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The stability of dispersions containing charged particles may obviously be regulated by salt. In some systems, the effective charge, as measured by the potential some small distance away from the particles, can have a sign opposite to the bare surface charge. If charge reversal takes place, there is typically a salt concentration regime within which colloidal stability increases with added salt. These experimental findings on dispersions have been corroborated by atomic force microscopy investigations, where an attraction is found at short separations. This attraction is stronger than expected from standard DLVO theory, and there has been considerable debate concerning its origin. In this work, we use simple coarse-grained models of these systems, where the bare surfaces carry a uniform charge density, and ion-specific adsorption is absent. Our hypothesis is that these experimental observations can be explained by such a simplistic pure Coulomb based model. Our approach entails grand canonical Metropolis Monte Carlo (MC) simulations as well as correlation-corrected Poisson-Boltzmann (cPB) calculations. In the former case, all ions have a common size, while the cPB utilizes a point-like model. We devote significant attention on apparent surface charge densities and interactions between large flat model surfaces immersed in either a 2:1 salt or a 3:1 salt. In contrast to most of the previous theoretical efforts in this area, we mainly focus on the weak long-ranged repulsion and its connection to an effective surface charge. We find a charge reversal and a concomitant development of a free energy barrier for both salts. The experimentally observed nonmonotonic dependence of colloidal stability on the salt concentration is reproduced using MC simulations as well as cPB calculations. A strong attraction is observed at short range for all investigated cases. We argue that in our model, all non-DLVO aspects can be traced to ion–ion correlations.

Due to the compact two-dimensional interlayer pore space and the high density of interlayer molecular adsorption sites, clay minerals are competitive adsorption materials for carbon dioxide capture. We demonstrate that with a decreasing interlayer surface charge in a clay mineral, the adsorption capacity for CO2 increases, while the pressure threshold for adsorption and swelling in response to CO2 decreases. Synthetic nickel-exchanged fluorohectorite was investigated with three different layer charges varying from 0.3 to 0.7 per formula unit of Si4O10F2. We associate the mechanism for the higher CO2 adsorption with more accessible space and adsorption sites for CO2 within the interlayers. The low onset pressure for the lower-charge clay is attributed to weaker cohesion due to the attractive electrostatic forces between the layers. The excess adsorption capacity of the clay is measured to be 8.6, 6.5, and 4.5 wt % for the lowest, intermediate, and highest layer charges, respectively. Upon release of CO2, the highest-layer charge clay retains significantly more CO2. This pressure hysteresis is related to the same cohesion mechanism, where CO2 is first released from the edges of the particles thereby closing exit paths and trapping the molecules in the center of the clay particles.

A basic logic gate based on conventional silicon transistors needs the combination of at least two transistors in series or parallel. Two-dimensional (2D) materials with atomic thickness and flexib...

Two-dimensional (2D) transition-metal dichalcogenide (TMDC)-based semiconducting van der Waals (vdW) heterostructures are considered as potential candidates for next-generation nanoelectronics due to their unique and tunable properties. Controlling the carrier type and band alignment in 2D TMDCs and their vdW heterostructures is critical for realizing heterojunctions with the desired performances and functionalities. In this report, controlling the carrier type and band alignment in a vertical MoTe2/MoS2 heterojunction is presented via thickness engineering and surface charge transfer doping. A highly rectifying p-n diode and a nonrectifying n-n junction are obtained with different MoTe2 thicknesses due to their different doping conditions. A vertical tunnel diode is subsequently achieved with a controlled oxygen plasma treatment, which selectively induces degenerate p-type doping to MoTe2, whereas the intrinsic n-type characteristic of MoS2 is maintained during the treatment. These techniques to realize multifunctional diodes are universal and applicable to emerging nanoelectronics based on 2D materials.

Phyllosilicate clays are layered structures with diverse nanoscale morphology depending on the composition. Size mismatch between the sheets can cause them to form nanoscrolls, a spiral structure with different inner and outer surface charges. The hydroxyls on the exposed surface of the nanoscrolls determine the adsorption properties and hydrophilicity of the surface. Vibrational sum frequency generation (VSFG) spectroscopy was applied to study the surface hydroxyls of nickel phyllosilicate (Ni3Si2O5(OH)4), revealing three distinct in-phase OH-stretch modes: 3642, 3645, and 3653 cm-1. The relative signs of the peaks allow their assignment as "outward" and "inward" pointing hydroxyls on the opposite sides of the scrolled sheet, consistent with the crystal structure. Orientational analysis of polarization-selected VSFG spectra is consistent with a broad (140-164°) step-function distribution of the OH-stretch tilt angles, which we attribute to the uncompensated portion of the scroll rolled more than a whole number of full turns.

Nanoparticle carriers show promise for drug delivery, including by inhalation, where the first barrier for uptake in the lungs is the monolayer pulmonary surfactant membrane that coats the air/alveoli interface and is critical to breathing. It is imperative to establish the fate of potential nanocarriers and their effects on the biophysical properties of the pulmonary surfactant. To this end, the impact of the nanoparticle surface charge on the lateral organization, thickness, and recompressibility of Langmuir monolayers of model phospholipid-only and phospholipid-protein mixtures was investigated using native and modified forms of nanophytoglycogen, a carbohydrate-based dendritic polymer extracted from corn as monodisperse nanoparticles. We show that the native (quasi-neutral) and anionic nanophytoglycogens have little impact on the phase behavior and film properties. By contrast, cationic nanophytoglycogen alters the film morphology and increases the hysteresis associated with the work of breathing due to its electrostatic interaction with the anionic phospholipids in the model systems. These findings specifically highlight the importance of surface charge as a selection criterion for inhaled nanoformulations.

Hydrophilic gold nanoclusters (Au NCs) whose physical and chemical properties are not susceptible to large changes in pH are greatly desired for diverse applications. Here, we design Au NCs protected by a hydroxyl-thiol ligand (e.g., 1-thioglycerol (TG)) with a molecular formula of Au34(TG)22 as a proof-of-concept for a Au NC model with near-neutral surface charge. Unlike hydrophilic thiols with charged functional groups (e.g., carboxylate-thiol) that are usually used for hydrophilic Au NCs, this type of Au NCs is protected by hydroxyl-thiols, which are less susceptible to the prevailing pH conditions as the hydroxyl group is less acidic than water. More interestingly, the resulting Au NCs also possess pH-independent fluorescence intensity, making them suitable for applications under strong acidic conditions, which are currently not available in the reported hydrophilic Au NCs.

