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Characteristics of sensitometric curves of radiographic films.

A new type of radiographic film, EDR (extended dose range) film, has been recently become available for film dosimetry. It is particularly attractive for composite isodose verification of intensity modulated radiation therapy because of its low sensitivity relative to the more common Kodak XV film. For XV film, the relationship between optical density and dose, commonly known as the sensitometric curve, depends linearly on the dose at low densities. Unlike XV film, the sensitometric curve of EDR film irradiated by megavoltage x rays is not linearly dependent on the dose at low densities. In this work, to understand the mechanisms governing the shape of the sensitometric curves, EDR film was studied with kilovoltage x rays, 60Co gamma rays, megavoltage x rays, and electron beams. As a comparison, XV film was also studied with the same beams mentioned above. The model originally developed by Silberstein [J. Opt. Soc. Am. 35, 93-107, 1945)] is used to fit experimental data. It is found that the single hit model can be used to predict the sensitometric curve for XV films irradiated by all beams used in this work and for EDR films exposed to kilovoltage x rays. For EDR film irradiated by 60Co gamma rays, megavoltage x rays, and electron beams, the double hit model is used to fit the sensitometric curves. For doses less than 100 cGy, a systematic difference between measured densities and that predicted by the double hit model is observed. Possible causes of the observed differences are discussed. The results of this work provide a theoretical explanation of the sensitometric behavior of EDR film.

Dose-Response Relationship, Radiation↗

Use of CEA TVS film for measuring high energy photon beam dose distributions.

CEA TVS film is a therapy verification film that has been recently introduced in the North American market. This film features linear characteristic curves for photon energies from 137Cs to 18 MV as reported by Cheng and Das [Med. Phys. 23, 1225 (1996)]. In Saskatoon, TVS film was investigated for its application in the measurement of dose distributions with 4 and 18 MV linacs and a 60Co unit. The TVS film jacket has a layer of conductive material that has a minimal effect on the film's response. Film sensitivity generally increases for exposures normal to the incident beam as compared with parallel exposures, but was highly dependent on beam energy and depth of measurement. Fractional depth doses obtained in the parallel orientation agreed well with ion chamber measurements for the linac beams at depths beyond Dmax; ion chamber measurements differed by a maximum of 1.6% and 2.6% for the 4 and 18 MV beams, respectively. In the buildup region, an increase in film response was found when compared to the ion chamber measurements for both linac beams. With the 60Co beam, the TVS film showed an increase in sensitivity with depth as the proportion of scattered soft x rays increases; the maximum difference between ion chamber and film fractional depth doses was 7.8%. The TVS film demonstrates a substantial improvement over Kodak X-Omat V film for measuring depth doses in the parallel orientation, for all beams considered. Generally, the results confirm TVS film as an accurate and practical dosimeter for the measurement of dose distributions in high energy photon beams.

Cesium Radioisotopes↗

[A study of dose distribution of high energy X-ray in lung measured by film method].

Measurement was carried out for 6 MV X-rays using an inhomogeneity phantom with films. The films were set parallel or perpendicular to the beam axis. Measurement data were compared with values obtained by a JARP dosimeter, to assess the accuracy of evaluation. 1) The data measured by perpendicular films showed underestimation but were more accurate than those measured by parallel films when compared with the JARP method. 2) The difference in measurement between the perpendicular films with multi-layers and a single layer was 0.4%. 3) The difference in measurement between packed and unpacked films was 1.5%. The former overestimated values, but they were closer to the JARP values than those of unpacked film. 4) In comparison with the JARP method, accuracy decreased in the following order: perpendicular packed film with multiple layers, perpendicular packed film with a single layer, perpendicular unpacked film with multiple layers, perpendicular unpacked film with a single layer, parallel film. 5) The values measured by films in the inhomogeneity phantom were closer to those measured by the JARP method than values measured in a water-equivalent phantom. The reason was that there was less scatter in the lung of the inhomogeneity phantom than in the water-equivalent phantom.

