Blood Phytosterol Concentration and Genetic Variant Associations in a Sample Population.

The main objective of this study was to determine plasma levels of PS and to study SNVs rs41360247, rs4245791, rs4148217, and rs11887534 of ABCG8 and the r657152 SNV at the ABO blood group locus in a sample of a population treated at our hospital, and to determine whether these SNVs are related to plasma PS concentrations. The secondary objective was to establish the variables associated with plasma PS concentrations in adults. Participants completed a dietary habit questionnaire and a blood sample was collected to obtain the following variables: campesterol, sitosterol, sitostanol, lanosterol, stigmasterol, biochemical parameters, and the SNVs. In addition, biometric and demographic variables were also recorded. In the generalized linear model, cholesterol and age were positively associated with total PS levels, while BMI was negatively related. For rs4245791, homozygous T allele individuals showed a significantly lower campesterol concentration compared with C homozygotes, and the GG alleles of rs657152 had the lowest levels of campesterol compared with the other alleles of the SNV. Conclusions: The screening of certain SNVs could help prevent the increase in plasma PS and maybe PNALD in some patients. However, further studies on the determinants of plasma phytosterol concentrations are needed.

Boosting the Oxygen Evolution Activity of FeNi Oxides/Hydroxides by Molecular and Atomic Engineering.

FeNi oxides/hydroxides are the best performing catalysts for oxidizing water at basic pH. Consequently, their improvement is the cornerstone to develop more efficient artificial photosynthetic systems. During the last 5 years different reports have demonstrated an enhancement of their activity by engineering their structures via: (1) modulation of the number of oxygen, iron and nickel vacancies; (2) single atoms (SAs) doping with metals such as Au, Ir, Ru and Pt; and (3) modification of their surface using organic ligands. All these strategies have led to more active and stable electrocatalysts for oxygen evolution rection (OER). In this Concept, we critically analyze these strategies using the most relevant examples.

High-resolution ultrasound tendon-to-bone distances in partial and complete finger flexor A2 pulley ruptures simulated in human cadaver dissection: toward understanding imaging of partial pulley ruptures.

Introduction: The A2 pulley tear is the most common injury in rock climbing. Whereas complete A2 pulley ruptures have been extensively researched, studies focused on partial A2 pulley ruptures are lacking. A2 pulleys rupture distally to proximally. High-resolution ultrasound imaging is considered the gold-standard tool for diagnosis and the most relevant ultrasound measurement is the tendon-to-bone distance (TBD), which increases when the pulley ruptures. The purpose of this study was to establish tendon-to-bone distance values for different sizes of partial A2 pulley ruptures and compare these values with those of complete ruptures. Material and methods: The sample consisted of 30 in vitro fingers randomly assigned to 5 groups: G1, no simulated tear (control); G2, simulated 5 mm tear (low-grade partial rupture); G3, simulated 10 mm tear (medium-grade partial rupture); G4, simulated 15 mm tear (high-grade partial rupture); and G5, simulated 20 mm or equivalent tear (complete rupture). A highly experienced sonographer blinded to the randomization process and dissections examined all fingers. Results: The tendon-to-bone distance measurements (medians and interquartile ranges) were as follows: G1, 0.95 mm (0.77-1.33); G2, 2.11 mm (1.78-2.33); G3, 2.28 mm (1.95-2.42); G4, 3.06 mm (2.79-3.28); and G5, 3.66 mm (3.55-4.76). Significant differences were found between non-torn pulleys and simulated partial and complete pulley ruptures. Discussion: In contrast, and inconsistent with other findings, no significant differences were found among the different partial rupture groups. In conclusion, the longer the partial pulley rupture, the higher the tendon-to-bone distance value. The literature is inconsistent regarding the tendon-to-bone distance threshold to diagnose a partial A2 pulley rupture. The minimum tendon-to-bone distance value for a partial rupture was 1.6 mm, and tendon-to-bone distance values above 3 mm suggest a high-grade partial pulley rupture (15 mm incision) or a complete pulley rupture.

MicroRNA cerebrospinal fluid profile during the early brain injury period as a biomarker in subarachnoid hemorrhage patients.

