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This study utilizes geostatistical modelling of magnetic susceptibility (MS) for geophysical prospection of archaeological stratigraphy at the Middle Stone Age rock shelter site of Pinnacle Point 5-6 North. These models are overlaid onto high-resolution photography of the stratigraphic sequence to study the lateral and vertical changes within the magnetic signature of the archaeological sequence and correlate these changes to micromorphological interpretations previously made at the site. In situ analysis is reinforced by laboratory magnetic mineralogical analysis utilizing MS; frequency-dependent susceptibility (chi(FD)); isothermal remanent magnetization; and anhysteric remanent magnetization to understand the composition of the magnetic minerals creating the in situ signature. This study shows that there is consistent variation in the magnetic signatures of the sequence that can be mapped with in situ MS; there is a correlation with laboratory analysis of magnetic mineralogy, which provides insight into changes in human behaviour; and our models correlate well with micromorphological interpretations of the site. info:eu-repo/semantics/publishedVersion

Microcoils provide a cost-effective approach to improve detection limits for mass-limited samples. Single-sided planar microcoils are advantageous in comparison to volume coils, in that the sample can simply be placed on top. However, the considerable drawback is that the RF field that is produced by the coil decreases with distance from the coil surface, which potentially limits more complex multi-pulse NMR pulse sequences. Unfortunately, 1 H NMR alone is not very informative for intact biological samples due to line broadening caused by magnetic susceptibility distortions, and 1 H-13 C 2D NMR correlations are required to provide the additional spectral dispersion for metabolic assignments in vivo or in situ. To our knowledge, double-tuned single-sided microcoils have not been applied for the 2D 1 H-13 C analysis of intact 13 C enriched biological samples. Questions include the following: Can 1 H-13 C 2D NMR be performed on single-sided planar microcoils? If so, do they still hold sensitivity advantages over conventional 5 mm NMR technology for mass limited samples? Here, 2D 1 H-13 C HSQC, HMQC, and HETCOR variants were compared and then applied to 13 C enriched broccoli seeds and Daphnia magna (water fleas). Compared to 5 mm NMR probes, the microcoils showed a sixfold improvement in mass sensitivity (albeit only for a small localized region) and allowed for the identification of metabolites in a single intact D. magna for the first time. Single-sided planar microcoils show practical benefit for 1 H-13 C NMR of intact biological samples, if localized information within ~0.7 mm of the 1 mm I.D. planar microcoil surface is of specific interest.

PURPOSE To develop a new technique that enables simultaneous quantification of whole-brain T1 , T2 , T2∗ , as well as susceptibility and synthesis of six contrast-weighted images in a single 9.1-minute scan. METHODS The technique uses hybrid T2 -prepared inversion-recovery pulse modules and multi-echo gradient-echo readouts to collect k-space data with various T1, T2, and T2∗ weightings. The underlying image is represented as a six-dimensional low-rank tensor consisting of three spatial dimensions and three temporal dimensions corresponding to T1 recovery, T2 decay, and multi-echo behaviors, respectively. Multiparametric maps were fitted from reconstructed image series. The proposed method was validated on phantoms and healthy volunteers, by comparing quantitative measurements against corresponding reference methods. The feasibility of generating six contrast-weighted images was also examined. RESULTS High quality, co-registered T1 , T2 , and T2∗ susceptibility maps were generated that closely resembled the reference maps. Phantom measurements showed substantial consistency (R2 > 0.98) with the reference measurements. Despite the significant differences of T1 (p < .001), T2 (p = .002), and T2∗ (p = 0.008) between our method and the references for in vivo studies, excellent agreement was achieved with all intraclass correlation coefficients greater than 0.75. No significant difference was found for susceptibility (p = .900). The framework is also capable of synthesizing six contrast-weighted images. CONCLUSION The MR Multitasking-based 3D brain mapping of T1 , T2 , T2∗ , and susceptibility agrees well with the reference and is a promising technique for multicontrast and quantitative imaging.

In an assisted self-assembly approach starting from the [Mn6 O2 (piv)10 (4-Me-py)2 (pivH)2 ] cluster a family of Mn-Ln compounds (Ln=Pr-Yb) was synthesised. The reaction of [Mn6 O2 (piv)10 (4-Me-py)2 (pivH)2 ] (1) with N-methyldiethanolamine (mdeaH2 ) and Ln(NO3 )3 ⋅ 6H2 O in MeCN generally yields two main structure types: for Ln=Tb-Yb a previously reported Mn5 Ln4 motif is obtained, whereas for Ln=Pr-Eu a series of Mn7 Ln3 clusters is obtained. Within this series the GdIII analogue represents a special case because it shows both structural types as well as a third Mn2 Ln2 inverse butterfly motif. Variation in reaction conditions allows access to different structure types across the whole series. This prompts further studies into the reaction mechanism of this cluster assisted self-assembly approach. For the Mn7 Ln3 analogues reported here variable-temperature magnetic susceptibility measurements suggest that antiferromagnetic interactions between the spin carriers are dominant. Compounds incorporating Ln=NdIII (2), SmIII (3) and GdIII (5) display SMM behaviour. The slow relaxation of the magnetisation for these compounds was confirmed by ac measurements above 1.8 K.

