Sample records for calorimetry

  1. Indirect calorimetry

    NARCIS (Netherlands)

    Gerrits, W.J.J.; Labussière, E.


    The use of indirect calorimetry to measure the heat production of men and animals has increased rapidly since the pioneering work of Lavoisier. Measurement of the consumption of oxygen and production of carbon dioxide are the basis for the measurement of heat production. Today, applications of indir

  2. Quantum Calorimetry (United States)

    Stahle, Caroline Kilbourne; McCammon, Dan; Irwin, Kent D.


    Your opponent's serve was almost perfect, but you vigorously returned it beyond his outstretched racquet to win the point. Now the tennis ball sits wedged in the chain-link fence around the court. What happened to the ball's kinetic energy? It has gone to heat the fence, of course, and you realize that if the fence were quite colder, you might be able to measure that heat and determine just how energetic your swing really was. Calorimetry has been a standard measurement technique since James Joule and Julius von Mayer independently concluded, about 150 years ago, that heat is a form of energy. But only in the past 15 years or so has calorimetry been applied, at millikelvin temperatures, to the measurement of the energy of individual photons and particles with exquisite sensitivity. In this article, we have tried to show that continuing research in low-temperature physics leads to a greater understanding of high-temperature astrophysics. Adaptations of the resulting spectrometers will be useful tool for fields of research beyond astrophysics.

  3. Dynamic Calorimetry for Students (United States)

    Kraftmakher, Yaakov


    A student experiment on dynamic calorimetry is described. Dynamic calorimetry is a powerful technique for calorimetric studies, especially at high temperatures and pressures. A low-power incandescent lamp serves as the sample. The ScienceWorkshop data-acquisition system with DataStudio software from PASCO Scientific displays the results of the…

  4. Dual-readout Calorimetry


    Akchurin, N.; Bedeschi, F.; Cardini, A.; Cascella, M.; Cei, F.; Pedis, D.; Fracchia, S.; Franchino, S.; Fraternali, M.; Gaudio, G.; P. Genova; Hauptman, J.; La Rotonda, L.; Lee, S.; Livan, M.(INFN Sezione di Pavia, Pavia, Italy)


    The RD52 Project at CERN is a pure instrumentation experiment whose goal is to understand the fundamental limitations to hadronic energy resolution, and other aspects of energy measurement, in high energy calorimeters. We have found that dual-readout calorimetry provides heretofore unprecedented information event-by-event for energy resolution, linearity of response, ease and robustness of calibration, fidelity of data, and particle identification, including energy lost to binding energy in n...

  5. Calorimetry Task Force Report

    CERN Document Server

    Abdullin, Salavat; Banerjee, Sunanda; Beauceron, Stephanie; Beaudette, Florian; Bhatti, Anwar; Chlebana, Frank; Cossutti, Fabio; Hirschauer, James; Ivanchenko, V; Jang, Dong Wook; Jun, Soon Yung; Kunori, Shuichi; Kroeger, Rob; Liu, Yanwen; Moeller, Anthony; Paulini, Manfred; Piperov, Stefan; Rahmat, Rahmat; Rovelli, Chiara; Safronov, Grigory; Sharma, Seema; Spiropulu, Maria; Yetkin, Taylan


    In this note we summarize the progress made by the calorimeter simulation task force (CaloTF) over the past year. The CaloTF was established in February 2008 in order to understand and reconcile the discrepancies observed between the CMS calorimetry simulation and test beam data recorded during 2004 and 2006. The simulation has been significantly improved by using a newer version of Geant4 and an improved physics list for the full CMS detector simulation. Simulation times have been reduced by introducing flexible parameterizations to describe showering in the calorimeter (using a Gflash-like approach) which have been tuned to the test beam data.

  6. Dual-readout Calorimetry

    CERN Document Server

    Akchurin, N; Cardini, A.; Cascella, M.; Cei, F.; De Pedis, D.; Fracchia, S.; Franchino, S.; Fraternali, M.; Gaudio, G.; Genova, P.; Hauptman, J.; La Rotonda, L.; Lee, S.; Livan, M.; Meoni, E.; Moggi, A.; Pinci, D.; Policicchio, A.; Saraiva, J.G.; Sill, A.; Venturelli, T.; Wigmans, R.


    The RD52 Project at CERN is a pure instrumentation experiment whose goal is to un- derstand the fundamental limitations to hadronic energy resolution, and other aspects of energy measurement, in high energy calorimeters. We have found that dual-readout calorimetry provides heretofore unprecedented information event-by-event for energy resolution, linearity of response, ease and robustness of calibration, fidelity of data, and particle identification, including energy lost to binding energy in nuclear break-up. We believe that hadronic energy resolutions of {\\sigma}/E $\\approx$ 1 - 2% are within reach for dual-readout calorimeters, enabling for the first time comparable measurement preci- sions on electrons, photons, muons, and quarks (jets). We briefly describe our current progress and near-term future plans. Complete information on all aspects of our work is available at the RD52 website

  7. Calorimetry of Nucleic Acids. (United States)

    Rozners, Eriks; Pilch, Daniel S; Egli, Martin


    This unit describes the application of calorimetry to characterize the thermodynamics of nucleic acids, specifically, the two major calorimetric methodologies that are currently employed: differential scanning (DSC) and isothermal titration calorimetry (ITC). DSC is used to study thermally induced order-disorder transitions in nucleic acids. A DSC instrument measures, as a function of temperature (T), the excess heat capacity (C(p)(ex)) of a nucleic acid solution relative to the same amount of buffer solution. From a single curve of C(p)(ex) versus T, one can derive the following information: the transition enthalpy (ΔH), entropy (ΔS), free energy (ΔG), and heat capacity (ΔCp); the state of the transition (two-state versus multistate); and the average size of the molecule that melts as a single thermodynamic entity (e.g., the duplex). ITC is used to study the hybridization of nucleic acid molecules at constant temperature. In an ITC experiment, small aliquots of a titrant nucleic acid solution (strand 1) are added to an analyte nucleic acid solution (strand 2), and the released heat is monitored. ITC yields the stoichiometry of the association reaction (n), the enthalpy of association (ΔH), the equilibrium association constant (K), and thus the free energy of association (ΔG). Once ΔH and ΔG are known, ΔS can also be derived. Repetition of the ITC experiment at a number of different temperatures yields the ΔCp for the association reaction from the temperature dependence of ΔH.

  8. Differential scanning calorimetry. (United States)

    Spink, Charles H


    Differential scanning calorimetry (DSC) has emerged as a powerful experimental technique for determining thermodynamic properties of biomacromolecules. The ability to monitor unfolding or phase transitions in proteins, polynucleotides, and lipid assemblies has not only provided data on thermodynamic stability for these important molecules, but also made it possible to examine the details of unfolding processes and to analyze the characteristics of intermediate states involved in the melting of biopolymers. The recent improvements in DSC instrumentation and software have generated new opportunities for the study of the effects of structure and changes in environment on the behavior of proteins, nucleic acids, and lipids. This review presents some of the details of application of DSC to the examination of the unfolding of biomolecules. After a brief introduction to DSC instrumentation used for the study of thermal transitions, the methods for obtaining basic thermodynamic information from the DSC curve are presented. Then, using DNA unfolding as an example, methods for the analysis of the melting transition are presented that allow deconvolution of the DSC curves to determine more subtle characteristics of the intermediate states involved in unfolding. Two types of transitions are presented for analysis, the first example being the unfolding of two large synthetic polynucleotides, which display high cooperativity in the melting process. The second example shows the application of DSC for the study of the unfolding of a simple hairpin oligonucleotide. Details of the data analysis are presented in a simple spreadsheet format.

  9. Combustion calorimetry experimental chemical thermodynamics

    CERN Document Server

    Sunner, Stig


    Combustion Calorimetry deals with expertise knowledge concerning the calorimetry of combustion reactions of an element or compound. After defining the use of units and physical constants, the book discusses the basic principles of combustion calorimetry and the various instruments and calorimeters used in the experiments to measure operations concerning temperatures and its time variations. One paper discusses the theory and design criteria of combustion calorimeter calibration. Another paper discusses the results obtained from a combustion calorimeter after it has measured the energy or entha

  10. Contactless Calorimetry for Levitated Samples (United States)

    Lee, M. C.; Dokko, W.


    Temperature and specific heat of hot sample measured with pyrometer in proposed experimental technique. Technique intended expecially for contactless calorimetry of such materials as undercooled molten alloys, samples of which must be levitated to prevent contamination and premature crystallization. Contactless calorimetry technique enables data to be taken over entire undercooling temperature range with only one sample. Technique proves valuable in study of undercooling because difference in specific heat between undercooled-liquid and crystalline phases at same temperature provides driving force to convert metastable undercooled phase to stable crystalline phase.

  11. Calorimetry at industrial electron accelerators

    DEFF Research Database (Denmark)

    Miller, Arne; Kovacs, A.


    Calorimetry is a convenient way to measure doses at industrial electron accelerators, where high absorbed doses (1-100 kGy) are delivered at dose rates of 102-105 Gy s-1 or even higher. Water calorimeters have been used for this purpose for several years, but recently other materials such as grap......Calorimetry is a convenient way to measure doses at industrial electron accelerators, where high absorbed doses (1-100 kGy) are delivered at dose rates of 102-105 Gy s-1 or even higher. Water calorimeters have been used for this purpose for several years, but recently other materials...

  12. Calorimetry fundamentals, instrumentation and applications

    CERN Document Server

    Sarge, Stefan M; Hemminger, Wolfgang


    Clearly divided into three parts, this practical book begins by dealing with all fundamental aspects of calorimetry. The second part looks at the equipment used and new developments. The third and final section provides measurement guidelines in order to obtain the best results. The result is optimized knowledge for users of this technique, supplemented with practical tips and tricks.

  13. Differential scanning calorimetry of coal (United States)

    Gold, P. I.


    Differential scanning calorimetry studies performed during the first year of this project demonstrated the occurrence of exothermic reactions associated with the production of volatile matter in or near the plastic region. The temperature and magnitude of the exothermic peak were observed to be strongly affected by the heating rate, sample mass and, to a lesser extent, by sample particle size. Thermal properties also were found to be influenced by oxidation of the coal sample due to weathering effects.

  14. Indirect calorimetry during incubation of hatching eggs

    NARCIS (Netherlands)

    Brand, van den H.; Heetkamp, M.J.W.; Kemp, B.


    Indirect calorimetry can be used during incubation of avian eggs to monitor the quality of the incubation process, the development of the embryo and the utilization of nutrients. Indirect calorimetry has several benefits above direct calorimetry, particularly in hatching eggs. However, to obtain rel

  15. Calorimetry of non-reacting systems

    CERN Document Server

    McCullough, John P


    Experimental Thermodynamics, Volume 1: Calorimetry of Non-Reacting Systems covers the heat capacity determinations for chemical substances in the solid, liquid, solution, and vapor states, at temperatures ranging from near the absolute zero to the highest at which calorimetry is feasible.This book is divided into 14 chapters. The first four chapters provide background information and general principles applicable to all types of calorimetry of non-reacting systems. The remaining 10 chapters deal with specific types of calorimetry. Most of the types of calorimetry treated are developed over a c

  16. Micromegas for imaging hadronic calorimetry

    CERN Document Server

    Adloff, C; Cap, S; Chefdeville, M; Dalmaz, A; Drancourt, C; Espargiliere, A; Gaglione, R; Gallet, R; Geffroy, N; Jacquemier, J; Karyotakis, Y; Peltier, F; Prast, J; Vouters, G


    The recent progress in R&D of the Micromegas detectors for hadronic calorimetry including new engineering-technical solutions, electronics development, and accompanying simulation studies with emphasis on the comparison of the physics performance of the analog and digital readout is described. The developed prototypes are with 2 bit digital readout to exploit the Micromegas proportional mode and thus improve the calorimeter linearity. In addition, measurements of detection efficiency, hit multiplicity, and energy shower profiles obtained during the exposure of small size prototypes to radioactive source quanta, cosmic particles and accelerator beams are reported. Eventually, the status of a large scale chamber (1{\\times}1 m2) are also presented with prospective towards the construction of a 1 m3 digital calorimeter consisting of 40 such chambers.

  17. Development of Quartz Fiber Calorimetry

    CERN Multimedia


    % RD40 \\\\ \\\\ Very Forward Calorimeters (VFCs) in LHC detectors should cover the pseudorapidity range from $\\eta$~=~2.5 to at least $\\eta$~=~5 in order to compute missing transverse energy and for jet tagging. Operation at such high rapidity requires the use of a calorimetry technique that is very radiation resistant, fast and insensitive to radioactivity (especially to neutrons). This can be accomplished through the Quartz-Calorimeter~(Q-Cal) concept of embedding silica core fibers, that resist to the Gigarad radiation level, into an absorber. In this calorimeter the shower particles produce light through the Cherenkov effect generating a signal less than 10~ns in duration. Unique to this new technology the visible energy of hadronic showers has a transverse dimension nearly an order of magnitude smaller than that in conventional calorimeters, enabling precise spatial resolution, sharper isolation cuts and better jet recognition against the minimum bias events background. Last but not least, most radioactive ...

  18. Automatic calorimetry system monitors RF power (United States)

    Harness, B. W.; Heiberger, E. C.


    Calorimetry system monitors the average power dissipated in a high power RF transmitter. Sensors measure the change in temperature and the flow rate of the coolant, while a multiplier computes the power dissipated in the RF load.

  19. Differential scanning calorimetry (DSC) of semicrystalline polymers. (United States)

    Schick, C


    Differential scanning calorimetry (DSC) is an effective analytical tool to characterize the physical properties of a polymer. DSC enables determination of melting, crystallization, and mesomorphic transition temperatures, and the corresponding enthalpy and entropy changes, and characterization of glass transition and other effects that show either changes in heat capacity or a latent heat. Calorimetry takes a special place among other methods. In addition to its simplicity and universality, the energy characteristics (heat capacity C(P) and its integral over temperature T--enthalpy H), measured via calorimetry, have a clear physical meaning even though sometimes interpretation may be difficult. With introduction of differential scanning calorimeters (DSC) in the early 1960s calorimetry became a standard tool in polymer science. The advantage of DSC compared with other calorimetric techniques lies in the broad dynamic range regarding heating and cooling rates, including isothermal and temperature-modulated operation. Today 12 orders of magnitude in scanning rate can be covered by combining different types of DSCs. Rates as low as 1 microK s(-1) are possible and at the other extreme heating and cooling at 1 MK s(-1) and higher is possible. The broad dynamic range is especially of interest for semicrystalline polymers because they are commonly far from equilibrium and phase transitions are strongly time (rate) dependent. Nevertheless, there are still several unsolved problems regarding calorimetry of polymers. I try to address a few of these, for example determination of baseline heat capacity, which is related to the problem of crystallinity determination by DSC, or the occurrence of multiple melting peaks. Possible solutions by using advanced calorimetric techniques, for example fast scanning and high frequency AC (temperature-modulated) calorimetry are discussed.

  20. Calorimetry and thermal methods in catalysis

    CERN Document Server

    Auroux, Aline


    The book is about calorimetry and thermal analysis methods, alone or linked to other techniques, as applied to the characterization of catalysts, supports and adsorbents, and to the study of catalytic reactions in various domains: air and wastewater treatment, clean and renewable energies, refining of hydrocarbons, green chemistry, hydrogen production and storage. The book is intended to fill the gap between the basic thermodynamic and kinetics concepts acquired by students during their academic formation, and the use of experimental techniques such as thermal analysis and calorimetry to answ

  1. Isothermal Titration Calorimetry in the Student Laboratory (United States)

    Wadso, Lars; Li, Yujing; Li, Xi


    Isothermal titration calorimetry (ITC) is the measurement of the heat produced by the stepwise addition of one substance to another. It is a common experimental technique, for example, in pharmaceutical science, to measure equilibrium constants and reaction enthalpies. We describe a stirring device and an injection pump that can be used with a…

  2. Final Technical Report CMS fast optical calorimetry

    Energy Technology Data Exchange (ETDEWEB)

    Winn, David R. [Fairfield Univ., CT (United States)


    This is the final report of CMS FAST OPTICAL CALORIMETRY, a grant to Fairfield University for development, construction, installation and operation of the forward calorimeter on CMS, and for upgrades of the forward and endcap calorimeters for higher luminosity and radiation damage amelioration.

  3. Calculation of Temperature Rise in Calorimetry. (United States)

    Canagaratna, Sebastian G.; Witt, Jerry


    Gives a simple but fuller account of the basis for accurately calculating temperature rise in calorimetry. Points out some misconceptions regarding these calculations. Describes two basic methods, the extrapolation to zero time and the equal area method. Discusses the theoretical basis of each and their underlying assumptions. (CW)

  4. HDTHe calorimetry v.1.0

    Energy Technology Data Exchange (ETDEWEB)


    The software generates predicted results of differential scanning calorimetry experiments for samples of palladium in a perforated capsule in an atmosphere containing a mixture of hydrogen isotopologues and helium. It can also be used to predict the results of absorption-desorption experiments at constant temperature and solid-phase isotopic ratio.

  5. Study of asphaltene precipitation by Calorimetry

    DEFF Research Database (Denmark)

    Verdier, Sylvain Charles Roland; Plantier, Frédéric; Bessières, David;


    of experiments showed that weak forces determine precipitation. Indeed, isothermal titration calorimetry could not detect any clear signal although this technique can detect low-energy transitions such as liquid-liquid equilibrium and rnicellization. The second series of tests proved that precipitation caused...

  6. Calibration and monitoring for crystal calorimetry

    CERN Document Server

    Zhu, Ren Yuan


    Crystal calorimetry provides excellent energy resolution in high energy and nuclear physics. The light output of heavy crystal scintillators, however, suffers from not negligible damage in radiation environment. A precision calibration and monitoring thus is crucial for maintaining crystal precision in situ. The performance of calibration and monitoring approaches used by BaBar, CLEO and L3 experiments are presented. The design and construction of a laser- based light monitoring system for CMS PWO calorimeter is also discussed.

  7. Foward Calorimetry in ALICE at LHC (United States)

    Chujo, Tatsuya; Alice Focal Collaboration


    We present an upgrade proposal for calorimetry in the forward direction, FOCAL, to measure direct photons in η = 3 . 3 - 5 . 3 in ALICE at the Large Hadron Collider (LHC). We suggest to use an electromagnetic calorimeter based on the novel technology of silicon sensors with W absorbers for photons, together with a conventional hadron calorimeter for jet measurements and photon isolation. The current status of the FOCAL R&D project will be presented.

  8. Scintillating Fibre Calorimetry at the LHC

    CERN Multimedia


    Good electromagnetic and hadronic calorimetry will play a central role in an LHC detector. The lead/scintillating fibre calorimeter technique provides a fast signal response well matched to the LHC rate requirements. It can be made to give equal response for electrons and hadrons (compensation) with good electromagnetic and hadronic energy resolutions.\\\\ \\\\ The aim of this R&D proposal is to study in detail the aspects that are relevant for application of this type of calorimeter in an LHC environment, including its integration in a larger system of detectors, e.g.~projective geometry, radiation hardness, light detection, calibration and stability monitoring, electron/hadron separation.....

  9. Isothermal calorimetry on enzymatic biodiesel production

    DEFF Research Database (Denmark)

    Fjerbæk, Lene


    information about effects taking place when using lipases immobilized on an inert carrier for transesterification of a triglyceride and an alcohol as for biodiesel production. The biodiesel is produced by rapeseed oil and methanol as well as ethanol and a commercial biocatalyst Novozym 435 from Novozymes...... containing a Candida Antarctica B lipase immobilized on an acrylic resin. The reaction investigated is characterized by immiscible liquids (oil, methanol, glycerol and biodiesel) and enzymes imm. on an inert carrier during reaction, which allows several effects to take place that during normal reaction...... conditions can not be elucidated. These effects have been observed with isothermal calorimetry bringing forth new information about the reaction of enzymes catalyzing transesterification. Enzymatic biodiesel production has until now not been investigated with isothermal microcalorimetry, but the results...

  10. Isothermal Titration Calorimetry to Characterize Enzymatic Reactions. (United States)

    Mazzei, Luca; Ciurli, Stefano; Zambelli, Barbara


    Isothermal titration calorimetry (ITC) is a technique that measures the heat released or absorbed during a chemical reaction as an intrinsic probe to characterize any chemical process that involves heat changes spontaneously occurring during the reaction. The general features of this method to determine the kinetic and thermodynamic parameters of enzymatic reactions (kcat, KM, ΔH) are described and discussed here together with some detailed applications to specific cases. ITC does not require any modification or labeling of the system under analysis, can be performed in solution, and needs only small amounts of enzyme. These properties make ITC an invaluable, powerful, and unique tool to extend the knowledge of enzyme kinetics to drug discovery.

  11. Isothermal Titration Calorimetry of Chiral Polymeric Nanoparticles. (United States)

    Werber, Liora; Preiss, Laura C; Landfester, Katharina; Muñoz-Espí, Rafael; Mastai, Yitzhak


    Chiral polymeric nanoparticles are of prime importance, mainly due to their enantioselective potential, for many applications such as catalysis and chiral separation in chromatography. In this article we report on the preparation of chiral polymeric nanoparticles by miniemulsion polymerization. In addition, we describe the use of isothermal titration calorimetry (ITC) to measure the chiral interactions and the energetics of the adsorption of enantiomers from aqueous solutions onto chiral polymeric nanoparticles. The characterization of chirality in nano-systems is a very challenging task; here, we demonstrate that ITC can be used to accurately determine the thermodynamic parameters associated with the chiral interactions of nanoparticles. The use of ITC to measure the energetics of chiral interactions and recognition at the surfaces of chiral nanoparticles can be applied to other nanoscale chiral systems and can provide further insight into the chiral discrimination processes of nanomaterials.

  12. Pressure perturbation calorimetry of unfolded proteins. (United States)

    Tsamaloukas, Alekos D; Pyzocha, Neena K; Makhatadze, George I


    We report the application of pressure perturbation calorimetry (PPC) to study unfolded proteins. Using PPC we have measured the temperature dependence of the thermal expansion coefficient, α(T), in the unfolded state of apocytochrome C and reduced BPTI. We have shown that α(T) is a nonlinear function and decreases with increasing temperature. The decrease is most significant in the low (2-55 °C) temperature range. We have also tested an empirical additivity approach to predict α(T) of unfolded state from the amino acid sequence using α(T) values for individual amino acids. A comparison of the experimental and calculated functions shows a very good agreement, both in absolute values of α(T) and in its temperature dependence. Such an agreement suggests the applicability of using empirical calculations to predict α(T) of any unfolded protein.

  13. Calorimetry for Fast Authentication of Edible Oils (United States)

    Angiuli, Marco; Bussolino, Gian Carlo; Ferrari, Carlo; Matteoli, Enrico; Righetti, Maria Cristina; Salvetti, Giuseppe; Tombari, Elpidio


    There are little data in the literature on how to authenticate edible oils through calorimetry techniques. However, oil melting curves can be used to represent correlations between calorimetric results and oil quality. A calorimetric method has been developed for studying the solid-liquid phase transitions of olive oil and seed oils, in which melting peak behavior is correlated to the type, quality, and composition of the oil. Good reproducible thermograms were obtained by defining precise protocols for use in testing, which take into account the specific characteristics of a particular oil. This approach does not replace classical analytical methods; nevertheless, it is believed that calorimetric tests could be a useful preliminary stage for quality testing. The calorimetric technique allows the detection of the adulterant (seed oils or refined olive oil), oil origin, and possible photo-oxidation degradation processes, before more complex and expensive procedures and analyses are applied.

  14. Differential scanning calorimetry techniques: applications in biology and nanoscience. (United States)

    Gill, Pooria; Moghadam, Tahereh Tohidi; Ranjbar, Bijan


    This paper reviews the best-known differential scanning calorimetries (DSCs), such as conventional DSC, microelectromechanical systems-DSC, infrared-heated DSC, modulated-temperature DSC, gas flow-modulated DSC, parallel-nano DSC, pressure perturbation calorimetry, self-reference DSC, and high-performance DSC. Also, we describe here the most extensive applications of DSC in biology and nanoscience.

  15. Current status of tritium calorimetry at TLK

    Energy Technology Data Exchange (ETDEWEB)

    Buekki-Deme, A.; Alecu, C.G.; Kloppe, B.; Bornschein, B. [Institute of Technical Physics, Tritium Laboratory Karsruhe - TLK, Karlsruhe Institute of Technology - KIT, Karlsruhe (Germany)


    Inside a tritium facility, calorimetry is an important analytical method as it is the only reference method for accountancy (it is based on the measurement of the heat generated by the radioactive decay). Presently, at Tritium Laboratory Karlsruhe (TLK), 4 calorimeters are in operation, one of isothermal type and three of inertial guidance control type (IGC). The volume of the calorimeters varies between 0.5 and 20.6 liters. About two years ago we started an extensive work to improve our calorimeters with regard to reliability and precision. We were forced to upgrade 3 of our 4 calorimeters due to the outdated interfaces and software. This work involved creating new LabView programs driving the devices, re-tuning control loops and replacing obsolete hardware components. In this paper we give a review on the current performance of our calorimeters, comparing it to recently available devices from the market and in the literature. We also show some ideas for a next generation calorimeter based on experiences with our IGC calorimeters and other devices reported in the literature. (authors)

  16. Determination of Purity by Differential Scanning Calorimetry (DSC). (United States)

    Brown, M. E.


    An exercise is presented which demonstrates the determination of sample purity by differential scanning calorimetry. Data and references are provided to enable the exercise to be carried out as a dry-lab experiment. (BB)

  17. Standard Procedure for Calibrating an Areal Calorimetry Based Dosimeter (United States)


    unlimited (P.A. Case No. TSRL-PA-2015-0136, 24 Sep 15). REFERENCES Beason, C. W. (2005). CLT As A Calorimeter. PowerPoint presentation dated 10 January...or sell any patented invention that may relate to them. This report was cleared for public release by the 88th ABW Public Affairs Office and presented for calibrating an areal calorimetry-based dosimeter. A detailed example of calibrating an areal calorimetry-based dosimeter is

  18. Continuing Studies on Lead/Scintillating Fibres Calorimetry (LFC)

    CERN Multimedia


    Starting from the results obtained in the framework of the LAA Project~2B, we propose a continuation of the R&D on lead/scintillating fibres calorimetry (``spaghetti calorimetry''), including further tests on the old calorimeter prototypes and the construction and testing of new prototypes. The main results we pursue concern the performances of a projective calorimeter built with new, cheaper, techniques and the radiation hardness of the scintillating fibres, the optimization of a preshower detector system is also studied.

  19. Application and use of isothermal calorimetry in pharmaceutical development. (United States)

    O'Neill, Michael A A; Gaisford, Simon


    There are many steps involved in developing a drug candidate into a formulated medicine and many involve analysis of chemical interaction or physical change. Calorimetry is particularly suited to such analyses as it offers the capacity to observe and quantify both chemical and physical changes in virtually any sample. Differential scanning calorimetry (DSC) is ubiquitous in pharmaceutical development, but the related technique of isothermal calorimetry (IC) is complementary and can be used to investigate a range of processes not amenable to analysis by DSC. Typically, IC is used for longer-term stability indicating or excipient compatibility assays because both the temperature and relative humidity (RH) in the sample ampoule can be controlled. However, instrument design and configuration, such as titration, gas perfusion or ampoule-breaking (solution) calorimetry, allow quantification of more specific values, such as binding enthalpies, heats of solution and quantification of amorphous content. As ever, instrument selection, experiment design and sample preparation are critical to ensuring the relevance of any data recorded. This article reviews the use of isothermal, titration, gas-perfusion and solution calorimetry in the context of pharmaceutical development, with a focus on instrument and experimental design factors, highlighted with examples from the recent literature.

  20. Perfusion calorimetry in the characterization of solvates forming isomorphic desolvates. (United States)

    Baronsky, Julia; Preu, Martina; Traeubel, Michael; Urbanetz, Nora Anne


    In this study, the potential of perfusion calorimetry in the characterization of solvates forming isomorphic desolvates was investigated. Perfusion calorimetry was used to expose different hydrates forming isomorphic desolvates (emodepside hydrates II-IV, erythromycin A dihydrate and spirapril hydrochloride monohydrate) to stepwise increasing relative vapour pressures (RVP) of water and methanol, respectively, while measuring thermal activity. Furthermore, the suitability of perfusion calorimetry to distinguish the transformation of a desolvate into an isomorphic solvate from the adsorption of solvent molecules to crystal surfaces as well as from solvate formation that is accompanied by structural rearrangement was investigated. Changes in the samples were confirmed using FT-Raman and FT-IR spectroscopy. Perfusion calorimetry indicates the transformation of a desolvate into an isomorphic solvate by a substantial exothermic, peak-shaped heat flow curve at low RVP which reflects the rapid incorporation of solvent molecules by the desolvate to fill the structural voids in the lattice. In contrast, adsorption of solvent molecules to crystal surfaces is associated with distinctly smaller heat changes whereas solvate formation accompanied by structural changes is characterized by an elongated heat flow. Hence, perfusion calorimetry is a valuable tool in the characterization of solvates forming isomorphic desolvates which represents a new field of application for the method.

  1. Application of solution calorimetry in pharmaceutical and biopharmaceutical research. (United States)

    Royall, P G; Gaisford, S


    In solution calorimetry the heat of solution (Delta(sol)H) is recorded as a solute (usually a solid) dissolves in an excess of solvent. Such measurements are valuable during all the phases of pharmaceutical formulation and the number of applications of the technique is growing. For instance, solution calorimetry is extremely useful during preformulation for the detection and quantification of polymorphs, degrees of crystallinity and percent amorphous content; knowledge of all of these parameters is essential in order to exert control over the manufacture and subsequent performance of a solid pharmaceutical. Careful experimental design and data interpretation also allows the measurement of the enthalpy of transfer (Delta(trans)H) of a solute between two phases. Because solution calorimetry does not require optically transparent solutions, and can be used to study cloudy or turbid solutions or suspensions directly, measurement of Delta(trans)H affords the opportunity to study the partitioning of drugs into, and across, biological membranes. It also allows the in-situ study of cellular systems. Furthermore, novel experimental methodologies have led to the increasing use of solution calorimetry to study a wider range of phenomena, such as the precipitation of drugs from supersaturated solutions or the formation of liposomes from phospholipid films. It is the purpose of this review to discuss some of these applications, in the context of pharmaceutical formulation and preformulation, and highlight some of the potential future areas where solution calorimetry might find applications.

  2. Liquid Argon Calorimetry with LHC-Performance Specifications

    CERN Multimedia


    % RD-3 Liquid Argon Calorimetry with LHC-Performance Specifications \\\\ \\\\Good electromagnetic and hadronic calorimetry will play a central role in an LHC detector. Among the techniques used so far, or under development, the liquid argon sampling calorimetry offers high radiation resistence, good energy resolution (electromagnetic and hadronic), excellent calibration stability and response uniformity. Its rate capabilities, however, do not yet match the requirements for LHC. \\\\ \\\\The aim of this proposal is to improve the technique in such a way that high granularity, good hermiticity and adequate rate capabilities are obtained, without compromising the above mentioned properties. To reach this goal, we propose to use a novel structure, the $^{\\prime\\prime}$accordion$^{\\prime\\prime}$, coupled to fast preamplifiers working at liquid argon temperature. Converter and readout electrodes are no longer planar and perpendicular to particles, as usual, but instead they are wiggled around a plane containing particles. ...

  3. Oxygen Consumption Rate and Energy Expenditure in Mice: Indirect Calorimetry. (United States)

    Kim, Eun Ran; Tong, Qingchun


    Global obesity epidemic demands more effective therapeutic treatments and better understanding of obesity pathophysiology. Since obesity results from energy imbalance, accurate quantification of energy intake and energy expenditure (EE) becomes an essential prerequisite to phenotype the cause for obesity development. Indirect calorimetry has long been used as one of the most established methods in EE quantification by detecting changes in levels of O2 consumption and CO2 production. In this article, we describe procedures and important considerations for an effective measurement using indirect calorimetry.

  4. Characterization of Novel Operation Modes for Secondary Emission Ionization Calorimetry (United States)

    Tiras, Emrah; Dilsiz, Kamuran; Ogul, Hasan; Snyder, Christina; Bilki, Burak; Onel, Yasar; Winn, David


    Secondary Emission (SE) Ionization Calorimetry is a novel technique to measure electromagnetic showers in high radiation environments. We have developed new operation modes by modifying the bias of the conventional PMT circuits. Hamamatsu single anode R7761 and multi-anode R5900-00-M16 Photomultiplier Tubes (PMTs) with modified bases are used as SE detector modules in our SE calorimetry prototype. In this detector module, the first dynode is used as the active media as opposed to photocathode. Here, we report the technical design of new modes and characterization measurements for both SE and PMT modes.

  5. Differential scanning calorimetry on mixtures of lecithin, lysolecithin and cholesterol

    NARCIS (Netherlands)

    Klopfenstein, W.E.; Kruyff, B. de; Verkleij, A.J.; Demel, R.A.; Deenen, L.L.M. van


    The effect of increasing concentrations of lysolecithin (1-palmitoyl-sn-glycerol-3-phosphorylcholine) on the gel → liquid crystal thermal transition of lecithin (1,2-dipalmitoyl-sn-glycerol-3-phosphorylcholine) in the aqueous phase was studied by differential scanning calorimetry (DSC). Lysolecithin

  6. Isothermal Titration Calorimetry Can Provide Critical Thinking Opportunities (United States)

    Moore, Dale E.; Goode, David R.; Seney, Caryn S.; Boatwright, Jennifer M.


    College chemistry faculties might not have considered including isothermal titration calorimetry (ITC) in their majors' curriculum because experimental data from this instrumental method are often analyzed via automation (software). However, the software-based data analysis can be replaced with a spreadsheet-based analysis that is readily…

  7. Preparation of Solid Derivatives by Differential Scanning Calorimetry. (United States)

    Crandall, E. W.; Pennington, Maxine


    Describes the preparation of selected aldehydes and ketones, alcohols, amines, phenols, haloalkanes, and tertiaryamines by differential scanning calorimetry. Technique is advantageous because formation of the reaction product occurs and the melting point of the product is obtained on the same sample in a short time with no additional purification…

  8. Differential Binding Models for Direct and Reverse Isothermal Titration Calorimetry. (United States)

    Herrera, Isaac; Winnik, Mitchell A


    Isothermal titration calorimetry (ITC) is a technique to measure the stoichiometry and thermodynamics from binding experiments. Identifying an appropriate mathematical model to evaluate titration curves of receptors with multiple sites is challenging, particularly when the stoichiometry or binding mechanism is not available. In a recent theoretical study, we presented a differential binding model (DBM) to study calorimetry titrations independently of the interaction among the binding sites (Herrera, I.; Winnik, M. A. J. Phys. Chem. B 2013, 117, 8659-8672). Here, we build upon our DBM and show its practical application to evaluate calorimetry titrations of receptors with multiple sites independently of the titration direction. Specifically, we present a set of ordinary differential equations (ODEs) with the general form d[S]/dV that can be integrated numerically to calculate the equilibrium concentrations of free and bound species S at every injection step and, subsequently, to evaluate the volume-normalized heat signal (δQ(V) = δq/dV) of direct and reverse calorimetry titrations. Additionally, we identify factors that influence the shape of the titration curve and can be used to optimize the initial concentrations of titrant and analyte. We demonstrate the flexibility of our updated DBM by applying these differentials and a global regression analysis to direct and reverse calorimetric titrations of gadolinium ions with multidentate ligands of increasing denticity, namely, diglycolic acid (DGA), citric acid (CIT), and nitrilotriacetic acid (NTA), and use statistical tests to validate the stoichiometries for the metal-ligand pairs studied.

  9. A study of ultra-strength polymer fibers via calorimetry (United States)

    Egorov, V. M.; Boiko, Yu. M.; Marikhin, V. A.; Myasnikova, L. P.; Radovanova, E. I.


    Xerogel reactor powders and supramolecular polyethylene fibers with various degrees of hood have been studied via differential scanning calorimetry. A higher strength of laboratory fibers in comparison with industrial ones is found to be achieved due to a multistage band high-temperature hood that causes the thermodynamic parameters of supramolecular polymer structure.

  10. What does calorimetry and thermodynamics of living cells tell us? (United States)

    Maskow, Thomas; Paufler, Sven


    This article presents and compares several thermodynamic methods for the quantitative interpretation of data from calorimetric measurements. Heat generation and absorption are universal features of microbial growth and product formation as well as of cell cultures from animals, plants and insects. The heat production rate reflects metabolic changes in real time and is measurable on-line. The detection limit of commercially available calorimetric instruments can be low enough to measure the heat of 100,000 aerobically growing bacteria or of 100 myocardial cells. Heat can be monitored in reaction vessels ranging from a few nanoliters up to many cubic meters. Most important the heat flux measurement does not interfere with the biological process under investigation. The practical advantages of calorimetry include the waiver of labeling and reactants. It is further possible to assemble the thermal transducer in a protected way that reduces aging and thereby signal drifts. Calorimetry works with optically opaque solutions. All of these advantages make calorimetry an interesting method for many applications in medicine, environmental sciences, ecology, biochemistry and biotechnology, just to mention a few. However, in many cases the heat signal is merely used to monitor biological processes but only rarely to quantitatively interpret the data. Therefore, a significant proportion of the information potential of calorimetry remains unutilized. To fill this information gap and to motivate the reader using the full information potential of calorimetry, various methods for quantitative data interpretations are presented, evaluated and compared with each other. Possible errors of interpretation and limitations of quantitative data analysis are also discussed.

  11. The Simulation of the ATLAS Liquid Argon Calorimetry

    CERN Document Server

    Archambault, J P; Carli, T; Costanzo, D; Dell'Acqua, A; Djama, F; Gallas, M; Fincke-Keeler, M; Khakzad, M; Kiryunin, A; Krieger, P; Leltchouk, M; Loch, P; Ma, H; Menke, S; Monnier, E; Nairz, A; Niess, V; Oakham, G; Oram, C; Pospelov, G; Rajagopalan, S; Rimoldi, A; Rousseau, D; Rutherfoord, J; Seligman, W; Soukharev, A; Strízenec, P; Tóth, J; Tsukerman, I; Tsulaia, V; Unal, G; Grahn, K J


    In ATLAS, all of the electromagnetic calorimetry and part of the hadronic calorimetry is performed by a calorimeter system using liquid argon as the active material, together with various types of absorbers. The liquid argon calorimeter consists of four subsystems: the electromagnetic barrel and endcap accordion calorimeters; the hadronic endcap calorimeters, and the forward calorimeters. A very accurate geometrical description of these calorimeters is used as input to the Geant 4-based ATLAS simulation, and a careful modelling of the signal development is applied in the generation of hits. Certain types of Monte Carlo truth information ("Calibration Hits") may, additionally, be recorded for calorimeter cells as well as for dead material. This note is a comprehensive reference describing the simulation of the four liquid argon calorimeteter components.

  12. Differential Scanning Calorimetry of Superelastic Nitinol for Tuneable Devices


    Feeney, Andrew; LUCAS, MARGARET


    Nitinol has been used to fabricate tuneable-frequency cymbal transducers by exploiting its solid-state phase transformation capability. The temperatures at which Nitinol transforms\\ud are commonly measured using differential scanning calorimetry (DSC). However, these\\ud measurements are shown to be inaccurate for superelastic Nitinol, reportedly attributed to residual stresses in the material resulting from the fabrication process. This study of DSC accuracy is conducted for untreated and hea...

  13. Accurate Measurement of Heat Capacity by Differential Scanning Calorimetry (United States)


    Experience with high quality heat capacity measurement by differential scanning calorimetry is summarized and illustrated, pointing out three major causes of error: (1) incompatible thermal histories of the sample, reference and blank runs; (2) unstable initial and final isotherms; (3) incompatible differences between initial and final isotherm amplitudes for sample, reference and blank runs. Considering these problems, it is shown for the case of polyoxymethylene that accuracies in heat capacity of 0.1 percent may be possible.

  14. Raman detected differential scanning calorimetry of polymorphic transformations in acetaminophen. (United States)

    Kauffman, John F; Batykefer, Linda M; Tuschel, David D


    Acetaminophen is known to crystallize in three polymorphic forms. Thermally induced transformations between the crystalline forms and the super-cooled liquid have been observed by differential scanning calorimetry (DSC), but the assignment of calorimetric transitions to specific polymorphic transformations remains challenging, because the transition temperatures for several transformations are close to one another, and the characteristics of the observed transitions depend on experimental variables that are often poorly controlled. This paper demonstrates the simultaneous application of DSC and Raman microscopy for the observation of thermally driven transitions between polymorphs of pharmaceutical materials. Raman detected differential scanning calorimetry (RD-DSC) has been used to monitor the DSC thermograms of super-cooled liquid acetaminophen and confirms the assignment of two exothermic transitions to specific polymorphic transformations. Principal component analysis of the Raman spectra have been used to determine the number of independent components that participate in the phase transformations, and multivariate regression has been used to determine transition temperatures from the spectral data. The influence of the laser excitation source on measured DSC thermograms has also been investigated, and it has been demonstrated that a baseline shift occurs in RD-DSC when a polymorphic transformation occurs between crystalline and amorphous forms. RD-DSC has been used to examine the influence of sample aging and sample pan configuration on the observed polymorphic transformations, and both of these variables were found to influence the thermal behavior of the sample. The results demonstrate the advantage of simultaneous Raman spectroscopy and differential scanning calorimetry for the unambiguous assignment of thermally driven polymorphic transformations.

  15. Simultaneous Thermodynamic and Kinetic Parameters Determination Using Differential Scanning Calorimetry

    Directory of Open Access Journals (Sweden)

    Nader Frikha


    Full Text Available Problem statement: The determination of reaction kinetics is of major importance, as for industrial reactors optimization as for environmental reasons or energy limitations. Although calorimetry is often used for the determination of thermodynamic parameters alone, the question that arises is: how can we apply the Differential Scanning Calorimetry for the determination of kinetic parameters. The objective of this study consists to proposing an original methodology for the simultaneous determination of thermodynamic and kinetic parameters, using a laboratory scale Differential Scanning Calorimeter (DSC. The method is applied to the dichromate-catalysed hydrogen peroxide decomposition. Approach: The methodology is based on operating of experiments carried out with a Differential Scanning Calorimeter. The interest of this approach proposed is that it requires very small quantities of reactants (about a few grams to be implemented. The difficulty lies in the fact that, using such microcalorimeters, the reactants temperature cannot directly be measured and a particular calibration procedure has thus to be developed, to determine the media temperature in an indirect way. The proposed methodology for determination of kinetics parameters is based on resolution of the coupled heat and mass balances. Results: A complete kinetic law is proposed. The Arrhenius parameters are determined as frequency factor k0 = 1.39×109 s−1 and activation energy E = 54.9 kJ mol−1. The measured enthalpy of reaction is ΔrH=−94 kJ mol−1. Conclusion: The comparison of the results obtained by such an original methodology with those obtained using a conventional laboratory scale reactor calorimetry, for the kinetics determination of, shows that this new approach is very relevant.

  16. Isothermal Titration Calorimetry: Assisted Crystallization of RNA-Ligand Complexes. (United States)

    Da Veiga, Cyrielle; Mezher, Joelle; Dumas, Philippe; Ennifar, Eric


    The success rate of nucleic acids/ligands co-crystallization can be significantly improved by performing preliminary biophysical analyses. Among suitable biophysical approaches, isothermal titration calorimetry (ITC) is certainly a method of choice. ITC can be used in a wide range of experimental conditions to monitor in real time the formation of the RNA- or DNA-ligand complex, with the advantage of providing in addition the complete binding profile of the interaction. Following the ITC experiment, the complex is ready to be concentrated for crystallization trials. This chapter describes a detailed experimental protocol for using ITC as a tool for monitoring RNA/small molecule binding, followed by co-crystallization.

  17. Fragment-Based Screening for Enzyme Inhibitors Using Calorimetry. (United States)

    Recht, Michael I; Nienaber, Vicki; Torres, Francisco E


    Isothermal titration calorimetry (ITC) provides a sensitive and accurate means by which to study the thermodynamics of binding reactions. In addition, it enables label-free measurement of enzymatic reactions. The advent of extremely sensitive microcalorimeters have made it increasingly valuable as a tool for hit validation and characterization, but its use in primary screening is hampered by requiring large quantities of reagents and long measurement times. Nanocalorimeters can overcome these limitations of conventional ITC, particularly for screening libraries of 500-1000 compounds such as those encountered in fragment-based lead discovery. This chapter describes how nanocalorimetry and conventional microcalorimetry can be used to screen compound libraries for enzyme inhibitors.

  18. Fast differential scanning calorimetry of liquid samples with chips

    DEFF Research Database (Denmark)

    Splinter, R.; van Herwaarden, A. W.; van Wetten, I. A.


    Based on a modified version of standard chips for fast differential scanning calorimetry, DSC of liquid samples has been performed at temperature scan rates of up to 1000 °C/s. This paper describes experimental results with the protein lysozyme, bovine serum, and olive oil. The heating and cooling....... The bovine serum measurements show two main peaks, in good agreement with standard DSC measurements. Olive oil has been measured, with good agreement for the cooling curve and qualitative agreement for the heater curve, compared to DSC measurements....

  19. Measuring thermal conductivity of powders with differential scanning calorimetry


    Pujula, Miquel; Sánchez-Rodríguez, Daniel; López-Olmedo, Joan Pere; Farjas Silva, Jordi; Roura Grabulosa, Pere


    This paper simplifies a recently proposed method for measuring the thermal conductivity of powders using differential scanning calorimetry (DSC) (Sa´nchez-Rodríguez et al. in J Therm Anal Calorim 121:469-473, 2015). With this method, a crucible is filled with powder and a spherical metal reference is partially sunk into it. The thermal resistance between the metal and the crucible wall at the metal melting point is obtained from the DSC melting peak slope. In the simplified method outlined in...

  20. Shashlik calorimetry a combined Shashlik + Preshower detector for LHC

    CERN Document Server

    Badier, J; Busata, A; CERN. Geneva. Detector Research and Development Committee


    Shashlik Calorimetry is a new technique which has been developed to read out the light from lead/scintillator sampling calorimeters, using wavelength shifters and optical fibres. The light yield is in excess of 10000 photons per GeV with fine lateral segmentation and minimum dead space. It is expected that such calorimeters can be buildt at relatively low cost. The first results on energy resolution and angular resolution, obtained in a non-projective prototype exposed to high energy electrons, are encouraging. Further research and development are essential before building a full scale projective detector.

  1. Isothermal titration calorimetry: general formalism using binding polynomials. (United States)

    Freire, Ernesto; Schön, Arne; Velazquez-Campoy, Adrian


    The theory of the binding polynomial constitutes a very powerful formalism by which many experimental biological systems involving ligand binding can be analyzed under a unified framework. The analysis of isothermal titration calorimetry (ITC) data for systems possessing more than one binding site has been cumbersome because it required the user to develop a binding model to fit the data. Furthermore, in many instances, different binding models give rise to identical binding isotherms, making it impossible to discriminate binding mechanisms using binding data alone. One of the main advantages of the binding polynomials is that experimental data can be analyzed by employing a general model-free methodology that provides essential information about the system behavior (e.g., whether there exists binding cooperativity, whether the cooperativity is positive or negative, and the magnitude of the cooperative energy). Data analysis utilizing binding polynomials yields a set of binding association constants and enthalpy values that conserve their validity after the correct model has been determined. In fact, once the correct model is validated, the binding polynomial parameters can be immediately translated into the model specific constants. In this chapter, we describe the general binding polynomial formalism and provide specific theoretical and experimental examples of its application to isothermal titration calorimetry.

  2. Advanced ion beam calorimetry for the test facility ELISE (United States)

    Nocentini, R.; Bonomo, F.; Pimazzoni, A.; Fantz, U.; Franzen, P.; Fröschle, M.; Heinemann, B.; Pasqualotto, R.; Riedl, R.; Ruf, B.; Wünderlich, D.


    The negative ion source test facility ELISE (Extraction from a Large Ion Source Experiment) is in operation since beginning of 2013 at the Max-Planck-Institut für Plasmaphysik (IPP) in Garching bei München. The large radio frequency driven ion source of ELISE is about 1×1 m2 in size (1/2 the ITER source) and can produce a plasma for up to 1 h. Negative ions can be extracted and accelerated by an ITER-like extraction system made of 3 grids with an area of 0.1 m2, for 10 s every 3 minutes. A total accelerating voltage of up to 60 kV is available, i.e. a maximum ion beam power of about 1.2 MW can be produced. ELISE is equipped with several beam diagnostic tools for the evaluation of the beam characteristics. In order to evaluate the beam properties with a high level of detail, a sophisticated diagnostic calorimeter has been installed in the test facility at the end of 2013, starting operation in January 2014. The diagnostic calorimeter is split into 4 copper plates with separate water calorimetry for each of the plates. Each calorimeter plate is made of 15×15 copper blocks, which act as many separate inertial calorimeters and are attached to a copper plate with an embedded cooling circuit. The block geometry and the connection with the cooling plate are optimized to accurately measure the time-averaged power of the 10 s ion beam. The surface of the blocks is covered with a black coating that allows infrared (IR) thermography which provides a 2D profile of the beam power density. In order to calibrate the IR thermography, 48 thermocouples are installed in as many blocks, arranged in two vertical and two horizontal rows. The paper describes the beam calorimetry in ELISE, including the methods used for the IR thermography, the water calorimetry and the analytical methods for beam profile evaluation. It is shown how the maximum beam inhomogeneity amounts to 13% in average. The beam divergence derived by IR thermography ranges between 1° and 4° and correlates

  3. Application of an open circuit indirect calorimetry system for gaseous exchange measurements in small ruminant nutrition




    [EN] The main objective of this Thesis was to study the energy metabolism in small ruminants under different nutrition sceneries. As methodology we utilized indirect calorimetry instead of direct calorimetry or feeding trials. Within indirect calorimetry we worked with a portable open circuit gas exchange system with a head hood. This open circuit respiration system permitted completed the whole energy balance and evaluate the efficiency of utilization of the energy of the diet for different ...

  4. Direct animal calorimetry, the underused gold standard for quantifying the fire of life. (United States)

    Kaiyala, Karl J; Ramsay, Douglas S


    Direct animal calorimetry, the gold standard method for quantifying animal heat production (HP), has been largely supplanted by respirometric indirect calorimetry owing to the relative ease and ready commercial availability of the latter technique. Direct calorimetry, however, can accurately quantify HP and thus metabolic rate (MR) in both metabolically normal and abnormal states, whereas respirometric indirect calorimetry relies on important assumptions that apparently have never been tested in animals with genetic or pharmacologically-induced alterations that dysregulate metabolic fuel partitioning and storage so as to promote obesity and/or diabetes. Contemporary obesity and diabetes research relies heavily on metabolically abnormal animals. Recent data implicating individual and group variation in the gut microbiome in obesity and diabetes raise important questions about transforming aerobic gas exchange into HP because 99% of gut bacteria are anaerobic and they outnumber eukaryotic cells in the body by ∼10-fold. Recent credible work in non-standard laboratory animals documents substantial errors in respirometry-based estimates of HP. Accordingly, it seems obvious that new research employing simultaneous direct and indirect calorimetry (total calorimetry) will be essential to validate respirometric MR phenotyping in existing and future pharmacological and genetic models of obesity and diabetes. We also detail the use of total calorimetry with simultaneous core temperature assessment as a model for studying homeostatic control in a variety of experimental situations, including acute and chronic drug administration. Finally, we offer some tips on performing direct calorimetry, both singly and in combination with indirect calorimetry and core temperature assessment.

  5. Modern Analysis of Protein Folding by Differential Scanning Calorimetry. (United States)

    Ibarra-Molero, Beatriz; Naganathan, Athi N; Sanchez-Ruiz, Jose M; Muñoz, Victor


    Differential scanning calorimetry (DSC) is a very powerful tool for investigating protein folding and stability because its experimental output reflects the energetics of all conformations that become minimally populated during thermal unfolding. Accordingly, analysis of DSC experiments with simple thermodynamic models has been key for developing our understanding of protein stability during the past five decades. The discovery of ultrafast folding proteins, which have naturally broad conformational ensembles and minimally cooperative unfolding, opens the possibility of probing the complete folding free energy landscape, including those conformations at the top of the barrier to folding, via DSC. Exploiting this opportunity requires high-quality experiments and the implementation of novel analytical methods based on statistical mechanics. Here, we cover the recent exciting developments in this front, describing the new analytical procedures in detail as well as providing experimental guidelines for performing such analysis.

  6. Novel investigation of enzymatic biodiesel reaction by isothermal calorimetry

    DEFF Research Database (Denmark)

    Søtoft, Lene Fjerbaek; Westh, Peter; Christensen, Knud V.


    Isothermal calorimetry (ITC) was used to investigate solvent-free enzymatic biodiesel production. The transesterification of rapeseed oil with methanol and ethanol was catalyzed by immobilized lipase Novozym 435 at 40 °C. The aim of the study was to determine reaction enthalpy for the enzymatic...... transesterification and to elucidate the mass transfer and energetic processes taking place. Based on the measured enthalpy and composition change in the system, the heat of reaction at 40 °C for the two systems was determined as −9.8 ± 0.9 kJ/mole biodiesel formed from rapeseed oil and methanol, and −9.3 ± 0.7 k...... thermodynamic properties such as reaction enthalpy and reaction rate, the difficulty in actually measuring the true non-mass-transfer-limited reaction kinetics is exposed by the high time resolution of ITC....

  7. Hydroxylamine nitrate self-catalytic kinetics study with adiabatic calorimetry. (United States)

    Liu, Lijun; Wei, Chunyang; Guo, Yuyan; Rogers, William J; Sam Mannan, M


    Hydroxylamine nitrate (HAN) is an important member of the hydroxylamine compound family with applications that include equipment decontamination in the nuclear industry and aqueous or solid propellants. Due to its instability and autocatalytic behavior, HAN has been involved in several incidents at the Hanford and Savannah River Site (SRS) [Technical Report on Hydroxylamine Nitrate, US Department of Energy, 1998]. Much research has been conducted on HAN in different areas, such as combustion mechanism, decomposition mechanism, and runaway behavior. However, the autocatalytic decomposition behavior of HAN at runaway stage has not been fully addressed due to its highly exothermic and rapid decomposition behavior. This work is focused on extracting HAN autocatalytic kinetics and analyzing HAN critical behavior from adiabatic calorimetry measurements. A lumped autocatalytic kinetic model for HAN and associated model parameters are determined. Also the storage and handling critical conditions of diluted HAN solution without metal presence are quantified.

  8. On the Interpretation of Low Temperature Calorimetry Data

    DEFF Research Database (Denmark)

    Kjeldsen, Ane Mette; Geiker, Mette Rica


    The effect of selected factors and phenomena on Low Temperature Calorimetry (LTC) results has been investigated, in order to determine the possibilities and limitations of using LTC for characterisation of the porosity of cement-based materials. LTC was carried out on a model material with mono...... gradients equilibrium cannot be obtained with the sample size used (1 g liquid). Correcting for non-equilibrium between reference block and sample, the Gibbs-Thomson equation seems applicable for estimation of pore sizes of the investigated size. The estimate may be further improved by taking the effect...... to limit transport of liquid, whereas heating should be undertaken at a low rate to limit the effect of non-equilibrium....


    Institute of Scientific and Technical Information of China (English)


    The glassy transition of the polyethylene terephthalate (PET) samples which have been subjected to solvent induced crystallization (SINC) was investigated by modulated differential scanning calorimetry (MDSC) and density measurement. The differential of heat capacity signal, d Cp/dT from MDSC, was used to monitor the SINC process. It reveals that the Tg temperature shifts to higher value with the advancement of SINC. When the toluene-immersing time was longer (168h), the detection of Tg become more difficult, because some smaller peaks emerged at the lower temperatures and these are explained as the movement of small segments in the amorphous region. These observed results are due to the morphology and structure introduced by the SINC process.

  10. Isothermal titration calorimetry of ion-coupled membrane transporters. (United States)

    Boudker, Olga; Oh, SeCheol


    Binding of ligands, ranging from proteins to ions, to membrane proteins is associated with absorption or release of heat that can be detected by isothermal titration calorimetry (ITC). Such measurements not only provide binding affinities but also afford direct access to thermodynamic parameters of binding--enthalpy, entropy and heat capacity. These parameters can be interpreted in a structural context, allow discrimination between different binding mechanisms and guide drug design. In this review, we introduce advantages and limitations of ITC as a methodology to study molecular interactions of membrane proteins. We further describe case studies where ITC was used to analyze thermodynamic linkage between ions and substrates in ion-coupled transporters. Similar type of linkage analysis will likely be applicable to a wide range of transporters, channels, and receptors.

  11. Isothermal titration calorimetry of membrane proteins - progress and challenges. (United States)

    Rajarathnam, Krishna; Rösgen, Jörg


    Integral membrane proteins, including G protein-coupled receptors (GPCR) and ion channels, mediate diverse biological functions that are crucial to all aspects of life. The knowledge of the molecular mechanisms, and in particular, the thermodynamic basis of the binding interactions of the extracellular ligands and intracellular effector proteins is essential to understand the workings of these remarkable nanomachines. In this review, we describe how isothermal titration calorimetry (ITC) can be effectively used to gain valuable insights into the thermodynamic signatures (enthalpy, entropy, affinity, and stoichiometry), which would be most useful for drug discovery studies, considering that more than 30% of the current drugs target membrane proteins. This article is part of a Special Issue entitled: Structural and biophysical characterisation of membrane protein-ligand binding.

  12. Applications of isothermal titration calorimetry in protein science

    Institute of Scientific and Technical Information of China (English)

    Yi Liang


    During the past decade,isothermal titration calorimetry (ITC)has developed from a specialist method for understanding molecular interactions and other biological processes within cells to a more robust,widely used method.Nowadays,ITC is used to investigate all types of protein interactions,including protein-protein interactions,protein-DNA/RNA interactions,protein-small molecule interactions and enzyme kinetics;it provides a direct route to the complete thermodynamic characterization of protein interactions.This review concentrates on the new applications of ITC in protein folding and misfolding,its traditional application in protein interactions,and an overview of what can be achieved in the field of protein science using this method and what developments are likely to occur in the near future.Also,this review discusses some new developments of ITC method in protein science,such as the reverse titration of ITC and the displacement method of ITC.

  13. Hadronic Shower Development in Iron-Scintillator Tile Calorimetry

    CERN Document Server

    Amaral, P; Anderson, K; Barreira, G; Benetta, R; Berglund, S; Biscarat, C; Blanchot, G; Blucher, E; Bogush, A A; Bohm, C; Boldea, V; Borisov, O; Bosman, M; Bromberg, C; Budagov, Yu A; Burdin, S; Caloba, L; Carvalho, J; Casado, M P; Castillo, M V; Cavalli-Sforza, M; Cavasinni, V; Chadelas, R; Chirikov-Zorin, I E; Chlachidze, G; Cobal, M; Cogswell, F; Colaço, F; Cologna, S; Constantinescu, S; Costanzo, D; Crouau, M; Daudon, F; David, J; David, M; Davidek, T; Dawson, J; De, K; Del Prete, T; De Santo, A; Di Girolamo, B; Dita, S; Dolejsi, J; Dolezal, Z; Downing, R; Efthymiopoulos, I; Engström, M; Errede, D; Errede, S; Evans, H; Fenyuk, A; Ferrer, A; Flaminio, V; Gallas, E; Gaspar, M; Gil, I; Gildemeister, O; Glagolev, V; Gomes, A; González, V; González de la Hoz, S; Grabskii, V; Graugès-Pous, E; Grenier, P; Hakopian, H H; Haney, M; Hansen, M; Hellman, S; Henriques, A; Hébrard, C; Higón, E; Holmgren, S O; Huston, J; Ivanyushenkov, Yu M; Jon-And, K; Juste, A; Kakurin, S; Karapetian, G V; Karyukhin, A N; Kopikov, S; Kukhtin, V; Kulchitskii, Yu A; Kurzbauer, W; Kuzmin, M; Lami, S; Lapin, V; Lazzeroni, C; Lebedev, A; Leitner, R; Li, J; Lomakin, Yu F; Lomakina, O V; Lokajícek, M; López-Amengual, J M; Maio, A; Malyukov, S; Marroquin, F; Martins, J P; Mazzoni, E; Merritt, F S; Miller, R; Minashvili, I A; Miralles, L; Montarou, G; Munar, A; Némécek, S; Nessi, Marzio; Onofre, A; Orteu, S; Park, I C; Pallin, D; Pantea, D; Paoletti, R; Patriarca, J; Pereira, A; Perlas, J A; Petit, P; Pilcher, J E; Pinhão, J; Poggioli, L; Price, L; Proudfoot, J; Pukhov, O; Reinmuth, G; Renzoni, G; Richards, R; Roda, C; Romance, J B; Romanov, V; Ronceux, B; Rosnet, P; Rumyantsev, V; Rusakovich, N; Sanchis, E; Sanders, H; Santoni, C; Santos, J; Sawyer, L; Says, L P; Seixas, J M; Selldén, B; Semenov, A; Shchelchkov, A S; Shochet, M; Simaitis, V; Sissakian, A N; Solodkov, A; Solovyanov, O; Sonderegger, P; Sosebee, M; Soustruznik, K; Spanó, F; Stanek, R; Starchenko, E A; Stephens, R; Suk, M; Tang, F; Tas, P; Thaler, J; Tokar, S; Topilin, N; Trka, Z; Turcot, A S; Turcotte, M; Valkár, S; Varandas, M J; Vartapetian, A H; Vazeille, F; Vichou, I; Vinogradov, V; Vorozhtsov, S B; Wagner, D; White, A; Wolters, H; Yamdagni, N; Yarygin, G; Yosef, C; Zaitsev, A; Zdrazil, M; Zúñiga, J


    The lateral and longitudinal profiles of hadronic showers detected by a prototype of the ATLAS Iron-Scintillator Tile Hadron Calorimeter have been investigated. This calorimeter uses a unique longitudinal configuration of scintillator tiles. Using a fine-grained pion beam scan at 100 GeV, a detailed picture of transverse shower behavior is obtained. The underlying radial energy densities for four depth segments and for the entire calorimeter have been reconstructed. A three-dimensional hadronic shower parametrization has been developed. The results presented here are useful for understanding the performance of iron-scintillator calorimeters, for developing fast simulations of hadronic showers, for many calorimetry problems requiring the integration of a shower energy deposition in a volume and for future calorimeter design.

  14. Applications of isothermal titration calorimetry in protein science. (United States)

    Liang, Yi


    During the past decade, isothermal titration calorimetry (ITC) has developed from a specialist method for understanding molecular interactions and other biological processes within cells to a more robust, widely used method. Nowadays, ITC is used to investigate all types of protein interactions, including protein-protein interactions, protein-DNA/RNA interactions, protein-small molecule interactions and enzyme kinetics; it provides a direct route to the complete thermodynamic characterization of protein interactions. This review concentrates on the new applications of ITC in protein folding and misfolding, its traditional application in protein interactions, and an overview of what can be achieved in the field of protein science using this method and what developments are likely to occur in the near future. Also, this review discusses some new developments of ITC method in protein science, such as the reverse titration of ITC and the displacement method of ITC.

  15. Monitoring RNA-ligand interactions using isothermal titration calorimetry. (United States)

    Gilbert, Sunny D; Batey, Robert T


    Isothermal titration calorimetry (ITC) is a biophysical technique that measures the heat evolved or absorbed during a reaction to report the enthalpy, entropy, stoichiometry of binding, and equilibrium association constant. A significant advantage of ITC over other methods is that it can be readily applied to almost any RNA-ligand complex without having to label either molecule and can be performed under a broad range of pH, temperature, and ionic concentrations. During our application of ITC to investigate the thermodynamic details of the interaction of a variety of compounds with the purine riboswitch, we have explored and optimized experimental parameters that yield the most useful and reproducible results for RNAs. In this chapter, we detail this method using the titration of an adenine-binding RNA with 2,6-diaminopurine (DAP) as a practical example. Our insights should be generally applicable to observing the interactions of a broad range of molecules with structured RNAs.

  16. Particle flow calorimetry at the international linear collider

    Indian Academy of Sciences (India)

    Mark A Thomson


    One of the most important requirements for a detector at the ILC is good jet energy resolution. It is widely believed that the particle flow approach to calorimetry is the key to achieving the goal of $0.3/\\sqrt{E(GeV)}$. This paper describes the current performance of the PandoraPFA particle flow algorithm. For 45 GeV jets in the Tesla TDR detector concept, the ILC jet energy resolution goal is reached. At higher energies the jet energy resolution becomes worse and can be described by the empirical expression: $_{E}/E ≈ 0.265/\\sqrt{E(GeV)} + 1.2 times 10^{-4} E(GeV)$.

  17. Front-End Electronics in calorimetry: from LHC to ILC

    Energy Technology Data Exchange (ETDEWEB)

    De La Taille, Ch.


    This report summarizes the electronics developments for liquid argon calorimeter read-out at LHC and the development carried out in the framework of the CALICE collaboration for those of the future linear collider (ILC). It also includes chips designed for multi-anode photomultipliers (MaPMT) used in the OPERA experiment or on ATLAS luminometer, which also find applications in medical imaging. Started in the early 90's, the development for ATLAS calorimetry was extremely challenging in terms of readout speed, radiation tolerance and measurement accuracy. The high speed has required a new approach using current-sensitive preamplifiers instead of charge sensitive ones and the redefinition of noise performance in terms of ENI. The preamplifiers developed at Orsay and the monolithic shapers are described in Chapter 1, including considerations of digital filtering, which was a new technique in our field. Chapter 2 is dedicated to the calibration system, designed and built by Orsay, for which the high performance and accuracy necessitated in-depth studies. The 3. chapter closes the studies for ATLAS with a summary of the detector measurements which had to be carried out on the 200 000 channels in order to understand and model the detector and achieve everywhere the accuracy and uniformity at per-cent level. These developments for ATLAS ended in 2004, although parallel work was also carried out for the NA48 and DO calorimeters which are not detailed here. The next generation of collider will require a new generation of calorimeters, much more granular, referred to as 'imaging calorimetry' with embedded read-out electronics. The ASICs developed for this purpose in the framework of the CALICE collaboration are described in Chapter 4. They integrate all the functionalities of amplification, digitization and read-out making them complex 'System-On-Chip' circuits extremely efficient that find many other applications. A family of 3 chips reads out the

  18. An evaluation of the use of calorimetry for shipper-receiver measurements of plutonium

    Energy Technology Data Exchange (ETDEWEB)

    Rodenburg, W.W.


    The purpose of this report is to evaluate the relative merit of using calorimetry for shipper-receiver (S-R) exchanges of Pu. In particular, this evaluation concentrates on the accountability and the diversion detection aspects of calorimetry. Three different modes of use were considered: (1) calorimetry alone, that is S-R exchanges based on power (wattage) measurements; (2) calorimetry plus chemical assay, similar to the present weight plus chemical assay system, and (3) calorimetry plus gamma-ray spectrometry, a totally nondestructive Pu assay method. The relative merit of ball three applications was judged using the present methods as a base case. Some of the factors considered were random and systematic errors, timeliness, costs (both operating and capital) and reliability.

  19. Novel investigation of enzymatic biodiesel reaction by isothermal calorimetry

    Energy Technology Data Exchange (ETDEWEB)

    Sotoft, Lene Fjerbaek, E-mail: [Institute of Chemical Engineering, Biotechnology and Environmental Technology, University of Southern Denmark, Campusvej 55, DK-5230 Odense M (Denmark); Westh, Peter [Department of Life Science and Chemistry, Roskilde University, PO Box 260, DK-4000 Roskilde (Denmark); Christensen, Knud V.; Norddahl, Birgir [Institute of Chemical Engineering, Biotechnology and Environmental Technology, University of Southern Denmark, Campusvej 55, DK-5230 Odense M (Denmark)


    Isothermal calorimetry (ITC) was used to investigate solvent-free enzymatic biodiesel production. The transesterification of rapeseed oil with methanol and ethanol was catalyzed by immobilized lipase Novozym 435 at 40 {sup o}C. The aim of the study was to determine reaction enthalpy for the enzymatic transesterification and to elucidate the mass transfer and energetic processes taking place. Based on the measured enthalpy and composition change in the system, the heat of reaction at 40 {sup o}C for the two systems was determined as -9.8 {+-} 0.9 kJ/mole biodiesel formed from rapeseed oil and methanol, and -9.3 {+-} 0.7 kJ/mole when rapeseed oil and ethanol was used. Simple Michaelis-Menten kinetics was not an appropriate choice for describing the kinetics of this heterogeneous system. The experiments demonstrated the possibility of investigating complex reaction mixtures using ITC. Although it is possible to determine thermodynamic properties such as reaction enthalpy and reaction rate, the difficulty in actually measuring the true non-mass-transfer-limited reaction kinetics is exposed by the high time resolution of ITC.

  20. A microfabrication-based approach to quantitative isothermal titration calorimetry. (United States)

    Wang, Bin; Jia, Yuan; Lin, Qiao


    Isothermal titration calorimetry (ITC) directly measures heat evolved in a chemical reaction to determine equilibrium binding properties of biomolecular systems. Conventional ITC instruments are expensive, use complicated design and construction, and require long analysis times. Microfabricated calorimetric devices are promising, although they have yet to allow accurate, quantitative ITC measurements of biochemical reactions. This paper presents a microfabrication-based approach to integrated, quantitative ITC characterization of biomolecular interactions. The approach integrates microfabricated differential calorimetric sensors with microfluidic titration. Biomolecules and reagents are introduced at each of a series of molar ratios, mixed, and allowed to react. The reaction thermal power is differentially measured, and used to determine the thermodynamic profile of the biomolecular interactions. Implemented in a microdevice featuring thermally isolated, well-defined reaction volumes with minimized fluid evaporation as well as highly sensitive thermoelectric sensing, the approach enables accurate and quantitative ITC measurements of protein-ligand interactions under different isothermal conditions. Using the approach, we demonstrate ITC characterization of the binding of 18-Crown-6 with barium chloride, and the binding of ribonuclease A with cytidine 2'-monophosphate within reaction volumes of approximately 0.7 µL and at concentrations down to 2mM. For each binding system, the ITC measurements were completed with considerably reduced analysis times and material consumption, and yielded a complete thermodynamic profile of the molecular interaction in agreement with published data. This demonstrates the potential usefulness of our approach for biomolecular characterization in biomedical applications.

  1. Study of Liquid Argon Dopants for LHC Hadron Calorimetry

    CERN Multimedia


    Hadron calorimetry based on the Liquid Argon Ionisation Chamber technique is one of the choice techniques for LHC-experimentation. A systematic study of the effect of selected dopants on Liquid Argon (LAr) will be carried out with the aim to achieve an improvement on: \\item (i)~``Fast Liquid Argon'' search and study of dopants to increase the drift velocity. It has been already shown that CH&sub4. added at a fraction of one percent increases the drift velocity by a factor of two or more. \\item (ii)~``Compensated Liquid Argon'' search and study of dopants to increase the response to densely ionising particles, resulting in improved compensation, such as photosensitive dopants. \\end{enumerate}\\\\ \\\\ Monitoring of the parameters involved in understanding the response of a calorimeter is essential. In case of doped LAr, the charge yield, the non-saturated drift velocity and the electron lifetime in the liquid should be precisely and simultaneously monitored as they all vary with the level of dopant concentrati...

