Interactions of Chemically Synthesized Ferrihydrite Nanoparticles with Human Serum Transferrin: Insights from Fluorescence Spectroscopic Studies.

Human serum transferrin (HST) is a glycoprotein involved in iron transport that may be a candidate for functionalized nanoparticles to bind and target cancer cells. In this study, the effects of the simple and doped with cobalt (Co) and copper (Cu) ferrihydrite nanoparticles (Fh-NPs, Cu-Fh-NPs, and Co-Fh-NPs) were studied by spectroscopic and molecular approaches. Fluorescence spectroscopy revealed a static quenching mechanism for all three types of Fh-NPs. All Fh-NPs interacted with HST with low affinity, and the binding was driven by hydrogen bonding and van der Waals forces for simple Fh-NPs and by hydrophobic interactions for Cu-Fh-NPs and Co-Fh-NPs binding, respectively. Of all samples, simple Fh-NPs bound the most to the HST binding site. Fluorescence resonance energy transfer (FRET) allowed the efficient determination of the energy transfer between HST and NPs and the distance at which the transfer takes place and confirmed the mechanism of quenching. The denaturation of the HST is an endothermic process, both in the case of apo HST and HST in the presence of the three types of Fh-NPs. Molecular docking studies revealed that Fh binds with a low affinity to HST (Ka = 9.17 × 103 M-1) in accord with the fluorescence results, where the interaction between simple Fh-NPs and HST was described by a binding constant of 9.54 × 103 M-1.

Effect of Deposition Working Power on Physical Properties of RF-Sputtered CdTe Thin Films for Photovoltaic Applications.

The main objective of this study was to determine the variation in the properties of cadmium telluride (CdTe) thin films deposited on a p-type Si substrate by the radio frequency magnetron sputtering technique at four different working powers (70 W, 80 W, 90 W, and 100 W). The substrate temperature, working pressure, and deposition time during the deposition process were kept constant at 220 °C, 0.46 Pa, and 30 min, respectively. To study the structural, morphological, and optical properties of the CdTe films grown under the mentioned experimental conditions, X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), and optical spectroscopy were used. For a better analysis of the films' structural and optical properties, a group of films were deposited onto optical glass substrates under similar deposition conditions. The electrical characterisation of Ag/CdTe/Al "sandwich" structures was also performed using current-voltage characteristics in the dark at different temperatures. The electrical measurements allowed the identification of charge transport mechanisms through the structure. New relevant information released by the present study points towards 90 W RF power as the optimum for obtaining a high crystallinity of ~1 µm nanostructured thin films deposited onto p-Si and optical glass substrates with optical and electrical properties that are suitable for use as absorber layers. The obtained high-quality CdTe nanostructured thin films are perfectly suitable for use as absorbers in CdTe thin-film photovoltaic cells.

Tuning the infrared resonance of thermal emission from metasurfaces working in near-infrared.

We simulated numerically and demonstrated experimentally that the thermal emittance of a metasurface consisting of an array of rectangular metallic meta-atoms patterned on a layered periodic dielectric structure grown on top of a metallic layer can be tuned by changing several parameters. The resonance frequency, designed to be in the near-infrared spectral region, can be tuned by modifying the number of dielectric periods, and the polarization and incidence angle of the incoming radiation. In addition, the absorbance/emittance value at the resonant wavelength can be tuned by modifying the orientation of meta-atoms with respect to the illumination direction.

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.

Relationship between the Formation of Magnetic Clusters and Hexagonal Phase of Gold Matrix in AuxFe1-x Nanophase Thin Films.

AuxFe1-x nanophase thin films of different compositions and thicknesses were prepared by co-deposition magnetron sputtering. Complex morpho-structural and magnetic investigations of the films were performed by X-ray Diffraction, cross-section Transmission Electron Microscopy, Selected Area Electron Diffraction, Magneto Optical Kerr Effect, Superconducting Quantum Interference Device magnetometry and Conversion Electron Mössbauer Spectroscopy. It was proven that depending on the preparation conditions, different configurations of defect α-Fe magnetic clusters, i.e., randomly distributed or auto-assembled in lamellar or filiform configurations, can be formed in the Au matrix. A close relationship between the Fe clustering process and the type of the crystalline structure of the Au matrix was underlined, with the stabilization of a hexagonal phase at a composition close to 70 at. % of Au and at optimal thickness. Due to different types of inter-cluster magnetic interactions and spin anisotropies, different types of magnetic order from 2D Ising type to 3D Heisenberg type, as well as superparamagnetic behavior of non-interacting Fe clusters of similar average size, were evidenced.

Biogenic Ferrihydrite Nanoparticles Produced by Klebsiella oxytoca: Characterization, Physicochemical Properties and Bovine Serum Albumin Interactions.

