AFM Force Measurements Research Articles

Insights into gypsum and silica scaling behaviors of dense Janus membranes in membrane distillation: The effect of varied surface properties

Dense Janus membranes (JMs) have emerged as potential candidates to address the tough scaling issue in hypersaline wastewater treatments for membrane distillation (MD). However, behaviors and mechanisms of various scalants on dense JMs have not been systematically investigated. Herein, we designed three dense JMs to simultaneously compare their anti-scaling properties against gypsum and silica in MD and focus on the critical role of varied surface property in scaling control. Results showed that dense JMs with highly positive gypsum-membrane interfacial energy and with strong electrical repulsion against silica species were more effective in resisting gypsum and silica, respectively. Scaled membrane characterization, quartz crystal microbalance monitoring, interfacial energy analysis and AFM force measurement revealed the distinct anti-scaling mechanisms. Highly hydrophilic surfaces without specific interactions with scaling ions provided robust thermodynamic barriers and less kinetically affected local supersaturations, preventing gypsum nucleation and growth. In contrast, positively charged surfaces favorably attracted negatively charged silica species with high reactivity, promoting subsequent polymerization with silicic acid that kinetically dominated silica scaling. Moreover, coexisting oversaturated gypsum and silica influenced the scaling behavior of each other, and surface properties of the preferentially formed scaled layer might also matter in scaling process. This study shall provide useful insights into the anti-scaling mechanisms of dense JMs in MD and highlight the potential of dense surface design as an effective scaling control strategy to pave the way for potential MD applications.

Effects of biodegradable dispersants on the separation flotation of chalcopyrite and serpentine

The presence of serpentine slime coating on the chalcopyrite surfaces severely affects the chalcopyrite floatability. In this study, three biodegradable polymers, namely polyaspartic acid (PASP), polyepoxy succinic acid (PESA), and hydrolyzed polymaleic (HPMA) were used as dispersants to disperse the chalcopyrite and serpentine particles. The micro-flotation experiments demonstrated that the application of dispersants in the flotation effectively reduced the negative impact of serpentine over a wide pH range, restoring the recovery rate of chalcopyrite to about 85%. The XPS analysis revealed that the dispersants could be adsorbed onto the mineral surfaces through the binding of carboxyl groups with the magnesium or copper sites. As a result, the surface potentials of serpentine changed from positive to negative, while that of the chalcopyrite became even more negative, resulting in a strong electrostatic repulsion between them, which effectively eliminated the covering of the serpentine on the chalcopyrite surface. The AFM force measurements indicate a weak interaction of the polycarboxylic acids dispersants with the surface of chalcopyrite. Consequently, the adsorption of dispersants on the chalcopyrite surface has an insignificant impact on the subsequent adsorption of collectors, which is further supported by the adhesion force measurements between the air bubble and mineral surfaces. Therefore, the application of polycarboxylic acid dispersants in the flotation significantly enhanced the floatability of chalcopyrite in the presence of the serpentine fines.

Nanoscale colocalized thermal and chemical mapping of pharmaceutical powder aerosols

Inhalation of pharmaceutical aerosol formulations is widely used to treat respiratory diseases. Spatially resolved thermal characterization offers promise for better understanding drug release rates from particles; however, this has been an analytical challenge due to the small particle size (from a few micrometers down to nanometers) and the complex composition of the formulations. Here, we employ nano-thermal analysis (nanoTA) to probe the nanothermal domain of a pharmaceutical aerosol formulation containing a mixture of fluticasone propionate (FP), salmeterol xinafoate (SX), and excipient lactose, which is widely used to treat asthma and chronic obstructive pulmonary disease (COPD). Furthermore, atomic force microscopy-infrared spectroscopy (AFM-IR) and AFM force measurements are performed to provide nanochemical and nanomechanical information to complement the nanothermal data. The colocalized thermal and chemical mapping clearly reveals the surface heterogeneity of the drugs in the aerosol particles and demonstrates the contribution of the surface chemical composition to the variation in the thermal properties of the particles. We present a powerful analytical approach for in-depth characterization of thermal/chemical/morphological properties of dry powder inhaler particles at micro- and nanometer scales. This approach can be used to facilitate the comparison between generics and reference inhalation products and further the development of high-performance pharmaceutical formulations.

