TWI468684B - Chemoselective molecule sensing ionic liquid materials - Google Patents
Chemoselective molecule sensing ionic liquid materials Download PDFInfo
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本發明係一種感測材料，尤其是一種藉由將具專一性化學反應的反應基團修飾離子液體而形成之具化學選擇性的離子液體感測材料。The present invention is a sensing material, particularly a chemoselective ionic liquid sensing material formed by modifying an ionic liquid with a reactive group having a specific chemical reaction.
按，離子液體，為陰陽離子所組成且熔點低於100℃的融鹽類(molten salt)，其與典型無機鹽類不同的是離子液體的陽離子為有機離子；再者，離子液體與傳統的熔融鹽類的差異在於熔融鹽類的熔點高達801℃，相對而言，離子液體的熔點則較低(＜100℃)，請見表一。According to the ionic liquid, a molten salt composed of an anion and a cation and having a melting point of less than 100 ° C. Unlike a typical inorganic salt, the cation of the ionic liquid is an organic ion; further, the ionic liquid and the conventional one The difference between molten salts is that the melting point of the molten salt is as high as 801 ° C, and the melting point of the ionic liquid is relatively low (<100 ° C), see Table 1.
而室溫中呈液態的熔融鹽類則是稱為室溫離子液體(room temperature ionic liquids,RTILs)。典型的室溫離子液，其陽離子通常是含氮或磷的有機化合物，而陰離子則可為有機或無機物，常見的陰陽離子如表二所示。The molten salts that are liquid at room temperature are called room temperature ionic liquids (RTILs). Typical room temperature ionic liquids, the cations are usually organic compounds containing nitrogen or phosphorus, and the anions can be organic or inorganic. The common anions and cations are shown in Table 2.
關於離子液體的發展可見於以下文獻：Walden,P. Bull. Acad. Imper. Sci.(st. Peterburg) 1914,1800、Hurley,F. H,;Wier,T. P.J .Electrochem .Soc . 1951,98 ,203-206、Chum,H. L.;Koch,V. R.;Miller,L. L.;Osteryoung,R. A.J .Am .Chem .Soc . 1975,97 ,3264-3265、Magnuson,D. K.;Bodly,J. W.;Evans,D. F.J .Solution Chem . 1984,13 . 583以及Wilkes,J. S.;Zaworotko,M. J.J .Chem .Soc .,Chem .Commun . 1992,965-967等。The development of ionic liquids can be found in Walden, P. Bull. Acad. Imper. Sci. (st. Peterburg) 1914, 1800, Hurley, F. H, Wier, TP J. Electrochem . Soc . 1951, 98 , 203-206, Chum, HL; Koch , VR; Miller, LL;.. Osteryoung, RA J Am Chem Soc 1975, 97, 3264-3265, Magnuson, DK;.. Bodly, JW;. Evans, DF J Solution Chem . 1984, 13. 583 and Wilkes, JS; Zaworotko, MJ J. Chem . Soc ., Chem . Commun . 1992, 965-967, et al.
如以下式一所示，一般離子液體的製備可由1-咪唑烷(1-alkylimidazole)與烷基醯胺(alikylnalide)進行取代反應，再與含有預期所得陰離子的鹼金族離子、銨離子或是銀鹽進行metathesis以製備離子液體，此可參看Baker,G. A.;Baker,S. N.;Pandey,S.;Bright,F. V. The Analyst 2005,130,800-808。式一所列出目前陽離子最常被使用的為1-烷基-3-甲基咪唑(1-alkyl-3-methylimidazolium)、N-烷基吡啶(N -alkylpyridinium)、N-甲基N-烷基吡啶(N -methyl-N -alkylpyrrolidinium)以及四烷基銨(tetraalkylammonium)等四類，而在陰離子方面則包含有機及無機陰離子[PF6 ]2 、[BF4 ]2 、[(CF3 SO2 )2 N]2 、[(C2 F5 SO2 )2 N]2 、[CF3 SO3 ]2 、[(C2 F5 )3 PF3 ]2 、[CF3 CO2 ]2 、[NiCl3 ]2 ,[SCN]2 、[(CN)2 N]2 以及[CH3 SO3 - ]。一般而言，缺電子的陰離子以及陽離子上烷基取代基越多所組成的離子液體越具疏水特性。As shown in the following formula 1, the preparation of a general ionic liquid can be carried out by substituting a 1-alkylimidazole with an alkylamine (alikylnalide), followed by an alkali metal ion or ammonium ion containing the desired anion. Silver salts are subjected to metathesis to prepare ionic liquids, see Baker, GA; Baker, SN; Pandey, S.; Bright, FV The Analyst 2005, 130, 800-808. A cationic type most commonly used currently listed as 1-alkyl-3-methylimidazolium (1-alkyl-3-methylimidazolium ), N- alkylpyridinium (N -alkylpyridinium), N- methyl-N- Four kinds of alkylpyridine ( N- methyl- N- alkylpyrrolidinium) and tetraalkylammonium, and anions include organic and inorganic anions [PF 6 ] 2 , [BF 4 ] 2 , [(CF 3 SO 2 ) 2 N] 2 , [(C 2 F 5 SO 2 ) 2 N] 2 , [CF 3 SO 3 ] 2 , [(C 2 F 5 ) 3 PF 3 ] 2 , [CF 3 CO 2 ] 2 , [NiCl 3 ] 2 , [SCN] 2 , [(CN) 2 N] 2 and [CH 3 SO 3 - ]. In general, the more electron-deficient anions and the more alkyl substituents on the cation, the more hydrophobic the ionic liquid is.
