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For the first time, this paper aimed to evaluate nine ionophore and synthetic coccidiostat residues in poultry muscle samples, obtained from different production types, by solid-liquid extraction followed by liquid chromatography with tandem mass spectrometry (LC-MS/MS). The fully validated methodology was successfully applied to a total of 101 chicken and turkey samples obtained from canteens, supermarkets, and home productions in Portugal. Halofuginone, diclazuril, decoquinate, narasin, lasalocid, and salinomycin were detected in 20.8% of the samples. Home raised samples showed a greater frequency, 47.1%. The synthetic coccidiostats halofuginone, diclazuril, and decoquinate were found in averages of 0.7 μg kg-1,2.9 μg kg-1, and 3.7 μg kg-1, respectively, while averages of 1.2 μg kg-1, 1.6 μg kg-1, and 1.3 μg kg-1 were found regarding the ionophores narasin, lasalocid, and salinomycin. As for the risk assessment, values lower than 8.06% of the acceptable daily intake (ADI) were observed, indicating that exposure to coccidiostats through consumption of poultry meat does not represent risk to consumers.

Hyaluronic acid (HA), the only non-sulphated glycosaminoglycan, serves numerous structural and biological functions in the human body, from providing viscoelasticity in tissues to creating hydrated environments for cell migration and proliferation. HA is also involved in the regulation of morphogenesis, inflammation and tumorigenesis through interactions with specific HA-binding proteins. Whilst the physicochemical and biological properties of HA have been widely studied for decades, the exact mechanisms by which HA exerts its multiple functions are not completely understood. Glycopolymers offer a simple and precise synthetic platform for the preparation of glycan analogues, being an alternative to the demanding synthetic chemical glycosylation. A library of homo, statistical and alternating HA glycopolymers were synthesised by reversible addition–fragmentation chain transfer polymerisation and post-modification utilising copper alkyne–azide cycloaddition to graft orthogonal pendant HA monosaccharides (N-acetyl glucosamine: GlcNAc and glucuronic acid: GlcA) onto the polymer. Using surface plasmon resonance, the binding of the glycopolymers to known HA-binding peptides and proteins (CD44, hyaluronidase) was assessed and compared to carbohydrate-binding proteins (lectins). These studies revealed potential structure-binding relationships between HA monosaccharides and HA receptors and novel HA binders, such as Dectin-1 and DEC-205 lectins. The inhibitory effect of HA glycopolymers on hyaluronidase (HAase) activity was also investigated suggesting GlcNAc- and GlcA-based glycopolymers as potential HAase inhibitors., Glycopolymers based on hyaluronan (HA) were synthesised as homopolymers and alternating copolymers and used as probes to study the interactions with known HA-binding proteins and peptides.

Made available in DSpace on 2021-06-25T10:46:23Z (GMT). No. of bitstreams: 0 Previous issue date: 2021-01-01 Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) The aim of this study is to evaluate whether the alterations in glucose metabolism and insulin resistance are mechanisms presented in cardiac remodelling induced by the toxicity of cigarette smoke. Male Wistar rats were assigned to the control group (C; n = 12) and the cigarette smoke-exposed group (exposed to cigarette smoke over 2 months) (CS; n = 12). Transthoracic echocardiography, blood pressure assessment, serum biochemical analyses for catecholamines and cotinine, energy metabolism enzymes activities assay; HOMA index (homeostatic model assessment); immunohistochemistry; and Western blot for proteins involved in energy metabolism were performed. The CS group presented concentric hypertrophy, systolic and diastolic dysfunction, and higher oxidative stress. It was observed changes in energy metabolism, characterized by a higher HOMA index, lower concentration of GLUT4 (glucose transporter 4) and lower 3-hydroxyl-CoA dehydrogenase activity, suggesting the presence of insulin resistance. Yet, the cardiac glycogen was depleted, phosphofructokinase (PFK) and lactate dehydrogenase (LDH) increased, with normal pyruvate dehydrogenase (PDH) activity. The activity of citrate synthase, mitochondrial complexes and ATP synthase (adenosine triphosphate synthase) decreased and the expression of Sirtuin 1 (SIRT1) increased. In conclusion, exposure to cigarette smoke induces cardiac remodelling and dysfunction. The mitochondrial dysfunction and heart damage induced by cigarette smoke exposure are associated with insulin resistance and glucose metabolism changes. Department of Internal Medicine Botucatu Medical School São Paulo State University-UNESP Faculty of Nutrition UFG – Univ Federal de Goiás Department of Chemical and Biological Sciences São Paulo State University-UNESP Department of Pathology and Legal Medicine Ribeirão Preto Medical School University of São Paulo Experimental Research Unit – UNIPEX Botucatu Medical School São Paulo State University-UNESP Department of Internal Medicine Botucatu Medical School São Paulo State University-UNESP Department of Chemical and Biological Sciences São Paulo State University-UNESP Experimental Research Unit – UNIPEX Botucatu Medical School São Paulo State University-UNESP CAPES: 001 FAPESP: 2014/24197-0 FAPESP: 2016/14547-0 FAPESP: 2016/25676-5

SUMMARY BACKGROUND: The aim of this study is to evaluate the peptidylarginine deiminase 4 (PAD 4) concentration and PADI4 polymorphisms as predictors of acute kidney injury (AKI) development, the need for renal replacement therapy (RRT), and mortality in patients with septic shock. METHODS: We included all individuals aged ≥ 18 years, with a diagnosis of septic shock at ICU admission. Blood samples were taken within the first 24 hours of the patient's admission to determine serum PAD4 concentration and its PADI4 polymorphism (rs11203367) and (rs874881). Patients were monitored during their ICU stay and the development of SAKI was evaluated. Among the patients in whom SAKI developed, mortality and the need for RRT were also evaluated. RESULTS: There were 99 patients, 51.5% of whom developed SAKI and of these, 21.5% needed RRT and 80% died in the ICU. There was no difference between PAD4 concentration (p = 0.116) and its polymorphisms rs11203367 (p = 0.910) and rs874881 (p = 0.769) in patients in whom SAKI did or did not develop. However, PAD4 had a positive correlation with plasma urea concentration (r = 0.269 and p = 0.007) and creatinine (r = 0.284 and p = 0.004). The PAD4 concentration and PADI4 polymorphisms were also not associated with RRT and with mortality in patients with SAKI. CONCLUSION: PAD4 concentration and its polymorphisms were not associated with SAKI development, the need for RRT, or mortality in patients with septic shock. However, PAD4 concentrations were associated with creatinine and urea levels in these patients. RESUMO OBJETIVO: Avaliar a concentração da peptidilarginina deiminase 4 (PAD4) e os polimorfismos de PADI4, como preditores de desenvolvimento de lesão renal aguda, necessidade de terapia renal substitutiva (TRS) e mortalidade em pacientes com choque séptico. MÉTODOS: Foram incluídos indivíduos com idade ≥18 anos, com diagnóstico de choque séptico na admissão na Unidade de Terapia Intensiva (UTI). Amostras de sangue foram coletadas nas primeiras 24 horas após a admissão do paciente para determinar a concentração sérica de PAD4 e seus polimorfismos PADI4 (rs11203367) e (rs874881). Os pacientes foram acompanhados durante a internação na UTI e tiveram avaliados desenvolvimento da lesão renal aguda séptica (Sepsis-induced acute kidney injury - Saki), necessidade TRS e mortalidade. RESULTADOS: Foram avaliados 99 pacientes; 51,5% desenvolveram Saki e, desses, 21,5% necessitaram de TRS e 80% morreram na UTI. Não houve diferença entre a concentração de PAD4 (p=0,116) e seus polimorfismos rs11203367 (p=0,910) e rs874881 (p=0,769) entre os pacientes. No entanto, o PAD4 apresentou correlação positiva com a concentração plasmática de ureia (r=0,269; p=0,007) e creatinina (r=0,284; p=0,004). A concentração de PAD4 e os polimorfismos da PADI4 também não foram associados à TRS e à mortalidade em pacientes com Saki. CONCLUSÕES: A concentração de PAD4 e seus polimorfismos não foram associados ao desenvolvimento de Saki, à necessidade de TRS ou à mortalidade em pacientes com choque séptico. No entanto, as concentrações de PAD4 foram associadas às concentrações de creatinina e ureia nesses pacientes.

