Science.gov

Sample records for calorimetry

  1. Calorimetry

    NASA Astrophysics Data System (ADS)

    Fabjan, C. W.; Fournier, D.

    This document is part of Part 1 'Principles and Methods' of Subvolume B 'Detectors for Particles and Radiation' of Volume 21 'Elementary Particles' of Landolt-Börnstein - Group I 'Elementary Particles, Nuclei and Atoms'. It contains the Section '3.2 Calorimetry' of Chapter '3 Particle Detectors and Detector Systems' with the content:

  2. Quantum Calorimetry

    NASA Technical Reports Server (NTRS)

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

    1999-01-01

    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. Quantum Calorimetry

    NASA Technical Reports Server (NTRS)

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

    1999-01-01

    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.

  4. Isothermal titration calorimetry and differential scanning calorimetry.

    PubMed

    Holdgate, Geoff

    2009-01-01

    Isothermal titration [Holdgate (BioTechniques 31:164-184, 2001); Ward and Holdgate (Prog. Med. Chem. 38:309-376, 2001); O'Brien et al. (2001) Isothermal titration calorimetry of biomolecules. In: Harding, S. E. and Chowdhry, B. Z. (eds.), Protein-Ligand Interactions: Hydrodynamics and Calorimetry, A Practical Approach. Oxford University Press, Oxford, UK] and differential scanning calorimetry [Jelesarov and Bosshard (J. Mol. Recognit. 12:3-18, 1999); Privalov and Dragan (Biophys. Chem. 126:16-24, 2007); Cooper et al. (2001) Differential scanning microcalorimetry. In: Harding, S. E. and Chowdhry, B. Z. (eds.), Protein-Ligand Interactions: Hydrodynamics and Calorimetry, A Practical Approach. Oxford University Press, Oxford, UK] are valuable tools for characterising protein targets, and their interactions with ligands, during the drug discovery process. The parameters obtained from these techniques: triangle DeltaH, triangle DeltaG, triangle DeltaS, and triangle DeltaC (p), are properties of the entire system studied and may be composed of many contributions, including the binding reaction itself, conformational changes of the protein and/or ligand during complexation, changes in solvent organisation or other equilibria linked to the binding process. Dissecting and understanding these components, and how they contribute to binding interactions, is a critical step in the ability to design ligands that have high binding affinity for the target protein.

  5. Dynamic Calorimetry for Students

    ERIC Educational Resources Information Center

    Kraftmakher, Yaakov

    2007-01-01

    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…

  6. Dynamic Calorimetry for Students

    ERIC Educational Resources Information Center

    Kraftmakher, Yaakov

    2007-01-01

    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…

  7. Advances in Calorimetry

    SciTech Connect

    Brau, James E.; Jaros, John A.; Ma, Hong

    2010-11-23

    We review recent advances in calorimetry for high-energy physics. We provide an overview of the fundamentals of calorimetry, then survey calorimeters used in recent experiments, which represent the current state of the art. We conclude with descriptions of several research and development efforts and discuss future directions of the field.

  8. Scintillator plate calorimetry

    SciTech Connect

    Price, L.E.

    1990-01-01

    Calorimetry using scintillator plates or tiles alternated with sheets of (usually heavy) passive absorber has been proven over multiple generations of collider detectors. Recent detectors including UA1, CDF, and ZEUS have shown good results from such calorimeters. The advantages offered by scintillator calorimetry for the SSC environment, in particular, are speed (<10 nsec), excellent energy resolution, low noise, and ease of achieving compensation and hence linearity. On the negative side of the ledger can be placed the historical sensitivity of plastic scintillators to radiation damage, the possibility of nonuniform response because of light attenuation, and the presence of cracks for light collection via wavelength shifting plastic (traditionally in sheet form). This approach to calorimetry is being investigated for SSC use by a collaboration of Ames Laboratory/Iowa State University, Argonne National Laboratory, Bicron Corporation, Florida State University, Louisiana State University, University of Mississippi, Oak Ridge National Laboratory, Virginia Polytechnic Institute and State University, Westinghouse Electric Corporation, and University of Wisconsin.

  9. Calorimetry for the SSC

    SciTech Connect

    Gordon, H.A.; Grannis, P.D.

    1984-01-01

    The activities related to calorimetry at Snowmass took place in three main areas. These were: (1) The performance criteria for SSC calorimetry, including the requirements on hermeticity, shower containment, segmentation and time resolution. The use of calorimetric means of particle identification was studied. (2) The study of triggering methods using calorimeter energy, angle and timing information. (3) A review of a wide variety of calorimeter materials for absorber and sampling, as well as several means of obtaining the readout of the energy deposits. 48 references, 10 figures, 1 table.

  10. Scintillator materials for calorimetry

    SciTech Connect

    Weber, M.J.

    1994-09-01

    Requirements for fast, dense scintillator materials for calorimetry in high energy physics and approaches to satisfying these requirements are reviewed with respect to possible hosts and luminescent species. Special attention is given to cerium-activated crystals, core-valence luminescence, and glass scintillators. The present state of the art, limitations, and suggestions for possible new scintillator materials are presented.

  11. Recent developments in silicon calorimetry

    SciTech Connect

    Brau, J.E.

    1990-11-01

    We present a survey of some of the recent calorimeter applications of silicon detectors. The numerous attractive features of silicon detectors are summarized, with an emphasis on those aspects important to calorimetry. Several of the uses of this technology are summarized and referenced. We consider applications for electromagnetic calorimetry, hadronic calorimetry, and proposals for the SSC.

  12. Calorimetry of Nucleic Acids.

    PubMed

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

    2015-12-01

    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.

  13. Differential scanning calorimetry.

    PubMed

    Spink, Charles H

    2008-01-01

    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.

  14. CALORIMETRY OF TRU WASTE MATERIALS

    SciTech Connect

    C. RUDY; ET AL

    2000-08-01

    Calorimetry has been used for accountability measurements of nuclear material in the US. Its high accuracy, insensitivity to matrix effects, and measurement traceability to National Institute of Standards and Technology have made it the primary accountability assay technique for plutonium (Pu) and tritium in the Department of Energy complex. A measurement of Pu isotopic composition by gamma-ray spectroscopy is required to transform the calorimeter measurement into grams Pu. The favorable calorimetry attributes allow it to be used for verification measurements, for production of secondary standards, for bias correction of other faster nondestructive (NDA) methods, or to resolve anomalous measurement results. Presented in this paper are (1) a brief overview of calorimeter advantages and disadvantages, (2) a description of projected large volume calorimeters suitable for waste measurements, and (3) a new technique, direct measurement of transuranic TRU waste alpha-decay activity through calorimetry alone.

  15. Contactless Calorimetry for Levitated Samples

    NASA Technical Reports Server (NTRS)

    Lee, M. C.; Dokko, W.

    1986-01-01

    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.

  16. Contactless Calorimetry for Levitated Samples

    NASA Technical Reports Server (NTRS)

    Lee, M. C.; Dokko, W.

    1986-01-01

    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.

  17. Differential scanning calorimetry of coal

    NASA Technical Reports Server (NTRS)

    Gold, P. I.

    1978-01-01

    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.

  18. Liquid scintillator tiles for calorimetry

    NASA Astrophysics Data System (ADS)

    Amouzegar, M.; Belloni, A.; Bilki, B.; Calderon, J.; De Barbaro, P.; Eno, S. C.; Hatakeyama, K.; Hirschauer, J.; Jeng, G. Y.; Pastika, N. J.; Pedro, K.; Rumerio, Paolo; Samuel, J.; Sharp, E.; Shin, Y. H.; Tiras, E.; Vishnevskiy, D.; Wetzel, J.; Yang, Z.; Yao, Y.; Youn, S. W.

    2016-11-01

    Future experiments in high energy and nuclear physics may require large, inexpensive calorimeters that can continue to operate after receiving doses of 50 Mrad or more. The light output of liquid scintillators suffers little degradation under irradiation. However, many challenges exist before liquids can be used in sampling calorimetry, especially regarding developing a packaging that has sufficient efficiency and uniformity of light collection, as well as suitable mechanical properties. We present the results of a study of a scintillator tile based on the EJ-309 liquid scintillator using cosmic rays and test beam on the light collection efficiency and uniformity, and some preliminary results on radiation hardness.

  19. Liquid scintillator tiles for calorimetry

    SciTech Connect

    Amouzegar, M.; Belloni, A.; Bilki, B.; Calderon, J.; Barbaro, P. De; Eno, S. C.; Hatakeyama, K.; Hirschauer, J.; Jeng, G. Y.; Pastika, N. J.; Pedro, K.; Rumerio, Paolo; Samuel, J.; Sharp, E.; Shin, Y. H.; Tiras, E.; Vishnevskiy, D.; Wetzel, J.; Yang, Z.; Yao, Y.; Youn, S. W.

    2016-11-28

    Future experiments in high energy and nuclear physics may require large, inexpensive calorimeters that can continue to operate after receiving doses of 50 Mrad or more. Also, the light output of liquid scintillators suffers little degradation under irradiation. However, many challenges exist before liquids can be used in sampling calorimetry, especially regarding developing a packaging that has sufficient efficiency and uniformity of light collection, as well as suitable mechanical properties. We present the results of a study of a scintillator tile based on the EJ-309 liquid scintillator using cosmic rays and test beam on the light collection efficiency and uniformity, and some preliminary results on radiation hardness.

  20. Liquid scintillator tiles for calorimetry

    DOE PAGES

    Amouzegar, M.; Belloni, A.; Bilki, B.; ...

    2016-11-28

    Future experiments in high energy and nuclear physics may require large, inexpensive calorimeters that can continue to operate after receiving doses of 50 Mrad or more. Also, the light output of liquid scintillators suffers little degradation under irradiation. However, many challenges exist before liquids can be used in sampling calorimetry, especially regarding developing a packaging that has sufficient efficiency and uniformity of light collection, as well as suitable mechanical properties. We present the results of a study of a scintillator tile based on the EJ-309 liquid scintillator using cosmic rays and test beam on the light collection efficiency and uniformity,more » and some preliminary results on radiation hardness.« less

  1. Dijet mass resolution and compensating calorimetry

    SciTech Connect

    Green, D.

    1991-05-01

    The calorimetry for SSC detectors has as its role the detection of the basic particles of the Standard Model. Those germane to calorimetry are quarks, photons, electrons, and gluons. Note that all the hadronic entities appear in the calorimetry as jets. The detection of single hadrons belongs to a past era when quark molecules'' were the focus of intense study. Thus, the goal of calorimetry at the SSC must be the study of jets. In particular, one must understand what defines the limits of accuracy of the jets. If there are intrinsic physical processes which limit the precision of jet measurements, then calorimetry which is more accurate is unnecessary if not wasteful. 5 refs., 5 figs.

  2. Tritium inventory measurements using calorimetry

    SciTech Connect

    Kapulla, H.; Kraemer, R.; Heine, R. )

    1992-03-01

    In the past calorimetry has been developed as a powerful tool in radiometrology. Calorimetric methods have been applied for the determination of activities, half lives and mean energies released during the disintegration of radioactive isotopes. The fundamental factors and relations which determine the power output of radioactive samples are presented and some basic calorimeter principles are discussed in this paper. At the Kernforschungszentrum Karlsruhe (KfK) a family of 3 calorimeters has been developed to measure the energy release from radiative waste products arising from reprocessing operations. With these calorimeters, radiative samples with sizes from a few cm{sup 3} to 2 {center dot}10{sup 5} cm{sup 3} and heat ratings ranging from a few nW to kW can be measured. After modifications of tits inner part the most sensitive calorimeter among the three calorimeters mentioned above would be best suited for measuring the tritium inventory in T-getters of the Amersham-type.

  3. Recent Work on Calorimetry at LANL

    SciTech Connect

    Santi, Peter A.; Hauck, Danielle K.

    2014-01-09

    This report is a briefing to collaborators at the Swedish Nuclear Fuel and Waste Management Company, Oskarshamn, Sweden, January 14, 2014. It describes the way in which calorimetry supports the safegurard mission.

  4. Automatic calorimetry system monitors RF power

    NASA Technical Reports Server (NTRS)

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

    1969-01-01

    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.

  5. Extruded scintillator for the Calorimetry applications

    NASA Astrophysics Data System (ADS)

    Dyshkant, A.; Rykalin, V.; Pla-Dalmau, A.; Beznosko, D.

    2006-10-01

    An extrusion line has been installed and successfully operated at FNAL (Fermi National Accelerator Laboratory) in collaboration with NICADD (Northern Illinois Center for Accelerator and Detector Development). This new Facility will serve to further develop and improve extruded plastic scintillator. Recently progress has been made in producing co-extruded plastic scintillator, thus increasing the potential HEP applications of this Facility. The current R&D work with extruded and co-extruded plastic scintillator for a potential ALICE upgrade, the ILC calorimetry program and the MINERvA experiment show the attractiveness of the chosen strategy for future experiments and calorimetry. We extensively discuss extruded and co-extruded plastic scintillator in calorimetry in synergy with new Solid State Photomultipliers. The characteristics of extruded and co-extruded plastic scintillator will be presented here as well as results with non-traditional photo read-out.

  6. Extruded scintillator for the calorimetry applications

    SciTech Connect

    Dyshkant, A.; Rykalin, V.; Pla-Dalmau, A.; Beznosko, D.; /SUNY, Stony Brook

    2006-08-01

    An extrusion line has been installed and successfully operated at FNAL (Fermi National Accelerator Laboratory) in collaboration with NICADD (Northern Illinois Center for Accelerator and Detector Development). This new Facility will serve to further develop and improve extruded plastic scintillator. Recently progress has been made in producing co-extruded plastic scintillator, thus increasing the potential HEP applications of this Facility. The current R&D work with extruded and co-extruded plastic scintillator for a potential ALICE upgrade, the ILC calorimetry program and the MINERvA experiment show the attractiveness of the chosen strategy for future experiments and calorimetry. We extensively discuss extruded and co-extruded plastic scintillator in calorimetry in synergy with new Solid State Photomultipliers. The characteristics of extruded and co-extruded plastic scintillator will be presented here as well as results with non-traditional photo read-out.

  7. Differential scanning calorimetry (DSC) of semicrystalline polymers.

    PubMed

    Schick, C

    2009-11-01

    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.

  8. Isothermal Titration Calorimetry in the Student Laboratory

    ERIC Educational Resources Information Center

    Wadso, Lars; Li, Yujing; Li, Xi

    2011-01-01

    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…

  9. Monte Carlo studies of uranium calorimetry

    SciTech Connect

    Brau, J.; Hargis, H.J.; Gabriel, T.A.; Bishop, B.L.

    1985-01-01

    Detailed Monte Carlo calculations of uranium calorimetry are presented which reveal a significant difference in the responses of liquid argon and plastic scintillator in uranium calorimeters. Due to saturation effects, neutrons from the uranium are found to contribute only weakly to the liquid argon signal. Electromagnetic sampling inefficiencies are significant and contribute substantially to compensation in both systems. 17 references.

  10. Calculation of Temperature Rise in Calorimetry.

    ERIC Educational Resources Information Center

    Canagaratna, Sebastian G.; Witt, Jerry

    1988-01-01

    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)

  11. Isothermal Titration Calorimetry in the Student Laboratory

    ERIC Educational Resources Information Center

    Wadso, Lars; Li, Yujing; Li, Xi

    2011-01-01

    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…

  12. HDTHe calorimetry v.1.0

    SciTech Connect

    Robinson, David B.; Cai, Trevor Y

    2016-01-12

    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.

  13. Final Technical Report CMS fast optical calorimetry

    SciTech Connect

    Winn, David R.

    2012-07-12

    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.

  14. Liquid argon calorimetry for the SSC

    SciTech Connect

    Gordon, H.A.

    1990-01-01

    Liquid argon calorimetry is a mature technique. However, adapting it to the challenging environment of the SSC requires a large amount of R D. The advantages of the liquid argon approach are summarized and the issues being addressed by the R D program are described. 18 refs.

  15. Calculation of Temperature Rise in Calorimetry.

    ERIC Educational Resources Information Center

    Canagaratna, Sebastian G.; Witt, Jerry

    1988-01-01

    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)

  16. Adsorption calorimetry in enhanced oil recovery

    SciTech Connect

    Noll, L.A.

    1988-05-01

    Adsorption calorimetry is a technique which has been used at the National Institute for Petroleum and Energy Reserch (NIPER) to help in the understanding of adsorption as it impacts enhanced oil recovery by chemical flooding. Abstraction of chemicals by reservoir minerals comprises a major obstacle to the technical and economic success of this process. Adsorption is also important in other fields such as catalysis, lubrication, ore flotation, and printing. Adsorption calorimetry is useful because it measures both the amount of adsorption and its enthalpy. The enthalpy helps to guide the extrapolation of adsorption to higher temperatures as well as acting as a probe of surface properties such as heterogeneity. Adsorption calorimetry helps to distinguish physical from chemisorption. It is also useful in distinguishing water-wet from oil-wet surfaces. This paper discusses flow adsorption calorimetry. The advantage of using a flowing system over the classic immersion technique is that it is fast and easy to use, and data for the entire isotherm are collected on a single sample of solid. In flow calorimetry the surface excess amount and the thermal data are obtained simultaneously on one and the same sample of solid, thus avoiding some sampling problems. Some disadvantages of the method are somewhat short equilibration times and the cumulative nature of the data. Aspects of adsorption of special interest to enhanced oil recovery such as the nature and charge of minerals, the structure and charge of surfactants, the effects of brine and temperature, and the effects of aqueous or hydrocarbon environment are important parameters of surfactant flooding; they are treated in this paper.

  17. Foward Calorimetry in ALICE at LHC

    NASA Astrophysics Data System (ADS)

    Chujo, Tatsuya; Alice Focal Collaboration

    2014-09-01

    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.

  18. Overabundance of carbon monoxide in calorimetry tests

    SciTech Connect

    Ree, F.H.; Pitz, W.J.; Thiel, M. van; Souers, P.C.

    1996-04-04

    The amount of carbon monoxide recovered from calorimetry tests of high explosives is far larger than the amount predicted by equilibrium calculations. The present kinetics study of PETN [(nitro(oxy)methyl]-propanediol dinitrate) has revealed that the cooling of the calorimetry bomb after detonation of a PETN sample sufficiently slows those reactions that would otherwise lead to equilibrium so that these reactions are effectively frozen in the time scale of recovery of detonation products. Among these reactions, those that can create CH{sub 4} are the most important ones. Their rates are generally slow at all temperatures relevant to calorimetry tests. This and the slowing down of a reaction, CO + H{sub 2}O {yields} H{sub 2} + CO{sub 2} at temperatures below 1500 K are the main caus of the freeze-out of CO. A possible slow rate of the soot formation (i.e., condensed carbon) is not responsible for it. The sensitivity of the present result to the cooling rate of the detonation products and to free radicals is also examined. 10 refs., 5 figs., 2 tabs.

  19. G-2 and CMS fast optical calorimetry

    SciTech Connect

    Winn, David R.

    2001-06-01

    The following projects are discussed: (A) Operation of the muon g-2 experiment at Brookhaven National Lab (Experiment E821), especially the pulsed laser calibration system, to test the standard model of forces, and to see if new forces may exist in the vacuum. (B) The second part of this project developed fast optical forward Cerenkov jet calorimetry used in the CMS experiment collaboration (US lead organization FermiLab) at CERN on the Large Hadron Collider, designed to detect new physics at the TeV scale, such as supersymmetry and the Higgs boson.

  20. From biochemistry to physiology: the calorimetry connection.

    PubMed

    Hansen, Lee D; Russell, Donald J; Choma, Christin T

    2007-01-01

    This article provides guidelines for selecting optimal calorimetric instrumentation for applications in biochemistry and biophysics. Applications include determining thermodynamics of interactions in non-covalently bonded structures, and determining function through measurements of enzyme kinetics and metabolic rates. Specific examples illustrating current capabilities and methods in biological calorimetry are provided. Commercially available calorimeters are categorized by application and by instrument characteristics (isothermal or temperature-scanning, reaction vessel volume, heat rate detection limit, fixed or removable reaction vessels, etc.). Advantages and limitations of commercially available calorimeters are listed for each application in biochemistry, biophysics, and physiology.

  1. Determining enzyme kinetics via isothermal titration calorimetry.

    PubMed

    Demarse, Neil A; Killian, Marie C; Hansen, Lee D; Quinn, Colette F

    2013-01-01

    Isothermal titration calorimetry (ITC) has emerged as a powerful tool for determining the thermodynamic properties of chemical or physical equilibria such as protein-protein, ligand-receptor, and protein-DNA binding interactions. The utility of ITC for determining kinetic information, however, has not been fully recognized. Methods for collecting and analyzing data on enzyme kinetics are discussed here. The step-by-step process of converting the raw heat output rate into the kinetic parameters of the Michaelis-Menten equation is explicitly stated. The hydrolysis of sucrose by invertase is used to demonstrate the capability of the instrument and method.

  2. Uniformity requirements in CMS hadron calorimetry

    SciTech Connect

    Green, D.

    1996-02-01

    Practical considerations of calorimeter systems require a specification of the allowed manufacturing tolerances. The tightness of these requirements directly makes an impact on the assembly costs of the calorimeter. For that reason, a precise and well defined set of criteria is mandatory. In addition, the intrinsic limitations of hadron calorimetry define the level of accuracy needed in the manufacture of such devices. Therefore, considerations of the limitations on energy measurement accuracy due to Physics should define the needed level of effort to produce a uniform calorimetric device.

  3. Calorimetry of the CMD-3 detector

    NASA Astrophysics Data System (ADS)

    Shebalin, V. E.; Akhmetshin, R. R.; Anisenkov, A. V.; Aulchenko, V. M.; Bashtovoy, N. S.; Epifanov, D. A.; Epshteyn, L. B.; Erofeev, A. L.; Grebenuk, A. A.; Grigoriev, D. N.; Ignatov, F. V.; Kazanin, V. F.; Kovalenko, O. A.; Kozyrev, A. N.; Kuzmenko, A. E.; Kuzmin, A. S.; Logashenko, I. B.; Mikhailov, K. Yu.; Okhapkin, V. S.; Razuvaev, G. P.; Ruban, A. A.; Shwartz, B. A.; Titov, V. M.; Talyshev, A. A.; Yudin, Yu. V.

    2016-07-01

    CMD-3 is a general purpose detector designed to study e+e- annihilation into hadrons. It is mounted at VEPP-2000 collider which operates in the wide energy range, E c . m . s = 0.32 - 2 GeV. The calorimetry at the detector is based on three subsystems: closest to the beam pipe barrel Liquid Xenon calorimeter, outer barrel calorimeter based on CsI scintillation crystals and the endcap calorimeter made of BGO scintillation crystals. We describe the structure of the calorimeters, their electronics and the energy calibration procedures.

  4. Calorimetry exchange program. Annual report, 1988

    SciTech Connect

    Lyons, J.E.

    1988-12-31

    The goals of the Calorimetry Sample Program are: 1. Discuss measurement differences, 2. Review and improve analytical measurements and methods, 3. Discuss new measurement capabilities, 4. Provide data to DOE on measurement capabilities to evaluate shipper- receiver differences, 5. Provide characterized or standard materials as necessary for exchange participants, 6. 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 or from data previously reported by that facility. Data included in this report is a compilation of all exchange data received in 1988. Since a large number of data points were recorded, a change was made to the analysis method to account for the uncertainty in the accepted values.

  5. Isothermal Titration Calorimetry to Characterize Enzymatic Reactions.

    PubMed

    Mazzei, Luca; Ciurli, Stefano; Zambelli, Barbara

    2016-01-01

    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.

  6. Higher Throughput Calorimetry: Opportunities, Approaches and Challenges

    PubMed Central

    Recht, Michael I.; Coyle, Joseph E.; Bruce, Richard H.

    2010-01-01

    Higher throughput thermodynamic measurements can provide value in structure-based drug discovery during fragment screening, hit validation, and lead optimization. Enthalpy can be used to detect and characterize ligand binding, and changes that affect the interaction of protein and ligand can sometimes be detected more readily from changes in the enthalpy of binding than from the corresponding free-energy changes or from protein-ligand structures. Newer, higher throughput calorimeters are being incorporated into the drug discovery process. Improvements in titration calorimeters come from extensions of a mature technology and face limitations in scaling. Conversely, array calorimetry, an emerging technology, shows promise for substantial improvements in throughput and material utilization, but improved sensitivity is needed. PMID:20888754

  7. Pressure perturbation calorimetry of unfolded proteins.

    PubMed

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

    2010-12-16

    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.

  8. Isothermal Titration Calorimetry of Chiral Polymeric Nanoparticles.

    PubMed

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

    2015-09-01

    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.

  9. Synergies between electromagnetic calorimetry and PET

    SciTech Connect

    Moses, William W.

    2002-07-30

    The instrumentation used for the nuclear medical imaging technique of Positron Emission Tomography (PET) shares many features with the instrumentation used for electromagnetic calorimetry. Both fields can certainly benefit from technical advances in many common areas, and this paper discusses both the commonalties and the differences between the instrumentation needs for the two fields. The overall aim is to identify where synergistic development opportunities exist. While such opportunities exist in inorganic scintillators, photodetectors, amplification and readout electronics, and high-speed computing, it is important to recognize that while the requirements of the two fields are similar, they are not identical, and so it is unlikely that advances specific to one field can be transferred without modification to the other.

  10. Titration Calorimetry Standards and the Precision of Isothermal Titration Calorimetry Data

    PubMed Central

    Baranauskienė, Lina; Petrikaitė, Vilma; Matulienė, Jurgita; Matulis, Daumantas

    2009-01-01

    Current Isothermal Titration Calorimetry (ITC) data in the literature have relatively high errors in the measured enthalpies of protein-ligand binding reactions. There is a need for universal validation standards for titration calorimeters. Several inorganic salt co-precipitation and buffer protonation reactions have been suggested as possible enthalpy standards. The performances of several commercial calorimeters, including the VP-ITC, ITC200, and Nano ITC-III, were validated using these suggested standard reactions. PMID:19582227

  11. Considerations for Calorimetry at a Super B Factory

    SciTech Connect

    Wisniewski, William

    2003-09-18

    The study of B physics at e{sup +}e{sup -} colliders running the {Upsilon} region imposes significant performance requirements on calorimetry. The environment of a very high luminosity B factor further restricts calorimetry choices. Calorimeter design is discussed in light of these constraints. A solution using scintillating crystals is explored.

  12. Differential Scanning Calorimetry Techniques: Applications in Biology and Nanoscience

    PubMed Central

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

    2010-01-01

    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. PMID:21119929

  13. Differential scanning calorimetry techniques: applications in biology and nanoscience.

    PubMed

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

    2010-12-01

    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.

  14. Melting by temperature-modulated calorimetry

    SciTech Connect

    Wunderlich, B.; Okazaki, Iwao; Ishikiriyama, Kazuhiko; Boller, A. |

    1997-09-01

    Well-crystallized macromolecules melt irreversibly due to the need of molecular nucleation, while small molecules melt reversibly as long as crystal nuclei are present to assist crystallization. Furthermore, imperfect crystals of low-molar-mass polymers may have a sufficiently small region of metastability between crystallization and melting to show a reversing heat-flow component due to melting of poor crystals followed by crystallization of imperfect crystals which have insufficient time to perfect before the modulation switches to heating and melts the imperfect crystals. Many metals, in turn. melt sharply and reversibly as long as nuclei remain after melting for subsequent crystallization during the cooling cycle. Their analysis is complicated, however, due to thermal conductivity limitations of the calorimeters. Polymers of sufficiently high molar mass, finally, show a small amount of reversible. local melting that may be linked to partial melting of individual molecules. Experiments by temperature-modulated calorimetry and model calculations are presented. The samples measured included poly(ethylene terephthalate)s, poly(ethylene oxide)s, and indium. Two unsolved problems that arose from this research involve the origin of a high, seemingly stable, reversible heat capacity of polymers in the melting region, and a smoothing of melting and crystallization into a close-to-elliptical Lissajous figure in a heat-flow versus sample-temperature plot.

  15. Differential scanning calorimetry of plant cell walls

    SciTech Connect

    Lin, Liangshiou; Varner, J.E. ); Yuen, H.K. )

    1991-03-15

    High-sensitivity differential scanning calorimetry has been used to study the phase transition of cell wall preparations of the elongating and mature regions of soybean hypocotyls and of celery epidermis and collenchyma strands. A step-like transition believed to be glass transition was observed in walls isolated from the elongating region of soybean hypocotyls at 52.9C. Addition of 1 mM CaCl{sub 2} to the cell wall preparation increased the transition temperature to 60.8C and greatly reduced the transition magnitude. In walls from the mature region, the transition was small and occurred at a higher temperature (60.1C). Addition of calcium to the mature region cell wall had little effect on the transition. Based on the known interactions between calcium and pectin, the authors propose that calcium affects the glass transition by binding to the polygalacturonate backbone of wall pectin, resulting in a more rigid wall with a smaller transition at a higher temperature. The mature region either has more calcium in the wall or has more methyl-esterified pectin, making it less responsive to added calcium.

  16. Current status of tritium calorimetry at TLK

    SciTech Connect

    Buekki-Deme, A.; Alecu, C.G.; Kloppe, B.; Bornschein, B.

    2015-03-15

    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)

  17. Immersion Calorimetry: Molecular Packing Effects in Micropores.

    PubMed

    Madani, S Hadi; Silvestre-Albero, Ana; Biggs, Mark J; Rodríguez-Reinoso, Francisco; Pendleton, Phillip

    2015-12-21

    Repeated and controlled immersion calorimetry experiments were performed to determine the specific surface area and pore-size distribution (PSD) of a well-characterized, microporous poly(furfuryl alcohol)-based activated carbon. The PSD derived from nitrogen gas adsorption indicated a narrow distribution centered at 0.57±0.05 nm. Immersion into liquids of increasing molecular sizes ranging from 0.33 nm (dichloromethane) to 0.70 nm (α-pinene) showed a decreasing enthalpy of immersion at a critical probe size (0.43-0.48 nm), followed by an increase at 0.48-0.56 nm, and a second decrease at 0.56-0.60 nm. This maximum has not been reported previously. After consideration of possible reasons for this new observation, it is concluded that the effect arises from molecular packing inside the micropores, interpreted in terms of 2D packing. The immersion enthalpy PSD was consistent with that from quenched solid density functional theory (QSDFT) analysis of the nitrogen adsorption isotherm. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Ice premelting during differential scanning calorimetry

    PubMed Central

    Wilson, PW; Arthur, JW; Haymet, AD

    1999-01-01

    Premelting at the surface of ice crystals is caused by factors such as temperature, radius of curvature, and solute composition. When polycrystalline ice samples are warmed from well below the equilibrium melting point, surface melting may begin at temperatures as low as -15 degrees C. However, it has been reported (. Biophys. J. 65:1853-1865) that when polycrystalline ice was warmed in a differential scanning calorimetry (DSC) pan, melting began at about -50 degrees C, this extreme behavior being attributed to short-range forces. We show that there is no driving force for such premelting, and that for pure water samples in DSC pans curvature effects will cause premelting typically at just a few degrees below the equilibrium melting point. We also show that the rate of warming affects the slope of the DSC baseline and that this might be incorrectly interpreted as an endotherm. The work has consequences for DSC operators who use water as a standard in systems where subfreezing runs are important. PMID:10545382

  19. Differential scanning calorimetry of plant cell walls.

    PubMed Central

    Lin, L S; Yuen, H K; Varner, J E

    1991-01-01

    High-sensitivity differential scanning calorimetry has been used to study the phase transition of cell wall preparations of the elongating and mature regions of soybean hypocotyls and of celery epidermis and collenchyma strands. A step-like transition believed to be glass transition was observed in walls isolated from the elongating region of soybean hypocotyls at 52.9 degrees C. Addition of 1 mM CaCl2 to the cell wall preparation increased the transition temperature to 60.8 degrees C and greatly reduced the transition magnitude. In walls from the mature region, the transition was small and occurred at a higher temperature (60.1 degrees C). Addition of calcium to the mature region cell wall had little effect on the transition. Based on the known interactions between calcium and pectin, we propose that calcium affects the glass transition by binding to the polygalacturonate backbone of wall pectin, resulting in a more rigid wall with a smaller transition at a higher temperature. The mature region either has more calcium in the wall or has more methyl-esterified pectin, making it less responsive to added calcium. PMID:11607163

  20. Calorimetry using organic scintillators, 'a sideways perspective'.

    SciTech Connect

    Proudfoot, J.

    1999-09-10

    Over the last two decades, calorimetry baaed on organic scintillators has developed into an excellent technology for many experimental situations in high energy physics. The primary difficulty, that of extracting the light signals, has benefited from two milestone innovations. The first was the use of wavelength-shifting bars to allow light to be efficiently collected from large areas of scintillator and then readily piped to a readout device. The second of these was the extension of this approach to plastic wavelength-shifting optical fibers whose great flexibility and small diameter allowed a minimum of detector volume to be compromised by the read-out. These two innovations coupled with inventiveness have produced many varied and successful calorimeters. Equal response to both hadronic and electromagnetic showers can be realized in scintillator-based calorimeters. However, in general this is not the case and it is likely that in the search for greater performance, in the future, combined tracking and calorimeter systems will be required.

  1. Hydration of thermally denatured lysozyme studied by sorption calorimetry and differential scanning calorimetry.

    PubMed

    Kocherbitov, Vitaly; Arnebrant, Thomas

    2006-05-25

    We have studied hydration (and dehydration) of thermally denatured hen egg lysozyme using sorption calorimetry. Two different procedures of thermal denaturation of lysozyme were used. In the first procedure the protein was denatured in an aqueous solution at 90 degrees C, in the other procedure a sample that contained 20% of water was denatured at 150 degrees C. The protein denatured at 90 degrees C showed very similar sorption behavior to that of the native protein. The lysozyme samples denatured at 150 degrees C were studied at several temperatures in the range of 25-60 degrees C. In the beginning of sorption, the sorption isotherms of native and denatured lysozyme are almost identical. At higher water contents, however, the denatured lysozyme can absorb a greater amount of water than the native protein due to the larger number of available sorption sites. Desorption experiments did not reveal a pronounced hysteresis in the sorption isotherm of denatured lysozyme (such hysteresis is typical for native lysozyme). Despite the unfolded structure, the denatured lysozyme binds less water than does the native lysozyme in the desorption experiments at water contents up to 34 wt %. Glass transitions in the denatured lysozyme were observed using both differential scanning calorimetry and sorption calorimetry. Partial molar enthalpy of mixing of water in the glassy state is strongly exothermic, which gives rise to a positive temperature dependence of the water activity. The changes of the free energy of the protein induced by the hydration stabilize the denatured form of lysozyme with respect to the native form.

  2. Advances in temperature derivative control and calorimetry

    SciTech Connect

    Hemmerich, J.L.; Loos, J.; Miller, A.; Milverton, P.

    1996-11-01

    Temperature stabilization by inertial feedback control has proven a powerful tool to create the ultrastable environment essential for high resolution calorimetry. A thermally insulated mass, connected to a base through Seebeck effect sensors (thermopiles) is used as a reference to control the base temperature. The thermopile signal is proportional to both the heat capacity of the reference mass and the derivative {dot {Theta}} of the base temperature {Theta}. Using vacuum insulation and bismuth telluride thermopiles, we designed and tested temperature derivative sensors (TDSs) with sensitivities up to 3300 VsK{sup {minus}1}. Standard industrial controllers with approximately {plus_minus}1 {mu}V input noise and stability, permit control of temperature derivatives to {plus_minus}3{times}10{sup {minus}10} Ks{sup {minus}1}. Single-cup thermoelectric calorimeters coupled to the TDS-controlled base permitted measurement of heat flow from samples in a power range from 3 {mu}W to 10 W with high accuracy ({plus_minus}100 ppm), resolution ({plus_minus}0.2 {mu}W), and reproducibility ({plus_minus}1 {mu}W). The design of two instruments is described in detail. Their performance is demonstrated on a variety of measurements, e.g., the determination of sample heat capacities with temperature ramp rates {dot {Theta}}={plus_minus}5{times}10{sup {minus}6} Ks{sup {minus}1}, the half-life of a 3 g tritium sample in a uranium getter bed, the decay heat of depleted uranium, and the heat evolution of epoxy resin. {copyright} {ital 1996 American Institute of Physics.}

  3. Fluorine as an oxidant in combustion calorimetry

    SciTech Connect

    O'Hare, P.A.G.

    1988-01-01

    Oxygen-bomb calorimetry has been used with some success over the years for the determination of enthalpies of formation ..delta../sub f/H/sub m//sup 0/ of inorganic compounds. This method, however, has a number of drawbacks, the most significant of which is the formation of complicated and ill-defined oxides as reaction products. Substitution of fluorine for oxygen, as the oxidizing gas, eliminates many of those problems. Because of the aggressive nature of fluorine, it can be used to study even the most refractory of materials, but its disadvantages are that it requires very careful handling and special apparatus. A portion of the present paper will discuss the precautions that must be taken, and the special calorimetric equipment that has been constructed. The main scope of the paper, however, is concerned with our recent results obtained for some high-purity chalcogenides. We have performed measurements on both the crystalline and vitreous forms of As/sub 2/Se/sub 3/. The enthalpies of formation have been deduced from the calorimetric enthalpies of fluorination. The following preliminary results at 298.15 K have been obtained and are compared in the paper with published values: ..delta../sub f/H/sub m//sup 0/(As/sub 2/Se/sub 3/, cr) = -(83.7+-4.5) kJ/center dot/mol/sup -1/ and ..delta../sub f/H/sub m//sup 0/(As/sub 2/Se/sub 3/, vit) = -(59.4+-4.3)kJ/center dot/mol/sup -1/. The enthalpy of transition is -(24.3+-3.9)kJ/center dot/mol/sup -1/, only about 60 per cent of the previous literature value. 27 refs., 2 figs., 6 tabs.

  4. Determination of Purity by Differential Scanning Calorimetry (DSC).

    ERIC Educational Resources Information Center

    Brown, M. E.

    1979-01-01

    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)

  5. Determination of Purity by Differential Scanning Calorimetry (DSC).

    ERIC Educational Resources Information Center

    Brown, M. E.

    1979-01-01

    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)

  6. Application of solution calorimetry in pharmaceutical and biopharmaceutical research.

    PubMed

    Royall, P G; Gaisford, S

    2005-06-01

    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.

  7. Application and use of isothermal calorimetry in pharmaceutical development.

    PubMed

    O'Neill, Michael A A; Gaisford, Simon

    2011-09-30

    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.

  8. Perfusion calorimetry in the characterization of solvates forming isomorphic desolvates.

    PubMed

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

    2011-09-18

    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.

  9. Oxygen Consumption Rate and Energy Expenditure in Mice: Indirect Calorimetry.

    PubMed

    Kim, Eun Ran; Tong, Qingchun

    2017-01-01

    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.

  10. Differential scanning calorimetry to quantify the stability of protein cages.

    PubMed

    Zhang, Yu; Ardejani, Maziar S

    2015-01-01

    Differential scanning calorimetry (DSC) is an experimental technique through which the differences in amount of heat required to maintain equal temperature between a sample and a reference cell are measured at various temperatures. The quantified heat relates to the differences in apparent heat capacity of the analytes. The data from DSC studies will thereby provide direct information about the energetics of thermally induced processes in the sample. Here we present a detailed protocol to quantify the thermostability of protein cage, bacterioferritin (BFR), using differential scanning calorimetry.

  11. Characterization of Novel Operation Modes for Secondary Emission Ionization Calorimetry

    NASA Astrophysics Data System (ADS)

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

    2017-01-01

    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.

  12. Differential Binding Models for Direct and Reverse Isothermal Titration Calorimetry.

    PubMed

    Herrera, Isaac; Winnik, Mitchell A

    2016-03-10

    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.

  13. Calorimetry Studies of Ammonia, Nitric Acid, and Ammonium Nitrate

    DTIC Science & Technology

    1979-10-01

    block nmmber) Calorimetry Heat of reaction Ammonium nitrate Heat capacity Nitric acid Heat of solution • Amonia 20. ABSTRACT r(Cmrtfe m,.re a N "no•a.•r sd...identical to the literature spectrum of W NO3. Anhydrous nitric acid was prepared by distillation of 90% HNO 3 from fuming sulfuric acid (oxides of nitrogen

  14. Isothermal Titration Calorimetry Can Provide Critical Thinking Opportunities

    ERIC Educational Resources Information Center

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

    2016-01-01

    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…

  15. Isothermal Titration Calorimetry Can Provide Critical Thinking Opportunities

    ERIC Educational Resources Information Center

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

    2016-01-01

    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…

  16. Superconducting phase in UGe2 by AC calorimetry

    NASA Astrophysics Data System (ADS)

    Taufour, Valentin; Aoki, Dai; Knebel, Georg; Flouquet, Jacques

    2012-12-01

    We report on the detection of the superconducting transition Tsc in the superconducting ferromagnet UGe2 by AC calorimetry under pressure. Our results confirm the small value of the specific heat jump. We suggest that this observation is intrinsic in origin and does not arises from a distribution of Tsc due to pressure gradient or sample defects.

  17. Preparation of Solid Derivatives by Differential Scanning Calorimetry.

    ERIC Educational Resources Information Center

    Crandall, E. W.; Pennington, Maxine

    1980-01-01

    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…

  18. A study of ultra-strength polymer fibers via calorimetry

    NASA Astrophysics Data System (ADS)

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

    2016-08-01

    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.

  19. Preparation of Solid Derivatives by Differential Scanning Calorimetry.

    ERIC Educational Resources Information Center

    Crandall, E. W.; Pennington, Maxine

    1980-01-01

    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…

  20. Comparison of Calorimetry: MIT and Fleischmann-Pons Systems

    NASA Astrophysics Data System (ADS)

    Miles, Melvin H.; Hagelstein, Peter

    2011-03-01

    The history of cold fusion shows that the MIT heat conduction calorimetry in 1990 reported a sensitivity of 40 mW while the Fleischmann-Pons Dewar calorimetry achieved a sensitivity of 0.1 mW. Additional information about the MIT calorimetry allows a more detailed analysis. The major finding is that the MIT calorimetric cell was so well insulated with glass wool (2.5 cm in thickness) that the major heat transport pathway was out of the cell top rather than from the cell into the constant temperature water bath. It can be shown for the MIT calorimeter that 58% of the heat transport was through the cell top and 42% was from the cell into the water bath. Analysis of the Fleischmann-Pons Dewar cell shows that under conditions similar to the MIT experiments, almost all of the heat flow would be from the Dewar calorimetric cell to the constant temperature water bath. Furthermore, the sensitivity of the Fleischmann- Pons temperature measurements was 0.001 K versus 0.1 K for the MIT calorimetric cell. Evaluations of the calorimetric equations and data analysis methods leads to the conclusion that the Fleischmann-Pons calorimetry was far superior to that of MIT.

  1. What does calorimetry and thermodynamics of living cells tell us?

    PubMed

    Maskow, Thomas; Paufler, Sven

    2015-04-01

    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.

  2. Fragility of Ionic Liquids Measured by Flash Differential Scanning Calorimetry

    NASA Astrophysics Data System (ADS)

    Tao, Ran; Gurung, Eshan; Quitevis, Edward L.; Simon, Sindee L.

    Ionic liquids are a class of materials that possess attractive properties. They generally have low rates of crystallization due to their bulky and asymmetrical ion structure, and are often considered as good glass-forming materials. In this work, a series of imidazolium-based ionic liquids with varying functionalities from aliphatic to aromatic groups and a fixed anion are characterized using fast scanning differential scanning calorimetry. The limiting fictive temperature Tf', which is equivalent to the glass transition temperature Tg, is measured on heating as a function of cooling rate using Flash differential scanning calorimetry. Different calculation methods are employed and compared for the determination of Tf'. The dynamic fragility is obtained for the series of ionic liquids, and using this data along with a compilation of data from the literature reveals the relationship between molecular structure and fragility for ionic liquids.

  3. Inherent limitations of fixed time servo-controlled radiometric calorimetry

    SciTech Connect

    Wetzel, J.R.; Duff, M.F.; Lemming, J.F.

    1987-01-01

    There has been some interest in low precision, short run time calorimetry measurements. This type of calorimetry measurement has been proposed for use when high precision measurements are not required, for example, to screen scrap containers to determine if there is enough material to be measured more accurately of for confirmatory measurements that only require low precision results. The equipment needed to make these measurements is a servo-controlled calorimeter with a sample preequilibration bath. The preequilibration bath temperature is set to the internal temperature of the calorimeter running at a fixed servo-controlled wattage level. The sample power value is determined at a fixed time form the sample loading into the calorimeter. There are some limitations and areas of uncertainties in the use of data obtained by this method. Data collected under controlled conditions demonstrate the limitations. Sample packaging, preequilibration time, and item wattage were chosen as the variables most likely to be encountered in a plant environment.

  4. The Philosophy and Feasibility of Dual Readout Calorimetry

    SciTech Connect

    Hauptman, John

    2006-10-27

    I will discuss the general physical ideas behind dual-readout calorimetry, their implementation in DREAM (Dual REAdout Module) with exact separation of scintillation and Cerenkov light, implementation with mixed light in DREAM fibers, anticipated implementation in PbWO4 crystals with applications to the 4th Concept detector and to CMS, use in high energy gamma-ray and cosmic ray astrophysics with Cerenkov and N2 fluorescent light, and implementation in the 4th Concept detector for muon identification.

