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Baraneedharan, P., Shankari, D., Arulraj, A., Sephra, P. J., Mangalaraja, R. V., & Khalid, M. (2023). Nanoengineering of MXene-Based Field-Effect Transistor Gas Sensors: Advancements in Next-Generation Electronic Devices. J. Electrochem. Soc., 180(10), 107501.
Abstract: In recent years, Two-Dimensional (2D) materials have gained significant attention for their distinctive physical and chemical properties, positioning them as promising contenders for the next generation of electronic technologies. One notable group within these materials is MXenes, which have exhibited remarkable breakthroughs across various technological domains, including catalysis, renewable energy, electronics, sensors, fuel cells, and supercapacitors. By making subtle modifications to the surface termination, introducing metal ions, precise etching timing, and applying surface functionalization, the characteristics of MXenes can be fine-tuned to achieve desired band structures, rendering them suitable for sensor design. This review focuses on the strategic development of gas sensors based on Field-Effect Transistors (FETs), thoroughly examining the latest progress in MXene-based material design and addressing associated challenges and future prospects. The review aims to provide a comprehensive overview of MXene, summarizing its current applications and advancements in FET-based gas sensing.
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Caceres, C., Moczko, E., Basozabal, I., Guerreiro, A., & Piletsky, S. (2021). Molecularly Imprinted Nanoparticles (NanoMIPs) Selective for Proteins: Optimization of a Protocol for Solid-Phase Synthesis Using Automatic Chemical Reactor. Polymers, 13(3), 314.
Abstract: Molecularly imprinted polymer nanoparticles (nanoMIPs) are receiving broad interest as robust and highly selective synthetic receptors for a variety of molecules. Due to their stability, inexpensive synthesis and easy implementation, they are considered a promising alternative to antibodies in sensors, diagnostics and separation applications. The most challenging targets for the production of synthetic receptors are proteins due to their fragile nature and the multitude of possible binding sites in their structure. Herein, we describe the modification and optimization of the protocol for synthesis of nanoMIPs with specificity for proteins using the prototype of an automated solid-phase synthesizer. Using an automated system gives an advantage for the simple, fast and fully controlled, reproducible production of nanoMIPs. The molecular imprinting in the reactor is performed using a template covalently immobilized on a solid support, in mild conditions suitable for preserving protein native structure. The validation of the protocol was made by assessing the ability to regenerate a solid-phase, and by measuring affinity and specificity of nanoparticles. As a model protein, we have chosen trypsin since its enzymatic activity can be easily monitored by using a commercial colorimetric assay. Different protocols were tested for their ability to improve the yield of high affinity nanoparticles in the final elution.
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Caceres, C., Morgado, M. D. G., Bozo, F. C., Piletsky, S., & Moczko, E. (2022). Rapid Selective Detection and Quantification of beta-Blockers Used in Doping Based on Molecularly Imprinted Nanoparticles (NanoMIPs). Polymers, 14(24), 5420.
Abstract: Human performance enhancing drugs (PEDs), frequently used in sport competitions, are strictly prohibited by the World Anti-Doping Agency (WADA). Biological samples collected from ath-letes and regular patients are continuously tested regarding the identification and/or quantification of the banned substances. Current work is focused on the application of a new analytical method, molecularly imprinted nanoparticles (nanoMIPs), to detect and determine concentrations of certain prohibited drugs, such as B-blockers, in water and human urine samples. These medications are used in the treatment of cardiovascular conditions, negative effects of adrenaline (helping to relief stress), and hypertension (slowing down the pulse and softening the arteries). They can also significantly increase muscle relaxation and improve heart efficiency. The new method of the detection and quantification of B-blockers is based on synthesis, characterization, and implementation of nanoMIPs (so-called plastic antibodies). It offers numerous advantages over the traditional methods, including high binding capacity, affinity, and selectivity for target molecules. Additionally, the whole process is less complicated, cheaper, and better controlled. The size and shape of the nanoMIPs is evaluated by dynamic light scattering (DLS) and transmission electron microscope (TEM). The affinity and selectivity of the nanoparticles are investigated by competitive pseudo enzyme-linked immunosorbent assay (pseudo-ELISA) similar to common immunoassays employing natural antibodies. To provide reliable results towards either doping detection or therapeutic monitoring using the minimal invasive method, the qualitative and quantitative analysis of these drugs is performed in water and human urine samples. It is demonstrated that the assay can detect B-blockers in water within the linear range 1 nmolmiddotL(-1)-1 mmolmiddotL(-1) for atenolol with the detection limit 50.6 ng mL(-1), and the linear range 1 mmolmiddotL(-1)-10 mmolmiddotL(-1) for labetalol with the detection limit of 90.5 ngmiddotmL(-1). In human urine samples, the linear range is recorded in the concentration range 0.1 mmolmiddotL(-1)-10 nmolmiddotL(-1) for atenolol and 1 mmolmiddotL(-1)-10 nmolmiddotL(-1) for labetalol with a detection limit of 61.0 ngmiddotmL(-1)for atenolol and 99.4 ngmiddotmL(-1) for labetalol.
