Late-Stage C(sp2)-C(sp3) Diversification via Nickel Oxidative Addition Complexes.

Herein, we describe nickel oxidative addition complexes (Ni-OACs) of drug-like molecules as a platform to rapidly generate lead candidates with enhanced C(sp3) fraction. The potential of Ni-OACs to access new chemical space has been assessed not only in C(sp2)-C(sp3) couplings but also in additional bond formations without recourse to specialized ligands and with improved generality when compared to Ni-catalyzed reactions. The development of an automated diversification process further illustrates the robustness of Ni-OACs, thus offering a new gateway to expedite the design-make-test-analyze (DMTA) cycle in drug discovery.

Temperature-Pressure Swing Process for Reactive Carbon Capture and Conversion to Methanol: Techno-Economic Analysis and Life Cycle Assessment.

A model was developed to conduct techno-economic analysis (TEA) and life cycle assessment (LCA) for reactive carbon capture (RCC) and conversion of carbon dioxide (CO2) to methanol. This RCC process is compared to a baseline commercialized flue gas CO2 hydrogenation process. An ASPEN model was combined with existing TEA and LCA models into a larger TEA/LCA framework in Python. From preliminary experimental data, the model found a levelized cost of $0.79/kg methanol for the baseline process and $0.99/kg for the RCC process. The cradle-to-gate carbon intensity of the baseline process was 0.50 kg-CO2e/kg-methanol, compared to 0.55 kg-CO2e/kg-methanol for the RCC process. However, water consumption for RCC (10.21 kg-H2O/kg-methanol) is greatly reduced compared to the baseline (12.89 kg-H2O/kg-methanol). Future improvements in hydrogen electrolysis costs will benefit the RCC. A target H2/methanol mass ratio of 0.26 was developed for RCC laboratory experiments to reduce methanol cost below the baseline. If a ratio of 0.24 can be achieved, a levelized cost of $0.76/kg methanol is projected, with a carbon intensity of 0.42 kg-CO2e/kg-methanol.

Exploring the cognitive profiles related to unimodal auditory versus multisensory hallucinations in schizophrenia-spectrum disorders.

INTRODUCTION: Hallucinations can be experienced across multiple sensory modalities, but psychiatric studies investigating the cognitive mechanisms of hallucinations have been somewhat restricted to the auditory domain. This study explored the cognitive profiles of individuals experiencing multisensory hallucinations (MH) in schizophrenia-spectrum disorders (SSD) and compared these to those experiencing unimodal auditory hallucinations (AH) or no hallucinations (NH). METHODS: Participants included SSD patients (n = 119) stratified by current hallucination status (NH, AH, MH) and nonclinical controls (NCs; n = 113). Group performance was compared across several cognitive domains: speed of processing, attention, working memory, verbal learning, visual learning, reasoning and problem-solving, social cognition, and inhibition. RESULTS: The clinical groups performed worse than NCs but differences between the clinical groups were not evident across most cognitive domains. Exploratory analyses revealed that the MH group was more impaired on the visual learning task compared to the NH (but not AH) group. CONCLUSIONS: Preliminary results suggest that impaired visual learning may be related to MH. This could be attributed to the presence of visual hallucinations (VH), or greater psychopathology, in this group. However, replication is needed, as well as the investigation of other potential cognitive mechanisms of MH.

The relationship between cognitive clusters and telomere length in bipolar-schizophrenia spectrum disorders.

