KR20230164416A - Composition for detecting lead ions comprising polydiacetylene liposome, method for preparing the same, and method for detecting lead ions - Google Patents
Composition for detecting lead ions comprising polydiacetylene liposome, method for preparing the same, and method for detecting lead ions Download PDFInfo
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- 239000002502 liposome Substances 0.000 title claims abstract description 66
- 150000002500 ions Chemical class 0.000 title claims abstract description 57
- 229920000015 polydiacetylene Polymers 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 24
- 239000000203 mixture Substances 0.000 title claims abstract description 19
- 238000001514 detection method Methods 0.000 claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 239000000178 monomer Substances 0.000 claims description 72
- LLCSWKVOHICRDD-UHFFFAOYSA-N buta-1,3-diyne Chemical group C#CC#C LLCSWKVOHICRDD-UHFFFAOYSA-N 0.000 claims description 69
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 26
- 239000002253 acid Substances 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- DIEDVCMBPCRJFQ-UHFFFAOYSA-N 10,12-tricosadiynoic acid Chemical compound CCCCCCCCCCC#CC#CCCCCCCCCC(O)=O DIEDVCMBPCRJFQ-UHFFFAOYSA-N 0.000 claims description 7
- 230000001678 irradiating effect Effects 0.000 claims description 7
- 238000004458 analytical method Methods 0.000 claims description 5
- IQQJOZKPAQNXRX-UHFFFAOYSA-N henicosa-8,10-diynoic acid Chemical compound CCCCCCCCCCC#CC#CCCCCCCC(O)=O IQQJOZKPAQNXRX-UHFFFAOYSA-N 0.000 claims description 4
- 238000012546 transfer Methods 0.000 claims description 4
- IEXIHWCBQMQDHC-KEIUHOJNSA-N 5,9-hexacosadienoic acid Chemical compound CCCCCCCCCCCCCCCC\C=C\CC\C=C\CCCC(O)=O IEXIHWCBQMQDHC-KEIUHOJNSA-N 0.000 claims 3
- RIBOAUYTPSDHSQ-UHFFFAOYSA-N C(CCCCCCCCC#CC#CCCCCCCCCCCCC)(=O)O.C(CCCCCCCCC#CC#CCCCCCCCCCCCC)(=O)O Chemical compound C(CCCCCCCCC#CC#CCCCCCCCCCCCC)(=O)O.C(CCCCCCCCC#CC#CCCCCCCCCCCCC)(=O)O RIBOAUYTPSDHSQ-UHFFFAOYSA-N 0.000 claims 3
- -1 carboxyl group Ion Chemical class 0.000 claims 1
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 abstract description 19
- 230000008859 change Effects 0.000 abstract description 8
- 239000003446 ligand Substances 0.000 abstract description 4
- 239000007864 aqueous solution Substances 0.000 abstract description 3
- 238000004737 colorimetric analysis Methods 0.000 abstract description 2
- 230000003287 optical effect Effects 0.000 abstract description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
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- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 description 10
- 238000000862 absorption spectrum Methods 0.000 description 10
- 150000001768 cations Chemical class 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 150000001412 amines Chemical group 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Substances OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
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- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
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- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
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- 150000003384 small molecules Chemical class 0.000 description 3
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- DYHSDKLCOJIUFX-UHFFFAOYSA-N tert-butoxycarbonyl anhydride Chemical compound CC(C)(C)OC(=O)OC(=O)OC(C)(C)C DYHSDKLCOJIUFX-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- BRRSNXCXLSVPFC-UHFFFAOYSA-N 2,3,4-Trihydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C(O)=C1O BRRSNXCXLSVPFC-UHFFFAOYSA-N 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 2
- 108091027757 Deoxyribozyme Proteins 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
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- ZPUDRBWHCWYMQS-UHFFFAOYSA-N pentacosa-10,12-diynoic acid Chemical compound CCCCCCCCCCCCC#CC#CCCCCCCCCC(O)=O ZPUDRBWHCWYMQS-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
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- 108020004414 DNA Proteins 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
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- 230000000694 effects Effects 0.000 description 1
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- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 210000000653 nervous system Anatomy 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
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- 239000003960 organic solvent Substances 0.000 description 1
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- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003950 stripping voltammetry Methods 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
- G01N31/22—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators
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- Biochemistry (AREA)
- General Physics & Mathematics (AREA)
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Abstract
본 발명은 폴리디아세틸렌(polydiacetylene) 리포좀을 포함하는 납 이온 검출용 조성물, 이의 제조 방법 및 납 이온 검출 방법에 관한 것으로서, 납 이온에 특이적인 리간드로서의 갈로일(galloyl) 그룹으로 수식된 폴리디아세틸렌 리포좀은 납 이온과 특이적으로 배위 결합을 형성하여, 수용액에서의 청색에서 적색으로의 광학적 변화를 일으키므로, 이를 효과적으로 비색 방법 기반의 민감성이 높은 납 이온 검출 방법에 이용할 수 있다.The present invention relates to a composition for detecting lead ions containing polydiacetylene liposomes, a method for producing the same, and a method for detecting lead ions, wherein polydiacetylene is modified with a galloyl group as a specific ligand for lead ions. Liposomes specifically form coordination bonds with lead ions, causing an optical change from blue to red in an aqueous solution, so they can be effectively used in a highly sensitive lead ion detection method based on a colorimetric method.
Description
본 발명은 폴리디아세틸렌(polydiacetylene) 리포좀을 포함하는 납 이온 검출용 조성물, 이의 제조 방법 및 납 이온 검출 방법에 관한 것으로서, 더욱 상세하게는 납 이온에 특이적인 리간드로서의 갈로일(galloyl) 그룹을 포함하는 폴리디아세틸렌 리포좀, 이의 제조 방법, 및 이를 이용한 납 이온 검출 방법에 관한 것이다.The present invention relates to a composition for detecting lead ions containing polydiacetylene liposomes, a method for producing the same, and a method for detecting lead ions, and more specifically, to a composition containing a galloyl group as a specific ligand for lead ions. It relates to a polydiacetylene liposome, a method for producing the same, and a method for detecting lead ions using the same.
납 이온은 생태계와 인간 건강을 위협할 수 있는 중금속의 한 종류로서, 토양의 납 오염은 작물의 성장을 방해하고, 작물 수확량과 품질을 감소시키며, 생태계 사슬을 통해 인간 체내에 축적될 시 면역 체계, 간, 신장, 신경계에 영향을 미칠 수 있다.Lead ions are a type of heavy metal that can threaten the ecosystem and human health. Lead contamination in soil hinders the growth of crops, reduces crop yield and quality, and accumulates in the human body through the ecosystem chain. , may affect the liver, kidneys, and nervous system.
현재 납 이온을 검출할 수 있는 방식으로 유도 결합 플라즈마(Inductively Coupled Plasma; ICP) 질량 분석법, 원자 흡수 분석법, 박리 전압 전류법 등이 사용되지만, 값비싼 장비와 긴 분석 시간, 전문 인력이 필요하다는 단점이 존재한다.Currently, inductively coupled plasma (ICP) mass spectrometry, atomic absorption spectrometry, and stripping voltammetry are used to detect lead ions, but the disadvantages are that they require expensive equipment, long analysis time, and specialized personnel. This exists.
