Cores e corantes dos bordados de Castelo Branco: interação de contextos formais e não formais na educação em química

Els brodats de colors de Castelo Branco (Portugal) van ser objecte del desenvolupament d'un projecte per millorar la relació entre l'educació formal i no formal en química i en la formació de professors i divulgadors de la cultura. La qüestió principal se centra en la possibilitat d'identificar i obtenir els tints antics i actuals que s'utilitzen per tenyir la seda. Es presenten dues activitats experimentals: l'extracció d'un colorant natural i l'ús de mordent amb un tint sintètic.The colourful embroidery of Castelo Branco (Portugal) was the theme for the development of a project that enhances the relationship between formal and non-formal contexts in chemistry education and in the training of teachers and cultural animators. The central question concerns the possibility of identifying and obtaining the old and modern dyes that are used for dyeing silk. We present two experimental activities: extraction of a natural dye and use of mordant with a synthetic dye

New Halogenated Phenylbacteriochlorins and Their Efficiency in Singlet-Oxygen Sensitization

Halogenated phenylbacteriochlorins are synthesized with high yields in a two-step procedure. They have strong absorbances in the red and are very stable to air and light at room temperature. Flash photolysis measurements show that the triplet states of these bacteriochlorins have 30 μs lifetimes in deaerated toluene, that are quenched with diffusion-controlled rate constants by molecular oxygen. Time-resolved photoacoustic measurements, with nanosecond and nanocalorie resolution, show that these bacteriochlorins sensitize the formation of singlet oxygen with nearly unity quantum yield. However, singlet-oxygen phosphorescence measurements indicate that physical quenching occurs before the singlet-oxygen molecules diffuse into solution, and nearly half of the sensitized singlet states are lost

Study of chemical sympathectomy in endotoxin-induced lethality and fibrin deposition

Study of chemical sympathectomy in endotoxin-induced lethality and fibrin deposition. Shock and the generalized Shwartzman reaction are well known features of endotoxin which have been shown to involve the sympathetic nervous system. The mechanism of sympathetic nervous system involvement with endotoxin injection was studied in rabbits chemically sympathectomized with 6-hydroxydopamine. Endotoxin, in doses producing a spectrum of morbidity and mortality in normal rabbits, was administered i.v. to chemically sympathectomized, normal, and unilateral renal surgically sympathectomized animals. Chemical sympathectomy produced a significant depletion of tissue norepinephrine which, in endotoxin recipient animals, was associated with a significantly lower mortality rate and greatly decreased fibrin deposition in the lungs and kidneys, despite intravascular coagulation. Unilateral renal sympathectomy afforded protection to the ipsilateral kidney, but data on mortality and systemic fibrin deposition were similar to those reported for normal rabbits given endotoxin. Six-hydroxydopamine prevents significant tissue injury secondary to endotoxin in this experimental model. In addition, the data provide direct evidence that an intact reactive sympathetic nervous system is essential for development of lethal toxicity and generalized Shwartzman reaction due to endotoxin.Etude de la sympathectomie chimique de la lethalité et des dépôts de fibrine chez animaux qui ont reçu l'endotoxine. Le choc et le phénomène de Schwartzman généralisé sont des conséquences bien connues de l'endotoxine et il a été montré que ces réactions impliquent le systéme nerveux sympathique. Le mécanisme de la mise en jeu du système nerveux sympathique par l'injection d'endotoxine a été étudié chez des lapins ayant subi une sympathectomie chimique par la 6-hydroxydopamine. L'endotoxine, aux doses qui déterminent une morbidité et une mortalité chez les lapins normaux, a été administrée par voie intraveineuse à des animaux normaux, ayant subi une sympathectomie chimique ou ayant subi une sympathectomie rénale, chirurgicale et unilatérale. La sympathectomie chimique a produit une déplétion significative de norépinéphrine tissulaire qui, chez les animaux qui ont reçu l'endotoxine, a été associée à une diminution significative de la mortalité et une diminution importante des dépôts de fibrine dans les poumons et les reins malgré la coagulation intravasculaire. La sympathectomie unilatérale a protégé le rein ipsilatéral mais la mortalité et les dépôts systémiques de fibrine ont été semblables à ceux observés chez les lapins normaux qui ont reçu l'endotoxine. La 6-hydroxydopamine diminue de façon significative les altérations tissulaires secondaires à l'endotoxine dans ce modèle expérimental. De surcroît, ces observations apportent la preuve directe de ce qu'un système nerveux sympathique intact et réactif est essentiel pour l'apparition de la léthalité et du phénomène de Schwartzman généralisé consécutifs à l'endotoxine

