Surface plasmon resonance and electrochemistry characterization of layer-by-layer self-assembled DNA and Zr4+ thin films, and their interaction with cytochrome c

Through electrostatic layer-by-layer (LbL) assembly, negatively charged calf thymus double stranded DNA (CTds-DNA), and positively charged Zr4+ ions were alternately deposited on gold substrate modified with chemisorbed cysteamine. Thus-prepared three-dimensional DNA networks were characterized by surface plasmon resonance (SPR) spectroscopy, X-ray photoelectron spectroscopy (XPS) and infrared reflection-absorption spectroscopy (IR-RAS). SPR spectroscopy indicates that the effective thickness of DNA monolayer in the (DNA/Zr4+), bilayer was 1.5 +/- 0.1 nm, which corresponds to the surface coverage of 79% of its full packed monolayer. At the same time, a linear increase of film thickness with increasing number of layers was also confirmed by SPR characterizations. The data of XPS and IR-RAS show that Zr4+ ions interact with both the phosphate groups and nitrogenous bases of DNA and load into the framework of DNA. Furthermore, the interactions between this composite film and heme protein cytochrome c (Cyt c) were investigated by SPR spectroscopy and electrochemistry. Compared with the adsorption of Cyt c on DNA monolayer, this composite multilayer film can obviously enhance the amount of immobilized Cyt c confirmed by SPR reflectivity-incident angle (R-theta) curves.

A Monte Carlo simulation of morphology and structure for thin films of symmetric triblock copolymer after quenching and annealing

Self-assembly thin films of symmetric triblock copolymer after annealing and quenching were examined by an effective Monte Carlo simulation method. The defects in the ordered lamellae of the thin films after quenching, which were dependent on the initialization of copolymer melts, are removed in the thin films after annealing. The mean-square gyration radius and end-to-end distance of copolymer chains in the thin films after annealing are smaller than those in the thin films after quenching because of the complete relaxation of polymer during annealing. We also find that the density of A block in the region near to the surface is higher than that in the interior of the thin films. As a result, it is different from the thin films of symmetric A(n)B(n) diblock copolymer, in which surface ordering forms before the interior, that ordering phenomena occurs first in the interior region in the thin films of symmetric A(n)B(m)A(n). triblocl copolymer.

The formation of ordered nanoholes in binary, chemically similar, symmetric diblock copolymer blend films

Binary symmetric diblock copolymer blends, that is, low-molecular-weight poly(styrene-block-methyl methacrylate) (PS-b-PMMA) and high-molecular-weight poly(styrene-block-methacrylate) (PS-b-PMA), self-assemble on silicon substrates to form structures with highly ordered nanoholes in thin films. As a result of the chemically similar structure of the PMA and the PMMA block, the PMMA chain penetrates through the large PMA block that absorbs preferentially on the polar silicon substrate. This results in the formation of nanoholes in the PS continuous matrix.

Vacuum-deposited submonolayer thin films of a three-ring bent-core compound

Submonolayer thin films of a three-ring bent-core (that is, banana-shaped) compound, m-bis(4-n-octyloxystyryl)benzene (m-OSB), were prepared by the vacuum-deposition method, and their morphologies, structures, and phase behavior were investigated by atomic force microscopy (AFM) and transmission electron microscopy (TEM). The films have island shapes ranging from compact elliptic or circular patterns at low temperatures (below 40 degreesC) to branched patterns at high temperatures (above 60 degreesC). This shape evolution is contrary to the prediction based on the traditional diffusion-limited aggregation (DLA) theory. AFM observations revealed that two different mechanisms governed the film growth, in which the compact islands were formed via a dewetting-like behavior, while the branched islands diffusion-mediated. It is suggested m-OSB forms a two-dimensional, liquid crystal at the low-temperature substrate that is responsible for the unusual formation of compact islands. All of the monolayer islands are unstable and apt to transform to slender bilayer crystals at room temperature. This phase transition results from the peculiar molecular shape and packing of the bent-core molecules and is interpreted as escaping from macroscopic net polarization by the formation of an antiferroelectric alignment.

Luminescent sol-gel thin films based on europium-substituted heteropolytungstates

Polyester thin films containing europium-substituted heteropolytungstate were obtained on quartz plate by the sol-gel method. The films exhibited the characteristic emission bands of the europium ion. The red to orange intensity ratio (R:O) of Eu3+ in the films increased as compared to the corresponding heteropolytungstate solids. The fluorescence lifetime of europium is shorter in the thin film than in the heteropolytungstate solid. The results indicated that the formation of europium-substituted heteropolytungstate/polyester thin film has great effect on the luminescence of europium- substituted heteropolytungstate.

