표면탄성파 및 양자폭포레이저를 적용한 고감도 화학작용제 검출기술에 관한 연구

김진욱 인하대학교 대학원 2021 국내석사

Chemical warfare agents (CWAs) can cause fatal damages to living species, resulting severe problems of mankind due to its toxicity and chemical reaction. Because these weapons are cheap, easily mass-produced, and can cause indiscriminate mass destruction, the Chemical Weapons Convention (CWC) signed in 1997 prohibited this chemical weapon, but the threat to chemical weapons still exists. In addition to these chemical weapons, toxic industrial chemicals (TICs) are emerging as a risk factor in industrial sites and people's lives. Therefore, it is becoming important to develop gas detection technology to prevent or minimize serious human injury early. In this study, a chemical detector based on surface acoustic wave (SAW) and quantum cascade laser (QCL) was built and its performance was evaluated by exposure test to CWA and TIC. The SAW sensor consists of a piezoelectric substrate, interdigital transducer (IDT), and a reflector, and is designed to operate at a resonant frequency of 250 MHz. Also, the POSS (polyhedral oligomeric silsesquioxane) and thiourea (TU)-based polymers with a hydrogen bond with nerve agents were used as sensing materials for detecting nerve agents. Four-channel SAW array devices with these SAW sensors were developed and CWA exposure tests were conducted for PC-based SAW array devices and portable SAW array devices. These three SAW sensors coated with each sensing materials showed significant frequency shifts against the nerve agent simulants and showed little response to other analyte vapors. As a result of exposure experiments on dimethyl methylphosphonate (DMMP) and sarin (GB), the POSS showed the highest sensitivity of these three sensors and is especially of practical utility because it can detect concentrations below median lethal concentration (LCt50) of GB. To confirm the reliability of POSS, the high-performance sensing material, a long-term stability test was carried out for 180 days, and the sensor will likely maintain good performance in the long-term if it prevents the initial degradation of performance. In the case of TIC detection using the SAW sensor, it confirmed that a SAW sensor coated with ZnO can detect CO, a type of TIC, and it is shown that the sensitivity to CO tends to increase as the deposition thickness of ZnO increases. A QCL-based detector, which is a contactless-type gas detector, can acquire the spectra of CWA and TIC, and consist of QCL, mid-IR photodetector, a driving circuit, and optics. DMMP and NH3 were measured using QCL-based infrared spectroscopy, and the characteristic band of these analytes was confirmed. Both DMMP gases and aerosols exhibit high R-square (0.99 and above) depending on the concentration in the characteristic band. DMMP also represent different spectra depending on the state (gas or liquids), indicating that changes in characteristic absorption lines occur depending on the distance between molecules. Also, NH3 spectra were acquired using QCL-based infrared spectroscopy, and absorbance of characteristic bands showed good linearity according to NH3 concentration.

Design and Synthesis of Trisaryl Phosphoric Triamide-Based Receptor for the Detection of Chemical Warfare Agents

