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Thin films composed of multiwalled carbon nanotubes, gold nanoparticles and myoglobin for humidity detection at room temperature.

Optically transparent and electrically conductive nanocomposite thin films consisting of multiwalled carbon nanotubes (MWCNTs), gold nanoparticles (GNPs) and myoglobin molecules that glue GNPs and MWCNTs together are fabricated for the first time on glass substrates from aqueous solution. The nanocomposite thin film is capable of varying its resistance, impedance or optical transmittance at room temperature in response to changes in ambient humidity. The conductometric sensitivity to relative humidity (RH) of the nanocomposite thin film is compared with those of the pure and Mb-functionalized MWCNT layers. The pure MWCNT layer shows a small increase in its resistance with increasing RH due to the effect of p-type semiconducting nanotubes present in the film. In contrast, a four times higher sensitivity to RH is observed for both the nanocomposite and Mb-functionalized MWCNT thin films. The sensitivity enhancement is attributable to swelling of the thin films induced by water absorption in the presence of Mb molecules, which increases the inter-nanotube spacing and thereby causes a further increase of the film resistance. A humidity change as low as DeltaRH=0.3 % has been readily detected by conductometry using the nanocomposite thin film.

Gold↗

Chitosan-alginate films prepared with chitosans of different molecular weights.

Chitosan-alginate polyelectrolyte complex (CS-AL PEC) is water insoluble and more effective in limiting the release of encapsulated materials compared to chitosan or alginate. Coherent CS-AL PEC films have been prepared in our laboratory by casting and drying suspensions of chitosan-alginate coacervates. The objective of this study was to evaluate the properties of the CS-AL PEC films prepared with chitosans of different molecular weights. Films prepared with low-molecular-weight chitosan (Mv 1.30 x 10(5)) were twice as thin and transparent, as well as 55% less permeable to water vapor, compared to films prepared with high-molecular-weight chitosan (Mv 10.0 x 10(5)). It may be inferred that the low-molecular-weight chitosan reacted more completely with the sodium alginate (M(v) 1.04 x 10(5)) than chitosan of higher molecular weight. A threshold molecular weight may be required, because chitosans of Mv 10.0 x 10(5) and 5.33 x 10(5) yielded films with similar physical properties. The PEC films exhibited different surface properties from the parent films, and contained a higher degree of chain alignment with the possible formation of new crystal types. The PEC films exhibited good in vitro biocompatibility with mouse and human fibroblasts, suggesting that they can be further explored for biomedical applications.

Animals↗

Modification of polyetherurethane for biomedical application by radiation induced grafting. II. Water sorption, surface properties, and protein adsorption of grafted films.

A series of polyetherurethane films grafted by means of gamma radiation with hydrophilic or reactive monomers (2-hydroxyethyl methacrylate, 2,3-epoxypropyl methacrylate, 2,3-dihydroxypropyl methacrylate, and acrylamide) and partially chemically modified were subjected to various physico-chemical investigation methods involving water sorption, contact angle, and protein adsorption measurements. From contact angle data the interfacial free energy gamma sw between grafted films and water was calculated. It was found that the water uptake of grafted films increases with grafting yield or, in the case of grafted and afterwards chemically modified films, with reaction yield; the diffusion coefficient of water in the modified films also increases with grafting yield. Contact angle studies revealed all grafted films to have surfaces more hydrophilic than the ungrafted trunk polymer. The degree of hydrophilicity--especially of HEMA-grafted films--strongly depends on grafting conditions. For some grafted samples with high surface hydrophilicity very low interfacial free energies approaching zero were measured. The study of the competitive adsorption of bovine serum albumin, gamma-globulin, and fibrinogen from a synthetic protein solution onto modified films showed that the adsorption of albumin increases markedly with increasing grafting yields, whereas the fibrinogen and gamma-globulin adsorption only slightly increases. A correlation between interfacial free energy and protein adsorption in the sense of the "minimum interfacial free energy hypothesis" was found only for samples with grafting yields below 5%. At higher grafting yields the increased surface area complicates the analysis.

