Cited by 33Spectroscopy and Quantum Chemical StudiesAdvanced NMR Techniques and ApplicationsElectrostatics and Colloid Interactions

Phosphates form spectroscopically dark state assemblies in common aqueous solutions

Open access
Straub, Joshua S., Nowotarski, Mesopotamia S., Lu, Jiaqi, Sheth, Tanvi, Jiao, Sally, Fisher, Matthew P. A., Shell, M. Scott, Helgeson, Matthew E. +2 more·2023·Proceedings of the National Academy of Sciences

Abstract

Phosphates and polyphosphates play ubiquitous roles in biology as integral structural components of cell membranes and bone, or as vehicles of energy storage via adenosine triphosphate and phosphocreatine. The solution phase space of phosphate species appears more complex than previously known. We present nuclear magnetic resonance (NMR) and cryogenic transmission electron microscopy (cryo-TEM) experiments that suggest phosphate species including orthophosphates, pyrophosphates, and adenosine phosphates associate into dynamic assemblies in dilute solutions that are spectroscopically "dark." Cryo-TEM provides visual evidence of the formation of spherical assemblies tens of nanometers in size, while NMR indicates that a majority population of phosphates remain as unassociated ions in exchange with spectroscopically invisible assemblies. The formation of these assemblies is reversibly and entropically driven by the partial dehydration of phosphate groups, as verified by diffusion-ordered spectroscopy (DOSY), indicating a thermodynamic state of assembly held together by multivalent interactions between the phosphates. Molecular dynamics simulations further corroborate that orthophosphates readily cluster in aqueous solutions. This study presents the surprising discovery that phosphate-containing molecules, ubiquitously present in the biological milieu, can readily form dynamic assemblies under a wide range of commonly used solution conditions, highlighting a hitherto unreported property of phosphate's native state in biological solutions.

The claims and statistics of this paper haven’t been checked yet.

Run the check — free, no account needed. It reads the open-access text and checks the sources it cites.

A few free checks a day · papers already verified open instantly · results are public

Integrity signals

Registry

Crossref · 10.1073/pnas.2206765120

Cites

47 of 47 references verified0 citation errors · 0 not checkable

Statistics

Claims the paper makes

The claims and statistics of this paper haven’t been checked yet.

Run the check — free, no account needed. It reads the open-access text and checks the sources it cites.

A few free checks a day · papers already verified open instantly · results are public

Claims other papers make about this one

Each is checked against this paper’s own text: does it say what the citing paper says it does?

  • Experiments on Posner clusters have been conducted, but their coherence has not yet been studied experimentally.

    “Furthermore, experiments on Posner clusters have been conducted to provide insights into their properties, but their coherence has not yet been studied experimentally [92,93,94,95,96].”

Self-check

Percentages, sums and reported differences re-computed from the paper’s own numbers.

The self-check needs the paper’s full text.

Cites

Flagged first, then by citations

Cited by

Sorted by citations

Authors
Straub, J. S., Nowotarski, M. S., Lu, J., Sheth, T., Jiao, S., Fisher, M. P. A., Shell, M. S., Helgeson, M. E., Jerschow, A., & Han, S.
Affiliations
  • University of California, Santa Barbara (US)
  • New York University (US)
Corresponding author
  • Jerschow, Alexej
  • Han, Songi
Venue
Proceedings of the National Academy of Sciences
Published
2022-12-29
Volume
120
Issue
1
Pages
e2206765120-e2206765120
ISSN
  • 0027-8424 (ISSN-L)
  • 1091-6490
OpenAlex
W4313333079
Cited by
33
References
47
Citations by year
2026: 3 · 2025: 8 · 2024: 18 · 2023: 3 · 2022: 1
FWCI
3.06
Type
journal article
Language
en
Open access
Locations
  • Proceedings of the National Academy of Sciences (publishedVersion, cc-by)
  • PubMed Central (publishedVersion, cc-by)
  • PubMed (publishedVersion)
  • eScholarship (California Digital Library) (submittedVersion, cc-by)
Funders
  • Heising-Simons Foundation (444063-57611-3)
  • National Science Foundation (1650114, CHE 2108205, CHE 2004217, MRI-1920299, DMR 1720256, OAC-1925717)
Topics
  • Physical Sciences › Physics and Astronomy › Atomic and Molecular Physics, and Optics › Spectroscopy and Quantum Chemical Studies
  • Physical Sciences › Chemistry › Spectroscopy › Advanced NMR Techniques and Applications
  • Physical Sciences › Chemistry › Physical and Theoretical Chemistry › Electrostatics and Colloid Interactions
Keywords
phosphate, polyphosphate, orthophosphate, pyrophosphate, adenosine phosphates, dehydration, multivalent interactions, entropic driving force, aqueous chemistry, energy storage
MeSH terms
Adenosine Triphosphate, Magnetic Resonance Spectroscopy, Phosphates, Polyphosphates, Solutions, Water, Microscopy, Electron, Transmission

About these checks

Registry, retraction, Cites and statistics results are computed, not judged, with one exception: a printed reference that no index lists is read once by a model before it counts as a citation error. Claims are extracted by a model and kept only when their quote appears verbatim in the text; each cited source is then checked, with a model’s help, for whether it says what the claim relies on. Those verdicts can be wrong — read the claim’s quote and the cited source before relying on one.

Statistics and arithmetic are recomputed, not judged.

Confidence bands are shown only for fields calibrated on our annotated test set. None is calibrated yet, so no band is shown.

What counts as a claim ›How we measure confidence ›How we check this ›

Are you an author, or do you see a problem with this page? Request a review