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1.
J Acoust Soc Am ; 155(2): 1048-1059, 2024 Feb 01.
Artigo em Inglês | MEDLINE | ID: mdl-38341739

RESUMO

A method is presented for estimating and reconstructing the sound field within a room using physics-informed neural networks. By incorporating a limited set of experimental room impulse responses as training data, this approach combines neural network processing capabilities with the underlying physics of sound propagation, as articulated by the wave equation. The network's ability to estimate particle velocity and intensity, in addition to sound pressure, demonstrates its capacity to represent the flow of acoustic energy and completely characterise the sound field with only a few measurements. Additionally, an investigation into the potential of this network as a tool for improving acoustic simulations is conducted. This is due to its proficiency in offering grid-free sound field mappings with minimal inference time. Furthermore, a study is carried out which encompasses comparative analyses against current approaches for sound field reconstruction. Specifically, the proposed approach is evaluated against both data-driven techniques and elementary wave-based regression methods. The results demonstrate that the physics-informed neural network stands out when reconstructing the early part of the room impulse response, while simultaneously allowing for complete sound field characterisation in the time domain.

2.
Sci Total Environ ; 893: 164815, 2023 Oct 01.
Artigo em Inglês | MEDLINE | ID: mdl-37315602

RESUMO

Severe water pollution issues due to legacy and contemporary pesticides exist in tropical regions and are linked to cash crops requiring intensive plant protection practices. This study aims to improve knowledge about contamination routes and patterns in tropical volcanic settings to identify mitigation measures and analyse risk. To this aim, this paper analyses four years of monitoring data from 2016 to 2019 of flow discharge and weekly pesticide concentrations in the rivers of two catchments grown predominantly with banana and sugar cane in the French West Indies. The banned insecticide chlordecone, applied in banana fields from 1972 to 1993, was still the major source of river contamination, while the currently used herbicide glyphosate, its metabolite aminomethylphosphonic acid (AMPA), and postharvest fungicides also exhibited high contamination levels. A value of 0.5 of the Gustafson Ubiquity Score (GUS) was shown to separate contaminant and noncontaminant pesticides, indicating a high vulnerability to pollution by pesticides in this tropical volcanic context. The patterns and routes of river exposure to pesticides differed markedly between the pesticides in accordance with the hydrological behaviour of volcanic islands and the history and nature of pesticide uses. Concerning chlordecone and its metabolites, observations confirmed previous findings of a main subsurface origin of river contamination by this compound but also showed large erratic short-term variations, suggesting the influence of fast surface transport processes such as erosion for legacy pesticides with large sorption capacity. Concerning herbicides and postharvest fungicides, observations have suggested that surface runoff and fast lateral flow in the vadose zone control river contamination. Accordingly, mitigation options need to be considered differently for each type of pesticide. Finally, this study points out the need for developing specific exposure scenarios for tropical agricultural contexts in the European regulation procedures for pesticide risk assessment.

3.
Environ Pollut ; 324: 121283, 2023 May 01.
Artigo em Inglês | MEDLINE | ID: mdl-36804884

RESUMO

Recently, Comte et al. (2022) re-examined the natural degradation of chlordecone (CLD) in the soils of the French West Indies (FWI) by introducing an additional 'dissipation parameter' into the WISORCH model developed by Cabidoche et al. (2009). Recent data sets of CLD concentrations in FWI soils obtained by Comte et al. enabled them optimizing the model parameters, resulting in significantly shorter estimates of pollution persistence than in the original model. Their conclusions jeopardize the paradigm of a very limited degradation of CLD in FWI soils, which may lead to an entire revision of the management of CLD contamination. However, we believe that their study is questionable on several important aspects. This includes potential biases in the data sets and in the modeling approach. It results in an inconsistency between the estimated dissipation half-life time (DT50) of five years that the authors determined for CLD and the fate of CLD in soil from the application period 1972-1993 until nowadays. Most importantly, a rapid dissipation of CLD in the field as proposed by Comte et al. is not sufficiently supported by data and estimates. Hence, the paradigm of long-term persistence of CLD in FWI soils is still to be considered.


