The rotational spectra, potential function, Born-Oppenheimer breakdown, and magnetic shielding of SnSe and SnTe

The pure rotational spectra of 27 isotopic species of SnSe and SnTe have been measured in the frequency range of 5-24 GHz using a Fabry-Perot-type resonator pulsed-jet Fourier-transform microwave spectrometer. Gaseous samples of both chalcogenides were prepared by laser ablation of suitable target rods and were stabilized in supersonic jets of Ar. Global multi-isotopolog analyses of all available high-resolution data produced spectroscopic Dunham parameters Y01, Y11, Y21, Y31, Y02, and Y12 for both species, as well as Born-Oppenheimer breakdown (BOB) coefficients delta01 for Sn, Se, and Te. A direct fit of the same data sets to an appropriate radial Hamiltonian yielded analytic potential energy functions and BOB radial functions for the X 1Sigma+ electronic state of both SnSe and SnTe. Additionally, the magnetic hyperfine interaction produced by the dipolar nuclei 119Sn, 117Sn, 77Se, and 125Te was observed, yielding first determinations of the corresponding spin-rotation coupling constants.     

Facile synthesis of hydrophobic fluoroalkyl functionalized silsesquioxane nanostructures

New fluorinated polyhedral oligomeric silsesquioxane (F-POSS) structures possessing a high degree of hydrophobicity have been prepared via a facile corner-capping methodology.     

Fourier transform microwave and millimeter wave spectroscopy of quinazoline, quinoxaline, and phthalazine

The pure rotational spectra of the bicyclic aromatic nitrogen heterocycle molecules, quinazoline, quinoxaline, and phthalazine, have been recorded and assigned in the region 13-87 GHz. An analysis, guided by ab initio molecular orbital predictions, of frequency-scanned Stark modulated, jet-cooled millimeter wave absorption spectra (48-87 GHz) yielded a preliminary set of rotational and centrifugal distortion constants. Subsequent spectral analysis at higher resolution was carried out with Fourier transform microwave (FT-MW) spectroscopy (13-18 GHz) of a supersonic rotationally cold molecular beam. The high spectral resolution of the FT-MW instrument provided an improved set of rotational and centrifugal distortion constants together with nitrogen quadrupole coupling constants for all three species. Density functional theory calculations at the B3LYP∕6-311+G?? level of theory closely predict rotational constants and are useful in predicting quadrupole coupling constants and dipole moments for such species.     

N-Methyl inversion and structure of six-membered heterocyclic rings: rotational spectrum of 1-methyl-4-piperidone

The conformational and structural properties of the six-membered heterocyclic ring of 1-methyl-4-piperidone have been observed in a jet-cooled supersonic expansion using Fourier transform microwave spectroscopy (FT-MW). The rotational spectrum evidenced two different conformations originated by nitrogen inversion, with the N-methyl group in either equatorial (most stable) or axial position. Additional observation of the rotational spectra for all possible carbon, nitrogen, and oxygen monosubstituted species (4 × (13)C, (15)N, (18)O) in natural abundance allowed us to determine substitution (r(s)) and effective structures (r(0)) for the equatorial conformer. Additional ab initio and DFT calculations provided comparative rotational parameters, structural data, conformational energies, and the axial-equatorial interconversion barrier. The structural data were compared with the related azabicycle of tropinone, revealing the molecular changes and structural relaxation associated with the presence of the two-carbon bridge in the latter molecule.     

Microwave observation of 41K79Br and 41K81Br from laser-ablated potassium bromide

The J = 2 ← 1 transitions of the previously unobserved isotopologues ⁴¹K⁷⁹Br and ⁴¹K⁸¹Br have been recorded with a pulsed-nozzle Fourier transform microwave spectrometer, newly combined with a 532 nm laser ablation source. Aspects of the experimental design are described. Rotational and nuclear quadrupole coupling constants are obtained and combined with published results for ³⁹K⁷⁹Br and ³⁹K⁸¹Br to produce a set of isotopically invariant parameters. New rotational transitions of ²³Na^35,37Cl, ³⁹K⁷⁹Br, and ³⁹K¹²⁷I have also been recorded. Excited vibrational states are not observed, indicating efficient cooling of the metal halides following the initial ablation event.     

