National Institute Of Materials Physics - Romania

This work focuses on the investigation of the liquid crystalline behavior and luminescence properties of the lanthanide complexes of Eu(III), Sm(III) and Tb(III) with N-biphenyl-alkylated-4-pyridone ligands. The organic ligands having a biphenyl group attached via a long flexible spacer with either 9 or 10 carbon atoms were synthesized by the reaction between 4-hydroxypyridine and the corresponding bromide compounds. The chemical structures of the organic and lanthanide complexes were assigned based on elemental analysis, single-crystal X-ray diffraction, H-1, C-13 NMR and IR spectroscopies, and thermogravimetric analysis (TGA). The X-ray diffraction analysis of a parent compound shows that the lanthanide ions are surrounded by three monodentate pyridone ligands and three bidentate nitrate ions, giving a 9-coordinate environment. The mesogenic behavior and the type of liquid crystalline phases exhibited by the new complexes were analyzed by differential scanning calorimetry (DSC) and polarizing optical microscopy (POM), and powder X-ray diffraction (XRD) studies. Only the lanthanide complexes with longer spacer (10) display a monotropic SmA phase, typically on a short thermal range (less than 10 degrees C). The complexes with shorter flexible chains (9) show no liquid crystalline properties with melting temperatures lower than their analogs with longer spacers. The emission spectra recorded in solid state at room temperatures show typical emission bands for each lanthanide ion employed (Eu(III), Tb(III) and Sm(III)).

Photodegradation of the aqueous solutions of acetylsalicylic acid, in the absence (ASA) and the presence of excipients (ASE), is demonstrated by the photoluminescence (PL). A shift of the PL bands from 342 and 338 nm to 358 and 361-397 nm for ASA and ASE in solid state and as aqueous solutions was reported. By exposure of the solution of ASA 0.3 M to UV light, a decrease in the PL band intensity was highlighted. This behavior was revealed for ASA in the presence of phosphate buffer (PB) having the pH equal to 6.4, 7, and 8 or by the interaction with NaOH 0.3 M. A different behavior was reported in the case of ASE. In the presence of PB, an increase in the intensity of the PL band of ASE simultaneously with a change of the ratio between the intensities of the bands at 361-364 and 394-397 nm was highlighted. The differences between PL spectra of ASA and ASE have their origin in the presence of salicylic acid (SAL). The interaction of ASE with NaOH induces a shift of the PL band at 405-407 nm. Arguments for the reaction of ASA with NaOH are shown by Raman scattering and FTIR spectroscopy.

In this paper, potassium based triple cation mixed-halide perovskite films were explored in order to enhance the stability and photovoltaic performance of perovskite based solar cells. It was found that adding potassium (K+) to a double cation mixed halide perovskite (FA(0.80)MA(0.20)PbI(2.8)Cl(0.2)), structural, morphological and optoelectronic properties of perovskites are improved. The perovskite films were prepared by one-step spin coating method with and without K+ and characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), UV-Vis spectroscopy, X-ray photoelectron spectroscopy (XPS), and photoluminescence spectroscopy (PL). The results indicate that potassium incorporation reduces significantly the yellow non-perovskite delta-phase formation and improves the perovskite film quality, thus contributing to the reduction of hysteresis, improves the stability and increases the PCE up to 12.51%. Furthermore, the doped devices exhibit reduced hysteresis and provide remarkable shelf stability by retaining more than 70% of the initial efficiency with low humidity over 850 h. (C) 2020 Elsevier B.V. All rights reserved.

Phase-change memories have reached an advanced degree of maturity, although, to be able to meet the increasing storage demand, multilevel capability is needed. A GeTe memristor is obtained in an amorphous state and it is subjected to a specific thermal treatment which initiates the transition toward the crystalline state. It is found that this crystalline state initialization process is highly beneficial for subsequently obtaining a large number of intermediate resistive states between the high and low resistive states. Multiple resistance levels are achieved by operating the devices in both DC sweeps and rectangular pulse modes in the low-voltage subthreshold regime. The conduction is modeled using a space charge limited conduction model, showing three distinct conduction regions in the high resistive state which merge toward a single conduction region as the low resistive state is approached. The obtained memristors can be used as multilevel nonvolatile memories or as synapses in neuromorphic computing.

In this work, new films containing composite materials based on blends of thermoplastic polymers of the polyurethane (TPU) and polyolefin (TPO) type, in the absence and presence of BaTiO3 nanoparticles (NPs) with the size smaller 100 nm, were prepared. The vibrational properties of the free films depending on the weight ratio of the two thermoplastic polymers were studied. Our results demonstrate that these films are optically active, with strong, broad, and adjustable photoluminescence by varying the amount of TPU. The crystalline structure of BaTiO3 and the influence of thermoplastic polymers on the crystallization process of these inorganic NPs were determined by X-ray diffraction (XRD) studies. The vibrational changes induced in the thermoplastic polymer's matrix of the BaTiO3 NPs were showcased by Raman scattering and FTIR spectroscopy. The incorporation of BaTiO3 NPs in the matrix of thermoplastic elastomers revealed the shift dependence of the photoluminescence (PL) band depending on the BaTiO3 NP concentration, which was capable of covering a wide visible spectral range. The dependencies of the dielectric relaxation phenomena with the weight of BaTiO3 NPs in thermoplastic polymers blends were also demonstrated.

