Nanocrystalline TiO2/Ti3C2Tx MXene composites with a tunable work function prepared using atmospheric pressure oxygen plasma.

Composites of TiO2 and Ti3C2Tx MXene are of great interest because they combine superior TiO2 photocatalytic activity with excellent MXene conductivity. As these composites have conventionally been prepared using methods requiring high temperatures, a process for producing similar materials at reduced temperature could be beneficial for applications in flexible and printed electronics. Therefore, we used low-temperature dielectric barrier discharge to develop a method for forming crystalline TiO2 by treating Ti3C2Tx MXene surfaces with high-power-density oxygen plasma comprising various energetic and reactive oxygen species, which oxidize MXene surfaces and form TiO2 nanoparticles on disordered graphitic carbon sheets within a few seconds. Scanning electron microscopy was used to observe the plasma-induced morphological changes to elucidate the TiO2 formation mechanism. The MXene surface chemistry was studied in detail using X-ray photoelectron spectroscopy and ab initio modelling. The crystalline phase of TiO2 was further studied using transmission electron microscopy and Raman spectroscopy. The results presented here suggest the formation of small anatase nanoparticles on the surface of MXenes within just seconds of plasma exposure. Nanoparticles grew with prolonged plasma treatment and a transition from anatase to rutile was observed. Considering that the temperature of plasma was always below 70 °C, the oxygen plasma process for the preparation of TiO2/Ti3C2Tx composites is an excellent candidate for application on temperature-sensitive substrates in flexible and printed electronics.

Facile fabrication of screen-printed MoS2 electrodes for electrochemical sensing of dopamine.

Molybdenum disulfide (MoS2) screen-printed working electrodes were developed for dopamine (DA) electrochemical sensing. MoS2 working electrodes were prepared from high viscosity screen-printable inks containing various concentrations and sizes of MoS2 particles and ethylcellulose binder. Rheological properties of MoS2 inks and their suitability for screen-printing were analyzed by viscosity curve, screen-printing simulation and oscillatory modulus. MoS2 inks were screen-printed onto conductive FTO (Fluorine-doped Tin Oxide) substrates. Optical microscopy and scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM/EDX) analysis were used to characterize the homogeneity, topography and thickness of the screen-printed MoS2 electrodes. The electrochemical performance was assessed through differential pulse voltammetry. Results showed an extensive linear detection of dopamine from 1 µM to 300 µM (R2 = 0.996, sensitivity of 5.00 × 10-8 A µM-1), with the best limit of detection being 246 nM. This work demonstrated the possibility of simple, low-cost and rapid preparation of high viscosity MoS2 ink and their use to produce screen-printed FTO/MoS2 electrodes for dopamine detection.

Gallic acid-coated silver nanoparticles as perspective drug nanocarriers: bioanalytical study.

The ability of silver nanoparticles (AgNPs) to be used as drug nanocarriers has helped rapidly to invent novel strategies to treat diseases, such as cancer. The nanoparticles may offer a valuable tool to novel pH-sensitive drug delivery systems in the present scenario because of their undergoing mechanisms associated with the regulated dissolution, aggregation, and generation of oxygen radicals as well. These processes could be monitored by electrochemical (bio)sensors that are less money and time-consuming compared to other analytical approaches, however, with comparable analytical performance. In this paper, synthesized and microscopically characterized gallic acid-coated AgNPs (GA-AgNPs) are investigated using spectral and electrochemical methods. To investigate the Ag+ release, a 21-day ageing experiment is performed spectrophotometrically, finding that the peak maximum of GA-AgNPs spectra diminished by 24.5%. The highest Ag+ content was electrochemically determined in the supernatant solution after centrifugation (6.97 µmol·L-1), while no significant concentration of silver ions in solution after redispersion was observed (1.26 µmol·L-1). The interaction experiment indicates a stabilization of GA-AgNPs in the presence of long-chain dsDNA as well as a mutual electrostatic interaction with DNA sugar-phosphate backbone. This interaction mechanism is confirmed by FTIR analysis, showing a shift (1049 to 1061 cm-1 and 913 to 964 cm-1) specific to DNA phosphate bands. Finally, doxorubicin-loaded GA-AgNPs are monitored for the specific drug release in the physiological and more reactive weakly acidic microenvironment. Hereby, electrochemical (bio)sensing of GA-AgNPs undergoing mechanisms shows a huge potential to be used for monitoring of drug delivery systems at cancer therapy.

