Matrix assisted pulsed laser evaporation processing of triacetate-pullulan polysaccharide thin films for drug delivery systems

We report the first successful deposition of triacetate-pullulan polysaccharide thin films by matrix assisted pulsed laser evaporation. We used a KrF* excimer laser source (λ = 248 nm, τ ≈ 20 ns) operated at a repetition rate of 10 Hz. We demonstrated by FTIR that our thin films are composed of triacetate-pullulan maintaining its chemical structure and functionality. The dependence on incident laser fluence of the induced surface morphology is analysed.     

Polycaprolactone biopolymer thin films obtained by matrix assisted pulsed laser evaporation

We report the successful deposition of polycaprolactone polymer by MAPLE using a KrF* excimer laser (λ = 248 nm, τ = 7 ns). According to FTIR spectra the deposited films have similar chemical structure to the dropcast material. The fluence plays a key role in optimizing the performances of MAPLE-synthesized polycaprolactone structures. We demonstrated that MAPLE allows for controlling the morphology of films to the level required in targeted drug delivery of pharmacologic agents.     

Matrix assisted pulsed laser evaporation of cinnamate-pullulan and tosylate-pullulan polysaccharide derivative thin films for pharmaceutical applications

We have demonstrated the successful thin film growth of two pullulan derivatives (cinnamate-pullulan and tosylate-pullulan) using matrix assisted pulsed laser evaporation (MAPLE). Our MAPLE system consisted of a KrF* laser, a vacuum chamber, and a rotating target holder cooled with liquid nitrogen. Fused silica and silicon (1 1 1) wafers were used as substrates. The MAPLE-deposited thin films were characterized by transmission spectrometry, profilometry, atomic force microscopy (AFM), Fourier transform infrared (FTIR) spectroscopy and Raman spectroscopy. The deposited layers ranged from 250 nm to 16.5 μm in thickness, depending on the laser fluence (0.065-0.5 J cm⁻²) and number of pulses applied for the deposition of one structure (1500-13,300). Our results confirmed that MAPLE was well-suited for the transfer of cinnamate-pullulan and tosylate-pullulan.     

Thin films of polymer mimics of cross-linking mussel adhesive proteins deposited by matrix assisted pulsed laser evaporation

Mussels secrete specialized adhesives known as mussel adhesive proteins, which allow attachment of the organisms to underwater marine environments. Obtaining large quantities of naturally derived mussel adhesive proteins adhesives has proven to date rather problematic, thus, synthetic analogs of mussel adhesive proteins have recently been developed. We report deposition of 1:100 and 1:1000 poly[(3,4-dihydroxystyrene)-co-styrene)] mussel adhesive protein analogs by matrix assisted pulsed laser evaporation (MAPLE) using an ArF* excimer laser source. The deposited films have been evaluated for their antifouling behavior. The MAPLE-deposited synthetic mussel adhesive protein analog thin films are homogenous and adhesive, making the use of these materials in thin film form a viable option.     

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.     

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.     

Processing of poly(1,3-bis-(p-carboxyphenoxy propane)-co-(sebacic anhydride)) 20:80 (P(CPP:SA)20:80) by matrix-assisted pulsed laser evaporation for drug delivery systems

We have demonstrated successful thin film growth of poly(1,3-bis-(p-carboxyphenoxy, propane)-co-(sebacic anhydride)) (20:80) by matrix-assisted pulsed laser evaporation using a KrF* excimer laser (λ = 248 nm, τ = 25 ns, ν = 10 Hz). The deposited thin films have been investigated by Fourier transform infrared spectroscopy, and atomic force microscopy. We have demonstrated that the main functional groups of poly(1,3-bis-(p-carboxyphenoxy, propane)-co-(sebacic anhydride)) (20:80) are present in the deposited film. The effect of matrix on both thin film structure and surface morphology was also examined. The goal of this work is to explore laser processing of this material to create suitable constructs for drug delivery applications.     

Enhanced cell affinity of poly(l-lactide) film by immobilizing phosphonized chitosan

Graft polymerization of acrylic acid (AA) onto poly(l-lactide) (PLLA) film by UV irradiation was carried out to develop surfaces for N-methylene phosphonic chitosan (NMPC) immobilization. The properties of modified films were discussed by colorimetric method, attenuated total reflection-Fourier transform infrared spectroscopy (ATR-FTIR), contact angles, atomic force microscopy (AFM) and osteoblast incubation. The results showed that AA solution concentration and irradiation time had effect on the graft carboxyl densities. Comparing the ATR-FTIR images, two new peaks at 1561 cm⁻¹ and 1632 cm⁻¹ proved that NMPC was immobilized on the film surface successfully. The water contact-angles were decreased from 90 ± 5° to 37 ± 5° after modification. The AFM images indicated that the surface of the combined film was rougher than that of untreated film. The grafted film provided an excellent substrate for the growth of osteoblast.     

