Surface morphology of thin lysozyme films produced by matrix-assisted pulsed laser evaporation (MAPLE)

Thin films of the protein, lysozyme, have been deposited by the matrix-assisted pulsed laser evaporation (MAPLE) technique. Frozen targets of 0.3-1.0 wt.% lysozyme dissolved in ultrapure water were irradiated by laser light at 355 nm with a fluence of 2 J/cm². The surface quality of the thin lysozyme films of different thickness deposited on 7 mm × 7 mm Si-〈1 0 0〉-wafers was investigated with scanning electron microscopy and atomic force microscopy. Already at comparatively low thickness, ∼20 nm, the substrate is covered by intact lysozyme molecules and fragments. The concentration of lysozyme in the ice matrix apparently does not play any significant role for the morphology of the film. The morphology obtained with MAPLE has been compared with results for direct laser irradiation of a pressed lysozyme sample (i.e. pulsed laser deposition (PLD)).     

Multifunctional thin films of lactoferrin for biochemical use deposited by MAPLE technique

Lactoferrin (Lf) is an iron-binding glycoprotein present in almost all mammalian secretions which plays an important role in host defense against microbial and viral infections. The protein has been reported to also have anti-inflammatory activity and antitumoral effects in vitro and in vivo.Thin films of Lf were deposited on silicon, quartz and Thermanox plastic coverslip substrates by Matrix Assisted Pulsed Laser Evaporation (MAPLE) technique, using a Nd:YAG laser working at 266 nm, at different laser fluences (0.1-0.8 J cm⁻²). The deposited layers have been characterized by Fourier Transformed Infra-Red spectroscopy (FTIR), and the morphology of the various substrates was investigated by Atomic Force Microscopy (AFM). The biocompatibility of lactoferrin thin films was evaluated for each substrate, by in vitro biochemical tests.     

Thin films of Cu(II)-o,o′-dihydroxy azobenzene nanoparticle-embedded polyacrylic acid (PAA) for nonlinear optical applications developed by matrix assisted pulsed laser evaporation (MAPLE)

Thin films based on two different metal-organic systems are developed by MAPLE and their nonlinear optical applications are explored. A complex of o,o′-dihydroxy azobenzene with Cu²⁺ cation is found to organize as a non-central symmetric crystallite. A simple protocol is developed for the in situ fabrication of highly monodisperse copper-complex nanoparticles in a polymer film matrix of polyacrylic acid. The thin films were deposited on quartz substrates by MAPLE (matrix assisted pulsed laser evaporation) using a Nd:YAG laser working at 355 nm. Atomic force microscopy (AFM), Fourier transform infrared (FTIR), X-ray photoelectron spectroscopy (XPS), and optical second harmonic generation (SHG) were performed on the samples. The optical limiting capability of the nanoparticle-embedded polymer film is investigated.     

Thin films of polyaniline deposited by MAPLE technique

Polyaniline (PAni) has important electro-conductive properties, high absorbance in microwave range and it is also frequently used in gas sensors because of its capability to convert chemical interactions into electrical signals. The methods of obtaining polyaniline in the form of thin films and/or nanostructures are complicated and request special physical and chemical treatments, both on the substrate surface and for the polymer itself.In this paper we applied matrix assisted pulsed lased evaporation (MAPLE) for obtaining thin films and nanostructures of polyaniline. In MAPLE, the target consisting of the material (usually 0.2-3 wt%) dissolved in a solvent is frozen and it is evaporated using a laser. In our case polyaniline-emeraldine salt (PAni-ES) was dissolved in xylene or toluene, frozen in liquid nitrogen and was used as target. The third and the fourth harmonics of a Nd-YAG laser (λ = 355 nm and 266 nm) were used as laser sources. The obtained films have been characterized by atomic force microscopy, dielectric spectroscopy and Fourier transform infrared spectroscopy. The influence of the solvent type and of the laser parameters (wavelengths and fluence) on the polyaniline structures composition and properties has been investigated.     

MAPLE deposition of Mn(III) metalloporphyrin thin films: Structural, topographical and electrochemical investigations

We report the deposition by MAPLE of metallized nanostructured (5,10,15,20-tetraphenyl)porphinato manganese(III) chloride thin films onto gold screen-printed electrodes, or 〈1 1 1〉 Si substrates. The deposited nanostructures were characterized by atomic force microscopy and exhibited globular structures with average diameters decreasing with laser fluence. Raman spectroscopy showed that no major decomposition appeared. We have investigated the Mn(III)-metalloporphyrin thin films by cyclic voltammetry in order to evaluate the potential bio/chemosensing activity on dopamine neurotransmitter analyte. We have found that the manganese(III)-porphyrin is appropriate as a single mediator for dopamine sensing in the specific case of gold screen-printed electrodes.     

