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91.
Direct arylation of the exocyclic amino groups of nucleosides represents a simple approach to N-aryl nucleoside derivatives. To date, one limitation has been that only electron-deficient aryl bromides and triflates possessed adequate reactivity for efficient, direct N-arylation of nucleosides. We demonstrate herein that Pd-Xantphos catalytic systems lead to successful N-arylation of suitably protected 2'-deoxyadenosine and 2'-deoxyguanosine with a wide range of aryl bromides. 相似文献
92.
93.
Kissell KR Hartman KB Van der Heide PA Wilson LJ 《The journal of physical chemistry. B》2006,110(35):17425-17429
X-ray photoelectron spectroscopy (XPS) along with inductively coupled plasma analysis (ICP-AE) and Raman spectroscopy have been used to define the location and to quantify the amount of iodine in HiPco SWNT samples loaded with molecular I(2) via sublimation (I(2)-SWNTs). The exterior-adsorbed I(2) can be removed (as I(-)) by reducing the sample of filled nanotubes with Na(0)/THF or by heating the I(2)-SWNTs to 300 degrees C (without reduction), leaving I(2) contained only within the interior of the SWNTs (I(2)@SWNTs) as proven by XPS. These I(2)@SWNTs contain approximately 25 wt % of I(2) and are stable without the loss of I(2) even after exposure to additional reduction with Na(0)/THF or upon heating to ca. 500 degrees C. 相似文献
94.
Futaba Fujie-Okamoto Ryan Jones Kyle Kolasinski Ping Zhang 《Graphs and Combinatorics》2013,29(4):901-912
Let G be a connected graph of order \({n\ge 3}\) and size m and \({f:E(G)\to \mathbb{Z}_n}\) an edge labeling of G. Define a vertex labeling \({f': V(G)\to \mathbb{Z}_n}\) by \({f'(v)= \sum_{u\in N(v)}f(uv)}\) where the sum is computed in \({\mathbb{Z}_n}\) . If f′ is one-to-one, then f is called a modular edge-graceful labeling and G is a modular edge-graceful graph. A graph G is modular edge-graceful if G contains a modular edge-graceful spanning tree. Several classes of modular edge-graceful trees are determined. For a tree T of order n where \({n\not\equiv 2 \pmod 4}\) , it is shown that if T contains at most two even vertices or the set of even vertices of T induces a path, then T is modular edge-graceful. It is also shown that every tree of order n where \({n\not\equiv 2\pmod 4}\) having diameter at most 5 is modular edge-graceful. 相似文献
95.
Jeffrey W. Labahn Timothy A. Sipkens Kyle J. Daun 《Combustion Theory and Modelling》2013,17(3):474-499
Conditional Source-term Estimation (CSE) obtains the conditional species mass fractions by inverting a Fredholm integral equation of the first kind. In the present work, a Bayesian framework is used to compare two different regularisation methods: zeroth-order temporal Tikhonov regulatisation and first-order spatial Tikhonov regularisation. The objectives of the current study are: (i) to elucidate the ill-posedness of the inverse problem; (ii) to understand the origin of the perturbations in the data and quantify their magnitude; (iii) to quantify the uncertainty in the solution using different priors; and (iv) to determine the regularisation method best suited to this problem. A singular value decomposition shows that the current inverse problem is ill-posed. Perturbations to the data may be caused by the use of a discrete mixture fraction grid for calculating the mixture fraction PDF. The magnitude of the perturbations is estimated using a box filter and the uncertainty in the solution is determined based on the width of the credible intervals. The width of the credible intervals is significantly reduced with the inclusion of a smoothing prior and the recovered solution is in better agreement with the exact solution. The credible intervals for temporal and spatial smoothing are shown to be similar. Credible intervals for temporal smoothing depend on the solution from the previous time step and a smooth solution is not guaranteed. For spatial smoothing, the credible intervals are not dependent upon a previous solution and better predict characteristics for higher mixture fraction values. These characteristics make spatial smoothing a promising alternative method for recovering a solution from the CSE inversion process. 相似文献
96.
