Characterization of a Robust CoII Fluorescent Complex Deposited Intact On HOPG

The new diimine fluorescent ligand ACRI‐1 based on a central acridine yellow core is reported along with its coordination complex [Co₂( ACRI‐1 )₂] ( 1 ), a fluorescent weak ferromagnet. Due to the strong fluorescence of the acridine yellow fluorophore, it is not completely quenched when the ligand is coordinated to Co^II. The magnetic properties of bulk complex 1 and its stability in solution have been studied. Complex 1 has been deposited on highly ordered pyrolitic graphite (HOGP) from solution. The thin films prepared have been characterized by AFM, time‐of‐flight secondary ion mass spectrometry (TOF‐SIMS), grazing incidence X‐ray diffraction (GIXRD), X‐ray absorption spectroscopy (XAS), X‐ray magnetic circular dichroism (XMCD) and theoretical calculations. The data show that the complex is robust and remains intact on the surface of graphite.     

Combining Complementary Ligands into one Framework for the Construction of a Ferromagnetically Coupled [MnIII12] Wheel

Phenolic oxime and diethanolamine moieties have been combined into one organic framework, resulting in the formation of a novel ligand type that can be employed to construct a rare and unusual dodecametallic Mn wheel, within which nearest neighbours are coupled ferromagnetically.     

Uncovering the Stoichiometry of Pyrococcus furiosus RNase P,a Multi‐Subunit Catalytic Ribonucleoprotein Complex,by Surface‐Induced Dissociation and Ion Mobility Mass Spectrometry

We demonstrate that surface‐induced dissociation (SID) coupled with ion mobility mass spectrometry (IM‐MS) is a powerful tool for determining the stoichiometry of a multi‐subunit ribonucleoprotein (RNP) complex assembled in a solution containing Mg²⁺. We investigated Pyrococcus furiosus (Pfu) RNase P, an archaeal RNP that catalyzes tRNA 5′ maturation. Previous step‐wise, Mg²⁺‐dependent reconstitutions of Pfu RNase P with its catalytic RNA subunit and two interacting protein cofactor pairs (RPP21?RPP29 and POP5?RPP30) revealed functional RNP intermediates en route to the RNase P enzyme, but provided no information on subunit stoichiometry. Our native MS studies with the proteins showed RPP21?RPP29 and (POP5?RPP30)₂ complexes, but indicated a 1:1 composition for all subunits when either one or both protein complexes bind the cognate RNA. These results highlight the utility of SID and IM‐MS in resolving conformational heterogeneity and yielding insights on RNP assembly.     

Synthesis of poly(4‐hydroxystyrene)‐based block copolymers containing acid‐sensitive blocks by living anionic polymerization

Living anionic polymerization of an acetal protected 4‐hydroxystyrene monomer, (4‐(2‐tetrahydropyranyloxy)styrene) (OTHPSt), and the chain extension of the poly(OTHPSt) anion with a variety of monomers including styrene, 4‐tert‐butylstyrene, methacryloyl polyhedral oligomeric silsesquioxane (MAPOSS) and hexamethylcyclotrisiloxane is demonstrated. The P(OTHPSt) homopolymer has a glass transition temperature well above room temperature, which facilitates handling and purification of the protected poly(4‐hydroxystyrene) (PHS). The resulting diblock copolymers have narrow dispersities <1.05. Chemoselective mild deprotection conditions for the P(OTHPSt) block were identified to prevent simultaneous degradation of the MAPOSS or dimethylsiloxane (DMS) block, thus allowing for the first reported synthesis of P(HS‐b‐DMS) and P(HS‐b‐MAPOSS). © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1458–1468     

Magnetic Relaxation in Single‐Electron Single‐Ion Cerium(III) Magnets: Insights from Ab Initio Calculations

Detailed ab initio calculations were performed on two structurally different cerium(III) single‐molecule magnets (SMMs) to probe the origin of magnetic anisotropy and to understand the mechanism of magnetic relaxations. The complexes [Ce^III{Zn^II(L)}₂(MeOH)]BPh₄ ( 1 ) and [Li(dme)₃][Ce^III(cot′′)₂] ( 1 ; L=N,N,O,O‐tetradentate Schiff base ligand; 2 ; DME=dimethoxyethane, COT′′=1,4‐bis(trimethylsilyl)cyclooctatetraenyldianion), which are reported to be zero‐field and field‐induced SMMs with effective barrier heights of 21.2 and 30 K respectively, were chosen as examples. CASSCF+RASSI/SINGLE_ANISO calculations unequivocally suggest that m_J|±5/2〉 and |±1/2〉 are the ground states for complexes 1 and 2 , respectively. The origin of these differences is rooted back to the nature of the ligand field and the symmetry around the cerium(III) ions. Ab initio magnetisation blockade barriers constructed for complexes 1 and 2 expose a contrasting energy‐level pattern with significant quantum tunnelling of magnetisation between the ground state Kramers doublet in complex 2 . Calculations performed on several model complexes stress the need for a suitable ligand environment and high symmetry around the cerium(III) ions to obtain a large effective barrier.     

Can CH⋅⋅⋅π Interactions Be Used To Design Single‐Chain Magnets?

This theoretical study suggests that CH???π stacking interactions between monomeric units can be used to design novel single‐chain magnets (SCMs), as the sign of coupling is predictable and such chains inherently yield negative axial anisotropy, a condition often difficult to achieve in conventional SCMs.     

