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21.
22.
Adding a Structural Context to the Deprotometalation and Trans‐Metal Trapping Chemistry of Phenyl‐Substituted Benzotriazole 下载免费PDF全文
Dr. M. Ángeles Fuentes Dr. Alan R. Kennedy Prof. Robert E. Mulvey Dr. John A. Parkinson Dr. Toni Rantanen Dr. Stuart D. Robertson Prof. Victor Snieckus 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(42):14812-14822
Organometallic bases are becoming increasingly complex, because mixing components can lead to bases superior to single‐component bases. To better understand this superiority, it is useful to study metalated intermediate structures prior to quenching. This study is on 1‐phenyl‐1H‐benzotriazole, which was previously deprotonated by an in situ ZnCl2 ? TMEDA/LiTMP (TMEDA=N,N,N′,N′‐tetramethylethylenediamine; TMP=2,2,6,6‐tetramethylpiperidide) mixture and then iodinated. Herein, reaction with LiTMP exposes the deficiency of the single‐component base as the crystalline product obtained was [{4‐R‐1‐(2‐lithiophenyl)‐1H‐benzotriazole ? 3THF}2], [R=2‐C6H4(Ph)NLi], in which ring opening of benzotriazole and N2 extrusion had occurred. Supporting lithiation by adding iBu2Al(TMP) induces trans‐metal trapping, in which C?Li bonds transform into C?Al bonds to stabilise the metalated intermediate. X‐ray diffraction studies revealed homodimeric [(4‐R′‐1‐phenyl‐1H‐benzotriazole)2], [R′=(iBu)2Al(μ‐TMP)Li], and its heterodimeric isomer [(4‐R′‐1‐phenyl‐1H‐benzotriazole){2‐R′‐1‐phenyl‐1H‐benzotriazole}], whose structure and slow conformational dynamics were probed by solution NMR spectroscopy. 相似文献
23.
A Statewide Implementation of the Critical Features of Professional Development: Impact on Teacher Outcomes 下载免费PDF全文
Carla C. Johnson Toni Sondergeld Janet B. Walton 《School science and mathematics》2017,117(7-8):341-349
This study is focused on a statewide implementation of the core conceptual framework for effective professional development in the United States. and associated impact on teacher quality and attitudes. The framework included content focus, active learning, coherence, duration, and collective participation. There were 252 participants in the study, who were involved in one of the five science or six mathematics programs. Findings indicated a significant impact on teacher quality for all participating programs. Teacher attitudes were positive at the baseline, and remained positive with some improvement at the end of the program. However, teacher perceived preparedness increased significantly across the duration of the program. Discussion of the findings and implications for professional development programs internationally are shared. 相似文献
24.
The term reactive oxygen species refers to small molecules that can oxidize, for example, nearby proteins, especially cysteine, methionine, tryptophan, and tyrosine residues. Tryptophan oxidation is always irreversible in the cell and can yield several oxidation products, such as 5-hydroxy-tryptophan (5-HTP), oxindolylalanine (Oia), kynurenine (Kyn), and N-formyl-kynurenine (NFK). Because of the severe effects that oxidized tryptophan residues can have on proteins, there is a great need to develop generally applicable and highly sensitive techniques to identify the oxidized residue and the oxidation product. Here, the fragmentation behavior of synthetic peptides corresponding to sequences recently identified in three skeletal muscle proteins as containing oxidized tryptophan residues were studied using postsource decay and collision-induced dissociation (CID) in matrix-assisted laser desorption/ionization (MALDI) time-of-flight (TOF)/TOF mass spectrometry (MS) and CID in an electrospray ionization (ESI) double quadrupole TOF-MS. For each sequence, a panel of five different peptides containing Trp, 5-HTP, Kyn, NFK, or Oia residue was studied. It was always possible to identify the modified positions by the y-series and also to distinguish the different oxidation products by characteristic fragment ions in the lower mass range by tandem MS. NFK- and Kyn-containing peptides displayed an intense signal at m/z 174.1, which could be useful in identifying accordingly modified peptides by a sensitive precursor ion scan. Most importantly, it was always possible to distinguish isomeric 5-HTP and Oia residues. In ESI- and MALDI-MS/MS, this was achieved by the signal intensity ratios of two signals obtained at m/z 130.1 and 146.1. In addition, high collision energy CID in the MALDI-TOF/TOF-MS also permitted the identification of these two isomeric residues by their v- and w-ions, respectively. 相似文献
25.
Five-step total syntheses of angelicoin A and B from 2,2,6-trimethyl-4-dioxinone are reported using late stage biomimetic aromatization reactions via diketo-dioxinones as intermediates. In addition, with angelicoin A, this aromatization was coupled with a palladium-catalyzed decarboxylative prenylation in a one-pot sequence as the key step. 相似文献
26.
Roe C Moragas Solá T Sasraku-Neequaye L Hobbs H Churcher I MacPherson D Stockman RA 《Chemical communications (Cambridge, England)》2011,47(26):7491-7493
The synthetic utility of S-mesitylsulfinimines for the synthesis of chiral amines and aziridines was examined through their reactions with Grignard reagents, with the ylides derived from trimethylsulfonium iodide and S-allyl-tetrahydrothiophenium bromide and through an aza-Darzens manifold, affording convenient access to a diverse range of highly substituted chiral amines and aziridines in high yields and excellent stereoselectivities. 相似文献
27.
The discovery of 5-formylcytosine in embryonic stem cell DNA 总被引:2,自引:0,他引:2
28.
Wenbin Du Denghui Liu Carla C. Johnson Toni A. Sondergeld Virginia L. J. Bolshakova Tamara J. Moore 《School science and mathematics》2019,119(2):105-114
This study of a state‐funded, 3‐year implementation of an integrated STEM professional development (PD) program for teachers from two middle schools in the midwestern U.S. examined if participants in the PD were enabled to transform their practice and perceptions of STEM. An integrated STEM approach includes a focus on the STEM disciplines, along with leveraging social studies/history and English/language arts as important context and tools for solving society’s biggest challenges. Findings in this study indicated that teachers implemented more effective STEM teaching strategies and had more positive perceptions regarding STEM overall. Further, participants became more aware of their personal needs for resources and support to teach through integrated STEM. Implications for research and practice are discussed. 相似文献
29.
30.
Willi Ammann Ren Richarz Toni Wirthlin Detlef Wendisch 《Magnetic resonance in chemistry : MRC》1982,20(4):260-265
2D NMR techniques (J-resolved 13C, 13C? 13C correlated, 1H? 13C correlated) were used to gather more chemical shift and coupling information on the pentacyclic triterpene, lupane. They confirm and complete 13C assignments made earlier, and corroborate the constitution and major configurational details of lupane. Lupane is a parent compound and spectral reference in the study of sedimental demethylated triterpenes. 相似文献