Nano-network with dual temperature and pH responsiveness based on copolymers of 2-hydroxyethyl methacrylate with 3,9-divinyl-2,4,8,10-tetraoxaspiro[5.5]-undecane

Abstract  

This study refers to the synthesis of a nano-network with dual temperature and pH responsiveness based on the 2-hydroxyethyl methacrylate (HEMA) copolymers with a comonomer with spiroacetal moiety and crosslinking capacity, namely 3,9-divinyl-2,4,8,10-tetraoxaspiro[5.5]-undecane (U). The copolymers were synthesized by radical emulsion polymerization, using 4,4′-azobis(cyanopentanoic acid) as initiator, in the presence of sodium lauryl sulfate as tensioactive agent and poly(vinyl alcohol) as protective colloid. Three copolymer variants were taken into study resulted from the different ratio between the comonomers (HEMA/U), which was about 98/2, 95/5, and 90/10, respectively. The copolymers were characterized by FTIR and thermal analysis. The copolymers sensitivity was evidenced by studying the evolution of the hydrodynamic radius and zeta potential of the polymeric particles as a function of pH. Thus, the particles size increases with the comonomer amount, from 193 nm in case of the homopolymer up to 253 nm for the copolymer with maximum content of the comonomer (10%). The increase of the particle hydrodynamic radius with the growth of temperature was also put into evidence.     

Magnetic resonance imaging follow-up of liver growth of neuroendocrine tumors in an experimental mouse model

Liver metastases in patients with gastroenteropancreatic (GEP) endocrine tumors represent the main factor of adverse prognosis in this tumor type and thus have a strong effect on the therapeutic strategies. Currently, magnetic resonance imaging (MRI) is considered the modality of choice for the noninvasive, in vivo detection of liver metastases. Dedicated MRI protocols suitable for following liver lesion evolution on an experimental model of endocrine tumors could be valuable. An experimental animal model mimicking the clinical situation of intrahepatic dissemination has been designed. The goal of this study was to characterize liver lesions in this athymic nude mouse model and assess the detection sensitivity of MRI using a physiological gating strategy optimized for high magnetic fields.     

Influence of topography on ground deformation at Mt. Vesuvius (Italy) by finite element modelling

Ground deformations are observed in connection with volcanic activity, and therefore, geodetic monitoring can provide significant indication of changes of equilibrium conditions. The aim of this paper is to study the deformation of Mount Vesuvius (Italy) caused by overpressure sources at various depths, using a commercial (Ansys) 3D finite element code, in the framework of linear elastic isotropic material behavior. Both homogenous and heterogeneous media with carbonate basement were analyzed to understand the influence of topography on the ground deformations. The topography of the Somma-Vesuvius was taken into account, using a digital terrain model, and the carbonate basement was schematically modelled by assuming two horizontal layers with different Young moduli. The presence of a strong deviation from axially symmetric pattern of the displacement field, and of small subsidence areas, was found. These characteristics are completely unknown from the simple Mogi model and by simplified topography model, as verified by ad hoc simulations. These preliminary results, showing areas of the volcanic edifice experiencing high deformation, can improve the determination of the sources of deformations, i.e. the most relevant problem in the volcano monitoring. Moreover, the knowledge of the deformation pattern, including the topography effects, can provide significant indications to optimize the location of sensors and the characteristics needed to design an efficient and reliable geodetic monitoring network able to detect shallow intrusion events.     

Model based,pulling rate,thermal and capillary conditions setting for silicon tube growth

In this paper a mathematical model based procedure for setting of pulling rate, capillary and thermal conditions to grow a silicon tube with prior established inner and outer radius by shaped growth with the catching boundary condition is presented. The model is defined by a set of three differential equations governing the evolution of outer radius, inner radius and the crystallization front level. The right hand members of the system of differential equations serve as tools for setting the above parameters. Numerical illustration and simulation of the growth process are presented.     

Palladium-catalyzed synthesis of 2-amino ketones from propargylic carbonates and secondary amines

A novel palladium-catalyzed approach to 2-amino ketones from arylpropargylic carbonates bearing neutral, electron-rich, and electron-poor aromatic rings and cyclic secondary amines containing useful functional groups such as cyano, chloro, and bromo substituents has been developed.     

