JP2005089353A - Method for controlling formation of clathrate compound using antifreeze protein - Google Patents
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Abstract
Description
本発明は、石油や天然ガスを輸送する際に輸送管中に生成し、閉塞事故を起こす原因となる包接化合物の生成を制御するため、水溶液中にタイプIIIの球状不凍タンパク質を溶解させることにより、生成過程を抑制する方法に関する。 The present invention dissolves type III globular antifreeze protein in an aqueous solution in order to control the production of clathrate compounds that are produced in transport pipes when oil and natural gas are transported and cause clogging accidents. The present invention relates to a method for suppressing the generation process.
包接化合物は、天然ガスなどの疎水性気体やフルオロカーボン、テトラヒドロフランのような溶剤等の分子(ゲスト分子と呼ぶ)と水(ホスト分子とも呼ばれる)とが低温高圧条件下で反応し、水(あるいは氷)への溶解度をはるかに超える高濃度にゲスト分子を包蔵した固体のことを言う。この物質は18世紀末に発見されているが、1950年代に高緯度地域の石油化学プラントにて輸送パイプが閉塞する事故が生じ、この原因物質として大きく注目された。その後こうした事故を防ぐため、生成を阻害する技術を中心に研究が進められてきた(例えば非特許文献1を参照)。 The clathrate compound is formed by reacting a hydrophobic gas such as natural gas or a molecule such as a solvent such as fluorocarbon or tetrahydrofuran (called a guest molecule) with water (also called a host molecule) under low temperature and high pressure conditions, and water (or A solid containing guest molecules at a concentration far exceeding the solubility in ice. This material was discovered at the end of the 18th century, but in the 1950s, an accident occurred in a high-latitude petrochemical plant where a transportation pipe was blocked, and it attracted much attention as the causative agent. Since then, in order to prevent such accidents, research has been conducted focusing on technology that inhibits generation (see, for example, Non-Patent Document 1).
包接化合物は、主として2種類の結晶構造をとる。ひとつはメタンガスや炭酸ガス等と反応して生成するI型結晶(立方晶、単位胞長約1.2nm)で、もうひとつはテトラヒドロフランやプロパンガス等と反応して生成するII型結晶(立方晶、単位胞長約1.7nm)である。いずれも水分子の作る格子からなるが、氷の結晶(六方晶、単位胞長a=0.45nm、c=0.74nm)とは異なる構造であり、水分子間距離もそれぞれ異なる。 Inclusion compounds mainly have two types of crystal structures. One is a type I crystal (cubic crystal, unit cell length of about 1.2 nm) produced by reaction with methane gas or carbon dioxide gas, and the other is a type II crystal (cubic crystal, produced by reaction with tetrahydrofuran, propane gas, etc.) Unit cell length is about 1.7 nm). Both are composed of lattices formed by water molecules, but have a different structure from ice crystals (hexagonal crystal, unit cell length a = 0.45nm, c = 0.74nm), and the distance between water molecules is also different.
化石燃料が次第に極地域、大水深地域に展開していく現在、包接化合物の生成抑制技術は古くて新しい技術として現在も研究対象となっている(例えば非特許文献2参照)。また海底の堆積物中や極域の永久凍土層中には、こうした化石燃料に付随するものばかりではない天然ガスが包接化合物の形で腑存していることが知られており、近年これらを天然ガス資源として開発するための開発研究が開始されている(例えば非特許文献3を参照)。さらに包接化合物の持つ高密度ゲスト分子包蔵性や生成・分解反応時のゲスト分子選択性等のユニークな特性を利用し、工業的に利用する技術についても検討が行われ始めている。例えば包接化合物を利用した混合ガスの分離技術としては、「ガスハイドレートを利用した混合ガスの分離および海水の淡水化方法」(特許文献1)や「同位体分離方法」(特許文献2)「希ガスの分離方法」(特許文献3)などが報告されており、従来から行われている混合ガス中の各成分の沸点差を利用した低温分離法、膜分離法、振動吸着分離法などの手法に比べて低エネルギー性、小設備性、低環境負荷性など優れた点を持つことが知られている。 As fossil fuels gradually develop in the polar regions and deep water regions, the clathrate compound formation suppression technology is an old and new technology that is still a subject of research (see Non-Patent Document 2, for example). In addition, it is known that natural gas not only associated with these fossil fuels is present in the form of clathrate compounds in sediments on the seabed and in the permafrost in the polar region. Development research for developing natural gas as a natural gas resource has been started (see, for example, Non-Patent Document 3). Furthermore, industrially utilized techniques have begun to be studied using the unique properties of the inclusion compound, such as high density guest molecule inclusion and guest molecule selectivity during generation and decomposition reactions. For example, as a separation technique of a mixed gas using an inclusion compound, “a separation method of a mixed gas and desalination of seawater using a gas hydrate” (Patent Document 1) and “isotope separation method” (Patent Document 2) The “rare gas separation method” (Patent Document 3) has been reported, and the conventional low-temperature separation method, membrane separation method, vibration adsorption separation method, etc. using the boiling point difference of each component in the mixed gas have been reported. Compared to this method, it is known to have excellent points such as low energy, small equipment, and low environmental load.
