High-resolution Calorimetry Research Articles

Mitochondrial function in skeletal muscle contributes to reproductive endothermy in tegu lizards (Salvator merianae).

In cyclic climate variations, including seasonal changes, many animals regulate their energy demands to overcome critical transitory moments, restricting their high-demand activities to phases of resource abundance, enabling rapid growth and reproduction. Tegu lizards (Salvator merianae) are ectotherms with a robust annual cycle, being active during summer, hibernating during winter, and presenting a remarkable endothermy during reproduction in spring. Here, we evaluated whether changes in mitochondrial respiratory physiology in skeletal muscle could serve as a mechanism for the increased thermogenesis observed during the tegu's reproductive endothermy. We performed high-resolution respirometry and calorimetry in permeabilized red and white muscle fibers, sampled during summer (activity) and spring (high activity and reproduction), in association with citrate synthase measurements. During spring, the muscle fibers exhibited increased oxidative phosphorylation. They also enhanced uncoupled respiration and heat production via adenine nucleotide translocase (ANT), but not via uncoupling proteins (UCP). Citrate synthase activity was higher during the spring, suggesting greater mitochondrial density compared to the summer. These findings were consistent across both sexes and muscle types (red and white). The current results highlight potential cellular thermogenic mechanisms in an ectothermic reptile that contribute to transient endothermy. Our study indicates that the unique feature of transitioning to endothermy through nonshivering thermogenesis during the reproductive phase may be facilitated by higher mitochondrial density, function, and uncoupling within the skeletal muscle. This knowledge contributes significant elements to the broader picture of models for the evolution of endothermy, particularly in relation to the enhancement of aerobic capacity.

Glass softening in the limit of high heating rates: Heterogeneous devitrification kinetics on nano, meso, and micrometer scale.

When heated rapidly, glasses often devitrify heterogeneously, i.e., by a softening front that originates at the surface of an amorphous film. Yet the fundamentals of this devitrification regime are not completely understood; depending on experimental conditions, the reported front propagation distances differ by an order of magnitude. Using a high-resolution fast scanning calorimetry technique, we have investigated the softening of glassy methylbenzene films with thicknesses between 30 and 1400nm. We confirm first that, in all films, the devitrification process begins with the formation of a softening front that propagates through the films over distances of ∼50nm and that the front propagation kinetics at this stage follow an Arrhenius law. However, we also show that, in films with thicknesses above 165nm, the front propagation does not terminate with the onset of bulk softening. Specifically, increasing the films' thicknesses above 165nm yields sharp, clearly discernible endotherms that precede the bulk softening endotherms and that are consistent with a two-fold increase in the enthalpic barrier to front propagation at a well-defined critical temperature. We term this phenomenon "Arrhenius discontinuity" and use reaction rate and continuum front dynamics theories to explain its origins and the physical nature of the resulting distinct heterogeneous devitrification processes. Finally, we discuss the findings in the context of recent theoretical, computational, and experimental studies of heterogeneous devitrification by other research groups.

Phase transitions study of the liquid crystal DIO with a ferroelectric nematic, a nematic, and an intermediate phase and of mixtures with the ferroelectric nematic compound RM734 by adiabatic scanning calorimetry.

High-resolution calorimetry has played a significant role in providing detailed information on phase transitions in liquid crystals. In particular, adiabatic scanning calorimetry (ASC), capable of providing simultaneous information on the temperature dependence of the specific enthalpy h(T) and on the specific heat capacity c_{p}(T), has proven to be an important tool to determine the order of transitions and render high-resolution information on pretransitional thermal behavior. Here we report on ASC results on the compound 2,3',4',5'-tetrafluoro[1,1'-biphenyl]-4-yl 2,6-difluoro-4-(5-propyl-1,3-dioxan-2-yl) benzoate (DIO) and on mixtures with 4-[(4-nitrophenoxy)carbonyl]phenyl 2,4-dimethoxybenzoate (RM734). Both compounds exhibit a low-temperature ferroelectric nematic phase (N_{F}) and a high-temperature paraelectric nematic phase (N). However, in DIO these two phases are separated by an intermediate phase (N_{x}). From the detailed data of h(T) and c_{p}(T), we found that the intermediate phase was present in all the mixtures over the complete composition range, albeit with strongly decreasing temperature width for that phase with decreasing mole fraction of DIO (x_{DIO}). The x_{DIO} dependence on the transition temperatures for both transitions could be well described by a quadratic function. Both these transitions were weakly first order. The true latent heat of the N_{x}-N transition of DIO was as low as L=0.0075±0.0005J/g and L=0.23±0.03J/g for the N_{F}-N_{x} transition, which is about twice the previously reported value of 0.115 J/g for the N_{F}-N transition in RM734. In the mixtures both transition latent heats decrease gradually with decreasing x_{DIO}. At all the N_{x}-N transitions pretransition fluctuation effects are absent and these transitions are purely but very weakly first order. As in RM734 the transition from the N_{F} to the higher-temperature phase exhibits substantial pretransitional behavior, in particular, in the high-temperature phase. Power-law analysis of c_{p}(T) resulted in an effective critical exponent α=0.88±0.1 for DIO and this value decreased in the mixtures with decreasing x_{DIO} toward α=0.50±0.05 reported for RM734. Ideal mixture analysis of the phase diagram was consistent with ideal mixture behavior provided the total transition enthalpy change was used in the analysis.