  2. The Electromagnetic Calorimetry of the PANDA Detector at FAIR (United States)

    Novotny, R. W.; PANDA Collaboration


    The PANDA collaboration at FAIR, Germany, will focus on undiscovered charm-meson states and glueballs in antiproton annihilations to study QCD phenomena in the non-perturbative regime. For fixed target experiments at the storage ring HESR a 4π-detector for tracking, particle ID and calorimetry is under development and construction to operate at high annihilation rates up to 20 MHz. The electromagnetic calorimeters are composed of a target spectrometer (EMC) based on PbWO4 crystals and a shashlyk-type sampling calorimeter at the most forward region. The EMC, comprising more than 15,000 crystals, is operated at a temperature of -25°C and read-out via large-area avalanche photo-diodes or vacuum phototriodes/tetrodes. The photo sensor signals are continuously digitized by sampling ADCs. More than 50% of the high quality PWO-II crystals are delivered and tested. The excellent performance with respect to energy, time and position information was determined over a shower energy range from 10 MeV up to 15 GeV by operating several prototype detectors. In addition, the concept of stimulated recovery has been investigated to recover radiation damage on- and off-line during the calorimeter operation. Besides the overall concept of the target spectrometer the response function of the shashlyk spectrometer down to photon energies even below 100 MeV is presented.

  3. Survey of the year 2008: applications of isothermal titration calorimetry. (United States)

    Falconer, Robert J; Penkova, Anita; Jelesarov, Ilian; Collins, Brett M


    Isothermal titration calorimetry (ITC) is a fast, accurate and label-free method for measuring the thermodynamics and binding affinities of molecular associations in solution. Because the method will measure any reaction that results in a heat change, it is applicable to many different fields of research from biomolecular science, to drug design and materials engineering, and can be used to measure binding events between essentially any type of biological or chemical ligand. ITC is the only method that can directly measure binding energetics including Gibbs free energy, enthalpy, entropy and heat capacity changes. Not only binding thermodynamics but also catalytic reactions, conformational rearrangements, changes in protonation and molecular dissociations can be readily quantified by performing only a small number of ITC experiments. In this review, we highlight some of the particularly interesting reports from 2008 employing ITC, with a particular focus on protein interactions with other proteins, nucleic acids, lipids and drugs. As is tradition in these reviews we have not attempted a comprehensive analysis of all 500 papers using ITC, but emphasize those reports that particularly captured our interest and that included more thorough discussions we consider exemplify the power of the technique and might serve to inspire other users.

  4. Characterization of membrane protein interactions by isothermal titration calorimetry. (United States)

    Situ, Alan J; Schmidt, Thomas; Mazumder, Parichita; Ulmer, Tobias S


    Understanding the structure, folding, and interaction of membrane proteins requires experimental tools to quantify the association of transmembrane (TM) helices. Here, we introduce isothermal titration calorimetry (ITC) to measure integrin αIIbβ3 TM complex affinity, to study the consequences of helix-helix preorientation in lipid bilayers, and to examine protein-induced lipid reorganization. Phospholipid bicelles served as membrane mimics. The association of αIIbβ3 proceeded with a free energy change of -4.61±0.04kcal/mol at bicelle conditions where the sampling of random helix-helix orientations leads to complex formation. At bicelle conditions that approach a true bilayer structure in effect, an entropy saving of >1kcal/mol was obtained from helix-helix preorientation. The magnitudes of enthalpy and entropy changes increased distinctly with bicelle dimensions, indicating long-range changes in bicelle lipid properties upon αIIbβ3 TM association. NMR spectroscopy confirmed ITC affinity measurements and revealed αIIbβ3 association and dissociation rates of 4500±100s(-1) and 2.1±0.1s(-1), respectively. Thus, ITC is able to provide comprehensive insight into the interaction of membrane proteins.

  5. Measuring Multivalent Binding Interactions by Isothermal Titration Calorimetry. (United States)

    Dam, Tarun K; Talaga, Melanie L; Fan, Ni; Brewer, Curtis F


    Multivalent glycoconjugate-protein interactions are central to many important biological processes. Isothermal titration calorimetry (ITC) can potentially reveal the molecular and thermodynamic basis of such interactions. However, calorimetric investigation of multivalency is challenging. Binding of multivalent glycoconjugates to proteins (lectins) often leads to a stoichiometry-dependent precipitation process due to noncovalent cross-linking between the reactants. Precipitation during ITC titration severely affects the quality of the baseline as well as the signals. Hence, the resulting thermodynamic data are not dependable. We have made some modifications to address this problem and successfully studied multivalent glycoconjugate binding to lectins. We have also modified the Hill plot equation to analyze high quality ITC raw data obtained from multivalent binding. As described in this chapter, ITC-driven thermodynamic parameters and Hill plot analysis of ITC raw data can provide valuable information about the molecular mechanism of multivalent lectin-glycoconjugate interactions. The methods described herein revealed (i) the importance of functional valence of multivalent glycoconjugates, (ii) that favorable entropic effects contribute to the enhanced affinities associated with multivalent binding, (iii) that with the progression of lectin binding, the microscopic affinities of the glycan epitopes of a multivalent glycoconjugate decrease (negative cooperativity), (iv) that lectin binding to multivalent glycoconjugates, especially to mucins, involves internal diffusion jumps, (bind and jump) and (v) that scaffolds of glycoconjugates influence their entropy of binding.

  6. Cure kinetics of epoxy matrix resin by differential scanning calorimetry (United States)

    Cizmecioglu, M.; Gupta, A.


    A study was made on the cure kinetics of an epoxy neat-resin (Narmco 5208) using Differential Scanning Calorimetry (DSC). Two interrelated analytical methods were applied to dynamic DSC data for evaluating the kinetic parameters, such as activation energy, E, the order of reaction, n, and the total heat of polymerization (or crosslinking), delta H sub t. The first method was proposed by Ellerstein (1968), and uses a thorough differential-integral analysis of a single DSC curve to evaluate the kinetic parameters. The second method was proposed by Kissinger (1957), and uses multiple DSC curves obtained at various heating rates to evaluate E regardless of n. Kinetic analysis of Narmco 5208 epoxy resin showed that the reaction order, n, is substantially affected by the rate of heating; i.e., n is approximately 2 at slow scan rates but is reduced to 1.5 at higher scan rates. The activation energy, E, is not affected by the scan rate, and the average value of E is 25.6 + or - 1.8 kcal/mole.

  7. Characterization of protein-protein interactions by isothermal titration calorimetry. (United States)

    Velazquez-Campoy, Adrian; Leavitt, Stephanie A; Freire, Ernesto


    The analysis of protein-protein interactions has attracted the attention of many researchers from both a fundamental point of view and a practical point of view. From a fundamental point of view, the development of an understanding of the signaling events triggered by the interaction of two or more proteins provides key information to elucidate the functioning of many cell processes. From a practical point of view, understanding protein-protein interactions at a quantitative level provides the foundation for the development of antagonists or agonists of those interactions. Isothermal Titration Calorimetry (ITC) is the only technique with the capability of measuring not only binding affinity but the enthalpic and entropic components that define affinity. Over the years, isothermal titration calorimeters have evolved in sensitivity and accuracy. Today, TA Instruments and MicroCal market instruments with the performance required to evaluate protein-protein interactions. In this methods paper, we describe general procedures to analyze heterodimeric (porcine pancreatic trypsin binding to soybean trypsin inhibitor) and homodimeric (bovine pancreatic α-chymotrypsin) protein associations by ITC.

  8. Application of pressure perturbation calorimetry to lipid bilayers. (United States)

    Heerklotz, Heiko; Seelig, Joachim


    Pressure perturbation calorimetry (PPC) is a new method that measures the heat consumed or released by a sample after a sudden pressure jump. The heat change can be used to derive the thermal volume expansion coefficient, alpha(V), as a function of temperature and, in the case of phase transitions, the volume change, DeltaV, occurring at the phase transition. Here we present the first report on the application of PPC to determine these quantities for lipid bilayers. We measure the volume changes of the pretransition and main transition of 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC), and the thermal expansivity of the fluid phase of DMPC and of two unsaturated lipids, 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine and 1,2-dioleoyl-sn-glycero-3-phosphocholine. The high sensitivity of PPC instrumentation gives accurate data for alpha(V) and DeltaV even upon the application of relatively low pressures of approximately 5 bar.

  9. Hot biological catalysis: isothermal titration calorimetry to characterize enzymatic reactions. (United States)

    Mazzei, Luca; Ciurli, Stefano; Zambelli, Barbara


    Isothermal titration calorimetry (ITC) is a well-described technique that measures the heat released or absorbed during a chemical reaction, using it as an intrinsic probe to characterize virtually every chemical process. Nowadays, this technique is extensively applied to determine thermodynamic parameters of biomolecular binding equilibria. In addition, ITC has been demonstrated to be able of directly measuring kinetics and thermodynamic parameters (kcat, KM, ΔH) of enzymatic reactions, even though this application is still underexploited. As heat changes spontaneously occur during enzymatic catalysis, ITC does not require any modification or labeling of the system under analysis and can be performed in solution. Moreover, the method needs little amount of material. These properties make ITC an invaluable, powerful and unique tool to study enzyme kinetics in several applications, such as, for example, drug discovery. In this work an experimental ITC-based method to quantify kinetics and thermodynamics of enzymatic reactions is thoroughly described. This method is applied to determine kcat and KM of the enzymatic hydrolysis of urea by Canavalia ensiformis (jack bean) urease. Calculation of intrinsic molar enthalpy (ΔHint) of the reaction is performed. The values thus obtained are consistent with previous data reported in literature, demonstrating the reliability of the methodology.

  10. Application of isothermal titration calorimetry in bioinorganic chemistry. (United States)

    Grossoehme, Nicholas E; Spuches, Anne M; Wilcox, Dean E


    The thermodynamics of metals ions binding to proteins and other biological molecules can be measured with isothermal titration calorimetry (ITC), which quantifies the binding enthalpy (ΔH°) and generates a binding isotherm. A fit of the isotherm provides the binding constant (K), thereby allowing the free energy (ΔG°) and ultimately the entropy (ΔS°) of binding to be determined. The temperature dependence of ΔH° can then provide the change in heat capacity (ΔC (p)°) upon binding. However, ITC measurements of metal binding can be compromised by undesired reactions (e.g., precipitation, hydrolysis, and redox), and generally involve competing equilibria with the buffer and protons, which contribute to the experimental values (K (ITC), ΔH (ITC)). Guidelines and factors that need to be considered for ITC measurements involving metal ions are outlined. A general analysis of the experimental ITC values that accounts for the contributions of metal-buffer speciation and proton competition and provides condition-independent thermodynamic values (K, ΔH°) for metal binding is developed and validated.

  11. Measuring the Kinetics of Molecular Association by Isothermal Titration Calorimetry. (United States)

    Vander Meulen, Kirk A; Horowitz, Scott; Trievel, Raymond C; Butcher, Samuel E


    The real-time power response inherent in an isothermal titration calorimetry (ITC) experiment provides an opportunity to directly analyze association kinetics, which, together with the conventional measurement of thermodynamic quantities, can provide an incredibly rich description of molecular binding in a single experiment. Here, we detail our application of this method, in which interactions occurring with relaxation times ranging from slightly below the instrument response time constant (12.5 s in this case) to as large as 600 s can be fully detailed in terms of both the thermodynamics and kinetics. In a binding titration scenario, in the most general case an injection can reveal an association rate constant (kon). Under more restrictive conditions, the instrument time constant-corrected power decay following each injection is simply an exponential decay described by a composite rate constant (kobs), from which both kon and the dissociation rate constant (koff) can be extracted. The data also support the viability of this exponential approach, for kon only, for a slightly larger set of conditions. Using a bimolecular RNA folding model and a protein-ligand interaction, we demonstrate and have internally validated this approach to experiment design, data processing, and error analysis. An updated guide to thermodynamic and kinetic regimes accessible by ITC is provided.

  12. Statistical analysis of plasma thermograms measured by differential scanning calorimetry. (United States)

    Fish, Daniel J; Brewood, Greg P; Kim, Jong Sung; Garbett, Nichola C; Chaires, Jonathan B; Benight, Albert S


    Melting curves of human plasma measured by differential scanning calorimetry (DSC), known as thermograms, have the potential to markedly impact diagnosis of human diseases. A general statistical methodology is developed to analyze and classify DSC thermograms to analyze and classify thermograms. Analysis of an acquired thermogram involves comparison with a database of empirical reference thermograms from clinically characterized diseases. Two parameters, a distance metric, P, and correlation coefficient, r, are combined to produce a 'similarity metric,' ρ, which can be used to classify unknown thermograms into pre-characterized categories. Simulated thermograms known to lie within or fall outside of the 90% quantile range around a median reference are also analyzed. Results verify the utility of the methods and establish the apparent dynamic range of the metric ρ. Methods are then applied to data obtained from a collection of plasma samples from patients clinically diagnosed with SLE (lupus). High correspondence is found between curve shapes and values of the metric ρ. In a final application, an elementary classification rule is implemented to successfully analyze and classify unlabeled thermograms. These methods constitute a set of powerful yet easy to implement tools for quantitative classification, analysis and interpretation of DSC plasma melting curves.

  13. On the feasibility of water calorimetry with scanned proton radiation. (United States)

    Sassowsky, M; Pedroni, E


    Water calorimetry is considered to be the most direct primary method to realize the physical quantity gray for absorbed dose to water. The Swiss Federal Office of Metrology and Accreditation (METAS) has routinely operated a water calorimeter as primary standard for photon radiation since 2001. Nowadays, cancer therapy with proton radiation has become increasingly important and is a well established method. In the framework of the ProScan project conducted by the Paul Scherrer Institute (PSI), the spot-scanning technique is prepared for the subsequent application in hospitals, and adjusted to the recent findings of clinical research. In the absence of primary standards for proton radiation, the metrological traceability is assured by calibrating secondary standards in 60Co radiation and correcting with calculated beam quality correction factors. It is internationally recognized that the development of primary standards for proton radiation is highly desirable. In a common project of PSI and METAS, it is investigated whether a modified version of the water calorimeter in operation at METAS is suitable as primary standard for scanned proton radiation. A feasibility study has been conducted to investigate the linear energy transfer (LET) dependence of the heat defect and the influence of the time and space structure of the scanned beam on the homogeneity and stability of the temperature field in the water calorimeter. Simulations are validated against experimental data of the existing calorimeter used with photon radiation and extended to scanned proton radiation.


    Institute of Scientific and Technical Information of China (English)

    Robert Shanks; Fei Chen; Gandara Amarasinghe


    Short chain branching has been characterized using thermal fractionation, a stepwise isothermal crystallization technique, followed by a melting analysis scan using differential scanning calorimetry. Short chain branching distribution was also characterized by a continuous slow cooling crystallization, followed by a melting analysis scan. Four different polyethylenes were studied: Ziegler-Natta gas phase, Ziegler-Natta solution, metallocene, constrained-geometry single site catalyzed polyethylenes. The branching distribution was calculated from a calibration of branch content with melting temperature. The lamellar thickness was calculated based on the thermodynamic melting temperature of each polyethylene and the surface free energy of the crystal face. The branching distribution and lamellar thickness distribution were used to calculate weight average branch content, mean lamellar thickness, and a branch dispersity index. The results for the branch content were in good agreement with the known comonomer content of the polyethylenes. A limitation was that high branch content polyethylenes did not reach their potential crystallization at ambient temperatures. Cooling to sub-ambient was necessary to equilibrate the crystallization, but melting temperature versus branch content was not applicable after cooling to below ambient because the calibration data were not performed in this way.


    Institute of Scientific and Technical Information of China (English)

    RobertShanks; FeiChan; GandaraAmarasinghe; RobertShanks


    Short chain branching has been characterized using thermal fractionation,a stepwise isothermal crystallization technique,followed by a melting analysis scan using differential scanning calorimetry.Short chain branching distribution was also characterized by a continuous slow cooling crystallization,followed by a melting analysis scan.Four different polyethylenes were studied:Ziegler-Natta gas phase,Ziegler-Natta solution,metallocene,constrained-geometry single site catalyzed polyethylenes.The branching distribution was calculated from a calibration of branch content with melting temperature.The lamellar thickness was calculated based on the thermodynamic melting temperature of each polyethylene and the surface free energy of the crystal face.The branching distribution and lamellar thickness distribution were used to calculate weight average branch content,mean lamellar thickness,and a branch dispersity index.The results for the branch content were in good agreement with the known comonomer content of the polyethylenes.A limitation was that high branch content polyethylenes did not reach their potential crystallization at ambient temperatures.Cooling to sub-ambient was necessary to equilibrate the crystallization,but melting temperature versus branch content was not applicable after cooling to below ambient because the calibration data were not performed in this way.

  16. Adiabatic calorimetry (RSST and VSP) tests with sodium acetate

    Energy Technology Data Exchange (ETDEWEB)

    Kirch, N.W.


    As requested in the subject reference, adiabatic calorimetry (RSST and VSP) tests have been performed with sodium acetate covering TOC concentrations from 3 to 7% with the following results: Exothermic activity noted around 200{degrees}C. Propagating reaction initiated at about 300{degrees}C. Required TOC concentration for propagation estimated at about 6 w% (dry mixture) or about 20 w% sodium acetate. Heat of reaction estimated to be 3.7 MJ per kg of sodium acetate (based on VSP test with 3 w% TOC and using a dry mixture specific heat of 1000 J kg{sup {minus}1} K{sup {minus}1}). Based upon the above results we estimate that a moisture content in excess of 14 w% would prevent a propagating reaction of a stoichiometric mixture of fuel and oxidizer ({approximately} 38 w% sodium acetate and {approximately}62 w% sodium nitrate). Assuming that the fuel can be treated as sodium acetate equivalent, and considering that the moisture content in the organic containing waste generally is believed to be in excess of 14 w%, it follows that the possibility of propagating reactions in the Hanford waste tanks can be ruled out.

  17. Calorimetry study of microwave absorption of some solid materials. (United States)

    He, Chun Lin; Ma, Shao Jian; Su, Xiu Juan; Chen, Yan Qing; Liang, Yu Shi


    In practice, the dielectric constant of a material varies the applied frequency the material composition, particle size, purity, temperature, physical state (solid or liquid), and moisture content. All of these parameters might change during processing, therefore, it is difficult to predict how well a material will absorb microwave energy in a given process. When the temperature is measured by a digital thermometer, it could not accurately reflect the true temperature of the bulk materials, especially for mixed materials. Thus, in this paper we measured the microwave absorption characteristics of different materials by calorimetry. The microwave power levels, irradiation times, and masses of the materials were varied. It was difficult to predict the microwave energy absorption characteristics of reagent-grade inorganic compounds based on their color, metallic cation, or water stoichiometry. CuO, MnO2, Fe3O4, and MnSO4 x H2O (Taishan) strongly absorbed microwave energy. Most of the remaining inorganic compounds were poor absorbers, with silica hardly absorbing any microwave energy. Carbon-based materials had significantly different microwave absorption characteristics. Activated carbon and coke were especially sensitive to microwaves, but different types of coal were poor absorbers. The jamesonite concentrate absorbed microwave energy strongly, while the zinc concentrate was a poor absorber.

  18. Applying fast calorimetry on a spent nuclear fuel calorimeter

    Energy Technology Data Exchange (ETDEWEB)

    Liljenfeldt, Henrik [Swedish Nuclear Fuel and Waste Management (Sweden); Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Uppsala Univ. (Sweden)


    Recently at Los Alamos National Laboratory, sophisticated prediction algorithms have been considered for the use of calorimetry for treaty verification. These algorithms aim to predict the equilibrium temperature based on early data and therefore be able to shorten the measurement time while maintaining good accuracy. The algorithms have been implemented in MATLAB and applied on existing equilibrium measurements from a spent nuclear fuel calorimeter located at the Swedish nuclear fuel interim storage facility. The results show significant improvements in measurement time in the order of 15 to 50 compared to equilibrium measurements, but cannot predict the heat accurately in less time than the currently used temperature increase method can. This Is both due to uncertainties in the calibration of the method as well as identified design features of the calorimeter that limits the usefulness of equilibrium type measurements. The conclusions of these findings are discussed, and suggestions of both improvements of the current calorimeter as well as what to keep in mind in a new design are given.

  19. PREFACE: XIV International Conference on Calorimetry in High Energy Physics (United States)

    Wang, Yifang


    The International Conferences on Calorimetry in High Energy Physics (also known as the Calor Conference series, started in October 1990 at Fermilab) address all aspects of calorimetric particle detection and measurement, with an emphasis on high energy physics experiments. The XIV International Conference on Calorimetry in High Energy Physics (Calor 2010) was held at the campus of the Institute of High Energy Physics, Beijing, China, from May 10-14, 2010. This conference brought together more than 110 participants from 20 countries, including senior scientists and young physicists. During the five days of the conference, 98 presentations were given in seven plenary sessions. The attendees had in-depth discussions on the latest developments and innovations in calorimetry, including the exciting new LHC results. From the presentations, 83 papers were published in this proceedings. The success of the conference was due to the participants' enthusiasm and the excellent talks given by the speakers, and to the conveners for organizing the individual sessions. We would like to thank the International Advisory Committee for giving us the opportunity to host this Conference in Beijing. Finally we would like to thank all the people involved in the organization of the Conference, who have provided valuable local support. Yifang WangChair of Local Organizing Committee International Advisory Committee M DanilovITEP Moscow M DiemozINFN Roma I A EreditatoBern F L FabbriINFN Frascati T KobayashiICEPP Tokyo M LivanPavia University & INFN P LubranoINFN Perugia S MagillANL Argonne A MaioLIPP Lisbon H OberlackMPI Munich A ParaFermilab R WigmansTTU Lubbock R YoshidaANL Argonne R ZhuCaltech Local Organizing Committee Y WangIHEP (Chair) Y GaoTshinghua University T HuIHEP (Scientific secretary) C LiUSTC W LiIHEP J LuIHEP P WangIHEP T XuIHEP L ZhouIHEP Session Conveners 1) Materials and detectors - Junguang Lu (IHEP), Francesca Nessi (CERN) 2) Algorithm and simulation - Nural Akchurin

  20. Calorimetry at the international linear collider. From simulation to reality

    Energy Technology Data Exchange (ETDEWEB)

    Wattimena, Nanda


    Calorimetry plays a crucial role in ongoing and upcoming high-energy physics experiments. To build a powerful calorimetric system with a performance tailored to the expected physics signatures, demands dedicated research and development of new readout technologies as well as dedicated reconstruction algorithms. The presented design of a calorimetric system which meets the high demands of precision physics at the future linear collider ILC, follows the paradigm of particle ow. Particle ow is a reconstruction principle that relies on a calorimetric system with high spatial granularity. In the detector optimisation process, the development of hardware and software are interlinked and cannot be judged independently. This thesis addresses two different aspects of detector optimisation, a test of the detector design against one example physics scenario and the development of a stable calibration procedure. In the rst part, a gauge-mediated Supersymmetry breaking scenario is used to test the design of the electromagnetic calorimeter in a full detector simulation study. The reconstruction of the neutralino properties, each decaying into a photon and a gravitino, requires a good energy resolution, as well as excellent position and angular resolution. The error bounds on the neutralino mass is strongly linked to the energy resolution, while the position and angular reconstruction of neutral particles is essential for the determination of the neutralino lifetime. The second part of this thesis focuses on the calibration procedure for a prototype of the hadron calorimeter. 7608 novel photodetectors are operated and tested in this prototype. They are exposed to beams of well de ned particle type and energy. The calibration is tested with a detailed study of electromagnetic showers inside the cubic-metre-sized prototype, with special attention paid towards the non-linearity correction. (orig.)

  1. Analysis of RNA folding and ligand binding by conventional and high-throughput calorimetry. (United States)

    Sokoloski, Joshua E; Bevilacqua, Philip C


    Noncoding RNAs serve myriad functions in the cell, but their biophysical properties are not well understood. Calorimetry offers direct and label-free means for characterizing the ligand-binding and thermostability properties of these RNA. We apply two main types of calorimetry--isothermal titration calorimetry (ITC) and differential scanning calorimetry (DSC)--to the characterization of these functional RNA molecules. ITC can describe ligand binding in terms of stoichiometry, affinity, and heat (enthalpy), while DSC can provide RNA stability in terms of heat capacity, melting temperature, and folding enthalpy. Here, we offer detailed experimental protocols for studying such RNA systems with commercially available conventional and high-throughput ITC and DSC instruments.

  2. Determination of Heats of Fusion: Using Differential Scanning Calorimetry for the AP Chemistry Courses. (United States)

    Temme, Susan M.


    Describes an exercise designed to be used in an Advanced Placement (AP) chemistry course to accompany the study of thermodynamics. Uses Differential Scanning Calorimetry in teaching the concepts of thermochemistry and thermodynamics. (JRH)

  3. An Integrated-Circuit Temperature Sensor for Calorimetry and Differential Temperature Measurement. (United States)

    Muyskens, Mark A.


    Describes the application of an integrated-circuit (IC) chip which provides an easy-to-use, inexpensive, rugged, computer-interfaceable temperature sensor for calorimetry and differential temperature measurement. Discusses its design and advantages. (JRH)

  4. Local Measurement of Fuel Energy Deposition and Heat Transfer Environment During Fuel Lifetime Using Controlled Calorimetry

    Energy Technology Data Exchange (ETDEWEB)

    Don W. Miller; Andrew Kauffmann; Eric Kreidler; Dongxu Li; Hanying Liu; Daniel Mills; Thomas D. Radcliff; Joseph Talnagi


    A comprehensive description of the accomplishments of the DOE grant titled, ''Local Measurement of Fuel Energy Deposition and Heat Transfer Environment During Fuel Lifetime using Controlled Calorimetry''.

  5. A Study of Concept Mapping as an Instructional Intervention in an Undergraduate General Chemistry Calorimetry Laboratory (United States)

    Stroud, Mary W.

    This investigation, rooted in both chemistry and education, considers outcomes occurring in a small-scale study in which concept mapping was used as an instructional intervention in an undergraduate calorimetry laboratory. A quasi-experimental, multiple-methods approach was employed since the research questions posed in this study warranted the use of both qualitative and quantitative perspectives and evaluations. For the intervention group of students, a convenience sample, post-lab concept maps, written discussions, quiz responses and learning surveys were characterized and evaluated. Archived quiz responses for non-intervention students were also analyzed for comparison. Students uniquely constructed individual concept maps containing incorrect, conceptually correct and "scientifically thin" calorimetry characterizations. Students more greatly emphasized mathematical relationships and equations utilized during the calorimetry experiment; the meaning of calorimetry concepts was demonstrated to a lesser extent.

  6. Laser-Shock Experiments: Calorimetry Measurements to TPa Pressures (United States)

    Jeanloz, R.


    Laser-driven shock experiments are more like calorimetry measurements, characterized by determinations of Hugoniot temperature (TH) as a function of shock velocity (US), rather than the equation-of-state measurements afforded by mechanical-impact experiments. This is because particle velocity (up) is often not accessible to direct measurement in laser-shock experiments, so must be inferred with reference to a material having a well-determined, independently calibrated Hugoniot equation of state (up is obtained from the impact velocity in traditional shock experiments, and the combination of US and up yields the pressure-density equation of state for the sample). Application of a Mie-Grüneisen model shows that the isochoric specific heat for a given phase is: CV = (US - c0)2 {s2US (dTH/dUS) + γ0 c0 s (TH/US)}-1 with US = c0 + s up, and γ0 is the zero-pressure Grüneisen parameter (γ/V = constant is assumed here). This result is a generalization to TH-US variables of the Walsh and Christian (1955) formula for the temperature rise along the Hugoniot of a given phase (identified here with a US - up relation that is locally linear); it can be analytically integrated to give TH(US) in terms of an average value of CV, if no phase transition takes place. Analysis of the TH-US slopes obtained from laser-shock measurements on MgO yields specific-heat values ranging from 1.02 (± 0.05) kJ/kg/K at 320-345 GPa and TH = 7700-9000 K to 1.50 (± 0.05) kJ/kg/K at 350-380 GPa and TH = 8700-9500 K. A fit to the absolute values of TH(US) in this pressure-temperature range gives CV = 1.26 (± 0.10) kJ/kg/K, in good accord with the Dulong-Petit value CV = 1.24 kJ/kg/K.

  7. Proposal for continuing studies on lead/scintillating fibres calorimetry (LFC)

    CERN Document Server

    Anzivino, Giuseppina; Bari, G; Basile, M; Bellagamba, L; Bencheikh, C; Boscherini, D; Bruni, G; Bruni, P; Buzuloiu, V; Cara Romeo, G; Chiarini, M; Cifarelli, Luisa; Cindolo, F; Ciralli, F; Contin, A; Dardo, M; De Pasquale, S; DeSalvo, R; Frasconi, F; Gheorghe, A; Giusti, P; Hao, E; Iacobucci, G; Laurenti, G; Lundin, M; Maccarrone, G D; Margotti, A; Massam, Thomas; Mondardini, M R; Nania, R; Peskov, Vladimir; Sartorelli, G; Scioni, M; Timellini, R; Wang, Y; Xu, C; You, K; Zichichi, Antonino; CERN. Geneva. Detector Research and Development Committee


    Starting from the results obtained in the framework of the LAA Project 2B, we propose a continuation of the R&D on lead/scintillating fibres calorimetry ("spaghetti calorimetry"), including further tests on the old calorimeter prototypes and the construction and testing of new prototypes. The main results we pursue concern the performances of a projective calorimeter built with new, cheaper techniques and the radiation hardness of the scintillating fibres; the optimization of a preshower detector system is also studied.

  8. DSC、MDSC测定物质比热容的比较%Comparison of differential scanning calorimetry and modulated differential scanning calorimetry in measurement of specific heat capacities

    Institute of Scientific and Technical Information of China (English)

    鲁红; 冯大春; 杨继佑


    实验用TA公司具有DSC、MDSC两种模式、具备先进Tzero技术的热流型DSCQ200热分析仪测定物质的比热容.对如何运用传统方法及调制方法测定物质的比热容进行了详细阐述;以氯化钾、苯甲酸、去离子水为测试样,对两种方法所得实验结果进行了分析比较.%The specific heat capacities of potassium choride, benzoic acid and deionized water samples were measured by DSCQ 200 tbermal analyzer in two different method (differential scanning calorimetry. DSC, and modulated differential scanning calorimetry. MDSC), The results obtained by two methods are compared.The questions in the application of DSC and MDSC are discussed in detail.

  9. Insights into glass transition and relaxation behavior using temperature-modulated differential scanning calorimetry

    DEFF Research Database (Denmark)

    Guo, Xiaoju; Mauro, J.C.; Allan, D.C.;

    Temperature-modulated differential scanning calorimetry (TMDSC) is based on conventional DSC but with a sinusoidally modulated temperature path. Our simulations of TMDSC signals prove that the frequency correction of non-reversing heat flow can give a master curve within a certain range of freque......Temperature-modulated differential scanning calorimetry (TMDSC) is based on conventional DSC but with a sinusoidally modulated temperature path. Our simulations of TMDSC signals prove that the frequency correction of non-reversing heat flow can give a master curve within a certain range...

  10. Aqueous solutions of proline and NaCl studied by differential scanning calorimetry at subzero temperatures

    DEFF Research Database (Denmark)

    Rasmussen, Peter Have; Jørgensen, Bo; Nielsen, Jette


    The hydration properties of proline are studied by differential scanning calorimetry (DSC) in aqueous solutions during freezing to -60 degrees C and subsequent heating to +20 degrees C. The concentration of proline in the freeze concentrated solution was estimated to approximately 50 wt% (w/w) in...

  11. Low-temperature transitions in cod and tuna determined by differential scanning calorimetry

    DEFF Research Database (Denmark)

    Jensen, Kristina Nedenskov; Jørgensen, Bo; Nielsen, Jette


    Differential scanning calorimetry measurements have revealed different thermal transitions in cod and tuna samples. Transition temperatures detected Lit -11degreesC, -15degreesC and -21degreesC were highly dependent on the annealing temperature. In tuna muscle an additional transition was observe...

  12. Subsite binding energies of an exo-polygalacturonase using isothermal titration calorimetry (United States)

    Thermodynamic parameters for binding of a series of galacturonic acid oligomers to an exo-polygalacturonase, RPG16 from Rhizopus oryzae, were determined by isothermal titration calorimetry. Binding of oligomers varying in chain length from two to five galacturonic acid residues is an exothermic proc...

  13. Thermodynamic profiling of Peptide membrane interactions by isothermal titration calorimetry: a search for pores and micelles

    DEFF Research Database (Denmark)

    Henriksen, Jonas Rosager; Andresen, Thomas Lars


    in mixed peptide-lipid micelles. We have investigated the mode of action of the antimicrobial peptide mastoparan-X using isothermal titration calorimetry (ITC) and cryo-transmission electron microscopy (cryo-TEM). The results show that mastoparan-X induces a range of structural transitions of POPC/POPG (3...

  14. Isothermal Titration Calorimetry and Macromolecular Visualization for the Interaction of Lysozyme and Its Inhibitors (United States)

    Wei, Chin-Chuan; Jensen, Drake; Boyle, Tiffany; O'Brien, Leah C.; De Meo, Cristina; Shabestary, Nahid; Eder, Douglas J.


    To provide a research-like experience to upper-division undergraduate students in a biochemistry teaching laboratory, isothermal titration calorimetry (ITC) is employed to determine the binding constants of lysozyme and its inhibitors, N-acetyl glucosamine trimer (NAG[subscript 3]) and monomer (NAG). The extremely weak binding of lysozyme/NAG is…

  15. Thermoreversible gelation of cellulose acetate solutions studied by differential scanning calorimetry

    NARCIS (Netherlands)

    Altena, F.W.; Schroder, J.S.; Huls, van de R.; Smolders, C.A.


    Thermoreversible gels of cellulose acetate can be obtained by cooling concentrated cellulose acetate solutions in solvent-nonsolvent mixtures of dioxane and water. Upon heating the gels, endothermic effects were observed with differential scanning calorimetry. The heat effects are ascribed to the me

  16. Levitation calorimetry. IV - The thermodynamic properties of liquid cobalt and palladium. (United States)

    Treverton, J. A.; Margrave, J. L.


    Some of the thermodynamic properties of liquid cobalt and palladium investigated by means of levitation calorimetry are reported and discussed. The presented data include the specific heats and heats of fusion of the liquid metals, and the emissivities of the liquid metal surfaces.

  17. Student Learning of Thermochemical Concepts in the Context of Solution Calorimetry. (United States)

    Greenbowe, Thomas J.; Meltzer, David E.


    Analyzes student performance on solution calorimetry problems in an introductory university chemistry class. Includes data from written classroom exams for 207 students and an extensive longitudinal interview with a student. Indicates learning difficulties, most of which appear to originate from failure to understand, that net increases and…

  18. Gamma Polari-Calorimetry with SOI pixels for proposals at Extreme Light Infrastructure (ELI-NP)

    CERN Document Server

    Homma, Kensuke


    We introduce the concept of Gamma Polari-Calorimetry (GPC) dedicated for proposals at Extreme Light Infrastructure in the Romanian site (ELI-NP). A simulation study shows that an assembly of thin SOI pixel sensors can satisfy our requirements to GPC.

  19. On the Frequency Correction in Temperature-Modulated Differential Scanning Calorimetry of Glass Transition

    DEFF Research Database (Denmark)

    Guo, Xiaoju; Mauro, J.C.; Allan, D.C.;


    Temperature-modulated differential scanning calorimetry (TMDSC) is based on conventional DSC but with a sinusoidally modulated temperature path. Simulations of TMDSC signals were performed for Corning EAGLE XG® glass over a wide range of modulation frequencies. Our results reveal that the frequen...

  20. Isoquinoline alkaloids and their binding with DNA: calorimetry and thermal analysis applications. (United States)

    Bhadra, Kakali; Kumar, Gopinatha Suresh


    Alkaloids are a group of natural products with unmatched chemical diversity and biological relevance forming potential quality pools in drug screening. The molecular aspects of their interaction with many cellular macromolecules like DNA, RNA and proteins are being currently investigated in order to evolve the structure activity relationship. Isoquinolines constitute an important group of alkaloids. They have extensive utility in cancer therapy and a large volume of data is now emerging in the literature on their mode, mechanism and specificity of binding to DNA. Thermodynamic characterization of the binding of these alkaloids to DNA may offer key insights into the molecular aspects that drive complex formation and these data can provide valuable information about the balance of driving forces. Various thermal techniques have been conveniently used for this purpose and modern calorimetric instrumentation provides direct and quick estimation of thermodynamic parameters. Thermal melting studies and calorimetric techniques like isothermal titration calorimetry and differential scanning calorimetry have further advanced the field by providing authentic, reliable and sensitive data on various aspects of temperature dependent structural analysis of the interaction. In this review we present the application of various thermal techniques, viz. isothermal titration calorimetry, differential scanning calorimetry and optical melting studies in the characterization of drug-DNA interactions with particular emphasis on isoquinoline alkaloid-DNA interaction.

  1. Thermal characterization of starch-water system by photopyroelectric technique and adiabatic scanning calorimetry (United States)

    Cruz-Orea, A.; Bentefour, E. H.; Jamée, P.; Chirtoc, M.; Glorieux, C.; Pitsi, G.; Thoen, J.


    Starch is one of the most important carbohydrate sources in human nutrition. For the thermal analysis of starch, techniques such as differential scanning calorimetry have been extensively used. As an alternative, we have applied a photopyroelectric (PPE) configuration and adiabatic scanning calorimetry (ASC) to study the thermal properties of starch-water systems. For this study we used nixtamalized corn flour and potato starch with different quantities of distilled water, in order to obtain samples with different moisture content. By using PPE and ASC methods we have measured, for each technique separately, the heat capacity by unit volume (ρcp) at room temperature for a corn flour sample at 90% moisture. The obtained values agree within experimental uncertainty. By using these techniques we also studied the thermal behavior of potato starch, at 80% moisture, in the temperature range where phase transitions occur. In this case the PPE signal phase could be used as a sensitive and versatile monitor for phase transitions.

  2. Laser Calorimetry Spectroscopy for ppm-level Dissolved Gas Detection and Analysis (United States)

    K. S., Nagapriya; Sinha, Shashank; Prashanth, R.; Poonacha, Samhitha; Chaudhry, Gunaranjan; Bhattacharya, Anandaroop; Choudhury, Niloy; Mahalik, Saroj; Maity, Sandip


    In this paper we report a newly developed technique – laser calorimetry spectroscopy (LCS), which is a combination of laser absorption spectroscopy and calorimetry - for the detection of gases dissolved in liquids. The technique involves determination of concentration of a dissolved gas by irradiating the liquid with light of a wavelength where the gas absorbs, and measuring the temperature change caused by the absorbance. Conventionally, detection of dissolved gases with sufficient sensitivity and specificity was done by first extracting the gases from the liquid and then analyzing the gases using techniques such as gas chromatography. Using LCS, we have been able to detect ppm levels of dissolved gases without extracting them from the liquid. In this paper, we show the detection of dissolved acetylene in transformer oil in the mid infrared (MIR) wavelength (3021 nm) region.

  3. Modulated Temperature Differential Scanning Calorimetry Theoretical and Practical Applications in Polymer Characterisation

    CERN Document Server

    Reading, Mike


    MTDSC provides a step-change increase in the power of calorimetry to characterize virtually all polymer systems including curing systems, blends and semicrystalline polymers. It enables hidden transitions to be revealed, miscibility to be accurately assessed, and phases and interfaces in complex blends to be quantified. It also enables crystallinity in complex systems to be measured and provides new insights into melting behaviour. All of this is achieved by a simple modification of conventional DSC. In 1992 a new calorimetric technique was introduced that superimposed a small modulation on top of the conventional linear temperature program typically used in differential scanning calorimetry. This was combined with a method of data analysis that enabled the sample’s response to the linear component of the temperature program to be separated from its response to the periodic component. In this way, for the first time, a signal equivalent to that of conventional DSC was obtained simultaneously with a measure ...

  4. Characterization of photomultiplier tubes in a novel operation mode for Secondary Emission Ionization Calorimetry (United States)

    Tiras, E.; Dilsiz, K.; Ogul, H.; Southwick, D.; Bilki, B.; Wetzel, J.; Nachtman, J.; Onel, Y.; Winn, D.


    Hamamatsu single anode R7761 and multi-anode R5900-00-M16 Photomultiplier Tubes have been characterized for use in a Secondary Emission (SE) Ionization Calorimetry study. SE Ionization Calorimetry is a novel technique to measure electromagnetic shower particles in extreme radiation environments. The different operation modes used in these tests were developed by modifying the conventional PMT bias circuit. These modifications were simple changes to the arrangement of the voltage dividers of the baseboard circuits. The PMTs with modified bases, referred to as operating in SE mode, are used as an SE detector module in an SE calorimeter prototype, and placed between absorber materials (Fe, Cu, Pb, W, etc.). Here, the technical design of different operation modes, as well as the characterization measurements of both SE modes and the conventional PMT mode are reported.

  5. Determination of the catalytic activity of binuclear metallohydrolases using isothermal titration calorimetry. (United States)

    Pedroso, Marcelo M; Ely, Fernanda; Lonhienne, Thierry; Gahan, Lawrence R; Ollis, David L; Guddat, Luke W; Schenk, Gerhard


    Binuclear metallohydrolases are a large and diverse family of enzymes that are involved in numerous metabolic functions. An increasing number of members find applications as drug targets or in processes such as bioremediation. It is thus essential to have an assay available that allows the rapid and reliable determination of relevant catalytic parameters (k cat, K m, and k cat/K m). Continuous spectroscopic assays are frequently only possible by using synthetic (i.e., nonbiological) substrates that possess a suitable chromophoric marker (e.g., nitrophenol). Isothermal titration calorimetry, in contrast, affords a rapid assay independent of the chromophoric properties of the substrate-the heat associated with the hydrolytic reaction can be directly related to catalytic properties. Here, we demonstrate the efficiency of the method on several selected examples of this family of enzymes and show that, in general, the catalytic parameters obtained by isothermal titration calorimetry are in good agreement with those obtained from spectroscopic assays.

  6. Effects of lipid membrane curvature on lipid packing state evaluated by isothermal titration calorimetry. (United States)

    Yokoyama, Hirokazu; Ikeda, Keisuke; Wakabayashi, Masaki; Ishihama, Yasushi; Nakano, Minoru


    In this report, we present a novel approach for the elucidation of the physicochemical properties of lipid membranes by isothermal titration calorimetry (ITC) to quantify the heat absorbed during the solubilization of vesicles into TritonX-100 micelles. By using large and small unilamellar vesicles for comparison, this method provides calorimetric data on the gel-to-liquid-crystalline phase transition and its curvature effects and, in particular, the enthalpy change upon membrane deformation from a planar to a curved shape, which cannot be obtained by the conventional approach using differential scanning calorimetry. The results showed quantitatively that the increase in membrane curvature increases the enthalpy of 1,2-dimyristoyl-sn-glycero-3-phosphocholine membranes both below and above the phase-transition temperature, and that the effect is more significant for the former condition. The calorimetric data obtained are further discussed in relation to the elastic bending energy of the membranes and membrane-peptide interaction.

  7. Laser Calorimetry Spectroscopy for ppm-level Dissolved Gas Detection and Analysis (United States)

    K. S., Nagapriya; Sinha, Shashank; R., Prashanth; Poonacha, Samhitha; Chaudhry, Gunaranjan; Bhattacharya, Anandaroop; Choudhury, Niloy; Mahalik, Saroj; Maity, Sandip


    In this paper we report a newly developed technique – laser calorimetry spectroscopy (LCS), which is a combination of laser absorption spectroscopy and calorimetry - for the detection of gases dissolved in liquids. The technique involves determination of concentration of a dissolved gas by irradiating the liquid with light of a wavelength where the gas absorbs, and measuring the temperature change caused by the absorbance. Conventionally, detection of dissolved gases with sufficient sensitivity and specificity was done by first extracting the gases from the liquid and then analyzing the gases using techniques such as gas chromatography. Using LCS, we have been able to detect ppm levels of dissolved gases without extracting them from the liquid. In this paper, we show the detection of dissolved acetylene in transformer oil in the mid infrared (MIR) wavelength (3021 nm) region. PMID:28218304

  8. Absolute dosimetry on a dynamically scanned sample for synchrotron radiotherapy using graphite calorimetry and ionization chambers (United States)

    Lye, J. E.; Harty, P. D.; Butler, D. J.; Crosbie, J. C.; Livingstone, J.; Poole, C. M.; Ramanathan, G.; Wright, T.; Stevenson, A. W.


    The absolute dose delivered to a dynamically scanned sample in the Imaging and Medical Beamline (IMBL) on the Australian Synchrotron was measured with a graphite calorimeter anticipated to be established as a primary standard for synchrotron dosimetry. The calorimetry was compared to measurements using a free-air chamber (FAC), a PTW 31 014 Pinpoint ionization chamber, and a PTW 34 001 Roos ionization chamber. The IMBL beam height is limited to approximately 2 mm. To produce clinically useful beams of a few centimetres the beam must be scanned in the vertical direction. In practice it is the patient/detector that is scanned and the scanning velocity defines the dose that is delivered. The calorimeter, FAC, and Roos chamber measure the dose area product which is then converted to central axis dose with the scanned beam area derived from Monte Carlo (MC) simulations and film measurements. The Pinpoint chamber measures the central axis dose directly and does not require beam area measurements. The calorimeter and FAC measure dose from first principles. The calorimetry requires conversion of the measured absorbed dose to graphite to absorbed dose to water using MC calculations with the EGSnrc code. Air kerma measurements from the free air chamber were converted to absorbed dose to water using the AAPM TG-61 protocol. The two ionization chambers are secondary standards requiring calibration with kilovoltage x-ray tubes. The Roos and Pinpoint chambers were calibrated against the Australian primary standard for air kerma at the Australian Radiation Protection and Nuclear Safety Agency (ARPANSA). Agreement of order 2% or better was obtained between the calorimetry and ionization chambers. The FAC measured a dose 3-5% higher than the calorimetry, within the stated uncertainties.

  9. Revisiting the streptavidin-biotin binding by using an aptamer and displacement isothermal calorimetry titration. (United States)

    Kuo, Tai-Chih; Tsai, Ching-Wei; Lee, Peng-Chen; Chen, Wen-Yih


    The association constant of a well-known streptavidin-biotin binding has only been inferred from separately measured kinetic parameters. In a single experiment, we obtained Ka 1 × 10(12)  M(-1) by using a streptavidin-binding aptamer and ligand-displacement isothermal titration calorimetry. This study explores the challenges of determining thermodynamic parameters and the derived equilibrium binding affinity of tight ligand-receptor binding.

  10. Investigation of used Conveyor Belts by the Differential Scanning Calorimetry Analysis

    Directory of Open Access Journals (Sweden)

    Lucia Knapcikova,


    Full Text Available In this paper is presented the use of differential scanning calorimetry analysis of the used conveyor belts. This method has been specifically tested on the individual components contained in the used conveyor belts esp. rubber pellets, cord and fabric. The result of the analysis is the determination of Tg temperature and melting temperatures (Tm by the components.Weanalyzed used conveyor belts and after this analysis it was determined components and their application to the industry

  11. Characterization of photomultiplier tubes in a novel secondary ionization mode for Secondary Emission Ionization Calorimetry

    CERN Document Server

    Tiras, E; Ogul, H; Southwick, D; Bilki, B; Nachtman, J; Onel, Y


    Hamamatsu single anode R7761 and multi-anode R5900-00-M16 Photomultiplier Tubes have been characterized for use in Secondary Emission Ionization Calorimetry study, that is a novel techique to measure the electromagnetic shower particles in extreme radiation environment. There are different SE modes used in the tests, developed from conventional PMT mode. Here, the technical design of secondary emission modules and characterization measurements of both SE modes and the PMT mode are reported.

  12. Application of calorimetry in evaluation of phase transformations in the selected hypoeutectic silumins

    Directory of Open Access Journals (Sweden)

    J. Szymszal


    Full Text Available The investigations of phase transformations described in this study were carried out on hypoeutectic alloys from the Al-Si during heating and cooling. The determination and analysis of characteristic temperature values from the solidification range was made by the DSC method in calorimetric investigations carried out on a high-temperature multi HTC Setaram scanning calorimeter. Applying the lever rule, the phase composition of the examined slumins was calculated and compared with the results of DSC calorimetry.

  13. Determination of the aggregation number for micelles by isothermal titration calorimetry

    DEFF Research Database (Denmark)

    Olesen, Niels Erik; Holm, Rene; Westh, Peter


    Isothermal titration calorimetry (ITC) has previously been applied to estimate the aggregation number (n), Gibbs free energy (ΔG), enthalpy (ΔH) and entropy (ΔS) of micellization. However, some difficulties of micelle characterization by ITC still remain; most micelles have aggregation numbers...... insight into optimal design of titration protocols for micelle characterization. By applying the new method, the aggregation number of sodium dodecyl sulphate and glycochenodeoxycholate was determined at concentrations around their critical micelle concentration (CMC)...

  14. Picosecond calorimetry

    DEFF Research Database (Denmark)

    Georgiou, Panayiotis; Vincent, Jonathan; Andersson, Magnus


    to rapidly heat liquid C H2 Cl2 using UV pulses of 100 fs duration. A significant x-ray diffraction signal is visible prior to the onset of thermal expansion, which characterizes a highly compressed superheated liquid. Liquid C H2 Cl2 then expands as a shock wave propagates through the sample...

  15. STAR Calorimetry

    Energy Technology Data Exchange (ETDEWEB)

    Jacobs, W W, E-mail: jacobsw@indiana.ed [Indiana University Cyclotron Facility and Department of Physics, 2401 Milo B. Sampson Lane, Bloomington IN 47408 (United States)


    The main STAR calorimeters comprise a full Barrel EMC and single Endcap EMC plus a Forward Meson Spectrometer. Together they give a nearly complete coverage over the range -1 < pseudorapidity < 4 and provide EM readout and triggering that help drive STAR physics capabilities. Their description, status, performance and operations (and a few physics anecdotes) are briefly presented and discussed.

  16. Mathematical model of cycad cones' thermogenic temperature responses: inverse calorimetry to estimate metabolic heating rates. (United States)

    Roemer, R B; Booth, D; Bhavsar, A A; Walter, G H; Terry, L I


    A mathematical model based on conservation of energy has been developed and used to simulate the temperature responses of cones of the Australian cycads Macrozamia lucida and Macrozamia. macleayi during their daily thermogenic cycle. These cones generate diel midday thermogenic temperature increases as large as 12 °C above ambient during their approximately two week pollination period. The cone temperature response model is shown to accurately predict the cones' temperatures over multiple days as based on simulations of experimental results from 28 thermogenic events from 3 different cones, each simulated for either 9 or 10 sequential days. The verified model is then used as the foundation of a new, parameter estimation based technique (termed inverse calorimetry) that estimates the cones' daily metabolic heating rates from temperature measurements alone. The inverse calorimetry technique's predictions of the major features of the cones' thermogenic metabolism compare favorably with the estimates from conventional respirometry (indirect calorimetry). Because the new technique uses only temperature measurements, and does not require measurements of oxygen consumption, it provides a simple, inexpensive and portable complement to conventional respirometry for estimating metabolic heating rates. It thus provides an additional tool to facilitate field and laboratory investigations of the bio-physics of thermogenic plants.

  17. Recent development of material calorimetry%材料量热学的发展现状

    Institute of Scientific and Technical Information of China (English)

    孙玉霞; 李荣德


    材料量热学是测量材料变化过程中与热有关的各种物理量(如热焓、熵值等)变化规律的一门学科,分析了国内外材料量热学的发展状况,尤其是对材料量热学中的热分析技术进行了论述,对热分析方法中的差热分析方法(DTA)和差示扫描量热法(DSC)的应用情况做了分析和展望.%Material calorimetry is a subject that measures the changing laws of physical quantities such as enthalpy and entropy that are related to thermal. Recent development of material calorimetry at home and abroad has been reviewed and especially Thermal Analysis (fA) in calorimetric methods has been discussed in the paper. Differential Thermal Analysis (DTA) and Differential Scanning Calorimetry (DSC) in thermal analysis have been analyzed in derail. Moreover, several suggestions have been put forward in the end.

  18. Percent relative cumulative frequency analysis in indirect calorimetry: application to studies of transgenic mice. (United States)

    Riachi, Marc; Himms-Hagen, Jean; Harper, Mary-Ellen


    Indirect calorimetry is commonly used in research and clinical settings to assess characteristics of energy expenditure. Respiration chambers in indirect calorimetry allow measurements over long periods of time (e.g., hours to days) and thus the collection of large sets of data. Current methods of data analysis usually involve the extraction of only a selected small proportion of data, most commonly the data that reflects resting metabolic rate. Here, we describe a simple quantitative approach for the analysis of large data sets that is capable of detecting small differences in energy metabolism. We refer to it as the percent relative cumulative frequency (PRCF) approach and have applied it to the study of uncoupling protein-1 (UCP1) deficient and control mice. The approach involves sorting data in ascending order, calculating their cumulative frequency, and expressing the frequencies in the form of percentile curves. Results demonstrate the sensitivity of the PRCF approach for analyses of oxygen consumption (.VO2) as well as respiratory exchange ratio data. Statistical comparisons of PRCF curves are based on the 50th percentile values and curve slopes (H values). The application of the PRCF approach revealed that energy expenditure in UCP1-deficient mice housed and studied at room temperature (24 degrees C) is on average 10% lower (p calorimetry is increasingly used, and the PRCF approach provides a novel and powerful means for data analysis.

  19. Reading and listening to music increase resting energy expenditure during an indirect calorimetry test. (United States)

    Snell, Blaire; Fullmer, Susan; Eggett, Dennis L


    Indirect calorimetry is often done early in the morning in a fasting state, with the subject unshowered and abstained from caffeine or other stimulants. Subjects often fall asleep, resulting in measurement of a sleeping metabolic rate rather than a resting metabolic rate. The objective of this study was to determine whether listening to self-selected relaxing music or reading an electronic device or magazine affects resting energy expenditure (REE) during measurement in healthy adults. A randomized trial comparing three different conditions (ie, resting, reading, and listening to music) was performed. Sixty-five subjects (36 female and 29 male) were used in final data analysis. Inclusion criteria included healthy subjects between the ages of 18 and 50 years with a stable weight. Exclusion criteria included pregnant or lactating women or use of medications known to affect metabolism. Results showed that reading either a magazine or an electronic device significantly increased REE by 102.7 kcal/day when compared with resting (Pmusic increased REE by 27.6 kcal/day compared with rest (P=0.0072). Based on our results, we recommend subjects refrain from reading a magazine or electronic device during an indirect calorimetry test. Whether or not the smaller difference found while listening to music is practically significant would be a decision for the indirect calorimetry test administrator.

  20. Application of calorimetry and thermal analysis to determine the liquid range and the environmental toxicity of ionic liquids


    Parajó Vieito, Juan José


    This PhD Thesis is focused on the applicability of thermal analysis and calorimetry techniques to determine phase transitions (through Differential Scanning Calorimetry (DSC)), thermal stability (measured by Thermogravimetric Analysis (TGA)) and ecotoxicity (trhough Thermal Activity Monitor (TAM) and seed germination response tests) of ionic liquids (ILs) to be used as lubricants and/or absorbents in heat pumps. The studied compounds are based on different anions (imide, triflate, sulphonate,...

  1. Differential scanning calorimetry in life science: thermodynamics, stability, molecular recognition and application in drug design. (United States)

    Bruylants, G; Wouters, J; Michaux, C


    All biological phenomena depend on molecular recognition, which is either intermolecular like in ligand binding to a macromolecule or intramolecular like in protein folding. As a result, understanding the relationship between the structure of proteins and the energetics of their stability and binding with others (bio)molecules is a very interesting point in biochemistry and biotechnology. It is essential to the engineering of stable proteins and to the structure-based design of pharmaceutical ligands. The parameter generally used to characterize the stability of a system (the folded and unfolded state of the protein for example) is the equilibrium constant (K) or the free energy (deltaG(o)), which is the sum of enthalpic (deltaH(o)) and entropic (deltaS(o)) terms. These parameters are temperature dependent through the heat capacity change (deltaCp). The thermodynamic parameters deltaH(o) and deltaCp can be derived from spectroscopic experiments, using the van't Hoff method, or measured directly using calorimetry. Along with isothermal titration calorimetry (ITC), differential scanning calorimetry (DSC) is a powerful method, less described than ITC, for measuring directly the thermodynamic parameters which characterize biomolecules. In this article, we summarize the principal thermodynamics parameters, describe the DSC approach and review some systems to which it has been applied. DSC is much used for the study of the stability and the folding of biomolecules, but it can also be applied in order to understand biomolecular interactions and can thus be an interesting technique in the process of drug design.

  2. Titration Calorimetry Applied to the Thermokinetics Study of Consecutive First-order Reactions

    Institute of Scientific and Technical Information of China (English)

    SHI Jing-Yan; LI Jie; WANG Zhi-Yong; LIU Yu-Wen; WANG Cun-Xin


    The thermokinetic mathematical models for consecutive first-order reactions in titration period and the stopped-titration reaction period were proposed for titration calorimetry, based on which, thermodynamic parameters (reaction enthalpies, △rHm1 and △rHm2) and kinetic parameters (rate constants, k1 and k2) of the consecutive first-order reactions could be obtained by directly simulating the calorimetric curve from a single experiment with the method of nonlinear least squares regression (NLLS).The reliability of the model has been verified by investigating the reaction of the saponification of diethyl succinate in an aqueous ethanol solvent.

  3. Catalytic reaction energetics by single crystal adsorption calorimetry: hydrocarbons on Pt(111). (United States)

    Lytken, Ole; Lew, Wanda; Campbell, Charles T


    Single crystal adsorption calorimetry provides essential information about the energetics of surface reactions on well-defined surfaces where the adsorbed reaction products can be clearly identified. In this tutorial review, we cover the essentials of that technique, with emphasis on our lab's recent advances in sensitivity and temperature range, and demonstrate what can be achieved through a review of selected example studies concerning adsorption and dehydrogenation of hydrocarbons on Pt(111). A fairly complete reaction enthalpy diagram is presented for the dehydrogenation of cyclohexane to benzene on Pt(111).

  4. Kinetic analysis of gluconate phosphorylation by human gluconokinase using isothermal titration calorimetry. (United States)

    Rohatgi, Neha; Guðmundsson, Steinn; Rolfsson, Óttar


    Gluconate is a commonly encountered nutrient, which is degraded by the enzyme gluconokinase to generate 6-phosphogluconate. Here we used isothermal titration calorimetry to study the properties of this reaction. ΔH, KM and kcat are reported along with substrate binding data. We propose that the reaction follows a ternary complex mechanism, with ATP binding first. The reaction is inhibited by gluconate, as it binds to an Enzyme-ADP complex forming a dead-end complex. The study exemplifies that ITC can be used to determine mechanisms of enzyme catalyzed reactions, for which it is currently not commonly applied.

  5. Using isothermal titration calorimetry to determine thermodynamic parameters of protein-glycosaminoglycan interactions. (United States)

    Dutta, Amit K; Rösgen, Jörg; Rajarathnam, Krishna


    It has now become increasingly clear that a complete atomic description of how biomacromolecules recognize each other requires knowledge not only of the structures of the complexes but also of how kinetics and thermodynamics drive the binding process. In particular, such knowledge is lacking for protein-glycosaminoglycan (GAG) complexes. Isothermal titration calorimetry (ITC) is the only technique that can provide various thermodynamic parameters-enthalpy, entropy, free energy (binding constant), and stoichiometry-from a single experiment. Here we describe different factors that must be taken into consideration in carrying out ITC titrations to obtain meaningful thermodynamic data of protein-GAG interactions.

  6. Study of the KNO3-Al2O3 system by differential scanning calorimetry (United States)

    Amirov, A. M.; Gafurov, M. M.; Rabadanov, K. Sh.


    The structural and the thermodynamic properties of potassium nitrate KNO3 and its composites with nanosized aluminum oxide Al2O3 have been studied by differential scanning calorimetry. It has been found that an amorphous phase forms in composites (1- x)KNO3- x Al2O3. The thermal effect corresponding to this phase has been observed at 316°C. It has been found that the phase transition heats of potassium nitrate decreased as the aluminum oxide fraction increased.

  7. Vitreous State Characterization of Pharmaceutical Compounds Degrading upon Melting by Using Fast Scanning Calorimetry. (United States)

    Corvis, Yohann; Wurm, Andreas; Schick, Christoph; Espeau, Philippe


    Fast scanning calorimetry, a technique mainly devoted to polymer characterization, is applied here for the first time to low molecular mass organic compounds that degrade upon melting, such as ascorbic acid and prednisolone. Due to the fast scan rates upon heating and cooling, the substances can be obtained in the molten state without degradation and then quenched into the glassy state. The hydrated form and the polymorphic Form 1 of prednisolone were investigated. It is shown that once the sesquihydrate dehydrates, a molten product is obtained. Depending on the heating rate, this molten phase may recrystallize or not into Form 1.

  8. Test in a beam of large-area Micromegas chambers for sampling calorimetry

    Energy Technology Data Exchange (ETDEWEB)

    Adloff, C.; Chefdeville, M., E-mail:; Dalmaz, A.; Drancourt, C.; Gaglione, R.; Geffroy, N.; Jacquemier, J.; Karyotakis, Y.; Koletsou, I.; Peltier, F.; Samarati, J.; Vouters, G.


    The application of Micromegas for sampling calorimetry puts specific constraints on the design and performance of this gaseous detector. In particular, uniform and linear response, low noise and stability against high ionisation density deposits are prerequisites for achieving good energy resolution. A Micromegas-based hadronic calorimeter was proposed for an application at a future linear collider experiment and three technologically advanced prototypes of 1×1 m{sup 2} were constructed. Their merits relative to the above-mentioned criteria are discussed on the basis of measurements performed at the CERN SPS test-beam facility.

  9. Test in a beam of large-area Micromegas chambers for sampling calorimetry

    CERN Document Server

    Adloff, C; Dalmaz, A; Drancourt, C; Gaglione, R; Geffroy, N; Jacquemier, J; Karyotakis, Y; Koletsou, I; Peltier, F; Samarati, J; Vouters, G


    Application of Micromegas for sampling calorimetry puts specific constraints on the design and performance of this gaseous detector. In particular, uniform and linear response, low noise and stability against high ionisation density deposits are prerequisites to achieving good energy resolution. A Micromegas-based hadronic calorimeter was proposed for an application at a future linear collider experiment and three technologically advanced prototypes of 1$\\times$1 m$^{2}$ were constructed. Their merits relative to the above-mentioned criteria are discussed on the basis of measurements performed at the CERN SPS test-beam facility.

  10. Differential scanning calorimetry: An invaluable tool for a detailed thermodynamic characterization of macromolecules and their interactions

    Directory of Open Access Journals (Sweden)

    Michael H Chiu


    Full Text Available Differential Scanning Calorimetry (DSC is a highly sensitive technique to study the thermotropic properties of many different biological macromolecules and extracts. Since its early development, DSC has been applied to the pharmaceutical field with excipient studies and DNA drugs. In recent times, more attention has been applied to lipid-based drug delivery systems and drug interactions with biomimetic membranes. Highly reproducible phase transitions have been used to determine values, such as, the type of binding interaction, purity, stability, and release from a drug delivery mechanism. This review focuses on the use of DSC for biochemical and pharmaceutical applications.

  11. Software solution for control and data acquisition in the pulse calorimetry method

    Directory of Open Access Journals (Sweden)

    Babić Marijana


    Full Text Available This work presents a software solution for adjusting, controlling, displaying, and acquiring parameters and data in the pulse calorimetry experimental technique for specific heat capacity, electrical resistivity, total hemispherical emissivity, and normal spectral emissivity measurements. The software has been developed under the LabVIEW platform, V.7.11, and an example of its application with measurement results is presented in a separate section. The total expanded uncertainty of obtained results for the specific heat capacity and electrical resistivity of palladium was 5% and 1 - 2%, respectively.

  12. Application of calorimetry in evaluation of phase transformations in the selected hypoeutectic silumins

    Directory of Open Access Journals (Sweden)

    J. Piątkowski


    Full Text Available The investigations of phase transformations described in this study were carried out on hypoeutectic alloys from the Al-Si system (AlSi3, AlSi6 and AlSi9 during heating and cooling. The determination and analysis of characteristic temperature values from the solidification range was made by the DSC method in calorimetric investigations carried out on a high-temperature multi HTC scanning calorimeter. Applying the lever rule, the phase composition of the examined silumins was calculated and compared with the results of DSC calorimetry, obtaining a good correlation of the results.

  13. Recommendations for improved data processing from expired gas analysis indirect calorimetry. (United States)

    Robergs, Robert A; Dwyer, Dan; Astorino, Todd


    There is currently no universally recommended and accepted method of data processing within the science of indirect calorimetry for either mixing chamber or breath-by-breath systems of expired gas analysis. Exercise physiologists were first surveyed to determine methods used to process oxygen consumption ((.)VO2) data, and current attitudes to data processing within the science of indirect calorimetry. Breath-by-breath datasets obtained from indirect calorimetry during incremental exercise were then used to demonstrate the consequences of commonly used time, breath and digital filter post-acquisition data processing strategies. Assessment of the variability in breath-by-breath data was determined using multiple regression based on the independent variables ventilation (VE), and the expired gas fractions for oxygen and carbon dioxide, FEO2 and FECO2, respectively. Based on the results of explanation of variance of the breath-by-breath (.)VO2 data, methods of processing to remove variability were proposed for time-averaged, breath-averaged and digital filter applications. Among exercise physiologists, the strategy used to remove the variability in (.)VO2 measurements varied widely, and consisted of time averages (30 sec [38%], 60 sec [18%], 20 sec [11%], 15 sec [8%]), a moving average of five to 11 breaths (10%), and the middle five of seven breaths (7%). Most respondents indicated that they used multiple criteria to establish maximum ((.)VO2 ((.)VO2max) including: the attainment of age-predicted maximum heart rate (HR(max)) [53%], respiratory exchange ratio (RER) >1.10 (49%) or RER >1.15 (27%) and a rating of perceived exertion (RPE) of >17, 18 or 19 (20%). The reasons stated for these strategies included their own beliefs (32%), what they were taught (26%), what they read in research articles (22%), tradition (13%) and the influence of their colleagues (7%). The combination of VE, FEO2 and FECO2 removed 96-98% of (.)VO2 breath-by-breath variability in incremental

  14. Thermodynamics of actinide complexation in solution at elevated temperatures: application of variable-temperature titration calorimetry. (United States)

    Rao, Linfeng


    Studies of actinide complexation in solution at elevated temperatures provide insight into the effect of solvation and the energetics of complexation, and help to predict the chemical behavior of actinides in nuclear waste processing and disposal where temperatures are high. This tutorial review summarizes the data on the complexation of actinides at elevated temperatures and describes the methodology for thermodynamic measurements, with the emphasis on variable-temperature titration calorimetry, a highly valuable technique to determine the enthalpy and, under appropriate conditions, the equilibrium constants of complexation as well.

  15. Impact of sample saturation on the detected porosity of hardened concrete using low temperature calorimetry

    DEFF Research Database (Denmark)

    Wu, Min; Johannesson, Björn


    The present work studied the impact of sample saturation on the analysis of pore volume and pore size distribution by low temperature (micro-)calorimetry. The theoretical background was examined, which emphasizes that the freezing/melting temperature of water/ice confined in non-fully saturated...... pores is further depressed compared with that when the pores are fully saturated. The study of the experimental data on hardened concrete samples showed that for a same concrete mix, the total pore volume detected from the capillary saturated samples was always lower than that of the vacuum saturated...

  16. Methodology of hot nucleus calorimetry and thermometry produced by nuclear reactions around Fermi energies; Methodologie de la calorimetrie et de la thermometrie des noyaux chauds formes lors de collisions nucleaires aux energies de Fermi

    Energy Technology Data Exchange (ETDEWEB)

    Vient, E


    This work deals with the calorimetry and thermometry of hot nuclei produced in collisions Xe + Sn between 25 and 100 MeV/u. The apparatus for hot nucleus physical characterization is the 4{pi} detector array Indra. This study was made by using the event generators Gemini, Simon and Hipse and a data-processing filter simulating the complete operation of the multi-detector. The first chapter presents the different ways of producing hot nuclei. In the second and third chapters, the author presents a critical methodological study of calorimetry and thermometry applied to hot nuclei, different methods are reviewed, their accuracy and application range are assessed. All the calorimetry methods rely on the assumption that we are able to discriminate decay products of the hot nucleus from evaporated particles. In the fourth chapter, the author gives some ways of improving calorimetry characterization of the hot nucleus. An alternative method of calorimetry is proposed in the fifth chapter, this method is based on the experimental determination of an evaporation probability that is deduced from the physical characteristics of the particles present in a restricted domain of the space of velocities.

  17. Monitoring of butter and animal fat oxidation stability by differential scanning calorimetry (DSC

    Directory of Open Access Journals (Sweden)

    Jasminka Sadadinović


    Full Text Available Oxidation of fat is one of the basic reactions which causes the depletion of butter and animal fat quality as well as other products containing them. Since the most of reaction products of fat oxidation are harmful for consumers' health, inadequate and scarce monitoring of edible fats and fat containing products quality, presents increased health risk as well as financial loss for the producers. In fat oxidation stability estimation, standard chemical methods were used (iodine number, acid number, peroxide number, anisidine number etc., which require time and chemical usage. Differential scanning calorimetry (DSC analysis presents the simple and efficient way for butter and animal fats oxidation stability estimation. Laboratory investigations were performed to monitor oxidation stability of butter and animal fat in fresh state, as well as in spent phase, used in frying process. The results obtained were compared to the results of standard chemical analysis, and they confirmed the reproducibility and applicability of differential scanning calorimetry in oxidation stability of butter and animal fats monitoring.

  18. Calorimetry exchange program quarterly data report, 2nd quarter CY93

    Energy Technology Data Exchange (ETDEWEB)

    Barnett, T.M.


    The goals of the Calorimetry Sample Exchange Program are to: discuss measurement differences; review and improve analytical measurements and methods; discuss new measurement capabilities; provide data to DOE on measurement capabilities to evaluate shipper-receiver differences; provide characterized or standard materials as necessary for exchange participants; and provide a measurement control program for plutonium analysis. A sample of PuO{sub 2} powder is available at each participating site for NDA measurement, including either or both calorimetry and high-resolution gamma-ray spectroscopy, the elements which are typically combined to provide a calorimetric assay of plutonium. The facilities measure the sample as frequently and to the level of precision which they desire, and then submit the data to the exchange for analysis. The data report includes summary tables for each measurement and charts showing the performance of each laboratory. Comparisons are made to the accepted values for the exchange sample and to data previously reported by that laboratory. This information is presented, in the form of quarterly and annual reports, intended for use by Exchange participants in measurement control programs, or to indicate when bias corrections may be appropriate. No attempt, however, has been made to standardize methods or frequency of data collection, calibration, or operating procedures. Direct comparisons between laboratories may, therefore, be misleading since data have not been collected to the same precision or for the same time periods.

