Multistate Dynamics and Kinetics of CO2 Activation by Ta+ in the Gas Phase: Insights into Single-Atom Catalysis.

The activation of carbon dioxide (CO2) by a transition-metal cation in the gas phase is a unique model system for understanding single-atom catalysis. The mechanism of such reactions is often attributed to a "two-state reactivity" model in which the high-energy barrier of a spin state correlating with ground-state reactants is avoided by intersystem crossing (ISC) to a different spin state with a lower barrier. However, such a "spin-forbidden" mechanism, along with the corresponding dynamics, has seldom been rigorously examined theoretically, due to the lack of global potential energy surfaces (PESs). In this work, we report full-dimensional PESs of the lowest-lying quintet, triplet, and singlet states of the TaCO2+ system, machine-learned from first-principles data. These PESs and the corresponding spin-orbit couplings enable us to provide an extensive theoretical characterization of the dynamics and kinetics of the reaction between the tantalum cation (Ta+) and CO2, which have recently been investigated experimentally at high collision energies using crossed beams and velocity map imaging, as well as at thermal energies using a selected-ion flow tube apparatus. The multistate quasi-classical trajectory simulations with surface hopping reproduce most of the measured product translational and angular distributions, shedding valuable light on the nonadiabatic reaction dynamics. The calculated rate coefficients from 200 to 600 K are also in good agreement with the latest experimental measurements. More importantly, these calculations revealed that the reaction is controlled by intersystem crossing, rather than potential barriers.

Dynamics of carbene formation in the reaction of methane with the tantalum cation in the gas phase.

The controlled activation of methane has drawn significant attention throughout various disciplines over the last few decades. In gas-phase experiments, the use of model systems with reduced complexity compared to condensed-phase catalytic systems allows us to investigate the intrinsic reactivity of elementary reactions down to the atomic level. Methane is rather inert in chemical reactions, as the weakening or cleavage of a C-H bond is required to make use of methane as C1-building block. The simplest model system for transition-metal-based catalysts is a mono-atomic metal ion. Only a few atomic transition-metal cations activate methane at room temperature. One of the most efficient elements is tantalum, which forms a carbene and releases molecular hydrogen in the reaction with methane: Ta+ + CH4 → TaCH2+ + H2. The reaction takes place at room temperature due to efficient intersystem crossing from the quintet to the triplet surface, i.e., from the electronic ground state of the tantalum cation to the triplet ground state of the tantalum carbene. This multi-state reactivity is often seen for reactions involving transition-metal centres, but leads to their theoretical treatment being a challenge even today. Chemical reactions, or to be precise reactive collisions, are dynamic processes making their description even more of a challenge to experiment and theory alike. Experimental energy- and angle-differential cross sections allow us to probe the rearrangement of atoms during a reactive collision. By interpreting the scattering signatures, we gain insight into the atomistic mechanisms and can move beyond stationary descriptions. Here, we present a study combining collision energy dependent experimentally measured differential cross sections with ab initio calculations of the minimum energy pathway. Product ion velocity distributions were recorded using our crossed-beam velocity map imaging experiment dedicated to studying transition-metal ion molecule reactions. TaCH2+ velocity distributions reveal a significant degree of indirect dynamics. However, the scattering distributions also show signatures of rebound dynamics. We compare the present results to the oxygen transfer reaction between Ta+ and carbon dioxide, which we recently studied.

Ta+ and Nb+ + CO2: intersystem crossing in ion-molecule reactions.

The reactions of Ta+ and Nb+ with CO2 proceed only by a highly efficient oxygen atom transfer reaction to the respective oxide at room temperature in the gas phase. Although the product spin states are not determined, thermochemistry dictates that they must be different from ground state quintet Ta+ and Nb+, implying that intersystem crossing (ISC) has occurred. Recent reactive scattering experiments found dominant indirect dynamics for the reaction with Ta+ hinting at a bottleneck along the reaction path. The question on the nature of the bottleneck, whether it involves a crossing point or a transition state, could not be finally answered because theory located both close to each other. Here, we aim at shedding further light onto the impact of intersystem crossing on the reaction dynamics and ultimately the reactivity of transition metal ion reactions in the gas phase. We employ a combination of thermal kinetics for Ta+ and Nb+ with CO2 using a selected-ion flow tube (SIFT) apparatus and differential scattering cross sections for Nb+ + CO2 from crossed-beam velocity map imaging. The reaction with niobium again shows dominant indirect dynamics and in general very similar dynamics compared to Ta+ + CO2. At thermal energies, both reactions show sub-collisional rate constants with small negative temperature dependencies. Experiments are complemented by high level quantum chemical calculations of the minimum energy pathway. Statistical modelling well-reproduces the experimental thermal rate constants, and suggests that the Nb+ reaction is rate-limited by the intersystem crossing at thermal energies.

