Magnetic Circular Dichroism Spectroscopy Research Articles

Sensitive detection of small polaron transitions in cesium-doped tungsten bronze CsxWO3 nanostructures using magnetic circular dichroism spectroscopy

Cesium-doped tungsten bronze CsxWO3 (CWO) has potential applications in the field of energy-saving products due to its high-near-infrared (NIR) shielding ability. We for the first time demonstrate sensitive detection of small polaron transitions in the NIR for CWO nanoarchitectures on the basis of magnetic circular dichroism (MCD) spectroscopy. Two different CWO nanostructures are prepared by organic colloidal and solvothermal methods. Cube-like CWO nanoparticles obtained by the colloidal method exhibit a broad absorption peak at 1500 nm and a weak shoulder at 950 nm, which can be attributed to the localized surface plasmon resonance (LSPR) and small polaron transition, respectively. On the other hand, CWO nanoparticles synthesized by the solvothermal protocol show only a single LSPR peak. Simultaneous deconvolution of both absorption and MCD spectra allows us to discuss the detailed nature of the electronic excitations, and consequently, MCD distinctly unveils the small-polaron transition unresolved in the absorption. Hence, the MCD spectroscopic technique can be a significant optical-modulation method allowing for design of magneto-optically active materials in nanophotonics.

Strong Rashba‐Dresselhaus Effect in Nonchiral 2D Ruddlesden‐Popper Perovskites

AbstractChirality transfer from organic chiral molecules to lead halides is theorized as the origin of the strong Rashba‐Dresselhaus effect causing large circular dichroism (CD) and circularly polarized luminescence (CPL) in metal halide perovskites (MHPs). Here, a concrete empirical evidence is provided that such strong CD and CPL can occur even in nonchiral 2D Ruddlesden‐Popper perovskites (RPPs) (BA)2(MA)n−1PbnI3n+1 (where MA = CH3NH3 and BA = CH3(CH2)3NH3). The CD and CPL responses occurring at the excitonic transition of the MHPs are strongest (≈100 mdeg and 4.8%, respectively) when a single lead halide octahedral [PbI6]4− layer is repeatedly stacked between two nonchiral molecules BA+ (n = 1). However, they are rapidly quenched as n increases. It is hypothesized that strong Rashba‐Dresselhaus splitting in the 2D RPPs originates the strong CD and CPL signatures. Density functional theory calculations reveal that the large interlayer distortions in the inorganic layers at the organic/inorganic interface give rise to the strong Rashba‐Dresselhaus splitting. A Rashba‐Dresselhaus field of ≈600 and ≈50 mT for n = 1 and 2, respectively, is estimated by magnetic circular dichroism spectroscopy. The studies may have significant impact on designing 2D RPPs with large Rashba‐Dresselhaus effects at room temperature for spintronic applications.

The Oxo-Wall Remains Intact: A Tetrahedrally Distorted Co(IV)-Oxo Complex.

In this paper, we report the preparation, spectroscopic and theoretical characterization, and reactivity studies of a Co(IV)-oxo complex bearing an N4-macrocyclic coligand, 12-TBC (12-TBC = 1,4,7,10-tetrabenzyl-1,4,7,10-tetraazacyclododecane). On the basis of the ligand and the structure of the Co(II) precursor, [CoII(12-TBC)(CF3SO3)2], one would assume that this species corresponds to a tetragonal Co(IV)-oxo complex, but the spectroscopic data do not support this notion. Co K-edge XAS data show that the treatment of the Co(II) precursor with iodosylbenzene (PhIO) as an oxidant at -40 °C in the presence of a proton source leads to a distinct shift in the Co K-edge, in agreement with the formation of a Co(IV) intermediate. The presence of the oxo group is further demonstrated by resonance Raman (rRaman) spectroscopy. Interestingly, the EPR data of this complex show a high degree of rhombicity, indicating structural distortion. This is further supported by the EXAFS data. Using DFT calculations, a structural model is developed for this complex with a ligand-protonated structure that features a Co═O···HN hydrogen bond and a four-coordinate Co center in a seesaw-shaped coordination geometry. Magnetic circular dichroism (MCD) spectroscopy further supports this finding. The hydrogen bond leads to an interesting polarization of the Co-oxo π-bonds, where one O(p) lone-pair is stabilized and leads to a regular Co(d) interaction, whereas the other π-bond shows an inverted ligand field. The reactivity of this complex in hydrogen atom and oxygen atom transfer reactions is discussed as well.