  19. Reference dosimetry for light-ion beams based on graphite calorimetry. (United States)

    Rossomme, S; Palmans, H; Thomas, R; Lee, N; Duane, S; Bailey, M; Shipley, D; Bertrand, D; Romano, F; Cirrone, P; Cuttone, G; Vynckier, S


    Developments in hadron therapy require efforts to improve the accuracy of the dose delivered to a target volume. Here, the determination of the absorbed dose under reference conditions was analysed. Based on the International Atomic Energy Agency TRS-398 code of practice, for hadron beams, the combined standard uncertainty on absorbed dose to water under reference conditions, derived from ionisation chambers, is too large. This uncertainty is dominated by the beam quality correction factors, [Formula: see text], mainly due to the mean energy to produce one ion pair in air, wair. A method to reduce this uncertainty is to carry out primary dosimetry, using calorimetry. A [Formula: see text]-value can be derived from a direct comparison between calorimetry and ionometry. Here, this comparison is performed using a graphite calorimeter in an 80-MeV A(-1) carbon ion beam. Assuming recommended TRS-398 values of water-to-graphite stopping power ratio and the perturbation factor for an ionisation chamber, preliminary results indicate a wair-value of 35.5 ± 0.9 J C(-1).

  20. Resistivity and AC calorimetry measurements on CeNiGe{sub 2} under pressure

    Energy Technology Data Exchange (ETDEWEB)

    Holmes, A.T. [KYOKUGEN, Osaka University, Toyonaka, Osaka 560-8531 (Japan)]. E-mail:; Muramatsu, T. [KYOKUGEN, Osaka University, Toyonaka, Osaka 560-8531 (Japan); Miyake, A. [KYOKUGEN, Osaka University, Toyonaka, Osaka 560-8531 (Japan); Kaczorowski, D. [KYOKUGEN, Osaka University, Toyonaka, Osaka 560-8531 (Japan); Institute of Low Temperature and Structure Research, Polish Academy of Sciences, P.O. Box 1410, 50-950 Wroclaw (Poland); Bukowski, Z. [Institute of Low Temperature and Structure Research, Polish Academy of Sciences, P.O. Box 1410, 50-950 Wroclaw (Poland); Kagayama, T. [KYOKUGEN, Osaka University, Toyonaka, Osaka 560-8531 (Japan); Shimizu, K. [KYOKUGEN, Osaka University, Toyonaka, Osaka 560-8531 (Japan)


    We present resistivity and AC calorimetry measurements of single crystalline CeNiGe{sub 2} under high pressure and low temperature in a diamond anvil cell. CeNiGe{sub 2} is a highly anisotropic, antiferromagnetic Kondo system at ambient pressure, located close to the boundary with non-magnetic systems. It has two ordering temperatures, T{sub N1}=3.9K and T{sub N2}=3.2K, which are suppressed under pressure. Between 0.7 and 1.4GPa only a single transition was identified, with T{sub N} reaching 1.9K by 1.4 GPa. At 1.9GPa two transitions could again be seen by AC calorimetry at 2.0 and 1.3K, accompanied by a qualitative change in the behaviour of the resistivity. The Sommerfeld coefficient showed a maximum of 755mJmol{sup -1}K{sup -2} at 1.4GPa, up from 448mJmol{sup -1}K{sup -2} at close to ambient pressure. The residual resistivity was found to decrease sharply above 1.4GPa after an initial increase with pressure.

  1. Chip calorimetry for evaluation of biofilm treatment with biocides, antibiotics, and biological agents. (United States)

    Morais, Frida Mariana; Buchholz, Friederike; Maskow, Thomas


    Any growth or bioconversion in biofilms is accompanied by the release of heat. The heat (in J) is tightly related to the stoichiometry of the respective process via law of Hess, and the heat production rate (in W or J/s) is additionally related to the process kinetics. This heat and the heat production rate can nowadays be measured by modern calorimetry with extremely high sensitivity. Flow-through calorimetry allows the measurement of bioprocesses in biofilms in real time, without the need of invasive sample preparation and disturbing of biofilm processes. Furthermore, it can be applied for long-term measurements and is even applicable to turbid media. Chip or miniaturized calorimeters have the additional advantages of extremely short thermal equilibration times and the requirement of very small amounts of media and chemicals. The precision of flow-through chip calorimeters (about 3 mW/L) allows the detection of early stages of biofilm development (about 10(5) bacteria cm(-2)).

  2. Thermal expansivities of peptides, polypeptides and proteins as measured by pressure perturbation calorimetry. (United States)

    Pandharipande, Pranav P; Makhatadze, George I


    The main goal of this work was to provide direct experimental evidence that the expansivity of peptides, polypeptides and proteins as measured by pressure perturbation calorimetry (PPC), can serve as a proxy to characterize relative compactness of proteins, especially the denatured state ensemble. This is very important as currently only small angle X-ray scattering (SAXS), intrinsic viscosity and, to a lesser degree, fluorescence resonance transfer (FRET) experiments are capable of reporting on the compactness of denatured state ensembles. We combined the expansivity measurements with other biophysical methods (far-UV circular dichroism spectroscopy, differential scanning calorimetry, and small angle X-ray scattering). Three case studies of the effects of conformational changes on the expansivity of polypeptides in solution are presented. We have shown that expansivity appears to be insensitive to the helix-coil transition, and appears to reflect the changes in hydration of the side-chains. We also observed that the expansivity is sensitive to the global conformation of the polypeptide chain and thus can be potentially used to probe hydration of different collapsed states of denatured or even intrinsically disordered proteins.

  3. Calorimetry, activity, and micro-FTIR analysis of CO chemisorption, titration, and oxidation on supported Pt (United States)

    Sermon, Paul A.; Self, Valerie A.; Vong, Mariana S. W.; Wurie, Alpha T.


    The value of in situ analysis on CO chemisorption, titration and oxidation over supported Pt catalysts using calorimetry, catalytic and micro-FTIR methods is illustrated using silica- and titania-supported samples. Isothermal CO-O and O2-CO titrations have not been widely used on metal surfaces and may be complicated if some oxide supports are reduced by CO titrant. However, they can illuminate the kinetics of CO oxidation on metal/oxide catalysts since during such titrations all O and CO coverages are scanned as a function of time. There are clear advantages in following the rates of the catalyzed CO oxidation via calorimetry and gc-ms simultaneously. At lower temperatures the evidence they provide is complementary. CO oxidation and its catalysis of CO oxidation have been extensively studied with hysteresis and oscillations apparent, and the present results suggest the benefits of a combined approach. Silica support porosity may be important in defining activity-temperature hysteresis. FTIR microspectroscopy reveals the chemical heterogeneity of the catalytic surfaces used; it is interesting that the evidence with regard to the dominant CO surface species and their reactivities with regard to surface oxygen for present oxide-supported Pt are different from those seen on graphite-supported Pt.

  4. A High-Throughput Biological Calorimetry Core: Steps to Startup, Run, and Maintain a Multiuser Facility. (United States)

    Yennawar, Neela H; Fecko, Julia A; Showalter, Scott A; Bevilacqua, Philip C


    Many labs have conventional calorimeters where denaturation and binding experiments are setup and run one at a time. While these systems are highly informative to biopolymer folding and ligand interaction, they require considerable manual intervention for cleaning and setup. As such, the throughput for such setups is limited typically to a few runs a day. With a large number of experimental parameters to explore including different buffers, macromolecule concentrations, temperatures, ligands, mutants, controls, replicates, and instrument tests, the need for high-throughput automated calorimeters is on the rise. Lower sample volume requirements and reduced user intervention time compared to the manual instruments have improved turnover of calorimetry experiments in a high-throughput format where 25 or more runs can be conducted per day. The cost and efforts to maintain high-throughput equipment typically demands that these instruments be housed in a multiuser core facility. We describe here the steps taken to successfully start and run an automated biological calorimetry facility at Pennsylvania State University. Scientists from various departments at Penn State including Chemistry, Biochemistry and Molecular Biology, Bioengineering, Biology, Food Science, and Chemical Engineering are benefiting from this core facility. Samples studied include proteins, nucleic acids, sugars, lipids, synthetic polymers, small molecules, natural products, and virus capsids. This facility has led to higher throughput of data, which has been leveraged into grant support, attracting new faculty hire and has led to some exciting publications.

  5. Resting energy expenditure and body composition in children with cancer: indirect calorimetry and bioimpedance analysis

    Directory of Open Access Journals (Sweden)

    M. V. Konovalova


    Full Text Available Resting energy expenditure (REE by indirect calorimetry and body composition by bioimpedance analysis are studied in three groups of children aged 5–18 years. Group 1 (n = 181 – patients in remission of cancer, group 2 (n = 55 – children with oncology diseases receiving chemotherapy or who are in the early period after hematopoietic stem cell transplantation, group 3 (n = 63 – children with non-malignant diseases of the gastrointestinal tract. To eliminate the influence of age and gender on the intergroup comparisons, body composition parameters were expressed as standardized values (z-scores relative to a reference group of healthy Russian children (n = 138,191. Group 1 was characterized by excess fat content with intact lean body mass, and groups 2 and 3 by protein depletion, more pronounced in Group 2 with a higher percentage of body fat. All used conventional formulas (WHO, Harris–Benedict and others in groups 1 and 3 underestimated REE as compared with indirect calorimetry. A new formula for REE, giving an unbiased estimate in the group 1 was proposed: REE (kcal/day = 28.7 × BCM (kg +10.5 × Height (cm – 38.6 × Age (years – 134, where BCM – body cell mass according to bioimpedance analysis (R2 = 0.67, the standard deviation of 196 kcal/day.

  6. Kinetics of enzymatic high-solid hydrolysis of lignocellulosic biomass studied by calorimetry. (United States)

    Olsen, Søren N; Lumby, Erik; McFarland, Kc; Borch, Kim; Westh, Peter


    Enzymatic hydrolysis of high-solid biomass (>10% w/w dry mass) has become increasingly important as a key step in the production of second-generation bioethanol. To this end, development of quantitative real-time assays is desirable both for empirical optimization and for detailed kinetic analysis. In the current work, we have investigated the application of isothermal calorimetry to study the kinetics of enzymatic hydrolysis of two substrates (pretreated corn stover and Avicel) at high-solid contents (up to 29% w/w). It was found that the calorimetric heat flow provided a true measure of the hydrolysis rate with a detection limit of about 500 pmol glucose s(-1). Hence, calorimetry is shown to be a highly sensitive real-time method, applicable for high solids, and independent on the complexity of the substrate. Dose-response experiments with a typical cellulase cocktail enabled a multidimensional analysis of the interrelationships of enzyme load and the rate, time, and extent of the reaction. The results suggest that the hydrolysis rate of pretreated corn stover is limited initially by available attack points on the substrate surface (10% conversion). This kinetic profile is interpreted as an increase in polymer end concentration (substrate for CBH) as the hydrolysis progresses, probably due to EG activity in the enzyme cocktail. Finally, irreversible enzyme inactivation did not appear to be the source of reduced hydrolysis rate over time.

  7. Application of differential scanning calorimetry in evaluation of solid state interactions in tablets containing acetaminophen. (United States)

    Mazurek-Wadołkowska, Edyta; Winnicka, Katarzyna; Czajkowska-Kośnik, Anna; Czyzewska, Urszula; Miltyk, Wojciech


    Differential scanning calorimetry (DSC) is an analytical procedure used to determine the differences in the heat flow generated or absorbed by the sample. This method allows to assess purity and polymorphic form of drug compounds, to detect interactions between ingredients of solid dosage forms and to analyze stability of solid formulations. The aim of this study was the assessment of compatibility between acetaminophen (API) and different types of excipients often used in tablets compression: polyvinylpyrrolidone, crospovidone, pregelatinized starch, microcrystalline cellulose and magnesium stearate by differential scanning calorimetry. The study contains results of thermal analysis of excipients and individually performed mixtures of these substances with acetaminophen before and after compression and after 6 months storage of tablets at different temperature and relative humidity conditions (25 +/- 2 degrees C /40 +/- 5% RH, 25 +/- 2 degrees C /60 +/- 5% RH, 40 +/- 2 degrees C /75 +/- 5% RH) for a period of 6 months. To detect possible changes of API chemical structure, gas chromatography-mass spectrometry (GC-MS) was also applied. GC-MS with electron impact ionization (EI) was employed to determine the fragmentation pattern of API. It was shown that the developed formulations showed excellent compatibility among all excipients used except Kollidon CL. The interaction with Kollidon CL is probably a result of a physical reaction as confirmed by GC-MS analyses. Obtained results revealed that DSC can be successfully applied to evaluate possible incompatibilities between acetaminophen and Kollidon.

  8. Volume and expansivity changes of micelle formation measured by pressure perturbation calorimetry. (United States)

    Fan, Helen Y; Nazari, Mozhgan; Chowdhury, Saria; Heerklotz, Heiko


    We present the application of pressure perturbation calorimetry (PPC) as a new method for the volumetric characterization of the micelle formation of surfactants. The evaluation is realized by a global fit of PPC curves at different surfactant concentration ranging, if possible, from below to far above the CMC. It is based on the knowledge of the temperature dependence of the CMC, which can for example be characterized by isothermal titration calorimetry. We demonstrate the new approach for decyl-β-maltopyranoside (DM). It shows a strong volume increase upon micelle formation of 16 ± 2.5 mL/mol (+4%) at 25 °C, and changes with temperature by -0.1 mL/(mol K). The apparent molar expansivity (E(S)) decreases upon micelle formation from 0.44 to 0.31 mL/(mol K) at 25 °C. Surprisingly, the temperature dependence of the expansivity of DM in solution (as compared with that of maltose) does not agree with the principal behavior described for polar (E(S)(T) decreasing) and hydrophobic (E(S)(T) increasing) solutes or moieties before. The results are discussed in terms of changes in hydration of the molecules and internal packing of the micelles and compared with the volumetric effects of transitions of proteins, DNA, lipids, and polymers.

  9. Calorimetry Sample Exchange analysis of data report for October--December, 1988

    Energy Technology Data Exchange (ETDEWEB)

    Lyons, J.E.


    The goals of the Calorimetry Sample Exchange Program are to: discuss measurement differences; review and improve analytical measurements and methods; discuss new measurement capabilities; provide data to DOE on measurement capabilities to evaluate shipper-receiver differences; provide characterized or standard materials as necessary for exchange participants; and provide a measurement control program for plutonium analysis. A sample of PuO{sub 2} powder is available at each participating site for NDA measurement, including either or both calorimetry and high-resolution gamma-ray spectroscopy, the elements which are typically combined to provide a calorimetric assay of plutonium. The facilities measure the sample as frequently and to the level of precision which they desire, and then submit the data to the Exchange for analysis. Statistical tests are used to evaluate the data and to determine if there are significant differences from accepted values for the exchange sample or from data previously reported by that facility. This information is presented, in the form of a quarterly report, intended for use by Exchange participants in measurement control programs, or to indicate when bias corrections may be appropriate. No attempt, however, has been made to standardize methods or frequency of data collection, calibration, or operating procedures. Direct comparisons between laboratories may, therefore, be misleading since data have not bee collected to the same precision or for the same time periods. The six participating laboratories are Lawrence Livermore, Los Alamos, MRC-Mound, Westinghouse Hanford, Rocky Flats, and Savannah River.

  10. Direct calorimetry of free-moving eels with manipulated thyroid status (United States)

    van Ginneken, Vincent; Ballieux, Bart; Antonissen, Erik; van der Linden, Rob; Gluvers, Ab; van den Thillart, Guido


    In birds and mammals, the thyroid gland secretes the iodothyronine hormones of which tetraiodothyronine (T4) is less active than triiodothyronine (T3). The action of T3 and T4 is calorigenic and is involved in the control of metabolic rate. Across all vertebrates, thyroid hormones also play a major role in differentiation, development and growth. Although the fish thyroidal system has been researched extensively, its role in thermogenesis is unclear. In this study, we measured overall heat production to an accuracy of 0.1 mW by direct calorimetry in a free-moving European eel ( Anguilla anguilla L.) with different thyroid status. Hyperthyroidism was induced by injection of T3 and T4, and hypothyroidism was induced with phenylthiourea. The results show for the first time at the organismal level, using direct calorimetry, that neither overall heat production nor overall oxygen consumption in eels is affected by hyperthyroidism. Therefore, we conclude that the thermogenic metabolism-stimulating effect of thyroid hormones (TH) is not present with a cold-blooded fish species like the European eel. This supports the concept that TH does not stimulate thermogenesis in poikilothermic species.

  11. PREFACE: 16th International Conference on Calorimetry in High Energy Physics (CALOR 2014) (United States)

    Novotny, Rainer W.


    The XVIth International Conference on Calorimetry in High Energy Physics - CALOR 2014 - was held in Giessen, Germany from 6-11 April 2014 at the Science Campus of the University. It was hosted by the Justus-Liebig-University and the HIC for FAIR Helmholtz International Center. The series of conferences on calorimetry were started in 1990 at Fermilab and are focusing primarily on operating and future calorimeter systems within the Hadron and High-Energy Physics community without neglecting the impact on other fields such as Astrophysics or Medical Imaging. Confirmed by the impressive list of over 70 oral presentations, 5 posters and over 100 attendees, the field of calorimetry appears alive and attractive. The present volume contains the written contributions of almost all presentations which can be found at Time slots of 15 or 30 minutes including discussion were allocated. The conference was accompanied by a small exhibition of several industrial companies related to the field. The day before the opening of the scientific program, Richard Wigmans gave an excellent and vivid tutorial on basic aspects on calorimetry meant as an introduction for students and conference attendees new in the field. The opening ceremony was used to give an impression of the present and future status and the scientific program of the new FAIR facility nearby at Darmstadt presented by Klaus Peters from GSI. The conference program of the first day was dedicated to the performance and required future upgrade of the LHC experiments, dominated by ATLAS, CMS and LHCb. The program of the next day contained specific aspects on electronics and readout as well as calorimetry in outer space. Several contributions discussed in detail new concepts for hadron calorimeters within the CALICE collaboration completed by a session on sampling calorimeters. The next sections were dedicated to operating and future calorimeters at various laboratories and covering a wide range of

  12. Heat capacity and transition behavior of sucrose by standard, fast scanning and temperature-modulated calorimetry

    Energy Technology Data Exchange (ETDEWEB)

    Magoń, A. [Department of Chemistry, University of Technology, 35-959 Rzeszów (Poland); Wurm, A.; Schick, C. [Department of Physics, University of Rostock, 18057 Rostock (Germany); Pangloli, Ph.; Zivanovic, S. [Department of Food Science and Technology, University of Tennessee, Knoxville, TN 37996 (United States); Skotnicki, M. [Department of Pharmaceutical Technology, Poznan University of Medical Sciences, 60-780 Poznań (Poland); Pyda, M., E-mail: [Department of Chemistry, University of Technology, 35-959 Rzeszów (Poland)


    Highlights: • Experimental, apparent heat capacity of sucrose was investigated by advanced thermal analysis. • Vibrational heat capacity of solid state was linked with a low temperature experimental heat capacity of sucrose. • Equilibrium melting parameters of sucrose were determined. • Decomposition, superheating of crystalline sucrose during melting process were presented. • TGA, DSC, TMDSC, and FSC are useful tools for characterization of sucrose. - Abstract: The heat capacity (C{sub p}) of crystalline and amorphous sucrose was determined using standard and quasi-isothermal temperature modulated differential scanning calorimetry. The results were combined with the published data determined by adiabatic calorimetry, and the C{sub p} values are now reported for the wide 5–600 K range. The experimental C{sub p} of solid sucrose at 5–300 K was used to calculate the vibrational, solid C{sub p} based on the vibrational molecular motions. The calculated solid and liquid C{sub p} together with the transition parameters for equilibrium conditions were used as references for detailed quantitative thermal analysis of crystalline and amorphous sucrose. Melting temperature (T{sub m}) of the crystalline sucrose was identified in a broad 442–465 K range with a heat of fusion of 40–46 J/mol determined at heating rates 0.5–20 K/min, respectively. The equilibrium T{sub m} and heat of fusion of crystalline sucrose were estimated at zero heating rate as T{sup o}{sub m} = 424.4 K and ΔH{sup o}{sub f} = 32 kJ/mol, respectively. The glass transition temperature (T{sub g}) of amorphous sucrose was at 331 K with a change in C{sub p} of 267 J/(mol K) as it was estimated from reversing heat capacity by quasi-isothermal TMDSC on cooling. At heating rates less than 30 K/min, thermal decomposition occurred during melting, while at extreme rate of 1000 K/s, degradation was not observed. Data obtained by fast scanning calorimetry (FSC) at 1000 K/s, showed that T{sub m} was

  13. Isothermal titration calorimetry and surface plasmon resonance allow quantifying substrate binding to different binding sites of Bacillus subtilis xylanase

    DEFF Research Database (Denmark)

    Cuyvers, Sven; Dornez, Emmie; Abou Hachem, Maher;


    Isothermal titration calorimetry and surface plasmon resonance were tested for their ability to study substrate binding to the active site (AS) and to the secondary binding site (SBS) of Bacillus subtilis xylanase A separately. To this end, three enzyme variants were compared. The first was a cat......Isothermal titration calorimetry and surface plasmon resonance were tested for their ability to study substrate binding to the active site (AS) and to the secondary binding site (SBS) of Bacillus subtilis xylanase A separately. To this end, three enzyme variants were compared. The first...

  14. Thermophysical analysis of II-VI semiconductors by PPE calorimetry and lock-in thermography

    Energy Technology Data Exchange (ETDEWEB)

    Streza, M.; Dadarlat, D. [National Institute for Research and Development of Isotopic and Molecular Technologies, 65-103 Donath, 400293 Cluj-Napoca (Romania); Strzałkowski, K. [Institute of Physics, Faculty of Physics, Astronomy and Informatics, Nicolaus Copernicus University, Grudziadzka 5, 87-100 (Poland)


    An accurate determination of thermophysical properties such as thermal diffusivity, thermal effusivity and thermal conductivity is extremely important for characterization and quality assurance of semiconductors. Thermal diffusivity and effusivity of some binary semiconductors have been investigated. Two experimental techniques were used: a contact technique (PPE calorimetry) and a non contact technique (lock-in thermography). When working with PPE, in the back (BPPE) configuration and in the thermally thick regim of the pyroelectric sensor, we can get the thermal diffusivity of the sample by performing a scanning of the excitation frequency of radiation. Thermal effusivity is obtained in front configuration (sensor directly irradiated and sample in back position) by performing a thickness scan of a coupling fluid. By using the lock-in thermography technique, the thermal diffusivity of the sample is obtained from the phase image. The results obtained by the two techniques are in good agreement. Nevertheless, for the determination of thermal diffusivity, lock-in thermography is preferred.

  15. Determination of ice content in hardened concrete by low-temperature calorimetry

    DEFF Research Database (Denmark)

    Wu, Min; Johannesson, Björn; Geiker, Mette Rica


    on the accumulated heat curves measured in the freezing and the melting process. Second, the ‘C-baseline’ is discussed in which a calculated baseline is used where the heat capacity of both water and ice and the phase changing behaviour under different testing temperatures are considered. It turns out that both...... calculate the ice contents at different temperatures in the freezing and melting process. It should be noted that there is no general agreement on how to obtain the important temperature dependence of the heat of fusion of water confined in small pores. By performing comparison studies, the present study......Low-temperature calorimetry has been used to determine the ice content in concrete at different temperatures when exposed to low-temperature environments. However, the analysis of the ice content from the measured data of heat flow is not straightforward. In this study, two important factors...

  16. Van’t Hoff global analyses of variable temperature isothermal titration calorimetry data (United States)

    Freiburger, Lee A.; Auclair, Karine; Mittermaier, Anthony K.


    Isothermal titration calorimetry (ITC) can provide detailed information on the thermodynamics of biomolecular interactions in the form of equilibrium constants, KA, and enthalpy changes, ΔHA. A powerful application of this technique involves analyzing the temperature dependences of ITC-derived KA and ΔHA values to gain insight into thermodynamic linkage between binding and additional equilibria, such as protein folding. We recently developed a general method for global analysis of variable temperature ITC data that significantly improves the accuracy of extracted thermodynamic parameters and requires no prior knowledge of the coupled equilibria. Here we report detailed validation of this method using Monte Carlo simulations and an application to study coupled folding and binding in an aminoglycoside acetyltransferase enzyme. PMID:28018008


    Directory of Open Access Journals (Sweden)

    Pavel Holba


    Full Text Available A short history on the development of thermometric methods are reviewed accentuating the role of Rudolf Bárta in underpinning special thermoanalytical conferences and new journal Silikáty in fifties as well as Vladimir Šatava mentioning his duty in the creation of the Czech school on thermoanalytical kinetics. This review surveys the innovative papers dealing with thermal analysis and the related fields (e.g. calorimetry, kinetics which have been published by noteworthy postwar Czechoslovak scholars and scientists and by their disciples in 1950-1980. Itemized 227 references with titles show rich scientific productivity revealing that many of them were ahead of time even at international connotation.

  18. Stability of some Cactaceae proteins based on fluorescence, circular dichroism, and differential scanning calorimetry measurements. (United States)

    Gorinstein, S; Zemser, M; Vargas-Albores, F; Ochoa, J L; Paredes-Lopez, O; Scheler, C; Aksu, S; Salnikow, J


    Characterization of three cactus proteins (native and denatured) from Machaerocereus gummosus (Pitahaya agria), Lophocereu schottii (Garambullo), and Cholla opuntia (Cholla), was based on electrophoretic, fluorescence, CD (circular dichroism), DSC (differential scanning calorimetry), and FT-IR (Fourier transform infrared) measurements. The obtained results of intrinsic fluorescence, DSC, and CD were dissimilar for the three species of cactus, providing evidence of differences in secondary and tertiary structures. Cactus proteins may be situated in the following order corresponding to their relative stability: Machaerocereus gummosus (Pitahaya agria) > Cholla opuntia (Cholla) > Lophocereu schottii (Garambullo). Thermodynamic properties of proteins and their changes upon denaturation (temperature of denaturation, enthalphy, and the number of ruptured hydrogen bonds) were correlated with the secondary structure of proteins and disappearance of alpha-helix.


    Directory of Open Access Journals (Sweden)

    Carolina A. Asmus


    Full Text Available The following study aims to quantify the release activation energy (Ea of hydrogen (H from lattice sites, reversible or irreversible, where the H can be trapped. Moreover, enthalpy changes associated with the main hydrogen (H trapping sites can be analyzed by means of differential scanning calorimetry (DSC. In this technique, the peak temperature measurement is determined at two different heating rates, 3ºC/min y 5ºC/min, from ambient temperature to 500°C. In order to simulate severe conditions of hydrogen income into resulfurized high strength steel, electrolytic permeation tests were performed on test tubes suitable for fatigue tests. Sometimes during charging, H promoters were aggregated to electrolytic solution. Subsequently, the test tubes were subjected to flow cycle fatigue tests. Finally, irreversible trap which anchor more strongly H atoms are MnS inclusions. Its role on hydrogen embrittlement during fatigue tests is conclusive.

  20. Electrospray techniques for the study of liquid energetics by hyperquenched glass calorimetry

    CERN Document Server

    Wang, L M; Angell, C A; Wang, Li-Min; Borick, Steve


    We describe an electrospray technique for in situ preparation, for differential scanning calorimetry study, of samples of molecular liquids quenched into the glassy state on extremely short time scales (hyperquenched). We study the case of propylene glycol PG in some detail. Using a fictive temperature method of obtaining the temperature dependence of enthalpy relaxation, we show that the electrospray method yields quenching rates of ~105 K/s, while the more common method, dropping a sealed pan of sample into liquid nitrogen, yields only 120 K/s. Hyperquenched samples start to relax exothermically far below the glass temperature, at a temperature where the thermal energy permits escape from the shallow traps in which the system becomes localized during hyperquenching. This permits estimation of the trap depths, which are then compared with the activation energy estimated from the fictive temperature of the glass and the relaxation time at the fictive temperature. The trap depth in molar energy units is compar...

  1. Granulometric structure, zeta potential and differential scanning calorimetry of native starch powders from Dioscorea spp.

    Directory of Open Access Journals (Sweden)

    Gildas K. Gbassi


    Full Text Available Starch powders from two cultivars of Dioscorea rotundata (DR were analysed on the physicochemical aspect. Granulometric structure, zeta potential and differential scanning calorimetry of starch powders showed the following properties. Various shapes with predominance of granule ranging from 10 to 40 μm were noted. The zeta potential of DR went from positive values to negative values as the pH was increasing from 2 to 8. From pH 2 to 4, the zeta potential was positive. A significant difference was obtained between each value (p > 0.05. The zeta potential took a negative value from pH 5 and above. The results of thermal analysis show that starches start swelling at 68.91.5 C. Enthalpy of gelatinization was about 15 J.g-1 .

  2. DNA heats up : Energetics of genome ejection from phage revealed by isothermal titration calorimetry

    CERN Document Server

    Jeembaeva, Meerim; Castelnovo, Martin; Evilevitch, Alex


    Most bacteriophages are known to inject their double-stranded DNA into bacteria upon receptor binding in an essentially spontaneous way. This downhill thermodynamic process from the intact virion toward the empty viral capsid plus released DNA is made possible by the energy stored during active packaging of the genome into the capsid. Only indirect measurements of this energy have been available until now using either single-molecule or osmotic suppression techniques. In this paper, we describe for the first time the use of isothermal titration calorimetry to directly measure the heat released (or equivalently the enthalpy) during DNA ejection from phage lambda, triggered in solution by a solubilized receptor. Quantitative analyses of the results lead to the identification of thermodynamic determinants associated with DNA ejection. The values obtained were found to be consistent with those previously predicted by analytical models and numerical simulations. Moreover, the results confirm the role of DNA hydrat...

  3. Partitioning of late gestation energy expenditure in ewes using indirect calorimetry and a linear regression approach

    DEFF Research Database (Denmark)

    Kiani, Alishir; Chwalibog, André; Nielsen, Mette O;


    study metabolizable energy (ME) intake ranges for twin-bearing ewes were 220-440, 350- 700, 350-900 kJ per metabolic body weight (W0.75) at week seven, five, two pre-partum respectively. Indirect calorimetry and a linear regression approach were used to quantify EE(gest) and then partition to EE......(conceptus) and EE(homeorhetic). Energy expenditure of basal metabolism of the non-gravid tissues (EE(bmng)), derived from the intercept of the linear regression equation of retained energy [kJ/W0.75] and ME intake [kJ/W(0.75)], was 298 [kJ/ W0.75]. Values of the intercepts of the regression equations at week seven...

  4. Binding of chrysoidine to catalase: spectroscopy, isothermal titration calorimetry and molecular docking studies. (United States)

    Yang, Bingjun; Hao, Fang; Li, Jiarong; Chen, Dongliang; Liu, Rutao


    Chrysoidine is an industrial azo dye and the presence of chrysoidine in water and food has become an environmental concern due to its negative effects on human beings. In this work, the interactions between chrysoidine and bovine liver catalase (BLC) were explored. Obvious loss in catalytic activity was observed after incubation of BLC with chrysoidine, and the inhibition effect of BLC was found to be of the non-competitive type. No profound conformational change of BLC occurs in the presence of chrysoidine as revealed by UV-vis absorption, circular dichroism and fluorescence spectroscopy studies. Isothermal titration calorimetry results indicate that catalase has two sets of binding sites for chrysoidine. Further, molecular docking simulations show that chrysoidine is located within the bottleneck in the main channel of the substrate to the active site of BLC, which explain the activity inhibition of BLC by chrysoidine.

  5. The complexity of condensed tannin binding to bovine serum albumin--An isothermal titration calorimetry study. (United States)

    Kilmister, Rachel L; Faulkner, Peta; Downey, Mark O; Darby, Samuel J; Falconer, Robert J


    Isothermal titration calorimetry was applied to study the binding of purified proanthocyanidin oligomers to bovine serum albumin (BSA). The molecular weight of the proanthocyanidin oligomer had a major impact on its binding to BSA. The calculated change in enthalpy (ΔH) and association constant (Ka) became greater as the oligomer size increased then plateaued at the heptameric oligomer. These results support a model for precipitation of proteins by proanthocyanidin where increased oligomer size enhanced the opportunity for cross linkages between proteins ultimately forming sediment-able complexes. The authors suggest tannin binding to proteins is opportunistic and involves multiple sites, each with a different Ka and ΔH of binding. The ΔH of binding comprises both an endothermic hydrophobic interaction and exothermic hydrogen bond component. This suggests the calculated entropy value (ΔS) for tannin-protein interactions is subject to a systematic error and should be interpreted with caution.

  6. Laboratory Annealing Experiments Of Refractory Silicate Grain Analogs Using Differential Scanning Calorimetry (United States)

    Kimura, Yuki; Nuth, Joseph A., III; Tsukamota, Katsuo; Kaito, Chihiro


    Exothermic reactions during the annealing of laboratory synthesized amorphous magnesium-bearing silicate particles used as grain analogs of cosmic dust were detected by differential scanning calorimetry (DSC) in air. With infrared spectroscopy and transmission electron microscopy, we show that cosmic dust could possibly undergo fusion to larger particles, with oxidation of magnesium silicide and crystallization of forsterite as exothermic reactions in the early solar system. The reactions begin at approximately 425, approximately 625, and approximately 1000 K, respectively, and the reaction energies (enthalpies) are at least 727, 4151, and 160.22 J per gram, respectively. During the crystallization of forsterite particles, the spectral evolution of the 10 micrometer feature from amorphous to crystalline was observed to begin at lower temperature than the crystallization temperature of 1003 K. During spectral evolution at lower temperature, nucleation and/or the formation of nanocrystallites of forsterite at the surface of the grain analogs was observed.

  7. Kinetics of trypsin-catalyzed hydrolysis determined by isothermal titration calorimetry. (United States)

    Maximova, Ksenia; Trylska, Joanna


    Isothermal titration calorimetry (ITC) was applied to determine enzymatic activity and inhibition. We measured the Michaelis-Menten kinetics for trypsin-catalyzed hydrolysis of two substrates, casein (an insoluble macromolecule substrate) and Nα-benzoyl-dl-arginine β-naphthylamide (a small substrate), and estimated the thermodynamic parameters in the temperature range from 20 to 37°C. The inhibitory activities of reversible (small molecule benzamidine) and irreversible (small molecule phenylmethanesulfonyl fluoride and macromolecule α1-antitrypsin) inhibitors of trypsin were also determined. We showed the usefulness of ITC for fast and direct measurement of inhibition constants and half-maximal inhibitory concentrations and for predictions of the mechanism of inhibition. ITC kinetic assays could be an easy and straightforward way to estimate Michaelis-Menten constants and the effectiveness of inhibitors as well as to predict the inhibition mechanism. ITC efficiency was found to be similar to that of classical spectrophotometric enzymatic assays.

  8. Thermodynamic signature of secondary nano-emulsion formation by isothermal titration calorimetry. (United States)

    Fotticchia, Iolanda; Fotticchia, Teresa; Mattia, Carlo Andrea; Netti, Paolo Antonio; Vecchione, Raffaele; Giancola, Concetta


    The stabilization of oil in water nano-emulsions by means of a polymer coating is extremely important; it prolongs the shelf life of the product and makes it suitable for a variety of applications ranging from nutraceutics to cosmetics and pharmaceutics. To date, an effective methodology to assess the best formulations in terms of thermodynamic stability has yet to be designed. Here, we perform a complete physicochemical characterization based on isothermal titration calorimetry (ITC) compared to conventional dynamic light scattering (DLS) to identify polymer concentration domains that are thermodynamically stable and to define the degree of stability through thermodynamic functions depending upon any relevant parameter affecting the stability itself, such as type of polymer coating, droplet distance, etc. For instance, the method was proven by measuring the energetics in the case of two different biopolymers, chitosan and poly-L-lysine, and for different concentrations of the emulsion coated with poly-L-lysine.

  9. Integration and global analysis of isothermal titration calorimetry data for studying macromolecular interactions. (United States)

    Brautigam, Chad A; Zhao, Huaying; Vargas, Carolyn; Keller, Sandro; Schuck, Peter


    Isothermal titration calorimetry (ITC) is a powerful and widely used method to measure the energetics of macromolecular interactions by recording a thermogram of differential heating power during a titration. However, traditional ITC analysis is limited by stochastic thermogram noise and by the limited information content of a single titration experiment. Here we present a protocol for bias-free thermogram integration based on automated shape analysis of the injection peaks, followed by combination of isotherms from different calorimetric titration experiments into a global analysis, statistical analysis of binding parameters and graphical presentation of the results. This is performed using the integrated public-domain software packages NITPIC, SEDPHAT and GUSSI. The recently developed low-noise thermogram integration approach and global analysis allow for more precise parameter estimates and more reliable quantification of multisite and multicomponent cooperative and competitive interactions. Titration experiments typically take 1-2.5 h each, and global analysis usually takes 10-20 min.

  10. Substrate binding properties of potato tuber ADP-glucose pyrophosphorylase as determined by isothermal titration calorimetry. (United States)

    Cakir, Bilal; Tuncel, Aytug; Green, Abigail R; Koper, Kaan; Hwang, Seon-Kap; Okita, Thomas W; Kang, ChulHee


    Substrate binding properties of the large (LS) and small (SS) subunits of potato tuber ADP-glucose pyrophosphorylase were investigated by using isothermal titration calorimetry. Our results clearly show that the wild type heterotetramer (S(WT)L(WT)) possesses two distinct types of ATP binding sites, whereas the homotetrameric LS and SS variant forms only exhibited properties of one of the two binding sites. The wild type enzyme also exhibited significantly increased affinity to this substrate compared to the homotetrameric enzyme forms. No stable binding was evident for the second substrate, glucose-1-phosphate, in the presence or absence of ATPγS suggesting that interaction of glucose-1-phosphate is dependent on hydrolysis of ATP and supports the Theorell-Chance bi bi reaction mechanism.

  11. A unified framework based on the binding polynomial for characterizing biological systems by isothermal titration calorimetry. (United States)

    Vega, Sonia; Abian, Olga; Velazquez-Campoy, Adrian


    Isothermal titration calorimetry (ITC) has become the gold-standard technique for studying binding processes due to its high precision and sensitivity, as well as its capability for the simultaneous determination of the association equilibrium constant, the binding enthalpy and the binding stoichiometry. The current widespread use of ITC for biological systems has been facilitated by technical advances and the availability of commercial calorimeters. However, the complexity of data analysis for non-standard models is one of the most significant drawbacks in ITC. Many models for studying macromolecular interactions can be found in the literature, but it looks like each biological system requires specific modeling and data analysis approaches. The aim of this article is to solve this lack of unity and provide a unified methodological framework for studying binding interactions by ITC that can be applied to any experimental system. The apparent complexity of this methodology, based on the binding polynomial, is overcome by its easy generalization to complex systems.

  12. Conformation and stability properties of B17: II. Analytical investigations using differential scanning calorimetry. (United States)

    Khachfe, Hassan M; Atkinson, David


    Thermal and stability properties of B17, the 17% N-terminal domain of apo B, were carried out using differential scanning calorimetry spectroscopy, where the thermal characteristics of the polypeptide were studied and analyzed. The heat capacity data of B17 showed that the protein undergoes two transitions between 50 and 90 °C, with T m's at 65.9 and 74.8 °C. While the first transition showed immediate reversibility, the second one-with the higher T m-necessitated a longer cooling (several days) period for its reversibility to be observed and both transitions could be seen in the heat capacity profile of B17. Moreover, the van't Hoff enthalpies determined via calorimetric measurements agreed with the values calculated from the CD analysis reported previously.

  13. Steady State Condition in the Measurement of VO2and VCO2by Indirect Calorimetry. (United States)

    Cadena, M; Sacristan, E; Infante, O; Escalante, B; Rodriguez, F


    Resting Metabolic Rate (RMR) is computed using VO2and VCO2short time 15-minute window measurement with Indirect Calorimetry (IC) instruments designed with mixing chamber. Steady state condition using a 10% variation coefficient criteria is the main objective to achieve metabolic long time prediction reliability. This study address how susceptible is the steady state VO2, VCO2measurement condition to the clino-orthostatic physiological maneuver. 30 young healthy subjects were analyzed. Only 18 passed the 10% variation coefficient inclusive criteria. They were exposed to 10 minutes clino-stage and 10 minutes orthostage. The hypothesis tests show not statistical significance (p< 0.1) in the average and variance analysis. It is concluded that the steady state is not influenced by the patient position IC test, probably because IC mixing chamber instruments are insensitive to detect a mayor physiological dynamics changes that can modify the steady state definition.

  14. Influence of gamma radiation on potato starch gelatinization studied by differential scanning calorimetry (United States)

    Cieśla, Krystyna; Eliasson, Ann-Charlotte


    The paper presents a study of the influence of the conditions applied during differential scanning calorimetry (DSC) measurements (concentration and heating rate) on the possible detection of the differences between gelatinization occurring in both non-irradiated and irradiated potato starch with a dose of 20 kGy. Differences in gelatinization of irradiated and non-irradiated potato starch during DSC analysis was attributed to the radiation induced destruction of crystalline ordering. This was confirmed by studies of the samples irradiated to very high doses (446 and 600 kGy), and by comparing with the effect of grinding. Changes of starch properties caused by radiodepolymerization—contrary to those caused by grinding—influences gelatinization behaviour much more than the WAXS crystallinity in solid state.

  15. Electromagnetic calorimetry with $PbWO^{4}$ in the energy regime below 1 GeV

    CERN Document Server

    Novotny, R; Döring, W; Hejny, V; Hofstäetter, A; Korzhik, M V; Metag, V; Ströher, H


    The study of the performance and application of PbWO/sub 4/ in electromagnetic calorimetry at energies far below 1 GeV has been continued. The significantly improved optical and scintillation properties of 15 cm long Nb/La-doped crystals, optimized for the ECAL /CMS calorimeter, are documented. The lineshape, energy and time response of a 5*5 matrix are tested with monoenergetic photons up to 790 MeV energy and compared to previous measurements. First attempts have been made to enhance the scintillation yield by suitable dopants (Mo, Tb) for applications at very low photon energies. As a first large scale project at medium energies, the proposed concept for a compact photon spectrometer to be implemented into the ANKE magnetic spectrometer at COSY (KFA Julich) is illustrated. (4 refs).

  16. Research and Development for the ATLAS Forward Calorimetry at the HL-LHC

    CERN Document Server

    Cheplakov, Alexander


    A total luminosity of 3000/fb is expected at the HL-LHC, which corresponds to total irradiation doses which are more than doubled compared to the original design, taking into account a safety factor of 2 representing our confidence in radiation background simulations. Moreover, the increased instantaneous luminosity will result in a much higher detector occupancy. The ATLAS Forward Calorimeters (FCal) will be affected by these factors. A rich R&D program is ongoing to evaluate the consequences of the LHC modernization and to investigate di_erent scenarios proposed for the Phase-II detector upgrade. This contribution will concentrate on simulation studies of the FCal degradation and on irradiation tests performed at the IBR-2m reactor in Dubna. Results from radiation-tolerant sensors and components of the future read-out and voltage distribution system for various upgrade options of the forward calorimetry will be presented.

  17. Energetics of methanol and formic acid oxidation on Pt(111): Mechanistic insights from adsorption calorimetry (United States)

    Silbaugh, Trent L.; Karp, Eric M.; Campbell, Charles T.


    The catalytic and electrocatalytic oxidation and reforming of methanol and formic acid have received intense interest due to potential use in direct fuel cells and as prototype models for understanding electrocatalysis. Consequently, the reaction energy diagram (energies of all the adsorbed intermediates and activation energies of all the elementary steps) have been estimated for these reactions on Pt(111) by density functional theory (DFT) in several studies. However, no experimental measurement of these energy diagrams have been reported, nor is there a consensus on the mechanisms. Here, we use energies of key intermediates on Pt(111) from single crystal adsorption calorimetry (SCAC) and temperature programmed desorption (TPD) to build a combined energy diagram for these reactions. It suggests a new pathway involving monodentate formate as a key intermediate, with bidentate formate only being a spectator species that slows the rate. This helps reconcile conflicting proposed mechanisms.

  18. Applications of high pressure differential scanning calorimetry to aviation fuel thermal stability research (United States)

    Neveu, M. C.; Stocker, D. P.


    High pressure differential scanning calorimetry (DSC) was studied as an alternate method for performing high temperature fuel thermal stability research. The DSC was used to measure the heat of reaction versus temperature of a fuel sample heated at a programmed rate in an oxygen pressurized cell. Pure hydrocarbons and model fuels were studied using typical DSC operating conditions of 600 psig of oxygen and a temperature range from ambient to 500 C. The DSC oxidation onset temperature was determined and was used to rate the fuels on thermal stability. Kinetic rate constants were determined for the global initial oxidation reaction. Fuel deposit formation is measured, and the high temperature volatility of some tetralin deposits is studied by thermogravimetric analysis. Gas chromatography and mass spectrometry are used to study the chemical composition of some DSC stressed fuels.

  19. A survey of the year 2002 literature on applications of isothermal titration calorimetry. (United States)

    Cliff, Matthew J; Ladbury, John E


    Isothermal titration calorimetry (ITC) is becoming widely accepted as a key instrument in any laboratory in which quantification of biomolecular interactions is a requisite. The method has matured with respect to general acceptance and application development over recent years. The number of publications on ITC has grown exponentially over the last 10 years, reflecting the general utility of the method. Here all the published works of the year 2002 in this area have been surveyed. We review the broad range of systems to which ITC is being directed and classify these into general areas highlighting key publications of interest. This provides an overview of what can be achieved using this method and what developments are likely to occur in the near future.

  20. Differential scanning calorimetry of blood plasma for clinical diagnosis and monitoring. (United States)

    Garbett, Nichola C; Mekmaysy, Chongkham S; Helm, C William; Jenson, A Bennett; Chaires, Jonathan B


    Differential scanning calorimetry (DSC) provides a useful method to study the unfractionated plasma proteome. Plasma from healthy individuals yields a reproducible signature thermogram which results from the weighted sum of the thermal denaturation of the most abundant plasma proteins. Further investigation of the thermogram for healthy individuals showed it to be sensitive to ethnicity and gender. DSC analysis of plasma from diseased individuals revealed significant changes in the thermogram which are suggested to result not from changes in the concentration of the major plasma proteins but from interactions of small molecules or peptides with these proteins. Closer examination of the diseased thermograms showed a thermogram characteristic of each disease. For cervical cancer, the DSC method yields a progressively shifted thermogram as the disease advances from pre-invasive conditions to late stage cancer. Our application of the DSC method has provided a potential tool for the early diagnosis, monitoring and screening of cancer patients.

  1. Probing the thermodynamics of protein-lipid interactions by isothermal titration calorimetry. (United States)

    Swamy, Musti J; Sankhala, Rajeshwer S


    Isothermal titration calorimetry is a highly sensitive technique for the study of molecular interactions. This method has been applied quite extensively to investigate the interaction of proteins with small ligands, other proteins, and nucleic acids as well as with drugs and metal ions. In this chapter, we describe the application of ITC for the investigation of thermodynamics of protein-lipid interaction. A number of parameters such as enthalpy of binding (ΔH), entropy of binding (ΔS), association constant (K (a)), binding stoichiometry (n), and free energy of binding (ΔG) can be obtained from a single calorimetric titration, providing a complete thermodynamic characterization of the interaction. The method is described in detail taking the major protein of the bovine seminal plasma, PDC-109, which exhibits a high preference for interaction with choline-containing lipids, as an example. The method can be applied to investigate the thermodynamics of the interaction of other soluble proteins with lipid membranes.

  2. Direct Coupling of SiPMs to Scintillator Tiles for Imaging Calorimetry and Triggering

    CERN Document Server

    Simon, Frank; Joram, Christian


    The recent availability of blue sensitive silicon photomultipliers allows the direct readout of blue emitting plastic scintillator tiles without the use of a wavelength shifting fiber. Such directly read out tiles, without light guides, are attractive for the use in highly granular calorimeters that use large numbers of individual cells and in other applications where very compact designs are needed. However, the total signal amplitude and the uniformity of the response can be problematic in such cases. We have developed a scanning setup to investigate the response of scintillator tiles with SiPM readout in detail. It was used to develop optimized scintillator tile geometries for highly granular hadronic calorimetry at future colliders and to investigate the feasibility of a SiPM readout for the trigger of the ATLAS ALFA luminosity detectors. We report on results obtained with specialized scintillator tile geometries, discuss first results obtained with directly coupled SiPM readout of the ATLAS ALFA trigger ...

  3. Measurement and Model Validation of Nanofluid Specific Heat Capacity with Differential Scanning Calorimetry

    Directory of Open Access Journals (Sweden)

    Harry O'Hanley


    Full Text Available Nanofluids are being considered for heat transfer applications; therefore it is important to know their thermophysical properties accurately. In this paper we focused on nanofluid specific heat capacity. Currently, there exist two models to predict a nanofluid specific heat capacity as a function of nanoparticle concentration and material. Model I is a straight volume-weighted average; Model II is based on the assumption of thermal equilibrium between the particles and the surrounding fluid. These two models give significantly different predictions for a given system. Using differential scanning calorimetry (DSC, a robust experimental methodology for measuring the heat capacity of fluids, the specific heat capacities of water-based silica, alumina, and copper oxide nanofluids were measured. Nanoparticle concentrations were varied between 5 wt% and 50 wt%. Test results were found to be in excellent agreement with Model II, while the predictions of Model I deviated very significantly from the data. Therefore, Model II is recommended for nanofluids.

  4. A digital Front-End and Readout MIcrosystem for calorimetry at LHC

    CERN Multimedia


    % RD-16 A Digital Front-End and Readout Microsystem for Calorimetry at LHC \\\\ \\\\Front-end signal processing for calorimetric detectors is essential in order to achieve adequate selectivity in the trigger function of an LHC experiment, with data identification and compaction before readout being required in the harsh, high rate environment of a high luminosity hadron machine. Other crucial considerations are the extremely wide dynamic range and bandwidth requirements, as well as the volume of data to be transferred to following stages of the trigger and readout system. These requirements are best met by an early digitalization of the detector information, followed by integrated digital signal processing and buffering functions covering the trigger latencies.\\\\ \\\\The FERMI (Front-End Readout MIcrosystem) is a digital implementation of the front-end and readout electronic chain for calorimeters. It is based on dynamic range compression, high speed A to D converters, a fully programmable pipeline/digital filter c...

  5. The oxidation of aluminum at high temperature studied by Thermogravimetric Analysis and Differential Scanning Calorimetry.

    Energy Technology Data Exchange (ETDEWEB)

    Coker, Eric Nicholas


    The oxidation in air of high-purity Al foil was studied as a function of temperature using Thermogravimetric Analysis with Differential Scanning Calorimetry (TGA/DSC). The rate and/or extent of oxidation was found to be a non-linear function of the temperature. Between 650 and 750 ÀC very little oxidation took place; at 850 ÀC oxidation occurred after an induction period, while at 950 ÀC oxidation occurred without an induction period. At oxidation temperatures between 1050 and 1150 ÀC rapid passivation of the surface of the aluminum foil occurred, while at 1250 ÀC and above, an initial rapid mass increase was observed, followed by a more gradual increase in mass. The initial rapid increase was accompanied by a significant exotherm. Cross-sections of oxidized specimens were characterized by scanning electron microscopy (SEM); the observed alumina skin thicknesses correlated qualitatively with the observed mass increases.

  6. Crystallization kinetics in liquid crystals with hexagonal precursor phases by calorimetry

    Energy Technology Data Exchange (ETDEWEB)

    Padmaja, Sunkara; Ajita, Narayanan; Potukuchi, Dakshina Murthy [Dept. of Physics, Jawaharlal Nehru Technological Univ., Kakinada (India); Srinivasulu, Maddasani; Girish, Sriram Ramchandra [Liquid Crystal Research Centre, Koneru Lakshmaiah Coll. of Engineering, Vaddeswaram (India); Pisipati, Venkata Gopala Krishna Murthy [Dept. of Chemistry, Manipal Inst. of Tech. (India)


    Design and characterization of Schiff based liquid crystalline nO.m compounds exhibiting hexagonal smectic phases are reported. Crystallization kinetics investigations are carried out in the liquid crystals (LCs) exhibiting hexagonal ordered orthogonal and tilted precursor LC phases by calorimetry. The Avrami theory is referred and results are analyzed. Influence of molecular ordering, structure, and dimensionality of the LC precursor phase on kinetics is studied. Effect of shape and flexibility of the molecule for nucleation and growth processes is investigated. Varying rate of kinetics reflects upon the transit of the system from constant type to independent type of nucleation. The trends in the Avrami parameter b and exponent n suggest sporadic nucleation. Crystal growth is interpreted as heterogeneous permeation of layered domains (or aggregates) formed by needle shaped calamitic molecules. Calorimetric observations at different crystallization temperatures CT and hold time t infer diffusion mediated crystallization. (orig.)

  7. New methodology developed for the differential scanning calorimetry analysis of polymeric matrixes incorporating phase change materials (United States)

    Barreneche, Camila; Solé, Aran; Miró, Laia; Martorell, Ingrid; Inés Fernández, A.; Cabeza, Luisa F.


    Nowadays, thermal comfort needs in buildings have led to an increase in energy consumption of the residential and service sectors. For this reason, thermal energy storage is shown as an alternative to achieve reduction of this high consumption. Phase change materials (PCM) have been studied to store energy due to their high storage capacity. A polymeric material capable of macroencapsulating PCM was developed by the authors of this paper. However, difficulties were found while measuring the thermal properties of these materials by differential scanning calorimetry (DSC). The polymeric matrix interferes in the detection of PCM properties by DSC. To remove this interfering effect, a new methodology which replaces the conventional empty crucible used as a reference in the DSC analysis by crucibles composed of the polymeric matrix was developed. Thus, a clear signal from the PCM is obtained by subtracting the new full crucible signal from the sample signal.

  8. Toward New High Temperature Reference Materials for Calorimetry and Thermal Analysis

    Directory of Open Access Journals (Sweden)

    Razouk R.


    Full Text Available The French National Metrology Laboratory LNE-LCM has developed a high temperature reference facility for accurate measurements of the specific heat capacity and of the enthalpy of fusion of materials over the temperature range [23 °C, 1000 °C]. The metrological approach was to modify a commercial Calvet calorimeter in order to lower the uncertainty of measurement and to insure the metrological traceability of the measurements to the SI units, in particular by designing a new calibration system. The enthalpies of fusion of pure metals (indium, tin and silver and of a binary alloy Ag-28Cu have been measured. The results obtained on the three pure metallic materials are in very good agreement with data obtained by other National Metrology Institutes (NMIs using adiabatic calorimetry.

  9. The Yang-Yang anomaly in liquid-liquid criticality: Experimental evidence from adiabatic scanning calorimetry (United States)

    Losada-Pérez, Patricia; Tripathi, Chandra Shekhar Pati; Leys, Jan; Cerdeiriña, Claudio A.; Glorieux, Christ; Thoen, Jan


    Using adiabatic scanning calorimetry, we have found the first experimental evidence of the Yang-Yang anomaly in liquid-liquid criticality from high-resolution two-phase isobaric heat capacity measurements for the binary mixture 3-pentanol + nitromethane. The results suggest a rather strong effect. The critical amplitude of the partial molar heat capacity is higher for the component with larger molecular volume, in accordance with the predictions of complete scaling as obtained from the customary observed asymmetric behavior of the coexistence-curve diameter. This consolidates complete scaling as the true formulation of fluid-fluid criticality. The quantitative analysis indicates that molecular size is not the only microscopic factor at play in asymmetric liquid-liquid criticality.

  10. Kinetics of Enzymatic High-Solid Hydrolysis of Lignocellulosic Biomass Studied by Calorimetry

    DEFF Research Database (Denmark)

    Olsen, Søren Nymand; Rasmussen, Erik Lumby; McFarland, K.C.;


    Enzymatic hydrolysis of high-solid biomass (>10% w/w dry mass) has become increasingly important as a key step in the production of second-generation bioethanol. To this end, development of quantitative real-time assays is desirable both for empirical optimization and for detailed kinetic analysis....... In the current work, we have investigated the application of isothermal calorimetry to study the kinetics of enzymatic hydrolysis of two substrates (pretreated corn stover and Avicel) at high-solid contents (up to 29% w/w). It was found that the calorimetric heat flow provided a true measure of the hydrolysis...... analysis of the interrelationships of enzyme load and the rate, time, and extent of the reaction. The results suggest that the hydrolysis rate of pretreated corn stover is limited initially by available attack points on the substrate surface (

  11. Design and First Measurements of an Alternative Calorimetry Chamber for the HZB Quadrupole Resonator

    CERN Document Server

    Keckert, Sebastian; Knobloch, Jens; Kugeler, Oliver


    The systematic research on superconducting thin films requires dedicated testing equipment. The Quadrupole Resonator (QPR) is a specialized tool to characterize the superconducting RF properties of circular planar samples. A calorimetric measurement of the RF surface losses allows the surface resistance to be measured with sub nano-ohm resolution. This measurement can be performed over a wide temperature and magnetic field range, at frequencies of 433, 866 and 1300 MHz. The system at Helmholtz-Zentrum Berlin (HZB) is based on a resonator built at CERN and has been optimized to lower peak electric fields and an improved resolution. In this paper the design of an alternative calorimetry chamber is presented, providing flat samples for coating which are easy changeable. All parts are connected by screwing connections and no electron beam welding is required. Furthermore this design enables exchangeability of samples between the resonators at HZB and CERN. First measurements with the new design show ambiguous r...

  12. From calorimetry to medical imaging: a shining example of successful transfer!

    CERN Multimedia

    Caroline Duc


    A team at CERN has drawn inspiration from calorimetry methods developed for high-energy physics to create a new positron-emission tomography system for use in medical imaging, which they’ve dubbed AX-PET. With support from European and American laboratories*, the project is reaching fruition, as initial tests confirm its promise.   Snapshot of a “phantom”, a test object, surrounded by the AX-PET photon detectors. Positron-emission tomography (PET) is a medical imaging technique based on the matter-antimatter interaction that can provide a three-dimensional representation of the metabolic activity of an organ. To do so, radioactive marker molecules are first injected into the subject. As the marker decays, it emits positrons (antimatter particles), which are annihilated upon encountering electrons in the surrounding environment. The resulting flash, consisting of two photons, is detected by the PET machine. In conventional PET systems, it is impossible to improv...

  13. Fluence correction factor for graphite calorimetry in a clinical high-energy carbon-ion beam (United States)

    Lourenço, A.; Thomas, R.; Homer, M.; Bouchard, H.; Rossomme, S.; Renaud, J.; Kanai, T.; Royle, G.; Palmans, H.


    The aim of this work is to develop and adapt a formalism to determine absorbed dose to water from graphite calorimetry measurements in carbon-ion beams. Fluence correction factors, {{k}\\text{fl}} , needed when using a graphite calorimeter to derive dose to water, were determined in a clinical high-energy carbon-ion beam. Measurements were performed in a 290 MeV/n carbon-ion beam with a field size of 11  ×  11 cm2, without modulation. In order to sample the beam, a plane-parallel Roos ionization chamber was chosen for its small collecting volume in comparison with the field size. Experimental information on fluence corrections was obtained from depth-dose measurements in water. This procedure was repeated with graphite plates in front of the water phantom. Fluence corrections were also obtained with Monte Carlo simulations through the implementation of three methods based on (i) the fluence distributions differential in energy, (ii) a ratio of calculated doses in water and graphite at equivalent depths and (iii) simulations of the experimental setup. The {{k}\\text{fl}} term increased in depth from 1.00 at the entrance toward 1.02 at a depth near the Bragg peak, and the average difference between experimental and numerical simulations was about 0.13%. Compared to proton beams, there was no reduction of the {{k}\\text{fl}} due to alpha particles because the secondary particle spectrum is dominated by projectile fragmentation. By developing a practical dose conversion technique, this work contributes to improving the determination of absolute dose to water from graphite calorimetry in carbon-ion beams.

  14. Differential scanning calorimetry and reaction kinetics studies of {gamma} + {alpha}{sub 2} Ti aluminide

    Energy Technology Data Exchange (ETDEWEB)

    Gupta, R.K., E-mail: [Vikram Sarabhai Space Centre, ISRO, Trivandrum 695 022 (India); Pant, Bhanu [Vikram Sarabhai Space Centre, ISRO, Trivandrum 695 022 (India); Agarwala, Vijaya [Indian Institute of Technology Roorkee, Roorkee 247 667 (India); Sinha, P.P. [Vikram Sarabhai Space Centre, ISRO, Trivandrum 695 022 (India)


    Reaction synthesis method for titanium aluminide processing consists of an exothermic reaction among alloying elements present and primarily between titanium and aluminium particles at specific temperature range. Study of this reaction helps in understanding the process of aluminide formation. Differential scanning calorimetry (DSC) study is the suitable method to study such reactions. In the present work, five different alloy mixtures based on Ti48Al2Cr2Nb0.1B are prepared and DSC study is carried out. Onset temperature, peak temperature and completion temperature of the major exothermic reaction is analyzed at different heating rates. Further, kinetics of the reaction is studied using Johnson-Mehl-Avrami equation. Activation energy and Avrami parameter are calculated and compared with the reported works on binary alloy. It has been observed that exothermic reaction is triggered by melting of aluminium. Boron assists in increasing the enthalpy of reaction by boride formation. Primary reaction product is found to be TiAl{sub 3}. Activation energy as well as Avrami parameter is found to have marginal variation due to small change in alloying elements in different alloys and due to heating rates in the same alloy. -- Highlights: Black-Right-Pointing-Pointer Reaction kinetics studies of Ti-aluminide alloy powder mixtures carried out. Black-Right-Pointing-Pointer Five compositions studied through non-isothermal differential scanning calorimetry. Black-Right-Pointing-Pointer Effect of minor boron addition and role of Ti particle size is noted. Black-Right-Pointing-Pointer Activation energies using JMA equations are between 169.5 and 192.49 kJ mol{sup -1}.

  15. Comparison of Indirect Calorimetry and Predictive Equations in Estimating Resting Metabolic Rate in Underweight Females

    Directory of Open Access Journals (Sweden)



    Full Text Available Background: Underweight as a public health problem in young women is associated with nutritional deficiencies, menstrual irregularity, eating disorders, reduced fertility, etc. Since resting metabolic rate (RMR is a necessary compo-nent in the development of nutrition support therapy, therefore we determined the accuracy of commonly used pre-dictive equations against RMR measured by indirect calorimetry among healthy young underweight females.Methods: This cross-sectional study was conducted on 104 underweight females aged 18-30 years old with body mass index (BMI <18.5 kg/m2 in 2013 . After collecting anthropometric data, body composition was measured by bioelec-tric impedance analysis (BIA. RMR was measured by using indirect calorimetry (FitMate™ and was estimated by 10 commonly used predictive equations. Comparisons were conducted using paired t-test. The accuracy of the RMR equations was evaluated on the basis of the percentage of subjects’ predicted RMR within 10% of measured RMR.Results: The mean BMI of subjects was 17.3±1.3 kg/m2. The measured RMR ranged 736-1490 kcal/day (mean 1084.7±175 kcal/day. Findings indicated that except Muller and Abbreviation, other equations significantly over es-timated RMR, compared to measured value (P<0.05. As an individual prediction accuracy, these predictive equations showed poor performance with the highest accuracy rate of 54.8% for Muller equation (22.1% under and 23.1% over-prediction and 43.3% for Abbreviation equation (31.7% under and 25% over-prediction, the percentage bias was 1.8% and 0.63% and RMSE was 162 and 173 kcal/d, respectively.Conclusion: Although Muller equation gave fairly acceptable prediction, more suitable new equations are needed to be developed to help better management of nutritional plans in young underweight people.

  16. Efficient Isothermal Titration Calorimetry Technique Identifies Direct Interaction of Small Molecule Inhibitors with the Target Protein. (United States)

    Gal, Maayan; Bloch, Itai; Shechter, Nelia; Romanenko, Olga; Shir, Ofer M


    Protein-protein interactions (PPI) play a critical role in regulating many cellular processes. Finding novel PPI inhibitors that interfere with specific binding of two proteins is considered a great challenge, mainly due to the complexity involved in characterizing multi-molecular systems and limited understanding of the physical principles governing PPIs. Here we show that the combination of virtual screening techniques, which are capable of filtering a large library of potential small molecule inhibitors, and a unique secondary screening by isothermal titration calorimetry, a label-free method capable of observing direct interactions, is an efficient tool for finding such an inhibitor. In this study we applied this strategy in a search for a small molecule capable of interfering with the interaction of the tumor-suppressor p53 and the E3-ligase MDM2. We virtually screened a library of 15 million small molecules that were filtered to a final set of 80 virtual hits. Our in vitro experimental assay, designed to validate the activity of mixtures of compounds by isothermal titration calorimetry, was used to identify an active molecule against MDM2. At the end of the process the small molecule (4S,7R)-4-(4-chlorophenyl)-5-hydroxy-2,7-dimethyl-N-(6-methylpyridin-2-yl)-4,6,7,8 tetrahydrIoquinoline-3-carboxamide was found to bind MDM2 with a dissociation constant of ~2 µM. Following the identification of this single bioactive compound, spectroscopic measurements were used to further characterize the interaction of the small molecule with the target protein. 2D NMR spectroscopy was used to map the binding region of the small molecule, and fluorescence polarization measurement confirmed that it indeed competes with p53.

  17. Validation and recovery rates of an indirect calorimetry headbox system used to measure heat production of cattle (United States)

    A headbox system was constructed at the University of Nebraska-Lincoln to determine heat production from dairy cattle using indirect calorimetry. The system was designed for use in a tie-stall barn to allow the animal to be comfortable and was mounted on wheels to transport between animals between s...

  18. Conductivity, calorimetry and phase diagram of the NaHSO4–KHSO4 system

    DEFF Research Database (Denmark)

    Hind, Hamma-Cugny; Rasmussen, Søren Birk; Rogez, J.;


    Physico-chemical properties of the binary system NaHSO4-KHSO4 were studied by calorimetry and conductivity, The enthalpy of mixing has been measured at 505 K in the full composition range and the phase diagram calculated. The phase diagram has also been constructed from phase transition temperatu...

  19. Influence of frost damage and sample preconditioning on the porosity characterization of cement based materials using low temperature calorimetry

    DEFF Research Database (Denmark)

    Wu, Min; Fridh, Katja; Johannesson, Björn;


    Low temperature calorimetry (LTC) can be used to study the meso-porosity of cement based materials. The influence of frost damage on the meso-porosity determination by LTC was explored on a model material MCM-41 and two cement pastes by conducting repeated cycles of freezing and melting measureme...

  20. The Thermal Stability and Domain Interactions of the Mannitol Permease of Escherichia coli. A Differential Scanning Calorimetry Study

    NARCIS (Netherlands)

    Meijberg, Wim; Schuurman-Wolters, Gea K.; Scheek, Ruud M.; Robillard, George T.


    The thermal stability and domain interactions in the mannitol transporter from Escherichia coli, enzyme IImtl, have been studied by differential scanning calorimetry. To this end, the wild type enzyme, IICBAmtl, as well as IICBmtl and IICmtl, were reconstituted into a dimyristoylphosphatidylcholine

  1. The thermal stability and domain interactions of the mannitol permease of Escherichia coli - A differential scanning calorimetry study

    NARCIS (Netherlands)

    Meijberg, W.; Schuurman-Wolters, G.K.; Scheek, R.M.; Robillard, G.T.


    The thermal stability and domain interactions in the mannitol transporter from Escherichia coli, enzyme IImtl, have been studied by differential scanning calorimetry. To this end, the wild type enzyme, IICBAmtl, as well as IICBmtl and IICmtl, were reconstituted into a dimyristoylphosphatidylcholine

  2. On the accuracy of instantaneous gas exchange rates, energy expenditure, and respiratory quotient calculations obtained in indirect whole room calorimetry (United States)

    The molar balance equations of indirect calorimetry are treated from the point of view of cause-effect relationship where the gaseous exchange rates representing the unknown causes heed to be inferred from a known noisy effect – gaseous concentrations. Two methods of such inversion are analyzed. Th...

  3. Structure-property relations in crystalline L-leucine obtained from calorimetry, X-rays, neutron and Raman scattering

    DEFF Research Database (Denmark)

    Facanha Filho, Pedro F.; Jiao, Xueshe; Freire, Paulo T. C.;


    We have studied the amino acid L-leucine (LEU) using inelastic neutron scattering, X-rays and neutron diffraction, calorimetry and Raman scattering as a function of temperature, focusing on the relationship between the local dynamics of the NH(3), CH(3), CH(2) and CO(2) moieties and the molecular...

  4. Determination of thermodynamic potentials and the aggregation number for micelles with the mass-action model by isothermal titration calorimetry

    DEFF Research Database (Denmark)

    Olesen, Niels Erik; Westh, Peter; Holm, René


    The aggregation number (n), thermodynamic potentials (ΔG, ΔH, ΔS) and critical micelle concentration (CMC) for 6 natural bile salts were determined on the basis of both original and previously published isothermal titration calorimetry (ITC) data. Different procedures to estimate parameters...

  5. Use of scanning calorimetry and microrespiration to determine effects of Bt toxin doses on Pandemis leafroller (Lepidoptera: Tortricidae) metabolism (United States)

    Differential scanning calorimetry and microrespiration were used to determine the effects of the biopesticide, Bt toxin, on the metabolism of infected Pandemis leafroller, Pandemis purusana (Kearfott). The metabolic heat rate, CO2 evolution, O2 consumption of 2nd and 3rd instars following a 2 h expo...

  6. Kinetic properties of two Rhizopus exo-polygalacturonase enzymes hydrolyzing galacturonic acid oligomers using isothermal titration calorimetry (United States)

    The kinetic characteristics of two Rhizopus oryzae exo-polygalacturonases acting on galacturonic acid oligomers (GalpA) were determined using isothermal titration calorimetry (ITC). RPG15 hydrolyzing (GalpA)2 demonstrated a Km of 55 uM and kcat of 10.3 s^-1^ while RPG16 was shown to have greater af...


    Energy Technology Data Exchange (ETDEWEB)

    Harbour, J; Vickie Williams, V; Tommy Edwards, T


    This report provides initial results on the measurement of heat of hydration of Saltstone mixes using isothermal calorimetry. The results were obtained using a recently purchased TAM Air Model 3116 Isothermal Conduction Calorimeter. Heat of hydration is an important property of Saltstone mixes. Greater amounts of heat will increase the temperature of the curing mix in the vaults and limit the processing rate. The heat of hydration also reflects the extent of the hydraulic reactions that turn the fluid mixture into a ''stone like'' solid and consequently impacts performance properties such as permeability. Determining which factors control these reactions, as monitored by the heat of hydration, is an important goal of the variability study. Experiments with mixes of portland cement in water demonstrated that the heats measured by this technique over a seven day period match very well with the literature values of (1) seven day heats of hydration using the standard test method for heat of hydration of hydraulic cement, ASTM C 186-05 and (2) heats of hydration measured using isothermal calorimetry. The heats of hydration of portland cement or blast furnace slag in a Modular Caustic Side Solvent Extraction Unit (MCU) simulant revealed that if the cure temperature is maintained at 25 C, the amount of heat released over a seven day period is roughly 62% less than the heat released by portland cement in water. Furthermore, both the blast furnace slag and the portland cement were found to be equivalent in heat production over the seven day period in MCU. This equivalency is due to the activation of the slag by the greater than 1 Molar free hydroxide ion concentration in the simulant. Results using premix (a blend of 10% cement, 45% blast furnace slag, and 45% fly ash) in MCU, Deliquification, Dissolution and Adjustment (DDA) and Salt Waste Processing Facility (SWPF) simulants reveal that the fly ash had not significantly reacted (undergone hydration

  8. A Guide to Differential Scanning Calorimetry of Membrane and Soluble Proteins in Detergents. (United States)

    Yang, Zhengrong; Brouillette, Christie G


    Differential scanning calorimetry (DSC) detects protein thermal unfolding by directly measuring the heat absorbed. Simple DSC experiments that require relatively small amounts of pure material can provide a wealth of information related to structure, especially with respect to domain architecture, without the need for a complete thermodynamic analysis. Thus, DSC is an ideal additional tool for membrane protein characterization and also offers several advantages over indirect thermal unfolding methods. Integral membrane proteins (IMPs) that comprise both large multitopic transmembrane domains (TMDs) and extramembranous domains (EMDs) are differentially affected by detergent interactions with both domains. In fact, in some cases, destabilization of the EMD by detergent may dominate overall IMP stability. This chapter will (1) provide a perspective on the advantages of DSC for membrane protein characterization and stability measurements, including numerous examples spanning decades of research; (2) introduce models for the interaction and destabilization of IMPs by detergents; (3) discuss two case studies from the authors' lab; and (4) offer practical advice for performing DSC in the presence of detergents.

