RESUMEN
BACKGROUND Paracoccidioidomycosis is an endemic mycosis in Central and South America caused by the thermally dimorphic fungus Paracoccidioides brasiliensis. Despite its self-limited course and usually asymptomatic infection, some patients may present with a systemic illness mimicking multiple conditions and thus question the general state of their immune system. CASE REPORT A 28-year-old male presented to the hospital with fever, dry cough, and non-pruritic rash with no characteristic distribution for the past 10 days. Past medical history revealed that the patient had worked as a farmer three years ago, had abused cocaine paste over the same period, and also had in the last month presented to the hospital for acute appendicitis. Initial laboratory tests revealed hypereosinophilia greater than 10,000 eosinophils/mL. Infection of P. brasiliensis was confirmed by lymph node, skin, and colonoscopy biopsies. After treatment with itraconazole, the patient's eosinophil count returned to normal and his symptoms resolved. CONCLUSIONS Paracoccidioidomycosis may present as a systemic illness with only marked eosinophilia on initial diagnostic tests. Furthermore, in our patient's case, the high degree of eosinophilia may have contributed towards the patient's appendicitis in the weeks preceding the subacute infection. It is possible that the patient's history of working at a farm and abusing cocaine paste may have contributed to the initial colonization by the fungus.
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Eosinofilia/etiología , Paracoccidioidomicosis/complicaciones , Adulto , Humanos , Masculino , Paracoccidioidomicosis/diagnósticoRESUMEN
Polynuclear manganese compounds have garnered interest as mimics and models of the water oxidizing complex (WOC) in photosystem II and as single molecule magnets. Molecular systems in which composition can be correlated to physical phenomena, such as magnetic exchange interactions, remain few primarily because of synthetic limitations. Here, we report the synthesis of a family of trimanganese(II) complexes of the type Mn3X3L (X = Cl-, H-, and MeO-) where L3- is a tris(ß-diketiminate) cyclophane. The tri(chloride) complex (2) is structurally similar to the reported tri(bromide) complex (1) with the Mn3X3 core having a ladder-like arrangement of alternating M-X rungs, whereas the tri(µ-hydride) (3) and tri(µ-methoxide) (4) complexes contain planar hexagonal cores. The hydride and methoxide complexes are synthesized in good yield (48% and 56%) starting with the bromide complex employing a metathesis-like strategy. Compounds 2-4 were characterized by combustion analysis, X-ray crystallography, X-band EPR spectroscopy, SQUID magnetometry, and infrared and UV-visible spectroscopy. Magnetic susceptibility measurements indicate that the Mn3 clusters in 2-4 are antiferromagnetically coupled, and the spin ground state of the compounds (S = 3/2 (1, 2) or S = 1/2 (3, 4)) is correlated to the identity of the bridging ligand and structural arrangement of the Mn3X3 core (X = Br, Cl, H, OCH3). Electrochemical experiments on isobutyronitrile solutions of 3 and 4 display broad irreversible oxidations centered at 0.30 V.
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Synthetic and characterization results of a new family of Fe(III) compounds stabilized by a trianionic [CF3-ONO](3-) pincer-type ligand are reported. The ligand possesses three negatively charged donors constrained to the meridional positions that provide sufficient electron density to stabilize high-valent metal complexes. Using the redox-insulated [CF3-ONO](3-), pentacoordinated square-pyramidal {[CF3-ONO]FeCl2}{LiTHF2}2 (3), dimeric µ-DME{[CF3-ONO]FeDME}2 (4), trigonal bipyramidal [CF3-ONO]Fe(bpy) (5), and octahedral [CF3-ONO]Fe(bpy)H2O (5·H2O) complexes are synthesized. An interesting feature of the [CF3-ONO](3-) pincer-type ligand is its ability to coordinate the metal center in both the more common meridional positions or occupying a face of a trigonal bipyramidal complex. The molecular structure of 3 contains structural features similar to those of a rare square-planar high-spin Fe(II) complex, and the important role of the counterions in stabilizing a square-plane is emphasized. SQUID magnetometry measurements of 3 reveal its high-spin character, and cyclic voltammetry measurements indicate high oxidation state species are unstable. However, all compounds can be reduced, and in particular 5 displays a reversible reduction event at -2255 mV versus ferrocene (Fc(+)/Fc) that can be assigned to either the Fe(I)/Fe(0) couple or 2,2'-bipyridine reduction.
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Aniones/química , Quelantes/química , Compuestos Férricos/química , 2,2'-Dipiridil/química , Compuestos Ferrosos/química , Halogenación , Ligandos , Metalocenos , Oxidación-ReducciónRESUMEN
Particles of formula Rb0.24Co[Fe(CN)6]0.74@K0.10Co[Cr(CN)6]0.70·nH2O with a light-responsive rubidium cobalt hexacyanoferrate (RbCoFe) core and a magnetic potassium cobalt hexacyanochromate (KCoCr) shell have been prepared and exhibit light-induced changes in the magnetization of the normally light-insensitive KCoCr shell, a new property resulting from the synergy between the core and shell of a coordination polymer heterostructure. A single batch of 135 ± 12 nm RbCoFe particles are used as seeds to generate three different core@shell samples, with KCoCr shell thicknesses of approximately 11, 23 and 37 nm, to probe the influence of the shell thickness over the particles' morphology and structural and magnetic properties. Synchrotron powder X-ray diffraction reveals that structural changes in the shell accompany the charge transfer induced spin transition (CTIST) of the core, giving direct evidence that the photomagnetic response of the shell is magnetomechanical in origin. The depth to which the KCoCr shell contributes to changes in magnetization is estimated to be approximately 24 nm when using a model that assumes a constant magnetic response of the core within the series of particles. In turn, the presence of the shell changes the nature of the CTIST of the core. As opposed to the usually observed first order transition exhibiting hysteresis, the CTIST becomes continuous in the core@shell particles.
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Luz , Magnetismo , Metales/química , Polímeros/química , Microscopía Electrónica de Transmisión , Difracción de PolvoRESUMEN
Coordination polymer thin film heterostructures of the Prussian blue analogue Ni(II)b[Cr(III)(CN)6](0.7)·nH2O (NiCr-PBA) and the 3D Hofmann-like spin crossover compound Fe(azpy)[Pt(CN)4]·xH2O {azpy = 4,4'-azopyridine} have been developed, and spin transition properties have been characterized via SQUID magnetometry and Raman spectroscopy. The magnetic response of the ferromagnetic NiCr-PBA layer (T(c) ≈ 70 K) can be altered by inducing the LIESST effect (light-induced excited spin state trapping) in the coupled paramagnetic Fe(II) spin crossover material. Whereas an increase in magnetization is measured for the single-phase Fe(azpy)[Pt(CN)4]·xH2O, a decrease in magnetization is observed for the heterostructure. These results indicate the LIESST effect alone cannot account for the sign and magnitude of the magnetization change in the heterostructure, but the temperature profile of the magnetization shows that significant changes in the NiCr-PBA network are correlated to the spin state of the Hofmann-like SCO network.