Observations of polyaniline surface morphology modification during doping and de-doping using atomic force microscopy

Chemically synthesized 30 m thick polyaniline films were studied during the doping and dedoping process by imaging the polymer surface using in situ atomic force microscopy (AFM). The polymer, which was initially in the base non-conducting form, was doped using aqueous solutions of both tosylic acid (pH = 0.2) and HCl (pH = 0.2 and 1.0). De-doping was accomplished by exposing the same doped polymer surface to NH₄OH (pH = 12) base solution. AFM images showed that it was necessary to cycle the polymer surface three times between acid and base before a reproducible surface morphology was established. For the case of doping with tosylic acid, AFM images showed that the polyaniline surface was immediately roughened; the changes in mean roughness for the base and acid conditions were ~ 5.4 and ~ 6.7 nm, respectively. In addition there appeared to be an increase in the size of surface channels and cracks. When doping with HCl (pH = 1.0), no change in surface morphology was observed; however, noticeable surface roughening occurred over 10 min for the case of the lower pH = 0.2 solution; mean roughness changes for the base and acid conditions were ~ 17.9 and 39.2 nm. Radio frequency measurements, which determined the polymer complex permittivity, and d.c. conductivity measurements were used to determine the level of doping in the samples studied by AFM which were exposed to acid solutions.     

Preparation, characterization and adsorption properties of chitosan nanoparticles for eosin Y as a model anionic dye

The present study dealt with the adsorption of eosin Y, as a model anionic dye, from aqueous solution using chitosan nanoparticles prepared by the ionic gelation between chitosan and tripolyphosphate. The nanoparticles were characterized by atomic force microscopy (AFM), size and zeta potential analysis. A batch system was applied to study the adsorption of eosin Y from aqueous solution by chitosan nanoparticles. The results showed that the adsorption of eosin Y on chitosan nanoparticles was affected by contact time, eosin Y concentration, pH and temperature. Experimental data followed Langmuir isotherm model and the adsorption capacity was found to be 3.333 g/g. The adsorption process was endothermic in nature with an enthalpy change (DeltaH) of 16.7 kJ/mol at 20-50 degrees C. The optimum pH value for eosin Y removal was found to be 2-6. The dye was desorbed from the chitosan nanoparticles by increasing the pH of the solution.     

Adsorption of chitosan onto carbonaceous surfaces and its application: atomic force microscopy study

The adsorption of chitosan onto highly ordered pyrolytic graphite(HOPG) surfaces and its applications have been studied by atomic force microscopy (AFM). The results indicated that chitosan topography formed on the HOPG surface significantly depends on the pH conditions and its concentration for the incubation. Under strongly acidic conditions (pH < 3.5) and at a concentration of 1 mg ml?1, chitosan formed into uniform network structures composed of fine chains. When the solution pH was changed from 3.5 to 6.5, chitosan tends to form a thicker film. Under neutral and basic conditions, chitosan changed into spherical nanoparticles, and their sizes were increased with increasing pH. Dendritic structures have been observed when the chitosan concentration was increased up to 5 mg ml?1. In addition, the chitosan topography can also be influenced by ionic strength and the addition of different metal ions. When 0.1 M metal ions Na+, Mg2+, Ca2+ and Cu2+ were added into the chitosan solution at pH 3.0 for the incubation, network structures, branched chains, block structures and dense networks attached with many small particles were observed, respectively. The potential applications of these chitosan structures on HOPG have been explored. Preliminary results characterized by AFM and XPS indicated that the chitosan network formed on the HOPG surface can be used for AFM lithography, selective adsorption of gold nanoparticles and DNA molecules.     

粗化液中钯离子对ABS塑料直接电镀的影响

粗化是实现活化液在ABS表面吸附的前提和获得良好结合力的必要条件.采用含痕量钯离子的铬酐-硫酸粗化液对ABS塑料表面进行化学粗化,用AFM、XPS和胶体钯吸附量等对粗化前后塑料的表面性能、价键状态和活性进行了考察.结果表明:钯离子加入到粗化液中对ABS表面的粗糙度影响不显著,粗化后的表面氧含量升高;随着粗化液中钯离子浓度的增加,胶体钯在ABS表面上的吸附量增加;增加粗化液中的Pd含量可使ABS表面在低浓度胶体钯溶液中达到与高浓度钯相同的吸附量,有效地降低了胶体钯的浓度.粗化液中加入钯离子不影响基体与镀层的结合力.     

