Impact of Graphene Oxide on SERS Enhancement of Arylated Gold Nanospheres: Mechanistic Insight.

The performance of gold nanospheres as substrates for surface-enhanced Raman spectroscopy (SERS) investigation has been compromised by their low adsorption efficiency, high colloidal dispersibility, and diminishing hot spots. However, gold nanosphere substrates modified using aryldiazonium gold(III) chemistry via durable gold-carbon bonds are promising for SERS enhancement due to their controlled organic layer density. In this study, arylated gold nanospheres AuNSs-COOH have shown SERS enhancement when incorporated into graphene oxide (GO) to form nanocomposites (NCs) labeled AuNSs-COOH/GO (AuNCs). Our investigation using X-ray photoelectron spectroscopy (XPS) surface analysis showed that the gold-aryl nanospheres reached their maximum SERS enhancement with an optimal coating. The evaluation included the Au 4f chemical environment and compact graphitic layers for the SERS substrate optimization. The fabricated AuNC substrates demonstrated superior efficiency and reproducibility. A broad linear range of 10-3-10-7 M 4-nitrophenol detection was obtained with exceptional repeatability, as evidenced by the relative standard deviation (RSD) of 9.32%. A detailed investigation of the energy profiles, particularly the valence band maximum (VBM) and band gap values of the substrate and analyte, depicted the electromagnetic (EM) and charge-transfer-induced enhancement and the role of GO inclusion in substrate efficiency in SERS enhancement mechanisms. The finite-difference time domain (FDTD) simulation results revealed that AuNCs incorporated with graphitic nanostructures exhibited the most substantial SERS effect through an EM field enhancement mechanism. This study demonstrated significant SERS enhancement using gold-aryl nanospheres when modified with GO, in contrast to the typical reliance on anisotropic nanostructures.

Flexible Copper Films Modification via Spontaneous Reduction of Aryldiazonium Gold Salts: Unraveling Surface Properties and Energy Profile.

In this study, we report the modification of flexible copper films via the spontaneous reduction of aryldiazonium gold salts [X-4-C6H4N≡N]AuCl4 (X═COOH, NO2). The electroless modification involves dipping of flexible copper films in the aryldiazonium gold solutions for a few seconds, under ambient conditions, followed by a washing step with deionized water to obtain a mechanically robust gold-aryl coating. The chemical composition, morphology, electronic structure, and optical properties of the gold-aryl layer and the flexibility of the modified copper films are supported by the results from X-ray photoelectron spectroscopy (XPS), electrochemistry, contact angle, scanning electron microscopy (SEM), and ultraviolet photoelectron spectroscopy (UPS). XPS surface analysis showed metallic gold in addition to C-C, C-O/C-N, and C═O functional groups from the grafted aryls. Cu 2p showed metallic copper as a major component and a small amount of Cu(II) ions. Wettability studies showed that Au-COOH@Cu increased the contact angle of the bare copper films from 68.0 ± 0.7° to 82.0° ± 0.7°, while Au-NO2@Cu increased the contact angle to 134.0° ± 0.3°. UPS energy profile analysis of [HOOC-4-C6H4N≡N]AuCl4 (valence band maximum = 1.91 eV) exhibited greater reducibility than [O2N-4-C6H4N≡N]AuCl4 (valence band maximum = 2.91 eV). The lower ionization potential of [HOOC-4-C6H4N≡N]AuCl4 (IP = 4.33 eV) enhanced the reactivity upon copper film contact, potentially inducing efficient energy level alignment, compared with [O2N-4-C6H4N≡N]AuCl4 (IP = 5.62 eV). UPS results were further supported by electrochemistry investigation which revealed that [HOOC-4-C6H4N≡N]AuCl4 is easily reducible compared with [O2N-4-C6H4N≡N]AuCl4. The findings presented here hold significant implications for developing flexible copper films and pave the way for future advancements in electronic material modification for industrial applications.

Highly flexible copper tape decorated with Ag nanoarrays as ultrasensitive SERS platforms for multi-hazardous pollutant sensing.