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Cáeres, C., Heusser, B., Garnham, A., & Moczko, E. (2023). The Major Hypotheses of Alzheimer's Disease: Related Nanotechnology-Based Approaches for Its Diagnosis and Treatment. Cells, 12(23), 2669.
Abstract: Alzheimer's disease (AD) is a well-known chronic neurodegenerative disorder that leads to the progressive death of brain cells, resulting in memory loss and the loss of other critical body functions. In March 2019, one of the major pharmaceutical companies and its partners announced that currently, there is no drug to cure AD, and all clinical trials of the new ones have been cancelled, leaving many people without hope. However, despite the clear message and startling reality, the research continued. Finally, in the last two years, the Food and Drug Administration (FDA) approved the first-ever medications to treat Alzheimer's, aducanumab and lecanemab. Despite researchers' support of this decision, there are serious concerns about their effectiveness and safety. The validation of aducanumab by the Centers for Medicare and Medicaid Services is still pending, and lecanemab was authorized without considering data from the phase III trials. Furthermore, numerous reports suggest that patients have died when undergoing extended treatment. While there is evidence that aducanumab and lecanemab may provide some relief to those suffering from AD, their impact remains a topic of ongoing research and debate within the medical community. The fact is that even though there are considerable efforts regarding pharmacological treatment, no definitive cure for AD has been found yet. Nevertheless, it is strongly believed that modern nanotechnology holds promising solutions and effective clinical strategies for the development of diagnostic tools and treatments for AD. This review summarizes the major hallmarks of AD, its etiological mechanisms, and challenges. It explores existing diagnostic and therapeutic methods and the potential of nanotechnology-based approaches for recognizing and monitoring patients at risk of irreversible neuronal degeneration. Overall, it provides a broad overview for those interested in the evolving areas of clinical neuroscience, AD, and related nanotechnology. With further research and development, nanotechnology-based approaches may offer new solutions and hope for millions of people affected by this devastating disease.
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Concha-Riedel, J., Antico, F. C., & Lopez-Querol, S. (2021). Mechanical strength, mass loss and volumetric changes of drying adobe matrices combined with kaolin and fine soil particles. Constr. Build. Mater., 312, 125246.
Abstract: Earthen construction represents almost 30% of the housing in developing countries, partially because of its low cost compared to steel and concrete construction, and also because the raw materials are available almost everywhere. One of the biggest disadvantages of earthen materials is the lack of information and variety on their constitutive materials, specifically their soil type. This work addresses the physical and mechanical properties of adobe matrices containing different concentrations of kaolin, which is a specific type of clay, as well as different proportions of fine particles of the original soil of the adobe matrix. All adobe matrices were manufactured with a SM-SC soil obtained from Santiago, Chile, and had concentrations of 0, 10, 30, and 50% of kaolin and 0, 10, 20, and 30% fines of the original soil content. It is concluded that the compressive strength of the studied earthen mixtures improves when kaolin is added to the mixture. The shrinkage of adobe matrices with kaolin compared to plain adobe matrices was reduced during the first days of age and stayed stable after that. This work shows that the inclusion of fines from the original soil (other than kaolin) did not significantly affect any of the studied properties. It also shows that the Unified Soil Classification System is not sufficient to characterize soils for adobe matrices.