BACKGROUND: Schizophrenia and bipolar disorder are complex mental illnesses that are associated with cognitive deficits. There is considerable cognitive heterogeneity that exists within both disorders. Studies that cluster schizophrenia and bipolar patients into subgroups based on their cognitive profile increasingly demonstrate that, relative to healthy controls, there is a severely compromised subgroup and a relatively intact subgroup. There is emerging evidence that telomere shortening, a marker of cellular senescence, may be associated with cognitive impairments. The aim of this study was to explore the relationship between cognitive subgroups in bipolar-schizophrenia spectrum disorders and telomere length against a healthy control sample. METHODS: Participants included a transdiagnostic group diagnosed with bipolar, schizophrenia or schizoaffective disorder (n = 73) and healthy controls (n = 113). Cognitive clusters within the transdiagnostic patient group, were determined using K-means cluster analysis based on current cognitive functioning (MATRICS Consensus Cognitive Battery scores). Telomere length was determined using quantitative PCRs genomic DNA extracted from whole blood. Emergent clusters were then compared to the healthy control group on telomere length. RESULTS: Two clusters emerged within the patient group that were deemed to reflect a relatively intact cognitive group and a cognitively impaired subgroup. Telomere length was significantly shorter in the severely impaired cognitive subgroup compared to the healthy control group. CONCLUSIONS: This study replicates previous findings of transdiagnostic cognitive subgroups and associates shorter telomere length with the severely impaired cognitive subgroup. These findings support emerging literature associating cognitive impairments in psychiatric disorders to accelerated cellular aging as indexed by telomere length.

Comparing Life-Cycle Emissions of Biofuels for Marine Applications: Hydrothermal Liquefaction of Wet Wastes, Pyrolysis of Wood, Fischer-Tropsch Synthesis of Landfill Gas, and Solvolysis of Wood.

Recent restrictions on marine fuel sulfur content and a heightened regulatory focus on maritime decarbonization are driving the deployment of low-carbon and low-sulfur alternative fuels for maritime transport. In this study, we quantified the life-cycle greenhouse gas and sulfur oxide emissions of several novel marine biofuel candidates and benchmarked the results against the emissions reduction targets set by the International Maritime Organization. A total of 11 biofuel pathways via four conversion processes are considered, including (1) biocrudes derived from hydrothermal liquefaction of wastewater sludge and manure, (2) bio-oils from catalytic fast pyrolysis of woody biomass, (3) diesel via Fischer-Tropsch synthesis of landfill gas, and (4) lignin ethanol oil from reductive catalytic fractionation of poplar. Our analysis reveals that marine biofuels' life-cycle greenhouse gas emissions range from -60 to 56 gCO2e MJ-1, representing a 41-163% reduction compared with conventional low-sulfur fuel oil, thus demonstrating a considerable potential for decarbonizing the maritime sector. Due to the net-negative carbon emissions from their life cycles, all waste-based pathways showed over 100% greenhouse gas reduction potential with respect to low-sulfur fuel oil. However, while most biofuel feedstocks have a naturally occurring low-sulfur content, the waste feedstocks considered here have higher sulfur content, requiring hydrotreating prior to use as a marine fuel. Combining the break-even price estimates from a published techno-economic analysis, which was performed concurrently with this study, the marginal greenhouse gas abatement cost was estimated to range from -$120 to $370 tCO2e-1 across the pathways considered. Lower marginal greenhouse gas abatement costs were associated with waste-based pathways, while higher marginal greenhouse gas abatement costs were associated with the other biomass-based pathways. Except for lignin ethanol oil, all candidates show the potential to be competitive with a carbon credit of $200 tCO2e-1 in 2016 dollars, which is within the range of prices recently received in connection with California's low-carbon fuel standard.

Factors Impacting Access and Engagement of Cognitive Remediation Therapy for People with Schizophrenia: A Systematic Review.

OBJECTIVES: Neurocognitive deficits are central in schizophrenia. Cognitive remediation has proven effective in alleviating these deficits, with medium effect sizes. However, sizeable attrition rates are reported, with the reasons still uncertain. Furthermore, cognitive remediation is not part of routine mental health care. We conducted a systematic review to investigate factors that influence access and engagement of cognitive remediation in schizophrenia. METHODS: We systematically searched the PubMed, Web of Science, and PsycINFO databases for peer-reviewed articles including a cognitive remediation arm, access, and engagement data, and participants with schizophrenia spectrum disorders aged 17-65 years old. Duplicates and studies without a distinct cognitive remediation component, protocol papers, single case studies, case series, and reviews/meta-analyses were excluded. RESULTS: We included 67 studies that reported data on access and engagement, and extracted quantitative and qualitative data. Access data were limited, with most interventions delivered on-site, to outpatients, and in middle- to high-income countries. We found a median dropout rate of 14.29%. Only a small number of studies explored differences between dropouts and completers (n = 5), and engagement factors (n = 13). Dropouts had higher negative symptomatology and baseline self-efficacy, and lower baseline neurocognitive functioning and intrinsic motivation compared to completers. The engagement was positively associated with intrinsic motivation, self-efficacy, perceived usefulness, educational level, premorbid intelligence quotient, baseline neurocognitive functioning, some neurocognitive outcomes, and therapeutic alliance; and negatively associated with subjective cognitive complaints. Qualitative results showed good acceptability of cognitive remediation, with some areas for improvement. CONCLUSIONS: Overall, access and engagement results are scarce and heterogeneous. Further investigations of cognitive remediation for inpatients, as well as remote delivery, are needed. Future clinical trials should systematically explore attrition and related factors. Determining influential factors of access and engagement will help improve the implementation and efficacy of cognitive remediation, and thus the recovery of people with schizophrenia.