Principal component analysis for the forensic discrimination of black inkjet inks based on the Vis-NIR fibre optics reflection spectra.

Nineteen black inkjet inks of six different brands were examined by fibre optics reflection spectroscopy in Visible and Near Infrared Region (Vis-NIR FORS) directly on paper with a view to achieving good resolution between them. These different inks were tested on nineteen different inkjet printers from three brands. Samples were obtained from prints by reflection probe. Processed reflection spectra in the range 500-1000 nm were used as samples in principal component analysis. Variability between spectra of the same ink obtained from different prints, as well as between spectra of square areas and lines was examined. For both spectra obtained from square areas and lines reference, Principal Component Analysis (PCA) models were created. According to these models, the inkjet inks were divided into clusters. PCA method is able to separate inks containing carbon black as main colorant from the other inks using other colorants. Some spectra were recorded from another piece of printer and used as validation samples. Spectra of validation samples were projected onto reference PCA models. According to position of validation samples in score plots it can be concluded that PCA based on Vis-NIR FORS can reliably differentiate inkjet inks which are included in the reference database. The presented method appears to be a suitable tool for forensic examination of questioned documents containing inkjet inks. Inkjet inks spectra were obtained without extraction or cutting sample with possibility to measure out of the laboratory.

Label-free detection of glycoproteins by the lectin biosensor down to attomolar level using gold nanoparticles.

We present here an ultrasensitive electrochemical biosensor based on a lectin biorecognition capable to detect concentrations of glycoproteins down to attomolar (aM) level by investigation of changes in the charge transfer resistance (Rct) using electrochemical impedance spectroscopy (EIS). On polycrystalline gold modified by an aminoalkanethiol linker layer, gold nanoparticles were attached. A Sambucus nigra agglutinin was covalently immobilised on a mixed self-assembled monolayer formed on gold nanoparticles and finally, the biosensor surface was blocked by poly(vinyl alcohol). The lectin biosensor was applied for detection of sialic acid containing glycoproteins fetuin and asialofetuin. Building of a biosensing interface was carefully characterised by a broad range of techniques such as electrochemistry, EIS, atomic force microscopy, scanning electron microscopy and surface plasmon resonance with the best performance of the biosensor achieved by application of HS-(CH2)11-NH2 linker and gold nanoparticles with a diameter of 20 nm. The lectin biosensor responded to an addition of fetuin (8.7% of sialic acid) with sensitivity of (338 ± 11) Ω decade(-1) and to asialofetuin (≤ 0.5% of sialic acid) with sensitivity of (109 ± 10) Ω decade(-1) with a blank experiment with oxidised asialofetuin (without recognisable sialic acid) revealing sensitivity of detection of (79 ± 13) Ω decade(-1). These results suggest the lectin biosensor responded to changes in the glycan amount in a quantitative way with a successful validation by a lectin microarray. Such a biosensor device has a great potential to be employed in early biomedical diagnostics of diseases such as arthritis or cancer, which are connected to aberrant glycosylation of protein biomarkers in biological fluids.

Ultrasensitive impedimetric lectin based biosensor for glycoproteins containing sialic acid.

We report on an ultrasensitive label-free lectin-based impedimetric biosensor for the determination of the sialylated glycoproteins fetuin and asialofetuin. A sialic acid binding agglutinin from Sambucus nigra I was covalently immobilised on a mixed self-assembled monolayer (SAM) consisting of 11-mercaptoundecanoic acid and 6-mercaptohexanol. Poly(vinyl alcohol) was used as a blocking agent. The sensor layer was characterised by atomic force microscopy, electrochemical impedance spectroscopy and X-ray photoelectron spectroscopy. The biosensor exhibits a linear range that spans 7 orders of magnitude for both glycoproteins, with a detection limit as low as 0.33 fM for fetuin and 0.54 fM for asialofetuin. We also show, by making control experiments with oxidised asialofetuin, that the biosensor is capable of quantitatively detecting changes in the fraction of sialic acid on glycoproteins. We conclude that this work lays a solid foundation for future applications of such a biosensor in terms of the diagnosis of diseases such as chronic inflammatory rheumatoid arthritis, genetic disorders and cancer, all of which are associated with aberrant glycosylation of protein biomarkers.