Atomic Force Microscopy Measurements Research Articles

N-Type Doping Effect of Anthracene-Based Cationic Dyes in Organic Electronics.

n-Type doping for improving the electrical characteristics and air stability of n-type organic semiconductors (OSCs) is important for realizing advanced future electronics. Herein, we report a selection method for an effective n-type dopant with an optimized structure and thickness based on anthracene cationic dyes with high miscibility induced by a molecular structure similar to that of OSCs. Among the doped OSCs evaluated, rhodamine B (RhoB)-doped OSC exhibits the highest density, a smallest roughness of 2.69 nm, a phase deviation of 0.85° according to atomic force microscopy measurements, and the highest electron mobility (μ), showing its high miscibility. Surface doping of RhoB affords the lowest contact resistance of 2.01 × 105 Ω cm compared to bulk and contact doping, resulting in an effective doping structure. The RhoB-doped OSC retains 81.63% of the original μ value of 6.13 × 10-2 cm2 V-1 s-1 after 15 days, whereas pristine OSC shows a lower μ of 2.33 × 10-2 cm2 V-1 s-1 and maintains only 4.41% of the original value after 15 days. Our findings demonstrate that this methodology is effective for the selection of a high-performance n-type dopant for OSCs toward the development of high-performance and air-stable n-type organic electronics.

Unveiling the 3D Morphology of Epitaxial GaAs/AlGaAs Quantum Dots.

Strain-free GaAs/AlGaAs semiconductor quantum dots (QDs) grown by droplet etching and nanohole infilling (DENI) are highly promising candidates for the on-demand generation of indistinguishable and entangled photon sources. The spectroscopic fingerprint and quantum optical properties of QDs are significantly influenced by their morphology. The effects of nanohole geometry and infilled material on the exciton binding energies and fine structure splitting are well-understood. However, a comprehensive understanding of GaAs/AlGaAs QD morphology remains elusive. To address this, we employ high-resolution scanning transmission electron microscopy (STEM) and reverse engineering through selective chemical etching and atomic force microscopy (AFM). Cross-sectional STEM of uncapped QDs reveals an inverted conical nanohole with Al-rich sidewalls and defect-free interfaces. Subsequent selective chemical etching and AFM measurements further reveal asymmetries in element distribution. This study enhances the understanding of DENI QD morphology and provides a fundamental three-dimensional structural model for simulating and optimizing their optoelectronic properties.

PyFMLab: Open-source software for atomic force microscopy microrheology data analysis

Background Atomic force microscopy (AFM) is one of the main techniques used to characterize the mechanical properties of soft biological samples and biomaterials at the nanoscale. Despite efforts made by the AFM community to promote open-source data analysis tools, standardization continues to be a significant concern in a field that requires common analysis procedures. AFM-based mechanical measurements involve applying a controlled force to the sample and measure the resulting deformation in the so-called force-distance curves. These may include simple approach and retract or oscillatory cycles at various frequencies (microrheology). To extract quantitative parameters, such as the elastic modulus, from these measurements, AFM measurements are processed using data analysis software. Although open tools exist and allow obtaining the mechanical properties of the sample, most of them only include standard elastic models and do not allow the processing of microrheology data. In this work, we have developed an open-source software package (called PyFMLab, as of python force microscopy laboratory) capable of determining the viscoelastic properties of samples from both conventional force-distance curves and microrheology measurements. Methods PyFMLab has been written in Python, which provides an accessible syntax and sufficient computational efficiency. The software features were divided into separate, self-contained libraries to enhance code organization and modularity and to improve readability, maintainability, testability, and reusability. To validate PyFMLab, two AFM datasets, one composed of simple force curves and another including oscillatory measurements, were collected on HeLa cells. Results The viscoelastic parameters obtained on the two datasets analysed using PyFMLab were validated against data processing proprietary software and against validated MATLAB routines developed before obtaining equivalent results. Conclusions Its open-source nature and versatility makes PyFMLab an open-source solution that paves the way for standardized viscoelastic characterization of biological samples from both force-distance curves and microrheology measurements.

