该研究是由办公室基础能源科学，化学科学，地质能源的美国能源部（DOE）的与生物科学部。 GEJ承认从鲍林团契及实验室指导研究和发展计划在太平洋西北国家实验室（PNNL）的支持。使用EMSL，由生物和环境研究的能源办公室的部门主办，位于西北太平洋国家实验室国家科学用户设施进行这项工作。西北太平洋国家实验室是由巴特尔为美国能源部运行。

1，COOH-SAM表面对黄金的质量选择离子软着陆准备<ol><li>获得平坦的黄金基板上硅（Si）或云母背衬材料。或者，根据在文献118119中所述的方法制备金膜在硅或云母表面。注意：使用的表面，有如下规格：1 平方厘米 或圆形和直径5毫米，525微米厚的硅层，50埃厚的Ti的粘附层，1000的Au层。 </li><li>将新鲜的金子在硅表面为玻璃闪烁小瓶，沉浸在纯（非变性）乙醇。 </li><li>将装有浸在乙醇中的金表面的闪烁瓶中为超声波清洁器和洗20分钟，以除去表面的碎屑。注意：不要用超声波清洗金云母表面，因为这会从云母基材分离的金膜。 </li><li>从样品瓶和干水洗除去金表面与流纯N 2，以防止从乙醇任何残留斑点的形成。 </li><li>将干燥后的金表面面对于紫外（UV）和清洁器照射20分钟，以除去表面的有机物质。 </li><li>在玻璃闪烁瓶中，制备5毫升的在非变性乙醇的16 mercaptohexadecanoic酸（COOH-SAM）的1 mM的解决方案。 </li><li>加盐酸至1％HCl的乙醇的最终浓度，以确保分子的羧酸基团的质子化。 </li><li>将经洗涤，干燥和紫外线清洁金表面面朝上装入的COOH-SAM解决方案确保了整个金表面被完全浸没在每个小瓶中。允许在黄金表面单层组装至少24小时在黑暗中（包装在铝箔瓶）。 </li><li>从在含有5ml的1％HCl的乙醇新闪烁瓶中的COOH-SAM溶液和地方除去表面。超声波清洗SAM表面5分钟，以除去任何物理吸附的分子FROM单层表面。 </li><li>从样品瓶中取出洗涤表面和冲洗用几个1ml等份的1％HCl的乙醇。干COOH-SAM下的氮气流面。 </li><li>用干净的金属镊子和戴手套放置SAM表面上三种金属样品的坐骑，这是每个软着陆仪器小心不要触碰前置金表面的工艺兼容。确保表面紧密就位，并且有表面的背侧和金属试样装入之间的强电接触固定的。 </li><li>采用软着陆工具（各稍有不同）的装载锁定试样导入功能，确保了闸阀分离的软着陆室仪器的样品引入区域被封闭。通过旋转涡轮分子真空泵和电离压力计和closi关闭使样品投入槽向上至大气压纳克阀到前级机械真空泵。 </li><li>当试样导入室达到大气压打开示例门和样品架固定牢固的机械手（xyz的阶段或z-译者）仪器的内部。关上门，打开阀门前级机械真空泵。当试样导入室达到10 -3托的压力，转动涡轮分子真空泵和电离压力计上。 </li><li>当试样导入室达到10 -5托 ​​的压力，打开闸阀的软着陆室。使用磁性操纵器或xyz的阶段来定位SAM表面与离子束线，开始软着陆。 </li></ol>的大众选择的三联吡啶钌为3 2 + 2。软着陆到COOH-SAM表面<ol><li>得到的三（2,2&#39; - 联吡啶基）二氯合钌（II）六水合物固体。溶解红色晶体在纯甲醇CReate储备溶液与10 -3 M的浓度由10或100倍稀释储备液用甲醇实现批量选择的三联吡啶钌为3 2 + M / Z = 285的最佳电离子电流。 </li><li>加载稀释液为1毫升的玻璃注射器中。使用注射泵，通过360微米外径80的偏置之间+2 +3千伏产生正离子微米内径熔融石英毛细管注入的解决方案。调整20-40微升/小时的注射泵的流速，以获得最佳的离子流和稳定的表面。 </li><li>调整四极杆质量过滤器的吡啶钌的质量3 2 + 离子 m / z = 285，防止品种较吡啶钌3 2 +其他的软着陆在表面上。使用高电阻通过一个真空静电计连接到所述衬底的电馈通，调节电压的离子光学元件的设置和射频离子引导，最大限度地离子电流吡啶钌和稳定性3 2 +测量在SAM表面。使实验运行的时间期间选择，以实现离子的所需覆盖的COOH-SAM的表面上。 </li><li>增加在软着陆工具的高压碰撞四极区域的电势梯度来创建的苛刻条件，使气相配位体从有机金属离子通过碰撞诱导解离剥离。注意：检查3软着陆工具，这也是代表其他两个工具，它是在图1的早期阶段中的一个的示意性框图的吡啶钌的碎片3 2 +离子发生区域4，增加施加到电动离子漏斗的背面板，以从包埋Ru（bpy）移除一个联吡啶配体的电压3 2 + M / Z = 285产生的气体相吡啶钌2 + M / Z = 207仪器81的区域4。大规模使用四极杆质​​量过滤器的仪器和软土地区6到COOH-SAM选择高活性undercoordinated碎片离子表面研究如何结扎的影响程度支持有机金属离子的特性。 </li><li>调整周边离子光学，包括施加到四极杆电极的直流电压，以及电导限制最大化质量选择的包埋Ru（bpy）的当前2 2 +碎片离子在表面上。 </li></ol> 3，分析原位 TOF-SIMS之前和暴露于反应气体后<ol><li>关闭注射器泵和高压到ESI发射极。