这项工作得到了赫尔辛基大学和简和阿托斯·埃克科基金会的支持。S.H.感谢伊拉斯谟®欧盟基金的奖学金。

1. Ag-Pd/ZrO2 NP 的合成 
注：在此过程中，Ag-Pd 中的 Pd 摩尔百分比对应为 1%，ZrO2 上的 Ag-Pd 负载对应为 3 wt.%。
<ol><li>将 1 克 ZrO2 粉末放置在 250 mL 烧杯中。</li>
	<li>在室温下，在剧烈的磁搅拌（500 转/升）下，将 50 mL 的 AgNO3 （aq） （0.0059 摩尔/L） 和 K2PdCl4 （aq） （0.00031 mol/L） 溶液添加到烧杯中。</li>
	<li>添加 10 mL 的赖氨酸 （0.53 M） 液态溶液。</li>
	<li>将混合物保持在剧烈搅拌（500转pm）下20分钟。</li>
	<li>20 分钟后，使用移液器以 1 mL/min 的速度，将新制备的 NaBH4 （aq） （0.035 M） 溶液的悬架加到 10 mL 中。在整个过程中保持悬架搅拌（500 rpm）。</li>
	<li>让混合物在室温下搅拌30分钟。</li>
</ol>2. 催化剂的分离和净化
<ol><li>将悬架转移到离心管中，以 3，260 x g的离心速度将固体与混合物分离 10 分钟。</li>
	<li>用移液器小心地去除液体相，并在管子中加入 15 mL 去离子水。<ol>
<li>剧烈摇动，直到获得固体的分散。如果不能实现良好的分散，将管子放在超声波浴池中5分钟。</li>
		<li>离心分散在3，260 x g 10分钟。</li>
	</ol>
</li>
	<li>使用去离子水重复两次（2.2 到 2.2.2.），然后一次使用乙醇代替水。</li>
	<li>取出乙醇，在60°C的烤箱中干燥固体12小时。</li>
	<li>通过各种显微镜、元素和光谱技术来描述已制备的 Ag-Pd/ZrO2 NP。</li>
</ol>3. Ag/ZrO2 NPs 的合成 
注：在此过程中，ZrO2 上的 Ag 加载对应于 3 wt.%。
<ol><li>将 1 克 ZrO2 粉末放置在 250 mL 烧杯中。</li>
	<li>在室温下，在剧烈的磁搅拌（500 rpm）下，将 50 mL 的 AgNO3 （aq） （0.0059 mol/L） 溶液添加到烧杯中。</li>
	<li>添加 10 mL 的赖氨酸 （0.53 M） 液态溶液。</li>
	<li>将混合物保持在剧烈搅拌（500转pm）下20分钟。</li>
	<li>20 分钟后，使用移液器以 1 mL/min 的速度，将新制备的 NaBH4 （aq） （0.035 M） 溶液的悬架加到 10 mL 中。在整个过程中保持悬架搅拌（500 rpm）。</li>
	<li>让混合物在室温下搅拌30分钟。</li>
</ol>4. 催化剂的分离和净化
<ol><li>将悬架转移到离心管中，以 3，260 x g的离心速度将固体与混合物分离 10 分钟。</li>
	<li>用移液器小心地去除液体相，并在管子中加入 15 mL 去离子水。<ol>
<li>剧烈摇动，直到观察到固体的分散。如果不能实现良好的分散，将管子放在超声波浴池中5分钟。</li>
		<li>离心分散在3，260 x g 10分钟。</li>
	</ol>
</li>
	<li>重复洗涤步骤（4.2至4.2.2.）两次使用去离子水，然后一次使用乙醇代替水。</li>
	<li>取出乙醇，在60°C的烤箱中干燥固体12小时。</li>