Inducing magnetic coupling between 4f elements is an ongoing challenge. To overcome this formidable difficulty, we incorporate highly delocalized tetrazinyl radicals, which strongly couple with f-block metallocenes to form discrete tetranuclear complexes. Synthesis, structure, and magnetic properties of two tetranuclear [(Cp*2 Ln)4 (tz. )4 ]⋅3(C6 H6 ) (Cp*=pentamethylcyclopentadienyl; tz=1,2,4,5-tetrazine; Ln=Dy, Gd) complexes are reported. An in-depth examination of their magnetic properties through magnetic susceptibility measurements as well as computational studies support a highly sought-after radical-induced "giant-spin" model. Strong exchange interactions between the LnIII ions and tz. radicals lead to a strong magnet-like behaviour in this molecular magnet with a large coercive field of 30 kOe.

The synthesis of phenalenyl-endcapped [5]cumulene as a cumulene-based singlet biradical and the spin correlation changes of one-dimensional aggregates are described. The high propensity for self-aggregation of phenalenyl rings and the introduction of bulky substituents into the appropriate positions led to the formation of a one-dimensional chain assembly. Single-crystal X-ray structural analysis indicated that the bond length alternation of the cumulene chain increased with decreasing temperature, along with improved overlapping of the phenalenyl rings. Variable-temperature Raman spectroscopy and magnetic susceptibility measurements revealed that a localized spin pair within the molecule decouples at low temperatures, and a continuum spin system involving intra- and intermolecular spin-spin interactions emerges in the one-dimensional chain.

We report the design, synthesis, structure, and properties of two complex layered phosphide nitrides, $Ak$Th$_2$Mn$_4$P$_4$N$_2$ ($Ak$ = Rb, Cs), which contain anti-fluorite-type [Mn$_2$P$_2$] bilayers separated by fluorite-type [Th2N2] layers as a result of the intergrowth between AkMn$_2$P$_2$ and ThMnPN. The new compounds are featured with an intrinsic hole doping associated with the interlayer charge transfer and a built-in chemical pressure from the [Th$_2$N$_2$] layers, both of which are reflected by the changes in the lattice and the atomic position of phosphorus. The measurements of magnetic susceptibility, electrical resistivity, and specific heat indicate existence of local moments as well as itinerant electrons in relation with d-p hybridizations. The expected dominant antiferromagnetic interactions with enhanced d-p hybridizations were demonstrated by the first-principles calculations only when additional Coulomb repulsions are included. The density of states at the Fermi level derived from the specific-heat analysis are 3.5 and 7.5 times of the calculated ones for Ak = Rb and Cs, respectively, suggesting strong electron correlations in the title compounds.

Purpose Myelin has long been the target of neuroimaging research. However, most available techniques can only provide a voxel-averaged estimate of myelin content. In the human brain, white matter fiber pathways connecting different brain areas and carrying different functions often cross each other in the same voxel. A measure that can differentiate the degree of myelination of crossing fibers would provide a more specific marker of myelination. Theory and Methods One MRI signal property that is sensitive to myelin is the phase accumulation. This sensitivity is used by measuring the phase accumulation of the signal remaining after diffusion-weighting, which is called diffusion-prepared phase imaging (DIPPI). Including diffusion-weighting before estimating the phase accumulation has two distinct advantages for estimating the degree of myelination: (1) It increases the relative contribution of intra-axonal water, whose phase is related linearly to the thickness of the surrounding myelin (in particular the log g-ratio); and (2) it gives directional information, which can be used to distinguish between crossing fibers. Here the DIPPI sequence is described, an approach is proposed to estimate the log g-ratio, and simulations are used and DIPPI data acquired in an isotropic phantom to quantify other sources of phase accumulation. Results The expected bias is estimated in the log g-ratio for reasonable in vivo acquisition parameters caused by eddy currents (~4%-10%), remaining extra-axonal signal (~15%), and gradients in the bulk off-resonance field ( Conclusion This new sequence may provide a g-ratio estimate per fiber population crossing within a voxel.

We report the single crystal XRD and MicroED structure, magnetic susceptibility, and EPR data of a series of CaMn3 IV O4 and YMn3 IV O4 complexes as structural and spectroscopic models of the cuboidal subunit of the oxygen-evolving complex (OEC). The effect of changes in heterometal identity, cluster geometry, and bridging oxo protonation on the spin-state structure was investigated. In contrast to previous computational models, we show that the spin ground state of CaMn3 IV O4 complexes and variants with protonated oxo moieties need not be S=9/2. Desymmetrization of the pseudo-C3 -symmetric Ca(Y)Mn3 IV O4 core leads to a lower S=5/2 spin ground state. The magnitude of the magnetic exchange coupling is attenuated upon oxo protonation, and an S=3/2 spin ground state is observed in CaMn3 IV O3 (OH). Our studies complement the observation that the interconversion between the low-spin and high-spin forms of the S2 state is pH-dependent, suggesting that the (de)protonation of bridging or terminal oxygen atoms in the OEC may be connected to spin-state changes.

