C-H···π interactions in the CHBrF2···HCCH weakly bound dimer

The microwave spectra of four isotopologues of the CHBrF(2)···HCCH weakly bound dimer have been measured in the 6-18 GHz region using chirped-pulse and Balle-Flygare Fourier-transform microwave spectroscopy. Spectra of (13)CH(79)BrF(2) and (13)CH(81)BrF(2) monomers have also been measured, and spectroscopic constants are reported. Measurement of spectra for the (79)Br and (81)Br isotopologues of CHBrF(2) complexed with both (12)C(2)H(2) and (13)C(2)H(2) have allowed the determination of a structure with C(s) symmetry for this complex. CHBrF(2) interacts with the triple bond of acetylene via a C-H···π contact (R(H···π) = 2.670(8) ?) with the Br atom lying in the ab plane, located 3.293(40) ? from a hydrogen atom of the HCCH molecule. The structure of CHBrF(2)···HCCH has been compared with recently studied related acetylene complexes, including a comparison with (and further structural analysis of) the CHClF(2)···HCCH complex.     

Biodegradable,implantable sustained release systems based on glutamic acid copolymers

Polymer pellets that contain drugs and may be implanted under the skin offer effective means for providing sustained, controlled drug therapy to humans and animals. Among the most useful drug delivery systems are those based on biodegradable polymers that ultimately are absorbed by the body — eliminating the need for their surgical removal. Copolymers of L-glutamic acid and γ-ethyl L-glutamate biodegrade to L-glutamic acid and ethanol, at rates that are determined by the initial copolymer composition. The materials are permeable to a wide range of drugs, including steroids, narcotic antagonists, peptide hormones, antimalarials, and anticancer agents. When fabricated into matrix rods or capsules, the copolymers have been used to release drugs in animals at constant rates for prolonged periods of time. p]In this study, rods composed of a blend of drug and copolymer were found to be useful for the long-term release (i.e., 6 to 24 months) of drugs having low aqueous solubility, such as progesterone and levonorgestrel. Capsules, composed of a copolymer sheath surrounding the drug, were better suited for shorter durations of release (i.e., up to 6 months) of drugs having higher aqueous solubility, such as luteinizing hormone-releasing hormone and naltrexone. The physical dimensions and copolymer compositions of either dosage form were readily varied to meet specific delivery rate and duration objectives while satisfying equally important degradation requirements.     

Characterization of C-H...π interactions in the structure of the CHClF(2)-HCCH weakly bound complex

The microwave spectra of four isotopologues of the CHClF(2)-HCCH dimer have been measured and used to determine the structure of the complex. An initial scan over the 7-18 GHz region using the chirped-pulse microwave spectrometer at the University of Virginia provided initial assignments of the (35)Cl and (37)Cl isotopologues, with two additional H(13)C(13)CH species assigned using the resonant cavity Balle-Flygare microwave spectrometer at Eastern Illinois University. For the most abundant isotopologue, the rotational constants and quadrupole coupling constants are: A = 3301.21(4) MHz, B = 1353.4268(19) MHz, C = 1153.7351(18) MHz, χ(aa) = 34.681(12) MHz, χ(bb) = -69.70(3) MHz, χ(cc) = 35.02(2) MHz and χ(ab) = -8.8(3) MHz, in good agreement with ab initio calculations at the MP2/6-311++G(2d,2p) level. The alignment of CHClF(2) with respect to acetylene reveals a C-Hπ interaction, with a secondary C-ClH-C interaction also present between the two monomers. The fitted distance between the CHClF(2) hydrogen atom and the center of the triple bond is 2.730(6) ?, the distance between the chlorine atom and the acetylenic hydrogen is 3.061(38) ?, and the C-Hπ angle is 148.2(6)°. In addition, the centrifugal distortion constants give an estimate of the binding energy for the weak interaction of about 4.9(5) kJ mol(-1), in reasonable agreement with several similar complexes.     

Water Triggers Hydrogen‐Bond‐Network Reshaping in the Glycoaldehyde Dimer

Carbohydrates are ubiquitous biomolecules in nature. The vast majority of their biomolecular activity takes place in aqueous environments. Molecular reactivity and functionality are, therefore, often strongly influenced by not only interactions with equivalent counterparts, but also with the surrounding water molecules. Glycoaldehyde (Gly) represents a prototypical system to identify the relevant interactions and the balance that governs them. Here we present a broadband rotational‐spectroscopy study on the stepwise hydration of the Gly dimer with up to three water molecules. We reveal the preferred hydrogen‐bond networks formed when water molecules sequentially bond to the sugar dimer. We observe that the dimer structure and the hydrogen‐bond networks at play remarkably change upon the addition of just a single water molecule to the dimer. Further addition of water molecules does not significantly alter the observed hydrogen‐bond topologies.     