Surface modification of hydroxyapatite nanoparticles by poly(l-phenylalanine) via ROP of l-phenylalanine N-carboxyanhydride (Pha-NCA)

The surface of hydroxyapatite nanoparticles was modified by poly(l-phenylalanine) via the ring opening polymerization (ROP) of l-phenylalanine N-carboxyanhydride. The preparation procedure was monitored by Fourier transform infrared spectroscopy (FTIR), and the modified hydroxyapatite was characterized by thermal gravimetric analysis (TGA) and X-ray diffraction (XRD). The results showed that the surface grafting amounts of poly(l-phenylalanine) on HA ranging from 20.26% to 38.92% can be achieved by tuning the reaction condition. The XRD patterns demonstrated that the crystalline structure of the modified hydroxyapatite was nearly the same with that of HA, implying that the ROP was an efficient surface modification method. The MTT assay proved that the biocompatibility of modified HA was very good, which showed the potential application of modified HA in bone tissue engineering.     

Nanocomposites of poly(l-lactide) and surface modified magnesia nanoparticles: Fabrication, mechanical property and biodegradability

A novel nanocomposite based on biodegradable poly(l-lactide) (PLLA) was prepared by the incorporation of surface modified magnesia (g-MgO) nanoparticles using a solution casting method. The mechanical properties, biodegradable properties and protein adhesion behavior of the g-MgO/PLLA nanocomposites were investigated. Scanning electron microscopy (SEM) results showed that g-MgO nanoparticles could comparatively uniformly disperse in PLLA matrix. The addition of g-MgO nanoparticles to PLLA matrix improved the tensile strength and elastic modulus, whereas reduced the elongation at break. The mass loss results showed that the nanocomposites with higher g-MgO content had faster degradation rates. The in vitro pH value determination results indicated that the g-MgO nanoparticles could neutralize effectively the lactic acid resulting from the degradation of PLLA. The g-MgO/PLLA nanocomposites exhibited enhanced protein adsorption, i.e., with the increase of g-MgO content, the amount of protein adsorption increased. The (5 wt%)g-MgO/PLLA nanocomposites adsorbed 33% more protein than the pure PLLA.     

Enhanced dielectric permittivity in poly (vinylidene) fluoride/multiwalled carbon nanotubes nanocomposite thin films fabricated by pulsed laser deposition

The fabrication of high quality thin films of poly (vinylidene fluoride) embedded with multiwalled carbon nanotubes using pulsed laser deposition technique is reported. The prepared films were characterized for structural, morphology and dielectric properties. The morphology analysis revealed uniform dispersion of multiwalled carbon nanotubes throughout the polymer matrix. X-ray diffraction results suggested that the poly (vinylidene fluoride) film is in amorphous phase while addition of multiwalled carbon nanotubes showed presence of crystalline peaks in the nanocomposites films. It was interesting to note that the nanocomposite films exhibits significant enhancement of the ferroelectric β-phase as evidenced by the X-ray diffraction and Fourier transform infrared spectroscopy results. The dielectric analysis shows a remarkable enhancement in the dielectric permittivity of nanocomposites with lower loss and conductivity level. The results can be attributed to the formation of minicapacitor network and relatively higher percolation threshold in the nanocomposites.     

Studies on physico-chemical properties of hydroxyethylammonium (l) tartrate monohydrate single crystals

In this paper, we report the growth and characterization of hydroxyethylammonium (l) tartrate monohydrate single crystals grown by slow evaporation solution technique. The X-ray diffraction analysis reveals that the crystal belongs to the monoclinic system having P2₁ space group. Photoinduced optical absorption effects were studied on the crystalline samples irradiated with CW 532 nm (green) and 689 nm (red) laser wavelengths. The relative second harmonic generation efficiency of the title crystal was found to be 1.4 times larger than that of KDP crystal. The thermal, mechanical, dielectric and optical studies of the single crystals were carried out to propose the material for useful applications. The reflectance and refractive indices were also evaluated from optical transmission spectrum. Further the electronic excitation calculations were carried out to understand the charge transfer mechanisms.     