Elite Athletes Successfully Return to the Preinjury Level of Sport Following Ankle Syndesmosis Injuries: A Systematic Review and Meta-Analysis.

OBJECTIVE: To comprehensively review and report the outcomes of ankle syndesmotic injury management in elite athletes. DATA SOURCES: Three databases were searched for articles reporting the rate of return to sport following treatment of ankle syndesmotic injuries in elite athletes (collegiate or professional level). Ten articles and 440 athletes were included. Articles reporting the rate of return to sport following high ankle sprain injury in elite athletes. Data collected included demographics, type of treatment received, and return to sport (RTS) information. A random effects model was used. MAIN RESULTS: The estimated overall rate of RTS was 99% (95% CI, 95.5-99.9). The mean time to RTS was 38 ± 18 (range, 14-137) days. Of the 440 athletes, 269 (269/440%, 61%) were treated nonoperatively (nonoperative group); the rate of RTS was 99.6%, and the athletes returned at a mean time of 29 ± 14 (range, 13-45) days. A total of 171 athletes (171 of 440%, 39%) underwent surgical treatment (operative group). All (171 of 171%, 100%) athletes returned at a mean time of 50.3 ± 13 (range, 41-137) days. Almost all athletes who underwent surgery had suture button fixation (164 of 171 athletes, 96%), and the mean time to RTS was 7 weeks with 9.1% complication rate. CONCLUSIONS: Elite athletes with ankle syndesmosis injury return to sport at an extremely high rates, following operative or nonoperative treatment. Return to the preinjury level of competition should be expected at 4 weeks and 7 weeks in high-level athletes who undergo nonoperative and operative management, respectively. Suture button fixation was used by the majority of studies reporting surgical management of ankle syndesmosis injuries in athletes.

Techno-economic Analysis of Sustainable Biofuels for Marine Transportation.

Renewable, low-carbon biofuels offer the potential opportunity to decarbonize marine transportation. This paper presents a comparative techno-economic analysis and process sustainability assessment of four conversion pathways: (1) hydrothermal liquefaction (HTL) of wet wastes such as sewage sludge and manure; (2) fast pyrolysis of woody biomass; (3) landfill gas Fischer-Tropsch synthesis; and (4) lignin-ethanol oil from the lignocellulosic ethanol biorefinery utilizing reductive catalytic fractionation. These alternative marine biofuels have a modeled minimum fuel selling price between $1.68 and $3.98 per heavy fuel oil gallon equivalent in 2016 U.S. dollars based on a mature plant assessment. The selected pathways also exhibit good process sustainability performance in terms of water intensity compared to the petroleum refineries. Further, the O and S contents of the biofuels vary widely. While the non-HTL biofuels exhibit negligible S content, the raw biocrudes via HTL pathways from sludge and manure show relatively high S contents (>0.5 wt %). Partial or full hydrotreatment can effectively lower the biocrude S content. Additionally, co-feeding with other low-sulfur wet wastes such as food waste can provide another option to produce raw biocrude with lower S content to meet the target with further hydrotreatment. This study indicates that biofuels could be a cost-effective fuel option for the marine sector. Marine biofuels derived from various feedstocks and conversion technologies could mitigate marine biofuel adoption risk in terms of feedstock availability and biorefinery economics.