Caleb A. Haynes Serafin Lopez Kyle A. Beran 《International journal of quantum chemistry》2019,119(19):e25992
Density-functional theory was applied to the investigation of the structural and electronic properties of C24 fullerene derivatives. Transition metals (TMs) from groups 11 and 12, in various oxidation and spin-states, are inserted at either endohedral (TM@C24) or exohedral (TM-C24) sites and their subsequent energetic stabilities are assessed. With the exception of Ag@C24, all derivatives are predicted to occupy a minimum on the potential energy surface. The optimized exohedral TM-C24 geometries yield TM-C bond lengths that are consistent with comparable carbon-metal bond lengths, and the overwhelming majority of the derivatives result in a slight deformation of the C24 cage as the bonding carbon takes on more sp3 character. All of the TM@C24 equilibrium structures maintain the integrity of the cage structure with a moderate increase in the diameter. All neutral exohedral and endohedral complexes favor the low spin-state; conversely, all of the charged exohedral complexes prefer the high spin-state, with the exception of Cu-C241+ molecular ion. The Group 12 charged endohedral derivatives prefer the low spin-state, whereas the Group 11 molecular ions do not necessarily exhibit a definitive trend. Analysis of the energetic data predicts that of the lowest energy endohedral molecular species only four are predicted to be energetically favorable in terms of insertion energy and an advantageous HOMO-LUMO gap: Cu@C242+, Ag@C241+, Au@C243+, and Zn@C242+. 相似文献
97.
Kyle A. Mandla Curtis E. Moore Arnold L. Rheingold Joshua S. Figueroa 《Angewandte Chemie (International ed. in English)》2019,58(6):1779-1783
Elemental white phosphorus (P4) is well recognized as a critical precursor to organophosphorus compounds. However, regulatory constraints stemming from the toxic and pyrophoric nature of white phosphorus have significantly limited its accessibility. Herein is described a new approach to white phosphorus storage and release based on a unique example of photolytic reductive elimination of the tetrahedral P4 molecule from a mononuclear cyclo‐P4 molybdenum complex. The latter functions as an air‐stable, chemically‐deactivated source of white phosphorus. The system features efficient photo‐release of white phosphorus using inexpensive violet LED sources. Additionally, high‐yield recapture of unspent white phosphorus by the molybdenum center can be achieved by post‐photolysis heating at convenient temperatures. 相似文献
98.
The influence of water column variability on low-frequency, shallow water geoacoustic inversion results is considered. The data are estimates of modal eigenvalues obtained from measurements of a point source acoustic field using a horizontal aperture array in the water column. The inversion algorithm is based on perturbations to a background waveguide model with seabed properties consistent with the measured eigenvalues. Water column properties in the background model are assumed to be known, as would be obtained from conductivity, temperature, and depth measurements. The scope of this work in addressing the impact of water column variability on inversion is twofold. Range-dependent propagation effects as they pertain to eigenvalue estimation are first considered. It is shown that mode coupling is important even for weak internal waves and can enhance modal eigenvalue estimates. Second, the effect of the choice of background sound speed profile in the water column is considered for its impact on the estimated bottom acoustic properties. It is shown that a range-averaged sound velocity profile yields the best geoacoustic parameter estimates. 相似文献
99.
100.
Dr. Peng Wang Dr. Chang-xin Huo Shuyao Lang Dr. Kyle Caution Dr. Setare Tahmasebi Nick Prof. Purnima Dubey Prof. Rajendar Deora Prof. Xuefei Huang 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(16):6513-6520
With the infection rate of Bordetella pertussis at a 60-year high, there is an urgent need for new anti-pertussis vaccines. The lipopolysaccharide (LPS) of B. pertussis is an attractive antigen for vaccine development. With the presence of multiple rare sugars and unusual glycosyl linkages, the B. pertussis LPS is a highly challenging synthetic target. In this work, aided by molecular dynamics simulation and modeling, a pertussis-LPS-like pentasaccharide was chemically synthesized for the first time. The pentasaccharide was conjugated with a powerful carrier, bacteriophage Qβ, as a vaccine candidate. Immunization of mice with the conjugate induced robust anti-glycan IgG responses with IgG titers reaching several million enzyme-linked immunosorbent assay (ELISA) units. The antibodies generated were long lasting and boostable and could recognize multiple clinical strains of B. pertussis, highlighting the potential of Qβ-glycan as a new anti-pertussis vaccine. 相似文献