Ab Initio Study of Trimethyl Phosphate:  Conformational Analysis, Dipole Moments, Vibrational Frequencies, and Barriers for Conformer Interconversion

George, Lisa; Viswanathan, K. S.; Singh, Surjit

doi:10.1021/jp9625570

Cited by 64 publications

(76 citation statements)

References 13 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 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%

“…The assumption of existence of a threefold symmetry axis appeared in many subsequent studies [20,[25][26][27]. However, in other works [30,31] it was duly noticed that there is no reason to assume that phosphate structures exhibit any overall symmetry. 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.…”

Section: Introductionmentioning

confidence: 99%

“…Higher level HF/6-31G** and MP2/6-31G** ab initio computations [23,31], however, yielded a different energy order for the three conformers: C 3 < C 1 < C s . In a recent theoretical study performed at the HF/PM3 level [14], the two-dimensional potential energy hyper-surface of TMP was calculated.…”

Section: Introductionmentioning

confidence: 99%

“…In early matrix works [19,20,22] there were some discrepancies regarding the nature of the observed conformers. But in the followup publications [23,31] it was concluded that only the C 3 and C 1 conformations would have significant population to be experimentally important. Vidya et al [22] studied the conformational cooling of TMP monomers isolated in matrices of argon and nitrogen.…”

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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Aqua‐mediated in situ synthesis of highly potent phosphorous functionalized flame retardant for cotton fabric

Dhumal,

Lokhande,

Bondarde

et al. 2023

J of Applied Polymer Sci

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Flame retardancy in various materials is becoming an increasingly important performance feature. In the textile industries, fire‐related problems have become an important concern over the decade. Herein, the polyvinyl alcohol (PVA) and graphene‐supported material were functionalized with trimethyl phosphate (TMP) for the synthesis of flame retardant (FR) composite material [graphene polymer functionalized trimethyl phosphate (GPTMP)] in the aqueous medium, which improves the stability of cotton fabric against flame. Graphene and PVA fabricated with phosphorus functional groups make the fabric more comfortable against fire and help to avoid further spreading of fire. The composite‐coated fabric sustains for a long time on continuous flame with maintaining its initial shape and size. The GPTMP‐coated fabric shows flame retardancy for up to 540 s on constant flame exposure, whereas control samples such as PVA‐, graphene oxide‐, and TMP‐coated fabrics resist for up to 15, 20, and 14 s, respectively. The limiting oxygen index (LOI) and vertical flammability test (VFT) for synthesized composites were performed to confirm and support the flame retardancy property of GPTMP. The GPTMP shows the 35% LOI value and forms the char length of 2.6 cm during VFT. This work provides a simple and eco‐friendly method to obtain novel GPTMP, which has a high potential as a FR for different fabrics, including cotton.

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Ab Initio Study of Trimethyl Phosphate: Conformational Analysis, Dipole Moments, Vibrational Frequencies, and Barriers for Conformer Interconversion

Cited by 64 publications

References 13 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

Aqua‐mediated in situ synthesis of highly potent phosphorous functionalized flame retardant for cotton fabric

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