National Institute Of Materials Physics - Romania

This work describes the development of a flexible uric acid (UA) biosensor based on palladium-coated submicrometer electrospun poly(methylmethacrylate) (PMMA) fibers metalized with gold and attached to polyethylene terephthalate substrate (Pd/Au/PMMA/PET). The morphological characterization conducted by scanning electron microscopy revealed nanoscale Pd dendritic structures. Electrochemical investigations in the absence and in the presence of redox probes demonstrated that these Pd nanostructures are responsible for a six-fold increase in the electroactive area and enhanced electron transfer kinetics when compared to the gold-coated electrospun fibers. The UA biosensor obtained by immobilizing the uricase enzyme (UrOx) onto the Pd/Au/PMMA/PET electrode surface, allowed UA detection with a sensitivity of 431 mu A cm(-2) mM(-1) and a limit of detection of 12 mu M. Investigation of the redox reactions of hydrogen peroxide (a product of the enzymatic oxidation of UA by UrOx) at the Pd/Au/PMMA/PET electrode demonstrated that the working principle of the biosensor is based on the reduction of PdO produced at the electrode surface during the spontaneous reduction of hydrogen peroxide on Pd. This allows a biosensor operating potential of -0.05 V (vs Ag/AgCl) with high selectivity. The UrOx/Pd/Au/PMMA/PET biosensor was applied for UA detection in body fluids (sweat, urine, and blood serum) with recovery values between 98 and 105%, which were validated by high-performance liquid chromatography analysis. The stability of the device was evaluated over a period of 3 months, retaining 78% of the initial sensitivity, and reproducibility with RSD = 4.9% was achieved. The analytical performance of the biosensor under harsh mechanical deformations and at physiological temperatures demonstrated the potential applications of the device to wearable sensing platforms.

SiGeSn nanocrystals (NCs) in oxides are of considerable interest for photo-effect applications due to the fine-tuning of the optical bandgap by quantum confinement in NCs. We present a detailed study regarding the silicon germanium tin (SiGeSn) NCs embedded in a nanocrystalline hafnium oxide (HfO2) matrix fabricated by using magnetron co-sputtering deposition at room temperature and rapid thermal annealing (RTA). The NCs were formed at temperatures in the range of 500-800 degrees C. RTA was performed to obtain SiGeSn NCs with surfaces passivated by the embedding HfO2 matrix. The formation of NCs and beta-Sn segregation were discussed in relation to the deposition and processing conditions by employing HRTEM, XRD and Raman spectroscopy studies. The spectral photosensitivity exhibited up to 2000 nm in short-wavelength infrared (SWIR) depending on the Sn composition was obtained. Comparing to similar results on GeSn NCs in SiO2 matrix, the addition of Si offers a better thermal stability of SiGeSn NCs, while the use of HfO2 matrix results in better passivation of NCs increasing the SWIR photosensitivity at room temperature. These results suggest that SiGeSn NCs embedded in an HfO2 matrix are a promising material for SWIR optoelectronic devices.

In this work, we demonstrate, for the first time, that coupling together the pyroelectric effect, the photovoltaic effect and the plasmonic effect is a novel method to significantly enhance the performance of self-powered photodetectors in the visible region. Photodetectors based on tri-layered heterojunction of n-Si/p-SnO/n-ZnO through the inclusion of silver (Ag) nanoparticles (NPs) at the SnO/ZnO interface were fabricated. The photo-response of the device, with excitation from a chopped 650 nm wavelength laser, was carefully investigated, and it was shown that the photodetector performance is enhanced the most with the inclusion of spheroidal Ag NPs with similar to 70 nm diameter. The Al/Si/SnO/Ag NPs/ZnO/ITO device exhibited an optimum responsivity, detectivity and sensitivity of 210.2 mA W-1, 5.47 x 109 Jones and 15.0 x 104, respectively, together with a rise and fall time of 2.3 and 51.3 mu s, respectively, at a laser power density of 317 mW cm-2 and at a chopper frequency of 10 Hz. The present photodetectors are more than twice as responsive as the current best-performing ZnO-based pyro-phototronic photodetectors and they also exhibit other competitive features, such as detectivity, and fall and rise times. Therefore, by exploiting the plasmonic effect of the Ag NPs together with the pyroelectric effect in a ZnO film, and the photovoltaic effect at a Si/SnO junction, all in a single device, photodetectors were developed with state-of-the-art performance for the visible region. Coupling together the pyroelectric effect, the photovoltaic effect and the plasmonic effect is a novel method to significantly enhance the performance of self-powered photodetectors in the visible region.

