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Experimental and theoretical study of [Ga 4 L 6 ] 12− and [In 4 L 6 ] 12− investigating guest encapsulation. Our study reveals that solvent composition, crucially affects entropy and guest binding, opening the door for tuning host–guest interactions.
Kinetic and isotopic assessments combined with theoretical calculations shed light on the mechanistic differences in terms of the number of hydrogen addition steps and the electronic charges of reactive hydrogen in the catalytic sequence leading to the Ar−OCH 3 scission of 2-methoxyphenol occurring at various interfaces of vapor−Ru, cyclohexane−Ru, and water−Ru. At vapor−Ru and cyclohexane−Ru interfaces, the initial hydrogen adatom (H*) additions on the phenyl ring disrupt its aromaticity, as a step required to occur before kinetically relevant Ar−OCH 3 scission on an ensemble of Ru sites. The number of H* addition events prerequisite to the formation of the kinetically relevant Ar−OCH 3 scission transition state, however, is larger at the cyclohexane−Ru interface than those at the vapor−Ru and water−Ru interfaces. The preferential solvation of 2-methoxyphenol derived reaction precursors and H* weakens their adsorption on Ru sites, which leads to a decrease in the activation barrier for the third H* addition step and in turn a larger number of H* additions. At the water−Ru interface, water as a polar protic solvent promotes the Ar−OCH 3 scission by enabling a mechanistically distinct catalytic route an adjacent water molecule from the solvent layer assists with the intramolecular proton shuttling from the hydroxyl group (−OH) to the vicinal methoxy group (−OCH 3 ) of 2-methoxyphenol, evolving a highly charged transition state that is further stabilized by the water solvent layer, thereby leading to Ar−OCH 3 scission rate constants that are much higher than those at the vapor−Ru interface and, when comparing at the same H 2 chemical potential, higher Ar−OCH 3 scission turnovers. Furthermore, these distinct mechanistic details of the Ar−OCH 3 scission at various reaction interfaces, inferred from experiment and theory, illustrate how a solvent either solvates reaction intermediates and transition states or directly participates in the formation of kinetically relevant transition states, leading to changes in the free energy landscape, thus rewriting the catalytic fates in hydrodeoxygenation reactions.
The goal of this project was development of low-cost aerogels to be used as cores of Vacuum Insulated Panels (VIP). The specific aims were: 1. Aerogels to be based on phenolic chemistry to minimize flammability. 2. Aerogels to be in monolithic form and to have mechanical properties sufficient to allow their use as cores of VIPs without collapsing after evacuation. 3. Aerogels to have a cost per kg lower than the cost of fumed silica, one of the most common VIP cores. The achievements are: 1. Phenolic aerogels have been fabricated in monolithic form with thermal conductivity of 0.023 W/m·K, density ~ 0.25 g/cm 3 and a modulus of compression > 10 MPa. The aerogels can withstand the stresses of VIP evacuation without any appreciable deformation. 2. Drying of aerogels was carried in the initial stages of the project via sublimation of frozen solvents, following the procedure described in M. F. Bertino and T. Selden, “Fabrication of Aerogels and Aerogel Composites by Ambient Pressure Sublimation of Frozen Solvents”, PCT/US20/39485. Monoliths as large as 30 x 30 x 2 cm can be fabricated with the proprietary ambient fabrication technique which are free of cracks and warping. 3. Cost analysis was carried out and refined multiple times, cost drivers were identified, and the fabrication procedure was streamlined. Our cost model yields an aerogel cost of $\$$5.78/kg, which compares well with the price of fumed silica ($\$$6.2/kg FOB New York as of March 2023). 4. The monoliths can be cut into custom shapes and used as VIP cores. Cores fabricated with our technique have a thermal conductivity λ = 0.011 W/m·K at a pressure >10 mbar. 5. A variant of the technology yielded fireproof materials, described in M. F. Bertino, T. Moon, G. Waller, J. Ko and D. Clifford, “Fireproof thermal insulation”, Provisional Patent Application 63/415,386. 6. A spin-off company was created (ThermaGel Innovations, Inc.) which licensed technologies developed under this award. PI Bertino is a board member of the newco which is now raising capital to build a pilot plant.
