Automation, live-cell imaging, and endpoint cell viability for prostate cancer drug screens.

Androgen deprivation therapy (ADT) is the standard of care for high risk and advanced prostate cancer; however, disease progression from androgen-dependent prostate cancer (ADPC) to lethal and incurable castration-resistant prostate cancer (CRPC) and (in a substantial minority of cases) neuroendocrine prostate cancer (NEPC) is common. Identifying effective targeted therapies is challenging because of acquired resistance to established treatments and the vast heterogeneity of advanced prostate cancer (PC). To streamline the identification of potentially active prostate cancer therapeutics, we have developed an adaptable semi-automated protocol which optimizes cell growth and leverages automation to enhance robustness, reproducibility, and throughput while integrating live-cell imaging and endpoint viability assays to assess drug efficacy in vitro. In this study, culture conditions for 72-hr drug screens in 96-well plates were established for a large, representative panel of human prostate cell lines including: BPH-1 and RWPE-1 (non-tumorigenic), LNCaP and VCaP (ADPC), C4-2B and 22Rv1 (CRPC), DU 145 and PC3 (androgen receptor-null CRPC), and NCI-H660 (NEPC). The cell growth and 72-hr confluence for each cell line was optimized for real-time imaging and endpoint viability assays prior to screening for novel or repurposed drugs as proof of protocol validity. We demonstrated effectiveness and reliability of this pipeline through validation of the established finding that the first-in-class BET and CBP/p300 dual inhibitor EP-31670 is an effective compound in reducing ADPC and CRPC cell growth. In addition, we found that insulin-like growth factor-1 receptor (IGF-1R) inhibitor linsitinib is a potential pharmacological agent against highly lethal and drug-resistant NEPC NCI-H660 cells. This protocol can be employed across other cancer types and represents an adaptable strategy to optimize assay-specific cell growth conditions and simultaneously assess drug efficacy across multiple cell lines.

Photoelectrochemical approaches for the conversion of lignin at room temperature.

The selective cleavage of C-C/C-O linkages represents a key step toward achieving the chemical conversion of biomass to targeted value-added chemical products under ambient conditions. Using photoelectrosynthetic solar cells is a promising method to address the energy intensive depolymerization of lignin for the production of biofuels and valuable chemicals. This feature article gives an in-depth overview of recent progress using dye-sensitized photoelectrosynthetic solar cells (DSPECs) to initiate the cleavage of C-C/C-O bonds in lignin and related model compounds. This approach takes advantage of N-oxyl mediated catalysis in organic electrolytes and presents a promising direction for the sustainable production of chemicals currently derived from fossil fuels.

The SLANT Score Predicts Poor Neurologic Outcome in Comatose Survivors of Cardiac Arrest: An External Validation Using a Retrospective Cohort.

BACKGROUND: Hypoxic brain injury is the leading cause of death in comatose patients following resuscitation from cardiac arrest. Neurological outcome can be difficult to prognosticate following resuscitation, and goals of care discussions are often informed by multiple prognostic tools. One tool that has shown promise is the SLANT score, which encompasses five metrics including initial nonshockable rhythm, leukocyte count after targeted temperature management, total adrenaline dose during resuscitation, lack of bystander cardiopulmonary resuscitation, and time to return of spontaneous circulation. This cohort study aimed to provide an external validation of this score by using a database of comatose cardiac arrest survivors from our institution. METHODS: We retrospectively queried our database of cardiac arrest survivors, selecting for patients with coma, sustained return of spontaneous circulation, and use of targeted temperature management to have a comparable sample to the index study. We calculated SLANT scores for each patient and separated them into risk levels, both according to the original study and according to a Youden index analysis. The primary outcome was poor neurologic outcome (defined by a cerebral performance category score of 3 or greater at discharge), and the secondary outcome was in-hospital mortality. Univariable and multivariable analyses, as well as a receiver operator characteristic curve, were used to assess the SLANT score for independent predictability and diagnostic accuracy for poor outcomes. RESULTS: We demonstrate significant association between a SLANT group with increased risk and poor neurologic outcome on univariable (p = 0.005) and multivariable analysis (odds ratio 1.162, 95% confidence interval 1.003-1.346, p = 0.046). A receiver operating characteristic analysis indicates that SLANT scoring is a fair prognostic test for poor neurologic outcome (area under the curve 0.708, 95% confidence interval 0.536-0.879, p = 0.024). Among this cohort, the most frequent SLANT elements were initial nonshockable rhythm (84.5%) and total adrenaline dose ≥ 5 mg (63.9%). There was no significant association between SLANT score and in-hospital mortality (p = 0.064). CONCLUSIONS: The SLANT score may independently predict poor neurologic outcome but not in-hospital mortality. Including the SLANT score as part of a multimodal approach may improve our ability to accurately prognosticate comatose survivors of cardiac arrest.