A highly flexible and cost-effective copper tape decorated with silver nanoparticles (Cu-TAg) has been developed for surface-enhanced Raman spectroscopy (SERS) sensing of multi-hazardous environmental pollutants. Highly ordered and spherical-shaped silver nanoarrays have been fabricated using a low-cost thermal evaporation method. The structural, morphological, and optical properties of Cu-TAg sensors have been studied and correlated to the corresponding SERS performances. The size of nanoparticles has been successively tuned by varying the deposition time from 5 to 25 s. The nanoparticle sizes were enhanced with an increase in the evaporation time. SERS investigations have revealed that the sensing potential is subsequently improved with an increase in deposition time up to 10 s and then deteriorates with further increase in Ag deposition. The highest SERS activity was acquired for an optimum size of ~ 37 nm; further simulation studies confirmed this observation. Moreover, Cu-TAg sensors exhibited high sensitivity, reproducibility, and recycling characteristics to be used as excellent chemo-sensors. The lower detection limit estimation revealed that it can sense even in the pico-molar range for sensing of rhodamine 6G and methylene blue. The estimated enhancement factor of the sensor is found to be 9.4 × 107. Molecular-specific sensing of a wide range of pollutants such as rhodamine 6G, alizarin red, methylene blue, butylated hydroxy anisole, and penicillin-streptomycin is demonstrated with high efficiencies for micromolar spiked samples. Copper tape functionalized with Ag arrays thus demonstrated to be a promising candidate for low-cost and reusable chemo-sensors for environmental remediation applications.

Evaluation of the nanofluid-assisted desalination through solar stills in the last decade.

Remote areas and poor communities are occasionally deprived of access to freshwater. It is, therefore, critical to providing a cheap and efficient desalination system that encourages the development of those communities and benefiting society at large. Solar stills are an affordable, direct method of water desalination, but its productivity is the critical challenge hindering its application. To ease this, research has focused on the role of nanofluids to improve heat transfer. Other works have focused on improving the design in consort with utilizing the nanofluids. This review reports and discusses the substantial role of nanofluids to enhance the productivity and energy utilization efficiency of the solar stills. Specifically, the mechanism of energy transfer between the nanoparticles and the base fluid. This includes both plasmonic and thermal effects. It is evident that nanofluid utilization in small fraction enhanced the thermal conductivity compared to base fluid alone. Alumina was found to be the most suitable nanoparticle used as nanofluid inside the solar stills due to its availability and lower cost. Still, other competitors such as carbon nanostructures need to be investigated as it provides higher enhancement of thermal conductivity. Also, several aspects of energy utilization enhancement have been discussed, including innovative application techniques. The challenges of such integrated systems are addressed as well.

Structural effects of silver-nanoprism-decorated Si nanowires on surface-enhanced Raman scattering.

Surface enhanced Raman scattering (SERS) is an important analytical tool for the optochemical detection of molecules. The enhancement is commonly achieved by engineering (i) novel types and morphologies of plasmonic nanomaterials, and (ii) patterned or roughened supporting substrates of high surface area for increased light scattering and molecule adsorption. Si substrates can be easily and reproducibly textured for effective SERS applications. In this work, silver nanoprisms (AgNPr) coated silicon nanowire (SiNWs) of different morphologies have been prepared by metal-assisted chemical etching and tested for SERS detection of R6G dye. By varying the etching time from 5 to 30 min, the nanowires' lengths increased from 2.4 to 10.5 µm and resulted in a variable topological morphology of the substrates in terms of bundles and valleys. We found that an optimum of 10 min etching time led to the highest SERS enhancement of R6G on AgNPr/SiNWs at 612 cm-1 Raman shift (30× compared to R6G/Si and 2× compared to R6G/AgNPr/Si), with a detection limit comparable to that of state-of-the-art performances (down to 5×10-10 M of R6G). Such an enhancement is attributed to a middle ground between increased overall surface area of SiNWs, and the available bundle tops trapping the AgNPr and R6G molecules.

