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In this work, we report, for the first time, the magnetite-functionalization and biological evaluation of eugenol by the co-precipitation method employed only Fe2+ under mild conditions and control from the amount of the incorporated magnetite. Magnetic nanoparticles were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier transform infrared (FTIR), and hydrodynamic size distribution (Zetasizer). SEM images showed that EUG·Fe3O4 is 200 nm in size and similar in shape to a nanoflower. The FTIR spectrum confirmed the presence of characteristic EUG and Fe3O4 bands in the EUG·Fe3O4 sample, while the XRD analysis showed that the magnetite functionalization with eugenol slightly affected the Fe3O4 crystal structure. The in vitro safety profile and cytotoxicity of free eugenol, magnetite pristine, EUG·Fe3O4 1:1, EUG·Fe3O4 1:5, and EUG·Fe3O4 1:10 was investigated using human cell lines (keratinocytes and melanoma). The results demonstrate the high biocompatibility of EUG·Fe3O4 in HaCat cells and the greater specificity for the A375 cell line. Furthermore, the magnetite-functionalized with eugenol decreased the toxic effects of free eugenol on healthy cells. Antibacterial tests were performed in different bacterial strains. The experimental data showed that among the magnetic compounds, the microorganisms were only sensitive to treatment with EUG·Fe3O4 1:1. Regarding the antibiofilm activity assay, it can be observed that only the EUG·Fe3O4 caused a significant decrease in biomass when compared to the positive control. Finally, it can be concluded that EUG·Fe3O4 proves to be a potential candidate for future studies for drug delivery of cancer and bacterial infections treatments.

We assessed hunters’ willingness to participate in a scheme to recover the costs associated with processing diseased game. The results indicated that fifty-one percent of the hunters in a region affected by chronic wasting disease are interested in such a scheme and willing to pay an average of $20 per animal. Their willingness to participate is affected by risk perception, hunting experience, use of processing services, and income. Further, establishing such a market-based scheme would be financially profitable to game processors and helpful to wildlife agencies interested in encouraging hunters’ harvest to reduce herds and facilitate effective disease surveillance.

Deer hunting is a major forest-based recreation activity in the US South. However, the recent discovery of chronic wasting disease (CWD) threatens deer hunting in the region. Stakeholders are interested in understanding how hunters perceive the risk and change their hunting behavior. This study found a significant change in hunters’ concerns after the first deer season since the discovery of CWD in Tennessee, USA. Results also showed that hunters’ short- and long-term intentions to hunt deer in the region were positively related to previous experience of hunting in CWD-affected areas, beliefs in the effectiveness of herd reduction to control CWD, concerns regarding potential decline in deer quality and changes in hunting regulations due to CWD, and trust in wildlife agency action. Hunters who hunt on public land and were concerned with deer and human health risk were less likely to hunt in the CWD region. These results are useful in understanding hunter behavior in response to wildlife disease and identifying variables that may help project immediate as well as long-term change in hunting demand in affected regions.

Toxoplasma gondii is a parasite of significant public health importance. We attempted to detect T. gondii contamination and assess advantages and disadvantages of contamination indicators through surveilling soil, wildlife, cats (Felis catus), and cows (Bos taurus) on a farm in Tennessee, U.S. in 2016 and 2017. Twenty-two soil samples were collected from the farm and subjected to oocyst flotation, DNA extraction, and polymerase chain reaction-restriction fragment length polymorphism (PCR-RFLP) targeting 18S ribosomal RNA (18S rRNA) gene to detect and identify T. gondii. Three samples (13.6%) were positive for the parasite; however, T. gondii DNA was not consistently detected from repeated tests. Blood samples were collected from small mammals, cats, and mesopredators live-trapped on the farm, and serum from 30 of the farm's cows were obtained. Serological testing by the modified agglutination test (MAT; cutoff 1:50) found 2.5% (1/40) of small mammals, 52.9% (9/17) of raccoons (Procyon lotor), and 50% (1/2) of domestic cats were seropositive for T. gondii antibodies. No antibodies were found in 16 opossums (Didelphis virginiana), two skunks (Mephitis mephitis), and 30 cows. Small mammal tissue samples were subjected to PCR-RFLP detection. Four out of 29 (13.7%) tissue samples were positive for T. gondii; however, T. gondii DNA was not consistently detected during repeated PCR-RFLP testing. Our results indicate the ability to detect T. gondii varies greatly by contamination indicator. We found detection of soil oocysts to be challenging, and results suggest limited utility of the method performed. The ability to detect T. gondii in animals was highly variable among species. Our research emphasizes the importance of a holistic approach when surveilling for T. gondii to compensate for shortcomings of each contamination indicator. Future research should be conducted to further investigate the most effective T. gondii surveillance methods and species with increased sample sizes at other agricultural facilities., Graphical abstract Image 1, Highlights • We investigated T. gondii contamination at a farm and the efficacy of T. gondii detection indicators through examining soil, small mammals, mesopredators, domestic cats, and agricultural animals • Soil oocyst detection was low suggesting limited utility of the method performed in the study region • Small rodents and agricultural animals had low detection of T. gondii • Mesopredators (i.e., raccoons and domestic cats) had the greatest affinity for T. gondii detection out of all tested animals and fomites • Multiple indicators of potential contamination should be examined when trying to detect T. gondii

Chronic Wasting Disease (CWD), a neurological disease affecting white-tailed deer has been found in many states including Tennessee. To design effective CWD management programs, stakeholders includ...

