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1.
J Am Chem Soc ; 146(18): 12645-12655, 2024 May 08.
Artigo em Inglês | MEDLINE | ID: mdl-38651821

RESUMO

The increased production of plastics is leading to the accumulation of plastic waste and depletion of limited fossil fuel resources. In this context, we report a strategy to create polymers that can undergo controlled depolymerization by linking renewable feedstocks with siloxane bonds. α,ω-Diesters and α,ω-diols containing siloxane bonds were synthesized from an alkenoic ester derived from castor oil and then polymerized with varied monomers, including related biobased monomers. In addition, cyclic monomers derived from this alkenoic ester and hydrosiloxanes were prepared and cyclized to form a 26-membered macrolactone containing a siloxane unit. Sequential ring-opening polymerization of this macrolactone and lactide afforded an ABA triblock copolymer. This set of polymers containing siloxanes underwent programmed depolymerization into monomers in protic solvents or with hexamethyldisiloxane and an acid catalyst. Monomers afforded by the depolymerization of polyesters containing siloxane linkages were repolymerized to demonstrate circularity in select polymers. Evaluation of the environmental stability of these polymers toward enzymatic degradation showed that they undergo enzymatic hydrolysis by a fungal cutinase from Fusarium solani. Evaluation of soil microbial metabolism of monomers selectively labeled with 13C revealed differential metabolism of the main chain and side chain organic groups by soil microbes.


Assuntos
Fusarium , Polimerização , Siloxanas , Siloxanas/química , Óleos de Plantas/química , Polímeros/química , Estrutura Molecular , Hidrolases de Éster Carboxílico
2.
Int J Biol Macromol ; 236: 123994, 2023 May 01.
Artigo em Inglês | MEDLINE | ID: mdl-36914059

RESUMO

The porous structure and hydrophilicity of coating shells affect the nutrient controlled-release performance of castor oil-based (CO) coated fertilizers. In order to solve these problems, in this study, the castor oil-based polyurethane (PCU) coating material was modified with liquefied starch polyol (LS) and siloxane, and a new coating material with cross-linked network structure and hydrophobic surface was synthesized, and used it to prepare the coated controlled-release urea (SSPCU). The results demonstrated that the cross-linked network formed by LS and CO improved the density and reduced the pores on the surface of the coating shells. The siloxane was grafted on the surface of coating shells to improve its hydrophobicity and thus delayed water entry. The nitrogen release experiment indicated that the synergistic effects of LS and siloxane improved the nitrogen controlled-release performance of bio-based coated fertilizers. Nutrient released longevity of SSPCU with 7 % coating percentage reached >63 days. Moreover, the nutrient release mechanism of coated fertilizer was further revealed by the analysis of the release kinetics analysis. Therefore, the results of this study provide a new idea and technical support for development of efficient and environment-friendly bio-based coated controlled-release fertilizers.


Assuntos
Fertilizantes , Siloxanas , Preparações de Ação Retardada/química , Óleo de Rícino , Nitrogênio/química
3.
Artigo em Inglês | MEDLINE | ID: mdl-35270319

RESUMO

Microalgae are widely used in the bioremediation of wastewaters due to their efficient removal of pollutants such as nitrogen, phosphorus, and contaminants of emerging concern (CECs). Siloxanes are CECs that reach wastewater treatment plants (WWTPs), leading to the production of biogas enriched with these compounds, associated with the breakdown of cogeneration equipment. The biological removal of siloxanes from wastewaters could be a sustainable alternative to the costly existing technologies, but no investigation has been performed using microalgal cultures for this purpose. This study evaluated the ability of Chlorella vulgaris to bioremediate primary (PE) and secondary (SE) urban effluents and remove volatile methylsiloxanes (VMSs). C. vulgaris grew successfully in both effluents, and approximately 86% of nitrogen and 80% of phosphorus were efficiently removed from the PE, while 52% of nitrogen and 87% of phosphorus were removed from the SE, and the presence of VMSs does not seem to have a negative influence on nutrient removal. Three out of the seven of the analysed VMSs were detected in the microalgal biomass at the end of the PE assay. However, dodecamethylcyclohexasiloxane (D6) was the one that accumulated to a greater extent, since 48% of the initial mass of D6 was detected in the biomass samples. D6 is one of the most lipophilic VMSs, which might contribute to the higher adsorption onto the surface of microalgae. Overall, the results indicate C. vulgaris' potential to remove specific VMSs from effluents.