The development of efficient signaling strategies is highly important for photoelectrochemical (PEC) immunoassay. We report here a new and efficient strategy for sensitive PEC immunoassay by tailoring the electrostatic interaction between the photoactive material and the electron donor. The photoelectric conversion of hexametaphosphate (HMP)-capped CdS quantum dots (QDs) in Na2SO3 solution is significantly boosted after Ca2+ incubation. The negative surface charges on CdS@HMP QDs decrease because of the complexation reaction between HMP and Ca2+, and the electrostatic repulsion between CdS@HMP QDs and electron donor (SO32-) becomes weak accordingly, leading to an improved electron-hole separation efficiency. Inspired by the PEC response of CdS@HMP QDs to Ca2+, a novel "signal-on" PEC immunoassay platform is established by employing CaCO3 nanoparticles as labels. By regulating the surface charge of CdS@HMP QDs with in situ-generated Ca2+ from CaCO3 labels, sensitive detection of the carcinoembryonic antigen (CEA) is achieved. The linear detection range is 0.005-50 ng mL-1 and the detection limit is 1 pg mL-1 for CEA detection. Our work not only provides a facile route to tailor the photoelectric conversion but also lays the foundation for sensitive PEC immunoassay by simply regulating the surface charge of photoactive materials.

Colloidal stability was investigated in two types of particle systems, namely, with bare (h-HNT) and polyimidazolium-functionalized (h-HNT-IP-2) alkali-treated halloysite nanotubes in solutions of metal salts and ionic liquids (ILs). The valence of the metal ions and the number of carbon atoms in the hydrocarbon chain of the IL cations (1-methylimidazolium (MIM+), 1-ethyl-3-methylimidazolium (EMIM+), 1-butyl-3-methylimidazolium (BMIM+), and 1-hexy1-3-methylimidazolium (HMIM+)) were altered in the measurements. For the bare h-HNT with a negative surface charge, multivalent counterions destabilized the dispersions at low values of critical coagulation concentration (CCC) in line with the Schulze-Hardy rule. In the presence of ILs, significant adsorption of HMIM+ took place on the h-HNT surface, leading to charge neutralization and overcharging at appropriate concentrations. A weaker affinity was observed for MIM+, EMIM+, and BMIM+, while they adsorbed on the particles to different extents. The order HMIM+ < BMIM+ < EMIM+ < MIM+ was obtained for the CCCs of h-HNT, indicating that HMIM+ was the most effective in the destabilization of the colloids. For h-HNT-IP-2 with a positive surface charge, no specific interaction was observed between the salt and the IL constituent cations and the particles, i.e., the determined charge and aggregation parameters were the same within experimental error, irrespective of the type of co-ions. These results clearly indicate the relevance of ion adsorption in the colloidal stability of the nanotubes and thus provide useful information for further design of processable h-HNT dispersions.

The adsorption and recovery of dysprosium ions (Dy3+) from industrial wastewater are necessary but still challenging. Herein, we constructed a series of defect-containing metal-organic frameworks (MOFs) [UiO-66-(COOH)2] using sodium benzoate (BCNa) as a modulator. Upon the formation of defects, the porosity and surface charge properties of the MOFs were improved, leading to a higher utilization ratio of active groups and higher adsorption capacities for Dy3+. The synthesized UiO-66-(COOH)2-B10 with an optimal addition of BCNa exhibited a superior adsorption capacity of 150.6 mg g-1. Fast adsorption occurred at ∼5 min, and equilibrium was reached at ∼60 min. Higher pH and temperature were found to be beneficial for boosting Dy3+ adsorption, and selective adsorption over other metal ions was achieved in a multicomponent solution. Further, FTIR spectroscopy and XPS investigations indicate that free carboxyl contributes to the capture of Dy3+. Thus, this work provides a promising strategy to enhance the utilization ratio of active groups and further adsorption performance.

Lipid bilayer interactions are essential to a vast range of biological functions, such as intracellular transport mechanisms. Surface charging mediated by concentration dependent ion adsorption and desorption on lipid headgroups alters electric double layers as well as van der Waals and steric hydration forces of interacting bilayers. Here, we directly measure bilayer interactions during charge modulation in a symmetrically polarized electrochemical three-mirror interferometer surface forces apparatus. We quantify polarization and concentration dependent hydration and electric double layer forces due to cation adsorption/desorption. Our results demonstrate that exponential hydration layer interactions effectively describe surface potential dependent surface forces due to cation adsorption at high salt concentrations. Hence, electric double layers of lipid bilayers are exclusively dominated by inner Helmholtz charge regulation under physiological conditions. These results are important for rationalizing bilayer behavior under physiological conditions, where charge and concentration modulation may act as biological triggers for function and signaling.

The factors contributing to the survival of enveloped viruses (e.g., influenza and SARS-CoV-2) on fomite surfaces are of societal interest. The bacteriophage Phi6 is an enveloped viral surrogate commonly used to study viability. To investigate how viability changes during the evaporation of droplets on polypropylene, we conducted experiments using a fixed initial Phi6 concentration while systematically varying the culture concentration and composition (by amendment with 2% fetal bovine serum (FBS), 0.08 wt % BSA, or 0.5 wt % SDS). The results were consistent with the well-founded relative humidity (RH) effect on virus viability; however, the measured viability change was greater than that previously reported for droplets containing either inorganic salts or proteins alone, and the protein effects diverged in 1× Dulbecco's modified Eagle's medium (DMEM). We attribute this discrepancy to changes in virus distribution during droplet evaporation that arise due to the variable solute drying patterns (i.e., the "coffee-ring" effect) that are a function of the droplet biochemical composition. To test this hypothesis, we used surface-enhanced Raman spectroscopy (SERS) imaging and three types of gold nanoparticles (pH nanoprobe, positively charged (AuNPs(+)), and negatively charged (AuNPs(-))) as physical surrogates for Phi6 and determined that lower DMEM concentrations, as well as lower protein concentrations, suppressed the coffee-ring effect. This result was observed irrespective of particle surface charge. The trends in the coffee-ring effect correlate well with the measured changes in virus infectivity. The correlation suggests that conditions resulting in more concentrated coffee rings provide protective effects against inactivation when viruses and proteins aggregate.

