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Intramolecular triplet-triplet energy transfer between nonconjugated molecular chromophores held together by rigid molecular frame at known separation distance and mutual orientation
The earth's atmosphere is made up of a number of gases in different relative amounts. Near sea level and up to about 90 km, the amount of these atmospheric gases in clean, relatively dry air is practically constant. Four of these gases, nitrogen, oxygen, argon, and carbon dioxide, make up 99.99 percent by volume of the atmosphere. Two gases, ozone and water vapor, change in relative amounts, but the total amount of these two is very small compared to the amount of the other gases. The atmospheric composition shown in a table can be considered valid up to 90 km geometric altitude. Above 90 km, mainly because of molecular dissociation and diffusive separation, the composition changes.
The atmosphere below 100 km is often referred to as the homosphere; the region above, the heterosphere. In the homosphere, constitutents are mixed, and average molecular weight is constant. In the heterosphere, diffusive separation occurs, and species tend to fractionate; average molecular weight decreases with height. Mixing in the homosphere has its source dynamical (wind) energy. Against this background turbulence, intermittent enhancements of turbulent intensity are observed. Some of these enhancements are long lived -- for example, a turbulent layer at approximately 86 km altitude seems to be almost a permanent feature of the (global) daytime D region, as oserved by partial reflection. This may well be a delineation of the mesopause level, since long-term radio meteor studies have shown approx. 85 km to be the breakpoint between thermospheric circulation above, and mesospheric circulation below. The use of stratosphere-troposphere (ST) radars in the lower atmosphere, and mesosphere-stratosphere-troposphere (MST) and partial-reflection radars in the mesosphere for height/time profiles of turbulent intensity is discussed.
The dense dusty molecular cloud core associated with the unusual protostellar source IRAS 16293-1422 (IRAS 1629A) was observed in the J = 2-1 transition of (C-12)O and (C-13)O. These observations indicate that IRAS 1629A is a source of an unusual high-velocity molecular outflow with four separate emission lobes. The morphology and velocity structure of the lobes may suggest the presence of a dual jet or double bipolar outflow system originating from the vicinity of IRAS 1269A. These observations resolve the outflowing gas into numerous high-velocity clumps which are either being continuously accelerated from low to high velocity along the entire length of the flow or are undergoing free-flow expansion.
The feasibility of using microwave power to thermally regenerate sorbents loaded with water vapor, CO2, and organic contaminants has been rigorously demonstrated. Sorbents challenged with air containing 0.5% CO2, 300 ppm acetone, 50 ppm trichloroethylene, and saturated with water vapor have been regenerated, singly and in combination. Microwave transmission, reflection, and phase shift has also been determined for a variety of sorbents over the frequency range between 1.3-2.7 GHz. This innovative technology offers the potential for significant energy savings in comparison to current resistive heating methods because energy is absorbed directly by the material to be heated. Conductive, convective and radiative losses are minimized. Extremely rapid heating is also possible, i.e., 1400 C in less than 60 seconds. Microwave powered thermal desorption is directly applicable to the needs of Advance Life Support in general, and of EVA in particular. Additionally, the applicability of two specific commercial applications arising from this technology have been demonstrated: the recovery for re-use of acetone (and similar solvents) from industrial waste streams using a carbon based molecular sieve; and the separation and destruction of trichloroethylene using ZSM-5 synthetic zeolite catalyst, a predominant halocarbon environmental contaminant. Based upon these results, Phase II development is strongly recommended.
We have inverted high-phase-angle Voyager images of Neptune to determine the atmospheric extinction coefficient as a function of altitude and the scattering phase function at a reference altitude. Comparisons between theoretical model and observations help separate the contributions from molecular Rayleigh and aerosol scattering and help determine the variation of the aerosol size, concentration, and scattering properties with altitude. Further comparisons between models and data allow us to place constraints on the location and composition of the hazes, the concentration and downward flux of certain condensible hydrocarbon gases, the eddy diffusion coefficient in the lower stratosphere, and the thermal profile in parts of Neptune's stratosphere. We find that a distinct stratospheric haze layer exists near 12(sub -1, sup +1) mbar in Neptune's lower stratosphere, most probably due to condensed ethane. The derived stratospheric haze production rate of 1.0(sub -0.3, sup +0.2) x 10(exp -15) g cm(exp -2) sec(exp -1) is substantially lower than photochemical model predictions. Evidence for hazes at higher altitudes also exists. Unlike the situation on Uranus, large particles (0.08-0.11 microns) may be present at high altitudes on Neptune (e.g., near 0.5 mbar), well above the region in which we expect the major hydrocarbon species to condense. Near 28 mbar, the mean particle size is about 0.13(sub -0.02, sup +0.02) microns with a concentration of 5(sub -3, sup +3) particles cm(exp -3). The cumulative haze extinction optical depth above 15 mbar in the clear filter is approx. 3 x 10(exp -3), and much of this extinction is due to scattering rather than absorption; thus, if our limb-scan sites are typical, the hazes cannot account for the stratospheric temperature inversion on Neptune and may not contribute significantly to atmospheric heating. We compare the imaging results with the results from other observations, including those of the Voyager Photopolarimeter Subsystem, and discuss differences between Neptune and Uranus.
