This research was carried out at the Jet Propulsion Laboratory, California Institute of Technology, under a contract with the National Aeronautics and Space Administration. We acknowledge the support by the NASA Astrobiology Institute (Icy Worlds). L.M.B. is supported by the NAI through the NASA Postdoctoral Program, administered by Oak Ridge Associated Universities through a contract with NASA. J.E.N. was supported through a US Department of Education PR/Award #: P031C110019 administered through Citrus College. We acknowledge useful discussions with members of the NAI Thermodynamics, Disequilibrium, and Evolution Focus Group and the Blue Marble Space Institute of Science.

1.安全注意事项<ol><li>使用个人防护装备（实验室外套，护目镜，丁腈手套，合适的鞋），以防止对化学品泄漏或受伤。使用注射器和针头，并注意不要穿刺手套。实验安装过程中要小心通过与首先进行注射，以检查是否有泄漏的装置，双蒸H 2 O（DDH 2 O的），并检查反应瓶上的立场的稳定性，添加化学品前。 </li><li>进行这项实验与任何化学花园配方，但我们用来模拟深海通风口反应物之一是一种有害化学品，硫化钠;因此，做整个实验在通风橱内，以防止曝光。 <ol><li>仅打开在通风柜瓶子的硫化钠和放置通风橱用于称重硫化物内的平衡。始终保持含硫化物的解决方案通风柜内，因为它们释放出有毒的硫化氢气体，同时还保持硫化物Ë液体，锐器，以及固体废弃物的容器在通风橱。感兴趣的另一种反应物为Fe（II）Cl 2中•4H 2 O，从而氧化在暴露于空气中，所以要小心，以保持溶液缺氧和生长的化学花园下缺氧顶空（例如，N 2或Ar），总是在通风橱或手套箱。 </li></ol></li></ol> 2.设置注射实验<ol><li>通过切断底部1厘米的100毫升的透明玻璃的压顶血清瓶（20毫米卷边密封闭合型），用玻璃切割器，使得，倒立时，容器是向大气开放创建玻璃“注射瓶”。由于这是可重复使用的，清洁的1 M盐酸酸浴O / N小瓶，然后一个新的实验之前，DDH 2 O的冲洗干净。 </li><li>制备注射瓶（ 图1）。 <ol><li>收集一门20毫米隔20 mm铝卷边密封，以及0.5〜10微升塑料吸管尖。为16G注射器NEedle，小心刺穿隔膜的中心孔，然后取出并丢弃在适当的锐器废物容器的针。 </li><li>插入枪头进针孔，进入橡胶隔膜将面临小瓶的卷曲顶部内侧的侧面。通过隔膜推枪头，以便它戳出的另一侧。 </li><li>卷曲密封与枪头隔膜到注入容器，使防水密封。当密封，进一步推枪头通过隔膜，以便它向外部伸出。 </li><li>贴上1/16“内径清晰灵活的抗化学腐蚀油管枪头（管道长度应达到从注射小瓶注射泵）;向上滑动的防水密封。 注意：这将是喷射管，通过用为16G针的注射器从另一端送入。 </li><li>检查是否有泄漏：将10毫升注射器填充DDH 2 O的用为16G针头插入管的另一端（平滑的管滑动直到针，小心不要刺破管的壁上）。慢慢注入使得DDH 2 O的向上移动管并进入反应容器的底部。确保注射器/管，管件/提示和压密封件防水。 </li></ol></li><li>夹紧在支架上在通风橱中注射小瓶，从而使注射将饲料从小瓶的底部。 注：多个小瓶可设置在一次和由单独的注射器同时加入。 </li><li>设置的电极，用于测量膜电位跨越的化学花园壁。始终使用其领先的“内幕”，哪些是“外面”的化学花园相同的约定。 <ol><li>切割绝缘电线（例如，铜），其从内部反应容器到达到万用表或数据记录器的引线的长度。离开松弛一点点的电线定位。 </li><li>条〜3个毫米的连线裸露在那个将位于反应小瓶内部的端部。在将要连接到万用表引线，条约1cm电线的另一端​​。 </li><li>固定导线以衡量整个化工园区膜电位。用于电线，将里面去的化学花园：将其插入枪头从中流体将送入容器的开口。 </li><li>推线中轻轻以确保与注射溶液接触，却远没有那么它将堵塞喷射流。对于外界线：位置，以便它会在与溶液储存器但不与化学花园沉淀接触。 </li><li>带或以其他方式固定导线，使它们可以在注入小瓶内部的实验（图2）期间不会移动。 </li><li>附加的导线的另一端​​部到万用表，并固定导线，使这些端部也不会在整个实验移动。 </li></ol></li><li>设置N 2 </子&gt;输气管线，将每个送入注射瓶之一。 <ol><li>分割从在 N 2源气体进料成几个管，使得存在一个N 2进料每次注射小瓶中。 </li><li>将每个N 2管，使其供给到注射小瓶中的一个的顶部空间。 </li></ol></li></ol> 3.准备化工园成长解决方案<ol><li>制备贮存溶液，加入100毫升每个实验。注意：在这个例子中，使用75毫米的 Fe 2+和25mM的Fe 3+作为沉淀阳离子（ 表1）。 <ol><li>由第一鼓泡DDH 2 O的以 N 2气体为每100毫升〜15分钟创建缺氧的解决方案。 </li><li>称取并添加的FeCl 2•4H 2 O和的FeCl 3•6H 2 O，轻轻搅拌，以溶解（未大力以便不引入氧气）。 </li><li>试剂溶解后，立即resum铁2+ /铁E光冒泡3+ 以 N 2气体解决方案，同时注射准备。 </li></ol></li><li>选择任何两个在表1所示的主注射溶液，并准备各10ml的。填有10毫升注射器到7 ml的标记与每个解的（一个针筒每个溶液）。更换针头帽，备用。 </li><li>备将20毫升二次注射溶液（硫化钠-小心）。 表 1中所示填充两个10 ml的注射器到7 ml的标记用此溶液，更换针帽，备用。始终保持在通风柜含硫化物溶液和注射器。 </li><li>笔芯的双蒸水从步骤2.2.5 2 O注射器;这些将被用于冲洗注入管。 </li></ol> 4.启动主注入<ol><li>使用所需的数据记录器的膜电位测量。衡量一个分隔符每个实验的潜力E通道，并设置扫描速率，得到的数据点的期望的量（例如，对于一个2小时注射，记录电位，每30秒就足够了）。 </li><li>固定在通风橱可编程注射泵主喷射注射器。 </li><li>使用废物烧杯赶上滴，并设置在注射器泵以很快的速度注入，直到注射器既开始滴入烧杯中。然后停止喷射（为了确保这两个注射器开始注入以完全相同的电平）。 </li><li>重新编程注射泵以每小时2毫升注入（用于校准所使用的注射器的类型），但不打的开始。 </li><li>插入DDH 2 O的注射器进入两个塑料注射管，并注入使水填充透明管最多在其进入主储存器的孔。将注射器在支架上，上述的注射小瓶中。 </li><li>倾将100ml 的 Fe 2+ / Fe的3+储液进EA的CH小瓶。 </li><li>根据需要，以保持在实验缺氧用于注射的持续时间调节N 2气行的流动。 </li><li>小心覆盖气密密封容器小瓶（例如，使用封口膜;不阻碍透过玻璃的视图）和插入的N 2进料到每个小瓶中（图3）。 </li><li>带上DDH 2 O的注射器（在管道仍插）跌旁边初次注射针筒。小心地将注塑管关闭DDH 2 O的注射器针头，并立即将其直接传送到主注射器针头之一。 （小心不要刺破管的壁上。） </li><li>开始注射，并开始记录膜电位。 </li></ol> 5.启动二次注入： <ol><li> 3小时后击中停止注射泵，一旦化工园区结构已经形成（6毫升被注射后）（Figu重新4），不断地产生一个膜电位（图5）。 </li><li>小心地取出从注射泵的主注射针筒（但保持其连接到该管道使结构没有干扰）;设置它们在支架上在上面的小瓶中的流体的水平，以使流体不能回流到注射器。 </li><li>固定二次注入硫化物注射器在注射器泵，并重复步骤4.3和4.4。 </li><li>删除辅助注射器1在从注射泵一个时间，和，同时保持上述在小瓶中的流体的水平的注射器，重复步骤4.9，传送管路从主注射器到辅助注射器（图6）。警惕，从储存器到注射器中的流体压力不会引起流体回流到注射器，因为这可能崩溃的化学花园。 </li><li>当传输完成后，小心地固定二级注射器日Ë注射泵。 </li><li>重新计划的注射泵注入以每小时2毫升，并打开始继续注射用新的注射液。 </li><li>安全地处理主喷射注射器。 </li></ol> 6.结束实验<ol><li>首先停止注射泵，然后停止录音的膜电位和保存数据。 </li><li>关闭N 2流量和删除线和封口膜从注射血管。 </li><li>如果需要的话，样品贮存溶液或沉淀进行进一步的分析。要仔细清除水库的解决方案，而不是打扰沉淀，用25毫升吸管仔细移液器关闭储液在几个等份，并丢弃浪费烧杯中的解决方案。 </li><li>松开注入容器一次一个，并将溶液倒入在通风橱浪费转印烧杯中。使用DDH 2 O的冲洗出沉淀物件。 </li><li>来回取下注射器米注射器泵，并且从管中提取它们，让多余的注入流体流失到废物转移烧杯中。清空注射器进入废物烧杯中，并在保持在通风橱硫化物尖锐件容器处置注射器。 </li><li>取下实验瓶的管子和一个固体废物袋进行处置。解卷曲密封和处置隔，印章，枪头。 </li><li>冲洗出来的玻璃实验瓶中，浸泡在1 M盐酸酸浴O / N。 （注意-玻璃器皿一直在与硫化钠接触会释放出有毒的硫化氢气体时，放置在酸性保持酸浴的通风橱内。） </li></ol>