Introduction: Delayed cerebral ischemia (DCI) is a dreadful complication present in up to 30% of patients with spontaneous subarachnoid hemorrhage (SAH). Indeed, DCI is one of the main causes of long-term disability in SAH, yet its prediction and prevention are troublesome in poor-grade SAH cases. In this prospective study, we explored the potential role of micro ribonucleic acid (microRNA, abbreviated miRNAs)-small non-coding RNAs involved in clue gene regulation at the post-transcriptional level-as biomarkers of neurological outcomes in SAH patients. Methods: We analyzed the expression of several miRNAs present in the cerebrospinal fluid (CSF) of SAH patients during the early stage of the disease (third-day post-hemorrhage). NanoString Technologies were used for the characterization of the CSF samples. Results: We found an overexpression of miRNAs in the acute stage of 57 SAH in comparison with 10 non-SAH controls. Moreover, a differential expression of specific miRNAs was detected according to the severity of clinical onset, but also regarding the development of DCI and the midterm functional outcomes. Conclusion: These observations reinforce the potential utility of miRNAs as prognostic and diagnostic biomarkers in SAH patients. In addition, the identification of specific miRNAs related to SAH evolution might provide insights into their regulatory functions of pathophysiological pathways, such as the TGF-ß inflammatory pathway and blood-brain barrier disruption.

Influence of Cocatalysts (Ni, Co, and Cu) and Synthesis Method on the Photocatalytic Activity of Exfoliated Graphitic Carbon Nitride for Hydrogen Production.

Exfoliated graphitic carbon nitride (ex-g-CN) was synthesized and loaded with non-noble metals (Ni, Cu, and Co). The synthesized catalysts were tested for hydrogen production using a 300-W Xe lamp equipped with a 395 nm cutoff filter. A noncommercial double-walled quartz-glass reactor irradiated from the side was used with a 1 g/L catalyst in 20 mL of a 10 vol% triethanolamine aqueous solution. For preliminary screening, the metal-loaded ex-g-CN was synthesized using the incipient wetness impregnation method. The highest hydrogen production was observed on the Ni-loaded ex-g-CN, which was selected to assess the impact of the synthesis method on hydrogen production. Ni-loaded ex-g-CN was synthesized using different synthesis methods: incipient wetness impregnation, colloidal deposition, and precipitation deposition. The catalysts were characterized by X-ray powder diffraction, X-ray photoelectron spectroscopy, nitrogen adsorption using the Brunauer-Emmett-Teller method, and transmission electron microscopy. The Ni-loaded ex-g-CN synthesized using the colloidal method performed best with a hydrogen production rate of 43.6 µmol h-1 g-1. By contrast, the catalysts synthesized using the impregnation and precipitation methods were less active, with 28.2 and 10.1 µmol h-1 g-1, respectively. The hydrogen production performance of the suspended catalyst (440 µmol m-2 g-1) showed to be superior to that of the corresponding immobilized catalyst (236 µmol m-2 g-1).

Unravelling the Mechanistic Pathway of the Hydrogen Evolution Reaction Driven by a Cobalt Catalyst.

A cobalt complex bearing a κ-N3 P2 ligand is presented (1+ or CoI (L), where L is (1E,1'E)-1,1'-(pyridine-2,6-diyl)bis(N-(3-(diphenylphosphanyl)propyl)ethan-1-imine). Complex 1+ is stable under air at oxidation state CoI thanks to the π-acceptor character of the phosphine groups. Electrochemical behavior of 1+ reveals a two-electron CoI /CoIII oxidation process and an additional one-electron reduction, which leads to an enhancement in the current due to hydrogen evolution reaction (HER) at Eonset =-1.6 V vs Fc/Fc+ . In the presence of 1 equiv of bis(trifluoromethane)sulfonimide, 1+ forms the cobalt hydride derivative CoIII (L)-H (22+ ), which has been fully characterized. Further addition of 1 equiv of CoCp*2 (Cp* is pentamethylcyclopentadienyl) affords the reduced CoII (L)-H (2+ ) species, which rapidly forms hydrogen and regenerates the initial CoI (L) (1+ ). The spectroscopic characterization of catalytic intermediates together with DFT calculations support an unusual bimolecular homolytic mechanism in the catalytic HER with 1+ .

Association between the Prime Diet Quality Score and depressive symptoms in a Mediterranean population with metabolic syndrome. Cross-sectional and 2-year follow-up assessment from PREDIMED-PLUS study.