Modification of interfacial spin-orbit torque in Co/Pt/oxide hybrid structures

We investigate current-induced spin-orbit torque (SOT) in Co/Pt/oxide systems by varying a sort of the oxide layer. When the Pt thickness is less than \ensuremath{\sim}2 nm, Pt at the interface of the oxide layer is magnetically polarized owing to the magnetic proximity effect. In these systems, fieldlike (FL) SOT depends significantly on the adjacent oxide material, whereas dampinglike SOT is almost irrelevant to oxides. The FL SOT efficiency of the $\mathrm{Pt}/\mathrm{Hf}{\mathrm{O}}_{2}$ sample is 2.2 times greater than that of the Pt/MgO sample at the maximum. X-ray magnetic circular dichroism spectroscopy reveals that the anisotropy of the Pt orbital magnetic moment varies with the oxide material, suggesting that the modulation of the electronic structure at the Pt/oxide interface contributes to SOT enhancement.

Magnetic Circular Dichroism Responses with High Sensitivity and Enhanced Spectral Resolution in Multipolar Plasmonic Modes of Silver Nanoparticles with Dimensions between 90 and 200 nm.

Characteristic features of magnetoplasmonic responses in higher-order multipolar (quadrupolar and octupolar) modes of Ag nanoparticles (from 90 to 200 nm in diameter) are demonstrated for the first time using magnetic circular dichroism (MCD) spectroscopy. In optical extinction spectra, with an increase in the size of the nanoparticles, the red shift of dipolar plasmon peaks and the appearance of higher-order multipolar resonances can reasonably be observed. Aside from the dipolar and quadrupolar modes, the octupolar plasmonic extinction is very weak and almost unresolved. In contrast, strikingly, MCD shows a very sharp and intense peak (or valley) for the octupolar resonance, meaning its unique properties with high sensitivity and enhanced spectral resolution. MCD responses assignable to the quadrupolar mode have a distinct derivative-like shape, which is different from those observed for Ag nanocubes and nanodecahedra in our previous studies. We then discuss this behavior from the viewpoint of size and/or polyhedral shape inhomogeneity.

The three-spin intermediate at the O-O cleavage and proton-pumping junction in heme-Cu oxidases.

Understanding the mechanistic coupling of molecular oxygen reduction and proton pumping for adenosine triphosphate synthesis during cellular respiration is the primary goal of research on heme-copper oxidases—the terminal complex in the membrane-bound electron transport chain. Cleavage of the oxygen-oxygen bond by the heme-copper oxidases forms the key intermediate PM, which initiates proton pumping. This intermediate is now experimentally defined by variable-temperature, variable-field magnetic circular dichroism spectroscopy on a previously unobserved excited state feature associated with its heme iron(IV)-oxo center. These data provide evidence that the iron(IV)-oxo in PM is magnetically coupled to both a copper(II) and a cross-linked tyrosyl radical in the active site. These results provide new insight into the oxygen-oxygen bond cleavage and proton-pumping mechanisms of heme-copper oxidases.

Strongly anisotropic antiferromagnetic coupling in EuFe2As2 revealed by stress detwinning

Of all parent compounds of iron-based high-temperature superconductors, EuFe2As2 exhibits by far the largest magnetostructural coupling due to the sizable biquadratic interaction between Eu and Fe moments. While the coupling between Eu antiferromagnetic order and Fe structural/antiferromagnetic domains enables rapid field detwinning, this prevents simple magnetometry measurements from extracting the critical fields of the Eu metamagnetic transition. Here we measure these critical fields by combining x-ray magnetic circular dichroism spectroscopy with in-situ tunable uniaxial stress and applied magnetic field. The combination of two tuning knobs allows us to separate the stress-detwinning of structural domains from the field-induced reorientation of Eu moments. Intriguingly, we find a spin-flip transition which can only result from a strongly anisotropic interaction between Eu planes. We argue that this anisotropic exchange is a consequence of the strong anisotropy in the magnetically ordered Fe layer, which presents a new form of higher-order coupling between Eu and Fe magnetism.

