Dendrimer-Mediated Adhesion between Vapor-Deposited Au and Glass or Si Wafers

Here, we report the use of amine-terminated poly(amidoamine) (PAMAM) dendrimers as adhesion promoters between vapor-deposited Au films and Si-based substrates. This method is relatively simple, requiring only substrate cleaning, dipping, and rinsing. Proof of concept is illustrated by coating glass slides and single-crystal Si wafers with monolayers of PAMAM dendrimers and then evaporating adherent, 150-nm-thick Au films atop the dendritic adhesion promoter. Scanning tunneling microscopy and cyclic voltammetry have been used to assess the surface roughness and electrochemical stability of the Au films. The effectiveness of the dendrimer adhesion layer is demonstrated using standard adhesive-tape peel tests.     

Immobilization of dendrimers on Si-C linked carboxylic acid-terminated monolayers on silicon(111)

Poly(amidoamine) dendrimers were attached to activated undecanoic acid monolayers, covalently linked to smooth silicon surfaces via Si-C bonds. The resulting ultra-thin dendrimer films were characterized by X-ray photoelectron spectroscopy (XPS), X-ray reflectometry (XR) and atomic force microscopy (AFM). XPS results suggested amide bond formation between the dendrimer and the surface carboxylic acid groups. XR yielded thicknesses of 10 Å for the alkyl region of the undecanoic acid monolayer and 12 Å for the dendrimer layer, considerably smaller than the diameter of these spherical macromolecules in solution. This was consistent with AFM images showing collapsed dendrimers on the surface. It was concluded that the deformation arose from a large number of amine groups on the surface of each dendrimer reacting efficiently with the activated surface, whereby the dendrimers can deform to fill voids while spreading over the activated surface to form a homogeneous macromolecular layer.     

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.     

Displacement Current of Nanodendrimer

In the Langmuir-Blodgett (LB) technique, a monolayer on the water surface is transferred onto a substrate, which is raised and dipped through the surface. From this, multilayers can be obtained in which constituent molecules are periodically arranged. The LB technique has attracted considerable interest in the fabrication of electrical and electronic devices. Many researchers have investigated the electrical properties of monolayer and multiplayer films. Dendrimers represent a new class of synthetic macromolecules characterized by a regularly branched tree-like structure. Multiple branching yields a large number of chain ends that distinguish dendrimers from conventional star-like polymers and microgels. The azobenzene dendrimer is one of the dendritic macromolecules that include the azo-group exhibiting a photochromic character. Due to the presence of the charge transfer element of the azo-group and its rod-shaped structure, these compounds are expected to have potential interest in electronics and photoelectronics, especially in nonlinear optics. In the present paper, we give pressure stimulation to organic thin films and detect the induced displacement current.     

Directional movement of dendritic macromolecules on gradient surfaces

A gradient-driven methodology has been developed to manipulate the movement of dendritic macromolecules. Poly(propyleneimine) dendrimers, labeled with rhodamine B, are attached to glass substrates via multiple imine bonds. The dendrimers are able to move on the surface by the hydrolysis and re-formation of these imine bonds. In the absence of an external stimulus, this random movement results in a two-dimensional diffusion on the substrate. We are able to bias the movement of these nanoparticles by means of an aldehyde gradient on the glass substrate.     

Nanofabrication of helical peptide-shelled dendrimers

This study describes nanofabrication of helical peptide-shelled dendrimers using a Langmuir monolayer technique. Poly(amido amine) dendrimers (G3) modified with poly(gamma-benzyl-L-glutamate) [number averaged degree of polymerization, n = 12, 17, and 34 (G3-PBLGs hereafter)] were newly prepared by graft polymerization of gamma-benzyl-L-glutamate-N-carboxy anhydride initiated with amino groups of the dendrimer surface. The hydrodynamic diameters of G3-PBLGs were determined to be 6.9 +/- 0.7, 8.2 +/- 1.0, and 11.9 +/- 1.7 nm for n = 12, 17, and 34, respectively, by means of dynamic light scattering. These values were consistent with the theoretical diameters of G3-PBLGs, which were calculated by considering the alpha-helical PBLG segment length. G3-PBLGs were found to form stable monomolecular films with high collapse pressures above 40 mN m-1 at the air-water interface. In addition, these monolayers could be successfully transferred onto various solid substrates. Circular dichroism and Fourier transfer infrared spectroscopies of the deposited G3-PBLGs monolayers showed that PBLG segments took an alpha-helical conformation over a wide range of surface pressure even on solid substrates as well as in bulk solutions. Monolayer thicknesses of these Langmuir-Blodgett films, estimated by x-ray photoelectron spectroscopy and atomic force microscopy, were compatible with the hydrodynamic diameters of G3-PBLGs.     