Atomic force microscopy: A nanoscopic view of microbial cell surfaces

The atomic force microscope (AFM) is a powerful instrument for microbiological investigation. It has evolved from an imaging tool used to investigate microbial surfaces at high resolution in their physiological environment into a lab-on-a-tip device, which allows more quantitative analysis of biological samples (from molecules to cells) in aqueous liquids. Atomic force microscopy provides information about the nanoscale architecture of microbes and about the localization and interactions of their individual constituents. Microbial interactions play essential roles in biology, medicine, ecology, biotechnology, food science and contribute to phenomena as varied as bacterial infections, biofilm formation, and bacterial adhesion to surfaces. In this review, we focus on recent developments offered by the rapid advances in AFM imaging and force spectroscopy with emphasizes on microbial research.     

Exceptionally low shear modulus in a prototypical imidazole-based metal-organic framework

Using Brillouin scattering, we measured the single-crystal elastic constants (C(ij)'s) of a prototypical metal-organic framework (MOF): zeolitic imidazolate framework (ZIF)-8 [Zn(2-methylimidazolate)(2)], which adopts a zeolitic sodalite topology and exhibits large porosity. Its C(ij)'s under ambient conditions are (in GPa) C(11)=9.522(7), C(12)=6.865(14), and C(44)=0.967(4). Tensorial analysis of the C(ij)'s reveals the complete picture of the anisotropic elasticity in cubic ZIF-8. We show that ZIF-8 has a remarkably low shear modulus G(min) < or approximately 1 GPa, which is the lowest yet reported for a single-crystalline extended solid. Using ab initio calculations, we demonstrate that ZIF-8's C(ij)'s can be reliably predicted, and its elastic deformation mechanism is linked to the pliant ZnN(4) tetrahedra. Our results shed new light on the role of elastic constants in establishing the structural stability of MOF materials and thus their suitability for practical applications.     

Mechanics: Non-classical, Non-quantum

A non-classical, non-quantum theory, or NCQ, is any fully consistent theory that differs fundamentally from both the corresponding classical and quantum theories, while exhibiting certain features common to both. Such theories are of interest for two primary reasons. Firstly, NCQs arise prominently in semi-classical approximation schemes. Their formal study may yield improved approximation techniques in the near-classical regime. More importantly for the purposes of this note, it may be possible for NCQs to reproduce quantum results over experimentally tested regimes while having a well defined classical limit, and hence are viable alternative theories. We illustrate an NCQ by considering an explicit class of NCQ mechanics. Here this class will be arrived at via a natural generalization of classical mechanics formulated in terms of a probability density functional.     

Supramolecular Chirality in Solvent‐Promoted Aggregation of Amphiphilic Porphyrin Derivatives: Kinetic Studies and Comparison between Solution Behavior and Solid‐State Morphology by AFM Topography

The solvent‐promoted aggregation behavior of some amphiphilic porphyrin derivatives bearing chiral functionality in the form of a charged L ‐proline group has been investigated by UV/Vis, resonance light scattering, fluorescence and circular dichroism spectroscopy. The investigated macrocycles give rise to aggregates featuring supramolecular chirality with high ellipticity. Kinetic studies reveal peculiar differences in the fashion of aggregation, depending on the intimate nature of the chiral functionality, namely, cationic (nitrogen‐quaternized L ‐proline, 3H₂ ) or anionic (carboxylate residue, 6H₂ ) group. Formation of anionic 6H₂ aggregates shows a diffusion‐limited kinetic behavior. AFM topography studies show formation of tighter globular structures. On the other hand, the corresponding 3H₂ aggregates are formed by a cooperative, fractal‐type decay, and appear as long‐fibrous, looser structures. In the templated aggregation of 3H₂ over preformed 6H₂ aggregates, AFM images show formation of globular structures with reduced sizes, as a likely consequence of shorter interchromophore distances, due to favorable Coulombic interactions. The results obtained show an interesting parallelism between the solution behavior and the solid‐state aggregate structures, corroborating the sergeant–soldier effect observed in the templated aggregation. The results presented give important insights for understanding the complex mechanisms involved in these issues, which are of key importance for the development of chiral supramolecular materials and stereoselective sensors and devices.     

Bloch wave homogenization of a non-homogeneous Neumann problem

In this paper, we use the Bloch wave method to study the asymptotic behavior of the solution of the Laplace equation in a periodically perforated domain, under a non-homogeneous Neumann condition on the boundary of the holes, as the size of the holes goes to zero more rapidly than the domain period. This method allows to prove that, when the hole size exceeds a given threshold, the non-homogeneous boundary condition generates an additional term in the homogenized problem, commonly referred to as “the strange term” in the literature.