Assuntos
Chlorella vulgaris , Microalgas , Biodegradação Ambiental , Biomassa , Nitrogênio/análise , Fósforo , Siloxanas/análise , Águas Residuárias/análise
4.
Crit Rev Toxicol ; 51(7): 571-590, 2021 08.
Artigo em Inglês | MEDLINE | ID: mdl-34877914

RESUMO

This review is a hypothesis driven, mechanistic evaluation of the potential for octamethylcyclotetrasiloxane (D4) to produce any effects via endocrine modes of action. D4 is a volatile, lipophilic liquid used in the production of high molecular weight dimethylsiloxane polymers. These are used in a variety of industrial, medical, cleaning, and personal care products, and they may contain low levels of residual D4. Low concentrations of D4 are found in the environment and there is potential for low level human exposure. All of the measured environmental and workplace levels of D4 fall below no observed effect levels (NOEL). Most of the effects of high dose D4 involve the female reproductive system. In the mature intact female rat following chronic high dose exposure, D4 may cause inhibition of mating and ovulation, decreased live litter sizes, small increases in the estrogen to progesterone ratio primarily through decreases in progesterone, and increases in uterine hyperplasia. When endogenous estrogens are very low, high dose D4 causes increases in some uterine parameters. To assess whether these high dose effects can be attributed to an endocrine mode of action, endpoints are ranked for relevance and strength, consistent with published concepts. When sufficient information is available the level of activity of D4 for producing the observed effect is compared with that of potent endocrines. The conclusions reached are that all of the effects of D4 fall well short of any established criteria for D4 to be capable of producing any adverse effect via an endocrine mode of action.


Assuntos
Siloxanas , Útero , Animais , Feminino , Nível de Efeito Adverso não Observado , Ratos , Reprodução , Siloxanas/toxicidade
5.
J Colloid Interface Sci ; 602: 394-405, 2021 Nov 15.
Artigo em Inglês | MEDLINE | ID: mdl-34139537

RESUMO

This paper reports a fresh and robust strategy to develop polyurethane/polysiloxane pressure-sensitive adhesives (PSAs) with excellent properties by replacing part of C5 petroleum resin with modified lignin. A unique aspect of this work is the use of renewable lignin to obtain modified monomers. The phenolic hydroxyl group of lignin is increased by 21.4% after demethylation, which will help to introduce 6-bromo-1-hexene into the lignin structure through Williamson method. The L3 lignin and C5 petroleum resin are mixed with polyurethane/polysiloxane prepolymer, and furthermore a series of PSAs are obtained under ultraviolet light. It turns out that L3 lignin can not only replace part of C5 petroleum resin, but also obtain attractive and controllable features. Especially when the mass ratio of C5 petroleum resin to L3 lignin is 6:4, compared with pure C5 petroleum resin, the 180° peel strength and the shear strength of PU46 are increased by 24.1% and 91.5% respectively. Additionally, the shear strength on the wood substrate is increased by 320.6%. This study provides an effective method for the preparation of high value-added lignin PSA, and expands the application fields of PSA.


Assuntos
Lignina , Petróleo , Adesivos , Poliuretanos , Siloxanas , Madeira
6.
Environ Int ; 152: 106471, 2021 07.
Artigo em Inglês | MEDLINE | ID: mdl-33676090

RESUMO

High concentrations (1.08 ng/g-3.61 mg/g) of methylsiloxanes, including cyclic analogs [octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6)], and linear analogs with 3-14 silicon atoms (L3-L14), have been detected in crude oil, additives and petroleum products from one petroleum refinery facility in China. Overall, the total mass load of Σmethylsiloxanes (1320 kg/day) in crude oil and additives was 1.5 times higher than that in petroleum products (857 kg/day), indicating their potential emissions in this facility, which were further confirmed by the find of their obvious emission through exhaust-gas (89.4 kg/day) and wastewater (4.70 kg/day). Σmethylsiloxanes emission from exhaust-gas discharge outlets of deep catalytic cracking units (60.6 kg/day) took up 68% of their total emission from all gas outlets. Overall, Σmethylsiloxanes in air (17.1-743 µg/m3) and soil samples [311 ng/g dw (dry weight) - 34.2 µg/g dw] from this facility were up to four orders of magnitude greater than those from surrounding areas, and plasma concentrations of Σmethylsiloxanes in current workers from this facility (7.4-609 ng/mL) were up to two orders of magnitude larger than those from reference group (

