Kinetic modeling of α-hydrogen abstractions from unsaturated and saturated oxygenate compounds by carbon-centered radicals.

Hydrogen abstractions are important elementary reactions in a variety of reacting media at high temperatures in which oxygenates and hydrocarbon radicals are present. Accurate kinetic data are obtained from CBS-QB3 ab initio (AI) calculations by using conventional transition-state theory within the high-pressure limit, including corrections for hindered rotation and tunneling. From the obtained results, a group-additive (GA) model is developed that allows the Arrhenius parameters and rate coefficients for abstraction of the α-hydrogen from a wide range of oxygenate compounds to be predicted at temperatures ranging from 300 to 1500 K.

TAP study of toluene total oxidation over a Co3O4/La-CeO2 catalyst with an application as a washcoat of cordierite honeycomb monoliths.

The total oxidation of toluene was studied over a Co3O4/La-CeO2 catalyst in a Temporal Analysis of Products (TAP) set-up in the temperature range 713 K to 873 K in the presence and absence of dioxygen. It has been demonstrated that the reaction proceeds via a Mars-van Krevelen mechanism. The reaction rate increased 8.

Kinetic modeling of hydrogen abstractions involving sulfur radicals.

One of the requisites for the development of detailed reaction networks is the availability of accurate kinetic data. Group additivity based models linking the Arrhenius parameters to structural characteristics of the transition state have proven to be a valuable tool to obtain those data. In this work, group additivity values are presented to allow a broad range of CH and SH hydrogen abstraction reactions by S radicals to be modeled.

Relationship between CT air trapping criteria and lung function in small airway impairment quantification.

Background: Small airways are regarded as the elective anatomic site of obstruction in most chronic airway diseases. Expiratory computed tomography (CT) is increasingly used to assess obstruction at this level but there is no consensus regarding the best quantification method. We aimed to evaluate software-assisted CT quantification of air trapping for assessing small airway obstruction and determine which CT criteria better predict small airway obstruction on single breath nitrogen test (SBNT).

Electroablation: a method for neurectomy and localized tissue injury.

Background: Tissue injury has been employed to study diverse biological processes such as regeneration and inflammation. In addition to physical or surgical based methods for tissue injury, current protocols for localized tissue damage include laser and two-photon wounding, which allow a high degree of accuracy, but are expensive and difficult to apply. In contrast, electrical injury is a simple and inexpensive technique, which allows reproducible and localized cell or tissue damage in a variety of contexts.

Morphology, projection pattern, and neurochemical identity of Cajal's "centrifugal neurons": the cells of origin of the tectoventrogeniculate pathway in pigeon (Columba livia) and chicken (Gallus gallus).

The nucleus geniculatus lateralis pars ventralis (GLv) is a prominent retinal target in all amniotes. In birds, it is in receipt of a dense and topographically organized retinal projection. The GLv is also the target of substantial and topographically organized projections from the optic tectum and the visual wulst (hyperpallium).

Influence of spherical aberration, stimulus spatial frequency, and pupil apodisation on subjective refractions.

Purpose: To test competing hypotheses (Stiles Crawford pupil apodising or superior imaging of high spatial frequencies by the central pupil) for the pupil size independence of subjective refractions in the presence of primary spherical aberration.

Methods: Subjective refractions were obtained with a variety of test stimuli (high contrast letters, urban cityscape, high and low spatial frequency gratings) while modulating pupil diameter, levels of primary spherical aberration and pupil apodisation. Subjective refractions were also obtained with low-pass and high-pass stimuli and using 'darker' and 'sharper' subjective criteria.

Healthcare program for sex workers: a public health priority.

Objective: The objective of this study was to propose a model of health care for sexual workers (SWs) and transvestites (Ts) groups who were historically excluded from health services.

Materials And Methods: A prospective descriptive/analytical study with an intervention stage was performed, focusing on the health status of SWs and Ts. Access to health system, inclusion into social programs, beneficiaries' participation, and rate of risk behaviors were variables measured before and after intervention that consist in a program based on promotion/prevention activities and complete health care service suitable to SW-T needs.