허재영 성균관대학교 일반대학원 2024 국내석사

Chemical warfare agents (CWAs) pose a persistent threat to human safety, and bis(2-chloroethyl) sulfide, or sulfur mustard (SM) is one of the most dangerous substances and is able to cause serious harm. Detecting SM gas is vital, but current methods have high-temperature requirements and limited selectivity, mainly because of the lack of CWA receptor development, and this makes them challenging to use. To address this issue, we present a trisaryl phosphoric triamide-based resin receptor that preferentially interacts with a SM simulant 2-chloroethyl ethyl sulfide (2-CEES) through dipole interactions. The receptor was synthesized through a facile process using an amine and a triethyl phosphate and the properties of its coating were enhanced using epoxy chemistry. The receptor's superior triamide structure was evaluated using a quartz crystal microbalance and reactivity was confirmed by observing the variations in reactivity according to the number of phosphoramides. The receptor showed better reactivity to 2-CEES vapor than to the known poly(epichlorohydrin) and showed selectivity to other volatile organic compounds. Moreover, its durability was evident even 30 days post-coating. The applicability of this receptor extends to array sensors, sound acoustic wave sensors, and chemo-resistive and chemo-capacitive sensors, and it promises advances in chemical warfare agent detection. 화학전략물질(CWAs)은 인간의 안전에 지속적인 위협을 안겨주는데, 이 중 이 화학작용제인 sulfur mustard 가스는 가장 위험한 물질 중 하나로 심각한 피해를 일으킬 수 있습니다. SM 가스를 감지하는 것은 중요하지만, 현재의 방법은 고온 요구 사항과 선택성이 제한되어 있어 CWA 수용체 개발에 있어서 부족함이 있습니다. 이 문제를 해결하기 위해, 우리는 2-클로로에틸 에틸 설파이드(2-CEES)와 상호작용하는 트리스아릴 포스포릭 트리아마이드 기반 수용체를 제안하였습니다. 이 수용체의 우수한 트리아마이드 구조는 쿼츠 석영 마이크로밸런스를 사용하여 평가되었습니다. 이 수용체는 알려진 폴리(에피클로로히드린)보다 반응성이 우수하며, 다른 휘발성 유기 화합물에 대한 선택성이 높게 나타났습니다. 또한, 코팅 후 30일이 지난 후에도 반응성이 거의 변하지 않는 결과를 보이며 내구성을 입증하였습니다. 이러한 수용체는 어레이 센서 등 다른 센서에도 적용 가능하며. 이를 통하여 화학전략물질 검출 분야의 진보를 약속합니다

Photothermally Active Core-Shell Catalyst based on UiO-66 and Polydopamine for Highly Effective Detoxification of Nerve Agents When Used with Amine-Derivatized Dendrimer Functionalized Silica Particle

