Search NASA⌕ Search

SEARCH · Search NASA

Results for “alkyls”

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 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Cyclic (Alkyl)(amino)carbene Ligands Enable Cu‐Catalyzed Markovnikov Protoboration and Protosilylation of Terminal Alkynes: A Versatile Portal to Functionalized Alkenes**

Abstract Regioselective hydrofunctionalization of alkynes represents a straightforward route to access alkenyl boronate and silane building blocks. In previously reported catalytic systems, high selectivity is achieved with a limited scope of substrates and/or reagents, with general solutions lacking. Herein, we describe a selective copper‐catalyzed Markovnikov hydrofunctionalization of terminal alkynes that is facilitated by strongly donating cyclic (alkyl)(amino)carbene (CAAC) ligands. Using this method, both alkyl‐ and aryl‐substituted alkynes are coupled with a variety of boryl and silyl reagents with high α‐selectivity. The reaction is scalable, and the products are versatile intermediates that can participate in various downstream transformations. Preliminary mechanistic experiments shed light on the role of CAAC ligands in this process.

Gao, Yang↗
DOE OSTI2025

Late-Stage Oxidation of C( sp 3 )─H Bonds with High Efficiency and Alkyl Group Dihydroxylation of Complex Molecules

Here, the late-stage oxidation of C(sp 3 )─H bonds is highly valuable for modulating the solubility and binding of bioactive compounds and for diversification of complex molecules. Undirected methods for C(sp 3 )─H oxidation are valuable for the installation of hydroxyl groups at sites remote from other functional groups present in the molecule, but existing catalysts are limited by low turnover numbers and lengthy ligand syntheses. Perfluorinated ruthenium porphyrins are highly active catalysts for the oxidation of alkyl C─H bonds, but the scope of the transformation with complex molecules under conditions of limiting substrate has not been investigated. We report that carbonylruthenium(II) tetrakis(pentafluorophenyl)porphyrin [Ru(TPFPP)(CO)] catalyzes the selective oxidation of tertiary C(sp 3 )─H bonds in a broad range of complex natural products and drugs, with turnover numbers as high as 1000, and the tolerance of the reaction to various functional groups was rapidly assessed by performing a model reaction in the presence of additives. We show how the combination of this undirected C(sp 3 )─H oxidation and a directed C(sp 3 )─H silylation and oxidation provides rapid access to highly oxidized, 1,2-diol derivatives of natural products by a formal dihydroxylation of an alkyl group.

Alcohols↗
DOE OSTI2023

A Straightforward Access to Cyclic (Alkyl)(amino)carbene Copper (I) Complexes

Here, the synthesis and characterization of cyclic (alkyl)(amino)carbene, bicyclic (alkyl)(amino)carbene and cyclic (amino)(barrelene)carbene copper (I) complexes is reported. These complexes are obtained via a scalable, versatile, green, and cost/user-friendly strategy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Crystallization-induced emission enhancement of alkyl chain-dependent pyrene-based luminogens: Visual detection of nitro-explosives

In view of the widespread applications and urgent need for efficient blue emitting materials, the synthesis of such materials has seen renewed interest. In the present work, three alkyl chain-dependent blue emitting pyrene-based luminogens were synthesized and characterized. Here, the experimental results show that these luminogens exhibited high photoluminescence efficiency both in solution (>86%) and in the solid state (>35%). Interestingly, 1,3,6,8-tetrakis (pentylphenyl)pyrene (TPPy), as a photoelectric functional material, was endowed with higher quantum yield (72%) and competitiveness due to a remarkable crystallization-induced emission enhancement (CIEE) property. More importantly, TPPy exhibits high sensitivity and selectivity for ortho-nitroaniline (o-NA) with low limit of detection (9.99 × 10 -8 M), which is mainly due to the distinctive odd-even effects of the terminal alkyl chain. The results demonstrate that this type of luminogen can potentially be utilized for practical applications in the field of contaminant or explosive detection as a sensitive and portable fluorimeter.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Multiscale Crystalline Structure of Confined Polypeptoid Films: The Effect of Alkyl Side Chain Branching