Factors Associated with Vaccine Hesitancy in the State of Alaska.

BACKGROUND: Vaccine hesitancy (VH) is a major public health problem which includes not only concerns about vaccine, but often includes beliefs not aligned with evidence. The etiology of VH is complicate, including genuine concerns about vaccine safety to beliefs in disproven or unsubstantiated theories. Understanding VH includes determining the factors associated with people most likely to be susceptible. OBJECTIVES: To identify characteristics of persons more likely to have VH based on perceived vaccine safety. DESIGN: We conducted a cross sectional, targeted online survey of 1,024 respondents. METHODS: The survey collected data on demographics and vaccine beliefs. A seven-question VH scale was created based on an extensive literature review. When measured, this scale had high internal validity based on Cronbach's Alpha (α = 0.80, 95% CI, 0.79, 0.82) and provided a continuous measurement to understand the VH degree. RESULTS: Persons reporting a conservative political ideology had the highest VH score ([Formula: see text] = 15.0), followed by other ([Formula: see text] =12.7), moderate ([Formula: see text] =9.29), and liberal ([Formula: see text] =6.72). Education level was another strong indicator of VH, decreasing from the highest score of high school graduates ( [Formula: see text] = 13.2) to graduate degree holders ([Formula: see text] = 9.22). CONCLUSION: The more conservative a person's political ideology, the higher the VHS. We asked for ideology, rather than political party, although they are related, they are not the same. Ideology influences more domains than voting patterns. Higher educational attainment shows a protective effect against VH. These findings have direct implication for public health interventions, new interventions should be designed to be more accessible for persons with less formal education and more amenable to persons who hold a more conservative ideology.

Kidney failure in Bardet-Biedl syndrome.

The aim of this study was to explore kidney failure (KF) in Bardet-Biedl syndrome (BBS), focusing on high-risk gene variants, demographics, and morbidity. We employed the Clinical Registry Investigating BBS (CRIBBS) to identify 44 (7.2%) individuals with KF out of 607 subjects. Molecularly confirmed BBS was identified in 37 KF subjects and 364 CRIBBS registrants. KF was concomitant with recessive causal variants in 12 genes, with BBS10 the most predominant causal gene (26.6%), while disease penetrance was highest in SDCCAG8 (100%). Two truncating variants were present in 67.6% of KF cases. KF incidence was increased in genes not belonging to the BBSome or chaperonin-like genes (p < 0.001), including TTC21B, a new candidate BBS gene. Median age of KF was 12.5 years, with the vast majority of KF occurring by 30 years (86.3%). Females were disproportionately affected (77.3%). Diverse uropathies were identified, but were not more common in the KF group (p = 0.672). Kidney failure was evident in 11 of 15 (73.3%) deaths outside infancy. We conclude that KF poses a significant risk for premature morbidity in BBS. Risk factors for KF include female sex, truncating variants, and genes other than BBSome/chaperonin-like genes highlighting the value of comprehensive genetic investigation.

Mn12 -Acetate Complexes Studied as Single Molecules.

