Field-Induced Single-Ion Magnet Behavior in Nickel(II) Complexes with Functionalized 2,2':6'-2″-Terpyridine Derivatives: Preparation and Magneto-Structural Study.

Two mononuclear nickel(II) complexes of the formula [Ni(terpyCOOH)2](ClO4)2∙4H2O (1) and [Ni(terpyepy)2](ClO4)2 MeOH (2) [terpyCOOH = 4'-carboxyl-2,2':6',2″-terpyridine and terpyepy = 4'-[(2-pyridin-4-yl)ethynyl]-2,2':6',2″-terpyridine] have been prepared and their structures determined by single-crystal X-ray diffraction. Complexes 1 and 2 are mononuclear compounds, where the nickel(II) ions are six-coordinate by the six nitrogen atoms from two tridentate terpy moieties. The mean values of the equatorial Ni-N bond distances [2.11(1) and 2.12(1) Å for Ni(1) at 1 and 2, respectively, are somewhat longer than the axial ones [2.008(6) and 2.003(6) Å (1)/2.000(1) and 1.999(1) Å (2)]. The values of the shortest intermolecular nickel-nickel separation are 9.422(1) (1) and 8.901(1) Å (2). Variable-temperature (1.9-200 K) direct current (dc) magnetic susceptibility measurements on polycrystalline samples of 1 and 2 reveal a Curie law behavior in the high-temperature range, which corresponds to magnetically isolated spin triplets, the downturn of the χMT product at lower temperatures being due to zero-field splitting effects (D). Values of D equal to -6.0 (1) and -4.7 cm-1 (2) were obtained through the joint analysis of the magnetic susceptibility data and the field dependence of the magnetization. These results from magnetometry were supported by theoretical calculations. Alternating current (ac) magnetic susceptibility measurements of 1 and 2 in the temperature range 2.0-5.5 K show the occurrence of incipient out-phase signals under applied dc fields, a phenomenon that is characteristic of field-induced Single-Molecule Magnet (SMM) behavior, which herein concerns the 2 mononuclear nickel(II) complexes. This slow relaxation of the magnetization in 1 and 2 has its origin in the axial compression of the octahedral surrounding at their nickel(II) ions that leads to negative values of D. A combination of an Orbach and a direct mechanism accounts for the field-dependent relation phenomena in 1 and 2.

Trinuclear Cobalt(II) Triple Helicate with a Multidentate Bithiazolebis(oxamate) Ligand as a Supramolecular Nanomagnet.

The cobalt(II)-mediated self-assembly of the potentially tris(chelating) N,N'-2,2'-(4,4'-bithiazole)bis(oxamate) (dabtzox) ligand gives a new metal-organic supramolecular nanomagnet of formula K6Co3(dabtzox)3·8H2O·MeOH (1) featuring a unique linear triple-stranded trinuclear structure of the helicate type.

Dual Band MEMS Directional Acoustic Sensor for Near Resonance Operation.

In this paper, we report on the design and characterization of a microelectromechanical systems (MEMS) directional sensor inspired by the tympana configuration of the parasitic fly Ormia ochracea. The sensor is meant to be operated at resonance and act as a natural filter for the undesirable frequency bands. By means of breaking the symmetry of a pair of coupled bridged membranes, two independent bending vibrational modes can be excited. The electronic output, obtained by the transduction of the vibration to differential capacitance and then voltage through charge amplifiers, can be manipulated to tailor the frequency response of the sensor. Four different frequency characteristics were demonstrated. The sensor exhibits, at resonance, mechanical sensitivity around 6 µm/Pa and electrical sensitivity around 13 V/Pa. The noise was thoroughly characterized, and it was found that the sensor die, rather than the fundamental vibration, induces the predominant part of the noise. The computed average signal-to-noise (SNR) ratio in the pass band is about 91 dB. This result, in combination with an accurate dipole-like directional response, indicates that this type of directional sensor can be designed to exhibit high SNR and selectable frequency responses demanded by different applications.

MEMS Underwater Directional Acoustic Sensor in Near Neutral Buoyancy Configuration.