	<li>然后，制备的Ag/ZrO2 NPs可以具有各种显微镜、元素和光谱技术的特点。</li>
</ol>5. LSPR激发（光照）下对硝基苯减少的质离子催化性能调查
<ol><li>将 30 毫克催化剂与磁性搅拌棒一起放置在 25 mL 圆底烧瓶中。</li>
	<li>在异丙醇（IPA）中加入5毫升的亚硝基苯溶液（0.03摩尔/升）到反应堆中。</li>
	<li>然后，加入11.22毫克KOH粉末（0.0002摩尔）。</li>
	<li>用砷流冒泡悬架1分钟，清除反应堆。清除后立即密封烧瓶。</li>
	<li>将反应堆放在温度控制的磁搅拌器（500 rpm）上方70°C加热的油浴中。</li>
	<li>使用波长为 425 nm 的 4 个 LED 灯作为光源对管子进行辐照，光强度为 0.5 W/cm2。从灯到反应瓶的距离应该是7厘米。</li>
	<li>让反应在 70 °C 下在强磁搅拌 （500 rpm） 下进行 2.5 小时。</li>
	<li>然后，关掉灯，打开反应堆，用注射器和针头收集1mL样品。通过 0.45 μm 过滤器过滤，将催化剂颗粒去除，放入气相色谱瓶中。</li>
</ol>6. 在没有LSPR激发的情况下的反应（黑暗条件）
<ol><li>遵循 5 中描述的相同步骤，但无需光照射。用铝箔包裹反应管，防止光线暴露。</li>
</ol>7. 气相色谱（GC）分析准备
<ol><li>准备含有约 30 mmol/L 硝基苯 （NB）、30 mmol/L 苯 （AN） 和 30 mmol/L 的偶氮苯 （AB） 的 IPA 溶液。</li>
	<li>使用合适的方法对解决方案进行 GC 分析。可以通过改变柱温和气流程序来测试不同的方法。选定的方法应能够在最短的保留期内分离与 IPA、NB、AN 和 AB 对应的峰值。</li>
	<li>选择该方法后，在 IPA 中编写一组 50 mM、25 mM、10 mM、5 mM 和 2.5 mM NB 的解决方案，并在 IPA 中编写另一组浓度相同的 AN 和 AB 解决方案。</li>
	<li>对已准备的解决方案进行 GC 分析。每个色谱图应呈现 2 个峰值：较高的峰值对应 IPA，下一个对应于 NB、AN 或 AB 的峰值。对于每个色谱图，请记下所有峰值的保留时间和峰值区域。</li>
	<li>通过绘制每个样本的浓度与峰值区域来跟踪 NB、AN 和 AB 的校准曲线。</li>
</ol>8. GC 分析
<ol><li>对第 5 步收集的样本进行 GC 分析。和6.与用于步骤7.2的相同方法。和7.4。</li>
	<li>对于每个色谱图，请记下保留时间和峰值区域，并使用之前绘制的校准曲线来确定样品中 NB、AN 和 AB 的浓度。</li>
	<li>使用方程计算硝基苯转换以及苯和苯的选择性： <img alt="Equation 1" src="/files/ftp_upload/61712/61712eq1.jpg"> <img alt="Equation 2" src="/files/ftp_upload/61712/61712eq2.jpg"> <img alt="Equation 3" src="/files/ftp_upload/61712/61712eq3.jpg"> <img alt="Equation 4" src="/files/ftp_upload/61712/61712eq4.jpg">在GC分析2.5小时后，初始NB浓度（0.03摩尔/升）和CNB、C AN、C AB分别对应于NB、AN和AB浓度。</li>
</ol>

