Marine Exopolysaccharide Complexed With Scandium Aimed as Theranostic Agents

(1) Background: Exopolysaccharide (EPS) derivatives, produced by Alteromonas infernus bacterium, showed anti-metastatic properties. They may represent a new class of ligands to be combined with theranostic radionuclides, such as ⁴⁷Sc/⁴⁴Sc. The goal of this work was to investigate the feasibility of such coupling. (2) Methods: EPSs, as well as heparin used as a drug reference, were characterized in terms of molar mass and dispersity using Asymmetrical Flow Field-Flow Fractionation coupled to Multi-Angle Light Scattering (AF4-MALS). The intrinsic viscosity of EPSs at different ionic strengths were measured in order to establish the conformation. To determine the stability constants of Sc with EPS and heparin, a Free-ion selective radiotracer extraction (FISRE) method has been used. (3) Results: AF4-MALS showed that radical depolymerization produces monodisperse EPSs, suitable for therapeutic use. EPS conformation exhibited a lower hydrodynamic volume for the highest ionic strengths. The resulting random-coiled conformation could affect the complexation with metal for high concentration. The LogK of Sc-EPS complexes have been determined and showing that they are comparable to the Sc-Hep. (4) Conclusions: EPSs are very promising to be coupled with the theranostic pair of scandium for Nuclear Medicine.     

Hydrogen oxidation near the second explosion limit in a flow reactor

This work investigates the oxidation of hydrogen near its second explosion limit in a turbulent flow reactor at pressures of 1 to 8 bar, temperatures of 950 K and an equivalence ratio of 0.035. The concentrations of H₂, O₂ and H₂O are measured along the reactor and simulated using several kinetic models from the literature. These experiments demonstrate evident negative pressure dependence from roughly 1 to 4 bar, with further increases in pressure resuming its positive impact on reaction rates. The simulated and measured species concentrations along the reactor generally agree within a factor of 2.Further investigation is then conducted to measure the rate coefficient of reaction H + O₂ (+ M) = HO₂ (+M) (R2), which is one of the most sensitive reactions in hydrogen's oxidation chemistry at these conditions. This investigation is conducted by using nitric oxide (NO) as a dopant and measuring the resulting, quasi-steady-state concentrations of NO₂. The rate coefficients are obtained at 950 – 1010 K. Combined with literature results, an Arrhenius expression is proposed, $k_{2,0}^{N_2}$ = 4.50 × 10²⁰ (T/K)^?1.73 [cm⁶ mole^?2 s^?1], for the reaction rate at the low-pressure limit over 500 K – 2000 K with N₂ as the bath gas. Simulations using the models from the literature with the proposed Arrhenius expression for this reaction then demonstrate improved agreement with the experiments.     

New ion exchange membrane derived from sulfochlorated polyether sulfone for electrodialysis desalination of brackish water

The purpose of this work is to study the desalination of brackish water using a new ion exchange membrane, made from sulfochlorated polyethersulfone (Cl‐PES), and crosslinked using aminated polyethersulfone (NH2‐PES) as a crosslinking reagent. This membrane, named ClNH2 membrane, has been obtained by reaction between Cl‐PES with 1.3 SO₂Cl groups per monomer unit and 0.2 equivalent amount of NH2‐PES. ClNH2 membrane has been characterized in terms of contact angle, transport number, intrinsic conductivity, and water uptake (as a function of temperature). Electrodialysis performances of the newly synthetized membranes have been measured using an electrodialysis cell at a laboratory scale and compared to commercial membranes. All the experiments have been performed using synthetic brackish water solutions prepared from sodium chloride salts with different concentrations (varying from 0.5 to 5.0 g/L). The concentration of different water samples obtained has been found to be below the amount recommended by the World Health Organization (WHO) for drinking water.     

