Single molecule force spectroscopy of smart poly(ferrocenylsilane) macromolecules: Towards highly controlled redox-driven single chain motors

We investigated various stimuli-responsive poly(ferrocenylsilane) (PFS) polymers as model systems for the realization of molecular motors powered by a redox process. Covalently end-grafted PFS on gold, as well as PFS homopolymers and block copolymers in ultrathin films, were studied by AFM-based single molecule force spectroscopy (SMFS). Surface confined PFS macromolecules were chemically oxidized by addition of tetracyanoethylene or were completely and reversibly oxidized (and reduced) in situ by applying an electrochemical potential. Chemical oxidation was successful only for the block copolymers. The entropic elasticity of neutral PFS chains (Kuhn length I_K∼0.40 nm) was found to be larger than that of oxidized PFS chains (I_K∼0.65 nm) in the lower force regime. The elasticities could be reversibly controlled in situ by adjusting the applied potential in electrochemical SMFS experiments. For a single PFS macromolecule (DP=80) operating cycle, a work output and an efficiency of 3.4×10⁻¹⁹ J and ∼5%, respectively, were estimated based on the single chain experimental data.     

Micromechanical properties of glassy and rubbery polymer brush layers as probed by atomic force microscopy

Carboxylic acid terminated polystyrene and polybutylacrylate were grafted from melt onto a silicon substrate modified with the epoxysilane monolayer. The tethered layers fabricated from polymers of different molecular weights are smooth, uniform, mechanically stable, and cover homogeneously the modified silicon surface. Micromechanical properties of the dry glassy and rubbery brush layers were measured with atomic force microscope. We observed that for the PS layers with the thickness higher than 7 nm, the average value of the elastic moduli reached 1.1 GPa, which is close, but still lower than the expected for bulk polymer. The elastic modulus of PS polymer brush layers dramatically depends upon molecular weight and follows the inverse law with segment molecular weight, M_c of 18,000 known for bulk PS. This result indicates that the process of the formation of the physical network within polymer melt of chains tethered to a solid substrate is similar to that occurring in unconstrained polymer melt. Under these conditions, three PS brush layers studied in this work represent different cases of chains without stable entanglements for M<M_c as well as chains with stable entanglements for brushes with M∼M_c. This transition shows itself in significant reduction of the compliance reflected in twofold increase in elastic modulus. Our estimation predicts that modest lowering of ‘limiting’ elastic modulus of 1.4 GPa can be expected for thicker polymer brushes.     

Visual characterization and quantitative measurement of artemisinin-induced DNA breakage

DNA conformational change and breakage induced by artemisinin, a traditional Chinese herbal medicine, have been visually characterized and quantitatively measured by the multiple tools of electrochemistry, UV-vis absorption spectroscopy, atomic force microscopy (AFM), and DNA electrophoresis. Electrochemical and spectroscopic results confirm that artemisinin can intercalate into DNA double helix, which causes DNA conformational changes. AFM imaging vividly demonstrates uneven DNA strand breaking induced by QHS interaction. To assess these DNA breakages, quantitative analysis of the extent of DNA breakage has been performed by analyzing AFM images. Basing on the statistical analysis, the occurrence of DNA breaks is found to depend on the concentration of artemisinin. DNA electrophoresis further validates that the intact DNA molecules are unwound due to the breakages occur at the single strands. A reliable scheme is proposed to explain the process of artemisinin-induced DNA cleavage. These results can provide further information for better understanding the anticancer activity of artemisinin.     

Morphology development and exclusion of noncrystalline polymer during crystallization in PVDF/PMMA blends

Morphology development during the crystallization of poly(vinylidene fluoride) (PVDF)/poly(methyl methacrylate) (PMMA) blends was investigated at various crystallization temperatures (T_C) by means of time-resolved light scattering measurements and atomic force microscopy (AFM). A coarse spherulite obtained at a high T_C of 162 °C was found to be developed with a two-step crystallization process. The ordering in the spherulites (Pr) increased with time at the early stages and then decreased at the later stages. The rate of spherulite growth started to decrease when Pr started to decrease. In contrast, in the compact spherulite obtained at a low T_C of 148 °C, Pr decreased monotonously with time while the growth rate was constant. AFM observation revealed that such characteristic crystallization behavior is attributed to the exclusion of PMMA from the crystal growth during the crystallization; i.e., the amount of excluded PMMA becomes larger as the distance from the spherulite center increases and the crystallization temperature rises.     