これらの技術開発において、包接化合物の生成・分解挙動を制御することは、きわめて重要である。特に前述したように、包接化合物の生成を抑制する技術についてはその応用範囲が広い。また包接化合物中の成長速度と、形成された包接化合物中のゲスト分子濃度との間には相関があり、必要な量のゲスト分子濃度をもつ包接化合物を得るためには、生成速度を制御する必要がある。 In these technological developments, it is extremely important to control the generation / decomposition behavior of inclusion compounds. In particular, as described above, the technology for suppressing the formation of clathrate compounds has a wide range of applications. In addition, there is a correlation between the growth rate in the inclusion compound and the concentration of the guest molecule in the formed inclusion compound. Need to control.
包接化合物の生成を抑制する技術としては、主として次のような2つの添加剤を用いる方法が主流である。ひとつは、包接化合物の平衡条件を抑制側にシフトさせる添加物(例えば海水やアルコールなど)を利用する方法であり、他のひとつは平衡条件はほとんど変化させないが生成した結晶を抑制する添加物(PVPなどの化学薬品)を利用する方法である。いずれの方法も実際の生産において利用されてはいるが、前者の添加物は包接化合物の成長を抑制するわけではないので、系がシフトした平衡条件になってしまうと包接化合物の生成を抑制することができない。また後者の添加物は現在も開発が進められているが、環境への影響評価などが十分に行われておらず、経済的な問題も多い。 As a technique for suppressing the formation of clathrate compounds, the following two methods are mainly used. One is a method that uses an additive (for example, seawater or alcohol) that shifts the equilibrium condition of the clathrate compound to the inhibitory side, and the other is an additive that suppresses the crystals that are formed while the equilibrium condition is hardly changed. This is a method using (chemicals such as PVP). Although both methods are used in actual production, the former additive does not suppress the growth of the clathrate compound. It cannot be suppressed. The latter additive is still under development, but the environmental impact assessment has not been conducted sufficiently and there are many economic problems.
Uchida et al. (1999)(非特許文献4)は炭酸ガス包接化合物の生成実験を行い、純水−炭酸ガス界面で生成される膜状包接化合物の成長速度を調べた。その結果、炭酸ガス包接化合物の成長速度は、その圧力下で生成を開始する時の温度の平衡温度からのずれ(過冷却度DT)の関数であらわされることがわかった。さらにUchida et al. (2002) (非特許文献5)は、同様の実験をNaClを含む水溶液で行い、NaCl水溶液−炭酸ガス界面で生成する包接化合物は、純水系よりも成長速度が遅いこと、またNaCl濃度が高いほど成長速度抑制効果が大きいことを見出した。 Uchida et al. (1999) (Non-Patent Document 4) conducted a production experiment of a carbon dioxide clathrate compound and investigated the growth rate of the film-like clathrate compound produced at the pure water-carbon dioxide interface. As a result, it was found that the growth rate of the carbon dioxide clathrate compound was expressed as a function of the deviation from the equilibrium temperature (the degree of supercooling DT) at the start of generation under the pressure. Furthermore, Uchida et al. (2002) (Non-Patent Document 5) conducted a similar experiment with an aqueous solution containing NaCl, and that the inclusion compound produced at the NaCl aqueous solution-carbon dioxide interface has a slower growth rate than the pure water system. Further, it was found that the higher the NaCl concentration, the greater the growth rate suppression effect.
包接化合物と同様の水素化合物系結晶である氷の生成抑制技術として、近年天然に産出する不凍タンパク質の利用技術開発が活発になっている。この不凍タンパク質は氷の結晶面上に選択的に付着し、その結晶成長を抑制する働きを持つといわれている。しかしながらその機能は氷の結晶構造に限定されて評価されている。 In recent years, the development of technology for utilizing antifreeze proteins produced naturally has become active as a technology for suppressing the formation of ice, which is the same hydrogen compound crystal as the clathrate compound. This antifreeze protein is said to selectively adhere on the crystal surface of ice and to suppress the crystal growth. However, its function is limited to the crystal structure of ice.
最近Zengら(非特許文献6)は、タイプIに分類されるらせん状不凍タンパク質がテトロヒドロフランやプロパンガスなどのII型包接化合物の生成を抑制する可能性を指摘した。しかしながら効果がII型結晶構造に対してのみ示されており、天然ガスの主成分であるメタンガスや炭酸ガスと反応して生成するI型包接化合物結晶への有効性についての報告はない。 Recently, Zeng et al. (Non-Patent Document 6) pointed out the possibility that helical antifreeze proteins classified as type I suppress the formation of type II inclusion compounds such as tetrohydrofuran and propane gas. However, the effect is shown only for the type II crystal structure, and there is no report on the effectiveness for the type I clathrate crystal produced by reaction with methane gas or carbon dioxide, which are the main components of natural gas.