離子液體已知能作為有機合成中的溶劑、藉其良好的導電性而能作為導電材料、或與其他導電鹽類一起用作電解質，相關應用可參看本國公告第I328234號、公告第I295292號等專利案。Ionic liquids are known as solvents in organic synthesis, can be used as conductive materials by their good electrical conductivity, or can be used as electrolytes together with other conductive salts. For related applications, refer to the national publication No. I328234, Announcement No. I295292 and the like. case.
另一方面，目前如污染氣體或揮發性有機氣體(VOCs)等皆係利用氣相質譜儀(GC-MS)來檢測，然而，GC-MS測量法卻需要昂貴的儀器設備以及所得的數據需要有技巧地分析，因而阻礙其使用的範圍；再者，GC-MS難以分析低分子量的VOCs[例如甲醛(formaldehyde)、氨(ammonia)等]，故有效感測化合物的材料及方法仍有待進一步的研究。On the other hand, currently, such as polluted gases or volatile organic gases (VOCs) are detected by gas chromatography mass spectrometry (GC-MS), however, GC-MS measurement requires expensive equipment and data needs. Technical analysis, thus hindering the scope of its use; in addition, GC-MS is difficult to analyze low molecular weight VOCs [such as formaldehyde, ammonia, etc.], so the materials and methods for effective sensing compounds still need further Research.
由於離子液體發展的時間不長，且目前研究也大多集中於其導電性質以及其作為溶劑和電解質的應用。而目前如GC-MS的檢測方法皆有缺點存在，因此在本發明人長期的研究以及不斷的試驗之下，發明出此具有化學專一選擇性之離子液體新感測材料。Since ionic liquids have not been developed for a long time, most of the current research has focused on their conductive properties and their use as solvents and electrolytes. At present, there are disadvantages in the detection methods such as GC-MS. Therefore, the inventors have invented this new ionic liquid sensing material with chemical specific selectivity under the long-term research and continuous experiment of the present inventors.
本發明之目的在於提供一種藉由將具專一性化學反應的反應基團修飾離子液體而形成之具化學選擇性的離子液體感測材料。It is an object of the present invention to provide a chemoselective ionic liquid sensing material formed by modifying an ionic liquid with a reactive group having a specific chemical reaction.
為達上述目的，本發明具有化學專一選擇性之離子液體新感測材料，其係包括經由具專一性化學反應的基團修飾之離子液體。To achieve the above object, the present invention has a chemically specific selective ionic liquid new sensing material comprising an ionic liquid modified via a group having a specific chemical reaction.
其中，該離子液體中的陽離子係選自於由吡啶陽離子(pyridinium)、吡咯烷離子(pyrrolidinium)、咪唑離子(imidazolium)、銨離子(ammonium)、鏻離子(phosphonium)以及鋶離子(sulfonium ion)所組成之群組。Wherein the cation in the ionic liquid is selected from the group consisting of pyridinium, pyrrolidinium, imidazolium, ammonium, phosphonium, and sulfonium ion. The group formed.
