Heat capacity of solid‐state biopolymers by thermal analysis

Heat capacities in the solid state of four globular proteins (bovine β‐lactoglobulin, chicken lysozyme, ovalbumine, and horse myoglobin) and of the poly(amino acid) poly(L ‐tryptophan) have been determined using the Advanced THermal Analysis System (ATHAS). The experimental measurements were performed with adiabatic and differential scanning calorimetry over wide temperature ranges. The heat capacities were linked to an approximate vibrational spectrum by making use of known group vibrations and of a set of parameters, Θ₁ and Θ₃, of the Tarasov function for the skeletal vibrations. Good agreement was found between experiments and calculations with root mean square errors mostly within ±3%. The experimental data were analyzed also with an empirical addition scheme using the known data for poly(amino acid)s measured earlier. Based on this study, vibrational heat capacities can now be predicted for all proteins with an accuracy comparable to common experiments. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 2093–2102, 1999     

Multidimensional solid state NMR of anisotropic interactions in peptides and proteins

Accurate determinations of chemical shift anisotropy (CSA) tensors are valuable for NMR of biological systems. In this review we describe recent developments in CSA measurement techniques and applications, particularly in the context of peptides and proteins. These techniques include goniometeric measurements of single crystals, slow magic-angle spinning studies of powder samples, and CSA recoupling under moderate to fast MAS. Experimental CSA data can be analyzed by comparison with ab initio calculations for structure determination and refinement. This approach has particularly high potential for aliphatic (13)C analysis, especially Calpha tensors which are directly related to structure. Carbonyl and (15)N CSA tensors demonstrate a more complex dependence upon hydrogen bonding and electrostatics, in addition to conformational dependence. The improved understanding of these tensors and the ability to measure them quantitatively provide additional opportunities for structure determination, as well as insights into dynamics.     

Heat capacity calorimetry

Experimental heat capacity measurements of α-ZrW₂O₈, and zeolitic polymorphs of SiO₂, BEA and MFI, have been made from 0.6 to 400 K. Measurements on β-ZrMo₂O₈ have been made from 8 to 400 K. Analysis of the results yields evidence for very low frequency modes in all four materials. These modes are responsible for negative thermal expansion behavior in α-ZrW₂O₈ and β-ZrMo₂O₈. Negative thermal expansion has been observed in some pure SiO₂ zeolites, but no studies have been made to look for it in BEA and MFI. The appearance of low frequency modes in these two zeolites suggests that temperature dependent structural investigations would be worthwhile. These modes are lower in energy than the Boson peak in vitreous silica. This revised version was published online in August 2006 with corrections to the Cover Date.     

Heat capacities of solid ortho—para mixtures of deuterium in the ordered state

The heat capacities of three ortho—para mixtures of solid deuterium in the rotationally ordered state as a function of temperature as well as the order—disorder transition temperature, T_c(x) for several compositions have been measured. The rotational heat capacities for all three mixtures, x (para or J = 1 mole fraction) = 0.69₉, 0.81₉ and 0.92₁ per mole of J = 1 species can be represented by a single function in terms of the reduced temperatures, T_c(x)/T, which to a good approximation is given by

, where Γ⁰_eff(1)/k = 1.0 deg is the effective electric quadrupolar coupling constant for the anisotropic interactions in pure para D₂ and T_c(1) = 4.05 degrees the order—disorder transition temperature. It is shown that this correlation follows from the assumption that both the libron energies and band widths of the libron modes scale with composition in a manner identical to the transition temperatures, namely

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Sensitive high resolution inverse detection NMR spectroscopy of proteins in the solid state

A new indirect detection scheme for obtaining (15)N/(1)H shift correlation spectra in crystalline proteins is described. Excellent water suppression is achieved without the need for pulsed field gradients, and using only a 2-step phase cycle. Careful attention to overall NMR instrument stability was found critical for obtaining the best resolution and sensitivity. Magnetic dilution by deuteration of the protein in combination with high-speed magic angle spinning produces (1)H resonances averaging only 0.22 ppm in width, and in some cases lines as narrow as 0.17 ppm are obtained. In application to two different polymorphs of ubiquitin, structure dependent differences in both (15)N and (1)H amide chemical shifts are observed. In one case, distinct shifts for different molecules in the asymmetric unit are seen, and all differ substantially from solution NMR shifts. A gain of 7 in sensitivity makes the method competitive with solution NMR as long as nanocrystalline samples are available.     

Heat capacity of fluoropolymers

The heat capacities of poly(vinyl fluoride), poly(vinylidene fluoride), and polytrifluoroethylene have been measured between 80 and 340°K. The results can be expressed as the sum of two terms: the optical contribution calculated from the vibrational band assignments in the literature and the acoustical contribution calculated according to the Tarasov continuum model. Combining our data with those for polyethylene and polytetrafluoroethylene, it is concluded that the force constant for one-dimensional intrachain interaction is approximately constant for all polymers with carbon backbones. The force constant for three-dimensional interchain interaction is one order of magnitude smaller than the one-dimensional force constant, and decreases when the hydrogen atoms in polyethylene are replaced by fluorine atoms. The thermodynamic functions for the three polymers have been evaluated. Glass transitions at 228°K and 305°K have been found in poly(vinylidene fluoride) and polytrifluoroethylene, respectively.     

