Fs Laser Patterning of Amorphous As2S3 Thin Films.

This study investigates the morphological changes induced by femtosecond (fs) laser pulses in arsenic trisulfide (As2S3) thin films and gold-arsenic trisulfide (Au\As2S3) heterostructures, grown by pulsed laser deposition (PLD). By means of a direct laser writing experimental setup, the films were systematically irradiated at various laser power and irradiation times to observe their effects on surface modifications. AFM was employed for morphological and topological characterization. Our results reveal a clear transition threshold between photoexpansion and photoevaporation phenomena under different femtosecond laser power regimes, occurring between 1 and 1.5 mW, irrespective of exposure time. Notably, the presence of a gold layer in the heterostructure minimally influenced this threshold. A maximum photoexpansion of 5.2% was obtained in As2S3 films, while the Au\As2S3 heterostructure exhibited a peak photoexpansion of 0.8%. The study also includes a comparative analysis of continuous-wave (cw) laser irradiation, confirming the efficiency of fs laser pulses in inducing photoexpansion effects.

Macrocyclic Compounds: Metal Oxide Particles Nanocomposite Thin Films Deposited by MAPLE.

Nanocomposite films based on macrocyclic compounds (zinc phthalocyanine (ZnPc) and 5,10,15,20-tetra(4-pyridyl) 21H,23H-porphyrin (TPyP)) and metal oxide nanoparticles (ZnO or CuO) were deposited by matrix-assisted pulsed laser evaporation (MAPLE). 1,4-dioxane was used as a solvent in the preparation of MAPLE targets that favor the deposition of films with a low roughness, which is a key feature for their integration in structures for optoelectronic applications. The influence of the addition of ZnO nanoparticles (~20 nm in size) or CuO nanoparticles (~5 nm in size) in the ZnPc:TPyP mixture and the impact of the added metal oxide amount on the properties of the obtained composite films were evaluated in comparison to a reference layer based only on an organic blend. Thus, in the case of nanocomposite films, the vibrational fingerprints of both organic compounds were identified in the infrared spectra, their specific strong absorption bands were observed in the UV-Vis spectra, and a quenching of the TPyP emission band was visible in the photoluminescence spectra. The morphological analysis evidenced agglomerated particles on the composite film surface, but their presence has no significant impact on the roughness of the MAPLE deposited layers. The current density-voltage (J-V) characteristics of the structures based on the nanocomposite films deposited by MAPLE revealed the critical role played by the layer composition and component ratio, an improvement in the electrical parameters values being achieved only for the films with a certain type and optimum amount of metal oxide nanoparticles.

Synthesis and Anti-Melanoma Activity of L-Cysteine-Coated Iron Oxide Nanoparticles Loaded with Doxorubicin.

In this study, we report on the synthesis of L-Cysteine (L-Cys)-coated magnetic iron oxide nanoparticles (NPs) loaded with doxorubicin (Dox). The Fe3O4-L-Cys-Dox NPs were extensively characterized for their compositional and morpho-structural features using EDS, SAED, XRD, FTIR and TEM. XPS, MÓ§ssbauer spectroscopy and SQUID measurements were also performed to determine the electronic and magnetic properties of the Fe3O4-L-Cys-Dox nanoparticles. Moreover, by means of a FO-SPR sensor, we evidenced and confirmed the binding of Dox to L-Cys. Biological tests on mouse (B16F10) and human (A375) metastatic melanoma cells evidenced the internalization of magnetic nanoparticles delivering Dox. Half maximum inhibitory concentration IC50 values of Fe3O4-L-Cys-Dox were determined for both cell lines: 4.26 µg/mL for A375 and 2.74 µg/mL for B16F10, as compared to 60.74 and 98.75 µg/mL, respectively, for unloaded controls. Incubation of cells with Fe3O4-L-Cys-Dox modulated MAPK signaling pathway activity 3 h post-treatment and produced cell cycle arrest and increased apoptosis by 48 h. We show that within the first 2 h of incubation in physiological (pH = 7.4) media, ~10-15 µM Dox/h was released from a 200 µg/mL Fe3O4-L-Cys-Dox solution, as compared to double upon incubation in citrate solution (pH = 3), which resembles acidic environment conditions. Our results highlight the potential of Fe3O4-L-Cys-Dox NPs as efficient drug delivery vehicles in melanoma therapy.

