Small Enthalpy Research Articles

Thermotropic and barotropic phase transitions on diacylphosphatidylethanolamine bilayer membranes

The bilayer phase transitions of four diacylphosphatidylethanolamines (PEs) with matched saturated acyl chains (Cn=12, 14, 16 and 18) and two PEs with matched unsaturated acyl chains containing a different kind of double bonds were observed by differential scanning calorimetry under atmospheric pressure and light-transmittance measurements under high pressure. The temperature-pressure phase diagrams for these PE bilayer membranes were constructed from the obtained phase-transition data. The saturated PE bilayer membranes underwent two different phase transitions related to the liquid crystalline (Lα) phase, the transition from the hydrated crystalline (Lc) phase and the chain melting (gel (Lβ) to Lα) transition, depending on the thermal history. Pressure altered the gel-phase stability of the bilayer membranes of PEs with longer chains at a low pressure. Comparing the thermodynamic quantities of the saturated PE bilayer membranes with those of diacylphosphatidylcholine (PC) bilayer membranes, the PE bilayer membranes showed higher phase-transition temperatures and formed more stable Lc phase, which originates from the strong interaction between polar head groups of PE molecules. On the other hand, the unsaturated PE bilayer membranes underwent the transition from the Lα phase to the inverted hexagonal (HII) phase at a high temperature and this transition showed a small transition enthalpy but high pressure-responsivity. It turned out that the kind of double bonds markedly affects both bilayer-bilayer and bilayer-nonbilayer transitions and the Lα/HII transition is a volume driven transition for the reconstruction of molecular packing. Further, the phase-transition behavior was explained by chemical potential curves of bilayer phases.

A quick-fix design of phase change material by particle blending and spherical agglomeration

The aims of this study were to impregnate polyethylene glycol (PEG) 4000 in low-cost silica fume (SF) to form phase change material (PCM) composites with cementitious value, and to provide a quick-fix design for PCM (1) with tailor-made thermal properties and behaviors by particle blending of two types of polyethylene (PEG)/silica fume (SF) composites having different PEG wt% loading, and (2) with enhanced physical properties by turning the powdery PEG/SF composites into round granules through spherical agglomeration. The simple composite blending method was used to broaden and tune the application temperatures in response to variable conditions and environments without the need of searching for new materials to mitigate global warming. Spherical agglomerates of PEG/SF composite exhibited a good homogeneity in thermal properties and low Carr’s indices indicating of excellent flowability, packability and compactibility, and offering an enhanced contact area for heat transfer and uniform mixing with other building materials. Noticeably, the agglomerates displayed higher heat capacity values of solid phase, Cps, and liquid phase, Cpl, than those of the composite determined by temperature-history method. The thermal stability of PEG75/SF composites was also attested by the small enthalpy loss, and the highly reproducible melting and solidification behaviors after more than 100 temperature cycles.

Thermodynamics of Helix-Coil Transitions of Polyalanine in Open Carbon Nanotubes.

Understanding structure formation in polypeptide chains and synthetic polymers encapsulated in pores is important in biology and nanotechnology. We present replica exchange molecular dynamics studies of the phase diagram for α-helix formation of capped polyalanine in nanotubes (NT) open to a water reservoir as a function of the NT diameter and hydrophobicity. A helix forms only in a narrow range of diameters, which surprisingly is comparable to the width of the ribosome tunnel. Increasing the hydrophobicity enhances helicity in the NT. Helix formation in polyalanine is driven by a small negative enthalpy and a positive entropy change at ≈300 K, in contrast to the large negative entropy change that destabilizes the helix and favors the coiled state in bulk water. There is an anticorrelation between water density inside the nanotube and structure formation. Confinement-induced helix formation depends on amino acid sequence. There is complete absence of helix in polyglutamine and polyserine confined to a open carbon nanotube.

Design Principles for High H2 Storage Using Chelation of Abundant Transition Metals in Covalent Organic Frameworks for 0-700 bar at 298 K.

