Metal N,N-dialkylcarbamates as easily available catalytic precursors for the carbon dioxide/propylene oxide coupling under ambient conditions

A series of previously reported homoleptic and non-homoleptic N,N-dialkylcarbamates of a range of non precious metals and N,N-dialkylcarbamate of Al(III) were investigated as easily available and inexpensive catalysts in the solventless synthesis of propylene carbonate (PC) from propylene oxide (PO) and CO2. By operating at atmospheric CO2 pressure at ambient temperature, excellent results were achieved using Ti(O2CNEt2)4, Al(O2CNR2)3 (R = Et, iPr), Cu(O2CNEt2)2 and Sn(O2CNEt2)4, in combination with NBu4X (X = Br or Cl) as a co-catalyst. The reactions of MCl2(O2CNEt2)2 (M = Ti, Zr) with amorphous silica were straightforward through partial release of both chlorido and carbamato ligands, and readily afforded solid materials which were characterized by ICP-OES and EDS analyses, coupled to SEM. These heterogeneous catalytic systems revealed less efficient than the homogeneous counterparts

Magneto-optical probe for investigation of multiphase fe oxide nanosystems

In iron oxide nanoparticles the transformation of the metastable magnetite phase to maghemite, through the oxidation of iron, often represents a major drawback for correct interpretation of their physical properties and their effective use in several applicative areas. To solve this issue we propose an innovative method for identifying the chemical composition of complex ferrite nanostructures based on magneto-optical (MO) spectroscopy. Spherical iron oxide nanoparticles with increasing size are investigated by magnetic circular dichroism (MCD) in the nUV-vis-nIR range (350-1000 nm). Particular attention is dedicated to the time evolution of the MO response, which is ascribable to the oxidation process of the nanomaterial. The measured MCD spectra show a complex line shape due to the overlap of several MO transitions. Deconvolution analysis of MCD hysteresis loops allows the interpretation of this complex response as the combination of two distinct contributions, originating from magnetite and maghemite domains in the nanoparticles. We consider this method a viable complement to conventional techniques for the discrimination of the two magnetic phases in nanostructured materials

NMR as evaluation strategy for cellular uptake of nanoparticles

Advanced nanostructured materials, such as gold nanoparticles, magnetic nanoparticles, and multifunctional materials, are nowadays used in many state-of-the-art biomedical application. However, although the engineering in this field is very advanced, there remain some fundamental problems involving the interaction mechanisms between nanostructures and cells or tissues. Here we show the potential of 1H NMR in the investigation of the uptake of two different kinds of nanostructures, that is, maghemite and gold nanoparticles, and of a chemotherapy drug (Temozolomide) in glioblastoma tumor cells. The proposed experimental protocol provides a new way to investigate the general problem of cellular uptake for a variety of biocompatible nanostructures and drugs. © 2014 American Chemical Society

Magnetothermally-responsive nanocarriers using confined phosphorylated halloysite nanoreactor for in situ iron oxide nanoparticle synthesis: a MW-assisted solvothermal approach

A family of easily recoverable magnetic and thermally responsive composite materials, with nanoscale dimensions, were synthesized by a rapid and simple solvothermal approach. The synthesis was thermally activated, accelerated, and controlled using a coaxial antenna to directly apply the microwave energy inside the solvothermal reactor. The composite materials were made up by a confined phosphorylated nanoreactor, namely halloysite nanotubes grafted on the inner lumen with phosphoric acid (HNTs-(H+-PO4)), that promoted the urea hydrolysis thus favoring the formation of a local alkaline environment to catalyze the homogeneous in situ precipitation of superparamagnetic iron oxide nanoparticles (IONs) selectively on their inner or outer surface. Two new MW-assisted solvothermal methodologies were used: 1) in the first the solvent is directly loaded into the MW-assisted reactor together with HNTs-(H+-PO4) mechanically preloaded with iron chloride and urea in the lumen 2) in the second the synthesis is preceded by a further pre-functionalization step of the iron salt with clove essential oil (EO) as a green functionalization agent. Structural, morphological, textural, and magnetic properties were assessed by TEM, N2 physisorption, TG-FTIR, ICP, XRD, magnetic and magnetic hyperthermia measurements. The MW-assisted solvothermal deposition of IONs was fully controlled using the phosphorylated nanoreactor, in short synthesis times, by a simple methodology following the principles of sustainable chemistry. IONs were selectively deposited on the outer surface or in the inner lumen of HNTs yielding easily recoverable superparamagnetic and thermally responsive nanocarriers suitable for applications like targeted hyperthermia therapy

Magnetophotonics for sensing and magnetometry toward industrial applications

Magnetic nanostructures sustaining different types of optical modes have been used for magnetometry and label-free ultrasensitive refractive index probing, where the main challenge is the realization of compact devices that are able to transfer this technology from research laboratories to smart industry. This Perspective discusses the state-of-the-art and emerging trends in realizing innovative sensors containing new architectures and materials exploiting the unique ability to actively manipulate their optical properties using an externally applied magnetic field. In addition to the well-established use of propagating and localized plasmonic fields, in the so-called magnetoplasmonics, we identified a new potential of the all-dielectric platforms for sensing to overcome losses inherent to metallic components. In describing recent advances, emphasis is placed on several feasible industrial applications, trying to give our vision on the future of this promising field of research merging optics, magnetism, and nanotechnology

Coexistence of plasmonic and magnetic properties in Au89Fe11 nanoalloys

We describe an environmentally friendly, top-down approach to the synthesis of Au89Fe11 nanoparticles (NPs). The plasmonic response of the gold moiety and the magnetism of the iron moiety coexist in the Au89Fe11 nanoalloy with strong modification compared to single element NPs, revealing a non-linear surface plasmon resonance dependence on the iron fraction and a transition from paramagnetic to a spin-glass state at low temperature. These nanoalloys are accessible to conjugation with thiolated molecules and they are promising contrast agents for magnetic resonance imaging

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