Name: reductive electropolymerization of a vinyl-containing poly-pyridyl complex on glassy carbon and fluorine-doped tin oxide electrodes
Uploaded: 2015-01-30T15:00:00.000+00:00
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Description: Watch this Scientific Journal Video about Reductive Electropolymerization of a Vinyl-containing Poly-pyridyl Complex on Glassy Carbon and Fluorine-doped Tin Oxide Electrodes at JoVE.com

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1.合成1 根据- :合成1（图4; 5,5&#39;- dvbpy是5,5&#39;-二乙烯基-2,2&#39;-联吡啶三联吡啶，2&#39;&#39;PhTpy是4&#39;-苯基-2,2&#39;6&#39;）步骤前面所述。18 2.准备的1 1.3毫单体溶液中的电解质溶液<ol><li>制备的四正丁基六氟磷酸盐的0.1M库存电解质溶液，TBAPF 6，在乙腈，MeCN中。 <ol><li>放置的MeCN过度活化的3埃分子筛或K 2 CO 3，24小时，以除去外来的 H 2 O. </li><li>将TBAPF 6（0.969克，2.50毫摩尔）在25.00毫升火焰干燥的容量瓶中。 </li><li>过滤分子筛或K 2 CO从干乙腈3微粒，并把包含TBAPF的25.00毫升容量瓶<suB&gt; 6至体积。 </li></ol></li><li>放置1（0.0049克，5.2×10 -6摩尔）的干燥4英钱的小瓶或10毫升圆底烧瓶中，并添加4.00为0.1M TBAPF 6在MeCN原液的溶液中。 </li><li>转移3.5-4.0毫升1的红橙色着色电解液成3-隔室池的中央室，其中每个隔室通过中等孔率玻璃料分离。 </li><li>快速填充3-隔室电池的外部隔室，以相等的高度的中央室原液，与部分剩余的干的0.1M TBAPF 6的MeCN中，以防止泄漏到外室中。注意:时间是一个重要的因素，因为在不同的隔室的解决方案会慢慢混合并显著改变主隔室的浓度，如果溶剂的高度是不一样的。 </li></ol> 3. Electropolymerize 1对3毫米直径的玻璃Ÿ碳电极或1.0 平方厘米FTO电极<ol><li>准备隔氮/氩气排气管和电极。 <ol><li>切缝到每3个橡胶隔，引导薄聚四氟乙烯，PTFE，管通过狭缝。 </li><li>通过所述隔片的1滑动的Ag / 硝酸银参比电极，将参考电极/ PTFE管/隔膜在所述外室中的一个，并密封与 ​​隔垫的隔室。 </li><li>通过不同的隔膜代替铂线/ PTFE管/隔膜引导铂线/纱布反电极在所述外室中的一个，并密封与隔垫的隔室。如果狭缝不足够大或导线足够硬，以防止弯曲的金属丝，可以使用一个大口径针穿过隔膜以引导铂丝反电极。 </li><li>通过剩余的隔膜引导新鲜抛光3毫米玻碳电极，并把它使得电极是suspended在溶液中，或对于一个FTO滑动，引导连接到通过隔膜的鳄鱼夹的导线，然后夹紧用鳄鱼夹在FTO滑动，并确保浸没当滑动的导电面是垂直于对置电极。 <ol><li>之前插入玻碳电极:通过将氧化铝（0.5微米）上的润湿抛光垫抛光的玻璃碳，然后，将电极在一个8字形运动，持续30秒，同时保持电极垂直于所述垫 - 向抛光电极各方均匀-和冲洗任何剩余的氧化铝关闭了H 2Ø水喷瓶跟一个乙腈喷瓶冲洗。 </li><li>前夹紧在FTO滑动:环绕一个30×10mm的FTO滑动，使得所述滑动件的10×10mm的部分被暴露的中心部分的非导电卡普顿胶带几层。 </li><li>通过放置/保持在FTO幻灯片在POSIT收集在FTO幻灯片的UV-Vis光谱离子在已经预定以确保一致性分光计的光束路径。 </li></ol></li></ol></li><li>脱曝气在3-隔室电化学电池的解决方案。 <ol><li> Tygon管的一端连接至氮/氩气供给，将另一端连接到含有MeCN中的气体洗涤器。 </li><li>剪下另一块聚乙烯管，一端连接到流出乙腈冲氮气/氩气，另一端连接到4路分流。 </li><li>连接根PTFE管到分离器4的方式的3余下的连接。 </li><li>淹没根PTFE管进入溶液中的每个隔室的，并打开氮气/氩气的流量，使得所述溶液的快速鼓泡开始。 </li><li>继续脱气溶液5-10分钟，然后将聚四氟乙烯管只是溶液的表面上方，/氩离开，以保持惰性气体正压上的系统，并防止溶液氮气流Çonvection造成起泡。 </li></ol></li><li>进行电化学实验。 <ol><li>从电位在3-隔室单元的相应电极连接的电极。 </li><li>执行循环伏安法，CV实验使用以下参数:开关电位= 0V和-1.81伏;扫描/扫描速率= 100毫伏/秒;周期= 5的号码。 </li><li>当CV实验完成后，从聚合溶液中除去工作（玻璃碳或FTO）电极和轻轻地从吸液管或喷射瓶，以除去任何剩余的单体溶液冲洗用MeCN所述电极的表面上。 </li></ol></li></ol> 4.表面覆盖测定<ol><li>放置漂洗工作电极中的的0.1M TBAPF 6 / MeCN中新鲜制备的溶液中含有一对电极和一个参考电极（优选在electropolymerizatio使用的相同的参考电极的电化学电池N）。 </li><li>执行循环伏安法，CV实验使用以下参数:开关电位= 0和1.5伏;扫描/扫描速率= 100毫伏/秒;循环数= 15。 </li><li>整合在阳极和阴极峰的电荷的吸附electropolymer钌（III / II）的耦合，所述阳极和阴极的峰下平均化的电荷，并使用等式1确定表面覆盖。 </li><li>对于在FTO幻灯片:地点/保持在紫外可见样品支架，使得所述射束路径通过着色膜的前面在预定位置在FTO滑动。在FTO幻灯片可以是湿法或干法，但在相同的条件下做比较作为空白谱下收集。 </li><li>减去用于收集该特定幻灯片的FTO光谱得到的频谱之前从薄膜上的FTO的频谱，以便产生的吸收光谱为电影本身电解。 </li></ol>

