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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.

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At least 91 records · Page 5

Deep eutectic solvents as green and sustainable diluents in headspace gas chromatography for the determination of trace level genotoxic impurities in pharmaceuticals

Genotoxic impurities (GTIs) are potential carcinogens that need to be controlled down to ppm or lower concentration levels in pharmaceuticals under strict regulations. The static headspace gas chromatography (HS-GC) coupled with electron capture detection (ECD) is an effective approach to monitor halogenated and nitroaromatic genotoxins. Deep eutectic solvents (DESs) possess tunable physico-chemical properties and low vapor pressure for HS-GC methods. In this study, zwitterionic and non-ionic DESs have been used for the first time to develop and validate a sensitive analytical method for the analysis of 24 genotoxins at sub-ppm concentrations. Compared to non-ionic diluents, zwitterionic DESs produced exceptional analytical performance and the betaine: 7 (1,4- butane diol) DES outperformed the betaine: 5 (1,4-butane diol) DES. Limits of detection (LOD) down to the 5-ppb concentration level were achieved in DESs. Wide linear ranges spanning over 5 orders of magnitude (0.005–100 µg g –1 ) were obtained for most analytes with exceptional sensitivities and high precision. The method accuracy and precision were validated using 3 commercially available drug substances and excellent recoveries were obtained. Finally, this study broadens the applicability of HS-GC in the determination of less volatile GTIs by establishing DESs as viable diluent substitutes for organic solvents in routine pharmaceutical analysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

An ab initio free energy study of the reaction mechanism and rate-limiting steps of CO 2 capture by aqueous glycine

Aqueous amino acids are promising absorbents for direct air capture (DAC) of CO 2 . Herein, we investigate the possibility of kinetic control of CO 2 absorption with aqueous anionic glycine (GLY - ) by employing extensive ab initio molecular dynamics simulations, free energy analysis, and reaction rate theory. We find that first GLY - binds to CO 2 by overcoming a barrier (7.4 kcal/mol) to form a zwitterion intermediate, which then releases a proton by overcoming a similar barrier. Despite the similarity in the barrier, zwitterion formation appears to be the rate-limiting step because it is two orders of magnitude slower (microseconds) than the proton release step. This is predominantly due to stronger nonequilibrium solvent effects for the former that cause many barrier-recrossing events and effectively slow down the reaction rate. Such a detailed fundamental understanding of the amino acid-based CO 2 -absorption mechanism and rates is key to improving the kinetic efficiency of DAC technology.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ion Transport and Crystal Rotation in Plastic Crystal Electrolytes Under Applied Electric Fields

Organic ionic plastic crystal electrolytes, containing a plastic crystal and lithium salt, offer a potential balance between mechanical and electrochemical properties for solid state lithium-ion battery electrolytes. These electrolytes contain multiple mobile ionic species (three or four), resulting in complex transport mechanisms which have not yet been established. Plastic crystals are defined by long-range positional order and short-range rotational disorder. It is therefore necessary to quantify changes in the local crystal structure of the electrolyte as current flows through it. Herein, we examine the electrochemical properties of pyrrolidinium-based plastic crystal electrolytes containing lithium salt and zwitterion additives, including measurements of current fraction and limiting current. We obtain species-specific insight into electrolyte transport using pulsed-field gradient nuclear magnetic resonance spectroscopy and find that, while the zwitterion additive increases ionic conductivity, it decreases lithium diffusivity with respect to other ionic components. With operando spatiotemporally resolved wide-angle X-ray scattering we observe location-specific crystal rotations due to the passage of ionic current. In conclusion, we posit that reducing energy dissipation due to rotation is essential for using plastic crystal electrolytes in practical applications.

