Exchange interactions in transition metal oxides: the role of oxygen spin polarization.

Magnetism of transition metal (TM) oxides is usually described in terms of the Heisenberg model, with orientation-independent interactions between the spins. However, the applicability of such a model is not fully justified for TM oxides because spin polarization of oxygen is usually ignored. In the conventional model based on the Anderson principle, oxygen effects are considered as a property of the TM ion and only TM interactions are relevant. Here, we perform a systematic comparison between two approaches for spin polarization on oxygen in typical TM oxides. To this end, we calculate the exchange interactions in NiO, MnO and hematite (Fe2O3) for different magnetic configurations using the magnetic force theorem. We consider the full spin Hamiltonian including oxygen sites, and also derive an effective model where the spin polarization on oxygen renormalizes the exchange interactions between TM sites. Surprisingly, the exchange interactions in NiO depend on the magnetic state if spin polarization on oxygen is neglected, resulting in non-Heisenberg behavior. In contrast, the inclusion of spin polarization in NiO makes the Heisenberg model more applicable. Just the opposite, MnO behaves as a Heisenberg magnet when oxygen spin polarization is neglected, but shows strong non-Heisenberg effects when spin polarization on oxygen is included. In hematite, both models result in non-Heisenberg behavior. The general applicability of the magnetic force theorem as well as the Heisenberg model to TM oxides is discussed.

Determination of the geometric structure of neutral niobium carbide clusters via infrared spectroscopy.

We report experimental vibrational spectra of small neutral niobium carbide clusters in the 350-850 cm-1 spectral range. Clusters were first irradiated by IR light and subsequently probed using UV light with photon energies just below the ionization threshold. Upon resonance with an IR vibrational mode, the number of cluster ions increases, allowing to record a vibrational spectrum. In complementary density functional theory calculations, we have simulated the IR spectra for several low-energy isomers. We were able to assign the spectra experimentally obtained for each cluster size to a specific geometric structure based on the match with the computed spectra. The number of the cluster sizes investigated here allows to follow the evolution of the geometric structure of the niobium and carbon components of clusters separately. For Nb6Cm (m = 4, 5, 6), we observe the emergence of the cubic crystal structures similar to the bulk.

The repopulation of electronic states upon vibrational excitation of niobium carbide clusters.

We study the infrared (IR) resonant heating of neutral niobium carbide clusters probed through ultraviolet photoionization spectroscopy. The IR excitation not only changes the photoionization spectra for the photon energies above the ionization threshold, but also modulates ion yield for energies significantly below it. An attempt to describe the experimental spectra using either Fowler's theory or thermally populated vibrational states was not successful. However, the data can be fully modeled by vibrationally and rotationally broadened discrete electronic levels obtained from Density Functional Theory (DFT) calculations. The application of this method to spectra with different IR pulse energies not only yields information about the excited electronic states in the vicinity of the HOMO level, populated by manipulation of the vibrational coordinates of a cluster, but also can serve as an extra indicator for the cluster isomeric structure and corresponding DFT-calculated electronic levels.

Effect of flying activity on capillary-fiber geometry in pigeon flight muscle.

The effect of flying activity on capillary density and geometry was investigated in pectoralis muscle of 4 wild-caught (W) pigeons (BW 233-348 g) perfusion-fixed in situ and processed for electron microscopy. Morphometric analysis revealed both differences and similarities with similar sampling sites (superficial and deep in central area of right or left pectoralis major muscle, approximately midway along cranio-caudal and lateral axis) in sedentary (S) pigeons. Differences were the greater fractional cross-sectional area of aerobic fibers (W, 82 +/- 2%; S, 63 +/- 6%; p = 0.006) and the greater volume density of mitochondria per volume of fiber (W, 22.0 +/- 1.3%; S, 15.7 +/- 1.7%; p = 0.011) in wild-caught pigeons. While glycolytic fibers were significantly narrower in W, the size of the majority of fibers comprising the muscles, i.e. aerobic fibers, was similar in the two groups. Other similarities were found in capillary-to-fiber ratio (W, 2.0 +/- 0.2; S, 2.1 +/- 0.2) and in the degree of orientation of capillaries in the two groups. In addition, both capillary density at a given fractional cross-sectional area of aerobic fibers and capillary length per fiber volume at a given mitochondrial volume density were similar in the two groups, indicating a proportional increase in capillarity and muscle aerobic capacity in W compared with S. Comparison of capillary numbers around aerobic fibers at a given mitochondrial volume per microns length of fiber showed no difference between W and S groups nor with previous data in muscles with wide differences in fiber size and mitochondrial density such as rat soleus, bat muscles and hummingbird flight muscles. This supported the notion of a tight correlation between capillary numbers around individual fibers and mitochondrial volume per unit length of fiber in aerobic muscles. It also supported the idea that it is the number of capillaries around the fibers rather than diffusion distance which determines O2 flux rates in highly aerobic muscles.

Stress failure of pulmonary capillaries in racehorses with exercise-induced pulmonary hemorrhage.

