National Institute Of Materials Physics - Romania

Shikonin, a natural compound with pharmaceutical properties, has attracted interest due to its anti-oxidant properties, potential anti-cancer activity and activity over several biological pathways, such as dsDNA transcription/replication of cancer cells and inhibition of pyruvate kinase M2. The electrochemical behavior of shikonin in aqueous media was investigated at glassy carbon electrodes by cyclic and differential pulse voltammetry. The reduction involves the quinone moiety and formation of a semiquinone intermediate. In the absence of dissolved oxygen, the reduction is reversible while in normal atmosphere leads to formation of superoxide cation. The oxidation occurs at the dihydroxy moiety and reversibility was only observed in acid electrolytes. A redox mechanism was proposed. The interaction between shikonin and dsDNA was evaluated in incubated solutions and in situ with the dsDNA-electrochemical biosensor. The mechanism of interaction is time-dependent and follows an initial binding step at the grooves of the double strand leading to conformational modifications recognized through the variation of guanine and adenine oxidation peaks. The in-situ electrochemical production of the semiquinone intermediate leads to a preferential interaction with guanine residues, promoting their oxidation and consequently occurrence 8-oxo-guanine. An interaction mechanism was proposed.

A non-conventional, bioinspired device based on polypyrrole coated electrospun fibrous microstructures, which simultaneously works as artificial muscle and mechanical sensor is reported. Fibrous morphology is preferred due to its high active surface which can improve the actuation/sensing properties, its preparation still being challenging. Thus, a simple fabrication algorithm based on electrospinning, sputtering deposition and electrochemical polymerization produced electroactive aligned ribbon meshes with analogous characteristics as natural muscle fibers. These can simultaneously generate a movement (by applying an electric current/potential) and sense the effort of holding weights (by measuring the potential/current while holding objects up to 21.1 mg). Electroactivity was consisting in a fast bending/curling motion, depending on the fiber strip width. The amplitude of the movement decreases by increasing the load, a behavior similar with natural muscles. Moreover, when different weights were hung on the device, it senses the load modification, demonstrating a sensitivity of about 7 mV/mg for oxidation and - 4 mV/mg for reduction. These results are important since simultaneous actuation and sensitivity are essential for complex activity. Such devices with multiple functionalities can open new possibilities of applications as e.g. smart prosthesis or lifelike robots.

IV-VI semiconductor quantum dots embedded into an inorganic matrix represent nanostructured composite materials with potential application in temperature sensor systems. This study explores the optical, structural, and morphological properties of a novel PbS quantum dots (QDs)-doped inorganic thin film belonging to the Al2O3-SiO2-P2O5 system. The film was synthesized by the sol-gel method, spin coating technique, starting from a precursor solution deposited on a glass substrate in a multilayer process, followed by drying of each deposited layer. Crystalline PbS QDs embedded in the inorganic vitreous host matrix formed a nanocomposite material. Specific investigations such as X-ray diffraction (XRD), optical absorbance in the ultraviolet (UV)-visible (Vis)-near infrared (NIR) domain, NIR luminescence, Raman spectroscopy, scanning electron microscopy-energy dispersive X-ray (SEM-EDX), and atomic force microscopy (AFM) were used to obtain a comprehensive characterization of the deposited film. The dimensions of the PbS nanocrystallite phase were corroborated by XRD, SEM-EDX, and AFM results. The luminescence band from 1400 nm follows the luminescence peak of the precursor solution and that of the dopant solution. The emission of the PbS-doped film in the NIR domain is a premise for potential application in temperature sensing systems.