The phenomenon of single molecule magnet (SMM) behavior of mixed valent Mn12 coordination clusters of general formula [MnIII 8 MnIV 4 O12 (RCOO)16 (H2 O)4 ] had been exemplified by bulk samples of the archetypal [MnIII 8 MnIV 4 O12 (CH3 COO)16 (H2 O)4 ] (4) molecule, and the molecular origin of the observed magnetic behavior has found support from extensive studies on the Mn12 system within crystalline material or on molecules attached to a variety of surfaces. Here we report the magnetic signature of the isolated cationic species [Mn12 O12 (CH3 COO)15 (CH3 CN)]+ (1) by gas phase X-ray Magnetic Circular Dichroism (XMCD) spectroscopy, and we find it closely resembling that of the corresponding bulk samples. Furthermore, we report broken symmetry DFT calculations of spin densities and single ion tensors of the isolated, optimized complexes [Mn12 O12 (CH3 COO)15 (CH3 CN)]+ (1), [Mn12 O12 (CH3 COO)16 ] (2), [Mn12 O12 (CH3 COO)16 (H2 O)4 ] (3), and the complex in bulk geometry [MnIII 8 MnIV 4 O12 (CH3 COO)16 (H2 O)4 ] (5). The found magnetic fingerprints - experiment and theory alike - are of a remarkable robustness: The MnIV 4 core bears almost no magnetic anisotropy while the surrounding MnIII 8 ring is highly anisotropic. These signatures are truly intrinsic properties of the Mn12 core scaffold within all of these complexes and largely void of the environment. This likely holds irrespective of bulk packing effects.

An Innovative Approach to Remote Electronic Health Onboarding Record Education Amid a Global Pandemic.

The COVID-19 pandemic required social and physical distancing to reduce the spread of disease. The reduction in meeting sizes made it difficult to offer traditional in-person EHR training to new and transferring employees. This paper aims to share how one nurse educator team used an innovative approach to transition traditional EHR onboarding education to synchronous remote learning during the global pandemic. Participants in the remote learning course (n = 94) were compared with those who had previously completed the traditional course (n = 110). Postcourse evaluations for each group were comparable. Remote learning participants found the technology conducive to training and reported higher scores for locating and reviewing patient information than those in the traditional course. Providing remote EHR education is comparable with traditional classroom education. Remote learning provided a safe, effective way to onboard new staff during the pandemic.

Novel antimicrobial ointment for infected wound healing in an in vitro and in vivo porcine model.

Microbial contamination of wounds is a significant problem that delays healing, particularly when bacterial biofilms are present. A novel combination of pectinic acid (PG) + caprylic acid (CAP) was previously found in vitro to be highly effective in eradicating various pathogens in biofilms with minimal cytotoxicity. In this study, a novel wound ointment was formulated with PG + CAP and first assessed in vitro using a well-established biofilm eradication model. In vitro, the PG + CAP ointment was shown to be efficacious in reducing the microbial biofilms. This ointment was then tested in vivo in two pilot porcine wound healing models, with and without Staphylococcus aureus microbial challenge. Ointments were applied to each wound daily, and healing by wound closure area measurement was assessed weekly over 4 weeks. After 4 weeks, pigs were sacrificed and wounds were scored for reepithelialization, inflammation, granulation tissue, and collagen deposition. We compared PG + CAP to hydroxyethylcellulose + glycerol ointment base (control) and MediHoney (comparator). In the porcine microbial challenge model, the novel antimicrobial PG + CAP wound ointment rapidly eradicated bacterial organisms embedded in wounds, was safe and well-tolerated, and was associated with enhanced healing compared to ointment base and MediHoney. Specifically, the cumulative histopathology, reepithelialization of epidermis, and mature granulation tissue in the wound bed was significantly better with PG + CAP than with control and MediHoney treatments. This ointment warrants further study as a non-antibiotic ointment for use in treating a wide array of infected wounds.

Facility-level characteristics associated with family planning and child immunization services integration in urban areas of Nigeria: a longitudinal analysis.