Film Dosimetry↗

Hydroxyapatite and fluor-hydroxyapatite layered film on titanium processed by a sol-gel route for hard-tissue implants.

A double-layered coating, consisting of a hydroxyapatite (HA) outer film and a fluor-hydroxyapatite (FHA) inner film, was produced on a Ti substrate by a sol-gel route to improve the biocompatibility and functionality of the system. Dissolution behavior of and in vitro cellular responses to the layered film were investigated. Calcium nitrate and triethyl phosphite were used for calcium and phosphate precursors, respectively, and ammonium fluoride was added as a fluorine-ion source for FHA. The FHA layer was deposited on Ti by spin coating and subsequent heat treatment at 550 degrees C for 30 min in air, and then the HA layer was laid down over the FHA-coated Ti under the same conditions. After heat treatment, characteristic apatite structures and phases were developed on both FHA and HA films. The cross-section view of the HA/FHA film clearly showed a double-layered structure on Ti with each layer approximately 0.6-0.8-microm thickness. The coating layer was highly uniform and dense, and adhered to Ti substrate strongly with an adhesion strength of about 40 MPa. The in vitro solubility of the HA/FHA layered film in a physiological solution was between that of HA and FHA pure film, and the dissolution profile was quite biphasic, that is, an initial rapid period and a slowdown with increasing time, reflecting the gradient solubility of the fast HA outer structure/slow FHA inner structure. The human osteoblast-like HOS TE85 cells cultured on the HA/FHA layered film attached, spread, and grew favorably. The proliferation rate of the cells on the layered film was significantly higher (considered at p < 0.05 for n = 6) than that on Ti substrate and was similar to that on pure HA film. The alkaline phosphatase (ALP) activity and osteocalcin (OC) produced by the cells on the layered film were significantly higher (considered at p < 0.05 for n = 6) than those on Ti substrate. Moreover, the ALP and OC levels of cells on the layered film showed the trends of HA outer/FHA inner structure with respect to culture period, that is, HA initially and FHA later. These observations suggest that the HA/FHA layered film on Ti obtained by a sol-gel route possesses gradient functionality in terms of solubility and cellular responses, and find that those parameters can be tailored for specific use in hard-tissue implants.

Biocompatible Materials↗

Thin liquid films and monolayers of DMPC mixed with PEG and phospholipid linked PEG.

In this work thin liquid films (TLFs) and monolayers at the air/water interface formed by dimyristoylphosphatidylcholine (DMPC) and by DMPC mixed with poly ethylene glycols (PEGs) and dimyristoylphosphatidylethanolamine (DMPE) linked PEGs were studied. Film forming dispersions were composed of two types of particles: liposomes and micelles. TLFs stability, threshold concentration C(t) (i.e., the minimum one for stable film formation), and hydrodynamic behavior were measured. At equivalent conditions, DMPC films were Newton black films (real bilayers), while DMPE-PEGs films were much thicker with free water between the monolayers. DMPE-PEG addition to DMPC films caused both C(t) decrease (depending on PEG moiety length and Mw) and change of TLF formation mechanism. TLFs' hydrodynamic behavior also strongly depended on DMPE-PEG content and Mw. It was observed that thinning of the DMPC and DMPE-PEGs films continued to different film types and thickness, being much thicker for the latter films. Addition of free PEGs (PEG-200/6000) did not alter TLF type or stability, but changed TLF thinning time, confirming that free PEGs with Mw<8000 could not penetrate in the membrane and alter "near-membrane" water layer viscosity. Monolayer studies showed improved formation kinetics of both adsorbed and spread films, decrease of surface tension (equilibrium and dynamic), and of film compression/decompression histeresis area in DMPE-PEGs monolayers compared with DMPC pure films. Our study shows that combining the models of phospholipid TLFs and monolayers provide the opportunity to investigate the properties of membrane surface and to clarify some mechanisms of its interactions with membrane-active agents.

