Structure, thermodynamics, and energy content of aluminum-cyclopentadienyl clusters

We present quantum chemistry simulations of aluminum clusters surrounded by a surface layer of cyclopentadiene-type ligands to evaluate the potential of such complexes as novel fuels or energetic materials. Density functional theory simulations are used to examine the aluminum-ligand bonding and its variation as the size of the aluminum cluster increases. The organometallic bond at the surface layer arises mainly from ligand charge donation into the Al p orbitals balanced with repulsive polarization effects. Functionalization of the ligand and changes in Al cluster size are found to alter the relative balance of these effects, but the surface organometallic bond generally remains stronger than Al-Al bonds elsewhere in the cluster. In large clusters, such as the experimentally observed Al(50)Cp(12)*, this suggests that unimolecular thermal decomposition likely proceeds through loss of surface AlCp* units, exposing the strained interior aluminum core. The calculated heats of combustion per unit volume for these systems are high, approaching 60% that of pure aluminum. We discuss the possibility of using organometallic aluminum clusters as a means of achieving rapid combustion in propellants and fuels.     

Determination of Aluminum, Calcium, and Magnesium in Fraser Fir, Balsam Fir, and Red Spruce Foliage and Soil from the Southern and Middle Appalachians

Spruce–fir forests form unique ecosystems in the eastern United States and Canada. These forests are composed of Fraser fir (Abies fraseri) and red spruce (Picea rubens) in the Southern Appalachians, and balsam fir (Abies balsamea) and red spruce in the middle and northern Appalachians. Decline of spruce–fir forests has been observed since the 1960s that has been attributed, at least in part, to acidic deposition. Acidic deposition has been reported to decrease the availability of calcium and increase the availability of aluminum and induce decline of red spruce at high elevation sites above 1800 m. Aluminum, calcium, and magnesium were determined in Fraser fir, balsam fir, and red spruce foliage and soil from sites in the southern and middle Appalachians in order to evaluate whether acidic deposition may play a role in the decline of the conifers. Our nutrient studies did not provide any evidence that acidic deposition was affecting the conifers.     

2D-Conductivity of thin Pd films condensed at low temperatures

Resistance measurements have been made on quenched condensed Pd films with thicknesses between 25 Å and 350Å. The films are prepared under different evaporation conditions by varying the system pressure between 10^?8 and 10^?5 mbar. Resistance minima with a logarithmic increase of the sheet resistance are observed for thick films (d<350Å) condensed under intentionally “bad” (10^?5 mbar) vacuum conditions, as well as for thin films (d<50Å) condensed at pressures around 10^?8 mbar. Structure investigations show that the thick films are granular. For these films the relation of granularity to 2D localization is discussed. The thin films are continuous and the logarithmic resistance increase is in agreement with predictions of 2D-theories.     

Q-band EPR and ENDOR of low temperature X-irradiated beta-D-fructose single crystals

Beta-D-fructose single crystals were in situ X-irradiated at 80 K and measured using electron paramagnetic resonance (EPR), electron nuclear double resonance (ENDOR) and ENDOR-induced EPR (EIE) techniques at Q-band (34 GHz) microwave frequencies. The measurements revealed the presence of at least four carbon-centered radicals stable at 80 K. By means of ENDOR angular variations in the three principal crystallographic planes, six proton hyperfine coupling tensors could be determined and were assigned to four different radicals by the aid of EIE. Two of the radicals exhibit only beta-proton hyperfine couplings and reveal almost identical EIE spectra. For the other two radicals, the major hyperfine splitting originates from a single alpha-proton hyperfine coupling and their EIE spectra were also quite similar. The similarity of the EIE spectra and hyperfine tensors led to the assumption that there are only two essentially different radical structures. The radical exhibiting only beta-proton hyperfine couplings was assigned to a C3 centered radical arising from H3 abstraction and the other radical suggested to be an open-ring species with a disrupted C2-C3 bond and a double C2-O2 bond. A possible formation mechanism for the latter open-ring radical is presented. By means of cluster density functional theory (DFT) calculations, the structures of the two radicals were determined and a fairly good agreement between the calculated and experimental hyperfine tensors was found.     

Density functional investigation of high-spin XY (X = Cr, Mo, W and Y = C, N, O) molecules

The performance of a density functional theory approach in calculating the equilibrium bond length, dipole moment, and harmonic vibrational frequency in a series of group 6 (Cr, Mo, W) transition metal-containing diatomic molecules is evaluated. Using flexible basis sets comprised of Slater type functions, a wide range of exchange-correlation functionals is investigated. Comparing with known experimental values and published results from high-level theoretical calculations, the most suitable functional form is selected. The importance of relativistic effects is checked, and predictions are made for several unknown dipole moments. The best agreement with experimental parameters is obtained when using a general gradient approximation, while special and hybrid functional forms give less accurate results.     

A Multi-Frequency EPR and ENDOR Study of Rh and Ir Complexes in Alkali and Silver Halides

Aliovalent Rh and Ir cations have been frequently used to influence the photographic properties of silver halide emulsions. The doping introduces several types of related defects with distinct trapping and recombination properties. EPR and ENDOR are, in principle, ideally suited for the determination of the microscopic structure of the individual centres but it will be demonstrated that well-chosen, sometimes sophisticated multi-frequency experiments are necessary in order to (partially) reach this goal. Model studies on single crystals of AgCl and NaCl also appeared indispensable for the unravelling of the spectra.

In the review of Rh-centres in NaCl and AgCl special attention is paid to methods that allow to detect cation vacancies near Rh^2? complexes. An alternative explanation for the high temperature behaviour of the [RhCl₆]^4? complexes in AgCl is presented.     

Viscoelastic-mapping of cellulose nanofibrils using low-total-force contact resonance force microscopy (LTF-CRFM)

Cellulose - Low-total-force contact resonance force microscopy (LTF-CRFM), an atomic force microscopy method, is introduced as a non-destructive means to quantify the local viscoelastic loss...     

Anion‐Mediated Effects on the Size and Mechanical Properties of Enzymatically Crosslinked Suckerin Hydrogels

The suckerin family of proteins, identified from the squid sucker ring teeth assembly, offers unique mechanical properties and potential advantages over other natural biomaterials. In this study, a small suckerin isoform, suckerin‐12, is used to create enzymatically crosslinked, macro‐scale hydrogels. Upon exposure to specific salt conditions, suckerin‐12 hydrogels contracted into a condensed state where mechanical properties are found to be modulated by the salt anion present. The rate of contraction is found to correlate well with the kosmotropic arm of the Hofmeister anion series. However, the observed changes in hydrogel mechanical properties are better explained by the ability of the salt to neutralize charges in suckerin‐12 by deprotonization or charge screening. Thus, by altering the anions in the condensing salt solution, it is possible to tune the mechanical properties of suckerin‐12 hydrogels. The potential for suckerins to add new properties to materials based on naturally‐derived proteins is highlighted.     

Friedel-Crafts alkylation of benzo[b]furan with activated cyclopropanes catalyzed by a calcium(II) complex

The synthesis of γ-benzo[b]furanyl malonates was achieved through the addition of benzo[b]furan to activated cyclopropanes. These Friedel-Crafts reactions were catalyzed by calcium bis(trifluoromethanesulfonimide), Ca(NTf₂)₂ with tetrabutylammonium hexafluorophosphine as a co-catalyst. The additions proceeded with complete regioselectivity and in good to excellent yield. Optimization of the reaction conditions and investigation into the scope of the methodology with regards to substitution on the cyclopropane are reported.