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PubMed2004

Fully-biodegradable poly(3-hydroxybutyrate)/poly(vinyl alcohol) blend films with compositional gradient.

Fully-biodegradable bacterial poly(3-hydroxybutyrate) (PHB)/chemosynthetic poly(vinyl alcohol) (PVA) blend films with compositional gradient from one surface to the other surface of the films were prepared by a dissolution-diffusion technique. Three kinds of PVA samples, high- and low-molecular weight atactic PVA and highly syndiotactic PVA (s-PVA), were used in order to investigate the effects of molecular weight and tactic structure on the generation of compositional gradient. The solution of PHB in 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP), which is also a good solvent for PVA, was cast on the PVA film and then the solvent HFIP was evaporated. By selecting the optimum volume of solvent and the evaporation rate, the PHB/PVA blend film with compositional gradient was obtained. The formation of compositional gradient was confirmed by FT-IR microscopy and ATR-FT-IR analysis. The 50%/50% PHB/s-PVA blend film with a nearly ideal compositional gradient, that is, the composition of PHB (or PVA) in the film changing gradually from 100% at one surface to 0% at the other surface of the film was obtained by casting PHB/HFIP solution on to the s-PVA film. Positional dependence of the absorbance of C==O and OH stretching bands along the film thickness direction for the PHB/S-PVA cast films.

Absorption↗
PubMed1996

Deposition and Thinning of the Human Tear Film

The exposed part of the eyeball is covered by a tear film, which is vital for the proper function of the eye. The film thickness has been measured to be roughly 10 μm; however, how a tear film of this thickness is generated has not been clearly explained. It is proposed that the tear film is deposited analogous to a coating process by the rising meniscus of the upper lid during a blink. A coating model is formulated that not only predicts correctly the film thickness, but also captures the postblink lipid spreading commonly observed in experiments. A deposited tear film thins rapidly near the tear meniscus surrounding the film. Numerical simulation of this thinning reveals that the minimum film height obeys a power law. When the minimum height reaches the effective range of dewetting intermolecular forces, the film ruptures. The thinning time therefore defines a breakup time, and the thinning law shows explicitly how this breakup time is related to tear viscosity, surface tension, meniscus radius, and initial and final film thicknesses. The calculated breakup time agrees with those observed experimentally.

Journal Article↗
PubMed1997

Characterization of Organofunctional Silane Films on Zinc Substrates

Organofunctional silane films formed on pure zinc substrates from aqueous solutions were characterized by ellipsometry, contact angle measurements, reflection absorption infrared spectroscopy (RAIR), X-ray photoelectron spectroscopy (XPS), and atomic force microscopy (AFM). The silanes studied were gamma-aminopropyltriethoxysilane (gamma-APS) and gamma-ureidopropyltrialkoxysilane (gamma-UPS). The deposition parameters included solution concentration, solution dipping time, and pH value of the applied solution. Effects of these deposition variables on the thickness of the film, the surface energy of the film, the chemical structure of the film, and the surface topography of the film are discussed. The effect of film aging time on the surface energy of silane-coated pure zinc substrates was also studied. It was found that the silane film thickness obtained depends primarily on the applied solution concentration and is independent of the solution dipping time. The molecular orientations of the applied silane film are determined by the pH value of the applied silane solution and the isoelectric point of the metal substrates. The deposition window in terms of pH value for zinc substrates was between 6 and 9. The total surface energy of silane-coated pure zinc substrate decreases steeply with film aging time for gamma-APS but not for gamma-UPS. The stability of both silane films improved after aging in the air.

Journal Article↗
PubMed1998

Stabilizing the Advancing Front of Thermally Driven Climbing Films.