Growth of multi-amine terminated poly(amidoamine) dendrimers on the surface of carbon nanotubes

An in situ repetitive divergent polymerization strategy was employed to grow multi-amine poly(amidoamine) dendritic macromolecules on the surfaces of multiwalled carbon nanotubes (MWNTs), affording novel three-dimensional (3D) molecular nanocomposites. The crude MWNTs were oxidized using H(2)SO(4)/HNO(3) = 3:1?(v/v) and then reacted with thionyl chloride, resulting in MWNTs functionalized with chlorocarbonyl groups (MWNT-COCl). MWNT-COCl, when reacted with an excess of ethylenediamine, produced amine-functionalized MWNT supported initiators (MWNT-NH(2)). Using the MWNT-NH(2) as the growth supporter and methylacrylate/ethylenediamine as building blocks, multi-amine dendritic poly(amidoamine) macromolecules were covalently grafted onto the sidewalls and ends of MWNTs via Michael addition reaction and amidation. Thermal gravimetric analysis (TGA) measurements showed that the weight ratio of the as-grown dendritic polymers on the MWNT surfaces lay in the 10%-50% range. The products were also characterized by Fourier transform infrared (FTIR), Raman, nuclear magnetic resonance (NMR), and transmission electron microscopy (TEM) analysis. The results indicate that the dendrimers are grafted onto the surface of MWNTs. The as-prepared nanocomposites exhibit excellent dispersibility in water.     

Characterization of self-assembled metallodendrimers in solution, in the gas phase, and at air/solid interfaces

It is found that 4,4'-bipyridines functionalized in their 3,3'-positions with Fréchet dendrons of 0th to 3rd generation self-assemble with (dppp)M(II) triflates (dppp: bis-(diphenylphosphino)propane; M = Pd, Pt) into metallo-supramolecular squares. They bear a nanometer-sized cavity inside an unpolar dendritic shell. A total of eight amide groups decorate the rims of the cavity connecting the dendrons to the square. Evidence for their formation up to the third generation comes from ESI-FTICR mass spectrometry and NMR experiments. Based on these results, the presence of significant amounts of other polygons or open-chain oligomers can be excluded. Exchange processes have been studied by variable-temperature NMR spectroscopy and by following the ligand exchanges between different squares by mass spectrometry. The ligand exchange is much slower for the Pt(II) squares as compared to their Pd(II) analogs. Visualization of films of these dendrimers using atomic force microscopy (AFM) provides information on their molecular dimensions. After deposition of a square monolayer on the surface, a slow reorganization within this layer is observed which leads to the formation of "tower-like" aggregates and multi-layer formation. The interplay of interactions between the dendrimers and the surface and interactions between different dendrimers are invoked to rationalize the observations.     

Thermodynamic and structural studies of mixed monolayers: Mutual mixing of DPPC and DPPG with DoTAP at the air–water interface

Phospholipid monomolecular films at the air–water interface are useful model membranes to understand miscibility among various components. Surface pressure (π)–area (A) isotherms of pure and mixed monolayers of dioleoyltrimethylammonium propane (DoTAP)–dipalmitoylphosphatidylcholine (DPPC) and DoTAP–dipalmitoyphosphatidylglycerol (DPPG) were constructed using a surface balance. DPPC and DPPG produced isotherms as expected and reported earlier. DoTAP, an unsaturated lipid, demonstrated a continuous π–A isotherm. Associative interactions were identified in DPPC–DoTAP mixtures compared to the pure components, while DPPG–DoTAP mixtures showed repulsive interaction up to an equimolar ratio. Compression moduli of the monolayers revealed that DPPC–DoTAP mixtures had increasing stability with increasing surface pressure, but addition of DoTAP to DPPG showed instability at low and intermediate concentrations. In both cases increased stability was returned at higher X_DoTAP values and surface pressures. Lipid monolayer film thickness values, determined on a gold coated glass substrate by surface plasmon resonance spectroscopy (SPR), indicated a systematic change in height profile for DPPC–DoTAP mixtures with increasing X_DoTAP. However, DPPG–DoTAP mixed monolayer systems demonstrated a biphasic response. The SPR data were in excellent agreement with our interpretation of the structure of solid supported lipid monolayers.     

