C-C Bond Formation Coupled with C-C Bond Cleavage during Oxidative Upgrading of Glycerol on a Nanoporous BiVO4 Photoanode.

Production of biodiesel generates glycerol as a 10 wt% byproduct. Therefore, efficient and selective glycerol upgrading is critical for the sustainable production of biodiesel as well as for the production of chemicals from renewable feedstocks. In this study, the photoelectrochemical glycerol oxidation reaction (GOR) was investigated using a nanoporous BiVO4 photoanode in pH 9.3 and pH 2 buffer solutions. In both solutions, glycolaldehyde (GCAD), a C2 species, was the major product, which has never been the major product in any previous electrochemical or photoelectrochemical GOR study. To produce GCAD from the C3 species glycerol, C-C cleavage should occur to produce C2 and C1 species with a 1:1 ratio. Intriguingly, our results show that, during photoelectrochemical GOR on BiVO4, more GCAD is produced than can be explained by simple C-C cleavage, meaning that GCAD is also produced from C-C coupling of two C1 species produced from C-C cleavage. This is equivalent to converting two glycerol molecules to three GCAD molecules, which offers an extraordinary way to maximize GCAD production. To gain further insight into the nature of this unprecedented C-C coupling during GOR, photoelectrochemical oxidation of intermediate oxidation products (glyceraldehyde and 1,3-dihydroxyacetone) and glycerol-1,3-13C2 was compared to that of standard glycerol. Photoelectrochemical GOR was also compared with electrochemical GOR on BiVO4 to interrogate whether light is critical for the observed C-C coupling. Results obtained from comprehensive control experiments revealed critical information about C-C cleavage and C-C coupling during GOR on BiVO4.

Equine non-septic tenosynovitis: A systematic literature review of site-specific pathological lesions, outcomes and surgical complications.

BACKGROUND: Non-septic tenosynovitis is a clinically relevant and often performance limiting musculoskeletal injury in the horse. OBJECTIVES: To review the published literature to determine which tendon sheaths are commonly affected by non-septic tenosynovitis and to describe the most frequently reported pathological lesions, outcomes, and surgical complications in equine non-septic tenosynovitis. STUDY DESIGN: Systematic review. METHODS: Literature searches were conducted in July 2021 from the online search engines PubMed, Scopus, Web of Science Core, VetMed Resource and ProQuest Theses & Dissertations. The inclusion criteria followed a participants, interventions, comparisons, outcome and study design (PICOS) approach. For inclusion, studies had to include live equids with non-septic tenosynovitis of any tendon sheath. Studies were excluded if they only described non-equine species, if they included data only on non-tendon sheath structures, or if they included data exclusively on cases of septic or contaminated tendon sheaths. Determination of non-sepsis relied on the diagnosis of the original authors; however, if non-sepsis was not explicitly specified, then cases that had a history of contamination of the sheath, a wound near the sheath or a positive bacterial culture were excluded from analysis. Data analysed included the distribution of structures affected by non-septic tenosynovitis, the most common pathological lesions identified within each sheath, and the most frequently reported surgical complications of non-septic tenosynovitis. The quality of each study was assessed using a methodological quality analysis. RESULTS: A total of 85 studies describing non-septic tenosynovitis in the horse were included. Across all 85 studies, there were a total of 2449 tendon sheaths in 2101 horses reported to be affected by non-septic tenosynovitis. The digital flexor sheath was the most reported structure to be diagnosed with non-septic tenosynovitis: 41/85 (48%) studies examined the digital flexor sheath exclusively, followed by the carpal flexor sheath, tarsal flexor sheath, carpal extensor sheaths, tarsal extensor sheaths, and one case of biceps brachii non-septic tenosynovitis. For most tendon sheaths, the most common pathological lesion was an intrathecal tear of a soft tissue structure, including tears of the deep digital flexor tendon and tears of the manica flexoria. Bilateral disease was most common in the carpal flexor sheath, where distal radial physeal exostoses were the most common pathological lesions. Less common causes of non-septic tenosynovitis included neoplasia, fracture of a bone adjacent to a tendon sheath, and mineralisation of an intrathecal tendon. The likelihood of return to previous level of athletic function following non-septic tenosynovitis of most structures was approximately 50%, and the most common complication was persistent effusion following tenoscopy. While iatrogenic infection following surgery was uncommon, it was most likely following tenoscopy of the digital flexor sheath. CONCLUSION: Non-septic tenosynovitis is commonly reported in equine athletes, with intra-thecal tears of the deep digital flexor tendon, superficial digital flexor tendon and manica flexoria frequently reported. Directions for future research include more thorough assessment of and reporting of complications following non-septic tenosynovitis and correlation of characteristics of intrathecal pathological lesions with clinical outcomes.