BACKGROUND: Unmet need for postpartum contraception is high. Integration of family planning with routine child immunization services may help to satisfy unmet need. However, evidence about the determinants and effects of integration has been inconsistent, and more evidence is required to ascertain whether and how to invest in integration. In this study, facility-level family planning and immunization integration index scores are used to: (1) determine whether integration changes over time and (2) identify whether facility-level characteristics, including exposure to the Nigerian Urban Reproductive Health Initiative (NURHI), are associated with integration across facilities in six urban areas of Nigeria. METHODS: This study utilizes health facility data collected at baseline (n = 400) and endline (n = 385) for the NURHI impact evaluation. Difference-in-differences models estimate the associations between facility-level characteristics, including exposure to NURHI, and Provider and Facility Integration Index scores. The two outcome measures, Provider and Facility Integration Index scores, reflect attributes that support integrated service delivery. These indexes, which range from 0 (low) to 10 (high), were constructed using principal component analysis. Scores were calculated for each facility. Independent variables are (1) time period, (2) whether the facility received the NURHI intervention, and (3) additional facility-level characteristics. RESULTS: Within intervention facilities, mean Provider Integration Index scores were 6.46 at baseline and 6.79 at endline; mean Facility Integration Index scores were 7.16 (baseline) and 7.36 (endline). Within non-intervention facilities, mean Provider Integration Index scores were 5.01 at baseline and 6.25 at endline; mean Facility Integration Index scores were 5.83 (baseline) and 6.12 (endline). Provider Integration Index scores increased significantly (p = 0.00) among non-intervention facilities. Facility Integration Index scores did not increase significantly in either group. Results identify facility-level characteristics associated with higher levels of integration, including smaller family planning client load, family planning training among providers, and public facility ownership. Exposure to NURHI was not associated with integration index scores. CONCLUSION: Programs aiming to increase integration of family planning and immunization services should monitor and provide targeted support for the implementation of a well-defined integration strategy that considers the influence of facility characteristics and concurrent initiatives.

Long-term complications and implant survival rates after cranioplastic surgery: a single-center study of 392 patients.

Cranioplasty (CP) is a standard procedure in neurosurgical practice for patients after (decompressive) craniectomy. However, CP surgery is not standardized, is carried out in different ways, and is associated with considerable complication rates. Here, we report our experiences with the use of different CP materials and analyze long-term complications and implant survival rates. We retrospectively studied patients who underwent CP surgery at our institution between 2004 and 2014. Binary logistic regression analysis was performed in order to identify risk factors for the development of complications. Kaplan-Meier analysis was used to estimate implant survival rates. A total of 392 patients (182 females, 210 males) with a mean age of 48 years were included. These patients underwent a total of 508 CP surgeries. The overall complication rate of primary CP was 33.2%, due to bone resorption/loosening (14.6%) and graft infection (7.9%) with a mean implant survival of 120 ± 5 months. Binary logistic regression analysis showed that young age (< 30 years) (p = 0.026, OR 3.150), the presence of multidrug-resistant bacteria (p = 0.045, OR 2.273), and cerebrospinal fluid (CSF) shunt (p = 0.001, OR 3.137) were risk factors for postoperative complications. The use of titanium miniplates for CP fixation was associated with reduced complication rates and bone flap osteolysis as well as longer implant survival rates. The present study highlights the risk profile of CP surgery. Young age (< 30 years) and shunt-dependent hydrocephalus are associated with postoperative complications especially due to bone flap autolysis. Furthermore, a rigid CP fixation seems to play a crucial role in reducing complication rates.

Development of integration indexes to determine the extent of family planning and child immunization services integration in health facilities in urban areas of Nigeria.

BACKGROUND: Integrating family planning into child immunization services may address unmet need for contraception by offering family planning information and services to postpartum women during routine child immunization visits. However, policies and programs promoting integration are often based on insubstantial or conflicting evidence about its effects on service delivery and health outcomes. While integration models vary, many studies measure integration as binary (a facility is integrated or not) rather than a multidimensional and varying continuum. It is thus challenging to ascertain the determinants and effects of integrated service delivery. This study creates Facility and Provider Integration Indexes, which measure capacity to support integrated family planning and child immunization services and applies them to analyze the extent of integration across 400 health facilities. METHODS: This study utilizes cross-sectional health facility (N = 400; 58% hospitals, 42% primary healthcare centers) and healthcare provider (N = 1479) survey data that were collected in six urban areas of Nigeria for the impact evaluation of the Nigerian Urban Reproductive Health Initiative. Principal Component Analysis was used to develop Provider and Facility Integration Indexes that estimate the extent of integration in these health facilities. The Provider Integration Index measures provider skills and practices that support integrated service delivery while the Facility Integration Index measures facility norms that support integrated service delivery. Index scores range from zero (low) to ten (high). RESULTS: Mean Provider Integration Index score is 5.42 (SD 3.10), and mean Facility Integration Index score is 6.22 (SD 2.72). Twenty-three percent of facilities were classified as having low Provider Integration scores, 32% as medium, and 45% as high. Fourteen percent of facilities were classified as having low Facility Integration scores, 38% as medium, and 48% as high. CONCLUSION: Many facilities in our sample have achieved high levels of integration, while many others have not. Results suggest that using more nuanced measures of integration may (a) more accurately reflect true variation in integration within and across health facilities, (b) enable more precise measurement of the determinants or effects of integration, and (c) provide more tailored, actionable information about how best to improve integration. Overall, results reinforce the importance of utilizing more nuanced measures of facility-level integration.