비록 지난 수십 년간 다양한 금속 이온들에 대한 형광 화학센서들을 개발하고자 하는 주목할 만한 노력들이 있어 왔으나, 납 이온에 선택적인 형광 화학센서들에 대한 보고들은 상대적으로 적었다. 현재 프로브들은 DNAzyme, 펩타이드, 단백질, 고분자 및 소분자들을 기반으로 한다. 그러나, 대부분의 상기 소분자 기반 프로브들은 유기 용매 또는 유기-물 혼합용매에서 수행되며, DNAzyme 또는 단백질 기반 프로브들은 높은 선택성을 나타내기는 하나 소분자 또는 고분자 기반 센서들에 비해 복잡한 공정을 요구한다.Although there have been notable efforts to develop fluorescent chemical sensors for various metal ions over the past few decades, there have been relatively few reports on fluorescent chemical sensors selective for lead ions. Current probes are based on DNAzymes, peptides, proteins, macromolecules, and small molecules. However, most of the above small molecule-based probes are performed in organic solvents or organic-water mixed solvents, and although DNAzyme or protein-based probes exhibit high selectivity, they require more complicated processes than small molecule or polymer-based sensors.
납 선택적 형광 센서들과 비교하여 납 선택적 비색 센서들은 거의 존재하지 않고, 현재 보고된 납 선택적 비색 센서들은 만족할 만한 선택성을 보이지 못해 실제 현장에 적용하기에 부적합하다는 단점이 있었다.Compared to lead-selective fluorescent sensors, there are almost no lead-selective colorimetric sensors, and the currently reported lead-selective colorimetric sensors do not show satisfactory selectivity, making them unsuitable for practical application.
검출용 센서의 소재로 연구되고 있는 폴리디아세틸렌(polydiacetylene)은 자가 조립된 디아세틸렌(diacetylene) 단량체의 광중합에 의해 만들어진다. 이 때 광중합 과정에서 화학적 개시제나 촉매가 요구되지 않기 때문에 합성이 매우 간단하다는 특징을 지닌다.Polydiacetylene, which is being studied as a material for detection sensors, is made by photopolymerization of self-assembled diacetylene monomers. At this time, since no chemical initiator or catalyst is required in the photopolymerization process, the synthesis is very simple.
폴리디아세틸렌이 센서 소재로 많이 연구되고 있는 주된 이유 중의 하나는 환경의 변화를 인식하여 온도, pH, 화학물질 그리고 단백질, DNA와 같은 생체 물질 등의 접근이나 결합이 이루어지면 적색으로 색 전이가 일어나게 되기 때문이다. 또한 육안으로도 쉽게 구별이 되는 선명한 청색-적색의 색 변화뿐만 아니라 청색에서는 형광이 나타나지 않고 적색에서는 형광이 나타난다는 특징이 있다.One of the main reasons why polydiacetylene is being widely studied as a sensor material is that it recognizes changes in the environment and changes color to red when temperature, pH, chemicals, and biological materials such as proteins and DNA approach or combine. Because it becomes. In addition, it not only has a clear blue-red color change that can be easily distinguished with the naked eye, but also has the characteristic that fluorescence does not appear in blue, but fluorescence appears in red.
이에 본 발명자들은 갈로일(galloyl) 그룹으로 수식된 폴리디아세틸렌(polydiacetylene) 리포좀을 제조하고, 이를 이용하여 납 이온의 검출 효과를 확인한 결과 민감성이 우수하고 다른 금속 양이온 대비 납 이온에 대한 선택성 또한 월등히 우수한 것을 확인하였다.Accordingly, the present inventors prepared a polydiacetylene liposome modified with a galloyl group and used it to confirm the detection effect of lead ions. As a result, the sensitivity was excellent and the selectivity for lead ions compared to other metal cations was also significantly higher. It was confirmed to be excellent.
이에, 본 발명의 목적은 갈로일 그룹으로 기능화된 디아세틸렌(diacetylene) 단량체 및 카르복실(carboxyl) 그룹으로 기능화된 디아세틸렌 단량체를 포함하는 폴리디아세틸렌 리포좀을 포함하는 납 이온 검출용 조성물을 제공하는 것이다.Accordingly, the object of the present invention is to provide a composition for detecting lead ions comprising a polydiacetylene liposome containing a diacetylene monomer functionalized with a galloyl group and a diacetylene monomer functionalized with a carboxyl group. will be.
본 발명의 다른 목적은 다음을 포함하는 납 이온 검출용 조성물의 제조 방법을 제공하는 것이다:Another object of the present invention is to provide a method for producing a composition for detecting lead ions comprising:
갈로일 그룹으로 기능화된 디아세틸렌 단량체 및 카르복실 그룹으로 기능화된 디아세틸렌 단량체를 포함하는 디아세틸렌 리포좀을 제조하는 리포좀 형성 단계; 및A liposome formation step of preparing a diacetylene liposome containing a diacetylene monomer functionalized with a galloyl group and a diacetylene monomer functionalized with a carboxyl group; and
상기 디아세틸렌 리포좀에 자외선(ultraviolet rays; UV)을 조사하여 폴리디아세틸렌 리포좀을 제조하는 광중합 단계.A photopolymerization step of producing polydiacetylene liposomes by irradiating ultraviolet rays (UV) to the diacetylene liposomes.
본 발명의 또 다른 목적은 갈로일 그룹으로 기능화된 디아세틸렌 단량체 및 카르복실 그룹으로 기능화된 디아세틸렌 단량체를 포함하는 폴리디아세틸렌 리포좀을 대상 시료에 접촉시키는 접촉 단계를 포함하는 납 이온 검출 방법을 제공하는 것이다.Another object of the present invention is to provide a lead ion detection method comprising a contact step of contacting a target sample with a polydiacetylene liposome containing a diacetylene monomer functionalized with a galloyl group and a diacetylene monomer functionalized with a carboxyl group. It is done.
본 발명의 또 다른 목적은 갈로일 그룹으로 기능화된 디아세틸렌 단량체 및 카르복실 그룹으로 기능화된 디아세틸렌 단량체를 포함하는 폴리디아세틸렌 리포좀의 납 이온 검출 용도에 관한 것이다.Another object of the present invention relates to the use of polydiacetylene liposomes containing diacetylene monomers functionalized with galloyl groups and diacetylene monomers functionalized with carboxyl groups for detecting lead ions.
본 발명은 폴리디아세틸렌(polydiacetylene) 리포좀을 포함하는 납 이온 검출용 조성물, 이의 제조 방법 및 납 이온 검출 방법에 관한 것으로, 본 발명에 따라 제조된 폴리디아세틸렌 리포좀은 민감성이 우수하고 다른 금속 양이온 대비 납 이온에 대한 선택성 또한 월등히 우수함을 나타낸다.The present invention relates to a composition for detecting lead ions containing polydiacetylene liposomes, a method for producing the same, and a method for detecting lead ions. The polydiacetylene liposomes prepared according to the present invention have excellent sensitivity and are superior to other metal cations. The selectivity for lead ions is also excellent.
본 발명자들은 갈로일(galloyl) 그룹으로 기능화된 디아세틸렌(diacetylene) 단량체 및 카르복실(carboxyl) 그룹으로 기능화된 디아세틸렌 단량체의 혼합 몰비를 최적화하여 납 이온의 검출에 효과적인 폴리디아세틸렌 리포좀을 제조함으로써, 기존에 사용되는 납 이온 검출 방식의 단점을 보완하고, 납 이온을 선택적으로 검출할 수 있는 고분자 복합체를 제공하였다.The present inventors optimized the mixing molar ratio of diacetylene monomer functionalized with a galloyl group and diacetylene monomer functionalized with a carboxyl group to prepare polydiacetylene liposomes that are effective in detecting lead ions. , complemented the shortcomings of the previously used lead ion detection method and provided a polymer complex that can selectively detect lead ions.
이하 본 발명을 더욱 자세히 설명하고자 한다.Hereinafter, the present invention will be described in more detail.
