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Incorporation of organic groups within the channel wall of spin-on mesostructured silica films by a vapor infiltration technique.

Organically functionalized mesoporous silica films have been prepared by a novel synthetic procedure that involves spin-coating of mesostructured silica films and a vapor infiltration (VI) technique, using organosiloxanes, before the removal of surfactant. The VI-treated mesostructured films were characterized using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and a field emission scanning electron microscope (FE-SEM). Nitrogen adsorption/desorption measurements were performed using films attached with a silicon substrate. The XRD and FE-SEM measurements show that the mesochannel wall, densified and modified with organosilyl groups by the VI treatment, hardly contracts under calcination. FE-SEM observations for the films' cross section support the view that organosiloxane vapor is not deposited on the surface of the film. These results show that organosiloxane molecules penetrate the film and are selectively incorporated into the silica wall. Thus, hydrophobic mesoporous silica films can be synthesized without a reduction in pore size, a result that cannot be attained by conventional grafting and co-condensation methods. The excellent high porosity and hydrophobicity of the mesostructured composite films may be of advantage for next-generation low-k dielectric films.

Journal Article↗

Film structures of poly(amido amine) dendrimers with an azacrown core and long alkyl chain spacers on water or Ag nanoparticle suspension.

Newly designed poly(amido amine) dendrimers, which have an azacrown core, hexyl spacers, and methyl ester terminals (aza-C6-PAMAM dendrimer), were spread at the air-water and air-silver nanoparticle suspension interfaces, and their film structures were examined by surface pressure-area (pi-A) and surface potential-area (DeltaV-A) isotherms and epifluorescence microscopy. It was revealed that generation (G) 1.5 aza-C6-PAMAM dendrimer on a water subphase formed homogeneous film with face-on configuration, and this configuration was maintained during compression. On the other hand, a G2.5 dendrimer film on the air-water interface took initially homogeneous and face-on configuration that was followed by the conformational change during compression. Using a silver nanoparticle suspension as subphase, G1.5 film was significantly reinforced, and the partial collapse (cracks) in the film appeared as network texture. For a G2.5 dendrimer film, the pi-A and DeltaV-A isotherm properties were similar to that on the water subphase except for the collapsed film; small spots instead of cracks were formed under the film after collapse. These effects of the silver nanoparticle may be due to the formation of a dendrimer/silver nanoparticle composite. The formation process of the nanocomposite film was verified by UV-vis spectroscopy. For the G1.5 dendrimer, silver clusters and nanoparticles adsorbed to the dendrimer film after spreading and formed a small amount of aggregates. During compression, the aggregation proceeded even at low surface pressure. For the G2.5 dendrimer, a dendrimer/nanoparticle composite was also formed after spreading. However, with the initial compression, the absorption bands of clusters, nanoparticles, and aggregate increased together. Upon further compression, while the bands of cluster and nanoparticles decreased, the bands of aggregate still increased. These results suggest that the G2.5 dendrimer covered the cluster and nanoparticles more efficiently than the G1.5 dendrimer did because of the larger molecular size.

Journal Article↗

Instabilities during the formation of electroactive polymer thin films.

The solvent-induced film structure of poly(n-vinyl carbazole) (PVK) thin films on indium tin oxide (ITO)-coated glass was examined. PVK thin films were prepared via spin-coating using five different solvents. We investigated the relationship between the solvent characteristics and film properties, including surface roughness and structure, film thickness, and density. The spin-coated polymer thin films are not in thermodynamic equilibrium; rather, the film properties are affected by the dynamics of the spin-coating process. We found that water present in tetrahydrofuran (THF) induces dewetting of PVK films during the spin-coating process. Solvents with a high evaporation rate lead to high surface roughness due to Marangoni convection. The results show that the surface roughness and structure of the films are dominated by the dynamics of the film formation process, rather than thermodynamic interactions between the polymer and solvents.

Journal Article↗

Molecular simulations of surface forces and film rupture in oil/water/surfactant systems.

