An unsteady helicopter rotor: Fuselage interaction analysis

A computational method was developed to treat unsteady aerodynamic interactions between a helicopter rotor, wake, and fuselage and between the main and tail rotors. An existing lifting line prescribed wake rotor analysis and a source panel fuselage analysis were coupled and modified to predict unsteady fuselage surface pressures and airloads. A prescribed displacement technique is used to position the rotor wake about the fuselage. Either a rigid blade or an aeroelastic blade analysis may be used to establish rotor operating conditions. Sensitivity studies were performed to determine the influence of the wake fuselage geometry on the computation. Results are presented that describe the induced velocities, pressures, and airloads on the fuselage and on the rotor. The ability to treat arbitrary geometries is demonstrated using a simulated helicopter fuselage. The computational results are compared with fuselage surface pressure measurements at several locations. No experimental data was available to validate the primary product of the analysis: the vibratory airloads on the entire fuselage. A main rotor-tail rotor interaction analysis is also described, along with some hover and forward flight

Frequency response calibration of recess-mounted pressure transducers

A technique is described for measuring the frequency response of pressure transducers mounted inside a model, where a narrow pipette leads to an orifice at the surface. An acoustic driver is mounted to a small chamber which has an opening at the opposite end with an O-ring seal to place over the orifice. A 3.18 mm (1/8 inch) reference microphone is mounted to one side of the chamber. The acoustic driver receives an input of white noise, and the transducer and reference microphone outputs are compared to obtain the frequency response of the pressure transducer. Selected results are presented in the form of power spectra for both the transducer and the reference, as well as the amplitude variation and phase shift between the two signals as a function of frequency. The effect of pipette length and the use of this technique for identifying both blocked orifices and faulty transducers are described

A polymorph of tetra­ethyl­ammonium chloride

The structure of the title compound, C8H20N+·Cl−, is compared with a polymorph that was described earlier in the same space group. Differences in the conformations of the ethyl groups of the cation exist between the polymorphs. This study is given here in order to provide additional unit-cell data for use in qualitative identification of crystalline samples obtained in syntheses in which Et4N+·Cl− is either used or generated

Relative Reactivity of the Metal-Amido versus Metal-Imido Bond in Linked Cp-Amido and Half-Sandwich Complexes of Vanadium

Treatment of (η5-C5H4C2H4NR)V(N-t-Bu)Me (R = Me, i-Pr) and CpV(N-p-Tol)(N-i-Pr2)Me (Cp = η5-C5H5) with B(C6F5)3 or [Ph3C][B(C6F5)4] results in formation of the corresponding cations, [(η5-C5H4C2H4NR)V(N-t-Bu)]+ and [CpV(N-p-Tol)(N-i-Pr2)]+. The latter could also be generated as its N,N-dimethylaniline adduct by treatment of the methyl complex with [PhNMe2H][BAr4] (Ar = Ph, C6F5). Instead, the analogous reaction with the linked Cp-amido precursor results in protonation of the imido-nitrogen atom. Sequential cyclometalation of the amide substituents gave cationic imine complexes [(η5-C5H4C2H4NCR'2)V(NH-t-Bu)]+ (R' = H, Me) and methane. Reaction of cationic [(η5-C5H4C2H4NR)V(N-t-Bu)]+ with olefins affords the corresponding olefin adducts, whereas treatment with 1 or 2 equiv of 2-butyne results in insertion of the alkyne into the vanadium-nitrogen single bond, affording the mono- and bis-insertion products [(η5-C5H4C2H4N(i-Pr)C2Me2)V(N-t-Bu)]+ and [(η5-C5H4C2H4N(i-Pr)C4Me4)V(N-t-Bu)]+. The same reaction with the half-sandwich compound [CpV(N-p-Tol)(N-i-Pr2)]+ results in a paramagnetic compound that, upon alcoholysis, affords sec-butylidene-p-tolylamine, suggesting an initial [2+2] cycloaddition reaction. The difference in reactivity between the V-N bond versus the V=N bond was further studied using computational methods. Results were compared to the isoelectronic titanium system CpTi(NH)(NH2). These studies indicate that the kinetic product in each system is derived from a [2+2] cycloaddition reaction. For titanium, this was found as the thermodynamic product as well, whereas the insertion reaction was found to be thermodynamically more favorable in the case of vanadium.

Vanadium (β-(Dimethylamino)ethyl)cyclopentadienyl Complexes with Diphenylacetylene Ligands

Reduction of the V(III) (β-(dimethylamino)ethyl)cyclopentadienyl dichloride complex [η5:η1-C5H4(CH2)2NMe2]VCl2(PMe3) with 1 equiv of Na/Hg yielded the V(II) dimer {[η5:η1-C5H4(CH2)2NMe2]V(µ-Cl)}2 (2). This compound reacted with diphenylacetylene in THF to give the V(II) alkyne adduct [η5:η1-C5H4(CH2)2NMe2]VCl(η2-PhC≡CPh). Further reduction of 2 with Mg in the presence of diphenylacetylene resulted in oxidative coupling of two diphenylacetylene groups to yield the diamagnetic, formally V(V), bent metallacyclopentatriene complex [η5:η1-C5H4(CH2)2NMe2]V(C4Ph4).

