Assessment of inspiration and technical quality in anteroposterior thoracic radiographs using machine learning.

INTRODUCTION: Chest radiographs are the most performed radiographic procedure, but suboptimal technical factors can impact clinical interpretation. A deep learning model was developed to assess technical and inspiratory adequacy of anteroposterior chest radiographs. METHODS: Adult anteroposterior chest radiographs (n = 2375) were assessed for technical adequacy, and if otherwise technically adequate, for adequacy of inspiration. Images were labelled by an experienced radiologist with one of three ground truth labels: inadequate technique (n = 605, 25.5 %), adequate inspiration (n = 900, 37.9 %), and inadequate inspiration (n = 870, 36.6 %). A convolutional neural network was then iteratively trained to predict these labels and evaluated using recall, precision, F1 and micro-F1, and Gradient-weighted Class Activation Mapping analysis on a hold-out test set. Impact of kyphosis on model accuracy was assessed. RESULTS: The model performed best for radiographs with adequate technique, and worst for images with inadequate technique. Recall was highest (89 %) for radiographs with both adequate technique and inspiration, with recall of 81 % for images with adequate technique and inadequate inspiration, and 60 % for images with inadequate technique, although precision was highest (85 %) for this category. Per-class F1 was 80 %, 81 % and 70 % for adequate inspiration, inadequate inspiration, and inadequate technique respectively. Weighted F1 and Micro F1 scores were 78 %. Presence or absence of kyphosis had no significant impact on model accuracy in images with adequate technique. CONCLUSION: This study explores the promising performance of a machine learning algorithm for assessment of inspiratory adequacy and overall technical adequacy for anteroposterior chest radiograph acquisition. IMPLICATIONS FOR PRACTICE: With further refinement, machine learning can contribute to education and quality improvement in radiology departments.

Coherent coupling between Vanadyl Phthalocyanine spin ensemble and microwave photons: towards integration of molecular spin qubits into quantum circuits.

Electron spins are ideal two-level systems that may couple with microwave photons so that, under specific conditions, coherent spin-photon states can be realized. This represents a fundamental step for the transfer and the manipulation of quantum information. Along with spin impurities in solids, molecular spins in concentrated phases have recently shown coherent dynamics under microwave stimuli. Here we show that it is possible to obtain high cooperativity regime between a molecular Vanadyl Phthalocyanine (VOPc) spin ensemble and a high quality factor superconducting YBa2Cu3O7 (YBCO) coplanar resonator at 0.5 K. This demonstrates that molecular spin centers can be successfully integrated in hybrid quantum devices.

Tm(iii) complexes undergoing slow relaxation of magnetization: exchange coupling and aging effects.

The present study focuses on the dynamic magnetic behaviour of exchange coupled 3d-4f complexes containing the scarcely investigated non-Kramers Tm3+ center, the 3d metal ions being either the low-spin Fe3+ (1) or the diamagnetic Co3+ (2) ion. Both complexes display field-induced slow relaxation of magnetization. The field and temperature dependences of the relaxation rate provided indication of relevant contributions from quantum tunnelling, direct, Orbach and Raman processes, with only minor effects from exchange coupling interactions. Furthermore, the aged sample of 2 exhibited an additional relaxation process, possibly due to structural modifications accompanied by solvent loss, highlighting the importance of a careful consideration of this factor when analysing the magnetization dynamics in solvated systems.

Giant spin-phonon bottleneck effects in evaporable vanadyl-based molecules with long spin coherence.

Vanadium(iv) complexes have recently shown record quantum spin coherence times that in several circumstances are limited by spin-lattice relaxation. The role of the environment and vibronic properties in the low temperature dynamics is here investigated by a comparative study of the magnetization dynamics as a function of crystallite size and the steric hindrance of the ß-diketonate ligands in VO(acac)2 (1), VO(dpm)2 (2) and VO(dbm)2 (3) evaporable complexes (acac- = acetylacetonate, dpm- = dipivaloylmethanate, and dbm- = dibenzoylmethanate). A pronounced crystallite size dependence of the relaxation time is observed at unusually high temperatures (up to 40 K), which is associated with a giant spin-phonon bottleneck effect. We model this behaviour by an ad hoc force field approach derived from density functional theory calculations, which evidences a correlation of the intensity of the phenomenon with ligand dimensions and the unit cell size.