Yap, Kyra M. K. [University of California, Berkele↗

Electron Spin-Polarization Dependent Damage to Chiral Amino Acid l-Histidine

The damage of approximately monolayer films of L-histidine by low-energy spin-polarized electrons (SPE) ejected from a magnetized cobalt substrate has been probed using X-ray photoelectron spectroscopy (XPS). Average damage cross sections for N-containing motifs of L-histidine are 25-30 and 2-5 Mb for zwitterions and neutral molecules, respectively. Here, the magnetization direction of the substrate, which controls the ejected SPE helicity, was reversed in situ, and statistically significant differences in the damage cross sections of 10-30% were measured between positive and negative electron helicities. This is the first measurement of spin dichroism (SD) in an amino acid. The differential cross sections suggest that inelastic scattering of SPE with chiral molecules could contribute to the persistence of one enantiomer vs the other under certain irradiation conditions, particularly for the zwitterionic species.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Hybrid-Supported Bilayers Formed with Mixed-Charge Surfactants on C 18 -Functionalized Silica Surfaces

Mixtures of cationic-anionic surfactants have been demonstrated to spontaneously form ordered monolayers at hydrophobic-hydrophilic boundaries including air-water and oil-water interfaces. Here, confocal Raman microscopy is used to investigate the structure of hybrid-supported surfactant bilayers (HSSBs) formed by deposition of a distal leaflet of mixed cationic-anionic surfactants onto a proximal leaflet of n-alkane (C 18 ) chains on the interior surfaces of chromatographic silica particles. The surface coverage of the two surfactants in a hybrid bilayer was determined from carbon analysis and the relative Raman scattering of their respective head-groups. Within the measurement uncertainty, the stoichiometric ratio of the two surfactants is one-to-one, equivalent to mixed-charge-surfactant monolayers at air-water and oil-water interfaces and consistent with the role of the head-group electrostatic interactions in their formation. When self-assembled on the hydrophobic surface, pairs of oppositely-charged n-alkyl-chain surfactants resemble a phospholipid (phosphati¬dylcholine) molecule, with its zwitterionic head group and two hydrophobic acyl-chain tails. Indeed, the structure of these hybrid-supported surfactant bilayers on C 18 -modified silica surfaces is similar to that of hybrid-supported lipid bilayers (HSLBs) on the same supports, but with denser and more-ordered n-alkyl chains. Hybrid-supported surfactant bilayers exhibit a melting phase transition (gel to liquid-crystalline phase) with structural and energetic characteristics similar to hybrid-supported bilayers prepared from a zwitterionic phospholipid of the same alkyl chain length. These mixed-charge surfactants on n-alkane modified silica are stable in water over time (months), results that suggest the potential use of these hybrid bilayers for generating supported lipid bilayer-like surfaces or for separation applications.

36 MATERIALS SCIENCE↗

Antivesiculation and Complete Unbinding of Tail-Tethered Lipids

Here, we report the effect of tail-tethering on vesiculation and complete unbinding of bilayered membranes. Amphiphilic molecules of a bolalipid, resembling the tail-tethered molecular structure of archaeal lipids, with two identical zwitterionic phosphatidylcholine headgroups self-assemble into a large flat lamellar membrane, in contrast to the multilamellar vesicles (MLVs) observed in its counterpart, monopolar nontethered zwitterionic lipids. The antivesiculation is confirmed by small-angle X-ray scattering (SAXS) and cryogenic transmission electron microscopy (cyro-TEM). With the net charge of zero and higher bending rigidity of the membrane (confirmed by neutron spin echo (NSE) spectroscopy), the current membrane theory would predict that membranes should stack with each other (aka “bind”) due to dominant van der Waals attraction, while the outcome of the nonstacking (“unbinding”) membrane suggests that the theory needs to include entropic contribution for the nonvesicular structures. This report pioneers an understanding of how the tail-tethering of amphiphiles affects the structure, enabling better control over the final nanoscale morphology.

36 MATERIALS SCIENCE↗

Cations Control Lipid Bilayer Memcapacitance Associated with Long-Term Potentiation