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Gacitua, M. A., Gonzalez, B., Majone, M., & Aulenta, F. (2014). Boosting the electrocatalytic activity of Desulfovibrio paquesii biocathodes with magnetite nanoparticles. Int. J. Hydrog. Energy, 39(27), 14540–14545.
Abstract: The production of reduced value-added chemicals and fuels using microorganisms as cheap cathodic electrocatalysts is recently attracting considerable attention. A robust and sustainable production is, however, still greatly hampered by a poor understanding of electron transfer mechanisms to microorganisms and the lack of strategies to improve and manipulate thereof. Here, we investigated the use of electrically-conductive magnetite (Fe3O4) nanoparticles to improve the electrocatalytic activity of a H-2-producing Desulfovibrio paquesii biocathode. Microbial biocathodes supplemented with a suspension of nanoparticles displayed increased H-2 production rates and enhanced stability compared to unamended ones. Cyclic voltammetry confirmed that Faradaic currents involved in microbially-catalyzed H-2 evolution were enhanced by the addition of the nanoparticles. Possibly, nanoparticles improve the extracellular electron path to the microorganisms by creating composite networks comprising of mineral particles and microbial cells. Copyright (C) 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
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Han, Z. Y., Chen, H., He, C. L., Dodbiba, G., Otsuki, A., Wei, Y. Z., et al. (2023). Nanobubble size distribution measurement by interactive force apparatus under an electric field. Sci. Rep., 13(1), 3663.
Abstract: Nanobubbles have been applied in many fields, such as environmental cleaning, material production, agriculture, and medicine. However, the measured nanobubble sizes differed among the measurement methods, such as dynamic light scattering, particle trajectory, and resonance mass methods. Additionally, the measurement methods were limited with respect to the bubble concentration, refractive index of liquid, and liquid color. Here, a novel interactive force measurement method for bulk nanobubble size measurement was developed by measuring the force between two electrodes filled with bulk nanobubble-containing liquid under an electric field when the electrode distance was changed in the nm scale with piezoelectric equipment. The nanobubble size was measured with a bubble gas diameter and also an effective water thin film layer covered with a gas bubble that was estimated to be approximately 10 nm based on the difference between the median diameter of the particle trajectory method and this method. This method could also be applied to the solid particle size distribution measurement in a solution.
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Kalyaan, A., Pinilla, P., Krijt, S., Mulders, G. D., & Banzatti, A. (2021). Linking Outer Disk Pebble Dynamics and Gaps to Inner Disk Water Enrichment. Astrophys. J., 921(1), 84.
Abstract: Millimeter continuum imaging of protoplanetary disks reveals the distribution of solid particles and the presence of substructures (gaps and rings) beyond 5-10 au, while infrared (IR) spectra provide access to abundances of gaseous species at smaller disk radii. Building on recent observational findings of an anti-correlation between the inner disk water luminosity and outer dust disk radius, we aim here at investigating the dynamics of icy solids that drift from the outer disk and sublimate their ice inside the snow line, enriching the water vapor that is observed in the IR. We use a volatile-inclusive disk evolution model to explore a range of conditions (gap location, particle size, disk mass, and alpha viscosity) under which gaps in the outer disk efficiently block the inward drift of icy solids. We find that inner disk vapor enrichment is highly sensitive to the location of a disk gap, yielding for each particle size a radial “sweet spot” that reduces the inner disk vapor enrichment to a minimum. For pebbles of 1-10 mm in size, which carry the most mass, this sweet spot is at 7-15 au, suggesting that inner gaps may have a key role in reducing ice delivery to the inner disk and may not allow the formation of Earths and super-Earths. This highlights the importance of observationally determining the presence and properties of inner gaps in disks. Finally, we argue that the inner water vapor abundance can be used as a proxy for estimating the pebble drift efficiency and mass flux entering the inner disk.
