The integration of metal oxide nanomaterials with mesoporous silica is a promising approach to exploiting the advantages of both types of materials. Traditional synthesis methods typically require multiple steps. This work instead presents a fast, one-step, template-free method for the synthesis of metal oxides homogeneously dispersed within mesoporous silica, including oxides of W, Ti, Nb, Ta, Sn, and Mo.
View Article and Find Full Text PDFThe biomass-derived platform chemicals furfural and 5-(hydroxymethyl)furfural (HMF) may be converted to α-angelica lactone (AnL) and levulinic acid (LA). Presently, LA (synthesized from carbohydrates) has several multinational market players. Attractive biobased oxygenated fuel additives, solvents, may be produced from AnL and LA via acid and reduction chemistry, namely alkyl levulinates and γ-valerolactone (GVL).
View Article and Find Full Text PDFHeterogeneous catalysis, which has served well the petrochemical industry, may valuably contribute towards a bio-based economy by sustainably enabling selective reactions to renewable chemicals. Carbohydrate-containing matter may be obtained from various widespread sources and selectively converted to furanic platform chemicals: furfural (Fur) and 5-(hydroxymethyl)furfural (Hmf). Valuable bioproducts may be obtained from these aldehydes via catalytic transfer hydrogenation (CTH) using alcohols as H-donors under relatively moderate reaction conditions.
View Article and Find Full Text PDFThe reaction of the macrocyclic cavitand cucurbit[6]uril (CB[6]) and the diaqua complex [MoOCl(HO)] in hydrochloric acid solution gave a water insoluble supramolecular compound with the general composition 2[MoOCl(HO)]·CB[6]·xHO·yHCl·z(CHCOCH) (2). Single crystal X-ray diffraction (XRD) analysis revealed the presence of barrel-shape supramolecular entities, {CB[6]·10(HO)}, aligned in layers which are shifted relative to adjacent layers to form a brick-like pattern. The CB[6]/water hydrogen-bonded entities further engage in intermolecular interactions with water, HCl and [MoOCl(HO)] molecules to form a three-dimensional (3D) framework.
View Article and Find Full Text PDFPhosphonate- and yttrium-based metal-organic frameworks (MOFs), formulated as [Y(Hbtp)]·5.5HO (1), [Y(Hbtp)]·2.5HO (2), (HO)[Y(Hbtp)(Hbtp)]·HO (3), and [Y(Hbtp)]·HO·0.
View Article and Find Full Text PDFA positively charged lamellar coordination polymer based on a flexible triphosphonic acid linker is reported. [Gd(H4 nmp)(H2 O)2 ]Cl⋅2 H2 O (1) [H6 nmp=nitrilotris(methylenephosphonic acid)] was obtained by a one-pot approach by using water as a green solvent and by forcing the inclusion of additional acid sites by employing HCl in the synthesis. Compound 1 acts as a versatile heterogeneous acid catalyst with outstanding activity in organic reactions such as alcoholysis of styrene oxide, acetalization of benzaldehyde and cyclohexanaldehyde and ketalization of cyclohexanone.
View Article and Find Full Text PDFMetal-free cucurbit[7]uril (CB7) solid-state assemblies promote acid-catalysed alcoholysis of aliphatic and aromatic epoxides under mild conditions to give β-alkoxy alcohols, which are important intermediates for the synthesis of a vast range of compounds such as bioactive pharmaceuticals. The catalytic process is heterogeneous and the catalyst can be reused in consecutive runs without any reactivation treatment. The acid species responsible for the catalytic activity of CB7 may be entrapped hydronium ions.
View Article and Find Full Text PDFThe tungsten oxide/2,2'-bipyridine hybrid material [WO3(2,2'-bpy)]·nH2O (n = 1-2) (1) has been prepared in near quantitative yield by the reaction of H2WO4, 2,2'-bpy, and H2O in the mole ratio of ca. 1:2:700 at 160 °C for 98 h in a rotating Teflon-lined digestion bomb. The solid-state structure of 1 was solved and refined through Rietveld analysis of high-resolution synchrotron X-ray diffraction data collected for the microcrystalline powder.
View Article and Find Full Text PDFObjective: To translate, cross-culturally adapt, and validate a specific questionnaire for the evaluation of celiac children and adolescents, the celiac disease DUX (CDDUX).
Methods: The steps suggested by Reichenheim and Moraes (2007) were followed to obtain conceptual, item, semantic, operational, and measurement equivalences. Four pediatric gastroenterologists; a researcher with tool validation background; three English teachers; and 33 celiac patients, aged 8-18 years, and their caregivers participated in the study.
Background: In recent years, a high prevalence of vitamin D deficiency amongst pregnant women and newborns has been observed throughout several regions of the world, especially in the presence of preeclampsia (PE) or obesity (OB). The aim of this study was to investigate whether nonobese and obese preeclamptic pregnant women and their newborns have low 25(OH)D compared with nonobese and obese nonpreeclamptic pregnant women; and to verify whether the maternal level of this vitamin correlates with the newborns' level.
