The authors have no acknowledgements.

순차 추가를 통해 CMP 박막 1. 합성 <ol><li> 운모에 금의 자기 조립 단분자막 (SAM) 작용. <ol><li> 에탄올 11 피페 운데 산 프로 파길 아미드 (14)의 1 mM의 용액 (SAM-용액)을 준비한다. 해결책은 분명하다까지 초음파 목욕을 사용하여 섞는다. 알루미늄 호일을 사용하여 빛으로부터 병을 보호합니다. </li><li> 아르곤 하에서 금 운모 웨이퍼를 얻습니다. 저장 용기로부터 인출 한 후 18 시간 동안 SAM-용액에 직접 운모 웨이퍼를 몰입. </li><li> , SAM-용액으로부터 제조 된 금 운모 웨이퍼를 타고 질소 기류 하에서 에탄올 건조 씻어. 이후 빛과 불활성 가스에 의해 보호 기판을 저장합니다. </li></ol></li><li> 전구체 솔루션을 제공합니다. <ol><li> 18.64 mg의 구리 촉매 (테트라 키스 (아세토 니트릴) 구리 (I) 헥사 플루오로 포스페이트), 20.83 mg을 테트라 페닐 메탄 (TPM) -alkyne와 24.22 mg을 TPM - 아 지드를 달아 별도의 쉬 렌크 플라스크에 각 구성 요소를 작성하십시오.TPM - 알킨 및 TPM - 아 지드 그림 1 참조, 합성 참조 (15)에 설명되어 있습니다. 대피 및 불활성 가스 (N 2, 아르곤) 3 회 리필. </li><li> 각각의 슈 렝크 플라스크에 25 ml의 물이없는 테트라 히드로 푸란 (THF)를 첨가. 알루미늄 호일을 사용하여 빛으로부터 TPM - 아 지드와 TPM-알킨과 플라스크를 보호합니다. </li></ol></li><li> CMP 제조를위한 장치를 준비합니다. 주 : 합성 장치는도 2에 도시된다. <ol><li> 250 ml의 한 구 둥근 바닥 플라스크를 사용합니다. 130 ML의 THF를 입력합니다. 알킨으로 코팅 준비 기판을 넣어 샘플 실에서 SAM을 종료했습니다. 기판이 직립되도록 샘플 홀더를 사용한다. </li><li> 환류 냉각기의 상단의 접합을 통해 쉬 렌크 라인에 장치를 연결합니다. </li><li> 3 회 대피 및 불활성 가스로 환기. </li></ol></li><li> 불활성 조건에서 연속 또한. <ol><li> 90 ° C로 히터를 설정하고 THF를 다시가 될 때까지 기다립니다플럭 싱. </li><li> 샘플 구획​​의 하단 출구 위에 샘플 구획​​으로부터 THF를 보자. 출구를 닫습니다. </li><li> 준비 TPM - 아 지드 시액 1 mL 및 격막과 스크류 캡을 통해 샘플 실에 구리 (I) 촉매 용액 0.5 ml를주세요. 반응 장치로 쉴 렌크 플라스크로부터 솔루션을 순차적으로 전송하는 중공 바늘 주사기를 사용한다. 참고 서열은 반응에 영향을 미치지 않는다. </li><li> 약 30 분을 기다립니다. </li><li> 샘플 구획​​의 하단 출구에 걸쳐 반응 액을 보자. 출구를 닫고 샘플을 세척하기위한 응축 된 THF를 수집합니다. 약 30 분을 기다립니다. </li><li> 샘플 구획​​의 하단에있는 출구를 통해 세척 용액을 보자. 출구를 닫습니다. </li><li> 준비 TPM-알킨 액 1 mL 및 격막과 스크류 캡을 통해 샘플 실에 구리 (I) 촉매 용액 0.5 ml를주세요. 중공으로 주사기를 사용하여바늘은 반응 장치에 쉴 렌크 플라스크로부터 솔루션을 순차적으로 전송한다. 참고 서열은 반응에 영향을 미치지 않는다. </li><li> 약 30 분을 기다립니다. </li><li> 샘플 구획​​의 하단 출구에 걸쳐 반응 액을 보자. 출구를 닫고 샘플을 세척하기위한 응축 된 THF를 수집합니다. 약 30 분을 기다립니다. </li><li> 반복 층의 원하는 양에 도달 할 때까지 1.4.9 1.4.3 단계. 