Probing the Interaction Mechanism of Sodium Oleate and Dodecyl Amine with Quartz Surfaces in the Presence of Ca2+ Ions by AFM Force Measurement.

Quartz is a key raw material in high-tech fields (such as photovoltaics and semiconductor microelectronics), and the most efficient extraction method of quartz is mineral flotation. Quartz activation plays a crucial role in mineral flotation. However, the mechanism underlying the process remains unclear, and the role of additional metal ions is controversial. In this study, the interaction forces between the quartz surface, the dodecylamine (DDA) cation/sodium oleate (NaOL) anion mixed collectors, and Ca2+ were analyzed using atomic force microscopy in order to systematically explore the activation process of quartz flotation. The results confirmed that the activation process was initialized from NaOL, which was adsorbed on the surface of a calcium-covered quartz surface. The existence of DDA inhibited the binding of Ca2+ to NaOL so that more Ca2+ was adsorbed on the quartz surface to provide the adsorption site for NaOL. Moreover, the best adsorption condition of Ca2+ + NaOL + DDA mixed solution was analyzed by quartz crystal microbalance with dissipation, and it demonstrated that the most stable chemisorption environment on the quartz surface was at pH 11.0. In these circumstances, Ca2+ could first adsorb in a point-like manner on the quartz surface, which was then adsorbed with a mixture of NaOL and DDA. This result showed that, at a specific pH, Ca2+ could encourage the coadsorption of cationic/anionic mixed collectors on quartz. This work provides an important new understanding of the intermolecular interactions that take place during complex mineral flotation processes between chemical additives and mineral surfaces. The methodology used in this study can be easily adapted to different interfacial processes, including water treatment, membrane technology, bioengineering, and oil production.

Machine learning framework for determination of elastic modulus without contact model fitting

Many contact models have been proposed for determining the elastic modulus of materials based on AFM force measurement. However, contact model fitting could be a challenging task since the elastic modulus usually varies depending on the tip parameters (i.e., radius and half-opening angle) which are difficult to determine in practice. Therefore, this study proposes a supervised machine learning (SML) regression framework for determining the elastic modulus without the need to either select an appropriate contact model or perform contact model fitting. In the proposed approach, the SML regressor learns the relationship between the force-displacement (FZ) features and the elastic modulus, and then predicts the elastic modulus of unseen samples directly from their FZ features. The predictive power of the proposed framework is demonstrated using both homogeneous materials (polydimethylsiloxane, polymethyl methacrylate, and polyvinyl alcohol), and heterogeneous materials (Staphylococcus aureus bacteria and methylammonium lead iodide). It is shown that the Gaussian process regression (GPR) model achieves a higher prediction accuracy than the multiple linear regression (MLR), random forest (RF), and support vector regression (SVR) models for both groups of materials. Particularly, GPR achieves a testing coefficient of determination value of up to 91.55% for homogeneous materials, and 82.73% for heterogeneous materials. Overall, the results confirm that the proposed SML regression framework is capable of determining the elastic modulus of both homogeneous and heterogeneous materials without the need for both contact model fitting and knowledge of tip shape.

Scalable, low-cost, and environment-friendly preparation of high strength carbon-matrix composites with tree-root-like structured reinforcements

The poor interfacial interaction between carbon fiber (CF) and a matrix is the main factor restricting the enhancement in performance of carbon-matrix composites. Herein, CF was modified via a facile high-speed blending with matrix pitch-cokes particles. AFM force measurements and 3D particle tracking simulations unlocked the blending CF@pitch-cokes assembly mechanism. Inspired by the strong interaction between tree roots and soil, a tree-root-like reinforced structure was designed and developed in carbon-matrix composites by the subsequent carbonization coupling effect between the pitch-cokes adsorbed CF surface and the carbonized matrix. It was found that the tree-root-like structure significantly improved the interfacial interaction and enhanced the mechanical properties of the carbon-matrix composites. Compared with the pristine CF reinforced composites, the compressive strength (158.33 ± 1.95 MPa) and flexural strength (36.65 ± 1.32 MPa) of the carbon-matrix composites with tree-root-like structures increased by 101.4% and 65.8%, respectively. A mechanical interlock mechanism is suggested to explain the enhanced mechanical properties of the composites. This work provides a facile strategy for improving the interface of CF-reinforced carbon-matrix composites and paves the way for scalable, low-cost, and environment-friendly processing of high strength composites.

