Details
| Original language | English |
|---|---|
| Pages (from-to) | 14128-14132 |
| Number of pages | 5 |
| Journal | Chemistry - A European Journal |
| Volume | 23 |
| Issue number | 57 |
| Publication status | Published - 12 Oct 2017 |
Abstract
Crystal formation is a highly debated problem. This report shows that the crystallization of l-(+)-tartaric acid from water follows a non-classical path involving intermediate hydrated states. Analytical ultracentrifugation indicates solution clusters of the initial stages aggregate to form an early intermediate. Terahertz spectroscopy performed during water evaporation highlights a transient increase in the absorption during nucleation; this indicates the recurrence of water molecules that are expelled from the intermediate phase. Besides, a transient resonance at 750 GHz, which can be assigned to a natural vibration of large hydrated aggregates, vanishes after the final crystal has formed. Furthermore, THz data reveal the vibration of nanosized clusters in the dilute solution indicated by analytical ultracentrifugation. Infrared spectroscopy and wide-angle X-ray scattering highlight that the intermediate is not a crystalline hydrate. These results demonstrate that nanoscopic intermediate units assemble to form the first solvent-free crystalline nuclei upon dehydration.
Keywords
- THz spectroscopy, cluster compounds, crystallization process, l-(+)-tartaric acid, non-classical nucleation
ASJC Scopus subject areas
- Chemical Engineering(all)
- Catalysis
- Chemistry(all)
- Organic Chemistry
Cite this
- Standard
- Harvard
- Apa
- Vancouver
- BibTeX
- RIS
In: Chemistry - A European Journal, Vol. 23, No. 57, 12.10.2017, p. 14128-14132.
Research output: Contribution to journal › Article › Research › peer review
}
TY - JOUR
T1 - Crystallization caught in the act with terahertz spectroscopy: non-classical pathway for L-(+)-tartaric acid.
AU - Soltani, A
AU - Gebauer, D
AU - Duschek, L
AU - Fischer, B
AU - Cölfen, H
AU - Koch, M
N1 - Funding information: We thank Prof. Desiraju for careful discussion about the THz results and commenting the manuscript. We thank Rose Rosen-berg, Johanna Scheck, and Masoud Farhadi-Khouzani for the AUC measurements and evaluation, and experimental assistance with WAXS and IR measurements, respectively. A.S. acknowledges funding from the German Academic Exchange Service (DAAD). D.G. thanks the Zukunftkolleg of the University of Konstanz for financial support.
PY - 2017/10/12
Y1 - 2017/10/12
N2 - Crystal formation is a highly debated problem. This report shows that the crystallization of l-(+)-tartaric acid from water follows a non-classical path involving intermediate hydrated states. Analytical ultracentrifugation indicates solution clusters of the initial stages aggregate to form an early intermediate. Terahertz spectroscopy performed during water evaporation highlights a transient increase in the absorption during nucleation; this indicates the recurrence of water molecules that are expelled from the intermediate phase. Besides, a transient resonance at 750 GHz, which can be assigned to a natural vibration of large hydrated aggregates, vanishes after the final crystal has formed. Furthermore, THz data reveal the vibration of nanosized clusters in the dilute solution indicated by analytical ultracentrifugation. Infrared spectroscopy and wide-angle X-ray scattering highlight that the intermediate is not a crystalline hydrate. These results demonstrate that nanoscopic intermediate units assemble to form the first solvent-free crystalline nuclei upon dehydration.
AB - Crystal formation is a highly debated problem. This report shows that the crystallization of l-(+)-tartaric acid from water follows a non-classical path involving intermediate hydrated states. Analytical ultracentrifugation indicates solution clusters of the initial stages aggregate to form an early intermediate. Terahertz spectroscopy performed during water evaporation highlights a transient increase in the absorption during nucleation; this indicates the recurrence of water molecules that are expelled from the intermediate phase. Besides, a transient resonance at 750 GHz, which can be assigned to a natural vibration of large hydrated aggregates, vanishes after the final crystal has formed. Furthermore, THz data reveal the vibration of nanosized clusters in the dilute solution indicated by analytical ultracentrifugation. Infrared spectroscopy and wide-angle X-ray scattering highlight that the intermediate is not a crystalline hydrate. These results demonstrate that nanoscopic intermediate units assemble to form the first solvent-free crystalline nuclei upon dehydration.
KW - THz spectroscopy
KW - cluster compounds
KW - crystallization process
KW - l-(+)-tartaric acid
KW - non-classical nucleation
UR - http://www.scopus.com/inward/record.url?scp=85028965724&partnerID=8YFLogxK
U2 - 10.1002/chem.201702218
DO - 10.1002/chem.201702218
M3 - Article
C2 - 28736825
VL - 23
SP - 14128
EP - 14132
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
SN - 0947-6539
IS - 57
ER -