この発明は、石油や天然ガスを輸送する際に輸送管中に生成し、あるいは工業的に生成された包接化合物スラリーの輸送管中で成長を続け、閉塞事故を起こす原因となる包接化合物の生成過程を制御するため、天然に産出し環境調和性の高いタイプIIIの球状不凍タンパク質を水溶液中に微量に溶解させることにより、生成過程を抑制する方法を提供することである。 The present invention relates to an inclusion compound which is produced in a transportation pipe when transporting oil or natural gas, or continues to grow in a transportation pipe of an industrially produced inclusion compound slurry and causes a clogging accident. In order to control the production process, a method for suppressing the production process is provided by dissolving a small amount of naturally produced type III globular antifreeze protein in an aqueous solution.
本発明者は包接化合物の生成に用いる水溶液やゲスト分子と、形成された包接化合物の生成過程について鋭意研究を重ねた結果、氷の生成制御に効果があることが報告された不凍タンパク質水溶液から包接化合物を形成させる際、包接化合物相の生成安定条件に達してから結晶が発生するまでの時間(生成誘導期間)が純水を用いたときより長くなること、また結晶が発生してから成長する速度が純水を用いたときより遅くなることを見出し、水溶液中のタイプIIIの球状不凍タンパク質の濃度に変化させても同様の成果が得られるという知見に基づいて本発明を完成するに至った。 As a result of earnest research on the formation process of the formed clathrate compound with the aqueous solution and guest molecule used for the clathrate compound generation, the present inventor has been reported to be effective in controlling the formation of ice. When an clathrate is formed from an aqueous solution, the time from the time when the clathrate phase formation stability condition is reached until the crystal is generated (generation induction period) is longer than when pure water is used, and the crystal is generated. The present invention is based on the finding that the same growth rate can be obtained even when the concentration is changed to the concentration of the type III globular antifreeze protein in the aqueous solution. It came to complete.
すなわち、本発明は、水とガス体および/または溶剤等の液体とから包接化合物が形成されるに際し、タイプIIIの球状不凍タンパク質を添加することにより該包接化合物の形成を抑制する包接化合物の形成抑制方法である。 That is, the present invention relates to an inclusion that suppresses the formation of an inclusion compound by adding a type III globular antifreeze protein when the inclusion compound is formed from water and a liquid such as a gas body and / or a solvent. This is a method for suppressing the formation of a contact compound.
さらに、本発明は、ガス体および/または溶剤等の液体を輸送・貯蔵する際に、タイプIIIの球状不凍タンパク質を添加し包接化合物の形成を抑制することを特徴とするガス体および/または液体の輸送・貯蔵方法である。 Further, the present invention provides a gas body and / or a gas body and / or a liquid body, such as a solvent, which comprises adding a type III globular antifreeze protein to suppress the formation of an inclusion compound. Or a method for transporting and storing liquids.
さらに、本発明は、ガス体および/または溶剤等の液体を輸送管により輸送する方法において、タイプIIIの球状不凍タンパク質を添加し包接化合物の形成を抑制することにより輸送管の閉塞を防止する方法である。 Further, the present invention prevents the clogging of the transport pipe by adding a type III globular antifreeze protein and suppressing the formation of clathrate compounds in the method of transporting a liquid such as a gas body and / or a solvent by the transport pipe. It is a method to do.
上記それぞれの方法において、ガス体としては、メタンやプロパンなどの炭化水素ガス、炭酸ガスや硫化水素などの酸性ガス、及びネオンやクリプトンなどの希ガスが挙げられ、液体としては、HFC-32やHFC-134aなどのフルオロカーボン、テトラヒドロフランやアセトンなどの有機溶剤、または上記ガス体との共存下で包接化合物を生成するメチルシクロヘキサンやイソペンタンなどの有機溶剤や液体炭化水素が挙げられる。 In each of the above methods, examples of the gas body include hydrocarbon gases such as methane and propane, acidic gases such as carbon dioxide and hydrogen sulfide, and rare gases such as neon and krypton, and examples of the liquid include HFC-32 and Examples include fluorocarbons such as HFC-134a, organic solvents such as tetrahydrofuran and acetone, or organic solvents such as methylcyclohexane and isopentane that form an inclusion compound in the presence of the above gas body, and liquid hydrocarbons.
また、使用するタイプIIIの球状不凍タンパク質は水溶液中での濃度が0.01 mg/mlで有効であり、上限の濃度については特に限定はない。 The type III globular antifreeze protein used is effective at a concentration of 0.01 mg / ml in an aqueous solution, and the upper limit concentration is not particularly limited.