BiVO4 Photoanodes for TEMPO-Mediated Benzyl Alcohol Oxidation in Organic Media.

The photoelectrochemical production of fuels, exemplified by light-driven water splitting to hydrogen and oxygen, offers a sustainable option to offset dependence on fossil fuels. A low-cost, efficient, and stable photoelectrochemical approach to solar fuels remains elusive but using similar materials and photoelectrodes for chemical production or biomass conversion offers an appealing alternative. This work reports a facile method for fabricating pristine (undoped) BiVO4 photoanodes to carry out TEMPO-mediated benzyl alcohol oxidation to benzaldehyde in organic media (TEMPO=2,2,6,6-tetramethylpiperidinyl-N-oxyl). The best performing BiVO4 photoanode studied here gave a faradaic efficiency (FE) of 85±5% for benzaldehyde formation in the presence of TEMPO and pyridine during a 2.5-hour reaction. Compared with direct electrocatalytic conversion under the same conditions, light capture and conversion by the BiVO4 surface decreased the required applied bias by 46 %. To our knowledge, this is the first report of visible light assisted, TEMPO-mediated benzyl alcohol oxidation using pristine BiVO4 photoanodes in organic media.

Political Campaign Contributions of Surgeons in the United States Throughout the 2020 Election Cycle.

Importance: Political engagement by the physician workforce is necessary to ensure continued representation of their interests in health care legislation. Limited data are available pertaining to the political involvement of US surgeons. Objective: To analyze the magnitude and distribution of political donations made by all US surgeons throughout the 2020 election cycle. Design, Setting, and Participants: Partisan and geographical differences in surgeon contributions by aggregating data (January 1 through December 31, 2020) from the US Federal Election Commission database were analyzed. Contributions were labeled as Republican, Democrat, or independent depending on the committee they were designated to. Main Outcomes and Measures: Differences in contributions to Republicans, Democrats, and independent candidates for all US surgeons and for subgroups. Results: For the 2020 election year, a total of 53 944 donations were made by surgeons in the United States, amounting to $9 223 350.68. Among all surgical specialties, the top 5 highest number of contributions were made from orthopedic surgeons (n = 15 081), ophthalmic surgeons (n = 14 836), neurological surgeons (n = 7481), urologists (n = 4544), and plastic surgeons (n = 4060). Of these donations, 59.46% (n = 32 107) were made to the Republican party ($5 420 326), 30.83% (n = 16 644) were made to the Democratic party ($1 612 775), and 9.71% (n = 5243) were made to nonpartisan (ie, independent) organizations ($2 190 250). Overall, pediatric surgeons reported the lowest mean contribution amount of $59.43, whereas thoracic surgeons reported the highest mean contribution amount of $225.19. Conclusions and Relevance: Health care legislation has an immense impact on how medicine is practiced and utilized. This analysis reveals a high degree of political activity of surgeons across different specialties and geographic regions.

Do Continuous Peripheral Nerve Blocks Decrease Home Opioid Use Following Anterior Cruciate Ligament Reconstruction in Children and Adolescents? The Envelope Please.