其中，該離子液體中的陰離子係選自於由聚合氯化鋁(aluminium chlorohydrate,AlnClm- )、六氟磷酸離子(PF6 - )、四氟硼酸離子(BF4 - )、硝酸根離子(NO3 - )、三氟甲基磺酸根離子(CF3 SO3 - )、三氟甲基磺醯根離子[(CF3 SO2 )2 N- ,NTf2 ]、三氟醋酸根離子(CF3 CO2 - )、醋酸根離子(CH3 CO2 - )、鹵素離子(X- )以及甲基磺酸根離子[CH3 SO3 - ,OMs- ]所組成之群組。Wherein the anion in the ionic liquid is selected from the group consisting of aluminium chlorohydrate (AlnClm - ), hexafluorophosphate ion (PF 6 - ), tetrafluoroborate ion (BF 4 - ), nitrate ion (NO) 3 - ), trifluoromethanesulfonate ion (CF 3 SO 3 - ), trifluoromethylsulfonate ion [(CF 3 SO 2 ) 2 N - , NTf 2 ], trifluoroacetate ion (CF 3 A group consisting of CO 2 - ), acetate ion (CH 3 CO 2 - ), halogen ion (X - ), and methylsulfonate ion [CH 3 SO 3 - , OMs - ].
其中，該具專一性化學反應的反應基團係選自於由胺化物(amine，如-NH2 、-NHR、-NR2 等)、亞胺(imine,-N=C-)、羧酸(carboxyl acid，-CO2 H)、酯類(ester)、腈(nitrile，-CN)、羥基(hydroxy，-OH)、硫醇(thiol，-SH)、烯化物(alkene)、炔化物(alkyne)、芳香類化合物(aromatic compound，Ar)、鹵化物(halo，X，即-F、-Cl、-Br、-I)、疊氮(azide，-N3 )、聯胺(hydrazine，-N2 )、醛化物(aldehyde，-CHO)、酮化物(ketone，-CO-)以及馬來醯亞胺(maleimide)所組成之群組。Wherein, the reactive group having a specific chemical reaction is selected from the group consisting of amines (such as -NH 2 , -NHR, -NR 2 , etc.), imines (imine, -N=C-), and carboxylic acids. (carboxyl acid, -CO 2 H), ester (ester), nitrile (nitrile, -CN), hydroxy (-OH), thiol (thiol, -SH), alkene (alkene), acetylide ( alkyne), aromatic compounds (aromatic compound, Ar), halide (halo, X, i.e. -F, -Cl, -Br, -I) , azide (azide, -N 3), hydrazine (hydrazine, - N 2 ), a group consisting of a aldehyde (aldehyde, -CHO), a ketone (ketone, -CO-), and a maleimide.
較佳的是，本發明之感測材料，其係選自於或 Preferably, the sensing material of the present invention is selected from or
本發明係一種新穎的感測材料，其係利用離子液體配合具有專一性化學反應的基團，而與待測化合物分子產生化學鍵結，鍵結後所產生的質量變化則可由石英晶體微天秤(quartz crystal microbalance，QCM)所測得，藉此方法即可準確得知待測化合物分子的種類，甚而可得知待測化合物分子的濃度，即使是低分子量的揮發性有機氣體亦可測量。The invention is a novel sensing material which utilizes an ionic liquid to match a group having a specific chemical reaction, and chemically bonds with a molecule of a compound to be tested, and the mass change produced after the bonding can be obtained by a quartz crystal microbalance ( According to the quartz crystal microbalance (QCM), the molecular type of the compound to be tested can be accurately known by this method, and even the concentration of the molecule to be tested can be known, even a low molecular weight volatile organic gas can be measured.
本發明係一種離子液體新感測材料，其包括經由具專一性化學反應的基團修飾之離子液體。請參看以下式二，其係本發明之離子液體新感測材料與感測氣體的反應式。圓形體代表離子液體、Y代表具專一性化學反應的基團、Z代表能與Y鍵結的待測化合物分子。The present invention is an ionic liquid new sensing material comprising an ionic liquid modified via a group having a specific chemical reaction. Please refer to the following formula 2, which is the reaction formula of the ionic liquid new sensing material and the sensing gas of the present invention. The circular body represents an ionic liquid, Y represents a group having a specific chemical reaction, and Z represents a molecule of a test compound capable of bonding with Y.
