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11.
Development and evaluation of gas and liquid chromatographic methods for the analysis of fatty amines
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Zachary S. Breitbach Choyce A. Weatherly Ross M. Woods Chengdong Xu Glenda Vale Alain Berthod Daniel W. Armstrong 《Journal of separation science》2014,37(5):558-565
In contrast to the plethora of publications on the separation of fatty acids, analogous studies involving fatty amines are scarce. A recently introduced ionic‐liquid‐based capillary column for GC was used to separate trifluoroacetylated fatty amines focusing on the analysis of a commercial sample. Using the ionic liquid column (isothermal mode at 200°C) it was possible to separate linear primary fatty amines from C12 to C22 chain length in less 25 min with MS identification. The log of the amine retention factors are linearly related to the alkyl chain length with a methylene selectivity of 0.117 kcal/mol for the saturated amines and 0.128 kcal/mol for the mono‐unsaturated amines. The sp2 selectivity for unsaturated fatty amines also could be calculated as 0.107 kcal/mol for the ionic liquid column. The commercial sample was quantified by GC with flame ionization detection (FID). An LC method also was developed with a reversed phase gradient separation using acetonitrile/formate buffer mobile phases and ESI‐MS detection. Native amines could be detected and identified by their single ion monitoring chromatograms even when partial coelution was observed. The analysis of the commercial sample returned results coherent with those obtained by GC–FID and with the manufacturer's data. 相似文献
12.
Azobenzene‐Functionalized Metal–Organic Polyhedra for the Optically Responsive Capture and Release of Guest Molecules
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Dr. Jinhee Park Dr. Lin‐Bing Sun Ying‐Pin Chen Zachary Perry Prof. Dr. Hong‐Cai Zhou 《Angewandte Chemie (International ed. in English)》2014,53(23):5842-5846
Stimuli‐responsive metal–organic polyhedra (srMOPs) functionalized with azobenzene showed UV‐irradiation‐induced isomerization from the insoluble trans‐srMOP to the soluble cis‐srMOP, whereas irradiation with blue light reversed this process. Guest molecules were trapped and released upon cis‐to‐trans and trans‐to‐cis isomerization of the srMOPs, respectively. This study provides a new direction in the ever‐diversifying field of MOPs, while laying the groundwork for a new class of optically responsive materials. 相似文献
13.
Jonathan W. Dube Cameron M. E. Graham Prof. Charles L. B. Macdonald Dr. Zachary D. Brown Prof. Philip P. Power Prof. Paul J. Ragogna 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(22):6739-6744
Two unique systems based on low‐coordinate main group elements that activate P4 are shown to quantitatively release the phosphorus cage upon short exposure to UV light. This reactivity marks the first reversible reactivity of P4, and the germanium system can be cycled 5 times without appreciable loss in activity. Theoretical calculations reveal that the LUMO is antibonding with respect to the main group element–phosphorus bonds and bonding with respect to reforming the P4 tetrahedron, providing a rationale for this unprecedented activity, and suggesting that the process is tunable based on the substituents. 相似文献
14.
Dr. Takaaki Mitsuhashi Dr. Lena Barra Zachary Powers Volga Kojasoy Andrea Cheng Feng Yang Dr. Yoshimasa Taniguchi Dr. Takashi Kikuchi Prof. Dr. Makoto Fujita Prof. Dr. Dean J. Tantillo Prof. Dr. John A. Porco Jr Prof. Dr. Ikuro Abe 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(52):23980-23989
Fungal meroterpenoids are a diverse group of hybrid natural products with impressive structural complexity and high potential as drug candidates. In this work, we evaluate the promiscuity of the early structure diversity-generating step in fungal meroterpenoid biosynthetic pathways: the multibond-forming polyene cyclizations catalyzed by the yet poorly understood family of fungal meroterpenoid cyclases. In total, 12 unnatural meroterpenoids were accessed chemoenzymatically using synthetic substrates. Their complex structures were determined by 2D NMR studies as well as crystalline-sponge-based X-ray diffraction analyses. The results obtained revealed a high degree of enzyme promiscuity and experimental results which together with quantum chemical calculations provided a deeper insight into the catalytic activity of this new family of non-canonical, terpene cyclases. The knowledge obtained paves the way to design and engineer artificial pathways towards second generation meroterpenoids with valuable bioactivities based on combinatorial biosynthetic strategies. 相似文献
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16.
