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Purpose: Salvage radical prostatectomy is rare due to the risk of postoperative complications. We compare salvage Retzius-sparing robotic assisted radical prostatectomy (SRS-RARP) with salvage standard robotic assisted radical prostatectomy (SS-RARP). Materials and Methods: A total of 72 patients across 9 centers were identified (40 SRS-RARP vs 32 SS-RARP). Demographics, perioperative data, and pathological and functional outcomes were compared using Student's t-test and ANOVA. Cox proportional hazard models and Kaplan-Meier curves were constructed to assess risk of incontinence and time to continence. Linear regression models were constructed to investigate postoperative pad use and console time. Results: Median followup was 23 vs 36 months for SRS-RARP vs SS-RARP. Console time and estimated blood loss favored SRS-RARP. There were no differences in complication rates or oncologic outcomes. SRS-RARP had improved continence (78.4% vs 43.8%, p 0-1 pad (HR 0.28, 95% CI 0.10-0.79, p=0.016), although not when defined as >0 pad (HR 0.56, 95% CI 0.31-1.01, p=0.053). On adjusted analysis SRS-RARP was associated with decreased pads per day. Lymph node dissection and primary treatment with stereotactic body radiation therapy were associated with longer console time. Conclusions: SRS-RARP is a feasible salvage option with significantly improved urinary function outcomes. This may warrant increased utilization of SRS-RARP to manage men who fail nonsurgical primary treatment for prostate cancer.

Direct methanol fuel cells (DMFCs) using alkaline electrolytes are of interest due to the applicability of nonprecious metal-based materials for electrocatalysts. However, the lack of understanding of the methanol oxidation reaction (MOR) mechanism in alkaline media hinders the development of active catalysts for the MOR. In this work, ambient-pressure XPS and in situ surface-enhanced infrared spectroscopy were performed on the Pt surface in order to gain experimental insights into the reaction pathway for the MOR. We present a comprehensive reaction mechanism for the MOR in alkaline media and show that the MOR proceeds via two different pathways depending on the electrode potential. We confirmed the formation of partially hydrogenated CO adsorbates [HxCOad···(OH) (1 < x < 3)] via water and/or hydroxide ion-mediated dissociation of methanol. The HxCOad···(OH) species were further dehydrogenated to COad in the potential range of 0.40-0.60 VRHE and subsequently oxidized to CO2 by reactive OHad on the Pt surface at 0.65 VRHE (pathway I). Furthermore, H3C-Oad intermediates were observed at potentials higher than 0.9 VRHE, at which the MOR proceeds mainly via H3C-Oad instead of COad intermediates (pathway II). The oxidation current related to this conversion from H3C-Oad to CO2 (pathway II) dominates the overall MOR current, suggesting that the H3C-Oad pathway could be one of the keys to enhancing the MOR activity in an alkaline environment. Our findings pave the way toward a design strategy for MOR electrocatalysts with improved activity based on the experimental reaction mechanisms that have been identified.

Racial disparities in prostate cancer have not been well characterized on a genomic level. Here we show the results of a multi-institutional retrospective analysis of 1,152 patients (596 African-American men (AAM) and 556 European-American men (EAM)) who underwent radical prostatectomy. Comparative analyses between the race groups were conducted at the clinical, genomic, pathway, molecular subtype, and prognostic levels. The EAM group had increased ERG (P, Walter Rayford, Alp Tuna Beksac et al. investigated gene expression alterations in African-American and European-American men who underwent radical prostatectomy for prostate cancer. The observed differences include higher expression of inflammation genes and lower expression of mismatch repair genes in African-American men.

Noncovalent interactions at electrified interfaces are key to improving activity for the oxygen evolution reaction (OER). Here, we showed that on RuO2(110) in alkaline solutions, OER activity is ca...

Understanding the nature of active sites is central to controlling (electro)catalytic activity. Here we employed surface X-ray scattering coupled with density functional theory and surface-enhanced infrared absorption spectroscopy to examine the oxygen evolution reaction on RuO2 surfaces as a function of voltage. At 1.5 VRHE, our results suggest that there is an –OO group on the coordinatively unsaturated ruthenium (RuCUS) site of the (100) surface (and similarly for (110)), but adsorbed oxygen on the RuCUS site of (101). Density functional theory results indicate that the removal of –OO from the RuCUS site, which is stabilized by a hydrogen bond to a neighbouring –OH (–OO–H), could be the rate-determining step for (100) (similarly for (110)), where its reduced binding on (100) increased activity. A further reduction in binding energy on the RuCUS site of (101) resulted in a different rate-determining step (–O + H2O – (H+ + e−) → –OO–H) and decreased activity. Our study provides molecular details on the active sites, and the influence of their local coordination environment on activity. Understanding the nature of active sites is central to controlling the activity of a given catalyst. This work combines operando characterization and computational techniques to examine the oxygen evolution reaction mechanism on RuO2 surfaces.

Purpose: Cisplatin-based neoadjuvant chemotherapy (NAC) followed by radical cystectomy (RC) is standard of care for muscle-invasive bladder cancer (MIBC). However, NAC is used in less than 20% of patients with MIBC. Our goal is to investigate factors that contribute to underutilization NAC to facilitate more routine incorporation into clinical practice. Materials and Methods: We identified 5,915 patients diagnosed with cT2-T3N0M0 MIBC who underwent RC between 2004 and 2014 from the National Cancer Database. Univariate and multivariable models were created to identify variables associated with NAC utilization. Results: Only 18.8% of patients received NAC during the study period. On univariate analyses, NAC utilization was more likely at academic hospitals, US South and Midwest (p

Optical coherence tomography has revolutionized the diagnosis and management of neovascular age-related macular degeneration. OCT-derived biomarkers have the potential to further guide therapeutic advancements with anti-vascular endothelial growth factor; however, the clinical convergence between these two tools remains suboptimal. Therefore, the aim of this review of literature was to examine the current data on OCT biomarkers and their prognostic value. Thirteen biomarkers were analyzed, and retinal fluid had the strongest-reported impact on clinical outcomes, including visual acuity, clinic visits, and anti-VEGF treatment regimens. In particular, intra-retinal fluid was shown to be associated with poor visual outcomes. Consistencies in the literature with regard to these OCT prognostic biomarkers can lead to patient-specific clinical decision making, such as early-initiated treatment and proactive monitoring. An integrated analysis of all OCT components in combination with new efforts toward automated analysis with artificial intelligence has the potential to further improve the role of OCT in nAMD therapy.