Heat capacity of cheese

The heat capacity of several samples of hard cheese, semi-hard cheese and soft cheese was determined by conventional differential scanning calorimetry (DSC) and by temperature modulated DSC. Additionally, the gross composition of the cheeses was analysed, and equations from the literature were used to calculate the heat capacity therefrom. Both analytical methods were suitable to determine the heat capacity of the cheese samples whereas only one out of three equations proposed for the calculation of the heat capacity of foods from composition data led to results which were comparable with analytical data. As the equation coefficients for particular constituents are responsible for the deviations in the calculated heat capacities the differences between calculated and measured values increase with a decreasing moisture content of the cheeses.     

Solvent free reactions in the solid state: solid state metathesis

Transition Metal Chemistry -     

Heat capacity functions of polystyrene in glassy and in liquid amorphous state and glass transition

The heat capacity or the specific heat is for any crystalline, partially amorphous or completely amorphous substance or material a significant thermodynamic property. The glass transition may be regarded as the melting point of amorphous substances and materials, a transition property of an outstanding technical importance. A crucial point is the fact that the presence of a glass transition is an unequivocal proof of an amorphous content of a material. Furthermore, the change of the specific heat at the glass transition temperature enables the quantitative determination of the amorphicity on a relative or absolute level of any substance or material. The absolute determination of the amorphicity affords a calibration with a reference corresponding to the material under investigation. The crystallinity for this reference substance must be known from the preparation and or by any independent analytical method. The literature data for the specific heat and the glass transition of polystyrene were collected and evaluated. Data were found for the specific heat in literature from 10 to 470 K. The data were unified for each of the reported temperature in a mean value and the corresponding standard deviation was determined. An excellent conformity was found in the glassy state of polystyrene with standard deviations lower than 0.7%. The standard deviations above the glass transition were considerably higher.     

Heat capacity of molten polymers

Heat capacities of molten polyethylene, polypropylene, poly-1-butene, polystyrene, and poly(methyl methacrylate) were measured over a wide range of temperature by using a differential scanning calorimeter. The upper limit of temperature was established for each polymer at about 10°K below the beginning of thermal decomposition. For poly-1-butene and poly(methyl methacrylate) the solid-state heat capacity was also measured starting from room temperature. Several samples of each polymer were used so that average values of heat capacities could be established (reported in 10°K intervals). The data revealed for all polymers a nearly linear increase of heat capacity with increasing temperature over the whole temperature range investigated.     

Nucleation of ordered solid phases of proteins via a disordered high-density state: phenomenological approach

Nucleation of ordered solid phases of proteins triggers numerous phenomena in laboratory, industry, and in healthy and sick organisms. Recent simulations and experiments with protein crystals suggest that the formation of an ordered crystalline nucleus is preceded by a disordered high-density cluster, akin to a droplet of high-density liquid that has been observed with some proteins; this mechanism allowed a qualitative explanation of recorded complex nucleation kinetics curves. Here, we present a simple phenomenological theory that takes into account intermediate high-density metastable states in the nucleation process. Nucleation rate data at varying temperature and protein concentration are reproduced with high fidelity using literature values of the thermodynamic and kinetic parameters of the system. Our calculations show that the growth rate of the near-critical and supercritical ordered clusters within the dense intermediate is a major factor for the overall nucleation rate. This highlights the role of viscosity within the dense intermediate for the formation of the ordered nucleus. The model provides an understanding of the action of additives that delay or accelerate nucleation and presents a framework within which the nucleation of other ordered protein solid phases, e.g., the sickle cell hemoglobin polymers, can be analyzed.     

Heat capacity of copper hydride

The heat capacity of copper hydride has been measured in the temperature range 2–60 and 60–250 K using two adiabatic calorimeters. Special procedure for the purification of CuH has been applied and a careful analysis of sample contamination has been performed. The experimental results have been extrapolated up to 300 K due to instability of the copper hydride at room temperature. From the temperature dependence of heat capacity the values of entropy S°(T), thermal part of enthalpy H°(T)−H°(0) and Gibbs function [−(G°(T)−H°(0))] have been calculated assuming S°(0)=0. The standard absolute entropy, standard entropy of formation from the elements and enthalpy of decomposition of copper hydride from the elements have been calculated and found to be 130.8 J K⁻¹ mol⁻¹ (H₂), −85.1 J K⁻¹ mol⁻¹ (H₂), −55.1 kJ mol⁻¹ (H₂), respectively. These new results gave the possibility of discussion on thermodynamic properties of copper hydride. Debye temperature has been for the first time determined experimentally.     

