Rodica Elena Ionescu

Large Scale Fabrication of Gold Nano-Structured Substrates Via High Temperature Annealing and Their Direct Use for the LSPR Detection of Atrazine

The present work is reporting on the fabrication of localized surface plasmonic resonant (LSPR) gold nano-structures on glass substrate by using different high annealing temperatures (500xa0°C, 550xa0°C, 600xa0°C) of initially created semi-continue gold films (2xa0nm and 5xa0nm) by the electron beam evaporation technique. Interestingly, well-defined gold nano-structures were also obtained from continuous 8xa0nm evaporated gold film - known as the value above gold percolated thickness - once exposed to high temperatures. The surface morphology and plasmonic spectroscopy of “annealed” nano-structures were controlled by key experimental parameters such as evaporated film thickness and annealing temperature. By using scanning electron microscopy (SEM) characterization of annealed surface it was noticed that the size and inter-particle distance between nano-structures were highly dependent on the evaporated thin film thickness, while the nanoparticle shape evolution was mainly affected by the employed annealing temperature. Due to the well-controlled morphology of gold nano-particles, prominent and stable LSPR spectra were observed with good plasmon resonance tunability from 546xa0nm to 780xa0nm that recommend the developed protocol as a robust alternative to fabricate large scale LSPR surface. An example of a LSPR-immunosensor is reported. Thus, the monoclonal anti-atrazine antibodies immobilizion on the “annealed” gold nano-structures, as well as the specific antigen (atrazine) recognition were monitored as variations of the resonance wavelength shifts and optical density changes in the extinction measurements.

A lower limit of detection for atrazine was obtained using bioluminescent reporter bacteria via a lower incubation temperature.

The present article reports on the influence of various atrazine concentrations to the response of genetically modified Escherichia coli TV1061 bacterial cells while modulating the experimental conditions. Interesting increases of bioluminescence signals are recorded for E. coli TV1061 bacteria in the presence of 10 μg/mL atrazine concentration named high-toxicity bacteria alert when compared with 1 μg/mL -10 fg/mL atrazine termed low-toxicity bacteria alert. Detecting the effect of atrazine via its effect on bioluminescence of bacteria has been carried out by two consecutive measurements (fresh and overnight modes) at different concentrations of analyte. We have shown that a more precise discrimination at lower-toxicity concentrations can be obtained through overnight incubation of bacteria with the analyte at 4 °C. In addition, centrifugation of bacterial cells and analyte dilutions has been performed in order to ensure a better interaction between the insoluble atrazine pesticide and the bacterial cells.

A facile and cost-effective TEM grid approach to design gold nano-structured substrates for high throughput plasmonic sensitive detection of biomolecules

A commercial TEM grid was used as a mask for the creation of extremely well-organized gold micro-/nano-structures on a glass substrate via a high temperature annealing process at 500 °C. The structured substrate was (bio)functionalized and used for the high throughput LSPR immunosensing of different concentrations of a model protein named bovine serum albumin.

Fate and Characterization Factors of Nanoparticles in Seventeen Subcontinental Freshwaters: A Case Study on Copper Nanoparticles

The lack of characterization factors (CFs) for engineered nanoparticles (ENPs) hampers the application of life cycle assessment (LCA) methodology in evaluating the potential environmental impacts of nanomaterials. Here, the framework of the USEtox model has been selected to solve this problem. On the basis of colloid science, a fate model for ENPs has been developed to calculate the freshwater fate factor (FF) of ENPs. We also give the recommendations for using the hydrological data from the USEtox model. The functionality of our fate model is proved by comparing our computed results with the reported scenarios in North America, Switzerland, and Europe. As a case study, a literature survey of the nano-Cu toxicology values has been performed to calculate the effect factor (EF). Seventeen freshwater CFs of nano-Cu are proposed as recommended values for subcontinental regions. Depending on the regions and the properties of the ENPs, the region most likely to be affected by nano-Cu is Africa (CF of 11.11 × 10(3) CTUe, comparative toxic units) and the least likely is north Australia (CF of 3.87 × 10(3) CTUe). Furthermore, from the sensitivity analysis of the fate model, 13 input parameters (such as depth of freshwater, radius of ENPs) show vastly different degrees of influence on the outcomes. The characterization of suspended particles in freshwater and the dissolution rate of ENPs are two significant factors.

Influence of carbon-based nanomaterials on lux-bioreporter Escherichia coli

The cytotoxic effects of carbon-based nanomaterials are evaluated via the induction of luminescent genetically engineered Escherichia coli bacterial cells. Specifically, two engineered E. coli bacteria strains of DPD2794 and TV1061 were incubated with aqueous dispersion of three carbon allotropes (multi-wall carbon nanotubes (MWCNTs), graphene nanosheets and carbon black nanopowders) with different concentrations and the resulting bioluminescence was recorded at 30°C and 25°C, respectively. The corresponding optical density changes of bacterial cells in the presence of various carbon nanomaterials were recorded as well. Based on these results, E. coli DPD2794 bacterial induction responds to a greater degree than E. coli TV1061 bacteria when exposed to various carbon-based nanomaterials. Finally, the surface morphology of E. coli DPD2794 bacteria cells before and after carbon-based nanomaterials treatment was observed using a field emission scanning electron microscope (FESEM), from which morphological changes from the presence of carbon-based nanomaterials were observed and discussed.

