Influence of interleukin-8 polymorphism on endometriosis-related pelvic pain.

Endometriosis presents a pro-inflammatory microenvironment influenced by cytokines, such as interleukin (IL)-8, which expression may be influenced by genetic polymorphisms. Therefore, we aimed to investigate the role of interleukin (IL)-8 rs4073 polymorphism in endometriosis' development and its related symptoms. A case-control study was conducted with 207 women with endometriosis and 193 healthy controls. Polymorphism was genotyped using a TaqMan validated assay. Associations were evaluated by binary logistic regression, using odds ratios (OR) and 95 % confidence intervals (CI), and P ≤ 0.05 was considered significant. Cases were younger (36 ± 6.8 versus 39 ± 8.4) and had lower body mass index (26.5 ± 5.3 versus 35.7 ± 6.3 Kg/m2) than controls (P < 0.001). Higher prevalence of symptoms and infertility was observed in cases, compared to controls (P < 0.001). Minor allele frequencies of IL-8 rs4073 (T) were 42.3 % and 39.9 % for cases and controls, respectively, and no associations were found between IL and 8 rs4073 polymorphism and endometriosis' prevalence or staging. However, the polymorphism was associated with chronic pelvic pain among cases (OR = 0.54; 95 %CI = 0.29-0.98). The IL-8 rs4073A > T polymorphism may contribute to lower IL-8 expression and, consequently, decrease endometriosis-related pelvic pain. These findings can support the early diagnosis of endometriosis' painful symptoms, preventing its complications, and allowing an individualized treatment.

Tuning the reactivity of carbon surfaces with oxygen-containing functional groups.

Oxygen-containing carbons are promising supports and metal-free catalysts for many reactions. However, distinguishing the role of various oxygen functional groups and quantifying and tuning each functionality is still difficult. Here we investigate the role of Brønsted acidic oxygen-containing functional groups by synthesizing a diverse library of materials. By combining acid-catalyzed elimination probe chemistry, comprehensive surface characterizations, 15N isotopically labeled acetonitrile adsorption coupled with magic-angle spinning nuclear magnetic resonance, machine learning, and density-functional theory calculations, we demonstrate that phenolic is the main acid site in gas-phase chemistries and unexpectedly carboxylic groups are much less acidic than phenolic groups in the graphitized mesoporous carbon due to electron density delocalization induced by the aromatic rings of graphitic carbon. The methodology can identify acidic sites in oxygenated carbon materials in solid acid catalyst-driven chemistry.

Ultrasoft Classical Systems at Zero Temperature.

At low temperatures, classical ultrasoft particle systems develop interesting phases via the self-assembly of particle clusters. In this study, we reach analytical expressions for the energy and the density interval of the coexistence regions for general ultrasoft pairwise potentials at zero temperatures. We use an expansion in the inverse of the number of particles per cluster for an accurate determination of the different quantities of interest. Differently from previous works, we study the ground state of such models, in two and three dimensions, considering an integer cluster occupancy number. The resulting expressions were successfully tested in the small and large density regimes for the Generalized Exponential Model α, varying the value of the exponent.

Electronic modulation of metal-support interactions improves polypropylene hydrogenolysis over ruthenium catalysts.

Ruthenium (Ru) is the one of the most promising catalysts for polyolefin hydrogenolysis. Its performance varies widely with the support, but the reasons remain unknown. Here, we introduce a simple synthetic strategy (using ammonia as a modulator) to tune metal-support interactions and apply it to Ru deposited on titania (TiO2). We demonstrate that combining deuterium nuclear magnetic resonance spectroscopy with temperature variation and density functional theory can reveal the complex nature, binding strength, and H amount. H2 activation occurs heterolytically, leading to a hydride on Ru, an H+ on the nearest oxygen, and a partially positively charged Ru. This leads to partial reduction of TiO2 and high coverages of H for spillover, showcasing a threefold increase in hydrogenolysis rates. This result points to the key role of the surface hydrogen coverage in improving hydrogenolysis catalyst performance.