  9. Torn human rotator cuff tendons have reduced collagen thermal properties on differential scanning calorimetry. (United States)

    Chaudhury, Salma; Holland, Christopher; Porter, David; Tirlapur, Uday K; Vollrath, Fritz; Carr, Andrew J


    The cause of the high failure rates often observed following rotator cuff tendon repairs, particularly massive tears, is not fully understood. Collagen structural changes have been shown to alter tendon thermal and mechanical properties. This study aimed to form a quantitative rather than qualitative assessment, of whether differences in collagen structure and integrity existed between small biopsies of normal, small, and massive rotator cuff tears using differential scanning calorimetry. Thermal properties were measured for 28 human biopsies taken intra-operatively from normal, small, and massive rotator cuff tendon tears in this powered study. Denaturation temperatures are represented by T(onset) (°C) and T(peak) (°C). The T(onset) is proposed to represent water-amide hydrogen bond breakage and resulting protein backbone mobility. T(peak) reportedly corresponds to the temperature at which the majority of proteins fall out of solution. Denaturation enthalpy (ΔH) should correlate with the amount of triple helical structure that is denatured. Fluorescence and confocal microscopy allowed quantitative validation. Small and massive rotator cuff tears had significantly higher T(onset), T(peak), and ΔH compared to controls. Polarized light microscopy of torn tendons confirmed greater collagen structural disruption compared to controls. These novel findings suggest greater quantifiable collagen structural disruption in rotator cuff tears, compared to controls. This study offers insight into possible mechanisms for the reduced strength of torn tendons and may explain why repaired tendons fail to heal.

  10. Alternative Calorimetry Based on the Photothermoelectric (PTE) Effect: Application to Magnetic Nanofluids (United States)

    Dadarlat, Dorin; Misse, Patrick R. N.; Maignan, Antoine; Guilmeau, Emmanuel; Turcu, Rodica; Vekas, Ladislau; Tudoran, Cristian; Depriester, Michael; Sahraoui, Abdelhak Hadj


    Photothermoelectric (PTE) calorimetry was applied for the first time for thermal characterization of liquids. Both back and front detection configurations, together with the thermal-wave resonator cavity (TWRC) scanning procedure, have been used in order to measure the thermal diffusivity and thermal effusivity of a particular magnetic nanofluid: carrier liquid—transformer oil, surfactant—oleic acid, nanoparticles' type—{Fe}3{O}4.The investigations were performed as a function of the nanoparticles' concentration. Small increases of thermal diffusivity (from 9.06× 10^{-8} {m}2{\\cdot } {s}^{-1} up to 9.84× 10^{-8} {m}2{\\cdot } {s}^{-1}) and thermal effusivity (from 450 {W}{\\cdot } {s}^{1/2}{\\cdot } {m}^{-2}{\\cdot } {K}^{-1} up to 520 {W}{\\cdot } {s}^{1/2}{\\cdot } {m}^{-2}{\\cdot } {K}^{-1}) with increasing concentration of {Fe}3{O}4 nanoparticles (from 0 up to 0.623 mg {Fe}3{O}4/{ml} fluid) were observed. The comparison with the photopyroelectric (PPE) method shows that PTE and PPE give similar results but, for the moment, PPE is more accurate.

  11. Application of Differential Scanning Calorimetry (DSC in study of phase transformations in ductile iron

    Directory of Open Access Journals (Sweden)

    R. Przeliorz


    Full Text Available The effect of heating rate on phase transformations to austenite range in ductile iron of the EN-GJS-450-10 grade was investigated. For studies of phase transformations, the technique of differential scanning calorimetry (DSC was used. Microstructure was examined by optical microscopy. The calorimetric examinations have proved that on heating three transformations occur in this grade of ductile iron, viz. magnetic transformation at the Curie temperature, pearlite→austenite transformation and ferrite→austenite transformation. An increase in the heating rate shifts the pearlite→austenite and ferrite→austenite transformations to higher temperature range. At the heating rate of 5 and 15°C/min, local extrema have been observed to occur: for pearlite→austenite transformation at 784°C and 795°C, respectively, and for ferrite→austenite transformation at 805°C and 821°C, respectively. The Curie temperature of magnetic transformation was extrapolated to a value of 740°C. Each transformation is related with a specific thermal effect. The highest value of enthalpy is accompanying the ferrite→austenite transformation, the lowest occurs in the case of pearlite→austenite transformation.

  12. Sub-picowatt resolution calorimetry with niobium nitride thin-film thermometer

    Energy Technology Data Exchange (ETDEWEB)

    Dechaumphai, Edward; Chen, Renkun, E-mail: [Department of Mechanical and Aerospace Engineering, University of California, San Diego, La Jolla, California 92093 (United States)


    High-resolution calorimetry has many important applications such as probing nanoscale thermal transport and studying the thermodynamics of biological and chemical systems. In this work, we demonstrated a calorimeter with an unprecedentedly high resolution at room temperature using a high-performance resistive thermometry material, niobium nitride (NbN{sub x}). Based on a theoretical analysis, we first showed that the heat flux resolution of a resistive-thermometry based calorimeter depends on the parasitic thermal conductance of the device and the temperature coefficient of resistance (TCR) of the thermometer, when the noise is limited by the Johnson noise. Based on this analysis, we then developed a calorimeter using NbN{sub x} as the thermometry material because it possesses both high TCR (∼0.67%/K) and a low thermal conductivity (k ∼ 1.1 W/m K). This calorimeter, when used with the modulated heating scheme, demonstrated an unprecedentedly high power resolution of 0.26 pW at room temperature. In addition, NbN{sub x} based resistive thermometry can also be extended to cryogenic temperature, where the TCR is shown to be significantly higher.

  13. Binding of Ru(terpyridine)(pyridine)dipyridophenazine to DNA studied with polarized spectroscopy and calorimetry. (United States)

    Mårtensson, Anna K F; Lincoln, Per


    Linear and circular dichroism (LD and CD) spectroscopy as well as isothermal titration calorimetry (ITC) have been used to investigate the interaction of Ru(tpy)(py)dppz(2+) (tpy = 2,2':6',2''-terpyridyl; py = pyridine; dppz = dipyrido[3,2-a:2'3'-c]phenazine) with DNA, providing detailed information about the DNA binding thermodynamics and binding geometry of the metal complex. Flow LD, CD and isotropic absorption indicate that Ru(tpy)(py)dppz(2+) bind to DNA from the minor groove with the dppz ligand intercalated between base pairs, very similar to its chiral structural isomers Δ- and Λ-Ru(bpy)2dppz(2+) (bpy = 2,2'-bipyridine). A simple cooperative binding model with one binding geometry provide an excellent fit for calorimetric and absorption titration data. The values of the neighbor interaction thermodynamic parameters for Ru(tpy)(py)dppz(2+) suggest that complexes bound contiguously prefer to have their tpy ligands oriented towards the same strand.

  14. The use of differential scanning calorimetry for the purity verification of pharmaceutical reference standards. (United States)

    Mathkar, S; Kumar, S; Bystol, A; Olawoore, K; Min, D; Markovich, R; Rustum, A


    Reference standards are routinely used in pharmaceutical industry to determine strength, content, and the quality of drug products, active pharmaceutical ingredients (API), preservatives, antioxidants and excipients. Traditionally, chromatographic techniques such as High Performance Liquid Chromatography (HPLC) and Gas Chromatography (GC) in conjunction with other analytical techniques have been used to determine the purity and strength of a specific lot of a compound for the purpose of qualifying the lot to use as a reference standard. The assigned purity of the reference standard for a wide variety of compounds can be verified using an absolute method such as Differential Scanning Calorimetry (DSC). In this paper, purity of 16 reference standards was determined by DSC and the results were then compared to the purity values that were obtained using HPLC and other analytical techniques. The results indicate that the purity obtained from DSC analysis is comparable to the chromatographic purity for organic compounds that are at least 98% pure. Use of DSC for purity determination is not appropriate if a compound lacks sharp melting point, decomposes in the defined temperature range or exhibits other thermal event(s) which interfere with the melting point of the compound. The use of DSC as an alternative and or complementary method to verify the purity of a compound as part of the pharmaceutical reference standard certification process is discussed.

  15. Applications of differential scanning calorimetry for thermal stability analysis of proteins: qualification of DSC. (United States)

    Wen, Jie; Arthur, Kelly; Chemmalil, Letha; Muzammil, Salman; Gabrielson, John; Jiang, Yijia


    Differential scanning calorimetry (DSC) has been used to characterize protein thermal stability, overall conformation, and domain folding integrity by the biopharmaceutical industry. Recently, there have been increased requests from regulatory agencies for the qualification of characterization methods including DSC. Understanding the method precision can help determine what differences between samples are significant and also establish the acceptance criteria for comparability and other characterization studies. In this study, we identify the parameters for the qualification of DSC for thermal stability analysis of proteins. We use these parameters to assess the precision and sensitivity of DSC and demonstrate that DSC is suitable for protein thermal stability analysis for these purposes. Several molecules from different structural families were studied. The experiments and data analyses were performed by different analysts using different instruments at different sites. The results show that the (apparent) thermal transition midpoint (T(m)) values obtained for the same protein by same and different instruments and/or analysts are quite reproducible, and the profile similarity values obtained for the same protein from the same instrument are also high. DSC is an appropriate method for assessing protein thermal stability and conformational changes.

  16. Forward calorimetry for heavy-ion physics at the STAR experiment (United States)

    Brown, Daniel; STAR Experiment at RHIC Collaboration; STAR Forward Calorimeter Group Team


    A forward calorimeter utilizing hadronic and electromagnetic calorimetry at the STAR experiment of RHIC will achieve a variety of physics goals. These goals include studying long-range rapidity correlations, event plane correlations in heavy-ion interactions, and studying the gluon contribution to the proton spin. Upgrades to the AGS E864 lead-scintillating fiber calorimeter have increased spatial resolution by utilizing cell pixelization. Light collection has been optimized and fringe field effects have been minimized by the introduction of Fresnel lenses and mu-metal shielding. A prototype consisting of a 2x3 cell stack was installed into the forward region of STAR for the end of run16. This prototype investigated the introduction of these new techniques as well as a trial of Silicon Photomultipliers (SiPMs) as an alternate to traditional Photomultiplier Tubes (PMTs). SiPMs do not suffer from fringe field effects, but are susceptible to radiation damage by neutrons, so their performance during the prototype operation was analyzed. This talk will discuss the effects of Fresnel lenses on light collection, mu-metal shielding effects on PMTs, and radiation effects on SiPMs.

  17. Single-strand DNA translation initiation step analyzed by Isothermal Titration Calorimetry

    Energy Technology Data Exchange (ETDEWEB)

    Damian, Luminita, E-mail: [CNRS, IPBS (Institut de Pharmacologie et de Biologie Structurale), 205 route de Narbonne, F-31077 Toulouse (France); Universite de Toulouse, UPS, IPBS, F-31077 Toulouse (France); IUB, School of Engineering and Science, D-28727 Bremen (Germany); Marty-Detraves, Claire, E-mail: [CNRS, IPBS (Institut de Pharmacologie et de Biologie Structurale), 205 route de Narbonne, F-31077 Toulouse (France); Universite de Toulouse, UPS, IPBS, F-31077 Toulouse (France); Winterhalter, Mathias [IUB, School of Engineering and Science, D-28727 Bremen (Germany); Fournier, Didier, E-mail: [CNRS, IPBS (Institut de Pharmacologie et de Biologie Structurale), 205 route de Narbonne, F-31077 Toulouse (France); Universite de Toulouse, UPS, IPBS, F-31077 Toulouse (France); Paquereau, Laurent, E-mail: [CNRS, IPBS (Institut de Pharmacologie et de Biologie Structurale), 205 route de Narbonne, F-31077 Toulouse (France); Universite de Toulouse, UPS, IPBS, F-31077 Toulouse (France)


    Is single-strand DNA translatable? Since the 60s, the question still remains whether or not DNA could be directly translated into protein. Some discrepancies in the results were reported about functional translation of single-strand DNA but all results converged on a similar behavior of RNA and ssDNA in the initiation step. Isothermal Titration Calorimetry method was used to determine thermodynamic constants of interaction between single-strand DNA and S30 extract of Escherichia coli. Our results showed that the binding was not affected by the nature of the template tested and the dissociation constants were in the same range when ssDNA (K{sub d} = 3.62 {+-} 2.1 x 10{sup -8} M) or the RNA corresponding sequence (K{sub d} = 2.7 {+-} 0.82 x 10{sup -8} M) bearing SD/ATG sequences were used. The binding specificity was confirmed by antibiotic interferences which block the initiation complex formation. These results suggest that the limiting step in translation of ssDNA is the elongation process.

  18. Thermodynamic Study on the Protonation Reactions of Glyphosate in Aqueous Solution: Potentiometry, Calorimetry and NMR spectroscopy. (United States)

    Liu, Bijun; Dong, Lan; Yu, Qianhong; Li, Xingliang; Wu, Fengchang; Tan, Zhaoyi; Luo, Shunzhong


    Glyphosate [N-(phosphonomethyl)glycine] has been described as the ideal herbicide because of its unique properties. There is some conflicting information concerning the structures and conformations involved in the protonation process of glyphosate. Protonation may influence the chemical and physical properties of glyphosate, modifying its structure and the chemical processes in which it is involved. To better understand the species in solution associated with changes in pH, thermodynamic study (potentiometry, calorimetry and NMR spectroscopy) about the protonation pathway of glyphosate is performed. Experimental results confirmed that the order of successive protonation sites of totally deprotonated glyphosate is phosphonate oxygen, amino nitrogen, and finally carboxylate oxygen. This trend is in agreement with the most recent theoretical work in the literature on the subject (J. Phys. Chem. A 2015, 119, 5241-5249). The result is important because it confirms that the protonated site of glyphosate in pH range 7-8, is not on the amino but on the phosphonate group instead. This corrected information can improve the understanding of the glyphosate chemical and biochemical action.

  19. Thermodynamics of the complexation of Hg(II) by cysteinyl peptide ligands using isothermal titration calorimetry

    Energy Technology Data Exchange (ETDEWEB)

    Ngu-Schwemlein, Maria, E-mail: [Department of Chemistry, Winston-Salem State University, Winston-Salem, NC 27110 (United States); Merle, John K.; Healy, Patrick; Schwemlein, Stefanie; Rhodes, Sade [Department of Chemistry, Winston-Salem State University, Winston-Salem, NC 27110 (United States)


    The present study was undertaken to better understand the complexation of mercury (II) by cysteine, histidine, tryptophan, and their di- and tri-peptides. Their mercury (II) binding affinities and associated thermodynamic parameters are evaluated by isothermal titration calorimetry. Cysteine S-donor atoms form the strongest complexes, which can be attributed to a more exothermic Hg-S soft acid and soft base interaction. These thiol S-donor peptide ligands show two sequential binding for mercury (II). Their stability constants for the first binding (10{sup 8} M{sup -1} to >10{sup 10} M{sup -1}) are largely due to favorable contribution of the enthalpy term to the free energy of complexation. As more mercury (II) ions are added, this enthalpy contribution decreases and the free energy of the second binding (10{sup 5} M{sup -1} to 10{sup 6} M{sup -1}) is partially compensated by the entropy term. The dependency of the fluorescence intensity for these peptides on mercury (II) concentration shows two different Stern-Volmer plots, which corroborates the calorimetric data and supports the formation of two types of stable complexes.

  20. Interaction of oridonin with human serum albumin by isothermal titration calorimetry and spectroscopic techniques. (United States)

    Li, Xiangrong; Yang, Zhenhua


    Oridonin has been traditionally and widely used for treatment of various human diseases due to its uniquely biological, pharmacological and physiological functions. In this study, the interaction between oridonin and human serum albumin (HSA) was investigated using isothermal titration calorimetry (ITC), in combination with fluorescence spectroscopy and UV-vis absorption spectroscopy. We found that the hydrogen bond and van der Waals force are the major binding forces in the binding of oridonin to HSA. The binding of oridonin to HSA is driven by favorable enthalpy and unfavorable entropy. Oridonin can quench the fluorescence of HSA through a static quenching mechanism. The binding constant between oridonin and HSA is moderate and the equilibrium fraction of unbound oridonin f(u) > 60%. Binding site I is found to be the primary binding site for oridonin. Additionally, oridonin may induce conformational changes of HSA and affect its biological function as the carrier protein. The results of the current study suggest that oridonin can be stored and transported from the circulatory system to reach its target organ to provide its therapeutic effects. But its side-effect in the clinics cannot be overlook. The study provides an accurate and full basic data for clarifying the binding mechanism of oridonin with HSA and is helpful for understanding its effect on protein function during the blood transportation process and its biological activity in vivo.

  1. Phosphate sorption by three potential filter materials as assessed by isothermal titration calorimetry. (United States)

    Lyngsie, Gry; Penn, Chad J; Hansen, Hans C B; Borggaard, Ole K


    Phosphorus eutrophication of lakes and streams, coming from drained farmlands, is a serious problem in areas with intensive agriculture. Installation of phosphate (P) sorbing filters at drain outlets may be a solution. The aim of this study was to improve the understanding of reactions involved in P sorption by three commercial P sorbing materials, i.e. Ca/Mg oxide-based Filtralite-P, Fe oxide-based CFH-12 and Limestone in two particle sizes (2-1 mm and 1-0.5 mm), by means of isothermal titration calorimetry (ITC), sorption isotherms, sequential extractions and SEM-EDS. The results indicate that P retention by CFH is due to surface complexation by rapid formation of strong Fe-P bonds. In contrast, retention of P by Filtralite-P and Limestone strongly depends on pH and time and is interpreted due to formation of calcium phosphate precipitate(s). Consequently, CFH can unambiguously be recommended as P retention filter material in drain outlets, whereas the use of Filtralite-P and Limestone has certain (serious) limitations. Thus, Filtralite-P has high capacity to retain P but only at alkaline pH (pH ≥ 10) and P retention by Limestone requires long-time contact and a high ratio between sorbent and sorbate.

  2. Microtubule-associated proteins and tubulin interaction by isothermal titration calorimetry. (United States)

    Tsvetkov, P O; Barbier, P; Breuzard, G; Peyrot, V; Devred, F


    Microtubules play an important role in a number of vital cell processes such as cell division, intracellular transport, and cell architecture. The highly dynamic structure of microtubules is tightly regulated by a number of stabilizing and destabilizing microtubule-associated proteins (MAPs), such as tau and stathmin. Because of their importance, tubulin-MAPs interactions have been extensively studied using various methods that provide researchers with complementary but sometimes contradictory thermodynamic data. Isothermal titration calorimetry (ITC) is the only direct thermodynamic method that enables a full thermodynamic characterization (stoichiometry, enthalpy, entropy of binding, and association constant) of the interaction after a single titration experiment. This method has been recently applied to study tubulin-MAPs interactions in order to bring new insights into molecular mechanisms of tubulin regulation. In this chapter, we review the technical specificity of this method and then focus on the use of ITC in the investigation of tubulin-MAPs binding. We describe technical issues which could arise during planning and carrying out the ITC experiments, in particular with fragile proteins such as tubulin. Using examples of stathmin and tau, we demonstrate how ITC can be used to gain major insights into tubulin-MAP interaction.

  3. Vascular Endothelial Growth Factor Peptide Ligands Explored by Competition Assay and Isothermal Titration Calorimetry. (United States)

    Reille-Seroussi, Marie; Gaucher, Jean-François; Desole, Claudia; Gagey-Eilstein, Nathalie; Brachet, Franck; Broutin, Isabelle; Vidal, Michel; Broussy, Sylvain


    The v114* cyclic peptide has been identified as a tight vascular endothelial growth factor (VEGF) ligand. Here we report on the use of isothermal titration calorimetry (ITC), 96-well plate competition assay, and circular dichroism (CD) to explore the binding determinants of a new set of related peptides. Anti-VEGF antibodies are currently used in the clinic for regulating angiogenesis in cancer and age-related macular degeneration treatment. In this context, our aim is to develop smaller molecular entities with high affinity for the growth factor by a structure activity relationship approach. The cyclic disulfide peptide v114* was modified in several ways, including truncation, substitution, and variation of the size and nature of the cycle. The results indicated that truncation or substitution of the four N-terminal amino acids did not cause severe loss in affinity, allowing potential peptide labeling. Increase of the cycle size or substitution of the disulfide bridge with a thioether linkage drastically decreased the affinity, due to an enthalpy penalty. The leucine C-terminal residue positively contributed to affinity. Cysteine N-terminal acetylation induced favorable ΔΔG° and ΔΔH° of binding, which correlated with free peptide CD spectra changes. We also propose a biochemical model to extrapolate Ki from IC50 values measured in the displacement assay. These calculated Ki correlate well with the Kd values determined by extensive direct and reverse ITC measurements.

  4. Thermodynamic Study of 8-Hydroxyquinoline by Adiabatic Calorimetry and Thermal Analysis

    Institute of Scientific and Technical Information of China (English)

    WANG Shao-Xu; TAN Zhi-Cheng; LI Yan-Sheng; TONG Bo; LI Ying; SHI Quan; ZHANG Jing-Nan


    A calorimetric study and thermal analysis for 8-hydroxyquinoline were performed.The low-temperature heat capacity of this compound was measured with a precise automated adiabatic calorimeter over the temperature range from 78 to 370 K.The melting point True,molar enthalpy △fusHm and molar entropy △fusSm of fusion of this sub-tively.The thermodynamic functions of the substance,such as molar enthalpy and entropy of fusion,and thermo-dynamic functions [Hr-H298.15] and [ST-S298.15] were derived from two polynomial equations of the experi-mental molar heat capacities against the reduced temperature fitted by the least square method.The melting tem-peratures for the sample and the absolutely pure compound have been obtained from fractional melting experiments to be 345.601 and 345.761 K,respectively,and the molar fraction purity of the sample was calculated to be 0.9978 according to the van't Hoff equation.The thermal stability of the compound was further investigated by differential scanning calorimetry(DSC).

  5. AC Calorimetry and Thermophysical Properties of Bulk Glass-Forming Metallic Liquids (United States)

    Johnson, William L.


    Thermo-physical properties of two bulk metallic glass forming alloys, Ti34Zr11Cu47Ni8 (VIT 101) and Zr57Nb5Ni12.6Al10CU15.4 (VIT 106), were investigated in the stable and undercooled melt. Our investigation focused on measurements of the specific heat in the stable and undercooled liquid using the method of AC modulation calorimetry. The VIT 106 exhibited a maximum undercooling of 140 K in free radiative cooling. Specific heat measurements could be performed in stable melt down to an undercooling of 80 K. Analysis of the specific heat data indicate an anomaly near the equilibrium liquidus temperature. This anomaly is also observed in y the temperature dependencies of the external relaxation time, the specific volume, and the surface tension; it is tentatively attributed to a phase separation in the liquid state. The VIT 101 specimen exhibited a small undercooling of about 50 K. Specific heat measurements were performed in the stable and undercooled melt. These various results will be combined with ground based work such as the measurement of T-T-T curves in the electrostatic levitator and low temperature viscosity and specific heat measurements for modeling the nucleation kinetics of these alloys.

  6. Changes in polymer foils used in food packaging tested by using differential scanning calorimetry

    Indian Academy of Sciences (India)

    J Gajdoš Kljusurić


    This work is an experimental study of the differential scanning calorimetry characterisation of polymer materials used in food packaging materials, such as polypropylene (0.03 mm), polyethylene (0.1 and 0.03 mm), poly(D-(-)--hydroxybutyrate) (powder), two-layered polypropylene (0.064 mm), and two-layered polypropylene with poly-vinylidene-chloride (0.012/0.021). The polymer stability was checked by simulation of conditions during food preparation in microwave ovens, sterilisation or rapid freezing. The materials were tested in the temperature range from 40 to 200°C at different scan rates from 2 to 30° C min-1 during heating or cooling. The enthalpies show a high correlation coefficient (0.964) with scan rate. All samples undergo phase change in the temperature range from 107 to 173°C during heating and enthalpies are in the range from 31.8 to 71.1 J g−1 Upon subsequent cooling from 200°C, the temperature range of phase changes is shifted to lower temperatures from 86 to 102°C with enthalpies ranging from 30.4 to 57.8 J g−1. Experiments with exposure of polymers to microwave radiation and freezing prove that the phase change considering the temperature range is very similar in all experiments.

  7. A novel optical calorimetry dosimetry approach applied to an HDR Brachytherapy source (United States)

    Cavan, A.; Meyer, J.


    The technique of Digital Holographic Interferometry (DHI) is applied to the measurement of radiation absorbed dose distribution in water. An optical interferometer has been developed that captures the small variations in the refractive index of water due to the radiation induced temperature increase ΔT. The absorbed dose D is then determined with high temporal and spatial resolution using the calorimetric relation D=cΔT (where c is the specific heat capacity of water). The method is capable of time resolving 3D spatial calorimetry. As a proof-of-principle of the approach, a prototype DHI dosimeter was applied to the measurement of absorbed dose from a High Dose Rate (HDR) Brachytherapy source. Initial results are in agreement with modelled doses from the Brachyvision treatment planning system, demonstrating the viability of the system for high dose rate applications. Future work will focus on applying corrections for heat diffusion and geometric effects. The method has potential to contribute to the dosimetry of diverse high dose rate applications which require high spatial resolution such as microbeam radiotherapy (MRT) or small field proton beam dosimetry but may potentially also be useful for interface dosimetry.

  8. DCal: A custom integrated circuit for calorimetry at the International Linear Collider

    Energy Technology Data Exchange (ETDEWEB)

    Hoff, James R.; Mekkaoui, Abderrazek; Yarema, Ray; /Fermilab; Drake, Gary; Repond, Jose; /Argonne


    A research and development collaboration has been started with the goal of producing a prototype hadron calorimeter section for the purpose of proving the Particle Flow Algorithm concept for the International Linear Collider. Given the unique requirements of a Particle Flow Algorithm calorimeter, custom readout electronics must be developed to service these detectors. This paper introduces the DCal or Digital Calorimetry Chip, a custom integrated circuit developed in a 0.25um CMOS process specifically for this International Linear Collider project. The DCal is capable of handling 64 channels, producing a 1-bit Digital-to-Analog conversion of the input (i.e. hit/no hit). It maintains a 24-bit timestamp and is capable of operating either in an externally triggered mode or in a self-triggered mode. Moreover, it is capable of operating either with or without a pipeline delay. Finally, in order to permit the testing of different calorimeter technologies, its analog front end is capable of servicing Particle Flow Algorithm calorimeters made from either Resistive Plate Chambers or Gaseous Electron Multipliers.

  9. Morphological Investigation into Starch Bio-Nanocomposites via Synchrotron Radiation and Differential Scanning Calorimetry

    Directory of Open Access Journals (Sweden)

    Huihua Liu


    Full Text Available We studied a hydrophilic, plasticized bionanocomposite system involving sorbitol plasticizer, amylose biopolymer, and montmorillonite (MMT for the presence of competitive interactions among them at different moisture content. Synchrotron analysis via small angle X-ray scattering (SAXS and thermal analysis using differential scanning calorimetry (DSC were performed to understand crystalline growth and the distribution of crystalline domains within the samples. The SAXS diffraction patterns showed reduced interhelix spacing in the amylose network indicating strong amylose-sorbitol interactions. Depending on the sorbitol and MMT concentration, these interactions also affected the free moisture content and crystalline domains. Domains of around 95 Å and 312 Å were found in the low-moisture-content samples as compared to a single domain of 95 Å in the high-moisture-content samples. DSC measurements confirmed that the MMT increased the onset and the melting temperature of nanocomposites. Moreover, the results showed that the ternary interactions among sorbitol-amylose-MMT supported the crystalline heterogeneity through secondary nucleation.

  10. A Universal Method for Fishing Target Proteins from Mixtures of Biomolecules using Isothermal Titration Calorimetry

    Energy Technology Data Exchange (ETDEWEB)

    Zhou, X.; Sun, Q; Kini, R; Sivaraman, J


    The most challenging tasks in biology include the identification of (1) the orphan receptor for a ligand, (2) the ligand for an orphan receptor protein, and (3) the target protein(s) for a given drug or a lead compound that are critical for the pharmacological or side effects. At present, several approaches are available, including cell- or animal-based assays, affinity labeling, solid-phase binding assays, surface plasmon resonance, and nuclear magnetic resonance. Most of these techniques are not easy to apply when the target protein is unknown and the compound is not amenable to labeling, chemical modification, or immobilization. Here we demonstrate a new universal method for fishing orphan target proteins from a complex mixture of biomolecules using isothermal titration calorimetry (ITC) as a tracking tool. We took snake venom, a crude mixture of several hundred proteins/peptides, as a model to demonstrate our proposed ITC method in tracking the isolation and purification of two distinct target proteins, a major component and a minor component. Identities of fished out target proteins were confirmed by amino acid sequencing and inhibition assays. This method has the potential to make a significant advancement in the area of identifying orphan target proteins and inhibitor screening in drug discovery and characterization.

  11. Application of differential scanning calorimetry to estimate quality and nutritional properties of food products. (United States)

    Parniakov, Oleksii; Bals, Olivier; Barba, Francisco J; Mykhailyk, Viacheslav; Lebovka, Nikolai; Vorobiev, Eugene


    Over the last years, both food researchers and food industry have shown an increased interest in finding techniques that can estimate the modifications in quality, nutritional and thermophysical properties of food products during processing and/or storage. For instance, differential scanning calorimetry (DSC) has attracted the interest of the scientific community because only a small amount of sample is needed for the analysis. Moreover, it does not require any specific sample preparation and it is a repeatable and reliable method. In addition, DSC methodology needs a short time of experiments compared to other techniques used for the same purpose. At this stage of investigation, there is a need to evaluate the commonly accepted and new emerging DSC applications in order to establish the optimum conditions of emerging processing. This paper reviews the current and new insights of DSC technique for the estimation of quality, nutritional and thermophysical properties of food products during conventional and emerging processing and/or subsequent storage. The estimation of the different properties in several food matrices after processing and/or storage is also discussed.

  12. Pressure perturbation calorimetry, heat capacity and the role of water in protein stability and interactions. (United States)

    Cooper, A; Cameron, D; Jakus, J; Pettigrew, G W


    It is widely acknowledged, and usually self-evident, that solvent water plays a crucial role in the overall thermodynamics of protein stabilization and biomolecular interactions. Yet we lack experimental techniques that can probe unambiguously the nature of protein-water or ligand-water interactions and how they might change during protein folding or ligand binding. PPC (pressure perturbation calorimetry) is a relatively new technique based on detection of the heat effects arising from application of relatively small pressure perturbations (+/-5 atm; 1 atm=101.325 kPa) to dilute aqueous solutions of proteins or other biomolecules. We show here how this can be related to changes in solvation/hydration during protein-protein and protein-ligand interactions. Measurements of 'anomalous' heat capacity effects in a wide variety of biomolecular interactions can also be related to solvation effects as part of a quite fundamental principle that is emerging, showing how the apparently unusual thermodynamics of interactions in water can be rationalized as an inevitable consequence of processes involving the co-operative interaction of multiple weak interactions. This leads to a generic picture of the thermodynamics of protein folding stabilization in which hydrogen-bonding plays a much more prominent role than has been hitherto supposed.

  13. Differential scanning calorimetry as a tool for protein folding and stability. (United States)

    Johnson, Christopher M


    Differential scanning calorimetry measures the heat capacity of states and the excess heat associated with transitions that can be induced by temperature change. The integral of the excess heat capacity is the enthalpy for this process. Despite this potentially intimidating sounding physical chemistry background, DSC has found almost universal application in studying biological macromolecules. In the case of proteins, DSC can be used to determine equilibrium thermodynamic stability and folding mechanism but can also be used in a more qualitative manner screening for thermal stability as an indicator for, ligand binding, pharmaceutical formulation or conditions conducive to crystal growth. DSC usually forms part of a wider biophysical characterisation of the biological system of interest and so the literature is diverse and difficult to categorise for the technique in isolation. This review therefore describes the potential uses of DSC in studying protein folding and stability, giving brief examples of applications from the recent literature. There have also been some interesting developments in the use of DSC to determine barrier heights for fast folding proteins and in studying complex protein mixtures such as human plasma that are considered in more detail.

  14. Single-experiment displacement assay for quantifying high-affinity binding by isothermal titration calorimetry. (United States)

    Krainer, Georg; Keller, Sandro


    Isothermal titration calorimetry (ITC) is the gold standard for dissecting the thermodynamics of a biomolecular binding process within a single experiment. However, reliable determination of the dissociation constant (KD) from a single titration is typically limited to the range 100 μM>KD>1 nM. Interactions characterized by a lower KD can be assessed indirectly by so-called competition or displacement assays, provided that a suitable competitive ligand is available whose KD falls within the directly accessible window. However, this protocol is limited by the fact that it necessitates at least two titrations to characterize one high-affinity inhibitor, resulting in considerable consumption of both sample material and time. Here, we introduce a fast and efficient ITC displacement assay that allows for the simultaneous characterization of both a high-affinity ligand and a moderate-affinity ligand competing for the same binding site on a receptor within a single experiment. The protocol is based on a titration of the high-affinity ligand into a solution containing the moderate-affinity ligand bound to the receptor present in excess. The resulting biphasic binding isotherm enables accurate and precise determination of KD values and binding enthalpies (ΔH) of both ligands. We discuss the theoretical background underlying the approach, demonstrate its practical application to metal ion chelation, explore its potential and limitations with the aid of simulations and statistical analyses, and elaborate on potential applications to protein-inhibitor interactions.

  15. Application of isothermal titration calorimetry as a tool to study natural product interactions. (United States)

    Callies, O; Hernández Daranas, A


    Covering: up to February 2015Over the past twenty-five years, isothermal titration calorimetry (ITC) has become a potent tool for the study a great variety of molecular interactions. This technique is able to provide a complete thermodynamic profile of an interaction process in a single experiment, with a series of advantages in comparison to other comparable techniques, such as less amount of sample or no need of chemical modification or labelling. It is thus not surprising that ITC has been applied to study the manifold types of interactions of natural products to get new insights into the molecular key factors implied in the complexation process of this type of compounds. This review provides an overview over the applications of ITC as a potent tool to investigate interactions of natural products with proteins, nucleic acids, oligosaccharides, and other types of receptors. The examples have been selected depending on the impact that this technique had during the investigation and revision of the interactions involved in the bioactivity of a compound, lead optimization or technical applications.

  16. Application of TZERO calibrated modulated temperature differential scanning calorimetry to characterize model protein formulations. (United States)

    Badkar, Aniket; Yohannes, Paulos; Banga, Ajay


    The objective of this study was to evaluate the feasibility of using T(ZERO) modulated temperature differential scanning calorimetry (MDSC) as a novel technique to characterize protein solutions using lysozyme as a model protein and IgG as a model monoclonal antibody. MDSC involves the application of modulated heating program, along with the standard heating program that enables the separation of overlapping thermal transitions. Although characterization of unfolding transitions for protein solutions requires the application of high sensitive DSC, separation of overlapping transitions like aggregation and other exothermic events may be possible only by use of MDSC. A newer T(ZERO) calibrated MDSC model from TA instruments that has improved sensitivity than previous models was used. MDSC analysis showed total, reversing and non-reversing heat flow signals. Total heat flow signals showed a combination of melting endotherms and overlapping exothermic events. Under the operating conditions used, the melting endotherms were seen in reversing heat flow signal while the exothermic events were seen in non-reversing heat flow signal. This enabled the separation of overlapping thermal transitions, improved data analysis and decreased baseline noise. MDSC was used here for characterization of lysozyme solutions, but its feasibility for characterizing therapeutic protein solutions needs further assessment.

  17. Quantifying the rates of relaxation of binary mixtures of amorphous pharmaceuticals with isothermal calorimetry. (United States)

    Alem, Naziha; Beezer, Anthony E; Gaisford, Simon


    While the use of isothermal calorimetry to quantify the rate of relaxation of one-phase amorphous pharmaceuticals, through application of models, is well documented, the resolution of the models to detect and quantify relaxation in systems containing two independent amorphous phases is not known. Addressing this knowledge gap is the focus of this work. Two fitting models were tested; the Kohlrausch-Williams-Watts model (KWW) and the modified-stretch exponential (MSE). The ability of each model to resolve relaxation processes in binary systems was determined with simulated calorimetric data. It was found that as long as the relaxation time constants of the relaxation processes were with 10(3) of each other, the models could determine that two events were occurring and could quantify the correct reaction parameters of each. With greater differences in the time constants, the faster process always dominates the data and the resolving power of the models is lost. Real calorimetric data were then obtained for two binary amorphous systems (sucrose-lactose and sucrose-indomethacin mixtures). The relaxation behaviour of all the single components was characterised as they relaxed individually to provide reference data. The ability of the KWW model to recover the expected relaxation parameters for two component data was impaired because of their inherently noisy nature. The MSE model reasonably recovered the expected parameters for each component for the sucrose-indomethacin system but not for the sucrose-lactose system, which may indicate a possible interaction in that case.

  18. Application of isothermal titration calorimetry and column chromatography for identification of biomolecular targets. (United States)

    Zhou, Xingding; Kini, R Manjunatha; Sivaraman, J


    This protocol describes a method for identifying unknown target proteins from a mixture of biomolecules for a given drug or a lead compound. This method is based on a combination of chromatography and isothermal titration calorimetry (ITC) where ITC is used as a tracking tool. The first step involves the use of ITC to confirm the binding of ligand to a component in the biomolecular mixture. Subsequently, the biomolecular mixture is fractionated by chromatography, and the binding of the ligand with individual fractions (or subfractions) is verified by ITC. The iteration of chromatographic purification on the fractions combined with ITC results in identifying the target protein. This method is useful when the target protein or ligand is unknown and/or not amenable to labeling, chemical modification or immobilization. This protocol has been successfully used by our team and by others to identify both low-abundance and highly abundant target proteins present in biomolecular mixtures. With this protocol, it takes approximately 3-5 d to identify the target protein from a mixture.

  19. Advances in the analysis of isothermal titration calorimetry data for ligand-DNA interactions. (United States)

    Buurma, Niklaas J; Haq, Ihtshamul


    Isothermal titration calorimetry (ITC) is a well established technique for the study of biological interactions. The strength of ITC is that it directly measures enthalpy changes associated with interactions. Experiments can also yield binding isotherms allowing quantification of equilibrium binding constants, hence an almost complete thermodynamic profile can be established. Principles and application of ITC have been well documented over recent years, experimentally the technique is simple to use and in ideal scenarios data analysis is trivial. However, ITC experiments can be designed such that previously inaccessible parameters can be evaluated. We outline some of these advances, including (1) exploiting different experimental conditions; (2) low affinity systems; (3) high affinity systems and displacement assays. In addition we ask the question: What if data cannot be fit using the fitting functions incorporated in the data-analysis software that came with your ITC? Examples where such data might be generated include systems following non 1:n binding patterns and systems where binding is coupled to other events such as ligand dissociation. Models dealing with such data are now appearing in literature and we summarise examples relevant for the study of ligand-DNA interactions.

  20. Enzyme activity determination on macromolecular substrates by isothermal titration calorimetry: application to mesophilic and psychrophilic chitinases. (United States)

    Lonhienne, T; Baise, E; Feller, G; Bouriotis, V; Gerday, C


    Isothermal titration calorimetry has been applied to the determination of the kinetic parameters of chitinases (EC by monitoring the heat released during the hydrolysis of chitin glycosidic bonds. Experiments were carried out using two different macromolecular substrates: a soluble polymer of N-acetylglucosamine and the insoluble chitin from crab shells. Different experimental temperatures were used in order to compare the thermodependence of the activity of two chitinases from the psychrophile Arthrobacter sp. TAD20 and of chitinase A from the mesophile Serratia marcescens. The method allowed to determine unequivocally the catalytic rate constant k(cat), the activation energy (E(a)) and the thermodynamic activation parameters (DeltaG(#), DeltaH(#), DeltaS(#)) of the chitinolytic reaction on the soluble substrate. The catalytic activity has also been determined on insoluble chitin, which displays an effect of substrate saturation by chitinases. On both substrates, the thermodependence of the activity of the psychrophilic chitinases was lower than that observed with the mesophilic counterpart.

  1. Recent advances and potential applications of modulated differential scanning calorimetry (mDSC) in drug development. (United States)

    Knopp, Matthias Manne; Löbmann, Korbinian; Elder, David P; Rades, Thomas; Holm, René


    Differential scanning calorimetry (DSC) is frequently the thermal analysis technique of choice within preformulation and formulation sciences because of its ability to provide detailed information about both the physical and energetic properties of a substance and/or formulation. However, conventional DSC has shortcomings with respect to weak transitions and overlapping events, which could be solved by the use of the more sophisticated modulated DSC (mDSC). mDSC has multiple potential applications within the pharmaceutical field and the present review provides an up-to-date overview of these applications. It is aimed to serve as a broad introduction to newcomers, and also as a valuable reference for those already practising in the field. Complex mDSC was introduced more than two decades ago and has been an important tool for the quantification of amorphous materials and development of freeze-dried formulations. However, as discussed in the present review, a number of other potential applications could also be relevant for the pharmaceutical scientist.

  2. Ring-shaped Calorimetry Information for a Neural eGamma Identification with ATLAS Detector

    CERN Document Server

    Da Fonseca Pinto, Joao Victor; The ATLAS collaboration; Oliveira Damazio, Denis; Seixas, Jose


    \\title{Ring-shaped Calorimetry Information for a Neural e/$\\gamma$ Identification with ATLAS Detector} After the successful operation of the Large Hadron Collider resulting with the discovery of the Higgs boson, a new data-taking period (Run 2) has started. For the first time, collisions are produced with energies of 13 TeV in the centre of mass. It is foreseen the luminosity increase, reaching values as high as $10^{34}cm^{-2}s^{-1}$ yet in 2015. These changes in experimental conditions bring a proper environment for possible new physics key-findings. ATLAS is the largest LHC detector and was designed for general-purpose physics studies. Many potential physics channels have electrons or photons in their final states. For efficient studies on these channels precise measurement and identification of such particles is necessary. The identification task consists of disentangling those particles (signal) from collimated hadronic jets (background). Reported work concerns the identification process based on the cal...

  3. Single-crystal adsorption calorimetry and density functional theory of CO chemisorption on fcc Co{110}. (United States)

    Liao, Kristine; Fiorin, Vittorio; Gunn, David S D; Jenkins, Stephen J; King, David A


    Using single-crystal adsorption calorimetry (SCAC) and density functional theory (DFT), the interaction of carbon monoxide on fcc Co{110} is reported for the first time. The results indicate that adsorption is consistent with molecular chemisorption at all coverages. The initial heat of adsorption of 140 kJ mol(-1) is found in the range of heat values calorimetrically measured on other ferromagnetic metal surfaces, such as nickel and iron. DFT adsorption energies are in good agreement with the experimental results, and comparison between SCAC and DFT for CO on other ferromagnetic surfaces is made. The calculated dissociation barrier of 2.03 eV implies that dissociation at 300 K is unlikely even at the lowest coverage. At high coverages during the adsorption-desorption steady state regime, a pre-exponential factor for CO desorption of 1.2 × 10(17) s(-1) is found, implying a localised molecular adsorbed state prior to desorption in contrast to what we found with Ni surfaces. This result highlights the importance of the choice of the pre-exponential factor in evaluating the activation energy for desorption.

  4. Assessment of fluidity of different invasomes by electron spin resonance and differential scanning calorimetry. (United States)

    Dragicevic-Curic, Nina; Friedrich, Manfred; Petersen, Silvia; Scheglmann, Dietrich; Douroumis, Dennis; Plass, Winfried; Fahr, Alfred


    The aim of this study was to investigate the influence of membrane-softening components (terpenes/terpene mixtures, ethanol) on fluidity of phospholipid membranes in invasomes, which contain besides phosphatidylcholine and water, also ethanol and terpenes. Also mTHPC was incorporated into invasomes in order to study its molecular interaction with phospholipids in vesicular membranes. Fluidity of bilayers was investigated by electron spin resonance (ESR) using spin labels 5- and 16-doxyl stearic acid and by differential scanning calorimetry (DSC). Addition of 1% of a single terpene/terpene mixture led to significant fluidity increase around the C16 atom of phospholipid acyl chains comprising the vesicles. However, it was not possible to differentiate between the influences of single terpenes or terpene mixtures. Incorporation of mTHPC into the bilayer of vesicles decreased fluidity near the C16 atom of acyl chains, indicating its localization in the inner hydrophobic zone of bilayers. These results are in agreement with DSC measurements, which showed that terpenes increased fluidity of bilayers, while mTHPC decreased fluidity. Thus, invasomes represent vesicles with very high membrane fluidity. However, no direct correlation between fluidity of invasomes and their penetration enhancing ability was found, indicating that besides fluidity also other phenomena might be responsible for improved skin delivery of mTHPC.

  5. Misuse of thermodynamics in the interpretation of isothermal titration calorimetry data for ligand binding to proteins. (United States)

    Pethica, Brian A


    Isothermal titration calorimetry (ITC) has given a mass of data on the binding of small molecules to proteins and other biopolymers, with particular interest in drug binding to proteins chosen as therapeutic indicators. Interpretation of the enthalpy data usually follows an unsound protocol that uses thermodynamic relations in circumstances where they do not apply. Errors of interpretation include incomplete definitions of ligand binding and equilibrium constants and neglect of the non-ideality of the solutions under study, leading to unreliable estimates of standard free energies and entropies of binding. The mass of reported thermodynamic functions for ligand binding to proteins estimated from ITC enthalpies alone is consequently of uncertain thermodynamic significance and utility. ITC and related experiments to test the protocol assumptions are indicated. A thermodynamic procedure avoiding equilibrium constants or other reaction models and not requiring protein activities is given. The discussion draws attention to the fundamental but neglected relation between the thermodynamic activity and bioactivity of drugs and to the generally unknown thermodynamic status of ligand solutions, which for drugs relates directly to effective therapeutic dosimetry.

  6. Comparative study of isomalt and sucrose by means of continuous indirect calorimetry. (United States)

    Thiébaud, D; Jacot, E; Schmitz, H; Spengler, M; Felber, J P


    Isomalt (Palatinit) an equimolar mixture of alpha-D-glucopyranosido-1,6-sorbitol and alpha-D-glucopyranosido-1,6-mannitol, was compared to sucrose in a prospective double-blind controlled crossover study. The acute effects of oral ingestion of 30-g loads of isomalt or sucrose on plasma glucose, insulin, free fatty acids (FFA), lactic acid, and carbohydrate (CHO) and lipid oxidation were studied over six hours by means of continuous indirect calorimetry in ten healthy normal-weight subjects. Unlike sucrose, whose ingestion was followed by significant changes in plasma glucose, insulin, and lactic acid during the first 60 minutes of the test, no significant changes in these parameters were observed following the administration of isomalt. The increase in CHO oxidation occurring between 30 and 150 minutes was significantly lower (P less than 0.01) following isomalt than after sucrose. Conversely, the decrease in lipid oxidation was significantly less (P less than 0.01) after isomalt in comparison to sucrose. It is concluded that the rise in CHO oxidation and in plasma glucose and insulin levels is markedly reduced when sucrose is replaced by an equal weight of isomalt. In contrast to other sugar substitutes, no increase in plasma lactic acid was observed after isomalt administration.

  7. Subsite binding energies of an exo-polygalacturonase using isothermal titration calorimetry

    Energy Technology Data Exchange (ETDEWEB)

    Mertens, Jeffrey A., E-mail: [Bioenergy Research Unit, National Center for Agricultural Utilization Research, Agricultural Research Service, U.S. Department of Agriculture, 1815 North University Street, Peoria, IL 61604 (United States); Hector, Ronald E.; Bowman, Michael J. [Bioenergy Research Unit, National Center for Agricultural Utilization Research, Agricultural Research Service, U.S. Department of Agriculture, 1815 North University Street, Peoria, IL 61604 (United States)


    Highlights: Black-Right-Pointing-Pointer Thermodynamics of (GalpA){sub n} oligomers binding to an exo-polygalacturonase. Black-Right-Pointing-Pointer Energetics of binding (GalpA){sub n} were determined by ITC. Black-Right-Pointing-Pointer Thermodynamic parameters attributable to individual subsites were determined. - Abstract: Thermodynamic parameters for binding of a series of galacturonic acid oligomers to an exo-polygalacturonase, RPG16 from Rhizopus oryzae, were determined by isothermal titration calorimetry. Binding of oligomers varying in chain length from two to five galacturonic acid residues is an exothermic process that is enthalpically driven and results in extremely tight binding of the substrate to RPG16. Binding energies in combination with prior biochemical data suggests that RPG16 has the potential for five subsites, -1 to +4, with the greatest contribution to binding energies arising from subsite -1/+1. While the enthalpic contribution to binding decreases substantially for subsites +2 to +4, beneficial entropic effects occur in subsites +3 and +4 leading to increased total free energy as the length of oligomer increases. This information will be useful for additional studies in determining the binding contributions of specific amino acids with mutant enzymes.

  8. Spectroscopy, calorimetry and molecular simulation studies on the interaction of catalase with copper ion. (United States)

    Hao, Fang; Jing, Mingyang; Zhao, Xingchen; Liu, Rutao


    In this research, the binding mechanism of Cu(2+) to bovine liver catalase (BLC) was studied by fluorescence spectroscopy, ultraviolet-visible (UV-vis) absorption spectroscopy, circular dichroism (CD) spectroscopy, isothermal titration calorimetry (ITC) and molecular docking methods. The cellar experiment was firstly carried out to investigate the inhibition effect of catalase. During the fluorescence quenching study, after correcting the inner filter effect (IFE), the fluorescence of BLC was found to be quenched by Cu(2+). The quenching mechanism was determined by fluorescence lifetime measurement, and was confirmed to be the dynamic mode. The secondary structure content of BLC was changed by the addition of Cu(2+), as revealed by UV-vis absorption and CD spectra, which further induces the decrease in BLC activity. Molecular simulation study indicates that Cu(2+) is located between two β-sheets and two random coils of BLC near to the heme group, and interacts with His 74 and Ser 113 residues near a hydrophilic area. The decrease of α-helix and the binding of His 74 are considered to be the major reason for the inhibition of BLC activity caused by Cu(2+). The ITC results indicate that the binding stoichiometry of Cu(2+) to catalase is 11.4. Moreover, the binding of Cu(2+) to BLC destroyed H-bonds, which was confirmed by the CD result.

  9. Prospects for true calorimetry on Kerr black holes in core-collapse supernovae and mergers

    CERN Document Server

    van Putten, Maurice H P M; Tagoshi, Hideyuki; Tatsumi, Daisuke; Masa-Katsu, Fujimoto; Della Valle, Massimo


    Observational evidence for black hole spin down has been found in the normalized light curves of long GRBs in the BATSE catalogue. Over the duration $T_{90}$ of the burst, matter swept up by the central black hole is susceptible to non-axisymmetries producing gravitational radiation with a negative chirp. A time sliced matched filtering method is introduced to capture phase-coherence on intermediate timescales, $\\tau$, here tested by injection of templates into experimental strain noise, $h_n(t)$. For TAMA 300, $h_n(f)\\simeq 10^{-21}$ Hz$^{-\\frac{1}{2}}$ at $f=1$ kHz gives a sensitivity distance for a reasonably accurate extraction of the trajectory in the time frequency domain of about $D\\simeq 0.07-0.10$ Mpc for spin fown of black holes of mass $M=10-12M_\\odot$ with $\\tau=1$ s. Extrapolation to advanced detectors implies $D\\simeq 35-50$ Mpc for $h_n(f)\\simeq 2\\times 10^{-24}$ Hz$^{-\\frac{1}{2}}$ around 1 kHz, which will open a new window to rigorous calorimetry on Kerr black holes.

  10. Isothermal calorimetry: a predictive tool to model drug-propellant interactions in pressurized metered dose systems. (United States)

    Ooi, Jesslynn; Gaisford, Simon; Boyd, Ben J; Young, Paul M; Traini, Daniela


    The purpose of this work was to evaluate gas perfusion isothermal calorimetry (ITC) as a method to characterize the physicochemical changes of active pharmaceutical ingredients (APIs) intended to be formulated in pressurized metered dose inhalers (pMDIs) after exposure to a model propellant. Spray dried samples of beclomethasone dipropionate (BDP) and salbutamol sulphate (SS) were exposed to controlled quantities of 2H,3H-decafluoropentane (HPFP) to determine whether ITC could be used as a suitable analytical method for gathering data on the behavioural properties of the powders in real time. The crystallization kinetics of BDP and the physiochemical properties of SS were successfully characterized using ITC and supported by a variety of other analytical techniques. Correlations between real and model propellant systems were also established using hydrofluoroalkane (HFA-227) propellant. In summary, ITC was found to be suitable for gathering data on the crystallization kinetics of BDP and SS. In a wider context, this work will have implications on the use of ITC for stability testing of APIs in HFA-based pMDIs.

  11. Magnetocaloric effect in Mn2-pyrazole-[Nb(CN)8] molecular magnet by relaxation calorimetry (United States)

    Pełka, R.; Gajewski, M.; Miyazaki, Y.; Yamashita, S.; Nakazawa, Y.; Fitta, M.; Pinkowicz, D.; Sieklucka, B.


    Magnetocaloric effect in {[Mn(pyrazole)4]2[Nb(CN)8]·4 H2O}n molecular magnet is reported. It crystallizes in tetragonal I41/a space group. The compound exhibits a phase transition to a long range magnetically ordered state at TN ≈ 22.8 K. Temperature dependences of the magnetic entropy change ΔSM as well as the adiabatic temperature change ΔTad due to applied field change μ0 ΔH in the range of 0.1-9 T have been inferred from the relaxation calorimetry measurements. A systematic approximate approach has been used to determine the lattice contribution to the heat capacity. The maximum value of ΔSM for μ0 ΔH = 5 T is 6.83 J mol-1 K-1 (6.65 J kg-1 K-1) at 24.3 K. The corresponding maximum value of ΔTad is 1.4 K at 23.8 K. The temperature dependence of the exponent n characterizing the field dependence of ΔSM has been estimated. It attains the value of 0.64 at the transition temperature, which is consistent with the 3D Heisenberg universality class. A hitherto unobserved two-peak structure has been revealed in the temperature dependence of ΔTad.

  12. PREFACE: XVth International Conference on Calorimetry in High Energy Physics (CALOR2012) (United States)

    Akchurin, Nural


    The XVth International Conference on Calorimetry in High Energy Physics, CALOR2012, was held in Santa Fe, New Mexico from 4-8 June 2012. The series of conferences on calorimetry started in 1990 at Fermilab, and they have been the premier event for calorimeter aficionados, a trend that CALOR2012 upheld. This year, several presentations focused on the status of the major calorimeter systems, especially at the LHC. Discussions on new and developing techniques in calorimetry took a full day. Excellent updates on uses of calorimeters or about ideas that are deeply rooted in particle physics calorimetry in astrophysics and neutrino physics were followed by talks on algorithms and special triggers that rely on calorimeters. Finally, discussions of promising current developments and ongoing R&D work for future calorimeters capped the conference. The field of calorimetry is alive and well, as evidenced by the more than 100 attendees and the excellent quality of over 80 presentations. You will find the written contributions in this volume. The presentations can be found at The first day of the conference was dedicated to the LHC. In two invited talks, Guillaume Unal (CERN) and Tommaso Tabarelli de Fatis (Universita' & INFN Milano Bicocca) discussed the critical role electromagnetic calorimeters play in the hunt for the Standard Model Higgs boson in ATLAS and CMS, respectively. The enhanced sensitivity for light Higgs in the two-gamma decay channel renders electromagnetic calorimeters indispensible. Much of the higher mass region was already excluded for the SM Higgs by the time of this conference, and after less than a month, on 4 July, CERN announced the discovery of a new boson at 125 GeV, a particle that seems consistent with the Higgs particle so far. Once again, without the electromagnetic calorimeters, this would not have been possible. Professor Geoffrey West from the Santa Fe Institute gave the keynote address. His talk, 'Universal Scaling Laws

  13. Breath test measurements in combination with indirect calorimetry for estimation of 13C-leucine oxidation in mink (Mustela vison)

    DEFF Research Database (Denmark)

    Tauson, Anne-Helene; Ali, Abdalla; Kanska, Katarzyna


    Gas exchange measurements by means of indirect calorimetry can be used to calculate quantitative substrate oxidation. The results represents average net oxidation values (substrate disappearance rate), but they cannot describe the dynamics of the oxidation processes. Breath test measurements...... to feeding and fasting. Twelve 1-year-old male mink (Mustela vison) were measured in each five consecutive periods by means of indirect calorimetry and simultaneous breath test. In Periods 1, 3 and 5, each lasting 3 days, the animals were fed ad libitum and Periods 2 and 4 were fasting periods, each of 48 h....... In Periods 1 and 5 all animals were fed a diet with a high quality fish meal (FISH; n=12), while in Period 3 half of the animals received the FISH diet (n=6) and the other half a diet with soy protein concentrate (SOY; n=6) as main protein source. An intraperitoneal injection of 1-13C-leucine was given...

  14. Comparison of steps and energy expenditure assessment in adults of Fitbit Tracker and Ultra to the Actical and indirect calorimetry. (United States)

    Adam Noah, J; Spierer, David K; Gu, Jialu; Bronner, Shaw


    Epidemic levels of inactivity are associated with chronic diseases and rising healthcare costs. To address this, accelerometers have been used to track levels of activity. The Fitbit and Fitbit Ultra are some of the newest commercially available accelerometers. The purpose of this study was to determine the reliability and validity of the Fitbit and Fitbit Ultra. Twenty-three subjects were fitted with two Fitbit and Fitbit Ultra accelerometers, two industry-standard accelerometers and an indirect calorimetry device. Subjects participated in 6-min bouts of treadmill walking, jogging and stair stepping. Results indicate the Fitbit and Fitbit Ultra are reliable and valid for activity monitoring (step counts) and determining energy expenditure while walking and jogging without an incline. The Fitbit and standard accelerometers under-estimated energy expenditure compared to indirect calorimetry for inclined activities. These data suggest the Fitbit and Fitbit Ultra are reliable and valid for monitoring over-ground energy expenditure.

  15. Kinetics of solid-gas reactions characterized by scanning AC nano-calorimetry with application to Zr oxidation (United States)

    Xiao, Kechao; Lee, Dongwoo; Vlassak, Joost J.


    Scanning AC nano-calorimetry is a recently developed experimental technique capable of measuring the heat capacity of thin-film samples of a material over a wide range of temperatures and heating rates. Here, we describe how this technique can be used to study solid-gas phase reactions by measuring the change in heat capacity of a sample during reaction. We apply this approach to evaluate the oxidation kinetics of thin-film samples of zirconium in air. The results confirm parabolic oxidation kinetics with an activation energy of 0.59 ± 0.03 eV. The nano-calorimetry measurements were performed using a device that contains an array of micromachined nano-calorimeter sensors in an architecture designed for combinatorial studies. We demonstrate that the oxidation kinetics can be quantified using a single sample, thus enabling high-throughput mapping of the composition-dependence of the reaction rate.

  16. Spin density wave (SDW) transition in Ru doped BaFeAs{sub 2} investigated by AC steady state calorimetry

    Energy Technology Data Exchange (ETDEWEB)

    Vinod, K., E-mail:; Sharma, Shilpam; Sundar, C. S.; Bharathi, A. [Low Temperature Studies Section, Condensed Matter Physics Division, Materials Science Group, Indira Gandhi Centre for Atomic Research (IGCAR), Kalpakkam-603102 (India)


    Heat capacity measurements were done on sub-micron sized BaFe{sub 2−x}Ru{sub x}As{sub 2} single crystals using thin film membrane based the AC steady state calorimetry technique. Noticeable thermal hysteresis is observed in the heat capacity of the BaFe{sub 2−x}Ru{sub x}As{sub 2} during cooling and warming cycles, indicating first order nature of the SDW transition.

  17. Calorimetry is not color-blind.Molecular insights on association processes in surfactant-polymer mixtures derived from calorimetric experiments

    Institute of Scientific and Technical Information of China (English)

    LOH Watson; BRINATTI Cesar


    This comment will review and discuss recent results obtained with the use of calorimetry in assessing molecular information from complex phenomena such as association in surfactant/polymer mixtures.These examples were selected to support the view that it is possible to ally the great sensitivity of modern calorimeters with carefully planned experiments and,sometimes,ancillary techniques in order to derive detailed information on molecular interactions.

  18. Label-Free Determination of the Dissociation Constant of Small Molecule-Aptamer Interaction by Isothermal Titration Calorimetry. (United States)

    Vogel, Marc; Suess, Beatrix


    Isothermal titration calorimetry (ITC) is a powerful label-free technique to determine the binding constant as well as thermodynamic parameters of a binding reaction and is therefore well suited for the analysis of small molecule-RNA aptamer interaction. We will introduce you to the method and present a protocol for sample preparation and the calorimetric measurement. A detailed note section will point out useful tips and pitfalls.

  19. On-line reaction monitoring of lithiation of halogen substituted acetanilides via in situ calorimetry, ATR spectroscopy, and endoscopy. (United States)

    Godany, Tamas A; Neuhold, Yorck-Michael; Hungerbühler, Konrad


    Lithiation of N-(4-chlorophenyl)-pivalamide (NCP) and two additional substituted acetanilides: 4-fluoroacetanilide (4-F) and 4-chloroacetanilide (4-Cl) has been monitored by means of calorimetry, on-line ATR-IR and UV/vis spectroscopy and endoscopy. The combined on-line monitoring revealed the differences between the reaction paths of the chosen substrates. Thus the product structure and the reaction times for the individual reaction steps can be determined in situ.

  20. Evaluation of peritoneal tissue by means of differential scanning calorimetry (DSC

    Directory of Open Access Journals (Sweden)

    Łukasz Pietrzyk


    Full Text Available Abdominal surgeries alter the integrity of the peritoneal layer and cause imbalances among immunological, inflammatory and angiogenic mechanisms within the tissue. During laparoscopic procedures a protective function of the peritoneal layer can be disturbed by the gas used to create a pneumoperitoneum. The aim of this study was to characterize peritoneal tissue by means of differential scanning calorimetry (DSC as a reference for future investigations on the influence of surgical procedures on the physicochemical state of the peritoneum. Thirty-seven patients participated in the study. Patients were divided into three groups according to the type of surgery: group H — patients who underwent hernia repair; group Ch — patients who underwent laparoscopic cholecystectomy; and group C — patients operated due to rectal cancer. It was observed that onset temperature (To, denaturation temperature (Tm and change of enthalpy (ΔH during thermal denaturation of peritoneal collagen in were significantly different for these three groups of patients. The mean values of onset temperature (To and denaturation temperature (Tm in group H were significantly lower, while DH in this group was significantly higher than in the two other groups (Ch and C. This preliminary study does not answer whether the differences in collagen denaturation found in peritoneal tissue from different groups of patients resulted from a different inherent state of the tissue, or from surgical procedures. However, the results suggest that DSC is an appropriate method to study subtle changes in the physicochemical condition of the peritoneum using small samples obtained during surgical procedures. (Folia Histochemica et Cytobiologica 2011; Vol. 49, No. 4, pp. 700–705

  1. Isothermal titration calorimetry uncovers substrate promiscuity of bicupin oxalate oxidase from Ceriporiopsis subvermispora

    Directory of Open Access Journals (Sweden)

    Hassan Rana


    Full Text Available Isothermal titration calorimetry (ITC may be used to determine the kinetic parameters of enzyme-catalyzed reactions when neither products nor reactants are spectrophotometrically visible and when the reaction products are unknown. We report here the use of the multiple injection method of ITC to characterize the catalytic properties of oxalate oxidase (OxOx from Ceriporiopsis subvermispora (CsOxOx, a manganese dependent enzyme that catalyzes the oxygen-dependent oxidation of oxalate to carbon dioxide in a reaction coupled with the formation of hydrogen peroxide. CsOxOx is the first bicupin enzyme identified that catalyzes this reaction. The multiple injection ITC method of measuring OxOx activity involves continuous, real-time detection of the amount of heat generated (dQ during catalysis, which is equal to the number of moles of product produced times the enthalpy of the reaction (ΔHapp. Steady-state kinetic constants using oxalate as the substrate determined by multiple injection ITC are comparable to those obtained by a continuous spectrophotometric assay in which H2O2 production is coupled to the horseradish peroxidase-catalyzed oxidation of 2,2′-azinobis-(3-ethylbenzthiazoline-6-sulfonic acid and by membrane inlet mass spectrometry. Additionally, we used multiple injection ITC to identify mesoxalate as a substrate for the CsOxOx-catalyzed reaction, with a kinetic parameters comparable to that of oxalate, and to identify a number of small molecule carboxylic acid compounds that also serve as substrates for the enzyme.

  2. Applications of differential scanning calorimetry to the study of thermal energy storage

    Energy Technology Data Exchange (ETDEWEB)

    Cantor, S.


    Differential scanning calorimetry (DSC) is a versatile tool for investigating the behavior of materials that store energy by melting or by undergoing solid-state transitions. Heating scans measure the enthalpy that can be stored and cooling scans yield the enthalpy that may be recovered from the material. Exotherms also provide information about supercooling. The automatic and rapid thermal cycling features of the instrument system can be used to greatly accelerate thermal decomposition that may arise from the daily duty cycle of the storage medium. These chemical reactions as well as those with containment or with substances added to improve performance can be detected from changes in the thermal spectra. In this study, DSC methods were applied to sodium sulfate decahydrate, paraffin wax, urea, and phthalimide. For Na/sub 2/SO/sub 4/.10H/sub 2/O, DSC measurements showed a decrease in heat of fusion with thermal cycling and, also, considerable supercooling; with added Na/sub 2/B/sub 4/O/sub 7/.10H/sub 2/O (borax), supercooling was greatly lessened but not entirely eliminated. Paraffin wax did not supercool nor were there any indications that thermal cycling or contact with aluminum degraded its thermal performance. Urea, when thermally cycled, decreased in melting point and in heat of fusion; this compound also supercooled about 50/sup 0/ in DSC experiments. Phthalimide, C/sub 6/H/sub 4/(CO)/sub 2/NH, did not decompose when thermally cycled through its melting point, but it did exhibit marked supercooling. However, lesser supercooling of urea and phthalimide in test-tube scale experiments suggests that supercooling derived from DSC should be applied with caution. For phthalimide, the enthalpy of fusion, determined in this study, equalled 48.1 cal/g.

  3. Approximate time to steady state resting energy expenditure using indirect calorimetry in young, healthy adults

    Directory of Open Access Journals (Sweden)

    Collin Popp


    Full Text Available Indirect calorimetry (IC measurements to estimate resting energy expenditure (REE necessitate a stable measurement period, or steady state (SS. There is limited evidence when assessing the time to reach SS in young, healthy adults. The aims of this prospective study are to determine the approximate time to necessary reach SS using open-circuit IC and to establish the appropriate duration of SS needed to estimate REE. One hundred young, healthy participants (54 males and 46 females; age = 20.6 ± 2.1 years; body weight = 73.6 ± 16.3 kg; height 172.5 ± 9.3 cm; BMI = 24.5 ± 3.8 kg/m2 completed IC measurement for approximately 30-minutes while the volume of oxygen (VO2 and volume of carbon dioxide (VCO2 were collected. SS was defined by variations in the VO2 and VCO2 of ≤10% coefficient of variation (%CV over a period of 5- consecutive minutes. The 30-minute IC measurement was divided into six 5-minute segments, S1, S2, S3, S4, S5 and S6. The results show that SS was achieved during S2 (%CV = 6.81 ± 3.2%, and the %CV continued to met the SS criteria for the duration of the IC measurement (S3= 8.07 ± 4.4%; S4 = 7.93 ± 3.7%; S5 = 7.75 ± 4.1%; S6 = 8.60 ± 4.6%. The current study found that in a population of young, healthy adults the duration of the IC measurement period could be a minimum of 10 minutes. The first 5-minute segment was discarded, while SS occurred by the second 5-minute segment.

  4. Resting energy expenditure of morbidly obese patients using indirect calorimetry: a systematic review. (United States)

    Kee, A-L; Isenring, E; Hickman, I; Vivanti, A


    The increasing proportion of acutely ill hospital patient admissions presenting with a morbidly obese body mass index (BMI ≥ 40 kg m(-2) ) as a comorbidity is an emerging clinical concern. Suboptimal food intake and malnutrition is prevalent in the acute care hospital setting. The energy requirements necessary to prevent malnutrition in acutely ill patients with morbid obesity remains unclear. The aim of this systematic review was to identify studies in the literature that have used indirect calorimetry to measure the resting energy expenditure of patients with morbid obesity to establish their minimum energy requirements and the implications for optimal feeding practices in acutely ill hospitalized patients. A total of 20 studies from PubMed, Cochrane Library and Embase met the inclusion criteria and were reviewed. All articles were graded using the Australian National Health and Medical Research Council levels of evidence and given a quality rating using the American Dietetic Association recommendations. Studies were categorized according to the mean BMI of its subjects. The most commonly measured resting energy expenditures for morbidly obese patients are between 2,000 and 3,000 kcal d(-1) (8,400-12,600 kJ d(-1) ). Activity and injury factors of acutely ill morbidly obese patients could result in significantly greater energy requirements for this patient group and are unlikely to be met by standard hospital menus. Establishing the minimum energy requirements for this population group will help inform adequate and accurate energy provision in the acute setting. Outcomes of underfeeding and overfeeding in morbidly obese patients warrant further research.

  5. Assessing Coupled Protein Folding and Binding Through Temperature-Dependent Isothermal Titration Calorimetry. (United States)

    Sahu, Debashish; Bastidas, Monique; Lawrence, Chad W; Noid, William G; Showalter, Scott A


    Broad interest in the thermodynamic driving forces of coupled macromolecular folding and binding is motivated by the prevalence of disorder-to-order transitions observed when intrinsically disordered proteins (IDPs) bind to their partners. Isothermal titration calorimetry (ITC) is one of the few methods available for completely evaluating the thermodynamic parameters describing a protein-ligand binding event. Significantly, when the effective ΔH° for the coupled folding and binding process is determined by ITC in a temperature series, the constant-pressure heat capacity change (ΔCp) associated with these coupled equilibria is experimentally accessible, offering a unique opportunity to investigate the driving forces behind them. Notably, each of these molecular-scale events is often accompanied by strongly temperature-dependent enthalpy changes, even over the narrow temperature range experimentally accessible for biomolecules, making single temperature determinations of ΔH° less informative than typically assumed. Here, we will document the procedures we have adopted in our laboratory for designing, executing, and globally analyzing temperature-dependent ITC studies of coupled folding and binding in IDP interactions. As a biologically significant example, our recent evaluation of temperature-dependent interactions between the disordered tail of FCP1 and the winged-helix domain from Rap74 will be presented. Emphasis will be placed on the use of publically available analysis programs written in MATLAB that facilitate quantification of the thermodynamic forces governing IDP interactions. Although motivated from the perspective of IDPs, the experimental design principles and data fitting procedures presented here are general to the study of most noncooperative ligand binding equilibria.