The burden of depression is increasing worldwide, specifically in older adults. Unhealthy dietary patterns may partly explain this phenomenon. In the Spanish PREDIMED-Plus study, we explored (1) the cross-sectional association between the adherence to the Prime Diet Quality Score (PDQS), an a priori-defined high-quality food pattern, and the prevalence of depressive symptoms at baseline (cross-sectional analysis) and (2) the prospective association of baseline PDQS with changes in depressive symptomatology after 2 years of follow-up. After exclusions, we assessed 6612 participants in the cross-sectional analysis and 5523 participants in the prospective analysis. An energy-adjusted high-quality dietary score (PDQS) was assessed using a validated FFQ. The cross-sectional association between PDQS and the prevalence of depression or presence of depressive symptoms and the prospective changes in depressive symptoms were evaluated through multivariable regression models (logistic and linear models and mixed linear-effects models). PDQS was inversely associated with depressive status in the cross-sectional analysis. Participants in the highest quintile of PDQS (Q5) showed a significantly reduced odds of depression prevalence as compared to participants in the lowest quartile of PDQS (Q1) (OR (95 %) CI = 0·82 (0·68, 0·98))). The baseline prevalence of depression decreased across PDQS quintiles (Pfor trend = 0·015). A statistically significant association between PDQS and changes in depressive symptoms after 2-years follow-up was found (ß (95 %) CI = -0·67 z-score (-1·17, -0·18). A higher PDQS was cross-sectionally related to a lower depressive status. Nevertheless, the null finding in our prospective analysis raises the possibility of reverse causality. Further prospective investigation is required to ascertain the association between PDQS and changes in depressive symptoms along time.

Insights into the light-driven hydrogen evolution reaction of mesoporous graphitic carbon nitride decorated with Pt or Ru nanoparticles.

Ru or Pt nanoparticles have been prepared following the organometallic approach and deposited onto the surface of mesoporous graphitic carbon nitride (mpg-CN). Three different Ru-based samples have also been compared to investigate the effect of 4-phenylpyridine as a stabilizing agent. The photocatalytic performance towards the hydrogen evolution reaction (HER) has been tested showing that all hybrid systems clearly outperform the photocatalytic activity of bare mpg-CN. In particular, Pt-decorated mpg-CN yields the largest H2 production upon visible-light irradiation (870 µmol h-1 g-1, TOF = 14.1 h-1, TON = 339 after 24 h) when compared with the Ru-based samples (137-155 µmol h-1 g-1, TOFs between 2.3-2.7 h-1, TONs between 54-57 after 24 h). Long-term photochemical tests (up to 65 h irradiation) show also an improved stability of the Pt-based samples over the Ru counterpart. Photophysical experiments aimed at rationalizing the photocatalytic performance of the different hybrid systems elucidate that the enhanced activity of the Pt-decorated mpg-CN over the Ru-based analogues arises from improved electron transfer kinetics from mpg-CN to the metal nanoparticles.

Consecutive Ligand-Based Electron Transfer in New Molecular Copper-Based Water Oxidation Catalysts.

Water oxidation to dioxygen is one of the key reactions that need to be mastered for the design of practical devices based on water splitting with sunlight. In this context, water oxidation catalysts based on first-row transition metal complexes are highly desirable due to their low cost and their synthetic versatility and tunability through rational ligand design. A new family of dianionic bpy-amidate ligands of general formula H2 LNn- (LN is [2,2'-bipyridine]-6,6'-dicarboxamide) substituted with phenyl or naphthyl redox non-innocent moieties is described. A detailed electrochemical analysis of [(L4)Cu]2- (L4=4,4'-(([2,2'-bipyridine]-6,6'-dicarbonyl)bis(azanediyl))dibenzenesulfonate) at pH 11.6 shows the presence of a large electrocatalytic wave for water oxidation catalysis at an η=830 mV. Combined experimental and computational evidence, support an all ligand-based process with redox events taking place at the aryl-amide groups and at the hydroxido ligands.

Tissue Distribution of Oleocanthal and Its Metabolites after Oral Ingestion in Rats.

Claims for the potential health benefits of oleocanthal (OLC), a dietary phenolic compound found in olive oil, are based mainly on in vitro studies. Little is known about the tissue availability of OLC, which is rapidly metabolized after ingestion. In this study, the distribution of OLC and its metabolites in rat plasma and tissues (stomach, intestine, liver, kidney, spleen, lungs, heart, brain, thyroid and skin) at 1, 2 and 4.5 h after the acute intake of a refined olive oil containing 0.3 mg/mL of OLC was examined by LC-ESI-LTQ-Orbitrap-MS. OLC was only detected in the stomach and intestine samples. Moreover, at 2 and 4.5 h, the concentration in the stomach decreased by 36% and 74%, respectively, and in the intestine by 16% and 33%, respectively. Ten OLC metabolites arising from phase I and phase II reactions were identified. The metabolites were widely distributed in rat tissues, and the most important metabolizing organs were the small intestine and liver. The two main circulating metabolites were the conjugates OLC + OH + CH3 and OLC + H2O + glucuronic acid, which may significantly contribute to the beneficial health effects associated with the regular consumption of extra virgin olive oil. However, more studies are necessary to determine the concentrations and molecular structures of OLC metabolites in human plasma and tissues when consumed with the presence of other phenolic compunds present in EVOO.