Polyhedral oligomeric silsesquioxane nanocomposite thin films via layer-by-layer electrostatic self-assembly

Fabrication of ultrathin polymer composite films with low dielectric constants has been demonstrated. Octa( aminophenyl) silsesquioxane (OAPS) was synthesized and assembled with poly( acrylic acid) (PAA) and poly( styrene sulfonate) (PSS) via a layer-by-layer electrostatic self-assembly technique to yield nanoporous ultrathin films. The OAPS was soluble in water at pH 3 or lower, and suitable pH conditions for the OAPS/PAA and OAPS/PSS assemblies were determined. The multilayer formation process was studied by contact angle analysis, X-ray photoelectron spectroscopy, atomic force microscopy, quartz crystal microgravimetry, UV-vis spectroscopy, and ellipsometry. The multilayer growth was found to be steady and uniform, and the analysis of the film surface revealed a rough topography due to OAPS aggregates. The incorporation of porous OAPS molecules into the thin films significantly lowered their dielectric constants. The OAPS/PAA multilayer thin film thus prepared exhibited a dielectric constant of 2.06 compared to 2.58 for pure PAA film. The OAPS/PAA multilayer film was heated to effect cross-linking between the OAPS and the PAA layers, and the transformation was verified by reflection-absorption Fourier transform infrared spectroscopy.

Photoluminescent properties of sol-gel derived (La, Gd)MgB5O10 : Ce3+/Tb3+ nanocrystalline thin films

Ce3+ and/or Tb3+-doped (La,Gd)MgB5O10 nanocrystalline thin films were deposited on silica glass substrates by a sol-gel dip-coating process using triethyl borate B(OC2H5)(3) as the boron source. The results of XRD indicated that the films have fully crystallized after annealing at 800 degrees C. The films are transparent, uniform and crack free with a thickness of about 300 nm, consisting of particles with an average grain size of 50 nm. The luminescence and energy transfer properties of Ce3+ and Tb3+ have been studied in the films. It is confirmed that the excitation energy of Ce3+ transfers to the Gd3+, migrates over the Gd3+ sublattices, trapped by the Tb3+ and resulted in its characteristic green emission (D-5(4)-F-7(5) at 543 nm) in GdMgB5O10 nanocrystalline films as in the powder phosphors.

Sol-gel synthesis and photoluminescent properties of LaPO4 : A (A = Eu3+, Ce3+, Tb3+) nanocrystalline thin films

Rare-earth ion (Eu3+, Tb3+, Ce3+)- doped LaPO4 nanocrystalline thin films and their patterning were fabricated by a Pechini sol-gel process combined with soft lithography on silicon and silica glass substrates. X-Ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), thermogravimetric and differential thermal analysis (TG-DTA), atomic force microscopy (AFM), scanning electron microcopy (SEM), optical microscopy, absorption and photoluminescence (PL) spectra as well as lifetimes were used to characterize the resulting films. The results of XRD indicate that the films begin to crystallize at 700 degreesC and the crystallinity increases with increasing annealing temperature. The morphology of the thin film depends on the annealing temperature and the number of coating layers. The 1000 degreesC annealed single layer film is transparent to the naked eye, uniform and crack-free with a thickness of about 200 nm and an average grain size of 100 nm. Patterned thin films with different strip widths ( 5 - 50 mm) were obtained by micromolding in capillaries ( soft lithography). The doped rare earth ions show their characteristic emission in the nanocrystalline LaPO4 films, i.e., Eu3+ D-5(0)-F-7(J) (J = 1, 2, 3, 4), Tb3+ D-5(3,4) - F-7(J) ( J = 6, 5, 4, 3, 2) and Ce3+ 5d-4f transition emissions, respectively. Both the lifetimes and the PL intensities of Eu3+ and Tb3+ increase with increasing annealing temperature, and the optimum concentrations for them were determined to be 5 mol% and 16 mol% of La3+ in LaPO4 thin films, respectively. An energy transfer phenomenon from Ce3+ to Tb3+ has been observed in LaPO4 nanocrystalline thin films, and the energy transfer efficiency depends on the doping concentration of Tb3+ if the concentration of Ce3+ is fixed.

Sol-gel fabrication, patterning and photoluminescent properties of LaPO4 : Ce3+, Tb3+ nanocrystalline thin films

Ce3+ and/or Tb3+-doped LaPO4 nanocrystalline thin films and their patterning were fabricated by a sol-gel process combined with soft lithography on silicon and quartz glass substrates. The results of XRD indicated that the films began to crystallize at 700 degreesC. The 1000 degreesC annealed single layer films are transparent by eyes, uniform and crack-free with a thickness of about 200 nm and an average grain size of 100 nm. Patterned thin film with different band widths (5-50 mum) were obtained by micro-molding in capillaries technique. The luminescence and energy transfer properties of Ce3+ and Tb3+ were studied in LaPO4 films.

