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WIREs Nanomed Nanobiotechnol
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Nanoscale thermal analysis for nanomedicine by nanocalorimetry

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Abstract Microfabricated nanocalorimeters sensitively measure the thermal properties of nanomaterials and can be used for biomedical and in vitro measurements. This review examines the capabilities of nanocalorimeters including specific applications to nanomedicine such as measurements of nanomaterial stability, protein crystallization, ligand–protein binding, phase transitions, phase separations, interfacial reactions, and sorption–desorption phenomena. Widespread adoption of nanotechnology into clinical medicine will require a more complete understanding of the basic properties of nanomaterials, the relationship between nanomaterial processing, and physical properties and a deeper understanding of how nanomaterial physical properties control biological interactions. Nanocalorimetry is suitable where high sensitivity and high‐rate thermal and thermodynamic measurements are needed. Because of their small size and rapid measurement speed, nanocalorimeters can be used for single measurements or with high throughput automation. WIREs Nanomed Nanobiotechnol 2012, 4:31–41. doi: 10.1002/wnan.155 This article is categorized under: Diagnostic Tools > Biosensing Therapeutic Approaches and Drug Discovery > Emerging Technologies Nanotechnology Approaches to Biology > Nanoscale Systems in Biology

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Chip‐based nanocalorimeters (a) design of a microfluidic nanocalorimeter on a parylene membrane with vacuum thermal isolation. (b) Enthalpy array based on a polyimide membrane with silicon thin‐film temperature sensors. (c) Photograph of a nanocalorimeter chip produced by the Allen group at the Cornell Nanofabrication Facility, similar chips are fabricated at the NIST Center for Nanoscale Science and Technology; these chips have a platinum heater that also serves as the temperature sensor on a silicon nitride membrane. (d) Photograph of a Xensor Integration chip with a small heater and thermopiles for temperature measurement. (Panel (a) reprinted with permission from Ref 4. Copyright 2009 National Academy of Sciences, USA; Panel (b) reprinted with permission from Ref 14. Copyright 2004 National Academy of Sciences, USA)

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Heat capacities of a Ni–Si interfacial reaction. The blue line is from a conventional differential scanning calorimeter (DSC) and the red line is based on nanocalorimetry measurements.

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Size dependence of the (a) melting points and (b) latent heat of fusion of Sn nanoparticles. The line is calculated and the points are measured. (Reprinted with permission from Ref 5. Copyright 1996 American Physical Society, http://prl.aps.org/abstract/PRL/v77/i1/p99_1)

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Crystallization of iPP at different cooling rates: 30, 60, 90, 120, 160, 200, 300, and 1000 K/second. (Source: provided by Prof. Christoph Schick).

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Enthalpy array signal. (a) Streptavidin–biotin binding reaction and (b) enzymatic phosphorylation (glucose‐hexokinase). The predicted peak height is based on the binding enthalpy and reaction conditions. (Reprinted with permission from Ref 14. Copyright 2004 National Academy of Sciences, USA)

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Nanocalorimetric measurement of urea hydrolysis with urease. The inset is the reaction energy. (Reprinted with permission from Ref 4. Copyright 2009 National Academy of Sciences, USA)

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Temperature uncertainty associated with measurements using ≈︁10 nL water droplets (no sample) with open chamber nanocalorimeters. A comparison to Figure 5 shows how critical 0.1 mK temperature resolution is for nanocalorimeter measurements. (a) 1 mK temperature drop and ≈︁0.02 mK/second apparent drift due to a difference in temperature between the water droplet released from a pipette and the chip surface followed by evaporation of water from the chip surface, (b) ≈︁0.14 mK temperature dip associated with a difference in temperature between a water droplet and the chip surface; a polydimethylsiloxane (PDMS) well restricts liquid movement here but adds to the thermal addenda.

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Measurements illustrating differences in methods, responses and testing environments. (a) Temperature versus applied power for two chips showing the differences in chip size and environment on thermal response. (b) Temperature versus time for a capacitive‐discharge nanocalorimeter chip for experiments with heating duration ranging from 8 to 60 milliseconds. The current limiting resistor was varied to reach the same maximum temperature with different pulse durations. For times longer than 20 milliseconds, the steady‐state heat losses dominate the response. (c) Measured temperature and voltage profile for a nanocalorimeter chip heated using a programed waveform; the shape of the voltage profile is based on theoretical device performance (equation based on Ref 19).

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Therapeutic Approaches and Drug Discovery > Emerging Technologies
Diagnostic Tools > Biosensing
Nanotechnology Approaches to Biology > Nanoscale Systems in Biology

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