Shrubs and Degraded Permafrost Pave the Way for Tree Establishment in Subarctic Peatlands

Arctic and subarctic ecosystems are changing rapidly in species composition and functioning as they warm twice as fast as the global average. It has been suggested that tree-less boreal landscapes may shift abruptly to tree-dominated states as climate warms. Yet, we insufficiently understand the conditions and mechanisms underlying tree establishment in the subarctic and arctic regions to anticipate how climate change may further affect ecosystem structure and functioning. We conducted a field experiment to assess the role of permafrost presence, micro-topography and shrub canopy on tree establishment in almost tree-less subarctic peatlands of northern Finland. We introduced seeds and seedlings of four tree-line species and monitored seedling survival and environmental conditions for six growing seasons. Our results show that once seedlings have emerged, the absence of permafrost can enhance early tree seedling survival, but shrub cover is the most important driver of subsequent tree seedling survival in subarctic peatlands. Tree seedling survival was twice as high under an intact shrub canopy than in open conditions after shrub canopy removal. Under unclipped control conditions, seedling survival was positively associated with dense shrub canopies for half of the tree species studied. These strong positive interactions between shrubs and trees may facilitate the transition from today's treeless subarctic landscapes towards tree-dominated states. Our results suggest that climate warming may accelerate this vegetation shift as permafrost is lost, and shrubs further expand across the subarctic.Peer reviewe

(R)-2′-Benz­yloxy-5,5′,6,6′,7,7′,8,8′-octa­hydro-1,1′-binaphthyl-2-ol

The mol­ecules of the title compound, C27H28O2, exhibit axial chirality. The planes of the aromatic rings of the tetra­lin ring systems make an angle of 85.72 (11)°. The non-aromatic rings adopt distorted half-chair conformations. In one of them, two C atoms of the four-atom aliphatic chain are disordered over two sites in a 0.75 (2):0.25 (2) ratio. The substituent phenyl ring is also disordered over two positions in a 0.59 (3):0.41 (3) ratio. There are no conventional hydrogen bonds joining the mol­ecules

Porphyrin–nanodiamond hybrid materials—active, stable and reusable cyclohexene oxidation catalysts

