Thermodynamic study of racemic ibuprofen separation by liquid chromatography using cellulose-based stationary phase

Ibuprofen is a nonsteroidal anti-inflammatory drug (NSAID), also known for its significant antipyretic and analgesic properties. This chiral drug is commercialized in racemic form; however, only S-(+)-ibuprofen has clinical activities. In this paper the effect of temperature change (from 288.15 to 308.15 K) on the ibuprofen resolution was studied. A column ( mm) packed with tris(3,5-dimethylphenylcarbamate) was used to obtain the thermodynamic parameters, such as enthalpy change (), entropy change (), variation enthalpy change (), variation entropy change (), and isoenantioselective temperature (). The mobile phase was a combination of hexane (99%), isopropyl alcohol (1%), and TFA (0.1%), as an additive. The conditions led to a selectivity of 1.20 and resolution of 4.55. The first peak, R-(−)-ibuprofen, presented an enthalpy change of 7.21 kJ/mol and entropy change of 42.88 kJ/K·mol; the last peak, S-(+)-ibuprofen, has an enthalpy change of 8.76 kJ/mol and 49.40 kJ/K·mol of entropy change2016CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICO - CNPQsem informaçã

Brainwave nets: Are sparse dynamic models susceptible to brain manipulation experimentation?

© Copyright © 2020 Nascimento, Pinto-Orellana, Leite, Edwards, Louzada and Santos. Sparse time series models have shown promise in estimating contemporaneous and ongoing brain connectivity. This paper was motivated by a neuroscience experiment using EEG signals as the outcome of our established interventional protocol, a new method in neurorehabilitation toward developing a treatment for visual verticality disorder in post-stroke patients. To analyze the [complex outcome measure (EEG)] that reflects neural-network functioning and processing in more specific ways regarding traditional analyses, we make a comparison among sparse time series models (classic VAR, GLASSO, TSCGM, and TSCGM-modified with non-linear and iterative optimizations) combined with a graphical approach, such as a Dynamic Chain Graph Model (DCGM). These dynamic graphical models were useful in assessing the role of estimating the brain network structure and describing its causal relationship. In addition, the class of DCGM was able to visualize and compare experimental conditions and brain frequency domains [using finite impulse response (FIR) filter]. Moreover, using multilayer networks, the results corroborate with the susceptibility of sparse dynamic models, bypassing the false positives problem in estimation algorithms. We conclude that applying sparse dynamic models to EEG data may be useful for describing intervention-relocated changes in brain connectivity

Splitting of multiple hydrogen molecules by bioinspired diniobium metal complexes: a DFT study

Splitting of molecular hydrogen (H2) into bridging and terminal hydrides is a common step in transition metal chemistry. Herein, we propose a novel organometallic platform for cleavage of multiple H2 molecules, which combines metal centers capable of stabilizing multiple oxidation states, and ligands bearing positioned pendant basic groups. Using quantum chemical modeling, we show that low-valent, early transition metal diniobium(II) complexes with diphosphine ligands featuring pendant amines can favorably uptake up to 8 hydrogen atoms, and that the energetics are favored by the formation of intramolecular dihydrogen bonds. This result suggests new possible strategies for the development of hydrogen scavenger molecules that are able to perform reversible splitting of multiple H2 molecules

Erosion losses from runoff: interaction of soil cover and erosion control practice

O escoamento da água oriunda das terras agricultadas é o principal fator poluente dos mananciais hídricos nas áreas rurais. Devido a esse fato, faz-se necessário o desenvolvimento e a aplicação de tecnologias que venham a reduzir descargas de resíduos indesejáveis. Nesse sentido, conduziu-se um experimento na área experimental do Departamento de Engenharia Rural - ESALQ/USP, Piracicaba - SP, com o objetivo de avaliar o efeito de diferentes condições de solo, (feijão, gramínea e solo nu) e diferentes práticas de controle de erosão (sulco de infiltração, terraço de infiltração e sem práticas de controle de erosão), buscando-se estimar o escoamento superficial. O delineamento estatístico adotado foi o em blocos aleatorizados, em esquema fatorial 3x3, perfazendo 9 tratamentos com 3 repetições. O período de coleta de dados pluviométricos foi de 06 de dezembro de 2007 a 11 de abril de 2008; para isto, utilizou-se de um pluviômetro, com 21,1 cm de diâmetro, instalado na área experimental. Observando-se as perdas de água, em relação às estruturas, tem-se em ordem decrescente de eficiência: Terraço, Sulco e Rampa; e com relação às coberturas, tem-se em ordem decrescente de eficiência: Feijão, Capim e Solo Nu

Low energy elastic and electronically inelastic electron scattering from biomolecules.