Depression, perceived disability and unemployment are associated with reduced life satisfaction in anorexia nervosa.

Life satisfaction is a core aspect of an individual's wellbeing and describes the subjective assessment of their quality of life. Reduced life satisfaction is frequently reported in anorexia nervosa (AN),  but the factors contributing to this are still unclear. This study sought to extend previous work by examining 12 potential correlates of AN life satisfaction. One hundred and five female AN patients were administered questionnaires assessing life satisfaction, depression, anxiety, stress, employment status, marital status, body mass index, eating disorder symptomatology, perceived disability and readiness for change. A stepwise linear regression revealed that only depression, perceived disability and employment status were significantly associated with AN life satisfaction. The findings thus highlight prevailing mood and personal functioning as critical foci for clinical management strategies in people with AN. Addressing depressive symptoms and perceived disability while bettering employment prospects could facilitate improved AN life satisfaction.

Cognitive heterogeneity in first-episode psychosis and its relationship with premorbid developmental adjustment.

BACKGROUND: Patients with schizophrenia spectrum disorders have been increasingly recognised to form cognitive subgroups with differential levels of impairment. Using cluster analytical techniques, this study sought to identify cognitive clusters in a sample of first-episode psychosis (FEP) patients and examine clinical and developmental differences across the resultant groups. METHODS: In total, 105 FEP patients in the University of California Los Angeles Aftercare Research Program were assessed for cognition, symptoms and premorbid developmental adjustment. Hierarchical cluster analysis with Ward's method and squared Euclidean distance was conducted, confirmed by discriminant function analysis and optimised with k-means clustering. The stability of the solution was evaluated through split-sample (random, 80 and 70% samples) and alternate method (average linkage method) replication via Cohen's κ analysis. Controlling for multiple comparisons, one-way analysis of variances examined group differences in symptom severity and premorbid adjustment. RESULTS: Three groups were identified: severely impaired (n = 27), moderately impaired (n = 41) and relatively intact (n = 37). There were no significant differences in symptom severity across the groups. Significant differences were observed for scholastic performance at three different developmental stages: childhood, early adolescence and late adolescence, with the relatively intact group demonstrating significantly better scholastic performance at all three stages than both the moderately impaired and severely impaired groups (who did not significantly differ from each other). CONCLUSIONS: The findings add to growing evidence that cognitive clusters in FEP mirror that of later-stage schizophrenia. They also suggest that premorbid scholastic performance may not just be a risk factor for developing schizophrenia, but is also related to cognitive impairment severity and potentially to prognosis.

The Relationship between Negative Symptoms and Both Emotion Management and Non-social Cognition in Schizophrenia Spectrum Disorders.

OBJECTIVE: There is ongoing debate regarding the relationship between clinical symptoms and cognition in schizophrenia spectrum disorders (SSD). The present study aimed to explore the potential relationships between symptoms, with an emphasis on negative symptoms, and social and non-social cognition. METHOD: Hierarchical cluster analysis with k-means optimisation was conducted to characterise clinical subgroups using the Scale for the Assessment of Negative Symptoms and Scale for the Assessment of Positive Symptoms in n = 130 SSD participants. Emergent clusters were compared on the MATRICS Consensus Cognitive Battery, which measures non-social cognition and emotion management as well as demographic and clinical variables. Spearman's correlations were then used to investigate potential relationships between specific negative symptoms and emotion management and non-social cognition. RESULTS: Four distinct clinical subgroups were identified: 1. high hallucinations, 2. mixed symptoms, 3. high negative symptoms, and 4. relatively asymptomatic. The high negative symptom subgroup was found to have significantly poorer emotion management than the high hallucination and relatively asymptomatic subgroups. No further differences between subgroups were observed. Correlation analyses revealed avolition-apathy and anhedonia-asociality were negatively correlated with emotion management, but not non-social cognition. Affective flattening and alogia were not associated with either emotion management or non-social cognition. CONCLUSIONS: The present study identified associations between negative symptoms and emotion management within social cognition, but no domains of non-social cognition. This relationship may be specific to motivation, anhedonia and apathy, but not expressive deficits. This suggests that targeted interventions for social cognition may also result in parallel improvement in some specific negative symptoms.