Variable temperature kinetic isotope effects demonstrate extensive tunnelling in the C-H activation reactivity of a transition metal-oxo complex.

There has been recent interest about how the rates of concerted proton electron transfer (CPET) are affected by the thermodynamic parameters of intermediates from stepwise PT or ET reactions. Semiclassical arguments have been used to explain these trends despite the importance of quantum mechanical tunneling in CPET reactions. Here we report variable temperature kinetic isotope effect (KIE) data for the reactivity of a terminal Co-oxo complex with C-H bonds. The KIEs for the oxidation of both 9,10-dihydroanthracene (DHA) and fluorene have significant tunneling contributions and fluorene has a largely temperature-insensitive KIE which is inconsistent with semiclassical models. These findings support recent calls for a more detailed understanding of tunneling effects in thermodynamically imbalanced CPET reactions.

Testing the Limits of Imbalanced CPET Reactivity: Mechanistic Crossover in H-Atom Abstraction by Co(III)-Oxo Complexes.

Transition metal-oxo complexes are key intermediates in a variety of oxidative transformations, notably C-H bond activation. The relative rate of C-H bond activation mediated by transition metal-oxo complexes is typically predicated on substrate bond dissociation free energy in cases with a concerted proton-electron transfer (CPET). However, recent work has demonstrated that alternative stepwise thermodynamic contributions such as acidity/basicity or redox potentials of the substrate/metal-oxo may dominate in some cases. In this context, we have found basicity-governed concerted activation of C-H bonds with the terminal CoIII-oxo complex PhB(tBuIm)3CoIIIO. We have been interested in testing the limits of such basicity-dependent reactivity and have synthesized an analogous, more basic complex, PhB(AdIm)3CoIIIO, and studied its reactivity with H-atom donors. This complex displays a higher degree of imbalanced CPET reactivity than PhB(tBuIm)3CoIIIO with C-H substrates, and O-H activation of phenol substrates displays mechanistic crossover to stepwise proton transfer-electron transfer (PTET) reactivity. Analysis of the thermodynamics of proton transfer (PT) and electron transfer (ET) reveals a distinct thermodynamic crossing point between concerted and stepwise reactivity. Furthermore, the relative rates of stepwise and concerted reactivity suggest that maximally imbalanced systems provide the fastest CPET rates up to the point of mechanistic crossover, which results in slower product formation.

Predictive control of selective secondary alcohol oxidation of glycerol on NiOOH.

Many biomass intermediates are polyols and selectively oxidizing only a primary or secondary alcohol group is beneficial for the valorization of these intermediates. For example, production of 1,3-dihydroxyacetone, a highly valuable oxidation product of glycerol, requires selective secondary alcohol oxidation. However, selective secondary alcohol oxidation is challenging due to its steric disadvantage. This study demonstrates that NiOOH, which oxidizes alcohols via two dehydrogenation mechanisms, hydrogen atom transfer and hydride transfer, can convert glycerol to 1,3-dihydroxyacetone with high selectivity when the conditions are controlled to promote hydrogen atom transfer, favoring secondary alcohol oxidation. This rational production of 1,3-dihydroxyacetone achieved by selectively enabling one desired dehydrogenation pathway, without requiring alteration of catalyst composition, demonstrates how comprehensive mechanistic understanding can enable predictive control over selectivity.

Repatriation of a historical North Atlantic right whale habitat during an era of rapid climate change.