Colloidal Probe Technique Optimization for Determination of Young's Modulus of Soft Adhesive Hydrogels.

Atomic force microscopy (AFM) is a valuable tool for determining the Young's modulus of a wide range of materials. However, it faces challenges, particularly when assessing adhesive materials like soft poly(N-isopropylacrylamide) (pNIPAM) hydrogels. This study focuses on enhancing the consistency and reliability of AFM measurements by functionally modifying AFM spherical tip cantilevers to address substrate adhesion issues with these hydrogels. Specifically, hydrophobic functionalization with 1H,1H,2H,2H-perfluorooctyltrichlorosilane (PFOCTS) emerged as the most effective approach, yielding consistent and reliable Young's modulus data across various pNIPAM hydrogel samples. This work highlights the importance of optimizing data acquisition in AFM, rather than relying on postprocessing, to reduce inconsistencies in Young's modulus assessment.

Insights into structure, morphology and conductivity of the earth-abundant NASICON phosphate, Na4MnFe(PO4)3.

Phosphate-based NASICON materials are an excellent candidate for both electrode and solid electrolyte materials in sodium-ion batteries (SIBs). The development of new NASICON materials with higher ionic and electronic conductivities based on low cost and abundant elements is necessary for advancement of SIBs. In this study, we report the structure, morphology and conductivity of the earth-abundant Mn/Fe-based NASICON phosphate Na4MnFe(PO4)3. Pure phase powders were synthesized by solution-assisted solid-state reaction, sol-gel and Pechini methods. From refined X-ray diffraction data, the prepared phosphate was found to crystallize in trigonal symmetry with space group R3̄c. The effect of synthesis method on microstructure and conductivity was investigated using scanning electron microscopy (SEM), atomic force microscopy (AFM) and impedance measurements. Smaller particle size and regular distribution of the powder was designed using a Pechini route. Impedance measurement showed a notable enhancement in conductivity, from 0.543 × 10-7 to 1.52 × 10-7 S cm-1 at 30 °C, when the powder synthesis method was altered from a solution-assisted solid-state reaction to the Pechini route, highlighting the remarkable effect of the synthesis method on conductivity.

Hypoxic extracellular vesicles from hiPSCs protect cardiomyocytes from oxidative damage by transferring antioxidant proteins and enhancing Akt/Erk/NRF2 signaling

BackgroundStem cell-derived extracellular vesicles (EVs) are an emerging class of therapeutics with excellent biocompatibility, bioactivity and pro-regenerative capacity. One of the potential targets for EV-based medicines are cardiovascular diseases (CVD). In this work we used EVs derived from human induced pluripotent stem cells (hiPSCs; hiPS-EVs) cultured under different oxygen concentrations (21, 5 and 3% O2) to dissect the molecular mechanisms responsible for cardioprotection.MethodsEVs were isolated by ultrafiltration combined with size exclusion chromatography (UF + SEC), followed by characterization by nanoparticle tracking analysis, atomic force microscopy (AFM) and Western blot methods. Liquid chromatography and tandem mass spectrometry coupled with bioinformatic analyses were used to identify differentially enriched proteins in various oxygen conditions. We directly compared the cardioprotective effects of these EVs in an oxygen-glucose deprivation/reoxygenation (OGD/R) model of cardiomyocyte (CM) injury. Using advanced molecular biology, fluorescence microscopy, atomic force spectroscopy and bioinformatics techniques, we investigated intracellular signaling pathways involved in the regulation of cell survival, apoptosis and antioxidant response. The direct effect of EVs on NRF2-regulated signaling was evaluated in CMs following NRF2 inhibition with ML385.ResultsWe demonstrate that hiPS-EVs derived from physiological hypoxia at 5% O2 (EV-H5) exert enhanced cytoprotective function towards damaged CMs compared to EVs derived from other tested oxygen conditions (normoxia; EV-N and hypoxia 3% O2; EV-H3). This resulted from higher phosphorylation rates of Akt kinase in the recipient cells after transfer, modulation of AMPK activity and reduced apoptosis. Furthermore, we provide direct evidence for improved calcium signaling and sustained contractility in CMs treated with EV-H5 using AFM measurements. Mechanistically, our mass spectrometry and bioinformatics analyses revealed differentially enriched proteins in EV-H5 associated with the antioxidant pathway regulated by NRF2. In this regard, EV-H5 increased the nuclear translocation of NRF2 protein and enhanced its transcription in CMs upon OGD/R. In contrast, inhibition of NRF2 with ML385 abolished the protective effect of EVs on CMs.ConclusionsIn this work, we demonstrate a superior cardioprotective function of EV-H5 compared to EV-N and EV-H3. Such EVs were most effective in restoring redox balance in stressed CMs, preserving their contractile function and preventing cell death. Our data support the potential use of hiPS-EVs derived from physiological hypoxia, as cell-free therapeutics with regenerative properties for the treatment of cardiac diseases.

