JPH10506132A - Responsive gel for selectively removing target substance from environment and method thereof - Google Patents

Abstract

(57) [Abstract] A responsive gel that selectively removes target substances from the environment is described. Three-dimensional reversibly responsive polymer gels form a binding site when they approach each other and consist of at least two binding sites for a target substance that has the ability to bind the target substance. The ties are combined with a responsive polymer component adapted to respond to changing environmental conditions and undergo reversible volume contraction and expansion. The polymer gel component has a volume contraction phase transition threshold different from the volume expansion phase transition leap value. The responsive gel is positioned such that when the polymer gel shrinks to a contracted state at the phase transition threshold, the binding sites are sufficiently close to each other and to the target substance so that the binding sites can bind the target substance. Be built. When the polymer expands to an expanded state at the phase transition threshold, the bonds are separated from each other. Methods for removing target substances from the environment are also described, wherein the polymer gels of the present invention have a binding affinity for the target substance, the binding site, and the binding moieties are bound to each other so as to bind the target substance at the binding site. Contacting the gel with a target substance that allows the gel to move into a contracted state so that the gel is sufficiently close to the target. A method for selectively removing a target substance and a target substance selected from another target substance solution is also described. In a preferred embodiment, the procedure for changing the environmental conditions comprises changing the temperature of the gel.

Description

DETAILED DESCRIPTION OF THE INVENTION       Responsive gel for selectively removing target substance from environment and method thereof   The invention described and claimed herein is by Foster Miller, Inc. Department of Energy (DOE) contract number given to ter Miller, Inc.) Partly assisted by issue DE-FGO2-94ER81667. The United States Government has Has certain rights.                                 Background of the Invention   Selective absorption and recovery of target molecules can be as biological as in the chemical and pharmaceutical industries. It is one of the most basic processes in the system. Nevertheless, nature Intended to retrieve the target material in contrast to the biological system taking place in the Many of the artificial systems that have been selected rely on the selectivity for the target substance and the target Lack of the ability to release quality reversibly. Often, the recovery of the target molecule is Requires extensive desorption and solvent cleaning, causing serious environmental problems.   Used to selectively recover target molecules from the environment containing the target substance As one example of a myriad of methods, we have discussed heavy metal contamination in water and wastewater. And take it easy. Some metals can be consumed as food in trace amounts. Is an essential component. However, many metals are toxic at high concentrations, It also affects kidney function. Commonly used to treat metal-containing water and wastewater There are many ways that can be done. The most commonly used processing technology is by its own precipitation, Alternatively, it depends on a combination with another processing method that increases the efficiency. Precipitation method is a drug By adding the product and adjusting the pH of the solution, a supersaturated solution is made, A precipitate is obtained. The sedimentation method is non-selective, and the residue (sludge ) And the residue must be disposed of. Subsequent purification process In this case, it is very difficult to separate and recover the metal from the precipitate. The sediment is low Phase separation is very difficult due to its high chemical concentration and its gelatinous nature. You. In the precipitation method, chemicals exceeding the amount required by stoichiometry (they are harmless In (If any), the metal is concentrated from the dilution water, The problem is that the total amount of substances to be done increases.   Other techniques used to recover metals from water include evaporation, ion exchange Replacement method, diaphragm separation method, and electrowinning method. The evaporation method uses water Is evaporated to condense the contaminated water. The main advantage of the evaporation method The point is that the metal concentrate can be reused as is at a certain concentration . The main drawback of the evaporation method is that it is an energy intensive method and its cost is That depends on the amount of water to be provided. The ion exchange method is related to metal removal and recovery. It is a well-established method, dating back to the 1950s. I The on-exchange method is used in the metal finishing industry for the production and reuse of deionized water. It has been used successfully to purify the plating and process baths used to perform the plating. The first disadvantage of the ion exchange method is that for continuous reuse, the ion exchange agent must be re-used. Lies in the fact that they must be born. Otherwise this method is extremely expensive Becomes However, this method is less expensive than the precipitation method due to the cost of regenerative chemicals. It is still uneconomical. As with the precipitation method, the total amount of sludge exceeds the stoichiometric amount. The addition of regenerating chemicals results in an increase. Another disadvantage of this method is It is generally non-selective and the recovery of certain metals is difficult. Specific gold Some genus-selective ion exchangers are commercially available. But this one The method requires a greater amount of regenerative chemicals.   Electrodialysis and reverse osmosis membranes are commercially available for pollution control and resource recovery . These are both sensitive to high operating costs and initial investment, membrane fouling and degradation. Economical achievement of a high concentration of brine, being non-selective, Metal recovery because it is difficult to recover the metal Not widely used for yield. The electrowinning method produces an electrical potential difference. Accompanied by feeding the spout and recovering the metal. The main application is from plating wash water Of cadmium and copper from immersion liquid of waste printed circuit boards. This way Inefficiency and the attendant economics are limited to applications with relatively concentrated solutions. You.   In summary, most of the methods used to treat metal-containing water have one of the following disadvantages: Or more: high operating costs, non-selective metal removal; use of processing chemicals Additional sludge beyond the stoichiometric requirements must be generated and disposed of. I have to.   Rikka and Tanaka "Phase Transition in Ionic Gels Indu ced by Copper Complexation ", Macromolecules, 18,83-85,1985, is acrylic A gel, a copolymer of amide and acrylic acid, has been developed. Gel is the target substance (copper⁺² Swelled with the solution of (ion) and increased as the acrylic acid content increased. This is because the gel acrylic acid absorbs copper ions as the gel volume expands. It indicates that Cu⁺²At higher concentrations, this dependence is reversed. The gel shrank as the acrylic acid content increased. Gel volume response The stimulant for is the target substance (copper) in solution. This gel system is used for gel regeneration That is, the stimulant that returns the gel to a collapsed state that can bind to the target It is impractical because of it. The gels and methods of the present invention have relatively low target substance concentrations. Rikka / Tanaka gels cause a volume response because they are used efficiently in certain cases In order to scrub, the concentration of the target substance must be changed, so it cannot be used. do not come. The acrylamide-acrylic acid gel used by Rikka and Tanaka , Not only because of the reasons listed above, but also because of the inability to regenerate with low-cost stimulants It is not suitable for removing heavy metals from groundwater having a high concentration, for example, 0.1-1M.                                 Summary of the Invention   The present invention relates to a responsive polymer gel having a unique property, and a target substance is removed from the environment. Can be used for selective removal. One embodiment of the gel of the present invention is a tertiary gel. An original reversible responsive polymer gel comprising at least two bonds to the target substance It has a joining portion, and the joining portion comes close to each other and forms a binding site In some cases, the bond is capable of binding the target substance. This joint connects with the gel This gel undergoes reversible volume contraction and expansion in response to changes in environmental conditions. A responsive polymer component that is adapted to run. The polymer gel component expands in volume It has a phase transition threshold for volume contraction that is different from the phase transition threshold for expansion. At the phase transition threshold The binding site binds to the target substance when the rimer gel contracts The joints should be close enough to each other and to the target material to be positioned In addition, a responsive gel has been constructed. The polymer expands to an expanded state at the phase transition threshold When inflated, the joints are disconnected from each other and from the target material. Target substance concentration Due to the different degrees and the different target substance types, the two phase transition thresholds are Most preferably, they are different from each other.   