Thermal Analysis of Polymers

Thermal analysis embraces a group of analytical methods in which a physical property - e.g. enthalpy, mass, volume or birefringence - is measured as a function of temperature. This paper briefly presents differential scanning calorimetry (DSC), differential thermal analysis (DTA), thermogravimetry (TG), thermal mechanical analysis (TMA) and thermal optical analysis (TOA) as methods and describes in more detail their application on polymers. Examples are presented to demonstrate that the use of these methods and the interpretation of the results obtained requires special attention. The non-equilibrium nature of different polymers is illustrated by the melting and crystallization behaviour of flexible-chain polymers, the glass transition of amorphous polymers and phase transitions in liquid crystalline polymers. The information provided by thermal analysis about the morphology of crystalline polymers, the morphology of polymer blends and the chemical stability of polymers is also discussed.     

热塑性结晶型全芳族聚酯酰亚胺的制备与聚集态结构

以对-亚苯基-双苯偏三酸酯二酐(BTAH)与4,4'-二胺基二苯醚(ODA)为单体采用两步法合成了一种全芳族热塑性结晶型聚酯酰亚胺.盖示扫描量热(DSC)结果显示其玻璃化转变温度为192℃,且聚合物在熔融过程中表现出熔融双峰.X射线衍射(WAXD)结果显示聚合物在室温以及在410℃和420℃处理后均在2θ为18°,23...     

Thermal Analysis of Polymers

Abstract

Thermal analysis embraces a group of analytical methods in which a physical property - e.g. enthalpy, mass, volume or birefringence - is measured as a function of temperature. This paper briefly presents differential scanning calorimetry (DSC), differential thermal analysis (DTA), thermogravimetry (TG), thermal mechanical analysis (TMA) and thermal optical analysis (TOA) as methods and describes in more detail their application on polymers. Examples are presented to demonstrate that the use of these methods and the interpretation of the results obtained requires special attention. The non-equilibrium nature of different polymers is illustrated by the melting and crystallization behaviour of flexible-chain polymers, the glass transition of amorphous polymers and phase transitions in liquid crystalline polymers. The information provided by thermal analysis about the morphology of crystalline polymers, the morphology of polymer blends and the chemical stability of polymers is also discussed.     

不同保护剂浓度和不同降温速率对脂质体玻璃化转变温度的影响

玻璃化转变是动力学的非平衡过程,玻璃化转变量温度是和过程有关的参数。测量了在降温速率分别为５℃/min和１０℃/miｎ,升温速率为１０℃／ｍｉｎ条件下,葡萄糖、蔗糖、甘露醇、海藻糖浓度为５％（Ｗ／Ｖ）的脂质体悬浮的玻璃化转变温度Ｔ‘g,在降温速率为５℃ｍｉｎ、升温为１０℃/min条件下,测量了葡萄糖、蔗糖、甘露醇、海藻糖浓度为１５％（Ｗ／Ｖ）的脂质体的Ｔ’ｇ;并分析了不同降温速率和不同保护剂浓度对脂质体玻璃化转变温度Ｔ’g的影响因素。     

An experimental confirmation of thermal transitions in native and regenerated spider silks

Biological structures such as spider silks are formed by proteins. The physical properties of such proteins are determined by environmental conditions such as temperature and humidity. In this paper, we confirm the thermal transitions that take place in spider silks using differential scanning calorimetry and study how the interaction of spider silk proteins with water affects the onset temperatures for these thermal processes. Native fibres and regenerated films of dragline silk and egg sac silk from Argiope argentata spiders were used to study thermal transitions of protein based structures. For the first time, differential scanning calorimetry (DSC) tests were carried out with spider silk samples of relatively large mass (10 mg). Previous attempts of DSC tests applied to spider silk samples failed to detect thermal transitions in a conclusive way. The tests reported here, however, show thermal transitions on both natural and regenerated samples that are in agreement with results from dynamic mechanical analysis (DMA) tests reported in the literature. The water content on spider silks seems to lower the temperatures at which such thermal transitions take place. The results also confirm that the amorphous regions of native and regenerated spider silk and silk worm silk give rise to similar thermal transitions.     

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

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

Measuring protein structure and stability of protein-nanoparticle systems with synchrotron radiation circular dichroism

We measure the structural and stability changes of proteins at nanomolar concentration upon interaction with nanoparticles. Using synchrotron radiation circular dichroism (SRCD), we measure a decrease of 6 °C in the thermal unfolding of human serum albumin upon interaction with silver nanoparticles while this does not happen with gold. The use of SRCD allows measuring critical parameters on protein-nanoparticle interactions, and it will provide experimental data on the relative stability of key biological proteins for nanotoxicology.     

