997 resultados para Polyhydric alcohol CsBr H2O ternary systems


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A multistage distillation column in which mass transfer and a reversible chemical reaction occurred simultaneously, has been investigated to formulate a technique by which this process can be analysed or predicted. A transesterification reaction between ethyl alcohol and butyl acetate, catalysed by concentrated sulphuric acid, was selected for the investigation and all the components were analysed on a gas liquid chromatograph. The transesterification reaction kinetics have been studied in a batch reactor for catalyst concentrations of 0.1 - 1.0 weight percent and temperatures between 21.4 and 85.0 °C. The reaction was found to be second order and dependent on the catalyst concentration at a given temperature. The vapour liquid equilibrium data for six binary, four ternary and one quaternary systems are measured at atmospheric pressure using a modified Cathala dynamic equilibrium still. The systems with the exception of ethyl alcohol - butyl alcohol mixtures, were found to be non-ideal. Multicomponent vapour liquid equilibrium compositions were predicted by a computer programme which utilised the Van Laar constants obtained from the binary data sets. Good agreement was obtained between the predicted and experimental quaternary equilibrium vapour compositions. Continuous transesterification experiments were carried out in a six stage sieve plate distillation column. The column was 3" in internal diameter and of unit construction in glass. The plates were 8" apart and had a free area of 7.7%. Both the liquid and vapour streams were analysed. The component conversion was dependent on the boilup rate and the reflux ratio. Because of the presence of the reaction, the concentration of one of the lighter components increased below the feed plate. In the same region a highly developed foam was formed due to the presence of the catalyst. The experimental results were analysed by the solution of a series of simultaneous enthalpy and mass equations. Good agreement was obtained between the experimental and calculated results.

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The selective conversion of alcohols to their carbonyl derivatives is a critical step towards a sustainable chemical industry. Heterogeneous Pd catalysts represent some of the most active systems known, even so further studies into the active species and role of support are required. Through controlling support mesostructure, using non-interconnected SBA-15 and interlinked SBA-16 and KIT-6, we have evaluated the role of pore architecture on supported Pd nanoparticles and their subsequent activity for liquid phase aerobic allylic alcohol selective oxidation.[1,2] These synthesised silica supports exhibit high surface areas (>800 m2g-1), and similar mesopore diameters (3.5 to 5 nm), but differ in their pore connectivity and arrangement; p6mm (SBA-15), I3mm (SBA-16) and I3ad (KIT-6). When evaluated alongside commercial non-mesoporous silica (200 m2 g-1) they promote enhanced Pd dispersion with interpenetrating assemblies providing further elevation. Macropore introduction into SBA-15, producing a hierarchical macro-mesoporous silica (MM-SBA-15), allows control over mesopore length and accessibility which escalates Pd distribution to levels akin to KIT-6 and SBA-16. Controlling dispersion, and likewise nanoparticle size, is thus facilitated through the choice of support and additionally Pd loading, with cluster sizes spanning 3.2 to 0.8 nm. X-ray spectroscopies indicate nanoparticles are PdO terminated with the oxide content a function of dispersion. Kinetic studies allude to surface PdO being the active site responsible, with a constant TOF observed, independent of loading and support. This confirms activity is governed by PdO density, whilst also overruling internal mass diffusion constraints. MM-SBA-15 facilitates superior activity and TOFs for long chain acyclic terpene alcohols due to reduced internal mass transport constraints.

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Memory deficits and executive dysfunction are highly prevalent among HIV-infected adults. These conditions can affect their quality of life, antiretroviral adherence, and HIV risk behaviors. Several factors have been suggested including the role of genetics in relation to HIV disease progression. This dissertation aimed to determine whether genetic differences in HIV-infected individuals were correlated with impaired memory, cognitive flexibility and executive function and whether cognitive decline moderated alcohol use and sexual transmission risk behaviors among HIV-infected alcohol abusers participating in an NIH-funded clinical trial comparing the efficacy of the adapted Holistic Health Recovery Program (HHRP-A) intervention to a Health Promotion Control (HPC) condition in reducing risk behaviors. ^ A total of 267 individuals were genotyped for polymorphisms in the dopamine and serotonin gene systems. Results yielded significant associations for TPH2, GALM, DRD2 and DRD4 genetic variants with impaired executive function, cognitive flexibility and memory. SNPs TPH2 rs4570625 and DRD2 rs6277 showed a risk association with executive function (odds ratio = 2.5, p = .02; 3.6, p = .001). GALM rs6741892 was associated with impaired memory (odds ratio = 1.9, p = .006). At the six-month follow-up, HHRP-A participants were less likely to report trading sex for food, drugs and money (20.0%) and unprotected insertive or receptive oral (11.6%) or vaginal and/or anal sex (3.2%) than HPC participants (49.4%, p^

