Search

Novel derivatives were prepared by reaction of aromatic amines with 2-(4-ethylphenoxymethyl)benzoyl isothiocyanate, affording the N-[2-(4-ethylphenoxymethyl) benzoyl]-N?-(substituted phenyl)thiourea. Structural elucidation of these compounds was performed by IR, NMR spectroscopy and elemental analysis. The new compounds were used in combination with Fe3O4 and polyvinylpyrrolidone (PVP) for the coating of medical surfaces. In our experiments, catheter pieces were coated by Matrix Assisted Pulsed Laser Evaporation (MAPLE) technique. The microbial adherence ability was investigated in 6 multi-well plates by using culture based methods. The obtained surfaces were also assessed for their cytotoxicity with respect to osteoblast cells, by using fluorescence microscopy and MTT assay. The prepared surfaces by advanced laser processing inhibited the adherence and biofilm development ability of Staphylococcus aureus and Pseudomonas aeruginosa tested strains while cytotoxic effects on the 3T3-E1 preosteoblasts embedded in layer shaped alginate hydrogels were not observed. These results suggest that the obtained medical surfaces, based on the novel thiourea derivatives and magnetic nanoparticles with a polymeric shell could represent a promising alternative for the development of new and effective anti-infective strategies. [ABSTRACT FROM AUTHOR]

Cinnamomum verum-functionalized Fe3O4 nanoparticles of 9.4 nm in size were laser transferred by matrix assisted pulsed laser evaporation (MAPLE) technique onto gastrostomy tubes (G-tubes) for antibacterial activity evaluation toward Gram positive and Gram negative microbial colonization. X-ray diffraction analysis of the nanoparticle powder showed a polycrystalline magnetite structure, whereas infrared mapping confirmed the integrity of C. verum (CV) functional groups after the laser transfer. The specific topography of the deposited films involved a uniform thin coating together with several aggregates of bio-functionalized magnetite particles covering the G-tubes. Cytotoxicity assays showed an increase of the G-tube surface biocompatibility after Fe3O4@CV treatment, allowing a normal development of endothelial cells up to five days of incubation. Microbiological assays on nanoparticle-modified G-tube surfaces have proved an improvement of anti-adherent properties, significantly reducing both Gram negative and Gram positive bacteria colonization. [ABSTRACT FROM AUTHOR]

This paper studies optical, chemical and photoinduced changes in amorphous AsS films, obtained by nanosecond pulsed-laser ablation of a As40S60 target. The arsenic content of the films is slightly higher than the target composition and depends on the ablation fluence. The photobleaching phenomenon appears after 1-2 min of bandgap laser irradiation. The refractive index diminishes by 0.07 and the transmission approximately doubles. It was established for the first time that films obtained by pulsed laser deposition exhibit a positive resist behavior in amine-containing etchant. The etching rate of the irradiated film was 0.12 µm/min, while as-deposited films have lower etching rate. The measured selectivity rate was of 14:1. A 2D high-quality hole array was produced by direct laser writing and further etching. The unusual behavior can be a result of different glass network formation during the condensation of AsSn molecules sputtered from the bulk target. This is different from the case of thermally evaporated films where AsS1 molecules only were identified in gas-phase by mass spectrometry. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

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 t a n δ 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. [ABSTRACT FROM AUTHOR]

Nanocomposite thin films, sensitive to methane at the room temperature (25–30 °C), have been prepared, starting from SnSe2 powder and Zn(II)-5,10,15,20-tetrakis-(4-aminophenyl)- -porphyrin (ZnTAPP) powder, that were fully characterized by XRD, UV-VIS, FT-IR, Nuclear Magnetic Resonance (1H-NMR and 13C-NMR), Atomic Force Microscopy (AFM), SEM and Electron Paramagnetic Resonance (EPR) techniques. Film deposition was made by drop casting from a suitable solvent for the two starting materials, after mixing them in an ultrasonic bath. The thickness of these films were estimated from SEM images, and found to be around 1.3 μm. These thin films proved to be sensitive to a threshold methane (CH4) concentration as low as 1000 ppm, at a room temperature of about 25 °C, without the need for heating the sensing element. The nanocomposite material has a prompt and reproducible response to methane in the case of air, with 50% relative humidity (RH) as well. A comparison of the methane sensing performances of our new nanocomposite film with that of other recently reported methane sensitive materials is provided. It is suitable for signaling gas presence before reaching the critical lower explosion limit concentration of methane at 50,000 ppm. [ABSTRACT FROM AUTHOR]

