Long-Term Accumulation, Biological Effects and Toxicity of BSA-Coated Gold Nanoparticles in the Mouse Liver, Spleen, and Kidneys.

Introduction: Gold nanoparticles are promising candidates as vehicles for drug delivery systems and could be developed into effective anticancer treatments. However, concerns about their safety need to be identified, addressed, and satisfactorily answered. Although gold nanoparticles are considered biocompatible and nontoxic, most of the toxicology evidence originates from in vitro studies, which may not reflect the responses in complex living organisms. Methods: We used an animal model to study the long-term effects of 20 nm spherical AuNPs coated with bovine serum albumin. Mice received a 1 mg/kg single intravenous dose of nanoparticles, and the biodistribution and accumulation, as well as the organ changes caused by the nanoparticles, were characterized in the liver, spleen, and kidneys during 120 days. Results: The amount of nanoparticles in the organs remained high at 120 days compared with day 1, showing a 39% reduction in the liver, a 53% increase in the spleen, and a 150% increase in the kidneys. The biological effects of chronic nanoparticle exposure were associated with early inflammatory and fibrotic responses in the organs and were more pronounced in the kidneys, despite a negligible amount of nanoparticles found in renal tissues. Conclusion: Our data suggest, that although AuNPs belong to the safest nanomaterial platforms nowadays, due to their slow tissue elimination leading to long-term accumulation in the biological systems, they may induce toxic responses in the vital organs, and so understanding of their long-term biological impact is important to consider their potential therapeutic applications.

Bifunctional Au-Sn-SiO2 catalysts promote the direct upgrading of glycerol to methyl lactate.

Valuable alkyl lactates can be obtained from (waste) glycerol, through a two-step process that entails (i) the oxidation of glycerol to dihydroxyacetone (DHA) catalyzed by support Au nanoparticles and (ii) a rearrangement of DHA with an alcohol effectively catalyzed by Sn-based heterogeneous catalysts. To solve selectivity and processing issues we propose to run the process as a cascade reaction, in one step, and with a single bifunctional catalyst. Tackling the challenge associated with the preparation of such bifunctional catalysts, here, an aerosol-assisted sol-gel route is exploited. The catalysts feature small Au nanoparticles (3-4 nm) embedded at the surface of mesoporous Sn-doped silica microspheres. The preparation successfully leads to insert both active sites in their most active forms, and in close proximity. With the bifunctional catalysts, the yield for the final product of the cascade reaction (methyl lactate) is higher than the DHA yield when only the first reaction is carried out. This highlights a beneficial substrate channeling effect which alleviates side reactions. Interestingly, the bifunctional catalysts also markedly outcompeted mechanical mixtures of the corresponding monofunctional Au- and Sn-based catalysts. Thus, the spatial proximity between the two active sites in bifunctional catalysts is identified as a key to stir the cascade reaction towards high lactate yield.

Propylene Metathesis over Molybdenum Silicate Microspheres with Dispersed Active Sites.

In this work, we demonstrate that amorphous and porous molybdenum silicate microspheres are highly active catalysts for heterogeneous propylene metathesis. Homogeneous molybdenum silicate microspheres and aluminum-doped molybdenum silicate microspheres were synthesized via a nonaqueous condensation of a hybrid molybdenum biphenyldicarboxylate-based precursor solution with (3-aminopropyl)triethoxysilane. The as-prepared hybrid metallosilicate products were calcined at 500 °C to obtain amorphous and porous molybdenum silicate and aluminum-doped molybdenum silicate microspheres with highly dispersed molybdate species inserted into the silicate matrix. These catalysts contain mainly highly dispersed MoOx species, which possess high catalytic activity in heterogeneous propylene metathesis to ethylene and butene. Compared to conventional silica-supported MoOx catalysts prepared via incipient wetness impregnation (MoIWI), the microspheres with low Mo content (1.5-3.6 wt %) exhibited nearly 2 orders of magnitude higher steady-state propylene metathesis rates at 200 °C, approaching site time yields of 0.11 s-1.

