Isothermal titration calorimetry in nanoliter droplets with subsecond time constants.

Isothermal titration calorimetry in nanoliter droplets with subsecond time constants.
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DOI:
10.1021/ac202026a
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发表时间:
2011-10-15
影响因子:
7.4
通讯作者:
Baudenbacher, Franz
Baudenbacher, Franz
中科院分区:
化学1区
文献类型:
--
作者:
Lubbers, Brad;Baudenbacher, Franz

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We reduced the reaction volume in microfabricated suspended-membrane titration calorimeters to nanoliter droplets and improved the sensitivities to below a nanowatt with time constants of around 100ms, The device performance was characterized using exothermic acid-base neutralizations and a detailed numerical model. The finite element based numerical model allowed us to determine the sensitivities within 1% and the temporal dynamics of the temperature rise in neutralization reactions as a function of droplet size. The model was used to determine the optimum calorimeter design (membrane size and thickness, junction area, and thermopile thickness) and sensitivities for sample volumes of 1 nl for silicon nitride and polymer membranes. We obtained a maximum sensitivity of 153 pW/√Hz for a 1 μm SiN membrane and 79 pW/√Hz for a 1 μm polymer membrane. The time constant of the calorimeter system was determined experimentally by using a pulsed laser to increase the temperature of nanoliter sample volumes. For a 2.5 nanoliter sample volume, we experimentally determined a noise equivalent power of 500 pW/√Hz and a 1/e time constant of 110ms for a modified commercially available infrared sensor with a thin-film thermopile. Furthermore, we demonstrated detection of 1.4 nJ reaction energies from injection of 25 pl of 1 mM HCl into a 2.5 nl droplet of 1 mM NaOH.
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