WO2008059274A1 - Dispositifs de capteurs - Google Patents

Dispositifs de capteurs Download PDF

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Publication number
WO2008059274A1
WO2008059274A1 PCT/GB2007/004393 GB2007004393W WO2008059274A1 WO 2008059274 A1 WO2008059274 A1 WO 2008059274A1 GB 2007004393 W GB2007004393 W GB 2007004393W WO 2008059274 A1 WO2008059274 A1 WO 2008059274A1
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WO
WIPO (PCT)
Prior art keywords
polymer
change
response
properties
measurable response
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PCT/GB2007/004393
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English (en)
Inventor
Linda Swanson
Steven Rimmer
Original Assignee
University Of Sheffield
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Publication date
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Publication of WO2008059274A1 publication Critical patent/WO2008059274A1/fr

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/48—Biological material, e.g. blood, urine; Haemocytometers
    • G01N33/50—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing
    • G01N33/58—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing involving labelled substances
    • G01N33/582—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing involving labelled substances with fluorescent label
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
    • G01N21/783—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour for analysing gases

Definitions

  • the present invention is concerned with polymeric materials and their use in detection systems. More specifically, the invention involves the preparation of crosslinked polymeric hydrogels and their application to the detection of materials in liquid and, more preferably, gaseous form.
  • the stimulus or trigger may be in the form_of, for example, a change in temperature or in pH conditions and this, in turn, may result from the introduction of an external agent into a system.
  • an acidic agent to an environment would result in a change in the pH value.
  • PMAA poly(methacrylic acid)
  • the volume of the polymer coil in water is known to expand very significantly over a narrow range of pH values as a solution becomes more basic. 1"6 .
  • Fluorescence spectroscopic measurements have proved to be an invaluable tool in monitoring the "smart" behaviour of polymer systems 4"10 , including those which show a response to temperature 7"10 .
  • modification of PMAA by simple copolymerization with styrene ⁇ ca. 24 wt%) changes the hydrophobic to hydrophilic balance within the macromolecule, and this serves to shift the conformational transition to higher pH 6 . Consequently, chemical modification of a polymer molecule effectively allows the smart response to be tuned to any desired pH.
  • the present invention seeks to provide smart polymers which may be used for the determination of changes in the surrounding environment. Said changes may comprise physical or chemical changes, but typically comprise chemical changes, or changes in temperature. More specifically, the present invention seeks to provide smart polymers wherein a conformational change occurs in response to the presence or absence of other chemical species.
  • a polymer adapted to provide a measurable response associated with a change in the properties of a system.
  • said polymer comprises a crosslinked polymer.
  • said crosslinked polymer comprises a hydrogel.
  • Hydrogels comprise linear or hyperbranched polymer chains which have been chemically crosslinked in order to hold the chains together in a three-dimensional network, such that the polymers will not redissolve and leach into the system.
  • Said hydrogels have a hydrated crosslinked gel structure which may be caused to collapse and dehydrate as a consequence of said change in said system, thereby resulting in the polymer chains coming into closer mutual proximity.
  • said polymer comprises a hyperbranched polymer.
  • Said system may comprise a liquid or a gaseous system.
  • Said change in the properties of said system comprises a physical or, preferably, a chemical change.
  • said chemical change comprises a change in pH.
  • said chemical change may result from the introduction of more complex chemical species into the system.
  • the change may be associated with the presence of a gas, such as carbon dioxide, which causes a change in pH of a system, or with the introduction of a chemical species capable of binding to, or otherwise interacting with - for example, degrading - the polymer according to the first aspect of the invention.
  • Typical examples of species capable of entering into such reactions include biomolecules such as proteins, polysaccharides, nucleic acids, or other low molecular species, whilst the binding of protons at pH sensitive groups provides a simple example of such groups providing means for detection of changes in pH.
  • Said measurable response is preferably a visible response.
  • said visible response comprises a colour change or volume change, such as the collapse of a gel structure.
  • said response is a visible response which comprises a colour change associated with the presence of luminescent probes attached to said polymer.
  • a polymer chain may be labelled by attachment of said probes, thereby allowing the physical conformation of the polymer to be determined by virtue of spectral changes associated with differences in the physical separation of polymer chains, and the consequent interactions - or lack of interactions - between the excited singlet state probes located on the different chains.