BACKGROUND This pilot assessed transfusion requirements during resuscitation with whole blood followed by standard component therapy (CT) versus CT alone, during a change in practice at a large urban Level I trauma center. METHODS This was a single-center prospective cohort pilot study. Male trauma patients received up to 4 units of cold-stored low anti-A, anti-B group O whole blood (LTOWB) as initial resuscitation followed by CT as needed (LTOWB + CT). A control group consisting of women and men who presented when LTOWB was unavailable, received CT only (CT group). Exclusion criteria included antiplatelet or anticoagulant medication and death within 24 hours. The primary outcome was total transfusion volume at 24 hours. Secondary outcomes were mortality, morbidity, and intensive care unit- and hospital-free days. RESULTS Thirty-eight patients received LTOWB, with a median of 2.0 (interquartile range [IQR] 1.0-3.0) units of LTOWB transfused. Thirty-two patients received CT only. At 24 hours after presentation, the LTOWB +CT group had received a median of 2,138 mL (IQR, 1,275-3,325 mL) of all blood products. The median for the CT group was 4,225 mL (IQR, 1,900-5,425 mL; p = 0.06) in unadjusted analysis. When adjusted for Injury Severity Score, sex, and positive Focused Assessment with Sonography for Trauma, LTOWB +CT group patients received 3307 mL of blood products, and CT group patients received 3,260 mL in the first 24 hours (p = 0.95). The adjusted median ratio of plasma to red cells transfused was higher in the LTOWB + CT group (0.85 vs. 0.63 at 24 hours after admission; p = 0.043. Adjusted mortality was 4.4% in the LTOWB + CT group, and 11.7% in the CT group (p = 0.19), with similar complications, intensive care unit-, and hospital-free days in both groups. CONCLUSION Beginning resuscitation with LTOWB results in equivalent outcomes compared with resuscitation with CT only. LEVEL OF EVIDENCE Therapeutic (Prospective study with 1 negative criterion, limited control of confounding factors), level III.

Complex oxides, such as ABO3 perovskites, are an important class of functional materials that exhibit a wide range of physical, chemical, and electrochemical properties, including high oxygen electrocatalytic activity, tunable electronic/ionic conductivity, and ferroelectricity. When complex oxides are engineered as thin films, their chemical and physical properties can be modified to be markedly different from their bulk form, providing additional degrees of freedom in materials design. In this review, we survey the landscape of strain-induced design of complex oxides in the context of oxygen electrocatalysis and ferroelectricity. First, we identify the role of strain in influencing oxide electronic properties, driven by the combination of modification of Bsingle bondO bond length and octahedral distortion in perovskites. We describe electronic structure parameters, such as the O 2p-band center, that quantitatively capture these electronic changes, highlighting the broad influence of the O 2p-band center on surface reactivity (oxygen adsorption and dissociation energy) and bulk defect energetics (oxygen vacancy formation and migration energy). Motivated by the promise of the influence of strain on material properties relevant for oxygen electrocatalysis and ferroelectricity, we describe the advances in state-of-the-art thin-film fabrication and characterization that have enabled a high degree of experimental control in realizing strain effects in oxide thin-film systems. In oxygen electrocatalysis, leveraging strain has not only resulted in activity enhancements relative to bulk unstrained material systems but also revealed mechanistic influences of oxide phenomena, such as bulk defect chemistry and transfer kinetics, on electrochemical processes. Similarly for ferroelectric properties, strain engineering can both enhance polarization in known ferroelectrics and induce ferroelectricity in material systems that would be otherwise non-ferroelectric in bulk. Based on understanding of a diverse range of perovskite functionalities, we offer perspectives on how further coupling of strain, oxygen electrocatalysis, and ferroelectricity opens up pathways toward the emergence of novel device design features with dynamic control of increasing complex chemical and high-performance electronic processes. Ministry of Education (MOE) Nanyang Technological University Accepted version This work was supported in part by the Skoltech-MIT Center for Electrochemical Energy. Z. F. acknowledges startup funding from Oregon State University. X.R.W. acknowledges supports from the Nanyang Assistant Professorship grant from Nanyang Technological University and Academic Research Fund Tier 1 (RG108/17 and RG177/18) from Singapore Ministry of Education, Singapore. K.A.S. was supported in part by the Linus Pauling Distinguished Post-Doctoral Fellowship Pacific Northwest National Laboratory (PNNL, Laboratory Directed Research and Development Program 69319). PNNL is a multiprogram national laboratory operated for DOE by Battelle. D. L. was supported by Advanced Support Program for Innovative Research ExcellenceI funding (#15540-18-47811) provided by the Office of the Vice President for Research at the University of South Carolina. R.J. and D.M. were supported by the National Science Foundation (NSF) Software Infrastructure for Sustained Innovation (SI2) award No. 1148011.

The electrochemical reduction of CO2 (CO2RR) to high-value products is an attractive means to simultaneously address the negative effects of increasing CO2 emissions and the ever-present societal d...

Background: Fournier’s gangrene (FG) is a rapidly progressing necrotizing fasciitis that carries a significant morbidity and mortality. The present study sought to identify the predisposing factors related to FG and validate the Fournier’s Gangrene Severity Index (FGSI) score as a prognostic tool in the care of the Fournier’s patient. Methods: Medstar Washington Hospital Center records were searched from January 2003 to February 2015 for all patients with a diagnosis code of FG, n=42. Epidemiologic data was collected for patients and used to calculate an FGSI score. Results: The average age was 53.45 yrs and M/F ratio was 39:1. Patients presented with an average 2.675 predisposing factors; the most common was diabetes mellitus (n=21) followed by hypertension (n=18). The most common etiology was periscrotal (n=25) next to perirectal (n=9). Streptococcus was the most common source of infection (n=14). Patients on average required three surgical interventions. The average and median hospitalization period was 19.625 and 11.5 days respectively. Eleven patients developed sepsis. Twenty-four (60%) patients experienced a complication. The overall mortality was 5% (n=2). The average FGSI on admission was 5.368. Multivariate analysis showed FGSI score correlates with more surgical intervention, longer hospitalization, sepsis, complication and mortality. Conclusions: The FGSI score predicts a greater likelihood of more surgical interventions, longer hospitalization period, sepsis, complications and mortality within this patient population. Diabetes mellitus continues to be the most common predisposing factors in FG patients. The mortality rate of 5% is much less than the historically reported 20–30% and may reflect improved understanding and care of this aggressive disease.

