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121.
Isaiah Adelabu Patrick TomHon Mohammad S. H. Kabir Shiraz Nantogma Mustapha Abdulmojeed Iuliia Mandzhieva Dr. Jessica Ettedgui Dr. Rolf E. Swenson Dr. Murali C. Krishna Prof. Thomas Theis Prof. Boyd M. Goodson Prof. Eduard Y. Chekmenev 《Chemphyschem》2022,23(2):e202100839
Signal Amplification By Reversible Exchange in SHield Enabled Alignment Transfer (SABRE-SHEATH) is investigated to achieve rapid hyperpolarization of 13C1 spins of [1-13C]pyruvate, using parahydrogen as the source of nuclear spin order. Pyruvate exchange with an iridium polarization transfer complex can be modulated via a sensitive interplay between temperature and co-ligation of DMSO and H2O. Order-unity 13C (>50 %) polarization of catalyst-bound [1-13C]pyruvate is achieved in less than 30 s by restricting the chemical exchange of [1-13C]pyruvate at lower temperatures. On the catalyst bound pyruvate, 39 % polarization is measured using a 1.4 T NMR spectrometer, and extrapolated to >50 % at the end of build-up in situ. The highest measured polarization of a 30-mM pyruvate sample, including free and bound pyruvate is 13 % when using 20 mM DMSO and 0.5 M water in CD3OD. Efficient 13C polarization is also enabled by favorable relaxation dynamics in sub-microtesla magnetic fields, as indicated by fast polarization buildup rates compared to the T1 spin-relaxation rates (e. g., ∼0.2 s−1 versus ∼0.1 s−1, respectively, for a 6 mM catalyst-[1-13C]pyruvate sample). Finally, the catalyst-bound hyperpolarized [1-13C]pyruvate can be released rapidly by cycling the temperature and/or by optimizing the amount of water, paving the way to future biomedical applications of hyperpolarized [1-13C]pyruvate produced via comparatively fast and simple SABRE-SHEATH-based approaches. 相似文献
122.
Dey KK Prasad S Ash JT Deschamps M Grandinetti PJ 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2007,185(2):326-330
A sensitivity enhancement method based on selective adiabatic inversion of a satellite transition has been employed in a (pi/2)CT-(pi)ST1-(pi/2)CT spectral editing sequence to both enhance and resolve multisite NMR spectra of quadrupolar nuclei. In addition to a total enhancement of 2.5 times for spin 3/2 nuclei, enhancements up to 2.0 times is reported for the edited sites in a mixture of rubidium salts. 相似文献
123.
Sivarama Krishna Reddy Vanga Hari Babu Bollikolla V. V. Satyanarayana Peruri 《Journal of heterocyclic chemistry》2021,58(3):892-899
An efficient catalyst-free one-pot three-component synthesis of penta-substituted pyrroles has been successfully developed. A variety of penta-substituted pyrroles were straightforwardly synthesized from good to excellent yields (78%–93%) by using easily accessible starting materials under mild conditions. This protocol also provided α-amino ketones in good yields (87%–98%) without column chromatography. 相似文献
124.
Michael Koch Karthikeyan Perumal Dr. Olivier Blacque Dr. Jai Anand Garg Dr. Ramanathan Saiganesh Dr. Senthamaraikannan Kabilan Prof. Dr. Kallupattu Kuppusamy Balasubramanian Dr. Koushik Venkatesan 《Angewandte Chemie (International ed. in English)》2014,53(25):6378-6382
Design of highly efficient phosphorescent emitters based on metal‐ and heavy atom‐free boron compounds has been demonstrated by taking advantage of the singlet fission process. The combination of a suitable molecular scaffold and appropriate electronic nature of the substituents has been utilized to tailor the phosphorescence emission properties in solution, neat solid, and in doped PMMA thin films. 相似文献
125.
Dr. Koushik Chandra Dr. Tapta Kanchan Roy Dr. Deborah E. Shalev Prof. Abraham Loyter Prof. Chaim Gilon Prof. R. Benny Gerber Prof. Assaf Friedler 《Angewandte Chemie (International ed. in English)》2014,53(36):9450-9455
We present a new approach for peptide cyclization during solid phase synthesis under highly acidic conditions. Our approach involves simultaneous in situ deprotection, cyclization and trifluoroacetic acid (TFA) cleavage of the peptide, which is achieved by forming an amide bond between a lysine side chain and a succinic acid linker at the peptide N‐terminus. The reaction proceeds via a highly active succinimide intermediate, which was isolated and characterized. The structure of a model cyclic peptide was solved by NMR spectroscopy. Theoretical calculations support the proposed mechanism of cyclization. Our new methodology is applicable for the formation of macrocycles in solid‐phase synthesis of peptides and organic molecules. 相似文献
126.
Organocatalytic Asymmetric Mannich Cyclization of Hydroxylactams with Acetals: Total Syntheses of (−)‐Epilupinine, (−)‐Tashiromine,and (−)‐Trachelanthamidine
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Dr. Dipankar Koley Yarkali Krishna Kyatham Srinivas Afsar Ali Khan Ruchir Kant 《Angewandte Chemie (International ed. in English)》2014,53(48):13196-13200
An asymmetric, organocatalytic, one‐pot Mannich cyclization between a hydroxylactam and acetal is described to provide fused, bicyclic alkaloids bearing a bridgehead N atom. Both aliphatic and aromatic substrates were used in this transformation to furnish chiral pyrrolizidinone, indolizidinone, and quinolizidinone derivatives in up to 89 % yield and 97 % ee. The total syntheses of (?)‐epilupinine, (?)‐tashiromine, and (?)‐trachelanthamidine also achieved to demonstrate the generality of the process. 相似文献
127.
