Enhancing T1 magnetic resonance imaging contrast with internalized gadolinium(III) in a multilayer nanoparticle.

Multifunctional nanoparticles for biomedical applications have shown extraordinary potential as contrast agents in various bioimaging modalities, near-IR photothermal therapy, and for light-triggered therapeutic release processes. Over the past several years, numerous studies have been performed to synthesize and enhance MRI contrast with nanoparticles. However, understanding the MRI enhancement mechanism in a multishell nanoparticle geometry, and controlling its properties, remains a challenge. To systematically examine MRI enhancement in a nanoparticle geometry, we have synthesized MRI-active Au nanomatryoshkas. These are Au core-silica layer-Au shell nanoparticles, where Gd(III) ions are encapsulated within the silica layer between the inner core and outer Au layer of the nanoparticle (Gd-NM). This multifunctional nanoparticle retains its strong near-IR Fano-resonant optical absorption properties essential for photothermal or other near-IR light-triggered therapy, while simultaneously providing increased T1 contrast in MR imaging by concentrating Gd(III) within the nanoparticle. Measurements of Gd-NM revealed a strongly enhanced T1 relaxivity (r1 ∼ 24 mM-1⋅s-1) even at 4.7 T, substantially surpassing conventional Gd(III) chelating agents (r1 ∼ 3 mM-1⋅s-1 at 4.7 T) currently in clinical use. By varying the thickness of the outer gold layer of the nanoparticle, we show that the observed relaxivities are consistent with Solomon-Bloembergen-Morgan (SBM) theory, which takes into account the longer-range interactions between the encapsulated Gd(III) and the protons of the H2O molecules outside the nanoparticle. This nanoparticle complex and its MRI T1-enhancing properties open the door for future studies on quantitative tracking of therapeutic nanoparticles in vivo, an essential step for optimizing light-induced, nanoparticle-based therapies.

Differences in the Aspect Ratio of Gold Nanorods that Induce Defects in Cell Membrane Models.

Understanding the interactions between biomolecules and nanomaterials is of great importance for many areas of nanomedicine and bioapplications. Although studies in this area have been performed, the interactions between cell membranes and nanoparticles are not fully understood. Here, we investigate the interactions that occur between the Langmuir monolayers of dipalmitoylphosphatidyl glycerol (DPPG) and dipalmitoylphosphatidyl choline (DPPC) with gold nanorods (NR)-with three aspect ratios-and gold nanoparticles. Our results showed that the aspect ratio of the NRs influenced the interactions with both monolayers, which suggest that the physical morphology and electrostatic forces govern the interactions in the DPPG-NR system, whereas the van der Waals interactions are predominant in the DPPC-NR systems. Size influences the expansion isotherms in both systems, but the lipid tails remain conformationally ordered upon expansion, which suggests phase separation between the lipids and nanomaterials at the interface. The coexistence of lipid and NP regions affects the elasticity of the monolayer. When there is coexistence between two phases, the elasticity does not reflect the lipid packaging state but depends on the elasticity of the NP islands. Therefore, the results corroborate that nanomaterials influence the packing and the phase behavior of the mimetic cell membranes. For this reason, developing a methodology to understand the membrane-nanomaterial interactions is of great importance.

Graphene oxide classification and standardization.

There is a need to classify and standardize graphene-related materials giving the growing use of this materials industrially. One of the most used and more difficult to classify is graphene oxide (GO). Inconsistent definitions of GO, closely relating it to graphene, are found in the literature and industrial brochures. Hence, although they have very different physicochemical properties and industrial applications, commonly used classifications of graphene and GO definitions are not substantial. Consequently, the lack of regulation and standardization create trust issues among sellers and buyers that impede industrial development and progress. With that in mind, this study offers a critical assessment of 34 commercially available GOs, characterized using a systematic and reliable protocol for accessing their quality. We establish correlations between GO physicochemical properties and its applications leading to rationale for its classification.

Accelerated Synthesis of Graphene Oxide from Graphene.