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Electroanal. Chem. Interfacial Electrochem. 115, 65-74 (1980).</li><li>Laviron, E. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=General+expression+of+the+linear+potential+sweep+voltammogram+in+the+case+of+diffusionless+electrochemical+systems.">General expression of the linear potential sweep voltammogram in the case of diffusionless electrochemical systems.</a> J. Electroanal. Chem. 101, 19-28 (1979).</li><li>Ratcliff, E. L., Jenkins, J. L., Nebesny, K., Armstrong, N. R. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Electrodeposited,+&#34;Textured&#34;+Poly(3-hexyl-thiophene)+(e-P3HT)+Films+for+Photovoltaic+Applications.">Electrodeposited, &#34;Textured&#34; Poly(3-hexyl-thiophene) (e-P3HT) Films for Photovoltaic Applications.</a> Chemistry of Materials. 20, 5796-5806 (2008).</li></ol>

No conflicts of interest declared.

电化学提供了一个大范围的可控变量是不常见的其他技术。除了 ​​标准的反应变量，如试剂（单体）浓度，温度，溶剂等 ，电解可以另外通过共同的电化学方法电化学实验参数控制。 CV扫描速率，切换电位，和循环次数影响electropolymers的沉积。例如，作为循环通过配体还原波的数量增加，所以也是表面覆盖。在这里提出的范围内，是线性的相对于执行的周期数（ 见表1）。 ...

