Role of Internal Motions and Molecular Geometry on the NMR Relaxation of Hydrocarbons

The role of internal motions and molecular geometry on $^1$H NMR relaxation times $T_{1,2}$ in hydrocarbons is investigated using MD (molecular dynamics) simulations of the autocorrelation functions for in{\it tra}molecular $G_R(t)$ and in{\it ter}molecular $G_T(t)$ $^1$H-$^1$H dipole-dipole interactions arising from rotational ($R$) and translational ($T$) diffusion, respectively. We show that molecules with increased molecular symmetry such as neopentane, benzene, and isooctane show better agreement with traditional hard-sphere models than their corresponding straight-chain $n$-alkane, and furthermore that spherically-symmetric neopentane agrees well with the Stokes-Einstein theory. The influence of internal motions on the dynamics and $T_{1,2}$ relaxation of $n$-alkanes are investigated by simulating rigid $n$-alkanes and comparing with flexible (i.e. non-rigid) $n$-alkanes. Internal motions cause the rotational and translational correlation-times $\tau_{R,T}$ to get significantly shorter and the relaxation times $T_{1,2}$ to get significantly longer, especially for longer-chain $n$-alkanes. Site-by-site simulations of $^1$H's along the chains indicate significant variations in $\tau_{R,T}$ and $T_{1,2}$ across the chain, especially for longer-chain $n$-alkanes. The extent of the stretched (i.e. multi-exponential) decay in the autocorrelation functions $G_{R,T}(t)$ are quantified using inverse Laplace transforms, for both rigid and flexible molecules, and on a site-by-site bases. Comparison of $T_{1,2}$ measurements with the site-by-site simulations indicate that cross-relaxation (partially) averages-out the variations in $\tau_{R,T}$ and $T_{1,2}$ across the chain of long-chain $n$-alkanes. This work also has implications on the role of nano-pore confinement on the NMR relaxation of fluids in the organic-matter pores of kerogen and bitumen

Phase diagram of iron, revised-core temperatures

Shock-wave experiments on iron preheated to 1573 K from 14 to 73 GPa, yield sound velocities of the γ- and liquid-phases. Melting is observed in the highest pressure (∼71 ± 2 GPa) experiments at calculated shock temperatures of 2775 ± 160 K. This single crossing of the γ-liquid boundary agrees with the γ-iron melting line of Boehler [1993], Saxena et al. [1993], and Jephcoat and Besedin [1997]. This γ-iron melting curve is ∼300°C lower than that of Shen et al. [1998] at 80 GPa. In agreement with Brown [2001] the discrepancy between the diamond cell melting data and the iron shock temperatures require the occurrence of yet another sub-solidus phase along the principal Hugoniot at ∼200 GPa. This would reconcile the static and dynamic data for iron's melting curve. Upward pressure and temperature extrapolation of the γ-iron melting curve to 330 GPa yields 5300 ± 400 K for the inner core-outer core boundary temperature

Shock temperatures and the melting point of iron

New measurements of the ratio of Fe to LiF and Al_2O_3 anvil thermal diffusivities are used to obtain revised shock temperatures for Fe. New results match Brown and McQueen’s (1) calculations of the temperatures of 5000 and 5800K at the 200 and 243 GPa transitions in Fe. New sound speed measurements along the Hugoniot of γ-Fe, centered at 1573K, demonstrate that this phase melts at ∼70 GPa and ∼2800 K and the γ phase does not occur above ∼93 GPa. At higher pressures, perhaps over the entire pressure range of the Earth’s molten outer core (132 to 330 GPa), the β (dhcp) phase, and not the ε phase, appears to be the solidus phase of pure Fe

Methane activation and exchange by titanium-carbon multiple bonds

We demonstrate that a titanium-carbon multiple bond, specifically an alkylidyne ligand in the transient complex, (PNP)Ti≡C^(t)Bu (A) (PNP^− = N[2-P(CHMe_2)_(2)-4-methylphenyl]_2), can cleanly activate methane at room temperature with moderately elevated pressures to form (PNP)Ti=CHtBu(CH_3). Isotopic labeling and theoretical studies suggest that the alkylidene and methyl hydrogens exchange, either via tautomerization invoking a methylidene complex, (PNP)Ti=CH_(2)(CH_(2)^(t)Bu), or by forming the methane adduct (PNP)Ti≡C^(t)Bu(CH_4). The thermal, fluxional and chemical behavior of (PNP)Ti=CH^(t)Bu(CH_3) is also presented in this study

Cerebral Air Embolism from Angioinvasive Cavitary Aspergillosis

Background. Nontraumatic cerebral air embolism cases are rare. We report a case of an air embolism resulting in cerebral infarction related to angioinvasive cavitary aspergillosis. To our knowledge, there have been no previous reports associating these two conditions together. Case Presentation. A 32-year-old female was admitted for treatment of acute lymphoblastic leukemia (ALL). Her hospital course was complicated by pulmonary aspergillosis. On hospital day 55, she acutely developed severe global aphasia with right hemiplegia. A CT and CT-angiogram of her head and neck were obtained demonstrating intravascular air emboli within the left middle cerebral artery (MCA) branches. She was emergently taken for hyperbaric oxygen therapy (HBOT). Evaluation for origin of the air embolus revealed an air focus along the left lower pulmonary vein. Over the course of 48 hours, her symptoms significantly improved. Conclusion. This unique case details an immunocompromised patient with pulmonary aspergillosis cavitary lesions that invaded into a pulmonary vein and caused a cerebral air embolism. With cerebral air embolisms, the acute treatment option differs from the typical ischemic stroke pathway and the provider should consider emergent HBOT. This case highlights the importance of considering atypical causes of acute ischemic stroke

Multi-Mission Power Analysis Tool (MMPAT) Version 3

The Multi-Mission Power Analysis Tool (MMPAT) simulates a spacecraft power subsystem including the power source (solar array and/or radioisotope thermoelectric generator), bus-voltage control, secondary battery (lithium-ion or nickel-hydrogen), thermostatic heaters, and power-consuming equipment. It handles multiple mission types including heliocentric orbiters, planetary orbiters, and surface operations. Being parametrically driven along with its user-programmable features can reduce or even eliminate any need for software modifications when configuring it for a particular spacecraft. It provides multiple levels of fidelity, thereby fulfilling the vast majority of a project s power simulation needs throughout the lifecycle. It can operate in a stand-alone mode with a graphical user interface, in batch mode, or as a library linked with other tools. This software can simulate all major aspects of a spacecraft power subsystem. It is parametrically driven to reduce or eliminate the need for a programmer. Added flexibility is provided through user-designed state models and table-driven parameters. MMPAT is designed to be used by a variety of users, such as power subsystem engineers for sizing power subsystem components; mission planners for adjusting mission scenarios using power profiles generated by the model; system engineers for performing system- level trade studies using the results of the model during the early design phases of a spacecraft; and operations personnel for high-fidelity modeling of the essential power aspect of the planning picture