Responsive polymer components include ionic bonds, hydrophobic bonds, hydrogen bonds and van der Waals Subject to volume changes mainly due to interaction, including Ruth binding, and responsiveness The polymer component is, for example, N-isopropylacrylamide. Is, for example, acrylic acid. The most preferred polymer gel of the present invention is Reversibly respond to temperature changes, and the gel has at least two different Having a phase transition temperature threshold.   A method for removing a target substance from the environment is to contact the polymer gel of the present invention with the target substance. And wherein the target substance has binding affinity at the binding site; Allowing the gel to enter a contracted state, wherein the joints are connected to each other and the target substance Forms a binding site that binds to the target substance by being sufficiently close to Is included. A further method of removing target substances from environments containing target substances is Contacting the margel with the target substance to be recovered; changing the temperature of the gel to Causing the gel to form a binding site by causing volume shrinkage of the gel, Binds the target substance to the gel. Once bonded, the volume expansion of the gel Change the temperature of the gel again to cause it. Release the target substance from the gel To regenerate the gel. Preferably, the temperature changing step and the regeneration step are substantially Is to happen at the same time. The most preferred means of gel regeneration is to combine the gel with the eluent. Contact.   The gel of the present invention selects a selected target substance from a solution of the target substance and another target substance. It can be selectively removed. This method allows gels to be more Target substances with a lower phase transition threshold in the presence of the target substance and other target substances. Contacting with the inventive polymer gel. Next, the environmental conditions of the gel are two goals The condition is changed to an intermediate condition of the phase transition threshold of the substance. The gel is changed to a contracted state, The bond is to bind each other and the two target substances with the lower phase transition threshold. Get close enough to the target substance. In a preferred embodiment, the step of changing the environmental conditions Changing the temperature of the fuel cell.   The responsive gels described herein remove target substances from the environment in which they are used. Has the potential to overcome many of the problems associated with the conventional methods used to ing. They are: (i) stimuli that do not themselves produce waste such as heat and light The ability to be regenerated by substances; (ii) the ability to be regenerated by inexpensive stimulants; (iii) ) Ability to be regenerated by small changes in external stimulants; (iv) reversibility; (v) target substance concentration. Ability to remove different target substances over a wide range of degrees; (vi) by gel regeneration While producing a highly concentrated target solution, remove the target from the solution. And the ability to reduce the concentration of the target substance solution; (vii) making one target substance the other (Viii) a wide range of harmless substances such as other inorganic salts Ability to remove target material from solution; and (ix) inexpensive to manufacture. Due to its unique properties, it has the potential to significantly reduce energy consumption.                               BRIEF DESCRIPTION OF THE FIGURES   Figure 1 shows that one is at the base concentration of the target substance (M = M_O), And one is At higher elution concentrations (M^recover) Target with gel with two phase transition thresholds 5 is a schematic illustration of substance binding and elution.   FIG. 2 shows the degree of swelling of NIPA / Acc (500 mM / 200 mM) copolymer gel⁺² It is a graph which made ion a function.   FIG. 3 shows the degree of swelling of the NIPA / Acc (500 mM / 200 mM) copolymer gel, It is a graph which made the kind of ion a function.   FIG. 4 shows the degree of swelling of the NIPA / AAm / Acc (648 mM / 8 mM / 8 mM) copolymer gel. And 1 mM calcium and copper ions as a function.   Figure 5 shows NIPA when the target substance concentration was 10 micromolar copper or calcium. 5 illustrates the swelling response of a / Acc (500 mM / 200 mM) copolymer gel.   FIG. 6 shows the degree of swelling of the NIPA / Acc (500 mM / 200 mM) copolymer gel at the same concentration of 3%. Different types of divalent metal ions (Cu⁺², Ca⁺², Fe⁺²) As a function.   FIG. 7 shows 0,10 uM of a copolymer gel made from NIPA (500 mM) and AAc (200 mM). , And the degree of swelling with 15 mM copper ions.   FIG. 8 shows the degree of swelling of NIPA-AAc gel as a function of target substance concentration at 35 ° C. Is shown.   FIG. 9 shows the degree of swelling of NIPA-AAc gel as a function of target substance concentration at 40 ° C. Is shown.   FIG. 10 shows the degree of swelling of the NIPA-AAc-AAm gel (188 mM / 256 mM / 256 mM) with the target substance concentration. Shown as a function of temperature at varying degrees (0 μM, 6.8 μM, and 50 μM).                               Detailed description of the invention Gel system     General considerations   The polymer gel of the present invention is a molecular machine, preferably a monomer building block. The combination of the two groups is included as a check component. However, dual gender It may be a single monomer building block with quality. One building block component May be ionized, and this is the part that binds to the target substance. The other structure The building block component contains a target material binding site, as described in further detail below. It allows the rimmer to undergo reversible volume contraction and expansion.   An important feature of the present invention is that both components work in concert with each other. Landmark The polymer bond is incorporated into the gel by polymerizing this monomer component. Therefore, it is bonded to the polymer and dispersed in the polymer. at least When the two target substance bonds attach to locations within the expanded gel, the gel is at least Could also form a single “binding site”. Combine target substances To do this, at least two target substance bonds are required.   That is, the target substance most preferably binds to the binding site only when the gel shrinks. I do. This is because the contraction of the gel causes the two bonds and the target substance to be sufficiently close to each other. Because two fingers are just approaching when picking an object. It is something that must be done. By selecting the monomer linkage, the poly It allows for practical adjustment of mer affinity and selectivity of target substances. In a sense, gel Consists of “muscles” and “tweezers” that recognize the target substance. “Pi "Set" can catch target material when "muscle" closes "tweezers" Yes, and release the target substance when the "muscle" opens it.   The proximity of the joints and the target material, and thus the formation of the gel binding sites, It can be adjusted by building block components that respond volumetrically. The gel is between the two endpoints For example, it can physically expand and contract between a contracted state and an expanded state. Hence the gel When is in a contracted state, a binding site is formed to bind the target molecule. But, When the gel is in its expanded state, the two or more joints are physically separated, Since the target substance is released from the binding, the binding affinity at the binding site is Can be weakened. This conversion is preferably reversible. The advantage of this configuration is that Slight changes in environmental conditions release the target material and recycle the polymer gel. The advantage is that the binding affinity can be reduced for use as a macromolecule.   The gel of the present invention is an intermediate substance between a liquid and a solid state. It consists of a crosslinked network. The term “gel” refers to a matrix in which polymer chains are interconnected. Three-dimensionally crosslinked polymer network containing liquid solvent captured by Rix Say. The term “polymer network” describes a three-dimensional, intertwined network. Refers to a polymer that has been crosslinked to form The term “gel” refers more specifically to the sample Liquid and solid states containing enough solvent molecules to cause microscopic changes in the size of Refers to the intermediate polymer network. This term also refers to substantially It is meant to include the gel in a "dry" state where all solvent has been removed. This term is Are primarily operational definitions. One definition of this term is that the mass of gel When a certain low value is reached in a drying oven or drying oven.   