WO2011071406A1 - Method and micro device for the extraction of traces of chemical substances with different polarities - Google Patents

Method and micro device for the extraction of traces of chemical substances with different polarities Download PDF

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Publication number
WO2011071406A1
WO2011071406A1 PCT/PT2010/000066 PT2010000066W WO2011071406A1 WO 2011071406 A1 WO2011071406 A1 WO 2011071406A1 PT 2010000066 W PT2010000066 W PT 2010000066W WO 2011071406 A1 WO2011071406 A1 WO 2011071406A1
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micro
extraction
adsorbent material
traces
different polarities
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PCT/PT2010/000066
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French (fr)
Portuguese (pt)
Inventor
José Manuel FLORÊNCIO NOGUEIRA
Ana Rita MENDÃO SILVA
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Universidade De Lisboa
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Publication of WO2011071406A1 publication Critical patent/WO2011071406A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3244—Non-macromolecular compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28016—Particle form
    • B01J20/28019—Spherical, ellipsoidal or cylindrical
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3206—Organic carriers, supports or substrates
    • B01J20/3208—Polymeric carriers, supports or substrates
    • B01J20/321—Polymeric carriers, supports or substrates consisting of a polymer obtained by reactions involving only carbon to carbon unsaturated bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3234—Inorganic material layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3291—Characterised by the shape of the carrier, the coating or the obtained coated product
    • B01J20/3293—Coatings on a core, the core being particle or fiber shaped, e.g. encapsulated particles, coated fibers
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • G01N1/40—Concentrating samples
    • G01N1/405—Concentrating samples by adsorption or absorption

Definitions

  • the invention is in the field of trace analysis (trace and ultra trace) of compounds with different polarities, focusing on compounds with. polar characteristics, as an alternative to other conventional or widely established extractive techniques for analytical enrichment.
  • the new extractive process will consist of suspending a new micro-device in the matrix to be analyzed with the medium under conventional agitation until: The equilibrium state is established.
  • the micro-device containing suitable adsorbents may be applied to actual matrices, particularly to aqueous samples of environmental or biological origin, among others, in order to extract chemical compounds of interest for further analysis using chromatographic, hyphenated and capillary electrophoresis techniques.
  • the SBSE in particular consists of a stir bar consisting of a magnet inserted into a closed inert glass tube and externally coated with a polydimethylsiloxane (PDMS) based polymeric film. be between 1 and 2 cm in length and the polymer volume up to 124 ⁇ L.
  • PDMS polydimethylsiloxane
  • the stir bar is placed on the sample under agitation and under optimized experimental conditions in order to promote the rotational motion in the liquid matrix and at the same time the extraction of substances with more supporting characteristics, ie , volatile and semi-volatile substances. Thereafter, the stir bar is placed in an on-line thermal desorption unit coupled to a gas chromatograph injector, the desorbed substances under appropriate heating conditions and further analyzed.
  • Desorption may also be promoted by off-line liquid extraction, with this option having unequivocal advantages over the possibility of using gas chromatography, liquid and even capillary electrophoresis for subsequent analysis of micro-extracted substances.
  • this analytical approach shows great limitations in the micro-extraction of polar solutes, since there are no commercially suitable polymeric phases for recovering compounds of these characteristics by SBSE.
  • An object of the invention is a novel method of sample preparation for trace extraction of organic solutes using a novel micro-device coated externally with adsorbent materials. Also object of the invention is that new micro-device. Still object of the invention is a method for obtaining the new micro-device.
  • the method provides for contacting the micro-device with stirring fluids containing analytes for a period of time, and the substances are subjected to adsorptive extraction with retention of at least one solute to the micro-device followed by liquid desorption with suitable organic solvents or solvent mixtures under ultrasonic conditions, thus allowing the substances to be back extracted for further analysis using instrumental analysis techniques, namely analytical separation techniques.
  • the new micro-device consists of a spherically shaped base externally coated with adsorbent materials, illustrative and non-limiting examples of activated carbon, zeolite, alumina, silica, calixeene. Contrary to the foregoing inventions, the proposed micro-device has no magnet in its constitution, and the agitation to achieve equilibrium is performed by means of a conventional Teflon magnetic bar.
  • the invention comprises a method for trace trace extraction of substances of different polarities, focusing mainly on those having more polar characteristics, which includes at least the following steps: a) placing a micro-device and a conventional magnetic stir bar in a sample consisting of a fluid with a density greater than that of the micro-device and less than that of the magnetic stir bar;
  • the method is further characterized in that the fluid or sample is generally comprised of aqueous solutions, hydroalcoholic mixtures among others.
