i want to do a experiment in a solvent which can hinder hydrogen-bonding. i know DMSO is one choice, however, the purification later is difficult for me , so i would like to choice dmf as the solvent,which has lower boiling point. does it work like dmso which is a h-bonding acceptor? thanks very much
Dear Huang,
DMF is considered as a hydrogen bond acceptor:
1-https://books.google.ps/books?id=1oEzkBplw8cC&pg=PA36&lpg=PA36&dq=DMF+is+a+hydrogen-bonding+acceptor+solvent&source=bl&ots=8JNUiBi3RT&sig=nsJgELj-jXZHxtQodXFKRwE0k8A&hl=en&sa=X&ved=0ahUKEwiz6p3CwOHLAhUMcBoKHYkPDkUQ6AEIIjAC#v=onepage&q=DMF%20is%20a%20hydrogen-bonding%20acceptor%20solvent&f=false
2-N, N-dimethylformamide (DMF) is a ‘universal’ solvent with the simplest amide structure. DMF has different interactions with many polymers and biomolecules. It is therefore necessary to study systematically the interactions in DMF itself first. In this study, both FT-IR and two molecular theoretical methods (MP2 and DFT/B3LYP) were used to study various hydrogen bonding interactions in DMF molecules based on its weak H-bonding donors CH/CH3 and strong H-bonding acceptor C = O. The possible H-bonding donors and acceptors in DMF molecules were first analysed followed by modelling the effect of different structural environments on vC = O bands in infrared spectra. Finally, H-bonding properties including distance, angles and the energy as well as the probability of H-bonding patterns were obtained. The results showed that there exist five possible different weak types of H-bonding dimers; among them, three dimers consist of a pair of weak H-bonds, whereas two other dimers have two pairs of H-bonds, leading to 14 (including eight different) H-bonds. Two types of dimers were dominant, whereas three others can be omitted.
http://www.tandfonline.com/doi/abs/10.1080/08927022.2013.775438
3-The hydrogen bonding interactions between cysteine and N,N-dimethylformamide (DMF) were studied at the extended hybrid functional DFT-X3LYP/6-311++G(d,p) level regarding their geometries, energies, vibrational frequencies, and topological features of the electron density. The quantum theory of atoms in molecules (QTAIM) and natural bond orbital (NBO) analyses were employed to elucidate the interaction characteristics in the complexes. The results show that two intermolecular hydrogen bonds (H-bonds) are formed in one complex except few complexes with one intermolecular H-bond. The H-bonds involving O atom of DMF as H-bond acceptor usually are red-shifting H-bonds, while the blue-shifting H-bond usually involve methyl of DMF or methenyl of cysteine moiety as H-bond donors. Both hydrogen bonding interaction and structural deformation play important roles in the relative stabilities of the complexes. Due to the π-bond cooperativity, the strongest H-bond is formed between hydroxyl of cysteine moiety and O atom of DMF, however, the serious deformation counteract the hydrogen bonding interaction to a great extent. The complex involves a stronger hydrogen bonding interaction as well as the smaller deformation is the most stable one. The electron density (ρb) as well as its Laplacian (∇2ρb) at the H-bond critical point predicted by QTAIM is strongly correlated with the H-bond structural parameter (δR H···Y) and the second-perturbation energies E(2) in the NBO scheme.
http://link.springer.com/article/10.1007%2Fs11224-010-9689-4
4-Structures and Hydrogen Bonding Analysis of N,N-Dimethylformamide and N,N-Dimethylformamide−Water Mixtures by Molecular Dynamics Simulations
Yi Lei , Haoran Li ,* Haihua Pan , and Shijun Han
Department of Chemistry, Zhejiang University, Hangzhou 310027, People's Republic of China
J. Phys. Chem. A, 2003, 107 (10), pp 1574–1583
DOI: 10.1021/jp026638+
Publication Date (Web): February 11, 2003
Copyright © 2003 American Chemical Society
Abstract
Pure N,N-dimethylformamide (DMF) and DMF−water mixtures are studied by molecular dynamics (MD) simulations. An OPLS all-atom force field is used for the simulation of DMF, revealing the local order and formation of the weak hydrogen bond of C−H···O, and TIP5P is adopted for the simulation of water and is compared with the latest X-ray and neutron diffraction experiment. Solution properties of DMF−water mixtures are investigated using radial distribution functions (RDFs) and hydrogen bonding properties. A significant composition dependence, which is attributed to the prevailing influence of the strongly polarizable amido of DMF and the clustering feature of water, is observed in the simulation. In addition, NMR experiments of DMF−water mixtures are used for the discussion of the hydrogen bonding effect. The results of the simulation are adopted to explain the NMR experiments by hydrogen bonding analysis. As a result, the magnetic anisotropy of the amido group is considered to play an important role in the chemical shift.