A MEMS directional acoustic sensor housed in an air cavity and operated underwater in a near-neutral buoyancy configuration is demonstrated. The sensor consists of two wings connected by a bridge and attached to a substrate by two centrally mounted torsional legs. The frequency response showed two resonant peaks corresponding to a rocking mode (wings moving in opposite directions) and a bending mode (wings moving in the same direction). Initial tests of the sensor using a shaker table showed that the response is highly dependent on the vibration direction. In air, the sensor showed a maximum sensitivity of about 95 mV/Pa with a cosine directional response. Underwater, the maximum sensitivity was about 37 mV/Pa with a similar cosine directional response. The measured maximum SNR was about 38 dB for a signal generated by a sound stimulus of 1 Pa when the sensor is operated near the bending resonance. The results indicate that this type of MEMS sensor can be operated in a near-neutral buoyant configuration and achieve a good directional response.

Europium(III), Terbium(III), and Gadolinium(III) Oxamato-Based Coordination Polymers: Visible Luminescence and Slow Magnetic Relaxation.

The reaction of aqueous solutions of EuIII, TbIII, and GdIII ions with Na2Hpcpa [H3pcpa = N-(4-carboxyphenyl)oxamic acid] afforded three new isostructural oxamate-containing lanthanide(III) coordination polymers of general formula {LnIII2(Hpcpa)3(H2O)5·H2O}n [Ln = Eu (1),Tb (2), and Gd(3)]. Their structure is made up of neutral zigzag chains running parallel to the [101] direction where double syn-syn carboxylate(oxamate)-bridged dilanthanide(III) pairs (Ln1 and Ln2) are linked by three Hpcpa2- ligands, one of them with the µ-κ2O,O':κO″ coordination mode and the other two with the µ3-κ2O,O':κO″:κO'''. Additionally, two of those chains are interlinked through hydrogen bonding and π-π type interactions, resulting in a porous structure with channels where water molecules are hosted. The emission properties of 1 and 2 are evaluated as a function of the temperature, exhibiting an emission in red and green, respectively. The external quantum yield for 2 is approximately 7 times that obtained for 1, indicating that the oxamate ligand is a better sensitizer for TbIII ions. The temperature dependence of the dc magnetic properties of 1-3 reveals a different magnetic behavior depending on the nature of the LnIII ion. A continuous decrease of χMT occurs for 1 upon cooling, and finally χMT tends to vanish, as expected for the thermal depopulation of the six magnetic 7FJ excited states (J = 1-6) of the EuIII ion with a nonmagnetic 7F0 ground state. χMT for 2 decreases sharply with decreasing the temperature due to the depopulation of the splitted mJ levels of the 7F7 ground state of the magnetically anisotropic TbIII ion. A very weak antiferromagnetic interaction between the magnetically isotropic GdIII ions across the double carboxylate(oxamate) bridge is responsible for the small decrease of χMT at low temperatures for 3. The dynamic (ac) magnetic properties of 2 and 3 reveal a slow magnetic relaxation with very incipient frequency-dependent χM″ signals below 6.0 K (2) and frequency-dependent χM″ peaks below 10.0 K (3) under nonzero applied dc magnetic fields, being thus new examples of field-induced single molecule magnets (SMMs).

Holmium(III) Single-Ion Magnet for Cryomagnetic Refrigeration Based on an MRI Contrast Agent Derivative.

The coexistence of field-induced blockage of the magnetization and significant magnetocaloric effects in the low-temperature region occurs in a mononuclear holmium(III) diethylenetriamine-N,N,N',N″,N″-pentaacetate complex, whose gadolinium(III) analogue is a commercial MRI contrast agent. Both properties make it a suitable candidate for cryogenic magnetic refrigeration, thus enlarging the variety of applications of this simple class of multifunctional molecular nanomagnets.

Fabrication of MEMS Directional Acoustic Sensors for Underwater Operation.