Synapses play a vital role in information processing, learning, and memory formation in the brain. By emulating the behavior of biological synapses, electronic synaptic devices hold the promise of enabling high-performance, energy-efficient, and scalable neuromorphic computing. Ferroelectric memristive devices integrate the characteristics of both ferroelectric and memristive materials and present a far-reaching potential as artificial synapses. Here, it is reported on a new ferroelectric device on silicon, a field-effect memristor, consisting of an epitaxial ultrathin ferroelectric Hf(0.5)Z(r0.5)O(2) film sandwiched between an epitaxial highly doped oxide semiconductor SrTiO3-delta and a top metal. Upon a low voltage of less than 2 V, the field-effect modulation in the semiconductor enables to access multiple states. The device works in a large time domain ranging from milliseconds down to tens of nanoseconds. By gradually switching the polarization by identical pulses, the ferroelectric diode devices can dynamically adjust the synaptic strength to mimic short- and long-term memory plasticity. Ionic contributions due to redox processes in the oxide semiconductor beneficially influence the device operation and retention.

Dense samples of MgB2, with a relative density of 98.3-99.1 %, were prepared by ex-situ spark plasma sintering using a raw powder supplied by Alfa Aesar. Samples were added with Ge-based organometallics (repagermanium/RGe, propagermaniu/PGe, linear Ge-based organometallic/GeSP, and Na-doped octamer/8THGP-Na) for the starting composition (MgB2)(Ge-based organometallics)0.0014. Except for the 8THGP-Na, they have a similar chemical composition in respect to Ge and C, while the crystal structure differs. Below 20 K, all studied additions increased the critical current density, Jc, and the irreversibility field, Hirr. Samples added with GeSP and 8THGPNa have marginal differences regarding superconducting characteristics. The best Jc and Hirr are obtained for the sample added with RGe. This sample has the highest amount of carbon in the crystal lattice of MgB2. Results point out that there is a complex influence of the additive on carbon behaviour. Although in general it is accepted that a higher amount of carbon produces higher Jc and Hirr, a comparison with the literature indicates that C-rich raw MgB2 powders (e.g. the C-enhanced MgB2 nanopowder produced by Pavezyum) are not suitable to promote strong superconductivity enhancement in the samples added with indicated organometallics, and the origin, states, and evolution of carbon should to be carefully assessed.

The bioavailability of the administered drugs that reach the systemic circulation is the first point in resolving the pathology of patients. Albumin-based nanoparticles represent an increasingly used strategy to deliver cancer drugs into cells that otherwise cannot overcome biological barriers. In this work, rutin (Ru), a flavonoid with anticancer and antioxidant potential, was incorporated into bovine serum albumin nanoparticles (BSA-Ru NPs), developed using the desolvation method, and the entire system was characterized and evaluated by scanning electron microscopy (SEM), atomic force microscopy (AFM), and UV-Vis absorption spectroscopy. The results showed that BSA and BSA-Ru NPs are uniformly distributed, have relatively large sizes, and have a time stability of more than 60%. Furthermore, the effect of these nanohybrids on the thermal stability of liposomal membranes was evaluated by surface plasmon resonance (SPR), cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS). The viability evaluation was assessed by the tetrazolium salt (3-(4,5-dimethylthiazol-2-yl)-5-(3-carboxymethoxyphenyl)-2-(4-sulfophenyl)-2H-tetrazolium) (MTS) protocol in the fibroblast L929 line and a high level of biocompatibility, confirmed by SEM results, was found.