Preferred gels are “reversible responsive”, ie, when an environmental change occurs, The modification acts so that all gels or their components undergo a reversible volume change. Get The device responds to changes in environmental conditions and undergoes a reversible volume change of at least 20 percent. Are preferred. This allows the gel to be filled with less liquid or dry Expands from a full state to a state filled with more liquid, or is filled with more liquid. It shrinks from a filled state to a state filled with less liquid. Reversible volume change is two With a transition between two equilibrium states (ie, swelling and contraction).   Gels can be manufactured in various forms, such as microporous gels. “ The term "microporous" refers to a continuous solid with a myriad of pores filled with fluid. Refers to the two-phase system of the body phase. “Microstructure” is the structure of a gel as defined herein (E.g., pores, voids, walls, etc.) with a scanning electron microscope or other microscope Possible, sizes range from 0.01 to about 100 microns. The gel is 0.01 It is "microporous" with pores ranging in size from about 10 microns to about 10 microns. Pore Gels are typically called "open cell" gels when several are interconnected It is. If all the pores of the gel are interconnected, the gel is "Vicontinuous" Gels. The pores are separated (not interconnected) and If the compartment is independent of other pores, the gel is a "closed cell" gel. The invention embraces all such morphological forms and combinations of these forms.   The reversible volume change of the whole gel or its components may be continuous, or May be discontinuous. "Continuous" volume changes are relatively large changes in environmental conditions Characterized by a reversible change in volume (ie, shrinkage and swelling) caused by You. In addition, at least one stable near the transition point between the swollen and contracted states There is a volume.   The gels of the present invention can be used in extremely small environmental conditions, such as A reversible transition from swelling to contraction and back again Such "discontinuous" volume changes. Such reversible gels are In the textbook, hereinafter referred to as “phase change” gel, The increase is referred to as a “phase transition threshold” (eg, a phase transition temperature threshold; a phase transition pH threshold; Energy threshold). Having undergone a phase transition, incorporated herein by reference. (Tanaka et al.) Describe a synthetic polymer gel No. 4,732,930 or J. of Hirotsu et al. Chm. Phys. 87:15 July 19 See page 87. There is no stable volume between swelling and shrinking state in phase transition, And in theory, expansion and / or contraction is caused by infinitely small environmental changes. You. Gels undergoing a continuous phase transition have the same total volume as gels undergoing a discontinuous phase transition Can have change. The response phenomenon is that many permanent cross-links exist as gels Was observed in the resulting polymer network. Tanaka, Physical Review Letters , Vol.40, no.12, pp820-823, 1978 and Tanaka et al. (Tanaka et al.),Physlcal Revi ew Letters , Vol. 38, No. 14, pp771-774, 1977; Tanaka et al.,Physical Review Letters. 5 Vol. 45, pg. 1636, 1980; Ilavsky,Macromolecul e s , Vol. 15, pg. 782, 1982; Hrouz et al.,Europ.Polym.J.,Vol.17, p g.361, 1981; Ohmine et al.,J . Chm. Physics.VOL.8, pg.6379,198 4; Tanaka et al.,Science,Vol.218, pg.462,1982 and Ilabski etc. (Ilavsky et al.), Polm . Bull.Vol. 7, pg, 107, 1982; Gehrke, "Responsive  Gels: Voume Transitions II "; ed K. Dusek, Springer-Verlag , New York, pp. 81-144 (1993); Li et al.,Ann.Rev.Mat.Sci., 22: 243-277 ( 1992); and Yu et al., Enzyme Microb.Technol., 15: 354-366 (1993). Are all incorporated herein by reference.   At the molecular level, the preferred responsive gels are primarily temperature, pH, light, solvent concentration Sensitive to small changes in a limited repertoire of "trigger" conditions in an environment consisting of . At the macro level, any change in environmental conditions causes a specific change in volume Can be imposed on the gel as a trigger. These environmental conditions are not necessary. But can be similar to the trigger and, but are not limited to, temperature, Changes in electric field, photon energy, pH, solvent composition, biomolecule concentration, pressure, etc. including. The responsive gel of the present invention is a molecular "transducer" that converts environmental conditions into appropriate triggers. (transducer) ". For example, the dye may be responsive to temperature. It may be introduced into a gel. The dye absorbs light of the selected energy and the photoenergy Designed to convert heat to heat, which causes the gel to warm at the phase transition threshold. Can undergo volume changes caused by degrees. References herein A. Suzuki and T. Tanaka (A. Suzuki and T. Tanaka), Na ture: 346: 6282 (1990).   As mentioned above, a significant drawback of the Ricca and Tanaka prior art responsive gels is that It is the fact that their phase transition threshold is caused by the effect of the concentration of the target substance. The most preferred gels of the present invention have a temperature or temperature that is easily generated and easily controlled. Is designed to have a phase transition caused by environmental factors such as light.   Furthermore, the method of the invention described below is important in this regard, Relies, in part, on other properties of the gel that have not been valued; Transition of the phase transition threshold when the concentration changes and different targets at the same target substance concentration This is the transition of the phase transition threshold due to the substance. We aim at the phase transition threshold of temperature-responsive gel It was observed that the temperature changed to a lower temperature as the substance concentration increased (see Example 2 and FIG. 2). See). In particular, when the target substance is a polyvalent ion, the binding affinity of the target substance contracts. It is believed to provide additional attractive force between the individual polymers of the gel. Theoretical For additional discussion, see this additional document, which is incorporated herein by reference. T. et al. Suggested that an attractive force reduced the phase transition threshold of the contracted gel. Naka, D.J.Fillmore, S.T.Sun, I.Nio, G.A.Silslow, and A.Shah (T.Tanka, D.J.Fillmore, S-T.Sun, I.Nihio, G.A.Swislow, and A.Shar), Phys, Rev .Letters, 45, 1636 (1980) and U.S. Patent 5,100,933 (Tanaka et al.). No. The phase transition threshold of light, pH and solvent responsive gels will also depend on the target substance concentration. Is affected. A gate that responds to various triggers of the procedures and environments described herein. Due to the known general principles of the development of gels, those skilled in the art The effect of the concentration of the target substance can be routinely measured.   Another important property of the gel of the present invention is that at a certain target substance concentration, the temperature-responsive gel is used. The phase transition threshold of the target is to shift to lower temperatures by changing the type of target substance. (See FIGS. 3 and 4). The target substance of the gel of the target substance of the selected size and type The binding affinity for the junction is primarily the chemical bond formed between the target substance and the binding site. Depends on the nature of the This affects the attractive force generated between the polymers of the gel and Therefore, it also affects the phase transition threshold. I. Polymer structure     A. Responsive component   The first requirement of the gel of the invention is that all gels or their reversibly volume changing The components undergo a reversible volume change. This requirement for the entire gel Must meet. Nevertheless, at least one component is required The gel will contain a bond, as long as it gives the desired volume response properties.   For example, the gels of the present invention meet the requirements for volume responsiveness and target substance binding sites. It may be a single material, such as a single polymer network. But the gel Two or more components, each component having different required properties; It is most preferred to have What can be produced as a copolymer gel is, for example, , One component forms at least one binding site with a binding affinity for the target substance The other component has the property of a volume change corresponding to changes in environmental conditions. One thing.   Intrinsically bonded monomers can be polymerized in the presence of a volume changing gel. With this type of gel For example, poly-N-isopropylacrylamide [NIPA: “responsive component”] -/ Including poly (acrylic acid) [bonding part].   The gel is an interpenetrating polymer network = I PN). IPN is a volumetric solution such as poly-N-isopropylacrylamide. Can be responsive, such as acrylic acid to match the system of the present invention. You may couple | bond with a coupling | bond part. IPN is one polymer element of IPN that provides binding And can have both properties such that the other polymer element gives responsiveness . The polymer of the interpenetrating gel to be filled may be a natural polymer, a synthetic polymer, or Can include crosslinked natural and synthetic polymers.   