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Memory deficits and executive dysfunction are highly prevalent among HIV-infected adults. These conditions can affect their quality of life, antiretroviral adherence, and HIV risk behaviors. Several factors have been suggested including the role of genetics in relation to HIV disease progression. This dissertation aimed to determine whether genetic differences in HIV-infected individuals were correlated with impaired memory, cognitive flexibility and executive function and whether cognitive decline moderated alcohol use and sexual transmission risk behaviors among HIV-infected alcohol abusers participating in an NIH-funded clinical trial comparing the efficacy of the adapted Holistic Health Recovery Program (HHRP-A) intervention to a Health Promotion Control (HPC) condition in reducing risk behaviors. A total of 267 individuals were genotyped for polymorphisms in the dopamine and serotonin gene systems. Results yielded significant associations for TPH2, GALM, DRD2 and DRD4 genetic variants with impaired executive function, cognitive flexibility and memory. SNPs TPH2 rs4570625 and DRD2 rs6277 showed a risk association with executive function (odds ratio = 2.5, p = .02; 3.6, p = .001). GALM rs6741892 was associated with impaired memory (odds ratio = 1.9, p = .006). At the six-month follow-up, HHRP-A participants were less likely to report trading sex for food, drugs and money (20.0%) and unprotected insertive or receptive oral (11.6%) or vaginal and/or anal sex (3.2%) than HPC participants (49.4%, p

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A Fourier transform infrared gas-phase method is described herein and capable of deriving the vapour pressure of each pure component of a poorly volatile mixture and determining the relative vapour phase composition for each system. The performance of the present method has been validated using two standards (naphthalene and ferrocene), and a Raoultâs plot surface of a ternary system is reported as proof-of-principle. This technique is ideal for studying solutions comprising two, three, or more organic compounds dissolved in ionic liquids as they have no measurable vapour pressures.