As known from thermodynamic principles, the surface tension of a liquid decreases with increasing temperature. This property can be used to force a liquid film to climb a vertical substrate whose lower end is held warmer than the top. The vertical gradient in surface tension generates a surface shear stress that causes the liquid film to spread upward spontaneously in the direction of higher surface tension. Experimental investigations have shown that the application of a large temperature gradient produces a thin climbing film whose leading edge develops a pronounced capillary rim which breaks up into vertical rivulets. In contrast, smaller temperature gradients produce thicker films whose profiles decrease monotonically toward the substrate with no evidence of a rim or subsequent film breakup. We have previously shown within linear stability analysis that a climbing film can undergo a fingering instability at the leading edge when the film is sufficiently thin or the shear stress sufficiently large for gravitational effects to be negligible. In this work we show that thicker films which experience significant drainage cannot form a capillary rim and spread in stable fashion. Gravitational drainage helps promote a straight advancing front and complete surface coverage. Our numerical predictions for the entire shape and stability of the climbing film are in good agreement with extensive experiments published years ago by Ludviksson and Lightfoot (AIChE J. 17, 1166 (1971)). We propose that the presence of a counterflow which eliminates the capillary rim can provide a simple and general technique for stabilizing thermally driven films in other geometries. Copyright 1998 Academic Press.

Journal Article↗
PubMed1998

Marginal Regeneration in Thin Vertical Liquid Films.

Marginal regeneration is the rate-determining drainage mechanism in mobile vertical liquid films stabilized with surfactants. Mysels, Frankel, and Shinoda explained this process from (thermal) thickness fluctuations, like capillary waves. The Laplace underpressure in the Plateau border would exert a larger force on a thick, rather than on a thinner film element. This force unbalance would make film elements of different thicknesses move in opposite directions so that they are exchanged at the border. However, experiments and simulations prove that marginal regeneration cannot be the result of thickness fluctuations. Our alternative view is, that marginal regeneration is due to surface tension gradients between the film and its borders. Drainage of film elements into the lower Plateau border causes a local excess of surfactant, and thereby local differences in surface tension. This causes film elements to flow and generates the thickness differences between the absorbed and emerging film elements. The rates of the Marangoni flows reflect the surface dilational properties. This Marangoni effect is a consequence of the compression of the film surface when a film element flows into the lower Plateau border. Marginal regeneration is then a mechanism which returns the surfactant back into the film. Copyright 1998 Academic Press.

Journal Article↗
PubMed2000

High Molecular Orientation in Mono- and Trilayer Polydiacetylene Films Imaged by Atomic Force Microscopy.

Atomically flat monolayer and trilayer films of polydiacetylenes have been prepared on mica and silicon using a horizontal deposition technique from a pure water subphase. Langmuir films of 10,12-pentacosadiynoic acid (I) and N-(2-ethanol)-10,12-pentacosadiynamide (II) were compressed to 20 mN/m and subsequently polymerized by UV irradiation at the air-water interface. Blue and red forms of the films were prepared by varying exposure times and incident power. Polymerization to the blue-phase films produced slight contractions of 2 and 5% for the films of II and I, respectively. Longer UV exposures yielded red-phase films with dramatic film contraction of 15 and 32% for II and I, respectively. The horizontal deposition technique provided transfer ratios of unity with minimal film stress or structure modification. Atomic force microscopy images revealed nearly complete coverage of the substrate with atomically flat films. Crystalline domains of up to 100 micrometers of highly oriented polydiacetylene molecules were observed. The results reported herein provide insight into the roles of molecular packing and chain orientations in converting the monomeric film to the polymerized blue and red phases. Copyright 2000 Academic Press.

Journal Article↗
PubMed2001

Effect of Molecular Weight on Packing during Latex Film Formation.

A UV-visible technique is used to study the evolution of transparency during film formation from latex particles. Latex particles with high and low molecular weight (HM and LM) polymethyl methacrylate (PMMA) are used to prepare films. Two sets of films with different latex content were prepared from HM and LM particles separately, by annealing PMMA particles above the glass transition temperature. Transmitted photon intensity, I(tr), from HM and LM films increased as the annealing temperature was increased. The increase in the transmitted photon intensity is attributed to the latex content (film thickness) for the annealed film samples. It is suggested that as the latex particles are packed (film thickness is increased) fewer voids or cracks are formed in the films. Positive and negative absorption coefficients are measured below and above 210 and 180 degrees C annealing temperatures for the HM and LM films. Packing coefficients are obtained for films in various latex contents. It is observed that LM particles are packed much easier than HM particles. Copyright 2001 Academic Press.