RuO2-based electrodes have been extensively studied for several electrochemical reactions. Earlier literature works claim RuO2-based catalysts to be active also for the electrocatalytic conversion of CO2 to methanol with high selectivity at very low overpotentials. Here we report a thorough investigation of RuO2 films and particles for the electrocatalytic reduction of CO2. The different experimental configurations explored in our work showed that H2 is basically the only reaction product under CO2 reduction conditions in contrast to earlier reports. In situ surface enhanced infrared absorption spectroscopy (SEIRAS) measurements revealed that CO bound to the RuO2 surface, albeit acting solely as spectator species. Our experiments indicated that adsorbed CO cannot be reduced further to methanol or other CO2 reduction products.

OBJECTIVE: This study aimed to assess whether diabetes mellitus (DM) or obesity is an independent risk factor for severe coronavirus disease 2019 (COVID-19) outcomes and to explore whether the risk conferred by one condition is modified by the other. METHODS: This retrospective cohort study of inpatient adults with COVID-19 used multivariable Cox regression to determine the independent effects of DM and obesity on the composite outcome of intubation, intensive care unit admission, or in-hospital mortality. Effect modification between DM and obesity was assessed with a statistical interaction term and an exploration of stratum-specific effects. RESULTS: Out of 3,533 patients, a total of 1,134 (32%) had DM, 1,256 (36%) had obesity, and 430 (12%) had both. DM and obesity were independently associated with the composite outcome (hazard ratio [HR] 1.14 [95% CI: 1.01-1.30] and HR 1.22 [95% CI: 1.05-1.43], respectively). A statistical trend for potential interaction between DM and obesity was observed (P = 0.20). Stratified analyses showed potential increased risk with obesity compared with normal weight among patients with DM (HR 1.34 [95% CI: 1.04-1.74]) and patients without DM (HR 1.18 [95% CI: 0.96-1.43]). CONCLUSIONS: DM and obesity are independent risk factors associated with COVID-19 severity. Stratified analyses suggest that obesity may confer greater risk to patients with DM compared with patients without DM, and this relationship requires further exploration.

Understanding the adsorption and oxidation of NO on metal oxides is of immense interest to environmental and atmospheric (bio)chemistry. Here, we show that the surface oxygen activity, defined as the oxygen 2p-band centre relative to the Fermi level, dictates the adsorption and surface coverage of NOx and the kinetics of NO oxidation for La1−xSrxCoO3 perovskites. Density functional theory and ambient-pressure X-ray photoelectron spectroscopy revealed favourable NO adsorption on surface oxygen sites. Increasing the surface oxygen activity by increasing the strontium substitution led to stronger adsorption and greater storage of NO2, which resulted in more adsorbed nitrogen-like species and molecular nitrogen formed upon exposure to CO. The NO oxidation kinetics exhibited a volcano trend with surface oxygen activity, centred at La0.8Sr0.2CoO3 and with an intrinsic activity comparable to state-of-the-art catalysts. We rationalize the volcano trend by showing that increasing the NO adsorption enhances the oxidation kinetics, although NO adsorption that is too strong poisons the surface oxygen sites with adsorbed NO2 to impede the kinetics. Understanding the mechanism for the catalytic conversion of NOx is crucial to develop superior greenhouse gas abatement schemes, although it remains challenging. Here, the authors reveal important aspects of the redox properties of NOx on a La1–xSrxCoO3 perovskite by a combination of density functional theory calculations and ambient-pressure X-ray photoelectron spectroscopy.

Layered lithium nickel, manganese, and cobalt oxides (NMC) are among the most promising commercial positive electrodes in the past decades. Understanding the detailed surface and bulk redox processes of Ni-rich NMC can provide useful insights into material design options to boost reversible capacity and cycle life. Both hard X-ray absorption (XAS) of metal K-edges and soft XAS of metal L-edges collected from charged LiNi0.6Mn0.2Co0.2O2 (NMC622) and LiNi0.8Mn0.1Co0.1O2 (NMC811) showed that the charge capacity up to removing ∼0.7 Li/f.u. was accompanied with Ni oxidation in bulk and near the surface (up to 100 nm). Of significance to note is that nickel oxidation is primarily responsible for the charge capacity of NMC622 and 811 up to similar lithium removal (∼0.7 Li/f.u.) albeit charged to different potentials, beyond which was followed by Ni reduction near the surface (up to 100 nm) due to oxygen release and electrolyte parasitic reactions. This observation points toward several new strategies to enhance reversible redox capacities of Ni-rich and/or Co-free electrodes for high-energy Li-ion batteries.

Electronic structure descriptors are computationally efficient quantities used to construct qualitative correlations for a variety of properties. In particular, the oxygen p-band center has been used to guide material discovery and fundamental understanding of an array of perovskite compounds for use in catalyzing the oxygen reduction and evolution reactions. However, an assessment of the effectiveness of the oxygen p-band center at predicting key measures of perovskite catalytic activity has not been made, and would be highly beneficial to guide future predictions and codify best practices. Here, we have used Density Functional Theory at the PBE, PBEsol, PBE+U, SCAN and HSE06 levels to assess the correlations of numerous measures of catalytic performance for a series of technologically relevant perovskite oxides, using the bulk oxygen p-band center as an electronic structure descriptor. We have analyzed correlations of the calculated oxygen p-band center for all considered functionals with the experimentally measured X-ray emission spectroscopy oxygen p-band center and multiple measures of catalytic activity, including high temperature oxygen reduction surface exchange rates, aqueous oxygen evolution current densities, and binding energies of oxygen evolution intermediate species. Our results show that the best correlations for all measures of catalytic activity considered here are made with PBE-level calculations, with strong observed linear correlations with the bulk oxygen p-band center (R2 = 0.81-0.87). This study shows that strong linear correlations between numerous important measures of catalytic activity and the oxygen p-band bulk descriptor can be obtained under a consistent computational framework, and these correlations can serve as a guide for future experiments and simulations for development of perovskite and related oxide catalysts.