Dimyristoylphosphatidylcholine↗

Interpretation accuracy of a CCD film digitizer.

There are no significant differences between the interpretations of radiographic images resulting from digitizing films using a recently developed CCD unit and the readings of the original films as measured by accuracy, sensitivity, specificity and ROC analysis. Digital imaging is rapidly becoming the basis of radiology practice resulting in the gradual elimination of conventional film examinations. Related to this trend is the ability of radiologists to provide reliable interpretations of imaging examinations using film digitization and soft copy display. An acceptable system must provide high-quality digital images to achieve the levels of diagnostic accuracy that are comparable to the interpretation of film. This study is an effort to contribute to the acceptance of digital imaging by testing the hypothesis.- The authors selected 120 radiographic examinations from the departmental film files which included chest, abdominal, extremity and other common procedures. Half of the cases contained specified abnormalities and half did not have such findings. All of the examinations had a high degree of diagnostic difficulty. The films were digitized on the CCD equipment and each of the four board certified radiologists who participated in the study interpreted each of the 120 cases, half on original film and half in the digitized format on a high resolution workstation. No radiologist read the same examination more than once. Data collection included variables such as perceived image quality, diagnostic difficulty and interpretation confidence. Accuracy measures were calculated and an ROC analysis was performed. As of this date, the preliminary results indicate acceptance of the hypothesis that there is no significant difference between the accuracy of film readings and the interpretations of the digitized images on a soft copy display. Differences noted in perceived image quality among readers were also not significant. The final results, including an ROC analysis, will be available in March 2002 when a paper is submitted for publication in the Journal of Digital Imaging. During the transition from conventional film practice to digital radiology there is a need to convert previous films to a digital format for comparison with new digital examinations and to facilitate expert reading and consultation on film procedures performed at distant sites. Diagnostic quality and cost effectiveness are key factors in the acceptability of film digitizers to meet these requirements. The preliminary results of this study are encouraging in that another option may be available to radiologists and administrators responsible for choosing equipment for the changing pratice of medical imaging.

Data Display↗

Synthesis of polyetherurethanes containing L-serine dipeptide and their use as materials for biomedical films.

Prepolymers, which were produced by the polyaddition reaction of polytetramethylene glycol (PTMG) or polyethylene glycol (PEG) and 4,4'-diphenylmethane diisocyanate (MDI) or hexamethylene diisocyanate (HMDI), were chain-extended with a linear dipeptide of L-serine (Z-Ser-Ser-OMe) or a cyclic dipeptide of L-serine [c-(Ser)2] to yield novel polyetherurethanes containing dipeptide segments. The relationship between the surface morphology and the biomedical properties of the film of the novel polyetherurethanes was investigated. The surface of PU(PTMG,Z-Ser-Ser-OMe,MDI) film was smooth, but fibrous structures were developed in the bulk of the film with increasing molecular weight of the PTMG segment. The antithrombogenicity of the film containing the low molecular weight PTMG segment was better than that of the usual polyetherurethane film without the dipeptide segments. The partial hydrolysis of the ester groups involved in the dipeptide segment improved the antithrombogenicity. In the surface and the bulk of PU[PTMG,c-(Ser)2,MDI] film, spherulite structures were developed when the molecular weight of the PTMG segment was high, while single crystals with a length of 3-4 microns were produced when the molecular weight of the PTMG segment was low. The antithrombogenicity of the film containing the high molecular weight PTMG segment was better than that of the usual polyetherurethane film without the dipeptide segments. PU(PTMG/PEG,Z-Ser-Ser-OMe,MDI) film and PU[PTMG/PEG,c-(Ser)2,MDI] film were permeated by uraemic toxins. The permeation was accelerated with increasing water content of the film and decreasing molecular weight of the solute. The oxygen permeability of the film of the polyetherurethane containing the linear or cyclic dipeptide segments was greater than that of polyetherurethane film which does not contain the dipeptide segments.