Atherosclerosis (AS) is a lipid-driven chronic inflammatory disease occurring at the arterial subendothelial space. Macrophages play a critical role in the initiation and development of AS. Herein, targeted codelivery of anti-miR 155 and anti-inflammatory baicalein is exploited to polarize macrophages toward M2 phenotype, inhibit inflammation and treat AS. The codelivery system consists of a carrier-free strategy (drug-delivering-drug, DDD), fabricated by loading anti-miR155 on baicalein nanocrystals, named as baicalein nanorods (BNRs), followed by sialic acid coating to target macrophages. The codelivery system, with a diameter of 150 nm, enables efficient intracellular delivery of anti-miR155 and polarizes M1 to M2, while markedly lowers the level of inflammatory factors in vitro and in vivo. In particular, intracellular fate assay reveals that the codelivery system allows for sustained drug release over time after internalization. Moreover, due to prolonged blood circulation and improved accumulation at the AS plaque, the codelivery system significantly alleviates AS in animal model by increasing the artery lumen diameter, reducing blood pressure, promoting M2 polarization, inhibiting secretion of inflammatory factors and decreasing blood lipids. Taken together, the codelivery could potentially be used to treat vascular inflammation., Graphical abstract Image 1Targeted codelivery of anti-miR 155 and anti-inflammatory drug, baicalein, by using a carrier-free strategy effectively promotes polarization of macrophages from M1 toward M2 in vitro and in vivo. The codelivery system has prolonged blood-circulation time and can accumulate in the plaque after intravenous injection. The platform is potent to combat vascular inflammation.

The pore distribution in activated carbon is crucial for its performance on adsorption processes. In desulfurization applications, the literature highlights the importance of pores from 5 to 10 A. However, little is known and reported about the range of ultramicropores smaller than 4 A, which has been found in commercial samples used for H2S retention. In order to clarify the influence of this fraction of pores on the H2S retention of typical biogas mixtures, measurements of multicomponent adsorption of hydrogen sulfide in the presence of carbon dioxide for activated carbon samples further impregnated with potassium hydroxide have been performed in column dynamics. Molecular simulation, XRF analysis and textural characterization were applied to aid the study. Results have shown that the H2S retention capacity in the presence of CO2 decreased significantly mainly in the impregnated samples. The degree of reduction in H2S retention indicates that ultramicropores can be of substantial importance through a synergistic immobilizing effect of H2S molecules. The better understanding of such an effect could improve the development of more efficient adsorbents for chemical industries.

The extracellular matrix (ECM) modulates a multitude of cell functions, and this regulation is provided by key ECM components forming a complex network. Hyaluronic acid (HA) is an abundant component of the ECM that binds to proteins and influences various activities of endothelial cells (ECs). Although the effect of soluble HA on cell spreading has been studied, the impact of peptide-bound HA has not yet been investigated in great detail. We aim to comprehensively study the roles of immobilized HA on the regulation of EC behavior compared to the more conventional use of soluble HA. A 2D model surface formed by self-assembled monolayers (SAMs) of a HA-binding peptide (Pep-1) is used as an anchor for HA immobilization. Mixed SAMs, consisting of thiolated Pep-1 and 1-octanethiol, are prepared and characterized by using ellipsometry and contact angle measurement. Full density Pep-1 SAMs are more hydrophilic and bind more HA than mixed SAMs. Cell spreading and migration are enhanced by immobilized low molecular weight (LMW) HA, which also facilitates cell alignment and elongation under laminar flow conditions and potentially drives directional migration. This effect is not mediated by the expression of CD44, and immobilized LMW HA is found to accelerate the assembly of focal adhesions. Such biomimetic surfaces provide new insights into the role of HA in regulating the spreading and phenotype of endothelial cells.

Made available in DSpace on 2019-10-06T17:18:55Z (GMT). No. of bitstreams: 0 Previous issue date: 2019-01-01 Debreceni Egyetem BACKGROUND/AIMS: Doxorubicin, a chemotherapy drug used successfully for years, could induce cardiotoxicity. Euterpe oleracea Mart. (açai) is a fruit high in antioxidant properties. The aim of this study was to evaluate doxorubicin-induced cardiotoxicity prevention after açai administration. METHODS: A total of 64 male Wistar rats were allocated into 4 groups: control (C), açai (A), doxorubicin (D) and açai-doxorubicin (DA). Rats received regular chow (C and D groups) or chow supplemented with açai 5% (A and DA groups) for 4 weeks. Subsequently, rats received doxorubicin 20 mg/kg (D and DA groups) or saline (C and A groups). Euthanasia was performed 48 hours after doxorubicin injection. Left ventricular function was evaluated by echocardiography in vivo and by isolated heart study ex vivo. Oxidative stress, myocardial metabolism and nitric oxide metabolite were evaluated by spectrophotometry, MMP-2 activity by zymography and caspase-3 and Bcl-2 protein expression by Western blot. RESULTS: Doxorubicin induced decreases in body weight, food and water ingestion. We observed decreases in left ventricular fractional shortening in rats treated with doxorubicin. Additionally, the same rats showed lower +dP/dt and -dP/dt during isolated heart study than those who did not receive doxorubicin. Doxorubicin injection increased caspase-3 protein expression, myocardium lipid hydroperoxide concentration, MMP-2 activity, phosphofructokinase and lactate dehydrogenase activity, and decreased β-hydroxyacyl-CoA dehydrogenase, pyruvate dehydrogenase, citrate synthase, complex I, complex II and ATP synthase activity in myocardium. Açai supplementation improved left ventricular fractional shortening, decreased myocardium lipid hydroperoxide concentration, MMP-2 activity, and improved β-hydroxyacyl-CoA dehydrogenase, phosphofructokinase, citrate synthase, complex II and ATP synthase enzymatic activities. We did not observe differences in nitric oxide metabolite concentrations between groups. CONCLUSION: Doxorubicin induced left ventricular dysfunction, increases in oxidative stress, changes in myocardium metabolism and MMP-2 activation. Açai supplementation was able to prevent these alterations. Medical School São Paulo State University (Unesp) Institute of Biosciences São Paulo State University (Unesp) Medical School São Paulo State University (Unesp) Institute of Biosciences São Paulo State University (Unesp) Debreceni Egyetem: 2018/03381-9

The resistance of pathogens to traditional antibiotics is currently a global issue of enormous concern. As the discovery and development of new antibiotics become increasingly challenging, synthetic antimicrobial lipopeptides (AMLPs) are now receiving renewed attention as a new class of antimicrobial agents. In contrast to traditional antibiotics, AMLPs act by physically disrupting the cell membrane (rather than targeting specific proteins), thus reducing the risk of inducing bacterial resistance. In this study, we use microsecond-timescale atomistic molecular dynamics simulations to quantify the interaction of a short AMLP (C16-KKK) with model bacterial lipid bilayers. In particular, we investigate how fundamental transmembrane properties change in relation to a range of lipopeptide concentrations. A number of structural, mechanical, and dynamical features are found to be significantly altered in a non-linear fashion. At 10 mol% concentration, lipopeptides have a condensing effect on bacterial bilayers, characterized by a decrease in the area per lipid and an increase in the bilayer order. Higher AMLP concentrations of 25 and 40 mol% destabilize the membrane by disrupting the bilayer core structure, inducing membrane thinning and water leakage. Important transmembrane properties such as the lateral pressure and dipole potential profiles are also affected. Potential implications on membrane function and associated proteins are discussed. Electronic supplementary material The online version of this article (10.1007/s00232-019-00068-3) contains supplementary material, which is available to authorized users.

We present molecular simulations of gases in mesoporous MOF MIL-100(Fe) impregnated with ionic liquids [Bmim+][PF6–] and [Bmim+][Tf2N–]. Adsorption of pure carbon dioxide, methane, nitrogen, and ty...

Pulmonary arterial hypertension is a fatal lung disease caused by the progressive remodeling of small pulmonary arteries (PAs). Sildenafil can prevent the remodeling of PAs, but conventional sildenafil formulations have shown limited treatment efficacy for their poor accumulation in PAs. Here, glucuronic acid (GlcA)-modified liposomes (GlcA-Lips) were developed to improve the delivery of sildenafil to aberrant over-proliferative PA smooth muscle cells via targeting the GLUT-1 (glucose transport-1), and, therefore, inhibiting the remodeling of PAs in a monocrotaline-induced PA hypertension model. GlcA-Lips encapsulating sildenafil (GlcA-sildenafil-Lips) had a size of 90 nm and a pH-sensitive drug release pattern. Immunostaining assay indicated the overexpression of GLUT-1 in PA smooth muscle cells. Cellular uptake studies showed a 1-fold increase of GlcA-Lips uptake by PA smooth muscle cells and pharmacokinetics and biodistribution experiments indicated longer blood circulation time of GlcA-Lips and increased ability to target PAs by 1-fold after 8 hours administration. Two-week treatment indicated GlcA-sildenafil-Lips significantly inhibited the remodeling of PAs, with a 32% reduction in the PA pressure, a 41% decrease in the medial thickening, and a 44% reduction of the right ventricle cardiomyocyte hypertrophy, and improved survival rate. Immunohistochemical analysis showed enhanced expression of caspase-3, after administration of GlcA-sildenafil-Lips, and reduced expression of P-ERK1/2 (phosphorylated ERK1/2) and HK-2 (hexokinase-2), and increased level of eNOS (endothelial nitric oxide synthase) and cyclic GMP (cGMP). In conclusion, targeted delivery of sildenafil to PA smooth muscle cells with GlcA-Lips could effectively inhibit the remodeling of PAs in the monocrotaline-induced PA hypertension.