Different medical devices for cutaneous wound healing such as patches and hydrogels containing biologically active principles were developed over time. In our study we proposed composite coatings based on PLGA (poly (lacticco- glycolic acid)) embedded with Ibuprofen (IBU) as potential dressings for topical wounds management. The PLGA:IBU materials were evaluated by performing long-term studies under biologically-simulated dynamic conditions and assessed in vitro for biological effects. IBU-loaded composite coatings, PLGA:IBU (2:1 and 10:1 wt. %) were obtained by combining dip-coating and drop-cast methods. The uniform PLGA:IBU (2:1) coatings resulted in slowly and progressive release of the drug and emphasized a pronounced IBU release starting from day 10 of dynamic evaluation. These observations were accompanied by noticeable mass variations and significant morphological modifications of the coatings. The viability and proliferation of the cells are not affected, irrespective of composite surface type or time of incubation. Cell adhesion and morphology investigations performed by fluorescence microscopy showed a predominantly round shape for THP-1 cells cultured on control material. On composite materials, the macrophages presented a modified morphology adapted to substrate content, and an increased cell shape with more evident actin filaments. All materials per se do not induce an inflammatory effect as revealed by TNF-α release measurements based on ELISA assay. Physical-chemical and biological characteristics of PLGA:IBU composite coatings revealed that these materials could represent useful medical devices in topical treatment of skin injures. Acknowledgement: This research received funding from Romanian National Authority for Scientific Research (CNCS– UEFISCDI), under the projects TERAMED 63PCCDI/2018 and Structural and Functional Proteomics Research Program of the Institute of Biochemistry of the Romanian Academy [ABSTRACT FROM AUTHOR]

Polymer nanoparticles (PNPs), one of the most innovative non-invasive approaches for drug delivery applications has the capacity to convey the therapeutic molecule directly into the target organ or tissue. Poly(D,L-lactideco- glycolide) (PLGA) is a synthetic polymer used in biological applications, approved by the Food and Drug Administration. PLGA posess the ability to efficiently entrap hydrophobic and hydrophilic drugs and have been shown to enhance the cellular uptake of entrapped bioactive compounds improving the drug efficacy. In our studies PLGA nanoparticles containing anti-inflammatory/antitumoral drugs were optimized for their physico-chemical properties in term of size and polidispersity index. Biocompatibility and intracellular uptake of FITC-PLGA were studied in different cell types (mouse embryonic fibroblasts - K41, mouse melanona cell - B16-F10, human hepatoma cell- HepaRG and epithelial cells from bovine kidney-MDBK) to develope a novel drug delivery systems usefull for antiinflammatory/ antitumoral therapy. PNPs interaction with mammalian cells was assessed by cytotoxicity measurement, fluorescence microscopy investigation, and flow cytometry quantitation. PLGA based NPs showed extremely low cytotoxicity only when delivered in high concentrations (over 2mg/mL). PLGA nanoparticles have the capacity to pass membrane barriers and showed increased tendency to aggregate, which could interfere with their potential function as drug carriers. Our studies revealed the conditions required for PLGA based NPs interactions with the cells and their intracellular uptake. The presented data are significant for the potential applications of PLGA-based NPs formulation as drug delivery vehicle. [ABSTRACT FROM AUTHOR]

