameter of ∼400 nm. To capture its underlying physics more accurately, our model takes into account the practical equilibrium chemistry reaction of functional carboxyl groups on the pore surface. Modeling results predict that in the mesoscale ionic diode prepared currents increase but the performance decreases with the increase of temperature, which is consistent with our experimental data and indicates that the ion transport properties apparently depend on the presence of highly mobile hydroxide ions. The results gathered can provide important guidance for the design of new mesoscale ionic diodes, enriching their applications in thermoelectric power and thermoresponsive chemical sensors.

A 3D network composed of V2O5 nanofibers was manufactured on a novel conductive printing paper [urea-LiClO4-PVA (ULP) deep eutectic solvent gel-doped graphite/printing paper, U-paper] for use as electrodes linked with a ULP neutral gel electrolyte for 3D network V2O5 wearable symmetric pseudocapacitors (WSSCs). The function of the ULP gel is not only that it can be doped into the conductive ink to decrease the resistance of the conductive printing paper but also that it increases the stability of V2O5-based electrodes. Moreover, 3D network V2O5 WSSCs containing the ULP gel can support high operating voltages of 4.0 V with great specific capacitance (160 F/g) and offer a high energy density (355 W h/kg at 0.2 kW/kg). The 3D network V2O5 WSSCs exhibit a superior cycling stability/durability after 5000 cycles (capacitance retention of ∼91%). Operando X-ray absorption spectroscopy experiments show the reversibility and pseudocapacitive properties of V2O5 from the ULP gel and offer the information of the oxidation states of vanadium during charge-discharge cycles. The 3D network V2O5 WSSCs with the ULP gel electrolyte show great potential prospective candidates for smarter 3D wearable energy-storage devices and Internet-of-Things applications.

A novel procedure for the Pd-catalyzed dual annulation reaction to synthesize the norneocryptolepine derivatives involving the concerted construction of two central heterocycles is reported. The further methylation of the norneocryptolepine to afford its alkaloid analog neocryptolepine implies that synthesis of various neocryptolepine derivatives is feasible. The oxidative addition of Pd(0) is indicated as the key step to activate the intramolecular addition of nitrile according to the mechanism study.

Single pores in the resistive-pulse technique are used as an analytics tool to detect, size, and characterize physical as well as chemical properties of individual objects such as molecules and particles. Each object passing through a pore causes a transient change of the transmembrane current called a resistive pulse. In high salt concentrations when the pore diameter is significantly larger than the screening Debye length, it is assumed that the particle size and surface charge can be determined independently from the same experiment. In this article we challenge this assumption and show that highly charged hard spheres can cause a significant increase of the resistive-pulse amplitude compared to neutral particles of a similar diameter. As a result, resistive pulses overestimate the size of charged particles by even 20%. The observation is explained by the effect of concentration polarization created across particles in a pore, revealed by numerical modeling of ionic concentrations, ion current, and local electric fields. It is notable that in resistive-pulse experiments with cylindrical pores, concentration polarization was previously shown to influence ionic concentrations only at pore entrances; consequently, additional and transient modulation of resistive pulses was observed when a particle entered or left the pore. Here we postulate that concentration polarization can occur across transported particles at any particle position along the pore axis and affect the magnitude of the entire resistive pulse. Consequently, the recorded resistive pulses of highly charged particles reflect not only the particles' volume but also the size of the depletion zone created in front of the moving particle. Moreover, the modeling identified that the effective surface charge density of particles depended not only on the density of functional groups on the particle but also on the capacitance of the Stern layer. The findings are of crucial importance for sizing particles and characterizing their surface charge properties.

Proton enhancement in an extended nanochannel is investigated by a continuum model consisting of three-dimensional Poisson-Nernst-Planck equations for the ionic mass transport of multiple ionic species with the consideration of surface chemistry on the nanochannel wall. The model is validated by the existing experimental data of the proton distribution inside an extended silica nanochannel. The proton enhancement behavior depends substantially on the background salt concentration, pH, and dimensions of the nanochannel. The proton enrichment at the center of the nanochannel is significant when the bulk pH is medium high (ca. 8) and the salt concentration is relatively low. The results gathered are informative for the development of biomimetic nanofluidic apparatuses and the interpretation of relevant experimental data.