Using Raman scattering and FTIR spectroscopy, new optical evidence for the assembly of sensors based on reduced graphene oxide (RGO) and polydiphenylamine (PDPA) for the electrochemical detection of the epidermal growth factor receptor (EGFR) are reported. The assembly process of the RGO sheets electrochemical functionalized with PDPA involves the chemical adsorption of 1,4-phenylene diisothiocyanate (PDITC), followed by an incubation with protein G in phosphate buffer (PB) solution and after that the interaction with EGFR antibodies solution. Taking into account the changes reported by Raman scattering and FTIR spectroscopy, a chemical mechanism of the assembling process for this sensor is proposed. The preliminary testing of the electrochemical activity of the sensors based on RGO and PDPA was reported by cyclic voltammetry.

A new method to obtain poly(vinyl chloride) (PVC) spheres, which consists of an interaction between commercial PVC grains and hexyl ethyl cellulose and lauroyl peroxide at a temperature of 60 degrees C, is reported. The addition of the graphene oxide (GO) sheets dispersed in dimethylformamide to the reaction mixture leads to the generation of composites made of PVC spheres coated with GO sheets. Scanning electron microscopy studies have demonstrated that this method allows for the transformation of PVC grains with sizes between 75 and 227 mu m into spheres with sizes varying from 0.7 to 3.5 mu m when the GO concentration in the PVC/GO composite mass increases from 0.5 to 5 wt.%. Our studies of Raman scattering and FTIR spectroscopy highlight a series of changes that indicate the appearance of ClCH=CH-, CH2=CCl-, and/or -CH=CCl- units as a result of PVC partial dehydrogenation. New -COO- and C-OH bonds on the GO sheet surfaces are induced during the preparation of PVC spheres coated with GO sheets. A photoluminescence (PL) band with a maximum at 325 nm is reported to characterize the PVC spheres. A PVC PL quenching process is demonstrated to be induced by the increase in the concentration of the GO sheets in the PVC/GO composite mass. The perspectives regarding the use of this composite as a flame-retardant material are also reported.

The investigation of the effect of carbon nanomaterials and lipids on the aggregation particularities of the amyloid beta/A beta(1-42) layers is important for understanding the generation mechanism of neuronal disorder and how it can be inhibited. Additionally, amyloids are nanomaterials with a wide area of potential applications from nanotechnology to biotechnology. This paper presents a study about the preparation of A beta(1-42) layer by two different methods, Langmuir-Blodgett (L-B) and drop cast (DC), on Si and Si covered by a layer of Buckminster fullerene, C-60, and on the effect of fullerene layer or/and cholesterol (Ch) on the generation of A beta(1-42) secondary structure forms, relevant for specific applications. AFM, SEM FTIR and Raman analysis offered details about the layer surface topography, morphology and particularities of the secondary structure generated in the process of A beta(1-42) molecules aggregation. This study showed that the presence of Ch inhibited the formation of fibrils in A beta(1-42) film deposited by L-B on Si covered by C-60 The structures developed during aggregation were correlated with the topography and roughness of the films. The presence of Ch determined a decrease in roughness for L-B film and increase in roughness for DC film deposited on Si covered by C-60 layer.

Gleditsia triacanthos is an aggressive invasive species in Eastern Europe, producing a significant number of pods that could represent an inexhaustible resource of raw material for various applications. The aim of this study was to extract cellulose from the Gleditsia triacanthos pods, characterize it by spectrophotometric and UHPLC-DAD-ESI/MS analysis, and use it to fabricate a wound dressing that is multi-functionalized with phenolic compounds extracted from the leaves of the same species. The obtained cellulose microfibers (CM) were functionalized, lyophilized, and characterized by ATR-FTIR and SEM. The water absorption and retention capacity as well as the controlled release of phenolic compounds with antioxidant properties evaluated in temporal dynamics were also determined. The antimicrobial activity against reference and clinical multi-drug-resistant Escherichia coli, Staphylococcus aureus, Pseudomonas aeruginosa, Acinetobacter baumannii, Enterobacter cloacae, Candida albicans, and Candida parapsilosis strains occurred immediately after the contact with the tested materials and was maintained for 24 h for all tested microbial strains. In conclusion, the multi-functionalized cellulose microfibers (MFCM) obtained from the reproductive organs of an invasive species can represent a promising alternative for the development of functional wound dressings with antioxidant and antimicrobial activity, as well as being a scalable example for designing cost-effective, circular bio-economy approaches to combat the accelerated spread of invasive species.

Multifunctional Bi- and Fe-modified carbon xerogel composites (CXBiFe), with different Fe concentrations, were obtained by a resorcinol-formaldehyde sol-gel method, followed by drying in ambient conditions and pyrolysis treatment. The morphological and structural characterization performed by X-ray diffraction (XRD), Raman spectroscopy, N-2 adsorption/desorption porosimetry, scanning electron microscopy (SEM) and scanning/transmission electron microscopy (STEM) analyses, indicates the formation of carbon-based nanocomposites with integrated Bi and Fe oxide nanoparticles. At higher Fe concentrations, Bi-Fe-O interactions lead to the formation of hybrid nanostructures and off-stoichiometric Bi2Fe4O9 mullite-like structures together with an excess of iron oxide nanoparticles. To examine the effect of the Fe content on the electrochemical performance of the CXBiFe composites, the obtained powders were initially dispersed in a chitosan solution and applied on the surface of glassy carbon electrodes. Then, the multifunctional character of the CXBiFe systems is assessed by involving the obtained modified electrodes for the detection of different analytes, such as biomarkers (hydrogen peroxide) and heavy metal ions (i.e., Pb2+). The achieved results indicate a drop in the detection limit for H2O2 as Fe content increases. Even though the current results suggest that the surface modifications of the Bi phase with Fe and O impurities lower Pb2+ detection efficiencies, Pb2+ sensing well below the admitted concentrations for drinkable water is also noticed.