电解是利用施加的电势以引发单体的前体的聚合直接在电极的表面上并已被利用来生产薄电活性和/或光化学活性多吡啶薄膜上的电极和半导体的表面上。1-4电催化的聚合技术， 5-10电子转移，11，12光化学，13-16电致变色，17和配位化学18已经研究了电聚合膜。这项技术最早是在北卡罗莱纳州的乙烯基3，5，7，8，11-15，19，20和吡咯6,9的电化学一个迈耶-穆雷合作大学，21-24衍生我TAL络合物对各种导电衬底。 图1给出了一些，当配位到金属配合物，已产生electropolymers共同吡啶基配体。在还原性电解，含乙烯基化合物的电解时发生缀合的乙烯基吡啶配体的减少，而与吡咯官能配位体，电解是由吡咯部分的氧化发起的，从而导致氧化电解（ 图2）。电解技术，用于直接连接几乎任何过渡金属配合物的任何电极上设置的一般化方法的目的开发的。该方法的多样性打开大门，electropolymer修饰电极的大量调查。 而相比之下，其他附接策略，这涉及直接接合到电极，电解提供了副antage不需要电极表面预修饰。因此它可以应用无论表面组成或形态4，10，25，以任何数量的导电基板，26这种多功能性是变化的物理性质的聚合物长度的增长的结果;所述单体可溶于电解液而是作为发生聚合和交联rigidifies薄膜，沉淀和物理吸附在电极表面发生（ 图3）。27 相比氧化物表面结合的羧酸酯，它们是不稳定的氧化物表面的水，或膦酸酯衍生的复合物，它们是不稳定的，在升高的pH值的，在太阳能燃料研究常用，这些界面的电极的聚合物膜结构提供了稳定性的额外的好处在各种媒体，包括有机溶剂和水在​​大的pH范围（0-14）。28-30电聚合还可以存大范围明显的表面覆盖范围，从亚单层至数十或数百当量单层，而羧酸盐或磷酸盐衍生复合接口结构局限于单层表面覆盖度的电影。 虽然任何数量的乙烯基或含吡咯吡啶基和聚吡啶化合物能够聚合的，使用[Ru II（PhTpy）（5,5&#39;- dvbpy）（MeCN中）]（PF 6）2，（1; PhTpy是4&#39;-苯基-2,2&#39;:6&#39;，2&#39;&#39; -三联吡啶; 5,5&#39;- dvbpy是5,5&#39;-二乙烯基-2,2&#39;-联吡啶; 图4）将被用作模型复杂证明还原电解上玻璃碳和氟掺杂的氧化锡，FTO，本报告中的电极1是现代electropolymer前体具有潜在的电的应用的一个例子，并且由于其金属对利GAND电荷转移，MLCT，吸收光谱躺在光光谱的可见光区，可以用UV-Vis光谱。18，30请注意，某些结果呈现此处为1已经发表在稍微修改的形式。18调查

<table><tbody><tr><td>Tetrabutylammonium hexafluorophosphate for electrochemical analysis, &amp;ge;99.0%</td><td>Sigma-Aldrich</td><td>86879-25G</td><td></td></tr><tr><td>Acetonitrile&amp;nbsp;(Optima LC/MS), Fisher Chemical</td><td>Fisher Scientific</td><td>A955-4</td><td></td></tr><tr><td>3 mm dia. Glassy Carbon Working Electrode</td><td>CH Instruments</td><td>CH104</td><td></td></tr><tr><td>Non-Aqueous Ag/Ag&lt;sup&gt;+&lt;/sup&gt; Reference Electrode w/ porous Teflon Tip</td><td>CH Instruments</td><td>CHI112</td><td></td></tr><tr><td>Platinum&amp;nbsp;gauze</td><td>Alfa Aesar</td><td>AA10282FF&amp;nbsp;</td><td></td></tr><tr><td>Electrode Polishing Kit</td><td>CH Instruments</td><td>CHI120</td><td></td></tr><tr><td>Cole-Parmer KAPTON TAPE 1/2&amp;nbsp;IN x 36&amp;nbsp;YD</td><td>Fisher Scientific</td><td>NC0099200</td><td></td></tr><tr><td>Fisherbrand Polypropylene Tubing 4-Way Connectors</td><td>Fisher Scientific</td><td>15-315-32B</td><td></td></tr><tr><td>500 ml Bottle, Gas Washing, Tall Form, Coarse Frit</td><td>Chemglass</td><td>CG-1114-15</td><td></td></tr><tr><td>3-compartment H-Cell for electrochemistry</td><td>Custom made H-cell with 3 compartments</td><td></td><td></td></tr></tbody></table>

reductive electropolymerization of a vinyl-containing poly-pyridyl complex on glassy carbon and fluorine-doped tin oxide electrodes

可控电极表面改性是在许多领域，特别是那些与太阳能电池的燃料的应用是重要的。电解是通过利用施加的电势来启动，在亥姆霍兹层基板的聚合镀层在电极的表面上的聚合物膜的一个表面改性技术。这种有用的技术，最早是由美国北卡罗来纳大学教堂山分校在20世纪80年代初穆雷梅耶尔合作建立并用来研究含无机复合物作为单体基材薄膜众多的物理现象。在这里，我们突出显示用无机复合涂层的电极的程序通过执行含乙烯基的聚吡啶基络合物的还原性电解到玻璃碳和氟掺杂氧化锡涂层的电极。电化学电池配置和故障排除程序的建议都包括在内。虽然不是ê这里xplicitly描述的，含吡咯的化合物的氧化电聚合遵循类似程序，以乙烯基类还原性电解，但远不如敏感为氧气和水。