Given their proposed use as trivalent actinide–lanthanide separation ligands, the role of molecular architecture on the radiation robustness of diglycolamide (DGA) molecules has been investigated. This study examined three prototypical molecules with differences in their aliphatic chain architecture: N,N,N′,N′-tetra(n-octyl)diglycolamide (TODGA), N,N,N′,N′-tetra(2-ethylhexyl)diglycolamide (T2EHDGA), and N,N′-dimethyl-N,N′-dioctyldiglycolamide (DMDODGA). Rate coefficients and activation parameters are reported for the reactivity of each DGA with the solvated electron (e solv − ) and the corresponding dodecane radical cation (RH˙ + ) over the temperature range of 10.0 to 44.1 °C. These measurements indicate that DMDODGA is the most chemically reactive with both transient radicals, which may be attributed to this molecule's more accessible backbone. Complementary gamma dose accumulation studies (≤ 600 kGy) under envisioned process conditions—50 mM DGA in n-dodecane solvent—afforded dose constants for the loss of DGA of d = (3.41 ± 0.07) × 10 −3 , (4.19 ± 0.09) × 10 −3 , and (4.65 ± 0.09) × 10 −3 kGy −1 for T2EHDGA, DMDODGA, and TODGA, respectively. These dose constants indicate that varying DGA architecture affords subtle differences in chemical reactivity, leading to varying rates of radiolytic degradation under envisioned actinide–lanthanide separation conditions. However, more ambitious DGA frameworks, such as modifying the backbone, branching of the aliphatic chains, and/or changing the size of the chain may be required for larger gains in radiolytic longevity while optimizing actinide–lanthanide selectivity.
Germanium Fabry-Perot etalons are commonly used in diode laser spectroscopy to establish relative frequency calibration scales for molecular absorption spectra. Typically the channel spectrum of the etalon is recorded simultaneously with the molecular spectrum as the laser injection current is tuned linearly, and the etalon free spectral range (fringe spacing) is used to measure the frequency separations among lines in the molecular spectrum. For this purpose, the etalon free spectral range must be known for the measurement wavelength, and this in turn relies on knowledge of the etalon length and the dispersive index at this wavelength. It is pointed out that the most satisfactory approach is to measure directly the free spectral range or dispersive index of the etalon at the wavelength of interest. A description is presented of measurements of this type, performed near 7.9 and 10.1 micrometers for a 7.7-cm long germanium etalon.
The use of a self-contained unit-gravity cell separation apparatus for separation of populations of mouse testicular cells is described. The apparatus, a Celsep (TM), maximizes the unit area over which sedimentation occurs, reduces the amount of separation medium employed, and is quite reproducible. Cells thus isolated have been good sources for isolation of DNA, and notably, high molecular weight RNA.
Broad-area single-quantum-well graded-index waveguide separate-confinement heterostructure lasers were fabricated by molecular beam epitaxy. A high external quantum efficiency of 79 percent and stable, single-lobed far-field patterns with a beam divergence as narrow as 0.8 deg (1.9 times diffraction limit) for a 100 micron-wide laser were obtained under pulsed conditions.
A liquid-chromatography technique has been developed for use in the quantitative analysis of urea (and of other nonvolatile organic compounds typically found with urea) dissolved in water. The technique involves the use of a column that contains an ion-exclusion resin; heretofore, this column has been sold for use in analyzing monosaccharides and food softeners, but not for analyzing water supplies. The prior technique commonly used to analyze water for urea content has been one of high-performance liquid chromatography (HPLC), with reliance on hydrophobic interactions between analytes in a water sample and long-chain alkyl groups bonded to an HPLC column. The prior technique has proven inadequate because of a strong tendency toward co-elution of urea with other compounds. Co-elution often causes the urea and other compounds to be crowded into a narrow region of the chromatogram (see left part of figure), thereby giving rise to low chromatographic resolution and misidentification of compounds. It is possible to quantitate urea or another analyte via ultraviolet- and visible-light absorbance measurements, but in order to perform such measurements, it is necessary to dilute the sample, causing a significant loss of sensitivity. The ion-exclusion resin used in the improved technique is sulfonated polystyrene in the calcium form. Whereas the alkyl-chain column used in the prior technique separates compounds on the basis of polarity only, the ion-exclusion-resin column used in the improved technique separates compounds on the basis of both molecular size and electric charge. As a result, the degree of separation is increased: instead of being crowded together into a single chromatographic peak only about 1 to 2 minutes wide as in the prior technique, the chromatographic peaks of different compounds are now separated from each other and spread out over a range about 33 minutes wide (see right part of figure), and the urea peak can readily be distinguished from the other peaks. Although the analysis takes more time in the improved technique, this disadvantage is offset by two important advantages: Sensitivity is increased. The minimum concentration of urea that can be measured is reduced (to between 1/5 and 1/3 of that of the prior technique) because it is not necessary to dilute the sample. The separation of peaks facilitates the identification and quantitation of the various compounds. The resolution of the compounds other than urea makes it possible to identify those compounds by use of mass spectrometry.
