1。蓝宝石细胞大会<ol><li>放置一个116大小垫环和210尺寸O形圈到活塞。确认O形圈材料与组装前在实验过程中使用的化学品兼容。 <ol><li>有的垫环有一台和弧形边缘。如果是这样的话，将平坦的边缘向下和对O形环的弯曲边缘。 </li></ol></li><li>螺纹杆插入使用棒状带螺纹端头（ 图3），所述活塞的底部。 </li><li>换杆一层实验室毛巾（或其它非磨蚀实验室湿巾），以防止在插入活塞进入细胞划伤。 </li><li>插入在单元中的活塞。这个步骤可以是困难的，所以力必须被使用。然而，重要的是确保只有O形环进入与孔壁的接触是很重要的。 </li><li>将一个8210大小垫环和210尺寸O型圈到顶部和底部端盖（ 图4）。注:t他底端盖是在水一方的配件连接。要注意，虽然在插入端盖，仅将O形环进入与孔壁接触。 </li><li>对准端盖，并通过安装支架，并通过铝隔板插入两个螺栓。 </li><li>松散地连接螺母。 </li><li>通过铝垫片和端盖孔，将剩下的两个螺栓。 </li><li>松散地连接螺母。 </li><li>锁紧所有螺帽8-10英尺/磅的扭矩。 </li><li>贴装组电池到支架上，通过在蓝宝石池的底部，然后通过旋转轴旋拧螺栓旋转轴。 安全注意事项: <ol><li>贴装组电池，以使阀的顶部端盖（用于加样）的开口面向远离用户应灾难性故障发生。 </li><li>将针阀的顶端具体地说，从用户背对。 </li></ol></li><li>将所有的高压管件，管道和热电偶顶部和底部端盖。连接高压油管包括一个卸压阀，在蓝宝石小区的加压侧。位于所述压力释放阀远离用户和电气设备（压力释放将导致水的释放）。 </li></ol> 2。蓝宝石细胞的安全处理注意:不要处理蓝宝石电池用裸手的油从皮肤转移会导致微裂纹或划痕不要将蓝宝石细胞实验台未受保护的 。在坚硬的表面很可能会划伤细胞，或有细胞滚动的风险。 务必检查电池是否有裂纹或缺陷之前使用 。 压力下运行的单元格时，将空气浴在向下位置，空气浴有两个目的:（1）在必要时控制温度和（2），以提供对个人和增压内容物之间的阻挡万一发生灾难性故障的小区。 <ol><li> 压力测试蓝宝石细胞每12次压力循环，一个循环的压力正在增加高于大气压力，然后减压。如果不经常使用，压力测试细胞每四个月。完整的压力测试与操作侧全是水。 安全注意事项:压力测试必须与不可压缩流体（ 如水 ）应在设备故障，而在压力下完成。 <ol><li>附加充水高压注射泵到样品入口连接（在细胞的顶端）和完全填充的单元格。 </li><li>关闭进样阀。 </li><li>运行注射器泵，使得几滴水离开高压油管。这是为了确保没有空气是在之前的连接线。 </li><li>连接的管连接到所述蓝宝石细胞在蓝宝石细胞的底部嵌合。 </li><li>填写底部的电池与水量TØ加压，压力监测，以发现任何可能的压降。 </li><li>逐渐增加的压力为0.1MPa以上的压力释放阀的设定值。收集从所述压力释放阀在一个小容器释放的水。 </li><li>减压至大气压。 </li><li>重置减压阀和高压注射泵。 </li></ol></li></ol> 3。蓝宝石电池装置的操作<ol><li>填写高压注射泵约半满水。在将所需量的水将通过在该实验将要运行的压力来确定。注意:不要完全填充高压注射泵，以便在需要时，系统可以减压。 </li><li>运行的高压注射泵，使得几滴水离开管子。这是为了确保没有空气是在之前的连接线。 </li><li>将管路以蓝宝石细胞拟合。 </li><li>开气体入口阀。 </li><li>填充细胞与水，直到活塞是在一个水平上的液体高度可以与高差测定。注意:如果在气体入口阀未打开，系统将变得加压。 </li><li>关闭气体入口阀。 </li><li>附加的气密注射器向样品入口连接（打开）和由拉回10毫升撤离小区。 </li><li>关闭进样阀。 </li><li>稍微用力在气密注射器一边慢慢打开进样阀</li><li>通过使用连接到所述样品入口的气密注射器再次注入样品的体积。注意:取决于注射器尺寸，蓝宝石细胞可能需要在旋转轴被倒置的空气浴不能在细胞完全上文提出。 </li><li>关闭阀门。 </li><li>质量之前和之后添加样品的注射器中。通过之前和之后添加的记录的注射器的质量测量样品的量。有一个小错误ASSOCIAT编辑用这种方法，由于残留在管道和管件的未知量的试样。 </li><li>在所需的温度设定空气浴。 </li><li>允许样品达到平衡之前，采取第一高度测量的高差。为了确保达到平衡重复测量，直到没有变化观察至少3倍。达到平衡的时间在很大程度上取决于在系统上和范围可以从几分钟到几小时。在完成该系统是观察的时间（24小时）一段时间，以确保平衡已经取得了初步的研究。 </li><li>黄金线与CO 2。添加CO 2以第一运行高压注射泵，以排出任何空气从管线（未连接的入口阀）。 </li><li>连接管的气体入口阀。 </li><li>打开进气阀，以蓝宝石细胞。测量的CO 2的量加入到系统中，通过记录之前的高压注射泵的体积和<html>折后的CO 2加 。 </li><li>检查对水高压注射泵的流速为零（在达到平衡后），以确保没有泄漏。 </li><li>通过用高压注射泵调节加压流体（水）施加压力到所需的值。 </li></ol> 4。清洁蓝宝石细胞在完成实验，清洗蓝宝石细胞。用溶剂反复冲洗清洁单元。拆卸电池（见协议5）如果需要清洁。 <ol><li>注入大约10毫升溶剂，其中所述样品是可溶的。 </li><li>摇在旋转轴上的细胞以清洁墙壁和活塞。 </li><li>逆转蓝宝石细胞并打开样品入口阀来清空单元格的内容。 </li><li>重复步骤。 </li><li>重复步骤以丙酮为溶剂。 </li><li>干细胞:打开所有阀门和热空气浴。 </li></ol>E"&gt; 5。拆卸蓝宝石细胞<ol><li>拆下接头油管。注:水会流失从蓝宝石细胞的底部。从蓝宝石细胞取出活塞是困难的，如果它是半升的细胞一旦系统被拆除。 </li><li>跑回水进入高压注射泵。 <ol><li>关闭样品入口阀和加压使细胞与CO 2。 </li><li>笔芯高压注射泵（&lt;5毫升/分钟）。 </li><li>请勿重新填充高压注射泵如果小区没有加压。打开进气阀泄到罩:如果单元正在运行的水返回到高压泵后仍加压。 </li><li>拆下油管从蓝宝石细胞将水供给。 </li></ol></li><li>拧松螺母和垫片的螺栓。 </li><li>取出螺栓。确保没有金属接触到的细胞接触。 <ol><li>如果螺栓不容易出来，轻点螺栓。 </li><li>大科端盖直客不碰细胞。 </li></ol></li><li>带螺纹杆裹在毛巾取出活塞。 </li></ol>