Learning from nature, many experimental results have revealed that biomimetic nanofluidics functionalized by pH-regulated polyelectrolyte (PE) brushes have significant potential for next-generation biosensing devices. The present study theoretically investigates for the first time the field effect on the Donnan potential and electrokinetic flow (EKF) in a biomimetic PE-modified nanochannel. The results obtained show that, in addition to the thickness and softness of the PE brush layer, the EKF velocity is tunable by modulating the Donnan potential of PE-modified nanochannels with a nanofluidic field effect transistor under various solution properties including pH and background salt concentration. The electrostatic gating effect on the Donnan potential depends significantly on the solution properties, but insignificantly on the thickness of the PE brush layer.

Many experimental results demonstrated that ion transport phenomena in nanofluidic devices are strongly dependent on the surface charge property of the nanochannel. In this study, active control of the surface charge property and the streaming current, generated by a pressure-driven flow, in a pH-regulated nanochannel using a field effect transistor (FET) are analyzed for the first time. Analytical expressions for the surface charge property and the streaming current/conductance have been derived taking into account multiple ionic species, surface chemistry reactions, and the Stern layer effect. The model is validated by the experimental data of the streaming conductance in the silica nanochannel available in the literature. Results show that the pH-dependent streaming conductance of the gated silica nanochannel is consistent with its modulated zeta potential; however, the salt concentration-dependent streaming conductance might be different from the zeta potential behavior, depending on the solution pH a...

Inspired by ion channels in biological cells where the intracellular and extracellular ionic concentrations are typically different, a salt concentration gradient through a charged nanopore is proposed to actively regulate its ion transport and selectivity. Results obtained show that, in addition to the ion current rectification phenomenon, a reversed ion selectivity of the nanopore occurs when the concentration gradient is sufficiently large. In addition, if the directions of the applied concentration gradient and electric field are identical, a reversed magnified electric field occurs near the cathode side of the nanopore. This induced field can be used to enhance the capture rate of biomolecules and is therefore capable of improving the performance of single biomolecule sensing using nanopores.

Fundamental understanding of ion transport phenomena in nanopores is crucial for designing the next-generation nanofluidic devices. Due to surface reactions of dissociable functional groups on the nanopore wall, the surface charge density highly depends upon the proton concentration on the nanopore wall, which in turn affects the electrokinetic transport of ions, fluid, and particles within the nanopore. Electrokinetic ion transport in a pH-regulated nanopore, taking into account both multiple ionic species and charge regulation on the nanopore wall, is theoretically investigated for the first time. The model is verified by the experimental data of nanopore conductance available in the literature. The results demonstrate that the spatial distribution of the surface charge density at the nanopore wall and the resulting ion transport phenomena, such as ion concentration polarization (ICP), ion selectivity, and conductance, are significantly affected by the background solution properties, such as the pH and salt concentration.

Active control of surface charge property and electroosmotic flow (EOF) in a silica-based nanochannel using a field effect transistor (FET) is analyzed for the first time taking the Stern layer effect into account. Approximations for surface charge property and EOF have been derived and validated by comparing their predictions with experimental data available in the literature. We show that, in addition to the background solution properties such as its pH and salt concentration, the field effect control of the zeta potential of the nanochannel wall and the EOF velocity depends highly on the surface capacitance of the Stern layer, stemming from the attraction of immobile counterions within that layer. The Stern layer effect becomes significant when the background salt concentration, solution pH, and/or the applied gate potential are relatively high. Results gathered provide valuable information for designing relevant gated nanofluidic devices for regulating ion, fluid flow, and biomolecule transport.

We modeled the electrophoresis of a soft cylindrical particle comprising a rigid core and a polyelectrolyte layer along the axis of a long, cylindrical pore, and the applicability of the model proposed is verified by the experimental data available in the literature. Previous analysis is extended to the case where the effects of double-layer polarization (DLP) and electroosmotic flow (EOF) can be significant. We show that the interaction between the particle's double layer and the pore, the competition between the effective charge density and the local electric field strength, and the presence of EOF yield interesting and significant results. For example, if EOF is absent, the particle mobility as the bulk salt concentration varies depends highly on the amount of fixed charge of its polyelectrolyte layer: if that amount is small, the mobility decreases monotonically with increasing bulk salt concentration, and if that amount is large, then the mobility shows a local maximum. At a high bulk salt concentration, the longer the particle the larger is its mobility, that trend is reversed if it is low. That local minimum vanishes when the boundary effect is important. If the pore is positively charged, a positively charged particle can be driven to the direction opposite to that of the applied electric field. These provide necessary information for the design of electrophoresis devices.