Relationship between Apical Periodontitis and Metabolic Syndrome and Cardiovascular Events: A Cross-Sectional Study.

AIM: Both apical periodontitis (AP) and metabolic syndrome (MetS) are associated with atherosclerotic cardiovascular disease (ACVD), the main cause of cardiovascular events. The aim of this study was to investigate the prevalence of AP and the oral inflammatory burden in control subjects and patients suffering cardiovascular events, analyzing the possible association between AP and the oral inflammatory burden with MetS. MATERIALS AND METHODS: Using a cross-sectional design, 83 patients suffering a cardiovascular event were recruited in the study group (SG), and 48 patients without cardiovascular events were included in the control group (CG). Periapical index (PAI) was used to diagnose AP, and total dental index (TDI) was used to assess the total oral inflammatory burden. Diagnosis of MetS was made by meeting three or more American Heart Association Scientific Statement components. RESULTS: In the multivariate logistic regression analysis, the number of teeth with AP (OR = 2.3; 95% C.I. = 1.3-4.3; p = 0.006) and TDI scores (OR = 1.5; 95% C.I. = 1.2-1.9; p = 0.001), significantly correlated with cardiovascular events. MetS was strongly associated (OR = 18.0; 95% C.I. = 6.5-49.7; p = 0000) with cardiovascular events. Higher TDI scores were significantly associated with MetS (OR = 1.3; 95% C.I. = 1.1-1.6; p = 0.003. Neither the number of root-filled teeth (RFT) (OR = 0.9; 95% C.I. = 0.6-1.3; p = 0.61) nor the number of teeth with apical periodontitis (OR = 1.1; 95% C.I. = 0.8-1.7; p = 0.49) were associated with MetS. CONCLUSIONS: Apical periodontitis is significantly associated with cardiovascular events. Total oral inflammatory burden assessed by TDI, but not AP alone, is associated with MetS.

Water oxidation electrocatalysis using ruthenium coordination oligomers adsorbed on multiwalled carbon nanotubes.

Photoelectrochemical cells that utilize water as a source of electrons are one of the most attractive solutions for the replacement of fossil fuels by clean and sustainable solar fuels. To achieve this, heterogeneous water oxidation catalysis needs to be mastered and properly understood. The search continues for a catalyst that is stable at the surface of electro(photo)anodes and can efficiently perform this reaction at the desired neutral pH. Here, we show how oligomeric Ru complexes can be anchored on the surfaces of graphitic materials through CH-π interactions between the auxiliary ligands bonded to Ru and the hexagonal rings of the graphitic surfaces, providing control of their molecular coverage. These hybrid molecular materials behave as molecular electroanodes that catalyse water oxidation to dioxygen at pH 7 with high current densities. This strategy for the anchoring of molecular catalysts on graphitic surfaces can potentially be extended to other transition metals and other catalytic reactions.

Local infiltration analgesia for total knee arthroplasty: Does a mixture of ropivacaine and epinephrine have an impact on hemodynamics? An observational cohort study.

PURPOSE: High doses of local anesthetic administered intra-articularly and peri-articularly during local infiltration analgesia (LIA) for total knee arthroplasty (TKA) may have potential effects on patient hemodynamics. The aim of this study was to know if hemodynamic changes are associated with LIA in patients undergoing TKA. METHODS: In a prospective observational design, elective patients undergoing orthopedic surgery for TKA and treated with LIA consisting of a mixture of ropivacaine (300 mg) and epinephrine (1 mg) were investigated for changes in selected hemodynamic parameters: heart rate (HR), non-invasively registered mean arterial blood pressure (MAP), and incidence of arrhythmias during the perioperative course, consisting of the following periods: period 1. from establishment of spinal anesthesia to prior to LIA administration, period 2. from administration of LIA to before release of ischemia tourniquet, period 3. from release ischemia tourniquet to end of surgery, and period 4. from transfer to the post anesthesia care unit to the ward. Statistical analysis was done with ANOVA-RM for the difference in means in repeated measurements, and with the Tukey Test between pairs. Data are presented as mean ± standard deviation. A P value <0.05 was considered significant. RESULTS: Ninety-nine patients (mean age 77 ± 8 years) were included. HR increased from period 2 to period 3 up to 16% (67 ± 14 to 77 ± 13 bpm, P < 0.001), and from period 2 to period 4 up to 21% (67 ± 14 to 81 ± 12 bpm, P < 0.001). MAP showed no significant changes from period 2 to period 3 (89 ± 13 to 87 ± 13 mmHg, P > 0.50), and from period 2 to period 4 (89 ± 13 to 91 ± 11 mmHg, P > 0.50). No arrhythmias were detected during follow-up. CONCLUSIONS: A mixture of ropivacaine and epinephrine for LIA, despite the high doses administered, does not have a negative impact on hemodynamics.