We use dissipative particle dynamics (DPD) and molecular models to simulate interacting oil/water/surfactant interfaces. The system comprises sections of two emulsion droplets separated by a film. The film is in equilibrium with a continuous phase, in analogy with the surface force apparatus. This is achieved by combining DPD with a Monte Carlo scheme to simulate a muVT ensemble. The setup enables the computation of surface forces as a function of the distance between the two interfaces, as well as the detection of film rupture. We studied monolayers of nonionic model surfactants at different densities and compared oil-water-oil and water-oil-water emulsion films. Between surfactant monolayers facing each other tails-on (water-oil-water films), we observed repulsive forces due to the steric interaction between overlapping hydrophobic tails. The repulsion increases with surfactant density. Conversely, no such repulsion is observed between surfactant monolayers facing each other heads-on. Instead, the film ruptures, the monolayers merge, and a channel forms between the two droplet phases. Film rupture can also be induced in the water-oil-water films by forcing the interfaces together. The separation at rupture increases for oil-water-oil films and decreases for water-oil-water films when the surfactant density increases. The results are in qualitative agreement with existing theories of emulsion stability in creams, in particular with the channel nucleation theory based on the natural curvature of surfactants.

Journal Article↗

Photochemical reaction, acidichromism, and supramolecular nanoarchitectures in the Langmuir-Blodgett films of an amphiphilic styrylquinoxaline derivative.

An amphiphilic styrylquinoxaline derivative, 3-(4-(hexadecyloxy)styryl)quinoxalin-2(1H)-one (SQC16), was newly synthesized to investigate their photochemical and gas responsive properties in organized molecular films. It was observed that SQC16 can spread as a monolayer on the subphases with various pH values and be subsequently transferred onto solid substrates. While SQC16 showed predominantly reversible trans-cis photoisomerization in methanol solution, it showed both photoisomerization and photodimerization in Langmuir-Blodgett (LB) films. Photodimerization was only observed in the LB film due to the face-to-face arrangement of the functional headgroup in the LB film, and the process was irreversible. In addition, the LB film showed acidichromism, i.e., when the film was exposed to HCl gas its color changed from yellow to red, and the color could be recovered after exposure to NH(3) gas. The process was reversible and could be repeated many times. An interesting surface morphology of the SQC16 LB film was revealed. It was observed that SQC16 can form nanowire architecture in the transferred one-layer LB film. This morphology can be changed upon photoirradiation or in gas reactions. Through the atomic force microscopy measurements it was suggested that the photodimerization predominantly occurred from the nanowire structures, while during the acidichromism the reaction occurred preferentially in the flat region. X-ray diffraction studies revealed that while layer distance showed a slight change for the LB film during acidichromism and photoreaction, the layer structure of SQC16 LB film was retained.

Membranes, Artificial↗

The effect of water or salt solution on thin hydrophobic films.

Hydrophobic films of polystyrene synthesized in bulk (PS) and by emulsion polymerization in the presence of the cationic surfactant cetyltrimethylammonium bromide (PS-CTAB) or the anionic surfactant sodium dodecyl sulfate (PS-SDS) were characterized by means of ellipsometry, contact angle measurements, and atomic force microscopy. Thin (approximately 65 nm) and thick (approximately 300 nm) films were spin-coated on hydrophilic silicon wafers. PS films presented scarcely tiny holes, while PS-CTAB and PS-SDS films presented holes and protuberances. The former were attributed to dewetting effects and the latter to surfactant clusters. The films were exposed to water or to a 0.1 mol/L NaCl solution for 24 h. Ex situ measurements evidenced strong topographic alterations after the exposure to the fluid. A model based on the diffusion of water (or electrolyte) molecules to the polymer/silcon dioxide interface through holes or defects on the film edges was proposed to explain the appearance of wrinkles and protuberances. In situ ellipsometric measurements were performed and compared with simulations, which considered either a water layer between a polymer and a silcon dioxide layer or an air layer between a polymer and water (medium). In the case of thin PS films, the ellipsometric angles evidenced a very thin (0.5-1.0 nm) air layer between water and the PS films. Upon increasing the PS film thickness, no air layer could be observed by ellipsometry. Regardless of the thickness, the ellipsometric data obtained for PS-CTAB and PS-SDS films did not indicate the presence of an air layer between them and the aqueous media. The dramatic changes in the topography of PS, PS-CTAB, and PS-SDS after immersion in salt solution were explained with proposed models. From a practical point of view, this study is particularly relevant because many hydrophobic polymers are used as substrates for biomedical purposes, where the physiological ionic strength is 0.15 mol/L NaCl.