BACKGROUND: Levels of opioid misuse and addiction among children and adolescents have reached alarming proportions. Exposure to opioids after surgery for anterior cruciate ligament reconstruction (ACLR), which is commonly performed in young athletes, increases this risk. This study was designed to evaluate whether continuous peripheral nerve block (CPNB) with placement of an elastomeric reservoir ball, compared with single-shot peripheral nerve block (SPNB), would decrease the need for home opioid analgesia and improve pain control after ACLR in children and adolescents. METHODS: Prospectively collected data from a consecutive cohort that underwent ACLR by a single surgeon were retrospectively reviewed. Patients who received ACLR with 72-hour CPNB were assigned to Group 1. Patients who received ACLR with SPNB were assigned to Group 2. Postoperative pain management included cryotherapy, oral acetaminophen, and ibuprofen. A prescription for 10 doses of hydrocodone/acetaminophen (5/325 mg) was provided in a sealed envelope with instructions that the prescription should only be used in the case of uncontrolled pain. Reports of no opioid use were corroborated by the unopened envelope and unfilled prescription. RESULTS: One hundred and ninety-six patients were enrolled in the study (SPNB=114 patients, CPNB=82 patients). Average age was 15±1.5 years (115 female). A total of 138 patients (70%) did not need home opioid analgesia after surgery. Of the 58 patients (30%) that did there were 35 (30.7%) in the SPNB group and 23 (28.0%) in the CPNB group (P=0.659). There were no differences between groups in demographics, operative data, or visual analog scale scores on any postoperative day. CONCLUSION: The findings of this study demonstrate equivalent pain control and opioid consumption in children and adolescents undergoing ACLR treated with either a CPNB or a SPNB. At-home opioid analgesia use can be negated after ACLR in 70% of children and adolescents. For the patients in this study who required opioids, average use was only 2 pills of 5 mg hydrocodone/325 mg acetaminophen, with no child using more than 10 pills. LEVEL OF EVIDENCE: Level II-therapeutic.

Enhanced Photocatalytic Alcohol Oxidation at the Interface of RuC-Coated TiO2 Nanorod Arrays.

Visible-light-driven organic oxidations carried out under mild conditions offer a sustainable approach to performing chemical transformations important to the chemical industry. This work reports an efficient photocatalytic benzyl alcohol oxidation process using one-dimensional (1D) TiO2 nanorod (NR)-based photoanodes with surface-adsorbed ruthenium polypyridyl photocatalysts at room temperature. The photocatalyst bis(2,2'-bipyridine)(4,4'-dicarboxy-2,2'-bipyridine)Ru(II) (RuC) was covalently anchored onto TiO2 nanorod arrays grown on fluorine-doped tin oxide (FTO) electrode surfaces (FTO|t-TiO2|RuC, t = the thickness of TiO2 NR). Under aerobic conditions, the photophysical and photocatalytic properties of FTO|t-TiO2|RuC (t = 1, 2, or 3.5 µm) photoanodes were investigated in a solution containing a hydrogen atom transfer mediator (4-acetamido-2,2,6,6-tetramethylpiperidine-N-oxyl, ACT) as cocatalyst. Dye-sensitized photoelectrochemical cells (DSPECs) using the FTO|t-TiO2|RuC (t = 1, 2, or 3.5 µm) photoanodes and ACT-containing electrolyte were investigated for carrying out photocatalytic oxidation of a lignin model compound containing a benzylic alcohol functional group. The best-performing anode surface, FTO|1-TiO2|RuC (shortest NR length), oxidized the 2° alcohol of the lignin model compound to the Cα-ketone form with a > 99% yield over a 4 h photocatalytic experiment with a Faradaic efficiency of 88%. The length of TiO2 NR arrays (TiO2 NRAs) on the FTO substrate influenced the photocatalytic performance with longer NRAs underperforming compared to the shorter arrays. The influence of the NR length is hypothesized to affect the homogeneity of the RuC coating and accessibility of the ACT mediator to the RuC-coated TiO2 surface. The efficient photocatalytic alcohol oxidation with visible light at room temperature as demonstrated in this study is important to the development of sustainable approaches for lignin depolymerization and biomass conversion.

High Prevalence of Lumbosacral Pathology in Patients with Greater Trochanteric Pain Syndrome.