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Abstract : Wastepaper sludge ash (WSA) is generated by a cogeneration station by burning wastepaper sludge. It mainly consists of amorphous aluminosilicate phase, anhydrite, gehlenite, calcite, lime, C2S, C3A, quartz, anorthite, traces of mayenite. Because of its free lime content (~10%), WSA suspension has a high pH (13). Previous researchers have found that the WSA composition has poor robustness and the variations lead to some unsoundness for Portland cement (PC) blended WSA concrete. This thesis focused on the use of WSA in different types of concrete mixes to avoid the deleterious effect of the expansion due to the WSA hydration. As a result, WSA were used in making alkali-activated materials (AAMs) as a precursor source and as a potential activator in consideration of its amorphous content and the high alkaline nature. Moreover, the autogenous shrinkage behavior of PC concrete at low w/b ratio was used in order to compensate the expansion effect due to WSA. The concrete properties as well as the volume change were investigated for the modified WSA blended concrete. The reaction mechanism and microstructure of newly formed binder were evaluated by X-ray diffraction (XRD), calorimetry, thermogravimetric analysis (TGA), scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDX). When WSA was used as precursor, the results showed incompatible reaction between WSA and alkaline solution. The mixtures were not workable and provided very low compressive strength no matter what kinds of chemical activators were used. This was due to the metallic aluminum in WSA, which releases abundant hydrogen gas when WSA reacts with strong alkaline solution. Besides, the results of this thesis showed that WSA can activate the glassy phase contained in slag, glass powder (GP) and class F fly ash (FFA) with an optimum blended ratio of 50:50. The WSA/slag (mass ratio of 50:50) mortar (w/b of 0.47) attained 46 MPa at 28 days without heat curing assistance. A significant fast setting was noticed for the WSA-activated binder due to the C3A phase, free lime and metallic aluminum contained in the WSA. Adding 5% of gypsum can delay the fast setting, but this greatly increased the potential risk of intern sulfate attack. The XRD, TGA and calorimetry analyses demonstrated the formation of ettringite, C-S-H, portlandite, hydrogarnet and calcium carboaluminate in the hydrated binder. The mechanical performance of different binder was closely related to the microstructure of corresponding binder which was proved by the SEM observation. The hydrated WSA/slag and WSA/FFA binder formed a C-A-S-H type of gel with lower Ca/Si ratio (0.47~1.6). A hybrid gel (i.e. C-N-A-S-H) was observed for the WSA/GP binder with a very low Ca/Si ratio (0.26) and Na/Si ratio (0.03). The SEM/EDX analyses displayed the formation of expansive gel (ettringite and thaumasite) in the gypsum added WSA/slag concrete. The gradual emission of hydrogen gas due to the reaction of WSA with alkaline environment significantly increased the porosity and degraded the microstructure of hydrated matrix after the setting. In the last phase of this research WSA-PC blended binder was tailored to form a high autogenous shrinkage concrete in order to compensate the initial expansion. Different binders were proportioned with PC, WSA, silica fume or slag. The microstructure and mechanical properties of concrete can be improved by decreasing w/b ratios and by incorporating silica fume or slag. The 28-day compressive strength of WSA-blended concrete was above 22 MPa and reached 45 MPa when silica fume was added. The PC concrete incorporating silica fume or slag tended to develop higher autogenous shrinkage at low w/b ratios, and thus the ternary binder with the addition of WSA inhibited the long term shrinkage due to the initial expansion property to WSA. In the restrained shrinkage test, the concrete ring incorporating the ternary binder (PC/WSA/slag) revealed negligible potential to cracking up to 96 days as a result of the offset effect by WSA expansion. The WSA blended regular concrete could be produced for potential applications with reduced expansion, good mechanical property and lower permeability.

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Objective: In the setting of the increasing use of closed systems for reconstitution and preparation of these drugs, we intend to analyze the correct use of these systems in the Hospital Pharmacy, with the objective to minimize the risks of exposure not only for those professionals directly involved, but also for all the staff in the unit, taking also into account efficiency criteria. Method: Since some systems protect against aerosol formation but not from vapours, we decided to review which cytostatics should be prepared using an awl with an air inlet valve, in order to implement a new working procedure. We reviewed the formulations available in our hospital, with the following criteria: method of administration, excipients, and potential hazard for the staff handling them. We measured the diameters of the vials. We selected drugs with Level 1 Risk and also those including alcohol-based excipients, which could generate vapours. Outcomes: Out of the 66 reviewed formulations, we concluded that 11 drugs should be reconstituted with this type of awl: busulfan, cabazitaxel, carmustine, cyclophosphamide, eribulin, etoposide, fotemustine, melphalan, paclitaxel, temsirolimus and thiotepa; these represented an 18% of the total volume of formulations. Conclusions: The selection of healthcare products must be done at the Hospital Pharmacy, because the use of a system with an air valve inlet only for those drugs selected led to an outcome of savings and a more efficient use of materials. In our experience, we confirmed that the use of the needle could only be avoided when the awl could adapt to the different formulations of cytostatics, and this is only possible when different types of awls are available. Besides, connections were only really closed when a single awl was used for each vial. The change in working methodology when handling these drugs, as a result of this study, will allow us to start different studies about environmental contamination as a future line of work.