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Mahajan, S. M., & Asenjo, F. A. (2023). Parametric amplification of electromagnetic plasma waves in resonance with a dispersive background gravitational wave. Phys. Rev. E, 107(3), 035205.
Abstract: It is shown that a subluminal electromagnetic plasma wave, propagating in phase with a background subluminal gravitational wave in a dispersive medium, can undergo parametric amplification. For these phenomena to occur, the dispersive characteristics of the two waves must properly match. The response frequencies of the two waves (medium dependent) must lie within a definite and restrictive range. The combined dynamics is represented by a Whitaker-Hill equation, the quintessential model for parametric instabilities. The exponential growth of the electromagnetic wave is displayed at the resonance; the plasma wave grows at the expense of the background gravitational wave. Different physical scenarios, where the phenomenon can be possible, are discussed.
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Pina, S., Candia-Onfray, C., Hassan, N., Jara-Ulloa, P., Contreras, D., & Salazar, R. (2021). Glassy Carbon Electrode Modified with C/Au Nanostructured Materials for Simultaneous Determination of Hydroquinone and Catechol in Water Matrices. Chemosensors, 9(5), 88.
Abstract: The simultaneous determination of hydroquinone and catechol was conducted in aqueous and real samples by means of differential pulse voltammetry (DPV) using a glassy carbon electrode modified with Gold Nanoparticles (AuNP) and functionalized multiwalled carbon nanotubes by drop coating. A good response was obtained in the simultaneous determination of both isomers through standard addition to samples prepared with analytical grade water and multivariate calibration by partial least squares (PLS) in winery wastewater fortified with HQ and CT from 4.0 to 150.00 mu M. A sensitivity of 0.154 mu A mu M-1 and 0.107 mu A mu M-1, and detection limits of 4.3 and 3.9 mu M were found for hydroquinone and catechol, respectively. We verified the reliability of the developed method by simultaneously screening analytes in spiked tap water and industrial wastewater, achieving recoveries over 80%. In addition, this paper demonstrates the applicability of chemometric tools for the simultaneous quantification of both isomers in real matrices, obtaining prediction errors of lower than 10% in fortified wastewater.
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Shanmugaraj, K., Mangalaraja, R. V., Campos, C. H., Singh, D. P., Aepuru, R., Thirumurugan, A., et al. (2023). Gold nanoparticles decorated two-dimensional TiO2 nanosheets as effective catalyst for nitroarenes and rhodamine B dye reduction in batch and continuous flow methods. Inorg. Chem. Commun., 149, 110406.
Abstract: Our environment is greatly endangered by the accumulation of various toxic organic pollutants that are continually produced through unavoidable human needs and the industrialization process. Herein, we report highly active gold nanoparticles (AuNPs) immobilized on two-dimensional (2D) TiO2 nanosheets (AuNPs-TiO2NSs) as a catalyst for the catalytic reduction of nitroarenes (NAs) such as 4-nitroaniline (4-NA), 4-(4-nitrophenyl)morpholine (4-NM), 4-(2-fluoro-4-nitrophenyl)morpholine (4-FNM) and rhodamine B (RhB) dye in the presence of sodium borohydride (NaBH4) medium. Initially, TiO2NSs are prepared by the hydrothermal treatment followed by the modification with 3-aminopropyl-trimethoxysilane (APTMS) coupling agent for strong anchoring of the AuNPs. HR-TEM images exhibit that AuNPs (2.30 +/- 0.06 nm) are immobilized on the surface of ultrathin 2-dimensional TiO2NSs. AuNPs-TiO2NSs catalyst shows excellent catalytic activity towards the reduction of various NAs (4-NA, 4-NM and 4-FNM) and RhB dye with maximum conversion efficiency of >98 %. Moreover, the pseudo-first-order rate constants are estimated as 5.50 x 10- 3 s- 1, 7.20 x 10- 3 s- 1, 6.40 x 10-3 s- 1 and 4.30 x 10-3 s- 1 for the reduction of 4-NA, 4-NM, 4-FNM, and RhB, respectively. For large-scale in-dustrial applications, AuNPs-TiO2NSs catalyst embedded in a continuous flow-fixed bed reactor for the catalytic reduction of 4-NA and RhB dye under optimized reaction conditions. AuNPs-TiO2NSs catalyst shows high con-version rates for 4-NA (>99 %) and RhB (>99%) along with excellent recyclability over 12 cycles in continuous flow fixed bed reactor. The mechanism of synthetic pathway and catalytic reduction of NAs and RhB dye over AuNPs-TiO2NSs catalyst are also proposed. This study may lead to the use AuNPs-TiO2NSs catalyst with superior recyclable catalytic efficiency in various catalytic reactions.
