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61.
H. Awad M. J. Stoudemayer L. Usher I. J. Amster A. Cohen U. Das R. M. Whittal J. Dimmock A. El‐Aneed 《Journal of mass spectrometry : JMS》2014,49(11):1139-1147
Unusual ionization behavior was observed with novel antineoplastic curcumin analogues during the positive ion mode of matrix‐assisted laser desorption ionization (MALDI) and dopant‐free atmospheric pressure photoionization (APPI). The tested compounds produced an unusual significant peak designated as [M ? H]+ ion along with the expected [M + H]+ species. In contrast, electrospray ionization, atmospheric pressure chemical ionization and the dopant‐mediated APPI (dopant‐APPI) showed only the expected [M + H]+ peak. The [M ? H]+ ion was detected with all evaluated curcumin analogues including phosphoramidates, secondary amines, amides and mixed amines/amides. Our experiments revealed that photon energy triggers the ionization of the curcumin analogues even in the absence of any ionization enhancer such as matrix, solvent or dopant. The possible mechanisms for the formation of both [M ? H]+ and [M + H]+ ions are discussed in this paper. In particular, three proposed mechanisms for the formation of [M ? H]+ were evaluated. The first mechanism involves the loss of H2 from the protonated [M + H]+ species. The other two mechanisms include hydrogen transfer from the analyte radical cation or hydride abstraction from the neutral analyte molecule. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
62.
Electrophile‐Induced Nucleophilic Substitution of the nido‐Dicarbaundecaborate Anion nido‐7,8‐C2B9H12− by Conjugated Heterodienes 下载免费PDF全文
Dr. René Frank Anup Kumar Adhikari Henry Auer Prof. Dr. Evamarie Hey‐Hawkins 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(5):1440-1446
Substitution of the dicarbaundecaborate anion nido‐7,8‐C2B9H12? ( 1 ) by precise hydride abstraction followed by nucleophilic attack usually leads to symmetric products 10‐R‐nido‐7,8‐C2B9H11. However, thioacetamide (MeC(S)NH2) as nucleophile and acetone/AlCl3 as hydride abstractor gave asymmetric 9‐[MeC(NHiPr)S]‐nido‐7,8‐C2B9H11 ( 2 ), whereas N,N‐dimethylthioacetamide (MeC(S)NMe2) gave the expected symmetric 10‐[MeC(NMe2)S]‐nido‐7,8‐C2B9H11 ( 4 ). For the formation of 2 , acetone and thioacetamide are assumed to give the intermediate MeC(S)N(CMe2) ( 3 ), which then attacks 1 with formation of 2 . Similarly, reaction of acetyliminium chloride [MeC(O)NH(CPh2)]Cl ( 5 ) with 1 in THF gave a mixture of 9‐ and 10‐substituted [MeC(NHCHPh2)O]‐nido‐7,8‐C2B9H11 ( 6 and 7 , respectively). These reactions are the first examples in which compounds (here heterodienes) that unite the functionalities of both hydride acceptor and nucleophilic site react with 1 in a bimolecular fashion. Furthermore, the analogous reaction of 1 and 5 (in an equilibrium mixture with acetyl chloride and benzophenone imine) in MeCN afforded 10‐[MeC(NCPh2)NH]‐nido‐7,8‐C2B9H11 ( 8 ) and MeC(O)NHCHPh2 ( 9 ). 相似文献
63.
We report on a teaching experiment intended to foster a concept of multiplication that would both subsume students’ multiple-groups concept of whole number multiplication and provide a conceptual basis for understanding multiplication of fractions. The teaching experiment, which used a rigorous single-subject methodology, began with an attempt to build on students’ multiple-groups concept by promoting generalizing assimilation. This was not totally successful and led to a redesign aimed at promoting reflective abstraction. Analysis of this latter phase led to several significant conclusions, which in turn led to a revised hypothetical learning trajectory. The revised trajectory aims to foster a concept of multiplication as a change in units. 相似文献
64.
Photoreactions with a Twist: Atropisomerism‐Driven Divergent Reactivity of Enones with UV and Visible Light 下载免费PDF全文
Nandini Vallavoju Avadakkam Sreenithya Anoklase J.‐L. Ayitou Dr. Steffen Jockusch Prof. Dr. Raghavan B. Sunoj Prof. Dr. Jayaraman Sivaguru 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(32):11339-11348
Light‐induced transformation of atropisomeric and achiral enones displays divergent reactivity. Photocyclization leading to 3,4‐dihydroquinolin‐2‐one was observed with achiral enone carboxamide, whereas the atropisomeric enone carboxamides underwent hydrogen abstraction leading to spiro‐β‐lactams. Detailed photochemical, photophysical, and theoretical investigations have provided insight into this divergent reactivity and selectivity. 相似文献
65.
