Beyond Density Functional Theory: the Multiconfigurational Approach to Model Heterogeneous Catalysis

Catalytic processes are crucially important for many practical chemical applications. Heterogeneous catalysts are especially appealing because of their high stability and the relative ease with which they may be recovered and reused. Computational modeling can play an important role in the design of more catalytically active materials through the identification of reaction mechanisms and the opportunity to assess hypothetical catalysts in silico prior to experimental verification. Kohn-Sham density functional theory (KS-DFT) is the most used method in computational catalysis because it is affordable and it gives results of reasonable accuracy in many instances. Furthermore, it can be employed in a “black-box” mode that does not require significant a priori knowledge of the system. However, KS-DFT has some limitations: it suffers from self-interaction error (sometime referred to as delocalization error), but a greater concern is that it provides an intrinsically single-reference description of the electronic structure, and this can be especially problematic for modeling catalysis when transition metals are involved. In this perspective, we highlight some noteworthy applications of KS-DFT to heterogeneous computational catalysis, as well as cases where KS-DFT fails accurately to describe electronic structures and intermediate spin states in open-shell transition metal systems. We next provide an introduction to state-of-the-art multiconfigurational (MC; also referred to as multireference (MR)) methods and their advantages and limitations for modeling heterogeneous catalysis. We focus on specific examples to which MC methods have 2 been applied and discuss the challenges associated with these calculations. We conclude by offering our vision for how the community can make further progress in the development of MC methods for application to heterogeneous catalysis

The role of cation-dependent chloride transporters in neuropathic pain following spinal cord injury

<p>Abstract</p> <p>Background</p> <p>Altered Cl^-homeostasis and GABAergic function are associated with nociceptive input hypersensitivity. This study investigated the role of two major intracellular Cl^-regulatory proteins, Na⁺-K⁺-Cl^-cotransporter 1 (NKCC1) and K⁺-Cl^-cotransporter 2 (KCC2), in neuropathic pain following spinal cord injury (SCI).</p> <p>Results</p> <p>Sprague-Dawley rats underwent a contusive SCI at T9 using the MASCIS impactor. The rats developed hyperalgesia between days 21 and 42 post-SCI. Thermal hyperalgesia (TH) was determined by a decrease in hindpaw thermal withdrawal latency time (WLT) between days 21 and 42 post-SCI. Rats with TH were then treated with either vehicle (saline containing 0.25% NaOH) or NKCC1 inhibitor bumetanide (BU, 30 mg/kg, i.p.) in vehicle. TH was then re-measured at 1 h post-injection. Administration of BU significantly increased the mean WLT in rats (p < 0.05). The group administered with the vehicle alone showed no anti-hyperalgesic effects. Moreover, an increase in NKCC1 protein expression occurred in the lesion epicenter of the spinal cord during day 2–14 post-SCI and peaked on day 14 post-SCI (p < 0.05). Concurrently, a down-regulation of KCC2 protein was detected during day 2–14 post-SCI. The rats with TH exhibited a sustained loss of KCC2 protein during post-SCI days 21–42. No significant changes of these proteins were detected in the rostral region of the spinal cord.</p> <p>Conclusion</p> <p>Taken together, expression of NKCC1 and KCC2 proteins was differentially altered following SCI. The anti-hyperalgesic effect of NKCC1 inhibition suggests that normal or elevated NKCC1 function and loss of KCC2 function play a role in the development and maintenance of SCI-induced neuropathic pain.</p