The most preferred volume responsive component is polymerization of all or some, single and multifunctional groups. Can consist of polymers made by copolymerization / crosslinking of possible vinyl monomers it can. Exemplary gels include N-ethylacrylamide, N-n-propylacryl Amide, N-n-propylmethylacrylamide, N-isopropylacrylamide, N-n-isopropylmethylacrylamide and N-cyclopropylacrylamide Una N-alkylacrylamide (or similar N-alkylmethylacrylamide ) Derivatives or hydroxypropyl acrylate-co-acrylamide, dia Seton acrylamide-co-hydroxyethyl acrylate, hydroxypropyl Acrylate-co-hydroxyethyl acrylate, ethyl acrylamide, Cyclopropylacrylamide, n-propylacrylamide, and isopropyl Acrylate (or similar methacrylate) copolymer such as acrylamide Can be included.   The reversible volume changing component of the present invention may also comprise a hydrophobically modified polyethylene glycol. And similar polymers are associated by strong hydrophobic interactions. Vinyl alcohol)-poly (acrylic acid) or poly (ethylene glycol)- For cross-linking of linear polymers by physical interaction such as poly (methacrylic acid) Therefore it can be made. Charge complexation and hydrogen bonding can also cause gels that are particularly sensitive to pH. Works well. Examples are poly (ethylene glycol) -poly (methacrylic acid) or Poly (vinyl alcohol) -poly (acrylic acid).   Also preferred are natural polymerizable starting materials that can be chemically crosslinked. Book An exemplary polymer that can be advantageously used in accordance with the invention is cellulose. Includes alkyl-substituted cellulose derivatives such as ethers. A sample as an example Lulose ether is methyl cellulose, hydroxyethyl cellulose, hydro Xypropylmethylcellulose, hydroxypropylcellulose, Includes chill cellulose and hydroxymethyl cellulose. Poly (L-proline), And poly (valine-proline-glycine-X-glycine) [where X is tyrosine Phenylalanine, leucine, valine, glutamic acid, lysine, glycine, And other amino acids] can also be used. Polysaccharides include, for example, starches, sugars, Chin, and hyaluronic acid.   The change in volume of the gels described herein is due to intermolecular forces (generally, essentially electrostatic). Which act to expand the polymer network); and Competition between at least one attractive force acting to contract the network The result.   The change in volume of the gels of the present invention is primarily between the polymer chains themselves and the polymer chains. It is caused by four basic forces acting between the and the solvent. The power is: alone or Works in combination with ionic, hydrophobic, hydrogen bonding and van der Waals binding Interaction. Each of these interactions is dependent on the volume of the preferred gel of the invention. You can be independently responsible for change. These basic forces are specific Most strongly affected by triggers. Changes in solvent concentration are due to van der Waals interaction. Temperature changes have the strongest effect on hydrophobic interactions and hydrogen bonding. And changes in pH have the strongest effect on ionic interactions.   Thus, responsive gels whose volume change is dominated by ionic interactions are Poly (acrylic acid) / poly (methacrylamidopropyltrimethyl) Ammonium chloride [MAPTAC]) / water; poly (acrylic acid) / poly (alkyl) Amide) / water, and the like. Shi -Siegel and Firestone,Macromolecules, 21: 3254- See 3259 (1988). This type of gel is sensitive to pH and has a higher pH Shrinks when exposed to lower pH environments.   Responsive gel, whose volume change is governed by hydrogen bonds, shrinks with decreasing temperature (Ie, expands at higher temperatures) and poly (acrylic) as one polymer. Acid), poly (acrylamide) as other polymer, and water as liquid medium Interpenetrating polymer consisting of dimethylacrylamide and methacrylic acid Exemplified by a copolymer. Responsive gels whose volume change is governed by hydrophobic interactions When the temperature is increased, it shrinks (ie expands at lower temperatures) and the poly (N- Isopropylacrylamide (NIPA). US Patent 4,863,613 See issue No. In addition, NIPA can be used to provide photoresponsive Can be coupled to molecular "transducers" such as phyllin or chlorophyllin. Volume change Gels dominated by van der Waals interactions are dominated by hydrogen bonds Exhibits temperature responsiveness in the same manner as gels, and is exemplified by polyacrylamide.   Responsive gels can be formulated to be governed by one or more fundamental forces. it can. In particular, gels composed of positively and negatively charged group copolymers are Meet your requirements. In these gels, the polymer fragments undergo ionic interactions and And interact with each other by hydrogen bonds. The combination of these forces is This results in the existence of a responding phase. Annaka, incorporated herein by reference Annaka and Tanaka,Nature 335: 430-432 (1992). The equation quantitatively accounts for all of these aspects of volume change. References herein T. Tanaka, D.J.Fillmore, S-T. Sun, I. Niio, G.A. T.Tanaka, D.J.Fillmore, S-T.Sun, I.Nihio, G.A.Swilslo w, and A. Shar), Phys.Rev.Letters,455 1636 (1980) and U.S. Patent No.5,100,933 (Tanaka et al.). For another theoretical description, see S.H. H. Gehrke), Adv.Polymer Science 110: 81-144 (1993).   The molar percentage of the responsive component of the gel can vary over a wide range. However, any combination of components results in a gel having the properties described herein. Not necessarily. Between having too many responsive components and having insufficient binding , There is a specific proportion of the responsive component / coupling that is appropriate for the chosen application You. The preferred range of the responsive component is between about 400 mM to about 5M, while typically 5 Joints with no more than M are suitable. To synthesize a gel with a range of component values No need for more than routine experimentation.     B. Joint   Selective ion exchange where various affinity groups for the selected target substance have been identified. In the field of exchange, there is a huge database. Nevertheless, chosen When the affinity group is used indiscriminately as the monomer component of the target substance binding of the present invention, The resulting gel is simply a selective ion exchange whether the gel is in an expanded or contracted state. Works like a heat exchanger. In this case, each binding site is a single binding site and the volume of the gel expands. Expansion and / or contraction does not affect the affinity of the single bond for the target substance. However, since the binding requires at least two parts, the binding component is low. Both are divided into two parts (ie, iminodiacetic acid is divided into two parts, each having an acetic acid group). If the binding component is synthesized in such a way that Contraction and swelling are determined by the binding affinity of the gel for the target substance (which Which is a distinguishing feature from prior art gels). Therefore, selected Whether a binding site is suitable for the gel of the present invention simply means that the target substance / affinity binding pair is known. It is not clear from the fact. Using routine experiments, one skilled in the art can Can be easily split into two components (or chemically(de novo) ), They can polymerize to form a responsive gel, and the binding sites are reassembled. Gel collection required to determine if it is active when the gel shrinks Contraction and expansion can take place.   The connection is preferably:   (i) glutamic acid, lysine, ornithine, aspartic acid, cysteine, hiss Functional side chains such as thiidine, tyrosine, and some of p-aminophenylalanine are also available. One alpha-amino acid;   (ii) diaminodicarboxylic acids such as diaminopimelic acid;   (iii) iminodiacetic acid and its derivatives;   (iv) anthranilic acid and its derivatives;   (v) salicylic acid and its derivatives;   (vi) diethylene triamine Including a part of. The binding sites specific for lead, zinc and copper are preferably:   (i) Due to its versatility to complex a wide range of metals, including Cu, Zn and Pb, ethylene Amine tetraacetic acid (EDTA);   (ii) pyrogallol for affinity for lead; and   (iii) picolylamines due to their low pH effect   May be included. Carmo, incorporated herein by reference. (Calmon), ("Specific Ion Exchangers", in Ion Exchange for Pollution Cont rol (Calmon, C. and Gold, H., eds.), Vol. II, 151-154, CRC Press, Boca Raton, FL, 1 979; and "Specific and Chelate Exchangers: New Functional Polymers for Wa ter and Wastewater Treatment, "J.A.W.W.A., 73, 652-656, 1981.   Examples of preferred target substance binding sites (and their contracted binding site types) Means carboxylic acid (polycarboxylic acid), iminodiacetic acid (EDTA), isothiouronium (Polyisothiouronium), oximes (eg dimethylglyoxime), and And picrylamine (dipicrylamine). Most preferably, the bond is When the gel expands, it does not bind to the target substance, but when the gel contracts, It is to combine with a standard substance.   