Biocompatible Materials↗

Adsorption of lysozyme to phospholipid and meibomian lipid monolayer films.

It is believed that a lipid layer forms the outer layer of the pre-ocular tear film and this layer helps maintain tear film stability by lowering its surface tension. Proteins of the aqueous layer of the tear film (beneath the lipid layer) may also contribute to reducing surface tension by adsorbing to, or penetrating the lipid layer. The purpose of this study was to compare the penetration of lysozyme, a tear protein, into films of meibomian lipids and phospholipids held at different surface pressures to determine if lysozyme were part of the surface layer of the tear film. Films of meibomian lipids or phospholipids were spread onto the surface of a buffered aqueous subphase. Films were compressed to particular pressures and lysozyme was injected into the subphase. Changes in surface pressure were monitored to determine adsorption or penetration of lysozyme into the surface film. Lysozyme penetrated a meibomian lipid film at all pressures tested (max=20 mN/m). It also penetrated phosphatidylglycerol, phosphatidylserine or phosphatidylethanolamine lipid films up to a pressure of 20 mN/m. It was not able to penetrate a phosphatidylcholine film at pressures >or=10 mN/m irrespective of the temperature being at 20 or 37 degrees C. However, it was able to penetrate it at very low pressures (<10 mN/m). Epifluorescence microscopy showed that the protein either adsorbs to or penetrates the lipid layer and the pattern of mixing depended upon the lipid at the surface. These results indicate that lysozyme is present at the surface of the tear film where it contributes to decreasing the surface tension by adsorbing and penetrating the meibomian lipids. Thus it helps to stabilize the tear film.

Adsorption↗

Investigation of novel alginate-magnesium aluminum silicate microcomposite films for modified-release tablets.

Physicochemical properties of sodium alginate-magnesium aluminum silicate (SA-MAS) composite films were investigated and a potential as a film former of SA-MAS dispersion for modifying drug release from tablets was evaluated as well. Interaction between SA and MAS in the composite films was revealed using FTIR spectroscopy. Thermal behavior of the composite films was changed due to the complexation of SA and MAS. Powder X-ray diffractometry data suggested that a higher crystallinity of the composite film and a phase-separated microcomposite were formed. The composite films in the ratios of 1:0.5 and 1:1 showed the increases of tensile strength and percentage of elongation when compared with SA films. Water vapor permeability of the composite films tended to increase with increasing ratio of MAS. The decreases in water uptake and drug permeability in 0.1 M HCl were found in the composite films. A positive charge drug, propranolol HCl, provided a higher affinity on the composite films than a weakly acidic nonelectrolyte, acetaminophen, resulting in a longer lag time and a higher partition coefficient depending on the content of MAS in the composite films. This was due to the complex formation of propranolol HCl and MAS. Using SEM, the tablets coated with SA-MAS dispersion had a smooth surface, while those with SA dispersion showed a pinholing on the surface, resulting in a faster drug release. The drug release profiles of the tablets could be modified by coating with the composite film at different coating levels. This finding suggests that MAS could improve physicochemical properties of the SA films, leading to a novel coating material of the SA-MAS dispersion for modifying drug release from tablets.

Absorption↗

Phase transitions in films of lung surfactant at the air-water interface.