Coupling molecular spin centers to microwave planar resonators: towards integration of molecular qubits in quantum circuits.

We present spectroscopic measurements looking for the coherent coupling between molecular magnetic centers and microwave photons. The aim is to find the optimal conditions and the best molecular features to achieve the quantum strong coupling regime, for which coherent dynamics of hybrid photon-spin states take place. To this end, we used a high critical temperature YBCO superconducting planar resonator working at 7.7 GHz and at low temperatures to investigate three molecular mononuclear coordination compounds, namely (PPh4)2[Cu(mnt)2] (where mnt2- = maleonitriledithiolate), [ErPc2]-TBA+ (where pc2- is the phtalocyaninato and TBA+ is the tetra-n-butylammonium cation) and Dy(trensal) (where H3trensal = 2,2',2''-tris(salicylideneimino)triethylamine). Although the strong coupling regime was not achieved in these preliminary experiments, the results provided several hints on how to design molecular magnetic centers to be integrated into hybrid quantum circuits.

Magnetic blocking in extended metal atom chains: a pentachromium(II) complex behaving as a single-molecule magnet.

Compound [Cr5(tpda)4Cl2] (H2tpda = N(2),N(6)-di(pyridin-2-yl)pyridine-2,6-diamine), an Extended Metal Atom Chain complex featuring two quadruply-bonded {Cr2} units, exhibits field-induced slow relaxation of its magnetization arising from the terminal chromium(II) ion and provides the first example of a chromium(II)-based Single-Molecule Magnet.

Determination of the relevant magnetic interactions in low-dimensional molecular materials: the fundamental role of single crystal high frequency EPR.

A new one-dimensional copper(II) complex with formula [Cu(hfac)(2)(N(3)TEMPO)](n) (hfac = hexafluoroacetylacetonate and N(3)TEMPO = 4-azido-2,2,6,6-tetramethylpiperidine-1-oxyl) has been synthesized and investigated by X-ray crystallography, magnetometry and multifrequency single crystal EPR. The system crystallizes in the P1 space group with two non equivalent copper(II) ions in the unit cell, the two nitroxide radicals being coordinated to Cu(1) in axial positions. The copper(II) ions are bridged by N(3)TEMPO radicals resulting in a zig-zag chain structure. The magnetic susceptibility data were at first satisfactorily modeled assuming an alternating spin chain along the monodimensional covalent skeleton, with a ferromagnetic interaction between Cu(1) and the nitroxide moieties and a weaker antiferromagnetic interaction between these and Cu(2) (J(1) = -13.8 cm(-1), J(2) = +2.4 cm(-1)). However, single crystal EPR studies performed at the X- and W-band clearly demonstrate that the observed magnetic monodimensional character of the complex is actually due to the intermolecular contacts involving N(3)TEMPO ligands. This prompted us to fit the magnetic data using a consistent model, pointing out the fundamental role of single crystal EPR data in defining a correct model to describe the magnetic properties of molecular low dimensional systems.

Single crystal EPR study at 95 GHz of a large Fe based molecular nanomagnet: toward the structuring of magnetic nanoparticle properties.

