Poly(triazine imide) with intercalation of Lithium and ChlorideiIons [(C3N3)2(NHxLi1−x)3⋅LiCl]: A Crystalline 2D Carbon Nitride network

Poly(triazine imide) with intercalation of lithium and chloride ions (PTI/Li+Cl−) was synthesized by temperature-induced condensation of dicyandiamide in a eutectic mixture of lithium chloride and potassium chloride as solvent. By using this ionothermal approach the well-known problem of insufficient crystallinity of carbon nitride (CN) condensation products could be overcome. The structural characterization of PTI/Li+Cl− resulted from a complementary approach using spectroscopic methods as well as different diffraction techniques. Due to the high crystallinity of PTI/Li+Cl− a structure solution from both powder X-ray and electron diffraction patterns using direct methods was possible; this yielded a triazine-based structure model, in contrast to the proposed fully condensed heptazine-based structure that has been reported recently. Further information from solid-state NMR and FTIR spectroscopy as well as high-resolution TEM investigations was used for Rietveld refinement with a goodness-of-fit (χ2) of 5.035 and wRp=0.05937. PTI/Li+Cl− (P63cm (no. 185); a=846.82(10), c=675.02(9) pm) is a 2D network composed of essentially planar layers made up from imide-bridged triazine units. Voids in these layers are stacked upon each other forming channels running parallel to [001], filled with Li+ and Cl− ions. The presence of salt ions in the nanocrystallites as well as the existence of sp2-hybridized carbon and nitrogen atoms typical of graphitic structures was confirmed by electron energy-loss spectroscopy (EELS) measurements. Solid-state NMR spectroscopy investigations using 15N-labeled PTI/Li+Cl− proved the absence of heptazine building blocks and NH2 groups and corroborated the highly condensed, triazine-based structure model.

The microstructure and properties of energetically deposited carbon nitride films

The intrinsic stress, film density and nitrogen content of carbon nitride (CNx) films deposited from a filtered cathodic vacuum arc were determined as a function of substrate bias, substrate temperature and nitrogen process pressure. Contour plots of the measurements show the deposition conditions required to produce the main structural forms of CNx including N-doped tetrahedral amorphous carbon (ta-C:N) and a variety of nitrogen containing graphitic carbons. The film with maximum nitrogen content (~ 30%) was deposited at room temperature with 1.0 mTorr N2 pressure and using an intermediate bias of - 400 V. Higher nitrogen pressure, higher bias and/or higher temperature promoted layering with substitutional nitrogen bonded into graphite-like sheets. As the deposition temperature exceeded 500 °C, the nitrogen content diminished regardless of nitrogen pressure, showing the meta-stability of the carbon-nitrogen bonding in the films. Hardness and ductility measurements revealed a diverse range of mechanical properties in the films, varying from hard ta-C:N (~ 50 GPa) to softer and highly ductile CN x which contained tangled graphite-like sheets. Through-film current-voltage characteristics showed that the conductance of the carbon nitride films increased with nitrogen content and substrate bias, consistent with the transition to more graphite-like films. © 2014 Elsevier B.V.

Characterization of antibody V segment diversity in the Tasmanian devil (Sarcophilus harrisii)

The Tasmanian devil (Sarcophilus harrisii) immune system has recently been under scrutiny because of the emergence of a contagious cancer, which has decimated devil numbers. Here we provide a comprehensive description of the Tasmanian devil immunoglobulin variable regions. We show that heavy chain variable (VH) and light chain variable (VL) repertoires are similar to those described in other marsupial taxa: VL diversity is high, but VH diversity is restricted and belongs only to clan III. As in other mammals, one VH and one Vλ germline family and multiple incomplete Vκ germline sequences were identified in the genome. High Vκ variation was observed in transcripts and we predict that it may have arisen by gene conversion and/or somatic mutations, as it does not appear to have originated from germline variation. Phylogenetic analyses revealed that devil VL gene segments are highly complex and ancient, with some lineages predating the separation of marsupials and eutherians. These results indicate that although the evolutionary history of immune genes lead to the expansions and contractions of immune gene families between different mammalian lineages, some of the ancestral immune gene variants are still maintained in extant species. A high degree of similarity was found between devil and other marsupial VH segments, demonstrating that they originated from a common clade of closely related sequences. The VL families had a higher variation than VH both between and within species. We suggest that, similar to other studied marsupial species, the complex VL segment repertoire compensates for the limited VH diversity in Tasmanian devils.

Systematic approach to the quantitative voltammetric analysis of the Fe III /Fe II component of the [α 2 -Fe(OH 2 )P 2 W 17 O 61 ] 7-/8- reduction process in buffered and unbuffered aqueous media

The one-electron reduction of [α2-FeIII(OH2)P2W17O61]7- at a glassy carbon electrode was investigated using cyclic and rotating-disk-electrode voltammetry in buffered and unbuffered aqueous solutions over the pH range 3.45−7.50 with an ionic strength of approximately 0.6 M maintained. The behavior is well-described by a square-scheme mechanism P + e- ↔ Q (E10/ = −0.275 V, k10/ = 0.008 cm s-1, and α1 = 1/2), PH+ + e- ↔ QH+ (E20/ = −0.036 V, k20/ = 0.014 cm s-1, and α2 = 1/2), PH+ ↔ P + H+ (KP = 3.02 × 10-6 M), and QH+ ↔ Q + H+ (KQ = 2.35 × 10-10 M), where P, Q, PH+, and QH+ correspond to [α2-FeIII(OH)P2W17O61]8-, [α2-FeII(OH)P2W17O61]9-, [α2-FeIII(OH2)P2W17O61]7-, and [α2-FeII(OH2)P2W17O61]8-, respectively; E10‘ and E20‘ are the formal potentials, k10‘ and k20‘ are the formal (standard) rate constants, and KP and KQ are the acid dissociation constants for the relevant reactions. The analysis for the buffered media is based on the approach of Laviron who demonstrated that a square scheme with fully reversible protonations, reversible or quasi reversible electron transfers with the assumption that α1 = α2, can be well-described by the behavior of a simple redox couple, ox + e- ↔ red, whose formal potential, Eapp0‘, and standard rate constant, kapp0‘, are straightforwardly derived functions of pH, as are the values of E10‘, k10‘, E20‘, k20‘, and KP (only three of the four thermodynamic parameters in a square scheme can be specified). It was assumed that αapp = 1/2, and the simulation program DigiSim was used to determine the values of Eapp0‘ and kapp0‘, which are required to describe the cyclic voltammograms obtained in buffered media in the pH range from 3.45 to 7.52 (buffer-related reactions which effect general acid−base catalysis are included in the simulations). DigiSim simulations of cyclic voltammograms obtained in unbuffered media yielded the values of E10‘ and k10‘; KQ was then directly computed from thermodynamic constraints. These simulations included additional reactions between the redox species and H2O. The value of the diffusion coefficient of the [α2-FeIII(OH2)P2W17O61]7-, 2.92 × 10-6 cm2 s-1, was determined using DigiSim simulations of voltammograms at a rotating disk electrode in buffered and unbuffered media at pH 3.45. The diffusion coefficients of all redox species were assumed to be identical. When the pH is greater than 6, instability of P (i.e., [α2-FeIII(OH)P2W17O61]8-) led to the loss of the reactant and precluded lengthy experimentation.