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91.
Wei Qin Rishabh Jain Francisco C. Robles Hernández Prof. Dr. Jeffrey D. Rimer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(23):5893-5898
Zeolite crystals can be used as seeds or aluminosilicate sources in syntheses to control polymorphs and/or reduce the quantity of organics used as structure-directing agents. A frequently invoked hypothesis for interzeolite transformations is that zeolites share some underlying similarity in structure, most notably in cases pertaining to organic-free syntheses. Herein, we show for the first time that ZSM-5 (MFI) can be directly obtained from USY (FAU) through an interzeolite transformation between parent–daughter structures lacking common building units in the absence of a structure-directing agent and seeds. We show that interzeolite transformation leads to a crystalline product with fewer defects. Our findings also reveal that ZSM-5 is a metastable intermediate that undergoes further transformation to mordenite (MOR) and quartz. The MFI-to-MOR transition is counter to reported trends for which transformations lead to structures with reduced molar volume. Herein, we propose mechanistic arguments that suggest the driving force for interzeolite transformation is more complex than guidelines posited in the literature. 相似文献
92.
ABSTRACT In this paper, we present a systematic roadmap for developing a robust and parallel multi-material reactive hydrodynamic solver that integrates historically stable algorithms with new and current modern methods to solve explosive system design problems. The Ghost Fluid Method and Riemann solvers were used to enforce appropriate interface boundary conditions. Improved performance in terms of computational work and convergence properties was achieved by modifying a local node sorting strategy that decouples ghost nodes, allowing us to set material boundary conditions via an explicit procedure, removing the need to solve a coupled system of equations numerically. The locality and explicit nature of the node sorting concept allows for greater levels of parallelism and lower computational cost when populating ghost nodes. Non-linear numerical issues endemic to the use of real Equations of State in hydro-codes were resolved by using more thermodynamically consistent forms allowing us to accurately resolve large density gradients associated with high energy detonation problems at material interfaces. Pre-computed volume tables were implemented adding to the robustness of the solver base. 相似文献
93.
We analyze the semilocal convergence of Steffensen's method, using a novel technique, which is based on recurrence relations, for solving systems of nonlinear equations. This technique allows analyzing the convergence of Steffensen's method to solutions of equations, where the function involved can be both differentiable and nondifferentiable. Moreover, this technique also allows enlarging the domain of starting points for Steffensen's method from certain predictions with the simplified Steffensen method. 相似文献
94.
Dr. Qaisar Nadeem Dr. Giuseppe Meola Dr. Henrik Braband Robin Bolliger Dr. Olivier Blacque Daniel Hernández-Valdés Prof. Dr. Roger Alberto 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(3):1213-1216
The labeling of (bio)molecules with metallic radionuclides such as 99mTc demands conjugated, multidentate chelators. However, this is not always necessary since phenyl rings can directly serve as integrated, organometallic ligands. Bis-arene sandwich complexes are generally prepared by the Fischer–Hafner reaction. In extension of this, we show that [99mTc(η6-C6R6)2]+-type complexes are directly accessible from water and [99mTcO4]−, even using arenes incompatible with Fischer–Hafner conditions. To unambiguously confirm the nature of these unprecedented 99mTc complexes, their rhenium homologous have been prepared by substituting naphthalene ligands in [Re(η6-C10H8)2]+ with the corresponding phenyl groups. The ease with which highly stable [99mTc(η6-C6R6)2]+ complexes are formed under standard labeling conditions enables a multitude of new potential imaging agents based on commercial pharmaceuticals or lead structures. 相似文献
95.
Numerical Algorithms - From the majorant principle of Kantorovich and the theoretical significance of Newton’s method, we obtain domains of existence and uniqueness of solution for nonlinear... 相似文献
96.
Can a Six‐Letter Alphabet Increase the Likelihood of Photochemical Assault to the Genetic Code?