Luminescence properties of RP1-xVxO4: A (R=Y, Gd, La; A=Sm3+Er3+ x=0, 0.5, 1) thin films prepared by pechini sol-gel process

Thin film phosphors with compositions of RP1-xVxO4: A (R = Y, Gd, La; A = Sm3+, Et3+; x = 0, 0.5, 1) have been prepared by a Pechini sol-gel process. X-Ray diffraction, atomic force microscopy (AFM), photoluminescence excitation and emission spectra were utilized to characterize the thin film phosphors. The results of XRD showed that a solid solution formed in YVxP1-xO4: A film series from x = 0 to x = 1 with zircon structure, which also held for GdVO4: A film. However, LaVO4: A film crystallized with a different structure, monazite. AFM study revealed that the phosphor films consisted of homogeneous particles ranging from 90 to 400 nm depending on the compositions. Upon short ultraviolet excitation, the films exhibit the characteristic Sm(3+ 4)G(5/2)-H-6(J) (J=5/2, 7/2, 9/2) emission in the red region and Er3+ H-2(11/2), S-4(3/2)-I-4(15/2) emission in the green region, respectively With the increase of x values in YVxP1-xO4: SM3+ (Er3+) films, the emission intensity Of SM3+ (Er3+) increases due to the increase of energy transfer probability from VO43- to Sm3+ (Er3+). Due to the structural effects, the Sm3+ (Er3+) shows similar spectral properties in YVO4 and GdVO4 films, which are much different from those in LaVO4 film.

Direct electrochemistry and surface plasmon resonance characterization of alternate layer-by-layer self-assembled DNA-myoglobin thin films on chemically modified gold surfaces

Alternate layer-by-layer (L-by-L) polyion adsorption onto gold electrodes coated with chemisorbed cysteamine gave stable, electroactive multilayer films containing calf thymus double stranded DNA (CT ds-DNA) and myoglobin (Mb). Direct, quasi-reversible electron exchange between gold electrodes and proteins involved the Mb heme Fe2+/Fe3+ redox couple. The formation of L-by-L (DNA/Mb), films was characterized by both in situ surface plasmon resonance (SPR) monitoring and cyclic voltammetry (CV). The effective thickness of DNA and Mb monolayers in the (DNA/Mb)l bilayer were 1.0 +/- 0.1 and 2.5 +/- 0.1 mn, corresponding to the surface coverage of similar to65% and similar to89% of its full packed monolayer, respectively. A linear increase of film thickness with increasing number of layers was confirmed by SPR characterizations. At pH 5.5, the electroactive Mb in films are those closest to the electrode surface; additional protein layers did not communicate with the electrode. CV studies showed that electrical communication might occur through hopping conduction via the electrode/base pair/Mb channel, thanks to the DNA-Mb interaction. After the uptake of Zn2+, a special electrochemical behavior, where MbFe(2+) acts as a DNA-binding reduction catalyst in the Zn2+-DNA/Mb assembly, takes place.

Pattern formation in polymer films under the mask

This paper presents a straightforward method for patterning thin films of polymers, i.e. a prepatterned mask is used to induce self-assembly of polymers and the resulting pattern is the same as the lateral structures in the mask on a submicrometre length scale, The patterns can be formed at above T-g + 30 degreesC in a short time and the external electric field is not crucial. Electrostatic force is assumed to be the driving force for the pattern transfer. Viscous fingering and novel stress-relief lateral morphology induced under the featureless mask are also observed and the formation mechanisms are discussed.

Luminescent self-assembled thin films based on rare earth-heteropolytungstate

earth (Eu3+, Dy3+)-heteropolytungstate thin films were fabricated by self-assembly method successfully. The thin films give off strong fluorescence, which can be observed by eyes upon UV irradiation. The characteristic emission behaviors of the rare earth ions in self-assembled thin film were investigated compared with those of the corresponding solids. It is noticed that the intensity ratio between D-5(0) --> F-7(2) and D-5(0) --> F-7(1) of Eu3+ and the intensity ratio between F-4(9/2) --> H-6(13/2) and F-4(9/2) --> H-6(15/2) of Dy3+ in the self-assembled films are different from those of the corresponding solids. Furthermore, the self-assembled films present shorter fluorescence lifetimes than the corresponding solids. The reasons for these results have been discussed.

Preparation and characterization of luminescent thin films doped with rare earth (Tb3+, Eu3+) complexes derived from a sol-gel process

Sol-gel derived luminescent thin films doped with rare earth (RE) complexes were prepared using an in-situ synthesis method with a two-step hydrolysis process and the luminescence spectra were measured. Fluorescence Lifetime and thermal stability were investigated. The results show that a broad excitation band indicates the formation of RE complexes in the solid thin films. RE ions, which are restrained in a silica matrix, present longer lifetime and higher thermal stability than that in DMF/PVB films containing the corresponding pure complexes. (C) 2000 Elsevier Science B.V. All rights reserved.

The single crystal-like banded textures in the films of a thermotropic liquid crystalline poly(aryl ether ketone) containing a lateral chloro group

The banded textures in the films of a thermotropic liquid crystalline poly(aryl ether ketone) containing a lateral chloro group have been studied by means of transmission electron microscopy(TEM), electron diffraction(ED) and atomic force microscopy (AFM). The crystallization-induced Landed texture without external shear can be formed when the thin films were annealed at the temperature range(320-330 degrees C) of the liquid crystalline state from the melt, The results show that the banded regions have high orientation of single crystal based on the orthorhombic packing and the growing direction of the Lands is along the b axis of the crystals, This kind of single crystal-like bands is due to the different orientation of the packing molecular chains, The molecular chains of the dark bands in the bright field electron micrograph are perpendicular to the film plane, while the ones of the bright Lands are tilt along the b axis with the tilt angle upto +/-20 degrees.