Understanding Work Group Culture on Rehabilitation Units: The Key to Facilitating Group Innovation and Promoting Integration

Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/93523/1/j.2048-7940.1996.tb01666.x.pd

Transition state energy decomposition study of acetate-assisted and internal electrophilic substitution C−H bond activation by (acac-O,O)_2Ir(X) complexes (X = CH_3COO, OH)

Chelate-assisted and internal electrophilic substitution type transition states were studied using a DFT-based energy decomposition method. Interaction energies for benzene and methane C−H bond activation by (acac-O,O)_2Ir(X) complexes (X = CH_3COO and OH) were evaluated using the absolutely localized molecular orbital energy decomposition analysis (ALMO-EDA). A ratio of ~1.5:1 for forward to reverse charge-transfer between (acac-O,O)_2Ir(X) and benzene or methane transition state fragments confirms “ambiphilic” bonding, the result of an interplay between the electrophilic iridium center and the internal base component. This analysis also revealed that polarization effects account for a significant amount of transition state stabilization. The energy penalty to deform reactants into their transition state geometry, distortion energy, was also used to understand the large activation energy difference between six-membered and four-membered acetate-assisted transition states and help explain why these complexes do not activate the methane C−H bond

Orientation Studies in the Dibenzofuran Series

2-Hydroxydibenzofuran on bromination gives 1-bromo-2-hydroxydibenzofuran (m.p., 123.5°) and 2-hydroxy-3-bromo-dibenzofuran (m. p., 143-144°). The corresponding products but in a different ratio are obtained by the bromination of 2-methoxydibenzofuran. The allyl ether of 2-hydroxydibenzofuran rearranges to 1-allyl-2-hydroxydihenzofuran (m.p., 82.5°-83°), the methyl ether of which melts at 68°. Also, 2-hydrozydibenzofuran and benzenediazonium chloride couple to give l-phenylazo-2-hyclroxydibenzofuran. The 3-hydroxydibenzofuran couples to give 2-phenylazo-3- hydroxydibenzofuran (m. p., 166°), the structure of which was established by conversion to 2-bromo-3-hydroxydibenzofuran (m.p., 166°), the structure of which was established by conversion to 2-bromo-3-hydroxydibenzofuran (m.p., 115°-116°)

Benzene C−H Bond Activation in Carboxylic Acids Catalyzed by O-Donor Iridium(III) Complexes: An Experimental and Density Functional Study

The mechanism of benzene C−H bond activation by [Ir(μ-acac-O,O,C^3)(acac-O,O)(OAc)]_2 (4) and [Ir(μ-acac-O,O,C^3)(acac-O,O)(TFA)]_2 (5) complexes (acac = acetylacetonato, OAc = acetate, and TFA = trifluoroacetate) was studied experimentally and theoretically. Hydrogen−deuterium (H/D) exchange between benzene and CD_(3)COOD solvent catalyzed by 4 (ΔH^‡ = 28.3 ± 1.1 kcal/mol, ΔS^‡ = 3.9 ± 3.0 cal K^(−1) mol^(−1)) results in a monotonic increase of all benzene isotopologues, suggesting that once benzene coordinates to the iridium center, there are multiple H/D exchange events prior to benzene dissociation. B3LYP density functional theory (DFT) calculations reveal that this benzene isotopologue pattern is due to a rate-determining step that involves acetate ligand dissociation and benzene coordination, which is then followed by heterolytic C−H bond cleavage to generate an iridium-phenyl intermediate. A synthesized iridium-phenyl intermediate was also shown to be competent for H/D exchange, giving similar rates to the proposed catalytic systems. This mechanism nicely explains why hydroarylation between benzene and alkenes is suppressed in the presence of acetic acid when catalyzed by [Ir(μ-acac-O,O,C^3)(acac-O,O)(acac-C^3)]_2 (3) (Matsumoto et al. J. Am. Chem. Soc. 2000, 122, 7414). Benzene H/D exchange in CF_(3)COOD solvent catalyzed by 5 (ΔH^‡ = 15.3 ± 3.5 kcal/mol, ΔS^‡ = −30.0 ± 5.1 cal K^(−1) mol^(−1)) results in significantly elevated H/D exchange rates and the formation of only a single benzene isotopologue, (C_(6)H_(5)D). DFT calculations show that this is due to a change in the rate-determining step. Now equilibrium between coordinated and uncoordinated benzene precedes a single rate-determining heterolytic C−H bond cleavage step

