Predicting enthalpies of molecular substances: application to LiBH4

For molecular substances exhibiting harmonic and nonharmonic vibrations, we present a first-principles approach to predict enthalpy differences between phases at finite temperatures, including solid-solid and melting. We apply it to the complex hydride LiBH4. Using ab initio molecular dynamics, we predict a structure for the high-T solid phase of lithium borohydride, and we propose an approximation to account for nonharmonic vibrations. We then predict the enthalpy changes for solid-solid transition, melting, and an H-storage reaction, all in agreement with experiment.     

Stochastic metallic-glass cellular structures exhibiting benchmark strength

By identifying the key characteristic "structural scales" that dictate the resistance of a porous metallic glass against buckling and fracture, stochastic highly porous metallic-glass structures are designed capable of yielding plastically and inheriting the high plastic yield strength of the amorphous metal. The strengths attainable by the present foams appear to equal or exceed those by highly engineered metal foams such as Ti-6Al-4V or ferrous-metal foams at comparable levels of porosity, placing the present metallic-glass foams among the strongest foams known to date.     

Water vapor: An extraordinary terahertz wave source under optical excitation

In modern terahertz (THz) sensing and imaging spectroscopy, water is considered a nemesis to be avoided due to strong absorption in the THz frequency range. Here we report the first experimental demonstration and theoretical implications of using femtosecond laser pulses to generate intense broadband THz emission from water vapor. When we focused an intense laser pulse in water vapor contained in a gas cell or injected from a gas jet nozzle, an extraordinarily strong THz field from optically excited water vapor is observed. Water vapor has more than 50% greater THz generation efficiency than dry nitrogen. It had previously been assumed that the nonlinear generation of THz waves in this manner primarily involves a free-electron plasma, but we show that the molecular structure plays an essential role in the process. In particular, we found that THz wave generation from H₂O vapor is significantly stronger than that from D₂O vapor. Vibronic activities of water cluster ions, occurring naturally in water vapor, may possibly contribute to the observed isotope effect along with rovibrational contributions from the predominant monomers.     

Thin SiC<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> layers prepared by hybrid laser–magnetron deposition

Thin SiC _x films were fabricated by hybrid laser–magnetron deposition system. KrF excimer laser was used for deposition of carbon and magnetron at the same time for sputtering of Si species. Films were fabricated in argon/hydrogen ambient with and without additional RF discharge. The substrate temperature was changed up to 700°C. Films topology, crystallinity, composition, chemical bonds and optical emission spectra were studied. Films were smooth and amorphous. Films of thickness 400–1000 nm were fabricated. Adhesion moved from 8 to 14 N, depending on deposition conditions.     

Differential etching of chalcogenides for infrared photonic waveguide structures

Chemical etching rates for two different chalcogenide glass compositions, As₄₀S₆₀ and As₂₄S₃₈Se₃₈, were studied using sodium hydroxide based etchant solutions. Etching was performed using a variation of standard photolithographic masking and wet-etching techniques. Variations in etch rate with NaOH concentration and glass composition were observed. The depth of etch was characterized using an optical profilometer. Etch rate differences as large as three orders of magnitude between these two glasses were observed at low NaOH concentration (0.053 M). We present a single variable etch rate curve of etch depth per time (nm/s) versus NaOH overall solution concentration (in M) for these two different chalcogenide glasses. This technology shows promise for fabricating photonic structures and has potential applications in fabricating novel photonic bandgap structures that will function in the long-wave infrared (LWIR) regime.     

MALDI MSI Reveals the Spatial Distribution of Protein Markers in Tracheobronchial Lymph Nodes and Lung of Pigs after Respiratory Infection

Respiratory infections are a real threat for humans, and therefore the pig model is of interest for studies. As one of a case for studies, Actinobacillus pleuropneumoniae (APP) caused infections and still worries many pig breeders around the world. To better understand the influence of pathogenic effect of APP on a respiratory system—lungs and tracheobronchial lymph nodes (TBLN), we aimed to employ matrix-assisted laser desorption/ionization time-of-flight mass spectrometry imaging (MALDI-TOF MSI). In this study, six pigs were intranasally infected by APP and two were used as non-infected control, and 48 cryosections have been obtained. MALDI-TOF MSI and immunohistochemistry (IHC) were used to study spatial distribution of infectious markers, especially interleukins, in cryosections of porcine tissues of lungs (necrotic area, marginal zone) and tracheobronchial lymph nodes (TBLN) from pigs infected by APP. CD163, interleukin 1β (IL-1β) and a protegrin-4 precursor were successfully detected based on their tryptic fragments. CD163 and IL-1β were confirmed also by IHC. The protegrin-4 precursor was identified by MALDI-TOF/TOF directly on the tissue cryosections. CD163, IL-1β and protegrin-4 precursor were all significantly (p < 0.001) more expressed in necrotic areas of lungs infected by APP than in marginal zone, TBLN and in control lungs.     

Cycloelimination of Imidazolidin‐2‐ylidene N‐Heterocyclic Carbenes: Mechanism and Insights into the Synthesis of Stable “NHC‐CDI” Amidinates

We report the discovery that 1,3‐bis(aryl)imidazolidin‐2‐ylidenes, one of the most widely studied classes of N‐heterocyclic carbenes (NHCs), undergo quantitative conversion to zwitterionic “NHC‐CDI” amidinates upon heating to ≈100 °C in solution. The mechanism of this novel NHC decomposition process is studied in detail. These studies enabled the rational synthesis of a new class of bench stable amidinates from a panel of NHCs and carbodiimides. We expect these constructs to find utility in a variety of applications.