Coexistence of Two Spin Frustration Pathways in the Quantum Spin Liquid Ca10Cr7O28.

Kagome antiferromagnetic lattices are of high interest because the geometric frustration is expected to give rise to highly degenerated ground states that may host exotic properties such as quantum spin liquid (QSL). Ca10Cr7O28 has been reported to display all the features expected for a QSL. At present, most of the literature reports on samples synthesized with starting materials ratio CaO/Cr2O3 3:1, which leads to a material with small amounts of CaCrO4 and CaO as secondary phases; this impurity excess affects not only the magnetic properties but also the structural ones. In this work, samples with starting material ratios CaO/Cr2O3 3:1, 2.9:1, 2.85:1, and 2.8:1 have been synthesized and studied by X-ray diffraction with Rietveld refinements, selected area electron diffraction measurements, high-resolution transmission electron microscopy (HRTEM), low-temperature magnetometry, and magnetic calorimetry. This result shows that a highly pure Ca10Cr7O28 phase is obtained for a CaO/Cr2O3 ratio of 2.85:1 instead of the 3:1 usually reported; the incorrect stoichiometric ratio leads to a larger distortion of the corner-sharing triangular arrangement of magnetic ions Cr+5 with S = 1/2 in the Kagome lattice. In addition, our study reveals that there exists another frustration pathway which is an asymmetric zigzag spin ladder along the directions [211], [12–1], and [1–1–1], in which the Cr–Cr distances are shorter than in the Kagome layers.

High-resolution calorimetry in pulsed magnetic fields.

We have developed a new calorimeter for measuring the thermodynamic properties in pulsed magnetic fields. Instrumental design is described along with the instrument construction details, including the sensitivity of a RuO2 thermometer. Operation of the calorimeter is demonstrated by measuring the heat capacity of three samples: pure germanium, CeCu2Ge2, and κ-(BEDT-TTF)2Cu[N(CN)2]Br, in pulsed fields up to 43.5T. Obtaining field stability is key in measuring high-resolution heat capacity under pulsed fields. We also examine the performance of the calorimeter by employing two measurement techniques: the quasi-adiabatic and dual-slope techniques. We demonstrate that the calorimeter developed in this study is capable of performing high-resolution calorimetry in pulsed magnetic fields, which opens the door to new opportunities for high-field thermodynamic studies.

Phase behaviour of n-CB liquid crystals confined to controlled pore glasses

In this review, we present the phase behaviour of liquid crystals (LCs) confined to Controlled-Pore Glasses (CPG) of various pore sizes. We consider either non-treated or silane-treated CPG pore surfaces, which impose parallel and homeotropic alignment to n-cyanobiphenyl (n-CB) LCs, respectively. The resulting nematic or smectic ordering depends on the characteristic void radii R and is well described in terms of the Landau-de Gennes free energy. Experimental data for different n-CB LCs, 5CB, 8CB, and 12CB, demonstrate phase transitions in orientation and translational degrees of freedom. In the bulk, 5CB and 8CB exhibit on cooling from the isotropic (I) phase the 1st order isotropic-nematic (I−N) phase transitions. In addition, 8CB also exhibits on further cooling a 2nd order nematic-smectic A (N−SmA) phase transition. 12CB, on the other hand, only has a 1st order isotropic-smectic A (I−SmA) phase transition. The bulk LCs exhibit a variety of different phase structures. When LCs are confined to porous media, their phase structures can be modified and even glass transition is possible.For LCs confined to CPG, the phase transition temperatures are shifted, depending on the pore size and the pore surface treatment. The Landau-de Gennes model predicts that the present phase transition shifts display inversely linear and inversely quadratic contributions in terms of the characteristic pore sizes. Furthermore, for strong enough confinement the phase transitions are replaced by gradual evolution of LCs order. These predictions are in line with nuclear magnetic resonance, small- angle X-ray scattering, and high-resolution calorimetry experimental observations.