Metal-Organic Frameworks with Metal Catecholates for O2/N2 Separation

Oxygen and nitrogen are widely produced feedstocks with diverse fields of applications, but are primarily obtained via the energy-intensive cryogenic distillation of air. More energy-efficient processes are desirable, and materials such as zeolites and metal-organic frameworks (MOFs) have been studied for air separation. Inspired by recent theoretical work identifying metal-catecholates for enhancement of O2 selectivity MOFs, in this work the computation-ready experimental (CoRE) database of MOF structures was screened to identify promising candidates for incorporation of metal catecholates. Based on structural requirements, preliminary Grand-Canonical Monte Carlo simulations, and further constraints to ensure the computational feasibility, over 5,000 structures were eliminated and four MOFs (UiO-66(Zr), Ce-UiO-66, MOF-5, and IRMOF-14) were treated with periodic density functional theory (DFT). Metal catecholates (Mg, Co, Ni, Zn, and Cd) were selected based on cluster DFT calculations and were added to the shortlisted MOFs. Periodic DFT was used to compute O2 and N2 binding energies near metal catecholates. We find that the binding energies are primarily dependent on the metals in the metal catecholates, all of which bind O2 quite strongly (80-258 kJ/mol) and have weaker binding for N2 (3-148 kJ/mol). Of those studied here, Cd-catecholated MOFs are identified as the most promisin

Traditional and Health-Related Philanthropy: The Role of Resources and Personality

I study the relationships of resources and personality characteristics to charitable giving, postmortem organ donation, and blood donation in a nationwide sample of persons in households in the Netherlands. I find that specific personality characteristics are related to specific types of giving: agreeableness to blood donation, empathic concern to charitable giving, and prosocial value orientation to postmortem organ donation. I find that giving has a consistently stronger relation to human and social capital than to personality. Human capital increases giving; social capital increases giving only when it is approved by others. Effects of prosocial personality characteristics decline at higher levels of these characteristics. Effects of empathic concern, helpfulness, and social value orientations on generosity are mediated by verbal proficiency and church attendance.

Individual Responses for Muscle Activation, Repetitions, and Volume during Three Sets to Failure of High- (80% 1RM) \u3ci\u3eversus\u3c/i\u3e Low-Load (30% 1RM) Forearm Flexion Resistance Exercise

This study compared electromyographic (EMG) amplitude, the number of repetitions completed, and exercise volume during three sets to failure of high- (80% 1RM) versus low-load (30% 1RM) forearm flexion resistance exercise on a subject-by-subject basis. Fifteen men were familiarized, completed forearm flexion 1RM testing. Forty-eight to 72 h later, the subjects completed three sets to failure of dumbbell forearm flexion resistance exercise with 80% (n = 8) or 30% (n = 7) 1RM. EMG amplitude was calculated for every repetition, and the number of repetitions performed and exercise volume were recorded. During sets 1, 2, and 3, one of eight subjects in the 80% 1RM group demonstrated a significant linear relationship for EMG amplitude versus repetition. For the 30% 1RM group, seven, five, and four of seven subjects demonstrated significant linear relationships during sets 1, 2, and 3, respectively. The mean EMG amplitude responses show that the fatigue-induced increases in EMG amplitude for the 30% 1RM group and no change in EMG amplitude for the 80% 1RM group resulted in similar levels of muscle activation in both groups. The numbers of repetitions completed were comparatively greater, while exercise volumes were similar in the 30% versus 80% 1RM group. Our results, in conjunction with those of previous studies in the leg extensors, suggest that there may be muscle specific differences in the responses to high- versus low-load exercise

Individual Responses for Muscle Activation, Repetitions, and Volume during Three Sets to Failure of High- (80% 1RM) \u3cem\u3eversus\u3c/em\u3e Low-Load (30% 1RM) Forearm Flexion Resistance Exercise