  5. The upgraded CDF front end electronics for calorimetry

    SciTech Connect

    Drake, G.; Frei, D.; Hahn, S.R.; Nelson, C.A.; Segler, S.L.; Stuermer, W.

    1991-11-01

    The front end electronics used in the calorimetry of the CDF detector has been upgraded to meet system requirements for higher expected luminosity. A fast digitizer utilizing a 2 {mu}Sec, 16 bit ADC has been designed and built. Improvements to the front end trigger circuitry have been implemented, including the production of 900 new front end modules. Operational experience with the previous system is presented, with discussion of the problems and performance goals.

  6. Differential scanning calorimetry of protein-lipid interactions.

    PubMed

    Cañadas, Olga; Casals, Cristina

    2013-01-01

    Differential scanning calorimetry (DSC) is a highly sensitive non-perturbing technique for measuring the thermodynamic properties of thermally induced transitions. This technique is particularly useful for the characterization of lipid/protein interactions. This chapter presents an introduction to DSC instrumentation, basic theory, and methods and describes DSC applications for characterizing protein effects on model lipid membranes. Examples of the use of DSC for the evaluation of protein effects on modulation of membrane domains and membrane stability are given.

  7. Accurate Measurement of Heat Capacity by Differential Scanning Calorimetry

    NASA Technical Reports Server (NTRS)

    1984-01-01

    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.

  8. Accurate Measurement of Heat Capacity by Differential Scanning Calorimetry

    NASA Technical Reports Server (NTRS)

    1984-01-01

    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.

  9. Thermal Properties of Trogamid by Conventional and Fast Scanning Calorimetry

    NASA Astrophysics Data System (ADS)

    Cebe, Peggy; Merfeld, John; Mao, Bin; Wurm, Andreas; Zhuravlev, Evgeny; Schick, Christoph

    We use conventional slow scan rate differential scanning calorimetry, and fast scanning chip-based calorimetry (FSC), to investigate the crystallization and melting behavior of Trogamid, a chemical relative of nylon. Fundamental thermal properties of Trogamid were studied, including the melt crystallization kinetics, heat of fusion, and the solid and liquid state heat capacities. Using slow scan DSC (at 5 K/min), Trogamid displays a glass transition relaxation process at ~133 C, melting endotherm peak at 250 C, and is stable upon repeated heating to 310 C. When using slow scan DSC, the isothermal melt crystallization temperatures were restricted to 225 C or above. Trogamid crystallizes rapidly from the melt and conventional calorimetry is unable to cool sufficiently fast to prevent nucleation and crystal growth prior to stabilization at lower crystallization temperatures. Using FSC we were able to cool nano-gram sizes samples at 2000 K/s to investigate a much lower range of melt crystallization temperatures, from 205-225 C. The experimental protocol for performing FSC on semicrystalline polymers to obtain liquid state heat capacity data will be presented. National Science Foundation, Polymers Program DMR-1206010; DAAD; Tufts Faculty Supported Leave.

  10. Biofilm research using calorimetry--a marriage made in heaven?

    PubMed

    Buchholz, Friederike; Harms, Hauke; Maskow, Thomas

    2010-12-01

    Aggregated bacteria growing on a surface, so-called biofilms, play an important role in technical processes like wastewater treatment, bioremediation, or bioprocessing. In contrast, problems arise when biofilm growth results in undesired processes that may cause huge financial losses, e.g., clogged pipes, microbially influenced corrosion or pathogenic contamination. For observation purposes and to develop efficient control strategies, real-time monitoring tools for biofilms are required. Among the large variety of tools used in biofilm research, calorimetry is rarely applied, even though many characteristics qualify it for biofilm investigation and monitoring. Calorimetric measurements are non-invasive and non-destructive, and can be applied to nearly any kind of samples (including heterogeneous or turbid solutions) without the need of special sample preparation. Online and real-time data acquisition reduces the labor and facilitates high-throughput measurements. The following article is meant to introduce and promote calorimetry as a future tool in biofilm research. It attempts an assessment of common, existent monitoring tools and specifically addresses the potential of calorimetry in this field. Copyright © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Raman detected differential scanning calorimetry of polymorphic transformations in acetaminophen.

    PubMed

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

    2008-12-15

    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.

  12. Calorimetry exchange program quarterly data report, fourth quarter CY92

    SciTech Connect

    Barnett, T.M.

    1992-12-31

    The goals of the Calorimetry Sample Exchange Program are: (1) discuss measurement differences (2) review and improve analytical measurements and methods (3) discuss new measurement capabilities (4) provide data to DOE on measurement capabilities to evaluate shipper- receiver differences (5) provide characterized or standard materials as necessary for exchange participants (6) provide a measurement control program for plutonium analysis A sample Of PUO2 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 reports as this document provides and as 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. A meeting of the participants of the Calorimetry Exchange is held annually at EG&G Mound Applied Technologies. The purposes of this meeting are to discuss measurement differences, problems, and new measurement capabilities, and to determine the additional activities needed to fulfill the goals of the Exchange.

  13. Calorimetry exchange program annual data report for 1992

    SciTech Connect

    Barnett, T.M.

    1992-12-31

    The goals of the Calorimetry Sample Exchange Program are: 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. A meeting of the participants of the Calorimetry Exchange is held annually at EG&G Mound Applied Technologies. The purposes of this meeting are to discuss measurement differences, problems, and new measurement capabilities, and to determine the additional activities needed to fulfill the goals of the Exchange. This document provides data for 1992.

  14. Isothermal titration calorimetry for studying protein-ligand interactions.

    PubMed

    Damian, Luminita

    2013-01-01

    Isothermal titration calorimetry (ITC) is a biophysical technique that allows a thermodynamic characterization of an interactive system. It is a free in solution technique that requires no labeling, using heat as signal. ITC allows simultaneous determination of affinity K a, stoichiometry n, enthalpy change ΔH and calculation of free energy change ΔG and entropy change ΔS in one single experiment. It is the only technique that allows direct enthalpy change measurement. By accessing the enthalpy change, we get a step closer in estimating the driving forces that characterize the interaction of a protein with a ligand, information much needed in the drug discovery process.

  15. Studying the allosteric energy cycle by isothermal titration calorimetry.

    PubMed

    Martinez-Julvez, Marta; Abian, Olga; Vega, Sonia; Medina, Milagros; Velazquez-Campoy, Adrian

    2012-01-01

    Isothermal titration calorimetry (ITC) is a powerful biophysical technique which allows a complete thermodynamic characterization of protein interactions with other molecules. The possibility of dissecting the Gibbs energy of interaction into its enthalpic and entropic contributions, as well as the detailed additional information experimentally accessible on the intermolecular interactions (stoichiometry, cooperativity, heat capacity changes, and coupled equilibria), make ITC a suitable technique for studying allosteric interactions in proteins. Two experimental methodologies for the characterization of allosteric heterotropic ligand interactions by ITC are described in this chapter, illustrated with two proteins with markedly different structural and functional features: a photosynthetic electron transfer protein and a drug target viral protease.

  16. Cell asymmetry correction for temperature modulated differential scanning calorimetry

    SciTech Connect

    Ishikiriyama, K.; Wunderlich, B. |

    1996-12-31

    The quality of measurement of heat capacity by differential scanning calorimetry (DSC) is based on strict symmetry of the twin calorimeter, which is important for temperature-modulated DSC. Heat capacities for sapphire-filled and empty aluminium calorimeters (pans) under designed cell imbalance caused by different pan-masses were measured. In addition, positive and negative signs of asymmetry were explored by analyzing the phase-shift between temperature and heat flow for sapphire and empty runs. The phase shifts change by more than 18{degree} depending on asymmetry sign. Once the asymmetry sign is determined, the asymmetry correction for modulated DSC can be made.

  17. Isothermal Titration Calorimetry of Membrane Proteins – Progress and Challenges

    PubMed Central

    Rajarathnam, Krishna; Rösgen, Jörg

    2013-01-01

    Summary 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. PMID:23747362

  18. Monitoring assembly of ribonucleoprotein complexes by isothermal titration calorimetry

    PubMed Central

    Recht, Michael I.; Ryder, Sean P.; Williamson, James R.

    2010-01-01

    Isothermal titration calorimetry (ITC) is a useful technique to study RNA-protein interactions, as it provides the only method by which the thermodynamic parameters of free energy, enthalpy, and entropy can be directly determined. This chapter presents a general procedure for studying RNA-protein interactions using ITC, and gives specific examples for monitoring the binding of Caenorhabditis elegans GLD-1 STAR domain to TGE RNA and the binding of Aquifex aeolicus S6:S18 ribosomal protein heterodimer to an S15-rRNA complex. PMID:18982287

  19. Scintillating tile/fiber calorimetry development at FNAL

    NASA Astrophysics Data System (ADS)

    Foster, G. W.; Freeman, J.; Hagstrom, R.

    1991-07-01

    The technique of calorimetry using scintillating tiles with waveshifting fibers imbedded in them for readout has been refined for use in SSC test calorimeters and for the CDF Endplug upgrade. The technique offers high light yield, good spatial uniformity, flexible readout mechanics and a very small "readout crack". Various production techniques have been developed and optimized, including control and correction of scintillator plate uniformity, techniques for splicing plastic fibers with low light losses, and laser-cutting of the groove in which the fiber is placed.

  20. Mechanics from Calorimetry: Probing the Elasticity of Responsive Hydrogels

    NASA Astrophysics Data System (ADS)

    Aangenendt, Frank J.; Mattsson, Johan; Ellenbroek, Wouter G.; Wyss, Hans M.

    2017-07-01

    Temperature-sensitive hydrogels based on polymers such as poly(N -isopropylacrylamide) (PNIPAM) undergo a volume phase transition in response to changes in temperature. During this transition, distinct changes in both thermal and mechanical properties are observed. Here, we illustrate and exploit the inherent thermodynamic link between thermal and mechanical properties by showing that the compressive elastic modulus of PNIPAM hydrogels can be probed using differential scanning calorimetry. We validate our approach by using conventional osmotic compression tests. Our method could be particularly valuable for determining the mechanical response of thermosensitive submicron-sized and/or oddly shaped particles, to which standard methods are not readily applicable.

  1. Water-based scintillators for large-scale liquid calorimetry

    SciTech Connect

    Winn, D.R.; Raftery, D.

    1985-02-01

    We have investigated primary and secondary solvent intermediates in search of a recipe to create a bulk liquid scintillator with water as the bulk solvent and common fluors as the solutes. As we are not concerned with energy resolution below 1 MeV in large-scale experiments, light-output at the 10% level of high-quality organic solvent based scintillators is acceptable. We have found encouraging performance from industrial surfactants as primary solvents for PPO and POPOP. This technique may allow economical and environmentally safe bulk scintillator for kiloton-sized high energy calorimetry.

  2. Differential Scanning Calorimetry (DSC) for the Analysis of Activated Carbon

    DTIC Science & Technology

    1991-10-01

    impregnation procedures . It is believed that Sutcliffe-Speakman is currently using coconut - shell as the carbon precursor (instead of the New Zealand coal...microstructure facilitate the adsorption process whereby all the undesirable materials are retained. For military deployment, the activated carbon is...AD-A245 899 H.P ’ l N dI dUenm / DIFFERENTIAL SCANNING CALORIMETRY (DSC) FOR THE ANALYSIS OF ACTIVATED CARBON (U) by S.H.C. a and L.E. Cameron DTIC x

  3. Isothermal Titration Calorimetry: Assisted Crystallization of RNA-Ligand Complexes.

    PubMed

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

    2016-01-01

    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.

  4. Fragment-Based Screening for Enzyme Inhibitors Using Calorimetry.

    PubMed

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

    2016-01-01

    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.

  5. Freeze-out of carbon monoxide in calorimetry tests

    SciTech Connect

    Ree, F.H.; Pitz, W.J.; Thiel, M. van

    1995-08-22

    The amount of carbon monoxide recovered from calorimetry tests of high explosives is far larger than the amount predicted by equilibrium calculations. The present analysis shows that chemical reactions which produce CH{sub 4} are the most important ones to lead to equilibrium below 1000 K but are effectively blocked by a rapid cooling of the calorimetric bomb. Furthermore, reaction CO + H{sub 2}O -> H{sub 2} + CO{sub 2}, which is the key reaction at T > 1000 K slows down at lower temperatures. The observed overabundance of CO is a direct consequence of both factors.

  6. The use of calorimetry in nuclear materials management

    SciTech Connect

    Nutter, J.D.; O`Hara, F.A.; Rodenburg, W.W.

    1996-07-01

    A calorimeter is a device to measure evolved or adsorbed heat. For our purposes, the heat measured is that associated with radioactive decay and the unit of measurement is the watt. Each time an atom decays, energy is released and absorbed by the surroundings and heat generated. For each isotope, this heat is a constant related to the energy of the decay particles and the half-life of the isotope. A point which is often overlooked is that calorimetry is one of the oldest techniques known for measuring radioactivity. In 1903, Pierre Curie and A. Laborde used a twin microcalorimeter to determine that one gram of radium generates about 100 calories per hour. Several months later, Curie and Dewar used liquid oxygen and hydrogen to show that the amount of energy developed by radium and other radioactive elements did not depend on temperature. At that time, this observation was extremely important. It indicated that the nature of radioactivity is entirely different and cannot be compared with any known phenomena. In all other thermal processes known in physics and chemistry, the rate at which heat is developed changes with temperature. In 1942, Monsanto was asked by General Leslie Groves, Head of the Manhattan Project, to accept the responsibility for the chemistry and metallurgy of radioactive polonium. Late in 1943, two Monsanto scientists began a study of the half-life of polonium-210 using calorimetry.

  7. Isothermal titration calorimetry: general formalism using binding polynomials.

    PubMed

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

    2009-01-01

    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.

  8. Calorimetry exchange program. Annual data report, Calendar Year 1993

    SciTech Connect

    Barnett, T.M.

    1996-08-01

    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. A meeting of the participants of the Calorimetry Exchange is held annually at EG&G Mound Applied Technologies. The purposes of this meeting are to discuss measurement differences, problems, and new measurement capabilities, and to determine the additional activities needed to fulfill the goals of the Exchange.

  9. Heat killing of bacterial spores analyzed by differential scanning calorimetry.

    PubMed

    Belliveau, B H; Beaman, T C; Pankratz, H S; Gerhardt, P

    1992-07-01

    Thermograms of the exosporium-lacking dormant spores of Bacillus megaterium ATCC 33729, obtained by differential scanning calorimetry, showed three major irreversible endothermic transitions with peaks at 56, 100, and 114 degrees C and a major irreversible exothermic transition with a peak at 119 degrees C. The 114 degrees C transition was identified with coat proteins, and the 56 degrees C transition was identified with heat inactivation. Thermograms of the germinated spores and vegetative cells were much alike, including an endothermic transition attributable to DNA. The ascending part of the main endothermic 100 degrees C transition in the dormant-spore thermograms corresponded to a first-order reaction and was correlated with spore death; i.e., greater than 99.9% of the spores were killed when the transition peak was reached. The maximum death rate of the dormant spores during calorimetry, calculated from separately measured D and z values, occurred at temperatures above the 73 degrees C onset of thermal denaturation and was equivalent to the maximum inactivation rate calculated for the critical target. Most of the spore killing occurred before the release of most of the dipicolinic acid and other intraprotoplast materials. The exothermic 119 degrees C transition was a consequence of the endothermic 100 degrees C transition and probably represented the aggregation of intraprotoplast spore components. Taken together with prior evidence, the results suggest that a crucial protein is the rate-limiting primary target in the heat killing of dormant bacterial spores.

  10. Detectors for Linear Colliders: Calorimetry at a Future Electron-Positron Collider (3/4)

    ScienceCinema

    None

    2016-07-12

    Calorimetry will play a central role in determining the physics reach at a future e+e- collider. The requirements for calorimetry place the emphasis on achieving an excellent jet energy resolution. The currently favoured option for calorimetry at a future e+e- collider is the concept of high granularity particle flow calorimetry. Here granularity and a high pattern recognition capability is more important than the single particle calorimetric response. In this lecture I will describe the recent progress in understanding the reach of high granularity particle flow calorimetry and the related R&D; efforts which concentrate on test beam demonstrations of the technological options for highly granular calorimeters. I will also discuss alternatives to particle flow, for example the technique of dual readout calorimetry.

  11. Detectors for Linear Colliders: Calorimetry at a Future Electron-Positron Collider (3/4)

    SciTech Connect

    2010-02-17

    Calorimetry will play a central role in determining the physics reach at a future e+e- collider. The requirements for calorimetry place the emphasis on achieving an excellent jet energy resolution. The currently favoured option for calorimetry at a future e+e- collider is the concept of high granularity particle flow calorimetry. Here granularity and a high pattern recognition capability is more important than the single particle calorimetric response. In this lecture I will describe the recent progress in understanding the reach of high granularity particle flow calorimetry and the related R&D; efforts which concentrate on test beam demonstrations of the technological options for highly granular calorimeters. I will also discuss alternatives to particle flow, for example the technique of dual readout calorimetry.

  12. Advanced ion beam calorimetry for the test facility ELISE

    NASA Astrophysics Data System (ADS)

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

    2015-04-01

    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

  13. Advanced ion beam calorimetry for the test facility ELISE

    SciTech Connect

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

    2015-04-08

    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 m{sup 2} 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 m{sup 2}, 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

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

    SciTech Connect

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

    2001-12-31

    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''.

  15. Direct Animal Calorimetry, the Underused Gold Standard for Quantifying the Fire of Life*

    PubMed Central

    Kaiyala, Karl J.; Ramsay, Douglas S.

    2012-01-01

    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. PMID:20427023

  16. Direct animal calorimetry, the underused gold standard for quantifying the fire of life.

    PubMed

    Kaiyala, Karl J; Ramsay, Douglas S

    2011-03-01

    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.

  17. Characterization of molecular interactions using isothermal titration calorimetry.

    PubMed

    Krell, Tino; Lacal, Jesús; García-Fontana, Cristina; Silva-Jiménez, Hortencia; Rico-Jiménez, Miriam; Lugo, Andrés Corral; Darias, José Antonio Reyes; Ramos, Juan-Luis

    2014-01-01

    Isothermal titration calorimetry (ITC) is based on a simple titration of one ligand with another and the small heat changes caused by the molecular interaction are detected. From one ITC experiment the complete set of thermodynamic parameters of binding including association and dissociation constants as well as changes in enthalpy, entropy, and free energy can be derived. Using this technique almost any type of molecular interaction can be analyzed. Both ligands are in solution, and there is no need for their chemical derivatization. There are no limits as to the choice of the analysis buffer, and the analysis temperature can be set between 4 and 80 °C. This technique has been primarily applied to study the interaction between various proteins of Pseudomonas with small molecule ligands. In addition, ITC has been used to study the binding of Pseudomonas proteins to target DNA fragments.

  18. Survey of the year 2009: applications of isothermal titration calorimetry.

    PubMed

    Falconer, Robert J; Collins, Brett M

    2011-01-01

    Isothermal titration calorimetry (ITC) is now an established and invaluable method for determining the thermodynamic constants, association constant and stoichiometry of molecular interactions in aqueous solutions. The technique has become widely used by biochemists to study protein interaction with other proteins, small molecules, metal ions, lipids, nucleic acids and carbohydrates; and nucleic acid interaction with small molecules. The drug discovery industry has utilized this approach to measure protein (or nucleic acid) interaction with drug candidates. ITC has been used to screen candidates, guide the design of potential drugs and validate the modelling used in structure-based drug design. Emerging disciplines including nanotechnology and drug delivery could benefit greatly from ITC in enhancing their understanding and control of nano-particle assembly, and drug binding and controlled release. 2010 John Wiley & Sons, Ltd.

  19. Isothermal Titration Calorimetry for Measuring Macromolecule-Ligand Affinity

    PubMed Central

    Duff,, Michael R.; Grubbs, Jordan; Howell, Elizabeth E.

    2011-01-01

    Isothermal titration calorimetry (ITC) is a useful tool for understanding the complete thermodynamic picture of a binding reaction. In biological sciences, macromolecular interactions are essential in understanding the machinery of the cell. Experimental conditions, such as buffer and temperature, can be tailored to the particular binding system being studied. However, careful planning is needed since certain ligand and macromolecule concentration ranges are necessary to obtain useful data. Concentrations of the macromolecule and ligand need to be accurately determined for reliable results. Care also needs to be taken when preparing the samples as impurities can significantly affect the experiment. When ITC experiments, along with controls, are performed properly, useful binding information, such as the stoichiometry, affinity and enthalpy, are obtained. By running additional experiments under different buffer or temperature conditions, more detailed information can be obtained about the system. A protocol for the basic setup of an ITC experiment is given. PMID:21931288

  20. Applications of isothermal titration calorimetry in protein science.

    PubMed

    Liang, Yi

    2008-07-01

    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.

  1. Monitoring RNA-ligand interactions using isothermal titration calorimetry.

    PubMed

    Gilbert, Sunny D; Batey, Robert T

    2009-01-01

    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.

  2. Hydroxylamine nitrate self-catalytic kinetics study with adiabatic calorimetry.

    PubMed

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

    2009-03-15

    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.

  3. Fast Scanning Calorimetry Studies of Supercooled Liquids and Glasses

    NASA Astrophysics Data System (ADS)

    Bhattacharya, Deepanjan

    This dissertation is a compilation of research results of extensive Fast Scanning Calorimetry studies of two non-crystalline materials: Toluene and Water. Motivation for fundamental studies of non-crystalline phases, a brief overview of glassy materials and concepts and definitions related to them is provided in Chapter 1. Chapter 2 provides fundamentals and details of experimental apparata, experimental protocol and calibration procedure. Chapter 3 & 4 provides extensive studies of stable non-crystalline toluene films of micrometer and nanometer thicknesses grown by vapor deposition at distinct deposition rates and temperatures and probed by Fast Scanning Calorimetry. Fast scanning calorimetry is shown to be extremely sensitive to the structure of the vapor-deposited phase and was used to characterize simultaneously its kinetic stability and its thermodynamic properties. According to our analysis, transformation of vapor -deposited samples of toluene during heating with rates in excess 100,000 K/s follows the zero-order kinetics. The transformation rate correlates strongly with the initial enthalpy of the sample, which increases with the deposition rate according to sub-linear law. Analysis of the transformation kinetics of vapor deposited toluene films of various thicknesses reveal a sudden increase in the transformation rate for films thinner than 250 nm. The change in kinetics correlates with the surface roughness scale of the substrate, which is interpreted as evidence for kinetic anisotropy of the samples. We also show that out-of-equilibrium relaxation kinetics and possibly the enthalpy of vapor-deposited (VD) films of toluene are distinct from those of ordinary supercooled (OS) phase even when the deposition takes place at temperatures above the glass softening (Tg). The implications of these findings for the formation mechanism and structure of vapor deposited stable glasses are discussed. Chapter 5 and 6 provide detailed Fast Scanning Calorimetry studies

  4. Modern Analysis of Protein Folding by Differential Scanning Calorimetry.

    PubMed

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

    2016-01-01

    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. © 2016 Elsevier Inc. All rights reserved.

  5. Review of MEMS differential scanning calorimetry for biomolecular study

    NASA Astrophysics Data System (ADS)

    Yu, Shifeng; Wang, Shuyu; Lu, Ming; Zuo, Lei

    2017-07-01

    Differential scanning calorimetry (DSC) is one of the few techniques that allow direct determination of enthalpy values for binding reactions and conformational transitions in biomolecules. It provides the thermodynamics information of the biomolecules which consists of Gibbs free energy, enthalpy and entropy in a straightforward manner that enables deep understanding of the structure function relationship in biomolecules such as the folding/unfolding of protein and DNA, and ligand bindings. This review provides an up to date overview of the applications of DSC in biomolecular study such as the bovine serum albumin denaturation study, the relationship between the melting point of lysozyme and the scanning rate. We also introduce the recent advances of the development of micro-electro-mechanic-system (MEMS) based DSCs.

  6. Do PICU patients meet technical criteria for performing indirect calorimetry?

    PubMed

    Beggs, Megan R; Garcia Guerra, Gonzalo; Larsen, Bodil M K

    2016-10-01

    Indirect calorimetry (IC) is considered gold standard for assessing energy needs of critically ill children as predictive equations and clinical status indicators are often unreliable. Accurate assessment of energy requirements in this vulnerable population is essential given the high risk of over or underfeeding and the consequences thereof. The proportion of patients and patient days in pediatric intensive care (PICU) for which energy expenditure (EE) can be measured using IC is currently unknown. In the current study, we aimed to quantify the daily proportion of consecutive PICU patients who met technical criteria to perform indirect calorimetry and describe the technical contraindications when criteria were not met. Prospective, observational, single-centre study conducted in a cardiac and general PICU. All consecutive patients admitted for at least 96 h were included in the study. Variables collected for each patient included age at admission, admission diagnosis, and if technical criteria for indirect calorimetry were met. Technical criteria variables were collected within the same 2 h each morning and include: provision of supplemental oxygen, ventilator settings, endotracheal tube (ETT) leak, diagnosis of chest tube air leak, provision of external gas support (i.e. nitric oxide), and provision of extracorporeal membrane oxygenation (ECMO). 288 patients were included for a total of 3590 patient days between June 2014 and February 2015. The main reasons for admission were: surgery (cardiac and non-cardiac), respiratory distress, trauma, oncology and medicine/other. The median (interquartile range) patient age was 0.7 (0.3-4.6) years. The median length of PICU stay was 7 (5-14) days. Only 34% (95% CI, 32.4-35.5%) of patient days met technical criteria for IC. For patients less than 6 months of age, technical criteria were met on significantly fewer patient days (29%, p < 0.01). Moreover, 27% of patients did not meet technical criteria for IC on any day

  7. NEUTRON-ENHANCED CALORIMETRY FOR HADRONS (NECH): FINAL REPORT

    SciTech Connect

    Andrew Stroud, Lee Sawyer

    2012-08-31

    We present the results of a project to apply scintillator technology recently developed at Louisiana Tech University to hadronic calorimetry. In particular, we developed a prototype calorimeter module incorporating scintillator embedded with metal oxide nanoparticles as the active layers. These metal oxide nanoparticles of gadolinium oxide, have high cross-sections for interactions with slow neutrons. As a part fo this research project, we have developed a novel method for producing plastic scintillators with metal oxide nanoparticles evenly distributed through the plastic without aggregation.We will test the performance of the calorimeter module in test beam and with a neutron source, in order to measure the response to the neutron component of hadronic showers. We will supplement our detector prototyping activities with detailed studies of the effect of neutron component on the resolution of hadronic energy measurements, particular in the next generation of particle flow calorimeters.

  8. Isothermal titration calorimetry of ion-coupled membrane transporters.

    PubMed

    Boudker, Olga; Oh, SeCheol

    2015-04-01

    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.

  9. Isothermal titration calorimetry of membrane proteins - progress and challenges.

    PubMed

    Rajarathnam, Krishna; Rösgen, Jörg

    2014-01-01

    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.

  10. Analysis of the Escherichia coli glucosamine-6-phosphate synthase activity by isothermal titration calorimetry and differential scanning calorimetry.

    PubMed

    Valerio-Lepiniec, Marie; Aumont-Nicaise, Magali; Roux, Céline; Raynal, Bertrand; England, Patrick; Badet, Bernard; Badet-Denisot, Marie-Ange; Desmadril, Michel

    2010-06-15

    Glucosamine-6-phosphate synthase (GlmS) is responsible for the first and rate-limiting step in the hexosamine biosynthetic pathway. It catalyzes the conversion of D-fructose-6P (F6P) into D-glucosamine-6P (GlcN6P) using L-glutamine (Gln) as nitrogen donor (synthase activity) according to an ordered bi-bi process where F6P binds first. In the absence of F6P, the enzyme exhibits a weak hydrolyzing activity of Gln into Glu and ammonia (glutaminase activity), whereas the presence of F6P strongly stimulates it (hemi-synthase activity). Until now, these different activities were indirectly measured using either coupled enzyme or colorimetric methods. In this work, we have developed a direct assay monitoring the heat released by the reaction. Isothermal titration calorimetry and differential scanning calorimetry were used to determine kinetic and thermodynamic parameters of GlmS. The direct determination at 37 degrees C of kinetic parameters and affinity constants for both F6P and Gln demonstrated that part of the ammonia produced by Gln hydrolysis in the presence of both substrates is not used for the formation of the GlcN6P. The full characterization of this phenomenon allowed to identify experimental conditions where this leak of ammonia is negligible. Enthalpy measurements at 25 degrees C in buffers of various heats of protonation demonstrated that no proton exchange with the medium occurred during the enzyme-catalyzed glutaminase or synthase reaction suggesting for the first time that both products are released as a globally neutral pair composed by the Glu carboxylic side chain and the GlcN6P amine function. Finally we showed that the oligomerization state of GlmS is concentration-dependent. Copyright (c) 2010 Elsevier Inc. All rights reserved.

  11. Thermal Properties of Silk Fibroin Using Fast Scanning Calorimetry

    NASA Astrophysics Data System (ADS)

    Cebe, Peggy; Partlow, Benjamin; Kaplan, David; Wurm, Andreas; Zhuravlev, Evgeny; Schick, Christoph

    We performed fast scanning chip-based calorimetry of silk protein using the Mettler Flash DSC1. We suggest the methodology by which to obtain quantitative information on the very first scan to high temperature, including the melting endotherm of the beta pleated sheets. For proteins, this first scan is the most important one, because the crystalline secondary structural features, the beta pleated sheets, melt after the first heating and cannot be thermally reintroduced. To obtain high quality data, the samples must be treated to drying and enthalpy relaxation sequences. The heat flow rates in heating and cooling must be corrected for asymmetric heat loses. We evaluate methods to obtain an estimate of the sample mass, finally choosing internal calibration using the known heat capacity increment at the glass transition. We report that even heating at rates of 2000 K/s, thermal degradation of silk cannot be totally avoided, though it can be minimized. Using a set of nineteen samples, we successfully determine the liquid state heat capacity of silk as: Cpliquid (T) = (1.98 +0.06) J/gK + T (6.82 +1.4) x10-4 J/gK2. Methods for estimation of the sample mass will be presented and compared. National Science Foundation, Polymers Program DMR-1206010; DAAD; Tufts Faculty Supported Leave.

  12. Calorimetry study of microwave absorption of some solid materials.

    PubMed

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

    2013-01-01

    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.

  13. Hot biological catalysis: isothermal titration calorimetry to characterize enzymatic reactions.

    PubMed

    Mazzei, Luca; Ciurli, Stefano; Zambelli, Barbara

    2014-04-04

    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.

  14. Hot Biological Catalysis: Isothermal Titration Calorimetry to Characterize Enzymatic Reactions

    PubMed Central

    Mazzei, Luca; Ciurli, Stefano; Zambelli, Barbara

    2014-01-01

    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. PMID:24747990

  15. Statistical analysis of plasma thermograms measured by differential scanning calorimetry.

    PubMed

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

    2010-11-01

    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.

  16. Application of pressure perturbation calorimetry to lipid bilayers.

    PubMed

    Heerklotz, Heiko; Seelig, Joachim

    2002-03-01

    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.

  17. Application of isothermal titration calorimetry in bioinorganic chemistry.

    PubMed

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

    2010-11-01

    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.

  18. On the feasibility of water calorimetry with scanned proton radiation

    NASA Astrophysics Data System (ADS)

    Sassowsky, M.; Pedroni, E.

    2005-11-01

    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.

  19. Proton Calorimetry and Gamma-Rays in Arp 220

    NASA Astrophysics Data System (ADS)

    Yoast-Hull, Tova; Gallagher, John S.; Zweibel, Ellen Gould

    2014-08-01

    Until recently, it was thought that starburst galaxies were both electron and proton calorimeters, making them especially bright in gamma-rays. However, with detections of starburst galaxies M82 and NGC 253 by Fermi, HESS, and VERITAS, we find that such galaxies are only partial proton calorimeters due to significant advection by galactic winds. Thus, to find cosmic-ray proton calorimeters, we must look for much denser systems. Previous models of the cosmic ray interactions in Arp 220 (e.g. Torres 2004) suggest it is a proton calorimeter and that it should already be detectable by Fermi. The Torres model suggests that if Arp 220 is a calorimeter, then it should have been detected in gamma-rays by Fermi at levels above current upper limits. We therefore must question. whether Arp 220 is a true proton calorimeter, and if so what other properties could be responsible for its low gamma ray flux. Here, we further explore the observed ranges on environmental properties and model the central nuclei to predict both the radio and gamma-ray spectra. We test the proton calorimetry hypothesis and estimate the observation time needed for a detection by Fermi for a range of assumptions about conditions in Arp 220.

  20. Applying fast calorimetry on a spent nuclear fuel calorimeter

    SciTech Connect

    Liljenfeldt, Henrik

    2015-04-15

    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.

  1. Mapping glycoside hydrolase substrate subsites by isothermal titration calorimetry

    PubMed Central

    Zolotnitsky, Gennady; Cogan, Uri; Adir, Noam; Solomon, Vered; Shoham, Gil; Shoham, Yuval

    2004-01-01

    Relating thermodynamic parameters to structural and biochemical data allows a better understanding of substrate binding and its contribution to catalysis. The analysis of the binding of carbohydrates to proteins or enzymes is a special challenge because of the multiple interactions and forces involved. Isothermal titration calorimetry (ITC) provides a direct measure of binding enthalpy (ΔHa) and allows the determination of the binding constant (free energy), entropy, and stoichiometry. In this study, we used ITC to elucidate the binding thermodynamics of xylosaccharides for two xylanases of family 10 isolated from Geobacillus stearothermophilus T-6. The change in the heat capacity of binding (ΔCp = ΔH/ΔT) for xylosaccharides differing in one sugar unit was determined by using ITC measurements at different temperatures. Because hydrophobic stacking interactions are associated with negative ΔCp, the data allow us to predict the substrate binding preference in the binding subsites based on the crystal structure of the enzyme. The proposed positional binding preference was consistent with mutants lacking aromatic binding residues at different subsites and was also supported by tryptophan fluorescence analysis. PMID:15277671

  2. [Differential scanning calorimetry of blood plasma in breast cancer patients].

    PubMed

    Zapf, István; Fekecs, Tamás; Moezzi, Medhi; Tizedes, György; Pavlovics, Gábor; Kálmán, Endre; Horváth, Péter Ors; Ferencz, Andrea

    2012-12-01

    Breast cancer is the commonest cause of cancer death in women worldwide. Its incidence has been increasing for many years in economically developed countries. Differential scanning calorimetry (DSC) is a thermoanalytical technique which monitors small heat changes between sample and reference materials. This examination is a validly efficient method for the demonstration of structural changes not only in the physical sciences, but in numerous human oncological diseases. The goal of this study was to measure DSC thermogram of blood plasma in breast cancer patients with different stages. Nineteen women with different tumor diameter (0.5-7.5 mm) and with or without regional lymph node metastases were involved in the study. Preoperatively peripheral blood samples were collected from the patients and from healthy controls, and plasma components were analysed by SETARAM micro DSC-II calorimeter. The diameter of the tumor tissue and the number of metastatic lymph nodes were evaluated on the basis of postoperative histological results. In the current study we found difference in changes of the thermal parameters (transition temperature, calorimetric enthalpy) of breast cancer patients' plasma components. Moreover, a tendency has been found for association of these results with tumor size and with the degree of regional lymph node involvement. Preliminary study of the clinical utility of DSC technology arises, even though there is no data in the literature. In cases of breast cancer the blood plasma may be suitable for DSC analysis for diagnosis or staging as well. In order to clarify the relationships we are planning further studies.

  3. The deconvolution of differential scanning calorimetry unfolding transitions.

    PubMed

    Spink, Charles H

    2015-04-01

    This paper is a review of a process for deconvolution of unfolding thermal transitions measured by differential scanning calorimetry. The mathematical background is presented along with illustrations of how the unfolding data is processed to resolve the number of sequential transitions needed to describe an unfolding mechanism and to determine thermodynamic properties of the intermediate states. Examples of data obtained for a simple two-state unfolding of a G-quadruplex DNA structure derived from the basic human telomere sequence, (TTAGGG)4TT are used to present some of the basic issues in treating the DSC data. A more complex unfolding mechanism is also presented that requires deconvolution of a multistate transition, the unfolding of a related human telomere structure, (TTAGGG)12 TT. The intent of the discussion is to show the steps in deconvolution, and to present the data at each step to help clarify how the information is derived from the various mathematical manipulations. Copyright © 2014. Published by Elsevier Inc.

  4. Differential scanning calorimetry to investigate G-quadruplexes structural stability.

    PubMed

    Pagano, Bruno; Randazzo, Antonio; Fotticchia, Iolanda; Novellino, Ettore; Petraccone, Luigi; Giancola, Concetta

    2013-11-01

    Differential Scanning Calorimetry (DSC) is a straightforward methodology to characterize the energetics of thermally-induced transitions of DNA and other biological macromolecules. Therefore, DSC has been used to study the thermodynamic stability of several nucleic acids structures. G-quadruplexes are among the most important non-canonical nucleic acid architectures that are receiving great consideration. This article reports examples on the contribution of DSC to the knowledge of G-quadruplex structures. The selected case studies show the potential of this method in investigating the structure stability of G-quadruplex forming nucleic acids, and in providing information on their structural complexity. Indeed, DSC can determine thermodynamic parameters of G-quadruplex folding/unfolding processes, but it can also be useful to reveal the formation of multiple conformations or the presence of intermediate states along the unfolding pathway, and to evaluate the impact of chemical modifications on their structural stability. This article aims to show that DSC is an important complementary methodology to structural techniques, such as NMR and X-ray crystallography, in the study of G-quadruplex forming nucleic acids. Copyright © 2013 Elsevier Inc. All rights reserved.

  5. Cure kinetics of epoxy matrix resin by differential scanning calorimetry

    NASA Technical Reports Server (NTRS)

    Cizmecioglu, M.; Gupta, A.

    1982-01-01

    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.

  6. The Electromagnetic Calorimetry of the PANDA Detector at FAIR

    NASA Astrophysics Data System (ADS)

    Novotny, R. W.; PANDA Collaboration

    2012-12-01

    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.

  7. On the feasibility of water calorimetry with scanned proton radiation.

    PubMed

    Sassowsky, M; Pedroni, E

    2005-11-21

    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.

  8. Measuring Multivalent Binding Interactions by Isothermal Titration Calorimetry.

    PubMed

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

    2016-01-01

    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.

  9. Differential Scanning Calorimetry (DSC) for planetary surface exploration

    NASA Technical Reports Server (NTRS)

    Gooding, James L.; Ming, Douglas W.

    1993-01-01

    Differential Scanning Calorimetry (DSC) is the quantitative measurement of the enthalpic response of a material to a systematic change in temperature. In practice, the heat flow into or outward from a sample is measured as the sample is heated or cooled at a carefully controlled rate. DSC superficially resembles, but is not the same as differential thermal analysis (DTA), which is the measurement of temperature differences between a sample and reference material as the pair is heated or cooled. The fundamental properties measured by DSC are enthalpies and temperatures of phase transitions and constant-pressure heat capacities. Depending on instrument design and the nature of the sample, high-quality DSC analyses can be obtained on only a few milligrams of solid materials. DSC requires direct contact with the sample and generally degrades, if not destroys, the sample as a consequence of heating. In laboratory applications, it is common to subject the gaseous effluent from the DSC to analysis by a separate evolved-gas analyzer (EGA).

  10. Measuring the Kinetics of Molecular Association by Isothermal Titration Calorimetry.

    PubMed

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

    2016-01-01

    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.

  11. Characterization of membrane protein interactions by isothermal titration calorimetry.

    PubMed

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

    2014-10-23

    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.

  12. Cure kinetics of epoxy matrix resin by differential scanning calorimetry

    NASA Technical Reports Server (NTRS)

    Cizmecioglu, M.; Gupta, A.

    1982-01-01

    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.

  13. Characterization of protein-protein interactions by isothermal titration calorimetry.

    PubMed

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

    2015-01-01

    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.

  14. A microfabrication-based approach to quantitative isothermal titration calorimetry.

    PubMed

    Wang, Bin; Jia, Yuan; Lin, Qiao

    2016-04-15

    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.

  15. PREFACE: XIV International Conference on Calorimetry in High Energy Physics

    NASA Astrophysics Data System (ADS)

    Wang, Yifang

    2011-03-01

    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

  16. An Integrated-Circuit Temperature Sensor for Calorimetry and Differential Temperature Measurement.

    ERIC Educational Resources Information Center

    Muyskens, Mark A.

    1997-01-01

    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)

  17. An Integrated-Circuit Temperature Sensor for Calorimetry and Differential Temperature Measurement.

    ERIC Educational Resources Information Center

    Muyskens, Mark A.

    1997-01-01

    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)

  18. A Study of Concept Mapping as an Instructional Intervention in an Undergraduate General Chemistry Calorimetry Laboratory

    NASA Astrophysics Data System (ADS)

    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.

  19. Identifying Hydrated Salts Using Simultaneous Thermogravimetric Analysis and Differential Scanning Calorimetry

    ERIC Educational Resources Information Center

    Harris, Jerry D.; Rusch, Aaron W.

    2013-01-01

    simultaneous thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) to characterize colorless, hydrated salts with anhydrous melting points less than 1100 degrees C. The experiment could be used to supplement the lecture discussing gravimetric techniques. It is…

  20. Determination of Heats of Fusion: Using Differential Scanning Calorimetry for the AP Chemistry Courses.

    ERIC Educational Resources Information Center

    Temme, Susan M.

    1995-01-01

    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)

  1. Parallelism between gradient temperature raman spectroscopy and differential scanning calorimetry results

    USDA-ARS?s Scientific Manuscript database

    Temperature dependent Raman spectroscopy (TDR) applies the temperature gradients utilized in differential scanning calorimetry (DSC) to Raman spectroscopy, providing a straightforward technique to identify molecular rearrangements that occur just prior to phase transitions. Herein we apply TDR and D...

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

    ERIC Educational Resources Information Center

    Temme, Susan M.

    1995-01-01

    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. Identifying Hydrated Salts Using Simultaneous Thermogravimetric Analysis and Differential Scanning Calorimetry

    ERIC Educational Resources Information Center

    Harris, Jerry D.; Rusch, Aaron W.

    2013-01-01

    simultaneous thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) to characterize colorless, hydrated salts with anhydrous melting points less than 1100 degrees C. The experiment could be used to supplement the lecture discussing gravimetric techniques. It is…

  4. Calorimetry in Medical Applications: Single-Photon Emission Computed Tomography and Positron Emission Tomography

    SciTech Connect

    Chen, C.-T.

    2006-10-27

    Positron emission tomography (PET) and single-photon emission computed tomography (SPECT), two nuclear medicine imaging modalities broadly used in clinics and research, share many common instrumentation, detector, and electronics technology platforms with calorimetry in high-energy physics, astronomy, and other physics sciences. Historically, advances made in calorimetry had played major roles in the development of novel approaches and critical technologies essential to the evolution of PET and SPECT. There have also been examples in which PET/SPECT developments had led to new techniques in calorimetry for other application areas. In recent years, several innovations have propelled advances in both calorimetry in general and PET/SPECT in particular. Examples include time-of-flight (TOF) measurements, silicon photomultipliers (SiPMs), etc.

  5. Analysis of RNA folding and ligand binding by conventional and high-throughput calorimetry.

    PubMed

    Sokoloski, Joshua E; Bevilacqua, Philip C

    2012-01-01

    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.

  6. Development of GEM-Based Digital Hadron Calorimetry Using the SLAC KPiX Chip

    SciTech Connect

    White, A.; /Texas U., Arlington /Washington U., Seattle /Unlisted /SLAC

    2012-04-12

    The development of Digital Hadron Calorimetry for the SiD detector Concept for the International Linear Collider is described. The jet energy requirements of the ILC physics program are discussed. The concept of GEM-based digital hadron calorimetry is presented, followed by a description of, and results from, prototype detectors. Plans are described for the construction of 1m{sup 2} GEM-DHCAL planes to be tested as part of a future calorimeter stack.

  7. Kinetics Characteristics of Nitrogen Hydrates Respond to Differential Scanning Calorimetry

    NASA Astrophysics Data System (ADS)

    Chen, Q.; Liu, C.; Ye, Y.; Gong, J.