<ol>
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A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=A+hydrothermally+precipitated+catalytic+iron+sulphide+membrane+as+a+first+step+toward+life.">A hydrothermally precipitated catalytic iron sulphide membrane as a first step toward life.</a> J. Mol. Evol. 39 (3), 231-243 (1994).</li><li>Barge, L. M., 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=Pyrophosphate+Synthesis+in+Iron+Mineral+Films+and+Membranes+Simulating+Prebiotic+Submarine+Hydrothermal+Systems.">Pyrophosphate Synthesis in Iron Mineral Films and Membranes Simulating Prebiotic Submarine Hydrothermal Systems.</a> Geochim. Cosmochim. Ac. 128, 1-12 (2014).</li><li>McGlynn, S. E., Kanik, I., Russell, M. J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Peptide+and+RNA+contributions+to+iron-sulphur+chemical+gardens+as+life's+first+inorganic+compartments,+catalysts,+capacitors+and+condensors.">Peptide and RNA contributions to iron-sulphur chemical gardens as life's first inorganic compartments, catalysts, capacitors and condensors.</a> Philos. T. R. Soc. S-A. 370, 3007-3022 (2012).</li><li>Cartwright, J. H. E., Escribano, B., Sainz-D&#237;az, C. I., Stocieck, L. S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Chemical-Garden+Formation,+Morphology,+and+Composition.+II.+Chemical+Gardens+in+Microgravity.">Chemical-Garden Formation, Morphology, and Composition. II. Chemical Gardens in Microgravity.</a> Langmuir. 27, 3294-3300 (2011).</li><li>Thouvenel-Romans, S., Steinbock, O. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Oscillatory+Growth+of+Silica+Tubes+in+Chemical+Gardens.">Oscillatory Growth of Silica Tubes in Chemical Gardens.</a> J. Am. Chem. Soc. 125, 4338-4341 (2003).</li><li>Batista, B. C., Cruz, P., Steinbock, O. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=From+Hydrodynamic+Plumes+to+Chemical+Gardens:+The+Concentration-Dependent+Onset+of+Tube+Formation.">From Hydrodynamic Plumes to Chemical Gardens: The Concentration-Dependent Onset of Tube Formation.</a> Langmuir. 30, 9123-9129 (2014).</li><li>Herschy, B., 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=An+origin-of-life+reactor+to+simulate+alkaline+hydrothermal+vents.">An origin-of-life reactor to simulate alkaline hydrothermal vents.</a> J. Mol. Evol. 79, 213-227 (2014).</li><li>Yamaguchi, A., Yamamoto, M., Takai, K., Ishii, T., Hashimoto, K., Nakamura, R. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Electrochemical+CO2+Reduction+by+Ni-containing+Iron+Sulfides:+How+Is+CO2+Electrochemically+Reduced+at+Bisulfide-Bearing+Deep-sea+Hydrothermal+Precipitates?.">Electrochemical CO2 Reduction by Ni-containing Iron Sulfides: How Is CO2 Electrochemically Reduced at Bisulfide-Bearing Deep-sea Hydrothermal Precipitates?.</a> Electrochim. Acta. 141, 311-318 (2014).</li><li>Hansen, H. C. B., Guldberg, S., Erbs, M., Koch, C. B. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Kinetics+of+nitrate+reduction+by+green+rusts&#8212;effects+of+interlayer+anion+and+Fe+(II):+Fe+(III)+ratio.">Kinetics of nitrate reduction by green rusts&#8212;effects of interlayer anion and Fe (II): Fe (III) ratio.</a> Appl. Clay Sci. 18 (1), 81-91 (2001).</li><li>Trolard, F., Bourri&#233;, G. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Fougerite+a+natural+layered+double+hydroxide+in+gley+soil:+habitus,+structure,+and+some+properties.">Fougerite a natural layered double hydroxide in gley soil: habitus, structure, and some properties.</a> Clay Minerals in Nature - Their Characterization, Modification and Application. , (2012).</li><li>van Oss, C. J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Specifically+Impermeable+Precipitate+Membranes.">Specifically Impermeable Precipitate Membranes.</a> Surface and Colloid Science. , 115-144 (1984).</li><li>Baaske, P., 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=Extreme+accumulation+of+nucleotides+in+simulated+hydrothermal+pore+systems.">Extreme accumulation of nucleotides in simulated hydrothermal pore systems.</a> P. Natl. Acad. Sci. USA. 104, 9346-9351 (2007).</li></ol>