Phospholipid bilayers can be described as capacitors whose capacitance per unit area (specific capacitance, C m ) is determined by their thickness and dielectric constant–independent of applied voltage. It is also widely assumed that the C m of membranes can be treated as a “biological constant”. Recently, using droplet interface bilayers (DIBs), it was shown that zwitterionic phosphatidylcholine (PC) lipid bilayers can act as voltage-dependent, nonlinear memory capacitors, or memcapacitors. When exposed to an electrical “training” stimulation protocol, capacitive energy storage in lipid membranes was enhanced in the form of long-term potentiation (LTP), which enables biological learning and long-term memory. LTP was the result of membrane restructuring and the progressive asymmetric distribution of ions across the lipid bilayer during training, which is analogous, for example, to exponential capacitive energy harvesting from self-powered nanogenerators. Here, we describe how LTP could be produced from a membrane that is continuously pumped into a nonequilibrium steady state, altering its dielectric properties. During this time, the membrane undergoes static and dynamic changes that are fed back to the system’s potential energy, ultimately resulting in a membrane whose modified molecular structure supports long-term memory storage and LTP. Here, we also show that LTP is very sensitive to different salts (KCl, NaCl, LiCl, and TmCl 3 ), with LiCl and TmCl 3 having the most profound effect in depressing LTP, relative to KCl. This effect is related to how the different cations interact with the bilayer zwitterionic PC lipid headgroups primarily through electric-field-induced changes to the statistically averaged orientations of water dipoles at the bilayer headgroup interface.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Hydration and Restructuring of Polar Polymer Interfaces: Implications in Antifouling and Responsive Materials

Manipulating polymer interfaces is crucial for understanding how structure influences function in applications spanning biofouling prevention to energy storage. Moreover, observing how polymers adapt their microscopic structure to changes in their local environment can reveal essential properties that govern their performance in such applications, providing key insights into how to design more effective interfaces. Here, in this study, a series of “grafting-from” polymer brushes with side chains varying in charge, are probed by sum frequency generation (SFG) and modeled using all-atom molecular dynamics (MD) simulations to elucidate how chemical makeup and charge mediate interfacial restructuring in dry versus hydrated states. Results show that charge, in progressing from nonpolar to cationic to zwitterionic, results in dramatic changes in interfacial structure and overall hydration. While net neutral systems, regardless of bulk phase polarity, show minimal interfacial water structuring, the cationic species exhibits strong bulk water signals from the surface potential. Meanwhile, the polymer brushes themselves restructure in water differently independent of charge, impacting the functional groups that are presented to the aqueous phase. Nonpolar and cationic species for instance undergo a change in alkyl group orientations to accommodate hydrating water molecules, whereas the zwitterionic polymer becomes completely disordered in water. Overall, the structure-based behavior trends presented herein have implications in antifouling applications and responsive material interfaces.

biointerface↗

Deactivating Emission in Azulene via Solvent-Induced (Anti)Aromaticity

Anti-Kasha emission is a coveted feature in optoelectronics, with promise in areas such as imaging, sensing, and the production of white-light LEDs via dual-photon emission. Despite being a rare feature in organic systems, anti-Kasha emission is readily observed in the deceptively simple molecule azulene, which possesses two bright singlet states in the UV–visible spectrum and readily emits from the S 2 state. With dominant anti-Kasha emission and decades of synthetic study, azulene is a perfect candidate for novel material fabrication; however, large gaps persist in understanding the photophysics of even the simple parent compound. These range from competing, experimentally unverified models of azulene reactivity and aromaticity to the unexplained deactivation of anti-Kasha emission in a host of azulene derivatives. Herein, we use fluorescence and transient absorption spectroscopies to explore the detailed solvent dependence of azulene photophysics. We discover a tunable reduction in the S 2 lifetime via weak complexation with aromatic solvents. Interestingly, our results are independent of polarity, highlighting the primacy of peripherally delocalized 10-π Hückel aromaticity over zwitterionic character. When the dipolar character is enhanced through chemical functionalization, we observe even greater sensitivity to solvent aromaticity and more rapid quenching, revealing the role of conical intersections in azulenes with zwitterionic excited states. Overall, this work provides essential mechanistic insight into the photophysics of azulene and reveals a simple new approach to control the excited-state aromaticity and anti-Kasha emission in this class of materials.