Factors associated with mortality, length of hospital stay and diagnosis of COVID-19: Data from a field hospital.

BACKGROUND: During the pandemic of COVID-19, phylogenetic changes have been observed in the characteristics of the virus, in the diagnosis and treatment of the disease. The clinical course and the severe form of the disease depends on several factors. This study characterized the beginning setting for patient care of COVID-19 in a referral center in one of the main capital cities of Brazil. In addition, were evaluated the factors associated with mortality, length of stay, and diagnostic outcome. METHODS: A cross-sectional study was conducted during May 2020 (n = 1100). The association of the variables with outcome was evaluated by a multivariable logistic regression model, using odds ratios (OR) and 95 % confidence intervals (CI). RESULTS: Overall, 76 % of patients were COVID-19 positive, and 70 % were diagnosed by RT-qPCR. The majority were male (56 %), and over 52 years old (74 %), 68 % had hypertension, 44 % had diabetes mellitus, and 32 % were obese. The mean length of stay was 10 ± 8 days, which was higher in the 34 % who died (≥14; OR=2; 95 %CI=1.4-4) and who had hypertension (OR=2; 95 %CI=1.3-3) (P < 0.001). The mean length of stay was also higher (P = 0.008) for those patients with pulmonary impairment ≥ 50 % (10.72 ± 8.24), than those with< 50 % (8.98 ± 6.81). Age (>62 and 65 years) was associated with longer hospitalization (OR=2; 95 %CI=1.4-3) and death (OR=6; 95 %CI=3-11). The time of sample collection for RT-qPCR was different between positive and negative tests (P = 0.001), with the time of 4-10 days showing a greater chance for virus detection (OR=2.9; 95 %CI=1.6-5). CONCLUSION: Death was associated with age and pulmonary impairment. The length of hospitalization was associated with age, hypertension, pulmonary impairment and death. The time of sample collection to perform RT-qPCR and the rapid test was associated with a positive result for COVID-19. These results highlight the ongoing challenge of diagnosing, treating, and mitigating the effects caused by the COVID-19 pandemic.

In Situ Tracking of Nonthermal Plasma Etching of ZIF-8 Films.

Surface characterization is critical for understanding the processes used for preparing catalysts, sorbents, and membranes. Nonthermal plasma (NTP) is a process that achieves high reactivity at low temperatures and is used to tailor the surface properties of materials. In this work, we combine the capabilities of infrared reflection absorption spectroscopy (IRRAS) with NTP for the in situ interrogation of zeolitic imidazolate framework-8 (ZIF-8) thin films to probe modifications in the material induced by oxygen and nitrogen plasmas. The IRRAS measurements in oxygen plasma reveal etching of organic ligands with sequential removal of the methyl group and imidazole ring and with the formation of carbonyl moieties (C═O). In contrast, nitrogen plasma induces mild etching and grafting of nitrile groups (-C≡N). Scanning electron microscopy imaging shows that oxygen plasma, at prolonged times, significantly degrades the ZIF-8 film at the grain boundaries. Treatment of ZIF-8 membranes using mild plasma conditions yields a fivefold enhancement for H2/N2 and CO2/CH4 ideal selectivities and an eightfold enhancement for CO2/N2 ideal selectivity. Additionally, the new tools described here can be used for spectroscopic in situ tracking of plasma-induced chemistry on thin films in general.

Solvent-free bottom-up patterning of zeolitic imidazolate frameworks.

Patterning metal-organic frameworks (MOFs) at submicrometer scale is a crucial yet challenging task for their integration in miniaturized devices. Here we report an electron beam (e-beam) assisted, bottom-up approach for patterning of two MOFs, zeolitic imidazolate frameworks (ZIF), ZIF-8 and ZIF-67. A mild pretreatment of metal oxide precursors with linker vapor leads to the sensitization of the oxide surface to e-beam irradiation, effectively inhibiting subsequent conversion of the oxide to ZIFs in irradiated areas, while ZIF growth in non-irradiated areas is not affected. Well-resolved patterns with features down to the scale of 100 nm can be achieved. This developer-free, all-vapor phase technique will facilitate the incorporation of MOFs in micro- and nanofabrication processes.

