Analysis Of Force-distance Curves Research Articles

Pile-Ups Formation in AFM-Based Nanolithography: Morpho-Mechanical Characterization and Removal Strategies.

In recent decades, great efforts have been made to develop innovative, effective, and accurate nanofabrication techniques stimulated by the growing demand for nanostructures. Nowadays, mechanical tip-based emerged as the most promising nanolithography technique, allowing the pattern of nanostructures with a sub-nanometer resolution, high reproducibility, and accuracy. Unfortunately, these nanostructures result in contoured pile-ups that could limit their use and future integration into high-tech devices. The removal of pile-ups is still an open challenge. In this perspective, two different AFM-based approaches, i.e., Force Modulation Mode imaging and force-distance curve analysis, were used to characterize the structure of pile-ups at the edges of nanogrooves patterned on PMMA substrate by means of Pulse-Atomic Force Lithography. Our experimental results showed that the material in pile-ups was less stiff than the pristine polymer. Based on this evidence, we have developed an effective strategy to easily remove pile-ups, preserving the shape and the morphology of nanostructures.

A Novel Topography and Elasticity Synchronous Measure Approach With an AFM

Atomic force microscopy (AFM) is a powerful tool to measure the topography or the mechanical properties of samples at the nanoscale. Currently, the method of force–distance curve analysis is usually adopted to obtain the mechanical properties by an AFM, which presents the drawbacks of long time consuming and impossibility to measure the topography and the mechanical properties simultaneously. To address these problems, this article proposes a novel topography/elasticity measurement approach, which efficiently obtains the topography and the mechanical properties of detected samples with a conventional AFM. To be specific, the set points for forward and backward scanning are carefully selected to be different, so as to yield different sample deformations and piezoactuator displacement, for the same point with forward and backward scanning. On this basis, a mathematical model is set up to simultaneously calculate the topography and Young’s modulus of the sample surface by carefully analyzing the obtained data from the scanning processes. In addition, considering the effect of $z$ -axis drift during the measurement process, an information fusion algorithm based on the least-squares method and the Kalman filter is proposed to successfully compensate for the drift and thus further improve the imaging quality. Experimental results are included to demonstrate the good performance of the proposed approach for topography and mechanical properties’ measurement.

Effect of Trypan Blue on Descemet Membrane Elasticity

To evaluate the effect of trypan blue on the elastic property of Descemet membrane (DM) by atomic force microscopy. Human corneas (n = 10) were obtained from the Illinois Eye Bank (Chicago, IL). The DM was isolated and divided into two halves, one half was stained with ophthalmic trypan blue (Vision Blue, 0.06%, DORC International), whereas the unstained other half served as control. The DM samples were then tested using the atomic force microscope. Data were analyzed using the Hertz model for the evaluation of the Young modulus of elasticity. Atomic force microscopy showed higher cantilever deflection on trypan blue-stained DM compared with control, and the difference was statistically significant (P = 0.03). Force-distance curve analysis also revealed a statistically significant increase in the Young modulus of elasticity in the trypan blue-stained samples (10.5 ± 1.4 kPa) compared with the control (5.8 ± 0.8 kPa), (P < 0.0001). Our results suggest that trypan blue may decrease DM elasticity and consequently increase its stiffness. This may influence the graft adherence when used for endothelial keratoplasty.

Particle detachment from fluid interfaces: theory vs. experiments.