打开分隔仪器的两个区域运转时的闸阀。使用磁性操纵器从软着陆室移动处理的表面内的分析阶段的TOF-SIMS部分仪器。 </li><li>从样品中分离的操纵器，并从SIMS分析室完全撤回。关闭软着陆和仪器的SIMS部分之间的闸阀，因为TOF-SIMS工作在低得多的压力比仪器的软着陆区域。 </li><li>为了进行TOF-SIMS实验中，加载该软件中的仪器控制文件，并确保该GA +源产生的一次离子的足够稳定的电流。注：聘请15千电子伏初级镓离子（GA +，500 pA的，5纳秒脉冲宽度，10 kHz重复率）来诱导软解吸从表面降落的材料。提取从表面喷出到该质量分析器上，它由三个独立的静电扇区的次级离子。 </li><li>获得在表面上的x轴和y轴的线剖面，以确定所述衬底（通常在表面上的中心上的离子的沉积点的中心第二3mm直径）。定位表面，使得Ga的+一次离子束入射离子的沉积点的中心。获取TOF-SIMS质谱5分钟。 </li><li>关闭主镓离子束和TOF-SIMS的高电压。使用磁性操纵的样品搬回到仪器的软着陆的一部分。确保闸阀分隔两个室进一步处理之前被关闭。 </li><li>使用上的软着陆室中的高真空泄漏阀引入超高纯氧气（O 2）的气体的流量控制，从一个气缸到仪器中。使用可调节的闸门阀的涡轮分子真空泵的前方节流在泵的泵送速度来实现的O 2的软着陆室内部10 -4乇的稳态压力。 </li><li>随着表面暴露于氧气 30分钟关闭泄漏阀，打开闸阀过日Ë涡轮分子真空泵，并允许剩余的O 2与抽走。之后在腔室中的压力下降，打开闸阀到仪器的SIMS的一部分，并使用该磁性操纵器来定位表面的分析平台上进行第二轮的TOF-SIMS分析。 </li><li>之后，如在3.3-3.4节所述，打开闸门阀及上述面位置后面的软着陆室，用于曝光的C 2 H 4为30分钟至10 -4乇得到的第二TOF-SIMS谱。如上所述再次进行二次离子质谱分析。 </li></ol> 4，分析原位 FT-ICR-SIMS期间和之后软着陆<ol><li>制备的SAM表面用于与原位 FT-ICR-SIMS仪器中相似，在第1条中所述的方式，但在圆形基板直径5毫米的实验。注意：使用的基板是激光切割的黄金涂硅晶片（5 nm的铬粘合层和多晶气相沉积金100纳米）。注意，最显着的区别是，在FT-ICR-SIMS仪器的表面定位的超导磁体的孔中。磁体的存在的必要条件是表面被放置在一个5英尺手册的z转换，以使它们能够在ICR单元的后板安全地和可调节地定位的端部。 </li><li>使用装载锁定界面，在位于6特斯拉磁体内部的ICR电池的后捕集板定位的圆形SAM表面。注：请注意，此仪器是配置为研究离子与表面相互作用97,120特别设计的6特斯拉的FT-ICR质谱仪。 </li><li>以类似于在第2描述的方式操作的FT-ICR-SIMS仪器的离子软着陆部。 </li><li>使用铯离子源创建的8千伏Cs +的主要离子的连续梁时溅射表面的ND离子软着陆之后。 </li><li>利用ESI源放置在90°走向的主要手段轴产生离子的软着陆。通过一个90°的弯曲四极杆120聚焦离子。注：请注意本仪器的几何形状便于吡啶钌3 2 +和传输的主要铯离子束表面从而使软着陆过程的监控期间和离子沉积后的同时实现软着陆。 </li><li>陷阱和分析来自用FT-ICR-MS的表面喷出的二次离子。注释：应用对应于大约10 10离子/厘米2（电流4 NA，持续时间80微秒，光斑为4.6毫米，每谱10次，约200个数据点）的总离子流对这些实验，持续静态SIMS的条件约7小时。平均每个SIMS谱超过10投相当于10秒〜采集时间。 </li><li>通过采样SAM surfa获得动力学数据中和离子沉积后厕每4分钟约7小时。 </li><li>使用文献中描述的121自动化模块化数据控制系统进行数据采集和仪器控制。 </li></ol> 5，分析原位 IRRAS期间和之后软着陆<ol><li>准备SAM表面以便与在类似第1节所述的方式就地 IRRAS仪器实验说明：请注意，从表面与z-译者认为是精确定位的IRRAS仪器结果的最大区别要定位在衬底处的抛物面镜的焦点，并与离子的束线。最大化红外光束和在表面上沉积的离子的光斑之间的重叠。 </li><li>进行在掠入射几何学的IRRAS实验采用的FTIR光谱仪配备有液氮冷却的汞 - 镉 - 碲化物（MCT）检测器。 </li><li>利用镀金的平面镜直接退出FTIR光谱仪上的抛物线金镜的光。从抛物面镜通过中红外线的线栅型偏振器和进入真空室通过一个视反射光。 </li><li>直接从光谱的红外光到COOH-SAM表面位于所述真空室的内部。注意：将真空室保持在10 -5乇时离子软着陆的压力。 </li><li>放置反光SAM在金表面的真空室内在使用电机驱动的Z-译者第一抛物面镜的焦点。 </li><li>反映IR光从SAM的表面和流出腔室的通过第二视口进入真空室中。使用第二个抛物面镜金从表面反射的光聚焦到一个MCT检测器。 </li><li>吹扫红外光束的通路中的真空室与N 2的外侧。 </li><li>交流在沉积过程中设置的时间间隔QUIRE光谱。 </li></ol>