Assuntos
Clordecona , Inseticidas , Poluentes do Solo , Clordecona/análise , Clordecona/metabolismo , Inseticidas/análise , Solo , Meia-Vida , Poluentes do Solo/análise , Índias Ocidentais
4.
J Acoust Soc Am ; 146(4): 2404, 2019 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-31671980

RESUMO

The acoustic properties of surfaces are commonly evaluated using samples of finite size, which generate edge diffraction effects that are often disregarded. This study makes use of sound scattering theory to characterize such finite samples. In a given sound field, the samples can be described by a unique complex directivity function called the far-field pattern. Numerical results show that the far-field pattern contains extensive information on the tested samples, including sound absorption and surface scattering, as well as scattering due to finiteness. In this paper, a method is introduced to estimate the far-field pattern of a finite sample. The method relies on measurements of the sound pressure and acoustic particle velocity in the near-field of the sample, and it makes use of the Helmholtz integral equation. The proposed technique is examined in an anechoic room where the sound field near the test sample is scanned with a three-dimensional sound intensity probe. The estimated far-field pattern is compared with numerical predictions up to 1 kHz.

5.
J Acoust Soc Am ; 146(1): 501, 2019 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-31370614

RESUMO

This study examines the estimation of the surface impedance of an absorber with microphone arrays. Two array geometries are compared-a rigid spherical array and a double layer planar array. The impedance is estimated via reconstructing the sound field (pressure and particle velocity) on the absorber's surface, using a plane wave expansion. The comparison is carried out by studying the numerical properties of the two arrays as well as through experimental tests.

6.
J Acoust Soc Am ; 141(6): 4115, 2017 06.
Artigo em Inglês | MEDLINE | ID: mdl-28618790

RESUMO

A method is proposed to estimate the surface impedance of a large absorptive panel from free-field measurements with a spherical microphone array. The method relies on the reconstruction of the pressure and the particle velocity on the studied surface using an equivalent source method based on spherical array measurements. The sound field measured by the array is mainly composed of an incident and a reflected wave, so it can be represented as a spatially sparse problem. This makes it possible to use compressive sensing in order to enhance the resolution and the quality of the estimation. The results indicate an accurate reconstruction for angles of incidence between 0° and 60°, and between approximately 200 and 4000 Hz. Additionally, experimental challenges are discussed, such as the sample's finiteness at low frequencies and the estimation of the background noise.

7.
J Environ Manage ; 171: 204-216, 2016 Apr 15.
Artigo em Inglês | MEDLINE | ID: mdl-26897554

RESUMO

Aided phytostabilisation using trees and fly ashes is a promising technique which has shown its effectiveness in the management of highly metal-contaminated soils. However, this success is generally established based on topsoil physicochemical analysis and short-term experiments. This paper focuses on the long-term effects of the afforestation and two fly ashes (silico-aluminous and sulfo-calcic called FA1 and FA2, respectively) by assessing the integrity of fly ashes 10 years after their incorporation into the soil as well as the vertical distribution of the physicochemical parameters and trace elements (TEs) in the amended soils (F1 and F2) in comparison with a non-amended soil (R). Ten years after the soil treatment, the particle size distribution analysis between fly ashes and their corresponding masses (fly ash + soil particles) showed a loss or an agglomeration of finer particles. This evolution matches with the appearance of gypsum (CaSO4 2H2O) in FA2m instead of anhydrite (CaSO4), which is the major compound of FA2. This finding corresponds well with the dissolution and the lixiviation of Ca, S and P included in FA2 along the F2 soil profile, generating an accumulation of these elements at 30 cm depth. However, no variation of TE contamination was found between 0 and 25 cm depth in F2 soil except for Cd. Conversely, Cd, Pb, Zn and Hg enrichment was observed at 25 cm depth in the F1 soil, whereas no enrichment was observed for As. The fly ashes studied, and notably FA2, were able to reduce Cd, Pb and Zn availability in soil and this capacity persists over the time despite their structural and chemical changes.


Assuntos
Cinza de Carvão/química , Metais Pesados/análise , Poluentes do Solo/análise , Solo/química , Oligoelementos/análise , Árvores/crescimento & desenvolvimento , Biodegradação Ambiental , França , Poluentes do Solo/química , Árvores/metabolismo
8.
Environ Geochem Health ; 37(4): 767-78, 2015 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-25663365