Made available in DSpace on 2019-10-06T16:06:02Z (GMT). No. of bitstreams: 0 Previous issue date: 2018-11-16 BACKGROUND: Oxidative stress is one potential mechanism that explain the direct effects of smoking on cardiac remodeling process. However, no study has compared different myocardial products of macromolecule oxidation after tobacco smoke exposure. Thus, the aim of this study was to investigate the lipid hydroperoxide (LH) levels, protein carbonyl concentrations and DNA damage in cardiac tissue of rats exposed to tobacco smoke. METHODS: Male Wistar rats were divided into two groups: group C (control, n = 14) composed of animals not exposed to cigarette smoke; group ETS (exposed to tobacco smoke, n = 14) composed by animals exposed to cigarette smoke. The animals were exposed to 2 month of ETS and morphological, biochemical and functional analyses were performed. RESULTS: Cardiac cotinine levels were elevated in the ETS group. In addition, the myocyte cross-sectional area was higher in the ETS group. (C = 266.6 ± 23.2 μm2 and ETS = 347.5 ± 15.1 μm2, p

Selecting a polymer depends on its characteristics, the properties of the drug and of the remaining ingredients in the formulation. The drug, when incorporated into a polymeric matrix, can show several advantages when compared with its conventional form. In this context, this work describes the preparation and characterization of polyethylene glycol (PEG 4000) and its derivative particles loaded with benznidazole, as well as evaluates their trypanocidal activity. In this work, reactions to modify the PEG 4000 polymer and the subsequent incorporation of the benznidazole were made. The nuclear magnetic resonance (NMR) analysis confirmed the efficiency in modifying the PEG chains. The morphology of polymeric films was observed by atomic force microscopy (AFM) and showed considerable changes on the film organization. The acetylation of PEG favored the stability of the system and an increase in the zeta potential from -14.83 to -25.54 mV was observed. Although encapsulation efficiency values between 30.14 and 39.48% were found, the enhanced benznidazole dissolution profile by microparticles enables the use of lower drug concentrations. This fact can be proven by the increased trypanocidal effect of benznidazole when encapsulated in BP3 microparticles. Finally, the high selectivity of the formulations for trypanocidal action guarantees their safety as an alternative for the treatment of the Chagas disease.

Made available in DSpace on 2021-06-25T10:52:48Z (GMT). No. of bitstreams: 0 Previous issue date: 2021-04-01 Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) Background: The purpose of this study was to evaluate urea to albumin ratio (UAR) as predictor of mortality in patients with septic shock. Methods: We included all individuals aged ≥ 18 years, with the diagnosis of septic shock at Intensive Care Unit (ICU) admission. Laboratorial and clinical data was recorded within the first 24 h of the patient's admission. Serum urea and albumin concentration were used for UAR calculation. All patients were followed during their ICU stay and the mortality rate was recorded. Results: 222 patients were included in the analysis; the mean age was 62.3 ± 15.1 years and 66% were male. Mortality rate during the ICU stay was 59.9% and the median UAR was 40.7 (24.5–66.1). The UAR was also higher in patients who died in the ICU and was positively correlated with APACHE II, SOFA score and CRP. The ROC ICU mortality development (AUC: 0.617; CI 95%: 0.541–0.693; p: 0.003) at the cutoff of ≥47.25. Furthermore, UAR values were associated with ICU mortality when adjusted by age, sex and APACHE II (OR: 1.011; CI95%:1.000–1.022; p = 0.043) and when adjusted by lactate (OR: 1.014; CI95%:1.003–1.024; p = 0.009). Conclusions: Our data suggest that UAR could play a role as predictor of ICU mortality in patients with septic shock. Department of Internal Medicine Botucatu Medical School UNESP – Univ Estadual Paulista Faculty of Nutrition Univ Federal de Goias UFG Department of Internal Medicine Botucatu Medical School UNESP – Univ Estadual Paulista CAPES: 2014/17262-0 FAPESP: 2017/21554-5

Dynamic photoresponsive synthetic hydrogels offer important advantages for biomaterials design, from the ability to cure hydrogels and encapsulate cells in situ to the light-mediated control of cell-spreading and tissue formation. We report the facile and effective photocuring and photoremodeling of disulfide-cross-linked hyaluronic acid hydrogels, based on photo-oxidation of corresponding thiol residues and their radical-mediated photodegradation. We find that the mechanical properties of disulfide hydrogels and the extent of their photoremodeling can be tuned by controlling the photo-oxidation and photodegradation reactions, respectively. This enables not only the photopatterning of the mechanical properties of hydrogels but also their self-healing and photomediated healing. Finally, we demonstrate the ability to encapsulate mesenchymal stromal cells within these materials and to regulate their protrusion and spreading in 3D matrices by controlling the mechanical properties of the disulfide networks. Therefore, synthetically accessible photoconfigurable disulfide hydrogels offer interesting opportunities for the design of soft biomaterials and the regulation of cell encapsulation and matrix remodeling for tissue engineering.

The insertion of functional groups in polymer compounds may facilitate their interaction with different drugs. PEG polymers are widely used for their low melting point, low toxicity, drug compatibility, and hydrophilicity. They are used as pharmaceutical excipients for the formulation of conventional or modified released drugs and are designed to be upgraded as drug-modulating controllers at specific sites in the body. Indomethacin has been used in the controlled release of drugs because it is a drug that have good interaction with different polymers. The drug is a non-steroidal anti-inflammatory drug used in the treatment of rheumatoid arthritis, osteoarthritis, spondylitis, and other disorders. In this work, PEG 4000 had its chain modified by organic reactions and their derivatives were emulsified to form microparticles using polyvinyl alcohol as an emulsifier. Posteriorly were also incorporated with indomethacin. The samples were characterized to prove the influence of indomethacin on the morphology and thermal behavior of this polymer. The controlled release was performed in the time from 0 to 240 min using the Ultraviolet Spectroscopy to quantify indomethacin released from the polymer matrix for these 4 hours. Releases over the time were satisfactory as concentrations increased over time, which we can conclude that the structural modification of PEG 4000 was beneficial in the release of the indomethacin drug.

Two fibrous clay minerals (sepiolite and palygorskite) have been employed as adsorbents to assess their adsorption capacity of pure CO2 in a volumetric setup. The raw sepiolite reached a CO2 uptake of 1.48 mmol g−1 due to the presence of nanocavities acting as a molecular sieve. Both sepiolite and palygorskite were modified by microwave-assisted acid treatment, which led to an increase in specific surface area and pore volume due to Mg2+ leaching, particularly in the case of sepiolite. However, the partial digestion of these fibrous structures does not improve CO2 adsorption uptake due to the progressive increase of the size of nanocavities. In a next step, both fibrous clay minerals were functionalized with amine species by different procedures (grafting with (3-Aminopropyl) triethoxysilane (APTES), impregnation with polyethyleneimine (PEI) and double functionalization by grafting with APTES and then impregnation with PEI. In all cases, it can be observed that the incorporation of amine species favors the chemical interaction between the amines species and the CO2 molecules, although it also produces obstruction of the nanochannels so the adsorption takes place mainly on the outer surface of the fibers. Finally, the incorporation of amine species by double functionalization led to the highest CO2 adsorbed concentration of 2.07 mmol g−1 at 760 mm Hg and 65 °C due to a larger proportion of available amines sites as well as the use of higher adsorption temperature, which favored the diffusion of CO2 molecules within the adsorbent.

The organic-inorganic adsorbent composed of polyethylenimine (PEI) grafted within organosilane-magadiite layers has been synthesized using different alkoxysilanes with different PEI loadings as a novel adsorbent for CO2 capture from postcombustion and natural gas. The synthesis was confirmed by XRD, 13C and 29Si NMR, TGA and elemental analysis. The increase of nitrogen concentration from PEI was proportional to the chloro- (CP) or glycidyloxypropyl (GM) pending groups’ concentration. However, there was a negative effect in the glycidyloxypropyl-magadiite in high concentration due to the size of this pending group. PEI-xCP-MAG and PEI-xGM-MAG adsorbents were subjected to CO2, N2, CH4, CO2/N2 (15/85 vol %) and CO2/CH4 (30/70 vol %) adsorption up to 20 bar at 75 °C. The experimental isotherms were fit using dual-site Sips (DSS) and Sips model. The parameters obtained from pure gases applied to the extended DSS and Sips model were able to predict the adsorbents selectivity. The selectivity presented expressive values which are comparable to MOF’s, zeolites, porous polymers and carbon, even with a low CO2 adsorption. The CO2/N2 and CO2/CH4 selectivities at 1 bar gas mixture were in the range of 111–279 and 10–83, respectively. The studied adsorbents are promising materials in CO2 capture at postcombustion.

