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In this paper, we describe a process to add value to the biomass derivatives (i.e., levulinic acid), converting it to bioadditives over solid Sn(II) exchanged Keggin heteropolyacid salts. These solid catalysts are an attractive alternative to the traditional soluble and corrosive Bronsted acid catalysts. Among Sn(II) heteropoly salts, the Sn1.5PW12O40 was the most active and selective catalyst, achieving high conversions (ca. 90 %) and selectivity (90–97 %) for alkyl esters and angelica lactone, the main reaction products. The impacts of the main reaction parameters (i.e., catalyst load, temperature, and the molar ratio of alcohol to acid) were investigated. The use of renewable raw material, and an efficient and recyclable catalyst are the main positive features of this process. The Sn1.5PW12O40 catalyst was easily recovered and reused without loss activity.

In this work, Sn(II)-exchanged silicotungstic acid salt (i.e., Sn2SiW12O40) was synthesized and evaluated as the catalyst on the acetalization of glycerol with acetone to produce solketal, a versatile bioadditive of fuel. The Sn2SiW12O40 salt was compared to the other solid Keggin heteropoly salts (i.e., Sn3/4PMo12O40, Sn3/4PW12O40), and liquid (i.e., HCl, H2SO4 and p-toluenesulfonic acid) catalysts. Amongst the catalysts assessed, it was the most active, achieving a high conversion (ca. > 99%, after 1 h reaction at room temperature) and selective (ca. 97%) toward the formation of solketal. Moreover, the Sn2SiW12O40 salt demonstrated to be more active than acid and precursor Tin (II) chloride salt, as well as other heteropoly salts and solid supported catalysts. The effects of the main reaction variables were assessed. The Sn(II) cation, as well as the silicotungstate anion, showed being essential to convert glycerol to solketal. Insights on the reaction mechanism were performed. In a simple recycle procedure, the solketal was purified, the acetone excess recycled, and the catalyst was reused without loss activity.

In order to investigate the effect of Lewis acidic metals on the acid properties of Keggin heteropolyacids catalysts, a set of metal-exchanged HPAs (i.e. M3/nPW12O40, M3/nPMo12O40 and M4/nSiW12O40 (M = Cu, Co and Mn, n = 2; M = Fe, n = 3) were synthesized and their activity on glycerol esterification with acetic acid was evaluated. This procedure avoids the use of corrosive Bronsted acid catalysts. Regardless of the heteropoly anion, the activity of catalysts in terms of metal cations followed the sequence: Fe3+> Cu2+> Mn2+> Co2+. It has been found that among the HPAs, only H4SiW12O40 has the acidic protons that can be successfully exchanged with Fe3+ cations, resulting in Fe4(SiW12O40)3 salt, the most active and selective catalyst. The highest conversion (ca.99.9%) was achieved in Fe4(SiW12O40)3-catalyzed esterification reactions, along with the highest selectivity for di and triacetyl glycerol (ca.55 and 42%, respectively). Effects of temperature, stoichiometry of reactants, concentration and nature of catalysts were assessed. A kinetic study of Fe4(SiW12O40)3 or H4SiW12O40-catalyzed reactions was conducted and the activation energy determined.

Vinceae comprises 9 genera and about 153 species. The genera differ greatly in a number of morphological traits, especially those relating to fruit and seeds, which resulted in their placement in different tribes and/or subtribes by earlier taxonomists. Here, 378 new chloroplast DNA sequences from 98 species from 5 tribes of the rauvolfioid grade were analyzed phylogenetically to test the monophyly of Vinceae, its 6 subtribes, and constituent genera, as well as the sectional treatments of Rauvolfia, and to find morphological synapomorphies for major clades. Vinceae, as currently circumscribed, was found to be monophyletic as were four of the six subtribes. Kopsia and Ochrosia were confirmed as successive sister groups to the rest. All nine genera currently recognized in the tribe were resolved as monophyletic, Laxoplumeria and Tonduzia for the first time. The broad circumscription of Petchia and Ochrosia proposed by previous authors was supported. The pantropical genus Rauvolfia is divided into two major lineages: one comprised entirely of paleotropical species, and the other the neotropical species, a recurring geographic pattern in the family. Surprisingly, the Hawaiian species of Vinceae have probably arisen by two different trans-oceanic routes, either by long-distance dispersal from Australasian (Ochrosia spp.) or Caribbean (Rauvolfia sandwicensis) ancestors. Within Rauvolfia, most of the sections, series and subseries recognized in previous classifications are paraphyletic. Only 2 of the 14 sections of Rauvolfia proposed by Pichon and 1 of the 11 sections proposed by Rao that are not monospecific were found to be monophyletic. Mapping of 30 morphological characters onto the molecular tree identified an unlobed upper wreath on the style head as an unambigous synapomorphy characterizing the tribe as well as synapomorphies for each of its genera. The two earliest-branching genera, Kopsia and Ochrosia, have dextrorse corolla lobe aestivation, in contrast to the sinistrorse corollas of the other Vinceae and the great majority of genera throughout the rauvolfioid grade. Drupes have arisen in parallel at least three times within Vinceae. The adaptations of the endocarp for water dispersal are possibly ancestral in the tribe, and the observed morphological differences between the drupaceous fruits of Kopsia/Ochrosia versus Petchia and Rauvolfia may be due to their abiotic versus biotic dispersal mode, respectively.