本発明により、水とガス体および/または溶剤等の液体から包接化合物が形成されるに際し、これらにタイプIIIの球状不凍タンパク質を添加することにより該包接化合物の形成を抑制することができた。そして、この方法をガス体および/または溶剤等の液体を輸送管により輸送する方法において適用することにより包接化合物の形成による輸送管等の閉塞を防止することができた。 According to the present invention, when an inclusion compound is formed from water and a liquid such as a gas body and / or a solvent, the formation of the inclusion compound can be suppressed by adding a type III globular antifreeze protein thereto. did it. By applying this method to a method of transporting a liquid such as a gas body and / or a solvent through a transport pipe, it was possible to prevent the transport pipe or the like from being blocked due to the formation of an inclusion compound.
本発明の方法は、包接化合物を生成し得るゲスト分子相(気相または液相)と水とを反応させる際に、包接化合物を形成し得る条件下においても生成反応が起こらない時間(生成誘導期間)を長くすることで包接化合物の生成を抑制する技術、及び生成反応が起きた後包接化合物が成長する速度を低下させることで包接化合物の生成を抑制する技術とからなっている。ここでいう不凍タンパク質とは、不凍能力を有するタンパク質のことである。不凍タンパク質はそのアミノ酸配列および分子形状によってタイプIからIVの4種類に分類される(図1参照)。図1において、(a)はタイプIの構造(一本のアルファヘリックス構造)を、(b)はタイプIIの構造(ジスルフィド結合を5つ有する、C-typeレクチンに類似した構造)を、(c)はタイプIIIの構造(ベータシート構造に富んだ球状構造)をそれぞれ示す。 In the method of the present invention, when a guest molecular phase (gas phase or liquid phase) capable of forming an inclusion compound is reacted with water, a time during which no generation reaction occurs even under conditions where an inclusion compound can be formed ( A technology that suppresses the generation of the clathrate compound by lengthening the generation induction period) and a technology that suppresses the generation of the clathrate compound by reducing the growth rate of the clathrate compound after the generation reaction has occurred. ing. The antifreeze protein here is a protein having antifreeze ability. Antifreeze proteins are classified into four types, type I to IV, according to their amino acid sequences and molecular shapes (see FIG. 1). In FIG. 1, (a) shows a type I structure (single alpha helix structure), (b) shows a type II structure (a structure similar to a C-type lectin having five disulfide bonds). c) shows a type III structure (spherical structure rich in beta sheet structure).
タイプIは分子量3300〜4500で、アミノ酸配列にはアラニンを多く含むという特徴をもつ。代表的なアミノ酸配列としてはカレイの一種winter flounder由来の配列が挙げられる(非特許文献7)。分子形状は図1(a)に示すように、1本のアルファへリックス構造をとる。タイプIIは分子量11000〜24000で、アミノ酸配列にはシステインを多く含むという特徴をもつ。代表的なアミノ酸配列としてはカジカの一種sea raven由来の配列が挙げられる(非特許文献8)。分子形状は図1(b)に示すように、ジスルフィド結合を5つ有し、C-typeレクチンに類似した構造をとる。タイプIIIは分子量6500〜14000で、アミノ酸配列の特徴は特に無い。代表的なアミノ酸配列としてはゲンゲの一種ocean pout由来配列が挙げられる(非特許文献9)。分子形状は図1(c)に示すように、ベータシート構造に富んだ球状構造をとる。タイプIVは分子量10000で、アミノ酸配列にはグルタミンを多く含むという特徴をもつ。代表的なアミノ酸配列としてはカジカの一種longhorn sculpin由来の配列が挙げられる(非特許文献10)。分子形状の特徴は4本のアルファへリックスバンドル構造と予測されているが、まだ構造解析されておらず、タイプI〜IIIに示すような明確な分子形状はまだ決定されていない。本発明で用いている不凍タンパク質は、タイプIIIに分類される球状タンパク質である。実施例で使用したタイプIIIの不凍タンパク質は、配列表の配列番号1で表されるアミノ酸配列を有する。ただし本発明でもたらされる効果は、当該アミノ酸配列に限定されるものではなく、広くタイプIIIの不凍タンパク質に当てはまるものである。また本発明においては凍結といっても氷化ではなく、包接化合物の生成を意味し、通常、不凍タンパク質(Antifreeze Protein, AFPと略記する)という名称を用いる。なお、本明細書においては、不凍タンパク質はタイプIIIの球状不凍タンパク質であることから文脈に応じてAFP(III)と略記する。 Type I has a molecular weight of 3300 to 4500 and has a characteristic that the amino acid sequence contains a large amount of alanine. Representative amino acid sequences include sequences derived from winter flounder, a kind of flatfish (Non-patent Document 7). As shown in FIG. 1 (a), the molecular shape has one alpha helix structure. Type II has a molecular weight of 11,000 to 24000, and has an amino acid sequence that is rich in cysteine. A typical amino acid sequence includes a sequence derived from sea raven, a kind of swordfish (Non-patent Document 8). As shown in FIG. 1 (b), the molecular shape has five disulfide bonds and has a structure similar to C-type lectin. Type III has a molecular weight of 6500 to 14000 and no particular amino acid sequence characteristics. A representative amino acid sequence