Measurements of Heat Capacity and Enthalpy of Phase Change Materials by Adiabatic Scanning Calorimetry

Phase change materials (PCMs) are substances exhibiting phase transitions with large latent heats that can be used as thermal storage materials with a large energy storage capacity in a relatively narrow temperature range. In many practical applications the solid–liquid phase change is used. For applications accurate knowledge of different thermal parameters has to be available. In particular, the temperature dependence of the enthalpy around the phase transition has to be known with good accuracy. Usually, the phase transitions of PCMs are investigated with differential scanning calorimetry (DSC) at fast dynamic scanning rates resulting in the effective heat capacity from which the (total) heat of transition can be determined. Here we present adiabatic scanning calorimetry (ASC) as an alternative approach to arrive simultaneously at the equilibrium enthalpy curve and at the heat capacity. The applicability of ASC is illustrated with measurements on paraffin-based PCMs and on a salt hydrate PCM.     

Early use of PEPA dialyzer for light chains removal and for the recovery from myeloma cast nephropathy: A case report

Chemotherapy and extracorporeal treatment reduce serum free light chains (FLCs) allowing the recovery of acute kidney injury (AKI) caused by myeloma cast nephropathy (MCN). We report the first case of recovery from AKI in a patient with MCN who underwent the removal of FLCs using the PEPA filter, with an undisclosed cut‐off, combined with chemotherapy for multiple myeloma (MM).     

Optical and thermal characterization of albumin protein solders

The effect of temperature on the optical and thermal properties of pure and indocyanine green-doped albumin protein solders as a function of wavelength has been studied between 25 degrees C and 100 degrees C. An increase in the group refractive index by up to 4% and a decrease in absorption coefficient (approximately 800 nm) by up to 8%, after denaturing the solder specimens in a constant-temperature water bath at temperatures of 60-100 degrees C, were not significant. The reduced scattering coefficient, however, increased rapidly with temperature as the solder changed from being a highly nonscattering medium at room temperature to a highly scattering medium at temperatures close to 70 degrees C. The thermal conductivity, thermal diffusivity, and heat capacity increased by up to 30%, 15%, and 10%, respectively. Finally, the frequency factor and activation energy were measured to be 3.17 x 10(56) s(-1) and 3.79 x 10(5) J mol(-1), respectively, for liquid protein solders (25% bovine serum albumin) and 3.50 x 10(57) s(-1) and 3.85 x 10(5) J mol(-1), respectively, for solid protein solders (60% bovine serum albumin). Incorporation of dynamic optical and thermal properties into modeling studies of laser tissue interactions could have a significant influence on the determination of the expected zone of damage.     

Study of thermally and chemically unfolded conformations of bovine serum albumin by means of dynamic light scattering

The change of conformation of a bovine serum albumin (BSA) has been characterized using dynamic light scattering (DLS). Structural properties were investigated as a function of chemical denaturant concentrations and a temperature. In pure water, the protein keeps its native size at guanidine hydrochloride (GdmCl) concentrations below 1 M and behaves like an excluded volume chain above 4 M. A transition in structure and properties of the protein seems to occur around a GdmCl concentration of 1.7 M. Still, this protein forms an unfolded conformation in presence of 6 M of urea concentration and the value of the diffusive virial coefficient indicates that the interactions between the polypeptide chain and solvent are repulsive. The true value of the T_m = 43 °C, has obtained by linear extrapolation to 0 M GdmCl.     

Encapsulation of Nano-Bortezomib in Apoptotic Stem Cell-Derived Vesicles for the Treatment of Multiple Myeloma

Extracellular vesicles (EVs) are lipid bilayer nanovesicles released from living or apoptotic cells that can transport DNA, RNA, protein, and lipid cargo. EVs play critical roles in cell–cell communication and tissue homeostasis, and have numerous therapeutic uses including serving as carriers for nanodrug delivery. There are multiple ways to load EVs with nanodrugs, such as electroporation, extrusion, and ultrasound. However, these approaches may have limited drug-loading rates, poor EV membrane stability, and high cost for large-scale production. Here, it is shown that apoptotic mesenchymal stem cells (MSCs) can encapsulate exogenously added nanoparticles into apoptotic vesicles (apoVs) with a high loading efficiency. When nano-bortezomib is incorporated into apoVs in culture-expanded apoptotic MSCs, nano-bortezomib-apoVs show a synergistic combination effect of bortezomib and apoVs to ameliorate multiple myeloma (MM) in a mouse model, along with significantly reduced side effects of nano-bortezomib. Moreover, it is shown that Rab7 regulates the nanoparticle encapsulation efficiency in apoptotic MSCs and that activation of Rab7 can increase nanoparticle-apoV production. In this study, a previously unknown mechanism to naturally synthesize nano-bortezomib-apoVs to improve MM therapy is revealed.     