Evaluation of a global algorithm for wavefront reconstruction for Shack-Hartmann wave-front sensors and thick fundus reflectors.

Purpose: Conventional aberration analysis by a Shack-Hartmann aberrometer is based on the implicit assumption that an injected probe beam reflects from a single fundus layer. In fact, the biological fundus is a thick reflector and therefore conventional analysis may produce errors of unknown magnitude. We developed a novel computational method to investigate this potential failure of conventional analysis.

Impact of preoperative marking coils on surgical and pathologic management of impalpable lung nodules.

Background: The management of occult lung lesions, particularly subsolid opacities, is a new challenge because they are difficult to localize during surgery and the number of lesions detected by computed tomography (CT) is increasing.

Methods: Between February 2008 and December 2011, preoperative CT-guided marking with coils was systematically carried out to localize presumed impalpable nodules before video-assisted thoracoscopic surgery (VATS). The procedure feasibility, reliability, and safety as well as its impact on the resection volume and on the pathologic examination strategy were examined.

Astigmatism impact on visual performance: meridional and adaptational effects.

Purpose: Astigmatic subjects are adapted to their astigmatism and perceptually recalibrate upon its correction. However, the extent to which prior adaptation to astigmatism affects visual performance, whether this effect is axis dependent, and the time scale of potential changes in visual performance after astigmatism correction are not known. Moreover, the effect of possible positive interactions of aberrations (astigmatism and coma) might be altered after recalibration to correction of astigmatism.

Group additive values for the gas-phase standard enthalpy of formation, entropy and heat capacity of oxygenates.

A complete and consistent set of 60 Benson group additive values (GAVs) for oxygenate molecules and 97 GAVs for oxygenate radicals is provided, which allow to describe their standard enthalpies of formation, entropies and heat capacities. Approximately half of the GAVs for oxygenate molecules and the majority of the GAVs for oxygenate radicals have not been reported before. The values are derived from an extensive and accurate database of thermochemical data obtained by ab initio calculations at the CBS-QB3 level of theory for 202 molecules and 248 radicals.

New potential therapeutic approach for the treatment of B-Cell malignancies using chlorambucil/hydroxychloroquine-loaded anti-CD20 nanoparticles.

Current B-cell disorder treatments take advantage of dose-intensive chemotherapy regimens and immunotherapy via use of monoclonal antibodies. Unfortunately, they may lead to insufficient tumor distribution of therapeutic agents, and often cause adverse effects on patients. In this contribution, we propose a novel therapeutic approach in which relatively high doses of Hydroxychloroquine and Chlorambucil were loaded into biodegradable nanoparticles coated with an anti-CD20 antibody.

Distal airway impairment in obese normoreactive women.

Background: Asthma-like symptoms are frequent in overweight and obesity, but the mechanism is unclear when airway hyperresponsiveness (AHR) is lacking. In this study, we focused on obese women with a clinical suspicion of asthma but negative methacholine challenge and tested distal airway hyperreactivity, explored by Forced Vital Capacity dose-response slope (FVC DRS).

Objective: To question AHR at the distal airway level in obese women.

Controlled synthesis of Mn3O4 nanoparticles in ionic liquids.

This work describes a simple one-step synthesis of Mn3O4 nanoparticles by thermal decomposition of [Mn(acac)2] (acac = acetylacetonate) using imidazolium ionic liquids (ILs) and a conventional solvent, oleylamine, for comparison. The Mn3O4 nanoparticles were characterized by XRD, ATR-FTIR, TEM, Raman, UV/VIS and magnetometry techniques. The addition of 1-n-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide IL (BMI·NTf2) yielded a smaller particle size (9.

Benzene adsorption on binary Pt3M alloys and surface alloys: a DFT study.

Benzene adsorption on Pt3M/Pt(111) surfaces and Pt3M(111) bulk alloys (M = Fe, Co, Ni, Cu, Pd, Ag, Au) is analyzed using density functional theory calculations on 4-layered slabs in the framework of catalyst development for aromatics hydrogenation. Segregation in the top layers was allowed for, accounting for the actual stoichiometric composition of the top layers rather than using simplified 'skin' or 'sandwich' structures. On the surfaces that do not segregate (M = Pd, Ag, Au), the preferred benzene adsorption site is the hollow Pt3-hcp(0) site.