<ol>
	<li>Hallett, J. P., Pollet, P., Eckert, C. A., Liotta, C. L. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Recycling+homogeneous+catalysts+for+sustainable+technology.">Recycling homogeneous catalysts for sustainable technology.</a> Catal. Org. React. 115, 395-404 (2007).</li><li>Hallett, J. 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=Hydroformylation+catalyst+recycle+with+gas-expanded+liquids.">Hydroformylation catalyst recycle with gas-expanded liquids.</a> Ind. Eng. Chem. Res. 47, 2585-2589 (2008).</li><li>Pollet, P., Hart, R. J., Eckert, C. A., Liotta, C. L. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Organic+Aqueous+Tunable+Solvents+(OATS):+A+Vehicle+for+Coupling+Reactions+and+Separations.">Organic Aqueous Tunable Solvents (OATS): A Vehicle for Coupling Reactions and Separations.</a> Accounts Chem. Res. 43, 1237-1245 (2010).</li><li>Fadhel, A. Z., 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=Exploiting+Phase+Behavior+for+Coupling+Homogeneous+Reactions+with+Heterogeneous+Separations+in+Sustainable+Production+of+Pharmaceuticals.">Exploiting Phase Behavior for Coupling Homogeneous Reactions with Heterogeneous Separations in Sustainable Production of Pharmaceuticals.</a> J. Chem. Eng. Data. 56, 1311-1315 (2011).</li><li>Briones, J. A., Mullins, J. C., Thies, M. C., Kim, B. U. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Ternary+Phase-Equilibria+for+Acetic+Acid-Water+Mixtures+with+Supercritical+Carbon+Dioxide.">Ternary Phase-Equilibria for Acetic Acid-Water Mixtures with Supercritical Carbon Dioxide.</a> Fluid Phase Equilib. 36, 235-246 (1987).</li><li>Wendland, M., Hasse, H., Maurer, G. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Multiphase+High-Pressure+Equilibria+of+Carbon-Dioxide-Water-Isopropanol.">Multiphase High-Pressure Equilibria of Carbon-Dioxide-Water-Isopropanol.</a> J. Supercrit. Fluid. 6, 211-222 (1993).</li><li>Traub, P., Stephan, K. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=High-Pressure+Phase-Equilibria+of+the+System+CO2+Water+Acetone+Measured+with+a+New+Apparatus.">High-Pressure Phase-Equilibria of the System CO2 Water Acetone Measured with a New Apparatus.</a> Chem. Eng. Sci. 45, 751-758 (1990).</li><li>Peng, D. -. Y., Robinson, D. B. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=A+New+Two-Constant+Equation+of+State.">A New Two-Constant Equation of State.</a> Ind. Eng. Chem. Fund. 15, 59-64 (1976).</li><li>Stryjek, R., Vera, J. H. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=PRSV+-+An+Improved+Peng-Robinson+Equation+of+State+with+New+Mixing+Rules+for+Strongly+Nonideal+Mixtures.">PRSV - An Improved Peng-Robinson Equation of State with New Mixing Rules for Strongly Nonideal Mixtures.</a> Can. J. Chem. Eng. 64, 334-340 (1986).</li><li>Michelsen, M. L. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=A+Modified+Huron-Vidal+Mixing+Rule+for+Cubic+Equations+of+State.">A Modified Huron-Vidal Mixing Rule for Cubic Equations of State.</a> Fluid Phase Equilib. 60, 213-219 (1990).</li><li>Lazzaroni, M. J., 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=High-pressure+phase+equilibria+of+some+carbon+dioxide-organic-water+systems.">High-pressure phase equilibria of some carbon dioxide-organic-water systems.</a> Fluid Phase Equilib. 224, 143-154 (2004).</li><li>Lazzaroni, M. J., Bush, D., Brown, J. S., Eckert, C. A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=High-pressure+vapor-liquid+equilbria+of+some+carbon+dioxide+plus+organic+binary+systems.">High-pressure vapor-liquid equilbria of some carbon dioxide plus organic binary systems.</a> J. Chem. Eng. Data. 50, 60-65 (2005).</li><li>Lazzaroni, M. J., Bush, D., Eckert, C. A., Glaser, R. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=High-pressure+vapor-liquid+equilibria+of+argon+plus+carbon+dioxide+2-propanol.">High-pressure vapor-liquid equilibria of argon plus carbon dioxide+2-propanol.</a> J. Supercrit. Fluid. 37, 135-141 (2006).</li><li>Laugier, S., Richon, D., Renon, H. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Simultaneous+Determination+of+Vapor-Liquid+Equilibiria+and+Volumetric+Properties+of+Ternary+Systems+with+a+New+Experimental+Apparatus.">Simultaneous Determination of Vapor-Liquid Equilibiria and Volumetric Properties of Ternary Systems with a New Experimental Apparatus.</a> Fluid Phase Equilib. 54, 19-34 (1990).</li><li>Fontalba, F., Richon, D., Renon, H. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Simultaneous+determination+of+vapor--liquid+equilibria+and+saturated+densities+up+to+45+MPa+and+433.">Simultaneous determination of vapor--liquid equilibria and saturated densities up to 45 MPa and 433.</a> 55, 944-951 (1984).</li><li>Lazzaroni, 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=.">.</a> Georgia Institute of Technology. , (2004).</li><li>Diandreth, J. R., Ritter, J. M., Paulaitis, M. E. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Experimental-Technique+for+Determining+Mixture+Compositions+and+Molar+Volumes+of+3+or+More+Equilibrium+Phases+at+Elevated+Pressures.">Experimental-Technique for Determining Mixture Compositions and Molar Volumes of 3 or More Equilibrium Phases at Elevated Pressures.</a> Ind. Eng. Chem. Res. 26, 337-343 (1987).</li></ol>