Journal Article↗
PubMed2001

Microstructure and Ion Exchange in Stearic Acid Langmuir-Blodgett Films Studied by Fourier Transform Infrared-Attenuated Total Reflection Spectroscopy.

Fourier transform infrared-attenuated total reflection (FTIR-ATR) spectra have been recorded of 11-layer Langmuir-Blodgett (LB) films of stearic acid deposited at various surface pressures (0.1, 15, and 35 mN/m), and the molecular orientation angles were evaluated quantitatively, which supplied insight into the molecular order with the alkyl chains tightly packed like crystal in the LB films deposited at the zero and higher surface pressures. These experimental results indicate that, in the Langmuir film as the precursor of LB films, stearic acid molecules self-aggregate to form two-dimensional crystalline domains already even at the zero surface pressure, which results in the inhomogeneity of monolayer. The analysis of dependence of nu(C=O) intensity on the surface pressure, surface density, and subphase temperature leads to the conclusion that the defects in LB films originate from the Langmuir film and be conserved upon deposition. Annealing below 50 degrees C and cooling could improve the monolayer homogeneity, and thus a defect-free or low-defect LB films can be deposited. Furthermore, ion exchange conducted in the LB films, on the other hand, confirms the existence of structure defects in LB films of stearic acid. The polar plane microstructure, lateral transport along the polar planes and the coordination types of stearic acid/cation system may be the rate-limiting process. The results have implication on the possible uses of stearic acid LB films as ion-exchange materials or sensors. Copyright 2001 Academic Press.

Journal Article↗
PubMed2004

Camptothecin-loaded films for the prevention of postsurgical adhesions.

OBJECTIVE AND DESIGN: The purpose of this work was to investigate the local application of camptothecin (CPT), a drug with anti-inflammatory, antiproliferative and antiangiogenic properties, as an inhibitor of surgical adhesion formation in rats. METHODS: The anti-adhesion properties of CPT were investigated using the cecal sidewall abrasion model in a total of 92 rats. An adhesion score for each animal was obtained based on the strength and extent of the adhesions. Significance was determined by Students t-test and p values less than 0.05 were considered significant. TREATMENT: The drug was administered by application of carbodiimide crosslinked hyaluronic acid (HA) films containing CPT at concentrations of 0, 0.6, 2.5 and 7.5% w/w at the site of surgical injury. The HA films were characterized by in vitro measurements of drug release rates. RESULTS: In this model the application of HA films alone, or 0, 0.6, 2.5 or 7.5% w/w CPT-loaded HA films, had a significant effect in reducing the mean strength and area of adhesions (3.8 +/- 2.7, 5.6 +/- 0.7, 1.3 +/- 0.7, 0.9 +/- 0.8, 0.7 +/- 1.0, respectively) when compared to those animals in which no film was placed (8.4 +/- 2.5). In addition, a significant difference was observed in the effect of 0.6, 2.5 and 7.5% w/w CPT-loaded films when compared to the HA or 0% CPT-loaded films (p < 0.05). No toxicity was observed in the rats following administration of these films. CONCLUSIONS: CPT loaded films inhibited the formation of adhesions in the rat cecal sidewall abrasion model. HA crosslinked with 2 mM carbodiimide and containing 20% w/w glycerol and 0.6, 2.5 or 7.5% w/w CPT are flexible, mucoadhesive, biocompatible controlled release films that can be used to prevent adhesion formation.

Animals↗
PubMed1981

Structure, composition, enzymatic activities of human erythrocyte and sarcoplasmic reticulum membrane films.

Air/water interface films were obtained from human erythrocytes and rabbit sarcoplasmic reticulum membranes at 'zero surface pressure. according to Verger, R and Pattus, F. (Chem. Phys. Lipids (1976) 16, 285-291). The lipid and protein distribution of these membrane films suggest that the film composition is determined by the composition of the membrane and the mode of integration of its components. When kept at low surface pressure, slow film expansion occurred due to unfolding of proteins at the interface. This process can be stopped by compressing the films at a higher surface pressure than 15 dyn/cm. Acetylcholinesterase activity from human erythrocyte films is highly dependent on the condensation state of the film. Ca2+-ATPase from sarcoplasmic reticulum films was still activable by Ca2+. Freeze-fracture studies on erythrocyte membrane films suggest the such films are monolayers in which proteins are randomly distributed.

