The authors would like to acknowledge the University of Colorado Boulder for its support of this work.

주의 :이 프로토콜에서 사용되는 화학 물질의 대부분은 유해 물질이다. 물질 안전 보건 자료 (MSDS)를 참조하고 이러한 물질 작업을 할 때 적절한 개인 보호 장비 (PPE)를 사용합니다. 시약 1. 정제, 제조 및 저장 <ol><li> 제조사의 프로토콜에 따라 용제 정제 시스템을 이용하여 사용되는 모든 용매 정제. 용매 정제 시스템을 사용할 수없는 경우, 건조제 (예를 들면, 분 자체 등 CAH 2) 증류를 사용한다. 일단 실온 글러브 박스에서 질소 분위기하에 저장 용매를 건조시켰다. </li><li> 제조사의 프로토콜에 따라, 진공 증류에 의해 정제하여 모든 단량체. 일단 냉장고에서 질소 대기하에 어두운 병에 저장 단량체 증류. </li><li> 제조사의 프로토콜에 따라, 진공 증류에 의해 정제 개시제. 저장 개시제의 증류하면냉장고에 질소 분위기 하에서 어두운 병. </li><li> 제조사의 프로토콜에 따라 승화 페 릴렌 정제. 승화되면, 실온에서 벤치 탑에 페 릴렌를 저장합니다. </li><li> CDCl3 중의 100g 병에 25.0 mg을 BHT를 추가하여 디 부틸 히드 록시 톨루엔 중수 소화 클로로포름 (BHT) (을 CDCl3)의 250 ppm의 솔루션을 준비합니다. 준비하고 벤치 탑에이 솔루션을 저장합니다. </li></ol> 광촉매로 페 릴렌를 사용하여 메틸 메타 크릴 레이트 2. 광중합 <ol><li> 모든 시약은 실온에 올 수 있습니다. 변색 또는 고체 입자의 형성과 같은 오염의 흔적이 없다 보장하기 위해 사용하기 전에 모든 시약을 검사합니다. </li><li> 질소 분위기의 글러브 박스에서, 20 ㎖ 섬광 유리 병에서 작은 교반 막대를 배치합니다. 2.36 밀리그램 (9.38 μmol, 1.00 eq.)를 페 릴렌의 추가. </li><li> 1.00 ml의 디메틸 포름 아미드 (DMF)를 추가합니다. </li><li> 이 혼합물에, 1.00 ㎖ (9.38 밀리몰 추가1000 eq.)를 메틸 메타 크릴 레이트 (MMA). </li><li> 1,600 rpm으로 설정하고 백색 발광 다이오드 (LED)의 스트립에 의해 조명 볶음 접시에 유리 병을 놓습니다. (예를 들어, 머리 위의 조명, 근처 창) 다른 광원에서 어떤 조명을 제한합니다. </li><li> 16.4 μl를 추가, (93.8 μmol, 10.0 당량.) 반응을 시작하려면 피펫을 통해 α-에틸 브로 모 아세테이트 (EBP)의. 참고 : 자연 태양 광을 사용하여이 반응을 수행하려면, 다음 유리 병을 밀봉, 단계 2.5을 무시하고, 위의 단계를 따라 글러브 박스에서 그것을 가지고, 자연 햇빛에 의해 조명 영역에 병을 놓습니다. </li><li> 상수 조명 아래에서 24 시간 동안 반응을 저어. 격리 및 단계 4.1의 지침에 따라 제품 폴리 (MMA)를 정화 - 4.4. </li></ol> 반응 키네틱 3. 분석 <ol><li> 벤치 탑에서 2 ㎖의 유리 병에을 CDCl3 용액에 BHT의 0.70 ml의 분배 및 격벽 캡으로 밀봉. 이 유리 병 내가 가져<html> 중합이 수행되는 글로브 박스를 NTO. </li><li> 반응 혼합물에 0.20 ml의 제거 주사기를 사용한다. CDCl3 중 BHT의 250 ppm의 용액을 함유하는 2 ml의 바이알에 주사기의 내용물을 주입한다. 