In this paper, we report a route to produce levoglucosan (LGA), a biomass-derived platform-molecule that is starting material to obtain various compounds of industrial interest, such as lipids, citric acid, ethanol, 5-hydroxymethylfurfural, furans, aromatic hydrocarbons among other biobased products. Among the several routes to obtain LGA, the fast pyrolysis of lignocellulosic biomass containing glucose monomer has received growing attention due to economic and environmental reasons. In this work, we have developed a new method based on the pretreatment of sugarcane bagasse before the fast pyrolysis with a series of Keggin-type heteropolyacids (i.e., H3PW12O40, H3PMo12O40, and H4SiW12O40), which are solid catalysts easy to handle. Sugarcane bagasse, a biomass waste generated at large scale by food and fuel industries was the feedstock selected. The effects of the main variables of the acid pretreatment such as the nature of the catalyst, time, and temperature of the process were assessed. The efficiency of different pretreatments was examined by the analysis of product distribution obtained from fast pyrolysis. This new method resulted in a significant increase in LGA yield (32 %) as compared to those from pure water pretreated (5 %) and untreated sugarcane bagasse (4 %). Among all the acid catalysts tested, the H3PW12O40 was the most active and selective, due to highest Bronsted acidity strength. The great improvement in LGA yield was attributed to the structural changes in sugarcane bagasse occurred during the acidic pretreatment, which were confirmed by thermal analysis (TG/ DTG) and scanning electron microscopy (SEM) performed before and after the treatment.

In this paper, several commercial transition metal salts were tested in acetalization reactions of glycerol with acetone to produce solketal (i.e., 2,2-dimethyl-1,3-dioxolan-4-yl)methanol). Among the salts assessed, Fe(NO3)3 9⋅H2O exhibited the highest catalytic activity, virtually converting all the glycerol to solketal, with 95% selectivity in short reaction time (ca. 30 min). Ferric nitrate is inexpensive, commercially available, non-corrosive and water-tolerant Lewis acid catalyst. Although soluble, it was easily recovered through a liquid-liquid extraction process followed by the drying of the aqueous phase and reused without loss activity or selectivity. The performance of Fe(NO3)3 was compared to other Lewis and Bronsted acid catalysts. Insights on the reaction mechanism were performed aiming to verify the effect of H+ ions generated by hydrolysis of metal catalysts throughout the reactions. This process described herein is an attractive option to the Bronsted acid-catalyzed routes because it is non-corrosive, avoids products neutralization steps and allow an easy recovery and reuse of catalyst.

In this work, metal cations exchanged silicotungstic acid salts were synthesized and evaluated as catalysts in furfural oxidative esterification reactions with hydrogen peroxide in alkyl alcohols solution. The protons of silicotungstic acid were totally exchanged with Co2+, Cu2+, Ni2+, Al3+, and Fe3+ cations, generating catalysts that were characterized by infrared spectroscopy, X-rays diffraction patterns, energy dispersive spectroscopy, scan electronic microscopy images, and thermal analyses. Isotherms of adsorption/ desorption of nitrogen provided the surface area, distribution, volume, and pores diameter. The strength and amount of the acid sites were determined by potentiometric titration curves. Noticeably, the oxidation of furfural proceeded without opening the furan ring. Furoic acid and alkyl furoate were the main reaction products, with the formation of the furfural acetal as a secondary product. The effect of main reaction parameters such as the H2O2: furfural molar ratio, the catalyst amount, and the temperature were studied. The reactivity of the furfural with other alkyl alcohols was also assessed. The solid, active, and easily synthesizable catalyst, and the use of an inexpensive and environmentally benign oxidant are positive aspects of this selective process for oxidative esterification of furfural.