作者没有竞争的经济利益或利益冲突。

蓝宝石电池装置是用于测量相行为，而不采样一个独特的工具，从而平衡是不受到干扰。为了确保精确的可重复的数据，也有在协议中的关键步骤（协议第4题为"操作的蓝宝石电池装置"），必须遵守。对于其中相位成分的测量是任何系统中，关键是要达到在测量之前平衡。蓝宝石细胞被放置在一个旋转轴，有利于混合，以更迅速地达到平衡。三元体系由三部分组成和3相（气 - 液 - 液），在固定的...

当反应被用亲水性催化剂和一种疏水性底物进行的，以形成一种疏水性的产品，这是很常见的采用混合溶剂中，以提供一种均匀的反应体系中。例如，THF-水，乙腈 - 水，通常的混合溶剂中的车辆为这些均相反应方法。理想情况下，这将是有利的发展中，反应是在均相条件下后跟一个诱导相分离，分离水相和有机溶剂成分下所进行的处理。亲水性催化剂随​​后将被定位在该有机相，水相和疏水性的产品。整个过程可以使产品的一个浅显的分离/隔离和回收催化剂的方法。水性有机溶剂可调（OATS）提供车辆来完成这一战略。在开发OATS的第一步是了解有机 - 水溶液作为福的相行为的有机/水比例nction，CO 2压力和温度。相分离后，加入CO 2的（ 即在每个阶段的横溶解度）的效率是重要的量化。实际上从工艺的角度来看，交溶解度可以直接转换到的不希望的，各相产物与催化剂的损失。因此，知道相组成为压力的函数是"真实世界"的应用程序的关键信息。取样方法都可用; 5-7然而，从高压系统直接取样，可能会改变系统的平衡，并导致相分离或闪烁，作为在样品管路压力或温度的突然变化造成的。因此，不会干扰系统，并实现了快速采集和重现性数据的方法是可取的。高压蓝宝石电池装置的确是一个多功能的工具来测量相行为不必取样。 ü唱高差，非常精确的体积测量可以被记录下来。这些实验体积测量，然后用状态（妇女Stryjek和维拉的修改）的鹏罗宾逊三次方程使用和修改休伦-维达 ​​尔混合规则来有效地计算出体积膨胀和相成分随温度和压力8-10的函数。这种技术是专门设计用来测量气 - 液 - 液系统的相平衡。应该强调指出，蓝宝石电池不适合于研究涉及固体系统。带导向的实验条件为OATS介导的反应，分离和催化剂的回收的选择高压蓝宝石细胞获得的数据。此外，蓝宝石细胞也被用于（1）测量溶剂膨胀（或膨胀），作为CO 2的压力与有机溶剂和离子液体的功能，（2）确定在多相系统中催化剂的分区作为压力的函数，溶剂系统的温度和（3）了解在压力下进行的复杂反应体系的相行为。在此，我们报告的高压蓝宝石电池装置（1）的描述，（2）可能的局限性和安全预防措施，（3）在其运作的协议，并原则结果（4）具体的证明。 上面所讨论的高压蓝宝石细胞被定制（ 图1）。平衡单元包括一个中空的圆柱体蓝宝石（50.8毫米外径×25.4±0.0001毫米内径x203.2毫米升）。该单元被分为两个腔室由活塞分隔。底电池包含用作加压流体（染成蓝色用于展示）水和顶部单元格中包含的平衡组件（ 图2）。空气浴定制建造的有机玻璃，以适应特定的设置和引擎盖大小。该单元被放置在一个温度控制的空气浴，这是保持与一个数字式温度控制内LER。在空气浴的温度与热电偶（K型）和数字读数监控。还有一个额外的热电偶（K型）蓝宝石细胞内，这也是监控与数字读数。压力测定用压力换能器和数字读出。两个高压，500毫升，能够保持压力超过10MPa的注射泵进行所需的操作。第一高压注射泵包含用来向系统加压的水。第二高压泵被用于引入CO 2（或其它气体）的系统。进气口是在所述蓝宝石细胞的顶部。压力控制用高压注射泵，以实现在活塞两侧的压力平衡。该单元被安装在一个旋转轴上，并混合是通过手动旋转整个单元来实现。 液体和蒸气量是通过测量弯月形液面的高度与micromete计算ř高差。对于位移小于50毫米，精度为0.01毫米;较大的位移，其精度为0.1mm。

<table border="0" cellpadding="0" cellspacing="0" width="623">
	<colgroup>
		<col />
		<col />
	</colgroup>
	<tbody>
		<tr height="21">
			<td height="21" style="height:21px;width:245px;">Hollow sapphire cylinder</td>
			<td style="width:379px;">50.8 mm O.D. &#215; 25.4&#177;0.0001 mm I.D. &#215; 203.2 mm L</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">Pressurizing fluid</td>
			<td>Water</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">Syringe pumps</td>
			<td>Teledyne Isco Model 500D</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">Digital temperature controller</td>