Preferred bonds are those that do not bind the target material in the expanded gel state. However, the individual joints are in a certain state in reality the joints are in a contracted state Has a much lower binding affinity, but also binds to the target substance to some extent in the expanded state I understand. The most common example is iminodiacetic acid, where the binding site is Get EDTA when reconstituted. Iminodiasetic is a divalent metal by itself It binds ions weakly, but once contracted, the resulting EDTA is particularly It binds certain divalent ions very strongly.   The joints are usually copolymerized during the polymerization of the gel into a responsive gel matrix or Crosslinked. Most preferably, when the responsive polymer component force is NIPA, Mers are synthesized with vinyl groups so that they are added to the NIPA matrix You.   The linkage is preferably about 1-100 moles per 100 monomer units in the polymer, More preferably, about 2-20 moles are added per 100 monomer units.   Biologically important molecules can also be separated by the gels and methods described herein. You. For example, the fragments of the variable region of the light and heavy immunoglobulin chains are Can be included as a connection. The production of antibodies and various fragments thereof is within the skill of the art. It is well within the scope of this work, and there is no known method for fixing these substances in a polymer. is there. The term "antibody" refers to monoclonal, polyclonal and target antibodies. Intended to include antibodies prepared by recombinant nucleic acid technology of high quality and selective responsiveness. To taste. The term “selective responsiveness” refers to the determination of one or more antigens of a target substance. Refers to an antibody that responds to a determinant and does not respond to other target substances. The antigenic determinant is usually amino Consist of chemically active surface groups of molecules such as acid or sugar side chains and specific It has specific three-dimensional structural characteristics as well as charge characteristics. As an example, the antibody is: (i) Immunize animals with target substances expressed by nuclei (eg, bacteria) or eukaryotic cells The cells should be able to use nucleotides for all or part of the target peptide. (Ii) all cells expressing all or part of the peptide Immunizing animals with vesicles Can be produced at the amino terminus (N-terminus) or at the carboxy terminus (C-terminus). Chosen In order to further improve the prospects for the production of To identify portions of the target substance that can be associated with increased immunogenicity in the amino acid sequence Can be analyzed. For example, the sequence of a peptide target may be a potentially immunogenic Computer analysis can be performed to identify surface epitopes. That's it Computer analysis includes antigen index, hydrophilicity, amphotropic helix or Including the creation of plots such as structural features like amphiphilic sheets Can be Preparation of monoclonal antibody binding portions directed to biologically relevant molecules All techniques used for antibody production by infinitely growing cell lines can be used. For example, the hybridoma technology initially developed by Kohler and Milstein (K ohler and Milstein, Nature, 256: 495-497, 1973), as well as trioma technology, human B- Cell hybridoma technology (Kozbor et al., Immunology Today, 4:72) and human EBV-hybridoma technology for producing clonal antibodies. Lallick etc.  et al.), U.S. Patent No. 5,001,065 and (Ladner et al. U.S. patents 4,704,69). 4 and 4,976,778) and references incorporated herein.   One skilled in the art will be able to obtain gels of the present invention that have suitable linkages for the selected target material. The other design rules required for this can be easily ascertained. Just as an example, The coordination chemistry of the metal ion has been established, and the copper ion has, for example, four carboxyls. Six electron-donating groups, such as oxygen in the hydroxyl group and nitrogen in the two amine groups. It is understood that it has six coordination positions to be created. For example, in this specification D.D.Ebbing, General Chemlstry (e d.M.S.Wrihtson), Houghton Mifflin Co., Boston, 1984.   Anions can also be suitable target substances. In this case, a suitable joint is It can contain amines, pyridines and amazines (see Calmon above) ).   Conventional methods of crosslinking monomer / polymer starting materials are known to be conventionally prepared. Used to synthesize gels of the invention from routine starting materials by routine experimentation it can. The polymerization reaction is carried out by a polymerization initiator such as ammonium persulfate, sodium metabisulfite. Or a free radical initiator such as azobisisobutyronitrile in a solvent, for example Started with dilution with or without dilution with water, lower alcohols, hydrocarbons, etc. You. However, solvents or polymerization initiators are also required to obtain polymerized products from the monomer mixture. Is not always an important factor and should be appropriately selected from conventionally known gelation methods Such a method is also applicable. The crosslinking reaction can also be triggered by ultraviolet or electron beam irradiation. Can wake up.   The polymers of the present invention can also be immobilized on a matrix or diaphragm. For example, the substance may be a support matrix, film or diaphragm, tube, hollow fiber, Solid fiber, molded object, solid particle, capsule, micelle or lipo It can be used for a some-like structure. In particular, N-isopropylacrylamide response It has been reported that the preparation of functional gel beads was based on emulsion or suspension polymerization. You. Hirose et al., Macrom, incorporated herein by reference. olecules 20,1342-4 (1987); U.S. Patent No. 5,183,879 to Yuasa et al. (to Yuasa et a l.); and Kojin Co., Ltd., Japanese Patent No. 90-260558 (to Kohjin Co., Ltd.). I want to be. In a typical suspension crosslinking method, an aqueous polymer suspension is a continuous organic suspension. Introduced into the product phase. The polymer suspension is not mixed in the continuous organic phase Must be something. As in the case of the cellulose ether polymer of the present invention If the polymer is present in the aqueous phase and is introduced into the continuous organic phase, The aqueous phase containing the polymer is known as “crosslinking”. Rocking or agitating within the continuous organic phase to disperse. The crosslinker is Crosslinks the polymer contained in the suspension. The crosslinking agent is preferably a difunctional or polyfunctional group A polymer in water droplets and two or more parts of a polymer chain Polymer network capable of reacting with water droplets, thereby retaining the size and shape of the water droplets To form a like structure. The crosslinking agent is added when or after the aqueous phase is dispersed in the continuous organic phase. May be added, but is typically added to the aqueous suspension before being dispersed in the organic phase . In addition, surfactants are used to stabilize water droplet formation and regulate water droplet size. May be added to the continuous organic phase. Antifoam, promotes water droplet formation and foams May be added to the aqueous solution in order to prevent this.     C. Crosslinking agent   An additional requirement for the practice of the present invention is that the gel is crosslinkable, preferably chemically It can be cross-linked. Reagent capable of reacting with two or more groups on a polymer Functions as a crosslinker and converts the polymer to a gel. Hydroxyl, amide , Polymers with responsive side groups such as carboxyls are easy to crosslink Note that the group is also a water-soluble group). It is convenient.   Suitable crosslinkers include acetaldehyde, formaldehyde, N, N'-methylene-bi Sacrylamide, ethylene glycol dimethacrylate, glycerin triac Glutaraldehyde, diglycidyl ether, such as lylate or divinylbenzene , Divinyl sulfone, diisocyanate, epichlorohydrin, phosphine chloride Olyl, trimetaphosphate, trimethylomelamine, polyacrolein and Includes cerium ion redox system. The concentration of the crosslinkable substance is From about 0.1 to about 10 mole percent based on some polymerizable material. The crosslinking agent is poly Results in partial cross-linking of the gel and changes in the mechanical strength, degree of swelling and It provides a means of adjusting the strength of the chemical trigger by varying the crosslink density. Preferred crosslinkers for polysaccharide volume changing components, especially cellulose ethers, are Dipic acid (Hexane diacid: HOOC (CH_Two)_FourCOOH), succinic acid (HOOC (CH_Two)_TwoCOOH), Malo Acid (propanedioic acid: CH_Two(COOH)_Two), Sebacic acid (decandioic acid: HOOC (CH_Two) COOH ), Glutaric acid (pentanedioic acid: HOOC (CH_Two)_ThreeCOOH) or 1,10-decanedicarbon It is a multifunctional carboxylic acid such as an acid. Dicals such as tartaric or malic acid Boxy hydroxy acids, as well as multifunctional compounds such as 1,2,3,4-butanetetracarboxylic acid The group carboxylic acids are also suitable. Unsaturated dibasic acids dry water-soluble polymers And / or used to physically crosslink by application of heat. For example, See U.S. Patent No. 3,379,720 (Reid,), which is incorporated herein by reference. I want to be illuminated.     