Search

BACKGROUND: The overall clinical benefit of thiazolidinediones (TZDs) as a treatment for hyperglycaemia can be difficult to assess because of the risk of congestive heart failure due to TZD-related fluid retention. Since prediabetic and diabetic patients are at high cardiovascular risk, the outcome and natural history of such risks need to be better understood. We aimed to examine the risk of congestive heart failure and of cardiac death in patients given TZDs. METHODS: We used a search strategy to identify 3048 studies. 3041 were excluded, and we did a systematic review and meta-analysis of the seven remaining randomised double-blind clinical trials of drug-related congestive heart failure in patients given TZDs (either rosiglitazone or pioglitazone). We calculated pooled random-effects estimates of the risk ratios for development of congestive heart failure in patients given TZDs compared with controls. The main outcome measures were development of congestive heart failure and the risk of cardiovascular death. FINDINGS: 360 of 20 191 patients who had either prediabetes or type 2 diabetes had congestive heart failure events (214 with TZDs and 146 with comparators). Results showed no heterogeneity of effects across studies (I2=22.8%; p for interaction=0.26), which indicated a class effect for TZDs. Compared with controls, patients given TZDs had increased risk for development of congestive heart failure across a wide background of cardiac risk (relative risk [RR] 1.72, 95% CI 1.21-2.42, p=0.002). By contrast, the risk of cardiovascular death was not increased with either of the two TZDs (0.93, 0.67-1.29, p=0.68). INTERPRETATION: Congestive heart failure in patients given TZDs might not carry the risk that is usually associated with congestive heart failure which is caused by progressive systolic or diastolic dysfunction of the left ventricle. Longer follow-up and better characterisation of such patients is needed to determine the effect of TZDs on overall cardiovascular outcome. [ABSTRACT FROM AUTHOR]

Extensive research in the last few decades has conclusively demonstrated the significant influence of experimental conditions, surfactants, and synthesis methods on semiconductors' properties in technological applications. Therefore, in this study, the synthesis of molybdenum oxide (MoO 3 ) was reported by the addition of 2.5 (MoO 3 _2.5), 5 (MoO 3 _5), 7.5 (MoO 3 _7.5), and 10 mL (MoO 3 _10) of nitric acid, obtaining the respective concentrations of 0.6, 1.10, 1.6, and 0.6 mol L -1 . In this study, all samples were synthesized by the hydrothermal method at 160 °C for 6 h. The materials obtained were structurally characterized by X-ray diffraction (XRD) and structural Rietveld refinement, Raman spectroscopy, and infrared spectroscopy (FTIR), confirming the presence of all crystallographic planes and bands associated with active modes for the pure hexagonal phase ( h -MoO 3 ) when the solution's concentration was 0.6 mol L -1 of nitric acid. For concentrations of 1.10, 1.60, and 2.10 mol L -1 , the presence of crystallographic planes and active modes associated with the formation of mixtures of molybdenum oxide polymorphs was confirmed, in this case, the orthorhombic, monoclinic, and hexagonal phases. X-ray photoelectron spectroscopy reveals the occurrence of the states Mo 4+ , Mo 5+ , and Mo 6+ , which confirm the predominance of the acid Lewis sites, corroborating the analysis by adsorption of pyridine followed by characterization by infrared spectroscopy. The images collected by scanning electron microscopy confirmed the information presented in the structural characterization, where microcrystals with hexagonal morphology were obtained for the MoO 3 _2.5 sample. In contrast, the MoO 3 _5, MoO 3 _7.5, and MoO 3 _10 samples exhibited hexagonal and rod-shaped microcrystals, where the latter morphology is characteristic of the orthorhombic phase. The catalytic tests carried out in the conversion of oleic acid into methyl oleate, using the synthesized samples as a heterogeneous catalyst, resulted in conversion percentages of 52.5, 58.6, 69.1, and 97.2% applying the samples MoO 3 _2.5, MoO 3 _5, MoO 3 _7.5, and MoO 3 _10, respectively. The optimization of the catalytic tests with the MoO 3 _10 sample revealed that the conversion of oleic acid into methyl oleate is a thermodynamically favorable process, with a variation in the Gibbs free energy between -67.3 kJ mol -1 and 83.4 kJ mol -1 as also, the energy value of activation of 24.6 kJ mol -1 , for the temperature range from 80 to 140 °C, that is, from 353.15 to 413.15 K, respectively. Meanwhile, the catalyst reuse tests resulted in percentages greater than 85%, even after the ninth catalytic cycle. Therefore, the expressive catalytic performance of the mixture of h -MoO 3 and α-MoO 3 (MoO 3 _10) phases is confirmed, associated with the synergistic effect, mainly due to the increase in the surface area and available Lewis sites of these phases.

Emerging contaminants, such as the hormone 17α-ethynylestradiol (EE), in aquatic environments pose a serious risk to both human and environmental health, making efficient removal essential. This study evaluated the effectiveness of three-dimensional porous carbon structures derived from poly(acrylic acid) (PAAc, Carbopol 990) as adsorbents for removing EE from aqueous solutions. Activated carbon materials were prepared using varying ratios of KOH as an activating agent (PAAc : KOH; 1 : 0 AAC, 1 : 1 AC1, 1 : 2 AC2, and 1 : 3 AC3). Adsorption tests were conducted by adding 10 mg of the adsorbent to 40 mL of an EE solution (100 ppm, 20 % acetonitrile in water). Analyses including TGA, XRD, and Raman spectroscopy were performed to evaluate the materials' structural properties and adsorption capacities. Among the materials, AC3 exhibited the highest adsorption capacity for EE (238 mg g -1 ), followed by AC2 (153 mg g -1 ) and AC1 (82 mg g -1 ). The superior efficiency of AC3 can be attributed to its larger surface area and pore volume, enabling greater interaction with EE molecules. These materials demonstrated higher adsorption capacities compared to commercial activated carbons and single-walled carbon nanotubes. This work opens new possibilities for developing efficient adsorbents, contributing to more effective and sustainable solutions for water purification and environmental protection., (© 2024 Wiley-VCH GmbH.)