Ethanol Dehydrogenation over Copper-Silica Catalysts: From Sub-Nanometer Clusters to 15 nm Large Particles.

Non-oxidative ethanol dehydrogenation is a renewable source of acetaldehyde and hydrogen. The reaction is often catalyzed by supported copper catalysts with high selectivity. The activity and long-term stability depend on many factors, including particle size, choice of support, doping, etc. Herein, we present four different synthetic pathways to prepare Cu/SiO2 catalysts (∼2.5 wt % Cu) with varying copper distribution: hydrolytic sol-gel (sub-nanometer clusters), dry impregnation (A̅ = 3.4 nm; σ = 0.9 nm and particles up to 32 nm), strong electrostatic adsorption (A̅ = 3.1 nm; σ = 0.6 nm), and solvothermal hot injection followed by Cu particle deposition (A̅ = 4.0 nm; σ = 0.8 nm). All materials were characterized by ICP-OES, XPS, N2 physisorption, STEM-EDS, XRD, RFC N2O, and H2-TPR and tested in ethanol dehydrogenation from 185 to 325 °C. The sample prepared by hydrolytic sol-gel exhibited high Cu dispersion and, accordingly, the highest catalytic activity. Its acetaldehyde productivity (2.79 g g-1 h-1 at 255 °C) outperforms most of the Cu-based catalysts reported in the literature, but it lacks stability and tends to deactivate over time. On the other hand, the sample prepared by simple and cost-effective dry impregnation, despite having Cu particles of various sizes, was still highly active (2.42 g g-1 h-1 acetaldehyde at 255 °C). Importantly, it was the most stable sample out of the studied materials. The characterization of the spent catalyst confirmed its exceptional properties: it showed the lowest extent of both coking and particle sintering.

CO2 Hydrogenation to Methanol with Ga- and Zn-Doped Mesoporous Cu/SiO2 Catalysts Prepared by the Aerosol-Assisted Sol-Gel Process*.

The preparation of copper-based heterogeneous catalysts dedicated to the hydrogenation of CO2 to methanol typically relies on multi-step procedures carried out in batch. These steps are precisely tailored to introduce the active phase (Cu) and the promoters (e. g., zinc, gallium) onto a preformed support to maximize catalyst performance. However, each process step can be associated with the formation of waste and with the consumption of energy, thereby negatively impacting the environmental performance of the overall catalyst preparation procedure. Here, a direct and continuous production process is proposed for the synthesis of efficient catalysts for the CO2 -to-methanol reaction. Gallium- and zinc-promoted mesoporous Cu-SiO2 catalysts were prepared in one step by the aerosol-assisted sol-gel process. The catalysts consisted of spherical microparticles and featured high specific surface area and pore volume, with interconnected pores of about 6 nm. A strong promoting effect of Ga and Zn was highlighted, boosting the selectivity for methanol at the expense of CO. Upon calcination, it was shown that Cu species (initially trapped in the silica matrix) underwent a migration towards the catalyst surface and a progressive sintering. After optimization, the catalysts obtained via such direct, continuous, simple, and scalable route could compete with the best catalysts reported in the literature and obtained via multi-step approaches.

Morphology Control in AgCu Nanoalloy Synthesis by Molecular Cu(I) Precursors.