Determination of the influence of the polymer structure and particle size on the film formation process of polymers by atomic force microscopy

The particle size and morphology of a synthetic polymer latex were shown to influence the film formation behavior. Theoretical models predict that small particles coalesce more easily than large colloids do.The influence of particle size and morphology of differently structured lattices on the film-formation process was investigated by atomic force microscopy (AFM). Sequences of AFM images were acquired over a certain temperature range or at room temperature as a function of time. From the resulting images the average particle diameter of the latex particles in the surface layer was determined as a function of the time or temperature. The resulting curves could be compared to observe differences in the film formation kinetics of the different lattices. These AFM studies confirmed that the film formation behavior is influenced by the particle size and particle morphology, but that the core/shell ratio of core-shell particles has no significant influence on the film formation kinetics.     

Measuring local viscoelastic properties of complex materials with tapping mode atomic force microscopy

Tapping mode atomic force microscopy is a technique to measure the topography and properties of surfaces involving a micro-cantilever with a tip at one end that is excited into an oscillation near its resonance frequency. The phase lag between the excitation signal and the observed oscillation is sensitive to local mechanical properties under certain experimental conditions. We have found that by using silicon as an internal standard reference surface we can unambiguously relate the phase lag to local viscoelastic properties of a polymeric material. A model describing this relation has been built, validated with experimental data and finally inverted such that it can be used to determine local properties. This allows us to measure high frequency local viscoelastic properties on length scales as small as several nanometers. This technique works well for relatively compliant polymer surfaces with a shear modulus less than about 1 GPa.     

Electrochemical deposition and characterization of NiFe coatings as electrocatalytic materials for alkaline water electrolysis

In this study, nickel (Cu/Ni), iron (Cu/Fe) and nickel-iron (Cu/NiFe) composite coatings with various chemical compositions were electrochemically deposited on a copper electrode and characterized using cyclic voltammetry (CV), atomic absorption spectroscopy (AAS), scanning electron microscopy (SEM) and atomic force microscopy (AFM) techniques in view of their possible applications as electrocatalytic materials for the hydrogen evolution reaction (HER) in an alkaline medium. The electrocatalytic activity of the coatings for the HER was studied in 1 M KOH solution using cathodic current-potential curves and electrochemical impedance spectroscopy (EIS) techniques. The presence of nickel along with iron increases the electrocatalytic activity of the electrode for the HER when compared to nickel and iron coatings individually. The HER activity of the composite coatings depends on the chemical composition of the alloys. The Cu/NiFe-3 electrode (with a molar concentration ratio of Ni²⁺:Fe²⁺ of 4:6 in the plating bath) was found to be the best suitable cathode material for the HER in an alkaline medium under the experimental conditions studied. Furthermore, the electrocatalytic activity of the Cu/NiFe-3 electrode for the HER was tested for extended periods of time in order to evaluate the change in the electrocatalytic activity of the electrode with operation time. The HER was activation controlled and has not been changed after electrolysis. A constant current density of 100 mA cm⁻² was applied to the electrolysis system, and the corrosion behavior of the Cu/NiFe-3 electrode was investigated after different operation times using EIS and linear polarization resistance (LPR) techniques. For comparison, the corrosion behavior of a Cu/NiFe-3 electrode to which current was not applied was also investigated. The corrosion tests showed that the corrosion resistance of the Cu/NiFe-3 cathode changed when a cathodic current was applied to the electrolysis system.     