Pulmonary surfactant maintains a putative surface-active film at the air-alveolar fluid interface and prevents lung collapse at low volumes. Porcine lung surfactant extracts (LSE) were studied in spread and adsorbed films at 23 +/- 1 degrees C using epifluorescence microscopy combined with surface balance techniques. By incorporating small amounts of fluorescent probe 1-palmitoyl-2-nitrobenzoxadiazole dodecanoyl phosphatidylcholine (NBD-PC) in LSE films the expanded (fluid) to condensed (gel-like) phase transition was studied under different compression rates and ionic conditions. Films spread from solvent and adsorbed from vesicles both showed condensed (probe-excluding) domains dispersed in a background of expanded (probe-including) phase, and the appearance of the films was similar at similar surface pressure. In quasistatically compressed LSE films the appearance of condensed domains occurred at a surface pressure (pi) of 13 mN/m. Such domains increased in size and amounts as pi was increased to 35 mN/m, and their amounts appeared to decrease to 4% upon further compression to 45 mN/m. Above pi of 45 mN/m the LSE films had the appearance of filamentous materials of finely divided dark and light regions, and such features persisted up to a pi near 68 mN/m. Some of the condensed domains had typical kidney bean shapes, and their distribution was similar to those seen previously in films of dipalmitoylphosphatidylcholine (DPPC), the major component of surfactant. Rapid cyclic compression and expansion of LSE films resulted in features that indicated a possible small (5%) loss of fluid components from such films or an increase in condensation efficiency over 10 cycles. Calcium (5 mM) in the subphase of LSE films altered the domain distribution, decreasing the size and increasing the number and total amount of condensed phase domains. Calcium also caused an increase in the value of pi at which the maximum amount of independent condensed phase domains were observed to 45 mN/m. It also induced formation of large amounts of novel, nearly circular domains containing probe above pi of 50 mN/m, these domains being different in appearance than any seen at lower pressures with calcium or higher pressures in the absence of calcium. Surfactant protein-A (SP-A) adsorbed from the subphase onto solvent-spread LSE films, and aggregated condensed domains in presence of calcium. This study indicates that spread or adsorbed lung surfactant films can undergo expanded to condensed, and possibly other, phase transitions at the air-water interface as lateral packing density increases. These phase transitions are affected by divalent cations and SP-A in the subphase, and possibly by loss of material from the surface upon cyclic compression and expansion.

1,2-Dipalmitoylphosphatidylcholine↗

A phase I comparative study of contraceptive vaginal films containing benzalkonium chloride and nonoxynol-9. Postcoital testing and colposcopy.

Benzalkonium chloride (BZK) has been shown in in vitro and in vivo studies to immobilize sperm, to be active against STD-causing organisms, and to penetrate and thicken cervical mucus. A US clinical study of a sponge containing 60 mg BZK showed life table pregnancy rates at 6 and 12 months of 11.7 and 18.9 per 100 women, respectively. BZK is not currently marketed in the US as a contraceptive. The present study aimed to assess 1) the ability of a new contraceptive vaginal film containing either of two doses of BZK to prevent the penetration of sperm into midcycle cervical mucus; 2) the effect of the film on the vaginal epithelium; and 3) the acceptability of the film. All results were compared with VCF, a currently marketed film containing nonoxynol-9 (N-9). Ten women underwent two baseline cycles of postcoital testing in which no film was used, followed by three test cycles in which Allendale-BZK film, a new film containing either 19 or 25 mg BZK, or VCF, containing 70 mg N-9, was used. The sequence of testing cycles was randomized. In each cycle, condoms were used prior to midcycle, then a midcycle cervical mucus specimen was examined to ensure midcycle characteristics and the absence of sperm. Each woman then had intercourse using either no film (baseline cycles) or a test film (test cycles) and returned 2-3 h afterwards. Cervical mucus was again assessed for adequacy and the presence of sperm. Each woman also underwent colposcopy, using a protocol developed by the World Health Organization. The average number of progressively motile sperm seen per high power field was as follows: first baseline cycle, 22.2; second baseline cycle, 22.1; test cycle with film containing 19 mg BZK, 0.2; test cycle with film containing 25 mg BZK, 0.0; and test cycle with VCF containing 70 mg N-9, 0.0. There was no significant difference between baseline cycles or among test cycles in the average number of progressively motile sperm seen (p = 0.78 and p > or = 0.75, respectively). The average number of progressively motile sperm seen in each test cycle did, however, differ significantly from the average number seen in either baseline cycle (p < 0.01). Colposcopy showed superficial de-epithelialization without underlying inflammation in 15-20% of baseline cycles, regardless of whether colposcopy was done before or after coitus; in 50% of cycles in which either dose of BZK was used; and in 69% of cycles in which VCF was used. In all cases women were asymptomatic. Erythema and petechiae were also seen on colposcopy although at a lower frequency than de-epithelialization. There was no difference in the acceptability of the films. A vaginal contraceptive containing either 19 or 25 mg BZK in a new film base appears to be comparable with VCF in preventing sperm from entering midcycle cervical mucus and may be somewhat less disruptive to the vaginal epithelium.

