Conformational behaviour of trimethyl phosphate studied by infrared spectroscopy

Streck, Roman; Barnes, Austin J.; Herrebout, Wouter A.; Veken, B.J. van der

doi:10.1016/0022-2860(95)09106-8

Cited by 35 publications

(19 citation statements)

References 10 publications

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“…TMP is a simple phosphate ester that has been extensively studied using a variety of methods including vibrational spectroscopy [13][14][15][16][17][18][19], NMR [14,20], microwave spectroscopy [21], and computational methods [14,17,18,[21][22][23][24]. Multiple conformers of TMP, designated as C1, C3, and Cs based upon their symmetry, have been found in the condensed and gas phases.…”

Section: ϩmentioning

confidence: 99%

A simple model for metal cation-phosphate interactions in nucleic acids in the gas phase: Alkali metal cations and trimethyl phosphate

Ruan

Huang

Rodgers

2008

J. Am. Soc. Mass Spectrom.

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Threshold collision-induced dissociation techniques are employed to determine the bond dissociation energies (BDEs) of complexes of alkali metal cations to trimethyl phosphate, TMP. Endothermic loss of the intact TMP ligand is the only dissociation pathway observed for all complexes. Theoretical calculations at the B3LYP/6-31G* level of theory are used to determine the structures, vibrational frequencies, and rotational constants of neutral TMP and the M ϩ (TMP) complexes. Theoretical BDEs are determined from single point energy calculations at the B3LYP/6-311ϩG(2d,2p) level using the B3LYP/6-31G* optimized geometries. The agreement between theory and experiment is reasonably good for all complexes except Li ϩ (TMP hosphate esters are integral parts of many biologically active molecules ranging from nucleic acids, lipids, and ATP to pesticides and nerve agents [1][2][3]. Serving as link components in nucleic acids, phosphate esters connect thousands of base pairs to form large molecules that contain the genetic information. These phosphate groups are deprotonated under physiological conditions. The resulting negative charges along the phosphate backbone are stabilized and neutralized by the binding of metal cations. Metal cations can and often do exert a significant influence on nucleic acid structure and genetic information transfer [4]. Metal cation binding reduces the repulsion between neighboring nucleotide units, and therefore influences the stabilization and structural dynamics of nucleic acids and lipids in membranes. For example, alkali and alkaline earth metal cations, including the most biologically important of these cations, Na ϩ and Mg 2ϩ , prefer to bind to a phosphate group rather than to the nucleobases or sugar moieties [5]. Mg 2ϩ is found to increase the melting temperature of DNA [6]. Metal cations may also be involved in the functioning of nucleic acids, e.g., metal cations are required for the proper functioning of all ribozymes [7]. Metal cation-nucleic acid interactions are currently of great interest because metal cations and metal cation-ligand complexes bind to DNA and regulate gene expression, act as drugs, or can be used as tools for molecular biology studies [8]. Hendry and Sargeson studied metal cation-promoted phosphate ester hydrolysis and found that the rate of hydrolysis is modulated by the size of the metal cation and the ease of formation of a four-membered chelate ring [9]. Dempcy and Bruice found a pentacoordinate intermediate for the catalysis of alkyl phosphate diesters [10]. Schneider and Kabelac et al. [11] studied the distribution of five metal cations (i.e., Na, and Zn 2ϩ ) and water around a negatively charged phosphate group from various crystal structures, and found that all of the cations prefer asymmetric monodentate coordination over bidentate coordination. Their ab initio calculations suggest that bidentate binding of these metal cations to an isolated phosphate group is preferred, but that the presence of even a single water molecule alters this preference. Ab...

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Section: ϩmentioning

confidence: 99%

A simple model for metal cation-phosphate interactions in nucleic acids in the gas phase: Alkali metal cations and trimethyl phosphate

Ruan

Huang

Rodgers

2008

J. Am. Soc. Mass Spectrom.

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“…In earlier experimental studies reporting the relative stabilities of the C 3 and C 1 forms [9,18], this conclusion was based on the change of the relative intensities of the signals ascribed to the individual conformers with the change of temperature. In such approach, degeneracy of conformational states is irrelevant.…”