The combination of materials to improve properties of interest has become one of the strategies widely used for numerous applications, including new catalysts, over the last few decades. In this study, silver molybdate (β-Ag 2 MoO 4 ) microcrystals were efficiently obtained by the hydrothermal method, obtaining composites with different amounts of graphene oxide (GO) (1, 2.5, 5, 7.5, and 10%, w/w) using the conventional hydrothermal method. The incorporation of GO on silver molybdate was confirmed by X-ray diffraction (XRD) and Raman spectroscopy, where the vibrational modes and crystallographic planes characteristic of the materials of interest were highlighted. The images collected by scanning electron microscopy (SEM) revealed the occurrence of plate-shaped structures (shells) anchored to the surface of the silver molybdate microcrystals (core). The optical properties showed that the materials presented E gap between 3.34 and 3.39 eV, where the sample with 7.5% of GO (GO@β-AgMo_7.5) was the one that presented energy for the conduction band, largely favorable to the formation of superoxide radicals through the photoexcitation process of electrons. The catalytic tests demonstrated that, among the samples obtained in this study, the sample with 7.5% of GO (GO@β-AgMo_7.5) exhibits superior photocatalytic performance against the dye rhodamine B (RhB) in an aqueous medium. Thus, the kinetics constant for photolysis (absence of catalysts) and for the sample β-AgMo and the sample with 7.5% of GO (GO@β-AgMo_7.5) are 0.38 × 10 -3 , 12 × 10 -3 , and 23.72 × 10 -3 min -1 , respectively. Therefore, it is 62.5 times more efficient in the degradation of the RhB dye, which confirms the promising photocatalytic properties of the obtained composite., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

In this study, calcium ferrites with different Ca : Fe atomic ratios (1 : 1, 1 : 2, 1 : 3 and 2 : 1) were prepared from Ca and Fe nitrates treated at 300, 700 and 900 °C and evaluated for phosphate adsorption and recovery from wastewater. TG, XRD, Mössbauer spectroscopy, SEM, VSM magnetic measurements, and BET analyses showed the formation of two different calcium ferrite phases, i.e. , CaFe 2 O 4 and Ca 2 Fe 2 O 5 at 700 and 900 °C. The adsorption results indicated that the formation of calcium ferrite structure is critical for phosphate adsorption/recovery. Evaluation of the pH, initial phosphate concentration, contact time, coexisting ions and desorption conditions showed remarkable adsorption capacities of 62-75 mg g -1 for CaFe1:2-700 and 28-43 mg g -1 for CaFe1:2-900. The phosphate adsorption on the Ca ferrite surfaces is so strong that the recovery/desorption showed limited efficiencies, e.g. , 15-39%., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

The iron mine tailings accumulation in dams is an environmental and economic problem. The composite based on high-density polyethylene/iron mine tailing production for the application of wood plastic and some items of domestic plastic industry can be a good alternative to reduce the rejects in the environment. This work presents the influence of the processing methodology in the mechanical, thermal and morphological properties of composites based on the high-density polyethylene/iron mine tailing. Four methodology processing by continuous and/or batch mixing were available. The iron mine tailing particles in the polymer matrix promoted an increase in mechanical strength and thermal stability. Besides, the particles acted as flame retardant. The iron mine tailing materials produced using batch mixing showed more significant modifications in the properties due to the better dispersion of the filler as shown by scanning electron microscopy.

In this work, the potential to use an iron mining waste (IW), rich in α-Fe 2 O 3 and α-FeOOH, for the development of composites based on graphitic carbon nitride (CN) is demonstrated. These materials were synthesized through a simple thermal treatment at 550 °C of a mixture containing melamine and different IW mass percentages, giving rise to the catalysts xIWCN (where x is related to the initial mass percentage of IW). The iron phases of the precursor were partially transformed throughout the formation of the composites, in such a way that a mixture of α-Fe 2 O 3 and γ-Fe 2 O 3 was observed in their final composition. Furthermore, structural defects were produced in the carbonaceous matrix of the materials, causing the fragmentation of g-C 3 N 4 and an increase of surface area. The catalytic activities of these composites were evaluated in reactions of peroxymonosulfate activation for the degradation of paracetamol. Among these materials, the composite 20IWCN showed the best catalytic activity, being able to degrade almost 90 % of the total paracetamol in only 20 min of reaction. This catalyst also demonstrated high chemical stability, being successfully utilized in five consecutive reaction cycles, with negligible iron leaching., (Copyright © 2020 Elsevier B.V. All rights reserved.)

