Researcher degrees of freedom in statistical software contribute to unreliable results: A comparison of nonparametric analyses conducted in SPSS, SAS, Stata, and R.

Researcher degrees of freedom can affect the results of hypothesis tests and consequently, the conclusions drawn from the data. Previous research has documented variability in accuracy, speed, and documentation of output across various statistical software packages. In the current investigation, we conducted Pearson's chi-square test of independence, Spearman's rank-ordered correlation, Kruskal-Wallis one-way analysis of variance, Wilcoxon Mann-Whitney U rank-sum tests, and Wilcoxon signed-rank tests, along with estimates of skewness and kurtosis, on large, medium, and small samples of real and simulated data in SPSS, SAS, Stata, and R and compared the results with those obtained through hand calculation using the raw computational formulas. Multiple inconsistencies were found in the results produced between statistical packages due to algorithmic variation, computational error, and statistical output. The most notable inconsistencies were due to algorithmic variations in the computation of Pearson's chi-square test conducted on 2 × 2 tables, where differences in p-values reported by different software packages ranged from .005 to .162, largely as a function of sample size. We discuss how such inconsistencies may influence the conclusions drawn from the results of statistical analyses depending on the statistical software used, and we urge researchers to analyze their data across multiple packages to check for inconsistencies and report details regarding the statistical procedure used for data analysis.

Reversible Growth of Gold Nanoparticles in the Low-Temperature Water-Gas Shift Reaction.

Supported gold nanoparticles are widely studied catalysts and are among the most active known for the low-temperature water-gas shift reaction, which is essential in fuel and energy applications, but their practical application has been limited by their poor thermal stability. The catalysts deactivate on-stream via the growth of small Au nanoparticles. Using operando X-ray absorption and in situ scanning transmission electron microscopy, we report direct evidence that this process can be reversed by carrying out a facile oxidative treatment, which redisperses the gold nanoparticles and restores catalytic activity. The use of in situ methods reveals the complex dynamics of supported gold nanoparticles under reaction conditions and demonstrates that gold catalysts can be easily regenerated, expanding their scope for practical application.

N-Heterocyclic Carbene Modified Palladium Catalysts for the Direct Synthesis of Hydrogen Peroxide.

Heterogeneous palladium catalysts modified by N-heterocyclic carbenes (NHCs) are shown to be highly effective toward the direct synthesis of hydrogen peroxide (H2O2), in the absence of the promoters which are typically required to enhance both activity and selectivity. Catalytic evaluation in a batch regime demonstrated that through careful selection of the N-substituent of the NHC it is possible to greatly enhance catalytic performance when compared to the unmodified analogue and reach concentrations of H2O2 rivaling that obtained by state-of-the-art catalysts. The enhanced performance of the modified catalyst, which is retained upon reuse, is attributed to the ability of the NHC to electronically modify Pd speciation.

Retrolabyrinthine transsigmoid approach to complex parabrainstem tumors in the posterior fossa.

OBJECTIVE: The surgical management of large and complex tumors of the posterior fossa poses a formidable challenge in neurosurgery. The standard retrosigmoid craniotomy approach has been performed at most neurosurgical centers; however, the retrosigmoid approach may not provide enough working space without significant retraction of the cerebellum. The transsigmoid approach provides wider and shallower surgical fields; however, there have been few clinical and no cadaveric studies on its usefulness. In the present study, the authors describe the transsigmoid approach in clinical cases and cadaveric specimens. METHODS: For the clinical study, the authors retrospectively reviewed the medical records and operative charts of patients who had been surgically treated for parabrainstem tumors using the transsigmoid approach between 1997 and 2019. They analyzed patient demographic and clinical data, as well as surgical and clinical outcomes. In the cadaveric study, they compared the surgical views obtained in different approaches (retrosigmoid, presigmoid, retrolabyrinthine, and transsigmoid) and measured the sigmoid sinus width at the level of the endolymphatic sac and the distance between the anterior edge of the sigmoid sinus and the endolymphatic sac on 35 sides in 19 cadaveric specimens. RESULTS: A total of 21 patients (6 males and 15 females) with a mean age of 42.2 (range 15-67) years were included in the clinical study. Eleven patients had meningioma, 7 had vestibular schwannoma, 2 had hemangioblastoma, and 1 had epidermoid cyst. Gross-total, near-total, and subtotal removal were achieved in 7 (33.3%), 3 (14.3%), and 11 (52.4%) patients, respectively. In the cadaveric study, 19 cadaveric specimens were used. The sigmoid sinus was cut in the middle, and the incision was extended from the retrosigmoid to the presigmoid dura. The dura was then retracted upward and downward like opening a door. The results indicated that this technique can widen the operative field anteriorly by approximately 2 cm as compared to the retrosigmoid approach and provides a better view anterior to the brainstem. CONCLUSIONS: The transsigmoid approach is useful for complex parabrainstem tumors in the posterior fossa because it provides a wider and shallower operative view with less retraction of the cerebellum. This enables safer tumor removal with less damage to important structures in the posterior fossa, resulting in better operative and clinical outcomes.