质量选择离子的软着陆，一般进行使用，存在于世界各地的几个实验室所专门配备这些实验独特的定制仪器。修改正在不断向这些工具以促成化合物的更广泛的电离，以达到更大的离子电流和更短的沉积时间，复软着陆，从而达到几个品种的同时沉积在表面上的不同位置，并允许更准确的选择离子通过两个质量 - 电荷之前，沉积率和离子迁移率。以类似的方式，表征技术的不断变化的阵容被加上?...

质量选择离子软着陆表面上仍然是目前的研究兴趣，由于技术的高度控制的新型材料1-6筹备证明能力的问题。最近作出的努力表示在筹备肽和蛋白质芯片的高通量生物筛选7,8，蛋白质分离和肽的构象富集9-12，共价连接使用大众选择的离子软着陆的潜在应用前景肽表面9,10,13,14，有机化合物的手性富集15，具体的氧化还原活性蛋白的电化学表征16-18，生产薄分子膜19,20中，大分子如石墨烯21和准备模型的处理通过离子簇22-39的软着陆催化剂体系，纳米粒子40-48和有机金属助mplexes到辅助材料19,49-56。通过多原子离子的软着陆修改曲面的概念于1977年57最初提出的厨师和同事，在随后的几年广泛的工具方法已被开发为大众选择的离子从天然气的沉积控制相表面上1,4,5。离子已经通过诸如电喷雾电离（ESI）10,58,59，基质辅助激光解吸/电离（MALDI）21，电子轰击电离（EI）60,61，脉冲电弧放电62，惰性气体冷凝36处理已产生，63，磁控溅射64,65，和激光汽化25,66,67。混合选择气相离子的前软着陆已经实现主要使用四极质量过滤器58,68,69，磁偏转装置70，和线性离子阱仪器8,59。特别诺塔在离子软着陆方法BLE提前最近发生的成功实施环境离子软，无功着陆由厨师和同事71,72。使用这些不同的离子化和大规模筛选技术，超高温（&lt;100 eV）的多原子离子与表面的相互作用进行了研究，以便更好地了解影响离子软着陆的效率和反应性和非反应性散射的竞争过程的因素以及表面诱导解离4,73-75。 明确定义的模型催化剂用于研究目的的准备已经大量选择的离子25,34,35,56,76-81的软着陆的一个特别富有成果的应用。在纳米簇，其中的物理和化学特性并呈线性簇的大小不会缩放的尺寸范围，它已被证明，添加或删除单个原子或从集群可能会大大影响日EIR化学反应82-84。这种纳米级的现象，这是由于量子限域，被令人信服地证明了Heiz和同事85为模型催化剂组成的八金原子（金8）支持上的一个缺陷丰富的氧化镁表面柔软降落集群。几个额外的研究提供了支持表面34,77,86,87簇的大小依赖性反应性的证据。此外，高分辨电子显微镜图像表明，含少至10 88和55 89原子簇可能主要是负责支持氧化铁批量合成的金催化剂的优异活性。采用质量选择的离子软着陆，它可以制备大小选择的簇和纳米颗粒不扩散和凝聚成的支撑材料90-92的表面上较大结构的稳定阵列。这些先前的研究表明，与连续ING的发展，大众选择的簇和纳米粒子的软着陆可能成为一个多功能的技术创造了利用大量相同的集群和纳米粒子在表面上的扩展阵列的自发行为高度活跃的非均相催化剂。这些极其良好定义的系统可用于研究目的以了解关键参数，例如簇的大小，形态，元素组成和表面覆盖率影响催化剂的活性，选择性和耐久性。 通常使用在溶液相作为均相催化剂的有机金属配合物也可通过质量选择的离子56,80,81的软着陆被固定在表面上。附离子金属-配体配合物，以固体支持物，以产生杂化有机-无机复合材料是目前研究中的催化和表面科学界93的有源区。总的目标是获得高选择性朝向的同时促进从催化剂和留在溶液中的反应物更容易的分离的产物溶液相的金属 - 配体配合物的所需产物。在这种方式中，表面固定化的有机金属络合物收割均相和非均相催化剂的优点。通过选择一个适当的基片也能够维持甚至提高周围的活性金属中心的有机配位体的环境，同时也实现较强的表面固定94。自组装单分子膜表面（SAMs）的黄金可能被终止与许多不同的官能团的，因此，理想的系统研究，通过大量选择的离子95的软着陆圈养有机金属复合物表面的可行性。此外，电离等方法常压热解吸电离（APTDI）此前已证明，以产生气相混合金属的无机络合物这是不可访问的，通过在溶液中合成96。与此类似，例如磁控溅射法65，气体聚集63和激光蒸发66非热动力学上限定的合成和离子化技术也可以与离子软着陆仪表提供支撑在一个多功能路由到新的无机簇和纳米颗粒表面。 