Bleeding into the lungs in thoroughbreds is extremely common; there is evidence that it occurs in essentially all horses in training. However, the mechanism is unknown. We tested the hypothesis that exercise-induced pulmonary hemorrhage (EIPH) is caused by stress failure of pulmonary capillaries. Three thoroughbreds with known EIPH were galloped on a treadmill, and after the horses were killed with intravenous barbiturate the lungs were removed, inflated, and fixed for electron microscopy. Ultrastructural studies showed evidence of stress failure of pulmonary capillaries, including disruptions of the capillary endothelial and alveolar epithelial layers, extensive collections of red blood cells in the alveolar wall interstitium, proteinaceous fluid and red blood cells in the alveolar spaces, interstitial edema, and fluid-filled protrusions of the endothelium into the capillary lumen. The appearances were consistent with the ultrastructural changes we have previously described in rabbit lungs at high capillary transmural pressures. Actual breaks in the endothelium and epithelium were rather difficult to find, and they were frequently associated with platelets and leukocytes that appeared to be plugging the breaks. The paucity of breaks was ascribed to their reversibility when the pressure was lowered and to the fact that 60-70 min elapsed between the gallop and the beginning of lung fixation. Capillary wall stress was calculated from pulmonary vascular pressures measured in a companion study (Jones et al. FASEB J. 6: A2020, 1992) and from measurements of the thickness of the blood-gas barrier and the radius of curvature of the capillaries. The value was as high as 8 x 10(5) dyn/cm2 (8 x 10(4) N/m2), which exceeds the breaking stress of most soft tissues. We conclude that stress failure of pulmonary capillaries is the mechanism of EIPH.

Geometry of blood-tissue exchange in bat flight muscle compared with bat hindlimb and rat soleus muscle.

We investigated the relationship between capillary-to-fiber geometry and muscle aerobic capacity by comparing the bat flight muscle (pectoralis muscle), i.e., an ultimate case of extreme O2 demand in a mammalian skeletal muscle, with bat hindlimb and rat soleus muscles. At a given sarcomere length (2.1 microns), fiber cross-sectional area was considerably smaller in bat muscles (pectoralis 318 +/- 10 microns 2, hindlimb 447 +/- 35 microns 2) than in rat soleus muscle (2,027 +/- 125 microns 2). Capillary number per fiber cross-sectional area was much greater in bat pectoralis (6,394 +/- 380/mm2) than in bat hindlimb and rat soleus muscle (2,865 +/- 238 and 1,301 +/- 129/mm2, respectively; all values normalized to 2.1-microns sarcomere length). At the same sarcomere length (2.1 microns), the degree of tortuosity and branching of capillaries were significantly greater in bat pectoralis than in bat hindlimb and rat soleus muscle. In bat flight muscle, capillary length per fiber volume was very high (9,025 +/- 342/mm2). It was 2.2- and 5.4-fold larger than in bat hindlimb and rat soleus, respectively. Mitochondria occupied 35.3 +/- 1.2, 16.5 +/- 1.3, and 6.1 +/- 0.9% of the muscle fiber volume in bat pectoralis, hindlimb, and rat soleus muscles, respectively. There was a strong correlation between capillary length (as well as capillary surface) per fiber volume and mitochondrial volume density in all muscles. Considering capillary supply and mitochondrial volume on an individual fiber basis, we found that 1) the number of capillaries around a fiber was linearly related to mitochondrial volume per micron length of fiber in the muscles but that 2) capillary surface per fiber surface, at given mitochondrial volume per micron length of fiber, was about twice as large in bat pectoralis as in rat soleus muscle, whereas in bat hindlimb it was intermediate between that in bat pectoralis and that in rat soleus muscle. This was due to the differences in fiber size (rat soleus greater than bat muscles) and capillary-to-fiber ratio (bat pectoralis greater than hindlimb) between the muscles. It is notable that in the bat, the substantially greater O2 transfer capacity of the flight muscle compared with hindlimb was achieved by increasing the size of the capillary-to-fiber interface, i.e., capillary-to-fiber surface, via an increase in capillary number rather than by substantially reducing fiber size.

The extracellular matrix of the human optic nerve.

The nerve fibers of the optic nerve are enclosed and segmented by extracellular matrix. With immunostains, we localized collagen types I through VI, laminin, and fibronectin in frozen sections of the extracellular matrix of the prelaminar, laminar, and retrolaminar human optic nerve. The internal limiting lamina of the optic nerve has an extracellular composition similar to the thicker adjacent retinal internal limiting lamina. We confirmed that the lamina cribrosa contains type IV collagen and laminin, whereas the sclera does not. The septa of the retrolaminar optic nerve appear as vascular inward extensions of the pia mater. The glial tube that lines the optic nerve extends forward from the retrolaminar optic nerve through the lamina cribrosa to end anteriorly at the retinal pigment epithelium. It does not separate the optic nerve from the adjacent sensory retina.

Muscle fiber size and chronic exposure to hypoxia.

Sarcomere length is practically never considered when fiber size and dependent variables are compared between muscles or experimental conditions. Because of the direct dependence of fiber cross-sectional area on muscle shortening, it is imperative to normalize measurements of fiber size, and related variables (e.g. capillary number/mm2 of fiber) to sarcomere length. We examined the relationship between fiber cross-sectional area and sarcomere length in muscles of animals chronically exposed to high altitude (deer mice, Peromyscus maniculatus, native to 3800 m, and rats, Sprague-Dawley, kept at the same altitude for 5 months) compared to sea-level controls. We found no difference in fiber cross-sectional area, normalized to sarcomere length, between high altitude and control animals in either species. It has been demonstrated that sarcomere length can vary by as much as 30-44% and 43-76% in biopsy and perfusion-fixed muscles, respectively. Therefore, identifying relatively small changes in fiber size in response to a given experimental condition in such material without normalizing for sarcomere length is difficult if not impossible. Furthermore, if the conditions of the investigation induce differences in sarcomere length between experimental and control animals, artifactual changes in fiber cross-sectional area will be produced.