Electropolymer增长遵守规定的CV实验（协议文本STEP 3.3.2）的进展情况时，最容易识别。 图5体现在0.071厘米2（3毫米直径）electropolymer增长，1玻碳电极。在实验的第一周期产生一个伏安大致类似于该预计为类似浓度（ 图5，黑色迹线），但的钌溶液在连续循环，通过第 1 次和第2 次的配体为本还原波，日益增强的电流是观察到的（ ...

Watch this Scientific Journal Video about Reductive Electropolymerization of a Vinyl-containing Poly-pyridyl Complex on Glassy Carbon and Fluorine-doped Tin Oxide Electrodes at JoVE.com

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

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.

在玻碳和氟掺杂的氧化锡电极的含乙烯基聚吡啶基复合还原电聚合

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

reductive-electropolymerization-vinyl-containing-poly-pyridyl-complex

Research

JoVE Journal

Chemistry

11.8K 次观看.  Virginia Military Institute. 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. 

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

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.

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

使用苝作为可见光光催化功能化的乙烯基单体原子转移自由基聚合

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

科研

化学

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.

电活性聚合物纳米粒子参展光热特性

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

工程学

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.

功能性降冰片烯的催化聚合插入一种简单高效的协议

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

Electrochemical Impedance Spectroscopy as a Tool for Electrochemical Rate Constant Estimation

Electrochemical impedance spectroscopy (EIS) was used for advanced characterization of organic electroactive compounds along with cyclic voltammetry (CV). In the case of fast reversible electrochemical processes, current is predominantly affected by the rate of diffusion, which is the slowest and limiting stage. EIS is a powerful technique that allows separate analysis of stages of charge transfer that have different AC frequency response. The capability of the method was used to extract the value of charge transfer resistance, which characterizes the rate of charge exchange on the electrode-solution interface. The application of this technique is broad, from biochemistry up to organic electronics. In this work, we are presenting the method of analysis of organic compounds for optoelectronic applications.

Electrochemical impedance spectroscopy (EIS) of species that undergo reversible oxidation or reduction in solution was used for determination of rate constants of oxidation or reduction.

电化学阻抗谱作为电化学速率常数估计的一种工具

Electrochemical impedance spectroscopy (EIS) was used for advanced characterization of organic electroactive compounds along with cyclic voltammetry (CV). ...

Raman and IR Spectroelectrochemical Methods as Tools to Analyze Conjugated Organic Compounds

In the presented work, two spectroelectrochemical techniques are discussed as tools for the analysis of the structural changes occurring in the molecule on the vibrational level of energy. Raman and IR spectroelectrochemistry can be used for advanced characterization of the structural changes in the organic electroactive compounds. Here, the step-by-step analysis by means of Raman and IR spectroelectrochemistry is shown. Raman and IR spectroelectrochemical techniques provide complementary information about structural changes occurring during an electrochemical process, i.e. allows for the investigation of redox processes and their products. The examples of IR and Raman spectroelectrochemical analysis are presented, in which the products of the redox reactions, both in solution and solid state, are identified.

A protocol of step-by-step Raman and IR spectroelectrochemical analysis is presented.

拉曼光谱和红外光谱电化学法作为分析共轭有机化合物的工具

In the presented work, two spectroelectrochemical techniques are discussed as tools for the analysis of the structural changes occurring in the molecule ...

Using Cyclic Voltammetry, UV-Vis-NIR, and EPR Spectroelectrochemistry to Analyze Organic Compounds

Cyclic voltammetry (CV) is a technique used in the analysis of organic compounds. When this technique is combined with electron paramagnetic resonance (EPR) or ultraviolet-visible and near-infrared (UV-Vis-NIR) spectroscopies, we obtain useful information such as electron affinity, ionization potential, band-gap energies, the type of charge carriers, and degradation information that can be used to synthesize stable organic electronic devices. In this study, we present electrochemical and spectroelectrochemical methods to analyze the processes occurring in active layers of an organic device as well as the generated charge carriers.

In this article, we describe electrochemical, electron paramagnetic resonance, and ultraviolet-visible and near-infrared spectroelectrochemical methods to analyze organic compounds for application in organic electronics.