Graphene oxide (GO) is an oxygenated functionalized form of graphene that has received considerable attention because of its unique physical and chemical properties that are suitable for a large number of industrial applications. Herein, GO is rapidly obtained directly from the oxidation of graphene using an environmentally friendly modified Hummers method. As the starting material consists of graphene flakes, intercalant agents are not needed and the oxidation reaction is enhanced, leading to orders of magnitude reduction in the reaction time compared to the conventional methods of graphite oxidation. With a superior surface area, the graphene flakes are quickly and more homogeneously oxidized since the flakes are exposed at the same extension to the chemical agents, excluding the necessity of sonication to separate the stacked layers of graphite. This strategy shows an alternative approach to quickly producing GO with different degrees of oxidation that can be potentially used in distinct areas ranging from biomedical to energy storage applications.

The Degree of Oxidation of Graphene Oxide.

We show that the degree of oxidation of graphene oxide (GO) can be obtained by using a combination of state-of-the-art ab initio computational modeling and X-ray photoemission spectroscopy (XPS). We show that the shift of the XPS C1s peak relative to pristine graphene, ΔEC1s, can be described with high accuracy by ΔEC1s=A(cO-cl)2+E0, where c0 is the oxygen concentration, A=52.3 eV, cl=0.122, and E0=1.22 eV. Our results demonstrate a precise determination of the oxygen content of GO samples.

Toxicity of gold nanorods on Ceriodaphnia dubia and Danio rerio after sub-lethal exposure and recovery.

Gold nanorods (AuNRs) are rod-shaped nanoparticles (NPs) with special optical properties that allow their application in several areas including photothermal therapy, diagnosis, drug and gene delivery, cellular imaging, and biosensors. Their high potential for many applications increases the possibility of release in aquatic environments, which can cause risks to organisms. In this study, we evaluated toxic effects of AuNRs on cladoceran and fish (Ceriodaphnia dubia and Danio rerio) and their recovery after post-exposure periods. The EC50 of 0.03 mg L-1 was found for C. dubia in the acute exposure. There was a significant decrease in the number of neonates produced and in the filtration rate of C. dubia after sub-lethal exposure to AuNRs. The toxic mechanism of these NPs to cladocerans was attributed to increases in the reactive oxygen species (ROS) generation. After 4 h of recovery in clean medium, C. dubia were able to reestablish the filtration rate. Enzymatic biomarkers for D. rerio showed significant increases in the activity of superoxide dismutase, catalase, and lipid peroxidation after sub-lethal exposure to AuNRs. These biomarkers were recovered after 168 h in clean water. These results are pivotal on the comprehension of AuNR toxicity to aquatic organisms and are useful in assessing this novel nanomaterial impacts on aquatic biota.

2D Electrolytes: Theory, Modeling, Synthesis, and Characterization.

A class of compounds sharing the properties of 2D materials and electrolytes, namely 2D electrolytes is described theoretically and demonstrated experimentally. 2D electrolytes dissociate in different solvents, such as water, and become electrically charged. The chemical and physical properties of these compounds can be controlled by external factors, such as pH, temperature, electric permittivity of the medium, and ionic concentration. 2D electrolytes, in analogy with polyelectrolytes, present reversible morphological transitions from 2D to 1D, as a function of pH, due to the interplay of the elastic and Coulomb energies. Since these materials show stimuli-responsive behavior to the environmental conditions, 2D electrolytes can be considered as a novel class of smart materials that expand the functionalities of 2D materials and are promising for applications that require stimuli-responsive demeanor, such as drug delivery, artificial muscles, and energy storage.

Photothermia and Activated Drug Release of Natural Cell Membrane Coated Plasmonic Gold Nanorods and ß-Lapachone.