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Alcohol is one of the oldest and most widely used drugs on the planet, but the cellular mechanisms by which it affects neural function are still poorly understood. Unlike other drugs of abuse, alcohol has no specific receptor in the nervous system, but is believed to operate through GABAergic and serotonergic neurotransmitter systems. Invertebrate models offer circuits of reduced numerical complexity and involve the same cell types and neurotransmitter systems as vertebrate circuits. The well-understood neural circuits controlling crayfish escape behavior offer neurons that are modulated by GABAergic inhibition, thus making tail-flip circuitry an effective circuit model to study the cellular mechanisms of acute alcohol exposure. Crayfish are capable of two stereotyped, reflexive escape behaviors known as tail-flips that are controlled by two different pairs of giant interneurons, the lateral giants (LG) and the medial giants (MG). The LG circuit has been an established model in the neuroscience field for more than 60 years and is almost completely mapped out. In contrast, the MG is still poorly understood, but has important behavioral implications in social behavior and value-based decision making. In this dissertation, I show that both crayfish tail-flip circuitry are physiologically sensitive to relevant alcohol concentrations and that this sensitivity is observable on the single cell level. I also show that this ethyl alcohol (EtOH) sensitivity in the LG can be changed by altering the crayfishâs recent social experience and by removing descending inputs to the LG. While the MG exhibits similar physiological sensitivity, its inhibitory properties have never been studied before this research. Through the use of electrophysiological and pharmacological techniques, I show that the MG exhibits many similar inhibitory properties as the LG that appear to be the result of GABA-mediated chloride currents. Finally, I present evidence that the EtOH-induced changes in the MG are blocked through pre-treatment of the potent GABAA receptor agonist, muscimol, which underlines the role of GABA in EtOHâs effects on crayfish tail-flip circuitry. The work presented here opens the way for crayfish tail-flip circuitry to be used as an effective model for EtOHâs acute effects on aggression and value-based decision making.

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This Ph.D. thesis concerns the synthesis of nanostructured Cu-containing materials to be used as electrode modifiers for the CO2 electroreduction in aqueous phase and the evaluation of their catalytic performances. Inspired by the fascinating concept of the artificial photosynthesis-oriented systems, several catalytic layers were electrochemically loaded on carbonaceous gas diffusion membranes, i.e., 3D structures that allow the design of eco-friendly materials for applications in green carbon recycling processes. In particular, early studies on Cu(I-II)-Cu(0) nanostructured materials were carried out to produce films on 4 cm2 sized supports by means of a fast and low-cost electrochemical procedure. Besides, through a screening of potentials, it was possible to find out a selective value for the CH3COOH production at -0.4 V vs RHE with a maximum productivity (1h reaction), ensured by the presence of the Cu+/Cu0 active redox couple (0.31 mmol gcat-1 h-1). On the basis of these results, further optimisations of the electrocatalyst chemical composition were carried out with the aim of (i) facilitating the interaction with CO2, (ii) increasing the dispersion of the catalytic active phase, and (iii) enhancing the CH3COOH productivity. To this aim, novel electrocatalysts based on layered double hydroxides (LDHs) were optimised, having as a final goal the formation of a new Cu2O-Cu0 based electrocatalyst derived from electrochemically achieved CuMgAl LDHs, subjected to calcination and reduction processes. The as-obtained electrocatalysts were tested for the selective production of CH3COOH and unprecedented results were obtained with the pristine CuMgAl LDH (2.0 mmol gcat-1 h-1). Additional characterisations of such an electrocatalyst have highlighted the possibility to achieve a ternary LDH in intimate contact with Cu2O-Cu0 species starting from the electrochemical deposition. The presence of these species, along with an alkaline environment on the electrode surface, were essential to preserve the selectivity towards the desired product, as confirmed by further operando studies.

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To evaluate associations between polymorphisms of the N-acetyltransferase 2 (NAT2), human 8-oxoguanine glycosylase 1 (hOGG1) and X-ray repair cross-complementing protein 1 (XRCC1) genes and risk of upper aerodigestive tract (UADT) cancer. A case-control study involving 117 cases and 224 controls was undertaken. The NAT2 gene polymorphisms were genotyped by automated sequencing and XRCC1 Arg399Gln and hOGG1 Ser326Cys polymorphisms were determined by Polymerase Chain Reaction followed by Restriction Fragment Length Polymorphism (PCR-RFLP) methods. Slow metabolization phenotype was significantly associated as a risk factor for the development of UADT cancer (p=0.038). Furthermore, haplotype of slow metabolization was also associated with UADT cancer (p=0.014). The hOGG1 Ser326Cys polymorphism (CG or GG vs. CC genotypes) was shown as a protective factor against UADT cancer in moderate smokers (p=0.031). The XRCC1 Arg399Gln polymorphism (GA or AA vs. GG genotypes), in turn, was a protective factor against UADT cancer only among never-drinkers (p=0.048). Interactions involving NAT2, XRCC1 Arg399Gln and hOGG1 Ser326Cys polymorphisms may modulate the risk of UADT cancer in this population.