주 : 하나의 층은 약 1 nm 두께이다. </li><li> , CMP 코팅 운모 기판을 꺼내 THF, 에탄올로 헹구고, 질소 기류 하에서 건조. </li></ol></li></ol> CMP Nanomembranes 2. 전송 <ol><li> 폴리 (메틸 메타 크릴 레이트) (PMMA) 용액. <ol><li> 에틸 아세테이트 중 4 % (중량) PMMA (996 kDa의 M)의 용액을 제조 하였다. 이 솔루션은 분명하다까지 PMMA는 초음파 목욕을 사용하여 녹인다. </li></ol></li><li> PMMA 용액을 스핀 코팅. <ol><li> RA 스핀 코터를 설정할MP 시간 0 RPM 4,000에서 10 초, 시간이 40 초를 들고와 4000 0 rpm으로 시간이 10 초 램프. </li><li> 스핀 코터에 CMP 운모 기판을 배치하고 완전히 피복 될 때까지 웨이퍼 상 PMMA 용액을 넣어. 스핀 코터를 시작합니다. </li><li> 스핀 코팅이 완료된 후 90 ℃에서 가열 플레이트 상에 5 분간 샘플을 넣어. </li><li> 운모 기판의 각 가장자리에서 1mm를 잘라. 가장자리를 잘라 가위를 사용합니다. </li></ol></li><li> PMMA의 전송의 CMP nanomembrane 코팅. <ol><li> 와 KI의 / H 2 O (1:10 M / M) I 2 / KI / H 2 O 솔루션 (: 4 : 40m / M / M 1)을 준비합니다. </li><li> 요리를 결정화 150 ㎖의 I 2 / KI H 2 O 솔루션을 입력하고 요리를 결정화 100 ㎖에서 KI / H 2 O 솔루션을 입력합니다. 나는 2 / KI / H 2 O 솔루션의 상단에, 용액에 접촉 운모로, 운모 기판 상에 PMMA 코팅 된 CMP 골드를 넣습니다. 이 가라 앉지 않도록주의.적어도 5 분을 기다립니다. </li><li> 나는 2 / KI / H 2 용액에 접촉 운모와 KI / H 2 O 솔루션의 상단에 O 솔루션에서 PMMA 코팅 된 CMP 금 운모 기판을 넣습니다. 이 가라 앉지 않도록주의. 적어도 5 분을 기다립니다. </li><li> 요리를 결정화 250 ㎖에 증류수를 입력합니다. 운모의 PMMA / CMP / 금 필름을 벗겨. 약간 증류수에, 하나의 가장자리에서 시작, 기판을 침지하여이 작업을 수행합니다. 운모는 물을 가리 키도록 기판을 유지. 참고 :이 절차는 그림 3에 표시됩니다. </li><li> 딥 - 코팅 된 실리콘 웨이퍼에 PMMA / CMP / 금. 그것은 수영 PMMA / CMP / 금 막의 가장자리에 닿을 때까지 웨이퍼 천천히 PMMA / CMP는 / 금에 접근하여이 작업을 수행합니다. 실리콘 웨이퍼는 PMMA / CMP / 금 막과 접촉하면 서서히 실리콘 웨이퍼를 꺼내. </li><li> 실리콘 웨이퍼로부터 PMMA / CMP은 / 금 막을 벗겨. 약간 하나 ED에서 시작, 기판을 침지하여이 작업을 수행GE, 나는 2 / KI / H 2 O 솔루션입니다. 15 분을 기다립니다. </li><li> 금이 완전히 에칭 된 후, 실리콘 웨이퍼를 통해 물 PMMA / CMP 막 옮긴다. 15 분을 기다립니다. </li><li> 세 번 단계를 반복 2.3.7 물과 멤브레인을 씻어. </li><li> 단계 2.3.5에서 설명한 방법을 통해, 목적하는 기판, 예를 들면, 현미경 슬라이드 또는 금 - 코팅 된 실리콘 웨이퍼를 세척 PMMA / CMP 막 옮긴다. 적어도 2 시간 동안 공기의 PMMA / CMP 기판 건조하자. </li></ol></li><li> PMMA의 해산. <ol><li> 아세톤에 PMMA / CMP 기판을 넣습니다. 30 분을 기다립니다. 기판을 꺼내 아세톤으로 씻어. </li><li> 단계를 반복 2.4.1 세 번. </li><li> 적어도 2 시간 동안 CMP 기판 건조하자. </li></ol></li></ol>

