Deceptively Simple NMR Spectra of Contiguously 13C-enriched Compounds

Contiguously 13C-enriched compounds are widely used in biosynthetic studies, since they effectively label a bonded pair of carbon atoms, rather than an individual atom. Such compounds are referred to as »bond labeled« compounds. With such substrates, the course of biosynthesis can be followed using 13C-NMR spectroscopy. When the enriched carbon atoms are chemically but not magnetically equivalent, the 13C-NMR spectra are unusual, and such spectra have been labeled "deceptively simple«. Furthermore, the use of standard NMR experiments such as DEPT (Distortionless Enhancement by Polarization Transfer) is complicated by the presence of homonuclear coupling between 13C nuclei. At natural abundance, the 13C nucleus is magnetically dilute and shows no homonuclear coupling. This paper analyzes the 13C-NMR spectra of a series of molecules derived from fully 13C-enriched acetylene, and explores some of the complications that arise in applying pulse NMR methods

Microstructural characterisation of TiAlTiAu and TiAlPdAu ohmic contacts to AlGaN/GaN

Ti/Al/Ti/Au and Ti/Al/Pd/Au contacts to AlGaN/GaN have been investigated to ascertain the effect of annealing temperature on the structural evolution of the contacts. Ti/Al/Ti/Au contacts become ohmic after rapid thermal annealing at 750°C or higher, corresponding to the formation of an interfacial TiN phase, with inclusions penetrating through the AlGaN layer observed after annealing at 950°C. The Pd layer is shown to be more efficient at inhibiting diffusion of Au to the interface than Ti. Ohmic behaviour was not seen with the Ti/Al/Pd/Au scheme. Either the presence of Au at the interface may improve ohmic behaviour, or the Ti:Al ratio is insufficient in this scheme

Functional asymmetry in the lysyl-tRNA synthetase explored by molecular dynamics, free energy calculations and experiment

BACKGROUND: Charging of transfer-RNA with cognate amino acid is accomplished by the aminoacyl-tRNA synthetases, and proceeds through an aminoacyl adenylate intermediate. The lysyl-tRNA synthetase has evolved an active site that specifically binds lysine and ATP. Previous molecular dynamics simulations of the heat-inducible Escherichia coli lysyl-tRNA synthetase, LysU, have revealed differences in the binding of ATP and aspects of asymmetry between the nominally equivalent active sites of this dimeric enzyme. The possibility that this asymmetry results in different binding affinities for the ligands is addressed here by a parallel computational and biochemical study. RESULTS: Biochemical experiments employing isothermal calorimetry, steady-state fluorescence and circular dichroism are used to determine the order and stoichiometries of the lysine and nucleotide binding events, and the associated thermodynamic parameters. An ordered mechanism of substrate addition is found, with lysine having to bind prior to the nucleotide in a magnesium dependent process. Two lysines are found to bind per dimer, and trigger a large conformational change. Subsequent nucleotide binding causes little structural rearrangement and crucially only occurs at a single catalytic site, in accord with the simulations. Molecular dynamics based free energy calculations of the ATP binding process are used to determine the binding affinities of each site. Significant differences in ATP binding affinities are observed, with only one active site capable of realizing the experimental binding free energy. Half-of-the-sites models in which the nucleotide is only present at one active site achieve their full binding potential irrespective of the subunit choice. This strongly suggests the involvement of an anti-cooperative mechanism. Pathways for relaying information between the two active sites are proposed. CONCLUSIONS: The asymmetry uncovered here appears to be a common feature of oligomeric aminoacyl-tRNA synthetases, and may play an important functional role. We suggest a manner in which catalytic efficiency could be improved by LysU operating in an alternating sites mechanism

Subsonic and Transonic Wind Tunnel Testing of Two Inflatable Aerodynamic Decelerators

Two inflatable aerodynamic decelerator designs were tested in the Transonic Dynamics Tunnel at the NASA Langley Research Center: a tension cone and an isotensoid. The tension cone consists of a flexible tension shell attached to a torus and the isotensoid employs a ram-air inflated envelope. Tests were conducted at Mach numbers from 0.3 to 1.08 and Reynolds numbers from 0.59 to 2.46 million. The main objective of these tests was to obtain static aerodynamic coefficients at subsonic and transonic speeds to supplement supersonic aerodynamic data for these same two designs. The axial force coefficients of both designs increased smoothly from subsonic through transonic Mach numbers. Dynamic data show significant oscillation of the tension cone and minimal oscillation of the isotensoid. The transonic and subsonic data will be used to assemble an inflatable decelerator aerodynamic database for use in computational analyses and system studies

Incomplete renal tubular acidosis as a predisposing factor for calcium phosphate stones in neuropathic bladder: a case report

We present a male tetraplegic patient, who developed stones in neuropathic bladder six times within a span of three years. Unusual features of this case are: (1) This patient started developing stones in urinary bladder thirteen years after sustaining spinal cord injury. (2) He was performing intermittent catheterisation and did not have an indwelling catheter. (3) The presenting symptom of vesical lithiasis was abdominal spasms and not urine infection. (4) The major component of the stones was calcium phosphate; magnesium ammonium phosphate was completely absent in the calculus on four occasions. (5) Proteus species were not grown from urine at any time. (6) This patient failed to acidify urine below a pH of 5.3 after taking simultaneously furosemide (40 mg) and fludrocortrisone (1 mg), which suggested incomplete renal tubular acidosis type 1

Microstructural characterisation of TiAlTiAu and TiAlPdAu ohmic contacts to AlGaN/GaN

Ti/Al/Ti/Au and Ti/Al/Pd/Au contacts to AlGaN/GaN have been investigated to ascertain the effect of annealing temperature on the structural evolution of the contacts. Ti/Al/Ti/Au contacts become ohmic after rapid thermal annealing at 750°C or higher, corresponding to the formation of an interfacial TiN phase, with inclusions penetrating through the AlGaN layer observed after annealing at 950°C. The Pd layer is shown to be more efficient at inhibiting diffusion of Au to the interface than Ti. Ohmic behaviour was not seen with the Ti/Al/Pd/Au scheme. Either the presence of Au at the interface may improve ohmic behaviour, or the Ti:Al ratio is insufficient in this scheme

Aerodynamic and Aeroelastic Characteristics of a Tension Cone Inflatable Aerodynamic Decelerator

The supersonic aerodynamic and aeroelastic characteristics of a tension cone inflatable aerodynamic decelerator were investigated by wind tunnel testing. Two sets of tests were conducted: one using rigid models and another using textile models. Tests using rigid models were conducted over a Mach number range from 1.65 to 4.5 at angles of attack from -12 to 20 degrees. The axial, normal, and pitching moment coefficients were found to be insensitive to Mach number over the tested range. The axial force coefficient was nearly constant (C(sub A) = 1.45 +/- 0.05) with respect to angle of attack. Both the normal and pitching moment coefficients were nearly linear with respect to angle of attack. The pitching moment coefficient showed the model to be statically stable about the reference point. Schlieren images and video showed a detached bow shock with no evidence of large regions of separated flow and/or embedded shocks at all Mach numbers investigated. Qualitatively similar static aerodynamic coefficient and flow visualization results were obtained using textile models at a Mach number of 2.5. Using inflatable textile models the torus pressure required to maintain the model in the fully-inflated configuration was determined. This pressure was found to be sensitive to details in the structural configuration of the inflatable models. Additional tests included surface pressure measurements on rigid models and deployment and inflation tests with inflatable models