Synthesis and self-assembly study of two-armed polymers containing crown ether core

Two functional crown ether initiator, bis[4′-(2-bromobutyryl)]dibenzo-18-crown-6 (BBDC) was synthesized through the condensation of dibenzo-18-crown-6 with 2-bromobutyric acid in the presence of polyphosphoric acid. Atom transfer radical polymerizations of styrene (St), methyl acrylate, methyl methacrylate and butyl acrylate were carried out in bulk to produce the polymers with well-controlled molecular weights and narrow molecular weight distributions (1.12-1.32). Based on ¹H NMR results, both the two bromides of BBDC initiated the polymerizations. The well-defined two-armed polymers were self-assemblized in the presence of potassium cations. Their morphologies of the film obtained were studied by atomic force microscopy with tapping mode.     

Matrix mediated alignment of single wall carbon nanotubes in polymer composite films

Alignment of single wall carbon nanotubes (SWNT) in liquid crystalline (LC) polymer matrix imparting orientation to the nanotubes along the nematic director was studied by atomic force microscopy, measurements of electrical conductivity and Raman spectroscopy of the composite in the directions parallel and perpendicular to the nematic director. The composites were prepared through dispersion of SWNT with LC monomer in a common solvent, their alignment in nematic monomer and consequent UV polymerization of the monomer. The anisotropy of electrical and optical properties of the system depends strongly on the concentration of the nanotubes in the range of 1-10% SWNT being especially strong for smaller concentrations and negligible at higher loads. A simple semi-quantitative model is suggested to account for the orientational behavior of nanotubes in nematic matrices. It successfully describes the observed anisotropy of physical properties at microscale (up to 200 μm) in terms of anchoring of the polymer chains to the nanotubes surface and adjustment of the nanotubes orientation to the nematic direction due to such coupling. The increasing disorientation of the nematic domains at higher nanotubes loads is explained as a development of larger number of LC defects induced by the nanotubes in the nematic matrix due to their intrinsic nature of aggregation. The anisotropy of physical properties at macro scale (several millimeters) is much smaller and less dependable on SWNT concentration because differently oriented LC domains effectively wash out the anisotropy.     

Synthesis of large single crystal diamond using combustion-flame method

A combustion flame method is used to synthesize large single crystal diamond in ambient atmosphere. The basic of this technique was originally described by Hirose and Kondo in 1988 [Hirose H, Komaki K. Eur Pat Appl 1988:EP324538]. The advantage of this method is the high growth rate of diamond films, which is about 60 μm/h [Alers P, Hanni W, Hintermann HE. A comparative study of laminar and turbulent oxygen-acetylene flames for diamond deposition. Diam Relat Mat 1992;2:393-6]. The diamond can grow on itself to achieve large single-crystal. Negative substrate-bias effects on diamond growth have been investigated. Diamonds films were characterized by scanning electron microscopy, Raman spectroscopy, and atomic force microscopy in tapping mode. For given conditions, diamond coatings with highly oriented {1 0 0} crystal facets were produced. Large singles crystals diamonds were obtained. The sizes of these crystals vary between 80 and 90 μm. These results are discussed with respect to the competing events occurring during the heteroepitaxial growth of diamond.     

Electron-transfer characteristics of ferrocene attached to single-walled carbon nanotubes (SWCNT) arrays directly anchored to silicon(1 0 0)

High-density, surface-mounted ferrocene has been prepared using covalent immobilisation of an alcohol substituted ferrocene derivative to a pre-assembled single-walled carbon nanotubes directly anchored to silicon(1 0 0) surface (SWCNTs-Si). The formation of these ferrocene-modified electrodes (Fc-SWCNTs-Si) has been followed using X-ray photoelectron spectroscopy and atomic force microscopy. Electrochemical results show the surface concentration of ferrocenemethanol molecules is 9.26 × 10⁻⁸ mol cm⁻², which is about 500-1000 times greater than the experimentally measured coverage of ferrocene directly attached to flat Si(1 0 0) surfaces. The reversible one-electron wave of the ferrocene/ferrocenium couple was observed at 490 mV versus Ag⁺/Ag and the apparent rate constant of electron transfer, k_app, was 21 s⁻¹. These results suggest these ferrocene-modified electrodes are excellent candidates for molecular memory devices.     