Ethanol and Water Adsorption in Conventional and Hierarchical All-Silica MFI Zeolites.

Hierarchical zeolites containing both micro- (<2 nm) and mesopores (2-50 nm) have gained increasing attention in recent years because they combine the intrinsic properties of conventional zeolites with enhanced mass transport rates due to the presence of mesopores. The structure of the hierarchical self-pillared pentasil (SPP) zeolite is of interest because all-silica SPP consists of orthogonally intergrown single-unit-cell MFI nanosheets and contains hydrophilic surface silanol groups on the mesopore surface while its micropores are nominally hydrophobic. Therefore, the distribution of adsorbed polar molecules, like water and ethanol, in the meso- and micropores is of fundamental interest. Here, molecular simulation and experiment are used to investigate the adsorption of water and ethanol on SPP. Vapor-phase single-component adsorption shows that water occupies preferentially the mesopore corner and surface regions of the SPP material at lower pressures (P/P 0 < 0.5) while loading in the mesopore interior dominates adsorption at higher pressures. In contrast, ethanol does not exhibit a marked preference for micro- or mesopores at low pressures. Liquid-phase adsorption from binary water-ethanol mixtures demonstrates a 2 orders of magnitude lower ethanol/water selectivity for the SPP material compared to bulk MFI. For very dilute aqueous solutions of ethanol, the ethanol molecules are mostly adsorbed inside the SPP micropore region due to stronger dispersion interactions and the competition from water for the surface silanols. At high ethanol concentrations (C EtOH > 700 g L-1), the SPP material becomes selective for water over ethanol.

Application of the experimental design in the optimization of a procedure for antimony (Sb) remediation in environmental samples employing mesoporous array.

This study describes the sustainable and eco-friendly synthesis of the silica-based mesoporous structure from the use of alternative amorphous silica extracted from rice husk ash (RHA). The mesoporous material was called MCM-48 (RHA), and its application as adsorbent to the antimony (Sb) remediation in environmental samples was tested. The adsorbent was prepared by an efficient and sustainable hydrothermal method, which exhibited an amorphous framework with type IV isotherms and type H1 hysteresis, and surface area, total pore volume, and pore diameter values of 820.9 m2 g-1, 0.6 cm3 g-1, and 3.7 nm, respectively. In addition, the MCM-48 (RHA) exhibited a three-dimensional cubic mesostructure (Ia3d space-group symmetry) with a narrow mesopore distribution, uniform spherical particles, and well-defined architecture. Multivariate optimization using a factorial design (24) was employed in the adsorption tests of Sb. The variables evaluated and the optimum conditions obtained were (i) adsorbent mass (45 mg); (ii) adsorption time (115 min); (iii) pH 2; and (iv) Sb initial concentration of 8 mol L-1. In these conditions, we found a maximum adsorption efficiency of Sb in the order of 95%. The adsorbent material proposed in this study proved to be efficient for Sb remediation in water samples under different experimental conditions. A total of five samples were analyzed and Sb concentrations on the order of 8 ppm were added, in which a removal efficiency of Sb raging between 88 and 96% was obtained for the remediation in real samples. In addition, the low cost of the synthesis of MCM-48 (RHA) in combination with its high and fast adsorption capacities offers a great promise for wastewater remediation, which makes it very attractive for environmental approaches.

Xenon Trapping in Metal-Supported Silica Nanocages.