  6. Binding of Cu(II) ions to peptides studied by fluorescence spectroscopy and isothermal titration calorimetry. (United States)

    Makowska, Joanna; Żamojć, Krzysztof; Wyrzykowski, Dariusz; Uber, Dorota; Wierzbicka, Małgorzata; Wiczk, Wiesław; Chmurzyński, Lech


    Steady-state and time-resolved fluorescence quenching measurements supported by Isothermal Titration Calorimetry (ITC) were used to study the interactions of Cu(2+) with four peptides. Two of them were taken from the N-terminal part of the FBP28 protein (formin binding protein) WW domain: Tyr-Lys-Thr-Ala-Asp-Gly-Lys-Thr-Tyr-NH2 (D9) and its mutant Tyr-Lys-Thr-Ala-Asn-Gly-Lys-Thr-Tyr-NH2 (D9_M) as well as two mutated peptides from the B3 domain of the immunoglobulin binding protein G derived from Streptococcus: Asp-Val-Ala-Thr-Tyr-Thr-NH2 (J1) and Glu-Val-Ala-Thr-Tyr-Thr-NH2 (J2). The measurements were carried out at 298.15K in 20mM 2-(N-morpholino)ethanesulfonic acid (MES) buffer solution with a pH of 6. The fluorescence of all peptides was quenched by Cu(2+) ions. The stoichiometry, conditional stability constants and thermodynamic parameters for the interactions of the Cu(2+) ions with D9 and D9_M were determined from the calorimetric data. The values of the conditional stability constants were additionally determined from fluorescence quenching measurements and compared with those obtained from calorimetric studies. There was a good correlation between data obtained from the two techniques. On the other hand, the studies revealed that J1 and J2 do not exhibit an affinity towards metal ions. The obtained results prove that fluorescence quenching experiments may be successfully used in order to determine stability constants of complexes with fluorescent ligands. Finally, based on the obtained results, the coordinating properties of the peptides towards the Cu(2+) ions are discussed.

  7. Practical utility and reliability of whole-room calorimetry in young children. (United States)

    Janssen, Xanne; Cliff, Dylan; Okely, Anthony D; Jones, Rachel A; Batterham, Marijka; Ekelund, Ulf; Brage, Søren; Reilly, John J


    The use of whole-room calorimetry (WRC) in young children can increase our understanding of children's energy balance. However, studies using WRC in young children are rare due to concerns about its feasibility. To assess the feasibility of WRC in young children, forty children, aged 4–6 years, were asked to follow a graded activity protocol while in a WRC. In addition, six children participated in two additional resting protocols to examine the effect of diet-induced thermogenesis on resting energy expenditure (REE) measures and the reliability of REE measurement. Refusals to participate and data loss were quantified as measures of practical utility, and REE measured after an overnight fast and after a 90-min fast were compared. In addition, both were compared to predicted BMR values using the Schofield equation. Our results showed that thirty (78·9 %) participants had acceptable data for all intensities of the activity protocol. The REE values measured after a 90-min fast (5·07 (SD 1·04) MJ/d) and an overnight fast (4·73 (SD 0·61) MJ/d) were not significantly different from each other (P= 0·472). However, both REE after an overnight fast and a 90-min fast were significantly higher than predicted BMR (3·96 (SD 0·18) MJ/d) using the Schofield equation (P= 0·024 and 0·042, respectively). We conclude that, with a developmentally sensitive approach, WRC is feasible and can be standardised adequately even in 4- to 6-year-old children. In addition, the effect of a small standardised breakfast, approximately 90 min before REE measurements, is likely to be small.

  8. Phase behavior in the system tetrahydrofuran-water-ammonia from calorimetry and Raman spectroscopy (United States)

    Munoz-Iglesias, Victoria; Vu, Tuan; Choukroun, Mathieu; Hodyss, Robert; Smythe, William; Sotin, Christophe


    From geochemical models and Cassini-Huygens mission data it can be postulated that the icy crust of Titan is composed by water ice, clathrate hydrates and ammonia hydrates. When the shell evolves thermically, the first minerals in dissociating are the ammonia hydrates. Ammonia is a powerful antifreeze, promoting the drop of the equilibrium curves of both water ice and clathrates to values as low as 170 K and 203 K respectively. Calorimetry, using a Setaram BT 2.15 Calvet calorimeter, has allowed to identify the different phases formed in the system THF-H2O-NH3 when the molar ratio H2O:THF is 1:X 17, which corresponds with the THF-clathrate stoichiometric ratio, and at NH3 concentrations up to 30 wt%. When X 17, the H2O is in excess; the formation of ammonia hydrates, water ice and THF-clathrate is observed. Since under this condition, all available THF is trapped in the clathrate, no THF-NH3 phase is observed. In all the scenarios, the release of NH3 (from the melting of THF-NH3 solid or ammonia hydrates) promotes partial dissociation of THF clathrates, which start at much lower temperature the equilibrium dissociation of the clathrates. This research is supported by an appointment to the NASA Postdoctoral Program at the Jet Propulsion Laboratory, California Institute of Technology, administered by Universities Space Research Association (USRA) through a contract with NASA. Support from the NASA Outer Planets Research program and government sponsorship acknowledged.

  9. Differential scanning calorimetry study of glass transition in frozen starch gels. (United States)

    Tananuwong, Kanitha; Reid, David S


    The effects of initial water content, maximum heating temperature, amylopectin crystallinity type, and annealing on the glass transition of starch gels were studied by differential scanning calorimetry (DSC). The glass transition temperatures of the frozen gels measured as the onset (T(g,onset)) or midpoint temperature (T(g,midpoint)), heat capacity change during the glass transition (deltaC(p)), unfrozen water of starch gels, and additional unfrozen water (AUW) arising from gelatinization were reported. The results show that T(g,onset) and T(g,midpoint) of the partially gelatinized gels are independent of the initial water content, while both of the T(g) values of the fully gelatinized gel increase as the initial water content increases. These observations might result from the difference in the level of structural disruption associated with different heating conditions, resulting in different gel structures as well as different concentrations of the sub-T(g) unfrozen matrix. The amylopectin crystallinity type does not greatly affect T(g,onset) and T(g,midpoint) of the gels. Annealing at a temperature near T(g,onset) increases both T(g,onset) and T(g,midpoint) of the gels, possibly due to an increase in the extent of the freeze concentration as evidenced by a decrease in AUW. Annealing results in an increase in the deltaC(p) value of the gels, presumably due to structural relaxation. A devitrification exotherm may be related to AUW. The annealing process decreases AUW, thus also decreasing the size of the exotherm.

  10. Digital holographic interferometry: A novel optical calorimetry technique for radiation dosimetry

    Energy Technology Data Exchange (ETDEWEB)

    Cavan, Alicia, E-mail: [Department of Physics and Astronomy, University of Canterbury, Private Bag 4800, Christchurch 8140, New Zealand and Christchurch Hospital, Private Bag 4710, Christchurch 8140 (New Zealand); Meyer, Juergen, E-mail: [Department of Radiation Oncology, University of Washington, 1959 Northeast Pacific Street, Box 356043, Seattle, Washington 98195 (United States)


    Purpose: To develop and demonstrate the proof-of-principle of a novel optical calorimetry method to determine radiation absorbed dose in a transparent medium. Methods: The calorimetric property of water is measured during irradiation by means of an interferometer, which detects temperature-induced changes in the refractive index that can be mathematically related to absorbed dose. The proposed method uses a technique called digital holographic interferometry (DHI), which comprises an optical laser interferometer setup and consecutive physical reconstruction of the recorded wave fronts by means of the Fresnel transform. This paper describes the conceptual framework and provides the mathematical basis for DHI dosimetry. Dose distributions from a high dose rate Brachytherapy source were measured by a prototype optical setup to demonstrate the feasibility of the approach. Results: The developed DHI dosimeter successfully determined absorbed dose distributions in water in the region adjacent to a high dose rate Brachytherapy source. A temperature change of 0.0381 K across a distance of 6.8 mm near the source was measured, corresponding to a dose of 159.3 Gy. The standard deviation in a typical measurement set was ±3.45 Gy (corresponding to an uncertainty in the temperature value of ±8.3 × 10{sup −4} K). The relative dose fall off was in agreement with treatment planning system modeled data. Conclusions: First results with a prototype optical setup and a Brachytherapy source demonstrate the proof-of-principle of the approach. The prototype achieves high spatial resolution of approximately 3 × 10{sup −5} m. The general approach is fundamentally independent of the radiation type and energy. The sensitivity range determined indicates that the method is predominantly suitable for high dose rate applications. Further work is required to determine absolute dose in all three dimensions.

  11. Volumetric characterization of ester- and ether-linked lipid bilayers by pressure perturbation calorimetry and densitometry. (United States)

    Tamai, Nobutake; Nambu, Yuko; Tanaka, Saeko; Goto, Masaki; Matsuki, Hitoshi; Kaneshina, Shoji


    We investigated the thermotropic volume behavior of dimyristoylphosphatidylcholine (DMPC), dipalmitoylphosphatidylcholine (DPPC) and dihexadecylphosphatidylcholine (DHPC) membranes using pressure perturbation calorimetry (PPC) and densitometry. The ln φ(2) vs temperature curves (φ(2): apparent molar volume of phospholipid) obtained from the PPC data using an analysis method that we developed agreed with the results from the density measurements for these lipids within the relative difference of about 0.62%. From those curves, the volume changes with the main transition were estimated at 18.0±0.49, 23.5±2.33 and 23.0±0.33 cm(3) mol(-1) for DMPC, DPPC and DHPC, respectively. For DPPC and DMPC, the average volume per methylene group of the hydrocarbon chains v(CH2) calculated by referring to the procedure by Nagle and Wilkinson was consistent with the previous result, which indicates that the DPPC bilayer in the gel state has denser hydrophobic bilayer core than the DMPC bilayer. For DHPC, the volume of the headgroup region v(H) was calculated to be 244 Å(3) by assuming that v(CH2) of DHPC equals that of DPPC above 45°C. This value was comparable to that of DPPC when the volume of the carbonyl groups was considered, which may signify that there is no significant conformational difference in the polar headgroups of both phospholipids. However, it was suggested from the consideration on v(H) of DHPC at 20°C that expansion of the headgroup region should occur as the interdigitated structure is formed, which means some conformational change of the headgroup region is induced by the interdigitation.

  12. Characterization of parvalbumin and polcalcin divalent ion binding by isothermal titration calorimetry. (United States)

    Henzl, Michael T


    The elucidation of structure-affinity relationships in EF-hand proteins requires a reliable assay of divalent ion affinity. In principle, isothermal titration calorimetry (ITC) should be capable of furnishing estimates for Ca2+- and Mg2+-binding constants in these systems. And because the method yields the binding enthalpy directly, ITC can provide a more detailed view of binding energetics than methods that rely on 45Ca2+ or fluorescent indicators. For several reasons, however, it is generally not possible to extract reliable binding parameters from single ITC experiments. Ca2+ affinity is often too high, and Mg2+ affinity is invariably too low. Moreover, least-squares minimization of multisite systems may not afford a unique fit because of strong parameter correlations. This chapter outlines a strategy for analyzing two-site systems that overcomes these obstacles. The method--which involves simultaneous, or global, least-squares analysis of direct and competitive ITC data--yields binding parameters for both Ca2+ and Mg2+. Application of the method is demonstrated for two systems. The S55D/E59D variant of rat alpha-parvalbumin, noteworthy for its elevated metal ion affinity, binds divalent ions noncooperatively and is amenable to analysis using an independent two-site model. On the other hand, Phl p 7, a pollen-specific EF-hand protein from timothy grass, binds Ca2+ with positive cooperativity. Divalent ion-binding data for the protein must be analyzed using a two-site Adair model.

  13. Quantifying high-affinity binding of hydrophobic ligands by isothermal titration calorimetry. (United States)

    Krainer, Georg; Broecker, Jana; Vargas, Carolyn; Fanghänel, Jörg; Keller, Sandro


    A fast and reliable quantification of the binding thermodynamics of hydrophobic high-affinity ligands employing a new calorimetric competition experiment is described. Although isothermal titration calorimetry is the method of choice for a quantitative characterization of intermolecular interactions in solution, a reliable determination of a dissociation constant (K(D)) is typically limited to the range 100 μM > K(D) > 1 nM. Interactions displaying higher or lower K(D) values can be assessed indirectly, provided that a suitable competing ligand is available whose K(D) falls within the directly accessible affinity window. This established displacement assay, however, requires the high-affinity ligand to be soluble at high concentrations in aqueous buffer and, consequently, poses serious problems in the study of protein binding involving small-molecule ligands dissolved in organic solvents--a familiar case in many drug-discovery projects relying on compound libraries. The calorimetric competition assay introduced here overcomes this limitation, thus allowing for a detailed thermodynamic description of high-affinity receptor-ligand interactions involving poorly water-soluble compounds. Based on a single titration of receptor into a dilute mixture of the two competing ligands, this competition assay provides accurate and precise values for the dissociation constants and binding enthalpies of both high- and moderate-affinity ligands. We discuss the theoretical background underlying the approach, demonstrate its practical application to metal ion chelation and high-affinity protein-inhibitor interactions, and explore its potential and limitations with the aid of simulations and statistical analyses.

  14. Application of calorimetry to microbial biodegradation studies of agrochemicals in oxisols. (United States)

    Critter, S A; Airoldi, C


    Calorimetry was used to monitor the inhibitory effect caused by the bipyridynium diquaternary salts paraquat, diquat, and phosphamidon on microbial activity in a Red Latosol soil (Oxisol). The thermal effect was recorded on samples composed of 1.50 g of soil, 6.0 mg of glucose, 6.0 mg of ammonium sulfate, and different masses of an inhibitor ranging from zero to 8.00 mg, under a controlled moisture content of 35%. Thermal effects of each pollutant on the degradation curves of glucose in the soil were compared. Increasing amounts of the inhibitor caused a decrease in the thermal effect from -2234 to -1987 kJ mol(-1) for paraquat, -1670 to -1306 kJ mol(-1) for diquat, and -2239 to -589 kJ mol(-1) for phosphamidon. The last xenobiotic agent caused a significant inhibitory effect on the microbial activity of the soil. The results of relative efficiency, eta = deltaH/deltaH', referring to the enthalpic value with (deltaH) and without (deltaH') agrochemical in the soil, exhibited a significant correlation. From this correlation obtained for the ranges 2.00 to 8.00, 1.30 to 8.00, and 1.20 to 5.80 mg of the agrochemicals paraquat, diquat, and phosphamidon, respectively, the following eta values were calculated: 0.993 to 0.894, 0.668 to 0.522, and 0.896 to 0.236, respectively, during the degradation of glucose in the soil. The largest relative efficiency for paraquat implies that this agrochemical can be metabolized by microbial activity.

  15. Following mechanical activation of salbutamol sulphate during ball-milling with isothermal calorimetry. (United States)

    Gaisford, Simon; Dennison, Mansa; Tawfik, Mahmoud; Jones, Matthew D


    Formulation of actives for pulmonary delivery with dry powder inhaler devices frequently requires a particle size reduction step. The high-energy forces imparted to a material during milling, as well as reducing particle size, can cause a significant change in physicochemical properties, in particular mechanical activation of the surface (manifested as generation of amorphous regions) which can affect formulated product performance. It is not clear whether particle size reduction occurs prior to, or concomitantly with, generation of amorphous content. In this study the formation of amorphous content with time in crystalline salbutamol sulphate was quantified with isothermal gas perfusion calorimetry as the sample was ball-milled. The data showed that the most particle size reduction occurred initially (d(0.5) dropping from 12.83+/-0.4 to 4.2+/-0.4 within 5 min). During this time period, no detectable amorphous content was observed. Between 5 and 15 min milling time the particle size distribution remained relatively constant but the amorphous content increased non-linearly with time. After 20 min milling time the particle size increased slightly. The data suggest that particle size reduction occurs initially upon application of a force to the crystal. Once maximum particle size reduction has occurred the crystal absorbs the force being applied and the crystal lattice becomes disordered. After extended milling the conditions in the ball mill (heat and/or humidity) may cause crystallisation of some of the amorphous material resulting in particle-particle fusion. It would appear that the ball-milling process could be optimised to achieve the desired particle size distribution but without any loss of crystalline structure.

  16. A Statistical Method and Tool to Account for Indirect Calorimetry Differential Measurement Error in a Single-Subject Analysis

    Directory of Open Access Journals (Sweden)

    Matthew S Tenan


    Full Text Available Indirect calorimetry and oxygen consumption (VO2 are accepted tools in human physiology research. It has been shown that indirect calorimetry systems exhibit differential measurement error, where the error of a device is systematically different depending on the volume of gas flow. Moreover, systems commonly report multiple decimal places of precision, giving the clinician a false sense of device accuracy. The purpose of this manuscript is to demonstrate the use of a novel statistical tool which models the reliability of two specific indirect calorimetry systems, Douglas bag and Parvomedics 2400 TrueOne, as univariate normal distributions and implements the distribution overlapping coefficient to determine the likelihood that two VO2 measures are the same. A command line implementation of the tool is available for the R programming language as well as a web-based graphical user interface. This tool is valuable for clinicians performing a single-subject analysis as well as researchers interested in determining if their observed differences exceed the error of the device.

  17. Fluorescence spectroscopic and calorimetry based approaches to characterize the mode of interaction of small molecules with DNA. (United States)

    Banerjee, Amrita; Singh, Jasdeep; Dasgupta, Dipak


    Ethidium bromide displacement assay by fluorescence is frequently used as a diagnostic tool to identify the intercalation ability of DNA binding small molecules. Here we have demonstrated that the method has pitfalls. We have employed fluorescence, absorbance and label free technique such as isothermal titration calorimetry to probe the limitations. Ethidium bromide, a non-specific intercalator, netropsin, a (A-T) specific minor groove binder, and sanguinarine, a (G-C) specific intercalator, have been used in our experiments to study the association of a ligand with DNA in presence of a competing ligand. Here we have shown that netropsin quenches the fluorescence intensity of an equilibrium mixture of ethidium bromide - calf thymus DNA via displacement of ethidium bromide. Isothermal titration calorimetry results question the accepted interpretation of the observed decrease in fluorescence of bound ethidium bromide in terms of competitive binding of two ligands to DNA. Furthermore, isothermal titration calorimetry experiments and absorbance measurements indicate that the fluorescence change might be due to formation of ternary complex and not displacement of one ligand by another.

  18. A Statistical Method and Tool to Account for Indirect Calorimetry Differential Measurement Error in a Single-Subject Analysis. (United States)

    Tenan, Matthew S


    Indirect calorimetry and oxygen consumption (VO2) are accepted tools in human physiology research. It has been shown that indirect calorimetry systems exhibit differential measurement error, where the error of a device is systematically different depending on the volume of gas flow. Moreover, systems commonly report multiple decimal places of precision, giving the clinician a false sense of device accuracy. The purpose of this manuscript is to demonstrate the use of a novel statistical tool which models the reliability of two specific indirect calorimetry systems, Douglas bag and Parvomedics 2400 TrueOne, as univariate normal distributions and implements the distribution overlapping coefficient to determine the likelihood that two VO2 measures are the same. A command line implementation of the tool is available for the R programming language as well as a web-based graphical user interface (GUI). This tool is valuable for clinicians performing a single-subject analysis as well as researchers interested in determining if their observed differences exceed the error of the device.

  19. Proceedings of the Eleventh International Conference on Calorimetry in Particle Physics (United States)

    Cecchi, Claudia

    The Pamela silicon tungsten calorimeter / G. Zampa -- Design and development of a dense, fine grained silicon tungsten calorimeter with integrated electronics / D. Strom -- High resolution silicon detector for 1.2-3.1 eV (400-1000 nm) photons / D. Groom -- The KLEM high energy cosmic rays collector for the NUCLEON satellite mission / M. Merkin (contribution not received) -- The electromagnetic calorimeter of the Hera-b experiment / I. Matchikhilian -- The status of the ATLAS tile calorimeter / J. Mendes Saraiva -- Design and mass production of Scintillator Pad Detector (SPD) / Preshower (PS) detector for LHC-b experiment / E. Gushchin -- Study of new FNAL-NICADD extruded scintillator as active media of large EMCal of ALICE at LHC / O. Grachov -- The CMS hadron calorimeter / D. Karmgard (contribution not received) -- Test beam study of the KOPIO Shashlyk calorimeter prototype / A. Poblaguev -- The Shashlik electro-magnetic calorimeter for the LHCb experiment / S. Barsuk -- Quality of mass produced lead-tungstate crystals / R. Zhu -- Status of the CMS electromagnetic calorimeter / J. Fay -- Scintillation detectors for radiation-hard electromagnetic calorimeters / H. Loehner -- Energy, timing and two-photon invariant mass resolution of a 256-channel PBWO[symbol] calorimeter / M. Ippolitov -- A high performance hybrid electromagnetic calorimeter at Jefferson Lab / A. Gasparian -- CsI(Tl) calorimetry on BESHI / T. Hu (contribution not received) -- The crystal ball and TAPS detectors at the MAMI electron beam facility / D. Watts -- Front-end electronics of the ATLAS tile calorimeter / R. Teuscher -- The ATLAS tilecal detector control system / A. Gomes -- Performance of the liquid argon final calibration board / C. de la Taille -- Overview of the LHCb calorimeter electronics / F. Machefert -- LHCb preshower photodetector and electronics / S. Monteil -- The CMS ECAL readout architecture and the clock and control system / K. Kloukinas -- Test of the CMS-ECAL trigger

  20. Direct measurement of electron beam quality conversion factors using water calorimetry

    Energy Technology Data Exchange (ETDEWEB)

    Renaud, James, E-mail:; Seuntjens, Jan [Medical Physics Unit, McGill University, Montréal, Québec H3G 1A4 (Canada); Sarfehnia, Arman [Medical Physics Unit, McGill University, Montréal, Québec H3G 1A4, Canada and Department of Radiation Oncology, University of Toronto, Toronto, Ontario M5S 3E2 (Canada); Marchant, Kristin [Allan Blair Cancer Centre, Saskatchewan Cancer Agency, Regina, Saskatchewan S4T 7T1, Canada and Department of Oncology, University of Saskatchewan, Saskatoon, Saskatchewan S7N 5A1 (Canada); McEwen, Malcolm; Ross, Carl [Ionizing Radiation Standards, National Research Council of Canada, Ottawa, Ontario K1A 0R6 (Canada)


    . General agreement between the relative electron energy dependence of the PTW Roos data measured in this work and a recent MC-based study are also shown. Conclusions: This is the first time that water calorimetry has been successfully used to measure electron beam quality conversion factors for energies as low as 6 MeV (R{sub 50} = 2.25 cm)

  1. MO-AB-BRA-03: Calorimetry-Based Absorbed Dose to Water Measurements Using Interferometry

    Energy Technology Data Exchange (ETDEWEB)

    Flores-Martinez, E; Malin, M; DeWerd, L [University of WI-Madison/ADCL, Madison, WI (United States)


    Purpose: Interferometry-based calorimetry is a novel technique to measure radiation-induced temperature changes allowing the measurement of absorbed dose to water (ADW). There are no mechanical components in the field. This technique also has the possibility of obtaining 2D dose distributions. The goal of this investigation is to calorimetrically-measure doses between 2.5 and 5 Gy over a single projection in a photon beam using interferometry and compare the results with doses calculated using the TG-51 linac calibration. Methods: ADW was determined by measuring radiation-induced phase shifts (PSs) of light passing through water irradiated with a 6 MV photon beam. A 9×9×9 cm{sup 3} glass phantom filled with water and placed in an arm of a Michelson interferometer was irradiated with 300, 400, 500 and 600 monitor units. The whole system was thermally insulated to achieve sufficient passive temperature control. The depth of measurement was 4.5 cm with a field size of 7×7 cm{sup 2}. The intensity of the fringe pattern was monitored with a photodiode and used to calculate the time-dependent PS curve. Data was acquired 60 s before and after the irradiation. The radiation-induced PS was calculated by taking the difference in the pre- and post-irradiation drifts extrapolated to the midpoint of the irradiation. Results were compared to computed doses. Results: Average comparison of calculated ADW values with interferometry-measured values showed an agreement to within 9.5%. k=1 uncertainties were 4.3% for calculations and 14.7% for measurements. The dominant source of uncertainty for the measurements was a temperature drift of about 30 µK/s caused by heat conduction from the interferometer’s surroundings. Conclusion: This work presented the first absolute ADW measurements using interferometry in the dose range of linac-based radiotherapy. Future work to improve measurements’ reproducibility includes the implementation of active thermal control techniques.

  2. Collecting variable-concentration isothermal titration calorimetry datasets in order to determine binding mechanisms. (United States)

    Freiburger, Lee A; Mittermaier, Anthony K; Auclair, Karine


    Isothermal titration calorimetry (ITC) is commonly used to determine the thermodynamic parameters associated with the binding of a ligand to a host macromolecule. ITC has some advantages over common spectroscopic approaches for studying host/ligand interactions. For example, the heat released or absorbed when the two components interact is directly measured and does not require any exogenous reporters. Thus the binding enthalpy and the association constant (Ka) are directly obtained from ITC data, and can be used to compute the entropic contribution. Moreover, the shape of the isotherm is dependent on the c-value and the mechanistic model involved. The c-value is defined as c = n[P]tKa, where [P]t is the protein concentration, and n is the number of ligand binding sites within the host. In many cases, multiple binding sites for a given ligand are non-equivalent and ITC allows the characterization of the thermodynamic binding parameters for each individual binding site. This however requires that the correct binding model be used. This choice can be problematic if different models can fit the same experimental data. We have previously shown that this problem can be circumvented by performing experiments at several c-values. The multiple isotherms obtained at different c-values are fit simultaneously to separate models. The correct model is next identified based on the goodness of fit across the entire variable-c dataset. This process is applied here to the aminoglycoside resistance-causing enzyme aminoglycoside N-6'-acetyltransferase-Ii (AAC(6')-Ii). Although our methodology is applicable to any system, the necessity of this strategy is better demonstrated with a macromolecule-ligand system showing allostery or cooperativity, and when different binding models provide essentially identical fits to the same data. To our knowledge, there are no such systems commercially available. AAC(6')-Ii, is a homo-dimer containing two active sites, showing cooperativity between

  3. Enhanced thermal property measurement of a silver zinc battery cell using isothermal calorimetry

    Energy Technology Data Exchange (ETDEWEB)

    Ubelhor, Ryan, E-mail: [Naval Surface Warfare Center, Crane Division, 300 Highway 361, Crane, IN 47522 (United States); Ellison, Daniel [Science Applications International Corporation, 300 Highway 361, Crane, IN 47522 (United States); Pierce, Cecilia [Naval Surface Warfare Center, Crane Division, 300 Highway 361, Crane, IN 47522 (United States)


    Highlights: • Design and construction of novel heat flow calorimeter for large battery cell. • Heat flow characterization of silver zinc battery under load. • Thermal efficiency determination of silver zinc battery under load. • Surface map of heat flow of silver zinc battery under load. - Abstract: The push for increased energy density of electrochemical cells highlights the need for novel electrochemical techniques as well as additional characterization methods for these cells in order to meet user needs and safety requirements. To achieve ever increasing energy densities and faster controlled release of that energy, all materials of construction must be constantly evaluated from electrode to casing and everything in-between. Increasing the energy density of the cell improves its utility, but it also increases the waste heat and maximum potential uncontrolled energy release. Design agents and system developers need new ways to monitor and classify the probability and severity of the catastrophic failures as well as the system characteristics during intended operation. To support optimization of these battery cells it is necessary to understand their thermal characteristics at rest as well as under prescribed charge and discharge cycles. One of the many calorimetric tools available to observe and record these characteristics is heat flow calorimetry. Typically, a heat flow calorimeter is operated isothermally and measures the sum heat released or consumed by a sample material inside of a calorimetric measuring cell. For this study an improved calorimetric measuring cell for a modified Hart 6209 precision temperature bath was designed and constructed to measure the heat flow of larger electrochemical cells (18 × 8 × 16 cm). This new calorimetric measuring cell is constructed to allow independent measurements of heat flow among each of the sample’s six sides in contrast to the typical one measurement of the average heat flow. Heat flows from 0.01 to 7

  4. Approximate Time to Steady-state Resting Energy Expenditure Using Indirect Calorimetry in Young, Healthy Adults. (United States)

    Popp, Collin J; Tisch, Jocelyn J; Sakarcan, Kenan E; Bridges, William C; Jesch, Elliot D


    Indirect calorimetry (IC) measurements to estimate resting energy expenditure (REE) necessitate a stable measurement period or steady state (SS). There is limited evidence when assessing the time to reach SS in young, healthy adults. The aims of this prospective study are to determine the approximate time to necessary reach SS using open-circuit IC and to establish the appropriate duration of SS needed to estimate REE. One hundred young, healthy participants (54 males and 46 females; age = 20.6 ± 2.1 years; body weight = 73.6 ± 16.3 kg; height 172.5 ± 9.3 cm; BMI = 24.5 ± 3.8 kg/m(2)) completed IC measurement for approximately 30 min while the volume of oxygen (VO2) and volume of carbon dioxide (VCO2) were collected. SS was defined by variations in the VO2 and VCO2 of ≤10% coefficient of variation (%CV) over a period of five consecutive minutes. The 30-min IC measurement was divided into six 5-min segments, such as S1, S2, S3, S4, S5, and S6. The results show that SS was achieved during S2 (%CV = 6.81 ± 3.2%), and the %CV continued to met the SS criteria for the duration of the IC measurement (S3 = 8.07 ± 4.4%, S4 = 7.93 ± 3.7%, S5 = 7.75 ± 4.1%, and S6 = 8.60 ± 4.6%). The current study found that in a population of young, healthy adults the duration of the IC measurement period could be a minimum of 10 min. The first 5-min segment was discarded, while SS occurred by the second 5-min segment.

  5. Characteristics and thermodynamics of the interaction of 6-shogaol with human serum albumin as studied by isothermal titration calorimetry

    Directory of Open Access Journals (Sweden)

    Shevin Rizal Feroz

    Full Text Available ABSTRACT The interaction between 6-shogaol, a pharmacologically active ginger constituent, and human serum albumin (HSA, the main in vivo drug transporter, was investigated using isothermal titration calorimetry (ITC. The value of the binding constant, Ka (5.02 ± 1.37 × 104 M−1 obtained for the 6-shogaol-HSA system suggested intermediate affinity. Analysis of the ITC data revealed feasibility of the binding reaction due to favorable enthalpy and entropy changes. The values of the thermodynamic parameters suggested involvement of van der Waals forces, hydrogen bonds and hydrophobic interactions in the 6-shogaol-HSA complex formation.

  6. Investigation of lipid membrane macro- and micro-structure using calorimetry and computer simulation: structural and functional relationships

    DEFF Research Database (Denmark)

    Jørgensen, Kent; Mouritsen, Ole G.


    The lipid bilayer part of biological membranes is a complex lipid mixture displaying cooperative phenomena. By means of differential scanning calorimetry and computer simulation techniques, the equilibrium and non-equilibrium properties of the large assembly of mutually interacting amphiphilic...... lipid molecules constituting the lipid bilayer have been investigated. The cooperative many-particle lipid bilayer behavior is manifested in terms of phase transitions and large-scale macroscopic phase equilibria. On a smaller nanometer length-scale, equilibrium structural and compositional fluctuations...... and proteins. (C) 1999 Published by Elsevier Science B.V. All rights reserved....

  7. Evaluation of enthalpy change due to hydrogen desorption for lithium amide/imide system by differential scanning calorimetry



    Enthalpy change (ΔH) due to hydrogen desorption (H-desorption) for the lithium amide/imide system was evaluated by differential scanning calorimetry (DSC) measurement. In order to obtain the accurate and precise value of ΔH, we have paid special attention to following two points for correcting raw experimental data. One is to determine a cell constant of DSC equipment, which was evaluated by using the TiO2-doped MgH2 compound as a reference because of its quite similar hydrogen desorption pro...

  8. Isothermal titration calorimetry study of a bistable supramolecular system: reversible complexation of cryptand[2.2.2] with potassium ions. (United States)

    del Rosso, Maria G; Ciesielski, Artur; Colella, Silvia; Harrowfield, Jack M; Samorì, Paolo


    Isothermal titration calorimetry (ITC) is used to investigate the thermodynamics of the complexation of potassium ions by 1,10-diaza-4,7,13,16,21,24-hexaoxabicyclo[8.8.8]hexacosane (cryptand[2.2.2]) in aqueous solution. By changing the pH of the solution it was possible to trigger the reversible complexation/decomplexation of the cryptand in consecutive in situ experiments and to assess for the first time the use of ITC to monitor the thermodynamics of a bistable system.

  9. Clinical Guide for the Use of Metabolic Carts: Indirect Calorimetry--No Longer the Orphan of Energy Estimation. (United States)

    Singer, Pierre; Singer, Joelle


    Critically ill patients often require nutrition support, but accurately determining energy needs in these patients is difficult. Energy expenditure is affected by patient characteristics such as weight, height, age, and sex but is also influenced by factors such as body temperature, nutrition support, sepsis, sedation, and therapies. Using predictive equations to estimate energy needs is known to be inaccurate. Therefore, indirect calorimetry measurement is considered the gold standard to evaluate energy needs in clinical practice. This review defines the indications, limitations, and pitfalls of this technique and gives practice suggestions in various clinical situations.

  10. Prediction of the self-accelerating decomposition temperature (SADT) for liquid organic peroxides from differential scanning calorimetry (DSC) measurements. (United States)

    Malow, M; Wehrstedt, K D


    We present a prediction (estimation, calculation, screening) method for the estimation of the self-accelerating decomposition temperature (SADT) for liquid organic peroxides from differential scanning calorimetry (DSC) measurements based on the concepts of thermal explosion theory originally introduced by Semonov which are adopted to our problem assuming nth-order reaction kinetics. For the peroxides under investigation, we demonstrate good agreement with the experimental SADT. This method can be used as a quick and easy applicable method for the estimation of the critical temperatures.

  11. Differential scanning calorimetry and fluorescence study of lactoperoxidase as a function of guanidinium-HCl, urea, and pH. (United States)

    Zelent, Bogumil; Sharp, Kim A; Vanderkooi, Jane M


    The stability of bovine lactoperoxidase to denaturation by guanidinium-HCl, urea, or high temperature was examined by differential scanning calorimetry (DSC) and tryptophan fluorescence. The calorimetric scans were observed to be dependent on the heating scan rate, indicating that lactoperoxidase stability at temperatures near Tm is controlled by kinetics. The values for the thermal transition, Tm, at slow heating scan rate were 66.8, 61.1, and 47.2 degrees C in the presence of 0.5, 1, and 2 M guanidinium-HCl, respectively. The extrapolated value for Tm in the absence of guanidinium-HCl is 73.7 degrees C, compared with 70.2 degrees C obtained by experiment; a lower experimental value without a denaturant is consistent with distortion of the thermal profile due to aggregation or other irreversible phenomenon. Values for the heat capacity, Cp, at Tm and Ea for the thermal transition decrease under conditions where Tm is lowered. At a given concentration, urea is less effective than guanidinium-HCl in reducing Tm, but urea reduces Cp relatively more. Both fluorescence and DSC indicate that thermally denatured protein is not random coil. A change in fluorescence around 35 degrees C, which was previously reported for EPR and CD measurements (Boscolo et al. Biochim. Biophys. Acta 1774 (2007) 1164-1172), is not seen by calorimetry, suggesting that a local and not a global change in protein conformation produces this fluorescence change.

  12. Experimental determination of the nucleation rates of undercooled micron-sized liquid droplets based on fast chip calorimetry

    Energy Technology Data Exchange (ETDEWEB)

    Simon, Christian, E-mail:; Peterlechner, Martin; Wilde, Gerhard


    Highlights: • Fast scanning calorimeter calibration with position dependence. • Calibration of fast scanning calorimeter during cooling. • Quantitative determination of nucleation rates by treating the undercooling as stochastic parameter - Abstract: Accurate thermal analyzes and calorimetry measurements depend on careful calibration measurements. For conventional differential scanning calorimeters (DSC) the calibration procedure is well known. The melting point of different pure metals is measured and compared with literature data to adjust the temperature reading of the calorimeter. Likewise, the measured melting enthalpies of standard reference substances serve for enthalpy calibration. Yet for fast chip calorimetry, new procedures need to be established. For the medium-area and large-area calorimeter chips, this procedure needs to be modified, because the calibration behavior depends on the position of the sample on the measurement area. Additionally, a way to calibrate the calorimeter for measurements performed during cooling will also be shown. For this second aspect, the athermal and diffusionless martensitic phase transformation of Ni{sub 49.9}–Ti{sub 50.1} at% was used. The well-calibrated sensor chips are ideally suited to perform nucleation rate density analyzes based on a statistical approach. Here, the nucleation rate densities of micron-sized pure Sn droplets that had been coated with a non-catalytic coating have been determined by experimental analysis of the statistical variance of the undercooling response.

  13. Evaluation of aluminosilicate glass sintering during differential scanning calorimetry; Estudo da sinterizacao de vidros aluminossilicatos por calorimetria exploratoria diferencial

    Energy Technology Data Exchange (ETDEWEB)

    Souza, Juliana Pereira de


    In this work a difference in the baseline in differential scanning calorimetry analyses, observed in a work where aluminosilicate glasses microspheres containing Ho were studied for application in selective internal radiotherapy as hepatocellular carcinoma treatment, was studied. The glasses with nominal composition 53,7 SiO{sub 2} .10,5 Al{sub 2}O{sub 3} . 35,8 MgO in %mol were produced from traditional melting. The first obtained were milled and sieved in the range of 45 a 63 μm. The material was used to produce glass microspheres by the gravitational fall method. The glass powder and the microspheres were characterized by X ray fluorescence spectrometry, laser diffraction, X ray diffraction, differential scanning calorimetry, differential thermal analysis, thermogravimetry, mass spectrometry, and scanning electron microscopy. After the thermal analyses, pellets were formed in the crucibles and were analyzed by scanning electron microscopy, X ray diffraction, and He pycnometry. The difference in the baseline was associated to the viscous flow sintering process and happens because of the decrease in the detected heat flow due to the sample shrinkage. Other events as concurrent crystallization with the sintering process were also studied. (author)

  14. An isothermal titration and differential scanning calorimetry study of the G-quadruplex DNA-insulin interaction. (United States)

    Timmer, Christine M; Michmerhuizen, Nicole L; Witte, Amanda B; Van Winkle, Margaret; Zhou, Dejian; Sinniah, Kumar


    The binding of insulin to the G-quadruplexes formed by the consensus sequence of the insulin-linked polymorphic region (ILPR) was investigated with differential scanning calorimetry (DSC) and isothermal titration calorimetry (ITC). The thermal denaturation temperature of insulin was increased by almost 4 °C upon binding to ILPR G-quadruplex DNA as determined by DSC. The thermodynamic parameters (K(D), ΔH, ΔG, and ΔS) of the insulin-G-quadruplex complex were further investigated by temperature-dependent ITC measurement over the range of 10-37 °C. The binding of insulin to the ILPR consensus sequence displays micromolar affinity in phosphate buffer at pH 7.4, which is mainly driven by entropic factors below 25 °C but by enthalpic terms above 30 °C. The interaction was also examined in several different buffers, and results showed that the observed ΔH is dependent on the ionization enthalpy of the buffer used. This indicates proton release upon the binding of G-quadruplex DNA to insulin. Additionally, the large negative change in heat capacity for this interaction may be associated with the dominant hydrophobicity of the amino acid sequence of insulin's β subunit, which is known to bind to the ILPR G-quadruplex DNA.

  15. Aggregation property of glycyrrhizic acid and its interaction with cyclodextrins analyzed by dynamic light scattering, isothermal titration calorimetry, and NMR. (United States)

    Izutani, Yusuke; Kanaori, Kenji; Oda, Masayuki


    The structural properties of glycyrrhizic acid, a sweet-tasting constituent of Glycyrrhiza glabra, and its interaction with cyclodextrins were analyzed using dynamic light scattering, isothermal titration calorimetry, and NMR. The dynamic light scattering and NMR studies showed that glycyrrhizic acid forms a water-soluble aggregate that disperses upon the addition of γ-cyclodextrin. The high sweetness of glycyrrhizic acid can be closely correlated with this aggregation, because the multimers of glycyrrhizic acid can simultaneously bind to the sweet taste receptors on the human tongue. The isothermal titration calorimetry experiments demonstrated that γ-cyclodextrin binds to glycyrrhizic acid more strongly than β-cyclodextrin, however, both reactions are accompanied by a favorable change in binding entropy. Considering the large negative change in heat capacity that is observed during the binding of γ-cyclodextrin, the main driving force for the binding is hydrophobic interactions with dehydration, which is typical for inclusion complex. NMR experiments showed that γ-cyclodextrin interacts with the central part of the aglycone moiety, not the glucuronic acid moieties, resulting in high binding affinity. It should also be noted that the two distinct complexes of glycyrrhizic acid with γ-cyclodextrin would exist in aqueous solution.

  16. PREFACE: XIII International Conference on Calorimetry in High Energy Physics (CALOR 2008) (United States)

    Livan, Michele


    The XIII International Conference on Calorimetry in High Energy Physics was held in Pavia, Italy, 26-30 May 2008, picking up the baton from the 2006 Conference in Chicago. The Conference took place in the unique environment of the Theresian Room of the University Library. The attendees were surrounded by over 40 000 books of general interest and culture, and had the opportunity to see precious volumes written by such people as Galileo, Volta and Faraday. The Workshop brought together more than 120 participants, including senior scientists as well as young physicists, confirming the central and ever-growing role of calorimeters in modern particle physics. The development of these detectors, as stressed by Professor Klaus Pretzl in his lectio magistralis, has made it possible to explore new frontiers in physics, and the present scenario is no exception to this rule. With the LHC experiments almost completely installed and ready to take data, the Conference was an ideal chance to review the status of the different projects, whose development has been followed and discussed throughout the entire Calor series, and to show that they are capable of meeting the design specifications. Other highlights were the performance and physics results of calorimeters installed in currently operating experiments. In the session on astrophysics and neutrinos, the contributions confirmed the key role of calorimeters in this sector and demonstrated their growing application even beyond the field of accelerator physics. Considerable time was devoted to the state-of-the-art techniques in the design and operation of the detectors, while the session on simulation addressed the importance of a thorough understanding of the shower development to meet the demanding requirements of present experiments. Finally, on the R&D side, the particle flow and dual read-out concepts confronted the challenges issued by the next generation of experiments. This complex material was reviewed in 83

  17. Change in physical structure of a phenol-spiked sapric histosol observed by Differential Scanning Calorimetry (United States)

    Ondruch, Pavel; Kucerik, Jiri; Schaumann, Gabriele E.


    Interactions of pollutants with soil organic matter (SOM), their fate and transformation are crucial for understanding of soil functions and properties. In past, many papers dealing with sorption of organic and inorganic compounds have been published. However, their aim was almost exceptionally fo-cused on the pollutants themselves, determination of sorption isotherms and influence of external factors, while the change in SOM supramolecular structure was usually ignored. The SOM structure is, however, very important, since the adsorbed pollutant might have a significant influence on soil stability and functions. Differential scanning calorimetry (DSC) represents a technique, which has been successfully used to analyze the physical structure and physico-chemical aging of SOM. It has been found out that water molecules progressively stabilize SOM (water molecule bridge (WaMB)) (Schaumann & Bertmer 2008). Those bridges connect and stabilize SOM and can be disrupted at higher temperature (WaMB transition; (Kunhi Mouvenchery et al. 2013; Schaumann et al. 2013). In the same temperature region melting of aliphatic moieties can be observed (Hu et al. 2000; Chilom & Rice 2005; Kucerik et al. submitted 2013). In this work, we studied the effect of phenol on the physical structure of sapric histosol. Phenol was dissolved in various solvents (water, acetone, hexane, methanol) and added to soils. After the evaporation of solvents by air drying, the sample was equilibrated at 76% relative humidity for 3 weeks. Using DSC, we investigated the influence of phenol on histosol structure and time dependence of melting temperature of aliphatic moieties and WaMB transition. While addition of pure organic solvent only resulted in slightly increased transition temperatures, both melting temperature and WaMB transition temperature were significantly reduced in most cases if phenol was dissolved in these solvents. Water treatment caused a decrease in WaMB transition temperature but

  18. Interactions in interesterified palm and palm kernel oils mixtures. II – Microscopy and Differential Scanning Calorimetry

    Directory of Open Access Journals (Sweden)

    Grimaldi, Renato


    Full Text Available Palm oil (PO and palm kernel oil (PKO compositions (100/0, 80/20, 60/40, 50/50, 40/60, 20/80 and 0/100 were interesterified in laboratory scale under predetermined conditions (0.4% sodium metoxide, 20 minutes, 100ºC. The fourteen samples, before and after interesterification, were characterized by Polarized Light Microscopy and Differential Scanning Calorimetry (DSC. Results showed the effect of various factors on the form and width of crystals. The mean area of crystals revealed the increase of crystals when PKO was added, with values varying from 2.7 x 10E3 µm2 to PO and 1.8 x 10E6 µm2 to PKO. After interesterification, the crystal widths were lower at PO/PKO 100/0, 80/20, 60/40, 20/80 fractions and were higher to anothers. The beta-prime polimorphic form was observed in the pure palm oil sample. The results showed in melting curves, onset values from –19.6ºC to more unsaturated peaks until 20.7ºC to more saturated ones. The higher values to more saturated peak in a melting curve to palm oil, 38.7 J.g-1 before and 48.4 J.g-1 after interesterification, showed a mores table saturated group. I n a genera l way, t h e interesterification promoted an increase of crystallization rate and a better compatibility between PO/PKO fractions.Fueron interesterificados en el laboratorio mezclas de aceite de palma (PO y aceite de palmiste (PKO en diferentes proporciones (100/0, 80/20, 60/40, 50/50, 40/60, 20/80 y 0/100 bajo condiciones predeterminadas (0.4% metoxido de sodio, 20 minutos, 100ºC. Las catorce muestras fueron caracterizadas antes y después de la interesterificación por Microscopía de Luz Polarizada y por Calorimetría Diferencial de Barrido (DSC. Los resultados mostraron el efecto de varios factores sobre la forma y anchura de los cristales. El área media de los cristales revela el aumento de tamaño de los mismos cuando aumenta la proporción de PKO, con valores que varían entre 2.7 x 10E3 µm2 para PO y 1.8 x 10E

  19. Evidence analysis library review of best practices for performing indirect calorimetry in healthy and non-critically ill individuals. (United States)

    Fullmer, Susan; Benson-Davies, Sue; Earthman, Carrie P; Frankenfield, David C; Gradwell, Erica; Lee, Peggy S P; Piemonte, Tami; Trabulsi, Jillian


    When measurement of resting metabolic rate (RMR) by indirect calorimetry is necessary, following evidence-based protocols will ensure the individual has achieved a resting state. The purpose of this project was to update the best practices for measuring RMR by indirect calorimetry in healthy and non-critically ill adults and children found the Evidence Analysis Library of the Academy of Nutrition and Dietetics. The Evidence Analysis process described by the Academy of Nutrition and Dietetics was followed. The Ovid database was searched for papers published between 2003 and 2012 using key words identified by the work group and research consultants, studies used in the previous project were also considered (1980 to 2003), and references were hand searched. The work group worked in pairs to assign papers to specific questions; however, the work group developed evidence summaries, conclusion statements, and recommendations as a group. Only 43 papers were included to answer 21 questions about the best practices to ensure an individual is at rest when measuring RMR in the non-critically ill population. In summary, subjects should be fasted for at least 7 hours and rest for 30 minutes in a thermoneutral, quiet, and dimly lit room in the supine position before the test, without doing any activities, including fidgeting, reading, or listening to music. RMR can be measured at any time of the day as long as resting conditions are met. The duration of the effects of nicotine and caffeine and other stimulants is unknown, but lasts longer than 140 minutes and 240 minutes, respectively. The duration of the effects of various types of exercise on RMR is unknown. Recommendations for achieving steady state, preferred gas-collection devices, and use of respiratory quotient to detect measurement errors are also given. Of the 21 conclusions statements developed in this systemic review, only 5 received a grade I or II. One limitation is the low number of studies available to address the

  20. Low-temperature polymorphic phase transition in a crystalline tripeptide L-Ala-L-Pro-Gly·H2O revealed by adiabatic calorimetry. (United States)

    Markin, Alexey V; Markhasin, Evgeny; Sologubov, Semen S; Ni, Qing Zhe; Smirnova, Natalia N; Griffin, Robert G


    We demonstrate application of precise adiabatic vacuum calorimetry to observation of phase transition in the tripeptide L-alanyl-L-prolyl-glycine monohydrate (APG) from 6 to 320 K and report the standard thermodynamic properties of the tripeptide in the entire range. Thus, the heat capacity of APG was measured by adiabatic vacuum calorimetry in the above temperature range. The tripeptide exhibits a reversible first-order solid-to-solid phase transition characterized by strong thermal hysteresis. We report the standard thermodynamic characteristics of this transition and show that differential scanning calorimetry can reliably characterize the observed phase transition with <5 mg of the sample. Additionally, the standard entropy of formation from the elemental substances and the standard entropy of hypothetical reaction of synthesis from the amino acids at 298.15 K were calculated for the studied tripeptide.


    Institute of Scientific and Technical Information of China (English)

    X.L. Xu; Z.W. Yu; S.J. Ji; J.C. Sun; Z.K. Hei


    Decomposition processes of the quenched Zn-Al alloys were studied by differentiai scanning calorimetry (DSC), X-ray diffraction (XRD) and transmission electron microscopy (TEM). The results show that the stabilities of supersaturated solid solution (SSS) of Zn-Al alloy and c' phase formed by quenching would reduce with increasing Zn content and precipitating η-Zn phases even when aging at ambient temperature,so that exothermic precipitation peak in DSC curve would disappear. The activation energy of the η-Zn precipitation and their reaction enthalpy were calculated and measured. The kinetics of α' decomposition or η-Zn formation was determined by XRD.The microstructure change during aging was observed by TEM.

  2. Starch transitions of different gluten free flour doughs determined by dynamic thermal mechanical analysis and differential scanning calorimetry. (United States)

    Moreira, R; Chenlo, F; Arufe, S


    Gluten-free flour doughs (three from different maize varieties and one from chestnut fruit) processed at the same consistency level (1.10 ± 0.07 N m) with different water absorption were used to determine the starch transitions by means of two different experimental techniques, differential scanning calorimetry (DSC) and dynamic thermal mechanical analysis (DMTA). The ranges of temperatures of gelatinization (G), amylopectin melting (M1), amylose-lipid complexes melting (M2) and amylose melting (M3) for all tested flour doughs were determined by both experimental techniques with acceptable agreement between them. The starch transitions in DMTA were determined by means of the elastic modulus (G, M1 and M2) or damping factor (G, M3) evolution with temperature. The temperatures and enthalpies of the transitions depended on water content, the nature and characteristics (mainly damaged starch) of the starch and the presence of other compounds (mainly lipid and sugars) in the flour doughs.

  3. Constraints on the Interactions between Dark Matter and Baryons from the X-ray Quantum Calorimetry Experiment

    CERN Document Server

    Erickcek, Adrienne L; McCammon, Dan; McGuire, Patrick C


    Although the rocket-based X-ray Quantum Calorimetry (XQC) experiment was designed for X-ray spectroscopy, the minimal shielding of its calorimeters, its low atmospheric overburden, and its low-threshold detectors make it among the most sensitive instruments for detecting or constraining strong interactions between dark matter particles and baryons. We use Monte Carlo simulations to obtain the precise limits the XQC experiment places on spin-independent interactions between dark matter and baryons, improving upon earlier analytical estimates. We find that the XQC experiment rules out a wide range of nucleon-scattering cross sections centered around one barn for dark matter particles with masses between 0.01 and 10^5 GeV. Our analysis also provides new constraints on cases where only a fraction of the dark matter strongly interacts with baryons.

  4. Determination of heat transfer coefficients at the polymer-mold-interface for injection molding simulation by means of calorimetry (United States)

    Stricker, M.; Steinbichler, G.


    Appropriate modeling of heat transfer from the polymer material to the injection mold is essential to achieve accurate simulation results. The heat transfer is commonly modeled using convective heat transfer and applying heat transfer coefficients (HTC) to the polymer-mold-interface. The set HTC has an influence on the results for filling pressure, cooling performance and shrinkage, among others. The current paper, presents a new strategy to measure HTC in injection molding experiments using Newtons law of cooling. The heat flux is calculated out of demolding heat (measured by means of calorimetry), injection heat (measured by means of an IR-sensor), cooling time and part mass. Cavity surface area, average mold surface temperature and average part surface temperature lead to the HTC.

  5. Whole-body fat oxidation determined by graded exercise and indirect calorimetry: a role for muscle oxidative capacity?

    DEFF Research Database (Denmark)

    Nordby, P; Saltin, B; Helge, J W


    subjects were recruited and categorized into an untrained (N=8, VO(2max) 3.5+/-0.1 L/min) and a trained (N=8, VO(2max) 4.6+/-0.2 L/min) group. Subjects performed a graded exercise test commencing at 60 W for 8 min followed by 35 W increments every 3 min. On a separate day, muscle biopsies were obtained...... from vastus lateralis and a 3 h bicycle exercise test was performed at 58% of VO(2max). Whole-body fat oxidation was calculated during prolonged and graded exercise from the respiratory exchange ratio using standard indirect calorimetry equations. Based on the graded exercise test, whole-body peak fat...... oxidation was determined. The body composition was determined by DEXA. Whole-body peak fat oxidation (250+/-25 and 462+/-33 mg/min) was higher (PVO(2max)) in trained compared with untrained subjects, respectively. Muscle...

  6. Analysis of the Pipe Heat Loss of the Water Flow Calorimetry System in EAST Neutral Beam Injector (United States)

    Hu, Chundong; Chen, Yu; Xu, Yongjian; Yu, Ling; Li, Xiang; Zhang, Weitang


    Neutral beam injection heating is one of the main auxiliary heating methods in controllable nuclear fusion research. In the EAST neutral beam injector, a water flow calorimetry (WFC) system is applied to measure the heat load on the electrode system of the ion source and the heat loading components of the beamline. Due to the heat loss in the return water pipe, there are some measuring errors for the current WFC system. In this paper, the errors were measured experimentally and analyzed theoretically, which lay a basis for the exact calculation of beam power deposition distribution and neutralization efficiency. supported by the National Magnetic Confinement Fusion Science Program of China (No. 2013GB101001) and the International Science & Technology Cooperation Program of China (No. 2014DFG61950)

  7. Synthesis kinetics of Mg_2Sn in Mg-Sn powder mixture using non-isothermal differential scanning calorimetry

    Institute of Scientific and Technical Information of China (English)

    WU Yu-feng; DU Wen-bo; ZUO Tie-yong


    The non-isothermal heating process of Mg-Sn powder mixture was studied by differential scanning calorimetry(DSC) technique and the synthesis kinetics of Mg_2Sn was evaluated by the model-free and model-fitting methods. The activation energy and conversion function of Mg_2Sn synthesis reaction are calculated to be 281.7 kJ/mol and g(α)=[-ln(1-α)]~(1/4), respectively. The reaction mechanism of 2Mg+Sn→Mg_2Sn under non-isothermal condition is regarded as "nucleation and growth". During the non-isothermal heating process, the phase transformation occurred in the Mg-Sn powder mixture was analyzed by XRD and the microstructure evolution of Mg_2Sn was observed by optical microscopy, which is in good agreement with the reaction mechanism of 2Mg+Sn→Mg_2Sn deduced from the kinetic evaluation.

  8. Binding of an Oligomeric Ellagitannin Series to Bovine Serum Albumin (BSA): Analysis by Isothermal Titration Calorimetry (ITC). (United States)

    Karonen, Maarit; Oraviita, Marianne; Mueller-Harvey, Irene; Salminen, Juha-Pekka; Green, Rebecca J


    A unique series of oligomeric ellagitannins was used to study their interactions with bovine serum albumin (BSA) by isothermal titration calorimetry. Oligomeric ellagitannins, ranging from monomer to heptamer and a mixture of octamer-undecamers, were isolated as individual pure compounds. This series allowed studying the effects of oligomer size and other structural features. The monomeric to trimeric ellagitannins deviated most from the overall trends. The interactions of ellagitannin oligomers from tetramers to octa-undecamers with BSA revealed strong similarities. In contrast to the equilibrium binding constant, enthalpy showed an increasing trend from the dimer to larger oligomers. It is likely that first the macrocyclic part of the ellagitannin binds to the defined binding sites on the protein surface and then the "flexible tail" of the ellagitannin coats the protein surface. The results highlight the importance of molecular flexibility to maximize binding between the ellagitannin and protein surfaces.

  9. Interaction of Ru(Ⅱ) Complex with Yeast tRNA Studied by Isothermal Titration Calorimetry

    Institute of Scientific and Technical Information of China (English)

    徐宏; 刘敛洪; 刘志刚; 梁毅; 张鹏; 杜芬; 周兵瑞; 计亮年


    The interaction of metal complex with RNA has been studied by isothermal titration calorimetry (ITC) for the first time. ITC experiments show that complex [Ru(phen)2MPIP]2+ {phen= 1,10-phenanthroline, MP[P-2-(4-methylphenyl)imidazo[4,5-f]-1, 10-phenanthroline} interacts with yeast tRNA in terms of a model for a singleset of identical sites through intercalation, which is consistent with our previous observation obtained from spectroscopic methods, and this binding process was driven by a moderately favorable enthalpy decrease in combination with a moderately favorable entropy increase, suggesting that ITC is an effective method for deep studying the interactions of metal complexes with RNA.

  10. Calorimetry and Langmuir-Blodgett studies on the interaction of a lipophilic prodrug of LHRH with biomembrane models. (United States)

    Sarpietro, Maria G; Accolla, Maria L; Santoro, Nancy; Mansfeld, Friederike M; Pignatello, Rosario; Toth, Istvan; Castelli, Francesco


    The interaction between an amphiphilic luteinizing hormone-releasing hormone (LHRH) prodrug that incorporated a lipoamino acid moiety (C12-LAA) with biological membrane models that consisted of multilamellar liposomes (MLVs) and phospholipid monolayers, was studied using Differential Scanning Calorimetry (DSC) and Langmuir-Blodgett film techniques. The effect of the prodrug C12[Q1]LHRH on the lipid layers was compared with the results obtained with the pure precursors, LHRH and C12-LAA. Conjugation of LHRH with a LAA promoiety showed to improve the peptide interaction with biomembrane models. Basing on the calorimetric findings, the LAA moiety aided the transfer of the prodrug from an aqueous solution to the biomembrane model.

  11. Evaluation of the Ignition Temperature in Thermal Explosion Synthesis of TiAl3 by Differential Scanning Calorimetry

    Institute of Scientific and Technical Information of China (English)


    Application of the Semenov theory of spontaneous ignition to evaluation of the critical temperature (Tc′) in thermal explosion (TE) synthesis was conducted with the Ti-75at pct Al binary system using nonisothermal differential scanning calorimetry (DSC) at different heating rates. And the critical temperature for isothermal TE is predicted to be 728.9°C by the multiple linear regression of Tc′s evaluated according to Semenov theory, which is close to the range of 740~745°C obtained from the isothermal DSC observation. This result proves that Semenov theory of spontaneous ignition is also feasible for TE synthesis in binary metallic systems like Ti-75 at. pct Al system.

  12. Binding between bixin and whey protein at pH 7.4 studied by spectroscopy and isothermal titration calorimetry. (United States)

    Zhang, Yue; Zhong, Qixin


    Bixin is the major coloring component of annatto used in manufacturing colored cheeses, but its presence in liquid whey causes undesirable quality of the recovered whey protein ingredients. The objective of this work was to study molecular binding between bixin and three major whey proteins (β-lactoglobulin, α-lactalbumin, and bovine serum albumin) at pH 7.4 using UV-vis absorption spectroscopy, fluorescence spectroscopy, isothermal titration calorimetry, and circular dichroism. These complementary techniques illustrated that the binding is a spontaneous complexation process mainly driven by hydrophobic interactions. The complexation is favored at a lower temperature and a higher ionic strength. At a lower temperature, the binding is entropy-driven, while it changes to an enthalpy-driven process at higher temperatures. The binding also increases the percentage of unordered secondary structures of proteins. Findings from this work can be used to develop whey protein recovery processes for minimizing residual annatto content in whey protein ingredients.

  13. Interaction of phenazinium dyes with double-stranded poly(A): spectroscopy and isothermal titration calorimetry studies. (United States)

    Khan, Asma Yasmeen; Saha, Baishakhi; Kumar, Gopinatha Suresh


    A comprehensive study on the binding of phenazinium dyes viz. janus green B, indoine blue, safranine O and phenosafranine with double stranded poly(A) using various spectroscopic and calorimetric techniques is presented. A higher binding of janus green B and indoine blue over safranine O and phenosafranine to poly(A) was observed from all experiments. Intercalative mode of binding of the dyes was inferred from fluorescence polarization anisotropy, iodide quenching and viscosity experiments. Circular dichroism study revealed significant perturbation of the secondary structure of poly(A) on binding of these dyes. Results from isothermal titration calorimetry experiments suggested that the binding was predominantly entropy driven with a minor contribution of enthalpy to the standard molar Gibbs energy. The results presented here may open new opportunities in the application of these dyes as RNA targeted therapeutic agents.

  14. Designing isothermal titration calorimetry experiments for the study of 1:1 binding: problems with the "standard protocol". (United States)

    Tellinghuisen, Joel


    Literature recommendations for designing isothermal titration calorimetry (ITC) experiments to study 1:1 binding, M+X -->/applicability of the ITC technique. These deficiencies are discussed here along with other misconceptions. Whether a specific binding process can be studied by ITC is determined less by c (the product of binding constant K and titrand concentration [M](0)) than by the total detectable heat q(tot) and the extent to which M can be converted to MX. As guidelines, with 90% conversion to MX, K can be estimated within 5% over the range 10 to 10(8)M(-1) when q(tot)/σ(q)≈700, where σ(q) is the standard deviation for estimation of q. This ratio drops to ~150 when the stoichiometry parameter n is treated as known. A computer application for modeling 1:1 binding yields realistic estimates of parameter standard errors for use in protocol design and feasibility assessment.

  15. Differential Scanning Calorimetry and Evolved Gas Analysis at Mars Ambient Conditions Using the Thermal Evolved Gas Analyzer (TEGA) (United States)

    Musselwhite, D. S.; Boynton, W. V.; Ming, Douglas W.; Quadlander, G.; Kerry, K. E.; Bode, R. C.; Bailey, S. H.; Ward, M. G.; Pathare, A. V.; Lorenz, R. D.


    Differential Scanning Calorimetry (DSC) combined with evolved gas analysis (EGA) is a well developed technique for the analysis of a wide variety of sample types with broad application in material and soil sciences. However, the use of the technique for samples under conditions of pressure and temperature as found on other planets is one of current C development and cutting edge research. The Thermal Evolved Gas Analyzer (MGA), which was designed, built and tested at the University of Arizona's Lunar and Planetary Lab (LPL), utilizes DSC/EGA. TEGA, which was sent to Mars on the ill-fated Mars Polar Lander, was to be the first application of DSC/EGA on the surface of Mars as well as the first direct measurement of the volatile-bearing mineralogy in martian soil.

  16. Differential Scanning Calorimetry and Evolved Gas Analysis at Mars Ambient Conditions Using the Thermal Evolved Gas Analyser (TEGA) (United States)

    Musselwhite, D. S.; Boynton, W. V.; Ming, D. W.; Quadlander, G.; Kerry, K. E.; Bode, R. C.; Bailey, S. H.; Ward, M. G.; Pathare, A. V.; Lorenz, R. D.


    Differential Scanning Calorimetry (DSC) combined with evolved gas analysis (EGA) is a well developed technique for the analysis of a wide variety of sample types with broad application in material and soil sciences. However, the use of the technique for samples under conditions of pressure and temperature as found on other planets is one of current development and cutting edge research. The Thermal Evolved Gas Analyzer (TEGA), which was designed, built and tested at the University of Arizona's Lunar and Planetary Lab (LPL), utilizes DSC/EGA. TEGA, which was sent to Mars on the ill-fated Mars Polar Lander, was to be the first application of DSC/EGA on the surface of Mars as well as the first direct measurement of the volatile-bearing mineralogy in martian soil. Additional information is available in the original extended abstract.

  17. High-Pressure Raman and Calorimetry Studies of Vanadium(III) Alkyl Hydrides for Kubas-Type Hydrogen Storage. (United States)

    Morris, Leah; Trudeau, Michel L; Reed, Daniel; Book, David; Antonelli, David M


    Reversible hydrogen storage under ambient conditions has been identified as a major bottleneck in enabling a future hydrogen economy. Herein, we report an amorphous vanadium(III) alkyl hydride gel that binds hydrogen through the Kubas interaction. The material possesses a gravimetric adsorption capacity of 5.42 wt % H2 at 120 bar and 298 K reversibly at saturation with no loss of capacity after ten cycles. This corresponds to a volumetric capacity of 75.4 kgH2  m(-3) . Raman experiments at 100 bar confirm that Kubas binding is involved in the adsorption mechanism. The material possesses an enthalpy of H2 adsorption of +0.52 kJ mol(-1) H2 , as measured directly by calorimetry, and this is practical for use in a vehicles without a complex heat management system.

  18. Eu(3+)-mediated polymerization of benzenetetracarboxylic acid studied by spectroscopy, temperature-dependent calorimetry, and density functional theory. (United States)

    Barkleit, Astrid; Tsushima, Satoru; Savchuk, Olesya; Philipp, Jenny; Heim, Karsten; Acker, Margret; Taut, Steffen; Fahmy, Karim


    Thermodynamic parameters for the complexation of Eu(3+) with pyromellitic acid (1,2,4,5-benzenetetracarboxylic acid, BTC) as a model system for polymerizable metal-complexing humic acids were determined using temperature-dependent time-resolved laser-induced fluorescence spectroscopy (TRLFS) and isothermal titration calorimetry (ITC). At low metal and ligand concentrations (+), 500 μM Eu(3+) and BTC) a temperature-dependent polymerization was observed, where BTC monomers are linked via coordinating shared Eu(3+) ions. The two methods lead to comparable thermodynamic data (ΔH = 18.5 ± 1.5/16.5 ± 0.1 kJ mol(-1); ΔS = 152 ± 5/130 ± 5 J mol(-1) K(-1); TRLFS/ITC) in the absence of polymerization. With the onset of polymerization, TRLFS reveals the water coordination number of the lanthanide, whereas calorimetry is superior in determining the thermodynamic data in this regime. Evaluating the heat uptake kinetics, the monomer and polymer formation steps could be separated by "time-resolved" ITC, revealing almost identical binding enthalpies for the sequential reactions. Structural features of the complexes were studied by Fourier-transform infrared (FTIR) spectroscopy in combination with density functional theory (DFT) calculations showing predominantly chelating coordination with two carboxylate groups in the monomeric complex and monodentate binding of a single carboxylate group in the polymeric complex of the polycarboxylate with Eu(3+). The data show that pyromellitic acid is a suitable model for the study of metal-mediated polymerization as a crucial factor in determining the effect of humic acids on the mobility of heavy metals in the environment.

  19. Combined use of titration calorimetry and spectrofluorimetry for the screening of the acidity of solid catalysts in different liquids

    Energy Technology Data Exchange (ETDEWEB)

    Gervasini, Antonella, E-mail: [Dipartimento di Chimica, Università degli Studi di Milano, via Camillo Golgi, 19, 20133 Milano (Italy); Auroux, Aline, E-mail: [Université Lyon 1, CNRS, UMR 5256, Institut de Recherches sur la Catalyse et l‘Environnement de Lyon (IRCELYON), 2 Avenue A. Einstein, 69626 Villeurbanne (France)


    Graphical abstract: Measurements of acidity of oxides of catalytic importance in various liquids open the possibility to know their effective acidity, which is related with their activity in liquid-heterogeneous catalysis. Titration-calorimetry alone or in connection with spectrofluorimetry is efficient for this scope. - Highlights: • Measurements of acidity of oxides of catalytic importance in various liquids. • Titration-calorimetry alone or in connection with spectrofluorimetry is efficient for this scope. • Effective acidities are expressed by given sample in various liquids. • Nb-containing samples are able to maintain acidity in protic liquids. - Abstract: The effective acid and base surface properties of selected acidic and basic samples of catalytic interest (alumina, titania, zirconia, silica–alumina, niobium oxide, niobium phosphate, boron nitride, and hydrotalcite) were measured by titration with basic and acidic molecular probes (aniline, 2-phenylethylamine, and phenol) in various liquids (cyclohexane, 1,4-dioxane, isopropanol, n-decane, and toluene) with different polar and protic characteristics. The combined use of a reaction calorimeter and a spectrofluorimeter has been performed. The set-up of the coupled technique and the most interesting results are shown here. The study confirmed that the acid–base properties of solids are deeply affected by the nature and properties of the liquid surrounding the samples. Few oxides are able to maintain their surface acidity in highly polar and protic solvents, in particular whose containing niobium. In general, the solvating and coordinative ability of the most polar and protic liquids caused remarkable loss of acidity/basicity of the oxide surfaces.

  20. Flow calorimetry of the sorption of butanols to elastin preparations and comparison with surface areas determined by krypton-85 adsorption. (United States)

    Robert, L; Robert, B; Houtman, J P; Stack, M V


    1. The apparent surface areas of elastin samples as well as of several other fibrous protein preparations (collagen, keratin, polymeric stroma of aorta) were determined using two different approaches: (a) the Brunauer-Emmett-Teller method with 85Kr and (b) microflow calorimetry with n- and tert.-butanol as adsorbents in a heptane stream. 2. Areas of heat signals obtained by flow calorimetry for the adsorption and desorption of n- and tert.-butanol were substantially equivalent; desorption was more protracted than adsorption, the difference between the speed of desorption and adsorption increased with decreasing chain length of the alcohols (methanol, ethanol, n-propanol and n-butanol). 3. An inverse linear relationship was found between the energy change recorded during the adsorption process and the chain length of the alcohols (methanol, ethanol, n-propanol, n-butanol). 4. Heats of adsorption of tert.-butanol were systematically found to be significantly lower than those of n-butanol with all the protein samples investigated. 5. The apparent surface areas of the protein samples determined with tert.-butanol were on the average of the same order or only slightly higher than those obtained with 85Kr. Results obtained with n-butanol were significantly higher. The difference between surface areas obtained with n- and tert.-butanol depended on the nature of the protein sample, on its method of preparation and to some extent on the residual humidity of the sample. 6. The results could be explained on the basis of the hydrophobic theory of elastin structure (see ref. 4) and confirmed our former conclusions (see ref. 3) concerning the significantly higher surface areas of elastin samples purified by different procedures as compared to collagen or to keratin. They also confirmed the accessibility of the surface of elastic fibers to the molecular probes used in the polymeric stroma of aorta.