  • a means for detecting a change in the properties of a system comprising a polymer according to the first aspect of the invention.
  • an apparatus incorporating means according to the second aspect of the invention.
  • a method for the determination of a change in the properties of a system comprising providing a polymer according to the first aspect of the invention.
  • Figure 1 illustrates the collapse of the of the gel structure of a polymer according to the invention on exposure to CO 2 ;
  • Figure 2 shows the coil collapse process of a polymer according to the invention at the lower critical solution temperature
  • Figure 3 illustrates the changes in LCST promoted by binding or chemical/biochemical reactions with polymers according to the invention
  • Figure 4 is a graph showing the response induced in a fluorescent linear PMAA sample on exposure to CO 2 ;
  • Figure 5 illustrates the mode by means of which an optical response is produced on collapse of a gel structure
  • Figure 6 shows the change in volume swelling of a CO 2 responsive film as the steady state concentration of CO 2 changes and the change in gas diffusion as the film swells and deswells;
  • Figure 7 is a fluorescence emission spectrum of the response of a fluorescently labelled hyperbranched polymer to a change in temperature in water below and above the critical temperature;
  • Figure 8 illustrates a device for the detection of carbon dioxide, which is illustrative of the invention.
  • a polymer comprising a hydrogel which is adapted to provide a measurable response to a change in the pH of a system, more particularly a gaseous system.
  • said polymer is adapted to provide a measurable response consequent upon the presence of carbon dioxide in a system, wherein the presence of said carbon dioxide causes an increase in the pH of the system.
  • said measurable response comprises an optical response which, most conveniently, is provided in the form of a visible colour change.
  • luminescent probes in said polymers, thereby facilitating the detection of a spectral change in response to a change in the system under consideration.
  • a measurable spectral difference is associated with a change in the confirmation of the polymer, as previously discussed.
  • the measurable response comprises a colour change, wherein said colour change is preferably associated with the presence of luminescent probes in said polymer, and said colour change is consequent upon a conformational change in the physical structure of said polymer.
  • luminescent hydrogels which contract in the presence of carbon dioxide producing a distinct fluorescence colour change. Said hydrogels take advantage of the fact that carbon dioxide, when dissolved in water, forms carbonic acid which, at high enough concentrations, decreases the pH of a solution.
  • dissolution of carbon dioxide in the water bound in the hydrogel structure is thereby able to induce a conformational change in the hydrogel.
  • the hydrogel In order to be suitable for the detection of carbon dioxide, the hydrogel must comprise a polymer having a chemical structure susceptible to attack by acid, such that a chemical reaction occurs which induces the said conformational change.
  • Typical polymers which are suitable for the said purpose comprise acid or basic end groups, preferably free carboxylic acid groups, or amino groups, typically tertiary amino groups.
  • favoured hydrogels are polymers and copolymers of carboxylic acid-containing monomers and amine-containing monomers.
  • Preferred monomers in this regard include acrylic acid, methacrylic acid, and various amino (meth)acrylate monomers.
  • Homo- and copolymers comprising these monomers are found to be particularly useful for the stated purpose, with methacrylic acid-based polymers and polymers derived from aminoethyl methacrylate being especially preferred.
  • methacrylic acid-based polymers and polymers derived from aminoethyl methacrylate being especially preferred.
  • Very favourable results have been achieved with linear poly(methacrylic acid) samples, which show a collapse in gel structure with increasing pH, whilst polymers derived from monomers such as 2-(diemthylamino)ethyl methacrylate are particularly effective in showing an expansion of the gel structure in the presence of carbon dioxide.
  • Suitable comonomers for the preparation of copolymers of the above monomers include water soluble monomers which carry no ionic charge, most particularly water soluble vinyl or acrylic monomers. Examples include N-vinyl caprolactam, N-vinyl pyrrolidone, or
  • (hydroxyl)alkyl (meth)acrylates such as ethyl methacrylate, propyl methacrylate or glycidyl methacrylate.
  • said comonomers are water soluble
  • (meth)acrylamides more preferably N-alkylacrylamides, most preferably N- isopropylacrylamide.
  • LCST critical solution temperature
  • the polymer chain In the event that the polymer chain is free to dissolve, i.e. it is not cross-linked, then the polymer precipitates from solution or forms particulate or gel structures. However, if the chains are constricted by being cross-linked into a network, then the LCST is observed as deswelling behaviour, which may be accompanied by the onset of turbidity and/or opacity. These are essentially thermal phenomena but the temperature of the LCST is very structure-dependent. Thus, changes in structure produce changes in the LCST and if these changes in LCST pass through the application temperature a transition is observed in response to the structural change.
