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At least 1,369 records · Page 76Linked to original sources
PubMed2003

[Experience with orbital implants in particular with porous hydroxyapatite materials].

PURPOSE: Various materials have been developed since the first implantation of a hydroxyapatite sphere in 1985. They are similar to the porous basic structure and imitate the biological behavior of coralline implants. This article presents own clinical experience with hydroxyapatite implants from 1993 to 2003 and compares own results and other porous orbital implants in the international scientific literature. RESULTS: The original hydroxyapatite implant is well tolerated and implant extrusion is rare. A retrospective analysis of 357 patients regarding this complication shows an extrusion rate of 2.6% over 10 years. The subjective positive tolerance of 71.2% corresponds to the results of international studies. After several stages of development the synthetic product (FCI3) is now comparable with the original product with regard to operative complications and subjective compatibility. Both orbital implants should be used with a protective covering to avoid premature extrusion and to facilitate suturing the extraocular muscles anterior. When using material from humane donors the material must be guaranteed to be completely sterile. The use of vicryl as an orbital plomb wrapping leads to contradictory reports in the literature. Hydroxyapatite ceramics in combination with silicone india rubber represent an alternative to the materials listed above and in this case a wrapping of the orbital plomb is unnecessary. Spherical orbital implants made of aluminum oxide (bioceramic implant) are an alternative to corraline hydroxyapatite implants. Because of their porous,crystalline structure bioceramic implants vascularize well. Porous polythylene orbital implants,which are not available in Germany, are economical, but due to their porosity and vascularization properties they are not comparable with pure hydroxyapatite or hydroxyapatite ceramics. FUTURE VIEW: The dynamic development of the infant anopthalmus adapted to the size growth of the orbita and the exact volume replenishment of the adult orbita cannot yet be fulfilled with the presently available porous hydroxyapatite materials and is the subject of future research.

Eye Enucleation↗
PubMed1996

Energetic particle environment in near-Earth orbit.

The hazard of exposure to high doses of ionizing radiation is one of the primary concerns of extended manned space missions and a continuous threat for the numerous spacecraft in operation today. In the near-Earth environment the main sources of radiation are solar energetic particles (SEP), galactic cosmic rays (GCR), and geomagnetically trapped particles, predominantly protons and electrons. The intensity of the SEP and GCR source depends primarily on the phase of the solar cycle. Due to the shielding effect of the Earth's magnetic field, the observed intensity of SEP and GCR particles in a near-Earth orbit will also depend on the orbital parameters altitude and inclination. The magnetospheric source strength depends also on these orbital parameters because they determine the frequency and location of radiation belt passes. In this paper an overview of the various sources of radiation in the near-Earth orbit will be given and first results obtained with the Solar, Anomalous, and Magnetospheric Particle Explorer (SAMPEX) will be discussed. SAMPEX was launched on 3 July 1992 into a near polar (inclination 82 degrees) low altitude (510 x 675 km) orbit. The SAMPEX payload contains four separate instruments of high sensitivity covering the energy range 0.5 to several hundred MeV/nucleon for ions and 0.4 to 30 MeV for electrons. This low altitude polar orbit with zenith-oriented instrumentation provides a new opportunity for a systematic study of the near-Earth energetic particle environment.

Cosmic Radiation↗
PubMed2000

Reduction of orbital frontal cortex volume in geriatric depression.

BACKGROUND: Postmortem studies have documented abnormalities in the medial orbital frontal cortex in depressed patients. In this study we evaluated whether atrophy of this region can be identified in older depressed patients using magnetic resonance imaging. METHODS: Twenty elderly patients meeting DSM-IV criteria for major depression and 20 matched control subjects were studied. The orbital frontal cortex was measured in both hemispheres using magnetic resonance imaging. RESULTS: Depressive patients had reduced volume in the total orbital frontal cortex, right orbital frontal cortex, and left orbital frontal cortex. CONCLUSIONS: Our finding of a reduction in orbital frontal cortex volume in both sides of the brain suggests that this region of the brain may have a critical role in the development of depression and raises questions about the etiology of the changes.