Physisorption is an effective route to meet hydrogen gas (H2) storage and delivery requirements for transportation because it is fast and fully reversible under mild conditions. However, most current candidates have too small binding enthalpies to H2 which leads to volumetric capacity less than 10 g/L compared to that of the system target of 40 g/L at 298 K. Accurate quantum mechanical (QM) methods were used to determine the H2 binding enthalpy of 5 linkers which were chelated with 11 different transition metals (Tm), including abundant first-row Tm (Sc through Cu), totaling 60 molecular compounds with more than 4 configurations related to the different number of H2 that interact with the molecular compound. It was found that first-row Tm gave similar and sometimes superior van der Waals interactions with H2 than precious Tm. Based on these linkers, 30 new covalent organic frameworks (COFs) were constructed. The H2 uptakes of these new COFs were determined using quantum mechanics (QM)-based force fields and grand canonical Monte Carlo (GCMC) simulations. For the first time, the range for the adsorption pressure was explored for 0-700 bar and 298 K. It was determined that Co-, Ni-, and Fe-based COFs can give high H2 uptake and delivery when compared to bulk H2 on this unexplored range of pressure.

Kinetic Insights into the Binding between the nSH3 Domain of CrkII and Proline-Rich Motifs in cAbl

The interaction between CrkII and cAbl is implicated in diverse cellular processes. This interaction starts with the binding of the N-terminal Src homology 3 (nSH3) domain of CrkII to the proline-rich motifs of cAbl (PRMscAbl). Despite its critical importance, the detailed binding mechanism between the nSH3 domain and PRMs remains elusive. In this study, we used nuclear magnetic resonance Carr-Purcell-Meiboom-Gill relaxation dispersion experiment to study the binding kinetics between the nSH3 domain of CrkII and PRMscAbl. Our results highlight that the nSH3 domain binds to three PRMscAbl with very high on- and off-rate constants, indicating the transient nature of the binding. To further characterize the binding transition state, we conducted the Eyring and linear free energy relationship analyses using temperature-dependent kinetic data. These data indicate that the binding transition state of the nSH3 domain and PRM is accompanied by small activation enthalpy, owing to partial desolvation of the transition state. These results also highlight the similarity between the transition and free states, in terms of structure and energetics. Although the binding of the nSH3 domain and PRM displays the features consistent with a diffusion-limited process within our experimental conditions, further tests are necessary to determine if the binding is a true diffusion-limited process.

Possible "Magnéli" Phases and Self-Alloying in the Superconducting Sulfur Hydride.

We theoretically give an infinite number of metastable crystal structures for the superconducting sulfur hydride H_{x}S under pressure. Previously predicted crystalline phases of H_{2}S and H_{3}S have been thought to have important roles for experimentally observed low and high T_{c}, respectively. The newly found structures are long-period modulated crystals where slablike H_{2}S and H_{3}S regions intergrow on a microscopic scale. The extremely small formation enthalpy for the H_{2}S-H_{3}S boundary indicated by first-principles calculations suggests possible alloying of these phases through the formation of local H_{3}S regions. The modulated structures and gradual alloying transformations between them not only explain the peculiar pressure dependence of T_{c} in sulfur hydride observed experimentally, but also could prevail in the experimental samples under various compression schemes.

Combined Turbine and Cycle Optimization for Organic Rankine Cycle Power Systems—Part B: Application on a Case Study

Organic Rankine cycle (ORC) power systems have recently emerged as promising solutions for waste heat recovery in low- and medium-size power plants. Their performance and economic feasibility strongly depend on the expander. The design process and efficiency estimation are particularly challenging due to the peculiar physical properties of the working fluid and the gas-dynamic phenomena occurring in the machine. Unlike steam Rankine and Brayton engines, organic Rankine cycle expanders combine small enthalpy drops with large expansion ratios. These features yield turbine designs with few highly-loaded stages in supersonic flow regimes. Part A of this two-part paper has presented the implementation and validation of the simulation tool TURAX, which provides the optimal preliminary design of single-stage axial-flow turbines. The authors have also presented a sensitivity analysis on the decision variables affecting the turbine design. Part B of this two-part paper presents the first application of a design method where the thermodynamic cycle optimization is combined with calculations of the maximum expander performance using the mean-line design tool described in part A. The high computational cost of the turbine optimization is tackled by building a model which gives the optimal preliminary design of an axial-flow turbine as a function of the cycle conditions. This allows for estimating the optimal expander performance for each operating condition of interest. The test case is the preliminary design of an organic Rankine cycle turbogenerator to increase the overall energy efficiency of an offshore platform. For an increase in expander pressure ratio from 10 to 35, the results indicate up to 10% point reduction in expander performance. This corresponds to a relative reduction in net power output of 8.3% compared to the case when the turbine efficiency is assumed to be 80%. This work also demonstrates that this approach can support the plant designer in the selection of the optimal size of the organic Rankine cycle unit when multiple exhaust gas streams are available.