Differentiation of Francisella tularensis Subspecies and Subtypes.

The highly infectious and zoonotic pathogen Francisella tularensis is the etiologic agent of tularemia, a potentially fatal disease if untreated. Despite the high average nucleotide identity, which is >99.2% for the virulent subspecies and >98% for all four subspecies, including the opportunistic microbe Francisella tularensis subsp. novicida, there are considerable differences in genetic organization. These chromosomal disparities contribute to the substantial differences in virulence observed between the various F. tularensis subspecies and subtypes. The methods currently available to genotype F. tularensis cannot conclusively identify the associated subpopulation without using time-consuming testing or complex scoring matrices. To address this need, we developed both single and multiplex quantitative real-time PCR (qPCR) assays that can accurately detect and identify the hypervirulent F. tularensis subsp. tularensis subtype A.I, the virulent F. tularensis subsp. tularensis subtype A.II, F. tularensis subsp. holarctica (also referred to as type B), and F. tularensis subsp. mediasiatica, as well as opportunistic F. tularensis subsp. novicida from each other and near neighbors, such as Francisella philomiragia, Francisella persica, and Francisella-like endosymbionts found in ticks. These fluorescence-based singleplex and non-matrix scoring multiplex qPCR assays utilize a hydrolysis probe, providing sensitive and specific F. tularensis subspecies and subtype identification in a rapid manner. Furthermore, sequencing of the amplified F. tularensis targets provides clade confirmation and informative strain-specific details. Application of these qPCR- and sequencing-based detection assays will provide an improved capability for molecular typing and clinical diagnostics, as well as facilitate the accurate identification and differentiation of F. tularensis subpopulations during epidemiological investigations of tularemia source outbreaks.

Proton transfer dynamics modified by CH-stretching excitation.

Gaining insight how specific rovibrational states influence reaction kinetics and dynamics is a fundamental goal of physical chemistry. Purely statistical approaches often fail to predict the influence of a specific state on the reaction outcome, evident in a great number of both experimental and theoretical studies. Most detailed insight in atomistic reaction mechanisms is achieved using accurate collision experiments and high level dynamics calculations. For ion-molecule reactions such experiments are scarce. Here we show the influence of symmetric CH-stretching vibration on the rate and dynamics of proton transfer in the reaction of F- + CH3I. We find a pronounced shift in the reaction dynamics for excited reactions from indirect to preferred direct dynamics at higher collision energy. Moreover, excited reactions occur at larger impact parameters. Finally, we compare vibrational excitation with collision energy and find that vibration is overall more efficient in promoting reactivity, which agrees with recent theoretical calculations.

Imaging Reaction Dynamics of F-(H2O) and Cl-(H2O) with CH3I.

The dynamics of microhydrated nucleophilic substitution reactions have been studied using crossed beam velocity map imaging experiments and quasiclassical trajectory simulations at different collision energies between 0.3 and 2.6 eV. For F-(H2O) reacting with CH3I, a small fraction of hydrated product ions I-(H2O) is observed at low collision energies. This product, as well as the dominant I-, is formed predominantly through indirect reaction mechanisms. In contrast, a much smaller indirect fraction is determined for the unsolvated reaction. At the largest studied collision energies, the solvated reaction is found to also occur via a direct rebound mechanism. The measured product angular distributions exhibit an overall good agreement with the simulated angular distributions. Besides nucleophilic substitution, also ligand exchange reactions forming F-(CH3I) and, at high collision energies, proton transfer reactions are detected. The differential scattering images reveal that the Cl-(H2O) + CH3I reaction also proceeds predominantly via indirect reaction mechanisms.

Threshold photodetachment spectroscopy of the astrochemical anion CN.