In this work, microelectromechanical systems (MEMS)-based directional acoustic sensors operating in an underwater environment are explored. The studied sensors consist of a free-standing single wing or two wings pivoted to a substrate. The sensors operate in a narrow frequency band determined by the resonant frequency of the mechanical structure. The electronic readout of the mechanical response is obtained using interdigitated comb finger capacitors attached to the wings. The characteristics of MEMS sensors immersed in silicone oil are simulated using finite element modeling. The performance of the sensors is evaluated both in air and underwater. For underwater testing and operation, the sensors are packaged in a housing containing silicone oil, which was specially developed to present near unity acoustic transmission. The measurements show that the resonant frequency of the sensors obtained in air shifts to a lower frequency when immersed in silicone oil, which is primarily due to the mass loading of the liquid. The peak sensitivity of the MEMS sensors is approximately 6 mV/Pa or -165 dB re 1 V/mPa, and the directional response shows a dipole pattern. The signal-to-noise ratio was found to be about 200 or 23 dB at 1 Pa incident sound pressure. The results show the potential of MEMS sensors to be used in underwater applications for sound source localization.

How the spin state tunes the slow magnetic relaxation field dependence in spin crossover cobalt(II) complexes.

A novel family of cobalt(II) compounds with tridentate pyridine-2,6-diiminephenyl type ligands featuring electron-withdrawing substituents of general formula [Co(n-XPhPDI)2](ClO4)2·S [n-XPhPDI = 2,6-bis(N-n-halophenylformimidoyl)pyridine with n = 4 (1-3) and 3 (4); X = I (1), Br (2 and 4) and Cl (3); S = MeCN (1 and 2) and EtOAc (3)] has been synthesised and characterised by single-crystal X-ray diffraction, electron paramagnetic resonance, and static (dc) and dynamic (ac) magnetic measurements combined with theoretical calculations. The structures of 1-4 consist of mononuclear bis(chelating) cobalt(II) complex cations, [CoII(n-XPhPDI)2]2+, perchlorate anions, and acetonitrile (1 and 2) or ethyl acetate (3) molecules of crystallisation. This unique series of mononuclear six-coordinate octahedral cobalt(II) complexes displays both thermally-induced low-spin (LS)/high-spin (HS) transition and field-induced slow magnetic relaxation in both LS and HS states. A complete LS ↔ HS transition occurs for 1 and 2, while it is incomplete for 4, one-third of the complexes being HS at low temperatures. In contrast, 3 remains HS in all the temperature range. 1 and 2 show dual spin relaxation dynamics under the presence of an applied dc magnetic field (Hdc), with the occurrence of faster- (FR) and slower-relaxing (SR) processes at lower (Hdc = 1.0 kOe) and higher fields (Hdc = 2.5 kOe), respectively. On the contrary, 3 and 4 exhibit only SR and FR relaxations, regardless of Hdc. Overall, the distinct field-dependence of the single-molecule magnet (SMM) behaviour along with this family of spin-crossover (SCO) cobalt(II)-n-XPhPDI complexes is dominated by Raman mechanisms and, occasionally, with additional temperature-independent Intra-Kramer [LS or HS (D > 0)] or Quantum Tunneling of Magnetisation mechanisms [HS (D < 0)] also contributing.

pH-Switching of the luminescent, redox, and magnetic properties in a spin crossover cobalt(ii) molecular nanomagnet.