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The development and maintenance of the sealing of the root canal system is the key to the success of root canal treatment. The resin-based adhesive material has the potential to reduce the microleakage of the root canal because of its adhesive properties and penetration into dentinal walls. Moreover, the irrigation protocols may have an influence on the adhesiveness of resin-based sealers to root dentin. The objective of the present study was to evaluate the effect of different irrigant protocols on coronal bacterial microleakage of gutta-percha/AH Plus and Resilon/Real Seal Self-etch systems. One hundred ninety pre-molars were used. The teeth were divided into 18 experimental groups according to the irrigation protocols and filling materials used. The protocols used were: distilled water; sodium hypochlorite (NaOCl)+eDTA; NaOCl+H3PO4; NaOCl+eDTA+chlorhexidine (CHX); NaOCl+H3PO4+CHX; CHX+eDTA; CHX+ H3PO4; CHX+eDTA+CHX and CHX+H3PO4+CHX. Gutta-percha/AH Plus or Resilon/Real Seal Se were used as root-filling materials. The coronal microleakage was evaluated for 90 days against Enterococcus faecalis. Data were statistically analyzed using Kaplan-Meier survival test, Kruskal-Wallis and Mann-Whitney tests. No significant difference was verified in the groups using chlorhexidine or sodium hypochlorite during the chemo-mechanical preparation followed by eDTA or phosphoric acid for smear layer removal. The same results were found for filling materials. However, the statistical analyses revealed that a final flush with 2% chlorhexidine reduced significantly the coronal microleakage. A final flush with 2% chlorhexidine after smear layer removal reduces coronal microleakage of teeth filled with gutta-percha/AH Plus or Resilon/Real Seal SE.

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To evaluate the effectiveness of Reciproc for the removal of cultivable bacteria and endotoxins from root canals in comparison with multifile rotary systems. The root canals of forty human single-rooted mandibular pre-molars were contaminated with an Escherichia coli suspension for 21 days and randomly assigned to four groups according to the instrumentation system: GI - Reciproc (VDW); GII - Mtwo (VDW); GIII - ProTaper Universal (Dentsply Maillefer); and GIV -FKG Race(â¢) (FKG Dentaire) (n = 10 per group). Bacterial and endotoxin samples were taken with a sterile/apyrogenic paper point before (s1) and after instrumentation (s2). Culture techniques determined the colony-forming units (CFU) and the Limulus Amebocyte Lysate assay was used for endotoxin quantification. Results were submitted to paired t-test and anova. At s1, bacteria and endotoxins were recovered in 100% of the root canals investigated (40/40). After instrumentation, all systems were associated with a highly significant reduction of the bacterial load and endotoxin levels, respectively: GI - Reciproc (99.34% and 91.69%); GII - Mtwo (99.86% and 83.11%); GIII - ProTaper (99.93% and 78.56%) and GIV - FKG Race(â¢) (99.99% and 82.52%) (P < 0.001). No statistical difference were found amongst the instrumentation systems regarding bacteria and endotoxin removal (P > 0.01). The reciprocating single file, Reciproc, was as effective as the multifile rotary systems for the removal of bacteria and endotoxins from root canals.