Preparation and characterization of clay based ceramic porous membranes and their use for the removal of lead ions from synthetic wastewater with an insight into the removal mechanism.

The present study explores the use of local clay from the United Arab Emirates (UAE) to prepare porous ceramic membranes (flat disk shape) for the purpose of removing toxic heavy metals from contaminated water. Four distinct ceramic membranes, crafted from locally sourced clay and incorporated with activated carbon and graphite, underwent careful and thorough preparation. The initial set of membranes was subjected to open-air sintering, resulting in the creation of mACA and mGrA membranes. Concurrently, a second set of meticulously prepared membranes underwent sintering under inert nitrogen conditions, yielding the formation of mACI and mGrI membranes, respectively. Prior to making the membranes, the clay material was characterized by thermogravimetric analysis (TGA), X-ray fluorescence (XRF), Fourier-transform infrared spectroscopy (FTIR), and X-ray diffraction analysis (XRD). The clay presented the lowest weight loss compared to AC and Gr, implying that these two materials could be used as porogen agents. The X-ray fluorescence results indicated that the natural clay contained 65.5 wt% of silicon dioxide (SiO2), aluminium oxide (Al2O3), and iron (III) oxide (Fe2O3) falling within the class C category of clays according to ASTM. The FTIR analysis showed different clay regions allocated to various stretching and deformation vibrations of hydroxide, organic fraction, and (Si, Al, Fe)-O groups. The XRD analysis revealed the presence of kaolinite, illite, smectite and calcite phyllite phases in the clay mineral. The membranes were characterized using FESEM, with those containing AC (used as porogen) exhibiting large pores clearly visible on the surface, and were tested for the removal of lead (Pb2+) ions from synthetic wastewater. The removal efficiencies of the membranes were 33 %, 75.2 %, 100 % and 100 % for mACA, mACI, mGrA and mGrI respectively after 100 min operation. The wettability of the membranes was found to follow the order mACI < mACA < mGrI < mGrA, which corroborated well with water fluxes of 7, 8, 112 and 214 L h-1 m-2 recorded after 60 min duration and 1.0 bar applied pressure. The mechanisms of filtration of Pb2+ ions were adsorption for the AC-based membranes (mACA, mACI) and a combination of adsorption and size exclusion for the Gr-based membranes (mGrA, mGrI).

Smart optical sensing of multiple antibiotic residues from wastewater effluents with ensured specificity using SERS assisted with multivariate analysis.

Surface-enhanced Raman spectroscopy offers great potential for rapid and highly sensitive detection of pharmaceuticals from environmental sources. Herein, we investigated the feasibility of label-free sensing of antibiotic residues from wastewater effluents with high specificity by combining with multivariate analysis. Highly ordered silver nanoarrays with ∼34 nm roughness have been fabricated using a cost-effective electroless deposition technique. As-fabricated Ag arrays showed superior LSPR effects with an enhancement factor of 8 × 107. Excellent reproducibility has also been noticed with RSD values within 11%, whilst the sensor showed good stability and reusability characteristics for being used as a low-cost and reusable sensor. SERS studies demonstrated that antibiotics-spiked wastewater effluents can be detected with high efficiency in a label-free method. The molecular fingerprint bands of antibiotics such as sulfamethoxazole, sulfadiazine, and ciprofloxacin were well analyzed in effluent, tap, and deionized water. It has been found that antibiotics can be detected near picomolar levels; meanwhile, liquid chromatography-mass spectrometry (LC-MS) exhibited a detection limit within nanomolar concentrations only. Furthermore, the specificity of SERS sensing has been further analyzed using a multivariate analysis method, principal component analysis followed by linear discriminant analysis (PCA-LDA); which showed prominent discrimination to distinguish each antibiotic residue from wastewater effluents. The current study presented the potential of Ag nanoarray sensors for rapid, highly specific, and cost-effective analysis of pharmaceutical products for environmental remediation applications.