다시 그려 중합 완전한 담금질을 위해 플런저 여러 번 누른다. </li><li> 이것은, NMR (핵 자기 공명) 분광학 튜브에 2 ㎖의 바이알의 내용물을 이동. %의 변환을위한 1 H NMR 분광법을 통해이 샘플을 분석 할 수 있습니다. (24) </li><li> 페 릴렌를 사용하여 메틸 메타 크릴 레이트의 중합의 구체적인 예를 들면, 미 반응 단량체 (δ = 3.62) (M)의 메톡 수소에 대응하는 피크 아래의 면적을 비교함으로써 샘플의 1H NMR 스펙트럼의 전환율을 계산하고 다음 식을 사용하여 중합체 (δ = 3.50) (P)의 메톡 수소에 대응하는 피크 아래의 면적 : 1 &quot;SRC =&quot;/ 파일 / ftp_upload / 53571 / 53571eq1.jpg &quot;/&gt; </li><li> 분석 후, 깨끗한 20 mL를 섬광 바이알로 NMR 분광법 튜브의 내용물을 붓는다. 감압하에 용매를 증발시켰다. 테트라 히드로 푸란 중 1.00 ㎖ (THF)에서 샘플을 재용. </li><li> 깨끗한 2 ㎖의 유리 병에 주사기 필터를 통해 샘플을 보낼 수 있습니다. 수 평균 분자량 (Mn), 중량 평균 분자량 (M w) 및 분산도 (DJ)를 결정하기 위해 멀티 앵글 빛 산란과 함께 겔 투과 크로마토 그래피 (GPC)를 통해 샘플을 분석한다. (24) </li></ol> 4. 분리 및 중합체 생성물의 정제 <ol><li> 메탄올의 50 배 과량으로 반응 혼합물의 내용물을 붓고, 적어도 1 시간 동안 교반을 시켜서 중합 반응을 종결. </li><li> 제조사에 따른 진공 여과하여 메탄올, 폴리 (메틸 메타 크릴 레이트)를 격리실험 계획안. 주 : 분리 방법은 제조 된 고분자에 따라 달라질 것이다. 폴리 메틸 메타 크릴 레이트 및 폴리스티렌, 진공 흡인 여과기를 사용하여 메탄올에서 침전 된 폴리머 필터. 폴리 (부틸 아크릴 레이트)의 경우, 점착성 중합체 메탄올 디 캔트. </li><li> 추가 100 mL의 메탄올 중에 폴리머를 헹군다. </li><li> 다시 용해 디클로로 메탄과 반복의 폴리머은 위의 두 번 4.3을 통해 4.1 단계를 반복합니다. </li></ol> 스티렌과의 MMA 매크로 개시제 5. 체인 확장은 폴리 (MMA)를 생산하는 -b - 폴리 (S) <ol><li> 모든 시약은 실온에 올 수 있습니다. 변색 또는 고체 입자의 형성과 같은 오염의 흔적이 없다 보장하기 위해 사용하기 전에 모든 시약을 검사합니다. </li><li> 질소 분위기의 글로브 박스 내에서, 폴리 (MMA) 136 mg의 (2.34 μmol, 1.00 당량.) 배치 매크로 개시제 작은 교반 막대를 갖춘 20 mL를 섬광 바이알로. </li><li> 0.59 mg을 페 릴렌 (2.34 μmol, 1.0 추가0 당량.). </li><li> 1.00 ml의 DMF를 추가합니다. </li><li> 1,600 rpm으로 설정하고 백색 LED 스트립 조명에 의해 저어 접시에 유리 병을 놓습니다. (예를 들어, 머리 위의 조명, 근처 창) 다른 광원에서 어떤 조명을 제한합니다. </li><li> 이 혼합물에, 피펫을 통해 스티렌 (S)의 1.24 ㎖ (11.7 밀리몰, 5000 당량.)를 추가합니다. </li><li> 상수 조명 아래에서 24 시간 동안 반응을 저어. 격리 및 제품 폴리 정화 (MMA) -b-폴리 단계 4.1의 지침에 따라 (S) - 4.4. </li></ol>