Hypoxic extracellular vesicles from hiPSCs protect cardiomyocytes from oxidative damage by transferring antioxidant proteins and enhancing Akt/Erk/NRF2 signaling

BackgroundStem cell-derived extracellular vesicles (EVs) are an emerging class of therapeutics with excellent biocompatibility, bioactivity and pro-regenerative capacity. One of the potential targets for EV-based medicines are cardiovascular diseases (CVD). In this work we used EVs derived from human induced pluripotent stem cells (hiPSCs; hiPS-EVs) cultured under different oxygen concentrations (21, 5 and 3% O2) to dissect the molecular mechanisms responsible for cardioprotection.MethodsEVs were isolated by ultrafiltration combined with size exclusion chromatography (UF + SEC), followed by characterization by nanoparticle tracking analysis, atomic force microscopy (AFM) and Western blot methods. Liquid chromatography and tandem mass spectrometry coupled with bioinformatic analyses were used to identify differentially enriched proteins in various oxygen conditions. We directly compared the cardioprotective effects of these EVs in an oxygen-glucose deprivation/reoxygenation (OGD/R) model of cardiomyocyte (CM) injury. Using advanced molecular biology, fluorescence microscopy, atomic force spectroscopy and bioinformatics techniques, we investigated intracellular signaling pathways involved in the regulation of cell survival, apoptosis and antioxidant response. The direct effect of EVs on NRF2-regulated signaling was evaluated in CMs following NRF2 inhibition with ML385.ResultsWe demonstrate that hiPS-EVs derived from physiological hypoxia at 5% O2 (EV-H5) exert enhanced cytoprotective function towards damaged CMs compared to EVs derived from other tested oxygen conditions (normoxia; EV-N and hypoxia 3% O2; EV-H3). This resulted from higher phosphorylation rates of Akt kinase in the recipient cells after transfer, modulation of AMPK activity and reduced apoptosis. Furthermore, we provide direct evidence for improved calcium signaling and sustained contractility in CMs treated with EV-H5 using AFM measurements. Mechanistically, our mass spectrometry and bioinformatics analyses revealed differentially enriched proteins in EV-H5 associated with the antioxidant pathway regulated by NRF2. In this regard, EV-H5 increased the nuclear translocation of NRF2 protein and enhanced its transcription in CMs upon OGD/R. In contrast, inhibition of NRF2 with ML385 abolished the protective effect of EVs on CMs.ConclusionsIn this work, we demonstrate a superior cardioprotective function of EV-H5 compared to EV-N and EV-H3. Such EVs were most effective in restoring redox balance in stressed CMs, preserving their contractile function and preventing cell death. Our data support the potential use of hiPS-EVs derived from physiological hypoxia, as cell-free therapeutics with regenerative properties for the treatment of cardiac diseases.