Tumor microenvironment (TME) responsive polymeric micelles are promising carriers for drug delivery. In order to meet the needs of various applications, multifarious TME-responsive switches are used to construct smart polymeric micelles, which causes the complexity and corpulence of the polymeric micelle system and increases the difficulty of preparation. In this study, we designed and synthesized an ingenious TME-responsive switch through grafting disulfide bond-modified piperidinepropionic acid (CPA) on copolymer poly(ethylene glycol)-b-poly(aspartate)(PEG-b-PAsp) and built a novel pH/reduction-responsive PEG-b-PAsp-g-CPA polymeric micelle delivery system. The CPA-pendants can reverse the surface charge of the polymeric micelle from negative to positive at pH 6.5 because of the protonation of piperidine groups, thereby enhancing the internalization of cell. Subsequently, more piperidine groups are protonated at pH 5.0 which will increase the hydrophilicity of polymeric micelles and cause the hydrophobic core to swell, thus making the disulfide bonds packed in the core to be more easily broken by GSH. With the synergistic effect of the pH-triggered protonation of piperidine groups and reduction triggered break of disulfide bonds, the polymeric micelles will disintegrate and achieve efficient intracellular drug release. The TME-responsive polymeric micelles exhibited good biological safety, enhanced internalization, and rapid intracellular doxorubicin (DOX) release in vitro. Moreover, the PEG-b-PAsp-g-CPA/DOX polymeric micelles showed excellent antitumor efficacy and low systemic toxicity in lung tumor-bearing BALB/C mice. These results indicated that the novel integrated TME-responsive switch CPA helps the PEG-b-PAsp-g-CPA polymeric micelles to obtain excellent TME-responsiveness and antitumor drug delivery capabilities, while it also makes the preparation of TME-responsive polymeric micelles simpler and more convenient. This work provides a new idea for the architecture of TME-responsive polymeric micelles.

Unique surface properties of aluminosilicate clay minerals arise from anisotropic distribution of surface charge across their layered structures. Yet, a molecular-level understanding of clay mineral surfaces has been hampered by the lack of analytical techniques capable of measuring surface charges at the nanoscale. This is important for understanding the reactivity, colloidal stability, and ion-exchange capacity properties of clay minerals, which constitute a major fraction of global soils. In this work, scanning ion conductance microscopy (SICM) is used for the first time to visualize the surface charge and topography of dickite, a well-ordered member of the kaolin subgroup of clay minerals. Dickite displayed a pH-independent negative charge on basal surfaces whereas the positive charge on edges increased from pH 6 to 3. Surface charges responded to malonate addition, which promoted dissolution/precipitation reactions. Results from SICM were used to interpret heterogeneous reactivity studies showing that gas-phase nitrous acid (HONO) is released from the protonation of nitrite at Al–OH(2)(+) groups on dickite edges at pH well above the aqueous pK(a) of HONO. This study provides nanoscale insights into mineral surface processes that affect environmental processes on the local and global scale.

Degenerately doped metal-oxide nanocrystals (NCs) show localized surface plasmon resonances (LSPRs) that are tunable via their tunable excess charge-carrier densities. Modulation of excess charge carriers has also been used to control magnetism in colloidal doped metal-oxide NCs. The addition of excess delocalized conduction-band (CB) electrons can be achieved through aliovalent doping or by postsynthetic techniques such as electrochemistry or photodoping. Here, we examine the influence of charge-compensating aliovalent dopants on the potentials of excess CB electrons in free-standing colloidal degenerately doped oxide NCs, both experimentally and through modeling. Taking Sn4+:In2O3 (ITO) NCs as a model system, we use spectroelectrochemical techniques to examine differences between aliovalent doping and photodoping. We demonstrate that whereas photodoping introduces excess CB electrons by raising the Fermi level relative to the CB edge, aliovalent impurity substitution introduces excess CB electrons by stabilizing the CB edge relative to an externally defined Fermi level. Significant differences are thus observed electrochemically between spectroscopically similar delocalized CB electrons compensated by aliovalent dopants and those compensated by surface cations (e.g., protons) during photodoping. Theoretical modeling illustrates the very different potentials that arise from charge compensation via aliovalent substitution and surface charge compensation. Spectroelectrochemical titrations allow the ITO NC band-edge stabilization as a function of Sn4+ doping to be quantified. Extremely large capacitances are observed in both In2O3 and ITO NCs, making these NCs attractive for reversible charge-storage applications.

Attapulgite (denoted as APT, also called palygorskite) has been regarded as the green material in the “21st century world” and has attracted widespread attention due to its advantages of low cost, natural abundance, nontoxic nature, and environmental friendliness. However, the limited adsorption sites and surface charges of natural APT greatly hinder its application as an adsorbent in industrial fields. In this work, natural APT was modified with sodium humate (SA) via a facile one-step hydrothermal process to improve its adsorption capacity and systematically studied its ability to remove methylene blue (MB) from aqueous solutions. The effect of hydrothermal modification in the presence of SA on the microscopic structure, morphology, and physicochemical properties of APT was studied by field-emission scanning electron microscopy, Fourier transform infrared spectrometry, X-ray diffraction, and Brunauer–Emmett–Teller analyses. The adsorption properties of the modified APT toward MB were evaluated systematically. The results demonstrated that the modified APT has a high adsorption capacity of 227.27 mg/g and also shows a high removal rate up to 99.7% toward MB in a dye solution with an initial concentration of 150 mg/L, which was a 64.7% increase as compared to that of raw APT. The adsorption kinetics could be fitted to the pseudo-second-order model, while the adsorption isotherm could be well-described with the Langmuir model. It was concluded that electrostatic attraction, hydrogen-bonding interaction, and chemical association are the main driving force during the adsorption process.

