The Relevance of the Interfacial Water Reactivity for Electrochemical CO Reduction on Copper Single Crystals.

The electrochemical reduction of CO2 is an important electrolysis reaction that enables the conversion of a waste gas to fuels or value-added chemicals. To make this reaction viable, a profound understanding of central intermediate steps, such as the CO electroreduction, is required. On Cu, the CO reduction reaction (CORR) is intimately linked to the hydrogen evolution reaction (HER) that proceeds via the reduction of water in alkaline or neutral electrolytes. Here, we demonstrate that the interaction of water or more specifically the water reduction kinetics on differently smooth Cu(100) and Cu(111) surfaces during the CORR in alkaline media significantly governs the CORR. On Cu(111), faster HER kinetics and the highest CORR activity are observed, even though HER and CORR onsets are more negative. While on Cu(100) small Cu ad-island clusters form in the cathodic potential range only when CO is present, structural changes appear on a larger length scale on Cu(111) both under CORR conditions and when no CO is present. These differences in the reconstruction characteristics may be attributed to the dominance of either the CORR and its intermediates or the HER on the different Cu surfaces. Therefore, the interfacial water reactivity is considered an essential activity descriptor for the CORR on Cu in alkaline media.

Investigation on the true identity of Entomobryanigriventris Stach, 1929 (Collembola, Entomobryidae) with the description of a new species.

The present paper gives a detailed and illustrated redescription of Entomobryanigriventris Stach, 1929, and the description of a new species collected from open sand steppe habitat in Hungary. Based on the colour pattern, E.arenaria Winkler, Flórián & Dányi, sp. nov. is close to E.violaceolineata Stach, 1963 but differs from it by the morphology of the labral papillae and the dorsal macrochaetotaxy of the head, Th II, and Abd II-IV. The new species is also characterised by dark ventral body colouration in adult specimens. In this regard, an overview of European Entomobrya species in which the dark ventral side may occur is also provided.

A laboratory-based multifunctional near ambient pressure X-ray photoelectron spectroscopy system for electrochemical, catalytic, and cryogenic studies.

A versatile multifunctional laboratory-based near ambient pressure x-ray photoelectron spectroscopy (XPS) instrument is presented. The entire device is highly customized regarding geometry, exchangeable manipulators and sample stages for liquid- and solid-state electrochemistry, cryochemistry, and heterogeneous catalysis. It therefore delivers novel and unique access to a variety of experimental approaches toward a broad choice of functional materials and their specific surface processes. The high-temperature (electro)catalysis manipulator is designed for probing solid state/gas phase interactions for heterogeneous catalysts including solid electrolyzer/fuel cell electrocatalysts at pressures up to 15 mbar and temperatures from room temperature to 1000 °C. The liquid electrochemistry manipulator is specifically designed for in situ spectroscopic investigations of polarized solid/liquid interfaces using aqueous electrolytes and the third one for experiments for ice and ice-like materials at cryogenic temperatures to approximately -190 °C. The flexible and modular combination of these setups provides the opportunity to address a broad spectrum of in situ and operando XPS experiments on a laboratory-based system, circumventing the limited accessibility of experiments at synchrotron facilities.

Robust and scalable single-molecule protein sequencing with fluorosequencing.

The need to accurately survey proteins and their modifications with ever higher sensitivities, particularly in clinical settings with limited samples, is spurring development of new single molecule proteomics technologies. Fluorosequencing is one such highly parallelized single molecule peptide sequencing platform, based on determining the sequence positions of select amino acid types within peptides to enable their identification and quantification from a reference database. Here, we describe substantial improvements to fluorosequencing, including identifying fluorophores compatible with the sequencing chemistry, mitigating dye-dye interactions through the use of extended polyproline linkers, and developing an end-to-end workflow for sample preparation and sequencing. We demonstrate by fluorosequencing peptides in mixtures and identifying a target neoantigen from a database of decoy MHC peptides, highlighting the potential of the technology for high sensitivity clinical applications.

Diverse Interactions: Root-Nodule Formation and Herb-Layer Composition in Black Locust (Robinia pseudoacacia) Stands.