Microwatt-Resolution Calorimeter for Studying the Reaction Thermodynamics of Nanomaterials at High Temperature and Pressure.

Calorimetry of reactions involving nanomaterials is of great current interest, but requires high-resolution heat flow measurements and long-term thermal stability. Such studies are especially challenging at elevated reaction pressures and temperatures. Here, we present an instrument for measuring the enthalpy of reactions between gas-phase reactants and milligram scale nanomaterial samples. This instrument can resolve the net change in the amount of gas-phase reactants due to surface reactions in an operating range from room temperature to 300 °C and reaction pressures of 10 mbar to 30 bar. The calorimetric resolution is shown to be <3 μW/√Hz, with a long-term stability <4 μW/hour. The performance of the instrument is demonstrated via a set of experiments involving H2 absorption on Pd nanoparticles at various pressures and temperatures. For this specific reaction, we obtained a mass balance resolution of 0.1 μmol/√Hz. Results from these experiments are in good agreement with past studies establishing the feasibility of performing high resolution calorimetry on milligram scale nanomaterials, which can be employed in future studies probing catalysis, phase transformations, and thermochemical energy storage.

Quantum Dot-Driven Stabilization of Liquid-Crystalline Blue Phases

Liquid crystals hosting nanoparticles comprise a fascinating research field, ranging from fundamental aspects of phase transitions to applications in optics and photonics. Liquid-crystalline phases exhibit topological defects that can be used for self-assembly of nanoparticles in periodical arrays and, at the same time, the nanoparticles can increase the stability range of liquid-crystalline phases. This has been experimentally demonstrated over the past few years in the case of blue phases that are present in some strongly chiral liquid crystals. Experimental results in quantum dot-driven blue phase stabilization are presented here by means of high-resolution calorimetry and polarizing optical microscopy. It is demonstrated that quantum-dots essentially stabilize the macroscopically amorphous blue phase III. There are discussed similarities and differences between the effects of spherical and anisotropic nanoparticles on blue phase stabilization; moreover, future prospects and trends in the field are addressed.

Polymorphic Transformations in Iron and Zirconium

Polymorphic transformations in iron of differing purity and zirconium iodide have been studied by the high-resolution calorimetry method. The hypothesis has been made that polymorphic transformations in zirconium, unlike those in iron, are governed by two mechanisms—diffusionless and diffusion. Which of them prevails depends on the temperature cycling rate and thermal history of the zirconium.

Blue phase stabilization by CoPt-decorated reduced-graphene oxide nanosheets dispersed in a chiral liquid crystal

We report on the effect of reduced-graphene oxide nanosheets decorated by CoPt nanoparticles on the blue phase range of a chiral liquid crystal. By means of high-resolution ac calorimetry and polarizing optical microscopy, it is demonstrated that a small concentration of these nanosheets induces the stabilization of a single blue phase structure in comparison to three blue phases existing in the pure compound. The results are compared with other liquid crystal-dispersed graphene studies, and, moreover, a short theoretical discussion of the stabilization effect is included.

A new synthetic methodology for pyridinic sucrose esters and their antibacterial effects against Gram-positive and Gram-negative strains

Described are the development of a new synthetic method using ultrasonic irradiation and sodium methoxide as catalyst for a series of pyridinic sucrose esters (py-SEs), derived from transesterification of sucrose with picolinic, nicotinic and isonicotinic methyl esters. The reaction was optimized using a 32 x 2 experimental design, the reaction time, temperature and sucrose: methyl ester molar ratio being evaluated. The method proved to be efficient for obtaining monosubstituted esters (≥83%) with high methyl ester consumption (≥79%). The monosubstituted py-SEs were isolated by semipreparative HPLC, characterized by high-resolution mass spectrometry, calorimetry, vibrational spectroscopy, and 1H and 13C NMR. The py-SEs were tested against E. coli, S. aureos, and P. aeruginosa bacteria with minimum inhibitory concentration values equal or inferior to the reference drugs for both E. coli and P. aeruginosa.