Methods: This is a cross-sectional study conducted with 179 pregnant women recruited immediately before delivery, divided into four groups: PE(+)/OB(-); PE(+)/OB(+); PE(-)/OB(+); and PE(-)/OB(-), with gestational age ≥ 34 weeks.
Rationalization of the synthetic conditions allowed the predictable fast sustainable preparation of [La2(H3nmp)2(H2O)4]·4.5H2O having a 1D coordination polymer. The material exhibits a remarkable chemical stability, can be converted into other layered compounds, and is an excellent catalyst surpassing other related materials.
View Article and Find Full Text PDFThe acid-catalyzed reaction of 5-(hydroxymethyl)-2-furfural with ethanol is a promising route to produce biofuels or fuel additives within the carbohydrate platform; specifically, this reaction may give 5-ethoxymethylfurfural, 5-(ethoxymethyl)furfural diethylacetal, and/or ethyl levulinate (bioEs). It is shown that sulfonated, partially reduced graphene oxide (S-RGO) exhibits a more superior catalytic performance for the production of bioEs than several other acid catalysts, which include sulfonated carbons and the commercial acid resin Amberlyst-15, which has a much higher sulfonic acid content and stronger acidity. This was attributed to the cooperative effects of the sulfonic acid groups and other types of acid sites (e.
View Article and Find Full Text PDFMicro/mesoporous chromium, aluminium-containing silicates of the type TUD-1 (Al-TUD-1, Cr-TUD-1, CrAl-TUD-1) and zeolite BEA, Cr-BEA, and related composites BEA/TUD-1 and Cr-BEA/TUD-1, were prepared, characterised, and tested as solid acids coupled with the ionic liquid (IL) 1-butyl-3-methylimidazolium chloride ([bmim]Cl) as solvent, in the transformation of D-glucose into 5-(hydroxymethyl)-2-furaldehyde (Hmf), at 120 °C. The chromium-containing catalytic systems lead to considerably higher Hmf yields in comparison to the related systems without chromium. The IL is a favourable solvent for this target reaction (in terms of Hmf yields reached) compared to water or dimethylsulfoxide.
View Article and Find Full Text PDFThe dioxomolybdenum(VI) complexes [MoO2Cl2(PzPy)] (1) and [MoO2(OSiPh3)2(PzPy)] (5) (PzPy = 2-[3(5)-pyrazolyl]pyridine) were synthesized and characterized by vibrational spectroscopy, with assignments being supported by DFT calculations. Complex 5 was additionally characterized by single crystal X-ray diffraction. Recrystallization of 1 under different conditions originated crystal structures containing either the mononuclear [MoO2Cl2(PzPy)] complex co-crystallized with 2-[3(5)-pyrazolyl]pyridinium chloride, binuclear [Mo2O4(μ2-O)Cl2(PzPy)2] complexes, or the oxodiperoxomolybdenum(VI) complex [MoO(O2)2Cl(PzPyH)], in which a 2-[3(5)-pyrazolyl]pyridinium cation weakly interacts with the Mo(VI) center via a pyrazolyl N-atom.
View Article and Find Full Text PDFThe one-pot acid-catalysed conversion of mono/di/polysaccharides (inulin, xylan, cellobiose, sucrose, glucose, fructose, xylose) into 2-furfuraldehyde (FUR) or 5-hydroxymethylfurfural (HMF) in the presence of aluminium-containing mesoporous TUD-1 (denoted as Al-TUD-1, Si/Al = 21), at 170 degrees C was investigated. Xylose gave 60% FUR yield after 6 h reaction; hexose-based mono/disaccharides gave less than 20% HMF yield; polysaccharides gave less than 20 wt % FUR or HMF yields after 6 h. For four consecutive 6 h batches of the xylose reaction in the presence of Al-TUD-1, the FUR yields achieved were similar, without significant changes in Si/Al ratio.
View Article and Find Full Text PDFThe reaction of [MoO(2)Cl(2)(bipy)] (1) (bipy = 2,2'-bipyridine) with water in a Teflon-lined stainless steel autoclave (100 degrees C, 19 h), in an open reflux system with oil bath heating (12 h) or in a microwave synthesis system (120 degrees C, 4 h), gave the molybdenum oxide/bipyridine hybrid material {[MoO(3)(bipy)][MoO(3)(H(2)O)]}(n) (2) as a microcrystalline powder in yields of 72-92%. The crystal structure of 2 determined from synchrotron X-ray powder diffraction data is composed of two distinct neutral one-dimensional polymers: an organic-inorganic polymer, [MoO(3)(bipy)](n), and a purely inorganic chain, [MoO(3)(H(2)O)](n), which are interconnected by O-H..
View Article and Find Full Text PDFArq Bras Endocrinol Metabol
December 2004
To know the prevalence of celiac disease (CD) in a group of children and adolescents with type I diabetes mellitus. A cross sectional study was conducted at the Instituto Materno Infantil de Pernambuco (IMIP) in March 2000. The sample consisted of 19 children and adolescents with type I diabetes mellitus that had the human anti-tissue transglutaminase antibodies assessed using kits from the Eurospital Laboratory.
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