Assuntos
Exposição Ocupacional , Petróleo , China , Monitoramento Ambiental , Humanos , Exposição Ocupacional/análise , Siloxanas/análise , Águas Residuárias
7.
ACS Appl Mater Interfaces ; 12(33): 37628-37636, 2020 Aug 19.
Artigo em Inglês | MEDLINE | ID: mdl-32814391

RESUMO

Multifunctional drug delivery systems were designed and engineered by template synthesis of a microporous organic polymer (MOP) and by postsynthetic modification. Hollow MOP spheres bearing Fe3O4 yolks (Fe3O4@Void@MOP) were prepared by the synthesis of MOP on Fe3O4@SiO2 nanoparticles and by successive silica etching. In addition to the magneto-thermal function of Fe3O4 yolks, an aggregation-induced emission (AIE) feature was incorporated into the Fe3O4@Void@MOP through a homocoupling of tetra(4-ethynylphenyl)ethylene to form Fe3O4@Void@MOP-TE. Folate groups were further introduced into Fe3O4@Void@MOP-TE through the postsynthetic modification based on the thiol-yne click reaction. The resultant Fe3O4@Void@MOP-TE-FA showed multifunctionality in antitumoral therapy via folate receptor targeting, doxorubicin delivery, AIE-based imaging, and the magneto-thermal feature.


Assuntos
Portadores de Fármacos/química , Óxido Ferroso-Férrico/química , Nanopartículas de Magnetita/química , Neoplasias/diagnóstico por imagem , Neoplasias/tratamento farmacológico , Siloxanas/química , Antineoplásicos/química , Antineoplásicos/farmacologia , Linhagem Celular Tumoral , Permeabilidade da Membrana Celular , Química Click , Terapia Combinada , Diagnóstico por Imagem , Doxorrubicina/química , Doxorrubicina/farmacologia , Liberação Controlada de Fármacos , Etilenos/química , Ácido Fólico/química , Humanos , Hipertermia Induzida , Indicadores e Reagentes/química , Porosidade , Dióxido de Silício/química , Compostos de Sulfidrila/química , Propriedades de Superfície
8.
Int J Biol Macromol ; 144: 682-689, 2020 Feb 01.
Artigo em Inglês | MEDLINE | ID: mdl-31857158

RESUMO

In the present study, the effect of plasma treatment on the structural properties of three granular corn starches (normal, Hylon V and Hylon VII) was investigated. Thermal (TGA/DSC), structural (XRD/FTIR) and chemical (XPS) properties were evaluated. Plasma treatment resulted in partial evaporation of water molecules changing the organization level of the double helices in the crystalline lamellae. Moreover, XRD results suggested a decrease of the long-range crystallinity and suggested changes in amylose chains after treatments. The crosslinking of modified amylose chains measured by XPS analysis resulted in variations in the gelatinization parameters as well as in its heterogeneous crystalline structure. The results indicate that the type and extent of changes in the structure of plasma-treated corn starch depends on the distribution of the water molecules inside the crystalline regions (helical water) and on the amylose content. In addition, the obtained results indicated that plasma treatment is a suitable method to modify starch without any incorporation of new elements from hexamethyldisiloxane (HMDSO), which only promotes stronger interactions between the starch main components.


Assuntos
Gases em Plasma/química , Siloxanas/química , Amido/química , Zea mays/química , Amilose/química , Reagentes de Ligações Cruzadas/química , Cristalização , Gelatina/química , Conformação Molecular , Propriedades de Superfície , Água
9.
Bioresour Technol ; 294: 122136, 2019 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-31539855

RESUMO

The removal of siloxanes (D4 and D5) and volatile organic contaminants (hexane, toluene and limonene) typically found in sewage biogas was investigated in a lab-scale biotrickling filter (BTF) packed with lava rock under anoxic conditions. Complete removal efficiencies for toluene and limonene were recorded at all empty bed residence time (EBRT) tested. The influence of EBRT was remarkable on the abatement of D5, whose removal decreased from 37% at 14.5 min to 16% at 4 min, while the removal of D4 and hexane remained below 16%. The packing material was supplemented with 20% of activated carbon aiming at increasing the mass transfer of the most hydrophobic pollutants. This strategy supported high removal efficiencies of 43 and 45% for hexane and D5 at the lowest EBRT. CO2 and silica were identified as mineralization products along with the presence of metabolites in the trickling solution such as dimethylsilanediol, 2-carene and α-terpinene.