Climate change is affecting species distributions in space and time. In the Gulf of Maine, one of the fastest-warming marine regions on Earth, rapid warming has caused prey-related changes in the distribution of the critically endangered North Atlantic right whale (Eubalaena glacialis). Concurrently, right whales have returned to historically important areas such as southern New England shelf waters, an area known to have been a whaling ground. We compared aerial survey data from two time periods (2013-2015; 2017-2019) to assess trends in right whale abundance in the region during winter and spring. Using distance sampling techniques, we chose a hazard rate key function to model right whale detections and used seasonal encounter rates to estimate abundance. The mean log of abundance increased by 1.40 annually between 2013 and 2019 (p = 0.004), and the mean number of individuals detected per year increased by 2.23 annually between 2013 and 2019 (R2 = 0.69, p = 0.001). These results demonstrate the current importance of this habitat and suggest that management options must continually evolve as right whales repatriate historical habitats and potentially expand to new habitats as they adapt to climate change.

Enzyme-Like Hydroxylation of Aliphatic C-H Bonds From an Isolable Co-Oxo Complex.

The selective hydroxylation of aliphatic C-H bonds remains a challenging but broadly useful transformation. Nature has evolved systems that excel at this reaction, exemplified by cytochrome P450 enzymes, which use an iron-oxo intermediate to activate aliphatic C-H bonds with k1 > 1400 s-1 at 4 °C. Many synthetic catalysts have been inspired by these enzymes and are similarly proposed to use transition metal-oxo intermediates. However, most examples of well-characterized transition metal-oxo species are not capable of reacting with strong, aliphatic C-H bonds, resulting in a lack of understanding of what factors facilitate this reactivity. Here, we report the isolation and characterization of a new terminal CoIII-oxo complex, PhB(AdIm)3CoIIIO. Upon oxidation, a transient CoIV-oxo intermediate is generated that is capable of hydroxylating aliphatic C-H bonds with an extrapolated k1 for C-H activation >130 s-1 at 4 °C, comparable to values observed in cytochrome P450 enzymes. Experimental thermodynamic values and DFT analysis demonstrate that, although the initial C-H activation step in this reaction is endergonic, the overall reaction is driven by an extremely exergonic radical rebound step, similar to what has been proposed in cytochrome P450 enzymes. The rapid C-H hydroxylation reactivity displayed in this well-defined system provides insight into how hydroxylation is accomplished by biological systems and similarly potent synthetic oxidants.

Neural correlates of walking post-stroke: neuroimaging insights from the past decade.

Walking dysfunction such as slow walking speed and reduced independent mobility are common impairments following stroke. Neural mechanisms of upper limb impairment and motor recovery have been highly studied, while less is known about the neural correlates of walking dysfunction and rehabilitation after stroke. Our objective was to review the literature on neuroimaging correlates of walking and walking recovery post-stroke to provide a more comprehensive picture of neurological regions of interest. We searched the databases PubMed, CINAHL, Web of Science, and Cochrane Trials for articles published in English between January 1, 2010 and November 30, 2020 that assessed walking after stroke through neuroimaging and various clinical measures. The following key words were used: stroke, gait, walking, rehabilitation, brain mapping, neuroimaging, neural control of walking, motor recovery and motor function, and resulted in eighteen articles included in this review. These articles revealed regions of interest associated with lower extremity impairment and walking post-stroke to include the putamen, caudate, insula, pallidum, superior temporal gyrus, internal capsule, superior longitudinal fasciculus, corticospinal tract, corona radiata, and white matter associated with the pedunculopontine nucleus. This information strengthens our understanding of supraspinal control of walking post-stroke. However, future research on lesion location, functional and structural connectivity, and walking deficits is needed to confidently associate specific brain regions and white matter tracts/connectivity with specific impairments. Greater insight into neuromechanisms associated with response to neurorehabilitation post-stroke could improve treatment selection and prediction of motor recovery.

Photodiagnostic services in the UK and Republic of Ireland: a British Photodermatology Group Workshop Report.

BACKGROUND: Photodiagnostic investigations are essential for the accurate diagnosis of abnormal cutaneous photosensitivity and provide important information for the management of patients with photodermatoses (cutaneous photosensitivity disorders). Although photodiagnosis has been undertaken since the early 1970s, specialist services in the United Kingdom (UK) and Republic of Ireland are limited and there is no formal guidance on diagnostic approach. Indeed, there is a limited literature in this area of methodology and diagnostic practice. OBJECTIVES: The primary objective was to undertake a British Photodermatology Group Workshop to review the role and activities of specialist centres in the UK and Republic of Ireland in order to ascertain whether there were consensus practices. Secondary objectives were to identify key priorities for service, training and research. METHODS: An initial detailed survey review of current activities was undertaken prior to the Workshop and data from this survey were used to inform discussion at the Workshop, which was attended by key photodermatology experts from the UK and Republic of Ireland. RESULTS/CONCLUSIONS: We have undertaken a detailed review of current Photodiagnostic Services in the UK and Republic of Ireland and report on our findings from the 12 centres and we have identified key areas of consensus practice. This is an important step in the process of standardising and optimising procedures and protocols and defining minimum clinical standards for photodiagnostic investigations, which are of such diagnostic importance in Dermatology.