Effects of surface oxidation on the pH-dependent surface charge of oxidized aluminum gallium nitride

Hypothesis: The properties of the oxidized surface for common materials, such as silicon and titanium, are known to be markedly different from the reduced surface. We hypothesize that surface-oxidized aluminum gallium nitride ((oxidized-AlGaN)/GaN) surface charge behavior is different to unoxidized AlGaN (with ultrathin native oxide only), which can be validated via surfactant adsorption. Understanding these differences will explain why (oxidized-AlGaN)/GaN-based sensors are better performing than AlGaN ones, which has been previously demonstrated but not understood.Experiments: The surface of an AlGaN/GaN structure was oxidized with hot piranha solution and oxygen plasma. AFM force measurements and imaging were performed to probe the charge properties of the surface in aqueous solutions of varying pH containing only an acid or base, or with an added ionic surfactant: cationic cetyltrimethylammonium bromide (CTAB) or anionic sodium dodecylsulfate (SDS).Findings: The (oxidized-AlGaN)/GaN surface is positively charged at pH 4 and pH 5.5, although pH 5.5 should be close to the isoelectric point of the surface. The surface is negatively charged at pH 10 and pH 12, and sufficiently charged to attract cooperative adsorption of CTAB aggregates at pH 12. At pH 2, the evidence is inconclusive, but the surface is most likely positively charged. Compared to unoxidized AlGaN, the (oxidized-AlGaN)/GaN surface shows a wider range of surface charge magnitude over pH values between 2 and 12. This suggests that the (oxidized-AlGaN)/GaN surface has a higher surface hydroxyl group density than unoxidized AlGaN, which explains the higher sensitivity for pH sensors based on (oxidized-AlGaN)/GaN structures.

Development of new sticky and conducting polymer surfaces for MEMS applications

The development of new surfaces, highly sticky and conducting, is a great challenge in the field of microdevices fabrication, and more precisely for the 3D assembly of microcomponents. Such surfaces were prepared by electrochemical deposition of polyaniline films. The films prepared from a phosphoric acid solution were more adhesive than the ones obtained in other acids. Indeed, the adhesion of the polyaniline films prepared in H3PO4 was found to be high (> 1 µN) and stable in time, as shown by AFM force measurements. The adhesion properties were correlated with the morphology, thickness and roughness of the polyaniline films, and the electrodeposition conditions (H3PO4 concentration and electrodeposition time) were optimized. The adhesion properties of this original polymer films were found to be similar to those of the best commercial glues. The conductivity of the polyaniline film was also demonstrated as well as the possibility for the polyaniline films to switch reversibly from a non-adhesive to an adhesive behavior. A wide range of applications, in the field of telecommunications, bioengineering, and more generally speaking MEMS (microelectromechanical systems) can be envisaged for these materials.

Revealing the Effects of Curcumin on SH-SY5Y Neuronal Cells: A Combined Study from Cellular Viability, Morphology, and Biomechanics.

In this work, the effects of curcumin on the viability, morphology, and nanomechanics of SH-SY5Y neuronal cells were investigated using a conventional cell viability test kit (CCK-8) and sophisticated AFM imaging and force measurement techniques. CCK-8 tests show that SH-SY5Y neuronal cells have a dose-response to curcumin in terms of viability that is dependent on the exposure durations. When exposed to a maximum dosage of 32 μg/mL used in the present study for 4 h, 24 h, and 48 h, the cell viability dropped to 73.4 ± 4.5%, 9.1 ± 3.2%, and 2.5 ± 1.2% of the control, correspondingly. AFM studies show that curcumin can induce the disappearance of synapses of the cells and the change of biomechanics. After exposure for 24 h at the concentration of 16 μg/mL, the viscous deformation of the cells decreased from 2.15 ± 0.02 to 1.58 ± 0.03 (×10-15 N·m), the elastic deformation increased from 1.26 ± 0.04 to 1.72 ± 0.07 (×10-15 N·m), and adhesion work decreased from 0.56 ± 0.07 to 0.39 ± 0.04 (×10-16 N·m). The morphological and mechanical changes obtained using AFM can be interpreted from optically observed cellular structural changes. The present study provides insights into the effects of curcumin on neuronal cells from both biological and biophysical aspects, which can help more comprehensively understand the interactions between curcumin and SH-SY5Y cells. The demonstrated techniques can be potentially used to assess the efficacy of bioactive constituents on cells or help screen drugs.

