High performance electrochemical CO2 reduction over Pd decorated cobalt containing nitrogen doped carbon.

Efficient electrocatalytic CO2 reduction reaction (eCO2RR) to various products, such as carbon monoxide (CO), is crucial for mitigating greenhouse gas emissions and enabling renewable energy storage. In this article, we introduce Pd nanoparticles which are deposited over in-house synthesized nitrogen doped tubular carbon (NC) whose ends are blocked with cobalt oxide (CoOx). This composite material is denoted as Pd@CoOx/NC. Among the series of synthesized electrocatalysts, the optimum ratio (Pd@CoOx/NC1) within this category exhibits exceptional performance, manifesting an 81% faradaic efficiency (FE) for CO generation which was quantitatively measured using a gas chromatograph. This remarkable efficiency can be attributed to several scientific factors. Firstly, the presence of Pd nanoparticles provides active sites for CO2 reduction. Secondly, the NC offer enhanced electrical conductivity and facilitate charge transfer during the reaction. Thirdly, the CoOx capping at the ends of the NC serves to stabilize the catalyst, favoring the formation of CO. The remarkable selectivity of the catalyst is further confirmed by the qualitative CO detection method using PdCl2 strips. Pd@CoOx/NC1 exhibits a high current density of 55 mA cm-2 and a low overpotential of 251 mV, outperforming Pd decorated multiwalled carbon nanotubes (Pd@MWCNTs) which shows a higher overpotential of 481 mV. Pd@CoOx/NC1 shows long-term stability at different potentials and rapid reaction kinetics. These findings highlight Pd@CoOx/NC1 as promising CO2 reduction catalysts, with implications for sustainable energy conversion techniques.

Pronounced effect of yttrium oxide on the activity of Pd/rGO electrocatalyst for formic acid oxidation reaction.

A highly efficient and stable electrocatalyst comprised of yttrium oxide (Y2O3) and palladium nanoparticles has been synthesized via a sodium borohydride reduction approach. The molar ratio of Pd and Y was varied to fabricate various electrocatalysts and the oxidation reaction of formic acid was checked. X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), and X-ray powder diffraction (XRD) are used to characterize the synthesized catalysts. Among the synthesized catalysts (PdyYx/rGO), the optimized catalyst i.e., Pd6Y4/rGO exhibits the highest current density (106 mA cm-2) and lowest onset potential compared to Pd/rGO (28.1 mA cm-2) and benchmark Pd/C (21.7 mA cm-2). The addition of Y2O3 to the rGO surface results in electrochemically active sites due to the improved geometric structure and bifunctional components. The electrochemically active surface area 119.4 m2 g-1 is calculated for Pd6Y4/rGO, which is ∼1.108, ∼1.24, ∼1.47 and 1.55 times larger than Pd4Y6/rGO, Pd2Y8/rGO, Pd/C and Pd/rGO, respectively. The redesigned Pd structures on Y2O3-promoted rGO give exceptional stability and enhanced resistance to CO poisoning. The outstanding electrocatalytic performance of the Pd6Y4/rGO electrocatalyst is ascribed to uniform dispersion of small size palladium nanoparticles which is possibly due to the presence of yttrium oxide.

Three-dimensional Ni4O4-cubane metal-organic framework as a high-performance electrocatalyst for urea oxidation.

The urea oxidation reaction (UOR) is considered to be a replacement of the sluggish anodic oxygen evolution reaction (OER) in overall water-splitting. A three-dimensional (3D) nickel-containing metal-organic framework {[NiII 2(pdaa)(OH)2(H2O)] n (MOF 1) (where, H2pdaa = 1,4-phenylene diacetic acid) was investigated as a robust and highly efficient electrocatalyst for the UOR. MOF 1 comprised 1D nickel(ii) chains crosslinked through Ni4O4 cubane units to form a 3D extended network. Dangling Ni⋯OH- groups were exposed in the MOF 1 structure, and could act as active catalytic centers for the UOR. MOF 1 required a very small onset potential of 1.18 V for urea oxidation in KOH (1 M) and urea (0.33 M) and had a low Tafel slope of 38.8 mV dec-1 (in contrast to 1.84 V for the oxygen evolution reaction). The overpotential required to attain a catalytic current density of 10 mA cm-2 was 1.24 V, which is much lower than that for many materials. Controlled potential electrolysis, powder X-ray diffraction, and X-ray photoelectron spectroscopy affirmed the physicochemical integrity of the catalyst over a 17 h test reaction. This work not only addresses the problem of urea contamination, it also helps to utilize it in an energy-conversion process.