RESUMO

Metal contamination of urban soils and homegrown vegetables has caused major concern. Some studies showed that cadmium (Cd) was among the most significant hazards in kitchen garden soils and prolonged exposure to this metal could cause deleterious health effects in humans. In general, most risk assessment procedures are based on total concentrations of metals in vegetables. The present study assesses human bioaccessibility of Cd in vegetables cultivated in smelter-impacted kitchen garden soils. Seven vegetables (radish, lettuce, French bean, carrot, leek, tomato, and potato) were considered. Using the UBM protocol (unified BARGE bioaccessibility method), the bioaccessibility of Cd was measured in raw/cooked vegetables. A considerable amount of Cd was mobilized from raw vegetables during the digestion process (on average 85% in the gastric phase and 69% in the gastrointestinal phase), which could be attributed to a high uptake of Cd during the growth of the vegetables. Most Cd is accumulated in the vacuoles of plant cells, except what is absorbed by the cell wall, allowing Cd to be released from plant tissues under moderate conditions. Cooking by the steaming process generally increased the bioaccessibility of Cd in French bean, carrot, and leek. For potato, few or no significant differences of Cd bioaccessibility were observed after the steaming process, while the frying process strongly decreased bioaccessibility in both phases. The estimation of metal bioaccessibility in vegetables is helpful for human health risk assessment.


Assuntos
Cádmio/metabolismo , Culinária , Poluentes do Solo/metabolismo , Verduras/química , Disponibilidade Biológica , Digestão , Contaminação de Alimentos/análise , França , Humanos , Metalurgia
9.
Evol Appl ; 7(9): 1094-106, 2014 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-25553070

RESUMO

While nonanadromous males (stream-resident and/or mature male parr) contribute to reproduction in anadromous salmonids, little is known about their impacts on key population genetic parameters. Here, we evaluated the contribution of Atlantic salmon mature male parr to the effective number of breeders (Nb) using both demographic (variance in reproductive success) and genetic (linkage disequilibrium) methods, the number of alleles, and the relatedness among breeders. We used a recently published pedigree reconstruction of a wild anadromous Atlantic salmon population in which 2548 fry born in 2010 were assigned parentage to 144 anadromous female and 101 anadromous females that returned to the river to spawn in 2009 and to 462 mature male parr. Demographic and genetic methods revealed that mature male parr increased population Nb by 1.79 and 1.85 times, respectively. Moreover, mature male parr boosted the number of alleles found among progenies. Finally, mature male parr were in average less related to anadromous females than were anadromous males, likely because of asynchronous sexual maturation between mature male parr and anadromous fish of a given cohort. By increasing Nb and allelic richness, and by decreasing inbreeding, the reproductive contribution of mature male parr has important evolutionary and conservation implications for declining Atlantic salmon populations.

10.
Mol Ecol ; 22(1): 187-200, 2013 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-23163395

RESUMO

In this study, we documented the breeding system of a wild population of Atlantic salmon (Salmo salar L.) by genetically sampling every returning adult and assessed the determinants of individual fitness. We then quantified the impacts of catch and release (C&R) on mating and reproductive success. Both sexes showed high variance in individual reproductive success, and the estimated standardized variance was higher for males (2.86) than for females (0.73). We found a weak positive relationship between body size and fitness and observed that fitness was positively correlated with the number of mates, especially in males. Mature male parr sired 44% of the analysed offspring. The impact of C&R on the number of offspring was size dependent, as the reproductive success of larger fish was more impaired than smaller ones. Also, there was an interactive negative effect of water temperature and air exposure time on reproductive success of C&R salmon. This study improves our understanding of the complex reproductive biology of the Atlantic salmon and is the first to investigate the impact of C&R on reproductive success. Our study expands the management toolbox of appropriate C&R practices that promote conservation of salmon populations and limit negative impacts on mating and reproductive success.


Assuntos
Aptidão Genética , Reprodução/genética , Salmo salar/genética , Animais , Tamanho Corporal , Feminino , Atividades Humanas , Humanos , Masculino , Repetições de Microssatélites , Quebeque , Comportamento Sexual Animal , Estresse Fisiológico
11.
Environ Monit Assess ; 185(4): 2999-3012, 2013 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-22791114

RESUMO

Metal contamination of urban soils and homegrown products has caused major concern. In Part 1, we investigated the long-term effects of a former smelter on the degree of kitchen garden-soil contamination and the quality of the homegrown vegetables from these gardens. The results showed that the soils retained a high level of contamination and that a large proportion of the vegetables produced did not comply with the legislation on the levels of metals allowed for human consumption. The present study aims to assess the associated potential health risk to local inhabitants through consumption of homegrown vegetables and ingestion of soil particles using a land use-based approach. For lead (Pb), the standard hazard quotient (HQ)-based risk assessment method was used to determine the HQ. For cadmium (Cd), the approach consisted of calculating the HQs and then deriving site-specific assessment criteria (SSAC) using the SNIFFER method. The results suggested that the exposure pathways considered should not engender any form of deleterious health effects for adults. For children, Pb was the main concern and induced a relatively high health risk through soil particle ingestion, and most total soil Cd concentrations exceeded the derived SSAC, in particular, through consumption of vegetables. The metal bioaccessibility in soils was incorporated into the methods to establish more realistic risk assessment measures. This study proposes an approach to integrate different human health risk assessment methods. Further investigations should complete the assessment to improve risk determination, e.g., the determination of metal bioaccessibility in vegetables.


