Chirality-dependent balance between hydrogen bonding and London dispersion in isolated (±)-1-indanol clusters.

The aggregation behavior of racemic and enantiopure 1-indanol has been studied by FTIR spectroscopy, resonant ion dip IR spectroscopy, and spontaneous Raman scattering in supersonic jets. This triple experimental approach, augmented by homology to related molecular fragments and dispersion-corrected DFT predictions, allows disentangling the complex spectroscopic signature in the OH stretch range. Evidence for chirality-sensitive aggregation via isolated OH···π bonds in competition with cooperative ···OH···OH···π patterns is collected. An accurate description of London dispersion forces provides the key to its explanation.

Adaptive aggregation of peptide model systems.

Jet-cooled infrared spectra of acetylated glycine, alanine, and dialanine esters and their dimers are reported in the amide A and amide I-III regions. They serve as particularly simple peptide aggregation models and are found to prefer a single backbone conformation in the dimer that is different from the most stable monomer backbone conformation. In the case of alanine, evidence for topology-changing chirality discrimination upon dimer formation is found. The jet spectroscopic results are compared to gas phase spectra and quantum chemical calculations. They provide reliable benchmarks for the evaluation of the latter in the field of peptide interactions.

Dimers of cyclic carbonates: chirality recognition in battery solvents and energy storage.

Dimers of ethylene carbonate and propylene carbonate are created in supersonic jet expansions and characterized by FTIR spectroscopy. Fermi resonances are switched on and off by dimerization. There is a unique centrosymmetric dimer of ethylene carbonate in a pronounced case of complementary chirality synchronization, contributing to its energy storage capacity at melting. Two chiral propylene carbonate molecules combine in more intricate ways. If they have the same handedness, one of them is forced into an axial conformation and the binding partner stays in the more stable equatorial structure. If they have opposite handedness, centrosymmetric dimers of either axial or equatorial conformations are formed. This suggests the usefulness of chirality control in elucidating ionic transport mechanisms in battery solvents and asymmetric catalysis in such solvents.

Communication: Where does the first water molecule go in imidazole?

Supersonic jet FTIR spectroscopy supplemented by (18)O substitution shows unambiguously that water prefers to act as an O-H···N hydrogen bond donor towards imidazole, instead of acting as a N-H···O acceptor. Previous matrix isolation, helium droplet, and aromatic substitution experiments had remained ambiguous, as are standard quantum chemical calculations. The finding is supported by a study of the analogous methanol complexes and by higher level quantum chemical calculations.

Radiographic study of the distribution of maxillary intraosseous vascular canal in Koreans.

BACKGROUND: This study aimed to investigate the distribution and prevalence of intraosseous loop (anastomosis between posterior superior alveolar artery and infraorbital artery) in Koreans detected on computed tomography (CT) images taken prior to sinus augmentation surgery. METHODS: From the 177 patients who underwent sinus augmentation with lateral approach at Ewha Womans University Department of Implant Dentistry, 284 CT scans were evaluated. The canal height (CH), ridge height (RH), and canal height from the sinus floor (CHS) were measured on para-axial views at the first premolar, first molar, and second molar. The horizontal positions of the bony canals in the lateral wall were also classified. One-way analysis of variance (ANOVA) and t test were used to estimate the statistical differences (p < 0.05). RESULTS: The intraosseous loops were detected in 92 CT scans (32 %). The mean vertical height of the bony canals from the alveolar crest (CH) was 23.45 ± 2.81, 15.92 ± 2.65, and 16.61 ± 2.92 mm at the second premolar, first molar, and second molar, respectively. In the horizontal positions of the bony canals, intraosseous type was the most predominant. The canal heights more than 15 mm and less than 17 mm were most prevalent (33.7 %) and those under 13 mm were 12.0 %. CONCLUSIONS: The radiographic findings in this study could be used to decide the lateral osteotomy line avoiding potential vascular complication. However, only one third of the canals could be detected in CT scans; a precaution should be taken for the possibility of severe bleeding during lateral osteotomy.

An alternative treatment option for a bony defect from large odontoma using recycled demineralization at chairside.

Odontoma is the most common odontogenic benign tumor, and the treatment of choice is generally surgical removal. After excision, bone grafts may be necessary depending on the need for further treatment, or the size and location of the odontoma. Although the osteogenic capacity of a demineralized tooth was verified as early as 1967 by Urist and many other investigators, the cumbersome procedure, including a long demineralization time, may be less than comfortable for clinicians. A modified ultrasonic technology, with periodic negative pressure and temperature control, facilitated rapid and aseptic preparation of demineralized teeth for bone grafts. This approach reduces the demineralization time dramatically (≤80 minutes), so that the graft material can be prepared chairside on the same day as the extraction. The purpose of this article is to describe two cases of large compound odonotomas used as graft material prepared chairside for enucleation-induced bony defects. These two clinical cases showed favorable wound healing without complications, and good bony support for future dental implants or orthodontic treatment. Finally, this report will suggest the possibility of recycling the benign pathologic hard tissue as an alternative treatment option for conventional bone grafts in clinics.

Molecular recognition in glycolaldehyde, the simplest sugar: two isolated hydrogen bonds win over one cooperative pair.

Carbohydrates are used in nature as molecular recognition tools. Understanding their conformational behavior upon aggregation helps in rationalizing the way in which cells and bacteria use sugars to communicate. Here, the simplest α-hydroxy carbonyl compound, glycolaldehyde, was used as a model system. It was shown to form compact polar C 2-symmetric dimers with intermolecular O-H⋅⋅⋅O=C bonds, while sacrificing the corresponding intramolecular hydrogen bonds. Supersonic jet infrared (IR) and Raman spectra combined with high-level quantum chemical calculations provide a consistent picture for the preference over more typical hydrogen bond insertion and addition patterns. Experimental evidence for at least one metastable dimer is presented. A rotational spectroscopy investigation of these dimers is encouraged, also in view of astrophysical searches. The binding motif competition of aldehydic sugars might play a role in chirality recognition phenomena of more complex derivatives in the gas phase.

Structural preferences, argon nanocoating, and dimerization of n-alkanols as revealed by OH stretching spectroscopy in supersonic jets.

n-Alkanols can occur in a multitude of energetically competitive conformational states. Using the OH stretching vibration as an infrared and Raman spectroscopic sensor in supersonic jet expansions, the torsional preferences around the Calpha-O and Cbeta-Calpha bonds are probed for n-propanol through n-hexanol. Raman detection is more powerful for isolated monomers, whereas IR spectroscopy is more sensitive for molecular complexes. The subtle IR vibrational shift induced by the nanocoating of n-alcohols with Ar atoms is shown to alternate with chain length. A large number of alcohol dimer absorptions is observed and subjected to collisional relaxation and nanocoating conditions. Essential features of the dimer spectra are modeled successfully by a simple force field approach. Exploratory quantum chemical calculations up to the MP2/aug-cc-pvqz level encourage a rigorous theoretical study of the subtle conformational aspects in monomers and possibly also in dimers of linear alcohols.