利用循环伏安法、紫外-近红外光谱和 EPR 光谱电化学对有机化合物进行分析

Cyclic voltammetry (CV) is a technique used in the analysis of organic compounds. When this technique is combined with electron paramagnetic resonance ...

Reactive Vapor Deposition of Conjugated Polymer Films on Arbitrary Substrates

We demonstrate a method of conformally coating conjugated polymers on arbitrary substrates using a custom-designed, low-pressure reaction chamber. Conductive polymers, poly(3,4-ethylenedioxythiophene) (PEDOT) and poly(3,4-propylenedioxythiophene) (PProDOT), and a semiconducting polymer, poly(thieno[3,2-b]thiophene) (PTT), were deposited on unconventional highly-disordered and textured substrates with high surface areas, such as paper, towels and fabrics. This reported deposition chamber is an improvement of previous vapor reactors because our system can accommodate both volatile and nonvolatile monomers, such as 3,4-propylenedioxythiophene and thieno[3,2-b]thiophene. Utilization of both solid and liquid oxidants are also demonstrated. One limitation of this method is that it lacks sophisticated in situ thickness monitors. Polymer coatings made by the commonly used solution-based coating methods, such as spin-coating and surface grafting, are often not uniform or susceptible to mechanical degradation. This reported vapor phase deposition method overcomes those drawbacks and is a strong alternative to common solution-based coating methods. Notably, polymer films coated by the reported method are uniform and conformal on rough surfaces, even at a micrometer scale. This feature allows for future application of vapor deposited polymers in electronics devices on flexible and highly textured substrates.

This paper presents a protocol for reactive vapor deposition of poly(3,4-ethylenedioxythiophene), poly(3,4-propylenedioxythiophene), and poly(thieno[3,2-b]thiophene) films on glass slides and rough substrates, such as textiles and paper.

任意基底上共轭聚合物薄膜的反应气相沉积

We demonstrate a method of conformally coating conjugated polymers on arbitrary substrates using a custom-designed, low-pressure reaction chamber. ...

Fabricating Degradable Thermoresponsive Hydrogels on Multiple Length Scales via Reactive Extrusion, Microfluidics, Self-assembly, and Electrospinning

While various smart materials have been explored for a variety of biomedical applications (e.g., drug delivery, tissue engineering, bioimaging, etc.), their ultimate clinical use has been hampered by the lack of biologically-relevant degradation observed for most smart materials. This is particularly true for temperature-responsive hydrogels, which are almost uniformly based on polymers that are functionally non-degradable (e.g., poly(N-isopropylacrylamide) (PNIPAM) or poly(oligoethylene glycol methacrylate) (POEGMA)). As such, to effectively translate the potential of thermoresponsive hydrogels to the challenges of remote-controlled or metabolism-regulated drug delivery, cell scaffolds with tunable cell-material interactions, theranostic materials with the potential for both imaging and drug delivery, and other such applications, a method is required to render the hydrogels (if not fully degradable) at least capable of renal clearance following the required lifetime of the material. To that end, this protocol describes the preparation of hydrolytically-degradable hydrazone-crosslinked hydrogels on multiple length scales based on the reaction between hydrazide and aldehyde-functionalized PNIPAM or POEGMA oligomers with molecular weights below the renal filtration limit. Specifically, methods to fabricate degradable thermoresponsive bulk hydrogels (using a double barrel syringe technique), hydrogel particles (on both the microscale through the use of a microfluidics platform facilitating simultaneous mixing and emulsification of the precursor polymers and the nanoscale through the use of a thermally-driven self-assembly and cross-linking method), and hydrogel nanofibers (using a reactive electrospinning strategy) are described. In each case, hydrogels with temperature-responsive properties similar to those achieved via conventional free radical cross-linking processes can be achieved, but the hydrazone cross-linked network can be degraded over time to re-form the oligomeric precursor polymers and enable clearance. As such, we anticipate these methods (which may be generically applied to any synthetic water-soluble polymer, not just smart materials) will enable easier translation of synthetic smart materials to clinical applications.

Protocols are described for the fabrication of degradable thermoresponsive hydrogels based on hydrazone cross-linking of polymeric oligomers on the bulk scale, microscale, and nanoscale, the latter for preparation of both gel nanoparticles and nanofibers.