Shankari V. Rajagopal Kurt M. Fujiwara Ruwan Senaratne Kevin Singh Zachary A. Geiger David M. Weld 《Annalen der Physik》2017,529(8)
Ultracold atomic physics experiments offer a nearly ideal context for the investigation of quantum systems far from equilibrium. We describe three related emerging directions of research into extreme non‐equilibrium phenomena in atom traps: quantum emulation of ultrafast atom‐light interactions, coherent phasonic spectroscopy in tunable quasicrystals, and realization of Floquet matter in strongly‐driven lattice systems. We show that all three should enable quantum emulation in parameter regimes inaccessible in solid‐state experiments, facilitating a complementary approach to open problems in non‐equilibrium condensed matter. 相似文献
17.
Xiaotong Zhang Eranda Wanigasekara Zachary S. Breitbach Edra Dodbiba Daniel W. Armstrong 《Rapid communications in mass spectrometry : RCM》2010,24(8):1113-1123
In previous studies, new electrospray ionization mass spectrometry (ESI‐MS) approaches were developed for the highly sensitive detection of singly and doubly charged anions in positive mode ESI‐MS by using specially synthesized dicationic and tricationic ion‐pairing agents, respectively. By detecting the positively charged ion complex in the positive mode, limits of detection (LODs) for the anions can be lowered by several magnitudes. In this work, we used eighteen newly synthesized tetracationic ion‐pairing agents, constructed with different geometries, linkages and cation moieties, for the detection of eighteen triply charged anions of different structural motifs. The LODs for these anions were from ten to several thousand times lower in the positive selective ion monitoring (SIM) mode than in the negative mode. These tetracationic agents also were shown to be useful for the detection of ?1 and ?2 anions. In addition, the LODs for ?3 anions can be further lowered by monitoring the product fragments of the ion‐pairing complexes in the single reaction monitoring (SRM) mode. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
18.
Himo F Demko ZP Noodleman L Sharpless KB 《Journal of the American Chemical Society》2002,124(41):12210-12216
It is well-known that azide salts can engage nitriles at elevated temperatures to yield tetrazoles; however, there is continued debate as to the mechanism of the reaction. Density functional theory calculations with the hybrid functional B3LYP have been performed to study different mechanisms of tetrazole formation, including concerted cycloaddition and stepwise addition of neutral or anionic azide species. The calculations presented here suggest a previously unsuspected nitrile activation step en route to an imidoyl azide, which then cyclizes to give the tetrazole. The activation barriers are found to correlate strongly with the electron-withdrawing potential of the substituent on the nitrile. 相似文献
19.
We theoretically explore the transfer of vortex states between atomic Bose-Einstein condensates and optical pulses using ultraslow and stopped light techniques. We find shining a coupling laser on a rotating two-component ground state condensate with a vortex lattice generates a probe laser field with optical vortices. We also find that optical vortex states can be robustly stored in the atomic superfluids for times, in Rb-87 condensates, limited only by the ground state coherence time. 相似文献
20.
Because of dispersion in head-related transfer functions (HRTFs), the interaural time difference (ITD) varies with frequency. This physical effect ought to have consequences for the size or shape of the auditory image of broadband noise because different frequency regions of the noise have different ITDs. However, virtual reality experiments suggest that human listeners are insensitive to head-related dispersion. The experiments of this article test that suggestion by experiments that isolate dispersion from amplitude effects in the HRTF and attempt to optimize the opportunity for detecting it. Nevertheless, the experiments find that the only effect of dispersion is to shift the lateralization of the auditory image. This negative result is explained in terms of the cross-correlation function for head-dispersed noise. Although the broad-band cross-correlation function differs considerably from 1.0, the cross-correlation functions within bands characteristic of auditory filters do not. A detailed study of the lateralization shifts show that the experimental shifts can be successfully calculated as an average of stimulus ITDs as weighted by Raatgever's frequency-weighting function (Thesis, Delft, The Netherlands, 1980). 相似文献