Electrocatalytic water oxidation on CuO-Cu2O modulated cobalt-manganese layered double hydroxide.

Layered double hydroxides (LDH) are potential electrocatalysts to address the sluggish oxygen evolution reaction (OER) of water splitting. In this work, copper oxide (CuO/Cu2O) nanoparticles are integrated with cobalt-manganese layered double hydroxide (CoMn-LDH) to enhance their performance towards OER. The catalyst is synthesized by growing CoMn-LDH nanosheets in the presence of CuO/Cu2O nanoparticles that were obtained by the calcination of the copper containing metal-organic framework (HKUST-1). The synthesized CoMn-LDH@CuO/Cu2O electrocatalyst shows excellent activity towards OER with an overpotential of 297 mV at a catalytic current density of 10 mA cm-2 and have a Tafel slope value of 89 mV dec-1. Moreover, a slight decrease in the performance parameters is observed until the 15 h of continuous operation. We propose that the conductive strength of CuO/Cu2O and its synergistic effect with the CoMn-LDH are responsible for the improved OER performance of the desired electrocatalyst.

A high-dose 24-hour tranexamic acid infusion for the treatment of significant gastrointestinal bleeding: HALT-IT RCT.

BACKGROUND: Tranexamic acid reduces blood loss in surgery and the risk of death in trauma patients. Meta-analyses of small trials suggest that tranexamic acid decreases the number of deaths from gastrointestinal bleeding, but these meta-analyses are prone to selection bias. OBJECTIVE: The trial provides reliable evidence of the effect of tranexamic acid on mortality, rebleeding and complications in significant acute gastrointestinal bleeding. DESIGN: A multicentre, randomised, placebo-controlled trial and economic analysis. Patients were assigned by selecting one treatment pack from a box of eight, which were identical apart from the pack number. Patients, caregivers and outcome assessors were masked to allocation. The main analyses were by intention to treat. SETTING: The setting was 164 hospitals in 15 countries, co-ordinated from the London School of Hygiene & Tropical Medicine. PARTICIPANTS: Adults with significant upper or lower gastrointestinal bleeding (n = 12,009) were eligible if the responsible clinician was substantially uncertain about whether or not to use tranexamic acid. The clinical diagnosis of significant bleeding implied a risk of bleeding to death, including hypotension, tachycardia or signs of shock, or urgent transfusion, endoscopy or surgery. INTERVENTION: Tranexamic acid (a 1-g loading dose over 10 minutes, then a 3-g maintenance dose over 24 hours) or matching placebo. MAIN OUTCOME MEASURES: The primary outcome was death due to bleeding within 5 days of randomisation. Secondary outcomes were all-cause and cause-specific mortality; rebleeding; need for endoscopy, surgery or radiological intervention; blood product transfusion; complications; disability; and days spent in intensive care or a high-dependency unit. RESULTS: A total of 12,009 patients were allocated to receive tranexamic acid (n = 5994, 49.9%) or the matching placebo (n = 6015, 50.1%), of whom 11,952 (99.5%) received the first dose. Death due to bleeding within 5 days of randomisation occurred in 222 (3.7%) patients in the tranexamic acid group and in 226 (3.8%) patients in the placebo group (risk ratio 0.99, 95% confidence interval 0.82 to 1.18). Thromboembolic events occurred in 86 (1.4%) patients in the tranexamic acid group and 72 (1.2%) patients in the placebo group (risk ratio 1.20, 95% confidence interval 0.88 to 1.64). The risk of arterial thromboembolic events (myocardial infarction or stroke) was similar in both groups (0.7% in the tranexamic acid group vs. 0.8% in the placebo group; risk ratio 0.92, 95% confidence interval 0.60 to 1.39), but the risk of venous thromboembolic events (deep-vein thrombosis or pulmonary embolism) was higher in tranexamic acid-treated patients than in placebo-treated patients (0.8% vs. 0.4%; risk ratio 1.85, 95% confidence interval 1.15 to 2.98). Seizures occurred in 38 patients who received tranexamic acid and in 22 patients who received placebo (0.6% vs. 0.4%, respectively; risk ratio 1.73, 95% confidence interval 1.03 to 2.93). In the base-case economic analysis, tranexamic acid was not cost-effective and resulted in slightly poorer health outcomes than no tranexamic acid. CONCLUSIONS: Tranexamic acid did not reduce death from gastrointestinal bleeding and, although inexpensive, it is not cost-effective in adults with acute gastrointestinal bleeding. FUTURE WORK: These results caution against a uniform approach to the management of patients with major haemorrhage and highlight the need for randomised trials targeted at specific pathophysiological processes. LIMITATIONS: Although this is one of the largest randomised trials in gastrointestinal bleeding, we cannot rule out a modest increase or decrease in death due to bleeding with tranexamic acid. TRIAL REGISTRATION: Current Controlled Trials ISRCTN11225767, ClinicalTrials.gov NCT01658124 and EudraCT 2012-003192-19. FUNDING: This project was funded by the National Institute for Health Research (NIHR) Health Technology Assessment programme and will be published in full in Health Technology Assessment; Vol. 25, No. 58. See the NIHR Journals Library website for further project information.