A W-band single-crystal EPR study has been performed on a molecular cluster comprising 19 iron(III) ions bridged by oxo- hydroxide ions, Fe(19), in order to investigate magnetic nanosystems with a behavior in between the one of Magnetic NanoParticles (MNP) and that of Single Molecule Magnets (SMM). The Fe(19) has a disk-like shape: a planar Fe(7) core with a brucite (Mg(OH)(2)) structure enclosed in a "shell" of 12 Fe(III) ions. EPR and magnetic measurements revealed an S = 35/2 ground state with an S = 33/2 excited state lying ∼ 8 K above. The presence of other low-lying excited states was also envisaged. Rhombic Zero Field Splitting (ZFS) tensors were determined, the easy axes lying in the Fe(19) plane for both the multiplets. At particular temperatures and orientations, a partially resolved fine structure could be observed which could not be distinguished in powder spectra, due to orientation disorder. The similarities of the EPR behavior of Fe(19) and MNP, together with the accuracy of single crystal analysis, helped to shed light on spectral features observed in MNP spectra, that is a sharp line at g = 2 and a low intensity transition at g = 4. Moreover, a theoretical analysis has been used to estimate the contribution to the total magnetic anisotropy of core and surface; this latter is crucial in determining the easy axis-type anisotropy, alike that of MNP surface.

Quantum tunnelling of the magnetization in a monolayer of oriented single-molecule magnets.

A fundamental step towards atomic- or molecular-scale spintronic devices has recently been made by demonstrating that the spin of an individual atom deposited on a surface, or of a small paramagnetic molecule embedded in a nanojunction, can be externally controlled. An appealing next step is the extension of such a capability to the field of information storage, by taking advantage of the magnetic bistability and rich quantum behaviour of single-molecule magnets (SMMs). Recently, a proof of concept that the magnetic memory effect is retained when SMMs are chemically anchored to a metallic surface was provided. However, control of the nanoscale organization of these complex systems is required for SMMs to be integrated into molecular spintronic devices. Here we show that a preferential orientation of Fe(4) complexes on a gold surface can be achieved by chemical tailoring. As a result, the most striking quantum feature of SMMs-their stepped hysteresis loop, which results from resonant quantum tunnelling of the magnetization-can be clearly detected using synchrotron-based spectroscopic techniques. With the aid of multiple theoretical approaches, we relate the angular dependence of the quantum tunnelling resonances to the adsorption geometry, and demonstrate that molecules predominantly lie with their easy axes close to the surface normal. Our findings prove that the quantum spin dynamics can be observed in SMMs chemically grafted to surfaces, and offer a tool to reveal the organization of matter at the nanoscale.

Metal dilution effects on entropy and light-induced valence tautomeric interconversion in a 1:1 cobalt-dioxolene complex.

The entropy and the light-induced valence tautomeric interconversions of solid solutions of the [Co(Me(2)tpa)(diox)](PF(6)).C(6)H(5)CH(3) complex [Me(2)tpa = bis(6-methyl-(2-pyridylmethyl))(2-pyridylmethyl)amine and diox = catecholato (DBCat) or semiquinonato (DBSQ) forms of 3,5-ditert-butylquinone] in the electronically innocent [Zn(Me(2)tpa)(DBSQ)](PF(6)).C(6)H(5)CH(3) host, in four different molar ratios, have been investigated. It has been found that the entropy driven transition is strongly affected by the Co:Zn molar ratio, whereas the relaxation rates of the optically induced high-spin Co(II)-DBSQ metastable state at cryogenic temperatures are nearly independent of the degree of solid dilution. These results are discussed in the framework of the Jortner theory for adiabatic radiationless multiphonon relaxation processes. It is suggested that the optical bistability in these systems is related to the single molecule properties rather than to the cooperative effects active in the lattice.

Molecular nanomagnets and magnetic nanoparticles: the EMR contribution to a common approach.

The current status and future developments of the use of electron magnetic resonance (EMR) for the investigation of magnetic nano-systems is here reviewed. The aim is to stimulate efforts to provide a unified view of the properties of magnetic nanoparticles (MNP) comprising a few hundred magnetic centres, and molecular nanomagnets which contain up to ca. one hundred magnetic centres (MNM). The size of the systems is becoming the same but the approaches to the interpretation of their properties are still different, being bottom up for the latter and top down for the former. We make the point here of the need for a common viewpoint, highlighting the status of the two fields and giving some hints for the future developments. EMR has been a powerful tool for the investigation of magnetic nano-objects and it can provide a tool of fundamental importance for the development of a unified view.

High-field/high-frequency EPR studies of spin clusters with integer spin: the multi-frequency approach.