Aged↗
PubMedDate not supplied

Ground and on-orbit command and data handling architectures for the Active Rack Isolation System microgravity flight experiment.

The Active Rack Isolation System [ARIS] International Space Station [ISS] Characterization Experiment, or ARIS-ICE for short, is a long duration microgravity characterization experiment aboard the ISS. The objective of the experiment is to fully characterize active microgravity performance of the first ARIS rack deployed on the ISS. Efficient ground and on-orbit command and data handling [C&DH] segments are the crux in achieving the challenging objectives of the mission. The objective of the paper is to provide an overview of the C&DH architectures developed for ARIS-ICE, with the view that these architectures may serve as a model for future ISS microgravity payloads. Both ground and on-orbit segments, and their interaction with corresponding ISS C&DH systems are presented. The heart of the on-orbit segment is the ARIS-ICE Payload On-orbit Processor, ARIS-ICE POP for short. The POP manages communication with the ISS C&DH system and other ISS subsystems and payloads, enables automation of test/data collection sequences, and provides a wide range of utilities such as efficient file downlinks/uplinks, data post-processing, data compression and data storage. The hardware and software architecture of the POP is presented and it is shown that the built-in functionality helps to dramatically streamline the efficiency of on-orbit operations. The ground segment has at its heart special ARIS-ICE Ground Support Equipment [GSE] software developed for the experiment. The software enables efficient command and file uplinks, and reconstruction and display of science telemetry packets. The GSE software architecture is discussed along with its interactions with ISS ground C&DH elements. A test sequence example is used to demonstrate the interplay between the ground and on-orbit segments.

Acceleration↗
PubMed1988

Orbital myositis involving the oblique muscles. An echographic study.

Idiopathic orbital myositis is a common nonspecific orbital inflammatory syndrome that can involve one or more of the extraocular muscles. Oblique muscle involvement is infrequently reported, possibly because such involvement is difficult to identify clinically or by computed tomography (CT). The authors reviewed seven cases of orbital myositis involving the oblique muscles solely or in association with rectus muscle involvement. Standardized echography demonstrated homogeneous low-reflective enlargement, diagnostic of myositis, of the superior and inferior oblique muscles and tendons along their courses. The finding of massive inferior chemosis was associated with involvement of the inferior oblique muscle. Although the disease typically responds to therapy with systemic steroids, residual gaze restriction may occur. The oblique muscles may be frequently involved in idiopathic orbital myositis when evaluated by standardized orbital echography. In these cases, echography provides rapid, accurate, and reliable confirmation of the diagnosis of myositis, differentiates other orbital inflammatory diseases, and provides an objective measure of the therapeutic response.

Adult↗
PubMed1999

Shape of the orbital opening: individual characterization and analysis of variability in modern humans, Gorilla gorilla, and Pan troglodytes.

The description of the human orbital shape is principally qualitative in the classical literature, and characterised by adjectives such as circular, rectangular or quadrangular. In order to provide a precise quantification and interpretation of this shape, a study based on automatic image analysis and Fourier analysis was carried out on 45 human skulls (30 males, 15 females), and for comparison on 61 skulls of Gorilla gorilla (40 males, 21 females), and 34 skulls of Pan troglodytes (20 males, 14 females). Sexual dimorphism in the shape of the orbital opening was not demonstrated. Its dominant morphological features could be characterized by Fourier analysis; elliptical elongation and quadrangularity were dominant morphological features of the shape of the orbital opening in the three species. Elliptical elongation was more marked in humans and Pan, whereas quadrangularity was particularly emphasized in Gorilla. An intraspecific variability of the shape of the orbital opening existed in humans, Gorilla and Pan, and seemed close in the three species. Interspecific partition between humans, Gorilla and Pan was demonstrated despite the variability observed in the three species studied. Interspecific differences between Gorilla and the Pan-humans group were principally explained by the differences in quadrangularity, and by differences in orientation of triangularity and pentagonality. Differences in the shape of the orbital opening between humans and Pan were principally explained by differences in hexagonality, and by differences in orientation of quadrangularity. A closeness of shape between some humans and some individuals in Pan and, to a lesser degree, with some individuals in Gorilla was observed, demonstrating the existence of a morphological continuum of the shape of the orbital opening in hominoids.