The authors declare that they have no competing financial interests.

通过注射方法的化学花园结构的形成可以通过连接包含产生沉淀反应离子任何两个解决方案来实现。有许多可能的反应系统，将产生的沉淀物的结构并发现反应离子和浓度的权利配方以生长所需结构是试验和错误的问题。注射溶液的流速由一个可编程注射器泵控制，这也可以实验之间变化，以模拟在自然系统中的流体流动的速率不同。化学园林结构取决于很多因素，包括组合物和流量，并且它是?...

“化学花园”是自组装开发无机沉淀物，其中对比化学物质的两种流体交互1,2。这些自组装的无机结构已经超过一个世纪的部分原因是由于他们的仿生外观的科学兴趣的主题，许多实验和理论研究已经进行，以了解化学园林系统3的各种复杂问题和可能的功能。化学园林自然的例子包括矿物“烟囱”的沉淀，围绕热水泉和冷泉增长，有人认为，这些可以提供合理的环境中生活出现4。为了发展一个化工园区模拟自然的热液喷口烟囱，水库的解决方案应该代表一个模拟的海洋成分和注射液应代表热液流体送入大海。这种O型的多功能性˚F实验不同的反应系统可以模拟几乎任何提议的海洋/热液流体化学，包括对早期地球或其它星球上的环境。在早期地球，海洋本来缺氧，酸性（pH值5-6），并且将含有溶解大气 CO 2和Fe 2+，以及铁III，镍离子， 锰离子，编号3-和NO 2 - 。此海水和超基洋壳之间的化学反应会产生含有氢和甲烷的碱性热液，在某些情况下硫化物（HS - ）4-8。形成在早期地球碱性通气环境烟囱可由此包含亚铁/铁羟基氧化物和铁/镍硫化物，并且已经提出，这些矿物质可能起到特定的催化和原酶功能朝向利用地球化学氧化还原/ pH梯度来驱动Metaboli游戏的出现SM 5。同样，在其他世界如可承办（或已托管）水/岩界面 - 例如早期的火星，木星的卫星木卫二，或土星的卫星土卫二 - 有可能是水/岩的化学能产生碱性发泄的环境能够驾驶生命起源前化学甚至提供可居住龛现存生命5,9-11。 经典的化学园实验涉及晶种的金属盐，例如，四水合氯化亚铁的FeCl 2•4H 2 O，浸没在含有反应性的阴离子， 如硅酸钠或“水玻璃”的溶液。金属盐溶解，创建包含的 Fe 2+的酸性溶液，随着更多的碱性溶液接口（含硅酸盐阴离子和OH - ）和被形成的无机膜的沉淀。在渗透压的膜膨​​胀，破裂，然后重新沉淀的t是新的流体界面。这个过程一直重复，直到晶体溶解，从而产生一个垂直取向的，自组织的沉淀结构具有复杂的形态在宏观和微观尺度。此沉淀过程导致横跨无机化学花园膜化学反衬解决方案的持续分离，带电物质穿过膜的差产生了膜电位12-14中 。化学花园结构是复杂的，表现出组分梯度从内部到外部13,15-19，和该结构的壁保持对比解决方案之间的分离很长时间，同时保持稍微渗透到离子。除了是一个理想的实验中用于教育目的（因为它们是简单，使课堂演示，并能教育学生的化学反应和自组织），化工园有科学意义的自我assemb交涉LY在动态，远离平衡系统，涉及可导致生产性的和有用的材料20,21的方法。 化学园林在实验室也可以通过注射方法进行培养，其中含有一种离子沉淀的溶液缓慢注入到包含所述共沉淀离子（或离子）的第二溶液。这导致类似于晶体生长实验化学花园结构的形成，不同之处在于该系统的性能和沉淀可更好地控制。注射方法有几个显著优点。它允许一个使用沉淀或结合物种的任何组合，以形成化学花园; 即多个沉淀离子可以结合到一个解决方案，和/或其它非沉淀组分可以被包括在任溶液，以吸附与沉淀物/反应。在化学产生的膜电位花园系统可以在注射实验来测定，如果一个电极结合到结构的内部，因此能够使系统的电化学研究。注射实验提供通过改变喷射率或总注射体积喂注射溶液成的化学园的内部受控的时间框架中的能力;因此，可以通过不同的解决方案依次饲料和使用沉淀的结构为陷阱或反应器中。结合，这些技术允许实验室模拟，可以在一个海底热液通风口都发生在一个天然化学花园系统的复杂过程，包括来自海洋之间许多同时沉淀反应形成的烟囱和泄流体（例如，制备金属硫化物，氢氧化物和/或碳酸盐和硅酸盐）5,22。这些技术也可以应用到任何化学花园反应体系，以允许形成新类型的的材料， 例如，分层管或管与吸附的反应性物质20,23。 我们这里详细的示例实验，其中包括两种化学花园，铁2+含结构在缺氧环境中的同步增长。在这个实验中，我们引入多磷酸盐和/或氨基酸的痕量到初始注射溶液，观察它们对结构的影响。的化工园区初步形成后，我们再切换注射液引入硫化物作为二次沉淀阴离子。膜电位的测定是在整个实验自动进行。本协议描述如何运行两个实验，在使用双注射泵一次;示所需的数据此过程的多次运行。相对较高的流量，在我们的实验中使用的水库和反应物浓度低pH值的目的是形成大烟囱沉淀在时间SC麦芽啤酒适合一天的实验室实验。然而，流体的流速在天然热水泉可以更加分散和（在早期地球系统 ，例如，Fe和S）沉淀物的浓度可能是震级低 4的命令;因此，结构化的沉淀物会形成较长的时间尺度和通风口可以活跃多年24,25几万。