In this paper a rapid overview of the main results obtained from the study with multi-frequency HF-EPR of molecular spin clusters possessing integer spin values is presented. In the first part, two antiferromagnetic rings with zero ground spin state are reported. It is illustrated how the HF-EPR study of the first excited states allows obtaining important information on this kind of spin clusters. In the second part, selected examples of single-molecule magnets (SMM) are treated, starting with complexes involving only a few magnetic ions and going on to more complex systems. Indeed, because of their large zero-field energy gaps, EPR studies of SMM deserve the use of high frequencies and high fields. The approach presented here is twofold. First the interest of studying a series of 'simple' SMM in order to understand the subtle mechanisms underlying their properties is stressed. Then a summary of our HF-EPR studies of the most investigated SMM, Mn12ac and Fe8 is presented.

Origin of second-order transverse magnetic anisotropy in Mn12-acetate.

The symmetry breaking effects for quantum tunneling of the magnetization in Mn12-acetate, a molecular nanomagnet, represent an open problem. We present structural evidence that the disorder of the acetic acid of crystallization induces sizable distortion of the Mn(III) sites, giving rise to six different isomers. Four isomers have symmetry lower than tetragonal and a nonzero second-order transverse magnetic anisotropy, which has been evaluated using a ligand field approach. The result of the calculation leads to an improved simulation of electron paramagnetic resonance spectra and justifies the tunnel splitting distribution derived from the field sweep rate dependence of the hysteresis loops.

Ising-type magnetic anisotropy in a cobalt(II) nitronyl nitroxide compound: a key to understanding the formation of molecular magnetic nanowires.

The compound [Co(hfac)2-(NITPhOMe)2] (2) (hfac = hexafluoroacetylacetonate, NITPhOMe = 4'-methoxyphenyl-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide) crystallizes in the triclinic P1 space group, a= 10.870(5), b = 11.520(5), c = 19.749(5) A, alpha = 78.05(5), beta = 84.20(5), gamma = 64.51(5) degrees, Z = 2. It can be considered a model system for studying the nature of the magnetic anisotropy of [Co(hfac)2(NITPhOMe)] (1), which was recently reported to behave as a molecular magnetic wire. The magnetic anisotropy of 2 was investigated by EPR spectroscopy and SQUID magnetometry both in the polycrystalline powder and in a single crystal. The experimental magnetic anisotropy was related to the anisotropy of the central ion and to the exchange interaction between the cobalt(II) ion and the radicals.

Hydroxo-bridged Cubane-type tetrairon(II) clusters supported by sterically-hindered carboxylate ligands.

A series of hydroxo-bridged cubane-type tetrairon(II) clusters, [Fe(4)(mu-OH)(4)(mu-O(2)CAr(4)(-)t(BuPh))(2)(mu-OTf)(2)L(4)] (L = C(5)H(5)N (1), 4-(t)BuC(5)H(4)N (2), 3-FC(5)H(4)N (3)), were synthesized by using a sterically hindered carboxylate ligand, 2,6-di(4-tert-butylphenyl)benzoate (Ar(4)(-)t(BuPh)CO(2)(-)). Three different bridging units that mediate weak antiferromagnetic coupling interactions between the metal centers support the unprecedented cubane-type [Fe(4)(mu-OH)(4)](4+) cores in 1-3. The solution structures of 1 and 3 probed by FT-IR and (19)F NMR spectroscopy are consistent with the solid-state geometry determined by X-ray crystallography. Zero-field Mössbauer spectra of 1-3 at 4.2 K are characteristic of high-spin iron(II) centers in nearly identical coordination environments. Compound 1 undergoes two irreversible oxidation processes at ca -10 and +880 mV (vs Fc/Fc(+)), the former approaching quasi-reversible behavior with increased scan rates and a narrow potential sweep range. Comparisons are made with analogous known [Fe(4)X(4)](n)()(+) (X = O, S) units, and the structural integrity of tetrairon fragments upon a change in oxidation state is discussed together with some possible biological implications.