Topographical heterogeneity in transparent PVA hydrogels studied by AFM

Physically crosslinked poly (vinyl alcohol) (PVA) hydrogels have a wide range of biomedical applications. Transparent and stable PVA hydrogels synthesized by freeze-thawing method are potential candidates to be used as tissue engineering scaffolds provided they exhibit suitable topographical roughness and surface energy. The effect of processing parameters i.e., polymer concentration and number of freeze-thaw cycles on the resulting topography of the freeze-thawed transparent hydrogels has been studied and quantified using non-contact mode of an atomic force microscope (AFM) and image analysis. Simultaneously captured phase contrast images have revealed significant information about morphological changes in the topographical features and crystallinity of the hydrogels. Topographical roughness was found to decrease as a function of number of freeze-thaw cycles.     

聚天冬氨酸/木质纤维素水凝胶的制备及吸附性能

采用水溶液聚合法合成聚天冬氨酸（PASP）/木质纤维素（LNC）水凝胶;考察了预处理时间、预处理温度、KMnO₄浓度、戊二醛用量、PASP的用量、反应时间以及反应温度对PASP/LNC水凝胶吸附Pb2+、Cd2+性能的影响;运用Langmuir吸附等温线计算PASP/LNC水凝胶最大吸附量;使用HNO₃对PASP/LNC水凝胶进行脱附再生实验;采用SEM和FTIR对水凝胶的结构进行表征。吸附结果表明:预处理时间15 min,预处理温度50 ℃、KMnO₄浓度0.06 mol·L-1、戊二醛用量1.00 g、PASP用量11 g、反应时间3.5 h且反应温度70 ℃时,对Pb2+、Cd2+的平衡吸附容量分别为980.39 mg·g-1、813.01 mg·g-1。 吸附/脱附循环实验表明:循环吸附脱附4次后PASP/LNC水凝胶吸附量仍较高,PASP/LNC水凝胶是一种可循环利用的吸附剂。表征结果表明:PASP/LNC水凝胶的表面有大小不等的孔隙,PASP的—COOH与LNC的O—H发生缩聚反应,形成具有三维网络结构的水凝胶。      

Evaluation of iron-based hybrid materials for heavy metal ions removal

The article presents in detail the results of the sorption of heavy metal ions such as Cu(II), Zn(II), Cd(II), and Zn(II) in the presence of ethylenediamine-N,N′-disuccinic acid as well as chromium(VI) on Purolite Arsen X^np and Lewatit FO36. Factors affecting the sorption equilibrium (sorbent dose, contact time, temperature, pH, and the presence of interfering ions) were studied. To compare the surface morphologies of the studied ion exchangers, scans using atomic force microscope were also recorded, and attenuated total reflectance infrared spectroscopy was applied to establish the adsorption mechanism. The main parameters affecting sorption are initial concentration of the solution, pH, and phase contact time. Temperature has only a slight influence. The kinetic data were fitted using the pseudo-first-order and pseudo-second-order models. In the case of Cr(VI) adsorption, the equilibriums on Purolite Arsen X^np and Lewatit FO36 were established within 60 min, in the case of Cu(II) and Zn(II) within 30–40 min and for Cd(II) and Pb(II) even less than 30 min. Moreover, it was found that the effectiveness of adsorption in the case of Cr(VI), Cu(II), Zn(II), Cd(II), and Pb(II) on Purolite ArsenX^np was higher than that on Lewatit FO36.     

Glow discharge plasma-induced immobilization of heparin and insulin on polyethylene terephthalate film surfaces enhances anti-thrombogenic properties

Polyethylene terephthalate (PET) films were treated with DC glow discharge plasma followed by graft copolymerization with acrylic acid (AA) and polyethylene glycol (PEG). The obtained PET–PEG was coupled to heparin or insulin molecules. The surfaces were then characterized by contact angle measurements, atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). The surface energies of the modified PET films were estimated using contact angle measurements, and the changes in crystallinity of the plasma-modified PET film surfaces were investigated by X-ray diffraction (XRD) analysis. The blood compatibilities of the surface-modified PETs were examined by in vitro thrombus formation, whole blood clotting time, platelet contact and protein adsorption experiments. The results revealed that the contact angle value decreased and that the interfacial tension between the modified PET films and blood protein was drastically diminished compared to unmodified PET film. The XPS results showed that the PET–AA surface containing carboxylic acid and the immobilized PET surface containing both carboxylic acid and amino groups exhibited a hydrophilic character, and AFM results showed marked morphological changes after grafting of AA, PEG and biomolecule immobilization. Heparin and insulin-coupled PET surfaces exhibited much less platelet adhesion and protein adsorption than the other surface-modified PET film surfaces.     

