AFM-IR Research Articles

Surface Heterogeneity in Amorphous Silica Nanoparticles Evidenced from Tapping AFM–IR Nanospectroscopy

In this work, we propose to evaluate and validate an emerging spectroscopic space-resolved technique: atomic force microscopy coupled with infrared spectroscopy (AFM-IR) for inorganic materials in tapping mode at the nanoscale. For this aim, a preliminary investigation of sample preparation techniques was done and the stability of tapping AFM-IR spectra was evaluated on reference samples [poly(methyl methacrylate) and silica]. It was concluded that for a homogeneous polymer, it is possible to compare AFM-IR spectra with conventional Fourier-transform infrared (FTIR) spectra obtained in transmission. When an inorganic solid is considered, AFM-IR spectra are different from the global FTIR spectrum which indicates that the AFM-IR technique probes a volume which is not representative of global composition, that is, the external surface layer. Moreover, local infrared spectra recorded in the tapping mode of the external surface are significantly different depending on the analyzed regions of the same particle and between particles of the amorphous silica, implying surface heterogeneity. The AFM-IR technique allows surface description of amorphous inorganic materials at the nanoscale and opens new frontiers in the characterization of functional nanoscale and crystalline materials.

An Another Protocol to Make Sulfur Embedded Ultrathin Sections of Extraterrestrial Small Samples.

Another protocol to make sulfur embedded ultrathin sections was developed for STXM–XANES, AFM–IR and TEM analyses of organic materials in small extraterrestrial samples. Polymerized liquid sulfur—instead of low-viscosity liquid sulfur—is the embedding media in this protocol. Due to high viscosity of the polymerized sulfur, the embedded samples stay near the surface of polymerized liquid sulfur, which facilitates trimming of glassy sulfur and ultramicrotomy of tiny embedded samples. In addition, well-continued ribbons of ultramicrotomed sections can be obtained, which are suitable for the above mentioned analyses. Because there is no remarkable difference in Carbon XANES spectra of Murchison IOM prepared by this protocol and by the conventional protocol, this protocol gives another alternative to prepare sulfur embedded ultramicrotomed sections.

Suppressed antiferromagnetic ordering and enhanced electrical conduction in doped iridate Sr2−xPrxIrO4

Sr2IrO4 has been shown to exhibit a novel Jeff = 1/2 Mott spin–orbit insulating state with antiferromagnetic ordering. In the present investigation, the effects of Pr substitution at Sr-site on structural, magnetic and electrical properties are studied in Sr2IrO4. Pr-doped samples still retain the insulating behavior, but with the increase of Pr doping concentration, the resistivity decreases. The magnetic properties show that long-range antiferromagnetic order is collapsed when the Pr doping content increases up to 20%, which may results from a competition between the AFM (Ir 5d electrons) and ferromagnetic (Pr 4 f electrons) coupling. In addition, Pr doping induces a spin glasslike state at low temperatures.

Molecular Orientation in Individual Electrospun Nanofibers Studied by Polarized AFM–IR

Molecular orientation is critical to the properties of fibers, yet analysis of electrospun nanofibers of small diameters is challenging due to limited spatial resolution of the characterization tec...

Evaluating Mechanical Properties of Polymers at the Nanoscale Level via Atomic Force Microscopy–Infrared Spectroscopy

The characterization and the optimization of packaging materials require accessing their composition with nanometric precision. A possible solution comes from atomic force microscopy–infrared spectroscopy (AFM–IR), capable of acquiring IR spectra with a spatial resolution surpassing the limit of infrared spectroscopy by far. Differentiating polyolefins, a typical component of packaging films, is complicated by the large similarity in the infrared response of this class of materials. Here, we propose a method with which to improve domains differentiation based on the analysis of IR spectra and viscoelastic properties, extracted via a routine similar to that employed in contact-resonance AFM.

Atomic force microscopy based infrared (AFM–IR) spectroscopy and nuclear resonance vibrational spectroscopy comparative study on malignant and benign human cancer cells and tissues under synchrotron radiation with the passage of time

Atomic force microscopy based infrared (AFM–IR) spectroscopy and nuclear resonance vibrational spectroscopy comparative study on malignant and benign human cancer cells and tissues under synchrotron radiation with the passage of time

In vivo atomic force microscopy–infrared spectroscopy of bacteria

A new experimental platform for probing nanoscale molecular changes in living bacteria using atomic force microscopy-infrared (AFM-IR) spectroscopy is demonstrated. This near-field technique is eminently suited to the study of single bacterial cells. Here, we report its application to monitor dynamical changes occurring in the cell wall during cell division in Staphylococcus aureus using AFM to demonstrate the division of the cell and AFM-IR to record spectra showing the thickening of the septum. This work was followed by an investigation into single cells, with particular emphasis on cell-wall signatures, in several bacterial species. Specifically, mainly cell wall components from S. aureus and Escherichia coli containing complex carbohydrate and phosphodiester groups, including peptidoglycans and teichoic acid, could be identified and mapped at nanometre spatial resolution. Principal component analysis of AFM-IR spectra of six living bacterial species enabled the discrimination of Gram-positive from Gram-negative bacteria based on spectral bands originating mainly from the cell wall components. The ability to monitor in vivo molecular changes during cellular processes in bacteria at the nanoscale opens a new platform to study environmental influences and other factors that affect bacterial chemistry.

