Gadolinium‐Decorated Silica Microspheres as Redox‐Responsive MRI Probes for Applications in Cell Therapy Follow‐Up

The redox microenvironment within a cell graft can be considered as an indicator to assess whether the graft is metabolically active or hypoxic. We present a redox‐responsive MRI probe based on porous silica microparticles whose surface has been decorated with a Gd‐chelate through a disulphide bridge. Such microparticles are designed to be interspersed with therapeutic cells within a biocompatible hydrogel. The onset of reducing conditions within the hydrogel is paralleled by an increased clearance of Gd, that can be detected by MRI.     

Modelling the soundscape quality of urban waterfronts by artificial neural networks

The renewal of the urban waterfronts has become a major focus of attention for politicians and decision makers in the city’s management programs. The recognition of the patterns that define the waterfronts’ identity is essential to select new strategies of intervention for the environmental recovery. In order to create adequate environments for everyday life within a sustainable development, new links between human senses, human perception and design need to be created. Within this wide approach, the landscape and the soundscape play a significant role and can become a key driving force in the implementation of the changes. New techniques have to be tested to identify the sonic and visual parameters capable to explain the specificity of a waterfront. With this purpose, an artificial neural network (ANN) was developed, and the relative importance of the input variables was evaluated. The collected database was also analysed by multiple linear regression (MLR) to compare the outcomes of both models. The urban waterfront of Naples (Italy) was chosen as case study. The results obtained show that the performance of the neural network is better than the one of the linear regression (rANN = 0.949, rMLR = 0.639). The interpretation of the relative importance method is also quite satisfactory in the ANN.     

Lanthanide Identity Governs Guest-Induced Dimerization in LnIII[15-MC N(L-pheHA)-5])3+ Metallacrowns

Series of lanthanide-containing metallic coordination complexes are frequently presented as structurally analogous, due to the similar chemical and coordinative properties of the lanthanides. In the case of chiral (Ln^III[15-MC _N(L-pheHA)-5])³⁺ metallacrowns (MCs), which are well established supramolecular hosts, the formation of dimers templated by a dicarboxylate guest (muconate) in solution of neutral pH is herein shown to have a unique dependence on the identity of the MC's central lanthanide. Calorimetric data and nuclear magnetic resonance diffusion studies demonstrate that MCs containing larger or smaller lanthanides as the central metal only form monomeric host-guest complexes whereas analogues with intermediate lanthanides (for example, Eu, Gd, Dy) participate in formation of dimeric host-guest-host compartments. The driving force for the dimerization event across the series is thought to be a competition between formation of highly stable MCs (larger lanthanides) and optimally linked bridging guests (smaller lanthanides).     

Field Study on Mobility and Persistence of Linuron and Monolinuron in Agricultural Soil

Abstract

A field site equipped with suction cup lysimeters was installed at Treviglio (BG) to assess the migration capacity of the herbicides linuron and monolinuron from topsoil to groundwater and to verify the appearance of their relevant transformation products in soil and water samples. A constant hydraulic head was applied in order to develop water saturation conditions in the upper layers. KCl was used as a tracer to evaluate water infiltration velocity through the vertical soil profile. The constant hydraulic head accelerated infiltration rates, while herbicide concentrations reached maximum contamination because soil adsorption capacity was underdeveloped. The results indicated two main processes of pesticide transport: firstly transport due mainly to water infiltration through macropores; secondly the transport driven by matrix flow. Linuron was found to be the most mobile herbicide, while chloroanilines were found to be the major transformation products of the herbicides considered.     

A Singular Limit Problem for Conservation Laws Related to the Camassa–Holm Shallow Water Equation

We consider a shallow water equation of the Camassa–Holm type, which contains nonlinear dispersive effects as well as fourth order dissipative effects. We prove that as the diffusion and dispersion parameters tend to zero, with a condition on the relative balance between these two parameters, smooth solutions of the shallow water equation converge to discontinuous weak solutions of a scalar conservation law. The proof relies on deriving suitable a priori estimates together with an application of the compensated compactness method in the L ^p setting.     

Modifying LnHPDO3A Chelates for Improved T1 and CEST MRI Applications

The new ligand HPDO3MA [(R,R,R,R)-10-(2-hydroxypropyl)-α,α′,α′′-trimethyl-1,4,7,10-tetraazacyclododecane-1,4,7-triacetic acid] was designed to combine and optimize the chemical properties of the macrocyclic ligands HPDO3A and DOTMA. The presence of the methyl groups on the acetic pendant arms of HPDO3A is expected to rigidify the structure of the ligand and favor an increase of the kinetic inertness of the Ln complexes. ¹H NMR spectra of Eu(HPDO3MA) displayed the presence of two pairs of diastereoisomers: SAP (square antiprismatic) and TSAP (twisted square antiprismatic) isomers (56 and 44 %, respectively). In addition, ¹H and ¹⁷O relaxometric NMR studies of Gd(HPDO3MA) showed approximately a 10 % increase in relaxivity and a faster water exchange rate with respect to Gd(HPDO3A). Moreover, a detailed chemical exchange saturation transfer (CEST) characterization of Yb(HPDO3MA) displayed a sensitivity about two times larger than that of Yb(HPDO3A) both in phantom and in cell labeling experiments. Finally, the kinetic inertness of Yb(HPDO3MA) was measured to be twice as high as that of Yb(HPDO3A), with a dissociation half-life at physiological pH of about 2500 years.     

Comparison between preparative methodologies of nanostructured carbon nitride and their use as selective photocatalysts in water suspension

Carbon nitride photocatalysts have been prepared by different methodologies, such as chemical ultrasonic irradiation (sonochemical treatment), hydrothermal and ball milling and thermoexfoliation, and have been used for the selective oxidation of 5-hydroxymethyl-2-furaldehyde (HMF) to form 2,5-furandicarboxyaldehyde (FDC) in water suspension both under UV and natural solar irradiation. The physico-chemical features of the photocatalysts have been studied by X-ray diffraction, infrared spectroscopy, UV–Vis diffuse reflectance spectroscopy, photoluminescence spectroscopy, scanning electron microscopy, and specific surface area measurements. The results indicate that exfoliation of carbon nitrides can increase the conversion of HMF and the selectivity to FDC. In particular, samples exfoliated by both thermal and acidic ultrasonic irradiation treatments showed the best photocatalytic performance.