Analysis of the Magnetic Coupling in a Mn(II)-U(V)-Mn(II) Single Molecule Magnet

[{Mn(TPA)I}{UO2(Mesaldien)}{Mn(TPA)I}]I formula (here TPA=tris(2-pyridylmethyl)amine and Mesaldien=N,N’-(2-aminomethyl)diethylenebis(salicylidene imine)) reported by Mazzanti and coworkers (Chatelain et al. Angew. Chem. Int. Ed. 2014 , 53, 13434) is so far the best Single Molecule Magnet (SMM) in the {3d–5f} class of molecules exhibiting barrier height of magnetization reversal as high as 81.0 K. In this work, we have employed a combination of ab initio CAS and DFT methods to fully characterize this compound and to extract the relevant spin Hamiltonian parameters. We show that the signs of the magnetic coupling and of the g-factors of the monomers are interconnected. The central magnetic unit [U^VO₂]⁺ is described by a Kramers Doublet (KD) with negative g-factors, due to a large orbital contribution. The magnetic coupling for the {Mn(II)-U(V)} pair is modeled by an anisotropic exchange Hamiltonian: all components are ferromagnetic in terms of spin moments, the parallel component J_Z twice larger as the perpendicular one J_⊥. The spin density distribution suggests that spin polarization on the U(V) center favors the ferromagnetic coupling. Further, the J_Z/J_⊥ ratio, which is related to the barrier height, was found to correlate to the corresponding spin contribution of the g-factors of the U(V) center. This correlation established for the first time offers a direct way to estimate this important ratio from the corresponding g^S-values, which can be obtained using traditional ab initio packages and hence has a wider application to other {3d–5f} magnets. It is finally shown that the magnetization barrier height is tuned by the splitting of the [U^VO₂]⁺ 5 f orbitals.     

A p‐Hydroxyphenacyl–Benzothiazole–Chlorambucil Conjugate as a Real‐Time‐Monitoring Drug‐Delivery System Assisted by Excited‐State Intramolecular Proton Transfer

Among the well‐known phototriggers, the p‐hydroxyphenacyl (pHP) group has consistently enabled the very fast, efficient, and high‐conversion release of active molecules. Despite this unique behavior, the pHP group has been ignored as a delivery agent, particularly in the area of theranostics, because of two major limitations: Its excitation wavelength is below 400 nm, and it is nonfluorescent. We have overcome these limitations by incorporating a 2‐(2′‐hydroxyphenyl)benzothiazole (HBT) appendage capable of rapid excited‐state intramolecular proton transfer (ESIPT). The ESIPT effect also provided two unique advantages: It assisted the deprotonation of the pHP group for faster release, and it was accompanied by a distinct fluorescence color change upon photorelease. In vitro studies showed that the p‐hydroxyphenacyl–benzothiazole–chlorambucil conjugate presents excellent properties, such as real‐time monitoring, photoregulated drug delivery, and biocompatibility.     

Kinetic study of the interaction of three glycine‐containing dipeptides with diaquaethylenediamineplatinum(II) in aqueous medium

The kinetics of the interaction of three glycine‐containing dipeptides, namely, glycine‐L‐leucine (Gly‐Leu), glycine‐L‐isoleucine (Gly‐Ile), and glycine‐valine (Gly‐Val) with [Pt(en)(H₂O)₂](ClO₄)₂ has been studied spectrophotometrically as a function of [substrate complex], [dipeptides] and temperature at a particular pH(4.0), where the substrate complex exists predominantly as the diaqua species and the dipeptides as a zwitterion. The substitution reaction shows two consecutive steps; the first is the ligand‐assisted anation and the second is the chelation step. The activation parameters for both the steps were evaluated using Eyring's equation. The low ΔH₁^≠ and large negative value of ΔS₁^≠ as well as ΔH₂^≠ and ΔS₂^≠ indicate an associative mode of activation for both the aqua ligand substitution processes. © 2011 Wiley Periodicals, Inc. Int J Chem Kinet 43: 498–506, 2011     

Studies on manganese-nodule leached residues; 1. Physicochemical characterization and its adsorption behavior toward Ni(2+) in aqueous system

Physicochemical characterization of manganese-nodule leached residues was carried out by chemical analyses, XRD, TG-DTA, surface area measurement, and FTIR techniques. The material is very fine-grained (<75 microm), is cryptocrystalline to amorphous in nature, and contains mainly of delta-MnO(2), quartz (alpha-SiO(2)), and zeolite/feldspar minerals. Physically adsorbed sulfates in the leached residue are removed by repeated water washing and the washed sample shows an appreciable increase in surface area. This is indicated by the absence of 1387 and 1099 cm(-1) peaks in the IR spectrum of the washed sample. The adsorption behavior of the washed sample toward Ni(2+) was recorded as a function of time, pH, temperature, and concentrations of adsorbent and adsorbate.     

Scaling behavior of a nonlinear oscillator with additive noise,white and colored

We study analytically and numerically the problem of a nonlinear mechanical oscillator with additive noise in the absence of damping. We show that the amplitude, the velocity and the energy of the oscillator grow algebraically with time. For Gaussian white noise, an analytical expression for the probability distribution function of the energy is obtained in the long-time limit. In the case of colored, Ornstein-Uhlenbeck noise, a self-consistent calculation leads to (different) anomalous diffusion exponents. Dimensional analysis yields the qualitative behavior of the prefactors (generalized diffusion constants) as a function of the correlation time. Received 10 October 2002 Published online 6 March 2003 RID="a" ID="a"e-mail: mallick@spht.saclay.cea.fr     

Analytic structure of ρ meson propagator at finite temperature

We analyse the structure of one-loop self-energy graphs for the ρ meson in real time formulation of finite temperature field theory. We find the discontinuities of these graphs across the unitary and the Landau cuts. These contributions are identified with different sources of medium modification discussed in the literature. We also calculate numerically the imaginary and the real parts of the self-energies and construct the spectral function of the ρ meson, which are compared with an earlier determination. A significant contribution arises from the unitary cut of the π ω loop, that was ignored so far in the literature.     

Markov property of continuous dislocation band propagation

Tensile tests were carried out by deforming polycrystalline samples of substitutional Al–2.5%Mg alloy at room temperature for a range of strain rates. The Portevin–Le Chatelier (PLC) effect was observed throughout the strain rate regime. The deformation bands in this region are found to be of type A in nature. From the analysis of the experimental stress time series data we could infer that the dynamics of type A dislocation band propagation is a Markov process.