The synthesis of nanoparticles inside microorganisms is an economical alternative to chemical and physical methods of nanoparticle synthesis. In this study, ferrihydrite nanoparticles synthesized by Klebsiella oxytoca bacterium in special conditions were characterized by scanning electron microscopy (SEM), energy-dispersive X-ray analysis (EDS), small-angle X-ray (SAXS), UV-Vis spectroscopy, fluorescence, fluorescence resonance energy transfer (FRET), and molecular docking. The morphology and the structure of the particles were characterized by means of SEM and SAXS. The elemental content was determined by means of the EDS method. The absorption properties of the ferrihydrite nanoparticles were investigated by UV-Vis spectroscopy. The binding mechanism of the biogenic ferrihydrite nanoparticles to Bovine Serum Albumin (BSA) protein, studied by fluorescence, showed a static and weak process, combined with FRET. Protein denaturation by temperature and urea in the presence of the ferrihydrite nanoparticles demonstrated their influence on the unfolding process. The AutoDock Vina and UCSF Chimera programs were used to predict the optimal binding site of the ferrihydrite to BSA and to find the location of the hydrophobic cavities in the sub-domain IIA of the BSA structure.

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.

Characterization of Monochromatic Aberrated Metalenses in Terms of Intensity-Based Moments.

Consistent with wave-optics simulations of metasurfaces, aberrations of metalenses should also be described in terms of wave optics and not ray tracing. In this respect, we have shown, through extensive numerical simulations, that intensity-based moments and the associated parameters defined in terms of them (average position, spatial extent, skewness and kurtosis) adequately capture changes in beam shapes induced by aberrations of a metalens with a hyperbolic phase profile. We have studied axial illumination, in which phase-discretization induced aberrations exist, as well as non-axial illumination, when coma could also appear. Our results allow the identification of the parameters most prone to induce changes in the beam shape for metalenses that impart on an incident electromagnetic field a step-like approximation of an ideal phase profile.

Modulation of the PLLA Morphology through Racemic Nucleation to Reach Functional Properties Required by 3D Printed Durable Applications.

This paper presents an alternative for enhancing the durability of poly (L-lactide) (PLLA) by racemic nucleation following stereo-complexation with a selected poly (D-lactide) (PLDA). The compounds are obtained by melt blending of a PLLA grade, previously designed for 3D printing but with a low heat deflection temperature and impact resistance, with grades of PLDA differing in their molecular weight (Mw), D-lactide content (DS) and concentration. Our method considered how to reveal the racemic nucleation caused by stereo-complexation and its influence on functional properties. The FTIR study we performed showed that, depending on Mw, DS and concentration of the stereo-complexer (PDLA) used, bigger or smaller spectral changes can occur. The stereo-complexation was confirmed by the DSC analysis and, for the selected compound, by the POM, SEM, AFM microscopies, functional property and shapeability as 3D printing filaments. All the obtained results sustain the idea that, if a PLLA with Mw of 4.5 × 104 g·mol-1 is modified with PDLA with a medium Mw of 11.6 × 104 g·mol-1, medium DS of 4% and 1% concentration, a racemic nucleation is possible. It produces a racemic polylactic acid (PDLLA) with improved durability and good shapeability as 3D printing filaments. These results are explicable if the dependence of the intermolecular interactions appears between the PLLA and stereo-complexer PDLA. To enlarge the durable applicability of racemic polylactic acid (PDLLA), future research should identify other parameters controling the PLA stereo-complexing as the intensifying the mobility of the macromolecules, the finding of the optimal recemic cristalization window.

Thickness Effect on Some Physical Properties of RF Sputtered ZnTe Thin Films for Potential Photovoltaic Applications.

Zinc telluride thin films with different thicknesses were grown onto glass substrates by the rf magnetron sputtering technique, using time as a variable growth parameter. All other deposition process parameters were kept constant. The deposited thin films with thickness from 75 to 460 nm were characterized using X-ray diffraction, electron microscopy, atomic force microscopy, ellipsometry, and UV-Vis spectroscopy, to evaluate their structures, surface morphology, topology, and optical properties. It was found out that the deposition time increase leads to a larger growth rate. This determines significant changes on the ZnTe thin film structures and their surface morphology. Characteristic surface metrology parameter values varied, and the surface texture evolved with the thickness increase. Optical bandgap energy values slightly decreased as the thickness increased, while the mean grains radius remained almost constant at ~9 nm, and the surface to volume ratio of the films decreased by two orders of magnitude. This study is the first (to our knowledge) that thoroughly considered the correlation of film thickness with ZnTe structuring and surface morphology characteristic parameters. It adds value to the existing knowledge regarding ZnTe thin film fabrication, for various applications in electronic and optoelectronic devices, including photovoltaics.

Effect of RF Power on the Physical Properties of Sputtered ZnSe Nanostructured Thin Films for Photovoltaic Applications.

