Applicability of the BET method for determining surface areas of microporous metal-organic frameworks

The surface area is one of the most important quantities for characterizing novel porous materials. The BET analysis is the standard method for determining surface areas from nitrogen adsorption isotherms and was originally derived for multilayer gas adsorption onto flat surfaces. Metal-organic frameworks (MOFs) are a relatively new class of crystalline, porous materials that have been shown to exhibit very large BET surface areas. These materials are microporous and possess surfaces that are far from flat. In some MOFs, adsorption occurs through a pore-filling mechanism rather than by layer formation. Thus, it is unclear whether BET surface area numbers reported for these materials are truly meaningful. Given the standard practice of reporting BET surface areas for novel porous materials, a critical test of the BET method is much needed. In this work, grand canonical Monte Carlo simulations were used to predict adsorption isotherms for nitrogen in a series of MOFs. The predicted isotherms were used as pseudoexperimental data to test the applicability of the BET theory for obtaining surface areas of microporous MOFs. BET surface areas calculated from the simulated isotherms agree very well with the accessible surface areas calculated directly from the crystal structures in a geometric fashion. In addition, the surface areas agree well with experimental reports in the literature. These results provide a strong validation that the BET theory can be used to obtain surface areas of MOFs.     

Endogenous Retinoic Acid Required to Maintain the Epidermis Following Ultraviolet Light Exposure in SKH‐1 Hairless Mice

Ultraviolet light B (UVB) exposure induces cutaneous squamous cell carcinoma (cSCC), one of the most prevalent human cancers. Reoccurrence of cSCC in high‐risk patients is prevented by oral retinoids. But oral retinoid treatment causes significant side effects; and patients develop retinoid resistance. Exactly how retinoids prevent UVB‐induced cSCC is currently not well understood. Retinoid resistance blocks mechanistic studies in the leading mouse model of cSCC, the UVB‐exposed SKH‐1 hairless mouse. To begin to understand the role of retinoids in UVB‐induced cSCC we first examined the localization pattern of key retinoid metabolism proteins by immunohistochemistry 48 h after UVB treatment of female SKH‐1 mice. We next inhibited retinoic acid (RA) synthesis immediately after UVB exposure. Acute UVB increased RA synthesis, signaling and degradation proteins in the stratum granulosum. Some of these proteins changed their localization; while other proteins just increased in intensity. In contrast, acute UVB reduced the retinoid storage protein lectin:retinol acyltransferase (LRAT) in the epidermis. Inhibiting RA synthesis disrupted the epidermis and impaired differentiation. These data suggest that repair of the epidermis after acute UVB exposure requires endogenous RA synthesis.     

Mechanisms Involved in Microbially Enhanced Oil Recovery

Microbial enhanced oil recovery (MEOR) represents a possible cost-effective tertiary oil recovery method. Although the idea of MEOR has been around for more than 75 years, even now little is known of the mechanisms involved. In this study, Draugen and Ekofisk enrichment cultures, along with Pseudomonas spp. were utilized to study the selected MEOR mechanisms. Substrates which could potentially stimulate the microorganisms were examined, and l-fructose, d-galacturonic acid, turnose, pyruvic acid and pyruvic acid methyl ester were found to be the best utilized by the Ekofisk fermentative enrichment culture. Modelling results indicated that a mechanism likely to be important for enhanced oil recovery is biofilm formation, as it required a lower in situ cell concentration compared with some of the other MEOR mechanisms. The bacterial cells themselves were found to play an important role in the formation of emulsions. Bulk coreflood and flow cell experiments were performed to examine MEOR mechanisms, and microbial growth was found to lead to possible alterations in wettability. This was observed as a change in wettability from oil wet (contact angle 154°) to water wet (0°) due to the formation of biofilms on the polycarbonate coupons.     

Solvent‐Dependent Fluorescence Lifetimes of Estrone, 17β‐Estradiol and 17α‐Ethinylestradiol

The fluorescence lifetimes of the estrogens, estrone, 17β‐estradiol and 17α‐ethinylestradiol, were studied in various solvents. The fluorescence lifetimes of 17β‐estradiol and 17α‐ethinylestradiol decreased from 4.7 to 0.9 ns as the solvent hydrogen bond accepting ability increased, in good agreement with other phenolic molecules. Estrone's two fluorescence bands had distinct lifetimes, with the 304 nm band having a lifetime shorter than 200 ps, reflecting efficient energy transfer to the carbonyl group, which had lifetimes ranging from 4.4 to 4.9 ns depending on the solvent. Solvent effects on the ¹ππ*, ¹πσ* and ¹nπ* states that are relevant to estrogen photophysics can adequately explain these trends. The solvent dependence on the excited states of these potent endocrine disruptors has significant implications for their photochemistry.     

