Characterisation and classification of automotive clear coats with Raman spectroscopy and chemometrics for forensic purposes

The clear coats from a collection of automotive paint samples of 139 vehicles, covering a range of Australian and international vehicle manufacturers and sold in Western Australia, were characterised using FT‐Raman spectroscopy. Principal component analysis (PCA) revealed 19 distinct classes that were associated with the vehicles' manufacturer and model, and in the case of Australian manufacturers, the years of manufacture. Linear discriminant analysis based on the PCA groupings gave excellent discrimination between the groups with 96.9% of the calibration set and 97.6% of the validation set being correctly classified. Although the sample set comprised only vehicles available in Australia, the methodology used is universal and hence applicable in any jurisdiction that is willing and able to generate a statistically significant data set and maintain and update it as new vehicles appear on the market. A FT‐Raman spectroscopy‐based database would rapidly provide information regarding vehicle origin and manufacture and hence generate investigative leads for questioned paint samples found at incident sites. Copyright © 2016 John Wiley & Sons, Ltd.     

Ammonium ion mediated resorcarene capsules: ESI-FTICRMS study on gas-phase structure and ammonium ion affinity of tetraethyl resorcarene and its per-methylated derivative

The ammonium ion binding affinities of tetraethyl resorcarene (1) and its per-methylated derivative (2) were studied by electrospray ionization Fourier transform ion cyclotron resonance (ESI-FTICR) mass spectrometry. Ten different ammonium ions were tested as guests for the resorcarenes. A strong tendency for complex formation was observed with all ammonium ions of size and charge distribution suitable for noncovalent interactions with the cavities of the resorcarene hosts 1 and 2. Although differences in ammonium ion affinities were observed between 1 and 2 due to the dissimilar conformations, the overall tendency was that increase in the degree of substitution and the length of carbon chain of the ammonium cation facilitated the complex formation until the sterical hindrance impeded the complexation. Dimeric as well as monomeric ammonium ion complexes were formed with resorcarene 1, but resorcarene 2 was unable to form the dimeric capsules because of the lack of H-bond donor possibilities. The nature of binding of the guest was further investigated with ion-molecule reactions and by determination of the single crystal X-ray structure of host 1 complexed with tetramethyl ammonium bromide.     

Regioselective acylation of aminoresorcinarenes

The acid catalyzed hydrolytic cleavage of the oxazine rings in the readily available tetraoxazine derivatives of resorcinarenes results in tetraaminoresorcinarenes. A similar process applied to C₂-symmetrical bisoxazine resorcinarene tetratosylates affords C_2v-symmetrical resorcinarenediamines. The mild acylation of these resorcinareneamines with BOC-anhydride or para-nitrophenyl ester proceeds selectively at the nitrogen atoms without affecting the hydroxyl groups. Most of the resulting resorcinareneamides are thus obtained in preparative yields and can be easily purified by simple crystallizations. In the crystalline state the compounds obtained are found to bind chloride anions through hydrogen bonds and electrostatic interactions and to display a chiral arrangement of hydrogen bonded functional groups at the wide rim of the macrocycle.     

Photodissociation of formyl fluoride in rare gas matrixes

Photodissociation of formyl fluoride (HCOF) is studied in Ar, Kr, and Xe matrixes at 248 and 193 nm excitation by following spectral changes in the infrared absorption spectra. In all matrixes, the main photodissociation products are CO/HF species, including CO-HF and OC-HF complexes and thermally unstable CO/HF species (a distorted CO/HF complex or a reaction intermediate), which indicate negligible cage exit of atoms produced via the C-F and C-H bond cleavage channels. However, the observation of traces of H, F, CO, CO(2), F(2)CO, FCO, and HRg(2)(+) (Rg = Kr or Xe) in Kr and Xe matrixes would imply some importance of other reaction channels too. The analysis of the decay curves of the precursor shows that dissociation efficiency of HCOF increases as Ar < Kr < Xe, the difference being the factor of 10 between Ar and Xe. Moreover, HCOF dissociates 20-50 times faster at 193 nm compared to 248 nm. Interestingly, whereas the CO/HF species are stable with respect to photolysis in Ar, they photobleach in Kr and Xe matrixes at 248 and 193 nm, even though the first excited states of CO and HF are not energetically accessible with 193 and 248 nm photons. In krypton matrix, the photodissociation of CO/HF species at 248 nm is observed to be a single photon process. Quantum chemical calculations of electronic excitation energies of CO-HF and OC-HF complexes show that the electronic states of HF and CO mostly retain their diatomic nature in the pair. This clearly demonstrates that photodissociation of CO/HF complexes is promoted by the surrounding rare gas lattice.     

Dense Packing on Uniform Lattices

We study the Hard Core Model on the graphs G obtained from Archimedean tilings i.e. configurations in {0,1} ^G with the nearest neighbor 1’s forbidden. Our particular aim in choosing these graphs is to obtain insight to the geometry of the densest packings in a uniform discrete set-up. We establish density bounds, optimal configurations reaching them in all cases, and introduce a probabilistic cellular automaton that generates the legal configurations. Its rule involves a parameter which can be naturally characterized as packing pressure. It can have a critical value but from packing point of view just as interesting are the noncritical cases. These phenomena are related to the exponential size of the set of densest packings and more specifically whether these packings are maximally symmetric, simple laminated or essentially random packings. Research partially supported by The Finnish Academy of Science and Letters.     

Non-Markovian quantum jumps

Open quantum systems that interact with structured reservoirs exhibit non-Markovian dynamics. We present a quantum jump method for treating the dynamics of such systems. This approach is a generalization of the standard Monte Carlo wave function (MCWF) method for Markovian dynamics. The MCWF method identifies decay rates with jump probabilities and fails for non-Markovian systems where the time-dependent rates become temporarily negative. Our non-Markovian quantum jump approach circumvents this problem and provides an efficient unraveling of the ensemble dynamics.