Matrix assisted pulsed laser evaporation of poly(d,l-lactide) thin films for controlled-release drug systems

We report the successful deposition of the porous polymer poly(d,l-lactide) by matrix assisted pulsed laser evaporation (MAPLE) using a KrF* excimer laser (248 nm, τ = 7 ns) operated at 2 Hz repetition rate. The chemical structure of the starting materials was preserved in the resulting thin films. Fluence played a key role in optimizing our depositions of the polymer. We demonstrated MAPLE was able to improve current approaches to grow high quality thin films of poly(d,l-lactide), including a porosity control highly required in targeted drug delivery.     

Laser deposition of cryoglobulin blood proteins thin films by matrix assisted pulsed laser evaporation

We report the first successful deposition of type II cryoglobulin blood protein thin films by matrix assisted pulsed laser evaporation (MAPLE) using a KrF^* excimer laser source (λ = 248 nm, τ_FWHM ≈ 20 ns) operated at a repetition rate of 10 Hz. We demonstrate by AFM and FTIR that MAPLE-deposited thin films consist of starting type II cryoglobulin only, maintaining its chemical structure and biological functionality, being properly collected and processed. The dependence on incident laser fluence of the induced surface morphology is presented. The presence of type II cryoglobulin was revealed as aggregates of globular material in the MAPLE-deposited thin films and confirmed by standard cryoglobulin tests.     

High fluence deposition of polyethylene glycol films at 1064 nm by matrix assisted pulsed laser evaporation (MAPLE)

Matrix assisted pulsed laser evaporation (MAPLE) has been applied for deposition of thin polyethylene glycol (PEG) films with infrared laser light at 1064 nm. We have irradiated frozen targets (of 1 wt.% PEG dissolved in water) and measured the deposition rate in situ with a quartz crystal microbalance. The laser fluence needed to produce PEG films turned out to be unexpectedly high with a threshold of 9 J/cm², and the deposition rate was much lower than that with laser light at 355 nm. Results from matrix assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) analysis demonstrate that the chemistry, molecular weight and polydispersity of the PEG films were identical to the starting material. Studies of the film surface with scanning electron microscopy (SEM) indicate that the Si-substrate is covered by a relatively homogenous PEG film with few bare spots.     

Characterization of polymer thin films obtained by pulsed laser deposition

The development of laser techniques for the deposition of polymer and biomaterial thin films on solid surfaces in a controlled manner has attracted great attention during the last few years. Here we report the deposition of thin polymer films, namely Polyepichlorhydrin by pulsed laser deposition. Polyepichlorhydrin polymer was deposited on flat substrate (i.e. silicon) using an NdYAG laser (266 nm, 5 ns pulse duration and 10 Hz repetition rate).The obtained thin films have been characterized by atomic force microscopy, scanning electron microscopy, Fourier transform infrared spectroscopy and spectroscopic ellipsometry.It was found that for laser fluences up to 1.5 J/cm² the chemical structure of the deposited polyepichlorhydrin polymer thin layers resembles to the native polymer, whilst by increasing the laser fluence above 1.5 J/cm² the polyepichlorohydrin films present deviations from the bulk polymer.Morphological investigations (atomic force microscopy and scanning electron microscopy) reveal continuous polyepichlorhydrin thin films for a relatively narrow range of fluences (1-1.5 J/cm²).The wavelength dependence of the refractive index and extinction coefficient was determined by ellipsometry studies which lead to new insights about the material.The obtained results indicate that pulsed laser deposition method is potentially useful for the fabrication of polymer thin films to be used in applications including electronics, microsensor or bioengineering industries.     

Matrix-assisted pulsed laser evaporation of polyfluorene thin films

Poly(9,9-dioctylfluorene) (PF8) thin films have been deposited by matrix-assisted pulsed laser evaporation (MAPLE) using a KrF excimer laser. The influence of the laser fluence (50-500 mJ/cm²) and the nature of the solvent (chloroform, toluene, tetrahydrofuran) on the films properties have been studied. The chemical composition of the deposited films was investigated by Fourier transform infrared (FTIR) spectroscopy and compared with the one of spin coated films. To investigate the effect of the deposition parameters on the optical properties of the films, photoluminescence (PL) measurements were performed. Poor structural and optical properties were observed for films deposited starting from chloroform solutions. When using toluene as solvent, the spectra characteristics improved with increasing laser fluence, while wide PL spectra were observed. The characteristic emission bands of the PF8 polymer were nicely detected for films deposited starting from a tetrahydrofuran (THF) solution. Moreover, in this last case, the PF8 structure is preserved at high laser fluences, too.