Indium tin oxide (ITO) thin films were grown on nanopatterned glass substrates by the pulsed laser deposition (PLD) technique. The deposition was carried out at 1.2 J/cm2 laser fluence, low oxygen pressure (1.5 Pa) and on unheated substrate. Arrays of periodic pillars with widths of ~350 nm, heights of ~250 nm, and separation pitches of ~1100 nm were fabricated on glass substrates using UV nanoimprint lithography (UV-NIL), a simple, cost-effective, and high throughput technique used to fabricate nanopatterns on large areas. In order to emphasize the influence of the periodic patterns on the properties of the nanostructured ITO films, this transparent conductive oxide (TCO) was also grown on flat glass substrates. Therefore, the structural, compositional, morphological, optical, and electrical properties of both non-patterned and patterned ITO films were investigated in a comparative manner. The energy dispersive X-ray analysis (EDX) confirms that the ITO films preserve the In2O3:SnO2 weight ratio from the solid ITO target. The SEM and atomic force microscopy (AFM) images prove that the deposited ITO films retain the pattern of the glass substrates. The optical investigations reveal that patterned ITO films present a good optical transmittance. The electrical measurements show that both the non-patterned and patterned ITO films are characterized by a low electrical resistivity (<2.8 × 10−4). However, an improvement in the Hall mobility was achieved in the case of the nanopatterned ITO films, evidencing the potential applications of such nanopatterned TCO films obtained by PLD in photovoltaic and light emitting devices. [ABSTRACT FROM AUTHOR]

• Anodized TiO 2 NTs on FTO glass were doped with N by annealing in NH 3. • Substitutional n was not detected in the samples which were post-annealed in air. • N was incorporated interstitially in pre- and post-(air)annealed samples. • Weakly bonded NO x species were removed by post-annealing in air. • The biggest effect on absorption red shift was due to the interstitial N. The ∼60 nm wide and ∼2 μm long TiO 2 nanotubes were obtained by anodization of Ti films sputtered on F-doped tin oxide glass. For N-doping the samples were annealed in ammonia atmosphere. The effect of pre- and post-annealing in air on the nature and amount of incorporated N was studied by X-ray photoelectron spectroscopy. By measuring the absorption spectra of the obtained samples and interpreting the corresponding Tauc plots it was shown that the sample annealed just in ammonia showed the highest visible light absorption even after sputtering cleaning and a decrease of N amount from 3.8% to 1%. Pre and/or post annealing in air led to smaller amount of incorporated N, that caused less pronounced absorption enhancement and smaller band gap narrowing compared to the sample annealed only in ammonia. By fitting of N 1 s line, the contribution that was assigned to substitutional N was detected only in the samples that did not sustained post-annealing. The study showed that post-annealing in air might lead to partial conversion of N atoms in TiO 2 to oxidized nitrogen species that are easily removed with sputtering. It is also possible that substitutional nitrogen was suppressed by oxygen from air to move to interstitial site. Weakly bonded NO x surface species, which are cleaned away by sputtering, can be removed by post-annealing in air. Those surface species could act as sensitizers and when their amounts are reduced, the core absorption properties, as a result of interstitial incorporation of N in TiO 2 structure, were revealed. Much lower visible light sensitization was achieved in the case of pre-annealed sample in comparison to sample without pre-annealing, regardless the same quantity and type of incorporated nitrogen. [ABSTRACT FROM AUTHOR]

This study investigates the morphological changes induced by femtosecond (fs) laser pulses in arsenic trisulfide (As 2 S 3 ) thin films and gold-arsenic trisulfide (Au\As 2 S 3 ) 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 As 2 S 3 films, while the Au\As 2 S 3 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.

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.

In this study, we report on the synthesis of L-Cysteine (L-Cys)-coated magnetic iron oxide nanoparticles (NPs) loaded with doxorubicin (Dox). The Fe 3 O 4 -L-Cys-Dox NPs were extensively characterized for their compositional and morpho-structural features using EDS, SAED, XRD, FTIR and TEM. XPS, Mӧssbauer spectroscopy and SQUID measurements were also performed to determine the electronic and magnetic properties of the Fe 3 O 4 -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 Fe 3 O 4 -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 Fe 3 O 4 -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 Fe 3 O 4 -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 Fe 3 O 4 -L-Cys-Dox NPs as efficient drug delivery vehicles in melanoma therapy.