funded by FCT-Foundation for Science and Technology, I.P., under projects UIDB/00313/2020; PTDC/QUI-OUT/27996/2017 (DUALPI); POCI-01-0145-FEDER-027996; POCI-01-0145-FEDER-016387; UIDB/50006/2020 (Associate Laboratory for Green Chemistry-LAQV); MATIS (CENTRO-010145-FEDER-00014); Base Funding-UIDB/50020/2020 of the Associate Laboratory LSRE-LCM-funded by national funds through FCT/MCTES (PIDDAC); and 5625-DRI-DAAD-2020/21. SACC also acknowledges FCT Investigador FCT program (IF/01381/2013/CP1160/CT0007) and Scientific Employment Stimulus -Institutional Call (CEECINST/00102/2018). The authors also thank Fundacao de Amparo a Pesquisa do Estado de Sao Paulo (FAPESP) for CEPOF 2013/07276-1, and INCT "Basic Optics and Applied to Life Sciences" (FAPESP 2014/50857-8, CNPq 465360/2014-9). A.R.L. Caires acknowledges CAPES-PrInt funding program (grant number 88887.353061/2019-00 and 88881.311921/2018-01). J.G.B. thanks the Dutch Research Council (NWO) for funding as a part of the Open Technology Programme (project number 16361). L.D. Dias thanks FAPESP for the Post-doc grant 2019/13569-8. F.M.S.R. thanks FCT for the PhD grant (PD/BD/114340/2016).The quest for active, yet “green” non-toxic catalysts is a continuous challenge. In this work, covalently linked hybrid porphyrin–nanodiamonds were prepared via ipso nitro substitution reaction and characterized by X-ray photoelectron spectroscopy (XPS), fluorescence spectroscopy, infrared spectroscopy (IR) and thermogravimetry-differential scanning calorimetry (TG-DSC). The amine-functionalized nanodiamonds (ND@NH2 ) and 2-nitro-5,10,15,20-tetra(4-trifluoromethylphenyl)porphyrin covalently linked to nanodiamonds (ND@βNH-TPPpCF3 ) were tested using Allium cepa as a plant model, and showed neither phytotoxicity nor cytotoxicity. The hybrid nanodiamond–copper(II)–porphyrin material ND@βNH-TPPpCF3-Cu(II) was also evaluated as a reusable catalyst in cyclohexene allylic oxidation, and displayed a remarkable turnover number (TON) value of ≈265,000, using O2 as green oxidant, in the total absence of sacrificial additives, which is the highest activity ever reported for said allylic oxidation. Additionally, ND@βNH-TPPpCF3-Cu(II) could be easily separated from the reaction mixture by centrifugation, and reused in three consecutive catalytic cycles without major loss of activity.publishersversionpublishe

Rhodium catalyzed hydroformylation of kaurane derivatives: A route to new diterpenes with potential bioactivity

Kaurenic and grandiflorenic acids are naturally occurring diterpenes whose biological activity has been described. Both acids contain an exocyclic methylenic double bond that allows further functionalization on their structure. In an attempt to expand the number of derivatives of these two natural products, we have undertaken a study on the hydroformylation of the methyl esters of the two acids and the trimethylsilyl ether of kaurenol. These substrates have been hydroformylated by using unmodified Rh catalysts, as well as Rh/PPh3 and Rh/tris-(o-t-butylphenyl)phosphite catalytic systems at 100 °C and 20 bar of CO/H2 (1:1). For the three substrates, the two Rh catalysts modified with P-donor ligands, produced high conversions and chemo- and regioselectivities in the diastereoisomeric pair of linear aldehydes. In all cases, the stereoselectivity observed is strongly dependent of the system used, being the most diastereoselective the least hindered unmodified Rh/CO catalyst. A correlation between the higher diastereoselectivity and the faster [beta]-elimination of the metal-alkyl intermediate observed in the unmodified system is discussed.http://www.sciencedirect.com/science/article/B6TF5-4RVMXFD-3/1/d27e671ad9e0b7fc325dfd0bdf413c7

Photophysical and Antibacterial Properties of Porphyrins Encapsulated inside Acetylated Lignin Nanoparticles

Lignin has recently attracted the attention of the scientific community, as a suitable raw material for biomedical applications. In this work, acetylated lignin was used to encapsulate five different porphyrins, aiming to preserve their photophysical properties, and for further use as antibacterial treatment. The obtained nanoparticles were physically characterized, through dynamic light scattering size measurement, polydispersity index and zeta potential values. Additionally, the photophysical properties of the nanoparticles, namely UV-vis absorption, fluorescence emission, singlet oxygen production and photobleaching, were compared with those of the free porphyrins. It was found that all the porphyrins were susceptible to encapsulation, with an observed decrease in their fluorescence quantum yield and singlet oxygen production. These nanoparticles were able to exert an effective photodynamic bactericide effect (blue-LED light, 450-460 nm, 15 J/cm(2)) on Staphylococcus aureus and Escherichia coli. Furthermore, it was achieved a photodynamic bactericidal activity on an encapsulated lipophillic porphyrin, where the free porphyrin failed to diminish the bacterial survival. In this work it was demonstrated that acetylated lignin encapsulation works as a universal, cheap and green material for the delivery of porphyrins, while preserving their photophysical properties.ERC Horizon H2020H2020 Marie Skłodowska-Curie Action