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Shanmugaraj, K., Mangalaraja, R. V., Campos, C. H., Udayabhaskar, R., Singh, D. P., Vivas, L., et al. (2023). Cu-Ni bimetallic nanoparticles anchored on halloysite nanotubes for the environmental remediation. Surf. Interfaces, 41, 103257.
Abstract: Hereby, we report the synthesis of CuNi bimetallic nanoparticles (NPs)-decorated halloysite nanotubes (CuNi/ HNTs) for the catalytic reduction of 4-nitroaniline (4-NA) and rhodamine B (RhB) dye in an aqueous medium at room temperature. In this work, CuNi/HNTs composites with different wt% of CuNi NPs were synthesized and characterized by various techniques such as SEM, EDS, XRD, TEM and XPS. The TEM characterization confirmed that the CuNi bimetallic NPs (similar to 11 nm) were successfully anchored onto the outer surface of HNTs. Among the prepared catalysts, Cu0.75Ni0.25/HNTs catalyst displayed highest catalytic activity in the reduction of 4-NA to its corresponding amino derivative in the presence of NaBH4 with a maximum conversion efficiency of >99% and an apparent rate constant k(app) of 0.152 s(- 1) within 30 s of reaction time. Notably, even after 15 cycles of catalytic reduction of 4-NA and RhB, there was no apparent deactivation of the catalytic activity of the Cu0.75Ni0.25/HNTs catalyst, demonstrating the excellent catalytic reusability and stability. The presence of CuNi NPs with low Ni content enhanced the catalytic activity due to the synergetic effect. Moreover, the continuous flow fixed bed reactor designed with Cu0.75Ni0.25/HNTs catalyst exhibited the potential application for the reduction of 4-NA and RhB dye under mild reaction conditions. Furthermore, the present catalytic system could be applicable for the treatment of various wastewater effluents.
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Slane, J., Vivanco, J., Rose, W., Ploeg, H. L., & Squire, M. (2015). Mechanical, material, and antimicrobial properties of acrylic bone cement impregnated with silver nanoparticles. Mater. Sci. Eng. C-Mater. Biol. Appl., 48, 188–196.
Abstract: Prosthetic joint infection is one of the most serious complications that can lead to failure of a total joint replacement. Recently, the rise of multidrug resistant bacteria has substantially reduced the efficacy of antibiotics that are typically incorporated into acrylic bone cement. Silver nanoparticles (AgNPs) are an attractive alternative to traditional antibiotics resulting from their broad-spectrum antimicrobial activity and low bacterial resistance. The purpose of this study, therefore, was to incorporate metallic silver nanoparticles into acrylic bone cement and quantify the effects on the cement's mechanical, material and antimicrobial properties. AgNPs at three loading ratios (025, 0.5, and 1.0% wt/wt) were incorporated into a commercial bone cement using a probe sonication technique. The resulting cements demonstrated mechanical and material properties that were not substantially different from the standard cement. Testing against Staphylococcus aureus and Staphylococcus epidermidis using Kirby-Bauer and time-kill assays demonstrated no antimicrobial activity against planktonic bacteria. In contrast, cements modified with AgNPs significantly reduced biofilm formation on the surface of the cement. These results indicate that AgNP-loaded cement is of high potential for use in primary arthroplasty where prevention of bacterial surface colonization is vital. (C) 2014 Elsevier B.V. All rights reserved.
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Suresh, R., Alvarez, A., Sandoval, C., Ramirez, E., Santander, P., Mangalaraja, R. V., et al. (2023). Fe2O3/NiO nanocomposites: synthesis, characterization and roxarsone sensing by Fourier transform infrared photoacoustic spectroscopy. New J. Chem., 47(27), 12806–12815.