以下表三列舉出本發明之具專一性化學反應的反應基團以及其能進行反應鍵結而可由石英晶體微天秤(quartz crystal microbalance所檢測的基團：Table 3 below lists the reactive groups of the present invention having a specific chemical reaction and the groups which can be reacted and bonded by a quartz crystal microbalance (quartz crystal microbalance:
本發明所述之「離子液體」，是由具陽離子性質的有機化合物[包含吡啶陽離子(pyridinium)、吡咯烷離子(pyrrolidinium)、咪唑離子(imidazolium)、銨離子(ammonium)、鏻離子(phosphonium)以及鋶離子(sulfonium ion)等)，再依據所需要的特性搭配不同形式的陰離子，包含聚合氯化鋁(aluminium chlorohydrate,Aln Clm - )、六氟磷酸離子(PF6 - )、四氟硼酸離子(BF4 - )、硝酸根離子(NO3 - )、三氟甲基磺酸根離子(CF3 SO3 - )、三氟甲基磺醯根離子[(CF3 SO2 )2 N- ,NTf2 ]、三氟醋酸根離子(CF3 CO2 - )、醋酸根離子(CH3 CO2 - )、鹵素離子(X- )、甲基磺酸根離子[CH3 SO3 - ,OMs- ]等所製得，離子液體在以下式二中由圓形體示意。The "ionic liquid" according to the present invention is an organic compound having cationic properties [including pyridinium, pyrrolidinium, imidazolium, ammonium, phosphonium). And sulfonium ion, etc., and according to the required characteristics, different types of anions, including aluminum chlorohydrate (Al n Cl m - ), hexafluorophosphate ion (PF 6 - ), tetrafluoro Boric acid ion (BF 4 - ), nitrate ion (NO 3 - ), trifluoromethylsulfonate ion (CF 3 SO 3 - ), trifluoromethylsulfonate ion [(CF 3 SO 2 ) 2 N - , NTf 2 ], trifluoroacetate ion (CF 3 CO 2 - ), acetate ion (CH 3 CO 2 - ), halogen ion (X - ), methanesulfonate ion [CH 3 SO 3 - , OMs - The ionic liquid is represented by a circular body in the following formula 2, etc.
本發明所述之「具專一性化學反應性的感測新材料」，可與待測的氣體化合物分子進行化學專一選擇性的反應，進而達到氣體化合物的檢測，在以下式二中示意為Y。其中Y包含，胺化物(amine，-NH2，-NHR，-NR2)、亞胺(imine，-N=C-)、羧酸(carboxyl acid，-CO2H)、酯類(ester)、腈(nitrile，-CN)、羥基(hydroxy，-OH)、硫醇(thiol，-SH)、烯化物(alkene)、炔化物(alkyne)、芳香類化合物(aromatic compound，Ar)、鹵化物(halo，X，-F，-Cl，-Br，-I)、疊氮(azide，-N3 )、聯胺(hydrazine，-N2 )、醛化物(aldehyde，-CHO)、酮化物(ketone，-CO-)、馬來醯亞胺(maleimide)等。The "new sensing material with specific chemical reactivity" described in the present invention can be chemically and selectively reacted with the gas compound molecules to be tested, thereby achieving detection of a gas compound, which is indicated as Y in the following formula 2 . Wherein Y, aminide (amine, -NH2, -NHR, -NR2), imine (imine, -N=C-), carboxylic acid (carboxyl acid, -CO2H), ester (ester), nitrile (nitrile) , -CN), hydroxy (-OH), thiol (-SH), alkene, alkyne, aromatic compound (Ar), halide (halo, X , -F, -Cl, -Br, -I), azide, -N 3 , hydrazine, -N 2 , aldehyde (-CHO), ketone (ketone, -CO) -), maleimide, etc.
本發明所述之「石英晶體微天秤(quartz crystal microbalance，QCM)」，其係一種用於偵測有機化合物分子的裝置，由於具專一性化學反應性的離子液體與待測化合物分子反應後，其質量會有明顯的改變，如此的改變可藉由石英晶體微天秤檢測出來。再者，由於石英晶體微天秤具有容易操作、低成本以及即時回應的優點，故本發明實施例皆採用石英晶體微天秤以檢測本發明之離子液體感測材料。The "quartz crystal microbalance (QCM)" of the present invention is a device for detecting molecules of an organic compound, which is reacted with a molecule of a compound to be tested by a specific chemically reactive ionic liquid. The quality will change significantly, and this change can be detected by the quartz crystal microbalance. Furthermore, since the quartz crystal microbalance has the advantages of easy operation, low cost, and instant response, the quartz crystal microbalance is used in the embodiments of the present invention to detect the ionic liquid sensing material of the present invention.