			<td>Omega CN76000</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">Digital readouts</td>
			<td>HH-22 Omega</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">Thermocouples</td>
			<td>Omega Type K</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">Pressure transducer &#38; readout</td>
			<td>Druck, DPI 260, PDCR 910</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">CO2</td>
			<td>SCF grade</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">Cathetometer</td>
			<td>Gaertner Scientific corporation or any scientific lab suppliers.&#160;</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">Relief valve</td>
			<td>Spring loaded releive valve (swagelok)</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">mounting bracket</td>
			<td>UNISTRUT&#160; bracket</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">Hollow spacers</td>
			<td>3/4 inch</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">4 stainless steel bolts, 4 nuts, 2 washers</td>
			<td>3/4 inch</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">3 O-rings&#160;</td>
			<td>Kalrez, 210 size&#160;&#160;</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">3 backing rings&#160;</td>
			<td>116 size for piston; 2 8210 size for end caps</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">1 multi-port fitting</td>
			<td>HiP</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">High pressure tubing</td>
			<td>Stainless steel, 1/16 in.</td>
		</tr>
	</tbody>
</table>

high-pressure sapphire cell for phase equilibria measurements of co2/organic/water systems

高压蓝宝石电池设备构建直观判断多相系统的组成没有物理采样。具体而言，蓝宝石细胞能够可视化的​​数据收集从多个负载解决一系列重大结余的精确确定相组成。三元相图可以被建立，以确定在每个阶段中的每个组件在给定条件下的比重。原则上，任何三元体系可以研究虽然三元系统（气 - 液 - 液）是本文所讨论的具体实施例。例如，该三元THF-水-CO 2系统进行了研究，在25和40℃和在本文中描述。至关重要的，这种技术不需要取样。绕过采样后的系统平衡点的可能的干扰，固有测量误差，并在压力下物理采样的技术难点是这种技术的一个显著益处。 Perhaps重要的是，蓝宝石细胞还能够直接目视观察阶段的行为。事实上，由于CO 2的压力增加时，均质的THF-水的溶液相分裂在约2MPa。利用这种技术，有可能容易和清楚地观察到浊点，并确定新形成的相作为压力的函数的组合物。 与蓝宝石细胞技术所获得的数据可以用于多种应用。在我们的例子中，我们测得肿胀和组成的可调溶剂，如气体膨胀液体，气体膨胀离子液体和有机水性可调系统（OATS）1-4。为最新的系统，燕麦，高压蓝宝石细胞激活的（1）的相行为的研究作为压力和温度的函数，（2）组合物的各相（气 - 液 - 液），作为压力的函数，并温度，并在两个液相催化剂（3）划分为压力的函数肯定和组成。最后，蓝宝石细胞是收集及时准确，重现性测量的一个特别有效的工具。