Enhancing the understanding of the glycerol to lactic acid reaction mechanism over AuPt/TiO2 under alkaline conditions.

The oxidation of glycerol under alkaline conditions in the presence of a heterogeneous catalyst can be tailored to the formation of lactic acid, an important commodity chemical. Despite recent advances in this area, the mechanism for its formation is still a subject of contention. In this study, we use a model 1 wt. % AuPt/TiO2 catalyst to probe this mechanism by conducting a series of isotopic labeling experiments with 1,3-13C glycerol. Optimization of the reaction conditions was first conducted to ensure high selectivity to lactic acid in the isotopic labeling experiments. Selectivity to lactic acid increased with temperature and concentration of NaOH, but increasing the O2 pressure appeared to influence only the rate of reaction. Using 1,3-13C glycerol, we demonstrate that conversion of pyruvaldehyde to lactic acid proceeds via a base-promoted 1,2-hydride shift. There was no evidence to suggest that this occurs via a 2,1-methide shift under the conditions used in this study.

Rationalization of the X-ray photoelectron spectroscopy of aluminium phosphates synthesized from different precursors.

The aim of this paper is to clarify the assignments of X-ray photoelectron spectra of aluminium phosphate materials prepared from the reaction of phosphoric acid with three different aluminium precursors [Al(OH)3, Al(NO3)3 and AlCl3] at different annealing temperatures. The materials prepared have been studied by X-ray photoelectron spectroscopy (XPS), powder X-ray diffraction (XRD), infrared spectroscopy and high-resolution solid-state 31P NMR spectroscopy. A progressive polymerization from orthophosphate to metaphosphates is observed by XRD, ATR-FTIR and solid state 31P NMR, and on this basis the oxygen states observed in the XP spectra at 532.3 eV and 533.7 eV are assigned to P-O-Al and P-O-P environments, respectively. The presence of cyclic polyphosphates at the surface of the samples is also evident.

Efficient Elimination of Chlorinated Organics on a Phosphoric Acid Modified CeO2 Catalyst: A Hydrolytic Destruction Route.

The development of efficient technologies to prevent the emission of hazardous chlorinated organics from industrial sources without forming harmful byproducts, such as dioxins, is a major challenge in environmental chemistry. Herein, we report a new hydrolytic destruction route for efficient chlorinated organics elimination and demonstrate that phosphoric acid-modified CeO2 (HP-CeO2) can decompose chlorobenzene (CB) without forming polychlorinated congeners under the industry-relevant reaction conditions. The active site and reaction pathway were investigated, and it was found that surface phosphate groups initially react with CB and water to form phenol and HCl, followed by deep oxidation. The high on-stream stability of the catalyst was due to the efficient generation of HCl, which removes Cl from the catalyst surface and ensures O2 activation and therefore deep oxidation of the hydrocarbons. Subsequent density functional theory calculations revealed a distinctly decreased formation energy of an oxygen vacancy at nearest (VO-1) and next-nearest (VO-2) surface sites to the bonded phosphate groups, which likely contributes to the high rate of oxidation observed over the catalyst. Significantly, no dioxins, which are frequently formed in the conventional oxidation route, were observed. This work not only reports an efficient route and corresponding phosphate active site for chlorinated organics elimination but also illustrates that the rational design of the reaction route can solve some of the most important challenges in environmental catalysis.