This study compared electromyographic (EMG) amplitude, the number of repetitions completed, and exercise volume during three sets to failure of high- (80% 1RM) versus low-load (30% 1RM) forearm flexion resistance exercise on a subject-by-subject basis. Fifteen men were familiarized, completed forearm flexion 1RM testing. Forty-eight to 72 h later, the subjects completed three sets to failure of dumbbell forearm flexion resistance exercise with 80% (n = 8) or 30% (n = 7) 1RM. EMG amplitude was calculated for every repetition, and the number of repetitions performed and exercise volume were recorded. During sets 1, 2, and 3, one of eight subjects in the 80% 1RM group demonstrated a significant linear relationship for EMG amplitude versus repetition. For the 30% 1RM group, seven, five, and four of seven subjects demonstrated significant linear relationships during sets 1, 2, and 3, respectively. The mean EMG amplitude responses show that the fatigue-induced increases in EMG amplitude for the 30% 1RM group and no change in EMG amplitude for the 80% 1RM group resulted in similar levels of muscle activation in both groups. The numbers of repetitions completed were comparatively greater, while exercise volumes were similar in the 30% versus 80% 1RM group. Our results, in conjunction with those of previous studies in the leg extensors, suggest that there may be muscle specific differences in the responses to high- versus low-load exercise

Macrophage phenotype in response to ECM bioscaffolds

Macrophage presence and phenotype are critical determinants of the healing response following injury. Downregulation of the pro-inflammatory macrophage phenotype has been associated with the therapeutic use of bioscaffolds composed of extracellular matrix (ECM), but phenotypic characterization of macrophages has typically been limited to small number of non-specific cell surface markers or expressed proteins. The present study determined the response of both primary murine bone marrow derived macrophages (BMDM) and a transformed human mononuclear cell line (THP-1 cells) to degradation products of two different, commonly used ECM bioscaffolds; urinary bladder matrix (UBM-ECM) and small intestinal submucosa (SIS-ECM). Quantified cell responses included gene expression, protein expression, commonly used cell surface markers, and functional assays. Results showed that the phenotype elicited by ECM exposure (MECM) is distinct from both the classically activated IFNγ + LPS phenotype and the alternatively activated IL-4 phenotype. Furthermore, the BMDM and THP-1 macrophages responded differently to identical stimuli, and UBM-ECM and SIS-ECM bioscaffolds induced similar, yet distinct phenotypic profiles. The results of this study not only characterized an MECM phenotype that has anti-inflammatory traits but also showed the risks and challenges of making conclusions about the role of macrophage mediated events without consideration of the source of macrophages and the limitations of individual cell markers

CCAFS midline synthesis – Ghana. Assessment of changes at household, village and organization levels since the 2011 CCAFS baseline surveys

In 2011, CCAFS carried out baseline surveys (household survey, a village study and an organizational survey) in 21 research sites across 17 countries within its five focus regions, using standardized baseline tools in each site. Seven years after the implementation of the baseline studies, the CCAFS program carried out surveys again in Lawra-Jirapa, Ghana as a test case to help determine whether a midline assessment in other sites would be worth the substantial investment that will be needed. The objective of the CCAFS midline surveys was to assess what kinds of changes have occurred and whether these changes are helping the households and villages adapt to and mitigate climate change. It also provided information at the village level about some basic indicators of natural resource utilization, organizational landscapes, information networks for weather and agricultural information, as well as mitigation baseline information, which can be compared across sites and monitored over time. The same tools were used with a few improvements to ensure comparability with the data collected in 2011. This info note provides a synthesis of the changes at the household, village and organizational levels emphasizing major indicators that have changed

CCAFS midline synthesis report - Ghana (GH0108)

In 2011, CCAFS carried out baseline surveys (household survey, a village study and an organizational survey) in 21 research sites across 17 countries within its five focus regions, using standardized baseline tools in each site. Seven years after the implementation of the baseline studies, the CCAFS program carried out surveys again in Lawra-Jirapa, Ghana as a test case to help determine whether a midline assessment in other sites would be worth the substantial investment that will be needed. The objective of the CCAFS midline surveys was to assess what kinds of changes have occurred and whether these changes are helping the households and villages adapt to and mitigate climate change. It also provided information at the village level about some basic indicators of natural resource utilization, organizational landscapes, information networks for weather and agricultural information, as well as mitigation baseline information, which can be compared across sites and monitored over time. The same tools were used with a few improvements to ensure comparability with the data collected in 2011