High energy storage quasi-solid-state supercapacitor enabled by metal chalcogenide nanowires and iron-based nitrogen-doped graphene nanostructures.

Transition metal selenides (TMS) have excellent research prospects and significant attention in supercapacitors (SCs) owing to their high electrical conductivity, superior electrochemical activity and excellent structural stability. However, the commercial utilization of TMS remains challenge due to their elaborate synthesis. Present study designed a hierarchical cobalt selenide (CoSe2) nanowire array on Ni-foam to serve as a positive electrode for asymmetric SCs (ASCs). The nanowires-like morphology of CoSe2 was highly advantageous for SCs, as it offered enhanced electrical conductivity, plenty of surface sites, and short ion diffusion. The as-obtained, CoSe2 nanowire electrode demonstrated outstanding electrochemical features, with an areal capacity of 1.08 mAh cm-2 at 3 mA cm-2, high-rate performance (69.5 % at 50 mA cm-2), as well as outstanding stability after 10,000 cycles. The iron titanium nitride@nitrogen-doped graphene (Fe-TiN@NG) was prepared as a negative electrode to construct the ASCs cell. The obtained ASCs cell illustrated an energy density of 91.8 W h kg-1 at a power density of 281.4 W kg-1 and capacity retention of 94.6% over 10,000 cycles. The overall results provide a more efficient strategy to develop redox-ambitious active materials with a high capacity for advanced energy-storage systems.

Fuel cells for carbon capture applications.

The harmful effect of carbon pollution leads to depletion of the ozone layer, which is one of the main challenges confronting the world. Although progress is made in developing different carbon dioxide (CO2) capturing methods, these methods are still expensive and face several technical challenges. Fuel cells (FCs) are efficient energy converting devices that produce energy via an electrochemical process. Recently varying kinds of fuel cells are considered as an effective method for CO2 capturing and/or conversion. Among the different types of fuel cells, solid oxide fuel cells (SOFCs), molten carbonate fuel cells (MCFCs), and microbial fuel cells (MFCs) demonstrated promising results in this regard. High-temperature fuel cells such as SOFCs and MCFCs are effectively used for CO2 capturing through their electrolyte and have shown promising results in combination with power plants or industrial effluents. An algae-based microbial fuel cell is an electrochemical device used to capture and convert carbon dioxide through the photosynthesis process using algae strains to organic matters and simultaneously power generation. This review present a brief background about carbon capture and storage techniques and the technological advancement related to carbon dioxide captured by different fuel cells, including molten carbonate fuel cells, solid oxide fuel cells, and algae-based fuel cells.

Faradic capacitive deionization (FCDI) for desalination and ion removal from wastewater.

Capacitive deionization (CDI) is one of the emerging desalination technologies that attracted much attention in the last years as a low-cost, energy-efficient, and environmentally-friendly alternative to other desalination technologies, such as multi-stage flash desalination (MSF) and multiple effect distillation (MED). The implementation of faradaic electrode materials is a promising method for enhancing CDI systems' performance by achieving higher salt removal characteristics, lower energy consumption, and better ion selectivity. Therefore, a novel CDI technology named Faradaic CDI (FCDI) that implements faradaic electrode materials arose as a high-performance CDI cell design. In this work, the application of FCDI cells in desalination and wastewater treatment systems is reviewed. First, the progress done on using various FCDI systems for saline water desalination is summarized and discussed. Next, the application of FCDI in wastewater treatment applications and selective ion removal is presented. A thorough comparison between FCDI and conventional carbon-based CDI is carried out in terms of working principle, electrode material's cost, salt removal performance, energy consumption, advantages, and disadvantages. Finally, future research consideration regarding FCDI technology is included to drive this technology closer towards practical application.

Ultra-sensitive and fast optical detection of the spike protein of the SARS-CoV-2 using AgNPs/SiNWs nanohybrid based sensors.