Assuntos
Cádmio/análise , Exposição Ambiental/análise , Jardinagem , Chumbo/análise , Metalurgia , Poluentes do Solo/análise , Adulto , Criança , Cidades , Dieta/estatística & dados numéricos , Exposição Ambiental/estatística & dados numéricos , Monitoramento Ambiental , Poluição Ambiental/estatística & dados numéricos , Humanos , Medição de Risco , Verduras/química
12.
Environ Monit Assess ; 185(5): 3665-80, 2013 May.
Artigo em Inglês | MEDLINE | ID: mdl-22886627

RESUMO

Soil contamination by metals engenders important environmental and health problems in northern France where a smelter (Metaleurop Nord) was in activity for more than a century. This study aims to look at the long-term effects of the smelter after its closedown by combining data on the degree of soil contamination and the quality of the crops grown (agricultural crops and homegrown vegetables) in these soils for a better assessment of the local population's exposure to Cd, Pb, and Zn. Seven years after the Metaleurop Nord closedown, (1) the agricultural and urban topsoils were strongly contaminated by Cd, Pb, and Zn; (2) the kitchen garden topsoils were even more polluted than the agricultural soils, with great variability in metal concentrations within the gardens studied; (3) a high proportion of the agricultural crops for foodstuffs did not conform with the European legislation; (4) for feedstuffs, most samples did not exceed the Cd and Pb legislation limits, indicating that feedstuffs may be an opportunity for most agricultural produce; and (5) a high proportion of the vegetables produced in the kitchen gardens did not conform with the European foodstuff legislation. The high contamination level of the soils studied continues to be a risk for the environment and the population's health. A further investigation (part 2) assesses the associated potential health risk for local inhabitants through consumption of homegrown vegetables and ingestion of soil particles by estimating the site-specific human health assessment criteria for Cd and Pb.


Assuntos
Produtos Agrícolas/química , Metais/análise , Poluentes do Solo/análise , Solo/química , Verduras/química , Exposição Ambiental/estatística & dados numéricos , Monitoramento Ambiental , Poluição Ambiental/estatística & dados numéricos , França , Humanos , Metalurgia , Medição de Risco
13.
Environ Pollut ; 160(1): 130-8, 2012 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-22035936

RESUMO

An investigation was undertaken to identify the most significant soil parameters that can be used to predict Cd, Pb, and Zn bioaccessibility in smelter-contaminated agricultural soils. A robust model was established from an extended database of soils by using: (i) a training set of 280 samples to select the main soil parameters, to define the best population to be taken into account for the model elaboration, and to construct multivariate regression models, and (ii) a test set of 110 samples to validate the ability of the regression models. Total carbonate, organic matter, sand, P(2)O(5), free Fe-Mn oxide, and pseudototal Al and trace element (TE) contents appeared as the main variables governing TE bioaccessibility. The statistical modeling approach was reasonably successful, indicating that the main soil factors influencing the bioaccessibility of TEs were taken into account and the predictions could be applicable for further risk evaluation in the studied area.


Assuntos
Monitoramento Ambiental , Metabolismo , Modelos Estatísticos , Poluentes do Solo/metabolismo , Solo/química , Oligoelementos/metabolismo , Agricultura , Humanos , Metalurgia , Modelos Biológicos , Poluentes do Solo/análise , Oligoelementos/análise
14.
Bioconjug Chem ; 19(7): 1491-5, 2008 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-18570391

RESUMO

In order to graft an amphiphilic polysaccharide to lipid nanocapsules, we present here a new method of dextran lipidation. The lipidation strategy is based on the formation of an oxime linkage between the amphiphilic hydroxylamine C16E20ONH2 and the reductive end of a 40 kDa dextran. This chemoselective reaction allows us to control the lipidation site and the number of lipid introduced on the dextran molecule. This new amphiphilic dextran was used to coat the surface of lipid nanocapsules. The coating efficiency was followed by dynamic light scattering and the presence of the polysaccharide was confirmed by (1)H NMR and observed by electronic microscopy.