The trend to replace petroleum-based products with sustainable alternatives has shifted research efforts toward plant-based materials such as cellulose nanocrystals (CNCs). CNCs show promise in numerous applications (e.g., composites and rheological modifiers); however, maximizing their performance often requires surface modifications with complex chemistries and purification steps. Presented here is a novel surface modification method with the potential to tune CNC properties through the in situ deposition of cellulose phosphate oligosaccharides during CNC production. This was achieved by leveraging the selective solubility of oligosaccharides, which are soluble at a low pH (during the CNC hydrolysis) yet become insoluble and precipitate onto CNC surfaces upon increasing pH during quenching. Oligosaccharide-coated CNCs demonstrated subtle changes including higher surface charge densities and lower water adsorption capacities and viscosities than their unmodified counterparts. CNC surface coverage was tuned by controlling the oligosaccharide degree of polymerization. Overall, this fundamental study introduces an easily scalable modification route that opens the door for expanded CNC functionality and applications.

This study reports a novel cross-linking approach to fabricate the hydrothermally neutralized silica hydrogel of SiO2-H3BO3-hexadecyltrimethoxysilane by grafting alkylsilane groups onto the nanoporous silica. The synthesized silica hydrogel possessed a large specific surface area of 51.3 m2g-1 and showed excellent dye adsorption capability of cationic dyes in neutral (pH 7) and alkaline (pH 9) medium from wastewater. The colloidal electrokinetic potential analysis revealed that the outstanding adsorption efficiency of cationic dyes over anionic dyes strongly relies on the surface charge of the hydrogels. Moreover, the hydrophobic interactions between the dye molecules and the hydrogels were studied, and it was found that the dye adsorption performance can be tuned by altering the concentration of hydrophobic reagents of the hydrogel. The dye adsorption mechanism was established, and the kinetic study suggested that the adsorption is a pseudo-second-order reaction. Adsorption isotherms at various equilibrium conditions fitted well with the Langmuir isotherm. Therefore, this strongly supports the promising and practical application of the prepared silica hydrogel. The recyclability of the hydrogel was studied, and it showed 90% adsorption efficiency by the regenerated gel up to 6 cycles, which has a high potential in wastewater treatment.

Vitrinite and inertinite, respectively, are the reactive and inert macerals for coal liquefaction, which could be effectively enriched in triboelectrostatic separation specialized in particle processing. Inertinite has a higher specific surface area and more pores than vitrinite and a more balanced mesopores distribution, while the mesopores in vitrinite are mainly focused in the 4 nm × 7 nm range. As for electrical properties, inertinite has a higher relative dielectric constant than vitrinite in all granularities, while its resistivity is only higher than vitrinite in the

Tunable gating graphene oxide (GO) membranes with high water permeance and precise molecular separation remain highly desired in smart nanofiltration devices. Herein, bioinspired by the filtration function of the renal glomerulus, we report a smart and high-performance graphene oxide membrane constructed via introducing positively charged polyethylenimine-grafted GO (GO-PEI) to negatively charged GO nanosheets. It was found that the additional GO-PEI component changed the surface charge, improved the hydrophilicity, and enlarged the nanochannels. The glomerulus-inspired graphene oxide membrane (G-GOM) shows a water permeance up to 88.57 L m-2 h-1 bar-1, corresponding to a 4 times enhancement compared with that of a conventional GO membrane due to the enlarged confined nanochannels. Meanwhile, owing to the electrostatic interaction, it can selectively remove positively charged methylene blue at pH 12 and negatively charged methyl orange at pH 2, with a removal rate of over 96%. The high and cyclic water permeance and highly selective organic removal performance can be attributed to the synergic effect of controlled nanochannel size and tunable electrostatic interaction in responding to the environmental pH. This strategy provides insight into designing pH-responsive gating membranes with tunable selectivity, representing a great advancement in smart nanofiltration with a wide range of applications.

Water-insoluble cationic poly(vinyl alcohol) (PVA) films were fabricated using a mixed aqueous solution of PVA and poly([2-(methacryloyloxy)ethyl]trimethylammonium chloride (METAC)-co-methacrylic acid (MAAc)-co-5-methacrylamido-1,2-benzoxaborole (MAAmBO)) copolymer (3D). The surface of the PVA film is typically negatively charged, and simple fabrication methods for water-insoluble PVA films with cationic surface charges are required to expand their application fields. METAC, which has a permanent positive charge owing to the presence of a quaternary ammonium cation, was selected as the cationic unit. The MAAc and MAAmBO units were used as two types of cross-linking structures for the thermal cross-linking of the hydroxy and carboxy groups of the MAAc unit (covalent bonding) as well as the diol and benzoxaborole groups of the MAAmBO unit (dynamic covalent bonding). The films were thermally cross-linked at 135 °C for 4 h without the addition of materials. After immersion in surplus water at 80 °C for 3 h, the cross-linked PVA/3D films retained almost 100% of their weights. The ζ-potential of the water-insoluble PVA/3D film was 9.4 ± 0.8 mV. The PVA/3D film was strongly dyed using anionic acid red 1 (AR1) because of its positively charged surface. Interestingly, it could also be slightly dyed using cationic methylene blue (MB) and became transparent (original state) after immersion in water for 2 days. These results suggested that positive and negative charges coexisted in the PVA/3D film, and the surface properties were positively inclined. Moreover, the degree of hemolysis of the PVA/3D films was similar to that of the negative control, which showed high blood compatibility. To our knowledge, this is the first report on the fabrication of water-insoluble cationic PVA films using two types of cross-linking structures containing carboxy and benzoxaborole groups. The cross-linked PVA films were analyzed using Fourier transform infrared (FT-IR) spectroscopy, differential scanning calorimetry (DSC), and contact angle (CA) and ζ-potential measurement, as well as by determining the mechanical properties, adsorption of charged molecules, and biocompatibility. These readily fabricated water-insoluble PVA films with positive charges can show potential applications in sensors, adsorption systems, and antimicrobial materials.