Magnetic optical rotary dispersion and magnetic circular dichroism in methylammonium lead halide perovskites.

Large magnetic optical rotary dispersion (Faraday rotation) has been demonstrated recently in methylammonium lead bromide. Here, we investigate the prospect of extending the active spectral range by altering the halogen. We also investigate the origins of large Faraday rotation in these diamagnetic materials using magnetic circular dichroism (MCD) spectroscopy and the Kramers-Kronig relations. We find that, while MAPbCl3 (MA = methylammonium) single crystals exhibit a large Verdet constant in the blue, no appreciable Faraday rotation is observed in the red/near infra-red for MAPbI3 single crystals. However, in all film samples, we find clear evidence of large MCD resulting from the Zeeman splitting of the highly resonant 1s exciton state. Our Kramers-Kronig calculations of Faraday rotation based on MCD data matches well with the dispersion of our experimental data for MAPbCl3 and MAPbBr3 , with some deviation in magnitude-demonstrating the excitonic nature of Faraday rotation in these materials. However, our calculations predict significant Faraday rotation in MAPbI3 , contrary to our experimental results, indicating a potential discrepancy between the properties of the thin film and single crystal.

Magnetic moment orientation and in-depth distribution of dysprosium near the surface of DyCo4.6 thin films from x-ray circularly polarized absorption

We have investigated the dysprosium distribution and its magnetic moment orientation at the region near the surface of ${\mathrm{DyCo}}_{4.4}$ and ${\mathrm{DyCo}}_{4.6}$ ferrimagnetic amorphous films with perpendicular magnetic anisotropy. X-ray magnetic circular dichroism spectroscopy of the films at the Dy ${M}_{4,5}$ and Co ${L}_{2,3}$ edges using total electron yield (TEY) detection was performed at 2 K and 300 K temperatures, and at sample orientations ranged from ${0}^{\ensuremath{\circ}}$ to ${70}^{\ensuremath{\circ}}$ with respect to the normal to the sample. The measurements showed an apparent partial decoupling between the cobalt and dysprosium magnetic sublattices. At RT, the magnetic moment per atom of dysprosium was below the minimum value expected if all dysprosium moments were Antiferromagnetic (AF) coupled to cobalt. At 2 K, the cobalt sublattice presented a surprisingly stronger magnetic anisotropy than the dysprosium sublattice. A detailed analysis of the circularly polarized spectra of the Dy ${M}_{5}$ edge, based on the deconvolution of the spectra in their related parallel, antiparallel, and transverse to ${J}_{z}$ spectral components, demonstrates that the spectra are composed by dysprosium with different magnetic moment distributions. The fit of the Dy ${M}_{5}$ spectra using the ${J}_{z}$ spectral components evidenced a gradation of dysprosium concentration due to segregation at the region probed by TEY. The topmost layer was magnetically uncoupled from cobalt. At RT, $25%$ of the dysprosium magnetic moments in the underlayer were found averaged oriented in the same direction of cobalt. The expected weak magnetic coupling of these dysprosium atoms to cobalt should explain the surprisingly lower magnetic anisotropy of the dysprosium sublattice compared to that of cobalt probed by TEY at 2 K.

Probing exchange bias at the surface of a doped ferrimagnetic insulator

With the realization of stress-induced perpendicular magnetic anisotropy, efficient spin-orbit torque switching, and room temperature topological Hall effect, interest in rare earth iron garnets has been revived in recent years for their potential in spintronic applications. In this study, we investigate the magnetic properties of micrometer-thick Bi and Ga substituted thulium iron garnets (BiGa:TmIG) grown by the liquid-phase epitaxy method. Above the magnetization compensation (MC) temperature, anomalous triple hysteresis is observed in BiGa:TmIG/Pt heterostructures by anomalous Hall effect measurements. X-ray magnetic circular dichroism and energy dispersive spectroscopy measurements reveal its origin as an internal exchange bias (EB) effect arising from inhomogeneities localized at the surface of the film. Possibly depending on the difference in thickness and defect realization of the EB layer, two types of magnetization reversal mechanisms, namely, the Stoner-Wohlfarth type and the reversible domain-wall motion type, are observed. Our results show that rich meta-magnetic phases exist in garnets close to MC, which can be robustly tuned by chemical composition engineering and conveniently probed by electrical transport measurements.