Ti-aluminosilicate gels were used as supports for the immobilization of Fe, Co, and Ni oxides (5%) by impregnation and synthesis of efficient photocatalysts for the degradation of beta-lactam antibiotics from water. Titanium oxide (1 and 2%) was incorporated into the zeolite network by modifying the gel during the zeolitization process. The formation of the zeolite Y structure and its microporous structure were evidenced by X-ray diffraction and N-2 physisorption. The structure, composition, reduction, and optical properties were studied by X-ray diffraction, H-2-TPR, XPS, Raman, photoluminescence, and UV-Vis spectroscopy. The obtained results indicated a zeolite Y structure for all photocatalysts with tetracoordinated Ti4+ sites. The second transitional metals supported by the post-synthesis method were obtained in various forms, such as oxides and/or in the metallic state. A red shift of the absorption edge was observed in the UV-Vis spectra of photocatalysts upon the addition of Fe, Co, or Ni species. The photocatalytic performances were evaluated for the degradation of cefuroxime in water under visible light irradiation. The best results were obtained for iron-immobilized photocatalysts. Scavenger experiments explained the photocatalytic results and their mechanisms. A different contribution of the active species to the photocatalytic reactions was evidenced.

This work reports the design and synthesis of novel oxadiazole-decorated azobenzenes, structural analysis of the resulting compounds and behavior under light irradiation. The synthetic strategy involved constructing amino functionalized heterocyclic key intermediates which were used either to yield electrophilic diazonium salts able to react with phenol moieties or as nucleophilic partners in Bayer-Mills reaction with nitroso-substituted derivatives. The amino-derived oxadiazole intermediates were investigated by absorption and emission spectroscopy providing blue and green emitted light. The target oxadiazole-decorated azobenzenes were structurally characterized, including solid-state structures, and subsequently used in irradiation experiments in order to take advantage of the azo group known to provide photoswitching abilities. We noticed quenching of the emissive properties in presence of the azo group; however, all compounds were very stable to repeated cycles of light irradiation. In addition, according to structural diversification we could obtain half-lives of the meta stable isomers within hours to hundreds of hours range. The experimental results were very well correlated with DFT calculations. The synthesis of novel oxadiazole-decorated azobenzenes using amino functionalised heterocyclic intermediates used either to provide electrophilic diazonium salts able to react with phenols or as nucleophilic partners in Bayer-Mills reaction is reported in this work. The oxadiazole-decorated azobenzenes were used in irradiation experiments to determine the parameters that characterize a photoswitch, yielding appealing results. The experimental results were very well correlated with DFT calculations.+image

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.

The primary objective of this research was to develop efficient solid catalysts that can directly convert the lactic acid (LA) obtained from lignocellulosic biomass into alanine (AL) through a reductive amination process. To achieve this, various catalysts based on ruthenium were synthesized using different carriers such as multi-walled carbon nanotubes (MWCNTs), beta-zeolite, and magnetic nanoparticles (MNPs). Among these catalysts, Ru/MNP demonstrated a remarkable yield of 74.0% for alanine at a temperature of 200 degrees C. This yield was found to be superior not only to the Ru/CNT (55.7%) and Ru/BEA (6.6%) catalysts but also to most of the previously reported catalysts. The characterization of the catalysts and their catalytic results revealed that metallic ruthenium nanoparticles, which were highly dispersed on the external surface of the magnetic carrier, significantly enhanced the catalyst's ability for dehydrogenation. Additionally, the -NH2 basic sites on the catalyst further facilitated the formation of alanine by promoting the adsorption of acidic reactants. Furthermore, the catalyst could be easily separated using an external magnetic field and exhibited the potential for multiple reuses without any significant loss in its catalytic performance. These practical advantages further enhance its appeal for applications in the reductive amination of lactic acid to alanine.