Herein, an efficient amphiphilic carbon catalyst produced by the reaction of bio-oil with sulfuric acid was used for the first time for the solvent-free glycerol ketalization with 2-propanone for solketal production (2,2-dimethyl-1,3-dioxolane-4-methanol) at room temperature. The catalyst synthesis, described previously, led to an amphiphilic carbon due to hydrophobic nanostructures, e.g. graphene, nanotube, nano-onions, nanographite, embedded in an amorphous carbon containing high concentration of hydrophilic oxygen and sulfonic surface groups with strong acid sites (ca. 0.3 mmol g−1). The amphiphilic catalyst promoted the formation of an emulsion from the two immiscible phases, glycerol and 2-propanone, which had a strong effect on the reaction interface and solketal yield. Glycerol ketalization at 25 °C and solvent-free showed conversions higher than 90%, using 0.6 wt% catalyst, 1:10 glycerol:2-propanone after 2 h. The catalyst can be recovered and reused four times without any significant activity loss.

In this work, a solid acid catalyst based on different nanostructures, e.g. graphene, nanotube, nano-onions, nanographite, embedded in amorphous carbon matrix was used as a catalyst on esterification reaction of oleic acid and methanol. The materials were characterized by transmission electron microscopy, elemental analysis, thermogravimetric analysis coupled with mass spectrometry, surface area analyses and potentiometric titration showing the presence of sulfonic acid sites (0.02-0.30 mmol g−1) on the carbon structures. The obtained materials were used as catalysts for the esterification of oleic acid with methanol (1:10 M ratio) showing conversions of 95 %, using 2.5 wt % at 100 °C for 3 h. Reuse reactions showed that catalytic activity decreased to 20% after 4 uses, probably due to leaching or methylation of sulfonic groups. Activation energy of the esterification reaction was also calculated, e.g. 52 kJ mol−1.

The area occupied by tropical forests in South America has continually experienced shrinkage since the Miocene, with the formation of the Dry Diagonal, which is composed of seasonally dry tropical forests and savannas (Caatinga, Cerrado, and Chaco). Here, we contribute to the understanding of the establishment of the Dry Diagonal by testing the hypotheses of “ancestral fragmentation” and of “colonization” to explain the current distribution of species in rocky humid formations of Cerrado, a Neotropical savanna in Brazil. Populations of Mandirola hirsuta (Gesneriaceae) were sampled in 25 localities; these cover the species’ entire geographical distribution, and the plastid intergenic regions psbA-trnH and trnQ-5′-rps16 were sequenced. The findings show that intrapopulation genetic variability was low, whereas interpopulation variability was high. We detected seven genetic groups that were geographically well delimited, and no signs of recent population expansion were observed. Divergence between the seven main lineages took place between the late Miocene and the Pliocene periods. In Approximate Bayesian Computation, the fragmentation scenario had a significantly higher probability than the colonization scenario. Results support the hypothesis of a former broader distribution for the humid vegetation, which was fragmented with the expansion of savannas; results also indicate population differentiation promoted by a rapid expansion of the Dry Diagonal.

In Brazil, 48% of the population use WhatsApp to share and discuss news. Currently, there are serious concerns that this platform can become a fertile ground for groups interested in disseminating misinformation, especially as part of articulated political campaigns. Particularly, WhatsApp provides an important space for users to engage in public conversations that worth attention, the public groups. These groups are suitable for political activism and social movement organization. Additionally, it is reasonable to assume that a malicious misinformation campaign might attempt to maximize the audience of a fake story by sharing it in existing public groups. In this paper, we present a system for gathering, analyzing and visualize public groups in WhatsApp. In addition to describe our methodology, we also provide a brief characterization of the content shared in 127 Brazilian groups. We hope our system can help journalists and researchers to understand the repercussion of events related to the Brazilian elections within these groups.