高压蓝宝石单元的示意图示于图2中 ，随着细胞的照片。样品是在顶部电池和底部电池是水蓝色染料用于演示目的。液体成分经由注射器和阀供给，而​​CO 2（气体组分）是通过高压注射泵泵送。压力可通过活塞来控制（水​​也通过高压注射泵在我们的设置馈送）。在液相和气相中可以清楚地看出，在细胞中，活塞上方。活塞的组件中的协议描述，并基本上是构造成与螺纹...

Watch this Scientific Journal Video about High-pressure Sapphire Cell for Phase Equilibria Measurements of CO2/Organic/Water Systems at JoVE.com

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

高压蓝宝石电池装置是研究，没有采样，相态下的各种压力的唯一工具。利用高差，非常精确的体积测量可记录测量液体膨胀和相组成。因此，这种合成方法，使产生（1）相多组分混合物的相平衡研究及催化剂或模型化合物作为压力的函数（2）分区的行为。

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. ...

high-pressure-sapphire-cell-for-phase-equilibria-measurements

Research

Education

JoVE Core

JoVE Journal

Physics

Chemistry

Unit 1

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

The Kinetic Theory of Gases

SCIENTISTS IN ACTION

13.4K 次观看.  Georgia Institute of Technology. 高压蓝宝石电池装置是研究，没有采样，相态下的各种压力的唯一工具。利用高差，非常精确的体积测量可记录测量液体膨胀和相组成。因此，这种合成方法，使产生（1）相多组分混合物的相平衡研究及催化剂或模型化合物作为压力的函数（2）分区的行为。 

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

Determination of the Gas-phase Acidities of Oligopeptides

Amino acid residues located at different positions in folded proteins often exhibit different degrees of acidities. For example, a cysteine residue located at or near the N-terminus of a helix is often more acidic than that at or near the C-terminus 1-6. Although extensive experimental studies on the acid-base properties of peptides have been carried out in the condensed phase, in particular in aqueous solutions 6-8, the results are often complicated by solvent effects 7. In fact, most of the active sites in proteins are located near the interior region where solvent effects have been minimized 9,10. In order to understand intrinsic acid-base properties of peptides and proteins, it is important to perform the studies in a solvent-free environment.
We present a method to measure the acidities of oligopeptides in the gas-phase. We use a cysteine-containing oligopeptide, Ala3CysNH2 (A3CH), as the model compound. The measurements are based on the well-established extended Cooks kinetic method (Figure 1) 11-16. The experiments are carried out using a triple-quadrupole mass spectrometer interfaced with an electrospray ionization (ESI) ion source (Figure 2). For each peptide sample, several reference acids are selected. The reference acids are structurally similar organic compounds with known gas-phase acidities. A solution of the mixture of the peptide and a reference acid is introduced into the mass spectrometer, and a gas-phase proton-bound anionic cluster of peptide-reference acid is formed. The proton-bound cluster is mass isolated and subsequently fragmented via collision-induced dissociation (CID) experiments. The resulting fragment ion abundances are analyzed using a relationship between the acidities and the cluster ion dissociation kinetics. The gas-phase acidity of the peptide is then obtained by linear regression of the thermo-kinetic plots 17,18.
The method can be applied to a variety of molecular systems, including organic compounds, amino acids and their derivatives, oligonucleotides, and oligopeptides. By comparing the gas-phase acidities measured experimentally with those values calculated for different conformers, conformational effects on the acidities can be evaluated.

The determination of the gas-phase acidities of cysteine-containing oligopeptides is described. The experiments are performed using a triple quadrupole mass spectrometer. The relative acidities of the peptides are measured using collision-induced dissociation experiments, and the quantitative acidities are determined using the extended Cooks kinetic method.

寡肽测定气相酸性

Amino acid residues located at different positions in folded proteins often exhibit different degrees of acidities. For example, a cysteine residue ...

科研

化学

Synthetic Methodology for Asymmetric Ferrocene Derived Bio-conjugate Systems via Solid Phase Resin-based Methodology

Early detection is a key to successful treatment of most diseases, and is particularly imperative for the diagnosis and treatment of many types of cancer. The most common techniques utilized are imaging modalities such as Magnetic Resonance Imaging (MRI), Positron Emission Topography (PET), and Computed Topography (CT) and are optimal for understanding the physical structure of the disease but can only be performed once every four to six weeks due to the use of imaging agents and overall cost. With this in mind, the development of &#8220;point of care&#8221; techniques, such as biosensors, which evaluate the stage of disease and/or efficacy of treatment in the clinician&#8217;s office and do so in a timely manner, would revolutionize treatment protocols.1 As a means to exploring ferrocene based biosensors for the detection of biologically relevant molecules2, methods were developed to produce ferrocene-biotin bio-conjugates described herein. This report will focus on a biotin-ferrocene-cysteine system that can be immobilized on a gold surface.