includes a sequence derived from ocean pout, which is a kind of spider (Non-patent Document 9). As shown in FIG. 1 (c), the molecular shape is a spherical structure rich in beta sheet structure. Type IV has a molecular weight of 10,000 and has a characteristic that the amino acid sequence contains a lot of glutamine. A typical amino acid sequence is a sequence derived from longhorn sculpin, a kind of swordfish (Non-patent Document 10). Although the molecular shape is predicted to be a four alpha helix bundle structure, the structure has not yet been analyzed, and a clear molecular shape as shown in types I to III has not yet been determined. The antifreeze protein used in the present invention is a globular protein classified into type III. The type III antifreeze protein used in the examples has the amino acid sequence represented by SEQ ID NO: 1 in the sequence listing. However, the effects brought about by the present invention are not limited to the amino acid sequences, but are broadly applicable to type III antifreeze proteins. In the present invention, the term “freezing” does not mean icing but the generation of an inclusion compound, and the name of antifreeze protein (AFP) is usually used. In the present specification, since the antifreeze protein is a type III globular antifreeze protein, it is abbreviated as AFP (III) depending on the context.
本発明において用いられる包接化合物を生成することのできるゲスト分子としては、メタンガスのほか、エタンガス、プロパンガスなどの天然ガスの主成分である炭化水素気体や炭酸ガス、窒素ガス、酸素ガス、硫化水素等の小さな分子、キセノンガス、アルゴンガス、クリプトンガスなどの希ガスが挙げられる。またフルオロカーボンやアンモニウム塩水溶液などのゲスト分子は、上記のゲスト分子と異なり常圧条件で包接化合物を生成することができる。ここでは炭酸ガスを用いて実施したが、本発明に用いた手法は、上記に示したようなゲスト分子に対しても一般的に成立する。 As guest molecules capable of generating an inclusion compound used in the present invention, in addition to methane gas, hydrocarbon gas or carbon dioxide gas, which is a main component of natural gas such as ethane gas, propane gas, nitrogen gas, oxygen gas, sulfide Examples include small molecules such as hydrogen, and rare gases such as xenon gas, argon gas, and krypton gas. Further, unlike the guest molecules described above, guest molecules such as fluorocarbon and ammonium salt aqueous solution can form an inclusion compound under normal pressure conditions. Although carbon dioxide gas was used here, the method used in the present invention is generally valid for guest molecules as described above.
本発明において用いられる水は、通常脱イオン・脱気した蒸留水を用いるが、塩や塩基等の不純物が多少含まれていても一般的に成立する。ただし、含まれる不純物の種類や濃度により、包接化合物の生成平衡条件がシフトする場合もあるため、得られる気体や包接化合物中の成分比が異なってくることもある。 The water used in the present invention is usually deionized / degassed distilled water, but generally holds even if some impurities such as salts and bases are contained. However, since the formation equilibrium condition of the clathrate compound may shift depending on the type and concentration of impurities contained, the component ratio in the obtained gas or clathrate compound may differ.
反応させる条件は、用いるゲスト分子と純水との反応から予想される平衡条件より低温・高圧条件である。例えば炭酸ガスを用いた場合、純水と反応して生成される包接化合物の平衡圧力は、273.2Kにおいて約1.2MPaである。従ってこのガスを用いる実験では1.2MPa以上の範囲で行われる。温度範囲は圧力条件によって任意であるが、不凍タンパク質が氷中にほとんど溶存しないため水溶液との反応条件のもとで行う方が好ましく、273.2K以上で行う。 The reaction conditions are lower temperature and higher pressure conditions than the equilibrium conditions expected from the reaction between the guest molecules used and pure water. For example, when carbon dioxide gas is used, the equilibrium pressure of the clathrate compound produced by reaction with pure water is about 1.2 MPa at 273.2K. Therefore, experiments using this gas are performed in the range of 1.2 MPa or more. The temperature range is arbitrary depending on the pressure condition, but since the antifreeze protein is hardly dissolved in ice, it is preferable to perform the reaction under the reaction condition with an aqueous solution, and it is performed at 273.2K or more.