Here we report the effect of alkyl side chain branching on melt-recrystallization of nanoconfined polypeptoid films using poly(N-octyl glycine) (PNOG) and poly(N-2-ethyl-1-hexyl glycine) (PNEHG) as model systems. Upon cooling from the isotropic melt, confined PNOG molecules recrystallize into a near-perfect orthorhombic crystal structure with the board-like molecules stacked face-to-face in the substrate-parallel direction, resulting in long-range ordered wormlike lamellae that occupy the entire film. By contrast, rod-like PNEHG molecules bearing branched N-2-ethyl-1-hexyl side chains stack into a columnar hexagonal mesophase with their backbones oriented parallel to the substrates, forming micron-sized sheaf-like superstructures under confinement, exposing large areas of empty spaces in the film. These findings highlight the effect of alkyl side chain branching on the packing motif and multiscale crystalline structure of polypeptoids under a nanoconfined geometry.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Engineering Enantiocomplementary Protoglobins for Stereoconvergent Construction of N -Alkylated α-Aminoketones

The synthesis of enantiopure compounds from a mixture of E/Z alkenes represents a notable challenge in synthetic chemistry. While enzymes excel in achieving unparalleled selectivity, their inherent specificity often confines activity to a single stereoisomeric substrate, consequently restricting the overall efficiency of such transformations. Here, we demonstrate that protoglobin-derived hemoproteins can catalyze stereoconvergent intermolecular amination using simple N-alkyl hydroxylamines as nitrene precursors, a transformation which remains elusive in synthetic chemistry. These engineered enzymes process E/Z mixtures of silyl enol ethers, enabling the precise incorporation of N-alkyl amino moieties (−NHAlkyl) into diverse molecular structures (up to 79% yield and 95% ee). Two complementary protoglobin variants were engineered using directed evolution to enable enantiodivergent synthesis of both enantiomers of α-aminoketones. This enzymatic platform achieves stereoconvergent and enantiodivergent transformations, facilitating the conversion of simple chemicals into an array of valuable pharmaceutical compounds featuring aminoketone functionalities.

Alcohols↗
DOE OSTI2023

Distinguishing photo-induced oxygen attack on alkyl chain versus conjugated backbone for alkylthienyl-benzodithiophene (BDTT)-based push–pull polymers

Synthetic design has enabled increasing power conversion efficiency advances in organic photovoltaics (OPV). One continuing knowledge gap is detailed understanding of single-material chemical (photo)stability. Many considerations are based on prior OPV-relevant donor homopolymer systems rather than the next-generation push–pull architectures. Generally, energetic offsets between the lowest occupied molecular orbital of the donor and molecular oxygen are assumed to dictate kinetics of photo-induced charge transfer to a super oxide radical. Herein we determine the ambient-induced photo-degradation pathways, presented as proposed site-specific arrow-pushing mechanisms, for five donor polymers all containing the same push unit – alkylthienyl-substituted-benzodithiophene (BDTT) – but with chemically distinct pull units. The donor-only polymer films were subject to controlled photobleaching in air as an accelerated degradation approach, coupled with simultaneous monitoring of absorptance. Sample subsets were periodically removed and analyzed with X-ray photoelectron spectroscopy, to evaluate near-surface chemical composition and oxygen additions to hetero reporter atoms on either the BDTT push unit or distinct pull unit (i.e., sulphur and nitrogen). Here, this methodology allows us to distinguish between different mechanisms of bond cleavage and formation. Overall, we find that neither polymer redox properties nor individual push or pull unit stability are sufficient to predict photo-oxidative degradation of these polymers. Rather, there is a greater dependence on the susceptibility of unique structural groups within a polymeric system. Alkyl chain oxygen addition is generally the first attack site and direct sulfur oxidation on the conjugated backbone occurs after saturation of the alkyl chain initiation sites. This work provides a standard that could be used to evaluate relative photo-oxidative (in)stability for new OPV materials quickly – prior to time-consuming device optimization – and demonstrates an effective methodology for correlating optical degradation with chemical structure alterations via spectroscopic signatures to guide synthetic design.