Assuntos
Biocombustíveis , Compostos Orgânicos Voláteis , Reatores Biológicos , Carvão Vegetal , Filtração , Esgotos , Siloxanas
10.
J Chromatogr A ; 1600: 112-126, 2019 Aug 30.
Artigo em Inglês | MEDLINE | ID: mdl-31128882

RESUMO

The solvation parameter model is used to characterize the retention properties of 25 siloxane-bonded type-B silica columns under typical reversed-phase liquid chromatography conditions with binary aqueous mobile phases containing 10-70% (v/v) methanol and acetonitrile. To further explore the affect of solvent type on column selectivity complementary information is presented for aqueous phases containing 10-70% (v/v) tetrahydrofuran for two columns. Columns were selected to include examples of all common column packing morphologies for small molecule separations (totally porous particles, superficially porous particles, organic-inorganic hybrid particles, and a monolith) and common topologies octadecylsiloxane-bonded (including phases with a polar-embedded group, mixed-mode phases with a short-chain siloxane-bonded polar functional group, sterically crowded, positive shield, and fluorine-containing phases); octylsiloxane-bonded; and various phenyl-containing stationary phases with different linker arms, pentafluorophenylalkyl and biphenyl groups. The column properties are reported as a system constant database and as system maps for the full range of mobile phase compositions. Selectivity differences are evaluated using principal component factor analysis to classify the columns into selectivity groups and correlation plots of the system constants for compared columns at all mobile phase compositions. The later is shown to be a suitable technique to identify (near) selectivity equivalent columns and varied columns suitable for method development. Contributions to retention from steric resistance and cation-exchange interactions not parameterized in the solvation parameter model are identified for columns and conditions where they may be important. It is shown that the interaction parameters employed in the hydrophobic-subtraction model have little overlap with those of the solvation parameter model and a quantitative comparison of column properties delineated by both models is not possible.


Assuntos
Cromatografia de Fase Reversa , Bases de Dados Factuais , Dióxido de Silício/química , Siloxanas/química , Solventes/química , Acetonitrilas/química , Interações Hidrofóbicas e Hidrofílicas , Indicadores e Reagentes , Metanol/química , Porosidade , Água/química
11.
Environ Sci Technol ; 53(7): 3558-3567, 2019 04 02.
Artigo em Inglês | MEDLINE | ID: mdl-30907086

RESUMO

In two oil-wastewater treatment stations of Shengli Oilfield, cyclic volatile methylsiloxanes (cVMS, D4-D6) in the wastewater stream were found to undergo chlorination during electro-oxidation process for wastewater containing chlorine ions (16.1-42.0 g/L). Their converted fractions were 4.71-28.0% for monochlorinated D4-D6 and 0.22-7.96% for dichlorinated D4, which were ∼2 orders of magnitude higher than those for hydroxylated products. Furthermore, portions of chlorinated methylsiloxanes retained in excess sludge were released to the surrounding soils. In soil samples ( n = 500), chlorinated methylsiloxanes concentrations (

Assuntos
Olea , Águas Residuárias , Medicamentos de Ervas Chinesas , Siloxanas , Solo
12.
Toxicol Lett ; 279 Suppl 1: 98-114, 2017 Oct 20.
Artigo em Inglês | MEDLINE | ID: mdl-28511864

RESUMO

Octamethylcyclotetrasiloxane (D4) and decamethylcyclopentasiloxane (D5) are low molecular weight cyclic volatile methyl siloxanes (cVMSs) primarily used as intermediates or monomers in the production of high molecular weight silicone polymers. The use of D4 as a direct ingredient in personal care products has declined significantly over the past 20 years, although it may be present as a residual impurity in a variety of consumer products. D5 is still used as an intentional ingredient in cosmetics, consumer products and in dry cleaning. Persons who may be exposed include occupational exposure for workers, and potential inhalation or dermal exposure for consumers and the general public. Because of the diverse use, especially of D5, and the potential for human exposure, a comprehensive program was undertaken to understand the kinetics, metabolism, enzyme induction and toxicity of D4 and D5 in rats following relevant routes of exposure. Physiologically based pharmacokinetic (PBPK) models utilizing these studies have been reported for D4 and D5 in the rat and human following dermal and inhalation exposures, with the oral uptake component of the model being limited in its description. Data from high dose oral studies in corn oil and simethicone vehicles and neat were used in the D4/D5 harmonized PBPK model development. It was uncertain if the inability to adequately describe the oral uptake was due to unrealistic high doses or unique aspects of the chemistry of D4/D5. Low dose studies were used to provide data to refine the description of oral uptake in the model by exploring the dose dependency and the impact of a more realistic food-like vehicle. Absorption, distribution, metabolism and elimination (ADME) of D4 and D5 was determined following a single low oral gavage dose of 14C-D4 and 14C-D5 at 30 and 100mg/kg body weight (bw), respectively, in a rodent liquid diet. Comparison of the low vs. high dose oral gavage administration of D4 and D5 demonstrated dose-dependent kinetic behavior. Data and modeling results suggest differences in metabolism between low and high dose administration indicating high dose administration results in or approaches non-linear saturated metabolism. These low dose data sets were used to refine the D4/D5 multi-route harmonized PBPK model to allow for a better description of the disposition and toxicokinetics of D4/D5 following oral exposure. With a refined oral uptake description, the model could be used in risk assessment to better define the internal dose of D4 and D5 following exposure to D4 and D5 via multiple routes.