In this work, iron oxide in the red mud (RM) waste was restructured to produce mesopores with surface [FeO x (OH) y ] sites for the efficient complexation/adsorption of β-lactam antibiotics. Red mud composed mainly by hematite was restructured by an acid/base process followed by a thermal treatment at 150-450 °C (MRM150, MRM200, MRM300, and MRM450) and fully characterized by Mössbauer, XRD, FTIR, BET, SEM, CHN, and thermogravimetric analyses. The characterization data showed a highly dispersed Fe 3+ oxyhydroxy phase, which was thermally dehydrated to a mesoporous α-Fe 2 O 3 with surface areas in the range of 141-206 m 2  g -1 . These materials showed high efficiencies (21-29 mg g -1 ) for the adsorption of β-lactam antibiotics, amoxicillin, cephalexin, and ceftriaxone, and the data was better fitted by the Langmuir model isotherm (R 2  = 0.9993) with monolayer adsorption capacity of ca. 39 mg g -1 for amoxicillin. Experiments such as competitive adsorption in the presence of phosphate and H 2 O 2 decomposition suggested that the β-lactamic antibiotics might be interacting with surface [FeO x (OH) y ] species by a complexation process. Moreover, the OH/Fe ratio, BET surface area and porosity indicated that this complexation is occurring especially on [FeO x (OH) y ] surf sites contained in the mesopore space.

In this work, the effect of controlled thermal treatment to tune biochar surface properties such as area/porosity, functionalities and reactivity was investigated. TG-MS, CHN, Raman, IR, BET, Zeta and SEM analyses suggested that thermal treatment led to the decomposition of an organic complex/amorphous phase to produce micropores based on graphene nanostructures and a strong increase on surface area from 3m 2 g -1 for biochar to 30, 408 and 590m 2 g -1 , at 400, 600 and 800°C, respectively. The treatment also led to a gradual decrease on oxygen content from 27 to 14wt% at 800°C due to decomposition of surface functionalities changing surface properties such as zeta potential, adsorption of anionic and cationic species and an increase on the activity for sulfide oxidation which is discussed in terms of increase in surface area and the presence of surface redox quinone groups., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

KOH activation of a mesophase pitch produces very efficient carbons for the removal of sulfide in aqueous solution, increasing the sulfur oxidation rate with the degree of activation of the carbon. These carbons are characterized by their graphitic structures, with domains of sizes of around 20 nm, and a moderate concentration of surface oxygen groups (0.2-0.5 mmol·g -1 ) dominating the basic groups. Because the activation leads first to a strong development of the micropores and later to a development of the mesopores, the surface area values are always high, reaching values of as high as 3250 m 2 ·g -1 in the most activated carbon, with a volume of mesopores of as high as 44% of the total pore volume. In the presence of this carbon, the sulfide oxidation rate is 100 times higher than that found for a commercial activated carbon, the results indicating that the porosity of the carbon, especially mesoporosity, plays a role more important than the structure or the chemical nature of the carbon in the kinetics of sulfide oxidation to different polysulfides.

In this study, a multistage treatment system was proposed to treat real pharmaceutical wastewater containing the antibiotic amoxicillin. Ozonation (O 3 ), and ozonation combined with aerobic biodegradation, were performed. The real pharmaceutical wastewater presented a high concentration of organic matter (TOC: 803 mg C·L -1 and COD: 2775 mg O 2 ·L -1 ), significant amoxicillin content (50 mg L -1 ) and acute ecotoxicity (Aliivibrio fischeri aTU: 48.22). Ozonation proved to be effective for amoxicillin degradation (up to 99%) and the results also indicated the removal of the original colour of the wastewater, with average consumption of 1 g of ozone. However, the ozonation system alone could not achieve complete mineralization. Therefore, a combination of ozonation and biodegradation in a multistage system was proposed in order to improve cost and treatment efficiency. The multistage treatment system presented promising results, achieving degradation of more than 99% of the amoxicillin, more than 98% of the original chemical oxygen demand (COD), and 90% of initial toxicity, with the consumption of approximately 500 mg of ozone. This indicates that this system could prevent dangerous and biorecalcitrant antibiotics from entering water resources., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

This work describes the synthesis, characterization, and application of an active heterogeneous photo-Fenton system obtained from two different wastes, i.e., laterite (an iron mining waste) and the acid aqueous fraction (AAF) from bio-oil production. AAF with high acidity (ca. 3 mol H+  L -1 ) and organic concentration (25 wt.%) obtained from biomass flash pyrolysis was used for the efficient extraction of Fe 3+ from laterite waste. After extraction, the mixture Fe 3+ /AAF was dried and treated at different temperatures, i.e., 500, 650, and 800 °C, to obtain Fe/C reactive composites. Mössbauer, XRD, TG, elemental analyses, and SEM/EDS showed the presence of highly disperse Fe oxide nanoparticles at 500 and 650 °C and Fe 0 particles in the material obtained at 800 °C with carbon contents varying from 74 to 80 %. The three composites were tested as heterogeneous catalysts in the photo-Fenton reaction for the oxidation of the model dye contaminant methylene blue, showing high activities at neutral pH.