<table border="0" cellpadding="0" cellspacing="0">
	<tbody>
		<tr>
			<td>Syringe Pump</td>
			<td>Fisher</td>
			<td>14-831-3</td>
			<td>Dual or multiple channel, depending on desired number of simultaneous experiments</td>
		</tr>
		<tr>
			<td>Ferrous chloride tetrahydrate</td>
			<td>Fisher</td>
			<td>I90500</td>
			<td>Ferrous Chloride Tetrahydrate (Crystalline/Certified)</td>
		</tr>
		<tr>
			<td>Ferric chloride hexahydrate</td>
			<td>Fisher</td>
			<td>I88-100&#160;</td>
			<td>Ferric&#160;Chloride&#160;Hexahydrate&#160;(Lumps/Certified ACS)</td>
		</tr>
		<tr>
			<td>Sodium hydroxide</td>
			<td>Sigma-Aldrich</td>
			<td>S5881</td>
			<td>reagent grade, &#8805;98%, pellets (anhydrous)</td>
		</tr>
		<tr>
			<td>Sodium sulfide nonahydrate</td>
			<td>Fisher</td>
			<td>S425212</td>
			<td>Sodium Sulfide Nonahydrate (Crystalline/Certified ACS).&#160; Store at -20C. Only open in a glove box or fume hood. Releases toxic H2S gas; all sulfide-containing solutions must be kept in a glove box or fume hood.</td>
		</tr>
		<tr>
			<td>Potassium pyrophosphate</td>
			<td>Sigma-Aldrich</td>
			<td align="right">322431</td>
			<td>97%, http://www.sigmaaldrich.com/catalog/product/aldrich/322431?lang=en&#38;region=US</td>
		</tr>
		<tr>
			<td>L-Alanine</td>
			<td>Sigma-Aldrich</td>
			<td>A7627</td>
			<td>http://www.sigmaaldrich.com/catalog/product/sigma/a7627?lang=en&#38;region=US</td>
		</tr>
		<tr>
			<td>Syringes (10cc)</td>
			<td>Fisher</td>
			<td>14-823-16E</td>
			<td>BD&#8482; Syringe with Luer-Lok Tips (Without Needle)</td>
		</tr>
		<tr>
			<td>Syringe needles (16 gauge)</td>
			<td>Fisher</td>
			<td>14-826-18B</td>
			<td>BD&#8482; General Use and PrecisionGlide Hypodermic Needles, 16 G x 1.5 in. (38mm)</td>
		</tr>
		<tr>
			<td>Tubing</td>
			<td>Cole Parmer</td>
			<td>EW-06407-71</td>
			<td>Tygon Lab Tubing, Non-DEHP, 1/16&#34;ID X 1/8&#34;OD</td>
		</tr>
		<tr>
			<td>Aluminum seals</td>
			<td>Fisher</td>
			<td>0337523C</td>
			<td>Thermo Scientific&#8482; National&#8482; Headspace 20mm Crimp Seals</td>
		</tr>
		<tr>
			<td>Gray butyl stoppers</td>
			<td>Fisher</td>
			<td>0337522AA</td>
			<td>Thermo Scientific&#8482; National&#8482; 20mm Septa for Headspace Vials</td>
		</tr>
		<tr>
			<td>Serum bottles</td>
			<td>Sigma-Aldrich</td>
			<td>33110-U</td>
			<td>Vials, crimp top, serum bottle, size 100 mL, clear glass, O.D. &#215; H 51.7 mm &#215; 94.5 mm. For these experiments, the bottom of the serum bottle should be cut off.</td>
		</tr>
		<tr>
			<td>Pipette tips</td>
			<td>VWR</td>
			<td>53511-682</td>
			<td>pipette tips 0.5-10 microliters</td>
		</tr>
		<tr>
			<td>Wire</td>
			<td>McMaster-Carr</td>
			<td>8073K661</td>
			<td>Solid Single-Conductor Wire, UL 1007/1569, 20 AWG, 300 VAC</td>
		</tr>
	</tbody>
</table>

chemical gardens as flow-through reactors simulating natural hydrothermal systems

Here we report experimental simulations of hydrothermal chimney growth using injection chemical garden methods. The versatility of this type of experiment allows for testing of various proposed ocean / hydrothermal fluid chemistries that could have driven reactions toward the origin of life in environments on the early Earth, early Mars, or even other worlds such as the icy moons of the outer planets. We show experiments that include growth of chemical garden structures under anoxic conditions simulating the early Earth, inclusion of trace components of phosphates / organics in the injection solution to incorporate them into the structure, a switch of the injection solution to introduce a secondary precipitating anion, and the measurement of membrane potentials generated by chemical gardens. Using this method, self-assembling chemical garden structures were formed that mimic the natural chimneys precipitated at submarine hydrothermal springs, and these precipitates can be used successfully as flow-through reactors by feeding through multiple successive &#8220;hydrothermal&#8221; injections.

一旦注射溶液开始送入贮存溶液，化学花园沉淀开始形成在流体界面和该结构继续生长在注射（ 图4-7）的过程。在这里报导的实验中，第一次注射是氢氧化钠（其可以被修改以包括L-丙氨酸和/或焦磷酸），和贮存溶液是1：铁3+ /的 Fe 2+的3混合物，得到的混合-redox态氢氧化铁沉淀。化学花园通常表现出双色形态-一些作品沉淀的是深绿色（表示可能的混合氢氧化合物）等片呈橙?...

Watch this Scientific Journal Video about Chemical Gardens as Flow-through Reactors Simulating Natural Hydrothermal Systems at JoVE.com

Chemical Gardens as Flow-through Reactors Simulating Natural Hydrothermal Systems

We describe chemical garden formation via injection experiments that allow for laboratory simulations of natural chemical garden systems that form at submarine hydrothermal vents.

化工园为直通式反应器模拟自然热液系统

Here we report experimental simulations of hydrothermal chimney growth using injection chemical garden methods. The versatility of this type of experiment ...

chemical-gardens-as-flow-through-reactors-simulating-natural

Research

JoVE Journal

Chemistry

14.4K 次观看.  California Institute of Technology. We describe chemical garden formation via injection experiments that allow for laboratory simulations of natural chemical garden systems that form at submarine hydrothermal vents.

视频: Chemical Gardens as Flow-through Reactors Simulating Natural Hydrothermal Systems

Free Radicals in Chemical Biology: from Chemical Behavior to Biomarker Development

The involvement of free radicals in life sciences has constantly increased with time and has been connected to several physiological and pathological processes. This subject embraces diverse scientific areas, spanning from physical, biological and bioorganic chemistry to biology and medicine, with applications to the amelioration of quality of life, health and aging. Multidisciplinary skills are required for the full investigation of the many facets of radical processes in the biological environment and chemical knowledge plays a crucial role in unveiling basic processes and mechanisms. We developed a chemical biology approach able to connect free radical chemical reactivity with biological processes, providing information on the mechanistic pathways and products. The core of this approach is the design of biomimetic models to study biomolecule behavior (lipids, nucleic acids and proteins) in aqueous systems, obtaining insights of the reaction pathways as well as building up molecular libraries of the free radical reaction products. This context can be successfully used for biomarker discovery and examples are provided with two classes of compounds: mono-trans isomers of cholesteryl esters, which are synthesized and used as references for detection in human plasma, and purine 5',8-cyclo-2'-deoxyribonucleosides, prepared and used as reference in the protocol for detection of such lesions in DNA samples, after ionizing radiations or obtained from different health conditions.