Spectroscopic and calorimetric investigations on the binding of phenazinium dyes safranine-O and phenosafranine to double stranded RNA polynucleotides

RNA targeting through small molecules that can selectively bind specific RNA structures is an important current strategy in therapeutic drug development. Towards this strategy a comparative study on the interaction of two phenazinium dyes, safranine-O and phenosafranine to double stranded RNAs, poly(I).poly(C), poly(A).poly(U) and poly(C).poly(G) was performed. Spectrophotometric and spectrofluorimetric studies revealed non-cooperative binding of the dyes to the duplex RNA with binding constants of the order 105M−1 with a higher affinity of safranine-O to poly(I).poly(C) followed by poly(A).poly(U) and poly(C).poly(G). Anisotropy and fluorescence quenching results confirmed an intercalation mode of binding for the dyes on these RNAs. Binding induced conformational changes in the RNA polynucleotides were revealed from circular dichroism data. Thermal melting study and DSC experiments demonstrated stabilization of dye-RNA complexes. Calorimetric studies revealed that the binding was accompanied by a large positive entropy term with a small negative enthalpy contributions. Significant hydrophobic forces in the complexation of the double stranded RNAs with the dyes were confirmed from the negative heat capacity changes. Enthalpy-entropy compensation was also observed in the binding. Parsing of the Gibbs energy suggested a larger non-electrostatic contribution in all the cases. The results presented here may be helpful to design new types of RNA-based therapeutic agents.

Nematic liquid crystals exhibiting high birefringence

Two fluorinated isothiocyanato nematic liquid crystalline compounds, 4′-butylcyclohexyl-3, 5-difluoro-4-isothiocyanatobiphenyl and 4′-pentylcyclohexyl-3, 5-difluoro-4-isothiocynatobiphenyl are studied in detail to obtain their different physical parameters. Optical polarizing microscopy, differential scanning calorimetry, density and dielectric studies have been carried out for the two samples. Both the samples were found to have high clearing temperature (>100 °C) and exhibit small enthalpy of transition. The two samples exhibit high optical birefringence (Δn > 0.2). The values of order parameters for the two samples were obtained using different approaches, namely, Vuks’, Neugebauer’s, modified Vuks’ and direct extrapolation method from birefringence data. Experimentally obtained values of order parameters have also been compared with theoretical Maier–Saupe values. The parallel and perpendicular components of dielectric permittivity values of the two compounds were also calculated and their anisotropy values were found to be small. The effect of temperature on the molecular dipole moment μ and the angle of inclination β of the dipole axis with the director have also been investigated in this work.

The Hydrophobic Effect in Solute Partitioning and Interfacial Tension.

Studies of the partitioning of hydrophobic solutes between water and nonpolar solvents provide estimates for the energy cost of creating hydrophobic-water contacts. This energy is a factor of three lower than the work of adhesion derived from interfacial tension measurements. This discrepancy noted by Tanford in 1979 is widely viewed as a serious challenge to our understanding of hydrophobic interactions. However, the interfacial energy of a water-alkane interface depends on chain length. A simple analysis of published data shows that the loss of rotational freedom of an alkane chain at an interface accounts quantitatively for the length-dependent contribution to interfacial tension, leaving a length-independent contribution very close to the free energy of transfer per unit of solvent accessible surface area. This analysis thus clarifies the discrepancy between the thermodynamic and interfacial tension measurements of hydrophobic interaction energy. Alkanes do not loose rotational freedom when transferred between two different liquid phases but they do at an interface. This reconciles the difference between microscopic and macroscopic measurements. Like the partitioning free energy, the work of adhesion also has a large entropy and small enthalpy at 20 oC.