PURPOSE: To establish prevalence of lumbar and lumbosacral pathologies in patients with hip abductor tendon disorders. METHODS: A retrospective review of patients' charts was conducted over a 5-year period, January 2013 to October 2018, using the S76 and M76 International Classification of Diseases Tenth Revision (ICD-10) codes. Patients with symptomatic and radiologically confirmed hip abductor tendon disorders (partial and full-thickness tear of the gluteus medius tear with or without gluteus minimus tearing) were included in the study. No exclusion criteria were applied. Patient medical history was examined for concurrent diagnoses of lumbar and lumbosacral pathologies (radiculopathy, lumbar stenosis, degenerative disc disease, and neurogenic claudication). RESULTS: One-hundred and three patients with hip abductor tendon disorders were identified. Forty-seven (45.6%) patients had low-grade partial abductor tears, while 56 (54.4%) of patients had a high-grade partial or complete abductor tear. Fifty (48.5%) patients carried a concomitant lumbosacral diagnosis, with 20 (19.4%) patients being diagnosed with lumbar stenosis and 45 (43.7%) being diagnosed with degenerative disc disease. CONCLUSION: Patients with hip abductor tendon disorders were associated with a high prevalence of underlying lumbar and lumbosacral pathologies. Nevertheless, a causal relationship between these conditions cannot be established. LEVEL OF EVIDENCE: Level IV. Retrospective Case Series.

Concentrated Bone Marrow Aspirate Is More Cellular and Proliferative When Harvested From the Posterior Superior Iliac Spine Than the Proximal Humerus.

PURPOSE: The purpose of this study is to determine whether concentrated bone marrow aspirate (cBMA) from the posterior superior iliac spine (PSIS) or proximal humerus (PH) produces a more productive cellular harvest in patients undergoing arthroscopic rotator cuff repair. METHODS: Patients under 80 years old undergoing surgery for arthroscopic rotator cuff repair were enrolled. Two 60 mL aliquots of BMA were harvested from each subject, one from the PSIS and one from the PH. Each aliquot was processed independently to create cBMA. Cellular composition was determined using an automated hemocytometer and proliferative potential was studied with colony forming unit (CFU) assays. RESULTS: Twelve patients were recruited (7 male, 5 female). The average age was 64.3 years (range 46.1-77.25 years) with body mass index of 26.8 (range 20.0-34.3). The average total nucleated cells (TNC) from PH was 18.7 × 106 cells/mL (95% confidence interval [CI], 4.4-33.0; standard deviation [SD], 24.8) with 3.9 CFU/mL (95% CI, 0.3-7.5, SD, 5.7). The average TNC count from the PSIS was 55.9 × 106 cells/mL (95% CI, 25.3-86.4; SD, 52.9) with 32.5 CFU/mL (95% CI, 11.5-53.5; SD, 33.1). The PSIS had a 3.0 times greater total nucleated cell yield (P = .014) and 8.3 times greater number of CFU/mL (P = .024) when compared to the PH. The average harvest time from the PSIS was 5.6 minutes and from the PH was 11.0 minutes (P = .043); harvest time did not account for additional time to prep and drape the PSIS. CONCLUSIONS: The cBMA harvested from the PSIS resulted in a 3.0 times greater cellular yield and an 8.3 times greater proliferative product than cBMA from the PH. CLINICAL RELEVANCE: When a more cellular cBMA product is sought to augment rotator cuff tear repair surgery, the PSIS is the preferred site for harvest.

Magnetic Resonance Imaging Predictive Model Determines Hamstring Autograft Size for Anterior Cruciate Ligament Reconstruction in Patients Under 18 Years Old.