In this work, we developed a route to synthesize fuel bioadditives based on simple and inexpensive commercial catalyst: iron(III) sulfate. This process is an alternative to the traditional Bronsted acid catalysts, avoiding steps to neutralize the catalyst, which generates a large amount of effluents and residues. High conversions (ca. 90%) and selectivity (90–97%) for alkyl esters of levulinic acid with carbon chain ranging from C6–C9 were obtained, when Fe2(SO4)3 was the catalyst. The role of each component catalyst system was studied, with a special attention on the reaction temperature, stoichiometry of reactants and catalyst concentration. We investigate the catalytic activity of others commercial transition metal salts (i.e., Fe2(SO4)3, FeCl3, CuSO4, FeSO4, MnSO4, NiSO4). Although soluble, the Fe2(SO4)3 catalyst was easily recovered by silica column chromatography, in the same step of products purification, and reused without loss activity. The use of renewable raw material and an efficient, inexpensive and recyclable catalyst are the main positive features of this process.

The catalytic activity of p-sulfonic acid calix[4]arene was studied in the transesterification reactions of Passiflora seed oil with methanol or ethanol. Calix[n]arenes are highly versatile organocatalysts and conversion rates >98 % were obtained for the transformation of Passiflora seed oil to its methyl or ethyl esters after 5 h of reaction in the presence of p-sulfonic acid calix[4]arene (3.52 mol % in ethanol; 5.28 mol % in methanol). Moreover, the organocatalyst was recovered and reused in two subsequent cycles without a significant decrease in the activity or selectivity. The use of a non-corrosive and reusable organocatalyst is the positive aspect of this process.

Biodiesel has become increasingly attractive because of its environmental benefits and production from renewable resources. The use of Jatropha curcas L. oil as the feedstock for biodiesel production has attracted growing interest because it is a non-edible oil. Herein, easy ambient sonic-spray ionization mass spectrometry (EASI–MS) was used to chemically characterize, at the molecular level, J. curcas L. oil and its biodiesel via monitoring its triacylglycerols (TAG), free fatty acids (FFA), and profiles of fatty acid methyl esters (FAME). The results provide further support for those obtained by the standard parameters of fuel quality. The EASI–MS analysis described herein is simple, requires only a tiny droplet of the sample, and is conducted without any pre-separation or chemical manipulation steps.

A finalidade deste artigo é mostrar como Heidegger concebe a essência da linguagem. Para isso, travamos uma conversa com ele mediante A Caminho da Linguagem, um diálogo que privilegia mais a escuta que a fala. Ouvimos seu apelo acerca da relação entre poesia e pensamento e da essência da linguagem. Analisamos quais as implicações do seu interesse pela etimologia e o que há em comum entre ele e os semanticistas da enunciação. O filósofo nos diz que, se pararmos, estamos mais perto da linguagem do que nos movimentando em sua busca.

In this work, the sources of contamination by Enterococcus spp. in a ricotta processing line were evaluated. The isolated strains were tested for virulence genes (gelE, cylA,B, M, esp, agg, ace, efaA, vanB), expression of virulence factors (hemolysin and gelatinase), and the resistance to 10 different antibiotics. Enterococcus faecium and Enterococcus faecalis were subjected to discriminatory identification by intergenic spacer region (ITS)-polymerase chain reaction and sequencing of the ITS region. The results showed that Enterococcus spp. was detected in the raw materials, environment samples and the final product. None of the 107 Enterococcus isolates were completely free from all virulence genes considered. A fraction of 21.5% of the isolates containing all of the genes of the cylA, B, M operon also expressed β-hemolysis. Most of the isolates showed the gelE gene, but only 9.3% were able to hydrolyze gelatin. In addition, 23.5% of the observed Enterococcus isolates had the vanB gene but were susceptible to vancomycin in vitro. The dissemination of antibiotic-resistant enterococci was revealed in this study: 19.3% of the E. faecium samples and 78.0% of the E. faecalis samples were resistant to at least one of the antibiotics tested. Sequencing of region discriminated 5 and 7 distinct groups among E. faecalis and E. faecium, respectively. Although some similarity was observed among some of the isolates, all E. faecalis and E. faecium isolates had genetic differences both in the ITS region and in the virulence profile, which makes them different from each other.

