Evaluation of the Stability of Diamine-Appended Mg2(dobpdc) Frameworks to Sulfur Dioxide.

Diamine-appended Mg2(dobpdc) (dobpdc4- = 4,4'-dioxidobiphenyl-3,3'-dicarboxylate) metal-organic frameworks are a promising class of CO2 adsorbents, although their stability to SO2─a trace component of industrially relevant exhaust streams─remains largely untested. Here, we investigate the impact of SO2 on the stability and CO2 capture performance of dmpn-Mg2(dobpdc) (dmpn = 2,2-dimethyl-1,3-propanediamine), a candidate material for carbon capture from coal flue gas. Using SO2 breakthrough experiments and CO2 isobar measurements, we find that the material retains 91% of its CO2 capacity after saturation with a wet simulated flue gas containing representative levels of CO2 and SO2, highlighting the robustness of this framework to SO2 under realistic CO2 capture conditions. Initial SO2 cycling experiments suggest dmpn-Mg2(dobpdc) may achieve a stable operating capacity in the presence of SO2 after initial passivation. Evaluation of several other diamine-Mg2(dobpdc) variants reveals that those with primary,primary (1°,1°) diamines, including dmpn-Mg2(dobpdc), are more robust to humid SO2 than those featuring primary,secondary (1°,2°) or primary,tertiary (1°,3°) diamines. Based on the solid-state 15N NMR spectra and density functional theory calculations, we find that under humid conditions, SO2 reacts with the metal-bound primary amine in 1°,2° and 1°,3° diamine-appended Mg2(dobpdc) to form a metal-bound bisulfite species that is charge balanced by a primary ammonium cation, thereby facilitating material degradation. In contrast, humid SO2 reacts with the free end of 1°,1° diamines to form ammonium bisulfite, leaving the metal-diamine bond intact. This structure-property relationship can be used to guide further optimization of these materials for CO2 capture applications.

Porous materials for carbon dioxide separations.

Global investment in counteracting climate change has galvanized increasing interest in carbon capture and sequestration (CCS) as a versatile emissions mitigation technology. As decarbonization efforts accelerate, CCS can target the emissions of large point-source emitters, such as coal- or natural gas-fired power plants, while also supporting the production of renewable or low-carbon fuels. Furthermore, CCS can enable decarbonization of difficult-to-abate industrial processes and can support net CO2 removal from the atmosphere through bioenergy coupled with CCS or direct air capture. Here we review the development of porous materials as next-generation sorbents for CO2 capture applications. We focus on stream- and sector-specific challenges while highlighting case studies within the context of the rapidly shifting energy landscape. We conclude with a discussion of key needs from the materials community to expand deployment of carbon capture technologies.

Overcoming Metastable CO2 Adsorption in a Bulky Diamine-Appended Metal-Organic Framework.

Carbon capture at fossil fuel-fired power plants is a critical strategy to mitigate anthropogenic contributions to global warming, but widespread deployment of this technology is hindered by a lack of energy-efficient materials that can be optimized for CO2 capture from a specific flue gas. As a result of their tunable, step-shaped CO2 adsorption profiles, diamine-functionalized metal-organic frameworks (MOFs) of the form diamine-Mg2(dobpdc) (dobpdc4- = 4,4'-dioxidobiphenyl-3,3'-dicarboxylate) are among the most promising materials for carbon capture applications. Here, we present a detailed investigation of dmen-Mg2(dobpdc) (dmen = 1,2-diamino-2-methylpropane), one of only two MOFs with an adsorption step near the optimal pressure for CO2 capture from coal flue gas. While prior characterization suggested that this material only adsorbs CO2 to half capacity (0.5 CO2 per diamine) at 1 bar, we show that the half-capacity state is actually a metastable intermediate. Under appropriate conditions, the MOF adsorbs CO2 to full capacity, but conversion from the half-capacity structure happens on a very slow time scale, rendering it inaccessible in traditional adsorption measurements. Data from solid-state magic angle spinning nuclear magnetic resonance spectroscopy, coupled with van der Waals-corrected density functional theory, indicate that ammonium carbamate chains formed at half capacity and full capacity adopt opposing configurations, and the need to convert between these states likely dictates the sluggish post-half-capacity uptake. By use of the more symmetric parent framework Mg2(pc-dobpdc) (pc-dobpdc4- = 3,3'-dioxidobiphenyl-4,4'-dicarboxylate), the metastable trap can be avoided and the full CO2 capacity of dmen-Mg2(pc-dobpdc) accessed under conditions relevant for carbon capture from coal-fired power plants.

Deep CCS: Moving Beyond 90% Carbon Dioxide Capture.