  1. Elucidating thermodynamic parameters for electron transfer proteins using isothermal titration calorimetry: application to the nitrogenase Fe protein. (United States)

    Sørlie, Morten; Chan, Jeannine M; Wang, Haijang; Seefeldt, Lance C; Parker, Vernon D


    Establishing thermodynamic parameters for electron transfer reactions involving redox proteins is essential for a complete description of these important reactions. While various methods have been developed for measuring the Gibbs free energy change (Delta G(HR) or E(m)) for the protein half-reactions, deconvolution of the respective contributions of enthalpy (Delta H(HR)) and entropy (Delta S(HR)) changes is much more challenging. In the present work, an approach is developed using isothermal titration calorimetry (ITC) that allows accurate determination of all of these thermodynamic parameters for protein electron transfer half-reactions. The approach was validated for essentially irreversible and reversible electron transfer reactions between well-characterized mediators and between mediators and the protein cytochrome c. In all cases, the measured thermodynamic parameters were in excellent agreement with parameters determined by electrochemical methods. Finally, the calorimetry approach was used to determine thermodynamic parameters for electron transfer reactions of the nitrogenase Fe protein [4Fe-4S](2+/+) couple in the absence or presence of MgADP or MgATP. The E(m) value was found to change from -290 mV in the absence of nucleotides to -381 mV with MgATP and -423 mV with MgADP, consistent with earlier values. For the first time, the enthalpy (Delta H(HR)) and entropy (Delta S(HR)) contributions for each case were established, revealing shifts in the contribution of each thermodynamic parameter induced by nucleotide binding. The results are discussed in the context of current models for electron transfer in nitrogenase.

  2. Insights into the binding of the drugs diclofenac sodium and cefotaxime sodium to serum albumin: calorimetry and spectroscopy. (United States)

    Sharma, Ruchika; Choudhary, Sinjan; Kishore, Nand


    Understanding physical chemistry underlying drug-protein interactions is essential to devise guidelines for the synthesis of target oriented drugs. Binding of a non-steroidal anti-inflammatory drug, diclofenac sodium (DCF) and an antibiotic drug, cefotaxime sodium (CFT) belonging to the family of cephalosporins with bovine serum albumin (BSA) has been examined using a combination of isothermal titration calorimetry (ITC), differential scanning calorimetry (DSC), steady state and time resolved fluorescence and circular dichroism spectroscopies. Binding affinity of both DCF and CFT with BSA is observed to be of the order of 10(4)M(-1), with the binding profiles fitting well to the single set of binding site model. The disagreement between calorimetric and van't Hoff enthalpies indicates non-adherence to a two-state binding process which could be attributed to changes in the conformation of the protein upon ligand binding as well as with increase in the temperature. Circular dichroism and the fluorescence results, however, do not show any major conformational changes upon binding of these drugs to BSA, and hence the discrepancy could be due to temperature induced conformational changes in the protein. The results of ionic strength dependence and binding in the presence of anionic, cationic and non-ionic surfactants indicate, involvement of more that a single type of interaction in the binding process. The ITC results for the binding of these drugs to BSA in presence of each other indicate that the binding sites for the two drugs are different, and therefore binding of one is not influenced by the other. The DSC results provide quantitative information on the effect of these drugs on the stability of serum albumin. The combined calorimetric and spectroscopic approach has provided a detailed analysis including thermodynamics of the binding of DCF and CFT with BSA qualitatively and quantitatively.

  3. A study of the growth for the microalga Chlorella vulgaris by photo-bio-calorimetry and other on-line and off-line techniques

    NARCIS (Netherlands)

    Patino, R.; Janssen, M.G.J.; Stockar, von U.


    Calorimetry and other on-line techniques are used for the first time as complement to the traditional off-line methods in order to follow the growth of the green Chlorella vulgaris microalgae. A 2-L photo-bio-reactor was adapted from a commercial calorimeter used previously to study heterotrophic mi

  4. On the characterization of host-guest complexes : Surface tension, calorimetry, and molecular dynamics of cyclodextrins with a non-ionic surfactant

    NARCIS (Netherlands)

    Pineiro, Angel; Banquy, Xavier; Perez-Casas, Silvia; Tovar, Edgar; Garcia, Abel; Villa, Alessandra; Amigo, Alfredo; Mark, Alan E.; Costas, Miguel


    Three host-guest systems have been characterized using surface tension (sigma), calorimetry, and molecular dynamics simulations (MD). The hosts were three native cyclodextrins (CD) and the guest the non-ionic carbohydrate surfactant octyl-beta-d-glucopyranoside. It is shown that, for any host-guest

  5. Characterization of the molecular distribution of drugs in glassy solid dispersions at the nano-meter scale, using differential scanning calorimetry and gravimetric water vapour sorption techniques

    NARCIS (Netherlands)

    van Drooge, D J; Hinrichs, W L J; Visser, M R; Frijlink, H W


    The molecular distribution in fully amorphous solid dispersions consisting of poly(vinylpyrrolidone) (PVP)-diazepam and inulin-diazepam was studied. One glass transition temperature (T-g), as determined by temperature modulated differential scanning calorimetry (TMDSC), was observed in PVP-diazepam

  6. Reversible amorphous-crystalline phase changes in a wide range of Se1-xTex alloys studied using ultrafast differential scanning calorimetry

    NARCIS (Netherlands)

    Vermeulen, Paul. A.; Momand, Jamo; Kooi, Bart J.


    The reversible amorphous-crystalline phase change in a chalcogenide material, specifically the Se1-xTex alloy, has been investigated for the first time using ultrafast differential scanning calorimetry. Heating rates and cooling rates up to 5000 K/s were used. Repeated reversible amorphous-crystalli

  7. Optimization of the scintillation parameters of the lead tungstate crystals for their application in high precision electromagnetic calorimetry; Optimisation des parametres de scintillation des cristaux de tungstate de plomb pour leur application dans la calorimetrie electromagnetique de haute precision

    Energy Technology Data Exchange (ETDEWEB)

    Drobychev, G


    In the frame of this dissertation work scintillation properties of the lead tungstate crystals (PWO) and possibilities of their use were studied foreseeing their application for electromagnetic calorimetry in extreme radiation environment conditions of new colliders. The results of this work can be summarized in the following way. 1. A model of the scintillations origin in the lead tungstate crystals which includes processes influencing on the crystals radiation hardness and presence of slow components in scintillations was developed. 2. An analysis of the influences of the PWO scintillation properties changes on the parameters of the electromagnetic calorimeter was done. 3. Methods of the light collection from the large scintillation elements of complex shape made of the birefringent scintillation crystal with high refraction index and low light yield in case of signal registration by a photodetector with sensitive surface small in compare with the output face of scintillator were Studied. 4. Physical principles of the methodology of the scintillation crystals certification during their mass production foreseeing their installation into a calorimeter electromagnetic were developed. Correlations between the results of measurements of the PWO crystals parameters by different methods were found. (author)

  8. PHOENIX: a scoring function for affinity prediction derived using high-resolution crystal structures and calorimetry measurements. (United States)

    Tang, Yat T; Marshall, Garland R


    Binding affinity prediction is one of the most critical components to computer-aided structure-based drug design. Despite advances in first-principle methods for predicting binding affinity, empirical scoring functions that are fast and only relatively accurate are still widely used in structure-based drug design. With the increasing availability of X-ray crystallographic structures in the Protein Data Bank and continuing application of biophysical methods such as isothermal titration calorimetry to measure thermodynamic parameters contributing to binding free energy, sufficient experimental data exists that scoring functions can now be derived by separating enthalpic (ΔH) and entropic (TΔS) contributions to binding free energy (ΔG). PHOENIX, a scoring function to predict binding affinities of protein-ligand complexes, utilizes the increasing availability of experimental data to improve binding affinity predictions by the following: model training and testing using high-resolution crystallographic data to minimize structural noise, independent models of enthalpic and entropic contributions fitted to thermodynamic parameters assumed to be thermodynamically biased to calculate binding free energy, use of shape and volume descriptors to better capture entropic contributions. A set of 42 descriptors and 112 protein-ligand complexes were used to derive functions using partial least-squares for change of enthalpy (ΔH) and change of entropy (TΔS) to calculate change of binding free energy (ΔG), resulting in a predictive r2 (r(pred)2) of 0.55 and a standard error (SE) of 1.34 kcal/mol. External validation using the 2009 version of the PDBbind "refined set" (n = 1612) resulted in a Pearson correlation coefficient (R(p)) of 0.575 and a mean error (ME) of 1.41 pK(d). Enthalpy and entropy predictions were of limited accuracy individually. However, their difference resulted in a relatively accurate binding free energy. While the development of an accurate and applicable

  9. Effect of polyglycerol esters additive on palm oil crystallization using focused beam reflectance measurement and differential scanning calorimetry. (United States)

    Saw, M H; Hishamuddin, E; Chong, C L; Yeoh, C B; Lim, W H


    The effect of 0.1-0.7% (w/w) of polyglycerol esters (PGEmix-8) on palm oil crystallization was studied using focused beam reflectance measurement (FBRM) to analyze the in-line changes of crystal size distribution during the crystallization. FBRM results show that 0.1-0.5% (w/w) of PGEmix-8 did not significantly affect nucleation but slightly retarded crystal growth. The use of 0.7% (w/w) additive showed greater heterogeneous nucleation compared to those with lower dosages of additive. Crystal growth was also greatly reduced when using 0.7% (w/w) dosage. The morphological study indicated that the palm oil crystals were smaller and more even in size than when more additive was added. Isothermal crystallization studies using differential scanning calorimetry (DSC) showed increased inhibitory effects on palm oil crystal growth with increasing concentration of PGEmix-8. These results imply that PGEmix-8 is a nucleation enhancing and crystal growth retarding additive in palm oil crystallization at 0.7% (w/w) dosage.

  10. Isothermal titration calorimetry for drug design: Precision of the enthalpy and binding constant measurements and comparison of the instruments. (United States)

    Linkuvienė, Vaida; Krainer, Georg; Chen, Wen-Yih; Matulis, Daumantas


    Isothermal titration calorimetry (ITC) is one of the most robust label- and immobilization-free techniques used to measure protein - small molecule interactions in drug design for the simultaneous determination of the binding affinity (ΔG) and the enthalpy (ΔH), both of which are important parameters for structure-thermodynamics correlations. It is important to evaluate the precision of the method and of various ITC instrument models by performing a single well-characterized reaction. The binding between carbonic anhydrase II and acetazolamide was measured by four ITC instruments - PEAQ-ITC, iTC200, VP-ITC, and MCS-ITC and the standard deviation of ΔG and ΔH was determined. Furthermore, the limit of an approach to reduce the protein concentration was studied for a high-affinity reaction (Kd = 0.3 nM), too tight to be measured by direct (non-displacement) ITC. Chemical validation of the enthalpy measurements is discussed.

  11. Enthalpy changes during photosynthetic water oxidation tracked by time-resolved calorimetry using a photothermal beam deflection technique. (United States)

    Krivanek, Roland; Dau, Holger; Haumann, Michael


    The energetics of the individual reaction steps in the catalytic cycle of photosynthetic water oxidation at the Mn(4)Ca complex of photosystem II (PSII) are of prime interest. We studied the electron transfer reactions in oxygen-evolving PSII membrane particles from spinach by a photothermal beam deflection technique, allowing for time-resolved calorimetry in the micro- to millisecond domain. For an ideal quantum yield of 100%, the enthalpy change, DeltaH, coupled to the formation of the radical pair Y(Z)(.+)Q(A)(-) (where Y(Z) is Tyr-161 of the D1 subunit of PSII) is estimated as -820 +/- 250 meV. For a lower quantum yield of 70%, the enthalpy change is estimated to be -400 +/- 250 meV. The observed nonthermal signal possibly is due to a contraction of the PSII protein volume (apparent DeltaV of about -13 A(3)). For the first time, the enthalpy change of the O(2)-evolving transition of the S-state cycle was monitored directly. Surprisingly, the reaction is only slightly exergonic. A value of DeltaH(S(3)-->S(0)) of -210 meV is estimated, but also an enthalpy change of zero is within the error range. A prominent nonthermal photothermal beam deflection signal (apparent DeltaV of about +42 A(3)) may reflect O(2) and proton release from the manganese complex, but also reorganization of the protein matrix.

  12. Differential scanning calorimetry studies of Se85Te15–Pb ( = 4, 6, 8 and 10) glasses

    Indian Academy of Sciences (India)

    N B Maharajan; N S Saxena; Deepika Bhandari; Mousa M Imran; D D Paudyal


    Results of differential scanning calorimetry (DSC) studies of Se85Te15–Pb ( = 4, 6, 8 and 10) glasses have been reported and discussed in this paper. The results have been analyzed on the basis of structural relaxation equation, Matusita’s equation and modified Kissinger’s equation. The activation energies of structural relaxation lie in between 226 and 593 kJ/mol. The crystallization growth is found to be onedimensional for all compositions. The activation energies of crystallization are found to be 100–136 kJ/mol by Matusita’s equation while 102–139 kJ/mol by modified Kissinger’s equation. The Hruby number (indicator of ease of glass forming and higher stability) is the highest for Se85Te9Pb6 glass while S factor (indicator of resistance to devitrification) is highest for Se85Te7Pb8 glass at all heating rates in our experiment. Further the highest resistance to devitrification has the highest value of structural activation energy and the activation energy of crystallization is maximum for the most stable glass by both Matusita’s equation and the modified Kissinger’s equation.

  13. Thermal and structural behavior of dioctadecyldimethylammonium bromide dispersions studied by differential scanning calorimetry and X-ray scattering.

    Directory of Open Access Journals (Sweden)

    Eloi Feitosa

    Full Text Available Dioctadecyldimethylammonium bromide (DODAB is a double chain cationic lipid, which assembles as bilayer structures in aqueous solution. The precise structures formed depend on, e.g., lipid concentration and temperature. We here combine differential scanning calorimetry (DSC and X-ray scattering (SAXS and WAXS to investigate the thermal and structural behavior of up to 120 mM DODAB in water within the temperature range 1-70 °C. Below 1 mM, this system is dominated by unilamellar vesicles (ULVs. Between 1 and 65 mM, ULVs and multilamellar structures (MLSs co-exist, while above 65 mM, the MLSs are the preferred structure. Depending on temperature, DSC and X-ray data show that the vesicles can be either in the subgel (SG, gel, or liquid crystalline (LC state, while the MLSs (with lattice distance d = 36.7 Å consist of interdigitated lamellae in the SG state, and ULVs in the LC state (no Bragg peak. Critical temperatures related to the thermal transitions of these bilayer structures obtained in the heating and cooling modes are reported, together with the corresponding transition enthalpies.

  14. A study of the relationship between water and anions of the Hofmeister series using pressure perturbation calorimetry. (United States)

    Bye, Jordan W; Falconer, Robert J


    Pressure perturbation calorimetry (PPC) was used to study the relationship between water and sodium salts with a range of different anions. At temperatures around 25 °C the heat on pressurisation (ΔQ) from 1 to 5 bar was negative for all solutions relative to pure water. The raw data showed that as the temperature rose, the gradient was positive relative to pure water and the transition temperature where ΔQ was zero was related to anion surface charge density and was more pronounced for the low-charge density anions. A three component model was developed comprising bulk water, the hydration layer and the solute to calculate the molar expansivity of the hydration layer around the ions in solution. The calculated molar expansivities of water in the hydration layer around the ions were consistently less than pure water. ΔQ at different disodium hydrogen phosphate concentrations showed that the change in molar enthalpy relative to pure water was not linear even as it approached infinite dilution suggesting that while hydration layers can be allocated to the water around ions this does not rule out interactions between water and ions extending beyond the immediate hydration layer.

  15. DMSO-Induced Dehydration of DPPC Membranes Studied by X-ray Diffraction, Small-Angle Neutron Scattering, and Calorimetry

    CERN Document Server

    Kiselev, M A; Kisselev, A M; Grabielle-Madelmond, C; Ollivon, M


    The influence of dimethyl sulfoxide (DMSO) on membrane thickness, multilamellar repeat distance, and phase transitions of 1,2-dipalmitoyl-sn-glycero-3-phosphatidylcholine (DPPC) was investigated by X-ray diffraction and small-angle neutron scattering (SANS). The differential scanning calorimetry (DSC) study of water freezing and ice melting was performed in the ternary DPPC /DMSO /water and binary DMSO /water systems. The methods applied demonstrated the differences in membrane structure in three sub-regions of the DMSO mole fraction (X_dmso): from 0.0 to 0.3 for the first, from 0.3 to 0.8 for the second, and from 0.9 to 1.0 for the third sub-region. The thickness of the intermembrane solvent at T =20C decreases from 14.4 +/- 1.8 A at X_dmso =0.0 to 7.8 +/- 1.8 A at X_dmso =0.1. The data were used to determine the number of free water molecules in the intermembrane space in the presence of DMSO. The results for 0.0 < X_dmso < 0.3 were explained in the framework of DMSO-induced dehydration of the interme...

  16. Analysis of the retrogradation of low starch concentration gels using differential scanning calorimetry, rheology, and nuclear magnetic resonance spectroscopy. (United States)

    Lewen, Kenneth S; Paeschke, Teri; Reid, Joshua; Molitor, Paul; Schmidt, Shelly J


    The retrogradation of 5, 10, 15, and 25% corn starch gels was measured using differential scanning calorimetry (DSC), rheology, and an array of NMR spectroscopy techniques. During the initial (retrogradation, an increase in G' corresponding to an increase in the number of solid protons participating in cross-relaxation (M(B)(0) was observed for all four concentrations studied. During the latter (>24 h) stage of retrogradation, amylopectin recrystallization becomes the dominant process as measured by an increase in deltaH(r) for the 25% starch gel, which corresponded to a further increase in. A decrease in the molecular mobility of the liquid component was observed by decreases in (17)O T(2), (1)H D(0), and T(2A). The value for T(2B) (the solid transverse relaxation time) did not change with concentration or time indicating that the mobility of the solid component does not change over time despite the conversion of the highly mobile starch fraction to the less mobile solid state during retrogradation.

  17. The thermal stability and domain interactions of the mannitol permease of Escherichia coli. A differential scanning calorimetry study. (United States)

    Meijberg, W; Schuurman-Wolters, G K; Boer, H; Scheek, R M; Robillard, G T


    The thermal stability and domain interactions in the mannitol transporter from Escherichia coli, enzyme IImtl, have been studied by differential scanning calorimetry. To this end, the wild type enzyme, IICBAmtl, as well as IICBmtl and IICmtl, were reconstituted into a dimyristoylphosphatidylcholine lipid bilayer. The changes in the gel to liquid crystalline transition of the lipid indicated that the protein was inserted into the membrane, disturbing a total of approximately 40 lipid molecules/protein molecule. The thermal unfolding profile of EIImtl exhibited three separate transitions, two of which were overlapping, that could be assigned to structural domains in the protein. Treatment with trypsin, resulting in the degradation of the water-soluble part of the enzyme while leaving the binding and translocation capability of the enzyme intact, resulted in a decrease of the Tm and enthalpy of unfolding of the membrane-embedded C domain. This effect was much more apparent in the presence of the substrate but only partly so in the presence of the substrate analog perseitol. These results are consistent with a recently proposed model (Meijberg, W., Schuurman-Wolters, G. K., and Robillard, G. T. (1998) J. Biol. Chem. 273, 7949-7946), in which the B domain takes part in the conformational changes during the substrate binding process.

  18. Characterization of a Friction Stir Weld in Aluminum Alloy 7055 Using Microhardness, Electrical Conductivity, and Differential Scanning Calorimetry (DSC) (United States)

    Bush, Ralph; Kiyota, Michelle; Kiyota, Catherine


    Optical microscopy, microhardness, electrical conductivity, and differential scanning calorimetry (DSC) were used to characterize the microstructure, hardness, and precipitate structure as a function of position in a friction stir weld, naturally aged for 10 years, in aluminum alloy 7055. Results are shown for the as-welded/naturally aged condition and for a weld that was post-aged using a -T76 regimen. The grain structure and microhardness results reveal the expected central recrystallized region, a thermo-mechanical affected zone (TMAZ), and heat-affected zone (HAZ) with typical changes in microhardness. DSC scans for the as-welded/naturally aged condition indicate a precipitate structure similar to that of a naturally aged condition in the central recrystallized region. Maximum precipitate coarsening and overaging occurs near the TMAZ/HAZ boundary with reduced precipitate dissolution and coarsening as the distance from the weld increases. The post-weld aging resulted in the transformation of GP zones to more stable precipitates plus coarsening of the more stable η' and η precipitates. A combination of DSC testing and CALPHAD calculations allowed calculation of precipitate volume fraction in the HAZ. The precipitate volume fraction decreased monotonically from 0.052 in the baseline material to 0.044 at the TMAZ/HAZ interface.

  19. Interaction between Heparin and Fibronectin:Using Quartz Crystal Microbalance with Dissipation, Immunochemistry and Isothermal Titration Calorimetry

    Institute of Scientific and Technical Information of China (English)

    LI Guicai; WANG Caiping; YANG Ping; ZHOU Jie; ZHU Pingchuan


    The adsorption behavior of heparin and ifbronectin was studied by quartz crystal microbalance with dissipation (QCM-D), and the interaction between heparin and fibronectin was evaluated using immunochemistry and isothermal titration calorimetry (ITC) measurement. The results showed that there was competitive adsorption between heparin and fibronectin, and the preadsorption of fibronectin could prevent subsequent heparin adsorption to some extent, and the adsorbed Hep/Fn complex on the surface was in a rigid form. The bioactivity of heparin and ifbronectin could be affected by the bulk concentration of each, and both heparin and ifbronectin in Hep/Fn complex formed under pH 4 condition displayed larger bioactivity than that formed under pH 7 condition. Moreover, the ifbronectin showed more exposed cell-binding sites at the pH value lower than physiological condition. The results of ITC further suggested that the interaction between heparin and ifbronectin under pH 4 was stronger than under pH 7, and the complex was also more stable. The study brings forth the detailed interaction between heparin and ifbronectin, which will be helpful for better understanding the interaction mechanism of the two biomolecules. The results may be potentially useful for the development of new generation of cardiovascular biomaterials.

  20. Real-time monitoring of the setting reaction of brushite-forming cement using isothermal differential scanning calorimetry. (United States)

    Hofmann, M P; Nazhat, S N; Gbureck, U; Barralet, J E


    The setting behavior of a brushite-forming cement (beta-tricalcium phosphate/mono calcium monophosphate) was investigated using an indentation technique (the Gillmore needles method) and isothermal differential scanning calorimetry (DSC). The two objectives of the study were to investigate whether DSC could be used to real-time monitor a fast-setting calcium phosphate cement (CPC) and to determine if it is possible to correlate DSC results directly with conventional setting-time measurements. Best-fit linear correlation analysis revealed that both the initial and final setting time (T(i) and T(f)) measured by indentation were strongly correlated to the maximum heat flow measured with DSC. It seems therefore possible to predict the setting times, usually achieved with user dependent indentation methods, of this specific fast setting CPC on the basis of objective DSC measurements. The drawbacks of DSC, however, are its overall complexity and expense and the fact that only exothermal reactions can be investigated in comparison to the Gillmore needles method, furthermore, it is not possible to monitor the complete reaction as the first 2 or 3 min are lost due to sample preparation and apparatus set up.

  1. Estimate of the thermal diffusivity of films with a sandwich structure by using pulsed transient analysis and AC calorimetry

    CERN Document Server

    Choi, M H; Park, C H; Kim, S W; Hahn, S H; Seong, D J; Kim, J C


    The thermal diffusivity in a direction perpendicular to an epoxy resin film sandwiched between two identical metal layers was measured not only by using a pulsed transient analysis but also by using AC calorimetry. The pulsed transient analysis utilized the surface-temperature decay of the heating pulse from a Q-switched, 2nd harmonic generated Nd:YAG laser. The temperature decay was measured with a HgCdTe infrared detector. After data collection, a nonlinear least-squares regression was performed to estimate the optimal values of several separate thermal parameters by fitting the data to the solutions. Additionally, the thermal diffusivity of the samples was obtained by using the AC calorimetric method which measured the frequency-dependent phase changes of the samples. The thermal diffusivities obtained by the two methods were in the range of 0.07 approx 0.09 x 10 sup - sup 2 cm sup 2 /s, agreed within 8 %, but were lower than the literature values. To improve the results, the contact heat resistance from t...

  2. Intrinsic thermodynamics of 4-substituted-2,3,5,6-tetrafluorobenzenesulfonamide binding to carbonic anhydrases by isothermal titration calorimetry. (United States)

    Zubrienė, Asta; Smirnovienė, Joana; Smirnov, Alexey; Morkūnaitė, Vaida; Michailovienė, Vilma; Jachno, Jelena; Juozapaitienė, Vaida; Norvaišas, Povilas; Manakova, Elena; Gražulis, Saulius; Matulis, Daumantas


    Para substituted tetrafluorobenzenesulfonamides bind to carbonic anhydrases (CAs) extremely tightly and exhibit some of the strongest known protein-small ligand interactions, reaching an intrinsic affinity of 2 pM as determined by displacement isothermal titration calorimetry (ITC). The enthalpy and entropy of binding to five CA isoforms were measured by ITC in two buffers of different protonation enthalpies. The pKa values of compound sulfonamide groups were measured potentiometrically and spectrophotometrically, and enthalpies of protonation were measured by ITC in order to evaluate the proton linkage contributions to the observed binding thermodynamics. Intrinsic means the affinity of a sulfonamide anion for the Zn bound water form of CAs. Fluorination of the benzene ring significantly enhanced the observed affinities as it increased the fraction of deprotonated ligand while having little impact on intrinsic affinities. Intrinsic enthalpy contributions to the binding affinity were dominant over entropy and were more exothermic for CA I than for other CA isoforms. Thermodynamic measurements together with the X-ray crystallographic structures of protein-ligand complexes enabled analysis of structure-activity relationships in this enzyme ligand system.

  3. Interaction of a dietary fiber (pectin) with gastrointestinal components (bile salts, calcium, and lipase): a calorimetry, electrophoresis, and turbidity study. (United States)

    Espinal-Ruiz, Mauricio; Parada-Alfonso, Fabián; Restrepo-Sánchez, Luz-Patricia; Narváez-Cuenca, Carlos-Eduardo; McClements, David Julian


    An in vitro gastrointestinal model consisting of oral, gastric, and intestinal phases was used to elucidate the impact of pectin on the digestion of emulsified lipids. Pectin reduced the extent of lipid digestion, which was attributed to its binding interactions with specific gastrointestinal components. The interaction of pectin with bile salts, lipase, CaCl2, and NaCl was therefore investigated by turbidity, microstructure, electrophoresis, and isothermal titration calorimetry (ITC) at pH 7.0 and 37 °C. ITC showed that the interaction of pectin was endothermic with bile salts, but exothermic with CaCl2, NaCl, and lipase. Electrophoresis, microstructure, and turbidity measurements showed that anionic pectin formed electrostatic complexes with calcium ions, which may have decreased lipid digestion due to increased lipid flocculation or microgel formation because this would reduce the surface area of lipid exposed to the lipase. This research provides valuable insights into the physicochemical and molecular mechanisms of the interaction of pectin with gastrointestinal components that may affect the rate and extent of lipid digestion.

  4. Influence of rare earth elements on solidification behavior of a high speed steel for roll using differential scanning calorimetry

    Institute of Scientific and Technical Information of China (English)

    WANG Mingjia; CHEN Lei; WANG Zixi; BAO Er


    The influence of rare earths (RE) on solidification behavior of a high speed steel for roll was investigated by using differential scanning calorimetry (DSC) in combination of microstructure analysis.It was found that the sequence of solidification was L→γ,L→γ+MC,L→γ+M2C,L→γ+M6C,respectively.The start temperature and the latent heat liberated by unit mass of L→γ and L→γ+MC increased with increase of RE addition,indicating that RE could trigger the crystallization of the primary γ and the MC carbide more effectively.The promoting effect of RE on the heterogeneous nucleation was believed to be an important cause of this effect.Grain refinement,discontinuous network of eutectic carbides and disperse and finer MC were observed in the samples with RE addition,moreover,RES could act as the heterogeneous nucleus of the MC.RE addition was favorable for stable M6C at the expense of the metastable M2C.

  5. The interaction of phenolic acids with Fe(III) in the presence of citrate as studied by isothermal titration calorimetry. (United States)

    Yang, Senpei; Bai, Guangling; Chen, Lingli; Shen, Qun; Diao, Xianmin; Zhao, Guanghua


    Under physiological conditions, exogenous chelators such as polyphenols might interact with non-protein bound ferric complexes, such as Fe(III)-citrate. Additionally, Fe(III) and citrate are widely distributed in various fruits and vegetables which are also rich in phenolic acids. In this study, we focus on the interaction between phenolic acids (gallic acid, methyl gallate and protocatechuic acid) and Fe(III) in the presence of excessive citrate by isothermal titration calorimetry (ITC) for thermodynamic studies, and stopped-flow absorption spectrometry for fast kinetic studies. Results reveal that all of these three phenolic acids can bind to the Fe(III) with the same stoichiometry (3:1). Moreover, the binding constants of these three compounds with Fe(III) are greatly dependent on ligand structure, and are much higher than that of Fe(III)-citrate. Based on their stoichiometry and superhigh binding constants, it is most likely that these three phenolic acids can displace the citrate to bind with one iron(III) ion to form a stable octahedral geometric structure, albeit at different rates. These findings shed light on the interaction between phenolic acids and Fe(III) in the presence of citrate under either physiological conditions or in a food system.

  6. Unraveling the thermodynamics and kinetics of RNA assembly: surface plasmon resonance, isothermal titration calorimetry, and circular dichroism. (United States)

    Hoogstraten, Charles G; Sumita, Minako; White, Neil A


    The mechanisms and driving forces of the assembly of RNA tertiary structure are a topic of much current interest. In several systems, including our own work in the docking transition of the hairpin ribozyme, intramolecular RNA tertiary folding has been converted into an intermolecular binding event, allowing the full power of contemporary biophysical techniques to be brought to bear on the analysis. We review the use of three such methods: circular dichroism to isolate the binding of multivalent cations coupled to tertiary assembly, surface plasmon resonance to determine the rates of association and dissociation, and isothermal titration calorimetry to dissect the thermodynamic contributions to RNA assembly events. We pay particular attention to practical aspects of these studies, such as careful preparation of samples with fixed free concentrations of cations in order to avoid errors due to ion depletion effects that are common in RNA systems. Examples of applications from our own work with the hairpin ribozyme are shown. Distinctions among the data handling procedures for the various techniques used and solution conditions encountered are also discussed.

  7. Assessment of lifetime resolution limits in time-resolved photoacoustic calorimetry vs. transducer frequencies: setting the stage for picosecond resolution. (United States)

    Schaberle, Fábio A; Rego Filho, Francisco de Assis M G; Reis, Luís A; Arnaut, Luis G


    Time-resolved photoacoustic calorimetry (PAC) gives access to lifetimes and energy fractions of reaction intermediates by deconvolution of the photoacoustic wave of a sample (E-wave) with that of the instrumental response (T-wave). The ability to discriminate between short lifetimes increases with transducer frequencies employed to detect the PAC waves. We investigate the lifetime resolution limits of PAC as a function of the transducer frequencies using the instrumental response obtained with the photoacoustic reference 2-hydroxybenzophenone in toluene or acetonitrile. The instrumental response was obtained for a set of transducers with central frequencies ranging from 0.5 MHz up to 225 MHz. The simulated dependence of the lifetime resolution with the transducer frequencies was anchored on experimental data obtained for the singlet state of naphthalene with a 2.25 MHz transducer. The shortest lifetime resolved with the 2.25 MHz transducer was 19 ns and our modelling of the transducer responses indicates that sub-nanosecond lifetimes of photoacoustic transients can be resolved with transducers of central frequencies above 100 MHz.

  8. Weak interactions in clobazam-lactose mixtures examined by differential scanning calorimetry: Comparison with the captopril-lactose system

    Energy Technology Data Exchange (ETDEWEB)

    Toscani, S. [Departement de Chimie - UMR 6226, Faculte des Sciences, Universite de Rennes 1, Batiment 10B, 263 avenue du General Leclerc, F-35042 Rennes Cedex (France); Cornevin, L. [Universite de Rennes 1, Faculte de Pharmacie, 2 Avenue Leon Bernard, F-35043 Rennes Cedex (France); Burgot, G., E-mail: [Universite de Rennes 1, Faculte de Pharmacie, Laboratoire de Chimie Analytique, EA 1274 ' Mouvement, sports, sante' , 2 Avenue Leon Bernard, F-35043 Rennes Cedex (France); CHGR Rennes, Pole Medico-Technique Pharmacie, F-35703 Rennes Cedex (France)


    Highlights: Black-Right-Pointing-Pointer Thermodynamic and kinetic parameters of weak interactions in binary systems by DSC. Black-Right-Pointing-Pointer Energy-barrier decrease for lactose dehydration induced by clobazam. Black-Right-Pointing-Pointer Recrystallisation of metastable liquid clobazam induced by anhydrous alpha lactose. Black-Right-Pointing-Pointer Decrease of lactose dehydration temperature in binary mixtures with captopril. Black-Right-Pointing-Pointer Increase of lactose dehydration enthalpy in binary mixtures with captopril. - Abstract: The thermal behaviour of binary mixtures of two drugs (clobazam and captopril, respectively) and a pharmaceutical excipient (lactose monohydrate) was measured with differential scanning calorimetry to determine thermodynamic and kinetic parameters (dehydration and melting enthalpies and dehydration and glass-transition activation energies) which might be affected by intermolecular interactions. A kinetic study showed that lactose dehydration is not a single-step conversion and that clobazam contributed to reduce the energy barrier for the bulk dehydration of the excipient. On the other hand, the physical interactions between metastable liquid clobazam and crystalline anhydrous {alpha}-lactose obtained from monohydrate dehydration gave rise to the recrystallisation of clobazam. In the captopril-lactose system, the liquid captopril influenced the lactose dehydration: a sharp increase of the dehydration enthalpy and a concurrent reduction of the dehydration temperature were observed. Finally, it turned out that solid-phase transitions were enhanced by the contact with a liquid phase.

  9. Temperature dependence of isothermal curing reaction of epoxy resin studied by modulated differential scanning calorimetry and infrared spectroscopy (United States)

    Yamasaki, Hideki; Morita, Shigeaki


    The isothermal curing reaction of bisphenol A diglycidyl ether epoxy (BADGE) resin with dimethyl diamino methane (DDM) hardener was investigated by means of modulated differential scanning calorimetry (MDSC) and infrared (IR) spectroscopy at 90, 100 and 120 °C. It was confirmed that the behavior of the bands assigned to the epoxy group, ether group, secondary amine and tertiary amine were different depending on temperature. At stoichiometric amounts of DDM and BADGE, the reaction at 90 and 100 °C compared with that at 120 °C, the oxirane or glycidyl group of epoxy resin and the secondary amine group were left even if reached at the end point of the reaction, and those reaction proceed as diffusion control continues longer. The reaction between 90 and 100 °C, it was different from the reactivity of the epoxy resin, various amino groups and ether group. Hence, the cured epoxy resin had a different composition. Moreover, it was also verified that the reactivity of the various amino groups and the etherification were difference, therefore, it was suggested that the cross-linkage construction of the cured resin at different temperature was different.

  10. Quantitative assays of the amount of diethylenetriaminepentaacetic acid conjugated to water-soluble polymers using isothermal titration calorimetry and colorimetry. (United States)

    Gouin, S; Winnik, F M


    The level of conjugation of diethylenetriaminepentaacetic acid (DTPA) to the polysaccharide sodium hyaluronan (HA) has been measured by a colorimetric assay, isothermal titration calorimetry (ITC), and (1)H NMR spectroscopy. The colorimetric assay is based on the red shift, upon complexation with gadolinium ion (Gd3+), of the wavelength of maximum absorption of the dye arsenazo III. It can be performed in a few minutes using as little as 10 microg of polymer with a detection limit of approximately 0.03 mmol of DTPA (gram of polymer)-1. The ITC measurements yield values of the amount of DTPA linked to HA identical to those obtained by colorimetry. The levels of DTPA conjugation calculated by integration of signals at 3.1-3.2 ppm (DTPA protons) and at 2.0 ppm (HA acetamide protons) in the 1H NMR spectrum of HA-DTPA are consistently overestimated by a factor of approximately 2, compared to the data obtained by ITC and colorimetry. The longer relaxation times of protons of the polymer backbone, compared to those of protons attached to the freely moving DTPA side-chains may account for the discrepancy.

  11. Raman scattering boson peak and differential scanning calorimetry studies of the glass transition in tellurium-zinc oxide glasses

    Energy Technology Data Exchange (ETDEWEB)

    Stavrou, E; Tsiantos, C; Tsopouridou, R D; Kripotou, S; Kontos, A G; Raptis, C [Department of Physics, National Technical University of Athens, GR-15780 Athens (Greece); Capoen, B; Bouazaoui, M [Laboratoire de Physique des Lasers, Atomes et Molecules (CNRS, UMR 8523), Batiment P-5, Centre d' Etudes et de Recherches Lasers et Applications (CERLA-FR CNRS 2416), Universite de Sciences et Technologies de Lille, F-59655 Villeneuve d' Ascq Cedex (France); Turrell, S; Khatir, S, E-mail: craptis@central.ntua.g [Laboratoire de Spectrochimie Infrarouge et Raman (CNRS 8516), Batiment C-5, Centre d' Etudes et de Recherches Lasers et Applications (CERLA-FR CNRS 2416), Universite de Sciences et Technologies de Lille, F-59655 Villeneuve d' Ascq Cedex (France)


    Raman scattering and differential scanning calorimetry (DSC) measurements have been carried out on four mixed tellurium-zinc oxide (TeO{sub 2}){sub 1-x}(ZnO){sub x} (x = 0.1, 0.2, 0.3, 0.4) glasses under variable temperature, with particular attention being given to the respective glass transition region. From the DSC measurements, the glass transition temperature T{sub g} has been determined for each glass, showing a monotonous decrease of T{sub g} with increasing ZnO content. The Raman study is focused on the low-frequency band of the glasses, the so-called boson peak (BP), whose frequency undergoes an abrupt decrease at a temperature T{sub d} very close to the respective T{sub g} values obtained by DSC. These results show that the BP is highly sensitive to dynamical effects over the glass transition and provides a means for an equally reliable (to DSC) determination of T{sub g} in tellurite glasses and other network glasses. The discontinuous temperature dependence of the BP frequency at the glass transition, along with the absence of such a behaviour by the high-frequency Raman bands (due to local atomic vibrations), indicates that marked changes of the medium range order (MRO) occur at T{sub g} and confirms the correlation between the BP and the MRO of glasses.

  12. Isothermal titration calorimetry study of the interaction of sweeteners with fullerenols as an artificial sweet taste receptor model. (United States)

    Chen, Zhong-Xiu; Guo, Gang-Min; Deng, Shao-Ping


    A fullerenol-based synthetic sweetness receptor model, consisting of polyhydroxy groups for potential hydrogen bond donor along with a spherical hydrophobic center, was proposed according to the widely accepted sweetness hypothesis. An isothermal titration calorimetry (ITC) technique was used to study mimetic interaction of this sweet receptor model with a series of sweeteners having increasing sweetness intensity. The results showed that ITC is an effective method to provide thorough and precise characterization of the energies of molecular complex formation. Binding of all of the studied sweeteners with fullerenols was found through two sets of site models. More heat was released from sweeter synthetic compounds binding with fullerenols than from less sweet carbohydrates. The results imply that hydrogen bond formation is necessary for the sweeteners to bind to the fullerenol receptor in the first stage, whereas hydrophobic effect and conformation changes that lead to favorable entropy changes occur in most cases. The preliminary results of this study help to cover the lack of information about the thermodynamic basis of understanding of the initiation of the sweet sensation. It also adds complementary physicochemical measurements available for comparison with the sweetness hypothesis. On the other hand, a correlation between the thermodynamic parameters and sweetness intensity has been made as well, which exhibits potential as a useful tool in sensory analysis.

  13. Thermal decomposition study of monovarietal extra virgin olive oil by simultaneous thermogravimetry/differential scanning calorimetry: relation with chemical composition. (United States)

    Vecchio, Stefano; Cerretani, Lorenzo; Bendini, Alessandra; Chiavaro, Emma


    Thermal decomposition of 12 monovarietal extra virgin olive oils from different geographical origins (eight from Italy, two from Spain, and the others from Tunisia) was evaluated by simultaneous thermogravimetry (TG) and differential scanning calorimetry (DSC) analyses. All extra virgin olive oils showed a complex multistep decomposition pattern with the first step that exhibited a quite different profile among samples. Thermal properties of the two peaks obtained by the deconvolution of the first step of decomposition by DSC were related to the chemical composition of the samples (triacylglycerols, fatty acids, total phenols and antioxidant activity). Onset temperatures of the thermal decomposition transition and T(p) values of both deconvoluted peaks as well as the sum of enthalpy were found to exhibit statistically significant correlations with chemical components of the samples, in particular palmitic and oleic acids and related triacylglycerols. Activation energy values of the second deconvoluted peak obtained by the application of kinetic procedure to the first step of decomposition were also found to be highly statistically correlated to the chemical composition, and a stability scale among samples was proposed on the basis of its values.

  14. Analysis of Mesoscopic Structured 2-Propanol/Water Mixtures Using Pressure Perturbation Calorimetry and Molecular Dynamic Simulation. (United States)

    Bye, Jordan W; Freeman, Colin L; Howard, John D; Herz, Gregor; McGregor, James; Falconer, Robert J


    In this paper we demonstrate the application of pressure perturbation calorimetry (PPC) to the characterization of 2-propanol/water mixtures. PPC of different 2-propanol/water mixtures provides two useful measurements: (i) the change in heat (ΔQ); and (ii) the [Formula: see text] value. The results demonstrate that the ΔQ values of the mixtures deviate from that expected for a random mixture, with a maximum at ~20-25 mol% 2-propanol. This coincides with the concentration at which molecular dynamics (MD) simulations show a maximum deviation from random distribution, and also the point at which alcohol-alcohol hydrogen bonds become dominant over alcohol-water hydrogen bonds. Furthermore, the [Formula: see text] value showed transitions at 2.5 mol% 2-propanol and at approximately 14 mol% 2-propanol. Below 2.5 mol% 2-propanol the values of [Formula: see text] are negative; this is indicative of the presence of isolated 2-propanol molecules surrounded by water molecules. Above 2.5 mol% 2-propanol [Formula: see text] rises, reaching a maximum at ~14 mol% corresponding to a point where mixed alcohol-water networks are thought to dominate. The values and trends identified by PPC show excellent agreement not only with those obtained from MD simulations but also with results in the literature derived using viscometry, THz spectroscopy, NMR and neutron diffraction.

  15. Characterization of the kinetic and thermodynamic landscape of RNA folding using a novel application of isothermal titration calorimetry. (United States)

    Vander Meulen, Kirk A; Butcher, Samuel E


    A novel isothermal titration calorimetry (ITC) method was applied to investigate RNA helical packing driven by the GAAA tetraloop-receptor interaction in magnesium and potassium solutions. Both the kinetics and thermodynamics were obtained in individual ITC experiments, and analysis of the kinetic data over a range of temperatures provided Arrhenius activation energies (ΔH(‡)) and Eyring transition state entropies (ΔS(‡)). The resulting rich dataset reveals strongly contrasting kinetic and thermodynamic profiles for this RNA folding system when stabilized by potassium versus magnesium. In potassium, association is highly exothermic (ΔH(25°C) = -41.6 ± 1.2 kcal/mol in 150 mM KCl) and the transition state is enthalpically barrierless (ΔH(‡) = -0.6 ± 0.5). These parameters are significantly positively shifted in magnesium (ΔH(25°C) = -20.5 ± 2.1 kcal/mol, ΔH(‡) = 7.3 ± 2.2 kcal/mol in 0.5 mM MgCl(2)). Mixed salt solutions approximating physiological conditions exhibit an intermediate thermodynamic character. The cation-dependent thermodynamic landscape may reflect either a salt-dependent unbound receptor conformation, or alternatively and more generally, it may reflect a small per-cation enthalpic penalty associated with folding-coupled magnesium uptake.

  16. Theoretical Aspects of Differential Scanning Calorimetry as a Tool for the Studies of Equilibrium Thermodynamics in Pharmaceutical Solid Phase Transitions. (United States)

    Faroongsarng, Damrongsak


    Although differential scanning calorimetry (DSC) is a non-equilibrium technique, it has been used to gain energetic information that involves phase equilibria. DSC has been widely used to characterize the equilibrium melting parameters of small organic pharmaceutical compounds. An understanding of how DSC measures an equilibrium event could make for a better interpretation of the results. The aim of this mini-review was to provide a theoretical insight into the DSC measurement to obtain the equilibrium thermodynamics of a phase transition especially the melting process. It was demonstrated that the heat quantity obtained from the DSC thermogram (ΔH) was related to the thermodynamic enthalpy of the phase transition (ΔH (P) ) via: ΔH = ΔH (P) /(1 + K (- 1)) where K was the equilibrium constant. In melting, the solid and liquefied phases presumably coexist resulting in a null Gibbs free energy that produces an infinitely larger K. Thus, ΔH could be interpreted as ΔH (P). Issues of DSC investigations on melting behavior of crystalline solids including polymorphism, degradation impurity due to heating in situ, and eutectic melting were discussed. In addition, DSC has been a tool for determination of the impurity based on an ideal solution of the melt that is one of the official methods used to establish the reference standard.

  17. Adiabatic calorimetry test of the reaction kinetics and self-heating model for 18650 Li-ion cells in various states of charge (United States)

    Chen, Wei-Chun; Wang, Yih-Wen; Shu, Chi-Min


    Use of adiabatic calorimetry to characterise thermal runaway of Li-ion cells is a crucial technique in battery safety testing. Various states of charge (SoC) of Li-ion cells were investigated to ascertain their thermal runaway features using a Vent Sizing Package 2 (VSP2) adiabatic calorimeter. To evaluate the thermal runaway characteristics, the temperature-pressure-time trajectories of commercial cylindrical cells were tested, and it was found that cells at a SoC of greater than 50% were subject to thermal explosion at elevated temperatures. Calorimetry data from various 18650 Li-ion cells with different SoC were used to calculate the thermal explosion energies and chemical kinetics; furthermore, a novel self-heating model based on a pseudo-zero-order reaction that follows the Arrhenius equation was found to be applicable for studying the exothermic reaction of a charged cell.

  18. Internal short circuit and accelerated rate calorimetry tests of lithium-ion cells: Considerations for methane-air intrinsic safety and explosion proof/flameproof protection methods


    Dubaniewicz, Thomas H.; DuCarme, Joseph P.


    Researchers with the National Institute for Occupational Safety and Health (NIOSH) studied the potential for lithium-ion cell thermal runaway from an internal short circuit in equipment for use in underground coal mines. In this third phase of the study, researchers compared plastic wedge crush-induced internal short circuit tests of selected lithium-ion cells within methane (CH4)-air mixtures with accelerated rate calorimetry tests of similar cells. Plastic wedge crush test results with meta...

  19. Avalanche correlations in the martensitic transition of a Cu-Zn-Al shape memory alloy: analysis of acoustic emission and calorimetry. (United States)

    Baró, Jordi; Martín-Olalla, José-María; Romero, Francisco Javier; Gallardo, María Carmen; Salje, Ekhard K H; Vives, Eduard; Planes, Antoni


    The existence of temporal correlations during the intermittent dynamics of a thermally driven structural phase transition is studied in a Cu-Zn-Al alloy. The sequence of avalanches is observed by means of two techniques: acoustic emission and high sensitivity calorimetry. Both methods reveal the existence of event clustering in a way that is equivalent to the Omori correlations between aftershocks in earthquakes as are commonly used in seismology.

  20. Study of the interaction between glucosamine hydrochloride and sodium dodecylsulphate micelles using conductometric, isothermal calorimetry, zeta-potential titrations, and NMR NOESY


    Alves,Marcos Roberto de Abreu; VIRTUOSO, Luciano Sindra


    The aim of this work was to investigate the influence of an anti-inflammatory agent, the bulky counterion named glucosamine (Gl+), in sodium dodecylsulphate (SDS) in 2 ways: 1) by titration of SDS solutions with different concentrations of Gl+; and 2) by titration of Gl+ with SDS solution with concentration close to the critical micellar concentration (cmc) (7.7 mM). In procedure 1, micellisation study by isothermal titration calorimetry (ITC) showed that the increase in Gl+ concentrat...

  1. Application of method of differential scanning calorimetry is for the study of mechanism of gelation of composition on the basis of carbonanotube

    Directory of Open Access Journals (Sweden)

    Е. Г. Привалко


    Full Text Available By differential scanning calorimetry method have been studied influence of nanotubes upon structure mechanism of gelation of composition. It is shown that particles of carbonanotube are active nucleation agents for crystallization of polipropilen. Crystallization takes place on the mechanism of the strained matrix. After by the got results, at content of carbonanotube of 1-2 % there are the best terms for crystallization of polymeric matrix

  2. Isothermal titration calorimetry as a powerful tool to quantify and better understand agglomeration mechanisms during interaction processes between TiO2 nanoparticles and humic acids


    Loosli, Frédéric; Vitorazi, Letícia; Berret, Jean-François; Stoll, Serge


    The association processes between engineered TiO2 nanoparticles and Suwannee River humic acids are investigated by isothermal titration calorimetry and by measuring the exchanged heat during the binding process, allowing the determination of thermodynamic (change in enthalpy, Gibbs free energy and entropy) and reaction (binding affinity constant, reaction stoichiometry) parameters. Our results indicate that strong TiO2–Suwannee River humic acid interactions are entropically and enthalpically ...

  3. Adsorption and adhesion energies of Pb on (1×1)-Mo2C/Mo(100) by calorimetry (United States)

    Smedh, M.; Diaz, S. F.; Campbell, C. T.


    This paper reports calorimetric measurements of the adsorption energy of Pb onto an ordered 1×1 Mo carbide thin film on Mo(100) at 300 K, as well as measurements of the sticking probability and film growth mode of this system. The heat of adsorption is constant up to a Pb coverage of 0.5 ML, with a value of 244.5±2 kJ/mol. Between 0.5 and 0.9 ML the heat decreases linearly to a value close to the heat of sublimation for bulk Pb, where it remains at higher coverages. The sticking probability increases linearly for submonolayer coverages from an initial value of about 0.97. At coverages above 0.8 0.9 ML it stays constant at 0.994. The growth mode is Stranski-Krastanov, with two-dimensional (2D) growth up to 0.9 ML and 3D island growth thereafter. A growth model, consisting of Pb adatoms not filling nearest neighbor sites up to 0.5 ML and random filling of nearest neighbor sites at higher coverages, provides a very good fit to the calorimetry data. The model involves a 14-kJ/mol Pb-Pb pairwise repulsion at nearest neighbor sites, as well as a 14-kJ/mol relaxation of the repulsion by slight relaxations from the site centers, when not constrained by other Pb nearest neighbors. The adhesion energy, from the integral heat of adsorption for multilayer Pb, is 194±10 μJ/cm2.

  4. State of the water in crosslinked sulfonated poly(ether ether ketone). Two-dimensional differential scanning calorimetry correlation mapping

    Energy Technology Data Exchange (ETDEWEB)

    Al Lafi, Abdul G. [Department of Chemistry, Atomic Energy Commission, Damascus, P.O. Box 6091 (Syrian Arab Republic); Hay, James N., E-mail: [The School of Metallurgy and Materials, College of Physical Sciences and Engineering, University of Birmingham, Edgbaston, Birmingham B15 2TT (United Kingdom)


    Highlights: • 2D-DSC mapping was applied to analyze the heat flow responses of hydrated crosslinked sPEEK. • Two types of loosely bond water were observed. • The first was bond to the sulfonic acid groups and increased with ion exchange capacity. • The second was attributed to the polar groups introduced by ions irradiation and increased with crosslinking degree. • DSC combined with 2D mapping provides a powerful tool for polymer structural determination. - Abstract: This paper reports the first application of two-dimensional differential scanning calorimetry correlation mapping, 2D-DSC-CM to analyze the heat flow responses of sulphonated poly(ether ether ketone), sPEEK, films having different ion exchange capacity and degrees of crosslinks. With the help of high resolution and high sensitivity of 2D-DSC-CM, it was possible to locate two types of loosely bound water within the structure of crosslinked sPEEK. The first was bound to the sulfonic acid groups and dependent on the ion exchange capacity of the sPEEK. The second was bound to other polar groups, either introduced by irradiation with ions and dependent on the crosslinking degree or present in the polymer such as the carbonyl groups or terminal units. The results suggest that the ability of the sulfonic acid groups in the crosslinked sPEEK membranes to adsorb water molecules is increased by crosslinking, probably due to the better close packing efficiency of the crosslinked samples. DSC combined with 2D correlation mapping provides a fast and powerful tool for polymer structural determination.

  5. Detection of cervical cancer biomarker patterns in blood plasma and urine by differential scanning calorimetry and mass spectrometry.

    Directory of Open Access Journals (Sweden)

    Nichola C Garbett

    Full Text Available Improved methods for the accurate identification of both the presence and severity of cervical intraepithelial neoplasia (CIN and extent of spread of invasive carcinomas of the cervix (IC are needed. Differential scanning calorimetry (DSC has recently been shown to detect specific changes in the thermal behavior of blood plasma proteins in several diseases. This methodology is being explored to provide a complementary approach for screening of cervical disease. The present study evaluated the utility of DSC in differentiating between healthy controls, increasing severity of CIN and early and advanced IC. Significant discrimination was apparent relative to the extent of disease with no clear effect of demographic factors such as age, ethnicity, smoking status and parity. Of most clinical relevance, there was strong differentiation of CIN from healthy controls and IC, and amongst patients with IC between FIGO Stage I and advanced cancer. The observed disease-specific changes in DSC profiles (thermograms were hypothesized to reflect differential expression of disease biomarkers that subsequently bound to and affected the thermal behavior of the most abundant plasma proteins. The effect of interacting biomarkers can be inferred from the modulation of thermograms but cannot be directly identified by DSC. To investigate the nature of the proposed interactions, mass spectrometry (MS analyses were employed. Quantitative assessment of the low molecular weight protein fragments of plasma and urine samples revealed a small list of peptides whose abundance was correlated with the extent of cervical disease, with the most striking plasma peptidome data supporting the interactome theory of peptide portioning to abundant plasma proteins. The combined DSC and MS approach in this study was successful in identifying unique biomarker signatures for cervical cancer and demonstrated the utility of DSC plasma profiles as a complementary diagnostic tool to evaluate

  6. Thermodynamics of calmodulin trapping by Ca2+/calmodulin-dependent protein kinase II: subpicomolar Kd determined using competition titration calorimetry. (United States)

    Tse, Joyce K Y; Giannetti, Anthony M; Bradshaw, J Michael


    Calmodulin (CaM) trapping by Ca2+/calmodulin-dependent protein kinase II (CaMKII) is a phenomenon whereby the affinity of CaM for CaMKII increases >1000-fold following CaMKII autophosphorylation. The molecular basis of this effect is not entirely understood. Binding of CaM to the phosphorylated and the unphosphorylated states of CaMKII is well mimicked by the interaction of CaM with two different length peptides taken from the CaM-binding region of CaMKII, peptides we refer to as the long and intermediate peptides. To better understand the conformational change accompanying CaM trapping, we have used isothermal titration calorimetry (ITC) to compare the binding thermodynamics of CaM to these peptides as well as to a shorter CaMKII-based peptide. Calorimetric analysis revealed that the enthalpy, rather than the entropy, distinguished binding of these three peptides. Furthermore, the heat capacity change was found to be similar for the long and intermediate peptides but smaller in magnitude for the short peptide. Direct titration of CaM with peptide provided the Kd value for the short peptide (Kd = 5.9 +/- 2.4 microM), but a novel, two-phased competitive binding strategy was necessary to ascertain the affinities of the intermediate (Kd = 0.17 +/- 0.06 nM) and long (Kd = 0.07 +/- 0.04 pM) peptides. To our knowledge, the Kd for the long peptide is the most potent measured to date using ITC. Together, the findings reported here support a model whereby the final conformational change accompanying CaM trapping buries little additional surface area but does involve formation of new hydrogen bonds and van der Waals contacts that contribute to formation of the high-affinity, CaM-trapped state.

  7. Physical-chemical characterization and stability study of alpha-trypsin at ph 3.0 by differential scanning calorimetry

    Energy Technology Data Exchange (ETDEWEB)

    Santos, A.M.C.; Santana, M.A.; Gomide, F.T.F.; Oliveira, J.S.; Vilas Boas, F.A.S.; Santoro, M.M.; Teixera, K.N. [Universidade Federal de Minas Gerais (UFMG), Belo Horizonte, MG (Brazil). Inst. de Ciencias Biologicas (ICB). Dept. de Bioquimica e Imunologia; Miranda, A.A.C.; Biondi, I. [Universidade Estadual de Feira de Santana (UEFS), BA (Brazil). Dept. de Ciencias Biologicas; Vasconcelos, A.B.; Bemquerer, M.P. [EMBRAPA Recursos Geneticos e Biotecnologia, Brasilia, DF (Brazil). Parque Estacao Biologica (PqEB)


    Full text: {alpha}-Trypsin is a serine-protease with a polypeptide chain of 223 amino acid residues and six disulfide bridges. It is a globular protein with predominance of antiparallel {beta}-sheet secondary structure and it has two domains with similar structures. In the present work, a stability study of {alpha}-trypsin in the acid pH range was performed and physical-chemical denaturation parameters were measured by using differential scanning calorimetry (DSC). The {alpha}-trypsin has a shelf-life (t{sub 95%}) of about ten months at pH 3.0 and 4 deg C and its hydrolysis into the {psi}-trypsin isoform is negligible during six months as monitored by mass spectrometry (Micromass Q-ToF). The observed {delta}H{sub cal}/{delta}H{sub vH} ratio is close to unity for {alpha}-trypsin denaturation, which suggests the occurrence of a two-state transition, devoid of molten-globule intermediates. At pH 3.0, {alpha}-trypsin unfolded with T{sub m} 325.9 K and {delta}H= 99.10 kcal mol{sup -1}, and the change in heat capacity between the native and unfolded forms of the protein was estimated to be 1.96 {+-} 0.18 kcal mol{sup -1} K{sup -1}. The stability of {alpha}-trypsin calculated at 298 K and at pH 3.0 was {delta}G{sub U} = 6.10 kcal mol{sup -1}. These values are in the range expected for a small globular protein. These results show that the thermodynamic parameters for unfolding of {beta}-trypsin do not change substantially after its conversion to {alpha}-trypsin.

  8. Thermodynamic Study of Interactions Between ZnO and ZnO Binding Peptides Using Isothermal Titration Calorimetry. (United States)

    Limo, Marion J; Perry, Carole C


    While material-specific peptide binding sequences have been identified using a combination of combinatorial methods and computational modeling tools, a deep molecular level understanding of the fundamental principles through which these interactions occur and in some instances modify the morphology of inorganic materials is far from being fully realized. Understanding the thermodynamic changes that occur during peptide-inorganic interactions and correlating these to structural modifications of the inorganic materials could be the key to achieving and mastering control over material formation processes. This study is a detailed investigation applying isothermal titration calorimetry (ITC) to directly probe thermodynamic changes that occur during interaction of ZnO binding peptides (ZnO-BPs) and ZnO. The ZnO-BPs used are reported sequences G-12 (GLHVMHKVAPPR), GT-16 (GLHVMHKVAPPR-GGGC), and alanine mutants of G-12 (G-12A6, G-12A11, and G-12A12) whose interaction with ZnO during solution synthesis studies have been extensively investigated. The interactions of the ZnO-BPs with ZnO yielded biphasic isotherms comprising both an endothermic and an exothermic event. Qualitative differences were observed in the isothermal profiles of the different peptides and ZnO particles studied. Measured ΔG values were between -6 and -8.5 kcal/mol, and high adsorption affinity values indicated the occurrence of favorable ZnO-BP-ZnO interactions. ITC has great potential in its use to understand peptide-inorganic interactions, and with continued development, the knowledge gained may be instrumental for simplification of selection processes of organic molecules for the advancement of material synthesis and design.

  9. Experimental determination of the (vapor + liquid) equilibrium data of binary mixtures of fatty acids by differential scanning calorimetry

    Energy Technology Data Exchange (ETDEWEB)

    Matricarde Falleiro, Rafael M. [LPT, Department of Chemical Processes (DPQ), School of Chemical Engineering, University of Campinas (UNICAMP), P.O. Box 6066, 13083-970 Campinas, SP (Brazil); Meirelles, Antonio J.A. [EXTRAE, Department of Food Engineering (DEA), School of Food Engineering, University of Campinas (UNICAMP), P.O. Box 6121, 13083-862 Campinas, SP (Brazil); Kraehenbuehl, Maria A., E-mail: mak@feq.unicamp.b [LPT, Department of Chemical Processes (DPQ), School of Chemical Engineering, University of Campinas (UNICAMP), P.O. Box 6066, 13083-970 Campinas, SP (Brazil)


    (Vapor + liquid) equilibrium (VLE) data for three binary mixtures of saturated fatty acids were obtained by differential scanning calorimetry (DSC). However, changes in the calorimeter pressure cell and the use of hermetic pans with holes (phi = 250 mm) in the lids were necessary to make it possible to apply this analytical technique, obtaining accurate results with smaller samples and shorter operational times. The systems evaluated in this study were: myristic acid (C{sub 14:0}) + palmitic acid (C{sub 16:0}), myristic acid (C{sub 14:0}) + stearic acid (C{sub 18:0}), and palmitic acid (C{sub 16:0}) + stearic acid (C{sub 18:0}), all measured at 50 mm Hg and with mole fractions between 0.0 and 1.0 in relation to the most volatile component of each diagram. The fugacity coefficients for the components in the vapor phase were calculated using the Hayden and O'Connell method [J.G. Hayden, J.P. O'Connell, Ind. Eng. Chem. Process Design Develop. 14 (3) (1975) 209-216] and the activity coefficients for the liquid phase were correlated with the traditional g{sup E} models (NRTL [H. Renon, J.M. Prausnitz, Aiche J. 14 (1968) 135-144], UNIQUAC [D.S. Abrams, J.M. Prausnitz, Aiche J. 21 (1975) 116-128], and Wilson [J.M. Prausnitz, N.L. Linchtenthaler, E.G. Azevedo, Molecular Thermodynamics of Fluid-phase Equilibria, River-Prentice Hall, Upper Saddle, 1999]). The sets of parameters were then compared in order to determine which adjustments best represented the VLE.

  10. Assessing the performance under ionising radiation of lead tungstate scintillators for EM calorimetry in the CLAS12 Forward Tagger

    Energy Technology Data Exchange (ETDEWEB)

    Fegan, S., E-mail: [Istituto Nazionale di Fisica Nucleare, Sezione di Genova and Dipartimento di Fisica dell' Universitá, Via Dodecaneso 33, 16146 Genova (Italy); Auffray, E. [CERN, European Organisation for Nuclear Research, Geneva (Switzerland); Battaglieri, M. [Istituto Nazionale di Fisica Nucleare, Sezione di Genova and Dipartimento di Fisica dell' Universitá, Via Dodecaneso 33, 16146 Genova (Italy); Buchanan, E. [University of Glasgow, Glasgow G12 8QQ (United Kingdom); Caiffi, B.; Celentano, A. [Istituto Nazionale di Fisica Nucleare, Sezione di Genova and Dipartimento di Fisica dell' Universitá, Via Dodecaneso 33, 16146 Genova (Italy); Colaneri, L.; D' Angelo, A. [Istituto Nazionale di Fisica Nucleare, Sezione Roma2 Tor Vergata and Università degli studi di Roma Tor Vergata, Via Scientifica 1, 00133 Roma (Italy); De Vita, R. [Istituto Nazionale di Fisica Nucleare, Sezione di Genova and Dipartimento di Fisica dell' Universitá, Via Dodecaneso 33, 16146 Genova (Italy); Dormenev, V. [II. Physikalisches Institut, Universität Gießen, 35392 Gießen (Germany); Fanchini, E. [Istituto Nazionale di Fisica Nucleare, Sezione di Genova and Dipartimento di Fisica dell' Universitá, Via Dodecaneso 33, 16146 Genova (Italy); Lanza, L. [Istituto Nazionale di Fisica Nucleare, Sezione Roma2 Tor Vergata and Università degli studi di Roma Tor Vergata, Via Scientifica 1, 00133 Roma (Italy); Novotny, R.W. [II. Physikalisches Institut, Universität Gießen, 35392 Gießen (Germany); and others


    The well-established technology of electromagnetic calorimetry using Lead Tungstate crystals has recently seen an upheaval, with the closure of one of the most experienced large-scale suppliers of such crystals, the Bogoroditsk Technical Chemical Plant (BTCP), which was instrumental in the development of mass production procedures for PWO-II, the current benchmark for this scintillator. Obtaining alternative supplies of Lead Tungstate crystals matching the demanding specifications of contemporary calorimeter devices now presents a significant challenge to detector research and development programmes. In this paper we describe a programme of assessment carried out for the selection, based upon the performance under irradiation, of Lead Tungstate crystals for use in the Forward Tagger device, part of the CLAS12 detector in Hall B at Jefferson Lab. The crystals tested were acquired from SICCAS, the Shanghai Institute of Ceramics, Chinese Academy of Sciences. The tests performed are intended to maximise the performance of the detector within the practicalities of the crystal manufacturing process. Results of light transmission, before and after gamma ray irradiation, are presented and used to calculate dk, the induced radiation absorption coefficient, at 420 nm, the peak of the Lead Tungstate emission spectrum. Results for the SICCAS crystals are compared with identical measurements carried out on Bogoroditsk samples, which were acquired for the Forward Tagger development program before the closure of the facility. Also presented are a series of tests performed to determine the feasibility of recovering radiation damage to the crystals using illumination from an LED, with such illumination available in the Forward Tagger from a light monitoring system integral to the detector.

  11. Electrostatic interactions in the binding pathway of a transient protein complex studied by NMR and isothermal titration calorimetry. (United States)

    Meneses, Erick; Mittermaier, Anthony


    Much of our knowledge of protein binding pathways is derived from extremely stable complexes that interact very tightly, with lifetimes of hours to days. Much less is known about weaker interactions and transient complexes because these are challenging to characterize experimentally. Nevertheless, these types of interactions are ubiquitous in living systems. The combination of NMR relaxation dispersion Carr-Purcell-Meiboom-Gill (CPMG) experiments and isothermal titration calorimetry allows the quantification of rapid binding kinetics for complexes with submillisecond lifetimes that are difficult to study using conventional techniques. We have used this approach to investigate the binding pathway of the Src homology 3 (SH3) domain from the Fyn tyrosine kinase, which forms complexes with peptide targets whose lifetimes are on the order of about a millisecond. Long range electrostatic interactions have been shown to play a critical role in the binding pathways of tightly binding complexes. The role of electrostatics in the binding pathways of transient complexes is less well understood. Similarly to previously studied tight complexes, we find that SH3 domain association rates are enhanced by long range electrostatics, whereas short range interactions are formed late in the docking process. However, the extent of electrostatic association rate enhancement is several orders of magnitudes less, whereas the electrostatic-free basal association rate is significantly greater. Thus, the SH3 domain is far less reliant on electrostatic enhancement to achieve rapid association kinetics than are previously studied systems. This suggests that there may be overall differences in the role played by electrostatics in the binding pathways of extremely stable versus transient complexes.

  12. An evaluation of the transition temperature range of super-elastic orthodontic NiTi springs using differential scanning calorimetry. (United States)

    Barwart, O; Rollinger, J M; Burger, A


    Differential scanning calorimetry (DSC) was used to determine the transition temperature ranges (TTR) of four types of super-elastic orthodontic nickel-titanium coil springs (Sentalloy). A knowledge of the TTR provides information on the temperature at which a NiTi wire or spring can assume superelastic properties and when this quality disappears. The spring types in this study can be distinguished from each other by their characteristic TTR during cooling and heating. For each tested spring type a characteristic TTR during heating (austenite transformation) and cooling (martensite transformation) was evaluated. The hysteresis of the transition temperature, found between cooling and heating, was 3.4-5.2 K. Depending on the spring type the austenite transformation started (As) at 9.7-17.1 degrees C and finished (Af) at 29.2-37 degrees C. The martensite transformation starting temperature (Ms) was evaluated at 32.6-25.4 degrees C, while Mf (martensite transformation finishing temperature) was 12.7-6.5 degrees C. The results show that the springs become super-elastic when the temperature increases and As is reached. They undergo a loss of super-elastic properties and a rapid decrease in force delivery when they are cooled to Mf. For the tested springs, Mf and As were found to be below room temperature. Thus, at room temperature and some degrees lower, all the tested springs exert super-elastic properties. For orthodontic treatment this means the maintenance of super-elastic behaviour, even when mouth temperature decreases to about room temperature as can occur, for example, during meals.

  13. Native ESI Mass Spectrometry Can Help to Avoid Wrong Interpretations from Isothermal Titration Calorimetry in Difficult Situations (United States)

    Wolff, Philippe; Da Veiga, Cyrielle; Ennifar, Eric; Bec, Guillaume; Guichard, Gilles; Burnouf, Dominique; Dumas, Philippe


    We studied by native ESI-MS the binding of various DNA-polymerase-derived peptides onto DNA-polymerase processivity rings from Escherichia coli, Pseudomonas aeruginosa, and Mycobacterium tuberculosis. These homodimeric rings present two equivalent specific binding sites, which leads to successive formation during a titration experiment of singly- and doubly occupied rings. By using the ESI-MS free-ring spectrum as a ruler, we derived by robust linear regression the fractions of the different ring species at each step of a titration experiment. These results led to accurate Kd values (from 0.03 to 0.5 μM) along with the probability of peptide loss due to gas phase dissociation (GPD). We show that this good quality is due to the increased information content of a titration experiment with a homodimer. Isothermal titration calorimetry (ITC) led with the same binding model to Kd(ITC) values systematically higher than their ESI-MS counterparts and, often, to poor fit of the ITC curves. A processing with two competing modes of binding on the same site requiring determination of two (Kd, ΔH) pairs greatly improved the fits and yielded a second Kd(ITC) close to Kd(ESI-MS). The striking features are: (1) ITC detected a minor binding mode ( 20%) of `low-affinity' that did not appear with ESI-MS; (2) the simplest processing of ITC data with only one (Kd, ΔH) pair led wrongly to the Kd of the low-affinity binding mode but to the ΔH of the high-affinity binding mode. Analogous misleading results might well exist in published data based on ITC experiments.