The use of waste biomass to produce adsorbent materials for the process of biogas upgrading might be a sustainable way to improve the energy matrix and help developing waste disposal technologies. The objective of this study was to prepare and evaluate activated carbons from coconut shell and babassu coconut, a waste biomass highly available at low cost. Both carbon samples were prepared by physical activation with CO2 and characterized by N2 adsorption isotherms at 77 K. The biosorbents produced from babassu and coconut shells presented BET surface areas of 1452 m2/g and 809 m2/g, respectively. Their applicability to upgrade biogas was assessed by experimental evaluation of pure (CO2 and CH4) and mixture (CO2/CH4) adsorption equilibrium data at 293 K and pressures up to 10 bar. The results were used to compare the performance of the samples prepared in this work with a commercial sample. Adsorption capacity for carbon dioxide was similar for both synthesized samples, but the activated carbon from coconut shell presented better properties for CO2/CH4 separation, as its selectivity (4.2 at 1 bar) and working capacity (1.0 mmol/g at 3 bar) are comparable to those of the commercial adsorbent over the low pressure range studied. This indicates that biomass waste is an interesting precursor for the production of activated carbons for biogas upgrading.

Wastewater from municipal sewage may be an interesting source of biogas, in which case siloxanes are commonly present above the spec limit to be used in power engines. On the other hand, residual sand from Wastewater Treatment (WWT) Plants is also rich in inorganic matter, which can be a suitable feedstock for the synthesis of porous inorganic adsorbents. This work describes the synthesis of an alternative adsorbent for siloxane adsorption using residual sand from a WWT plant. The ultimate goal was to find a substitute for commercial activated carbons or silicas currently employed in siloxane removal from biogas. The residual sand was subject to thermal and acid treatment, which successfully increased its silicon content while developing adequate internal porosity. The textural characteristics and the chemical composition of the new adsorbent were similar to those found in commercial silica gels. Liquid phase adsorption isotherms and uptake rate curves were measured for siloxanes Octamethylcyclotetrasiloxane (D4) and decamethylcyclopentasiloxane (D5). The siloxane uptakes and adsorption kinetics were comparable and even superior to those found in commercial silicas, especially at low adsorbate concentrations. These results demonstrate the potential of residual sand from WWT as a suitable raw material to produce a good adsorbent for the removal of cyclic siloxanes from biogas.

Porous clay heterostructures (PCH) have been synthesized from raw bentonite, obtaining porous materials with high surface area and micro-, meso- and macroporosity. Both raw bentonite and PCH have been evaluated in CO2 adsorption processes at 1 bar and 25 °C. In both cases, adsorption isotherms were well fitted using the Langmuir model, obtaining an increase of the CO2 adsorption from 0.112 mmol CO2 g−1 for the raw bentonite to 0.640 mmol CO2 g−1 in the PCH. In order to improve the CO2 adsorption capacity, raw bentonite and PCH were functionalized with amine species, via grafting using 3-aminopropyltriethoxysilane (APTES) and via impregnation with polyethylenimine (PEI) or tetraethylenepentamine (TEPA). The isotherms of the amine-functionalized samples were adjusted to the Dual-Langmuir model, which assumes the coexistence of physical and chemical adsorption sites. From the profiles of the CO2 isotherms, it can been observed that grafted-PCH with APTES shows the coexistence of physical and chemical interactions, reaching 1.023 mmol CO2 g−1. The adsorption of CO2 on PCH impregnated with TEPA and mainly with PEI is governed by chemical interactions between the amine species located in the porous structure and/or on the surface of the adsorbent and the CO2 molecules, attaining maximum values of 1.644 and 1.465 mmol CO2 g−1 for TEPA and PEI, respectively.

Made available in DSpace on 2018-12-11T17:12:32Z (GMT). No. of bitstreams: 0 Previous issue date: 2017-08-01 Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) The objective of this study was to evaluate the influence of tomato or lycopene supplementation on cardiac remodeling after myocardial infarction (MI). Male Wistar rats were assigned to four groups: the sham group (animals that underwent simulated surgery) that received a standard chow (S; n=18), the infarcted group that received a standard chow (MI; n=13), the infarcted group supplemented with lycopene (1 mg of lycopene/kg body weight/day) (MIL; n=16) and the infarcted group supplemented with tomato (MIT; n=16). After 3 months, morphological, functional and biochemical analyses were performed. The groups MIL and MIT showed decreased interstitial fibrosis induced by infarction. Tomato supplementation attenuated the hypertrophy induced by MI. In addition, tomato and lycopene improved diastolic dysfunction evaluated by echocardiographic and isolated heart studies, respectively. The MI group showed higher levels of cardiac TNF-α compared to the MIL and MIT groups. Decreased nuclear factor E2-related factor 2 was measured in the MIL group. Lipid hydroperoxide levels were higher in the infarcted groups; however, the MIT group had a lower concentration than did the MI group [S=223±20.8, MI=298±19.5, MIL=277±26.6, MIT=261±28.8 (nmol/g); n=8; P

The increasing worldwide demand for energy bound to a strong dependence of fossil fuels has considerably intensified the concentration of greenhouse gases in the atmosphere, reaching alarming levels. Among those gases, carbon dioxide is considered the main responsible for global warming due to its higher concentration. In order to mitigate the negative effects of global warming and to reduce emissions, many technologies have been developed in the last decades to separate and recover carbon dioxide (CO 2 ) at different capture scenarios. Adsorption processes rely on the use of highly porous solids such as activated carbons, which are either commercially. Pressure Swing Adsorption (PSA) is a cyclic adsorption process, which allows continuous separation of gas streams. PSA is performed by periodic changes of pressure aiming the optimization of contaminants removal and is considered viable for separation of CO 2 from flue gases containing about 5-15% v/v. To achieve a certain performance, a PSA process may consist of several steps, columns and cycle time. One of the most basic configurations comprises four steps: pressurization, feed, blowdown and purge. The performance of a PSA process is usually evaluated by the purity, recovery and productivity reached. This study presents experimental and simulated data obtained from a bench-scale PSA, with a maximum pressure of 6 bar for pressurization and feed steps and minimum of 1 bar for blowdown and purge steps. The unit was tested with a mixture containing 85% of N 2 and 15% of CO 2 (on a molar basis). Carbon dioxide and nitrogen breakthrough curves were obtained under typical conditions of post combustion capture. A mathematical-phenomenological model combining momentum, mass and heat balances and using the Linear Driving Force approach (LDF) for mass transport and Langmuir model for equilibrium was applied in this study to simulate the dynamic behavior of the process. The performance tests presented productivity of 15 mol h -1 kg-ads -1 and, according to the changes of step time, N 2 purity of 97.7%. The model predicted reasonably the breakthrough curves and temperature profiles, with more precision for the latter. The combination of the simulation tool with and experimental PSA unit is very valuable for a deeper understanding of the involved phenomena and helpful with the design of optimized and efficient CO 2 adsorption-based capture processes.

Sepiolite was treated in HNO 3 solutions with the assistance of microwave radiation. This treatment caused the progressive depletion of Mg 2+ , the gradual degradation of the sepiolite structure and the formation of an amorphous silica phase, which contributes to a noticeable increase of the surface area. The use of microwaves during acid treatment, after few minutes, led to materials with similar S BET to those obtained after 48 h with conventional heating methods. The influence of mineralogical impurities, crystallinity and chemical composition in the reactivity of sepiolite to this treatment was also studied. The obtained materials were impregnated with polyethylenimine and assessed for CO 2 capture and CO 2 /N 2 selectivity at different temperatures. Experimental equilibrium data were fitted to Langmuir and Sips models. The adsorption data revealed that sepiolite can be an interesting adsorbent for CO 2 capture, achieving a capacity of 1.70 mmol g −1 at 338 K and 1 bar, providing a high CO 2 /N 2 selectivity (440 mol CO 2 /mol N 2 ).

Essentials Inhibitors of protein disulfide isomerase (PDI) have been considered a new antithrombotic class. CxxC is a PDI-targeted peptide that has been previously shown to inhibit its reductase activity. CxxC binds to surface PDI and inhibits ADP- and thrombin-evoked platelet activation and aggregation. CxxC binds to Cys400 on CGHC redox motif of PDI a’ domain, a site for PDI prothrombotic activity. SummaryBackground Protein disulfide isomerase (PDI) plays a major role in platelet aggregation, and its inhibitors have emerged as novel antithrombotic drugs. In previous work, we designed a peptide based on a PDI redox motif (CGHC) that inhibited both PDI reductase activity and PDI-modulated superoxide generation by neutrophil Nox2. Thus, we hypothesized that this peptide would also inhibit platelet aggregation by association with surface PDI. Methods Three peptides were used: CxxC, containing the PDI redox motif; Scr, presenting a scrambled sequence of the same residues and AxxA, with cysteines replaced by alanine. These peptides were tested under platelet aggregation and flow cytometry protocols to identify their possible antiplatelet activity. We labeled membrane free thiol and electrospray ionization liquid chromatography tandem mass spectrometry to test for an interaction. Results CxxC decreased platelet aggregation in a dose-dependent manner, being more potent at lower agonist concentrations, whereas neither AxxA nor Scr peptides exerted any effect. CxxC decreased aIIbb3 activation, but had no effect on the other markers. CxxC also decreased cell surface PDI pulldown without interfering with the total thiol protein content. Finally, we detected the addition of one CxxC molecule to reduced PDI through binding to Cys400 through mass spectrometry. Interestingly, CxxC did not react with oxidized PDI. Discussion CxxC has consistently shown its antiplatelet effects, both in PRP and washed platelets, corroborated by decreased aIIbb3 activation. The probable mechanism of action is through a mixed dissulphide bond with Cys400 of PDI, which has been shown to be essential for PDI‘s actions. Conclusion In summary, our data support antiplatelet activity for CxxC through binding to Cys400 in the PDI a0 domain, which can be further exploited as a model for sitedriven antithrombotic agent development.