Acetylcholinesterase↗
PubMed1994

The trigger film in nurse education.

The use of video in education is now common place. Most Colleges of Nursing and Midwifery have access to the equipment for making and/or showing their own films. Video cannot be used indiscriminately and assumed to be effective. Many educational videos are entertaining but encourage a passive audience. As a result the materials may be enjoyable but the learning achieved, disappointing. An application of video that involves the student in active learning is the trigger film. This is a short piece of film, generally only a few minutes long whose aim is to stimulate and provoke learning. It is a unique form of film possessing special characteristics. The use of the trigger film in other areas of education is documented but its application to nurse education not widely explored. A trigger film has been produced by the author and used with nursing students (RN/Dip HE) to explore professional issues. The trigger film has been found to be an excellent stimulus for discussion and particularly effective for analysis of complex issues. Evaluation by students has been overwhelmingly positive. The trigger film lends itself to exploitation within nurse education. It is particularly useful for learning within the Affective Domain (Baud & Pearson 1979). This paper will discuss the use of video in nurse education, the concept of the trigger film and the use and evaluation of the authors own film.

Decision Making↗
PubMed1994

Is weekly port filming adequate for verifying patient position in modern radiation therapy?

PURPOSE: The objective of this study is to use daily electronic portal imaging to evaluate weekly port filming in detecting patient set-up position. METHODS AND MATERIALS: A computer-based portal alignment method was used to quantify the field displacements on 191 digitized weekly port films and 848 daily electronic portal images in 21 radiation therapy patients. An electronic portal image data set as a control for actual daily treatment position was used to evaluate weekly port films with respect to same-day field displacement, rate of field placement error detection, and prediction of subsequent daily field displacements. RESULTS: The field displacements measured on a port film frequently deviated from the corresponding field displacements on the electronic portal image obtained in the same treatment set-up. A linear regression analysis showed that the curves fitted to the same-day field displacements had slopes that differed significantly from unity (p < 0.001). Overall, the respective frequencies of field placement error, beyond clinical tolerance limits of 5, 7, and 10 mm (corresponding to head and neck, thoracic, and pelvic sites) for port filming and electronic portal imaging were 11% and 14% (p = 0.4) in the X-direction (lateral or anteroposterior) and 24% and 13% (p = .0001) in the Y-direction (caphalad-caudad). When the data were broken down by anatomical region, this discrepancy was found to be mainly due to the differences in the thorax, and head and neck image data sets. For thoracic fields, error in Y-shifts was 28% by port filming, but only 9% by portal imaging (p = 0.01). In the head and neck region, 18% of the port films exceeded tolerance, whereas only 6% of the electronic portal images did (p = 0.0001). Field displacements on the treatment set-ups between the acquisition of port films were not predicted by those films. CONCLUSION: There are discrepancies between the field displacements and field placement errors detected by weekly port films and daily electronic portal images. This study suggests that improved methods of treatment verification may be necessary in modern radiation therapy.

Diagnostic Imaging↗
PubMed2005

Tissue anti-adhesion potential of ibuprofen-loaded PLLA-PEG diblock copolymer films.