The ability of mononuclear first-row transition metal complexes as dynamic molecular systems to perform selective functions under the control of an external stimulus that appropriately tunes their properties may greatly impact several domains of molecular nanoscience and nanotechnology. This study focuses on two mononuclear octahedral cobalt(ii) complexes of formula {[CoII(HL)2][CoII(HL)L]}(ClO4)3·9H2O (1) and [CoIIL2]·5H2O (2) [HL = 4'-(4-carboxyphenyl)-2,2':6',2''-terpyridine], isolated as a mixed protonated/hemiprotonated cationic salt or a deprotonated neutral species. This pair of pH isomers constitutes a remarkable example of a dynamic molecular system exhibiting reversible changes in luminescence, redox, and magnetic (spin crossover and spin dynamics) properties as a result of ligand deprotonation, either in solution or solid state. In this last case, the thermal-assisted spin transition coexists with the field-induced magnetisation blockage of "faster" or "slower" relaxing low-spin CoII ions in 1 or 2, respectively. In addition, pH-reversible control of the acid-base equilibrium among dicationic protonated, cationic hemiprotonated, and neutral deprotonated forms in solution enhances luminescence in the UV region. Besides, the reversibility of the one-electron oxidation of the paramagnetic low-spin CoII into the diamagnetic low-spin CoIII ion is partially lost and completely restored by pH decreasing and increasing. The fine-tuning of the optical, redox, and magnetic properties in this novel class of pH-responsive, spin crossover molecular nanomagnets offers fascinating possibilities for advanced multifunctional and multiresponsive magnetic devices for molecular spintronics and quantum computing such as pH-effect spin quantum transformers.

Single-molecule magnet behaviour and catalytic properties of tetrahedral Co(II) complexes bearing chloride and 1,2-disubstituted benzimidazole as ligands.

Five cobalt(II) complexes of formula [CoCl2(Ln)2] [1 with L1 = 1-benzyl-2-phenyl-1H-benzimidazole, 2 with L2 = 2-(furan-2-yl)-1-(furan-2-ylmethyl)-1H-benzimidazole, 3 with L3 = 1-(4-chlorobenzyl)-2-(4-chlorophenyl)-1H-benzimidazole, 4 with L4 = 1-(2-methoxybenzyl)-2-(2-methoxyphenyl)-1H-benzimidazole and 5 with L5 = 2-(thiophen-2-yl)-1-(thiophen-2-ylmethyl)-1H-benzimidazole] have been synthesised, spectroscopically characterised and cryomagnetically investigated. The crystal structures of 1, 3, 4 and 5 have been determined by X-ray diffraction on single crystals. Each cobalt(II) ion is four-coordinate in a distorted tetrahedral environment built by two chloride anions and two benzimidazole ligands. The neutral molecules are well separated from each other, shortest intermolecular cobalt⋯cobalt distances being greater than 9.0 Å. Static (dc) magnetic susceptibility measurements in the temperature range 2.0-300 K of 1-5 reveal the occurrence of a Curie law behaviour of magnetically non-interacting spin quadruplets in the high-temperature domain with a downturn at low temperatures due to magnetic anisotropy. The values of the D and E/D parameters for these compounds vary in the ranges -8.75 to +8.96 cm-1 and 0.00140 to 0.23, respectively. Dynamic (ac) magnetic susceptibility measurements of 1-5 show slow magnetic relaxation in the lack (1) or under the presence (1-5) of applied dc magnetic fields, a feature which is typical of single-molecule magnet behaviour (SMM). The analysis of the ac data shows that a thermally activated Orbach relaxation mechanism dominates this behaviour. Complexes 1-5 also act as efficient and highly selective eco-friendly catalysts in the coupling reaction between CO2 and epoxides to produce cyclic carbonates under solvent-free conditions. Under optimized reaction conditions, different epoxides were converted to the respective cyclic carbonate, with excellent conversions, using catalyst 4.

Polarization-independent tunable spectral slicing filter in Ti:LiNbO3.

A two-port polarization-independent tunable spectral slicing filter at the 1530 nm wavelength regime is presented. The design utilizes an asymmetric interferometer with a sparse index grating along its arms. The sparse grating makes it possible to select equally spaced frequency channels from an incident WDM signal and to place nulls between them to coincide with the signal comb frequency. The number of selected channels and nulls between them depends on the number of coupling regions used in the sparse grating. The free spectral range depends on the spacing between the coupling regions. The Z-transform method is used to synthesize the filter and determine the spectral response. The operation of a device with six coupling regions is demonstrated, and good agreement with theoretical predictions is obtained. A 3 dB bandwidth of ∼1 nm and thermal tuning over a range of ∼13 nm are measured.

A rare isostructural series of 3d-4f cyanido-bridged heterometallic squares obtained by assembling [FeIII{HB(pz)3}(CN)3]- and LnIII ions: synthesis, X-ray structure and cryomagnetic study.

