On Tautomerism and Amphoterism: An In-Depth Structural and Physicochemical Characterization of Ammeline and Some of Its Salts.

Ammeline is a simple, readily available, molecular compound, which has been known for nearly 200 years. Despite that, no proper structural characterization of ammeline has been conducted so far. For this reason, the prevalent tautomeric form of ammeline in the solid remained unknown to this date. In the course of this study, its crystal structure was finally established by single-crystal X-ray diffraction. In this structure, ammeline is exclusively found as its 4,6-diamino-1,3,5-triazin-2(1H)-one tautomer and adopts layered structure with an exceptionally high hydrogen bond density. Ammeline shows an interesting amphoteric behavior. Therefore, the synthesis and structural characterization of some of its salts were carried out to investigate the influence of the protonation degree on its molecular structure. In particular, the crystal structure of silver ammelinate monohydrate was solved as the first reported structure containing deprotonated ammeline. Moreover, the crystal structures of three different modifications of ammelinium perchlorate were elucidated and the transformation conditions between them were studied. Lastly, the crystal structure of ammelinediium diperchlorate monohydrate, containing unprecedented doubly protonated ammeline, was determined. The products' thermal behavior was studied by differential thermal analysis and thermogravimetric analysis. The perchlorate salts were additionally examined for their potential as insensitive high-energy-density materials.

The Adjustability of Physicochemical Properties: Comparison of 1-Vinyl-5H-tetrazole and 1-Allyl-5H-tetrazole as Ligands in 3d Metal Energetic Coordination Compounds.

Energetic coordination compounds (ECCs) show promising properties to be used as potential substitutes for highly toxic lead-containing primary explosives. The concept is to combine the three building blocks: (i) ligand, (ii) transition metal, and (iii) anion, acting as (i) fuel, (ii) matrix, and (iii) oxidizer (e.g., ClO4-, NO3-, ClO3-) or energetic component (e.g., DN-, N3-, picrate, styphnate, trinitrophloroglucinate). By variation of the ligands, the complexes' properties can be adjusted toward their desired performance and sensitivities. In the present study, 1-vinyl-5H-tetrazole (1-VTZ, 1) and 1-allyl-5H-tetrazole (1-ATZ, 2) were used as nitrogen-rich endothermic ligands to form 3d metal (Mn2+, Fe2+, Cu2+, Zn2+, Co2+, Ni2+)-based ECCs. The influence of the introduction of an unsaturated C-C bond (1-ETZ vs 1-VTZ and 1-PTZ vs 1-ATZ) on the performance and sensitivity of the complexes is discussed, as is the lengthening of the alkenyl chain (1-VTZ vs 1-ATZ). For further insights, the novel complexes were compared to literature-known complexes based on N1-substituted C2- and C3-derived tetrazole ligands, respectively. The ligand 1-VTZ (1) was prepared by elimination of hydrogen chloride from 1-(2-chloroethyl)-5H-tetrazole in methanolic KOH solution. 1-ATZ (2) was obtained by a heterocyclization reaction of allylamine with triethyl orthoformate and sodium azide in an acetic acid medium. All compounds were intensively characterized with analytical methods such as XRD, IR, EA, DTA, TGA, and sensitivity measurements (IS and FS). The energetic performances were visibly evaluated in fast heating experiments. Furthermore, PETN initiation and laser ignition experiments were carried out for promising ECCs.

Nitratoethyl-5H-tetrazoles: improving the oxygen balance through application of organic nitrates in energetic coordination compounds.