  14. Accelerating rate calorimetry studies of the reactions between ionic liquids and charged lithium ion battery electrode materials

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Yadong; Dahn, J.R. [Department of Physics and Atmospheric Science, Dalhousie University, Halifax, NS (Canada); Zaghib, K.; Guerfi, A. [Institut de Recherche d' Hydro-Quebec, 1800 Lionel-Boulet, Varennes, Que. (Canada); Bazito, Fernanda F.C.; Torresi, Roberto M. [Instituto de Quimica Universidade de Sao Paulo, CP 26077, 05513-970 Sao Paulo (Brazil)


    Using accelerating rate calorimetry (ARC), the reactivity between six ionic liquids (with and without added LiPF{sub 6}) and charged electrode materials is compared to the reactivity of standard carbonate-based solvents and electrolytes with the same electrode materials. The charged electrode materials used were Li{sub 1}Si, Li{sub 7}Ti{sub 4}O{sub 12} and Li{sub 0.45}CoO{sub 2}. The experiments showed that not all ionic liquids are safer than conventional electrolytes/solvents. Of the six ionic liquids tested, 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide (EMI-FSI) shows the worst safety properties, and is much worse than conventional electrolyte. 1-Ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (EMI-TFSI) and 1-propyl-1-methylpyrrolidinium bis(fluorosulfonyl)imide (Py13-FSI) show similar reactivity to carbonate-based electrolyte. The three ionic liquids 1-butyl-2,3-dimethylimidazolium bis(trifluoromethanesulfonyl)imide (BMMI-TFSI), 1-butyl-1-methylpiperidinium bis(trifluoromethanesulfonyl)imide (Pp14-TFSI) and N-trimethyl-N-butylammonium bis(trifluoromethanesulfonyl)imide (TMBA-TFSI) show similar reactivity and are much safer than the conventional carbonate-based electrolyte. A comparison of the reactivity of ionic liquids with common anions and cations shows that ionic liquids with TFSI{sup -} are safer than those with FSI{sup -}, and liquids with EMI{sup +} are worse than those with BMMI{sup +}, Py13{sup +}, Pp14{sup +} and TMBA{sup +}. (author)

  15. Native ESI Mass Spectrometry Can Help to Avoid Wrong Interpretations from Isothermal Titration Calorimetry in Difficult Situations (United States)

    Wolff, Philippe; Da Veiga, Cyrielle; Ennifar, Eric; Bec, Guillaume; Guichard, Gilles; Burnouf, Dominique; Dumas, Philippe


    We studied by native ESI-MS the binding of various DNA-polymerase-derived peptides onto DNA-polymerase processivity rings from Escherichia coli, Pseudomonas aeruginosa, and Mycobacterium tuberculosis. These homodimeric rings present two equivalent specific binding sites, which leads to successive formation during a titration experiment of singly- and doubly occupied rings. By using the ESI-MS free-ring spectrum as a ruler, we derived by robust linear regression the fractions of the different ring species at each step of a titration experiment. These results led to accurate Kd values (from 0.03 to 0.5 μM) along with the probability of peptide loss due to gas phase dissociation (GPD). We show that this good quality is due to the increased information content of a titration experiment with a homodimer. Isothermal titration calorimetry (ITC) led with the same binding model to Kd(ITC) values systematically higher than their ESI-MS counterparts and, often, to poor fit of the ITC curves. A processing with two competing modes of binding on the same site requiring determination of two (Kd, ΔH) pairs greatly improved the fits and yielded a second Kd(ITC) close to Kd(ESI-MS). The striking features are: (1) ITC detected a minor binding mode ( 20%) of `low-affinity' that did not appear with ESI-MS; (2) the simplest processing of ITC data with only one (Kd, ΔH) pair led wrongly to the Kd of the low-affinity binding mode but to the ΔH of the high-affinity binding mode. Analogous misleading results might well exist in published data based on ITC experiments.

  16. Calorimetry triggering in ATLAS

    CERN Document Server

    Igonkina, O; Adragna, P; Aharrouche, M; Alexandre, G; Andrei, V; Anduaga, X; Aracena, I; Backlund, S; Baines, J; Barnett, B M; Bauss, B; Bee, C; Behera, P; Bell, P; Bendel, M; Benslama, K; Berry, T; Bogaerts, A; Bohm, C; Bold, T; Booth, J R A; Bosman, M; Boyd, J; Bracinik, J; Brawn, I, P; Brelier, B; Brooks, W; Brunet, S; Bucci, F; Casadei, D; Casado, P; Cerri, A; Charlton, D G; Childers, J T; Collins, N J; Conde Muino, P; Coura Torres, R; Cranmer, K; Curtis, C J; Czyczula, Z; Dam, M; Damazio, D; Davis, A O; De Santo, A; Degenhardt, J; Delsart, P A; Demers, S; Demirkoz, B; Di Mattia, A; Diaz, M; Djilkibaev, R; Dobson, E; Dova, M, T; Dufour, M A; Eckweiler, S; Ehrenfeld, W; Eifert, T; Eisenhandler, E; Ellis, N; Emeliyanov, D; Enoque Ferreira de Lima, D; Faulkner, P J W; Ferland, J; Flacher, H; Fleckner, J E; Flowerdew, M; Fonseca-Martin, T; Fratina, S; Fhlisch, F; Gadomski, S; Gallacher, M P; Garitaonandia Elejabarrieta, H; Gee, C N P; George, S; Gillman, A R; Goncalo, R; Grabowska-Bold, I; Groll, M; Gringer, C; Hadley, D R; Haller, J; Hamilton, A; Hanke, P; Hauser, R; Hellman, S; Hidvgi, A; Hillier, S J; Hryn'ova, T; Idarraga, J; Johansen, M; Johns, K; Kalinowski, A; Khoriauli, G; Kirk, J; Klous, S; Kluge, E-E; Koeneke, K; Konoplich, R; Konstantinidis, N; Kwee, R; Landon, M; LeCompte, T; Ledroit, F; Lei, X; Lendermann, V; Lilley, J N; Losada, M; Maettig, S; Mahboubi, K; Mahout, G; Maltrana, D; Marino, C; Masik, J; Meier, K; Middleton, R P; Mincer, A; Moa, T; Monticelli, F; Moreno, D; Morris, J D; Mller, F; Navarro, G A; Negri, A; Nemethy, P; Neusiedl, A; Oltmann, B; Olvito, D; Osuna, C; Padilla, C; Panes, B; Parodi, F; Perera, V J O; Perez, E; Perez Reale, V; Petersen, B; Pinzon, G; Potter, C; Prieur, D P F; Prokishin, F; Qian, W; Quinonez, F; Rajagopalan, S; Reinsch, A; Rieke, S; Riu, I; Robertson, S; Rodriguez, D; Rogriquez, Y; Rhr, F; Saavedra, A; Sankey, D P C; Santamarina, C; Santamarina Rios, C; Scannicchio, D; Schiavi, C; Schmitt, K; Schultz-Coulon, H C; Schfer, U; Segura, E; Silverstein, D; Silverstein, S; Sivoklokov, S; Sjlin, J; Staley, R J; Stamen, R; Stelzer, J; Stockton, M C; Straessner, A; Strom, D; Sushkov, S; Sutton, M; Tamsett, M; Tan, C L A; Tapprogge, S; Thomas, J P; Thompson, P D; Torrence, E; Tripiana, M; Urquijo, P; Urrejola, P; Vachon, B; Vercesi, V; Vorwerk, V; Wang, M; Watkins, P M; Watson, A; Weber, P; Weidberg, T; Werner, P; Wessels, M; Wheeler-Ellis, S; Whiteson, D; Wiedenmann, W; Wielers, M; Wildt, M; Winklmeier, F; Wu, X; Xella, S; Zhao, L; Zobernig, H; de Seixas, J M; dos Anjos, A; Asman, B; Özcan, E


    The ATLAS experiment is preparing for data taking at 14 TeV collision energy. A rich discovery physics program is being prepared in addition to the detailed study of Standard Model processes which will be produced in abundance. The ATLAS multi-level trigger system is designed to accept one event in 2 105 to enable the selection of rare and unusual physics events. The ATLAS calorimeter system is a precise instrument, which includes liquid Argon electro-magnetic and hadronic components as well as a scintillator-tile hadronic calorimeter. All these components are used in the various levels of the trigger system. A wide physics coverage is ensured by inclusively selecting events with candidate electrons, photons, taus, jets or those with large missing transverse energy. The commissioning of the trigger system is being performed with cosmic ray events and by replaying simulated Monte Carlo events through the trigger and data acquisition system.

  17. Calorimetry in a Nutshell. (United States)

    Markow, Peter


    Provides information on nutritional caloric value determination. Describes the chemical components of peanuts. Explains how to construct a soda can calorimeter for determining the heat released by a burning nut. Describes how to determine calories and kilocalories. Author asserts the activity can be adopted for children of any age. (eight…

  18. LC-Circuit Calorimetry

    CERN Document Server

    Bossen, Olaf


    We present a new type of calorimeter in which we couple an unknown heat capacity with the aid of Peltier elements to an electrical circuit. The use of an electrical inductance and an amplifier in the circuit allows us to achieve autonomous oscillations, and the measurement of the corresponding resonance frequency makes it possible to accurately measure the heat capacity with an intrinsic statistical error that decreases as ~t^{-3/2} with measuring time t, as opposed to a corresponding error ~t^{-1/2} in the conventional alternating current (a.c.) method to measure heat capacities. We have built a demonstration experiment to show the feasibility of the new technique, and we have tested it on a gadolinium sample at its transition to the ferromagnetic state.

  19. New ideas in calorimetry

    CERN Document Server

    Botner, O


    The hadron calorimeter for the CERN ISR experiment R807 is of the fission compensating type, using /sup 238/U as absorber. The possibility of replacing part of the uranium by more easily accessible material without destroying the good properties of a pure uranium- scintillator calorimeter has been investigated. (0 refs).

  20. Hadronic Imaging Calorimetry

    CERN Document Server

    Kaplan, Alexander; Schultz-Coulon, Hans-Christian; Dubbers, Dirk

    This thesis focuses on a prototype of a highly granular hadronic calorimeter at the planned International Linear Collider optimized for the Particle Flow Approach. The 5.3 nuclear interaction lengths deep sandwich calorimeter was built by the CALICE collaboration and consists of 38 active plastic scintillator layers. Steel is used as absorber material and the active layers are subdivided into small tiles. In total 7608 tiles are read out individually via embedded Silicon Photomultipliers (SiPM). The prototype is one of the first large scale applications of these novel and very promising miniature photodetectors. The work described in this thesis comprises the commissioning of the detector and the data acquisition with test beam particles over several months at CERN and Fermilab. The calibration of the calorimeter and the analysis of the recorded data is presented. A method to correct for the temperature dependent response of the SiPM has been developed and implemented. Its successful application shows that it...

  1. Development of Imaging Calorimetry

    CERN Document Server

    Bilki, Burak; Xia, Lei


    This paper will argue for continued effort in developing imaging calorimeters for future colliders and/or upgrades to existing detectors. Imaging calorimeters offer a plethora of advantages beyond their application in conjunction with Particle Flow Algorithms. Further R&D is needed to turn the first generation prototypes into viable detectors for colliding beam experiments.

  2. High Flux Calorimetry. (United States)


    These approaches are based on proven principles which have served the thermal test community well for years. Other concepts hold promise of being able to...8217. --......- - ... .... - - The thermal test community has developed instrumentation which is quite suitable for the moderate, and relatively constant, flux...on the maximum phase II system fluence of 400 cal/cm2 . Second, the present thermal test community will have confidence in the performance of an

  3. Investigation of Phase Mixing in Amorphous Solid Dispersions of AMG 517 in HPMC-AS Using DSC, Solid-State NMR, and Solution Calorimetry. (United States)

    Calahan, Julie L; Azali, Stephanie C; Munson, Eric J; Nagapudi, Karthik


    Intimate phase mixing between the drug and the polymer is considered a prerequisite to achieve good physical stability for amorphous solid dispersions. In this article, spray dried amorphous dispersions (ASDs) of AMG 517 and HPMC-as were studied by differential scanning calorimetry (DSC), solid-state NMR (SSNMR), and solution calorimetry. DSC analysis showed a weakly asymmetric (ΔTg ≈ 13.5) system with a single glass transition for blends of different compositions indicating phase mixing. The Tg-composition data was modeled using the BKCV equation to accommodate the observed negative deviation from ideality. Proton spin-lattice relaxation times in the laboratory and rotating frames ((1)H T1 and T1ρ), as measured by SSNMR, were consistent with the observation that the components of the dispersion were in intimate contact over a 10-20 nm length scale. Based on the heat of mixing calculated from solution calorimetry and the entropy of mixing calculated from the Flory-Huggins theory, the free energy of mixing was calculated. The free energy of mixing was found to be positive for all ASDs, indicating that the drug and polymer are thermodynamically predisposed to phase separation at 25 °C. This suggests that miscibility measured by DSC and SSNMR is achieved kinetically as the result of intimate mixing between drug and polymer during the spray drying process. This kinetic phase mixing is responsible for the physical stability of the ASD.

  4. Low validity of the Sensewear Pro3 activity monitor compared to indirect calorimetry during simulated free living in patients with osteoarthritis of the hip

    DEFF Research Database (Denmark)

    Hermann, Andreas; Ried-Larsen, Mathias; Jensen, Andreas Kryger;


    BACKGROUND: To validate physical activity estimates by the Sensewear Pro3 activity monitor compared with indirect calorimetry during simulated free living in patients diagnosed with osteoarthritis of the hip pre or post total hip arthroplasty. METHODS: Twenty patients diagnosed with hip osteoarth......BACKGROUND: To validate physical activity estimates by the Sensewear Pro3 activity monitor compared with indirect calorimetry during simulated free living in patients diagnosed with osteoarthritis of the hip pre or post total hip arthroplasty. METHODS: Twenty patients diagnosed with hip...... osteoarthritis (10 pre- and 10 post total hip arthroplasty; 40% female; age: 63.3 ± 9.0; BMI: 23.7 ± 3.7). All patients completed a 2 hour protocol of simulated free living with 8 different typical physical activity types. Energy consumption (kcal/min) was estimated by the Sense Wear pro3 Armband activity...... monitor and validated against indirect calorimetry (criterion method) by means of a portable unit (Cosmed K4b2). Bias and variance was analyzed using functional ANOVA. RESULTS: Mean bias during all activities was 1.5 Kcal/min 95%CI [1.3; 1.8] corresponding to 72% (overestimation). Normal gait speed showed...

  5. SU-E-T-410: Fringe Stability and Phase Shift Measurements in a Michelson Interferometer for Optical Calorimetry

    Energy Technology Data Exchange (ETDEWEB)

    Flores-Martinez, E; Malin, M [UW-Madison, Madison, WI (United States); DeWerd, L [University of WI-Madison/ADCL, Madison, WI (United States)


    Purpose: To identify the variables limiting the resolution of a Michelson interferometer used to measure phase shifts (PS) in water as part of a radiometric calorimeter. Methods: We investigated the output stability of a He-Ne laser and a laser diode. The short and long term stability of the fringe pattern in a Michelson interferometer was tested with different types of lasers, thermal insulation arrangements, damping systems and optical mounts to optimize system performance. PS were induced by electrically heating water in a 1 cm quartz cuvette located in one of the interferometer arms. The PS was calculated from fringe intensity changes and compared to a calculated PS using thermocouple-measured temperature changes in the water. Results: The intensity of the laser diode is more stable, but the gas laser’s profile is more suitable for fringe analysis and has better temporal coherence. The laser requires a warm-up time of 4 hours before its output is stabilized (SNR>95). The fringe’s stability strongly depends on the thermal insulation. When the interferometer is exposed to ambient temperature swings of 0.7 K, it is not possible to stabilize the fringe pattern. Enclosing the system in a 2.5 cm-thick Styrofoam box improves the SNR, but further insulation will be needed to increase the SNR above 50. High frequency noise is significantly reduced by damping the system.Inducing a temperature rise in water, starting at 299 K, the average temperature increase for a 2π PS is 0.29 ± 0.02 K and the proportionality constant is -21.1 ± 0.8 radians/K. This is 5.8% lower than the calculated value using the thermocouple. Conclusion: Interferometric PS measurements of temperature may provide an alternative to thermistors for water calorimetry. The resolution of the current prototype is limited by ambient temperature stability. Calculated and measured thermally-induced PS in water agreed to within 5.8%.

  6. Evaluation of polymerization of an experimental bonding resin cured with light emitting diodes using Differential Scanning Calorimetry

    Directory of Open Access Journals (Sweden)

    Jafarzadekashi T.


    Full Text Available "nBackground and Aim: Extent of polymerization (Ep is the rate at which methacrylate C=C bonds are converted to aliphatic C-C bonds. The higher the Ep value, the better the polymerization of the polymer. If the polymer dose not polymerize sufficiently, it could have destructive effects e.g. releasing monomer, initiator, free radical or insufficient polymerization of hybrid layer. Therefore, measuring the Ep value is very important. Light-emitting diodes (LEDs are becoming increasingly popular in dental practice as they have a long life expectancy. LEDs do not generate infrared wavelength, and have a constant light output. Therefore, comparison of LED and Quartz tungsten halogen (QTH from the point of Ep is important. Differential Scanning Calorimetry (DSC is a proper tool for determining the Ep value, monitoring the process of reaction and reaction kinetics. The aim of this study was to measure the Ep value of a dental bonding containing camphorquinone/amine photoinitiator which were cured by LED and QTH using DSC. "nMaterials and Methods: In this experimental study, 2.5 mg of bonding material were placed in DSC aluminum pans. Two different light cures, LED & QTH (Coltene Company Coltolux ®75 LED Curing Light, were used in this study. The light guide was positioned at a distance of 9mm from the base of the sample chamber. Each sample was photopolymerized for 30 seconds, and the DSC curves were obtained after 100 seconds from initiation of photopolimerization of each sample, at both 23oC and 37oC. The heat of photopolymerization (DH was calculated from the area under the peak of the differential temperature curve. Five samples were used for each condition. The data was analyzed by two-way ANOVA. "nResults: There was highly significant difference between two temperatures in the experimental bonding (pvalue<0.001. Representative DSC curves showed the same kinetic behavior for LED and QTH. "nConclusion: The results revealed that the Ep generated by

  7. Detection of conformational changes in immunoglobulin G using isothermal titration calorimetry with low-molecular-weight probes. (United States)

    Rispens, Theo; Lakemond, Catriona M M; Derksen, Ninotska I L; Aalberse, Rob C


    Proteins for therapeutic use may contain small amounts of partially misfolded monomeric precursors to postproduction aggregation. To detect these misfolded proteins in the presence of an excess of properly folded protein, fluorescent probes such as 8-anilino-1-naphthalene sulfonate (ANS) are commonly used. We investigated the possibility of using isothermal titration calorimetry (ITC) to improve the detection of this type of conformational change using hydrophobic probes. As a case study, conformational changes in human polyclonal immunoglobulin G (IgG) were monitored by measuring the enthalpies of binding of ANS using ITC. Results were compared with those using fluorescence spectroscopy. IgG heated at 63 degrees C was used as a model system for "damaged" IgG. Heat-treated IgG can be detected already at levels below 5% with both ITC and fluorescence. However, ITC allows a much wider molar probe-to-protein ratio to be sampled. In particular, using reverse titration experiments (allowing high probe-to-protein ratios not available to fluorescence spectroscopy), an increase in the number of binding sites with a K(d)>10 mM was observed for heat-treated IgG, reflecting subtle changes in structure. Both ITC and fluorescence spectroscopy showed low background signals for native IgG. The nature of the background signals was not clear from the fluorescence measurements. However, further analysis of the ITC background signals shows that a fraction (8%) binds ANS with a dissociation constant of approximately 0.2 mM. Measurements were also carried out at pH 4.5. Precipitation of IgG was induced by ANS at concentrations above 0.5 mM, interfering with the ITC measurements. Instead, with the nonfluorescent probes 4-amino-1-naphthalene sulfonate and 1-naphthalene sulfonate, no precipitation is observed. These probes yield differences in the enthalpies of binding to heated and nonheated IgG similar to ANS. The data illustrate that ITC with low-molecular-weight probes is a versatile

  8. Hydration water and peptide dynamics--two sides of a coin. A neutron scattering and adiabatic calorimetry study at low hydration and cryogenic temperatures. (United States)

    Bastos, Margarida; Alves, Nuno; Maia, Sílvia; Gomes, Paula; Inaba, Akira; Miyazaki, Yuji; Zanotti, Jean-Marc


    In the present work we bridge neutron scattering and calorimetry in the study of a low-hydration sample of a 15-residue hybrid peptide from cecropin and mellitin CA(1-7)M(2-9) of proven antimicrobial activity. Quasielastic and low-frequency inelastic neutron spectra were measured at defined hydration levels - a nominally 'dry' sample (specific residual hydration h = 0.060 g/g), a H2O-hydrated (h = 0.49) and a D2O-hydrated one (h = 0.51). Averaged mean square proton mobilities were derived over a large temperature range (50-300 K) and the vibrational density of states (VDOS) were evaluated for the hydrated samples. The heat capacity of the H2O-hydrated CA(1-7)M(2-9) peptide was measured by adiabatic calorimetry in the temperature range 5-300 K, for different hydration levels. The glass transition and water crystallization temperatures were derived in each case. The existence of different types of water was inferred and their amounts calculated. The heat capacities as obtained from direct calorimetric measurements were compared to the values derived from the neutron spectroscopy by way of integrating appropriately normalized VDOS functions. While there is remarkable agreement with respect to both temperature dependence and glass transition temperatures, the results also show that the VDOS derived part represents only a fraction of the total heat capacity obtained from calorimetry. Finally our results indicate that both hydration water and the peptide are involved in the experimentally observed transitions.

  9. Thermal Analysis of Whole Bacterial Cells Exposed to Potassium Permanganate Using Differential Scanning Calorimetry: a Biphasic Dose-Dependent Response to Stress

    Directory of Open Access Journals (Sweden)

    Marina K. Abuladze


    Full Text Available Differential scanning calorimetry (DSC was applied to estimate the impact of the toxic oxidant potassium permanganate (PM on the intracellular structural and functional alterations at whole cell level using soil bacteria Arthrobacter oxydans as a model culture. Differential scanning calorimetry (DSC was applied in order to estimate the impact of the toxic oxidant potassium permanganate (PM on the intracellular structural and functional alterations at the whole cell level using the soil bacteria Arthrobacter oxydans as a model culture. We compared the total melting heat and the temperature of DNA-protein complex (DNP melting at the PM application prior to the calorimetry measurement and after 24-h exposure at the concentration range 0.02–1.4 mM. The initial oxidative effect caused changes in the pattern of the whole cell melting spectra (mainly at the temperature range 56–78°C, the decrease of Tmax °C DNP melting, and did not influence significantly the total heat of bacterial melting at different concentrations of PM. The prolonged effect of permanganate up to 24 h was characterized by a biphasic dose-dependent response to stress estimated by the DSC technique and the colony-forming assay. The low doses of PM (0.02 and 0.2 mM stimulated cell proliferation, and increased the total whole cell melting heat and the temperature of DNP melting. The toxic effect of PM up to 0.04 mM reduced cell viability, changed the character of multipeaked thermograms, and lowered the total melting heat and the temperature of DNP melting in a concentration-dependent manner. This study presents the DSC method for evaluating and monitoring the effects of exposure to potential human and environmental toxicants.

  10. Thermodynamics of the formation of complexes of copper(II) ions and glycylglycine in aqueous solutions at 298 K according to calorimetry data (United States)

    Kochergina, L. A.; Emel'yanov, A. V.


    Heat effects of the interaction between glycylglycine and copper(II) nitrate solutions are measured by direct calorimetry at a [metal] : [ligand] ratio of 1 : 5 and at different pH values of the solution. The measurements are made at a temperature of 298.15 K and ionic strengths of 0.25, 0.50, and 0.75. KNO3 is used as a background electrolyte. The thermodynamic characteristics of complex formation by the peptide and copper(II) ions in aqueous solutions are determined. Standard enthalpies of the formation of complex particles in aqueous solutions are calculated.

  11. Differential scanning calorimetry (DSC) as a tool for probing the reactivity of polyynes relevant to hexadehydro-Diels-Alder (HDDA) cascades. (United States)

    Woods, Brian P; Hoye, Thomas R


    The differential scanning calorimetry (DSC) behavior of a number of alkyne-rich compounds is described. The DSC trace for each compound exhibits an exothermic event at a characteristic onset temperature. For the tri- and tetraynes whose [4 + 2] HDDA reactivity in solution has been determined, these onset temperatures show a strong correlation with the cyclization activation energy. The studies reported here exemplify how the data available through this operationally simple analytical technique can give valuable insights into the thermal behavior of small molecules.

  12. Evaluation of thermal stability of paraffin wax by differential scanning calorimetry; Avaliacao da estabilidade termica de parafina por calorimetria diferencial de varredura

    Energy Technology Data Exchange (ETDEWEB)

    Godinho, K.O.; Silva, A.G.P.; Holanda, J.N.F. [Universidade Estadual do Norte Fluminense (LAMAV/UENF), Campos dos Goytacazes, RJ (Brazil). Grupo de Materiais Ceramicos], Email:


    Phase change materials for heat storage are used as passive solar energy storage materials, which can be impregnated into construction materials. In this work the thermal stability (heating/cooling cycle) of the paraffin wax was investigated using differential scanning calorimetry. The latent heat and fusion temperature were determined for the following thermal cycles: 0, 30, 180 and 360. The thermal stability for paraffin wax infiltrated in support of gypsum was also determined. The experimental results showed that the paraffin wax showed good thermal stability in the states pure and infiltrated for up to 360 thermal cycles. (author)

  13. Solid state and sub-cooled liquid vapour pressures of substituted dicarboxylic acids using Knudsen Effusion Mass Spectrometry (KEMS and Differential Scanning Calorimetry

    Directory of Open Access Journals (Sweden)

    A. M. Booth


    Full Text Available Solid state vapour pressures of a selection of substituted dicarboxylic acids have been measured using Knudsen Effusion Mass Spectrometry (KEMS. Enthalpies of fusion and melting points obtained using Differential Scanning Calorimetry (DSC were used to obtain sub-cooled liquid vapour pressures. They have been compared to estimation methods used on the E-AIM website. These methods are shown to poorly represent -OH groups in combination with COOH groups. Partitioning calculations have been performed to illustrate the impact of the different estimation methods on organic aerosol mass compared to the use of experimental data.

  14. Solid state and sub-cooled liquid vapour pressures of substituted dicarboxylic acids using Knudsen Effusion Mass Spectrometry (KEMS and Differential Scanning Calorimetry

    Directory of Open Access Journals (Sweden)

    A. M. Booth


    Full Text Available Solid state vapour pressures of a selection of atmospherically important substituted dicarboxylic acids have been measured using Knudsen Effusion Mass Spectrometry (KEMS over a range of 20 K (298–318 K. Enthalpies of fusion and melting points obtained using Differential Scanning Calorimetry (DSC were used to obtain sub-cooled liquid vapour pressures. They have been compared to estimation methods used on the E-AIM website. These methods are shown to poorly represent – OH groups in combination with COOH groups. Partitioning calculations have been performed to illustrate the impact of the different estimation methods on organic aerosol mass compared to the use of experimental data.

  15. Heat capacity measurements on YbGd2–Zr2O7 ( = 0, 1, 2) ceramics by differential scanning calorimetry

    Indian Academy of Sciences (India)

    Zhan-Guo Liu; Jia-Hu Ouyang; Yu Zhou


    YbGd2–Zr2O7 ( = 0, 1, 2) ceramics were pressureless-sintered using ceramic powders acquired by chemical-coprecipitation and calcination methods. Heat capacities of YbGd2–Zr2O7 were measured with a heat flux-type differential scanning calorimetry in the temperature range of 298–1200 K. At 298 K, the heat capacities of Gd2Zr2O7, YbGdZr2O7 and Yb2Zr2O7 were 214, 221 and 230 J.K-1 mol-1, respectively.

  16. Exploration of Energy Metabolism in the Mouse Using Indirect Calorimetry: Measurement of Daily Energy Expenditure (DEE) and Basal Metabolic Rate (BMR). (United States)

    Meyer, Carola W; Reitmeir, Peter; Tschöp, Matthias H


    Current comprehensive mouse metabolic phenotyping involves studying energy balance in cohorts of mice via indirect calorimetry, which determines heat release from changes in respiratory air composition. Here, we describe the measurement of daily energy expenditure (DEE) and basal metabolic rate (BMR) in mice. These well-defined metabolic descriptors serve as meaningful first-line read-outs for metabolic phenotyping and should be reported when exploring energy expenditure in mice. For further guidance, the issue of appropriate sample sizes and the frequency of sampling of metabolic measurements is also discussed.

  17. A quantitative differentiation method for plastic bags by infrared spectroscopy, thickness measurement and differential scanning calorimetry for tracing the source of illegal drugs. (United States)

    Causin, Valerio; Marega, Carla; Carresi, Pietro; Schiavone, Sergio; Marigo, Antonio


    Fifty shopping bags, commonly encountered in the packaging of drug doses, were characterized by thickness measurements, infrared spectroscopy and differential scanning calorimetry. By these very straightforward and inexpensive techniques, without sample preparation, nearly all the considered samples could be discriminated. Ninety-seven percent of the possible pairs of white, apparently similar dull polymer films were differentiated. The rather large degree of variability existing in grocery bags, even though they are mass produced, was shown, confirming that these items can be useful in tracing the source of illicit drug doses.

  18. Direct calorimetry identifies deficiencies in respirometry for the determination of resting metabolic rate in C57Bl/6 and FVB mice. (United States)

    Burnett, Colin M L; Grobe, Justin L


    Substantial research efforts have been aimed at identifying novel targets to increase resting metabolic rate (RMR) as an adjunct approach to the treatment of obesity. Respirometry (one form of "indirect calorimetry") is unquestionably the dominant technique used in the obesity research field to assess RMR in vivo, although this method relies upon a lengthy list of assumptions that are likely to be violated in pharmacologically or genetically manipulated animals. A "total" calorimeter, including a gradient layer direct calorimeter coupled to a conventional respirometer, was used to test the accuracy of respirometric-based estimations of RMR in laboratory mice (Mus musculus Linnaeus) of the C57Bl/6 and FVB background strains. Using this combined calorimeter, we determined that respirometry underestimates RMR of untreated 9- to 12-wk-old male mice by ∼10-12%. Quantitative and qualitative differences resulted between methods for untreated C57Bl/6 and FVB mice, C57Bl/6 mice treated with ketamine-xylazine anesthesia, and FVB mice with genetic deletion of the angiotensin II type 2 receptor. We conclude that respirometric methods underestimate RMR in mice in a magnitude that is similar to or greater than the desired RMR effects of novel therapeutics. Sole reliance upon respirometry to assess RMR in mice may lead to false quantitative and qualitative conclusions regarding the effects of novel interventions. Increased use of direct calorimetry for the assessment of RMR and confirmation of respirometry results and the reexamination of previously discarded potential obesity therapeutics are warranted.

  19. Temperature dependence of adsorption of PEGylated lysozyme and pure polyethylene glycol on a hydrophobic resin: comparison of isothermal titration calorimetry and van't Hoff data. (United States)

    Werner, Albert; Hackemann, Eva; Hasse, Hans


    The influence of temperature on the adsorption of PEGylated lysozyme and pure PEG on Toyopearl PPG-600M, a hydrophobic resin, is studied by batch equilibrium measurements and pulse response experiments. Differently PEGylated lysozymes are used for the studies, enabling a systematic variation of the solute properties. Either ammonium sulfate or sodium chloride are added. The enthalpy of adsorption is calculated from a van't Hoff analysis based on these data. It is also directly measured by Isothermal Titration Calorimetry. In the investigated temperature range from 5 °C to 35 °C adsorption is favored by higher temperatures and hence endothermic. The results of the van't Hoff analysis of the equilibrium and the pulse response data agree well. Discrepancies between enthalpies of adsorption obtained by calorimetry and van't Hoff analysis are found and discussed. We conclude that the most likely explanation is that thermodynamic equilibrium is not reached in the experiments even though they were carried out carefully and in the generally accepted way.

  20. Interactions of phenol with cationic micelles of hexadecyltrimethylammonium bromide studied by titration calorimetry, conductimetry, and 1H NMR in the range of low additive and surfactant concentrations. (United States)

    Chaghi, Radhouane; de Ménorval, Louis-Charles; Charnay, Clarence; Derrien, Gaëlle; Zajac, Jerzy


    Interactions of phenol (PhOH) with micellar aggregates of hexadecyltrimethylammonium bromide (HTAB) in aqueous solutions at surfactant concentrations close to the CMC and phenol contents of 1, 5, or 10 mmol kg(-1) have been investigated at 303 K by means of titration calorimetry, solution conductimetry, and (1)H NMR spectroscopy. Estimates of the main thermodynamic parameters related to HTAB micellization were made for PhOH/HTAB/H(2)O systems based on the specific conductivity measurements and calorimetric determination of the cumulative enthalpy of dilution as functions of the surfactant concentration at a fixed additive content. The combined analysis of the results obtained in H(2)O solutions pointed to the preferential location of PhOH in the outer micelle parts by an enthalpy-driven mechanism. Additional PhOH molecules were located increasingly deeper within the micelle core. The (1)H NMR study of PhOH solubilization by 1.5 mmol kg(-1) HTAB solutions in D(2)O indicated that the two categories of the solubilization site became saturated with the solubilizate already at the lowest additive content. Dissimilar amounts of the solubilized material in H(2)O and D(2)O solutions were ascribed to the difference in the initial micelle structures formed in the two solvents, as inferred from calorimetry and (1)H NMR studies of the HTAB micellization in D(2)O and H(2)O.

  1. Application of In-Line Mid-Infrared (MIR) Spectroscopy Coupled with Calorimetry for the Determination of the Molar Enthalpy of Reaction between Ammonium Chloride and Sodium Nitrite. (United States)

    Kartnaller, Vinicius; Mariano, Danielly C O; Cajaiba, João


    The reaction between ammonium chloride and sodium nitrite has been known for its application as a source of heat because of its large enthalpy of reaction, for which it has been used by the oil industry. There have been no known calorimetric studies for the experimental determination of its molar enthalpy of reaction, which is necessary in order to predict the limits achieved for up-scale applications. Attenuated total reflection Fourier transform infrared spectroscopy (ATR FT-IR) and reaction calorimetry were used to determine this value by using a simple methodology. Both techniques were used concomitantly as a source of information regarding the time-dependent moles converted (Δn) and the amount of exchanged heat (ΔH). The molar enthalpy of reaction was calculated to be -74 ± 4 kcal mol(-1). The percentage between the confidence interval and the calculated value was 5.4%, which shows that the methodology was precise. After the determination of the molar enthalpy of reaction, it was proved that the ATR FT-IR alone was able to be used as a substitute for the reaction calorimetry technique, in which the IR signal is converted to the heat information, presenting as an easier technique for the monitoring of the heat released by this system for future applications.

  2. HypCal, a general-purpose computer program for the determination of standard reaction enthalpy and binding constant values by means of calorimetry. (United States)

    Arena, Giuseppe; Gans, Peter; Sgarlata, Carmelo


    The program HypCal has been developed to provide a means for the simultaneous determination, from data obtained by isothermal titration calorimetry, of both standard enthalpy of reaction and binding constant values. The chemical system is defined in terms of species of given stoichiometry rather than in terms of binding models (e.g., independent or cooperative). The program does not impose any limits on the complexity of the chemical systems that can be treated, including competing ligand systems. Many titration curves may be treated simultaneously. HypCal can also be used as a simulation program when designing experiments. The use of the program is illustrated with data obtained with nicotinic acid (niacin, pyridine-3 carboxylic acid). Preliminary experiments were used to establish the rather different titration conditions for the two sets of titration curves that are needed to determine the parameters for protonation of the carboxylate and amine groups.

  3. Capillary Condensation, Freezing, and Melting in Silica Nanopores: A Sorption Isotherm and Scanning Calorimetry Study on Nitrogen in Mesoporous SBA-15

    CERN Document Server

    Moerz, Sebastian T; Huber, Patrick; 10.1103/PhysRevB.85.075403


    Condensation, melting and freezing of nitrogen in a powder of mesoporous silica grains (SBA-15) has been studied by combined volumetric sorption isotherm and scanning calorimetry measurements. Within the mean field model of Saam and Cole for vapor condensation in cylindrical pores a liquid nitrogen sorption isotherm is well described by a bimodal pore radius distribution. It encompasses a narrow peak centered at 3.3 nm, typical of tubular mesopores, and a significantly broader peak characteristic of micropores, located at 1 nm. The material condensed in the micropores as well as the first two adsorbed monolayers in the mesopores do not exhibit any caloric anomaly. The solidification and melting transformation affects only the pore condensate beyond approx. the second monolayer of the mesopores. Here, interfacial melting leads to a single peak in the specific heat measurements. Homogeneous and heterogeneous freezing along with a delayering transition for partial fillings of the mesopores result in a caloric fr...

  4. Non-additive response of blends of rice and potato starch during heating at intermediate water contents: A differential scanning calorimetry and proton nuclear magnetic resonance study. (United States)

    Bosmans, Geertrui M; Pareyt, Bram; Delcour, Jan A


    The impact of different hydration levels, on gelatinization of potato starch (PS), rice starch (RS) and a 1:1 blend thereof, was investigated by differential scanning calorimetry and related to nuclear magnetic resonance proton distributions of hydrated samples, before and after heating. At 20% or 30% hydration, the visual appearance of all samples was that of a wet powder, and limited, if any, gelatinization occurred upon heating. At 30% hydration, changes in proton distributions were observed and related to plasticization of amorphous regions in the granules. At 50% hydration, the PS-RS blend appeared more liquid-like than other hydrated samples and showed more pronounced gelatinization than expected based on additive behavior of pure starches. This was due to an additional mobile water fraction in the unheated PS-RS blend, originating from differences in water distribution due to altered stacking of granules and/or altered hydration of PS due to presence of cations in RS.

  5. Low-temperature phase transition in glycine-glutaric acid co-crystals studied by single-crystal X-ray diffraction, Raman spectroscopy and differential scanning calorimetry. (United States)

    Zakharov, Boris A; Losev, Evgeniy A; Kolesov, Boris A; Drebushchak, Valeri A; Boldyreva, Elena V


    The occurrence of a first-order reversible phase transition in glycine-glutaric acid co-crystals at 220-230 K has been confirmed by three different techniques - single-crystal X-ray diffraction, polarized Raman spectroscopy and differential scanning calorimetry. The most interesting feature of this phase transition is that every second glutaric acid molecule changes its conformation, and this fact results in the space-group symmetry change from P2(1)/c to P1. The topology of the hydrogen-bonded motifs remains almost the same and hydrogen bonds do not switch to other atoms, although the hydrogen bond lengths do change and some of the bonds become inequivalent.

  6. Characteristics of rose hip (Rosa canina L.) cold-pressed oil and its oxidative stability studied by the differential scanning calorimetry method. (United States)

    Grajzer, Magdalena; Prescha, Anna; Korzonek, Katarzyna; Wojakowska, Anna; Dziadas, Mariusz; Kulma, Anna; Grajeta, Halina


    Two new commercially available high linolenic oils, pressed at low temperature from rose hip seeds, were characterised for their composition, quality and DPPH radical scavenging activity. The oxidative stability of oils was assessed using differential scanning calorimetry (DSC). Phytosterols, tocopherols and carotenoids contents were up to 6485.4; 1124.7; and 107.7 mg/kg, respectively. Phenolic compounds determined for the first time in rose hip oil totalled up to 783.55 μg/kg, with a predominant presence of p-coumaric acid methyl ester. Antiradical activity of the oils reached up to 3.00 mM/kg TEAC. The acid, peroxide and p-anisidine values as well as iron and copper contents indicated good quality of the oils. Relatively high protection against oxidative stress in the oils seemed to be a result of their high antioxidant capacity and the level of unsaturation of fatty acids.

  7. A preliminary study of the influence of ions in the pore solution of hardened cement pastes on the porosity determination by low temperature calorimetry

    DEFF Research Database (Denmark)

    Wu, Min; Johannesson, Björn; Geiker, Mette


    Thermodynamic modeling was used to predict the ionic concentrations in the pore solution of cement pastes at different temperatures during a freezing and melting measurement in low temperature calorimetry (LTC) studies. By using the predicted ionic concentrations, the temperature depressions caused...... by the ions presented in the pore solution were determined. The influence of the freezing/melting point depression caused by the ions on the determined pore size distribution by LTC was demonstrated. Thermodynamic modeling using the program PHREEQC was performed on the cylinder and powder samples of cement...... pastes prepared by two types of cements, i.e., CEM 132.5 R and CEM III/B 42.5 N. Using the modeled ionic concentrations, the calculated differential pore size distributions for the studied samples with and without considering the temperature depression caused by the ions in the pore solution were...

  8. Evaluation of shrinkage temperature of bovine pericardium tissue for bioprosthetic heart valve application by differential scanning calorimetry and freeze-drying microscopy

    Directory of Open Access Journals (Sweden)

    Virgilio Tattini Jr


    Full Text Available Bovine pericardium bioprosthesis has become a commonly accepted device for heart valve replacement. Present practice relies on the measurement of shrinkage temperature, observed as a dramatic shortening of tissue length. Several reports in the last decade have utilized differential scanning calorimetry (DSC as an alternative method to determine the shrinkage temperature, which is accompanied by the absorption of heat, giving rise to an endothermic peak over the shrinkage temperature range of biological tissues. Usually, freeze-drying microscope is used to determine collapse temperature during the lyophilization of solutions. On this experiment we used this technique to study the shrinkage event. The aim of this work was to compare the results of shrinkage temperature obtained by DSC with the results obtained by freeze-drying microscopy. The results showed that both techniques provided excellent sensitivity and reproducibility, and gave information on the thermal shrinkage transition via the thermodynamical parameters inherent of each method.

  9. The application of differential scanning calorimetry as a mean to determine the oxidative stability of vegetable oils and its comparison with Rancimat

    Directory of Open Access Journals (Sweden)

    Yousef Ramezan


    Full Text Available Differential scanning calorimetry (DSC and Rancimat apparatus have been used to evaluate the oxidative stability of eight different edible vegetable oils. Rancimat apparatus was operated at 110 ⁰C with an air flow of 18-20 L/hand measures the induction period (IP of the selected samples. The DSC technique involved the oxidation of the samples in an oxygen flow DSC cell when the cell temperature was set at isothermal temperatures of 100, 110, 120 and 130 ⁰C. Oxidative induction time (T0 determined by the time, where a rapid exothermic reaction were occurred between oil and oxygen. The results showed that unsaturated edible oils are more susceptible to oxidation in short time, than saturated one. Furthermore, the results indicated that there is a good correlation (p<0.0001 between DSC T0 and the Rancimat values.

  10. Detection of a minor amorphous phase in crystalline etoricoxib by dynamic mechanical analysis: comparison with Raman spectroscopy and modulated differential scanning calorimetry. (United States)

    Clas, Sophie-Dorothee; Lalonde, Karine; Khougaz, Karine; Dalton, Chad R; Bilbeisi, Rana


    Detection and quantification of the amorphous phase of etoricoxib bulk drug substances, a selective cycloogenase-2 inhibitor used for the treatment of osteoarthritis, rheumatoid arthritis, and dental pain, was carried out using modulated differential scanning calorimetry (MDSC), dynamic mechanical analysis (DMA), and Raman spectroscopy. Detection of amorphous content in pharmaceutical powders by DMA is a special application of dynamic mechanical spectroscopy. DMA was found to be a sensitive technique, able to detect the presence of an amorphous phase in a crystalline phase at concentrations as low as 0.5%. The limit of detection (LOD) determined for DMA was 2.5%. In comparison, Raman spectroscopy and MDSC had LOD values of 2% and 5% amorphous, respectively.

  11. Application of isothermal titration calorimetry for characterizing thermodynamic parameters of biomolecular interactions: peptide self-assembly and protein adsorption case studies. (United States)

    Kabiri, Maryam; Unsworth, Larry D


    The complex nature of macromolecular interactions usually makes it very hard to identify the molecular-level mechanisms that ultimately dictate the result of these interactions. This is especially evident in the case of biological systems, where the complex interaction of molecules in various situations may be responsible for driving biomolecular interactions themselves but also has a broader effect at the cell and/or tissue level. This review will endeavor to further the understanding of biomolecular interactions utilizing the isothermal titration calorimetry (ITC) technique for thermodynamic characterization of two extremely important biomaterial systems, viz., peptide self-assembly and nonfouling polymer-modified surfaces. The advantages and shortcomings of this technique will be presented along with a thorough review of the recent application of ITC to these two areas. Furthermore, the controversies associated with the enthalpy-entropy compensation effect as well as thermodynamic equilibrium state for such interactions will be discussed.

  12. Comparison of high sensitivity micro differential scanning calorimetry with X-ray powder diffractometry and FTIR spectroscopy for the characterization of pharmaceutically relevant non-crystalline materials. (United States)

    Song, M; Liebenberg, W; De Villiers, M M


    In this study, high sensitivity micro differential scanning calorimetry (MDSC) in the scanning of dynamic mode was compared to X-ray powder diffractometry (XRPD) for quantifying amorphous nifedipine in mixtures crystalline nifedipine. This technique was also compared with FTIR for quantifying polymorph A of chloramphenicol palmitate (CAP) and poly DL-lactide-co-glycolide) (PLGA) in pharmaceutical formulations. The limit of determination (LOD) achieved by MDSC were 0.06% compared to 5% for XRPD quantification of amorphous nifedipine and 0.02% compared to 7% for IR quanitfication of polymorph A of CAP. As little as 0.165 mg PLGA could be measured in excipients mixtures. Desirable linearity and repeatability were established in all cases.

  13. Internal short circuit and accelerated rate calorimetry tests of lithium-ion cells: Considerations for methane-air intrinsic safety and explosion proof/flameproof protection methods. (United States)

    Dubaniewicz, Thomas H; DuCarme, Joseph P


    Researchers with the National Institute for Occupational Safety and Health (NIOSH) studied the potential for lithium-ion cell thermal runaway from an internal short circuit in equipment for use in underground coal mines. In this third phase of the study, researchers compared plastic wedge crush-induced internal short circuit tests of selected lithium-ion cells within methane (CH4)-air mixtures with accelerated rate calorimetry tests of similar cells. Plastic wedge crush test results with metal oxide lithium-ion cells extracted from intrinsically safe evaluated equipment were mixed, with one cell model igniting the chamber atmosphere while another cell model did not. The two cells models exhibited different internal short circuit behaviors. A lithium iron phosphate (LiFePO4) cell model was tolerant to crush-induced internal short circuits within CH4-air, tested under manufacturer recommended charging conditions. Accelerating rate calorimetry tests with similar cells within a nitrogen purged 353-mL chamber produced ignitions that exceeded explosion proof and flameproof enclosure minimum internal pressure design criteria. Ignition pressures within a 20-L chamber with 6.5% CH4-air were relatively low, with much larger head space volume and less adiabatic test conditions. The literature indicates that sizeable lithium thionyl chloride (LiSOCl2) primary (non rechargeable) cell ignitions can be especially violent and toxic. Because ignition of an explosive atmosphere is expected within explosion proof or flameproof enclosures, there is a need to consider the potential for an internal explosive atmosphere ignition in combination with a lithium or lithium-ion battery thermal runaway process, and the resulting effects on the enclosure.

  14. Adsorption calorimetry during metal vapor deposition on single crystal surfaces: Increased flux, reduced optical radiation, and real-time flux and reflectivity measurements (United States)

    Sellers, Jason R. V.; James, Trevor E.; Hemmingson, Stephanie L.; Farmer, Jason A.; Campbell, Charles T.


    Thin films of metals and other materials are often grown by physical vapor deposition. To understand such processes, it is desirable to measure the adsorption energy of the deposited species as the film grows, especially when grown on single crystal substrates where the structure of the adsorbed species, evolving interface, and thin film are more homogeneous and well-defined in structure. Our group previously described in this journal an adsorption calorimeter capable of such measurements on single-crystal surfaces under the clean conditions of ultrahigh vacuum [J. T. Stuckless, N. A. Frei, and C. T. Campbell, Rev. Sci. Instrum. 69, 2427 (1998)]. Here we describe several improvements to that original design that allow for heat measurements with ˜18-fold smaller standard deviation, greater absolute accuracy in energy calibration, and, most importantly, measurements of the adsorption of lower vapor-pressure materials which would have previously been impossible. These improvements are accomplished by: (1) using an electron beam evaporator instead of a Knudsen cell to generate the metal vapor at the source of the pulsed atomic beam, (2) changing the atomic beam design to decrease the relative amount of optical radiation that accompanies evaporation, (3) adding an off-axis quartz crystal microbalance for real-time measurement of the flux of the atomic beam during calorimetry experiments, and (4) adding capabilities for in situ relative diffuse optical reflectivity determinations (necessary for heat signal calibration). These improvements are not limited to adsorption calorimetry during metal deposition, but also could be applied to better study film growth of other elements and even molecular adsorbates.

  15. Nucleation behavior of melted Bi films at cooling rates from 10{sup 1} to 10{sup 4} K/s studied by combining scanning AC and DC nano-calorimetry techniques

    Energy Technology Data Exchange (ETDEWEB)

    Xiao, Kechao; Vlassak, Joost J., E-mail:


    Highlights: • We proposed a general data reduction scheme that combines scanning AC and DC calorimetry results for the study of reaction kinetics. • Calorimetry measurements at cooling rates ranging from 30 K/s to 20,000 K/s were achieved. • Upon initial melting, the Bi thin-film sample breaks up into thousands of isolated islands, and highly repeatable nucleation behavior is observed. • The nucleation rate of melted Bi is calculated, which can be well described by classical nucleation theory over a wide range of cooling rates. - Abstract: We study the nucleation behavior of undercooled liquid Bi at cooling rates ranging from 10{sup 1} to 10{sup 4} K/s using a combination of scanning DC and AC nano-calorimetry techniques. Upon initial melting, the Bi thin-film sample breaks up into silicon nitride-coated isolated islands. The number of islands in a typical sample is sufficiently large that highly repeatable nucleation behavior is observed, despite the stochastic nature of the nucleation process. We establish a data reduction technique to evaluate the nucleation rate from DC and AC calorimetry results. The results show that the driving force for the nucleation of melted Bi is well described by classical nucleation theory over a wide range of cooling rates. The proposed technique provides a unique and efficient way to examine nucleation kinetics with cooling rates over several orders of magnitude. The technique is quite general and can be used to evaluate reaction kinetics in other materials.

  16. Comparison between absorbed dose to water standards established by water calorimetry at the LNE-LNHB and by application of international air-kerma based protocols for kilovoltage medium energy x-rays. (United States)

    Perichon, N; Rapp, B; Denoziere, M; Daures, J; Ostrowsky, A; Bordy, J-M


    Nowadays, the absorbed dose to water for kilovoltage x-ray beams is determined from standards in terms of air-kerma by application of international dosimetry protocols. New standards in terms of absorbed dose to water has just been established for these beams at the LNE-LNHB, using water calorimetry, at a depth of 2 cm in water in accordance with protocols. The aim of this study is to compare these new standards in terms of absorbed dose to water, to the dose values calculated from the application of four international protocols based on air-kerma standards (IAEA TRS-277, AAPM TG-61, IPEMB and NCS-10). The acceleration potentials of the six beams studied are between 80 and 300 kV with half-value layers between 3.01 mm of aluminum and 3.40 mm of copper. A difference between the two methods smaller than 2.1% was reported. The standard uncertainty of water calorimetry being below 0.8%, and the one associated with the values from protocols being around 2.5%, the results are in good agreement. The calibration coefficients of some ionization chambers in terms of absorbed dose to water, established by application of calorimetry and air-kerma based dosimetry protocols, were also compared. The best agreement with the calibration coefficients established by water calorimetry was found for those established with the AAPM TG-61 protocol.

  17. Influência de alguns parâmetros experimentais nos resultados de análises calorimétricas diferenciais - DSC Influence of some experimental parameters on the results of differential scanning calorimetry - DSC.

    Directory of Open Access Journals (Sweden)

    Cláudia Bernal


    Full Text Available A series of experiments were performed in order to demonstrate to undergraduate students or users of the differential scanning calorimetry (DSC, that several factors can influence the qualitative and quantitative aspects of DSC results. Saccharin, an artificial sweetner, was used as a probe and its thermal behavior is also discussed on the basis of thermogravimetric (TG and DSC curves.

  18. Thermodynamic Insight into the Solvation and Complexation Behavior of U(VI) in Ionic Liquid: Binding of CMPO with U(VI) Studied by Optical Spectroscopy and Calorimetry. (United States)

    Wu, Qi; Sun, Taoxiang; Meng, Xianghai; Chen, Jing; Xu, Chao


    The complexation of U(VI) with octylphenyl-N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO, denoted as L) in ionic liquid (IL) C4mimNTf2 was investigated by UV-vis absorption spectrophotometry and isothermal titration calorimetry. Spectro-photometric titration suggests that three successive complexes, UO2Lj(2+) (j = 1-3), formed both in "dry" (water content U(VI) is much stronger, with stability constants of the respective complexes more than 1 order of magnitude higher than that in wet IL. Energetically, the complexation of U(VI) with CMPO in dry IL is mainly driven by negative enthalpies. In contrast, the complexation in wet IL is overwhelmingly driven by highly positive entropies as a result of the release of a large amount of water molecules from the solvation sphere of U(VI). Moreover, comparisons between the fitted absorption spectra of complexes in wet IL and that of extractive samples from solvent extraction have identified the speciation involved in the extraction of U(VI) by CMPO in ionic liquid. The results from this study not only offer a thermodynamic insight into the complexation behavior of U(VI) with CMPO in IL but also provide valuable information for understanding the extraction behavior in the corresponding solvent extraction system.

  19. Orthogonal Methods for Characterizing the Unfolding of Therapeutic Monoclonal Antibodies: Differential Scanning Calorimetry, Isothermal Chemical Denaturation, and Intrinsic Fluorescence with Concomitant Static Light Scattering. (United States)

    Temel, Deniz B; Landsman, Pavel; Brader, Mark L


    Evaluating prospective protein pharmaceutical stability from accelerated screening is a critical challenge in biotherapeutic discovery and development. Measurements of protein unfolding transitions are widely employed for comparing candidate molecules and formulations; however, the interrelationships between intrinsic protein conformational stability and pharmaceutical robustness are complex and thermal unfolding measurements can be misleading. Beyond the discovery phase of drug development, astute formulation design is one of the most crucial factors enabling the protein to resist damage to its higher order structure-initially from bioprocessing stresses, then from stresses encountered during its journey from the product manufacturing site to the bloodstream of the patient. Therapeutic monoclonal antibodies are multidomain proteins that represent a large and growing segment of the biotechnology pipeline. In this chapter, we describe how differential scanning calorimetry may be leveraged synergistically with isothermal chemical denaturation and intrinsic fluorescence with concomitant static light scattering to elucidate characteristics of mAb unfolding and aggregation that are helpful toward understanding and designing optimal pharmaceutical compositions for these molecules.

  20. Effect of pH on the complexation of kaempferol-4'-glucoside with three β-cyclodextrin derivatives: isothermal titration calorimetry and spectroscopy study. (United States)

    Zheng, Yan; Dong, Li-Na; Liu, Min; Chen, Aiju; Feng, Shangcai; Wang, Bingquan; Sun, Dezhi


    The utilization of kaempferol and its glycosides in food and pharmaceutical industries could be improved by the formation of inclusion complexes with cyclodextrins at different pH. This study explores the complexation of kaempferol-4'-glucoside with sulfobutyl ether-β-cyclodextrin (SBE-β-CD), hydroxypropyl-β-cyclodextrin (HP-β-CD), and methylated-β-cyclodextrin (M-β-CD) in phosphate buffer solutions of different pH using isothermal titration calorimetry, UV-vis absorption and proton nuclear magnetic resonance spectroscopy at 298.2 K. Experimental results showed that kaempferol-4'-glucoside binds with the three β- cyclodextrins in the same 1:1 stoichiometry. The rank order of stability constants is SBE-β-CD > HP-β-CD > M-β-CD at the same pH level and pH 6.0 > pH 7.4 > pH 9.0 for the same cyclodextrin. The binding of kaempferol-4'-glucoside with the three β-cyclodextrin derivatives is synergistically driven by enthalpy and entropy at pH 6.0 and enthalpy-driven at pH 7.4 and 9.0. The possible inclusion mode was that in the cavity of β-CD is included the planar benzopyranic-4-one part of the kaempferol-4'-glucoside.

  1. A systematic study on the reactivity of different grades of charged Li[NixMnyCoz]O2 with electrolyte at elevated temperatures using accelerating rate calorimetry (United States)

    Ma, Lin; Nie, Mengyun; Xia, Jian; Dahn, J. R.


    The reactivity between charged Li[NixMnyCoz]O2 (NMC, with x + y + z = 1, x:y:z = 1:1:1 (NMC111), 4:4:2 (NMC442), 5:3:2 (NMC532), 6:2:2 (NMC622) and 8:1:1 (NMC811)) and traditional carbonate-based electrolytes at elevated temperatures was systematically studied using accelerating rate calorimetry (ARC). The ARC results showed that the upper cut-off potential and NMC composition strongly affect the thermal stability of the various NMC grades when traditional carbonate-based electrolyte was used. Although higher cut-off potential and higher Ni content can help increase the energy density of lithium ion cells, these factors generally increase the reactivity between charged NMC and electrolyte at elevated temperatures. It is hoped that this report can be used to help guide the wise selection of NMC grade and upper cut-off potential to achieve high energy density Li-ion cells without seriously compromising cell safety.

  2. Measurement of Nanomolar Dissociation Constants by Titration Calorimetry and Thermal Shift Assay – Radicicol Binding to Hsp90 and Ethoxzolamide Binding to CAII

    Directory of Open Access Journals (Sweden)

    Vilma Michailovienė


    Full Text Available The analysis of tight protein-ligand binding reactions by isothermal titration calorimetry (ITC and thermal shift assay (TSA is presented. The binding of radicicol to the N-terminal domain of human heat shock protein 90 (Hsp90aN and the binding of ethoxzolamide to human carbonic anhydrase (hCAII were too strong to be measured accurately by direct ITC titration and therefore were measured by displacement ITC and by observing the temperature-denaturation transitions of ligand-free and ligand-bound protein. Stabilization of both proteins by their ligands was profound, increasing the melting temperature by more than 10 ºC, depending on ligand concentration. Analysis of the melting temperature dependence on the protein and ligand concentrations yielded dissociation constants equal to 1 nM and 2 nM for Hsp90aN-radicicol and hCAII-ethoxzolamide, respectively. The ligand-free and ligand-bound protein fractions melt separately, and two melting transitions are observed. This phenomenon is especially pronounced when the ligand concentration is equal to about half the protein concentration. The analysis compares ITC and TSA data, accounts for two transitions and yields the ligand binding constant and the parameters of protein stability, including the Gibbs free energy and the enthalpy of unfolding.

  3. Low temperature (down to 450 C) annealed TiAl contacts on N-type gallium nitride characterized by differential scanning calorimetry

    Energy Technology Data Exchange (ETDEWEB)

    Thierry-Jebali, Nicolas [Laboratoire des Multimateriaux et Interfaces, UMR-CNRS 5615, Universite Claude Bernard Lyon 1, 43 Boulevard du 11 Novembre 1918, 69622 Villeurbanne Cedex (France); STMicroelectronics, R and D department, 11 rue Pierre et Marie Curie, 37100 Tours (France); Menard, Olivier [STMicroelectronics, R and D department, 11 rue Pierre et Marie Curie, 37100 Tours (France); Laboratoire de Microelectronique de Puissance, Universite Francois Rabelais de Tours, 1 rue Pierre et Marie Curie, 37100 Tours (France); Chiriac, Rodica; Brylinski, Christian [Laboratoire des Multimateriaux et Interfaces, UMR-CNRS 5615, Universite Claude Bernard Lyon 1, 43 Boulevard du 11 Novembre 1918, 69622 Villeurbanne Cedex (France); Collard, Emmanuel [STMicroelectronics, R and D department, 11 rue Pierre et Marie Curie, 37100 Tours (France); Cayrel, Frederic; Alquier, Daniel [Laboratoire de Microelectronique de Puissance, Universite Francois Rabelais de Tours, 1 rue Pierre et Marie Curie, 37100 Tours (France)


    This work reports on Differential Scanning Calorimetry (DSC) measurements performed on Ti-Al metallic layers stacks deposited on n{sup +}-GaN. The aim is to get better understanding of the mechanisms leading to ohmic contact formation during the annealing stage. Two exothermic peaks were found, one below 500 C and the other one around 660 C. They can be respectively attributed to Al{sub 3}Ti and Al{sub 2}Ti compounds formation. The locations of these peaks provide clear evidence of solid-solid reactions. Lowest contact resistance is well correlated with the presence of Al{sub 3}Ti compound, corresponding to Al(200nm)/Ti(50nm) stoichiometric ratio. Subsequently, Al(200 nm)Ti(50 nm) stacks on n{sup +}-GaN were annealed from 400 C to 650 C. Specific Contact Resistivity (SCR) values stay in the mid 10{sup -5} {omega}.cm{sup 2} range for annealing temperatures between 450 C and 650 C. Such low-temperature annealed contacts on n+-GaN may open new device processing routes, simpler and cheaper, in which Ohmic and Schottky contacts are annealed together. (copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  4. Capillary condensation, freezing, and melting in silica nanopores: A sorption isotherm and scanning calorimetry study on nitrogen in mesoporous SBA-15 (United States)

    Moerz, Sebastian T.; Knorr, Klaus; Huber, Patrick


    Condensation, melting, and freezing of nitrogen in a powder of mesoporous silica grains (SBA-15) has been studied by combined volumetric sorption isotherm and scanning calorimetry measurements. Within the mean-field model of Saam and Cole for vapor condensation in cylindrical pores, a liquid nitrogen sorption isotherm is well described by a bimodal pore radius distribution. It encompasses a narrow peak centered at 3.3 nm, typical of tubular mesopores, and a significantly broader peak characteristic of micropores, located at 1 nm. The material condensed in the micropores as well as the first two adsorbed monolayers in the mesopores do not exhibit any caloric anomaly. The solidification and melting transformation affects only the pore condensate beyond approximately the second monolayer of the mesopores. Here, interfacial melting leads to a single peak in the specific-heat measurements. Homogeneous and heterogeneous freezing along with a delayering transition for partial fillings of the mesopores result in a caloric freezing anomaly similarly complex and dependent on the thermal history to that observed for argon in SBA-15. The axial propagation of the crystallization in pore space is more effective in the case of nitrogen than previously observed for argon, which we attribute to differences in the crystalline textures of the pore solids.

  5. Unraveling the impact of hydroxylation on interactions of bile acid cationic lipids with model membranes by in-depth calorimetry studies. (United States)

    Singh, Manish; Bajaj, Avinash


    We used eight bile acid cationic lipids differing in the number of hydroxyl groups and performed in-depth differential scanning calorimetry studies on model membranes doped with different percentages of these cationic bile acids. These studies revealed that the number and positioning of free hydroxyl groups on bile acids modulate the phase transition and co-operativity of membranes. Lithocholic acid based cationic lipids having no free hydroxyl groups gel well with dipalmitoylphosphatidylcholine (DPPC) membranes. Chenodeoxycholic acid lipids having one free hydroxyl group at the 7'-carbon position disrupt the membranes and lower their co-operativity. Deoxycholic acid and cholic acid based cationic lipids have free hydroxyl groups at the 12'-carbon position, and at 7'- and 12'-carbon positions respectively. Doping of these lipids at high concentrations increases the co-operativity of membranes suggesting that these lipids might induce self-assembly in DPPC membranes. These different modes of interactions between cationic lipids and model membranes would help in future for exploring their use in DNA/drug delivery.

  6. Direct determination of k Q for Farmer-type ionization chambers in a clinical scanned carbon ion beam using water calorimetry (United States)

    Osinga-Blättermann, J.-M.; Brons, S.; Greilich, S.; Jäkel, O.; Krauss, A.


    Until now, the dosimetry of carbon ions with ionization chambers has not reached the same level of accuracy as that of high-energy photons. This is mainly caused by the approximately threefold larger uncertainty of the k Q factor of ionization chambers, which, due to the lack of experimental data, is still derived by calculations. Measurements of absorbed dose to water, D w, by means of water calorimetry have now been performed in the entrance channel of a scanned 6 cm  ×  6 cm radiation field of 429 MeV/u carbon ions, allowing the direct calibration of ionization chambers and thus the experimental determination of k Q. Within this work, values for k Q have been determined for the Farmer-type ionization chambers FC65-G and TM30013. A detailed investigation of the radiation field enabled the accurate determination of correction factors needed for both calorimetric and ionometric measurements. Finally, a relative standard measurement uncertainty of 0.8% (k  =  1) could be achieved for the experimental k Q values. For both chambers, the experimental k Q factors were found to be about 1% larger than those tabulated in the German DIN 6801-1 protocol, whereas compared to the theoretical values stated in the TRS-398 protocol, the experimental k Q value agrees within 0.4% for the TM30013 chamber but is about 1% lower in the case of the FC65-G chamber.

  7. Establishment of Heat Treatment Process for Modified 440A Martensitic Stainless Steel Using Differential Scanning Calorimetry and Thermo-Calc Calculation

    Directory of Open Access Journals (Sweden)

    Huei-Sen Wang


    Full Text Available To provide a suitable microstructure and mechanical properties for modified Grade 440A martensitic stainless steel (MSS, which could facilitate the further cold deformation process (e.g., cold rolling, this work used differential scanning calorimetry (DSC and Thermo-Calc software to determine three soaking temperatures for annealing heat treatment processes (HT1, HT2 and HT3. To verify the feasibility of the proposed annealing heat treatment processes, the as-received samples were initially heated to 1050 °C (similar to the on-line working temperature for 30 min and air quenched to form a martensitic structure. The air-quenched samples were then subjected to three developed annealing heat treatment conditions. The microstructure and mechanical properties of the heat-treated samples were then investigated. Test results showed that considering the effects of the microstructure and the hardness, the HT1, the HT2 or the soaking temperatures between the HT1 and HT2 were the most recommended processes to modified Grade 440A MSS. When using the recommended processes, their carbides were fine and more evenly distributed, and the microhardness was as low as 210 Hv, which can be applied to the actual production process.

  8. Determination of thermodynamic potentials and the aggregation number for micelles with the mass-action model by isothermal titration calorimetry: A case study on bile salts. (United States)

    Olesen, Niels Erik; Westh, Peter; Holm, René


    The aggregation number (n), thermodynamic potentials (ΔG, ΔH, ΔS) and critical micelle concentration (CMC) for 6 natural bile salts were determined on the basis of both original and previously published isothermal titration calorimetry (ITC) data. Different procedures to estimate parameters of micelles with ITC were compared to a mass-action model (MAM) of reaction type: n⋅S⇌Mn. This analysis can provide guidelines for future ITC studies of systems behaving in accordance with this model such as micelles and proteins that undergo self-association to oligomers. Micelles with small aggregation numbers, as those of bile salts, are interesting because such small aggregates cannot be characterized as a separate macroscopic phase and the widely applied pseudo-phase model (PPM) is inaccurate. In the present work it was demonstrated that the aggregation number of micelles was constant at low concentrations enabling determination of the thermodynamic potentials by the MAM. A correlation between the aggregation number and the heat capacity was found, which implies that the dehydrated surface area of bile salts increases with the aggregation number. This is in accordance with Tanford's principles of opposing forces where neighbouring molecules in the aggregate are better able to shield from the surrounding hydrophilic environment when the aggregation number increases.

  9. Thermodynamic insights into drug-surfactant interactions: Study of the interactions of naporxen, diclofenac sodium, neomycin, and lincomycin with hexadecytrimethylammonium bromide by using isothermal titration calorimetry. (United States)

    Choudhary, Sinjan; Talele, Paurnima; Kishore, Nand


    The success of drug delivery depends on the efficiency of the route of administration, which in turn relies on properties of the drug and its transport vehicle. A quantitative knowledge of association of drugs with transport vehicles is lacking when the latter are in the category of self assembled structures. The work reported in this manuscript addresses the mechanism of partitioning of naproxen, diclofenac sodium, neomycin and lincomycin in the micelles of hexadecytrimethylammonium bromide and that is quantitatively based on the measurement of thermodynamic parameters of interactions by using isothermal titration calorimetry. The addressed mechanism of partitioning is based on the identification of the type of interactions of these drugs with the surfactant micelles and monomers, along with the effect of the former on the micellization properties of the surfactant. The conclusions are based on the interpretation of the values of partitioning constant, standard molar enthalpy change, standard molar entropy change and the stoichiometry of the interaction. The results of this study have implications for deriving guidelines for the target oriented synthesis of new drugs that are to be used for effective delivery via micellar media.

  10. Interaction of arginine with protein during refolding process probed by amide H/D exchange mass spectrometry and isothermal titration calorimetry. (United States)

    Zhao, Dawei; Liu, Yongdong; Zhang, Guifeng; Zhang, Chun; Li, Xiunan; Wang, Qingqing; Shi, Hong; Su, Zhiguo


    Arginine has been widely used as low molecular weight additive to promote protein refolding by suppressing aggregate formation. However, methods to investigate the role of arginine in protein refolding are often limited on protein's global conformational properties. Here, hydrogen/deuterium exchange mass spectrometry (HDX-MS) was used to study the effects of arginine on recombinant human granulocyte colony-stimulating factor (rhG-CSF) refolding at the scale of peptide mapping. It was found that deuteration levels of rhG-CSF refolded with arginine was higher than that without arginine during the whole refolding process, but they became almost the same when the refolding reached equilibrium. This phenomenon indicated that arginine could protect some amide deuterium atoms from being exchanged with hydrogen, but the protection diminished gradually along with refolding proceeding. Enzymatic digestion revealed six particular peptides of 16-47, 72-84, 84-93, 114-124, 145-153 and 154-162 were mainly responsible for the deuteration, and all of them dominantly located in protein's α-helix domain. Furthermore, thermodynamics analysis by isothermal titration calorimetry provided direct evidence that arginine could only react with denatured and partially refolded rhG-CSF. Taking all of the results together, we suggest that arginine suppresses protein aggregation by a reversible combination. At the initial refolding stage, arginine could combine with the denatured protein mainly through hydrogen bonding. Subsequently, arginine is gradually excluded from protein with protein's native conformation recovering.

  11. Water absorption of freeze-dried meat at different water activities: a multianalytical approach using sorption isotherm, differential scanning calorimetry, and nuclear magnetic resonance. (United States)

    Venturi, Luca; Rocculi, Pietro; Cavani, Claudio; Placucci, Giuseppe; Dalla Rosa, Marco; Cremonini, Mauro A


    Hydration of freeze-dried chicken breast meat was followed in the water activity range of aw=0.12-0.99 by a multianalytical approach comprising of sorption isotherm, differential scanning calorimetry (DSC), and nuclear magnetic resonance (NMR). The amount of frozen water and the shape of the T2-relaxogram were evaluated at each water content by DSC and NMR, respectively. Data revealed an agreement between sorption isotherm and DSC experiments about the onset of bulk water (aw=0.83-0.86), and NMR detected mobile water starting at aw=0.75. The origin of the short-transverse relaxation time part of the meat NMR signal was also reinvestigated through deuteration experiments and proposed to arise from protons belonging to plasticized matrix structures. It is proved both by D2O experiments and by gravimetry that the extra protons not contributing to the water content in the NMR experiments are about 6.4% of the total proton NMR CPMG signal of meat.