實施例Example
1. 本發明之感測材料的合成方法1. Method for synthesizing sensing material of the present invention
離子液體的合成已為本發明所屬技術領域中具有通常知識者所知悉，而在經過本發明以上揭露後，本發明所屬技術領域中具有通常知識者亦可依照一般化學合成方法，考量使各種離子液體以及具專一選擇性化學反應的反應基團的特性而進行修飾。The synthesis of ionic liquids is known to those of ordinary skill in the art to which the present invention pertains, and after the above disclosure of the present invention, those having ordinary knowledge in the art to which the present invention pertains may also consider various ions in accordance with general chemical synthesis methods. Modifications are made by the nature of the liquid and the reactive groups with a specific selective chemical reaction.
2. 使用本發明之感測材料所進行的檢測方法2. Detection method using the sensing material of the present invention
先將已用高揮發有機溶液稀釋(如甲醇、乙醇等純化物或乙腈等)的液態感測材料混合，再將上述混合物塗佈於一石英片的表面上，將溶劑蒸發後，即在該石英片的表面形成塗層，以獲得一以感測材料為基質的薄膜感測晶片。First, the liquid sensing material which has been diluted with a highly volatile organic solution (such as a purified product such as methanol or ethanol or acetonitrile, etc.) is mixed, and the mixture is applied onto the surface of a quartz plate, and after the solvent is evaporated, The surface of the quartz plate is coated to obtain a thin film sensing wafer based on the sensing material.
之後，再令塗層與待測化合物分子進行反應，藉由石英晶體微天秤(PSS QCM system)測量震盪頻率的變化，即可得知該待測化合物分子的種類與濃度。Then, the coating is reacted with the molecule of the test compound, and the variation of the oscillation frequency is measured by a quartz crystal micro-scale (PSS QCM system) to know the type and concentration of the molecule of the test compound.
例一：SIL1對於化合物的化學專一選擇性反應Example 1: SIL1 chemical specific selective reaction of compounds
依下述方法合成SIL1；Synthesizing SIL1 according to the following method;
測試一：將3.3 nL的SIL1沉積於石英片的表面而形成厚度為300 nm的薄膜，並使其與七種待測氣體分子進行反應，該等待測氣體分子分別是水、乙醇、乙酸乙酯、丙烷、丙醛、苯甲醛及丙酮，上述皆為412 ppb之氣體。使用石英晶體微天秤(PSS QCM system)進行測量，其係在室溫下以乾燥空氣做為輸送氣體，流速為3 mL/min進行上述氣體的檢測。Test 1: Deposit 3.3 nL of SIL1 on the surface of quartz plate to form a film with a thickness of 300 nm, and react it with seven gas molecules to be tested. The gas molecules waiting for measurement are water, ethanol and ethyl acetate respectively. , propane, propionaldehyde, benzaldehyde and acetone, all of which are 412 ppb of gas. The measurement was carried out using a quartz crystal microbalance (PSS QCM system) using dry air as a transport gas at a flow rate of 3 mL/min for the detection of the above gas.
結果：請參看圖一所示，SIL1僅對於醛化物(丙醛、苯甲醛)和酮化物(丙酮)有專一選擇性的化學反應，而且醛化物和酮化物之間，因為反應性的差異造成在震盪頻率上又有明顯的區別。Results: As shown in Figure 1, SIL1 has a specific selective chemical reaction only for the aldehydes (propionaldehyde, benzaldehyde) and ketones (acetone), and the difference between the aldehydes and ketones is due to the difference in reactivity. There is a clear difference in the frequency of oscillation.
測試二：將3.3 nL的SIL1沉積於石英片的表面而形成厚度為300 nm的薄膜，並使其與水、丙酮、苯甲醛以及甲酸，上述皆為412 ppb之氣體。使用QCM進行測量，其係在室溫下以乾燥空氣做為輸送氣體，流速為3 mL/min進行上述氣體的檢測。Test 2: 3.3 nL of SIL1 was deposited on the surface of the quartz plate to form a film having a thickness of 300 nm and made into a gas of 412 ppb with water, acetone, benzaldehyde and formic acid. The measurement was carried out using QCM using dry air as a transport gas at room temperature and a flow rate of 3 mL/min for the detection of the above gas.
結果：請參看圖二所示，藉由SIL1可明顯區別水、丙酮、苯甲醛以及甲酸，其中甲酸的震盪頻率變化最大，其次為苯甲醛，丙酮則稍微有變化。Results: Please refer to Figure 2, water, acetone, benzaldehyde and formic acid can be clearly distinguished by SIL1. The oscillation frequency of formic acid changes the most, followed by benzaldehyde, and acetone slightly changes.
