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David M. Koshy Dr. Shucheng Chen Dr. Dong Un Lee Dr. Michaela Burke Stevens Ahmed M. Abdellah Samuel M. Dull Gan Chen Dr. Dennis Nordlund Dr. Alessandro Gallo Dr. Christopher Hahn Dr. Drew C. Higgins Dr. Zhenan Bao Dr. Thomas F. Jaramillo 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(10):4072-4079
Ni,N-doped carbon catalysts have shown promising catalytic performance for CO2 electroreduction (CO2R) to CO; this activity has often been attributed to the presence of nitrogen-coordinated, single Ni atom active sites. However, experimentally confirming Ni−N bonding and correlating CO2 reduction (CO2R) activity to these species has remained a fundamental challenge. We synthesized polyacrylonitrile-derived Ni,N-doped carbon electrocatalysts (Ni-PACN) with a range of pyrolysis temperatures and Ni loadings and correlated their electrochemical activity with extensive physiochemical characterization to rigorously address the origin of activity in these materials. We found that the CO2R to CO partial current density increased with increased Ni content before plateauing at 2 wt % which suggests a dispersed Ni active site. These dispersed active sites were investigated by hard and soft X-ray spectroscopy, which revealed that pyrrolic nitrogen ligands selectively bind Ni atoms in a distorted square-planar geometry that strongly resembles the active sites of molecular metal–porphyrin catalysts. 相似文献
3.
Kirralee J. Burke Dr. Liam J. Stephens Dr. Melissa V. Werrett Prof. Philip C. Andrews 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(34):7657-7671
A series of homoleptic and heteroleptic bismuth(III) flavonolate complexes derived from six flavonols of varying substitution have been synthesised and structurally characterised. The complexes were evaluated for antibacterial activity towards several problematic Gram-positive (Staphylococcus aureus, methicillin-resistant Staphylococcus aureus (MRSA), and vancomycin-resistant Enterococcus (VRE)) and Gram-negative (Escherichia coli, Pseudomonas aeruginosa) bacteria. The cell viability of COS-7 (monkey kidney) cells treated with the bismuth flavonolates was also studied to determine the effect of the complexes on mammalian cells. The heteroleptic complexes [BiPh(L)2] (in which L=flavonolate) showed good antibacterial activity towards all of the bacteria but reduced COS-7 cell viability in a concentration-dependent manner. The homoleptic complexes [Bi(L)3] exhibited activity towards the Gram-positive bacteria and showed low toxicity towards the mammalian cell line. Bismuth uptake studies in VRE and COS-7 cells treated with the bismuth flavonolate complexes indicated that Bi accumulation is influenced by both the substitution of the flavonolate ligands and the degree of substitution at the bismuth centre. 相似文献
4.
Antonio J. LaPorte Jack E. Feldner Jan C. Spies Tom J. Maher Prof. Martin D. Burke 《Angewandte Chemie (International ed. in English)》2023,62(40):e202309566
Multifunctional organoboron compounds increasingly enable the simple generation of complex, Csp3-rich small molecules. The ability of boron-containing functional groups to modify the reactivity of α-radicals has also enabled a myriad of chemical reactions. Boronic esters with vacant p-orbitals have a significant stabilizing effect on α-radicals due to delocalization of spin density into the empty orbital. The effect of coordinatively saturated derivatives, such as N-methyliminodiacetic acid (MIDA) boronates and counterparts, remains less clear. Herein, we demonstrate that coordinatively saturated MIDA and TIDA boronates stabilize secondary alkyl α-radicals via σB-N hyperconjugation in a manner that allows site-selective C−H bromination. DFT calculated radical stabilization energies and spin density maps as well as LED NMR kinetic analysis of photochemical bromination rates of different boronic esters further these findings. This work clarifies that the α-radical stabilizing effect of boronic esters does not only proceed via delocalization of radical character into vacant boron p-orbitals, but that hyperconjugation of tetrahedral boron-containing functional groups and their ligand electron delocalizing ability also play a critical role. These findings establish boron ligands as a useful dial for tuning reactivity at the α-carbon. 相似文献
5.
Selective Activation of C=C Bond in Sustainable Phenolic Compounds from Lignin via Photooxidation: Experiment and Density Functional Theory Calculations 下载免费PDF全文
Morgan Zielinski Luke A. Burke Alexander Samokhvalov 《Photochemistry and photobiology》2015,91(6):1332-1339
Lignocellulosic biomass can be converted to high‐value phenolic compounds, such as food additives, antioxidants, fragrances and fine chemicals. We investigated photochemical and heterogeneous photocatalytic oxidation of two isomeric phenolic compounds from lignin, isoeugenol and eugenol, in several nonprotic solvents, for the first time by experiment and the density functional theory (DFT) calculations. Photooxidation was conducted under ambient conditions using air, near‐UV light and commercial P25 TiO2 photocatalyst, and the products were determined by TLC, UV–Vis absorption spectroscopy, HPLC‐UV and HPLC‐MS. Photochemical and photocatalytic oxidation of isoeugenol proceeds via the mild oxidative “dimerization” to produce the lignan dehydrodiisoeugenol (DHDIE), while photooxidation of eugenol does not proceed. The DFT calculations suggest a radical stepwise mechanism for the oxidative “dimerization” of isoeugenol to DHDIE as was calculated for the first time. 相似文献
6.