Radical-based biomimetic chemistry has been applied to building-up libraries necessary for biomarker development.

自由基化学生物学的化学行为，生物标记开发

The involvement of free radicals in life sciences has constantly increased with time and has been connected to several physiological and pathological ...

科研

化学

High-pressure Sapphire Cell for Phase Equilibria Measurements of CO2/Organic/Water Systems

The high pressure sapphire cell apparatus was constructed to visually determine the composition of multiphase systems without physical sampling. Specifically, the sapphire cell enables visual data collection from multiple loadings to solve a set of material balances to precisely determine phase composition. Ternary phase diagrams can then be established to determine the proportion of each component in each phase at a given condition. In principle, any ternary system can be studied although ternary systems (gas-liquid-liquid) are the specific examples discussed herein. For instance, the ternary THF-Water-CO2 system was studied at 25 and 40&#160;&#176;C and is described herein. Of key importance, this technique does not require sampling. Circumventing the possible disturbance of the system equilibrium upon sampling, inherent measurement errors, and technical difficulties of physically sampling under pressure is a significant benefit of this technique. Perhaps as important, the sapphire cell also enables the direct visual observation of the phase behavior. In fact, as the CO2 pressure is increased, the homogeneous THF-Water solution phase splits at about 2 MPa. With this technique, it was possible to easily and clearly observe the cloud point and determine the composition of the newly formed phases as a function of pressure.
The data acquired with the sapphire cell technique can be used for many applications. In our case, we measured swelling and composition for tunable solvents, like gas-expanded liquids, gas-expanded ionic liquids and Organic Aqueous Tunable Systems (OATS)1-4. For the latest system, OATS, the high-pressure sapphire cell enabled the study of (1) phase behavior as a function of pressure and temperature, (2) composition of each phase (gas-liquid-liquid) as a function of pressure and temperature and (3) catalyst partitioning in the two liquid phases as a function of pressure and composition. Finally, the sapphire cell is an especially effective tool to gather accurate and reproducible measurements in a timely fashion.

High-pressure Sapphire Cell for Phase Equilibria Measurements of CO2/Organic/Water Systems

The high pressure sapphire cell apparatus is a unique tool to study, without sampling, phase behavior under a wide range of pressures. Using a cathetometer, very precise volume measurements can be recorded to measure liquid expansion and phase composition. Thus, this synthetic method enables the study of (1) phase equilibria of multi-component mixtures and (2) the partition behavior of catalyst or model compounds as a function of pressure.

高压蓝宝石细胞对CO的相平衡测量<sub&gt; 2</sub&gt; /有机/水系统

The high pressure sapphire cell apparatus was constructed to visually determine the composition of multiphase systems without physical sampling. ...

Ethylene Polymerizations Using Parallel Pressure Reactors and a Kinetic Analysis of Chain Transfer Polymerization

We demonstrate a method for high-throughput catalyst screening using a parallel pressure reactor starting from the initial synthesis of a nickel &#945;-diimine ethylene polymerization catalyst. Initial polymerizations with the catalyst lead to optimized reaction conditions, including catalyst concentration, ethylene pressure and reaction time. Using gas-uptake data for these reactions, a procedure to calculate the initial rate of propagation (kp) is presented. Using the optimized conditions, the ability of the nickel &#945;-diimine polymerization catalyst to undergo chain transfer with diethylzinc (ZnEt2) during ethylene polymerization was investigated. A procedure to assess the ability of the catalyst to undergo chain transfer (from molecular weight and 13C NMR data), calculate the degree of chain transfer, and calculate chain transfer rates (ke) is presented.

A protocol for the high-throughput analysis of polymerization catalyst, chain transfer polymerizations, polyethylene characterization, and reaction kinetic analysis is presented.

乙烯聚合中使用并联电抗器的压力和链转移聚合的动力学分析

We demonstrate a method for high-throughput catalyst screening using a parallel pressure reactor starting from the initial synthesis of a nickel ...

Development of a Backbone Cyclic Peptide Library as Potential Antiparasitic Therapeutics Using Microwave Irradiation

Protein-protein interactions (PPIs) are intimately involved in almost all biological processes and are linked to many human diseases. Therefore, there is a major effort to target PPIs in basic research and in the pharmaceutical industry. Protein-protein interfaces are usually large, flat, and often lack pockets, complicating the discovery of small molecules that target such sites. Alternative targeting approaches using antibodies have limitations due to poor oral bioavailability, low cell-permeability, and production inefficiency.
Using peptides to target PPI interfaces has several advantages. Peptides have higher conformational flexibility, increased selectivity, and are generally inexpensive. However, peptides have their own limitations including poor stability and inefficiency crossing cell membranes. To overcome such limitations, peptide cyclization can be performed. Cyclization has been demonstrated to improve peptide selectivity, metabolic stability, and bioavailability. However, predicting the bioactive conformation of a cyclic peptide is not trivial. To overcome this challenge, one attractive approach it to screen a focused library to screen in which all backbone cyclic peptides have the same primary sequence, but differ in parameters that influence their conformation, such as ring size and position.
We describe a detailed protocol for synthesizing a library of backbone cyclic peptides targeting specific parasite PPIs. Using a rational design approach, we developed peptides derived from the scaffold protein Leishmania receptor for activated C-kinase (LACK). We hypothesized that sequences in LACK that are conserved in parasites, but not in the mammalian host homolog, may represent interaction sites for proteins that are critical for the parasites&#39; viability. The cyclic peptides were synthesized using microwave irradiation to reduce reaction times and increase efficiency. Developing a library of backbone cyclic peptides with different ring sizes facilitates a systematic screen for the most biological active conformation. This method provides a general, fast, and facile way to synthesize cyclic peptides.