Plasmonic gold nanoparticles present extraordinary potential for near-infrared photothermal and triggered-therapeutic release treatments of solid tumors. In this study, we create a multifunctional nanocarrier in which PEG-coated gold nanorods are grouped into natural cell membrane vesicles (CM) from lung cancer (A549) cells and loaded with ß-lapachone (CM-ß-Lap-PEG-AuNRs). ß-Lapachone (ß-Lap) is an anticancer agent activated by the enzyme NADP(H):quinine oxidoreductase (NQO1), commonly found at higher levels in cancer cells. The irradiation with near-infrared (NIR) laser leads to disruption of the vesicles and release of the PEG-AuNRs and ß-Lap. The system presents an enhanced in vitro cytotoxicity against A549 cancer cells, which can be attributed to the specific cytotoxicity of ß-Lap combined with heat generated by laser irradiation of the AuNRs. In agreement, in vivo treatment with CM-ß-Lap-PEG-AuNRs and irradiation shows a histopathological recovery from nonmuscle invasive bladder cancer of most of the animals with only one cycle of application and irradiation. Such multifunctional platform is a promissing candidate for improved activated drug release and phototherapy.

Ultrasmall (<2 nm) Au@Pt Nanostructures: Tuning the Surface Electronic States for Electrocatalysis.

The ability to tune the electronic properties of nanomaterials has played a major role in the development of sustainable energy technologies. Metallic nanocatalysts are at the forefront of these advances. Their unique properties become even more interesting when we can control the distribution of the electronic states in the nanostructure. Here, we provide a comprehensive evaluation of the electronic surface states in ultrasmall metallic nanostructures by combining experimental and theoretical methods. The developed strategy allows the controlled synthesis of bimetallic nanostructures in the core-shell configuration, dispensing of the use of any surfactant or stabilizing agents, which usually inactivate important surface phenomena. The synthesized ultrasmall Au@Pt nanoarchitecture (∼1.8 nm) presents an enhanced performance catalyzing the hydrogen evolution reaction. First-principles calculations of projected and space-resolved local density of states of Au55@Pt92 (core-shell), Au55Pt92 (alloy), and Pt147 nanoparticles show a prominent increase in the surface electronic states for the core-shell bimetallic nanomaterial. It arises from a more-effective charge transfer from gold to the surface platinum atoms in the core-shell configuration. In pure Pt147 or Au55Pt92 alloy nanoparticles, a great part of the electronic states near the Fermi level is buried in the core atoms, disabling these states for catalytic applications. The proposed experimental-theoretical approach may be useful for the design of other systems composed of metallic nanoparticles supported on distinct substrates, such as two-dimensional materials and porous matrices. These nanomaterials find several applications not only in heterogeneous catalysis but also in sensing and optoelectronic devices.

Engineering two-dimensional gold nanostructures using graphene oxide nanosheets as a template.

The rich plasmon resonance modes and local field enhancements of two-dimensional (2D) noble metal nanostructures have boosted their application in distinct areas like catalysis, photonics, medicine and sensing. Here, we develop a unique strategy for the controlled growth of asymmetric 2D gold nanostructures in aqueous media using graphene oxide as a template. By performing mild reduction of gold ions on the surface of Au seeds (∼2 nm) attached to graphene oxide nanosheets, the anisotropic growth of 2D gold nanostructures can be carried out through a simple procedure with a tunable control of the final size, shape and thickness, and consequently on their optical properties, without using surfactants.

Toxicity of copper oxide nanoparticles to Neotropical species Ceriodaphnia silvestrii and Hyphessobrycon eques.

The increase of production and consumption of copper oxide nanostructures in several areas contributes to their release into aquatic ecosystems. Toxic effects of copper oxide nanoparticles (CuO NPs), in particular, on tropical aquatic organisms are still unknown, representing a risk for biota. In this study, the effects of rod-shaped CuO NPs on the Neotropical species Ceriodaphnia silvestrii and Hyphessobrycon eques were investigated. We also compared the toxicity of CuO NPs and CuCl2 on these species to investigate the contribution of particles and cupper ions to the CuO NPs toxicity. Considering the low copper ions release from CuO NPs (<1%), our results revealed that the toxicity of CuO NPs to C. silvestrii and H. eques was mainly induced by the NPs. The 48 h EC50 for C. silvestrii was 12.6 ±â€¯0.7 µg Cu L-1 and for H. eques the 96 h LC50 was 211.4 ±â€¯57.5 µg Cu L-1 of CuO NPs. There was significant decrease in reproduction, feeding inhibition and increase in reactive oxidative species (ROS) generation in C. silvestrii exposed to CuO NPs. In fish H. eques, sublethal exposure to CuO NPs caused an increase in ROS generation in gill cells and an increase in cells number that were in early apoptotic and necrotic stages. Our results showed that CuO NPs caused toxic effects to C. silvestrii and H. eques and ROS play an important role in the toxicity pathway observed. Data also indicated that C. silvestrii was among the most sensitive species for CuO NPs. Based on predicted environmental concentration in water bodies, CuO NPs pose potential ecological risks for C. silvestrii and H. eques and other tropical freshwater organisms.