Discrete Element Method Simulation of Particulate Material Fracture Behavior on a Stretchable Single Filter Fiber with Additional Gas Flow

This study presents a comprehensive discrete element method (DEM) simulation approach for the stretching of a filter fiber with a separated polydisperse particle structure on top. For a realistic interaction between the fiber surface and the particles, the original surface of the polymer fiber was projected onto the surface of the fiber cylinder using surface imaging technologies (atomic force microscopy (AFM) and white-light interferometry). In addition, the adhesive forces between particle–fiber and particle–particle contacts were calibrated in the DEM domain using values from self-conducted AFM measurements. Fiber stretching was implemented by the linear motion of small periodic fiber elements. Discretization problems were resolved through studying the stretching of a fiber segment at the size of 8 mm. A critical fiber element length was discovered to be ≈100 μm for minimizing discretization dependencies during the cracking of the particle structure. The number and density of particle–particle contacts within the particle loading on the fiber were obtained at two different elongation rates. Effects such as densification of the particulate structure and increased detachment due to additional air flow were demonstrated.

Stability of bubble-particle hetero-coagulates accessed by atomic force microscopy to understand the froth flotation of agglomerating hydrophobic fines

The key microprocesses, which determine the efficiency in froth flotation are the formation and breakage of particle-bubble hetero-coagulates. Agglomeration can be used to increase the recovery of fine particles < 20 µm. Here the stability of hetero-coagulates consisting of agglomerates and gas bubble determines the process performance. Therefore, the stability of agglomerate-bubble hetero-coagulates was accessed by atomic force microscopy (AFM) on particle-laden gas bubbles, agglomerates and pristine gas bubbles without particles in the interface. The force and work of adhesion from AFM measurements were compared to the detaching force and the detaching energy that act on agglomerate-bubble and particle-bubble hetero-coagulates under turbulent conditions, similar to those in a flotation cell. This comparison provides the maximum size of agglomerates and single particles that can remain attached to the gas bubbles at a given energy dissipation rate. The results suggest that the size of agglomerates attached to gas bubbles can grow beyond the Kolmogorov length, which limits the size of agglomerates under turbulent conditions. The findings are supported by in-line probe images of agglomerate-bubble hetero-coagulates that were captured in an aerated stirred tank under turbulent conditions. It was further shown that the particle detachment from particle-laden bubbles is governed by the deformation of the underlying gas bubble and the local particle coverage.

On the role of water in regulating the mechanics of collagen fibers

The mechanical properties of collagen fiber–based materials have garnered considerable attention owing to their application in various hydration environments. Herein, we conducted a comprehensive investigation on the mediatory role of water in the mechanical properties and structure of collagen fibers. Lower hydration levels are conducive to the mechanical strength, particularly the tensile and tear properties, and reduce the softness of collagen fibers as well as the D-period and the lateral spacing between collagen molecules. Atomic force microscopy measurements indicate that lower hydration levels also enhance the roughness, adhesion force and lateral forces between collagen fibers. Theoretical calculations further reveal that the hydration level regulates weaker components of water-mediated interactions, such as electrostatic and van der Waals forces, which dominate the resistance against mechanical shock. Our findings provide valuable insights into the role of water in regulating the mechanical behaviour of collagen fibers, thereby contributing to the development of novel high-performance collagen fiber materials.