D. catalyst   Free radical initiators such as ammonium persulfate or sodium metabisulfite A polymerization initiator is not usually required in the method of the present invention. However, hydroxide Thus, a catalyst that catalyzes the reaction with polyvinyl sulfone is required. II. How to selectively remove target substances     A. General considerations   The general procedure is to shrink a gel that has no bound target substance (I) placing the binding monomer group in close proximity to form the binding site; (Ii) increasing the strength of the affinity between the target substance and the binding site; and (iii) ) Desolvate the gel. The gel is then regenerated. This reduces the strength of the affinity binding This is achieved by placing it in its inflated state to reduce. Then from the active site to the target An eluent is added to displace the quality metal ions and dissolve the target substance in the gel. Replace with appropriate ions from syneresis.   In order to prove the principle of the present invention, a bonding monomer (acrylic acid (CH_Two= CHCOOH) = Acc ) And N-isopropylacrylamide (CH_Two= CHCONHCH (CH_Three)_Two= NIPA) Limmer was synthesized. See Example 1. Pure NIPA gel changes temperature When allowed to occur, a reversible volume change occurred at 33 ° C. in water. At least two acris The carboxyl group of the luic acid monomer can form a binding site with one divalent cation. You.   When copper ions of the target substance are added to the gel as a solution, the inside of the expanded polymer Was the same as the outside of the polymer. When the gel is shrunk, The target substance in the supernatant solution is shown to show that only the binding site appears when the Metal ions decreased. The supernatant solution is separated from the gel and the gel is Inflated. Very little target material was released from the gel.   In another experiment, the supernatant solution was separated from the gel and the gel was swollen in hydrochloric acid. I was sent. The concentration of the target substance in the acid is about 3-4 times the initial concentration of the target substance in the acid. Was. These experiments suggest the following principle: (i) The binding site is the gel in its expanded state In both cases, the target substance ions disappear when reaching Due to the need for a neutral state of charge, the swollen gel was still weakly attached. (ii) To replace the metal ion of the target substance,⁺Ions or other cations are eyes It must be replaced for the metal ion of the standard. Deionized water is very low Low concentration (10-⁸M) H⁺And this is the only Displace the target material metal from the joint. Hydrochloric acid, however, has its high ionic substitution  H⁺Contributes fast enough for concentration. Conversely, anionic target substances are hydroxy Elution with a base such as NaOH is required to provide the sill anion.   In other experiments, the phase transition temperature threshold gradually decreased when the target substance metal ion was added. Fell down. This decrease is due to extra polymer between the target material metal ions. It is due to gravity. The magnitude of the transition increased with the target substance concentration. Landmark The transition of the phase transition temperature threshold due to the change in the concentration of Can be used.   The method of target substance recovery from solution involves two basic operations: (i) eye recovery from solution Removal of the standards and their affinity binding into the contracted gel matrix; Elution (removal) and recovery of target material from Remove target material from solution and repeat The principle of recovery has been successfully proven, especially with respect to heavy metal recovery, and And the relationship between volume change and the triggering of environmental conditions (eg, temperature, light, pH). This is schematically illustrated in FIG. See Examples 1 and 2.   The operating method of the selected method is (a) the chemical and physical properties of the gel, and (b) Affinity binding of the target substance to the gel matrix and (c) Elution and recovery of the standard.     1. Sorption   An exemplary sorption process for a heavy metal target is as follows: (see FIG. 1): concentration M_O Assuming a solution of the target substance copper ions, and we concentrate copper ions and more High concentration M^RECOVERI want to collect it. The first phase transition threshold is M_OAt T_OAnd And the second threshold is M^RECOVERAt T^RECOVERIt is. Where target substance concentration T due to the lowering of the phase transition threshold due to the increase in^RECOVER<T_OIt is.   First, the swollen gel is subjected to some environmental conditions T_A(<T_O) In the first solution (M_O ); T^RECOVERIs T_OLower or equal. Copper ions are free from gel Spreading in and out of. Condition is T_B(Ie higher temperature, more light , Higher pH: where T^RECOVER<T_BAnd T_B> T_O). Gel is volumetric shrinkage And the active site is close to the binding site so that the gel is loaded with copper ions Formed. Solvent is expelled from the shrinking gel and the outside of the shrinking gel The supernatant solution is diluted and discarded or recovered as a more pure solvent Is done.     2. Elution / regeneration   The elution solution is then contacted with the gel and the solution concentration of the target After that, M^RECOVER(See FIG. 1). The condition is then T_C<Or = T_A<T^RECOVER<T_O(Ie lower the temperature, lower the light, pH Lower). The bound copper ions are eluted and the concentration M^RECOVER> M_OReleased in You. The elution solution contains cations (ie, HCl, NaCl), and the metal ions in the gel The cation (hydrogen or sodium ion) that replaces all is selected. Gel is now Or swelled and wet, without large amounts of metal ions, and as a regenerated gel I'm ready to go to the next cycle. The second cycle places the gel in the first solution Start with things. Figure 1 shows an example of shrinking as the size of environmental conditions increases However, gels can also be synthesized to show the opposite trend and from the scope of the invention Without deviating, the method of target substance extraction can be changed accordingly.   The difference in selectivity or affinity for the target substance molecule is represented by the difference in phase transition threshold. Is shown. See Example 3 and FIG. We assume that the phase transition threshold temperature is divalent The cations Ca, Co, Mg, and Mn proved to be almost the same. Substantive Great transitions were observed for the divalent cations Zn, Co, Fe, and Pb. Selective absorption Recovery is achieved by utilizing the difference in phase transition temperature threshold between different target materials it can. For example, we have Cu⁺²Ion to Ca⁺²I want to separate it from ions. gel By choosing the temperature of shrinkage midway between the phase transition threshold temperatures of calcium and copper (T_Cu <T_A<T_Ca), More Cu⁺²The ions accumulate in the contracted gel.   Such a choice is actually the same for NIPA / Acc / AAm (684 mM / 8 TnM / 8 mM) gel 684, respectively. Cu with concentration (1mM)⁺²And Ca⁺²Achieved by immersion in a solution of ions at 40 ° C Was. Please refer to FIG. In the range of concentrations at which the gel shrinks, There is great selectivity. Gel is Ca⁺²5 times more Cu than ions⁺²Absorbed ions . The selectivity was broken when the gel swelled.   Figure 5 shows the swelling response of NIPA / AAc (500 mM / 200 mM) when the target substance was 10 micromolar. Illustrate the answer. The phase transition is now discontinuous (the arrow is clear between the expanded and contracted states). Volume change without apparent intermediate volume state; black triangle: calcium ion and black Squares: compare copper ions). FIG. 5 also shows target substance concentration versus phase transition threshold. Illustrate the effects of At the phase transition temperature threshold of gel shrinkage in copper ions, the copper concentration of the gel is To be increased (solid square: down arrow), the same gel at the new higher copper concentration Compare with inflation (open square: upward arrow).   The volume response is significantly dependent on the type of metal ion. Determines the nature of the gel phase transition In experiments to do this, three different divalent metal ions were considered: Cu⁺², C a,⁺²And Fe⁺²(FIG. 6). The fact that they are different allows the identification of those ions. Made it easier. Gels appear to be least selective for calcium. These individual Ions are selectively selected by selecting appropriate temperatures for gel shrinkage and expansion. Can be collected. Example 1 Properties of Responsive Gel   The gel system consists of N-isopropylacrylamide (NIPA), acrylic acid (AAc), And acrylamide (AAm) copolymers. Polymer gels are mainly One is responsible for the volume phase transition, ie NIPA, and the other is the selective capture of metal ions And AAm and AAm. Ionic monomer (AAc and AAm) add non-ionic NIPA gel to pH, electric field and solution electrolyte. Be sensitive.   