  • Structural changes may, of course, be brought about by means of binding events or chemical/biochemical reactions, and this situation is illustrated in Figure 3, where it is shown that, for a given application temperature T, then a transition will occur as the LCST changes from LCST-1 to LCST-2 and from LCST-1 to LCST-3.
  • the labelling of a gel with a donor and acceptor species would allow collapse of individual polymer chains and consequent shrinkage of the entire network to be monitored by non radiative energy transfer; in an expanded gel, for example, green fluorescence may be observed, whereas, on collapse of the hydrogel, red fluorescence is detected.
  • UV curing may be used to coat a carbon dioxide responsive crosslinked polymer on a surface.
  • Said crosslinked polymer is adapted to swell in the presence of carbon dioxide, and to shrink back to its original dimensions as the level of carbon dioxide decreases.
  • This system requires the use of monomeric and/or oligomeric units that are capable of copolymerisation in situ, and can be formulated with commercially available resins and diluents known in the art of UV curing of lacquers and inks.
  • Said embodiment finds particular application in respect of food packaging, and this is an area of technology to which the present invention is particularly suited.
  • valve system for the degassing of freshly roasted coffee in flexible packaging.
  • Said valve system is built into the laminate packaging and comprises channels, which provide a one-way system that allows carbon dioxide to be released from the packaging, but also prevents gases from entering.
  • Silicon oil is preferably used to keep the channels closed after degassing, and to prevent air from entering from the outside environment. The degassing process for freshly ground coffee takes several hours and, for coffee beans, several days. Following degassing, the silicon seal is required to remain intact in order to prevent the coffee from being spoilt.
  • valve it is possible for the valve to become damaged during transportation, most commonly through either adhesive failure at the oil/laminate interface, or cohesive failure of the silicon oil.
  • present invention is able to offer improvements in this regard by allowing for coating of the valve laminate with a UV- curable, CO 2 -responsive lacquer.
  • the application and curing process which are required are in line with current lamination processes, so that the additional layer can be added without significant modification of the prior art process and, hence, its application is easily and cheaply achieved.
  • a coating is formulated with low molecular weight, pH sensitive (and thus also CO 2 responsive) monomers, together with commercial resins and diluents commonly used in the art in order to produce a coated valve.
  • said pH sensitive monomers comprise at least one oligomeric component, most preferably at least one diacrylate oligo(methacrylate), which can be prepared using prior art synthetic procedures 12"15 .
  • Figure 6 A schematic illustration of the operation of a valve coated with a CO 2 responsive polymer is shown in Figure 6, which depicts an expanded film (grey area) that allows carbon dioxide to diffuse through the valve. Expansion results because the steady state concentration of carbon dioxide in the film, resulting from the pressure of carbon dioxide in the bag, is high.
  • Hydrogels of this type may find application in connection with a wide variety of other foodstuffs.
  • the gels can act as fresh produce ripening indicators in respect of fruit and vegetables since, when these products ripen, they release volatiles, the level of which can be related to the degree of maturity of the produce.
  • the volatiles released typically comprise carbon dioxide and/or ethylene.
  • the polymers according to the first aspect of the invention may be used in conjunction with foodstuffs such as fish, meat and poultry, as well as a large range of dairy products, such as milk, cream, butter and, most especially, cheese, all of which release volatile materials on ⁇ ageing.
  • Volatile materials that are particularly suited to detection in the context of the present invention include any volatile amine functional compound, any volatile acidic compound, or any volatile compound that can bind to specific groups present on the polymer.
  • Labelling of a hydrogel with a luminescent donor and acceptor species allows shrinkage of the entire network to be monitored by energy transfer so that different coloured fluorescence is observed from the expanded gel and the collapsed gel, since the two luminescent species can communicate with one another in the latter state.
  • the degree of contraction may be controlled by means of the polymer composition, and controlling this feature of the invention allows for tuning of the spectrum of the signal produced in the presence of the volatile products which act as triggers for the collapse of the hydrogel.
  • the polymers according to the first aspect of the invention may find wide application in the food and biomedical fields, due to their varying "smart" responses to changes in various system parameters, such as pH.
  • these polymers may in addition to being used as, for example, pH sensors, be employed to detect proteins and bacteria.
  • Suitable polymers are available which are capable of complexing with proteins and, from these materials, fluorescent hydrogels may be prepared which will complex to, and therefore detect, proteins.
  • Such polymers may find application in biological assays, wherein an optical colour change results upon detection of a protein.
  • said polymers have potential use in detecting bacteria in infected wounds, and in germ warfare.