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Brennan Ashwood Marvin Pollum Prof. Dr. Carlos E. Crespo‐Hernández 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(46):16648-16656
In 2014, two unnatural nucleosides, d5SICS and dNaM, were shown to selectively base pair and replicate with high fidelity in a modified strain of E. coli, thus effectively expanding its genetic alphabet from four to six letters. More recently, a significant reduction in cell proliferation was reported in cells cultured with d5SICS, and putatively with dNaM, upon exposure to brief periods of near‐visible radiation. The photosensitizing properties of the lowest‐energy excited triplet state of both d5SICS and dNaM were implicated in their cytotoxicity. Importantly, however, the excited‐state mechanisms by which near‐visible excitation populates the triplet states of d5SICS and dNaM are currently unknown. In this study, steady‐state and time‐resolved spectroscopies are combined with quantum‐chemical calculations in order to reveal the excited‐state relaxation mechanisms leading to efficient population of the triplet states in these unnatural nucleosides in solution. It is shown that excitation of d5SICS or dNaM with near‐visible light leads overwhelmingly to ultrafast population of their triplet states on the femtosecond time scale. The results presented in this work lend strong support to the proposal that photoexcitation of these unnatural nucleosides can accelerate oxidatively generated damage to DNA and other biomolecules within the cellular environment. 相似文献
97.
98.
Zaira Domínguez Javier Hernández Lorena Silva-Gutiérrez Magali Salas-Reyes Mario Sánchez Gabriel Merino 《Phosphorus, sulfur, and silicon and the related elements》2013,188(4):772-784
The effect of electron-withdrawing (EW) and electron-releasing (ER) substituents on the 31P NMR chemical shifts and the structural parameters of a series of tris-(p-X-aryl)selenophosphates is reported in this article. Similarly to O-aryl phosphates and O-aryl thiophosphates, EW groups attached to aromatic rings induce a shielding effect on the 31P NMR signal. After a detailed experimental and theoretical analysis, we confirmed that the selenium atom is the main part responsible for the charge density transfer toward phosphorus through a back-bonding effect. The obtained 1JP-Se values for the complete series agree with this observation. Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file. 相似文献
99.
Self‐assembled monolayers of cucurbit[6]uril (CB[6]) on a gold electrode have been used for 4,4′‐oxydialine (ODA) analysis. The formation of the supramolecular complex between ODA and CB[6] was used for the molecular selection and the electroanalytical determination of this analyte. In addition to this, all the parameters affecting the modification of the gold electrode and the determination of 4,4′‐oxydianiline were optimized by square wave voltammetry. Upon the electrode modification, pentanethiol was employed to fill up the exposed surface between CB[6] molecules. The calculated detection and determination limits were 0.06 µg mL?1 and 0.19 µg mL?1, respectively, with good accuracy and precision as shown by the calculated values for the relative error and relative standard deviation (Er=0.1 % and RDS=2.9 %; n=10 ). Moreover, the developed methodology was successfully applied to the 4,4′‐oxydialine determination in real wastewaters and shoe‐dyeing samples. 相似文献
100.
Photoactive materials based on dye molecules incorporated into thin films or bulk solids are useful for applications as photosensitization, photocatalysis, solar cell sensitization and fluorescent labeling, among others. In most cases, high concentrations of dyes are desirable to maximize light absorption. Under these circumstances, the proximity of dye molecules leads to the formation of aggregates and statistical traps, which dissipate the excitation energy and lower the population of excited states. The search for enhancement of light collection, avoiding energy wasting requires accounting the photophysical parameters quantitatively, including the determination of quantum yields, complicated by the presence of light scattering when particulate materials are considered. In this work we summarize recent advances on the photophysics of dyes in light‐scattering materials, with particular focus on the effect of dye concentration. We show how experimental reflectance, fluorescence and laser‐induced optoacoustic spectroscopy data can be used together with theoretical models for the quantitative evaluation of inner filter effects, fluorescence and triplet formation quantum yields and energy transfer efficiencies. 相似文献