The issues of excessive CEO compensation and gender pay gaps garner much attention from management scholars and the general public. In this study, we integrate these topics and explore the complex interdependent nature of how CEOs influence directors’ evaluative perceptions about appropriate levels of CEO compensation and whether female and male CEOs do so in different ways. Drawing from role congruity theory and previous research on executive compensation, we use a configurational approach to identify how CEOs achieve high levels of compensation through different combinations of influence arising from their power, origin, tenure, similarities with evaluators, and organizational conditions. Using fuzzy set qualitative comparative analysis with a matched pair sample of female and male CEOs from 2010 to 2016, we find there are multiple configurations of influence conditions by which female and male CEOs achieve high compensation. Our inductive analysis, unpacking how these configurations differ between female and male CEOs, shows four distinct influence mechanisms: leveraging power and role empathy, trailblazer responsibility, leveraging power and similarity, and leveraging role empathy. These mechanisms highlight the ways influence conditions complement or mutually reinforce one another in different ways for female and male CEOs. Implications for theory and research about the unique challenges female executives face in achieving equitable treatment in the workplace are also discussed.

SummaryWildlife reintroduction projects often face resistance from local residents who see potential conflicts with the species or lack trust or confidence in the agencies and professionals involved in reintroduction. Yet the linkages between trust, confidence, risk perceptions, attitudes towards the species and local support for its reintroduction are not well known. The Dual-Mode Model of Cooperation and Cognitive Hierarchy Model were theoretical frameworks used to shed light on these linkages by exploring the potential roles trust and confidence play as mediators between risk perceptions and attitudes towards, and support for, reintroduced elk in Tennessee (USA). A mail survey of 1005 residents living in the five-county area surrounding the North Cumberland Elk Restoration Zone assessed resident attitudes and risk perceptions towards the reintroduced elk, trust towards the managing wildlife agency and support for continued conservation efforts. A structural equation model revealed that trust and confidence play positive roles in mitigating risk perceptions and improving support for the reintroduction of elk. The findings confirm the roles public trust and confidence play in wildlife reintroductions and should help agencies work towards building local trust and confidence, minimizing risks, improving attitudes and increasing the chances for successful outcomes for the species and people.

Microparticle size, encapsulation efficiency and probiotic viability for resistance to simulated gastrointestinal conditions and stability under different storage conditions for 120 days were studied. The size of the microparticles ranged from 24.4 μm (pectin treatment) to 462 μm (pectin + inulin treatment). The pectin + rice bran and pectin + inulin encapsulation matrices presented the highest encapsulation efficiency, 91.24% and 90.59%, respectively. All treatments provided greater protection to the microorganism after passage through the simulated gastrointestinal tract when compared to the free microorganism. Regarding the viability in different storage conditions, at 25 °C the probiotics remained viable in all treatments for 120 days. At the temperature of −18 °C, the pectin + hi-maize and pectin + rice bran treatments preserved the microorganism viable for 90 days. At 7 °C, the pectin + rice bran treatment remained viable during the 120 days of storage.

Many efforts have been recently made to improve the digestion efficiency by using powerful equipment or by using an auxiliary reagent. In this work, an alternative method is reported, which explores a digestion system based on a single reaction chamber (SRC) technology pressurized with O2 for reducing the amount of acid, without impairing the digestion efficiency. Before digestion, the system was pressurized with compressed air (20 bar, 20% O2) while the temperature was evaluated from 180 up to 270 °C. The procedure was also carried out under O2 pressure (20 bar). For each temperature several acid concentrations were evaluated (0.1 to 3 mol L−1 HNO3), being possible to correlate the effectiveness of each acid concentration with temperature. The proposed method was applied to the simultaneous digestion of several organic matrices with variable content of fat, protein, and carbohydrate (whole milk powder, bovine liver, parsley, and linseed). The residual carbon content was lower than 4% (C lower than 200 mg L−1 in digests), showing the high digestion efficiency of the proposed approach. Up to 250 mg of all food matrices were digested using a sub-stoichiometric amount of HNO3 (1 mol L−1 solution), which was only achieved due to the use of O2 as an auxiliary reagent. Barium, Ca, Cu, Fe, K, Mg, Mn, Na, Sr, and Zn were determined by ICP-OES, and the accuracy was better than 95% for standard reference materials of corn bran, whole milk powder, and bovine liver. It is an important feature, being in agreement with green chemistry recommendations because very low amounts of reagents are required for sample digestion, as well as low amounts of residues are generated.