  • an alternative preferred embodiment of the invention envisages a polymer which comprises a hyperbranched polymer adapted to provide a measurable response associated with the introduction of a chemical species into a system, wherein the measurable response is consequent upon the presence of chemically reactive end groups in the polymer, these end groups reacting with the newly introduced species.
  • the reactive end group comprises a pH sensitive group which reacts with hydrogen ions generated on an increase in the acidity of a system, or an end group which is capable of reaction with a more complex molecule, such as a biomolecule.
  • Preferred examples of reactions with biomolecules include binding reactions or degradation reactions which may occur on interaction with, for example, proteins, polysaccharides, nucleic acids, enzymes, and other low molecular species.
  • suitable enzymes include collagenase, peptidases, and proteases such as Arg-gingipain, protease V8 and elastase. It has been found that copolymers according to the invention which incorporate (meth)acrylamide comonomers are particularly suitable for use in biomedical applications, such as bacteriological sensing procedures.
  • the degree of expansion or contraction after the application of the stimulus is dependent on the fraction of the responsive component in the gel, so that formulations with high fractions of responsive component change more than those with lower fractions.
  • the magnitude of the observed change is seen to be a function of the polymer composition.
  • This phenomenon affords the possibility of quantifying the response because the spectrum produced after application of the stimulus is dependent on the distance between the donor and acceptor. This distance changes as the degree of contraction (swelling) changes.
  • the principle of fluorescence energy transfer or fluorescence resonance energy transfer is well established, particularly in biology, and examples of the application of the technique to the study of conformational changes in macromolecules have also been reported 16"17 .
  • the present invention goes well beyond the prior art, since it provides for (i) combining the effects of controlling the degrees of collapse in gels, (ii) using fluorescence energy transfer to detect the collapse, and (iii) ultimately using the smart response induced by volatiles to sense the presence of those volatiles.
  • the present invention provides novel polymers, means, systems and methods for providing a measurable response associated with a change in the properties of a system.
  • the invention therefore, provides polymers, most preferably hydrogels, which may be used in the manufacture of a variety of sensors having wide application.
  • fluorescence energy transfer may be used to provide a measurable response with said hydrogel sensors, allowing for the measurement of swelling and de-swelling in said sensors.
  • Said measurable response is associated with the transfer of excitation energy from a fluorescent excited donor molecule such that the excited state lifetime of the donor molecule decreases.
  • a further preferred embodiment of the invention envisages a polymer which comprises a hyperbranched polymer having chemically reactive end groups capable of, for example, participating in binding reactions with other species or of undergoing degradation on interaction with other species.
  • volume change may be achieved by coiling and uncoiling of the polymer chains, causing the polymers to swell and de-swell in response to changing environmental conditions.
  • the present invention offers scope for the production of polymeric sensors finding use in a wide range of different applications.
  • This example illustrates the optical response to a change in shape of a hyperbranched polymer triggered by temperature
  • FIG. 7 there is presented the steady state fluorescence emission spectrum of the response of a fluorescently labelled hyperbranched polymer to a change in temperature in water below and above the critical temperature.
  • the sample is hyperbranched poly(N-isopropylacrylamide) containing acenaphthylene (1 mole%) as the donor and anthryl methylmethacrylate (1 mole%) as the acceptor.
  • the change in shape of the macromolecule from an expanded chain to a compact globule, triggered by the temperature, is revealed by an increase in the degree of energy transfer between the fluorescent donor and acceptor: the fluorescence from the acceptor is enhanced between 400-500 nm at 45 0 C.
  • This example relates to the response of a hydrogel film to carbon dioxide.
  • FIG 8 there is depicted a device for the detection of carbon dioxide according to the invention.
  • the device comprises a photocrosslinked hydrogel film 1 , containing 50 wt% dimethylamino ethylmethacrylate and 50 wt% butylmethacryalte dimethacrylate, coated between layers of PET film 2 located between the upper and lower chambers 3 and 4, both of which are fitted with manometers 5 and 6.
  • the hydrogel film was treated with buffer solution at pH 10.
  • Nitrogen gas was introduced into the lower chamber, and no change in pressure was observed in the upper chamber, indicating that the gas could not permeate through the film. Under these conditions, the hydrogel is in the collapsed form and acts as a barrier. CO 2 was subsequently piped into the lower chamber, and the presence of this gas caused swelling of the hydrogel, thereby allowing the gas to diffuse into the upper chamber where an increase in pressure was detected. This shows that in the acidic form the gel is in the expanded state, thereby allowing diffusion of CO 2 .