Label-free potentiometric detection of DNA molecules using a field-effect transistor (FET) with a gold gate offers an electrical sensing platform for rapid, straightforward, and inexpensive analyses of nucleic acid samples. To induce DNA hybridization on the FET sensor surface to enable potentiometric detection, probe DNA that is complementary to the target DNA has to be immobilized on the FET gate surface. A common method for probe DNA functionalization is based on thiol-gold chemistry, immobilizing thiol-modified probe DNA on a gold gate with thiol-gold bonds. A self-assembled monolayer (SAM), based on the same thiol-gold chemistry, is also needed to passivate the rest of the gold gate surface to prevent non-specific adsorption and to enable favorable steric configuration of the probe DNA. Herein, the applicability of such FET based potentiometric DNA sensing was carefully investigated, using a silicon nanoribbon FET (SiNRFET) with a gold sensing gate modified with thiol-gold chemistry. We discover that the potential of the gold sensing electrode was determined by the mixed potential of the gold-thiol and gold-oxygen redox interactions. This mixed potential gives rise to a redox buffer effect which buffers the change in the surface charge induced by the DNA hybridization, thus suppressing the potentiometric signal. Analogous redox buffer effects may also be present for other types of potentiometric detections of biomarkers based on thiol-gold chemistry.

We aimed to prepare metal oxide materials with the optimal surface charge by preparing mixed films of non-modified metal oxide nanoparticles (NPs) with dissimilar isoelectric points (iep). The purpose of preparing such surfaces was to expand the use of metal oxide materials in environments where the solution pH cannot be changed. Langmuir films of SiO2 (iep: pH 2-3) and TiO2 (iep: pH 5-6.6) NPs were first prepared at air-100 mM NaCl aqueous interfaces. This subphase allowed the formation of stable films of the NPs without the need to modify the NPs with surface-active chemicals, whose presence may detrimentally change the properties of the films. The Langmuir films were then transferred and sintered to silicon wafers and their physical properties were characterized using atomic force microscopy (AFM). The AFM images showed that the films were composed of NP aggregates. The average size of the aggregates decreased, and the uniformity of the aggregate sizes and their inter-aggregate spacing increased with the addition of SiO2 NPs to the film of TiO2 NPs. These changes were explained by an increased electrostatic and steric repulsion between the aggregates formed at the air-100 mM NaCl interface due to the adsorption of negatively charged SiO2 NPs to the slightly positively charged TiO2 aggregates. The force-distance curves measured between a SiO2 probe and the sintered films of SiO2 and/or TiO2 NPs in a 1.0 mM NaCl solution adjusted to pH 4 showed that the magnitude of the repulsive force decreased with an increased number of TiO2 NPs in the film. This force change indicated that the surface charge changed when different types of NPs were mixed. These results indicate that mixing different NP types in a Langmuir film at an air-aqueous interface can help change the physical properties of the transferred film.

Cationic nanoparticles are known to interact with biological membranes and often cause serious membrane damage. Therefore, it is important to understand the molecular mechanism for such interactions and the factors that impact the degree of membrane damage. Previously, we have demonstrated that spatial distribution of molecular charge at cationic nanoparticle surfaces plays an important role in determining the cellular uptake and membrane damage of these nanoparticles. In this work, using diamond nanoparticles (DNPs) functionalized with five different amine-based surface ligands and small phospholipid unilamellar vesicles (SUVs), we further investigate how chemical features and conformational flexibility of surface ligands impact nanoparticle/membrane interactions. 31P-NMR T2 relaxation measurements quantify the mobility changes in lipid dynamics upon exposing the SUVs to functional DNPs, and coarse-grained molecular dynamics simulations further elucidate molecular details for the different modes of DNP-SUV interactions depending on the surface ligands. Collectively, our results show that the length of the hydrophobic segment and conformational flexibility of surface ligands are two key factors that dictate the degree of membrane damage by the DNP, while the amount of surface charge alone is not predictive of the strength of interaction.

Nanofluidic diodes are capable of rectifying the electrical current by several orders of magnitude. In the current state of affairs, determining the rectification factor is not possible as it depends on many system parameters. In this work, we systematically scan the effects of geometry and excess counterion concentrations (i.e., surface charge effects). We show that the current-voltage response varies between the two extreme behaviors of unipolar and bipolar responses. The exact behavior depends on the geometry and surface charge properties of the system. Here, we have gone beyond the typical setup that only considers the dynamics within the nanochannel itself and we have included the effects of the adjoining microchannels. Systems that include both nanochannels and microchannels exhibit the classical signatures of concentration polarization, such as ionic depletion and enrichment. Here, where we have scanned a wide range of parameters, we show that bipolar and semi-bipolar systems exhibit a wider range of phenomena that are intrinsically more complicated. Our system characterization is for both, the much more investigated case of steady state and the less investigated, but equally interesting, time-transient case. For example, it is common to characterize the system by its steady-state result (current-voltage response, rectification factor, and transport number). Here, we demonstrate that the time-transient behavior of the fluxes can also be used to characterize the system, and that the time-dependent rectification factors and transport numbers are meaningful. The systematic approach taken in this work, and the results presented herein, can be used to further elucidate the complicated behavior of the current-voltage response of nanofluidic diodes and to rationalize experimental results. The insights of this work can be used to enhance and improve the design of all nanofluidic diodes.

Triboelectric generators (TENGs) have been extensively studied as a new energy for low cost and the universally applicable prospect. Meanwhile, perovskites have been applied in TENG and show a good performance in view of high carrier mobility, long life and dielectric properties. The asymmetry structure of the orthogonal phase CsPbBr3 perovskite endows it with ferroelectric property and induces the misalignment of the positive and negative charge centers. Herein, the surface energy of halogen doped inorganic CsPbX3 (X = Cl-, Br-) perovskites are theoretically investigated by density functional theory (DFT) calculation, the crystal polarizability of pristine CsPbBr3 is improved from 0.47 Ry a.u. to 0.52 Ry a.u. (CsPbCl3), indicating the polarizability of CsPbCl3 is higher than CsPbBr3. In addition, the build-in electric field (Ebuild-in) of perovskite materials can be enhanced by the spontaneous polarization and the aligned dipoles in the Ebuild-in could further improve the tribo-electrostatic electric field by retaining more triboelectric surface charges. In the end, CsPbCl3 achieved a power of 3.06 W m-2 compared to the power of 1.34 W m-2 of CsPbBr3. This work focuses on the regulation of crystal planes using spontaneous polarization of perovskite toward achieving a high built-in electric field for enhancing triboelectric surface charge density.