Jang, Woon Jin 고려대학교 대학원 2023 국내석사

Chemical warfare agents (CWAs) are considered a great threat to society due to their ability to cause paralysis and death even with a small amount of exposure. Metal-organic frameworks (MOFs) are promising catalysts with abundant catalytic active sites for the detoxification of organophosphate base nerve agents. In this work, a noble type of core-shell material (Fe3O4@PD@UiO-66) was developed for use as a catalyst in the decomposition of toxic organophosphate. This core-shell structured catalyst consisted of three layers: iron oxide, polydopamine (PD), and MOFs (UiO-66). The magnetic iron oxide core was introduced to facilitate quick recovery and reuse of the catalyst after the reaction. PD layer has strong near-infrared (NIR) absorption and emits heat to increase reaction speed. MOFs layer was synthesized to layer-by-layer epitaxial strategy. N-ethylmorphloine (NEM) is commonly used as regenerators in the hydrolysis of CWAs using MOFs. In this study, silica particles modified with PAMAM dendrimers (D4) were introduced to replace NEM (NH2-DS). PAMAM has numerous amine groups that can regenerate MOFs catalyst effectively. The mixture of Fe3O4@PD@UiO-66 and NH2-DS worked perfectly as a heterogeneous catalyst for degrading DMNP. Under IR irradiation, the PD layer absorb IR and converts it into heat energy, increasing the catalytic activities of MOFs with a 5 min of half-life. Without IR irradiation, the half-life of DMNP decreased to 45 min, with the same catalyst mixture. Additionally, various bases were also modified on the surface of Fe3O4@PD@UiO-66 and tested to hydrolysis without regenerators. At the last, Fe3O4@PD@UiO-66 and NH2-DS mixture was tested to decompose real chemical warfare agents, including sarin (GB), soman (GD) and VX, under IR-LED irradiation. Remarkably, GB was effectively decomposed with a half-life of 4.2 min, and GD demonstrated a half-life of 8.7 min. VX was hydrolyzed with a half-life of 14.0 min. 화학무기는 적은 양의 노출로 마비와 죽음에 이르게 하기 때문에 사회에 큰 위협이 되어 왔습니다. 유기금속 복합체 (MOFs)는 신경작용제를 제독 할 수 있는 많은 활성 부위가 있기 때문에 유기인산 기반의 신경작용제를 매우 효율적으로 제독 할 수 있습니다. 이번 연구에서는 새로운 코어-쉘 구조의 물질을 (Fe3O4@PD@UiO-66) 이용하여 독성 유기인산화물을 분해하는 촉매로써 사용하였습니다. 이 코어=쉘 구조의 촉매는 3가지 층으로 이루어져 있습니다. 산화철, 폴리도파민 (PD), 그리고 유기금속 복합체(UiO-66)로 이뤄져 있습니다. 자성이 있는 산화 철 코어는 반응 후 빠르게 회수하여 재사용을 하기 위해 선택이 되었습니다. 폴리도파민 층은 근적외선에서 강한 흡수를 보이고 열을 방출하여 반응속도를 증가시킵니다. 금속 유기 복합체 층적 (layer-by-layer) 합성 방법으로 합성하였습니다. 금속 유기 복합체를 이용하여 화학작용제를 가수분해하는 반응에는 일반적으로 N-에틸모폴린을 이용하여 촉매를 재생합니다. 이번 연구에서는 PAMAM 덴드리머 (D4)를 붙인 실리카를 N-에틸모폴린을 대신하기 위해 사용을 하였습니다. PAMAM은 수많은 아민 그룹을 가지고 있고 금속 유기 복합체를 효과적으로 재생 시킬 수 있습니다. 코어-쉘 촉매와 덴드리머 기능화된 실리카 혼합물은 불균일 촉매로써 DMNP를 효과적으로 분해를 합니다. 적외선을 조사하면, 폴리도파민 층은 적외선을 흡수하고 열을 방출하여 반응을 촉진 시켰고, DMNP는 5분의 반감기를 가지고 분해가 되었습니다. IR을 조사하지 않는 조건에서는 DMNP는 45분의 반감기를 가지고 분해 되었습니다. 추가적으로, 다양한 염기를 코어-쉘 촉매에 붙여서 촉매를 재생하기 위한 시도도 하였습니다. 마지막으로, 코어-쉘 촉매와 덴드리머 기능화된 실리카의 혼합물이 사린 (GB), 소만 (GD) 그리고 VX를 비롯한 여러 가지 실 작용제를 적외선 조사 하에 분해하는데 사용이 되었습니다. 사린은 4.2분의 반감기를 가지고 소만은 8.7 분의 반감기를 가졌으며, VX는 14.0분의 반감기를 가지고 가수분해 반응이 일어났습니다.

Preparation and Characterization of Zr-MOF Polymer Composite to Detoxify Toxic Compound

NGO HOANG LONG University of Science and Technology - KITECH Scho 2020 국내박사

Nerve agents are a class of chemical warfare agents which were usedduring war time. Until now, scientists are still doing researches to find betterdetoxification processes for the safety of humans especially the soldiers onbattlefields. In the past, toxic compounds were usually absorbed by porous materialas common activated carbon, however the amount and lasting protectionbased on the absorbent amount that is the limitation of this approaching.Directly decomposing the toxic compound is the potential method that wasreported in recent years by using metal-containing material. Metal organicframework, a class of highly porous material, is the mixing of porousmaterial and containing metal-site. By constructed from metal-nodes andorganic linker lead MOF structure to diverse and suitable for thedetoxification of a lot of nerve agents. To expand the application of MOF onthe detoxified process, MOF particles was embed in the polymer matrix.The composite materials was introduced in the decomposition of MPO. In this thesis, two kind of composite material was synthesized andinvestigated the decomposition properties. The PVA/BPEI@MOF-808 shows a MPO decomposition conversion 60% for 3 hours and up to 92%for 24 hours in water condition. This is first research about the MPOdecomposition by film coating in the aqueous solution. Keyword: Chemical warfare agents, nerve agents simulants, peelablecoating, metal-organic framework, methylparaoxon.