Synthesis and characterization of L-histidine capped silver nanoparticles

L-histidine capped Ag nanoparticles have been synthesized by a hydrothermal method. Spherical Ag nanoparticles with average diameter ranging from 9 to 21 nm can be obtained by tuning the reaction pH and the reactant ratio. The topography, surface and internal structures of the histidine capped Ag nanoparticles have been characterized by transmission electron microscopy (TEM), atomic force microscopy (AFM), dynamic light scattering, X-ray photoelectron spectroscopy (XPS), X-ray Diffraction (XRD), Raman spectroscopy and UV–vis absorption spectroscopy. Surface enhanced Raman scattering (SERS) results revealed that the Ag colloid in present study have a structure that the imidazole moiety of histidine is bound on the Ag surface and COO^? group is exposed outward. The as-synthesized Ag colloidal solution was very stable and can be stored at room temperature at least one month. In addition, it was found that the solution color of Ag colloid can change from yellow to reddish-brown by addition of the NiCl₂ solution, which may have potential application for Ni²⁺ detection.     

Novel concept for the aggregation structure of fatty acid monolayers on the water surface and direct observation of molecular arrangements in their monolayers

The aggregation structure of fatty acid monolayers on water subphases of different pH’s was investigated by means of transmission electron microscopy. Fatty acid monolayers exhibited the phase transition from an amorphous state to a crystalline one by surface compression in the case of a highly dissociated state of hydrophilic groups, whereas they did not show the phase transition in the case of a slightly dissociated state. The aggregation structure of monolayers on the water surface was systematically classified into “the crystalline monolayer”, “the amorphous monolayer” and “the compressing crystallized monolayer” with respect to thermal and chemical (intermolecular repulsive) factors. Molecular-resolution images of fatty acid molecules in the monolayers on mica substrate were successfully observed with an atomic force microscope (AFM) for the first time. The AFM image of a lignoceric acid monolayer prepared at a surface pressure of 5mNm⁻¹ showed a two-dimensional periodic structure with locally disordered molecular arrangements. Also, the nondestructive AFM image observation was successful for a stearic acid monolayer which was prepared by a multistep creep method, indicating that a high mechanical stability of the monolayer is inevitably required for the nondestructive AFM observation.     

Determination of the ionization state of 11-thioundecyl-1-phosphonic acid in self-assembled monolayers by chemical force microscopy

The present article describes the preparation and preliminary characterization of a novel phosphate-functionalized self-assembled monolayer (SAM) and the determination of the surface ionization states of the phosphate headgroup in aqueous solutions by chemical force microscopy (CFM). The phosphate headgroup used was PO(OH)2, a diprotic acid. The adhesion force between an AFM probe and a flat substrate, both of which were chemically modified with the same phosphate SAM, was also measured as a function of pH and ionic strength. At low ionic strength (10(-4) M), two peaks were observed in the force titration curve (adhesion force versus pH) at pH 4.5 and 8.4. The two peaks are positioned 2.4 and 1.2 pH units higher, respectively, than the acid dissociation constants obtained for the phosphate group free in aqueous solution. At high ionic strength (10(-1) M), the adhesion forces were reduced by 1 order of magnitude and the peaks were replaced by shoulders similar to those previously reported for acid force titrations. On the basis of JKR theory, the surface pKa values of the phosphate group in high ionic strength solutions were found to be 4.5 and 7.7, respectively. However, in light of the effects of ionic strength on the force titration curves, we discuss the applicability of JKR theory to nanoscopic measurements of adhesion force and surface pKa.     

An amperometric uric acid biosensor based on Bis[sulfosuccinimidyl] suberate crosslinker/3-aminopropyltriethoxysilane surface modified ITO glass electrode

A label free, amperometric uric acid biosensor is described by immobilizing enzyme uricase through a self assembled monolayer (SAM) of 3-aminopropyltriethoxysilane (APTES) using a crosslinker, Bis[sulfosuccinimidyl]suberate (BS³) on an indium-tin-oxide (ITO) coated glass plate. The biosensor (uricase/BS³/APTES/ITO) was characterized by, scanning electron microscopy (SEM), atomic force microscopy (AFM) and electrochemical techniques. Chronoamperometric response was measured as a function of uric acid concentration in aqueous solution (pH 7.4). The biosensor shows a linear response over a concentration range of 0.05 to 0.58 mM with a sensitivity of 39.35 μA mM ^− 1. The response time is 50 s reaching to a 95% steady state current value and about 90% of enzyme activity is retained for about 7 weeks. These results indicate an efficient binding of enzyme with the crosslinker over the surface of APTES modified ITO glass plates, which leads to an improved sensitivity and shelf life of the biosensor.     