An instrumental approach to combining confocal microspectroscopy and 3D scanning probe nanotomography

In the past decade correlative microscopy, which combines the potentials of different types of high-resolution microscopies with a variety of optical microspectroscopy techniques, has been attracting increasing attention in material science and biological research. One of outstanding solutions in this area is the combination of scanning probe microscopy (SPM), which provides data on not only the topography, but also the spatial distribution of a wide range of physical properties (elasticity, conductivity, etc.), with ultramicrotomy, allowing 3D multiparametric examination of materials. The combination of SPM and ultramicrotomy (scanning probe nanotomography) is very appropriate for characterization of soft multicompound nanostructurized materials, such as polymer matrices and microstructures doped with different types of nanoparticles (magnetic nanoparticles, quantum dots, nanotubes, etc.), and biological materials. A serious problem of this technique is a lack of chemical and optical characterization tools, which may be solved by using optical microspectroscopy.Here, we report the development of an instrumental approach to combining confocal microspectroscopy and 3D scanning probe nanotomography in a single apparatus. This approach retains all the advantages of SPM and upright optical microspectroscopy and allows 3D multiparametric characterization using both techniques. As the first test of the system developed, we have performed correlative characterization of the morphology and the magnetic and fluorescent properties of fluorescent magnetic microspheres doped with a fluorescent dye and magnetic nanoparticles. The results of this study can be used to obtain 3D volume images of a specimen for most high-resolution near-field scanning probe microscopies: SNOM, TERS, AFM–IR, etc. This approach will result in development of unique techniques combining the advantages of SPM (nanoscale morphology and a wide range of physical parameters) and high-resolution optical microspectroscopy (nanoscale chemical mapping and optical properties) and allowing simultaneous 3D measurements.

Ligand-Dependent Nanoparticle Clustering within Lipid Membranes Induced by Surrounding Medium.

The interactions between hydrophobic or semihydrophobic gold and silver nanoparticles (NPs) and a dimyristoylphosphatidylcholine (DMPC) bilayer as a model cell membrane in two ionic solutions result in the structural reorganization within the bilayer manifested as locally increased nanomechanical compaction in the vicinity of NP clusters as well as changed overall thermotropic properties. The effects of NP surface charge and hydrophobicity were examined using AFM imaging, force spectroscopy and IR spectroscopy. The NP clustering occurred during hydration process of dry films containing both the DMPC molecules and the NPs by the mechanism in which the number of bilayer deformations was reduced by NP clustering. The force spectroscopy showed increased bilayer density around (semi)hydrophobic NP clusters and thus locally increased lateral compaction of the bilayer. The strengthening effect was observed for both the silver and the gold NPs in a high ionic strength solution such as seawater, while it was absent under physiological conditions. The local lipid rearrangement induces the long-range lipid reorganization resulting in the bilayer phase transition shifting toward lower or higher temperatures depending on the solution ionic strength (at the most by -1.0 °C in phosphate buffered saline and at the most by +0.5 °C in seawater).

Nanoscale spectroscopy and imaging of hemoglobin

Sub diffraction limited infrared absorption imaging of hemoglobin was performed by coupling IR optics with an atomic force microscope. Comparisons between the AFM topography and IR absorption images of micron sized hemoglobin features are presented, along with nanoscale IR spectroscopic analysis of the metalloprotein.

Well-Defined Carboxyl-Terminated Alkyl Monolayers Grafted onto H−Si(111): Packing Density from a Combined AFM and Quantitative IR Study

This work demonstrates that well-defined mixed carboxyl-terminated/methyl-terminated alkyl monolayers can be prepared in one step on H-terminated Si(111) via direct photochemical hydrosilylation of undecylenic acid and 1-decene mixtures. As evidenced by AFM imaging and IR spectroscopy, a final rinse in hot acetic acid leaves the functionalized surface atomically smooth and perfectly free of physisorbed contaminants while unwanted material remains atop the monolayer with most other common solvents. The compositional surface chemistry was determined from a truly quantitative IR (ATR geometry) study in the range of 900-4000 cm(-)(1). Results prove that neither surface oxidation nor grafting through the carboxyl end groups occurs. Monolayers are fairly dense for such bulky end groups, with a total molecular surface density of approximately 2.7 10(14) cm(-)(2) corresponding to a surface coverage of 0.35 (maximum theoretical value approximately 0.5). Careful analysis of the CH- and COOH-related IR bands reveals that the composition of the grafted layers is richer in acid chains than the starting grafting mixture. A simple model is presented that shows that the grafting kinetics is about twice as fast for undecylenic acid as for 1-decene. Complementary electrochemical impedance measurements indicate the excellent electronic properties of the interface with a very low density of gap states. They also show that the acid terminal groups promote the penetration of water in the outer part of the organic film.

Self-assembling monolayer formation of glucose oxidase covalently attached on 11-aminoundecanethiol monolayers on gold.

Glucose oxidase (GOx) has been attached covalently to form uniform enzyme monolayers on self-assembled monolayers (SAMs) from 11-aminoundecanethiol (AUDT) by taking advantage of chemical oxidation of GOx carbohydrate residues followed by coupling the resulting 'aldehydic' enzyme with the terminal amino group in the SAM as characterized by AFM imaging, IR, QCM, and electrochemical measurements.