후막 형성법을 이용한 화학작용제 검출용 마이크로 가스센서 시스템의 제작

곽준혁 경북대학교 대학원 2008 국내석사

Micro array gas sensor system based on PDA has been manufactured to detect chemical warfare agent (CWA). The PDA is small, portable and flexible system, so it can be easily adapted to soldiers at the battlefield. Tin oxide thick film based gas sensors have been fabricated and their gas response characteristics have been examined for four simulant gases of chemical warfare agent. The sensing materials are prepared by two synthesis methods such as ball-milling process and co-precipitation process. Al2O3 4 wt.% and In2O3 2 wt.% are added to SnO2 by physical ball milling process. ZnO 2 wt.% and ZrO2 1 wt.% are added to SnO2 by co-precipitation method. Metal catalyst is deposited to improve the stability on the sensing film by using the micro dropping method. And back-side etching technique, one of the micro electro mechanical system (MEMS) technologies, is used to reduce the power consumption of sensor. The fabricated heater power have been consumed about 65 mW at operating temperature of 300 ℃. Response characteristics are examined for test gases. Test gases are DMMP, DCP, CH3CN and CH2Cl2 that are used as simulant gases of chemical warfare agents. These sensors show high sensitivity more than 50 % at 500 ppb concentration for test gases and good repeatability. The sensor array identities among four simulant gases through the principal component analysis (PCA). Also, classification of gases is studied using adaptive resonance theory (ART II) that is one of the neural network algorithm. And the results are shown in the PDA system. The system has detected chemical warfare agents excellently.

Surface Modification of Ordered Mesoporous Carbon (OMC) by Diazonium Chemistry for DMMP Sensor

황윤경 성균관대학교 일반대학원 2016 국내석사

Organophosphate (OP) compounds are a family of organic compounds having phosphorus. It is mainly employed pesticides and chemical warfare agents36, 37. Because this compound is highly toxic chemicals, it destroys the environment and harms to human body. In recent years, OP has aroused interest in environmental and security fields due to their use in pesticides and as chemical warfare agents. For this reason, a great effort to detection OP and monitoring of exposures to chemical warfare agents become increasingly important. In this research, we synthesis the functionalized ordered mesoporous carbon via the diazonium chemistry, which is in-situ generated and reacted with the carbon surface. And it have designed for the gas-phase detection of toxic nerve agents simulator such as dimethyl methylphosphonate (DMMP) using a quartz crystal microbalance (QCM) technology. DMMP was chosen as a simulant for the presence of P=O, P-CH3 and P-OCH3 functional groups38, 39, which as exist in the nerve agents. We have prepared adjust functional group ratio on carbon surface (CMK-3) and applied to DMMP detection. The synthesized material was identified by small angle X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), N2 sorption isotherms, elementary analysis, thermogravimetric analysis (TGA) and titration to examine the surface acidic properties. And DMMP sensing properties were characterized by a quartz crystal microbalance (QCM) technique. In the sensing properties, sulfonated CMK-3 (carbon vs. sulfonic group = 1:0.01, 1:0.05, 1:0.1) shows 21.4, 29 and 33 Hz/ppm∙μg upon exposure to 50ppm DMMP, respectively. These values are more highly than pristine CMK-3 (17 Hz/ppm∙μg) and all samples have good reproducible properties.