Ferroelectric spin crossover (SCO) behavior is demonstrated to occur in the cobalt(II) complex, [Co(FPh-terpy)2 ](BPh4 )2 ⋅3ac (1⋅3 ac; FPh-terpy=4'-((3-fluorophenyl)ethynyl)-2,2':6',2''-terpyridine) and is dependent on the degree of 180° flip-flop motion of the ligand's polar fluorophenyl ring. Single crystal X-ray structures at several temperatures confirmed the flip-flop motion of fluorobenzene ring and also gave evidence for the SCO behavior with the latter behavior also confirmed by magnetic susceptibility measurements. The molecular motion of the fluorobenzene ring was also revealed using solid-state 19 F NMR spectroscopy. Thus the SCO behavior is accompanied by the flip-flop motion of the fluorobenzene ring, leading to destabilization of the low spin cobalt(II) state; with the magnitude of rotation able to be controlled by an electric field. This first example of spin-state conversion being dependent on the molecular motion of a ligand-appended fluorobenzene ring in a SCO cobalt(II) compound provides new insight for the design of a new category of molecule-based magnetoelectric materials.

Actinide +VI complexes ( AnVI = UVI , NpVI and PuVI ) with dipicolinic acid derivatives were synthesized and characterized by powder XRD, SQUID magnetometry and NMR spectroscopy. In addition, NpVI and PuVI complexes were described by first principles CAS based and two-component spin-restricted DFT methods. The analysis of the 1 H paramagnetic NMR chemical shifts for all protons of the ligands according to the X-rays structures shows that the Fermi contact contribution is negligible in agreement with spin density determined by unrestricted DFT. The magnetic susceptibility tensor is determined by combining SQUID, pNMR shifts and Evans' method. The SO-RASPT2 results fit well the experimental magnetic susceptibility and pNMR chemical shifts. The role of the counterions in the solid phase is pointed out; their presence impacts the magnetic properties of the NpVI complex. The temperature dependence of the pNMR chemical shifts has a strong 1/T contribution, contrarily to Bleaney's theory for lanthanide complexes. The fitting of the temperature dependence of the pNMR chemical shifts and SQUID magnetic susceptibility by a two-Kramers-doublet model for the NpVI complex and a non-Kramers-doublet model for the PuVI complex allows for the experimental evaluation of energy gaps and magnetic moments of the paramagnetic center.

Made available in DSpace on 2021-06-25T12:39:10Z (GMT). No. of bitstreams: 0 Previous issue date: 2021-02-26 Brazilian Coordinating Body for Higher-Level Staff Improvement Spanish Ministry of Economy and Competitiveness Global demand for soil information has led to investigations that have adopted ways to estimate soil attributes quickly and effectively. In this context, magnetic susceptibility (chi) has gained prominence because it is a technique capable of estimating other attributes that are more difficult to acquire. This study aimed to (a) evaluate the performance of chi for the prediction of sand, silt, clay, hue, hematite/(hematite + goethite) ratio, Fe content of pedogenic iron oxides, and remaining phosphorus and (b) develop maps of chi, soil attributes and attributes predicted by chi in the state of Rio Grande do Sul (RS), Brazil. Here, 198 soil samples under forest and native pasture were used for testing the potential of chi as a predictive technique, separating the data into calibration (n(c) = 149) and validation sets (n(v) = 49). Linear regression was used to obtain the pedotransfer equations according to soil classes and lithology. To visualize the distribution of the values of chi and other soil attributes in RS, maps were made with the real values of chi and the real and estimated values of soil attributes. The great range of the chi values and related attributes was associated with the lithological and pedological influence, allowing the construction of predictive models that encompass a large gradient of chi. In the predictions made in groups, the attributes of Oxisols and Ultisols were best estimated by chi; however, among the lithology groups, the extrusive igneous rocks stood out. Univ Fed Rio Grande do Sul, Fac Agron, Dept Soils, BR-91540000 Porto Alegre, RS, Brazil Univ Cordoba, Dept Agron, Cordoba 14071, Spain Univ Marilia, Ctr Agr Sci, BR-17525902 Marilia, SP, Brazil State Univ Sao Paulo, Res Grp Caracterizacao Solo Fins Manejo Especif, Dept Soils & Fertilizers, BR-14883292 Jaboticabal, Brazil State Univ Sao Paulo, Res Grp Caracterizacao Solo Fins Manejo Especif, Dept Soils & Fertilizers, BR-14883292 Jaboticabal, Brazil Spanish Ministry of Economy and Competitiveness: AGL 2017-87074-C2-2-R