Journal Article↗

X-ray and neutron reflectometry study of glow-discharge plasma polymer films.

Radio-frequency glow-discharge plasma polymer thin films of allylamine (AA) and hexamethyldisiloxane (HMDSO) were prepared on silicon wafers and analyzed by a combination of X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), X-ray reflectometry (XRR), and neutron reflectometry (NR). AFM and XRR measurements revealed uniform, smooth, defect-free films of 20-30 nm thickness. XPS measurements gave compositional data on all elements in the films with the exception of hydrogen. In combination with XRR and NR, the film composition and mass densities (1.46 and 1.09 g cm(-)(3) for AA and HMDSO, respectively) were estimated. Further NR measurements were conducted with the AA and HMDSO films in contact with water at neutral pH. Three different H(2)O/D(2)O mixtures were used to vary the contrast between the aqueous phase and the polymer. The amount of water penetrating the film, as well as the number of labile protons present, was determined. The AA film in contact with water was found to swell by approximately 5%, contain approximately 3% water, and have approximately 24% labile protons. The HDMSO polymer was found to have approximately 6% labile protons, no thickness increase when in contact with water, and essentially no solvent penetration into the film. The difference in the degree of proton exchange within the films was attributed to the substantially different surface and bulk chemistries of the two films.

Journal Article↗

Mechanical properties of interfacial films formed by lysozyme self-assembly at the air-water interface.

We present the first characterization of the mechanical properties of lysozyme films formed by self-assembly at the air-water interface using the Cambridge interfacial tensiometer (CIT), an apparatus capable of subjecting protein films to a much higher level of extensional strain than traditional dilatational techniques. CIT analysis, which is insensitive to surface pressure, provides a direct measure of the extensional stress-strain behavior of an interfacial film without the need to assume a mechanical model (e.g., viscoelastic), and without requiring difficult-to-test assumptions regarding low-strain material linearity. This testing method has revealed that the bulk solution pH from which assembly of an interfacial lysozyme film occurs influences the mechanical properties of the film more significantly than is suggested by the observed differences in elastic moduli or surface pressure. We have also identified a previously undescribed pH dependency in the effect of solution ionic strength on the mechanical strength of the lysozyme films formed at the air-water interface. Increasing solution ionic strength was found to increase lysozyme film strength when assembly occurred at pH 7, but it caused a decrease in film strength at pH 11, close to the pI of lysozyme. This result is discussed in terms of the significant contribution made to protein film strength by both electrostatic interactions and the hydrophobic effect. Washout experiments to remove protein from the bulk phase have shown that a small percentage of the interfacially adsorbed lysozyme molecules are reversibly adsorbed. Finally, the washout tests have probed the role played by additional adsorption to the fresh interface formed by the application of a large strain to the lysozyme film and have suggested the movement of reversibly bound lysozyme molecules from a subinterfacial layer to the interface.

Air↗

Calcium phosphate thin film processing by pulsed laser deposition and in situ assisted ultraviolet pulsed laser deposition.

Calcium orthophosphates (CaP) and hydroxyapatite (HA) were intensively studied in order to design and develop a new generation of bioactive and osteoconductive bone prostheses. The main drawback now in the CaP and HA thin films processing persists in their poor mechanical characteristics, namely hardness, tensile and cohesive strength, and adherence to the metallic substrate. We report here a critical comparison between the microstructure and mechanical properties of HA and CaP thin films grown by two methods. The films were grown by KrF* pulsed laser deposition (PLD) or KrF* pulsed laser deposition assisted by in situ ultraviolet radiation emitted by a low pressure Hg lamp (UV-assisted PLD). The PLD films were deposited at room temperature, in vacuum on Ti-5Al-2.5Fe alloy substrate previously coated with a TiN buffer layer. After deposition the films were annealed in ambient air at 500-600 degrees C. The UV-assisted PLD films were grown in (10(-2)-10(-1) Pa) oxygen directly on Ti-5Al-2.5Fe substrates heated at 500-600 degrees C. The films grown by classical PLD are crystalline and stoichiometric. The films grown by UV-assisted PLD were crystalline and exhibit the best mechanical characteristics with values of hardness and Young modulus of 6-7 and 150-170 GPa, respectively, which are unusually high for the calcium phosphate ceramics. To the difference of PLD films, in the case of UV-assisted PLD, the GIXRD spectra show the decomposition of HA in Ca(2)P(2)O(7), Ca(2)P(2)O(9) and CaO. The UV lamp radiation enhanced the gas reactivity and atoms mobility during processing, increasing the tensile strength of the film, while the HA structure was destroyed.

