Nanozymes based on octahedral platinum nanocrystals with {111} surface facets: glucose oxidase mimicking activity in electrochemical sensors

The ability of shape-controlled octahedral Pt nanoparticles to act as nanozyme mimicking glucose oxidase enzyme is reported. Extended {111} particle surface facets coupled with a size comparable to natural enzymes and easy-to-remove citrate coating give high affinity for glucose, comparable to the enzyme as proven by the steady-state kinetics of glucose electrooxidation. The easy and thorough removal of the citrate coating, demonstrated by X-ray photoelectron spectroscopy analysis, allows a highly stable deposition of the nanozymes on the electrode. The glucose electrochemical detection (at -0.2 V vs SCE) shows a linear response between 0.36 and 17 mM with a limit of detection of 110 mu M. A good reproducibility has been achieved, with an average relative standard deviation (RSD) value of 9.1% (n = 3). Similarly, a low intra-sensor variability has been observed, with a RSD of 6.6% (n = 3). Moreover, the sensor shows a long-term stability with reproducible performances for at least 2 months (RSD: 7.8%). Tests in saliva samples show the applicability of Pt nanozymes to commercial systems for non-invasive monitoring of hyperglycemia in saliva, with recoveries ranging from 92 to 98%

Co-precipitation of oppositely charged nanoparticles: the case of mixed ligand nanoparticles

Colloid stability is of high importance in a multitude of fields ranging from food science to biotechnology. There is strong interest in studying the stability of small particles (of a size of a few nanometres) with complex surface structures, that make them resemble the complexity of proteins and other natural biomolecules, in the presence of oppositely charged nanoparticles. While for nanoparticles with homogeneously charged surfaces an abrupt precipitation has been observed at the neutrality of charges, data are missing about the stability of nanoparticles when they have more complex surface structures, like the presence of hydrophobic patches. To study the role of these hydrophobic patches in the stability of nanoparticles a series of negatively charged nanoparticles has been synthesized with different ratios of hydrophobic content and with control on the structural distribution of the hydrophobic moiety, and then titrated with positively charged nanoparticles. For nanoparticles with patchy nanodomains, the influence of hydrophobic content was observed together with the influence of the size of the nanoparticles. By contrast, for nanoparticles with a uniform distribution of hydrophobic ligands, size changes and hydrophobic content did not play any role in co-precipitation behaviour. A comparison of these two sets of nanoparticles suggests that nanodomains present at the surfaces of nanoparticles are playing an important role in stability against co-precipitation

Ultra-small octahedral PtNP-labeled antibodies as an ultrasensitive nanozyme probe for chemiluminescence detection in bioanalytics

Chemiluminescence (CL)-based probes are one of the most sensitive detection principles in nanodiagnostics. A widely used system is the CL substrate for peroxidase (HRP) employed to label a variety of molecules ranging from small steroids to protein. The CL cocktail for HRP is based on luminol or its analogues, hydrogen peroxide, and an enhancer, allowing the detection of submolar concentrations of the enzyme-labeled analyte. The catalyst of the CL reaction, namely HRP, can be replaced by other more practical and highly stable nano-catalysts/nanozymes; among them, recent studies have demonstrated the superior performance of Pt nanomaterials [1]. In this work, we propose the use of ultra-small (3 nm) citrate-coated octahedral Pt nanocrystals prepared by a new wet chemical reduction method in aqueous environment and conjugated to a secondary human IgG antibody, as an ultrasensitive probe for luminol/hydrogen peroxide CL detection. Conjugates with different nanocrystal-to-antibody molar ratios were first fully characterized and purified by Field-Flow Fractionation (FFF) [2]. FFF confirms the homogeneous size of the conjugated which represents a fundamental parameter for their efficiency. The FFF-selected purified conjugates are homogeneous in size and highly concentrated, and readily available for downstream CL tests, an important requirement for the use of FFF as semi-prep step. First results demonstrate the applicability of Pt nanocrystals as probes for CL detection. Indeed the Pt nanocrystals-antibodies CL signal has been measured for the different nanoparticles-IgG molar ratios, showing an increasing signal as a function of nanoparticles concentration with the possibility to detect IgG down to 10-12 M, value close to that obtained using HRP [3]. In addition, the light signal reaches a steady state value for more than 30 minutes, thus facilitating the assay handling. These results paves the way to the use of Pt nanomaterials, highly monodisperse in size and shape and with easy-to-remove coating, for the production of highly efficient catalysts/nanozymes for CL applications and the development of simple and rapid new tests

Contact angle and adsorption energies of nanoparticles at the air-liquid interface determined by neutron reflectivity and molecular dynamics