Collagen fibrils act like nanoscale cables in the extracellular matrix of vertebrate tissues and provide a scaffold for cells to attach to. However, beyond this mechanical function, the surface charge of collagen fibrils is also likely to play an important role. Here, we show that native, type I collagen fibrils from a mammal tendon exhibit a particular dependence of surface charge on longitudinal strain. Fibrils first become more positive with strain of up to 10% and then become more negative again with strain between 10 and 17%. The effect correlates with the stiffness of fibrils and can be explained by structural rearrangements, which expose hidden, ionizable residues. Fibrils treated with glutaraldehyde did not show any change in surface charge when strained. The electrical surface potential, which is directly related to the number ratio of exposed amine and carboxy groups on the surface, was determined by Kelvin-probe force microscopy of fibrils attached on an extensible, thin polymer film. By stretching the film, a large number of individual fibrils could be strained simultaneously without resorting to sophisticated nanomechanical devices. It is conceivable that cells react to such changes of the fibril charge and that this effect is an additional contributor, besides mechanics, to a number of physiological processes. It may also need to be considered in the design of tissue-engineering scaffolds.

Gas-responsive nanochannels have great relevance for applications in many fields. Inspired by CO2-sensitive ion channels, herein we present an approach for designing solid-state nanochannels that allow controlled regulation of ion transport in response to alternate CO2/N2 stimuli. The pillar[5]arene (P5N) bearing diethylamine groups can convert into the water-soluble host P5C, containing cationic tertiary ammonium salt groups after absorbing CO2. Subsequently, the nanochannel walls are tailored using P5N-based host-guest chemistry. The ion transport rate of K+ in the P5N nanochannels under CO2 was 1.66 × 10-4 mol h-1 m-2, whereas that under N2 was 7.98 × 10-4 mol h-1 m-2. Notably, there was no significant change to the ion current after eight cycles, which may indicate the stability and repeatability of CO2-activated ion nanochannels. It is speculated that the difference in ion conductance resulted from the change in wettability and surface charge within the nanochannels in response to the gas stimuli. Achieving CO2-activated ion transport in solid-state nanochannels opens new avenues for biomimetic nanopore systems and advanced separation processes.

Low permeability and chlorine resistance of normal thin-film composite (TFC) membranes restrict their practical applications in many fields. This study reports the preparation of a high chlorine-resistant TFC membrane for forward osmosis (FO) by incorporating corn stalk-derived N-doped carbon quantum dots (N-CQDs) into the selective polyamide (PA) layer to construct a polydopamine (PDA) sub-layer (PTFCCQD). Membrane modification is characterized by surface morphology, hydrophilicity, Zeta potential, and roughness. Results show that TFCCQD (without PDA pretreatment) and PTFCCQD membranes possess greater negative surface charges and thinner layer-thickness (less than 68 nm). With N-CQDs and PDA pretreatment, the surface roughness of the PTFCCQD membrane decreases significantly with the co-existence of microsized balls and flocs with a dense porous structure. With the variation of concentration and type of draw solution, the PTFCCQD membrane exhibits an excellent permeability with low J(reverse salt flux)/J(water flux) values (0.1-0.25) due to the enhancement of surface hydrophilicity and the shortening of permeable paths. With 16,000 ppm·h chlorination, reverse salt flux of the PTFCCQD membrane (8.4 g m-2 h-1) is far lower than those of TFCCQD (136.2 g m-2 h-1), PTFC (127.6 g m-2 h-1), and TFC (132 g m-2 h-1) membranes in FO processes. The decline of salt rejection of the PTFCCQD membrane is only 8.2%, and the normalized salt rejection maintains 0.918 in the RO system (16,000 ppm·h chlorination). Super salt rejection is ascribed to the existence of abundant N-H bonds (N-CQDs), which are preferentially chlorinated by free chlorine to reduce the corrosion of the PA layer. The structure of the PA layer is stable during chlorination also due to the existence of various active groups grafted on the surface. This study may pave a new direction for the preparation of durable biomass-derivative (N-CQD)-modified membranes to satisfy much more possible applications.

Ultrathin nanoporous (NP) films are an emerging field for selective and effective ion/molecular separation and electrochemical sensing applications. We describe selective ion permeation in surface-functionalized ultrathin NP SiO2 films (NP SiO2-NH2). The ultrathin NP SiO2 films with ca. 8 nm thickness were prepared from silsesquioxane-containing blend polymer Langmuir-Blodgett films (nanosheets) using the photo-oxidation method. The porous SiO2 surface was modified with a pH-responsive amine-containing silane coupling agent. Selective ion permeation was demonstrated under acidic pH conditions (pH ≤ 6) using two equally sized redox probes: negative (Fe(CN)63-/4-) and positive (Ru(NH3)62+/3+) ions. The current density for Fe(CN)63-/4- decreased as the pH value increased to pH = 6, whereas it increased for Ru(NH3)62+/3+. Control measurements revealed that the probes can penetrate the pores of nonfunctionalized SiO2 films irrespective of pH values, indicating that both the size and the surface charge response contributed to selective ion permeation. Results obtained from this study pave the way for new applications in molecular separation and sensing applications based on ultrathin nanoporous films (

Dense polymeric films based on network-forming cellulose nanofibrils (CNFs) have excellent mechanical properties but are limited by moisture sensitivity. Here, interfibrillar effects from CNF surface properties are investigated. TEMPO-oxidized CNFs and two native CNFs are prepared with a similar length and width, to exclude geometrical effects. The CNFs have different surface properties in terms of sorbed hemicellulose content, hemicellulose molar mass, and surface charge. Moisture sorption, structural changes, and mechanical properties at different relative humidities are characterized. The presence of sorbed hemicelluloses in the interfibrillar interphase has favorable effects on the mechanical tensile properties. Surface-charged carboxyls increased moisture sorption and film thickness swelling and reduced the mechanical properties. A comparison with biaxially oriented polyethylene terephthalate films provides a perspective into the structure and properties of CNF films. The present study shows the importance of the interfibrillar interface and interphase region for mechanical film properties, including moisture effects.