Spatial distributions and interstellar reaction processes

Methyl formate presents a challenge for the conventional chemical mechanisms assumed to guide interstellar organic chemistry. Previous studies of potential formation pathways for methyl formate in interstellar clouds ruled out gas-phase chemistry as a major production route, and more recent chemical kinetics models indicate that it may form efficiently from radical-radical chemistry on ice surfaces. Yet, recent chemical imaging studies of methyl formate and molecules potentially related to its formation suggest that it may form through previously unexplored gas-phase chemistry. Motivated by these findings, two new gas-phase ion-molecule formation routes are proposed and characterized using electronic structure theory with conformational specificity. The proposed reactions, acid-catalyzed Fisher esterification and methyl cation transfer, both produce the less stable trans-conformational isomer of protonated methyl formate in relatively high abundance under the kinetically controlled conditions relevant to interstellar chemistry. Gas-phase neutral methyl formate can be produced from its protonated counterpart through either a dissociative electron recombination reaction or a proton transfer reaction to a molecule with larger proton affinity. Retention (or partial retention) of the conformation in these neutralization reactions would yield trans-methyl formate in an abundance that exceeds predictions under thermodynamic equilibrium at typical interstellar temperatures of ≤100 K. For this reason, this conformer may prove to be an excellent probe of gas-phase chemistry in interstellar clouds. Motivated by new theoretical predictions, the rotational spectrum of trans-methyl formate has been measured for the first time in the laboratory, and seven lines have now been detected in the interstellar medium using the publicly available PRIMOS survey from the NRAO Green Bank Telescope.     

Observation of a double C-H···π interaction in the CH2ClF···HCCH weakly bound complex

The structure of the CH(2)ClF···HCCH dimer has been determined using both chirped-pulse and resonant cavity Fourier-transform microwave spectroscopy. The complex has C(s) symmetry and contains both a double C-H···π interaction, in which one π-bond acts as acceptor to two hydrogen atoms from the CH(2)ClF donor, and a weak C-H···Cl interaction, with acetylene as the donor. Analysis of the rotational spectra of four isotopologues (CH(2)(35)ClF···H(12)C(12)CH, CH(2)(37)ClF···H(12)C(12)CH, CH(2)(35)ClF···H(13)C(13)CH, and CH(2)(37)ClF-H(13)C(13)CH) has led to a structure with C-H···π distances of 3.236(6) ? and a C-H···Cl distance of 3.207(22) ?, in good agreement with ab initio calculations at the MP2/6-311++G(2d,2p) level. Both weak contacts are longer than those observed in similar complexes containing a single C-H···π interaction that lies in the C(s) plane; however, this appears to be the first double C-H···π contact to be studied by microwave spectroscopy, so there is little data for direct comparison. The rotational and chlorine nuclear quadrupole coupling constants for the most abundant isotopologue are: A = 5262.899(14) MHz, B = 1546.8074(10) MHz, C = 1205.4349(7) MHz, χ(aa) = 28.497(5) MHz, χ(bb) = -65.618(13) MHz, and χ(cc) = 37.121(8) MHz.     

Rotational Signatures of Dispersive Stacking in the Formation of Aromatic Dimers

The aggregation of aromatic species is dictated by inter‐ and intramolecular forces. Not only is characterizing these forces in aromatic growth important for understanding grain formation in the interstellar medium, but it is also imperative to comprehend biological functions. We report a combined rotational spectroscopic and quantum‐chemical study on three homo‐dimers, comprising of diphenyl ether, dibenzofuran, and fluorene, to analyze the influence of structural flexibility and the presence of heteroatoms on dimer formation. The structural information obtained shows clear similarities between the dimers, despite their qualitatively different molecular interactions. All dimers are dominated by dispersion interactions, but the dibenzofuran dimer is also influenced by repulsion between the free electron pairs of the oxygen atoms and the π‐clouds. This study lays the groundwork for understanding the first steps of molecular aggregation in systems with aromatic residues.     

Rotational spectrum of three conformers of 3,3-difluoropentane: Construction of a 480 MHz bandwidth chirped-pulse Fourier-transform microwave spectrometer

The rotational spectra for three conformers of 3,3-difluoropentane have been measured using both a newly constructed narrow bandwidth chirped-pulse Fourier-transform microwave spectrometer and a Balle-Flygare resonant cavity Fourier-transform microwave spectrometer. The chirped-pulse instrument produces a microwave pulse spanning up to 480 MHz bandwidth in the 7-18 GHz region by mixing a 1 μs chirped pulse (of up to 240 MHz bandwidth) from an arbitrary function generator with the output from a microwave synthesizer.Rotational spectra for the normal isotopic species and all possible ¹³C single substitutions were observed for the gauche-gauche and anti-gauche conformers, allowing a Kraitchman substitution structure and an inertial fit structure to be determined. ¹³C isotopic species and dipole moment components were not measurable for the less intense anti-anti species as a result of partially resolved fine splitting. Details of the new chirped-pulse instrument will be described and the structural results will be presented and compared with ab initio data for 3,3-difluoropentane.     

Water Triggers Hydrogen-Bond-Network Reshaping in the Glycoaldehyde Dimer

Carbohydrates are ubiquitous biomolecules in nature. The vast majority of their biomolecular activity takes place in aqueous environments. Molecular reactivity and functionality are, therefore, often strongly influenced by not only interactions with equivalent counterparts, but also with the surrounding water molecules. Glycoaldehyde (Gly) represents a prototypical system to identify the relevant interactions and the balance that governs them. Here we present a broadband rotational-spectroscopy study on the stepwise hydration of the Gly dimer with up to three water molecules. We reveal the preferred hydrogen-bond networks formed when water molecules sequentially bond to the sugar dimer. We observe that the dimer structure and the hydrogen-bond networks at play remarkably change upon the addition of just a single water molecule to the dimer. Further addition of water molecules does not significantly alter the observed hydrogen-bond topologies.