Acute gastrointestinal bleeding (bleeding from the gut) is a common emergency and an important cause of death and illness worldwide. In the UK, more than 65,000 people each year are admitted to hospital because of acute gastrointestinal bleeding; approximately 10% of them die within 30 days. Gastrointestinal bleeding is also common in low- and middle-income countries. The care of patients with gastrointestinal bleeding has improved in recent decades, but death rates remain high. Gastrointestinal bleeding is often caused by stomach ulcers, but also by liver damage owing to alcohol or hepatitis C infection. An effective and affordable treatment for gastrointestinal bleeding could save many lives and may reduce the need for blood transfusions, which is important because blood is a scarce resource in some health-care settings. Tranexamic acid, also known as TXA, is a cheap drug that reduces bleeding in other conditions. It helps blood to clot, thereby decreasing bleeding. A trial in bleeding accident victims found that tranexamic acid reduced the chances of bleeding to death, without any increase in side effects. We wanted to find out if tranexamic acid safely improves outcomes in patients with gastrointestinal bleeding, particularly to prevent deaths. To investigate this, the HALT-IT (Haemorrhage ALleviation with Tranexamic acid ­ Intestinal system) trial studied 12,009 patients with significant gastrointestinal bleeding in 164 hospitals across 15 countries. Half of the patients received tranexamic acid and the other half received a dummy drug, called a placebo. The treatments were assigned randomly and given in addition to all other treatments needed. Neither the patient nor the doctor knew which treatment a patient received. The trial showed that tranexamic acid did not reduce deaths from gastrointestinal bleeding. Instead, tranexamic acid was linked to an increased risk of complications, including unwanted blood clots (such as deep-vein thrombosis) and seizures. The economic analysis indicated that giving tranexamic acid to patients with gastrointestinal bleeding does not represent value for money for the NHS.

ZIF-12/Fe-Cu LDH Composite as a High Performance Electrocatalyst for Water Oxidation.

Layered double hydroxides (LDH) are being used as electrocatalysts for oxygen evolution reactions (OERs). However, low current densities limit their practical applications. Herein, we report a facile and economic synthesis of an iron-copper based LDH integrated with a cobalt-based metal-organic framework (ZIF-12) to form LDH-ZIF-12 composite (1) through a co-precipitation method. The as-synthesized composite 1 requires a low overpotential of 337 mV to achieve a catalytic current density of 10 mA cm-2 with a Tafel slope of 89 mV dec-1. Tafel analysis further demonstrates that 1 exhibits a slope of 89 mV dec-1 which is much lower than the slope of 284 mV dec-1 for LDH and 172 mV dec-1 for ZIF-12. The slope value of 1 is also lower than previously reported electrocatalysts, including Ni-Co LDH (113 mV dec-1) and Zn-Co LDH nanosheets (101 mV dec-1), under similar conditions. Controlled potential electrolysis and stability test experiments show the potential application of 1 as a heterogeneous electrocatalyst for water oxidation.

Zinc-Coordination Polymer-Derived Porous Carbon-Supported Stable PtM Electrocatalysts for Methanol Oxidation Reaction.