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</ol>

The authors have nothing to disclose.

CMP-필름의 합성을위한 촉매의 용액을 신선한이어야한다. 깨진 촉매 (즉, 산화) 솔루션의 푸른 색채로 표시됩니다. 신선한 액은 무색이다. 중요한 점은 스핀 코팅 후 PMMA 운모 기판의 가장자리를 절단하는 것이다. 또한, 기판에 결함이 절단 예정 즉, 각각의 스폿은 PMMA 인해 누락 된 금 층, 운모 기판과 접촉 할 수 있었다. 그렇지 금층 용이 운모 기판으로부터 박리 될 수 없다. 분리는 하나의 에지 또는 코너에서 시작 후 또한, 운모 기판으로부터 금층의 박리 관한 금 층이 완전히 분리 될 때까지, 하나는이 가장자리에서 계속한다. 요오드 용액 ​​또는 물에 요오드 용액으로부터 수조에서 실리콘 웨이퍼, 예와 PMMA / CMP 막의 전송하는 동안, 그 중요멤브레인은 건조하지 않습니다. 막이 실리콘 웨이퍼 상에 건조 후에는 다시 분리하는 것은 거의 불가능하다. PMMA를 용해시킨 후, 각각의 세정 단계가 조심스럽게 수행되어야한다; 막에서 중첩 된 가장자리는 기판으로부터 막으로 제거 될 수 있습니다. 이때 시료의 크기는 샘플 구획​​의 크기에 의해 제한된다. 각 사이클은 약 2 시간이 필요하기 때문에 제조 된 CMP 막의 두께는 반응 시간에 의해 제한된다. 덜 노동 집약적 합성 반응 장치는 사이펀을 추가함으로써 변형 될 수있다; 결과적으로 샘플 구획​​ 자동 슬렛 추출기에 필적 비워 질 것이다. 우리의 기술은 얇은 공액 다공성 폴리머 필름 처리 된 CMP nanomembranes를 얻기 희생 기판의 사용을 결합한다. CMP의 nanomembranes의 합성으로 인해 아직 가능하지분말 CMP의 낮은 가공성. 다른 기술에 비해, 예 SURMOFs 7의 제조에, 우리가 사용하는 용매의 양의 감소를 달성했다. 특히 SURMOF 생산의 경우에는 헹굼 단계 인해 환류 THF의 사용으로,이 경우, 용매의 높은 소모가 우리 대폭 THF의 소비를 줄일 수있다. 우리는 제시된 방법은 기공 크기 및 화학 친화력을 통해 제어에 의해 선택도 및 투과도를 미세 조정하기 때문에 가능성의 가스 응용 프로그램과 액상 분리를 찾을 것으로 기대합니다. 또, 촉매, 센서, 또는 유기 전자 같은 다른 애플리케이션에 적합한 기능적 빌딩 블록으로부터 CMP 재료의 합성 모듈은 또한 기재 처리 방법으로부터 이익을 얻을 수.

The preparation of ultra-thin polymer membranes is of high interest for applications in gas separation and nanofiltration. Challenges in the synthesis are represented by (a) the control of the membrane thickness and the homogeneity and (b) transfer of such fragile membranes. To overcome challenge (a), molecular layer-by-layer synthesis1 has shown great promise in controlling the thickness and homogeneity of thin films grown at the solid-liquid interface.2,3 Controlling the number of layers linearly controls the film thickness. The l-b-l method has been successfully used to fabricate surface mounted metal organic frameworks (SURMOFs),4-7 also the synthesis of thin polymer films via l-b-l reaction of polymer chains was demonstrated.8 The challenge (b) concerns the handling of these ultra-thin membranes. To avoid rupture or wrinkling of the nanomembranes sacrificial supports of coatings have shown great promise. 9
Here we will present a detailed protocol for synthesis of conjugated microporous polymer (CMP)10-13 thin films through sequential addition of the molecular building blocks, with desired thickness and composition. The preparation of free-standing CMP nanomembranes is achieved by using a sacrificial support. To handle and transfer the CMP nanomembranes to other supports we will describe a simple protocol to protect the membranes with sacrificial coatings and their upfloating to the liquid air interface and subsequent transfer using dip-coating.

<table><tbody><tr><td>Acetone</td><td>VWR BDH Prolabo</td><td>20066.330</td><td>AnalR NORMAPUR</td></tr><tr><td>Potassium iodide</td><td>VWR BDH Prolabo</td><td>26846.292</td><td>AnalR NORMAPUR</td></tr><tr><td>Ethyl acetate</td><td>VWR BDH Prolabo</td><td>23882.321</td><td>AnalR NORMAPUR</td></tr><tr><td>Tetrahydrofuran (THF)</td><td>VWR BDH Prolabo</td><td>28559.320</td><td>HiPerSolv CHROMANORM</td></tr><tr><td>THF waterfree</td><td>Merck Millipore</td><td>1.08107.1001</td><td>SeccoSolv</td></tr><tr><td>Iodine</td><td>Sigma-Aldrich</td><td>20,777-2</td><td></td></tr><tr><td>Tetrakis(acetonitrile) copper(I) hexafluoro-phosphate</td><td>Sigma-Aldrich</td><td>346276-5G</td><td></td></tr><tr><td>Poly(methyl methacrylate) 996 kDa (PMMA)</td><td>Sigma-Aldrich</td><td>182265-25G</td><td></td></tr><tr><td>1.1.1.1 Methanetetrayltetrakis(4-azidobenzene) (TPM-azide)</td><td></td><td></td><td>Provided by AK Prof. Br&amp;auml;se. Institute of organic chemistry, Karlsruhe Institute of Technology. Synthesized according to &lt;sup&gt;9&lt;/sup&gt;.</td></tr><tr><td>1.1.1.1 Methanetetrayltetrakis(4-ethinylenebenzene) (TPM-alkyne)</td><td></td><td></td><td>Provided by AK Prof. Br&amp;auml;se. Institute of organic chemistry, Karlsruhe Institute of Technology. Synthesized according to &lt;sup&gt;9&lt;/sup&gt;.</td></tr><tr><td>11-thioacetyl-undecaneacid propargylamide</td><td></td><td></td><td>Provided by AK Prof. Br&amp;auml;se. Institute of organic chemistry, Karlsruhe Institute of Technology. Synthesized according to &lt;sup&gt;8&lt;/sup&gt;.</td></tr><tr><td>gold/titan coated silicium-wafer</td><td>Georg Albert PVD, 76857 Silz, Germany</td><td></td><td></td></tr><tr><td>gold coated mica</td><td>Georg Albert PVD, 76857 Silz, Germany</td><td></td><td></td></tr></tbody></table>

layer-by-layer synthesis and transfer of freestanding conjugated microporous polymer nanomembranes