CEMENT BURNS.

BACKGROUND: Burns are a common condition presenting to the emergency department; the majority are thermal burns. The treatment for thermal burns and chemical burns differs greatly, and prompt recognition of a chemical burn is necessary. An often unrecognized and underestimated type of chemical burn is an alkali burn from wet cement. CASE REPORT: A 7-year-old boy was transferred from an outside facility for evaluation of burns after exposure to wet cement. The patient underwent partial decontamination at the outside facility with polyethylene glycol and, to prevent ongoing alkali burns, the patient necessitated further decontamination with irrigation. Burn surgery was consulted for additional evaluation. The patient required no further intervention and the patient was discharged to home and made a full recovery. WHY SHOULD AN EMERGENCY PHYSICIAN BE AWARE OF THIS?: Serious morbidity and mortality can occur from unrecognized cement burns, and early decontamination and evaluation by a burn surgeon is necessary. It is critical that emergency physicians both recognize and appropriately treat this condition in a timely manner to prevent adverse outcomes.

Statistical analysis of C-H activation by oxo complexes supports diverse thermodynamic control over reactivity.

Transition metal oxo species are key intermediates for the activation of strong C-H bonds. As such, there has been interest in understanding which structural or electronic parameters of metal oxo complexes determine their reactivity. Factors such as ground state thermodynamics, spin state, steric environment, oxygen radical character, and asynchronicity have all been cited as key contributors, yet there is no consensus on when each of these parameters is significant or the relative magnitude of their effects. Herein, we present a thorough statistical analysis of parameters that have been proposed to influence transition metal oxo mediated C-H activation. We used density functional theory (DFT) to compute parameters for transition metal oxo complexes and analyzed their ability to explain and predict an extensive data set of experimentally determined reaction barriers. We found that, in general, only thermodynamic parameters play a statistically significant role. Notably, however, there are independent and significant contributions from the oxidation potential and basicity of the oxo complexes which suggest a more complicated thermodynamic picture than what has been shown previously.

Establishing a physical health monitoring service for patients on depot antipsychotic medication.

INTRODUCTION: Patients with major mental illness are recognised to be at risk of premature death for a multitude of reasons. This initiative aimed to improve the physical health monitoring of patients prescribed depot antipsychotic medication in a catchment area of ~36 000 in Ireland. OBJECTIVES: International best practice recommends monitoring of blood tests, physical parameters such as weight, BMI, waist circumference and blood pressure, and side effects of patients prescribed antipsychotic medication. A clinic was established to target these interventions. METHODS: A cohort of patients receiving antipsychotics in long-acting injectable form was chosen. A twice-yearly, multidisciplinary health monitoring clinic was established. Evaluation involved an audit of medical records which measured the proportion of those attending the clinic who had blood test monitoring and physical parameters recorded. RESULTS: Before the clinic's implementation, 30% of patients had evidence of some blood test monitoring, 9% had evidence of complete blood testing and one patient had evidence of physical health parameters having been recorded. One year after the implementation 78% of patients had evidence of some blood test monitoring, 61% had evidence of full blood test monitoring and 100% had evidence of physical parameters recorded. CONCLUSIONS: The clinic was positively received by patients, and led to improved teamwork. Recommendations include organising concurrent psychiatric and phlebotomy clinics so that patients may avail of psychiatric review and blood testing at a single appointment. As a result of the increased focus on physical health monitoring, a similar project is planned to target all patients prescribed antipsychotics.

Transendoscopic Ventriculocordectomy Using Monopolar Electrosurgical Instrumentation for Conjunctive Treatment of Laryngeal Hemiplegia in Horses: 24 Cases (2017-2019).