Discovery of Sexual Dimorphisms in Metabolic and Genetic Biomarkers

Metabolomic profiling and the integration of whole-genome genetic association data has proven to be a powerful tool to comprehensively explore gene regulatory networks and to investigate the effects of genetic variation at the molecular level. Serum metabolite concentrations allow a direct readout of biological processes, and association of specific metabolomic signatures with complex diseases such as Alzheimer's disease and cardiovascular and metabolic disorders has been shown. There are well-known correlations between sex and the incidence, prevalence, age of onset, symptoms, and severity of a disease, as well as the reaction to drugs. However, most of the studies published so far did not consider the role of sexual dimorphism and did not analyse their data stratified by gender. This study investigated sex-specific differences of serum metabolite concentrations and their underlying genetic determination. For discovery and replication we used more than 3,300 independent individuals from KORA F3 and F4 with metabolite measurements of 131 metabolites, including amino acids, phosphatidylcholines, sphingomyelins, acylcarnitines, and C6-sugars. A linear regression approach revealed significant concentration differences between males and females for 102 out of 131 metabolites (p-values<3.8 x 10(-4); Bonferroni-corrected threshold). Sex-specific genome-wide association studies (GWAS) showed genome-wide significant differences in beta-estimates for SNPs in the CPS1 locus (carbamoyl-phosphate synthase 1, significance level: p<3.8 x 10(-10); Bonferroni-corrected threshold) for glycine. We showed that the metabolite profiles of males and females are significantly different and, furthermore, that specific genetic variants in metabolism-related genes depict sexual dimorphism. Our study provides new important insights into sex-specific differences of cell regulatory processes and underscores that studies should consider sex-specific effects in design and interpretation

X-ray absorption spectroscopy systematics at the tungsten L-edge

A series of mononuclear six-coordinate tungsten compounds spanning formal oxidation states from 0 to +VI, largely in a ligand environment of inert chloride and/or phosphine, has been interrogated by tungsten L-edge X-ray absorption spectroscopy. The L-edge spectra of this compound set, comprised of [W&lt;sup&gt;0&lt;/sup&gt;(PMe&lt;sub&gt;3&lt;/sub&gt;)&lt;sub&gt;6&lt;/sub&gt;], [W&lt;sup&gt;II&lt;/sup&gt;Cl&lt;sub&gt;2&lt;/sub&gt;(PMePh&lt;sub&gt;2&lt;/sub&gt;)&lt;sub&gt;4&lt;/sub&gt;], [W&lt;sup&gt;III&lt;/sup&gt;Cl&lt;sub&gt;2&lt;/sub&gt;(dppe)&lt;sub&gt;2&lt;/sub&gt;][PF&lt;sub&gt;6&lt;/sub&gt;] (dppe = 1,2-bis(diphenylphosphino)ethane), [W&lt;sup&gt;IV&lt;/sup&gt;Cl&lt;sub&gt;4&lt;/sub&gt;(PMePh&lt;sub&gt;2&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;], [W&lt;sup&gt;V&lt;/sup&gt;(NPh)Cl&lt;sub&gt;3&lt;/sub&gt;(PMe&lt;sub&gt;3&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;], and [W&lt;sup&gt;VI&lt;/sup&gt;Cl&lt;sub&gt;6&lt;/sub&gt;] correlate with formal oxidation state and have usefulness as references for the interpretation of the L-edge spectra of tungsten compounds with redox-active ligands and ambiguous electronic structure descriptions. The utility of these spectra arises from the combined correlation of the estimated branching ratio (EBR) of the L&lt;sub&gt;3,2&lt;/sub&gt;-edges and the L&lt;sub&gt;1&lt;/sub&gt; rising-edge energy with metal Z&lt;sub&gt;eff&lt;/sub&gt;, thereby permitting an assessment of effective metal oxidation state. An application of these reference spectra is illustrated by their use as backdrop for the L-edge X-ray absorption spectra of [W&lt;sup&gt;IV&lt;/sup&gt;(mdt)&lt;sub&gt;2&lt;/sub&gt;(CO)&lt;sub&gt;2&lt;/sub&gt;] and [W&lt;sup&gt;IV&lt;/sup&gt;(mdt)&lt;sub&gt;2&lt;/sub&gt;(CN)&lt;sub&gt;2&lt;/sub&gt;]&lt;sup&gt;2–&lt;/sup&gt; (mdt&lt;sup&gt;2–&lt;/sup&gt; = 1,2-dimethylethene-1,2-dithiolate), which shows that both compounds are effectively W&lt;sup&gt;IV&lt;/sup&gt; species. Use of metal L-edge XAS to assess a compound of uncertain formulation requires: 1) Placement of that data within the context of spectra offered by unambiguous calibrant compounds, preferably with the same coordination number and similar metal ligand distances. Such spectra assist in defining upper and/or lower limits for metal Z&lt;sub&gt;eff&lt;/sub&gt; in the species of interest; 2) Evaluation of that data in conjunction with information from other physical methods, especially ligand K-edge XAS; 3) Increased care in interpretation if strong π-acceptor ligands, particularly CO, or π-donor ligands are present. The electron-withdrawing/donating nature of these ligand types, combined with relatively short metal-ligand distances, exaggerate the difference between formal oxidation state and metal Z&lt;sub&gt;eff&lt;/sub&gt; or, as in the case of [W&lt;sup&gt;IV&lt;/sup&gt;(mdt)&lt;sub&gt;2&lt;/sub&gt;(CO)&lt;sub&gt;2&lt;/sub&gt;], add other subtlety by modulating the redox level of other ligands in the coordination sphere