Effect of self-constructed concept map with peer feedback on chemistry learning outcome

Concept mapping remains widely used in education. However, little is known about how self-constructed concept maps and peer feedback can improve student learning outcomes in chemistry. We investigated the effects of peer feedback on concept mapping and how it improves students' learning performance in a large second-semester, introductory chemistry course. Three hundred and twenty students were randomly assigned to one of two concept mapping conditions: self-constructed concept map with peer feedback and self-constructed concept map without peer feedback. Each group constructed concept maps that depicted the relationship between concepts on the topic of intermolecular force. The results showed that students in the self-constructed concept map with peer feedback condition outperformed students in the no peer feedback condition in chemistry learning outcome. Overall, this study demonstrates that peer feedback enhances the effectiveness of learning with generative concept maps. The implications and future directions are discussed.     

Dense or Porous Packing? Two‐Dimensional Self‐Assembly of Star‐Shaped Mono‐, Bi‐, and Terpyridine Derivatives

The self‐assembly behavior of five star‐shaped pyridyl‐functionalized 1,3,5‐triethynylbenzenes was studied at the interface between an organic solvent and the basal plane of graphite by scanning tunneling microscopy. The mono‐ and bipyridine derivatives self‐assemble in closely packed 2D crystals, whereas the derivative with the more bulky terpyridines crystallizes with porous packing. DFT calculations of a monopyridine derivative on graphene, support the proposed molecular model. The calculations also reveal the formation of hydrogen bonds between the nitrogen atoms and a hydrogen atom of the neighboring central unit, as a small nonzero tunneling current was calculated within this region. The title compounds provide a versatile model system to investigate the role of multivalent steric interactions and hydrogen bonding in molecular monolayers.     

Natural gas storage cycles: Influence of nonisothermal effects and heavy alkanes

A mathematical model is developed for examining the influence of nonisothermal effects and accumulation of heavy alkanes on natural gas storage cycles. The model is solved for the charge and discharge steps of the cycle. This is the first study to solve the natural gas storage problem for a nonisothermal charge of natural gas containing impurities. We examine both adiabatic and isothermal operation of natural gas and pure methane storage cycles on BPL carbon and an activated carbon prepared from coconut shells. Our simulations show for both carbons that the adiabatic gas storage cycles operate under subcooled conditions with respect to the feed temperature due to long discharge times and the desorption heat. It is also shown that degradation of gas storage performance due to impurities depends more on selectivity of the material for heavy alkanes than on adsorption capacities.     

On the temperature dependence of amide I frequencies of peptides in solution

The temperature dependence of the amide I vibrational frequencies of peptides in solution was investigated. In D2O, the amide I' bands of both an alpha-helical oligopeptide, the random-coil poly(L-lysine), and the simplest amide, N-methyl acetamide (NMA), exhibit linear frequency shifts of approximately 0.07 cm(-1)/degrees C with increasing temperature. Similar amide I frequency shifts are also observed for NMA in both polar (acetonitrile and DMSO) and nonpolar (1,4-dioxane) organic solvents, thus ruling out hydrogen-bonding strength as the cause of these effects. The experimental NMA amide I frequencies in the organic solvents can be accurately described by a simple theory based on the Onsager reaction field with temperature-dependent solvent dielectric properties and a solute molecular cavity. DFT-level calculations (BPW91/cc-pVDZ) for NMA with an Onsager reaction field confirm the significant contribution of the molecular cavity to the predicted amide I frequencies. Comparison of the computations to experimental data shows that the frequency-dependent response of the reaction field, taken into account by the index of refraction, is crucial for describing the amide I frequencies in polar solvents. The poor predictions of the model for the NMA amide I band in D2O might be due, in part, to the unknown temperature dependence of the refractive index of D2O in the mid-IR range, which was approximated by the available values in the visible region.