E-cadherin binds to desmoglein to facilitate desmosome assembly.

Desmosomes are adhesive junctions composed of two desmosomal cadherins: desmocollin (Dsc) and desmoglein (Dsg). Previous studies demonstrate that E-cadherin (Ecad), an adhesive protein that interacts in both trans (between opposing cells) and cis (on the same cell surface) conformations, facilitates desmosome assembly via an unknown mechanism. Here we use structure-function analysis to resolve the mechanistic roles of Ecad in desmosome formation. Using AFM force measurements, we demonstrate that Ecad interacts with isoform 2 of Dsg via a conserved Leu-175 on the Ecad cis binding interface. Super-resolution imaging reveals that Ecad is enriched in nascent desmosomes, supporting a role for Ecad in early desmosome assembly. Finally, confocal imaging demonstrates that desmosome assembly is initiated at sites of Ecad mediated adhesion, and that Ecad-L175 is required for efficient Dsg2 and desmoplakin recruitment to intercellular contacts. We propose that Ecad trans interactions at nascent cell-cell contacts initiate the recruitment of Dsg through direct cis interactions with Ecad which facilitates desmosome assembly.

In Situ Gelation-Induced Death of Cancer Cells Based on Proteinosomes.

Hydrogels are an excellent type of material that can be utilized as a platform for cell culture. However, when a bulky hydrogel forms on the inside of cancer cells, the result would be different. In this study, we demonstrate a method for in situ gelation inside cancer cells that can efficiently induce cell death. Glutathione-responsive proteinosomes with good biocompatibility were prepared as carriers for sodium alginate to be endocytosed by cancer cells, where the chelation between sodium alginate and free calcium ions in the culture medium occurs during the diffusion process. The uptake of the hydrogel-loaded proteinosomes into the cancer cells, and then the triggered release of hydrogel with concomitant aggregation, was well-confirmed by monitoring the change of the Young's modulus of the cells based on AFM force measurements. Accordingly, when a large amount of hydrogel formed in cells, the cell viability would be inhibited by ∼90% by MTT assay at a concentration of 5.0 μM of hydrogel-loaded proteinosomes after 48 h incubation, which clearly proves the feasibility of the demonstrated method for killing cancer cells. Although more details regarding the mechanism of cell death should be conducted in the near future, such a demonstrated method of in situ gelation inside cells provides another choice for killing cancer cells.

Substrate effects on cell-envelope deformation during early-stage Staphylococcus aureus biofilm formation.

Bacterial adhesion to a surface is the first step in biofilm formation, and adhesive forces between the surface and a bacterium are believed to give rise to planktonic-to-biofilm phenotypic changes. Here we use Focused-Ion-Beam (FIB) tomography with backscattered scanning electron microscopy (SEM) to image Staphyolococcus aureus (S. aureus) biofilms grown on Au-coated polystyrene (PS) and Au-coated PS modified by mixed thiols of triethylene glycol mono-11-mercaptoundecyl ether (EG3) and 1-dodecanethiol (CH3). The FIB-SEM technique enables a direct measurement of the contact area between individual bacteria and the substrate. The area of adhesion is effectively zero on the EG3 substrate. It is nonzero on all of the other substrates and increases with increasing hydrophobicity. The fact that the contact area is highest on the unmodified gold, however, indicates that other forces beyond hydrophobicity are significant. The magnitude of bacterial deformation suggests that the adhesive forces are on the order of a few nN, consistent with AFM force measurements reported in the literature. The resolution afforded by electron microscopy furthermore enables us to probe changes in the cell-envelope thickness, which decreases within and near the contact area relative to other parts of the same bacterium. This finding supports the idea that mechanosensing due to stress-induced membrane thinning plays a role in the planktonic-to-biofilm transition associated with bacterial adhesion.