pH-dependent adsorption of Au nanoparticles on chemically modified Si3N4 MEMS devices

Microelectromechanical systems (MEMS) are devices that represent the integration of mechanical and electrical components in the micrometer regime. Self-assembled monolayers (SAMs) can be used to functionalise the surface of MEMS resonators in order to fabricate chemically specific mass sensing devices. The work carried out in this article uses atomic force microscopy (AFM) and X-ray photoemission spectroscopy (XPS) data to investigate the pH-dependent adsorption of citrate-passivated Au nanoparticles to amino-terminated Si₃N₄ surfaces. AFM, XPS and mass adsorption experiments, using ‘flap’ type resonators, show that the maximum adsorption of nanoparticles takes place at pH = 5. The mass adsorption data, obtained using amino functionalised ‘flap’ type MEMS resonators, shows maximum adsorption of the Au nanoparticles at pH = 5 which is in agreement with the AFM and XPS data, which demonstrates the potential of such a device as a pH responsive nanoparticle detector.     

Effect of substrate temperature on corrosion performance of nitrogen doped amorphous carbon thin films in NaCl solution

Nitrogen doped amorphous carbon (a-C:N) thin films were deposited on p-Si substrates by DC magnetron sputtering at varying substrate temperature from room temperature (RT) to 300 °C. The bonding structure, surface morphology and adhesion strength of the a-C:N films were investigated by using X-ray photoelectron spectroscopy (XPS), micro-Raman spectroscopy, atomic force microscopy (AFM) and micro-scratch testing. The corrosion behavior of the a-C:N films was evaluated by potentiodynamic polarization test in a 0.6 M NaCl solution. The results indicated that the corrosion resistance of the films depended on the sp³-bonded cross-link structure that was significantly affected by the substrate temperature.     

Field emission studies of CVD diamond thin films: effect of acid treatment

Field emission from CVD diamond thin films deposited on silicon substrate has been studied. The diamond films were synthesized using hot filament chemical vapor deposition technique. Field emission studies of as-deposited and acid-treated films were carried out using ‘diode’ configuration in an all metal UHV chamber. Upon acid treatment, the field emission current is found to decrease by two orders of magnitude with increase in the turn-on voltage by 30%. This has been attributed to the removal of sp² content present in the film due to acid etching. Raman spectra of both the as-deposited and acid-treated films exhibit identical spectral features, a well-defined peak at 1333 cm⁻¹ and a broad hump around 1550 cm⁻¹, signatures of diamond (sp³ phase) and graphite (sp² phase), respectively. However upon acid treatment, the ratio (I_d/I_g) is observed to decrease which supports the speculation of removal of sp² content from the film. The surface roughness was studied using atomic force microscopy (AFM). The AFM images indicate increase in the number of protrusions with slight enhancement in overall surface roughness after acid etching. The degradation of field emission current despite an increase in film surface roughness upon acid treatment implies that the sp² content plays significant role in field emission characteristics of CVD diamond films.     

Writing with Fluid: Structuring Hydrogels with Micrometer Precision by AFM in Combination with Nanofluidics

Hydrogels have many applications in biomedical surface modification and tissue engineering. However, the structuring of hydrogels after their formation represents still a major challenge, in particular due to their softness. Here, a novel approach is presented that is based on the combination of atomic force microscopy (AFM) and nanofluidics, also referred to as FluidFM technology. Its applicability is demonstrated for supramolecular hydrogel films that are prepared from low‐molecular weight hydrogelators, such as derivates of 1,3,5‐benzene tricarboxamides (BTAs). BTA films can be dissolved selectively by ejecting alkaline solution through the aperture of a hollow AFM‐cantilever connected to a nanofluidic controller. The AFM‐based force control is essential in preventing mechanical destruction of the hydrogels. The resulting “chemical writing” process is studied in detail and the influence of various parameters, such as applied pressure and time, is validated. It is demonstrated that the achievable structuring precision is primarily limited by diffusion and the aperture dimensions. Recently, various additive techniques have been presented to pattern hydrogels. The here‐presented subtractive approach can not only be applied to structure hydrogels from the large class of reversibly formed gels with superior resolution but would also allow for the selective loading of the hydrogels with active substances or nanoparticles.     