In this work, solid wastes from the flocculation step of a drinking water treatment plant were used as starting material to obtain CO2 adsorbents upon thermal treatment and a pillaring strategy. Thermally treated solid waste and pillared materials were characterized by XRD, FTIR, TGA, N2 adsorption–desorption isotherms at 77 K, XPS and elemental analysis. From the characterization results, it was found that the introduction of silica pillars was successful, leading to heterostructured materials with higher specific surface area and pore volume. In order to improve the CO2 adsorption capacity, pillared materials were functionalized by grafting with (3-aminopropyl)triethoxysilane (APTES)and impregnation with polyethylenimine (PEI). Pillared materials could be loaded with up to 50 wt% PEI. PEI-impregnated pillared adsorbents were tested for CO2 adsorption at 298 and 348 K and CO2/N2 adsorption at 348 K using a Magnetic Suspension Balance equipped with a mixture gas dosing (Rubotherm, Germany). Langmuir and Sips models were used to fit monocomponent and mixture experimental data, considering two different sites for CO2 adsorption. At 1 bar, 50PEI-SiFe (loaded with 50 wt% PEI) adsorbed 2.5 and 3.6 mmol CO2 g−1 at 298 and 348 K, respectively and exhibited an extremely high CO2/N2 selectivity (above 150 mol CO2/mol N2 at 348 K). Nevertheless, PEI loaded adsorbents still exhibit a lower amine efficiency as compared to APTES-grafted counterparts, due to diffusion restrictions caused by the high viscosity of the impregnated polymer.

The present research evaluates the adsorption of reactive dyes, Remazol Violet 5R (RV5R) and Acid Blue 25 (AB25), using Porous Clay Heterostructures (PCHs) prepared from natural bentonite. Natural bentonite, PCH with silica pillars (Si-PCH) and PCH with silica-zirconia (SiZr-PCH) were characterized by elemental analysis, XRD, N 2 adsorption-desorption at − 196 °C, FT-IR, TG and XPS. The adsorption experiments were carried out in a stirred tank in order to evaluate the effect of pH, contact time and initial concentration. The adsorption isotherms were well fitted by Langmuir (L), Langmuir-Freundlich (LF) and Redlich Peterson (RP) models. The equilibrium data were described using the Langmuir-Freundlich model for both dyes and both materials, obtaining a maximum adsorption capacity of 209.9 mg g − 1 and 265.9 mg g − 1 for AB25 using Si-PCH and SiZr-PCH, respectively. In the case of RV5R, the maximum adsorption capacity was 127.07 mg g − 1 and 185.7 mg g − 1 for Si-PCH and SiZr-PCH, respectively. The adsorption process takes place by electrostatic interactions between the silanol groups of the PCHs with functional groups of the dyes, such as amine or hydroxyl. From the obtained results, it can be concluded that PCHs showed to be a promising material for the adsorption of dye.

This work focuses on the optimization of cellulase production by two Trichoderma strains. A 24 full factorial design was used to evaluate the effects of four factors in the optimization of cellulase production (filter paper assay—FPA): crude glycerol, microcrystalline cellulose, yeast extract and ammonium sulfate. In fermentation with Trichoderma CMIAT 054 strain the largest FPA (138.48 FPU L−1) occurred with 25.0 g L−1 of cellulose, 10.0 g L−1 of crude glycerol, 1.4 g L− 1 of yeast extract and 3.5 g L− 1 of ammonium sulfate in the culture medium. In tests with Trichoderma CMIAT 041 strain the highest FPA (89.35 FPU L−1) occurred with 25.0 g L−1 of cellulose, 20.0 g L−1 of crude glycerol, 0.6 g L−1 of yeast extract and 1.5 g L−1 of ammonium sulfate in the culture medium. ANOVA showed a correlation coefficient of 93 and 88% for Trichoderma CMIAT 054 and CMIAT 041 strains, respectively. Reduced regression models for the cellulase produced by these strains were obtained.

The glycocalyx is the immediate pericellular matrix that surrounds many cell types, including endothelial cells (ECs), and is typically composed of glycans (glycosaminoglycans, proteoglycans, and glycoproteins). The endothelial glycocalyx is rich in hyaluronic acid (HA), which plays an important role in the maintenance of vascular integrity, although fundamental questions about the precise molecular regulation mechanisms remain unanswered. Here, we investigate the contribution of HA to the regulation of endothelial function using model surfaces. The peptide sequence GAHWQFNALTVR, previously identified by phage display with strong binding affinity for HA and named Pep-1, was thiolated at the N-terminal to form self-assembled monolayers (SAMs) on gold (Au) substrates, and microcontact printing (μCP) was used to develop patterned surfaces for the controlled spatial presentation of HA. Acetylated Pep-1 and a scrambled sequence of Pep-1 were used as controls. The SAMs and HA-coated surfaces were characterized by X-ray photoelectron spectroscopy (XPS), contact angle measurements, and quartz crystal microbalance with dissipation (QCM-D) monitoring, which confirmed the binding and presence of thiolated peptides on the Au surfaces and the deposition of HA. Fluorescence microscopy showed the localization of fluorescently labelled HA only on areas printed with Pep-1 SAMs. Cell culture studies demonstrated that low molecular weight HA improved the adhesion of human umbilical vein endothelial cells (HUVECs) to the substrate and also stimulated their migration. This research provides insight into the use of SAMs for the controlled presentation of HA with defined size in cultures of HUVECs to study their functions.

Despite the successful application of LNA/2OMe-FISH procedures for bacteria detection, there is a lack of knowledge on the properties that affect hybridization. Such information is crucial for the rational design of protocols. Hence, this work aimed to evaluate the effect of three essential factors on the LNA/2OMe hybridization stephybridization temperature, NaCl concentration and type and concentration of denaturant (formamide, ethylene carbonate and urea). This optimization was performed for 3 Gram-negative bacteria (Escherichia coli, Pseudomonas aeruginosa and Citrobacter freundii) and 2 Gram-positive bacteria (Enterococcus faecalis and Staphylococcus epidermidis), employing the response surface methodology and a Eubacteria probe. In general, it was observed that a high NaCl concentration is beneficial (from 2 M to 5 M), regardless of the denaturant used. Urea, formamide and ethylene carbonate are suitable denaturants for LNA/2OMe-FISH applications; but urea provides higher fluorescence intensities among the different bacteria, especially for gram-positive bacteria and for P. aeruginosa. However, a unique optimal protocol was not found for all tested bacteria. Despite this, the results indicate that a hybridization solution with 2 M of urea and 4 M of NaCl would be a proper starting point. Furthermore, a hybridization temperature around 62°C, for 14 bp probes with LNA monomers at every third position of 2?OMe and 64% of GC content, should be use in initial optimization of new LNA/2OMe-FISH protocols., This work was financially supportedby project POCI-01-0145-FEDER-006939 (Laboratory for Process Engineering, Environment, Biotechnology and Energy – UID/EQU/00511/2013),POCI-01-0145-FEDER-006684 (Center of Biological Engineering - UID/BIO/04469) funded by EuropeanRegional Development Fund (ERDF) through COMPETE2020– Programa Operacional Competitividade e Internacionalização (POCI), and by national funds (PIDDAC) through FCT – Fundação para a Ciência e a Tecnologia/MCTES; NORTE-01-0145-FEDER-000004- BioTecNorte operation,funded by the EuropeanRegional Development Fund under the scope of Norte2020 Programa Operacional Regional do Norte; PostDoctoral Fellowship SFRH/BPD/121601/2016 (Andreia S. Azevedo) and PhD Fellowship SFRH/ BD/118860/2016 (Ricardo M. Fernandes) supportedby national funds throughFCT Fundação para a Ciência e a Tecnologia; Project PTDC/DTP-PIC/4562/2014 – POCI-01-0145FEDER-016678 (Coded-FISH) and Project POCI01-0145-FEDER-030431(CLASInVivo), funded by FEDER funds through COMPETE2020- Programa Operacional Competitividade e Internacionalização (POCI) and by national funds through FCT Fundação para a Ciência e a Tecnologia, I.P., info:eu-repo/semantics/publishedVersion

Thiamin is a hydrosoluble vitamin that plays a role in several biological processes, mainly in glucose metabolism. There are several risk factors for developing thiamin deficiency, such as malnutrition, refeeding syndrome, gastrointestinal surgery, and alcoholism. Recently, the role of thiamin in critically ill patients has gained prominence, and the prevalence of thiamin deficiency was found to be increased in patients with severe burns, major surgery, septic shock, end-stage renal disease, and heart failure. In adults, thiamin deficiency presents as encephalopathy, dry beriberi (with neurological signs and symptoms), or wet beriberi (with cardiovascular signs and symptoms). Thiamin deficiency can be diagnosed clinically, and all clinicians should be aware of this disease, especially in patients with risk factors for thiamin deficiency. Thiamin supplementation should be started as early as possible in patients suspected to have thiamin deficiency. Treatment is safe, inexpensive, simple, and life-saving. Diagnosis is confirmed on a positive response to treatment.