  • the method is further characterized in that the sample is stirred until the equilibrium is reached within a period of not less than 30 minutes.
  • the method is further characterized in that the extractants are of various origin, namely pesticides and their metabolites, drugs, hygiene and personal care pharmaceuticals, natural metabolites, natural products, among others.
  • the method is further characterized in that the magnetic stirring bar may be conventionally coated with "teflon".
  • the method is further characterized in that the solvent is selected from a group including: pH controlled aqueous solutions, alcohols, acetonitrile, organic acids and other types of organic solvents.
  • the invention further comprises a micro-device for trace extraction of substances of different polarities, comprising a spherical support which may have different diameters and be coated with adsorbent materials.
  • the micro-device will have a variable number of beads, coated with the adsorbent material, which are joined by a wire,
  • the micro-device is further characterized in that the support and the yarn may be, in a non-limiting example, polystyrene and cotton based respectively.
  • the micro-device is further characterized in that the adsorbent material is selected from a group including activated charcoals, zeolites, aluminas, silicas, calixeenes, finely divided inorganic solids, among other type of laboratory prepared adsorbents.
  • the adsorbent material is selected from a group including activated charcoals, zeolites, aluminas, silicas, calixeenes, finely divided inorganic solids, among other type of laboratory prepared adsorbents.
  • the invention further comprises a method for obtaining a trace device for extracting trace substances. with different polarities characterized by including the following steps:
  • the micro-device consists of a support made up of several 2 mm medium diameter polystyrene spheres (1) joined by a thread which may, for example, be cotton.
  • the yarn and beads are placed into a vial already containing some finely divided adsorbent material and the vial is subsequently filled with the adsorbent material so that all the beads are covered by the adsorbent material (2).
  • the flask containing the polystyrene bead yarn coated with the solid material is placed in an oven at a given temperature and at a given time depending on the type of adsorbent material used. Usually a temperature of 160 ° C is used for 2 h.
  • the adhering material adheres to the surface of the polystyrene beads and is fixed by. thermal action. Subsequently, the thread (3) containing the polystyrene spheres already covered by the adsorbent material is removed from the flask and the number of spheres required for further analysis is joined, usually between 5 and 10 spheres. Cut the thread and collect various micro-devices. In the end, the micro-device supported with the solid material is treated to remove excess adsorbent and cleaned with . a suitable solvent. . The prepared micro-device is then able to be placed in a flask (4) containing a liquid sample (5) under stirring by means of a magnetic bar (6), suspended in the area below the formation of the liquid vortex (7).
  • the micro-device (8) has appropriate density for this purpose relative to the fluid or sample, extracting substances with different polarities after establishing the equilibrium state. Contrary to the previous inventions, the proposed micro-device does not have any magnetic material in its constitution, and the agitation to reach equilibrium is performed by means of a conventional Teflon magnetic bar or other material suitable for this function.
  • Figure 3 exemplifies some results obtained, where it is possible to observe the chromatograms resulting from this methodology in the analysis of different types of compounds in different types of real aqueous matrices, followed by HPLC analysis.
  • substances studied in aqueous media were antibiotics (sulfathiazole-9, sulfamethoxazole ⁇ 10, sulfadimethoxine-11, trimethoprim-12 and enrofloxacin-13).
  • Analytical micro-devices containing suitable adsorbents can be easily applied to real samples in various scientific areas, namely aqueous matrices with environmental origin, among others, in order to extract compounds with different polarities of interest, for further analysis using chromatographic techniques. , hyphenated well with capillary electrophoresis.

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  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
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  • Sampling And Sample Adjustment (AREA)

Abstract

The present invention relates to a method and a device for analytical extraction, wherein the micro device is externally covered with finely divided adsorbent materials (for example, activated charcoal, inorganic solids, etc.). The present invention is essentially directed to the analysis of traces (traces and ultra-traces) of compounds with different polarities, focusing on compounds with more polar characteristics, and represents an alternative to other conventional or widely established extraction techniques for enrichment purposes. The micro devices containing suitable adsorbents are applied to real matrices, particularly to aqueous samples of environmental or biological origin, inter alia, in order to extract chemical compounds of interest for subsequent analysis. The extractive process consists of the suspension of the micro device in the matrix to be analysed while the medium remains under conventional stirring until the equilibrium state is established. The present invention is applied for environmental or biological analysis.