Effect of Aluminum Nanostructured Electrode on the Properties of Bulk Heterojunction Based Heterostructures for Electronics.

The properties of organic heterostructures with mixed layers made of arylenevinylene-based polymer donor and non-fullerene perylene diimide acceptor, deposited using Matrix Assisted Pulsed Laser Evaporation on flat Al and nano-patterned Al electrodes, were investigated. The Al layer electrode deposited on the 2D array of cylindrical nanostructures with a periodicity of 1.1 µm, developed in a polymeric layer using UV-Nanoimprint Lithography, is characterized by an inflorescence-like morphology. The effect of the nanostructuring on the optical and electrical properties was studied by comparison with those of the heterostructures based on a mixed layer with fullerene derivative acceptor. The low roughness of the mixed layer deposited on flat Al was associated with high reflectance. The nano-patterning, which was preserved in the mixed layer, determining the light trapping by multiple scattering, correlated with the high roughness and led to lower reflectance. A decrease was also revealed in photoluminescence emission both at UV and Vis excitation of the mixed layer, with the non-fullerene acceptor deposited on nano-patterned Al. An injector contact behavior was highlighted for all Al/mixed layer/ITO heterostructures by I-V characteristics in dark. The current increased, independently of acceptor (fullerene or non-fullerene), in the heterostructures with nano-patterned Al electrodes for shorter conjugation length polymer donors.

Cadmium Ions' Trace-Level Detection Using a Portable Fiber Optic-Surface Plasmon Resonance Sensor.

Environmental pollution with cadmium (Cd) is a major concern worldwide, with prolonged exposure to this toxic heavy metal causing serious health problems, such as kidney damage, cancer, or cardiovascular diseases, only to mention a few. Herein, a gold-coated reflection-type fiber optic--surface plasmon resonance (Au-coated FO-SPR) sensor is manufactured and functionalized with (i) bovine serum albumin (BSA), (ii) chitosan, and (iii) polyaniline (PANI), respectively, for the sensitive detection of cadmium ions (Cd2+) in water. Then, the three sensor functionalization strategies are evaluated and compared one at a time. Out of these strategies, the BSA-functionalized FO-SPR sensor is found to be highly sensitive, exhibiting a limit of detection (LOD) for Cd2+ detection at nM level. Moreover, the presence of Cd2+ on the FO-SPR sensor surface was confirmed by the X-ray photoelectron spectroscopy (XPS) technique and also quantified consecutively for all the above-mentioned functionalization strategies. Hence, the BSA-functionalized FO-SPR sensor is sensitive, provides a rapid detection time, and is cheap and portable, with potential applicability for monitoring trace-level amounts of Cd within environmental or potable water.

Efficient Decrease in Corrosion of Steel in 0.1 M HCl Medium Realized by a Coating with Thin Layers of MnTa2O6 and Porphyrins Using Suitable Laser-Type Approaches.

The purpose of this research is to meet current technical and ecological challenges by developing novel steel coating systems specifically designed for mechanical equipment used in aggressive acid conditions. Homogeneous sandwich-type layered films on the surface of steel electrodes were realized using a pseudo-binary oxide, MnTa2O6, and two different substituted porphyrin derivatives, namely: 5-(4-carboxy-phenyl)-10,15,20-tris (4-methyl-phenyl)-porphyrin and 5-(4-methyl-benzoate)-10,15,20-tris (4-methyl-phenyl)-porphyrin, which are novel investigated compound pairs. Two suitable laser strategies, pulsed laser deposition (PLD) and matrix-assisted pulsed laser evaporation (MAPLE), were applied in order to prevent porphyrin decomposition and to create smooth layers with low porosity that are extremely adherent to the surface of steel. The electrochemical measurements of corrosion-resistant coating performance revealed that in all cases in which the steel electrodes were protected, a significant value of corrosion inhibition efficiency was found, ranging from 65.6 to 83.7%, depending on the nature of the porphyrin and its position in the sandwich layer. The highest value (83.7%) was obtained for the MAPLE/PLD laser deposition of 5-(4-carboxy-phenyl)-10,15,20-tris (4-methyl-phenyl)-porphyrin/MnTa2O6(h), meaning that the inhibitors adsorbed and blocked the access of the acid to the active sites of the steel electrodes.