A simple and general method for the synthesis of cyclic peptides using microwave irradiation is outlined. This procedure enables the synthesis of backbone cyclic peptides with a collection of different conformations while retaining the side chains and the pharmacophoric moieties., and therefore, allows to screen for the bioactive conformation.

一个主干环肽库作为潜在的抗寄生虫治疗微波辐射的发展

Protein-protein interactions (PPIs) are intimately involved in almost all biological processes and are linked to many human diseases. Therefore, there is ...

Synthesis and Characterization of Supramolecular Colloids

Control over colloidal assembly is of utmost importance for the development of functional colloidal materials with tailored structural and mechanical properties for applications in photonics, drug delivery and coating technology. Here we present a new family of colloidal building blocks, coined supramolecular colloids, whose self-assembly is controlled through surface-functionalization with a benzene-1,3,5-tricarboxamide (BTA) derived supramolecular moiety. Such BTAs interact via directional, strong, yet reversible hydrogen-bonds with other identical BTAs. Herein, a protocol is presented that describes how to couple these BTAs to colloids and how to quantify the number of coupling sites, which determines the multivalency of the supramolecular colloids. Light scattering measurements show that the refractive index of the colloids is almost matched with that of the solvent, which strongly reduces the van der Waals forces between the colloids. Before photo-activation, the colloids remain well dispersed, as the BTAs are equipped with a photo-labile group that blocks the formation of hydrogen-bonds. Controlled deprotection with UV-light activates the short-range hydrogen-bonds between the BTAs, which triggers the colloidal self-assembly. The evolution from the dispersed state to the clustered state is monitored by confocal microscopy. These results are further quantified by image analysis with simple routines using ImageJ and Matlab. This merger of supramolecular chemistry and colloidal science offers a direct route towards light- and thermo-responsive colloidal assembly encoded in the surface-grafted monolayer.

A protocol for the synthesis and characterization of colloids coated with supramolecular moieties is described. These supramolecular colloids undergo self-assembly upon the activation of the hydrogen-bonds between the surface-anchored molecules by UV-light.

超分子胶体的合成与表征

Control over colloidal assembly is of utmost importance for the development of functional colloidal materials with tailored structural and mechanical ...

Laser-heating and Radiance Spectrometry for the Study of Nuclear Materials in Conditions Simulating a Nuclear Power Plant Accident

Major and severe accidents have occurred three times in nuclear power plants (NPPs), at Three Mile Island (USA, 1979), Chernobyl (former USSR, 1986) and Fukushima (Japan, 2011). Research on the causes, dynamics, and consequences of these mishaps has been performed in a few laboratories worldwide in the last three decades. Common goals of such research activities are: the prevention of these kinds of accidents, both in existing and potential new nuclear power plants; the minimization of their eventual consequences; and ultimately, a full understanding of the real risks connected with NPPs. At the European Commission Joint Research Centre&#39;s Institute for Transuranium Elements, a laser-heating and fast radiance spectro-pyrometry facility is used for the laboratory simulation, on a small scale, of NPP core meltdown, the most common type of severe accident (SA) that can occur in a nuclear reactor as a consequence of a failure of the cooling system. This simulation tool permits fast and effective high-temperature measurements on real nuclear materials, such as plutonium and minor actinide-containing fission fuel samples. In this respect, and in its capability to produce large amount of data concerning materials under extreme conditions, the current experimental approach is certainly unique. For current and future concepts of NPP, example results are presented on the melting behavior of some different types of nuclear fuels: uranium-plutonium oxides, carbides, and nitrides. Results on the high-temperature interaction of oxide fuels with containment materials are also briefly shown.

We present experiments in which real nuclear fuel, cladding, and containment materials are laser heated to temperatures beyond 3,000 K while their behavior is studied by radiance spectroscopy and thermal analysis. These experiments simulate, on a laboratory scale, the formation of a lava-phase following a nuclear reactor core meltdown.

核材料在核电厂事故模拟条件下的激光加热和辐射光谱研究

Major and severe accidents have occurred three times in nuclear power plants (NPPs), at Three Mile Island (USA, 1979), Chernobyl (former USSR, 1986) and ...

Minimum Burning Pressures of Water-based Emulsion Explosives

This manuscript describes a protocol to measure the minimum pressure required for sustained burning of water-based emulsion explosives. Pumping water-based emulsion explosives for blasting applications can be very hazardous, as demonstrated by a number of pump accidents around the globe in the last decades, including some that resulted in fatalities. In Canada, the recognition of this hazard has led to the development of pumping guidelines that were endorsed by both the explosives industry and the Explosive Regulatory Division of the Canadian government. In these guidelines, it was noted that the minimum burning pressures (MBP) measured in a laboratory would provide a good guide to characterize the behaviour of these products in pumping systems. The same guidelines also call for the design of pump systems that prevent, whenever possible, pressures from exceeding the MBP of the product being pumped. At the time of publication of these guidelines, a methodology existed for measuring such MBP values but it had never been validated to measure the MBP of ammonium nitrate water-based emulsions (AWEs). AWEs are now used much more widely than any other water-based explosives and precursors in on-site bulk loading operations.
The Canadian Explosives Research Laboratory (CanmetCERL) has been conducting research over the last ten years to develop a validated testing protocol to measure and interpret representative MBP values for AWEs. The test, as it is performed today, will be described and the critical components will be justified by reference to recent published data. Results of MBP measurements, for a range of AWE products, will be presented. Inclusion of the MBP test in the test standards for the authorization of high explosives in Canada will also be discussed.