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The authors have nothing to disclose.

프로토콜이 중합 법의 특정 예를 보여 있지만,이 반응을 수행하는 연구자에게 제공되는 옵션은 상당히 광범위하다. 수정은 ATRP이 수행되는 어떤 특정 photoredox의 최적화를 허용하는 프로토콜에 걸쳐 점의 개수로 할 수있다. 조사를 받고,이 반응에 대한 새로운 단량체, 개시제 및 촉매로, 화학 양론 용매를 할 수있는 반응을 수행하는 데 사용되는 반응 조건의 최적화의 일부로서 수정한다. 또한 개?...

The synthesis of technologically advanced polymers requires precise control over polymer molecular weight, dispersity (&#208;), composition, and architecture.1,2 Controlled radical polymerizations (CRPs)3-8 have revolutionized the synthesis of well-defined polymers, with atom transfer radical polymerization (ATRP) being the most used CRP, largely due to operational simplicity and synthetic versatility.9-14 The crux of ATRP is the ability to reversibly deactivate the polymerization, controlling the equilibrium between a propagating radical and a dormant species. Enforcing a low concentration of active radicals greatly minimizes bimolecular termination pathways and allows for the synthesis of well-defined polymers. 
Traditional ATRP relies on a transition metal catalyst to mediate this equilibrium.3 These metal catalysts contaminate the polymer product and impede implementation in biomedical or electronic applications while also raising environmental concerns. Although significant strides have been made to reduce the catalyst concentration to ppm levels, these methodologies require more demanding experimental conditions and metal contamination is still not entirely eliminated.15,16
Reversible addition-fragmentation transfer17,18 and nitroxide-mediated polymerizations19,20 are CRPs that do not require metal catalysts, although they have been used less often than ATRP.3 Recently, reversible chain-transfer21 and reversible complexation22,23 variants of ATRP that can use organic catalysts were reported. However, these methodologies require the use of alkyl iodide initiators and are not effective with the alkyl bromides commonly employed in ATRP. A highly desirable CRP would match the performance, feasibility, and robustness of traditional ATRP while being catalyzed by an organic catalyst under mild conditions.
Here, we describe a methodology for the radical polymerization of functionalized vinyl monomers using perylene as a visible-light photocatalyst. Through optimization of parameters such as stoichiometry, concentration, time, and light flux, the molecular weight of the polymers can be controlled.24, 25 Similar methodologies have been recently introduced using phenothiazine derivatives as photocatalysts for metal-free ATRP.26, 27 Because researchers in the field of polymerization catalysis are constantly developing new catalytic systems, the ability to compare catalyst performance across a number of metrics is vital. This ability to make comparisons relies heavily upon procedural consistency and clarity on the part of the researchers performing the experiments. As such, it is our goal that this video will be used to help precisely communicate the methods by which these polymers are synthesized and characterized.

<table><tbody><tr><td>perylene, min 98.0%</td><td>TCI America</td><td>TCP0078-025G</td><td>purify by sublimation</td></tr><tr><td>&lt;em&gt;N,N&lt;/em&gt;-dimethylformamide</td><td>VWR</td><td>EM-DX1726-1</td><td>Omnisolv</td></tr><tr><td>methyl methacrylate, 99%</td><td>VWR</td><td>200000-678</td><td>distilled prior to use, stored in refrigerator</td></tr><tr><td>ethyl &amp;alpha;-bromophenyl acetate&amp;nbsp;</td><td>Aldrich</td><td>554065</td><td>distilled prior to use stored in refrigerator</td></tr><tr><td>butylated hydroxytoluene&amp;nbsp;</td><td>Aldrich</td><td>W218405</td><td></td></tr><tr><td>Chloroform-D</td><td>Cambridge Isotope Labs</td><td>DLM-7-100</td><td></td></tr><tr><td>tetrahydrofuran</td><td>VWR</td><td>EM-TX0279-1</td><td>Omnisolv</td></tr><tr><td>methanol</td><td>VWR</td><td>BDH1135</td><td></td></tr><tr><td>dichloromethane</td><td>VWR</td><td>EM-DX0831-1</td><td>Omnisolv</td></tr><tr><td>styrene, 99%</td><td>VWR</td><td>AAAA18481-0F</td><td>distilled prior to use, stored in refrigerator</td></tr><tr><td>glass scintillation vial, 20&amp;nbsp;ml</td><td>VWR</td><td>66022-065</td><td></td></tr><tr><td>screw top vial, 2 ml</td><td>Agilent</td><td>5182-0715</td><td></td></tr><tr><td>septum cap for screw top vial</td><td>Agilent</td><td>5182-0717</td><td></td></tr><tr><td>heavy wall pressure vessel, 100 ml</td><td>Synthware</td><td>P160005&amp;nbsp;</td><td></td></tr><tr><td>syringe, 1 ml norm-ject</td><td>VWR</td><td>89174-491</td><td></td></tr><tr><td>NMR tube</td><td>New Era</td><td>NE-UL5-7&#039;</td><td></td></tr><tr><td>nylon syringe filter, 0.45&amp;nbsp;&amp;#956;m</td><td>VWR</td><td>28143-240</td><td></td></tr><tr><td>glovebox</td><td>Mbraun</td><td>LABstar</td><td></td></tr><tr><td>solvent purification system</td><td>Mbraun</td><td>MB-SPS-800</td><td></td></tr><tr><td>stirplate</td><td>IKA</td><td>3582401</td><td></td></tr><tr><td>light-emitting diodes</td><td>Creative Lighting Solutions</td><td>CL-FRS1210-5M-12V-WH</td><td>2x 12-inch strips of 5500 K white LEDs were used for illumination</td></tr><tr><td>12 V DC power supply for LEDs</td><td>Creative Lighting Solutions</td><td>CL-PS16001-40W</td><td></td></tr><tr><td>high performance liquid chromatograph&amp;nbsp;</td><td>Agilent</td><td>G1310B, G1322A, G1329B, G1316A</td><td></td></tr><tr><td>gel permeation size-exclusion columns</td><td>Agilent</td><td>PL1110-6500</td><td></td></tr><tr><td>multi-angle light scattering detector</td><td>Wyatt</td><td>WTREOS</td><td></td></tr><tr><td>differential refractometer</td><td>Wyatt</td><td>WTREX</td><td></td></tr></tbody></table>