In this work, [FeOx(OH)y]/Al2O3 composites with different Fe oxyhydroxy contents, i.e. 10, 20 and 50wt% treated at 150, 200, 300 and 450°C were investigated as adsorbents of β-lactamic antibiotics, i.e. cephalexin, ceftriaxone and especially amoxicillin, from aqueous solutions. The obtained results showed that the nature of the surface Fe(3+) species play a fundamental role on the adsorption process. The most efficient adsorption was obtained for the sample 150Fe50A (50% [FeOx(OH)y] supported in Al2O3 treated at 150°C) whereas the thermal treatment at higher temperatures caused a strong decrease on the adsorption capacity. Mössbauer, XRD, FTIR, Raman, TG-MS, SEM, CHN and BET of the composite 150Fe50A suggested an approximate composition of FeO0.65(OH)1.7 whereas at 450°C strong dehydroxylation process takes place to form FeO1.4(OH)0.21. These results combined with competitive adsorption using amoxicillin mixed with phosphate or H2O2 suggest that the antibiotic molecules adsorb by complexation on surface sites likely based on FeOx(OH)y by the replacement of the labile OH ligands., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Amphiphilic magnetic composites were produced based on chrysotile mineral and carbon structures by chemical vapor deposition at different temperatures (600-900 °C) and cobalt as catalyst. The materials were characterized by elemental analysis, X-ray diffraction, vibrating sample magnetometry, adsorption and desorption of N2, Raman spectroscopy, scanning electronic microscopy, and thermal analysis showed an effective growth of carbon structures in all temperatures. It was observed that at 800 and 900 °C, a large amount of carbon structures are formed with fewer defects than at 600 and 700 °C, what contributes to their stability. In addition, the materials present magnetic phases that are important for their application as catalysts and adsorbents. The materials have shown to be very active to remove the oil dispersed in a real sample of emulsified wastewater from biodiesel production and to remove methylene blue by adsorption and oxidation via heterogeneous Fenton mechanism., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Hydrophobic cavities produced by cetyltrimethylammonium cation (CTA(+)) exchanged and trapped in the interlayer space of montmorillonite were used to remove the harmful hormone contaminant ethinyl estradiol (EE2) from water. X-ray diffraction, thermogravimetry/derivative thermogravimetry, elemental analysis (carbon, hydrogen, nitrogen), Fourier transform infrared, scanning electron microscopy/energy dispersive spectroscopy, Brunauer-Emmett-Teller and contact angle analyses showed that the intercalation of 9, 16 and 34 wt% CTA(+) in the montmorillonite resulted in the d001 expansion from 1.37 to 1.58, 2.09 and 2.18 nm, respectively. EE2 adsorption experiments showed that the original clay montmorillonite does not remove EE2 from water whereas the intercalated composites showed high efficiency with adsorption capacities of 4.3, 8.8 and 7.3 mg g(-1) for M9CTA(+), M16CTA(+) and M34CTA(+), respectively. Moreover, experiments with montmorillonite simply impregnated with cetyltrimethylammonium bromide showed that the intercalation of CTA(+) to form the hydrophobic cavity is very important for the adsorption properties. Simple solvent extraction can be used to remove the adsorbed EE2 without significant loss of CTA(+), which allows the recovery and reuse of the adsorbent for at least five times.

This paper describes a new, efficient and versatile method for the sampling and preconcentration of PAH in environmental water matrices using special hybrid magnetic carbon nanotubes. These N-doped amphiphilic CNT can be easily dispersed in any aqueous matrix due to the N containing hydrophilic part and at the same time show high efficiency for the adsorption of different PAH contaminants due to the very hydrophobic surface. After adsorption, the CNT can be easily removed from the medium by a simple magnetic separation. GC/MS analyses showed that the CNT method is more efficient than the use of polydimethylsiloxane (PDMS) with much lower solvent consumption, technical simplicity and time, showing good linearity (range 0.18-80.00 μg L(-1)) and determination coefficient (R(2) > 0.9810). The limit of detection ranged from 0.05 to 0.42 μg L(-1) with limit of quantification from 0.18 to 1.40 μg L(-1). Recovery (n=9) ranged from 80.50 ± 10 to 105.40 ± 12%. Intraday precision (RSD, n=9) ranged from 1.91 to 9.01%, whereas inter day precision (RSD, n=9) ranged from 7.02 to 17.94%. The method was applied to the analyses of PAH in four lake water samples collected in Belo Horizonte City, Brazil., (Copyright © 2015 Elsevier B.V. All rights reserved.)

In this work, unique amphiphilic magnetic hybrid carbon nanotubes (CNTs) are synthesized and used as tensioactive nanostructures in different applications. These CNTs interact very well with aqueous media due to the hydrophilic N-doped section, whereas the undoped hydrophobic one has strong affinity for organic molecules. The amphiphilic character combined with the magnetic properties of these CNTs opens the door to completely new and exciting applications in adsorption science and catalysis. These amphiphilic N-doped CNTs can also be used as powerful tensioactive emulsification structures. They can emulsify water/organic mixtures and by a simple magnetic separation the emulsion can be easily broken. We demonstrate the application of these CNTs in the efficient adsorption of various molecules, in addition to promoting biphasic processes in three different reactions, i.e. transesterification of soybean oil, quinoline extractive oxidation with H2O2 and a metal-catalyzed aqueous oxidation of heptanol with molecular oxygen.

In this work, reactive iron nanoparticles dispersed in a carbon matrix were produced by the controlled thermal decomposition of Fe(3+) ions in sucrose. During the sucrose decomposition, the Fe(3+) ions are reduced to form iron nanometric cores dispersed in a porous carbonaceous matrix. The materials were prepared with iron contents of 1, 4, and 8 wt.% and heated at 400, 600, and 800 °C. Analyses by X-ray diffraction, Mössbauer spectroscopy, magnetization measurements, Raman spectroscopy, termogravimetric analyses, BET surface area, scanning, and transmission electron microscopy showed that at 400 °C, the materials are composed essentially of Fe3O4 particles, while treatments at higher temperatures, i.e., 600 and 800 °C, produced phases such as Fe(0) and Fe3C. The composites were tested for the oxidation of methylene blue with H2O2 by a Fenton-type reaction and also H2O2 decomposition, showing better performance for the material containing 8 % of iron heated at 400 and 600 °C. These results are discussed in terms of Fe(2+) surface species in the Fe3O4 nanoparticles active for the Fenton reaction.