CMP와 같은 큰 표면적 재료는 그들의 탁월한 열적 및 화학적 안정성과 결합 작용기의 혼입이 높은 변동 및 낮은 밀도로, 최근 관심을 끌고있다 성장. 예컨대 스핀 코팅과 같은 통상의 기술 적용이 가능하지 않기 때문에 그러나, 그들의 자연 불용성은 처리 문제를 일으킨다. 특히 CMP와 같은 박막의 처리가 바람직하다 막 애플리케이션을 위해, 프로세싱 문제는 상업적인 응용을 방해했다. 여기에서 우리는 분자 층별로 레이어 (LBL) 합성을 통해 기능화 기판에 CMP 박막의 계면 합성을 설명합니다. 이 프로세스는 원하는 두께 및 조성물 심지어 원하는 조성 구배를 가진 필름을 제조 할 수있다. 희생 지지체의 사용은 지지체의 용해 후 의해 자립 막 제조를 허용합성. 이러한 초박형 자립 막을 처리하기 위해 희생 코팅과 보호 nanomembranes의 파열을 방지하기 위해, 큰 가능성을 보여 주었다. 원하는 기판 nanomembranes를 전송하려면, 도포 막은 공기 - 액체 계면에서 upfloated 후 침지 코팅을 통해 전달된다.

멤브레인 (16)도 4는 금 웨이퍼에 전사 CMP-막으로부터 IRRA - 스펙트럼을 도시 적외선 반사 흡수 분광기 (IRRAS).에 의해 특징 지어진다. 방향족 백본의 진동에서 전형적인 밴드 1,605cm -1, 1,515cm -1과 1,412cm -1에 있습니다. 미 반응 아 지드 및 알킨 그룹 2,125cm -1 1,227cm -1 특성 밴드가 관찰 될 수있다.도 5는 주사 전자 현미경 (SEM) 이미지를 보여준다. 독립 구조로 서있는 멤브레인은 명확하게 볼 수 있습니다. <img alt="그림 1" src="/files/ftp_upload/53324/53324fig1highres.jpg" width="550" /> 도 1 분자 빌딩 블록. (A) TPM-알킨 및 (B) TPM 지드의 분자 구조. <a href="https://www-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/53324/53324fig1large.jpg" target="_blank">경기 수</a>쉽게이 그림의 더 큰 버전을 보려면 여기를 클릭하십시오. <img alt="그림 2" src="/files/ftp_upload/53324/53324fig2highres.jpg" width="700" /> 그림 2. 반응 장치. CMP 박막의 레이어로 레이어 합성에 설정합니다. 장치는 THF, 환류 냉각기 THF 증기를 이끌 스팀 유로 용 저장조로서 하나 구 둥근 바닥 플라스크로 구성되어있다. THF 응축은 샘플 실에 수집됩니다. 화학 물질은 격막과 스크류 캡을 통해 삽입 될 수있다. 샘플 실이 바닥 배출구를 통해 비워집니다. <a href="https://www-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/53324/53324fig2large.jpg" target="_blank">이 그림의 더 큰 버전을 보려면 여기를 클릭하십시오.</a> <img alt="그림 3" src="/files/ftp_upload/53324/53324fig3highres.jpg" width="500" /> 그림 3. 운모를 제거. </stroNG&gt; PMMA / CMP 막은 운모 기판의 에지로부터 분리하기 시작한다. PMMA / CMP의 절반이 물 위에 떠있는, 나머지 절반은 여전히 운모 기판에 부착되어있다. <a href="https://www-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/53324/53324fig3large.jpg" target="_blank">이 그림의 더 큰 버전을 보려면 여기를 클릭하십시오.</a> <img alt="그림 4" src="/files/ftp_upload/53324/53324fig4highres.jpg" width="700" /> 그림 4. IRRA - 스펙트럼. 금 웨이퍼에 전사 CMP-막에서 IRRA-스펙트럼. 1605, 1515 및 1,412cm의 방향족 백본의 진동에서 밴드 -1 CMP-막에 대한 특성이다. 사용 된 배경에. 때문에 CD 진동은 <a href="https://www-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/53324/53324fig4large.jpg" target="_blank">이 그림의 더 큰 버전을 보려면 여기를 클릭하십시오.</a> 5. SEM 이미지를 그림. CMP-막의 SEM-이미지. 독립 구조로 서있는 막 멋지게 표시됩니다. (린데의 허가, P 재판 등 화학 이잖아요 26, 7189 -.... 7193. 저작권 2014 미국 화학 학회.) <a href="https://www-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/53324/53324fig5large.jpg" target="_blank">이 그림의 더 큰 버전을 보려면 여기를 클릭하십시오.</a>