Microparticle adsorption and self-assembly at fluid interfaces are strongly affected by the particle three-phase contact angle θ. On the single-particle level, θ can be determined by several techniques, including colloidal-probe AFM, the gel-trapping technique (GTT) and the freeze-fracture shadow-casting (FreSCa) method. While GTT and FreSCa provide contact angle distributions measured over many particles, colloidal-probe AFM measures the wettability of an individual (specified) particle attached onto an AFM cantilever. In this paper, we extract θ for smooth microparticles through the analysis of force-distance curves upon particle approach and retraction from the fluid interface. From each retraction curve, we determine: (i) the maximal force, Fmax; (ii) the detachment distance, Dmax; and (iii) the work for quasistatic detachment, W. To relate Fmax, Dmax and W to θ, we developed a detailed theoretical model based on the capillary theory of flotation. The model was validated in three different ways. First, the contact angles, evaluated from Fmax, Dmax and W, are all close in value and were used to calculate the entire force-distance curves upon particle retraction without any adjustable parameters. Second, the model was successfully applied to predict the experimental force-distance curve of a truncated sphere, whose cut is positioned below the point of particle detachment from the interface. Third, our theory was confirmed by the excellent agreement between the particle contact angles obtained from the colloidal-probe AFM data and the ensemble-average contact angles measured by both GTT and FreSCa. Additionally, we devised a very accurate closed-form expression for W (representing the energy barrier for particle detachment), thus extending previous results in the literature.

Evaluation of Chemical Interactions between Small Molecules in the Gas Phase Using Chemical Force Microscopy.

Chemical force microscopy analyzes the interactions between various chemical/biochemical moieties in situ. In this work we examined force-distance curves and lateral force to measure the interaction between modified AFM tips and differently functionalized molecular monolayers. Especially for the measurements in gas phase, we investigated the effect of humidity on the analysis of force-distance curves and the images in lateral force mode. Flat chemical patterns composed of different functional groups were made through micro-contact printing and lateral force mode provided more resolved analysis of the chemical patterns. From the images of 1-octadecanethiol/11-mercapto-1-undecanoic acid patterns, the amine group functionalized tip brought out higher contrast of the patterns than an intact silicon nitride tip owing to the additional chemical interaction between carboxyl and amine groups. For more complex chemical interactions, relative chemical affinities toward specific peptides were assessed on the pattern of 1-octadecanethiol/phenyl-terminated alkanethiol. The lateral image of chemical force microscopy reflected specific preference of a peptide to phenyl group as well as the hydrophobic interaction.

Multiscale sensing of antibody-antigen interactions by organic transistors and single-molecule force spectroscopy.

Antibody-antigen (Ab-Ag) recognition is the primary event at the basis of many biosensing platforms. In label-free biosensors, these events occurring at solid-liquid interfaces are complex and often difficult to control technologically across the smallest length scales down to the molecular scale. Here a molecular-scale technique, such as single-molecule force spectroscopy, is performed across areas of a real electrode functionalized for the immunodetection of an inflammatory cytokine, viz. interleukin-4 (IL4). The statistical analysis of force-distance curves allows us to quantify the probability, the characteristic length scales, the adhesion energy, and the time scales of specific recognition. These results enable us to rationalize the response of an electrolyte-gated organic field-effect transistor (EGOFET) operated as an IL4 immunosensor. Two different strategies for the immobilization of IL4 antibodies on the Au gate electrode have been compared: antibodies are bound to (i) a smooth film of His-tagged protein G (PG)/Au; (ii) a 6-aminohexanethiol (HSC6NH2) self-assembled monolayer on Au through glutaraldehyde. The most sensitive EGOFET (concentration minimum detection level down to 5 nM of IL4) is obtained with the first functionalization strategy. This result is correlated to the highest probability (30%) of specific binding events detected by force spectroscopy on Ab/PG/Au electrodes, compared to 10% probability on electrodes with the second functionalization. Specifically, this demonstrates that Ab/PG/Au yields the largest areal density of oriented antibodies available for recognition. More in general, this work shows that specific recognition events in multiscale biosensors can be assessed, quantified, and optimized by means of a nanoscale technique.

The influence of aminophylline on the nanostructure and nanomechanics of T lymphocytes: an AFM study.