This study was designed to evaluate the effect of polyethylene glycol (PEG) and nonsteroidal anti-inflammatory drug (ibuprofen) on the prevention of postsurgical tissue adhesion. For this, poly(L-lactic acid) (PLLA)-PEG diblock copolymers were synthesized by ring opening polymerization of L-lactide and methoxy polyethylene glycol (Mw 5000) of different compositions. The synthesized copolymers were characterized by gel permeation chromatography and 1H-nuclear magnetic resonance spectroscopy. PLLA-PEG copolymer films were prepared by solvent casting. The prepared copolymer films were more flexible and hydrophilic than the control PLLA film, as investigated by the measurements of glass transition temperature, water absorption content, and water contact angle. The drug release behavior from the ibuprofen (10 wt%)-loaded copolymer films was examined by high performance liquid chromatography. It was observed that the drug was released gradually up to about 40% of total loading amount after 20 days, depending on PEG composition; more drug release from the films with higher PEG compositions. In vitro cell adhesions on the copolymer films with/without drug were compared by the culture of NIH/3T3 mouse embryo fibroblasts on the surfaces. For in vivo evaluation of tissue anti-adhesion potential, the copolymer films with/without drug were implanted between the cecum and peritoneal wall defects of rats and their tissue adhesion extents were compared. It was observed that the ibuprofen-containing PLLA-PEG films with high PEG composition (particularly PLLA113-PEG113 film with PEG composition, 50 mol%) were very effective in preventing cell or tissue adhesion on the film surfaces, probably owing to the synergistic effects of highly mobile, hydrophilic PEG and anti-inflammatory drug, ibuprofen.

Abdominal Wall↗
PubMed2005

Magnetron co-sputtered silicon-containing hydroxyapatite thin films--an in vitro study.

The use of silicon-substituted hydroxyapatite (Si-HA) as a biomaterial has been reported recently. In vivo testing has shown that Si-HA promotes early bonding of the bone/implant interface. In order to extend its usage to major load-bearing applications such as artificial hip replacement implants, it has been proposed that the material could be used in the form of a coating on implant surfaces. This paper reports a preliminary study of the biocompatibility of magnetron co-sputtered silicon-containing hydroxyapatite (Si-HA) coatings on a metallic substrate. Magnetron co-sputtered Si-HA films of thickness 600 nm with a Si content of approximately 0.8 wt% were produced on titanium substrates. X-ray diffraction analysis showed that the as-deposited Si-HA films were either amorphous or made up of very small crystals. The crystallinity of Si-HA films was increased after post-deposition heat treatment at 700 degrees C for 3 h, and the principal peaks were attributable to HA. The formation of nano-scale silicon-calcium phosphate precipitates was noted on the heat-treated films. In vitro cell culture has demonstrated that human osteoblast-like cells attached and grew well on all films, with the highest cell growth and signs of mineralisation observed on the heat-treated Si-HA films. In addition, many focal contacts were produced on the films and the cells had well-defined actin cytoskeletal organisation. This work shows that as-deposited and heat-treated Si-HA films have excellent bioactivity and are good candidates when rapid bone apposition is required. Furthermore, heat-treated Si-HA films have improved biostability compared to as-deposited films under physiological conditions.

Actins↗
PubMed2006

Bioactivity and cytocompatibility of zirconia (ZrO(2)) films fabricated by cathodic arc deposition.

Zirconium oxide thin films were fabricated on silicon wafers using a filtered cathodic arc system in concert with oxygen plasma. The structure and phase composition of the zirconium oxide thin films were characterized by atomic force microscopy (AFM), X-ray diffraction (XRD), Rutherford backscattering spectrometry (RBS), and transmission electron microscopy (TEM). The bioactivity was assessed by investigating the formation of apatite on the film surface after soaking in simulated body fluids. Bone marrow mesenchymal stem cells (BMMSC) were used to further evaluate the cytocompatibility of the materials. The results indicate that the films are composed of stoichiometric ZrO(2) and the composition is quite uniform throughout the thickness. Bone-like apatite can be formed on the surface of the ZrO(2) thin film in our SBF immersion experiments, suggesting that the surface is bioactive. The outermost layer of the ZrO(2) thin film comprises nano-sized particles that can be identified by AFM images taken on the thin film surface and TEM micrographs obtained from the interface between the ZrO(2) thin film and apatite layer. The nanostructured surface is believed to be the key factor that apatite is induced to precipitate on the surface. Bone marrow mesenchymal stem cells are observed to grow and proliferate in good states on the film surface. Our results show that ZrO(2) thin films fabricated by cathodic arc deposition exhibit favorable bioactivity and cytocompatibility.

