Due to their high gyromagnetic ratio, there is considerable interest in measuring distances and correlations involving protons, but such measurements are compounded by the simultaneous recoupling of chemical shift anisotropy (CSA). This secondary recoupling adds additional modulations to the signal intensities that ultimately lead to t-noise and signal decay. Recently, Venkatesh et al. demonstrated that the addition of CSA refocusing periods during H-X dipolar recoupling led to sequences with far higher stability and performance. Herein, we describe a related effort and develop a symmetry-based recoupling sequence that continually refocuses the H CSA. This sequence shows superior performance to the regular and t-noise eliminated D-HMQC sequences in the case of spin-1/2 nuclei and comparable performance to the later for half-integer quadrupoles.
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http://dx.doi.org/10.1016/j.ssnmr.2022.101807 | DOI Listing |
Biochemistry
January 2025
Department of Chemistry, Washington University in St. Louis, One Brookings Drive, St. Louis, Missouri 63130, United States.
Branch-point syntheses in nonribosomal peptide assembly are rare but useful strategies to generate tripodal peptides with advantageous hexadentate iron-chelating capabilities, as seen in siderophores. However, the chemical logic underlying the peptide branching by nonribosomal peptide synthetase (NRPS) often remains complex and elusive. Here, we review the common strategies for the biosynthesis of branched nonribosomal peptides (NRPs) and present our biochemical investigation on the NRPS-catalyzed assembly of fimsbactin A, a branched mixed-ligand siderophore produced by the human pathogenic strain .
View Article and Find Full Text PDFAstrobiology
January 2025
NASA Goddard Space Flight Center, Greenbelt, Maryland, USA.
Meteoritic impacts on planetary surfaces deliver a significant amount of energy that can produce prebiotic organic compounds such as cyanides, which may be a key step to the formation of biomolecules. To study the chemical processes of impact-induced organic synthesis, we simulated the physicochemical processes of hypervelocity impacts (HVI) in experiments with both high-speed C projectiles and laser ablation. In the first approach, a C beam was accelerated to collide with ammonium nitrate (NHNO) to reproduce the shock process and plume generation of meteoritic impacts on nitrogen-rich planetary surfaces.
View Article and Find Full Text PDFOrg Lett
January 2025
Key Laboratory of Precision and Intelligent Chemistry, University of Science and Technology of China, Hefei, Anhui 230026, China.
A 1,1-hydroboration of alkynylgermanes with unique -Ge/B stereochemistry under transition-metal-free conditions is reported. Mechanistic studies suggest that a pathway involving α-boration followed by a stepwise 1,2-Ge/H shift on the intermediate structurally lies between an alkyne-Ge π complex and a typical vinyl cation. The resulting Ge/B bimetallic modules, along with a /Ge/B trimetallic variant, can be conveniently transformed into trisubstituted olefins through iterative divergent cross-coupling.
View Article and Find Full Text PDFAdv Mater
January 2025
Tsinghua Shenzhen International Graduate School, Tsinghua University, Shenzhen, 518055, China.
Commercialization of lithium-sulfur (Li-S) batteries is largely limited by polysulfide shuttling and sluggish kinetics. Herein, 2D nanochannel interlayer composed of alternatively-stacked porous silica nanosheets (PSN) and TiCT-MXene are developed. The 2D nanochannels with selective cation transport characteristics facilitate lithium ion rapid transport, while reject the translocation of polysulfide anions across the separator.
View Article and Find Full Text PDFFerroelectric polarization is considered to be an effective strategy to improve the oxygen evolution reaction (OER) of photoelectrocatalysis. The primary challenge is to clarify how the polarization field controls the OER dynamic pathway at a molecular level. Here, electrochemical fingerprint tests were used, together with theoretical calculations, to systematically investigate the free energy change in oxo and hydroxyl intermediates on TiO-BaTiO core-shell nanowires (BTO@TiO) upon polarization in different pH environments.
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