Poly(vinyl pyridine) coatings cross-linked with transition metal complexes as active layers for biosensors sensitive to protein adsorption and cell adhesion

The possibility of application of poly(4-vinyl pyridine) layers cross-linked with transition metal complexes as active layers in biomedical sensors was tested. The successful modification of the P4VP coating with CuBr2 or ZnBr2 was verified using time of flight - secondary ion mass spectrometry and X-ray photoelectron spectroscopy. The topography and wettability of the coatings were examined by using atomic force microscopy and water contact angles measurements, respectively. Tests of biological activity of coatings indicated strong protein adsorption, good biocompatibility, and no antimicrobial activity. The potential of the coatings to be used as active layers of biosensors was verified, by systematic impedance-based measurements, which showed the sensitivity of the P4VP:CuBr2 coatings to the presence of proteins and cells in different concentrations. The high selectivity of the coatings toward the defined analyte was confirmed by the specific antigen–antibody immunoreaction, and the possibility of in situ monitoring of protein adsorption and cell adhesion also for individual cells was presented. Finally, the conductive response of a bilayer system that mimics Organic Field Effect Transistor was shown. These results point to a great potential for both coatings to serve as active layers of sensitive and highly selective biosensors.

Tuning the Topo-Morphological properties of ITO Films using Al-Ag interlayer for Low-Resistance Optoelectronics Devices

Indium tin oxide (ITO) is recently attracting intense attention for application as transparent conducting electrode in different optoelectronic devices including solar cells, liquid crystal displays and organic light emitting diodes. This is attributed to their high optical transmittance in the visible region and good electrical conductivity. In this work, surface topological-morphological (topo-morphological) and electrical properties of ITO based multilayer films with aluminum-silver (Al-Ag) metal interlayer (ITO/Al-Ag/ITO) are investigated after post annealing treatment at 300-500oC by atomic force microscopic (AFM), field emission scanning electron microscopy (FESEM), four-point probe and hall-effect techniques respectively. The ITO/Al-Ag/ITO films are deposited by direct current and radio frequency magnetron sputtering techniques on p-type Si at room temperature. The results showed a smooth surface topology by as-deposited film with films smoothness improving after post annealing treatment as analyzed by AFM method. Sharp crystallites peaks were obtained by all the films with smaller peaks diffusing and recombining to form larger films with increasing post-annealing temperature. The films root means square roughness increased as the temperature increases with film annealed at 500oC showing a superior and enhanced microstructure. Compared to as-deposited film, careful observation shows that surface morphology smoothness increased with increase in temperature with films annealed at 400oC and 500oC showing highest increasing surface smoothness pattern as determined by FESEM technique. Similarly, higher grain sizes are observed especially by films annealed at 400oC and 500oC due to the heat absorption which causes the particles to expand thereby narrowing the grain boundaries and subsequently improve the surface smoothness. These FESEM findings are consistent with AFM measurements confirming the high surface property and enhanced grain size with increasing post annealing temperature. The films exhibit decreased electrical resistivity and sheet resistance while carrier concentration and Hall mobility increased with increasing post annealing treatment indicating highest corresponding values of...

Remotely Controlled Surface Charge Modulation of Magnetoelectric Nanogenerators for Swift and Efficient Drug Delivery.

We have developed a highly efficient technique of magnetically controlled swift loading and release of doxorubicin (DOX) drug using a magnetoelectric nanogenerator (MENG). Core-shell nanostructured MENG with a magnetostrictive core and piezoelectric shell act as field-responsive nanocarriers and possess the capability of field-triggered drug release in a cancerous environment. MENGs generate a surface electric dipole when subjected to a magnetic field due to the strain-mediated magnetoelectric effect. The capability of directional magnetic field-assisted modulation of the surface electrical dipole of MENG provides a mechanism to create/break ionic bonds with DOX molecules, which facilitates efficient drug attachment and on-demand swift detachment of the drug at a targeted site. The magnetic field-assisted drug-loading mechanism was minutely analyzed using spectrophotometry and Raman spectroscopy. The detailed time-dependent analysis of controlled drug release by the MENG under unidirectional and rotating magnetic field excitation was conducted using field-emission scanning electron microscopy, energy-dispersive X-ray, and atomic force microscopic measurements. In vitro, experiments validate the cytocompatibility and magnetically assisted on-demand and swift DOX drug delivery by the MENG near MCF-7 breast cancer cells, which results in a significant enhancement of cancer cell killing efficiency. A state-of-the-art experiment was performed to visualize the nanoscale magnetoelectric effect of MENG using off-axis electron holography under Lorentz conditions.