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G. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Surface+Plasmon+Resonance+in+Bimetallic+Core-Shell+Nanoparticles.">Surface Plasmon Resonance in Bimetallic Core-Shell Nanoparticles.</a> Journal of Physical Chemistry C. 119 (29), 16836-16845 (2015).</li><li>Liu, Z., Huang, Y., Xiao, Q., Zhu, H. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Selective+reduction+of+nitroaromatics+to+azoxy+compounds+on+supported+Ag-Cu+alloy+nanoparticles+through+visible+light+irradiation.">Selective reduction of nitroaromatics to azoxy compounds on supported Ag-Cu alloy nanoparticles through visible light irradiation.</a> Green Chemistry. 18 (3), 817-825 (2016).</li><li>Chaiseeda, K., Nishimura, S., Ebitani, K. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Gold+nanoparticles+supported+on+alumina+as+a+catalyst+for+surface+plasmon-enhanced+selective+reductions+of+nitrobenzene.">Gold nanoparticles supported on alumina as a catalyst for surface plasmon-enhanced selective reductions of nitrobenzene.</a> ACS Omega. 2 (10), 7066-7070 (2017).</li><li>Peiris, S., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Metal+nanoparticle+photocatalysts:+emerging+processes+for+green+organic+synthesis.">Metal nanoparticle photocatalysts: emerging processes for green organic synthesis.</a> Catalysis Science and Technology. 6 (2), 320-338 (2016).</li><li>Garc&#237;a-Garc&#237;a, I., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Silver-Based+Plasmonic+Catalysts+for+Carbon+Dioxide+Reduction.">Silver-Based Plasmonic Catalysts for Carbon Dioxide Reduction.</a> ACS Sustainable Chemistry and Engineering. 8 (4), 1879-1887 (2020).</li><li>Agrawal, A., Johns, R. W., Milliron, D. J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Control+of+Localized+Surface+Plasmon+Resonances+in+Metal+Oxide+Nanocrystals.">Control of Localized Surface Plasmon Resonances in Metal Oxide Nanocrystals.</a> Annual Review of Materials Research. 47 (1), 1-31 (2017).</li><li>Lounis, S. D., Runnerstrom, E. L., Llord&#233;s, A., Milliron, D. J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Defect+chemistry+and+Plasmon+physics+of+colloidal+metal+oxide+Nanocrystals.">Defect chemistry and Plasmon physics of colloidal metal oxide Nanocrystals.</a> Journal of Physical Chemistry Letters. 5 (9), 1564-1574 (2014).</li><li>Rej, S., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Determining+Plasmonic+Hot+Electrons+and+Photothermal+Effects+during+H2+Evolution+with+TiN-Pt+Nanohybrids.">Determining Plasmonic Hot Electrons and Photothermal Effects during H2 Evolution with TiN-Pt Nanohybrids.</a> ACS Catalysis. 10 (9), 5261-5271 (2020).</li><li>Barragan, A. A., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Photochemistry+of+Plasmonic+Titanium+Nitride+Nanocrystals.">Photochemistry of Plasmonic Titanium Nitride Nanocrystals.</a> The Journal of Physical Chemistry C. 123 (35), 21796-21804 (2019).</li></ol>