Description

DESCRIÇÃO  DESCRIPTION
"MÉTODO E MICRO-DISPOSITIVO PARA A EXTRACÇÃO VESTIGIAL DE SUBSTÂNCIAS QUÍMICAS COM DIFERENTES POLARIDADES" "METHOD AND MICRO-DEVICE FOR VESTIGIAL EXTRACTION OF CHEMICAL SUBSTANCES WITH DIFFERENT POLARITIES"
Âmbito da invenção Scope of the invention
A invenção insere-se no campo da análise vestigial (traços e ultra-traços) de compostos com diferentes polaridades, incidindo nos compostos com. características mais polares, apresentando-se como alternativa a outras técnicas extractivas convencionais ou largamente estabelecidas para enriquecimento analítico. 0 novo processo extractivo consistirá na suspensão de um novo micro-dispositivo na matriz a analisar ficando o meio sob agitação convencional até: se estabelecer O estado de equilíbrio.. O micro- dispositivo contendo adsorventes adequados, poderá ser aplicado a matrizes reais, particularmente a amostras aquosas com origem ambiental ou biológica entre outras, no sentido de extrair compostos químicos com interesse para análise posterior com recurso a técnicas cromatográficas, hifenadas e electroforese capilar.  The invention is in the field of trace analysis (trace and ultra trace) of compounds with different polarities, focusing on compounds with. polar characteristics, as an alternative to other conventional or widely established extractive techniques for analytical enrichment. The new extractive process will consist of suspending a new micro-device in the matrix to be analyzed with the medium under conventional agitation until: The equilibrium state is established. The micro-device containing suitable adsorbents may be applied to actual matrices, particularly to aqueous samples of environmental or biological origin, among others, in order to extract chemical compounds of interest for further analysis using chromatographic, hyphenated and capillary electrophoresis techniques.
Antecedentes da invenção Background of the invention
É amplamente conhecido, particularmente na técnica de cromatografia gasosa, o uso de dispositivos para microextracção, que por "espaço de cabeça" ("headspace") quer directamente na matriz e subsequente análise com recurso a dessorção térmica em unidades apropriadas e acopladas aos respectivos injectores destes sistemas cromatográficos . Esta abordagem é principalmente usada pára a análise vestigial de compostos com características de volatilidade elevada e que não sejam simultaneamente termolábeis . Dentro deste domínio analítico, foram introduzidas recentemente as técnicas de extracção sortiva designadas por "microextracção em fase sólida" (SPME: "Solid Phase Microextraction") e "extracção sortiva em barra de agitação" (SBSE: "Stir Bar Sorptive Extraction") , embora a última tenha demonstrado maior capacidade analítica para extracção de analitos ao nível vestigial. Confrontar os registos US2005/0288183 Al e US6,815,216 B2. A SBSE em particular, consiste numa barra de agitação, constituída por um magnete inserido dentro de um tubo de vidro inerte e fechado sendo revestido externamente por um filme de uma fase polimérica à base de polidimetilsiloxano (PDMS: "polydimethylsiloxane" ) , podendo este dispositivo ter entre 1 a 2 cm em comprimento e o volume do polímero ir até 124 μL. Do ponto de vista da manipulação analítica, a barra de agitação é colocada na amostra em estudo sob agitação e em condições experimentais optimizadas, de forma a promover o movimento de rotação na matriz líquida e simultaneamente a extracção das substâncias com características mais apoiares, ou seja, substâncias voláteis e semi-voiáteis . Posteriormente, a barra de agitação é colocada numa unidade de dessorção térmica acoplada ("on-line") ao injôctor de um cromatografo gasoso, sendo as substâncias dessorvidas em condições de aquecimento adequadas, e posteriormente analisadas. A dessorção pode igualmente ser promovida por retro-extracção líquida ("off-line") , apresentando esta opçãò: vantagens inequívocas relativamente à possibilidade de recurso a cromatografia gasosa, líquida e até electroforese capilar para análise subsequente das substâncias micro-extraidas . Apesar das potencialidades desta abordagem analítica, a mesma evidencia grandes limitações na micro-extracção de solutos polares, uma vez que ainda não existem comercialmente fases poliméricas adequadas para recuperar compostos com estas características por SBSE. It is widely known, particularly in the art of gas chromatography, the use of micro-extraction devices which by headspace either directly in the matrix and subsequent analysis using thermal desorption in appropriate units coupled to the respective injectors. of these chromatographic systems. This approach is mainly used for trace analysis of compounds with high volatility characteristics that are not simultaneously thermolabile. Within this analytical domain, the techniques for sorting "Solid Phase Microextraction" (SPME) and "Stir Bar Sorptive Extraction" (SBSE) have recently been introduced. although the latter showed greater analytical capacity for trace extraction of analytes. Compare US2005 / 0288183 A1 and US6,815,216 B2. The SBSE in particular consists of a stir bar consisting of a magnet inserted into a closed inert glass tube and externally coated with a polydimethylsiloxane (PDMS) based polymeric film. be between 1 and 2 cm in length and the polymer volume up to 124 μL. From the point of view of analytical manipulation, the stir bar is placed on the sample under agitation and under optimized experimental conditions in order to promote the rotational motion in the liquid matrix and at the same time the extraction of substances with more supporting characteristics, ie , volatile and semi-volatile substances. Thereafter, the stir bar is placed in an on-line thermal desorption unit coupled to a gas chromatograph injector, the desorbed substances under appropriate heating conditions and further analyzed. Desorption may also be promoted by off-line liquid extraction, with this option having unequivocal advantages over the possibility of using gas chromatography, liquid and even capillary electrophoresis for subsequent analysis of micro-extracted substances. Despite the potentialities of this analytical approach, it shows great limitations in the micro-extraction of polar solutes, since there are no commercially suitable polymeric phases for recovering compounds of these characteristics by SBSE.