Effect of Ligand Chelation and Sacrificial Oxidant on the Integrity of Triazole-Based Carbene Iridium Water Oxidation Catalysts.

We report the effect of replacing the pyridine group in the chelating trz Ir-water oxidation catalysts by a benzoxazole and a thiazole moiety. We have also evaluated if the presence of bidentate ligands is crucial for high activities and to avoid the decomposition into undesired heterogeneous layers. The catalytic performance of these benzoxazole/thiazole-triazolidene Ir-complexes in water oxidation was studied at variable pH using either CAN (pH = 1) or NaIO4 (pH = 5.6 and 7). Electrocatalytic experiments indicated that while CAN-mediated water oxidation led to catalyst heterogeneization irrespective of the triazolylidene substituent, periodate as sacrificial oxidant preserved a homogeneously active species. Repetitive additions of sacrificial oxidant indicates higher integrity of the Ir-complex with a thiazole-substituted triazolylidene compared to ligands featuring a benzoxazole as chelating donor or no chelating group at all. Rigid chelation of the thiazole group was also established from stability measurements under highly acidic, oxidizing, and high ionic strength conditions.

Prospective Randomized Study on Stapled Anopexy Height and Its Influence on Recurrence for Hemorrhoidal Disease Treatment.

OBJECTIVES: To know the influence of the stapled line height (SLH) in the recurrence rate and the postoperative disturbances in stapled anopexy (SA) for the treatment of hemorrhoids. DESIGN: Simple randomized double-blind controlled clinical trial. Randomization with closed-envelope technique in two groups with two different SLH. SETTING: Colorectal Surgery Unit. Department of General Surgery. Hospital de Mataró (Barcelona, Spain). PARTICIPANTS: 119 patients with the diagnosis of symptomatic third- and fourth-grade hemorrhoids were included. INTERVENTION: SA was performed with two different SLH: group A, 4.5 cm (58 patients) and group B, 6 cm (61 patients) from the external anal verge. Postoperative disturbances were evaluated by a colorectal surgeon who was blind for the randomization and pain was measured (visual analogic scale) one week and 3 months after surgery. Mean operative time, number of hemostatic stitches performed and resected mucosal area were considered as well. Mean follow-up was 11.05 ± 1.6 years. RESULTS: Differences between the operative time and resected mucosa-submucosa area were not found. The patients of group A needed a significantly higher number of stitches for intraoperative bleeding control along the stapled line. We did not found differences between both groups in terms of postoperative pain neither anorectal disturbances. At the follow-up, persistence of symptomatology was 10.41% in group A and 10.71% in group B, without statistically significance. Neither mortality nor undesirable effects occurred in the series. CONCLUSIONS: SLH do not influence the recurrence rate neither the postoperative evolution in SA. TRIAL REGISTRATION: Clinical Trials NCT03383926.

Organocatalytic vs. Ru-based electrochemical hydrogenation of nitrobenzene in competition with the hydrogen evolution reaction.

The electrochemical reduction of organic contaminants allows their removal from water. In this contribution, the electrocatalytic hydrogenation of nitrobenzene is studied using both oxidized carbon fibres and ruthenium nanoparticles supported on unmodified carbon fibres as catalysts. The two systems produce azoxynitrobenzene as the main product, while aniline is only observed in minor quantities. Although PhNO2 hydrogenation is the favoured reaction, the hydrogen evolution reaction (HER) competes in both systems under catalytic conditions. H2 formation occurs in larger amounts when using the Ru nanoparticle based catalyst. While similar reaction outputs were observed for both catalytic systems, DFT calculations revealed some significant differences related to distinct interactions between the catalytic material and the organic substrates or products, which could pave the way for the design of new catalytic materials.