pH-Dependent Hydration Change in a Gd-Based MRI Contrast Agent with a Phosphonated Ligand

The heptadentate ligand L was shown to form an extremely stable Gd complex at neutral pH with a pGd value of 18.4 at pH 7.4. The X-ray crystal structures of the complexes formed with Gd and Tb displayed two very different coordination behaviors being, respectively, octa- and nonacoordinated. The relaxometric properties of the Gd complex were studied by field-dependent relaxivity measurements at various temperatures and by ¹⁷O NMR spectroscopy. The pH-dependence of the longitudinal relaxivity profile indicated large changes around neutral pH leading to a very large value of 10.1 mm ⁻¹⋅s⁻¹ (60 MHz, 298 K) at pH 4.7. The changes were attributed to an increase of the hydration number from one water molecule in basic conditions to two at acidic pH. A similar trend was observed for the luminescence of the Eu complex, confirming the change in hydration state. DOSY experiments were performed on the Lu analogue, pointing to the absence of dimers in solution in the considered pH range. A breathing mode of the complex was postulated, which was further supported by ¹H and ³¹P NMR spectroscopy of the Yb complex at varying pH and was finally modeled by DFT calculations.     

Fluorescent macrocyclic chemosensor for Zn(II) detection at alkaline pH values

ABSTRACT

The new macrocyclic ligand L (28,29-dimethoxy-27-oxa-8,11,14,17,25,26-hexaazatetracyclo[22.2.1.1(2,6).1(19,23)]nonacosa-2,4,6(28),19,21,23(29),24,26(1)-octaene) has been synthesised. It contains a tetramine chain and the 2,5-bis(2-methoxy-3-metyl-phenyl)-1,3,4-oxadiazole (PPD-OMe) chromophore, acting as coordinating and sensing units, respectively.

The fluorescent emission of L depends on the pH being highly fluorescent at pH = 2 and not emitting from pH >10. The studies highlighted that L is a PET mediated emitting chemosensor, being the PET effect regulated by the degree of the tetraamine protonation.

L coordinates metal ions (Cu(II), Zn(II) and Cd(II)) in water giving rise to an OFF-ON fluorescent response for the presence of Zn(II) ion thus signalling its presence in the medium. This response is particularly notable at pH = 9 allowing to extend the Zn(II) sensing also in the alkaline pH field.     

Word problems and ceers

This note addresses the issue as to which ceers can be realized by word problems of computably enumerable (or, simply, c.e.) structures (such as c.e. semigroups, groups, and rings), where being realized means to fall in the same reducibility degree (under the notion of reducibility for equivalence relations usually called “computable reducibility”), or in the same isomorphism type (with the isomorphism induced by a computable function), or in the same strong isomorphism type (with the isomorphism induced by a computable permutation of the natural numbers). We observe, e.g., that every ceer is isomorphic to the word problem of some c.e. semigroup, but (answering a question of Gao and Gerdes) not every ceer is in the same reducibility degree of the word problem of some finitely presented semigroup, nor is it in the same reducibility degree of some non-periodic semigroup. We also show that the ceer provided by provable equivalence of Peano Arithmetic is in the same strong isomorphism type as the word problem of some non-commutative and non-Boolean c.e. ring.     

The Skew Normal multivariate risk measurement framework

Computational Management Science - In this paper, we consider a random vector $$X=left( X_1,X_2right) $$ following a multivariate Skew Normal distribution and we provide an explicit formula for...     

Effect of 300 and 500 MPa pressure treatments on starch–water adsorption/desorption isotherms and hysteresis

Pressure treatments of 300 and 500?MPa during 15?min were found to change starch–water sorption (adsorption and desorption) isotherms and the hysteresis effect, particularly the 500?MPa. This last treatment shifted the adsorption/desorption isotherms downward, compared with non-treated starch and starch treated at 300?MPa. The observed hysteresis effect decreased with the increase in pressure level in the whole a_w range, indicating that adsorption and desorption isotherms became closer. Guggenheim–Anderson–De Boer and Brunauer–Emmett–Teller model parameters Cb, Cg, K and Mm also showed changes caused by pressure, the latter being lower in the pressure-processed samples, thus indicating possible changes on microbial and (bio)chemical stabilities of pressure-processed food products containing starch.     

The structure of a collineation group preserving an oval in a projective plane of odd order

We investigate the structure of a collineation groupG preserving an oval in a finite projective plane of odd order and we obtain several results aboutG, whenG is a2-group. These results are then used to investigate the structure ofG/O(G) in the general case and, in particular, that ofF*(G/O(G)).This research was supported in part by a grant from the M.U.R.S.T.     

Polynomial Stability to Three-Dimensional Magnetoelastic Waves

In this work we show that the energy associated to the linear three-dimensional magneto-elastic system decays polynomially to zero as time goes to infinity, provided the initial data is smooth enough.