본 발명의 일 양태는 갈로일 그룹으로 기능화된 디아세틸렌 단량체 및 카르복실 그룹으로 기능화된 디아세틸렌 단량체를 포함하는 폴리디아세틸렌 리포좀을 포함하는 납 이온 검출용 조성물이다.One aspect of the present invention is a composition for detecting lead ions comprising a polydiacetylene liposome containing a diacetylene monomer functionalized with a galloyl group and a diacetylene monomer functionalized with a carboxyl group.
상기 갈로일 그룹은 납 이온과 배위 결합을 형성하는 것일 수 있다.The galloyl group may form a coordination bond with lead ions.
본 발명에 있어서 상기 갈로일 그룹으로 기능화된 디아세틸렌 단량체는 하기 화학식 1의 구조를 갖는 것일 수 있다:In the present invention, the diacetylene monomer functionalized with the galloyl group may have the structure of the following formula (1):
[화학식 1][Formula 1]
. .
본 발명에 있어서 상기 카르복실 그룹으로 기능화된 디아세틸렌 단량체는 10,12-트리코사디노익산(10,12-tricosadiynoic acid; TCDA), 10,12-펜타코사디노익산(10,12-pentacosadiynoic acid; PCDA), 및 8,10-헤네이코사디노익산(8,10-heneicosadiynoic acid; HCDA)로 이루어진 군으로부터 선택되는 1종 이상인 것일 수 있고, 예를 들어, TCDA인 것일 수 있으나, 이에 한정되는 것은 아니다.In the present invention, the diacetylene monomer functionalized with the carboxyl group includes 10,12-tricosadiynoic acid (TCDA), 10,12-pentacosadiynoic acid; It may be one or more selected from the group consisting of PCDA), and 8,10-heneicosadiynoic acid (HCDA), for example, TCDA, but is limited thereto. no.
본 발명에 있어서 상기 조성물은 갈로일 그룹으로 기능화된 디아세틸렌 단량체 및 카르복실 그룹으로 기능화된 디아세틸렌 단량체를 0.1:9.9 내지 5.0:5.0의 몰비로 포함하는 것일 수 있고, 바람직하게는 0.1:9.9 내지 4.0:6.0, 0.1:9.9 내지 3.0:7.0, 0.1:9.9 내지 2.0:8.0, 0.1:9.9 내지 1.0:9.0, 1.0:9.0 내지 5.0:5.0, 1.0:9.0 내지 4.0:6.0, 또는 1.0:9.0 내지 3.0:7.0의 몰비로 포함하는 것일 수 있고, 예를 들어, 1.0:9.0 내지 2.0:8.0의 몰비로 포함하는 것일 수 있으나, 이에 한정되는 것은 아니다.In the present invention, the composition may include a diacetylene monomer functionalized with a galloyl group and a diacetylene monomer functionalized with a carboxyl group at a molar ratio of 0.1:9.9 to 5.0:5.0, preferably 0.1:9.9 to 0.1:9.9. 4.0:6.0, 0.1:9.9 to 3.0:7.0, 0.1:9.9 to 2.0:8.0, 0.1:9.9 to 1.0:9.0, 1.0:9.0 to 5.0:5.0, 1.0:9.0 to 4.0:6.0, or 1.0:9.0 to 3.0 It may be included at a molar ratio of :7.0, for example, it may be included at a molar ratio of 1.0:9.0 to 2.0:8.0, but is not limited thereto.
본 발명의 다른 양태는 다음을 포함하는 납 이온 검출용 조성물의 제조 방법이다:Another aspect of the present invention is a method of preparing a composition for detecting lead ions comprising:
갈로일 그룹으로 기능화된 디아세틸렌 단량체 및 카르복실 그룹으로 기능화된 디아세틸렌 단량체를 포함하는 디아세틸렌 리포좀을 제조하는 리포좀 형성 단계; 및A liposome formation step of preparing a diacetylene liposome containing a diacetylene monomer functionalized with a galloyl group and a diacetylene monomer functionalized with a carboxyl group; and
상기 디아세틸렌 리포좀에 자외선(ultraviolet rays; UV)을 조사하여 폴리디아세틸렌 리포좀을 제조하는 광중합 단계.A photopolymerization step of producing polydiacetylene liposomes by irradiating ultraviolet rays (UV) to the diacetylene liposomes.
본 발명에 있어서 상기 갈로일 그룹으로 기능화된 디아세틸렌 단량체는 하기 화학식 1의 구조를 갖는 것일 수 있다.In the present invention, the diacetylene monomer functionalized with a galloyl group may have the structure of Formula 1 below.
[화학식 1][Formula 1]
상기 제조 방법은 리포좀 형성 단계의 수행에 필요한 갈로일 그룹으로 기능화된 디아세틸렌 단량체를 제조하기 위한 방법으로서 다음 단계를 추가적으로 포함하는 것일 수 있다:The above production method is a method for producing a diacetylene monomer functionalized with a galloyl group required to perform the liposome formation step and may additionally include the following steps:
카르복실 그룹으로 기능화된 디아세틸렌 단량체의 카르복실 작용기(Carboxyl functional group)를 NHS(N-Hydroxysuccinimide) 작용기로 치환하여, NHS 작용기로 수식된 디아세틸렌 단량체를 합성하는 제1 유기 합성 단계;A first organic synthesis step of replacing the carboxyl functional group of the diacetylene monomer functionalized with a carboxyl group with an NHS (N-Hydroxysuccinimide) functional group to synthesize a diacetylene monomer modified with an NHS functional group;
상기 제1 유기 합성 단계에서 제조된 디아세틸렌 단량체의 NHS 작용기를 아민 그룹으로 치환하여, 아민 말단 그룹을 가지는 디아세틸렌 단량체를 합성하는 제2 유기 합성 단계; 및A second organic synthesis step of synthesizing a diacetylene monomer having an amine end group by replacing the NHS functional group of the diacetylene monomer prepared in the first organic synthesis step with an amine group; and
상기 제2 유기 합성 단계에서 제조된 디아세틸렌 단량체의 아민 말단 그룹을 갈로일 그룹으로 기능화하여, 갈로일 그룹으로 기능화된 디아세틸렌 단량체(PCDA-Galloyl)를 합성하는 제3 유기 합성 단계.A third organic synthesis step of functionalizing the amine terminal group of the diacetylene monomer prepared in the second organic synthesis step with a galloyl group to synthesize a diacetylene monomer functionalized with a galloyl group (PCDA-Galloyl).
상기 제1 유기 합성 단계의 수행에 필요한 카르복실 그룹으로 기능화된 디아세틸렌 단량체는 10,12-트리코사디노익산(TCDA), 10,12-펜타코사디노익산(PCDA), 및 8,10-헤네이코사디노익산(HCDA)로 이루어진 군으로부터 선택되는 1종 이상인 것일 수 있고, 예를 들어, PCDA인 것일 수 있으나, 이에 한정되는 것은 아니다.Diacetylene monomers functionalized with carboxyl groups required to carry out the first organic synthesis step include 10,12-tricosadinoic acid (TCDA), 10,12-pentacosadinoic acid (PCDA), and 8,10-h. It may be one or more types selected from the group consisting of neicosadinoic acid (HCDA), for example, PCDA, but is not limited thereto.
본 발명에 있어서 상기 리포좀 형성 단계의 수행에 필요한 카르복실 그룹으로 기능화된 디아세틸렌 단량체는 10,12-트리코사디노익산(TCDA), 10,12-펜타코사디노익산(PCDA), 및 8,10-헤네이코사디노익산(HCDA)로 이루어진 군으로부터 선택되는 1종 이상인 것일 수 있고, 예를 들어, TCDA인 것일 수 있으나, 이에 한정되는 것은 아니다.In the present invention, diacetylene monomers functionalized with carboxyl groups necessary for performing the liposome formation step include 10,12-tricosadinoic acid (TCDA), 10,12-pentacosadinoic acid (PCDA), and 8,10 -It may be one or more types selected from the group consisting of heneicosadinoic acid (HCDA), for example, TCDA, but is not limited thereto.