Assuntos
Poluentes Ambientais/metabolismo , Siloxanas/metabolismo , Tecido Adiposo/química , Administração por Inalação , Glândulas Suprarrenais/química , Animais , Área Sob a Curva , Isótopos de Carbono , Poluentes Ambientais/sangue , Poluentes Ambientais/química , Poluentes Ambientais/farmacocinética , Feminino , Trato Gastrointestinal/química , Fígado/química , Pulmão/química , Masculino , Ovário/química , Ratos , Ratos Endogâmicos F344 , Siloxanas/química , Siloxanas/farmacocinética , Baço/química , Testículo/química , Distribuição Tecidual , Útero/química
13.
J Chromatogr A ; 1503: 21-31, 2017 Jun 23.
Artigo em Inglês | MEDLINE | ID: mdl-28487120

RESUMO

In the present work we propose new variants of chiral stationary phases (CSP) with tert-butylcarbamoylquinine (tBuCQN) as chiral selector molecule. Four tBuCQN-CSPs with distinct bonding chemistries are compared in terms of their pH-dependent surface charge by ζ-potential determinations, by achiral and chiral liquid chromatographic tests and LC-ESI-MS hyphenation. In one embodiment tBuCQN was immobilized on 3-mercaptopropylmethylsilyl-modified silica by thiol-ene click reaction (brush type CSP with selector coverage of 0.38mmol/g). In another embodiment, poly-(3-mercaptopropyl)-methylsiloxane was coated onto vinylized silica particles in presence of tBuCQN and radical initiator. The tBuCQN selector was then immobilized onto the polysiloxane film which in turn was crosslinked to the vinyl-surface in a simultaneous double click reaction leading to a CSP with enhanced stability due to multiple linkages (0.29mmol/g tBuCQN). Aliquots of each of the two CSPs were further modified by oxidation of free residual thiol groups to sulfonic acid functionalities to obtain strongly acidic endcapping groups which act as immobilized counterions of the chiral WAX CSPs (0.2mmol/g sulfonic acid co-ligands for brush type CSP). This caused secondary repulsive interactions, hence balanced interactions of the target analytes (chiral acids) at the WAX site and decreased non-specific interactions. Furthermore, this rendered possible the use of milder elution conditions, i.e. lower ionic strength, for acidic compounds. Separation performance was maintained and slightly improved, respectively, when using polar organic or reversed-phase type elution mode in chiral separations which were significantly accelerated (isoeluotropic conditions could be achieved with ca. factor 40 lower counterion concentration in the mobile phase). Thus, LC-ESI-MS enantiomer separations could be readily performed at very low ionic strength conditions (10mM acetate) which is favorable due to less ion suppression. In addition to this the newly developed stationary phases showed complementary retention profiles in RP- and HILIC-mode which make these type of stationary phases also promising tools for achiral applications in pharmaceutical analysis, especially as orthogonal separation principle e.g. in 2D-LC and impurity profiling.