Ultrafine grain formation and coating mechanism arising from a blast coating process: A transmission electron microscopy analysis 下载免费PDF全文
Conor F. Dunne Kevin Roche Arne Janssen Xiangli Zhong M.G. Burke Barry Twomey Kenneth T. Stanton 《Surface and interface analysis : SIA》2017,49(12):1271-1278
This article examines the substrate/coating interface of a coating deposited onto mild steel and stainless steel substrates using an ambient temperature blast coating technique known as CoBlast. The process uses a coincident stream of an abrasive blast medium and coating medium particles to modify the substrate surface. The hypothesis for the high bond strength is that the abrasive medium roughens the surface while simultaneously disrupting the passivating oxide layer of the substrate, thereby exposing the reactive metal that then reacts with the coating medium. The aim of this study is to provide greater insight into the coating/substrate bonding mechanism by analysing the interface between a hydroxyapatite coating on both mild and stainless steel substrates. The coating adhesion was measured via a tensile test, and bond strengths of approximately 45 MPa were measured. The substrate/coating interface was examined using transmission electron microscopy and selected area diffraction. The analysis of the substrate/coating interface revealed the presence of ultrafine grains in both the coating and substrate at interface associated with deformation at the interface caused by particle impaction during deposition. The chemical reactivity resulting from the creation of these ultrafine grains is proposed to explain the high adhesive strength of CoBlast coatings. 相似文献
7.
This paper concerns smoothing by infimal convolution for two large classes of functions: convex, proper and lower semicontinous as well as for (the nonconvex class of) convex-composite functions. The smooth approximations are constructed so that they epi-converge (to the underlying nonsmooth function) and fulfill a desirable property with respect to graph convergence of the gradient mappings to the subdifferential of the original function under reasonable assumptions. The close connection between epi-convergence of the smoothing functions and coercivity properties of the smoothing kernel is established. 相似文献
8.
Although ischemic heart disease tends to cluster in families, previous studies have reported a modest (2-fold increased risk) to strong (10-fold increased risk) contribution of family history to the explanation of disease occurrence. The authors assessed the familial aggregation of early-onset myocardial infarction in 11,307 adults aged <65 years who participated in the Third National Health and Nutrition Examination Survey. Logistic regression was used to obtain odds ratios (ORs) and 95% confidence intervals (CIs). A parental history was more common in those with (n = 237) than in those without (n = 11,070) a myocardial infarction (19.8 vs. 7.9%, p < or = 0.01). Adults with a parental history were also more likely to have multiple risk factors for cardiovascular disease (OR for four or five risk factors compared with none: 2.9, 95% CI: 1.4, 6.3). After multivariate adjustment, the likelihood of myocardial infarction was more than three times greater among adults with a parental history than among those without (95% CI: 1.7, 6.7). A maternal history of myocardial infarction was strongly associated (OR = 6.1, 95% CI: 2.1, 17.4) with an increased likelihood of myocardial infarction, and a paternal history was associated with a 3-fold (95% CI: 1.5, 6.3) increased likelihood of myocardial infarction after adjustment for cardiovascular disease risk factors. These results suggest a familial aggregation of early-onset myocardial infarction and show that family history is strongly associated with cardiovascular disease risk factors. 相似文献
9.
Burke W Acheson L Botkin J Bridges K Davis A Evans J Frias J Hanson J Kahn N Kahn R Lanier D Pinsky LE Press N Lloyd-Puryear MA Rich E Stevens N Thomson E Wartman S Wilson M 《Community genetics》2002,5(2):138-146
The Genetics in Primary Care (GPC) project is a USA national faculty development initiative with the goal of enhancing the training of medical students and primary care residents by developing primary care faculty expertise in genetics. Educational strategies were developed for the project by an executive committee with input from an advisory committee, comprising individuals with primary care, medical education and genetics expertise. These committees identified the key issues in genetics education for primary care as (1) considering inherited disease in the differential diagnosis of common disorders; (2) using appropriate counseling strategies for genetic testing and diagnosis, and (3) understanding the implications of a genetic diagnosis for family members. The group emphasized the importance of a primary care perspective, which suggests that the clinical utility of genetic information is greatest when it has the potential to improve health outcomes. The group also noted that clinical practice already incorporates the use of family history information, providing a basis for discussing the application of genetic concepts in primary care. Genetics and primary care experts agreed that educational efforts will be most successful if they are integrated into existing primary care teaching programs, and use a case-based teaching format that incorporates both clinical and social dimensions of genetic disorders. Three core clinical skills were identified: (1) interpreting family history; (2) recognizing the variable clinical utility of genetic information, and (3) acquiring cultural competency. Three areas of potential controversy were identified as well: (1) the role of nondirective counseling versus shared decision-making in discussions of genetic testing; (2) the intrinsic value of genetic information when it does not influence health outcomes, and (3) indications for a genetics referral. The project provides an opportunity for ongoing discussion about these important issues. 相似文献
10.
The purpose of this short essay is to introduce students and other newcomers to the basic ideas and uses of modern electronic density functional theory, including what kinds of approximations are in current use, and how well they work (or not). The complete newcomer should find it orients them well, while even longtime users and aficionados might find something new outside their area. Important questions varying in difficulty and effort are posed in the text, and are answered in the Supporting Information. © 2012 Wiley Periodicals, Inc. 相似文献