Journal Article↗

Victim reactions in aggressive erotic films as a factor in violence against women.

The present study was designed to investigate whether the behavioral characteristics of the people in erotic films and the nature of the targets available for aggression afterward can affect subsequent aggression. In Experiment 1, male subjects were angered by a male or female confederate. They were then shown a neutral film or one of three erotic films. The erotic films differed in terms of their aggressive content (two were aggressive and one was nonaggressive) and the reactions of the female victim in the two aggressive films (positive vs. negative). Subjects were then allowed to aggress against the confederate via electric shock. Results indicated that films had no effect on male targets whereas both types of aggressive erotic films increased aggression toward the female. In Experiment 2, the effects of the above films on nonangry viewers were investigated with only female confederates. Results indicated that angered male subjects were more aggressive toward the female after viewing either aggressive erotic film but that only the positive-outcome aggressive film increased aggression in nonangered subjects. Both the theoretical and applied aspects of aggressive and nonaggressive erotica are discussed.

Aggression↗

Assessment of root resorption and root shape: periapical vs panoramic films.

A radiographic examination is an essential part of the diagnostic process in orthodontics. However, what radiographs are needed to properly evaluate root shape and position? Most clinicians order panoramic or periapical radiographs in addition to the cephalometric radiograph. The purpose of this study was to find out whether one type of film is more accurate than the other in the pretreatment evaluation of root shape and the posttreatment computation of apical root resorption. Pretreatment and posttreatment panoramic films and full-mouth periapical films from 42 patients who completed fixed orthodontic treatment were assessed for tooth length and root shape. Panoramic films showed significantly greater average apicaL root resorption than periapical films for the 743 teeth surveyed. The greatest differences were found in the lower incisors, the least in the maxillary incisors. Classification of root shape was significantly different between the 2 types of radiographs. Root dilacerations and other abnormal shapes, clearly visible on periapical films, often appeared normal on panoramic films. The findings strongly suggest that root shape is much harder to assess on panoramic films. We conclude that, in cases where the apices are obscured or other factors are present that might suggest higher risk for root resorption or vertical bone loss, periapical films should be ordered. The use of panoramic films to measure pre- and posttreatment root resorption may overestimate the amount of root loss by 20% or more.

Adolescent↗

Specific migration of di-(2-ethylhexyl)adipate (DEHA) from plasticized PVC film: results from an enforcement campaign.

A control campaign on the correct labelling of plasticized PVC film according to current legislation on food contact materials has been performed. Analytical methods based on the isotope dilution technique were developed. For enforcement purposes, the films were exposed to the official food simulant, olive oil, followed by clean-up using size exclusion chromatography and final determination of di-(2-ethylhexyl) adipate (DEHA) by combined capillary gas chromatography and mass spectrometry (GC-MS). In the initial screening, the samples were exposed to the alternative food simulant, isooctane, and DEHA could be determined by GC-MS without further clean-up. A good consistency between results from the two different methods was obtained. During the campaign, 49 samples of PVC films, the majority intended for use in retail shops, were sampled from importers and wholesalers by the Municipal Food Control Units. Initially, all films were screened for the migration into isooctane (exposed 2 h at 40 degrees C) of DEHA and other potentially present low molecular weight plasticizers using full scanning mass spectrometry. Films showing a substantial migration of DEHA were further tested with olive oil according to the declared field of application (exposed for 10 days at 40 degrees C). In 47 of the 49 films the migrate contained a substantial amount of DEHA. In 46 films the migration exceeded the specific migration limit of 3 mg/dm2 after use of the relevant reduction factor given in legislation. However, because of the general uncertainty of the analytical method and because the variation in the thickness of the films was calculated to be 1 mg/dm2, the action limit in this campaign was 4 mg/cm2. A migration higher than this action limit was found in 42 films (89% of the samples) and these films were deemed to be illegal according to their present declared field of application as given by their labelling. In a few cases, some migration of the plasticizer di-n-butyl phthalate was seen.