Watch this Scientific Journal Video about Layer-by-layer Synthesis and Transfer of Freestanding Conjugated Microporous Polymer Nanomembranes at JoVE.com

Layer-by-layer Synthesis and Transfer of Freestanding Conjugated Microporous Polymer Nanomembranes

In this paper we describe the interfacial synthesis of conjugated microporous polymers (CMP) on sacrificial substrates, and the dissolution of the substrate for the preparation of freestanding CMP nanomembranes. In addition, we will describe how the fragile nanomembranes can be transferred to other substrates.

레이어로 레이어 합성 및 독립 구조로 서있는 공역 미세 다공성 고분자 Nanomembranes의 전송

CMP as large surface area materials have attracted growing interest recently, due to their high variability in the incorporation of functional groups in ...

layer-layer-synthesis-transfer-freestanding-conjugated-microporous

Nanyang Technological University

Research

JoVE Journal

Chemistry

9.4K 조회수.  Karlsruhe Institute of Technology. In this paper we describe the interfacial synthesis of conjugated microporous polymers (CMP) on sacrificial substrates, and the dissolution of the substrate for the preparation of freestanding CMP nanomembranes. In addition, we will describe how the fragile nanomembranes can be transferred to other substrates.

비디오: Layer-by-layer Synthesis and Transfer of Freestanding Conjugated Microporous Polymer Nanomembranes

Towards Biomimicking Wood: Fabricated Free-standing Films of Nanocellulose, Lignin, and a Synthetic Polycation

Woody materials are comprised of plant cell walls that contain a layered secondary cell wall composed of structural polymers of polysaccharides and lignin. Layer-by-layer (LbL) assembly process which relies on the assembly of oppositely charged molecules from aqueous solutions was used to build a freestanding composite film of isolated wood polymers of lignin and oxidized nanofibril cellulose (NFC). To facilitate the assembly of these negatively charged polymers, a positively charged polyelectrolyte, poly(diallyldimethylammomium chloride) (PDDA), was used as a linking layer to create this simplified model cell wall. The layered adsorption process was studied quantitatively using quartz crystal microbalance with dissipation monitoring (QCM-D) and ellipsometry. The results showed that layer mass/thickness per adsorbed layer increased as a function of total number of layers. The surface coverage of the adsorbed layers was studied with atomic force microscopy (AFM). Complete coverage of the surface with lignin in all the deposition cycles was found for the system, however, surface coverage by NFC increased with the number of layers. The adsorption process was carried out for 250 cycles (500 bilayers) on a cellulose acetate (CA) substrate. Transparent free-standing LBL assembled nanocomposite films were obtained when the CA substrate was later dissolved in acetone. Scanning electron microscopy (SEM) of the fractured cross-sections showed a lamellar structure, and the thickness per adsorption cycle (PDDA-Lignin-PDDA-NC) was estimated to be 17 nm for two different lignin types used in the study. The data indicates a film with highly controlled architecture where nanocellulose and lignin are spatially deposited on the nanoscale (a polymer-polymer nanocomposites), similar to what is observed in the native cell wall.

The objective of this research was to form synthetic plant cell wall tissue using layer-by-layer assembly of nanocellulose fibrils and isolated lignin assembled from dilute aqueous suspensions.&#160; Surface measurement techniques of quartz crystal microbalance and atomic force microscopy were used to monitor the formation of the polymer-polymer nanocomposite material.

Nanocellulose, 리그닌의 날조 된 자립형 필름, 및 합성 폴리 양이온 : Biomimicking 나무를 향하여

Woody materials are comprised of plant cell walls that contain a layered secondary cell wall composed of structural polymers of polysaccharides and ...

연구

화학

A Technique to Functionalize and Self-assemble Macroscopic Nanoparticle-ligand Monolayer Films onto Template-free Substrates

This protocol describes a self-assembly technique to create macroscopic monolayer films composed of ligand-coated nanoparticles1,2. The simple, robust and scalable technique efficiently functionalizes metallic nanoparticles with thiol-ligands in a miscible water/organic solvent mixture allowing for rapid grafting of thiol groups onto the gold nanoparticle surface. The hydrophobic ligands on the nanoparticles then quickly phase separate the nanoparticles from the aqueous based suspension and confine them to the air-fluid interface. This drives the ligand-capped nanoparticles to form monolayer domains at the air-fluid interface.&#160; The use of water-miscible organic solvents is important as it enables the transport of the nanoparticles from the interface onto template-free substrates.&#160; The flow is mediated by a surface tension gradient3,4 and creates macroscopic, high-density, monolayer nanoparticle-ligand films.&#160; This self-assembly technique may be generalized to include the use of particles of different compositions, size, and shape and may lead to an efficient assembly method to produce low-cost, macroscopic, high-density, monolayer nanoparticle films for wide-spread applications.