Enhanced Activity and Stability of Gold/Ceria-Titania for the Low-Temperature Water-Gas Shift Reaction.

Gold supported on ceria-zirconia is one of the most active low temperature water-gas shift catalysts reported to date but rapid deactivation occurs under reaction conditions. In this study, ceria-titania was evaluated as an alternative catalyst support. Materials of different Ce:Ti compositions were synthesized using a sol-gel methodology and gold was supported onto these using a deposition-precipitation method. They were then investigated as catalysts for the low-temperature water-gas shift reaction. Au/Ce0.2Ti0.8O2 exhibited superior activity and stability to a highly active, previously reported gold catalyst supported on ceria-zirconia. High activity and stability was found to be related to the support comprising a high number of oxygen defect sites and a high specific surface area. These properties were conducive to forming a highly active catalyst with well-dispersed Au species.

Investigating the Influence of Fe Speciation on N2O Decomposition Over Fe-ZSM-5 Catalysts.

The influence of Fe speciation on the decomposition rates of N2O over Fe-ZSM-5 catalysts prepared by Chemical Vapour Impregnation were investigated. Various weight loadings of Fe-ZSM-5 catalysts were prepared from the parent zeolite H-ZSM-5 with a Si:Al ratio of 23 or 30. The effect of Si:Al ratio and Fe weight loading was initially investigated before focussing on a single weight loading and the effects of acid washing on catalyst activity and iron speciation. UV/Vis spectroscopy, surface area analysis, XPS and ICP-OES of the acid washed catalysts indicated a reduction of ca. 60% of Fe loading when compared to the parent catalyst with a 0.4 wt% Fe loading. The TOF of N2O decomposition at 600 °C improved to 3.99 × 103 s-1 over the acid washed catalyst which had a weight loading of 0.16%, in contrast, the parent catalyst had a TOF of 1.60 × 103 s-1. Propane was added to the gas stream to act as a reductant and remove any inhibiting oxygen species that remain on the surface of the catalyst. Comparison of catalysts with relatively high and low Fe loadings achieved comparable levels of N2O decomposition when propane is present. When only N2O is present, low metal loading Fe-ZSM-5 catalysts are not capable of achieving high conversions due to the low proximity of active framework Fe3+ ions and extra-framework ɑ-Fe species, which limits oxygen desorption. Acid washing extracts Fe from these active sites and deposits it on the surface of the catalyst as FexOy, leading to a drop in activity. The Fe species present in the catalyst were identified using UV/Vis spectroscopy and speculate on the active species. We consider high loadings of Fe do not lead to an active catalyst when propane is present due to the formation of FexOy nanoparticles and clusters during catalyst preparation. These are inactive species which lead to a decrease in overall efficiency of the Fe ions and consequentially a lower TOF.

A Kinetic Study of Methane Partial Oxidation over Fe-ZSM-5 Using N2 O as an Oxidant.

Catalytic methane oxidation using N2 O was investigated at 300 °C over Fe-ZSM-5. This reaction rapidly produces coke (retained organic species), and causes catalyst fouling. The introduction of water into the feed-stream resulted in a significant decrease in the coke selectivity and an increase in the selectivity to the desired product, methanol, from ca. 1 % up to 16 %. A detailed investigation was carried out to determine the fundamental effect of water on the reaction pathway and catalyst stability. The delplot technique was utilised to identify primary and secondary reaction products. This kinetic study suggests that observed gas phase products (CO, CO2 , CH3 OH, C2 H4 and C2 H6 ) form as primary products whilst coke is a secondary product. Dimethyl ether was not detected, however we consider that the formation of C2 products are likely to be due to an initial condensation of methanol within the pores of the zeolite and hence considered pseudo-primary products. According to a second order delplot analysis, coke is considered a secondary product and its formation correlates with CH3 OH formation. Control experiments in the absence of methane revealed that the rate of N2 O decomposition is similar to that of the full reaction mixture, indicating that the loss of active alpha-oxygen sites is the likely cause of the decrease in activity observed and water does not inhibit this process.

Activation and Deactivation of Gold/Ceria-Zirconia in the Low-Temperature Water-Gas Shift Reaction.