Cobalt-containing perovskite oxides are promising electrocatalysts for the oxygen evolution reaction (OER) in alkaline electrolyzers. However, a lack of fundamental understanding of oxide surfaces impedes rational catalyst design for improved activity and stability. We couple electrochemical studies of epitaxial La1−xSrxCoO3−δ films with in situ and operando ambient pressure X-ray photoelectron spectroscopy to investigate the surface stoichiometry, adsorbates, and electronic structure. In situ investigations spanning electrode compositions in a humid environment indicate that hydroxyl and carbonate affinity increase with Sr content, leading to an increase in binding energy of metal core levels and the valence band edge from the formation of a surface dipole. The maximum in hydroxylation at 40% Sr is commensurate with the highest OER activity, where activity scales with greater hole carrier concentration and mobility. Operando measurements of the 20% Sr-doped oxide in alkaline electrolyte indicate that the surface stoichiometry remains constant during OER, supporting the idea that the oxide electrocatalyst is stable and behaves as a metal, with the voltage drop confined to the electrolyte. Furthermore, hydroxyl and carbonate species are present on the electrode surface even under oxidizing conditions, and may impact the availability of active sites or the binding strength of adsorbed intermediates via adsorbate–adsorbate interactions. For covalent oxides with facile charge transfer kinetics, the accumulation of hydroxyl species with oxidative potentials suggests the rate of reaction could be limited by proton transfer kinetics. This operando insight will help guide modeling of self-consistent oxide electrocatalysts, and highlights the potential importance of carbonates in oxygen electrocatalysis.

Understanding the interaction of CO2 with perovskite metal oxide surfaces is crucial for the design of various perovskite (electro)chemical functionalities, such as solid oxide fuel cells, catalyti...

Rutile RuO2 catalysts are the most active pure metal oxides for oxygen evolution; however, they are also unstable toward dissolution. Herein, we study the catalytic activity and stability of oriented thin films of RuO2 with (111), (101), and (001) orientations, in comparison to a (110) single crystal and commercial nanoparticles. These surfaces were all tested in aqueous solutions of 0.05 M H2SO4. The initial catalyst activity ranked as follows: (001) > (101) > (111) ≈ (110). We complemented our activity data with inductively coupled plasma mass spectroscopy, to measure Ru dissolution products occurring in parallel to oxygen evolution. In contrast to earlier reports, we find that, under our experimental conditions, there is no correlation between the activity and stability.

The electrochemical CO2 reduction reaction (CO2RR) has gained attention recently due to rising concern over atmospheric carbon levels, but catalyst selectivity and efficiency remain a challenge, particularly for products other than CO. Here, we report the selective formation of formate using a sulfide-derived copper (SD-Cu) catalyst for CO2RR. On the basis of in situ and postelectrolysis spectroscopy, we propose that this selectivity is due to stronger binding of the CO intermediate originating from remaining subsurface sulfur atoms.

Rutile RuO2 is a highly active catalyst for a number of (electro)chemical reactions in aqueous solutions or in humid environments. However, the study of the interaction of RuO2 surfaces with water has been confined largely to the ultra-high vacuum environment, and to the thermodynamically stable (110) surface. In this work, we combine ambient pressure X-ray photoelectron spectroscopy, in situ surface diffraction and density functional theory calculations to investigate how four different facets of RuO2 interact with water under humid and electrochemical environments. The vacant coordinatively unsaturated Ru site (CUS) allows for the adsorption and dissociation of water molecules. Different surfaces exhibit unique binding energetics for -H2O and -OH and can allow for different degrees of hydrogen bonding between the adsorbates. Consequently, the degree of water dissociation is found to be sensitive to the surface crystallographic orientation - being maximum for the (101) surface, followed by the (110), (001) and (100) surfaces. This study identifies crystallographic orientation as an important parameter to tune not only the density of active sites but also the energetics for water dissociation; this finding is of great significance for many catalytic reactions, where water is a key reactant, or product.

The reduction and oxidation (redox) of transition metals allow storing charge/energy in Li-ion batteries and electrochemical capacitors and play an important role in catalysis of electrochemical reactions, such as oxygen reduction reaction (ORR) in fuel cells and metal-air batteries and oxygen evolution reaction (OER) in electrolytic cells. In this review, we present and discuss a universal origin of inductive effect associated with metal substitution in Ni, Co, Fe, Mn-based complexes, (hydr-)oxides, and lithium intercalation compounds by alignment of the electron levels of metal complex redox with partially filled metal d-state and oxygen p-state of oxides on the absolute energy scale. Increased redox potentials of metal complexes and oxides are shown to correlate with the increased electronegativity of the substituting metal, which results in the enhancement of the ORR/OER activity. Such observations provide new insights into potential strategies to optimize ORR/OER catalytic activity by tuning the redox properties of metal sites.

Catalysts for chemical and electrochemical reactions underpin many aspects of modern technology and industry, from energy storage and conversion to toxic emissions abatement to chemical and materials synthesis. This role necessitates the design of highly active, stable, yet earth-abundant heterogeneous catalysts. In this Review, we present the perovskite oxide family as a basis for developing such catalysts for (electro)chemical conversions spanning carbon, nitrogen, and oxygen chemistries. A framework for rationalizing activity trends and guiding perovskite oxide catalyst design is described, followed by illustrations of how a robust understanding of perovskite electronic structure provides fundamental insights into activity, stability, and mechanism in oxygen electrocatalysis. We conclude by outlining how these insights open experimental and computational opportunities to expand the compositional and chemical reaction space for next-generation perovskite catalysts.