A new series of cyanido-bridged {FeIIILnIII}2 neutral molecular squares of general formula [Fe{HB(pz)3}(CN)(µ-CN)2Ln(NO3)2(pyim)(Ph3PO)]2·2CH3CN [Ln = Ce (1), Pr (2), Nd (3), Gd (4), Tb (5), Dy (6) and Er (7); {HB(pz)3}- = hydrotris(pyrazolyl)borate, pyim = 2-(1H-imidazol-2-yl)pyridine and Ph3PO = triphenylphosphine oxide] were obtained by reacting the low-spin [Fe{HB(pz)3}(CN)3]- species with the preformed [LnIII(pyim)(NO3)2(pyim)(Ph3PO)]+ complex anions (generated in situ by mixing the nitrate salt of each Ln(III) ion with pyim and Ph3PO molecules). Single-crystal X-ray diffraction studies show that 1-7 are isostructural compounds that crystallize in the triclinic P1̄ space group. Their crystal structures consist of centrosymmetric cyanido-bridged {FeIIILnIII}2 molecular squares where two [Fe{HB(pz)3}(CN)3]- units adopt bis-monodentate coordination modes towards two [LnIII(pyim)(NO3)2(pyim)(Ph3PO)]+ moieties. The cis-oriented convergent sites from both low-spin FeIII and LnIII fragments form a quasi square-shaped molecule in which the 3d and 4f ions alternatively occupy the corners of the square. Both FeIII ions show a distorted octahedral surrounding (C3v symmetry), whereas the LnIII ions exhibit a distorted muffin-like geometry (Cs symmetry) in 1-7. The intramolecular FeIII⋯LnIII distances across the two cyanido-bridges range from ca. 5.48/5.46 up to ca. 5.58/5.61 Å. The molecular squares in 1-7 are interlinked through hydrogen bonds, weak π⋯π stacking and very weak C-H⋯π type interactions into three-dimensional supramolecular networks. The analysis of the solid-state direct-current (dc) magnetic susceptibility data of 1-7 in the temperature range 1.9-300 K reveals the occurrence of weak intra- and intermolecular antiferromagnetic interactions. The small intramolecular antiferromagnetic couplings in 4 compare well with those previously reported for parent systems. Although the coexistence of the spin-orbit coupling (SOC) of the low-spin iron(III) and lanthanide(III) ions in the remaining compounds together with the ligand field effects mask the visualization and make difficult the evaluation of the possible magnetic interactions in them, we were able to do it through a SOC model applied on exact or effective Hamiltonians. Frequency-dependent alternating current magnetic susceptibility signals in the temperature range 2.0-9.0 K under zero and non-zero static fields were observed for 5-7 which indicate slow magnetic relaxation (SMM) behavior. The usual absence of χ''M maxima moved us to estimate their energy barriers through ln(χ''M/ χ'M) vs. 1/T plots, obtaining values from 25 to 40 cm-1.

Field-induced slow magnetic relaxation and magnetocaloric effects in an oxalato-bridged gadolinium(iii)-based 2D MOF.

The coexistence of field-induced slow magnetic relaxation and moderately large magnetocaloric efficiency in the supra-Kelvin temperature region occurs in the 2D compound [Gd(ox)3(H2O)6]n·4nH2O (1), a feature that can be exploited in the proof-of-concept design of a new class of slow-relaxing magnetic materials for cryogenic magnetic refrigeration.

Electronic phase shift measurement for the determination of acoustic wave DOA using single MEMS biomimetic sensor.

