Search NASA⌕ Search

SEARCH · Search NASA

Results for “ALKYLATION”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 217 records · Page 12
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Conical intersection and coherent vibrational dynamics in alkyl iodides captured by attosecond transient absorption spectroscopy

The photodissociation dynamics of alkyl iodides along the C–I bond are captured by attosecond extreme-ultraviolet (XUV) transient absorption spectroscopy employing resonant ∼20 fs UV pump pulses. The methodology of previous experiments on CH3I [Chang et al., J. Chem. Phys. 154, 234301 (2021)] is extended to the investigation of a C–I bond-breaking reaction in the dissociative A-band of C2H5I, i-C3H7I, and t-C4H9I. Probing iodine 4d core-to-valence transitions in the XUV enables one to map wave packet bifurcation at a conical intersection in the A-band as well as coherent vibrations in the ground state of the parent molecules. Analysis of spectroscopic bifurcation signatures yields conical intersection crossing times of 15 ± 4 fs for CH3I, 14 ± 5 fs for C2H5I, and 24 ± 4 fs for i-C3H7I and t-C4H9I, respectively. Observations of coherent vibrations, resulting from a projection of A-band structural dynamics onto the ground state by resonant impulsive stimulated Raman scattering, indirectly reveal multimode C–I stretch and CCI bend vibrations in the A-bands of C2H5I, i-C3H7I, and t-C4H9I.

Chang, Kristina F. (ORCID:000000022315039X)↗
DOE OSTI2023

The multichannel i -propyl + O2 reaction system: A model of secondary alkyl radical oxidation

The i-propyl + O2 reaction mechanism has been investigated by definitive quantum chemical methods to establish this system as a benchmark for the combustion of secondary alkyl radicals. Focal point analyses extrapolating to the ab initio limit were performed based on explicit computations with electron correlation treatments through coupled cluster single, double, triple, and quadruple excitations and basis sets up to cc-pV5Z. The rigorous coupled cluster single, double, and triple excitations/cc-pVTZ level of theory was used to fully optimize all reaction species and transition states, thus, removing some substantial flaws in reference geometries existing in the literature. The vital i-propylperoxy radical (MIN1) and its concerted elimination transition state (TS1) were found 34.8 and 4.4 kcal mol−1 below the reactants, respectively. Two β-hydrogen transfer transition states (TS2, TS2′) lie above the reactants by (1.4, 2.5) kcal mol−1 and display large Born–Oppenheimer diagonal corrections indicative of nearby surface crossings. An α-hydrogen transfer transition state (TS5) is discovered 5.7 kcal mol−1 above the reactants that bifurcates into equivalent α-peroxy radical hanging wells (MIN3) prior to a highly exothermic dissociation into acetone + OH. The reverse TS5 → MIN1 intrinsic reaction path also displays fascinating features, including another bifurcation and a conical intersection of potential energy surfaces. An exhaustive conformational search of two hydroperoxypropyl (QOOH) intermediates (MIN2 and MIN3) of the i-propyl + O2 system located nine rotamers within 0.9 kcal mol−1 of the corresponding lowest-energy minima.

Chemistry↗
DOE OSTI2024

NEXAFS spectroscopy of alkylated benzothienobenzothiophene thin films at the carbon and sulfur K-edges

Alkylated benzothienobenzothiophenes are an important class of organic semiconductors that exhibit high performance in solution-processed organic field-effect transistors. In this work, we study the near-edge x-ray absorption fine-structure (NEXAFS) spectra of 2,7-didecyl[1]benzothieno[3,2-b][1]benzothiophene (C 10 -BTBT) at both the carbon and sulfur K-edges. Angle-resolved experiments of thin films are performed to characterize the dichroism associated with molecular orientation. First-principles calculations using the density functional theory-based many-body x-ray absorption spectroscopy (MBXAS) method are also performed to correlate the peaks observed and their dichroism with transitions to specific antibonding molecular orbitals. Interestingly, the dichroism of the dominant, lowest energy peak is opposite at the carbon and sulfur K-edges. While the low-energy peak at the carbon K-edge is assigned to carbon 1s → π* transitions with transition dipole moment (TDM) perpendicular to the planar BTBT core, the dominant low energy peak at the sulfur K-edge is assigned to sulfur 1s → σ* transitions with TDM oriented along the long axis of the BTBT core. These differences at the sulfur and carbon K-edges are understood through the MBAXS simulations that find a reordering of the energy of the lowest energy π* and σ* transitions at the sulfur K-edge due to the strong localization of the σ* orbital over the sulfur atom. This work highlights differences in the NEXAFS spectra of organic semiconductors at carbon and sulfur K-edges and provides new insights into peak assignment and x-ray dichroism relevant for studying the molecular orientation of organic semiconductor films.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Al-alkyls as acceptor dopant precursors for atomic-scale devices