PURPOSE: To evaluate the predictive value of magnetic resonance imaging in determining hamstring autograft size preoperatively for pediatric anterior cruciate ligament reconstruction. METHODS: We conducted an analysis of patients younger than 18 years who underwent quadrupled hamstring autograft anterior cruciate ligament reconstruction. Semitendinosus tendon (ST) and gracilis tendon (GT) cross-sectional areas were measured on preoperative knee magnetic resonance imaging scans. Height, weight, body mass index, and sex were analyzed using ordinal regression analysis. A classification and regression tree (CART) was constructed to identify predictors of the predetermined intraoperative graft size of 8 mm or greater. Sensitivity and specificity were determined based on specified predictors. RESULTS: This study included 102 patients (52 female and 50 male patients). The average age was 15.8 ± 1.4 years. At the time of surgery, 38 patients (37.3%) had open physes, with an average age of 13.4 ± 0.96 years. Of the 102 patients, 55 (53.9%) had 8-mm or larger grafts, 31 (30.4%) had 7.5-mm grafts, and 16 (15.7%) had 7-mm or smaller grafts. In 12 patients (31.6%) with open physes, the graft size was less than 8 mm. Male patients were more likely to have 8-mm or larger grafts (P < .001), as were patients with a greater height (170.1 ± 7.3 cm vs 161.1 ± 12.0 cm, P = .013) and those with a greater weight (79.7 ± 23.4 kg vs 57.1 ± 16.2 kg, P = .005). For all patients, predictive modeling determined that if the cross-sectional areas of the ST and GT were 31.2 mm2 or greater, then 87.5% of patients would have a graft size of 8 mm or greater with an 80% sensitivity and 74% specificity. Similarly, if the cross-sectional areas of the ST and GT were 31.4 mm2 or greater in patients with open physes, then 100% of patients would have a graft size of 8 mm or greater with a 46% sensitivity and 99% specificity. CONCLUSIONS: A preoperative summation of the cross-sectional areas of the ST and GT greater than 31 mm2 in patients younger than 18 years with open or closed physes can help the surgeon preoperatively predict which patients will have an intraoperative graft size of 8 mm or greater. The risk factors for a smaller graft size include female sex, a shorter height, and a lighter weight. LEVEL OF EVIDENCE: Level III, retrospective comparative study.

Measuring the Acetabular Index: An Accurate and Reliable Alternative Method of Measurement.

OBJECTIVE. In children (4 months to 8 years old), radiographic measurements of the acetabular index are the preferred method to assess developmental hip dysplasia. However, the acetabular index has been criticized as having variable reliability owing to difficulty identifying the correct anatomic landmarks. An alternative method of measuring the acetabular index using the ischium is being proposed to avoid the variability of the triradiate cartilage line as a reference point. With the alternative method, the acetabular index is derived by measuring the angle between a line connecting the ischial tuberosi-ties and a line connecting the inferomedial and superolateral edges of the acetabulum. The purpose of this study was to evaluate the accuracy and reliability of this alternative method of measuring the acetabular index compared with the traditional method. MATERIALS AND METHODS. Children 4 months to 8 years old who presented for evaluation of developmental dysplasia of the hip were included. Two physicians, each using both the traditional and the alternative method, measured acetabular indexes on all radiographs. Accuracy was defined as mean absolute error less than 6°. Reliability was calculated by means of intraclass correlation coefficient (ICC). RESULTS. Pelvic radiographs of 40 children (324 hips) were included. The mean age was 23.7 months (range, 4-96 months) and mean acetabular index was 24.2° (range, 8-50°). The alternative method was associated with mean absolute error of 2.50°, which is significantly below the threshold of 6° (t < 0.001). Intrarater reliability for the traditional method was high (ICC, 0.81) and for the alternative method was very high (ICC, 0.92). Interrater reliability for the traditional method was high (ICC, 0.89) and for the alternative method was very high (ICC, 0.91). CONCLUSION. Measuring the acetabular index using the alternative method has very high accuracy and intrarater and interrater reliability.

Sustainable hydrogen production from water using tandem dye-sensitized photoelectrochemical cells.

If generated from water using renewable energy, hydrogen could serve as a carbon-zero, environmentally benign fuel to meet the needs of modern society. Photoelectrochemical cells integrate the absorption and conversion of solar energy and chemical catalysis for the generation of high value products. Tandem photoelectrochemical devices have demonstrated impressive solar-to-hydrogen conversion efficiencies but have not become economically relevant due to high production cost. Dye-sensitized solar cells, those based on a monolayer of molecular dye adsorbed to a high surface area, optically transparent semiconductor electrode, offer a possible route to realizing tandem photochemical systems for H2 production by water photolysis with lower overall material and processing costs. This review addresses the design and materials important to the development of tandem dye-sensitized photoelectrochemical cells for solar H2 production and highlights current published reports detailing systems capable of spontaneous H2 formation from water using only dye-sensitized interfaces for light capture.