Porous carbon (PC) is obtained by carbonizing a zinc-coordination polymer (MOF-5) at 950 °C and PtM (M = Fe, Co, Ni, Cu, Zn) nanoparticles (NPs), which are deposited on PC using the polyol method. Structural and morphological characterizations of the synthesized materials are carried out by powder X-ray diffraction (PXRD), X-ray photoelectron spectroscopy (XPS), and high-resolution transmission electron microscopy (HRTEM), and the porosity was determined using a N2 adsorption/desorption technique. The results revealed that PtM NPs are alloyed in the fcc phase and are well dispersed on the surface of PC. The electrochemical results show that PtM/PC 950 catalysts have higher methanol oxidation reaction (MOR) performances than commercial Pt/C (20%) catalysts. After 3000 s of chronoamperometry (CA) test, the MOR performances decreased in the order of Pt1Cu1/PC 950 > Pt1Ni1/PC 950 > Pt1Fe1/PC 950 > Pt1Zn1/PC 950 > Pt1Co1/PC 950. The high MOR activities of the synthesized catalysts are attributed to the effect of M on methanol dissociative chemisorption and improved tolerance of Pt against CO poisoning. The high specific surface area and porosity of the carbon support have an additional effect in boosting the MOR activities. Screening of the first row transition metals (d 5+n , n = 1, 2, 3, 4, 5) alloyed with Pt binary catalysts for MOR shows that Pt with d 8 (Ni) and d 9 (Cu) transition metals, in equivalent atomic ratios, are good anode catalysts for alcohol fuel cells.

Concomitant Therapy versus Triple Therapy: Efficacy in H. Pylori Eradication and Predictors of Treatment Failure.

OBJECTIVE: To compare concomitant therapy (CT) and triple therapy (TRT) for success in helicobacter (H.) pylori eradication and identify factors associated with treatment failure. STUDY DESIGN: Quasi-experimental comparative study. PLACE AND DURATION OF STUDY: Department of Medicine and Gastroenterology, Services Institute of Medical Sciences from December 2018 till July 2019. METHODOLOGY: Patients with H. pylori infection were randomly assigned to receive two weeks of either CT or TRT. H. pylori eradication was confirmed by repeat biopsy four weeks post-treatment. Treatment outcome was compared using Chi-square test, while binary logistic regression identified predictors of treatment failure. RESULTS: Two hundred and eleven patients with H. pylori infection, having mean age 40.15 (±13.04) and male/female ratio 0.9/1 (100/111) after randomisation, were treated with CT in 105 patients (49.8%) and TRT in 106 patients (50.2%). H. pylori was eradicated in 84.3% (150/178) patients with completed follow-up. H. pylori eradication was achieved in 91.9% of CT group as compared to 77.2% in TRT group (p = 0.007, OR 3.38: 95% CI 1.3-8.3). Age ≥40 years (p = 0.02), symptoms duration >6 months (p = 0.001), and prior proton pump inhibitor use for >4 weeks (p = 0.01), were identified as independent predictors of treatment failure. CONCLUSION: CT achieves better H. pylori eradication than TRT. Older age, longer duration of illness, and previous proton pump inhibitor use were independent predictors of H. pylori treatment failure. Key Words: Concomitant therapy, Eradication, H. pylori, Triple therapy.

Anticancer evaluation of a manganese complex on HeLa and MCF-7 cancer cells: design, deterministic solvothermal synthesis approach, Hirshfeld analysis, DNA binding, intracellular reactive oxygen species production, electrochemical characterization and density functional theory.

Herein, a deterministic solvothermal strategy was employed to synthesize an efficient anticancer agent 'cis-dichlorobis(1,10-phenanthroline)manganese(II)' (Mn(phen)2Cl2). A single-crystal X-ray diffraction analysis revealed that Mn(phen)2Cl2 crystallizes in a triclinic system with the space group P-1. Cyclic voltammetric studies of Mn(phen)2Cl2 indicated that the electrode process occurs only due to complex formation and has a diffusion-controlled mechanism. Density functional theory estimations showed that the Mn(phen)2Cl2 is quite stable and exists in sextet spin state (five unpaired electrons) as the most stable form and hence, Mn(phen)2Cl2 is a high spin complex. Mn(phen)2Cl2 demonstrated significant anticancer potential against HeLa and MCF-7 cancer cells and less toxic behaviour towards normal BHK-21 cells. Fluorescence imaging confirmed that the production of reactive oxygen species (ROS) in HeLa cells by Mn(phen)2Cl2 induces oxidized fluorescence of dichlorofluorescein which emitted fluorescence at 530 nm after excitation at 488 nm. The microscopic investigation of apoptotic effect of Mn(phen)2Cl2 using propidium iodide and 4',6-diamidino-2-phenylindole staining indicated that nuclear condensation, cell detachment and shrinkage occur after treatment with IC50 values of Mn(phen)2Cl2. Furthermore, an assessment of caspase-9 and caspase-3 activity after exposure to Mn(phen)2Cl2 in HeLa cells indicated that at IC50 values of Mn(phen)2Cl2, 1.5 fold and 4.8 fold increase in caspase-9 and caspase-3 activity, respectively, occurs. The measurement of mitochondrial membrane potential of a cationic dye (JC-1) showed a decrease in mitochondrial membrane potential in both HeLa and MCF-7 cells depicting that compound might have adopted intrinsic pathway of apoptosis. Ability of Mn(phen)2Cl2 to interact with HS-DNA demonstrates hyperchromicity with slight blue shift from 269 nm to 265 nm showing a non-covalent interaction with Gibbs free energy of ΔG = -14.62 kJ/mol. Communicated by Ramaswamy H. Sarma.