The synthesis of asymmetric species of ferrocene is challenging using solution techniques. This report focuses on the methods carried out to produce a ferrocene-biotin bioconjugate using facile and clean reactions accomplished via solid-phase synthesis. Incorporation of a thiolate moiety is shown to impart the ability for immobilization on gold surfaces.

合成方法通过固相树脂为基础的方法不对称二茂铁产生的生物共轭系统

Early detection is a key to successful treatment of most diseases, and is particularly imperative for the diagnosis and treatment of many types of cancer. ...

High Precision Zinc Isotopic Measurements Applied to Mouse Organs

We present a procedure to measure with high precision zinc isotope ratios in mouse organs. Zinc is composed of 5 stable isotopes (64Zn, 66Zn, 67Zn, 68Zn and 70Zn) which are naturally fractionated between mouse organs. We first show how to dissolve the different organs in order to free the Zn atoms; this step is realized by a mixture of HNO3 and H2O2. We then purify the zinc atoms from all the other elements, in particular from isobaric interferences (e.g., Ni), by anion-exchange chromatography in a dilute HBr/HNO3 medium. These first two steps are performed in a clean laboratory using high purity chemicals. Finally, the isotope ratios are measured by using a multi-collector inductively-coupled-plasma mass-spectrometer, in low resolution. The samples are injected using a spray chamber and the isotopic fractionation induced by the mass-spectrometer is corrected by comparing the ratio of the samples to the ratio of a standard (standard bracketing technique).&#160;This full typical&#160;procedure produces an isotope ratio with a 50 ppm (2 s.d.) reproducibility.

We present the technique to measure with high precision zinc isotope ratios in mouse organs.

适用于鼠标机关高精度锌同位素测量

We present a procedure to measure with high precision zinc isotope ratios in mouse organs. Zinc is composed of 5 stable isotopes (64Zn, 66Zn, 67Zn, 68Zn ...

Dissolution Dynamic Nuclear Polarization Instrumentation for Real-time Enzymatic Reaction Rate Measurements by NMR

The main limitation of NMR-based investigations is low sensitivity. This prompts for long acquisition times, thus preventing real-time NMR measurements of metabolic transformations. Hyperpolarization via dissolution DNP circumvents part of the sensitivity issues thanks to the large out-of-equilibrium nuclear magnetization stemming from the electron-to-nucleus spin polarization transfer. The high NMR signal obtained can be used to monitor chemical reactions in real time. The downside of hyperpolarized NMR resides in the limited time window available for signal acquisition, which is usually on the order of the nuclear spin longitudinal relaxation time constant, T1, or, in favorable cases, on the order of the relaxation time constant associated with the singlet-state of coupled nuclei, TLLS. Cellular uptake of endogenous molecules and metabolic rates can provide essential information on tumor development and drug response. Numerous previous hyperpolarized NMR studies have demonstrated the relevancy of pyruvate as a metabolic substrate for monitoring enzymatic activity in vivo. This work provides a detailed description of the experimental setup and methods required for the study of enzymatic reactions, in particular the pyruvate-to-lactate conversion rate in presence of lactate dehydrogenase (LDH), by hyperpolarized NMR.

The sensitivity enhancement provided by dissolution dynamic nuclear polarization (DNP) enables following metabolic processes in real time by NMR and MRI. The characteristics and performances of a dedicated dissolution DNP setup designed for study enzymatic reactions are discussed.

溶出动态核极化仪器用NMR实时酶反应速率测量

The main limitation of NMR-based investigations is low sensitivity. This prompts for long acquisition times, thus preventing real-time NMR measurements of ...

High Pressure Single Crystal Diffraction at PX^2

In this report we describe detailed procedures for carrying out single crystal X-ray diffraction experiments with a diamond anvil cell (DAC) at the GSECARS 13-BM-C beamline at the Advanced Photon Source. The DAC program at 13-BM-C is part of the Partnership for Extreme Xtallography (PX^2) project. BX-90 type DACs with conical-type diamond anvils and backing plates are recommended for these experiments. The sample chamber should be loaded with noble gas to maintain a hydrostatic pressure environment. The sample is aligned to the rotation center of the diffraction goniometer. The MARCCD area detector is calibrated with a powder diffraction pattern from LaB6. The sample diffraction peaks are analyzed with the ATREX software program, and are then indexed with the RSV software program. RSV is used to refine the UB matrix of the single crystal, and with this information and the peak prediction function, more diffraction peaks can be located. Representative single crystal diffraction data from an omphacite (Ca0.51Na0.48)(Mg0.44Al0.44Fe2+0.14Fe3+0.02)Si2O6 sample were collected. Analysis of the data gave a monoclinic lattice with P2/n space group at 0.35 GPa, and the lattice parameters were found to be: a = 9.496 &#177;0.006 &#197;, b = 8.761 &#177;0.004 &#197;, c = 5.248 &#177;0.001 &#197;, &#946; = 105.06 &#177;0.03&#186;, &#945; = &#947; = 90&#186;.

In this report, we describe detailed procedures for carrying out single crystal X-ray diffraction experiments with a diamond anvil cell at the GSECARS 13-BM-C beamline at the Advanced Photon Source. ATREX and RSV programs are used to analyze the data.