Hao Wang Dr. Hari Krishna Bisoyi Dr. Bing-Xiang Li Dr. Michael E. McConney Dr. Timothy J. Bunning Prof. Quan Li 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(7):2706-2709
Visible-light-driven molecular switches endowing reversible modulation of the functionalities of self-organized soft materials are currently highly sought after for fundamental scientific studies and technological applications. Reported herein are the design and synthesis of two novel halogen bond donor based chiral molecular switches that exhibit reversible photoisomerization upon exposure to visible light of different wavelengths. These chiral molecular switches induce photoresponsive helical superstructures, that is, cholesteric liquid crystals, when doped into the commercially available room-temperature achiral liquid crystal host 5CB, which also acts as a halogen-bond acceptor. The induced helical superstructure containing the molecular switch with terminal iodo atoms exhibits visible-light-driven reversible unwinding, that is, a cholesteric–nematic phase transition. Interestingly, the molecular switch with terminal bromo atoms confers reversible handedness inversion to the helical superstructure upon irradiation with visible light of different wavelengths. This visible-light-driven, reversible handedness inversion, enabled by a halogen bond donor molecular switch, is unprecedented. 相似文献
128.
Our work is focused on facile synthesis and modification of amylopectin‐grafted block copolymers by using reversible addition?fragmentation chain transfer (RAFT) polymerization technique. This technique yields polymers with controlled molecular weight and low polydispersity indexes and is feasible with a wide range of monomers. Five different grades of amylopectin‐grafted polymethacrylic acid and polyacrylamide block copolymers have been synthesized via RAFT, by varying the amount of acrylamide employing amylopectin‐based macro chain transfer agent. Graft copolymers have been upgraded as smart responsive graft copolymers, through the incorporation of iron oxide nanoparticles (IONPs) via condensation reaction. The polymeric materials have been extensively characterized by energy‐dispersive X‐ray analysis, Fourier transform infrared spectroscopy, proton magnetic resonance spectroscopy, scanning electron microscopy, ultraviolet‐visible spectroscopy, gel permeation chromatography, transmission electron microscopy, thermogravimetric analysis, and X‐ray diffraction analysis. Normal and responsive graft copolymers have been studied for removal of model contaminant (kaolin), and responsive graft copolymers have been used to remove methylene blue dye (without using any adsorbent) from water by applying external magnetic field. The upgraded block copolymers have shown best performance in wastewater treatment. 相似文献
129.
Yuanbin Zhang Jianbo Hu Rajamani Krishna Lingyao Wang Lifeng Yang Xili Cui Simon Duttwyler Huabin Xing 《Angewandte Chemie (International ed. in English)》2020,59(40):17664-17669
Separation of acetylene (C2H2) from carbon dioxide (CO2) or ethylene (C2H4) is important in industry but limited by the low capacity and selectivity owing to their similar molecular sizes and physical properties. Herein, we report two novel dodecaborate‐hybrid metal–organic frameworks, MB12H12(dpb)2 (termed as BSF‐3 and BSF‐3‐Co for M=Cu and Co), for highly selective capture of C2H2. The high C2H2 capacity and remarkable C2H2/CO2 selectivity resulted from the unique anionic boron cluster functionality as well as the suitable pore size with cooperative proton‐hydride dihydrogen bonding sites (B?Hδ????Hδ+?C≡C?Hδ+???Hδ??B). This new type of C2H2‐specific functional sites represents a fresh paradigm distinct from those in previous leading materials based on open metal sites, strong electrostatics, or hydrogen bonding. 相似文献
130.
A new sol–gel hybrid methyltrimethoxysilane‐chloropropyltriethoxysilane was prepared as sorbent for solid‐phase extraction. The extraction efficiency of the prepared sol–gel hybrid methyltrimethoxysilane‐chloropropyltriethoxysilane was assessed by using three selected organophosphorus pesticides, namely, chlorpyrifos, profenofos, and malathion. Gas chromatography–mass spectrometry was used for detection of organophosphorus pesticides. Several vital parameters were optimized to identify the best extraction conditions. Under the optimum extraction conditions, solid‐phase extraction‐methyltrimethoxysilane‐chloropropyltriethoxysilane method showed good linearity range (0.05‐1 μg/mL) with coefficient of determination more than 0.995. The limits of detection obtained were in the range of 0.01–0.07 μg/mL and limits of quantification ranging from 0.03 to 0.21 μg/mL. The limits of detection obtained for the developed method were 2.3–6.5× lower than the limits of detection of commercial octadecyl silica sorbent. Real samples analysis was carried out by applying the developed method on red apple and purple grape samples. The developed method exhibited good recoveries (88.33–120.7%) with low relative standard deviations ranging from 1.6 to 3.3% compared to commercial octadecyl silica sorbent, which showed acceptable recoveries (70.3–100.2%) and relative standard deviations (6.3–8.8%). The solid‐phase extraction‐methyltrimethoxysilane‐chloropropyltriethoxysilane method is presented as an alternative extraction method for determination of organophosphorus pesticides. 相似文献