atom transfer radical polymerization of functionalized vinyl monomers using perylene as a visible light photocatalyst

A standardized technique for atom transfer radical polymerization of vinyl monomers using perylene as a visible-light photocatalyst is presented. The procedure is performed under an inert atmosphere using air- and water-exclusion techniques. The outcome of the polymerization is affected by the ratios of monomer, initiator, and catalyst used as well as the reaction concentration, solvent, and nature of the light source. Temporal control over the polymerization can be exercised by turning the visible light source off and on. Low dispersities of the resultant polymers as well as the ability to chain-extend to form block copolymers suggest control over the polymerization, while chain end-group analysis provides evidence supporting an atom-transfer radical polymerization mechanism.

표 1은이 방법을 통해 달성 중합 결과의 범위를 보여줍니다. 이러한 데이터는 페 릴렌은 관능 비닐 모노머 다수의 중합 용 광촉매로서 기능 할 수 있음을 보여준다. 특정 단량체, 용제, 화학 양론, 개시제 및 광원 반응 매개 변수 중 임의의 조정은도 1. 매우 좋은 다소 넓은 범위의 분자량 및 dispersities 변화와 중합체로 연결 사슬 - 결과를 나타낸다 ?...

Watch this Scientific Journal Video about Atom Transfer Radical Polymerization of Functionalized Vinyl Monomers Using Perylene as a Visible Light Photocatalyst at JoVE.com

Atom Transfer Radical Polymerization of Functionalized Vinyl Monomers Using Perylene as a Visible Light Photocatalyst

가시광 광촉매 페 릴렌 사용 관능 비닐 모노머의 원자 이동 라디칼 중합

A method for the atom transfer radical polymerization of functionalized vinyl monomers using perylene as a visible-light photocatalyst is described.

A standardized technique for atom transfer radical polymerization of vinyl monomers using perylene as a visible-light photocatalyst is presented. The ...

atom-transfer-radical-polymerization-functionalized-vinyl-monomers

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11.6K 조회수.  University of Colorado Boulder. A method for the atom transfer radical polymerization of functionalized vinyl monomers using perylene as a visible-light photocatalyst is described.

비디오: Atom Transfer Radical Polymerization of Functionalized Vinyl Monomers Using Perylene as a Visible Light Photocatalyst

Reductive Electropolymerization of a Vinyl-containing Poly-pyridyl Complex on Glassy Carbon and Fluorine-doped Tin Oxide Electrodes

Controllable electrode surface modification is important in a number of fields, especially those with solar fuels applications. Electropolymerization is one surface modification technique that electrodeposits a polymeric film at the surface of an electrode by utilizing an applied potential to initiate the polymerization of substrates in the Helmholtz layer. This useful technique was first established by a Murray-Meyer collaboration at the University of North Carolina at Chapel Hill in the early 1980s and utilized to study numerous physical phenomena of films containing inorganic complexes as the monomeric substrate. Here, we highlight a procedure for coating electrodes with an inorganic complex by performing reductive electropolymerization of the vinyl-containing poly-pyridyl complex onto glassy carbon and fluorine doped tin oxide coated electrodes. Recommendations on electrochemical cell configurations and troubleshooting procedures are included. Although not explicitly described here, oxidative electropolymerization of pyrrole-containing compounds follows similar procedures to vinyl-based reductive electropolymerization but are far less sensitive to oxygen and water.

A procedure for performing reductive electropolymerization of vinyl-containing compounds onto glassy carbon and fluorine doped tin-oxide coated electrodes is presented. Recommendations on electrochemical cell configurations and troubleshooting procedures are included. Although not explicitly described here, oxidative electropolymerization of pyrrole-containing compounds follows similar procedures to vinyl-based reductive electropolymerization.