The black locust (Robinia pseudoacacia L.) is the second-most abundant deciduous tree in forest plantations, and one of the most important invasive woody species worldwide. The species has a strong transformer capacity, especially expressed by its nitrogen enrichment effect caused by nitrogen-fixing bacteria living in its root-nodules. The aim of this study was to explore the mutually interacting factors of nitrogen-fixing root-nodules, site characteristics, and herb-layer composition of 28 North Hungarian black locust stands. In the herb-layers of the study sites, a total of 121 plant species were identified, representing a relatively low species richness. The studied black locust stands showed high variability both in their herb-layer compositions and root-nodule formation, but no clear relationship could be demonstrated between these characteristics. The PCA component with which the species richness and Shannon-Wiener diversity index were strongly correlated was negatively associated with all root-nodule parameters (number, surface area, and weight), supporting the biodiversity-reducing effect of black locust by its nitrogen-fixing bacteria. All of the root-nodule parameters were negatively correlated with the PCA factor predominantly determined by stand age, confirming that the root-nodule biomass decreases as time progresses.

Platelets as a prognostic factor for patients with adenocarcinoma of the gastroesophageal junction.

OBJECTIVE: The aim of this study was to investigate the prognostic role of plasma platelet count (PLT), mean platelet volume (MPV), and the combined COP-MPV score in patients with resectable adenocarcinomas of the gastroesophageal junction. BACKGROUND: Platelet activation, quantified by PLT and elevated MPV, plays an essential part in the biological process of carcinogenesis and metastasis. An increased preoperative COP-MPV is associated with poor survival in various tumor entities. METHODS: Data of 265 patients undergoing surgical resection for adenocarcinoma of the gastroesophageal junction were abstracted. COP-MPV score was defined for each patient. Utilizing univariate and multivariate Cox proportional hazard analyses, survival was determined. RESULTS: In univariate analysis, elevated PLT (HR 3.58, 95% CI 2.61-4.80, p<0.001) and increased COP-MPV (HR 0.27, 95% CI 0.17-0.42, p<0.001 and HR 0.42, 95% CI 0.29-0.60, p<0.001) significantly correlated with shorter patients' overall and disease-free survival, for all 256 patients, as well as in the subgroups of neoadjuvantly treated (p<0.001) and primarily resected patients (p<0.001). COP-MPV remained a significant prognostic factor in multivariate analysis for OS. However, PLT alone showed significant diminished OS and DFS in all subgroups (p<0.001) in univariate and multivariate analysis. CONCLUSION: PLT is a potent independent prognostic biomarker for survival in a large prospective cohort of patients with resectable adenocarcinoma of the gastroesophageal junction. Additionally, we confirm that the COP-MPV score is significantly associated with worse outcome in these patients, but has no benefit in comparison to PLT.

Prognostic significance of mean corpuscular volume in patients with pancreatic ductal adenocarcinoma and multimodal treatment.

AIM OF THE STUDY: Mean corpuscular volume (MCV) has shown mounting evidence as a prognostic indicator in a number of malignancies. The aim of this study was to examine the prognostic potential of pretherapeutic MCV among patients with pancreatic ductal adenocarcinoma (PDAC) who underwent upfront resection or resection after neoadjuvant treatment (NT). PATIENTS AND METHODS: Consecutive patients with PDAC who underwent pancreatic resection between 1997 and 2019 were included in this study. Neoadjuvantly treated patients' serum MCV was measured before NT and before surgery. In patients undergoing upfront resection serum MCV was measured before surgery. Median MCV values were used as cut-off to distinguish high from low MCV values. RESULTS: Five hundred and forty-nine (438 upfront resected and 111 neoadjuvantly treated) patients were included in this study. Multivariate analysis revealed, that high MCV before and after NT, were independent negative prognostic factors for overall survival (P<0.01, respectively). Furthermore, the median MCV value from before to after NT increased significantly (P<0.001, Wilcoxon signed-rank test) and was (P=0.03, Wilcoxon rank sum test) associated with tumor response to NT. CONCLUSION: High MCV is an independent adverse prognostic factor in patients with resectable neoadjuvantly treated PDAC and may qualify as useful indicator to help physicians to provide personalized prognostication.

Electroreduction of CO2 in a Non-aqueous Electrolyte-The Generic Role of Acetonitrile.