The Reversible Formation of Tight Ion Pairs within Platinum(II) Complexes – A Study of Thermodynamic Parameters Governing Noncovalent Interactions

AbstractCompounds like [(HR2DTO)Pt(H2R2DTO)][Cl] (DTO = dithiooxamidate; R = ethyl or benzyl) can be involved in acid–base reactions in chloroform, playing the role of either the acid or the base partner. When the complexes react with pyridines, neutral complexes like [(HR2DTO)2Pt] are formed. Such processes are characterized by small enthalpy changes, so they are substantially entropy‐driven. We explained this as a consequence of the solvent released when HCl is transferred from tight‐ion‐pair platinum compounds to pyridines. When [(HR2DTO)Pt(H2R2DTO)][Cl] species react with HCl, complexes like [(H2R2DTO)Pt(H2R2DTO)][Cl]2 are formed, where a new weak hydrogen‐bonding‐based interaction of the type N···H–Cl is present; however, the measured enthalpy changes show values typical of a strong interaction (R = ethyl, ΔH° = –146.3 ± 9.7 kJ mol–1; R = benzyl, ΔH° = –67.7 ± 2.0 kJ mol–1), apparently too large for hydrogen bonding. Also, the entropy lowering is too large to be attributable to a simple association process (R = ethyl, ΔS° = –398 ± 32 J K–1 mol–1; R = benzyl, ΔS° = –154 ± 7 J K–1 mol–1). Both large enthalpy and entropy lowering have been attributed to the role played by the solvent in the acid–base processes. In the present systems, the solvent strongly affects not only the entropy factor, but also the enthalpy factor. Such conclusions can be generalized to give useful information for controlling similar noncovalent, electrostatic interactions.

Thermodynamics of self-assembling of mixture of a cationic gemini surfactant and sodium dodecylsulfate in aqueous solution: Calorimetry, conductivity and surface pressure measurements

The thermodynamics and phase behavior of mixtures of cationic gemini surfactant decanediyl-α,ω-bis(dodecyldimethylammonium bromide) (12-10-12) and sodium dodecylsulfate (SDS) were studied in the dilute SDS-rich region. The enthalpy of interaction between both surfactant monomers before the critical micelle concentration for the mixture (cmcmix) was determined by isothermal titration calorimetry (ITC). After the cmcmix, ITC results exhibited a first process associated with a large endothermic enthalpy change followed by a second one with a very small exothermic enthalpy change. In the same regions, the conductivity curves show an increase in slope after the break, followed by a plateau region, respectively for the two processes. The combined results from the various methodologies used lead us to propose that the first process reflects the formation of non-spherical micelles and the second one the vesicle formation. The area per catanionic complex was obtained through surface pressure measurements, leading to an apparent packing parameter ⩾1. The observed behavior may be rationalized on the basis of the hypothesis that both surfactants distribute asymmetrically in the vesicle bilayers and unevenly in the non-spherical micelle. In order to get structural information Cryo-TEM experiments were performed, which provided images that support this interpretation. From all the information gathered a phase diagram was mapped, including three one-phase regions of spherical micelles, non-spherical micelles and vesicles.

Targeting of 1-Naphthyl acetyl spermine to DNA: A calorimetric and spectroscopic investigation

Isothermal titration calorimetry, UV optical melting, differential scanning calorimetry, circular dichroism and ethidium bromide displacement experiments were employed to study the interaction of the polyamine analogue 1-naphthyl acetyl spermine with DNA. The mode of binding was evaluated by hoechst 33258 displacement assay. Calorimetric studies divulged the binding of 1-naphthyl acetyl spermine to DNA to be endothermic with affinity (7.10±0.20)·105mol−1·dm3. The interaction was entropy driven with a small enthalpy contribution that was unfavourable. The binding was characterised by total enthalpy–entropy compensation and high standard molar heat capacity values. The interaction led to strong stabilization of the DNA melting. Circular dichroism studies revealed significant structural perturbation of the DNA on binding of 1-naphthyl acetyl spermine. Displacement assay with hoechst 33258 proved the minor groove binding mechanism of the analogue. Ethidium bromide displacement assay corroborated the ability of the spermine analogue to displace ethidium bromide from the DNA scaffold. Salt dependent studies reiterated the involvement of electrostatic interaction in the binding along with the strong involvement of hydrophobic interactions.