유리 탄소와 불소 도핑 된 주석 산화물 전극에 비닐 함유 폴리 피리 딜 단지의 환원 적 전기 중합

Controllable electrode surface modification is important in a number of fields, especially those with solar fuels applications. Electropolymerization is ...

연구

화학

Electroactive Polymer Nanoparticles Exhibiting Photothermal Properties

A method for the synthesis of electroactive polymers is demonstrated, starting with the synthesis of extended conjugation monomers using a three-step process that finishes with Negishi coupling. Negishi coupling is a cross-coupling process in which a chemical precursor is first lithiated, followed by transmetallation with ZnCl2. The resultant organozinc compound can be coupled to a dibrominated aromatic precursor to give the conjugated monomer. Polymer films can be prepared via electropolymerization of the monomer and characterized using cyclic voltammetry and ultraviolet-visible-near infrared (UV-Vis-NIR) spectroscopy. Nanoparticles (NPs) are prepared via emulsion polymerization of the monomer using a two-surfactant system to yield an aqueous dispersion of the polymer NPs. The NPs are characterized using dynamic light scattering, electron microscopy, and UV-Vis-NIR-spectroscopy. Cytocompatibility of NPs is investigated using the cell viability assay. Finally, the NP suspensions are irradiated with a NIR laser to determine their effectiveness as potential materials for photothermal therapy (PTT).

A protocol is presented for the synthesis and preparation of nanoparticles consisting of electroactive polymers.

전기 활성 고분자 나노 입자 출전 광열 등록

A method for the synthesis of electroactive polymers is demonstrated, starting with the synthesis of extended conjugation monomers using a three-step ...

공학

Facile Synthesis of Worm-like Micelles by Visible Light Mediated Dispersion Polymerization Using Photoredox Catalyst

Presented herein is a protocol for the facile synthesis of worm-like micelles by visible light mediated dispersion polymerization. This approach begins with the synthesis of a hydrophilic poly(oligo(ethylene glycol) methyl ether methacrylate) (POEGMA) homopolymer using reversible addition-fragmentation chain-transfer (RAFT) polymerization. Under mild visible light irradiation (&#955; = 460 nm, 0.7 mW/cm2), this macro-chain transfer agent (macro-CTA) in the presence of a ruthenium based photoredox catalyst, Ru(bpy)3Cl2 can be chain extended with a second monomer to form a well-defined block copolymer in a process known as Photoinduced Electron Transfer RAFT (PET-RAFT). When PET-RAFT is used to chain extend POEGMA with benzyl methacrylate (BzMA) in ethanol (EtOH), polymeric nanoparticles with different morphologies are formed in situ according to a polymerization-induced self-assembly (PISA) mechanism. Self-assembly into nanoparticles presenting POEGMA chains at the corona and poly(benzyl methacrylate) (PBzMA) chains in the core occurs in situ due to the growing insolubility of the PBzMA block in ethanol. Interestingly, the formation of highly pure worm-like micelles can be readily monitored by observing the onset of a highly viscous gel in situ due to nanoparticle entanglements occurring during the polymerization. This process thereby allows for a more reproducible synthesis of worm-like micelles simply by monitoring the solution viscosity during the course of the polymerization. In addition, the light stimulus can be intermittently applied in an ON/OFF manner demonstrating temporal control over the nanoparticle morphology.

This article describes a process for producing polymeric self-assembled nanoparticles using visible light mediated dispersion polymerization. Using low energy visible light to control the polymerization allows for the reproducible formation of self-assembled worm-like micelles at high solids content.

Photoredox 촉매를 사용하여 가시 광선 중재 분산 중합에 의해 웜 형상 미셀 손쉬운 합성

Presented herein is a protocol for the facile synthesis of worm-like micelles by visible light mediated dispersion polymerization. This approach begins ...

A Simple and Efficient Protocol for the Catalytic Insertion Polymerization of Functional Norbornenes

Norbornene can be polymerized by a variety of mechanisms, including insertion polymerization whereby the double bond is polymerized and the bicyclic nature of the monomer is conserved. The resulting polymer, polynorbornene, has a very high glass transition temperature, Tg, and interesting optical and electrical properties. However, the polymerization of functional norbornenes by this mechanism is complicated by the fact that the endo substituted norbornene monomer has, in general, a very low reactivity. Furthermore, the separation of the endo substituted monomer from the exo monomer is a tedious task. Here, we present a simple protocol for the polymerization of substituted norbornenes (endo:exo ca. 80:20) bearing either a carboxylic acid or a pendant double bond. The process does not require that both isomers be separated, and proceeds with low catalyst loadings (0.01 to 0.02 mol%). The polymer bearing pendant double bonds can be further transformed in high yield, to afford a polymer bearing pendant epoxy groups. These simple procedures can be applied to prepare polynorbornenes with a variety of functional groups, such as esters, alcohols, imides, double bonds, carboxylic acids, bromo-alkyls, aldehydes and anhydrides.

