Inductive Effects on Intramolecular Hydrogen Bond Strength: An Investigation of the Effect of an Electron-Withdrawing CF3 Group Adjacent to an Alcohol Hydrogen Bond Donor.

This combined experimental and theoretical study seeks to determine the role that inductive effects have on hydrogen bonds by an investigation into the change in intramolecular hydrogen bond strength in 2-amino-1-trifluoromethylethanol (2ATFME) relative to that in 2-aminoethanol (2AE). Toward this end, the rotational spectra of the normal, 13C, and 15N isotopologues have been measured using Fourier transform microwave spectroscopy and fit to the rotational, quadrupole coupling, and centrifugal distortion constants of the Watson A-reduction Hamiltonian. Structural parameters used to characterize the strength of the intramolecular hydrogen bond have been determined from the experimental structures of both 2ATFME and 2AE as well as from MP2/6-311++G(d,p) calculations. A comparison of these parameters in 2ATFME with those of 2AE indicates that the electron-withdrawing trifluoromethyl CF3 group strengthens the hydrogen bond. These include a 4% decrease in the distance between the donor and acceptor heavy atoms of the hydrogen bond, a 6% increase toward linearity of the OH···N angle, and a 23% decrease of the COH···N torsional angle toward planarity in 2ATFME relative to 2AE. This trend toward increased intramolecular hydrogen bond strength in 2ATFME is also observed within the ab initio structures.

Competing Intramolecular Hydrogen Bond Strengths and Intermolecular Interactions in the 4-Aminobutanol-Water Complex.

We seek to determine the effect of competing intermolecular hydrogen bonds from water on the preferred conformation of 4-aminobutanol (4AB) monomers stabilized by intramolecular hydrogen bonds. Toward this end, the rotational spectrum of the 4-aminobutanol-H2O complex was recorded using Fourier transform microwave spectroscopy and fit to the rotational, quadrupole coupling, and centrifugal distortion constants of the Watson S-reduction Hamiltonian. The experimental results are consistent with a 4AB-water complex that preserves the intramolecular hydrogen bond within the 4AB monomer and forms a single intermolecular bond with water acting as a donor. The experimental monomer structure agrees well with the lowest energy conformation calculated at the MP2/6-311++G(d,p) level of theory. Upon complex formation and the introduction of competing intermolecular bonds from water, only small changes in the OH···N intramolecular hydrogen bond and backbone torsional angles of the 4-aminobutanol monomer are observed. Similar small changes were observed for the shorter chain 3-aminopropanol amino alcohol monomer when complexed with water, in contrast to the 2-aminoethanol-H2O complex. In the latter, a large change in the backbone torsional angle and a breaking of the intramolecular hydrogen bond were observed. Thus, extending the methylene chain results in an increase in the strength of the intramolecular hydrogen bond in unbranched amino alcohols.

Isotopic Dependence of the Hydrogen-Transfer-Triggered Methyl-Group Rotation in Deuterated 5-Methyltropolone.

We present here the first experimental study of the microwave spectrum of deuterated 5-methyltropolone, a molecule which exhibits two large-amplitude motions: an intramolecular hydrogen transfer (deuterium transfer in the current case of deuterated 5-methyltropolone) and a methyl torsion. The main goal of this study was to get information on the isotopic dependence of the main tunneling parameters of 5-methyltropolone in the framework of the two dimensional tunneling formalism, which previously has shown some counterintuitive results for isotopic dependence of tunneling parameters in 2-methylmalonaldehyde. Measurements were carried out by Fourier-transform microwave spectroscopy in the 9 GHz to 26 GHz frequency range. Theoretical analysis was carried out using a tunneling-rotational Hamiltonian based on a G12 m extended-group-theory formalism. Our global fit of 384 transitions to 17 molecular parameters gave a weighted root-mean-square deviation of 0.8. The current study on the isotopic dependence of the main tunneling parameters in 5-methyltropolone supports the assumption of possible "leakage" between tunneling parameters in the two-dimensional tunneling formalism in use.

Interplay of Intermolecular and Intramolecular Hydrogen Bonds on Complex Formation: The 3-Aminopropanol-Water van der Waals Complex.

This combined experimental and theoretical study answers the question whether the intramolecular hydrogen-bond strength in amino alcohols is dependent on the ring size. For this purpose, the rotational spectrum of the 3-aminopropanol-H2O van der Waals complex was recorded using Fourier-transform microwave spectroscopy and fit to the rotational, quadrupole coupling, and centrifugal distortion constants of the Watson A-reduction Hamiltonian. The experimental results are consistent with an ab initio conformation calculated at the MP2/6-311++G(d,p) level that involves the lowest energy 3-aminopropanol monomer and consists of a hydrogen bonding network. The calculated global minimum ab initio complex however comprises a higher energy monomer conformation of 3-aminopropanol. Upon complex formation with water, the O-H····N intramolecular hydrogen bond and OCCN backbone conformation of the lower energy monomer remain unchanged, in contrast to 2-aminoethanol. This behavior is consistent with the increasing strength of the intramolecular hydrogen bond of linear amino alcohols as a function of increasing chain length.

Rotational spectra and computational analysis of two conformers of leucinamide.