(1) Background: The treatment of dental cavities and restoration of tooth shape requires specialized materials with specific clinical properties, including being easy to model, light-cured, having a natural color, reduced shrinkage, a hardness similar to hydroxyapatite, and no leakage. The dimensional stability of resin composite materials is affected by polymerization shrinkage, degree of conversion (number of pi carbon bonds converted into sigma ones), thermal contraction and expansion, and interactions with an aqueous environment. (2) Methods: The materials used in our investigation were two composite resins with similar polymer matrices, but different filler (micro/nano filler). To evaluate the properties of samples, we employed the pycnometer technique (pycnometer from Paul Marienfeld Gmbh, Lauda-Konigshofen, Germany), RAMAN spectroscopy technique (MiniRam Equipment from B&W Tek Inc., Plainsboro Township, NJ, USA; 785 nm laser source), SEM and EDX (FEI Inspect S.). (3) Results: The size of the filler plays an important role in the polymerization: for the pycnometric results, the larger particle filler (Sample 1) seems to undergo a rapid polymerization during the 45 s curing, while the nanoparticle filer (Sample 2) needs additional curing time to fully polymerize. This is related to a much larger porosity, as proved by SEM images. The lower degree of conversion, as obtained by Raman spectroscopy, in the same geometry means that the same volume is probed for both samples, but Sample 1 is more porous, which means less amount of polymer is probed for Sample 1. (4) Conclusions: For the two composites, we obtained a degree of conversion of 59% for Sample 1 and 93% for Sample 2, after 45 s of curing.

This is the first report regarding the effect of gamma irradiation on chitosan-coated magnesium-doped hydroxyapatite (x(Mg) = 0.1; 10 MgHApCh) layers prepared by the spin-coating process. The stability of the resulting 10 MgHApCh gel suspension used to obtain the layers has been shown by ultrasound measurements. The presence of magnesium and the effect of the irradiation process on the studied samples were shown by X-ray photoelectron spectroscopy (XPS). The XPS results obtained for irradiated 10 MgHApCh layers suggested that the magnesium and calcium contained in the surface layer are from tricalcium phosphate (TCP; Ca-3(PO4)(2)) and hydroxyapatite (HAp). The XPS analysis has also highlighted that the amount of TCP in the surface layer increased with the irradiation dose. The energy-dispersive X-ray spectroscopy (EDX) evaluation showed that the calcium decreases with the increase in the irradiation dose. In addition, a decrease in crystallinity and crystallite size was highlighted after irradiation. By atomic force microscopy (AFM) we have obtained images suggesting a good homogeneity of the surface of the non-irradiated and irradiated layers. The AFM results were also sustained by the scanning electron microscopy (SEM) images obtained for the studied samples. The effect of gamma-ray doses on the Fourier transform infrared spectroscopy (ATR-FTIR) spectra of 10 MgHApCh composite layers was also evaluated. The in vitro antifungal assays proved that 10 MgHApCh composite layers presented a strong antifungal effect, correlated with the irradiation dose and incubation time. The study of the stability of the 10 MgHApCh gel allowed us to achieve uniform and homogeneous layers that could be used in different biomedical applications.

Electrospun polymeric fibers present an emerging alternative for the development of flexible electronics, enabling applications in wearable sensors and biosensors for continuous monitoring, and actuators for tissue engineering. The possibility to prepare sub-micrometric polymeric scaffolds, their processing for increasing the conductivity, their modification with different materials, conductive polymers and biomolecules in order to obtain functional flexible electrodes, allows the development of innovative devices for healthcare, and biomedical applications. In this review, the impact of metallized electrospun polymeric fibers in electrochemical (bio)sensors and actuators is discussed. A relation between their structure and functionality is provided, alongside with an overview of the different methods to obtain functional conductive fibers.

ZnO nanostructures were electrochemically synthesized on Cu and on chemical vapor deposited (CVD)-graphene/Cu electrodes. The deposition was performed at different electrode potentials ranging from -0.8 to -1.2 V, employing a zinc nitrate bath, and using voltametric and chronoamperometric techniques. The effects of the electrode nature and of the working electrode potential on the structural, morphological, and optical properties of the ZnO structures were investigated. It was found that all the samples crystallize in hexagonal wurtzite structure with a preferential orientation along the c-axis. Scanning electron microscopy (SEM) images confirm that the presence of a graphene covered electrode led to the formation of ZnO nanowires with a smaller diameter compared with the deposition directly on copper surface. The photoluminescence (PL) measurements revealed that the ZnO nanowires grown on graphene/Cu exhibit stronger emission compared to the nanowires grown on Cu. The obtained results add another possibility of tailoring the properties of such nanostructured films according to the specific functionality required.

