Stringent requirement for electrophiles in the facile solvolytic hydrolysis of neutral sulfate ester salts

Goren, Mayer B.; Kochansky, Mary E.

doi:10.1021/jo00960a016

Cited by 27 publications

(10 citation statements)

References 2 publications

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“…The conversion of inorganic SO 4 = observed in these experiments suggests that the organosulfates are stable during the vaporization or ionization of the AMS detection process. Although hydrolysis of the ester bond may also occur, it typically arises after intense heating in H 2 O; it is known that even under harsh hydrolytic conditions many sulfate esters, including those of steroids and simple alcohols, are highly resistant to hydrolysis [ Goren and Kochansky , 1973; Young and Maw , 1958]. The apparent stability of organosulfates suggests that the conventional filter‐based inorganic SO 4 = measurements using aqueous extraction methods probably underestimate the total SO 4 = burden in atmospheric aerosols.…”

Section: Resultsmentioning

confidence: 99%

Organosulfate formation during the uptake of pinonaldehyde on acidic sulfate aerosols

Liggio¹,

Li²

2006

Geophysical Research Letters

139

170

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[1] Organosulfates are observed in studies of pinonaldehyde reactions with acidic sulfate aerosols using aerosol mass spectrometry, during which a significant fraction of the pinonaldehyde reaction products were found to consist of organosulfate compounds that account for 6 -51% of the initial SO 4 = mass. Resultant aerosol mass spectra were consistent with proposed sulfate ester mechanisms, which likely form stable products. The existence of organosulfates was also confirmed in studies of the reaction system in bulk solution. The formation of organosulfates suggests that conventional inorganic SO 4 = chemical analysis may underestimate total SO 4 = mass in ambient aerosols. Citation: Liggio, J., and S.-M. Li (2006), Organosulfate formation during the uptake of pinonaldehyde on acidic sulfate aerosols, Geophys.

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Section: Resultsmentioning

confidence: 99%

Organosulfate formation during the uptake of pinonaldehyde on acidic sulfate aerosols

Liggio¹,

Li²

2006

Geophysical Research Letters

139

170

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“…Hydrolysis of sulfate esters requires an elevated temperature (ca 100 C) even in strongly acidic solution [69, 70], and Ba 2+ does not precipitate the sulfate from sulfate esters without prior hot hydrolysis [71]. The estimates of average soluble blood cell [SO 4 2− ] were carried out at room temperature in pH 2 solution, and the BaSO 4 precipitate was removed immediately by centrifugation.…”

Section: Resultsmentioning

confidence: 99%

XAS spectroscopy, sulfur, and the brew within blood cells from Ascidia ceratodes

Frank

Hedman

2014

Journal of Inorganic Biochemistry

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We report the first use of K-edge x-ray absorption spectroscopy (XAS) as a direct spectroscopic probe of pH and cytosolic emf within living cells. A new accuracy metric of model-based fits to K-edge spectra is further developed. Sulfur functional groups in three collections of living blood cells and one sample of cleared blood plasma from the tunicate Ascidia ceratodes were speciated using K-edge XAS. Cysteine and cystine, the preferred thiol-disulfide model, averaged about 12% of total sulfur. Sulfate monoesters and cyclic diesters unexpectedly constituted 36% of blood cell sulfur. Soluble sulfate averaged about 25% across the three blood cell samples, while the ratio of SO42− to HSO4− implied average signet ring vacuolar pH values of 0.85, 1.4, or 3.1. Intracellular (VSO4)+ was unobserved, while [V(RSO3)n](3−n)+ was detected in the two lowest pH blood cell samples. About 5% of sulfur was distributed as mono- or dibenzothiophene or ethylene-epi-sulfide, or as a thiadiazole reminiscent of the polycarpathiamines. Blood plasma was dominated by sulfate (83%), but with 15% of an alkylsulfate ester and about 2% of low-valent sulfur. Gravimetric analysis of soluble sulfate yielded average concentrations of blood cell sulfur. Average [cysteine] and [cystine] (ranging ~10–30 mM and ~20–90 mM, respectively) implied a blood-cell cytosolic emf values of approximately −0.20 V. High cellular [cysteine] is consistent with the proposed model for enzymatic reduction of vanadate by endogenous thiol, wherein the trajectory of metal site-symmetry is controlled and directed through to a thermodynamically favored 7-coordinate V(III) product.

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“…The latter could anyway be 9 3.03 m, 7.50; 6.7-7. identified via MS ( Figure 3, panel C). Attempts to desulfate the final mixture with H 2 SO 4 solutions following described procedures [17] failed, giving rise to product degradation. To limit the extent of this side reaction, 10% of thiocresol was added as the appropriate scavenger for Pmc protecting groups [18], obtaining 2% of the undesired product.…”

Section: Resultsmentioning

confidence: 99%

Solid-phase synthesis of MEN 11270, a new cyclic peptide kinin B2 receptor antagonist

et al. 2000

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Stringent requirement for electrophiles in the facile solvolytic hydrolysis of neutral sulfate ester salts

Cited by 27 publications

References 2 publications

Organosulfate formation during the uptake of pinonaldehyde on acidic sulfate aerosols

Organosulfate formation during the uptake of pinonaldehyde on acidic sulfate aerosols

XAS spectroscopy, sulfur, and the brew within blood cells from Ascidia ceratodes

Solid-phase synthesis of MEN 11270, a new cyclic peptide kinin B2 receptor antagonist

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