Human olfactory receptor-based CNT-FET sensor for the detection of DMMP as a simulant of sarin

유진 서울대학교 대학원 2018 국내석사

Dimetyl metylphosphonate (DMMP) is a simulant of sarin that representative of nerve agents. Sarin is an organophosphorus toxic compound that is an inhibitor of acetylcholinesterase which paralyzes human neurotransmission and autonomic nervous system. Detection of these nerve agents is important for safety from terrorism and military threats. Although there have been many studies on sensors for detecting DMMP as simulant of sarin, they still showed some limitations in specificity, sensitivity and practicality. To overcome these limitations, we applied a human olfactory receptor (hOR)-based single-walled carbon nanotube-field effect transistor (swCNT-FET). The hOR has high specificity for certain target molecule and swCNT-FET has high sensitivity that could convert biological signal to electrical one. Through hORs screening, hOR2T7 had high selectivity for DMMP and it was produced, purified and reconstituted for development of hOR2T7-conjugated bioelectronic nose (hOR2T7 B-nose). These hOR2T7 B-nose was able to selectively detect DMMP at a concentration of 10 fM. This shows the ultrasensitive and selective performance for the detection of DMMP as a tool for sensing CWAs, which could be used for practical application in field of safety.

Preparation of polymeric nanofiber composites using simultaneous electrospinning/electrospraying and their application to protective materials

류수열 Seoul National University 2016 국내박사

Nanomaterials demonstrate interesting physical and chemical properties compared with conventional materials. Various types of new materials, such as nanoparticle, nanorod, nanosphere and nanofiber, have been investigated. The creation of new functional nanomaterials contributes significantly to the innovation of nanoscience and nanotechnologies. Among them, electrospun nanofibers have been attracting the attention of highly functional materials due to their enhanced properties, such as high surface to volume ratio, very high porosity compared to other conventional fibers. So, nanofibers have been studied for various applications in fields of filtration, tissue engineering, sensor, protective material, electronic and photonic material and drug delivery. In this study, the polymeric nanofiber composites were developed using simultaneous electrospinning/electrospraying, then applied to protective materials. In chapter 2, two types of electrospun polyamide nanofiber composites in which Ag-TiO2 was located either in the interior or on the surface of the nanofiber using electrospinning and simultaneous electrospinning/electrospray (SEE) process, respectively. The performance of the obtained Ag-TiO2-embedded nanofiber composite (interior located Ag-TiO2: AT-in-NF) and Ag-TiO2-decorated nanofiber composite (surface located Ag-TiO2: AT-sur-NF) was compared by evaluating the decolorization of methylene blue (MB) stain and their antimicrobial ability. It was concluded that the positioning of nanomaterial additives is a crucial factor in the enhanced performance of such nanofiber composites, and provide a guide for designing and optimizing nanofiber composites with superior catalytic activities. In chapter 3, a potential application of nanofibrous composite materials impregnated the MgO and POM adsorbents was exhibited as an inner layer for the permeable protective clothing against CWA. The nanofiber composites, which were consisted of both polyamide nanofiber and adsorbents (MgO and POM), were prepared using the SEE process. The nanofiber composites were compared to neat polyamide nanofiber mat by evaluating the permeability of air, moisture and protectability against gas chemical warfare simulants. It was suggested that the high possibility of the application of the nanofiber composites to the inner layer of permeable protective clothing. In chapter 4, it was reported that electrospun meta-aramid nanofibers with enhanced chemical stability and mechanical property using sequential post-treatment for removal of salt in the nanofiber and regeneration of crystalline structure. The aligned meta-aramid nanofibers with LiCl salt was prepared using electrospinning apparatus with drum-collector. The washing and heating sequential post-treated nanofiber mats showed improved chemicals stability. Furthermore, in order to estimate the possibility of their application to an outer layer for permeable protective clothing having the repellency against liquid chemical warfare simulants, the surface of meta-aramid nanofibers was modified via treatment using water and oil repellent. In chapter 5, lightweight nanofibrous assemblies with high protection ability against chemical warfare agents (CWAs) were developed using laminated outer and inner layers based on aromatic and aliphatic polyamide nanofiber composites with CWA adsorbents magnesium oxide and polyoxometalate. Thickness, weight density (weight per area), cool/warm feeling and air/moisture permeability of the assembly were compared with the permeable protective clothing of Korea Army as a reference. The thickness and weight density were variated according to the number of stacking, and finally, the lightweight assemblies with high protectability against CWA can be developed. The assembly surpassed the reference in the cool feeling property, and provided good resistance to the penetration of chemical warfare agents in gas form, while still allowing significant water vapor transmission to promote evaporate cooling of the body. The development of the assembly suggests new approach to improving performance of a permeable protective materials, and provides a guide for designing and optimizing the permeable protective clothing.

