Characterization of Functional Groups in Estuarine Dissolved Organic Matter by DNP-enhanced 15N and 13C Solid-State NMR

Estuaries are key ecosystems with unique biodiversity and are of high economic importance. Along the estuaries, variations in environmental parameters, such as salinity and light penetration, can modify the characteristics of dissolved organic matter (DOM). Nevertheless, there is still limited information about the atomic-level transformations of DOM in this ecosystem. Solid-state NMR spectroscopy provides unique insights into the nature of functional groups in DOM. A major limitation of this technique is its lack of sensivity, which results in experimental time of tens of hours for the acquisition of ¹³C NMR spectra and generally precludes the observation of ¹⁵N nuclei for DOM. We show here how the sensitivity of solid-state NMR experiments on DOM of Seine estuary can be enhanced using dynamic nuclear polarization (DNP) under magic-angle spinning. This technique allows the acquisition of ¹³C NMR spectra of these samples in few minutes, instead of hours for conventional solid-state NMR. Both conventional and DNP-enhanced ¹³C NMR spectra indicate that the ¹³C local environments in DOM are not strongly modified along the Seine estuary. Furthermore, the sensitivity gain provided by the DNP allows the detection of ¹⁵N NMR signal of DOM, in spite of the low nitrogen content. These spectra reveal that the majority of nitrogen is in the amide form in these DOM samples and show an increased disorder around these amide groups near the mouth of the Seine.     

Theranostic Approach for the Protein Corona of Polysaccharide Nanoparticles

Polysaccharide nanoparticles are promising materials in the wide range of disciplines such as medicine, nutrition, food production, agriculture, material science and others. They excel not only in their non‐toxicity and biodegradability but also in their easy preparation. As well as inorganic particles, a protein corona (PC) around polysaccharide nanoparticles is formed in biofluids. Moreover, it has been considered that the overall response of the organism to nanoparticles presence depends on the PC. This review summarises scientific publications about the structural chemistry of polysaccharide nanoparticles and their impact on theranostic applications. Three strategies of implementation of the PC in theranostics have been discussed: I) Utilisation of the PC in therapy; II) How the composition of the PC is analysed for specific disease markers; III) How the formed PC can interact with the immune system and enhances the immunomodulation or immunoelimination. Thus, the findings from this review can contribute to improve the design of drug delivery systems. However, it is still necessary to elucidate the mechanisms of nano‐bio interactions and discover new connections in nanoscale research.     

Microstructure and physico-chemical transformation of some common woods from Cameroon during drying

Journal of Thermal Analysis and Calorimetry - The influence of drying on the microstructure, physical and chemical properties of some tropical wood species has been investigated using...     

Electrochemical Behavior of Ce(IV)/Ce(III) Couple in N,N-Di(2-ethylhexyl)-n-butanamide (DEHBA), N,N-Di(2-ethylhexyl)-iso-butanamide (DEHiBA), and N,N-Di(2-ethylhexyl)-3,3-dimethyl Butanamide (DEHDMBA)

In this work we report on the electrochemical behavior of Ce(IV)/Ce(III) redox couple in pure N,N-dialkyl amides (N,N-DA), namely N,N-di(2-ethylhexyl)-n-butanamide (DEHBA), N,N-di(2-ethylhexyl)-iso-butanamide (DEHiBA), and N,N-di(2-ethylhexyl)-3,3-dimethyl butanamide (DEHDMBA) equilibrated with nitric aqueous solutions as an entry to the direct electrochemical characterization of plutonium in these extractants. Ce(IV)/Ce(III) redox process was used as a model. Its potential (E_1/2≅1.02 V/SCE) is not affected by the temperature and the nature of the N,N-DA and this clearly indicates that the functionalities of these extractants produce the same relative effect on both +IV and +III oxidation states of the cerium cation. Linear variations of the current intensity of the reduction peak of Ce(IV) with the concentration of Ce(IV)/N,N-DAs/HNO₃(5 M) solutions were obtained from cyclic voltammograms recorded at 25 °C and 40 °C. Due to the poor definition of the voltammograms in DEHiBA and DEHDMBA, such characterization allows only the evaluation of the performances of the chemical extraction of Ce(IV) from aqueous nitric acid solution by the undiluted DEHBA. To our knowledge, the electrochemical behavior of Ce(IV)/Ce(III) in N,N-DAs was not previously studied and our findings will for sure open the door for further investigations in this field.     