14 SOLAR ENERGY↗
DOE OSTI2025

Aluminosilicate-mediated C(sp 2 )–H alkylation of furans using allylic alcohols

Alkyl furans have a variety of applications and therefore numerous approaches exist for their synthesis. While these methods can be effective, there are various drawbacks largely associated with the waste generated. Herein we report a novel method for the direct coupling of readily available furans with allylic alcohols. These include terpenoid alcohols such as geraniol and prenol, which are readily available from renewable, bio-derived feedstocks. Furthermore, the reaction is facilitated using aluminosilicates, including zeolites. It was found that Y-type zeolites were highly effective at mediating the coupling with furan, giving the 2-alkylated furan high yields. While various allylic alcohols were effective for this reaction, the identity of the furan proved to have a drastic impact on reactivity. For substituted furans, the reaction proved most effective with an amorphous aluminosilicate and calculations later revealed potential key factors in further developing and generalizing this methodology.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Stabilization of reactive rare earth alkyl complexes through mechanistic studies

Rare earth tris(alkyl) complexes such as M(CH 2 SiMe 3 ) 3 (sol) n are widely used as precursors for many compounds and as homogeneous catalysts for alkene polymerization and alkane functionalization. However, the thermal instability of those most conveniently made from the commercially available lithium salt of the neosilyl anion, LiCH 2 SiMe 3 , Li(r), restricts their utility. We present a new range of synthetically useful, more kinetically stable rare earth neosilyl solvates, derived from a full kinetic study of the various possible decomposition mechanisms of 7 known and 12 new solvated rare earth neosilyl complexes M(CH 2 SiMe 3 ) 3 (sol) n M = Sc(III), Y(III), Lu(III), Sm(III), and sol = THF; TMEDA; DMPE; diglyme ((CH 3 ) 2 (OCH 2 CH 2 ) 2 O, G 2 ), triglyme ((CH 3 ) 2 (OCH 2 CH 2 ) 3 O, G 3 ). Surprisingly, simply using higher-denticity donors to sterically disfavor neosilyl γ-H elimination is not effective. While Sc(r) 3 ((CH 3 ) 2 (OCH 2 CH 2 ) 2 O) has a half-life, t 1/2 , of 258.1 h, six times longer than for Sc(r) 3 (C 4 H 8 O) 2 (t 1/2 = 43 h), Lu(r) 3 ((CH 3 ) 2 (OCH 2 CH 2 ) 2 O) and Y(r) 3 ((CH 3 ) 2 (OCH 2 CH 2 ) 2 O) do not show the expected, analogous increased t 1/2 . This is because new decomposition pathways appear for poorly fitting donors. Finally, kinetic studies demonstrate the impact of small, and increasing amounts of LiCl on the kinetics of the reactivity of the smaller alkyls Y(r) 3 (THF) 2 and Lu(r) 3 (THF) 2 ; molecules used in hydrocarbon chemistry and catalysis for fifty years. A new route to pure Y(r) 3 (THF) 2 , which avoids the traditional use of Li(r), is presented.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Design and synthesis of diazirine‐containing dyes for polypropylene fibre: A study on the effect of alkyl chain

