NMR spectral analysis of strongly second-order 6-, 8-, 9- and 10- spin-systems (1H─19F, 19F─19F,and 13C─19F) in perfluorotoluyl- and tetrafluoro-pyridyl-aromatics using the lineshape method ANATOLIA

A simple to use nuclear magnetic resonance analysis method has been tested on complex ¹H, ¹⁹F, and ¹³C multiplets. This open-source line-shape analysis method analysis of total lineshape (ANATOLIA)¹ provides some significant advantages over traditional assign-iterate methods of NMR spectral analysis by avoiding false minima and progressing optimisation to the global minimum. The target molecules are 1-perfluorotol-4-yl-2-perfluorotol-4-yl-oxymethyl-1H-benzimidazole (molecule-I) and 1-tetrafluoropyrid-4-yl-2-tetrafluoropyrid-4-yl-thio-1H-benzimidazole (molecule-II) which were produced as part of a family of fluorinated drug scaffolds prepared for anticancer and antiparasitic screening. Spectra display significant second-order effects with ¹H Δδ = 3.68 and 4.67 Hz for the aromatic hydrogen “triplets”, with ¹⁹F ⁴J_AA', ⁴J_BB', ⁴J_XX', and ⁴J_YY' coupling constants range from +4.8 to −14.0 Hz and for ¹³C-isotopomers ¹⁹F Δδ of up to 111.56 Hz. A spin-system of six coupling nuclei (H_aH_bH_cH_d F_YF_Y') was analysed in 12 s, a spin-system of nine coupling fluorine nuclei (AA'BB'CCC-YY') was analysed within 2 min, and 10 coupling nuclei (XX'YY'ZZZ-BB'-H_d) was optimised in 6 min using a laptop computer. ANATOLIA was also robust enough to be able to yield accurate spectral values from inaccurate input values. In both compounds, a fluorine–fluorine coupling constant was identified between the two fluoro-aromatic rings (F_BB' and F_YY') of +4.05 and +4.67 Hz and attributed to a through-space interaction. Ab initio structure optimisations and coupling constant calculations provided useful input data for spectral analysis. A modern ¹⁹F nuclear magnetic resonance spectrum of perfluorotoluene (octafluorotoluene) and analysis from 1975 was used as a test data set to assess ANATOLIA.     

The effects of season and soil type on microbial degradation of gasoline residues from incendiary devices

The primary task of a fire debris chemist is to determine if there is an ignitable liquid present in a fire debris sample and, if so, to classify it according to its boiling point and carbon number range. However, in organic-rich substrates such as soil, the ignitable liquid residue is subject to microbial degradation due to the ease with which bacteria can metabolize the various hydrocarbons present. This is a rapid process which is problematic in many forensic laboratories as fire debris is often stored for extended periods of time due to case backlog. Although microbial degradation has been studied in laboratory samples, it has not been well-studied in “real-world” samples, which have not only been exposed to microbial degradation but have also suffered the effects of weathering due to the intense heat of the fire. In this work, the effects of microbial degradation of gasoline from an incendiary device have been evaluated over time. In addition to visually monitoring chromatographic changes, this work also utilizes multivariate statistical techniques to simplify the complex data set and elucidate trends that might not otherwise be observed. Results indicate a clear difference between glass samples, which suffered the loss of low boiling compounds, and soil, which suffered the loss of the normal alkanes and lesser substituted aromatics. Also, devices deployed on lawn soil and in the winter season appear to show the most extensive degradation of gasoline. Finally, while the ratio of the C₃-alkylbenzenes is significantly altered in soil samples recovered from large devices, the overall chromatographic profile of gasoline recovered from smaller incendiary devices is significantly lower.

Contact welding study of carbon nanotube with ZnO nanowire

Study of proton beam induced welding of multiwall carbon nanotubes (MWCNTs) with ZnO nanowires (NWs) has been carried out by proton (H⁺) beam irradiation. The samples were irradiated by 70-keV proton (H⁺) ion beams at different substrate temperatures. The irradiation-induced defects in CNTs and ZnO NWs were greatly reduced at elevated temperature. The crystalline structure of ZnO NWs and MWCNTs were found to remain stable after the irradiation at 700 K. As a preparation step, a coupling of two parallel ZnO NWs with irradiation has also been demonstrated. The welding mechanisms of MWCNTs and ZnO NWs were also been suggested. These two welding processes between same and distinct nanostructures to form homo- and hetero-junctions have provided an opportunity to mass produce interconnecting one-dimensional structures used for the manufacturing of future nanowire-based electronic circuits and devices.     

Pattern propagation in nonlinear dissipative systems

We discuss the problem of pattern selection in situations where a stable, nonuniform state of a nonlinear dissipative system propagates into an initially unstable, homogeneous region. Our strategy is to consider this process as a generalization of front propagation in a nonlinear diffusion problem for which rigorous results are known; and we point out that these known properties are consistent with a marginal-stability hypothesis that has been suggested in the theory of dendritic crystal growth. We then describe a more general interpretation of the marginal-stability hypothesis and, finally, present numerical evidence for its validity from three different pattern-forming models.     