Biofuel Options for Marine Applications: Technoeconomic and Life-Cycle Analyses.

This study performed technoeconomic and life-cycle analyses to assess the economic feasibility and emission benefits and tradeoffs of various biofuel production pathways as an alternative to conventional marine fuels. We analyzed production pathways for (1) Fischer-Tropsch diesel from biomass and cofeeding biomass with natural gas or coal, (2) renewable diesel via hydroprocessed esters and fatty acids from yellow grease and cofeeding yellow grease with heavy oil, and (3) bio-oil via fast pyrolysis of low-ash woody feedstock. We also developed a new version of the Greenhouse gases, Regulated Emissions, and Energy use in Transportation (GREET) marine fuel module for the estimation of life-cycle greenhouse gas (GHG) and criteria air pollutant (CAP) emissions of conventional and biobased marine fuels. The alternative fuels considered have a minimum fuel selling price between 2.36 and 4.58 $/heavy fuel oil gallon equivalent (HFOGE), and all exhibit improved life-cycle GHG emissions compared to heavy fuel oil (HFO), with reductions ranging from 40 to 93%. The alternative fuels also exhibit reductions in sulfur oxides and particulate matter emissions. Additionally, when compared with marine gas oil and liquified natural gas, they perform favorably across most emission categories except for cases where carbon and sulfur emissions are increased by the cofed fossil feedstocks. The pyrolysis bio-oil offers the most promising marginal CO2 abatement cost at less than $100/tonne CO2e for HFO prices >$1.09/HFOGE followed by Fischer-Tropsch diesel from biomass and natural gas pathways, which fall below $100/tonne CO2e for HFO prices >$2.25/HFOGE. Pathways that cofeed fossil feedstocks with biomass do not perform as well for marginal CO2 abatement cost, particularly at low HFO prices. This study indicates that biofuels could be a cost-effective means of reducing GHG, sulfur oxide, and particulate matter emissions from the maritime shipping industry and that cofeeding biomass with natural gas could be a practical approach to smooth a transition to biofuels by reducing alternative fuel costs while still lowering GHG emissions, although marginal CO2 abatement costs are less favorable for the fossil cofeed pathways.

Potential Socioeconomic and Environmental Effects of an Expanding U.S. Bioeconomy: An Assessment of Near-Commercial Cellulosic Biofuel Pathways.

This paper showcases the suitability of an environmentally extended input-output framework to provide macroeconomic analyses of an expanding bioeconomy to allow for adequate evaluation of its benefits and trade-offs. It also exemplifies the framework's applicability to provide early design stage evaluations of emerging technologies expected to contribute to a future bioeconomy. Here, it is used to compare the current United States (U.S.) bioeconomy to a hypothetical future containing additional cellulosic ethanol produced from two near-commercial pathways. We find that the substitution of gasoline with cellulosic ethanol is expected to yield socioeconomic net benefits, including job growth and value added, and a net reduction in global warming potential and nonrenewable energy use. The substitution fares comparable to or worse than that for other environmental impact categories including human toxicity and eutrophication potentials. We recommend that further technology advancement and commercialization efforts focus on reducing these unintended consequences through improved system design and innovation. The framework is seen as complementary to process-based technoeconomic and life cycle assessments as it utilizes related data to describe specific supply chains while providing analyses of individual products and portfolios thereof at an industrial scale and in the context of the U.S. economy.

A psychosocial intervention for individuals with advanced chronic kidney disease: A feasibility randomized controlled trial.