Although much progress has been made in the illustration of the mechanism of aminophylline (AM) treating asthma, there is no data about its effect on the nanostructure and nanomechanics of T lymphocytes. Here, we presented atomic force spectroscopy (AFM)-based investigations at the nanoscale level to address the above fundamental biophysical questions. As increasing AM treatment time, T lymphocytes' volume nearly double increased and then decreased. The changes of nanostructural features of the cell membrane, i.e., mean height of particles, root-mean-square roughness (Rq), crack and fragment appearance, increased with AM treatment time. T lymphocytes were completely destroyed with 96-h treatment, and they existed in the form of small fragments. Analysis of force-distance curves showed that the adhesion force of cell surface decreased significantly with the increase of AM treatment time, while the cell stiffness increased firstly and then decreased. These changes were closely correlated to the characteristics and process of cell oncosis. In total, these quantitative and qualitative changes of T lymphocytes' structure and nanomechanical properties suggested that AM could induce T lymphocyte oncosis to exert anti-inflammatory effects for treating asthma. These findings provide new insights into the T lymphocyte oncosis and the anti-inflammatory mechanism and immune regulation actions of AM.

Efficient broken line fitting procedure for analysis of force spectroscopy curves in chemical force microscopy

The procedure for the analysis of force-distance curves in chemical force microscopy is presented. This procedure is based upon the Broken Line Fitting algorithm with an adaptation of knots positions. The strength of this method relies on the fact that it has O(N) complexity, which means that it is as efficient as standard peak detection techniques utilized by commercially available software. It is shown by means of computer simulations that the algorithm is able to detect snap-out points of a height comparable to a noise level, which is a significant improvement in comparison to previously reported techniques. The proposed method is also resistant to base line distortions. Using this procedure for an analysis of CH3-CH3 interactions enabled measurements of interactions between only two molecules, which has been confirmed experimentally. The obtained results strongly support validity of the Johnson-Kendall-Roberts model at the sub-nanometer scale.

Mechanism of Nanoparticle Formation from Ternary Coground Phenytoin and Its Derivatives

The mechanism of drug nanoparticle formation of phenytoin (DPH) and its derivatives monomethylphenytoin (MDPH) and dimethylphenytoin (DMDPH) was investigated. The drug, polyvinylpyrrolidone K17 (PVP), and sodium dodecyl sulfate were coground to obtain the ground mixture (GM). The DPH GM was amorphous; however, MDPH and DMDPH GMs contained drug crystals. Spectral changes in infrared and (13)C solid-state nuclear magnetic resonance were observed in the DPH GM, partially observed in the MDPH GM, and hardly observed in the DMDPH GM. Mean particle sizes of the DPH, MDPH, and DMDPH GM nanosuspension were almost the same; however, stability after storage differed in the order of DPH > MDPH > DMDPH. The intermolecular interaction between the drug and PVP reflected not only the crystallinity of the drug in the GM but also the stability of the GM suspension. The size and stiffness of drug nanoparticles were evaluated using atomic force microscopy. Crystallization of the amorphous GM and agglomeration of the primary nanocrystals were observed in the DPH GM suspension. In contrast, primary nanocrystals were observed in the DMDPH GM suspension. The size of the drug nanocrystals formed from the different molecular states of the drug in the GM reflects the agglomerated states in water and stability.

Chain Stiffness of Elastin-Like Polypeptides

The hydrodynamic radii of a series of genetically engineered monodisperse elastin like polypeptides (ELP) was determined by dynamic light scattering in aqueous solution as function of molar mass. Utilizing the known theoretical expression for the hydrodynamic radius of wormlike chains, the Kuhn statistical segment length was determined to be lk = 2.1 nm, assuming that the length of the peptide repeat unit was b = 0.365 nm, a value derived for a coiled conformation of ELP. The resulting chain stiffness is significantly larger than previously reported by force-distance curve analysis (lk < 0.4 nm). The possible occurrence of superstructures, such as hairpins or helices, would reduce the contour length of the ELP, further increasing lk. Accordingly, the value lk = 2.1 nm reported here represents a lower limit of the chain stiffness for ELP.