作者没有什么可透露的。

该方法描述的结果表明，Pd（或其他催化但非质子金属）的内在催化活性可以通过双金属合金NPs35中的可见光照射通过LSPR激发显著增强。在这种情况下，Ag（或其他质离子金属）能够通过LSPR激发从可见光照射中获取能量。LSPR激发导致热电荷载体（热电子和孔）的形成和局部加热5，14，15，16，17，18，19。</s...

在金属纳米粒子（NPs）的几种应用中，催化值得特别关注。催化在可持续的未来发挥着核心作用，有助于减少能源消耗，更好地利用原材料，并使反应条件更清洁1，2，3，4。因此，催化的进展可以为提高化学过程的原子效率提供工具，使它们更清洁、更经济、更环保。金属NP包括银（Ag）、金（Au）或铜（Cu），可以通过局部表面质子共振（LSPR）激发5、6、7、8在纳米尺度上与光相互作用的独特方式，在可见范围内显示有趣的光学特性。在这些NP中，称为质子NP，LSPR包括事件光子（来自来袭电磁波）与电子5、6、7、8的集体运动的共振相互作用。这种现象发生在一个典型的频率，这取决于大小，形状，组成，和介电常数的环境9，10，11。例如，对于Ag、Au和Cu，这些频率的范围从可见到近红外，为利用太阳能激发其LSPR 5、6、7、8、12、13提供了可能性。
最近，人们已经证明，质子核动力学中的LSPR激发有助于加快速率，控制分子转换5，14，15，16，17，18，19的选择性。这催生了一个叫做质子催化的领域，它专注于利用光的能量来加速、驱动和/或控制化学转化5、14、15、16、17、18、19。在此背景下，已确定质离子NP中的LSPR激发可导致高能热电子和孔的形成，称为LSPR激发热载体。这些载体可以通过电子或振动激活15，16与吸附物种相互作用。除了提高反应率外，该过程还可以提供传统热化学驱动过程无法进入的替代反应途径，为控制反应选择性20、21、22、23、24、25开辟了新的途径。重要的是，值得注意的是，质粒衰变也会导致热消散，导致NP附近的温度上升，这也有助于加快反应速率15，16。
由于这些有趣的特点，质子催化已成功地应用于各种分子转换18。然而，一个重要的挑战依然存在。虽然 Ag 和 Au 等质离子 NP 在可见和近红外范围内具有出色的光学特性，但其催化性能在转化范围方面是有限的。换句话说，它们对于几个转换没有表现出良好的催化性能。此外，在催化中很重要的金属，如铂金（Pd）和铂金（Pt），不支持可见或近高射能范围内的LSPR激发。为了弥补这一差距，含有质离子和催化金属的双金属NP代表一个有效的策略20，26，27，28，29。在这些系统中，质离子金属可以用作天线，通过LSPR从光激发中获取能量，然后用于驱动、加速和控制催化金属的分子转换。因此，这种策略使我们能够超越传统的质离子金属NPs20，26，27，28，29的质离子催化。
该协议描述了 ZrO 2（Ag-Pd/ZrO2）上支持的双金属银铂（Ag-Pd）合金 NP 的简单合成，可作为质离子催化的质子催化系统。Ag-Pd/ZrO2 NP 由 ZrO2支持上的相应金属前体共同浸渍而制备，然后同时减少30个。这种方法导致在 ZrO2支座表面直接形成大小约为 10 nm 的双金属 NP。NP 由 1 摩尔% 的 Pd 组成，以最大限度地减少催化金属的利用，同时最大限度地提高由此产生的 Ag-Pd NP 的光学特性。演示了在质离子催化中应用Ag-Pd/ZrO2 NPs的议定书，用于减少硝基苯。我们使用425 nm LED照明为LSPR激发。进行气相色谱检查，以监测在暗光照射条件下减少反应的转换和选择性。LSPR 激发导致与纯热驱动条件相比，Ag-Pd/ZrO2 NP 的催化性能增强，并控制选择性。此协议中描述的方法基于简单的光催化反应设置，加上气相色谱，可适应广泛的分子转换和 NP 组成。因此，这种方法使得光催化活性的描述成为可能，在转换和反应选择性方面，不同的NP和无数的液相转换。我们相信这篇文章将为新来者和更有经验的科学家提供重要的指导方针和见解。

<table border="0" cellpadding="0" cellspacing="0" style="width:727px;" width="726">
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		<tr height="42">
			<td height="42" style="height:42px;width:427px;">2-Propanol (anhydrous, 99.5%)</td>
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			<td style="width:96px;">Sigma-Aldrich</td>
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			<td style="width:96px;">Sigma-Aldrich</td>
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preparation of silver-palladium alloyed nanoparticles for plasmonic catalysis under visible-light illumination

质离子纳米粒子（NPs）中的局部表面质子共振（LSPR）可以加速和控制各种分子转换的选择性。当支持这些范围内LSPR激发的质粒纳米粒子被用作催化剂时，这为使用可见光或近射光作为驱动和控制反应的可持续输入开辟了可能性。不幸的是，对于几种催化金属（如铂（Pd）来说，情况并非如此。克服这一限制的一个策略是采用含有质离子和催化金属的双金属NP。在这种情况下，质离子金属中的LSPR激发有助于加速和控制催化组件驱动的转化。本文报告的方法侧重于在ZrO 2（Ag-Pd/ZrO2）上支持的双金属银-铂（Ag-Pd）NPs的合成，该点作为质粒催化系统。NP 的编制是通过在 ZrO2支持上共同浸渍相应的金属前体，然后同时减少导致直接在 ZrO2支持上形成双金属 NP。然后，Ag-Pd/ZrO2 NP 被用作质离子催化剂，用于通过 LED 灯在 425 nm 照明下减少硝基苯。使用气相色谱（GC），可以监测暗光照射条件下减少反应的转换和选择性，证明在将非质子Pd与质离子金属Ag合金后，LSPR激发下的催化性能和对选择性的控制增强。该技术可适应广泛的分子转化和NPs成分，有助于描述不同类型催化在转化和选择性方面的质离子催化活性。

图 1A 显示了含有纯 ZrO2 氧化物（左）和 Ag-Pd/ZrO2 NP（右）的固体样品的数码照片。这种颜色从白色（ZrO2）到棕色（Ag-Pd/ZrO2）的变化为Ag-Pd NP在ZrO2 表面的沉积提供了初步的定性证据。 图 1B 显示了来自 Ag-Pd/ZrO2 NP（蓝色跟踪）以及 ZrO2（ 黑色跟踪）和 Ag/ZrO2 NP（红色跟踪）的紫外线可见吸...

