Large-scale dendrimer-based uneven nanopatterns for the study of local arginine-glycine-aspartic acid （RGD） density effects on cell adhesion

Cell adhesion processes are governed by the nanoscale arrangement of the extracellular matrix （ECM）, being more affected by local rather than global concentrations of cell adhesive ligands. In many cell-based studies, grafting of dendrimers on surfaces has shown the benefits of the local increase in concentration provided by the dendritic configuration, although the lack of any reported surface characterization has limited any direct correlation between dendrimer disposition and cell response. In order to establish a proper correlation, some control over dendrimer surface deposition is desirable. Here, dendrimer nanopatterning has been employed to address arginine-glycine-aspartic acid （RGD） density effects on cell adhesion. Nanopatterned surfaces were fully characterized by atomic force microscopy （AFM）, scanning tunneling microscopy （STM） and X-ray photoelectron spectroscopy （XPS）, showing that tunable distributions of cell adhesive ligands on the surface are obtained as a function of the initial dendrimer bulk concentration. Cell experiments showed a clear correlation with dendrimer surface layout： Substrates presenting regions of high local ligand density resulted in a higher percentage of adhered cells and a higher degree of maturation of focal adhesions （FAs）. Therefore, dendrimer nano- patterning is presented as a suitable and controlled approach to address the effect of local ligand density on cell response. Moreover, due to the easy modification of dendrimer peripheral groups, dendrimer nanopatterning can be further extended to other ECM ligands having density effects on cells.     

Photolithographic patterning of dendrimer monolayers and pattern-selective adsorption of linear macromolecules

Alkyl groups of n-octadecyltrimethoxysilane (ODS) in a self-assembled monolayer on a silicon substrate were oxidized to carboxyl groups by partial irradiation of vacuum ultra-violet light under the photomask, producing a COOH/ODS line pattern. After active esterification of carboxyl groups, two kinds of amine-terminated dendrimers, poly(propyleneimine) and poly(amido amine) (PAMAM) dendrimers, were immobilized on a COOH line through amide-bond so that photolithographic dendrimer/ODS pattern was finally fabricated. Preparation was certified by atomic force microscopy (AFM) and surface-enhanced infrared absorption spectroscopy at transmission mode. Adsorption of linear macromolecules was examined on PAMAM dendrimer/ODS pattern. After adsorption of poly-L-glutamic acid (PGA) at a pH below alpha-helix--random coil transition, rod-shape texture was observed only on the dendrimer line in an AFM image. This texture is an aggregate of alpha-helical PGA. Sodium hyaluronate and DNA were also adsorbed selectively on the dendrimer line, keeping the line profile, although characteristic textures were not observed.     

Surface and nanoindentation studies on nanocrystalline titanium diboride thin film deposited by magnetron sputtering

A detailed study on the mechanical, structural and surface characteristics of nanocrystalline TiB₂ films deposited on Si-100 substrates by direct current (DC) magnetron sputtering was carried out. X-ray photoelectron spectroscopy (XPS), atomic force microscope (AFM), nanoindentaion and X-ray diffraction (XRD) studies on these films were performed. Magnetron sputtered titanium diboride coatings had a maximum hardness of 36 GPa and elastic modulus of 360 GPa. From the XRD analyses, the films were found to grow in (00l) direction-oriented perpendicular to the substrate. The AFM analysis of the films showed the variation of grain size between 30 and 50 nm. The high-resolution AFM images revealed arrangements of atoms resembling lattice and the interplanar spacings measured on the image also showed the orientation of grains in the (001) direction. Nanoindentation studies at very shallow depths showed a continuous increase of hardness and modulus with indentation depth up to 40 nm due to tip blunting and presence of oxides on the film surface (confirmed from the XPS study). The elastic recovery was approximately 69% for 100 nm depth whereas it was 52% for 1000 nm depth.     