Assuntos
Cromatografia Líquida/métodos , Espectrometria de Massas , Ânions/química , Íons/química , Concentração Osmolar , Quinina/análogos & derivados , Quinina/química , Dióxido de Silício/química , Siloxanas/química , Estereoisomerismo , Compostos de Sulfidrila/química
14.
Oncotarget ; 8(5): 8143-8153, 2017 Jan 31.
Artigo em Inglês | MEDLINE | ID: mdl-28042958

RESUMO

PURPOSE: To investigate dynamic contrast enhanced-MRI (DCE-MRI) in the preoperative chemo-radiotherapy (CRT) assessment for locally advanced rectal cancer (LARC) compared to18F-fluorodeoxyglucose positron emission tomography/computed tomography (18F-FDG PET/CT). METHODS: 75 consecutive patients with LARC were enrolled in a prospective study. DCE-MRI analysis was performed measuring SIS: linear combination of percentage change (Δ) of maximum signal difference (MSD) and wash-out slope (WOS). 18F-FDG PET/CT analysis was performed using SUV maximum (SUVmax). Tumor regression grade (TRG) were estimated after surgery. Non-parametric tests, receiver operating characteristic were evaluated. RESULTS: 55 patients (TRG1-2) were classified as responders while 20 subjects as non responders. ΔSIS reached sensitivity of 93%, specificity of 80% and accuracy of 89% (cut-off 6%) to differentiate responders by non responders, sensitivity of 93%, specificity of 69% and accuracy of 79% (cut-off 30%) to identify pathological complete response (pCR). Therapy assessment via ΔSUVmax reached sensitivity of 67%, specificity of 75% and accuracy of 70% (cut-off 60%) to differentiate responders by non responders and sensitivity of 80%, specificity of 31% and accuracy of 51% (cut-off 44%) to identify pCR. CONCLUSIONS: CRT response assessment by DCE-MRI analysis shows a higher predictive ability than 18F-FDG PET/CT in LARC patients allowing to better discriminate significant and pCR.


Assuntos
Quimiorradioterapia Adjuvante , Imageamento por Ressonância Magnética , Terapia Neoadjuvante , Tomografia por Emissão de Pósitrons combinada à Tomografia Computadorizada , Neoplasias Retais/diagnóstico por imagem , Neoplasias Retais/terapia , Adulto , Idoso , Área Sob a Curva , Meios de Contraste/administração & dosagem , Procedimentos Cirúrgicos do Sistema Digestório , Feminino , Fluordesoxiglucose F18/administração & dosagem , Humanos , Nanopartículas de Magnetita/administração & dosagem , Masculino , Pessoa de Meia-Idade , Imagem de Perfusão/métodos , Valor Preditivo dos Testes , Curva ROC , Compostos Radiofarmacêuticos/administração & dosagem , Neoplasias Retais/irrigação sanguínea , Neoplasias Retais/patologia , Fluxo Sanguíneo Regional , Indução de Remissão , Reprodutibilidade dos Testes , Siloxanas/administração & dosagem , Resultado do Tratamento
15.
Biomed Res Int ; 2016: 1404567, 2016.
Artigo em Inglês | MEDLINE | ID: mdl-27868060

RESUMO

The present study deals with the enzymatic synthesis of biodiesel by transesterification of Jatropha oil (Jatropha curcas L.) with ethanol in a solvent-free system. Seven commercial lipase preparations immobilized by covalent attachment on epoxy-polysiloxane-polyvinyl alcohol composite (epoxy-SiO2-PVA) were tested as biocatalysts. Among them, immobilized lipases from Pseudomonas fluorescens (lipase AK) and Burkholderia cepacia (lipase PS) were the most active biocatalysts in biodiesel synthesis, reaching ethyl ester yields (FAEE) of 91.1 and 98.3% at 72 h of reaction, respectively. The latter biocatalyst exhibited similar performance compared to Novozym® 435. Purified biodiesel was characterized by different techniques. Transesterification reaction carried out under microwave irradiation exhibited higher yield and productivity than conventional heating. The operational stability of immobilized lipase PS was determined in repeated batch runs under conventional and microwave heating systems, revealing half-life times of 430.4 h and 23.5 h, respectively.


Assuntos
Biocombustíveis , Jatropha/química , Lipase/metabolismo , Óleos de Plantas/química , Biocatálise , Burkholderia cepacia/metabolismo , Compostos de Epóxi/química , Éter/química , Meia-Vida , Calefação , Micro-Ondas , Álcool de Polivinil/química , Pseudomonas fluorescens/metabolismo , Siloxanas/química
16.
Environ Pollut ; 218: 595-604, 2016 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-27476425