Abstract The dyeing of polypropylene fabrics utilising conventional‐disperse dyes often meets poor colour yield and fastness problems, fundamentally caused by the low affinity between dyes and polypropylene fibres. In this article, a new class of hydrophobic reactive dyes that can react with polypropylene were designed using diazirine moiety as a reactive group, azo structure as a chromophore, and an ester group as a linking bridge. The difference among these dyes was the alkyl chain length on the azo chromophore, which was used to fine‐tune the affinity between the dyes and fibre. The structures of the synthesised dyes and intermediates were characterised and confirmed using nuclear magnetic resonance, mass spectrometry, and infrared spectrometry. The absorption and thermal properties of the dyes were also studied to ensure their feasibility for dyeing application. In addition, the diazirine dyes were successfully applied to dye polypropylene fabrics using a two‐step process by dyeing in a non‐aqueous solvent and fixing it under heating. The dyes and polypropylene fibre were demonstrated to react, where the fixation values were in the range 64.5–76.4%. The systematic study of the structure–property relationship demonstrated the positive effect of the alkyl chain in promoting colour yield, however, accompanied by a slightly reduced fixation value. Due to the chemical bonding of the dye molecules to the fibre, the dyed polypropylene fabrics exhibited excellent colour fastness property, making the dyeing technology very promising for future industrial applications.

Guo, Guangluo↗
DOE OSTI2023

Low-temperature upcycling of polyolefins into liquid alkanes via tandem cracking-alkylation

Selective upcycling of polyolefin waste has been hampered by the relatively high temperatures that are required to cleave the carbon-carbon (C–C) bonds at reasonably high rates. We present a distinctive approach that uses a highly ionic reaction environment to increase the polymer reactivity and lower the energy of ionic transition states. Combining endothermic cleavage of the polymer C–C bonds with exothermic alkylation reactions of the cracking products enables full conversion of polyethylene and polypropylene to liquid isoalkanes (C 6 to C 10 ) at temperatures below 100°C. Both reactions are catalyzed by a Lewis acidic species that is generated in a chloroaluminate ionic liquid. The alkylate product forms a separate phase and is easily separated from the reactant catalyst mixture. The process can convert unprocessed postconsumer items to high-quality liquid alkanes with high yields.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Processes for the preparation of alkyl furans using bifunctional copper catalysts

The present disclosure relates to the selective hydrodeoxygenation (HDO) of bio-based furanic ketones with a bifunctional copper-based catalyst in the presence of a solvent to prepare alkyl furans with high yield, purity, and scalability. The alkyl furans prepared herein are useful in the preparation of surfactants.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Donor End-Capped Alkyl Chain Length Dependent Non-Radiative Energy Loss in All-Small-Molecule Organic Solar Cells

A critical bottleneck for further efficiency breakthroughs in organic solar cells (OSCs) is to minimize the non-radiative energy loss (eΔV nr ) while maximizing the charge generation. With the development of highly emissive low-bandgap non-fullerene acceptors, the design of high-performance donors becomes critical to enable the blend with the electroluminescence quantum efficiency to approach or surpass the pristine acceptor. Herein, by shortening the end-capped alkyl chains of the small-molecular donors from hexyl (MPhS-C6) to ethyl (MPhS-C2), the material obtained aggregation that was insensitive to thermal annealing (TA) along with condensed packing simultaneously. The former leads to small phase separation and suppressed upshifts of the highest occupied molecular orbital energy level during TA, and the latter facilitates its efficient charge-transport at aggregation-less packing. Hence, the ΔV nr decreases from 0.242 to 0.182 V, from MPhS-C6 to MPhS-C2 based OSCs. An excellent PCE of 17.11% is obtained by 1,8-diiodoctane addition due to almost unchanged high J sc (26.6 mA cm –2 ) and V oc (0.888 V) with improved fill factor, which is the record efficiency with the smallest energy loss (0.497 eV) and ΔV nr (0.192 V) in all-small-molecule OSCs. Finally, these results emphasize the potential material design direction of obtaining concurrent TA-insensitive aggregation and condensed packing to maximize the device performances with a super low ΔV nr .