Capacitive Photodetector Thin-Film Cells of Cu-As2S3-Cu as Revealed by Dielectric Spectroscopy.

The As2S3-Cu interface was studied by dielectric spectroscopy measurements on Cu-As2S3-Cu thin film heterostructure samples to assess the charge carriers' contribution to the electrical properties of such an interface. Three-dimensional printed masks ensured good reproducibility during the PLD deposition of heterostructure samples. The samples were tested for electrical conductivity and AC photoconductivity by dielectric spectroscopy measurements. DC bias voltages and light were applied to the samples. The electrical capacity of the thin film heterostructure can be modified electrically and optically. We observed long-term photoconductivity with a time dependency that was not exponential, and a quick change of the electrical capacity, indicating the potential of the heterostructure cells as photodetector candidates.

Effects of Solvent Additive and Micro-Patterned Substrate on the Properties of Thin Films Based on P3HT:PC70BM Blends Deposited by MAPLE.

Lately, there is a growing interest in organic photovoltaic (OPV) cells due to the organic materials' properties and compatibility with various types of substrates. However, their efficiencies are low relative to the silicon ones; therefore, other ways (i.e., electrode micron/nanostructuring, synthesis of new organic materials, use of additives) to improve their performances are still being sought. In this context, we studied the behavior of the common organic bulk heterojunction (P3HT:PC70BM) deposited by matrix-assisted pulsed laser evaporation (MAPLE) with/without 0.3% of 1,8-diiodooctane (DIO) additive on flat and micro-patterned ITO substrates. The obtained results showed that in the MAPLE process, a small quantity of additive can modify the morphology of the organic films and decrease their roughness. Besides the use of the additive, the micro-patterning of the electrode leads to a greater increase in the absorption of the studied photovoltaic structures. The inferred values of the filling factors for the measured cells in ambient conditions range from 19% for the photovoltaic structures with no additive and without substrate patterning to 27% for the counterpart structures with patterning and a small quantity of additive.

Arylenevinylene Oligomer-Based Heterostructures on Flexible AZO Electrodes.

We investigated the optical and electrical properties of flexible single and bi-layer organic heterostructures prepared by vacuum evaporation with a p-type layer of arylenevinylene oligomers, based on carbazole, 3,3' bis(N hexylcarbazole)vinylbenzene = L13, or triphenylamine, 1,4 bis [4 (N,N' diphenylamino)phenylvinyl] benzene = L78, and an n-type layer of 5,10,15,20-tetra(4-pyrydil)21H,23H-porphyne = TPyP. Transparent conductor films of Al-doped ZnO (AZO) with high transparency, >90% for wavelengths > 400 nm, and low resistivity, between 6.9 × 10-4 Ω·cm and 23 × 10-4 Ω·cm, were deposited by pulsed laser deposition on flexible substrates of polyethylene terephthalate (PET). The properties of the heterostructures based on oligomers and zinc phthalocyanine (ZnPc) were compared, emphasizing the effect of the surface morphology. The measurements revealed a good absorption in the visible range of the PET/AZO/arylenevinylene oligomer/TPyP heterostructures and a typical injection contact behavior with linear (ZnPc, L78) or non-linear (L13) J-V characteristics in the dark, at voltages < 0.4 V. The heterostructure PET/AZO/L78/TPyP/Al showed a current density of ~1 mA/cm2 at a voltage of 0.3 V. The correlation between the roughness exponent, evaluated from the height-height correlation function, grain shape, and electrical behavior was analyzed. Consequently, the oligomer based on triphenylamine could be a promising replacement of donor ZnPc in flexible electronic applications.

Composite Drug Delivery System Based on Amorphous Calcium Phosphate-Chitosan: An Efficient Antimicrobial Platform for Extended Release of Tetracycline.