    2012-12-01

    In this study, a high pressure differential scanning calorimetry (HP DSC) based on thermo-analytical technique was applied to investigate the kinetics and thermodynamics characteristics of nitrogen hydrates. Nitrogen hydrates was synthesized in the sample vessel under different pressures as temperature decreased from 293 to 233 K with a constant cooling rate of 0.2 K/min controlled by the DSC. To measure the hydrates dissociation enthalpies , the temperature was slowly raised up from 233 to 293 K at a constant rate ranging of 0.05 K/min. 1. Peak area on the heat flow curves represents the amount of heat during phase transition. In these experiments, the total water added to the sample vessel (mt) is already known. By integrating the peak areas of ice and hydrate, we know the total heats of ice (Qi) and hydrate (Qh), respectively. As the heat of ice per gram can be measured easily (336.366 J/g), the mass of ice (mi) can be obtain. Then, the dissociation heat of nitrogen hydrate per gram (Hh ) can be calculated by the equation: H(J/g)=Qh/(mt-mi) It is shown that the dissociation heats of nitrogen hydrates are a little larger than ice, but do not change a lot with different pressures. The average value of dissociation heat is 369.158 J/g. 2. During the DSC cooling stage, hydrate formed at temperature much lower than equilibrium. The biggest sub-cooling is about 291 K, while the smallest one is about 279 K. However, during these experiments, the pressure did not show obvious relationship with sub-cooling. It confirmed that even the proper conditions were achieved, formation was still a stochastic process. For one thing, due to the random distribution of dissolved gas in water, the interfacial tension and the water activity were not equal in the whole system. And if there was a free gas phase, which leads to different fugacity on water-gas interface, the stochastic behavior would be more significant in the sample vessel. 3. The energy released from hydrates formation as

  8. VO2 and VCO2 variabilities through indirect calorimetry instrumentation.

    PubMed

    Cadena-Méndez, Miguel; Escalante-Ramírez, Boris; Azpiroz-Leehan, Joaquín; Infante-Vázquez, Oscar

    2013-01-01

    The aim of this paper is to understand how to measure the VO2 and VCO2 variabilities in indirect calorimetry (IC) since we believe they can explain the high variation in the resting energy expenditure (REE) estimation. We propose that variabilities should be separately measured from the VO2 and VCO2 averages to understand technological differences among metabolic monitors when they estimate the REE. To prove this hypothesis the mixing chamber (MC) and the breath-by-breath (BbB) techniques measured the VO2 and VCO2 averages and their variabilities. Variances and power spectrum energies in the 0-0.5 Hertz band were measured to establish technique differences in steady and non-steady state. A hybrid calorimeter with both IC techniques studied a population of 15 volunteers that underwent the clino-orthostatic maneuver in order to produce the two physiological stages. The results showed that inter-individual VO2 and VCO2 variabilities measured as variances were negligible using the MC while variabilities measured as spectral energies using the BbB underwent 71 and 56% (p < 0.05), increase respectively. Additionally, the energy analysis showed an unexpected cyclic rhythm at 0.025 Hertz only during the orthostatic stage, which is new physiological information, not reported previusly. The VO2 and VCO2 inter-individual averages increased to 63 and 39% by the MC (p < 0.05) and 32 and 40% using the BbB (p < 0.1), respectively, without noticeable statistical differences among techniques. The conclusions are: (a) metabolic monitors should simultaneously include the MC and the BbB techniques to correctly interpret the steady or non-steady state variabilities effect in the REE estimation, (b) the MC is the appropriate technique to compute averages since it behaves as a low-pass filter that minimizes variances, (c) the BbB is the ideal technique to measure the variabilities since it can work as a high-pass filter to generate discrete time series able to accomplish

  9. Enzyme-catalyzed and binding reaction kinetics determined by titration calorimetry.

    PubMed

    Hansen, Lee D; Transtrum, Mark K; Quinn, Colette; Demarse, Neil

    2016-05-01

    Isothermal calorimetry allows monitoring of reaction rates via direct measurement of the rate of heat produced by the reaction. Calorimetry is one of very few techniques that can be used to measure rates without taking a derivative of the primary data. Because heat is a universal indicator of chemical reactions, calorimetry can be used to measure kinetics in opaque solutions, suspensions, and multiple phase systems and does not require chemical labeling. The only significant limitation of calorimetry for kinetic measurements is that the time constant of the reaction must be greater than the time constant of the calorimeter which can range from a few seconds to a few minutes. Calorimetry has the unique ability to provide both kinetic and thermodynamic data. This article describes the calorimetric methodology for determining reaction kinetics and reviews examples from recent literature that demonstrate applications of titration calorimetry to determine kinetics of enzyme-catalyzed and ligand binding reactions. A complete model for the temperature dependence of enzyme activity is presented. A previous method commonly used for blank corrections in determinations of equilibrium constants and enthalpy changes for binding reactions is shown to be subject to significant systematic error. Methods for determination of the kinetics of enzyme-catalyzed reactions and for simultaneous determination of thermodynamics and kinetics of ligand binding reactions are reviewed. Copyright © 2015 Elsevier B.V. All rights reserved.

  10. Picowatt Resolution Calorimetry for Micro and Nanoscale Energy Transport Studies

    NASA Astrophysics Data System (ADS)

    Sadat, Seid H.

    Precise quantification of energy transport is key to obtaining insights into a wide range of phenomena across various disciplines including physics, chemistry, biology and engineering. This thesis describes technical advancements into heat-flow calorimetry which enable measurement of energy transport at micro and nanoscales with picowatt resolution. I have developed two types of microfabricated calorimeter devices and demonstrated single digit picowatt resolution at room temperature. Both devices incorporate two distinct features; an active area isolated by a thermal conductance (GTh) of less than 1 microW/K and a high resolution thermometer with temperature resolution (DeltaTres) in the micro kelvin regime. These features enable measurements of heat currents (q) with picowatt resolution (q= Th xDeltaTres). In the first device the active area is suspended via silicon nitride beams with excellent thermal isolation (~600 nW/K) and a bimaterial cantilever (BMC) thermometer with temperature resolution of ~6 microK. Taken together this design enabled calorimetric measurements with 4 pW resolution. In the second device, the BMC thermometry technique is replaced by a high-resolution resistance thermometry scheme. A detailed noise analysis of resistance thermometers, confirmed by experimental data, enabled me to correctly predict the resolution of different measurement schemes and propose techniques to achieve an order of magnitude improvement in the resolution of resistive thermometers. By incorporating resistance thermometers with temperature resolution of ~30 microK, combined with a thermal isolation of ~150 nW/K, I demonstrated an all-electrical calorimeter device with a resolution of ~ 5 pW. Finally, I used these calorimeters to study Near-Field Radiative Heat Transfer (NF-RHT). Using these devices, we studied--for the first time--the effect of film thickness on the NF-RHT between two dielectric surfaces. We showed that even a very thin film (~50 nm) of silicon

  11. [Analysis of energy expenditure in adults with cystic fibrosis: comparison of indirect calorimetry and prediction equations].

    PubMed

    Fuster, Casilda Olveira; Fuster, Gabriel Olveira; Galindo, Antonio Dorado; Galo, Alicia Padilla; Verdugo, Julio Merino; Lozano, Francisco Miralles

    2007-07-01

    Undernutrition, which implies an imbalance between energy intake and energy requirements, is common in patients with cystic fibrosis. The aim of this study was to compare resting energy expenditure determined by indirect calorimetry with that obtained with commonly used predictive equations in adults with cystic fibrosis and to assess the influence of clinical variables on the values obtained. We studied 21 patients with clinically stable cystic fibrosis, obtaining data on anthropometric variables, hand grip dynamometry, electrical bioimpedance, and resting energy expenditure by indirect calorimetry. We used the intraclass correlation coefficient (ICC) and the Bland-Altman method to assess agreement between the values obtained for resting energy expenditure measured by indirect calorimetry and those obtained with the World Health Organization (WHO) and Harris-Benedict prediction equations. The prediction equations underestimated resting energy expenditure in more than 90% of cases. The agreement between the value obtained by indirect calorimetry and that calculated with the prediction equations was poor (ICC for comparisons with the WHO and Harris-Benedict equations, 0.47 and 0.41, respectively). Bland-Altman analysis revealed a variable bias between the results of indirect calorimetry and those obtained with prediction equations, irrespective of the resting energy expenditure. The difference between the values measured by indirect calorimetry and those obtained with the WHO equation was significantly larger in patients homozygous for the DeltaF508 mutation and in those with exocrine pancreatic insufficiency. The WHO and Harris-Benedict prediction equations underestimate resting energy expenditure in adults with cystic fibrosis. There is poor agreement between the values for resting energy expenditure determined by indirect calorimetry and those estimated with prediction equations. Underestimation was greater in patients with exocrine pancreatic insufficiency and

  12. Effect of Body Position on Energy Expenditure of Preterm Infants as Determined by Simultaneous Direct and Indirect Calorimetry.

    PubMed

    Bell, Edward F; Johnson, Karen J; Dove, Edwin L

    2017-04-01

    Background Indirect calorimetry is the standard method for estimating energy expenditure in clinical research. Few studies have evaluated indirect calorimetry in infants by comparing it with simultaneous direct calorimetry. Our purpose was (1) to compare the energy expenditure of preterm infants determined by these two methods, direct calorimetry and indirect calorimetry; and (2) to examine the effect of body position, supine or prone, on energy expenditure. Study Design We measured energy expenditure by simultaneous direct (heat loss by gradient-layer calorimeter corrected for heat storage) and indirect calorimetry (whole-body oxygen consumption and carbon dioxide production) in 15 growing preterm infants during two consecutive interfeeding intervals, once in the supine position and once in the prone position. Results The mean energy expenditure for all measurements in both positions did not differ significantly by the method used: 2.82 (standard deviation [SD] 0.42) kcal/kg/h by direct calorimetry and 2.78 (SD 0.48) kcal/kg/h by indirect calorimetry. The energy expenditure was significantly lower, by 10%, in the prone than in the supine position, whether examined by direct calorimetry (2.67 vs. 2.97 kcal/kg/h, p < 0.001) or indirect calorimetry (2.64 vs. 2.92 kcal/kg/h, p = 0.017). Conclusion Direct calorimetry and indirect calorimetry gave similar estimates of energy expenditure. Energy expenditure was 10% lower in the prone position than in the supine position.

  13. [An experimental study on ischemically induced brain damage by whole body calorimetry and pathohistology in the gerbil].

    PubMed

    Kishi, H

    1998-05-01

    Moderate hypothermia has been reported to mitigate neuronal damage in the gerbil brain following brief periods of forebrain ischemia, but the relationship between brain damage and whole body calorimetry has not been clarified. We report the effect of hypothermia on the brain damage by whole body calorimetry using Bio Dynamic Calorimeter (BDC200, ESCO Ltd JAPAN). Although it is an indirect method, whole body calorimetry may be able to measure the brain damage, thereby enabling investigations on alleviation of brain damage.

  14. The physics of compensating calorimetry and the new CALOR89 code system

    SciTech Connect

    Gabriel, T.A.; Brau, J.E.; Bishop, B.L.

    1989-03-01

    Much of the understanding of the physics of calorimetry has come from the use of excellent radiation transport codes. A new understanding of compensating calorimetry was introduced four years ago following detailed studies with a new CALOR system. Now, the CALOR system has again been revised to reflect a better comprehension of high energy nuclear collisions by incorporating a modified high energy fragmentation model from FLUKA87. This revision will allow for the accurate analysis of calorimeters at energies of 100's of GeV. Presented in this paper is a discussion of compensating calorimetry, the new CALOR system, the revisions to HETC, and recently generated calorimeter related data on modes of energy deposition and secondary neutron production (E < 50 MeV) in infinite iron and uranium blocks. 38 refs., 5 figs., 5 tabs.

  15. Multi-slope warm-up calorimetry of Integrated Dewar-Detector Assemblies

    NASA Astrophysics Data System (ADS)

    Veprik, Alexander; Shlomovich, Baruch; Tuito, Avi

    2015-05-01

    Boil-off isothermal calorimetry of Integrated Dewar-Detector Assemblies (IDDA) is a routine part of acceptance testing. In this traditional approach, the cryogenic liquid coolant (typically LN2) is allowed to naturally boil off from the Dewar well to the atmosphere. The parasitic heat load is then evaluated as the product of the latent heat of vaporization and the "last drop" boil-off rate monitored usually by a mass flow meter. An inherent limitation of this technique is that it is applicable only at the fixed boiling temperature of the chosen liquid coolant, for example, 77K for LN2. There is a need, therefore, to use other (often exotic) cryogenic liquids when calorimetry is needed at temperatures other than 77K. A further drawback is related to the transitional nature of last drop boiling, which manifests itself in development of enlarged bubbles, explosions and geysering. This results in an uneven flow rate and also affects the natural temperature gradient along the cold finger. Additionally, mass flow meters are known to have limited measurement accuracy. The above considerations especially hold true for advanced High Operational Temperature IDDAs, typically featuring short cold fingers and working at 150K and above. In this work, we adapt the well-known technique of dual-slope calorimetry and show how accurate calorimetry may be performed by precooling the IDDA and comparing the warm-up slopes of the thermal transient processes under different trial added heat loads. Because of the simplicity, accuracy and ability to perform calorimetry literally at any temperature of interest, this technique shows good potential for replacing traditional boil-off calorimetry.

  16. Monitoring of an RNA Multistep Folding Pathway by Isothermal Titration Calorimetry

    PubMed Central

    Reymond, Cédric; Bisaillon, Martin; Perreault, Jean-Pierre

    2009-01-01

    Abstract Isothermal titration calorimetry was used to monitor the energetic landscape of a catalytic RNA, specifically that of the hepatitis delta virus ribozyme. Using mutants that isolated various tertiary interactions, the thermodynamic parameters of several ribozyme-substrate intermediates were determined. The results shed light on the impact of several tertiary interactions on the global structure of the ribozyme. In addition, the data indicate that the formation of the P1.1 pseudoknot is the limiting step of the molecular mechanism. Last, as illustrated here, isothermal titration calorimetry appears to be a method of choice for the elucidation of an RNA's folding pathway. PMID:19134473

  17. Building process knowledge using inline spectroscopy, reaction calorimetry and reaction modeling--the integrated approach.

    PubMed

    Tummala, Srinivas; Shabaker, John W; Leung, Simon S W

    2005-11-01

    For over two decades, reaction engineering tools and techniques such as reaction calorimetry, inline spectroscopy and, to a more limited extent, reaction modeling, have been employed within the pharmaceutical industry to ensure safe and robust scale-up of organic reactions. Although each of these techniques has had a significant impact on the landscape of process development, an effective integrated approach is now being realized that combines calorimetry and spectroscopy with predictive modeling tools. This paper reviews some recent advances in the use of these reaction engineering tools in process development within the pharmaceutical industry and discusses their potential impact on the effective application of the integrated approach.

  18. Tin clusters that do not melt: Calorimetry measurements up to 650 K

    NASA Astrophysics Data System (ADS)

    Breaux, Gary A.; Neal, Colleen M.; Cao, Baopeng; Jarrold, Martin F.

    2005-02-01

    Recent theoretical studies [K. Joshi, D. G. Kanhere, and S. A. Blundell, Phys. Rev. B 67, 235413 (2003)] predict that Sn20 melts at around 1200K . We have performed calorimetry measurements on unsupported Sn18+ , Sn19+ , Sn20+ , and Sn21+ in an effort to test this prediction. We find that these tin clusters disappear well below their predicted melting temperature due to dissociation. Calorimetry measurements performed up to around 650K show some small features (which may be due to localized structural changes) but no clear melting transitions. Hence, tin clusters in this size regime do not melt—they sublime.

  19. Thermodynamics of Surfactants, Block Copolymers and Their Mixtures in Water: The Role of the Isothermal Calorimetry

    PubMed Central

    De Lisi, Rosario; Milioto, Stefania; Muratore, Nicola

    2009-01-01

    The thermodynamics of conventional surfactants, block copolymers and their mixtures in water was described to the light of the enthalpy function. The two methodologies, i.e. the van’t Hoff approach and the isothermal calorimetry, used to determine the enthalpy of micellization of pure surfactants and block copolymers were described. The van’t Hoff method was critically discussed. The aqueous copolymer+surfactant mixtures were analyzed by means of the isothermal titration calorimetry and the enthalpy of transfer of the copolymer from the water to the aqueous surfactant solutions. Thermodynamic models were presented to show the procedure to extract straightforward molecular insights from the bulk properties. PMID:19742173

  20. Small pad RPCs as detector for high granularity digital hadron calorimetry

    NASA Astrophysics Data System (ADS)

    Ammosov, V.; Gapienko, V.; Ivanilov, A.; Sefkow, F.; Semak, A.; Sviridov, Yu.; Usenko, E.; Zaets, V.

    2004-11-01

    Requirements for sampling hadron calorimetry with gaseous active medium and digital read-out for a future linear e+e--collider (FLC) are formulated. Monogap glass Resistive Plate Chamber (RPC) prototypes equipped with 1cm2 read-out pads and operated in saturated avalanche and streamer modes are studied as a possible detector for digital hadron calorimetry. Operating characteristics of the prototypes such as induced charges, efficiencies and fired pad multiplicities are measured for different gas mixtures, gas gap widths and anode thicknesses, electronics thresholds, beam incident angle and intensity. Choice of RPC working performance is outlined.

  1. Direct absorbed dose to water determination based on water calorimetry in scanning proton beam delivery

    SciTech Connect

    Sarfehnia, A.; Clasie, B.; Chung, E.; Lu, H. M.; Flanz, J.; Cascio, E.; Engelsman, M.; Paganetti, H.; Seuntjens, J.

    2010-07-15

    Purpose: The aim of this manuscript is to describe the direct measurement of absolute absorbed dose to water in a scanned proton radiotherapy beam using a water calorimeter primary standard. Methods: The McGill water calorimeter, which has been validated in photon and electron beams as well as in HDR {sup 192}Ir brachytherapy, was used to measure the absorbed dose to water in double scattering and scanning proton irradiations. The measurements were made at the Massachusetts General Hospital proton radiotherapy facility. The correction factors in water calorimetry were numerically calculated and various parameters affecting their magnitude and uncertainty were studied. The absorbed dose to water was compared to that obtained using an Exradin T1 Chamber based on the IAEA TRS-398 protocol. Results: The overall 1-sigma uncertainty on absorbed dose to water amounts to 0.4% and 0.6% in scattered and scanned proton water calorimetry, respectively. This compares to an overall uncertainty of 1.9% for currently accepted IAEA TRS-398 reference absorbed dose measurement protocol. The absorbed dose from water calorimetry agrees with the results from TRS-398 well to within 1-sigma uncertainty. Conclusions: This work demonstrates that a primary absorbed dose standard based on water calorimetry is feasible in scattered and scanned proton beams.

  2. Isothermal Titration Calorimetry and Macromolecular Visualization for the Interaction of Lysozyme and Its Inhibitors

    ERIC Educational Resources Information Center

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

    2015-01-01

    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…

  3. Student Learning of Thermochemical Concepts in the Context of Solution Calorimetry.

    ERIC Educational Resources Information Center

    Greenbowe, Thomas J.; Meltzer, David E.

    2003-01-01

    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…

  4. Protein Unfolding Coupled to Ligand Binding: Differential Scanning Calorimetry Simulation Approach

    ERIC Educational Resources Information Center

    Celej, Maria Soledad; Fidelio, Gerardo Daniel; Dassie, Sergio Alberto

    2005-01-01

    A comprehensive theoretical description of thermal protein unfolding coupled to ligand binding is presented. The thermodynamic concepts are independent of the method used to monitor protein unfolding but a differential scanning calorimetry is being used as a tool for examining the unfolding process.

  5. Student Learning of Thermochemical Concepts in the Context of Solution Calorimetry.

    ERIC Educational Resources Information Center

    Greenbowe, Thomas J.; Meltzer, David E.

    2003-01-01

    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…

  6. Thermodynamic investigations of protein's behaviour with ionic liquids in aqueous medium studied by isothermal titration calorimetry.

    PubMed

    Bharmoria, Pankaj; Kumar, Arvind

    2016-05-01

    While a number of reports appear on ionic liquids-proteins interactions, their thermodynamic behaviour using suitable technique like isothermal titration calorimetry is not systematically presented. Isothermal titration calorimetry (ITC) is a key technique which can directly measure the thermodynamic contribution of IL binding to protein, particularly the enthalpy, heat capacities and binding stoichiometry. Ionic liquids (ILs), owing to their unique and tunable physicochemical properties have been the central area of scientific research besides graphene in the last decade, and growing unabated. Their encounter with proteins in the biological system is inevitable considering their environmental discharge though most of them are recyclable for a number of cycles. In this article we will cover the thermodynamics of proteins upon interaction with ILs as osmolyte and surfactant. The up to date literature survey of IL-protein interactions using isothermal titration calorimetry will be discussed and parallel comparison with the results obtained for such studies with other techniques will be highlighted to demonstrate the accuracy of ITC technique. Net stability of proteins can be obtained from the difference in the free energy (ΔG) of the native (folded) and denatured (unfolded) state using the Gibbs-Helmholtz equation (ΔG=ΔH-TΔS). Isothermal titration calorimetry can directly measure the heat changes upon IL-protein interactions. Calculation of other thermodynamic parameters such as entropy, binding constant and free energy depends upon the proper fitting of the binding isotherms using various fitting models. Copyright © 2015 Elsevier B.V. All rights reserved.

  7. Levitation calorimetry. IV - The thermodynamic properties of liquid cobalt and palladium.

    NASA Technical Reports Server (NTRS)

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

    1971-01-01

    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.

  8. Accelerating rate calorimetry: A new technique for safety studies in lithium systems

    NASA Technical Reports Server (NTRS)

    Ebner, W. B.

    1982-01-01

    The role of exothermic reactions in battery test modes is discussed. The exothermic reactions are characterized with respect to their time-temperature and time-pressure behavior. Reactions occuring for any major exotherm were examined. The accelerating rate calorimetry methods was developed to study lithium cells susceptibility to thermal runaway reactions following certain abuse modes such as forced discharge into reversal and charging.

  9. Determination of caloric values of agricultural crops and crop waste by Adiabatic Bomb Calorimetry

    USDA-ARS?s Scientific Manuscript database

    Calorific values of agricultural crops and their waste were measured by adiabatic bomb calorimetry. Sustainable farming techniques require that all potential sources of revenue be utilized. A wide variety of biomass is beginning to be used as alternative fuels all over the world. The energy potentia...

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

    USDA-ARS?s Scientific Manuscript database

    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...

  11. Benchmark testing of DIII-D neutral beam modeling with water flow calorimetry

    SciTech Connect

    Rauch, J. M.; Crowley, B. J.; Scoville, J. T.; Murphy, C. J.

    2016-06-02

    Power loading on beamline components in the DIII-D neutral beam system is measured in this paper using water flow calorimetry. The results are used to benchmark beam transport models. Finally, anomalously high heat loads in the magnet region are investigated and a speculative hypothesis as to their origin is presented.

  12. Examination of water phase transitions in Loblolly pine and cell wall components by differential scanning calorimetry

    Treesearch

    Samuel L. Zelinka; Michael J. Lambrecht; Samuel V. Glass; Alex C. Wiedenhoeft; Daniel J. Yelle

    2012-01-01

    This paper examines phase transformations of water in wood and isolated wood cell wall components using differential scanning calorimetry with the purpose of better understanding "Type II water" or "freezable bound water" that has been reported for cellulose and other hydrophilic polymers. Solid loblolly pine (Pinus taeda...

  13. Monolithic front-end preamplifiers for a broad range of calorimetry applications

    SciTech Connect

    Radeka, V.; Rescia, S.; Manfredi, P.F.; Speziali, V. |

    1993-12-31

    The present paper summarizes the salient results of a research and development activity in the area of low noise preamplifiers for different applications in calorimetry. Design target for all circuits considered here are low noise, ability to cope with broad energy ranges and radiation hardness.

  14. Isothermal Titration Calorimetry and Macromolecular Visualization for the Interaction of Lysozyme and Its Inhibitors

    ERIC Educational Resources Information Center

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

    2015-01-01

    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. Protein Unfolding Coupled to Ligand Binding: Differential Scanning Calorimetry Simulation Approach

    ERIC Educational Resources Information Center

    Celej, Maria Soledad; Fidelio, Gerardo Daniel; Dassie, Sergio Alberto

    2005-01-01

    A comprehensive theoretical description of thermal protein unfolding coupled to ligand binding is presented. The thermodynamic concepts are independent of the method used to monitor protein unfolding but a differential scanning calorimetry is being used as a tool for examining the unfolding process.

  16. Calorimetry-Derived Composition Vectors to Resolve Component Raman Spectra in Phospholipid Phase Transitions.

    PubMed

    Kitt, Jay P; Bryce, David A; Harris, Joel M

    2016-07-01

    Multidimensional least squares analysis is a well-established technique for resolving component vibrational spectra from mixed samples or systems. Component resolution of temperature-dependent vibrational spectra is challenging, however, due to the lack of a suitable model for the variation in sample composition with temperature. In this work, analysis of temperature-dependent Raman spectra of lipid membranes is accomplished by using "concentration" vectors independently derived from enthalpy changes determined by differential scanning calorimetry. Specifically, the lipid-bilayer phase transitions of DMPC (1,2-dipalmitoyl-sn-glycero-3-phosphocholine) are investigated through Raman spectra acquired from individual, optically trapped vesicles in suspension as a function of temperature. Heat capacity profiles of the same vesicle suspension are measured using differential scanning calorimetry and numerically integrated to generate enthalpy change curves of each phase transition, which are in turn used to construct composition vectors. Multidimensional least squares analysis optimized for a fit to these composition vectors allows resolution of the component spectra corresponding to gel, ripple, and liquid-crystalline phases of the DMPC. The quality of fit of the calorimetry-derived results is confirmed by unstructured residual differences between the data and the model, and a composition variation predicted by the resolved spectra that matches the calorimetry results. This approach to analysis of temperature-dependent spectral data could be readily applied in other areas of materials characterization, where one is seeking to learn about structural changes that occur through temperature-dependent phase transitions.

  17. Calorimetry exchange program quarterly data report for, January 1989--March 1989

    SciTech Connect

    Lyons, J.E.; McClelland, T.M.

    1996-08-01

    The goals of the calorimetry sample exchange program are to: discuss measurement differences; improve analytical methods; discuss new measurement capabilities; provide data to DOE on measurement capabilities to evaluate shipper-receiver differences; provide standardized materials as necessary; and provide a measurement control program for plutonium analysis. A sample of plutonium dioxide powder is available at each participating site for NDA analysis.

  18. Accelerating rate calorimetry: A new technique for safety studies in lithium systems

    NASA Technical Reports Server (NTRS)

    Ebner, W. B.

    1982-01-01

    The role of exothermic reactions in battery test modes is discussed. The exothermic reactions are characterized with respect to their time-temperature and time-pressure behavior. Reactions occuring for any major exotherm were examined. The accelerating rate calorimetry methods was developed to study lithium cells susceptibility to thermal runaway reactions following certain abuse modes such as forced discharge into reversal and charging.

  19. Levitation calorimetry. IV - The thermodynamic properties of liquid cobalt and palladium.

    NASA Technical Reports Server (NTRS)

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

    1971-01-01

    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.

  20. Isoquinoline alkaloids and their binding with DNA: calorimetry and thermal analysis applications.

    PubMed

    Bhadra, Kakali; Kumar, Gopinatha Suresh

    2010-11-01

    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. Methodological evaluation of indirect calorimetry data in lean and obese rats.

    PubMed

    Rafecas, I; Esteve, M; Fernández-López, J A; Remesar, X; Alemany, M

    1993-11-01

    1. The applicability of current indirect calorimetry formulae to the study of energy and substrate balances on obese rats has been evaluated. The energy consumption of series of 60-day rats of Wistar, lean and obese Zucker stock were studied by means of direct and indirect calorimetry, and by establishing their energy balance through measurement of food intake and retention. Calorimetric studies encompassed a 24 h period, with gas and heat output measurements every 2 or 5 min, respectively, for direct and indirect calorimetry. 2. The analysis of fat composition (diet, whole rat, and synthesized and oxidized fat) showed only small variations that had only a limited effect on the overall energy equation parameters. 3. A gap in the nitrogen balance, which represents a urinary N excretion lower than the actual protein oxidized, resulted in significant deviations in the estimation of carbohydrate and lipid oxidized when using the equations currently available for indirect calorimetry. 4. Analysis of the amino acid composition of diet and rat protein as well as of the portion actually oxidized, and correcting for the nitrogen gap allowed the establishment of a set of equations that gave better coincidence of the calculated data with the measured substrate balance. 5. The measured heat output of all rats was lower than the estimated values calculated by means of either indirect calorimetry of direct energy balance measurement; the difference corresponded to the energy lost in water evaporation, and was in the range of one-fifth of total energy produced in the three rat stocks. 6. Wistar rats showed a biphasic circadian rhythm of substrate utilization, with alternate lipid synthesis/degradation that reversed that of carbohydrate, concordant with nocturnal feeding habits. Zucker rats did not show this rhythm; obese rats synthesized large amounts of fat during most of the light period, consuming fat at the end of the dark period, which suggests more diurnal feeding habits

  2. The mechanism of interactions between tea polyphenols and porcine pancreatic alpha-amylase: Analysis by inhibition kinetics, fluorescence quenching, differential scanning calorimetry and isothermal titration calorimetry.

    PubMed

    Sun, Lijun; Gidley, Michael J; Warren, Frederick J

    2017-10-01

    This study aims to use a combination of biochemical and biophysical methods to derive greater mechanistic understanding of the interactions between tea polyphenols and porcine pancreatic α-amylase (PPA). The interaction mechanism was studied through fluorescence quenching (FQ), differential scanning calorimetry (DSC) and isothermal titration calorimetry (ITC) and compared with inhibition kinetics. The results showed that a higher quenching effect of polyphenols corresponded to a stronger inhibitory activity against PPA. The red-shift of maximum emission wavelength of PPA bound with some polyphenols indicated a potential structural unfolding of PPA. This was also suggested by the decreased thermostability of PPA with these polyphenols in DSC thermograms. Through thermodynamic binding analysis of ITC and inhibition kinetics, the equilibrium of competitive inhibition was shown to result from the binding of particularly galloylated polyphenols with specific sites on PPA. There were positive linear correlations between the reciprocal of competitive inhibition constant (1/Kic ), quenching constant (KFQ ) and binding constant (Kitc ). The combination of inhibition kinetics, FQ, DSC and ITC can reasonably characterize the interactions between tea polyphenols and PPA. The galloyl moiety is an important group in catechins and theaflavins in terms of binding with and inhibiting the activity of PPA. © 2017 The Authors. Molecular Nutrition & Food Research Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Direct calorimetry: a brief historical review of its use in the study of human metabolism and thermoregulation.

    PubMed

    Kenny, Glen P; Notley, Sean R; Gagnon, Daniel

    2017-07-08

    Direct calorimetry is the gold standard means of measuring human metabolic rate and its use has been fundamental for understanding metabolism in health and disease. While metabolic rate is now more commonly estimated indirectly from measures of the oxygen consumed during respiration, direct calorimetry provides the user with the unique capacity to quantify the heat produced from aerobic and anaerobic metabolism by measuring heat exchange between the body and the environment. This review provides a brief historical overview of the fundamental concepts which underlie direct calorimetry, of pioneer scientists which developed these concepts into functional pieces of equipment and the subsequent use of direct calorimetry to advance our understanding of energy balance, nutrition, and the pathogenesis of metabolic diseases. Attention is directed to seminal studies that successfully employed direct calorimetry to verify that the law of energy conservation also applies to human beings and to establish the validity of indirect calorimetry. Finally, we discuss the more recent use of direct calorimetry for the measurement of whole-body heat exchange and body heat storage in the study of human thermoregulation.

  4. Laser Calorimetry Spectroscopy for ppm-level Dissolved Gas Detection and Analysis

    PubMed Central

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

    2017-01-01

    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

  5. Laser Calorimetry Spectroscopy for ppm-level Dissolved Gas Detection and Analysis

    NASA Astrophysics Data System (ADS)

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

    2017-02-01

    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.

  6. Inherent limitations of fixed-time, servo-controlled radiometric calorimetry

    SciTech Connect

    Wetzel, J.R.; Lemming, J.F.; Duff, M.F.

    1987-01-01

    Interest has been shown in using fixed-time, servo-controlled calorimetry to shorten the measurement times for certain samples that require low precision values (3 to 5%). This type of calorimeter measurement could be particularly useful for screening scrap samples to determine whether there is a need for a more accurate measurement or for certain confirmatory measurements for which low precision numbers are sufficient. The equipment required for this type of measurement is a servo-controlled calorimeter and a preconditioning unit. Samples to be measured are placed in the preconditioning unit, which is maintained at the internal temperature of the calorimeter. The power value for the sample is determined at a fixed time after loading into the calorimeter, for example, 30 min. When a calorimeter is operated using a fixed cutoff time, there are additional sources of uncertainty that need to be considered. The major factors affecting the uncertainty of the calorimetry power values are discussed. 2 refs., 4 figs.

  7. Laser Calorimetry Spectroscopy for ppm-level Dissolved Gas Detection and Analysis.

    PubMed

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

    2017-02-20

    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.

  8. Thermal characterization of starch-water system by photopyroelectric technique and adiabatic scanning calorimetry

    NASA Astrophysics Data System (ADS)

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

    2003-01-01

    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.

  9. Characterization of photomultiplier tubes in a novel operation mode for Secondary Emission Ionization Calorimetry

    NASA Astrophysics Data System (ADS)

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

    2016-10-01

    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.

  10. Determination of the catalytic activity of binuclear metallohydrolases using isothermal titration calorimetry.

    PubMed

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

    2014-03-01

    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.

  11. Thermal conformational changes of bovine fibrinogen by differential scanning calorimetry and circular dichroism.

    PubMed

    Chen, Y; Mao, H; Zhang, X; Gong, Y; Zhao, N

    1999-11-01

    The thermal denaturation of bovine fibrinogen has been investigated using differential scanning calorimetry (DSC) and circular dichroism (CD) spectroscopy. Differential scanning calorimetry measurements were carried out while changing the scan-rate. The transition at 57 degrees C was found to be irreversible and highly scan-rate dependent, suggesting that the denaturation is, at least in part, under kinetic control. The secondary structural changes at various temperatures were monitored by far-ultraviolet CD spectroscopy. These results show that the DSC transition for the thermal denaturation of bovine fibrinogen can be interpreted in terms of a kinetic process, N --> F, where k is a first-order kinetic constant that changes with temperature according to the Arrhenius equation. An important transition peak was observed at 78.8 degrees C which is attributed to the C-terminal parts of the Aalpha chains of fibrinogen.

  12. Nutrition Assessment With Indirect Calorimetry in Patients Evaluated for Left Ventricular Assist Device Implantation.

    PubMed

    Yost, Gardner; Gregory, Mary; Bhat, Geetha

    2015-10-01

    Malnutrition is known to negatively impact the clinical course of advanced heart failure and is associated with increased mortality following left ventricular assist device (LVAD) implantation. Appropriate assessment of nutrition requirements in these patients is critical in their clinical care, yet there has been little discussion on how to best determine resting energy expenditure (REE) in the hospital setting. We investigated the use of indirect calorimetry in a group of patients with advanced heart failure. Results from preoperative indirect calorimetry testing in 98 patients undergoing evaluation for LVAD candidacy were collected. REE was compared with 10 predictive equations that estimated caloric need based on a range of patient-specific demographic and clinical variables. This study enrolled 22 female and 76 male patients with a mean age of 59.4 ± 12.5 years, body mass index of 29.6 ± 6.0 kg/m(2), and ejection fraction of 19.4 ± 6.6%. The average REE by indirect calorimetry in this group was 1610.0 ± 612.7 kcal/d. All predictive equations significantly overestimated REE. However, those equations intended for use in the critically ill demonstrated the greatest accuracy, with the Brandi equation achieving both the highest correlation (r = 0.605, P < .001) and the lowest standard error of the estimate (504.8 kcal/d). Indirect calorimetry may be reliably and safely used to determine caloric requirements in patients with advanced heart failure. The use of predictive equations based on demographic and clinical parameters appears to generate inaccurate estimations of REE in these patients. However, equations designed for use in critically ill patients better estimate nutrition requirements than those designed for healthy individuals. © 2015 American Society for Parenteral and Enteral Nutrition.

  13. Absolute dosimetry on a dynamically scanned sample for synchrotron radiotherapy using graphite calorimetry and ionization chambers

    NASA Astrophysics Data System (ADS)

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

    2016-06-01

    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.

  14. VO2sim 0.1: Using Simulation to Understand Measurement Error in Indirect Calorimetry

    DTIC Science & Technology

    2015-08-01

    experimental VO2 measures (liters/minute) obtained at the same exercise workload are put into the function with the “cosmed_k4b2” indicated as the...calorimetry is commonly used in military research to examine the energetic cost of exercise during various perturbations and as a risk factor for injury...making. A common study design within the Army and in other exercise applications is a test-retest design. Failure to control for expected variability

  15. Differential scanning calorimetry investigations on Eu-doped fluorozirconate-based glass ceramics

    PubMed Central

    Paßlick, C.; Ahrens, B.; Henke, B.; Johnson, J. A.; Schweizer, S.

    2010-01-01

    The properties of Eu-doped fluorochlorozirconate (FCZ) glass ceramics upon thermal processing and the influence of Eu-doping on the formation of BaCl2 nanocrystals therein have been investigated. Differential scanning calorimetry indicates that higher Eu-doping shifts the crystallization peak of the nanocrystals in the glass to lower temperatures, while the glass transition temperature remains constant. The activation energy and the thermal stability parameters for the BaCl2 crystallization are determined. PMID:21286235

  16. Characterization of Polyamide 66 Obturator Materials by Differential Scanning Calorimetry and Size-Exclusion Chromatography

    DTIC Science & Technology

    2005-12-01

    Characterization of Polyamide 66 Obturator Materials by Differential Scanning Calorimetry and Size-Exclusion Chromatography 5c. PROGRAM ELEMENT NUMBER 5d...lamellar plane, resulting in a “ pleated ” crystallite. The second crystalline phase found in PA66, the β-phase, is also triclinic and characterized...Each solution was injected into the SEC instrument for analysis after filtration through a 0.45-µm syringe filter . Each solution was prepared

  17. Combined laser calorimetry and photothermal technique for absorption measurement of optical coatings

    SciTech Connect

    Li Bincheng; Blaschke, Holger; Ristau, Detlev

    2006-08-10

    To the best of our knowledge, a combined sensitive technique employing both laser calorimetry and a surface thermal lens scheme for measuring absorption values of optical coatings is presented for the first time. Laser calorimetric and pulsed surface thermal lens signals are simultaneously obtained with a highly reflecting UV coating sample irradiated at 193 nm. The advantages and potential applications of the combined technique and the experimental factors limiting the measurement sensitivity are discussed.

  18. Combined laser calorimetry and photothermal technique for absorption measurement of optical coatings.

    PubMed

    Li, Bincheng; Blaschke, Holger; Ristau, Detlev

    2006-08-10

    To the best of our knowledge, a combined sensitive technique employing both laser calorimetry and a surface thermal lens scheme for measuring absorption values of optical coatings is presented for the first time. Laser calorimetric and pulsed surface thermal lens signals are simultaneously obtained with a highly reflecting UV coating sample irradiated at 193 nm. The advantages and potential applications of the combined technique and the experimental factors limiting the measurement sensitivity are discussed.

  19. Absolute dosimetry on a dynamically scanned sample for synchrotron radiotherapy using graphite calorimetry and ionization chambers.

    PubMed

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

    2016-06-07

    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.

  20. Revisiting the streptavidin-biotin binding by using an aptamer and displacement isothermal calorimetry titration.

    PubMed

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

    2015-03-01

    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.

  1. The use of calorimetry in the biophysical characterization of small molecule alkaloids binding to RNA structures.

    PubMed

    Kumar, Gopinatha Suresh; Basu, Anirban

    2016-05-01

    RNA has now emerged as a potential target for therapeutic intervention. RNA targeted drug design requires detailed thermodynamic characterization that provides new insights into the interactions and this together with structural data, may be used in rational drug design. The use of calorimetry to characterize small molecule-RNA interactions has emerged as a reliable and sensitive tool after the recent advancements in biocalorimetry. This review summarizes the recent advancements in thermodynamic characterization of small molecules, particularly some natural alkaloids binding to various RNA structures. Thermodynamic characterization provides information that can supplement structural data leading to more effective drug development protocols. This review provides a concise report on the use of isothermal titration calorimetry (ITC) and differential scanning calorimetry (DSC) techniques in characterizing small molecules, mostly alkaloids-RNA interactions with particular reference to binding of tRNA, single stranded RNA, double stranded RNA, poly(A), triplex RNA. It is now apparent that a combination of structural and thermodynamic data is essential for rational design of specific RNA targeted drugs. Recent advancements in biocalorimetry instrumentation have led to detailed understanding of the thermodynamics of small molecules binding to various RNA structures paving the path for the development of many new natural and synthetic molecules as specific binders to various RNA structures. RNA targeted drug design, that remained unexplored, will immensely benefit from the calorimetric studies leading to the development of effective drugs for many diseases. Copyright © 2015 Elsevier B.V. All rights reserved.

  2. Graphite calorimetry for absorbed dose measurements in heavy-ion beams

    NASA Astrophysics Data System (ADS)

    Sakama, M.; Kanai, T.; Fukumura, A.

    In order to sophisticate the radiotherapy high accuracy knowledge of the absorbed dose delivered to the patient is essential The main methods of absolute dosimetry are indicated as follows a Dosimetry by ion chamber b Fricke dosimetry and c Calorimetry The calorimetry is most direct method of dosimetry due to direct measurement of energy deposit in principle and no requirement of information of radiation fields for the calibration Many countries tend to adopt the calorimetry to determine the standard absorbed dose to water and become to be capable of deciding the absorbed dose in precision of about 0 6 for photon and electron beams Despite the recent progress of particle therapy the parameters such as w-value and stopping power ratio for ionization chambers in the particles is not obtained accurately Therefore that causes uncertainty in determination of the absolute dose For this reason we developed a graphite calorimeter to obtain high precision absorbed dose and reduce the uncertainty for various beams When the absorbed dose of 1 Gy is irradiated to the sensitive volume the temperature rise is about 1 4 milliKelvins The performance require the resolution of plus or minus 7 micro Kelvins to measure it in precision of plus or minus 0 5 The stability within several micro Kelvins per minute is necessary to obtain measurable background The miniature glass bead thermistors were embedded in the sensitive volume to perform active control of temperature The resistance change of these thermistors is approximately 0 68 Ohms and 488 micro Ohms at

  3. Thermodynamics of biphasic lanthanide extraction by tripodal diglycolamide: a solution calorimetry study.

    PubMed

    Ansari, Seraj A; Mohapatra, Prasanta K; Verboom, Willem; Rao, Linfeng

    2016-11-01

    Isothermal titration calorimetry was employed for the direct measurement of the enthalpy of extraction (ΔHextr) of Eu(NO3)3 by using a tripodal diglycolamide (T-DGA) ligand dissolved in n-dodecane containing 5% (v/v) 2-decanol. The enthalpy of extraction obtained by titration calorimetry was in good agreement with the enthalpy of extraction calculated from the temperature dependence of the distribution coefficients by using the van't Hoff equation. The Gibbs free energy and the entropy of extraction (ΔGextr and ΔSextr) for the extraction of Eu(NO3)3 by T-DGA were also obtained by solvent extraction experiments. The complexation of Eu(3+) with T-DGA in a mixture of acetonitrile/nitric acid was also studied by spectrophotometry and calorimetry to determine the stability constants and the enthalpy of complexation (ΔHcomp) for the Eu(3+)/T-DGA complexes in a single phase. The enthalpy of complexation, though obtained in a solvent different from that in the solvent extraction, allows a rough estimate of the enthalpy of phase transfer of the Eu(3+)/T-DGA complexes from the aqueous phase to the organic phase.

  4. AC calorimetry of H2O at pressures up to 9 GPa in diamond anvil cells

    NASA Astrophysics Data System (ADS)

    Geballe, Zachary M.; Struzhkin, Viktor V.

    2017-06-01

    If successfully developed, calorimetry at tens of GPa of pressure could help characterize phase transitions in materials such as high-pressure minerals, metals, and molecular solids. Here, we extend alternating-current calorimetry to 9 GPa and 300 K in a diamond anvil cell and use it to study phase transitions in H2O. In particular, water is loaded into the sample chambers of diamond-cells, along with thin metal heaters (1 μm-thick platinum or 20 nm-thick gold on a glass substrate) that drive high-frequency temperature oscillations (20 Hz to 600 kHz; 1 to 10 K). The heaters also act as thermometers via the third-harmonic technique, yielding calorimetric data on (1) heat conduction to the diamonds and (2) heat transport into substrate and sample. Using this method during temperature cycles from 300 to 200 K, we document melting, freezing, and proton ordering and disordering transitions of H2O at 0 to 9 GPa, and characterize changes in thermal conductivity and heat capacity across these transitions. The technique and analysis pave the way for calorimetry experiments on any non-metal at pressures up to ˜100 GPa, provided a thin layer (several μm-thick) of thermal insulation supports a metallic thin-film (tens of nm thick) Joule-heater attached to low contact resistance leads inside the sample chamber of a diamond-cell.

  5. CALOR2012 XVth International Conference on Calorimetry in High Energy Physics

    SciTech Connect

    Akchurin, Nural .

