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Encapsulation of contrast imaging agents by polypropyleneimine-based dendrimers†

International audiencePolypropyleneimines (PPIs) functionalized by glycerol-based entities are prepared and characterized by diffusion-ordered spectroscopy NMR. Showing low cytotoxicity against MRC5 fibroblasts, their encapsulation capacities of gadolinium complexes was evaluated. T1 measurements were performed to determine the relaxivity of the encapsulated gadopentetate dimeglumine (GdBOPTA) in dendrimers of fourth and fifth generation (GD-PPI-4 and GD-PPI-5). Comparison of the GdBOPTA relaxivity and the relaxivity of GdBOPTA-loaded dendrimers showed a slight increase of the gadolinium chelate relaxivit

Steric Decompression of Picket-Strapped Porphyrins for the Synthesis of Side-Differentiated Chelates

A general method to synthesize various αβαβ bis-strapped porphyrins, with a different functionalization on each side of the macrocycle, is described. The resulting new chelates may find applications as analogues of heme protein active sites, bifunctional chelates, or specific bis-chelating molecules with potential medical utility

Gd3+ Complexes Conjugated to Cyclodextrins: Hydroxyl Functions Influence the Relaxation Properties

In the search for improvement in the properties of gadolinium-based contrast agents, cyclodextrins (CDs) are interesting hydrophilic scaffolds with high molecular weight. The impact of the hydrophilicity of these systems on the MRI efficacy has been studied using five β-CDs substituted with DOTA or TTHA ligands which, respectively, allow for one (q = 1) or no water molecule (q = 0) in the inner coordination sphere of the Gd3+ ion. Original synthetic pathways were developed to immobilize the ligands at C-6 position of various hydroxylated and permethylated β-CDs via an amide bond. To describe the influence of alcohol and ether oxide functions of the CD macrocycle on the relaxation properties of the Gd3+ complexes, 1H Nuclear Magnetic Relaxation Dispersion (NMRD) profiles, and 17O transverse relaxation rates have been measured at various temperatures. The differences observed between the hydroxylated and permethylated β-CDs bearing non-hydrated GdTTHA complexes can be rationalized by a second sphere contribution to the relaxivity in the case of the hydroxylated derivatives, induced by hydrogen-bound water molecules around the hydroxyl groups. In contrast, for the DOTA analogs the exchange rate of the water molecule directly coordinated to the Gd3+ is clearly influenced by the number of hydroxyl groups present on the CD, which in turn influences the relaxivity and gives rise to a very complex behavior of these hydrophilic systems.</jats:p

Towards an understanding of the structural performance of future electrified roads: a finite element simulation study

Nowadays, many novel technologies are under investigations for making our road infrastructure functionbeyond providing mobility and embrace other features that can promote the sustainability developmentof road transport sector. These new roads are often referred to as multifunctional or ‘smart’ roads. Focusin this paper is given to the structural aspects of a particular smart road solution called electrified road or‘eRoad’, which is based on enabling the inductive power transfer technology to charge electric vehiclesdynamically. Specifically, a new mechanistic-based methodology is firstly presented, using a finiteelement simulation and an advanced constitutive model for the asphalt concrete materials. Based onthis, the mechanical responses of a potential eRoad structure under typical traffic loading conditions arepredicted and analysed thoroughly. The main contributions of this paper include thus: (1) introducing anew methodology for analysing a pavement structure purely based on mechanistic principles; (2) utilisingthis methodology for the investigation of a future multifunctional road pavement structure, such as aneRoad; and (3) providing some practical guidance for an eRoad pavement design and the implementationinto practice.</p

The Preparation of New Phosphorus-Centered Functional Groups for Modified Oligonucleotides and Other Natural Phosphates

Efforts to develop synthetic methodologies allowing the preparation of α,α– difluorophosphonothioates, α,α–difluorophosphonodithioates, α,α–difluorophosphono- trithioates, and α,α–difluorophosphinates are reviewed in the light of applications in the field of modified oligonucleotides and cyclitol phosphates. Two successful approaches have been developed, based either on the addition of phosphorus-centered radicals onto gem–difluoroalkenes or on a process involving the addition of lithiodifluorophosphono- thioates 91 onto a ketone and the subsequent deoxygenation reaction of the adduct. The radical route successfully developed a practical route to α,α–difluoro–H–phosphinates which proved to be useful intermediates to a variety of phosphate isosters. The ionic route led to the first preparation of phosphonodifluoromethyl analogues of nucleoside– 3’–phosphates