Severe acute respiratory syndrome SARS-CoV-2 virus led to notable challenges amongst researchers in view of development of new and fast detecting techniques. In this regard, surface-enhanced Raman spectroscopy (SERS) technique, providing a fingerprint characteristic for each material, would be an interesting approach. The current study encompasses the fabrication of a SERS sensor to study the SARS-CoV-2 S1 (RBD) spike protein of the SARS-CoV-2 virus family. The SERS sensor consists of a silicon nanowires (SiNWs) substrate decorated with plasmonic silver nanoparticles (AgNPs). Both SiNWs fabrication and AgNPs decoration were achieved by a relatively simple wet chemical processing method. The study deliberately projects the factors that influence the growth of silicon nanowires, uniform decoration of AgNPs onto the SiNWs matrix along with detection of Rhodamine-6G (R6G) to optimize the best conditions for enhanced sensing of the spike protein. Increasing the time period of etching process resulted in enhanced SiNWs' length from 0.55 to 7.34 µm. Furthermore, the variation of the immersion time in the decoration process of AgNPs onto SiNWs ensued the optimum time period for the enhancement in the sensitivity of detection. Tremendous increase in sensitivity of R6G detection was perceived on SiNWs etched for 2 min (length=0.90 µm), followed by 30s of immersion time for their optimal decoration by AgNPs. These SiNWs/AgNPs SERS-based sensors were able to detect the spike protein at a concentration down to 9.3 × 10-12 M. Strong and dominant peaks at 1280, 1404, 1495, 1541 and 1609 cm-1 were spotted at a fraction of a minute. Moreover, direct, ultra-fast, facile, and affordable optoelectronic SiNWs/AgNPs sensors tuned to function as a biosensor for detecting the spike protein even at a trace level (pico molar concentration). The current findings hold great promise for the utilization of SERS as an innovative approach in the diagnosis domain of infections at very early stages.

Atmospheric pressure air microplasma current time series for true random bit generation.

Generating true random bits of high quality at high data rates is usually viewed as a challenging task. To do so, physical sources of entropy with wide bandwidth are required which are able to provide truly random bits and not pseudorandom bits, as it is the case with deterministic algorithms and chaotic systems. In this work we demonstrate a reliable high-speed true random bit generator (TRBG) device based on the unpredictable electrical current time series of atmospheric pressure air microplasma (APAMP). After binarization of the sampled current time series, no further post-processing was needed in order for the bitstreams to pass all 15 tests of the NIST SP 800-22 statistical test suite. Several configurations of the system have been successfully tested at different sampling rates up to 100 MS/s, and with different inter-electrode distances giving visible/non-visible optical emissions. The cost-effectiveness, simplicity and ease of implementation of the proposed APAMP system compared to others makes it a very promising solution for portable TRBGs.

Biosynthesis, Characterization, and Evaluation of the Cytotoxic Effects of Biologically Synthesized Silver Nanoparticles from Cyperus conglomeratus Root Extracts on Breast Cancer Cell Line MCF-7.

Over recent years, metal nanoparticles have largely been investigated due to their potential activities. This study focused on synthesizing silver nanoparticles (AgNPs) using the desert plant Cyperus conglomeratus, which is the most abundant species on the sand dunes in the UAE, and their anticancer activity. The synthesized AgNPs were characterized using UV-visible spectra, X-ray diffraction, energy dispersive X-ray spectroscopy, fourier transform infrared spectroscopy, dynamic light scattering, and scanning electron microscope. The results showed that the AgNPs are monodispersed and mostly spherical in shape. The cytotoxicity effects were investigated against breast cancer cells MCF-7 and normal fibroblast using MTT assay which showed selective cytotoxicity against MCF-7 with an IC50 at 5 µg/mL but not fibroblast. Moreover, the apoptotic effects were confirmed using annexin V-FITC-PI double staining kit and real-time PCR for apoptotic genes. Therefore, our results revealed potential anticancer applications of the C. conglomeratus biosynthesized silver nanoparticles.

Origins of bandgap bowing in compound-semiconductor common-cation ternary alloys.

