Linear {NiII–LnIII–NiII} Complexes Containing Twisted Planar Ni(μ‐phenolate)2Ln Fragments: Synthesis,Structure, and Magnetothermal Properties

Sequential reaction of a multisite LH₄ ligand {2‐[2‐hydroxy‐3‐(hydroxymethyl)‐5‐methylbenzylideneamino]‐2‐methylpropane‐1,3‐diol} with appropriate lanthanide salts followed by the addition of Ni(NO₃)₂ ? 6 H₂O in a 4:1:2 stoichiometric ratio in the presence of triethylamine afforded four heterobimetallic trinuclear complexes [Ni₂Gd(LH₃)₄] ? 3 NO₃ ? 3 MeOH ? H₂O ? CH₃CN ( 1 ), [Ni₂Tb(LH₃)₄] ? 3 NO₃ ? 3 MeOH ? CH₃CN ( 2 ), [Ni₂Dy(LH₃)₄] ? 3 NO₃ ? 3 MeOH ? H₂O ? CH₃CN ( 3 ), and [Ni₂Ho(LH₃)₄] ? 3 NO₃ ? 3 MeOH ? H₂O ? CH₃CN ( 4 ). Complexes 1 – 4 possess linear trimetallic cores with a central lanthanide ion. Magnetic studies revealed a predominant ferromagnetic interaction between the Ni and Ln centers. Alternating current susceptibility measurements of complex 3 showed a small frequency dependence of the out‐of‐phase signal, χ′′_M , under zero direct current field, but without achieving a net maximum above 2 K. Magnetic studies on 1 revealed that it has a significant magnetocaloric effect.     

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.     

Optimization of ultrasound-assisted extraction of phenolic compounds from Sesamum indicum

Abstract

Effective extraction of phyto-biomolecules insures retaining maximum functionality along with higher recovery. In this study, ultrasound-solvent assisted extraction (USAE) was employed for optimal extraction of phyto-biomolecules from Sesamum indicum (sesame) leaves using the approach of Response Surface Methodology (RSM). The optimized condition of 200?W power, 59% methanol concentration with 1:14?g/mL solid–liquid ratio and 15?min of extraction time yielded 367.39?±?1.85?mg GAE/100?g of total phenolic content, 96.72?±?3.27% of free radical scavenging activity and 81.20?±?2.87% of iron chelating activity respectively. The extract consist of essential phytocomponents like gallic acid, chlorogenic acid, and quercetin with lipid peroxidation activities of >50% over incubation time of 48?h. Also, showed antimicrobial activity against various Gram’s negative and positive food borne pathogens. The results of this study implied the importance of USAE for effective and optimum recovery of phyto-biomolecules from Sesame leaves with retained functional properties.     

Heterometallic Triply‐Bridging Bis‐Borylene Complexes

Triply‐bridging bis‐{hydrido(borylene)} and bis‐borylene species of groups 6, 8 and 9 transition metals are reported. Mild thermolysis of [Fe₂(CO)₉] with an in situ produced intermediate, generated from the low‐temperature reaction of [Cp*WCl₄] (Cp*=η⁵‐C₅Me₅) and [LiBH₄?THF] afforded triply‐bridging bis‐{hydrido(borylene)}, [(μ₃‐BH)₂H₂{Cp*W(CO)₂}₂{Fe(CO)₂}] ( 1 ) and bis‐borylene, [(μ₃‐BH)₂{Cp*W(CO)₂}₂{Fe(CO)₃}] ( 2 ). The chemical bonding analyses of 1 show that the B?H interactions in bis‐{hydrido (borylene)} species is stronger as compared to the M?H ones. Frontier molecular orbital analysis shows a significantly larger energy gap between the HOMO‐LUMO for 2 as compared to 1 . In an attempt to synthesize the ruthenium analogue of 1 , a similar reaction has been performed with [Ru₃(CO)₁₂]. Although we failed to get the bis‐{hydrido(borylene)} species, the reaction afforded triply‐bridging bis‐borylene species [(μ₃‐BH)₂{WCp*(CO)₂}₂{Ru(CO)₃}] ( 2′ ), an analogue of 2 . In search for the isolation of bridging bis‐borylene species of Rh, we have treated [Co₂(CO)₈] with nido‐[(RhCp*)₂(B₃H₇)], which afforded triply‐bridging bis‐borylene species [(μ₃‐BH)₂(RhCp*)₂Co₂(CO)₄(μ‐CO)] ( 3 ). All the compounds have been characterized by means of single‐crystal X‐ray diffraction study; ¹H, ¹¹B, ¹³C NMR spectroscopy; IR spectroscopy and mass spectrometry.     

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.     

Simultaneous occurrence of energy transfer and photoinduced electron transfer in interactions of hen egg white lysozyme with 4-nitroquinoline-1-oxide

The carcinogenic drug 4-nitroquinoline-1-oxide (4NQO) has been found to bind with the protein hen egg white lysozyme as evident from fluorescence quenching experiments. The binding constant and stoichiometry have been determined. The values of the thermodynamic parameters indicate that the interaction is an enthalpy-driven spontaneous phenomenon. The experimental value of change in free energy is similar to that obtained from the docking study. The far UV circular dichroism spectra show some changes in the secondary structure of protein. The high value of bimolecular quenching constant leads to the possibility of Förster resonance energy transfer (FRET). Along with FRET, the photoinduced electron transfer (PET) from tryptophan residue of protein to 4NQO has also been evident from the transient absorption spectra obtained in laser flash photolysis experiments. The simultaneous occurrence of FRET and PET is the key factor for quenching of intrinsic fluorescence of the protein as it binds with the drug.