MEMS acoustic sensors have been developed to mimic the highly-accurate sound-locating system of the Ormia ochracea fly, which detects sound wavelengths much larger than its hearing organ. A typical ormia-based MEMS directional sound sensor possesses two coupled wings that vibrate in response to sound according to a superposition of its two main resonant modes, rocking and bending. Vibrations are transduced into electronic signals by interdigitated comb finger capacitors at each wing's end along with a capacitance measuring circuitry. A sensor designed to exhibit resonant modes closely placed in frequency, enhancing their coupling, was operated with a closed cavity behind the wings. Simultaneous and independent measurements of electronic signals generated at each of the single sensor wings were used to determine incident sound direction of arrival (DOA). DOA was found proportional to the phase shift between them and to the difference over the sum of their amplitudes as well. Single sensor phase shift DOA measurement presented a resolution better than 3° for sound pressure levels of 25 mPa or greater. These results indicate that a single sensor operating in closed-cavity configuration can provide hemispherical unambiguous direction of arrival of sound waves which wavelength is much larger than the sensor size.

Electroswitching of the single-molecule magnet behaviour in an octahedral spin crossover cobalt(ii) complex with a redox-active pyridinediimine ligand.

Thermal-assisted spin crossover and field-induced slow magnetic relaxation coexist in the solid state for the mononuclear cobalt(ii) complex with the non-innocent 2,6-bis(N-4-methoxyphenylformimidoyl)pyridine ligand. One-electron oxidation of the paramagnetic low-spin CoII ion (SCo = 1/2) to the diamagnetic low-spin CoIII ion (SCo = 0) leads to the electroswitching of the slow magnetic relaxation in acetonitrile solution.

Intermolecular interaction energies and magnetic properties of spin-isolated multinuclear CuII complexes.

Dinuclear CuII complexes with 3,5-dinitrobenzoates and 2,2'-bipyridine (2) or 1,10-phenanthroline (3) were synthesized and characterized. A complete energy framework analysis using the HF/3-21G energy model was performed which found that dispersion forces and C-H...O interactions are responsible for the crystal structure features. The magnetic properties of the complexes show a weak magnetic exchange between spins, resulting in low exchange constants of -2.72 (1) cm-1 and -1.10 (1) cm-1 for complexes (2) and (3), respectively. This results from the low overlap between magnetic orbitals induced by 3,5-dinitrobenzoate bridges and the arrangement of the magnetic orbitals. Consequently, the dinuclear complexes (2) and (3) behave as spin-isolated multinuclear CuII species in contrast to the trinuclear complex with similar ligands.

A giant hybrid organic-inorganic octahedron from a narrow rim carboxylate calixarene.

Here we discovered an unprecedented giant octahedral coordination compound bearing 16 Zn2+, 12 Na+, 8 O2-, 4 OH-, 13 H2O and 6 L4- ligands [L4- = fully deprotonated tetra(carboxymethoxy)calix[4]arene]. Its structure was elucidated by single-crystal X-ray diffraction, wavelength-dispersive X-ray spectroscopy and MALDI-TOF mass spectrometry. This compound, Zn8Na6L6⊃Zn8Na6O8(OH)4(H2O)13 (external⊃internal), has eight tetrahedral zinc ions forming the coordination vertices of an outermost cube where carboxylate groups from the sodium calixarenes are anchored. Its core consists of eight Zn2+, six Na+, eight O2-, and four OH- distributed over three layers, besides thirteen coordinated H2O molecules.

2D and 3D mixed MII/CuII metal-organic frameworks (M = Ca and Sr) with N,N'-2,6-pyridinebis(oxamate) and oxalate: preparation and magneto-structural study.