BackgroundOptimal dosing of methotrexate (MTX) in rheumatoid arthritis (RA) remains challenging. To this end, monitoring of intracellular MTX polyglutamates (MTX-PGs) in red blood cells (RBCs) has been investigated as a potential marker of MTX (non-)response, with contradictory results. As enucleated, non-proliferative cells, mature RBCs lack regulated folate metabolism and are devoid of folylpolyglutamate synthetase (FPGS) activity catalyzing the conversion of MTX to MTX-PGs. Therefore, it has been argued that analysis of MTX-PG in immune-effector cells, represented by peripheral blood mononuclear cells (PBMCs), would be more relevant. However, no prospective study has been performed measuring MTX-PG levels in PBMCs nor in comparison with RBCs.ObjectivesTo investigate the pharmacokinetics of MTX-PG accumulation in RBCs and PBMCs in newly diagnosed RA patients in the early phase of MTX treatment.MethodsIn a clinical prospective cohort study (Methotrexate Monitoring (NTR7149)), RA patients were administered MTX op to 25 mg/week, as described before. (1) At 1, 2, 3 and 6 months after start of therapy, blood was collected and RBCs were isolated by centrifugation and PBMCs after Ficoll density gradient centrifugation. MTX-PG1-6 concentrations in these cells were analyzed using a UPLC-MS/MS method with including custom-made stable isotopes of MTX-PG1-6 as internal standards. (2) UPLC-MS/MS measurements for MTX-PG1-6 were performed with a Waters Acquity BEH C18 column coupled to an AB Sciex 6500+ with the ESI operating on the positive mode. MTX dosing and concomitant treatments were in conformity with clinical practice. (3)Results46 consecutive patients were included in this study; 76% female, mean age: 57.8 years, mean baseline DAS28-ESR: 3.5, as described before. (1) Mean dosage was 10.5 mg (SD: 1.5) at baseline, 16.3 mg (2.5) at month 1, 22.7 mg (4.5) at month 2, 19.5 mg (6.3) at month 3 and 19.1 mg (6.2) at month 6.MTX-PG accumulation in PBMCs and RBCs revealed a disparate profile in both MTX-PG distribution and absolute accumulation levels (Figure 1A/B). Remarkably, MTX-PG distribution in PBMCs was mainly composed of MTX-PG1 (58%), and to a lesser extent MTX-PG2 (27%) and MTX-PG3 (15%). Longer chain MTX-PG4-6 were also detectable in PBMCs, but at lower levels (mean: 4.0 – 6.7 fmol/10^6 cells) than MTX-PG1-3. Moreover, this MTX-PG distribution profile in PBMCs remained constant over a MTX therapy period of 6 months (Figure 1A). The RBC MTX-PG accumulation profile shows mainly MTX-PG1 and lower levels of MTX-PG2-6 at 1 month after the start of therapy. After 3 months of therapy, MTX-PG3 is the main PG-moiety with also MTX-PG4,5,6 being detected. This profile is largely similar after 6 months of therapy. With respect to total intracellular MTX-PG1-6 accumulation, PBMCs had significantly (p1-6 levels in RBCs and PBMCs at all time points were weakly correlated (r=0.41, pFigure 1.Individual MTX-PG concentrations in PBMCs (A) and RBCs (B) during the first 6 months of MTX administration (note the different scaling of the y-axes). At 6 months, 36 patients were still on MTX treatment. Panel (C): Spearman’s correlation plot of total MTX-PGs in RBCs versus PBMCs of all time points.The disparate MTX-PG accumulation and distribution profiles in PBMCs versus RBCs of RA patients may be associated with the shorter life span of PBMCs and the low FPGS activity in RBCs. (4)No significant relation between MTX-PGs and DAS28 was found (data not shown).ConclusionThis study shows that in newly diagnosed RA patients starting MTX therapy, MTX-PG concentrations in PBMCs are significantly 10-20-fold higher than in RBCs over a period of 6 months, with a disparate MTX-PG distribution profile in PBMCs (highest: MTX-PG1) than RBCs (highest: MTX-PG3).References[1]RCF Hebing, Arthr Rheum (2021)[2]E den Boer, Anal Bioanal Chem (2013)[3]J Smolen, Ann Rheum Dis (2020)[4]IB Muller, Ther Drug Monit (2019)AcknowledgementsAcknowledgements: We would like to thank all participating patients and Pfizer (grant 53233663 / WI230458), AmsterdamUMC (AI&II extension grant) and NVKC (Noyons grant 2018)Disclosure of InterestsRenske Hebing Grant/research support from: Pfizer (grant 53233663 / WI230458), NVKC (Netherlands Society for Clinical Chemistry, Noyons grant 2018) and AmsterdamUMC (extension grant), Marry Lin: None declared, Eduard Struys: None declared, Sohaila Mahmoud: None declared, Ittai Muller: None declared, Sandra Heil: None declared, Pieter Griffioen: None declared, WIllem Lems: None declared, Bart van den Bemt Speakers bureau: Pfizer, UCB, Sanofi-Aventis, Galapagos, Amgen and Eli Lilly, Michael Nurmohamed Grant/research support from: Pfizer grant 53233663 / WI230458, Gerrit Jansen: None declared, Robert De Jonge Grant/research support from: NVKC (Netherlands Society for Clinical Chemistry, Noyons grant)

The characterization and identification of inorganic solids present in Brazilian crude oil emulsions were performed after the application of the ASTM D4807 procedure by scanning electron microscopy...