RESUMO

The potential of wastewater treatment plants (WWTPs) to act as sources of poly and perfluoroalkyl substances (PFASs), volatile methyl siloxanes (VMSs) and organic UV-filters to the atmosphere was investigated. Target compounds included: PFASs (fluorotelomer alcohols (FTOHs), perfluorooctane sulfonamides/sulfonamidoethanols (FOSAs/FOSEs), perfluroalkyl sulfonic acids (PFSAs) and perfluroalkyl carboxylic acids (PFCAs)), cyclic VMSs (D3 to D6), linear VMSs (L3 to L5) and eight UV-filters. Emissions to air were assessed at eight WWTPs using paired sorbent-impregnated polyurethane foam passive air samplers, deployed during summer 2013 and winter 2014. Samplers were deployed on-site above the active tank and off-site as a reference. Several types of WWTPs were investigated: secondary activated sludge in urban areas (UR-AS), secondary extended aeration in towns (TW-EA) and facultative lagoons in rural areas (RU-LG). The concentrations of target compounds in air were ∼1.7-35 times higher on-site compared to the corresponding off-site location. Highest concentrations in air were observed at UR-AS sites while the lowest were at RU-LG. Higher air concentrations (∼2-9 times) were observed on-site during summer compared to winter, possibly reflecting enhanced volatilization due to higher wastewater temperatures or differences in influent wastewater concentrations. A significant positive correlation was obtained between concentrations in air and WWTP characteristics (influent flow rate and population in the catchment of the WWTP); whereas a weak negative correlation was obtained with hydraulic retention time. Emissions to air were estimated using a simplified dispersion model. Highest emissions to air were seen at the UR-AS locations. Emissions to air (g/year/tank) were highest for VMSs (5000-112,000) followed by UV-filters (16-2000) then ΣPFASs (10-110).


Assuntos
Poluentes Atmosféricos/análise , Fluorocarbonos/análise , Siloxanas/análise , Atmosfera , Monitoramento Ambiental , Poliuretanos , Esgotos/química , Compostos Orgânicos Voláteis/análise , Águas Residuárias/química
17.
J Chromatogr A ; 1460: 160-72, 2016 Aug 19.
Artigo em Inglês | MEDLINE | ID: mdl-27470095

RESUMO

Current gas chromatographic (GC) methods for the analysis of fatty acids (FA) were optimized primarily for the quantification of the trans 18:1 FAs (18:1 tFAs) produced during the partial hydrogenation of fats and oils. Recent regulatory action regarding the application of partial hydrogenation in the processing of edible fats and oils may reshape the FA composition of these products. The higher content in 18:3 tFAs compared to 18:1 tFAs of most refined non-hydrogenated vegetable oils (RNHVO), and the challenge in their quantification applying current methods, suggest the need for new methodologies. This manuscript describes a simple GC method for the analysis of FAs in RNHVOs utilizing a 100m (0.25mm I.D.) capillary column coated with poly(90% biscyanopropyl/10% cyanopropylphenyl siloxane) (90% BCS). The optimization of the chromatographic conditions and the detection of co-eluting compounds were carried out by applying comprehensive two dimensional gas chromatography with online reduction (GC-OR×GC). Results showed that 90% BCS capillary columns operated at the elution temperature of 162°C provide the separation of the 18:1, 18:2 and 18:3 tFAs, contained in RNHVOs, from other components. A minor constituent of Canola oil, 16:3n-3, partially co-eluted with trans-18:1 FAMEs. This simple GC method showed the ability to measure trans-fat in RNHVOs at the level of 0.5g/100g, providing comparable quantitative results to the more complex GC×GC methodology.


Assuntos
Cromatografia Gasosa , Óleos de Plantas/química , Polímeros/química , Siloxanas/química , Ácidos Graxos trans/análise , Ácidos Graxos/química , Hidrogenação , Oxirredução , Temperatura
18.
Talanta ; 156-157: 119-125, 2016 Aug 15.
Artigo em Inglês | MEDLINE | ID: mdl-27260443

RESUMO

Chlorogenic acid (CGA) is a polyphenol derivative that widely exists in higher plants like fruits, vegetables, black teas, and some traditional Chinese medicines. In this work, we have proposed a sensitive and selective electrochemical sensor for detection of CGA. The sensor was based on a glassy carbon electrode (GCE) modified with a functional platform by grafting vinyltrimethoxysilane (VTMS) in multi-walled carbon nanotubes (MWCNTs) and covered by a molecularly imprinted siloxane (MIS) film prepared using the sol-gel process. The VTMS was grafted onto the surface of the MWCNTs via in situ free radical polymerization. The MIS was obtained from the acid-catalyzed hydrolysis/condensation of a solution consisting of tetraethoxysilane (TEOS), phenyltriethoxysilane (PTEOS), (3-aminopropyl)trimethoxysilane (APTMS), and CGA as a template molecule. The modification procedure was evaluated by differential pulse voltammetry (DPV) and scanning electron microscopy (SEM). Under optimized operational conditions, a linear response was obtained covering a concentration ranging from 0.08µmolL(-1) to 500µmolL(-1) with a detection limit (LOD) of 0.032µmolL(-1). The proposed sensor was applied to CGA determination in coffee, tomato, and apple samples with recoveries ranging from 99.3% to 108.6%, showing a promising potential application in food samples. Additionally, the imprinted sensor showed a significantly higher affinity for target CGA than the non-imprinted siloxane (NIS) sensor.