Transition metal carbides, especially Mo2C, are praised to be efficient electrocatalysts to reduce CO2 to valuable hydrocarbons. However, on Mo2C in an aqueous electrolyte, exclusively the competing hydrogen evolution reaction takes place, and this discrepancy to theory was traced back to the formation of a thin oxide layer at the electrode surface. Here, we study the CO2 reduction activity at Mo2C in a non-aqueous electrolyte to avoid such passivation and to determine products and the CO2 reduction reaction pathway. We find a tendency of CO2 to reduce to carbon monoxide. This process is inevitably coupled with the decomposition of acetonitrile to a 3-aminocrotonitrile anion. Furthermore, a unique behavior of the non-aqueous acetonitrile electrolyte is found, where the electrolyte, instead of the electrocatalyst, governs the catalytic selectivity of the CO2 reduction. This is evidenced by in situ electrochemical infrared spectroscopy on different electrocatalysts as well as by density functional theory calculations.

The Effects of Postacute Rehabilitation on Mortality, Chronic Care Dependency, Health Care Use, and Costs in Sepsis Survivors.

Rationale: Sepsis often leads to long-term functional deficits and increased mortality in survivors. Postacute rehabilitation can decrease long-term sepsis mortality, but its impact on nursing care dependency, health care use, and costs is insufficiently understood. Objectives: To assess the short-term (7-12 months postdischarge) and long-term (13-36 months postdischarge) effect of inpatient rehabilitation within 6 months after hospitalization on mortality, nursing care dependency, health care use, and costs. Methods: An observational cohort study used health claims data from the health insurer AOK (Allgemeine Ortskrankenkasse). Among 23.0 million AOK beneficiaries, adult beneficiaries hospitalized with sepsis in 2013-2014 were identified by explicit codes from the International Classification of Diseases, Tenth Revision. The study included patients who were nonemployed presepsis, for whom rehabilitation is reimbursed by the AOK and thus included in the dataset, and who survived at least 6 months postdischarge. The effect of rehabilitation was estimated by statistical comparisons of patients with rehabilitation (treatment group) and those without (reference group). Possible differential effects were investigated for the subgroup of ICU-treated sepsis survivors. The study used inverse probability of treatment weighting based on propensity scores to adjust for differences in relevant covariates. Costs for rehabilitation in the 6 months postsepsis were not included in the cost analysis. Results: Among 41,918 6-month sepsis survivors, 17.2% (n = 7,224) received rehabilitation. There was no significant difference in short-term survival between survivors with and without rehabilitation. Long-term survival rates were significantly higher in the rehabilitation group (90.4% vs. 88.7%; odds ratio [OR] = 1.2; 95% confidence interval [95% CI] = 1.1-1.3; P = 0.003). Survivors with rehabilitation had a higher mean number of hospital readmissions (7-12 months after sepsis: 0.82 vs. 0.76; P = 0.014) and were more frequently dependent on nursing care (7-12 months after sepsis: 47.8% vs. 42.3%; OR = 1.2; 95% CI = 1.2-1.3; P < 0.001; 13-36 months after sepsis: 52.5% vs. 47.5%; OR = 1.2; 95% CI = 1.1-1.3; P < 0.001) compared with those without rehabilitation, whereas total health care costs at 7-36 months after sepsis did not differ between groups. ICU-treated sepsis patients with rehabilitation had higher short- and long-term survival rates (short-term: 93.5% vs. 90.9%; OR = 1.5; 95% CI = 1.2-1.7; P < 0.001; long-term: 89.1% vs. 86.3%; OR = 1.3; 95% CI = 1.1-1.5; P < 0.001) than ICU-treated sepsis patients without rehabilitation. Conclusions: Rehabilitation within the first 6 months after ICU- and non-ICU-treated sepsis is associated with increased long-term survival within 3 years after sepsis without added total health care costs. Future work should aim to confirm and explain these exploratory findings.

Mitogenomes of the two historical species Seiraferrarii Parona, 1888 and Seirapallidipes Reuter, 1895 (Collembola, Entomobryidae, Seirinae) with their phylogenetic placement within Seirinae.

The present paper reports the first occurrence of Seiraferrarii Parona, 1888 from Hungary. On this occasion, molecular analyses were performed on both S.ferrarii and another historical species of the genus, S.pallidipes Reuter, 1895, originally described from Hungary. Using low-coverage whole-genome sequencing, the complete mitogenomes were assembled and annotated using MitoZ. To test the phylogenetic placement of both species, we performed maximum likelihood and Bayesian analyses using a matrix containing 14 Seirinae species and two outgroups. Both resultant trees showed that the European populations of the sampled Seira spp. likely derive from ancestral branches of Seirinae, compared to the Asian and American populations. Our results put in question the monophyly of the genus Seira, as already observed in previous studies.