Adsorption↗

Influence of discharge power level on the properties of hydroxyapatite films deposited on Ti6A14V with RF magnetron sputtering.

The effects of discharge radiofrequency (RF) power and film thickness were studied on the characteristics of Ca5(PO4)3OH (hydroxyapatite) thin films fabricated by RF magnetron sputtering. The structure and chemical composition were investigated with alpha-step (thickness), scanning electron microscopy (SEM), X-ray diffraction (XRD), Rutherford backscattering spectrometry (RBS), and infrared absorption spectrometry (FTIR). The films were analyzed as-sputtered and after annealing at 550 degrees C under argon flow. SEM showed that the film surfaces had no cracks or other defects. X-ray diffraction showed that the deposited films were amorphous with low-discharge RF power, and crystalline with high-discharge RF power. After annealing, all the films had the same crystalline structure as apatite. However, the RBS measurements revealed that all films had a higher calcium-phosphate ratio than standard synthetic hydroxyapatite. Furthermore, statistical testing of the RBS data revealed the existence of only a weak correlation between the Ca/P ratio and the discharge power level. Although all sputtered films showed phosphate bonds in the infrared spectrum, only after annealing did the OH bonds of hydroxyapatite become visible.

Alloys↗

The effect of surface chemistry and nanotopography of titanium nitride (TiN) films on 3T3-L1 fibroblasts.

The cell-material interaction of 3T3-L1 fibroblasts with TiN films was studied in vitro. TiN films were deposited onto glass substrates to thicknesses of 0.2 and 1.0 microm by pulsed dc reactive magnetron sputtering. For comparison TiN films were deposited by closed field unbalanced magnetron sputter ion plating by Teer Coatings Ltd. (Hartlebury, UK) to result in TiN films with similar surface chemistries but having increased topographical features. TiN films were characterized using X-ray diffraction, X-ray photoelectron spectroscopy, and atomic force microscopy. The cell-material interaction was examined morphologically by monitoring fibroblast attachment and growth and comparing to a control substrate. At early time points increased numbers of 3T3-L1 fibroblasts were found to preferentially attach to TiN films with an increase in the percentage of surface interstitial nitrogen and also with decreased topographical features. At later time points the presence of nanotopography appeared to play a greater role than the effects of surface chemistry and resulted in increased numbers of attached 3T3-L1 fibroblasts. The results show that by changing the deposition route and parameters to produce TiN films, the resultant films can be used to investigate the cellular response to surfaces of differing chemistry and topography.

3T3 Cells↗

Grafting amine-terminated branched architectures from poly(L-lactide) film surfaces for improved cell attachment.

Poly(L-lactide) (PLL) has been used as a bioabsorbable material in the medical and pharmaceutical fields. The unmodified hydrophobic PLL surface generally has low cell affinity; thus, modification of PLL film surface properties is necessary to improve its use as a biomaterial. Our surface modification method involved the use of photografting and typical wet chemistry to create branched architectures containing amine functionalities on the periphery of the grafted layers. Amine (-NH2) groups were first introduced on the PLL film surface by photoinduced grafting of 4,4'-diaminobenzophenone and the grafted branched architectures were created by subsequent reactions with succinic acid and tris(2-aminoethyl) amine. The resulting film surface was analyzed using contact angle goniometry and X-ray photoelectron spectroscopy. MC3T3 fibroblasts were cultured on unmodified PLL film and PLL films grafted with the branched structures and the films were subsequently analyzed by optical microscopy. The contact angle goniometry results showed an initial decrease and subsequent plateau in the water contact angles for the PLL films with each successive generation of the branched architectures. The X-ray photoelectron spectroscopy data provided insight into the structure of the grafted layer and revealed an increase in the nitrogen content with each generation. Optical micrographs showed enhanced cell attachment and viability on the surface-modified PLL films.

Amines↗

Electron diffraction and diffraction contrast imaging of thin organic films.