Fundamental aspects of electric double layer force-distance measurements at liquid-solid interfaces using atomic force microscopy.

Atomic force microscopy (AFM) force-distance measurements are used to investigate the layered ion structure of Ionic Liquids (ILs) at the mica surface. The effects of various tip properties on the measured force profiles are examined and reveal that the measured ion position is independent of tip properties, while the tip radius affects the forces required to break through the ion layers as well as the adhesion force. Force data is collected for different ILs and directly compared with interfacial ion density profiles predicted by molecular dynamics. Through this comparison it is concluded that AFM force measurements are sensitive to the position of the ion with the larger volume and mass, suggesting that ion selectivity in force-distance measurements are related to excluded volume effects and not to electrostatic or chemical interactions between ions and AFM tip. The comparison also revealed that at distances greater than 1 nm the system maintains overall electroneutrality between the AFM tip and sample, while at smaller distances other forces (e.g., van der waals interactions) dominate and electroneutrality is no longer maintained.

Mechanically affected zone in AFM force measurements — Focus on actual probe tip geometry

The estimation of a mechanically affected zone (MAZ) during AFM force measurements on polymers or composites requires a precise knowledge of the probe tip geometry. A new calibration method is proposed to determine the tip geometry from force measurements on reference materials. The test is then modelled by finite element method in order to validate the probe geometry and to determine the (MAZ) on these materials. The numerical simulation is used to show the influence of test parameters and sample elastic modulus on the impacted volume. The evolution of MAZ diameter and depth with Young's modulus and sample displacement can be correctly described by two analytical models. It is then possible to predict the lateral resolution or depth penetration associated to an AFM force measurement on a given polymer. The aim is to optimize test parameters to characterize mechanical interphases at nanometre scale in multiphase materials and to measure polymer surfaces modulus in thin layer systems.

Direct AFM force measurements between air bubbles in aqueous monodisperse sodium poly(styrene sulfonate) solutions

Structural forces play an important role in the rheology, processing and stability of colloidal systems and complex fluids, with polyelectrolytes representing a key class of structuring colloids. Here, we explore the interactions between soft colloids, in the form of air bubbles, in solutions of monodisperse sodium poly(styrene sulfonate) as a model polyelectrolyte. It is found that by self-consistently modelling the force oscillations due to structuring of the polymer chains along with deformation of the bubbles, it is possible to precisely predict the interaction potential between approaching bubbles. In line with polyelectrolyte scaling theory, two distinct regimes of behaviour are seen, corresponding to dilute and semi-dilute polymer solutions. It is also seen that by blending monodisperse systems to give a bidisperse sample, the interaction forces between soft colloids can be controlled with a high degree of precision. At increasing bubble collision velocity, it is revealed that hydrodynamic flow overwhelms oscillatory structural interactions, showing the important disparity between equilibrium behaviour and dynamic interactions.

Study of PNA–DNA hybridization by AFM-based single-molecule force spectroscopy

Abstract The PNA–DNA interaction was probed with single-molecule AFM force measurements. The PNA sequence with only six thymine bases, p(T)6, could form stable hybrids with the complementary DNA sequence of d(A)6. Rupture of the p(T)6–d(A)6 hybrids required forces of around 148 pN, which was larger than the forces to unbind short DNA duplex that were usually below 100 pN. Fitting into the rupture force–loading rate correlation produced kinetic parameters that describe the PNA–DNA interaction, which were the thermal force scale (fβ) to be 17.5 pN, the distance to the energy barrier for dissociation (Δx) to be 0.23 nm, and the dissociation rate constant at zero force (koff) to be 2.5 s−1, respectively. The results highlighted the stronger binding affinity between PNA and DNA than between DNA and DNA. And by changing the DNA sequence to d(AAGAAA) with a single-base mismatch, no specific rupture events were observed, confirming the high sensitivity of PNA–DNA hybridization to base mismatch. This single-molecule force study probes into the energetic and kinetic aspects of PNA–DNA interactions that are not accessible by conventional bulk methods, leading to deeper understanding of PNA–DNA interactions.