为了发展质量选择的离子软着陆成为一个成熟的技术，材料的制备，这是至关重要的信息分析方法，可以加上软着陆仪器之前来探测表面的化学和物理性质，期间和沉积后离子。迄今，大量的技术已被应用于此目的，包括二次离子质谱（SIMS）19,97-100，程序升温脱附和反应50,52，激光解吸电离101，脉冲分子束反应102，红外光谱（FTIR和Raman）98103104，表面增强拉曼光谱103,105，腔衰荡光谱106， X-射线光电子能谱35107，扫描隧道显微镜33,108-111，原子力显微镜112-114，和透射电子显微镜39。然而，为了最准确地描述制备或通过离子软着陆改性的表面，这是至关重要的，可以在原地无基材到环境中，在实验室的曝光进行的分析。 在原位进行的以前的分析提供了洞察如软降落离子的离子电荷随着时间的推移37,38,115,116的减少的现象，软解吸降落离子从表面52时，效率和动能的离子反应着陆14,81的依赖和大小的影响在集群和纳米颗粒沉积到的催化活性表面117。通过举例的方式，在我们的实验室，我们有系统地研究了不同地对空导弹3的表面质子化肽的电荷还原动力学。这些实验是用一种独特的软着陆仪耦合到执行的傅立叶变换离子回旋共振二次离子质谱仪（FT-ICR-SIMS），使在表面的原位分析期间和离子97的软着陆之后。为了扩大在这些分析能力，其他金融工具构建，允许在使用IRRAS 104面软降落离子的原位表征。这个表面敏感的红外技术使键的形成和破坏过程，以及在复 ​​合离子和表面层的构象变化进行实时期间和软着陆12后监测。例如，使用IRRAS它是表明，离子软着陆可用于共价固定化于N-羟基琥珀酰亚胺基酯的官能化自组装膜13,14大规模筛选多肽。 在此，我们说明了位于被用于原位 TOF-SIMS，FT-ICR-SIMS设计的太平洋西北国家实验室三个独特的定制工具的能力，并通过质量选择离子软着陆生产的基板的IRRAS分析到表面。作为一个代表性的系统，我们提出业绩质量选择的有机金属钌三（联吡啶）二价阳离子的软着陆[茹（联吡啶）3] 2 +到羧酸终止地对空导弹（COOH-SAMs）的制备固定化的有机金属配合物。它表明， 在原位 TOF-SIMS提供了非常高的灵敏度和大的整体的动态范围，帮助确定低丰度物种包括反应中间体的优点，可能仅被预发送的时间表面上短周期。 TOF-SIMS还提供了深入了解，从在气相之前，软着陆的有机金属离子除去的配体，影响其朝向固定化在表面上的效率和对气体分子的化学反应性。采用原位 FT-ICR-SIMS互补特性提供了见解的电荷减少，中和表面上的双电荷离子的解吸附动力学，而在原位 IRRAS探测周围的带电金属中心，这可能影响该有机配位体的结构的电子性质和固定化离子的反应性。总的来说，我们说明如何质量选择离子通过SIMS和IRRAS 原位分析结合的软着陆提供了洞察良好定义的物种和它有一个范围广泛的科学努力的影响面之间的相互作用。

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in situ sims and ir spectroscopy of well-defined surfaces prepared by soft landing of mass-selected ions

质量选择离子软着陆表面上是一个功能强大的方法对高度控制材料使用传统的合成技术是不可访问的准备。用二次离子质谱（SIMS）和红外反射吸收光谱（IRRAS）耦合软着陆原位表征使定义良好的表面分析清洁真空条件下进行。在我们的实验室制作了三个软着陆工具的功能是用于说明表面结合的有机金属化合物的代表制度编制的质量选择钌的三软着陆（联吡啶）二价阳离子，[茹（联吡啶）3] 2 +（联吡啶=联吡啶），到羧酸终止黄金（COOH-地空导弹自组装单层膜表面）， 在飞行时间的原位 （TOF）-SIMS提供了洞察软降落离子的反应性。此外，充电还原动力学，中和德吸附发生在COOH-SAM期间和离子软着陆使用原位傅立叶变换离子回旋共振（FT-ICR）-SIMS测量的研究后， 在原位 IRRAS实验提供深入了解的周围的金属中心的有机配位体的结构是通过COOH-SAM有机金属离子的固定面扰动通过软着陆。总的来说，三个工具提供关于支撑在表面良好定义的物种的化学成分，反应性和结构的互补信息。

