Primary iliac venous aneurysm is an exceedingly rare abnormality that can be complicated by pulmonary embolism, thrombosis, and rupture. Here we report the case of an otherwise healthy 40-year-old ...man with a unilateral external iliac vein aneurysm without any evidence of an arteriovenous fistula, proximal stenosis, or obstruction, as reported on computed tomography. Pulmonary embolism was diagnosed using 99mTc-macroaggregated albumin scintigraphy. To prevent life-threatening complications, we treated the patient with anticoagulant therapy and performed aneurysmectomy with reconstruction using a saphenous vein graft patch. Although postoperative venography showed obstruction of the external iliac vein, the patient remained asymptomatic.
Emergence of biochemical homochirality is an intriguing topic, and none of the proposed scenarios has encountered a unanimous consensus. Candidates for naturally occurring processes, which may ...originate chiral selection, involve interaction of matter with light and molecular collisions. We performed and report here: (1) simulations of photodissociation of an oriented chiral molecule by linearly polarized (achiral) light observing that the angular distribution of the photofragments is characteristic of each enantiomer and both differ from the racemic mixture; and (2) molecular dynamics simulations (elastic collisions of oriented hydrogen peroxide, one of the most simple chiral molecules, with Ne atom) demonstrating that the scattering and the recoil angles are specific of the enantiomeric form. The efficacy of non-chiral light (in the case of photodissociation) and of non-chiral projectile (in the case of collisions) is due to the molecular orientation, as an essential requirement to observe chiral effects. The results of the simulations, that we report in this article, provide the background for the perspective realization of experiments which go beyond the well-documented ones involving interaction of circularly polarized laser (chiral light) with the matter, specifically by making use of non-chiral, i.e. linearly polarized or unpolarized light sources, and also by obtaining chiral effects with no use at all of light, but simply inducing them by molecular collisions. The case of vortices is discussed in a companion paper.
A new reaction scheme is proposed to account for roaming and chaotic behaviors in collisional and photo-initiated molecular-beam reactions, where nonadiabatic dynamics plays a key role and the ...collapse of superposition of wave functions is considered to be important in the beginning of the present scheme. Since the feature of molecular orbitals of reagents is crucial in reaction, we showed how to map out the spatial distribution of the relevant HOMO molecular orbitals of CH
3
Cl in the impact of fast electrons. We identified by experiment that the multiple overlap of nearby molecular orbitals affects even the vibrational motion of adjacent molecule DCl of the transient ClDCl chemical species. We also showed dynamical steric effects in the HBr + OH four-atom reaction as a manifestation of the nonadiabatic dynamics in complex systems. The roaming mechanism in the photo-initiated reaction of methyl formate is clarified in detail by experiment as well as the QCT trajectory calculation, where the conical intersection region plays an essential role. We suggest that two types of roaming trajectories coexist, i.e., deterministic and chaotic roaming trajectories based on classical trajectory calculations. To clarify the nonadiabatic dynamics in the roaming mechanism for non-collinear three-dimensional (3D) collisions, a new model of the 3D Polanyi rule is proposed as the extension of the well-established 2D Polanyi rule. In the 3D Polanyi rule, it is expected that the curvature and torsion of Frenet–Serret formulas in three-dimensional space would provide us key concepts in understanding reaction dynamics.
Competitive bond dissociation mechanisms for bromoacetyl chloride and 2‐ and 3‐bromopropionyl chloride following the 1n(O)→π*(CO) transition at 234–235 nm are investigated. Branching ratios for ...CBr/CCl bond fission are found by using the (2+1) resonance‐enhanced multiphoton ionization (REMPI) technique coupled with velocity ion imaging. The fragment branching ratios depend mainly on the dissociation pathways and the distances between the orbitals of Br and the CO chromophore. CCl bond fission is anticipated to follow an adiabatic potential surface for a strong diabatic coupling between the n(O)π*(CO) and np(Cl)σ*(CCl) bands. In contrast, CBr bond fission is subject to much weaker coupling between n(O)π*(CO) and np(Br)σ*(CBr). Thus, a diabatic pathway is preferred for bromoacetyl chloride and 2‐bromopropionyl chloride, which leads to excited‐state products. For 3‐bromopropionyl chloride, the available energy is not high enough to reach the excited‐state products such that CBr bond fission must proceed through an adiabatic pathway with severe suppression by nonadiabatic coupling. The fragment translational energies and anisotropy parameters for the three molecules are also analyzed and appropriately interpreted.
Busted open: Insight into the mechanisms causing CCl and CBr bond fission of bromoacetyl chloride and 2‐ and 3‐bromopropionyl chloride by following the 1n(O)→π*(CO) transition is obtained. The figure shows the center‐of‐mass translational energy distributions of ground‐state Br formation through a diabatic pathway for the dissociation of 2‐bromopropionyl chloride.
Adsorption and reaction of hydrogen (deuterium) on thin gold films grown on Ir{1
1
1} surface at ∼100 K have been studied with temperature-programmed desorption using a quadrupole mass spectrometer. ...Thin Au{1
1
1} films are epitaxially grown on the Ir{1
1
1}. Surprisingly, H
2 (D
2) can dissociatively adsorb on these Au{1
1
1} films, although it is well known that Au surfaces are noble enough not to dissociate hydrogen molecules Nature 376 (1995) 238. Moreover, we found that H (D) atoms can be confined into a Au thin film and/or the interface between an Ir surface and the thin Au film. We demonstrate how reactive thin Au films are.
A 63-year-old man was diagnosed with hypertrophic obstructive cardiomyopathy. Echocardiography revealed asymmetrical left ventricular hypertrophy, systolic anterior movement (SAM) of mitral leaflets ...causing an outflow tract pressure gradient of 52mmHg, and moderate mitral regurgitation (MR) directed posteriorly in the left atrium. Four years later, when the patient was admitted for mild congestive heart failure, SAM and left ventricular outflow obstruction were absent, and prolapse of the posterior mitral leaflet was causing anteriorly-directed severe MR. Rupture of the chordae tendineae was responsible for the mitral prolapse and for the abolition of the outflow obstruction.
The transition metal–benzene (1:1) complexes are synthesized by laser evaporation method followed by the size and structure selection with 2-m long electrostatic hexapole field. Electric dipole ...moments of half-sandwich type binary complexes for a series of the transition metals, i.e. Ti, V, Co, and Ni, with benzene molecule were determined by measuring the focusing curves, namely the dependence of the focused beam intensity upon the hexapole field strength. It is found that the dipole moments of Ti–C
6H
6 and V–C
6H
6 are larger than the ones of Co–C
6H
6 and Ni–C
6H
6. Such large dipole moments of Ti–C
6H
6 and V–C
6H
6 can be ascribed to the strong orbital interaction due to charge transfer between the metal atom and benzene molecule.
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