AIM: The current study evaluated the feasibility and preliminary efficacy of a psychosocial intervention, the Kidney Optimal Health Program, in reducing symptoms of depression and anxiety in individuals with advanced chronic kidney disease. METHODS: Patients with stage 4 or 5 chronic kidney disease were randomized to either a nine-session psychosocial intervention programme or usual care. Feasibility was assessed through recruitment and retention rates and programme acceptability. Participants completed assessments of depression, anxiety and psychosocial health at baseline and at 3-, 6- and 12-month follow-up. A repeated-measures analysis of variance was used to compare groups on outcomes over time. RESULTS: One hundred and twenty-eight patients were screened for eligibility; 84 consented to participant and were randomized to receive the intervention (N = 42) or usual care (N = 42). 27 (32.1%) participants withdrew prior to baseline assessment. Of those who completed the baseline assessment (N = 57), trial retention was high (75.4% at 3-month, 80.7% at 6-month and 70.2% at 12-month follow-up). Participants reported high levels of programme acceptability. The patients who completed the intervention (N = 17) demonstrated significantly decreased depression at 12-month follow-up compared to the usual care group (N = 13). CONCLUSION: The results support the feasibility of the Kidney Optimal Health Program intervention in recruitment, retention and programme acceptability with an improved screening protocol. Preliminary support is provided for improvement in depressive symptoms in patients with advanced chronic kidney disease. Further investigation through a fully powered randomized controlled trial is warranted.

Outcomes of iliac crest bone marrow aspirate injection for the treatment of recalcitrant Achilles tendinopathy.

BACKGROUND: Achilles tendinopathy is a common cause of posterior ankle and heel pain in both active and sedentary patients. Though the majority of patients respond to first-line non-operative management including activity modification, immobilization, orthotics, and physical therapy with stretching and eccentric strengthening, there is no consensus for patients who fail these treatments. We evaluate the role of iliac crest bone marrow aspirate (BMA) injections as a treatment option for recalcitrant cases. METHODS: A retrospective chart review was conducted of patients with refractory Achilles tendinopathy treated with iliac crest BMA concentrate injection. Symptoms were assessed using the numeric rating system (NRS) pain score at the pre-operative visit and at six, 12, 24, and 48 weeks postoperatively. Post-operative complications were recorded. RESULTS: A total of 15 patients (15 feet) with recalcitrant Achilles tendinopathy (5 insertional, 8 non-insertional, 2 combined) treated with iliac crest BMA concentrate injections were included in the study. Average age was 53.2 years (range, 25 to 64), average BMI was 27.1 kg/m2 (range, 18.4 to 34.4), and average duration of symptoms prior to BMA injection was 2.3 years (range, 1 to 7). Pre-operatively, average NRS was 6.26 (95% CI, 5.04 to 7.49), with significant improvement at six weeks (mean, 4.26; 95% CI, 2.94 to 5.59; p = 0.04), ten weeks (mean, 4.13; 95% CI, 2.91 to 5.35; p = 0.012), 24 weeks (mean, 3.40; 95% CI, 2.05 to 4.75; p = 0.03), and 48 weeks (mean, 2.60; 95% CI, 1.14 to 4.06; p = 0.007) post-operatively. Overall, there was trending improvement over the 48-week follow-up period, with a mean improvement in NRS of - 3.22 (95% CI, - 1.06 to - 5.38; p = 0.007) at final follow-up. There was no discernable difference between insertional and non-insertional tendinopathy, and there were no incidences of post-operative complications. CONCLUSION: Iliac crest BMA appears to be a safe, effective, and potentially lasting treatment option for patients with intractable, insertional and non-insertional Achilles tendinopathy. Patients demonstrated and maintained statistically significant decrease in NRS pain score post-operatively with no complications at the donor or injection site.

Emotional discomfort mediates the relationship between self-efficacy and subjective quality of life in people with schizophrenia.

BACKGROUND: In people with schizophrenia, self-efficacy (i.e. the belief in one's capability to perform particular tasks/skills) is associated with and motivates performance of social, health and independent living behaviours. Less well known is whether self-efficacy is associated with subjective quality of life (sQoL) or whether psychopathology impacts this relationship. AIMS: Measure whether greater self-efficacy is associated with greater community functioning and sQoL and whether emotional discomfort mediates this relationship. METHOD: Fifty-two community living people with schizophrenia completed measures of self-efficacy for everyday living and social situations, clinical symptoms, sQoL and community functioning. RESULTS: Greater everyday living and social self-efficacy was significantly correlated with greater sQoL and community functioning and lower emotional discomfort (p < 0.05). Only social self-efficacy was correlated with negative symptoms. The relationship between both aspects of self-efficacy and sQoL was, however, mediated by emotional discomfort. Greater confidence in performing social and everyday living behaviours therefore indirectly impacted sQoL through reducing emotional distress. CONCLUSIONS: Holding negative capability self-beliefs may contribute to poorer outcome for people with schizophrenia. Intervention aimed at facilitating recovery should therefore provide opportunities to develop knowledge and skills required for success in desired life roles and the belief that tasks required for success can be performed.