Three heterobimetallic complexes of formula [Ca2Cu3(mpyba)2(2-apyma)(H2O)7]·8.3H2O (1), [Sr2Cu3(mpyba)2(2-apyma)(H2O)8]·11.6H2O (2) and [Sr4.5Cu4(mpyba)4(ox)(H2O)20]·8.5H2O (3) [H4mpyba = N,N'-2,6-pyridinebis(oxamic acid), 2-apyma = 2-(6-aminopyridinyl)oxamate and ox = oxalate] have been synthesized and structurally characterized. Complexes 1 and 2 are isostructural compounds, with tricopper(ii) units having mpyba and its hydrolytic product (2-apyma) as ligands. They are interlinked through strontium(ii) (1) and calcium(ii) (2) ions to afford neutral two-dimensional networks. Two of the copper(ii) ions are five-coordinate in distorted square pyramidal (Cu3) and trigonal bipyramidal (Cu1) surroundings, whereas the other (Cu2) is six-coordinate in an elongated octahedral environment. The main difference between their structures, apart from the number of water molecules, resides in the nature of the alkaline earth cation coordinated to the oxamate fragments, Sr2+ (1)/Ca2+ (2), which exhibit eight and seven coordination, respectively. The π-π interactions and an extensive network of hydrogen bonds in 1 and 2 lead to supramolecular 3D structures. The relatively small size of their cavities, in the micropore domain, hinders the inclusion of N2 but allows CO2 adsorption (0.45 and 0.52 mmol g-1 for 1 and 2, respectively). The structure of 3 is made up of [3,3] metallacyclophane-type motifs, having the formula [Cu2(mpyba)2(H2O)2]4-. These act as tetrakis(bidentate) ligands towards the strontium(ii) ions (Sr1, Sr2 and Sr3), leading to a sheet-like polymer growing in the bc plane, which extends further along the crystallographic a axis by a bis(chelating) oxalate between the Sr1 atoms. The investigation of the magnetic properties of 1-3 in the temperature range 1.9-300 K shows the occurrence of an overall antiferromagnetic behaviour for 1 and 2 [J12 = J23 = -9.71(2) (1) and -10.81(5) cm-1 (2), with the Hamiltonian being defined as H = -J12S1·S2 - J23S2·S3 + gßH[S1 + S2 + S3], and a ferromagnetic coupling within the dicopper(ii) metallacylophane unit of 3 [J = +1.86(1) cm-1 through the Hamiltonian H = -JS1·S2 + gßH(S1 + S2)]. Simple orbital symmetry considerations (1-3) and the spin polarization mechanism (3) account for the observed magnetic properties.

Há relação entre custos hospitalares e tempo porta-balão? / Is there an association between hospital costs and door-to-balloon time?

O tempo porta-balão (TPB) tornou-se uma medida de desempenho e é foco de iniciativas de melhoria da qualidade assistencial. Este estudo teve como objetivo avaliar a relação entre o TPB e seu impacto nos custos de internação hospitalar. Métodos: Pacientes tratados com intervenção coronária percutânea primária, entre 2008 e 2013, foram divididos de acordo com o TPB < ou ≥ 90 minutos. Todos os custos registrados na alta hospitalar foram ajustados por meio do Índice de Variação de Custos Médico-Hospitalares.Resultados: Foram incluídos 141 pacientes, agrupados em TPB < 90 minutos (n = 77) e TPB ≥ 90 minutos(n = 64). Os TPB foram 64,0 ± 14,1 minutos e 133,8 ± 35,2 minutos, respectivamente. Não foram observadasdiferenças nos desfechos clínicos entre os grupos. Os custos foram de R$ 34.883,24 ± 27.749,46, sendo ocusto médio para TPB < 90 minutos de R$ 33.194,24 ± 27.387,61, e para TPB ≥ 90 minutos, de R$ 36.947,58± 28.267,80 (p = 0,43). Os custos, segundo a artéria culpada, foram de R$ 29.588,53 ± 16.358,85 para acoronária direita; R$ 48.494,62 ± 44.015,04 para a circunflexa; e de R$ 34.016,96 ± 26.503,94 paraa descendente anterior. Houve diferença entre os custos dos procedimentos relativos à artéria circunflexacomparados aos da coronária direita ou da descendente anterior (p = 0,01), mas não houve diferença entre os custos relativos à coronária direita, comparados à descendente anterior (p = 0,68). Conclusões: Não houve diferença nos custos hospitalares, no âmbito da saúde suplementar, quando os grupos foram divididos de acordo com o TPB. Os desfechos clínicos foram semelhantes, e foi encontrada uma diferença de custos em pacientes com a artéria circunflexa culpada...