Reactions initiated by collisions with low-energy secondary electrons has been found to be the prominent\ud mechanism toward the radiation damage on living tissues through DNA strand breaks. Now it is widely accepted\ud that during the interaction with these secondary species the selective breaking of chemical bonds is triggered\ud by dissociative electron attachment (DEA), that is, the capture of the incident electron and the formation\ud of temporary negative ion states [1,2,3]. One of the approaches largely used toward a deeper understanding\ud of the radiation damage to DNA is through modeling of DEA with its basic constituents (nucleotide bases,\ud sugar and other subunits). We have tried to simplify this approach and attempt to make it comprehensible\ud at a more fundamental level by looking at even simple molecules. Studies involving organic systems such as\ud carboxylic acids, alcohols and simple ¯ve-membered heterocyclic compounds are taken as starting points for\ud these understanding. In the present study we investigate the role played by elastic scattering and electronic\ud excitation of molecules on electron-driven chemical processes. Special attention is focused on the analysis of\ud the in°uence of polarization and multichannel coupling e®ects on the magnitude of elastic and electronically\ud inelastic cross-sections. Our aim is also to investigate the existence of resonances in the elastic and electronically\ud inelastic channels as well as to characterize them with respect to its type (shape, core-excited or Feshbach),\ud symmetry and position. The relevance of these issues is evaluated within the context of possible applications\ud for the modeling of discharge environments and implications in the understanding of mutagenic rupture of DNA\ud chains. The scattering calculations were carried out with the Schwinger multichannel method (SMC) [4] and\ud its implementation with pseudopotentials (SMCPP) [5] at di®erent levels of approximation for impact energies\ud ranging from 0.5 eV to 30 eV.\ud References\ud [1] B. Boudai®a, P. Cloutier, D. Hunting, M. A. Huels and L. Sanche, Science 287, 1658 (2000). [2] X. Pan, P.\ud Cloutier, D. Hunting and L. Sanche, Phys. Rev. Lett. 90, 208102 (2003). [3] F. Martin, P. D. Burrow, Z. Cai,\ud P. Cloutier, D. Hunting and L. Sanche, Phys. Rev. Lett. 93, 068101 (2004). [4] K. Takatsuka and V. McKoy,\ud Phys. Rev. A 24, 2437 (1981); ibid. Phys. Rev. A 30, 1734 (1984). [5] M. H. F. Bettega, L. G. Ferreira and\ud M. A. P. Lima, Phys. Rev. A 47, 1111 (1993)

Hydrogenated Benzene in Circumstellar Environments: Insights into the Photostability of Super-hydrogenated PAHs

Polycyclic aromatic hydrocarbons (PAHs), comprised of fused benzene (C6H6) rings, emit infrared radiation (3–12 μm) due to the vibrational transitions of the C–H bonds of the aromatic rings. The 3.3 μm aromatic band is generally accompanied by the band at 3.4 μm assigned to the vibration of aliphatic C–H bonds of compounds such as PAHs with an excess of peripheral H atoms (Hn–PAHs). Herein we study the stability of fully hydrogenated benzene (or cyclohexane, C6H12) under the impact of stellar radiation in the photodissociation region (PDR) of NGC 7027. Using synchrotron radiation and time-of-flight mass spectrometry, we investigated the ionization and dissociation processes at energy ranges of UV (10–200 eV) and soft X-rays (280–310 eV). Density Functional Theory (DFT) calculations were used to determine the most stable structures and the relevant low-lying isomers of singly charged C6H12 ions. Partial Ion Yield (PIY) analysis gives evidence of the higher tendency toward dissociation of cyclohexane in comparison to benzene. However, because of the high photoabsorption cross-section of benzene at the C1s resonance edge, its photodissociation and photoionization cross-sections are enhanced, leading to a higher efficiency of dissociation of benzene in the PDR of NGC 7027. We suggest that a similar effect is experienced by PAHs in X-ray photon-rich environments, which ultimately acts as an auxiliary protection mechanism of super-hydrogenated polycyclic hydrocarbons. Finally, we propose that the single photoionization of cyclohexane could enhance the abundance of branched molecules in interstellar and circumstellar media