Learning curve assessment for total ankle replacement using the transfibular approach.

BACKGROUND: Total ankle arthroplasty is an increasingly effective option for the treatment of end-stage arthritis. One recent innovation utilizes a transfibular, lateral approach. Like any new system, there is likely a learning curve associated with its use. We analyzed a series of patients who received a total ankle arthroplasty via a transfibular approach to state if it is possible to identify and to evaluate effects of a learning curve in the use of this novel total ankle replacement system. METHODS: 76 consecutive patients meeting inclusion and exclusion criteria were retrospectively analyzed. All patients had a minimum of 24 months of follow-up. Intraoperative parameters, preoperative and postoperative subjective outcome scores, radiographic parameters, and complications were recorded and evaluated. RESULTS: There were significant learning curve effects on various surgical and postoperative parameters. Surgical time decreased with the curve stabilizing after the 16th patient. With regard to patient outcomes, a learning curve was identified for the VAS, AOFAS, and SF-12 MCS scores. The number of patients required to stabilize these curves were 21, 13, and 16, respectively. Alignment as measured by alpha and gamma angles also improved with experience, with the curves stabilizing at 18 and 15 patients, respectively. There was a larger number cases required for complication rates, with the curve stabilizing after the 39th patient. No significant learning curve was found for ankle ROM, SF-12 PCS, beta angle, tibio-talar ratio (TTR), or tibio-talar surface angle (TTS). CONCLUSIONS: This study demonstrates a significant learning curve with respect to operative time, patient outcomes, and radiographic parameters. Extrapolating this information, we urge surgeons to adequately familiarize themselves with any new implant through a training program in a high-volume center. LEVEL OF EVIDENCE: IV, case series.

Rhodium(III)-Catalyzed Synthesis of Skipped Enynes via C(sp3 )-H Alkynylation of Terminal Alkenes.

The RhIII -catalyzed allylic C-H alkynylation of non-activated terminal alkenes leads selectively to linear 1,4-enynes at room-temperature. The catalytic system tolerates a wide range of functional groups without competing functionalization at other positions. Similarly, the vinylic C-H alkynylation of α,ß- and ß,γ- unsaturated amides gives conjugated Z-1,3-enynes and E-enediynes.

Iridium-Catalyzed Acid-Assisted Hydrogenation of Oximes to Hydroxylamines.

We found that cyclometalated cyclopentadienyl iridium(III) complexes are uniquely efficient catalysts in homogeneous hydrogenation of oximes to hydroxylamine products. A stable iridium C,N-chelation is crucial, with alkoxy-substituted aryl ketimine ligands providing the best catalytic performance. Several Ir-complexes were mapped by X-ray crystal analysis in order to collect steric parameters that might guide a rational design of even more active catalysts. A broad range of oximes and oxime ethers were activated with stoichiometric amounts of methanesulfonic acid and reduced at room temperature, remarkably without cleavage of the fragile N-O bond. The exquisite functional group compatibility of our hydrogenation system was further demonstrated by additive tests. Experimental mechanistic investigations support an ionic hydrogenation platform, and suggest a role for the Brønsted acid beyond a proton source. Our studies provide deep understanding of this novel acidic hydrogenation and may facilitate its improvement and application to other challenging substrates.

Questioning the status of aberrant speech patterns as psychiatric symptoms.

Speech disturbances manifest in various psychiatric conditions and demonstrate temporal variability in relation to acute and stable symptom periods. They can be externally assessed, which facilitates their potential use as an objective marker of illness stage. Continued research will have positive implications for diagnostics and long-term management in clinical settings.