由上述測試一和二可知SIL1確實是一種能夠對於醛化物、酮化物及羧酸化合物具有化學專一選擇性的感測材料。From the above tests 1 and 2, it is known that SIL1 is indeed a sensing material capable of having chemical specific selectivity for aldehydes, ketones and carboxylic acid compounds.
測試三：以SIL1測試不同濃度的2-丁酮(2-butanone,C4H8O)，分別為0 ppb、7.6 ppb、15.2 ppb、22.8 ppb、38.0 ppb以及53.2 ppb，以及不同濃度的丁醛(butyraldehyde,C4H8O)，分別為0 ppb、60.8 ppb、91.2 ppb、120.4 ppb以及150.5 ppb。Test 3: Different concentrations of 2-butanone (C4H8O) were tested by SIL1 at 0 ppb, 7.6 ppb, 15.2 ppb, 22.8 ppb, 38.0 ppb and 53.2 ppb, respectively, and different concentrations of butyraldehyde (butyraldehyde, C4H8O), 0 ppb, 60.8 ppb, 91.2 ppb, 120.4 ppb, and 150.5 ppb, respectively.
結果：請參看圖三所示，SIL1對於不同濃度的2-丁酮和丁醛能夠以QCM測出不同的震盪頻率，2-丁酮檢測靈敏度約是在148 ppb時可測得約1 Hz的檢測訊號，而丁醛檢測靈敏度約是在4.5 ppb時可測得約1 Hz的檢測訊號。Results: As shown in Figure 3, SIL1 can measure different oscillation frequencies by QCM for different concentrations of 2-butanone and butyraldehyde. The detection sensitivity of 2-butanone is about 1 Hz at 148 ppb. The detection signal, while the butyraldehyde detection sensitivity is about 1 Hz detection signal measured at 4.5 ppb.
由上述測試三可知SIL1可因為待測氣體分子的反應性質不同，即使是相同的分子量(2-丁酮和丁醛具有相同分子量)，在QCM上所得到的檢測訊號仍可以有明顯的區分。It can be seen from Test 3 above that SIL1 can be distinguished because the reaction properties of the gas molecules to be tested are different, even if the same molecular weight (2-butanone and butyraldehyde have the same molecular weight), the detection signals obtained on QCM can be clearly distinguished.
測試四：以SIL1測試不同濃度的甲醛，其濃度分別為3.8 ppb、7.6 ppb以及11.4 ppb。Test 4: Different concentrations of formaldehyde were tested with SIL1 at concentrations of 3.8 ppb, 7.6 ppb, and 11.4 ppb, respectively.
結果：請參看圖四所示，SIL1對於不同濃度的甲醛亦可測出不同的震盪頻率，甲醛檢測靈敏度約是在8.4 ppb時可測得約1 Hz的檢測訊號。Results: Please refer to Figure 4, SIL1 can also detect different oscillation frequencies for different concentrations of formaldehyde. The sensitivity of formaldehyde detection is about 1 Hz at 8.4 ppb.
由上述測試四可知SIL1能夠對於具有專一選擇性化學反應的待測氣體分子之濃度進行區分。From Test 4 above, it is known that SIL1 can distinguish the concentration of gas molecules to be tested having a specific selective chemical reaction.
例二：SIL2對於化合物的化學專一選擇性反應Example 2: Chemical specific selective reaction of SIL2 to compounds
SIL2的合成方法請參看例一所示之步驟。For the synthesis method of SIL2, please refer to the steps shown in Example 1.
測試一：將10 nL的SIL2、SIL2和1 mol%三氟甲磺酸鈧[Sc(OTf)3](作為催化劑)混合液以及[雙(三氟甲基磺醯)亞胺][三氟甲基磺醯根離子]([b-3C-im][NTf2])(結構式如下)和1 mol% Sc(OTf)3混合液沉積於石英片的表面而形成厚度為909 nm的薄膜，並使其分別與28.5 ppb的丙基胺(propylamine)氣體進行反應。使用QCM system進行測量，其係在室溫下以乾燥空氣做為輸送氣體，流速為3.8 mL/min進行丙基胺的檢測。Test 1: 10 nL of SIL2, SIL2 and 1 mol% of lanthanum triflate [Sc(OTf)3] (as catalyst) and [bis(trifluoromethylsulfonyl)imide][trifluoro A mixture of methylsulfonate ion]([b-3C-im][NTf2]) (structured as follows) and 1 mol% Sc(OTf)3 was deposited on the surface of the quartz plate to form a film having a thickness of 909 nm. They were each reacted with 28.5 ppb of propylamine gas. The measurement was carried out using a QCM system using dry air as a transport gas at room temperature and a flow rate of 3.8 mL/min for propylamine detection.