Sumário da invenção Summary of the invention
Um objecto da invenção é um novo método de preparação de amostras para extracção vestigial de solutos orgânicos utilizando um novo micro-dispositívo revestido externamente com materiais adsorventes. Igualmente objecto da invenção é aquele novo micro-dispositivo . Ainda objecto da invenção é um método para obtenção do novo micro-dispositivo.  An object of the invention is a novel method of sample preparation for trace extraction of organic solutes using a novel micro-device coated externally with adsorbent materials. Also object of the invention is that new micro-device. Still object of the invention is a method for obtaining the new micro-device.
O método prevê a entrada em contacto do micro-dispositivo com fluídos sob agitação que contêm substâncias a analisar, durante um determinado tempo, sendo as substâncias sujeitas a extracção adsortiva promovendo-se a retenção de pelo menos um soluto ao micro-dispositivo, seguida de dessorçâo líquida com solventes orgânicos adequados ou misturas de solventes em condições ultra-s.ónicas, permitindo assim que as substâncias sejam retro-extraídas para serem posteriormente analisadas com recurso a técnicas instrumentais de análise, nomeadamente, técnicas de separação analítica. The method provides for contacting the micro-device with stirring fluids containing analytes for a period of time, and the substances are subjected to adsorptive extraction with retention of at least one solute to the micro-device followed by liquid desorption with suitable organic solvents or solvent mixtures under ultrasonic conditions, thus allowing the substances to be back extracted for further analysis using instrumental analysis techniques, namely analytical separation techniques.
O novo micro-dispositivo é constituído por uma base com formato esférico revestido externamente com materiais adsorventes, de que são exemplos ilustrativos e não limitativos carvões activados, zeólitos, aluminas, sílicas, calixarenos. Ao contrário das invenções antecedentes, o micro-dispositivo proposto não apresenta na sua constituição nenhum magneto, sendo a agitação para se atingir o equilíbrio efectuada através de uma barra magnética em "teflon" convencional. Breve descrição das figuras The new micro-device consists of a spherically shaped base externally coated with adsorbent materials, illustrative and non-limiting examples of activated carbon, zeolite, alumina, silica, calixeene. Contrary to the foregoing inventions, the proposed micro-device has no magnet in its constitution, and the agitation to achieve equilibrium is performed by means of a conventional Teflon magnetic bar. Brief Description of the Figures
A descrição que se segue tem por base as figuras em anexo, sem qualquer carácter limitativo e que representam: The following description is based on the attached figures, without limitation and representing:
Figura 1 - Esboço lateral do micro-dispositivo . Figure 1 - Side sketch of the micro device.
Figura 2 - Exemplificação do processo extractivo numa amostra liquida.  Figure 2 - Example of the extractive process in a liquid sample.
Figura 3 - Resultados de aplicação do método.  Figure 3 - Results of method application.