In this work, a new approach is presented for the modification of the hazardous steel industry waste BFD (Blast Furnace Dust) into a versatile material for application in environmental remediation processes. Tar pitch, another waste, was used to agglomerate the very fine (submicrometric) dust particles to produce a compact and robust pelletized material that under simple thermal treatment produces notably reactive reduced Fe phases. SEM, TG/DTA, Mössbauer, XRD, Raman, BET and elemental analyses indicated that the tar/BFD composite (1:1wt ratio) pellets treated at 400, 600 and 800°C lead to tar decomposition to form a carbon binding coat concomitant with the reduction of the Fe oxides to produce primarily Fe3O4 (magnetite), FeO (wüstite) and Fe(0). Preliminary reactivity studies indicated that these treated composites, especially at 800°C, are active for the reduction of Cr(VI)aq and for the elimination of textile dye via reduction and the Fenton reaction., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

A unique bistable copper-metallacyclic complex is used as an elegant molecular switch for the reversible formation of emulsions by simple pH variation. This switch may have several exciting applications in biphasic processes such as catalysis and separation science technologies.

In this work, chrysotile was used as support to grow carbon nanotubes and nanofibers to produce fibrous amphiphilic magnetic nanostructured composites. Iron impregnated on the chrysotile surface at 1, 5 and 15 wt% was used as catalyst to grow carbon nanostructures by CVD (chemical vapor deposition) with ethanol at 800°C. Raman, TG/DTA, Mössbauer, XRD, BET, SEM, TEM, elemental analyses and contact angle measurements suggested the formation of a complex amphiphilic material containing up to 21% of nanostructured hydrophobic carbon supported on hydrophilic Mg silicate fibers with magnetic Fe cores protected by carbon coating. Adsorption tests for the hormone ethynilestradiol (EE), a hazardous water contaminant, showed remarkable adsorption capacities even compared to high surface area activated carbon and multiwall carbon nanotubes. These results are discussed in terms of the hydrophobic surface of the carbon nanotubes and nanofibers completely exposed and accessible for the adsorption of the EE molecules combined with the hydrophilic Mg silicate surface which allows good dispersion in water. The composites are magnetic and after adsorption the dispersed particles can be removed by a simple magnetic process. Moreover, the fibrous composites can be conformed as threads, screens and pellets to produce different filtering media., (Copyright © 2013 Elsevier B.V. All rights reserved.)

In this work, hybrid magnetic amphiphilic composites were prepared by the catalytic growth of carbon nanotubes (CNTs) and nanofibers CNF on layered silicates fragments. SEM, TEM, Raman, XRD, Mössbauer, TG/DTA showed that CVD with CH(4) at 800°C produced CNF and magnetic Fe cores fixed on the surface of microfragments of silicates layers. Due to the amphiphilic character, the composites can be easily dispersed in water and efficiently adsorb hydrophobic contaminant molecules. For example, the composites showed remarkable adsorption capacities for the hormone ethinylestradiol, e.g. 2-4 mg m(-2), compared to ca. 0.1 mg m(-2) obtained for high surface area activated carbon and multiwall CNT. These results are discussed in terms of a high hydrophobic exposed surface area of the CNT and CNF fixed on the layered silicates fragments surface. Moreover, the composites can be easily removed from water by a simple magnetic separation process., (Copyright © 2012 Elsevier Inc. All rights reserved.)

In this work, it is demonstrated how a novel technique based on temperature-programmed chemical vapor deposition (TPCVD) can be used to investigate the synthesis of carbon nanotubes (CNTs) from methane on a classic catalyst FeMo(x)/MgO (x = 0.07, 0.35 and 1.00). TPCVD monitors carbon deposition by measuring H2 formed during CH4 decomposition and affords information on the different catalytic species, deactivation process, reaction kinetics and carbon yields. The obtained results showed for FeMgO catalyst a simple TPCVD peak related to the production of carbon beginning at 760 degrees C with maximum at 800 degrees C followed by a rapid deactivation resulting in a low carbon yield. The addition of Mo to Fe/MgO catalyst completely changes the TPCVD profile with the formation of a new catalytic species active at temperatures higher than 900 degrees C, which is stable and continuously decomposes CH4 to produce high carbon yields. Raman, TG/DTG, Mössbauer, SEM, TEM, XRD and TPR analyses suggested that this active catalytic phase is likely related to Fe-Mo and Fe-Mo-C phases active to produce single wall and mainly multiwall carbon nanotubes.

Percutaneous approaches to mitral regurgitation remain largely investigational. In the last decade, novel percutaneous strategies have opened new options in the treatment of valvular heart disease. Several studies are currently underway to determine the benefits of transcatheter mitral valve repair therapy. Transcatheter chordal procedures are being developed, including chordal cutting and chordal implantation. Transcatheter valve implantation in the mitral position might offer a desirable alternative in selected patients and has been accomplished in a compassionate fashion on rare occasions in patients who are not candidates for surgical valve repair or replacement., (Copyright © 2012. Published by Elsevier Inc.)

A magnetic fraction (15%) from a waste of foundry sand (WFS), composed of sand, carbon, bentonite clay and iron (10%) was modified by thermal treatment at 400, 600 and 800°C under inert atmosphere. Mössbauer analyses showed that the thermal treatment increased the amount of Fe(3)O(4) from 25 to 55% by reduction of Fe(2)O(3) and highly dispersed Fe(3+) by the carbon present in the waste. The Fe(3)O(4) caused a significant increase on the activity of two important reactions with application in environmental remediation: the Fenton oxidation of indigo carmine dye with H(2)O(2) and the reduction of Cr(VI) to Cr(III). The magnetic fraction of WFS was also mixed with hematite (Fe(2)O(3)) and thermally treated at 400, 600 and 800°C. This treatment produced large amounts of surface Fe(3)O(4) and increased substantially the rate of Fenton reaction as well as Cr(VI) reduction. This reactivity combined with the presence of carbon (an adsorbent for organic contaminants), bentonite clay (an adsorbent for metallic contaminants) and the granulometry/packing/hydrodynamic features make WFS a promising material for use in reactive permeable barriers., (Copyright © 2011 Elsevier B.V. All rights reserved.)