Aqueous phase heterogeneous catalysis is important to various industrial processes, including biomass conversion, Fischer–Tropsch synthesis, and electrocatalysis. Accurate calculation of solvation thermodynamic properties is essential for modeling the performance of catalysts for these processes. Explicit solvation methods employing multiscale modeling, e.g., involving density functional theory and molecular dynamics have emerged for this purpose. Although accurate, these methods are computationally intensive. This study introduces machine learning (ML) models to predict solvation thermodynamics for adsorbates on a Pt(111) surface, aiming to enhance computational efficiency without compromising accuracy. In particular, ML models are developed using a combination of molecular descriptors and fingerprints and trained on previously published water–adsorbate interaction energies, energies of solvation, and free energies of solvation of adsorbates bound to Pt(111). These models achieve root mean square error values of 0.09 eV for interaction energies, 0.04 eV for energies of solvation, and 0.06 eV for free energies of solvation, demonstrating accuracy within the standard error of multiscale modeling. Feature importance analysis reveals that hydrogen bonding, van der Waals interactions, and solvent density, together with the properties of the adsorbate, are critical factors influencing solvation thermodynamics. Furthermore, these findings suggest that ML models can provide rapid and reliable predictions of solvation properties. This approach not only reduces computational costs but also offers insights into the solvation characteristics of adsorbates at Pt(111)–water interfaces.
For many years chlorofluorocarbon (CFC ) based solvents, such as Freon and 1,1,1, Trichloroethane (TCA), were used as bearing cleaning solvents for space mechanisms. The 1995 ban on the production of ozone depleting chemicals (ODC) such as CFCs caused a change to new ODC-free cleaners for the precision bearing cleaning. With this change the question arises what effect if any do these new cleaners have on long term bearing life. The purpose of this study was to evaluate this effect. A one year test using 60 small electrical motors (two bearings per motor) was conducted in a high vacuum environment (2.0* 10(exp -6) torr) at a temperature of 90C. Prior to testing the bearings were cleaned with one of four cleaners. These cleaners included two aqueous based cleaners, a CFC based cleaner and supercritical carbon dioxide. Three space compatible greases were tested. After testing the mass of each lubricated bearing was measured both pre and post test. Along with mass loss measurements a profilometer trace of each bearing was taken to measure post test wear of the bearings. In addition the bearings were visually examined and analyzed using an optical microscope.
Molecular mixtures and/or formulations are of great importance in fields ranging from materials science to pharmaceuticals to chemistry. In batteries, electrolytes are complex molecular mixtures consisting of multiple salts and solvents and additives at different concentrations that dictate battery capacity, safety, and cycle life, among others. Unfortunately, due to the complex composition and infinite design space as well as the conflicting property requirements, electrolyte design is the rate-determining step in the design of next generation battery chemistries. In this work, we develop a transformer-based generative AI model − ElectrolyteGPT − capable of generating solvents and electrolyte formulations to satisfy a wide range of desired property requirements. First, we curate an electrolyte-relevant database and develop a new line notation for formulations. Then, we show that ElectrolyteGPT can generate solvents and formulations conditioned on a wide range of important electrolyte properties such as ionic conductivity, oxidative stability, Coulombic efficiency, viscosity, and more. Finally, we experimentally synthesize the generated solvents and fabricate the electrolyte formulations and show that they can meet the desired property requirements and enable longterm cycling in energy-dense anode-free lithium metal batteries. Our work showcases the ability of generative models to address challenges in molecular mixture design for next generation batteries.
The ellipticity of the vapor-liquid interface above mixtures of methylcyclohexane (C7H14) and perfluoromethylcyclohexane (C7F14) has been measured near the consolute point T(c) = 318.6 K. The data are consistent with a model of the interface that combines a short-ranged density-vs height profile in the vapor phase with a much longer-ranged composition-versus-height profile in the liquid. The value of the free parameter produced by fitting the model to the data is consistent with results from two other simple mixtures and a mixture of a polymer and solvent. This experiment combines precision ellipsometry of the vapor-liquid interface with in situ measurements of refractive indices of the liquid phases, and it precisely locates the consolute point.
A summary and updating of previous work on the use of radiation chemistry for the preparation of pure materials are presented. Work was chiefly concerned with the reduction of metal salts in solution to the free metal using 2 MeV electrons. Metals deposited from aqueous solution are copper, silver, zinc, cadmium, thallium, tin, lead, antimony, iron, nickel, cobalt, and palladium. Dry organic solvents were evaluated for the deposition of metals based on a study involving deposition of antimony from soltions of antimony (III) chloride. The use of organic liquids for the preparation of anhydrous metal halides is also presented. Reaction mechanisms for both organic liquids and aqueous system are discussed.