Descrição detalhada da invenção Detailed Description of the Invention
A invenção compreende um método para micro-extracção vestigial de substâncias com diferentes polaridades, incidindo principalmente nos que apresentam características mais polares, que inclui pelo menos as seguintes etapas: a) colocação de um micro-dispositivo e de uma barra magnética de agitação convencional numa amostra constituída por um fluído com densidade superior à do micro-dispositivo e inferior à da barra magnética de agitação;  The invention comprises a method for trace trace extraction of substances of different polarities, focusing mainly on those having more polar characteristics, which includes at least the following steps: a) placing a micro-device and a conventional magnetic stir bar in a sample consisting of a fluid with a density greater than that of the micro-device and less than that of the magnetic stir bar;
b) agitação da amostra durante um período de tempo adequado através da barra magnética de agitação convencional; b) shaking the sample for a suitable period of time through the conventional stirring magnetic bar;
c) extracção das substâncias com diferentes polaridades para os materiais adsorventes constituintes do micro- dispositivo após se estabelecer o estado de equilíbrio; d) após extracção, colocação do micro-dispositivo em volume de solvente ou mistura de solventes, sob condições optimizadas (ex. pH) adequadas à retroextracção ou dessorção líquida dos solutos inicialmente extraídos da amostra, em particular os analitós com características polares . c) extraction of substances with different polarities to the adsorbent materials constituting the micro-device after establishing the equilibrium state; (d) after extraction, placing the microplate in solvent volume or solvent mixture under optimal conditions (eg pH) suitable for back-extraction or liquid desorption of solutes initially extracted from the sample, in particular polar analytes.
0 método é caracterizado adicionalmente pór o fluído ou amostra ser genericamente constituído por soluções aquosas, misturas hidroalcoólicas entre outras. 0 método é caracterizado adicionalmente por a agitação da amostra se realizar até se alcançar o estado de equilíbrio num período nunca inferior a 30 minutos. The method is further characterized in that the fluid or sample is generally comprised of aqueous solutions, hydroalcoholic mixtures among others. The method is further characterized in that the sample is stirred until the equilibrium is reached within a period of not less than 30 minutes.
0 método é ainda caracterizado adicionalmente por as substâncias â extrair terem diversa origem, nomeadamente, pesticidas e respectivos metabolitos, drogas, produtos farmacêuticos de higiene e cuidado pessoal, metabolitos naturais, produtos naturais, entre outros. The method is further characterized in that the extractants are of various origin, namely pesticides and their metabolites, drugs, hygiene and personal care pharmaceuticals, natural metabolites, natural products, among others.
0 método é caracterizado adicionalmente por a barra magnética de agitação poder ser convencional revestida com "teflon".  The method is further characterized in that the magnetic stirring bar may be conventionally coated with "teflon".
0 método é caracterizado adicionalmente por o solvente ser seleccionado de um grupo incluindo: soluções aquosas a pH controlado, álcoois, acetonitrilo, ácidos orgânicos e outros tipos, de solventes orgânicos.  The method is further characterized in that the solvent is selected from a group including: pH controlled aqueous solutions, alcohols, acetonitrile, organic acids and other types of organic solvents.
A invenção compreende ainda um micro-dispositivo para extracção vestigiàl de substâncias com diferentes polaridades caracterizado, por incluir um suporte esférico, podendo ter diferentes diâmetros e ser revestido por materiais adsorventes.  The invention further comprises a micro-device for trace extraction of substances of different polarities, comprising a spherical support which may have different diameters and be coated with adsorbent materials.
0 micro-dispositivo terá um número variável de esferas, revestidas pelo material adsorvente, que estão unidas por um fio,  The micro-device will have a variable number of beads, coated with the adsorbent material, which are joined by a wire,
0 micro-dispositivo é caracterizado adicionalmente por o suporte e o fio poderem ser, num exemplo não limitativo, à base de poliestireno e de algodão respectivamente .  The micro-device is further characterized in that the support and the yarn may be, in a non-limiting example, polystyrene and cotton based respectively.
O micro-dispositivo é caracterizado adicionalmente por o material adsorvente ser seleccionado de um grupo incluindo carvões activados, zeólitos, aluminas, sílicas, calixarenos , sólidos inorgânicos finamente divididos, entre outro tipo de adsorventes preparados laboratorialmente. The micro-device is further characterized in that the adsorbent material is selected from a group including activated charcoals, zeolites, aluminas, silicas, calixeenes, finely divided inorganic solids, among other type of laboratory prepared adsorbents.
A invenção compreende ainda um método para obtenção de um micro-dispositivo para extracção- vestígial de substâncias com diferentes polaridades caracterizado por incluir as seguintes etapas: The invention further comprises a method for obtaining a trace device for extracting trace substances. with different polarities characterized by including the following steps:
a) colocação das esferas de poliestireno no fio;  (a) placement of polystyrene beads on the wire;
b) revestimento' das esferas com material adsorvente finamente dividido por acção térmica durante um determinado período de tempo; b) coating 'balls with finely divided adsorbent material by thermal action over a given period of time;
c) remoção do excesso do material adsorvente por lavagem ultra-sónica ou por agitação com água ou com um solvente orgânico .  c) removing excess adsorbent material by ultrasonic washing or by stirring with water or an organic solvent.