Rotational spectra were recorded for two isotopic species of two conformers of the amide derivative of leucine in the range of 10.5-21 GHz and fit to a rigid rotor Hamiltonian. Ab initio calculations at the MP2/6-311++G(d,p) level identified the low energy conformations with different side chain configurations; the rotational spectra were assigned to the two lowest energy ab initio structures. We recorded 16 a- and b-type rotational transitions for conformer 1; the rotational constants of the normal species are A = 2275.6(2), B = 1033.37(2) and C = 911.71(5) MHz. We recorded 23 a- and b-type rotational transitions for conformer 2; the rotational constants of the normal species are A = 2752.775(8), B = 843.502(1) and C = 796.721(1) MHz. The rotational spectra of the (15)N(amide) isotopomer of each conformer were recorded and the atomic coordinates of the amide nitrogen were determined by Kraitchman's method of isotopic substitution. The experimentally observed structures are significantly different from the crystal structures of leucinamide and the gas-phase structures of leucine, and a natural bond orbital analysis revealed the donor-acceptor interactions governing side chain configuration.

Physical and chemical characterization of residential oil boiler emissions.

The toxicity of emissions from the combustion of home heating oil coupled with the regional proximity and seasonal use of residential oil boilers (ROB) is an important public health concern. Yet scant physical and chemical information about the emissions from this source is available for climate and air quality modeling and for improving our understanding of aerosol-related human health effects. The gas- and particle-phase emissions from an active ROB firing distillate fuel oil (commonly known as diesel fuel) were evaluated to address this deficiency. Ion chromatography of impactor samples showed that the ultrafine ROB aerosol emissions were approximately 45% (w/w) sulfate. Gas chromatography-mass spectrometry detected various n-alkanes at trace levels, sometimes in accumulation mode particles, and out of phase with the size distributions of aerosol mass and sulfate. The carbonaceous matter in the ROB aerosol was primarily light-adsorbing elemental carbon. Gas chromatography-atomic emission spectroscopy measured a previously unrecognized organosulfur compound group in the ROB aerosol emissions. High-resolution transmission electron microscopy of ROB soot indicated the presence of a highly ordered primary particle nanostructure embedded in larger aggregates. Organic gas emissions were measured using EPA Methods TO-15 and TO-11A. The ROB emitted volatile oxygenates (8 mg/(kg of oil burned)) and olefins (5 mg/(kg of oil burned)) mostly unrelated to the base fuel composition. In the final analysis, the ROB tested was a source of numerous hazardous air pollutants as defined in the Clean Air Act Amendments. Approximations conducted using emissions data from the ROB tests show relatively low contributions to a regional-level anthropogenic emissions inventory for volitile organic compounds, PM2.5, and SO2 mass.

Validation studies of thermal extraction-GC/MS applied to source emissions aerosols. 1. Semivolatile analyte-nonvolatile matrix interactions.

In this work, we develop a novel validation approach for studying how nonvolatile aerosol matrixes of considerably different chemical composition potentially affect the thermal extraction (TE)-GC/MS quantification of a wide range of trace semivolatile organic markers. The nonvolatile matrixes of a set of source emissions aerosols are first operationally isolated by thermally clearing the aerosols of their native semivolatile organic matter. TE-GC/MS analysis is then performed in triplicate on matrixes refortified with multilevel organic compound standard suites. The spiking of empty thermal extraction tubes and blank quartz filters is introduced as experimental control and also allows for the calculation of method detection limits. For the vast majority of organic compounds fortifying the matrixes (e.g., the alkane, alkene, cycloalkane, sterane, and phthalate classes), the analytical bias observed was classified as either minor or nonexistent. Furthermore, compound recoveries were generally highly reproducible, demonstrating relative standard deviations of less than 20%. For a diesel engine exhaust sample, significant matrix effects for the six- and seven-ring polycyclic aromatic hydrocarbons (PAHs) are observed and ascribed to the high proportion of elemental carbon in the sample. Our results suggest that TE-GC/MS may underestimate inhalation exposures to PAHs (with 5 rings or more) in atmospheric aerosols replete with diesel engine exhaust (e.g., near roadways or in polluted urban air). Due to its stability and representativeness, the use of a thermally cleared particulate matter matrix for validation purposes is probably expandable to additional sample pretreatment and instrumental techniques also being applied to quantify organic molecular markers in source and atmospheric aerosols.

The microwave spectrum of a two-top peptide mimetic: the N-acetyl alanine methyl ester molecule.

The rotational spectrum of N-acetyl alanine methyl ester, a derivative of the biomimetic, N-acetyl alanine N'-methyl amide or alanine dipeptide, has been measured using a mini Fourier transform spectrometer between 9 and 25 GHz as part of a project undertaken to determine the conformational structures of various peptide mimetics from the torsion-rotation parameters of low-barrier methyl tops. Torsion-rotation splittings from two of the three methyl tops capping the acetyl end of the -NH-C(=O)- and the methoxy end of -C(=O)-O- groups account for most of the observed lines. In addition to the AA state, two E states have been assigned and include an AE state having a torsional barrier of 396.45(7) cm(-1) (methoxy rotor) and an EA state having a barrier of 64.96(4) cm(-1) (acetyl rotor). The observed torsional barriers and rotational constants of alanine dipeptide and its methyl ester are compared with predictions from Möller-Plesset second-order perturbation theory (MP2) and density functional theory (DFT) in an effort to explore systematic errors at the two levels of theory. After accounting for zero-point energy differences, the torsional barriers at the MP2/cc-pVTZ level are in excellent agreement with experiment for the acetyl and methoxy groups while DFT predictions range from 8% to 80% too high or low. DFT is found to consistently overestimate the overall molecular size while MP2 methods give structures that are undersized. Structural discrepancies of similar magnitude are evident in previous DFT results of crystalline peptides.