Kinetics of homolytic substitutions by hydrogen atoms at thiols and sulfides.

Thermodynamic and kinetic data in the temperature range 300-1500 K are calculated for 94 homolytic substitution reactions by a hydrogen atom at thiols and sulfides with the CBS-QB3//BMK/6-311G(2d,d,p) method. The studied reactions were found to proceed according to a one-step mechanism. A group additivity (GA) method is presented to model the Arrhenius parameters of this reaction family.

[About non-specific prophylaxis of infections typical for organized groups].

Respiratory tract infections and pyodermia are typical for personnel doing military service under conscription. Risk of progression of these infections is connected with activation of carry-over of causative agents among military personnel during replacement and decrease in immunity of conscripts. Usage of medication "Karmolis Kapli" for the purpose of prophylaxis allows to reduce cases of respiratory tract infections among the military personnel.

[Acute kidney injury secondary to steroid-induced tumor lysis in an adolescent with acute lymphoblastic leukemia: role of urinary alkalinisation and peritoneal dialysis].

An adolescent with acute lymphoblastic leukemia developed an early and severe tumor lysis syndrome with acute kidney injury after a low and single dose of steroids. Renal dysfunction was attributed primarily to phosphate nephropathy with nephrocalcinosis due to extreme elevations of phosphate in blood. Urinary alkalinization probably contributed to this development.

[About the estimation of non specific protective effect of vaccination against infections actual for military personnel].

Flue and other respiratory diseases morbidity of servicemen of training students are researched. Epidemiological and economic effectiveness of flue vaccine "Bakcuspun" (Vaksigrip) is estimated. Its non-specific protective effect in case of acute respiratory diseases and pyodermia is shown.

Laminar segregation of GABAergic neurons in the avian nucleus isthmi pars magnocellularis: a retrograde tracer and comparative study.

The isthmic complex is part of a visual midbrain circuit thought to be involved in stimulus selection and spatial attention. In birds, this circuit is composed of the nuclei isthmi pars magnocellularis (Imc), pars parvocellularis (Ipc), and pars semilunaris (SLu), all of them reciprocally connected to the ipsilateral optic tectum (TeO). The Imc conveys heterotopic inhibition to the TeO, Ipc, and SLu via widespread γ-aminobutyric acid (GABA)ergic axons that allow global competitive interactions among simultaneous sensory inputs.

Wood-derived olefins by steam cracking of hydrodeoxygenated tall oils.

Tall oil fractions obtained from Norwegian spruce pulping were hydrodeoxygenated (HDO) at pilot scale using a commercial NiMo hydrotreating catalyst. Comprehensive two dimensional gas chromatography (GC×GC) showed that HDO of both tall oil fatty acids (TOFA) and distilled tall oil (DTO) produced highly paraffinic hydrocarbon liquids. The hydrotreated fractions also contained fatty acid methyl esters and norabietane and norabietatriene isomers.

Synthesis, characterization and sorption properties of NH2-MIL-47.

An amino functionalized vanadium-containing Metal Organic Framework, NH(2)-MIL-47, has been synthesized by a hydrothermal reaction in an autoclave. Alternatively, a synthesis route via microwave enhanced irradiation has been optimized to accelerate the synthesis. The NH(2)-MIL-47 exhibits the same topology as MIL-47, in which the V center is octahedrally coordinated.

Kinetics of α hydrogen abstractions from thiols, sulfides and thiocarbonyl compounds.

Hydrogen abstraction reactions involving organosulfur compounds play an important role in many industrial, biological and atmospheric processes. Despite their chemical relevance, little is known about their kinetics. In this work a group additivity model is developed that allows predicting the Arrhenius parameters for abstraction reactions of α hydrogen atoms from thiols, alkyl sulfides, alkyl disulfides and thiocarbonyl compounds by carbon-centered radicals at temperatures ranging from 300 to 1500 K.