Piezoelectric inkjet printing of polymers: Stem cell patterning on polymer substrates

Generating patterns of cells on surfaces is of great significance not only for fundamental studies in biomedical science but also for the creation of functional customized tissue or organs in regenerative medicine. In this paper, arbitrary, complex stem cell patterns were created using piezoelectric inkjet printing of biocompatible polymers. After a systematic study with different inkjet process variables, various poly(lactic-co-glycolic acid) (PLGA) patterns were fabricated on a polystyrene (PS) substrate. Human adipose-derived stem cells (hASCs) were isolated from subcutaneous adipose tissue and were seeded on the PLGA-patterned PS substrate which consists of areas either favorable (PLGA) or unfavorable (bare PS) to cell adhesion. The hASC stably attached, proliferated within the PLGA patterns, thus, complex and confluent hASC patterns were created. Polymer micro-patterning by inkjet printing could be an effective technique to control cell adhesion geometry, leading to arbitrary cell patterning on surfaces.     

Characterization of network morphology in anion binding hydrogels used for wastewater remediation

This work reports on morphological features of hydrogels, which have been used for the ultimate removal and recovery of nutrient and toxic anions from wastewater effluents. The sorbent used was crosslinked polyamine (PAA·HCl) polymeric hydrogels. The surface topography and morphology of these hydrogels were characterized by tapping mode atomic force microscopy. The change of the gel surface in response to the degree of crosslinking was observed via phase imaging. The crosslinker amount affects both the crosslink density and uniformity. Phase images were recorded at moderate to hard tapping conditions (A_sp/A₀=0.3-0.6) and related to surface stiffness variations associated with Young's modulus (E) change. Bright ellipse and sponge-like domains of submicrometer scale were found on irregularly crosslinked gels, while the gel topography was uniform in gels that were prepared with a more regular distribution of crosslinks. The observed AFM domain size was strongly affected by the gel's degree of crosslinking.     

Automatic hammering of nano-patterns on special polymer film by using a vibrating AFM tip

ABSTRACT: Complicated nano-patterns with linewidth less than 18 nm can be automatically hammered by using atomic force microscopy (AFM) tip in tapping mode with high speed. In this study, the special sample was thin poly(styrene-ethylene/butylenes-styrene) (SEBS) block copolymer film with hexagonal spherical microstructures. An ordinary silicon tip was used as a nano-hammer, and the entire hammering process is controlled by a computer program. Experimental results demonstrate that such structure-tailored thin films enable AFM tip hammering to be performed on their surfaces. Both imprinted and embossed nano-patterns can be generated by using a vibrating tip with a larger tapping load and by using a predefined program to control the route of tip movement as it passes over the sample's surface. Specific details for the fabrication of structure-tailored SEBS film and the theory for auto-hammering patterns were presented in detail.     

Controlled fabrication of non-fluoro polymer composite film with hierarchically nano structured fibers

Hierarchically nano structured composite fibers were fabricated and characterized. The fibers composed of expanded polystyrene foam (EPF) embedded with varying graphite content were spray coated onto glass substrate. The FESEM and AFM images indicate well dispersed graphite and formation of thin nano fibers, which exhibited water contact angle of 151°. Diameter of a single fiber was noted to be ∼500 nm. The uniqueness of the present method is use of fluorine free raw materials, environment benign solvents and feasibility of applying over large surfaces.     

Applying VHB acrylic elastomer as a cell culture and stretchable substrate

Elastomers are flexible polymers with low young’s modulus and high failure strain. VHB, considered as an acrylic elastomer, is widely used in smart materials due to its dielectric and electromechanical actuating properties. To the best of our knowledge, this polymer has not been applied as cell culture and stretching substrate and this role has played by PDMS. Herein, we present the structural properties of VHB vs. PDMS and then prove the safety of using this polymer as cell culture substrate by different viability assays. Moreover, we analyzed the effect of stretching of VHB substrate on the cultured cells.     