Herein, an efficient and environmentally benign tin-based process who is a simple and available commercially catalyst, was used in the glycerol ketalization with different ketones at room temperature and solvent-free reactions. Although being a molecule highly functionalized, glycerol was selectively converted to ketal in all the SnCl2-catalyzed reactions. A high regioselectivity (ca. 78–99 % for 1,3-dioxolane derivatives) was achieved for ketones with straight or cyclic chain having up to six carbon atoms. Conversely, glycerol ketalization with branched carbon chain ketones containing six carbon atoms (i.e. 4-methyl-2-pentanone) resulted in the equimolar formation of two isomers products (i.e. cis and trans-1,3-dioxolane isomers glycerol derivatives). The main reaction parameters such as the ketone nature, reactants stoichiometry and catalyst concentration were assessed. The SnCl2 catalyst operate at mild and solvent-free reaction conditions and was successively recovered and reused without activity loss. Tin-catalyzed glycerol ketal synthesis

This study aimed to elucidate the responses of the Neotropical fish Lophiosilurus alexandri exposed to ammonia and nitrite, following a period of recovering. Acute toxicity tests lasted 96h, subchronic toxicity tests lasted eight days and the detoxification trial lasted four days. Groups of 12 juveniles were maintained in 90-L tanks and treated with increasing concentrations of ammonia and nitrite, except during the recovery test. All treatments were performed with two replicates. The median lethal concentrations (LC50) of 24, 48, 72 and 96h were estimated at 30.12; 24.35; 19.24 and 18.68mg·L-1 TA-N; 5.37; 4.57; 3.75 and 3.66mg·L-1 NH3-N and 20.37; 7.78; 7.09 and 5.86mg·L-1 NO2--N, respectively. The NO2- caused significant decrease in hematocrit and increase in the urea levels during short-term exposure, with recovery of homeostasis after the subchronic and detox period. Acute exposure to ammonia increased the enzyme profile of transaminases, glucose and urea. Urea concentration remained high in the subchronic and detox tests. Histopathologies were observed in animals exposed to ammonia in both toxicity tests. It was highlighted detachment of epithelium, hyperemia and necrosis in the gills. Exposure to NO2- caused epithelium detachment and aneurysm. Vacuolization and swelling of hepatocytes were the most common injury for both nitrogenous compounds. We concluded that the L. alexandri has moderate tolerance to ammonia and nitrite. The recovery period revealed remedial response to ammonia and nitrite exposure.

Objective The transcriptional repressor DREAM is involved in thyroid-specific gene expression, thyroid enlargement and nodular development, but its clinical utility is still uncertain. In this study we aimed to investigate whether DREAM mRNA levels differ in different thyroid tumors and how this possible difference would allow the use of DREAM gene expression as molecular marker for diagnostic and/or prognosis purpose. Materials and methods We quantified DREAM gene mRNA levels and investigated its mutational status, relating its expression and genetic changes to diagnostic and prognostic features of 200 thyroid tumors, being 101 malignant [99 papillary thyroid carcinomas (PTC) and 2 anaplastic thyroid carcinomas] and 99 benign thyroid lesions [49 goiter and 50 follicular adenomas (FA)]. Results Levels of mRNA of DREAM gene were higher in benign (0.7909 ± 0.6274 AU) than in malignant (0.3373 ± 0.6274 AU) thyroid lesions (p < 0.0001). DREAM gene expression was able to identify malignancy with 66.7% sensitivity, 85.4% specificity, 84.2% positive predictive value (PPV), 68.7% negative predictive value (NPV), and 75.3% accuracy. DREAM mRNA levels were also useful distinguishing the follicular lesions FA and FVPTC with 70.2% sensitivity, 73.5% specificity, 78.5% PPV, 64.1% NPV, and 71.6% accuracy. However, DREAM gene expression was neither associated with clinical features of tumor aggressiveness, nor with recurrence or survival. Six different genetic changes in non-coding regions of DREAM gene were also found, not related to DREAM gene expression or tumor features. Conclusion We suggest that DREAM gene expression may help diagnose thyroid nodules, identifying malignancy and characterizing follicular-patterned thyroid lesions; however, it is not useful as a prognostic marker.

Machaerium villosum is an important tree species from Southeastern Brazil. We report hereby 10 new microsatellite markers to investigate the structure and genetic diversity of this species. Ninety-seven alleles were detected in 60 specimens from a natural population in Minas Gerais State. High genetic diversity has been found. The mean observed and expected heterozygosities were 0.771 and 0.802, respectively. One locus showed significant Hardy-Weinberg departure and five loci combinations showed significant linkage disequilibrium. These 10 new microsatellite loci will be used to evaluate the genetic diversity of this species in order to understand the fragmentation effects of the Brazilian Atlantic Rain Forest.