Understanding how nanomaterials interact with interfaces is essential to control their self-assembly as well as their optical, electronic, and catalytic properties. We present here an experimental approach based on neutron reflectivity (NR) that allows the in situ measurement of the contact angles of nanoparticles adsorbed at fluid interfaces. Because our method provides a route to quantify the adsorption and interfacial energies of the nanoparticles in situ, it circumvents problems associated with existing indirect methods, which rely on the transport of the monolayers to substrates for further analysis. We illustrate the method by measuring the contact angle of hydrophilic and hydrophobic gold nanoparticles, coated with perdeuterated octanethiol (d-OT) and with a mixture of d-OT and mercaptohexanol (MHol), respectively. The contact angles were also calculated via atomistic molecular dynamics (MD) computations, showing excellent agreement with the experimental data. Our method opens the route to quantify the adsorption of complex nanoparticle structures adsorbed at fluid interfaces featuring different chemical compositions

Citrate-coated, size-tunable octahedral platinum nanocrystals: a novel route for advanced electrocatalysts

The development of green and scalable syntheses for the preparation of size- and shape-controlled metal nanocrystals is of high interest in many areas, including catalysis, electrocatalysis, nanomedicine, and electronics. In this work, a new synthetic approach based on the synergistic action of physical parameters and reagents produces size-tunable octahedral Pt nanocrystals, without the use of catalyst-poisoning reagents and/or difficult-to-remove coatings. The synthesis requires only sodium citrate, ascorbic acid, and fine control of the reduction rate in aqueous environment. Pt octahedral nanocrystals with particle size as low as 7 nm and highly developed {111} facets have been achieved, as demonstrated by Transmission Electron Microscopy, X-ray Diffraction, and electrochemical methods. The absence of sticky molecules together with the high quality of the surface renders these nanocrystals ideal candidates in electrocatalysis. Notably, 7 nm bismuth-decorated octahedral nanocrystals exhibit superior performance for the electro-oxidation of formic acid in terms of both specific and mass activities.JMF and VM acknowledge financial support from MINECO (projects CTQ2016-76221-P and CTQ2016-76231-C2-2-R (AEI/FEDER, UE)). JSG acknowledges financial support from VITC (Vicerrectorado de Investigación y Transferencia de Conocimiento) of the University of Alicante (UATALENTO16-02)

Polymer surfactant mixtures confined at the air/water and solid/waste interfaces

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Platinum Nanoparticles Decrease Reactive Oxygen Species and Modulate Gene Expression without Alteration of Immune Responses in THP-1 Monocytes

Platinum nanoparticles (PtNPs) attract great attention due to their efficient catalysis and good degree of cytocompatibility, but information about their effects on the human immune system is still missing. Monocytes are key cells of the innate immune system and the understanding of their reactions to PtNPs is crucial in view of any feasible application to human pathologies. Here, we evaluate the internalization of citrate-coated PtNPs into THP-1 monocytes and its consequences on immune cell responses. We found that the presence of intracellular PtNPs efficiently reduce reactive oxygen species (ROS) without affecting cell viability. The physiological expression of the immune receptors Cluster of Differentiation 14 (CD14), CD11b, CC-Chemokine Receptor 2 (CCR2) and CCR5 and the expression of cytokines and chemokines are not compromised by the presence of PtNPs within THP-1 cells. On the other hand, the treatment with PtNPs modulates the transcription of sixty genes, some of them involved in lipopolysaccharide (LPS) signaling in different cells. However, the treatment with PtNPs of monocytes does not compromise the LPS-induce increase of cytokines in THP-1 monocytes in vitro. Our results demonstrate that citrate-coated PtNPs are non-toxic, perform efficient intracellular reactive oxygen species (ROS) scavenging activity and possess good immune-compatibility, suggesting them as feasible synthetic enzymes for applications in nanomedicine

From a Chemotherapeutic Drug to a High-Performance Nanocatalyst: A Fast Colorimetric Test for Cisplatin Detection at ppb Level

A rapid point-of-care method for the colorimetric detection of cisplatin was developed, exploiting the efficient conversion of the chemotherapeutic drug into a high-performance nanocatalyst with peroxidase enzyme mimics. This assay provides high specificity and ppb-detection sensitivity with the naked eye or a smartphone-based readout, outperforming many standard laboratory-based techniques. The nanocatalyst-enabled colorimetric assay can be integrated with machine-learning methods, providing accurate quantitative measurements. Such a combined approach opens interesting perspectives for the on-site monitoring of both chemotherapeutic patients to achieve optimal treatments and healthcare workers to prevent their unsafe exposure

From a Chemotherapeutic Drug to a High-Performance Nanocatalyst: A Fast Colorimetric Test for Cisplatin Detection at ppb Level

A rapid point-of-care method for the colorimetric detection of cisplatin was developed, exploiting the efficient conversion of the chemotherapeutic drug into a high-performance nanocatalyst with peroxidase enzyme mimics. This assay provides high specificity and ppb-detection sensitivity with the naked eye or a smartphone-based readout, outperforming many standard laboratorybased techniques. The nanocatalyst-enabled colorimetric assay can be integrated with machinelearning methods, providing accurate quantitative measurements. Such a combined approach opens interesting perspectives for the on-site monitoring of both chemotherapeutic patients to achieve optimal treatments and healthcare workers to prevent their unsafe exposure