We present an investigation into the existence and origins of bandgap bowing in compound-semiconductor common-cation ternary alloys. As examples, we consider CdSe(x)Te(1-x) and ZnSe(1-x)Te(x) alloys. A calculation, based on the sp(3)s(*) tight-binding method including spin-orbit coupling within the framework of the virtual crystal approximation, is employed to determine the bandgap energy, local density of states and atomic charge states versus composition and valence-band offset. The results show that (i) in the valence band, the top states are mainly contributed by Te atoms. The degree of ionicity of all atoms is found to vary linearly with mole fraction x. (ii) There is a strong competition between the anions (Se and Te) in trapping/losing charges and this competition is the main reason for the bandgap bowing character. (iii) There is a reasonable agreement between the calculated results and the available photoluminescence data. (iv) The bowing parameter is found to increase with increasing valence-band offset and increasing lattice mismatch.

Exogenous Production of Silver Nanoparticles by Tephrosia apollinea Living Plants under Drought Stress and Their Antimicrobial Activities.

Nanoparticle (NP) synthesis by biological systems is more cost-effective, safe, and environmentally friendly when compared to currently used chemical and physical methods. Although many studies have utilized different plant extracts to synthesize NPs, few studies have incorporated living plants. In this study, silver nanoparticles (AgNPs) were synthesized exogenously by Tephrosia apollinea living plant system under the combined stresses of silver nitrate and different levels of drought stress simulated by Polyethylene glycol (PEG) (0, -0.1, -0.2, and -0.4 MPa for three and six days). Biomass, cell death, and H2O2 content were evaluated to determine the toxicological effect of the treatments on the plant. More severe effects were detected in day 6 plants compared to day 3 plants, and at higher drought levels. UV-visible spectrum, energy dispersive X-ray spectroscopy, X-ray diffraction, scanning electron microscope, and Fourier transform infrared spectroscopy were used to detect and characterize the T. apollinea synthesized NPs. The shapes of the NPs were spherical and cubic with different phytochemicals being the possible capping agents. Broth microdilution was used to determine the antimicrobial activity of the NPs against Escherichia coli and Staphylococcus aureus. In this case, antimicrobial activity increased at higher PEG concentrations. Bactericidal effects were observed against E. coli, while only bacteriostatic effects were detected against S. aureus.

Acid-functionalized carbon nanofibers for high stability, thermoelectrical and electrochemical properties of nanofluids.

Carbon-based nanofluids are viewed as promising thermal fluids for heat transfer applications. However, other properties, such as electrical conductivity and electrochemical behavior, are usually overlooked and rarely investigated despite their importance for the overall performance characterization of a given application. In this study, we synthesized PAN-based carbon nanofibers (CNF) by electrospinning, and characterized them using electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, Raman spectroscopy, and thermogravimetric analysis. Thermoelectrical and electrochemical measurements were carried out on nanofluids. We found that, although CNF nanofluids exhibit good thermal and electrical properties with a negligible corrosive effect, the suspensions tend to sediment within a few days. However, acid treatment of CNF (F-CNF), which resulted in the shortening of the fibers and the appearance of surface-oxygenated species, made F-CNF-based nanofluids exhibit superior stability in water that extended for more than 90 days, with consistent and superior thermal and electrical properties.

Copper Nanoparticles Induced Genotoxicty, Oxidative Stress, and Changes in Superoxide Dismutase (SOD) Gene Expression in Cucumber (Cucumis sativus) Plants.