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.

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.

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.

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/cm 2 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.

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.

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.

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.

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.

Staggered gap radial heterojunctions based on ZnO-Cu x O core-shell nanowires are used as water stable photocatalysts to harvest solar energy for pollutants removal. ZnO nanowires with a wurtzite crystalline structure and a band gap of approximately 3.3 eV are obtained by thermal oxidation in air. These are covered with an amorphous Cu x O layer having a band gap of 1.74 eV and subsequently form core-shell heterojunctions. The electrical characterization of the ZnO pristine and ZnO-Cu x O core-shell nanowires emphasizes the charge transfer phenomena at the junction and at the interface between the nanowires and water based solutions. The methylene blue degradation mechanism is discussed taking into consideration the dissolution of ZnO in water based solutions for ZnO nanowires and ZnO-Cu x O core-shell nanowires with different shell thicknesses. An optimum thickness of the Cu x O layer is used to obtain water stable photocatalysts, where the ZnO-Cu x O radial heterojunction enhances the separation and transport of the photogenerated charge carriers when irradiating with UV-light, leading to swift pollutant degradation.

We report on the fabrication of dye-sensitized solar cells with a TiO 2 buffer layer between the transparent conductive oxide substrate and the mesoporous TiO 2 film, in order to improve the photovoltaic conversion efficiency of the device. The buffer layer was fabricated by pulsed laser deposition whereas the mesoporous film by the doctor blade method, using TiO 2 paste obtained by the sol-gel technique. The buffer layer was deposited in either oxygen (10 Pa and 50 Pa) or argon (10 Pa and 50 Pa) onto transparent conducting oxide glass kept at room temperature. The cross-section scanning electron microscopy image showed differences in layer morphology and thickness, depending on the deposition conditions. Transmission electron microscopy studies of the TiO 2 buffer layers indicated that films consisted of grains with typical diameters of 10 nm to 30 nm. We found that the photovoltaic conversion efficiencies, determined under standard air mass 1.5 global (AM 1.5G) conditions, of the solar cells with a buffer layer are more than two times larger than those of the standard cells. The best performance was reached for buffer layers deposited at 10 Pa O 2 . We discuss the processes that take place in the device and emphasize the role of the brush-like buffer layer in the performance increase.

Anodization of titanium film sputtered on fluorine doped tin oxide (FTO) glass was performed to obtain highly ordered ∼2 μm long and ∼60 nm wide TiO 2 nanotubes. The titania films were annealed in ammonia atmosphere to enable the doping with N. The annealing did not affect the nanotubular morphology and the porosity remained open which is a very important requirement for further deposition of CdS quantum dots. The analysis done by transmission electron microscopy (TEM) has shown that the N-doped nanotubes have a smaller interplanar distance as compared to the undoped ones, whose interplanar distance corresponded to anatase phase. This difference was attributed to the N doping and the Sn migration from the substrate, as demonstrated by energy dispersive spectroscopy (EDS) combined with electron energy loss spectroscopy (EELS). The near edge X-ray absorption fine structure (NEXAFS) analysis clearly demonstrated that also the doped TiO 2 film has anatase phase. Regarding the chemical composition of the studied samples, the X-ray photoelectron spectroscopy (XPS) and synchrotron radiation photoelectron spectroscopy (SRPES) analyses have shown that N is incorporated both interstitially and substitutionally in the TiO 2 lattice, with a decreased contribution of the interstitial after ionic sputtering. The shift of the valence band maximum (VBM) position for the doped TiO 2 vs. the undoped TiO 2 proved the narrowing of the band gap. The CdS/TiO 2 films show bigger VBM shifting that can be attributed to CdS deposit. Comparing the absorption spectra of the bare undoped and doped TiO 2 samples, it was noticed that the doping causes a red shift from 397 to 465 nm. Furthermore, the CdS deposition additionally enhances the absorption in the visible range (575 nm for undoped TiO 2 /CdS and 560 nm for doped TiO 2 /CdS films)., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)