Dip-pen nanolithography on (bio)reactive monolayer and block-copolymer platforms: deposition of lines of single macromolecules

The application of atomic force microscopy (AFM) tip-mediated molecular transfer (dip-pen nanolithography or DPN) to fabricate nanopatterned (bio)reactive platforms based on dendrimers on reactive self-assembled monolayer (SAM) and polymer thin films is discussed. The transfer of high-molar-mass polyamidoamine (PAMAM) dendrimers (generation 5) and the rapid in situ covalent attachment of the deposited adsorbates onto reactive N-hydroxysuccinimide (NHS) terminated SAMs on gold and NHS-activated polystyrene-block-poly(tert-butyl acrylate) (PS(690)-b-PtBA(1210)) block copolymer thin films were investigated as strategies to suppress line broadening by surface diffusion in DPN. By exploiting carefully controlled environmental conditions (such as temperature and relative humidity), scan rates, and in particular the covalent attachment of the dendrimers to the reactive films, the observed line broadening and hence the lateral diffusion of dendrimers was substantially less pronounced compared to that observed with DPN of thiols on gold. By this method, high-definition patterns of dendrimers were conveniently fabricated down to 30-nm length scales. The presence of primary amino groups in the deposited dendrimers ultimately offers the possibility to anchor biochemically relevant molecules, such as proteins and polypeptides, to these nanostructured platforms for a wide range of possible applications in the life sciences and in particular for the investigation of controlled cell-surface interactions.     

两亲性聚对苯乙撑的合成及其LB膜研究

本文通过wittig反应合成出了具有两亲性的聚对苯乙撑（PPV）类衍生物,通过核磁和红外对其进行了相关鉴定,并将其铺展上水面上,制得了稳定的单分子膜,并通过计算其单分子面积,研究了其分子在空气／水界面上的取向排列。在对多层LB膜的紫外光谱研究中发现,紫外吸光强度和层数成正比,说明该聚合物的单分子膜在转移过程中膜内分子的取向、构象及堆积方式没有随层数的增加而改变。     

Kinetic and equilibrium binding analysis of protein-ligand interactions at poly(amidoamine) dendrimer monolayers

The interaction of streptavidin (SA) with a biotinylated surface has been of great interest in the development of an interfacial layer for protein immobilization based on self-assembled monolayers (SAMs) and polymeric layers. Here, we demonstrate the unique characteristics of protein-ligand interactions on dendrimer monolayers based on kinetic and equilibrium binding analyses. With amine-ended poly(amidoamine) dendrimers from the first (G1) to fourth (G4) generation, the formation of even, compact dendrimer monolayers on gold was confirmed using FT-IR spectroscopy and ellipsometry. For the SA-biotin interaction, quantitative analysis of bound SA using surface plasmon resonance showed that the saturation binding level of SA was fairly higher in all dendrimer layers when compared to other tested systems of 11-mercaptoundecylamine SAMs and a poly(L-lysine) layer. Kinetic studies revealed that the initial binding rate of SA up to the saturation level was 2-fold higher in all dendrimer layers than in the SAMs regardless of the surface density of functionalized biotin. Concurrently, the dendrimer layers led to much higher values of sticking probability, which is defined as the probability that the SA molecule adsorbs upon collision with a biotinylated surface, at a fixed SA coverage, and prolonged the significant levels around the maximum probability with increasing SA coverage. Plots of the saturation coverage of SA versus the SA concentration in solution showed that SA binding onto the biotinylated G1 and G3 layers fit to a Langmuir isotherm model. Taken together, faster binding of SA and highly ordered packing of the molecules seems to be achieved through typical properties of the dendrimer monolayers such as surface distribution of functionalized biotin, surface corrugation, and flexibility of highly branched larger dendrimers, which provides a guideline for the construction and analysis of an interfacial layer in biosensing applications.     