1- and 2-Nitratoethyl-5H-tetrazole (1-NET and 2-NET) were prepared through nitration of the respective alkyl alcohol using 100% nitric acid. A mixture of 1- and 2-hydroxyethyl-5H-tetrazole was obtained after alkylation of 1,5H-tetrazole. Also, a one-pot synthesis of 1-hydroxyethyl-5H-tetrazole was developed enabling the selective preparation of 1-NET. Both organic nitrates were characterized by 1H, 13C, and 1H-15N HMBC NMR spectroscopy. In addition, calculations using the Hirshfeld method and the EXPLO5 code were performed. Principally, 20 energetic coordination compounds involving the d-metals Mn, Cu, Zn, and Ag, each structurally characterized by low temperature single crystal X-ray diffraction, were prepared based on 1-NET and 2-NET. Of these complexes, 18 were obtained as pure bulk materials, and therefore, characterized for impact, friction, and ball drop impact sensitivity, as well as electrostatic discharge and thermal stability using differential thermal analysis. Hot plate and hot needle tests were performed mostly showing strong deflagrations making the complexes candidates for green combustion catalysts. Furthermore, successful PETN initiation experiments were carried out for several complexes and all ECCs were investigated by laser ignition experiments.

Coexisting frequency combs spaced by an octave in a monolithic quantum cascade laser.

Quantum cascade lasers are proving to be instrumental in the development of compact frequency comb sources at mid-infrared and terahertz frequencies. Here we demonstrate a heterogeneous terahertz quantum cascade laser with two active regions spaced exactly by one octave. Both active regions are based on a four-quantum well laser design and they emit a combined 3 mW peak power at 15 K in pulsed mode. The two central frequencies are 2.3 THz (bandwidth 300 GHz) and 4.6 THz (bandwidth 270 GHz). The structure is engineered in a way that allows simultaneous operation of the two active regions in the comb regime, serving as a double comb source as well as a test bench structure for all waveguide internal self-referencing techniques. Narrow RF beatnotes (∼ 15 kHz) are recorded showing the simultaneous operation of the two combs, whose free-running coherence properties are investigated by means of beatnote spectroscopy performed both with an external detector and via self-mixing. Comb operation in a highly dispersive region (4.6 THz) relying only on gain bandwidth engineering shows the potential for broad spectral coverage with compact comb sources.

Broadband terahertz amplification in a heterogeneous quantum cascade laser.

We demonstrate a broadband terahertz amplifier based on ultrafast gain switching in a quantum cascade laser. A heterogeneous active region is processed into a coupled cavity metal-metal waveguide device and provides broadband terahertz gain that allows achieving an amplification bandwidth of more than 500 GHz. The temporal and spectral evolution of a terahertz seed pulse, which is generated in an integrated emitter section, is presented and an amplification factor of 21 dB is reached. Furthermore, the quantum cascade amplifier emission spectrum of the emerging sub-nanosecond terahertz pulse train is measured by time-domain spectroscopy and reveals discrete modes between 2.14 and 2.68 THz.

Dynamics of ultra-broadband terahertz quantum cascade lasers for comb operation.

We present an experimental investigation of the multimode dynamics and the coherence of terahertz quantum cascade lasers emitting over a spectral bandwidth of ~1THz. The devices are studied in free-running and under direct RF modulation. Depending on the pump current we observe different regimes of operation, where RF spectra displaying single and multiple narrow beat-note signals alternate with spectra showing a single beat-note characterized by an intense phase-noise, extending over a bandwidth up to a few GHz. We investigate the relation between this phase-noise and the dynamics of the THz modes through the electro-optic sampling of the laser emission. We find that when the phase-noise is large, the laser operates in an unstable regime where the lasing modes are incoherent. Under RF modulation of the laser current such instability can be suppressed and the modes coherence recovered, while, simultaneously, generating a strong broadening of the THz emission spectrum.

Synthetic Inhibitors of Cell Adhesion: A Glycopeptide from E-Selectin Ligand 1 (ESL-1) with the Arabino Sialyl Lewisx Structure.

Particularly selective methods are required for the synthesis of arabino sialyl Lewisx glycopeptides owing to the acid-labile ß-arabinopyranoside bond. It is important for the inhibition of cell adhesion that the arabino sialyl Lewisx glycopeptide 1, which contains the Gly 672 -Asp 681 sequence of the E-selectin Ligand 1 (ESL-1), binds ten times more strongly than sialyl Lewisx to E-selectin, although it is monovalent and does not contain L-fucose, which is considered essential.