The influence of electroosmotic flow (EOF) on the electrophoretic behavior of a particle is investigated by considering a rigid sphere in a charge-regulated, zwitterionic cylindrical pore filled with an aqueous solution containing multiple ionic species. This extends conventional analyses to a more general and realistic case. Taking a pore with pK(a) = 7 and pK(b) = 2 (point of zero charge is pH = 2.5) filled with an aqueous NaCl solution as an example, several interesting results are observed. For instance, if pH5.5, the particle mobility is influenced mainly by boundary effect, and is influenced by both EOF and boundary effects if pH ≥ 5.5. If pH is sufficiently high, the particle behavior is dominated by EOF, which might alter the direction of electrophoresis. The ratio of (pore radius/particle radius) influences not only the boundary effect, but also the strength of EOF. If the boundary effect is insignificant, the mobility varies roughly linearly with log(bulk salt concentration). These findings are of practical significance to both the interpretation of experimental data and the design of electrophoresis devices.

Nanopores functionalized with synthetic or biological polyelectrolyte (PE) brushes have significant potentials to rectify ionic current and probe single biomacromolecules. In this work, electric-field-induced ion transport and the resulting conductance in a PE-modified nanopore are theoretically studied using a continuum-based model, composed of coupled Poisson–Nernst–Planck (PNP) equations for the ionic mass transport, and Stokes and Brinkman equations for the hydrodynamic fields in the exterior and interior of the PE layer, respectively. Because of the competition between the transport of counterions and co-ions in the nanopore, two distinct types of ion concentration polarization (CP) occur at either opening of the PE-modified nanopore. These distinct CP behaviors, which significantly affect the nanopore conductance, can be easily manipulated by adjusting the bulk salt concentration and the imposed potential bias. The induced CP in the PE-modified nanopore is more appreciable than that in the correspon...

The effect of the local liquid permittivity surrounding the DNA nanoparticle, referred to as the local permittivity environment (LPE) effect, on its electrokinetic translocation through a nanopore is investigated for the first time using a continuum-based model, composed of the coupled Poisson–Nernst–Planck (PNP) equations for the ionic mass transport and the Stokes and Brinkman equations for the hydrodynamic fields in the region outside of the DNA and within the ion-penetrable layer of the DNA nanoparticle, respectively. The nanoparticle translocation velocity and the resulting current deviation are systematically investigated for both uniform and spatially varying permittivities surrounding the DNA nanoparticle under various conditions. The LPE effect in general reduces the particle translocation velocity. The LPE effect on the current deviation is insignificant when the imposed electric field is relatively high. However, when the electric field and the bulk electrolyte concentration are relatively low,...

The surface charge property of nanofluidic devices plays an essential role in electrokinetic transport of ions, fluids, and particles in them. The nanofluidic field effect transistor (FET), referring to a nanochannel embedded with an electrically controllable gate electrode, provides a simple way to rapidly regulate its surface charge property, which in turn controls the electrokinetic transport phenomena within the nanochannel. In this study, approximate analytical expressions are derived for the first time to estimate the surface-charge property and electroosmotic flow (EOF) in charge-regulated nanochannels tuned by the nanofluidic FET and are validated by comparing their predictions to the existing experimental data available from the literature. The control of the surface charge property as well as the EOF by the nanofluidic FET depends on the pH and ionic concentration of the aqueous solution.

The electrophoresis of a polyelectrolyte, an entirely porous, charged nanoparticle, in various types of aqueous electrolyte solution is modeled taking account of the presence of multiple ionic species, and its applicability is verified by the experimental data of succinoglycan in the literature. We show that, in addition to the electroosmotic flow around a polyelectrolyte, two types of competing polarization effect are also significant: counterion polarization and co-ion polarization, both of them depend largely on the thickness of the double layer. The presence of these two polarization effects yields profound and interesting electrophoretic behaviors that are distinct to polyelectrolytes. The results gathered provide necessary theoretical background for the interpretation of various types of electrophoresis data in practice. Typical examples include that of a nanopore-based sensing device used, for instance, in DNA sequencing.

The Joule heating effect is inevitable in electrophoresis operations. To assess its influence on the performance of electrophoresis, we consider the case of a charge-regulated particle in a solution containing multiple ionic species at temperatures ranging from 298 to 308 K. Using an aqueous SiO(2) dispersion as an example, we show that an increase in the temperature leads to a decrease in both the dielectric constant and the viscosity of the liquid phase, and an increase in both the diffusivity of ions and the particle surface potential. For a particle having a constant surface potential, its electrophoretic mobility is most influenced by the variation in the liquid viscosity as the temperature varies, but for a charged-regulated particle both the liquid viscosity and the surface potential can play an important role. Depending upon the level of pH, the degree of increase in the mobility can be on the order of 40% for a 5 K increase in the temperature. The presence of double-layer polarization, which is significant when the surface potential is sufficiently high, has the effect of inhibiting that increase in the mobility. This implies that the influence of the temperature on the mobility of the particle is most significant when the pH is close to the point of zero charge.