본 발명에 있어서 상기 리포좀 형성 단계는 갈로일 그룹으로 기능화된 디아세틸렌 단량체 및 카르복실 그룹으로 기능화된 디아세틸렌 단량체를 0.1:9.9 내지 5.0:5.0의 몰비로 하여 수행되는 것일 수 있고, 바람직하게는 0.1:9.9 내지 4.0:6.0, 0.1:9.9 내지 3.0:7.0, 0.1:9.9 내지 2.0:8.0, 0.1:9.9 내지 1.0:9.0, 1.0:9.0 내지 5.0:5.0, 1.0:9.0 내지 4.0:6.0, 또는 1.0:9.0 내지 3.0:7.0의 몰비로 하여 수행되는 것일 수 있고, 예를 들어, 1.0:9.0 내지 2.0:8.0의 몰비로 하여 수행되는 것일 수 있으나, 이에 한정되는 것은 아니다.In the present invention, the liposome forming step may be performed using a diacetylene monomer functionalized with a galloyl group and a diacetylene monomer functionalized with a carboxyl group at a molar ratio of 0.1:9.9 to 5.0:5.0, preferably 0.1. :9.9 to 4.0:6.0, 0.1:9.9 to 3.0:7.0, 0.1:9.9 to 2.0:8.0, 0.1:9.9 to 1.0:9.0, 1.0:9.0 to 5.0:5.0, 1.0:9.0 to 4.0:6.0, or 1.0: It may be performed at a molar ratio of 9.0 to 3.0:7.0, for example, may be performed at a molar ratio of 1.0:9.0 to 2.0:8.0, but is not limited thereto.
상기 광중합 단계는 100 내지 380 nm의 자외선을 조사하여 수행되는 것일 수 있고, 바람직하게는 100 내지 350 nm, 100 내지 300 nm, 150 내지 380 nm, 150 내지 350 nm, 150 내지 300 nm, 200 내지 380 nm, 200 내지 350 nm, 200 내지 300 nm, 250 내지 380 nm, 또는 250 내지 350 nm의 자외선을 조사하여 수행되는 것일 수 있고, 예를 들어, 250 내지 300 nm의 자외선을 조사하여 수행되는 것일 수 있으나, 이에 한정되는 것은 아니다.The photopolymerization step may be performed by irradiating ultraviolet rays of 100 to 380 nm, preferably 100 to 350 nm, 100 to 300 nm, 150 to 380 nm, 150 to 350 nm, 150 to 300 nm, 200 to 380 nm. It may be performed by irradiating ultraviolet rays of 200 to 350 nm, 200 to 300 nm, 250 to 380 nm, or 250 to 350 nm, for example, it may be performed by irradiating ultraviolet rays of 250 to 300 nm. However, it is not limited to this.
본 발명의 또 다른 양태는 갈로일 그룹으로 기능화된 디아세틸렌 단량체 및 카르복실 그룹으로 기능화된 디아세틸렌 단량체를 포함하는 폴리디아세틸렌 리포좀을 대상 시료에 접촉시키는 접촉 단계를 포함하는 납 이온 검출 방법이다.Another aspect of the present invention is a lead ion detection method comprising the step of contacting a target sample with a polydiacetylene liposome containing a diacetylene monomer functionalized with a galloyl group and a diacetylene monomer functionalized with a carboxyl group.
본 발명에 있어서 상기 갈로일 그룹으로 기능화된 디아세틸렌 단량체는 하기 화학식 1의 구조를 갖는 것일 수 있다.In the present invention, the diacetylene monomer functionalized with a galloyl group may have the structure of Formula 1 below.
[화학식 1][Formula 1]
본 발명에 있어서 상기 카르복실 그룹으로 기능화된 디아세틸렌 단량체는 10,12-트리코사디노익산(TCDA), 10,12-펜타코사디노익산(PCDA), 및 8,10-헤네이코사디노익산(HCDA)로 이루어진 군으로부터 선택되는 1종 이상인 것일 수 있고, 예를 들어, TCDA인 것일 수 있으나, 이에 한정되는 것은 아니다.In the present invention, the diacetylene monomer functionalized with the carboxyl group is 10,12-tricosadinoic acid (TCDA), 10,12-pentacosadinoic acid (PCDA), and 8,10-heneicosadinoic acid ( It may be one or more types selected from the group consisting of HCDA), for example, TCDA, but is not limited thereto.
본 발명에 있어서 상기 폴리디아세틸렌 리포좀은 갈로일 그룹으로 기능화된 디아세틸렌 단량체 및 카르복실 그룹으로 기능화된 디아세틸렌 단량체를 0.1:9.9 내지 5.0:5.0의 몰비로 포함하는 것일 수 있고, 바람직하게는 0.1:9.9 내지 4.0:6.0, 0.1:9.9 내지 3.0:7.0, 0.1:9.9 내지 2.0:8.0, 0.1:9.9 내지 1.0:9.0, 1.0:9.0 내지 5.0:5.0, 1.0:9.0 내지 4.0:6.0, 또는 1.0:9.0 내지 3.0:7.0의 몰비로 포함하는 것일 수 있고, 예를 들어, 1.0:9.0 내지 2.0:8.0의 몰비로 포함하는 것일 수 있으나, 이에 한정되는 것은 아니다.In the present invention, the polydiacetylene liposome may include a diacetylene monomer functionalized with a galloyl group and a diacetylene monomer functionalized with a carboxyl group at a molar ratio of 0.1:9.9 to 5.0:5.0, preferably 0.1. :9.9 to 4.0:6.0, 0.1:9.9 to 3.0:7.0, 0.1:9.9 to 2.0:8.0, 0.1:9.9 to 1.0:9.0, 1.0:9.0 to 5.0:5.0, 1.0:9.0 to 4.0:6.0, or 1.0: It may be included at a molar ratio of 9.0 to 3.0:7.0, for example, may be included at a molar ratio of 1.0:9.0 to 2.0:8.0, but is not limited thereto.
본 발명에 있어서 상기 방법은 폴리디아세틸렌 리포좀을 대상 시료에 접촉시킨 후 색 전이 여부를 확인하는 분석 단계를 추가적으로 포함하는 것일 수 있다.In the present invention, the method may additionally include an analysis step of checking whether color transfer occurs after contacting the polydiacetylene liposome with the target sample.
상기 분석 단계는 아래 수식을 통해 계산한 비색 반응 값(Colorimetric response, CR(%))을 기준으로 하여 대상 시료와의 접촉 전후의 흡수 스펙트럼을 비교함으로써 색 전이 여부에 따른 납 이온의 검출 여부 및 농도를 확인할 수 있다.The analysis step compares the absorption spectrum before and after contact with the target sample based on the colorimetric response (CR (%)) calculated using the formula below to determine whether lead ions are detected and their concentration depending on whether color transfer occurs. You can check.
위 수식에서 는 중합한 청색 폴리디아세틸렌 샘플의 값이며 A는 자외선-가시광선 흡수 스펙트럼에서 청색 또는 적색에 해당하는 파장의 흡광도(Absorbance)를 나타낸다. 는 납 이온을 첨가하여 비색 전이가 발생한 폴리디아세틸렌 샘플의 흡수 스펙트럼에서 나타나는 청색 또는 적색에 해당하는 파장의 흡광도 값으로부터 얻어진 값이다.In the above formula of the polymerized blue polydiacetylene sample. value, and A represents the absorbance of the wavelength corresponding to blue or red in the ultraviolet-visible light absorption spectrum. is obtained from the absorbance value of the wavelength corresponding to blue or red appearing in the absorption spectrum of the polydiacetylene sample in which colorimetric transition occurred by adding lead ions. It is a value.