Growth and characterization of organic nonlinear optical crystal: l-Valinium salicylate (LVS)

The new organic NLO crystal l-valinium salicylate (LVS) was grown by slow evaporation method using the mixed solvent of methanol and water in equal ratio. The crystal structure parameters were observed by powder and single crystal X-ray diffraction (XRD). The various functional groups present in the grown crystal were confirmed by Fourier transform infrared spectroscopy (FTIR) technique. ¹H and ¹³C Fourier transform nuclear magnetic resonance (FT-NMR) spectra were recorded to elucidate the molecular structure. The optical absorption study confirmed the good transmission window of the title crystal suitable for optical applications. The second harmonic generation (SHG) efficiency of LVS was confirmed by Kurtz Perry technique.     

Lead-free ferroelectric BaTiO3 doped-(Na0.5Bi0.5)TiO3 thin films processed by pulsed laser deposition technique

The difficulties in synthesizing phase pure BaTiO₃ doped-(Na_0.5Bi_0.5)TiO₃ are known. In this work, we reporting the optimized pulsed laser deposition (PLD) conditions for obtaining pure phase 0.92(Na_0.5Bi_0.5)TiO₃-0.08BaTiO₃, (BNT-BT_0.08), thin films. Dielectric, ferroelectric and piezoelectric properties of BNT-BT_0.08, thin films deposited by PLD on Pt/TiO₂/SiO₂/Si substrates are investigated in this paper. Perovskite structure of BNT-BT_0.08 thin films with random orientation of nanocrystallites has been obtained by deposition at 600 °C. The relative dielectric constant and loss tangent at 100 kHz, of BNT-BT_0.08 thin film with 530 nm thickness, were 820 and 0.13, respectively. Ferroelectric hysteresis measurements indicated a remnant polarization value of 22 μC/cm² and a coercive field of 120 kV/cm. The piezoresponse force microscopy (PFM) data showed that most of the grains seem to be constituted of single ferroelectric domain. The as-deposited BNT-BT_0.08 thin film is ferroelectric at the nanoscale level and piezoelectric.     

Synthesis,growth and characterization of l-threonine zinc acetate (LTZA) NLO single crystal

Single crystals of l-threonine zinc acetate (LTZA) were grown from an aqueous solution by slow evaporation technique. Single crystal X-ray diffraction analysis reveals that the crystal belongs to monoclinic system. The optical transmission study reveals the transparency of the crystal in the entire visible region and the cut off wavelength has been found to be 350 nm. The optical band gap is found to be 3.55 eV. The microhardness studies reveal the mechanical strength of the grown crystal. The dielectric constant and dielectric loss were carried out for the grown crystal. Photoconductivity measurements carried out on the grown crystal reveal the negative photoconducting nature.     

Effect of deposition temperature on orientation and electrical properties of (K0.5Na0.5)NbO3 thin films by pulsed laser deposition

Lead-free ferroelectric K_0.5Na_0.5NbO₃ (KNN) thin films have been prepared on Pt/TiO₂/SiO₂/Si substrates by pulsed laser deposition process. The structures, crystal orientations and electrical properties of thin films have been investigated as a function of deposition temperature from 680 °C to 760 °C. It is found that the deposition temperature plays an important role in the structures, crystal orientations and electrical properties of thin films. The crystallization of thin films improves with increasing deposition temperature. The thin film deposited at 760 °C exhibits strong (0 0 1) preferential orientation, large dielectric constant of 930 and the remnant polarization of 8.54 μC/cm².     

Nucleation kinetics,growth and hardness parameters of l-alanine alaninium picrate (LAAP) single crystals

Amino acids are considered to be the building blocks of proteins and are gaining importance due to their interesting optical behavior. l-alanine is an amino acid which dissolves in water and it can react with other acids to form new compounds. In this work, l-alanine is mixed with picric acid to prepare l-alanine alaninium picrate (LAAP) salt. Solubility and metastable zone width were measured for LAAP salt and induction period was measured at different supersaturation ratios. The critical nucleation parameters were evaluated based on the classical theory of homogeneous nucleation. Using the optimized nucleation parameters, single crystals of LAAP salt were grown by slow evaporation technique. XRD and FTIR studies were carried out to understand structural and molecular formation of the crystal. Microhardness measurements were performed on the grown LAAP crystal and various parameters such as work hardening constant, stiffness constant, yield strength, resistance pressure and corrected hardness were evaluated. Nonlinear optical behavior of the sample was analyzed.     

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.