The electrophoresis of a charge-regulated particle is modeled under the conditions where the dispersion medium contains multiple ionic species and the influence of a boundary can be significant. The conditions assumed in this study are much closer to reality than those of the available analyses in the literature, and, therefore, the results gathered provide valuable information to both theoreticians and experimentalists. For illustration, we consider the electrophoresis of a sphere in a cylindrical pore filled with four kinds of ionic species, namely, H(+), OH(-), Na(+), and Cl(-); these ions are usually present in experiments where the bulk pH is adjusted by HCl and NaOH. We show that the presence of the pore has the effect of inhibiting the polarization of the double layer near a particle, thereby influencing both quantitatively and qualitatively the electrophoretic behavior of the particle. If the pore is charged, then the effect of electroosmotic flow needs be considered, yielding interesting phenomena that might play a key role in practice.

The diffusiophoresis of a soft spherical particle normal to two parallel disks subject to an applied ionic concentration gradient is modeled theoretically. The soft particle, which comprises a rigid core and a porous membrane layer, is capable of simulating a wide class of particles such as biocolloids and particles covered by an artificial membrane layer; a rigid particle can also be recovered as the limiting case where the membrane layer is infinitely thin. The problem considered simulates, for example, the chemotaxis of cells or microorganisms. We show that the presence of the membrane layer is capable of yielding complicated diffusiophoretic behavior when the sign of the charge carried by that layer is different from that on the surface of the rigid core of the particle. Both the sign and the magnitude of the diffusiophoretic velocity of a particle can be adjusted through varying the friction coefficient of its membrane layer. These results are of practical significance, for example, in the case where diffusiophoresis is adopted as a separation operation or as a tool to carry and/or control the rate of drug release.

Although theoretical analyses on electrophoresis are ample in the literature, most of them focused on the one- or two-dimensional problems for a simpler treatment; available results for the three-dimensional case, which may be closer to reality, are extremely limited. The electrophoresis of a soft, finite cylindrical particle positioned eccentrically along the axis of a narrow cylindrical pore is modeled in this study. The type of particle considered is capable of mimicking a wide class of nonrigid entities such as biocolloids and particles covered by an artificial polymer layer in practice. The electrophoretic behaviors of the particle under various conditions are simulated. We show that if the membrane layer of a particle is charged, then its electrophoretic behavior depends largely on its aspect ratio, eccentricity, and relative size, the thickness of double layer, and the thickness of the membrane layer, which might not be the case if that layer is uncharged. In addition, the electrophoretic mobility ...

The boundary effect on the electrophoresis of a soft spherical particle, which comprises a rigid core and a porous layer, along the axis of a cylindrical pore is analyzed under the conditions of low surface potential and weak applied electric field. The porous layer of the particle is of charge-regulated nature where the distribution of fixed charge depends on the degree of dissociation/association reaction of the ionizable function groups contained in the porous layer. The pore might be charged, implying that the effect of electroosmotic flow can play a role. The influences of the nature of the porous layer of a particle, the thickness of the double layer, the pH of the bulk liquid, and the relative size of a pore on the electrophoretic behavior of the particle are investigated. Several unexpected and interesting results are obtained. For instance, if the pH value of the bulk liquid or the thickness of the membrane layer takes a medium large value, the electrophoretic mobility of the particle has a local maximum as the thickness of the double layer varies.

The influence of a charged boundary on the electrophoretic behavior of an entity in a non-Newtonian fluid is studied by considering a sphere at an arbitrary position in a spherical cavity filled with a Carreau fluid under the conditions of low surface potential and weak applied electric field. The dependence of the mobility of a sphere on its position in a cavity, the size of a cavity, the thickness of a double layer, and the nature of a fluid is investigated. In addition to the fact that the effect of shear-thinning is advantageous to the movement of a sphere, several other interesting results are also observed. For instance, if an uncharged sphere is in a positively charged cavity, where the electroosmotic flow and the induced charge on the sphere surface play a role, the effect of shear-thinning is important only if the thickness of the double layer is either sufficiently thin or sufficiently thick. However, this might not be the case if a positively charged sphere is in an uncharged cavity.