The interplay of self-assembly and target binding in centrin 1 from Toxoplasma gondii

Centrins are conserved calcium (Ca2+)-binding proteins typically associated with centrosomes that have been implicated in several biological processes. In Toxoplasma gondii, a parasite that causes toxoplasmosis, three centrin isoforms have been recognized. We have recently characterized the metal binding and structural features of isoform 1 (TgCEN1), demonstrating that it possesses properties consistent with a role as a Ca2+ sensor and displays a Ca2+-dependent tendency to self-assemble. Herein, we expanded our studies, focusing on the self-association and target binding properties of TgCEN1 by combining biophysical techniques including dynamic light scattering, isothermal titration calorimetry, nuclear magnetic resonance, circular dichroism, and fluorescence spectroscopy. We found that the self-assembly process of TgCEN1 depends on different physicochemical factors, including Ca2+ concentration, temperature, and protein concentration, and is mediated by both electrostatic and hydrophobic interactions. The process is completely abolished upon removal of the first 21-residues of the protein and is significantly reduced in the presence of a binding target peptide derived from the human XPC protein (P17-XPC). Titration of P17-XPC to the intact protein and isolated domains showed that TgCEN1 possesses two binding sites with distinct affinities and Ca2+ sensitivity; a high-affinity site in the C-lobe which may be constitutively bound to the peptide and a low-affinity site in the N-lobe which is active only upon Ca2+ stimulus. Overall, our results suggest a specific mechanism of TgCEN1 for Ca2+-modulated target binding and support a N-to-C self-assembly mode, in which the first 21-residues of one molecule likely interact with the C-lobe of the other.

Optical and magneto-optical properties of rhodium nanostructures with different morphologies: Insight into the absorption bump in the UV region

In this study, magneto-optical properties of Rh nanostructures including nanocubes, nanomultipods, and nanotetrahedra, as promising candidates for UV plasmonics, are studied using magnetic circular dichroism (MCD) spectroscopy to obtain better insight into the characteristic absorption bump observed in the UV region. In any nanostructure, unexpectedly, the MCD responses are different from those ascribed to typical localized surface plasmon resonance (LSPR) behaviors in their sign and profile, indicating the distinct absence of LSPR signals. Simultaneous deconvolution of absorption and MCD suggests an appreciable contribution of size and/or morphology-dependent interband transitions of rhodium to their responses.

Physico-chemical characterization of bilirubin-10-sulfonate and comparison of its acid\u2013base behavior with unconjugated bilirubin

Unconjugated bilirubin (UCB) is the end-product of heme catabolism in the intravascular compartment. Although beneficial for human health when mildly elevated in the body, when present at greater than a critical threshold concentration, UCB exerts toxic effects that are related to its physico-chemical properties, particularly affecting the central nervous system. The aim of the present study was to characterize bilirubin-10-sulfonate (ranarubin), a naturally occurring bile pigment, including determination of its mixed acidity constants (pKa*). Thanks to the presence of the sulfonic acid moiety, this compound is more polar compared to UCB, which might theoretically solve the problem with an accurate determination of the UCB pKa* values of its propionic acid carboxylic groups. Bilirubin-10-sulfonate was synthesized by modification of a previously described procedure; and its properties were studied by mass spectrometry (MS), nuclear magnetic resonance (NMR), infrared (IR), and circular dichroism (CD) spectroscopy. Determination of pKa* values of bilirubin-10-sulfonate and UCB was performed by capillary electrophoresis with low pigment concentrations in polar buffers. The identity of the synthesized bilirubin-10-sulfonate was confirmed by MS, and the pigment was further characterized by NMR, IR, and CD spectroscopy. The pKa values of carboxylic acid moieties of bilirubin-10-sulfonate were determined to be 5.02, whereas those of UCB were determined to be 9.01. The physico-chemical properties of bilirubin-10-sulfonate were partially characterized with low pKa* values compared to those of UCB, indicating that bilirubin-10-sulfonate cannot be used as a surrogate pigment for UCB chemical studies. In addition, using a different methodological approach, the pKa* values of UCB were found to be in a mildly alkaline region, confirming the conclusions of a recent critical re-evaluation of this specific issue.