The total concentration of both groups was 700 mM, ie [NIPA] + [AAc] + [AAm] = 700 mM. fixed. These components are combined with 8.6 mM N, N'-methylenebisacrylamide (BIS). Crosslinked and deionized distilled water using standard methods of free radical copolymerization Was dissolved. The polymerization (gelling) is carried out at room temperature (20 ° C.) and 1.76 mM Initiated by the addition of ammonium phosphate (APS) and 8.6 mM tetramethylethylene Assisted by the addition of rangeamine (TEMED). After gelation is complete, the gel remains Soaked in plenty of water to wash away existing chemicals. The wet gel is then drained to a 450 μm Squeezed through the screen.   This NIPA-based gel has the following properties: (i) at room temperature the gel swells State; (ii) when the temperature is increased above its phase transition temperature threshold, the matrix The gel shrinks, releasing all liquid in it (contains no ionic monomers ([AAc + [AAm] = 0) The phase transition temperature of the gel in distilled water is about 34 ° C.); When the reactive monomer was added to NIPA, the gel was ionized and the gel was exposed to distilled water. Phase transition temperature threshold increases above 34 ° C .; and (iv) the gel contains metals When placed in solution, the phase transition temperature threshold drops below and corresponds to that of distilled water. The transition of the phase transition temperature threshold monotonically increases with the metal concentration.   The advantage of these gels is that the negative charge of the gel is permanently attached to the gel matrix, The diffusion time of the metal into the pore structure is relatively high, in units of seconds for particles in microns That's fast. In the NIPA-AAc-AAm gel system, AAc and AAm bind Acts as a part and is covalently bound to the NIPA matrix.   The swelling or swelling of the gel as a function of the stimulus used to initiate the response of the gel The experimental setup for determining shrinkage is generally of diameter d_O(110 μm or 140 μm in diameter) This is a test tube containing a micropipette made by Lass. Pre-gel solution is a micropipette After being added to the gelling is completed inside the pipette. Glass at one end of pipette The gel is cut and removed from around the gel. Pipettes are regulated Suspended in a larger test tube. For example, the gel responds to temperature At times, the pipette is placed in a temperature controlled bath and the temperature is changed. thorn The diameter of the gel exposed to the aggressive substance is measured optically by a microscope and the temperature Recorded as a function. When determining the effect of copper concentration on gel diameter, a constant concentration ( And temperature) are run over the gel and the equilibrium gel diameter, d, is measured. Then the temperature is changed and the measurement is taken again. In some cases, the behavior of the gel is reversible The temperature is continuously increased and continuously decreased to ensure that .   Table 1 shows the composition of the gel for which the swelling curve was determined.   These gels show different swelling curves and except at concentrations of AAc below 64 mM. All gels show significant changes in phase transition temperature threshold as a function of target substance concentration Was. FIGS. 2 and 7 show five different copper ion concentrations: 0, 1 μM, 3 μM, 10 μM, and 15 μM. Shows the diameter of a copolymer gel made from NIPA (500 mM) and AAc (200 mM) in mM. You. As the copper ion concentration increased, there was a sharp decrease in the phase transition threshold, which It demonstrates the feasibility of performing copper ion removal from solution using these gels. volume The response becomes continuous at higher target substance concentrations (15 mM).   Figures 8 and 9 show the degree of swelling of NIPA-AAc gel as a function of target substance concentration. You. The temperature was fixed at 35 ° C. in FIG. 8 and at 40 ° C. in FIG. taller than At temperature (FIG. 9), the transition is discontinuous. FIG. 10 shows various target substance concentrations (0 μM, 6.8 swelling of NIPA-AAc-AAm gel (188 mM / 256 mM / 256 mM) in μM and 50 μM) The fit is shown as a function of temperature and shows a discontinuous transition only in distilled water. Example 2: Sorption of gel   The batch experiment was performed in the following manner. About 10 including NIPA-AAc (500mM: 200mM) Gram wet gel (including distilled water) contains 50 mL of copper chloride solution at various concentrations Put in a beaker. The dry weight of the gel is 0.1 gram. Solutions and gels are linked Stirred continuously. The solution is heated to 45-50 ° C, a few degrees above the gel phase transition temperature. And the gel shrank. Next, the metal concentration of the supernatant was determined by atomic absorption spectrophotometry. Measured. The supernatant is drawn off and slightly more than 20 ml of eluent (sodium chloride) Was added to the gel at a temperature below the phase transition temperature. The gel expands and copper ions Was released. The copper concentration of the supernatant was measured.   Test results showing the sorption of metals from solution are shown in Table 2.   The percentage of removal is the total amount of metal removed from solution by the gel, Consider first that the concentration has been diluted by the water in the gel first, Divided by the amount of metal found in   Table 2 shows that, except for zinc, the gel has more metal found in the pore volume of the gel. To show that AAc actually binds to the target metal in solution. Remove Based on previous efficiencies, lead appears to be most strongly bound by AAc and then copper Or iron; zinc does not appear to be strongly bound by AAC. In the raw material solution The presence of sodium does not alienate the wicking of the gel to copper. For the selected gel In contrast, binding may be limited by the target substance concentration in the initial solution. Goal If the substance concentration is already too high in the raw solution, the gel will bind more gel You may not have the ability to do so. Between the capacity of the gel and the total amount of ions in the solution There is an optimal ratio that gives the best recovery. Example 3: Gel elution and regeneration   First, the target substance, 0.1 mM sodium salt solution bound by gel shrinkage Used to elute the gel. Less than 10 percent of the metal in the gel elutes Was. Hydrochloric acid was then used to elute the gel. The test results are shown in Table 3.   In general, most of the metal bound on the gel matrix is eluted with HCl. Recovered, and the concentration of metals in the wash solution was about three times higher than that of the stock solution . Utility / application   The application of this technology is to prevent pollution, especially to remove metal ions and wastewater and metal plating. Includes recovery / concentration of valuable metal ions from process solutions such as immersion liquids. Precious metal In the ionic form, the salt or other salt thereof can be prepared using the gel or method of the present invention. It can be conveniently separated from metal compounds. Metals are gold, silver, platinum, palladium, iris Including indium, osmium, rhodium and ruthenium. The term “salt” is acceptable Soluble salts (including their solvated simple and complex ions) and insoluble salts and metals Intended to include esters, "compound" includes soluble and insoluble oxides, Including a combination of metal and non-metal, such as gold telluride or silver arsenide. Intended. Typical noble metal simple / complex ions are silver nitratoplatinate, perylene Silver diamine oxalate, platinum monohydroxychloric acid, platinum tetramine Acid salt (II), chloride hydrate, nitratopentamine platinum nitrate, gold chloride, silver nitrate , And zinc tetramine perrhenate. The ions to be processed are ores, Includes industrial waste and concentrates obtained from water purification or ore processing. For example, On forms include mining of free metals, metal salts or metal compounds; jewelry processing; plating solutions; Photographic film production and development; and from heavy metal contamination processing. Metal cation Typical salts that come out of the solution are fluorantimonate, fluotitanate, Get Ammonium rumanate, potassium metavanadate, and cobalt nitrate , Cyanocuprate, ferrate, metagermanate heptahydrate, iron oxalate, molybdenum Denate, tungstate, and sodium silicotungstate dodecahydrate including. Metal cation raw materials are made from smelting, free metal, metal salts, or metal compounds. Results from manufacturing processes, plating solutions, and heavy metal contamination treatments.   Other applications include removal of calcium from hard water and removal of sodium or hydrogen. Water softening replaced; nitrate found in drinking water sources (generated from fertilizer) Of negatively charged ions, such as, from solution; contamination control; medicine and recombinant D Biological separation in NA production process, especially from medium to dilute bouillon Purification of product; purification is very highly selective for product and similar chemistry To remove impurities of physical function and physical properties. Equivalent   Various changes or modifications of the preferred embodiments can be made within the scope of the present invention. That should be understood. Therefore, all matters included in the above description are examples It is intended to be construed as illustrative and not in a limiting sense.