Improved interfacial properties of carbon fiber/epoxy composites through grafting polyhedral oligomeric silsesquioxane on carbon fiber surface

Carbon fibers were grafted with a layer of uniform octaglycidyldimethylsilyl POSS in an attempt to improve the interfacial properties between carbon fibers and epoxy matrix. Atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and dynamic contact angle analysis were performed to characterize the carbon fibers. AFM results show that the grafting of POSS significantly increased the carbon fiber surface roughness. XPS indicates that oxygen-containing functional groups obviously increased after modification. Dynamic contact angle analysis shows that the surface energy of modified carbon fibers is much higher than that of the untreated ones. Results of the mechanical property tests show that interlaminar shear strength (ILSS) increased from 68.8 to 90.5 MPa and impact toughness simultaneously increased from 2.62 to 3.59 J.     

Direct electrochemistry of laccase immobilized on au nanoparticles encapsulated-dendrimer bonded conducting polymer: application for a catechin sensor

The direct electrochemistry of laccase was promoted by Au nanoparticle (AuNP)-encapsulated dendrimers (Den), which was applied for the detection of catechin. To increase the electrical properties, AuNPs were captured in the interiors of the dendrimer (Den-AuNPs) as opposed to attachment at the periphery of dendrimer. To prepare Den-AuNPs, the Au(III) ions were first coordinated in the interior of dendrimer with nitrogen ligands and then reduced to form AuNPs. The size of AuNPs encapsulated within the interior of the dendrimer was determined to be 1.7 +/- 0.4 nm. AuNPs-encapsulated dendrimers were then used to covalently immobilize laccase (PDATT/ Den(AuNPs)/laccase) through the formation of amide bonds between carboxylic acid groups of the dendrimer and the amine groups of laccase. Each layer of the PDATT/Den(AuNPs)/laccase probe was characterized using CV, EIS, QCM, XPS, SEM, and TEM. The PDATT/Den(AuNPs)/laccase probe displayed a well-defined direct electron-transfer (DET) process of laccase. The quasi-reversible redox peak of the Cu redox center of the laccase molecule was observed at -0.03/+0.13 V vs Ag/AgCl, and the electron-transfer rate constant was determined to be 1.28 s (-1). A catechin biosensor based on the electrocatalytic process by direct electrochemistry of laccase was developed. The linear range and the detection limit in the catechin analysis were determined to be 0.1-10 and 0.05 +/- 0.003 microM, respectively. Interference effects from various phenolic and polyphenolic compounds were also studied, and the general applicability of the biosensor was evaluated by selective analysis of real samples of catechin.     

Monolayer studies of sugar- and nucleoside-terminated dendrimers at the air–water interface

Sugar- and adenosine-terminated dendrimers, [1,2-o-Isopropylideneribosyl-(G₁-12acid), -(G₂-36acid)] and [Adenosyl-(G₁-12acid), -(G₂-36acid)], were synthesized using Newkome's dendrimer synthetic method. Langmuir and Langmuir–Blodgett (LB) monolayers of these dendrimers have been constructed and characterized at the air–water interface and on solid substrates by measuring surface pressure–molecular area (Π–A) isotherms, atomic force microscopy (AFM), ellipsometry and contact angle measurement. Π–A isotherms and AFM images showed that these dendrimers formed stable and homogeneous monolayers without aggregation on pure water surface. The first and second generation of sugar-terminated dendrimers show molecular areas of 647 and 1359 Ų, respectively. Ellipsometry measurement indicates that the thickness of both the first and the second generation of sugar-terminated dendrimers were about 10 Å. This reflects a flat orientation of both molecules at the air–water interface. On the other hand, the first generation of adenosine-terminated dendrimer shows an area of 105.6 Ų per molecule with a thickness of 16 Å, and for the second generation, the area was 738.4 Ų with a thickness of 27 Å. These results suggested that adenosine-terminated dendrimers maintain a spherical form at the air–water interface. It was found that small difference in the structure of thymine and uracil in the subphase critically affects the interaction of the molecules and conformation of the dendrimers at the interface.     

A new strategy for assembling multifunctional nanocomposites with iron oxide and amino-terminated PAMAM dendrimers

A new strategy for assembling multifunctional nanocomposites with magnetic particles and amino dendrimers was reported. In this strategy, the amino terminated PAMAM G5.0 and Fe₃O₄ NPs prepared by co-deposition method and further modified by aminosilane by two sol–gel processes were combined with the hydrophilic spacer of PEG dicarboxylate by amidation. The nanocomposites were characterized by means of X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), atom force microscopy (AFM), superconducting quantum interference device (SQUID) magnetometer, and hydrophilicity analysis. The results showed that the multifunctional nanocomposites were spherical with the mean diameter of 180 nm and exhibited good dispersion and hydrophilicity. The new strategy put forward here provides an effective route to functionalizing Fe₃O₄ NPs with various amino dendrimers for drug and gene delivery as well as biological detection.     