A new species of Entomobrya Rondani, 1861 (Collembola, Entomobryidae, Entomobryinae) from Croatia with the redescription of Entomobrya margaretae Gruia, 1967.

In the present paper, a new species of the genus Entomobrya is described from Croatia. E. silvicola sp. nov. has a unique colour pattern that distinguishes it from other Entomobrya species in Europe and worldwide. Besides the different colour pattern, there are notable differences in the dorsal macrochaetotaxy and other characters that distinguish the new species from the other Entomobrya sharing the same dorsal macrochaetotaxy formula of Abd IIIII. Herein, we also provide the redescription of E. margaretae Gruia, 1967, based on topotypic specimens, of which a neotype was designated.

Who Does the Job? How Copper Can Replace Noble Metals in Sustainable Catalysis by the Formation of Copper-Mixed Oxide Interfaces.

Following the need for an innovative catalyst and material design in catalysis, we provide a comparative approach using pure and Pd-doped LaCu x Mn1-x O3 (x = 0.3 and 0.5) perovskite catalysts to elucidate the beneficial role of the Cu/perovskite and the promoting effect of Cu y Pd x /perovskite interfaces developing in situ under model NO + CO reaction conditions. The observed bifunctional synergism in terms of activity and N2 selectivity is essentially attributed to an oxygen-deficient perovskite interface, which provides efficient NO activation sites in contact with in situ exsolved surface-bound monometallic Cu and bimetallic CuPd nanoparticles. The latter promotes the decomposition of the intermediate N2O at low temperatures, enhancing the selectivity toward N2. We show that the intelligent Cu/perovskite interfacial design is the prerequisite to effectively replace noble metals by catalytically equally potent metal-mixed-oxide interfaces. We have provided the proof of principle for the NO + CO test reaction but anticipate the extension to a universal concept applicable to similar materials and reactions.

Solutions in microbiome engineering: prioritizing barriers to organism establishment.

Microbiome engineering is increasingly being employed as a solution to challenges in health, agriculture, and climate. Often manipulation involves inoculation of new microbes designed to improve function into a preexisting microbial community. Despite, increased efforts in microbiome engineering inoculants frequently fail to establish and/or confer long-lasting modifications on ecosystem function. We posit that one underlying cause of these shortfalls is the failure to consider barriers to organism establishment. This is a key challenge and focus of macroecology research, specifically invasion biology and restoration ecology. We adopt a framework from invasion biology that summarizes establishment barriers in three categories: (1) propagule pressure, (2) environmental filtering, and (3) biotic interactions factors. We suggest that biotic interactions is the most neglected factor in microbiome engineering research, and we recommend a number of actions to accelerate engineering solutions.

A new species of Pseudosinella Schäffer, 1897 (Collembola, Entomobryidae) from Hungary and Romania, with redescription of the related species Pseudosinellahuetheri Stomp, 1971.

A new species of the genus Pseudosinella Schäffer, 1897 from Hungary and Romania is described and illustrated. Pseudosinellahartnerae sp. nov. belongs to the group with 5+5 eyes, and can be identified by its unique labial chaetotaxy (M1m2rel1L2) within this group. Pseudosinellahuetheri Stomp, 1971, the closest related species sharing the same dorsal macrochaetae formula (R0R1R2001/00/0101+2), is also redescribed here based on the holotype. Comparative analysis between the two species and among other related species is provided.

Incorporating Biogeochemistry into Dryland Restoration.

Dryland degradation is a persistent and accelerating global problem. Although the mechanisms initiating and maintaining dryland degradation are largely understood, returning productivity and function through ecological restoration remains difficult. Water limitation commonly drives slow recovery rates within drylands; however, the altered biogeochemical cycles that accompany degradation also play key roles in limiting restoration outcomes. Addressing biogeochemical changes and resource limitations may help improve restoration efforts within this difficult-to-restore biome. In the present article, we present a synthesis of restoration literature that identifies multiple ways biogeochemical understandings might augment dryland restoration outcomes, including timing restoration around resource cycling and uptake, connecting heterogeneous landscapes, manipulating resource pools, and using organismal functional traits to a restoration advantage. We conclude by suggesting ways to incorporate biogeochemistry into existing restoration frameworks and discuss research directions that may help improve restoration outcomes in the world's highly altered dryland landscapes.

Interfacial Water Structure as a Descriptor for Its Electro-Reduction on Ni(OH)2-Modified Cu(111).