Alternation of Magnetic Anisotropy Accompanied by Metal-Insulator Transition in Strained Ultrathin Manganite Heterostructures

Fundamental understanding of interfacial magnetic properties in ferromagnetic heterostructures is essential to utilize ferromagnetic materials for spintronic device applications. In this paper, we investigate the interfacial magnetic and electronic structures of epitaxial single-crystalline LaAlO$_3$ (LAO)/La$_{0.6}$Sr$_{0.4}$MnO$_3$ (LSMO)/Nb:SrTiO$_3$ (Nb:STO) heterostructures with varying LSMO-layer thickness, in which the magnetic anisotropy strongly changes depending on the LSMO thickness due to the delicate balance between the strains originating from both the Nb:STO and LAO layers, using x-ray magnetic circular dichroism (XMCD) and photoemission spectroscopy (PES). We successfully detect the clear change of the magnetic behavior of the Mn ions concomitant with the thickness-dependent metal-insulator transition (MIT). Our results suggest that double-exchange interaction induces the ferromagnetism in the metallic LSMO film under tensile strain caused by the SrTiO$_3$ substrate, while superexchange interaction determines the magnetic behavior in the insulating LSMO film under compressive strain originating from the top LAO layer. Based on those findings, the formation of a magnetic dead layer near the LAO/LSMO interface is attributed to competition between the superexchange interaction via Mn 3$d_{3z^2-r^2}$ orbitals under compressive strain and the double-exchange interaction via the 3$d_{x^2-y^2}$ orbitals.

A new phenolic acid ester from solid culture of Colletotrichum capsici, an endophytic fungus from Paeonia lactiflora

A new phenolic acid ester, 4'-hydroxyphenylethyl 4,8(R)-dihydroxyphenylpropionate(1), was isolated from an endophytic fungus Colletotrichum capsici of Paeonia lactiflora roots, along with eight known phenolic derivatives, tyrosol(2), 2-(4-hydroxyphenyl) ethyl acetate(3), methyl p-hydroxyphenylacetate(4), methyl m-hydroxyphenylacetate(5), 4-(4-hydroxyphene-thoxy)-4-oxobutanoic acid(6), 4-hydroxyphenethyl methyl succinate(7), trichodenol B(8) and 4-hydroxyphenethyl 2-(4-hydroxyphenyl) acetate(9). Their structures were identified by a combination of high-resolution electrospray ionization mass spectrometry(HR-ESI-MS), nuclear magnetic resonance(NMR) spectroscopy, ultraviolet(UV) spectroscopy and electronic circular dichroism(ECD) spectroscopy. Compounds 2-9 were isolated from this fungus for the first time.

Rare-earth orbital moment contributions to the magnetic anisotropy in magnetostrictive Tb0.3Dy0.7Fe2

Soft x-ray Magnetic Circular Dichroism spectroscopy at the Dy and Tb M4,5 and the Fe L2,3 edges was performed on a sputter deposited polycrystalline Terfenol-D (Tb0.3Dy0.7Fe2) film on sapphire substrates at temperatures from 100 to 300 K to evaluate the elementwise contribution to the magnetocrystalline anisotropy and coercive field. The elemental spin and orbital magnetic moments were calculated using the x-ray Magnetic Circular Dichroism sum rules. As temperatures decreased, the Tb and Fe moments plateau at 200 K with values of 7.6 μB/atom and 1.8 μB/atom, respectively, while the Dy moment increases to 8.9 μB/atom at 100 K. Between 300 and 200 K, the change in magnetic anisotropy is dominated by thermally induced magnetoelastic effects while for temperatures below 200 K magnetocrystalline anisotropy (MCA) changes are dominant. The MCA changes below 200 K appear to be due to increases in the Dy orbital moment with decreasing temperature in this temperature regime.

Cyclo[9]pyrrole: Selective Synthesis of [34]Nonaphyrin(0.0.0.0.0.0.0.0.0).

Cyclo[9]pyrrole, a ring-expanded porphyrin without meso-bridges and having an odd number of pyrroles, was synthesized via the oxidative coupling of 2,2':5',2″-terpyrrole. X-ray crystallography showed a C2-like symmetry with a large root-mean-square deviation. The optical properties and electronic structures were analyzed using magnetic circular dichroism spectroscopy and time-dependent density functional theory calculations.