    2015-05-04

    The International Conferences on Calorimetry in High Energy Physics, or the CALOR series, have always been where the calorimeter experts come together to review the state of calorimetry and bring forth new ideas every two years. The fteenth conference, CALOR2012, in Santa Fe was no exception. Although they were built roughly a decade ago, we are now witnessing the exceptional power of the LHC calorimeters and the crucial role they have been playing in the discovery of the 125 GeV Higgs-like boson. As we ruminate on the coming generation of experiments at the next (linear) collider and on the upgrades at the LHC, we are heartened by the substantial advances we made in calorimetry in the last decade. These advances will certainly help uncover new physics in the years to come, not only at colliders but also in astroparticle experiments that take advantage of natural elements such as air, water, and ice. The proceedings were published by the IOP in Journal of Physics, Vol 404 2011. The conference web site is calor2012.ttu.edu.

  6. Mathematical model of cycad cones' thermogenic temperature responses: inverse calorimetry to estimate metabolic heating rates.

    PubMed

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

    2012-12-21

    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.

  7. Percent relative cumulative frequency analysis in indirect calorimetry: application to studies of transgenic mice.

    PubMed

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

    2004-12-01

    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 < 0.0001) than in littermate controls. The gradual acclimation of mice to 12 degrees C caused a near-doubling of .VO2 in both UCP1-deficient and control mice. At this lower environmental temperature, there were no differences in .VO2 between groups. The latter is likely due to augmented shivering thermogenesis in UCP1-deficient mice compared with controls. With the increased availability of murine models of metabolic disease, indirect calorimetry is increasingly used, and the PRCF approach provides a novel and powerful means for data analysis.

  8. Calorimetry Exchange Program Quarterly Data Report, 4th Quarter CY91

    SciTech Connect

    McClelland, T.M.

    1996-07-01

    The goals of the Calorimetry Sample Exchange Program are: (1) Discuss measurement differences, (2) Review and improve analytical measurements and methods, (3) Discuss new measurement capabilities, (4) Provide data to DOE on measurement capabilities to evaluate shipper-receiver differences, (5) Provide characterized or standard materials as necessary for exchange participants, (6) 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 been collected to the same precision or for the same time periods. A meeting of the participants of the Calorimetry Exchange is held annually at EG&G Mound Applied Technologies. The purposes of this meeting are to discuss measurement differences, problems, and new measurement capabilities, and to determine the additional activities needed to fulfill the goals of the Exchange.

  9. Differential scanning calorimetry in life science: thermodynamics, stability, molecular recognition and application in drug design.

    PubMed

    Bruylants, G; Wouters, J; Michaux, C

    2005-01-01

    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.

  10. Reading and listening to music increase resting energy expenditure during an indirect calorimetry test.

    PubMed

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

    2014-12-01

    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 (P<0.0001); however, there was no difference in REE between the electronic device and magazine. Listening to self-selected relaxing music 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. Copyright © 2014 Academy of Nutrition and Dietetics. Published by Elsevier Inc. All rights reserved.

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

    PubMed Central

    Chiu, Michael H.; Prenner, Elmar J.

    2011-01-01

    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. PMID:21430954

  12. Using Isothermal Titration Calorimetry to Determine Thermodynamic Parameters of Protein–Glycosaminoglycan Interactions

    PubMed Central

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

    2015-01-01

    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. PMID:25325962

  13. Recommendations for improved data processing from expired gas analysis indirect calorimetry.

    PubMed

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

    2010-02-01

    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.

    PubMed

    Rao, Linfeng

    2007-06-01

    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. Study of the KNO3-Al2O3 system by differential scanning calorimetry

    NASA Astrophysics Data System (ADS)

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

    2016-09-01

    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.

  16. Energy storage capacity of reversible liquid phase Diels-Alder reactions as determined by drop calorimetry

    SciTech Connect

    Chung, C.P.

    1983-01-01

    Several Diels-Alder reactions were evaluated as possible candidates for energy storage. The goal was to use simple drop calorimetry to screen reactions and to identify those with high energy storage capacities. The dienes used were furan and substituted furans. The dienophiles used were maleic anhydride and substituted maleic anhydrides. Sixteen reactions have been examined. Three had energy storage capacities that were increased due to reaction (maleic anhydride and 2-methyl furan, maleic anhydride and 2-ethyl furan, maleic anhydride and 2,5-dimethyl furan). The remaining thirteen showed no increase in apparent heat capacity due to reaction.

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

    PubMed

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

    2008-10-01

    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).

  18. Resistive Micromegas for sampling calorimetry, a study of charge-up effects

    NASA Astrophysics Data System (ADS)

    Chefdeville, M.; Karyotakis, Y.; Geralis, T.; Titov, M.

    2016-07-01

    Micromegas, as a proportional and compact gaseous detector, is well suited for sampling calorimetry. The limitation of occasional sparking has now been lifted by means of resistive electrodes but at the cost of current-dependent charge-up effects. These effects are studied in this contribution, with an emphasis on gain variations during operation at high particle rate and under heavy ionisation. Results are reproduced by a simple model of charging-up which will be used for detector design optimisation in the future.

  19. Calorimetry of matrix-isolated sodium nitrite NaNO2

    NASA Astrophysics Data System (ADS)

    Egorov, V. M.; Markov, Yu. F.; Roginskii, E. M.; Stukova, E. V.

    2016-11-01

    Differential scanning calorimetry has been used to carry out a high-precision study of sodium nitrite NaNO2 incorporated into different silicate nanoporous matrices. Heat-capacity maxima due to smeared ferroelectric phase transitions have been discovered. Characteristics (intensity, half-width, phase-transition temperature, etc.) of the maxima have been investigated. Heat-capacity maxima related to an incommensurable phase transition have been reliably identified. The maxima can be attributed to the formation of appropriate orientation of sodium-nitrite nanocrystals in matrix pores.

  20. Glassy behavior of denatured DNA films studied by differential scanning calorimetry.

    PubMed

    Valle-Orero, Jessica; Garden, Jean-Luc; Richard, Jacques; Wildes, Andrew; Peyrard, Michel

    2012-04-12

    We use differential scanning calorimetry (DSC) to study the properties of DNA films, made of oriented fibers, heated above the thermal denaturation temperature of the double helical form. The films show glassy properties that we investigate in two series of experiments, a slow cooling at different rates followed by a DSC scan upon heating and aging at a temperature below the glass transition. Introducing the fictive temperature to characterize the glass allows us to derive quantitative information on the relaxations of the DNA films, in particular to evaluate their enthalpy barrier. A comparison with similar aging studies on PVAc highlights some specificities of the DNA samples.

  1. Water flow calorimetry measurements of heat loads for a volume production H/sup -/ source

    SciTech Connect

    Purgalis, P.; Ackerman, G.; Kwan, J.; Wells, R.P.

    1987-10-01

    The design of volume-production H/sup -/ sources requires the knowledge of heat loads on the source components. The arc and filament heater power input to a 20 cm diameter x 23 cm long source can be 50 kW or higher, practically all of which is absorbed in the cooling water. Water flow calorimetry measurements were made to determine the heat loads on the bucket walls, grid no. 1, and magnetic filter rods. The measurements are presented for two different filament locations, for three different values of arc power, and for three values of source gas pressure. 1 ref., 4 figs., 2 tabs.

  2. Using isothermal titration calorimetry to determine thermodynamic parameters of protein-glycosaminoglycan interactions.

    PubMed

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

    2015-01-01

    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.

  3. Kinetic analysis of gluconate phosphorylation by human gluconokinase using isothermal titration calorimetry.

    PubMed

    Rohatgi, Neha; Guðmundsson, Steinn; Rolfsson, Óttar

    2015-11-30

    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.

  4. Vitreous State Characterization of Pharmaceutical Compounds Degrading upon Melting by Using Fast Scanning Calorimetry.

    PubMed

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

    2015-06-04

    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.

  5. Calorimetry in superfluid He II to measure losses in superconducting magnets

    SciTech Connect

    Caspi, S.

    1982-04-01

    A method using calorimetry to measure magnet losses in pressurized Helium II is described. The isothermal nature of He II is used in measuring the overall heat capacity of the system and the net refrigeration power. During the measurements, the refrigeration power is held fixed, and the system (400 liters) temperature is near 1.92 K. The calorimetric measurement was calibrated against known power inputs between 1 and 20 W. This technique can even measure heat loads higher than the available refrigeration. Results of loss measurement on two dipole magnets are reported.

  6. Applications of isothermal titration calorimetry - the research and technical developments from 2011 to 2015.

    PubMed

    Falconer, Robert J

    2016-10-01

    Isothermal titration calorimetry is a widely used biophysical technique for studying the formation or dissociation of molecular complexes. Over the last 5 years, much work has been published on the interpretation of isothermal titration calorimetry (ITC) data for single binding and multiple binding sites. As over 80% of ITC papers are on macromolecules of biological origin, this interpretation is challenging. Some researchers have attempted to link the thermodynamics constants to events at the molecular level. This review highlights work carried out using binding sites characterized using x-ray crystallography techniques that allow speculation about individual bond formation and the displacement of individual water molecules during ligand binding and link these events to the thermodynamic constants for binding. The review also considers research conducted with synthetic binding partners where specific binding events like anion-π and π-π interactions were studied. The revival of assays that enable both thermodynamic and kinetic information to be collected from ITC data is highlighted. Lastly, published criticism of ITC research from a physical chemistry perspective is appraised and practical advice provided for researchers unfamiliar with thermodynamics and its interpretation. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

  7. Chip calorimetry for fast and reliable evaluation of bactericidal and bacteriostatic treatments of biofilms.

    PubMed

    Buchholz, F; Wolf, A; Lerchner, J; Mertens, F; Harms, H; Maskow, T

    2010-01-01

    Chip calorimetry is introduced as a new monitoring tool that provides real-time information about the physiological state of biofilms. Its potential for use for the study of the effects of antibiotics and other biocides was tested. Established Pseudomonas putida biofilms were exposed to substances known to cause toxicity by different mechanisms and to provoke different responses of defense and resistance. The effects of these compounds on heat production rates were monitored and compared with the effects of these compounds on the numbers of CFU and intracellular ATP contents. The real-time monitoring potential of chip calorimetry was successfully demonstrated by using as examples the fast-acting poisons formaldehyde and 2,4-dinitrophenol (DNP). A dosage of antibiotics initially increased the heat production rate. This was discussed as being the effect of energy-dependent resistance mechanisms (e.g., export and/or transformation of the antibiotic). The subsequent reduction in the heat production rate was attributed to the loss of activity and the death of the biofilm bacteria. The shapes of the death curves were in agreement with the assumed variation in the levels of exposure of cells within the multilayer biofilms. The new monitoring tool provides fast, quantitative, and mechanistic insights into the acute and chronic effects of a compound on biofilm activity while requiring only minute quantities of the biocide.

  8. Technical memo on PbF/sub 2/ as a Cherenkov radiator for EM calorimetry

    SciTech Connect

    Anderson, D.F.

    1989-06-26

    It is apparent that the ever increasing rates and radiation levels found in high-energy physics are excluding more and more instrumental techniques. Those techniques that are remaining are often pushed to their theoretical limits. This situation reaches an extreme at the proposed luminosity of the SSC. Also, it is fair to say that at the SSC, after the accelerator itself, calorimetry will be the next most important physics tool. Therefore, we should be ever alert to new calorimetry techniques which may operate in this demanding environment. The material lead fluoride, PbF/sub 2/, has a real potential of yielding a very compact, high-resolution electromagnetic calorimeter that is both fast and radiation hard. PbF/sub 2/ is not a scintillator but a Cherenkov radiator like lead glass, but with a radiation length even harder shorter than of BGO. This memo discusses this property as well as comparison PbF/sub 2/ to other scintillating materials. 2 refs., 14 figs., 1 tab.

  9. Heat of supersaturation-limited amyloid burst directly monitored by isothermal titration calorimetry

    PubMed Central

    Ikenoue, Tatsuya; Lee, Young-Ho; Kardos, József; Yagi, Hisashi; Ikegami, Takahisa; Naiki, Hironobu; Goto, Yuji

    2014-01-01

    Amyloid fibrils form in supersaturated solutions via a nucleation and growth mechanism. Although the structural features of amyloid fibrils have become increasingly clearer, knowledge on the thermodynamics of fibrillation is limited. Furthermore, protein aggregation is not a target of calorimetry, one of the most powerful approaches used to study proteins. Here, with β2-microglobulin, a protein responsible for dialysis-related amyloidosis, we show direct heat measurements of the formation of amyloid fibrils using isothermal titration calorimetry (ITC). The spontaneous fibrillation after a lag phase was accompanied by exothermic heat. The thermodynamic parameters of fibrillation obtained under various protein concentrations and temperatures were consistent with the main-chain dominated structural model of fibrils, in which overall packing was less than that of the native structures. We also characterized the thermodynamics of amorphous aggregation, enabling the comparison of protein folding, amyloid fibrillation, and amorphous aggregation. These results indicate that ITC will become a promising approach for clarifying comprehensively the thermodynamics of protein folding and misfolding. PMID:24753579

  10. Calorimetry, activity, and micro-FTIR analysis of CO chemisorption, titration, and oxidation on supported Pt

    NASA Technical Reports Server (NTRS)

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

    1990-01-01

    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.

  11. Kinetics of enzymatic high-solid hydrolysis of lignocellulosic biomass studied by calorimetry.

    PubMed

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

    2011-03-01

    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) but becomes proportional to enzyme dosage (excess of attack points) at later stages (>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.

  12. Recent developments for the analysis of data obtained from isothermal calorimetry.

    PubMed

    O'Neill, M A A

    2005-06-01

    Isothermal calorimetry is rapidly becoming an indispensable tool for the quantitative determination of a variety of kinetic and thermodynamic parameters for a wide range of systems. In particular calorimetry is finding increased application to the investigation of stability and incompatibility of pharmaceutical materials. In order to draw meaningful conclusions and to predict behaviour in related systems it is necessary to have the means to calculate accurately parameters such as the rate constant and enthalpy. To this end several groups have been developing equations which describe calorimetric output in these terms. This paper will briefly outline some of these equations and discuss some of the limitations that currently exist in their application. A particular emphasis is placed on the recent developments relating to the application of these equations to flow calorimetric data. The main application of these equations is usually found in the pharmaceutical industry. Pharmaceutical formulations are usually extremely complex mixtures consisting of many different excipients as well as the active drug. Because of these large numbers of ingredients it is often observed that multiple chemical and physical process occur over the lifetime of the study. This complexity is then reflected in the calorimetric data rendering the application of the simple equations useless. Dealing with this complexity is a major issue amongst the calorimetric community and some of the recent advances in this field are also discussed.

  13. Volume and expansivity changes of micelle formation measured by pressure perturbation calorimetry.

    PubMed

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

    2011-03-01

    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.

  14. Application of differential scanning calorimetry in evaluation of solid state interactions in tablets containing acetaminophen.

    PubMed

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

    2013-01-01

    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.

  15. Direct calorimetry of free-moving eels with manipulated thyroid status

    NASA Astrophysics Data System (ADS)

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

    2007-02-01

    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.

  16. Precipitation Kinetics in Solutionized Aluminum Alloy 2124: Determination by Scanning and Isothermal Calorimetry

    NASA Astrophysics Data System (ADS)

    Smith, George W.

    1998-03-01

    Kinetics and energetics of precipitation in solutionized aluminum alloy 2124 have been determined by differential scanning calorimetry (DSC) and differential isothermal calorimetry (DIC). DSC experiments at 7 temperature scan rates, analyzed by a Kissinger method, gave activation energies and rate constants. DIC experiments yielded time constants from a 2-exponential fit and a rate-averaging technique. It appears that the 2-exponential fit is applicable when two distinct processes contribute to precipitation, while the rate-averaged time constant is appropriate when one process is dominant. Activation energies and time constants from DSC and DIC agree well for both GP zone formation and precipitation. Kinetics results for GP zone dissolution were obtainable only from DSC experiments. DSC and DIC both indicate that, after GP zones have formed and dissolved, two processes are involved in precipitation, as DSC studies of Badini et al. showed for a comparable alloy (2024). The two precipitation mechanisms in alloy 2124 may involve formation of CuAl2 and CuMgAl2 phases. ΔQ, the heat evolved during GP zone formation and precipitation, was measured by DICover the temperature range 30 to 300 ^^oC. At the temperature of maximum GP zone formation rate ( 70 ^^oC) ΔQ ≈ -14.7 J/g; at the precipitation maximum ( 270 ^^oC) ΔQ ≈ -27.2 J/g.

  17. Interaction of gymnemic acid with cyclodextrins analyzed by isothermal titration calorimetry, NMR and dynamic light scattering.

    PubMed

    Izutani, Yusuke; Kanaori, Kenji; Imoto, Toshiaki; Oda, Masayuki

    2005-12-01

    The physiological phenomenon that the antisweet taste effect of gymnemic acid (GA) is diminished by application of gamma-cyclodextrin (gamma-CD) to the mouth was evaluated at the molecular level using isothermal titration calorimetry, NMR and dynamic light scattering. These analyses showed that GA specifically binds to gamma-CD. Thermodynamic analysis using isothermal titration calorimetry revealed that the association constant of GA and gamma-CD is 10(5)-10(6) m(-1) with favorable enthalpy and entropy changes. The heat capacity change was negative and large, despite the change in accessible surface area upon binding being small. These thermodynamics indicate that the binding is dominated by hydrophobic interactions, which is in agreement with inclusion complex formation of gamma-CD. In addition, NMR measurements showed that in solution the spectra of GA are broad and sharpened by the addition of gamma-CD, indicating that unbound GA is in a water-soluble aggregate that is dispersed when it forms a complex with gamma-CD. Dynamic light scattering showed that the average diameter of unbound GA is > 30 nm and that of GA and gamma-CD complex is 2.2 nm, similar to unbound gamma-CD, supporting the aggregate property of GA and the inclusion complexation of GA by gamma-CD.

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

    SciTech Connect

    Barnett, T.M.

    1993-12-31

    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. Thermal behavior and phase identification of Valsartan by standard and temperature-modulated differential scanning calorimetry.

    PubMed

    Skotnicki, Marcin; Gaweł, Agnieszka; Cebe, Peggy; Pyda, Marek

    2013-10-01

    Thermal behavior of angiotensin II type 1 (AT1) receptor antagonist, Valsartan (VAL), was examined employing thermogravimetric analysis (TGA), standard differential scanning calorimetry (DSC) and temperature-modulated differential scanning calorimetry (TMDSC). The stability of VAL was measured by TGA from 25 to 600°C. Decomposition of Valsartan starts around 160°C. The DSC curve shows two endotherms, occurring around 80°C and 100°C, related to evaporation of water and enthalpy relaxation, respectively. Valsartan was identified by DSC as an amorphous material and it was confirmed by X-ray powder diffraction. The glass transition of fresh Valsartan appears around 76°C (fictive temperature). TMDSC allows separation of the total heat flow rate into reversing and nonreversing parts. The nonreversing curve corresponds to the enthalpy relaxation and the reversing curve shows changes of heat capacity around 94°C. In the second run, TMDSC curve shows the glass transition process occurring at around 74°C. Results from standard DSC and TMDSC of Valsartan were compared over the whole range of temperature.

  20. Aggregation of bovine insulin probed by DSC/PPC calorimetry and FTIR spectroscopy.

    PubMed

    Dzwolak, Wojciech; Ravindra, Revanur; Lendermann, Julia; Winter, Roland

    2003-09-30

    Pressure perturbation calorimetry (PPC), differential scanning calorimetry (DSC), and time-resolved Fourier transform infrared spectroscopy (FTIR) have been employed to investigate aggregation of bovine insulin at pH 1.9. The aggregation process exhibits two distinguished phases. In the first phase, an intermediate molten globule-like conformational state is transiently formed, reflected by loose tertiary contacts and a robust H/D-exchange. This is followed by unfolding of the native secondary structure. The unfolding of insulin is fast, endothermic, partly reversible, and accompanied by a volume expansion of approximately 0.2%. The second phase consists of actual aggregation: an exothermic irreversible process revealing typical features of nucleation-controlled kinetics. The volumetric changes associated with the second phase are small. The concentration-dependence of DSC scans does not support a monomer intermediate model. While insulin aggregation under ambient pressure is fast and quantitative, pressure as low as 300 bar is sufficient to prevent the aggregation completely, as high-pressure FTIR spectroscopy revealed. This is explained in terms of the high pressure having an adverse effect on the thermal unfolding of insulin, and therefore preventing occurrence of the aggregation-prone intermediate. A comparison of the aggregation in H(2)O and D(2)O shows that the isotopic substitution has diverse effects on both the phases of aggregation. In heavy water, a more pronounced volume expansion accompanies the unfolding stage, while only the second phase shifts to higher temperature.

  1. A High-Throughput Biological Calorimetry Core: Steps to Startup, Run, and Maintain a Multiuser Facility.

    PubMed

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

    2016-01-01

    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.

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

    PubMed

    Pandharipande, Pranav P; Makhatadze, George I

    2015-04-01

    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. Chip calorimetry for evaluation of biofilm treatment with biocides, antibiotics, and biological agents.

    PubMed

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

    2014-01-01

    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)).

  4. Reference dosimetry for light-ion beams based on graphite calorimetry.

    PubMed

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

    2014-10-01

    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).

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

    SciTech Connect

    Lyons, J.E.

    1989-12-31

    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.

  6. Resistivity and AC calorimetry measurements on CeNiGe2 under pressure

    NASA Astrophysics Data System (ADS)

    Holmes, A. T.; Muramatsu, T.; Miyake, A.; Kaczorowski, D.; Bukowski, Z.; Kagayama, T.; Shimizu, K.

    2007-03-01

    We present resistivity and AC calorimetry measurements of single crystalline CeNiGe2 under high pressure and low temperature in a diamond anvil cell. CeNiGe2 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=3.9 K and T=3.2 K, which are suppressed under pressure. Between 0.7 and 1.4 GPa only a single transition was identified, with TN reaching 1.9 K by 1.4 GPa. At 1.9 GPa two transitions could again be seen by AC calorimetry at 2.0 and 1.3 K, accompanied by a qualitative change in the behaviour of the resistivity. The Sommerfeld coefficient showed a maximum of 755 mJ mol-1 K-2 at 1.4 GPa, up from 448 mJ mol-1 K-2 at close to ambient pressure. The residual resistivity was found to decrease sharply above 1.4 GPa after an initial increase with pressure.

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

    NASA Astrophysics Data System (ADS)

    Novotny, Rainer W.

    2015-02-01

    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 http://calor2014.de. 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

  8. Phase Polymorphism of [Co(DMSO)6](BF4)2 Studied by Differential Scanning Calorimetry

    NASA Astrophysics Data System (ADS)

    Migdał-Mikuli, Anna; Skoczylas, Łukasz; Szostak, Elżbieta

    2006-04-01

    Five solid phases of [Co(DMSO)6](BF4)2 have been detected by differential scanning calorimetry (DSC). Phase transitions were detected between the following solid phases: stable KIb↔ stable KIa at T̅C4 = (328±2) K, metastable KIII ↔ undercooled phase K0 at T̅C3 = (383±4) K, metastable KII ↔ undercooled K0 at T̅C2 = (399±2) K and stable KIa ↔ stable K0 at T̅C1 = (404±1) K. The title compound melts at Tm = 440 K. From the entropy changes at the melting point and at phase transitions it can be concluded that the phases K0 and undercooled K0 are orientationally dynamically disordered crystals. The stable phases KIa, KIb are ordered solid phases. The metastable phases KII and KIII are probably solid phases with a high degree of orientational dynamical disorder

  9. Direct Measurement of Glyconanoparticles and Lectin Interactions by Isothermal Titration Calorimetry

    PubMed Central

    Wang, Xin; Matei, Elena; Gronenborn, Angela M.; Ramström, Olof; Yan, Mingdi

    2012-01-01

    Glyconanomaterials have shown high potential in applications including bioanalysis and nanomedicine. Here, a quantitative analytical technique, based on isothermal titration calorimetry, was developed to characterize the interactions between glyconanoparticles and lectins. By titrating lectins into the glyconanoparticle solution, the apparent dissociation constant, thermodynamic parameters, and the number of binding sites were derived simultaneously. For the glyconanoparticles-lectin binding pairs investigated, a 3–5 orders of magnitude affinity enhancement over the free ligand-lectin interactions was observed which can be attributed to the multivalent ligand presentation on the nanoparticles. The impact of ligand density was also studied, and results showed that the affinity increased with the number of glycans on the nanoparticle. PMID:22548468

  10. Probing the thermodynamics of protein-lipid interactions by isothermal titration calorimetry.

    PubMed

    Swamy, Musti J; Sankhala, Rajeshwer S

    2013-01-01

    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.

  11. Van't Hoff global analyses of variable temperature isothermal titration calorimetry data.

    PubMed

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

    2012-01-10

    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.

  12. Direct measurement of glyconanoparticles and lectin interactions by isothermal titration calorimetry.

    PubMed

    Wang, Xin; Matei, Elena; Gronenborn, Angela M; Ramström, Olof; Yan, Mingdi

    2012-05-15

    Glyconanomaterials have shown high potential in applications including bioanalysis and nanomedicine. Here, a quantitative analytical technique, based on isothermal titration calorimetry, was developed to characterize the interactions between glyconanoparticles and lectins. By titrating lectins into the glyconanoparticle solution, the apparent dissociation constant, thermodynamic parameters, and the number of binding sites were derived simultaneously. For the glyconanoparticles-lectin binding pairs investigated, a 3-5 order of magnitude affinity enhancement over the free ligand-lectin interactions was observed which can be attributed to the multivalent ligand presentation on the nanoparticles. The impact of ligand density was also studied, and results showed that the affinity increased with the number of glycans on the nanoparticle.

  13. Probing the binding of (+)-catechin to bovine serum albumin by isothermal titration calorimetry and spectroscopic techniques

    NASA Astrophysics Data System (ADS)

    Li, Xiangrong; Hao, Yongbing

    2015-07-01

    In this study, the interaction between (+)-catechin and bovine serum albumin (BSA) was investigated using isothermal titration calorimetry (ITC), in combination with fluorescence spectroscopy, UV-vis absorption spectroscopy, and Fourier transform infrared (FT-IR) spectroscopy. Thermodynamic investigations reveal that the electrostatic interaction and hydrophobic interaction are the major binding forces in the binding of (+)-catechin to BSA. The binding of (+)-catechin to BSA is synergistically driven by enthalpy and entropy. Fluorescence experiments suggest that (+)-catechin can quench the fluorescence of BSA through a static quenching mechanism. The obtained binding constants and the equilibrium fraction of unbound (+)-catechin show that (+)-catechin can be stored and transported from the circulatory system to reach its target organ. Binding site I is found to be the primary binding site for (+)-catechin. Additionally, as shown by the UV-vis absorption, synchronous fluorescence spectroscopy and FT-IR, (+)-catechin may induce conformational and microenvironmental changes of BSA.

  14. Differential scanning calorimetry to investigate the compatibility of ciprofloxacin hydrochloride with excipients.

    PubMed

    Fathy, M; Hassan, M A; Mohamed, F A

    2002-12-01

    The compatibility between ciprofloxacin hydrochloride (CFX) and some excipients was evaluated using differential scanning calorimetry (DSC). Physical mixture, coground mixture, compressed mixture and kneaded mixture were prepared to study the effect of sample manipulation. In addition, the samples of physical mixture were also accelerated at 55 degrees C for three weeks to obtain more reliable conclusions. Different types of excipients currently used in tablet or capsule formulations namely, calcium phosphate dibasic dihydrate (Emcompress), magnesium stearate lactose, sorbitol, mannitol, croscarmellose sodium (Ac-Di-Sol), sodium carboxymethyl starch (Primojel), microcrystalline cellulose (Avicel PH 101, Emcocil) were examined. The DSC scan of CFX displayed two endothermic peaks probably as a result of a fusion process followed by a decomposition process. CFX appeared to interact with sorbitol, mannitol, Ac-Di-Sol, Primojel, Avicel PH 101 and Emcocil.

  15. Fast Scanning Calorimetry study of non-equilibrium relaxation in fragile organic liquids

    NASA Astrophysics Data System (ADS)

    Sadtchenko, Vlad; Bhattacharya, Deepanjan; O'Reilly, Liam

    2013-03-01

    Fast scanning calorimetry (FSC), capable of heating rates in excess of 1000000 K/s, was combined with vapor deposition technique to investigate non-equilibrium relaxation in micrometer thick viscous liquid films of several organic compounds (e.g.2-ethyl-1-hexanol, Toluene, and 1-propanol) under high vacuum conditions. Rapid heating of samples, vapor deposited at temperatures above their standard glass softening transition (Tg), resulted in observable endotherms which onset temperatures were strongly dependent on heating rate and the deposition temperature. Furthermore, all of the studied compounds were characterized by distinct critical deposition temperatures at which observation of endotherm became impossible. Based on the results of these studies, we have developed a simple model which makes it possible to infer the equilibrium enthalpy relaxation times for liquids from FSC data. We will discuss implications of these studies for contemporary models of non-equilibrium relaxation in glasses and supercooled liquids. Supported by NSF Grant 1012692.

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

    SciTech Connect

    Streza, M.; Dadarlat, D.; Strzałkowski, K.

    2013-11-13

    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.

  17. Binding of chrysoidine to catalase: spectroscopy, isothermal titration calorimetry and molecular docking studies.

    PubMed

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

    2013-11-05

    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. Copyright © 2013 Elsevier B.V. All rights reserved.

  18. Integration and global analysis of isothermal titration calorimetry data for studying macromolecular interactions.

    PubMed

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

    2016-05-01

    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.

  19. Differential scanning calorimetry study--assessing the influence of composition of vegetable oils on oxidation.

    PubMed

    Qi, Baokun; Zhang, Qiaozhi; Sui, Xiaonan; Wang, Zhongjiang; Li, Yang; Jiang, Lianzhou

    2016-03-01

    The thermal oxidation of eight different vegetable oils was studied using differential scanning calorimetry (DSC) under non-isothermal conditions at five different heating rates (5, 7.5, 10, 12.5, and 15°C/min), in a temperature range of 100-400°C. For all oils, the activation energy (Ea) values at Tp were smaller than that at Ts and Ton. Among all the oils, refined palm oil (RPO) exhibited the highest Ea values, 126.06kJ/mol at Ts, 134.7kJ/mol at Ton, and 91.88kJ/mol at Tp. The Ea and reaction rate constant (k) values at Ts, Ton, and Tp were further correlated with oil compositions (fatty acids and triacylglycerols) using Pearson correlation analysis. The rate constant (k) and Ea of all oils exhibited varying correlations with FAs and TAGs, indicating that the thermal oxidation behaviors were affected by oil compositions.

  20. A survey of the year 2002 literature on applications of isothermal titration calorimetry.

    PubMed

    Cliff, Matthew J; Ladbury, John E

    2003-01-01

    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.

  1. Differential scanning calorimetry of blood plasma for clinical diagnosis and monitoring.

    PubMed

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

    2009-06-01

    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.

  2. Applications of isothermal titration calorimetry in biophysical studies of G-quadruplexes.

    PubMed

    Pagano, Bruno; Mattia, Carlo Andrea; Giancola, Concetta

    2009-07-02

    G-quadruplexes are higher-order nucleic acids structures formed by G-rich sequences that are stabilized by tetrads of hydrogen-bonded guanine bases. Recently, there has been growing interest in the study of G-quadruplexes because of their possible involvement in many biological processes. Isothermal titration calorimetry (ITC) has been proven to be a useful tool to study the energetic aspects of G-quadruplex interactions. Particularly, ITC has been applied many times to determine the thermodynamic properties of drug-quadruplex interactions to screening among various drugs and to address drug design. In the present review, we will focus on the ITC studies of G-quadruplex structures and their interaction with proteins and drugs and the most significant results will be discussed.

  3. Characterization of latex-antineoplastic drug complexes by differential scanning calorimetry and microphotography.

    PubMed

    Gallardo, V; Ruiz, M A; Morales, E; Zouaki, J; Campos, J; Conejo-García, A; Gallo, M A; Espinosa, A

    2006-12-01

    Choline kinase inhibitors have recently been identified as potentially useful antitumoral agents. Here we determine the best conditions for obtaining drug-polymer complexes with 5-fluorouracil (5-FU), and JCR791B, a new drug representing a significant advance in the development of new molecules to inhibit tumour proliferation. As polymers we used the cellulose derivatives Aquacoat and Aquateric. The variables in the adsorption process measured were time to adsorbent-adsorbate equilibrium, pH and concentration. The drug-polymer complexes were characterized by differential scanning calorimetry and microphotography. Our results show that adsorption of 5-FU and JCR was similar with both polymers although slightly greater with Aquacoat. The chemical structure of the drug and its solubility in water and oil are fundamental characteristics that determine the performance of polymers as drug carriers able to provide controlled release.

  4. Influence of gamma radiation on potato starch gelatinization studied by differential scanning calorimetry

    NASA Astrophysics Data System (ADS)

    Cieśla, Krystyna; Eliasson, Ann-Charlotte

    2002-05-01

    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.

  5. Assessing hydration disturbances from concrete aggregates with radiation shielding properties by isothermal calorimetry

    NASA Astrophysics Data System (ADS)

    Wadsö, Lars; Cooper-Jensen, Carsten P.; Bentley, Phillip M.

    2017-04-01

    Spallation sources create a large amount of neutrons with energies up to the GeV range. To shield for these neutrons, steel and concrete are important materials. By adding different aggregates to normal concrete, one can improve the shielding effect of the concrete. Some of these aggregates can influence the rate of hydration (reaction) of the cement or even completely inhibit the hydration. It is thus good practice to start the investigation of new shielding concretes by assessing the rate of cement hydration in the presence of new aggregates. This is preferably made with isothermal (heat conduction) calorimetry. In this paper we describe such tests made with a large number of different potential aggregates for a shielding concrete. We found a full range of influence on the hydration, from no influence to severely disturbed. In some cases smaller particles gave more disturbance.

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

    SciTech Connect

    Coker, Eric Nicholas

    2013-10-01

    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.

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

    NASA Astrophysics Data System (ADS)

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

    2016-08-01

    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.

  8. Characterization of Thermal Behavior of Epoxy Composites Reinforced with Curaua Fibers by Differential Scanning Calorimetry

    NASA Astrophysics Data System (ADS)

    Barcelos, Mariana A.; Ribeiro, Carolina Gomes D.; Ferreira, Jordana; Vieira, Janaina da S.; Margem, Frederico M.; Monteiro, Sergio N.

    Epoxy composites reinforced with natural lignocellulosic fibers have, in recent times, been gaining attention in engineering areas as lighter and cheaper alternatives for traditional composites such as the "fiberglass". The curaua fiber is the one strongest today being considered as reinforcement of composites for automobile interior parts. In fact, several studies are currently being dedicated to curaua fiber composites since physical and mechanical properties are required for practical uses. In this work, the thermal behavior of epoxy composites reinforced with up to 30 % in volume of curaua fibers was investigated by differential scanning calorimetry, DSC. The results showed endothermic and exothermic events associated with water release and possible molecular chain amorphous transformation. Comparison with similar composites permitted to propose mechanism that explains this DSC thermal behavior.

  9. The Frontier of Modern Calorimetry: Hardware Advances and Application in Particle Physics Analysis

    NASA Astrophysics Data System (ADS)

    Medvedeva, Tatiana

    While the last missing components of the SM puzzle seem to be successfully found, particle physicists remain hungry for what might be there, beyond the cosy boundaries of the well studies elementary particle world. However, the sophisticated technique of data analysis and acute Monte Carlo simulations remain fruitless. It appears that the successful intrusion into the realm, in which we were not welcome so far, may require a very different implication of effort. All those results might suggest, though banal, that we need an improvement on the hardware side. Indeed, the hadronic calorimeter of CMS is no competitor to its other state-of-art components. This obstacle in many cases significantly complicates the flow of the physics analysis. Besides, the era of high luminosity LHC operation in the offing is calling for the same. After exploration of the analysis debri with 8TeV collision data, we investigate various approaches for better calorimetry for the CMS detector.

  10. Theoretical studies of hadronic calorimetry for high luminosity, high energy colliders

    SciTech Connect

    Brau, J.E.; Gabriel, T.A.

    1989-01-01

    Experiments at the high luminosity, high energy colliders of the future are going to demand optimization of the state of the art of calorimetry design and construction. During the past few years, the understanding of the basic phenomenology of hadron calorimeters has advanced through paralleled theoretical and experimental investigations. The important underlying processes are reviewed to set the framework for the presentation of recent calculations of the expected performance of silicon detector based hadron calorimeters. Such devices employing uranium are expected to achieve the compensation condition (that is, e/h approx. 1.0) based on the understanding that has been derived from the uranium-liquid argon and uranium-plastic scintillator systems. In fact, even lead-silicon calorimeters are found to achieve the attractive value for the e/h ratio of 1.16 at 10 GeV. 62 refs., 22 figs., 3 tabs.

  11. THE HYDROLYSIS AND OXIDATION BEHAVIOR OF LITHIUM BOROHYDRIDE AND MAGNESIUM HYDRIDE DETERMINED BY CALORIMETRY

    SciTech Connect

    Brinkman, K; Donald Anton, D; Joshua Gray, J; Bruce Hardy, B

    2008-03-13

    Lithium borohydride, magnesium hydride and the 2:1 'destabilized' ball milled mixtures (2LiBH{sub 4}:MgH{sub 2}) underwent liquid phase hydrolysis, gas phase hydrolysis and air oxidation reactions monitored by isothermal calorimetry. The experimentally determined heats of reaction and resulting products were compared with those theoretically predicted using thermodynamic databases. Results showed a discrepancy between the predicted and observed hydrolysis and oxidation products due to both kinetic limitations and to the significant amorphous character of observed reaction products. Gas phase and liquid phase hydrolysis were the dominant reactions in 2LiBH{sub 4}:MgH{sub 2} with approximately the same total energy release and reaction products; liquid phase hydrolysis displayed the maximum heat flow for likely environmental exposure with a peak energy release of 6 (mW/mg).

  12. Electron beam water calorimetry measurements to obtain beam quality conversion factors.

    PubMed

    Muir, Bryan R; Cojocaru, Claudiu D; McEwen, Malcolm R; Ross, Carl K

    2017-07-08

    To provide results of water calorimetry and ion chamber measurements in high-energy electron beams carried out at the National Research Council Canada (NRC). There are three main aspects to this work: (a) investigation of the behavior of ionization chambers in electron beams of different energies with focus on long-term stability, (b) water calorimetry measurements to determine absorbed dose to water in high-energy beams for direct calibration of ion chambers, and (c) using measurements of chamber response relative to reference ion chambers, determination of beam quality conversion factors, kQ , for several ion chamber types. Measurements are made in electron beams with energies between 8 MeV and 22 MeV from the NRC Elekta Precise clinical linear accelerator. Ion chamber measurements are made as a function of depth for cylindrical and plane-parallel ion chambers over a period of five years to investigate the stability of ion chamber response and for indirect calibration. Water calorimetry measurements are made in 18 MeV and 22 MeV beams. An insulated enclosure with fine temperature control is used to maintain a constant temperature (drifts less than 0.1 mK/min) of the calorimeter phantom at 4°C to minimize effects from convection. Two vessels of different designs are used with calibrated thermistor probes to measure radiation induced temperature rise. The vessels are filled with high-purity water and saturated with H2 or N2 gas to minimize the effect of radiochemical reactions on the measured temperature rise. A set of secondary standard ion chambers are calibrated directly against the calorimeter. Finally, several other ion chambers are calibrated in the NRC (60) Co reference field and then cross-calibrated against the secondary standard chambers in electron beams to realize kQ factors. The long-term stability of the cylindrical ion chambers in electron beams is better (always <0.15%) than plane-parallel chambers (0.2% to 0.4%). Calorimetry measurements made

  13. Fragility of supercooled liquids from differential scanning calorimetry traces: theory and experiment.

    PubMed

    Fivez, J; Longuemart, S; Glorieux, C

    2012-01-28

    Starting from the Debye model for frequency-dependent specific heat and the Vogel-Fulcher-Tammann (VFT) model for its relaxation time, an analytic expression is presented for the heat capacity versus temperature trace for differential scanning calorimetry (DSC) of glass transitions, suggesting a novel definition of the glass transition temperature based on a dimensionless criterion. An explicit expression is presented for the transition temperature as a function of the VFT parameters and the cooling rate, and for the slope as a function of fragility. Also a generalization of the results to non-VFT and non-Debye relaxation is given. Two unique ways are proposed to tackle the inverse problem, i.e., to extract the fragility from an experimental DSC trace. Good agreement is found between theoretically predicted DSC traces and experimental DSC traces for glycerol for different cooling rates.

  14. Fragility of supercooled liquids from differential scanning calorimetry traces: Theory and experiment

    NASA Astrophysics Data System (ADS)

    Fivez, J.; Longuemart, S.; Glorieux, C.

    2012-01-01

    Starting from the Debye model for frequency-dependent specific heat and the Vogel-Fulcher-Tammann (VFT) model for its relaxation time, an analytic expression is presented for the heat capacity versus temperature trace for differential scanning calorimetry (DSC) of glass transitions, suggesting a novel definition of the glass transition temperature based on a dimensionless criterion. An explicit expression is presented for the transition temperature as a function of the VFT parameters and the cooling rate, and for the slope as a function of fragility. Also a generalization of the results to non-VFT and non-Debye relaxation is given. Two unique ways are proposed to tackle the inverse problem, i.e., to extract the fragility from an experimental DSC trace. Good agreement is found between theoretically predicted DSC traces and experimental DSC traces for glycerol for different cooling rates.

  15. Calorimetry as a tool for understanding biomolecular interactions and an aid to drug design.

    PubMed

    Ladbury, John E

    2010-08-01

    The binding of two biomolecules viewed from the atomic level is highly complex. It involves the formation or removal of many individual non-covalent bonds both between the interacting molecules as well as with solvent. Currently, our understanding of the thermodynamic quantification of biomolecular interactions is somewhat naïve. ITC (isothermal titration calorimetry) provides a rapid route to a full thermodynamic characterization of a biomolecular interaction. Armed with these data, what are we really able to understand about complex formation and can any of this information provide a useful tool to aid drug development? Correlations between thermodynamic data and structural detail have been investigated, allowing insight into ways in which these can be used to understand protein-ligand interactions and provide input into the decision-making process in drug development.

  16. Online particle detection with Neural Networks based on topological calorimetry information

    NASA Astrophysics Data System (ADS)

    Ciodaro, T.; Deva, D.; de Seixas, J. M.; Damazio, D.

    2012-06-01

    This paper presents the latest results from the Ringer algorithm, which is based on artificial neural networks for the electron identification at the online filtering system of the ATLAS particle detector, in the context of the LHC experiment at CERN. The algorithm performs topological feature extraction using the ATLAS calorimetry information (energy measurements). The extracted information is presented to a neural network classifier. Studies showed that the Ringer algorithm achieves high detection efficiency, while keeping the false alarm rate low. Optimizations, guided by detailed analysis, reduced the algorithm execution time by 59%. Also, the total memory necessary to store the Ringer algorithm information represents less than 6.2 percent of the total filtering system amount.

  17. Exploring the binding mechanism of phosphoramidate derivative with DNA: Spectroscopy, calorimetry and modeling

    NASA Astrophysics Data System (ADS)

    Wang, Gongke; Wu, Hongwei; Wang, Dongchao; Yan, Changling; Lu, Yan

    2013-03-01

    In this study, one of the amino phosphine ester derivatives α-(3-hydroxy-4-methoxyphenyl)-N-phenyl-α-aminophosphonate (HMPAP) was synthesized, and the molecular interaction of HMPAP with ct-DNA has been investigated by UV-Vis absorption spectra, fluorescence spectra, isothermal titration calorimetry (ITC) and molecular modeling. The binding constant (Kb) of HMPAP to ct-DNA at different temperatures were calculated from fluorescence spectra. According to the UV-Vis absorption spectra, ethidium bromide displacement studies and ITC experimental results, we can conclude that HMPAP is an intercalator. The molecular modeling results indicated that HMPAP can slide into the G-C rich region of ct-DNA. ITC data showed that ct-DNA/HMPAP binding is enthalpy controlled. Furthermore, the results obtained from molecular modeling corroborated the experimental results obtanied from spectroscopic and ITC investigations.

  18. Conformation and stability properties of B17: II. Analytical investigations using differential scanning calorimetry.

    PubMed

    Khachfe, Hassan M; Atkinson, David

    2013-04-01

    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.

  19. What can we get from varying scan rate in protein differential scanning calorimetry?

    PubMed

    Amani, Mojtaba; Moosavi-Movahedi, Ali A; Kurganov, Boris I

    2017-06-01

    Differential scanning calorimetry has many advantages over other techniques to study the thermal stability of proteins due to its direct measurement of thermodynamic parameters. Most proteins undergo irreversible thermal denaturation causing their thermogram to be scan rate dependent. We modeled reversible and irreversible protein thermograms at varying scan rates. The complete Lumry-Eyring model was used to model the irreversible thermograms at various values of T1/2 (temperature at which equilibrium constant equals unity) and T* (temperature at which rate constant equals 1min(-1)). Our results have shown that the thermal effects of two processes are integrated with decreasing the T* relative to T1/2. It is also shown that the shape of second derivatives of thermograms under different conditions have specific pattern which can be used to judge and estimate the correct model for protein denaturation. Copyright © 2017 Elsevier B.V. All rights reserved.