Threshold photodetachment spectroscopy has been performed on the molecular anion CN- at both 16(1) K and 295(2) K in a 22-pole ion trap and at 295(2) K from a pulsed ion beam. The spectra show a typical energy dependence of the detachment cross section yielding a determination of the electron affinity of CN to greater precision than has previously been known at 31 163(16) cm-1 [3.864(2) eV]. Allowed s-wave detachment is observed for CN-, but the dependence of the photodetachment cross section near the threshold is perturbed by the long-range interaction between the permanent dipole moment of CN and the outgoing electron. Furthermore, we observe a temperature dependence of the cross section near the threshold, which we attribute to a reduction of the effective permanent dipole due to higher rotational excitation at higher temperatures.

Polymethylmethacrylate patient-matched implants (PMMA-PMI) for complex and revision cranioplasty: analysis of long-term complication rates and patient outcomes.

Objective: Cranioplasty (CP) is associated with high complication rates and patient-matched implants (PMI) are frequently used for CP. However, only limited data are available regarding complication rates of PMI-based CP after complex or failed primary CP. Here we report our experience with the use of polymethylmethacrylate (PMMA) PMI for this purpose.Method: We analyzed all patients with complex or failed primary CP and subsequent implantation of PMMA-PMI between 2010 and 2015 at our institution.Results: A total of 67 patients (29 females, 38 males) with a mean age of 43 years (range: 13-74 years) were included in the study. Primary PMI-CP was performed in 18 patients with destructive or osteolytic bone tumors. Secondary PMI-CP was performed in 49 patients. Complications occurred in 14 patients with an overall complication rate of 21.7% during a mean follow-up of 39.7 ± 23.4 month. Approximately two-thirds of the patients reported a good quality of life after the initial event and subsequent CP. The majority of patients (>90%) was satisfied with the cosmetic result.Conclusion: Surgical CP with PMMA-PMI appears to be a suitable method for patients with failed or complex CP. Complication rates are comparable to those reported for primary CP.

The Evaluation of Joint Mobilization Dosage on Ankle Range of Motion in Individuals With Decreased Dorsiflexion and a History of Ankle Sprain.

CONTEXT: Mulligan's Mobilization with Movement (MWM) is a common intervention used to address dorsiflexion range of motion (DFROM) impairments. However, the treatment dosage of MWMs varies within the literature. OBJECTIVE: The aim of this study was to examine the effect of serial MWM application on DFROM. DESIGN: Repeated-measures cohort. SETTING: A Midwestern University and the surrounding community. PARTICIPANTS: A total of 18 adults (13 females; age = 29 [12.87] y; DFROM = 30.26° [4.60°]) with decrease dorsiflexion (<40°) participated. Inclusion criteria consisted of a history of ≥1 ankle sprain, ≥18 years old, no lower-extremity injury in the last 6 months, and no history of foot/ankle surgery. INTERVENTION: Participants completed a single data collection session consisting of 10 individual sets of MWMs. MAIN OUTCOME MEASURES: DFROM was taken at baseline and immediately after each intervention set (post 1, post 2, … post 10). DFROM was measured with a digital inclinometer on the anterior aspect of the tibia during the weight-bearing lunge test with the knee straight and knee bent. Analysis of variances examined DFROM changes over time. Post hoc analysis evaluated sequential pairwise comparisons and changes from baseline at each time point. RESULTS: Analysis of variance results indicated a significant time main effect for weight-bearing lunge test with knee bent (P < .001) and a nonsignificant effect for weight-bearing lunge test with knee straight (P < .924). Post hoc analysis indicated improvements in the weight-bearing lunge test with knee bent at each timepoint compared with baseline (P < .005). Post 2 improved compared with post 1 (P = .027). No other pairwise sequential comparisons were significant (P > .417). CONCLUSIONS: MWMs significantly improved acute knee bent DFROM and indicated that after 2 sets of MWMs, no further DFROM improvements were identified. Future research should investigate the lasting effects of DFROM improvements with variable MWM dosages.

Unexpected Indirect Dynamics in Base-Induced Elimination.

