Dissolution-dynamic nuclear polarization (d-DNP) {is a|is really a|is actually a|can be a|is often a|is usually a} state-of-the-art {technology|technologies} {that can|that may|that will|that could|which will|which can} {dramatically|significantly|drastically|substantially|considerably} {enhance|improve|boost} the detection sensitivity of nuclear magnetic resonance (NMR). DNP NMR has been applied to {small|little|tiny|modest|smaller|compact} molecules with {stable|steady} isotopes and has been {used|utilized|employed|utilised|applied|made use of} to {obtain|acquire|get|receive} metabolic and physiological {information|info|details|data|facts|information and facts} in vivo. {However|Nevertheless|Nonetheless|Even so|On the other hand|Having said that}, the hyperpolarized state exponentially decays back {to the|towards the|for the} thermal equilibrium state, {depending on|based on|according to} the spin-lattice relaxation time (T1). This signal decay has remained {a major|a significant} {problem|issue|difficulty|dilemma|challenge|trouble} {associated|related|connected|linked} with this {technology|technologies}. {Therefore|Consequently|As a result|For that reason|Thus|Hence}, DNP NMR molecular probes {useful|helpful|beneficial|valuable} for in vivo {analysis|evaluation} {have been|happen to be|have already been} {limited|restricted} to naturally occurring {small|little|tiny|modest|smaller|compact} molecules that inherently show {long|lengthy|extended} T1. {While|Whilst|Although|Even though|When|Though} peptides are promising targets for DNP NMR {studies|research}, {because of|due to|as a result of} the limitation in T1, DNP NMR molecular probes applicable in vivo {have been|happen to be|have already been} {limited|restricted} to amino acids or dipeptides. Herein we propose a 13C-labeling {strategy|technique|method|approach|tactic} to {utilize|make use of|use} the C-terminal [1-13C]Gly-d2 residue for realizing {long|lengthy|extended} T1 in peptides. Structure-based T1 relaxation {analysis|evaluation} of amino acids and peptides revealed that (1) T1 {does not|doesn’t|will not} {decrease|reduce|lower} monotonically with {increasing|growing|escalating|rising} molecular weight and ({2|two}) T1 {is not|isn’t|just isn’t|is just not|will not be} {significantly|considerably|substantially|drastically} {affected|impacted} by a side chain {on the|around the} neighboring amino acid residue. These findings {suggest|recommend} that the C-terminal [1-13C]Gly-d2 residue affords sufficiently {long|lengthy|extended} T1 for biological {uses|utilizes|makes use of}, even in oligopeptides, and {allowed|permitted} us to {develop|create} 13C-b- casomorphin-5 (Tyr-Pro-Phe-Pro-[1-13C]Gly-d2, T1 = 24 ± {4|four} s at {3|three} T in H2O) and 13C-glutathione (g-Glu-Cys-[1-13C]Gly-d2, T1 = 58 ± {3|three} s at {3|three} T in H2O) as DNP NMR probes with {long|lengthy|extended} T1. We succeeded in in vivo detection of enzymatic conversions {of these|of those} two probes. These {results|outcomes|final results|benefits} demonstrate the utility of our {strategy|technique|method|approach|tactic} and would contribute to {further|additional} expansion {of the|from the|in the|on the|with the|of your} substrate scope for DNP applications. Benzaldoxime Purity 2-Bromo-5-(difluoromethyl)pyrazine Chemscene PMID:35567400
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