  20. Amphiphilic naproxen prodrugs: differential scanning calorimetry study on their interaction with phospholipid bilayers.

    PubMed

    Giuffrida, Maria Chiara; Pignatello, Rosario; Castelli, Francesco; Sarpietro, Maria Grazia

    2017-09-01

    Naproxen, a nonsteroid anti-inflammatory drug studied for Alzheimer's disease, was conjugated with lipoamino acids (LAA) directly or through a diethylamine (EDA) spacer to improve the drug lipophilicity and the interaction with phospholipid bilayers. The interaction of naproxen and its prodrugs with biomembrane models consisting of dimyristoylphosphatidylcholine multilamellar vesicles was studied by differential scanning calorimetry. The transfer of prodrugs from a lipophilic carrier to a biomembrane model was also studied. Naproxen conjugation to lipoamino acids improves its interaction with biomembrane models and affects the transfer from a lipophilic carrier to biomembrane model. LAA portion may localize between the phospholipid chains; the entity of the interaction depends not only on the presence of the spacer but also on the LAA chain length. Variation of LAA portion can modulate the naproxen prodrugs affinity towards the biological membrane as well as towards the lipophilic carrier. © 2017 Royal Pharmaceutical Society.

  1. Resolving glass transition in Te-based phase-change materials by modulated differential scanning calorimetry

    NASA Astrophysics Data System (ADS)

    Chen, Yimin; Mu, Sen; Wang, Guoxiang; Shen, Xiang; Wang, Junqiang; Dai, Shixun; Xu, Tiefeng; Nie, Qiuhua; Wang, Rongping

    2017-10-01

    Glass transitions of Te-based phase-change materials (PCMs) were studied by modulated differential scanning calorimetry. It was found that both Ge2Sb2Te5 and GeTe are marginal glass formers with ΔT (= T x ‑ T g) less than 2.1 °C when the heating rate is below 3 °C min‑1. The fragilities of Ge2Sb2Te5 and GeTe can be estimated as 46.0 and 39.7, respectively, around the glass transition temperature, implying that a fragile-to-strong transition would be presented in such Te-based PCMs. The above results provide direct experimental evidence to support the investigation of crystallization kinetics in supercooled liquid PCMs.

  2. Laboratory Annealing Experiments Of Refractory Silicate Grain Analogs Using Differential Scanning Calorimetry

    NASA Technical Reports Server (NTRS)

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

    2010-01-01

    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.

  3. Study of Polymer Glasses by Modulated Differential Scanning Calorimetry in the Undergraduate Physical Chemistry Laboratory

    NASA Astrophysics Data System (ADS)

    Folmer, J. C. W.; Franzen, Stefan

    2003-07-01

    Recent technological advances in thermal analysis present educational opportunities. In particular, modulated differential scanning calorimetry (MDSC) can be used to contrast reversing and nonreversing processes in practical laboratory experiments. The introduction of these concepts elucidates the relationship between experimental timescales and reversibility. The latter is a key concept of undergraduate thermodynamics theory that deserves reinforcement. In this paper, the theory and application of MDSC to problems of current interest is outlined with special emphasis on the contrast between crystallization and vitrification. Glass formation deserves greater emphasis in the undergraduate curriculum. Glass transitions are increasingly recognized as an important aspect of materials properties and dynamics in fields ranging from polymer science to protein folding. The example chosen for study is a comparison of polyethylene glycol and atactic polypropylene glycol. The experiment is easily performed in a typical three-hour lab session.

  4. Stability of some Cactaceae proteins based on fluorescence, circular dichroism, and differential scanning calorimetry measurements.

    PubMed

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

    1999-02-01

    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.

  5. Kinetic analysis of nonisothermal differential scanning calorimetry of 1,3-dipalmitoyl-2-oleoylglycerol.

    PubMed

    Smith, Kevin W; Cain, Fred W; Talbot, Geoff

    2005-04-20

    The crystallization of fats has been extensively studied because of its importance in the processing of food and food ingredients. Differential scanning calorimetry (DSC) is widely used in such studies. The aim of this study was to examine the determination of kinetic parameters from nonisothermal DSC crystallization of a model fat, 1,3-dipalmitoyl-2-oleoylglycerol. We applied peak and isoconversional methods to determine activation energies and compared these techniques with a nonparametric method, which separates the temperature dependence and degree of crystallization dependence of the crystallization rate. The Johnson-Mehl-Avrami-Erofeyev-Kolmogorov (JMAEK) model provided the best fit to the data, while the temperature dependence of the rate constant was best explained by a Vogel-Fulcher relationship, where the reference temperature was the melting point of the crystallizing species.

  6. Determination of the solubility of crystalline low molar mass compounds in polymers by differential scanning calorimetry.

    PubMed

    Rager, Timo

    2014-06-01

    A mathematical equation has been derived to calculate the liquidus for a binary system consisting of an amorphous polymer and a crystalline low molar mass compound. The experimental input to this equation is an interaction enthalpy, which is derived from the variation of the melting enthalpy with composition in differential scanning calorimetry (DSC) experiments. The predictive power of the equation has been tested with mixtures of acetylsalicylic acid, carbamazepine, or intraconazole with poly(ethylene glycol) as well as mixtures of carbamazepine with poly(acrylic acid), poly(hydroxystyrene), or poly(vinylpyrrolidone). It has been confirmed that the evaluation of the melting enthalpy in DSC is a suitable method to identify the preferred solute-polymer combinations for thermodynamically stable molecular dispersions.

  7. Use of Differential Scanning Calorimetry (DSC) in the Characterization of EPDM/PP Blends

    NASA Astrophysics Data System (ADS)

    Stelescu, Maria Daniela; Airinei, Anton; Grigoras, Cristian; Niculescu-Aron, Ileana-Gabriela

    2010-12-01

    New polyolefinic thermoplastic elastomers based on the ethylene-propylene-diene monomer (EPDM) and polypropylene (PP) containing an EPDM elastomer of the last generation (Nordel NDR 47130), obtained by polymerization in the gaseous phase with metallocene catalysis, were prepared and characterized. The melting and crystallization behavior of these blends was investigated by differential scanning calorimetry. It is observed that the melting temperature, crystallization temperature, and crystallinity degree increase with an increase of PP loading. The influence of the blend composition on the physico-mechanical characteristics was discussed using statistical processing of the experimental data. Two compatibilizing procedures were utilized to improve the physico-mechanical characteristics of the samples: an addition method using different compatibilizing agents and dynamical vulcanization with three types of crosslinking systems. Significant improvements of the tensile strength and tear strength were noted by dynamic crosslinking, and the best results were obtained using a crosslinking system based on phenolic resin and tin chloride.

  8. Laser induced absorption at 355nm in silica studied by calorimetry and photothermal deflection

    SciTech Connect

    Dijon, J.; Van Oost, E.; Pelle, C.; Lyan, P.

    1996-12-31

    Laser calorimetry is used to measure low losses of optical samples on the third harmonic of a YAG laser. During the experiments, degradation of bare SiO2 substrate was observed. This degradation consists of an absorption increasing with the laser pulse number. The observed evolution depends on the kind of silica tested and particularly on the OH content of the material. The observed evolution required both changes in the electron content of the existing traps and the creation of new traps or color centers. Using an Argon laser at 351 nm, relaxation of YAG induced absorption was observed. This point enables an evolution mechanism to be proposed related to charge modification of the existing traps and to a multiphoton absorption process during the YAG irradiation.

  9. Measurement of protein stability and protein denaturation in cells using differential scanning calorimetry.

    PubMed

    Lepock, James R

    2005-02-01

    Many methods exist for measuring and studying protein denaturation in vitro. However, measuring protein denaturation in cells under conditions relevant to heat shock presents problems due to cellular complexity and high levels of light scattering that interfere with optical techniques. A general method for measuring protein denaturation in cells using high sensitivity differential scanning calorimetry (DSC) is given. Profiles of specific heat (c(p) vs. temperature) are obtained providing information about transitions in cellular components including the denaturation of proteins. The specific approaches employed with erythrocytes, bacteria, and mammalian cells are described, and an identification of several features of the DSC profiles is given. Protein denaturation on the level of roughly 7-20% occurs for commonly used heat shocks in mammalian cells.

  10. Laboratory Annealing Experiments Of Refractory Silicate Grain Analogs Using Differential Scanning Calorimetry

    NASA Technical Reports Server (NTRS)

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

    2010-01-01

    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.

  11. Thermodynamic signature of secondary nano-emulsion formation by isothermal titration calorimetry.

    PubMed

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

    2014-12-09

    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.

  12. A unified framework based on the binding polynomial for characterizing biological systems by isothermal titration calorimetry.

    PubMed

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

    2015-04-01

    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.

  13. Dual-Readout Calorimetry for High-Quality Energy Measurements. Final Report

    SciTech Connect

    Wigmans, Richard; Nural, Akchurin

    2013-09-01

    This document constitutes the final report on the project Dual-Readout Calorimetry for High-Quality Energy Measurements. The project was carried out by a consortium of US and Italian physicists, led by Dr. Richard Wigmans (Texas tech University). This consortium built several particle detectors and tested these at the European Center for Nuclear Research (CERN) in Geneva, Switzerland. The idea arose to use scintillating crystals as dual-readout calorimeters. Such crystals were of course already known to provide excellent energy resolution for the detection of particles developing electromagnetic (em) showers. The efforts to separate the signals from scintillating crystals into scintillation and Cerenkov components led to four different methods by which this could be accomplished. These methods are based on a) the directionality, b) spectral differences, c) the time structure, and d) the polarization of the signals.

  14. The complexity of condensed tannin binding to bovine serum albumin--An isothermal titration calorimetry study.

    PubMed

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

    2016-01-01

    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.

  15. Kinetics of trypsin-catalyzed hydrolysis determined by isothermal titration calorimetry.

    PubMed

    Maximova, Ksenia; Trylska, Joanna

    2015-10-01

    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.

  16. Substrate binding properties of potato tuber ADP-glucose pyrophosphorylase as determined by isothermal titration calorimetry.

    PubMed

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

    2015-06-04

    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.

  17. Applications of high pressure differential scanning calorimetry to aviation fuel thermal stability research

    NASA Technical Reports Server (NTRS)

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

    1985-01-01

    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.

  18. Differential scanning calorimetry study of deoxyadenosine and its water of hydration

    NASA Astrophysics Data System (ADS)

    Cooper, R. L.; Lee, S. A.

    2002-03-01

    Elucidating the interactions between the hydration of water and DNA is important for understanding the function of DNA. Differential scanning calorimetry (DSC) has been used to measure the activation energy and enthalpy associated with the removal of this water from the nucleoside deoxyadenosine (dA). Pristine samples were found to contain water of crystallization since the samples were prepared from solution by evaporation. Following an initial dehydration, it is necessary to expose the dA to a relative humidity above 84 percent in order to rehydrate the sample. For such rehydrated samples, the DSC measurements yield 1.60 ± 0.20 eV/H_20 and 175 ± 80 J/g for the activation energy and enthalpy, respectively. These energies remain the same for all higher relative humidities. We provide a simple model of this rehydration process.

  19. FLUKA studies of hadron-irradiated scintillating crystals for calorimetry at the High-Luminosity LHC

    NASA Astrophysics Data System (ADS)

    Quittnat, Milena; CMS Collaboration

    2015-02-01

    Calorimetry at the High-Luminosity LHC (HL-LHC) will be performed in a harsh radiation environment with high hadron fluences. The upgraded CMS electromagnetic calorimeter design and suitable scintillating materials are a focus of current research. In this paper, first results using the Monte Carlo simulation program FLUKA are compared to measurements performed with proton-irradiated LYSO, YSO and cerium fluoride crystals. Based on these results, an extrapolation to the behavior of an electromagnetic sampling calorimeter, using one of the inorganic scintillators above as an active medium, is performed for the upgraded CMS experiment at the HL-LHC. Characteristic parameters such as the induced ambient dose, fluence spectra for different particle types and the residual nuclei are studied, and the suitability of these materials for a future calorimeter is surveyed. Particular attention is given to the creation of isotopes in an LYSO-tungsten calorimeter that might contribute a prohibitive background to the measured signal.

  20. Energy expenditure in children predicted from heart rate and activity calibrated against respiration calorimetry.

    PubMed

    Treuth, M S; Adolph, A L; Butte, N F

    1998-07-01

    The purpose of this study was to predict energy expenditure (EE) from heart rate (HR) and activity calibrated against 24-h respiration calorimetry in 20 children. HR, oxygen consumption (VO2), carbon dioxide production (VCO2), and EE were measured during rest, sleep, exercise, and over 24 h by room respiration calorimetry on two separate occasions. Activity was monitored by a leg vibration sensor. The calibration day (day 1) consisted of specified behaviors categorized as inactive (lying, sitting, standing) or active (two bicycle sessions). On the validation day (day 2), the child selected activities. Separate regression equations for VO2, VCO2, and EE for method 1 (combining awake and asleep using HR, HR2, and HR3), method 2 (separating awake and asleep), and method 3 (separating awake into active and inactive, and combining activity and HR) were developed using the calibration data. For day 1, the errors were similar for 24-h VO2, VCO2, and EE among methods and also among HR, HR2, and HR3. The methods were validated using measured data from day 2. There were no significant differences in HR, VO2, VCO2, respiratory quotient, and EE values during rest, sleep, or over the 24 h between days 1 and 2. Applying the linear HR equations to day 2 data, the errors were the lowest with the combined HR/activity method (-2.6 +/- 5.2%, -4.1 +/- 5.9%, -2.9 +/- 5.1% for VO2, VCO2, and EE, respectively). To demonstrate the utility of the HR/activity method, HR and activity were monitored for 24 h at home (day 3). Free-living EE was predicted as 7,410 +/- 1,326 kJ/day. In conclusion, the combination of HR and activity is an acceptable method for determining EE not only for groups of children, but for individuals.

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

    PubMed

    Aliasgharzadeh, Soghra; Mahdavi, Reza; Asghari Jafarabadi, Mohammad; Namazi, Nazli

    2015-06-01

    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 component in the development of nutrition support therapy, therefore we determined the accuracy of commonly used predictive equations against RMR measured by indirect calorimetry among healthy young underweight females. This cross-sectional study was conducted on 104 underweight females aged 18-30 years old with body mass index (BMI) <18.5 kg/m(2) in 2013. After collecting anthropometric data, body composition was measured by bioelectric 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. The mean BMI of subjects was 17.3±1.3 kg/m(2). 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 estimated 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. 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.

  2. Supramolecular interactions between β-lapachone with cyclodextrins studied using isothermal titration calorimetry and molecular modeling.

    PubMed

    Xavier-Junior, Francisco H; Rabello, Marcelo M; Hernandes, Marcelo Z; Dias, Marília E S; Andrada, Otoni H M S; Bezerra, Beatriz P; Ayala, Alejandro P; Santos-Magalhães, Nereide S

    2017-11-01

    Supramolecular interactions between β-lapachone (β-lap) and cyclodextrins (CDs) were investigated by isothermal titration calorimetry. The most favorable host: guest interaction was characterized using X-ray powder diffraction (XRD), differential scanning calorimetry and thermogravimetry (DSC/TG), spectroscopy (FT-IR), spectroscopy (2D ROESY) nuclear magnetic resonance (NMR), and molecular modeling. Phase solubility diagrams showed β-, HP-β-, SBE-β-, γ-, and HP-γ-CDs at 1.5% (w/w) allowed an increase in apparent solubility of β-lap with enhancement factors of 12.0, 10.1, 11.8, 2.4, and 2.2, respectively. β-lap has a weak interaction with γ- and HP-γ-CDs and tends to interact more favorably with β-CD and its derivatives, especially SBE-β-CD (K = 4160 M(-1) ; ΔG = -20.66 kJ·mol(-1) ). Thermodynamic analysis suggests a hydrophobic interaction associated with the displacement of water from the cavity of the CD by the β-lap. In addition, van der Waals forces and hydrogen bonds were responsible for the formation of complexes. Taken together, the results showed intermolecular interactions between β-lap and SBE-β-CD, thereby confirming the formation of the inclusion complex. Molecular docking results showed 2 main orientations in which the interaction of benzene moiety at the wider rim of the SBE-β-CD is the most stable (average docking energy of -7.0 kcal/mol). In conclusion, β-lap:SBE-β-CD is proposed as an approach for use in drug delivery systems in cancer research. Copyright © 2017 John Wiley & Sons, Ltd.

  3. Irreversible Denaturation of Maltodextrin Glucosidase Studied by Differential Scanning Calorimetry, Circular Dichroism, and Turbidity Measurements

    PubMed Central

    Goyal, Megha; Chaudhuri, Tapan K.; Kuwajima, Kunihiro

    2014-01-01

    Thermal denaturation of Escherichia coli maltodextrin glucosidase was studied by differential scanning calorimetry, circular dichroism (230 nm), and UV-absorption measurements (340 nm), which were respectively used to monitor heat absorption, conformational unfolding, and the production of solution turbidity. The denaturation was irreversible, and the thermal transition recorded at scan rates of 0.5–1.5 K/min was significantly scan-rate dependent, indicating that the thermal denaturation was kinetically controlled. The absence of a protein-concentration effect on the thermal transition indicated that the denaturation was rate-limited by a mono-molecular process. From the analysis of the calorimetric thermograms, a one-step irreversible model well represented the thermal denaturation of the protein. The calorimetrically observed thermal transitions showed excellent coincidence with the turbidity transitions monitored by UV-absorption as well as with the unfolding transitions monitored by circular dichroism. The thermal denaturation of the protein was thus rate-limited by conformational unfolding, which was followed by a rapid irreversible formation of aggregates that produced the solution turbidity. It is thus important to note that the absence of the protein-concentration effect on the irreversible thermal denaturation does not necessarily means the absence of protein aggregation itself. The turbidity measurements together with differential scanning calorimetry in the irreversible thermal denaturation of the protein provided a very effective approach for understanding the mechanisms of the irreversible denaturation. The Arrhenius-equation parameters obtained from analysis of the thermal denaturation were compared with those of other proteins that have been reported to show the one-step irreversible thermal denaturation. Maltodextrin glucosidase had sufficiently high kinetic stability with a half-life of 68 days at a physiological temperature (37°C). PMID

  4. Irreversible denaturation of maltodextrin glucosidase studied by differential scanning calorimetry, circular dichroism, and turbidity measurements.

    PubMed

    Goyal, Megha; Chaudhuri, Tapan K; Kuwajima, Kunihiro

    2014-01-01

    Thermal denaturation of Escherichia coli maltodextrin glucosidase was studied by differential scanning calorimetry, circular dichroism (230 nm), and UV-absorption measurements (340 nm), which were respectively used to monitor heat absorption, conformational unfolding, and the production of solution turbidity. The denaturation was irreversible, and the thermal transition recorded at scan rates of 0.5-1.5 K/min was significantly scan-rate dependent, indicating that the thermal denaturation was kinetically controlled. The absence of a protein-concentration effect on the thermal transition indicated that the denaturation was rate-limited by a mono-molecular process. From the analysis of the calorimetric thermograms, a one-step irreversible model well represented the thermal denaturation of the protein. The calorimetrically observed thermal transitions showed excellent coincidence with the turbidity transitions monitored by UV-absorption as well as with the unfolding transitions monitored by circular dichroism. The thermal denaturation of the protein was thus rate-limited by conformational unfolding, which was followed by a rapid irreversible formation of aggregates that produced the solution turbidity. It is thus important to note that the absence of the protein-concentration effect on the irreversible thermal denaturation does not necessarily means the absence of protein aggregation itself. The turbidity measurements together with differential scanning calorimetry in the irreversible thermal denaturation of the protein provided a very effective approach for understanding the mechanisms of the irreversible denaturation. The Arrhenius-equation parameters obtained from analysis of the thermal denaturation were compared with those of other proteins that have been reported to show the one-step irreversible thermal denaturation. Maltodextrin glucosidase had sufficiently high kinetic stability with a half-life of 68 days at a physiological temperature (37°C).

  5. Fluence correction factor for graphite calorimetry in a clinical high-energy carbon-ion beam

    NASA Astrophysics Data System (ADS)

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

    2017-04-01

    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.

  6. Efficient Isothermal Titration Calorimetry Technique Identifies Direct Interaction of Small Molecule Inhibitors with the Target Protein.

    PubMed

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

    2016-01-01

    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.

  7. Effects of energy supplementation on energy losses and nitrogen balance of steers fed green-chopped wheat pasture I. Calorimetry

    USDA-ARS?s Scientific Manuscript database

    Providing an energy supplement to cattle grazing high-quality wheat pasture can increase average daily gain; however the effects on greenhouse gas emissions are not known. Therefore we used 10 British cross-bred steers (initial weight: 206 ± 10.7 kg) in a respiration calorimetry study to evaluate t...

  8. Thermodynamic characteristics of the acid-base equilibria of taurine in aqueous solutions, according to calorimetry data

    NASA Astrophysics Data System (ADS)

    Gridchin, S. N.; Shekhanov, R. F.; Pyreu, D. F.

    2015-02-01

    Enthalpies of the neutralization and protonation of taurine (HL) are measured by direct calorimetry at 298.15 K and ionic strengths of 0.3, 0.5, and 1.0 (KNO3). The standard thermodynamic characteristics of HL protolytic equilibria are calculated.

  9. Kinetic properties of two Rhizopus exo-polygalacturonase enzymes hydrolyzing galacturonic acid oligomers using isothermal titration calorimetry

    USDA-ARS?s Scientific Manuscript database

    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...

  10. Validation and recovery rates of an indirect calorimetry headbox system used to measure heat production of cattle

    USDA-ARS?s Scientific Manuscript database

    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...

  11. On the accuracy of instantaneous gas exchange rates, energy expenditure, and respiratory quotient calculations obtained in indirect whole room calorimetry

    USDA-ARS?s Scientific Manuscript database

    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...

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

    USDA-ARS?s Scientific Manuscript database

    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...

  13. Evaluation of three flame retardant (FR) grey cotton blend nonwoven fabrics using micro-scale combustion calorimetry

    USDA-ARS?s Scientific Manuscript database

    Unbleached (grey or greige) cotton nonwoven (NW) fabrics (with 12.5% polypropylene scrim) were treated with three phosphate-nitrogen based FR formulations and evaluated with micro-scale combustion calorimetry (MCC). Heat release rate (HRR), Peak heat rate (PHRR), temperature at peak heat release ra...

  14. HEAT OF HYDRATION OF SALTSTONE MIXES-MEASUREMENT BY ISOTHERMAL CALORIMETRY

    SciTech Connect

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

    2007-07-02

    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 reactions) after seven

  15. Prevalence of Underprescription or Overprescription of Energy Needs in Critically Ill Mechanically Ventilated Adults as Determined by Indirect Calorimetry: A Systematic Literature Review.

    PubMed

    Tatucu-Babet, Oana A; Ridley, Emma J; Tierney, Audrey C

    2016-02-01

    Underfeeding and overfeeding has been associated with adverse patient outcomes. Resting energy expenditure can be measured using indirect calorimetry. In its absence, predictive equations are used. A systematic literature review was conducted to determine the prevalence of underprescription and overprescription of energy needs in adult mechanically ventilated critically ill patients by comparing predictive equations to indirect calorimetry measurements. Ovid MEDLINE, CINAHL Plus, Scopus, and EMBASE databases were searched in May 2013 to identify studies that used both predictive equations and indirect calorimetry to determine energy expenditure. Reference lists of included publications were also searched. The number of predictive equations that underestimated or overestimated energy expenditure by ±10% when compared to indirect calorimetry measurements were noted at both an individual and group level. In total, 2349 publications were retrieved, with 18 studies included. Of the 160 variations of 13 predictive equations reviewed at a group level, 38% underestimated and 12% overestimated energy expenditure by more than 10%. The remaining 50% of equations estimated energy expenditure to within ±10 of indirect calorimetry measurements. On an individual patient level, predictive equations underestimated and overestimated energy expenditure in 13-90% and 0-88% of patients, respectively. Differences of up to 43% below and 66% above indirect calorimetry values were observed. Large discrepancies exist between predictive equation estimates and indirect calorimetry measurements in individuals and groups. Further research is needed to determine the influence of indirect calorimetry and predictive equation limitations in contributing to these observed differences. © 2015 American Society for Parenteral and Enteral Nutrition.

  16. Evaluation of Staphylococcus aureus DNA aptamer by enzyme-linked aptamer assay and isothermal titration calorimetry.

    PubMed

    Bayraç, Ceren; Öktem, Hüseyin Avni

    2017-02-01

    To monitor the specificity of Staphylococcus aureus aptamer (SA-31) against its target cell, we used enzyme-linked aptamer assay. In the presence of target cell, horseradish peroxidase-conjugated streptavidin bound to biotin-labeled SA-31 showed specific binding to S  aureus among 3 different bacteria with limit of detection of 10(3) colony-forming unit per milliliter. The apparent Ka was 1.39 μM(-1)  ± 0.3 μM(-1) . The binding of SA-31 to membrane proteins extracted from cell surface was characterized using isothermal titration calorimetry, and the effect of changes in binding temperature and salt concentrations of binding buffer was evaluated based on thermodynamic parameters (Ka , ΔH, and ΔG). Since binding of aptamer to its targets solely depends on its 3-dimensional structure under experimental conditions used in selection process, the change in temperature and ion concentration changed the affinity of SA-31 to its target on surface of bacteria. At 4°C, SA-31 did not show an affinity to its target with poor heat change upon injection of membrane fraction to aptamer solution. However, the apparent association constants of SA-31 slightly varied from Ka  = 1.56 μM(-1)  ± 0.69 μM(-1) at 25°C to Ka  = 1.03 μM(-1)  ± 0.9 μM(-1) at 37°C. At spontaneously occurring exothermic binding reactions, affinities of S aureus aptamer to its target were also 9.44 μM(-1)  ± 0.38 μM(-1) at 50mM, 1.60 μM(-1)  ± 0.11 μM(-1) at 137mM, and 3.28 μM(-1)  ± 0.46 μM(-1) at 200 mM of salt concentration. In this study, it was demonstrated that enzyme-linked aptamer assay and isothermal titration calorimetry were useful tools for studying the fundamental binding mechanism between a DNA aptamer and its target on the outer surface of S aureus.

  17. Phase Polymorphism of [Mn(DMSO)6](BF4)2 Studied by Differential Scanning Calorimetry

    NASA Astrophysics Data System (ADS)

    Migdał-Mikuli, Anna; Skoczylas, Łukasz

    2008-12-01

    The tetrafluoroborate of hexadimethylsulfoxidemanganese(II) was synthesized and studied by differential scanning calorimetry. Five solid phases of [Mn(DMSO)6](BF4)2 were revealed. Specifically, four phase transitions of the first order were detected between the following solid phases: stable KIb↔stable KIa at TC4 = 215 K; metastable KIII↔overcooled K0 at TC3 = 354 K; metastable KII↔overcooled K0 at TC2 =377 K; stable KIa→stable K0 at TC1 =385 K. [Mn(DMSO)6](BF4)2 starts to decompose at 400 K with a loss of one DMSO molecule per formula unit and forms [Mn(DMSO)5](BF4)2 which next decomposes in one step to MnF2 at the temperature range of 460 - 583 K. From the entropy changes it can be concluded that the phases K0 and metastable KII are orientationally dynamically disordered (ODDIC) crystals. The stable phases KIb and KIa are ordered solid phases.

  18. Deconvolution of complex differential scanning calorimetry profiles for protein transitions under kinetic control.

    PubMed

    Toledo-Núñez, Citlali; Vera-Robles, L Iraís; Arroyo-Maya, Izlia J; Hernández-Arana, Andrés

    2016-09-15

    A frequent outcome in differential scanning calorimetry (DSC) experiments carried out with large proteins is the irreversibility of the observed endothermic effects. In these cases, DSC profiles are analyzed according to methods developed for temperature-induced denaturation transitions occurring under kinetic control. In the one-step irreversible model (native → denatured) the characteristics of the observed single-peaked endotherm depend on the denaturation enthalpy and the temperature dependence of the reaction rate constant, k. Several procedures have been devised to obtain the parameters that determine the variation of k with temperature. Here, we have elaborated on one of these procedures in order to analyze more complex DSC profiles. Synthetic data for a heat capacity curve were generated according to a model with two sequential reactions; the temperature dependence of each of the two rate constants involved was determined, according to the Eyring's equation, by two fixed parameters. It was then shown that our deconvolution procedure, by making use of heat capacity data alone, permits to extract the parameter values that were initially used. Finally, experimental DSC traces showing two and three maxima were analyzed and reproduced with relative success according to two- and four-step sequential models.

  19. Simultaneous Differential Scanning Calorimetry and Thermogravimetric Analysis of Portland Cement as a Function of Age

    NASA Astrophysics Data System (ADS)

    Trník, Anton; Scheinherrová, Lenka; Kulovaná, Tereza; Černý, Robert

    2016-01-01

    We study the hydration and pozzolanic reactions of an ordinary Portland cement as a function of age, using the differential scanning calorimetry and thermogravimetry. The measurements are done for 2 days, 7 days, 28 days, 90 days, 180 days, and 360 days cured samples in order to monitor the rate of hydration. The investigation is performed in the temperature range from 25° C to 1000° C with a heating rate 5° C {\\cdot} min^{-1} in an argon atmosphere. The temperature, enthalpy, and mass change during the decomposition of calcium silicate hydrate gels, ettringite, portlandite, vaterite, and calcite are determined, and the changes in the portlandite amount are estimated in dependence on the time of hydration. We found out that the temperature and enthalpy of liberation of physically bound water, C-S-H gels and ettringite decomposition (all occurring from 50° C to 250° C) and Portlandite decomposition (420° C to 530° C) decrease with hydration time of studied samples. On the other hand, vaterite and calcite decomposition (530° C to 850° C) the temperature varies and the enthalpy increases with hydration time of samples.

  20. Immersion calorimetry of fine coal particles and its relation to flotation

    SciTech Connect

    Melkus, T.G.; Chiang, S.H.; Wen, W.W.

    1987-01-01

    A Setaram C-80 heat flux microcalorimeter was used to study the surface and interfacial properties of fine coal particles in water containing flotation agents via heat of immersion measurements. Heat of immersion (..delta..H/sub imm/) is usually a small exothermic quantity and can be used to characterize a solid in terms of its relative hydrophobicity or hydrophilicity. The effects of coal type, surface oxidation, mineral matter content, kerosene concentration, and pH on the wetting characteristics were investigated. Although coal is a heterogeneous mixture of organic and inorganic materials, immersional calorimetry has proven to be quite helpful in measuring surface properties of coal, and the following conclusions can be drawn: The heat of immersion decreased with increasing kerosene concentration, which corresponds to the coal particles increasing hydrophobicity; in varying the pH, the ..delta..H/sub imm/ went through a minimum at a pH value of 6.5 to 7.0, which coincides with the reported optimum pH range for flotation; both oxidation and clay slime coating (addition of kaolin), which are known to make the coal less hydrophobic, increased the ..delta..H/sub imm/; and the trends that were shown to exist in the heat of immersion measurements (for varying kerosene concentration, pH oxidation, and clay slime coating) correlated well with independent flotation experiments. 16 refs., 6 figs., 2 tabs.

  1. Thermal stability of Phaseolus vulgaris leucoagglutinin: a differential scanning calorimetry study.

    PubMed

    Biswas, Shyamasri; Kayastha, Arvind M

    2002-09-30

    Phaseolus vulgaris phytohemagglutinin L is a homotetrameric-leucoagglutinating seed lectin. Its three-dimensional structure shows similarity with other members of the legume lectin family. The tetrameric form of this lectin is pH dependent. Gel filtration results showed that the protein exists in its dimeric state at pH 2.5 and as a tetramer at pH 7.2. Contrary to earlier reports on legume lectins that possess canonical dimers, thermal denaturation studies show that the refolding of phytohemagglutinin L at neutral pH is irreversible. Differential scanning calorimetry (DSC) was used to study the denaturation of this lectin as a function of pH that ranged from 2.0 to 3.0. The lectin was found to be extremely thermostable with a transition temperature around 82 degrees C and above 100 degrees C at pH 2.5 and 7.2, respectively. The ratio of calorimetric to vant Hoff enthalpy could not be calculated because of its irreversible-folding behavior. However, from the DSC data, it was discovered that the protein remains in its compact-folded state, even at pH 2.3, with the onset of denaturation occurring at 60 degrees C.

  2. Isothermal calorimetry: impact of measurements error on heat of reaction and kinetic calculations.

    PubMed

    Papadaki, Maria; Nawada, Hosadu P; Gao, Jun; Fergusson-Rees, Andrew; Smith, Michael

    2007-04-11

    Heat flow and power compensation calorimetry measures the power generation of a reaction via an energy balance over an appropriately designed isothermal reactor. However, the measurement of the power generated by a reaction is a relative measurement, and calibrations are used to eliminate the contribution of a number of unknown factors. In this work the effect of the error in the measurement of temperature of electric power used in the calibrations and the heat transfer coefficient and baseline is assessed. It has been shown that the error in all aforementioned quantities reflects on the baseline and it can have a very serious impact on the accuracy of the measurement. The influence of the fluctuation of ambient temperature has been evaluated and a means of a correction that reduces its impact has been implemented. The temperature of dosed material is affected by the heat loses if reaction is performed at high temperature and low dosing rate. An experimental methodology is presented that can provide means of assessment of the actual temperature of the dosed material. Depending on the reacting system, the heat of evaporation could be included in the baseline, especially if non-condensable gases are produced during the course of the reaction.

  3. Assessment of fluidity of different invasomes by electron spin resonance and differential scanning calorimetry.

    PubMed

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

    2011-06-30

    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.

  4. A survey of the year 2006 literature on applications of isothermal titration calorimetry.

    PubMed

    Okhrimenko, Oksana; Jelesarov, Ilian

    2008-01-01

    Isothermal titration calorimetry (ITC) is a fast and robust method to determine the energetics of association reactions in solution. The changes in enthalpy, entropy and heat capacity that accompany binding provide unique insights into the balance of forces driving association of molecular entities. ITC is used nowadays on a day-to-day basis in hundreds of laboratories. The method aids projects both in basic and practice-oriented research ranging from medicine and biochemistry to physical chemistry and material sciences. Not surprisingly, the range of studies utilizing ITC data is steadily expanding. In this review, we discuss selected results and ideas that have accumulated in the course of the year 2006, the focus being on biologically relevant systems. Theoretical developments, novel applications and studies that provide a deeper level of understanding of the energetic principles of biological function are primarily considered. Following the appearance of a new generation of titration calorimeters, recent papers provide instructive examples of the synergy between energetic and structural approaches in biomedical and biotechnological research.

  5. A survey of the year 2007 literature on applications of isothermal titration calorimetry.

    PubMed

    Bjelić, Sasa; Jelesarov, Ilian

    2008-01-01

    Elucidation of the energetic principles of binding affinity and specificity is a central task in many branches of current sciences: biology, medicine, pharmacology, chemistry, material sciences, etc. In biomedical research, integral approaches combining structural information with in-solution biophysical data have proved to be a powerful way toward understanding the physical basis of vital cellular phenomena. Isothermal titration calorimetry (ITC) is a valuable experimental tool facilitating quantification of the thermodynamic parameters that characterize recognition processes involving biomacromolecules. The method provides access to all relevant thermodynamic information by performing a few experiments. In particular, ITC experiments allow to by-pass tedious and (rarely precise) procedures aimed at determining the changes in enthalpy and entropy upon binding by van't Hoff analysis. Notwithstanding limitations, ITC has now the reputation of being the "gold standard" and ITC data are widely used to validate theoretical predictions of thermodynamic parameters, as well as to benchmark the results of novel binding assays. In this paper, we discuss several publications from 2007 reporting ITC results. The focus is on applications in biologically oriented fields. We do not intend a comprehensive coverage of all newly accumulated information. Rather, we emphasize work which has captured our attention with originality and far-reaching analysis, or else has provided ideas for expanding the potential of the method. Copyright (c) 2008 John Wiley & Sons, Ltd.

  6. Interaction of human serum albumin with short polyelectrolytes: a study by calorimetry and computer simulations.

    PubMed

    Yu, Shun; Xu, Xiao; Yigit, Cemil; van der Giet, Markus; Zidek, Walter; Jankowski, Joachim; Dzubiella, Joachim; Ballauff, Matthias

    2015-06-21

    We present a comprehensive study of the interaction of human serum albumin (HSA) with poly(acrylic acid) (PAA; number average degree of polymerization: 25) in aqueous solution. The interaction of HSA with PAA is studied in dilute solution as a function of the concentration of added salt (20-100 mM) and temperature (25-37 °C). Isothermal titration calorimetry (ITC) is used to analyze the interaction and to determine the binding constant and related thermodynamic data. It is found that only one PAA chain is bound per HSA molecule. The free energy of binding ΔGb increases with temperature significantly. ΔGb decreases with increasing salt concentration and is dominated by entropic contributions due to the release of bound counterions. Coarse-grained Langevin computer simulations treating the counterions in an explicit manner are used to study the process of binding in detail. These simulations demonstrate that the PAA chains are bound in the Sudlow II site of HSA. Moreover, ΔGb is calculated from the simulations and found to be in very good agreement with the measured data. The simulations demonstrate clearly that the driving force of binding is the release of counterions in full agreement with the ITC-data.

  7. Reversible Melting of UHMMPE and PE Extended-chain Crystals Detected by Temperature-modulated Calorimetry

    NASA Astrophysics Data System (ADS)

    Pak, Jeongihm; Wunderlich, Bernhard

    2002-03-01

    The melting and crystallization of gel-spun, ultrahigh molar mass polyethylene (UHMMPE) and polyethylene extended-chain crystals (ECC) are analyzed with both, standard differential scanning calorimetry (DSC) and a temperature-modulated DSC. For short-chain, flexible molecules up to 10 nm length, reversible melting was found last year, as expected for small molecules. Longer oligomers melted almost fully irreversibly. Medium to high molar mass polyethylene, in contrast, show again a small reversing and reversible component in the high-temperature melting region. It was proposed in the literature, that this effect in the polyethylene is solely caused by "fold-surface melting." To test this theory and to look for additional effects on the lateral surfaces, the new morphologies are quantitatively compared with the prior analyzed samples. The UHMMPE contains a mobile, oriented mesophase and few folded chains. The ECC has no chain folds and less than 2fraction. In both cases reversing melting and crystallization is observed. --- Supported by NSF, Polymers Program, DMR-9703692, and the Div. of Mat. Sci., BES, DOE at ORNL, managed by UT-Batelle, LLC, for the U.S. Department of Energy, under contract number DOE-AC05-00OR22725.

  8. Strategies for assessing proton linkage to bimolecular interactions by global analysis of isothermal titration calorimetry data.

    PubMed

    Coussens, Nathan P; Schuck, Peter; Zhao, Huaying

    2012-09-01

    Isothermal titration calorimetry (ITC) is a traditional and powerful method for studying the linkage of ligand binding to proton uptake or release. The theoretical framework has been developed for more than two decades and numerous applications have appeared. In the current work, we explored strategic aspects of experimental design. To this end, we simulated families of ITC data sets that embed different strategies with regard to the number of experiments, range of experimental pH, buffer ionization enthalpy, and temperature. We then re-analyzed the families of data sets in the context of global analysis, employing a proton linkage binding model implemented in the global data analysis platform SEDPHAT, and examined the information content of all data sets by a detailed statistical error analysis of the parameter estimates. In particular, we studied the impact of different assumptions about the knowledge of the exact concentrations of the components, which in practice presents an experimental limitation for many systems. For example, the uncertainty in concentration may reflect imperfectly known extinction coefficients and stock concentrations or may account for different extents of partial inactivation when working with proteins at different pH values. Our results show that the global analysis can yield reliable estimates of the thermodynamic parameters for intrinsic binding and protonation, and that in the context of the global analysis the exact molecular component concentrations may not be required. Additionally, a comparison of data from different experimental strategies illustrates the benefit of conducting experiments at a range of temperatures.

  9. Systematic differential scanning calorimetry studies of the cure of carbon fiber - epoxy composite prepregs

    SciTech Connect

    Walkup, C.M.; Morgan, R.J.; Hoheisel, T.H.

    1983-11-01

    High performance C fiber-epoxy composite laminates are fabricated from uncured C fiber-epoxy prepreg material. Diaminodiphenyl sulfone (DDS) cured tetraglycidyl 4,4' diaminodiphenyl methane (TGDDM) epoxies, whose cure reactions are accelerated by BF/sub 3/:amine catalysts, are the most common composite matrices utilized in these high performance composites. To process reproducible composites requires an understanding of the cure reactions and how these reactions are modified by the BF/sub 3/:amine catalysts. In this paper we report systematic differential scanning calorimetry (DSC) studies of the constituents of BF/sub 3/:NH/sub 2/C/sub 2/H/sub 5/ catalyzed TGDDM-DDS epoxies and their mixtures; the effect of BF/sub 3/:NH/sub 2/C/sub 2/H/sub 5/ concentration on the cure reactions; the nature of the catalyzed cure reactions and the environmental sensitivity of the catalyst. DSC studies are also reported on the cure reaction characteristics and environmental sensitivity of commercial C fiber-TGDDM-DDS epoxy prepregs.

  10. Lipoprotein lipase activity and interactions studied in human plasma by isothermal titration calorimetry.

    PubMed

    Reimund, Mart; Kovrov, Oleg; Olivecrona, Gunilla; Lookene, Aivar

    2017-01-01

    LPL hydrolyzes triglycerides in plasma lipoproteins. Due to the complex regulation mechanism, it has been difficult to mimic the physiological conditions under which LPL acts in vitro. We demonstrate that isothermal titration calorimetry (ITC), using human plasma as substrate, overcomes several limitations of previously used techniques. The high sensitivity of ITC allows continuous recording of the heat released during hydrolysis. Both initial rates and kinetics for complete hydrolysis of plasma lipids can be studied. The heat rate was shown to correspond to the release of fatty acids and was linearly related to the amount of added enzyme, either purified LPL or postheparin plasma. Addition of apoC-III reduced the initial rate of hydrolysis by LPL, but the inhibition became less prominent with time when the lipoproteins were triglyceride poor. Addition of angiopoietin-like protein (ANGPTL)3 or ANGPTL4 caused reduction of the activity of LPL via a two-step mechanism. We conclude that ITC can be used for quantitative measurements of LPL activity and interactions under in vivo-like conditions, for comparisons of the properties of plasma samples from patients and control subjects as substrates for LPL, as well as for testing of drug candidates developed with the aim to affect the LPL system. Copyright © 2017 by the American Society for Biochemistry and Molecular Biology, Inc.

  11. Binding of copper to lysozyme: Spectroscopic, isothermal titration calorimetry and molecular docking studies.

    PubMed

    Jing, Mingyang; Song, Wei; Liu, Rutao

    2016-07-05

    Although copper is essential to all living organisms, its potential toxicity to human health have aroused wide concerns. Previous studies have reported copper could alter physical properties of lysozyme. The direct binding of copper with lysozyme might induce the conformational and functional changes of lysozyme and then influence the body's resistance to bacterial attack. To better understand the potential toxicity and toxic mechanisms of copper, the interaction of copper with lysozyme was investigated by biophysical methods including multi-spectroscopic measurements, isothermal titration calorimetry (ITC), molecular docking study and enzyme activity assay. Multi-spectroscopic measurements proved that copper quenched the intrinsic fluorescence of lysozyme in a static process accompanied by complex formation and conformational changes. The ITC results indicated that the binding interaction was a spontaneous process with approximately three thermodynamical binding sites at 298K and the hydrophobic force is the predominant driven force. The enzyme activity was obviously inhibited by the addition of copper with catalytic residues Glu 35 and Asp 52 locating at the binding sites. This study helps to elucidate the molecular mechanism of the interaction between copper and lysozyme and provides reference for toxicological studies of copper. Copyright © 2016 Elsevier B.V. All rights reserved.

  12. Applications of pressure perturbation calorimetry to study factors contributing to the volume changes upon protein unfolding.

    PubMed

    Pandharipande, Pranav P; Makhatadze, George I

    2016-05-01

    Pressure perturbation calorimetry (PPC) is a biophysical method that allows direct determination of the volume changes upon conformational transitions in macromolecules. This review provides novel details of the use of PPC to analyze unfolding transitions in proteins. The emphasis is made on the data analysis as well as on the validation of different structural factors that define the volume changes upon unfolding. Four case studies are presented that show the application of these concepts to various protein systems. The major conclusions are: 1. Knowledge of the thermodynamic parameters for heat induced unfolding facilitates the analysis of the PPC profiles. 2. The changes in the thermal expansion coefficient upon unfolding appear to be temperature dependent.3.Substitutions on the protein surface have negligible effects on the volume changes upon protein unfolding. 4. Structural plasticity of proteins defines the position dependent effect of amino acid substitutions of the residues buried in the native state. 5. Small proteins have positive volume changes upon unfolding which suggests difference in balance between the cavity/void volume in the native state and the hydration volume changes upon unfolding as compared to the large proteins that have negative volume changes. The information provided here gives a better understanding and deeper insight into the role played by various factors in defining the volume changes upon protein unfolding. Copyright © 2015 Elsevier B.V. All rights reserved.