We describe the catalytic insertion polymerization of 5-norbornene-2-carboxylic acid and 5-vinyl-2-norbornene to form functional polymers with a very high glass transition temperature.

기능 노보 넨의 촉매 삽입 중합을위한 간단하고 효율적인 프로토콜

Norbornene can be polymerized by a variety of mechanisms, including insertion polymerization whereby the double bond is polymerized and the bicyclic ...

Preparation of Polyoxometalate-based Photo-responsive Membranes for the Photo-activation of Manganese Oxide Catalysts

This paper presents a method to prepare charge-transfer chromophores using polyoxotungstate (PW12O403-), transition metal ions (Ce3+ or Co2+), and organic polymers, with the aim of photo-activating oxygen-evolving manganese oxide catalysts, which are important components in artificial photosynthesis. The cross-linking technique was applied to obtain a self-standing membrane with a high PW12O403- content. Incorporation and structure retention of PW12O403- within the polymer matrix were confirmed by FT-IR and micro-Raman spectroscopy, and optical characteristics were investigated by UV-Vis spectroscopy, which revealed successful construction of the metal-to-metal charge transfer (MMCT) unit. After deposition of MnOx oxygen evolving catalysts, photocurrent measurements under visible light irradiation verified the sequential charge transfer, Mn &#8594; MMCT unit &#8594; electrode, and&#160;the photocurrent intensity was consistent with the redox potential of the donor metal (Ce or Co). This method provides a new strategy for preparing integrated systems involving catalysts and photon-absorption parts for use with photo-functional materials.

Here, we present a protocol to prepare charge transfer chromophores based on a polyoxometalate/polymer composite membrane.

사진-망간 산화물 촉매의 활성화에 대 한 Polyoxometalate 기반 사진 반응 막의 준비

This paper presents a method to prepare charge-transfer chromophores using polyoxotungstate (PW12O403-), transition metal ions (Ce3+ or Co2+), and organic ...

[(DPEPhos)(bcp)Cu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst

Our group recently reported the use of [(DPEPhos)(bcp)Cu]PF6 as a general copper-based photoredox catalyst which proved efficient to promote the activation of a broad variety of organic halides, including unactivated ones. These can then participate in various radical transformations such as reduction and cyclization reactions, as well as in the direct arylation of several (hetero)arenes. These transformations provide a straightforward access to a range of small molecules of interest in synthetic chemistry, as well as to biologically active natural products. Altogether, [(DPEPhos)(bcp)Cu]PF6 acts as a convenient photoredox catalyst which appears to be an attractive, cheap and complementary alternative to the state-of-the-art iridium- and ruthenium-based photoredox catalysts. Here, we report a detailed protocol for the synthesis of [(DPEPhos)(bcp)Cu]PF6, as well as NMR and spectroscopic characterizations, and we illustrate its use in synthetic chemistry for the direct arylation of (hetero)arenes and radical cyclization of organic halides. In particular, the direct arylation of N-methylpyrrole with 4-iodobenzonitrile to afford&#160;4-(1-methyl-1H-pyrrol-2-yl)benzonitrile and the radical cyclization of N-benzoyl-N-[(2-iodoquinolin-3-yl)methyl]cyanamide to afford natural product luotonin A are detailed. The scope and limitations of this copper-based photoredox catalyst are also briefly discussed.

[DPEPhosbcpCu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst

Detailed and general protocols are presented for the synthesis of [(DPEPhos)(bcp)Cu]PF6, a general copper-based photoredox catalyst, and for its use in synthetic chemistry for the direct arylation of C-H bonds in (hetero)arenes and radical cyclization of organic halides.

[(Bcp)] PF6: 일반적이 고 광범위 하 게 적용 가능한 구리 기반 포토에도 x 촉매

Our group recently reported the use of [(DPEPhos)(bcp)Cu]PF6 as a general copper-based photoredox catalyst which proved efficient to promote the ...