Syntheses of Water-Soluble Silver(II)-Phthalocyanines toward Optical Sensing for Thiol Detection.

Water-soluble silver(II)-phthalocyanine complexes (AgPcs), tetrakis{4-(N-alkylpyridinium)thio}phthalocyaninato silver(II) tetrafluoroborate, [Ag(tRpySpc)](BF4)4, (R = Me and Et), have been synthesized for the first time by quaternization of pyridyl groups of tetrakis(4-pyridylthio)phthalocyaninato silver(II) by using Meerwein reagents and characterized by ESI-MS, elemental analyses, and optical absorption spectroscopy. Although they strongly aggregate in water, the presence of appropriate surfactants, such as polyethyleneglycol-monooleyl ether (n = approximately 50; PEG50) and sodium dodecyl sulfate, effectively disaggregates them to monomeric species. The spectral properties of the AgPcs and their aggregates in aqueous and nonaqueous solutions have been investigated by optical absorption, emission, and magnetic circular dichroism spectroscopy. These AgPcs rapidly react with thiols such as cysteine, glutathione, homocysteine, and sodium 2-sulfanylethanesulfonate (even on the order of 0.01 mM) in aqueous PEG50 solutions at room temperature to liberate the corresponding macrocyclic ligand, H2Pc, but not with the other amino-acid analogs without sulfhydryl groups. The molar ratio of thiol to AgPc has been determined to be 1:1. Since AgPcs are essentially nonfluorescent at room temperature, while H2Pcs emit intense red fluorescence, AgPcs can be a potent thiol-sensor toward bioimaging.

Direct coordination of pterin to FeII enables neurotransmitter biosynthesis in the pterin-dependent hydroxylases

The pterin-dependent nonheme iron enzymes hydroxylate aromatic amino acids to perform the biosynthesis of neurotransmitters to maintain proper brain function. These enzymes activate oxygen using a pterin cofactor and an aromatic amino acid substrate bound to the FeII active site to form a highly reactive FeIV = O species that initiates substrate oxidation. In this study, using tryptophan hydroxylase, we have kinetically generated a pre-FeIV = O intermediate and characterized its structure as a FeII-peroxy-pterin species using absorption, Mössbauer, resonance Raman, and nuclear resonance vibrational spectroscopies. From parallel characterization of the pterin cofactor and tryptophan substrate-bound ternary FeII active site before the O2 reaction (including magnetic circular dichroism spectroscopy), these studies both experimentally define the mechanism of FeIV = O formation and demonstrate that the carbonyl functional group on the pterin is directly coordinated to the FeII site in both the ternary complex and the peroxo intermediate. Reaction coordinate calculations predict a 14 kcal/mol reduction in the oxygen activation barrier due to the direct binding of the pterin carbonyl to the FeII site, as this interaction provides an orbital pathway for efficient electron transfer from the pterin cofactor to the iron center. This direct coordination of the pterin cofactor enables the biological function of the pterin-dependent hydroxylases and demonstrates a unified mechanism for oxygen activation by the cofactor-dependent nonheme iron enzymes.

Magneto-luminescent nanostructures for biomedicine

Magneto-luminescent nanosystems can be widely applied in biomedicine, namely for disease theranostics, early tumor imaging, and as drug delivery and hyperthermia agents. The creation of such systems using superparamagnetic iron oxide nanoparticles (SPIONs) and semiconductor quantum dots (QDs) approach is popular, since SPIONs are characterized by excellent magnetic properties and zero coercive force, and QDs have advantages over the majority of organic phosphors. In this work, the alloyed (CdxZn1-xSeyS1-y)/ZnS quantum dots are used to reduce the probability of Förster Resonance Energy Transfer or electron transfer, that quench QD photoluminescence, due to a thick gradient semiconductor shell. Moreover, Magnetic Circular Dichroism (MCD) spectroscopy has been successfully applied as a method for monitoring both magnetic properties and colloidal stability of magnetic nanoparticles in a solution, which is crucial for their biomedical applications. The simplicity of SPION/QDs nanostructure formation due to the sequential addition of a SPION solution to a QD solution is a major advantage of this approach. It was demonstrated that these SPION/QDs nanostructures are stable, can be efficiently absorbed by the HeLa cells, and do not show high cytotoxicity at low concentrations (up to 25 nM).