Search

The need for magnetic 2D materials that are stable to the enviroment and have high Curie temperatures is very important for various electronic and spintronic applications. We have found that two-dimensional porphyrin-type aza-conjugated microporous polymer crystals are such a material (Fe-aza-CMPs). Fe-aza-CMPs are stable to CO, CO2, and O2 atmospheres and show unusual adsorption, electronic, and magnetic properties. Indeed, they are semiconductors with small energy band gaps ranging from 0.27 eV to 0.626 eV. CO, CO2, and O2 molecules can be attached in three different ways where single, double, or triple molecules are bound to iron atoms in Fe-aza-CMPs. For different attachment configurations we find that for CO and CO2 a uniform distribution of the molecules is most energetically favorable while for O2 molecules aggregation is most energetically preferable. The magnetic moments decrease from 4 to 2 to 0 for singly, doubly, triply occupied configurations for all gasses respectively. The most interesting magnetic properties are found for O2 molecules attached to the Fe-aza-CMP. For a single attachment configuration we find that an antiferromagnetic state is favorable. When two O2 molecules are attached, the calculations show the highest exchange integral with a value of J = 1071 μeV. This value has been verified by two independent methods where in the first method J is calculated by the energy difference between ferromagnetic and anitferromagnetic configurations. The second method is based on the frozen magnon approach where the magnon dispersion curve has been fitted by the Ising model. For the second method J has been estimated at J = 1100 μeV in excellent agreement with the first method.

In this work we study a low-cost two-dimensional ferromagnetic semiconductor with possible applications in biomedicine, solar cells, spintronics, and energy and hydrogen storage. From first principle calculations we describe the unique electronic, transport, optical, and magnetic properties of a π-conjugated micropore polymer (CMP) with three iron atoms placed in the middle of an isolated pore locally resembling heme complexes. This material exhibits strong Fe-localized dz2 bands. The bandgap is direct and equal to 0.28 eV. The valence band is doubly degenerate at the Γ-point and for larger k-wavevectors the HOMO band becomes flat with low contribution to charge mobility. The absorption coefficient is roughly isotropic. The conductivity is also isotropic with the nonzero contribution in the energy range 0.3-8 eV. The xy-component of the imaginary part of the dielectric tensor determines the magneto-optical Faraday and Kerr rotation. Nonvanishing rotation is observed in the interval of 0.5-5.0 eV. This material is found to be a ferromagnet of an Ising type with long-range exchange interactions with a very high magnetic moment per unit cell, m = 6 μB. The exchange integral is calculated by two independent methods: (a) from the energy difference between ferromagnetic and antiferromagnetic states and (b) from a magnon dispersion curve. In the former case Jnn = 27 μeV. In the latter case the magnon dispersion is fitted by the Ising model with the nearest and next-nearest neighbor spin interactions. From these estimations we find that Jnn = 19.5 μeV and Jnnn = -3 μeV. Despite the different nature of the calculations, the exchange integrals are only within 28% difference.

A new species of marine algae Picochlorum celeri was obtained by enriching for fast reproductive rates under constant high irradiance in semi-continuous culture. Several rapidly-growing cell lines were isolated from the enrichment culture by bringing up cultures from single cells in very high light. Therefore, individual cells are very resilient to inhibition by light. This is a prominent characteristic of this P. celeri in all cell lines. Measured oxygen evolution rates were unusually high. One of these lines is able to double in as short as 2.0 h. Doubling times of other cell lines were between 2.4 and 3.5 h. This species is characterized by high pigment content, high absorption cross section, and an antenna size that is very responsive to irradiance becoming very small at high irradiance.

Because of the importance of ferromagnetism at room temperature, we search for new materials that can exhibit a non-vanishing magnetic moment at room temperature and at the same time can be used in spintronics. The experimental results indicate that d0 ferromagnetism without any magnetic impurities takes place in PbS films made of close-packed lead sulfide nanoparticles of 30 nm. To explain the existence of the d0 ferromagnetism, we propose a model where various PbS bulk and surface configurations of Pb-vacancies are analyzed. The bulk configurations have a zero magnetic moment while the two surface configurations with Pb vacancies with the same non-vanishing magnetic moments and lowest ground state energies contribute to the total magnetization. Based on the experimental value of the saturation magnetization, 0.2 emu g−1, we have found that the calculated Pb vacancy concentration should be about 3.5%, which is close to typical experimental values. Besides being very important for applications, there is one feature of PbS d0 ferromagnetism that makes this material special for fundamental research: PbS ferromagnetism can exhibit topologically driven spatial magnetic moment distributions (e.g., magnetic skyrmions) due to large spin–orbit coupling.