Simple Fe(NO3)2·9H2O was demonstrated to be able to catalyze the oxidation of monoterpenes by hydrogen peroxide in methyl alcohol solution. Compared with the previous iron-catalyzed methods, the present procedure avoids the use of stabilizing ligands, additives, and corrosive peroxide organic oxidants. A novel, simple and highly efficient catalyst system was developed for oxidizing monoterpenes into a valuable derivates using hydrogen peroxide, an environmentally friendly oxidant. Possible steps involved in the Fe(III)-catalyzed oxidation of β-pinene by hydrogen peroxide into myrtenol methyl ether in methyl alcohol

Background Extended-spectrum β-lactamases (ESBLs) are increasingly prevalent in Enterobacter spp., posing a challenge to the treatment of infections caused by this microorganism. The purpose of this retrospective study was to evaluate the prevalence, risk factors, and clinical outcomes of inpatients with bacteremia caused by ESBL and non ESBL-producing Enterobacter spp. in a tertiary hospital over the period 2004–2008. Methods The presence of bla CTX-M , bla TEM , bla SHV , and bla PER genes was detected by polymerase chain reaction (PCR) and nucleotide sequence analysis. Genetic similarity between strains was defined by pulsed-field gel electrophoresis (PFGE). Results Enterobacter spp. was identified in 205 of 4907 of the patients who had positive blood cultures during hospitalization. Of those cases, 41 (20%) were ESBL-producing Enterobacter spp. Nosocomial pneumonia was the main source of bacteremia caused by ESBL-producing Enterobacter spp. The presence of this microorganism was associated with longer hospital stays. The ESBL genes detected were: CTX-M-2 (23), CTX-M-59 (10), CTX-M-15 (1), SHV-12 (5), and PER-2 (2). While Enterobacter aerogenes strains showed mainly a clonal profile, Enterobacter cloacae strains were polyclonal. Conclusion Although no difference in clinical outcomes was observed between patients with infections by ESBL-producing and non-ESBL-producing strains, the detection of ESBL in Enterobacter spp. resulted in the change of antimicrobials in 75% of cases, having important implications in the decision-making regarding adequate antimicrobial therapy.

Dissertação de Mestrado Integrado em Arquitetura, com a especialização em Arquitetura, apresentada na Faculdade de Arquitetura da Universidade de Lisboa para obtenção do grau de Mestre. Submitted by Pilar Lago (mpilar@fa.utl.pt) on 2017-04-06T12:27:30Z No. of bitstreams: 1 MC_DCRefugiados2016.pdf: 10359448 bytes, checksum: 397f7c6e06506e59740b5e921609e7c3 (MD5) Made available in DSpace on 2017-04-06T12:27:30Z (GMT). No. of bitstreams: 1 MC_DCRefugiados2016.pdf: 10359448 bytes, checksum: 397f7c6e06506e59740b5e921609e7c3 (MD5) Previous issue date: 2016-12-06 N/A

Dissertação de Mestrado Integrado em Arquitetura, com a especialização em Arquitetura, apresentada na Faculdade de Arquitetura da Universidade de Lisboa para obtenção do grau de Mestre. N/A

In this work, monolacunary Keggin heteropolyacid salts containing sodium as the countercation were synthesized and evaluated as catalysts on the camphene oxidation with hydrogen peroxide. Under reaction conditions (i.e., 333 K, air atmosphere, CH3CN solution), camphene (1) was selectively oxidized by H2O2, generating two rare products; camphene aldehyde (1a) and camphenylic acid (1b), which have attractive olfactive properties. Notably, these uncommon compounds were obtained with the camphene preserving their carbon skeletal. Among the lacunar Keggin heteropolyacid salts, the Na7PW11O39 lacunar salt was the most active and selective toward oxidation products, completely converting the camphene to (1a) and (1b) products. The catalyst load, the oxidant: camphene molar ratio and the reaction temperature allowed to control the (1a)/ (1b) proportion.