Rigidity percolation in particle-laden foams

We study the viscoelastic behavior of aqueous foam mixed with solid noncolloidal particles. We show that adding a tiny amount of grains can enhance the elastic and loss shear moduli by more than 1 order of magnitude. The scaling of these moduli with solid volume fraction is in qualitative agreement with that predicted by an effective-medium rigidity percolation model. We present a simple model, based on capillary attraction, to explain the particle-size dependence of the threshold.     

Long-range repulsive interaction between molecules on a metal surface induced by charge transfer

The adsorption of a molecular electron donor on Au(111) is characterized by the spontaneous formation of a superlattice of monomers spaced several nanometers apart. The coverage-dependent molecular pair distributions obtained from scanning tunneling microscopy data reveal an intermolecular long-range repulsive potential, which decreases as the inverse of the molecular separation. Density functional theory calculations show a charge accumulation in the molecules due to electron donation into the metal. Our results suggest that electrostatic repulsion between molecules persists on the surface of a metal.     

Click approaches in sol–gel chemistry

The combination of the copper-catalyzed alkyne-azide cycloaddition (CuAAC) reaction with sol–gel processing enables the versatile preparation of sol–gel materials under different shapes with targeted functionalities through a diversity-oriented approach. In this account, the development of the CuAAC reaction under anhydrous conditions for the synthesis of sol–gel precursors and for the assembling of magnetic nanoparticles on self-assembled monolayers is related, as well as the use of the classical CuAAC methodologies for the functionalization of mesoporous silica nanoparticles and microdots arrays. Coupling CuAAC and Sol–Gel will result in simplified preparations of multifunctional materials with controlled morphologies.     

The Effects of Formulation on Imidacloprid Dissipation in Grapes and Vine Leaves and on Required Pre-Harvest Intervals under Lebanese Climatic Conditions

In this study, imidacloprid, a systemic insecticide, currently having a specified European Commission MRL value for vine leaves (2 mg kg⁻¹), was applied on a Lebanese vineyard under different commercial formulations: as a soluble liquid (SL) and water dispersible granules (WDG). In Lebanon, many commercial formulations of imidacloprid are subject to the same critical good agricultural practice (cGAP). It was, therefore, important to verify the variability in dissipation patterns according to matrix nature and formulation type. Random samplings of grapes and vine leaves were performed starting at 2 days until 18 days after treatment. Residue extractions were performed according to the QuEChERS method and the analytical determination using liquid chromatography coupled to tandem mass spectrometry (LC-MS-MS). The SL formulation yielded significantly higher initial deposit than the WDG formulation on grapes and vine leaves. The formulation type did not significantly affect the dissipation rates; the estimated half-lives in grapes and vine leaves were 0.5 days for all imidacloprid formulations. No pre-harvest intervals were necessary on grapes. PHIs of 3.7 days for the SL formulation and 2.8 days for the WDG formulation were estimated on vine leaves. The results showed that the type of formulation and the morphological and physiological characteristics of the matrix had an effect on the initial deposits, and thus residue levels, but not on the dissipation patterns.     

Ring opening polymerization of cyclic organosilicon compounds: Recent progress

A novel initiator, i.e. trimethylsilylmethyllithium has been successfully used for the ring opening polymerization of cyclosiloxanes in toluene, in the presence of the cryptand [211]. Suitable conditions have been found in which monomodal distributions of molecular weights of polysiloxanes are observed by GPC, even in the case of D₄ and 1,3,5,7-tetramethyl-1,3,5,7-tetravinyl cyclotetra siloxane (D₄Vi) polymerizations. Moreover, kinetics of propagation and of formation of cyclosiloxanes can be followed by ²⁹Si or ¹³C NMR spectroscopy on living polymer solutions. The rate of propagation of hexaethylcyclotrisiloxane is 120 times lower than that of the corresponding dimethylated analog D₃, under the same conditions.