通过反应挤出、微流体、自组装和电纺丝制备多长尺度可降解 Thermoresponsive 水凝胶

While various smart materials have been explored for a variety of biomedical applications (e.g., drug delivery, tissue engineering, bioimaging, etc.), ...

生物工程

Electrochemical Preparation of Poly(3,4-Ethylenedioxythiophene) Layers on Gold Microelectrodes for Uric Acid-Sensing Applications

Two different methods for the synthesis of poly(3,4-ethylenedioxythiophene) (PEDOT) on gold electrodes are described, using electropolymerization of 3,4-ethylenedioxythiophene (EDOT) monomer in an aqueous and an organic solution. Cyclic voltammetry (CV) was used in the synthesis of PEDOT thin layers. Lithium perchlorate (LiClO4) was used as a dopant in both aqueous (aqueous/acetonitrile (ACN)) and organic (propylene carbonate (PC)) solvent systems. After the PEDOT layer was created in the organic system, the electrode surface was acclimatized by successive cycling in an aqueous solution for use as a sensor for aqueous samples. 
The use of an aqueous-based electropolymerization method has the potential benefit of removing the acclimatization step to have a shorter sensor preparation time. Although the aqueous method is more economical and environmentally friendly than the organic solvent method, superior PEDOT formation is obtained in the organic solution. The resulting PEDOT electrode surfaces were characterized by scanning electron microscopy (SEM), which showed the constant growth of PEDOT during electropolymerization from the organic PC solution, with rapid fractal-type growth on gold (Au) microelectrodes.

Electrochemical Preparation of Poly3,4-Ethylenedioxythiophene Layers on Gold Microelectrodes for Uric Acid-Sensing Applications

We describe aqueous and organic solvent systems for the electropolymerization of poly(3,4-ethylenedioxythiophene) to create thin layers on the surface of gold microelectrodes, which are used for sensing low molecular weight analytes.

在金微电极上电化学制备聚（3，4-乙烯二氧噻吩）层在尿酸传感应用中

Two different methods for the synthesis of poly(3,4-ethylenedioxythiophene) (PEDOT) on gold electrodes are described, using electropolymerization of ...

Vapor Phase Deposition of Electroactive Poly(3,4-ethylenedioxythiophene) onto Electrospun Commodity Polymer Nanofibers

This study investigates the preparation of polyacrylonitrile (PAN) nanofibers through electrospinning to create highly porous and strong materials for applications in water purification, electrocatalysis, and biomedicine. The uniformly white PAN nanofiber mats were cut into 2 cm x 2 cm coupons to ensure consistency. After electrospinning, these nanofibers were coated with an electroactive polymer (EAP) using chemical vapor deposition, with iron (III) chloride (FeCl3) serving as an oxidant for polymerizing 3,4-ethylenedioxythiophene (EDOT) into poly(3,4-ethylenedioxythiophene) (PEDOT). The study examined the impact of different FeCl3 concentrations on PEDOT deposition on the PAN coupons. PEDOT deposition led to an increase in coupon weight. Scanning electron microscopy (SEM) revealed increases in the diameter of the nanofibers treated with increasing FeCl3 oxidant concentration, although higher FeCl3&#160;concentrations caused inter-fiber bridging, implying a concomitant decrease in inter-fiber spacing. Energy dispersive X-ray spectroscopy (EDS) was used to confirm the presence of Fe, Cl, and S in the nanofibers, with sulfur content rising with FeCl3&#160;concentration used, suggesting increased PEDOT deposition efficiency with increasing oxidant concentration. Mechanical testing showed that PEDOT-coated PAN fibers had improved tensile strength and toughness in the hydrated state compared to pure PAN nanofibers. These results highlight the crucial role of FeCl3&#160;concentration in influencing the morphology and properties of PAN-PEDOT composites, enhancing their suitability for applications such as water purification, tissue engineering, biosensing, catalysis, and energy storage.

This paper describes a simple technique for coating electrospun PAN nanofibers with electroactive polymers using vapor deposition. The effects of the oxidant FeCl&#8323; on the deposition of poly(3,4-ethylenedioxythiophene) coatings on PAN were investigated to understand and optimize polymer growth, fiber diameter, and overall mechanical strength of the nanofiber mats.

电活性聚（3,4-乙烯二氧噻吩）在电纺商品聚合物纳米纤维上的气相沉积

This study investigates the preparation of polyacrylonitrile (PAN) nanofibers through electrospinning to create highly porous and strong materials for ...