3-Hydroxybenzene 1,2,4-trisphosphate 4 is a new myo-inositol 1,4,5-trisphosphate analogue based on the core structure of benzene 1,2,4-trisphosphate 2 with an additional hydroxyl group at position-3, and is the first noninositol based compound to be a substrate for inositol 1,4,5-trisphosphate 5-phosphatase. In physicochemical studies on 2, when three equivalents of protons were added, the (31)P NMR spectrum displayed monophasic behaviour in which phosphate-1 and phosphate-2 behaved independently in most of the studied pH range. For compound 4, phosphate-2 and phosphate-4 interacted with the 3-OH group, which does not titrate at physiological pH, displaying complex biphasic behaviour which demonstrated co-operativity between these groups. Phosphate-1 and phosphate-2 strongly interacted with each other and phosphate-4 experienced repulsion because of the interaction of the 3-OH group. Benzene 1,2,4-trisphosphate 2 is resistant to inositol 1,4,5-trisphosphate type I 5-phosphatase catalysed dephosphorylation. However, surprisingly, 3-hydroxybenzene 1,2,4-trisphosphate 4 was dephosphorylated by this 5-phosphatase to give the symmetrical 2,3-dihydroxybenzene 1,4-bisphosphate 16. The extra hydroxyl group is shown to form a hydrogen bond with the vicinal phosphate groups at -15 degrees C, and (1)H NMR titration of the ring and hydroxyl protons in 4 shows the OH proton to be strongly stabilized as soon as the phosphate groups are deprotonated. The effect of the phenolic 3-OH group in compound 4 confirms a critical role for the 6-OH group of the natural messenger in the dephosphorylation mechanism that persists even in radically modified analogues.

3The synthesis of gold nanoparticles (Au NPs) from HAuCl 4 by using EDTA as a reducing 4 agent is investigated for the first time by using UV-Vis spectroscopy, transmission electron 5 microscopy (TEM), and dynamic light scattering (DLS). We show that the size of resulting Au 6 NPs is dictated by the reactivity of ionic Au(III) species and the charge density of EDTA 7 molecules with pH. Moreover by varying the pH of the reaction media, the size of Au NPs can 8 be tuned from 25 to 100 nm. Investigation of the nucleation and growth of Au NPs by time 9resolved UV-Vis and TEM revealed the presence of nanowires that progressively increases in 10 size at the same time the connected network is fragmented into small segments before the final 11 spherical particles are formed. The identification of reaction intermediates and final products 12 resulting from the reduction of Au(III) by EDTA was possible by recording several 1D-and 2D-13Nuclear Magnetic Resonance (NMR) spectra. Our results show that Au(III) reduction to Au (0) 14 NPs by EDTA is accompanied by decarbonylation of EDTA and the formation of formaldehyde 15 which, depending on pH, interferes in the reduction process and contributes to the synthesis. 16Beside the immense flexibility that can be provided by EDTA for further conjugation with 17 functional molecules to diversify the surface functionality and in turn broaden the application, 18 many synthetic routes concerned with the elaboration of nanoshells and core-shell metal 19 nanoparticles use a large excess of the toxic formaldehyde as a reducing agent. Given the interest 20 in biomedical applications of such nanomaterials and the important role of formaldehyde as a 21 reducing agent in the synthesis process, using EDTA as a reducing agent can be a good starting 22 point for minimizing or replacing formaldehyde use in the synthesis. 23

Malonamides are known and extensively studied for their lanthanide and actinide extracting properties. Those studies have also highlighted aggregated phenomena and a splitting of the organic phase, in some particular experimental conditions. To explain this behaviour of extractants, 1 H NMR was used to study micellar phenomena by the determination of the self-diffusion coefficients of two malonamides only different by the length of their alkyl chain (DMDBTDMA and DMDBPMA), in presence of n-dodecane and for systems saturated with water or anhydrous. Several information on the aggregates and on the malonamide supramolecular structure were obtained by fitting the curves of self-diffusion coefficient vs. concentration and by conjugated NMR experimental data to potentiometric titrations and physical measurements.