Exploring asphaltene aggregation: Model systems based on toluene-heptane mixtures

This work evaluates how chemical characteristics, such as polarity and aromaticity, can affect asphaltene aggregation. The asphaltene fraction was extracted from two different crude oils by precipitation in n-heptane, and these extracted asphaltenes were named A and B. Based on infrared spectroscopy (FTIR) and nuclear magnetic resonance (NMR) analyses, we found that asphaltenes B present greater aromaticity. According to X-ray photoelectron spectroscopy (XPS), asphaltene B showed higher heteroatom content. Model systems based on toluene/n-heptane/asphaltene (0.05 g/L) were prepared to evaluate the aggregation/precipitation of asphaltenes. Dynamic light scattering (DLS) analysis of aggregation kinetics revealed that aromatic asphaltenes with higher heteroatom content tend to form larger aggregates. Moreover, hydroxyl content exhibits a greater impact on aggregation compared to diffusivity. Furthermore, once the aggregates reach a critical size, the suspension stability is reduced, and the aggregates sediment. The atomic force microscopy (AFM) and DLS results revealed a wide range of particle size distribution. The larger clusters likely consisted of smaller aggregates that adhered together. Still, we highlight that the sizes of these aggregates determined by AFM are not directly comparable to the measurements obtained from DLS. The drying of the samples for the AFM measurements probably affects the asphaltene aggregation process. For this reason, the results obtained from the AFM and DLS techniques are not comparable.

Vacancy Ordering in Ultrathin Copper Oxide Films on Cu(111).

Oxide thin films grown on metal surfaces have wide applications in catalysis and beyond owing to their unique surface structures compared to their bulk counterparts. Despite extensive studies, the atomic structures of copper surface oxides on Cu(111), commonly referred to as "44" and "29", have remained elusive. In this work, we demonstrated an approach for the structural determination of oxide surfaces using element-specific scanning tunneling microscopy (STM) imaging enhanced by functionalized tips. This approach enabled us to resolve the atomic structures of "44" and "29" surface oxides, which were further corroborated by noncontact atomic force microscopy (nc-AFM) measurements and Monte Carlo (MC) simulations. The stoichiometry of the "44" and "29" frameworks was identified as Cu23O16 and Cu16O11, respectively. Contrary to the conventional hypothesis, we observed ordered Cu vacancies within the "44" structure manifesting as peanut-shaped cavities in the hexagonal lattice. Similarly, a combination of Cu and O vacancies within the "29" structure leads to bean-shaped cavities within the pentagonal lattice. Our study has thus resolved the decades-long controversy on the atomic structures of "44" and "29" surface oxides, advancing our understanding of copper oxidation processes and introducing a robust framework for the analysis of complex oxide surfaces.

Strong Covalent Coupling in Vertically Layered SnSe2/PTAA Heterojunctions Enabled High Performance Inorganic-Organic Hybrid Photodetectors.

Controllable large-scale integration of two-dimensional (2D) materials with organic semiconductors and the realization of strong coupling between them still remain challenging. Herein, we demonstrate a wafer-scale, vertically layered SnSe2/PTAA heterojunction array with high light-trapping ability via a low-temperature molecular beam epitaxy method and a facile spin-coating process. Conductive probe atomic force microscopy (CP-AFM) measurements reveal strong rectification and photoresponse behavior in the individual SnSe2 nanosheet/PTAA heterojunction. Theoretical analysis demonstrates that vertically layered SnSe2/PTAA heterojunctions exhibit stronger C-Se covalent coupling than that of the conventional tiled type, which could facilitate more efficient charge transfer. Benefiting from these advantages, the SnSe2/PTAA heterojunction photodetectors with an optimized PTAA concentration show high performance, including a responsivity of 41.02 A/W, an external quantum efficiency of 1.31 × 104%, and high uniformity. The proposed approach for constructing large-scale 2D inorganic-organic heterostructures represents an effective route to fabricate high-performance broadband photodetectors for integrated optoelectronic systems.