Door-to-balloon time (DBT) has become a measure of performance and is the focus in quality of care improvement initiatives. This study aimed to evaluate the association between DBT and its impacton hospital costs. Methods: Patients treated with primary percutaneous coronary intervention between 2008 and 2013 were divided according to the DBT < or ≥ 90 minutes. All costs recorded at hospital discharge were adjusted bythe Medical-Hospital Cost Variation Index. Results: A total of 141 patients were included, grouped as DBT < 90 minutes (n = 77) and DBT ≥ 90 minutes(n = 64). DBT was 64.0 ± 14.1 minutes and 133.8 ± 35.2 minutes, respectively. There were no diferences in clinical outcomes between the groups. The costs were R$ 34,883.24 ± 27,749.46, with the mean cost for DBT < 90 minutes being R$ 33,194.24 ± 27,387.61 and the cost for DBT ≥ 90 minutes R$ 36,947.58 ±28,267.80 (p = 0.43). The costs, according to the culprit artery, were R$ 29,588.53 ± 16,358.85 for the rightcoronary artery; R$ 48,494.62 ± 44,015.04 for the left circumflex artery; and R$ 34,016.96 ± 26,503.94 forthe left anterior descending artery. There was a difference between the costs of procedures related to theleft circumflex artery when compared to the right coronary or left anterior descending arteries (p = 0.01),but there was no difference between the costs related to the right coronary, when compared to the left anterior descending artery (p = 0.68). Conclusions: There was no difference in hospital costs regarding the private health insurance, when the groups were divided according to the DBT. Clinical outcomes were similar and a difference in costs wasfound for patients with the circumflex artery as the culprit vessel...

Estudo multicêntrico dos resultados das trocas valvares com o uso da bioprótese Biocar no Estado de Minas Gerais / Results with implanted bioprothesis in Biocor in the state of Minas Gerais, Brazil

No período de março de 1981 a março de 1988, foram implantadas 2324 biopróteses, em 2016 pacientes, em 5 Centros do Estado de Minas Gerais. Este estudo inclui somente a análise dos pacientes submetidos a troca valvar aórtica (n = 603) e mitral (n = 1110), isoladamente. Neste grupo ( = 1713) , a mortalidade hospitalar foi de 104 pacientes (6,1%). Dos 1609 pacientes que receberam alta hospitalar, conseguimos o seguimento de 1101 pacientes (64,3). Esta análise corresponde a um período de 1 a 84 meses, com média de 48 meses e com um seguimento cumulativo d; aórticas (n = 385) = 1230 pacientes/ano; mitrais (n = 716) = 3018 pacientes/ano. Foram registradas 102 complicaçöes tardias em 716 pacientes mitrais (14,24%) e 51 complicaçöes no grupo aórtico (13,2%). Com relaçäo à faixa etária, encontramos 220 pacientes menores de 20 anos (mitrais = 176/aórticos = 44) e, neste subgrupo, as disfunçöes valvares incidiram em 43% dos pacientes mitrais e em 29% dos pacientes aórticos. A endocardite protética foi mais encontrada nos aórticos (45%) do que nos mitrais (29,7%). Dos 1101 pacientes, 62 foram reoperados, com mortalidade hospitalar de 12,6%. A reoperaçäo por disfunçäo valvar foi mais freqüente no grupo mitral com idade inferior a 20 anos. A curva atuarial livre de mortalidade relacionada à bioprótese foi de 97,1% (32/1101 pacientes). No grupo aórtico, 96,9% estiveram livres de disfunçäo valvar ao final de 7 anos, enquanto que, no grupo mitral, este índice foi de 95,2%. Nos pacientes menores de 20 anos do grupo mitral, encontramos o maior índice de falência valvar (85,3% livre após 7 anos). Ao final deste estudo, a maior parte destes pacientes encontrava-se em classe funcional I e II. Embora a incidência de reoperaçäo seja expressiva, esta é aceitável, tendo em vista que as biopróteses oferecem uma alternativa mais segura do que as próteses mecânicas, durante este mesmo período do seguimento. A análise destes resultados sugere a continuaçäo de pesquisas que tornem possível a fabricaçäo de um substituto valvar ideal. Todavia, estes resultados comparam-se, de modo favorável, a resultados com biopróteses semelhantes da literatura mundial