  12. Mechanistic investigation of the interaction between bisquaternary antimicrobial agents and phospholipids by liquid secondary ion mass spectrometry and differential scanning calorimetry. (United States)

    Pashynskaya, V A; Kosevich, M V; Gömöry, A; Vashchenko, O V; Lisetski, L N


    Mechanisms of interaction between the antimicrobial drugs decamethoxinum and aethonium, which are based on bisquaternary ammonium compounds, and a phospholipid component of biological membranes, dipalmitoylphosphatidylcholine, were studied by means of liquid secondary ion mass spectrometry (LSIMS) and differential scanning calorimetry (DSC). Supramolecular complexes of the drugs with this phospholipid were recorded under secondary ion mass spectrometric conditions. The dependence of the structures of these complexes on structural parameters of the dications of the bisquaternary ammonium compounds was demonstrated. Tandem mass spectrometric investigations of the metastable decay of doubly charged ions of decamethoxinum and aethonium complexes with dipalmitoylphosphatidylcholine allowed estimation of structural parameters of these complexes in the gas phase. Interactions of decamethoxinum and aethonium with model membrane assemblies built from hydrated dipalmitoylphosphatidylcholine were studied using DSC. It was shown that while both drugs can interact with model membranes, the mechanisms of such interactions for decamethoxinum and aethonium differ. The correlation between the nature of these interactions and structural and electronic parameters of the dications of the two bisquaternary agents is discussed. Interpretation of combined mass spectrometric and calorimetric experimental data led to proposals that the molecular mechanisms of antimicrobial action of bisquaternary ammonium compounds are related to their effect on the membrane phospholipid components of microbial cells.

  13. Thermotropic phase behaviour of alpha-dipalmitoylphosphatidylcholine multibilayers is influenced to various extents by carotenoids containing different structural features--evidence from differential scanning calorimetry. (United States)

    Kostecka-Gugała, Anna; Latowski, Dariusz; Strzałka, Kazimierz


    Carotenoids are the effective modulators of physical properties of model and natural membranes. To demonstrate the relationship between the structure of carotenoids and their effect on the molecular dynamics of membranes, we have investigated the influence of five structurally different carotenoids: beta-carotene, lycopene, lutein, violaxanthin, zeaxanthin and additionally carotane--a fully saturated derivative of beta-carotene, on thermotropic phase behaviour of dipalmitoylphosphatidylcholine (DPPC) multilamellar vesicles by means of differential scanning calorimetry (DSC). The results obtained indicate that the carotenoids used modulated the thermotropic properties of multibilayers to various extents, broadening the pretransition and the main phase transition peaks and shifting them to lower temperatures. Pronounced decrease of pretransition enthalpy (DeltaH(p)) proves that carotenoids very strongly alter the membrane properties in its gel phase. Comparison of the influence of several carotenoids shows that a rigid, polyisoprenoid chain plays a basic role in altering the thermotropic properties of such membranes and the presence of rings without oxygen-containing groups has a minor significance for the observed interactions. Carotenoids containing epoxy and/or hydroxy groups attached to their rings modify the thermotropic phase behaviour of DPPC multilamellar vesicles stronger than carotenes--a result of their orientation in the DPPC bilayer.

  14. Energy consumption assessment by indirect calorimetry in critically ill children%危重症患儿能量代谢评估研究进展

    Institute of Scientific and Technical Information of China (English)

    施惠宣(综述); 陆国平(审校)


    Nutritional and metabolic disorders are the common problems in PICU. They often lead to deterioration in child nutrition and vice versa. Reasonable assessment of the energy consumption can provide theoretical basis for proper nutrition support in critically ill children. In this review, the methods of evaluating the energy consumption which included energy metabolism measurement and prediction equations were introduced, and the importance of indirect calorimetry was emphasized. Meanwhile, the research situation of energy consumption assessment at home and abroad and the current status of its clinical application were also reviewed.%营养代谢紊乱是儿科重症监护病房中的常见问题,疾病常导致患儿营养状况恶化,而营养不良则不利于疾病预后。合理的能量消耗评估可为危重症患儿合理的营养支持提供理论依据。文章介绍相关的能量代谢评估方法,包括能量代谢测得法及公式预测法,并强调间接能量测定法的重要性;同时综述国内外研究情况及其临床应用现状。

  15. Dimyristoylphosphatidylcholine/C16 : 0-ceramide binary liposomes studied by differential scanning calorimetry and wide- and small-angle X-ray scattering

    DEFF Research Database (Denmark)

    Holopainen, J.M.; Lemmich, J.; Richter, F.


    hydrated binary membranes composed of dimyristoylphosphatidylcholine (DMPC) and N-palmitoyl-ceramide (C16:0-ceramide, up to a mole fraction X-cer = 0.35) were resolved in further detail by high-sensitivity differential scanning calorimetry (DSC) and x-ray diffraction. Both methods reveal very strong...... of the studied compositions there is an endotherm in the region close to the T-m for DMPC. At X-cer greater than or equal to 0.03 a second endotherm is evident at higher temperatures, starting at 32.1 degrees C and reaching 54.6 degrees C at X-cer = 0.30. X-ray small-angle reflection heating scans reveal.......35. In the fluid phase increasing X-cer from 0.06 to 0.35 augments d from 61 Angstrom to 64 Angstrom. An L-beta/L-alpha (ripple/fluid) phase coexistence region is observed at high temperatures (from 31 to 56.5 degrees C) when X-cer > 0.03. With cooling from temperatures above 50 degrees C we observe a slow...

  16. Energies of peptide peptide and peptide water hydrogen bonds in collagen: Evidences from infrared spectroscopy, quartz piezogravimetry and differential scanning calorimetry (United States)

    Boryskina, O. P.; Bolbukh, T. V.; Semenov, M. A.; Gasan, A. I.; Maleev, V. Ya.


    The aim of the present work is a quantitative estimation of energies of peptide-peptide N 1sbnd H 1⋯O 2dbnd C 2 and peptide-water hydrogen bonds in collagen type I and model collagen polypeptide poly(Gly-Pro-Pro). Being a challenging theoretical task this is also an issue that can clarify the physical basis of stability of collagen structures that play a very important structural role in connective tissue. The study was performed on the basis of a complex approach of a number of experimental techniques, namely infrared spectroscopy, quartz piezogravimetry and differential scanning calorimetry. Our results indicate that binding of 3-4 water molecules of the internal hydration shell to each -Gly-X-Y- unit of poly(Gly-Pro-Pro) and collagen leads to simultaneous conformational reorganization of the triple helix and strengthening of the peptide-peptide hydrogen bonds. Enthalpies of hydration of poly(Gly-Pro-Pro) and collagen constitute -10.9 and -12.2 kJ/mol, respectively. Enthalpies of peptide-peptide N 1sbnd H 1⋯O 2dbnd C 2 hydrogen bonds are -7.6 and -6.0 kJ/mol in poly(Gly-Pro-Pro) and collagen, correspondently. The results obtained can be used for evaluation of the impacts of energies of different types of interactions into the total energy of stabilization of native triple helical collagen and poly(Gly-Pro-Pro).

  17. An investigation into the subambient behavior of aqueous mannitol solutions using differential scanning calorimetry, cold stage microscopy, and X-ray diffractometry. (United States)

    Kett, Vicky L; Fitzpatrick, Shaun; Cooper, Brett; Craig, Duncan Q M


    The subambient behavior of aqueous mannitol solutions is of considerable relevance to the preparation of freeze dried formulations. In this investigation the properties of 3% w/v mannitol solutions were investigated using differential scanning calorimetry (DSC), cold stage microscopy (CSM), and X-ray diffraction (XRD) to identify the thermal transitions and structural transformations undergone by this system. It was found that on cooling from ambient the system formed ice at circa -20 degrees C while a further exotherm was seen at approximately -30 degrees C. Upon reheating an endotherm was seen at circa -30 degrees C followed immediately by an exotherm at circa -25 degrees C. Temperature cycling indicated that the thermal transitions observed upon reheating were not reversible. Modulated temperature DSC (MTDSC) indicated that the transitions observed upon reheating corresponded to a glass transition immediately followed by recrystallization, XRD data showed that recrystallization was into the beta form. Annealing at -35 degrees C for 40 min prior to cooling and reheating resulted in a maximum enthalpy being observed for the reheating exotherm. It is concluded that on cooling 3% w/v aqueous mannitol solutions an amorphous phase is formed that subsequently recrystallises into the beta form. The study has also shown that DSC, CSM, and XRD are useful complementary techniques for the study of frozen systems.

  18. Interactions of a cationic antimicrobial (ε-polylysine) with an anionic biopolymer (pectin): an isothermal titration calorimetry, microelectrophoresis, and turbidity study. (United States)

    Chang, Yuhua; McLandsborough, Lynne; McClements, David Julian


    ε-Polylysine (ε-PL) is a food-grade cationic antimicrobial that is highly effective against a range of food pathogens and spoilage organisms. In compositionally complex environments, like those found in most foods and beverages, the antimicrobial activity of cationic ε-PL is likely to be impacted by its interactions with anionic components. The purpose of this study was to characterize the interactions between cationic ε-polylysine and an anionic biopolymer (high methoxyl pectin, HMP) using isothermal titration calorimetry (ITC), microelectrophoresis (ME), and turbidity measurements. ITC and ME measurements indicated that ε-PL bound to pectin, while turbidity measurements indicated that the complexes formed could be either soluble or insoluble depending on solution composition. Ionic strength and pH were also shown to affect the interactions significantly, highlighting their electrostatic origin. This study demonstrates that ε-PL can form either soluble or insoluble complexes with anionic biopolymers depending on the composition of the system. Our study provides basic knowledge that will facilitate the more rational application of ε-PL in complex food systems.

  19. Studying multisite binary and ternary protein interactions by global analysis of isothermal titration calorimetry data in SEDPHAT: application to adaptor protein complexes in cell signaling. (United States)

    Houtman, Jon C D; Brown, Patrick H; Bowden, Brent; Yamaguchi, Hiroshi; Appella, Ettore; Samelson, Lawrence E; Schuck, Peter


    Multisite interactions and the formation of ternary or higher-order protein complexes are ubiquitous features of protein interactions. Cooperativity between different ligands is a hallmark for information transfer, and is frequently critical for the biological function. We describe a new computational platform for the global analysis of isothermal titration calorimetry (ITC) data for the study of binary and ternary multisite interactions, implemented as part of the public domain multimethod analysis software SEDPHAT. The global analysis of titrations performed in different orientations was explored, and the potential for unraveling cooperativity parameters in multisite interactions was assessed in theory and experiment. To demonstrate the practical potential and limitations of global analyses of ITC titrations for the study of cooperative multiprotein interactions, we have examined the interactions of three proteins that are critical for signal transduction after T-cell activation, LAT, Grb2, and Sos1. We have shown previously that multivalent interactions between these three molecules promote the assembly of large multiprotein complexes important for T-cell receptor activation. By global analysis of the heats of binding observed in sets of ITC injections in different orientations, which allowed us to follow the formation of binary and ternary complexes, we observed negative and positive cooperativity that may be important to control the pathway of assembly and disassembly of adaptor protein particles.

  20. Technical decision making with higher order structure data: utilization of differential scanning calorimetry to elucidate critical protein structural changes resulting from oxidation. (United States)

    Arthur, Kelly K; Dinh, Nikita; Gabrielson, John P


    Differential scanning calorimetry (DSC) is a useful tool for monitoring thermal stability of the molecular conformation of proteins. Here, we present an example of the sensitivity of DSC to changes in stability arising from a common chemical degradation pathway, oxidation. This Note is part of a series of industry case studies demonstrating the application of higher order structure data for technical decision making. For this study, six protein products from three structural classes were evaluated at multiple levels of oxidation. For each protein, the melting temperature (Tm ) decreased linearly as a function of oxidation; however, differences in the rate of change in Tm , as well as differences in domain Tm stability were observed across and within structural classes. For one protein, analysis of the impact of oxidation on protein function was also performed. For this protein, DSC was shown to be a leading indicator of decreased antigen binding suggesting a subtle conformation change may be underway that can be detected using DSC prior to any observable impact on product potency. Detectable changes in oxidized methionine by mass spectrometry (MS) occurred at oxidation levels below those with a detectable conformational or functional impact. Therefore, by using MS, DSC, and relative potency methods in concert, the intricate relationship between a primary structural modification, changes in conformational stability, and functional impact can be elucidated.

  1. Improving the dispersity of detonation nanodiamond: differential scanning calorimetry as a new method of controlling the aggregation state of nanodiamond powders. (United States)

    Korobov, Mikhail V; Volkov, Dmitry S; Avramenko, Natalya V; Belyaeva, Lubov' A; Semenyuk, Pavel I; Proskurnin, Mikhail A


    Detonation nanodiamond (ND) is a suitable source material to produce unique samples consisting of almost uniform diamond nanocrystals (d = 3-5 nm). Such samples exist in the form of long stable aqueous dispersions with narrow size distribution of diamond particles. The material is finding ever increasing application in biomedicine. The major problem in producing monodispersed diamond colloids lies in the necessity of deagglomeration of detonation soot and/or removing of clusters formed by already isolated core particles in dry powders. To do this one must have an effective method to monitor the aggregation state or dispersity of powders and gels prior to the preparation of aqueous dispersions. In the absence of dispersity control at various stages of preparation the reproducibility of properties of existing ND materials is poor. In this paper we introduce differential scanning calorimetry (DSC) as a new tool capable to distinguish the state of aggregation in dry and wetted ND materials and to follow changes in this state under different types of treatment. Samples with identical X-ray diffraction patterns (XRD) and high resolution transmission electron microscopy (HRTEM) images gave visibly different DSC traces. Strong correlation was found between dynamic light scattering (DLS) data for colloids and DSC parameters for gels and powders of the same material. Based on DSC data we improved dispersity of existing ND materials and isolated samples with the best possible DSC parameters. These were true monodispersed easily dispersible fractions of ND particles with diameters of ca. 3 nm.

  2. Probing of the combined effect of bisquaternary ammonium antimicrobial agents and acetylsalicylic acid on model phospholipid membranes: differential scanning calorimetry and mass spectrometry studies. (United States)

    Kasian, N A; Pashynska, V A; Vashchenko, O V; Krasnikova, A O; Gömöry, A; Kosevich, M V; Lisetski, L N


    A model molecular biosystem of hydrated dipalmitoylphosphatidylcholine (DPPC) bilayers that mimics cell biomembranes is used to probe combined membranotropic effects of drugs by instrumental techniques of molecular biophysics. Differential scanning calorimetry reveals that doping of the DPPC model membrane with individual bisquaternary ammonium compounds (BQAC) decamethoxinum, ethonium, thionium and acetylsalicylic acid (ASA) leads to lowering of the membrane melting temperature (Tm) pointing to membrane fluidization. Combined application of the basic BQAC and acidic ASA causes an opposite effect on Tm (increase), corresponding to the membrane densification. Thus, modulation of the membranotropic effects upon combined use of the drugs studied can be revealed at the level of model membranes. Formation of noncovalent supramolecular complexes of the individual BQACs and ASA with DPPC molecules, which may be involved in the mechanism of the drug-membrane interaction at the molecular level, is demonstrated by electrospray ionization (ESI) mass spectrometry. In the ternary (DPPC + ASA + BQAC) model systems, the stable complexes of the BQAC dication with the ASA anion, which may be responsible for modulation of the membranotropic effects of the drugs, were recorded by ESI mass spectrometry. The proposed approach can be further developed for preliminary evaluation of the combined effects of the drugs at the level of model lipid membranes prior to tests on living organisms.

  3. Calorimetry investigations of milled α-tricalcium phosphate (α-TCP) powders to determine the formation enthalpies of α-TCP and X-ray amorphous tricalcium phosphate. (United States)

    Hurle, Katrin; Neubauer, Juergen; Bohner, Marc; Doebelin, Nicola; Goetz-Neunhoeffer, Friedlinde


    One α-tricalcium phosphate (α-TCP) powder was either calcined at 500°C to obtain fully crystalline α-TCP or milled for different durations to obtain α-TCP powders containing various amounts of X-ray amorphous tricalcium phosphate (ATCP). These powders containing between 0 and 71wt.% ATCP and up to 2.0±0.1wt.% β-TCP as minor phase were then hydrated in 0.1M Na2HPO4 aqueous solution and the resulting heat flows were measured by isothermal calorimetry. Additionally, the evolution of the phase composition during hydration was determined by in situ XRD combined with the G-factor method, an external standard method which facilitates the indirect quantification of amorphous phases. Maximum ATCP hydration was reached after about 1h, while that of crystalline α-TCP hydration occurred between 4 and 11h, depending on the ATCP content. An enthalpy of formation of -4065±6kJ/mol (T=23°C) was calculated for ATCP (Ca3(PO4)2), while for crystalline α-TCP (α-Ca3(PO4)2) a value of -4113±6kJ/mol (T=23°C) was determined.

  4. Identification and quantification of the crystalline structures of poly(vinylidene fluoride) sutures by wide-angle X-ray scattering and differential scanning calorimetry. (United States)

    Laroche, G; Lafrance, C P; Prud'homme, R E; Guidoin, R


    The outstanding biocompatibility of the polyvinylidene fluoride (PVDF) monofilament suture together with other desirable characteristics, such as ease of handling and resistance to biodegradation, makes it an attractive alternative monofilament suture material for cardiovascular surgery. However, to achieve a high performance suture, the polymeric raw material must be exposed to different treatments, which lead to different degrees and types of crystallization. Since these crystalline modifications deeply influence the mechanical characteristics and the biostability of the sutures, the authors hereby propose a method of quantifying the different structures of PVDF using wide angle X-ray diffraction (WAXD) and differential scanning calorimetry (DSC). The commercial devices are achieved by coloring and processing the polymeric raw material. The white and unprocessed 4-0 unswaged suture presents 19% of the alpha phase, 38% of the beta structure, and no gamma form. Coloration increases the amount of the beta phase by 5-9% at the expense of the alpha phase. On the other hand, processing the fibers lead to the conversion of some of the amorphous phase to the gamma structure, the importance of which is 6-7%. Finally, tensile measurements performed on the different PVDF fibers clearly proves that their mechanical characteristics depend on the presence of these crystalline forms in the polymeric structure of PVDF.

  5. The differences in binding 12-carbon aliphatic ligands by bovine β-lactoglobulin isoform A and B studied by isothermal titration calorimetry and X-ray crystallography. (United States)

    Loch, Joanna I; Bonarek, Piotr; Polit, Agnieszka; Swiątek, Śylwia; Dziedzicka-Wasylewska, Marta; Lewiński, Krzysztof


    Isoforms A (LGB-A) and B (LGB-B) of bovine lactoglobulin, the milk protein, differ in positions 64 (D↔G) and 118 (V↔A). Interactions of LGB-A and LGB-B with sodium dodecyl sulfate (SDS), dodecyltrimethylammonium chloride (DTAC) and lauric acid (LA), 12-carbon ligands possessing differently charged polar groups, were investigated using isothermal titration calorimetry and X-ray crystallography, to study the proton linkage phenomenon and to distinguish between effects related to different isoforms and different ligand properties. The determined values of ΔS and ΔH revealed that for all ligands, binding is entropically driven. The contribution from enthalpy change is lower and shows strong dependence on type of buffer that indicates proton release from the protein varying with protein isoform and ligand type and involvement of LA and Asp64 (in isoform A) in this process. The ligand affinities for both isoforms were arranged in the same order, DTAC enthalpy, resulting in almost identical ΔG for complexes of both isoforms. The determined crystal structures showed that substitution in positions 64 and 118 did not influence the overall structure of LGB complexes. The chemical character of the ligand polar group did not affect the position of its aliphatic chain in protein β-barrel, indicating a major role of hydrophobic interactions in ligand binding that prevailed even with the repulsion between positively charged DTAC and lysine residues located at binding site entrance.

  6. Affinity between TBC1D4 (AS160 phosphotyrosine-binding domain and insulin-regulated aminopeptidase cytoplasmic domain measured by isothermal titration calorimetry

    Directory of Open Access Journals (Sweden)

    SangYoun Park*, Keon Young Kim, Sunmin Kim & Young Seok Yu


    Full Text Available Uptake of circulating glucose into the cells happens via the insulin-mediated signalling pathway, which translocates the glucosetransporter 4 (GLUT4 vesicles from the intracellular compartmentto the plasma membrane. RabㆍGTPases are involvedin this vesicle trafficking, where RabㆍGTPase-activatingproteins (RabGAP enhance the GTP to GDP hydrolysis.TBC1D4 (AS160 and TBC1D1 are functional RabGAPs in theadipocytes and the skeletonal myocytes, respectively. Theseproteins contain two phosphotyrosine-binding domains (PTBsat the amino-terminus of the catalytic RabGAP domain. Thesecond PTB has been shown to interact with the cytoplasmicregion of the insulin-regulated aminopeptidase (IRAP of theGLUT4 vesicle. In this study, we quantitatively measured the∼μM affinity (KD between TBC1D4 PTB and IRAP using isothermaltitration calorimetry, and further showed that IRAP residues1-49 are the major region mediating this interaction. Wealso demonstrated that the IRAP residues 1-15 are necessarybut not sufficient for the PTB interaction.

  7. Kinetics of Cold-Cap Reactions for Vitrification of Nuclear Waste Glass Based on Simultaneous Differential Scanning Calorimetry - Thermogravimetry (DSC-TGA) and Evolved Gas Analysis (EGA)

    Energy Technology Data Exchange (ETDEWEB)

    Rodriguez, Carmen P.; Pierce, David A.; Schweiger, Michael J.; Kruger, Albert A.; Chun, Jaehun; Hrma, Pavel R.


    For vitrifying nuclear waste glass, the feed, a mixture of waste with glass-forming and modifying additives, is charged onto the cold cap that covers 90-100% of the melt surface. The cold cap consists of a layer of reacting molten glass floating on the surface of the melt in an all-electric, continuous glass melter. As the feed moves through the cold cap, it undergoes chemical reactions and phase transitions through which it is converted to molten glass that moves from the cold cap into the melt pool. The process involves a series of reactions that generate multiple gases and subsequent mass loss and foaming significantly influence the mass and heat transfers. The rate of glass melting, which is greatly influenced by mass and heat transfers, affects the vitrification process and the efficiency of the immobilization of nuclear waste. We studied the cold-cap reactions of a representative waste glass feed using both the simultaneous differential scanning calorimetry thermogravimetry (DSC-TGA) and the thermogravimetry coupled with gas chromatography-mass spectrometer (TGA-GC-MS) as complementary tools to perform evolved gas analysis (EGA). Analyses from DSC-TGA and EGA on the cold-cap reactions provide a key element for the development of an advanced cold-cap model. It also helps to formulate melter feeds for higher production rate.

  8. 差示扫描量热法评价聚山梨酯80质量%Quality Evaluation of Polysorbate 80 by a Differential Scanning Calorimetry

    Institute of Scientific and Technical Information of China (English)

    韩荣; 李蒙; 张海燕; 齐云; 杨明; 廖永红


    Objective To investigate the applicability of differential scanning calorimetry ( DSC ) to evaluate the quality of polysorbate 80. Methods Eight different brands of polysorbate 80 were characterized by DSC, and the melting points and peak shape of polysorbate 80 were analyzed. The hemolysis of rabbit in vitro induced by polysorbate 80 was determined with ELISA at 540 nm, whilst the muscle irritation was tested by using creatine kinase ( CK ) kit following exposure of L6 cells with polysorbate 80. Results DSC thermograms showed an excellent reproducibility for the same brand and same batch of polysorbate 80 with the RSD of melting points within 5%. In addition, they were sensitive and distinguished difference between batches or brands of polysorbate 80. DSC thermograms was directly related to the quality. Different batches of polysorbate 80 presented different DSC thermograms, demonstrating differences within constituents of samples, which was confirmed by the results of hemolysis and muscle irritation. Conclusion DSC has the potential to be utilized as a semi-quantitative means for the quality evaluation of polysorbate 80.%目的 研究差示扫描量热法(differential scanning calorimetry,DSC)作为聚山梨酯80质量评价方法的可行性.方法 采用DSC对8个不同品牌的聚山梨酯80进行表征,分析DSC图谱中熔点和峰型;采用酶标法测定聚山梨酯80对家兔体外溶血的影响;采用肌酸激酶(creatine kinase,CK)试剂盒测定聚山梨酯80对L6细胞的刺激性.结果 同一品牌同一批聚山梨酯80熔点相对标准偏差(relative standard deviation,RSD)在5%以内,重复性良好.DSC热分析图具有较好的灵敏度,可甄别批次间成分存在的一定差异.DSC热分析图的差异和品质有直接的相关性,不同品牌的聚山梨酯80呈现差异较大的热分析图,表明这些样品成分差异较大,这一结果得到了体外溶血性和骨骼肌刺激性实验结果的证实.结论 DSC

  9. Crystallization kinetics of Fe-B based amorphous alloys studied in-situ using X-rays diffraction and differential scanning calorimetry

    Directory of Open Access Journals (Sweden)

    Santos D.R. dos


    Full Text Available The crystallization processes for the amorphous metallic alloys Fe74B17Si2Ni4Mo3 and Fe86B6Zr7Cu1 (at. % were investigated using X-rays diffraction measurements performed in-situ during Joule-heating, with simultaneous monitoring of the electrical resistance. We determined the main structural transitions and crystalline phases formed during heating, and correlated these results to the observed resistance variations. As the annealing current is increased, the resistance shows an initial decrease due to stress relaxation, followed by a drop to a minimum value due to massive nucleation and growth of alpha-Fe nanocrystals. Further annealing causes the formation of small fractions of Fe-B, B2Zr or ZrO2, while the resistance increases due to temperature enhancement. In situ XRD measurements allowed the identification of metastable phases, as the gamma-Fe phase which occurs at high temperatures. The exothermal peaks observed in the differential scanning calorimetry (DSC for each alloy corroborate the results. We also have performed DSC measurements with several heating rates, which allowed the determination of the Avrami exponent and crystallization activation energy for each alloy. The obtained activation energies (362 and 301 kJ/mol for Fe-B-Zr-Cu; 323 kJ/mol for Fe-B-Si-Ni-Mo are comparable to reported values for amorphous iron alloys, while the Avrami exponent values (n = 1.0 or n = 1.2 are consistent with diffusion controlled crystallization processes with nucleation rates close to zero.

  10. Mechanochemical effect in the iron(III) spin crossover complex [Fe(3-MeO-salenEt2]PF6 as studied by heat capacity calorimetry. (United States)

    Sorai, Michio; Burriel, Ramón; Westrum, Edgar F; Hendrickson, David N


    Magnetic and thermal properties of the iron(III) spin crossover complex [Fe(3MeO-salenEt)(2)]PF(6) are very sensitive to mechanochemical perturbations. Heat capacities for unperturbed and differently perturbed samples were precisely determined by adiabatic calorimetry at temperatures in the 10-300 K range. The unperturbed compound shows a cooperative spin crossover transition at 162.31 K, presenting a hysteresis of 2.8 K. The anomalous enthalpy and entropy contents of the transition were evaluated to be Delta(trs)H = 5.94 kJ mol(-1) and Delta(trs)S = 36.7 J K(-1) mol(-1), respectively. By mechanochemical treatments, (1) the phase transition temperature was lowered by 1.14 K, (2) the enthalpy and entropy gains at the phase transition due to the spin crossover phenomenon were diminished to Delta(trs)H = 4.94 kJ mol(-1) and Delta(trs)S = 31.1 J K(-1) mol(-1), and (3) the lattice heat capacities were larger than those of the unperturbed sample over the whole temperature range. In spite of different mechanical perturbations (grinding with a mortar and pestle and grinding in a ball-mill), two sets of heat capacity measurements provided basically the same results. The mechanochemical perturbation exerts its effect more strongly on the low-spin state than on the high-spin state. It shows a substantial increase of the number of iron(III) ions in the high-spin state below the transition temperature. The heat capacities of the diamagnetic cobalt(III) analogue [Co(3MeO-salenEt)(2)]PF(6) also were measured. The lattice heat capacity of the iron compounds has been estimated from either the measurements on the cobalt complex using a corresponding states law or the effective frequency distribution method. These estimations have been used for the evaluation of the transition anomaly.

  11. Label-free characterization of carbonic anhydrase-novel inhibitor interactions using surface plasmon resonance, isothermal titration calorimetry and fluorescence-based thermal shift assays. (United States)

    Rogez-Florent, Tiphaine; Duhamel, Laetitia; Goossens, Laurence; Six, Perrine; Drucbert, Anne-Sophie; Depreux, Patrick; Danzé, Pierre-Marie; Landy, David; Goossens, Jean-François; Foulon, Catherine


    This work describes the development of biophysical unbiased methods to study the interactions between new designed compounds and carbonic anhydrase II (CAII) enzyme. These methods have to permit both a screening of a series of sulfonamide derivatives and the identification of a lead compound after a thorough study of the most promising molecules. Interactions data were collected using surface plasmon resonance (SPR) and thermal shift assay (TSA). In the first step, experiments were performed with bovine CAII isoform and were extended to human CAII. Isothermal titration calorimetry (ITC) experiments were also conducted to obtain thermodynamics parameters necessary for the processing of the TSA data. Results obtained with this reference methodology demonstrate the effectiveness of SPR and TSA. KD values obtained from SPR data were in perfect accordance with ITC. For TSA, despite the fact that the absolute values of KD were quite different, the same affinity scale was obtained for all compounds. The binding affinities of the analytes studied vary by more than 50 orders of magnitude; for example, the KD value determined by SPR were 6 ± 4 and 299 ± 25 nM for compounds 1 and 3, respectively. This paper discusses some of the theoretical and experimental aspects of the affinity-based methods and evaluates the protein consumption to develop methods for the screening of further new compounds. The double interest of SPR, that is, for screening and for the quick thorough study of the interactions parameters (ka , kd , and KD ), leads us to choose this methodology for the study of new potential inhibitors.

  12. Characterization of pegylated liposomal mitomycin C lipid-based prodrug (Promitil®) by high sensitivity differential scanning calorimetry and cryogenic transmission electron microscopy. (United States)

    Wei, Xiaohui; Patil, Yogita; Ohana, Patricia; Amitay, Yasmine; Shmeeda, Hilary; Gabizon, Alberto; Barenholz, Yechezkel


    The effect of a lipidated prodrug of mitomycin C (MLP) on the membrane of a pegylated liposome formulation (PL-MLP), also known as Promitil®, was characterized through high-sensitivity differential scanning calorimetry (DSC), and cryo-TEM. The thermodynamic analysis demonstrated that MLP led to the formation of heterogeneous domains in the membrane plane of PL-MLP. MLP concentrated in prodrug-rich domains, arranged in high-ordered crystal-like structures, as suggested by the sharp and high enthalpy endotherm in the 1st heating scanning. After thiolytic cleavage of mitomycin C from MLP by dithiotreitol (DTT) treatment, the crystal-like prodrug domain disappears and a homogeneous membrane with stronger lipid interactions and higher phase transition temperature compared with the blank (MLP-free) liposomes is observed by DSC. In parallel, the rod-like discoid liposomes and the "kissing liposomes" seen by cryo-TEM in the PL-MLP formulation disappear, and liposome mean size and polydispersity increase after DTT treatment. Both MLP and the residual post-cleavage lipophilic moiety of the prodrug increased rigidity of the liposome membrane as indicated by DSC. These results confirm that MLP is inserted in the PL-MLP liposome membrane via its lipophilic anchor, and its mitomycin C moiety located mainly at the region of the phospholipid glycerol backbone and polar head-group. We hypothesize that Π-Π stacking between the planar aromatic rings of the mitomycin C moieties leads to the formation of prodrug-rich domains with highly ordered structure on the PL-MLP liposome membrane. This thermodynamically stable conformation may explain the high stability of the PL-MLP formulation. These results also provide us with an interesting example of the application of high sensitivity DSC in understanding the composition-structure-behavior dynamics of liposomal nanocarriers having a lipid-based drug as pharmaceutical ingredient.

  13. Combination of chemometrically assisted voltammetry, calorimetry, and circular dichroism as a new method for the study of bioinorganic substances: application to selenocystine metal complexes. (United States)

    Gusmão, Rui; Prohens, Rafel; Díaz-Cruz, José Manuel; Ariño, Cristina; Esteban, Miquel


    Selenium-containing compounds play an important role in antioxidant defense systems, binding to toxic metals, preventing their uptake into cells, and thus protecting cells from metal-induced formation of reactive oxygen species. Here, we present a proposal for a relatively new method as a complement to the more usual methods used in selenium studies. A systematic study of the metal-binding properties of selenocystine (SeCyst) in the presence of divalent metal cations (Cd, Co, Hg, Ni, and Zn) is reported. Isothermal titration calorimetry provides thermodynamic parameters of the systems. Titrations produced curves that could be fit reasonably well to the one set of sites model. The data clearly demonstrate that one M(2+) binds one SeCyst molecule, and the stable M(SeCyst) complex is formed under these conditions. The order of the SeCyst binding constant for the metal ions is Hg(2+) > Cd(2+) ~ Zn(2+) > Ni(2+)> Co(2+). Cadmium ion was selected as a modulator for the behavior of SeCyst in the presence of a nonessential metal, and zinc was selected for the case of an essential element. These interactions of SeCyst with Cd(2+) and Zn(2+), either individually or combined, were studied in aqueous buffered solutions at physiological pH by differential pulse polarography and circular dichroism spectroscopy. Furthermore, recently developed chemometric tools were applied to differential pulse polarography data obtained in mixtures of SeCyst and glutathione in the presence of Cd(2+) at physiological pH.

  14. Effect of CdTe quantum dots size on the conformational changes of human serum albumin: results of spectroscopy and isothermal titration calorimetry. (United States)

    Yang, Bingjun; Liu, Rutao; Hao, Xiaopeng; Wu, Yongzhong; Du, Jie


    Quantum dots (QDs) are recognized as some of the most promising candidates for future applications in biomedicine. However, concerns about their safety have delayed their widespread application. Human serum albumin (HSA) is the main protein component of the circulatory system. It is important to explore the interaction of QDs with HSA for the potential in vivo application of QDs. Herein, using spectroscopy and isothermal titration calorimetry (ITC), the effect of glutathione-capped CdTe quantum dots of different sizes on the HSA was investigated. After correction for the inner filter effect, the fluorescence emission spectra and synchronous fluorescence spectra showed that the microenvironment of aromatic acid residues in the protein was slightly changed when the glutathione (GSH)-cadmium telluride (CdTe) QDs was added, and GSH-CdTe QDs with larger particle size exhibited a much higher effect on HSA than the small particles. Although a ground-state complex between HSA and GSH-CdTe QDs was formed, the UV-vis absorption and circular dichroism spectroscopic results did not find appreciable conformational changes of HSA. ITC has been used for the first time to characterize the binding of QDs with HSA. The ITC results revealed that the binding was a thermodynamically spontaneous process mainly driven by hydrophobic interactions, and the binding constant tended to increase as the GSH-CdTe QDs size increased. These findings are helpful in understanding the bioactivities of QDs in vivo and can be used to assist in the design of biocompatible and stable QDs.

  15. Continuous gradient temperature Raman spectroscopy and differential scanning calorimetry of N-3DPA and DHA from -100 to 10°C. (United States)

    Broadhurst, C Leigh; Schmidt, Walter F; Nguyen, Julie K; Qin, Jianwei; Chao, Kuanglin; Aubuchon, Steven R; Kim, Moon S


    Docosahexaenoic acid (DHA, 22:6n-3) is exclusively utilized in fast signal processing tissues such as retinal, neural and cardiac. N-3 docosapentaenoic acid (n-3DPA, 22:5n-3), with just one less double bond, is also found in the marine food chain yet cannot substitute for DHA. Gradient temperature Raman spectroscopy (GTRS) applies the temperature gradients utilized in differential scanning calorimetry (DSC) to Raman spectroscopy, providing a straightforward technique to identify molecular rearrangements that occur near and at phase transitions. Herein we apply GTRS and both conventional and modulated DSC to n-3DPA and DHA from -100 to 20°C. Three-dimensional data arrays with 0.2°C increments and first derivatives allowed complete assignment of solid, liquid and transition state vibrational modes. Melting temperatures n-3DPA (-45°C) and DHA (-46°C) are similar and show evidence for solid-state phase transitions not seen in n-6DPA (-27°C melt). The C6H2 site is an elastic marker for temperature perturbation of all three lipids, each of which has a distinct three dimensional structure. N-3 DPA shows the spectroscopic signature of saturated fatty acids from C1 to C6. DHA does not have three aliphatic carbons in sequence; n-6DPA does but they occur at the methyl end, and do not yield the characteristic signal. DHA appears to have uniform twisting from C6H2 to C12H2 to C18H2 whereas n-6DPA bends from C12 to C18, centered at C15H2. For n-3DPA, twisting is centered at C6H2 adjacent to the C2-C3-C4-C5 aliphatic moiety. These molecular sites are the most elastic in the solid phase and during premelting.

  16. A short period of fasting before surgery conserves basal metabolism and suppresses catabolism according to indirect calorimetry performed under general anesthesia. (United States)

    Yoshimura, Shinichiro; Fujita, Yoshihito; Hirate, Hiroyuki; Kusama, Nobuyoshi; Azami, Takafumi; Sobue, Kazuya


    It is recommended that the period of fasting before elective surgery should be shortened to facilitate a rapid recovery by preventing catabolism. We examined the effects of a short period of fasting on metabolism by performing indirect calorimetry (IC) under general anesthesia. A prospective observational study involving 26 consecutive patients who underwent elective surgery and whose metabolism was evaluated using IC during anesthesia was conducted. The patients were divided into two groups, those who fasted for 10 h (group L). Oxygen consumption, the volume of carbon dioxide emissions (VCO2), the respiratory quotient (RQ), resting energy expenditure (REE), and basal energy expenditure (BEE) were compared. The REE, VCO2, and RQ of group L (17.7 ± 2.3 kcal/kg/day, 118.5 ± 20.8 ml/min, and 0.71 ± 0.12, respectively) were significantly lower than those of group S (19.7 ± 2.3 kcal/kg/day, 143.6 ± 30.9 ml/min, and 0.81 ± 0.09, respectively) (P < 0.05). In group L, the relationship between REE and BEE was weaker (r(2) = 0.501) and the BEE-REE slope was less steep (REE = 0.419BEE + 509.477) than those seen in group S (r(2) = 0.749 and REE = 1.113BEE - 376.111, respectively). Our findings suggest that a short period of fasting (<8 h) before surgery is more strongly associated with the conservation of basal metabolism.

  17. Probing the binding of Cu(2+) ions to a fragment of the Aβ(1-42) polypeptide using fluorescence spectroscopy, isothermal titration calorimetry and molecular dynamics simulations. (United States)

    Makowska, Joanna; Żamojć, Krzysztof; Wyrzykowski, Dariusz; Żmudzińska, Wioletta; Uber, Dorota; Wierzbicka, Małgorzata; Wiczk, Wiesław; Chmurzyński, Lech


    Steady-state and time-resolved fluorescence quenching measurements supported by isothermal titration calorimetry (ITC) and molecular dynamics simulations (MD), with the NMR-derived restraints, were used to investigate the interactions of Cu(2+) ions with a fragment of the Aβ(1-42) polypeptide, Aβ(5-16) with the following sequence: Ac-Arg-His-Asp-Ser-Gly-Tyr-Glu-Val-His-His-Gln-Lys-NH2, denoted as HZ1. The studies presented in this paper, when compared with our previous results (Makowska et al., Spectrochim. Acta A 153: 451-456), show that the affinity of the peptide to metal ions is conformation-dependent. All the measurements were carried out in 20mM 2-(N-morpholino)ethanesulfonic acid (MES) buffer solution, pH6.0. The Stern-Volmer equations, along with spectroscopic observations, were used to determine the quenching and binding parameters. The obtained results unequivocally suggest that Cu(2+) ions quench the fluorescence of HZ1 only through a static quenching mechanism, in contrast to the fragment from the N-terminal part of the FPB28 protein, with sequence Ac-Tyr-Lys-Thr-Ala-Asp-Gly-Lys-Thr-Tyr- NH2 (D9) and its derivative with a single point mutation: Ac-Tyr-Lys-Thr-Ala-Asn-Gly-Lys-Thr-Tyr- NH2 (D9_M), where dynamic quenching occurred. The thermodynamic parameters (ΔITCH, ΔITCS) for the interactions between Cu(2+) ions and the HZ1 peptide were determined from the calorimetric data. The conditional thermodynamic parameters suggest that, under the experimental conditions, the formation of the Cu(2+)-HZ1 complex is both an enthalpy and entropy driven process.

  18. Characterization of the 1st and 2nd EF-hands of NADPH oxidase 5 by fluorescence, isothermal titration calorimetry, and circular dichroism

    Directory of Open Access Journals (Sweden)

    Wei Chin-Chuan


    Full Text Available Abstract Background Superoxide generated by non-phagocytic NADPH oxidases (NOXs is of growing importance for physiology and pathobiology. The calcium binding domain (CaBD of NOX5 contains four EF-hands, each binding one calcium ion. To better understand the metal binding properties of the 1st and 2nd EF-hands, we characterized the N-terminal half of CaBD (NCaBD and its calcium-binding knockout mutants. Results The isothermal titration calorimetry measurement for NCaBD reveals that the calcium binding of two EF-hands are loosely associated with each other and can be treated as independent binding events. However, the Ca2+ binding studies on NCaBD(E31Q and NCaBD(E63Q showed their binding constants to be 6.5 × 105 and 5.0 × 102 M-1 with ΔHs of -14 and -4 kJ/mol, respectively, suggesting that intrinsic calcium binding for the 1st non-canonical EF-hand is largely enhanced by the binding of Ca2+ to the 2nd canonical EF-hand. The fluorescence quenching and CD spectra support a conformational change upon Ca2+ binding, which changes Trp residues toward a more non-polar and exposed environment and also increases its α-helix secondary structure content. All measurements exclude Mg2+-binding in NCaBD. Conclusions We demonstrated that the 1st non-canonical EF-hand of NOX5 has very weak Ca2+ binding affinity compared with the 2nd canonical EF-hand. Both EF-hands interact with each other in a cooperative manner to enhance their Ca2+ binding affinity. Our characterization reveals that the two EF-hands in the N-terminal NOX5 are Ca2+ specific. Graphical abstract

  19. Deep Learning on Imaging Calorimetry


    Mahapatra, Jayesh; Pierini, Maurizio; Vlimant, Jean-Roch; Spiropulu, Maria


    Abstract Particle reconstruction is a significant task in analysis of CMS data. Currently physics based algorithms in conjunction with CMS readouts are used. In this project we explored deep learning as a technique for photon identification and reconstruction on the public LCD CaloImage dataset. Several network architectures were tested for performing classification (photon vs pion discrimination) and regression analysis of energy of particle hits. The performance of the topologies were p...

  20. Digital Calorimetry Using Pixel Sensors

    NARCIS (Netherlands)

    Reicher, M.


    The subject of this thesis is a new type of electromagnetic calorimeter, which is not based on proportionality of deposited energy, but instead on counting the number of showering particles. This calorimeter is a proof of principle for a proposed upgrade of the ALICE experiment at the Large Hadron C

  1. Combined Isothermal Titration and Differential Scanning Calorimetry Define Three-State Thermodynamics of fALS-Associated Mutant Apo SOD1 Dimers and an Increased Population of Folded Monomer. (United States)

    Broom, Helen R; Vassall, Kenrick A; Rumfeldt, Jessica A O; Doyle, Colleen M; Tong, Ming Sze; Bonner, Julia M; Meiering, Elizabeth M


    Many proteins are naturally homooligomers, homodimers most frequently. The overall stability of oligomeric proteins may be described in terms of the stability of the constituent monomers and the stability of their association; together, these stabilities determine the populations of different monomer and associated species, which generally have different roles in the function or dysfunction of the protein. Here we show how a new combined calorimetry approach, using isothermal titration calorimetry to define monomer association energetics together with differential scanning calorimetry to measure total energetics of oligomer unfolding, can be used to analyze homodimeric unmetalated (apo) superoxide dismutase (SOD1) and determine the effects on the stability of structurally diverse mutations associated with amyotrophic lateral sclerosis (ALS). Despite being located throughout the protein, all mutations studied weaken the dimer interface, while concomitantly either decreasing or increasing the marginal stability of the monomer. Analysis of the populations of dimer, monomer, and unfolded monomer under physiological conditions of temperature, pH, and protein concentration shows that all mutations promote the formation of folded monomers. These findings may help rationalize the key roles proposed for monomer forms of SOD1 in neurotoxic aggregation in ALS, as well as roles for other forms of SOD1. Thus, the results obtained here provide a valuable approach for the quantitative analysis of homooligomeric protein stabilities, which can be used to elucidate the natural and aberrant roles of different forms of these proteins and to improve methods for predicting protein stabilities.

  2. Simulations of Gamma-Ray Burst Jets in a Stratified External Medium: Dynamics, Afterglow Light Curves, Jet Breaks, and Radio Calorimetry (United States)

    De Colle, Fabio; Ramirez-Ruiz, Enrico; Granot, Jonathan; Lopez-Camara, Diego


    gradually, causing only a mild flattening in the radio light curve that might be hard to discern when k = 2. Late-time radio calorimetry, which makes use of a spherical flow approximation near the non-relativistic transition, is likely to consistently overestimate the true energy by up to a factor of a few for k = 2, but likely to either overpredict or underpredict it by a smaller factor for k = 0, 1.


    Energy Technology Data Exchange (ETDEWEB)

    De Colle, Fabio; Ramirez-Ruiz, Enrico [TASC, Department of Astronomy and Astrophysics, University of California, Santa Cruz, CA 95064 (United States); Granot, Jonathan [Racah Institute of Physics, The Hebrew University, Jerusalem 91904 (Israel); Lopez-Camara, Diego, E-mail: [Instituto de Ciencias Nucleares, Universidad Nacional Autonoma de Mexico, Ap. 70-543, 04510 D.F. (Mexico)


    in a clear bump-like feature in the light curve. However, for larger k values the jet decelerates more gradually, causing only a mild flattening in the radio light curve that might be hard to discern when k = 2. Late-time radio calorimetry, which makes use of a spherical flow approximation near the non-relativistic transition, is likely to consistently overestimate the true energy by up to a factor of a few for k = 2, but likely to either overpredict or underpredict it by a smaller factor for k = 0, 1.

  4. Assessing sleeping energy expenditure in children using heart-rate monitoring calibrated against open-circuit indirect calorimetry: a pilot study. (United States)

    Beghin, L; Michaud, L; Guimber, D; Vaksmann, G; Turck, D; Gottrand, F


    Total energy expenditure (EE) can be assessed in children by the heart-rate (HR) monitoring technique calibrated against open-circuit indirect calorimetry (IC). In this technique, sleeping EE is usually estimated as the lowest value of a 30 min resting EE measurement x 0 x 90 to give an average for the total sleeping period. However, sleeping is a dynamic process in which sleeping EE is modulated by the effect of factors such as body movement and different sleep stages. The aim of the present study was to determine a new method to improve the sleeping EE measurement by taking into account body movements during sleep. Twenty-four non-obese children participated in the present study. All subjects passed through a calibration period. HR and EE measured by IC were simultaneously collected during resting, the postprandial period, and during different levels of activity. Different methods for computing sleeping EE (resting with different breakpoints ('flex point' HR with linear regression or 'inflection point' (IP) HR with the third order polynomial regression equation (P3)) were compared with EE measured for least 2.0 h in eight sleeping children. The best method of calculation was then tested in sixteen children undergoing HR monitoring and with a body movement detector. In a subset of eight children undergoing simultaneous sleeping EE measurement by IC and HR, the use of the equation resting when HRIP during the sleeping period gave the lowest difference (1 (sd 5.4) %) compared with other methods (linear or polynomial regressions). The new formula was tested in an independent subset of sixteen other children. The difference between sleeping EE computed with the formula resting and sleeping EE computed with resting when HRIP during sleeping periods was significant (13 (sd 5.9) %) only for active sleeping subjects (n 6 of 16 subjects). The correlation between the difference in the results from the two methods of calculation and body movements was close (r 0

  5. 量热技术在铷光谱灯中的应用研究%The Application Study of Differential Scanning Calorimetry Technique in Rubidium Discharge Lamp

    Institute of Scientific and Technical Information of China (English)

    冯浩; 崔敬忠


    铷光谱灯是铷原子钟的核心部件。在铷光谱灯的研制中差式扫描量热技术( DSC)是不可或缺的测量手段和研究方法之一。本文通过对长期老化跟踪测量的铷量消耗数据拟合,得到了目前使用的铷灯的铷量消耗模型。分析结果显示:铷与灯泡内的杂质反应消耗了约37.5μg金属铷,铷的消耗率稳定在0.23μg/ hr ,预计10年使用寿命期内铷的消耗量约106μg。铷熔融曲线的熔点和纯度测量结果显示:铷的熔点和纯度在老化开始前2个月变化明显,具有较好的相关性。老化6个月以后铷的熔点和纯度从老化开始前的36℃和99.56%提高到39.5℃和99.84%,并趋于稳定,其变化趋势与老化初期铷量的消耗规律较好地吻合。%The rubidium ( Rb ) spectral lamp is the critical component of Rb gas cell atomic fre-quency standard. As a measuring tool and research method the differential scanning calorimetry technique was indispensable in the manufacture of rubidium spectral lamp. Through fitting the rubidium consump-tion data obtained by Long-term tracing measurement, the consumption model of a rubidium spectral lamp used currently was established. The analysis result shows that the reactive loss of Rb consume about 37. 5μg metal rubidium, The speed of rubidium consumption maintain constant at 0. 23 microgram per square root of hour. The predicted total rubidium consumption in the ten years lifetime is about 106μg. The measurment result of melting point and purity of rubidium in lamp show that in the first two months, the melting point and purity change sharply with close relativity. After six months aging time, the melting point and purity of rubidium reach at 39 . 5℃ and 99 . 8% from initial 36℃ and 99 . 5% which is fit to the trend of rubidium consumption.

  6. Search for the scalar partner of the top quark and contribution to the improvement of the calorimetry of the experiment D zero for the phase 2 of Tevatron; Recherche du partenaire supersymetrique du quark top et contribution a l'amelioration de la calorimetrie de l'experience D zero pour la phase 2 du tevatron

    Energy Technology Data Exchange (ETDEWEB)

    Olivier, B


    Supersymmetry could be the most natural extension of the Standard Model. In this thesis we present a new search for the sTop, the hypothetical scalar partner of the Top quark, that we performed in the framework of the Minimal Supersymmetric Standard Model (MSSM), using the Run I data of the DO experiment, which corresponds to an integrated luminosity of 108 pb{sup -1}. We selected events with one electron, one muon and missing transverse energy in the final state, which can be the decay product of pair of sTop quarks in 3 (t-tilde {yields} bl{nu}-tilde), or 4-body (t-tilde {yields} b{chi}-tilde{sub 1}{sup 0}l{nu}{sub l}). No signal is seen and the results are interpreted in terms of limits on the sTop production cross-section and exclusion regions in the parameter space (m{sub t}-tilde,m{sub {chi}}-tilde{sub 1{sup 0}}) or (m{sub t}-tilde,m{sub {nu}}-tilde). This new type of selection at the Tevatron for the search of the sTop allowed us to put stronger constraints than those previously published at LEP or at the Tevatron in the t-tilde {yields} bl{nu}-tilde channel, and the first limits ever set in the 4-body decay channel. For the 3-body channel, assuming that the sneutrino is the lightest supersymmetric particle (LSP), the excluded region at 95% confidence level extends up to a sTop mass of 142 (130) GeV if the sneutrino mass (m{sub {nu}}-tilde) is 43 (86) GeV. If the 4-body decay channel dominates, assuming that the neutralino is the LSP, the limit depends on the sneutrino mass. If it is light enough (m{sub {nu}}-tilde {approx}< 100 GeV) this limit reaches a sTop mass of 132 GeV for a neutralino mass of 60 GeV. In all searches for new particles, the calorimetry plays a crucial role from the experimental point of view. The expected increase in integrated luminosity in the Run II which started on the 1. of March 2001, and the detector upgrade which has been achieved over the last three years will allow to extend these exclusion domains or to discover the sTop. We

  7. DSC studies of gamma irradiation influence on gelatinisation and amylose-lipid complex transition occurring in wheat starch[Wheat starch; Gelatinisation; Amylose-lipid complex transition; Gamma irradiation; Differential scanning calorimetry, DSC

    Energy Technology Data Exchange (ETDEWEB)

    Ciesla, K. E-mail:; Eliasson, A.-C


    Differential scanning calorimetry studies are presented dealing with the influence of gamma irradiation (carried out in the solid state) on the structure of amylose-lipid complex in wheat starch. Suspensions of the control and the wheat starch irradiated with a 30 kGy gamma rays (characterised by starch-to-water ratio of 1:1 and ca. 1:4) were examined during several courses of heating and cooling at rates of 2.5 and 10 deg. C min{sup -1}. Differences were observed between enthalpy and temperature of gelatinisation and amylose-lipid complex transition as well as retrogradation taking place in the suspensions and gels of the control and the irradiated starch. The influence of the preceding heating and cooling on further transformations of the amylose-lipid complex differs for the control and the irradiated samples.

  8. Estudio del gasto energético en la anorexia nerviosa: concordancia entre calorimetría indirecta y diferentes ecuaciones Study of energy expenditure in anorexia nervosa: agreement between indirect calorimetry and several equations

    Directory of Open Access Journals (Sweden)

    M.ª C. Cuerda Compés


    Full Text Available El tratamiento nutricional es fundamental en la anorexia nerviosa (AN, si bien la reposición de nutrientes debe hacerse de forma progresiva para evitar la aparición del síndrome de realimentación. Objetivo: Comparar el gasto energético en reposo (GER mediante calorimetría indirecta con el estimado con diferentes fórmulas en mujeres con AN. Material y Métodos: Estudiamos 21 mujeres ingresadas con AN (DSM-IV, edad 17 (DE 5,9 rango 12-34 años. El tiempo de ingreso fue 55,1 ± 20,7 días (21-91. La valoración nutricional inicial incluyó antropometría (IMC, PTC, PSE, CMB,CMMB y bioimpedancia tetrapolar (HoltainBC. La calorimetría indirecta (CI se realizó tras ayuno nocturno (Deltatrac TM II MBM-200. En 9 pacientes se repitió el mismo estudio antes del alta. Comparamos el GER (kcal/24 h medido por CI con el obtenido por diferentes ecuaciones [Fleisch, Harris-Benedict (HB, FAO, Schofield-HW (SHW, Schebendach] mediante el coeficiente de correlación intraclase (CCI y el método de Bland y Altman. Resultados: El estado nutricional mejoró significativamente durante la hopitalización. El 50% del peso recuperado fue masa grasa. El GER aumentó significativamente durante el ingreso. Las fórmulas sobrestimaron el GER respecto al obtenido por CI (p Nutritional management is essential in anorexia nervosa (AN, although nutrient replenishment must be done progressively to prevent the occurrence of re-alimentation syndrome. Objective: to compare resting energy expenditure (REE by means of indirect calorimetry and by different equations in AN female patients. Material and methods: we studied 21 women admitted for AN (DSM-IV, mean age 17 years (SD 5.9, range 12-34 years. Admission stay was 55.1 ± 20.7 days (21-91. Initial nutritional assessment included anthropometrics (BMJ, TSF, SSE, MAC, MAMC and tetrapolar bioimpedance (HoltainBC. Indirect calorimetry (IC was done after overnight fasting (DeltatracTM II MBM-200. In 9 patients, the same study

  9. Conformational restriction approach to β-secretase (BACE1) inhibitors III: effective investigation of the binding mode by combinational use of X-ray analysis, isothermal titration calorimetry and theoretical calculations. (United States)

    Yonezawa, Shuji; Fujiwara, Kenichiro; Yamamoto, Takahiko; Hattori, Kazunari; Yamakawa, Hidekuni; Muto, Chie; Hosono, Motoko; Tanaka, Yoshikazu; Nakano, Toru; Takemoto, Hiroshi; Arisawa, Mitsuhiro; Shuto, Satoshi


    For further investigation of BACE1 inhibitors using conformational restriction with sp(3) hybridized carbon, we applied this approach to 6-substituted aminopyrimidone derivatives 3 to improve the inhibitory activity by reducing the entropic energy loss upon binding to BACE1. Among eight stereoisomers synthesized, [trans-(1'R,2'R),6S] isomer 6 exhibited the best BACE1 inhibitory activity, which was statistically superior to that of the corresponding ethylene linker compound (R)-3. Combinational examinations of the binding mode of 6 were performed, which included isothermal titration calorimetry (ITC), X-ray crystallographic structure analysis and theoretical calculations, to clarify the effect of our conformational restriction approach. From the ITC measurement, the binding entropy of 6 was found to be ∼0.5kcal larger than that of (R)-3, which is considered to be affected by conformational restriction with a cyclopropane ring.

  10. Application of Differential Scanning Calorimetry (DSC) in Analysis of Oils%差示扫描量热法(DSC)在油脂分析中的应用

    Institute of Scientific and Technical Information of China (English)

    宋菲; 王挥; 陈卫军; 赵松林


    In the research of physical properties and the processing products of oils, differential scanning calorimetry (DSC) as a thermal analysis technology is widely used. This paper introduces the application of DSC in the determination of oil composition, crystallization and melting, oxidation and oxidation kinetics and adulteration of oils. This thermal analysis method has very broad prospects in oil scientific research and actual production.%介绍差示扫描量热法(DSC)在测定油脂的组分、结晶与融化、氧化及氧化动力学和油脂掺假等方面的应用,以及热分析法在油脂的科学理论研究和实际生产中的应用前景。

  11. Determination of Activation Energy of Polymer Molecular Chain by Differential Scanning Calorimetry%DSC用于高聚物分子链迁移活化能的测定

    Institute of Scientific and Technical Information of China (English)

    郭健; 靳新慧; 和涛


    本文介绍了差示扫描量热仪 (DSC) 的应用与活化能的定义及其发展, 并利用DSC进行了高聚物分子链迁移活化能的测试, 发现应用DSC测定迁移活化能是较为准确简便的一种方法.%This paper introduce the application of differential scanning calorimetry(DSC),activation energy's definition and development. The author using DHC determine the activation energy of polymer molecular chain. It is found that the applica-tion of DSC in the determination of migration and activation energy is a simple and accurate method.

  12. Simultaneous Synchrotron WAXD and Fast Scanning (Chip) Calorimetry: On the (Isothermal) Crystallization of HDPE and PA11 at High Supercoolings and Cooling Rates up to 200 °C s(-1). (United States)

    Baeten, Dorien; Mathot, Vincent B F; Pijpers, Thijs F J; Verkinderen, Olivier; Portale, Giuseppe; Van Puyvelde, Peter; Goderis, Bart


    An experimental setup, making use of a Flash DSC 1 prototype, is presented in which materials can be studied simultaneously by fast scanning calorimetry (FSC) and synchrotron wide angle X-ray diffraction (WAXD). Accumulation of multiple, identical measurements results in high quality, millisecond WAXD patterns. Patterns at every degree during the crystallization and melting of high density polyethylene at FSC typical scanning rates from 20 up to 200 °C s(-1) are discussed in terms of the temperature and scanning rate dependent material crystallinities and crystal densities. Interestingly, the combined approach reveals FSC thermal lag issues, for which can be corrected. For polyamide 11, isothermal solidification at high supercooling yields a mesomorphic phase in less than a second, whereas at very low supercooling crystals are obtained. At intermediate supercooling, mixtures of mesomorphic and crystalline material are generated at a ratio proportional to the supercooling. This ratio is constant over the isothermal solidification time.

  13. Avaliação nutricional de pacientes com cirrose pelo vírus da hepatite C: a aplicação da calorimetria indireta Nutritional assessment in patients with cirrhosis: the use of indirect calorimetry

    Directory of Open Access Journals (Sweden)

    Catarina Bertaso Andreatta Gottschall


    .BACKGROUND: Malnutrition is frequent in cirrhotic patients, and its assessment is difficult. Functional assessment through a dynamometer is a simple method and could minimize these drawbacks. Harris-Benedict prediction formulae estimates the resting energy expenditure but has not been validated for this population. One alternative is the use of indirect calorimetry. AIM: To assess nutritional status in cirrhotic patients and estimates the resting energy expenditure through indirect calorimetry and compares it to Harris-Benedict. PATIENTS AND METHODS: Thirty four adult hepatitis C cirrhotic outpatients were studied, classified by Child-Pugh and model of end-stage liver disease score. The resting energy expenditure was predicted through Harris-Benedict and measured by indirect calorimetry. Nutritional assessment was done through anthropometry, subjective global assessment, hand-grip strength and a 3-day recall. RESULTS: Fifteen (44.2% were Child-Pug A, 12 (35.3% B and 7 (20.6% C, and 33 (97.1% had model of end-stage liver disease scores less than 20. The resting energy expenditure predicted was higher than the measured (Harris-Benedict 1404.5 ± 150.3 kcal; indirect calorimetry 1059.9 ± 309.6 kcal. The prevalence of malnutrition varied between methods (body mass index, muscle arm circumference, subjective global assessment, triceps skinfold thickness and hand-grip strength: 0; 5.9; 17.6; 35.3 and 79.4%, accordingly. Calories and proteins intake were 80% and 85% of recommended amounts and there was inadequate intake of calcium, magnesium, iron and zinc. CONCLUSION: Malnutrition was frequent and hand-grip strength seemed to be the most sensitive method for its diagnosis. Calories and protein intakes were inadequate. Considering that the predicted resting energy expenditure was higher than the measured one and the need to offer higher caloric intake, the use of the predicting equation may replace indirect calorimetry.

  14. Calorimetría indirecta en el enfermo crítico: validez de la medición Indirect calorimetry in critical ill patients: validity of measurement for ten minutes

    Directory of Open Access Journals (Sweden)

    P. Marsé Milla


    Full Text Available Objetivo: No existen estándares definidos sobre la duración y frecuencia de la medición de la calorimetría indirecta, hecho que tiene importancia en la práctica asistencial diaria. Se valora el grado de concordancia entre el gasto energético en reposo (GER medido en un espacio de tiempo corto (10 minutos frente a otro prolongado (1 hora. Pacientes: Se estudiaron 60 pacientes críticos, sedoanalgesiados y conectados a ventilación mecánica. Intervenciones: El GER se determinó mediante un computador metabólico (Engström Eliza en condiciones de reposo. Se valoró la reproducibilidad y el grado de acuerdo de las mediciones hechas en ambos períodos de tiempo. Resultados: Los valores medios de las determinaciones de GER a 10 y 60 minutos fueron de 1818 ± 319 Kilocalorías/día y de 1815 ± 318 Kcal/día. Los límites de acuerdo entre ambos tiempos fueron de -101 a + 117 Kilocalorías/día y la correlación fue significativa (r = 0.98, p Goal: There are no gold standards on the duration and frequency of the measurement of indirect calorimetry, a fact of importance in daily clinical practice. An assessment of is made of the degree of concordance between energy expenditure at rest (EER measured over a short interval (10 minutes versus another prolonged measurement (1 hour. Patients: Sixty critically-ill patients, under sedation and analgesia with connection to mechanical ventilation, were studied. Interventions: EER values were determined by means of a metabolic computer analysis (Engström Eliza at rest. The reproducibility and the degree of concordance were assessed in the measurements made with both periods. Results: The mean values of the EER determinations at 10 and 60 minutes were 1,818 ± 319 kilocalories/day and 1,815 ± 318 Kcal/day. The limits of the concordance between both times were -101 and +117 kilocalories/day and the correlation was significant (r = 0.98, p < 0.0001. Conclusions: In critically-ill patients under sedation and

  15. Non-isothermal crystallization kinetics and glass-forming ability of Ti{sub 41}Zr{sub 25}Be{sub 28}Fe{sub 6} bulk metallic glass investigated by differential scanning calorimetry

    Energy Technology Data Exchange (ETDEWEB)

    Gong, Pan; Zhao, Shaofan; Yao, Kefu [Tsinghua University, School of Materials Science and Engineering, Beijing (China); Wang, Xin [Hebei University of Technology, School of Materials Science and Engineering, Tianjin (China)


    The non-isothermal crystallization kinetics and glass-forming ability of Ti{sub 41}Zr{sub 25}Be{sub 28}Fe{sub 6} glassy alloy were investigated by differential scanning calorimetry. The activation energies corresponding to the characteristic temperatures have been calculated by Kissinger and Ozawa equations. Based on Kissinger-Akahira-Sunose and Ozawa-Flynn-Wall models, it has been found that the local activation energy is higher at the beginning of the crystallization process for the first exothermic peak. The local Avrami exponent indicates that the first-step crystallization is mainly a high-dimensional nucleation and growth with an increasing nucleation rate. According to the calculated fragility index, Ti{sub 41}Zr{sub 25}Be{sub 28}Fe{sub 6} alloy can be classified as ''strong glass former.'' The studied alloy also possesses a critical size up to centimeter order, and the high glass-forming ability is probably related to the relatively low Gibbs energy difference between the liquid and crystalline states. The critical cooling rate of Ti{sub 41}Zr{sub 25}Be{sub 28}Fe{sub 6} glassy alloy has also been determined using Barandiaran-Colmenero's method. (orig.)

  16. Life Predication of Polypropylene Using Accelerated Aging Method Based Differential Scanning Calorimetry%DSC加速老化试验方法在PP寿命估算中的应用

    Institute of Scientific and Technical Information of China (English)

    孟鑫; 石靖; 裘志浩; 辛忠


    Arrhenius equation which showed the relationship between the oxidation induction time(OIT) and the aging temperature was established based on OIT measured under different temperature by using differential scanning calorimetry (DSC) accelerated aging test method, and the OIT of polypropylene at different temperature was quickly estimated by using Arrhenius equation. The results showed that the estimates based on Arrhenius equation was effective, which was a good method for screening antioxidant formula.%利用差示扫描量热( DSC)加速老化试验方法,以不同温度下测得的氧化诱导时间(OIT)为基础,建立温度寿命相关的阿伦尼乌斯方程,并以此对不同温度下聚丙烯的寿命进行快速估算.结果表明,其估算结果有效,是筛选抗氧剂配方的一种较好的方法.

  17. Application of Cross-C orrelation and Calorimetry in Meas urement of Qil-Water Two Phase Flow%相关分析及量热法在油水两相流测量中的应用

    Institute of Scientific and Technical Information of China (English)

    何安定; 李斌; 周芳德; 任长春


    用相关分析及量热法相结合用于油水两相流测量,并进行了相应的理论分析和试验研究。利用上下游温升的相关性测量总流流量,再用量热法来测量油水比,从而得到油水两相的各自流量。同时,在以前研究的基础上对实验段进行了必要的改进。结果表明,这有利于提高测量精度。%Cross-correlation and calorimetry were applied in the measurement of oil-water two phase flow. The tot al flow rate was calculated from t he correlativity between two tempe rature probes, and the oil-water r atio was got by means of calorimetry. Thus the flow rate for oil and water was obtained respectively. Moreover, the test segment was imp roved based on the previous studies. And the result showed that the accuracy was improved greatly.

  18. In vitro model of infected stratum corneum for the efficacy evaluation of poloxamer 407-based formulations of ciclopirox olamine against Trichophyton rubrum as well as differential scanning calorimetry and stability studies. (United States)

    Täuber, Anja; Müller-Goymann, Christel C


    Superficial fungal skin infections are a common disease and concern 20-25% of the world's population with the dermatophyte Trichophyton rubrum being the main trigger. Due to autoinoculation, fungal skin infections of the feet (tinea pedis) often occur simultaneously with fungal nail infections (onychomycosis). Therefore, the overall objective was the development and characterisation of poloxamer 407-based formulations with the antimycotic active ingredient ciclopirox olamine (CPX) for simultaneous antifungal therapy. The formulations consisted of poloxamer 407, water, isopropyl alcohol, propylene glycol and medium chain triglycerides in given ratios. The in vitro antifungal efficacy against T. rubrum was tested in a novel in vitro model of infected stratum corneum in comparison to a marketed semi-solid formulation containing 1% (w/w) ciclopirox olamine and a marketed nail lacquer containing 8% ciclopirox. Several liquid poloxamer 407-based formulations with only 1% CPX completely inhibited fungal growth after 6 days of incubation, whereas the marketed semi-solid formulation did not inhibit fungal growth. Differential scanning calorimetry studies revealing the interaction between the formulations and the SC showed that increasing isopropyl alcohol/propylene glycol concentrations as well as increasing CPX concentrations caused increasing endothermic transition shifts. Moreover, stability studies at 30 °C exhibited only a slight decrease of the CPX amount after 12 months of storage. Each formulation contained >90% of the initial CPX concentration after termination of the stability studies.

  19. Investigation of magnetocaloric effect in La0.45Pr0.25Ca0.3MnO3 by magnetic, differential scanning calorimetry and thermal analysis (United States)

    Aparnadevi, M.; Barik, S. K.; Mahendiran, R.


    We investigated magnetocaloric effect in La0.45Pr0.25Ca0.3MnO3 by direct methods (changes in temperature and latent heat) and indirect method (magnetization isotherms). This compound undergoes a first-order paramagnetic to ferromagnetic transition with TC=200 K upon cooling. The paramagnetic phase becomes unstable and it transforms into a ferromagnetic phase under the application of magnetic field, which results in a field-induced metamagnetic transition (FIMMT). The FIMMT is accompanied by release of latent heat and temperature of the sample as evidenced from differential scanning calorimetry and thermal analysis experiments. A large magnetic entropy change of ΔSm=-7.2 J kg-1 K-1 at T=212.5 K and refrigeration capacity of 228 J kg-1 are found for a field change of ΔH=5 T. It is suggested that destruction of magnetic polarons and growth of ferromagnetic phase accompanied by a lattice volume change with increasing magnetic field is responsible for the large magnetocaloric effect in this compound.

  20. Detecting thermal hysteresis activity of the total protein in insects with differential scanning calorimetry%应用差示扫描量热法检测昆虫总蛋白的热滞活性

    Institute of Scientific and Technical Information of China (English)

    崔宁宁; 宋希明; 邹元平; 郝树广; 许永玉; 王宪辉


    产生抗冻蛋白是寒带昆虫抵御低温的重要机制之一,但检测其活性仍存在一些困难,尤其对于个体较小的昆虫样品.为了探索差示扫描量热法是否适于检测昆虫总蛋白的热滞活性,本研究利用差示扫描量热法对黄粉虫Tenebrio molitor幼虫的总蛋白和血淋巴分别进行了热滞活性检测.结果表明:黄粉虫总蛋白的热滞活性(0.49~0.98℃)要低于血淋巴(2.54 ~4.34C).通过这种方法,进一步检测了3种在内蒙古大兴安岭林区采集到的越冬昆虫:稠李巢蛾Yponomeuta evonymallus幼虫、舞毒蛾Lymantria dispar卵和落叶松八齿小蠹Ips subelongatus成虫.结果发现,它们都存在热滞活性,其中稠李巢蛾的热滞活性为0.34 ~0.43℃,舞毒蛾的热滞活性为0.35~0.42℃,落叶松八齿小蠹的热滞活性为0.37 ~0.40℃,说明这3种昆虫能以产生抗冻蛋白的方式作为越冬策略之一.本研究表明通过差示扫描量热法检测昆虫总蛋白是否存在热滞活性来判断抗冻蛋白的存在是可行的.%Producing antifreeze proteins is one of the most important mechanisms underlying insect cold tolerance. However, detecting the activity of antifreeze proteins still has some difficulties, especially when only a few of insect samples are available from fields. In order to explore if differential scanning calorimetry (DSC) can be used to detect thermal hysteresis activity ( THA) of the total protein in insects, the THA of the total protein and hemolymph from Tenebrio molitor larvae was detected by DSC. The results showed that the THA of the total protein (0. 49 -0. 98t ) is lower than that of hemolymph (2. 54 -4. 341) in T. molitor. In addition, we collected three overwintering insect species (Lymantria dispar larvae, Yponomeuta evonymallus eggs and Ips subelongatus adults) in the Daxing' anling Forest Region in Inner Mongolia, and then prepared their total protein. Using DSC, the THA of the total protein from the three