The large-scale deployment of carbon capture technologies is expected to play a crucial role in efforts to meet stringent climate targets set forth by the Paris Agreement, but current models rely heavily upon carbon dioxide removal (CDR) strategies for which viability at the gigatonne scale is uncertain. While most 1.5 and 2 °C scenarios project rapid decarbonization of the energy sector facilitated by carbon capture and sequestration (CCS), they generally assume that CCS units can only capture ∼90% of the CO2 in coal and natural gas combustion flues because this was previously considered the optimal condition for aqueous amine scrubbers. In this Perspective, we discuss a small but growing body of literature that examines the prospect of moving significantly beyond 90% capture-a concept we term deep CCS-in light of recent developments in materials and process design. The low incremental costs associated with performing varying degrees of deep CCS suggest that this approach is not only feasible but may also alleviate burdens placed upon CDR techniques facing significant barriers to large-scale deployment. We estimate that rapid deployment of deep CCS in deep decarbonization pathways could avoid more than 1 gigatonne of CO2 globally each year. The principles of deep CCS could also be applied directly to the CDR strategy of employing bioenergy with CCS, which could lead to a significant alleviation of the land and freshwater burden associated with this technology.

Cooperative Carbon Dioxide Adsorption in Alcoholamine- and Alkoxyalkylamine-Functionalized Metal-Organic Frameworks.

A series of structurally diverse alcoholamine- and alkoxyalkylamine-functionalized variants of the metal-organic framework Mg2 (dobpdc) are shown to adsorb CO2 selectively via cooperative chain-forming mechanisms. Solid-state NMR spectra and optimized structures obtained from van der Waals-corrected density functional theory calculations indicate that the adsorption profiles can be attributed to the formation of carbamic acid or ammonium carbamate chains that are stabilized by hydrogen bonding interactions within the framework pores. These findings significantly expand the scope of chemical functionalities that can be utilized to design cooperative CO2 adsorbents, providing further means of optimizing these powerful materials for energy-efficient CO2 separations.

Cooperative carbon capture and steam regeneration with tetraamine-appended metal-organic frameworks.

Natural gas has become the dominant source of electricity in the United States, and technologies capable of efficiently removing carbon dioxide (CO2) from the flue emissions of natural gas-fired power plants could reduce their carbon intensity. However, given the low partial pressure of CO2 in the flue stream, separation of CO2 is particularly challenging. Taking inspiration from the crystal structures of diamine-appended metal-organic frameworks exhibiting two-step cooperative CO2 adsorption, we report a family of robust tetraamine-functionalized frameworks that retain cooperativity, leading to the potential for exceptional efficiency in capturing CO2 under the extreme conditions relevant to natural gas flue emissions. The ordered, multimetal coordination of the tetraamines imparts the materials with extraordinary stability to adsorption-desorption cycling with simulated humid flue gas and enables regeneration using low-temperature steam in lieu of costly pressure or temperature swings.

Challenges and opportunities for adsorption-based CO2 capture from natural gas combined cycle emissions.

In recent years, the power sector has shown a growing reliance on natural gas, a cleaner-burning fuel than coal that emits approximately half as much CO2 per kWh of energy produced. This rapid growth in the consumption of natural gas has led to increased CO2 emissions from gas-fired power plants. To limit the contribution of fossil fuel combustion to atmospheric CO2 levels, carbon capture and sequestration has been proposed as a potential emission mitigation strategy. However, despite extensive exploration of solid adsorbents for CO2 capture, few studies have examined the performance of adsorbents in post-combustion capture processes specific to natural gas flue emissions. In this perspective, we emphasize the importance of considering gas-fired power plants alongside coal-fired plants in future analyses of carbon capture materials. We address specific challenges and opportunities related to adsorptive carbon capture from the emissions of gas-fired plants and discuss several promising candidate materials. Finally, we suggest experiments to determine the viability of new CO2 capture materials for this separation. This broadening in the scope of current carbon capture research is urgently needed to accelerate the deployment of transformational carbon capture technologies.

Enhancing the first enzymatic step in the histidine biosynthesis pathway increases the free histidine pool and nickel tolerance in Arabidopsis thaliana.

Naturally selected nickel (Ni) tolerance in Alyssum lesbiacum has been proposed to involve constitutively high levels of endogenous free histidine. Transgenic Arabidopsis thaliana expressing a Salmonella typhimurium ATP phosphoribosyl transferase enzyme (StHisG) resistant to feedback inhibition by histidine contained approximately 2-fold higher histidine concentrations than wild type plants. Under exposure to a toxic Ni concentration, biomass production in StHisG expressing lines was between 14- and 40-fold higher than in wild-type plants. This suggested that enhancing the first step in the histidine biosynthesis pathway is sufficient to increase the endogenous free histidine pool and Ni tolerance in A. thaliana.