Charge distribution in bis-dioxolene radical metal complexes. synthesis and DFT characterization of dinuclear Co(III) and Cr(III) complexes with a mixed-valent, S = 1/2 semiquinone-catecholate ligand.

Bis-dioxolene bridged dinuclear metal complexes of general formula M2(CTH)2(diox-diox)(PF6)n (n = 2, 3; M = Co(III), Cr(III); CTH = tetraazamacrocycle) have been synthesized using the bis-bidentate ligand 5,5'-di-tert-butyl-3,3',4,4'-tetrahydroxybiphenyl. These complexes were characterized by means of ESR, UV-vis, temperature dependent magnetic susceptibility, and cyclic voltammetry. Our results unambiguously suggest that the tripositive dimetal cations can be described as containing a fully delocalized bis-dioxolene trinegative radical ligand (Cat-Sq) bridging two tripositive metal cations. In this frame the sextet electronic ground state characterizes the Cr2(CTH)2(Cat-SQ)3+ as a result of the antiferromagnetic coupling of the radical bridging ligand with the two equivalent paramagnetic metal centers. The electronic and geometrical structure and the magnetic properties of Cat-Sq and of its complexes have been studied with density functional theory.

A bis-bidentate dioxolene ligand induces thermal hysteresis in valence tautomerism interconversion processes.

The use of a bis-bidentate ligand in a solid cobalt dioxolene complex affords the necessary cooperative properties that lead to thermal hysteresis in a valence tautomeric interconversion equilibrium.

Tuning the magnetic properties of the high-spin molecular cluster Fe8.

The synthesis, crystal structure, and magnetic characterization of a high-spin cluster comprising eight iron ions are presented in this contribution. The cluster has formula [(tacn)6Fe8O2(OH)12Br4.3(ClO4)3.7]·6H2O (Fe8pcl), where tacn is the organic ligand 1,4,7-triazacyclononane. It can be considered a derivative of Fe8 Br8 , a cluster whose low-temperature magnetization dynamics has been extensively investigated, in which four of the bromide ions have been replaced by perchlorate anions. The structure of the central core of the two molecules, [Fe8O(OH)12(tacn)6](8+), is essentially the same, but Fe8pcl has a higher symmetry (the bromide derivative crystallizes in the acentric P1 space group while Fe8pcl crystallizes in the monoclinic P2(1)/c space group). The magnetic properties of Fe8pcl suggest it is very similar to Fe8Br8 having a S=10 ground state as well. The zero-field splitting parameters were accurately determined by high field-high frequency EPR (HF-EPR) measurements. The two clusters have similar axial anisotropy D but Fe8pcl has a larger transverse anisotropy E: The value of E/D is 0.21 for the perchlorate derivative but 0.19 for Fe8Br8. AC susceptibility measurements revealed the cluster behaves like a superparamagnetic particle. However, due to the occurrence of large terms in the transverse anisotropy, the temperature dependence of the relaxation time cannot be reproduced by a simple Arrhenius law model. As observed in the bromide derivative, below 350 mK the relaxation time becomes temperature independent and indicating that a pure tunneling regime is attained. The comparison of the tunneling rate in the two clusters shows that in the perchlorate derivative the relaxation process is 35 times faster. The observed ratio of the tunneling rates is in reasonable agreement with that calculated from the tunneling splitting, namely the energy difference between the two almost-degenerate lowest levels Ms =±10, in the two clusters.

Antiferromagnetic Coupling in a Gadolinium(III) Semiquinonato Complex.

The strongest antiferromagnetic coupling to Gd(III) so far reported was found for the complex [Gd(Hbpz(3))(2)(dtbsq)] small middle dot2 CHCl(3) (1; Hbpz(3)=hydrotris(pyrazolyl)borate; dtbsq=3,5-di-tert-butylsemiquinonato; see structure). At 245 K the magnetic susceptibility of 1 is lower than expected for two uncorrelated spins of 7/2 and 1/2, and the lowering of chiT with increasing temperature suggests that this is due to antiferromagnetic interaction between Gd(III) and the radical.