Shock Processing of Amino Acids Leading to Complex Structures—Implications to the Origin of Life

The building blocks of life, amino acids, are believed to have been synthesized in the extreme conditions that prevail in space, starting from simple molecules containing hydrogen, carbon, oxygen and nitrogen. However, the fate and role of amino acids when they are subjected to similar processes largely remain unexplored. Here we report, for the first time, that shock processed amino acids tend to form complex agglomerate structures. Such structures are formed on timescales of about 2 ms due to impact induced shock heating and subsequent cooling. This discovery suggests that the building blocks of life could have self-assembled not just on Earth but on other planetary bodies as a result of impact events. Our study also provides further experimental evidence for the ‘threads’ observed in meteorites being due to assemblages of (bio)molecules arising from impact-induced shocks.     

Magnetic exchange interactions and magneto-structural correlations in heterobridged μ-phenoxo-μ(1,1)-azide dinickel(II) compounds: a combined experimental and theoretical exploration

This investigation presents the syntheses, crystal structures, magnetic properties, and density functional theoretical modeling of magnetic behavior of two heterobridged μ-phenoxo-μ(1,1)-azido dinickel(II) compounds [Ni(II)(2)(L(1))(2)(μ(1,1)-N(3))(N(3))(H(2)O)]·CH(3)CH(2)OH (1) and [Ni(II)(2)(L(2))(2)(μ(1,1)-N(3))(CH(3)CN)(H(2)O)](ClO(4))·H(2)O·CH(3)CN (2), where HL(1) and HL(2) are the [1+1] condensation products of 3-methoxysalicylaldehyde and 1-(2-aminoethyl)-piperidine (for HL(1))/4-(2-aminoethyl)-morpholine (for HL(2)), along with density functional theoretical magneto-structural correlations of μ-phenoxo-μ(1,1)-azido dinickel(II) systems. Compounds 1 and 2 crystallize in orthorhombic (space group Pbca) and monoclinic (space group P2(1)/c) systems, respectively. The coordination environments of both metal centers are distorted octahedral. The variable-temperature (2-300 K) magnetic susceptibilities at 0.7 T of both compounds have been measured. The interaction between the metal centers is moderately ferromagnetic; J = 16.6 cm(-1), g = 2.2, and D = -7.3 cm(-1) for 1 and J = 16.92 cm(-1), g = 2.2, and D(Ni1) = D(Ni2) = -6.41 cm(-1) for 2. Broken symmetry density functional calculations of exchange interaction have been performed on complexes 1 and 2 and provide a good numerical estimate of J values (15.8 cm(-1) for 1 and 15.35 cm(-1) for 2) compared to experiments. The role of Ni-N bond length asymmetry on the magnetic coupling has been noted by comparing the structures and J values of complexes 1 and 2 together with previously published dimers 3 (Eur. J. Inorg. Chem. 2009, 4982), 4 (Inorg. Chem. 2004, 43, 2427), and 5 (Dalton Trans. 2008, 6539). Our extensive DFT calculations reveal an important clue to the mechanism of coupling where the orientation of the magnetic orbitals seems to differ with asymmetry in the Ni-N bond lengths. This difference in orientation leads to a large change in the overlap integral between the magnetic orbitals and thus the magnetic coupling. DFT calculations have also been extended to develop several magneto-structural correlations in this type of complexes and the correlation aim to focus on the asymmetry of the Ni-N bond lengths reveal that the asymmetry plays a proactive role in governing the magnitude of the coupling. From a completely symmetric Ni-N bond length, two behaviors have been noted: with a decrease in bond length there is an increase in the ferromagnetic coupling, while an increase in the bond lengths leads to a decrease in ferromagnetic interaction. The later correlation is supported by experiments. The magnetic properties of 1, 2, and three previously reported related compounds have been discussed in light of the structural parameters and also in light of the theoretical correlations determined here.     

Bioanalytical method development,validation and quantification of dorsomorphin in rat plasma by LC‐MS/MS

The present investigation describes the development and validation of a sensitive liquid chromatography–mass spectrometry/mass spectrometry (LC‐MS/MS) method for the estimation of dorsomorphin in rat plasma. A sensitive LC‐MS/MS method was developed using multiple reaction monitoring mode, with the transition of m/z (Q1/Q3) 400.2/289.3 for dorsomorphin and m/z (Q1/Q3) 306.2/236.3 for zaleplon. Chromatographic separation was achieved on a reverse phase Agilent XDB C₁₈ column (100 × 4.6 mm, 5 µm). The mobile phase consisted of acetonitrile and 5 mm ammonium acetate buffer (pH 6.0) 90:10 v/v, at a flow rate of 0.8 mL/min. The effluence was ionized in positive ion mode by electrospray ionization (ESI) and quantitated by mass spectrometry. The retention times of dorsomorphin and internal standard were found to be 2.13 and 1.13 min, respectively. Mean extraction recovery of dorsomorphin and internal standard in rat plasma was above 80%. Dorsomorphin calibration curve in rat plasma was linear (r² ≥ 0.99) ranging from 0.005 to 10 µg/mL. Inter‐day and intra‐day precision and accuracy were found to be within 85–115% (coefficient of variation). This method was successfully applied for evaluation of the oral pharmacokinetic profile of dorsomorphin in male Wistar rats. Copyright © 2013 John Wiley & Sons, Ltd.