3D Printing and In Situ Surface Modification via Type I Photoinitiated Reversible Addition-Fragmentation Chain Transfer Polymerization

3D printing provides facile access to geometrically complex materials. However, these materials have intrinsically linked bulk and interfacial properties dependent on the chemical composition of the resin. In the current work, 3D printed materials are post-functionalized using the 3D printer hardware via a secondary surface-initiated polymerization process, thus providing independent control over the bulk and interfacial material properties. This process begins with preparing liquid resins, which contain a monofunctional monomer, a crosslinking multifunctional monomer, a photochemically labile species that enables initiation of polymerization, and critically, a thiocarbonylthio compound which facilitates reversible addition-fragmentation chain transfer (RAFT) polymerization. The thiocarbonylthio compound, known commonly as a RAFT agent, mediates the chain growth polymerization process and provides polymeric materials with more homogeneous network structures. The liquid resin is cured in a layer-by-layer fashion using a commercially available digital light processing 3D printer to give three-dimensional materials having spatially controlled geometries. The initial resin is removed and replaced with a new mixture containing functional monomers and photoinitiating species. The 3D printed material is then exposed to light from the 3D printer in the presence of the new functional monomer mixture. This allows photoinduced surface-initiated polymerization to occur from the latent RAFT agent groups on the surface of the 3D printed material. Given the chemical flexibility of both resins, this process allows a wide range of 3D printed materials to be produced with tailorable bulk and interfacial properties.

3D Printing and In Situ Surface Modification via Type I Photoinitiated Reversible Addition-Fragmentation Chain Transfer Polymerization

The present protocol describes the digital light processing-based 3D printing of polymeric materials using type I photoinitiated reversible addition-fragmentation chain transfer polymerization and the subsequent in situ material post-functionalization via surface-mediated polymerization. Photoinduced 3D printing provides materials with independently tailored and spatially controlled bulk and interfacial properties.

3D 프린팅 및 타입 I 광개시를 통한 현장 표면 개질 가역 추가 단편화 체인 이송 중합

3D printing provides facile access to geometrically complex materials. However, these materials have intrinsically linked bulk and interfacial properties ...

Photochemical Initiation Of Radical Polymerization Reactions

Source: David C. Powers, Tamara M. Powers, Texas A&#38;M
In this video, we will carry out the photochemically initiated polymerization of styrene to generate polystyrene, which is an important commodity plastic. We will learn the fundamentals of photochemistry and use simple photochemistry to initiate radical polymerization reactions. Specifically, in this module we will examine the photochemistry of benzoyl peroxide and its role as a photo-initiator of styrene polymerization reactions. In the described experiments, we will investigate the role of wavelength, photon absorption, and excited state structure on the efficiency (measured as quantum yield) of photochemical reactions.

급진적 중합 반응의 광화학 개시

Source: David C. Powers, Tamara M. Powers, Texas A&#38;M
In this video, we will carry out the photochemically initiated polymerization of styrene to ...