Xenon (Xe) is a valuable and scarce noble gas used in various applications, including lighting, electronics, and anesthetics, among many others. It is also a volatile byproduct of the nuclear fission of uranium. A novel material architecture consisting of silicate nanocages in contact with a metal surface and an approach for trapping single Xe atoms in these cages is presented. The trapping is done at low Xe pressures and temperatures between 400 and 600 K, and the process is monitored in situ using synchrotron-based ambient pressure X-ray photoelectron spectroscopy. Release of the Xe from the cages occurs only when heating to temperatures above 750 K. A model that explains the experimental trapping kinetics is proposed and tested using Monte Carlo methods. Density functional theory calculations show activation energies for Xe exiting the cages consistent with experiments. This work can have significant implications in various fields, including Xe production, nuclear power, nuclear waste remediation, and nonproliferation of nuclear weapons. The results are also expected to apply to argon, krypton, and radon, opening an even more comprehensive range of applications.

Few-Unit-Cell MFI Zeolite Synthesized using a Simple Di-quaternary Ammonium Structure-Directing Agent.

Synthesis of a pentasil-type zeolite with ultra-small few-unit-cell crystalline domains, which we call FDP (few-unit-cell crystalline domain pentasil), is reported. FDP is made using bis-1,5(tributyl ammonium) pentamethylene cations as structure directing agent (SDA). This di-quaternary ammonium SDA combines butyl ammonium, in place of the one commonly used for MFI synthesis, propyl ammonium, and a five-carbon nitrogen-connecting chain, in place of the six-carbon connecting chain SDAs that are known to fit well within the MFI pores. X-ray diffraction analysis and electron microscopy imaging of FDP indicate ca. 10 nm crystalline domains organized in hierarchical micro-/meso-porous aggregates exhibiting mesoscopic order with an aggregate particle size up to ca. 5 µm. Al and Sn can be incorporated into the FDP zeolite framework to produce active and selective methanol-to-hydrocarbon and glucose isomerization catalysts, respectively.

Electron beam induced modification of ZIF-8 membrane permeation properties.

Modification of the gas permeation properties of ZIF-8 membranes using electron beam irradiation is reported. 3.8 and 3.2 fold enhancements in ideal selectivity for CO2/N2 and CO2/CH4 can be achieved with less than 1 min exposure time.

Multiway Calibration Strategies in Laser-Induced Breakdown Spectroscopy: A Proposal.

In this study, a new approach to laser-induced breakdown spectroscopy (LIBS) data modeling using multiway algorithms was investigated. Two case studies, parallel factor analysis (PARAFAC) and unfolded-partial least-squares with residual bilinearization (U-PLS/RBL) algorithms were used in (1) the determination of Al, Cu, and Fe in samples of reference material of printed circuit board (PCB) from electronic waste and (2) the determination of Ca, K, and Mg in samples of a human mineral supplement, where depth was used to obtain multidimensional data in the first case and delay-time in the second. In addition, univariate calibration was applied and compared with the multiway approaches. In all cases, the calibration data set was prepared from salts. PARAFAC showed satisfactory results in the first study, with low prediction errors and good accuracy for most samples, and the U-PLS/RBL algorithm presented the best performance for mineral supplement samples.

ZIF-8 Membrane Permselectivity Modification by Manganese(II) Acetylacetonate Vapor Treatment.

Vapor-phase treatment of ZIF-8 membranes with manganese(II) acetylacetonate (Mn(acac)2 ) allows permselectivity tuning. Propylene/propane selectivity increases from 31 to 210 after the Mn(acac)2 treatment at 165 °C for 30 min, while selectivities increase from 14.6 to 242 for H2 /CH4 , from 2.9 to 38 for CO2 /CH4 , from 2.4 to 29 for CO2 /N2 , and from 2.9 to 7.5 for O2 /N2 , after Mn(acac)2 treatment at 175 °C for 30 min. Stable equimolar propylene/propane mixture selectivity of 165 at ambient temperature and 4 bar equimolar feed with a propylene flux of 8.3×10-4  mol m-2 s-1 is established. A control experiment excludes thermal treatment alone causing these changes. XPS analysis reveals the presence of Mn(acac)2 on the outer surface of the vapor-treated ZIF-8 membranes while no other changes are detectable by X-ray diffraction and infrared spectroscopy.