1，调查茹的反应（联吡啶）3 2 +对COOH-地对空导弹采用原位 TOF-SIMS 质量选择的有机金属离子的软着陆到官能化的自组装膜，首先说明利用原位 TOF-SIMS提供最大的灵敏度朝向检测中的单层沉积的离子和单个分子以及化学反应的任何产品之间形成加合物的下列曝光表面反应性气体。双电荷吡啶钌3 +离子的溶解和离解固相亚磷酸三（2,2&#...

Watch this Scientific Journal Video about In Situ SIMS and IR Spectroscopy of Well-defined Surfaces Prepared by Soft Landing of Mass-selected Ions at JoVE.com

In Situ SIMS and IR Spectroscopy of Well-defined Surfaces Prepared by Soft Landing of Mass-selected Ions

质量选择离子软着陆表面上是一个功能强大的方法对高度控制的新型材料的准备。再加上通过原位二次离子质谱（SIMS）和红外反射吸收光谱（IRRAS）分析，软着陆提供前所未有的见解的良好定义的物种与表面的相互作用。

在质谱选择离子软着陆准备好定义的表面原位二次离子质谱和红外光谱

Soft landing of mass-selected ions onto surfaces is a powerful approach for the highly-controlled preparation of materials that are inaccessible using ...

in-situ-sims-ir-spectroscopy-well-defined-surfaces-prepared-soft

Research

JoVE Journal

Chemistry

In Situ SIMS and IR Spectroscopy of Well-defined Surfaces Prepared by Soft Landing of Mass-selected Ions

18.0K 次观看.  Pacific Northwest National Laboratory. 质量选择离子软着陆表面上是一个功能强大的方法对高度控制的新型材料的准备。再加上通过原位二次离子质谱（SIMS）和红外反射吸收光谱（IRRAS）分析，软着陆提供前所未有的见解的良好定义的物种与表面的相互作用。 

视频: In Situ SIMS and IR Spectroscopy of Well-defined Surfaces Prepared by Soft Landing of Mass-selected Ions

Dynamic Electrochemical Measurement of Chloride Ions

This protocol describes the dynamic measurement of chloride ions using the transition time of a silver silver chloride (Ag/AgCl) electrode. Silver silver chloride electrode is used extensively for potentiometric measurement of chloride ions concentration in electrolyte. In this measurement, long-term and continuous monitoring is limited due to the inherent drift and the requirement of a stable reference electrode. We utilized the chronopotentiometric approach to minimize drift and avoid the use of a conventional reference electrode. A galvanostatic pulse is applied to an Ag/AgCl electrode which initiates a faradic reaction depleting the Cl&#713; ions near the electrode surface. The transition time, which is the time to completely deplete the ions near the electrode surface, is a function of the ion concentration, given by the Nernst equation. The square root of the transition time is in linear relation to the chloride ion concentration. Drift of the response over two weeks is negligible (59 &#181;M/day) when measuring 1 mM [Cl&#713;]using a current pulse of 10 Am-2. This is a dynamic measurement where the moment of transition time determines the response and thus is independent of the absolute potential. Any metal wire can be used as a pseudo-reference electrode, making this approach feasible for long-term measurement inside concrete structures.

Dynamic measurement of chloride ions is presented. Transition time of an Ag/AgCl electrode, during a chronopotentiometric technique, can give the concentration of chloride ions in electrolyte. This method does not require a stable conventional reference electrode.

氯离子的动态电化学测试

This protocol describes the dynamic measurement of chloride ions using the transition time of a silver silver chloride (Ag/AgCl) electrode. Silver silver ...

科研

化学

In Situ Characterization of Hydrated Proteins in Water by SALVI and ToF-SIMS

This work demonstrates in situ characterization of protein biomolecules in the aqueous solution using the System for Analysis at the Liquid Vacuum Interface (SALVI) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). The fibronectin protein film was immobilized on the silicon nitride (SiN) membrane that forms the SALVI detection area. During ToF-SIMS analysis, three modes of analysis were conducted including high spatial resolution mass spectrometry, two-dimensional (2D) imaging, and depth profiling. Mass spectra were acquired in both positive and negative modes. Deionized water was also analyzed as a reference sample. Our results show that the fibronectin film in water has more distinct and stronger water cluster peaks compared to water alone. Characteristic peaks of amino acid fragments are also observable in the hydrated protein ToF-SIMS spectra. These results illustrate that protein molecule adsorption on a surface can be studied dynamically using SALVI and ToF-SIMS in the liquid environment for the first time.

