Loading...
Please wait, while we are loading the content...
A comparative VCD study of methyl mandelate in methanol, dimethyl sulfoxide, and chloroform: explicit and implicit solvation models.
| Content Provider | Semantic Scholar |
|---|---|
| Author | Poopari, Mohammad Reza Dezhahang, Zahra Xu, Yunjie Calvin |
| Copyright Year | 2013 |
| Abstract | Vibrational absorption (VA) and vibrational circular dichroism (VCD) spectra of methyl mandelate, a prototype chiral molecule, in a series of organic solvents, namely methanol (MeOH-d(4)), dimethyl sulfoxide (DMSO-d(6)), and chloroform (CDCl(3)), have been measured in the finger print region from 1800 to 1150 cm(-1). Implicit solvation models in the form of polarizable continuum model and explicit solvation models have been employed independently and simultaneously. The goal is to evaluate their efficiencies in dealing with solvent effects in each solution and to establish a general strategy to adequately account for effects of solvents. Molecular dynamics (MD) simulation and radial distribution function analysis have been performed to aid the construction of the explicit solvation models. Initial geometry searches have been carried out at the B3LYP/6-31G(d) level for the methyl mandelate monomer and its explicit 1 : 1 and 1 : 2 solute-solvent hydrogen-bonded complexes. B3LYP/cc-pVTZ has been used for all the final geometry optimizations, the vibrational frequency, VA and VCD intensity, and optical rotation dispersion (ORD) calculations. The results show that inclusion of solvent explicitly and implicitly at the same time has significant impacts on the appearance of the VA and VCD spectra, and is crucial for reliable spectral assignments when solvents are capable of hydrogen-bonding interactions with solutes. When no strong solvent-solute hydrogen-bonding interactions in the case of chloroform are expected, the gas phase monomer model is adequate for spectral interpretation, while inclusion of implicit solvation improves the frequency agreement with experiment. ORD spectra of methyl mandelate in the aforementioned solvents at different concentrations under 5 excitation wavelengths have also been measured. The comparison between the calculated and the experimental ORD spectra supports the conclusions drawn from the VA and VCD investigations. |
| Starting Page | 600 |
| Ending Page | 600 |
| Page Count | 1 |
| File Format | PDF HTM / HTML |
| Alternate Webpage(s) | http://www.rsc.org/suppdata/cp/c2/c2cp42722b/c2cp42722b.pdf |
| PubMed reference number | 23247722v1 |
| Alternate Webpage(s) | https://doi.org/10.1039/c2cp42722b |
| DOI | 10.1039/c2cp42722b |
| Journal | Physical chemistry chemical physics : PCCP |
| Volume Number | 15 |
| Issue Number | 5 |
| Language | English |
| Access Restriction | Open |
| Subject Keyword | 5-norbornene-2,3-dimethanol Bortezomib/Cyclophosphamide/Dexamethasone Regimen Chloroform Circular Dichroism Circular Dichroism, Vibrational Clomiphene Dimethyl Sulfoxide Efficiency Excitation Hydrogen Methanol Molecular Dynamics Optical Rotation Organic solvent product Pyschological Bonding Solvents Spectrophotometry, Atomic Absorption Sulfoxides methyl mandelate monomer solute wavelength |
| Content Type | Text |
| Resource Type | Article |