Forensic analysis of hand-written documents using laser-induced breakdown spectroscopy (LIBS) and chemometrics.

With the use of Laser Induced Breakdown Spectroscopy (LIBS), fast and semi non-destructive elemental analysis of ball-point pen writings has been performed directly from paper surfaces, aiming to obtain maximum differentiation between pens with a minimum number of pulses. The instrumental variables, the delay time, laser pulse energy and number of pulses per point, were evaluated through factorial design and optimum values were obtained through a quadratic regression model. Several atomic emission lines were tested as fingerprints in order to improve the differentiation between the tested inks and the range of 212-228 and 324-328 nm, which corresponds to Cu emission, demonstrated to be the best alternative as a discriminatory factor for two pens of the same color. However, the background contribution of cheque paper limited the multielement profile of the technique. Seventeen different pens were analyzed. Principal Component Analysis (PCA) treatment was used to classify the samples in clusters and to assemble hyperspectral images in order to obtain visual differentiation of the inks in a scores map. The results obtained by LIBS analysis were verified by microwave-assisted digestion of inks and analysis by ICP OES. Lastly, a real situation test was conducted where a forged document was analyzed by the proposed methodology as an alternative to distinguish between two inks of the same color, originating from different pens. For this proof of concept study, seventeen samples were evaluated, but further studies related to heterogeneity between pulses and samples should be carried out.

Phosphonate-Modified UiO-66 Brønsted Acid Catalyst and Its Use in Dehydra-Decyclization of 2-Methyltetrahydrofuran to Pentadienes.

Phosphorus-modified all-silica zeolites exhibit activity and selectivity in certain Brønsted acid catalyzed reactions for biomass conversion. In an effort to achieve similar performance with catalysts having well-defined sites, we report the incorporation of Brønsted acidity to metal-organic frameworks with the UiO-66 topology, achieved by attaching phosphonic acid to the 1,4-benzenedicarboxylate ligand and using it to form UiO-66-PO3 H2 by post-synthesis modification. Characterization reveals that UiO-66-PO3 H2 retains stability similar to UiO-66, and exhibits weak Brønsted acidity, as demonstrated by titrations, alcohol dehydration, and dehydra-decyclization of 2-methyltetrahydrofuran (2-MTHF). For the later reaction, the reported catalyst exhibits site-time yields and selectivity approaching that of phosphoric acid on all-silica zeolites. Using solid-state NMR and deprotonation energy calculations, the chemical environments of P and the corresponding acidities are determined.

ZIF-8 Membrane Separation Performance Tuning by Vapor Phase Ligand Treatment.

Vapor phase ligand treatment (VPLT) of 2-aminobenzimidazole (2abIm) for 2-methylimidazole (2mIm) in ZIF-8 membranes prepared by two different methods (LIPS: ligand induced permselectivation and RTD: rapid thermal deposition) results in a notable shift of the molecular level cut-off to smaller molecules establishing selectivity improvements from ca. 1.8 to 5 for O2 /N2 ; 2.2 to 32 for CO2 /CH4 ; 2.4 to 24 for CO2 /N2 ; 4.8 to 140 for H2 /CH4 and 5.2 to 126 for H2 /N2 . Stable (based on a one-week test) oxygen-selective air separation performance at ambient temperature, 7 bar(a) feed, and 1 bar(a) sweep-free permeate with a mixture separation factor of 4.5 and oxygen flux of 2.6×10-3  mol m-2 s-1 is established. LIPS and RTD membranes exhibit fast and gradual evolution upon a 2abIm-VPLT, respectively, reflecting differences in their thickness and microstructure. Functional reversibility is demonstrated by showing that the original permeation properties of the VPLT-LIPS membranes can be recovered upon 2mIm-VPLT.

ssDNA-amphiphile architecture used to control dimensions of DNA nanotubes.