With the increased use of metal nanoparticles (NPs), their access to the food chain has become a main concern to scientists and holds controversial social implications. This research particularly sheds light on copper nanoparticles (CuNP), as they have been commonly used in several industries nowadays. In this study, we investigated the phytotoxicity of CuNP on cucumber (Cucumis sativus) plants grown hydroponically. Atomic Absorption Spectroscopy (AAS), X-Ray Fluorescence (XRF), and Scanning Electron Microscopy (SEM) analysis confirmed that C. sativus treated with CuNP accumulated CuNP in the plant tissues, with higher levels in roots, with amounts that were concentration dependent. Furthermore, genotoxicity was assessed using Random amplified polymorphic DNA (RAPD) technique, and our results showed that CuNP caused genomic alterations in C. sativus. Phenotypical, physiological, and biochemical changes were assessed by determining the CuNP treated plant's total biomass, chlorophyll, H2O2 and MDA contents, and electrolyte leakage percentage. The results revealed notable adverse phenotypical changes along with decreased biomass and decreased levels of the photosynthetic pigments (Chlorophyll a and b) in a concentration-dependent manner. Moreover, CuNP induced damage to the root plasma membrane as determined by the increased electrolyte leakage. A significant increase in H2O2 and MDA contents were detected in C. sativus CuNP treated plants. Additionally, copper-zinc superoxide dismutase (Cu-Zn SOD) gene expression was induced under CuNP treatment. Overall, our results demonstrated that CuNP of 10-30 nm size were toxic to C. sativus plants. This finding will encourage the safe production and disposal NPs. Thus, reducing nano-metallic bioaccumulation into our food chain through crop plants; that possesses a threat to the ecological system.

Inhibition of exosome release by ketotifen enhances sensitivity of cancer cells to doxorubicin.

Exosomes released from cancer cells support metastasis and growth of recipient cells and increase their resistance to chemotherapy. Therapeutic targeting of exosomes is a promising area in cancer research. Our aim is to test the effect of the mast cell stabilizer ketotifen on exosomes release from cancer cells and how this can modify their response to doxorubicin. Exosomes release from three cancer cell lines (MCF7, HeLa and BT549) was assessed by scan electron microscope and exosomes quantification kit. Doxorubicin export within exosomes was monitored flurometrically and cellular sensitivity to doxorubicin ± ketotifen was measured by sulphorhodamine-B and colony formation assays. The three cell lines release different amounts of exosomes with the highest quantity released from BT549 followed by MCF7 and then HeLa. Ketotifen (10 µmol L-1) reduced exosomes release in all three cell lines with different efficiency (HeLa>MCF7>BT549). Doxorubicin export via exosomes was highest in BT549, lower in HeLa and lowest in MCF7 cells. Pretreatment with ketotifen sensitized the cells to doxorubicin (HeLa>MCF7>BT549) with a sensitization factor of 27, 8 and 1.25 respectively. Increased sensitivity of cells to doxorubicin by ketotifen was proportional to its effect on exosomes release. Our data is the first report of ketotifen modulating exosomes release from cancer cells and opens the avenue for exosomes-targeting cancer therapy. The differential effects of ketotifen on doxorubicin exosomal export in the cell lines studied, suggests an opportunity of pharmacological enhancement of doxorubicin anti-tumor activity in some but not all cancer types.

Reduced Graphene Oxide Thin Film on Conductive Substrates by Bipolar Electrochemistry.

Recent years have shown an increased interest in developing manufacturing processes for graphene and its derivatives that consider the environmental impact and large scale cost-effectiveness. However, today's most commonly used synthesis routes still suffer from their excessive use of harsh chemicals and/or the complexity and financial cost of the process. Furthermore, the subsequent transfer of the material onto a substrate makes the overall process even more intricate and time-consuming. Here we describe a single-step, single-cell preparation procedure of metal-supported reduced graphene oxide (rGO) using the principle of bipolar electrochemistry of graphite in deionized water. Under the effect of an electric field between two stainless steel feeder electrodes, grapheme layers at the anodic pole of the wireless graphite were oxidized into colloidal dispersion of GO, which migrated electrophoretically towards the anodic side of the cell, and deposited in the form of rGO (d(002) = 0.395 nm) by van der Waals forces. For substrates chemically more susceptible to the high anodic voltage, we show that the electrochemical setup can be adapted by placing the latter between the wireless graphite and the stainless steel feeder anode. This method is straightforward, inexpensive, environmentally-friendly, and could be easily scaled up for high yield and large area production of rGO thin films.