Absorption↗

Atomic Force Microscopy to Characterize Antimicrobial Peptide-Induced Defects in Model Supported Lipid Bilayers

Antimicrobial peptides (AMPs) interact with bacterial cell membranes through a variety of mechanisms, causing changes extending from nanopore formation to microscale membrane lysis, eventually leading to cell death. Several AMPs also disrupt mammalian cell membranes, despite their significantly different lipid composition and such collateral hemolytic damage hinders the potential therapeutic applicability of the AMP as an anti-microbial. Elucidating the mechanisms underlying the AMP–membrane interactions is challenging due to the variations in the chemical and structural features of the AMPs, the complex compositional variations of cell membranes and the inadequacy of any single experimental technique to comprehensively probe them. (1) Background: Atomic Force Microscopy (AFM) imaging can be used in combination with other techniques to help understand how AMPs alter the orientation and structural organization of the molecules within cell membranes exposed to AMPs. The structure, size, net charge, hydrophobicity and amphipathicity of the AMPs affect how they interact with cell membranes of differing lipid compositions. (2) Methods: Our study examined two different types of AMPs, a 20-amino acid, neutral, α-helical (amphipathic) peptide, alamethicin, and a 13-amino acid, non-α-helical cationic peptide, indolicidin (which intramolecularly folds, creating a hydrophobic core), for their interactions with supported lipid bilayers (SLBs). Robust SLB model membranes on quartz supports, incorporating predominantly anionic lipids representative of bacterial cells, are currently not available and remain to be developed. Therefore, the SLBs of zwitterionic egg phosphatidylcholine (PC), which represents the composition of a mammalian cell membrane, was utilized as the model membrane. This also allows for a comparison with the results obtained from the Quartz Crystal Microbalance with Dissipation (QCM-D) experiments conducted for these peptides interacting with the same zwitterionic SLBs. Further, in the case of alamethicin, because of its neutrality, the lipid charge may be less relevant for understanding its membrane interactions. (3) Results: Using AFM imaging and roughness analysis, we found that alamethicin produced large, unstable defects in the membrane at 5 µM concentrations, and completely removed the bilayer at 10 µM. Indolicidin produced smaller holes in the bilayer at 5 and 10 µM, although they were able to fill in over time. The root-mean-square (RMS) roughness values for the images showed that the surface roughness caused by visible defects peaked after peptide injection and gradually decreased over time. (4) Conclusions: AFM is useful for helping to uncover the dynamic interactions between different AMPs and cell membranes, which can facilitate the selection and design of more efficient AMPs for use in therapeutics and antimicrobial applications.

Swana, Kathleen W.↗

Lipid composition for the delivery of therapeutic cargos

A construct includes a core comprising an external surface and a plurality of pores, a cargo disposed in a pore of the plurality of pores, the cargo comprising a CRISPR Cas9 component or a nucleic acid sequence encoding a CRISPR Cas9 component; and a coating coupled to the core, wherein the coating comprises a cationic lipid, a pegylated lipid, a zwitterionic lipid, and a sterol. The coating may comprise a molar ratio of about 1 cationic lipid to 1 zwitterionic lipid to 0.9 sterol to 0.15 PEGylated lipid, wherein each molar ratio optionally varies by about plus or minus 10%. A method of treatment is also provided.

Negrete, Oscar↗

Advanced Mineral Separations with Novel Simulated Moving Beds

Lithium is a critical mineral that is widely used in batteries and energy storage applications, making it increasingly important in the next few decades. To meet the growing demand for lithium and secure domestic supply chains, there is a need to exploit unconventional lithium resources. However, utilizing current lithium extraction processes is challenging due to the high salinity in those resources. Thus, it is essential to develop energy-efficient, and less chemical-intensive separation processes that can exploit high-salinity lithium resources. Accordingly, this project aims to design a novel zwitterionic stationary phase and use it to develop a continuous chromatography process to recover LiCl minerals from traditionally unexploited domestic saline resources. The developed zwitterionic stationary phase allows fractionating minerals based on their different sorbent affinities under water elution. A systematically designed continuous process can separate lithium from other minerals, reducing the risk of material fouling and the overall chemical consumption to produce battery-grade lithium. This approach is expected to significantly enhance the efficiency and sustainability of the lithium extraction process while also reducing the environmental impact associated with traditional processes. At the end of the project, the technology will be demonstrated in continuous mode using a simulated moving bed (SMB) to recover >100 g of LiCl from real resource waters. The U.S.-based resources that this project targets for LiCl recovery are formation water, oil-produced water, and geothermal brines, supplied by Standard Lithium Ltd. and Shell Inc, respectively.

