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1.
Dr. Zhoulong Fan Katherine L. Bay Dr. Xiangyang Chen Zhe Zhuang Han Seul Park Dr. Kap-Sun Yeung Prof. Dr. K. N. Houk Prof. Dr. Jin-Quan Yu 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(12):4800-4807
A simple and efficient nitrile-directed meta-C−H olefination, acetoxylation, and iodination of biaryl compounds is reported. Compared to the previous approach of installing a complex U-shaped template to achieve a molecular U-turn and assemble the large-sized cyclophane transition state for the remote C−H activation, a synthetically useful phenyl nitrile functional group could also direct remote meta-C−H activation. This reaction provides a useful method for the modification of biaryl compounds because the nitrile group can be readily converted to amines, acids, amides, or other heterocycles. Notably, the remote meta-selectivity of biphenylnitriles could not be expected from previous results with a macrocyclophane nitrile template. DFT computational studies show that a ligand-containing Pd–Ag heterodimeric transition state (TS) favors the desired remote meta-selectivity. Control experiments demonstrate the directing effect of the nitrile group and exclude the possibility of non-directed meta-C−H activation. Substituted 2-pyridone ligands were found to be key in assisting the cleavage of the meta-C−H bond in the concerted metalation–deprotonation (CMD) process. 相似文献
2.
Dr. Sevan D. Houston Dr. Hui Xing Prof. Paul V. Bernhardt Timothy J. Vanden Berg Dr. John Tsanaktsidis Dr. G. Paul Savage Prof. Craig M. Williams 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(11):2735-2739
The scope and limitations of Eaton's rhodium(I)-catalyzed valence isomerization of cubane to cyclooctatetraene (COT) were investigated in the context of functional group tolerability, multiple substitution modes and the ability of cubane-alcohols to undergo one-pot tandem Ley–Griffith Wittig reactions in the absence of a transition metal catalyst. 相似文献
3.
Katherine A. Seaton 《International Journal of Mathematical Education in Science & Technology》2019,50(7):1063-1072
ABSTRACTTo date, the way that academic misconduct is manifested in undergraduate mathematics coursework has been unexamined in the literature, with the consequence that policy and preventive education can fail to address it appropriately. This paper describes the particular features of the responses expected in mathematical tasks and provides concrete examples of what lapses of integrity look like in this context. The intent is to lay groundwork for discussion and a response to this issue from within our discipline. 相似文献
4.
Dr. Radu Custelcean Neil J. Williams Charles A. Seipp 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2015,127(36):10671-10675
An effective approach to sulfate separation from aqueous solutions is based on the crystallization of extended [SO4(H2O)52−]n sulfate–water clusters with a bis(guanidinium) ligand. The ligand was generated in situ by hydrazone condensation in water, thereby bypassing the need for elaborate syntheses, tedious purifications, and organic solvents. Crystallization of sulfate–water clusters represents an alternative approach to the now established sulfate separation strategies that involve encapsulation of the “naked” anion. 相似文献
5.
Chemorheology investigation of a glassy epoxy thermoset on tensile plastic flow and fracture morphology 下载免费PDF全文
Stephen F. Foster Emily A. Hoff Greg W. Curtzwiler Eric B. Williams Kevin B. Davis Derek L. Patton James W. Rawlins 《Journal of Polymer Science.Polymer Physics》2015,53(19):1333-1344
Reproducible and uncharacteristic tensile stress–strain behavior of cured glassy epoxy‐amine networks produces distinctive fracture surfaces. Test specimens exhibiting plastic flow result in mirror‐like fracture surfaces, whereas samples that fail during yield or strain softening regions possess nominal mirror‐mist‐hackle topography. Atomic force microscopy and scanning electron microscopy reveal branched nodule morphologies in the 50‐nm size scale that may be responsible for the unusual tensile properties. Current hypothesis is that plastic flow of the glassy thermoset occurs through the existence and deformation of these nodular nanostructures. The thermal cure profile of the epoxy‐amine thermoset affects the size and formation of the nodular nanostructure. Eliminating vitrification during thermoset polymerization forms a more continuous phase, reduction in size of the nodules, and eliminates the capacity of the material to yield in plastic flow. This maximizes nanostructure connectivity of the glassy epoxy‐amine thermoset and reduces strain to failure significantly. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1333–1344. 相似文献
6.
7.