Assuntos
Antioxidantes/análise , Ácido Clorogênico/análise , Técnicas Eletroquímicas/métodos , Análise de Alimentos/métodos , Impressão Molecular/métodos , Nanotubos de Carbono/química , Siloxanas/química , Café/química , Limite de Detecção , Solanum lycopersicum/química , Malus/química , Nanotubos de Carbono/ultraestrutura , Transição de Fase
19.
Environ Sci Pollut Res Int ; 23(13): 13200-9, 2016 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-27023806

RESUMO

The occurrence and fate of four cyclic (D3 to D6) and 10 linear (L5 to L14) siloxanes were investigated in influent and effluent wastewater, sludge from a wastewater treatment plant (WWTP), and surrounding air and soil within the WWTP in Harbin, Northeast China. The mean concentrations of total siloxanes in influent and effluent were 4780 and 997 ng/L and in excess sludge and aerobic sludge were 25.1 and 32.3 µg/g dw, respectively. The concentrations in air and soil within the WWTP were 243 ng/m(3) and 4960 ng/g dw, respectively. A similar composition profile of siloxanes in influent and sludge suggests their same source. Seasonal variation with concentration was comprehensively studied. It was found that temperature and rainfall are the two important factors for the seasonal variation of siloxanes. Adsorption with sewage sludge was the major way for the removal of siloxanes during the municipal wastewater treatment process. Overall, on a daily basis, the mass loading of the Σsiloxanes into the WWTP, out of the WWTP with the effluent and sludge, were estimated to be 3.0, 0.6 and 1.3 kg, respectively. In general, 21 % of siloxanes were discharged into the receiving body (Songhua River), 43 % of siloxanes were absorbed on sludge, and 36 % of siloxanes were lost during the whole process of WWTP.


Assuntos
Siloxanas/análise , Águas Residuárias/química , Poluentes Químicos da Água/análise , Adsorção , Poluentes Atmosféricos/análise , China , Rios , Estações do Ano , Esgotos/análise , Solo/química
20.
J Biomed Mater Res A ; 104(6): 1398-407, 2016 06.
Artigo em Inglês | MEDLINE | ID: mdl-26822463

RESUMO

In first part of this experiment, biocompatibility of the newly developed electroactive polyurethane/siloxane films containing aniline tetramer moieties was demonstrated with proliferation and differentiation of C2C12 myoblasts. Here we further assessed the cytocompatibility of the prepared samples with HL1-cell line, the electrophysiological properties and the patch clamp recording of the seeded cells over the selected electroactive sample. Presence of electroactive aniline tetramer in the structure of polyurethane/siloxane led to the increased expression of cardiac-specific genes of HL-1 cells involved in muscle contraction and electrical coupling. Our results showed that expression of Cx43, TrpT-2, and SERCA genes was significantly increased in conductive sample compared to tissue culture plate and the corresponding non-conductive analogous. The prepared materials were not only biocompatible in terms of cellular toxicity, but did not alter the intrinsic electrical characteristics of HL-1 cells. Embedding the electroactive moiety into the prepared films improved the properties of these polymeric cardiac construct through the enhanced transmission of electrical signals between the cells. Based on morphological observation, calcium imaging and electrophysiological recordings, we demonstrated the potential applicability of these materials for cardiac tissue engineering. © 2016 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 104A: 1398-1407, 2016.


Assuntos
Óleo de Rícino/química , Condutividade Elétrica , Fenômenos Eletrofisiológicos , Coração/fisiologia , Poliuretanos/química , Siloxanas/química , Animais , Linhagem Celular , Forma Celular , Regulação da Expressão Gênica , Potenciais da Membrana , Camundongos , Reação em Cadeia da Polimerase em Tempo Real , Engenharia Tecidual/métodos
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