Animals↗
PubMed2004

Vibrational circular dichroism of carbohydrate films formed from aqueous solutions.

Vibrational circular dichroism (VCD) spectra in the entire 2000-900 cm(-1) region have been recorded, for the first time, for films of carbohydrates prepared from aqueous solutions. Eight different carbohydrates, alpha-D-glucopyranosyl-(1-->4)-D-glucose, cyclomaltohexaose, alpha-D-glucopyranosyl alpha-D-glucopyranoside, beta-D-glucopyranosyl-(1-->6)-D-glucose, beta-D-glucopyranosyl-(1-->4)-D-glucose, D-glucose, and both enantiomers of 6-deoxygalactose and of allose, were investigated. The VCD spectra obtained for films are found to be identical to the corresponding spectra obtained for aqueous solutions of carbohydrates. These measurements demonstrate several advantages of significant importance. The strong infrared absorption of water has prevented, in the past, the pursuit for routine applications of VCD in determining the structures of carbohydrates in aqueous solutions. This limitation is not present for film studies because water solvent is removed in the process of preparing the films. Also, strong infrared absorption of water at 1650 cm(-1) requires the use of very short-pathlength (6 microm) cells for measurements on aqueous solutions. This requirement and concomitant inconveniences (such as laborious assembling of a demountable liquid cell or purchasing an expensive variable pathlength liquid cell) have been eliminated for film measurements. The removal of interfering water absorption in film studies resulted in higher light throughput and better signal-to-noise ratios for VCD measurements. Another point of significance is that the amount of carbohydrate sample required for VCD measurements on films is approximately one to two orders of magnitude smaller than that required for corresponding VCD measurements on aqueous solutions. Since carbohydrate samples can now be studied as films, VCD spectroscopy becomes much more broadly applicable for carbohydrates than previously believed. The present work, in combination with other film measurements in our laboratory, indicate that VCD studies on films can be used more generally, providing a convenient and powerful approach for probing structural information for biologically important compounds.

Carbohydrate Conformation↗
PubMed2004

Thermodynamic consideration on single oil in water emulsion film stabilized by cationic surfactant.

The emulsion film has become the focus of the study of emulsion because the film stability and structure play a crucial role on the whole stability and structure of emulsions. In this study, the single emulsion film stabilized by tetradecyltrimethylammonium bromide (C14TAB) in dodecane phase has been investigated thermodynamically. In order to make clear the theoretical treatment, it has been reviewed how the thermodynamic quantities of extremely thin films are defined and how it is related to the experimental variables such as temperature, pressure, and concentrations of solutes. By using the equations demonstrated here, the film tension and film surface tension, which were evaluated from the measurement of contact angle between the emulsion film and the surrounding bulk meniscus, have been inspected thermodynamically from the viewpoint of the influence of added salt (KBr) concentration on the structure of thin emulsion film. In addition, the comparison of the results obtained has also been made between the foam and emulsion films to reveal the effect of an ambient dodecane phase on the properties of the film.

Journal Article↗
PubMed2005

Dynamic organization of mixed Langmuir films of glucose oxidase and stearylamine at the air-water interface.

The structure and the dynamic organization of a mixed Langmuir film of glucose oxidase and stearylamine at the air-water interface have been studied. The film has been first characterized at the air-water interface by surface pressure/area isotherms. The dynamics of the mixed film was studied by following the evolution of the film area at a constant pressure and the evolution of the pressure at a constant area. After transfer of the films on solid substrates, the chemical composition of the mixed film has been quantified by UV-vis and IR spectroscopies. These characterizations were carried out in order to study the incorporation of glucose oxidase into the stearylamine film, and its influence on the structural evolution of the film. From these results, the dynamic organization of this mixed film may be described. For short times, glucose oxidase molecules interact with stearylamine molecules in solution or at the interface; these interactions would lead to the formation of a complex between stearylamine and glucose oxidase molecules. For long times (at least 3 h), a homogeneous mixed film constituted essentially of this complex is obtained at the air-water interface. A detailed analysis by atomic force microscopy allowed us to support this model and the existence of the glucose oxidase/stearylamine complex.

Air↗