図2は本発明で使用した包接化合物生成観測装置である。この装置は炭酸ガス−純水(または塩水)系での包接化合物生成速度測定に用いられており(非特許文献5)不凍タンパク水溶液の効果を定量的に比較するために適している。一定量の水試料を高圧容器HV中に入れ全体を恒温槽TB中に入れて所定温度にする。その後HV中の空気を排気しボンベBよりゲスト分子試料をHV中へ導入し、所定圧力にする。そして恒温槽の設定を下げて包接化合物生成条件へ持っていく。温度・圧力が包接化合物生成条件になった時刻をゼロとし、温度・圧力を熱電対TC、圧力計PGで計測し、記録計Rにて記録する。 FIG. 2 shows the clathrate compound production observation apparatus used in the present invention. This apparatus is used for measuring the rate of inclusion compound formation in a carbon dioxide gas-pure water (or salt water) system (Non-Patent Document 5) and is suitable for quantitatively comparing the effects of antifreeze protein aqueous solutions. A fixed amount of water sample is put in a high-pressure vessel HV, and the whole is put in a thermostat TB to a predetermined temperature. After that, the air in the HV is exhausted, and the guest molecule sample is introduced into the HV from the cylinder B, and is set to a predetermined pressure. Then, the setting of the thermostatic chamber is lowered and brought to the inclusion compound generation conditions. The time when the temperature / pressure reaches the inclusion compound generation condition is set to zero, and the temperature / pressure is measured with the thermocouple TC and the pressure gauge PG, and is recorded with the recorder R.
包接化合物の生成の確認は、観測窓Wからの目視観測、および生成熱放出に伴う系の温度上昇によって行う。また包接化合物の成長速度は、観測窓から系内の様子を顕微鏡MSで観測し、その変化をビデオカメラVTRで録画して得られた画像を解析することで測定した。 Confirmation of the generation of the clathrate compound is performed by visual observation from the observation window W and by the temperature rise of the system accompanying the generated heat release. The growth rate of the clathrate compound was measured by observing the inside of the system with a microscope MS through an observation window and analyzing the image obtained by recording the change with a video camera VTR.
なお生成速度の測定実験の後、系内の温度を上昇させて包接化合物を分解させ、その分解温度を測定することによって不凍タンパク質水溶液による平衡条件の変化を確認した。 After the experiment for measuring the production rate, the temperature in the system was increased to decompose the inclusion compound, and the decomposition temperature was measured to confirm the change in the equilibrium condition due to the antifreeze protein aqueous solution.
従来AFPは氷の結晶構造に特有の大きさを持っており、そのため成長結晶面に選択的に配意して成長を抑制するというメカニズムが提案されていた。しかしながら本発明で適応した包接化合物は、氷の一種である水素結合系の結晶ではあるが、その結晶構造は氷と異なり、同じ機能を期待することができなかった。しかしながら本発明で示されたように、0.01 mg/ml(10-3 wt%)という微量な添加により大きな成長阻害効果が得られた。AFP自体は天然に産出される物質であるため、化学薬品で合成された形成抑制剤とは異なり環境調和性が高い。またNaClのように反応容器や輸送管等を腐食する恐れも少ないという利点を持っている。 Conventionally, AFP has a size unique to the crystal structure of ice, and therefore a mechanism has been proposed in which the growth is restrained by selectively giving consideration to the crystal plane of growth. However, the clathrate compound adapted in the present invention is a hydrogen-bonded crystal that is a kind of ice, but its crystal structure is different from ice, and the same function cannot be expected. However, as shown in the present invention, a large growth inhibitory effect was obtained by adding a small amount of 0.01 mg / ml (10 −3 wt%). Since AFP itself is a naturally produced substance, it is environmentally friendly, unlike formation inhibitors synthesized with chemicals. Moreover, it has the advantage that there is little possibility of corroding the reaction vessel and the transport pipe, etc. like NaCl.
平衡条件を変えずに核生成を抑制するという特徴を持つことから、結晶成長の駆動力を低く抑えることによって包接化合物の成長は著しく抑制されることとなる。また成長速度が抑制されるという特徴から、ゲスト分子−水界面で生成される膜状包接化合物の成長速度を抑制することになり、気・液接触型での反応装置系においても、生成速度の低下が観測されることが期待される。 Since the nucleation is suppressed without changing the equilibrium condition, the growth of the clathrate compound is remarkably suppressed by suppressing the driving force of crystal growth to a low level. In addition, the growth rate is suppressed, so the growth rate of the film inclusion compound generated at the guest molecule-water interface is suppressed. It is expected that a decrease will be observed.
以上のことから、本発明の以下の実施例で示した系のほか、同じ結晶構造を持つメタン包接化合物、異なる結晶構造を持つプロパン包接化合物や多くのフルオロカーボン包接化合物、準包接化合物と呼ばれるアンモニア塩を用いた包接化合物などの生成抑制剤として利用することが可能であることが示された。従ってこれらの包接化合物を利用する技術に関して、本発明による生成制御法を適応することが可能である。 From the above, in addition to the systems shown in the following examples of the present invention, methane clathrate compounds having the same crystal structure, propane clathrate compounds having different crystal structures, many fluorocarbon clathrate compounds, quasi clathrate compounds It was shown that it can be used as a production inhibitor for clathrate compounds using ammonia salts called as Therefore, the production control method according to the present invention can be applied to the technology using these clathrate compounds.