Animals↗
PubMed1997

Spin-Orbit Mixing and Nephelauxetic Effects in the Electronic Spectra of Nickel(II)-Encapsulating Complexes Involving Nitrogen and Sulfur Donors.

A study of spin-orbit mixing and nephelauxetic effects in the electronic spectra of nickel(II)-encapsulating complexes involving mixed nitrogen and sulfur donors is reported. As the number of sulfur donors is systematically varied through the series [Ni(N(6)(-)(x)()S(x)())](2+) (x = 0-6), the spin-forbidden (3)A(2g) --> (1)E(g) and (3)A(2g) --> (1)A(1g) transitions undergo a considerable reduction in energy whereas the spin-allowed transitions are relatively unchanged. The [Ni(diAMN(6)sar)](2+) and [Ni(AMN(5)Ssar)](2+) complexes exhibit an unusual band shape for the (3)A(2g) --> (3)T(2g) transition which is shown to arise from spin-orbit mixing of the E spin-orbit levels associated with the (1)E(g) and (3)T(2g) states. A significant differential nephelauxetic effect also arises from the covalency differences between the t(2g) and e(g) orbitals with the result that no single set of Racah B and C interelectron repulsion parameters adequately fit the observed spectra. Using a differential covalency ligand-field model, the spectral transitions are successfully reproduced with three independent variables corresponding to 10Dq and the covalency parameters f(t) and f(e), associated with the t(2g) and e(g) orbitals, respectively. The small decrease in f(t) from unity is largely attributed to central-field covalency effects whereas the dramatic reduction in f(e) with increasing number of sulfur donors is a direct consequence of the increased metal-ligand covalency associated with the sulfur donors. Covalency differences between the t(2g) and e(g) orbitals also result in larger 10Dq values than those obtained simply from the energy of the (3)A(2g) --> (3)T(2g) spin-allowed transition.

Journal Article↗
PubMed2000

Variable-energy photoelectron spectroscopy of substituted rhenium and manganese pentacarbonyls: molecular orbital assignments and the interatomic resonant effect.

High-resolution variable-energy photoelectron spectra of M(CO)5X [M = Re, X = Re(CO)5, Cl, Br, and I; and M = Mn, X = Mn(CO)5 and Br] are reported. Tunable synchrotron radiation is used to distinguish the Re 5d and Br 4p orbital based peaks for the controversial Re(CO)5Br. Our results provide firm molecular orbital assignments for all of these molecules. The valence orbital in the ordering of ionization energies for M(CO)5Cl (M = Mn and Re) and Mn(CO)5Br is a 1(M-X) > e(X) > b2(M) > e(M); but for M(CO)5I (M = Mn and Re) and Re(CO)5Br the ordering is a1(M-X) > e(M) > b2(M) > e(X). The crossover of the HOMO in the Re molecules due to the change in the halogen electronegativities occurs at Re(CO)5Br. The metal np-->nd resonance is observed for all of these molecules. For molecules like M2(CO)10 (M = Re and Mn) and Mn(CO)5Br, the observation of this np-->nd resonance is useful in assigning the metal nd based orbitals in their valence level spectra. However, for molecules like Re(CO)5X (X = Br and Cl), a np-->nd type resonance is observed on bands arising from both Re 5d and halogen mp based orbitals. This new resonant effect on the ligand-based orbitals is shown to be mainly due to the interatomic resonant effect. The core and valence level chemical shifts of these compounds are treated using Jolly's approach to confirm the assignments for the valence level spectra of some of these molecules. The high-resolution inner valence and core level spectra of these compounds are reported. Broadening of Re 4f, Br 3d, and I 4d core level spectra is discussed. The Auger peaks are observed in the high-resolution, high-intensity Br 3d of Re(CO)5Br and I 4d of Re(CO)5I spectra.

Journal Article↗
PubMed2001

Geometry of simple molecules: nonbonded interactions, not bonding orbitals, and primarily determine observed geometries.