Enhancement of protection of aluminum through dopamine impregnation into hybrid sol–gel monolayers

The present work involves the incorporation of dopamine (DA) into the hybrid sol–gel monolayers (Hy) consisting of (3-glycidoxypropyl)methyldiethoxysilane and Tetraethyl orthosilicate. The resultant doped hybrid layers coated over aluminum surface was characterized by FT-IR, UV–Vis, XRD, EDX and SEM analyses. The corrosion behavior of bare and coated aluminum substrates in 3.5 % NaCl medium was examined by cyclic voltammetry, potentiodynamic polarization and electrochemical impedance spectroscopy techniques. Results from the electrochemical measurements showed that the DA impregnated Hy sol–gel monolayers offered better corrosion protection with superior coating thickness than the Hy sol–gel monolayers without DA. The enhancement of protection could be attributed to the fact that DA promote the formation of strongly bonded and densely packed monolayer films, which show better adhesion than the conventional silane systems.     

Poly(amidoamine) dendrimers as nanoscale diffusion probes in sol-gel films investigated by total internal reflection fluorescence spectroscopy

Three generations of poly(amidoamine) dendrimers were dye-labeled and chemically modified to have terminal carboxyl groups and used as variably sized probes to study diffusion in thin sol-gel films. Total internal reflection fluorescence spectroscopy experiments, both correlation and concentration-jump measurements, were employed to measure the relative populations and effective diffusion coefficients of dendrimers in the films. For films prepared from small (27-nm) silica particles, larger dendrimers could be completely excluded from penetrating the sol-gel structure. In films made of larger (150-nm) particles with correspondingly larger pores, concentration-jump experiments showed that larger dendrimers are excluded from more of the intraparticle pore space than small dendrimers. Similarly, fluorescence-correlation measurements showed that the diffusion of smaller dendrimers exhibited greater tortuosity than larger dendrimers in the interparticle pores of the film. The smaller dendrimers explore a greater volume of smaller, more convoluted pores, whereas larger dendrimers penetrate a smaller volume of larger, more open pores.     

De novo growth of poly(amidoamine) dendrimers on the surface of multi-walled carbon nanotubes

Carbon nanotubes (CNTs) are often used after modification. Poly(amidoamine) (PAMAM) dendrimers modified CNTs have attracted attentions due to their rich terminal amino groups. However, direct grafting of PAMAM dendrimers on CNTs’ surface is limited by the steric hindrance and its supply. De novo growth of PAMAM on multi-walled carbon nanotubes (MWCNTs), i.e., PAMAM@CNTs, is expected to eliminate the limits since the adopted reagents are readily available small molecular chemicals. It was realized using a divergent method and a “grafting from” technique by alternate amidization of terminal ester groups with ethylenediamine and Michael addition of methyl acrylate to the yielding amino groups. Spectral analysis, including Fourier transform infrared, Raman, hydrogen nuclear magnetic resonance, and X-ray photo-electron spectroscopy, verified that the functional groups were covalently grafted on the surface of MWCNTs, while thermogravimetric and elemental analysis showed that these groups were exponentially grown on MWCNTs, suggesting the formation of a dendritic PAMAM. Besides, high resolution transmission electron microscopy also confirmed that the spherical PAMAM was formed on the CNTs’ surface and an average particle size of 15–20 nm for G8.0-dendrimers was obtained.     

Influence of polyvinyl pyrrolidone on the formation and properties of ZnO thin films in chemical bath deposition

Thin films consisting of ZnO nanoparticles were prepared by solvolysis from solutions of zinc acetate, polyvinyl pyrrolidone (PVP) and sodium hydroxide in 2-propanol at temperatures of 328 K. Uniform, photoluminescent films with homogeneous surface coverage were obtained on silicon wafers modified with SO₃–H terminated self-assembled monolayers (SAMs). High resolution transmission electron micrographs and the corresponding electron diffraction patterns in combination with X-ray Photoelectron Spectroscopy revealed that nanocrystalline wurtzite-type ZnO is present in the films.     