Adipates↗

Contamination characteristics and degradation behavior of low-density polyethylene film residues in typical farmland soils of China.

Low-density polyethylene (LDPE) film residues left in farmlands due to agricultural activities were extensively investigated to evaluate the present pollution situation by selecting the typical areas with LDPE film application, including Harbin, Baoding, and Handan of China. The survey results demonstrated that the film residues were ubiquitous within the investigated areas and the amount reached 2,400-8,200 g ha(-1). Breakage rates of the film residues were almost at the same level in the studied fields. There were relatively small amounts of film residues remaining in neighboring farmland fields without application of LDPE film. The studies showed that the sheets of LDPE residues had the same oxidative deterioration, which was probably due to photodegradation instead of biodegradation. The higher molecular weight components of the LDPE film gradually decreased, which were reflected by the appearance of some small flakes detached from the film bodies. LDPE films in the investigated fields gradually deteriorated and the decomposing levels developed with their left time increasing. The degradation behaviors of LDPE films were confirmed by using Fourier transform infrared (FTIR), scanning electron microscopic (SEM), and gel permeation chromatography analyses.

Agriculture↗

Physical properties and molecular behavior of chitosan films.

Chitosan films, varying in molecular weight and degree of deacetylation, were prepared by a casting technique using acetic acid as a dissolving vehicle. The physicochemical properties of the films were characterized. Both molecular weight and degree of deaceylation affected the film properties. Powder X-ray diffraction patterns and differential scanning calorimetry thermograms of all chitosan films indicated their amorphous state to partially crystalline state with thermal degradation temperature lower than 280-300 degrees C. The increase in molecular weight of chitosan would increase the tensile strength and elongation as well as moisture absorption of the films, whereas the increase in degree of deacetylation of chitosan would either increase or decrease the tensile strength of the films depending on its molecular weight. Moreover, the higher the degree of deacetylation of chitosan the more brittle and the less moisture absorption the films became. All chitosan films were soluble in HCl-KCl buffer (pH 1.2), normal saline, and distilled water. They swelled in phosphate buffer (pH 7.4), and cross-linking between chitosan and phosphate anions might occur Finally, transmission infrared and 13C-NMR spectra supported that chitosan films prepared by using acetic acid as a dissolving were chitosonium acetate films.

Administration, Cutaneous↗

Influence of chlorpheniramine maleate on topical hydroxypropylcellulose films produced by hot-melt extrusion.

The objective of this investigation is to study the influence of chlorpheniramine maleate (CPM) on the chemical and physical-mechanical properties of hydroxypropylcellulose (HPC) hot-melt extruded films without the use of a traditional plasticizer HPC films containing CPM in concentrations of 1, 5, and 10 wt% were prepared by hot-melt extrusion utilizing a Randcastle Microtruder (Model #RCP-0750) with a 6-in. flex-film die. The physical-mechanical properties including tensile strength and percent elongation were determined on an Instron according to the ASTM standards. Glass transition temperatures and thermal analysis of the extruded films were determined utilizing a DSC 2920 Modulated DSC and Thermal Analyst 2000 software. The crystalline properties of the drug, polymer, and extruded films were studied via wide angle X-ray diffraction (XRD) using a Philips Vertical Scanning Diffractometer (Type 42273, Philips Electronic Instrument, Mount Vernon, NY). Gel permeation chromatography was used to study the stability of the polymer matrix as a function of different concentrations of CPM and processing conditions. CPM functioned as an effective plasticizer, increasing percent elongation and decreasing tensile strength in a concentration dependent manner All three concentrations of extruded films exhibited a 10- to 12-fold decrease in tensile strength in contrast to a fourfold increase in percent elongation when testing was performed perpendicular to flow vs. in the direction of flow. The drug was also shown by XRD and DSC data to be in solution in the HPC matrix within the films up to the 10% level. In addition, CPM functioned as a processing aid in the extrusion of hot-melt films, stabilizing the weight-average molecular weight of HPC and allowing for film processing at lower temperatures. CPM could potentially be a candidate antihistamine for transdermal or transmucosal applications in film devices prepared by hot-melt extrusion technology.