As nanoparticle preparation methods employing bottom-up procedures rely on the use of molecular precursors, the chemical composition and bonding of these precursors have a decisive effect on nanoparticle formation and their resulting morphology and properties. We synthesized the Cu(I) complexes [Cu(PPh3)2(bea)] (1, bea = benzoate) and [Cu(PPh3)3(Hphta)] (2, phta = phthalate) by reducing the corresponding Cu(II) mono- and dicarboxylates with triphenylphosphine. We characterized 1 and 2 by single-crystal X-ray diffraction analysis, elemental analyses, infrared and nuclear magnetic resonance spectroscopy, and mass spectrometry and obtained complete information about their structures in the solid state and in solution. Also, we examined their thermal stability in oleylamine and determined their decomposition temperatures to be used as the minimal reaction temperature in metal nanoparticle synthesis. The complexes 1 and 2 differ in the number of reducing PPh3 ligands and the strength of carboxylate bonding to the Cu(I) center. Therefore, we employed them in combination with [Ag(NH2C12H25)2]NO3 as molecular precursors in the solvothermal hot injection synthesis of AgCu nanoalloys in oleylamine and demonstrated their influence on the elemental distribution, phase composition, particle size distribution, shape, morphology, and optical properties of the resulting nanoparticles. The nanoalloy particles from the benzoate complex 1 were oblate and polydisperse and exhibited two surface plasmons at 393 and 569 nm, which is caused by their Janus-type structure. The nanoparticles prepared from the phthalate complex 2 were round and monodisperse and exhibited one plasmon at 413 nm, as they formed an AgCu solid solution with a random distribution of the elements in a particle.

Comparing the acidities of aqueous, frozen, and freeze-dried phosphate buffers: Is there a "pH memory" effect?

The concept of "pH memory" has been established in the literature for the correlation between the pH of a pre-lyophilization solution and the ionization state of freeze-dried powder (lyophile). In this paper, the concept of "pH memory" is explored for the system of an aqueous solution, a frozen solution, and a lyophile. Sodium and potassium phosphate buffers in the pH range of 5-9 were frozen and lyophilized with sulfonephthalein indicators as acidity probes, and their Hammett acidity functions were compared to the initial pH of the aqueous solution. The results show that the acidities of the lyophiles are somewhat changed compared to the initial pHs, but the acidities in the frozen state differ more substantially. The Hammett acidity functions of the frozen buffers were found to be markedly dissimilar from the initial pH, especially in the sodium phosphate frozen at 233K, where an increase in the initial pH led to a decrease in the Hammett acidity function of the frozen state at a certain pH range. The large acidification observed after freezing the sodium phosphate buffer was not detected in the lyophiles after the sample had been dried; the phenomenon is explained considering the formed crystals analyzed by X-ray powder diffraction. The results suggest that monitoring the final acidity of a lyophile is not sufficient to predict all the acidity changes throughout the whole lyophilization process. The importance of well-controlled freezing and lyophilization conditions follows from the results of the research.

Heat-induced spinodal decomposition of Ag-Cu nanoparticles.

Solvothermal synthesis was used for Ag-Cu nanoparticle (NP) preparation from metallo-organic precursors. The detailed NP characterization was performed to obtain information about nanoparticle microstructure and both phase and chemical compositions. The resulting nanoparticles exhibited chemical composition inside a FCC_Ag + FCC_Cu two-phase region. The microstructure study was performed by various methods of electron microscopy including high-resolution transmission electron microscopy (HRTEM) at an atomic scale. The HRTEM and X-ray diffraction studies showed that the prepared nanoparticles form the face centred cubic (FCC) crystal lattice where the silver atoms are randomly mixed with copper. The CALPHAD approach was used for predicting the phase diagram of the Ag-Cu system in both macro- and nano-scales. The predicted spinodal decomposition of the metastable Ag-Cu nanoparticles was experimentally induced by heating on an X-ray powder diffractometer (HT XRD). The nucleation of the Cu-rich phase was detected and its growth was studied. Changes in the Ag-rich phase were observed in situ by X-ray diffraction under vacuum. The heat treatment was conducted at different maximum temperatures up to 450 °C and the resulting particle product was analysed. The experiments were complemented by differential scanning calorimetry (DSC) measurements up to liquidus temperature. The start temperatures of the spinodal phase transformation and particle aggregation were evaluated.