Toward a Rational Design of Highly Folded Peptide Cation Conformations. 3D Gas-Phase Ion Structures and Ion Mobility Characterization

Heptapeptide ions containing combinations of polar Lys, Arg, and Asp residues with non-polar Leu, Pro, Ala, and Gly residues were designed to study polar effects on gas-phase ion conformations. Doubly and triply charged ions were studied by ion mobility mass spectrometry and electron structure theory using correlated ab initio and density functional theory methods and found to exhibit tightly folded 3D structures in the gas phase. Manipulation of the basic residue positions in LKGPADR, LRGPADK, KLGPADR, and RLGPADK resulted in only minor changes in the ion collision cross sections in helium. Replacement of the Pro residue with Leu resulted in only marginally larger collision cross sections for the doubly and triply charged ions. Disruption of zwitterionic interactions in doubly charged ions was performed by converting the C-terminal and Asp carboxyl groups to methyl esters. This resulted in very minor changes in the collision cross sections of doubly charged ions and even slightly diminished collision cross sections in most triply charged ions. The experimental collision cross sections were related to those calculated for structures of lowest free energy ion conformers that were obtained by extensive search of the conformational space and fully optimized by density functional theory calculations. The predominant factors that affected ion structures and collision cross sections were due to attractive hydrogen bonding interactions and internal solvation of the charged groups that overcompensated their Coulomb repulsion. Structure features typically assigned to the Pro residue and zwitterionic COO-charged group interactions were only secondary in affecting the structures and collision cross sections of these gas-phase peptide ions.

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One water molecule stabilizes the cationized arginine zwitterion

Singly hydrated clusters of lithiated arginine, sodiated arginine, and lithiated arginine methyl ester are investigated using infrared action spectroscopy and computational chemistry. Whereas unsolvated lithiated arginine is nonzwitterionic, these results provide compelling evidence that attachment of a single water molecule to this ion makes the zwitterionic form of arginine, in which the side chain is protonated, more stable. The experimental spectra of lithiated and sodiated arginine with one water molecule are very similar and contain spectral signatures for protonated side chains, whereas those of lithiated arginine and singly hydrated lithiated arginine methyl ester are different and contain spectral signatures for neutral side chains. Calculations at the B3LYP/6-31++G** level of theory indicate that solvating lithiated arginine with a single water molecule preferentially stabilizes the zwitterionic forms of this ion by 25-32 kJ/mol and two essentially isoenergetic zwitterionic structure are most stable. In these structures, the metal ion either coordinates with the N-terminal amino group and an oxygen atom of the carboxylate group (NO coordinated) or with both oxygen atoms of the carboxylate group (OO coordinated). In contrast, the OO-coordinated zwitterionic structure of sodiated arginine, both with and without a water molecule, is clearly lowest in energy for both ions. Hydration of the metal ion in these clusters weakens the interactions between the metal ion and the amino acid, whereas hydrogen-bond strengths are largely unaffected. Thus, hydration preferentially stabilizes the zwitterionic structures, all of which contain strong hydrogen bonds. Metal ion size strongly affects the relative propensity for these ions to form NO or OO coordinated structures and results in different zwitterionic structures for lithiated and sodiated arginine clusters containing one water molecule.     

Lead zirconate titanate-nickel zink ferrite thick-film composites: obtaining by the screen printing technique and magnetoelectric properties

Layered thick-film composites containing one lead zirconate titanate (PZT) layer, one nickel zinc ferrite (NZF) layer, two PZT-NZF layers, or three PZT-NZF-PZT layers each 40–50 μm thick are prepared. The layers are applied by screen printing on a ceramic aluminum oxide substrate with a preformed contact (conducting) layer. The dielectric properties of the composites are studied in the temperature interval 80–900 K and the frequency interval 25 Hz-1 MHz. Polarized samples exhibit piezoelectric, pyroelectric, and magnetoelectric effects. In tangentially magnetized two- and three-layer composites, the magnetoelectric conversion factor equals 57 kV/(m T) at low frequencies and reaches 2000 kV/(m T) at the mechanical resonance frequency.     