Photocatalytic hydrogen evolution from biomass conversion.

Biomass has incredible potential as an alternative to fossil fuels for energy production that is sustainable for the future of humanity. Hydrogen evolution from photocatalytic biomass conversion not only produces valuable carbon-free energy in the form of molecular hydrogen but also provides an avenue of production for industrially relevant biomass products. This photocatalytic conversion can be realized with efficient, sustainable reaction materials (biomass) and inexhaustible sunlight as the only energy inputs. Reported herein is a general strategy and mechanism for photocatalytic hydrogen evolution from biomass and biomass-derived substrates (including ethanol, glycerol, formic acid, glucose, and polysaccharides). Recent advancements in the synthesis and fundamental physical/mechanistic studies of novel photocatalysts for hydrogen evolution from biomass conversion are summarized. Also summarized are recent advancements in hydrogen evolution efficiency regarding biomass and biomass-derived substrates. Special emphasis is given to methods that utilize unprocessed biomass as a substrate or synthetic photocatalyst material, as the development of such will incur greater benefits towards a sustainable route for the evolution of hydrogen and production of chemical feedstocks.

The effects of thoracoplasty on immediate post-operative recovery in adolescent idiopathic scoliosis.

PURPOSE: The purpose of this study was to evaluate differences in pain, opiate utilization and oxygen (O2) consumption during the immediate post-operative course for patients undergoing posterior spinal fusion (PSF) for adolescent idiopathic scoliosis (AIS) with and without thoracoplasty. METHODS: Patients aged 10-21 years old that had undergone PSF for AIS were identified from 1/1/16-8/1/18. A cohort of patients that did not have a thoracoplasty group was used as a control group. A standardized pain protocol (rapid response pathway) was implemented on all patients. A retrospective chart review was performed. Pre-operative, operative and post-operative data and SRS scores were analyzed. RESULTS: Forty-six patients (38 girls, 8 boys) were included, 23 in each group. The average age was 15.2 years (range 12.0-19.3) and BMI was 20.9 (range 13.1-37.6). Differences in visual analog scores, post-operative oxygen and narcotic consumption were not statistically significant on any POD. Total opiate utilization was 146.06 morphine milligram equivalents (MME) in the control group and 149.41 MME in the thoracoplasty group (p = 0.78). One-year SRS self-image scores were higher in the thoracoplasty group (4.24 vs 3.96) (p = 0.007). There was no difference in length of hospitalization (3.6 vs 3.5 days), levels fused (12.9 vs 12.9) or blood loss (334.1 vs 413.5 mL). There was one pleural effusion and no instances of intercostal neuralgia or pneumothorax in the thoracoplasty group. CONCLUSION: There is no increase in immediate post-operative pain, narcotic use or oxygen consumption when a thoracoplasty is performed with a PSF for AIS. Improved SRS self-image scores were seen after thoracoplasty.

A molecular tandem cell for efficient solar water splitting.

Artificial photosynthesis provides a way to store solar energy in chemical bonds. Achieving water splitting without an applied external potential bias provides the key to artificial photosynthetic devices. We describe here a tandem photoelectrochemical cell design that combines a dye-sensitized photoelectrosynthesis cell (DSPEC) and an organic solar cell (OSC) in a photoanode for water oxidation. When combined with a Pt electrode for H2 evolution, the electrode becomes part of a combined electrochemical cell for water splitting, 2H2O → O2 + 2H2, by increasing the voltage of the photoanode sufficiently to drive bias-free reduction of H+ to H2 The combined electrode gave a 1.5% solar conversion efficiency for water splitting with no external applied bias, providing a mimic for the tandem cell configuration of PSII in natural photosynthesis. The electrode provided sustained water splitting in the molecular photoelectrode with sustained photocurrent densities of 1.24 mA/cm2 for 1 h under 1-sun illumination with no applied bias.

Outcomes following surgical management of inguinal-related groin pain in athletes: a case series.