A simple, robust and scalable technique to functionalize and self-assemble macroscopic nanoparticle-ligand monolayer films onto template-free substrates is described in this protocol.

템플릿이없는 기판에 육안 나노 입자 - 리간드 단층 필름을 기능화 및 자기 조립 기술

This protocol describes a self-assembly technique to create macroscopic monolayer films composed of ligand-coated nanoparticles1,2. The simple, robust and ...

Fabrication of Large-area Free-standing Ultrathin Polymer Films

This procedure describes a method for the fabrication of large-area and ultrathin free-standing polymer films. Typically, ultrathin films are prepared using either sacrificial layers, which may damage the film or affect its mechanical properties, or they are made on freshly cleaved mica, a substrate that is difficult to scale. Further, the size of ultrathin film is typically limited to a few square millimeters. In this method, we modify a surface with a polyelectrolyte that alters the strength of adhesion between polymer and deposition substrate. The polyelectrolyte can be shown to remain on the wafer using spectroscopy, and a treated wafer can be used to produce multiple films, indicating that at best minimal amounts of the polyelectrolyte are added to the film. The process has thus far been shown to be limited in scalability only by the size of the coating equipment, and is expected to be readily scalable to industrial processes. In this study, the protocol for making the solutions, preparing the deposition surface, and producing the films is described.

We describe a method for the fabrication of large-area (up to 13 cm diameter) and ultrathin (as thin as 8 nm) polymer films. Instead of using a sacrificial interlayer to delaminate the film from its substrate, we use a self-limiting surface treatment suitable for arbitrarily large areas.

대 면적의 제작은 초박막 고분자 필름을 무료 서

This procedure describes a method for the fabrication of large-area and ultrathin free-standing polymer films.  Typically, ultrathin films are prepared ...

Fabrication of the Thermoplastic Microfluidic Channels

In our lab, we have successfully isolated nucleic acids directly from microliter and submicroliter volumes of human blood, urine and stool using polymer/nanoparticle composite microscale lysis and solid phase extraction columns. The recovered samples are concentrated, small volume samples that are PCRable, without any additional cleanup. Here, we demonstrate how to fabricate thermoplastic microfluidic chips using hot embossing and heat sealing. Then, we demonstrate how to use in situ light directed surface grafting and polymerization through the sealed chip to form the composite solid phase columns. We demonstrate grafting and polymerization of a carbon nanotube/polymer composite column for bacterial cell lysis. We then show the lysis process followed by solid phase extraction of nucleic acids from the sample on chip using a silica/polymer composite column. The attached protocols contain detailed instructions on how to make both lysis and solid phase extraction columns.

Here we demonstrate how to fabricate thermoplastic microfluidic chips using hot embossing and heat sealing. Then we demonstrate how to use in situ light directed surface grafting and polymerization through the sealed chip to form the composite solid phase columns.

열가 소성 Microfluidic 채널 제작

In our lab, we have successfully isolated nucleic acids directly from microliter and submicroliter volumes of human blood, urine and stool using ...

생물학

Formation of Biomembrane Microarrays with a Squeegee-based Assembly Method

Lipid bilayer membranes form the plasma membranes of cells and define the boundaries of subcellular organelles. In nature, these membranes are heterogeneous mixtures of many types of lipids, contain membrane-bound proteins and are decorated with carbohydrates. In some experiments, it is desirable to decouple the biophysical or biochemical properties of the lipid bilayer from those of the natural membrane. Such cases call for the use of model systems such as giant vesicles, liposomes or supported lipid bilayers (SLBs). Arrays of SLBs are particularly attractive for sensing applications and mimicking cell-cell interactions. Here we describe a new method for forming SLB arrays. Submicron-diameter SiO2 beads are first coated with lipid bilayers to form spherical SLBs (SSLBs). The beads are then deposited into an array of micro-fabricated submicron-diameter microwells. The preparation technique uses a "squeegee" to clean the substrate surface, while leaving behind SSLBs that have settled into microwells. This method requires no chemical modification of the microwell substrate, nor any particular targeting ligands on the SSLB. Microwells are occupied by single beads because the well diameter is tuned to be just larger than the bead diameter. Typically, more 75% of the wells are occupied, while the rest remain empty. In buffer SSLB arrays display long-term stability of greater than one week. Multiple types of SSLBs can be placed in a single array by serial deposition, and the arrays can be used for sensing, which we demonstrate by characterizing the interaction of cholera toxin with ganglioside GM1. We also show that phospholipid vesicles without the bead supports and biomembranes from cellular sources can be arrayed with the same method and cell-specific membrane lipids can be identified.

Supported lipid bilayers and natural membrane particles are convenient systems that can approximate the properties of cell membranes and be incorporated in a variety of analytical strategies. Here we demonstrate a method for preparing microarrays composed of supported lipid bilayer-coated SiO2 beads, phospholipid vesicles or natural membrane particles.