Assuntos
Dextranos/química , Portadores de Fármacos/síntese química , Lipídeos/química , Nanocápsulas/química , Portadores de Fármacos/química , Hidroxilamina/química , Oxirredução
15.
Muscle Nerve ; 37(5): 601-10, 2008 May.
Artigo em Inglês | MEDLINE | ID: mdl-18335470

RESUMO

Exercise intolerance and undue fatigue are common complaints in patients with Charcot-Marie-Tooth (CMT) disease. Reduced physical ability is due directly to the disease, but it is also due to physical deconditioning. The aim of this study was to test whether 24 weeks of interval-training exercise (ITE) cycling can significantly improve physiological, neuromuscular, and functional capacities and alleviate fatigue in CMT patients. Eight CMT patients (4 CMT1A and 4 CMT2) participated in ITE for 3 nonconsecutive days per week. Cardiovascular fitness, muscle strength, fatigue resistance, and functional capacities were measured before and after 12 weeks of supervised hospital training and again after another 12 weeks of unsupervised home training. Training was well tolerated. There were significant improvements in cardiorespiratory capacities, isokinetic concentric strength, and functional ability measurements. All patients experienced an improvement in their self-reported visual analogic scale for fatigue and pain during training. However, there was no significant change in their isometric force production and indices of fatigue resistance after training. Although the improvement in exercise tolerance may be due in part to reversal of the deconditioning effect of their related sedentary lifestyle, this clinical trial suggests that ITE can benefit CMT patients especially in their functional performance and subjective perception of pain and fatigue. Moreover, the improvement observed at the end of the first supervised period ITE was maintained after the second unsupervised home period, although there was no further improvement in performance and tolerance.


Assuntos
Doença de Charcot-Marie-Tooth/complicações , Terapia por Exercício , Tolerância ao Exercício/fisiologia , Fadiga/etiologia , Fadiga/reabilitação , Atividades Cotidianas , Adulto , Análise de Variância , Doença de Charcot-Marie-Tooth/reabilitação , Creatina Quinase/sangue , Eletromiografia , Feminino , Humanos , Masculino , Contração Muscular/fisiologia , Força Muscular/fisiologia , Consumo de Oxigênio , Aptidão Física/fisiologia , Fatores de Tempo
16.
Eur J Med Chem ; 42(1): 114-24, 2007 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-17011671

RESUMO

As part of a drug delivery project, four aldehydes of the type Pam-Lys(Pam)-spacer-CO-CHO were synthesized to be included in targeting colloids. Though amphiphilic, they were obtained within reasonable yields (18-55%) and with high RP-HPLC purity ( approximately 90%). Parallely, six complementary targeting peptides of the type H(2)N-NH-CH(2)-CO-spacer-YGRGDSP-NH(2) were prepared to be anchored onto colloids. Isolated yields are related to the spacer length and nature. To easily and rapidly modulate the distance between the peptide and the vesicle, every partners were elaborated on solid phase and the expected constructions were obtained by hydrazone ligation. One possible application is presented here with multilamellar vesicles targeting HUVEC cells. Preliminary results prove that the fine-tuning of the spacer length permits to optimize the recognition toward the target cells.


Assuntos
Aldeídos/química , Hidrazonas/química , Oligopeptídeos/química , Aldeídos/síntese química , Células Cultivadas , Coloides , Portadores de Fármacos , Sistemas de Liberação de Medicamentos , Células Endoteliais/metabolismo , Endotélio Vascular/citologia , Humanos , Hidrazonas/síntese química , Integrinas/metabolismo , Ligantes , Oligopeptídeos/síntese química , Oligopeptídeos/metabolismo , Relação Estrutura-Atividade , Veias Umbilicais/citologia
17.
Int J Pharm ; 312(1-2): 144-50, 2006 Apr 07.
Artigo em Inglês | MEDLINE | ID: mdl-16480839