Tailoring the Structure of Two‐Dimensional Self‐Assembled Nanoarchitectures Based on NiII–Salen Building Blocks

The synthesis of a series of Ni^II–salen‐based complexes with the general formula of [Ni(H₂L)] (H₄L=R²‐N,N′‐bis[R¹‐5‐(4′‐benzoic acid)salicylidene]; H₄L1: R²=2,3‐diamino‐2,3‐dimethylbutane and R¹=H; H₄L2: R²=1,2‐diaminoethane and R¹=tert‐butyl and H₄L3: R²=1,2‐diaminobenzene and R¹=tert‐butyl) is presented. Their electronic structure and self‐assembly was studied. The organic ligands of the salen complexes are functionalized with peripheral carboxylic groups for driving molecular self‐assembly through hydrogen bonding. In addition, other substituents, that is, tert‐butyl and diamine bridges (2,3‐diamino‐2,3‐dimethylbutane, 1,2‐diaminobenzene or 1,2‐diaminoethane), were used to tune the two‐dimensional (2D) packing of these building blocks. Density functional theory (DFT) calculations reveal that the spatial distribution of the LUMOs is affected by these substituents, in contrast with the HOMOs, which remain unchanged. Scanning tunneling microscopy (STM) shows that the three complexes self‐assemble into three different 2D nanoarchitectures at the solid–liquid interface on graphite. Two structures are porous and one is close‐packed. These structures are stabilized by hydrogen bonds in one dimension, while the 2D interaction is governed by van der Waals forces and is tuned by the nature of the substituents, as confirmed by theoretical calculations. As expected, the total dipolar moment is minimized     

Direct Oxidative Coupling of N‐Acetyl Indoles and Phenols for the Synthesis of Benzofuroindolines Related to Phalarine

Inspired by the biogenetic synthesis of benzofuroindoline‐containing natural products, we designed an oxidative coupling between phenol and N‐acetyl indoles. This straightforward and direct radical process, mediated by 2,3‐dichloro‐5,6‐dicyano‐1,4‐benzoquinone and FeCl₃ allowed the regioselective synthesis of benzofuro[3,2‐b]indolines, whose structure is found in the natural product phalarine.     

Effective Utilization of NIR Wavelengths for Photo‐Controlled Polymerization: Penetration Through Thick Barriers and Parallel Solar Syntheses

This contribution details an efficient and controlled photopolymerization regulated by far‐red (λ=680 nm) and NIR (λ=780 and 850 nm) light in the presence of aluminium phthalocyanine and aluminium naphthalocyanine. Initiating radicals are generated by photosensitization of peroxides affording an effective strategy that provides controlled polymerization of a variety of monomers with excellent living characteristics. Critically, long wavelength irradiation provides penetration through thick barriers, affording unprecedented rates of controlled polymerization that can open new and exciting applications. Furthermore, a more optimized approach to performing solar syntheses is presented. By combining the narrow Q‐bands of these photocatalysts with others possessing complementary absorptions, layered, independent polymerizations and organic transformations may be performed in parallel under a single broadband emission source, such as sunlight.     

Advances on the Determination of the Astatine Pourbaix Diagram: Predomination of AtO(OH)2− over At− in Basic Conditions

It is generally assumed that astatide (At^?) is the predominant astatine species in basic aqueous media. This assumption is questioned in non‐complexing and non‐reductive aqueous solutions by means of high‐pressure anion‐exchange chromatography. Contrary to what is usually believed, astatide is found to be a minor species at pH=11. A different species, which also bears a single negative charge, becomes predominant when the pH is increased beyond 7. Using competition experiments, an equilibrium constant value of 10^?6.9 has been determined for the formation of this species from AtO(OH) with the exchange of one proton. The identification of this species, AtO(OH)₂^?, is achieved through relativistic quantum mechanical calculations, which rule out the significant formation of the AtO₂^? species, while leading to a hydrolysis constant of AtO(OH) in excellent agreement with experiment when the AtO(OH)₂^? species is considered. Beyond the completion of the Pourbaix diagram of astatine, this new information is of interest for the development of ²¹¹At radiolabeling protocols.     

Stepwise and concerted electron-transfer/bond breaking reactions. solvent control of the existence of unstable pi ion radicals and of the activation barriers of their heterolytic cleavage

Available data from various sources seem to indicate an important role of solvation in the cleavage rates of intermediate pi ion radicals, in the passage from concerted to stepwise electron-transfer/bond breaking reaction pathways and even in the very existence of pi ion radicals. After preliminary computations treating the solvent as dielectric continuum, these expectations are examined with the help of a simple model system involving the anion radical of ONCH(2)Cl and two molecules of water, which allows the application of advanced computational techniques and a treatment of these solvent effects that emphasizes the role of solvent molecules that sit close to the charge centers of the molecule. A pi ion radical minimum indeed appears upon introduction of the two water molecules, and cleavage is accompanied by their displacement toward the leaving anion, thus offering a qualitative mimicry of the experimental observations.