Detection of fungal DNA in effusion associated with acute and serous otitis media.

OBJECTIVES/HYPOTHESIS: Routine bacterial and viral cultures of middle ear fluid are often negative, suggesting that other infectious agents may be involved. Because of the similarities between the paranasal sinuses and middle ear space and the recent recognition of fungi as important pathogens in inflammation of the paranasal sinuses, we investigated the potential role of fungi in acute otitis media and serous otitis media using culture and polymerase chain reaction techniques. STUDY DESIGN: Prospective study. METHODS: Middle ear effusions of 29 patients who underwent myringotomy and pressure equalization tube placement for persistent serous otitis media or recurrent acute otitis media were collected. Fungal culture of the effusion samples was performed on potato flake agar. DNA from the effusion was isolated using standard techniques. Polymerase chain reaction, using radiolabeled universal fungus primer for internal transcribed spacer of 5.8s ribosomal DNA, was performed to detect the presence of any fungal DNA in the samples. RESULTS: Culture of middle ear effusions showed no evidence of fungal growth. Polymerase chain reaction analysis was able to detect the constituent ribosomal DNA of a single fungal genome. Fungal DNA was present in 34% of middle ear effusion samples. CONCLUSIONS: Fungal DNA is present in recurrent acute otitis media and serous otitis media suggesting that it may play an etiological role in serous otitis media and acute otitis media. However, additional studies are necessary to delineate the role of fungi in the pathogenesis of otitis media.

Cochlear implant outcomes in the elderly.

OBJECTIVE: This study aimed to review cochlear implantation with respect to surgical and auditory outcomes in subjects aged 70 years and older. STUDY DESIGN: Retrospective chart review. SETTING: Tertiary referral centers. PATIENTS: Sixty-five patients aged 70 years or older at the time of implantation were compared to a group of patients aged <70 years. INTERVENTION: Patients underwent multichannel cochlear implantation with either the Clarion or Nucleus device. MAIN OUTCOME MEASURE: Presence or absence of surgical complications and auditory performance with open-set word and sentence recognition testing. RESULTS: In patients implanted at age 70 or older, significant improvement in speech understanding was demonstrated in performance scores using Consonant Nucleus Consonant words, Central Institute for the Deaf sentences, and Hearing in Noise Test sentences at 3, 6, and 12 months when compared to preimplantation scores. However, their performance was slightly poorer when compared to a control group of patients <70 years of age in the same measures at 3, 6, and 12 months. CONCLUSIONS: The elderly population showed significant improvement in auditory performance tests following cochlear implantation compared to their preimplantation scores but performed less well than younger patients.

The role of botulinum toxin type B (Myobloc) in the treatment of hyperkinetic facial lines.

Botulinum toxin type B was studied for the management of hyperkinetic facial lines. It showed clinical longevity of up to 12 weeks on subjective rating scales and 8 weeks on objective rating scales. Botulinum toxin type B has shown relative safety but can have autonomic side effects at higher total doses, which limits the possibility of continued dose escalation. Although these findings may preclude its use as a primary modality for the use in hyperkinetic facial lines, botulinum toxin type B still has a role in the treatment of the aesthetic patient and is yet another tool in the armamentarium of aesthetic practitioners.

A validated rating scale for hyperkinetic facial lines.

OBJECTIVE: To test the reliability of a simple rating system to describe hyperkinetic facial lines. METHODS: A rated numeric kinetic line scale was developed and presented to 11 postresidency physicians specializing in aesthetic facial care. These physicians independently reviewed photographs of 20 patients, first at rest, then with activation of the frontalis, corrugator, and orbicularis oculi muscles. Kappa statistics for multiple raters were used to assess interobserver reliability. RESULTS: The nonweighted kappa values were between 0.4 and 0.8 for the frontalis, corrugator, and orbicularis muscle groups. This represents moderate to substantial observer agreement and is highly significant for each muscle group. CONCLUSIONS: A new rating scale for hyperkinetic facial lines accounts for facial appearance at rest and with expression. It is easily used and has interobserver reliability. As the only objective and validated scale for hyperkinetic facial lines, this rated numeric kinetic line scale is recommended for the evaluation of pretreatment and posttreatment results in patients undergoing therapy for this problem. Moreover, an alternative scale rating resting and kinetic lines as independent variables is also being developed. Both must be considered to evaluate treatment outcomes when using neurotoxins.