The application of lateral force microscopy to particle removal in aqueous polymer solutions

Abstraet-An atomic force microscope (AFM) has been used to examine the effect of a typical polymeric dispersant on the adhesion between an iron oxide sphere and a silicon wafer in the presence and absence of shear. Two separate methods for the determination of the lateral spring constant (k₁) of AFM cantilevers were employed. Determination of k₁ allows the absolute, rather than relative, shear force to be extracted from the lateral force output of the AFM. A comparison is made between the pull-off force (no shear) and the lateral force as the dispersant concentration and loading force are varied. While in both cases the magnitude of the forces decrease with increasing dispersant concentration, the effect is much less marked for the lateral force. A linear increase in removal forces with increasing loading force was observed. For a given load, the removal force is typically an order of magnitude smaller in the presence of shear.     

Structures and morphologies of cast and plastically strained polyamide 6 films as evidenced by confocal Raman microspectroscopy and atomic force microscopy

Both confocal Raman microspectroscopy and atomic force microscopy (AFM) have been undertaken to study the crystalline and the morphological aspects of cast PA 6 films at a sub-microscopic scale. The percentages of the different crystalline structures present within PA 6 cast films, i.e. the monoclinic α, the pseudo-hexagonal β, and the monoclinic γ, have been measured by confocal Raman microspectroscopy. In cast films, the prevailing structure is the β one. AFM has been used to characterize the morphology of the PA 6 films. Simultaneously, the deformed state has been considered as well. Our main interest has been to follow the evolution of the percentage of each crystalline structure as a function of the plastic deformation mechanisms which are responsible of the yielding of PA 6 films: shear banding for temperatures T lower than 160 °C and formation of fibrils for      

Structure of polymer within the coating: an atomic force microscopy and small angle neutrons scattering study

Synthetic latex is widely used as a binder in waterbased paints. Upon dehydration of the dispersion, latex particles are brought into contact with mineral pigments: this process results in coating structuration and consolidation. This composite layer is described as a porous mineral structure, whose pores are covered by latex particles. Therefore, it is of fundamental interest to study the ordering of binder particles in the coating, and the wetting of pigments by polymer particles, toward understanding properties of coating such as: optical properties, adhesion, cohesion, sensitivity to water, etc. In this regard, we have used small angle neutron scattering and atomic force microscopy to study the ordering, the spreading, and the adhesion of latex particles on calcium carbonate within the coating. We discuss the structure of the coating.     

Oil-acrylic hybrid latexes as binders for waterborne coatings

The combination of the characteristics of oil, or alkyd, emulsions and acrylic latexes in a waterborne binder has been the object of various studies in the past. Strategies for combining the positive properties of alkyds, e.g. autoxidative curing, gloss and penetration in wood, with the fast drying and gloss and color retention properties of acrylic latexes have mainly been directed towards the modification of the alkyd with an acrylate during alkyd synthesis followed by emulsification. This paper describes the preparation and application of oil-acrylic hybrid latexes as binders for waterborne coatings. The hybrid latexes were prepared using hydroperoxidized triglycerides as initiators for the mini-emulsion polymerization of acrylates in an Fe(II)/EDTA/SFS redox system. The particle morphology of hybrids initiated by fatty-acid hydroperoxides was compared with tert-butyl hydroperoxide-initiated systems. Cryo-TEM analysis indicated that, whereas tert-butyl hydroperoxide initiation resulted in the formation of heterogeneous particles, fatty-acid hydroperoxide-initiated hybrid particles showed no intra-particle heterogeneity. An AFM study of the film formation process of the oil/alkyd-acrylic hybrid latexes showed that phase separation occurred between the oil and the acrylic phases upon drying, resulting in films that consist of deformed acrylic particles embedded in a continuous matrix of oil. This results in a very smooth surface of the film.