Objective: To examine ankle-brachial index (ABI) abnormalities in patients with type 2 diabetes and coronary artery disease (CAD)., Research Design and Methods: An ABI was obtained in 2,240 patients in the Bypass Angioplasty Revascularization Investigation 2 Diabetes (BARI 2D) Trial. ABIs were classified as: normal, 0.91-1.3; low, ≤ 0.9; high, >1.3; or noncompressible artery (NC). Baseline characteristics were examined according to ABI and by multivariate analysis. RESULTS ABI was normal in 66%, low in 19%, and high in 8% of patients, and 6% of patients had NC. Of the low ABI patients, 68% were asymptomatic. Using normal ABI as referent, low ABI was independently associated with smoking, female sex, black race, hypertension, age, C-reactive protein, diabetes duration, and lower BMI. High ABI was associated with male sex, nonblack race, and higher BMI; and NC artery was associated with diabetes duration, higher BMI, and hypertension., Conclusions: ABI abnormalities are common and often asymptomatic in patients with type 2 diabetes and CAD.

Composites based on iron supported on high surface area activated carbon were prepared and characterized with (57)Fe Mössbauer spectroscopy, X-ray diffraction, saturation magnetization measurements and temperature-programmed reduction. Upon thermal treatment, the supported iron oxides react with carbon to yield reduced chemical species, i.e. Fe(3)O(4) and Fe(0). This so produced composite was found to be highly efficient in two environmental applications: (i) degradation of textile dye and (ii) reduction of Cr(VI) in aqueous medium. Sequential reuses evidenced a progressive chemical deactivation of the composites due to a corresponding oxidation of the reactive species. Even after being virtually deactivated, the initial chemical reducing ability of the composites can be regenerated by heating at 800 degrees C under N(2) atmosphere, and then reused for several consecutive times., (Copyright (c) 2010 Elsevier Ltd. All rights reserved.)

A series of bulk and Al(2)O(3)-supported perovskite oxides of the type LaMn(1-x-y)Fe(x)Mo(y)O(3) (x = 0.00-0.90 and y = 0.00-0.09) were synthesized by the citric acid complexation-gelation method followed by annealing in air at 800 degrees C. For all samples, the local environment and the chemical state and concentration of surface species were determined. Mössbauer spectra revealed the only presence of octahedral Fe(3+) ions dispersed in the perovskite structure, however well-crystallized together with a poorly crystalline LaFeO(3) phases were detected for larger substitutions (x = 0.90). A similar picture was obtained for Mo-loaded (y = 0.02 and 0.05) samples but a new phase most likely related to Fe(3+) ions dispersed aside from the perovskite structure was found for larger substitutions (y = 0.09). Together with these structures, supported samples showed the presence of LaFeO(3) nanoparticles. Finally, photoelectron spectroscopy indicated that the chemical state and composition of the samples in the surface region (2-3 nm) approaches that of the bulk. For the unsupported substituted samples, iron (and molybdenum) enters into the perovskite structure while manganese tends to be slightly segregated. Moreover, in supported perovskites, a fraction of Mo and La atoms interact with the alumina surface. All these oxides were active in methane combustion and best performance was recorded for the Fe-rich composition (x = 0.9) in which both Mn(3+) and Mo(3+) ions were in the same proportion (y = 0.05).

In this work, controlled reduction of red mud with H(2) was used to produce active systems for two different environmental applications, i.e. the heterogeneous Fenton reaction and the reduction of Cr(VI). Mössbauer, powder X-ray diffraction, thermal analyses and scanning electron microscopy analyses showed that at different temperatures, i.e. 300, 400, 500 and 600 degrees C, H(2) reduces red mud to different phases, mainly Fe(3)O(4), Fe(0)/Fe(3)O(4) and Fe(0). These Fe phases are dispersed on Al, Si and Ti oxides present in the red mud and show high reactivity towards two environmental applications, i.e. the heterogeneous Fenton reaction and the reduction of Cr(VI). Reduction with H(2) at 400 degrees C showed the best results for the oxidation of the model dye methylene blue with H(2)O(2) at neutral pH due to the presence of the composite Fe(0)/Fe(3)O(4). The reduced red mud at 500-600 degrees C produced Fe(0) highly active for the reduction of Cr(VI) in aqueous medium. Another feature of these red mud based system is that after deactivation due to extensive use they can be completely regenerated by simple treatment with H(2)., (Copyright (c) 2009 Elsevier Ltd. All rights reserved.)

Objective: The purpose of this study was to determine whether high-sensitivity C-reactive protein (hsCRP) levels differ among patients with acute aortic syndromes (AAS) and if hsCRP could predict their long-term outcomes., Design: Retrospective observational study., Setting: Cleveland Clinic Hospital, Cleveland, Ohio., Patients: 115 consecutive patients with AAS admitted to the cardiac intensive care unit., Interventions: HsCRP and other laboratory data were measured within 24 h of admission. Demographic, imaging and laboratory data were obtained at the time of presentation. For the long-term survival analysis, the social security death index was used to determine all-cause mortality., Main Outcome Measures: HsCRP levels among AAS patients., Results: Hospital mortality was 4.3% for AAS patients. HsCRP levels differed significantly among AAS; the median hsCRP was higher in the aortic dissection group (49 mg/l) than in those with penetrating aortic ulcer (28 mg/l), symptomatic aortic aneurysm (14 mg/l), and intramural haematoma (10 mg/l); (p=0.02). In multivariable analysis, aortic dissection patients had higher hsCRP levels than intramural haematoma (p=0.03) and symptomatic aortic aneurysm (p=0.04) patients, after adjusting for age and gender. Multivariable Cox regression analyses showed that elevated hsCRP levels at presentation were associated with a higher long-term mortality (p=0.007)., Conclusions: Among patients with AAS, those with aortic dissection have the highest hsCRP levels at presentation. Elevated hsCRP independently predicted a higher long-term mortality in AAS patients.