Atomically precise ultradoping of silicon is possible with atomic resists, area-selective surface chemistry, and a limited set of hydride and halide precursor molecules, in a process known as atomic precision advanced manufacturing (APAM). It is desirable to expand this set of precursors to include dopants with organic functional groups and in this work we consider aluminium alkyls, to expand the applicability of APAM. We explore the impurity content and selectivity that results from using trimethyl aluminium and triethyl aluminium precursors on Si(001) to ultradope with aluminium through a hydrogen mask. Comparison of the methylated and ethylated precursors helps us understand the impact of hydrocarbon ligand selection on incorporation surface chemistry. Combining scanning tunneling microscopy and density functional theory calculations, we assess the limitations of both classes of precursor and extract general principles relevant to each.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Acute Limonene Toxicity in Escherichia coli Is Caused by Limonene Hydroperoxide and Alleviated by a Point Mutation in Alkyl Hydroperoxidase AhpC

ABSTRACT Limonene, a prime component of citrus peel oil, has a number of applications related to microbiology. The antimicrobial properties of limonene make it a popular disinfectant and food preservative, while its possibility as a biofuel component has made it the target of renewable production efforts through microbial metabolic engineering. For both applications, an understanding of microbial sensitivity or tolerance to limonene is crucial, but the mechanism of limonene toxicity remains enigmatic. In this study, we characterized a limonene-tolerant strain of Escherichia coli and found a mutation in ahpC , encoding alkyl hydroperoxidase, which alleviated limonene toxicity. We demonstrate that the acute toxicity previously attributed to limonene is largely due to the common oxidation product limonene hydroperoxide, which forms spontaneously in aerobic environments. The mutant AhpC protein with an L-to-Q change at position 177 (AhpC L177Q ) was able to alleviate this toxicity by reducing the hydroperoxide to a more benign compound. We reveal that the degree of limonene toxicity is a function of its oxidation level and that nonoxidized limonene has relatively little toxicity to wild-type E. coli cells. Our results have implications for both the renewable production of limonene and the applications of limonene as an antimicrobial.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2013

Electrophilic Metal Alkyl Chemistry in New Ligand Environments

The goals of this project were to design new electrophilic metal alkyl complexes and to exploit these systems in fundamental studies of olefin polymerization and other important and new catalytic reactions. A key target reaction is insertion copolymerization of olefins and polar CH 2 =CHX vinyl monomers such as vinyl halides and vinyl ethers. During the period covered by this report we (i) investigated the properties of ortho-alkoxy-arylphosphine ligands in Ni-based olefin polymerization catalysts, (ii) studied the synthesis of double-end-capped polyethylene using group 4 metal catalysts that contain tris-pyrazolylborate ligands, (iii) explored the ethylene insertion reactivity of group 4 metal tris-pyrazolyl-borate complexes, (iv) showed that (α- diimine)PdMe + species undergo multiple insertion of silyl vinyl ethers, (v) synthesized and explored the reactivity of base-free Ni benzyl complexes that contain ortho-phosphino-arene sulfonate ligands, (vi) established the mechanism of the reaction of vinyl chloride with (α- diimine)PdMe + catalysts, (vii) explored the role of cationic polymerization and insertion chemistry in the reactions of vinyl ethers with (α-diimine)PdMe + species, (viii) discovered a new class of self-assembled tetranuclear Pd catalysts that produce high molecular weight linear polyethylene and copolymerize ethylene and vinyl fluoride, and (ix) developed model systems that enabled investigation of cis-trans isomerization of {phosphine-sulfonate}Pd(II) complexes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Beyond alkyl transfer: Synthesis of main group metal (Mg, Ca, Zn) silyl and tris(oxazolinyl)borato complexes and their stoichiometric and catalytic reactions with borane Lewis acids and carbonyls

Recently, the fundamental knowledge of main group metal chemistry has grown. This progress is crucial for the further development of main group metal compounds in silicon chemistry and catalysis and for advancing their applications as green alternatives to many rare earth and transition metal compounds. This thesis focuses on reactivity beyond the welldocumented alkyl-transfer applications for main group metals, and it highlights examples of reactions with Lewis acids and the reduction of carbonyls.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1971

Alkyl substituent effects on gas-phase acidities - The influence of hybridization.

Exploration of the effect on acidity of alkyl groups bonded to trigonal and digonal carbon. Some results on the relative acidities of toluene and p-xylene, and acetylene and substitute acetylenes, as determined by ion cyclotron resonance (icr) spectroscopy, are described. Some limitations of the CNDO/2 calculation method are discussed.

Brauman, J. I.↗
NASA NTRS1971

Electron-impact promoted fragmentation of alkyl-n-/1-phenylethyl/-carbamates of primary, secondary and tertiary alcohols.

The mass spectra of twenty alkyl carbamates derived from primary, secondary, and tertiary alcohols are investigated, using deuterium labeling and high-resolution mass spectrometry. Several of the primary and secondary alcohol derivatives are found to yield an ion formally equivalent to the product ion of a McLafferty rearrangement. Deuterium labeling, however, revealed a lack, in these carbamate derivatives, of the usual site specificity associated with the McLafferty rearrangement. A double hydrogen rearrangement process was observed in the mass spectra of several carbamates derived from tertiary alcohols.