聚偏氟乙烯膜表面丙烯酸接枝改性研究

采用自由基接枝聚合反应制备了丙烯酸改性的聚偏氟乙烯膜,研究了单体浓度对接枝率的影响,测定了改性后样品的红外光谱、表面接触角、水通量、蛋白吸附等.结果表明,通过自由基接枝聚合,丙烯酸接枝到膜的表面,明显提高膜的亲水性.接枝后膜的水通量也非常明显下降,特别是在高丙烯酸浓度下.改性的膜的通量对溶液的pH值有明确的响应关系,表明接枝链在水中的溶胀对膜的性能有显著的影响.蛋白吸附实验表明,改性后的膜相比未改性膜有较高的吸附量,而且在酸性情况下,膜的吸附量较大,这主要与丙烯酸和蛋白质之间的相互作用有关.     

Titration force microscopy on supported lipid bilayers

The use of chemically modified atomic force microscopy (AFM) probes allows us to measure the surface charges of supported planar lipid bilayers with high sensitivity through the force spectroscopy operation mode. By controlling the chemistry of the tip, we can perform a classical analytical chemistry titration where the titration agent is a weak acid (attached to the AFM tip) with the particularity of being performed in surface rather than in solution and, especially, at the nanometric scale. Thus, the AFM tip acts as a real "nanosensor". The approaching curves of the force plots reveal that electrostatic interactions between the tip and the supported membrane play a key role. Besides, the plot of the adhesion force (measured from the retracting curve of the force plots) versus pH displays a nonsigmoidal shape with a peak in the adhesion force attributed to high-energy hydrogen bonds. One of these peaks corresponds to the pKa of the surface under study and the other to the pKa of the titrating probe attached to the tip.     

Vibrational and AFM studies of adsorption of glycine on DLC and silicon-doped DLC

A better understanding of protein adsorption onto surfaces of materials is required to control biocompatibility and bioactivity. Diamond-like carbon (DLC) is known to have excellent biocompatibility. Various samples of a-C:H and silicon-doped a-C:H thin films (Si-DLC) were deposited onto silicon substrates using plasma-enhanced chemical vapour deposition (PECVD). Subsequently, the adsorption of the simplest amino acid glycine onto the surfaces of the thin films was investigated to elucidate the mechanisms involved in protein adhesion. The physicochemical characteristics of the surfaces, before and after adsorption of glycine, were investigated using Raman spectroscopy and atomic force microscopy (AFM). The Raman study highlighted a slight decrease in the I _D/I _G ratio with increasing the silicon dopant levels. Following exposure to glycine solutions, the presence of bands at ~1735 and ~1200 cm⁻¹ indicates that the adsorption of glycine onto the surfaces has taken place. Glycine was bound to the surfaces via both deprotonated carboxyl and protonated amino groups whilst, as the silicon content in the DLC film increased the adsorption of glycine decreased. AFM analysis showed that the surface roughness increased following exposure to glycine. These results show that at low silicon doping the adsorption of the amino acid was enhanced whilst increased doping levels led to a reduced adsorption compared to undoped DLC. Therefore, doping of DLC may provide an approach to control the protein adsorption.     

The interfacial behaviour of single poly(N,N-dimethylacrylamide) chains as a function of pH

We have studied the pH-dependent conformational behaviour of poly(N,N-dimethylacrylamide) (PDMAc) at silicon and gold surfaces using single-molecule force spectroscopy and a quartz crystal microbalance (QCM). Despite the pH dependence, nuclear magnetic resonance and titration experiments demonstrate that PDMAc is not a weak polybase. The interaction between single chains and a silicon surface (with native oxide layer intact) in aqueous solution was investigated using force spectroscopy. Single-molecule force measurements were performed using thiol-functionalized PDMAc and gold-coated AFM cantilevers. The forces of interaction between PDMAc and the native oxide-coated silicon surface vary with the pH. The shape of the retraction curve for low pH solution includes a greater number of 'train' conformations, which suggests a stronger interaction with the surface relative to the surrounding media at low pH. The adsorption behaviour of PDMAc, from liquid onto silicon surfaces, was monitored using a QCM, which shows greater PDMAc adsorption onto silicon at low pH. The force spectroscopy and QCM investigations confirm that the PDMAc chain is more extended and stiffer in low pH solution. We attribute the pH-dependent behaviour to an increased number of hydrogen bonding sites on the silicon surface at low pH.