To determine the outcomes of a limited surgical intervention, consisting of neurolysis, inguinal wall repair and/or adductor debridement of adhesions based on intraoperative findings. Retrospective case series. Outpatient orthopedic/general surgery clinic. Fifty-one athletes treated surgically for inguinal-related groin pain from 2009 to 2015. Limited surgical intervention, consisting of neurolysis, inguinal wall repair and/or adductor debridement based on intra-operative findings. Ability to return to sport at the same level, time to return to play. Fifty-one athletes were included in the study with an average follow-up of 4.42 years (range 2.02-7.01). The average age was 24.2 years (range 16-49) and consisted of 94.0% males and 6.0% females. Nerve entrapment was demonstrated in 96.2% of cases with involvement of the ilioinguinal in 92.5%, the iliohypogastric in 30.8% and the genitofemoral in 13.2%. Attenuation of the posterior inguinal wall was present and repaired in 79.3% of cases. Scar tissue was present around the adductor origin and required debridement in 56.7% of cases. Forty-nine (96.1%) athletes returned to sport at the same level of play at an average of 5.9 weeks. Two athletes required a revision surgery. High rates of return to sport were achieved after surgery for inguinal-related groin pain that addresses the varying pathology and associated nerve entrapment.

Hydrogen Peroxide Disproportionation with Manganese Macrocyclic Complexes of Cyclen and Pyclen.

The catalase family of enzymes, which include a variety with a binuclear manganese active site, mitigate the risk from reactive oxygen species by facilitating the disproportionation of hydrogen peroxide into molecular oxygen and water. In this work, hydrogen peroxide disproportionation using complexes formed between manganese and cyclen or pyclen were investigated due to the spectroscopic similarities with the native MnCAT enzyme. Potentiometric titrations were used to construct speciation diagrams that identify the manganese complex compositions at different pH values. Each complex behaves as a functional mimic of catalase enzymes. UV-visible spectroscopic investigations of the H2O2 decomposition reaction yielded information about the structure of the initial catalyst and intermediates that include monomeric and dimeric species. The results indicate that rigidity imparted by the pyridine ring of pyclen is a key factor in increased TON and TOF values measured compared to cyclen.

A stable dye-sensitized photoelectrosynthesis cell mediated by a NiO overlayer for water oxidation.

In the development of photoelectrochemical cells for water splitting or CO2 reduction, a major challenge is O2 evolution at photoelectrodes that, in behavior, mimic photosystem II. At an appropriate semiconductor electrode, a water oxidation catalyst must be integrated with a visible light absorber in a stable half-cell configuration. Here, we describe an electrode consisting of a light absorber, an intermediate electron donor layer, and a water oxidation catalyst for sustained light driven water oxidation catalysis. In assembling the electrode on nanoparticle SnO2/TiO2 electrodes, a Ru(II) polypyridyl complex was used as the light absorber, NiO was deposited as an overlayer, and a Ru(II) 2,2'-bipyridine-6,6'-dicarboxylate complex as the water oxidation catalyst. In the final electrode, addition of the NiO overlayer enhanced performance toward water oxidation with the final electrode operating with a 1.1 mA/cm2 photocurrent density for 2 h without decomposition under one sun illumination in a pH 4.65 solution. We attribute the enhanced performance to the role of NiO as an electron transfer mediator between the light absorber and the catalyst.

Youth Kicker's Knee: Lateral Distal Femoral Hemiphyseal Arrest Secondary to Chronic Repetitive Microtrauma.

Year-round competitive sports place the youth athlete at risk for injury from chronic repetitive stress. Stress injuries to the distal femoral physis in adolescents are rare. This report highlights three male youth soccer players who presented with a lateral distal femoral hemiphyseal arrest and a subsequent unilateral genu valgum deformity in their dominant "kicking leg" due to repetitive microtrauma, a phenomenon we refer to as youth kicker's knee. Mean age was 14.2 years, and all participated in year-round soccer and American football. Imaging demonstrated aberration of the distal lateral femoral physis. All patients were surgically treated. Our series illustrates a unique presentation of a chronic overuse injury in hyper sporting adolescents resulting in an ipsilateral genu valgum deformity. Understanding adolescent growth and developmental characteristics is paramount to appropriate care, prevention, and treatment of physeal injuries that may occur from repetitive overuse and avoid surgery in these young athletes when possible.