MoS2 used for effective hydrogen evolution mainly depends on the activity of Mo–S edge sites. The exposure of abundant active edge sites has become an important way to broadly enhance the MoS2 cata...

The dispersion behavior of DNA duplex-carrying colloidal particles in aqueous high-salt solutions shows extraordinary selectivity against the duplex terminal sequence. We investigated the interparticle force between DNA duplex-carrying polystyrene (dsDNA-PS) microparticles in aqueous salt solutions and examined their behavior in relation to the duplex terminal sequences. Force-distance (F-D) curves for a pair of dsDNA-PS particles were recorded with a dual-beam optical tweezers system with the two optically trapped particles closely approaching each other. Interestingly, only 3-5% of the oligo-DNA strands on the dsDNA-PS particles formed a duplex with complementary DNAs, and the F-D curves showed a distinct specificity to the duplex terminal sequences in the interparticle force at a high-NaCl concentration; a clear attraction peak was observed in F-D curves only when the duplex terminal was a complementary base pair. The attractive strength reached 2.6 ± 0.5 pN at 500 mM NaCl and 4.3 ± 1.0 pN at 750 mM NaCl. By sharp contrast, no significant attraction occurred for the particles with mismatched duplex terminals even at 750 mM NaCl. Similar duplex terminal-specificity in the interparticle force was also confirmed for dsDNA-PS particles in divalent MgCl2 solutions. Considering that the duplex terminal sequences on the dsDNA-PS particles showed only a negligible difference in their surface charges under identical salt conditions, we concluded that the interparticle attraction observed only for the dsDNA-PS particles with complementary duplex terminals is attributable to the salt-facilitated stacking interaction between the paired terminal nucleobases (i.e., blunt-end stacking) on the dsDNA-PS surfaces. Our results thus demonstrate the occurrence of a duplex terminal-specific interparticle force between dsDNA-PS particles under high-salt conditions.

Nanoparticles with multifunctionality and high colloidal stability are essential for biomedical applications. However, their use is often hindered by the formation of thick coating shells and/or nanoparticle agglomeration. Herein, we report a single nanoparticle coating strategy to form 1 nm polymeric shells with a variety of chemical functional groups and surface charges. Under exposure to alternating magnetic field, nanosecond thermal energy pulses trigger a polymerization in the region only a few nanometers from the magnetic nanoparticle (MNP) surface. Modular coatings containing functional groups, according to the respective choice of monomers, are possible. In addition, the surface charge can be tuned from negative through neutral to positive. We adopted a coating method for use in biomedical targeting studies where obtaining compact nanoparticles with the desired surface charge is critical. A single MNP with a zwitterionic charge can provide excellent colloidal stability and cell-specific targeting.

A substantial amount of water used for fracking shale formations is trapped by capillary and interfacial forces. Such trapped water is detrimental to gas production because of its potential to obstruct gas’s desorption and, subsequently, its flow path. Surfactants are proposed to alleviate the problem; however, further insight is required to understand the underlying mechanism. In this study, a cationic surfactant, namely, cetyltrimethylammonium bromide (CTAB), and a clay-rich Marcellus shale are used to investigate and explain the mechanism. The study encompasses a series of systematic experiments and molecular simulations. First, laboratory measurements of CH₄–brine interfacial tension, CH₄ surface excess, and zeta potential at different CTAB concentrations were conducted. Then, we evaluated CH₄ adsorption in Marcellus shale before and after treatment with CTAB. Second, a molecular dynamics simulation by GROMACS software was used to explain the phenomenon at the molecular level. Experimental results indicated that CTAB reduced the CH₄–brine interfacial tension by up to 80%. The zeta potential data showed that shale’s dominant surface charge was altered from negative to positive after treatment with CTAB. Furthermore, the presence of CTAB has significantly influenced the distribution of CH₄ in the aqueous phase as indicated by the changes in the CH₄ surface excess concentration. Moreover, the adsorbed CH₄ amount decreased with increasing CTAB concentration when the CTAB concentration was kept below the critical micelle concentration (CMC). The reduction in adsorbed CH4 was explained by the molecular dynamics simulation results, which revealed a 62% shrinkage in vertical distances between CH₄ molecules and clays after introducing CTAB. Simulation findings also unfold that CTAB has reduced the density distribution of CH₄ molecules along with clay layers by 64%. One of the more significant result of this study is that surfactants injected at above CMC values can lessen fracking water trapping by reducing CH₄ brine interfacial tension, changing surface charges, and reducing molecular distances between CH₄ and hydrophilic clays.

In recent years, controlling and manipulating the materials’ surface charges have gained significant attention because of efficient application in various fields such as catalysis, dye adsorption, ...

U(VI) and Eu(III), as representative elements of the hexavalent actinide and trivalent lanthanides (always as a chemical analogue for trivalent actinide), respectively, have attracted more and more attentions due to the widespread use of nuclear energy. Much effort has been focused on developing versatile materials for their uptake from aqueous solution. For the first time, we report here UiO-66 and its mono- (UiO-66-COOH) and di-carboxyl (UiO-66-2COOH) functional derivatives as robust adsorbents for efficient U(VI) and Eu(III) removal. It is found that the introduction of carboxyl groups greatly reduces the surface charge of UiO-66, thus guaranteeing excellent adsorption capacity at low pH. At pH = 3, for example, the adsorption capacity of UiO-66-2COOH for U(VI) and Eu(III) is more than 100 and 60 mg/g, respectively, while almost no adsorption occurs for pristine UiO-66. At pH = 4, both UiO-66-COOH and UiO-66-2COOH show high performance on U(VI) and Eu(III) removal. UiO-66-COOH has adsorption capacities of 80 and 43 mg/g for U(VI) and Eu(III), respectively, while the values for UiO-66-2COOH reach 150 and 80 mg/g, respectively. Also, all these materials achieve adsorption equilibrium within 100 min. More importantly, combining the needs of practical applications and the characteristics of high stability, high porosity, and excellent adsorption performance of UiO-66-2COOH, dynamic adsorption column experiments were successfully conducted; ∼99% U(VI)/Eu(III) can be efficiently adsorbed, and >90% adsorbed U(VI)/Eu(III) can be re-collected with dilute nitric acid solution, even after four adsorption-desorption cycles. The findings of this work demonstrate the application potential of metal-organic framework materials to remove radionuclides from environmental samples or nuclear waste liquids.