Controlling the dimensions of DNA nanotubes is of great interest as they can be used in different applications ranging from functional elements in nanodevices to carriers for drug delivery. ssDNA-amphiphiles composed of a ssDNA headgroup, a hydrophobic dialkyl tail and a polycarbon spacer between the tail and the headgroup, self-assemble into hollow DNA nanotubes by forming bilayer nanotapes that transition from twisted nanotapes, to helical nanotapes, to nanotubes. The presence of the DNA nanotubes is verified via cryo-TEM and SAXS. We further explore the effect of the ssDNA secondary structure and tail length on the assembly of the ssDNA-amphiphiles. We demonstrate that the presence of intermolecular G-quadruplexes in the ssDNA sequence dictates the nanotube length. The nanotube diameter is controlled by the hydrophobic tail length, and coarse-grained molecular dynamics simulations are employed to elucidate the tail design impact on assembly.

Vapor- and Liquid-Phase Adsorption of Alcohol and Water in Silicalite-1 Synthesized in Fluoride Media.

In this work, batch-adsorption experiments and molecular simulations are employed to probe the adsorption of binary mixtures containing ethanol or a linear alkane-1,n-diol solvated in water or ethanol onto silicate-1. Since the batch-adsorption experiments require an additional relationship to determine the amount of solute (and solvent adsorbed, as only the bulk liquid reservoir can be probed directly, molecular simulations are used to provide a relationship between solute and solvent adsorption for input to the experimental bulk measurements. The combination of bulk experimental measurements and simulated solute-solvent relationship yields solvent and solute loadings that are self-consistent with simulation alone, and allow for an assessment of the various assumptions made in literature. At low solution concentrations, the solute loading calculated is independent of the assumption made. At high concentrations, a negligent choice of assumption can lead to systematic overestimation or underestimation of calculated solute loading.

Understanding the unique sorption of alkane-α, ω-diols in silicalite-1.

Adsorption equilibria of alkane-α, ω-diols (propane-1,3-diol, butane-1,4-diol, pentane-1,5-diol, and hexane-1,6-diol) from aqueous solution onto an all-silica zeolite of the type mordenite framework inverted (MFI, also known as silicalite-1) are obtained by simulations and experiments at T = 323 K and also for pentane-1,5-diol (C5) at 348 and 383 K. After an initial slow rise, isotherms at T = 323 K exhibit steep changes in loading, reaching saturation at 10, 9, 8, and 7 molec/uc as the number of carbon atoms of the diols increases from 3 to 6. The abrupt change in loading corresponds to a minimum in the free energy of adsorption (from vapor to zeolite) that is associated with a rapid rise in the number of hydrogen bonds per sorbate molecule due to the formation of large clusters. For C5 at low loading, the centers-of-mass primarily occupy the channel intersections with oxygens oriented along the straight channels where intermolecular hydrogen bonds are formed. At saturation loading, the C5 centers-of-mass instead occupy the straight and zig-zag channels, and nearly all C5 molecules are involved in a percolating hydrogen-bonding network (this also occurs for C6). With increasing temperature, the C5 isotherm decreases in steepness as the minimum in free energy of adsorption decreases in depth and a less-ordered structure of the adsorbed molecules results in a lower number of diol-diol hydrogen bonds. However, the C5 isotherm does not shift significantly in concentration of the adsorption onset, as the free energies of solvation and adsorption increase by similar and compensating amounts. At T = 323 and 348 K, the steep change for the C5 adsorption isotherm is found to be a phase transition (as indicated by a bimodal distribution of unit cell occupancies at intermediate loading) from a less-dense phase with only small hydrogen-bonded clusters to an ordered solid phase with loadings of 8 molec/uc. At T = 383 K, the sorbates are less ordered, the distribution of occupancies becomes unimodal at intermediate loading, and the loading rises more gradually with concentration. Several different enhanced sampling methods are utilized for these simulations.