The applications of electron diffraction and diffraction contrast electron microscopy with which to study the structure and dynamics of organic thin films are discussed. The techniques of making thin film deposits on substrates and of forming free-standing thin films over holes on the substrate are described. Selected area electron diffraction and diffraction contrast imaging techniques for thin film studies are elaborated, and examples are given. Methods to reduce radiation damage and environmental protection of the thin film specimen are outlined. The interpretation of electron diffraction and imaging data is given for three cases: 1) The effects of film tilting and molecular tilting (with respect to the film plane) are examined. 2) The detection of phase transition is illustrated. 3) The use of labels to mark film domains is shown together with the measurement of dynamic movement.

Chemistry, Organic↗

Epstein-Barr virus (types 1 and 2) in the tear film in Sjogren's syndrome and HIV infection.

Evidence of Epstein-Barr virus (EBV) shedding in the saliva and tear film has been sought to explain the pathogenesis of the oral and ocular features of Sjogren's syndrome. Patients with human immunodeficiency virus (HIV) infection are purported to have a higher incidence of keratoconjunctivitis sicca. Twenty patients with definite Sjogren's syndrome (primary and secondary), 19 with HIV infection, and 15 normal controls were recruited and studied. Human herpes viruses (EBV 1 and 2, CMV, HZV, and HSV-1) in tear film were detected by polymerase chain reaction of DNA extracted from Schirmer strips. HSV-1, VZV, and CMV were not detected in any tear samples. EBV-1 DNA was found in the tear film of 4 patients with Sjogren's syndrome, which was not significantly different from the control group (P = 0.18). Twelve patients with HIV infection had evidence of EBV-1 in their tears, which was significantly different from controls (P = 0.0002) and patients with Sjogren's syndrome (P = 0.014). EBV-2 was found in 3 patients with HIV and in 1 patient with secondary Sjogren's syndrome, and was always found as a co-infection with EBV-1 (P = 0.01). This represents the first report examining EBV types 1 and 2 in the tear film and also EBV in the tear film of patients with HIV. Shedding of EBV in the tear film was not related to the presence of keratoconjunctivitis sicca in Sjogren's syndrome. EBV-2 co-infection with EBV-1 has not been previously reported in the tear film. EBV infection is abnormally regulated in Sjogren's syndrome and HIV, and it is likely that the presence of EBV in the tear film is related to the patients' altered immune status.

Adolescent↗

Water vapor sorption of hot-melt extruded hydroxypropyl cellulose films: effect on physico-mechanical properties, release characteristics, and stability.

Hot-melt extrusion technology was used to prepare thin polymer films containing hydroxypropyl cellulose and clotrimazole (CT). Films containing hydroxypropyl celluloses of different molecular weight and the drug were investigated for moisture-sorption, mechanical properties, and release characteristics. Stability of the films was also studied at 25 degrees C/60% relative humidity (RH) and 40 degrees C/75% RH for up to 3 months. To study the moisture-sorption of the hot-melt extruded films, a rapid dynamic vapor sorption technique was used. Mechanical properties were evaluated using the Texture Analyzer. The molecular weight of the polymer had a significant effect on the mechanical and release characteristics of the films but did not influence the equilibrium moisture content in the films stored at RHs ranging from 0 to 90%. However, the time to reach equilibrium was longer for the higher molecular weight polymers. The drug release rate was dependent on the rate of erosion, which in turn depended on the molecular weight of the polymer. The films were stable at 25 degrees C/60% RH for up to 3 months with no significant degradation or recrystallization of CT. However, recrystallization of the drug was observed within the films stored in accelerated stability conditions at the end of 3 months in which only 92.9% (+/-1.9) CT remained.

Cellulose↗

Sustained release of drugs from ethylcellulose--polyethylene glycol films and kinetics of drug release.