critical minerals↗

Absorption cycle apparatus and related method

An absorption cycle apparatus including a working fluid is presented. The working fluid includes a metal halide, water and a zwitterion additive, wherein the zwitterion additive includes an amino acid, 2,2′-[(phosphonomethyl)imino]diaceticacid, 3-[(2-hydroxyethyl)amino]-1-propanesulfonic acid, or combinations thereof. A method of controlling crystallization in a working fluid of an absorption cycle apparatus is also presented.

Tang, Ching-Jen↗

Effectiveness of PCE superplasticizers in calcined clay blended cements

Highlights: • Cements containing 0–40 wt% of a calcined clay rich in meta kaolin were studied. • The calcined clay decreases fluidity of the blended cements considerably. • In cement, the calcined clay adsorbs a large amount of Ca{sup 2+} ions. • A common HPEG polycarboxylate superplasticizer fluidizes OPC/CC blends best. • A zwitterionic PCE also fluidizes well and adsorbs in similar amounts as HPEG. The impact of a calcined clay (CC) rich in meta kaolin (~50 wt%) present in composite cements at 0–40% substitution rate for the clinker was studied relative to the dispersing force of different PCE superplasticizers. It was found that CC increases the water demand of the blended cements considerably (+85% for the 60:40 blend vs. neat OPC). Furthermore, PCEs which fluidize OPC best also provide optimal performance in CC blended cements, but require much higher dosages (in OPC/CC 60:40, 4–6 times as compared to neat OPC). In all systems, HPEG-PCE produced superior dispersing performance over anionic MPEG-PCEs. A mechanistic study involving zeta potential measurements revealed that the initially negatively charged calcined clay surface adsorbs huge amounts of Ca{sup 2+} ions from the pore solution, thus facilitating adsorption of anionic PCE superplasticizers. The results signify that commercially available PCE products can effectively fluidize OPC/CC blended cements.

36 MATERIALS SCIENCE↗

Synergistic foam stabilization and transport improvement in simulated fractures with polyelectrolyte complex nanoparticles: Microscale observation using laser etched glass micromodels

Inaccessibility to direct pore scale observation in hydrocarbon recovery of tight shale formations poses a great challenge to water-energy nexus initiatives and necessitates the use of high throughput technologies to emulate environmentally friendly processes. Herein, we employ a precise glass micromodel fabrication and visualization method to isolate the supercritical CO 2 bubbles surrounded by CO 2 -water lamella prepared in saline produced water stabilized with molecular complexation of zwitterionic surfactants (ZS) and polyelectrolyte complex nanoparticles (PECNP). The Selective Laser Enhanced Etching (SLE) technique was selected for micromodel simulation of high-pressure flow. Two representative designs, (1) fracture/micro-crack network 28 and (2) fracture/matrix were etched on fused silica glass with a laser printing machine and scCO 2 foam was injected to study the foamability, propagation, stability, and fluid loss properties. The highly monodispersed and uniformly distributed array of scCO 2 bubbles were detected in flow of scCO 2 foam in highly saline brine containing ionic complexes of positively charged PECNPs and ZS, whereas foam flow with the lamella containing ZS in fractures offered a noticeably large and polydisperse array of scCO 2 bubbles. scCO 2 bubble motion and deformation were traced, and local description of foam flow was visually examined. The confined array of scCO 2 bubbles stabilized by ZS in microcracks was affected by bubble growth and coalescence, whereas the super-populated array of monodispersed scC O2 bubbles with lamella containing complexes of PECNP and ZS were able to fill the channels with stable configurations within the timeframe of comparative stability measurements. The ability of complex fluid to prevent the formation damage was evaluated through fluid loss visualization in micromodels. Probing scCO 2 foam transport in homogenous porous media revealed smaller volume leak-off for scCO 2 foam containing PECNP-ZS ionic complexes.