The production and use of nanoparticles (NPs) in different fields increased in the last years. However, some NPs have toxicological properties, making these materials potential emerging pollutants. Therefore, it is important to investigate the uptake, transformation, translocation, and deposition of NPs in plants. In this work, laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) and micro X-ray fluorescence (μ-XRF) were used to investigate the uptake and translocation of La2O3 NPs to stem and leaves of Pfaffia glomerata (Spreng.) Pedersen after in vitro cultivation of plants in the presence of 400 mg L-1 of La2O3 NPs. By using LA-ICP-MS and μ-XRF, image of the spatial distribution of La in the leaves was obtained, where higher concentration of La was observed in the main veins. Differences in the signal profile of La in leaves of plants cultivated in the presence of bulk La2O3 (b-La2O3) and La2O3 NPs were observed. Sharp peaks of La indicated that NPs were transported to the stems and leaves of plants treated with La2O3 NPs. Both LA-ICP-MS and μ-XRF techniques have shown to be useful for detecting NPs in plants, but LA-ICP-MS is more sensitive than μ-XRF and allowed better detection and visualization of La distribution in the whole leaf.

A sample preparation method using only H2O2 in the single reaction chamber system (SRC-H2O2) for medical foods (MFs) digestion and further elemental determination by inductively coupled plasma optical emission spectrometry (ICP OES) was proposed. Digestion of some refractory substances (RS), such as, histidine, linoleic acid, phenylalanine and tryptophan, was also investigated. For the method development important parameters, such as, maximum temperature and pressure of SRC system, volume of H2O2 and sample mass were evaluated. Digestion efficiency was evaluated based on the concentration of residual carbon (RC) of final digests. The optimized method conditions were 1 g of sample, 6 mL of 50% H2O2 and maximum temperature and pressure of 250 °C and 160 bar, respectively. The digests obtained using the optimized conditions presented concentration of RC lower than 720 mg L−1. The accuracy of SRC-H2O2 method was evaluated by analysis of reference material (RM) NIST 8435 (whole milk powder) and by comparison between results obtained using the proposed method and those obtained by digestion with concentrated HNO3 (SRC-HNO3). Significant differences were not observed comparing the results of SRC-H2O2 with reference values of RM and SRC-HNO3. Limits of detection obtained by the proposed method ranged from 0.01 to 88 μg g−1 for all elements determined by ICP OES. SRC-H2O2 method provided digests of individual constituents (sodium caseinate, corn syrup and sunflower oil) of MFs and RS with residual carbon content (RCC) lower than 10% (calculated based on molar and sample masses), except for linoleic acid (RCC of 17%). These same compounds were also digested using SRC-HNO3 method and the RCC values were significantly lower than than those found by SRC-H2O2, except for aromatic amino acids (tryptophan and phenylalanine). The final acidity of digests obtained using SRC-H2O2 was negligible that is convenient for elemental determination using ICP-based techniques and agrees with green analytical chemistry requirements.

In this work, a method based on pyrohydrolysis of high purity nuclear grade alumina and subsequent F determination by ion chromatography (IC) and ion selective electrode (ISE) was developed. After pyrohydrolysis, F was absorbed in a suitable solution (50 mmol L−1 (NH4)2CO3, 50 mmol L−1 NH4OH, and also water were evaluated). Using the selected conditions, it was possible to digest a high sample mass (500 mg) in only 10 min. The following analytical parameters were evaluated: pyrohydrolysis temperature (550 to 1050 °C), time of reaction (2.5 to 20 min), air flow-rate (0.1 to 0.4 L min−1), water flow-rate (0.1 to 1.0 mL min−1), and the use of V2O5 (200 mg), as an auxiliary reagent. Quantitative F recoveries were obtained using air and water flow-rates pumped through the reactor at 0.2 L min-1 and 0.5 mL min−1, respectively. Only water was required as absorbing solution and the use of V2O5, generally recommended for inorganic matrices, was not necessary. Detection limits of 2.0 and 3.6 μg g−1 using IC and ISE, respectively, were obtained. Accuracy was evaluated by recovery tests and also by comparison with the results obtained by high resolution continuum source graphite furnace molecular absorption spectrometry (HR-CS GF MAS). Suitable recoveries for F were obtained (95%) and no statistical difference (95% of confidence level) was observed for the results obtained by HR-CS GF MAS. Pyrohydrolysis allowed the F volatilization in a relatively short time avoiding the use of concentrated reagents and making possible further determination by both analytical techniques (IC or ISE). The pyrohydrolysis method was considered suitable for further F determination, avoiding excessive dilution of digests or matrix matching approaches, making this method a suitable option for routine F determination in nuclear grade alumina samples.

This study microencapsulated anthocyanin compounds extracted from blueberry (Vaccinium spp.) by spray drying using different inlet air temperatures (120, 140 and 160 °C) and wall materials (maltodextrin DE20 and hi-maize) to evaluate the microcapsule characteristics, stability and behavior under simulated gastrointestinal tract conditions. The encapsulation efficiency, moisture content, water activity, particle size, determination of total monomeric anthocyanins, storage stability, morphology and simulated gastrointestinal conditions were analyzed as responses. The microcapsules produced with different wall materials and different inlet temperatures presented an encapsulation efficiency between 74.40 and 85.22%. The microcapsule which presented the lowest degradation constant (0.0060) and longest half-life (115.47 days) during storage was treatment T3 (9% maltodextrin DE20 and 9% hi-maize) at 140 °C. Treatment T3 also presented more uniform particles, ensuring a better protection and retention of the active material. Microencapsulation was effective in protection during storage and improved the delivery of compounds of interest under the simulated gastrointestinal conditions in comparison to the free extract during all the steps that comprised the simulated gastric system.