RESUMO

Spherulites are new promising multilamellar vesicles that we study in a drug delivery context. The sterilization of spherulites suspensions is a necessary step before biological tests and later, before pharmaceutical applications (for example, parenteral or local injections). Among all sterilizing operations, the filtration through 0.22 microm sterilizing-grade filters (of the type Millex (Ø 4 mm) by Millipore) is easy and rapid, and we decided to study it as a mean to obtain sterile suspensions. The spherulites diameter is usually comprised between 0.2 and 0.5 microm but bigger vesicles occur and reach Ø 1 microm. The effects of such filters on vesicles' size and lipids' concentration were then compromised. After examination of this challenging operation, results proved that the sterilizing filtration had no effect on these two parameters whatever the formulation chosen. Then, the possible release of amaranth, an encapsulated hydrophilic dye was followed. With the formulations and in spite of a filter diameter inferior to that of the vesicles, the encapsulation yields were not significantly different before and after the filtration and no leakage could be detected. Finally, the spherulites' functionality after sterilizing filtration was studied under the chemical angle: vesicles containing an amphiphilic reactive anchor (CholE3ONH2) were still able to bind covalently a peptidic molecular recognition pattern. The ligation was quantified by fluorimetry as high as for non-filtrated suspensions. Thus, though spherulites can present a diameter superior to that of the sterilizing filters, their passage through them do not alter the physico-chemical properties of these vesicles.


Assuntos
Portadores de Fármacos/química , Filtração/métodos , Esterilização/métodos , Corante Amaranto/química , Bactérias/isolamento & purificação , Contagem de Colônia Microbiana , Corantes , Contaminação de Medicamentos , Bicamadas Lipídicas/química , Oligopeptídeos/química , Tamanho da Partícula , Fosfatidilcolinas/química , Suspensões , Temperatura
18.
Chemistry ; 11(24): 7315-21, 2005 Dec 09.
Artigo em Inglês | MEDLINE | ID: mdl-16161172

RESUMO

As part of a drug-delivery project, we designed and synthesised a novel hydroxylamine cholesterol-based anchor to ensure the chemoselective ligation of recognition patterns onto multilamellar vesicles by oxime ligation. The entry of a glyoxylyl peptide into the vesicles was unexpectedly assisted by the formation of the alpha-oxo oxime bond. We studied extensively the kinetic and thermodynamic aspects of this phenomenon. Briefly, for a glyoxylyl peptide, the speed and ability to enter the vesicle were dependent upon 1) the presence of a hydroxylamine anchor of the type CholE3ONH2, 2) the amount of peptide engaged in the ligation and 3) the flip-flop motion permitted by the different formulations, in which the presence of cholesterol seems to play an important role.


Assuntos
Oximas/química , Peptídeos/química , Cromatografia Líquida de Alta Pressão , Cinética , Ressonância Magnética Nuclear Biomolecular , Espectrometria de Fluorescência , Espectrometria de Massas de Bombardeamento Rápido de Átomos , Espectrometria de Massas por Ionização e Dessorção a Laser Assistida por Matriz
19.
Proc Natl Acad Sci U S A ; 101(43): 15279-84, 2004 Oct 26.
Artigo em Inglês | MEDLINE | ID: mdl-15492229

RESUMO

The incorporation of lipophilic ligands into the bilayer membrane of vesicles offers the possibility to induce, upon binding of suitable metal ions, a variety of processes, in particular vesicle aggregation and fusion and generation of vesicle arrays, under the control of specific metal-ligand recognition events. Synthetic bipyridine lipoligands Bn bearing a bipyridine unit as head group were prepared and incorporated into large unilamellar vesicles. The addition of Ni2+ or Co2+ metal ions led to the formation of complexes MBn and MBn2 followed by spontaneous fusion to generate giant multilamellar vesicles. The metal ion complexation was followed by UV spectroscopy and the progressive fusion could be visualized by optical dark-field and fluorescence microscopies. Vesicle fusion occurred without leakage of the aqueous compartments and resulted in the formation of multilamellar giant vesicles because of the stacking of the lipoligands Bn. The fusion process required a long enough oligoethylene glycol spacer and a minimal concentration of lipoligand within the vesicle membrane. Metallosupramolecular systems such as the present one offer an attractive way to induce selective intervesicular processes, such as vesicle fusion, under the control of molecular recognition between specific metal ions and lipoligands incorporated in the bilayer membrane. They provide an approach to the design of artificial "tissue-mimetics" through the generation of polyvesicular arrays of defined architecture and to the control of their functional properties.


Assuntos
Metais/metabolismo , Varredura Diferencial de Calorimetria , Cátions , Ligantes , Luz , Bicamadas Lipídicas , Espectroscopia de Ressonância Magnética , Microscopia de Fluorescência , Espalhamento de Radiação , Espectrofotometria Ultravioleta
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