  13. A universal method for fishing target proteins from mixtures of biomolecules using isothermal titration calorimetry

    PubMed Central

    Zhou, Xingding; Sun, Qingxiang; Kini, R. Manjunatha; Sivaraman, J.

    2008-01-01

    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. PMID:18621915

  14. Real-Time Monitoring of Membrane-Protein Reconstitution by Isothermal Titration Calorimetry

    PubMed Central

    2013-01-01

    Phase diagrams offer a wealth of thermodynamic information on aqueous mixtures of bilayer-forming lipids and micelle-forming detergents, providing a straightforward means of monitoring and adjusting the supramolecular state of such systems. However, equilibrium phase diagrams are of very limited use for the reconstitution of membrane proteins because of the occurrence of irreversible, unproductive processes such as aggregation and precipitation that compete with productive reconstitution. Here, we exemplify this by dissecting the effects of the K+ channel KcsA on the process of bilayer self-assembly in a mixture of Escherichia coli polar lipid extract and the nonionic detergent octyl-β-d-glucopyranoside. Even at starting concentrations in the low micromolar range, KcsA has a tremendous impact on the supramolecular organization of the system, shifting the critical lipid/detergent ratios at the onset and completion of vesicle formation by more than 2-fold. Thus, equilibrium phase diagrams obtained for protein-free lipid/detergent mixtures would be misleading when used to guide the reconstitution process. To address this issue, we demonstrate that, even under such nonequilibrium conditions, high-sensitivity isothermal titration calorimetry can be exploited to monitor the progress of membrane-protein reconstitution in real time, in a noninvasive manner, and at high resolution to yield functional proteoliposomes with a narrow size distribution for further downstream applications. PMID:24354292

  15. Determination of kinetics and heat of hydrolysis for non-homogenous substrate by isothermal calorimetry.

    PubMed

    Tafoukt, D; Soric, A; Sigoillot, J-C; Ferrasse, J-H

    2017-04-01

    The competitiveness of the second-generation bioethanol by biotechnological process requires an effective and quantitative control of biochemical reactions. In this study, the potential of isothermal calorimetry technique to measure heat and kinetics of a non-homogeneous substrate enzymatic hydrolysis is intended. Using this technique, optimum temperature of the enzymes used for lignocellulosic molecules hydrolysis was determined. Thus, the amount of substrate-to-enzyme ratio was highlighted as an important parameter of the hydrolysis yield. Furthermore, a new enzymes' cocktail efficiency consisting of a mix of cellulases and cellobiose dehydrogenase (CDH) was qualified by this technique. The results showed that this cocktail allowed the production of a high amount of gluconic acid that could improve the attractiveness of these second-generation biofuels. From the set of experiments, the hydrolysis heat of wheat straw was derived and a meaningful value of -32.2 ± 3.2 J g(-1) (gram reducing sugars product) is calculated. Then, isothermal measurements were used to determine kinetic constants of the cellulases and CDH mix on wheat straw. Results showed that this enzyme cocktail has an optimal rate at 45 °C in the range of temperatures tested (40-55 °C).

  16. Appropriateness of the definition of 'sedentary' in young children: Whole-room calorimetry study.

    PubMed

    Reilly, John J; Janssen, Xanne; Cliff, Dylan P; Okely, Anthony D

    2015-09-01

    The present study aimed to measure the energy cost of three common sedentary activities in young children to test whether energy expended was consistent with the recent consensus definition of 'sedentary' as 'any behaviour conducted in a sitting or reclining posture and with an energy cost ≤ 1.5 metabolic equivalents (METs)' (Sedentary Behaviour Research Network, 2012). Observational study. Whole-room calorimetry measures of television viewing, sitting at a table drawing and reading, and sitting on the floor playing with toys were made in 40 young children (mean age 5.3 years, SD 1.0). The energy cost of each sedentary activity was consistent with the recent consensus definition of sedentary: 1.17 METs (95% CI 1.07-1.27) for TV viewing; 1.38 METs (95% CI 1.30-1.46) for sitting at a table; and 1.35 METs (95% CI 1.28-1.43) for floor-based play. Common sedentary activities in young children have energy costs which are consistent with the recent consensus definition of 'sedentary', and the present study is supportive of this definition. Copyright © 2014 Sports Medicine Australia. Published by Elsevier Ltd. All rights reserved.

  17. Application of isothermal titration calorimetry as a tool to study natural product interactions.

    PubMed

    Callies, O; Hernández Daranas, A

    2016-07-28

    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.

  18. Pressure perturbation calorimetry, heat capacity and the role of water in protein stability and interactions.

    PubMed

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

    2007-12-01

    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.

  19. Differential scanning calorimetry as a tool for protein folding and stability.

    PubMed

    Johnson, Christopher M

    2013-03-01

    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.

  20. Application of differential scanning calorimetry to estimate quality and nutritional properties of food products.

    PubMed

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

    2016-05-31

    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.

  1. Application of TZERO calibrated modulated temperature differential scanning calorimetry to characterize model protein formulations.

    PubMed

    Badkar, Aniket; Yohannes, Paulos; Banga, Ajay

    2006-02-17

    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.

  2. Advances in the analysis of isothermal titration calorimetry data for ligand-DNA interactions.

    PubMed

    Buurma, Niklaas J; Haq, Ihtshamul

    2007-06-01

    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.

  3. Enzyme activity determination on macromolecular substrates by isothermal titration calorimetry: application to mesophilic and psychrophilic chitinases.

    PubMed

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

    2001-02-09

    Isothermal titration calorimetry has been applied to the determination of the kinetic parameters of chitinases (EC 3.2.1.14) 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.

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

    PubMed

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

    2016-05-25

    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.

  5. Application of isothermal titration calorimetry and column chromatography for identification of biomolecular targets.

    PubMed

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

    2011-02-01

    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.

  6. Quantifying the rates of relaxation of binary mixtures of amorphous pharmaceuticals with isothermal calorimetry.

    PubMed

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

    2010-10-31

    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.

  7. Calorimetry Minisensor for the Localised Measurement of Surface Heat Dissipated from the Human Body

    PubMed Central

    Socorro, Fabiola; Rodríguez de Rivera, Pedro Jesús; Rodríguez de Rivera, Manuel

    2016-01-01

    We have developed a calorimetry sensor that can perform a local measurement of the surface heat dissipated from the human body. The operating principle is based on the law of conductive heat transfer: heat dissipated by the human body passes across a thermopile located between the individual and a thermostat. Body heat power is calculated from the signals measured by the thermopile and the amount of power dissipated across the thermostat in order to maintain a constant temperature. The first prototype we built had a detection area measuring 6 × 6 cm2, while the second prototype, which is described herein, had a 2 × 2 cm2 detection area. This new design offers three advantages over the initial one: (1) greater resolution and three times greater thermal sensitivity; (2) a twice as fast response; and (3) it can take measurements from smaller areas of the body. The sensor has a 5 mW resolution, but the uncertainty is greater, up to 15 mW, due to the measurement and calculation procedure. The order of magnitude of measurements made in healthy subjects ranged from 60 to 300 mW at a thermostat temperature of 28 °C and an ambient room temperature of 21 °C. The values measured by the sensor depend on the ambient temperature and the thermostat’s temperature, while the power dissipated depends on the individual’s metabolism and any physical and/or emotional activity. PMID:27827977

  8. Polymorphism in nimodipine raw materials: development and validation of a quantitative method through differential scanning calorimetry.

    PubMed

    Riekes, Manoela Klüppel; Pereira, Rafael Nicolay; Rauber, Gabriela Schneider; Cuffini, Silvia Lucia; de Campos, Carlos Eduardo Maduro; Silva, Marcos Antonio Segatto; Stulzer, Hellen Karine

    2012-11-01

    Due to the physical-chemical and therapeutic impacts of polymorphism, its monitoring in raw materials is necessary. The purpose of this study was to develop and validate a quantitative method to determine the polymorphic content of nimodipine (NMP) raw materials based on differential scanning calorimetry (DSC). The polymorphs required for the development of the method were characterized through DSC, X-ray powder diffraction (XRPD) and Raman spectroscopy and their polymorphic identity was confirmed. The developed method was found to be linear, robust, precise, accurate and specific. Three different samples obtained from distinct suppliers (NMP 1, NMP 2 and NMP 3) were firstly characterized through XRPD and DSC as polymorphic mixtures. The determination of their polymorphic identity revealed that all samples presented the Modification I (Mod I) or metastable form in greatest proportion. Since the commercial polymorph is Mod I, the polymorphic characteristic of the samples analyzed needs to be investigated. Thus, the proposed method provides a useful tool for the monitoring of the polymorphic content of NMP raw materials.

  9. Isothermal calorimetry: a predictive tool to model drug-propellant interactions in pressurized metered dose systems.

    PubMed

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

    2014-01-30

    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.

  10. Calorimetry Minisensor for the Localised Measurement of Surface Heat Dissipated from the Human Body.

    PubMed

    Socorro, Fabiola; Rodríguez de Rivera, Pedro Jesús; Rodríguez de Rivera, Manuel

    2016-11-06

    We have developed a calorimetry sensor that can perform a local measurement of the surface heat dissipated from the human body. The operating principle is based on the law of conductive heat transfer: heat dissipated by the human body passes across a thermopile located between the individual and a thermostat. Body heat power is calculated from the signals measured by the thermopile and the amount of power dissipated across the thermostat in order to maintain a constant temperature. The first prototype we built had a detection area measuring 6 × 6 cm², while the second prototype, which is described herein, had a 2 × 2 cm² detection area. This new design offers three advantages over the initial one: (1) greater resolution and three times greater thermal sensitivity; (2) a twice as fast response; and (3) it can take measurements from smaller areas of the body. The sensor has a 5 mW resolution, but the uncertainty is greater, up to 15 mW, due to the measurement and calculation procedure. The order of magnitude of measurements made in healthy subjects ranged from 60 to 300 mW at a thermostat temperature of 28 °C and an ambient room temperature of 21 °C. The values measured by the sensor depend on the ambient temperature and the thermostat's temperature, while the power dissipated depends on the individual's metabolism and any physical and/or emotional activity.

  11. Binding of copper to lysozyme: Spectroscopic, isothermal titration calorimetry and molecular docking studies

    NASA Astrophysics Data System (ADS)

    Jing, Mingyang; Song, Wei; Liu, Rutao

    2016-07-01

    Although copper is essential to all living organisms, its potential toxicity to human health have aroused wide concerns. Previous studies have reported copper could alter physical properties of lysozyme. The direct binding of copper with lysozyme might induce the conformational and functional changes of lysozyme and then influence the body's resistance to bacterial attack. To better understand the potential toxicity and toxic mechanisms of copper, the interaction of copper with lysozyme was investigated by biophysical methods including multi-spectroscopic measurements, isothermal titration calorimetry (ITC), molecular docking study and enzyme activity assay. Multi-spectroscopic measurements proved that copper quenched the intrinsic fluorescence of lysozyme in a static process accompanied by complex formation and conformational changes. The ITC results indicated that the binding interaction was a spontaneous process with approximately three thermodynamical binding sites at 298 K and the hydrophobic force is the predominant driven force. The enzyme activity was obviously inhibited by the addition of copper with catalytic residues Glu 35 and Asp 52 locating at the binding sites. This study helps to elucidate the molecular mechanism of the interaction between copper and lysozyme and provides reference for toxicological studies of copper.

  12. Thermodynamics of cationic lipid-DNA complex formation as studied by isothermal titration calorimetry.

    PubMed

    Pozharski, Edwin; MacDonald, Robert C

    2002-07-01

    The detailed analysis of the cationic lipid-DNA complex formation by means of isothermal titration calorimetry is presented. Most experiments were done using 1,2-dioleyl-sn-glycero-3-ethylphosphocholine (EDOPC), but basic titrations were also done using DOTAP, DOTAP:DOPC, and DOTAP:DOPE mixtures. Complex formation was endothermic with less than 1 kcal absorbed per mole of lipid or DNA charge. This enthalpy change was attributed to DNA-DNA mutual repulsion within the lamellar complex. The exception was DOTAP:DOPE-containing lipoplex for which the enthalpy of formation was exothermic, presumably because of DOPE amine group protonation. Experimental conditions, namely, direction and titration increment as well as concentration of titrant, which dictate the structure of resulting lipoplex (whether lamellar complex or DNA-coated vesicle), were found to affect the apparent thermodynamics of complex formation. The structure, in turn, influences the biological properties of the lipoplex. If the titration of lipid into DNA was carried out in large increments, the DeltaH was larger than when the injection increments were smaller, a finding that is consistent with increased vesicle disruption under large increments and which is expected theoretically. Cationic lipid-DNA binding was weak in high ionic strength solutions, however, the effective binding constant is within micromolar range because of macromolecular nature of the interaction.

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

    NASA Astrophysics Data System (ADS)

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

    2016-12-01

    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.

  14. Porosity and Surface Properites of SBA-15 with Grafted PNIPAAM: A Water Sorption Calorimetry Study

    PubMed Central

    2011-01-01

    Mesoporous silica SBA-15 was modified in a three-step process to obtain a material with poly-N-isopropylacrylamide (PNIPAAM) grafted onto the inner pore surface. Water sorption calorimetry was implemented to characterize the materials obtained after each step regarding the porosity and surface properties. The modification process was carried out by (i) increasing the number of surface silanol groups, (ii) grafting 1-(trichlorosilyl)-2-(m-/p-(chloromethylphenyl) ethane, acting as an anchor for (iii) the polymerization of N-isopropylacrylamide. Water sorption isotherms and the enthalpy of hydration are presented. Pore size distributions were calculated on the basis of the water sorption isotherms by applying the BJH model. Complementary measurements with nitrogen sorption and small-angle X-ray diffraction are presented. The increase in the number of surface silanol groups occurs mainly in the intrawall pores, the anchor is mainly located in the intrawall pores, and the intrawall pore volume is absent after the surface grafting of PNIPAAM. Hence, PNIPAAM seals off the intrawall pores. Water sorption isotherms directly detect the presence of intrawall porosity. Pore size distributions can be calculated from the isotherms. Furthermore, the technique provides information regarding the hydration capability (i.e., wettability of different chemical surfaces) and thermodynamic information. PMID:21928772

  15. Thermodynamic Study on the Protonation Reactions of Glyphosate in Aqueous Solution: Potentiometry, Calorimetry and NMR spectroscopy.

    PubMed

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

    2016-03-10

    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.

  16. Isothermal titration calorimetry studies of neutral salt effects on the thermodynamics of micelle formation.

    PubMed

    Kresheck, Gordon C

    2009-05-14

    Isothermal titration calorimetry, ITC, was used to determine the enthalpy and heat capacity changes that accompany micelle formation of decyldimethylphosphine oxide, APO10, from 15-79 degrees C in the presence of representative neutral salts from the Hofmeister series. The solutions investigated were water, 0.2, 0.5, and 1.0 NaCl, 0.5 M NaF, KCl, KI, guanidinium chloride (GuHCl) and mannitol, and 0.333 M Na2SO4. The heat capacity change at 25 degrees C (but not the cmc) and the parameter that describes the temperature dependence of the heat capacity change, B (cal/(mol K2)), appear to be correlated. Calculated values of the ion effects on micelle formation from a recent salt ion partitioning model (SPM) of Pegram and Record [J. Phys. Chem. B 2007, 111, 5411-5417] were quantitatively related to the experimental value of the solute free energy increment (SFEI). Use of this model requires a calculation of the solvent accessible area (ASA), which yields values for the extent of hydration of the micelle interior. An alternate method to determine the ASA based on the heat capacity change for micelle formation at 25 degrees C of APO8-12 yielded values for the number of buried carbon atoms (5-12) versus previous estimates (4-8) from analysis of the B parameter.

  17. Phlogopite: high temperature solution calorimetry, thermodynamic properties, Al-Si and stacking disorder, and phase equilibria

    SciTech Connect

    Clemens, J.D.; Circone, S.; Navrotsky, A.; McMillan, P.F.; Smith, B.K.; Wall, V.J.

    1987-09-01

    Two structural features complicate the thermodynamics of synthetic and natural micas. The first is a varying degree of tetrahedral Al-Si disorder. Raman spectroscopic study of phlogopite synthesized above 600/sup 0/C suggests a disordered Al-Si distribution. Calculations of the P-T locus of the geologically important equilibrium: Phl + 3Qtz = 3En + Sa + H/sub 2/O, using the authors thermochemical data, agree within experimental error with the results of calculations based on the best available phase equilibrium data only if a tetrahedrally disordered phlogopite is assumed. Such calculations are very sensitive to uncertainties in ..delta..H/sup 0/ and ..delta..HG/sup 0/, and reversed phase equilibrium experiments remain essential to obtaining reliable estimates of thermodynamic properties. In contrast to these Al-Si disordered phlogopites, some biotites of low temperature parageneses (<600/sup 0/C) may have substantial Al-Si order. A variable Al-Si distribution has a substantial effect on the configurational entropy and therefore on the free energy of the mica in question. The second structural complication is stacking disorder, which is present in phlogopite synthesized at 650/sup 0/C but not in the 850/sup 0/C sample. The enthalpy difference between these two samples, determined by solution calorimetry, is smaller than the experimental uncertainty of +/- 1.0 kcal mol/sup -1/. Thus there appears to be little driving force for ordering, and micas with disordered stacking sequences may persist in many geologic environments.

  18. Energetics of genome ejection from phage revealed by isothermal titration calorimetry

    NASA Astrophysics Data System (ADS)

    Jeembaeva, Meerim; Jonsson, Bengt; Castelnovo, Martin; Evilevitch, Alex

    2009-03-01

    It has been experimentally shown that ejection of double-stranded DNA from phage is driven by internal pressure reaching tens of atmospheres. This internal pressure is partially responsible for delivery of DNA into the host cell. While several theoretical models and simulations nicely describe the experimental data of internal forces either resisting active packaging or equivalently favoring spontaneous ejection, there are no direct energy measurements available that would help to verify how quantitative these theories are. We performed direct measurements of the enthalpy responsible for DNA ejection from phage λ, using Isothermal Titration Calorimetry. The phage capsids were ``opened'' in vitro by titrating λ into a solution with LamB receptor and the enthalpy of DNA ejection process was measured. In his way, enthalpy stored in λ was determined as a function of packaged DNA length comparing wild-type phage λ (48.5 kb) with a shorter λ-DNA length mutant (37.7 kb). The temperature dependence of the ejection enthalpy was also investigated. The values obtained were in good agreement with existing models and provide a better understanding of ds- DNA packaging and release mechanisms in motor-packaged viruses (e.g., tailed bacteriophages, Herpes Simplex, and adenoviruses).

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

    PubMed

    Mårtensson, Anna K F; Lincoln, Per

    2015-02-28

    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.

  20. Forward calorimetry for heavy-ion physics at the STAR experiment

    NASA Astrophysics Data System (ADS)

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

    2017-01-01

    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.

  1. Global analysis of riboswitches by small-angle X-ray scattering and calorimetry

    PubMed Central

    Zhang, Jinwei; Jones, Christopher P.; Ferré-D’Amaré, Adrian R.

    2014-01-01

    Riboswitches are phylogenetically widespread non-coding mRNA domains that directly bind cellular metabolites and regulate transcription, translation, RNA stability or splicing via alternative RNA structures modulated by ligand binding. The details of ligand recognition by many riboswitches have been elucidated using X-ray crystallography and NMR. However, the global dynamics of riboswitch-ligand interactions and their thermodynamic driving forces are less understood. By compiling the work of many laboratories investigating riboswitches using small-angle X-ray scattering (SAXS) and isothermal titration calorimetry (ITC), we uncover general trends and common themes. There is a pressing need for community-wide consensus experimental conditions to allow results of riboswitch studies to be compared rigorously. Nonetheless, our meta-analysis reveals considerable diversity in the extent to which ligand binding reorganizes global riboswitch structures. It also demonstrates a wide spectrum of enthalpy-entropy compensation regimes across riboswitches that bind a diverse set of ligands, giving rise to a relatively narrow range of physiologically relevant free energies and ligand affinities. From the strongly entropy-driven binding of glycine to the predominantly enthalpy-driven binding of c-di-GMP to their respective riboswitches, these distinct thermodynamic signatures reflect the versatile strategies employed by RNA to adapt to the chemical natures of diverse ligands. Riboswitches have evolved to use a combination of long-range tertiary interactions, conformational selection, and induced fit to work with distinct ligand structure, charge, and solvation properties. PMID:24769285

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

    SciTech Connect

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

    2011-02-15

    Observational evidence for black hole spin down has been found in the normalized light curves of long gamma-ray bursts in the BATSE catalog. Over the duration T{sub 90} of the burst, matter swept up by the central black hole is susceptible to nonaxisymmetries, producing gravitational radiation with a negative chirp. A time-sliced matched filtering method is introduced to capture phase coherence on intermediate time scales, {tau}, here tested by the injection of templates into experimental strain noise, h{sub n}(t). For TAMA 300, h{sub n}(f){approx_equal}10{sup -21} Hz{sup -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{approx_equal}0.07-0.10 Mpc for the spin down of black holes of mass M=10-12M{sub {center_dot}} with {tau}=1 s. Extrapolation to advanced detectors implies D{approx_equal}35-50 Mpc for h{sub n}(f){approx_equal}2x10{sup -24} Hz{sup -1/2} around 1 kHz, which will open a new window to rigorous calorimetry on Kerr black holes.

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

    PubMed

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

    2013-03-21

    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. Real-time monitoring of membrane-protein reconstitution by isothermal titration calorimetry.

    PubMed

    Jahnke, Nadin; Krylova, Oxana O; Hoomann, Torben; Vargas, Carolyn; Fiedler, Sebastian; Pohl, Peter; Keller, Sandro

    2014-01-07

    Phase diagrams offer a wealth of thermodynamic information on aqueous mixtures of bilayer-forming lipids and micelle-forming detergents, providing a straightforward means of monitoring and adjusting the supramolecular state of such systems. However, equilibrium phase diagrams are of very limited use for the reconstitution of membrane proteins because of the occurrence of irreversible, unproductive processes such as aggregation and precipitation that compete with productive reconstitution. Here, we exemplify this by dissecting the effects of the K(+) channel KcsA on the process of bilayer self-assembly in a mixture of Escherichia coli polar lipid extract and the nonionic detergent octyl-β-d-glucopyranoside. Even at starting concentrations in the low micromolar range, KcsA has a tremendous impact on the supramolecular organization of the system, shifting the critical lipid/detergent ratios at the onset and completion of vesicle formation by more than 2-fold. Thus, equilibrium phase diagrams obtained for protein-free lipid/detergent mixtures would be misleading when used to guide the reconstitution process. To address this issue, we demonstrate that, even under such nonequilibrium conditions, high-sensitivity isothermal titration calorimetry can be exploited to monitor the progress of membrane-protein reconstitution in real time, in a noninvasive manner, and at high resolution to yield functional proteoliposomes with a narrow size distribution for further downstream applications.

  5. Advantages of isothermal titration calorimetry for xylanase kinetics in comparison to chemical-reducing-end assays.

    PubMed

    Baumann, Martin J; Murphy, Leigh; Lei, Nina; Krogh, Kristian B R M; Borch, Kim; Westh, Peter

    2011-03-01

    In lignocellulosic raw materials for biomass conversion, hemicelluloses constitute a substantial fraction, with xylan being the primary part. Although many pretreatments reduce the amount or change the distribution of xylan, it is important to degrade residual xylan so as to improve the overall yield. Typically, xylanase reaction rates are measured in stopped assays by chemical quantification of the reducing ends. With isothermal titration calorimetry (ITC), the heat flow of the hydrolysis can be measured in continuous fashion, with the reaction rate being directly proportional to the heat flow. Reaction enthalpies for carbohydrate hydrolysis are typically below 5kJ/mol, which is the limiting factor for straight forward calorimetric quantification of enzymatic reaction rates using current ITC technology. To increase the apparent reaction enthalpy, we employed a subsequent oxidation of hydrolysis products by carbohydrate oxidase and catalase. Here we show that the coupled assay with carbohydrate oxidase and catalase can be used to measure enzyme kinetics of a GH10 xylanase from Aspergillus aculeatus on birch xylan and wheat arabinoxylan. Results are discussed in the light of a critical analysis of the sensitivity of four chemical-reducing-end quantification methods using well-characterized substrates. 2010 Elsevier Inc. All rights reserved.

  6. Characterization of amorphous solids with weak glass transitions using high ramp rate differential scanning calorimetry.

    PubMed

    Katayama, Derrick S; Carpenter, John F; Manning, Mark Cornell; Randolph, Theodore W; Setlow, Peter; Menard, Kevin P

    2008-02-01

    Measurement of the glass transition temperature (T(g)) of proteins and other high molecular weight polymers in the amorphous state is often difficult, since the transition is extremely weak, that is, the DeltaC(p) at the glass transition temperature is small. For example, little is known about the solid-state properties of hydroxyethyl starch (HES), which is beginning to become more commonly evaluated as a bulking agent in pharmaceutical products. For weak thermal events, such as the change in heat capacity at the T(g) of a pure protein or large synthetic polymer, increased heating rate should produce greater sensitivity in terms of heat flow. Recent innovations in rapid scanning technology for differential scanning calorimetry (DSC) allow measurements on materials where the thermal events are difficult to detect by conventional DSC. In the current study, measurements of the T(g) of proteins in the solid state, amorphous pharmaceutical excipients which have small DeltaC(p) at the glass transition temperature, and bacterial spores, have all been made using high ramp rate DSC, providing information on materials that was inaccessible using conventional DSC methods.

  7. Differential scanning calorimetry as a screening technique in compatibility studies of DHEA extended release formulations.

    PubMed

    Mora, P Corvi; Cirri, M; Mura, P

    2006-09-11

    Differential scanning calorimetry (DSC) was used as a screening technique for assessing the compatibility of DHEA as ternary complex with alpha-cyclodextrin and glycine (c-DHEA) with some excipients suitable for preparation of sustained-release matrix tablets by direct compression. The effect of sample mechanical treatment due to the compression process was also evaluated. In order to investigate the possible interactions between the components, the DSC curves of c-DHEA and each selected excipient were compared with those of their 1:1 w/w physical mixtures, before and after compression, in order to evaluate any possible solid state modification. FT-IR spectroscopy and X-ray powder diffractometry were used as complementary techniques to adequately implement and assist in interpretation of the DSC results. On the basis of DSC results, c-DHEA was found to be compatible with xanthan gum, hydroxypropylmethylcellulose, sodium starch glycolate (Explotab), polyvinylacetate-polyvinylpirrolidone (Kollidon SR) and sodium chloride. Some drug-excipient interaction was observed with dextrate hydrate (Emdex), mannitol and Magnesium stearate. Finally, the behaviour of the complete formulation, in the presence of all the excipients selected by means of the compatibility study, was investigated, in order to verify the absence of reciprocal interactions among the components.

  8. Ionic liquids: differential scanning calorimetry as a new indirect method for determination of vaporization enthalpies.

    PubMed

    Verevkin, Sergey P; Emel'yanenko, Vladimir N; Zaitsau, Dzmitry H; Ralys, Ricardas V; Schick, Christoph

    2012-04-12

    Differential scanning calorimetry (DSC) has been used to measure enthalpies of synthesis reactions of the 1-alkyl-3-methylimidazolium bromide [C(n)mim][Br] ionic liquids from 1-methylimidazole and n-alkyl bromides (with n = 4, 5, 6, 7, and 8). The optimal experimental conditions have been elaborated. Enthalpies of formation of these ionic liquids in the liquid state have been determined using the DSC results according to the Hess Law. The ideal-gas enthalpies of formation of [C(n)mim][Br] were calculated using the methods of quantum chemistry. They were used together with the DSC results to derive indirectly the enthalpies of vaporization of the ionic liquids under study. In order to validate the indirect determination, the experimental vaporization enthalpy of [C(4)mim][Br] was measured by using a quartz crystal microbalance (QCM). The combination of reaction enthalpy measurements by DSC with modern high-level first-principles calculations opens valuable indirect thermochemical options to obtain values of vaporization enthalpies of ionic liquids.

  9. Atomic hydrogen concentration in a diamond depositing dc arcjet determined by calorimetry

    SciTech Connect

    Juchmann, W.; Luque, J.; Jeffries, J.B.

    1997-06-01

    The fraction of hydrogen dissociated in the plume of a dc arcjet used for diamond deposition is determined by calorimetry to be 0.33{plus_minus}0.12. A dc arc is struck in a mixture of argon and hydrogen at 90 psi and the effluent is expanded through a converging/diverging nozzle into a reactor maintained at 25 Torr. Methane ({lt}1{percent}) is added to the luminous gas plume in the diverging nozzle. This supersonic jet impinges on a water cooled molybdenum substrate, and diamond thin film grows from the reactive mixture. The electrical power input of the arcjet (1.6 kW) is balanced by the power losses due to cooling of the nozzle, enthalpy change in the gas, ionization of the gas, dissociation of H{sub 2}, and the directed velocity of the gas phase. The gas temperature is determined by linear laser-induced fluorescence (LIF) measurements of several rotational lines of NO seeded to the gas plume. The velocity of the gas plume is obtained via the Doppler shift between LIF signals measured simultaneously in a stationary reference cell and in the arcjet. The atomic hydrogen fraction increases as a function of the feedstock H{sub 2}/Ar ratio and with increasing input power to the arcjet. {copyright} {ital 1997 American Institute of Physics.}

  10. Applications of differential scanning calorimetry for thermal stability analysis of proteins: qualification of DSC.

    PubMed

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

    2012-03-01

    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.

  11. Simulating SiD Calorimetry: Software Calibration Procedures and Jet Energy Resolution

    SciTech Connect

    Cassell, Ron; /SLAC

    2009-02-23

    Simulated calorimeter performance in the SiD detector is examined. The software calibration procedures are described, as well as the perfect pattern recognition PFA reconstruction. Performance of the SiD calorimeters is summarized with jet energy resolutions from calorimetry only, perfect pattern recognition and the SiD PFA algorithm. Presented at LCWS08[1]. Our objective is to simulate the calorimeter performance of the SiD detector, with and without a Particle Flow Algorithm (PFA). Full Geant4 simulations using SLIC[2] and the SiD simplified detector geometry (SiD02) are used. In this geometry, the calorimeters are represented as layered cylinders. The EM calorimeter is Si/W, with 20 layers of 2.5mm W and 10 layers of 5mm W, segmented in 3.5 x 3.5mm{sup 2} cells. The HAD calorimeter is RPC/Fe, with 40 layers of 20mm Fe and a digital readout, segmented in 10 x 10mm{sup 2} cells. The barrel detectors are layered in radius, while the endcap detectors are layered in z(along the beam axis).

  12. Miniaturized calorimetry - a new method for real-time biofilm activity analysis.

    PubMed

    Lerchner, J; Wolf, A; Buchholz, F; Mertens, F; Neu, T R; Harms, H; Maskow, T

    2008-08-01

    The partial dissipation of Gibbs energy as heat reflects the metabolic dynamic of biofilms in real time and may also allow quantitative conclusions about the chemical composition of the biofilm via Hess' law. Presently, the potential information content of heat is hardly exploited due to the low flexibility, the low throughput and the high price of conventional calorimeters. In order to overcome the limitations of conventional calorimetry a miniaturized calorimeter for biofilm investigations has been evaluated. Using four thermopiles a heat production with spatial and temporal resolutions of 2.5 cm(-1) and 2 s(-1) could be determined. The limit of detection of the heat flow measurement was 20 nW, which corresponds to the cell density of an early stage biofilm (approx. 3x10(5) cells cm(-2)). By separating biofilm cultivation from the actual heat measurement, a high flexibility and a much higher throughput was achieved if compared with conventional calorimeters. The approach suggested allows cultivation of biofilms in places of interest such as technological settings as well as in nature followed by highly efficient measurements in the laboratory. Functionality of the miniaturized calorimeter was supported by parallel measurements with confocal laser scanning microscopy and a fiber optic based oxygen sensor using the oxycaloric equivalent (-460 kJ mol-O2(-1)).

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

    SciTech Connect

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

    2008-01-01

    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.

  14. High-precision isothermal titration calorimetry with automated peak-shape analysis.

    PubMed

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

    2012-06-05

    Isothermal titration calorimetry (ITC) is a powerful classical method that enables researchers in many fields to study the thermodynamics of molecular interactions. Primary ITC data comprise the temporal evolution of differential power reporting the heat of reaction during a series of injections of aliquots of a reactant into a sample cell. By integration of each injection peak, an isotherm can be constructed of total changes in enthalpy as a function of changes in solution composition, which is rich in thermodynamic information on the reaction. However, the signals from the injection peaks are superimposed by the stochastically varying time-course of the instrumental baseline power, limiting the precision of ITC isotherms. Here, we describe a method for automated peak assignment based on peak-shape analysis via singular value decomposition in combination with detailed least-squares modeling of local pre- and postinjection baselines. This approach can effectively filter out contributions of short-term noise and adventitious events in the power trace. This method also provides, for the first time, statistical error estimates for the individual isotherm data points. In turn, this results in improved detection limits for high-affinity or low-enthalpy binding reactions and significantly higher precision of the derived thermodynamic parameters.

  15. A Guide to Differential Scanning Calorimetry of Membrane and Soluble Proteins in Detergents.

    PubMed

    Yang, Zhengrong; Brouillette, Christie G

    2016-01-01

    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.

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

    SciTech Connect

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

    2005-10-01

    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.

  17. Biomolecule-nanoparticle interactions: Elucidation of the thermodynamics by isothermal titration calorimetry.

    PubMed

    Huang, Rixiang; Lau, Boris L T

    2016-05-01

    Nanomaterials (NMs) are often exposed to a broad range of biomolecules of different abundances. Biomolecule sorption driven by various interfacial forces determines the surface structure and composition of NMs, subsequently governs their functionality and the reactivity of the adsorbed biomolecules. Isothermal titration calorimetry (ITC) is a nondestructive technique that quantifies thermodynamic parameters through in-situ measurement of the heat absorption or release associated with an interaction. This review highlights the recent applications of ITC in understanding the thermodynamics of interactions between various nanoparticles (NPs) and biomolecules. Different aspects of a typical ITC experiment that are crucial for obtaining accurate and meaningful data, as well as the strengths, weaknesses, and challenges of ITC applications to NP research were discussed. ITC reveals the driving forces behind biomolecule-NP interactions and the effects of the physicochemical properties of both NPs and biomolecules by quantifying the crucial thermodynamics parameters (e.g., binding stoichiometry, ΔH, ΔS, and ΔG). Complimentary techniques would strengthen the interpretation of ITC results for a more holistic understanding of biomolecule-NP interactions. The thermodynamic information revealed by ITC and its complimentary characterizations is important for understanding biomolecule-NP interactions that are fundamental to the biomedical and environmental applications of NMs and their toxicological effects. Copyright © 2016 Elsevier B.V. All rights reserved.

  18. Misuse of thermodynamics in the interpretation of isothermal titration calorimetry data for ligand binding to proteins.

    PubMed

    Pethica, Brian A

    2015-03-01

    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. Copyright © 2014 Elsevier Inc. All rights reserved.

  19. Analysis of Diffusional Solidification in a Wide-Gap Brazing Powder Mixture Using Differential Scanning Calorimetry

    NASA Astrophysics Data System (ADS)

    Corbin, Stephen F.; Murray, D. Clark; Bouthillier, Alain

    2016-12-01

    The diffusional solidification (DS) of a mixed powder system, consisting of pure Ni base metal powder and BNi-2 braze powder, suitable for wide-gap brazing was investigated using differential scanning calorimetry (DSC) and parallel microstructural examination. It was determined that very little interdiffusion between the powders developed in the solid state prior to braze powder melting. Once liquid formed, rapid DS occurred such that, when the powders were loosely mixed together, only 20 to 50 wt pct of the potential liquid fraction actually developed, leading to poor densification. Separating the braze and Ni into a layered structure leads to less DS, increased liquid formation ( i.e., 35 to 80 wt pct of the potential liquid fraction) and improved densification. The rate of isothermal solidification in layered structures consisting of 30 and 40 wt pct BNi-2 braze material was determined using DSC. After 30 minutes of braze time at 1323 K (1050 °C), complete IS occurred, thus avoiding the formation of a continuous network of large borides. The final microstructure of the IS mixtures consisted of a continuous matrix of solid solution Ni, with isolated and dispersed borides.

  20. Study of temperature dependent zirconium silicide phases in Zr/Si structure by differential scanning calorimetry

    NASA Astrophysics Data System (ADS)

    Faruque, Sk Abdul Kader Md; Ranjan Bhattachryya, Satya; Sinha, Anil Kumar; Chakraborty, Supratic

    2016-02-01

    The differential scanning calorimetry (DSC) technique is employed to study the formation of different silicide compounds of Zr thin-film deposited on a 100 μm-thick Si (1 0 0) substrate by dc sputtering. A detailed analysis shows that silicide layers start growing at  ∼246 °C that changes to stable ZrSi2 at 627 °C via some compounds with different stoichiometric ratios of Zr and Si. It is further observed that oxygen starts reacting with Zr at  ∼540 °C but a stoichiometric ZrO2 film is formed after complete consumption of Zr metal at 857 °C. A further rise in temperature changes a part of ZrSi2 to Zr-Silicate. The synchrotron radiation-based grazing incidence x-ray diffraction and x-ray photoelectron spectroscopy studies also corroborate the above findings. Atomic force microscopy is also carried out on the samples. It is evident from the observations that an intermixing and nucleation of Zr and Si occur at lower temperature prior to the formation of the interfacial silicate layer. Zr-Silicate formation takes place only at a higher temperature.

  1. The use of differential scanning calorimetry for the purity verification of pharmaceutical reference standards.

    PubMed

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

    2009-04-05

    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.

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

    SciTech Connect

    Dechaumphai, Edward; Chen, Renkun

    2014-09-15

    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.

  3. Torn human rotator cuff tendons have reduced collagen thermal properties on differential scanning calorimetry.

    PubMed

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

    2011-12-01

    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.

  4. Study on the interaction of amino phosphine ester derivatives with DNA by spectroscopy, modeling and calorimetry.

    PubMed

    Lu, Yan; Wang, Gongke; Tang, Wen; Hao, Xiaoxiao; Xu, Meihua; Li, Xiang

    2011-11-01

    The binding properties of amino phosphate ester derivatives, compound 1 and 2 with calf thymus DNA (CT-DNA) were investigated by UV spectra, fluorescence spectra, molecular modeling and isothermal titration calorimetry (ITC). The intrinsic binding constants K(b) of compound 1 and 2 with CT-DNA were determined by fluorescence spectroscopy and ITC, respectively. The results indicated that the two compounds bind to CT-DNA with different binding affinity, which is in the order of compound 1>compound 2. At the same time, fluorescence spectra suggested that the mechanism of the binding of the two compounds to CT-DNA is a static enhancing type. According to the ethidium bromide displacement experiments, UV spectra, molecular modeling and ITC studies, it can be concluded that compound 1 and 2 are intercalators that can slide into the G-C rich region of CT-DNA. Furthermore, ITC data showed that compound/DNA binding is enthalpy controlled. Copyright © 2011 Elsevier B.V. All rights reserved.

  5. Heat resistance of viable but non-culturable Escherichia coli cells determined by differential scanning calorimetry.

    PubMed

    Castro-Rosas, Javier; Gómez-Aldapa, Carlos Alberto; Villagómez Ibarra, José Roberto; Santos-López, Eva María; Rangel-Vargas, Esmeralda

    2017-10-16

    Several reports have suggested that the viable but non-culturable (VBNC) state is a resistant form of bacterial cells that allows them to remain in a dormant form in the environment. Nevertheless, studies on the resistance of VBNC bacterial cells to ecological factors are limited, mainly because techniques that allow this type of evaluation are lacking. Differential scanning calorimetry (DSC) has been used to study the thermal resistance of culturable bacteria but has never been used to study VBNC cells. In this work, the heat resistance of Escherichia coli cells in the VBNC state was studied using the DSC technique. The VBNC state was induced in E. coli ATCC 25922 by suspending bacterial cells in artificial sea water, followed by storage at 3 ± 2°C for 110 days. Periodically, the behaviour of E. coli cells was monitored by plate counts, direct viable counts and DSC. The entire bacterial population entered the VBNC state after 110 days of storage. The results obtained with DSC suggest that the VBNC state does not confer thermal resistance to E. coli cells in the temperature range analysed here. © FEMS 2017. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

  6. Differential Scanning Calorimetry - A Method for Assessing the Thermal Stability and Conformation of Protein Antigen.

    PubMed

    Durowoju, Ibrahim B; Bhandal, Kamaljit S; Hu, Jian; Carpick, Bruce; Kirkitadze, Marina

    2017-03-04

    Differential scanning calorimetry (DSC) is an analytical technique that measures the molar heat capacity of samples as a function of temperature. In the case of protein samples, DSC profiles provide information about thermal stability, and to some extent serves as a structural "fingerprint" that can be used to assess structural conformation. It is performed using a differential scanning calorimeter that measures the thermal transition temperature (melting temperature; Tm) and the energy required to disrupt the interactions stabilizing the tertiary structure (enthalpy; ∆H) of proteins. Comparisons are made between formulations as well as production lots, and differences in derived values indicate differences in thermal stability and structural conformation. Data illustrating the use of DSC in an industrial setting for stability studies as well as monitoring key manufacturing steps are provided as proof of the effectiveness of this protocol. In comparison to other methods for assessing the thermal stability of protein conformations, DSC is cost-effective, requires few sample preparation steps, and also provides a complete thermodynamic profile of the protein unfolding process.

  7. Differential Scanning Calorimetry — A Method for Assessing the Thermal Stability and Conformation of Protein Antigen

    PubMed Central

    Durowoju, Ibrahim B.; Bhandal, Kamaljit S.; Hu, Jian; Carpick, Bruce; Kirkitadze, Marina

    2017-01-01

    Differential scanning calorimetry (DSC) is an analytical technique that measures the molar heat capacity of samples as a function of temperature. In the case of protein samples, DSC profiles provide information about thermal stability, and to some extent serves as a structural “fingerprint” that can be used to assess structural conformation. It is performed using a differential scanning calorimeter that measures the thermal transition temperature (melting temperature; Tm) and the energy required to disrupt the interactions stabilizing the tertiary structure (enthalpy; ∆H) of proteins. Comparisons are made between formulations as well as production lots, and differences in derived values indicate differences in thermal stability and structural conformation. Data illustrating the use of DSC in an industrial setting for stability studies as well as monitoring key manufacturing steps are provided as proof of the effectiveness of this protocol. In comparison to other methods for assessing the thermal stability of protein conformations, DSC is cost-effective, requires few sample preparation steps, and also provides a complete thermodynamic profile of the protein unfolding process. PMID:28287565

  8. Differential scanning calorimetry as a complementary diagnostic tool for the evaluation of biological samples.

    PubMed

    Garbett, Nichola C; Brock, Guy N

    2016-05-01

    Differential scanning calorimetry (DSC) is a tool for measuring the thermal stability profiles of complex molecular interactions in biological fluids. DSC profiles (thermograms) of biofluids provide specific signatures which are being utilized as a new diagnostic approach for characterizing disease but the development of these approaches is still in its infancy. This article evaluates several approaches for the analysis of thermograms which could increase the utility of DSC for clinical application. Thermograms were analyzed using localized thermogram features and principal components (PCs). The performance of these methods was evaluated alongside six models for the classification of a data set comprised of 300 systemic lupus erythematosus (SLE) patients and 300 control subjects obtained from the Lupus Family Registry and Repository (LFRR). Classification performance was substantially higher using the penalized algorithms relative to localized features/PCs alone. The models were grouped into two sets, the first having smoother solution vectors but lower classification accuracies than the second with seemingly noisier solution vectors. Coupling thermogram technology with modern classification algorithms provides a powerful diagnostic approach for analysis of biological samples. The solution vectors from the models may reflect important information from the thermogram profiles for discriminating between clinical groups. DSC thermograms show sensitivity to changes in the bulk plasma proteome that correlate with clinical status. To move this technology towards clinical application the development of new approaches is needed to extract discriminatory parameters from DSC profiles for the comparison and diagnostic classification of patients. Copyright © 2015 Elsevier B.V. All rights reserved.

  9. Fibrinogen adsorption on zinc oxide nanoparticles: a Micro-Differential Scanning Calorimetry analysis.

    PubMed

    Lousinian, S; Missopolinou, D; Panayiotou, C

    2013-04-01

    Understanding the interactions between proteins and surfaces (nanoparticles or films) is crucial for the fabrication and improvement of biomedical devices in direct contact with human blood. The aim of this work is the study of the interaction of fibrinogen (Fib) with zinc oxide nanoparticles. The nanoparticles were either synthesized chemically or were commercially available, having different size. Zinc oxide nanoparticles are known for their antibacterial properties, and Fib adsorption is studied in view of combining the antibacterial and desirable clotting behavior of a single material. The thermal properties of the Fib solution were studied by Micro-Differential Scanning Calorimetry. For the consideration of the compositional and structural properties of the nanoparticles, Fourier Transform Infrared Spectroscopy and Scanning Electron Microscopy were employed, respectively. Through the changes of the thermal properties of Fib upon adsorption that were observed by microDSC, the mechanisms of the protein adsorption were revealed. It seems that electrostatic (for the D and E domains) and hydrophobic interactions (for the aC chains) were responsible for the adsorption and the protein structural changes caused by it. The discrepancy between the Fib adsorption percentages on homemade and commercially available zinc oxide nanoparticles can be attributed to their different size. Copyright © 2013 Elsevier Inc. All rights reserved.