Interplay between various crystalline and hexatic-B phases in 75OBC liquid crystal: X-ray diffraction and calorimetry study

ABSTRACT X-ray diffraction and high-resolution adiabatic calorimetry have been used to study the polymorphic behaviour of 75OBC liquid crystal. On heating of 75OBC from the room temperature, the crystal phase (Cr-I) melts directly to smectic A (Sm-A) and then to isotropic phase. On cooling from isotropic phase the 75OBC undergoes successive transitions to Sm-A, hexatic B (Hex-B), crystalline (Cr-II) phases, and next to another crystal phase – Cr-III. The latter two crystalline phases were shown to relax slowly to Cr-I phase, which is stable at low temperatures. X-ray data indicate that the Cr-II phase possesses orthorhombic lattice with herringbone in-plane order of the molecules (Cr-E). The Cr-I and Cr-III phases belong to different low symmetry monoclinic lattices. Our results demonstrate a complex polymorphism of 75OBC compound: the thermodynamic pathway that involves monotropic Hex-B and orthorhombic Cr-E phases corresponds to a local thermodynamic minimum, while the other ones showing melting from the Cr-I to Sm-A phase belongs to the global minimum. The similar thermal behaviour was observed for other members of nmOBC homologous series, possessing a Sm-A – Hex-B – Cr-E phase sequence on cooling. The 75OBC polymorphic behaviour is discussed in terms of molecular packing and stability of Cr-E orthorhombic lattice that precedes the transition to the Hex-B phase.

Scintillating crystals for the Neutral Particle Spectrometer in Hall C at JLab

This paper discusses the quality and performance of currently available PbWO4 crystals of relevance to high-resolution electromagnetic calorimetry, e.g. detectors for the Neutral Particle Spectrometer at Jefferson Lab or those planned for the Electron–Ion Collider. Since the construction of the Compact Muon Solenoid (CMS) at the Large Hadron Collider (LHC) and early PANDA (The antiProton ANnihilations at DArmstadt) electromagnetic calorimeter (ECAL) the worldwide availability of high quality PbWO4 production has changed dramatically. We report on our studies of crystal samples from SICCAS/China and CRYTUR/Czech Republic that were produced between 2014 and 2019.

Особенности полиморфных превращений в железе и цирконии

Features of the polymorphic transformations in iron of different purity and zirconium iodide were studied using high-resolution calorimetry methods. It has been suggested that the polymorphic transformations in zirconium, in contrast to the polymorphic transformations in iron, were controlled by two mechanisms: diffusion-free and diffusion. The relationship between them depends on the rate of thermal cycling and the thermal background of zirconium.

The effect of CoPt-coated reduced-graphene oxide nanosheets upon the Smectic-A to Smectic-C* phase transition of a chiral liquid crystal

ABSTRACTWe report on high-resolution calorimetry and small-angle X-ray scattering measurements along the Smectic-A to chiral Smectic-C* phase transition of the liquid crystal 4-(2-methyl butyl) phenyl 4-n-octylbiphenyl-4-carboxylate with dispersed, CoPt nanoparticle-coated reduced-graphene oxide nanosheets. The temperature dependence of heat capacity and smectic layer spacing are obtained in the vicinity of Smectic-A to chiral Smectic-C* phase transition. Though no remarkable pretransitional effects are present, the critical fits show a crossover from mean-field near a tricritical point to classical mean-field compared to pure liquid crystal. The X-ray data yield a dilation of smectic layer thickness, indicating the assembly of graphene oxide nanosheets between the smectic layers.

High-resolution adiabatic calorimetry of supercooled water

Liquid water exhibits anomalous behavior in the supercooled region. A popular hypothesis to explain supercooled water’s anomalies is the existence of a metastable liquidliquid transition terminating at a critical point. The hypothesized phase transition is not directly accessible in a bulk experiment because it is expected to occur in “no-man’s” below the kinetic stability limit of the liquid phase at about 233 K, the temperature of homogeneous ice formation. Therefore, verifications of this hypothesis are usually based on extrapolations from the experimentally accessible region. In this work, we present the results of highresolution adiabatic calorimetry measurements of cold and supercooled liquid water in the range from 294 to 244 K, the lowest temperature of water’s supercooling achieved so far in a bulk adiabatic-calorimetry experiment. The resolution of the measurements is also record-high, with the average statistical (random) error of about 0.1%. The data are consistent with adiabatic-calorimetry measurements of supercooled water earlier reported by Tombari et al (1999 Chem. Phys. Lett. 300 749) but significantly deviate from differential-scanning calorimetry measurements in emulsified water reported by Angell et al (1982 J. Phys. Chem. 86 998) and by Archer and Carter (2000 J. Phys. Chem. 104 8563) Consequences of the new heat-capacity data in interpretation of the nature of water’s anomalies are discussed.