(A) novel approach toward degradation of Chemical Warfare Agents (CWA) : direct detoxification of sulfur mustard simulant by UV-C irradiation

최이태 Graduate School, Korea University 2021 국내석사

Detoxification of chemical warfare agents (CWAs) is an important part of protecting from chemical terrorism. To protect against these risks, it is necessary to develop materials that are resistant to CWAs and to have a system in place that can be deciphered immediately. Therefore, studies to decipher it have been underway since decades ago. However, instantaneous decomposition remains challenging when the photo-catalysts such as TiO2 and ZnO are applied. Reactive oxygen species (ROS) are highly reactive molecules. Through this, it is widely used in food, medicine, and chemical fields. Therefore, ROS is drawing attention as a potential substance that decomposes CWAs. We are trying to solve the difficulty of immediate disassembly using ROS. Recently we found that oxidation of CWAs is possible using ultraviolet (UV) irradiation without any photocatalyst. UV is known to have enough energy to break-down or trigger the decomposition of CWAs. Especially, UV-C (200~280 nm) are good candidates because of their high energy. Herein, we report a strategy for decontamination of a CWA simulant including 2-CEES (2-chloroethyl ethyl sulfide) under UV-C (273 nm) irradiation in liquid phase. 2-CEES is a simulant of mustard gas. Furthermore, we also examed a solvent effect on the decomposition such as dichloromethane (MC), acetone and acetonitrile (AcCN). Interestingly, 2-CEES underwent to a non-toxic material, CEESO, with 98% conversion within 9 minutes when acetonitrile was used. Such an oxidation rate was significantly higher compared to those of the corresponding photo-decompositon research reported so far. What’s more, we demonstrated the use of oxygen in mechanisms through the singlet oxygen (1O2) scavenger experiment.

Photothermally enhanced catalytic activity of metal oxide composites for detoxification of chemical warfare agent simulant

김예지 Graduate School, Korea University 2022 국내석사

Various organophosphate compounds are used as nerve agents of chemical warfare agents (CWAs), insecticides, and pesticides. Willingly or not, these compounds continuously threaten human health due to the inherent property of acetylcholinesterase (AChE) inhibition. Among them, the nerve agents of CWAs are the main lethal agents which can cause permanent damage even after treatment. To detoxify these toxic organophosphate compounds, various catalysts such as metal oxides, metal-organic frameworks (MOFs), and enzymes are examined during the past decades. But each catalyst has different advantages and disadvantages for detoxification usage. In the case of metal oxides, excellent thermal and chemical stabilities are the main advantage. However, the decomposition rate of organophosphate chemicals is relatively slow compared to other catalysts. To increase the conversion rate, the photothermal material hybrid catalysts were recently investigated. In this thesis, the MgO hybrid composite catalyzed the transesterification reaction of toxic organophosphates and produced non-toxic products without undesired side products. The MgO particles were embedded into pores of the mesoporous silica (SBA-15) and the MgO@SBA-15 composites were linked to graphene oxide (GO). The large pore size of SBA-15 (6 nm) is enough that the chemicals easily path through without interference. Moreover, under infrared (IR) light-emitting diode (LED), the temperature of the reaction solvent was increased by the photothermal effect of GO. High reaction temperature accelerated the conversion rate of degradation. The half-life (t1/2) of DMNP was deceased 30 min to 15 min. Additionally, the catalytic activity of MgO@SBA-15@GO was maintained after five times of reuse thanks to the great thermal, chemical stability. Herein, the properties of the MgO hybrid composite and the enhanced decomposition performance by photothermal effect were studied.