Binding of the alkaloid aristololactam-β-D-glucoside and daunomycin to human hemoglobin: spectroscopy and calorimetry studies

The interaction of the plant alkaloid aristololactam-β-D-glucoside (ADG) and the anticancer agent daunomycin (DAN) with human hemoglobin was studied by different spectroscopic and calorimetric methods. The binding affinity values of ADG and DAN, estimated from spectroscopic experiments, were 3.79 × 104 and 6.68 × 104 M−1, respectively. From circular dichroism, 3D fluorescence, and FTIR studies it was observed that, DAN induced stronger conformational changes than ADG in the protein. From synchronous fluorescence spectroscopy results, a pronounced shift in the maximum emission wavelength of tyrosine residues was observed in both cases suggesting that the drugs changed the polarity around tyrosine residues with marginal change around the tryptophan residues. The thermodynamics of the binding interaction analyzed using microcalorimetry presented single binding events that were exothermic in nature in both cases. The binding was driven by large positive standard molar entropy changes with small favorable enthalpy contributions. Negative heat capacity changes in both cases are correlated to the involvement of significant hydrophobic forces in the complexation process. The affinity of DAN to Hb was higher than that of ADG.

Microcalorimetry and spectroscopic studies on the binding of dye janus green blue to deoxyribonucleic acid

The interaction of the phenazinium dye janus green blue (JGB) with deoxyribonucleic acid was investigated using isothermal titration calorimetry and thermal melting experiments. The calorimetric data were supplemented by spectroscopic studies. Calorimetry results suggested the binding affinity of the dye to DNA to be of the order of 105 M−1. The binding was predominantly entropy driven with a small negative favorable enthalpy contribution to the standard molar Gibbs energy change. The binding became weaker as the temperature and salt concentration was raised. The temperature dependence of the standard molar enthalpy changes yielded negative values of standard molar heat capacity change for the complexation revealing substantial hydrophobic contribution in the DNA binding. An enthalpy–entropy compensation behavior was also observed in the system. The salt dependence of the binding yielded the release of 0.69 number of cations on binding of each dye molecule. The non-polyelectrolytic contribution was found to be the predominant force in the binding interaction. Thermal melting studies revealed that the DNA helix was stabilized against denaturation by the dye. The binding was also characterized by absorbance, resonance light scattering and circular dichroism spectral measurements. The binding constants from the spectral results were close to those obtained from the calorimetric data. The energetic aspects of the interaction of the dye JGB to double-stranded DNA are supported by strong binding revealed from the spectral data.

Interaction of toxic azo dyes with heme protein: Biophysical insights into the binding aspect of the food additive amaranth with human hemoglobin

A biophysical study on the interaction of the food colorant amaranth with hemoglobin was undertaken. Spectrophotometric and spectrofluorimetric studies proposed for an intimate binding interaction between the dye and the protein. The dye quenched the fluorescence of the protein remarkably and the mechanism of quenching was found to be static in nature. Synchronous fluorescence studies suggested that the polarity around the tryptophan residues was altered in the presence of amaranth whereas the polarity around tyrosine residues remained largely unaltered. 3D fluorescence, FTIR and circular dichroism results suggested that the binding reaction caused conformational changes in hemoglobin. The negative far-UV CD bands exhibited a significantly large decrease in magnitude in the presence of amaranth. From calorimetry studies it was established that the binding was driven by a large positive entropic contribution and a small but favorable enthalpy change.

Spatial analysis and quantification of the thermodynamic driving forces in protein-ligand binding: binding site variability.