  10. Differential scanning calorimetry as a tool to investigate the transfer of anticancer drugs to biomembrane model.

    PubMed

    Sarpietro, Maria Grazia; Accolla, Maria Lorena; Celia, Christian; Grattoni, Alessandro; Castelli, Francesco; Fresta, Massimo; Ferrari, Mauro; Paolino, Donatella

    2013-08-01

    Different anticancer drugs clinically approved by international regulatory organizations present poor water solubility and low stability after systemic injection. Their administration requires suitable carriers capable of maximizing therapeutic efficacy. Lipid and polymeric nanotherapeutics, particularly liposomes, are widely used to deliver chemotherapeutics in the clinic. The interaction between chemotherapeutics and biocompatible lipids and polymers can affect their efficacy and play a pivotal role in chemotherapy. Phospholipids are the main components of liposomes and their interactions with therapeutic agents are widely investigated in the pharmaceutical field using differential scanning calorimetry (DSC). In this work, DSC was exploited to investigate the interaction between hydrophobic chemotherapeutics, i.e. docetaxel, tamoxifen and lapatinib, with lipid vesicles. Lipid carriers are prepared using dimyristoylphosphatidylcholine (DMPC), a phosphatidylcholine derivative, showing the same physicochemical features of the main lipids in the biological membranes. DMPC was used as a biological membrane model to evaluate interaction, passage, diffusion, and adsorption of chemotherapeutics. These processes were evaluated through the variation of thermotropic parameters of the biological membrane model. DSC studies were carried out in heating and cooling mode. Results demonstrated a modification of calorimetric curves and this effect is strictly related to the molar fraction and physicochemical features of chemotherapeutics. Furthermore, the interaction between chemotherapeutics and biological membranes affects their internalization and distribution inside tumors and this process depends on gel-liquid crystal transition of phospholipids. DSC results provide suitable information about this effect and can be used as tool to predict further interaction between chemotherapeutics and biological membranes.

  11. Deconvolution Analysis for Classifying Gastric Adenocarcinoma Patients Based on Differential Scanning Calorimetry Serum Thermograms

    PubMed Central

    Vega, Sonia; Garcia-Gonzalez, María Asuncion; Lanas, Angel; Velazquez-Campoy, Adrian; Abian, Olga

    2015-01-01

    Recently, differential scanning calorimetry (DSC) has been acknowledged as a novel tool for diagnosing and monitoring several diseases. This highly sensitive technique has been traditionally used to study thermally induced protein folding/unfolding transitions. In previous research papers, DSC profiles from blood samples of patients were analyzed and they exhibited marked differences in the thermal denaturation profile. Thus, we investigated the use of this novel technology in blood serum samples from 25 healthy subjects and 30 patients with gastric adenocarcinoma (GAC) at different stages of tumor development with a new multiparametric approach. The analysis of the calorimetric profiles of blood serum from GAC patients allowed us to discriminate three stages of cancer development (I to III) from those of healthy individuals. After a multiparametric analysis, a classification of blood serum DSC parameters from patients with GAC is proposed. Certain parameters exhibited significant differences (P < 0.05) and allowed the discrimination of healthy subjects/patients from patients at different tumor stages. The results of this work validate DSC as a novel technique for GAC patient classification and staging, and offer new graphical tools and value ranges for the acquired parameters in order to discriminate healthy from diseased subjects with increased disease burden. PMID:25614381

  12. Mechanic Insight into Aggregation of Lysozyme by Ultrasensitive Differential Scanning Calorimetry and Sedimentation Velocity.

    PubMed

    Wu, Sha; Ding, Yanwei; Zhang, Guangzhao

    2015-12-31

    Folding and aggregation of proteins profoundly influence their functions. We have investigated the effects of thermal history, concentration and pH on the denaturation and refolding of lysozyme by using ultrasensitive differential scanning calorimetry (US-DSC) and sedimentation velocity (SV) via analytical ultracentrifugation (AUC). The former is sensitive to small energy change whereas the latter can differentiate the oligomers such as dimer and trimer from individual protein molecules. Our studies reveal that the degree of denaturation irreversibility increases as heating times increases. The denaturation temperature (Td) and enthalpy change (ΔH) are influenced by heating rate since the denaturation is not in equilibrium during the heating. We can obtain Td and ΔH in equilibrium by extrapolation of heating rate to zero. In a dilute solution, no aggregation but unfolding happens in the denaturation. However, when the concentration is above a critical value (∼15.0 mg/mL), lysozyme molecules readily form trimers or other oligomers. Lysozyme molecules unfold into stretched chains at pH > 6.0, which would further forms large aggregates. The formation of aggregates makes the refolding of lysozyme impossible.

  13. Evaluation of the thermal property of bovine intramuscular adipose tissue using differential scanning calorimetry.

    PubMed

    Kimura, Noriyuki; Nishimura, Nana; Iwama, Nagako; Aihara, Yoshito; Ogawa, Yasuki; Miyaguchi, Yuji

    2017-10-01

    The thermal property of bovine intramuscular adipose tissue (IAT) was evaluated using differential scanning calorimetry (DSC) and compared with the melting point temperature (MP) of the fat extract of IAT, which was measured using the slip point method. The beef samples were classified according to the beef marbling score (BMS). Beef with a high BMS contained less protein than that with middle or low BMS. Beef with a high BMS contained significantly more fat than that with a low BMS (P < 0.05). The endothermic point temperature (EP) of IAT, measured by DSC, was significantly higher than the MP of IAT fat (P < 0.05). The EP showed no significant difference among the three marbling grade groups. Although the MP was correlated with the monounsaturated fatty acids (MUFA) content of IAT (R(2)  = 0.505), there was no correlation between the EP and the MUFA (R(2)  = 0.040). However, the EP of IAT treated with collagenase was relatively highly correlated with the MP (R(2)  = 0.655). Thus, these results suggested that DSC analysis would give us the practical thermal information regarding the melt-in the-mouth of beef such as the gelatinization of collagen, along with the melting of fat in IAT. © 2017 The Authors. Animal Science Journal published by John Wiley & Sons Australia, Ltd on behalf of Japanese Society of Animal Science.

  14. Deconvolution analysis for classifying gastric adenocarcinoma patients based on differential scanning calorimetry serum thermograms.

    PubMed

    Vega, Sonia; Garcia-Gonzalez, María Asuncion; Lanas, Angel; Velazquez-Campoy, Adrian; Abian, Olga

    2015-01-23

    Recently, differential scanning calorimetry (DSC) has been acknowledged as a novel tool for diagnosing and monitoring several diseases. This highly sensitive technique has been traditionally used to study thermally induced protein folding/unfolding transitions. In previous research papers, DSC profiles from blood samples of patients were analyzed and they exhibited marked differences in the thermal denaturation profile. Thus, we investigated the use of this novel technology in blood serum samples from 25 healthy subjects and 30 patients with gastric adenocarcinoma (GAC) at different stages of tumor development with a new multiparametric approach. The analysis of the calorimetric profiles of blood serum from GAC patients allowed us to discriminate three stages of cancer development (I to III) from those of healthy individuals. After a multiparametric analysis, a classification of blood serum DSC parameters from patients with GAC is proposed. Certain parameters exhibited significant differences (P < 0.05) and allowed the discrimination of healthy subjects/patients from patients at different tumor stages. The results of this work validate DSC as a novel technique for GAC patient classification and staging, and offer new graphical tools and value ranges for the acquired parameters in order to discriminate healthy from diseased subjects with increased disease burden.

  15. A new quantitative method to measure activity of ice structuring proteins using differential scanning calorimetry.

    PubMed

    Hassa-Roudsari, Majid; Goff, H Douglas

    2012-01-01

    There are very few quantitative assays to measure the activity of antifreeze proteins (AFPs, or Ice Structuring Proteins, ISPs) and these can be prone to various inaccuracies and inconsistencies. Some methods rely only on unassisted visual assessment. When microscopy is used to measure ice crystal size, it is critical that standardized procedures be adopted, especially when image analysis software is used to quantify sizes. Differential Scanning Calorimetry (DSC) has been used to measure the thermal hysteresis activity (TH) of AFPs. In this study, DSC was used isothermally to measure enthalpic changes associated with structural rearrangements as a function of time. Differences in slopes of isothermal heat flow vs. time between winter wheat ISP or AFP type I containing samples, and those without ISP or AFP type I were demonstrated. ISP or AFP type I containing samples had significantly higher slopes compared to those without ISP or AFP type I. Samples with higher concentration of ISP or AFP type I showed higher slope values during the first hour and took up to 3 hr to attain equilibrium. Differences were attributed to activity of the proteins at the ice interface. Proteinaceous activity of ISPs or AFP type I was confirmed by loss of activity after treatment with protease.

  16. Differential scanning calorimetry as a complementary diagnostic tool for the evaluation of biological samples

    PubMed Central

    Garbett, Nichola C.; Brock, Guy N.

    2015-01-01

    Background Differential scanning calorimetry (DSC) is a tool for measuring the thermal stability profiles of complex molecular interactions in biological fluids. DSC profiles (thermograms) of biofluids provide specific signatures which are being utilized as a new diagnostic approach for characterizing disease but the development of these approaches is still in its infancy. Methods This article evaluates several approaches for the analysis of thermograms which could increase the utility of DSC for clinical application. Thermograms were analyzed using localized thermogram features and principal components (PCs). The performance of these methods was evaluated alongside six models for the classification of a data set comprised of 300 systemic lupus erythematosus (SLE) patients and 300 control subjects obtained from the Lupus Family Registry and Repository (LFRR). Results Classification performance was substantially higher using the penalized algorithms relative to localized features / PCs alone. The models were grouped into two sets, the first having smoother solution vectors but lower classification accuracies than the second with seemingly noisier solution vectors. Conclusions Coupling thermogram technology with modern classification algorithms provides a powerful diagnostic approach for analysis of biological samples. The solution vectors from the models may reflect important information from the thermogram profiles for discriminating between clinical groups. General significance DSC thermograms show sensitivity to changes in the bulk plasma proteome that correlate with clinical status. To move this technology towards clinical application the development of new approaches is needed to extract discriminatory parameters from DSC profiles for the comparison and diagnostic classification of patients. PMID:26459005

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

    NASA Astrophysics Data System (ADS)

    Dechaumphai, Edward; Chen, Renkun

    2014-09-01

    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 (NbNx). 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 NbNx 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, NbNx based resistive thermometry can also be extended to cryogenic temperature, where the TCR is shown to be significantly higher.

  18. Interfacial chemistry at metal/CdTe contacts as probed by differential scanning calorimetry

    NASA Astrophysics Data System (ADS)

    Lin, W.-Y.; Wei, C.; Rajeshwar, K.

    1994-10-01

    All four possible chemical reactivity patterns, namely, outdiffusion of Te (metal-Cd alloy formation), Cd outdiffusion (metal telluride compound formation), comparable chemical reactivity of the metal towards both Cd and Te (no Cd or Te outdiffusion), and chemical inertness of the metal towards CdTe, were differentiated via the differential scanning calorimetry (DSC) technique from a study of the interaction of nine different metals toward CdTe powder. The fusion signatures of free Cd or Te, exotherms due to compound or alloy formation, along with the thermal transitions of the metal telluride and/or the intermetallic were used for this purpose. These reactivity patterns are discussed within the framework of two different thermodynamic models. Both virgin and chemically etched CdTe surfaces were examined, and found to exhibit rather different reactivity trends towards the metal. The ramifications of these results in terms of the electronic properties of metal/CdTe contacts are discussed. Finally, DSC is shown to be useful for probing alterations in the CdTe surface chemistry as a result of the etch treatment.

  19. Investigations of cosmetically treated human hair by differential scanning calorimetry in water.

    PubMed

    Wortmann, F-J; Springob, C; Sendelbach, G

    2002-01-01

    By applying differential scanning calorimetry (DSC) on human hair in water, the thermal stability of hair' major morphological components is determined. Against the background of the two-phase model for alpha-keratins, these components are identified as the partially helical, fibrous intermediate filaments (IF) and the intermediate filament associated-proteins (IFAP) as a cross-linked, amorphous matrix. DSC yields the denaturation enthalpy deltaH(D), which depends on the amount and structural integrity of the alpha-helical material, and the temperature T(D), which is kinetically controlled by the cross-link density of the matrix. To assess the effects of cosmetic treatments, hairs were investigated that had undergone either multiple bleaching or perm-waving treatments. The respective dependencies between denaturation temperature and enthalpy show that both morphological components are similarly affected by bleaching, while reductive damage, in comparison, is more pronounced in the IFs. For both types of treatments, changes in enthalpy follow apparent first-order kinetics with respect to the number of treatments as well as treatment time (perm-waving), yielding characteristic reaction rate constants. It appears that DSC in water is an especially suitable method to determine the kinetics of damage formation in human hair resulting from cosmetic treatments.

  20. Non-invasive techniques for assessing carbohydrate flux: I. Measurement of depletion by indirect calorimetry.

    PubMed

    Murgatroyd, P R; Sonko, B J; Wittekind, A; Goldberg, G R; Ceesay, S M; Prentice, A M

    1993-01-01

    Glycogen forms the smallest yet most labile energy substrate store. Therefore studying carbohydrate flux may be crucial to understanding the regulation of energy balance. Indirect calorimetry has been used to measure carbohydrate oxidation overnight and during exercise in nine fasted subjects. Overnight carbohydrate oxidation (averaging 2.85 +/- 0.8 g h-1) was assumed to be derived primarily from hepatic glycogen since subjects were inactive or asleep, and since glucose oxidized after gluconeogenesis from protein is measured as protein oxidation. Lower-limb muscle glycogen stores were depleted by repeated 30-min periods of cycle ergometry at 45% VO2max until exhaustion (8 +/- 1 periods). The carbohydrate oxidation rate decreased as exercise progressed. Quadratic curves yielded a close fit to each individual's exercise carbohydrate depletion data (mean multiple correlation r = 0.9996) and provided excellent inter-subject discrimination. Total (muscle plus liver) glycogen stores prior to exercise were estimated by extrapolation of the depletion curves to zero oxidation rate. This produced an extrapolation of the depletion curves to zero oxidation rate. This produced an estimate (174 +/- 61 g) which compared well with predictions (208 +/- 43 g) based on reference values for muscle mass and initial glycogen content. The results demonstrate that non-invasive estimates of glycogen status can be obtained from accurate respiratory exchange data.

  1. Microscopy and calorimetry as complementary techniques to analyze sugar crystallization from amorphous systems.

    PubMed

    Mazzobre, María F; Aguilera, José M; Buera, María P

    2003-03-14

    A comparison of microscopic and macroscopic techniques to evaluate sugar crystallization kinetics is presented using amorphous lactose and lactose-trehalose mixtures. Polarized light video microscopy (PLV) and differential scanning calorimetry (DSC) were applied to measure crystallization kinetics, induction times and time for complete sugar crystallization at different storage temperatures (60-95 degrees C). DSC was also employed to measure the glass transition temperature (T(ag)) of the systems. PLV permitted direct observation, in real time, of growth of individual crystals and morphological aspects at a scale not detected by DSC. Taking the average of several microscopic observations, the results for temperature dependence of crystallization rate and time to complete lactose crystallization were similar to those obtained by DSC. Both PLV and DSC techniques showed that the presence of trehalose delayed lactose crystallization, without affecting the T(ag) value. For the analysis of sugar crystallization in amorphous systems, PLV and DSC proved to be complementary techniques. Validation of results obtained by PLV with results from DSC opens a new area of microstructural analysis of crystallizing systems.

  2. Thermodynamic analysis of Bacillus subtilis endospore protonation using isothermal titration calorimetry

    NASA Astrophysics Data System (ADS)

    Harrold, Zoë R.; Gorman-Lewis, Drew

    2013-05-01

    Bacterial proton and metal adsorption reactions have the capacity to affect metal speciation and transport in aqueous environments. We coupled potentiometric titration and isothermal titration calorimetry (ITC) analyses to study Bacillus subtilis spore-proton adsorption. We modeled the potentiometric data using a four and five-site non-electrostatic surface complexation model (NE-SCM). Heats of spore surface protonation from coupled ITC analyses were used to determine site specific enthalpies of protonation based on NE-SCMs. The five-site model resulted in a substantially better model fit for the heats of protonation but did not significantly improve the potentiometric titration model fit. The improvement observed in the five-site protonation heat model suggests the presence of a highly exothermic protonation reaction circa pH 7 that cannot be resolved in the less sensitive potentiometric data. From the log Ks and enthalpies we calculated corresponding site specific entropies. Log Ks and site concentrations describing spore surface protonation are statistically equivalent to B. subtilis cell surface protonation constants. Spore surface protonation enthalpies, however, are more exothermic relative to cell based adsorption suggesting a different bonding environment. The thermodynamic parameters defined in this study provide insight on molecular scale spore-surface protonation reactions. Coupled ITC and potentiometric titrations can reveal highly exothermic, and possibly endothermic, adsorption reactions that are overshadowed in potentiometric models alone. Spore-proton adsorption NE-SCMs derived in this study provide a framework for future metal adsorption studies.

  3. Isothermal titration calorimetry as a tool to determine the thermodynamics of demicellization processes

    NASA Astrophysics Data System (ADS)

    Kessler, Anne; Zeeb, Benjamin; Kranz, Bertolt; Menéndez-Aguirre, Orquídea; Fischer, Lutz; Hinrichs, Jörg; Weiss, Jochen

    2012-10-01

    Demicellization of a 90 mM sodium dodecyl sulfate (SDS) solution in water at 10, 22, and 30 °C was studied by isothermal titration calorimetry (ITC). ΔH of the demicellization process was strongly temperature dependent, having an exothermic progression (-20.4 ± 0.9 kJ/mol, max) at 10 °C and an endothermic one (3.7 ± 1.2 kJ/mol, max) at 30 °C. ΔH for micelle dilution followed a slightly endothermic progression (0.9 ± 0.5 kJ/mol at 30 °C, 0.7 ± 1.3 kJ/mol at 22 °C, and 0.0 ± 0.5 kJ/mol at 10 °C) at all studied temperatures. No differences in ΔH for micelle dilution and demicellization was observed at 22 °C. The temperature dependence of ΔH measured by ITC could be related to hydrophobic interactions. Therefore, ITC was shown to be a useful tool to describe the thermodynamics of demicellization processes and in addition to determine alterations in ΔH caused by changes in hydrophobic and steric/electrostatic interactions.

  4. Probing the binding of procyanidin B3 to human serum albumin by isothermal titration calorimetry

    NASA Astrophysics Data System (ADS)

    Li, Xiangrong; Yan, Yunhui

    2015-02-01

    Proanthocyanidins are a mixture of monomers, oligomers, and polymers of flavan-3-ols that are widely distributed in the plant kingdom. One of the most widely studied proanthocyanidins is procyanidin B3. In this study, the interaction between procyanidin B3 and human serum albumin (HSA) was investigated using isothermal titration calorimetry (ITC). Thermodynamic investigations reveal that the hydrogen bond and van der Waals force are the major binding forces in the binding of procyanidin B3 to HSA. The binding of procyanidin B3 to HSA is driven by favorable enthalpy and unfavorable entropy. The obtained binding constant for procyanidin B3 with HSA is in the intermediate range and the equilibrium fraction of unbound procyanidin B3 fu > 90% at the physiological concentration of HSA shows that procyanidin B3 can be stored and transported from the circulatory system to reach its target site. The stoichiometric binding number n approximately equals to 1, suggesting that one molecule of procyanidin B3 combines with one molecule of HSA and no more procyanidin B3 binding to HSA occurs at the concentration used in this study.

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

    SciTech Connect

    Damian, Luminita; Marty-Detraves, Claire; Winterhalter, Mathias; Fournier, Didier; Paquereau, Laurent

    2009-07-31

    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.

  6. A novel optical calorimetry dosimetry approach applied to an HDR Brachytherapy source

    NASA Astrophysics Data System (ADS)

    Cavan, A.; Meyer, J.

    2013-06-01

    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.

  7. Thermodynamics of cationic lipid-DNA complex formation as studied by isothermal titration calorimetry.

    PubMed Central

    Pozharski, Edwin; MacDonald, Robert C

    2002-01-01

    The detailed analysis of the cationic lipid-DNA complex formation by means of isothermal titration calorimetry is presented. Most experiments were done using 1,2-dioleyl-sn-glycero-3-ethylphosphocholine (EDOPC), but basic titrations were also done using DOTAP, DOTAP:DOPC, and DOTAP:DOPE mixtures. Complex formation was endothermic with less than 1 kcal absorbed per mole of lipid or DNA charge. This enthalpy change was attributed to DNA-DNA mutual repulsion within the lamellar complex. The exception was DOTAP:DOPE-containing lipoplex for which the enthalpy of formation was exothermic, presumably because of DOPE amine group protonation. Experimental conditions, namely, direction and titration increment as well as concentration of titrant, which dictate the structure of resulting lipoplex (whether lamellar complex or DNA-coated vesicle), were found to affect the apparent thermodynamics of complex formation. The structure, in turn, influences the biological properties of the lipoplex. If the titration of lipid into DNA was carried out in large increments, the DeltaH was larger than when the injection increments were smaller, a finding that is consistent with increased vesicle disruption under large increments and which is expected theoretically. Cationic lipid-DNA binding was weak in high ionic strength solutions, however, the effective binding constant is within micromolar range because of macromolecular nature of the interaction. PMID:12080142

  8. Neutron monitoring and electrode calorimetry experiments in the HIP-1 Hot Ion Plasma

    NASA Technical Reports Server (NTRS)

    Reinmann, J. J.; Layman, R. W.

    1977-01-01

    Results are presented for two diagnostic procedures on HIP-1: neutron diagnostics to determine where neutrons originated within the plasma discharge chamber and electrode calorimetry to measure the steady-state power absorbed by the two anodes and cathodes. Results are also reported for a hot-ion plasma formed with a continuous-cathode rod, one that spans the full length of the test section, in place of the two hollow cathodes. The outboard neutron source strength increased relative to that at the midplane when (1) the cathode tips were moved farther outboard, (2) the anode diameters were increased, and (3) one of the anodes was removed. The distribution of neutron sources within the plasma discharge chamber was insensitive to the division of current between the two cathodes. For the continuous cathode, increasing the discharge current increased the midplane neutron source strength relative to the outboard source strength. Each cathode absorbed from 12 to 15 percent of the input power regardless of the division of current between the cathodes. The anodes absorbed from 20 to 40 percent of the input power. The division of power absorption between the anodes varied with plasma operating conditions and electrode placement.

  9. Interaction of oridonin with human serum albumin by isothermal titration calorimetry and spectroscopic techniques.

    PubMed

    Li, Xiangrong; Yang, Zhenhua

    2015-05-05

    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.

  10. Phosphate sorption by three potential filter materials as assessed by isothermal titration calorimetry.

    PubMed

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

    2014-10-01

    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.

  11. Microtubule-associated proteins and tubulin interaction by isothermal titration calorimetry.

    PubMed

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

    2013-01-01

    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.

  12. Single-experiment displacement assay for quantifying high-affinity binding by isothermal titration calorimetry.

    PubMed

    Krainer, Georg; Keller, Sandro

    2015-04-01

    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.

  13. AC Calorimetry and Thermophysical Properties of Bulk Glass-Forming Metallic Liquids

    NASA Technical Reports Server (NTRS)

    Johnson, William L.

    2000-01-01

    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.

  14. Vascular Endothelial Growth Factor Peptide Ligands Explored by Competition Assay and Isothermal Titration Calorimetry.

    PubMed

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

    2015-08-25

    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.

  15. Spectroscopy, calorimetry and molecular simulation studies on the interaction of catalase with copper ion.

    PubMed

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

    2015-02-01

    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.

  16. Toxic effects of chrysoidine on human serum albumin: isothermal titration calorimetry and spectroscopic investigations.

    PubMed

    Sun, Haoyu; Liu, Yingxue; Li, Meng; Han, Songlin; Yang, Xudan; Liu, Rutao

    2016-03-01

    Chrysoidine is widely used in industry as a type of azo dye, and is sometimes used illegally as a food additive despite its potential toxicity. Human serum albumin (HSA) is one of the most important proteins in blood plasma and possesses major physiological functions. In the present study, the conformational and functional effects of chrysoidine on HSA were investigated by isothermal titration calorimetry (ITC), multiple spectroscopic methods, a molecular docking study and an esterase activity assay. Based on the ITC results, the binding stoichiometry of chrysoidine to HSA was estimated to be 1.5:1, and was a spontaneous process via a single hydrogen bond. The binding of chrysoidine to HSA induced dynamic quenching in fluorescence, and changes in secondary structure and in the microenvironment of the Trp-214 residue. In addition, the hydrogen bond (1.80 Å) formed between the chrysoidine molecule and the Gln-211 residue. The esterase activity of HSA decreased following the addition chrysoidine due to the change in protein structure. This study details the direct interaction between chrysoidine and HSA at the molecular level and the mechanism for toxicity as a result of the functional changes induced by HSA structural variation upon binding to chrysoidine in vitro. This study provides useful information towards detailing the transportation mechanism and toxicity of chrysoidine in vivo.

  17. Isothermal titration calorimetry determination of individual rate constants of trypsin catalytic activity.

    PubMed

    Aguirre, César; Condado-Morales, Itzel; Olguin, Luis F; Costas, Miguel

    2015-06-15

    Determination of individual rate constants for enzyme-catalyzed reactions is central to the understanding of their mechanism of action and is commonly obtained by stopped-flow kinetic experiments. However, most natural substrates either do not fluoresce/absorb or lack a significant change in their spectra while reacting and, therefore, are frequently chemically modified to render adequate molecules for their spectroscopic detection. Here, isothermal titration calorimetry (ITC) was used to obtain Michaelis-Menten plots for the trypsin-catalyzed hydrolysis of several substrates at different temperatures (278-318K): four spectrophotometrically blind lysine and arginine N-free esters, one N-substituted arginine ester, and one amide. A global fitting of these data provided the individual rate constants and activation energies for the acylation and deacylation reactions, and the ratio of the formation and dissociation rates of the enzyme-substrate complex, leading also to the corresponding free energies of activation. The results indicate that for lysine and arginine N-free esters deacylation is the rate-limiting step, but for the N-substituted ester and the amide acylation is the slowest step. It is shown that ITC is able to produce quality kinetic data and is particularly well suited for those enzymatic reactions that cannot be measured by absorption or fluorescence spectroscopy.

  18. PREFACE: XVth International Conference on Calorimetry in High Energy Physics (CALOR2012)

    NASA Astrophysics Data System (ADS)

    Akchurin, Nural

    2012-12-01

    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 calor2012.ttu.edu. 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

  19. Energy dispersive x-ray diffractometry as a tool alternative to differential scanning calorimetry for investigating polymer phase transitions

    NASA Astrophysics Data System (ADS)

    Rossi-Albertini, V.; Isopo, A.; Caminiti, R.; Tentolini, U.

    2002-02-01

    Recently, a technique based on energy dispersive x-ray diffraction has been proposed to follow the polymer phase transitions. However, the potentialities of this method were not clear, as well as the experimental conditions in which it is more convenient than differential scanning calorimetry, generally used for the same purpose. In the present letter, the answer to this question is provided. It is shown that the two methods are complementary, rather than equivalent, the heating rate being the relevant parameter to establish which is preferable. The demonstration of this statement is given through the observation of the complex thermal properties of a reference sample studied in both ways at progressively lower heating rates. The connection between such unusual application of x-ray diffraction and the differential scanning calorimetry is discussed in terms of the two possible definitions of entropy.

  20. Comparison of steps and energy expenditure assessment in adults of Fitbit Tracker and Ultra to the Actical and indirect calorimetry.

    PubMed

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

    2013-10-01

    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.

  1. Evaluation of the interaction of coumarins with biomembrane models studied by differential scanning calorimetry and Langmuir-Blodgett techniques.

    PubMed

    Sarpietro, Maria Grazia; Giuffrida, Maria Chiara; Ottimo, Sara; Micieli, Dorotea; Castelli, Francesco

    2011-04-25

    Three coumarins, scopoletin (1), esculetin (2), and esculin (3), were investigated by differential scanning calorimetry and Langmuir-Blodgett techniques to gain information about the interaction of these compounds with cellular membranes. Phospholipids assembled as multilamellar vesicles or monolayers (at the air-water interface) were used as biomembrane models. Differential scanning calorimetry was employed to study the interaction of these coumarins with multilamellar vesicles and to evaluate their absorption by multilamellar vesicles. These experiments indicated that 1-3 interact in this manner to different extents. The Langmuir-Blodgett technique was used to study the effect of these coumarins on the organization of phospholipids assembled as a monolayer. The data obtained were in agreement with those obtained in the calorimetric experiments.

  2. Kinetics of solid-gas reactions characterized by scanning AC nano-calorimetry with application to Zr oxidation

    SciTech Connect

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

    2014-10-27

    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.

  3. Spin density wave (SDW) transition in Ru doped BaFeAs2 investigated by AC steady state calorimetry

    NASA Astrophysics Data System (ADS)

    Vinod, K.; Sharma, Shilpam; Sundar, C. S.; Bharathi, A.

    2015-06-01

    Heat capacity measurements were done on sub-micron sized BaFe2-xRuxAs2 single crystals using thin film membrane based the AC steady state calorimetry technique. Noticeable thermal hysteresis is observed in the heat capacity of the BaFe2-xRuxAs2 during cooling and warming cycles, indicating first order nature of the SDW transition.

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

    SciTech Connect

    Vinod, K. Sharma, Shilpam; Sundar, C. S.; Bharathi, A.

    2015-06-24

    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.

  5. Comparative results of autogenous ignition temperature measurements by ASTM G 72 and pressurized scanning calorimetry in gaseous oxygen

    NASA Technical Reports Server (NTRS)

    Bryan, C. J.; Lowrie, R.

    1986-01-01

    The autogenous ignition temperature of four materials was determined by ASTM (G 72) and pressurized differential scanning calorimetry at 0.68-, 3.4-, and 6.8-MPa oxygen pressure. All four materials were found to ignite at lower temperatures in the ASTM method. The four materials evaluated in this program were Neoprene, Vespel SP-21, Fluorel E-2160, and nylon 6/6.

  6. Comparative results of autogenous ignition temperature measurements by ASTM G 72 and pressurized scanning calorimetry in gaseous oxygen

    NASA Technical Reports Server (NTRS)

    Bryan, C. J.; Lowrie, R.

    1986-01-01

    The autogenous ignition temperature of four materials was determined by ASTM (G 72) and pressurized differential scanning calorimetry at 0.68-, 3.4-, and 6.8-MPa oxygen pressure. All four materials were found to ignite at lower temperatures in the ASTM method. The four materials evaluated in this program were Neoprene, Vespel SP-21, Fluorel E-2160, and nylon 6/6.

  7. Label-Free Determination of the Dissociation Constant of Small Molecule-Aptamer Interaction by Isothermal Titration Calorimetry.

    PubMed

    Vogel, Marc; Suess, Beatrix

    2016-01-01

    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.

  8. Calorimetry on a Chip: Toward Heat Capacities of Microgram Quantities of Iron-bearing Minerals

    NASA Astrophysics Data System (ADS)

    Navrotsky, A.; Hellman, F.; Dorogova, M.; Cooke, D.; Queen, D.

    2005-12-01

    Heat capacities, standard entropies, and magnetic phase transitions in iron-bearing mantle minerals are poorly known because conventional adiabatic calorimetry requires samples too large to be synthesized at very high pressure. Specific heat measurements on microgram sized samples are based on a Si-micromachined calorimetry device. These devices have been in use for a decade in the physics and materials science community for measurements on metals and on selected oxides such as CoO. These calorimeters on a chip have been used for both thin films and small bulk samples. Different designs have been optimized for different uses, but the heart of the device is a thin (1800 ?) 0.5 x 0.5 cm2 amorphous Si3N4 membrane supported by a 1 x 1 cm2 Si frame. On one side of this membrane, we deposit and pattern thin film heater, thermometers, and electrical leads of appropriate resistance and temperature coefficient. On the other side, in a 0.25 x 0.25 cm2 area at the center, we deposit the sample and a thermally conducting material such as gold or copper. This thin membrane provides the necessary thermal isolation of sample from environment, while still providing a sample/thermometer platform. On the frame are matching thermometers to those on the membrane to permit a high sensitivity differential temperature measurement. We have made thousands of these devices and have measured hundreds. The devices are metallurgically stable and physically robust under cycling between 4.2 K and 1000 K, and can withstand photolithographic processing. Because of the nature of the fabrication process, reproducibility of specific heat addenda and of thermal link between sample and environment is very good, varying from device to device by less than 5%. Samples are measured using the relaxation method, requiring a separate determination of the thermal link between sample and environment (the steady state increase of the sample temperature with the sample heater turned on) and the time constant of

  9. Quantifying Natural Organic Matter with Calorimetry - assessing system complexity to build a central view C stability

    NASA Astrophysics Data System (ADS)

    Liles, G. C.; Bower, J.; Henneberry, Y.; Horwath, W. R.

    2010-12-01

    Characterizing the status and stability of natural organic matter (NOM) is central to understanding the flux, attenuation and function of C in the biosphere. A diversity of stabilizing factors (climate, mineralogy, chemical recalcitrance) have required a range of analytical approaches and methods that are site or discipline specific making unified assessments difficult. Aggregated, these efforts support our working models of NOM as a dynamic body but, overall, lack analytical simplicity and reproducibility. In particular, the robustness and resolution to assess NOM across systems of increasing complexity is lacking. Calorimetry has been central to chemistry and material science characterizing a broad range of organic and inorganic materials and their mixtures illustrating composition, purity and stability. Differential scanning calorimetry - thermogravimetry (DSC-TG) provides the flexibility and resolution to quantify the complexity found within NOM with precise quantification of material mass loss (TG) and energetic (DSC) under controlled atmospheric and heating conditions. DSC-TG is data rich providing a range of qualitative and quantitative metrics: peak shape, exothermic energy yield, mass loss, and determination of enthalpy, to characterize NOM stability from low (dissolved organic carbon - DOC) through high (compost and soils) molecular weights (MW) at increasing levels of organo-metallic complexity. Our research investigates the influence of biochemical recalcitrance and its alteration by oxides employing three natural systems of varying complexity as experimental models: aquatic - DOC and DOC with metal flocculants (low MW - low complexity), compost - processed with and without metal oxides (mixed MW - increasing complexity) and forest soils - under varying management and litter inputs (mixed MW - most complexity). Samples were analyzed by DSC-TG (zero-air - 20 C/min - ambient to > 800C) and assessed for three temperature/exothermic reaction regions (200

  10. Fasting substrate oxidation at rest assessed by indirect calorimetry: is prior dietary macronutrient level and composition a confounder?

    PubMed

    Miles-Chan, J L; Dulloo, A G; Schutz, Y

    2015-07-01

    Indirect calorimetry, the measurement of O₂ consumption and CO₂ production, constitutes an invaluable tool as the most common method for analyzing whole-body energy expenditure, and also provides an index of the nature of macronutrient substrate oxidation--namely, carbohydrate (CHO) versus fat oxidation. The latter constitutes a key etiological factor in obesity as this condition can only develop when total fat oxidation is chronically lower than total exogenous fat intake. The standardization of indirect calorimetry measurements is essential for accurately tracking the relative proportion of energy expenditure derived from CHO and fat oxidation. Here we analyze literature data to show that the average fasting respiratory quotient typically shifts from approximately 0.80 to 0.90 (indicating a doubling of resting CHO oxidation) in response to a switch in dietary CHO intake (as % energy) from 30 to 60%. This underscores the importance of taking into account dietary macronutrient composition prior to indirect calorimetry studies in the interpretation of data on substrate utilization and oxidation.

  11. Fluorescence spectroscopic and calorimetry based approaches to characterize the mode of interaction of small molecules with DNA.

    PubMed

    Banerjee, Amrita; Singh, Jasdeep; Dasgupta, Dipak

    2013-07-01

    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.

  12. Differential scanning calorimetry study of glass transition in frozen starch gels.

    PubMed

    Tananuwong, Kanitha; Reid, David S

    2004-06-30

    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.

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

    NASA Astrophysics Data System (ADS)

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

    2016-01-01

    Steady-state and time-resolved fluorescence quenching measurements supported by Isothermal Titration Calorimetry (ITC) were used to study the interactions of Cu2 + 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 298.15 K in 20 mM 2-(N-morpholino)ethanesulfonic acid (MES) buffer solution with a pH of 6. The fluorescence of all peptides was quenched by Cu2 + ions. The stoichiometry, conditional stability constants and thermodynamic parameters for the interactions of the Cu2 + 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 Cu2 + ions are discussed.

  14. Phase behavior in the system tetrahydrofuran-water-ammonia from calorimetry and Raman spectroscopy

    NASA Astrophysics Data System (ADS)

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

    2016-10-01

    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 <, = or > 17, which corresponds with the THF-clathrate stoichiometric ratio, and at NH3 concentrations up to 30 wt%. When X < 17, THF is in excess; all the H2O forms clathrates, no ammonia hydrates are observed, and the excess THF interacts with NH3 to form a NH3-THF phase. 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.

  15. Characterization of lipophilic gemcitabine prodrug-liposomal membrane interaction by differential scanning calorimetry.

    PubMed

    Castelli, Francesco; Sarpietro, Maria Grazia; Ceruti, Maurizio; Rocco, Flavio; Cattel, Luigi

    2006-01-01

    Gemcitabine is an anticancer agent rapidly deaminated to the inactive metabolite 2',2'-difluorodeoxyuridine. Its stability as well as bioavailability can be increased by making prodrugs. A series of lipophilic prodrugs of gemcitabine were synthesized by linking the 4-amino group with valeroyl, lauroyl, and stearoyl linear acyl derivatives. We studied, by the differential scanning calorimetry technique, and compared the interaction of pure gemcitabine and its prodrugs with dimyristoylphosphatidylcholine and distearoylphosphatidylcholine vesicles with the aim of demonstrating if the gemcitabine prodrug is more able than the pure gemcitabine to interact with lipid vesicles employed both as model biomembranes and as carriers in the transport of antitumor drugs. These studies, carried out by static and kinetic calorimetric measurements, give evidence that the increase of the prodrug's lipophilic character improves the interaction with lipid bilayers, favoring the absorption through the lipid barriers and allowing the liposomes to work (when the prodrug is inserted inside the vesicles) as a lipophilic carrier which is able to deliver the drug near the cell surface. The use of different prodrugs modified in their lipophilic character, of different kinds of vesicles (multilamellar and unilamellar), and of different kinds of vesicles forming phospholipids permitted us to determine the better equilibrium between in-vesicle solubility and through-vesicle diffusion of the drug, important in the preformulative studies of antitumor carriers based on phospholipid formulations. Such studies suggest that the prodrug lipophilic tail should modulate the transport and the release of gemcitabine inside the cellular compartments, and the efficiency of the liposomal system is related to the length of the prodrug's acyl chain which has to match the phospholipid acyl chain allowing or retarding the migration through the lipid release device.

  16. Determination of affinity and efficacy of acetylcholinesterase inhibitors using isothermal titration calorimetry.

    PubMed

    Draczkowski, Piotr; Tomaszuk, Anna; Halczuk, Pawel; Strzemski, Maciej; Matosiuk, Dariusz; Jozwiak, Krzysztof

    2016-05-01

    Acetylcholinesterase (AChE), an enzyme rapidly terminating nerve signals at synapses of cholinergic neurons is an important drug target in treatment of Alzheimer's disease and related memory loss conditions. Here we present comprehensive use of isothermal titration calorimetry (ITC) for investigation of AChE kinetics and AChE-inhibitor interactions. Acetylcholinesterase (AChE, EC 3.1.1.7) from Electrophorus electricus was assayed for interactions with five well known AChE inhibitors, galanthamine, tacrine, donepezil, edrophonium and ambenonium. In ITC experiments the inhibitors were injected to the enzyme solution solely (for thermodynamic characterization of binding) or in presence of the substrate, acetylcholine (for determination of inhibitors potency). Detailed description of various experimental protocols is presented, allowing evaluation of inhibitors potency (in terms of IC50 and Ki) and thermodynamic parameters of the binding. The potency of tested inhibitors was in nano to micromolar range which corresponded to activities determined in conventional method. Binding of all inhibitors showed to be enthalpy driven and obtained Ka values demonstrated good correlation with the data from standard Ellman's assay. Obtained results confirmed the usability of the ITC technique for comprehensive characterization of AChE-inhibitor interactions and AChE kinetics. The method reduced the complexity of reaction mixture and interference problems with the advantage of using natural substrates. The work reports complete thermodynamic characteristics of the AChE - inhibitor complexes. Due to the universal character of ITC measurements, described protocols can be easily adapted to other enzymatic systems. Copyright © 2015 Elsevier B.V. All rights reserved.

  17. Pressure Perturbation Calorimetry of Apolipoproteins in Solution and in Model Lipoproteins

    PubMed Central

    Benjwal, Sangeeta; Gursky, Olga

    2009-01-01

    High-density lipoproteins (HDL) are complexes of lipids and proteins (termed apolipoproteins) that remove cell cholesterol and protect from atherosclerosis. Apolipoproteins contain amphipathic α-helices that have high content (≥1/3) and distinct distribution of charged and apolar residues, adopt molten globule-like conformations in solution, and bind to lipid surfaces. We report the first pressure perturbation calorimetry (PPC) study of apolipoproteins. In solution, the main HDL protein, apoA-I, shows relatively large volume contraction, ΔVunf=-0.33%, and an apparent reduction in thermal expansivity upon unfolding, Δαunf≤0, which has not been observed in other proteins. We propose that these values are dominated by increased charged residue hydration upon α-helical unfolding, which may result from disruption of multiple salt bridges. At 5°C, apoA-I shows large thermal expansion coefficient, α(5°) = 15·10-4 K-1, that rapidly declines upon heating from 5-40°C, α(40°)-α(5°)=-4·10-4 K-1; apolipoprotein C-I shows similar values of α(5°) and α(40°). These values are larger than in globular proteins. They indicate dominant effect of charged residue hydration, which may modulate functional apolipoprotein interactions with a broad range of their protein and lipid ligands. The first PPC analysis of a protein-lipid complex is reported, which focuses on the chain melting transition in model HDL containing apoA-I or apoC-I, dimyristoyl phosphatidylcholine, and 0–20% cholesterol. The results may provide new insights into volumetric properties of HDL that modulate metabolic lipoprotein remodeling during cholesterol transport. PMID:19927327

  18. Use of isothermal titration calorimetry to study surfactant aggregation in colloidal systems.

    PubMed

    Loh, Watson; Brinatti, César; Tam, Kam Chiu

    2016-05-01

    Isothermal titration calorimetry (ITC) is a general technique that allows for precise and highly sensitive measurements. These measurements may provide a complete and accurate thermodynamic description of association processes in complex systems such as colloidal mixtures. This review will address uses of ITC for studies of surfactant aggregation to form micelles, with emphasis on the thermodynamic studies of homologous surfactant series. We will also review studies on surfactant association with polymers of different molecular characteristics and with colloidal particles. ITC studies on the association of different homologous series of surfactants provide quantitative information on independent contribution from their apolar hydrocarbon chains and polar headgroups to the different thermodynamic functions associated with micellization (Gibbs energy, enthalpy and entropy). Studies on surfactant association to polymers by ITC provide a comprehensive description of the association process, including examples in which particular features revealed by ITC were elucidated by using ancillary techniques such as light or X-ray scattering measurements. Examples of uses of ITC to follow surfactant association to biomolecules such as proteins or DNA, or nanoparticles are also highlighted. Finally, recent theoretical models that were proposed to analyze ITC data in terms of binding/association processes are discussed. This review stresses the importance of using direct calorimetric measurements to obtain and report accurate thermodynamic data, even in complex systems. These data, whenever possible, should be confirmed and associated with other ancillary techniques that allow elucidation of the nature of the transformations detected by calorimetric results, providing a complete description of the process under scrutiny. Copyright © 2015 Elsevier B.V. All rights reserved.

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

    PubMed

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

    2016-01-15

    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. Copyright © 2015 Elsevier B.V. All rights reserved.

  20. Digital holographic interferometry: a novel optical calorimetry technique for radiation dosimetry.

    PubMed

    Cavan, Alicia; Meyer, Juergen

    2014-02-01

    To develop and demonstrate the proof-of-principle of a novel optical calorimetry method to determine radiation absorbed dose in a transparent medium. 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. 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(-4) K). The relative dose fall off was in agreement with treatment planning system modeled data. 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(-4) 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.

  1. Volumetric characterization of ester- and ether-linked lipid bilayers by pressure perturbation calorimetry and densitometry.

    PubMed

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

    2012-04-01

    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. Copyright © 2011 Elsevier B.V. All rights reserved.

  2. Application of calorimetry to microbial biodegradation studies of agrochemicals in oxisols.

    PubMed

    Critter, S A; Airoldi, C

    2001-01-01

    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.

