Investigation of the LCST-Thermoresponsive Behavior of Novel Oligo(Ethylene Glycol)-Modified Pentafluorostyrene Homopolymers

Amphiphilic tetrafluorostyrene monomers (EFS8) carrying in the para position an oligoethylene glycol chain containing 8 oxyethylenic units on average were synthesized and used for preparation via activator regenerated by electron transfer atom transfer radical polymerization (ARGET-ATRP) of the corresponding amphiphilic homopolymers (pEFS8-x) with different degrees of polymerization (x = 26 and 46). Combining light transmittance and nano-differential scanning calorimetry (n-DSC) measurements revealed that pEFS8-x homopolymers displayed a lower critical solution temperature (LCST) thermoresponsive behavior in water solutions. Moreover, n-DSC measurements revealed the presence in heating scans of a broad endothermic peak ascribable to the dehydration process of the polymer single chains (unimers) and their collapse into aggregates. Consistently, dynamic light scattering (DLS) measurements showed below the LCST the presence of small nanostructures with a hydrodynamic diameter size Dh of 6–7 nm, which collapsed into concentration-dependent larger multichain aggregates (Dh = 300–3000 nm) above LCST. Interestingly, n-DSC data showed that the unimer-aggregate transition was reversible up to a specific temperature (Trev) of each homopolymer, which in any case was higher than Tmax. When heating above Trev the transition was no longer reversible, causing the shift of Tonset and Tmax at lower values, thus suggesting an increase in hydrophobicity of the polymer systems associated with a temperature-dependent dehydration process

Fast and Eco–friendly Microwave-Assisted Synthesis of Silver Nanoparticles using Rosemary Essential Oil as Renewable Reducing Agent

A green and fast methodology was developed to synthesize silver nanoparticlesusing rosemary essential oil (EO) as a renewable reducing agent. The synthesis process was microwave (MW) assisted, using acoaxialdipole antenna immersed into the reaction medium. This configuration was used to promote both: i) rosemary EO extraction by hydrodistillation, and ii) silver nanoparticle synthesis in an aqueous solution at atmosphericpressure. The effect of two different silver salt substrates and the time reaction on the morphology of the silver nanoparticles was explored. The coaxial microwave assisted hydrodistillation of rosemary yields 0.4%(w/w) in 30 min and contains ethers (17%), ketones (50%) and alcohols (15%). Silver nanoparticles with a tuneable particle size (from 7 to 18 nm) and morphology(from spherical to round-like shapes)were obtained in reaction times ranging from 2to 30 min. The nanoparticle formation was followed b yU V-vis spectroscopy and SEM imaging

Guidelines for a correct evaluation of deep eutectic solvents thermal stability

Deep eutectic solvents (DESs) are a class of versatile and green emerging materials. Despite the huge amounts of applications proposed in the last years, studies on their thermal stability are often missing. In this short review, we propose a guide for a correct evaluation of DES thermal stability, conducted mainly by dynamical thermogravimetry (TGA). We collected all the data reported in the literature on choline chloride (ChCl)-based DESs, as proof of concept to show the potentialities of the technique, highlighting all the parameters that need to be considered for a correct analysis, with particular attention to the possible sources of misleading interpretations (e.g. the adsorbed water, or the formation of undesired products during DES preparation). In many cases, the additional use of isothermal TGA, or TGA coupled with online techniques such as Fourier Infra-Red Spectroscopy or Mass Spectrometry, may help for the data interpretation. Besides, we summarize in a graph the degradation temperatures of many DESs and their precursors, intended as an operative guide to choosing the correct DES for different applications. The findings reported to date, highlight the potentialities of thermal analysis on DESs, as a powerful tool to obtain essential information on their applicability, and to implement the knowledge of their nanostructure from a molecular point of view

Thermal and morphological investigations of alkali activated materials based on Sicilian volcanic precursors (Italy)

Insights on thermal behavior and microstructures of AAMs based on Sicilian volcanic precursors (i.e., volcanic ash, "ghiara" and pumice) have been performed. A multidisciplinary approach by means of thermogravimetric analysis coupled to Fourier Transform Infrared Spectroscopy and X-ray Computed Microtomography has been used with the aim to define the influence of reactants involved in the process. The obtained results show: i) the increase of metakaolin shifts the gas emission toward lower temperatures; ii) the positive relation between mass loss and liquid/solid ratio; iii) the influence of particle size of precursors on the pore development

Thermodynamic Evaluation of the Interactions between Anticancer Pt(II) Complexes and Model Proteins

In this work, we have analysed the binding of the Pt(II) complexes ([PtCl(4′-phenyl-2,2′:6′,2″-terpyridine)](CF3SO3) (1), [PtI(4′-phenyl-2,2′:6′,2″-terpyridine)](CF3SO3) (2) and [PtCl(1,3-di(2-pyridyl)benzene) (3)] with selected model proteins (hen egg-white lysozyme, HEWL, and ribonuclease A, RNase A). Platinum coordination compounds are intensively studied to develop improved anticancer agents. In this regard, a critical issue is the possible role of Pt-protein interactions in their mechanisms of action. Multiple techniques such as differential scanning calorimetry (DSC), electrospray ionization mass spectrometry (ESI-MS) and UV-Vis absorbance titrations were used to enlighten the details of the binding to the different biosubstrates. On the one hand, it may be concluded that the affinity of 3 for the proteins is low. On the other hand, 1 and 2 strongly bind them, but with major binding mode differences when switching from HEWL to RNase A. Both 1 and 2 bind to HEWL with a non-specific (DSC) and non-covalent (ESI-MS) binding mode, dominated by a 1:1 binding stoichiometry (UV-Vis). ESI-MS data indicate a protein-driven chloride loss that does not convert into a covalent bond, likely due to the unfavourable complexes’ geometries and steric hindrance. This result, together with the significant changes of the absorbance profiles of the complex upon interaction, suggest an electrostatic binding mode supported by some stacking interaction of the aromatic ligand. Very differently, in the case of RNase A, slow formation of covalent adducts occurs (DSC, ESI-MS). The reactivity is higher for the iodo-compound 2, in agreement with iodine lability higher than chlorine

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

Insights into structural and dynamical features of water at halloysite interfaces probed by DFT and classical molecular dynamics simulations

Density functional theory calculations and classical molecular dynamics simulations have been used to investigate the structure and dynamics of water molecules on kaolinite surfaces and confined in the interlayer of a halloysite model of nanometric dimension. The first technique allowed us to accurately describe the structure of the tetrahedral–octahedral slab of kaolinite in vacuum and in interaction with water molecules and to assess the performance of two widely employed empirical force fields to model water/clay interfaces. Classical molecular dynamics simulations were used to study the hydrogen bond network structure and dynamics of water adsorbed on kaolinite surfaces and confined in the halloysite interlayer. The results are in nice agreement with the few experimental data available in the literature, showing a pronounced ordering and reduced mobility of water molecules at the hydrophilic octahedral surfaces of kaolinite and confined in the halloysite interlayer, with respect to water interacting with the hydrophobic tetrahedral surfaces and in the bulk. Finally, this investigation provides new atomistic insights into the structural and dynamical properties of water–clay interfaces, which are of fundamental importance for both natural processes and industrial applications