Watch this Scientific Journal Video about Preparation of Silver-Palladium Alloyed Nanoparticles for Plasmonic Catalysis under Visible-Light Illumination at JoVE.com

Preparation of Silver-Palladium Alloyed Nanoparticles for Plasmonic Catalysis under Visible-Light Illumination

这里介绍了在 ZrO 2 （Ag-Pd/ZrO2）上支持的银铂 （Ag-Pd） 合金纳米粒子 （NPs） 合成的协议。该系统允许从可见光照射中获取能量，以加速和控制分子转化。在Ag-Pd/ZrO2 NPs催化的光照射下，硝基苯的减少就说明了这一点。

在可见光照射下为质子催化准备银-铂合金纳米粒子

Localized surface plasmon resonance (LSPR) in plasmonic nanoparticles (NPs) can accelerate and control the selectivity of a variety of molecular ...

preparation-silver-palladium-alloyed-nanoparticles-for-plasmonic

Research

JoVE Journal

Chemistry

5.4K 次观看.  University of Helsinki. 这里介绍了在 ZrO 2 （Ag-Pd/ZrO2）上支持的银铂 （Ag-Pd） 合金纳米粒子 （NPs） 合成的协议。该系统允许从可见光照射中获取能量，以加速和控制分子转化。在Ag-Pd/ZrO2 NPs催化的光照射下，硝基苯的减少就说明了这一点。

视频: Preparation of Silver-Palladium Alloyed Nanoparticles for Plasmonic Catalysis under Visible-Light Illumination

Gyroid Nickel Nanostructures from Diblock Copolymer Supramolecules

Nanoporous metal foams possess a unique combination of properties - they are catalytically active, thermally and electrically conductive, and furthermore, have high porosity, high surface-to-volume and strength-to-weight ratio. Unfortunately, common approaches for preparation of metallic nanostructures render materials with highly disordered architecture, which might have an adverse effect on their mechanical properties. Block copolymers have the ability to self-assemble into ordered nanostructures and can be applied as templates for the preparation of well-ordered metal nanofoams. Here we describe the application of a block copolymer-based supramolecular complex - polystyrene-block-poly(4-vinylpyridine)(pentadecylphenol) PS-b-P4VP(PDP) - as a precursor for well-ordered nickel nanofoam. The supramolecular complexes exhibit a phase behavior similar to conventional block copolymers and can self-assemble into the bicontinuous gyroid morphology with two PS networks placed in a P4VP(PDP) matrix. PDP can be dissolved in ethanol leading to the formation of a porous structure that can be backfilled with metal. Using electroless plating technique, nickel can be inserted into the template&#39;s channels. Finally, the remaining polymer can be removed via pyrolysis from the polymer/inorganic nanohybrid resulting in nanoporous nickel foam with inverse gyroid morphology.

This article describes the preparation of well-ordered nickel nanofoams via electroless metal deposition onto nanoporous templates obtained from self-assembled diblock copolymer based supramolecules.

Gyroid镍纳米结构的嵌段共聚物超分子

Nanoporous metal foams possess a unique combination of properties - they are catalytically active, thermally and electrically conductive, and furthermore, ...

科研

化学

Preparation of Silica Nanoparticles Through Microwave-assisted Acid-catalysis

Microwave-assisted synthetic techniques were used to quickly and reproducibly produce silica nanoparticle sols using an acid catalyst with nanoparticle diameters ranging from 30-250 nm by varying the reaction conditions. Through the selection of a microwave compatible solvent, silicic acid precursor, catalyst, and microwave irradiation time, these microwave-assisted methods were capable of overcoming the previously reported shortcomings associated with synthesis of silica nanoparticles using microwave reactors. The siloxane precursor was hydrolyzed using the acid catalyst, HCl. Acetone, a low-tan &#948; solvent, mediates the condensation reactions and has minimal interaction with the electromagnetic field. Condensation reactions begin when the silicic acid precursor couples with the microwave radiation, leading to silica nanoparticle sol formation. The silica nanoparticles were characterized by dynamic light scattering data and scanning electron microscopy, which show the materials&#39; morphology and size to be dependent on the reaction conditions. Microwave-assisted reactions produce silica nanoparticles with roughened textured surfaces that are atypical for silica sols produced by St&#246;ber&#39;s methods, which have smooth surfaces.

