Insights into the Post‐Translational Methylation of Arginine from Studies of Guanidinium–Water Nanodroplets

McQuinn, Keri; McIndoe, J. Scott; Hof, Fraser

doi:10.1002/chem.200800101

Cited by 16 publications

(15 citation statements)

References 48 publications

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“…The disagreement of our gas-phase calculations and solution-phase NMR spectroscopy data, taken together with the large deviations from the expected enthalpy and entropy of binding, suggest an anomalous solvation effect that operates only in the case of aDMA. We and others have looked, and failed to find any significant solvation differences between aDMA and sDMA in prior studies, [26,27] and the origins of the differences that we observe for the binding of these two isomers to 1 remain unclear.…”

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confidence: 48%

“…[22] More interesting is the comparison to arginine, because it is also cationic and is also subject to post-translational methylations that render it more hydrophobic than its parent unmethylated form. [26,27] Arginine can exist in nature as three distinct methylated forms: monomethylarginine (MMA), symmetric dimethylarginine (sDMA), and asymmetric dimethylarginine (aDMA; Figure 1). [2,28] For Arg, as for Lys, our studies of binding to 1 show that affinity increases with increasing methylation (Table 1).…”

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confidence: 99%

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A Simple Calixarene Recognizes Post‐translationally Methylated Lysine

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A Simple Calixarene Recognizes Post‐translationally Methylated Lysine

et al. 2009

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“…This is consistent with previous reports on the hydration of the gdn compounds. 23-27 The formation of gdn dimers 23-25,50 possibly accounts for this low hydration level.…”

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confidence: 99%

UV Resonance Raman and DFT Studies of Arginine Side Chains in Peptides: Insights into Arginine Hydration

2013

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We examined the UV resonance Raman (UVRR) spectra of four models of the arg side chain, guanidinium (gdn), ethylguanidinium (EG), arginine (arg) and Ac-arg-OMe (AAO) in H2O and D2O, in order to identify spectral markers that report on the environment of the arg side chain. To elucidate the resonance Raman enhancement mechanism of the arg side chain, we used DFT to calculate the equilibrium geometries of the electronic ground state and the first excited state. We determined the vibrational mode frequencies of the ground state and the first derivative of the first electronic excited state potential energy with respect to each vibrational normal mode of the electronic ground state at the electronic ground state equilibrium geometry. The DFT calculations and the potential energy distributions reveal that, in addition to the gdn group C-N stretching vibrations, the C-N bond stretching vibration of the gdn group-methylene linkage is also strongly resonance enhanced in EG, arg and AAO. From the UVRR spectra, we find that the Raman cross section and frequency of the ~1170 cm−1 vibration of the arg side chain depends on its hydration state and can be used to determine the hydration state of the arg side chain in peptides and proteins. We examined the hydration of the arg side chain in two polyala peptides and found that in the α-helical conformation the arg side chain in the AEP peptide (sequence: A9RA3EA4RA2) is less hydrated than that in the AP peptide (sequence: A8RA4RA4RA2).

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“…Posey's system was rediscovered by Vékey [45], who also used saturated curtain gas to generate heavily solvated ions (2 to 100 solvent molecules). Indeed, if the solvent is water, the experiment is even easier, as the source can simply be set up under "cold-flooding" conditions (low temperature, high sample flow rate, low desolvation gas flow rate) and ions, whether singly or multiply charged, can be observed as highly hydrated species [46,47].…”

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confidence: 99%

Gas-phase reactivity of ruthenium carbonyl cluster anions

Henderson

Kwok

McIndoe

2008

J. Am. Soc. Mass Spectrom.

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Partially-ligated anionic ruthenium carbonyl clusters react with alkenes, arenes, and alkanes in the gas phase; the products undergo extensive C-H activation and lose dihydrogen and carbon monoxide under collision-induced dissociation conditions. Triethylsilane and phenylsilane are also reactive towards the unsaturated clusters, and oxygen was shown to rapidly break down the cluster core by oxidative cleavage of the metal-metal bonds. These qualitative gas-phase reactivity studies were conducted using an easily-installed and inexpensive modification of a commercial electrospray ionization mass spectrometer. Interpretation of the large amounts of data generated in these studies is made relatively straightforward by employing energydependent electrospray ionization mass spectrometry (EDESI-MS). here are many examples of reactions between molecules and metal cluster ions in the gas phase, and the area has been well reviewed [1,2]. Of intense current interest are those systems in which catalytic reactions (homogeneous or heterogeneous) are modeled [3,4]. The information gleaned from these studies is particularly advantageous in systems where little or nothing is known about reactivity. Interest in the area stems from the fact that the chemistry of highly reactive, metallic nanoparticles is fundamentally difficult to study, and it is high surface area metals and metal oxides that are responsible for the most industrially important heterogeneous catalytic reactions. Any means of gaining insight into the mechanism of these reactions may prove useful in designing more efficient and more selective catalysts. The absence of surfaces, solvents, and counterions make the gas phase a considerably less complicated environment than that found in solution. Just how good the correspondence is between gas-phase and solution results is subject to active debate [5][6][7], but there is little argument that the gas phase benefits from the reduction in the number of variables, especially when dealing with complicated systems. The gas-phase reactivity of a wide variety of partially ligated clusters have been studied, including oxides [8 -11] [18]. and even some mixed species [19,20]. However, for the most part, the extent of ligation is low and, correspondingly, so is the relevance to solution chemistry. Homogeneous catalysis is generally performed under conditions that are relatively mild and in which the catalysts maintain a (near) complete coordination sphere, so the comparison with nearly naked gas-phase metal clusters is somewhat tenuous (though interestingly, may more closely approximate the conditions of heterogeneous catalysis, which frequently involves unligated metal particles on a surface) [21,22].Some work has also been done on partially ligated carbonyl clusters; an early paper by Ridge [23] example by Ridge demonstrated that in a Fourier transform ion cyclotron resonance mass spectrometer (FTICR-MS), partially ligated cationic transition-metal carbonyl clusters generated by electron ionization reacted readily with cycl...

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Insights into the Post‐Translational Methylation of Arginine from Studies of Guanidinium–Water Nanodroplets

Cited by 16 publications

References 48 publications

A Simple Calixarene Recognizes Post‐translationally Methylated Lysine

A Simple Calixarene Recognizes Post‐translationally Methylated Lysine

UV Resonance Raman and DFT Studies of Arginine Side Chains in Peptides: Insights into Arginine Hydration

Gas-phase reactivity of ruthenium carbonyl cluster anions

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