The forces responsible for the observed geometries of the YX(3) (Y = N or P; X = H, F, or Cl) molecules were studied through ab initio computations at the HF-SCF/6-31G level. The calculated molecular orbitals were grouped as contributing primarily to (a) the covalent bonds, (b) the terminal atom nonbonding electrons (for X = F or Cl), and (c) the central atom nonbonding electrons. This grouping was accomplished through 3-D plotting and an atomic population analysis of the molecular orbitals. The molecules were then moved through a X-Y-X angular range from 90 degrees to 119 degrees, in four or five degree increments. Single-point calculations were done at each increment, so as to quantify the energy changes in the molecular orbital groups as a function of geometry. These calculations show that the nonbonding electrons are much more sensitive to geometry change than are the bonding orbitals, particularly in the trihalide compounds. The molecular orbitals representing the nonbonding electrons on the terminal atoms (both valence and core electrons) contribute to the spreading forces, as they favor a wider X-Y-X angle. The contracting forces, which favor a smaller X-Y-X angle, consist of the orbitals comprising the nonbonding electrons on the central atom (again, both valence and core electrons). The observed geometry is seen as the balance point between these two sets of forces. A simple interaction-distance model of spreading and contracting forces supports this hypothesis. Highly linear trends are obtained for both the nitrogen trihalides (R(2) = 0.981) and phosphorus trihalides (R(2) = 0.992) when the opposing forces are plotted against each other. These results suggest that a revision of the popular conceptual models (hybridization and VSEPR) of molecular geometry might be appropriate.

Journal Article↗
PubMed2003

L-edge X-ray absorption spectroscopy of non-heme iron sites: experimental determination of differential orbital covalency.

X-ray absorption spectroscopy has been utilized to obtain the L-edge multiplet spectra for a series of non-heme ferric and ferrous complexes. Using these data, a methodology for determining the total covalency and the differential orbital covalency (DOC), that is, differences in covalency in the different symmetry sets of the d orbitals, has been developed. The integrated L-edge intensity is proportional to the number of one-electron transition pathways to the unoccupied molecular orbitals as well as to the covalency of the iron site, which reduces the total L-edge intensity and redistributes intensity, producing shake-up satellites. Furthermore, differential orbital covalency leads to differences in intensity for the different symmetry sets of orbitals and, thus, further modifies the experimental spectra. The ligand field multiplet model commonly used to simulate L-edge spectra does not adequately reproduce the spectral features, especially the charge transfer satellites. The inclusion of charge transfer states with differences in covalency gives excellent fits to the data and experimental estimates of the different contributions of charge transfer shake-up pathways to the t(2g) and e(g) symmetry orbitals. The resulting experimentally determined DOC is compared to values calculated from density functional theory and used to understand chemical trends in high- and low-spin ferrous and ferric complexes with different covalent environments. The utility of this method toward problems in bioinorganic chemistry is discussed.

Absorptiometry, Photon↗
PubMed2005

Evidence for d orbital aromaticity in square planar coinage metal clusters.

Quantitative evidence for the existence of aromaticity involving the d orbitals of transition metals is provided for the first time. The doubly bridged square planar (D(4)(h)()) coinage metal clusters (M(4)Li(2), M = Cu (1), Ag (2), and Au (3)) are characterized as aromatic by their substantial nucleus independent chemical shifts (NICS) values in the centers (-14.5, -14.1, and -18.6, respectively). Nevertheless, the participation of p orbitals in the bonding (and cyclic electron delocalization) of 1-3 is negligible. Instead, these clusters benefit strongly from the delocalization of d and to some extent s orbitals. The same conclusion applies to Tsipis and Tsipis' H-bridged D(4)(h)() Cu(4)H(4) ring (4). Canonical MO-NICS analysis of structures 1-3 shows the total diatropic d orbital contributions to the total NICS to be substantial, although the individual contributions of the five sets of filled d orbitals vary. The d orbital aromaticity of Cu(4)Li(2) also is indicated by its atomization energy, 243.2 kcal/mol, which is larger than Boldyrev's doubly (sigma and pi) aromatic Al(4)Li(2) (215.9 kcal/mol).

Journal Article↗
PubMed2004

An orbital phase theory for the torquoselectivity of the ring-opening reactions of 3-substituted cyclobutenes: geminal bond participation.