ENFET glucose biosensor produced with dendrimer encapsulated Pt nanoparticles

The biosensors based on ENFETs for direct glucose concentration analysis have been fabricated by introducing dendrimer encapsulated Pt nanoparticles and glucose oxidase (GOx) via a layer-by-layer self-assembly method. The free amine groups located on each poly(amidoamine) dendrimer molecule were exploited to immobilize enzyme through covalent attachment. Depending on metal nanoparticles within dendrimers and biocompatibility of dendrimers, the fabricated glucose sensitive ENFET shows obviously enhanced sensitivity and extended lifetime compared with the conventional ones. The fabricated sensor has a linear range of 0.25–2.0 mM, and a detection limit of ca. 0.15 mM. The influence of buffer concentration, ionic strength and pH was discussed. The biosensor also has good stability, which response could be used for detecting of glucose samples at intervals for at least 1 month when it stored in dry state at 4 °C.     

Improvement of adhesion of fucoidan on polyethylene terephthalate surface using gas plasma treatments

Attachment of polysaccharide fucoidan to the polyethylene terephthalate (PET) polymer surface was studied by X-ray photoelectron spectroscopy (XPS). Fucoidan has antithrombogenic and anticoagulant properties and is therefore a promising coating for vascular graft implants for improving their hemocompatibility. Samples of PET polymer were first modified by nitrogen plasma treatment in order to change the surface wettability and to introduce amino groups to the surface, which act as a linker for further binding of fucoidan. Plasma treated samples were then incubated for 30 min in fucoidan solution. The presence of fucoidan layer on the polymer surface was demonstrated by appearance of S2p signal in the XPS spectra of the coated PET samples. The procedure for immobilization of fucoidan on PET surface was optimized by varying pH value of fucoidan solution from 5 to 7.4. The best results were obtained when using lower pH value pH = 5. At these conditions the thickness of the fucoidan coating was estimated to about 7 nm.     

Grafting carbon nanotubes onto carbon fiber by use of dendrimers

A novel method is developed for grafting carbon nanotubes (CNTs) onto the carbon fiber (CF) surface by use of dendrimers. CF surface is functionalized by an adsorbed dendrimers layer. After an oxidation treatment, CNTs with carboxyl, carbonyl or hydroxyl groups are grafted onto the amino-functionalized CFs via chemical interactions. Homogeneous multi-scale structures with different CNT densities and lengths are gained successfully. Functional groups and morphology of the resulting materials are examined by X-ray photoelectronspectroscopy (XPS), Fourier transform-infrared spectrometer (FTIR), and scanning electron microscopy (SEM).     

Very high temperature chemical vapor deposition of new carbon thin films using organic semiconductor molecular beam sources

We carried out the preparation and characterization of new carbon films deposited using an organic molecular beam deposition apparatus with very high substrate temperature (from room temperature to 2670 K), which we newly developed. When we irradiated molecular beam of organic semiconductor perylene tetracarboxylic acid dianhydride (PTCDA) on Y_0.07Zr_0.93O₂ (111) at 2170 K, a new carbon material was formed via decomposition and fusing of the molecules. The films were characterized with an atomic force microscope (AFM), Raman spectroscopy, X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). Zirconium carbide (ZrC) films were identified beneath the topmost carbon layer by XRD and XPS analyses, which results from chemical reactions of the substrate and the molecules. Partially graphitized aromatic rings of PTCDA were observed from Raman spectroscopy. The present technique – very high temperature chemical vapor deposition using organic semiconductor sources – will be useful to study a vast unexplored field of covalent carbon solids.     