http://pubs.acs.org/doi/abs/10.1021/jp026638%2B
Hoping this will be helpful,
Rafik
Dear Huang,
DMF is considered as a hydrogen bond acceptor:
1-https://books.google.ps/books?id=1oEzkBplw8cC&pg=PA36&lpg=PA36&dq=DMF+is+a+hydrogen-bonding+acceptor+solvent&source=bl&ots=8JNUiBi3RT&sig=nsJgELj-jXZHxtQodXFKRwE0k8A&hl=en&sa=X&ved=0ahUKEwiz6p3CwOHLAhUMcBoKHYkPDkUQ6AEIIjAC#v=onepage&q=DMF%20is%20a%20hydrogen-bonding%20acceptor%20solvent&f=false
2-N, N-dimethylformamide (DMF) is a ‘universal’ solvent with the simplest amide structure. DMF has different interactions with many polymers and biomolecules. It is therefore necessary to study systematically the interactions in DMF itself first. In this study, both FT-IR and two molecular theoretical methods (MP2 and DFT/B3LYP) were used to study various hydrogen bonding interactions in DMF molecules based on its weak H-bonding donors CH/CH3 and strong H-bonding acceptor C = O. The possible H-bonding donors and acceptors in DMF molecules were first analysed followed by modelling the effect of different structural environments on vC = O bands in infrared spectra. Finally, H-bonding properties including distance, angles and the energy as well as the probability of H-bonding patterns were obtained. The results showed that there exist five possible different weak types of H-bonding dimers; among them, three dimers consist of a pair of weak H-bonds, whereas two other dimers have two pairs of H-bonds, leading to 14 (including eight different) H-bonds. Two types of dimers were dominant, whereas three others can be omitted.
http://www.tandfonline.com/doi/abs/10.1080/08927022.2013.775438
3-The hydrogen bonding interactions between cysteine and N,N-dimethylformamide (DMF) were studied at the extended hybrid functional DFT-X3LYP/6-311++G(d,p) level regarding their geometries, energies, vibrational frequencies, and topological features of the electron density. The quantum theory of atoms in molecules (QTAIM) and natural bond orbital (NBO) analyses were employed to elucidate the interaction characteristics in the complexes. The results show that two intermolecular hydrogen bonds (H-bonds) are formed in one complex except few complexes with one intermolecular H-bond. The H-bonds involving O atom of DMF as H-bond acceptor usually are red-shifting H-bonds, while the blue-shifting H-bond usually involve methyl of DMF or methenyl of cysteine moiety as H-bond donors. Both hydrogen bonding interaction and structural deformation play important roles in the relative stabilities of the complexes. Due to the π-bond cooperativity, the strongest H-bond is formed between hydroxyl of cysteine moiety and O atom of DMF, however, the serious deformation counteract the hydrogen bonding interaction to a great extent. The complex involves a stronger hydrogen bonding interaction as well as the smaller deformation is the most stable one. The electron density (ρb) as well as its Laplacian (∇2ρb) at the H-bond critical point predicted by QTAIM is strongly correlated with the H-bond structural parameter (δR H···Y) and the second-perturbation energies E(2) in the NBO scheme.
http://link.springer.com/article/10.1007%2Fs11224-010-9689-4
4-Structures and Hydrogen Bonding Analysis of N,N-Dimethylformamide and N,N-Dimethylformamide−Water Mixtures by Molecular Dynamics Simulations
Yi Lei , Haoran Li ,* Haihua Pan , and Shijun Han
Department of Chemistry, Zhejiang University, Hangzhou 310027, People's Republic of China
J. Phys. Chem. A, 2003, 107 (10), pp 1574–1583
DOI: 10.1021/jp026638+
Publication Date (Web): February 11, 2003
Copyright © 2003 American Chemical Society
Abstract
Pure N,N-dimethylformamide (DMF) and DMF−water mixtures are studied by molecular dynamics (MD) simulations. An OPLS all-atom force field is used for the simulation of DMF, revealing the local order and formation of the weak hydrogen bond of C−H···O, and TIP5P is adopted for the simulation of water and is compared with the latest X-ray and neutron diffraction experiment. Solution properties of DMF−water mixtures are investigated using radial distribution functions (RDFs) and hydrogen bonding properties. A significant composition dependence, which is attributed to the prevailing influence of the strongly polarizable amido of DMF and the clustering feature of water, is observed in the simulation. In addition, NMR experiments of DMF−water mixtures are used for the discussion of the hydrogen bonding effect. The results of the simulation are adopted to explain the NMR experiments by hydrogen bonding analysis. As a result, the magnetic anisotropy of the amido group is considered to play an important role in the chemical shift.
http://pubs.acs.org/doi/abs/10.1021/jp026638%2B
Hoping this will be helpful,
Rafik
There are solvent parameters that measure solvents as h-bond acceptors and h-bond donors. The first is the Kamlet-Taft alpha and beta parameters. The second is Hunter's solvation model. Both of which can be "googled" or researched easily.
Other solvents could also be hydrogen acceptors: dimethoxyethane, tetrahydrofuran, diethyl ether. And they are also easier to clean than DMF.
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