We have used the single‐pulse shock tube technique with postshock GC/MS product analysis to investigate the mechanism and kinetics of the unimolecular decomposition of isopropanol, a potential biofuel, and of its reaction with H atoms at 918‐1212 K and 183‐484 kPa. Experiments employed dilute mixtures in argon of isopropanol, a radical scavenger, and, for H‐atom studies, two different thermal precursors of H. Without an added H source, isopropanol decomposes in our studies predominantly by molecular dehydration. Added H atoms significantly augment decomposition, mainly by abstraction of the tertiary and primary hydrogens, reactions that, respectively, lead to acetone and propene as stable organic products. Traces of acetaldehyde were observed in some experiments above ≈ 1100 K and establish branching limits for minor decomposition pathways. To quantitatively account for secondary chemistry and optimize rate constants of interest, we employed the method of uncertainty minimization using polynomial chaos expansions (MUM‐PCE) to carry out a unified analysis of all datasets using a chemical model–based originally on JetSurF 2.0. We find: k(isopropanol → propene + H2O) = 10(13.87 ± 0.69) exp(?(33 099 ± 979) K/ T) s?1 at 979‐1212 K and 286‐484 kPa, with a factor of two uncertainty (2σ), including systematic errors. For H atom reactions, optimization yields: k(H + isopropanol → H2 + p‐C3H6OH) = 10(6.25 ± 0.42) T2.54 exp(?(3993 ± 1028) K /T) cm3 mol?1 s?1 and k(H + isopropanol → H2 + t‐C3H6OH) = 10(5.83 ± 0.37) T2.40 exp(?(1507 ± 957) K /T) cm3 mol?1 s?1 at 918‐1142 K and 183‐323 kPa. We compare our measured rate constants with estimates used in current combustion models and discuss how hydrocarbon functionalization with an OH group affects H abstraction rates. 相似文献
66.
Highly effective exaction (up to 97%) of noble metal Au, Pt, or Pd as MCl4n? form (i.e., AuCl4?, PtCl42?, or PdCl42?) from NanMCl4 aqueous solution have been achieved on the basis of the interactions between MCl4n? and cyclo[2](2,6-di(1H-imidazol-1-yl)pyridine)[2](2,6-bisbromomethyl)pyridine (14+). 相似文献
67.
68.
Jing Xu Yuhong Ma Jingyi Xie F.J. Xu Wantai Yang 《Journal of polymer science. Part A, Polymer chemistry》2011,49(12):2755-2760
A universal photoassisted pathway to functionalize polymeric surfaces is presented by transferring the inert surface sp3 C? H bonds into reactive groups, such as ? SO3H, ? NH2, ? SH, and ? COOH. The proposed method uses acetone as photoinitiator and different phenols with a para substituent XR as the reactants. Acetone excited by UV irradiation acts as a pair of scissors cutting both the surface C? H bonds of the polymer substrate and the O? H bonds of phenol, leading to the formation of carbon‐centered surface chain free radicals and oxygen‐centered phenoxy free radicals. By coupling of these two radicals, a variety of functional X groups with an R spacer from XR species of different phenol reactants were readily bonded to the polymeric surfaces, where phenol reactants included 4‐hydroxylbenzene sulfonic acid for ? SO3H, p‐aminophenol and tyramine for ? NH2, 4‐hydroxythiophenol for ? SH, and tyrosine for ? COOH. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011 相似文献
69.
Long Zhao Ralf I. Kaiser Wenchao Lu Musahid Ahmed Mikhail M. Evseev Eugene K. Bashkirov Valeriy N. Azyazov Christina Tönshoff Florian Reicherter Holger F. Bettinger Alexander M. Mebel 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(28):11430-11434
A representative, low-temperature gas-phase reaction mechanism synthesizing polyacenes via ring annulation exemplified by the formation of pentacene (C22H14) along with its benzo[a]tetracene isomer (C22H14) is unraveled by probing the elementary reaction of the 2-tetracenyl radical (C18H11.) with vinylacetylene (C4H4). The pathway to pentacene—a prototype polyacene and a fundamental molecular building block in graphenes, fullerenes, and carbon nanotubes—is facilitated by a barrierless, vinylacetylene mediated gas-phase process thus disputing conventional hypotheses that synthesis of polycyclic aromatic hydrocarbons (PAHs) solely proceeds at elevated temperatures. This low-temperature pathway can launch isomer-selective routes to aromatic structures through submerged reaction barriers, resonantly stabilized free-radical intermediates, and methodical ring annulation in deep space eventually changing our perception about the chemistry of carbon in our universe. 相似文献
70.
Hongjiang Ren 《Molecular physics》2013,111(23):3663-3672
The mechanism of H abstraction reactions for Isoflurane with the OH radical was investigated using density functional theory and G3(MP2) duel theory methods. The geometrical structures of all the species were fully optimised at B3LYP/6-311++G** level of theory. Thermochemistry data were obtained by utilising the high accurate model chemistry method G3(MP2) combined with the standard statistical thermodynamic calculations. Gibbs free energies were used for the reaction channels analysis. All the reaction channels were confirmed throughout the intrinsic reaction coordinate analysis. The results show that two channels were obtained, which correspond to P(1) and P(2) with the respective activation barriers of 63.03 and 54.82 kJ/mol. The rate constants for the two channels over a wide temperature range of 298.15–2000 K were predicted and the calculated data are in agreement with the experimental one. The results show that P(2) is the dominant reaction channel under 800 K and above 800 K, it can be found that P(1) will be more preferable reaction channel. 相似文献