We apply an orbital phase theory to the torquoselectivity of the electrocyclic reactions of 3-substituted (X) cyclobutenes. The torquoselectivity is shown to be controlled by the orbital-phase relation of the reacting pi(CC) and sigma(CC) bonds with the sigma(CX) bond geminal to the sigma(CC) bond to be cleaved. The inward rotation of electron-donating sigma(CX) bonds and outward rotation of electron-withdrawing sigma(CX) bonds have been deduced from the orbital-phase theory. Enhancement of the inward rotation by the electron-donating capability of the sigma(CX) bonds is confirmed by the correlation between the torquoselectivity and sigma(CX) orbital energy. The orbital overlaps between the geminal sigma(CX) (sigma(CH)) and sigma(CC) bonds are found to be important as well. Unsaturated substituents with low-lying unoccupied pi orbitals also promote the inward rotation.

Journal Article↗
PubMed2004

Rationale for the acidity of Meldrum's acid. Consistent relation of C-H acidities to the properties of localized reactive orbital.

Detailed investigation on the origin of the acidity of the alpha-protons of a set of the carbonyl molecules was carried out on the basis of properties of the localized molecular orbital. An anomalously high acidity of Meldrum's acid, as compared with those of dimedone and dimethyl malonate, is one of the well-known but unresolved issues. The well-localized sigma orbitals of the C-H bonds at the alpha-position of the carbonyl groups can be obtained with the reactive hybrid orbital (RHO) theory. We found that the energy levels of the unoccupied RHOs of the C-H moiety of Meldrum's acid and other carbonyl compounds showed a good linear correlation with the experimental deprotonation energies. This is probably because the deprotonation reaction to form the proposed naked anions in a polar solvent is a highly endothermic process, in which the thermodynamic energy differences between the neutral molecules and the corresponding anions approximately coincide with the activation energies. We also investigated the effect of the conformational change upon deprotonation on the electron-accepting energy level of the relevant C-H bonds of cyclic/acyclic and monocarbonyl/dicarbonyl compounds. A conformational change occurs in the cases of cyclic six-membered compounds, but its influence on the reactivity of the C-H bond is small. The acidity of dicarbonyl compounds, including Meldrum's acid, showed a good correlation with the deviations from the perpendicular position of the dihedral angles of the relevant C-H bond with respect to the adjacent carbonyl C=O bond. This angle parameter can be related to the magnitude of the in-phase orbital interaction between the sigma(CH) and pi(C)(=)(O) orbitals, which facilitate electron acceptance. These results indicated that the acidity of the alpha-proton of carbonyl compounds can be represented in terms of the electron-accepting orbital levels of the unoccupied RHO of the C-H moiety. All the linear relationships found in the present work strongly suggested that the acidity of Meldrum's acid, which is conventionally regarded as an anomaly, is consistent with those of the other carbonyl compounds.

Journal Article↗
PubMed2004

Tomographic imaging of molecular orbitals.

Single-electron wavefunctions, or orbitals, are the mathematical constructs used to describe the multi-electron wavefunction of molecules. Because the highest-lying orbitals are responsible for chemical properties, they are of particular interest. To observe these orbitals change as bonds are formed and broken is to observe the essence of chemistry. Yet single orbitals are difficult to observe experimentally, and until now, this has been impossible on the timescale of chemical reactions. Here we demonstrate that the full three-dimensional structure of a single orbital can be imaged by a seemingly unlikely technique, using high harmonics generated from intense femtosecond laser pulses focused on aligned molecules. Applying this approach to a series of molecular alignments, we accomplish a tomographic reconstruction of the highest occupied molecular orbital of N2. The method also allows us to follow the attosecond dynamics of an electron wave packet.

Journal Article↗
PubMed2004

Relativistic spin-orbit effects on hyperfine coupling tensors by density-functional theory.