04 OIL SHALES AND TAR SANDS↗

Modeling and mitigating fouling of microfiltration membranes for microalgae dewatering

Dewatering is energy-intensive for microalgae production, and microfiltration (MF) membranes are attractive because of their high energy efficiency. However, the membranes suffer from fouling by organic matter in the algae solutions, and there needs fundamental understanding of membrane fouling with actual algae solutions. Herein we thoroughly evaluate the dewatering performance of commercial polyethersulfone (PES) MF membranes using an integrated experiment and modeling approach. The effect of algae concentration, testing time, feed flow rate, and chemical cleaning on the dewatering performance and fouling-layer morphology are investigated. The fouling behavior can be successfully described using the Hermia and gel layer models with a gel concentration of 48 g/L for algae solutions. Furthermore, the PES membrane surface was grafted with hydrophilic zwitterions, which mitigated the fouling. For example, when challenged with 10 g/L algae solution in dead-end cells, the pristine and modified membrane exhibit water permeance of 80 and 170 L m – 2 h –1 bar –1 , respectively. Finally, three cycles of dewatering and NaOH cleaning were performed to demonstrate the promise of the MF membranes for practical dewatering application.

42 ENGINEERING↗

Indium and thallium extraction into betainium bis(trifluoromethylsulfonyl)imide ionic liquid from aqueous hydrochloric acid media

The partitioning behavior of indium and thallium ions between aqueous hydrochloric acid solutions and hydrophobic betainium bis(trifluoromethylsulfonyl)imide ionic liquid was studied using a standard liquid–liquid extraction technique. The experiments were mainly carried out by means of a radiochemical method, using 111 In and 201 Tl medical radionuclides at an ultra-trace concentration. Both mono- and trivalent thallium were utilized and the highest oxidation state (3+) was produced by adding either chlorine or bromine water to the aqueous phase prior to extraction. The metal ion transfer was optimized by varying the aqueous concentration of hydrochloric acid and by introducing zwitterionic betaine as an extracting agent into the aqueous phase. It was found that the highest D values of In(III), Tl(III) and Tl(I) in the investigated chemical systems were up to 200, 70, and 1, respectively. The influence of the addition of lithium salt, having common with the ionic liquid counterion, and the variation of mixing time on the distribution ratio of the metal ions were also studied. Finally, to understand the underlying extraction mechanism of the metal ions and to propose the predominant extracted species, mathematical models based on ion pair formation and ion exchange were developed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Stable High‐Conductivity Ethylenedioxythiophene Polymers via Borane‐Adduct Doping

Efficient doping of polymer semiconductors is required for high conductivity and efficient thermoelectric performance. Lewis acids, e.g., B(C 6 F 5 ) 3 , have been widely employed as dopants, but the mechanism is not fully understood. 1:1 “Wheland type” or zwitterionic complexes of B(C 6 F 5 ) 3 are created with small conjugated molecules 3,6-bis(5-(7-(5-methylthiophen-2-yl)-2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)thiophen-2-yl)-2,5-dioctyl-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione [oligo_DPP(EDOT) 2 ] and 3,6-bis(5''-methyl-[2,2':5',2''-terthiophen]-5-yl)-2,5-dioctyl-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione [oligo_DPP(Th) 2 ]. Using a wide variety of experimental and computational approaches, the doping ability of these Wheland Complexes with B(C 6 F 5 ) 3 are characterized for five novel diketopyrrolopyrrole-ethylenedioxythiophene (DPP-EDOT)-based conjugated polymers. The electrical properties are a strong function of the specific conjugated molecule constituting the adduct, rather than acidic protons generated via hydrolysis of B(C 6 F 5 ) 3 , serving as the oxidant. It is highly probable that certain repeat units/segments form adduct structures in p -type conjugated polymers which act as intermediates for conjugated polymer doping. Electronic and optical properties are consistent with the increase in hole-donating ability of polymers with their cumulative donor strengths. The doped film of polymer (DPP(EDOT) 2 -(EDOT) 2 ) exhibits exceptionally good thermal and air-storage stability. The highest conductivities, ≈300 and ≈200 S cm -1 , are achieved for DPP(EDOT) 2 -(EDOT) 2 doped with B(C 6 F 5 ) 3 and its Wheland complexes.

36 MATERIALS SCIENCE↗