Pereira, W. E.↗
NASA NTRS1984

Modification of epoxy-reinforced glass-cloth composites with a perfluorinated alkyl ether elastomer

A perfluorinated alkyl ether diacyl fluoride prepolymer (molecular weight about 1500) was coreacted with Epon 828 epoxy resin and diamino diphenyl sulfone to obtain an elastomer-toughened, glass-cloth composite. Improvements in flexural toughness, impact resistance, and water resistance, without loss of strength, modulus of elasticity or a lowering of the glass-transition temperature, were realized over those of the unmodified composite. Factors concerning optimization of the process are discussed. Results suggest that a simultaneously interpenetrating polymer network may be formed which gives rise to a measured improvement in composite mechanical properties.

Rosser, R. W.↗
NASA NTRS1992

Ignition delays, heats of combustion, and reaction rates of aluminum alkyl derivatives used as ignition and combustion enhancers for supersonic combustion

The subject of this paper is the design of supersonic combustors which will be required in order to achieve the needed reaction rates in a reasonable sized combustor. A fuel additive approach, which is the focus of this research, is the use of pyrophorics to shorten the ignition delay time and to increase the energy density of the fuel. Pyrophoric organometallic compounds may also provide an ignition source and flame stabilization mechanism within the combustor, thus permitting use of hydrocarbon fuels in supersonic combustion systems. Triethylaluminum (TEA) and trimethylaluminum (TMA) were suggested for this application due to their high energy density and reactivity. The objective here is to provide comparative data for the ignition quality, the energy content, and the reaction rates of several different adducts of both TEA and TMA. The results of the experiments indicate the aluminum alkyls and their more stable derivatives reduce the ignition delay and total reaction time to JP-10 jet fuel. Furthermore, the temperature dependence of ignition delay and total reaction time of the blends of the adducts are significantly lower than in neat JP-10.

Ryan, Thomas W., III↗
NASA NTRS2000

Alkyl Pyrocarbonate Electrolyte Additives for Performance Enhancement of Li Ion Cells

Lithium ion rechargeable batteries are being developed for various aerospace applications under a NASA-DoD Interagency program. These applications require further improvements in several areas, specifically in the cycle life for LEO and GEO satellites and in the low temperature performance for the Mars Lander and Rover missions. Accordingly, we have been pursuing research studies to achieve improvement in the low temperature performance, long cycle life and active life of Li ion cells. The studies are mainly focused on electrolytes, to identify newer formulations of new electrolyte additives to enhance Li permeability (at low temperatures) and stability towards the electrode. The latter approach is particularly aimed at the formation suitable SEI (solid electrolyte interphase) on carbon electrodes. In this paper, we report the beneficial effect of using alkyl pyrocarbonates as electrolyte additives to improve the low temperature performance of Li ion cells.

Smart, M. C.↗
NASA NTRS1947

Knock-Limited Power Outputs from a CFR Engine Using Internal Coolants: Four Alkyl Amines, Three Alkanolamines, Six Amides, and Eight Heterocyclic Compounds - 3

An investigation of the antiknock effectiveness of various additive-water solutions when used as internal coolants has been conducted at the NACA Cleveland laboratory. Nine compounds have been previously run in a CFR engine and the results are presented. In an effort to find a good anti-knock-coolant additive with more desirable physical properties than those of the nine compounds previously investigated, water solutions of four alkyl amines, three alkanolamines, six amides, and eight heterocyclic compounds were investigated and the results are presented.

Imming, Harry S.↗
NASA NTRS2009

Lubricated Bearing Lifetimes of a Multiply Alkylated Cyclopentane and a Linear Perfluoropolyether Fluid in Oscillatory Motion at Elevated Temperatures in Ultrahigh Vacuum

Bearing life tests in vacuum with three space liquid lubricants, two multiply alkylated cyclopentanes (MACs) and a linear perfluoropolyether (PFPE) were performed. Test conditions included: an 89 N axial load (mean Hertzian stress 0.66 GPa), vacuum level below 7x10(exp -4) Pa, and a +/-30deg dither angle. Dither rate was 75 cycles per minute. Higher (110 to 122 C) and lower temperature tests (75 C) were performed. For the higher temperature tests, the PFPE, Fomblin (Ausimont SpA) Z25 outperformed Pennzane (Shell Global Solutions) X-2000 by more than an order of magnitude. Lubricant evaporation played a key role in these high temperature results. At 75 C, the order was reversed with both Pennzane X-1000 and X-2000 outperforming Fomblin Z25 by more than an order of magnitude. Most Pennzane tests were suspended without failure. The primary failure mechanism in these lower temperature tests was lubricant consumption in the tribocontacts.

Braza, Joseph↗