One major warning emerging during the first worldwide combat against healthcare-associated infections concerns the key role of the surface in the storage and transfer of the virus. Our study is based on the laser coating of surfaces with an inorganic/organic composite mixture of amorphous calcium phosphate-chitosan-tetracycline that is able to fight against infectious agents, but also capable of preserving its activity for a prolonged time, up to several days. The extended release in simulated fluids of the composite mixture containing the drug (tetracycline) was demonstrated by mass loss and UV-VIS investigations. The drug release profile from our composite coatings proceeds via two stages: an initial burst release (during the first hours), followed by a slower evolution active for the next 72 h, and probably more. Optimized coatings strongly inhibit the growth of tested bacteria (Enterococcus faecalis and Escherichia coli), while the drug incorporation has no impact on the in vitro composite's cytotoxicity, the coatings proving an excellent biocompatibility sustaining the normal development of MG63 bone-like cells. One may, therefore, consider that the proposed coatings' composition can open the prospective of a new generation of antimicrobial coatings for implants, but also for nosocomial and other large area contamination prevention.

Chemical Degradation of Methylene Blue Dye Using TiO2/Au Nanoparticles.

Gold nanoparticles (~10 nm) were deposited on titanium dioxide nanoparticles (~21 nm) and the material obtained was characterized using IR, UV-Vis, N2 adsorption-desorption isotherm, DLS, EDS (EDX), TEM, XPS, and XRD techniques. It was found that the methylene blue dye is degraded in the presence of this material when using hydrogen peroxide as the oxidant. Tests were performed at 2, 4, 6, and 24 h, with hydrogen peroxide contents varying from 1 to 5 mg/mL. Longer exposure time and a higher content of oxidant led to the degradation of methylene blue dye at up to 90%. The material can be reused several times with no loss of activity.

Sensitive pH Monitoring Using a Polyaniline-Functionalized Fiber Optic-Surface Plasmon Resonance Detector.

In this work, we report results on the fabrication and characterization of a surface plasmon resonance (SPR) pH sensor using platinum (Pt) and polyaniline (PANI) layers successively coated over an unclad core of an optical fiber (FO). The plasmonic thin Pt layer was deposited using a magnetron sputtering technique, while the pH-sensitive PANI layer was synthesized using an electroless polymerization method. Moreover, the formation of PANI film was confirmed by X-ray photoelectron spectroscopy (XPS) technique and its surface morphology was investigated using scanning electron microscopy (SEM). It was found that the PANI/Pt-coated FO-SPR pH sensor exhibits a fast and linear response in either acid or alkali solutions (pH operational range: 1 to 14). The proposed FO-SPR sensor could be used for biomedical applications, environmental monitoring or any remote, real-time on-site measurements.

A polyaniline/platinum coated fiber optic surface plasmon resonance sensor for picomolar detection of 4-nitrophenol.

The paper reports for the first time an innovative polyaniline (PANI)/platinum (Pt)-coated fiber optic-surface plasmon resonance (FO-SPR) sensor used for highly-sensitive 4-nitrophenol (4-NP) pollutant detection. The Pt thin film was coated over an unclad core of an optical fiber (FO) using a DC magnetron sputtering technique, while the 4-NP responsive PANI layer was synthetized using a cost-effective electroless polymerization method. The presence of the electrolessly-grown PANI on the Pt-coated FO was observed by field-emission scanning electron microscopy and subsequently evidenced by energy dispersive X-ray analysis. These FO-SPR sensors with a demonstrated bulk sensitivity of 1515 nm/RIU were then employed for 4-NP sensing, exhibiting an excellent limit-of-detection (LOD) in the low picomolar range (0.34 pM). The proposed sensor's configuration has many other advantages, such as low-cost production, small size, immunity to electromagnetic interferences, remote sensing capability, and moreover, can be operated as a "stand-alone device", making it thus well-suited for applications such as "on-site" screening of extremely low-level trace pollutants.

Electrolyte-Dependent Modification of Resistive Switching in Anodic Hafnia.