In this study, we use a mixed methods research design to investigate how national cultural forces may impede or enhance the positive impact of females’ economic and political empowerment on increasing gender diversity of corporate boards. Using both a longitudinal correlation-based methodology and a configurational approach with fuzzy-set qualitative comparative analysis, we integrate theoretical mechanisms from gender schema and institutional theories to develop a mid-range theory about how female empowerment and national culture shape gender diversity on corporate boards around the world. With our configurational approach, we conceptually and empirically model the complexity that is associated with the simultaneous interdependencies, both complementary and substitutive ones, between female empowerment processes and various cultural dimensions. Our findings contribute unique insights to research focused on board gender diversity as well as provide information for firm decision makers and policymakers about possible solutions for addressing the continuing issue of the underrepresentation of women on corporate boards.

Wild hogs (Sus scrofa) are an invasive, non-native species quickly gaining ground on private, as well as public, lands in Tennessee and much of the United States. Wildlife management personnel may benefit from assessing stakeholders’ views towards various management options to control and eradicate wild hogs. A statewide mail survey of 5000 randomly selected landowners in Tennessee counties known to have wild hogs yielded 1620 completed responses (33% response rate). Using this dataset, an index of potential for conflict among landowner groups was computed for each of eleven management options, which varied from leaving the wild hogs alone, to both lethal and non-lethal options. Results indicate varying levels of potential for conflict depending on hunter status, wild hog hunter status, presence of wild hogs on land, percent of income derived from land, and amount of land damage caused by wild hogs. Overall, three management options including leaving the wild hogs alone, allowing sale of wild hogs, and capturing and relocating were found unacceptable whereas many other options including capturing and killing, providing technical assistance to landowners and educating people on preventing damage were found to have high level of acceptability and most consensus among landowner subgroups. Findings will be useful in understanding how support for wild hog control options vary across population segments, and which options are likely to see more or less resistance from certain landowners.

Nutritional support strongly influence the nutritional status of the surgical neoplastic patients. This study aimed to evaluate the influence of food consumption on the perioperative nutritional status of hospitalized patients with neoplasia of the upper (UGIT) and lower (LGIT) gastrointestinal tract. Methods: Observational, longitudinal, and prospective study. Data collected: food consumption, Subjective Global Assessment, anthropometry, laboratory tests. Results: Eighty patients were followed up: 43 (54%) in the UGIT and 37 (46%) in the LGIT. The consumption in the perioperative period was lower than the usual consumption in the UGIT and LGIT groups, respectively, of energy (14.2 ± 6.5; 22.8 ± 11.2 Kcal/kg/d, p < 0.001; 13.6 ± 1.2; 19.0 ± 2.0 Kcal/kg/d; p = 0.014), protein (1.1 ± 0.7; 0.6 ± 0.3 g/kg/d, p < 0.001; 0.8 ± 0.1; 0.5 ± 0.1 g/kg/d; p = 0.058), selenium, zinc and copper. Most patients presented in the UGIT and LGIT groups, respectively, worsening malnutrition and muscle depletion according to the Subjective Global Assessment (61.9%; 51.4%) and hypoalbuminemia, mainly in the UGIT in the postoperative. Conclusion: Low food consumption during the perioperative period associated with prolongation of the postoperative fasting period worsens the nutritional status of patients undergoing surgery of the gastrointestinal tract for neoplasia, especially in the UGIT group.

Rice husk is an agricultural lignocellulosic-rich waste which can be used in the production of second-generation ethanol. A biomass pretreatment is necessary to release structural sugars because of the recalcitrance-related properties of lignin and silicon. The use of a long chain imidazolium ionic liquid (IL), 1-hexadecyl-3-methylimidazolium bromide ([C16MIM][Br−]), for rice husk pretreatment is reported for the first time. The influence of the [C16MIM][Br−]:water ratio and temperature on reducing sugars yield was investigated using an experimental design. Structural, chemical, and morphological modifications were observed by Scanning Electron Microscopy (SEM), X-Ray Diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR) and Thermogravimetric Analysis (TGA). Higher temperature (160°C) and lower water content (1:5, IL:water) improved sugar yield. The validation assay (180°C, 1:20 IL:water ratio, 10% (w/v) of biomass, 12 h) resulted in 38% yield of reducing sugars and 60% dissolution of biomass, whereas untreated biomass showed only 0.18% yield of reducing sugars. The characterization analysis confirmed the changes in rice husk structure and morphology after pretreatment with IL. Rice husk pretreatment with [C16MIM][Br−] resulted in a higher concentration of reducing sugars compared to untreated biomass. Therefore, solid ionic liquids combined with water could be used as an alternative solvent for lignocellulosic biomass pretreatment.