Purpose Measuring the transverse-relaxation rate R 2 ' provides valuable information in quantitative evaluation of tissue microstructure, for example, in terms of oxygenation levels. Here, we propose an alternating unbalanced SSFP pulse sequence for rapid whole-brain 3D R 2 ' mapping. Methods Unlike currently practiced, spin echo-based R 2 ' measurement techniques, the proposed method alternates between SSFP-FID and SSFP-ECHO modes for rapid 3D encoding of transverse relaxation rates expressed as R2 + R 2 ' and R2 - R 2 ' . Z-shimming gradients embedded into multi-echo trains of each SSFP module are designed to achieve relative immunity to large-scale magnetic-field variations (ΔB0 ). Appropriate models for the temporal evolution of the two groups of SSFP signals were constructed with ΔB0 -induced modulations accounted for, leading to ΔB0 -corrected estimation of R2 , R 2 ' , and R 2 ∗ (= R2 + R 2 ' ). Additionally, relative magnetic susceptibility (Δχ) maps were obtained by quantitative susceptibility mapping of the phase data. Numerical simulations were performed to optimize scan parameters, followed by in vivo studies at 3 T in 7 healthy subjects. Measured parameters were evaluated in six brain regions, and subjected to interparameter correlation analysis. Results The resultant maps of R 2 ' and additionally derived R2 , R 2 ∗ , and Δχ all demonstrated the expected contrast across brain territories (eg, deep brain structures versus cortex), with the measured values in good agreement with previous reports. Furthermore, regression analyses yielded strong linear relationships for the transverse relaxation parameters ( R 2 ' , R2 , and R 2 ∗ ) against Δχ. Conclusion Results suggest feasibility of the proposed method as a practical and reliable means for measuring R 2 ' , R2 , R 2 ∗ , and Δχ across the entire brain.

Addition of the bipyridyl-embedded cycloparaphenylene nanohoop bipy[9]CPP to [Fe{H2 B(pyz)2 }] (pyz=pyrazolyl) produces the distorted octahedral complex [Fe(bipy[9]CPP){H2 B(pyz)2 }2 ] (1). The molecular structure of 1 shows that the nanohoop ligand contains a non-planar bipy unit. Magnetic susceptibility measurements indicate spin-crossover (SCO) behaviour with a T1/2 of 130 K, lower than that of 160 K observed with the related compound [Fe(bipy){H2 B(pyz)2 }2 ] (2), which contains a conventional bipy ligand. A computational study of 1 and 2 reveals that the curvature of the nanohoop leads to the different SCO properties, suggesting that the SCO behaviour of iron(II) can be tuned by varying the size and diameter of the nanohoop.

Three new hetero-metallic copper(II)-manganese(II) complexes, [(CuL)2 Mn3 (C6 H5 CO2 )6 ] (1), [(CuL)2 Mn(CH3 CO2 )2 ] (2), and {[(CuL)2 Mn(C6 H5 CH2 CO2 )2 ] ⋅ 2CH3 CN} (3), have been synthesized using [CuL] as ''metalloligand'' (where H2 L=N,N'-bis(2-hydroxynaphthyl-methylidene)-1,3-propanediamine). Single-crystal structural analyses show an almost linear penta-nuclear structure for complex 1 where a square planar [CuL] unit is connected to each of the two terminal MnII ions of a linear, centrosymmetric [Mn3 (benzoate)6 ] unit through the double phenoxido bridges. Both complexes 2 and 3 possess a linear tri-nuclear structure where two terminal square-pyramidal [CuL] units are bonded to the central MnII ion through double phenoxido oxygen atoms along with a syn-syn bridging acetate (for 2)/phenyl acetate (for 3). All three complexes exhibit catecholase, and phenoxazinone synthase-like activities under aerial conditions. For catecholase like activity, the turnover numbers (kcat ) are 595, 40, and 205 h-1 whereas, for phenoxazinone synthase like activity, the turnover numbers are 25, 4, and 11 h-1 for complexes 1-3, respectively. The mechanism of both catalytic oxidase activities is proposed on the basis of mass spectral evidences. Variable-temperature (2-300 K) dc molar magnetic susceptibility measurements of 1 reveal antiferromagnetic interactions between the Cu-Mn centres (J1 =-29.3 cm-1 ), and also between the Mn-Mn centres of the [Mn3 (benzoate)6 ] unit (J2 =-0.68 cm-1 ). On increasing the magnetic field at 2 K, its ground spin state changes from S=3/2 to S=5/2 at 4 T, attributable to the low value of J2 which makes the excited spin states close in energy with the ground spin state. Complexes 2 and 3 show antiferromagnetic coupling interactions between the Cu-Mn pairs with J values of -9.51, and -5.32 cm-1 , respectively.