본 발명은 폴리디아세틸렌(polydiacetylene) 리포좀을 포함하는 납 이온 검출용 조성물, 이의 제조 방법 및 납 이온 검출 방법에 관한 것으로서, 납 이온에 특이적인 리간드로서의 갈로일(galloyl) 그룹으로 수식된 폴리디아세틸렌 리포좀은 납 이온과 특이적으로 배위 결합을 형성하여, 수용액에서의 청색에서 적색으로의 광학적 변화를 일으키므로, 이를 효과적으로 비색 방법 기반의 민감성이 높은 납 이온 검출 방법에 이용할 수 있다.The present invention relates to a composition for detecting lead ions containing polydiacetylene liposomes, a method for producing the same, and a method for detecting lead ions, wherein polydiacetylene is modified with a galloyl group as a specific ligand for lead ions. Liposomes specifically form coordination bonds with lead ions, causing an optical change from blue to red in an aqueous solution, so they can be effectively used in a highly sensitive lead ion detection method based on a colorimetric method.
도 1은 본 발명의 일 실시예에 따라 제조된 갈로일 그룹으로 수식된 폴리디아세틸렌 리포좀의 합성 및 납 이온 검출에 관한 모식도이다.
도 2a는 본 발명의 일 실시예에 따라 합성된 NHS 작용기로 수식된 디아세틸렌 단량체(PCDA-NHS)의 1H-핵자기공명 스펙트럼(Nuclear magnetic resonance spectroscopy; NMR) 분석 결과 그래프이다.
도 2b는 본 발명의 일 실시예에 따라 합성된 아민 말단 그룹을 가지는 디아세틸렌 단량체(PCDA-EDA)의 NMR 분석 결과 그래프이다.
도 2c는 본 발명의 일 실시예에 따라 합성된 갈로일 그룹으로 기능화된 디아세틸렌 단량체(PCDA-Galloyl)의 NMR 분석 결과 그래프이다.
도 3a는 본 발명의 일 실시예에 따라 합성된 PCDA-Galloyl:TCDA(10,12-Tricosadiynoic acid; 10,12-트리코사디노익산)를 1:9 몰비로 하여 제조된 PCDA-Galloyl 폴리디아세틸렌 리포좀의 납 이온 농도별 비색 반응 값을 나타낸 그래프이다.
도 3b는 본 발명의 일 실시예에 따라 합성된 PCDA-Galloyl:TCDA를 2:8 몰비로 하여 제조된 PCDA-Galloyl 폴리디아세틸렌 리포좀의 납 이온 농도별 비색 반응 값을 나타낸 그래프이다.
도 3c는 본 발명의 일 실시예에 따라 합성된 PCDA-Galloyl:TCDA를 3:7 몰비로 하여 제조된 PCDA-Galloyl 폴리디아세틸렌 리포좀의 납 이온 농도별 비색 반응 값을 나타낸 그래프이다.
도 4a는 본 발명의 일 실시예에 따라 합성된 PCDA-Galloyl 폴리디아세틸렌 리포좀의 납 이온에 대한 UV-vis 흡수 스펙트럼을 나타낸 그래프이다.
도 4b는 본 발명의 일 실시예에 따라 합성된 PCDA-Galloyl 폴리디아세틸렌 리포좀의 납 이온 농도 대비 비색 반응 값을 나타낸 선형 상관관계 그래프이다.
도 5a는 본 발명의 일 실시예에 따라 합성된 PCDA-Galloyl 폴리디아세틸렌 리포좀의 금속 양이온들에 대한 흡수 스펙트럼을 나타낸 그래프이다.
도 5b는 본 발명의 일 실시예에 따라 합성된 PCDA-Galloyl 폴리디아세틸렌 리포좀의 금속 양이온들에 대한 선택성을 나타낸 그래프이다.Figure 1 is a schematic diagram of the synthesis and lead ion detection of polydiacetylene liposomes modified with a galloyl group prepared according to an embodiment of the present invention.
Figure 2a is a graph showing the results of 1 H-nuclear magnetic resonance spectroscopy (NMR) analysis of a diacetylene monomer (PCDA-NHS) modified with an NHS functional group synthesized according to an embodiment of the present invention.
Figure 2b is a graph showing the results of NMR analysis of a diacetylene monomer (PCDA-EDA) having an amine terminal group synthesized according to an embodiment of the present invention.
Figure 2c is a graph showing the results of NMR analysis of a diacetylene monomer (PCDA-Galloyl) functionalized with a galloyl group synthesized according to an embodiment of the present invention.
Figure 3a shows PCDA-Galloyl polydiacetylene prepared by using PCDA-Galloyl:TCDA (10,12-Tricosadiynoic acid; 10,12-tricosadiynoic acid) synthesized according to an embodiment of the present invention at a molar ratio of 1:9. This is a graph showing the colorimetric response values for each liposome lead ion concentration.
Figure 3b is a graph showing the colorimetric response values of PCDA-Galloyl polydiacetylene liposomes synthesized according to an embodiment of the present invention using PCDA-Galloyl:TCDA at a molar ratio of 2:8 according to lead ion concentration.
Figure 3c is a graph showing the colorimetric response values of PCDA-Galloyl polydiacetylene liposomes synthesized according to an embodiment of the present invention using PCDA-Galloyl:TCDA at a molar ratio of 3:7 according to lead ion concentration.
Figure 4a is a graph showing the UV-vis absorption spectrum for lead ions of PCDA-Galloyl polydiacetylene liposome synthesized according to an embodiment of the present invention.
Figure 4b is a linear correlation graph showing the colorimetric response value versus lead ion concentration of PCDA-Galloyl polydiacetylene liposomes synthesized according to an embodiment of the present invention.
Figure 5a is a graph showing the absorption spectrum for metal cations of PCDA-Galloyl polydiacetylene liposome synthesized according to an embodiment of the present invention.
Figure 5b is a graph showing the selectivity for metal cations of PCDA-Galloyl polydiacetylene liposome synthesized according to an embodiment of the present invention.
이하, 본 발명을 하기의 실시예에 의하여 더욱 상세히 설명한다. 그러나 이들 실시예는 본 발명을 예시하기 위한 것일 뿐이며, 본 발명의 범위가 이들 실시예에 의하여 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail through the following examples. However, these examples are only for illustrating the present invention, and the scope of the present invention is not limited by these examples.
본 명세서 전체에 걸쳐, 특정 물질의 농도를 나타내기 위하여 사용되는 "%"는 별도의 언급이 없는 경우, 고체/고체는 (중량/중량)%, 고체/액체는 (중량/부피)%, 그리고 액체/액체는 (부피/부피)%이다.Throughout this specification, “%” used to indicate the concentration of a specific substance means (weight/volume)% for solid/solid, (weight/volume)% for solid/liquid, and Liquid/liquid is (volume/volume)%.
제조예 1: 갈로일 그룹 기능화 단량체(PCDA-Galloyl) 합성Preparation Example 1: Synthesis of galloyl group functionalized monomer (PCDA-Galloyl)
납 이온과 특이적으로 배위 결합을 통해 결합할 수 있는 리간드인 갈로일(Galloyl) 그룹으로 기능화된 단량체 PCDA-Galloyl을 유기 합성하기 위하여, 총 세 단계의 과정을 거쳐 수행하였다.In order to organically synthesize the monomer PCDA-Galloyl functionalized with a Galloyl group, a ligand that can specifically bind to lead ions through a coordination bond, a total of three steps were performed.