Hydrogen is a critically important molecule in the chemicals and energy industries, driving the need for efficient purification technologies such as membrane-based separations. However, polymer membranes often suffer from physical aging, leading to decreased gas permeability over time. This study leverages the unique aging behavior of contorted microporous polymers, synthesized via catalytic arene-norbornene annulation (CANAL) polymerization, to enhance molecular sieving for H 2 separations. While prior studies demonstrated a 1000% increase in H 2 /CH 4 selectivity with minimal permeability loss over 150 days, we extend this investigation to hyperaged (∼1 year) CANAL polymers and evaluate their performance under various conditions of industrial relevance. We report a remarkable 6100% increase in H 2 /CH 4 selectivity and a 2400% improvement in H 2 /N 2 selectivity, with only a 55% decline in H 2 permeability. These membranes exhibit excellent long-term stability in binary and ternary gas mixtures and at elevated temperatures. Additionally, extended aging enhances H 2 /CO 2 selectivity beyond the 2008 upper bound due to improved size-sieving. High-temperature permeation experiments and grand canonical Monte Carlo simulations reveal that H 2 permeability increases from 570 to 3500 barrer as the temperature rises from 35 °C to 190 °C, while H 2 /CO 2 selectivity declines from 14 to 3 due to the higher diffusion activation energy of CO 2 . Despite this tradeoff, hyperaged CANAL membranes maintain performance beyond the 200 °C upper bound, having selectivity–permeability performance comparable to many state-of-the-art membranes for H 2 /CO 2 separations. As a result, this study highlights the robustness and industrial viability of ultra-selective CANAL polymers for hydrogen purification, contributing to advancements in clean energy and sustainable separation technologies.
Ubiquilins are molecular chaperones that play multifaceted roles in proteostasis, with point mutations in UBQLN2 leading to altered phase-separation properties and amyotrophic lateral sclerosis (ALS). Our mechanistic understanding of this essential process has been hindered by a lack of structural information on the STI1 domain, which is essential for ubiquilin chaperone activity and phase separation. Here, we present the first crystal structure of a ubiquilin-family STI1 domain bound to a transmembrane domain (TMD), and show that ALS mutations disrupt the STI1-TMD interaction. We further demonstrate that ubiquilins contain multiple conserved internal sequences that bind to the STI1 domain, including the PXX-repeat region that is a hotspot for ALS mutations. We propose that these placeholder sequences prevent solvent exposure of the STI1 hydrophobic groove and contribute to the multivalency that drives ubiquilin phase-separation. Together, this work provides a new paradigm for understanding how STI1 domains modulate ubiquilin chaperone activity and phase separation, and offers insights into the molecular basis of ALS pathogenesis.
Efficient and stable water adsorbents are essential for removing moisture from natural gas and olefins during their production. Industrial desiccants such as alumina and zeolites require high regeneration temperatures, while metal-organic frameworks often suffer from limited long-term stability and reusability. Here, we introduce a new type of molecular desiccants (M-PyC) that, in principle, can be reused indefinitely. These simple molecular coordination complexes undergo fully reversible phase transitions between crystalline and amorphous states through the decoordination (bond breaking) and recoordination (bond reforming) of water molecules. They exhibit high water uptake (30 wt%) and superb selectivity, excluding hydrocarbons entirely. Their effectiveness for dehydration, combined with low regeneration temperature, fast desorption kinetics, low-cost and green synthesis, easy scalability to kilogram quantities, and essentially unlimited recyclability, makes them truly competitive dehydration agents for industrial separations. The use of amorphous molecular adsorbents, where crystallinity and porosity are no longer stringent requirements, and the adsorption-desorption process entirely under ambient air, offers a conceptually different approach to adsorption-based separation science and potentially realistic solution to the long-standing challenge of sustained stability in coordinate-bonded adsorbents.