高压单晶衍射PX ^ 2

In this report we describe detailed procedures for carrying out single crystal X-ray diffraction experiments with a diamond anvil cell (DAC) at the ...

A Straightforward Method for Glucosinolate Extraction and Analysis with High-pressure Liquid Chromatography (HPLC)

Glucosinolates are a well-studied and highly diverse class of natural plant compounds. They play important roles in plant resistance, rapeseed oil quality, food flavoring, and human health. The biological activity of glucosinolates is released upon tissue damage, when they are mixed with the enzyme myrosinase. This results in the formation of pungent and toxic breakdown products, such as isothiocyanates and nitriles. Currently, more than 130 structurally different glucosinolates have been identified. The chemical structure of the glucosinolate is an important determinant of the product that is formed, which in turn determines its biological activity. The latter may range from detrimental (e.g., progoitrin) to beneficial (e.g., glucoraphanin). Each glucosinolate-containing plant species has its own specific glucosinolate profile. For this reason, it is important to correctly identify and reliably quantify the different glucosinolates present in brassicaceous leaf, seed, and root crops or, for ecological studies, in their wild relatives. Here, we present a well-validated, targeted, and robust method to analyze glucosinolate profiles in a wide range of plant species and plant organs. Intact glucosinolates are extracted from ground plant materials with a methanol-water mixture at high temperatures to disable myrosinase activity. Thereafter, the resulting extract is brought onto an ion-exchange column for purification. After sulfatase treatment, the desulfoglucosinolates are eluted with water and the eluate is freeze-dried. The residue is taken up in an exact volume of water, which is analyzed by high-pressure liquid chromatography (HPLC) with a photodiode array (PDA) or ultraviolet (UV) detector. Detection and quantification are achieved by conducting comparisons of the retention times and UV spectra of commercial reference standards. The concentrations are calculated based on a sinigrin reference curve and well-established response factors. The advantages and disadvantages of this straightforward method, when compared to faster and more technologically advanced methods, are discussed here.

A Straightforward Method for Glucosinolate Extraction and Analysis with High-pressure Liquid Chromatography HPLC

Here, we describe in great detail an established and robust protocol for the extraction of glucosinolates from ground plant materials. After an on-column sulfatase treatment of the extracts, the desulfoglucosinolates are eluted and analyzed by high-pressure liquid chromatography.

简捷方法对硫甙的提取与分析用高压液相色谱法（HPLC）

Glucosinolates are a well-studied and highly diverse class of natural plant compounds. They play important roles in plant resistance, rapeseed oil ...

Measurements of Long-range Electronic Correlations During Femtosecond Diffraction Experiments Performed on Nanocrystals of Buckminsterfullerene

The precise details of the interaction of intense X-ray pulses with matter are a topic of intense interest to researchers attempting to interpret the results of femtosecond X-ray free electron laser (XFEL) experiments. An increasing number of experimental observations have shown that although nuclear motion can be negligible, given a short enough incident pulse duration, electronic motion cannot be ignored. The current and widely accepted models assume that although electrons undergo dynamics driven by interaction with the pulse, their motion could largely be considered &#39;random&#39;. This would then allow the supposedly incoherent contribution from the electronic motion to be treated as a continuous background signal and thus ignored. The original aim of our experiment was to precisely measure the change in intensity of individual Bragg peaks, due to X-ray induced electronic damage in a model system, crystalline C60. Contrary to this expectation, we observed that at the highest X-ray intensities, the electron dynamics in C60 were in fact highly correlated, and over sufficiently long distances that the positions of the Bragg reflections are significantly altered. This paper describes in detail the methods and protocols used for these experiments, which were conducted both at the Linac Coherent Light Source (LCLS) and the Australian Synchrotron (AS) as well as the crystallographic approaches used to analyse the data.

We describe an experiment designed to probe the electronic damage induced in nanocrystals of Buckminsterfullerene (C60) by intense, femtosecond pulses of X-rays. The experiment found that, surprisingly, rather than being stochastic, the X-ray induced electron dynamics in C60 are highly correlated, extending over hundreds of unit cells within the crystals1.

在纳米富勒的飞秒衍射实验的长程电子关联的测量

The precise details of the interaction of intense X-ray pulses with matter are a topic of intense interest to researchers attempting to interpret the ...

A Convenient Method for Extraction and Analysis with High-Pressure Liquid Chromatography of Catecholamine Neurotransmitters and Their Metabolites