Tetracyanopentacenequinone, a powerful electron acceptor, is fused directly to the porphyrin π-system to create a new class of donor-acceptor conjugates. Owing to the direct fusion and electron-deficient property of tetracyanopentacenequinone, strong intramolecular charge transfer both in the ground and excited states was witnessed. As a control, porphyrin fused with pentacenequinone was also investigated. Upon complete spectral and electrochemical characterization, the excited state properties were initially probed by time-dependent DFT studies, and the occurrence of electron transfer from different excited states was established. Free-energy calculations revealed higher exothermic electron transfer (>600 mV) than the control pentacenequinone-porphyrin systems. Pump-probe studies covering broad spatial and temporal regions revealed efficient excited state charge separation. This was unlike the control pentacenequinone-porphyrin system, where slow charge separation was witnessed only in the case of the zinc derivatives but not the free-base ones, followed by the populating of the triplet excited state. The lifetimes of the charge-separated states ranged between 30–500 ps depending on the solvent and metal ion in the porphyrin cavity. Nanosecond transient absorption studies established the charge recombination path to populate the triplet state of porphyrin or directly to the ground state as a function of solvent polarity and the nature of the conjugate. Furthermore, the significance of cross-conjugated tetracyanopentacenequinone fused directly to the porphyrin π system in promoting highly exothermic and efficient charge separation, irrespective of its cross conjugation, is borne out from this study.
A novel photochemical method for liquid-phase deposition of metal films is described. In the liquid phase deposition scheme, a metal containing compound and a metal-metal bonded carbonyl complex are dissolved together in a polar solvent and the mixture is irradiated using a UV laser. The optical arrangement consists of a HeCd laser which provides 7 mW of power at a wavelength of 325 nm in the TEM(OO) mode. The beam is attenuated and may be expanded to a diameter of 5-20 mm. Experiments with photochemical deposition of silver films onto glass and quartz substrates are described in detail. Mass spectrometric analysis of deposited silver films indicated a deposition rate of about 1 A/s at incident power levels of 0.01 W/sq cm. UV laser-induced copper and palladium films have also been obtained. A black and white photograph showing the silver Van Der Pauw pattern of a solution-deposited film is provided.
An experimental correlation is derived for gas absorption at a turbulent, shear-free liquid interface. The correlation is expressed in terms of the liquid-side turbulence intensity, liquid-side macroscale, and the properties of the diffusing gas and solvent. The transfer coefficient increases linearly with rms velocity up to a point where the eddy Reynolds number reaches a critical (Schmidt number dependent) value. At higher velocities, there is a more rapid linear rise. The slope of the lower Reynolds number region is proportional to the square root of the diffusivity; at Reynolds numbers much higher than that of the break point, the slope becomes independent of diffusivity.
For many years chlorofluorocarbon (CFC) based solvents, such as CFC-113 and 1,1,1, trichloroethane (TCA), were used as bearing cleaning solvents for space mechanism bearings. The 1995 ban on the production of ozone depleting chemicals (ODC) such as CFCs caused a change requiring the use of ODC-free cleaners for precision bearing cleaning. With this change the question arises; what effect if any do these new cleaners have on long term bearing life? The purpose of this study was to evaluate this effect. A one year test using 60 small electrical motors (two bearings per motor) was conducted in a high vacuum environment (2.0 x 10(exp -6) torr) at a temperature of 90 C. Prior to testing the bearings were cleaned with one of four cleaners. These cleaners included two aqueous based cleaners, a CFC based cleaner and supercritical carbon dioxide. Three space compatible greases were tested. After testing, the mass of each lubricated bearing was measured both pre and post test. Along with mass loss measurements a profilometer trace of each bearing was taken to measure post test wear of the bearings. In addition, the bearings were visually examined and analyzed using an optical microscope.
Methods are provided for forming spherical multilamellar microcapsules having alternating hydrophilic and hydrophobic liquid layers, surrounded by flexible, semi-permeable hydrophobic or hydrophilic outer membranes which can be tailored specifically to control the diffusion rate. The methods of the invention rely on low shear mixing and liquid-liquid diffusion process and are particularly well suited for forming microcapsules containing both hydrophilic and hydrophobic drugs. These methods can be carried out in the absence of gravity and do not rely on density-driven phase separation, mechanical mixing or solvent evaporation phases. The methods include the process of forming, washing and filtering microcapsules. In addition, the methods contemplate coating microcapsules with ancillary coatings using an electrostatic field and free fluid electrophoresis of the microcapsules. The microcapsules produced by such methods are particularly useful in the delivery of pharmaceutical compositions.