Cutaneous Leishmaniasis (CL): A Cross-Sectional Community Based Survey on Knowledge, Attitude and Practices in a Highly Endemic Area of Waziristan (KPK Province), Pakistan.

Recent outbreaks of Cutaneous Leishmaniasis (CL) in Waziristan make the disease a public health concern in Khyber Pakhtunkhwa (KPK) province, Pakistan. The awareness and behavior of local community towards the disease is an important factor towards effective control and management of CL in endemic areas of Pakistan. A cross-sectional community based survey was piloted in new emerging district of North Waziristan Agency (KPK province), Pakistan from August 2019- February 2020. The study aimed to examine the Knowledge, Attitude and Practices (KAP) of the local community members regarding CL. The results revealed that majority of the participants were male. Only 48.2% participants have knowledge about CL and the respondents had a moderate knowledge of CL vector and the disease. Few of the respondents were aware that CL is caused by sand flies, their breeding place, biting time, transmission of CL and control measures. Skin infection and sand-flies were the main disease symptoms and disease vector were known to some of the respondents. Most of the respondents showed positive attitude towards disease seriousness and believed that the disease could be cured and can be treated through modern medicines. Admission to hospitals, cleanliness and use of bed nets were the treatment measures for the disease in suspected patients, whereas some believed that the use of bed nets could be helpful in preventing the leishmaniasis. Moderate knowledge of the CL and its transmission in the study area emphasize the need to initiate health education and awareness campaigns to reduce the disease risk and burden in this highly endemic area in near future.

Bed side teaching: Student's perception and its correlation with academic performance.

OBJECTIVE: To determine student's perception of bedside clinical teaching and to correlate it with their performance in assessment. METHODS: This cross-sectional study of correlational survey was conducted at Services Institute of Medical Sciences in September 2019, involving students of final professional year who filled a proforma to rate their bedside teaching experience during clinical rotations using rating scale. Mean scores of items were determined with score < 3 reflecting dis-satisfaction. Mean scores were compared between high and low performing students using student's t test. RESULTS: Total of 160 students participated. Physical environment domain was assigned lowest scores by students (mean 2.94±0.74) followed by teaching task by teachers (3.04±0.72), group dynamics (3.16±0.81) and patient comfort and attitude towards patient (3.87±0.60). Teaching task by teacher had maximum stems with scores < 3 needing significant improvement. Students with low academic performance were more unsatisfied with group dynamics of bedside teaching (p value 0.009), especially lack of equal opportunities of participation for every member (p value <0.000) in clinical rotations. CONCLUSION: Small size group with adequate space for bedside training and faculty training can enhance learning experience of students. Ensuring active participation of each group member during bedside learning can improve academic performance of students.

Stable and Efficient PtRu Electrocatalysts Supported on Zn-BTC MOF Derived Microporous Carbon for Formic Acid Fuel Cells Application.

Highly efficient, well-dispersed PtRu alloy nanoparticles supported on high surface area microporous carbon (MPC) electrocatalysts, are prepared and tested for formic acid oxidation reaction (FAOR). The MPC is obtained by controlled carbonization of a zinc-benzenetricarboxylate metal-organic framework (Zn-BTC MOF) precursor at 950°C, and PtRu (30 wt.%) nanoparticles (NPs) are prepared and deposited via a polyol chemical reduction method. The structural and morphological characterization of the synthesized electrocatalysts is carried out using powder X-ray diffraction (PXRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), an energy dispersive X-ray (EDX) technique, and gas adsorption analysis (BET). The FAOR performance of the catalysts is investigated through cyclic voltammetry (CV), chronoamperometry (CA), and electrochemical impedance spectroscopy (EIS). A correlation between high electrochemical surface area (ECSA) and high FAOR performance of the catalysts is observed. Among the materials employed, Pt1Ru2/MPC 950 with a high electrochemical surface area (25.3 m2 g-1) consequently showed superior activity of the FAOR (I r = 9.50 mA cm-2 and J m = 2,403 mA mg Pt - 1 ) at room temperature, with improved tolerance and stability toward carbonaceous species. The superior electrochemical performance, and tolerance to CO-poisoning and long-term stability is attributed to the high surface area carbon support (1,455 m2 g-1) and high percentage loading of ruthenium (20 wt.%). The addition of Ru promotes the efficiency of electrocatalyst by offering FAOR via a bifunctional mechanism.