The surface tension of polymer liquids

An experimental and theoretical review of the surface tension of polymer liquids is presented. New experimental methods for polymer surface tension measurement are reviewed. Numerous theoretical and empirical approaches are briefly described. Strong emphasis is placed on the accuracy and limitations of the thermodynamic information which are used as input to many of if not all these theories. It is shown that, by using accurate thermodynamic bulk properties for these liquids including polar polymers, one can use a simple corresponding states principle to describe the temperature and molecular weight dependences of the surface tension with no adjustable parameters to within a few per cent, even though the actual surface tensions may vary by a few hundred per cent. Any small inaccuracies in the predictions arise from conformational entropic effects or because one cannot accurately compute the 'real' cohesive energy density of a polymer liquid from thermodynamic properties alone. The results of recent measurements on high molecular weight polymers are compared with previous work on lower molecular weight liquids. We use the polyethylene and polytetrafluoroethylene oligomeric series to illustrate the uses and limitations of thermodynamicdata for the prediction of surfacetension. The temperature and molecular weightdependences of the surface tensions of these polymers are dominated by the dependence of the bulk thermodynamic properties on temperature and molecular weight. Limited discussion is also given to studies of copolymers and blends using surface tension and complementary techniques.     

The surface tension of polymer liquids

A brief review of the surface tension of polymer liquids is presented. A strong emphasis is placed on recent measurements of surface tensions of homologous liquid series up to high-molecular-weight polymers, and the thermodynamic liquid properties of these same homologous series obtained from sources such as pressure-volume-temperature (PVT) data. The accuracy and limitations of the thermodynamic information which are used as input to many of the theories applied to the surface properties of polymer molecules are discussed. By scaling the surface tension data using a true measure of the cohesive energy density of the liquid state, we can clearly observe the entropic contribution to the surface tension caused by the conformational restriction of a large molecule at the liquid-vapor interface. The scaling implies the existence of a corresponding states principle for both polymer liquids and for low-molecular-weight liquids. The ramifications of the existence of a corresponding states principle for the surface tension of polymer melts are discussed. One consequence of the corresponding states principle is that it allows us to use surface tension measurements to compute the cohesive energy density of polymer melts using PVT data.     

Effects of substrate on surface morphology, crystallinity, and photoluminescence properties of sputtered ZnO nano films

Effects of substrate on crystallinity, surface morphology, and luminescence properties of radio frequency sputtered zinc oxide (ZnO) thin films were investigated. A variety of materials such as Si (100), Si (111), Al₂O₃, quartz, and silicon carbide (SiC) wafers were examined as substrates for deposition of ZnO thin films. The results showed smooth and uniform growth of c-axis orientation films. The thickness of the layers was about 50 nm. The average grain sizes of films were about 10, 13, and 12 nm for Si (111), quartz, and SiC samples, respectively. The deposited film on Al₂O₃ showed the largest grain size, about 500 nm. Grazing incidence x-ray diffraction patterns of the samples revealed that sputtered layers on Al₂O₃ and quartz had better crystallinity with higher peak at (002) orientation compared to Si and SiC substrates. Moreover, the Al₂O₃ sample exhibited a weak peak at position of (100) planes of ZnO too. The photoluminescence spectra of the samples showed a typical luminescence behavior with a broad UV band, including a main peak at around 388 nm and a weak shoulder peak at around 381 nm, corresponding with bound excitonic recombination and free excitonic recombination, respectively. The luminescence peak revealed that the intensity of UV emission is not necessarily dependent on the grain sizes and the micro-structural quality of ZnO films.     

Synthesis of certain pyrazolo[3,4-d]pyrimidin-3-one nucleosides

Synthesis of the pyrazolo[3,4-d]pyrimidin-3-one congeners of guanosine, adenosine and inosine is described. Glycosylation of 3-methoxy-6-methylthio-1H-pyrazolo[3,4-d]pyrimidin-4(5H)-one ( 13 ) with 1-O-acetyl-2,3,5-tri-O-benzoyl-D-ribofuranose ( 16 ) in the presence of boron trifluoride etherate gave 3-methoxy-6-methylthio-1-(2,3,5-tri-O-benzoyl-β-D-ribofuranosyl)pyrazolo[3,4-d]pyrimidin-4(5H)-one ( 17 ) which, after successive treatments with 3-chloroperoxybenzoic acid and methanolic ammonia, afforded 6-amino-3-methoxy-1-β-D-ribofuranosylpyrazolo[3,4-d]pyrimidin-4(5H)one ( 18 ). The guanosine analog, 6-amino-1-β-D-ribofuranosylpyrazolo[3,4-d]pyrimidine-3,4(2H,5H)-dione ( 21 ), was made by sodium iodide-chlorotrimethylsilane treatment of 6-amino-3-methoxy-1-(2,3,5-tri-O-acetyl-β-D-ribofuranosyl)pyrazolo[3,4-d]pyrimidin-4(5H)one ( 19 ), followed by sugar deprotection. Treatment of the adenine analog, 4-amino-1H-pyrazolo[3,4-d]pyrimidin-3(2H)-one ( 11 ), according to the high temperature glycosylation procedure yielded a mixture of N-1 and N-2 ribosyl-attached isomers. Deprotection of the individual isomers afforded 4-amino-3-hydroxy-1-βribofuranosylpyrazolo-[3,4-d]pyrimidine ( 26 ) and 4-amino-2-β-D-ribofuranosylpyrazolo[3,4-d]pyrimidin-3(7H)-one ( 27 ). The structures of 26 and 27 were established by single crystal X-ray diffraction analysis. The inosine analog, 1-β-D-ribofuranosylpyrazolo[3,4-d]pyrimidine-3,4(2H,5H)-dione ( 28 ), was synthesized enzymatically by direct ribosylation of 1H-pyrazolo[3,4-d]pyrimidine-3,4(2H,5H)-dione ( 8 ) with ribose-1-phosphate in the presence of purine nucleoside phosphorylase, and also by deamination of 26 with adenosine deaminase.