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무기 화학

Free-Radical Chain Reaction and Polymerization of Alkenes

The conversion of alkenes to macromolecules called polymers is a reaction of high commercial importance. The structure of the polymer is defined by a repeating unit, while the terminal groups are considered insignificant. The average degree of polymerization represents the number of repeating units in the polymer molecule and is denoted by the subscript n.
<img alt="Polymer chain structure diagram; hydrocarbon backbone with side groups, chemistry, material science." src="/files/ftp_upload/11773/11773_PT_Figure_1.svg" style="text-align: center; height: 60px;" data-altupdatedat="1747908711000" data-alt="Figure1">
Alkenes undergo polymerization via a free-radical mechanism involving three steps: initiation, propagation, and termination. 
Radicals are generated in the initiation step by heating a small quantity of free-radical initiators such as benzoyl peroxide. The benzoyloxy radical loses CO2 and forms a phenyl radical (Ph·), which adds to the double bond of the alkene to initiate the polymerization process. One of the electrons of the alkene π bond pairs with one electron from the phenyl radical to form a new C–C bond.
<img alt="Radical reaction mechanism diagram, benzoyl peroxide decomposition into radicals, chemical process." src="/files/ftp_upload/11773/11773_PT_Figure_2.svg" style="text-align: center; height: 60px;" data-altupdatedat="1747908711000" data-alt="Figure2">
<img alt="Chemical reaction diagram of phenyl cation formation via decarboxylation process with equations." src="/files/ftp_upload/11773/11773_PT_Figure_3.svg" style="text-align: center; height: 60px;" data-altupdatedat="1747908711000" data-alt="Figure3">
<img alt="Chemical reaction diagram showing radical polymerization steps with benzene and propylene." src="/files/ftp_upload/11773/11773_PT_Figure_4.svg" style="text-align: center; height: 80px;" data-altupdatedat="1747908711000" data-alt="Figure4">
In the propagation step, the carbon radical generated in the initiation step adds to another molecule of alkene to generate a new radical. The continuous addition of alkene monomers at the radical site yields the polymer.
<img alt="Allylic polymerization process, chemical reaction equation, polymer chain formation." src="/files/ftp_upload/11773/11773_PT_Figure_5.svg" style="text-align: center; height: 80px;" data-altupdatedat="1747908711000" data-alt="Figure5">
The termination step of the free-radical mechanism occurs via recombination or disproportionation. In a recombination step, two growing chains form a bond at their radical sites.
<img alt="Polymerization process diagram with structural formulas and reaction arrows." src="/files/ftp_upload/11773/11773_PT_Figure_6.svg" style="text-align: center; height: 60px;" data-altupdatedat="1747908711000" data-alt="Figure6">
In termination by disproportionation, a β-hydrogen atom is transferred from one radical to another radical center, resulting in two non-radical products.
<img alt="Free radical reaction diagram; benzyl radical formation; organic chemistry mechanism." src="/files/ftp_upload/11773/11773_PT_Figure_7.svg" style="text-align: center; height: 300px;" data-altupdatedat="1747908711000" data-alt="Figure7">
The free-radical polymerization of ethylene yields low-density polyethylene (LDPE), where the low density is a consequence of significant branching in the polymer chains. Articles made from polymers surround us in various forms, such as food packaging materials, plastic bags, bottles, stationery, and automotive parts.

Free-radical Polymerization Reaction of Alkenes

자유 라디칼 연쇄 반응 및 알켄의 중합

The conversion of alkenes to macromolecules called polymers is a reaction of high commercial importance. The structure of the polymer is defined by a ...

유기화학

주요 용어 및 개념

Radical Chain-Growth Polymerization: Overview

Chain-growth or addition polymerization is successive addition reactions of monomers with a polymer chain. In radical chain-growth polymerization, the reaction proceeds via a free-radical intermediate. The free radical is formed from radical initiators, which spontaneously generate free radicals by homolytic fission. Organic peroxides (such as dibenzoyl peroxide, as shown in Figure 1) or azo compounds are popular radical initiators. A low concentration ratio of radical initiator to monomer is used to minimize radical coupling.
<img alt="Figure1" src="/files/ftp_upload/12920/12920_PT_Figure_1.svg" style="text-align: center; height: 75px;" />
Figure 1: The homolytic fission reaction of radical initiator dibenzoyl peroxide to generate benzoyloxy radicals and the subsequent decomposition to phenyl radicals
This free radical initiates polymerization by reacting with a monomer molecule. Unsaturated monomers are suitable for radical chain-growth polymerization; a substituent group across the unsaturated bond that stabilizes the free radical increases the reaction feasibility. Ethylene, propylene, vinyl chloride, and styrene are examples of monomers that can be polymerized via free-radical chain-growth polymerization.
The reaction between a monomer and a free radical generates a new free radical. This new radical reacts with another monomer and creates yet another free radical. The polymer chain grows as the reaction between free-radical intermediates and monomers repeats sequentially. Typically, the propagation step repeats one thousand to ten thousand times before the termination of polymerization.
Often, chain transfer reagents, such as thiol, are used to control the molecular weight (Figure 2). A chain transfer agent must be sufficiently reactive to transfer a hydrogen atom to the growing chain to terminate the polymer growth. The resultant radical must add to a double bond in the monomer to initiate polymerization.
<img alt="Figure2" src="/files/ftp_upload/12920/12920_PT_Figure_2_.svg" style="text-align: center; height: 150px;" />
Figure 2: (Top): The termination reaction of chain transfer agent thiol and a growing polymer chain; (Bottom): Subsequent reaction of thiol radical and monomer molecule to initiate polymer growth
Inhibitors are the reagents used to reduce the reactivity of radicals in the growing polymer chain. Figure 3 depicts the reaction of benzoquinone as an inhibitor.
<img alt="Figure3" src="/files/ftp_upload/12920/12920_PT_Figure_3.svg" style="text-align: center; height: 200px;" />
Figure 3: The reaction between chain inhibitor benzoquinone and a growing polymer chain to generate a less reactive free radical

Radical Chain-Growth Polymerization: 개요

Chain-growth or addition polymerization is successive addition reactions of monomers with a polymer chain. In radical chain-growth polymerization, the ...