Post-ERCP Pancreatitis: Risk factors and role of NSAIDs in primary prophylaxis.

OBJECTIVE: To determine efficacy of diclofenac suppository in reducing post-ERCP pancreatitis (PEP) and identify risk factors for PEP. METHODS: This is a placebo-based prospective study at Department of Medicine & Gastroenterology, Services Institute of Medical Sciences / Services Hospital, Lahore performed from January 2018 to June 2019. Patients were randomized to receive diclofenac suppository or glycerine suppository before ERCP. Both groups were compared for PEP using chi square x2 test while risk factors for PEP were determined using binary logistic regression. RESULTS: Total of 165 patients with mean age 49.1(±15.2) and male to female ratio 1/1.6 (63/102) were included. Among 82 (49.7%) patients in diclofenac group, 8 (9.7%) developed pancreatitis while 19(22.9%) of 83(50.3%) in placebo group had PEP (p value 0.02). After multivariate analysis, age>45 years (p value 0.014, OR 3.2), Bilirubin >3 mg/dl (p value 0.004 OR 3.58), time to cannulation> 5 minutes (p value<0.000 OR 9.2), use of precut (p value< 0.000 OR 4.9), pancreatic duct cannulation (p value 0.000 OR 5.46) and total procedure time >30 minutes (p value 0.01 OR 3.92) were risk factors for PEP. CONCLUSION: Pre-procedure Diclofenac suppository reduces post-ERCP pancreatitis. Age > 45 years, serum bilirubin > 3 mg/dl, cannulation time > 5 minutes, use of precut, pancreatic duct cannulation and procedure time > 30 minutes are risk factors for post-ERCP pancreatitis.

Magnetic Phase Transitions in a Ni4 O4 -Cubane-Based Metal-Organic Framework.

An unprecedented spin cluster-based network architecture {[NiII 2 (pdaa)(OH)2 (H2 O)]n (H2 pdaa=1,4-phenylene diacetic acid)}, comprising 1D linear chains of NiII ions crosslinked via Ni4 O4 cubanes, forms under hydrothermal conditions; this 3D coordination network exhibits magnetic ordering at 23.9 K as well as a second magnetic ordering process at 2.8 K likely associated with a structural phase transition.

CaO-Promoted Graphene-Supported Palladium Nanocrystals as a Universal Electrocatalyst for Direct Liquid Fuel Cells.

Here, we present the fabrication of a reduced graphene oxide-supported PdCa (PdCa/rGO) alloyed catalyst via a NaBH4 reduction method for direct alcohol fuel cells in basic medium and direct formic acid fuel cells in acidic medium. Powder X-ray diffraction, energy-dispersive X-ray spectroscopy, scanning electron microscopy, transmission electron microscopy, high-resolution transmission electron microscopy, X-ray photoelectron spectroscopy, Brunauer-Emmett-Teller, inductively coupled plasma mass spectrometry, and Raman spectroscopy are used to characterize the PdCa/rGO catalyst. We proved that the calcium oxide significantly enhances the electrocatalytic methanol, ethanol, and formic acid oxidation over the Pd/rGO surface. The obtained mass activities for PdCa/rGO are 4838.06, 4674.70, and 3906.49 mA mg-1 for formic acid, methanol, and ethanol, respectively. Long-term stability, high activity, and high level of tolerance to CO poisoning of the PdCa/rGO electrocatalyst are attributed to the presence of calcium oxide. These results prove that the PdCa/rGO catalyst has improved electrocatalytic performance for the oxidation of formic acid, methanol, and ethanol with reference to the Pd/rGO.

Conductive Self-Assembled Monolayers of Paramagnetic {CoII Co 4 III } and { Co 4 II Co 2 III } Coordination Clusters on Gold Surfaces.