Numa forma de realização da invenção, o micro-dispositivo consiste num suporte constituído por diversas esferas em poliestireno com 2 mm de diâmetro médio (1), unidas por um fio que poderá, por exemplo, ser de algodão. 0 fio e as esferas são colocados dentro de um frasco contendo já algum material adsorvente finamente dividido enchendo-se posteriormente o frasco com o material adsorvente de forma á que todas as esferas fiquem cobertas pelo material adsorvente (2) . O frasco contendo o fio com as esferas em poliestireno revestido com o material sólido é cõlocadò num forno a uma determinada temperatura e a um determinado tempo consoante o tipo de material adsorvente utilizado. Normalmente utiliza-se uma temperatura de 160°C durante 2 h. 0 material adosrvente adere à superfície das esferas de poliestireno, ficando fixo por. acção térmica. Posteriormente, retira-se do frasco o fio (3) contendo as esferas de poliestireno já cobertas pelo material adsorvente e une-se o número de esferas necessário para posterior análise, normalmente entre 5 a 10 esferas. Corta- se o fio e recòlhem-se vários micro-dispositivos . No final, o micro-dispositivo suportado com o material sólido é tratado no sentido de retirar o excesso de adsorvente e limpo com. um solvente apropriado.. O micro-dispositivo preparado está então em condições de se colocado num frasco (4) contendo uma amostra liquida (5) sob agitação por intermédio de uma barra magnética (6), ficando em suspensão na zona abaixo à formação do vortex liquido (7)·, uma vez que o micro-dispositivo (8) tem densidade apropriada para este efeito relativamente ao fluido ou amostra, procedendo à extracção de substâncias com diferentes polaridades após se estabelecer o estado de equilíbrio. Ao contrário das invenções anteriores, o micro- dispositivo proposto não apresenta na sua constituição nenhum material magnético, sendo a agitação para se atingir o equilíbrio efectuada por intermédio de uma barra magnética convencional em "teflon" ou outro material adequado a essa função. In one embodiment of the invention, the micro-device consists of a support made up of several 2 mm medium diameter polystyrene spheres (1) joined by a thread which may, for example, be cotton. The yarn and beads are placed into a vial already containing some finely divided adsorbent material and the vial is subsequently filled with the adsorbent material so that all the beads are covered by the adsorbent material (2). The flask containing the polystyrene bead yarn coated with the solid material is placed in an oven at a given temperature and at a given time depending on the type of adsorbent material used. Usually a temperature of 160 ° C is used for 2 h. The adhering material adheres to the surface of the polystyrene beads and is fixed by. thermal action. Subsequently, the thread (3) containing the polystyrene spheres already covered by the adsorbent material is removed from the flask and the number of spheres required for further analysis is joined, usually between 5 and 10 spheres. Cut the thread and collect various micro-devices. In the end, the micro-device supported with the solid material is treated to remove excess adsorbent and cleaned with . a suitable solvent. . The prepared micro-device is then able to be placed in a flask (4) containing a liquid sample (5) under stirring by means of a magnetic bar (6), suspended in the area below the formation of the liquid vortex (7). · Since the micro-device (8) has appropriate density for this purpose relative to the fluid or sample, extracting substances with different polarities after establishing the equilibrium state. Contrary to the previous inventions, the proposed micro-device does not have any magnetic material in its constitution, and the agitation to reach equilibrium is performed by means of a conventional Teflon magnetic bar or other material suitable for this function.
Aplicação e vantagens da invenção Application and advantages of the invention
Na aplicação desta metodologia na análise de substâncias com diferentes polaridades, incidindo nas que apresentam uma maior polaridade obtiveram-se resultados significativos que evidenciam excelente desempenho deste processo analítico, quando  The application of this methodology in the analysis of substances with different polarities, focusing on those with higher polarity, obtained significant results that show excellent performance of this analytical process when
comparados com outras metodologias propostas na literatura.. A figura 3 exemplifica alguns resultados obtidos, onde é possível observar os cromatogramas resultantes desta metodologia na análise de diversos tipos de compostos em diferentes tipos de matrizes aquosas reais, seguida de análise por HPLC. Exemplos de substâncias estudadas em meio aquoso foram antibióticos (sulfatiazoÍ-9, sulfametoxazol^ 10, sulfadimetoxina-11, trímetoprim-12 e enrofloxacina-13 )compared to other methodologies proposed in the literature. Figure 3 exemplifies some results obtained, where it is possible to observe the chromatograms resulting from this methodology in the analysis of different types of compounds in different types of real aqueous matrices, followed by HPLC analysis. Examples of substances studied in aqueous media were antibiotics (sulfathiazole-9, sulfamethoxazole ^ 10, sulfadimethoxine-11, trimethoprim-12 and enrofloxacin-13).