Downhole nuclear magnetic resonance technology was applied in four boreholes intersecting glaciomarine sediments of the Ottawa Valley, Ontario. The study evaluated the ability of slim‐hole nuclear magnetic resonance tools to measure in situ volumetric water contents (porosities in saturated sediments) for geohazard and hydrogeological applications. The sediments are composed of clay‐ and silt‐sized grains of glacially eroded rock flour derived from the Precambrian Shield containing trace amounts of magnetic minerals, and porosities ranging from 40 to 74 porosity units (PU, 1% porosity = 1 PU). Two nuclear magnetic resonance instruments were deployed with echo times of 0.5 and 1.0 ms, and diameters of investigation ranging from 14.0 to 30.5 cm. Quantitative nuclear magnetic resonance porosities in the sediments were typically within ±5 PU (95% within ±10 PU) of core calibration data sets in the silty clays where threshold bulk magnetic susceptibility values were

We investigate the relative fractions of remanent and induced magnetization of the fillings of neolithic long pits in order to develop remanent magnetization as an additional parameter for the archaeological interpretation of magnetic maps. We determine the Koenigsberger ratio – the ratio between induced and remanent magnetization intensities – for key targets by combining magnetic mapping with downhole measurements of susceptibility, numerical modelling, and inversion computations. The susceptibility data were acquired in drill holes along profiles crossing the targets identified by magnetic mapping. The targets of this exemplary study are house-accompanying pits at the Linearbandkeramik site Vráble ‘Farské’. For this purpose, we conducted auger drillings with a point distance of 25 cm and measured the susceptibility with a downhole susceptometer. The resulting two-dimensional susceptibility distributions were used to calculate synthetic magnetic anomalies corresponding to the case of solely induced magnetization. The comparison to the observed magnetic data showed a considerable discrepancy that can only be explained with remanent magnetization. To determine the Koenigsberger ratio we developed a new interpretation approach, using parts of the measured susceptibility distribution as a basis function. The free parameters of this numerical problem are determined by non-linear inversion. We applied the novel approach to six exemplary profiles and found Koenigsberger ratios between 1.6 and 10.5 with the majority of the values being smaller than 4. These values apply to soil volumes with susceptibility values larger than 27–160 × 10-5 SI. Laboratory measurements on soil samples were used to examine the possible causes of the observed magnetization. The analyses suggest that the increase in susceptibility and remanent magnetization in the pits is caused by an increase of the population of magnetotactic bacteria and deposition of magnetized material, followed by the alignment of the ferrimagnetic iron compounds in the waterlogged environment of the pits and accumulation of viscous remanent magnetization.

Anisotropic NMR has gained increasing popularity to determine the structure and specifically the configuration of small, flexible, non-crystallizable molecules. However, it suffers from the necessity to dissolve the analyte in special media such as liquid crystals or polymer gels. Generally, small degrees of alignment are also caused by an anisotropic magnetic susceptibility of the molecule, for example, induced by aromatic moieties. For this mechanism, the alignment can be predicted via density functional theory. Here we show that both residual dipolar couplings and residual chemical shift anisotropies can be acquired from natural products without special sample preparation using magnetically induced alignment. On the two examples of the novel natural product gymnochrome G and the alkaloid strychnine, these data, together with the predicted alignment, yield the correct configuration with high certainty.

PURPOSE Many conventional ex vivo magnetic resonance imaging (MRI) setups utilize cylindrical or other nonspherical tissue containers which can cause static field (B0 ) inhomogeneity affecting the accuracy of the measurements in an orientation-dependent manner. In this work we demonstrate an experimental method to obtain MRI of ex vivo tissue samples held in a spherical container in order to minimize bulk susceptibility-induced B0 inhomogeneity in arbitrary orientations. METHODS B0 inhomogeneity caused by tissue-air susceptibility mismatch can be theoretically eliminated if the surface of susceptibility discontinuity is spherical. This situation can be approximated by putting a tissue sample in a spherical shell filled with materials with tissue-like magnetic susceptibility. We achieved this on an intact monkey brain by (a) holding the brain with a three-dimensional (3D)-printed holder with tissue-like (within 0.5 ppm) susceptibility, and (b) enclosing the brain and the holder in an acrylic spherical shell filled with diamagnetic liquid. Furthermore, the sphere and the radio-frequency coil for MRI were mounted on a 3D-printed frame designed to reduce B0 inhomogeneity contributions. The sphere could be rotated freely without disturbing the RF coil to facilitate multi-orientation imaging. We verified our setup by mapping B0 in the monkey brain at 13 different orientations in a human 7T scanner, and measuring orientation-dependent R2∗ relaxation rates in the white and gray matters of the brain. The results were then compared with a setup where the brain was held inside a cylindrical container. RESULTS In all orientations, the B0 standard deviation in the brain in the spherical setup (converted to Larmor frequency offset) was less than about 10 Hz. This corresponds to two-sigma deviation of B0 of