[Procedure amendment] [Submission date] April 16, 1997 [Content of amendment] [Fig. 1] FIG. 2 FIG. 3 FIG. 4 FIG. 5 FIG. 6 FIG. 7 FIG. 8 FIG. 9 FIG. 10

────────────────────────────────────────────────── ─── Continuation of front page    (72) Inventor English, Anthony E             British Columbia, Canada             I0N 2W, Roberts             Creek, General Delivery             Without ground) (72) King, Kathleen Rose             United States Massachusetts 01775,             Stowe, Farm Road 39 (72) Inventor Levi, Ronda Dalmage             United States Massachusetts 01748,             Hopkinton, Ash Street 53 (72) Inventor Masamune, Satoru             United States Massachusetts 02159,             Newton, Brooklyn Street             182 (72) Inventor Wang, Changnan             United States Massachusetts 02140,             Cambridge, Linge Avenue 402,             Apartments 135 [Continuation of summary] Target substances selected from other target substance solutions. A method of leaving is also described. In a preferred embodiment the environmental condition The procedure for changing the temperature does not involve changing the gel temperature. You.

Claims (1)

[Claims] 1. (i) at least two bonds to the target substance, wherein the at least When the two binding portions come close to each other to form a binding site, the at least Also two binding sites are capable of binding the target substance;   (ii) a responsive polymer component that binds to the at least two linkages, wherein Responsive polymer components reversibly shrink and expand in volume in response to changes in environmental conditions. The polymer gel has a phase transition threshold of swelling. The polymer gel has a contraction phase transition threshold different from that of the polymer gel at the phase transition threshold. When contracting, the binding site is reduced to allow the binding site to bind to the target substance. The two bonds are sufficiently close to each other and to the target substance, Expands to an expanded state at the phase transition threshold, at least two joints The responsive gels are constructed such that they are separated from each other and from the target substance;   A three-dimensional reversible responsive polymer gel having: 2. Due to differences in the concentration of the target material, the expansion and contraction phase transition thresholds differ from each other. The reversibly responsive polymer gel according to claim 1, 3. At a given target substance concentration, swelling and expansion may occur due to differences in the type of target substance. 2. The reversible responsive switch according to claim 1, wherein the phase transition thresholds of compression and contraction are different from each other. Lima gel. 4. The gel is in a contracted state and comprises a target substance bound to the contracted gel. 4. The reversibly responsive polymer gel according to item 3). 5. The responsive polymer component comprises an ionic bond, a hydrophobic bond, a hydrogen bond, and a fan. Selected primarily from the group consisting of Delwars bonds, primarily due to interactions 2. The reversibly responsive polymer gel according to claim 1, which undergoes a volume change. 6. The responsive polymer component is N-isopropylacrylamide. 2. The reversibly responsive polymer gel according to claim 1, wherein 7. Each of the at least two bonds is the same and the oxime, Crylic acid, iminodiacetic acid and its derivatives, salicylic acid and its derivatives, picolyl Amines, isothiouronium, anthranilic acid and its derivatives, Claims selected from the group consisting of amines and picrylamine 2. The reversibly responsive polymer gel according to item 1. 8. Each of the at least two bonds is the same, and 2. The composition of claim 1, wherein the composition is selected from the group consisting of gin and amazine. Reversible responsive polymer gel. 9. Each of the at least two junctions is identical and alpha- 2. The reversibly responsive polymer gel of claim 1 comprising a fragment of a amino acid. Ten. The alpha-amino acid is glutamic acid, lysine, ornithine, aspart Formic acid, cysteine, histidine, tyrosine, and p-aminophenylalanine 10. The reversible responsive polymer of claim 9, selected from the group consisting of: -Gel. 11． The responsive polymer and the linkage are in a molar weight ratio of about 2.5 to 1. 7. The reversibly responsive polymer gel according to item 6 above. 12． The gel is reversibly responsive to changes in gel temperature and has two distinct phases. 4. The reversibly responsive polymer gel according to claim 3, having a transition temperature threshold. 13. Contacting the reversible responsive polymer gel according to claim 3 with a target substance. Wherein said target substance has a binding affinity for said binding site; and   Allowing the gel to enter a contracted state, wherein the at least two joints are Bonds that combine with the target substance by bringing them sufficiently close to each other and to the target substance Form a rank,   Of removing target substances from the environment, including 14. A target from which the reversible responsive polymer gel according to claim 3 is to be recovered. Contact with quality;   By altering the temperature of the gel to cause its volume shrinkage, Forming a joint site;   Altering the temperature of the gel to cause volume expansion of the gel; and   Regenerating the gel by releasing a target substance from the gel;   A method for removing a target substance from an environment containing the target substance. 15． Claim 14 wherein the step of changing the temperature and the step of regenerating occur substantially simultaneously. The method described in the section. 16． A gel regeneration step involves contacting the gel with an eluent and removing the target material from the swollen gel. 15. The method of claim 14, comprising replacing the quality. 17． A reversible responsive polymer gel according to claim 3, wherein the target substance and other Contacting the gel with the other material in the target material. Have a lower phase transition threshold than in the target material;   The environmental condition of the gel is set to a condition intermediate between the phase transition thresholds of the target substance and the other target substance. Change;   Allowing the gel to move into a contracted state, wherein the at least two joints are By bringing them sufficiently close to each other and to the target substance, one of the two Binds to the lower target material,   Selected target substances from target substance and solutions of other target substances. How to remove. 18． The contacting step involves contacting the gel with two different divalent cation target substances. 18. The method according to claim 17, comprising: 19. The step of changing the environmental condition includes changing a temperature of the gel. 17. The method according to item 17.