Cast films composed of different ratios of polyethylene glycol and ethylcellulose containing salicylic acid, caffeine, and tripelennamine as model dispersed drugs were prepared and exhibited sustained release. The drug content of the film declined at an apparent first-order rate initially, whereas the drug quantity released was proportional to the square root of time. Data analysis validated the latter treatment, which is in accordance with the diffusional matrix model, and disproved the validity of the apparent first-order conformity. The release rates were independent of film thickness and proportional to drug concentration in pure ethylcellulose films; in polyethylene glycol--ethylcellulose films, a positive deviation from linearity was observed. The logarithm of the rate constant was proportional to the fraction of polyethylene glycol in the film. Unlike in pure ethylcellulose films, the release rate in mixed films was altered by a change in the external fluid pH.

Caffeine↗

Measurement of protection afforded by ultraviolet-absorbing window film using an in vitro model of photodamage.

BACKGROUND AND OBJECTIVES: The effects of chronic sun damage including telangiectasias, solar lentigos, rhytides, enlarged pores, sagging skin, and pre-cancerous and cancerous growths are among the most common presenting complaints in a dermatologist's office. These changes are often worse on the driver's side of the face, emphasizing the role of UVA exposure received while driving in producing these changes. This study was undertaken to measure the ability of car window glass alone and in combination with ultraviolet (UV)-absorbing film to reduce UV-damage as measured using an established in vitro model of photoprotection. STUDY DESIGN MATERIALS AND METHODS: Using the 3T3 neutral red uptake photoprotection assay with solar simulating radiation (SSR) administered by a xenon arc solar simulator, we measured the photoprotection ability of auto glass, window film that filters UV radiation, and the combination of window film and auto glass. RESULTS: As measured by the 3T3 neutral red uptake photoprotection assay, auto glass reduced cell death from SSR by 29%, while window film reduced it 90%, and the combination of auto glass and film reduced cell death by 93%, when compared to unfiltered SSR. CONCLUSIONS: Window film that filters UV radiation results in dramatic reductions in cytotoxicity when measured by the neutral red uptake photoprotection assay. Widespread use of window film provides an ever-present barrier to ultraviolet A (UVA) exposure and could potentially reduce the detrimental effects of UVA, including photoaging, skin cancer, and ocular damage, such as cataracts. In addition, such film is essential for patients suffering from conditions sensitive to UV radiation, such as lupus erythematosis.

Animals↗

FTIR and UV-Vis Spectroscopic Studies of Black Soap Film.

FTIR and UV-vis spectroscopies have been employed to investigate the self-assembly features of a black soap film (BSF) prepared from aqueous solution consisting of 10(-2) M cetyltrimethylammonium bromide (CTAB) and 10(-3) M thiazole yellow (TY) in the liquid-crystalline and gel states, respectively. The construction of two surfactant monolayers of the soap film is independent of the thickness of aqueous core, and the thickness is approximately 1.7 nm at equilibrium. In the liquid-crystalline state, the methylene segments of the hydrocarbon chains are averagely oriented at an angle of 70 degrees with respect to the film normal, and the alkyl chains take a long-range interaction to improve the film elasticity. The TY molecules in the film are horizontally aligned at the monolayer interface in the J-aggregate form. The double-negatively charged TY aggregate greatly enhances the film stability. Dye neutral red is further introduced into the CTAB soap film, the film lifetime is related to the type of the added dyes, in the order of cationic < nonionic < anionic. Copyright 1998 Academic Press.

Journal Article↗

Luminescent properties of tris(2,2'-bipyridine)ruthenium(II) in sol-gel-processed dip-coated thin films.