1-1. NHS 작용기로 수식된 디아세틸렌 단량체(PCDA-NHS)의 유기 합성1-1. Organic synthesis of diacetylene monomer (PCDA-NHS) modified with NHS functional groups
먼저, NHS 활성화된 단량체(PCDA-NHS)를 유기 합성하기 위하여, PCDA 단량체의 카르복실 작용기(Carboxyl functional group)를 EDC(1-Ethyl-3-[3-dimethylami-nopropyl]-carbodiimide hydrochloride)를 통해 활성화시킨 다음 NHS(N-Hydroxysuccinimide) 작용기로 치환하여 PCDA-NHS를 유기 합성하였다.First, in order to organically synthesize the NHS-activated monomer (PCDA-NHS), the carboxyl functional group of the PCDA monomer was converted to EDC (1-Ethyl-3-[3-dimethylami-nopropyl]-carbodiimide hydrochloride). After activation, PCDA-NHS was organically synthesized by substitution with N-Hydroxysuccinimide (NHS) functional group.
구체적으로, PCDA(10, 12-pentacosadiynoic acid) (0.50 g, 1.34 mmol)를 MC(Methylene Chloride) 10 mL에 용해시켰으며 EDC(0.30 g, 1.57 mmol), NHS(0.17 g, 1.48 mmol)를 첨가하였다. 상온에서 4시간 동안 교반한 후 감압 증류를 통해 MC를 제거하였으며, EA(Ethyl Acetate)와 탈이온수를 사용하여 추출하고 고염수(Brine) 5 mL를 첨가하여 세척하였다. 유기층의 수용액을 황산마그네슘(MgSO4)을 사용하여 건조시킨 후 필터링하였다. 용매를 제거하여 최종 반응 산물 PCDA-NHS(0.53 g, 84.1% yield)를 수득하였으며, 구조는 1H-핵자기공명분광법(Nuclear magnetic resonance spectroscopy; NMR)을 통해 도 2a와 같이 분석하였다.Specifically, PCDA (10, 12-pentacosadiynoic acid) (0.50 g, 1.34 mmol) was dissolved in 10 mL of MC (Methylene Chloride), and EDC (0.30 g, 1.57 mmol) and NHS (0.17 g, 1.48 mmol) were added. did. After stirring at room temperature for 4 hours, MC was removed through reduced pressure distillation, extracted using EA (Ethyl Acetate) and deionized water, and washed by adding 5 mL of high saline water (brine). The aqueous solution of the organic layer was dried using magnesium sulfate (MgSO 4 ) and then filtered. The solvent was removed to obtain the final reaction product PCDA-NHS (0.53 g, 84.1% yield), and the structure was analyzed through 1 H-nuclear magnetic resonance spectroscopy (NMR) as shown in Figure 2a.
1-2. 아민 말단 그룹을 가지는 디아세틸렌 단량체(PCDA-EDA)의 유기 합성1-2. Organic synthesis of diacetylene monomers with amine terminal groups (PCDA-EDA)
다음 아민 말단 그룹을 가지는 단량체 합성을 위해, 상기 제조예 1-1에서 합성된 PCDA-NHS 및 에틸렌다이아민(EDA)을 결합하였다. 이때 두 개의 아민 말단을 가지는 EDA의 한 부분을 보호하기 위해 Di-tert-butyl Dicarbonate(Di-Boc)을 결합한 EDA-BOC 형태를 사용하였다.To synthesize a monomer having the following amine terminal group, PCDA-NHS and ethylenediamine (EDA) synthesized in Preparation Example 1-1 were combined. At this time, to protect one part of EDA that has two amine terminals, an EDA-BOC form combining Di-tert-butyl Dicarbonate (Di-Boc) was used.
구체적으로, 상기 제조예 1-1에서 수득한 PCDA-NHS(0.53 g, 1.12 mmol) 및 EDA-BOC(0.18 g, 1.12 mmol)을 실온에서 밤새 반응하여 PCDA-EDA-BOC(0.38 g, 66.2% yield)를 수득하였다. TFA(Trifluoroacetic acid) 200 μL를 처리하여 BOC을 떼어내고, 감압 증류를 통해 MC를 제거하였다. MC 및 소듐 바이카보네이트(sodium bicarbonate)로 추출하였으며, CH2Cl2-MeOH(10:1 v/v) 용매를 사용하여 실리카-겔(Silica-gel) 크로마토그래피 방식으로 정제하였다. 용매를 제거하여 최종 산물 단량체인 PCDA-EDA(0.24 g, 76.7% yield)를 수득하였으며, 구조는 NMR을 통해 도 2b와 같이 분석하였다.Specifically, PCDA-NHS (0.53 g, 1.12 mmol) and EDA-BOC (0.18 g, 1.12 mmol) obtained in Preparation Example 1-1 were reacted at room temperature overnight to produce PCDA-EDA-BOC (0.38 g, 66.2%). yield) was obtained. BOC was removed by treating with 200 μL of TFA (Trifluoroacetic acid), and MC was removed through reduced pressure distillation. It was extracted with MC and sodium bicarbonate, and purified by silica-gel chromatography using CH 2 Cl 2 -MeOH (10:1 v/v) solvent. The solvent was removed to obtain the final product monomer, PCDA-EDA (0.24 g, 76.7% yield), and the structure was analyzed through NMR as shown in Figure 2b.
1-3. 갈로일 그룹으로 기능화된 디아세틸렌 단량체(PCDA-Galloyl)의 유기 합성1-3. Organic synthesis of diacetylene monomer functionalized with galloyl groups (PCDA-Galloyl)
최종적으로, 갈로일 그룹으로 기능화된 단량체(PCDA-Galloyl)를 합성하기 위하여, 2,3,4-trihydroxybenzoic acid(0.06 g, 0.35 mmol)을 CH2Cl2-MeOH(10:1 v/v) 용매에 용해시킨 후, EDC(0.08 g, 0.44 mmol) 및 NHS(0.05 g, 0.42 mmol)를 첨가하여 실온에서 30분 동안 활성화하였다.Finally, to synthesize a monomer functionalized with a galloyl group (PCDA-Galloyl), 2,3,4-trihydroxybenzoic acid (0.06 g, 0.35 mmol) was dissolved in CH 2 Cl 2 -MeOH (10:1 v/v). After dissolving in a solvent, EDC (0.08 g, 0.44 mmol) and NHS (0.05 g, 0.42 mmol) were added and activated for 30 minutes at room temperature.
동시에, PCDA-EDA(0.1 g, 0.24 mmol)을 CH2Cl2-MeOH(10:1 v/v) 용매에 용해하여 TEA(Triethylamine)(68 μL, 0.04 mmol)를 첨가하고 30분 동안 교반하며 반응시켰다.At the same time, PCDA-EDA (0.1 g, 0.24 mmol) was dissolved in CH 2 Cl 2 -MeOH (10:1 v/v) solvent, TEA (Triethylamine) (68 μL, 0.04 mmol) was added, and stirred for 30 minutes. reacted.
30분 후, 상기 두 용액(solution)을 혼합하여 실온에서 밤새 교반하였다. 반응 후 CH2Cl2-MeOH(10:1 v/v) 용매와 탈이온수를 사용하여 추출하였으며 추출 과정을 2-3회 반복한 후, CH2Cl2-MeOH(10:1 v/v) 용매를 사용하여 실리카-겔 크로마토그래피 방식으로 정제하였다. 최종적으로, PCDA-Galloyl(0.10 g, 79.4% yield)을 수득하였으며, 결합 구조는 NMR을 사용하여 도 2c와 같이 분석하였다.After 30 minutes, the two solutions were mixed and stirred at room temperature overnight. After the reaction, extraction was performed using CH 2 Cl 2 -MeOH (10:1 v/v) solvent and deionized water, and the extraction process was repeated 2-3 times, followed by CH 2 Cl 2 -MeOH (10:1 v/v). It was purified by silica-gel chromatography using a solvent. Finally, PCDA-Galloyl (0.10 g, 79.4% yield) was obtained, and the binding structure was analyzed using NMR as shown in Figure 2c.