(a) , analgésicos e alcalóides (paracetamol-14 e cafeína-15)(a) Analgesics and alkaloids (acetaminophen-14 and caffeine-15)
(b) e hormonas sexuais esteróides (estriol-16, 19- norétisterona-17 , estrona-18, 17p-estradÍol-19-, dietilstilbestrol-20, norgestrel-21 , progesterona-22 e mestranol-23 ) (c) , conforme pode. ser observado na figura 3. Todos estes resultados evidenciaram uma eficiência muito superior quando comparada a outras metodologias de técnicas sorptivas, nomeadamente, SPME e SBSE à base de PDMS . Para efeitos de comparação com esta última técnica, verificou-se que no caso de paracetamol, cafeína e antibióticos a recuperação era nula embora com o novo micro-dispositivo se obtiveram recuperações compreendidas entre 50 e 92 % . Para hormonas sexuais esteróides: veríficou-se ainda que para as mais apoiares a recuperação obtida foi semelhante, mas para as mais polares obteve-se uma eficiência sete vezes superior . (b) and steroid sex hormones (estriol-16, 19-norethysterone-17, estrone-18, 17p-estradiol-19-, diethylstilbestrol-20, norgestrel-21, progesterone-22 and mestranol-23) (c) as can. be observed in figure 3. All these results showed a much higher efficiency when compared to other methodologies of snake techniques, namely SPME and SBSE based on PDMS. For comparison with the latter technique, it was found that in the case of acetaminophen, caffeine and antibiotics the recovery was null although with the new micro-device recoveries between 50 and 92% were obtained. For steroid sex hormones : it was also found that for the most supportive the recovery was similar, but for the most polar obtained a seven times higher efficiency.
Os micro-dispositivos analíticos contendo adsorventes adequados poderão ser facilmente aplicados a amostras reais em diversas áreas científicas, nomeadamente, matrizes aquosas com origem ambiental, entre outras, no sentido de extrair compostos com diferentes polaridades com interesse, para análise posterior com recurso a técnicas cromatográficas, hifenadas bem com electroforese capilar.  Analytical micro-devices containing suitable adsorbents can be easily applied to real samples in various scientific areas, namely aqueous matrices with environmental origin, among others, in order to extract compounds with different polarities of interest, for further analysis using chromatographic techniques. , hyphenated well with capillary electrophoresis.

Claims

REIVINDICAÇÕES
1. Um micro-dispositivo para extracção vestigial de substâncias polares caracterizado por compreender pelo menos um suporte esférico, podendo ter diferentes diâmetros, revestido por um material adsorvente.  1. A micro-device for the trace extraction of polar substances, comprising at least one spherical support, which may have different diameters, coated with an adsorbent material.
Micro-dispositivo de acordo com a reivindicação 1 caracterizado por o suporte esférico ser um número variável de esferas, revestidas pelo material adsorvente , que estão unidas por um fio. Micro device according to Claim 1, characterized in that the spherical support is a variable number of balls, coated with the adsorbent material, which are joined by a thread.
3. Micro-dispositivo de acordo com qualquer uma das reivindicações 1-2, caracterizado por o suporte esférico ser à base de poliestireno.. Micro device according to any one of claims 1-2, characterized in that the spherical support is based on polystyrene.
4. Micro-dispositivo de acordo com qualquer uma das reivindicações 1-2, caracterizado por o fio ser,, de algodão . Micro device according to any one of claims 1-2, characterized in that the yarn is made of cotton.
5. Micro-dispositivo de acordo com a reivindicação 1, caracterizado por o material adsorvente ser seleccionado de um grupo incluindo carvões activados, zeólitos, aluminas, sílicas, calixarenos, sólidos inorgânicos finamente divididos, entre outro tipo de adsorventes preparados laboratorialmente . Micro-device according to Claim 1, characterized in that the adsorbent material is selected from a group including activated charcoals, zeolites, aluminas, silicas, calixeenes, finely divided inorganic solids, among other types of laboratory prepared adsorbents.