Coexisting Ordered States, Local Equilibrium-like Domains, and Broken Ergodicity in a Non-turbulent Rayleigh-B\xe9nard Convection at Steady-state

A challenge in fundamental physics and especially in thermodynamics is to understand emergent order in far-from-equilibrium systems. While at equilibrium, temperature plays the role of a key thermodynamic variable whose uniformity in space and time defines the equilibrium state the system is in, this is not the case in a far-from-equilibrium driven system. When energy flows through a finite system at steady-state, temperature takes on a time-independent but spatially varying character. In this study, the convection patterns of a Rayleigh-Bénard fluid cell at steady-state is used as a prototype system where the temperature profile and fluctuations are measured spatio-temporally. The thermal data is obtained by performing high-resolution real-time infrared calorimetry on the convection system as it is first driven out-of-equilibrium when the power is applied, achieves steady-state, and then as it gradually relaxes back to room temperature equilibrium when the power is removed. Our study provides new experimental data on the non-trivial nature of thermal fluctuations when stable complex convective structures emerge. The thermal analysis of these convective cells at steady-state further yield local equilibrium-like statistics. In conclusion, these results correlate the spatial ordering of the convective cells with the evolution of the system’s temperature manifold.

Тепловые эффекты при кристаллизации сплавов с неограниченной и ограниченной растворимостью компонентов

The processes of crystallization of two-component alloys with unrestricted and limited solubility of the constituent components were investigated by the method of differential high-resolution scanning calorimetry. It was found that in all cases a jump in the heat evolution of crystallization that is noticeable in magnitude and speed is recorded directly below the liquidus line. Traditional approaches in describing the development of crystallization processes in the intercritical temperature range do not provide an explanation for the observed phenomena. It is assumed that the observed effects are associated with the formation of a large number of local microvolumes (concentration fluctuations) enriched in the leading crystallization component. Their appearance precedes the beginning of processes of spontaneous formation of a large number of crystals in a noticeable volume of the liquid phase.

Nanocalorimetric evidence for nematic superconductivity in the doped topological insulator Sr0.1Bi2Se3

Spontaneous rotational-symmetry breaking in the superconducting state of doped $\mathrm{Bi}_2\mathrm{Se}_3$ has attracted significant attention as an indicator for topological superconductivity. In this paper, high-resolution calorimetry of the single-crystal $\mathrm{Sr}_{0.1}\mathrm{Bi}_2\mathrm{Se}_3$ provides unequivocal evidence of a two-fold rotational symmetry in the superconducting gap by a \emph{bulk thermodynamic} probe, a fingerprint of nematic superconductivity. The extremely small specific heat anomaly resolved with our high-sensitivity technique is consistent with the material's low carrier concentration proving bulk superconductivity. The large basal-plane anisotropy of $H_{c2}$ is attributed to a nematic phase of a two-component topological gap structure $\vec{\eta} = (\eta_{1}, \eta_{2})$ and caused by a symmetry-breaking energy term $\delta (|\eta_{1}|^{2} - |\eta_{2}|^{2}) T_{c}$. A quantitative analysis of our data excludes more conventional sources of this two-fold anisotropy and provides the first estimate for the symmetry-breaking strength $\delta \approx 0.1$, a value that points to an onset transition of the second order parameter component below 2K.

Heating treatments affect the thermal behaviour of doxorubicin loaded in PEGylated liposomes

Doxil® is a stealth marketed PEGylated liposomal formulation, containing the anticancer drug doxorubicin. After loading via a pH gradient, fibrillar supramolecular structures of doxorubicin sulfate originates inside the core of the liposomes. Recently, the crystallinity of doxorubicin sulfate has been confirmed by high-resolution calorimetry. However, no detailed information are available on the nature of doxorubicin sulfate nanocrystals and on the effect of different thermal treatments. Thus, the aim of this work was to characterize the thermal behaviour of Doxil® in comparison to the unloaded liposomes using microcalorimetry, dynamic light scattering and high-resolution ultrasound spectroscopy (HR-US). Different thermal programmes were applied with the aim to highlight the effect of the treatments on the formulation. The used techniques confirmed the ordered state of doxorubicin nanocrystals inside PEGylated liposomes. Particularly, microcalorimetry and HR-US highlighted the changes in the thermal behaviour of the drug under different heating programmes. Doxorubicin nanocrystals were found to be stable after heating up to 80°C, but an irreversible thermal behaviour was observed after a prolonged heating at elevated temperature (2h at 80°C). The non-reversibility could be related to the formation of a different ordered structure and enhanced by the slight leakage of the drug occurring after a prolonged heating.