제조예 2: 갈로일 그룹으로 수식된 폴리디아세틸렌 리포좀의 합성Preparation Example 2: Synthesis of polydiacetylene liposome modified with galloyl group
PCDA-Galloyl 리포좀은 두 단량체 PCDA-Galloyl:TCDA를 (a) 1:9, (b) 2:8, (c) 3:7의 몰 비율로 다양하게 제조하였다. (a) 1:9의 경우, PCDA-Galloyl 0.4 mg 및 TCDA(10,12-Tricosadiynoic acid; 디아세틸렌 단량체) 1.9 mg를 사용하였으며, (b) 2:8의 경우 PCDA-Galloyl 0.7 mg 및 TCDA 1.7 mg, (c) 3:7의 경우 PCDA-Galloyl 1.0 mg 및 TCDA 1.5 mg를 계량하였다.PCDA-Galloyl liposomes were prepared from two monomers, PCDA-Galloyl:TCDA, at various molar ratios of (a) 1:9, (b) 2:8, and (c) 3:7. (a) For 1:9, 0.4 mg of PCDA-Galloyl and 1.9 mg of TCDA (10,12-Tricosadiynoic acid; diacetylene monomer) were used, and (b) for 2:8, 0.7 mg of PCDA-Galloyl and 1.7 mg of TCDA were used. mg, (c) for 3:7, 1.0 mg of PCDA-Galloyl and 1.5 mg of TCDA were weighed.
구체적으로, 두 단량체를 CH2Cl2-MeOH(10:1 v/v) 용매 1 mL에 용해시킨 후 질소 가스를 퍼징(purging)하여 필름상으로 만들었다. 여기에 탈이온수 3.5 mL를 첨가하여 80℃에서 20분 동안 초음파 수조에서 소니케이션하여 분산한 뒤, 0.45 μm 크기의 기공을 가지는 시린지 필터를 사용하여 용액을 필터링한 후 4℃에서 오버나잇(overnight) 반응시켜 자가 조립을 유도함으로써 디아세틸렌 리포좀을 형성하였다. 자가 조립된 디아세틸렌 리포좀에 5분 동안 254 nm 자외선(ultraviolet rays; UV)을 조사하여 청색 상의 PCDA-Galloyl 폴리디아세틸렌 리포좀을 합성하였다.Specifically, the two monomers were dissolved in 1 mL of CH 2 Cl 2 -MeOH (10:1 v/v) solvent and then purged with nitrogen gas to form a film. Add 3.5 mL of deionized water, sonicate and disperse in an ultrasonic bath at 80°C for 20 minutes, filter the solution using a syringe filter with pores of 0.45 μm, and leave overnight at 4°C. Diacetylene liposomes were formed by inducing self-assembly through reaction. Blue-phase PCDA-Galloyl polydiacetylene liposomes were synthesized by irradiating the self-assembled diacetylene liposomes with 254 nm ultraviolet rays (UV) for 5 minutes.
시험예 1: 갈로일 그룹으로 수식된 폴리디아세틸렌 리포좀의 최적화Test Example 1: Optimization of polydiacetylene liposomes modified with galloyl groups
상기 PCDA-Galloyl 폴리디아세틸렌 리포좀에 다양한 농도(0, 3, 5, 10, 30, 50 μM)의 납 이온을 반응시킨 뒤 비색 변화 이미지와 정량적 비색 반응 값(CR, %)을 측정하고 이로부터 납 이온 검출의 가장 최적의 비율을 결정하고자 하였다.After reacting the PCDA-Galloyl polydiacetylene liposome with lead ions at various concentrations (0, 3, 5, 10, 30, 50 μM), the colorimetric change image and quantitative colorimetric response value (CR, %) were measured, and from this, We sought to determine the most optimal rate of lead ion detection.
도 3a에서 확인할 수 있듯이, PCDA-Galloyl:TCDA의 몰비 1:9로 제조된 PCDA-Galloyl 폴리디아세틸렌 리포좀은 50 μM의 납 이온을 첨가했을 때 약 46.66 ± 1.373%의 비색 반응 값과 청색에서 적색으로 가장 뚜렷한 색 전이를 나타냈다.As can be seen in Figure 3a, PCDA-Galloyl polydiacetylene liposomes prepared at a molar ratio of PCDA-Galloyl:TCDA of 1:9 showed a colorimetric response value of about 46.66 ± 1.373% and a change from blue to red when 50 μM of lead ion was added. showed the most distinct color transition.
도 3b에서 확인할 수 있듯이, PCDA-Galloyl:TCDA의 몰비 2:8로 구성된 PCDA-Galloyl 폴리디아세틸렌 리포좀의 최대 비색 반응 값은 약 32.49 ± 1.787%로 좀 더 약한 비색 변화를 보여주었다.As can be seen in Figure 3b, the maximum colorimetric response value of PCDA-Galloyl polydiacetylene liposomes composed of PCDA-Galloyl:TCDA molar ratio of 2:8 was about 32.49 ± 1.787%, showing a weaker colorimetric change.
도 3c에서 확인할 수 있듯이, PCDA-Galloyl:TCDA의 몰비 3:7로 구성된 PCDA-Galloyl 폴리디아세틸렌 리포좀은 20% 미만의 가장 약한 비색 반응 값을 보였다.As can be seen in Figure 3c, PCDA-Galloyl polydiacetylene liposomes composed of PCDA-Galloyl:TCDA molar ratio of 3:7 showed the weakest colorimetric response value of less than 20%.
따라서, 납 이온 검출을 위한 최적의 비율로 1:9 몰비를 선택하였다.Therefore, a 1:9 molar ratio was selected as the optimal ratio for lead ion detection.
시험예 2: 갈로일 그룹으로 수식된 폴리디아세틸렌 리포좀의 민감성 평가Test Example 2: Sensitivity evaluation of polydiacetylene liposomes modified with galloyl group
갈로일 그룹으로 수식된 폴리디아세틸렌 리포좀(PCDA-Galloyl:TCDA (1:9)로 구성된 PCDA-Galloyl)의 납 이온 검출 민감성을 평가하기 위해 총 100 μL의 반응 용액에 최종 농도가 0-50 μM이 되도록 납 이온을 첨가하였으며, 5분 동안 반응시킨 후 육안으로 색 변화를 관찰했을 뿐만 아니라 220-800 nm 범위의 흡수 스펙트럼을 분석하였다.To evaluate the sensitivity of polydiacetylene liposomes modified with galloyl groups (PCDA-Galloyl composed of PCDA-Galloyl:TCDA (1:9)) for lead ion detection, final concentrations of 0–50 μM were added to a total of 100 μL of reaction solution. Lead ions were added to achieve this, and after reacting for 5 minutes, the color change was observed with the naked eye and the absorption spectrum in the 220-800 nm range was analyzed.
납 이온 검출의 민감성을 정량화하기 위해 비색 반응 값(Colorimetric response, CR(%))을 계산하였다. 비색 반응 값은 아래 수식을 통해 계산되었다.Colorimetric response (CR (%)) was calculated to quantify the sensitivity of lead ion detection. The colorimetric response value was calculated using the formula below.
위 수식에서 는 중합한 청색 폴리디아세틸렌 샘플의 값이며 A는 자외선-가시광선 흡수 스펙트럼에서 청색 또는 적색에 해당하는 파장의 흡광도(Absorbance)를 나타낸다. 는 납 이온을 첨가하여 비색 전이가 발생한 폴리디아세틸렌 샘플의 흡수 스펙트럼에서 나타나는 청색 또는 적색에 해당하는 파장의 흡광도 값으로부터 얻어진 값이다.In the above formula of the polymerized blue polydiacetylene sample. value, and A represents the absorbance of the wavelength corresponding to blue or red in the ultraviolet-visible light absorption spectrum. is obtained from the absorbance value of the wavelength corresponding to blue or red appearing in the absorption spectrum of the polydiacetylene sample in which colorimetric transition occurred by adding lead ions. It is a value.