Anodic HfO2 memristors grown in phosphate, borate, or citrate electrolytes and formed on sputtered Hf with Pt top electrodes are characterized at fundamental and device levels. The incorporation of electrolyte species deep into anodic memristors concomitant with HfO2 crystalline structure conservation is demonstrated by elemental analysis and atomic scale imaging. Upon electroforming, retention and endurance tests are performed on memristors. The use of borate results in the weakest memristive performance while the citrate demonstrates clear superior memristive properties with multilevel switching capabilities and high read/write cycling in the range of 106. Low temperature heating applied to memristors shows a direct influence on their behavior mainly due to surface release of water. Citrate-based memristors show remarkable properties independent on device operation temperatures up to 100 °C. The switching dynamic of anodic HfO2 memristors is discussed by analyzing high resolution transmission electron microscope images. Full and partial conductive filaments are visualized, and apart from their modeling, a concurrency of filaments is additionally observed. This is responsible for the multilevel switching mechanism in HfO2 and is related to device failure mechanisms.

Degradation Behavior of Polymers Used as Coating Materials for Drug Delivery-A Basic Review.

The purpose of the work was to emphasize the main differences and similarities in the degradation mechanisms in the case of polymeric coatings compared with the bulk ones. Combined with the current background, this work reviews the properties of commonly utilized degradable polymers in drug delivery, the factors affecting degradation mechanism, testing methods while offering a retrospective on the evolution of the controlled release of biodegradable polymeric coatings. A literature survey on stability and degradation of different polymeric coatings, which were thoroughly evaluated by different techniques, e.g., polymer mass loss measurements, surface, structural and chemical analysis, was completed. Moreover, we analyzed some shortcomings of the degradation behavior of biopolymers in form of coatings and briefly proposed some solving directions to the main existing problems (e.g., improving measuring techniques resolution, elucidation of complete mathematical analysis of the different degradation mechanisms). Deep studies are still necessary on the dynamic changes which occur to biodegradable polymeric coatings which can help to envisage the future performance of synthesized films designed to be used as medical devices with application in drug delivery.

Bioactive Ibuprofen-Loaded PLGA Coatings for Multifunctional Surface Modification of Medical Devices.

To modulate the biofunctionality of implantable medical devices commonly used in clinical practice, their surface modification with bioactive polymeric coatings is an attractive and successful emerging strategy. Biodegradable coatings based on poly(lactic acid-co-glycolic acid), PLGA, represent versatile and safe candidates for surface modification of implantable biomaterials and devices, providing additional tunable ability for topical delivery of desired therapeutic agents. In the present study, Ibuprofen-loaded PLGA coatings (PLGA/IBUP) were obtained by using the dip-coating and drop-casting combined protocol. The composite materials demonstrated long-term drug release under biologically simulated dynamic conditions. Reversible swelling phenomena of polymeric coatings occurred in the first two weeks of testing, accompanied by the gradual matrix degradation and slow release of the therapeutic agent. Irreversible degradation of PLGA coatings occurred after one month, due to copolymer's hydrolysis (evidenced by chemical and structural modifications). After 30 days of dynamic testing, the cumulative release of IBUP was ~250 µg/mL. Excellent cytocompatibility was revealed on human-derived macrophages, fibroblasts and keratinocytes. The results herein evidence the promising potential of PLGA/IBUP coatings to be used for surface modification of medical devices, such as metallic implants and wound dressings.

Bioactive Coatings Based on Hydroxyapatite, Kanamycin, and Growth Factor for Biofilm Modulation.

The occurrence of opportunistic local infections and improper integration of metallic implants results in severe health conditions. Protective and tunable coatings represent an attractive and challenging selection for improving the metallic devices' biofunctional performances to restore or replace bone tissue. Composite materials based on hydroxyapatite (HAp), Kanamycin (KAN), and fibroblast growth factor 2 (FGF2) are herein proposed as multifunctional coatings for hard tissue implants. The superior cytocompatibility of the obtained composite coatings was evidenced by performing proliferation and morphological assays on osteoblast cell cultures. The addition of FGF2 proved beneficial concerning the metabolic activity, adhesion, and spreading of cells. The KAN-embedded coatings exhibited significant inhibitory effects against bacterial biofilm development for at least two days, the results being superior in the case of Gram-positive pathogens. HAp-based coatings embedded with KAN and FGF2 protein are proposed as multifunctional materials with superior osseointegration potential and the ability to reduce device-associated infections.