以下、本発明を実施例により具体的に説明する。但し、本発明の技術的範囲はこれら実施例に限定されるものではない。
脱イオン・脱気処理した蒸留水試料に配列番号1で示されるAFP(III)を所定の濃度で溶かした水溶液一滴(約0.5 cm3)を、図2に示す高圧反応容器HV(内容積約10 cm3)中に封入し、恒温槽TB中に入れる。その際、HV中に残存していた空気はバルブV2を開けて真空ポンプVPにて脱気する。脱気後バルブV2は閉じる。
Hereinafter, the present invention will be specifically described by way of examples. However, the technical scope of the present invention is not limited to these examples.
One drop (about 0.5 cm 3 ) of an aqueous solution in which AFP (III) represented by SEQ ID NO: 1 is dissolved in a deionized / degassed distilled water sample at a predetermined concentration is added to a high-pressure reaction vessel HV (with an internal volume of about Enclose in 10 cm 3 ) and place in a thermostatic chamber TB. At that time, the air remaining in the HV is deaerated by the vacuum pump VP by opening the valve V2. The valve V2 is closed after deaeration.
その後バルブV1を開けてボンベBより炭酸ガス試料をHV中へ導入し、所定圧力まで昇圧させた後、バルブV1を閉じる。そして温度圧力が所定条件になったことを確認した後、恒温槽TBの設定を下げて温度を所定温度にする。設定圧力における包接化合物生成温度に達した後、界面上に包接化合物が生成するのを観測する。 Thereafter, the valve V1 is opened, a carbon dioxide gas sample is introduced into the HV from the cylinder B, the pressure is increased to a predetermined pressure, and then the valve V1 is closed. Then, after confirming that the temperature and pressure are in a predetermined condition, the setting of the thermostatic chamber TB is lowered to bring the temperature to a predetermined temperature. After reaching the clathrate generation temperature at the set pressure, observe the clathrate compound formation on the interface.
図3はAFP(III)を0.01mg/ml溶かした水溶液を用いたときの、炭酸ガス包接化合物生成までの温度Tの時間t変化を示す。恒温槽温度は263.2Kに設定し、系内圧力は約5 MPaとした。このときの平衡温度は、分解実験の結果純水−炭酸ガス系で求められる包接化合物の平衡温度である約283.2Kと同じであった。 FIG. 3 shows the time t change of the temperature T until the formation of the carbon dioxide clathrate compound when an aqueous solution in which 0.01 mg / ml of AFP (III) is dissolved is used. The thermostatic chamber temperature was set to 263.2K, and the internal pressure was set to about 5 MPa. The equilibrium temperature at this time was the same as about 283.2 K which is the equilibrium temperature of the clathrate compound determined in the pure water-carbon dioxide system as a result of the decomposition experiment.
繰返し実験を行った結果、包接化合物は温度低下中には生成せず、ほとんどの場合設定温度(264.2 K)に達してからしばらく期間をおいて生成した。従って生成に必要な過冷却度DTは、約18Kとなった。また生成にかかる誘導期間は30〜120分と見積もられた。純水を用いたときの炭酸ガス包接水和物の生成条件は、同じ設定において過冷却度は10K以下であり、生成誘導期間は20分未満である(非特許文献4)。すなわちAFP添加により、炭酸ガス包接化合物の生成が著しく阻害されたことが示された。 As a result of repeated experiments, the clathrate compound was not produced during the temperature drop, and in most cases, it was produced after a while after reaching the set temperature (264.2 K). Therefore, the degree of supercooling DT required for generation was about 18K. The induction period for generation was estimated to be 30 to 120 minutes. The production conditions of carbon dioxide clathrate hydrate when using pure water are the same setting, the degree of supercooling is 10K or less, and the production induction period is less than 20 minutes (Non-Patent Document 4). That is, it was shown that the addition of AFP significantly inhibited the formation of carbon dioxide clathrate compounds.
Zengら(2003)(非特許文献6)の行ったタイプIに分類されるらせん状不凍タンパク質を用いた実験では、273.2Kに温度を保持した時に、24時間以内に核生成が起こる確率を持ってその性能を評価していた。従って本実施例と直接比較することは難しいが、不凍能力に濃度依存性があることと、本実施例で用いたAFP濃度がZengらの論文に記載された濃度より10倍以上希薄であることから、本発明で用いた不凍タンパク質の不凍能力のほうが勝っていると考えられる。 In an experiment using a spiral antifreeze protein classified as Type I conducted by Zeng et al. (2003) (Non-Patent Document 6), when the temperature was maintained at 273.2 K, the probability of nucleation occurring within 24 hours was I had to evaluate its performance. Therefore, it is difficult to make a direct comparison with this example, but the antifreeze capacity is concentration-dependent, and the AFP concentration used in this example is more than 10 times less than the concentration described in Zeng et al. Therefore, it is considered that the antifreeze ability of the antifreeze protein used in the present invention is superior.