Robust Strategies for Automated AFM Force Curve Analysis—II: Adhesion-Influenced Indentation of Soft, Elastic Materials

In the first of this two-part discourse on the extraction of elastic properties from atomic force microscopy (AFM) data, a scheme for automating the analysis of force-distance curves was introduced and experimentally validated for the Hertzian (i.e., linearly elastic and noninteractive probe-sample pairs) indentation of soft, inhomogeneous materials. In the presence of probe-sample adhesive interactions, which are common especially during retraction of the rigid tip from soft materials, the Hertzian models are no longer adequate. A number of theories (e.g., Johnson-Kendall-Roberts and Derjaguin-Muller-Toporov), covering the full range of sample compliance relative to adhesive force and tip radius, are available for analysis of such data. We incorporated Pietrement and Troyon's approximation (2000, "General Equations Describing Elastic Indentation Depth and Normal Contact Stiffness Versus Load," J. Colloid Interface Sci., 226(1), pp. 166-171) of the Maugis-Dugdale model into the automated procedure. The scheme developed for the processing of Hertzian data was extended to allow for adhesive contact by applying the Pietrement-Troyon equation. Retraction force-displacement data from the indentation of polyvinyl alcohol gels were processed using the customized software. Many of the retraction curves exhibited strong adhesive interactions that were absent in extension. We compared the values of Young's modulus extracted from the retraction data to the values obtained from the extension data and from macroscopic uniaxial compression tests. Application of adhesive contact models and the automated scheme to the retraction curves yielded average values of Young's modulus close to those obtained with Hertzian models for the extension curves. The Pietrement-Troyon equation provided a good fit to the data as indicated by small values of the mean-square error. The Maugis-Dugdale theory is capable of accurately modeling adhesive contact between a rigid spherical indenter and a soft, elastic sample. Pietrement and Troyon's empirical equation greatly simplifies the theory and renders it compatible with the general automation strategies that we developed for Hertzian analysis. Our comprehensive algorithm for automated extraction of Young's moduli from AFM indentation data has been expanded to recognize the presence of either adhesive or Hertzian behavior and apply the appropriate contact model.

Evaluation of the Mechanical Properties of Carbon Black Reinforced Natural Rubber by Atomic Force Microscopy

Atomic force microscopy (AFM) has an advantage of obtaining topographic and mechanical properties at the same time. In analyzing the force-distance curve using Hertz theory, Young's modulus is obtained with nanometer-scale resolution. Furthermore, sample deformation by the force exerted is also estimated from the force-distance curve analysis. We can reconstruct a real topographic image by incorporating apparent height with deformation image. We applied this method for obtaining information on mechanical properties of carbon black reinforced natural rubber. We were able to obtain Young's modulus distribution image together with apparent topographic and reconstructed real topographic images. Then we were able to recognize three regions; rubber, carbon black (or bound rubber) and interfacial regions. Though the existence of these regions had been investigated by pulsed nuclear magnetic resonance, this paper would be the first report on the quantitative evaluation of the interfacial region in real space.

原子間力顕微鏡によるカーボンブラック充てん天然ゴムの力学物性評価

Atomic force microscopy (AFM) has an advantage of obtaining topographic and mechanical properties at the same time. In analyzing the force-distance curve using Hertz theory, Young's modulus is obtained with nanometer-scale resolution. Furthermore, sample deformation by the force exerted is also estimated from the force-distance curve analysis. We can reconstruct a real topographic image by incorporating apparent height with deformation image. We applied this method for obtaining information on mechanical properties of carbon black reinforced natural rubber. We were able to obtain Young's modulus distribution image together with apparent topographic and reconstructed real topographic images. Then we were able to recognize three regions; rubber, carbon black (or bound rubber) and interfacial regions. Though the existence of these regions had been investigated by pulsed nuclear magnetic resonance, this paper would be the first report on the quantitative evaluation of the interfacial region in real space.

Detailed analysis of forces influencing lateral resolution for Q-control and tapping mode

The recently introduced active quality factor control for dynamic force microscopy (Q-control) in liquids promises higher sensitivity, and thus, smaller interaction forces compared to normal tapping (intermittent contact) mode. By a careful analysis of force distance curves, we show that the lateral resolution obtained on fragile biological membranes is actually comparable for both modes if scan parameters are optimized accordingly. In addition, Q-control is limited to small scan rates only.