Silica nanoparticles were prepared using acid-catalysis of a siloxane precursor and microwave-assisted synthetic techniques resulting in the controlled growth of nanomaterials ranging from 30-250 nm in diameter. The growth dynamics can be controlled by varying the initial silicic acid concentration, time of the reaction, and temperature of reaction.

Microwave-assisted synthetic techniques were used to quickly and reproducibly produce silica nanoparticle sols using an acid catalyst with nanoparticle ...

Synthesis of Immunotargeted Magneto-plasmonic Nanoclusters

Magnetic and plasmonic properties combined in a single nanoparticle provide a synergy that is advantageous in a number of biomedical applications including contrast enhancement in novel magnetomotive imaging modalities, simultaneous capture&#160;and detection of circulating tumor cells (CTCs),&#160;and multimodal molecular imaging combined with photothermal therapy of cancer cells. These applications have stimulated significant interest in development of protocols for synthesis of magneto-plasmonic nanoparticles with optical absorbance in the near-infrared (NIR) region and a strong magnetic moment. Here, we present a novel protocol for synthesis of such hybrid nanoparticles that is based on an oil-in-water microemulsion method. The unique feature of the protocol described herein is synthesis of magneto-plasmonic nanoparticles of various sizes from primary blocks which also have magneto-plasmonic characteristics. This approach yields nanoparticles with a high density of magnetic and plasmonic functionalities which are uniformly distributed throughout the nanoparticle volume. The hybrid nanoparticles can be easily functionalized by attaching antibodies through the Fc moiety leaving the Fab portion that is responsible for antigen binding available for targeting.

Here, we describe a protocol for synthesis of magneto-plasmonic nanoparticles with a strong magnetic moment and a strong near-infrared (NIR) absorbance. The protocol also includes antibody conjugation to the nanoparticles through the Fc moiety for various biomedical applications which require molecular specific targeting.

Immunotargeted的合成磁等离子团簇

Magnetic and plasmonic properties combined in a single nanoparticle provide a synergy that is advantageous in a number of biomedical applications ...

Preparation and Characterization of SDF-1&#945;-Chitosan-Dextran Sulfate Nanoparticles

Chitosan (CS) and dextran sulfate (DS) are charged polysaccharides (glycans), which form polyelectrolyte complex-based nanoparticles when mixed under appropriate conditions. The glycan nanoparticles are useful carriers for protein factors, which facilitate the in vivo delivery of the proteins and sustain their retention in the targeted tissue. The glycan polyelectrolyte complexes are also ideal for protein delivery, as the incorporation is carried out in aqueous solution, which reduces the likelihood of inactivation of the proteins. Proteins with a heparin-binding site adhere to dextran sulfate readily, and are, in turn, stabilized by the binding. These particles are also less inflammatory and toxic when delivered in vivo. In the protocol described below, SDF-1&#945; (Stromal cell-derived factor-1&#945;), a stem cell homing factor, is first mixed and incubated with dextran sulfate. Chitosan is added to the mixture to form polyelectrolyte complexes, followed by zinc sulfate to stabilize the complexes with zinc bridges. The resultant SDF-1&#945;-DS-CS particles are measured for size (diameter) and surface charge (zeta potential). The amount of the incorporated SDF-1&#945; is determined, followed by measurements of its in vitro release rate and its chemotactic activity in a particle-bound form.

Preparation and Characterization of SDF-1&amp;#945;-Chitosan-Dextran Sulfate Nanoparticles

The objective of this protocol is to incorporate SDF-1&#945;, a stem cell homing factor, into dextran sulfate-chitosan nanoparticles. The resultant particles are measured for their size and zeta potential, as well as the content, activity, and in vitro release rate of SDF-1&#945; from the nanoparticles.

SDF-1α - 壳聚糖硫酸葡聚糖纳米粒子的制备与表征

Chitosan (CS) and dextran sulfate (DS) are charged polysaccharides (glycans), which form polyelectrolyte complex-based nanoparticles when mixed under ...