結果：請參看圖五(A)所示，SIL2以及SIL2和1 mol%Sc(OTf)3混合之薄膜分別使震盪頻率移動5Hz和2Hz，即對於丙基胺有專一選擇性的化學反應；但未經修飾的[雙(三氟甲基磺醯)亞胺][三氟甲基磺醯根離子]離子液體卻對丙基胺沒有任何反應，故可知未經修飾的離子液體對於待測基團並無專一選擇性的化學反應，因此單獨的離子液體無法作為感測材料。再者，由圖五(A)還可得知在丙甲胺濃度為28.5 ppb時，檢測訊號是一不可逆的檢測結果。Results: Referring to Figure 5 (A), SIL2 and SIL2 and 1 mol% Sc(OTf)3 mixed films respectively shifted the oscillation frequency by 5 Hz and 2 Hz, which is a specific selective chemical reaction for propylamine; The unmodified [bis(trifluoromethylsulfonyl)imine][trifluoromethylsulfonate ion] ionic liquid does not react with propylamine, so it is known that the unmodified ionic liquid is for the base to be tested. The group does not have a specific selective chemical reaction, so a separate ionic liquid cannot be used as a sensing material. Furthermore, it can be seen from Fig. 5 (A) that the detection signal is an irreversible detection result when the concentration of methylamine is 28.5 ppb.
測試二：以SIL2和1 mol% Sc(OTf)3混合薄膜晶片以及[b-3C-im][NTf2]和1 mol% Sc(OTf)3混合之薄膜晶片測量不同濃度的丙基胺，其濃度分別為0 ppb、17.1 ppb、34.2 ppb、51.3 ppb、85.5 ppb以及119.7 ppb。Test 2: Different concentrations of propylamine were measured using SIL2 and 1 mol% Sc(OTf)3 mixed film wafers and [b-3C-im][NTf2] and 1 mol% Sc(OTf)3 mixed film wafers. The concentrations were 0 ppb, 17.1 ppb, 34.2 ppb, 51.3 ppb, 85.5 ppb, and 119.7 ppb, respectively.
結果：請參看圖五(B)所示，未經修飾的離子液體對於任何濃度的丙基胺皆無反應，而SIL2薄膜晶片對於不同濃度的丙基胺則有不同的震盪頻率，當以SIL2和1 mol%Sc(OTf)3混合之薄膜晶片感測丙基胺時，檢測靈敏度約是在2.5 ppb時可測得約1 Hz的檢測訊號。圖五(B)的濃度與訊號的線性關係更可再次證明本發明之感測材料能夠對於待測氣體分子的濃度加以進行定量的檢測。Results: Referring to Figure 5 (B), the unmodified ionic liquid did not react to any concentration of propylamine, while the SIL2 thin film wafer had different oscillation frequencies for different concentrations of propylamine, when SIL2 and When the 1 mol% Sc(OTf)3 mixed film wafer senses propylamine, the detection sensitivity is about 1 Hz when the detection sensitivity is about 2.5 ppb. The linear relationship between the concentration and the signal of Fig. 5(B) can further prove that the sensing material of the present invention can quantitatively detect the concentration of the gas molecules to be tested.
測試三：將10 nL的SIL2與不同的三氟甲磺酸鹽(metal triflates)製作成厚度為909nm的薄膜晶片，其分別為三氟甲磺酸鋁、三氟甲磺酸銅、三氟甲磺酸鑭、三氟甲磺酸鎂、三氟甲磺酸鈧、三氟甲磺酸釤、三氟甲磺酸鐿，再與28.5 ppm的丙基胺反應，以QCM測量各薄膜晶片上震盪頻率的移動量，以了解以不同三氟甲磺酸鹽對於催化轉氨反應(transimination reaction)的影響。Test 3: 10 nL of SIL2 and different metal triflates were made into thin film wafers with a thickness of 909 nm, which were respectively aluminum triflate, copper triflate, trifluoromethyl Sulfonium sulfonate, magnesium triflate, bismuth triflate, bismuth triflate, bismuth triflate, and then reacted with 28.5 ppm of propylamine to measure the oscillation on each thin film wafer by QCM The amount of shift in frequency to understand the effect of different triflate on the catalytic transamination reaction.