Nanostructured LiFe5O8 by a Biogenic Method for Applications from Electronics to Medicine.

The physical properties of the cubic and ferrimagnetic spinel ferrite LiFe5O8 has made it an attractive material for electronic and medical applications. In this work, LiFe5O8 nanosized crystallites were synthesized by a novel and eco-friendly sol-gel process, by using powder coconut water as a mediated reaction medium. The dried powders were heat-treated (HT) at temperatures between 400 and 1000 °C, and their structure, morphology, electrical and magnetic characteristics, cytotoxicity, and magnetic hyperthermia assays were performed. The heat treatment of the LiFe5O8 powder tunes the crystallite sizes between 50 nm and 200 nm. When increasing the temperature of the HT, secondary phases start to form. The dielectric analysis revealed, at 300 K and 10 kHz, an increase of ε' (≈10 up to ≈14) with a tanδ almost constant (≈0.3) with the increase of the HT temperature. The cytotoxicity results reveal, for concentrations below 2.5 mg/mL, that all samples have a non-cytotoxicity property. The sample heat-treated at 1000 °C, which revealed hysteresis and magnetic saturation of 73 emu g-1 at 300 K, showed a heating profile adequate for magnetic hyperthermia applications, showing the potential for biomedical applications.

Organic Thin Films Based on DPP-DTT:C60 Blends Deposited by MAPLE.

The matrix-assisted pulsed laser evaporation (MAPLE) technique was used for depositing thin films based on a recently developed conjugated polymer, poly[2,5-(2-octyldodecyl)-3,6-diketopyrrolopyrrole-alt-5,5-(2,5-di(thien-2-yl)thieno [3,2-b]thiophene)] (DPP-DTT) and fullerene C60 blends. The targets used in the MAPLE process were obtained by freezing chloroform solutions with different DPP-DTT:C60 weight ratios, with the MAPLE deposition being carried at a low laser fluence, varying the number of laser pulses. The structural, morphological, optical, and electrical properties of the DPP-DTT:C60 blend layers deposited by MAPLE were investigated in order to emphasize the influence of the DPP-DTT:C60 weight ratio and the number of laser pulses on these features. The preservation of the chemical structure of both DPP-DTT and C60 during the MAPLE deposition process is confirmed by the presence of their vibrational fingerprints in the FTIR spectra of the organic thin films. The UV-VIS and photoluminescence spectra of the obtained organic layers reveal the absorption bands attributed to DPP-DTT and the emission bands associated with C60, respectively. The morphology of the DPP-DTT:C60 blend films consists of aggregates and fibril-like structures. Regardless the DPP-DTT:C60 weight ratio and the number of laser pulses used during the MAPLE process, the current-voltage characteristics recorded, under illumination, of all structures developed on the MAPLE deposited layers evidenced a photovoltaic cell behavior. The results proved that the MAPLE emerges as a viable technique for depositing thin films based on conjugated polymers featured by a complex structure that can be further used to develop devices for applications in the solar cell area.

Proteomics of regenerated tissue in response to a titanium implant with a bioactive surface in a rat tibial defect model.

Due to their excellent mechanical and biocompatibility properties, titanium-based implants are successfully used as biomedical devices. However, when new bone formation fails for different reasons, impaired fracture healing becomes a clinical problem and affects the patient's quality of life. We aimed to design a new bioactive surface of titanium implants with a synergetic PEG biopolymer-based composition for gradual delivery of growth factors (FGF2, VEGF, and BMP4) during bone healing. The optimal architecture of non-cytotoxic polymeric coatings deposited by dip coating under controlled parameters was assessed both in cultured cells and in a rat tibial defect model (100% viability). Notably, the titanium adsorbed polymer matrix induced an improved healing process when compared with the individual action of each biomolecules. High-performance mass spectrometry analysis demonstrated that recovery after a traumatic event is governed by specific differentially regulated proteins, acting in a coordinated response to the external stimulus. Predicted protein interactions shown by STRING analysis were well organized in hub-based networks related with response to chemical, wound healing and response to stress pathways. The proposed functional polymer coatings of the titanium implants demonstrated the significant improvement of bone healing process after injury.