A Simple Method for the Size Controlled Synthesis of Stable Oligomeric Clusters of Gold Nanoparticles under Ambient Conditions

Reducing dilute aqueous HAuCl4 with sodium thiocyanate (NaSCN) under alkaline conditions produces 2 to 3 nm diameter nanoparticles. Stable grape-like oligomeric clusters of these yellow nanoparticles of narrow size distribution are synthesized under ambient conditions via two methods. The delay-time method controls the number of subunits in the oligoclusters by varying the time between the addition of HAuCl4 to alkaline solution and the subsequent addition of reducing agent, NaSCN. The yellow oligoclusters produced range in size from ~3 to ~25 nm. This size range can be further extended by an add-on method utilizing hydroxylated gold chloride (Na+[Au(OH4-x)Clx]-) to auto-catalytically increase the number of subunits in the as-synthesized oligocluster nanoparticles, providing a total range of 3 nm to 70 nm. The crude oligocluster preparations display narrow size distributions and do not require further fractionation for most purposes. The oligoclusters formed can be concentrated &#62;300 fold without aggregation and the crude reaction mixtures remain stable for weeks without further processing. Because these oligomeric clusters can be concentrated before derivatization they allow expensive derivatizing agents to be used economically. In addition, we present two models by which predictions of particle size can be made with great accuracy.

We describe a simple method for producing highly stable oligomeric clusters of gold nanoparticles via the reduction of chloroauric acid (HAuCl4) with sodium thiocyanate (NaSCN). The oligoclusters have a narrow size distribution and can be produced with a wide range of sizes and surface coats.

根据环境条件的金纳米粒子的稳定低聚簇的大小控制合成的一种简便方法

Reducing dilute aqueous HAuCl4 with sodium thiocyanate (NaSCN) under alkaline conditions produces 2 to 3 nm diameter nanoparticles. Stable grape-like ...

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 ...

HKUST-1 as a Heterogeneous Catalyst for the Synthesis of Vanillin

Vanillin (4-hydoxy-3-methoxybenzaldehyde) is the main component of the extract of vanilla bean. The natural vanilla scent is a mixture of approximately 200 different odorant compounds in addition to vanillin. The natural extraction of vanillin (from the orchid Vanilla planifolia, Vanilla tahitiensis and Vanilla pompon) represents only 1% of the worldwide production and since this process is expensive and very long, the rest of the production of vanillin is synthesized. Many biotechnological approaches can be used for the synthesis of vanillin from lignin, phenolic stilbenes, isoeugenol, eugenol, guaicol, etc., with the disadvantage of harming the environment since these processes use strong oxidizing agents and toxic solvents. Thus, eco-friendly alternatives on the production of vanillin are very desirable and thus, under current investigation. Porous coordination polymers (PCPs) are a new class of highly crystalline materials that recently have been used for catalysis. HKUST-1 (Cu3(BTC)2(H2O)3, BTC = 1,3,5-benzene-tricarboxylate) is a very well known PCP which has been extensively studied as a heterogeneous catalyst. Here, we report a synthetic strategy for the production of vanillin by the oxidation of trans-ferulic acid using HKUST-1 as a catalyst.

The conversion of trans-ferulic acid to vanillin was achieved by heterogeneous catalysis. HKUST-1 was employed in this synthesis and the essential step in the catalytic process was the generation of unsaturated metal sites. Thus, when the catalyst was activated under vacuum, full vanillin conversion (yield of 95%) was obtained.

科大-1作为香兰素的合成的非均相催化剂

Vanillin (4-hydoxy-3-methoxybenzaldehyde) is the main component of the extract of vanilla bean. The natural vanilla scent is a mixture of approximately ...

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.