図4は同じ実験系における、炭酸ガス包接化合物の成長速度を示す。横軸には過冷却度DTをとり、縦軸にはビデオ画像から求めた膜状包接化合物の成長速度vfをとった。図中点線は純水−炭酸ガス系における成長速度を示し(非特許文献4)、実線は濃度10wt%のNaCl水溶液−炭酸ガス系における成長速度の過冷却度依存性を示している(非特許文献5)これらの結果と比較すると、濃度0.01 mg/mlのAFP(III)水溶液−炭酸ガス系における成長速度は、海水の3倍以上の濃度のNaCl水溶液と同等の成長抑制効果を持つことが示唆された。AFPの濃度を重量パーセントで表すと10-3 wt%のオーダーとなるため、本発明で用いたAFPの包接化合物生成抑制効果はNaClの104倍であるといえる。 FIG. 4 shows the growth rate of the carbon dioxide clathrate compound in the same experimental system. The horizontal axis represents the degree of supercooling DT, and the vertical axis represents the growth rate v f of the film clathrate compound determined from the video image. In the figure, the dotted line indicates the growth rate in the pure water-carbon dioxide system (Non-Patent Document 4), and the solid line indicates the supercooling degree dependency of the growth rate in the 10 wt% NaCl aqueous solution-carbon dioxide system (Non-patent Document 4). Reference 5) Compared with these results, the growth rate in the 0.01 mg / ml AFP (III) aqueous solution-carbon dioxide system has the same growth-inhibiting effect as the NaCl aqueous solution with a concentration three times that of seawater. It was suggested. When the concentration of AFP is expressed in weight percent, it is on the order of 10 −3 wt%. Therefore, it can be said that the clathrate compound formation inhibitory effect of AFP used in the present invention is 10 4 times that of NaCl.
Zengら(2003)(非特許文献6)の行ったタイプIに分類されるらせん状不凍タンパク質を用いた実験では、プロパンガスの消費率からその性能を評価していた。従って本実施例と直接比較することは難しいが、生成速度抑制能力に極端な優位性が無いことと、本実施例で用いたAFP(III)濃度がZengらの論文(非特許文献6)に記載された濃度より100倍以上希薄であることから、本発明で用いたAFP(III)の生成速度抑制能力のほうが勝っていると考えられる。 In an experiment using a spiral antifreeze protein classified as Type I conducted by Zeng et al. (2003) (Non-Patent Document 6), the performance was evaluated from the consumption rate of propane gas. Therefore, although it is difficult to directly compare with this example, there is no extreme superiority in the production rate suppression capability, and the AFP (III) concentration used in this example is described in a paper by Zeng et al. Since it is more than 100 times dilute from the stated concentration, it is considered that the ability to suppress the production rate of AFP (III) used in the present invention is superior.
実施例1と同様にして、AFP(III)の濃度を0.1 mg/ml〜1 mg/mlにした水溶液と炭酸ガスとを試料として用いた実験を行い、同様な条件下で炭酸ガス包接化合物の生成誘導期間が純水−炭酸ガス系に比べて長くなり、成長速度もAFP(III)濃度0.01 mg/mlの場合とほぼ同じくらいに抑制された。従って、AFP(III)の濃度による効果の変化は、濃度の違いほど大きくはなかった。 In the same manner as in Example 1, an experiment was conducted using an aqueous solution having a concentration of AFP (III) of 0.1 mg / ml to 1 mg / ml and carbon dioxide as a sample. The generation induction period was longer than that of the pure water-carbon dioxide system, and the growth rate was suppressed to about the same level as when the AFP (III) concentration was 0.01 mg / ml. Therefore, the change in effect due to the concentration of AFP (III) was not as great as the difference in concentration.
B:ガス用の高圧ボンベ
V1,V2:弁
HV:高圧反応容器
TB:恒温槽
SM:水溶液(試料)
PG:圧力計
TC:温度計
R:記録計
VP:真空ポンプ
W:観測窓
MS:顕微鏡
VHS:ビデオカメラ
B: High-pressure cylinder for gas
V1, V2: Valve
HV: High-pressure reactor
TB: Thermostatic bath
SM: Aqueous solution (sample)
PG: Pressure gauge
TC: Thermometer
R: Recorder
VP: Vacuum pump
W: Observation window
MS: Microscope
VHS: Video camera
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