Administration, Intravaginal↗

Organic esters of plasticizers affecting the water absorption, adhesive property, glass transition temperature and plasticizer permanence of eudragit acrylic films.

The materials used in film coating technology are very important tools for pharmaceutical applications. The effects of four organic esters used as plasticizers (triacetin, diethyl phthalate (DEP), dibutyl phthalate (DBP) and tributyl citrate (TBC)) on the water absorption behavior and adhesive property of Eudragit films and on the glass transition temperature (T(g)) and plasticizer permanence of Eudragit E film were investigated. The results indicate that the water absorption of these Eudragit films was dependent on the type of Eudragit polymers and plasticizers used. Eudragit E film plasticized with triacetin showed a slight water absorption, but when plasticized with DEP, DBP or TBC did not. All Eudragit RL films showed significant uptake of water, but Eudragit RS films exhibited a lesser degree of water absorption. The adhesion (tack value) of all Eudragit films was markedly increased when the concentration of plasticizer was greater than 25%. Eudragit E film exhibited a greater adhesiveness than the Eudragit RL or RS film, particularly with higher plasticizer concentration. Weight loss of the Eudragit E film plasticized with triacetin or DEP was more pronounced with aging, but when plasticized with DBP or TBC weight loss was not seen. The results indicate that TBC may be the best choice of plasticizer for Eudragit film, particularly for the Eudragit E film.

Acrylic Resins↗

Bioadhesive properties of hydroxypropylcellulose topical films produced by hot-melt extrusion.

The objective of this study was to investigate the in vivo bioadhesive properties of hydroxypropylcellulose (HPC) films containing seven polymer additives on the epidermis of 12 human subjects, including two ethnic sub-groups. HPC films containing polyethylene glycol (PEG 3350) alone, Vitamin E TPGS (TPGS) 5%, sodium starch glycolate 5%, Eudragit E-100 5%, carbomer 974P and 971P 5%, and polycarbophil 5%, all with and without plasticizer, were prepared by hot-melt extrusion utilizing a Randcastle Microtruder (Model #RCP-0750). Bioadhesion testing was performed using a Chatillon digital force gauge DFGS50 attached to a Chatillon TCD-200 motorized test stand to determine force of adhesion (FA), elongation at adhesive failure (EAF), and modulus of adhesion (MA) for the 12 films tested. In vivo, the TPGS-incorporated film exhibited a two-fold increase in FA when compared to the control film containing the PEG 3350 5%. The carbomer 971P and polycarbophil containing films were determined to have the highest FA and EAF, and the lowest MA of all films tested. The film containing carbomer 971P had a higher FA than the film containing 974P. In addition, films in one ethnic sub-group exhibited higher FA and EAF than the other. Force--deflection profiles obtained from these experiments indicate that the force of adhesion, elongation at adhesive failure and modulus of adhesion are a function of the polymer additive in the HPC extruded films. The incorporation of carbomer 971P and a polycarbophil into HPC films increased bioadhesion significantly when compared to the film containing HPC and PEG 3350. Differences in FA and EAF were discovered between two ethnic sub-groups tested.