Base-induced elimination (E2) and bimolecular nucleophilic substitution (SN2) are two of the most versatile reactions that are important in preparative organic chemistry. These stereospecific reactions are often found in direct competition with each other. Elimination can proceed via two distinct transition states, referred to as anti and syn, of which anti is commonly energetically favored. To investigate the intrinsic dynamics of base-induced elimination, reactions under single-collision conditions are required. Here, we present reactive scattering results on the prototype reaction of the fluoride anion with tert-butyl halides. The observed mechanistic fingerprints are associated with the E2 reaction, because steric hindrance at the α-carbon suppresses the SN2 reaction [Carrascosa, E.; Meyer, J.; Zhang, J.; Stei, M.; Michaelsen, T.; Hase, W. L.; Yang, L.; Wester, R. Nat. Commun. 2017, 8, 25]. The reaction coordinate shows energetically submerged transition states, with anti favored over syn, and we found a very shallow prereaction well for anti. We predominantly found indirect dynamics for a range of collision energies, which can be separated into three remarkably different mechanisms. At low collision energies, the first is a large impact parameter indirect mechanism which leads to a forward-backward symmetric scattering signature. The second mechanism is attributed to low-impact parameter reactions with a near-statistical partitioning of the total available energy. The majority of events are associated with widespread isotropic scattering. Unexpectedly, the product ion kinetic energy distributions are independent of collision energy. We associate this with dynamic trapping in a prereaction well supported by a large centrifugal potential. These measured fingerprints support that atomistic reaction dynamics cannot be predicted based on stationary arguments alone.

Long-term impact of a community-led sanitation campaign in India, 2005-2016.

OBJECTIVE: To evaluate the long-term impact of a community-led total sanitation campaign in rural India. METHODS: Local organizations in Odisha state, India worked with researchers to evaluate a community-led total sanitation campaign, which aimed to increase the demand for household latrines by raising awareness of the social costs of poor sanitation. The intervention ran from February to March 2006 in 20 randomly-selected villages and 20 control villages. Within sampled villages, we surveyed a random subset of households (around 28 households per village) at baseline in 2005 and over the subsequent 10-year period. We analysed changes in latrine ownership, latrine functionality and open defecation among approximately 1000 households. We estimated linear probability models that examined differences between households in intervention and control villages in 2006, 2010 and 2016. FINDINGS: In 2010, 4 years after the intervention, ownership of latrines was significantly higher (29.3 percentage points; 95% confidence interval, CI: 17.5 to 41.2) and open defecation was significantly lower (-6.8 percentage points; 95% CI: -13.1 to -1.0) among households in intervention villages, relative to controls. In 2016, intervention households continued to have higher rates of ever owning a latrine (26.3 percentage points; 95% CI: 20.9 to 31.8). However, latrine functionality and open defecation were no longer different across groups, due to both acquisition of latrines by control households and abandonment and deterioration of latrines in intervention homes. CONCLUSION: Future research should investigate how to maintain and rehabilitate latrines and how to sustain long-term behaviour change.

Topographic diversity of fungal and bacterial communities in human skin.

Traditional culture-based methods have incompletely defined the microbial landscape of common recalcitrant human fungal skin diseases, including athlete's foot and toenail infections. Skin protects humans from invasion by pathogenic microorganisms and provides a home for diverse commensal microbiota. Bacterial genomic sequence data have generated novel hypotheses about species and community structures underlying human disorders. However, microbial diversity is not limited to bacteria; microorganisms such as fungi also have major roles in microbial community stability, human health and disease. Genomic methodologies to identify fungal species and communities have been limited compared with those that are available for bacteria. Fungal evolution can be reconstructed with phylogenetic markers, including ribosomal RNA gene regions and other highly conserved genes. Here we sequenced and analysed fungal communities of 14 skin sites in 10 healthy adults. Eleven core-body and arm sites were dominated by fungi of the genus Malassezia, with only species-level classifications revealing fungal-community composition differences between sites. By contrast, three foot sites--plantar heel, toenail and toe web--showed high fungal diversity. Concurrent analysis of bacterial and fungal communities demonstrated that physiologic attributes and topography of skin differentially shape these two microbial communities. These results provide a framework for future investigation of the contribution of interactions between pathogenic and commensal fungal and bacterial communities to the maintainenace of human health and to disease pathogenesis.