36 MATERIALS SCIENCE↗
DOE OSTI2026

Synthesis and Reactivity of Heteroleptic U 4+ Alkyl, Benzyl, and Hydride Imidophosphorane Complexes

A series of heteroleptic U 4+ benzyl, neopentyl, and methyl complexes supported by the imidophosphorane ligand, [N = P(N,N′-ditert-butylethylenediamide)(diethylamide)] 1− (NP*), were synthesized from the monoiodide precursor, [UI(NP*) 3 ]. These heteroleptic complexes were synthesized through the selective formation of [UI(NP*) 3 ] under transmetalation conditions in the reaction between [UI 4 (1,4-dioxane) 2 ] and K[NP*]. Formation of the homoleptic complex [U(NP*) 4 ] was not observed even in the presence of excess K[NP*]. The oxidation and hydrogenolysis reactivity of the neopentyl complex, [U(Npt)- (NP*) 3 ] (Npt = neopentyl) was explored. While cyclic voltammetry indicates a potentially isolable U5+ alkyl cation, chemical oxidation of the neopentyl complex results in the isolation of a cationic U 4+ complex with a bound diethyl ether in the primary coordination sphere, [U4+(NP*)) 3 (Et 2 O)][(BArF 24 )] (BArF 24 = tetrakis(3,5-bis(trifluoromethyl)phenyl)borate). Notably, hydrogenolysis of [U(Npt)(NP*) 3 ] with H2 gas at −20 °C results in the formation of a terminal hydride intermediate confirmed by in situ NMR spectroscopy and deuterium labeling with D 2 . The connectivity and structural parameters of this hydride intermediate, [UH(NP*) 3 ], which rapidly thermally decomposes to the homoleptic complex, [U(NP*) 4 ], can be confirmed by single-crystal X-ray diffraction studies of a crystal grown by chilling the reaction mixture. The identity of [U(NP*) 4 ] was confirmed by its direct, bulk synthesis from [U(Me)(NP*) 3 ] and HNP* in a protonolysis reaction.

Alkyls↗
DOE OSTI2024

Synthesis of Perdeuterated Alkyl Amines/Amides with Pt/C as Catalyst under Mild Conditions

A convenient method for the synthesis of perdeuterated alkyl amides/amines is disclosed. Perdeuterated acetyl amides can be achieved by a hydrogen–deuterium (H/D) exchange protocol with Pt/C as a catalyst and D 2 O as a deuterium source under mild conditions. Further, after removal or reduction of the acetyl group, this protocol can provide perdeuterated primary, secondary, and tertiary amines, which are difficult to achieve via other methods.

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

Pushing and Pulling: A Dual pH Trigger Controlled by Varying the Alkyl Tail Length in Heme Coordinating Peptide Amphiphiles

Some organisms in nature that undergo anaerobic respiration utilize 1D nanoscale arrays of densely packed cytochromes containing the molecule heme. The assemblies can be mimicked with 1D nanoscale fibrils composed of peptide amphiphiles designed to coordinate heme in dense arrays. To create such materials and assemblies it is critical to understand the assembly process and what controls the various aspects of hierarchical assembly. MD simulations suggest that shorter alkyl chains on the peptide lead to more dynamic structures than the peptides with longer chains that yield kinetically trapped states. The hydration parameters manifest themselves experimentally through the observation of a dual pH trigger which controls the peptide assembly rate, the heme binding affinity, and heme organization kinetics. Great strides in understanding the relative complexity of the self-assembly process in relation to incorporating a functional moiety like heme opens up many possibilities in developing abiotic assemblies for bioelectronic devices and assemblies

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

Cyclic (Alkyl)(amino)carbenes (CAACs) in Ruthenium Olefin Metathesis

Discovered in 2005, cyclic (alkyl)(amino)carbenes (CAACs) have led to numerous discoveries in the field of ruthenium olefin metathesis, until then largely dominated by the well-known N-heterocyclic carbenes (NHCs). Compared to the latter, CAACs are simultaneously more nucleophilic (σ-donating) and electrophilic (π-accepting), which leads to very strong metal-carbene bonds. Consequently, CAAC-ruthenium complexes are very robust, which leads to enhanced catalytic activities, as exemplified by the industrially relevant ethenolysis of unsaturated fatty acids (up to of 390,000 TON). Furthermore, we provide a comprehensive overview of the impact of CAAC ligands in olefin metathesis, including results which are discribed in patents.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