結果：請參看表四所式，由其可知三氟甲磺酸鈧對於轉氨反應的催化效果最強，故上述測試一和二皆使用三氟甲磺酸鈧作為催化劑。RESULTS: Please refer to the formula in Table 4, which shows that the ruthenium triflate has the strongest catalytic effect on the transamination reaction. Therefore, the above tests 1 and 2 all use lanthanum triflate as a catalyst.
例三：具有化學專一選擇性之離子液體的合成方法Example 3: Synthetic method of chemically specific selective ionic liquid
於下列反應式1係示範合成具有羧酸修飾的離子液體；反應式2係示範合成具有醇類修飾的離子液體；反應式3係示範合成具有胺化物修飾的離子液體和聯胺修飾的離子液體。The following reaction formula 1 is exemplified to synthesize an ionic liquid having a carboxylic acid modification; the reaction formula 2 is an exemplary synthesis of an ionic liquid having an alcohol modification; and the reaction formula 3 is an exemplary synthesis of an ionic liquid having an amine compound modification and a hydrazine-modified ionic liquid. .
由上述實施例可知，本發明新穎之感測材料能用以測量各式的化合物分子，因此應用範圍廣泛，且利用石英晶體微天秤進行測量亦具有容易操作、低成本以及即時回應的優點，故此種具專一性化學反應的反應基團修飾之離子液體感測材料確實具有極高的產業利用性。It can be seen from the above embodiments that the novel sensing material of the present invention can be used to measure various compound molecules, and thus has a wide range of applications, and the measurement by the quartz crystal microbalance scale has the advantages of easy operation, low cost, and instant response. Reactive group-modified ionic liquid sensing materials with specific chemical reactions do have extremely high industrial applicability.
雖然在前文中為了說明起見，對本發明進行了詳細的描述，但應理解，這些詳細描寫僅僅是為了說明，在不偏離本發明的精神和範圍的情況下，所屬技術領域中具有通常知識者可對所作的任何修飾仍屬於本發明之範疇。Although the present invention has been described in detail hereinabove in the foregoing description of the embodiments of the invention Any modifications that may be made remain within the scope of the invention.
圖一係本發明之SIL1感測不同待測氣體分子再以QCM測量所得之震盪頻率變化圖。Figure 1 is a graph showing the oscillation frequency variation of the SIL1 of the present invention for sensing different gas molecules to be measured and then measuring by QCM.
圖二係本發明之SIL1感測水、丙酮、苯甲醛以及甲酸再以QCM測量所得之震盪頻率變化圖。Figure 2 is a graph showing the fluctuation frequency of SIL1 of the present invention for sensing water, acetone, benzaldehyde and formic acid measured by QCM.
圖三係本發明之SIL1測試不同濃度的2-丁酮和丁醛再以QCM測量所得之震盪頻率變化圖。Figure 3 is a graph showing the variation of the oscillation frequency obtained by measuring the concentration of 2-butanone and butyraldehyde at different concentrations of SIL1 of the present invention.
圖四係本發明之SIL1對於不同濃度的甲醛以QCM測量所得之震盪頻率變化圖。Figure 4 is a graph showing the oscillation frequency variation of the SIL1 of the present invention measured by QCM for different concentrations of formaldehyde.
圖五(A)係本發明SIL2薄膜晶片、SIL2和1mol% Sc(OTf)3 混合薄膜晶片以及[b-3C-im][NTf2 ]和1mol% Sc(OTf)3 混合薄膜晶片對於丙基胺以QCM測量所得之震盪頻率變化圖。Figure 5 (A) shows a SIL2 thin film wafer, a SIL2 and 1 mol% Sc(OTf) 3 mixed thin film wafer of the present invention, and a [b-3C-im][NTf 2 ] and 1 mol% Sc(OTf) 3 mixed thin film wafer for a propyl group. The oscillating frequency change plot of the amine measured by QCM.
圖五(B)係本發明SIL2和1mol% Sc(OTf)3 混合薄膜晶片以及[b-3C-im][NTf2 ]和1mol% Sc(OTf)3 混合薄膜晶片對於不同濃度之丙基胺以QCM測量所得之震盪頻率變化圖。Figure 5 (B) is a SIL2 and 1 mol% Sc(OTf) 3 mixed film wafer of the present invention and a [b-3C-im][NTf 2 ] and 1 mol% Sc(OTf) 3 mixed film wafer for different concentrations of propylamine The oscillating frequency change graph obtained by QCM measurement.
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