Moving toward shared realities through empathy in mathematical modeling: An ecological systems theory approach

The mathematics education community has routinely called for mathematics tasks to be connected to the real world. However, accomplishing this in ways that are relevant to students’ lived experiences can be challenging. Meanwhile, mathematical modeling has gained traction as a way for students to learn mathematics through real-world connections. In an open problem to the mathematics education community, this paper explores connections between the mathematical modeling and the nature of what is considered relevant to students. The role of empathy is discussed as a proposed component for consideration within mathematical modeling so that students can further relate to real-world contexts as examined through the lens of Ecological Systems Theory. This is contextualized through a classroom-tested example entitled “Tiny Homes as a Solution to Homelessness” followed by implications and conclusions as they relate to mathematics education.     

Magnetic structure of the quasi-one-dimensional frustrated antiferromagnet LiCu<Subscript>2</Subscript>O<Subscript>2</Subscript> with Spin <Emphasis Type="Italic">S</Emphasis> = 1/2

The magnetic properties of LiCu₂O₂ single-crystal samples without twinning are investigated using electron spin resonance and nuclear magnetic resonance spectroscopy. The experimental results obtained are described in terms of the model of a planar spiral antiferromagnet for the orientation of the magnetic field H ‖ b or H ‖ c and the model of a collinear spin-modulated antiferromagnet for the orientation of the static magnetic field H ‖ a.     

Observation of polarization in bottomonium production at square root of s = 38.8 GeV

We present a measurement of the polarization observed for bottomonium states produced in p-Cu collisions at square root of s = 38.8 GeV. The angular distribution of the decay dimuons of the Upsilon(1S) state shows no polarization at small values of the fractional longitudinal momentum x(F) and transverse momentum p(T) but significant positive transverse production polarization for either p(T)>1.8 GeV/c or for x(F)>0.35. The Upsilon(2S+3S) (unresolved) states show a large transverse production polarization at all values of x(F) and p(T) measured. These observations challenge NRQCD calculations of the polarization expected in the hadronic production of bottomonium states.     

Magnetic structure of low-dimensional LiCu2O2 multiferroic according to 63,65Cu and 7Li NMR studies

The complex NMR study of the magnetic structure of LiCu₂O₂ multiferroic has been performed. It has been shown that the spin spirals in LiCu₂O₂ are beyond the ab, bc, and ac crystallographic planes. The external magnetic field applied along the c axis of the crystal does not change the spatial orientation of spirals in Cu²⁺ chains. A magnetic field of H ₀ = 94 kOe applied along the a and b axes rotates the planes of spin spirals in chains, tending to orient the normal n of spirals along the external magnetic field. The rotation angle of the planes of the magnetic moments are maximal at H ₀ ?? b.     

One-neutron knockout from individual single-particle states of 11Be

The structure of the halo nucleus 11Be has been studied using the reaction 9Be(11Be,10Be+gamma)X at 60 MeV/nucleon. The ground state structure of 11Be is determined by comparing the experimental cross sections to a calculation combining spectroscopic factors from the shell model with l-dependent single-particle cross sections obtained in an eikonal model. This experiment shows the dominant 1s single-particle character of the 11Be ground state and indicates a small contribution of 0d admixture in the wave function. After correction for the approximately 22% intensity to excited levels, a clean and precise distribution of parallel momentum for knockout from the 1s halo wave function is obtained for the first time.     

Electrodynamic Characteristics of Solid Solutions Pb(Fe1 – xScx)2/3W1/3O3 in a Broad Spectral Range

Physics of the Solid State - The methods of broadband dielectric spectroscopy are used to study the effect of substitution of Fe3+ by Sc3+ in Pb(Fe1&nbsp;–&nbsp;xScx)2/3W1/3O3 solid...