Section: Theoretical Calculationsmentioning

confidence: 99%

“…Indeed, experimental studies could not confirm [18] or had excluded [32] the possibility of occurrence of the TMP molecule in a conformation with the C 3v symmetry. Streck et al [9] also noticed that Ôthe splittings observed for the C-O antisymmetric stretching, PO 3 antisymmetric stretching and PO 3 antisymmetric deformation modes originate in part from the presence of two conformers. However, in these regions the degeneracy of the modes is lifted in the lower symmetry conformer(s) and thus two bands are observed even under conditions in which the C 3 symmetry conformer is absentÕ.…”

Section: Introductionmentioning

confidence: 98%

“…In fact, the problem of conformational isomerism in TMP has been addressed many times during several decades. The molecule has been extensively studied in the past using vibrational spectroscopy in solutions [7][8][9][10][11][12][13][14][15][16][17][18][19], in gaseous [18,20] and solid [17][18][19] phases, and isolated in cryogenic matrices [19][20][21][22][23][24]; NMR spectroscopy [14,15,25]; electron diffraction [26]; dipole moments and Kerr constants methods [7,27]; dielectric loss spectroscopy [28]; and theoretically [14,21,[29][30][31]. And this big list of references is far from being complete.…”

Section: Introductionmentioning

confidence: 99%

“…It has been experimentally observed that changes of the electric properties of the medium strongly influence the conformational equilibrium in TMP [7][8][9]. In weakly polar solvents, the most stable form corresponds to the C 3 symmetry conformer.…”

Section: Introductionmentioning

confidence: 99%

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Conformational properties of trimethyl phosphate monomer

Reva

Simão

Fausto

2005

Chemical Physics Letters

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Conformational isomerism of trimethylphosphate (TMP) has been studied de novo. TMP monomers were isolated in low temperature xenon matrices at different substrate temperatures and characterized using FTIR spectroscopy. At the lowest temperature, three different conformers, with overall molecular symmetries C 3 , C 1 and C s , were shown to co-exist in the matrix. Increase of the sample temperature led to conformational cooling, with the two minor conformers being depopulated successively, following an order of increasing stability. Initially, the less stable C s conformer converted to the C 1 form and, at higher temperatures, the C 1 conformer converted to the global energy minimum, C 3 . Interpretation of the experimental data was supported by extensive calculations of the vibrational spectra and barriers to the conformational interconversion.

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Intermediate Phase‐Free Process for Methylammonium Lead Iodide Thin Film for High‐Efficiency Perovskite Solar Cells

et al. 2021

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Solvent engineering by Lewis‐base solvent and anti‐solvent is well known for forming uniform and stable perovskite thin films. The perovskite phase crystallizes from an intermediate Lewis‐adduct upon annealing‐induced crystallization. Herein, it is explored the effects of trimethyl phosphate (TMP), as a novel aprotic Lewis‐base solvent with a low donor number for the perovskite film formation and photovoltaic characteristics of perovskite solar cells (PSCs). As compared to dimethylsulfoxide (DMSO) or dimethylformamide (DMF), the usage of TMP directly crystallizes the perovskite phase, i.e., reduces the intermediate phase to a negligible degree, right after the spin‐coating, owing to the high miscibility of TMP with the anti‐solvent and weak bonding in the Lewis adduct. Interestingly, the PSCs based on methylammonium lead iodide (MAPbI3) derived from TMP/DMF‐mixed solvent exhibit a higher average power conversion efficiency of 19.68% (the best: 20.02%) with a smaller hysteresis in the current‐voltage curve, compared to the PSCs that are fabricated using DMSO/DMF‐mixed (19.14%) or DMF‐only (18.55%) solvents. The superior photovoltaic properties are attributed to the lower defect density of the TMP/DMF‐derived perovskite film. The results indicate that a high‐performance PSC can be achieved by combining a weak Lewis base with a well‐established solvent engineering process.

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Conformational behaviour of trimethyl phosphate studied by infrared spectroscopy

Cited by 35 publications

References 10 publications

A simple model for metal cation-phosphate interactions in nucleic acids in the gas phase: Alkali metal cations and trimethyl phosphate

A simple model for metal cation-phosphate interactions in nucleic acids in the gas phase: Alkali metal cations and trimethyl phosphate

Conformational properties of trimethyl phosphate monomer

Intermediate Phase‐Free Process for Methylammonium Lead Iodide Thin Film for High‐Efficiency Perovskite Solar Cells

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