A second-order perturbation theory treatment of spin-orbit corrections to hyperfine coupling tensors has been implemented within a density-functional framework. The method uses the all-electron atomic mean-field approximation and/or spin-orbit pseudopotentials in incorporating one- and two-electron spin-orbit interaction within a first-principles framework. Validation of the approach on a set of main-group radicals and transition metal complexes indicates good agreement between all-electron and pseudopotential results for hyperfine coupling constants of the lighter nuclei in the system, except for cases in which scalar relativistic effects become important. The nonrelativistic Fermi contact part of the isotropic hyperfine coupling constants is not always accurately reproduced by the exchange-correlation functionals employed, particularly for the triplet and pi-type doublet radicals in the present work. For this reason, ab initio coupled-cluster singles and doubles with perturbative triples results for the first-order contributions have been combined in the validation calculations with the density-functional results for the second-order spin-orbit contributions. In the cases where spin-orbit corrections are of significant magnitude relative to the nonrelativistic first-order terms, they improve the agreement with experiment. Antisymmetric contributions to the hyperfine tensor arise from the spin-orbit contributions and are discussed for the IO2 radical, whereas rovibrational effects have been evaluated for RhC, NBr, and NI.

Journal Article↗
PubMed2004

The investigation of spin-orbit effect for the F((2)P)+HD reaction.

In this paper, we employ the time-dependent quantum wave packet method to study the reaction of F((2)P(3/2), (2)P(1/2)) with HD on the Alexander-Stark-Werner potential energy surface. The reaction probabilities and total integral cross sections of the spin-orbit ground and excited states for the two possible products of the system are calculated. Because the reaction channel of the excited spin-orbit state is closed at the resonance energy, the resonance feature does not appear in the reaction probabilities and cross section for the F((2)P(1/2))+HD(v=j=0)-->HF+D reaction, in contrast with that found for the ground spin--orbit state. We also compare the average cross sections of the two possible products with the experimental measurement. The resonance peak in the present average cross section for the HF+D product is slightly larger than the experimental result, but much smaller than that of the single-state calculations on the potential energy surface of Stark and Werner. It seems that the spin--orbit coupling would play a relatively important role in this reaction. Moreover, the isotope effects of the ground and excited spin--orbit states and the reactivity of the two product channels from the excited spin--orbit state are presented.

Journal Article↗
PubMed2005

Orbital-optimized coupled-cluster theory does not reproduce the full configuration-interaction limit.

It is shown that due to the mixing of the usual projection approach of coupled cluster with variational orbital optimization, orbital-optimized coupled cluster (OCC) fails to reproduce the full configuration-interaction (full CI) limit when the cluster operator becomes complete. It is pointed out that the fulfillment of the projected singles equations, which define the orbital gradient in Brueckner coupled cluster (BCC), is mandatory for a correct behavior. As numerical examples we present general OCC and BCC calculations up to the full CI limit on CH(2) and an active-space model of ozone. The observed deviations of OCC from full CI are of the order of the correlation error obtained in calculations with up to quadruples excitations. Thus the failure of OCC may be considered tolerable in more approximate calculations but clearly prohibitive for any benchmark application. For applications to active-space models a hybrid approach for OCC is suggested in which for active particle-hole rotations the Brueckner orbital gradient is employed, whereas for the remaining orbital rotations the variational orbital gradient is retained.

Journal Article↗
PubMed2005

Fast localized orthonormal virtual orbitals which depend smoothly on nuclear coordinates.

We present here an algorithm for computing stable, well-defined localized orthonormal virtual orbitals which depend smoothly on nuclear coordinates. The algorithm is very fast, limited only by diagonalization of two matrices with dimension the size of the number of virtual orbitals. Furthermore, we require no more than quadratic (in the number of electrons) storage. The basic premise behind our algorithm is that one can decompose any given atomic-orbital (AO) vector space as a minimal basis space (which includes the occupied and valence virtual spaces) and a hard-virtual (HV) space (which includes everything else). The valence virtual space localizes easily with standard methods, while the hard-virtual space is constructed to be atom centered and automatically local. The orbitals presented here may be computed almost as quickly as projecting the AO basis onto the virtual space and are almost as local (according to orbital variance), while our orbitals are orthonormal (rather than redundant and nonorthogonal). We expect this algorithm to find use in local-correlation methods.

Algorithms↗