Dielectric relaxation and proton field-cycling NMR relaxometry study of dimethyl sulfoxide/glycerol mixtures down to glass-forming temperatures

Literature Information

Publication Date 2020-04-02
DOI 10.1039/D0CP00501K
Impact Factor 3.676
Authors

Max Flämig, Liana Gabrielyan, Rafael Minikejew, Shiraz Markarian, Ernst A. Rössler


View Original

Abstract

Mixtures of glycerol and dimethyl sulfoxide (DMSO) are studied by dielectric spectroscopy (DS) and by 1H field-cycling (FC) NMR relaxometry in the entire concentration range and down to glass-forming temperatures (170–323 K). Molecular dynamics is accessed for 0 < xDMSO ≤ 0.64, at higher concentration phase separation occurs. The FC technique provides the frequency dependence of the spin–lattice relaxation rate which is transformed to the susceptibility representation and thus allows comparing NMR and DS results. The DS spectra virtually do not change with xDMSO and T, only the relaxation times become shorter. This is in contrast to the non-associated mixture toluene/quinaldine for which strong spectral changes occur. The FC relaxation spectra of glycerol in solution with DMSO or (deuterated) DMSO-d6 display a bimodal structure with a high-frequency part reflecting rotational and a low-frequency part reflecting translational dynamics. Regarding the rotational contribution in the glycerol/DMSO-d6 mixtures, no spectral change with xDMSO and T is observed. Yet, the non-deuterated mixture reveals a broader relaxation spectrum. Time constants τrot(T) probed by the two techniques complement each, a range 10−11 s < τ < 10 s is covered. The glass transition temperature Tg(xDMSO) is determined, yielding Tg = 149.5 ± 1 K of pure DMSO by extrapolation. Analysing the low-frequency FC NMR spectra allows to determine the diffusion coefficient Dtrans. Its logarithm shows a linear xDMSO-dependence as does lg τrot. The ratio Dtrans/Drot is independent of xDMSO and its low value indicates large separation of translation and rotation. The corresponding unphysically small hydrodynamic radius indicates strong failure of Stokes–Einstein–Debye relation. Such anomaly is taken as characteristics of a 3d hydrogen-bonded network. We conclude, although DMSO is an aprotic liquid the molecule is continuously incorporated in the hydrogen network of glycerol. Both molecules display common dynamics, i.e., no decoupling of the component dynamics is found in contrast to quinaldine/toluene with a similar Tg difference of its components.

Related Literature

Recent advances of hydrogels as smart dressings for diabetic wounds

Xu Wang, Yuhan Yang, Weifeng Zhao, Zhou Zhu, Xibo Pei

2024-01-11 Review Article

DOI: 10.1039/D3TB02355A

Sulfonate compounds embraced from acid copper electroplating baths as innovative additives for alkaline Zn batteries

Katerina Bogomolov, Ekaterina Grishina

2023-10-18 Paper

DOI: 10.1039/D3TA04612E

Contents list

2023-11-15 Front/Back Matter

DOI: 10.1039/D3NP90050A

Contents list

2023-11-14 Front/Back Matter

DOI: 10.1039/D3TA90246C

Nanostructured metal oxide heterojunctions for chemiresistive gas sensors

Shuai Ma

2023-11-02 Review Article

DOI: 10.1039/D3TA04953A

Overall control of the quality consistency of Citri Retriculatae Pericapium by combining HPLC fingerprint, terahertz time-domain spectroscopy and chemometrics

Xinyi Wang, Jiajia Fan, Yong Guo, Lili Lan, Qian Li, Guoxiang Sun

2024-01-10 Paper

DOI: 10.1039/D3NJ04725C

Modular three-component synthesis of 6H-benzochromenone based blue luminogens under catalyst- and solvent-free conditions

Thangavel Pavithra, Karthiyayini Gnanaoli, Deepan Babu Rajkumar, Arulmozhi Puhazhendhi, Soumya Sivalingam, Natarajan Sampath, Subbiah Nagarajan, Vellaisamy Sridharan, C. Uma Maheswari

2024-01-01 Paper

DOI: 10.1039/D3NJ04721K

Chemical capacitance measurements reveal the impact of oxygen vacancies on the charge curve of LiNi0.5Mn1.5O4−δ thin films