Gold (Au) on ceria-zirconia is one of the most active catalysts for the low-temperature water-gas shift reaction (LTS), a key stage of upgrading H2 reformate streams for fuel cells. However, this catalyst rapidly deactivates on-stream and the deactivation mechanism remains unclear. Using stop-start scanning transmission electron microscopy to follow the exact same area of the sample at different stages of the LTS reaction, as well as complementary X-ray photoelectron spectroscopy, we observed the activation and deactivation of the catalyst at various stages. During the heating of the catalyst to reaction temperature, we observed the formation of small Au nanoparticles (NPs; 1-2 nm) from subnanometer Au species. These NPs were then seen to agglomerate further over 48 h on-stream, and most rapidly in the first 5 h when the highest rate of deactivation was observed. These findings suggest that the primary deactivation process consists of the loss of active sites through the agglomeration and possible dewetting of Au NPs.

Supercritical Antisolvent Precipitation of Amorphous Copper-Zinc Georgeite and Acetate Precursors for the Preparation of Ambient-Pressure Water-Gas-Shift Copper/Zinc Oxide Catalysts.

A series of copper-zinc acetate and zincian georgeite precursors have been produced by supercritical CO2 antisolvent (SAS) precipitation as precursors to Cu/ZnO catalysts for the water gas shift (WGS) reaction. The amorphous materials were prepared by varying the water/ethanol volumetric ratio in the initial metal acetate solutions. Water addition promoted georgeite formation at the expense of mixed metal acetates, which are formed in the absence of the water co-solvent. Optimum SAS precipitation occurs without water to give high surface areas, whereas high water content gives inferior surface areas and copper-zinc segregation. Calcination of the acetates is exothermic, producing a mixture of metal oxides with high crystallinity. However, thermal decomposition of zincian georgeite resulted in highly dispersed CuO and ZnO crystallites with poor structural order. The georgeite-derived catalysts give superior WGS performance to the acetate-derived catalysts, which is attributed to enhanced copper-zinc interactions that originate from the precursor.

The effect of sodium species on methanol synthesis and water-gas shift Cu/ZnO catalysts: utilising high purity zincian georgeite.

The effect of sodium species on the physical and catalytic properties of Cu/ZnO catalysts derived from zincian georgeite has been investigated. Catalysts prepared with <100 ppm to 2.1 wt% Na+, using a supercritical CO2 antisolvent technique, were characterised and tested for the low temperature water-gas shift reaction and also CO2 hydrogenation to methanol. It was found that zincian georgeite catalyst precursor stability was dependent on the Na+ concentration, with the 2.1 wt% Na+-containing sample uncontrollably ageing to malachite and sodium zinc carbonate. Samples with lower Na+ contents (<100-2500 ppm) remained as the amorphous zincian georgeite phase, which on calcination and reduction resulted in similar CuO/Cu particle sizes and Cu surface areas. The aged 2.1 wt% Na+ containing sample, after calcination and reduction, was found to comprise of larger CuO crystallites and a lower Cu surface area. However, calcination of the high Na+ sample immediately after precipitation (before ageing) resulted in a comparable CuO/Cu particle size to the lower (<100-2500 ppm) Na+ containing samples, but with a lower Cu surface area, which indicates that Na+ species block Cu sites. Activity of the catalysts for the water-gas shift reaction and methanol yields in the methanol synthesis reaction correlated with Na+ content, suggesting that Na+ directly poisons the catalyst. In situ XRD analysis showed that the ZnO crystallite size and consequently Cu crystallite size increased dramatically in the presence of water in a syn-gas reaction mixture, showing that stabilisation of nanocrystalline ZnO is required. Sodium species have a moderate effect on ZnO and Cu crystallite growth rate, with lower Na+ content resulting in slightly reduced rates of growth under reaction conditions.

Synergy and Anti-Synergy between Palladium and Gold in Nanoparticles Dispersed on a Reducible Support.