The extraction and analysis of catecholamine neurotransmitters in biological fluids is of great importance in assessing nervous system function and related diseases, but their precise measurement is still a challenge. Many protocols have been described for neurotransmitter measurement by a variety of instruments, including high-pressure liquid chromatography (HPLC). However, there are shortcomings, such as complicated operation or hard-to-detect multiple targets, which cannot be avoided, and presently, the dominant analysis technique is still HPLC coupled with sensitive electrochemical or fluorimetric detection, due to its high sensitivity and good selectivity. Here, a detailed protocol is described for the pretreatment and detection of catecholamines with high pressure liquid chromatography with electrochemical detection (HPLC-ECD) in real urine samples of infants, using electrospun composite nanofibers composed of polymeric crown ether with polystyrene as adsorbent, also known as the packed-fiber solid phase extraction (PFSPE) method. We show how urine samples can be easily precleaned by a nanofiber-packed solid phase column, and how the analytes in the sample can be rapidly enriched, desorbed, and detected on an ECD system. PFSPE greatly simplifies the pretreatment procedures for biological samples, allowing for decreased time, expense, and reduction of the loss of targets. 
Overall, this work illustrates a simple and convenient protocol for solid-phase extraction coupled to an HPLC-ECD system for simultaneous determination of three monoamine neurotransmitters (norepinephrine (NE), epinephrine (E), dopamine (DA)) and two of their metabolites (3-methoxy-4-hydroxyphenylglycol (MHPG) and 3,4-dihydroxy-phenylacetic acid (DOPAC)) in infants' urine. The established protocol was applied to assess the differences of urinary catecholamines and their metabolites between high-risk infants with perinatal brain damage and healthy controls. Comparative analysis revealed a significant difference in urinary MHPG between the two groups, indicating that the catecholamine metabolites may be an important candidate marker for early diagnosis of cases at risk for brain damage in infants.

We present a convenient solid-phase extraction coupled to high-pressure liquid chromatography (HPLC) with electrochemical detection (ECD) for simultaneous determination of three monoamine neurotransmitters and two of their metabolites in infants' urine. We also identify the metabolite MHPG as a potential biomarker for the early diagnosis of brain damage for infants.

用高压液相色谱法提取和分析儿茶酚胺神经递质及其代谢物的简便方法

The extraction and analysis of catecholamine neurotransmitters in biological fluids is of great importance in assessing nervous system function and ...

Development and Validation of Chromium Getters for Solid Oxide Fuel Cell Power Systems

Degradation of cathode in solid oxide fuel cells (SOFC) remains a major concern for the long-term performance stability and operational reliability. The presence of gas phase chromium species in air has demonstrated significant cathode performance degradation during long-term exposure due to unwanted compound formation at the cathode and electrolyte interface which retards the oxygen reduction reaction (ORR). We have demonstrated a novel method to mitigate the cathode degradation using chromium getters which capture the gas phase chromium species before it is ingested in the cathode chamber. Low-cost getter materials, synthesized from alkaline earth and transition metal oxides, are coated on the cordierite honeycomb substrate for application in the SOFC power systems. As-fabricated getters have been screened by chromium transpiration tests for 500 h in humidified air atmosphere in presence of chromium vapor. Selected getters have been further validated utilizing electrochemical tests. Typically, electrochemical performance of SOFCs (lanthanum strontium manganite (LSM) &#449; yttria stabilized zirconia (YSZ) &#449; Pt) was measured at 850 &#176;C in the presence and absence of Cr getter. For the 100 h cell tests containing getters, stable electrochemical performance was maintained, whereas the cell performance in the absence of Cr getters rapidly decreased in 10 h. Analyses of Nyquist plots indicated significant increase in the polarization resistance within the first 10 h of the cell operation. Characterization results from posttest SOFCs and getters have demonstrated the high efficiency of chromium capture for the mitigation of cell degradation.

Cathode poisoning from airborne contaminants in trace levels remains a major concern for long-term stability of high-temperature electrochemical systems. We provide a novel method to mitigate the cathode degradations using getters, which capture airborne contaminants at high temperature before entering electrochemically active stack area.

固体氧化物燃料电池动力系统的铬获取器的开发和验证

Degradation of cathode in solid oxide fuel cells (SOFC) remains a major concern for the long-term performance stability and operational reliability. The ...

Ultrafast Time-resolved Near-IR Stimulated Raman Measurements of Functional &#960;-conjugate Systems

Femtosecond time-resolved stimulated Raman spectroscopy is a promising method of observing the structural dynamics of short-lived transients with near infrared (near-IR) transitions, because it can overcome the low sensitivity of spontaneous Raman spectrometers in the near-IR region. Here, we describe technical details of a femtosecond time-resolved near-IR multiplex stimulated Raman spectrometer that we have recently developed. A description of signal generation and optimization, measurement, data acquisition, and calibration and correction of recorded data is provided as well. We present an application of our spectrometer to analyze the excited-state dynamics of &#946;-carotene in toluene solution. A C=C stretch band of &#946;-carotene in the second lowest excited singlet (S2) state and the lowest excited singlet (S1) state is clearly observed in the recorded time-resolved stimulated Raman spectra. The femtosecond time-resolved near-IR stimulated Raman spectrometer is applicable to the structural dynamics of &#960;-conjugate systems from simple molecules to complex materials.

Details of signal generation and optimization, measurement, data acquisition, and data handling for a femtosecond time-resolved near-IR stimulated Raman spectrometer are described. A near infrared stimulated Raman study on the excited-state dynamics of &#946;-carotene in toluene is shown as a representative application.

超快时间解析近红外刺激拉曼测量功能 +偶联系统

Femtosecond time-resolved stimulated Raman spectroscopy is a promising method of observing the structural dynamics of short-lived transients with near ...