Amazonian pollen assemblages reflect biogeographic gradients and forest cover

Aim Pollen assemblages are commonly used to reconstruct past climates yet have not yet been used to reconstruct past human activities, including deforestation. We aim to assess (i) how pollen assemblages vary across biogeographic and environmental gradients, (ii) the source area of pollen assemblages from lake sediment samples and (iii) which pollen taxa can best be used to quantify deforested landscapes. Location Amazonia. Taxon Plantae. Methods Pollen assemblages (N = 65) from mud‐water interface samples (representing modern conditions) of lake sediment cores were compared with modern gradients of temperature, precipitation and elevation. Pollen assemblages were also compared with local‐scale estimates of forest cover at 1, 2, 5, 10, 20 and 40 km buffers around each lake.ResultsOver 250 pollen types were identified in the samples, and pollen assemblages were able to accurately differentiate biogeographic regions across the basin, corresponding with gradients in temperature and precipitation. Poaceae percentages were the best predictor of deforestation, and had a significant negative relationship with forest cover estimates. These relationships were strongest for the 1 km buffer area, weakening as buffer sizes increased.Main conclusionsThe diverse Amazonian pollen assemblages strongly reflect environmental gradients, and percentages of Poaceae best reflect local‐scale variability in forest cover. Our results of modern pollen‐landscape relationships can be used to provide a foundation for quantitative reconstructions of climate and deforestation in Amazonia

Sleep deprivation affects inflammatory marker expression in adipose tissue

<p>Abstract</p> <p/> <p>Sleep deprivation has been shown to increase inflammatory markers in rat sera and peripheral blood mononuclear cells. Inflammation is a condition associated with pathologies such as obesity, cancer, and cardiovascular diseases. We investigated changes in the pro and anti-inflammatory cytokines and adipokines in different depots of white adipose tissue in rats. We also assessed lipid profiles and serum levels of corticosterone, leptin, and adiponectin after 96 hours of sleep deprivation.</p> <p>Methods</p> <p>The study consisted of two groups: a control (C) group and a paradoxical sleep deprivation by 96 h (PSD) group. Ten rats were randomly assigned to either the control group (C) or the PSD. Mesenteric (MEAT) and retroperitoneal (RPAT) adipose tissue, liver and serum were collected following completion of the PSD protocol. Levels of interleukin (IL)-6, interleukin (IL)-10 and tumour necrosis factor (TNF)-α were analysed in MEAT and RPAT, and leptin, adiponectin, glucose, corticosterone and lipid profile levels were analysed in serum.</p> <p>Results</p> <p>IL-6 levels were elevated in RPAT but remained unchanged in MEAT after PSD. IL-10 protein concentration was not altered in either depot, and TNF-α levels decreased in MEAT. Glucose, triglycerides (TG), VLDL and leptin decreased in serum after 96 hours of PSD; adiponectin was not altered and corticosterone was increased.</p> <p>Conclusion</p> <p>PSD decreased fat mass and may modulate the cytokine content in different depots of adipose tissue. The inflammatory response was diminished in both depots of adipose tissue, with increased IL-6 levels in RPAT and decreased TNF-α protein concentrations in MEAT and increased levels of corticosterone in serum.</p

Curcumin encapsulation in nanostructures for cancer therapy: a 10-year overview

Journal pre-proofsCurcumin (CUR) is a phenolic compound present in some herbs, including Curcuma longa Linn. (turmeric rhizome), with a high bioactive capacity and characteristic yellow color. It is mainly used as a spice, although it has been found that CUR has interesting pharmaceutical properties, acting as a natural antioxidant, anti-inflammatory, antimicrobial, and antitumoral agent. Nonetheless, CUR is a hydrophobic compound with low water solubility, poor chemical stability, and fast metabolism, limiting its use as a pharmacological compound. Smart drug delivery systems (DDS) have been used to overcome its low bioavailability and improve its stability. The current work overviews the literature from the past 10 years on the encapsulation of CUR in nanostructured systems, such as micelles, liposomes, niosomes, nanoemulsions, hydrogels, and nanocomplexes, emphasizing its use and ability in cancer therapy. The studies highlighted in this review have shown that these nanoformulations achieved higher solubility, improved tumor cytotoxicity, prolonged CUR release, and reduced side effects, among other interesting advantages.This study was funded by the Coordination for Higher Level Graduate Improvements (CAPES/Brazil, finance code 001), National Council for Scientific and Technological Development (CNPq/Brazil, PIBIC process #123483/2020-4), State of São Paulo Research Foundation (FAPESP/Brazil, processes #2017/10789-1, #2018/10799-0, #2018/06475-4, #2018/07707-6, #2019/08549-8, and #2020/03727-2). This work was also supported by the Portuguese Foundation for Science and Technology (FCT) under the scope of the strategic funding of UIDB/04469/2020 unit and the project AgriFood XXI (NORTE-01-0145-FEDER-000041) funded by the European Regional Development Fund under the scope of Norte2020 - Programa Operacional Regional do Norte. Our Figures were created with BioRenderinfo:eu-repo/semantics/publishedVersio