BackgroundPharmacokinetics of methotrexate (MTX) after oral and subcutaneous administration to RA patients differs: MTX levels in plasma and MTX-polyglutamate (MTX-PG) accumulation in erythrocytes are higher during equidosed subcutaneous compared to oral MTX treatment. (1,2) No data are available whether administration route of MTX differentially impacts the intracellular concentrations of MTX-PGs in peripheral blood mononuclear cells (PBMCs) during MTX therapy.ObjectivesTo investigate the pharmacokinetics of MTX-PGs in PBMCs of newly diagnosed RA patients receiving oral or subcutaneous MTX in the early phase (1, 2, 3 and 6 months) of MTX treatment.MethodsIn a clinical prospective cohort study (MeMo study (NTR7149)), RA patients wereadministered oral (n=24) or subcutaneous (n=22) MTX up to 25 mg MTX/week, as described before. (1) At 1, 2, 3 and 6 months after the start of therapy, PBMCs were isolated via Ficoll density gradient centrifugation. Individual MTX-PG forms (MTX-PG1-6) in PBMCs were analyzed by a UPLC-MS/MS method including custom-made stable isotopes of MTX-PG1-6 as internal standards (3). UPLC-MS/MS measurements of the PBMCs were performed with a Waters Acquity BEH C18 column coupled to an AB Sciex 6500+ with the ESI operating on the positive mode. Dosing, concomitant treatments and DAS28-ESR assessments were in conformity with clinical practice. (4)Results46 consecutive patients were included in this study; 76% female, mean age: 57.8 years, BMI: 25.8, smokers: 20%, mean baseline DAS28-ESR: 3.5, as described before. (1) MTX dose at baseline was 10.5 mg (SD: 1.5) for both groups, 15.4 mg (4.4) and 16.8 mg (1.8) at 1 month, 22.8 mg (3.9) and 22.4 mg (5.2) at 2 months, 20.1 mg (6.3) and 20.8 mg (5.6) at 3 months, and 19.7 mg (6.1) and 18.5 mg (6.7) at 6 months for oral and subcutaneous use, respectively. MTX-PG analyses in PBMCs for individual and total MTX-PGs revealed no significant differences between oral and subcutaneous administration groups at 1, 2, 3, and 6 months (Figure 1). Linear regression of LN transformed MTX-PG levels in PBMCs and administration route, corrected for age, baseline DAS28, smoking, BMI, eGFR and MTX dose, showed a trend towards higher MTX-PG levels in PBMCs after subcutaneous MTX administration compared to oral administration (data not shown). MTX-PG distribution in PBMCs was mainly composed of MTX-PG1 (58%), and to a lesser extent MTX-PG2 (27%) and MTX-PG3 (15%). Longer chain MTX-PGs beyond MTX-PG4 were detectable in PBMCs, but at levels lower than MTX-PG1-3 (mean: 4.0 – 6.7 fmol/106 cells). Total MTX-PG accumulation in PBMCs was approximately 10-20 fold higher than in erythrocytes. PBMC accumulation was rather stable, whereas RBC MTX-PG accumulation increased between 1 to 3 months to reach a plateau (Figure 1).Figure 1.Loess regression of MTX-PG concentrations in PBMCs (MTX-PG1-3) and RBCs (MTX-PG1-6) of RA patients during the first 6 months of oral or subcutaneous MTX administration. At 6 months, 18 patients using oral and 18 patients using subcutaneous MTX were still continuing MTX treatment. Means (lines) and SE (grey areas) are depicted.ConclusionThis study demonstrated that MTX-PG accumulation in PBMCs early on in the MTX treatment of RA patients was not significantly different between oral or subcutaneous MTX administration routes.References[1]RCF Hebing et al, Arthritis Rheum (2021); 60:339-348[2]M Hoekstra et al, J Rheumatol (2004); 31:645-8[3]E Den Boer et al, Anal Bioanal Chem (2013); 405: 1673-1681[4]J Smolen et al, Ann Rheum Dis (2020); 79:685-699AcknowledgementsWe would like to thank all participating patients and Pfizer (grant 53233663 / WI230458), NVKC (Noyons grant) and AmsterdamUMC (AI&II extension grant).Disclosure of InterestsRenske Hebing Grant/research support from: Pfizer, grant number 53233663 / WI230458, Amsterdam UMC (AI&II extension grant), NVKC (Netherlands Society for Clinical Chemistry, Noyons grant), Marry Lin: None declared, Eduard Struys: None declared, Sohaila Mahmoud: None declared, Ittai Muller: None declared, WIllem Lems: None declared, Bart van den Bemt Speakers bureau: Pfizer, UCB, Sanofi-Aventis, Galapagos, Amgen and Eli Lilly, Gerrit Jansen: None declared, Robert De Jonge Grant/research support from: NVKC (Netherlands Society for Clinical Chemistry, Noyons grant), Michael Nurmohamed Grant/research support from: Pfizer grant