스퀴지 기반의 조립 방법과 생체막 마이크로 어레이의 형성

Lipid bilayer membranes form the plasma membranes of cells and define the boundaries of subcellular organelles. In nature, these membranes are ...

생체공학

Preparation of Light-responsive Membranes by a Combined Surface Grafting and Postmodification Process

In order to modify the surface tension of commercial available track-edged polymer membranes, a procedure of surface-initiated polymerization is presented. The polymerization from the membrane surface is induced by plasma treatment of the membrane, followed by reacting the membrane surface with a methanolic solution of 2-hydroxyethyl methacrylate (HEMA). Special attention is given to the process parameters for the plasma treatment prior to the polymerization on the surface. For example, the influence of the plasma-treatment on different types of membranes (e.g.&#160;polyester, polycarbonate, polyvinylidene fluoride) is studied. Furthermore, the time-dependent stability of the surface-grafted membranes is shown by contact angle measurements. When grafting poly(2-hydroxyethyl methacrylate) (PHEMA) in this way, the surface can be further modified by esterification of the alcohol moiety of the polymer with a carboxylic acid function of the desired substance. These reactions can therefore be used for the functionalization of the membrane surface. For example, the surface tension of the membrane can be changed or a desired functionality as the presented light-responsiveness can be inserted. This is demonstrated by reacting PHEMA with a carboxylic acid functionalized spirobenzopyran unit which leads to a light-responsive membrane. The choice of solvent plays a major role in the postmodification step and is discussed in more detail in this paper. The permeability measurements of such functionalized membranes are performed using a Franz cell with an external light source. By changing the wavelength of the light from the visible to the UV-range, a change of permeability of aqueous caffeine solutions is observed.

A plasma-induced polymerization procedure is described for the surface-initiated polymerization on polymer membranes. Further postmodification of the grafted polymer with photochromic substances is presented with a protocol of conducting permeability measurements of light-responsive membranes.

결합 표면의 접목 및 Postmodification 과정에 의한 빛의 응답 멤브레인의 제조

In order to modify the surface tension of commercial available track-edged polymer membranes, a procedure of surface-initiated polymerization is ...

Fabricating Reactive Surfaces with Brush-like and Crosslinked Films of Azlactone-Functionalized Block Co-Polymers

In this paper, fabrication methods that generate novel surfaces using the azlactone-based block co-polymer, poly (glycidyl methacrylate)-block-poly (vinyl dimethyl azlactone) (PGMA-b-PVDMA), are presented. Due to the high reactivity of azlactone groups towards amine, thiol, and hydroxyl groups, PGMA-b-PVDMA surfaces can be modified with secondary molecules to create chemically or biologically functionalized interfaces for a variety of applications. Previous reports of patterned PGMA-b-PVDMA interfaces have used traditional top-down patterning techniques that generate non-uniform films and poorly controlled background chemistries. Here, we describe customized patterning techniques that enable precise deposition of highly uniform PGMA-b-PVDMA films in backgrounds that are chemically inert or that have biomolecule-repellent properties. Importantly, these methods are designed to deposit PGMA-b-PVDMA films in a manner that completely preserves azlactone functionality through each processing step. Patterned films show well-controlled thicknesses that correspond to polymer brushes (~90 nm) or to highly crosslinked structures (~1-10 &#956;m). Brush patterns are generated using either the parylene lift-off or interface directed assembly methods described and are useful for precise modulation of overall chemical surface reactivity by adjusting either the PGMA-b-PVDMA pattern density or the length of the VDMA block. In contrast, the thick, crosslinked PGMA-b-PVDMA patterns are obtained using a customized micro-contact printing technique and offer the benefit of higher loading or capture of secondary material due to higher surface area to volume ratios. Detailed experimental steps, critical film characterizations, and trouble-shooting guides for each fabrication method are discussed.

Surface fabrication methods for patterned deposition of nanometer thick brushes or micron thick, crosslinked films of an azlactone block co-polymer are reported. Critical experimental steps, representative results, and limitations of each method are discussed. These methods are useful for creating functional interfaces with tailored physical features and tunable surface reactivity.

브러쉬 모양의 반응 표면 날조 및 Azlactone 기능성된 블록 공동 고분자의 가교 된 영화

In this paper, fabrication methods that generate novel surfaces using the azlactone-based block co-polymer, poly (glycidyl methacrylate)-block-poly (vinyl ...