A rational approach to modulating easy-axis magnetic anisotropy by varying the axial donor ligand in heptacoordinated FeII complexes has been explored. In this series of complexes with formulae of [Fe(H4 L)(NCS)2 ]⋅3 DMF⋅0.5 H2 O (1), [Fe(H4 L)(NCSe)2 ]⋅3 DMF⋅0.5 H2 O (2), and [Fe(H4 L)(NCNCN)2 ]⋅DMF⋅H2 O (3) [H4 L=2,2'-{pyridine-2,6-diylbis(ethan-1-yl-1-ylidene)}bis(N-phenylhydrazinecarboxamide)], the axial positions are successively occupied by different nitrogen-based π-donor ligands. Detailed dc and ac magnetic susceptibility measurements reveal the existence of easy-axis magnetic anisotropy for all of the complexes, with 1 [Ueff =21 K, τ0 =1.72×10-6 s] and 2 [Ueff =25 K, τ0 =2.25×10-6 s] showing field-induced slow magnetic relaxation behavior. However, both experimental studies and theoretical calculations indicate the magnitude of the D value of complex 3 to be larger than those of complexes 1 and 2 due to the axial bond angle being smaller than that for an ideal geometry. Detailed analysis of the field and temperature dependences of relaxation time for 1 and 2 has revealed that multiple relaxation processes (quantum tunneling of magnetization, direct, and Raman) are involved in slow magnetic relaxation for both of these complexes. Magnetic dilution experiments support the role of intermolecular short contacts.

A combined structural, magnetic and thermoelectric study of polycrystalline ternary MIn2S4 (M = Mn, Fe, Co, Ni) thiospinels is presented. All compounds crystallize with MgAl2O4-type structure. Rietveld refinement analysis confirmed that the preferred crystallographic position of transition metal element changes from mainly tetrahedral 8a for Mn to exclusively octahedral 16d for Ni (i.e. increase of the inversion parameter). Magnetic susceptibility measurements revealed M-elements to possess 2+ oxidation state in MIn2S4. All these compounds order antiferromagnetically with Neel temperatures T-N ranging from 5-13 K. The studied thiospinels are n-type semiconductors with large values of electrical resistivity rho > 0.6 omega center dot m at room temperature. An increase of the inversion parameter leads to a reduction of the determined activation energies, as well as to a more disorder-like behavior of thermal conductivity. The highest thermoelectric Figure of merit ZT was observed for MIn2S4 with M = Fe, Ni, which adopt inverse spinel structure.

We present a facile strategy to prepare the molecularly imprinted polymers layer on the surface of Fe3 O4 nanoparticles with core-shell structure via sol-gel condensation for recognition and enrichment of triclosan. The Fe3 O4 nanoparticles were first synthesized by a solvothermal method. Then, template triclosan was self-assembled with the functional monomer 3-aminopropyltriethoxysilane on the silica-coated Fe3 O4 nanoparticles in the presence of ethanol and water. Finally, the molecularly imprinted polymers were formed on the surface of silica-coated Fe3 O4 nanoparticles to obtain the product. The morphology, magnetic susceptibility, adsorption, and recognition property of magnetic molecularly imprinted polymers were characterized using transmission electron microscopy, Fourier transform infrared spectroscopy, X-ray diffractometry, vibrating sample magnetometry, and re-binding experiments. The magnetic molecularly imprinted polymers showed binding sites with good accessibility, fast adsorption rate, and high adsorption capacity (218.34 μg/g) to triclosan. The selectivity of magnetic molecularly imprinted polymers was evaluated by the rebinding capability of triclosan and two other structural analogues (phenol and p-chlorophenol) in a mixed solution and good selectivity with an imprinting factor of 2.46 was obtained. The application of triclosan removal in environmental samples was demonstrated.

Five varieties of Belgian black marbles are investigated in order to discriminate them. Their age ranges from Frasnian (Golzinne) to Visean (Dinant, Theux, Basècle, Lives). Three methods were used: petrography, magnetic susceptibility and geochemistry of major elements and Rare Earth Elements (REE). The petrographic analyze reveals 16 microfacies reflecting very quiet environments, sporadically perturbed by more energetic phenomena like turbidites or storms. These microfacies are integrated in two depositional models: a quiet offshore setting, below or close to the storm wave base (Salet, Basècles) and a shallow but very restricted zone, protected from waves and currents (Lives and Golzinne). The magnetic susceptibility results show that all the black marbles are characterized by very low, even slightly negative values, except the Golzinne one which shows higher values. Geochemical data allow to discriminate between the Theux black marble (low SiO2 content), and the Basècles samples (low Al2O3, K2O and REE contents). These methods could be useful to determine/refine the origin of archaeological stones, even if all these analyses are destructive. Two archeologic samples were investigated in order to identify their possible origin.