Investigations on tip-based large area nanofabrication and nanometrology using a planar nanopositioning machine (NFM-100)

This paper explores large area application of tip-based nanofabrication by field emission scanning probe lithography and showcases the simultaneous possibility of atomic force microscopy on macroscopic scales. This is made possible by the combination of tip-based technology and a planar nanopositioning and nanomeasuring machine. Using long range atomic force microscopy measurement of regular grating structures, the performance of the machine is thoroughly characterized over the full 100 mm range of motion of the positioning machine, which was confirmed by repeated measurements. After initially focussing on achieving the minimum line width of < 40 nm in microscopic areas, a grating with a pitch of 1 μm is additionally fabricated over a total length of 10 mm, whereby the dimensions and deviations are also considered.

Toward coupling across inorganic/organic hybrid interfaces: polyaniline-coated gold nanoparticles with 4-aminothiophenol as gold-anchoring moieties

AbstractThe chemical binding between metal nanoparticles and (semi-)conductive polymer layers is essential to control the (opto-)electronic properties of such hybrid materials. Current approaches that achieve a conjugated binding of organic (semi-)conductive ligands to metal nanoparticles demonstrated promising functional properties, but are based on tedious multi-step organic synthesis to incorporate the required binding moieties at the chain ends of targeted macromolecular species. Herein, we explore the pre-functionalization of gold nanoparticles with p-aminothiophenol and subsequent surfactant-assisted formation of a poly(aniline) (PANI) shell as a means to access gold/PANI core–shell-type nanoparticles with enhanced conductive properties. Controlled surface deposition of these hybrid nanoparticles is achieved via template-assisted self-assembly. For these surface-deposited nanoparticles, charge transport properties are characterized at the nanoscale by conductive atomic force microscopy measurements and show a significant conductivity increase of our core–shell particles as compared to reference particles formed by conventional surfactant-assisted PANI-shell formation. Graphical Abstract

Quinoline derivatives as corrosion inhibitors for mild steel in acid medium: Deeper insights from experimental, ab initio density functional theory modeling, and in silico ecotoxicity investigations

Two (E)-2-(((2-((7-chloroquinolin-4-yl)amino)ethyl)imino)methyl)-4-R-phenol Schiff bases derivatives CMN (R = NO2) and CMP (R = H) were successfully prepared. Then, CMN and CMP were evaluated as corrosion inhibitors for 1020 mild steel in 1.0 mol L–1 HCl using different methods. Gravimetric experiments have shown that CMN and CMP reach efficiencies of 80 and 91% at 1.45 mmol L–1. Atomic Force Microscopy (AFM) and Scanning Electron Microscopy (SEM) measurements have indicated the formation of a protective adsorbed film on the mild steel surface. Electrochemical Impedance Spectroscopy (EIS), Linear Polarization Resistance (LPR), Potentiodynamic Polarization (PP), and Electrochemical Frequency Modulation (EFM) have also shed some light on electrochemical behavior of compounds. These data have depicted better polarization resistance and lower corrosion current density in the presence of both organic molecules, also proving that the process is controlled by charge transfer and that CMN and CMP are mixed-type corrosion inhibitors. ab initio Density Functional Theory (DFT) investigated how two quinoline-based molecules (CMN and CMP) prevent corrosion on iron surfaces. Simulations revealed CMP bonds more strongly to iron than CMN, leading to better protection. Simulations also showed that these inhibitor molecules form a protective layer on the iron, slowing down the movement of corrosive substances. Environment risk assessment through QSAR-based models have indicated that the corrosion inhibitors do not have the potential to bioaccumulate in fish. Still, the acute and chronic toxicity values at the different trophic levels investigated call for attention for environmentally friendly structural optimization.