Tako-tsubo cardiomyopathy (TTC) is increasingly diagnosed in the United States, especially in the Caucasian population. To evaluate the clinical features and outcome of patients with TTC, we evaluated 34 patients (32 women and 2 men) 22 to 88 years of age (mean 66 +/- 14) who fulfilled the following criteria: (1) akinesia or dyskinesia of the apical and/or midventricular segments of the left ventricle with regional wall motion abnormalities that extended beyond the distribution of a single epicardial vessel and (2) absence of obstructive coronary artery disease. Twenty-five patients (74%) presented with chest pain, 20 patients (59%) presented with dyspnea, and 8 patients (24%) presented with cardiogenic shock. Twenty-two patients (65%) had ST-segment elevation and 14 patients (41%) had T-wave inversion on presentation. Twenty-five patients (74%) reported a preceding stressful event. Cardiac biomarkers were often mildly increased, with a mean troponin I (peak) of 13.9 +/- 24. Mean +/- SD left ventricular ejection fractions were 28 +/- 10% at time of presentation and 51 +/- 14 at time of follow-up (p <0.0001). Two patients (6%) died during the hospital stay. Average duration of hospital stay was 6.6 +/- 6.2 days. In conclusion, TTC is common in postmenopausal women with preceding physical or emotional stress. It predominantly involves the apical portion of the left ventricle and patients with this condition have a favorable outcome with appropriate medical management. The precise cause remains unclear.

Highly reactive carbon/Fe composites were prepared from tar used as a carbon source, and hematite (alpha-Fe(2)O(3)), a widespread naturally available iron oxide. Tar was impregnated on hematite and thermally treated under N(2) atmosphere. Mössbauer, powder X-ray diffraction and magnetization data suggested that treatment at 400 and 600 degrees C produced only magnetite (Fe(3)O(4)) whereas at 800 degrees C mainly metallic iron (Fe(0)) was produced. Raman, TG and XRD analyses of the different composites revealed the presence of amorphous and graphitic carbon highly dispersed on the iron oxide surface. The composites obtained at 800 degrees C were very efficient in reducing aqueous Cr(VI), as CrO(4)(2-), even compared to finely ground commercial Fe(0). XPS and Mössbauer data showed that after five consecutive reuses, the composites deactivated, due to the surface oxidation of Fe(0). A simple treatment at 800 degrees C completely regenerated the composite by reducing Fe(3+) species allowing several reuses.

Individuals with type 2 diabetes are more likely to experience a myocardial infarction and have worse outcomes compared with nondiabetic individuals. The underlying pathophysiology of the atherosclerotic process is accentuated but not significantly different in patients with type 2 diabetes. In addition, the prothrombotic state associated with diabetes may also contribute to the higher incidence of and worse prognosis after myocardial infarction. Difficulties of re-establishing vessel patency by thrombolytic or mechanical means due to diffuse coronary disease, altered vessel structure, and prothrombotic state can contribute to the high morbidity and mortality in these patients. The concurrent metabolic dysfunction contributes to impair compensatory mechanisms, which can increase infarct size and cause more impairment of left ventricular function. Aggressive medical therapy and careful modulation of glucose metabolism in the acute and follow-up phase of a myocardial infarction may favorably influence outcome.

We describe the use of highly reactive Fe(0)/Fe3O4 composites for the reduction of Cr(VI) species in aqueous medium. The composites were prepared by simple mechanical alloying of metallic iron and magnetite in different proportions, i.e. Fe(0) 25, 50, 75 and 90wt%. While after 3h of reaction pure Fe(0) and pure Fe3O4 showed only a low reduction efficiency of 15% and 25% Cr(VI) conversion, respectively, the composites, in particular Fe(0)(25wt%)/Fe3O4, showed a remarkable activity with ca. 65% Cr(VI) conversion. Kinetic experiments showed a high reaction rate during the first 3h, which subsequently decreased strongly, probably due to a pH increase from 6 to 8. Experiments with composites based on Fe(0)/alpha-Fe2O3, Fe(0)/gamma-Fe2O3 and Fe(0)/FeOOH showed very low activities, suggesting that Fe(oct)2+ in the magnetite structure plays an important role in the reaction. Scanning and high resolution electron microscopies and Mössbauer spectra (transmission and conversion electron Mössbauer spectroscopy) indicated that the mechanical alloying process promotes a strong interaction and interface between the metallic and oxide phases, with the Fe(0) particles completely covered by Fe3O4 particles. The high efficiency of the composite Fe(0)/Fe3O4 for Cr(VI) reduction is discussed in terms of a special mechanism where an electron is transferred from Fe(0) to magnetite to reduce Fe(oct)3+ to Fe(oct)2+, which is active for Cr(VI) reduction.

Atrial septal defects are a common congenital cardiac abnormality in adults. lndividuals with atrial septal defects carry the risk to develop cardiac problems such as right ventricle volume overload, pulmonary hypertension, atrial fibrillation, and more rarely paradoxical embolic events. Surgery was the standard treatment for symptomatic patients with atrial septal defects for decades. More recently, percutaneous transcatheter closure of atrial septal defects in adults using a closure device has become an alternative to surgery in selected patients.