We present an apparatus based on hot-wire ignition in a pressurized enclosure and an associated methodology to measure the minimum pressure required to induce sustained combustion in water-based emulsion explosives. This method improves product characterization to allow one to use them more safely during pumping and mixing operations.

水性乳化炸药的最小燃烧压力

This manuscript describes a protocol to measure the minimum pressure required for sustained burning of water-based emulsion explosives. Pumping ...

Utilization of Stop-flow Micro-tubing Reactors for the Development of Organic Transformations

A new reaction screening technology for organic synthesis was recently demonstrated by combining elements from both continuous micro-flow and conventional batch reactors, coined stop-flow micro-tubing (SFMT) reactors. In SFMT, chemical reactions that require high pressure can be screened in parallel through a safer and convenient way. Cross-contamination, which is a common problem in reaction screening for continuous flow reactors, is avoided in SFMT. Moreover, the commercially available light-permeable micro-tubing can be incorporated into SFMT, serving as an excellent choice for light-mediated reactions due to a more effective uniform light exposure, compared to batch reactors. Overall, the SFMT reactor system is similar to continuous flow reactors and more superior than batch reactors for reactions that incorporate gas reagents and/or require light-illumination, which enables a simple but highly efficient reaction screening system. Furthermore, any successfully developed reaction in the SFMT reactor system can be conveniently translated to continuous-flow synthesis for large scale production.

A protocol for organic reaction screening using stop-flow micro-tubing (SFMT) reactors employing gaseous reactants and/or visible-light mediated reactions is presented.

停止流动微管反应器在有机转化发展中的应用

A new reaction screening technology for organic synthesis was recently demonstrated by combining elements from both continuous micro-flow and conventional ...

Reducing Willow Wood Fuel Emission by Low Temperature Microwave Assisted Hydrothermal Carbonization

Biomass is a sustainable fuel, as its CO2 emissions are reintegrated in biomass growth. However, the inorganic precursors in the biomass cause a negative environmental impact and slag formation. The selected short rotation coppice (SRC) willow wood has a high ash content (<img alt="Equation 1" src="/files/ftp_upload/58970/58970eq1.jpg" /> = 1.96%) and, therefore, a high content of emission and slag precursors. Therefore, the reduction of minerals from SRC willow wood by low temperature microwave assisted hydrothermal carbonization (MAHC) at 150 &#176;C, 170 &#176;C, and 185 &#176;C is investigated. An advantage of MAHC over conventional reactors is an even temperature conductance in the reaction medium, as microwaves penetrate the whole reactor volume. This allows a better temperature control and a faster cooldown. Therefore, a succession of depolymerization, transformation and repolymerization reactions can be analyzed effectively. In this study, the analysis of the mass loss, ash content and composition, heating values and molar O/C and H/C ratios of the treated and untreated SCR willow wood showed that the mineral content of the MAHC coal was reduced and the heating value increased. The process water showed a decreasing pH and contained furfural and 5-methylfurfural. A process temperature of 170 &#176;C showed the best combination of energy input and ash component reduction. The MAHC allows a better understanding of the hydrothermal carbonization process, while a large-scale industrial application is unlikely because of the high investment costs.

A protocol for the emission precursor depletion from low quality biomass by low temperature microwave assisted hydrothermal carbonization treatment is presented. This protocol includes the microwave parameters and the analysis of the biocoal product and process water.

低温微波辅助热液碳化降低柳树燃料排放

Biomass is a sustainable fuel, as its CO2 emissions are reintegrated in biomass growth. However, the inorganic precursors in the biomass cause a negative ...

Separation of Uranium and Thorium for 230Th-U Dating of Submarine Hydrothermal Sulfides

The age of a submarine hydrothermal sulfide is a significant index for estimating the size of hydrothermal ore deposits. Uranium and thorium isotopes in the samples can be separated for 230Th-U dating. This article presents a method to purify and separate U and Th isotopes in submarine hydrothermal sulfide samples. Following this technique, the separated U and Th fractions can meet measuring requirements by multi-collector inductively coupled plasma mass spectrometry (MC-ICPMS). The age of the hydrothermal sulfide sample can be calculated by measuring the present-day activity ratios of 230Th/238U and 234U/238U. A super clean room is necessary for this experiment. Cleaned regents and supplies are used to reduce the contamination during the sample processes. Balance, hotplate, and centrifuge are also used. The sulfide sample is powdered for analysis and less than 0.2 g sample is used. Briefly, the sample is weighed, dissolved, added to 229Th-233U-236U double spike solution, Fe co-precipitated, and separated on an anion-exchange resin extraction column. Approximately 50 ng U is consumed for 230Th-U dating of sulfides sample by MC-ICPMS.

Separation of Uranium and Thorium for 230Th-U Dating of Submarine Hydrothermal Sulfides

The protocol describes a method to purify and separate the U and Th nuclide in submarine hydrothermal sulfide sample with Fe co-precipitation and extraction chromatography for 230Th-U disequilibrium dating.

海底热液硫化物230Th-U测定铀和铀的分离

The age of a submarine hydrothermal sulfide is a significant index for estimating the size of hydrothermal ore deposits. Uranium and thorium isotopes in ...