The CO2 electroreduction reaction (CO2RR) is a promising avenue to convert greenhouse gases into high-value fuels and chemicals, in addition to being an attractive method for storing intermittent renewable energy. Although polycrystalline Cu surfaces have long been known to be unique in their capabilities of catalyzing the conversion of CO2 to higher-order C1 and C2 fuels, such as hydrocarbons (CH4, C2H4, etc.) and alcohols (CH3OH, C2H5OH), product selectivity remains a challenge. Rational design of more selective catalysts would greatly benefit from a mechanistic understanding of the complex, multiproton, and multielectron conversion of CO2. In this study, we select three metal catalysts (Pt, Au, Cu) and apply in situ surface enhanced infrared absorption spectroscopy (SEIRAS) and ambient-pressure X-ray photoelectron spectroscopy (APXPS), coupled to density-functional theory (DFT) calculations, to get insight into the reaction pathway for the CO2RR. We present a comprehensive reaction mechanism for the CO2RR and show that the preferential reaction pathway can be rationalized in terms of metal-carbon (M-C) and metal-oxygen (M-O) affinity. We show that the final products are determined by the configuration of the initial intermediates, C-bound and O-bound, which can be obtained from CO2 and (H)CO3, respectively. C1 hydrocarbons are produced via OCH3,ad intermediates obtained from O-bound CO3,ad and require a catalyst with relatively high affinity for O-bound intermediates. Additionally, C2 hydrocarbon formation is suggested to result from the C-C coupling between C-bound COad and (H)COad, which requires an optimal affinity for the C-bound species, so that (H)COad can be further reduced without poisoning the catalyst surface. It is suggested that the formation of C1 alcohols (CH3OH) is the most challenging process to optimize, as stabilization of the O-bound species would both accelerate the formation of key intermediates (OCH3,ad) but also simultaneously inhibit their desorption from the catalyst surface. Our findings pave the way toward a design strategy for CO2RR catalysts with improved selectivity, based on the experimental/theoretical reaction mechanisms that have been identified. These results also suggest that designing the electronic structure of the catalyst is not the sole determining factor to achieve highly selective CO2RR catalysis; rather, tuning additional experimental reaction conditions such as electrolyte-intermediate interactions also become critical.

Electrocatalytic reduction of CO2 (CO2RR) is an attractive method of converting CO2 to solar fuels. Much research in this field has been focused on developing novel catalysts to enhance the activity and product distribution (selectivity). Copper has been studied widely as it can produce both one carbon (C1) products such as methane and formate, and products with two or more carbons (C2+) such as ethylene, ethanol, and n-propanol1. Copper is not immune from the competing hydrogen evolution reaction: the poor solubility of CO2 in water (~34 mM at ambient conditions) limits the CO2RR current density, and hydrogen generation is favored if the aqueous CO2 concentration becomes locally undersaturated close to the catalyst during CO2RR2. This limitation is even more pronounced for nanotextured copper, because the increased active surface area leads to faster depletion of local CO2 thereby promoting hydrogen evolution over CO2RR. Hence, overcoming these CO2 availability limitations can enable higher CO2RR activity while reducing co-evolution of hydrogen. In this work, we develop a gasphilic CO2 trap that increases gas-liquid mass transfer and maintains supersaturated CO2 concentration around the catalyst during CO2RR. Gasphilic surfaces need a special combination of surface chemistry and texture to capture bubbles and form a sheet of gas underwater which is called a plastron3. By creating pyramidal textures, CO2 bubbles are efficiently captured within the textures and form a CO2 plastron. When this plastron is placed proximal to both smooth and nanostructured copper catalysts during CO2RR, the current density is enhanced and maintained throughout the reaction, when compared to two commonly used methods of CO2 delivery: headspace and bubbling in the bulk electrolyte. The plastron allows for quick replenishment of CO2 during the CO2RR reaction in the vicinity of the catalyst. As a result, the H2 Faradaic efficiency is reduced from 33% to 13% on smooth copper, and from 62% to 33% on nanostructured copper. This is accompanied by an increased production of C2+ products including ethylene, ethanol and propanol, as well as acetone and acetate at Faradaic efficiencies exceeding 1%. We highlight the importance of this catalyst-proximal plastron approach by comparing against recent aqueous-phase CO2RR studies, and discuss how this approach can inform optimal design of continuous CO2RR systems such as gas-diffusion electrodes. [1] Nitopi, S., Bertheussen, E., Scott, S. B., Liu, X., Engstfeld, A. K., Horch, S., Seger, B., Stephens, I. E. L., Chan, K., Hahn, C., Nørskov, J. K., Jaramillo, T. F. & Chorkendorff, I. Progress and Perspectives of Electrochemical CO2 Reduction on Copper in Aqueous Electrolyte. Chem. Rev. 119, 7610–7672 (2019). [2] Lobaccaro, P., R. Singh, M., Lee Clark, E., Kwon, Y., T. Bell, A. & W. Ager, J. Effects of temperature and gas–liquid mass transfer on the operation of small electrochemical cells for the quantitative evaluation of CO2 reduction electrocatalysts. Physical Chemistry Chemical Physics 18, 26777–26785 (2016). [3] Panchanathan, D., Rajappan, A., Varanasi, K. K. & McKinley, G. H. Plastron Regeneration on Submerged Superhydrophobic Surfaces Using In Situ Gas Generation by Chemical Reaction. ACS Appl. Mater. Interfaces 10, 33684–33692 (2018).

Summary Electrochemical reduction of carbon dioxide (CO2RR) is an attractive approach toward converting CO2 to solar fuels. Novel catalyst chemistries and morphologies may provide high selectivity to both one-carbon (C1) and two-carbon (C2) products over hydrogen; however, the limited aqueous solubility of CO2 restricts the CO2RR current density. Here, we demonstrate how gasphilic bubble-trap surfaces enhance mass transfer and enrich and maintain CO2 concentration during CO2RR by forming a catalyst-proximal plastron layer, consequently increasing the CO2RR activity on both smooth and nanostructured copper as compared to the conventional headspace or bubbling modes of CO2 delivery. The H2 Faradaic efficiency is suppressed from 33% to 13% on smooth copper and from 62% to 33% on nanostructured copper, accompanied by enhanced formation of C2+ products, including ethylene, propanol, and ethanol, and >1% acetone and acetate. We highlight the importance of the catalyst-proximal plastron approach by comparing against recent aqueous-phase CO2RR studies.