Objective: The objective of this study is to evaluate the safety, efficacy, and owner satisfaction following electrosurgical ventriculocordectomy (EVC), in conjunction with prosthetic laryngoplasty, in equine clinical cases affected with left- or right-sided recurrent laryngeal neuropathy. Methods: Retrospective data analysis of clinical signalment, surgery, athletic outcome, intra- and postoperative complications, and postoperative examinations from clinical cases wherein EVC was performed in conjunction with traditional prosthetic laryngoplasty from one practice. Owners were contacted by phone or email for a follow-up questionnaire. Results: Twenty-four horses underwent unilateral EVC, performed transendoscopically under sedated restraint, using monopolar electrosurgical instrumentation successfully. One horse experienced excessive intraoperative hemorrhage. No horses demonstrated postoperative complications. Twenty cases had a history of increased airway noise prior to surgery. In 15 of these cases (15/20, 75%), the airway noise was reported as fully improved post-surgery. Eighteen cases had a history of exercise intolerance prior to surgery. In 15 of these cases (15/18; 83%), the exercise intolerance was reported as resolved. Conclusion: EVC, in conjunction with prosthetic laryngoplasty, can contribute to improvement of RLN symptoms and aid in the effective return to athletic work. Performing transendoscopic ventriculocordectomy with monopolar electrosurgical instrumentation provides comparable clinical outcomes to traditional techniques using a diode laser or direct excision via laryngotomy.

Experimental Evidence for p Ka-Driven Asynchronicity in C-H Activation by a Terminal Co(III)-Oxo Complex.

C-H activation by transition metal oxo complexes is a fundamental reaction in oxidative chemistry carried out by both biological and synthetic systems. This centrality has motivated efforts to understand the patterns and mechanisms of such reactivity. We have therefore thoroughly examined the C-H activation reactivity of the recently synthesized and characterized late transition metal oxo complex PhB ( tBuIm)3CoIIIO. Precise values for the p Ka and BDFEO-H of the conjugates of this complex have been experimentally determined and provide insight into the observed reactivity. The activation parameters for the reaction between this complex and 9,10-dihydroanthracene have also been measured and compared to previous literature examples. Evaluation of the rates of reaction of PhB( tBuIm)3CoIIIO with a variety of hydrogen atom donors demonstrates that the reactivity of this complex is dependent on the p Ka of the substrate of interest rather than the BDEC-H. This observation runs counter to the commonly cited reactivity paradigm for many other transition metal oxo complexes. Experimental and computational analysis of C-H activation reactions by PhB( tBuIm)3CoIIIO reveals that the transition state for these processes contains significant proton transfer character. Nevertheless, additional experiments strongly suggest that the reaction does not occur via a stepwise process, leading to the conclusion that C-H activation by this CoIII-oxo complex proceeds by a p Ka-driven "asynchronous" concerted mechanism. This result supports a new pattern of reactivity that may be applicable to other systems and could result in alternative selectivity for C-H activation reactions mediated by transition metal oxo complexes.

Adverse effects of topical photodynamic therapy: a consensus review and approach to management.

BACKGROUND: Topical photodynamic therapy (PDT) is widely used to treat superficial nonmelanoma skin cancer and dysplasia, and is generally well tolerated. However, as with all treatments, adverse effects may occur and awareness may facilitate approaches to prevention and management. OBJECTIVES: To review the available evidence relating to the adverse effects of topical PDT, to help inform recommendations in updated clinical guidelines produced by the British Association of Dermatologists and British Photodermatology Group, and the efficacy of preventative and therapeutic approaches. METHODS: This review summarizes the published evidence related to the adverse effects of topical PDT and attempts to interpret this evidence in the context of patient risk and management. RESULTS: Pain and discomfort during PDT are acute adverse effects, which can be minimized through the use of modified and low-irradiance PDT regimens and do not therefore usually limit successful treatment delivery. Other adverse effects include the risk of contact allergy to photosensitizer prodrugs, although this is rare but should be kept in mind, particularly for patients who have received multiple PDT treatments to larger areas. There are no other significant documented longer-term risks and, to date, no evidence of cumulative toxicity or photocarcinogenic risk. CONCLUSIONS: Topical PDT is usually well tolerated, reinforcing the utility of this important therapeutic option in dermatology practice. The main acute adverse effect of pain can typically be minimized through preventative approaches of modified PDT regimens. Other adverse effects are uncommon and generally do not limit treatment delivery.