The NASA White Sands Test Facility (WSTF) is developing cleaning and verification processes to replace currently used chlorofluorocarbon-113- (CFC-113-) based processes. The processes being evaluated include both aqueous- and solvent-based techniques. The presentation will include the findings of investigations of aqueous cleaning and verification processes that are based on a draft of a proposed NASA Kennedy Space Center (KSC) cleaning procedure. Verification testing with known contaminants, such as hydraulic fluid and commonly used oils, established correlations between nonvolatile residue and CFC-113. Recoveries ranged from 35 to 60 percent of theoretical. WSTF is also investigating enhancements to aqueous sampling for organics and particulates. Although aqueous alternatives have been identified for several processes, a need still exists for nonaqueous solvent cleaning, such as the cleaning and cleanliness verification of gauges used for oxygen service. The cleaning effectiveness of tetrachloroethylene (PCE), trichloroethylene (TCE), ethanol, hydrochlorofluorocarbon-225 (HCFC-225), tert-butylmethylether, and n-Hexane was evaluated using aerospace gauges and precision instruments and then compared to the cleaning effectiveness of CFC-113. Solvents considered for use in oxygen systems were also tested for oxygen compatibility using high-pressure oxygen autoignition and liquid oxygen mechanical impact testing.
Research conducted at Tuskegee University concentrates on electrical contacts to GaN films and their characterization with the objective of understanding contact formation and realizing low-resistance metal contacts. Contact properties are known to be strongly related to surface preparation. It appears that the as-received material had a thin oxide film on the surface of the GaN film. Various cleaning treatments were employed in order to render the surface contamination free and removal of the oxide film. Metal films were then deposited by e-beam evaporation. Electrical characteristics of these contacts indicated that the optimal treatment was an organic solvent cleaning followed by etching in buffered oxide solution. Contacts established with Al were observed to be ohmic in nature, whereas Au, Cr, Ti, and Pt exhibit rectifying contacts. Platinum contacts were almost ideal as shown by an ideality factor of 1.02.
Since 1981, NASA has routinely collected interplanetary dust particles (IDPs) in the stratosphere by inertial impact onto silicone oil-coated flat plate collectors deployed on the wings of high-altitude aircraft [1]. The highly viscous oil traps and localizes the particles, which can fragment during collection. Particles are removed from the collectors with a micromanipulator and washed of the oil using organic solvents, typically hexane or xylene. While silicone oil is an efficient collection medium, its use is problematic. All IDPs are initially coated with this material (polydimethylsiloxane, n(CH3)2SiO) and traces of oil may remain after cleaning. The solvent rinse itself is also a concern as it likely removes indigenous organics from the particles. To avoid these issues, we used a polyurethane foam substrate for the oil-free stratospheric collection of IDPs.
Interactions between pre-cured phenolic polymer chains and a solvent have a significant impact on the structure and properties of the final post-cured phenolic resin. Developing an understanding of the nature of these interactions is important and will aid in the selection of the proper solvent that will lead to the desired final product. Here, we investigate the role of the phenolic chain structure and the solvent type on the overall solvation performance of the system through ab initio techniques and molecular dynamics simulations. Two types of solvents are considered: ethylene glycol (EGL) and H2O. Three phenolic chain structures are considered, including two novolac-type chains with either an ortho-ortho (OON) or an ortho-para (OPN) backbone network and a resole-type (RES) chain with an ortho-ortho network. Each system is characterized through a structural analysis of the solvation shell and the hydrogen-bonding environment as well as through a quantification of the solvation free energy along with partitioned interaction energies between specific molecular species. The combination of simulations and the analyses indicate that EGL provides a higher solvation free energy than H2O due to more energetically favorable hydrophilic interactions as well as favorable hydrophobic interactions between CH element groups. In addition, the phenolic chain structure significantly affects the solvation performance, with OON having limited intermolecular hydrogen-bond formations, while OPN and RES interact more favorably with the solvent molecules. The results suggest that a resole-type phenolic chain with an ortho-para network should have the best solvation performance in EGL, H2O, and other similar solvents.
Although the potency of conventional anesthetics correlates with lipophilicity, an affinity to water also is essential. It was recently found that compounds with very low affinities to water do not produce anesthesia regardless of their lipophilicity. This finding implies that clinical anesthesia might arise because of interactions at molecular sites near the interface of neuronal membranes with the aqueous environment and, therefore, might require increased concentrations of anesthetic molecules at membrane interfaces. As an initial test of this hypothesis, we calculated in molecular dynamics simulations the free energy profiles for the transfer of anesthetic 1,1,2-trifluoroethane and nonanesthetic perfluoroethane across water-membrane and water-hexane interfaces. Consistent with the hypothesis, it was found that trifluoroethane, but not perfluoroethane, exhibits a free energy minimum and, therefore, increased concentrations at both interfaces. The transfer of trifluoroethane from water to the nonpolar hexane or interior of the membrane is accompanied by a considerable, solvent-induced shift in the conformational equilibrium around the C-C bond.