Phase transitions in graphs on orientable surfaces

Let be the orientable surface of genus and denote by the class of all graphs on vertex set with edges embeddable on . We prove that the component structure of a graph chosen uniformly at random from features two phase transitions. The first phase transition mirrors the classical phase transition in the Erd?s‐Rényi random graph chosen uniformly at random from all graphs with vertex set and edges. It takes place at , when the giant component emerges. The second phase transition occurs at , when the giant component covers almost all vertices of the graph. This kind of phenomenon is strikingly different from and has only been observed for graphs on surfaces.     

A Highly Lewis Acidic Strontium ansa-Arene Complex for Lewis Acid Catalysis and Isobutylene Polymerization

The potential of a dicationic strontium ansa-arene complex for Lewis acid catalysis has been explored. The key to its synthesis was a simple salt metathesis from SrI₂ and 2 Ag[Al(OR^F)₄], giving the base-free strontium-perfluoroalkoxyaluminate Sr[Al(OR^F)₄]₂ (OR^F=OC(CF₃)₃). Addition of an ansa-arene yielded the highly Lewis acidic, dicationic strontium ansa-arene complex. In preliminary experiments, the complex was successfully applied as a catalyst in CO₂-reduction to CH₄ and a surprisingly controlled isobutylene polymerization reaction.     

Volatile organic compounds in head and neck squamous cell carcinoma—An in vitro pilot study

Owing to the lack of specific symptoms, diagnosis of head and neck squamous cell carcinoma (HNSCC) may be delayed. We evaluated volatile organic compounds in tumor samples from patients suffering from HNSCC and tested the hypothesis that there is a characteristic altered composition in the headspace of HNSCC compared with control samples from the same patient with normal squamous epithelium. These results provide the basis for future noninvasive breath analysis in HNSCC. Headspace air of suspected tumor and contralateral control samples in 20 patients were analyzed using ion-mobility spectrometry. Squamous cell carcinoma was diagnosed in 16 patients. In total, we observed 93 different signals in headspace measurements. Squamous cell carcinomas revealed significantly higher levels of volatile cyclohexanol (0.54 ppb_v, 25th to 75th percentiles 0.35–0.86) compared with healthy squamous epithelium (0.24 ppb_v, 25th to 75th percentiles 0.12–0.3; p < 0.001). In conclusion, head and neck squamous cell carcinoma emitted significantly higher levels of volatile cyclohexanol in headspace compared with normal squamous epithelium. These findings form the basis for future breath analysis for diagnosis, therapy control and the follow-up of HNSSC to improve therapy and aftercare.     

Comparison of monomethoxy‐, dimethoxy‐, and trimethoxysilane anchor groups for surface‐initiated RAFT polymerization from silica surfaces

The immobilization of reversible addition–fragmentation chain transfer (RAFT) agents on silica for surface‐initiated RAFT polymerizations (SI‐RAFT) via the Z‐group approach was studied systematically in dependence of the functionality of the RAFT‐agent anchor group. Monoalkoxy‐, dialkoxy‐, and trialkoxy silyl ether groups were incorporated into trithiocarbonate‐type RAFT agents and bound to planar silica surfaces as well as to silica nanoparticles. The immobilization efficiency and the structure of the bound RAFT‐agent film varied strongly in dependence of the used solvent (toluene vs. 1,2‐dimethoxyethane) and the anchor group functionality, as evidenced by atomic force microscopy, transmission electron microscopy, dynamic light scattering, and UV/Vis spectroscopy. Surface‐initiated RAFT polymerizations using functionalized silica nanoparticles revealed that grafted oligomers, which often occur in SI‐RAFT, are not formed within the crosslinked structures that originate from the immobilization, and that RAFT‐agent films that show less aggregation during the immobilization are more efficient during SI‐RAFT in terms of polymer grafting density. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 103–113     

Copper(II) complexes bearing cyclobutanecarboxylate and pyridine ligands: a new series of dinuclear paddle-wheel complexes

Monatshefte für Chemie - Chemical Monthly - Four members of a new series of paddle-wheel copper(II) complexes bearing cyclobutanecarboxylate as bridging ligand with pyridine derived ligands in...     

Sr3P3N7: Complementary Approach by Ammonothermal and High-Pressure Syntheses

Nitridophosphates exhibit an intriguing structural diversity with different structural motifs, for example, chains, layers or frameworks. In this contribution the novel nitridophosphate Sr₃P₃N₇ with unprecedented dreier double chains is presented. Crystalline powders were synthesized using the ammonothermal method, while single crystals were obtained by a high-pressure multianvil technique. The crystal structure of Sr₃P₃N₇ was solved and refined from single-crystal X-ray diffraction and confirmed by powder X-ray methods. Sr₃P₃N₇ crystallizes in monoclinic space group P2/c. Energy-dispersive X-ray and Fourier-transformed infrared spectroscopy were conducted to confirm the chemical composition, as well as the absence of NH_x functionality. The optical band gap was estimated to be 4.4 eV using diffuse reflectance UV/Vis spectroscopy. Upon doping with Eu²⁺, Sr₃P₃N₇ shows a broad deep-red to infrared emission (λ_em=681 nm, fwhm≈3402 cm⁻¹) with an internal quantum efficiency of 42 %.     

A Journey from Thermally Tunable Synthesis to Spectroscopy of Phenylmethanimine in Gas Phase and Solution

Phenylmethanimine is an aromatic imine with a twofold relevance in chemistry: organic synthesis and astrochemistry. To tackle both aspects, a multidisciplinary strategy has been exploited and a new, easily accessible synthetic approach to generate stable imine-intermediates in the gas phase and in solution has been introduced. The combination of this formation pathway, based on the thermal decomposition of hydrobenzamide, with a state-of-the-art computational characterization of phenylmethanimine laid the foundation for its first laboratory observation by means of rotational electric resonance spectroscopy. Both E and Z isomers have been accurately characterized, thus providing a reliable basis to guide future astronomical observations. A further characterization has been carried out by nuclear magnetic resonance spectroscopy, showing the feasibility of this synthetic approach in solution. The temperature dependence as well as possible mechanisms of the thermolysis process have been examined.