Z-Selectivity in Olefin Metathesis with Chelated Ru Catalysts: Computational Studies of Mechanism and Selectivity

The mechanism and origins of Z-selectivity in olefin metathesis with chelated Ru catalysts were explored using density functional theory. The olefin approaches from the “side” position of the chelated Ru catalysts, in contrast to reactions with previous unchelated Ru catalysts that favor the bottom-bound pathway. Steric repulsions between the substituents on the olefin and the N-substituent on the N-heterocyclic carbene ligand lead to highly selective formation of the Z product

Static spheres around spherically symmetric black hole spacetime

Unique features of particle orbits produce novel signatures of gravitational observable phenomena, and are quite useful in testing compact astrophysical objects in general relativity or modified theories of gravity. Here we observe a representative example that a static, spherically symmetric black hole solution with nonlinear electrodynamics admits static points at finite radial distance. Each static point thus produces a static sphere, on which a massive test particle can remain at rest at arbitrary latitudes with respect to an asymptotic static observer. As a result, the well-known static Dyson spheres can be implemented by such orbits. More interestingly, employing a topological argument, we disclose that stable and unstable static spheres (if they exist) always come in pairs in an asymptotically flat spacetime. In contrast to this, the counterpart naked singularity has one more stable static sphere than the unstable one. Our results have potential applications in testing black holes in standard Maxwell and nonlinear electrodynamics, as well as in uncovering the underlying astronomical observation effects in other gravitational theories beyond general relativity.Comment: 7 pages, 4 figures. Published versio

Functionalization of single-walled carbon nanotubes using isotropic plasma treatment: Resonant Raman spectroscopy study

Functionalization of single-walled carbon nanotubes sSWNTsd by isotropic plasma treatment was studied using resonant Raman spectroscopy. It was shown that plasma-induced functionalization results in the uniaxial isotropic constriction of the nanotubes but preserves their overall structural integrity. It was demonstrated that NH3 ·H2O and hexamethyldisiloxan plasmas yield various types of conductivity for semiconducting SWNTs

Functionalization of single-walled carbon nanotubes using isotropic plasma treatment: Resonant Raman spectroscopy study

Functionalization of single-walled carbon nanotubes sSWNTsd by isotropic plasma treatment was studied using resonant Raman spectroscopy. It was shown that plasma-induced functionalization results in the uniaxial isotropic constriction of the nanotubes but preserves their overall structural integrity. It was demonstrated that NH3 ·H2O and hexamethyldisiloxan plasmas yield various types of conductivity for semiconducting SWNTs

Dangling-bond charge qubit on a silicon surface

Two closely spaced dangling bonds positioned on a silicon surface and sharing an excess electron are revealed to be a strong candidate for a charge qubit. Based on our study of the coherent dynamics of this qubit, its extremely high tunneling rate ~ 10^14 1/s greatly exceeds the expected decoherence rates for a silicon-based system, thereby overcoming a critical obstacle of charge qubit quantum computing. We investigate possible configurations of dangling bond qubits for quantum computing devices. A first-order analysis of coherent dynamics of dangling bonds shows promise in this respect.Comment: 17 pages, 3 EPS figures, 1 tabl

In vitro characterization of sonothrombolysis and echocontrast agents to treat ischemic stroke

The development of adjuvant techniques to improve thrombolytic efficacy is important for advancing ischemic stroke therapy. We characterized octafluoropropane and recombinant tissue plasminogen activator (rt-PA)-loaded echogenic liposomes (OFP t-ELIP) using differential interference and fluorescence microscopy, attenuation spectroscopy, and electrozone sensing. The loading of rt-PA in OFP t-ELIP was assessed using spectrophotometry. Further, it was tested whether the agent shields rt-PA against degradation by plasminogen activator inhibitor-1 (PAI-1). An in vitro system was used to assess whether ultrasound (US) combined with either Definity or OFP t-ELIP enhances rt-PA thrombolysis. Human whole blood clots were mounted in a flow system and visualized using an inverted microscope. The perfusate consisted of either (1) plasma alone, (2) rt-PA, (3) OFP t-ELIP, (4) rt-PA and US, (5) OFP t-ELIP and US, (6) Definity and US, or (7) rt-PA, Definity, and US (n = 16 clots per group). An intermittent US insonation scheme was employed (220 kHz frequency, and 0.44 MPa peak-to-peak pressures) for 30 min. Microscopic imaging revealed that OFP t-ELIP included a variety of structures such as liposomes (with and without gas) and lipid-shelled microbubbles. OFP t-ELIP preserved up to 76% of rt-PA activity in the presence of PAI-1, whereas only 24% activity was preserved for unencapsulated rt-PA. The use of US with rt-PA and Definity enhanced lytic efficacy (p \u3c 0.05) relative to rt-PA alone. US combined with OFP t-ELIP enhanced lysis over OFP t-ELIP alone (p \u3c 0.01). These results demonstrate that ultrasound combined with Definity or OFP t-ELIP can enhance the lytic activity relative to rt-PA or OFP t-ELIP alone, respectively

Racial disparities in kidney transplant waitlist appearance in Chicago: Is it race or place?

BackgroundPrior work has demonstrated how neighborhood poverty and racial composition impact racial disparities in access to the deceased donor kidney transplant waitlist, both nationally and regionally. We examined the association between neighborhood characteristics and racial disparities in time to transplant waitlist in Chicago, a diverse city with continued neighborhood segregation.MethodsUsing data from the United States Renal Data System (USRDS) and the US Census, we investigated time from dialysis initiation to kidney transplant waitlisting for African American and white patients in Chicago using cause‐specific proportional hazards analyses, adjusting for individual sociodemographic and clinical characteristics, as well as neighborhood poverty and racial composition.ResultsIn Chicago, African Americans are significantly less likely than whites to appear on the renal transplant waitlist (HR 0.73, P < .05). Compared to whites in nonpoor neighborhoods, African Americans in poor neighborhoods are significantly less likely to appear on the transplant waitlist (HR 0.61, P < .05). Over 69% of African Americans with ESRD live in these neighborhoods.ConclusionsConsistent with national data, African Americans in Chicago have a lower likelihood of waitlisting than whites. This disparity is explained in part by neighborhood poverty, which impacts the majority of African American ESRD patients in Chicago.Peer Reviewedhttps://deepblue.lib.umich.edu/bitstream/2027.42/144246/1/ctr13195_am.pdfhttps://deepblue.lib.umich.edu/bitstream/2027.42/144246/2/ctr13195.pd

Z-Selective Ethenolysis with a Ruthenium Metathesis Catalyst: Experiment and Theory

The Z-selective ethenolysis activity of chelated ruthenium metathesis catalysts was investigated with experiment and theory. A five-membered chelated catalyst that was successfully employed in Z-selective cross metathesis reactions has now been found to be highly active for Z-selective ethenolysis at low ethylene pressures, while tolerating a wide variety of functional groups. This phenomenon also affects its activity in cross metathesis reactions and prohibits crossover reactions of internal olefins via trisubstituted ruthenacyclobutane intermediates. In contrast, a related catalyst containing a six-membered chelated architecture is not active for ethenolysis and seems to react through different pathways more reminiscent of previous generations of ruthenium catalysts. Computational investigations of the effects of substitution on relevant transition states and ruthenacyclobutane intermediates revealed that the differences of activities are attributed to the steric repulsions of the anionic ligand with the chelating groups