Carbon microfibers (CMF) from polymeric substrates, such as polyacrylonitrile (PAN) have been proposed in the literature as potential CO2 adsorbents due to their high porosity and high content of nitrogen. They are flexible materials, whose adsorption properties may be modified by tailoring synthesis conditions, aiming at a given target, e.g. enhance CO2 selectivity over other gases. The response surface is a well-known empirical method to assess the effect of two or more variables on the behavior of one response variable. In this work, we examined the impact of carbonization temperature and PAN solution concentration (variables) on the response variables BET specific surface area and adsorbed concentration of CO2 and CH4. It has been found that BET area and CH4 adsorbed concentration are directly affected by the temperature of carbonization of fibers, whereas PAN solution concentration has much less impact on these two responses. However, for CO2 adsorbed concentration as response variable, both carbonization temperature and PAN solution concentration play a major role. Optimal conditions were found for carbonization temperature at 800 °C and PAN concentration between 9 and 10%.

The traditional mesoporous silica (SBA-15) was synthesized by hydrothermal route. The swelling agents 1,3,5-trymethylbenzene (TMB) and heptane were used to expand the pore size and fluoride (NH4F) was used to modify the length of the pores, leading to porous silicas with different textural properties. The adsorbents, identified as SBA-15 (S), SBA-15 (S1) (TMB), SBA-15 (S2) (TMB and NH4F) and SBA-15 (S3) (NH4F and heptane), were characterized regarding their texture, mesoscopic ordering and chemical surface and finally their adsorption capacity was evaluated using three model biomolecules (Bovine Serum Albumin – BSA, Lysozyme – LYS and Cellulase – CEL). Adsorption behavior of BSA, LYS and CEL onto these SBA-15 samples was investigated by batch experiments at 25 °C. Highest biomolecule uptake obtained for S2 and S3 were attributed to the larger pore diameter, shorter channel length and the formation of interparticle voids, which provides easier access of these biomolecules to the surface of the adsorbent and minimized the diffusion problems. All cellulase adsorption isotherms followed Henry’s Law. The adsorption capacity of cellulase in S2 was 250 mg/g for a liquid-phase equilibrium concentration of 6 mg/mL, while BSA and LYS adsorption isotherms were well fit by the Langmuir model and the maximum adsorption capacities were 581 and 786 mg/g, respectively.

In this work, non-calcined Mg–Al and Zn–Al layered double hydroxides (LDHs) with molar ratio of 3:1 were investigated for the adsorption of bovine serum albumin (BSA). Both LDHs were synthesized using the co-precipitation method and were characterized by X-ray diffraction, N2 adsorption–desorption isotherm at −196 °C, elemental analysis and X-ray photoelectron spectroscopy. The adsorption of BSA was evaluated in a batch adsorption system to assess the influence of buffer solution and buffer pH, contact time and initial concentration. Fixed-bed adsorption experiments were also performed in order to evaluate the dynamic adsorption behavior of BSA on the LDH as well as the regenerability of this material. In the batch adsorption experiments, the maximum amount of BSA adsorbed was reached at its isoelectric point (pI = 4.8) with 50 mM acetate buffer for Mg–Al LDH and pH 6.7 with 50 mM 2-(N-morpholino)ethanesulfonic acid (MES) buffer for Zn–Al LDH. The Langmuir and Langmuir–Freundlich models provided maximum equilibrium adsorption capacity of 338.74 and 346.54 mg g−1for Zn-Al LDH, respectively, and 196.12 and 197.80, respectively, for Mg-Al LDH. Column experiments were carried out with a constant flow of 1 mL min−1, varying the feed concentration of BSA solutions from 1.0 to 2.0 mg mL−1. An average of 98 % of BSA injected into the column was retained, and a completely elution was reached using 50 mM sodium phosphate with pH 12.

Considering the thermodynamic grand potential for more than one adsorbate in an isothermal system, we generalize the model of adsorption-induced deformation of microporous carbons developed by Kowalczyk et al. [1]. We report a comprehensive study of the effects of adsorption-induced deformation of carbonaceous amorphous porous materials due to adsorption of carbon dioxide, methane and their mixtures. The adsorption process is simulated by using the Grand Canonical Monte Carlo (GCMC) method and the calculations are then used to analyze experimental isotherms for the pure gases and mixtures with different molar fraction in the gas phase. The pore size distribution determined from an experimental isotherm is used for predicting the adsorption-induced deformation of both pure gases and their mixtures. The volumetric strain (ε) predictions from the GCMC method are compared against relevant experiments with good agreement found in the cases of pure gases. Fil: Cornette, Valeria Cecilia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Física Aplicada "Dr. Jorge Andrés Zgrablich". Universidad Nacional de San Luis. Facultad de Ciencias Físico Matemáticas y Naturales. Instituto de Física Aplicada "Dr. Jorge Andrés Zgrablich"; Argentina Fil: Alexandre de Oliveira, José Carlos. Universidade Estadual do Ceará; Brasil Fil: Yelpo, Victor Antonio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Física Aplicada "Dr. Jorge Andrés Zgrablich". Universidad Nacional de San Luis. Facultad de Ciencias Físico Matemáticas y Naturales. Instituto de Física Aplicada "Dr. Jorge Andrés Zgrablich"; Argentina Fil: Azevedo, Diana. Universidade Estadual do Ceará; Brasil Fil: López, Raúl Horacio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Física Aplicada "Dr. Jorge Andrés Zgrablich". Universidad Nacional de San Luis. Facultad de Ciencias Físico Matemáticas y Naturales. Instituto de Física Aplicada "Dr. Jorge Andrés Zgrablich"; Argentina

A series of nanoporous carbons was obtained by physical activation of polyethylene terephthalate and investigated for the separation of CO2 from flue gas. The prepared carbons exhibited extremely low functionalization—negligible content in oxygen and other heteroatoms—accompanied by well-developed porous networks consisting of gradually increasing surface areas and micropore volumes. Such features allowed to study the role of nanopore confinement in the separation of carbon dioxide in CO2/N2 gas mixtures. The analysis of the adsorption isotherms of individual gases and their mixtures revealed different trends for the CO2 uptake and the selectivity. Whereas CO2 uptake was larger in the carbons with higher burn-off degree, the selectivity of CO2 over N2 was favored in the carbons with a higher fraction of narrow micropores. The differential adsorption enthalpy curves are typical of highly microporous samples reaching values close to those found in zeolites for low loadings. Data also show that the choice of the best adsorbent for cyclic gas adsorption and separation processes should consider a broad context, taking into account various parameters simultaneously such as gas selectivity, working capacity, adsorption enthalpy and energy consumption in the synthesis of the adsorbent.

Harmful cyanobacterial blooms have become increasingly common in freshwater ecosystems in recent decades, mainly due to eutrophication and climate change. Water becomes unreliable for human consumption. Here, we report a comprehensive study carried out to investigate the water quality of several Campina Grande reservoirs. Our approach included metagenomics, microbial abundance quantification, ELISA test for three cyanotoxins (microcystin, nodularins, and cylindrospermopsin), and in vivo ecotoxicological tests with zebrafish embryos. Cytometry analysis showed high cyanobacterial abundance, while metagenomics identified an average of 10.6% of cyanobacterial sequences, and demonstrated the presence of Microcystis, Cylindrospermopsis, and toxin coding genes in all ponds. Zebrafish embryos reared with pond water had high mortality and diverse malformations. Among the ponds analyzed, Araçagi showed the highest lethality (an average of 62.9 ± 0.8%), followed by Boqueirão (lethality average of 62.5 ± 0.8%). Here, we demonstrate that water from ponds undergoing extremely drought conditions have an abundance of potentially harmful cyanobacteria and their toxins. Our findings are consistent with a scenario in which polluted drinking water poses a great risk to human health.