Andreas E. Bumberger, Sergej Ražnjević, Zaoli Zhang, Gernot Friedbacher, Juergen Fleig

2023-10-16 Paper

DOI: 10.1039/D3TA05086F

Construction of a metal–oxide interface through alloy nanoparticles to enhance CO2 electrolysis

Xu Huang, Hui Sun, Xuewei He, Yunkai Ruan, Lizhen Gan

2023-12-13 Paper

DOI: 10.1039/D3NJ04854C

You might also like

Compound Q&A

How should waste containing N-Methoxy-N-methyl-1,3-thiazole-5-carboxamide (CAS: 898825-89-3) be handled?

Waste containing N-Methoxy-N-methyl-1,3-thiazole-5-carboxamide (CAS: 898825-89-3...

898825-89-3N-Methoxy-N-methyl-1...
Compound Q&A

How should N-(4-Biphenylyl)dibenzo[b,d]furan-4-amine (CAS: 1318338-47-4) be stored?

N-(4-Biphenylyl)dibenzo[b,d]furan-4-amine should be stored in a tightly sealed c...

1318338-47-4N-(4-Biphenylyl)dibe...
Compound Q&A

What is the market or research trend for 3-Acetamido-5-amino-2,4,6-triiodobenzoic acid (CAS: 1713-07-1)?

The market for 3-Acetamido-5-amino-2,4,6-triiodobenzoic acid (CAS: 1713-07-1) is...

1713-07-13-Acetamido-5-amino-...
Compound Q&A

How should Benzyl 2-O-acetyl-3,4,6-tri-O-benzyl-beta-D-galactopyranoside (CAS: 61820-03-9) be stored?

Benzyl 2-O-acetyl-3,4,6-tri-O-benzyl-beta-D-galactopyranoside (CAS: 61820-03-9) ...

61820-03-9Benzyl 2-O-acetyl-3,...
Compound Q&A

What regulatory guidelines apply to 2-Ethylpiperazine dihydrochloride (CAS: 438050-52-3)?

2-Ethylpiperazine dihydrochloride (CAS: 438050-52-3) is regulated under the Glob...

438050-52-32-Ethylpiperazine di...
Compound Q&A

What regulatory guidelines apply to 1,1'-[1,3-Phenylenebis(methylene)]bis(3-methyl-1H-pyrrole-2,5-dione) (CAS: 119462-56-5)?

1,1'-[1,3-Phenylenebis(methylene)]bis(3-methyl-1H-pyrrole-2,5-dione) (CAS: 11946...

119462-56-51,1'-[1,3-Phenyleneb...
Compound Q&A

Are there alternatives to 5-Fluoro-2-(1-pyrrolidinyl)pyridine (CAS: 1287217-79-1) in synthesis?

Several alternatives can be used in the synthesis of 5-Fluoro-2-(1-pyrrolidinyl)...

1287217-79-15-Fluoro-2-(1-pyrrol...
Compound Q&A

What precautions should be taken when handling 6-Bromoimidazo[1,2-a]pyridin-8-amine (CAS: 676371-00-9)?

When handling 6-Bromoimidazo[1,2-a]pyridin-8-amine, it is important to wear appr...

676371-00-96-Bromoimidazo[1,2-a...
Compound Q&A

Are there alternatives to (2S,4R)-4-(4-Nitrobenzyl)pyrrolidine-2-carboxylic acid hydrochloride (CAS: 1049740-22-8) in synthesis?

Alternatives to (2S,4R)-4-(4-Nitrobenzyl)pyrrolidine-2-carboxylic acid hydrochlo...

1049740-22-8(2S,4R)-4-(4-Nitrobe...

Source Journal

Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
Articles per Year: 3036

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

Recommended Compounds

Recommended Suppliers

Disclaimer
This page provides academic journal information for reference and research purposes only. We are not affiliated with any journal publishers and do not handle publication submissions. For publication-related inquiries, please contact the respective journal publishers directly.
If you notice any inaccuracies in the information displayed, please contact us at support@chemtradehub.com. We will promptly review and address your concerns.