Reduction of Capacity Fading in High-Voltage NMC Batteries with the Addition of Reduced Graphene Oxide.

Lithium-ion batteries for electric vehicles (EV) require high energy capacity, reduced weight, extended lifetime and low cost. EV manufacturers are focused on Ni-rich layered oxides because of their promising attributes, which include the ability to operate at a relatively high voltage. However, these cathodes, usually made with nickel-manganese-cobalt (NMC811), typically experience accelerated capacity fading when operating at a high voltage. In this research, reduced graphene oxide (rGO) is added to a NMC811 cathode material to improve the performance in cyclability studies. Batteries made with rGO/NMC811 cathodes showed a 17% improvement in capacity retention after 100 cycles of testing over a high-voltage operating window of 2.5-4.5 V.

How Does the Local Electrostatic Field Influence Emitted Wavelengths and Bioluminescent Intensities of Modified Heteroaromatic Luciferins?

The firefly chromophore, oxyluciferin, is in the pocket of the firefly luciferase and is surrounded by the side-chains of some amino acid residues. The charged residues produce the local electrostatic field (LEF) around the oxyluciferin. The emitted wavelengths and intensities of the oxyluciferin and its heterocyclic analogs under the LEF are examined. The common overlapping volumes of the HOMO and LUMO explain why the oscillator strengths vary under the LEF. Three average Ex change rates of the first excited energy are introduced to measure what luciferins are more sensitive to the LEF. The first excited energies and intensities in two enzymatic-like microenvironments are simulated via the LEF. The oscillator strengths and the net electric charges of the O6' and the O4 are applied to explain the experimental bioluminescent intensities.

Theoretical investigation into the structural, thermochemical, and electronic properties of the decathio[10]circulene.

For the first time, a theoretical study has been performed on the prototypical decathio[10]circulene (C(20)S(10)) species, which is an analogue of the novel octathio[8]circulene "Sulflower" molecule (C(16)S(8)). Examinations of the singlet and triplet states of C(20)S(10) were made at the B3LYP/6-311G(d) level. Local minima of C(2) and C(s) symmetry were found for the lowest singlet and triplet states, respectively. The stability of C(20)S(10) was assessed by calculating the ΔH°(f) of C(16)S(8) and C(20)S(10) and the ΔH(o) for their decomposition into C(2)S units. Frontier molecular orbital plots show that structural adjacent steric factors along with the twist and strain orientations of C(20)S(10) do not disturb the aromatic π-delocalizing effects. In fact, C(20)S(10) maintains the same p(z) HOMO character as C(16)S(8). These similarities are further verified by density-of-states characterization. Calculated infrared spectra of C(16)S(8) and C(20)S(10) show broad similarities. Molecular electrostatic potential results reveal that eight of the peripheral sulfur atoms are the most electronegative atoms in the molecule, while the interior ten-membered ring exhibits virtually no electronegativity.

In vitro evaluation of cytotoxicity of engineered carbon nanotubes in selected human cell lines.

In this study, we used a systematic approach to study and compare the in vitro cytotoxicity of selected engineered carbon nanotubes (CNTs) to test cell lines including human skin keratinocytes, lung cells and lymphocytes. Results of fluorescein diacetate (FDA) uptake in T4 lymphocyte A3 cells indicated cytotoxicity caused by single-walled carbon nanotubes (SWCNTs) at concentrations of 2, 5 and 10ppm. At 2ppm, the SWCNT treatment group retained 71.3% viability compared to the PBS control group. At 10ppm, cellular viability further decreased to 56.5% of the PBS control group. In the skin keratinocyte HaCaT cells and lung MSTO-211H cells, the SWCNT did not demonstrate any cytotoxicity at concentrations of 2 and 5ppm but slightly inhibited HaCaT cells and caused significant toxicity to MSTO-211H cells at 10ppm. Multi-walled carbon nanotube (MWCNT) testing showed significant cytotoxicity to A3 cells in a dose-dependent manner. At 10ppm the viability of the cells decreased to 89.1% compared to the PBS control. In MSTO-211H cells, MWCNT caused significant toxicity at concentrations of 2ppm and higher. By comparison, HaCaT cells were inhibited significantly only at 10ppm. Overall, the test CNTs inhibited cellular viabilities in a concentration, cell type, and CNT type-dependent pattern. The viabilities of the MWCNT-impacted cells are higher than the corresponding SWCNT groups. We speculate that on a per volume basis, the greater availability of defects and contaminants for cellular interaction may contribute to the higher cytotoxicity of SWCNT in this study. The interaction between the SWCNTs and A3 lymphocytes was also observed by scanning electron microscopy. The mechanism for causing cell death in this study was attributed to apoptosis and necrosis after physical penetration by CNTs and oxidative stress via formation of reactive oxygen species.

Thioglycolic acid on the gold (111) surface and Raman vibrational spectra.

The interaction of thioglycolic acid (HSCH(2)COOH) with the Au(111) surface is investigated, and it is found that at the low coverage the molecule lies down on the substrate. If the mercaptan-hydrogen atom is eliminated, the resulting SCH(2)COOH molecule is randomly oriented on the surface. If the carboxylic acid group in the HSCH(2)COOH molecule is deprotonated instead, the HSCH(2)COO(-) molecule lies down on the surface. However, when the mercaptan-hydrogen atom in the HSCH(2)COO(-) molecule is removed, the resulting SCH(2)COO(-) molecule rises up to a certain level on the substrate. The calculated Raman vibrational spectra decipher which compounds and atomic displacements contribute to the corresponding frequencies. We thus propose a consistent mechanism for the deposition of thioglycolic acid on the Au(111) surface.

How does an external electrical field affect adsorption patterns of thiol and thiolate on the gold substrate?

The responsive behavior of methanethiol and methylthiolate molecules on the Au(111) surface with an applied electrical potential is studied, and it is shown how the sulfur adsorption site, the S-H bond orientation and the interacting energy change with an external electric field strength. The electron charge density corresponding to an electric field minus that obtained in zero field, with zero-field optimal geometry, is calculated to explain the responsive behavior. The interacting energy for the intact methanethiol adsorption is larger than that for the dissociative one, showing that an external electric field cannot make the hydrogen dissociate from the sulfur.

Sensitivity modeling study for an ozone occurrence during the 1996 Paso Del Norte Ozone Campaign.

Surface ozone pollution has been a persistent environmental problem in the US and Europe as well as the developing countries. A key prerequisite to find effective alternatives to meeting an ozone air quality standard is to understand the importance of local anthropogenic emissions, the significance of biogenic emissions, and the contribution of long-range transport. In this study, an air quality modeling system that includes chemistry and transport, CMAQ, an emission processing model, SMOKE, and a mesoscale numerical meteorological model, WRF, has been applied to investigate an ozone event occurring during the period of the 1996 Paso del Norte Ozone Campaign. The results show that the modeling system exhibits the capability to simulate this high ozone occurrence by providing a comparable temporal variation of surface ozone concentration at one station and to capture the spatial evolution of the event. Several sensitivity tests were also conducted to identify the contributions to high surface ozone concentration from eight VOC subspecies, biogenic VOCs, anthropogenic VOCs and long-range transportation of ozone and its precursors. It is found that the reductions of ETH, ISOP, PAR, OLE and FORM help to mitigate the surface ozone concentration, and like anthropogenic VOCs, biogenic VOC plays a nonnegligible role in ozone formation. But for this case, long-range transport of ozone and its precursors appears to produce an insignificant contribution.