Because of the importance of ferromagnetism at room temperature, we search for new materials that can exhibit a non-vanishing magnetic moment at room temperature and at the same time can be used in spintronics. The experimental results indicate that d0 ferromagnetism without any magnetic impurities takes place in PbS films made of close-packed lead sulfide nanoparticles of 30 nm. To explain the existence of the d0 ferromagnetism, we propose a model where various PbS bulk and surface configurations of Pb-vacancies are analyzed. The bulk configurations have a zero magnetic moment while the two surface configurations with Pb vacancies with the same non-vanishing magnetic moments and lowest ground state energies contribute to the total magnetization. Based on the experimental value of the saturation magnetization, 0.2 emu g-1, we have found that the calculated Pb vacancy concentration should be about 3.5%, which is close to typical experimental values. Besides being very important for applications, there is one feature of PbS d0 ferromagnetism that makes this material special for fundamental research: PbS ferromagnetism can exhibit topologically driven spatial magnetic moment distributions (e.g., magnetic skyrmions) due to large spin-orbit coupling.

The aggregation of ammonium borate salts in hydrocarbon was investigated by 1H, 19F, and 11B pulsed field gradient (PFG) NMR. The molecular self-diffusion coefficients of the borate salts, [C(C6H5)3][B(C6F5)4], [N(CH3)2(n-C18H37)2][B(C6F5)4], [N(n-C18H37)4][B(C6F5)4], a neutral borane compound, and a siloxane model compound were measured in toluene, cyclohexane, hexane, and a solvent of mixed alkanes. Diffusion coefficients were determined from the echo attenuation of the stimulated echo pulsed field gradient NMR signal as described by Stejskal and Tanner. In all of the samples studied, the echo decay was observed to be a pure exponential decay, corresponding to a single diffusion coefficient within the resolution of the NMR experiment. The hydrodynamic radius of an equivalent diffusing sphere was calculated from the experimental diffusion coefficients using the Stokes−Einstein relation. We found that the neutral borane and siloxane model compounds are monomeric (nonaggregated) in both the aliphatic and a...

Spherical tensor operators are used to simplify the relaxation terms of the Redfield equation. A method for treating relaxation is developed using trace-normalized spherical tensor operators. The Redfield equation is recast as a set of coupled linear differential equations for the expectation values of a complete set of spherical tensor operators. A single spin-1/2 particle is treated, and the correspondence of the equation of motion with the Bloch equation is demonstrated. The advantage of the spherical tensor approach is that both the coherent and relaxation terms of the equation of motion are written as matrices that operate on a common vector consisting of the expectation values of spin variables. The process used to construct the equation of motion helps to organize the various contributions to spin relaxation and can be applied uniformly regardless of spin system size. As an example, the relaxation of a two-spin system by the chemical shift anisotropy and dipolar Hamiltonians is developed using the spherical tensor formalism. © 2006 Wiley Periodicals, Inc. Concepts Magn Reson Part A 28A: 270–290, 2006

Both the oxygen diffusion rate and the oxygen solubility vary with depth into the interior of biological membranes. The product of these two gradients generates a single gradient, a permeability gradient, which is a smooth continuous function of the distance from the center of the membrane. Using electron paramagnetic resonance and the spin-probe method, the relaxation gradient of oxygen, which is directly proportional to the permeability gradient, is the quantity that can be directly measured in membranes under physiological conditions. The gradient obtained provides a calibrated ruler for determining the membrane depth of residues either from loop regions of membrane-binding proteins or from the membrane-exposed residues of transmembrane proteins. We have determined the relaxation gradient of oxygen in zwitterionic and anionic phospholipid membranes by attaching a single nitroxide probe to a transmembrane alpha-helical polypeptide at specific residues. The peptide ruler was used to determine the depth of penetration of the calcium-binding loops of the C2 domain of cytosolic phospholipase A(2). The positions of selected residues of this membrane-binding protein that penetrate into the membrane, determined using this ruler, compared favorably with previous determinations using more complex methods. The relaxation gradient constrains the possible values of the membrane-dependent oxygen concentration and the oxygen diffusion gradients. The average oxygen diffusion coefficient is estimated to be at least 2-fold smaller in the membrane than that in water.