The thermodynamic driving forces behind small molecule-protein binding are still not well-understood, including the variability of those forces associated with different types of ligands in different binding pockets. To better understand these phenomena we calculate spatially resolved thermodynamic contributions of the different molecular degrees of freedom for the binding of propane and methanol to multiple pockets on the proteins Factor Xa and p38 MAP kinase. Binding thermodynamics are computed using a statistical thermodynamics based end-point method applied on a canonical ensemble comprising the protein-ligand complexes and the corresponding free states in an explicit solvent environment. Energetic and entropic contributions of water and ligand degrees of freedom computed from the configurational ensemble provide an unprecedented level of detail into the mechanisms of binding. Direct protein-ligand interaction energies play a significant role in both nonpolar and polar binding, which is comparable to water reorganization energy. Loss of interactions with water upon binding strongly compensates these contributions leading to relatively small binding enthalpies. For both solutes, the entropy of water reorganization is found to favor binding in agreement with the classical view of the "hydrophobic effect". Depending on the specifics of the binding pocket, both energy-entropy compensation and reinforcement mechanisms are observed. It is notable to have the ability to visualize the spatial distribution of the thermodynamic contributions to binding at atomic resolution showing significant differences in the thermodynamic contributions of water to the binding of propane versus methanol.

Design of an air-cooled condenser for engine coolant waste heat recovery

A novel design process for a parallel multi-flow type air-cooled condenser of a dual-loop waste heat recovery system with Rankine steam cycles, for improving the fuel efficiency of gasoline automobiles, has been investigated, focusing on reduction of the pressure drop inside the micro-tubes. The low temperature condenser plays a role in dissipating heat from the system, by sufficiently condensing the low temperature loop working fluid. However, the refrigerant has low enough evaporation temperature to recover the waste heat from engine coolant of about 100°C, but has small saturation enthalpy, so that excessive mass flow rate of the LT working fluid, e.g. over 150 g/s, causes an enormously large pressure drop of the working fluid, to maintain the heat dissipation performance of more than 20 kW. This paper has dealt with a scheme to design a low temperature condenser that has reduced the pressure drop, while ensuring the required thermal performance from the waste heat recovery system. The number of passes, arrangement of the tubes of each pass, and positions of the inlet and outlet pipes on the header are the most critical parameters affecting flow uniformity through all the tubes of the condenser. For the purpose of the performance predictions and parametric study for the LT condenser, we have developed a 1-dimensional userfriendly performance prediction program that feasibly calculates the phase change of the working fluid in the tubes. The proposed design process enables design engineers to find the optimum values of the numbers of passes and tubes of the multiflow condenser, for the reduction of the pressure drop sustaining the heat exchange performance. An example is presented through the proposed design process, and compared with an experiment.

Ductile-brittle transition behaviour of PLA/o-MMT films during the physical aging process

The ductile-brittle transition behaviour of organo modified montmorillonite-based Poly(lactic acid) films (PLA/o-MMT) was analysed using the Essential Work of Fracture (EWF) methodology, Small Punch Tests (SPT) and Enthalpy relaxation analysis. While the EWF methodology could only be applied successfully to de-aged samples, small punch test (SPT) was revealed as more effective for a mechanical characterization during the transient behaviour from duc- tile to brittle. According to differential scanning calorimetry (DSC) results, physical aging at 30°C of PLA/o-MMT samples exhibited slower enthalpy relaxation kinetics as compared to the pristine polymer. Although all samples exhibited an equiv- alent thermodynamic state after being stored one week at 30°C, significant differences were observed in the mechanical performances. These changes could be attributed to the toughening mechanisms promoted by o-MMT.

Calorimetry and thermal analysis studies on the binding of 13-phenylalkyl and 13-diphenylalkyl berberine analogs to tRNAphe

The interaction of 13- monophenylalkyl and diphenylalkyl berberine analogs with tRNAphe has been investigated using various thermochemical techniques like thermal melting, isothermal titration calorimetry, and differential scanning calorimetry experiments. Thermal melting studies revealed that all the analogs stabilized the tRNAphe better than berberine. The binding affinity for the analogs was of the order of 105 M−1. Calorimetry results suggested that the binding of these analogs was predominantly entropy driven with small negative enthalpy contribution to the standard molar Gibbs energy. The temperature dependence of the standard molar enthalpy changes yielded negative values of standard molar heat capacity changes for the complexation revealing substantial hydrophobic contribution in the RNA binding of these analogs. An enthalpy–entropy compensation behavior was also seen in all the systems. The diphenylalkyl analogs were found to be more effective tRNAphe binders compared to the monophenylalkyl analogs. The utility of the present work lies in understanding the structural and energetic aspects of the interaction of these berberine analogs with tRNA, which may be useful in the development of RNA-targeted drugs.