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The aim of this work was to characterize the effects of partial inhibition of respiratory complex I by rotenone on H2O2 production by isolated rat brain mitochondria in different respiratory states. Flow cytometric analysis of membrane potential in isolated mitochondria indicated that rotenone leads to uniform respiratory inhibition when added to a suspension of mitochondria. When mitochondria were incubated in the presence of a low concentration of rotenone (10 nm) and NADH-linked substrates, oxygen consumption was reduced from 45.9 ± 1.0 to 26.4 ± 2.6 nmol O2 mg(-1) min(-1) and from 7.8 ± 0.3 to 6.3 ± 0.3 nmol O2 mg(-1) min(-1) in respiratory states 3 (ADP-stimulated respiration) and 4 (resting respiration), respectively. Under these conditions, mitochondrial H2O2 production was stimulated from 12.2 ± 1.1 to 21.0 ± 1.2 pmol H2O2 mg(-1) min(-1) and 56.5 ± 4.7 to 95.0 ± 11.1 pmol H2O2 mg(-1) min(-1) in respiratory states 3 and 4, respectively. Similar results were observed when comparing mitochondrial preparations enriched with synaptic or nonsynaptic mitochondria or when 1-methyl-4-phenylpyridinium ion (MPP(+)) was used as a respiratory complex I inhibitor. Rotenone-stimulated H2O2 production in respiratory states 3 and 4 was associated with a high reduction state of endogenous nicotinamide nucleotides. In succinate-supported mitochondrial respiration, where most of the mitochondrial H2O2 production relies on electron backflow from complex II to complex I, low rotenone concentrations inhibited H2O2 production. Rotenone had no effect on mitochondrial elimination of micromolar concentrations of H2O2. The present results support the conclusion that partial complex I inhibition may result in mitochondrial energy crisis and oxidative stress, the former being predominant under oxidative phosphorylation and the latter under resting respiration conditions.

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The aim of this study was to evaluate by photoelastic analysis stress distribution on short and long implants of two dental implant systems with 2-unit implant-supported fixed partial prostheses of 8âmm and 13âmm heights. Sixteen photoelastic models were divided into 4 groups: I: long implant (5 à 11âmm) (Neodent), II: long implant (5 à 11âmm) (Bicon), III: short implant (5 à 6âmm) (Neodent), and IV: short implants (5 à 6âmm) (Bicon). The models were positioned in a circular polariscope associated with a cell load and static axial (0.5âKgf) and nonaxial load (15°, 0.5âKgf) were applied to each group for both prosthetic crown heights. Three-way ANOVA was used to compare the factors implant length, crown height, and implant system (α = 0.05). The results showed that implant length was a statistically significant factor for both axial and nonaxial loading. The 13âmm prosthetic crown did not result in statistically significant differences in stress distribution between the implant systems and implant lengths studied, regardless of load type (P > 0.05). It can be concluded that short implants showed higher stress levels than long implants. Implant system and length was not relevant factors when prosthetic crown height were increased.

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Pathological conditions associated with the impairment of nitric oxide (NO) production in the vasculature, such as Raynaud's syndrome and diabetic angiopathy, have stimulated the development of new biomaterials capable of delivering NO topically. With this purpose, we modified poly(vinyl-alcohol) (PVA) by chemically crosslinking it via esterification with mercaptosuccinic acid. This reaction allowed the casting of sulfhydrylated PVA (PVA-SH) films. Differential scanning calorimetry and X-ray diffractometry showed that the crosslinking reaction completely suppressed the crystallization of PVA, leading to a non-porous film with a homogeneous distribution of -SH groups. The remaining free hydroxyl groups in the PVA-SH network conferred partial hydrophylicity to the material, which was responsible for a swelling degree of ca. 110%. The PVA-SH films were subjected to an S-nitrosation reaction of the -SH groups, yielding a PVA containing S-nitrosothiol groups (PVA-SNO). Amperometric and chemiluminescence measurements showed that the PVA-SNO films were capable of releasing NO spontaneously after immersion in physiological medium. Laser Doppler-flowmetry, used to assess the blood flow in the dermal microcirculation, showed that the topical application of hydrated PVA-SNO films on the health skin led to a dose- and time-dependent increase of more than 5-fold in the dermal baseline blood flow in less than 10min, with a prolonged action of more than 4h during continuous application. These results show that PVA-SNO films might emerge as a new material with potential for the topical treatment of microvascular skin disorders.