Growth of ZnO nanostructures on Si by means of plasma immersion ion implantation and deposition

Crystalline zinc oxide (ZnO) nanostructures have been grown on Si substrates by means of Plasma Based Ion Implantation and Deposition (PIII&D) at a temperature of about 300 °C and in the presence of an argon glow discharge. In the process a crucible filled with small pieces of metallic zinc plays the role of the anode of the discharge itself, being polarized by positive DC voltage of about 400 V. Electrons produced by thermionic emission by an oxide cathode (Ba, Sr, Ca)O impact this crucible, causing its heating and vaporization of Zn. Partial ionization of Zn atoms takes place due to collisions with plasma particles. High negative voltage pulses (7 kV/40 μs/250 Hz) applied to the sample holder causes the implantation of metallic zinc into Si surface, while Zn deposition happens between pulses. After annealing at 700 °C, strong UV and various visible photoluminescence bands are observed at room temperature, as well as the presence of ZnO nanoparticles. The coated surface was characterized in detail using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), energy dispersive spectroscopy (EDS), scanning electron microscopy (SEM), atomic force microscopy (AFM) and photoluminescence (PL) spectroscopy. XRD indicated the presence of only ZnO peaks after annealing. The composition analysis by EDS revealed distinct Zn/O stoichiometry relation depending on the conditions of the process. AFM images showed the formation of columns in the nanoscale range. Topography viewed by SEM showed the formation of structures similar to cactus with nanothorns. Depth analysis performed by XPS indicated an increase of concentration of metallic Zn with increasing depth and the exclusive presence of ZnO for outer regions. PIII&D allowed to growing nanostructures of ZnO on Si without the need of a buffer layer.     

The effect of substrate temperature on the oxidation behavior of erbium thick films

The effect of substrate temperature on the oxidation behavior of erbium thick films, fabricated by electron-beam vapor deposition (EBVD), was investigated by X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and scanning electron microscopy (SEM). The erbium thick film is black when it is deposited at substrate temperature below 450 °C and turns gray at higher substrate temperature in a vacuum pressure of approximately 1.5 × 10⁻⁶ Torr, which indicates that the thickness of erbium oxide layer formed on the surface of erbium films increases with the decreasing substrate temperature. XPS depth profile results demonstrate that the thickness of the surface erbium oxide layer of erbium film deposited at substrate temperature of 550 and 350 °C are about 50 and 75 nm, respectively. The thicker oxide layer at lower substrate temperatures may be attributed to grain size and the dynamic vacuum condition around the substrates. Other possible factors involved in the oxidation behavior are also discussed.     

Bioactive multilayer thin films of charged N,N-disubstituted hydrazine phosphorus dendrimers fabricated by layer-by-layer self-assembly

Charged N,N-disubstituted hydrazine phosphorus-containing dendrimers are deposited either as alternate all-dendrimers multilayers or alternating with linear polymers on 3-mercaptopropionic acid or 3-aminopropyldimethylethoxysilane coated surfaces via electrostatic layer-by-layer self-assembly. The behavior of the film formation is investigated by surface plasmon resonance spectroscopy and ellipsometry. Fetal cortical rat neurons were cultured on the dendrimer films in order to investigate the influence of the surface charge of the outermost layer on their adhesion and maturation. It was found that neurons attached preferentially and matured slightly faster on film surfaces terminated with positively charged dendrimers than on negatively charged surfaces.     

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.     

Ar + H2 plasma etching for improved adhesion of PVD coatings on steel substrates

Ar + H₂ plasma cleaning has been described for the surface modification of the steel substrates, which removes oxides and other contaminants from substrate surface effectively leading to a better adhesion of the physical vapor deposited (PVD) coatings. Approximately 1.1-1.3 μm thick TiAlN coatings were deposited on plasma treated (Ar and Ar + H₂) and untreated mild steel (MS) substrates. A mechanism has been put forward to explain the effect of plasma treatment on the substrate surface based upon the data obtained from X-ray photoelectron spectroscopy (XPS), field-emission scanning electron microscopy (FESEM) and atomic force microscopy (AFM). The XPS measurements on untreated and Ar + H₂ plasma etched MS substrates indicated that the untreated substrate surface mainly consisted of Fe₃O₄, whereas, after etching the concentration of oxides decreased considerably. The FESEM and the AFM results showed changes in the surface morphology and an increase in the substrate roughness as a result of Ar + H₂ plasma etching. Removal of oxide/contaminants, formation of coarser surface and increased substrate surface roughness as a result of Ar + H₂ plasma etching facilitate good mechanical interlocking at the substrate surface, leading to a better adhesion of the deposited PVD coatings. The adhesion of TiAlN coating could be increased further by incorporating a very thin Ti interlayer.     