Coal mining is an anthropogenic stressor that has impacted terrestrial and semi-aquatic wildlife in the Appalachian Plateau since European settlement. Creation of grassland and early-successional habitats resulting from mining in a forested landscape has resulted in novel, non-analog habitat conditions. Depending on the taxa, the extent of mining on the landscape, and reclamation practices, effects have ranged across a gradient of negative to positive. Forest-obligate species such as woodland salamanders and forest-interior birds or those that depend on aquatic systems in their life cycle have been most impacted. Others, such as grassland and early-successional bird species have responded favorably. Some bat species, as an unintended consequence, use legacy deep mines as winter hibernacula in a region with limited karst geology. Recolonization of impacted wildlife often depends on life strategies and species’ vagility, but also on altered or arrested successional processes on the post-surface mine landscape. Many wildlife species will benefit from Forest Reclamation Approach practices going forward. In the future, managers will be faced with decisions about reforestation versus maintaining open habitats depending on the conservation need of species. Lastly, the post-mined landscape currently is the focal point for a regional effort to restore elk (Cervus canadensis) in the Appalachians. Published version

Direct sampling graphite furnace atomic absorption spectrometry (DS-GF AAS) was proposed for Mg and Ca determination in desalted crude oil. A Zeeman-effect background correction system with variable magnetic field was used and measurements were carried out with low and high sensitivity. Pyrolysis and atomization temperatures, calibration with aqueous standards and the effect of sample mass to be introduced into the atomizer were evaluated. The use of chemical modifiers was not necessary for both elements. For Mg determination, two sensitivity conditions (high and low, respectively) were used: i) main absorption line (285.2 nm), 2-field mode (0.8 T) and gas stop flow during the atomization and ii) secondary absorption line (202.6 nm), 2-field mode (0.8 T) and gas stop flow during the atomization. For Ca determination, three low-sensitivity conditions using the main absorption line (422.7 nm) and variable magnetic field were used: i) 3-field dynamic mode (0.6–0.8 T) and gas stop flow during the atomization, ii) 3-field dynamic mode (0.4–0.8 T) and gas stop flow during the atomization and iii) 3-field dynamic mode (0.6–0.8 T) and gas flow during the atomization. The characteristic mass and limit of quantification for the highest sensitivity condition were 0.3 pg and 1.2 ng g−1 for Mg and 4.8 pg and 0.1 µg g−1 for Ca, respectively. For all sensitivity conditions, good linearity (R2 above 0.997) and relative standard deviation below 14% were achieved. Accuracy for DS-GF AAS method was evaluated by results comparison with those obtained by GF AAS after microwave-assisted digestion, which were in agreement. Additionally, recovery tests were carried out and recoveries for both analytes ranged from 92 to 107%. The use of DS-GF AAS provides some advantages such as simplicity, low risk of contamination and up to twelve measurements can be performed per hour.

Deep eutectic solvents (DES) have been used as sustainable media for the synthesis of more efficient nanoparticle-based catalysts. However, the effects of DES deposition on the catalytic activity of metal oxide nanoparticles like TiO2 are unknown. Thus, the goal of this study was to facilitate the deposition of DES onto TiO2 surfaces and investigate how this coating modulates the catalytic activity of TiO2 in the photodecomposition of organic dyes. Results for the thermal and spectroscopic properties of the TiO2 coated with DES in relation to pure materials indicated interactions between these two materials, confirming the deposition of DES onto the TiO2 surface. Different choline chloride : HBD molar ratios had little impact on the thermal stability, phase transitions, crystallization and amorphization of the mixture. In general, the catalytic activity of TiO2 coated with DES was reduced. However, TiO2 covered with ChCl : malonic acid (1 : 2) showed the best catalytic activity and it was better as greater the amount of DES used in the surface deposition.

A simple, rapid, low-cost method was proposed for the imaging of Pseudomonas aeruginosa biofilms on metallic surfaces using an infrared camera. Stainless steel coupons were cooled to generate a thermal gradient in relation to biofilm for active thermography (AT). Both cooling and image acquisition times were optimized and the images obtained with AT were compared with those from scanning electron microscopy. A free software (Thermofilm) was developed for image processing and the results were compared with the software ImageJ, with good agreement (from 87.7 to 103.8%). Images of coupons treated with sanitizer (peracetic acid) were obtained to show the applicability of the proposed method for biofilm studies. All analytical steps could be performed in 3 min in a noncontact, nondestructive, low-cost, portable, and easy-to-use way.

RATIONALE A method for the determination of rare earth elements in carbonatite rocks by inductively coupled plasma mass spectrometry (ICP-MS) was developed. METHODS An alkaline rock, carbonatite, was submitted to ultrasound-assisted extraction (USAE) using an ultrasound bath, a cup horn system or an ultrasound probe. The main USAE parameters were evaluated, such as extraction time (1 to 30 min), extraction temperature (20 to 100°C) and ultrasound amplitude (10 to 100%). For ICP-MS, a desolvation system (APEX-Q) was used to reduce interference in lanthanide determination. To evaluate if the effect of ultrasound improved extraction, experiments were carried out using magnetic stirring (500 rpm) for comparison. RESULTS The temperature and ultrasound amplitude optimized for the method were 70°C and 40%, respectively, using dilute nitric acid (3% v/v). Quantitative analyte recoveries were obtained using an ultrasound bath (25 kHz/100 W) which allowed for the simultaneous extraction of twelve replicates. CONCLUSIONS All the results obtained with the use of ultrasound systems were better than those obtained with mechanical stirring. The extracts were suitable for ICP-MS analysis and the results were in agreement with those obtained by the reference method (using wet acid digestion). Based on the results, the use of USAE can be considered an alternative method for sample preparation of carbonatite rocks, under milder conditions, for further ICP-MS analysis.