The measurement of spin-lattice relaxation rates from spin labels, such as nitroxides, in the presence and absence of spin relaxants provides information that is useful for determining biomolecular properties such as nucleic acid dynamics and the interaction of proteins with membranes. We compare X-band continuous wave (CW) and pulsed or time domain (TD) EPR methods for obtaining spin-lattice relaxation rates of spin labels across the entire range of rotational motion to which relaxation rates are sensitive. Model nitroxides and spin-labeled biological species are used to illustrate the potential complications that arise in extracting relaxation data under conditions typical to biological experiments. The effect of super hyperfine (SHF) structure is investigated for both CW and TD spectra. First and second harmonic absorption and dispersion CW spectra of the nitroxide spin label, TEMPOL, are all fit simultaneously to a model of SHF structure over a range of microwave amplitudes. The CW spectra are novel because all harmonics and microwave phases were acquired simultaneously using our homebuilt CW/TD spectrometer. The effect of the SHF structure on the pulsed free induction decay (FID) and pulsed saturation recovery spectrum is shown for both protonated and deuterated TEMPOL. We present novel pulsed saturation recovery measurements on biological molecules, including spin-lattice relaxation rates of spin-labeled proteins and spin-labeled double-stranded DNA. The impact of structure and dynamics on relaxation rates are discussed in the context of each of these examples. Collisional relaxation rates with oxygen and transition metal paramagnetic relaxants are extracted using both continuous wave and time domain methods. The extent of the errors inherent in the CW method and the advantages of pulsed methods for unambiguously measuring collisional relaxation rates are discussed. Spin-lattice relaxation rates, determined by both CW and pulsed methods, are used to determine the electrostatic potential on the surface of a protein.

We present a novel form of the equation of motion from Bloch-Wangness-Redfield theory (BWRT) that is in a representation-independent operator form. The equation has no time restrictions on it and incorporates Boltzmann equilibrium. We show that this new form gives results consistent with traditional BWRT and limits to BWRT when the additional restrictions and approximations of BWRT are applied to the new equation of motion. The new form shows how the usual equations for relaxation may be easily modified to include detailed balance and to avoid the long-standing problem that certain relaxation rates incorrectly become large when the lattice fluctuation rates become small; that is, the relaxation rates determined from this new approach avoid the BWRT "catastrophe". The new formulation leads to a more complete description of both longitudinal and transverse relaxation in magnetic resonance and takes into account the oscillatory nature of the relaxation of both transverse and longitudinal components in all motional regimes including the slow motion regime. The approach is of direct benefit to spectroscopists because it is described in terms of relaxation rates of observables.

The optical properties of organic chromophores, in the class of nonlinear optical molecules, have improved dramatically. These chromophores have large hyperpolarizability and large permanent dipole moments, in excess of 10 D. When these molecules are mixed with a host polymer at high chromophore density and processed using an aligning electric poling field, the resulting material does not have the electro-optic (EO) response promised by the individual molecules. We have used equilibrium statistical mechanics, and Monte Carlo (MC) methods in a lattice-based model, to investigate how the molecular properties translate into the EO response of the material. We compare our MC results with a previously developed analytic theory and find good agreement when certain assumptions about the analytic theory are made. By use of the MC methods to compute order parameters for chromophores at high density on a lattice in the presence of an external uniform poling field, we find that greater order and hence greater EO per...