Methyl Internal Rotation in Fruit Esters: Chain-Length Effect Observed in the Microwave Spectrum of Methyl Hexanoate

The gas-phase structures of the fruit ester methyl hexanoate, CH₃-O-(C=O)-C₅H₁₁, have been determined using a combination of molecular jet Fourier-transform microwave spectroscopy and quantum chemistry. The microwave spectrum was measured in the frequency range of 3 to 23 GHz. Two conformers were assigned, one with C_s symmetry and the other with C₁ symmetry where the γ-carbon atom of the hexyl chain is in a gauche orientation in relation to the carbonyl bond. Splittings of all rotational lines into doublets were observed due to internal rotation of the methoxy methyl group CH₃-O, from which torsional barriers of 417 cm⁻¹ and 415 cm⁻¹, respectively, could be deduced. Rotational constants obtained from geometry optimizations at various levels of theory were compared to the experimental values, confirming the soft degree of freedom of the (C=O)-C bond observed for the C₁ conformer of shorter methyl alkynoates like methyl butyrate and methyl valerate. Comparison of the barriers to methyl internal rotation of methyl hexanoate to those of other CH₃-O-(C=O)-R molecules leads to the conclusion that though the barrier height is relatively constant at about 420 cm⁻¹, it decreases in molecules with longer R.     

The LAM of the Rings: Large Amplitude Motions in Aromatic Molecules Studied by Microwave Spectroscopy

Large amplitude motions (LAMs) form a fundamental phenomenon that demands the development of specific theoretical and Hamiltonian models. In recent years, along with the strong progress in instrumental techniques on high-resolution microwave spectroscopy and computational capacity in quantum chemistry, studies on LAMs have become very diverse. Larger and more complex molecular systems have been taken under investigation, ranging from series of heteroaromatic molecules from five- and six-membered rings to polycyclic-aromatic-hydrocarbon derivatives. Such systems are ideally suited to create families of molecules in which the positions and the number of LAMs can be varied, while the heteroatoms often provide a sufficient dipole moment to the systems to warrant the observation of their rotational spectra. This review will summarize three types of LAMs: internal rotation, inversion tunneling, and ring puckering, which are frequently observed in aromatic five-membered rings such as furan, thiophene, pyrrole, thiazole, and oxazole derivatives, in aromatic six-membered rings such as benzene, pyridine, and pyrimidine derivatives, and larger combined rings such as naphthalene, indole, and indan derivatives. For each molecular class, we will present the representatives and summarize the recent insights on the molecular structure and internal dynamics and how they help to advance the field of quantum mechanics.     

PLLA Coating of Active Implants for Dual Drug Release

Cochlear implants, like other active implants, rely on precise and effective electrical stimulation of the target tissue but become encapsulated by different amounts of fibrous tissue. The current study aimed at the development of a dual drug release from a PLLA coating and from the bulk material to address short-term and long-lasting release of anti-inflammatory drugs. Inner-ear cytocompatibility of drugs was studied in vitro. A PLLA coating (containing diclofenac) of medical-grade silicone (containing 5% dexamethasone) was developed and release profiles were determined. The influence of different coating thicknesses (2.5, 5 and 10 µm) and loadings (10% and 20% diclofenac) on impedances of electrical contacts were measured with and without pulsatile electrical stimulation. Diclofenac can be applied to the inner ear at concentrations of or below 4 × 10⁻⁵ mol/L. Release of dexamethasone from the silicone is diminished by surface coating but not blocked. Addition of 20% diclofenac enhances the dexamethasone release again. All PLLA coatings serve as insulator. This can be overcome by using removable masking on the contacts during the coating process. Dual drug release with different kinetics can be realized by adding drug-loaded coatings to drug-loaded silicone arrays without compromising electrical stimulation.