Interfaces between molecular organic architectures and oxidic substrates are a central feature of biosensors and applications of biomimetics in science and technology. For phospholipid bilayers, the large range of pH- and ionic strength-dependent surface charge densities adopted by titanium dioxide and other oxidic surfaces leads to a rich landscape of phenomena that provides exquisite control of membrane interactions with such substrates. Using neutron reflectometry measurements, we report sharp, reversible transitions that occur between closely surface-associated and weakly coupled states. We show that these states arise from a complex interplay of the tunable length scale of electrostatic interactions with the length scale arising from other forces that are independent of solution conditions. A generalized free energy potential, with its inputs only derived from established measurements of surface and bilayer properties, quantitatively describes these and previously reported observations concerning the unbinding of bilayers from supporting substrates.

Nanopore-based detection techniques, with a wide range of transport properties, exhibit impressive selectivity and sensitivity for analytes. To expand the application of nanoporous sensors, real-time and fast detection of targets, all within a portable device, is highly desired for nanopore-based sensors. In addition, to improve the accuracy of the output signal, more appropriate readout methods also need to be explored. In this manuscript, we describe a nanopore-based electrode, regarded as NAC-P6-PC@AuE, prepared by coupling a pillararene-based nanoporous membrane with an electrochemical impedance measurement method. The fabricated device is demonstrated by exposing pillararene-based receptors to trace amounts of pesticide molecules. NAC-P6-PC@AuE devices exhibit distinguished selectivity to quinotrione, as well as the ability to quantify quinotrione with a limit of quantitation (LOQ) of 10 nM. The mechanism that allows sensing was verified using finite-element simulations and may be explained as host-guest-induced surface charge shielding, which influences the electrochemical response of probe molecules. The applications of this nanopore-based electrode may be extended toward other target molecules by decorating the nanopore surfaces with specifically chosen receptors.

The reservoir rock is made up of different minerals and its surface chemistry is influenced by the reservoir environment. Well operations implemented during the life of a field induce changes in th...

Nanoparticle carriers are effective drug delivery vehicles. Along with other design parameters including size, composition, and surface charge, particle shape strongly influences cellular uptake. How nanoparticle geometry affects targeted delivery under physiologically relevant conditions, however, is inconclusive. Here, we demonstrate that nanoconstruct core shape influences the dynamics of targeting ligand-receptor interactions on cancer cell membranes. By single-particle tracking of translational and rotational motion, we compared DNA aptamer AS1411 conjugated gold nanostars (AS1411-AuNS) and 50-nm gold spheres (AS1411-50NPs) on cells with and without targeted nucleolin membrane receptors. On nucleolin-expressing cells, AS1411-AuNS exhibited faster velocities under directed diffusion and translated over larger areas during restricted diffusion compared to AS1411-50NPs, despite their similar protein corona profiles. On nucleolin-inhibited cells, AS1411-AuNS showed faster rotation dynamics over smaller translational areas, while AS1411-50NPs did not display significant changes in translation. These differences in translational and rotational motions indicate that nanoparticle shape affects how targeting nanoconstructs bind to cell-membrane receptors.

The high electrical conductivity of 1T'-WTe2 deserves particular attention and may show a high potential for hydrogen evolution reaction (HER) catalysis. However, the actual activity certainly does not match expectations, and the inferior HER activity is actually still ambiguous at the atomic level. Unraveling the underlying HER behaviors of 1T'-WTe2 will give rise to a new family of HER catalysts. Our structural analysis reveals that the inferior activity could result from insufficient charge density around the Te site and blocked adsorption channel at the W site, which cause too weak hydrogen adsorption. Herein, we fabricated a single WTe2 sheet-based electrocatalytic microdevice for directly extracting enhanced HER activity of doped electronegative F atoms. The overpotential at -10 mA cm-2 reduced to 0.27 V after F doping compared to 0.45 V for the original state. In situ electrochemical measurement and electrical tests on a single sheet indicate that doped F can regulate surface charge and hydrogen adsorption behavior. Furthermore, the theory simulation uncovers that the smaller atomic radius of F contributes to an empty coordination environment; meanwhile, strong electronegativity induces hydrogen adsorption. Thus, the ΔGH* at W sites around the doped F is as low as 0.18 eV. Synergistically modulating the charge properties and opening steric hindrance provides a new pathway to rationally construct electrocatalysts and beyond.

The self-assembly of block copolymers in a confined space has been proven to be a facile and robust strategy for fabricating assembled structures with various potential applications. Herein, we employed a new pH-responsive polymer self-assembly method to regulate ion transport inside artificial nanochannels. The track-etched asymmetric nanochannels were functionalized with PS22k-b-P4VP17k/hPS4k blend polymers, and the ionic conductance and rectification properties of the proposed system were investigated. The pH-actuated changes in the surface charge and wettability resulted in the selective pH-gated ionic transport behavior. The designed system showed a good switching property to the pH stimulus and could recover during the repetitive experiments. The gating ability of the polymer-nanochannel system increased with increasing the weight of the homopolymer, and the proposed platform demonstrated robust stability and reusability. Numerical and the dissipative particle dynamics simulations were implemented to emulate the pH-dependent self-assembling behavior of diblock copolymers in a confined space, which were consistent with the experimental observations. As an example of the self-assembly of polymers in nanoconfinements, this work provides a facile and robust strategy for the regulation of ion transport in synthetic nanochannels. Meanwhile, this work can be further extended to design artificial smart nanogates for various applications such as mass delivery and energy harvesting.