Spin trapping, a technique used to characterize short-lived free radicals, consists of using a nitrone or nitroso compound to "trap" an unstable free radical as a long-lived aminoxyl that can be characterized by EPR spectroscopy. The resultant aminoxyl exhibits hyperfine splitting constants that are dependent on the spin trap and the free radical. Such is the case with 2,2-dimethyl-5-hydroxy-1-pyrrolidinyloxyl (DMPO-OH) and 2,2-dimethyl-5-hydroperoxy-1-pyrrodinyloxyl (DMPO-OOH) whose hyperfine splitting constants, A(N) = A(H) = 14.9 G and A(N) = 14.3 G, A(H)(beta) = 11.7 G, and A(H)(gamma) = 1.25 G, respectively, have been used to demonstrate the generation of HO(*) and O(2)(*)(-). However, to date, the source of the apparent A(H)(gamma) hyperfine splitting in DMPO-OOH is not known. We consider three possible explanations to account for the unique EPR spectrum of DMPO-OOH. The first is that the gamma-splitting arises from one of the hydrogen atoms at either carbon 3 or carbon 4 of DMPO-OOH. The second is that the gamma-splitting originates from the hydrogen atom of DMPO-OOH. The third is that the conformational properties of DMPO-R change upon going from DMPO-OH to DMPO-OOH. Experimental and theoretical chemical approaches as well as EPR spectral modeling were used to investigate which of these hypotheses may explain the asymmetric EPR spectrum of DMPO-OOH. From these studies it is shown that the 12-line EPR spectrum of DMPO-OOH results not from any proximal hydrogen, but from additional conformers of DMPO-OOH. Thus, the 1.25 G hyperfine splitting, which has been assigned as a gamma-splitting, is actually from two individual EPR spectra associated with different conformers of DMPO-OOH.

The Lorentzian line shape is the most basic line shape found in field swept continuous wave electron paramagnetic resonance (CW EPR). CW EPR employs Zeeman field modulation for detection purposes. The absorption signal at the first harmonic of modulation is the standard CW EPR signal. Under weak modulation conditions the first harmonic in-phase absorption signal is equivalent to the derivative of the unmodulated Lorentzian line shape. When the field modulation amplitude is appreciable, the distorted first harmonic absorption line shape can still be expressed by a simple analytic formula, as long as the modulation frequency is sufficiently low. We state this often-overlooked formula for the first harmonic signal, and exhibit its extension to arbitrary harmonics. Certain commonly used properties of the weak modulation (derivative Lorentzian) spectrum, such as the peak-to-peak height dependence on microwave power, are also stated in a form that fully takes account of the modulation amplitude. These analytic expressions are compared to numerical simulations of a version of the Bloch equation that contains modulation explicitly. A simple experimental example of overmodulation is also provided to show how the analytic formulas quantitatively account for the effects of modulation amplitude. The impact of modulation on the interpretation of EPR spectra is important given the frequent use of overmodulation when sample concentrations are low, such as in biological EPR studies. The simple analytic formulas demonstrated here are limited by the same physical considerations that limit applicability of the Lorentzian line shape. However, because the Lorentzian line shape is often appealed to in the interpretation of EPR spectra, its simple extension to the regime of appreciable modulation offers valuable insight. For example, the observation that the doubly integrated intensity of the first harmonic absorption spectrum has microwave power dependence that is insensitive to modulation amplitude is demonstrated explicitly. In contrast, the standard formula for the microwave power dependence of the first harmonic peak-to-peak absorption height is modified in a nontrivial way when the modulation amplitude is included. © 2004 Wiley Periodicals, Inc. Concepts Magn Reson Part A 23A: 38–48, 2004

Organic electro-optic (EO) materials have recently been prepared that exhibit EO coefficients in the range of 60–100 pm/V at the telecommunications wavelengths of 1.3 and 1.55 μm. The demonstration of devices with low drive voltage (0.8–2.0 V), together with high bandwidths (40–100 GHz) and low insertion loss (