In Situ Characterization of Hydrated Proteins in Water by SALVI and ToF-SIMS

This work presents a protocol for liquid handling and sample introduction to a microchannel for in situ time-of-flight secondary ion mass spectrometry analysis of protein biomolecules in an aqueous solution.

在水中水合蛋白原位表征SALVI和TOF-SIMS

This work demonstrates in situ characterization of protein biomolecules in the aqueous solution using the System for Analysis at the Liquid Vacuum ...

TiO2-coated Hollow Glass Microspheres with Superhydrophobic and High IR-reflective Properties Synthesized by a Soft-chemistry Method

This manuscript proposes a soft-chemistry method to develop superhydrophobic and highly IR-reflective hollow glass microspheres (HGM). The anatase TiO2 and a superhydrophobic agent were coated on the HGM surface in one step. TBT and PFOTES were selected as the Ti source and the superhydrophobic agent, respectively. They were both coated on the HGM, and after the hydrothermal process, the TBT turned to anatase TiO2. In this way, a PFOTES/TiO2-coated HGM (MCHGM) was prepared. For comparison, PFOTES single-coated HGM (F-SCHGM) and TiO2 single-coated HGM (Ti-SCHGM) were synthesized as well. The PFOTES and TiO2 coatings on the HGM surface were demonstrated through X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy-dispersive detector (EDS) characterizations. The MCHGM showed a higher contact angle (153&#176;) but a lower sliding angle (16&#176;) than F-SCHGM, with a contact angle of 141.2&#176; and a sliding angle of 67&#176;. In addition, both Ti-SCHGM and MCHGM displayed similar IR reflectivity values, which were about 5.8% higher than the original HGM and F-SCHGM. Also, the PFOTES coating barely changed the thermal conductivity. Therefore, F-SCHGM, with a thermal conductivity of 0.0479 W/(m&#183;K), was quite like the original HGM, which was 0.0475 W/(m&#183;K). MCHGM and Ti-SCHGM were also similar. Their thermal conductivity values were 0.0543 W/(m&#183;K) and 0.0543 W/(m&#183;K), respectively. The TiO2 coating slightly increased the thermal conductivity, but with the increase in reflectivity, the overall heat-insulation property was enhanced. Finally, since the IR-reflecting property is provided by the HGM coating, if the coating is fouled, the reflectivity decreases. Therefore, with the superhydrophobic coating, the surface is protected from fouling, and its lifetime is also prolonged.

TiO2-coated Hollow Glass Microspheres with Superhydrophobic and High IR-reflective Properties Synthesized by a Soft-chemistry Method

This manuscript proposes a soft-chemistry method to synthesize superhydrophobic, TiO2-coated hollow glass microspheres (HGM) with high IR-reflective properties.

二氧化钛<sub&gt; 2</sub与由软化学法合成的超疏水性和高IR反射属性&gt;涂覆的空心玻璃微球

This manuscript proposes a soft-chemistry method to develop superhydrophobic and highly IR-reflective hollow glass microspheres (HGM). The anatase TiO2 ...

In Situ Characterization of Shewanella oneidensis MR1 Biofilms by SALVI and ToF-SIMS

Bacterial biofilms are surface-associated communities that are vastly studied to understand their self-produced extracellular polymeric substances (EPS) and their roles in environmental microbiology. This study outlines a method to cultivate biofilm attachment to the System for Analysis at the Liquid Vacuum Interface (SALVI) and achieve in situ chemical mapping of a living biofilm by time-of-flight secondary ion mass spectrometry (ToF-SIMS). This is done through the culturing of bacteria both outside and within the SALVI channel with our specialized setup, as well as through optical imaging techniques to detect the biofilm presence and thickness before ToF-SIMS analysis. Our results show the characteristic peaks of the Shewanella biofilm in its natural hydrated state, highlighting upon its localized water cluster environment, as well as EPS fragments, which are drastically different from the same biofilm's dehydrated state. These results demonstrate the breakthrough capability of SALVI that allows for in situ biofilm imaging with a vacuum-based chemical imaging instrument.

In Situ Characterization of Shewanella oneidensis MR1 Biofilms by SALVI and ToF-SIMS

This article presents a method for growing a biofilm for in situ time-of-flight secondary ion mass spectrometry for chemical mapping in its hydrated state, enabled by a microfluidic reactor, System for Analysis at the liquid Vacuum Interface. The Shewanella oneidensis MR-1 with green fluorescence protein was used as a model.

原位萨尔和 TOF-SIMS希瓦氏菌 oneidensis MR1 生物膜的表征

Bacterial biofilms are surface-associated communities that are vastly studied to understand their self-produced extracellular polymeric substances (EPS) ...