Administration, Topical↗

Biomechanical and microstructural characteristics of a collagen film-based corneal stroma equivalent.

The growth in refractive surgeries and corneal replacements has fueled interest in the development of a tissue-engineered cornea. This study characterizes the microstructure and biomechanical properties of film-based corneal stroma equivalents over time in culture. The increased collagen density in the films was hypothesized to result in improved mechanical properties both initially and over time. The microstructure of the film-based stromal equivalent was examined using atomic force microscopy and scanning electron microscopy; the mechanical properties, relaxed modulus, and ultimate tensile strength were quantified using uniaxial tensile testing. The dense, film-based stromal equivalent had a lamellae-like microstructure, which was notably different than the porous structure of sponges used previously. Seeded human corneal stromal fibroblasts remained on the surface of the film rather than migrating into the film and produced fibers of extracellular matrix with diameters of 35-75 nm. After an initial decrease during hydration, the relaxed modulus and ultimate tensile strength for fully hydrated collagen films were 0.4 +/- 0.2 MPa and 0.3 +/- 0.1 MPa, respectively. The mechanical properties of cell-seeded films mimicked those of control films. While further studies are needed to quantify the optical properties, the dense, lamellae-like structure of collagen films is a feasible scaffold for the development of tissue-engineered stroma.

Animals↗

Characterization of 75:25 poly(l-lactide-co-epsilon-caprolactone) thin films for the endoluminal delivery of adipose-derived stem cells to abdominal aortic aneurysms.

Abdominal aortic aneurysms occur in 5-7% of men over the age of 60 and their incidence is rising. Current therapies remove the affected tissue or prevent blood flow through the aneurysm, but do not repair the underlying structural changes of the vascular wall. Adipose tissue derived stem cells (ADSCs) seeded on a biodegradable thin film and delivered endoluminally to the aneurysm site could potentially repair the vessel wall, preventing growth and rupture of the aneurysm. In this study, the mechanical and degradation properties of a novel 75:25 poly(l-lactide-co-epsilon-caprolactone) (PLCL) thin film, as well as, the effects of different surface structures on stem cell adherence and resistance to shear stress was investigated. It was possible to reproducibly create films of consistent physical properties. These films degraded approximately 50% in 6 month, which would be a sufficient time to allow cells to engraft in the aortic wall. Ethylene oxide treatment significantly increased the stiffness and yield stress of the films, which exhibit >700% elongation. Treatment of the films with NaOH and HCl induced the formation of surface texture on the films; however, this texture did not affect stem cell adherence or resistance to delamination by shear stress when compared to nontreated or fibronectin-coated films. These results indicate that PLCL thin films have a sufficient degradation time and mechanical strength to serve as a scaffold in vivo for ADSCs, and that ADSCs seeded on the thin film can withstand a range of physiologic shear stresses.

Adipose Tissue↗

Effect of lauric acid and nisin-impregnated soy-based films on the growth of Listeria monocytogenes on turkey bologna.

Research in development of antimicrobial packaging applications for further processed meats has become more common with recent outbreaks of contamination of these products. In this present study, lauric acid (8%, wt/wt) and 2.5% pure nisin (4%, wt/wt) were incorporated singly and together into thermally compacted soy films. Biocide-impregnated films were compared to control films containing no biocide for inhibition of Listeria monocytogenes in liquid medium and on turkey bologna surface. L. monocytogenes suspended in 1% peptone medium exposed to control films increased from 106 to 10(9) after 48 h exposure at 22 C. Films with nisin alone suppressed cell numbers 1 log cfu/mL after 2 h but cell numbers increased to 10(8) after 24 and 48 h at 22 C. Films containing lauric acid and nisin completely eliminated detectable cells from a 10(6) culture after 8 h of exposure to the liquid medium (22 C). Refrigerated bologna exposed to control films increased by 0.5 log from 10(6) after 21 d at 4 C. Nisin films reduced cell numbers on turkey bologna from 10(6) to 10(5) after 21 d, as did films containing nisin and lauric acid. Films with lauric acid alone reduced L. monocytogenes culture from 10(6) to < 102 after 48 h and by 1 log on turkey bologna after 21 d.

Animals↗