The most widely used method for determining the total acid number (TAN) in crude oils is American Society for Testing and Materials (ASTM) D664, which is subject to interference from hydrolyzable salts. This study investigated and determined at which salt concentration NaCl, CaCl2, MgCl2, and SrCl2 significantly interfere with the determination of the TAN in crude oil using the ASTM D664 method. To evaluate the influence of salts on the titration solvent of ASTM D664 and crude oil, pure chloride salts, and two mixtures of these salts, were added to the titration solvents (at 1500–8000 mg kg−1) and water-in-oil emulsions (alpha and gamma). Precipitation was observed during the titrations of these solvents. Analysis of the precipitates via gravimetric analysis, X-ray diffraction, and attenuated total reflection Fourier transform infrared spectroscopy demonstrated that they were composed of Ca(OH)2, Mg(OH)2, and Sr(OH)2. The alpha oil exhibited an increase in acidity from 0.28 up to 2.47 mg KOH g−1 with the chloride salt mixtures, whereas gamma oil exhibited an increase in acidity from 2.26 up to 4.17 mg KOH g−1 with the chloride salt mixtures. One hundred milligrams of CaCl2, MgCl2, or SrCl2 remaining in the oil was sufficient to interfere with the in TAN determination using the ASTM D664 method.

Probiotics are used as dietary supplements with beneficial health effects mainly due to modulating the human intestinal microbiota, although they must withstand adverse environmental conditions and arrive at the target site in sufficient quantities. Co-microencapsulating alternative compounds such as those extracted from blueberries, besides enriching the phytochemical microcapsules, protect the probiotic cells of Lactobacillus rhamnosus. The microcapsules were produced by spray drying using the concentrations of 0% (control; Microencapsulated-0%), 10% (Microencapsulated-10%), 50% (Microencapsulated-50%), and 100% (Microencapsulated-100%) of blueberry extract in relation to the total volume (100 mL). The L. rhamnosus release profile of the microcapsules after exposure to the simulated gastrointestinal system increased at 100% concentration with intestinal counts of 6.97 log CFU/g, while the lowest survival rate was observed using ME-50%. The microcapsules also showed improved thermal resistance compared to free cells, and the ones with 100% extract (ME-100%) had better protective effects. In addition, co-microencapsulation increased the storage stability of probiotics with stability of up to 14 days at −18 °C. In short, this study demonstrates that the co-microencapsulation of the blueberry extract provided positive effects on L. rhamnosus survival and demonstrates its promising application in food.

This study examines the human and relational capital attributes that enable Chief Executive Officers (CEOs) to acquire structural power in Chinese listed firms, and whether gender differences intervene in the attributes that explain this structural power. We show that CEOs with elite education, longer years of education and work experience and more outside directorships are more likely to gain structural power in Chinese listed firms. However, female CEOs are less likely than male CEOs to achieve similar structural power, while only outside directorships, as a proxy for relational capital, compensate for this gender inequality. Employing human capital theory, our study advances the knowledge on CEO leadership by revealing the role of human and relational attributes to explain CEO structural power. Further, our study provides new insights about upward mobility and gender inequality in a fast emerging economy.

Bio-nanosilica was obtained from rice husk thought an alternative ultrasound process and, the material was used to adsorb Crystal Violet (CV) dye from aqueous effluents. Ultrasound modified bio-nanosilica (UM-nSiO2) presented better characteristics than standard nano-silica (nSiO2), demonstrating that ultrasound technique has great potential to generate a promising material for adsorption purposes. The adsorption study was carried out by the kinetic curves, equilibrium isotherms and thermodynamics. Pseudo-second order model was the best to represent the kinetic curves. To represent the equilibrium curves, BET and Freundlich were suitable. Bio-nanosilica attained adsorption capacity of 495 mg g−1 and removal percentage of 98%, being an efficient adsorbent for CV dye.

Rare earth elements (REEs) have several applications but the effects on environment are not well known. Therefore, the aim of this work is to establish a method for direct solid sample analysis by laser ablation-inductively coupled plasma mass spectrometry (LA-ICP-MS) to evaluate the concentration and distribution of REEs in cultivated and non-cultivated soil. Samples were collected in two areas to 40 cm of depth. The LA-ICP-MS method is easy to be implemented and the sample treatment is very fast comprising only its drying, grounding and pressing as a pellet. The accuracy of the method was evaluated by using a certified reference material (BCR 667 – Estuarine Sediment, Institute for Reference Materials and Measurements (IRMM)) where good agreement with the certified values was obtained. Analyte recovery at two levels of concentration (2.5 and 15.0 μg g−1) was also performed and recoveries in the range of 85%–120% were achieved, values that are acceptable for LA-ICP-MS analysis. In general, the concentration of the REEs is higher in the cultivated soil and increased from the surface to deeper layers, which can be a consequence of fertilizer application.

A statistical optimization of tartrazine dye removal process from aqueous solution by heterogeneous photo–Fenton process using Fe2O3-supported ZSM-5 catalyst was performed. ZSM-5 support was prepar...