We demonstrate an oxide-stabilized III–V photoelectrode architecture for solar fuel production from water in neutral pH. For this tunable architecture we demonstrate 100% Faradaic efficiency for hydrogen evolution, and incident photon-to-current efficiencies (IPCE) exceeding 50%. High IPCE for hydrogen evolution is a consequence of the low-loss interface achieved via epitaxial growth of a thin oxide on a GaAs solar cell. Developing optimal energetic alignment across the interfaces of the photoelectrode using well-established III–V technology is key to obtaining high performance. This advance constitutes a critical milestone towards efficient, unassisted fuel production from solar energy.

The utility of radical prostatectomy (RP) for locally-advanced prostate cancer remains unknown. Retrospective data has shown equivalent oncologic outcomes compared to radiation therapy (RT). RP may provide local tumor control and prevent secondary interventions from local invasion, and may decrease costs.Using SEER-Medicare data from 1995-2011 we identified men with locally-advanced prostate cancer undergoing RP or RT. Rates of post-treatment diagnoses and interventions were identified using ICD-9 and CPT codes. Skeletal related events (SRE), androgen deprivation therapy (ADT) utilization, all-cause mortality, prostate cancer-specific mortality, and costs were compared.A total of 8367 men with locally-advanced prostate cancer were identified (6200 RP, 2167 RT). RT was associated with increased urinary obstruction, hematuria, infection, and cystoscopic intervention while RP was associated with increased urethral stricture intervention and erectile dysfunction. Compared to RT, RP was associated with decreased all-cause mortality (3.1 versus 5.2 deaths/100-person-years, p0.001), prostate cancer-specific mortality (0.8 versus 2.0 deaths/100-person-years, p0.001), SREs (2.0 versus 3.4 events/100 person-years, p0.001), and ADT utilization overall (7.4 versus 33.8 doses/100-person-years, p0.001) and3 years after treatment (3.6 versus 4.6 doses/100-person-years, p0.001). Overall and cancer specific costs were significantly lower for RP versus RT.RT for locally-advanced prostate cancer has a higher incidence of mortality, secondary diagnoses and interventions, SRE, and ADT utilization compared to RP. This may lead to increased costs and have implications for quality of life. Our findings support the utility of RP in appropriately selected men with locally-advanced prostate cancer given the possible decreased morbidity and survival benefit.

The electrochemical CO

Fully integrated transparent devices require versatile architectures for energy storage, yet typical battery electrodes are thick (20-100 μm) and composed of optically absorbent materials. Reducing the length scale of active materials, assembling them with a controllable method and minimizing electrode thickness should bring transparent batteries closer to reality. In this work, the rapid and controllable spin-spray layer-by-layer (SSLbL) method is used to generate high quality networks of 1D nanomaterials: single-walled carbon nanotubes (SWNT) and vanadium pentoxide (V2O5) nanowires for anode and cathode electrodes, respectively. These ultrathin films, deposited with ∼2 nm/bilayer precision are transparent when deposited on a transparent substrate (>87% transmittance) and electrochemically active in Li-ion cells. SSLbL-assembled ultrathin SWNT anodes and V2O5 cathodes exhibit reversible lithiation capacities of 23 and 7 μAh/cm(2), respectively at a current density of 5 μA/cm(2). When these electrodes are combined in a full cell, they retain ∼5 μAh/cm(2) capacity over 100 cycles, equivalent to the prelithiation capacity of the limiting V2O5 cathode. The SSLbL technique employed here to generate functional thin films is uniquely suited to the generation of transparent electrodes and offers a compelling path to realize the potential of fully integrated transparent devices.

The relation between ecological and genetic divergence of Helvella species (saddle fungi) has been perplexing. While a few species have been clearly demonstrated to be ectomycorrhizal fungi, ecological roles of many other species have been controversial, alternately considered as either saprotrophic or mycorrhizal. We applied SATe to build an inclusive deoxyribonucleic acid sequence alignment for the internal transcribed spacers (ITS) of annotated Helvella species and related environmental sequences. Phylogenetic informativeness of ITS and its regions were assessed using PhyDesign. Mycorrhizal lineages present a diversity of ecology, host type and geographic distribution. In two Helvella clades, no HelvellaITS sequences were recovered from root tips. Inclusion of environmental sequences in the ITS phylogeny from these sequences has the potential to link these data and reveal Helvella ecology. This study can serve as a model for revealing the diversity of relationships between unculturable fungi and their potential plant hosts. How non-mycorrhizal life styles within Helvella evolved will require expanded metagenomic investigation of soil and other environmental samples along with study of Helvella genomes.

The slow kinetics of the oxygen evolution reaction (OER) is the main cause of energy loss in many low temperature energy storage techniques, such as metal air batteries and water splitting. A better understanding of both the OER mechanism and the degradation mechanism on different transition metal (TM) oxides is critical for the development of the, next generation of oxides as OER catalysts. In this paper, we systematically investigated the catalytic mechanism and lifetime of ABO(3-delta) perovskite catalysts for the OER, where A = Sr or Ca and B = Fe or Co. During the OER process, the Fe-based AFeO(3-delta) oxides with (delta approximate to 0.5 demonstrate no activation of lattice oxygen or pH dependence of the OER activity, which is different from the SrCoO25 with similar oxygen 2p-band position relative to the Fermi level. The difference was attributed to the larger changes in the electronic structure during the transition from the oxygen-deficient brownmillerite structure to the fully oxidized perovskite structure and the poor conductivity in Fe-based oxides, which hinders the uptake of oxygen from the electrolyte to the lattice under oxidative potentials. The low stability of Fe-based perovskites under OER conditions in a basic electrolyte also contributes to the different OER mechanism compared with the Co-based perovskites. This work reveals the influence of TM composition and electronic structure on the catalytic mechanism and operational stability of the perovskite OER catalysts.