도 4a에서 확인할 수 있듯이, 청색일 때 특징적으로 나타나는 640 nm에서의 흡수 피크는 납 이온의 농도가 증가함에 따라 점차적으로 감소하고, 적색으로의 전이를 나타내는 540 nm에서의 새로운 피크는 점차 증가하는 것을 관찰할 수 있었다.As can be seen in Figure 4a, the absorption peak at 640 nm, which is characteristic for blue, gradually decreases as the concentration of lead ions increases, and the new peak at 540 nm, which indicates the transition to red, gradually increases. could be observed.
이러한 결과를 납 이온 농도에 대한 PCDA-Galloyl 리포좀의 CR 값의 선형 상관관계 그래프로 나타내었다.These results were expressed in a linear correlation graph of the CR value of PCDA-Galloyl liposomes versus lead ion concentration.
도 4b에서 확인할 수 있듯이, 0-10 μM의 납 이온 농도 범위에서 PCDA-Galloyl 리포좀의 CR 값은 좋은 선형 관계(R2= 0.981)를 보였고, 여기서 계산된 LOD(Limit of detection; 검출 한계)는 0.773 μM이다.As can be seen in Figure 4b, the CR value of PCDA-Galloyl liposomes in the lead ion concentration range of 0-10 μM showed a good linear relationship (R 2 = 0.981), and the limit of detection (LOD) calculated here was It is 0.773 μM.
PCDA 단량체에 기능화된 갈로일 그룹(Galloyl Group)은 폴리디아세틸렌이 형성될 때 외부로 노출되도록 설계되었다. 갈로일 그룹은 납 이온과 배위 결합을 형성할 수 있는 것으로 알려져 있다. 따라서, 납 이온의 농도가 증가함에 따라 폴리디아세틸렌 표면에 위치하는 갈로일 그룹과 납 이온 사이의 상호 작용이 더 커지게 되고, 폴리디아세틸렌 내부의 공액 백본 뒤틀림 또한 더 크게 발생하여, 적색으로의 색 전이 정도가 커지는 것으로 추정된다.The galloyl group functionalized in the PCDA monomer was designed to be exposed to the outside when polydiacetylene is formed. It is known that galloyl groups can form coordination bonds with lead ions. Therefore, as the concentration of lead ions increases, the interaction between the galloyl group located on the surface of polydiacetylene and lead ions becomes larger, and the conjugate backbone distortion inside polydiacetylene also occurs more, resulting in a red color. It is estimated that the degree of color transfer increases.
시험예 3: 갈로일 그룹으로 수식된 폴리디아세틸렌 리포좀의 선택성 평가Test Example 3: Selectivity evaluation of polydiacetylene liposomes modified with galloyl group
갈로일 그룹으로 수식된 폴리디아세틸렌 리포좀의 납 이온 검출 선택성을 평가하기 위하여, 납 이온(Pb2+)의 결합 과정에서 경쟁할 수 있는 금속 양이온[나트륨(Na+), 칼슘(Ca2+), 마그네슘(Mg2+), 철(Fe3+), 니켈(Ni2+)]들을 총 100 μL의 반응 용액에서 200 μM 농도로 폴리디아세틸렌과 5분 동안 반응시켰다. 이후 220-800 nm 범위의 흡수 스펙트럼을 분석하여 납 이온 검출의 선택성을 확인하기 위한 비색 반응 값을 계산하였다.To evaluate the lead ion detection selectivity of polydiacetylene liposomes modified with galloyl groups, metal cations [sodium (Na + ), calcium (Ca 2+ ) that can compete in the binding process of lead ions (Pb 2+ ) were used. , magnesium (Mg 2+ ), iron (Fe 3+ ), nickel (Ni 2+ )] were reacted with polydiacetylene at a concentration of 200 μM in a total of 100 μL of reaction solution for 5 minutes. Afterwards, the absorption spectrum in the 220-800 nm range was analyzed to calculate the colorimetric response value to confirm the selectivity of lead ion detection.
도 5a에서 확인할 수 있듯이, 납 이온을 제외한 다른 금속 이온에 대해서는 Galloyl-PCDA 리포좀의 흡수 스펙트럼 변화가 무시할 수 있는 수준인 것으로 나타났다. 따라서, 납 이온을 제외한 모든 금속 이온과의 반응 후 적색으로 변이 시 보이는 540 nm에서의 흡수 피크를 확인할 수 없었고, 이로부터 개발된 Galloyl-PCDA 리포좀은 납 이온에 대한 선택성이 매우 큰 것으로 확인되었다.As can be seen in Figure 5a, the absorption spectrum change of Galloyl-PCDA liposome was found to be negligible for other metal ions except lead ions. Therefore, the absorption peak at 540 nm, which is visible when the color changes to red after reaction with all metal ions except lead ions, could not be confirmed, and the Galloyl-PCDA liposome developed from this was confirmed to have very high selectivity for lead ions.
이어서 납 이온 및 금속 양이온의 첨가에 의한 흡수 스펙트럼의 변화를 육안으로 확인한 결과와 비색 반응 값을 계산하였다.Subsequently, the changes in the absorption spectrum due to the addition of lead ions and metal cations were visually confirmed and the colorimetric response values were calculated.
도 5b에서 확인할 수 있듯이, 납 이온을 제외한 다른 금속 양이온들과 Galloyl-PCDA 리포좀을 반응시킨 후 색 전이는 무시할 수 있는 수준이었고, CR(%) 값도 5% 미만이었다. 이는 개발한 Galloyl-PCDA 리포좀 시스템이 다른 금속 양이온이 존재하는 상황에서도 납 이온과만 선택적으로 반응하여 납 이온만을 효과적으로 모니터링할 수 있음을 보여주는 결과이다.As can be seen in Figure 5b, after reacting the Galloyl-PCDA liposome with metal cations other than lead ions, the color transition was negligible, and the CR (%) value was less than 5%. This result shows that the developed Galloyl-PCDA liposome system can effectively monitor only lead ions by reacting selectively with lead ions even in the presence of other metal cations.
Claims (13)
[화학식 1]
.The composition for detecting lead ions according to claim 1, wherein the diacetylene monomer functionalized with a galloyl group has the structure of the following formula (1):
[Formula 1]
.
갈로일(galloyl) 그룹으로 기능화된 디아세틸렌(diacetylene) 단량체 및 카르복실(carboxyl) 그룹으로 기능화된 디아세틸렌 단량체를 포함하는 디아세틸렌(polydiacetylene) 리포좀을 제조하는 리포좀 형성 단계; 및
상기 디아세틸렌 리포좀에 자외선(ultraviolet rays; UV)을 조사하여 폴리디아세틸렌 리포좀을 제조하는 광중합 단계.Method for preparing a composition for detecting lead ions comprising:
A liposome formation step of preparing a polydiacetylene liposome containing a diacetylene monomer functionalized with a galloyl group and a diacetylene monomer functionalized with a carboxyl group; and
A photopolymerization step of producing polydiacetylene liposomes by irradiating ultraviolet rays (UV) to the diacetylene liposomes.
[화학식 1]
.The method of claim 5, wherein the diacetylene monomer functionalized with a galloyl group has the structure of the following formula (1):
[Formula 1]
.
[화학식 1]
.The method of detecting lead ions according to claim 9, wherein the diacetylene monomer functionalized with a galloyl group has the structure of the following formula (1):
[Formula 1]
.
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