Background The role of radiomics against clinical and histologic standard has been repeatedly demonstrated, although the integration of high-throughput imaging into a multidimensional prediction model is still in its early dawn. Thus, the aim of the present study was to determine whether CT-derived radiomic features (CT-RFs) might intercept the landscaped arrangement of the tumor immune microenvironment (TIME), offering a novel non-invasive assessment of prognostic factors in NSCLC. Methods A cohort of 100 (70 training and 30 validation) surgically resected NSCLC was investigated. TIME was classified according to PD-L1 and Tumor Infiltrating Lymphocytes (TILs) levels and further defined as hot, intermediate or cold by the relative contribution of effector and suppressor phenotypes. Extracted CT-RFs were correlated to TIME profiles and ROC curves were used to test the accuracy of the radiomic predictor. The impact of integrated radio-immune parameters on clinical outcome was estimated by Kaplan Meier method. Results Patient-specific tissue immune profiles were reflected by a strong correlation between CT-RFs and TIME parameters (U-Mann Whitney Test). Cluster Tendency and GrayLevelNonUniformity were upregulated in PD-L1high and TILs rich tumors (p Conclusions Specific TIME profiles inscribe radiomic features resulting in a radio-immune signature with prognostic impact on NSCLC. Legal entity responsible for the study University of Parma. Funding University of Parma. Disclosure All authors have declared no conflicts of interest.

In this work, the activity of Sn(II)-Keggin heteropolyacid salts (i.e., Sn3/2PW12O40 and Sn3/2PMo12O40) was investigated on the etherification reactions of glycerol with tert-butyl alcohol. Tin(II) heteropoly catalysts were easily synthesized and characterized by analyses of FT-IR/ATR, TG/DSC, MEV/EDS, XRD, BET, and potentiometric titration with n-butylamine. The activity of heteropoly salts was compared to the precursor heteropolyacids and SnSO4 catalysts. The Sn3/2PW12O40-catalyzed etherification achieved the highest tert-butyl glycerol ethers selectivity (ca. 90%) after 4 h of reaction at 363 K. The selectivity toward mono-glyceryl tert-butyl ether (i.e., an efficient surfactant) or di-tert-butyl glyceryl ether (i.e., a fuel bioadditive) can be tailored by an adequate adjustment of the reaction parameters (i.e., catalyst loading, reactant stoichiometry). Glycerol ethers were characterized by 1H and 13C NMR and infrared spectroscopy and mass spectrometry.

The Fe(III)-catalyzed aerobic oxidation of monoterpenes in CH3OH has been developed, in which simple Fe(III) salts are used as catalysts in the absence of stabilizing ligands. Remarkably, Fe(NO3)3 catalyst efficiently promotes the oxidation of monoterpenes under air or dioxygen. The highest TON and TOF reached 476 and 162 h− 1, respectively. In general, reactions with 1.0–9.0 mol% of catalyst reached high conversions (ca. 90–99%) and high oxidation products selectivity (ca. 80%). Notably, α-pinene and β-pinene were selectively oxidized into only allylic product, myrtenol methyl ether. The significant breakthroughs of this simple oxidative process are the use of inexpensive Fe(III) salts as catalysts and environmentally-friendly oxidants (air or dioxygen).

The interest in the development of efficient and environmentally benign catalysts for esters synthesis has increased exponentially, mainly due to the demand for biodiesel. In general, fatty esters are used as bioadditive, cosmetic ingredients, polymers, and, more recently, biofuel. Nevertheless, most of the production processes use nonrecyclable and homogenous alkaline catalysts, which results in the reactors corrosion, large generation of effluents, and residues on the steps of separation and catalyst neutralization. Heterogeneous acid catalysts can answer these demands and are an environmentally benign alternative extensively explored. Remarkably, solid acid catalysts based on tin have been shown highly attractive for the biodiesel production, mainly via FFA esterification reactions. This review describes important features related to be the synthesis, stability to, and activity of heterogeneous tin catalysts in biodiesel production reactions.

The selective transformation of glycerol into value-added products remains a challenging task due to its polyfunctional nature. Conversion of glycerol into 2,2-dimethyl-1,3-dioxolane-4-methanol (i.e., solketal) was efficiently catalyzed by SnCl2 at room temperature and in solvent-free conditions. Solketal is an useful additive for the formulation of gasoline, diesel, and biodiesel. Tin chloride, an inexpensive, water-tolerant, and minimally corrosive Lewis acid catalyst, has demonstrated excellent catalytic behavior in the acetalisation of glycerol with acetone to yield solketal with a higher efficiency than traditional Bronsted acids (i.e., p-toluenesulfonic acid or sulfuric acid). The effects of various parameters, such as catalyst loading, acetone/glycerol molar ratio, and temperature on the selectivity and conversion of glycerol was investigated in detail. Although used in the homogeneous phase, the SnCl2 catalyst was easily recovered and reused without any reactivation treatment up to six times, keep...

