We report a systematic study of the stoichiometric reactions of isolated arylpalladium hydroxo and halide complexes with arylboronic acids and aryltrihydroxyborates to evaluate the relative rates of the two reaction pathways commonly proposed to account for transmetalation in the Suzuki-Miyaura reaction. On the basis of the relative populations of the palladium and organoboron species generated under conditions common for the catalytic process and the observed rate constants for the stoichiometric reactions between the two classes of reaction components, we conclude that the reaction of a palladium hydroxo complex with boronic acid, not the reaction of a palladium halide complex with trihydroxyborate, accounts for transmetalation in catalytic Suzuki-Miyaura reactions conducted with weak base and aqueous solvent mixtures.
Summer Lecture Series 2007: Chris Somerville, Director of the Energy Biosciences Institute and an award-winning plant biochemist with Berkeley Lab's Physical Biosciences Division, is a leading authority on the structure and function of plant cell walls. He discusses an overview of some of the technical challenges associated with the production of cellulosic biofuels, which will require an improved understanding of a diverse range of topics in fields such as agronomy, chemical engineering, microbiology, structural biology, genomics, environmental sciences, and socioeconomics.
No abstract is provided for this article.
Chemical compounds can be dissociated by contacting the same with a p/n type semi-conductor photochemical diode having visible light as its sole source of energy. The photochemical diode consists of low cost, readily available materials, specifically polycrystalline iron oxide doped with silicon in the case of the n-type semi-conductor electrode, and polycrystalline iron oxide doped with magnesium in the case of the p-type electrode. So long as the light source has an energy greater than 2.2 electron volts, no added energy source is needed to achieve dissociation.
Vertical integration of healthcare services has been viewed by hospitals as an effective strategy for maintaining institutional viability in the face of increased competitive pressures. This paper examines the effects of vertical integration on hospital utilization and market share, based on the experience of a selected set of hospitals that developed primary care group practices as part of a national demonstration program conducted over the period 1976 to 1982. Inpatient days and admissions for the average hospital increased 9.0 percent and 8.2 percent, respectively, over the initial four-year period of group operation, while average market share of inpatient days and admissions rose by 4.9 percent and 3.6 percent, respectively. The establishment of the group practices also helped most hospitals achieve a more favorable outpatient payor mix.
Visual illusion is the fallacious perception of reality or some actually existing object. In this paper, we imitate the mechanism of Ehrenstein illusion, neon color spreading illusion, watercolor illusion, Kanizsa illusion, shifted edges illusion, and hybrid image illusion using the Open Source Computer Vision Library (OpenCV). We also imitate these illusions using Cellular Neural Networks (CNNs). These imitations suggest that some illusions are processed by high-level brain functions. We next apply the morphological gradient operation to anomalous motion illusions. The processed images are classified into two kinds of images, which correspond to the central drift illusion and the peripheral drift illusion, respectively. It demonstrates that the contrast of the colors plays an important role in the anomalous motion illusion. We also imitate the anomalous motion illusions using both OpenCV and CNN. These imitations suggest that some visual illusions may be processed by the illusory movement of animations.
This paper demonstrates a new visual motion estimation technique that is able to recover high degree-of-freedom articulated human body configurations in complex video sequences. We introduce the use of a novel mathematical technique, the product of exponential maps and twist motions, and its integration into a differential motion estimation. This results in solving simple linear systems, and enables us to recover robustly the kinematic degrees-offreedom in noise and complex self occluded configurations. We demonstrate this on several image sequences of people doing articulated full body movements, and visualize the results in re-animating an artificial 3D human model. We are also able to recover and re-animate the famous movements of Eadweard Muybridge’s motion studies from the last century. To the best of our knowledge, this is the first computer vision based system that is able to process such challenging footage and recover complex motions with such high accuracy. 1
A diabetes text-messaging program provided instrumental and emotional support for participants and may have contributed to clinically meaningful improvements in HbA<sub>1c</sub>. Patients who were more engaged demonstrated greater improvement. Program improvements, such as linkages to clinical care, hold potential for improving patient engagement and ultimately, improving clinical outcomes.
When subjected to alternating stresses, most materials degrade, e.g., suffer premature failure, due to a phenomenon known as fatigue. It is generally accepted that in brittle materials, such as ceramics, fatigue can only take place in toughened solids, i.e., premature fatigue failure would not be expected in materials such as single crystal silicon. The results of this study, however, appear to be at odds with the current understanding of brittle material fatigue. Twelve thin-film (/spl sim/20 /spl mu/m thick) single crystal silicon specimens were tested to failure in a controlled air environment (30/spl plusmn/0.1/spl deg/C, 50/spl plusmn/2% relative humidity). Damage accumulation and failure of the notched cantilever beams were monitored electrically during the "fatigue life" test. Specimen lives ranged from about 10 s to 48 days, or 1/spl times/106 to 1/spl times/1011 cycles before failure over stress amplitudes ranging from approximately 4 to 10 GPa. A variety of mechanisms are discussed in light of the fatigue life data and fracture surface evaluation.
A ruthenium-catalyzed intermolecular, anti-Markovnikov hydroamination of vinylarenes with secondary aliphatic and benzylic amines is reported. The combination of Ru(cod)(2-methylallyl)2, 1,5-bis(diphenylphosphino)pentane, and triflic acid was the most effective catalyst of those tested. Control reactions conducted without ligand or acid did not form the amine. The reaction of morpholine, piperidine, 4-phenylpiperazine, 4-BOC-piperazine, 4-piperidone ethylene ketal, and tetrahydroisoquinoline with styrene in the presence of 5 mol % of this catalyst formed the corresponding beta-phenethylamine products in 64-96% yield, with 99% regioselectivity, and without enamine side products. Acyclic amines such as n-hexylmethylamine and N-benzylmethylamine reacted with styrene in 63 and 50% yields, respectively. Alkyl-, methoxy-, and trifluoromethyl-substituted styrenes reacted with morpholine in the presence of this catalyst or a related one containing 1,1'-bis(diisopropylphosphino)ferrocene as ligand to give the products in 51-91%. Further, the hydroamination of alpha-methyl styrene was observed for the first time with a homogeneous transition metal catalyst. Preliminary mechanistic studies showed that the reaction occurred by direct, irreversible, anti-Markovnikov hydroamination and that the mechanism of the ruthenium-catalyzed hydroamination is likely to be distinct from that of the recently reported rhodium-catalyzed reaction.