During urgent archaeological excavations in the city of Plovdiv (South Bulgaria), a Roman pottery workshop was found, including several dome kilns, ceramic sherds, and a large clay deposit incorporating yellow and gray clay layers. A set of the ceramic specimens (kitchenwares and tablewares) and raw clay samples were investigated using a portable device for X-ray fluorescence and laboratory equipment for magnetic measurements, aiming to provide specific information about the origin and firing technology of the pottery. Despite significant difference in calcium content between local raw clay and pottery samples, we conclude that local natural clay sources were used and the initial stages of production involved clay purification, although we cannot rule out the procurement of more distant clay sources. Magnetic susceptibility testing allowed for determination of the maximum firing temperatures, showing that the pottery were fired predominantly at 780°C, with some samples being fired at temperatures up to 860°C. Magnetic analyses show that kitchenwares were fired under more uniform conditions than the tablewares, which undoubtedly reflected in the quality of the vessels produced.

A magnetotelluric finite‐element modelling algorithm is developed, which is capable of handling three‐dimensional conductive and magnetic anisotropic anomalies. Different from earlier three‐dimensional magnetotelluric anisotropic modelling methods, the algorithm we presented has taken the magnetic anisotropy into consideration. The variational equations are produced by the Galerkin method and the governing equations are solved using a hexahedral vector edge finite‐element method. The accuracy of this algorithm is firstly validated by comparing its solutions with the results of finite‐difference method for a three‐dimensional conductive arbitrary anisotropic model, and then validated by comparing with analytical solutions for a one‐dimensional magnetic model. The responses of four kinds of models under different conditions are studied, and some conclusions are obtained. It shows that for materials with a high magnetic permeability, its influence on magnetotelluric responses cannot be ignored in some circumstances. Especially, if the magnetic susceptibility is exceptionally high, it may really distort the apparent resistivities of lower resistive anomalies. These conclusions are also beneficial for magnetotelluric survey.

Reactions of [Mn(H2 dapsc)Cl2 ]⋅H2 O (dapsc=2,6- diacetylpyridine bis(semicarbazone)) with K3 [Fe(CN)6 ] and (PPh4 )3 [Fe(CN)6 ] lead to the formation of the chain polymeric complex {[Mn(H2 dapsc)][Fe(CN)6 ][K(H2 O)3.5 ]}n ⋅1.5n H2 O (1) and the discrete pentanuclear complex {[Mn(H2 dapsc)]3 [Fe(CN)6 ]2 (H2 O)2 }⋅4 CH3 OH⋅3.4 H2 O (2), respectively. In the crystal structure of 1 the high-spin [MnII (H2 dapsc)]2+ cations and low-spin hexacyanoferrate(III) anions are assembled into alternating heterometallic cyano-bridged chains. The K+ ions are located between the chains and are coordinated by oxygen atoms of the H2 dapsc ligand and water molecules. The magnetic structure of 1 is built from ferrimagnetic chains, which are antiferromagnetically coupled. The complex exhibits metamagnetism and frequency-dependent ac magnetic susceptibility, indicating single-chain magnetic behavior with a Mydosh-parameter φ=0.12 and an effective energy barrier (Ueff /kB ) of 36.0 K with τ0 =2.34×10-11 s for the spin relaxation. Detailed theoretical analysis showed highly anisotropic intra-chain spin coupling between [FeIII (CN)6 ]3- and [MnII (H2 dapsc)]2+ units resulting from orbital degeneracy and unquenched orbital momentum of [FeIII (CN)6 ]3- complexes. The origin of the metamagnetic transition is discussed in terms of strong magnetic anisotropy and weak AF interchain spin coupling.

Purpose To characterize the magnetic susceptibility changes of liver fibrosis using susceptibility tensor imaging. Methods Liver biopsy tissue samples of patients with liver fibrosis were obtained. Three-dimensional gradient-echo and diffusion-weighted images were acquired at 9.4 T. Susceptibility tensors of the samples were calculated using the gradient-echo phase signal acquired at 12 different orientations relative to the B0 field. Susceptibility anisotropy of the liver collagen fibers was quantified and compared with diffusion anisotropy, measured by DTI. For validation, a comparison was made to histology including hematoxylin and eosin staining, iron staining, and Masson's trichrome staining. Results Areas with strong diamagnetic susceptibility were observed in the tissue samples forming fibrous patterns. This diamagnetic susceptibility was highly anisotropic. Both the mean magnetic susceptibility and susceptibility anisotropy of collagen fibers exhibited a strong contrast against the surrounding nonfibrotic tissues. The same regions also showed an elevated diffusion anisotropy but with much lower tissue contrast. Masson's trichrome staining identified concentrated collagens in the fibrous regions with high susceptibility anisotropy, and a linear correlation was found between the susceptibility anisotropy and the histology-based staging. Conclusion Diamagnetic susceptibility indicates the presence of collagen in the fibrotic liver tissues. Mapping magnetic susceptibility anisotropy may serve as a potential marker to quantify collagen fiber changes in patients with liver fibrosis.