Adhesives↗

The influence of film-induced mood on pain perception.

It has been shown that a person's mood can influence pain tolerance. Films have been used as a means of inducing a desired mood. The effect on pain perception of film type and film length to induce mood was investigated. Previous research with brief humorous films had not indicated any unique advantage of humor over distraction approaches. Other recent research had indicated that after exposure to film stimulation there is a need to wait approximately 40 min before physiological changes can be obtained. Thus, the present study varied both film type and length and introduced a 30-min waiting period following the mood induction via film prior to exposure to cold-pressor pain. Two hundred subjects in nine different groups participated in the study. Three types of films were used: (1) humorous, (2) holocaust, (3) neutral. Three lengths of each type were also used: 15 min, 30 min, and 45 min. In addition, a tenth no-film group served as a control for the effects of a film. Each subject was given a baseline trial of cold-pressor pain, a trial immediately following the film and a trial 30 min later. Results indicated an advantage in increased pain tolerance for the humorous film and an increased pain tolerance for the longer film regardless of type only after the 30-min waiting period. Results were discussed from a pain theoretical perspective with emphasis placed on returning to psychological manipulations of the sensory aspects of pain and not just the cognitive/emotional/motivational dimensions.

Adolescent↗

Study of layer-by-layer self-assembled viscoelastic films on thickness-shear mode resonator surfaces.

We describe quartz crystal electroacoustic admittance studies in thickness shear mode resonators loaded with self-assembled multilayers composed of alternate layers of glucose oxidase (GOx) and poly(allylamine) covalently attached to [Os(bpy)2ClPyCOH]- , (PAH-Os), deposited on a 3-mercaptopropanesulfonic acid (MPS)-modified gold on the quartz crystal. The complex acoustic impedance parameters, R(S) and X(LS) of a lumped-element Butterworth-Van Dyke (BVD) resonator have been determined for organized thin films of different thickness obtained by varying the number of enzyme layers, n, in (PAH-Os)n(GOx)n structures. The ellipsometric film thickness and mass for dry enzyme multilayer films and films in contact with water were evaluated, and the average film density was estimated. By combination of the estimated film thickness and density, the expression for the surface mechanical impedance of the lumped-element modified resonator (Granstaff and Martin model), and the liquid density and viscosity, we simulate the layer-by-layer film growth on the basis of the measured electroacoustic impedance. The complex impedance X(LS) and R(S) increase with film thickness and the enzyme films can be regarded as acoustically thin in the reduced state for films thinner than 600 nm. We have also measured electroacoustic parameters for PAH-Os/GOx self-assembled multilayers under electrochemical perturbation in a buffer electrolytic solution. The electrostatically self-assembled multilayers behaved as lossy viscoelastic films at 10 MHz with G'f and G''f on the order of 10(6) Pa. The films became viscoelastic upon oxidation to Os(III), resulting in an increase of R(S) and X(LS) in the oxidized state with the number of (PAH-Os)(GOx) bilayers due to film swelling and an increase in the shear moduli during oxidation.

Allylamine↗

Direct electrochemistry of myoglobin in titanate nanotubes film.