The luminescence decay and spectral behavior of ruthenium(II)-tris-1,2-bipyridine dichloride dissolved in different organically modified silicate gel matrixes were investigated. Dip-coated thin films were synthesized from tetraethoxysilane (TEOS), methyltriethoxysilane (MTEOS), ethyltriethoxysilane (ETEOS), and methyl- trimethoxysilane (MTMOS). A blue shift in the ruthenium complex emission spectrum with respect to the aqueous solution was observed for all the films on the sol to gel conversion. This spectral shift was slightly dependent on the precursor used to obtain the films and independent of the reaction pH to prepare the "sol". In the data treatment of the time-resolved luminescence measurements, it was assumed that the distribution of the luminophore in the films was nonhomogeneous. The analysis of the luminescence decay profiles was based on a multisite model. All decay curves are best described by a double-exponential model. The parameters of the decay components depended principally on the thermal treatment used in the processing of the films. The lifetimes decreased and the emission espectra showed a red shift with the increase in the drying temperature. A luminescence quenching of the ruthenium complex in the films by dissolved oxygen in aqueous solution was also observed. The quenching rate constant obtained from the preexponential amplitude-weighted mean lifetimes (tau(M)) was in the order of 10(9) M(-1) s(-1). When a phenolic derivative was used as quencher the process rate was greatly reduced compared to the quenching in water. It would seem that the metallic complex sequestered within the film is placed either into a higher microviscosity microenvironment or in a location which the phenolic quencher cannot access. In both cases, the quenching plot based on tau(o)(M)/tau(M) could be fitted satisfactorily by a sum of two terms of Stern-Volmer. This fact is indicative of the matrix microheterogeneity for the films and is fully consistent with the biexponential nature of the luminescence intensity decay profiles.

Journal Article↗

Of an extracellular matrix in human pre-corneal tear film.

A theory relating viscosity to fluid flow rates in human tear film was developed and from that theory arises a relationship between viscosity, tear-film thickness and vertical drainage rates at the air-tear interface. Human tears were collected in capillary tubes at rates, on average, of less than 1 microliter min-1. Protein concentration was slightly higher than values reported in the literature and electrophoretic distributions of tear-film proteins were normal. Viscosity of the tear films were measured at 35 degrees C (physiological temperature). Vertical flow rates of tear film were measured in the inter-blink period either by observing the movement of lipid plaques at the air-tear interface or by observing naturally occurring contaminant specs (size around 1 micron). Tear film vertical flow rates were at least an order of magnitude lower than those predicted from collected tear-fluid viscosity measurements. It was concluded that collected tears are not representative of the whole pre-corneal tear film and that the tear film includes a fluid flow-inhibiting matrix whose structural components have a longer time-constant of exchange than the soluble proteins of the collected tear fluid.

Adult↗

Determination of molecular orientational order in cold-stretched poly(p-phenylene vinylene) thin films by DECODER 13C NMR.

The properties of poly(p-phenylene vinylene) (PPV) films depend on the degree of orientational order present in the films. Recently, Dermaut et al. reported a novel cold-stretching technique (Macromolecules 33, 5634-5637 (2000)) in which chain alignment can be introduced into PPV precursor films by uniaxially stretching them prior to the thermal elimination reaction that forms PPV. The two-dimensional direction exchange with correlation for orientation-distribution evaluation and reconstruction (DECODER) 13C NMR technique was applied to both unstretched PPV films and PPV films that were uniaxially cold stretched to a draw ratio lambda = l/l0 = 5. The unstretched films were found to be moderately ordered, comprised of a component present at 80% with a Gaussian distribution of 60 degrees fwhm, while the remaining 20% is isotropically distributed. A distribution of 9 degrees +/- 3 degrees fwhm was measured by NMR in good agreement with IR dichroism measurements for the uniaxially cold-stretched films, establishing that a high degree of orientational order can be introduced by cold stretching PPV films.

Anisotropy↗

Tear film-contact lens interactions.