Effect of sitagliptin on energy metabolism and brown adipose tissue in overweight individuals with prediabetes:a randomised placebo-controlled trial

Aims/hypothesis: The aim of this study was to evaluate the effect of sitagliptin on glucose tolerance, plasma lipids, energy expenditure and metabolism of brown adipose tissue (BAT), white adipose tissue (WAT) and skeletal muscle in overweight individuals with prediabetes (impaired glucose tolerance and/or impaired fasting glucose). Methods: We performed a randomised, double-blinded, placebo-controlled trial in 30 overweight, Europid men (age 45.9 \xc2\xb1 6.2\xc2\xa0years; BMI 28.8 \xc2\xb1 2.3\xc2\xa0kg/m2) with prediabetes in the Leiden University Medical Center and the Alrijne Hospital between March 2015 and September 2016. Participants were initially randomly allocated to receive sitagliptin (100\xc2\xa0mg/day) (n = 15) or placebo (n = 15) for 12\xc2\xa0weeks, using a randomisation list that was set up by an unblinded pharmacist. All people involved in the study as well as participants were blinded to group assignment. Two participants withdrew from the study prior to completion (both in the sitagliptin group) and were subsequently replaced with two new participants that were allocated to the same treatment. Before and after treatment, fasting venous blood samples and skeletal muscle biopsies were obtained, OGTT was performed and body composition, resting energy expenditure and [18F] fluorodeoxyglucose ([18F]FDG) uptake by metabolic tissues were assessed. The primary study endpoint was the effect of sitagliptin on BAT volume and activity. Results: One participant from the sitagliptin group was excluded from analysis, due to a distribution error, leaving 29 participants for further analysis. Sitagliptin, but not placebo, lowered glucose excursion (\xe2\x88\x9240%; p < 0.003) during OGTT, accompanied by an improved insulinogenic index (+38%; p < 0.003) and oral disposition index (+44%; p < 0.003). In addition, sitagliptin lowered serum concentrations of triacylglycerol (\xe2\x88\x9229%) and very large (\xe2\x88\x9246%), large (\xe2\x88\x9235%) and medium-sized (\xe2\x88\x9224%) VLDL particles (all p < 0.05). Body weight, body composition and energy expenditure did not change. In skeletal muscle, sitagliptin increased mRNA expression of PGC1\xce\xb2 (also known as PPARGC1B) (+117%; p < 0.05), a main controller of mitochondrial oxidative energy metabolism. Although the primary endpoint of change in BAT volume and activity was not met, sitagliptin increased [18F] FDG uptake in subcutaneous WAT (sWAT; +53%; p < 0.05). Reported side effects were mild and transient and not necessarily related to the treatment. Conclusions/interpretation: Twelve weeks of sitagliptin in overweight, Europid men with prediabetes improves glucose tolerance and lipid metabolism, as related to increased [18F] FDG uptake by sWAT, rather than BAT, and upregulation of the mitochondrial gene PGC1\xce\xb2 in skeletal muscle. Studies on the effect of sitagliptin on preventing or delaying the progression of prediabetes into type 2 diabetes are warranted. Trial registration: ClinicalTrials.gov NCT02294084. Funding: This study was funded by Merck Sharp & Dohme Corp, Dutch Heart Foundation, Dutch Diabetes Research Foundation, Ministry of Economic Affairs and the University of Granada