Abstract PS03-08: Spatial biomechanics determines fate in breast cancer

Abstract Background: With the recent advancements of spatial omics, it has become increasingly recognized that spatial analysis the of tumor architecture is key to decipher the heterogenous intratumoral relationships between different tumor components and provide better understanding of cancer therapy resistance, as well as help to identify potential targets for personalized therapy. The challenge of the discovery and implementation of such biomarkers still lays in the technological and methodological difficulties, and their translation into clinical practice. In parallel a major advancement in cancer research has been the recognition of the importance of cancer biomechanical properties in cancer progression, metastasis, and therapy response. Methods: We developed a new computational platform to identify biomechanical drivers of cancer outcome from spatial omics data. We used it to identify recurring spatial patterns of these markers within the tumor microenvironment, and define the spatial scale of heterogeneity of such patterns. Our dataset consists in 700 primary breast cancer baseline samples analyzed with two 30-marker imaging mass cytometry panels to identify cancer, immune, and stromal cells and structures and their biomechanical states. Our patient cohort includes 20+ years of follow up, with up to 6 samples per patient from 64 patients alive 12 years post diagnosis, and 49 patients lost to breast cancer deaths. Patients were treated with surgery, radiation, chemotherapy, endocrine therapy, or combinations of these post-surgery. Based on this approach, we derived a new three-parameter quantitative metric of preferential spatial co-localization between different cells or structures, and we use this metric to stratify patients into responders and non-responders with the aid of single and multivariate survival analysis. Finally, we include a correlation with Atomic Force Microscopy to identify the mechanical signature of these driving patterns in breast cancer. Results: Our work enabled the identification of tumor-immune-stromal spatial patterns that drive breast cancer outcome and their spatial scale. Among our results, we were able to further define spatial regions of hypoxia-driven EMT. We found these regions to be usually on the scale of 50 mm radius, and enriched in presence of unspecified immune cells. They are also more frequent in ER+ areas, with high NaKATPase activity. Our analysis also shed light on the controversy on the role of fibroblasts. We have found that the presence of a strong, spatially structured stroma, in fibroblast-rich regions is a strong predictor of positive outcome. Similarly, in our analysis collagen cross-linking emerges as a positive control factor in Vimentin-rich microenvironments, offering new interpretation to the role of the ECM structure. Importantly, our first principle approach allows for the identification of driving structures beyond heterogeneity, and thus enables easy extension to additional datasets. Finally, when correlating these patterns with Atomic force microscopy measurements, we can clearly see that patterns predictive of poor survival present a clear heterogeneous stiffness signature, as opposed to a very homogenous good survival pattern signature. Conclusion: These results confirm the importance of spatial distribution of biomechanical drivers in cancer, offering new avenues of physics-based therapeutic targets. Our results also offer a solid base to inform machine learning algorithms on how to significantly parametrize spatial patterns in breast cancer for clinical significance. Furthermore, we demonstrate for the first time the use of Atomic Force Microscopy as a single biomarker for these patterns in breast cancer with a direct correlation based on pathology matching. Citation Format: Sara Nizzero, Maria Pelaez Soni, Gregory Zaugg, Mariam Gachechiladze, Yitian Xu, Licheng Zhang, Junjun Zheng, Brian Menegaz, Lee B Jordan, Colin A Purdie, Philip R Quinlan, Chandandeep Nagi, Karla A Sepulveda, Philipp Oertle, Tobias A Appenzeller, Marko Loparic, Zhihui Wang, Shu-Hsia Chen, Vittorio Cristini, Marija Plodinec, Alastair Thompson. Spatial biomechanics determines fate in breast cancer [abstract]. In: Proceedings of the 2023 San Antonio Breast Cancer Symposium; 2023 Dec 5-9; San Antonio, TX. Philadelphia (PA): AACR; Cancer Res 2024;84(9 Suppl):Abstract nr PS03-08.