Heat capacity of vanadium-oxygen alloy

Heat capacities of vanadium-oxygen alloys with various compositions, VO_0.0834, VO_0.1127, VO_0.1245, and VO_0.1296, were measured from 320 to 920K by adiabatic scanning calorimetry. A heat capacity anomaly due to order-disorder rearrangement of oxygen atoms was observed for all the compositions. The transition temperatures from α′ to β phase were found to be 780, 791, 786, and 768K for VO_0.0839, VO_0.1127, VO_0.1245, and VO_0.1296, respectively. The transition temperatures from β′ to β were also observed to be 665 and 660K for VO_0.1245 and VO_0.1296, respectively, but they shifted to lower temperatures in repeated measurements. The excess heat capacity due to order-disorder transition was obtained by assuming that the heat capacity can be expressed as the sum of a harmonic term of lattice vibration, a dilational term, an electronic term, and an anharmonic term of lattice vibration. The entropy changes due to the transition for VO_0.0834, VO_0.1127, VO_0.1245, VO_0.1296 were determined from the excess heat capacities to be 1.90, 2.88, 2.82, and 2.88 J K^?1 mole^?1, respectively, values which were explained by calculating the entropy changes due to the order-disorder rearrangement of oxygen atoms in the superstructures of VO_x alloys. From the O/V dependence of the transition temperature and entropy change, the most stable composition of the α′ phase was thought to be V₄₈O₅.     

Heat capacity of crystalline GaN

The heat capacity of gallium nitride has been measured by DSC method using DuPont Thermal Analyst 2100, DSC 951 unit in the temperature range (300–850 K). The temperature dependence of the heat capacity can be presented in the following form: C _p=32.960+0.162·10⁻¹ T+2360170T ⁻²-775370000T ⁻³.     

Heat capacity of LiInTe2

The heat capacity of LiInTe₂ at constant pressure was measured with an adiabatic vacuum calorimeter in the temperature rangeT=7–300 K. The standard molar enthalpyH _m ⁰ —H _m ⁰ (0) and the standard molar entropyS ⁰ (T) were calculated. From a theoretical analysis, the contribution to the heat capacity due to the lattice anharmonicity was estimated.The increased effect of the lattice anharmonicity in LiInTe₂ is caused by specific properties of the Li-Te bond.

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Zusammenfassung Die Wärmekapazität von LiInTe₂ bei konstantem Druck wurde mit einem adiabatischen Vakuumkalorimeter im Temperaturbereich 7 T 300 K bestimmt. Die molare StandardenthalpieH _m ⁰ — H _m ⁰ (0) und die molare StandardentropieS ⁰ (T) wurden berechnet. Aus einer theoretischen Analys wurde der Anteil der Gitteranharmonizität an der Wärmekapazität abgeschätzt. Der erhöhte Einfluss der Gitteranharmonitität in LiInTe₂ wird durch spezifische Eigenschaften der Li-Te-Bindung verursacht

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7–300 LiInTe₂. H _M ⁰ -H _M ⁰ (0) S ⁰(T). . LiInTe₂ Li-.

     

Retarded solid state reactions

Reconstructive phase transitions and formation or decomposition reactions in the solid state exhibit in DTA-measurements a more or less great hysteresis between the temperatures from heating and cooling curves; at worst the reaction can be suppressed completely. By e.m.f.vs. T-measurements in appropriate galvanic cells for solid electrolytes equilibrium temperatures in the case of such kinetic hindrance can be determined and additionally the existence of metastable states can be proved.

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Zusammenfassung Rekonstruktive Phasenumwandlungen sowie Bildungs- und Zersetzungsreaktionen im festen Zustand zeigen bei DTA-Messungen eine mehr oder minder große Hysteresis zwischen den aus Aufheiz- bzw. Abkühlkurven ermittelten Temperaturen; schlimmstenfalls kann die Festkörperreaktion völlig unterdrückt sein. Mißt man in geeigneten galvanischen Zellen für Festelektrolyte EMK-gegen-T-Kurven, so erhält man auch im Falle kinetischer Hemmungen Gleichgewichtstemperaturen und kann darüber hinaus das Vorliegen metastabiler Zustände nachweisen.

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We have to thank the Deutsche Forschungsgemeinschaft and the Fonds der Chemischen Industry for supporting our work from the outset.     

Selective solid state photooxidant

Irradiation of biphenyl encapsulated in the cavities of a NaZSM-5 zeolite framework has been reported to result in the formation of an extremely long-lived radical cation. Here, we show that such zeolite encapsulated radical cations can act as irreversible one-electron oxidants for simple alkenes and dienes, in a solid-state analogue to solution-phase cosensitization. Compared to the well-known semiconductor photooxidizers, such as titanium dioxide, the NaZSM-5 zeolite-based solid photooxidants exhibit enhanced selectivity based on oxidation potential, molecular size and shape, and Lewis base character.