Two polynuclear cobalt(II,III) complexes, [Co5(N3)4(N-n-bda)4(bza·SMe)2] (1) and [Co6(N3)4(N-n-bda)2(bza·SMe)5(MeOH)4]Cl (2), where Hbza·SMe = 4-(methylthio)benzoic acid and N-n-H2bda = N-n-butyldiethanolamine, were synthesized and fully characterized by various techniques. Compound 1 exhibits an unusual, approximately C 2-symmetric {CoII Co 4 III } core of two isosceles Co3 triangles with perpendicularly oriented planes, sharing a central, high-spin CoII ion residing in a distorted tetrahedral coordination environment. This central CoII ion is connected to four outer, octahedrally coordinated low-spin CoIII ions via oxo bridges. Compound 2 comprises a semi-circular { Co 4 II Co 2 III } motif of four non-interacting high-spin CoII and two low-spin CoIII centers in octahedral coordination environments. Self-assembled monolayers (SAMs) of 1 and 2 were physisorbed on template-stripped gold surfaces contacted by an eutectic gallium-indium (EGaIn) tip. The acquired current density-voltage (I-V) data revealed that the cobalt-based SAMs are more electrically robust than those of the previously reported dinuclear {CuIILnIII} complexes with Ln = Gd, Tb, Dy, or Y (Schmitz et al., 2018a). In addition, between 170 and 220°C, the neutral, mixed-valence compound 1 undergoes a redox modification, yielding a {Co5}-based coordination cluster (1-A) with five non-interacting, high-spin octahedral CoII centers as indicated by SQUID magnetometry analysis in combination with X-ray photoelectron spectroscopy and infrared spectroscopy. Solvothermal treatment of 1 results in a high-nuclearity coordination cluster, [Co10(N3)2(N-n-bda)6(bza·SMe)6] (3), containing 10 virtually non-interacting high-spin CoII centers.

Factors affecting the outcome of hospitalization among liver cirrhosis patients.

OBJECTIVES: To determine the factors affecting the outcome of hospitalization in patients suffering liver cirrhosis hospitalized to tertiary care hospital, Gujranwala, Pakistan. METHODS: After informed consent, the data of liver cirrhosis patients with age >12 years hospitalized from June 2016 to May 2017 was collected by purposive sampling. The outcome of the hospitalization in term of 'death' and 'no death' was noted. Statistical analysis was done using SPSS version 25. Bivariate analysis as well binary logistic regression was performed to ascertain the effect of different predictors like gender, age, history of diabetes mellitus, etiology of cirrhosis, presence of hepatic encephalopathy at presentation, presence of upper GI bleed, and tracheobronchial aspiration on the likelihood that death would be the outcome in liver cirrhosis patients. RESULTS: Amongst total of 1304 patients, 15.7% died during hospitalization. The mean age of those who died was 58.08 + 14.49 years. Bivariate analysis suggested that mortality was significantly higher in group of patients who had hepatic encephalopathy at presentation (p<0.01), no upper gi bleed (p<0.01), and who got tracheobronchial aspiration during hospitalization (p<0.01). It did not differ significantly in male/female gender (p=0.504), diabetic/non-diabetic groups (p=0.652), with viral/non-viral etiology of cirrhosis (p=0.918). Binary logistic regression revealed that patients who had tracheobronchial aspiration were 12.392 times more likely to die than who had no tracheobronchial aspiration. Similarly, patients who presented in hepatic encephalopathy were 7.862 times more likely to die than who presented without hepatic encephalopathy. CONCLUSION: The inpatient mortality rate amongst cirrhotic patients was high. Age, gender, history of diabetes, viral etiology of cirrhosis did not significantly contribute in the mortality of these patients. The patients who presented in hepatic encephalopathy, and who suffered tracheobronchial aspiration during hospitalization were more likely to die. Excellence in hepatic encephalopathy management and prevention from aspiration can effectively reduce the mortality rate of cirrhotic patients in our hospitals.

Primary prophylaxis of hepatic encephalopathy in decompensated cirrhosis: Low dose vs. full dose rifaximin.