Dr. Katherine Villa Dr. Jan Vyskočil Dr. Yulong Ying Dr. Jaroslav Zelenka Prof. Martin Pumera 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(14):3039-3043
Yeasts play a key role in the production of alcoholic beverages by fermentation processes. However, because of their continuous growth, they commonly cause spoilage of the final product. Herein, we introduce dual magnetic/light-responsive self-propelled microrobots that can actively move in a beer sample and capture yeast cells. The presence of magnetic nanoparticles on the surface of the microrobots enables their magnetic actuation under fuel-free conditions. In addition, their photoactivity under visible-light irradiation leads to an overall enhancement of their swimming and yeast removal capabilities. It was found that after the application of the microrobots into a real unfiltered beer sample, these micromachines were able to remove almost 100 % of residual yeasts. In addition, these microrobots could also be added at the initial step of the fermentation process without altering the final beer properties, such as alcohol level, color, and pH. This work demonstrates the potential of using externally actuated microrobots as an innovative and low-cost solution for avoiding yeast spoilage in complex liquid environments, such as alcoholic beverages. Therefore, these autonomous self-propelled microrobots open new avenues for future applications in the food industry. 相似文献
8.
Madeleine A. Dallaston Dr. Sevan D. Houston Prof. Craig M. Williams 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(52):11966-11970
With the burgeoning interest in cage motifs for bioactive molecule discovery, and the recent disclosure of 1,4-cubane-dicarboxylic acid impact sensitivity, more research into the safety profiles of cage scaffolds is required. Therefore, the impact sensitivity and thermal decomposition behavior of judiciously selected starting materials and synthetic intermediates of cubane, bicyclo[1.1.1]pentane (BCP), and bicyclo[2.2.2]octane (BCO) were evaluated via hammer test and sealed cell differential scanning calorimetry, respectively. Iodo-substituted systems were found to be more impact sensitive, whereas hydroxymethyl substitution led to more rapid thermodecomposition. Cubane was more likely to be impact sensitive with these substituents, followed by BCP, whereas all BCOs were unresponsive. The majority of derivatives were placed substantially above Yoshida thresholds—a computational indicator of sensitivity. 相似文献
9.
Dr. Lidia A. Maslovskaya Dr. Andrei I. Savchenko Prof. Elizabeth H. Krenske Dr. Sharon Chow Tina Holt Dr. Victoria A. Gordon Dr. Paul W. Reddell Carly J. Pierce Prof. Peter G. Parsons Prof. Glen M. Boyle Prof. Andrei G. Kutateladze Prof. Craig M. Williams 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(51):11862-11867
Structurally unique halimanes EBC-232 and EBC-323, isolated from the Australian rainforest plant Croton insularis, proved considerably difficult to elucidate. The two diastereomers, which consist an unusual oxo-6,7-spiro ring system fused to a dihydrofuran, were solved by unification and consultation of five in silico NMR elucidation and prediction methods [i.e., ACDLabs, olefin strain energy (OSE), DP4, DU8+ and TD DFT CD]. Structure elucidation challenges of this nature are prime test case examples for empowering future AI learning in structure elucidation. 相似文献
10.
Huiye Zhong Wei-Shang Lo Tiantian Man Benjamin P. Williams Dan Li Dr. Sheng-Yu Chen Prof. Dr. Hao Pei Prof. Dr. Li Li Prof. Dr. Chia-Kuang Tsung 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(57):12931-12935
DNAzymes are a promising class of bioinspired catalyst; however, their structural instability limits their potential. Herein, a method to stabilize DNAzymes by encapsulating them in a metal–organic framework (MOF) host is reported. This biomimetic mineralization process makes DNAzymes active under a wider range of conditions. The concept is demonstrated by encapsulating hemin-G-quadruplex (Hemin-G4) into zeolitic imidazolate framework-90 (ZIF-90), which indeed increases the DNAzyme's structural stability. The stabilized DNAzymes show activities in the presence of Exonuclease I, organic solvents, or high temperature. Owing to its elevated stability and heterogeneous nature, it is possible to perform catalysis under continuous-flow conditions, and the DNAzyme can be reactivated in situ by introducing K+. Moreover, it is found that the encapsulated DNAzyme maintains its high enantiomer selectivity, demonstrated by the sulfoxidation of thioanisole to (S)-methyl phenyl sulfoxide. This concept of stabilizing DNAzymes expands their potential application in chemical industry. 相似文献