Monodisperse sequenced peptides and peptoids present unique nano-structures based on their self-assembled secondary and tertiary structures. However, the generation of peptide and peptoid hybrid oligomers in a sequence-defined manner via Ugi multicomponent reaction has not yet been studied. Herein, we report a synthetic strategy that enables both the modification of peptides as well as the generation of sequence-defined peptide-peptoid hybrid structures. Our synthetic methodology rests on the fusion of solid phase peptide synthesis with Ugi multicomponent reactions. We evidence that a diversity of chemical functionalities can be inserted into peptides or used in the design of peptide-peptoid hybrids exploiting a wide functional array including amines, carboxylic acids, hydrocarbons, carbohydrates as well as polymers, introducing a sequence-defined synthetic platform technology for precision peptoid hybrids.

The scaffold-free tissue engineering using spheroids is pointed out as an approach for optimizing the delivery system of cartilage construct. In this study, we aimed to evaluate the micromolded nonadhesive hydrogel (MicroTissues®) for spheroid compaction (2-day culture) and spontaneous chondrogenesis (21-day culture) using cartilage progenitors cells (CPCs) from human nasal septum without chondrogenic stimulus. CPC spheroids showed diameter stability (486 μm ± 65), high percentage of viable cells (88.1 ± 2.1), and low percentage of apoptotic cells (2.3%). After spheroid compaction, the synthesis of TGF-β1, TGF-β2, and TGF-β3 was significantly higher compared to monolayer (p<0.005). Biomechanical assay revealed that the maximum forces applied to spheroids after chondrogenesis were 2.6 times higher than for those cultured for 2 days. After spontaneous chondrogenesis, CPC spheroids were entirely positive for N-cadherin, collagen type II and type VI, and aggrecan and chondroitin sulfate. Comparing to monolayer, the expression of SOX5 and SOX6 genes analyzed by qPCR was significantly upregulated (p<0.01). Finally, we observed the capacity of CPC spheroids starting to fuse. To the best of our knowledge, this is the first time in the scientific literature that human CPC spheroids were formed by micromolded nonadhesive hydrogel, achieving a successful scaffold-free cartilage engineering without chondrogenic stimulus (low cost).

Made available in DSpace on 2018-12-11T17:15:24Z (GMT). No. of bitstreams: 0 Previous issue date: 2017-11-01 Background/Aims: This study aimed to discern whether the cardiac alterations caused by retinoic acid (RA) in normal adult rats are physiologic or pathologic. Methods and Results: Wistar rats were assigned into four groups: control animals (C, n = 20) received a standard rat chow; animals fed a diet supplemented with 0.3 mg/kg/day all-trans-RA (AR1, n = 20); animals fed a diet supplemented with 5 mg/kg/day all-trans-RA (AR2, n = 20); and animals fed a diet supplemented with 10 mg/kg/day all-trans-RA (AR3, n = 20). After 2 months, the animals were submitted to echocardiogram, isolated heart study, histology, energy metabolism status, oxidative stress condition, and the signaling pathway involved in the cardiac remodeling induced by RA. RA increased myocyte cross-sectional area in a dose-dependent manner. The treatment did not change the morphological and functional variables, assessed by echocardiogram and isolated heart study. In contrast, RA changed catalases, superoxide dismutase, and glutathione peroxidases and was associated with increased values of lipid hydroperoxide, suggesting oxidative stress. RA also reduced citrate synthase, enzymatic mitochondrial complex II, ATP synthase, and enzymes of fatty acid metabolism and was associated with increased enzymes involved in glucose use. In addition, RA increased JNK 1/2 expression, without changes in TGF-β, PI3K, AKT, NFκB, S6K, and ERK. Conclusion: In normal rats, RA induces cardiac hypertrophy in a dose-dependent manner. The non-participation of the PI3K/Akt pathway, associated with the participation of the JNK pathway, oxidative stress, and changes in energy metabolism, suggests that cardiac remodeling induced by RA supplementation is deleterious. São Paulo State University (Unesp) Botucatu Medical School Internal Medicine Department São Paulo State University (Unesp) Institute of Biosciences of Botucatu Chemistry and Biochemistry Department São Paulo State University (Unesp) Botucatu Medical School Internal Medicine Department São Paulo State University (Unesp) Institute of Biosciences of Botucatu Chemistry and Biochemistry Department

In this work, we have investigated how the typical honeycomb arrangement of SBA-15 and the mechanisms of CO 2 uptake are affected by the addition of chemicals upon synthesis (to modify pore width and length) and post-synthesis amine functionalization. SBA-15 was synthesized hydrothermally by a conventional route (S00) and such synthesis was then subject to modifications: by adding heptane as a swelling agent (S10) and increasing amounts of ammonium fluoride (S11, S12, S13 and S14) to shorten channels length. All of the synthesized silicas were then subject to APTES grafting and PEI impregnation. CO 2 isotherms were obtained for the pure and amine-loaded samples. They were fitted to the Dual-Site Langmuir model for all functionalized adsorbents, so that it was possible to discriminate the relative importance of chemisorption and physisorption sites. The increasingly disordered frameworks brought about by fluoride addition led to the formation of mesocellular silica foams (MCFs), which were not advantageous to increase CO 2 uptakes in the case of amine-grafting because they have a lower silanol density and hence bind less nitrogen as compared to the conventional SBA-15. In the case of PEI-impregnation, it was found that an addition of a low amount of fluoride is important in the regulation of the chemisorption/physisorption ratio. Promising CO 2 uptakes (2.3 mmol CO 2 /g or 4.6 mmol/g PEI at 25 °C and 1 bar) were found for a load of 50% (wt) PEI in MCF synthesized with the highest NH 4 F/SiO 2 molar ratio (equal to 0.065), which was attributed to a better accessibility of amino groups to CO 2 , as compared to the conventional SBA-15 support subject to the same PEI load.

This double-blind, phase 3 study assessed the efficacy and safety of ganitumab plus gemcitabine as first-line treatment of metastatic pancreatic cancer. The study was stopped after a preplanned futility analysis indicated a positive outcome was unlikely at primary analysis. Ganitumab plus gemcitabine had manageable toxicity but did not improve OS versus gemcitabine alone in unselected patients. Background This double-blind, phase 3 study assessed the efficacy and safety of ganitumab combined with gemcitabine as first-line treatment of metastatic pancreatic cancer. Patients and methods Patients with previously untreated metastatic pancreatic adenocarcinoma were randomly assigned 2 : 2 : 1 to receive intravenous gemcitabine 1000 mg/m2 (days 1, 8, and 15 of each 28-day cycle) plus placebo, ganitumab 12 mg/kg, or ganitumab 20 mg/kg (days 1 and 15 of each cycle). The primary end point was overall survival (OS). Secondary end points included progression-free survival (PFS), safety, and efficacy by levels of circulating biomarkers. Results Overall, 322 patients were randomly assigned to placebo, 318 to ganitumab 12 mg/kg, and 160 to ganitumab 20 mg/kg. The study was stopped based on results from a preplanned futility analysis; the final results are reported. Median OS was 7.2 months [95% confidence interval (CI), 6.3-8.2] in the placebo arm, 7.0 months (95% CI, 6.2-8.5) in the ganitumab 12-mg/kg arm [hazard ratio (HR), 1.00; 95% CI, 0.82-1.21; P = 0.494], and 7.1 months (95% CI, 6.4-8.5) in the ganitumab 20-mg/kg arm (HR, 0.97; 95% CI, 0.76-1.23; P = 0.397). Median PFS was 3.7, 3.6 (HR, 1.00; 95% CI, 0.84-1.20; P = 0.520), and 3.7 months (HR, 0.97; 95% CI, 0.77–1.22; P = 0.403), respectively. No unexpected toxicity was observed with ganitumab plus gemcitabine. The circulating biomarkers assessed [insulin-like growth factor-1 (IGF-1), IGF-binding protein-2, and -3] were not associated with a treatment effect on OS or PFS by ganitumab. Conclusion Ganitumab combined with gemcitabine had manageable toxicity but did not improve OS, compared with gemcitabine alone in unselected patients with metastatic pancreatic cancer. Clinical trial registration ClinicalTrials.gov NCT01231347.

The CO2 adsorption capacity of different functionalized mesoporous silicas of the SBA-15 type was investigated and the influence of textural properties and the effect of the silicon source on the CO2 uptake studied. Several adsorbents based on SBA-15 were synthesized using sodium silicate as silicon source, replacing the commonly used tetraethyl orthosilicate (TEOS). Thus, we synthesized three couples of supports, two at room temperature (RT, RT-F), two hydrothermal (HT, HT-F) and two hydrothermal with addition of swelling agent (1,3,5-triisopropylbenzene) (TiPB, TiPB-F). Within each couple, one of the materials was synthesized with ammonium fluoride (NH4F). The supports were functionalized via grafting 3-aminopropyltriethoxysilane (APTES) and via impregnation with polyethylenimine ethylenediamine branched (PEI). The adsorption behavior of the pure materials was described well by the Langmuir model, whereas for the amine-silicas, a Dualsite Langmuir model was applied, which allowed us to qualify and quantify two different adsorption sites. Among the materials synthesized, only the SBA-15 synthesized at room temperatures (RT) improved its properties as an adsorbent with the addition of fluoride when the silicas were functionalized with APTES. The most promising result was the TiPB-F/50PEI silica which at 75 °C and 1 bar CO2 captured 2.21 mmol/g.