Spectroscopic investigations of poly(propyleneimine)dendrimers using the solvatochromic probe phenol blue and comparisons to poly(amidoamine) dendrimers.

The physical and chemical properties of PPI dendrimers' interior were investigated using the fluorescent, solvatochromic probe phenol blue. In aqueous solutions of each generation studied, two discrete dye populations were clearly observed. PPI dendrimers were shown to form a tight, nonpolar association with the vast majority of available dye, within the dendrimer interior, near the core. In the steady-state fluorescence emission spectra, a microenvironment of decreasing polarity in increasingly larger-generation PPI dendrimers (up to G3) was seen for the associated probe. Each of the remaining larger-generation dendrimers provided a microenvironment of essentially equal polarity. Fluorescence anisotropy values for phenol blue in the PPI dendrimers demonstrated the dye's sensitivity to the changing molecular volumes of the dendrimer generations. Model compounds that mimicked PPI's surface groups and branching moieties were used to better define the associated dye's location. The mimics further confirmed that phenol blue was associated inside the dendrimer, where it did not interact with the dendrimer surface groups. The comparison of amine-terminated PPI and PAMAM dendrimers clearly demonstrated the effects of their structural differences and the ability of phenol blue to have sensed those differences, including the initiator core length, branching unit length, and branching unit chemical composition.     

以酯端基PAMAM树形分子为模板在N，M-二甲基甲酰胺溶剂中制备金纳米粒子

用UV-vis、FT-IR光谱研究了HAuCl4和酯端基聚酰胺胺(PAMAM)树形分子在N，N-二甲基甲酰胺(DMF)溶剂中的相互作用，提出HAuCl4与树形分子之间的络合机理：[AuCl4]^-离子与质子化叔胺基团形成离子对，Au^3 离子与PAMAM树形分子上的酯基和酰胺基团形成配位作用。在DMF溶剂中酯端基PAMAM树形分子与HAuCl4配位后用柠檬酸钠还原形成金纳米粒子，UV-vis光谱和TEM图像分析表明了随树形分子代数的增加，金纳米粒子的直径减小，并提出了树形分子-金纳米复合物的结构模型：(1)较低代数的树形分子环绕在金粒子的外围；(2)在较高代数的树形分子空腔内部封装金纳米粒子。     

Amine-terminated TEG-derived PAMAM dendrimer as template for preparation of gold nanoparticles in water

Nano-sized monodisperse gold particles (AuNPs) have received significant attention in the past decade, due to their unique physical properties and good chemical stability, which can lead to a wide variety of potential applications. In this work, TEG-derived PAMAM dendrimers with amine-terminating groups were synthesized and characterized by ¹H NMR and FT-IR. These dendrimers were investigated as the templates for preparation of gold nanoparticles through the reduction of HAuCl₄ by NaBH₄ in water. Stable gold nanoparticles with diameters around 10 nm were obtained in the presence of G2.0 – G5.0 dendrimers and characterized by UV-Vis spectroscopy, transmission electron microscopy (TEM) and dynamic light scattering (DLS). The particle size of the produced AuNPs decreased with increasing dendrimer generations. A dendrimer of higher generation has a rigid structure with many end groups on the surface and may play a powerful role in the growth of the AuNPs, as well as having a solid stabilization effect on the AuNPs.     

Arsenic ion implantation induced structural effects in C60 films

C₆₀ films grown on Si (001) by vacuum evaporation were implanted with 100 keV positive arsenic ions to various doses in the range 1 × 10¹³ to 1 × 10¹⁵ ions/cm². The structural properties of the implanted films were studied using X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and atomic force microscopy (AFM). XPS results indicate the formation of arsenic buried layer within C₆₀ film leading to the anisotropy stress in the film. XRD results reveal the preferential orientation of the film along the (531) plane on implantation and it can be due to the re-alignment of the grains as evidenced by our AFM measurement. AFM measurements also reveal the reduction in the grain size and the surface roughness on implantation.