There is a significant controversy on whether race should be a factor in considering active surveillance for low-risk prostate cancer. To address this question, we analyzed a multi-institution database to assess racial disparity between African-American and White-American men with low risk prostate cancer who were eligible for active surveillance but underwent radical prostatectomy. A retrospective analysis of prospectively collected clinical, pathologic and oncologic outcomes of men with low-risk prostate cancer from seven tertiary care institutions that underwent radical prostatectomy from 2003-2014 were used to assess potential racial disparity. Of the 333 (14.8%) African-American and 1923 (85.2%) White-American men meeting active surveillance criteria, African-American men were found to be slightly younger (57.5 vs 58.5 years old; p = 0.01) and have higher BMI (29.3 v 27.9; p < 0.01), pre-op PSA (5.2 v 4.7; p < 0.01), and maximum percentage cancer on biopsy (15.1% v 13.6%; p < 0.01) compared to White-American men. Univariate and multivariate analysis demonstrated similar rates of upgrading, upstaging, positive surgical margin, and biochemical recurrence between races. These results suggest that single institution studies recommending more stringent AS enrollment criteria for AA men with a low-risk prostate cancer may not capture the complete oncologic landscape due to institutional variability in cancer outcomes. Since all seven institutions demonstrated no significant racial disparity, current active surveillance eligibility should not be modified based upon race until a prospective study has been completed.

Renal angioinfarction (RAI) has been used for various indications in the management of renal tumors. While historically used for palliation of local symptoms (pain or hematuria), this technique has theoretical use in facilitating radical nephrectomy by allowing early ligation of the renal vein, decreasing blood loss and creating edema in resection planes. A common impediment to embolization is the development of postembolization syndrome (PES), which has been reported to have an incidence as high as 89%. This study reports the authors' experience with RAI as a safe palliative and adjunctive procedure over 4 years.From 2008 to 2011, 113 patients underwent complete RAI at Washington Hospital Center for palliative or adjunctive therapy by an interventional radiologist. Procedures were performed in a radiology suite using mild sedation with vascular access obtained by femoral artery puncture. RAI was performed by subsegmental injection of polyvinyl alcohol particles.All 113 patients underwent successful RAI with confirmation of total arterial flow ablation via postprocedure arteriogram: 38 underwent embolization for preoperative adjunctive therapy, 34 for palliation of renal mass, 36 for trauma/hemorrhage and five for symptomatic renal artery pseudoaneurysm after partial nephrectomy. PES occurred in 33 out of 75 patients (44.0%), with symptomatic PES in only two patients (2.6%). No major complications (Clavien grade III) occurred. Thirty-eight patients were excluded from analysis as they underwent radical nephrectomy within 24 h, preventing accurate assessment of PES.RAI is a safe and reliable procedure for palliation of renal masses, as an adjunctive procedure for radical nephrectomy, and for conservative management of renal hemorrhage or aneurysm. PES occurs in relatively few patients, with no major complications, and should not impede clinical consideration of this procedure.

Gleason score from biopsy specimens is important for prostate cancer (PCa) risk stratification and influences treatment decisions. Gleason score upgrading (GSU) between biopsy and surgical pathology specimens has been reported as high as 50 % and presents a challenge in counseling low-risk patients. While recent studies have investigated predictors of GSU, populations in these studies have been largely Caucasian. We report our analysis of predictors of GSU in a large urban African-American population. A total of 959 patients with D’Amico low-risk prostate cancer underwent radical prostatectomy at Georgetown University or Washington Hospital Center between January 2005 and July 2012. Race, age, PSA, body mass index (BMI), cancer of the prostate risk assessment (CAPRA) score, and transrectal ultrasound (TRUS) biopsy characteristics (percent of biopsy cores showing adenocarcinoma, highest percent of biopsy core involved with cancer, and measured TRUS prostate volume) were analyzed with both univariate and multivariate analyses to identify significant predictors of GSU while controlling for clinical parameters. Of the 959 cases, 288 (30.0 %) were upgraded on final pathologic specimen with approximately 38 % (133/355) of African-American patients experiencing GSU. BMI (P = 0.02), percent positive biopsy cores (P

Laparoscopic and robotic partial nephrectomy have become the preferred option for surgical management of incidentally discovered small renal tumors. Currently there is no consensus on which aspects of the procedure should be performed laparoscopically versus robotically. We believe that combining a laparoscopic exposure and hilar dissection followed by tumor extirpation and renorrhaphy with robotic assistance provides improved perioperative outcomes compared to a pure robotic approach alone. We performed a comparison of perioperative outcomes between combined laparoscopic-robotic partial nephrectomy-or hybrid procedure-and pure robotic partial nephrectomy (RPN). A multi-center retrospective analysis of patients undergoing RPN and hybrid PN using the da Vinci S system(®) was performed. Patient data were reviewed for demographic and perioperative variables. Statistical analysis was performed using the Welch t test and linear regression, and nonparametric tests with similar significance results. Thirty-one patients underwent RPN while 77 patients underwent hybrid PN between 2007 and 2011. Preoperative variables were comparable in both groups with the exception of lesion size and nephrometry score which were significantly higher in patients undergoing hybrid PN. Length of surgery, estimated blood loss and morphine used were significantly less in the hybrid group, while warm ischemia time was significantly longer. The difference in WIT was accounted for in this data by adjusting for nephrometry score. In our multi-center series, the hybrid approach was associated with a shorter operative time, reduced blood loss and lower narcotic usage. We believe this approach is a valid alternative to RPN.

Purpose Robotic-assisted laparoscopic prostatectomy (RALP) offers reportedly comparable oncologic outcomes for localized disease compared with open radical retropubic prostatectomy (ORRP). However, the oncologic efficacy of RALP in locally-advanced prostate cancer (PCa) is less clear. We report and compare our experience with RALP and ORRP in men with locally advanced PCa. Methods Patients with locally advanced PCa (stage T3 or greater) were identified in both robotic and open cohorts. Clinicopathologic features including age, clinical stage, prostate-specific antigen, surgical margins, and Gleason score were reviewed. We further examined the incidence of positive surgical margins, the effect of the surgical learning curve on margins, and the need for adjuvant therapy. Results From 1997 to 2010, 1,011 patients underwent RALP and 415 patients were identified who underwent radical retropubic prostatectomy (RRP) across four institutions. 140 patients in the RALP group and 95 in the RRP group had locally advanced PCa on final pathology. The overall robotic positive margin rate 47.1% compared with 51.4% in the RRP group. A trend towards a lower positive margin rate was seen after 300 cases in the RALP group, with 66.7% positive margin rate in the first 300 cases compared with 41.8% in the latter 700 cases. In addition, a lower incidence of biochemical recurrence was also noted in the latter cases (30.6% vs. 9.5%). Conclusions Up to 2 out of 3 men undergoing RALP for locally-advanced PCa had positive margins during our initial experience. However, with increasing surgeon experience the overall positive margin rate decreased significantly and was comparable to the positive margin rate for patients with locally advanced disease undergoing ORRP over four academic institutions. We also noted a lower incidence of biochemical recurrence with increasing RALP experience, suggesting better oncologic outcomes with higher volume. Given this data, RALP has comparable oncologic outcomes compared to ORRP, especially with higher volume surgeons.