Highly active and stable bimetallic Au-Pd catalysts have been extensively studied for several liquid-phase oxidation reactions in recent years, but there are far fewer reports on the use of these catalysts for low-temperature gas-phase reactions. Here we initially established the presence of a synergistic effect in a range of bimetallic Au-Pd/CeZrO4 catalysts, by measuring their activity for selective oxidation of benzyl alcohol. The catalysts were then evaluated for low-temperature WGS, CO oxidation, and formic acid decomposition, all of which are believed to be mechanistically related. A strong anti-synergy between Au and Pd was observed for these reactions, whereby the introduction of Pd to a monometallic Au catalyst resulted in a significant decrease in catalytic activity. Furthermore, monometallic Pd was more active than Pd-rich bimetallic catalysts. The nature of the anti-synergy was probed by several ex situ techniques, which all indicated a growth in metal nanoparticle size with Pd addition. However, the most definitive information was provided by in situ CO-DRIFTS, in which CO adsorption associated with interfacial sites was found to vary with the molar ratio of the metals and could be correlated with the catalytic activity of each reaction. As a similar correlation was observed between activity and the presence of Au0* (as detected by XPS), it is proposed that peripheral Au0* species form part of the active centers in the most active catalysts for the three gas-phase reactions. In contrast, the active sites for the selective oxidation of benzyl alcohol are generally thought to be electronically modified gold atoms at the surface of the nanoparticles.

Stable amorphous georgeite as a precursor to a high-activity catalyst.

Copper and zinc form an important group of hydroxycarbonate minerals that include zincian malachite, aurichalcite, rosasite and the exceptionally rare and unstable--and hence little known and largely ignored--georgeite. The first three of these minerals are widely used as catalyst precursors for the industrially important methanol-synthesis and low-temperature water-gas shift (LTS) reactions, with the choice of precursor phase strongly influencing the activity of the final catalyst. The preferred phase is usually zincian malachite. This is prepared by a co-precipitation method that involves the transient formation of georgeite; with few exceptions it uses sodium carbonate as the carbonate source, but this also introduces sodium ions--a potential catalyst poison. Here we show that supercritical antisolvent (SAS) precipitation using carbon dioxide (refs 13, 14), a process that exploits the high diffusion rates and solvation power of supercritical carbon dioxide to rapidly expand and supersaturate solutions, can be used to prepare copper/zinc hydroxycarbonate precursors with low sodium content. These include stable georgeite, which we find to be a precursor to highly active methanol-synthesis and superior LTS catalysts. Our findings highlight the value of advanced synthesis methods in accessing unusual mineral phases, and show that there is room for exploring improvements to established industrial catalysts.

Primary spinal intramedullary adrenal cortical adenoma associated with spinal dysraphism: case report.

OBJECTIVE: The authors report a primary spinal intramedullary adrenal cortical adenoma in a patient with spinal dysraphism presenting with bilateral leg pain and urinary frequency. METHODS: Magnetic resonance imaging, L2 laminectomy with resection of mass, and pathological and immunohistochemical analysis of resected mass revealed the diagnosis. RESULTS: Microscopic and immunohistochemical findings confirmed the diagnosis as a primary intramedullary tumor of adrenal cortical origin. CONCLUSION: The occurrence of a primary adrenal tumor in the spinal cord is rare and difficult to explain based on our understanding of embryology. A review of the relevant literature and discussion of the pathophysiology and clinical implications is provided.

Religion/spirituality in African-American culture: an essential aspect of psychiatric care.

There is an astonishing diversity of religious beliefs and practices in the history of African Americans that influences the presentation, diagnosis, and management of both physical and mental disorders. The majority of African Americans, however, are evangelical Christians with religious experiences originating in the regions of ancient Africa (Cush, Punt, and to a great extent, Egypt), as well as black adaptation of Hebraic, Jewish, Christian, and Islamic beliefs and rituals. Consequently, more than 60 of the nation's 125 medical schools offer classes in spirituality and health. Although there is a lack of empirical evidence that religion improves health outcomes, physicians should understand patients as a biopsychosocial-spiritual whole. Asking about religion/spirituality during a health assessment can help the physician determine whether religious/spiritual factors will influence the patient's medical decisions and compliance. Two psychiatric case histories of African Americans are presented in which religion/spirituality significantly influenced treatment decisions and results. Neither of these patients suffered major debilitating medical comorbidity.