A trough with radial compression for studies of monolayers and fabrication of Langmuir-Blodgett films

A new type of Langmuir trough with radial compression is reported for studies of monolayer properties and fabrication of Langmuir-Blodgett (LB) films. The trough included twenty curved diaphragms, which form a circular shape on water and compress monolayers. Typical monolayers of arachidic acid, DL--phosphatidylcholine dipalmitoyl, cellulose tridecanoate, and poly (butyl methacrylate) showed reproducible surface pressure-area isotherms with radial compression. Flow profiles were studied of monolayers on cellulose tridecanoate and poly(butyl methacrylate) and suggested that the monolayers are radially compressed with no particular film disturbance. A Wilhelmy glass plate preserved no deflection in the subphase surface from low to high surface pressures during the film compression and decompression; no pressure excess causing the deflection, which is frequently observed in the case of the film compression with a sliding barrier, was found on both sides of the Wilhelmy plate. Application of the radial compression enabled to do a symmetrical deposition for the fabrication of LB films.     

平整二钛酸钾薄膜的制备及其气相光催化活性

采用溶胶-凝胶法制备了K2Ti2O5薄膜并进行表征;在K2Ti2O5薄膜表面上形成致密的十八烷基三氯硅烷(C18H37SiCl3,OTS)单层自组装膜(SAMs);用OTS SAMs 水接触角变化研究薄膜的气相光催化活性;测量了薄膜的光电流响应.研究发现:K2Ti2O5薄膜表面平整、均匀、致密、在玻璃基片上透明;在紫外和可见光区都有光吸收;K2Ti2O5薄膜上OTS SAMs在空气中用254nm的紫外光照射时降解速度比在TiO2薄膜上快;K2Ti2O5薄膜产生阳极光电流,比TiO2薄膜具有更强的光激发和更稳定的光电流响应.结果表明,K2Ti2O5薄膜在空气中用紫外光照射能很有效的分解OTS SAMs,是一种很好的治理气相有机污染物的光催化剂.     

The Development of Light‐Emitting Dendrimers for Displays

Dendrimers are now an important class of light‐emitting material for use in organic light‐emitting diodes (OLEDs). Dendrimers are branched macromolecules that consist of a core, one or more dendrons, and surface groups. The different parts of the macromolecule can be selected to give the desired optoelectronic and processing properties. The first light‐emitting dendrimers were fluorescent but more recently highly efficient phosphorescent dendrimers have been developed. OLEDs containing light‐emitting dendrimers have been reported to have external quantum efficiencies of up to 16 %. The solubility of the dendrimers opens the way for simple processing and a new class of flat‐panel displays. In this Review we show how the structure of the light‐emitting dendrimers controls key features such as intermolecular interactions and charge transport, which are important for all OLED materials. The advantages of the dendrimer architecture for phosphorescent emitters and the way the structure can be varied to enhance materials performance and device design are illustrated.     

X-ray photoelectron spectroscopy, time-of-flight secondary ion mass spectrometry, and principal component analysis of the hydrolysis, regeneration, and reactivity of N-hydroxysuccinimide-containing organic thin films

N-Hydroxysuccinimide (NHS) esters are widely used as leaving groups to activate covalent coupling of amine-containing biomolecules onto surfaces in academic and commercial surface immobilizations. Their intrinsic hydrolytic instability is well-known and remains a concern for maintaining stable, reactive surface chemistry, especially for reliable longer term storage. In this work, we use X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry (TOF-SIMS) to investigate surface hydrolysis in NHS-bearing organic thin films. Principal component analysis (PCA) of both positive and negative ion TOF-SIMS data was used to correlate changes in the well-defined NHS ester oligo(ethylene glycol) (NHS-OEG) self-assembled monolayers to their surface treatment. From PCA results, multivariate peak intensity ratios were developed for monitoring NHS reactivity, thin-film thickness, and oxidation of the monolayers during surface hydrolysis. Aging in ambient air for up to 7 days resulted in hydrolysis of some fraction of bound NHS groups, oxidation of some resident thiol groups, and deposition of adventitious hydrocarbon contaminants onto the monolayers. Overnight film immersion under water produced complete hydrolysis and removal of the NHS chemistry, as well as removal of some of the thiolated OEG chains. NHS regeneration of the hydrolyzed surfaces was assessed using the same multivariable peak intensity ratio as well as surface coupling with amine-terminated molecules. Both aqueous and organic NHS regeneration methods produced surfaces with bound NHS concentrations approximately 50% of the bound NHS concentration on freshly prepared NHS-OEG monolayers. Precise methods for quantifying NHS chemistry on surfaces are useful for quality control processes required in surface technologies that rely on reliable and reproducible reactive ester coupling. These applications include microarray, microfluidic, immunoassay, bioreactor, tissue engineer-ing, and biomedical device fabrication.