Theta-glass capillaries in electrospray ionization: rapid mixing and short droplet lifetimes.
Theta-glass capillaries in electrospray ionization: rapid mixing and short droplet lifetimes.
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DOI：
10.1021/ac502545r
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发表时间：
2014-09-16
影响因子：
7.4
通讯作者：
Williams, Evan R.
中科院分区：
文献类型：
--
作者：
Mortensen, Daniel N.;Williams, Evan R.
在电喷雾过程中，使用由theta玻璃毛细管制备的双管式毛细管式电喷雾发射器来混合溶液。用内标连续监测每桶的相对流率。18-冠-6与K+的络合反应在电喷雾过程中达到平衡，说明电喷雾也发生了完全混合。简化的扩散模型表明，混合发生在不到一毫秒的时间内，而根据弹道微滴聚合时间估计的湍流贡献表明，完全混合发生在几微秒内。这一混合时间比之前与质谱仪耦合的任何混合器都要短2个数量级。本文研究了L抗坏血酸还原2，6-二氯吲哚酚的反应，并用质谱仪进行了监测。根据该反应在本体液中的反应速率常数，得到S的表观反应时间为2 74±6 0μ。这一反应时间是液滴寿命的上限，因为液滴的表面积与体积比和试剂浓度随着液滴的蒸发而增加，并且一些产品在液滴形成之前在泰勒锥体中形成。根据其他人在液滴中测得的反应速度比在本体溶液中的反应速度增加，真正的液滴寿命可能比上限低1-3个数量级，即27μS到270 ns之间。在这些实验中实现的快速混合和短液滴寿命应该能够使用质谱学来监测许多不同的快速反应。
Double-barrel wire-in-a-capillary electrospray emitters prepared from theta-glass capillaries were used to mix solutions during the electrospray process. The relative flow rate of each barrel was continuously monitored with internal standards. The complexation reaction of 18-crown-6 and K+, introduced from opposite barrels, reaches equilibrium during the electrospray process, suggesting that complete mixing also occurs. A simplified diffusion model suggests that mixing occurs in less than a millisecond, and contributions of turbulence, estimated from times of coalescing ballistic microdroplets, suggest that complete mixing occurs within a few microseconds. This mixing time is 2 orders of magnitude less than in any mixer previously coupled to a mass spectrometer. The reduction of 2,6-dichloroindophenol by l-ascorbic acid was performed using the theta-glass emitters and monitored using mass spectrometry. On the basis of the rate constant of this reaction in bulk solution, an apparent reaction time of 274 ± 60 μs was obtained. This reaction time is an upper limit to the droplet lifetime because the surface area to volume ratio and the concentration of reagents increase as the droplet evaporates and some product formation occurs in the Taylor cone prior to droplet formation. On the basis of increases in reaction rates measured by others in droplets compared to rates in bulk solution, the true droplet lifetime is likely 1–3 orders of magnitude less than the upper limit, i.e., between 27 μs and 270 ns. The rapid mixing and short droplet lifetime achieved in these experiments should enable the monitoring of many different fast reactions using mass spectrometry.
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影响因子：
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