We analyzed the adsorption of CO2 in a Cu-BTC metal-organic framework (MOF) impregnated with ionic liquids (ILs) experimentally and by molecular simulation using the Monte Carlo method. The ILs [bmim][PF6] and [bmim][Tf2N] were impregnated in concentrations of 1, 5 and 10 wt%. Monte Carlo computations showed maximum impregnation load of approximately 30 wt% and improved CO2 adsorption up to 2 bar for all the concentrations tested. Experimentally, the impregnated material was carefully characterized and CO2 isotherms were measured. High concentrations of IL solution (10 wt%) had a pronounced detrimental effect on the textural properties of Cu-BTC, whereas for low concentration (5 wt%), no improvement in CO2 adsorption was observed. Based on the experimental and simulated data, the suitability of Cu-BTC as a target MOF for IL impregnation was examined. This work was supported by the Brazilian research agencies, CNPq and CAPES. E.O. Jardim thanks the CNPq (Brazil) for her grant.

The effect of a-amylase degradation on the release of gentamicin from starch-conjugated chitosan microparticles was investigated up to 60 days. Scanning electron micro- scopic observations showed an increase in the porosity and surface roughness of the microparticles as well as reduced diameters. This was confirmed by 67% weight loss of the microparticles in the presence of a-amylase. Over time, a highly porous matrix was obtained leading to increased per- meability and increased water uptake with possible diffusion of gentamicin. Indeed, a faster release of gentamicin was observed with a-amylase. Starch-conjugated chitosan par- ticles are non-toxic and highly biocompatible for an osteo- blast (SaOs-2) and fibroblast (L929) cell line as well as adipose-derived stem cells. When differently produced starch-conjugated chitosan particles were tested, their cyto- toxic effect on SaOs-2 cells was found to be dependent on the crosslinking agent and on the amount of starch used. V C

Neonicotinoids are the most prominent group of insecticides in the world and are commercialized in over 120 countries for the control of agricultural pests mainly due to their broad-spectrum activity and versatility in application. Though non-target soil organisms are likely to be exposed during application, there is paucity of information in scientific literature regarding their sensitivity to neonicotinoids. This study attempts to fill this gap by evaluating, under laboratory conditions, the chronic toxicity of the neonicotinoids thiacloprid and acetamiprid, through their commercial formulations (CF), to the soil invertebrates Folsomia candida, Eisenia andrei and Enchytraeus crypticus. Results obtained indicate that the relative reproductive sensitivity of the test organisms can be expressed as: F. candida = E. andrei > E. crypticus (for acetamiprid CF) and E. andrei > F. candida > E. crypticus (for thiacloprid CF). To extrapolate from laboratory test results to field conditions, predicted environmental concentrations (PECs) and predicted no-effect concentrations were derived. Calculated toxicity-exposure ratios (TER = EC10/PEC) were below trigger values for acetamiprid and thiacloprid, when estimated with initial PEC. While estimated hazard quotients (HQ = PEC/PNEC), were greater than the European Commission trigger value. Therefore, with the current data under standard environmental risk assessment schemes it can be considered that the risk of thiacloprid and acetamiprid to the soil compartment is unacceptable. However, further research into the effects of these substances on different organisms is required to increase the confidence in the risk assessment estimates for instance, by calculating hazardous concentrations using species sensitivity distribution curves.

Made available in DSpace on 2018-12-11T17:11:01Z (GMT). No. of bitstreams: 0 Previous issue date: 2017-04-04 Background: Over the past years, several cardiac risk indices were evaluated and modified, including Goldman, Detsky, and Lee scores. The predictive capacity of these scores in hip fracture patients is lacking. Thus, our objective was to compare the Goldman, Detsky, and Lee scores as predictors of mortality in 6 months after hip fracture. Methods: We prospectively evaluated 80 consecutive patients with hip fractures, over the age of 65 admitted to an orthopedic ward at Botucatu Medical School. Patient demographic information, Goldman, Detsky and Lee scores were recorded. All patients were followed for 6 months after hip fracture, and mortality was recorded. Multiple logistic regression analyses were performed for mortality prediction. Results: The mortality rate was 23% after a 6-month follow-up period. Patients who died had advanced age and the majority of them were male. They also had lower values of handgrip strength, and higher values of creatinine and urea. In the multiple logistic regression models when adjusted by age, gender, handgrip strength and creatinine, Goldman’s score (OR:3.025; 95%CI:1.022-8.953; p:0.046), but not Detsky (OR:2.328; 95%CI:0.422-12.835; p:0.332) and Lee (OR:1.262; 95%CI:0.649-2.454; p:0.494), was associated with mortality 6 months after hip fracture. Each 1 category increase in Goldman score increased the mortality to more than 3-fold. Conclusions: In conclusion, our data suggest that Goldman score, but not Detsky or Lee indices, predicts mortality associated with hip fracture at up to 6 months post-injury. Internal Medicine Department Botucatu Medical School UNESP - Univ Estadual Paulista, Rubião Júnior s/n Surgery and Orthopedic Department Botucatu Medical School UNESP - Univ Estadual Paulista Internal Medicine Department Botucatu Medical School UNESP - Univ Estadual Paulista, Rubião Júnior s/n Surgery and Orthopedic Department Botucatu Medical School UNESP - Univ Estadual Paulista

The aim of this work was to evaluate the ability of Cibacron Blue F-3GA dye-ligand chitosan/alginate epoxide on human IgG adsorption under different buffer systems at 25 mmol L−1: Morpholinoethane sulfonic acid, morpholinopropane sulfonic acid, hydroxyethylpiperazine ethanesulfonic acid and tris-hydroxymethyl aminomethane (Tris–HCl). Batch adsorption studies were performed in order to evaluate the effect of buffer pH and nature on IgG uptake as well the equilibrium isotherms. Chromatographic experiments were performed with both human IgG (high purity) and human serum and each buffer with NaCl 1.0 M was used in the elution step. Best results (maximum equilibrium adsorption capacity of 110.9 mg g−1) were found at pH 7.8 with Tris–HCl buffer. The Langmuir–Freundlich model provided a good fit for the adsorption isotherm. In chromatographic experiments with high purity IgG and Tris/HCl buffer, IgG dynamic adsorption capacity onto E-Ch/Al-Cibacron was 13.4 mg g−1, which accounted for 60 % of IgG injected into the column. Chromatographic experiments with diluted (tenfold) human serum were conducted and it was found by electrophoresis that IgG is preferentially adsorbed with respect to other proteins using all buffers systems, especially with Tris–HCl. The amount of desorbed protein from E-Ch/Al-Cibacron was around 7.0 mg g−1 for all buffers. The new stationary phase showed high affinity for IgG and may be a potential adsorbent for human IgG purification.

Desulfurization of benzothiophene/isooctane mixtures and gasoline (42.5 and 1000 ppmw S) was studied by batch and fixed bed experiments using PdCl2 supported on mesoporous silica of SBA-15 type (PdCl2/SBA-15). The Pd-loaded silica was prepared by solid-phase impregnation of the metal halide on the mesoporous siliceous matrix (SBA-15). SBA-15 and PdCl2/SBA-15 were characterized with N2 adsorption/desorption isotherms, small angle X-ray diffraction and transmission electron microscopy (TEM). Then desulfurization of benzothiophene/isooctane mixtures and gasoline (42.5 ppmw S) with these sorbents was investigated by batch and fixed bed experiments. PdCl2/SBA-15 showed much higher capacity for sulfur adsorption than both the starting material and PdCl2 itself. A mathematical model was used to represent the breakthrough curves for adsorption and desorption runs in fixed bed, providing very good agreement between numerical simulations and adsorption data. The spent PdCl2/SBA-15 was regenerated using isooctane as eluent, and the regenerated PdCl2/SBA-15 was tested again for the desulfurization of 1000 ppm S gasoline (down to 50 ppm). The results showed that the sulfur adsorption capacity at the break point (C = 50 ppm) remained nearly unchanged for three cycles, even though XPS elemental analysis for the fresh and spent adsorbent revealed some degree of leaching of the metal from the external surface, particularly as Pd(II). In conclusion, PdCl2/SBA-15 appears to be a robust adsorbent for desulfurization of liquid fuels and the model proposed herein was able to predict deep desulfurization of gasoline in cyclic mode.