The High Spectral Resolution Lidar (HSRL) system was developed for the remote measurement of atmospheric optical properties. Measurements are obtained by the separation of the backscattered signal into aerosol and molecular channels using a high spectral resolution Fabry-Perot optical interferometer to separate the aerosol contributions to backscatter near the laser wavelength from the Doppler-shifted molecular component of the backscatter. The transmitter consists of an optically pumped pulsed dye laser of the oscillator-amplifier design which emits at 467.88 nm, with a bandwidth of less than 0.3 pm. The transmitter and receiver share a common Schmidt-Cassegrain telescope, although they do not share the same field stop, but rather two conjugate stops. The HSRL system uses a computer-controlled dual-channel photon-counting data acquisition system providing for stable measurements at very low power levels and an excellent dynamic range. The system has been used to obtain airborne measurements of height profiles of aerosol and molecular backscatter cross sections.
Molecular-level insights into reactive separations are crucial for the design of new conversion pathways of carbon dioxide (CO 2 ). This work explores a postulated pathway that directs CO 2 to undergo inverse-electron-demand Diels–Alder reactions to produce heterocycles using the CO 2 chemically fixed on water-lean solvent molecules. Density functional theory calculations are applied to evaluate the lowest unoccupied molecular orbital (LUMO) energies of three types of reactants (1,3-butadiene, 1,3-cyclohexadiene, and 1,2,4,5-tetrazine) with various functional substituents. These calculations also provide a data set (5.8k data) for developing a machine learning model to efficiently predict LUMO energies. A computational screening of LUMO energies for an additional 47k diene and tetrazine candidates is performed, and a list of candidates with lowered LUMO energies by electron-withdrawing substituents is provided. These candidates are further examined by their reaction energy barriers computed from the interatomic potential or density functional theory. Two major energy barriers are identified, one for the proton transfer within the water-lean solvent and the other for the CO 2 transfer from the solvent molecule to the reactant candidate (diene or tetrazine). The functional substituents have a more significant impact on the second barrier but a very slight one on the first barrier. This exploratory work demonstrates a new possibility for guiding experimental efforts toward the chemical conversion of fixated CO 2 to value-added compounds.
Understanding complex, multistep chemical reactions at the molecular level is a major challenge whose solution would greatly benefit the design and optimization of numerous chemical processes. The separation of rare-earth (4f) and actinide (5f) elements is an example where improving our chemical understanding is important for designing and optimizing new chemistries, even with a limited number of observations. Here, in this work, we leverage data-driven artificial intelligence and machine-learning approaches to develop kinetic reaction networks that describe the liquid–liquid extraction mechanism of uranium using N,N-di-2-ethylhexyl-isobutyramide (DEHiBA). Specifically, we compare and contrast the properties of two classes of models: (1) purely data-driven models that are regularized using chemistry-agnostic, L1 regression and (2) chemistry-informed models that are regularized using relative reaction energies provided by quantum mechanical calculations. We observe that purely data-driven models are unbiased, simple, and accurate in their predictions of experimental measurements when provided with sufficient data but are difficult to fully constrain and interpret. In contrast, chemistry-informed models exhibit significantly improved chemical interpretability and consistency, providing a detailed description of the separation process while achieving high accuracy through ensemble averaging. Overall, the dominant species predicted to be extracted into the organic phase is UO 2 (NO 3 ) 2 (DEHiBA) 2 , agreeing with experimental slope analysis, thermodynamic modeling, EXAFS, and crystal structures. This work demonstrates that leveraging the fundamental structure of the problem can lead to efficient learning schemes that provide both accurate predictions and chemical insights at a low computational cost.
Ion transport properties in polymer electrolytes have been widely studied under rigorously dry and highly water-swollen conditions. However, the transition between these extremes, i.e., the low hydration regime, is still poorly understood at the molecular level and relevant to applications ranging from battery electrolytes to electrophoretic separations. Here, in this study, we apply atomistic molecular dynamics simulations to probe the role of hydration on ion mobilities and conductivities in LiTFSI-doped polyethers at low water content (less than 10% water by volume), which corresponds to 0−80% relative humidity conditions. With increasing water content, Li + ions exhibit two distinct regimes in their mobilities. At low water content, the majority of the Li + ions are weakly hydrated (two or fewer water molecules per Li + ion), maintaining strong interactions with their polymer solvation cage, and therefore exhibit only a weak increase in mobility relative to dry conditions. As water content increases, Li + ions form complete hydration shells, residing within water-rich domains that promote faster mobilities. Further, Li + mobilities increase more significantly in polymer electrolytes composed of more hydrophilic polymers and higher salt concentrations due to the formation of larger water-rich domains. In contrast, TFSI − has comparatively weak interactions with both the polymer and water, exhibiting a monotonic increase in mobility as a function of water content. Overall, these results help clarify the molecular mechanisms underlying ionic mobilities and conductivities in polymer electrolytes at low water content.