Fabrication and Testing of Catalytic Aerogels Prepared Via Rapid Supercritical Extraction

Protocols for preparing and testing catalytic aerogels by incorporating metal species into silica and alumina aerogel platforms are presented. Three preparation methods are described: (a) the incorporation of metal salts into silica or alumina wet gels using an impregnation method; (b) the incorporation of metal salts into alumina wet gels using a co-precursor method; and (c) the addition of metal nanoparticles directly into a silica aerogel precursor mixture. The methods utilize a hydraulic hot press, which allows for rapid (&#60;6 h) supercritical extraction and results in aerogels of low density (0.10 g/mL) and high surface area (200-800 m2/g). While the work presented here focuses on the use of copper salts and copper nanoparticles, the approach can be implemented using other metal salts and nanoparticles. A protocol for testing the three-way catalytic ability of these aerogels for automotive pollution mitigation is also presented. This technique uses custom-built equipment, the Union Catalytic Testbed (UCAT), in which a simulated exhaust mixture is passed over an aerogel sample at a controlled temperature and flow rate. The system is capable of measuring the ability of the catalytic aerogels, under both oxidizing and reducing conditions, to convert CO, NO and unburned hydrocarbons (HCs) to less harmful species (CO2, H2O and N2). Example catalytic results are presented for the aerogels described.

Here we present protocols for preparing and testing catalytic aerogels by incorporating metal species into silica and alumina aerogel platforms. Methods for preparing materials using copper salts and copper-containing nanoparticles are featured. Catalytic testing protocols demonstrate the effectiveness of these aerogels for three-way catalysis applications.

快速超临界萃取制备催化气凝胶的制备与试验研究

Protocols for preparing and testing catalytic aerogels by incorporating metal species into silica and alumina aerogel platforms are presented. Three ...

Rapid Nanoprobe Signal Enhancement by In Situ Gold Nanoparticle Synthesis

The use of nanoprobes such as gold, silver, silica or iron-oxide nanoparticles as detection reagents in bioanalytical assays can enable high sensitivity and convenient colorimetric readout. However, high densities of nanoparticles are typically needed for detection. The available synthesis-based enhancement protocols are either limited to gold and silver nanoparticles or rely on precise enzymatic control and optimization. Here, we present a protocol to enhance the colorimetric readout of gold, silver, silica, and iron oxide nanoprobes. It was observed that the colorimetric signal can be improved by up to a 10000-fold factor. The basis for such signal enhancement strategies is the chemical reduction of Au3+ to Au0. There are several chemical reactions that enable the reduction of Au3+ to Au0. In the protocol, Good&#39;s buffers and H2O2 are used and it is possible to favor the deposition of Au0 onto the surface of existing nanoprobes, in detriment of the formation of new gold nanoparticles. The protocol consists of the incubation of the microarray with a solution consisting of chloroauric acid and H2O2 in 2-(N-morpholino)ethanesulfonic acid pH 6 buffer following the nanoprobe-based detection assay. The enhancement solution can be applied to paper and glass-based sensors. Moreover, it can be used in commercially available immunoassays as demonstrated by the application of the method to a commercial allergen microarray. The signal development requires less than 5 min of incubation with the enhancement solution and the readout can be assessed by naked eye or low-end image acquisition devices such as a table-top scanner or a digital camera.

Rapid Nanoprobe Signal Enhancement by In Situ Gold Nanoparticle Synthesis

In this work, a protocol for signal enhancement of nanoprobe-based biosensing is presented. The protocol is based on the reduction of chloroauric acid onto the surface of existing nanoprobes that consist of gold, silver, silica or iron-oxide nanoparticles.

原位金纳米粒子合成快速 Nanoprobe 信号增强

The use of nanoprobes such as gold, silver, silica or iron-oxide nanoparticles as detection reagents in bioanalytical assays can enable high sensitivity ...

In Situ Lithiated Reference Electrode: Four Electrode Design for In-operando Impedance Spectroscopy

Extending operating voltage of Li-ion batteries results in higher energy output from these devices. High voltages, however, may trigger or accelerate multiple processes responsible for long-term performance decay. Given the complexity of physical processes occurring inside the cell, it is often challenging to achieve a full understanding of the root causes of this performance degradation. This difficulty arises in part from the fact that any electrochemical measurement of a battery will return the combined contributions of all components in the cell. Incorporation of a reference electrode can solve part of the problem, as it allows the electrochemical reactions of the cathode and the anode to be individually probed. A variation in the voltage range experienced by the cathode, for example, can indicate alterations in the pool of cyclable lithium ions in the full-cell. The structural evolution of the many interphases existing in the battery can also be monitored, by measuring the contributions of each electrode to the overall cell impedance. Such wealth of information amplifies the reach of diagnostic analysis in Li-ion batteries and provides valuable input to the optimization of individual cell components. In this work, we introduce the design of a test cell able to accommodate multiple reference electrodes, and present reference electrodes that are appropriate for each specific type of measurement, detailing the assembly process in order to maximize the accuracy of the experimental results.

The incorporation of reference electrodes in a Li-ion battery provides valuable information to elucidate degradation mechanisms at high voltages. In this article, we present a cell design that accommodates multiple reference electrodes, along with the assembly steps to assure maximum accuracy of the data obtained in electrochemical measurements.

原位锂化参考电极: 四原位阻抗谱的电极设计

Extending operating voltage of Li-ion batteries results in higher energy output from these devices. High voltages, however, may trigger or accelerate ...