Homography-based ground plane detection using a single on-board camera

This study presents a robust method for ground plane detection in vision-based systems with a non-stationary camera. The proposed method is based on the reliable estimation of the homography between ground planes in successive images. This homography is computed using a feature matching approach, which in contrast to classical approaches to on-board motion estimation does not require explicit ego-motion calculation. As opposed to it, a novel homography calculation method based on a linear estimation framework is presented. This framework provides predictions of the ground plane transformation matrix that are dynamically updated with new measurements. The method is specially suited for challenging environments, in particular traffic scenarios, in which the information is scarce and the homography computed from the images is usually inaccurate or erroneous. The proposed estimation framework is able to remove erroneous measurements and to correct those that are inaccurate, hence producing a reliable homography estimate at each instant. It is based on the evaluation of the difference between the predicted and the observed transformations, measured according to the spectral norm of the associated matrix of differences. Moreover, an example is provided on how to use the information extracted from ground plane estimation to achieve object detection and tracking. The method has been successfully demonstrated for the detection of moving vehicles in traffic environments

Recurrent myocardial infarction in a young cocaine abuser

Cocaine increases the risk of cardiovascular diseases, including myocardial infarction. We herein describe a case of a 22-year-old man with a long history of cocaine abuse. He presented at our institution because of acute coronary syndrome with ST segment elevation. Emergency coronary angiography revealed ostial occlusion of the left anterior descending artery, which required desobstruction and implantation of a bare metal stent. Angioplasty was complicated 4 months later by in-stent restenosis requiring reintervention. This case highlights myocardial infarction as a cocaineinduced effect. Appropriate treatment and cessation of cocaine abuse may prevent cardiovascular complications and recurrences

Public perception and knowledge on nanotechnology: A study based on a citizen science approach

Even with the widespread use of nanomaterials (NMs) in everyday life, consumer knowledge about the functionality, benefits, and possible dangers of nanotechnology (NT) is still modest. As with any developing technology, its public perception has direct implications on future policies and has to be taken into account by academia and industry alike. As part of the “Nan-O-Style” interdisciplinary research project, an online survey was conducted using a Citizen Science-guided approach. The main goal was to evaluate the current levels of knowledge and the attitude towards NT among the general Austrian public and to determine how differing sociodemographic factors may affect these. Over the course of 17 months, a total of 1067 responses were collected and quantitatively analysed. We found that while Austrians display a generally optimistic view and a positive attitude towards NT, there are still remaining concerns about its safety and possible risks. Participants expressed great desire for more information about NT and its applications, as well as for clear labelling and transparency of products containing NMs. Notably, we found that age did not affect the general attitude towards NT nor the levels of NT awareness. While participants with a university degree were generally more knowledgeable on this specific topic, surprisingly, there were no significant differences in the attitude towards NT among people from different educational backgrounds. Similar to previous studies, we observed that male participants demonstrated a more positive attitude towards NT and scored slightly higher in our NT quiz compared to female participants. However, female participants voiced greater desire for more information and transparency regarding NMs. Interestingly, while participants with a negative attitude towards NT scored lowest on the NT quiz, they also expressed the least interest in receiving more NT-related information. This illustrates a difficulty in mitigating public aversion solely by providing more information

Oxy-functionalization of nucleophilic rhenium(I) metal carbon bonds catalyzed by selenium(IV)

We report that SeO_2 catalyzes the facile oxy-functionalization of (CO)_5Re(I)-Me^(δ−) with IO_4− to generate methanol. Mechanistic studies and DFT calculations reveal that catalysis involves methyl group transfer from Re to the electrophilic Se center followed by oxidation and subsequent reductive functionalization of the resulting CH_3Se(VI) species. Furthermore, (CO)_3Re(I)(Bpy)-R (R = ethyl, n-propyl, and aryl) complexes show analogous transfer to SeO_2 to generate the primary alcohols. This represents a new strategy for the oxy-functionalization of M−R^(δ−) polarized bonds