Zinc selenide (ZnSe) thin films were deposited by RF magnetron sputtering in specific conditions, onto optical glass substrates, at different RF plasma power. The prepared ZnSe layers were afterwards subjected to a series of structural, morphological, optical and electrical characterizations. The obtained results pointed out the optimal sputtering conditions to obtain ZnSe films of excellent quality, especially in terms of better optical properties, lower superficial roughness, reduced micro-strain and a band gap value closer to the one reported for the ZnSe bulk semiconducting material. Electrical characterization were afterwards carried out by measuring the current-voltage (I-V) characteristics at room temperature, of prepared "sandwich"-like Au/ZnSe/Au structures. The analysis of I-V characteristics have shown that at low injection levels there is an Ohmic conduction, followed at high injection levels, after a well-defined transition voltage, by a Space Charge Limited Current (SCLC) in the presence of an exponential trap distribution in the band gap of the ZnSe thin films. The results obtained from all the characterization techniques presented, demonstrated thus the potential of ZnSe thin films sputtered under optimized RF plasma conditions, to be used as alternative environmentally-friendly Cd-free window layers within photovoltaic cells manufacturing.

Synthesis of titanium nitride via hybrid nanocomposites based on mesoporous TiO2/acrylonitrile.

In the present study, the synthesis of titanium nitride (TiN) by carbothermal reduction nitridation (CRN) reaction using nanocomposites made of mesoporous TiO2/acrylonitrile with different content of inorganic phase were explored. The choice of hybrid nanocomposite as precursor for the synthesis of TiN was made due to the possibility of having an intimate interface between the organic and inorganic phases in the mixture that can favours CRN reaction. Subsequently, the hybrid composites have been subjected to four-step thermal treatments at 290 °C, 550 °C, 1000 °C and 1400 °C under nitrogen atmosphere. The XRD results after thermal treatment at 1000 °C under nitrogen flow show the coexistence of two crystalline phases of TiO2, i.e. anatase and rutile, as well as TiN phase, together with the detection of amorphous carbon that proved the initiation of CRN reaction. Furthermore, the observations based on XRD patterns of samples thermally treated at 1400 °C in nitrogen atmosphere were in agreement with SEM analysis, that shows the formation of TiN by CRN reaction via hybrid nanocomposites mesoporous TiO2/acrylonitrile.

GeSn/SiO2 Multilayers by Magnetron Sputtering Deposition for Short-Wave Infrared Photonics.

The development of short-wave infrared (SWIR) photonics based on GeSn alloys is of high technological interest for many application fields, such as the Internet of things or pollution monitoring. The manufacture of crystalline GeSn is a major challenge, mainly because of the low miscibility of Ge and Sn. The use of embedded GeSn nanocrystals (NCs) by magnetron sputtering is a cost-effective and efficient method to relax the growth conditions. We report on the use of GeSn/SiO2 multilayer deposition as a way to control the NC size and their insulation. The in situ prenucleation of NCs during deposition was followed by ex situ rapid thermal annealing. The nanocrystallization of 20×(11nm_Ge0.865Sn0.135/1.5nm_SiO2) multilayers leads to formation of GeSn NCs with ∼16% Sn concentration and ∼9 nm size. Formation of GeSn domes that are vertically correlated contributes to the nanocrystallization process. The absorption limit of ∼0.4 eV in SWIR found by ellipsometry is in agreement with the spectral photosensitivity. The ITO/20×(GeSn NC/SiO2)/p-Si/Al diodes show a maximum value of the SWIR photosensitivity at a reverse voltage of 0.5 V, with extended sensitivity to wavelengths longer than 2200 nm. The multilayer diodes have higher photocurrent efficiency compared to diodes based on a thick monolayer of GeSn NCs.

Epitaxial GeSn Obtained by High Power Impulse Magnetron Sputtering and the Heterojunction with Embedded GeSn Nanocrystals for Shortwave Infrared Detection.

GeSn alloys have the potential of extending the Si photonics functionality in shortwave infrared (SWIR) light emission and detection. Epitaxial GeSn layers were deposited on a relaxed Ge buffer on Si(100) wafer by using high power impulse magnetron sputtering (HiPI-MS). Detailed X-ray reciprocal space mapping and HRTEM investigations indicate higher crystalline quality of GeSn epitaxial layers deposited by Ge HiPI-MS compared to commonly used radio frequency magnetron sputtering (RF-MS). To obtain a rectifying heterostructure for SWIR light detection, a layer of GeSn nanocrystals (NCs) embedded in oxide was deposited on the epitaxial GeSn one. Embedded GeSn NCs are obtained by cosputtering deposition of (Ge1-xSnx)1-y(SiO2)y layers and subsequent rapid thermal annealing at a low temperature of 400 °C. Intrinsic GeSn structural defects give p-type behavior, while the presence of oxygen leads to the n-character of the embedded GeSn NCs. Such an embedded NCs/epitaxial GeSn p-n heterostructure shows superior photoelectrical response up to 3 orders of magnitude increase in the 1.2-2.5 µm range, as compared to performances of diode based only on embedded NCs.