Bioluminescence enhancement through an added washing protocol enabling a greater sensitivity to carbofuran toxicity

The effects of carbofuran toxicity on a genetically modified bacterial strain E. coli DPD2794 were enhanced using a new bioluminescent protocol which consisted of three consecutive steps: incubation, washing and luminescence reading. Specifically, in the first step, several concentrations of carbofuran aqueous solutions were incubated with different bacterial suspensions at recorded optical densities for different lengths of time. Thereafter, the resulting bacterial/toxicant mixtures were centrifuged and the aged cellular supernatant replaced with fresh medium. In the final step, the carbofuran- induced bioluminescence to the exposed E. coli DPD2794 bacteria was shown to provide a faster and higher intensity when recorded at a higher temperature at30°C which is not usually used in the literature. It was found that the incubation time and the replacement of aged cellular medium were essential factors to distinguish different concentrations of carbofuran in the bioluminescent assays. From our results, the optimum incubation time for a light ON bioluminescence detection of the effect of carbofuran was 6h. Thanks to the replacement of the aged cellular medium, a group of additional peaks starting around 30min were observed and we used the corresponding areas under the curve (AUC) at different contents of carbofuran to produce the calibration curve. Based on the new protocol, a carbofuran concentration of 0.5pg/mL can be easily determined in a microtiter plate bioluminescent assay, while a non-wash protocol provides an unexplainable order of curve evolutionswhich does not allow the user to determine the concentration.

Fabrication of an atrazine acoustic immunosensor based on a drop-deposition procedure

Among the various novel analytical systems, immunosensors based on acoustic waves are of emerging interest because of their good sensitivity, real-time monitoring capability, and experimental simplicity. In this work, piezoelectric immunosensors were constructed for the detection of atrazine through the immobilization of specific monoclonal anti-atrazine antibodies on thiolated modified quartz crystal microbalances (QCMs). The immunoassay was conducted by a novel drop-deposition procedure using different atrazine dilutions in phosphate buffer solution ranging from 10-10 to 10-1 mg/mL. The immunoreactions between varying contents of atrazine and its antibody were dynamically exhibited through in situ monitoring of the frequency and motional resistance changes over 20 min. Thus, atrazine recognition by the anti-atrazine antibody leads to a decrease of the resonant frequency that is proportional to a given atrazine concentration. Interestingly, the motional resistance also increased proportionally during the measurements, which could be attributed to the specific viscoelastic properties and/or conformation changes of the antibodies once the immunoreactions occurred. By combining the measurements of frequency with those of motional resistance, additional information was provided about the interaction between the atrazine-named antigen and its respective antibody. Finally, the analytical specificity of the immunosensor to atrazine was evaluated through the response to a nonspecific anti-human IgG antibody-modified QCM crystal under the same drop conditions.

On-line biosensor for the detection of putative toxicity in water contaminants.

Potential threat on drinking water requires monitoring solutions, such as the one proposed herein, as a real-time, wide ranged, water monitoring system to detect the presence of toxicants in water. We studied the role of a selected number of parameters affecting performance and, thus, improved the prototype into an optimized next-generation device, resulting in enabling increased measurement duration, coupled with increased sensitivity. The chosen parameters in question were the peristaltic flow system, the fiber probe matrix stability through a re-design of the fiber probe holder and flow unit cell, as well as the modulation of bacterial medium concentration to increase bioreporter performance while keeping biofouling in check. Measurements were made with spiked samples and validated with polluted field-collected samples.

Fabrication of Annealed Gold Nanostructures on Pre-Treated Glow-Discharge Cleaned Glasses and Their Used for Localized Surface Plasmon Resonance (LSPR) and Surface Enhanced Raman Spectroscopy (SERS) Detection of Adsorbed (Bio)molecules

Metallic nanoparticles are considered as active supports in the development of specific chemical or biological biosensors. Well-organized nanoparticles can be prepared either through expensive (e.g., electron beam lithography) or inexpensive (e.g., thermal synthesis) approaches where different shapes of nanoparticles are easily obtained over large solid surfaces. Herein, the authors propose a low-cost thermal synthesis of active plasmonic nanostructures on thin gold layers modified glass supports after 1 h holding on a hot plate (~350 °C). The resulted annealed nanoparticles proved a good reproducibility of localized surface plasmon resonance (LSPR) and surface enhanced Raman spectroscopy (SERS) optical responses and where used for the detection of low concentrations of two model (bio)chemical molecules, namely the human cytochrome b5 (Cyt-b5) and trans-1,2-bis(4-pyridyl)ethylene (BPE).

Freshwater Sediment Characterization Factors of Copper Oxide Nanoparticles

Wide use of engineered nanoparticles (ENPs) is likely to result in the eventually accumulation of ENPs in sediment. The benthic organisms living in sediments may suffer relatively high toxic effects of ENPs. This study has selected copper oxide nanoparticles (nano-CuO) as a research object. To consider the impacts of spatial heterogeneity on ENPs toxicity, the characterization factor (CF) derived from life cycle assessment (LCA) methodology is used as an indicator in this study. A nano-specific fate model has been used to calculate the freshwater sediment fate factor (FF) of nano-CuO. A literature survey of the nano-CuO toxicology values has been performed to calculate the effect factor (EF). Seventeen freshwater sediment CFs of nano-CuO are proposed as recommended values for subcontinental regions. The region most likely to be affected by nano-CuO is northern Australia (CF of 21.01103 CTUe, comparative toxic units) and the least likely is northern Europe and northern Canada (CF of 8.55103 CTUe). These sediment CFs for nano-CuO could be used in the future when evaluating the ecosystem impacts of products containing nano-CuO by LCA method.