Human group IIA phospholipase A(2) (hGIIA) is secreted from a number of cells during inflammation and is known to interact strongly with anionic membranes and to exhibit potent Gram-positive bactericidal activity. This protein contains 23 cationic residues, which are scattered over its entire surface, resulting in a high pI of 9.39. To understand the molecular basis for the selective binding of hGIIA to anionic membranes, 14 single-site, spin-labeled hGIIA proteins were analyzed in the presence and absence of vesicles of anionic phospholipid by time domain and continuous wave electron paramagnetic resonance (EPR) spin relaxant techniques. Surprisingly, for hGIIA bound to anionic vesicles, all of the spin labels were highly protected from water-soluble spin relaxants. Together with light scattering studies, these EPR results suggest the formation of a supramolecular aggregate involving clusters of hGIIA molecules bridging together multiple vesicles. This anomalous mode of binding of hGIIA to anionic phospholipid explains previous data in which charge reversal mutation of a few cationic residues on multiple faces of hGIIA leads to a comparable and modest reduction in affinity of the protein for anionic vesicles. In the presence of mixed micelles composed of 10% anionic phospholipids in Triton X-100 a monodisperse protein-lipid complex is formed. Under these conditions, the EPR methods were used to map the surface of hGIIA that constitutes the interfacial binding site (IBS). The IBS of hGIIA consists of the highly hydrophobic surface that surrounds the opening to the active site slot.

A method involving electron paramagnetic resonance spectroscopy of a site-selectively spin-labeled peripheral membrane protein in the presence and absence of membranes and of a water-soluble spin relaxant (chromium oxalate) has been developed to determine how bee venom phospholipase A 2 sits on the membrane. Theory based on the Poisson-Boltzmann equation shows that the rate of spin relaxation of a protein-bound nitroxide by a membrane-impermeant spin relaxant depends on the distance (up to tens of angstroms) from the spin probe to the membrane. The measurements define the interfacial binding surface of this secreted phospholipase A 2 .

Electron paramagnetic resonance (EPR) pulsed saturation recovery (pSR) measurements of spin-lattice relaxation rates have been made on nitroxide-containing fatty acids embedded in lipid bilayers by Hyde and co-workers. The data have been collected for a number of spin-labeled fatty acids at several microwave spectrometer frequencies (from 2 to 35 GHz). We compare these spin-lattice relaxation rates to those predicted by the Redfield theory incorporating several mechanisms. The dominant relaxation mechanism at low spectrometer frequencies is the electron-nuclear dipolar (END) process, with spin rotation (SR), chemical shift anisotropy (CSA), and a generalized spin diffusion (GSD) mechanism all contributing. The use of a wide range of spectrometer frequencies makes clear that the dynamics cannot be modeled adequately by rigid-body isotropic rotational motion. The dynamics of rigid-body anisotropic rotational motion is sufficient to explain the experimental relaxation rates within the experimental error. More refined models of the motion could have been considered, and our analysis does not rule them out. However, the results demonstrate that measurements at only two suitably chosen spectrometer frequencies are sufficient to distinguish anisotropic from isotropic motion. The results presented demonstrate that the principal mechanisms responsible for anisotropically driven spin-lattice relaxation are well understood in the liquids regime.

The Bloch equation containing a Zeeman modulation field is solved analytically by treating the Zeeman modulation frequency as a perturbation. The absorption and dispersion signals at both 0 degrees and 90 degrees modulation phase are obtained. The solutions are valid to first order in the modulation frequency, but are otherwise valid for any value of modulation amplitude or microwave amplitude. A first order treatment of modulation frequency is shown to be a valid approximation over a wide range of typical experimental EPR conditions. The solutions derived from the Bloch equation suggest that the effect of over-modulation on first and second harmonic EPR spectra can be formulated as a mathematical filter that smoothes and broadens the under-modulated signal. The only adjustable filter parameter is a width that is equivalent to the applied peak-to-peak modulation amplitude. The true spin-spin and spin-lattice relaxation rates are completely determined from the under-modulated spectrum. The filters derived from the analytic solutions of the Bloch equation in the linear limit of modulation frequency are tested against numerical solutions of the Bloch equation that are valid for any modulation frequency to show their applicability. The filters are further tested using experimental EPR spectra. Experimental under-modulated spectra are mathematically filtered and compared with the experimental over-modulated spectra. The application of modulation filters to STEPR spectra is explored and limitations are discussed.