Abstract: The Fe2O3/NiO nanocomposite was prepared through facile mixing of pure Fe2O3 and NiO nanoparticles. Pure metal oxides were synthesized by the glycine aided hydrothermal method. The crystal structure was determined by X-ray diffraction (XRD) analysis. Both scanning electron microscopy (SEM) and transmission electron microscopy (TEM) clearly show that the NiO nanospheres were homogeneously distributed on Fe2O3 nanoplates. Fourier transform infrared (FTIR) spectra reveal that functionalization by glycine induces carboxylic and amino groups on the surface of nanoparticles. The optical properties such as light absorption behavior and band gap of the Fe2O3/NiO nanocomposite were determined by UV-Visible diffuse reflectance spectroscopy (DRS UV-Vis). The roxarsone (ROX) sensing behavior of the Fe2O3/NiO nanocomposite was evaluated by using Fourier transform infrared (FTIR) – photoacoustic spectroscopy (PAS) that allowed quantitative sensing of the ROX@Fe2O3/NiO complex. The photoacoustic signals of ROX were clearly observed in the FTIR-PAS spectra, particularly in the range of 1700 to 1000 cm(-1) without spectral interference from the composite. Furthermore, principal component analysis (PCA) and partial least square (PLS) regression models were applied to calibrate and validate ROX quantification. The PLS model exhibited the best performance in predicting the ROX concentration through ROX@Fe2O3/NiO samples. This proof of concept suggests that the Fe2O3/NiO nanocomposite has improved adsorption and spectral features by FTIR-PAS for sensing of organometallic compounds such as ROX.
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Valle, H., Palao-Suay, R., Aguilar, M. R., Lerma, T. A., Palencia, M., Mangalaraja, R. V., et al. (2023). Nanocarrier of α-Tocopheryl Succinate Based on a Copolymer Derivative of (4,7-dichloroquinolin-2-yl)methanol and Its Cytotoxicity against a Breast Cancer Cell Line. Polymers, 15(22), 4342.
Abstract: In order to improve the water solubility and, therefore, bioavailability and therapeutic activity of anticancer hydrophobic drug alpha-tocopherol succinate (alpha-TOS), in this work, copolymers were synthesized via free radicals from QMES (1-[4,7-dichloroquinolin-2-ylmethyl]-4-methacryloyloxyethyl succinate) and VP (N-vinyl-2-pirrolidone) using different molar ratios, and were used to nanoencapsulate and deliver alpha-TOS into cancer cells MCF-7. QMES monomer was chosen because the QMES pendant group in the polymer tends to hydrolyze to form free 4,7-dichloro-2-quinolinemethanol (QOH), which also, like alpha-TOS, exhibit anti-proliferative effects on cancerous cells. From the QMES-VP 30:70 (QMES-30) and 40:60 (QMES-40) copolymers obtained, it was possible to prepare aqueous suspensions of empty nanoparticles (NPs) loaded with alpha-TOS by nanoprecipitation. The diameter and encapsulation efficiency (%EE) of the QMES-30 NPs loaded with alpha-TOS were 128.6 nm and 52%; while for the QMES-40 NPs loaded with alpha-TOS, they were 148.8 nm and 65%. The results of the AlamarBlue assay at 72 h of treatment show that empty QMES-30 NPs (without alpha-TOS) produced a marked cytotoxic effect on MCF-7 breast cancer cells, corresponding to an IC50 value of 0.043 mg mL-1, and importantly, they did not exhibit cytotoxicity against healthy HUVEC cells. Furthermore, NP-QMES-40 loaded with alpha-TOS were cytotoxic with an IC50 value of 0.076 mg mL-1, demonstrating a progressive release of alpha-TOS; however, the latter nanoparticles were also cytotoxic to healthy cells in the range of the assayed concentrations. These results contribute to the search for a new polymeric nanocarrier of QOH, alpha-TOS or other hydrophobic drugs for the treatment of cancer or others diseases treatable with these drugs.
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