Primary paratesticular sarcomas are rare, affecting primarily older men between the ages of 50 and 80 years. They are the most common tumors of the paratesticular region and usually present insidiously as an asymptomatic slow-growing mass. Because of the rarity of these tumors, there is no common consensus regarding the best management, especially in the adjuvant setting. In adults, 75–80% arise from the spermatic cord and the remainder from the epididymis, tunic, or testicular appendages. Among the malignant tumors, the most common histotype is liposarcoma (46.4%), followed by leiomyosarcoma (20%), malignant fibrous histiocytomas (13%), and embryonal rhabdomyosarcoma (9%). Of these, rhabdomyosarcoma, rare after the age of 40, is the most common malignant mesenchymal tumor in children and is considered the most aggressive sarcoma. It has an increased ability to spread via the lymphatic or hematogenous route. The main dissemination pattern of adult paratesticular sarcomas is by local invasion through the contiguous inguinal canal and less commonly via hematogenous or lymphatic channels. Surgery represents the first and the most effective therapeutic approach to most paratesticular sarcomas, and overall, the prognosis after diagnosis has been related to grading, size, depth of invasion, and surgical margin status.

Numerous studies have reported electronic activity descriptors of oxygen evolution reaction (OER) for oxide catalysts under a single reaction mechanism. However, recent works have revealed that a single mechanism is not at play across oxide chemistries. These works underscore a need to deeply investigate the electronic structure details of active oxide catalysts and how they align with the OER potential, which is critical to understanding the interfacial charge-transfer kinetics that dictate catalytic mechanisms. In this work, we use soft X-ray emission and absorption spectroscopy of perovskites to analyze the partial density of states on an absolute energy scale, from which energetic barriers for electron transfer and surface deprotonation were estimated and correlated with OER activity. Through this lens, we identify that decreasing the solid-state charge-transfer energy of perovskites can change the mechanisms of the OER from electron-transfer-limited to proton–electron-coupled, to proton-transfer-limited reactions. This concept is supported by the analysis of potential energy surfaces for sequential and concerted proton–electron transfer pathways using a Marcus model. Our work highlights the importance of understanding the physical origin of experimental OER activity trends with electronic descriptors and the need to promote surface deprotonation from oxides to discover new catalysts with enhanced activity.

Transition metal oxides present a promising alternative to noble metals for oxygen electrocatalysis, including cobalt-containing perovskite oxides for the oxygen evolution reaction (OER) in alkaline electrolyzers. However, a lack of fundamental understanding of oxide surfaces impedes rational catalyst design for improved activity and stability. Investigation of epitaxial oxide thin films allows quantification of the intrinsic activity, as well as examination of their chemical speciation in an aqueous environment using ambient pressure X-ray photoelectron spectroscopy (AP-XPS). We couple electrochemical studies of epitaxial La1-xSrxCoO3 -δ films with in situ and operando AP-XPS to investigate the surface chemistry and electronic structure. By quantifying the formation of hydroxyl (OH) groups in situ, we compare the relative affinity of different surfaces for this key reaction intermediate in oxygen electrocatalysis. Operando measurements of La0.8Sr0.2CoO3 -δ in alkaline electrolyte indicate that the surface is stable during OER and behaves as a metal, with the voltage drop confined to the electrolyte. Furthermore, OH and carbonate species persist on the electrode surface even under oxidizing conditions, and may impact the availability of active sites or the binding strength of adsorbed intermediates via adsorbate-adsorbate interactions. The accumulation of OH species with oxidative potentials suggests that, for covalent oxides with facile charge transfer kinetics, the rate of reaction could be limited by proton transfer kinetics. This operando insight highlights the potential importance of carbonates in oxygen electrocatalysis and will help guide modeling of self-consistent oxide electrocatalysts.

Nausea and vomiting are common side effects from radiotherapy that can interfere with gastrointestinal (GI) cancer patients’ quality of life (QOL). This study described the subjective experience of patients with radiation-induced nausea and vomiting (RINV) and its relation to QOL. Forty-eight patients treated with abdominal radiotherapy alone or with concomitant chemoradiotherapy were followed in a prospective study. All episodes of nausea, vomiting, and antiemetic use were recorded daily for the treatment period and the week following completion of therapy. QOL was assessed weekly using the Functional Living Index—Emesis QOL Tool (FLIE) and the EORTC QLQ-C30 core questionnaire (C30). In total, 351 episodes of nausea severity, duration, onset time, and 154 outcomes of vomiting onset times and contents were documented. The median nausea severity experienced per episode was 5 (on a scale from 1 to 10), and the most common durations of nausea were 30 min or less and constant nausea all day and night. The most common location of nausea was the abdomen. Longer nausea duration, great nausea severities, and the location of nausea experienced had significant adverse relationships to multiple QOL items on both the FLIE and the C30. In addition, the onset timing and number of vomiting episodes were related to the majority of all FLIE and QOL scores. Patient’s subjective experiences of RINV directly correlated to the worsening of QOL outcomes. The identification and amelioration of these RINV experiences could improve QOL.

Photoelectric hot carrier generation in metal-semiconductor junctions can enable optical-to-electrical energy conversion at photon energies below the bandgap of the semiconductor. Here, we present the simulated and experimental results of our wafer-scale Au/TiO2 metallic-semiconductor photonic crystal (MSPhC). We demonstrate a broadband sub-bandgap photoresponse with a FWHM of 235 nm centered at 590 nm due to surface plasmon absorption, and we also show a photoresponse enhancement factor of 4.5 at 639 nm compared to a flat chip. Photoresponse is also shown to increase with decreasing metal thickness down to 13 nm. Applications of our results could lead to low-cost and robust photoelectrochemical and thermo-photovoltaic devices.