Work of adhesion between mucin macromolecule and calcium-alginate gels on molecular level

The bioadhesion of biopolymers to mucus layers is of great interest for the development of drug delivery systems. Herein we use AFM force measurements to evaluate the interaction on molecular level between a mucin macromolecule attached to an AFM tip and a calcium-alginate gel layer. The total work of adhesion is measured from the AFM force curves depending on different parameters: time of contact, G/M ratio of the alginate, and crosslink ratio of the gel. The total work of adhesion is found to be in the range of 1×10−19 to 6×10−18J. The results show that the work of adhesion increases with the time of contact but it is independent from the molecular mass of the alginate, the G/M ratio of the alginate and crosslink ratio of the gel.

Mechanical Characterization of Ultrathin DLC Suspended Membranes for CMUT Applications

To increase the spatial resolution of CMUT based ultrasound imaging, the feasibility of devices made of arrays of vibrating areas in the square micrometer range is investigated. The manufacturing and characterization of ultrathin diamond like carbon suspended membranes that can act as the mobile electrode of capacitive micromachined ultrasonic transducers are described. To get significant displacements, the membrane thickness must be reduced to the nanometer range. Consequently, a 5 to 20nm thick Ni/DLC/Ni stack is first deposited by electron cyclotron resonance. The three-layer stack is then transferred on test devices to form suspended membranes over 0.5 to 2μm wide trenches. The device characterization includes SEM imaging and AFM force measurements. The mechanical properties of the suspended sheets were extracted, which allows the determination of the bending rigidity (1 x 10-14 to 20 x10-14N.m) of the mobile part of the transducer. This parameter is required for device modelling as it integrates the properties of the final membrane (material, thickness, surface alteration, etc.).

AFM-Based Study of the Interaction Forces between Ceria, Silicon Dioxide and Polyurethane Pad during Non-Prestonian Polishing of Silicon Dioxide Films

A colloidal AFM-based method was used to understand the role of diallyldimethyl ammonium chloride (DADMAC) molecules in non-Prestonian silicon dioxide removal obtained using ceria-based slurries. A series of force-distance measurements between silicon dioxide films, polyurethane IC1000 polishing pad and ceria abrasives in liquid media with and without DADMAC molecules were made. It was shown that at 15 mM concentration, DADMAC molecules yield non-Prestonian behavior by interfering between ceria particles and the oxide film. The effects of the DADMAC additive on the removal rates of the oxide films and their corresponding coefficients of friction (COFs) values were also investigated. Finally, the correlation between AFM force measurements, removal rates and COF values measured during polishing are discussed. Interestingly, below a threshold COF value of ∼0.23 to 0.24, corresponding to a threshold down pressure of ∼2psi for both 15 mM and 25 mM DADMAC concentration, no oxide film removal was observed.

Direct AFM force measurements between air bubbles in aqueous polydisperse sodium poly(styrene sulfonate) solutions: Effect of collision speed, polyelectrolyte concentration and molar mass

Interactions between colliding air bubbles in aqueous solutions of polydisperse sodium poly(styrene sulfonate) (NaPSS) using direct force measurements were studied. The forces measured with deformable interfaces were shown to be more sensitive to the presence of the polyelectrolytes when compared to similar measurements using rigid interfaces. The experimental factors that were examined were NaPSS concentration, bubble collision velocity and polyelectrolyte molar mass. These measurements were then compared with an analytical model based on polyelectrolyte scaling theory in order to explain the effects of concentration and bubble deformation on the interaction between bubbles. Typically structural forces from the presence of monodisperse polyelectrolyte between interacting surfaces may be expected, however, it was found that the polydispersity in molar mass resulted in the structural forces to be smoothed and only a depletion interaction was able to be measured between interacting bubbles. It was found that an increase in number density of NaPSS molecules resulted in an increase in the magnitude of the depletion interaction. Conversely this interaction was overwhelmed by an increase in the fluid flow in the system at higher bubble collision velocities. Polymer molar mass dispersity plays a significant role in the interactions present between the bubbles and has implications that also affect the polyelectrolyte overlap concentration of the solution. Further understanding of these implications can be expected to play a role in the improvement in operations in such fields as water treatment and mineral processing where polyelectrolytes are used extensively.