Elemental-sensitive Detection of the Chemistry in Batteries through Soft X-ray Absorption Spectroscopy and Resonant Inelastic X-ray Scattering

Energy storage has become more and more a limiting factor of today's sustainable energy applications, including electric vehicles and green electric grid based on volatile solar and wind sources. The pressing demand of developing high-performance electrochemical energy storage solutions, i.e., batteries, relies on both fundamental understanding and practical developments from both the academy and industry. The formidable challenge of developing successful battery technology stems from the different requirements for different energy-storage applications. Energy density, power, stability, safety, and cost parameters all have to be balanced in batteries to meet the requirements of different applications. Therefore, multiple battery technologies based on different materials and mechanisms need to be developed and optimized. Incisive tools that could directly probe the chemical reactions in various battery materials are becoming critical to advance the field beyond its conventional trial-and-error approach. Here, we present detailed protocols for soft X-ray absorption spectroscopy (sXAS), soft X-ray emission spectroscopy (sXES), and resonant inelastic X-ray scattering (RIXS) experiments, which are inherently elemental-sensitive probes of the transition-metal 3d and anion 2p states in battery compounds. We provide the details on the experimental techniques and demonstrations revealing the key chemical states in battery materials through these soft X-ray spectroscopy techniques.

Here, we present a protocol for typical experiments of soft X-ray absorption spectroscopy (sXAS) and resonant inelastic X-ray scattering (RIXS) with applications in battery material studies.

软 x 射线吸收光谱和共振非弹性 x 射线散射法检测电池化学成分的元素敏感度

Energy storage has become more and more a limiting factor of today's sustainable energy applications, including electric vehicles and green electric grid ...

Accumulation and Analysis of Cuprous Ions in a Copper Sulfate Plating Solution

Knowledge of the behavior of cuprous ions (monovalent copper ion: Cu(I)) in a copper sulfate plating bath is important for improving the plating process. We successfully developed a method to quantitatively and easily measure Cu(I) in a plating solution and used it for evaluation of the solution. In this paper, a quantitative absorption spectrum measurement and a time-resolved injection measurement of Cu(I) concentrations by a color reaction are described. This procedure is effective as a method to reproduce and elucidate the phenomenon occurring in the plating bath in the laboratory. First, the formation and accumulation process of Cu(I) in solution by electrolysis of a plating solution is shown. The amount of Cu(I) in the solution is increased by electrolysis at higher current values &#8203;&#8203;than the usual plating process. For the determination of Cu(I), BCS (bathocuproinedisulfonic acid, disodium salt), a reagent that selectively reacts with Cu(I), is used. The concentration of Cu(I) can be calculated from the absorbance of the Cu(I)-BCS complex. Next, the time measurement of the color reaction is described. The color reaction curve of Cu(I) and BCS measured by the injection method can be decomposed into an instantaneous component and a delay component. By analysis of these components, the holding structure of Cu(I) can be clarified, and this information is important when predicting the quality of the plating film to be produced. This method is used to facilitate the evaluation of the plating bath in the production line.

Here, accumulation of cuprous ions in a copper sulfate plating solution in a model experiment and an analysis based on quantitative measurements are described. This experiment reproduces the accumulation process of cuprous ions in the plating bath.

硫酸铜镀液中铜离子的积累与分析

Knowledge of the behavior of cuprous ions (monovalent copper ion: Cu(I)) in a copper sulfate plating bath is important for improving the plating process. ...

Analysis of Complex Molecules and Their Reactions on Surfaces by Means of Cluster-Induced Desorption/Ionization Mass Spectrometry

Desorption/Ionization Induced by Neutral SO2 Clusters (DINeC) is employed as a very soft and efficient desorption/ionization technique for mass spectrometry (MS) of complex molecules and their reactions on surfaces. DINeC is based on a beam of SO2 clusters impacting on the sample surface at low cluster energy. During cluster-surface impact, some of the surface molecules are desorbed and ionized via dissolvation in the impacting cluster; as a result of this dissolvation-mediated desorption mechanism, low cluster energy is sufficient and the desorption process is extremely soft. Both surface adsorbates and molecules of which the surface is composed of can be analyzed. Clear and fragmentation-free spectra from complex molecules such as peptides and proteins are obtained. DINeC does not require any special sample preparation, in particular no matrix has to be applied. The method yields quantitative information on the composition of the samples; molecules at a surface coverage as low as 0.1 % of a monolayer can be detected. Surface reactions such as H/D exchange or thermal decomposition can be observed in real-time and the kinetics of the reactions can be deduced. Using a pulsed nozzle for cluster beam generation, DINeC can be efficiently combined with ion trap mass spectrometry. The matrix-free and soft nature of the DINeC process in combination with the MSn capabilities of the ion trap allows for very detailed and unambiguous analysis of the chemical composition of complex organic samples and organic adsorbates on surfaces.

Neutral SO2 clusters of low kinetic energy (&#60; 0.8 eV/constituent) are used to desorb complex surface molecules such as peptides or lipids for further analysis by means of mass spectrometry using an ion trap mass spectrometer. No special sample preparation is required, and real-time observation of reactions is possible.