使用Photoredox催化剂蠕虫状胶束的简便合成可见光介导的分散聚合

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

Imine Metathesis by Silica-Supported Catalysts Using the Methodology of Surface Organometallic Chemistry

With this protocol, a well-defined singlesite silica-supported heterogeneous catalyst [(&#8801;Si-O-)Hf(=NMe)(&#951;1-NMe2)] is designed and prepared according to the methodology developed by surface organometallic chemistry (SOMC). In this framework, catalytic cycles can be determined by isolating crucial intermediates. All air-sensitive materials are handled under inert atmosphere (using gloveboxes or a Schlenk line) or high vacuum lines (HVLs, &#60;10-5 mbar). The preparation of SiO2-700 (silica dehydroxylated at 700 &#176;C) and subsequent applications (the grafting of complexes and catalytic runs) requires the use of HVLs and double-Schlenk techniques. Several well-known characterization methods are used, such as Fourier-transform infrared spectroscopy (FTIR), elemental microanalysis, solid-state nuclear magnetic resonance spectroscopy (SSNMR), and state-of-the-art dynamic nuclear polarization surface enhanced NMR spectroscopy (DNP-SENS). FTIR and elemental microanalysis permit scientists to establish the grafting and its stoichiometry. 1H and 13C SSNMR allows the structural determination of the hydrocarbon ligands coordination sphere. DNP SENS is an emerging powerful technique in solid characterization for the detection of poorly sensitive nuclei (15N, in our case). SiO2-700 is treated with about one equivalent of the metal precursor compared to the amount of surface silanol (0.30 mmol&#183;g-1) in pentane at room temperature. Then, volatiles are removed, and the powder samples are dried under dynamic high vacuum to afford the desired materials [(&#8801;Si-O-)Hf(&#951;2&#960;-MeNCH2)(&#951;1-NMe2)(&#951;1-HNMe2)]. After a thermal treatment under high vacuum, the grafted complex is converted into metal imido silica complex [(&#8801;Si-O-)Hf(=NMe)(&#951;1-NMe2)]. [(&#8801;Si-O-)Hf(=NMe)(&#951;1-NMe2)] effectively promotes the metathesis of imines, using the combination of two imine substrates, N-(4-phenylbenzylidene)benzylamine, or N-(4-fluorobenzylidene)-4-fluoroaniline, with N-benzylidenetert-butylamine as substrates. A significantly lower conversion is observed with the blank runs; thus, the presence of the imido group in [(&#8801;Si-O-)Hf(=NMe)(&#951;1-NMe2)] is correlated to the catalytic performance.

A new group IV metal catalyst for imine metathesis is prepared by grafting amine metal complex onto dehydroxylated silica. Surface metal fragments are characterized using FT-IR, elemental microanalysis, and solid-state NMR spectroscopy. Further dynamic nuclear polarization surface enhanced NMR spectroscopy experiments complement the determination of the coordination sphere.

利用表面有机金属化学方法，利用硅支持的催化剂进行Imine金属分析

With this protocol, a well-defined singlesite silica-supported heterogeneous catalyst [(&#8801;Si-O-)Hf(=NMe)(&#951;1-NMe2)] is designed and prepared ...

Performing Spectroscopy on Plasmonic Nanoparticles with Transmission-Based Nomarski-Type Differential Interference Contrast Microscopy

Differential interference contrast (DIC) microscopy is a powerful imaging tool that is most commonly employed for imaging microscale objects using visible-range light. The purpose of this protocol is to detail a proven method for preparing plasmonic nanoparticle samples and performing single particle spectroscopy on them with DIC microscopy. Several important steps must be followed carefully in order to perform repeatable spectroscopy experiments. First, landmarks can be etched into the sample substrate, which aids in locating the sample surface and in tracking the region of interest during experiments. Next, the substrate must be properly cleaned of debris and contaminants that can otherwise hinder or obscure examination of the sample. Once a sample is properly prepared, the optical path of the microscope must be aligned, using Kohler Illumination. With a standard Nomarski style DIC microscope, rotation of the sample may be necessary, particularly when the plasmonic nanoparticles exhibit orientation-dependent optical properties. Because DIC microscopy has two inherent orthogonal polarization fields, the wavelength-dependent DIC contrast pattern reveals the orientation of rod-shaped plasmonic nanoparticles. Finally, data acquisition and data analyses must be carefully performed. It is common to represent DIC-based spectroscopy data as a contrast value, but it is also possible to present it as intensity data. In this demonstration of DIC for single particle spectroscopy, the focus is on spherical and rod-shaped gold nanoparticles.

The goal of this protocol is to detail a proven approach for the preparation of plasmonic nanoparticle samples and for performing single particle spectroscopy on them with differential interference contrast (DIC) microscopy.