공학

Electrophoretic Crystallization of Ultrathin High-performance Metal-organic Framework Membranes

We report the synthesis of thin, highly intergrown, polycrystalline metal-organic framework (MOF) membranes on a wide range of unmodified porous and non-porous supports (polymer, ceramic, metal, carbon, and graphene). We developed a novel crystallization technique, which is termed the ENACT approach: the electrophoretic nuclei assembly for the crystallization of highly intergrown thin films (ENACT). This approach allows for a high density of heterogeneous nucleation of MOFs on a chosen substrate via the electrophoretic deposition (EPD) directly from the precursor sol. The growth of well-packed MOF nuclei leads to a highly intergrown polycrystalline MOF film. We show that this simple approach can be used for the synthesis of thin, intergrown zeolite imidazole framework (ZIF)-7 and ZIF-8 films. The resulting 500 nm-thick ZIF-8 membranes show a considerably high H2 permeance (8.3 x 10-6 mol m-2 s-1 Pa-1) and ideal gas selectivities (7.3 for H2/CO2, 15.5 for H2/N2, 16.2 for H2/CH4, and 2655 for H2/C3H8). An attractive performance for C3H6/C3H8 separation is also achieved (a C3H6 permeance of 9.9 x 10-8 mol m-2 s-1 Pa-1 and a C3H6/C3H8 ideal selectivity of 31.6 at 25 &#176;C). Overall, the ENACT process, owing to its simplicity, can be extended to synthesize intergrown thin films of a wide range of nanoporous crystalline materials.

A simple, reproducible, and versatile approach for the synthesis of intergrown, polycrystalline metal-organic framework membranes on a wide range of unmodified porous and non-porous supports is presented.

Ultrathin 높은 성능 금속-유기 프레임 워크 막의 전기 이동 화

We report the synthesis of thin, highly intergrown, polycrystalline metal-organic framework (MOF) membranes on a wide range of unmodified porous and ...

Procedure for the Transfer of Polymer Films Onto Porous Substrates with Minimized Defects

The fabrication of devices containing thin film composite membranes necessitates the transfer of these films onto the surfaces of arbitrary support substrates. Accomplishing this transfer in a highly controlled, mechanized, and reproducible manner can eliminate the creation of macroscale defect structures (e.g., tears, cracks, and wrinkles) within the thin film that compromise device performance and the usable area per sample. Here, we describe a general protocol for the highly controlled and mechanized transfer of a polymeric thin film onto an arbitrary porous support substrate for eventual use as a water filtration membrane device. Specifically, we fabricate a block copolymer (BCP) thin film on top of a sacrificial, water-soluble poly(acrylic acid) (PAA) layer and silicon wafer substrate. We then utilize a custom-designed, 3D-printed transfer tool and drain chamber system to deposit, lift-off, and transfer the BCP thin film onto the center of a porous anodized aluminum oxide (AAO) support disc. The transferred BCP thin film is shown to be consistently placed onto the center of the support surface due to the guidance of the meniscus formed between the water and the 3D-printed plastic drain chamber. We also compare our mechanized transfer-processed thin films to those that have been transferred by hand with the use of tweezers. Optical inspection and image analysis of the transferred thin films from the mechanized process confirm that little-to-no macroscale inhomogeneities or plastic deformations are produced, as compared to the multitude of tears and wrinkles produced from manual transfer by hand. Our results suggest that the proposed strategy for thin film transfer can reduce defects when compared to other methods across many systems and applications.

We present a procedure for highly controlled and wrinkle-free transfer of block copolymer thin films onto porous support substrates using a 3D-printed drain chamber. The drain chamber design is of general relevance to all procedures involving transfer of macromolecular films onto porous substrates, which is normally done by hand in an irreproducible fashion.

결함이 최소화된 다공성 기판에 폴리머 필름 을 이송하는 절차

The fabrication of devices containing thin film composite membranes necessitates the transfer of these films onto the surfaces of arbitrary support ...

Microscopic Visualization of Porous Nanographenes Synthesized through a Combination of Solution and On-Surface Chemistry

On-surface synthesis has recently been regarded as a promising approach for the generation of new molecular structures. It has been particularly successful in the synthesis of graphene nanoribbons, nanographenes and intrinsically reactive and instable, yet attractive species. It is based on the combination of solution chemistry aimed at preparation of appropriate molecular precursors for further ultra-high vacuum surface assisted transformations. This approach also owes its success to an incredible development of characterization techniques, such as scanning tunneling/atomic force microscopy and related methods, which allow detailed, local characterization at atomic scale. While the surface-assisted synthesis can provide molecular nanostructures with outstanding precision, down to single atoms, it suffers from basing on metallic surfaces and often limited yield. Therefore, the extension of the approach away from metals and the struggle to increase productivity seem to be significant challenges toward wider applications. Herein, we demonstrate the on-surface synthesis approach for generation of non-planar nanographenes, which are synthesized through a combination of solution chemistry and sequential surface-assisted processes, together with the detailed characterization by scanning probe microscopy methods.

<meta charset="utf8"></head><body>용액과 표면 화학의 조합을 통해 합성된 다공성 nanographenes의 현미경 시각화

A combination of solution and surface assisted synthesis opens new directions in the atomically precise synthesis of nanostructures. Scanning tunneling microscopy (STM) supplemented by non-contact atomic force microscopy (nc-AFM) enables detailed characterization of newly designed and generated carbon-based nano-objects.