The hydrogen evolution reaction (HER) has been crucial for the development of fundamental knowledge on electrocatalysis and electrochemistry, in general. In alkaline media, many key questions concerning pH-dependent structure-activity relations and the underlying activity descriptors remain unclear. While the presence of Ni(OH)2 deposited on Pt(111) has been shown to highly improve the rate of the HER through the electrode's bifunctionality, no studies exist on how low coverages of Ni(OH)2 influence the electrocatalytic behavior of Cu surfaces, which is a low-cost alternative to Pt. Here, we demonstrate that Cu(111) modified with 0.1 and 0.2 monolayers (ML) of Ni(OH)2 exhibits an unusual non-linear activity trend with increasing coverage. By combining in situ structural investigations with studies on the interfacial water orientation using electrochemical scanning tunneling microscopy and laser-induced temperature jump experiments, we find a correlation between a particular threshold of surface roughness and the decrease in the ordering of the water network at the interface. The highly disordered water ad-layer close to the onset of the HER, which is only present for 0.2 ML of Ni(OH)2, facilitates the reorganization of the interfacial water molecules to accommodate for charge transfer, thus enhancing the rate of the reaction. These findings strongly suggest a general validity of the interfacial water reorganization as an activity descriptor for the HER in alkaline media.

Drivers of seedling establishment success in dryland restoration efforts.

Restoration of degraded drylands is urgently needed to mitigate climate change, reverse desertification and secure livelihoods for the two billion people who live in these areas. Bold global targets have been set for dryland restoration to restore millions of hectares of degraded land. These targets have been questioned as overly ambitious, but without a global evaluation of successes and failures it is impossible to gauge feasibility. Here we examine restoration seeding outcomes across 174 sites on six continents, encompassing 594,065 observations of 671 plant species. Our findings suggest reasons for optimism. Seeding had a positive impact on species presence: in almost a third of all treatments, 100% of species seeded were growing at first monitoring. However, dryland restoration is risky: 17% of projects failed, with no establishment of any seeded species, and consistent declines were found in seeded species as projects matured. Across projects, higher seeding rates and larger seed sizes resulted in a greater probability of recruitment, with further influences on species success including site aridity, taxonomic identity and species life form. Our findings suggest that investigations examining these predictive factors will yield more effective and informed restoration decision-making.

True Nature of the Transition-Metal Carbide/Liquid Interface Determines Its Reactivity.

Compound materials, such as transition-metal (TM) carbides, are anticipated to be effective electrocatalysts for the carbon dioxide reduction reaction (CO2RR) to useful chemicals. This expectation is nurtured by density functional theory (DFT) predictions of a break of key adsorption energy scaling relations that limit CO2RR at parent TMs. Here, we evaluate these prospects for hexagonal Mo2C in aqueous electrolytes in a multimethod experiment and theory approach. We find that surface oxide formation completely suppresses the CO2 activation. The oxides are stable down to potentials as low as -1.9 V versus the standard hydrogen electrode, and solely the hydrogen evolution reaction (HER) is found to be active. This generally points to the absolute imperative of recognizing the true interface establishing under operando conditions in computational screening of catalyst materials. When protected from ambient air and used in nonaqueous electrolyte, Mo2C indeed shows CO2RR activity.

Operando Fourier-transform infrared-mass spectrometry reactor cell setup for heterogeneous catalysis with glovebox transfer process to surface-chemical characterization.

We describe a new type of operando Fourier transform infrared (FTIR)-mass spectrometry setup for surface-chemical and reactivity characterization of heterogeneous catalysts. On the basis of a sophisticated all-quartz FTIR reactor cell, capable of operating between room temperature and 1000 °C in reactive gas atmospheres, the setup offers a unique opportunity to simultaneously collect and accordingly correlate FTIR surface-chemical adsorption data of the active catalyst state and FTIR gas phase data with complementary reactivity data obtained via mass spectrometry in situ. The full set of catalytic operation modes (recirculating static and flow reactor conditions) is accessible and can be complemented with a variety of temperature-programmed reaction modes or thermal desorption. Due to the unique transfer process involving a home-built portable glovebox to avoid air exposure, a variety of complementary quasi in situ characterization methods for the pre- and post-reaction catalyst states become accessible. We exemplify the capabilities for additional x-ray photoelectron spectroscopy characterization of surface-chemical states, highlighting the unique strength of combining adsorption, electronic structure, and reactivity data to gain detailed insight into the reactive state of a Cu/ZrO2 heterogeneous catalyst during methanol steam reforming operation.