Titanate nanotubes (TNT) were proven to be efficient support matrixes for the immobilization of myoglobin (Mb). A comparative study was performed using the corresponding analogue, nanocrystalline anatase TiO2 (TNP). UV-visible absorption and FT-IR spectra show that Mb was not obviously denatured in TNT film in contrast to the significant denaturation of Mb in TNP film. Cyclic voltammetry and square wave voltammetry measurements were carried out using the Mb-TNT or Mb-TNP cast film-covered basal plane pyrolytic graphite electrode. The Mb-TNT film gave a well-defined, nearly reversible redox couple with the apparent formal peak potential (Ep) of -0.239 V (vs Ag/AgCl) in pH 5.5 buffer, whereas a relatively smaller, quais-reversible redox pair with Ep of -0.263 V was observed for the Mb-TNP film. The amounts of electroactive Mb in TNT film and TNP film were 15 and 10%, respectively. Moreover, the Mb-TNT film exerted facile direct electron transfer with the apparent heterogeneous electron-transfer rate constant (kET) of 86+/-7 s-1, almost 4 times the 22+/-5 s-1 value for the Mb-TNP membrane and higher than other Mb-entrapped films reported. Additionally, the Mb-TNT film demonstrates good electrocatalytic reduction of hydrogen peroxide with a detection limit of 0.6 microM, much lower than the 3.0 microM value for the Mb-TNP electrode and other Mb-related film-modified electrodes reported so far. The Mb-TNT film exhibits higher peroxidase-like activity with the apparent Michaelis-Menton constant (KM) of 140 microM, significantly lower than the 1300 microM value for the Mb-TNP film. The functional hydroxyl group and the surface charge as well as tubular morphology of TNT are important factors to stabilize the bound protein.

Electrochemistry↗

Degradability of polysaccharides multilayer films in the oral environment: an in vitro and in vivo study.

Biomedical devices and modified biomaterial surfaces constitute an expanding research domain in the dental field. However, such oral applications have to face a very particular environment containing specific physiological conditions and specific enzymes. To evaluate their suitability in the development of novel oral applications, the degradability of polyelectrolyte multilayer films made of the natural polysaccharides chitosan and hyaluronan (CHI/HA) was investigated in vitro and in vivo in a rat mouth model. The films were either native or cross-linked using a water-soluble carbodiimide (EDC) in combination with N-hydroxysulfosuccinimide. The in vitro degradation of the films by different enzymes present in the oral environment, such as lysozyme and amylase, was followed by quartz crystal microbalance measurements and confocal laser scanning microscopy observations after being film labeled with CHI(FITC). Whereas native films were subjected to degradation by all the enzymes, cross-linked films were more resistant to enzymatic degradation. Films were also put in contact with whole saliva, which induced a slow degradation of the native films over an 18 h period. The in vivo degradation of the films deposited on polymer disks and sutured in the rat mouth was followed over a 3 day period. Whereas film degradation is fast for native films, it is much slower for the cross-linked ones. More than 60% of these films remained on the disks after 3 days in the mouth. Taken together, these results suggest that the multilayer films made of natural polysaccharides are of high potential interest for oral applications, especially as drug release systems, offering various degradation rates and consequent release characteristics.

Animals↗

Self-assembly of monoglycerides in beta-lactoglobulin adsorbed films at the air-water interface. Structural, topographical, and rheological consequences.

In this work, we have analyzed the structural, topographical, and surface dilatational characteristics of pure beta-lactoglobulin adsorbed films and the effect of the self-assembly of monoglycerides (monopalmitin or monoolein) in beta-lactoglobulin films at the air-water interface. Measurements were performed in a single device that incorporates a Wilhelmy-type film balance, Brewster angle microscopy, and interfacial dilatational rheology. The structural and topographical characteristics of beta-lactoglobulin adsorbed and spread films are similar. However, the surface dilatational modulus of beta-lactoglobulin films shows a complex behavior depending on film formation. The self-assembly of monoglyceride in a beta-lactoglobulin adsorbed film has an effect on the structural, topographical, and dilatational properties of the mixed films, depending on the interfacial composition and the surface pressure (pi). At low pi, a mixed film of monoglyceride and beta-lactoglobulin may exist. At high pi (after the collapse of beta-lactoglobulin), the mixed films are dominated by monoglyceride molecules. However, the small amounts of collapsed beta-lactoglobulin have a significant effect on the surface dilatational properties of the mixed films. Protein displacement by monoglyceride is higher for monopalmitin than for monoolein. However, some degree of interaction exists between proteins and monoglycerides, and these interactions are more evident in adsorbed films than in spread films.

Adsorption↗