Spinosad is an insect control agent that is derived from a naturally occurring soil bacterium and is effective on several classes of insects, especially Lepidoptera larvae. Spinosad is registered in many countries for use on a variety of crops, including cotton, corn, soybeans, fruits, and vegetables. Residue methods utilizing high-performance liquid chromatography (HPLC) with ultraviolet (UV) detection have been described for determining spinosad and its metabolites in environmental and food matrices. These residue methods typically involve an extraction with organic solvents, followed by purification using liquid-liquid partitioning and/or solid phase extraction prior to measurement by HPLC-UV. The residue methods determine the active ingredients (spinosyns A and D) and up to three minor metabolites (spinosyn B, spinosyn K, and N-demethylspinosyn D). The methods have validated limits of quantitation ranging from 0.010 to 0.040 microgram/g. This paper briefly reviews the residue methodology for spinosad and metabolites in food and environmental matrices and provides a summary of method validation results for 61 different sample types, including newly published results for 37 additional crop matrices and processed commodities.

A selective and sensitive method utilizing liquid chromatography-mass spectrometry (LC-MS) has been developed for determining residues of the natural insect control agent spinosad in several crop matrices that are difficult to analyze by HPLC with UV detection. The method determines the active ingredients (spinosyns A and D) and three minor metabolites (spinosyns B and K and N-demethylspinosyn D) in alfalfa hay, wheat hay, wheat straw, sorghum fodder, and corn stover. The analytes are extracted from the samples with an acetonitrile/water solution, and the extracts are purified by solid phase extraction with a C(18) disk and a silica cartridge. All five analytes are determined simultaneously in a single injection using positive atmospheric pressure chemical ionization LC-MS with selected ion monitoring. The average recoveries ranged from 69 to 96% with standard deviations ranging from 4 to 15%. The method has a validated limit of quantitation of 0. 01 microgram/g and a limit of detection of 0.003 microgram/g. The LC-MS method can also provide residue confirmation in addition to quantitation.

6H-Isoindolo[2,1-a]indoles (5, 7, 10, 13), 5,6-dihydroindolo[2,1-a]isoquinolines (20, 21), and 6,7-dihydro-5H-benzo[c]azepino[2,1-a]indoles (23, 25, 27, 30) have been prepared as melatonin analogues to investigate the nature of the binding site of the melatonin receptor. The affinity of analogues was determined in a radioligand binding assay using cloned human mt1 and MT2 receptor subtypes expressed in NIH 3T3 cells. Agonist and antagonist potency was measured using the pigment aggregation response of a clonal line of Xenopus laevis melanophores. The 2-methoxyisoindolo[2,1-a]indoles (7a−d) showed much higher binding affinities than the parent isoindoles (5a−e), and whereas 7a−c were agonists in the functional assay, 7d and 5a−e were antagonists. The 2-ethoxyisoindolo[2,1-a]indoles (10a−d) showed reduced binding affinities compared to their methoxy analogues, while the 5-chloro derivative 13 showed a considerable reduction in binding affinity and potency compared to 7a. The 10-methoxy-5,6-dihydroindolo[2,1...

Residue methods were developed for the quantitation of spinosad and metabolites in leafy vegetables, peppers, and tomatoes. The compounds were extracted with a solution of acetonitrile/water. The extract was purified and concentrated by C18 Empore disk extraction, followed by silica and cyclohexyl solid-phase extraction. All five analytes in the purified extract were determined simultaneously by reversed-phase high-performance liquid chromatography with ultraviolet detection. For all analytes in six different commodities, the average recoveries ranged from 77 to 97% with standard deviations ranging from 2 to 7%. The limits of quantitation and detection were 0.01 and 0.003 μg/g, respectively. These results compare favorably with those obtained by replacing the Empore disk extraction with liquid−liquid partitioning in the method. Analysis of cabbages sprayed with [14C]spinosyn A from a residue study indicated that the Empore disk extraction provided a cleaner final extract. Confirmation of analytes was perf...

A series of 4-substituted 2-guanidinothiazoles has been found to inhibit the gastric proton-pump enzyme H+,K(+)-ATPase. In general, these compounds were reversible inhibitors of canine gastric H+,K(+)-ATPase, competitive at the K+ site, and selective relative to canine renal Na+,K(+)-ATPase. Structure-activity relationship (SAR) studies on this series revealed no general replacement for the guanidinothiazole. On the other hand, use of pyrrolyl, phenyl, and indolyl groups as the C-4 substituent yielded active compounds. Extensive studies of substitution patterns on these 4-aryl groups led to more active compounds, but no consistent SAR became apparent. Monosubstitution of the guanidine and substitution of the thiazole at C-5 both often led to increased activity, but combining these changes generated compounds less active than the parents. Despite 100-fold improvement in in vitro inhibitory potency, only a 3-fold increase in gastric antisecretory activity in rats was observed for these agents.