Apparent rate constants, at acidic pH and neutral pH for the reaction of a family of ester-containing 5-carboxyl-5-methyl-1-pyrroline N-oxides with superoxide (O2*-) were estimated, using ferricytochrome c as a competitive inhibitor. It was of interest to note that the rate constants were similar among the different nitrones and not that significantly different from that found for 5-(diethoxyphosphoryl)-5-dimethyl-1-pyrroline N-oxide. At acidic pH, the rate constant for spin trapping O2*- was 3-fold greater than that at physiological pH. Subsequent experiments determined the half-life of aminoxyls, derived from the reaction of these nitrones with O2*-. The EPR spectra were modeled by using a global analysis method. The results clearly demonstrated that EPR spectra of all the aminoxyls were inconsistent with a model that included a single gamma-hydrogen splitting. A better interpretation modeled them as two diastereomers with identical nitrogen splittings and slightly different beta-hydrogen splittings. Detailed line width analyses slightly favored an equal line width-unequal population ratio for the two diastereomers.

Utilizing guidance from quantum and statistical mechanics, the electro-optic coefficients of organic materials have been increased to values greater than 100 pm/V at telecommunication wavelengths (e.g., to 130 pm/V at 1.3 microns). Electro-optic materials now afford significant advantages in terms of bandwidth and electro-optic activity over inorganic materials such as lithium niobate. Moreover, organic materials have also been found to be quite processable permitting the fabrication, by reactive ion etching and photolithographic techniques, of 3-D active waveguide structures and integration with both VLSI semiconductor electronics and silica fiber optics. Stripline, cascaded prism, and microresonator structures have been fabricated, as have low-optical-loss coupling structures. A number of prototype devices demonstrating superior performance have been produced; however, the long-term, in-field performance of such devices still remains to be evaluated. Nevertheless, significant advances have been made in improving the thermal and photochemical stability of organic materials and in defining the mechanisms that define these stabilities (by testing under accelerated conditions). The role of nanoscale architecture in systematically improving stability of organic electro-optic materials, as well as contributing to enhanced electro-optic activity and reduced optical loss, has been clarified.

Employing guidance from quantum and statistical mechanics, the electro-optic activity of organic materials has been increased to values greater than 100 pm/V at telecommunication wavelengths (e.g., 130 pm/V at 1.3 microns). Electro-optic materials now afford significant advantages in terms of bandwidth and electro-optic activity over competitive inorganic materials such as lithium niobate. Organic materials have also been found to be quite processable permitting the fabrication by reactive ion etching and photolithographic techniques of 3-D active waveguide structures and integration with both VLSI semiconductor electronics and silica fiber optics. Both stripline and microresonator structures have been fabricated, as have low-optical-loss coupling structures. A number of prototype devices demonstrating superior performance have been demonstrated; however, the long-term, in-field performance of such devices still remains to be evaluated. This article focuses on statistical mechanical theoretical methods that have aided the design of improved materials.

The C2 domain of cytosolic phospholipase A 2 (C2 cPLA2 ) plays an important role in calcium-dependent transfer of the protein from the cytosol to internal cellular membranes as a prelude for arachidonate release from membrane phospholipids. By using a recently developed electron paramagnetic resonance approach together with 13 site-specifically nitroxide spin labeled C2 cPLA2 s and membrane-permeant and -impermeant spin relaxants, we have determined the orientation of C2 cPLA2 with respect to the surface of vesicles of the phospholipid 1,2-dioleoyl- sn -glycero-3-phosphomethanol. The structure reveals that the two calcium-binding regions on C2 cPLA2 that display hydrophobic residues, CBR1 and CBR3, are partially inserted into the core of the membrane. CBR2 that contains predominantly hydrophilic residues is close to the membrane but not inserted. The long axis of the cylindrical C2 cPLA2 molecule is tilted with respect to the bilayer normal, which brings a cluster of basic protein residues close to the phospholipid headgroups. Such an orientation places the two bound calcium ions close to the membrane surface. All together, the results provide structural support for previous proposals that binding of C2 cPLA2 to the membrane interface is driven in part by insertion of hydrophobic surface loops into the membrane core. The results are contrasted with previous studies of the interfacial binding of the first C2 domain of synaptotagmin I, which has shorter surface loops that display basic residues for electrostatic interaction with the bilayer surface.