Hierarchical functionalization of flax fibers with ZnO nanostructures was achieved by electroless deposition to improve the interfacial adhesion between the natural fibers and synthetic matrix in composite materials. The structural, morphological, thermal and wetting properties of the pristine and ZnO-coated flax fibers were investigated. Thus, the ZnO-coated flax fabric discloses an apparent contact angle of similar to 140 degrees immediately after the placement of a water droplet on its surface. An assessment of the interfacial adhesion at the yarn scale was also carried out on the flax yarns coated with ZnO nanostructures. Thus, after the ZnO functionalization process, no significant degradation of the tensile properties of the flax yarns occurs. Furthermore, the single yarn fragmentation tests revealed a notable increase in the interfacial adhesion with an epoxy matrix, reductions of 36% and 9% in debonding and critical length values being measured compared to those of the pristine flax yarns, respectively. The analysis of the fracture morphology by scanning electron microscopy and X-ray microtomography highlighted the positive role of ZnO nanostructures in restraining debonding phenomena at the flax fibers/epoxyresin matrix interphase.

The present work reports a new configuration of soft artificial muscle based on a web of metal covered nylon 6/6 micrometric fibers attached to a thin polydimethylsiloxane (PDMS) film. The preparation process is simple and implies the attachment of metalized fiber networks to a PDMS sheet substrate while heating and applying compression. The resulting composite is versatile and can be cut in different shapes as a function of the application sought. When an electric current passes through the metallic web, heat is produced, leading to local dilatation and to subsequent controlled deformation. Because of this, the artificial muscle displays a fast and ample movement (maximum displacement of 0.8 cm) when applying a relatively low voltage (2.2 V), a consequence of the contrast between the thermal expanse coefficients of the PDMS substrate and of the web-like electrode. It was shown that the electrical current producing this effect can originate from both direct electric contacts, and untethered configurations i.e. radio frequency induced. Usually, for thermal activated actuators the heating is produced by using metallic films or conductive carbon-based materials, while here a fast heating/cooling process is obtained by using microfiber-based heaters. This new approach for untethered devices is an interesting path to follow, opening a wide range of applications were autonomous actuation and remote transfer of energy are needed.

The use of gold nanoparticles/superoxide dismutase (AuNP/SOD) bioconjugates is described as building blocks in SOD biosensor development for the quantification of superoxide in cell culture media. AuNP functionalization with 11-mercaptoundecanoic acid (MUA) and 4-mercaptobenzoic acid (MBA) (AuNPMUA and AuNPMBA) was used to improve SOD immobilization through EDC/NHS coupling using their -COOH terminus, leading to the formation of more stable bioconjugates. AuNP and AuNP/SOD bioconjugates were characterized by SEM to determine their size and morphology, UV-Vis for optical properties, FT-IR, and Raman spectroscopies for chemical functional group analysis and EDX for elemental analysis. Electrochemical methods were used to characterize the Au/AuNP-modified electrodes. For the optimization of the biosensor architecture, different AuNP/enzyme bioconjugates were prepared by varying the amount of both enzyme and AuNP, as well as their incubation time. Finally, the biosensors incorporating the bioconjugates were characterized by fixed potential amperometry and voltammetric analysis in order to establish the enzymatic mechanism and to elucidate the best biosensor architecture for monitoring superoxide in cell culture media. The best sensitivity value for superoxide detection corresponded to 41.2 nA mu M cm(-2), achieved by a biosensor based on AuNPMBA/SOD bioconjugates monitored through fixed potential amperometry at 0.3 V vs. Ag/AgCl, with a limit of detection of 1.0 mu M, and overall very good operational stability, maintaining 91% of the initial sensitivity after 30 days. Finally, the optimized biosensor was employed for the quantification of successive additions of superoxide in cell culture media, with excellent recovery values.