Contemporary contact lenses, when considered in perspective, are remarkably effective; the remaining primary challenge, however, appears to be the relationship of the contact lens to the tear film. The number of contact lens wearers in the United States is no longer increasing, perhaps the result of discomfort which may occur initially, preventing contact lens wear, or which may develop over a period of years, resulting in termination of wear. Contemporary lenses can usually provide comfort if tear film integrity can be maintained. The environmental humidity is a critical component in the formation and thickness of the lipid layer for both the preocular and the prelens tear films, thus influencing tear film stability and evaporation. A common clinical observation is the gradual development of discomfort over 10 or more years of contact lens wear by patients who initially are totally asymptomatic. This discomfort, probably the result of compromise to the tear film occurring with age, frequently leads to discontinuation of contact lens wear. Intermittent discontinuation of contact lens wear may also occur as the result of seasonal discomfort when the relative humidity is low, or when the nature of the visual demand, as in extended VDT operation, inhibits blinking. The fragile tear film and its relation to contact lenses is readily understood by two quotations: "The human tear film is rather unstable, but it is regenerated by frequent blinking", and "When a contact lens is placed in the eye, the lens alters the normal structure of the tear film and affects its rate of evaporation.(ABSTRACT TRUNCATED AT 250 WORDS)

Blinking↗

Digital radiography and film scanners: automating the transition to filmless radiology.

To facilitate the integration of digital radiography (DR) and legacy film/screen technology, we have devised a methodology for film digitization that optimizes workflow and integrates well with the picture archiving and communication system (PACS). This work was performed at Mercy Medical Center (Cedar Rapids, IA) using a film digitizer with built-in Digital Imaging and Communications in Medicine (DICOM) communication. The radiology department at Mercy has one DR system and three separate film/screen systems. The DR system software suite features DICOM Modality Worklist capability to provide complete radiology information system (RIS) integration functionality. This provides for patient demographic information to be automatically downloaded from the RIS worklist to populate the DICOM image header. Likewise, we have taken advantage of the film scanner's DICOM capability to develop software linking it with the hospital RIS. This capability provides a worklist downloading functionality equivalent to that of the DR. Patient demographics can then be rapidly downloaded as each film is digitized. The worklist capability of the scanner is essential in several respects. First, it guarantees that patient demographic information is completely accurate and, therefore, that the digitized x-ray image will be merged with the correct patient file in the PACS. Additionally, high film scanner throughput is achieved, guaranteeing that all inpatient-digitized films are as readily available on the PACS as their DR image counterparts. The digitized images have proven to be of diagnostic quality on the typical 1K by 1K PACS workstation. Also, as patients are admitted to the hospital, prior films from the radiology archive are digitized to form a readily available patient history for in-house physicians. Over time, we are building archival patient histories of soft-copy images that will enable increased availability of patient x-rays to both in-hospital and outside referring physicians, especially as more internet-viewing software becomes available to the out-of-hospital medical community. Finally, the results of this study show that high-throughput RIS integration of film scanning equipment is a key component to making a graceful transition to the filmless hospital as more DR systems are installed.

Humans↗

Non-destructive 3D-characterization of Zn 2-2x Cu x In x S 2-thin films with ion beam analysis.

Thin layers of ZnS-CuInS(2) mixed crystals (called ZCIS) are promising absorber materials for thin film solar cell applications. The ZCIS-films investigated in this study were grown on (001)GaP, SiO(2) and CeO(2)/Al(2)O(3) with different elemental compositions by Pulsed Laser Deposition (PLD). In order to optimize the sample preparation process a quantitative three-dimensional (i.e. laterally and depth resolved) determination of the compositions and thicknesses of the ZCIS-films is needed. It is demonstrated how this difficult analytical task can be addressed with ion microbeam analysis. For this purpose the films have been analysed non-destructively by means of Rutherford Backscattering Spectrometry (RBS) and Particle Induced X-ray Emission (PIXE) using a 2 MeV He(+) ion microbeam at the high-energy ion nanoprobe LIPSION. A large variation in film thickness caused by particulates deposited on the film was observed. The elemental compositions of the film and the particulates have been determined and compared with the target composition. The deviations found varied substantially for the individual elements. It could be concluded from these measurements, that the quality of the sintered PLD-target is of crucial importance for the roughness of the films. Furthermore concentration-depth-profiles of the individual elements have been derived non-destructively by means of RBS.

Journal Article↗