Hot Hole Photoelectrochemistry on Au@SiO2@Au Nanoparticles.

There is currently a worldwide need to develop efficient photocatalytic materials that can reduce the high-energy cost of common industrial chemical processes. One possible solution focuses on metallic nanoparticles (NPs) that can act as efficient absorbers of light due to their surface plasmon resonance. Recent work indicates that small NPs, when photoexcited, may allow for efficient electron or hole transfer necessary for photocatalysis. Here we investigate the mechanisms behind hot hole carrier dynamics by studying the photodriven oxidation of citrate ions on Au@SiO2@Au core-shell NPs. We find that charge transfer to adsorbed molecules is most efficient at higher photon energies but still present with lower plasmon energy. On the basis of these experimental results, we develop a simple theoretical model for the probability of hot carrier-adsorbate interactions across the NP surface. These results provide a foundation for understanding charge transfer in plasmonic photocatalytic materials, which could allow for further design and optimization of photocatalytic processes.

Synthesis, Physico-Chemical Properties, and Biomedical Applications of Gold Nanorods--A Review.

The development of new systems for diagnostic and therapeutic applications is a topic of intense and growing interest. The unique optical and electronic properties exhibited by gold-based nanomaterials have proved to be valuable for a wide range of biomedical applications. Recently, great attention has been given to rod-shaped gold nanomaterials, especially because of their electronic absorption band in the near infrared region, where maximum radiation penetration through tissue occurs. This feature has allowed the use of gold nanorods for in vivo imaging, with different techniques, and photothermal therapy. Furthermore, gold nanorods can be functionalized with a wide variety of biomolecules for cancer cell targeting. Moreover, their versatility and unique properties have generated much enthusiasm in medicine. The present review aims to show the recent advances in the synthesis and applications of gold nanorods in medical areas.

Synthesis and characterization of jacalin-gold nanoparticles conjugates as specific markers for cancer cells.

New nanobiocomposites that combine nanoparticles and biomolecules have been shown very relevant for medical applications. Recently, cancer diagnostics and treatment have benefited from the development of nanobiocomposites, in which metallic or magnetic nanoparticles are conjugated with specific biomolecules for selective cell uptake. Despite recent advances in this area, the biomedical applications of these materials are still limited by the low efficiency of functionalization, low stability, among other factors. In this study, we report the synthesis of jacalin-conjugated gold nanoparticles, a nanoconjugate with potential application in medical areas, especially for cancer diagnosis. Jacalin is a lectin protein and it was employed due to its ability to recognize the Galß1-3GalNAc disaccharide, which is highly expressed in tumor cells. Gold nanoparticles (AuNPs) were synthesized in the presence of generation 4 polyamidoamine dendrimer (PAMAM G4) and conjugated with fluorescein isothiocyanate (FITC)-labeled jacalin. The AuNPs/jacalin nanoconjugates were characterized by transmission electron microscopy (TEM), dynamic light scattering (DLS) and vibrational spectroscopy (FTIR). We also performed an investigation using isothermal titration calorimetry (ITC) and fluorescence quenching measurements to understand the interactions occurring between the AuNPs and jacalin, which revealed that the nanoconjugate formation is driven by an entropic process with good affinity. Furthermore, in vitro tests revealed that the AuNPs/jacalin-FITC nanoconjugates exhibited higher affinity for leukemic K562 cells than for healthy mononuclear blood cells, which could be useful for biomedical applications, including cancer cells imaging.