  3. Characterization of parvalbumin and polcalcin divalent ion binding by isothermal titration calorimetry.

    PubMed

    Henzl, Michael T

    2009-01-01

    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.

  4. Quantifying high-affinity binding of hydrophobic ligands by isothermal titration calorimetry.

    PubMed

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

    2012-12-18

    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.

  5. Following mechanical activation of salbutamol sulphate during ball-milling with isothermal calorimetry.

    PubMed

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

    2010-06-30

    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.

  6. New insights into the mechanism of dihydrodipicolinate synthase using isothermal titration calorimetry.

    PubMed

    Muscroft-Taylor, Andrew C; Soares da Costa, Tatiana P; Gerrard, Juliet A

    2010-03-01

    Thermodynamic binding information, obtained via isothermal titration calorimetry (ITC), provides new insights into the binding of substrates, and of allosteric inhibitor interactions of dihydrodipicolinate synthase (DHDPS) from Escherichia coli. DHDPS catalyses the first committed step in (S)-lysine biosynthesis: the Schiff-base mediated aldol condensation of pyruvate with (S)-aspartate semi-aldehyde. Binding studies indicate that pyruvate is a weak binder (0.023 mM) but that (S)-ASA does not interact with the enzyme in the absence of a Schiff-base with pyruvate. These results support the assignment of a ping pong catalytic mechanism in which enthalpically driven Schiff-base formation (DeltaH = -44.5 +/- 0.1 kJ mol(-1)) provides the thermodynamic impetus for pyruvate association. The second substrate, (S)-ASA, was observed to bind to a Schiff-base mimic (DeltaH = -2.8 +/- 0.1 kJ mol(-1)) formed through the reduction of the intermediate pyruvyl-Schiff-base complex. The binding interaction of (S)-lysine was characterised as a cooperative event in which an entropic pre-organisation step (TDeltaS = 17.6 +/- 1.1 kJ mol(-1)) precedes a secondary enthalpic association (DeltaH = -21.6 +/- 0.2 kJ mol(-1)). This allosteric association was determined to be of a mixed competitive nature in which heterotropic ligand cooperativity was observed to subtly influence the binding events. These results offer new insights into the inhibition of this enzyme, a validated antibiotic target.

  7. Improved pyroelectric detectors for single crystal adsorption calorimetry from 100 to 350 K

    NASA Astrophysics Data System (ADS)

    Lew, Wanda; Lytken, Ole; Farmer, Jason A.; Crowe, Matthew C.; Campbell, Charles T.

    2010-02-01

    The adsorption of atoms and molecules on single crystal surfaces allows one to produce well-characterized atomic, molecular, or dissociated adsorbates. Microcalorimetric measurement of the resulting adsorption energies, i.e., single crystal adsorption calorimetry, allows determination of the standard enthalpies of formation of these adsorbates. Methods are described for making an improved heat detector for such measurements, which greatly improves the signal-to-noise ratio, particularly at low temperatures (down to 100 K). The heat detector is an adaptation of a previously introduced design, based on a metallized pyroelectric polymer (β-polyvinylidene fluoride), which is pressed against the back of a single crystal during measurement but removed during sample preparation and annealing. The improvement is achieved by selectively etching the metal coating of the polymer, thus reducing the pyro- and piezoelectric noise from all nonessential regions of the polymer. We, furthermore, describe how to achieve a better thermal contact between the sample and the pyroelectric polymer, without increasing the thermal mass of the detector, resulting in significantly improved sensitivities for both 1 and 127 μm thick samples. The result is a detector which, using 1 μm samples, is ˜40 times more sensitive at 100 K than the traditional polymer-based detector, showing a pulse-to-pulse standard deviation in the heat of adsorption of just 1.3 kJ/mol with gas pulses containing only 1.1% of a monolayer onto Pt(111), for which 1 ML (monolayer) is 1.5×1015 species/cm2. For measurements at 300 K, where especially pyroelectric noise is likely of less concern, the new design improves the sensitivity 3.6-fold compared to the traditional detector. These improvements are furthermore used to propose a new detector design that is able to measure heats of adsorption on samples as thick as 127 μm with reasonable sensitivity.

  8. New developments in calorimetry and thermal analysis above 2000 °C

    NASA Astrophysics Data System (ADS)

    Navrotsky, A.; Ushakov, S.; Kapush, D.; Pavlik, A.; Fyhrie, M.

    2016-12-01

    Thermochemical and structural data above 2000 °C for many refractory oxides, including those of the rare earths, are largely absent. Fusion enthalpies are essential for modeling igneous processes, as are volume changes and enthalpies of high temperature phase transitions . The following set of new experimental techniques has been developed for high temperature studies: i) A commercial ultra-high-temperature differential thermal analyzer (DTA)was modified for use to 2500 °C with sealed crucibles and enthalpies of fusion for La2O3 X-phase (78 kJ/mol at 2300 °C), LaAlO3 perovskite (124 kJ/mol at 2134 °C), MgAl2O4 spinel (180 kJ/mol at 2113 °C) were successfully measured. ii) X-ray and neutron diffraction on crystalline laser heated levitated samples has been used to obtain thermal expansion, refine high temperature crystal structure and for in situ study of phase transitions and melting in variable atmospheres using levitators at the Advanced Photon Source and the Spallation Neutron Source. Pre-melting phase transitions in Y2O3, Ho2O3 and Er2O3 from cubic bixbyite-type structures to disordered hexagonal phases are accompanied by 3-4 % decrease in volume. iii) Drop-and-catch (DnC) calorimetry on laser heated aerodynamically levitated samples was developed to allow direct measurement of fusion enthalpies in various atmospheres. The DnC technique was validated by measurement of fusion enthalpy of Al2O3 corundum (120 kJ/mol at 2054 °C) and used to measure fusion enthalpy of cubic bixbyite type Y2O3 (119 kJ/mol at 2430 °C) and Yb2O3 (97 kJ/mol at 2435 °C). Further methodologiccal improvements and applications to earth and planetary materials are discussed.

  9. Interaction between vitamin D 2 and magnesium in liposomes: Differential scanning calorimetry and FTIR spectroscopy studies

    NASA Astrophysics Data System (ADS)

    Toyran, Neslihan; Severcan, Feride

    2007-08-01

    Magnesium (Mg 2+) ion is of great importance in physiology by its intervention in 300 enzymatic systems, its role in membrane structure, its function in neuromuscular excitability and vitamin D metabolism and/or action. In the present study, the interaction of Mg 2+, at low (1 mole %) and high (7 mole %) concentrations with dipalmitoyl phosphatidylcholine (DPPC) liposomes has been studied in the presence and absence of vitamin D 2 (1 mole %) by using two noninvasive techniques, namely differential scanning calorimetry (DSC) and Fourier transform infrared (FTIR) spectroscopy. DSC studies reveal that the presence of vitamin D 2 in the pure or Mg 2+ (at both low and high concentrations) containing liposomes diminishes the pretransition. The calorimetric results also reveal that, inclusion of Mg 2+ (more significantly at high concentration) into pure or vitamin D 2 containing DPPC liposomes increases the main phase transition temperature. The investigation of the CH 2 symmetric, the CH 3 asymmetric, the C dbnd O stretching, and the PO2- antisymmetric double bond stretching bands in FTIR spectra with respect to changes occurring in the wavenumber and/or the bandwidth values as a function of temperature reveal that, inclusion of vitamin D 2 or Mg 2+ into pure DPPC liposomes orders and decreases the dynamics of the acyl chains in both gel and liquid-crystalline phases and does not induce hydrogen bond formation in the interfacial region. Furthermore, the dynamics of the head groups of the liposomes decreases in both phases. Our findings reveal that, simultaneous presence of vitamin D 2 and Mg 2+ alters the effect of each other, which is reflected as a decrease in the interactions between these two additives within the model membrane.

  10. Prediction of VO2max from a new field test based on portable indirect calorimetry.

    PubMed

    Flouris, Andreas D; Metsios, Giorgos S; Famisis, Konstantinos; Geladas, Nikos; Koutedakis, Yiannis

    2010-01-01

    We assessed the validity and reliability of the new 15m square shuttle run test (SST) for predicting laboratory treadmill test (TT) maximal oxygen uptake (VO(2 max)) compared to the 20 m multistage shuttle run test (MST) in 45 adult males. Thirty participants performed a TT and a SST once to develop a VO( 2max) prediction model. The remaining 15 participants performed the TT and MST once and the SST twice for cross-validation purposes. Throughout testing V O(2max) was determined via portable indirect calorimetry while blood lactate concentration was assessed at the fifth recovery minute. Comparisons of TT V O(2 max) (51.3+/-3.1 ml kg(-1)min(-1)) with SST measured (51.2+/-3.2 ml kg(-1)min(-1)) and predicted (50.9+/-3.3 ml kg(-1)min(-1)) V O(2 max) showed no differences while TT blood lactate was higher compared to SST (10.3+/-1.7 mmol vs. 9.7+/-1.7 mmol, respectively). In contrast, MST measured (53.4+/-3.5 ml kg(-1)min(-1)) and predicted (57.0+/-4.5 ml kg(-1)min(-1)) V O(2 max) and blood lactate (11.2+/-2.0 mmol) were significantly higher compared to TT. No test-retest differences were detected for SST measured and predicted V O(2 max) and blood lactate. It is concluded that the SST is a highly valid and reliable predictive test for V O(2 max). Copyright (c) 2009 Sports Medicine Australia. Published by Elsevier Ltd. All rights reserved.

  11. Active metabolic weight estimation using bioimpedance, indirect calorimetry and the clino-ortho maneuver.

    PubMed

    Cadena, Miguel; Azpiroz, Joaquin; Borja, Gisella; Medel, Humberto; Sandoval, Hector; Rodriguez, Fausto; Flores, Francisco; Flores, Pedro

    2010-01-01

    The resting energy expenditure (REE) and substrate utilization are computed by indirect calorimetry technique (ICT). The REE represents 80-85% of the total energy expenditure (TEE) but only accounts for the 7% of the actual body weight (ABW). The TEE is produced by the organs plus muscles, whereas the REE accounts only for the main organs. An important problem comes up when the REE is computed throughout the fat free mass (FFM) computation or anthropometric measurements because they do not explain the tremendous catabolic variability by ICT when subjects show the same body composition. Therefore, the aim of this work is to develop a method to compute the metabolic active weight (MAW) as a new form that may help to understand the catabolic activity of the body composition. The premise was the clino-ortho maneuver can split the ABW in two parts: one in which the MAW reflects the FFM catabolism while the second part was not considered since there is not energy requirement in it. The experiment design studied 37 young volunteers undergoing the clino-ortho maneuver during fast and postprandial conditions. The results showed REE increments of 21% during phase I (fast), while in phase II (postprandial) only 14% was achieved in ortho-postprandial. Therefore, the computed MAWs were 65.5Kg and 58Kg, respectively, when the ABW average was 70 Kg and the FFM was 50 Kg. One first conclusion was that the 15.5 Kg of the MAW above the FFM could explain a catabolic equivalence which can be exclusively related to the fast-ortho position which can help to classify exclusively the dynamic over activity of the FFM.

  12. An improved estimation of mean body temperature using combined direct calorimetry and thermometry.

    PubMed

    Snellen, J W

    2000-06-01

    The conventional method used to estimate the change in mean body temperature (dMBT) is by taking X% of a body core temperature and (1-X)% of weighted mean skin temperature, the value of X being dependent upon ambient temperature. This technique is used widely, despite opposition from calorimetrists. In the present paper we attempt to provide a better method. Minute-by-minute changes in dMBT, as assessed using calorimetry, and 21 (20 if esophageal temperature was unavailable) various regional temperatures (dRBTs), as assessed using thermometry, including 6 subcutaneous measures, were collected from 7 young male adults at 6 calorimeter temperatures. Since a calorimeter measures only changes in heat storage, which can be converted to dMBT, all body temperatures are expressed as changes from the reasonably constant pre-exposure temperatures. The following three aspects were investigated. (1) The prediction of dMBT from the 21 (or 20) dRBTs with multi-linear regression analysis (MLR). This yields two results, model A with rectal temperature (dTre) alone, and model B with dTre and esophageal temperature (dTes). (2) The prediction of dMBT from dTre with or without dTes and 13 skin surface temperatures combined to one weighted mean skin temperature (dTsk), using MLR. This results in models C and D. Six more models (E-J) were added, representing the above two sets in various combinations with four factors. (3) The conventional method calculated with four values for X. Model A predicted better than 0.3 degree C in 70% of the cases. Model I was the best amongst the models with 13 weighted skin temperatures (better than 0.3 degree C in 60% of the cases). The conventional method was erratic.

  13. Use of Indirect Calorimetry to Detect Overfeeding in Critically Ill Children: Finding the Appropriate Definition.

    PubMed

    Kerklaan, Dorian; Hulst, Jessie M; Verhoeven, Jennifer J; Verbruggen, Sascha C A T; Joosten, Koen F M

    2016-10-01

    Overfeeding during critical illness is associated with adverse effects such as metabolic disturbances and increased risk of infection. Because of the lack of sound studies with clinical endpoints, overfeeding is arbitrarily defined as the ratio caloric intake/measured resting energy expenditure (mREE) or alternatively as a comparison of measured respiratory quotient (RQ) to the predicted RQ based on the macronutrient intake (RQmacr). We aimed to compare definitions of overfeeding in critically ill mechanically ventilated children based on mREE, RQ, and caloric intake to find an appropriate definition. Indirect calorimetry measurements were performed in 78 mechanically ventilated children, median age 6.3 months. Enteral and/or parenteral nutrition was provided according to the local guidelines. Definitions used to indicate overfeeding were the ratio caloric intake/mREE of >110% and >120% and by the measured RQ > RQmacr + 0.05. The proportion of patients identified as overfed varied widely depending on the definition used, ranging from 22% (RQ > RQmacr + 0.05), to 40% and 50% (caloric intake/mREE of >120% and >110%, respectively). Linear regression analysis showed that all patients would be identified as overfed with the definition RQ > RQmacr + 0.05 when the ratio caloric intake/mREE exceeded 165%. Caloric intake was higher in children with a standard deviation-score weight for age <-2. The proportion of mechanically ventilated patients identified as overfed ranged widely depending on the definition applied. These currently used definitions fail to take into account several relevant factors affecting metabolism during critical illness and are therefore not generally applicable to the pediatric intensive care unit population.

  14. The Physics of the Far-infrared-Radio Correlation. I. Calorimetry, Conspiracy, and Implications

    NASA Astrophysics Data System (ADS)

    Lacki, Brian C.; Thompson, Todd A.; Quataert, Eliot

    2010-07-01

    The far-infrared (FIR) and radio luminosities of star-forming galaxies are linearly correlated over a very wide range in star formation rate, from normal spirals like the Milky Way to the most intense starbursts. Using one-zone models of cosmic ray (CR) injection, cooling, and escape in star-forming galaxies, we attempt to reproduce the observed FIR-radio correlation (FRC) over its entire span. The normalization and linearity of the FRC, together with constraints on the CR population in the Milky Way, have strong implications for the CR and magnetic energy densities in star-forming galaxies. We show that for consistency with the FRC, ~2% of the kinetic energy from supernova explosions must go into high-energy primary CR electrons and that ~10%-20% must go into high-energy primary CR protons. Secondary electrons and positrons are likely comparable to or dominate primary electrons in dense starburst galaxies. We discuss the implications of our models for the magnetic field strengths of starbursts, the detectability of starbursts by Fermi, and CR feedback. Overall, our models indicate that both CR protons and electrons escape from low surface density galaxies, but lose most of their energy before escaping dense starbursts. The FRC is caused by a combination of the efficient cooling of CR electrons (calorimetry) in starbursts and a conspiracy of several factors. For lower surface density galaxies, the decreasing radio emission caused by CR escape is balanced by the decreasing FIR emission caused by the low effective UV dust opacity. In starbursts, bremsstrahlung, ionization, and inverse Compton cooling decrease the radio emission, but they are countered by secondary electrons/positrons and the dependence of synchrotron frequency on energy, both of which increase the radio emission. Our conclusions hold for a broad range of variations in our fiducial model, such as those including winds, different magnetic field strengths, and different diffusive escape times.

  15. Evaluation of inductive heating energy of ITER toroidal field conductor by calorimetry

    NASA Astrophysics Data System (ADS)

    Ozeki, H.; Suwa, T.; Saito, T.; Matsui, K.; Isono, T.; Kawano, K.; Takahashi, Y.

    2017-05-01

    The influence of a fast electromagnetic perturbation, such as plasma disruption, on the ITER toroidal field (TF) coil conductor was studied. When a fast magnetic field change is superimposed, the TF conductor is inductively heated by internally generated eddy currents. To measure the inductive heating (IH) energy amount by calorimetry, an IH experiment using short TF conductor samples with length of 20 cm was performed in a liquid He bath. The sample components used were a TF conductor, TF jacket and a TF conductor cable. A 60-turn, single layer solenoid coil was installed around each sample as an IH coil. Also, the Joule heat of the IH coil was solely measured to subtract its thermal contribution from the other samples. A 1 kHz sinusoidal AC current was applied to each IH coil, changing the current amplitude. The heat generated in the samples, including the IH coil, was eventually absorbed into the liquid He, and the liquid He was then vaporized. Thus, the heat amount was measured by a He level sensor inside a gas collection cylinder attached above the sample. The validity of the experimental results was confirmed by comparing them with computation results of the IH energy of the samples with a computation model. Also, the consumed energy was calculated from the measured waveforms of the applied AC voltage and current to the samples. As the result, the measured and calculated IH energy were found to be in good agreement. Finally, based on the results of the experiment, the minimum magnetic field strength, which triggers quench of the TF conductor by fast dumping like plasma disruption, was evaluated using estimated TF conductor minimum quench energy.

  16. Differential scanning calorimetry of gliomas: a new tool in brain cancer diagnostics?

    PubMed

    Chagovetz, Alexis A; Quinn, Colette; Damarse, Neil; Hansen, Lee D; Chagovetz, Alexander M; Jensen, Randy L

    2013-08-01

    Thermal stability signatures of complex molecular interactions in biological fluids can be measured using differential scanning calorimetry (DSC). Evaluating the thermal stability of plasma proteomes offers a method of producing a disease-specific "signature" (thermogram) in neoplastic and autoimmune diseases. The authors describe the use of DSC with human brain tumor tissue to create unique thermograms for correlation with histological tumor classification. Primary brain tumors were classified according to the World Health Organization classification. Tumor samples were digested and assayed by a DSC calorimeter. Experimental thermograms were background subtracted and normalized to the total area of transitions to exclude concentration effects. The resulting thermograms were analyzed by applying 2-state, scaled, Gaussian distributions. Differences in glioma-specific signatures are described by using calculated parameters at transitions that are characterized, in the equilibrium approximation, by a melting temperature (Tm), an apparent enthalpy change (ΔH), and a scaling factor related to the relative abundance of the materials denatured in the transition (Aw). Thermogram signatures of glioblastoma multiforme and low-grade astrocytomas were differentiated by calculated values of Aw3 and Tm4, those of glioblastoma multiforme and oligodendrogliomas were differentiated by Aw2, ΔH2, ΔH4, and Tm4, and those of low-grade astrocytomas and oligodendroglioma were differentiated by Aw4. Our preliminary results suggest that solid brain tumors exhibit specific thermogram profiles that are distinguishable among glioma grades. We anticipate that our results will form the conceptual base of a novel diagnostic assay based on tissue thermograms as a complement to currently used histological analysis.

  17. Analysis of IgG kinetic stability by differential scanning calorimetry, probe fluorescence and light scattering.

    PubMed

    Nemergut, Michal; Žoldák, Gabriel; Schaefer, Jonas V; Kast, Florian; Miškovský, Pavol; Plückthun, Andreas; Sedlák, Erik

    2017-08-19

    Monoclonal antibodies of the immunoglobulin G (IgG) type have become mainstream therapeutics for the treatment of many life-threatening diseases. For their successful application in the clinic and a favorable cost-benefit ratio, the design and formulation of these therapeutic molecules must guarantee long-term stability for an extended period of time. Accelerated stability studies, e.g., by employing thermal denaturation, have the great potential for enabling high-throughput screening campaigns to find optimal molecular variants and formulations in a short time. Surprisingly, no validated quantitative analysis of these accelerated studies has been performed yet, which clearly limits their application for predicting IgG stability. Therefore, we have established a quantitative approach for the assessment of the kinetic stability over a broad range of temperatures. To this end, differential scanning calorimetry (DSC) experiments were performed with a model IgG, testing chaotropic formulations and an extended temperature range, and they were subsequently analyzed by our recently developed three-step sequential model of IgG denaturation, consisting of one reversible and two irreversible steps. A critical comparison of the predictions from this model with data obtained by an orthogonal fluorescence probe method, based on 8-anilinonaphthalene-1-sulfonate binding to partially unfolded states, resulted in very good agreement. In summary, our study highlights the validity of this easy-to-perform analysis for reliably assessing the kinetic stability of IgGs, which can support accelerated formulation development of monoclonal antibodies by ranking different formulations as well as by improving colloidal stability models. © 2017 The Protein Society.

  18. Quantitative crystallinity determination for E1010, a novel carbapenem antibiotic, using differential scanning calorimetry.

    PubMed

    Kushida, Ikuo

    2012-03-01

    The objective of this study was to develop a quantitative crystallinity analysis method for the bulk drug of E1010 ((+)-(4R,5S,6S)-6-[(R)-1-hydroxyethyl]-3-[(2S,4S)-2-[(R)-1-hydroxy-1-[(R)-pyrrolidin-3 -yl]methyl]pyrrolidin-4-yl]thio-4-methyl-7-oxo-1-azabicyclo[3.2.0]hept-2-ene-2-carboxylic acid monohydrochloride), a novel carbapenem antibiotic. X-ray analyses, thermal analyses and hygroscopicity measurements were used to elucidate the crystal structure and the solid state properties. To develop a quantitative method for the crystallinity of E1010 bulk drug, the relationship between enthalpy change obtained by differential scanning calorimetry (DSC) and crystalline form ratio was investigated. E1010 bulk drug was found to exist in a crystalline trihydrate formed in two layers, i.e. a layer of E1010 free form, and a layer consisting of chloride ions and water molecules. The thermal analysis showed an endothermic peak derived from dehydration with the loss of crystal lattices at around 100°C as an onset. The enthalpy change value for the endothermic peak correlated well with crystalline content in binary physical mixtures of the crystalline trihydrate and the amorphous form. In addition, for nine lots of the bulk drug, a positive correlation between the enthalpy change and chemical stability in the solid state was observed. This quantitative analysis of crystallinity using DSC could be applicable for the quality control of the bulk drug to detect variability among manufacturing batches and to estimate the chemical stability of partially amorphous samples. © 2011 The Author. JPP © 2011 Royal Pharmaceutical Society.

  19. Does thermodynamic stability of peritoneal collagen change during laparoscopic cholecystectomies? A differential scanning calorimetry (DSC) study.

    PubMed

    Torres, Kamil; Trębacz, Hanna; Bącik-Donica, Magdalena; Atras, Agnieszka; Torres, Anna; Plewa, Zbigniew

    2014-09-01

    Carbon dioxide pneumoperitoneum used during laparoscopic surgeries alters the integrity of the peritoneum and results in denudation of the basal lamina that might cause altered immune response, inhibited fibrinolysis, hypoxia, and acidosis. The changes in the structure of pneumoperitoneum were described as bulging of mesothelial cells, irregular cell junction's cell membrane degradation, and mesodermal edema. As denaturation of peritoneal proteins reflects overall condition of its structure and interactions with the surrounding molecules, the physical status of collagen was assessed on the basis of parameters of thermal denaturation measured by DSC method. Twenty-four female patients operated on due to cholelithiasis were enrolled in this study. Laparoscopic cholecystectomy was performed using standard four-trocar technique, and standard values of insufflated carbon dioxide pneumoperitoneum were used. After trocar placement, the first collection of peritoneal sample (sample A) was performed. The second peritoneal sample (sample B) was collected after the removal of gall bladder. Differential scanning calorimetry (Q200 calorimeter, TA Instruments) was performed on samples defrosted at room temperature. In all samples of peritoneum, a nonreversible endothermal process recognized as denaturation was observed. Sample B obtained at the end of surgery did not differ from sample A obtained at the beginning in terms of all parameters under study. Temperature of denaturation in A and B was correlated only marginally, but enthalpy and specific heat were significantly correlated. The analysis of data from DSC measurements did not reveal differences in physical stability of collagen in peritoneal samples obtained at the beginning and at the end of surgery. Significant negative correlations between duration of CO2 pneumoperitoneum and enthalpy of denaturation in sample B were found. Differences in enthalpy of denaturation may reflect a quantitative relation between amount of

  20. Differential scanning calorimetry predicts the critical quality attributes of amorphous glibenclamide.

    PubMed

    Mah, Pei T; Laaksonen, Timo; Rades, Thomas; Peltonen, Leena; Strachan, Clare J

    2015-12-01

    Selection of a crystallinity detection tool that is able to predict the critical quality attributes of amorphous formulations is imperative for the development of process control strategies. The main aim of this study was to determine the crystallinity detection tool that best predicts the critical quality attributes (i.e. physical stability and dissolution behaviour) of amorphous material. Glibenclamide (model drug) was milled for various durations using a planetary mill and characterised using Raman spectroscopy and differential scanning calorimetry (DSC). Physical stability studies upon storage at 60°C/0% RH and dissolution studies (non-sink conditions) were performed on the milled glibenclamide samples. Different milling durations were needed to render glibenclamide fully amorphous according to Raman spectroscopy (60min) and onset of crystallisation using DSC (150min). This could be due to the superiority of DSC (onset of crystallisation) in detecting residual crystallinity in the samples milled for between 60 and 120min, which were not detectable with Raman spectroscopy. The physical stability upon storage and dissolution behaviour of the milled samples improved with increased milling duration and plateaus were reached after milling for certain periods of time (physical stability - 150min; dissolution - 120min). The residual crystallinity which was detectable with DSC (onset of crystallisation), but not with Raman spectroscopy, adversely affected the critical quality attributes of milled glibenclamide samples. In addition, mathematical simulations were performed on the dissolution data to determine the solubility advantages of the milled glibenclamide samples and to describe the crystallisation process that occurred during dissolution in pH7.4 phosphate buffer. In conclusion, the onset of crystallisation obtained from DSC measurements best predicts the critical quality attributes of milled glibenclamide samples and mathematical simulations based on the

  1. Modulation calorimetry in diamond anvil cells. II. Joule-heating design and prototypes

    NASA Astrophysics Data System (ADS)

    Geballe, Zachary M.; Struzhkin, Viktor V.; Townley, Andrew; Jeanloz, Raymond

    2017-04-01

    Part I shows that quantitative measurements of heat capacity are theoretically possible inside diamond anvil cells via high-frequency Joule heating (100 kHz-10 MHz), opening up the possibility of new methods to detect and characterize transformations at high-pressure such as the glass transitions, melting, magnetic orderings, and the onset of superconductivity. Here, we test the possibility outlined in Part I, using prototypes and detailed numerical models. First, a coupled electrical-thermal numerical model shows that specific heat of metals inside diamond cells can be measured directly using ˜1 MHz frequency, with <10 % accuracy. Second, we test physical models of high-pressure experiments, i.e., diamond-cell mock-ups. Metal foils of 2-6 μm-thickness are clamped between glass insulation inside diamond anvil cells. Fitting data from 10 Hz to ˜30 kHz, we infer the specific heat capacities of Fe, Pt, and Ni with ±20%-30% accuracy. The electrical test equipment generates -80 dBc spurious harmonics, which overwhelm the thermally induced harmonics at higher frequencies, disallowing the high precision expected from numerical models. An alternative Joule-heating calorimetry experiment, on the other hand, does allow absolute measurements with <10 % accuracy, despite the -80 dBc spurious harmonics: the measurement of thermal effusivity, √{ρc k } (ρ, c, and k being density, specific heat, and thermal conductivity), of the insulation surrounding a thin-film heater. Using a ˜50 nm-thick Pt heater surrounded by glass and 10 Hz-300 kHz frequency, we measure thermal effusivity with ±6 % accuracy inside the sample chamber of a diamond anvil cell.

  2. Use of differential scanning calorimetry to detect canola oil (Brassica napus L.) adulterated with lard stearin.

    PubMed

    Marikkar, Jalaldeen Mohammed Nazrim; Rana, Sohel

    2014-01-01

    A study was conducted to detect and quantify lard stearin (LS) content in canola oil (CaO) using differential scanning calorimetry (DSC). Authentic samples of CaO were obtained from a reliable supplier and the adulterant LS were obtained through a fractional crystallization procedure as reported previously. Pure CaO samples spiked with LS in levels ranging from 5 to 15% (w/w) were analyzed using DSC to obtain their cooling and heating profiles. The results showed that samples contaminated with LS at 5% (w/w) level can be detected using characteristic contaminant peaks appearing in the higher temperature regions (0 to 70°C) of the cooling and heating curves. Pearson correlation analysis of LS content against individual DSC parameters of the adulterant peak namely peak temperature, peak area, peak onset temperature indicated that there were strong correlations between these with the LS content of the CaO admixtures. When these three parameters were engaged as variables in the execution of the stepwise regression procedure, predictive models for determination of LS content in CaO were obtained. The predictive models obtained with single DSC parameter had relatively lower coefficient of determination (R(2) value) and higher standard error than the models obtained using two DSC parameters in combination. This study concluded that the predictive models obtained with peak area and peak onset temperature of the adulteration peak would be more accurate for prediction of LS content in CaO based on the highest coefficient of determination (R(2) value) and smallest standard error.

  3. Fourier transform infrared spectroscopy and differential scanning calorimetry studies of fatty acid homogeneous ceramide 2.

    PubMed

    Chen, H; Mendelsohn, R; Rerek, M E; Moore, D J

    2000-09-29

    Ceramides provide a major component of the barrier function of skin. An understanding of barrier organization requires a detailed characterization of ceramide phase behavior and molecular interactions. Toward this end, Fourier transform infrared (FTIR) and differential scanning calorimetry (DSC) studies of ceramide 2 analogues (non-hydroxylated fatty acid N-acyl sphingosines) of specific chain lengths (C(14), C(16), C(18), C(20)) are presented. In addition, the molecular interactions of the individual chains in each molecule are elucidated through thermotropic FTIR studies of derivatives possessing perdeuterated fatty acid chains. DSC data showed a much smaller chain length variation (for the C(16), C(18), C(20) derivatives) in the main order-disorder transition temperature (approx. 93+/-1 degrees C) than is observed in the corresponding series of phosphatidylcholines, consistent with minimal ceramide hydration. The temperature dependence of the methylene stretching and scissoring modes revealed a solid-solid phase transition at 20-25 degrees C below the main order-disorder transition accompanied by chain packing alterations from orthorhombic-->hexagonal subcells. The chain packing transition was accompanied by enhanced penetration of water into the polar region. This was deduced from the temperature dependence of the amide I and II modes, which provide direct evidence for H-->D exchange. The CD(2) scissoring mode splitting of the deuterated fatty acid constituent of the C(16), C(18), C(20) chains revealed preferential segregation of microdomains (3-5 chains) of this species within the orthorhombic phase. In contrast, the sphingosine base chains appeared to be sufficiently separated so as to inhibit interchain vibrational coupling between them. FTIR spectroscopy provides a convenient means for characterizing domain formation, chain packing, and hydration sites of these phases, which are highly ordered under physiological conditions.

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

    SciTech Connect

    Cavan, Alicia; Meyer, Juergen

    2014-02-15

    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.

  5. Assessing Coupled Protein Folding and Binding Through Temperature-Dependent Isothermal Titration Calorimetry.

    PubMed

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

    2016-01-01

    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. Practical utility and reliability of whole-room calorimetry in young children.

    PubMed

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

    2013-05-28

    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.

  7. Estimation of drug solubility in polymers via differential scanning calorimetry and utilization of the fox equation.

    PubMed

    Haddadin, Raja; Qian, Feng; Desikan, Sridhar; Hussain, Munir; Smith, Ronald L

    2009-01-01

    The solubility of drugs in polyethylene glycol 400 (PEG 400) was estimated and rank ordered using a differential scanning calorimetry (DSC) method and the Fox Equation. Drug-polymer binary mixtures of six compounds (Ibuprofen, Indomethacin, Naproxen, and three proprietary compounds: PC-1 through PC-3) with PEG 400 were heat treated using a three-cycle DSC method to establish a correlation between equilibrium solubility and temperature. Thermal events such as heat of fusion, heat of recrystallization and glass transition temperature, T(g), were used to calculate the drug solubility at multiple higher temperatures through the Fox Equation. Subsequently, a van't Hoff plot was constructed to estimate the drug solubility at room temperature, and the values were compared with those measured by HPLC. With the exception of Naproxen, room temperature solubilities of the remaining drug compounds in PEG 400 were determined by this thermal method approach, and compared with those measured by HPLC: 26.7% vs. 24.7% for Ibuprofen, 5.8% vs. 9.6% for Indomethacin, 3.1 % vs. 1.5% for PC-1, 2.3% vs. 1.3% for PC-2, and 1.4% vs. 0.2% for PC-3 in PEG 400. There was good concordance in solubility rank order estimates between the two methods. These collective results support the potential utility of the thermal method as an alternative to other methods for estimation of drug solubility in polymers which is an important determinant in the design of physically-stable amorphous systems.

  8. Thermal porosity analysis of croscarmellose sodium and sodium starch glycolate by differential scanning calorimetry.

    PubMed

    Faroongsarng, Damrongsak; Peck, Garnet E

    2003-12-30

    The aim of the study was to demonstrate the applicability of differential scanning calorimetry (DSC) on porosity analysis for cellulose and starch. Croscarmellose sodium (CCS) and sodium starch glycolate (SSG) were allowed to sorb moisture in 85%, 90%, 95%, and 100% relative humidity (RH) at 40 degrees C for 24 hours. The pretreated samples were then subjected to DSC running temperature ranging from 25 degrees C to -50 degrees C at a cooling rate of 10 degrees C/min. The cooling traces of water crystallization, if present, were transformed to porosity distribution via capillary condensation using Kelvin's equation. The porosity analysis of CCS and SSG was also done using nitrogen adsorption as a reference method. It was found that sorbed water could not be frozen (in cases of 85% and 90% RH) until the moisture content exceeded a cutoff value (in cases of 95% and 100% RH). The nonfreezable moisture content was referred to tightly bound, plasticizing water, whereas the frozen one may be attributed to loosely bound water condensation in pore structure of CCS and SSG surfaces. Not only capillary condensation but also the tightly bound, nonfreezable monolayer water lying along the inner pores of the surface contributed to porosity determination. Good agreement with less than 5% deviation of mean pore size was observed when the results were compared with nitrogen adsorption. The narrower pore size distributions, however, were obtained because of the limitations of the technique. It was concluded that pore analysis by DSC could be successful. Further research needs to be done to account for limitations and to extend the applicability of the technique.

  9. Proceedings of the Eleventh International Conference on Calorimetry in Particle Physics

    NASA Astrophysics Data System (ADS)

    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

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

    PubMed

    Renaud, James; Sarfehnia, Arman; Marchant, Kristin; McEwen, Malcolm; Ross, Carl; Seuntjens, Jan

    2015-11-01

    electron energy dependence of the PTW Roos data measured in this work and a recent MC-based study are also shown. 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 (R50=2.25 cm).

  11. Collecting Variable-concentration Isothermal Titration Calorimetry Datasets in Order to Determine Binding Mechanisms

    PubMed Central

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

    2011-01-01

    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

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

    SciTech Connect

    Renaud, James Seuntjens, Jan; Sarfehnia, Arman; Marchant, Kristin; McEwen, Malcolm; Ross, Carl

    2015-11-15

    . 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)

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

    SciTech Connect

    Flores-Martinez, E; Malin, M; DeWerd, L

    2015-06-15

    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.

  14. Tetraether bolaform amphiphiles as models of archaebacterial membrane lipids: Synthesis, differential scanning calorimetry, and monolayer studies

    SciTech Connect

    Kim, J.M.; Thompson, D.H. )

    1992-02-01

    Four racemic tetraether lipids containing a single 1,[omega]-polymethylene chain ([omega] = 16, 20) bridging two glycerophosphate headgroups (bolaform amphiphiles) have been synthesized. These materials have been characterized at the air-water interface by monolayer balance methods and in buffered solution by differential scanning calorimetry (DSC) and negative stain transmission electron microscopy (TEM). Molecular areas in excess of 100 [angstrom][sup 2]/molecule at 40 mN/m[sup 2] were observed for all bolaamphiphiles studied, suggesting a U-shaped molecular conformation that places both phosphate headgroups in the water subphase. Aqueous dispersions of these lipids have thermal and morphological properties that depend on molecular structure and solution pH. Phase transition temperatures (T[sub c]) of the structural isomers, 2,2[prime]-di-O-decyl-1, 1[prime]-O-eicosamethylene-rac-diglycero-3,3[prime]-diphosphate (PS20) and 1,1[prime]-di-O-decyl-2,2[prime]-O-eicosamethylene-3,3[prime]-diphosphate (SS20), were 49 and 38 [degrees]C, respectively, at pH 2.5. A reduction in the observed T[sub c] of [approximately] 14 [degrees]C occurred when the pH was raised to 8.1. The closely related structural analogue, 1,1[prime]-O-eicosamethylene-2-O-eicosyl-rac-diglycero-3,2[prime], 3[prime]-diphosphate (PA20), has a T[sub c] 85 [degrees]C. No phase transition was observed above 5 [degrees]C for 2,2[prime]-O-dioctyl-1,1 [prime]-O-hexadecylmethylene-rac-diglycero-3, 3[prime]-disphosphoric acid (PS16). Multilamellar structures with hydrocarbon-region spacings of 24-30 [angstrom] and overall lengths approaching 0.3 [mu]m were observed by negative stain electron microscopy. The observed lamellae distance is in good agreement with the membrane thickness expected for a bolaamphiphile in its all-anti conformation. 56 refs., 8 figs., 1 tab.

  15. Black carbon quantification in charcoal-enriched soils by differential scanning calorimetry

    NASA Astrophysics Data System (ADS)

    Hardy, Brieuc; Cornelis, Jean-Thomas; Leifeld, Jens

    2015-04-01

    Black carbon (BC), the solid residue of the incomplete combustion of biomass and fossil fuels, is ubiquitous in soil and sediments, fulfilling several environmental services such as long-term carbon storage. BC is a particularly important terrestrial carbon pool due to its large residence time compared to thermally unaltered organic matter, which is largely attributed to its aromatic structure. However, BC refers to a wide range of pyrogenic products from partly charred biomass to highly condensed soot, with a degree of aromaticity and aromatic condensation varying to a large extend across the BC continuum. As a result, BC quantification largely depends on operational definitions, with the extraction efficiency of each method varying across the entire BC range. In our study, we investigated the adequacy of differential scanning calorimetry (DSC) for the quantification of BC in charcoal-enriched soils collected in the topsoil of pre-industrial charcoal kilns in forest and cropland of Wallonia, Belgium, where charcoal residues are mixed to uncharred soil organic matter (SOM). We compared the results to the fraction of the total organic carbon (TOC) resisting to K2Cr2O7 oxidation, another simple method often used for BC measurement. In our soils, DSC clearly discriminates SOM from chars. SOM is less thermally stable than charcoal and shows a peak maximum around 295°C. In forest and agricultural charcoal-enriched soils, three peaks were attributed to the thermal degradation of BC at 395, 458 and 523°C and 367, 420 and 502 °C, respectively. In cropland, the amount of BC calculated from the DSC peaks is closely related (slope of the linear regression = 0.985, R²=0.914) to the extra organic carbon content measured at charcoal kiln sites relative to the charcoal-unaffected adjacent soils, which is a positive indicator of the suitability of DSC for charcoal quantification in soil. The first BC peak, which may correspond to highly degraded charcoal, contributes to a

  16. Approximate Time to Steady-state Resting Energy Expenditure Using Indirect Calorimetry in Young, Healthy Adults

    PubMed Central

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

    2016-01-01

    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 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. PMID:27857943

  17. Differential scanning calorimetry study of glycerinated rabbit psoas muscle fibres in intermediate state of ATP hydrolysis

    PubMed Central

    Dergez, Timea; Lőrinczy, Dénes; Könczöl, Franciska; Farkas, Nelli; Belagyi, Joseph

    2007-01-01

    Background Thermal denaturation experiments were extended to study the thermal behaviour of the main motor proteins (actin and myosin) in their native environment in striated muscle fibres. The interaction of actin with myosin in the highly organized muscle structure is affected by internal forces; therefore their altered conformation and interaction may differ from those obtained in solution. The energetics of long functioning intermediate states of ATP hydrolysis cycle was studied in muscle fibres by differential scanning calorimetry (DSC). Results SETARAM Micro DSC-II was used to monitor the thermal denaturation of the fibre system in rigor and in the presence of nucleotide and nucleotide analogues. The AM.ADP.Pi state of the ATP hydrolysis cycle has a very short lifetime therefore, we mimicked the different intermediate states with AMP.PNP and/or inorganic phosphate analogues Vi and AlF4 or BeFx. Studying glycerol-extracted muscle fibres from the rabbit psoas muscle by DSC, three characteristic thermal transitions were detected in rigor. The thermal transitions can be assigned to myosin heads, myosin rods and actin with transition temperatures (Tm) of 52.9 ± 0.7°C, 57.9 ± 0.7°C, 63.7 ± 1.0°C. In different intermediate states of the ATP hydrolysis mimicked by nucleotide analogues a fourth thermal transition was also detected which is very likely connected with nucleotide binding domain of myosin and/or actin filaments. This transition temperature Tm4 depended on the mimicked intermediate states, and varied in the range of 66°C – 77°C. Conclusion According to DSC measurements, strongly and weakly binding states of myosin to actin were significantly different. In the presence of ADP only a moderate change of the DSC pattern was detected in comparison with rigor, whereas in ADP.Pi state trapped by Vi, AlF4 or BeFx a remarkable stabilization was detected on the myosin head and actin filament which is reflected in a 3.0 – 10.0°C shift in Tm to higher

  18. SU-E-T-267: Development of the Compact Graphite Calorimetry System for the High Energy Photon Beam

    SciTech Connect

    Kim, B. C.; Kim, I. J.; Kim, J. H.; Yi, C. Y.

    2015-06-15

    Purpose: Graphite calorimeter systems are used for the absolute photon dosimetry. But many electronics are demanded in order to measure the tiny temperature changes. Minimizing the control system is needed to make a portable graphite calorimeter. Methods: A Domen-type graphite calorimetry system is constructing to measure the absorbed dose of the high energy photon beam. The graphite calorimeter divided into three parts, Core, Jacket, and Shield. In order to measure the temperature rising of the core due to the radiation accurately, the temperatures of the jacket and the shield should be controlled properly. A commercial temperature controller (Model 350, Lake Shore Cryogenics) was used to minimize the size of control system for making a portable graphite calorimetry system at the cost of the measurement uncertainty. The PID control of the jacket is conducted by the software (LabView) and Model 350 maintain the temperature of shield. Results: Our design value of the heat deposition power in the core is 0.04 mW for the dose rate of 3 Gy/min where the temperature sensitivity of the graphite is 1.4 mK/Gy. While the residuals of the Steinhart-hart equation fitting for the core thermistor were less than 0.1 mK, the temperature resolution of Model 350 is 1 mK. The temperature of the shield was kept within the 5 mK when the room temperature variation was about 0.5 K. Conclusion: The resolution of Model 350 for the temperature measurement and control is not good enough as the control system for the compact graphite calorimetry system. But The performance of Model 350 is good enough to maintain the temperature of the shield constantly. The Model 350 will be replaced by the AC resistance bridge (Model 372, Lake Shore Cryogenics) for the core temperature measurement and the jacket control.

  19. Phase Polymorphism of [Mn(DMSO)6](ClO4)2 Studied by Differential Scanning Calorimetry

    NASA Astrophysics Data System (ADS)

    Migdał-Mikuli, Anna; Szostak, Elżbieta

    2005-04-01

    Six solid phases of [Mn(DMSO)6](ClO4)2 have been detected by differential scanning calorimetry. The phase transitions were found between the following solid phases: stable KIc ↔ stable KIb at TC5 = 225 K, metastable KIII ↔ metastable KII at TC4 = 322 K, stable KIb ↔ stable KIa at TC3 = 365 K, metastable KII↔overcooled K0 at TC2 = 376 K and stable KIa→stable K0 at TC1 = 379 K. The title compound melts at Tm = 488 K.

  20. Temperature-modulated calorimetry of the frequency dependence of the glass transition of poly(ethylene terephthalate) and ....

    SciTech Connect

    Wunderlich, B.; Okazaki, I.

    1997-03-01

    Temperature-modulated differential scanning calorimetry, TMDSC, is new technique that permits to measure the apparent heat capacity vs modulation frequency. The method is briefly described and a quasi- isothermal measurement method is used to derive the kinetic parameters for PET and PS. A first-order kinetics expression was used to describe the approach to equilibrium and point out the limits caused by asymmetry and cooperativity of the kinetics. Use of a complex description of heat capacity and entropy is discussed. Activation energies vary from 75 to 350 kJ/mol, dependent on thermal pretreatment and the preexponential factor is correlated with the activation energy.