The molecule (E)-(5-(3-anthracen-9-yl-allylidene)-2,2-dimethyl-[1,3] dioxane-4,6-dione) (E-AYAD) undergoes E→Z photoisomerization. In the solid state, this photoisomerization process can initiate a physical transformation of the crystal that is accompanied by a large volume expansion (ca. 10 times), loss of crystallinity, and growth of large pores. This physical change requires approximately 10 % conversion of the E isomer to the Z isomer and results in a gel-like solid with decreased stiffness that still retains its mechanical integrity. The induced porosity allows the expanding gel to engulf superparamagnetic nanoparticles from the surrounding liquid. The trapped superparamagnetic nanoparticles impart a magnetic susceptibility to the gel, allowing it to be moved by a magnetic field. The photoinduced phase transition, starting with a compact crystalline solid instead of a dilute solution, provides a new route for in situ production of functional porous materials.

Strong wildfires pose significant damage to all soil qualities and lead to land degradation. The complex nature and properties of fire‐derived materials require multidisciplinary efforts for their reliable characterization. The main objective of our study was to evaluate the suitability of magnetic properties of fire‐affected soils as proxy parameters for wildfire severity and to relate magnetic signature of burnt soils to carbon and nitrogen contents as influenced by wildfires. We present mineral magnetic investigation of 22 sites with wildfire‐affected soils and 17 nonburnt soils from nearby locations. We employed measurements of magnetic susceptibility and anhysteretic remanence in combination with scanning and transmission electron microscopy observations on magnetic particles from burnt soils and ashes. Bulk soil and vegetation ash analyses of total carbon and nitrogen, organic carbon, and elemental content were carried out as well. We show that pyrogenic magnetic enhancement is restricted to the uppermost 0‐ to 2‐cm soil depth and can be used as a proxy for wildfire severity. Strong wildfires lead to the production of nanometer‐sized superparamagnetic magnetite and/or maghemite particles and smaller amount of single‐domain fraction. These strongly magnetic minerals have typical characteristics of high‐temperature combustion products with spherical shape and diameters between 0.1 and 2 μm. Fire‐affected soils show relative enrichment with phosphorous, manganese, and heavy metals (Cu, Pb, Zn, Ni, Co, and As) calculated with respect to soils from nonburnt nearby localities. Our results demonstrate the potential of environmental magnetic methods as an additional tool for assessment of wildfire severity and the content of main soil nutrients.

A diamagnetic AuI4 CoIII2 hexanuclear complex, [Au4 Co2 (dppe)2 (l-nmc)4 ]2+ ([1L-nmc ]2+ ; dppe=1,2-bis(diphenylphosphino)ethane, l-H2 nmc=N-methyl-l-cysteine), was newly synthesized by the reaction of [Co(l-nmc)2 ]- with [Au2 Cl2 (dppe)] and crystallized with different inorganic anions (X=ClO4- , NO3- , Cl- , SO42- ) to produce ionic solids ([1L-nmc ]Xn ). Single-crystal X-ray analysis revealed that all the solids crystallize in the chiral space group F432 with a face-centered-cubic lattice structure consisting of supramolecular octahedra of complex cations. The paramagnetic nature of all the solids was evidenced by magnetic susceptibility measurements, showing the variation of the oxidation states of two cobalt centers in [1L-nmc ]n+ from CoII1.00 CoIII1.00 for X=ClO4- or NO3- to CoII0.67 CoIII1.33 for X=Cl- , via CoII0.83 CoIII1.17 for X=SO42- . The difference in the CoII/III mixed-valences was explained by the difference in sizes and charges of counter anions accommodated in lattice interstices with a fixed volume.

Two trinuclear copper phosphonate complexes, [Cu3 (pda)3 (tBuPO3 )]⋅2(Et3 NH) (1) and [Cu3 (pda)3 (PhPO3 )]⋅2(Et3 NH) (2), have been synthesized and investigated by a combination of X-ray crystallography, PXRD, magneto- and electrochemistry, EPR, in situ UV-vis spectroelectrochemistry and DLS. The two complexes feature almost identical crystal structures, the anions of which are both supported by pda2- and tBuPO3 2- /PhPO3 2- groups, bridging three five-coordinated CuII atoms to form a crown-like structure. This is the first time that trinuclear copper phosphonate complexes have been isolated and characterized. Magnetic susceptibility measurements reveal that complexes 1 and 2 both display overall ferromagnetic characters, but with different exchange interactions between the metal ions within the two clusters. The electrocatalytic activity for water oxidation of the two complexes was preliminarily investigated, which reveals that both of the two complexes can carry out electrocatalytic water oxidation in a neutral system owing to the introduction of phosphonate ligands into the complexes, with a TOF of about 0.82 s-1 (1) and 0.58 s-1 (2), respectively. We propose that the presence of phosphonate ligands may affect the magnetic property and catalytic activity of the complexes.

In two closely related series of eight-coordinate lanthanide complexes, a switch in the sign of the dominant ligand field parameter and striking variations in the sign, amplitude and orientation of the main component of the magnetic susceptibility tensor as the Ln3+ ion is permuted conspire to mask modest changes in NMR paramagnetic shifts, but are evident in Yb EPR and Eu emission spectra.