OBJECTIVE: To compare efficacy of high vs low dose rifaximin for primary prophylaxis of portosystemic encephalopathy (PSE) in decompensated liver cirrhosis. METHODS: In a quasi-experimental double blind randomized study at Services Institute of Medical Sciences (SIMS), Lahore from August 2017 to August 2018, patients of decompensated cirrhosis with no previous PSE were randomized to receive twice daily rifaximin 200mg in Group-A and 550mg in Group-B. Patients were followed for 6 months for development of PSE. RESULTS: In 75 included patients, mean age was 53.8(±10.7) years and male/female ratio was 0.97/1(37/38). After randomization, 34 (45.3%) patients were included in Group-A and 41 (54.7%) patients in Group-B. During 6 month follow up 24 (32%) patients developed PSE, 12 (35.2%) in Group-A and 12 (29.2%) in Group-B, difference was not significant (p value 0.57). In 6 months, 13 (17.3%) patient died, 6 (17.6%) in Group-A and 7 (17.07%) patients in Group-B, difference not significant (p value 0.94). Patients who died had higher bilirubin (p < 0.00), higher serum creatinine (p 0.05), high CTP score (p 0.04) and worse MELD score (p 0.004). CONCLUSION: Rifaximin is not effective for primary prophylaxis of overt hepatic encephalopathy in decompensated cirrhosis patients.

Tranexamic acid for acute gastrointestinal bleeding (the HALT-IT trial): statistical analysis plan for an international, randomised, double-blind, placebo-controlled trial.

BACKGROUND: Acute gastrointestinal (GI) bleeding is an important cause of mortality worldwide. Bleeding can occur from the upper or lower GI tract, with upper GI bleeding accounting for most cases. The main causes include peptic ulcer/erosive mucosal disease, oesophageal varices and malignancy. The case fatality rate is around 10% for upper GI bleeding and 3% for lower GI bleeding. Rebleeding affects 5-40% of patients and is associated with a four-fold increased risk of death. Tranexamic acid (TXA) decreases bleeding and the need for blood transfusion in surgery and reduces death due to bleeding in patients with trauma and postpartum haemorrhage. It reduces bleeding by inhibiting the breakdown of fibrin clots by plasmin. Due to the methodological weaknesses and small size of the existing trials, the effectiveness and safety of TXA in GI bleeding is uncertain. The Haemorrhage ALleviation with Tranexamic acid - Intestinal system (HALT-IT) trial aims to provide reliable evidence about the effects of TXA in acute upper and lower GI bleeding. METHODS: The HALT-IT trial is an international, randomised, double-blind, placebo-controlled trial of tranexamic acid in 12,000 adults (increased from 8000) with acute upper or lower GI bleeding. Eligible patients are randomly allocated to receive TXA (1-g loading dose followed by 3-g maintenance dose over 24 h) or matching placebo. The main analysis will compare those randomised to TXA with those randomised to placebo on an intention-to-treat basis, presenting the results as effect estimates (relative risks) and confidence intervals. The primary outcome is death due to bleeding within 5 days of randomisation and secondary outcomes are: rebleeding; all-cause and cause-specific mortality; thromboembolic events; complications; endoscopic, radiological and surgical interventions; blood transfusion requirements; disability (defined by a measure of patient's self-care capacity); and number of days spent in intensive care or high-dependency units. Subgroup analyses for the primary outcome will consider time to treatment, location of bleeding, cause of bleed and clinical Rockall score. DISCUSSION: We present the statistical analysis of the HALT-IT trial. This plan was published before the treatment allocation was unblinded. TRIAL REGISTRATION: Current Controlled Trials, ID: ISRCTN11225767. Registered on 3 July 2012; Clinicaltrials.gov, ID: NCT01658124. Registered on 26 July 2012.

A trinuclear cobalt-based coordination polymer as an efficient oxygen evolution electrocatalyst at neutral pH.

The dearth of an efficient, robust, abundant and cost-effective water oxidation catalyst is debatably the major hurdle for the technological advancement of artificial photosynthesis devices. Herein, a three dimensional (3D) cobalt-based coordination polymer {[Co3(pyz)(fa)3(dmso)2]·2H2O}n, (1) (pyz = pyrazine, fa = fumarate, dmso = dimethyl sulfoxide) has been synthesized and demonstrated to act as an efficient electrocatalyst towards water oxidation at neutral pH. Compound 1 displays a stair-like arrangement parallel to the b-axis, with the cobalt clusters arranged in a zigzag fashion, and contains small, honeycomb-like channels parallel to the c-axis. Compound 1 shows a remarkable activity for water oxidation and attains a current density of 1 mA.cm-2 at low overpotential (η = 257 mV) with a Tafel slope value of 80.5 mV.dec-1. This high performance of 1 in catalysing the water oxidation reaction is attributed to its unique 3-D architecture. The results of electrochemical investigations, including long-term and controlled potential electrolysis, are anticipated to guide the forthcoming advancement in creating efficient, cheap and noble metal (Pt/Ru/Ir) free catalysts for the water oxidation reaction.