In this work, the effect of incorporation of M2+ species, i.e. Co2+, Mn2+ and Ni2+, into the magnetite structure to increase the reactivity towards H2O2 reactions was investigated. The following magnetites Fe3-xMnxO4, Fe3-xCoxO4 and Fe3-xNixO4 and the iron oxides Fe3O4, gamma-Fe2O3 and alpha-Fe2O3 were prepared and characterized by Mössbauer spectroscopy, XRD, BET surface area, magnetization and chemical analyses. The obtained results showed that the M2+ species at the octahedral site in the magnetite strongly affects the reactivity towards H2O2, i.e. (i) the peroxide decomposition to O2 and (ii) the oxidation of organic molecules, such as the dye methylene blue and chlorobenzene in aqueous medium. Experiments with maghemite, gamma-Fe2O3 and hematite, alpha-Fe2O3, showed very low activities compared to Fe3O4, suggesting that the presence of Fe2+ in the oxide plays an important role for the activation of H2O2. The presence of Co or Mn in the magnetite structure produced a remarkable increase in the reactivity, whereas Ni inhibited the H2O2 reactions. The obtained results suggest a surface initiated reaction involving Msurf2+ (Fe, Co or Mn), producing HO radicals, which can lead to two competitive reactions, i.e. the decomposition of H2O2 or the oxidation of organics present in the aqueous medium. The unique effect of Co and Mn is discussed in terms of the thermodynamically favorable Cosurf3+ and Mnsurf3+ reduction by Femagnetite2+ regenerating the active species M2+.

Electrospray ionization (ESI) mass spectrometry (MS) and tandem mass spectrometry (MS/MS) were used to monitor the oxidation of phenol by a novel heterogeneous Fenton system based on a Fe(0)/Fe(3)O(4) composite and H(2)O(2). On-line ESI-MS(/MS) shows that this heterogeneous system promotes prompt oxidation of phenol to hydroquinone, which is subsequently oxidized to quinone, other cyclic poly-hydroxylated intermediates and an acyclic carboxylic acid. A peroxide-type intermediate, probably formed via an electrophilic attack of HOO(.) on the phenol ring, was also intercepted and characterized. ESI-MS(/MS) monitoring of the oxidation of two other model aromatic compounds, benzene and chlorobenzene, indicates the participation of analogous intermediates. These results suggest that oxidation by the heterogeneous system is promoted by highly reactive HO(.) and HOO(.) radicals generated from H(2)O(2) on the surface of the Fe(0)/Fe(3)O(4) composite via a classical Fenton-like mechanism., (Copyright (c) 2006 John Wiley & Sons, Ltd.)

In this work a novel heterogeneous Fenton system based on Fe(0)/Fe3O4 composites is described. The composites with several Fe(0)/Fe3O4 ratios were prepared by two different methods, i.e. mechanical alloying of Fe(0) and Fe3O4 powders and controlled reduction of Fe3O4 with H2. Reaction studies and detailed Conversion Electron Mössbauer surface characterization of the composites Fe(0)/Fe3O4, Fe(0), Fe3O4, alpha-Fe2O3 and gamma-Fe2O3 suggested that Fe2+surf species are essential to produce an active Fenton system. Kinetic studies for the oxidation of the dye methylene blue, used as an organic model molecule, and for the peroxide decomposition suggest that the reactions proceed via HO* radicals generated from Fe2+surf species and H2O2 in a Fenton like mechanism. The increase in activity caused by the addition of Fe(0) is discussed in terms of a creation of Fe2+surf species during the preparation of the composite and by an electron transfer mechanism from Fe(0) to Fe3+surf during the Fenton reaction to regenerate the Fe2+surf active species.

In this work Fenton's reagent was used to treat activated carbon saturated with organochloro compounds for the oxidation of the adsorbed contaminants and the regeneration of the carbon adsorbent. Activated carbon containing adsorbed chlorinated model substrates such as chlorobenzene, tetrachloroethylene, chloroform or 1,2-dichloropropane was treated with Fenton's reagent at room temperature resulting in a rapid consumption of the organochloro compounds. Thermogravimetric, infrared, BET surface area and MIMS adsorption studies showed that Fenton's treatment has no significant effect on the physico-chemical properties of the activated carbon. The used carbon adsorbents can be efficiently regenerated and recycled with no loss of its adsorption capacity even after five consecutive treatments with Fenton's reagent., (Copyright 2002 Elsevier Science Ltd.)

Chloroform formation during the chlorination of simple organic molecules modeling humic substances, such as phenol and di- and trihydroxybenzenes, was studied by on-line membrane introduction mass spectrometry (MIMS). Under the reaction conditions employed, chloroform was rapidly formed from 1,3-dihydroxybenzene, 1, 4-dihydroxybenzene, phenol and 1,2,3-trihydroxybenzene with yields of 17, 13, 7 and 5%, respectively. With the exception of aniline, which afforded a 17% chloroform yield, non-phenolic compounds, such as nitrobenzene, chlorobenzene, toluene, benzene and cyclohexanol, furnished low yields. Mechanistic studies showed that phenol is chlorinated consecutively and produces initially chlorophenol. It is suggested that chloroform might be formed mainly from chlorinated 3, 5-cyclohexadienone-type intermediates. MIMS was also used to determine the reaction rates and to study the kinetics of the chlorination. A good Hammett linear correlation for an electrophilic substitution mechanism was found for the compounds C(6)H(5)X (X = NH(2), OH, CH(3), H, Cl and NO(2))., (Copyright 2000 John Wiley & Sons, Ltd.)