In this work, the efficiency of Lewis acid catalysts, SnX2 (X = F−, Cl−, Br−, or −OAc), was investigated on the esterification reactions of fatty acids (i.e., myristic, palmitic, stearic, oleic, linoleic, and linoleic) with different alcohols (i.e., methyl, ethyl, propyl, isopropyl, and butyl alcohol). Tin(II) bromide was the most active catalyst in all reactions studied. We investigated the effects of main reaction parameters, such as catalyst concentration, temperature, and nature of alcohol and fatty acid. The highest activity of SnBr2 catalyst was discussed in terms of its lower activation energy, higher Lewis acid strength, and higher softness of anionic ligand. Finally, the SnBr2 catalyst can be easily recovered and reused without loss of catalytic activity. Effect of the tin catalyst nature on the oleic acid esterification with ethyl alcohol.

A novel process was developed for oxidative desulfurization (ODS) in the absence of a phase transfer catalyst (PTC) using only Keggin heteropolyacids and their aluminum salts as catalysts. Reactions were performed in biphasic mixtures of isooctane/acetonitrile, with dibenzothiophene (DBT) as a model sulfur compound and hydrogen peroxide as the oxidant. Remarkably, only the AlPMo12O40-catalyzed reactions resulted in complete oxidation of DBT into DBT sulfone, which was totally extracted by acetonitrile, reducing the sulfur content of isooctane from the 1000 ppm to 12O40 > H3PMo12O40 > AlPW12O40 > H3PW12O40. The absence of a PTC, acidic organic peroxides, and the use of hydrogen peroxide, an environmentally benign oxidant, make up the positive aspects of AlPMo12O40-catalyzed ODS reactions. In these reactions, high rates of DBT removal (ca. 100%) were achieved within a short time (ca. 2 hours) and under mild reaction conditions.

The aim of this study was to investigate the association between three polymorphisms involved in the oxidative stress pathway and fetal hemoglobin (Hb F) levels in patients with sickle cell anemia in a Brazilian population. One hundred and seven patients with sickle cell anemia were recruited for genomic DNA extraction. The levels of Hb F, sex and age were evaluated. Three polymorphisms, rs4673:T>C and rs9932581:G>A in the CYBA gene and rs2071746:A>T in the HMOX1 gene, were identified through direct sequencing. Hb F levels were not associated with sex, age, or the polymorphisms rs4673:T>C and rs9932581:G>A. However, the TT genotype of the rs2071746:A>T polymorphism was associated with increased levels of Hb F (p value = 0.0131). We observed an association between the TT genotype of the rs2071746:A>T polymorphism, present in the HMOX1 gene, and increased levels of Hb F, indicating the presence of a new marker related to Hb F levels in sickle cell anemia patients.

In Brazil, common bean (Phaseolus vulgaris L.) productivity is severely affected by drought stress due to low technology cultivation systems. Our purpose was to identify differentially expressed genes in roots of a genotype tolerant to water deficit (BAT 477) when submitted to an interruption of irrigation during its development. A SSH library was constructed taking as “driver” the genotype Carioca 80SH (susceptible to drought). After clustering and data mining, 1572 valid reads were obtained, resulting in 1120 ESTs (expressed sequence tags). We found sequences for transcription factors, carbohydrates metabolism, proline-rich proteins, aquaporins, chaperones and ubiquitins, all of them organized according to their biological processes. Our suppressive subtractive hybridization (SSH) library was validated through RT-qPCR experiment by assessing the expression patterns of 10 selected genes in both genotypes under stressed and control conditions. Finally, the expression patterns of 31 ESTs, putatively related to drought responses, were analyzed in a time-course experiment. Our results confirmed that such genes are more expressed in the tolerant genotype during stress; however, they are not exclusive, since different levels of these transcripts were also detected in the susceptible genotype. In addition, we observed a fluctuation in gene regulation over time for both the genotypes, which seem to adopt and adapt different strategies in order to develop tolerance against this stress.