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Abstract

L'invention concerne un polymère conçu pour fournir une réponse mesurable associée avec un changement des propriétés d'un système, et un moyen, un appareil et un procédé de détection dudit changement. Le polymère comprend de préférence un hydrogel, le changement des propriétés du système comprend un changement de pH, et la réponse mesurable comprend un changement de couleur. De manière davantage préférée, le changement de couleur est associé avec la présence de sondes luminescentes attachées au polymère. Un deuxième aspect de la présente invention concerne un moyen de détection d'un changement dans les propriétés d'un système, ledit moyen comprenant un polymère selon le premier aspect de la présente invention. Des modes de réalisation particulièrement préférés de la présente invention comprennent des capteurs à hydrogel et des polymères hyperramifiés qui ont un large éventail d'applications différentes. L'invention offre des avantages particuliers dans le domaine de l'emballage alimentaire et des biotechnologies.
PCT/GB2007/004393 2006-11-18 2007-11-16 Dispositifs de capteurs WO2008059274A1 (fr)

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GB0623043.7 2006-11-18
GB0623043A GB0623043D0 (en) 2006-11-18 2006-11-18 Sensor devices

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CN101787095A (zh) * 2010-03-12 2010-07-28 江苏工业学院 一种通过氧化聚合制备超支化聚合物的方法
WO2010094976A1 (fr) 2009-02-20 2010-08-26 University Of Sheffield Nouvelle utilisation de polymères
WO2013083993A1 (fr) 2011-12-07 2013-06-13 The University Of Manchester Microdétecteur
CN103657718A (zh) * 2012-09-05 2014-03-26 中国石油化工股份有限公司 用于制备碳酸亚烷酯的树脂催化剂及其方法
WO2015027057A1 (fr) 2013-08-23 2015-02-26 Elwha Llc Sélection et administration d'agents de traitement basées sur un profil microbien
US9186278B2 (en) 2013-11-27 2015-11-17 Elwha Llc Systems and devices for sampling and profiling microbiota of skin
US9390312B2 (en) 2013-08-23 2016-07-12 Elwha Llc Systems, methods, and devices for assessing microbiota of skin
US9456777B2 (en) 2013-08-23 2016-10-04 Elwha Llc Systems, methods, and devices for assessing microbiota of skin
US9526480B2 (en) 2013-11-27 2016-12-27 Elwha Llc Devices and methods for profiling microbiota of skin
US9526450B2 (en) 2013-11-27 2016-12-27 Elwha Llc Devices and methods for profiling microbiota of skin
US9549703B2 (en) 2013-11-27 2017-01-24 Elwha Llc Devices and methods for sampling and profiling microbiota of skin
US9557331B2 (en) 2013-08-23 2017-01-31 Elwha Llc Systems, methods, and devices for assessing microbiota of skin
US9610037B2 (en) 2013-11-27 2017-04-04 Elwha Llc Systems and devices for profiling microbiota of skin
CN107022049A (zh) * 2017-04-17 2017-08-08 华东交通大学 一种具有co2刺激响应型智能聚合物微球的制备方法
US9805171B2 (en) 2013-08-23 2017-10-31 Elwha Llc Modifying a cosmetic product based on a microbe profile
US9811641B2 (en) 2013-08-23 2017-11-07 Elwha Llc Modifying a cosmetic product based on a microbe profile
CN106279551B (zh) * 2015-05-29 2018-09-14 天津大学 抗撕裂水凝胶在制备二氧化碳响应器件中的应用
CN111521601A (zh) * 2020-04-22 2020-08-11 中国科学院宁波材料技术与工程研究所 一种比率型荧光高分子水凝胶在海鲜新鲜度检测中的应用
CN113461974A (zh) * 2021-07-28 2021-10-01 吉林大学 一种气体响应表面润滑水凝胶及其制备方法

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Cited By (27)

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Publication number Priority date Publication date Assignee Title
WO2010094976A1 (fr) 2009-02-20 2010-08-26 University Of Sheffield Nouvelle utilisation de polymères
CN101787095A (zh) * 2010-03-12 2010-07-28 江苏工业学院 一种通过氧化聚合制备超支化聚合物的方法
WO2013083993A1 (fr) 2011-12-07 2013-06-13 The University Of Manchester Microdétecteur
CN103657718B (zh) * 2012-09-05 2015-09-09 中国石油化工股份有限公司 用于制备碳酸亚烷酯的树脂催化剂及其方法
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