6. Um método para micro-extracção vestigial de substâncias com diferentes polaridades caracterizado por compreender as seguintes etapas: 6. A method for trace micro-extraction of substances with different polarities comprising the following steps:
a) colocação de um micro-dispositivo de acordo com as reivindicações 1 a 5, e de uma barra magnética de agitação convencional numa amostra constituída por um fluído com densidade superior à do micro-dispositivo e inferiox à da barra magnética de agitação; a) placing a micro-device according to claims 1 to 5 and a conventional stirring magnetic bar in a sample consisting of a fluid with a density higher than that of the micro-device and less than that of the magnetic stir bar;
b) agitação da amostra durante um período de tempo adequado através da barra magnética de agitação convencional ; b) shaking the sample for a suitable period of time through the conventional stirring magnetic bar;
c) extracção das. substâncias polares para os materiais adsorventes constituintes do micro-dispositivo após se estabelecer o estado de equilíbrio; c) extraction of. polar substances to the adsorbent materials constituting the micro-device after equilibrium has been established;
d) após extracção, colocação do micro-dispositivo em volume de solvente ou mistura de solventes, sob condições optimizadas (ex. pH) adequadas à retroextracçâo ou dessorção líquida dos solutos inicialmente extraídos da amostra, em particular os analitos com características polares . (d) after extraction, placing the microplate in solvent volume or solvent mixture under optimal conditions (eg pH) suitable for back-extraction or liquid desorption of initially extracted solutes, in particular analytes with polar characteristics.
7. Método de acordo com a reivindicação 6 caracterizado por o fluído ser genericamente soluções aquosas,: misturas hidroalcoóliças entre outras. Method according to claim 6, characterized in that the fluid is generally aqueous solutions, hydroalcoholic mixtures among others.
8. Método de acordo com a reivindicação 6 caracterizado por a agitação da amostra se realizar até se alcançar o estado de, equilíbrio num período nunca inferior a 30 minutos . Method according to claim 6, characterized in that the sample is agitated until equilibrium is reached within a period of not less than 30 minutes.
9. Método de acordo com a reivindicação 6 caracterizado por as substâncias- polares terem diversa origem, nomeadamente, pesticidas e respectivos metaboii tos , drogas, produtos farmacêuticos de higiene e cuidado pessoal, metabolltos naturais, produtos naturais, entre outros. A method according to claim 6, characterized in that the polar substances are of various origin, namely pesticides and their metabolites, drugs, hygiene and personal care pharmaceuticals, natural metabolites, natural products, among others.
10. Método de acordo com a reivindicação 6 caracterizado por a barra magnética de agitação convencional ser revestida com "teflon". Method according to claim 6, characterized in that the conventional stirring magnetic bar is coated with "teflon".
11. Método de acordo com a reivindicação 6 caracterizado por o solvente ou mistura de solventes ser seleccionado de um grupo incluindo: soluções aquosas a pH controlado, álcoois, acetonitrilo, ácidos Orgânicos e outros tipos de solventes orgânicos. A method according to claim 6 characterized in that the solvent or solvent mixture is selected from a group including: pH controlled aqueous solutions, alcohols, acetonitrile, organic acids and other types of organic solvents.
12. Método para obtenção do micro-dispositivõ descrito nas reivindicações 1 a 5, caracterizado por incluir as seguintes etapas : Method for obtaining the micro-device described in claims 1 to 5, characterized in that it comprises the following steps:
a) colocação de esferas de poliestireno num fio; (a) placing polystyrene spheres on a wire;
b) revestimento das esferas com material adsorvente finamente dividido por acção térmica durante um determinado período de tempo; b) coating the beads with thermally finely divided adsorbent material over a period of time;
c) remoção do excesso do material adsorvente por lavagem ultra-sónica ou por agitação com água ou com um solvente orgânico . c) removing excess adsorbent material by ultrasonic washing or by stirring with water or an organic solvent.
1 3. Uso do micro-disposítívo descrito nas reivindicações a 5 e obtido pelo método descrito na reivindicação caracterizado por ser usado para; análise vestigial amostras com diferentes polaridades. Use of the micro-device described in claims a 5 and obtained by the method described in the claim characterized in that it is used for; trace analysis samples with different polarities.
PCT/PT2010/000066 2009-12-12 2010-12-13 Method and micro device for the extraction of traces of chemical substances with different polarities WO2011071406A1 (en)

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US6825046B1 (en) * 1999-08-12 2004-11-30 Her Majesty The Queen In Right Of Canada, As Represented By The Minister Of Health Micro extraction technique
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Publication number Priority date Publication date Assignee Title
WO1994005401A1 (en) * 1992-09-04 1994-03-17 Pont-A-Mousson S.A. Method for fabricating a gas adsorption means, adsorption means and sanitazing plant
DE19913809A1 (en) * 1999-03-26 2000-10-19 Gerstel Systemtechnik Gmbh Concentration of dilute soluble species for analysis, comprises adsorbing onto coated magnetic stirrer impeller elements, and desorption in gas chromatograph
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