Regulation of protein binding toward a ligand on chromatographic matrixes by masking and forced-releasing effects using thermoresponsive polymer

A novel concept of affinity regulation based on masking and forced-releasing effects using a thermoresponsive polymer was elucidated. Affinity chromatographic matrixes were prepared using either poly(glycidyl methacrylate-co-ethyleneglycol dimethacrylate) or poly(glycidyl methacrylate-co-triethyleneglycol dimethacrylate) beads immobilized with ligand molecule, Cibacron Blue F3G-A (CB), together with poly(N-isopropylacrylamide) (PIPAAm), a polymer with a cloud point of 32 degrees C. Two different lengths of spacer molecules were used for the immobilization of CB while maintaining the PIPAAm size constant. Chromatographic analyses using bovine serum albumin as a model protein showed a clear correlation between spacer length and binding capacity at temperatures lower than the lower critical solution temperature (LCST) of PIPAAm. The binding capacity under the LCST was significantly reduced only when the calculated spacer length was shorter than the mean size of the extended PIPAAm. Furthermore, the adsorbed protein could be desorbed (released) from the matrix surface by lowering the temperature to below the LCST while maintaining other factors such as pH and ion strength. Selective recovery of human albumin from human sera was demonstrated using this newly developed thermoresponsive affinity column.     

Thermal characterization of amorphous selenium films obtained by low-temperature photodeposition

The thermal treatment structural behaviour of amorphous selenium (a-Se) films as obtained by a low-temperature photodeposition process was studied. Differential scanning calorimetry (DSC) measurements were used to obtain detailed information regarding the structural changes in the temperature range of –50–250 C. Our understanding of the crystallization behaviour was also aided by scanning electron microscopy (SEM) and X-ray diffraction analysis (XRD). The results were compared to other observations made on structural transitions of a-Se obtained traditionally by high-temperature processes such as quenching from the melt and vacuum deposition. Comparing the DSC thermograms clearly shows that the low-temperature photodeposition process gives a different structural transition behaviour of a-Se during thermal crystallization. Specifically new transitions were observed structurally in the temperature range 80–160C.     

In situ TEM observation of heterogeneous phase transition of a constrained single-crystalline Ag2Te nanowire

Laterally epitaxial single crystalline Ag2Te nanowires (NWs) are synthesized on sapphire substrates by the vapor transport method. We observed the phase transitions of these Ag2Te NWs via in situ transmission electron microscopy (TEM) after covering them with Pt layers. The constrained NW shows phase transition from monoclinic to a body-centered cubic (bcc) structure near the interfaces, which is ascribed to the thermal stress caused by differences in the thermal expansion coefficients. Furthermore, we observed the nucleation and growth of bcc phase penetrating into the face-centered cubic matrix at 200 °C by high-resolution TEM in real time. Our results would provide valuable insight into how compressive stresses imposed by overlayers affect behaviors of nanodevices.     

Bioactivated collagen-based scaffolds embedding protein-releasing biodegradable microspheres: tuning of protein release kinetics

In tissue engineering, the recapitulation of natural sequences of signaling molecules, such as growth factors, as occurring in the native extracellular matrix (ECM), is fundamental to support the stepwise process of tissue regeneration. Among the manifold of tissue engineering strategies, a promising one is based on the creation of the chrono-programmed presentation of different signaling proteins. This approach is based upon the integration of biodegradable microspheres, loaded with suitable protein molecules, within scaffolds made of collagen and, in case, hyaluronic acid, which are two of the fundamental ECM constituents. However, for the design of bioactivated gel-like scaffolds the determination of release kinetics must be performed directly within the tissue engineering template. In this work, biodegradable poly(lactic-co-glycolic)acid (PLGA) microspheres were produced by the multiple emulsion-solvent evaporation technique and loaded with rhodamine-labelled bovine serum albumin (BSA-Rhod), a fluorescent model protein. The microdevices were dispersed in collagen gels and collagen-hyaluronic acid (HA) semi-interpenetrating networks (semi-IPNs). BSA-Rhod release kinetics were studied directly on single microspheres through confocal laser scanning microscopy (CLSM). To thoroughly investigate the mechanisms governing protein release from PLGA microspheres in gels, BSA-Rhod diffusion in gels was determined by fluorescence correlation spectroscopy (FCS), and water transport through the microsphere bulk was determined by dynamic vapor sorption (DVS). Moreover, the decrease of PLGA molecular weight and glass transition temperature (T_g) were determined by gel permeation chromatography (GPC) and differential scanning calorimetry (DSC), respectively. Results indicate that protein release kinetics and delivery onset strongly depend on the complex interplay between protein transport through the PLGA matrix and in the collagen-based release media, and water sequestration within the scaffolds, related to the scaffold hydrophilicity, which is dictated by HA content. The proper manipulation of all these features may thus allow the obtainment of a fine control over protein sequential delivery and release kinetics within tissue-engineering scaffolds.     

Chemical-induced unfolding of cofactor-free protein monitored by electrochemistry

Protein folding has been studied extensively with an aim to better understanding of the relationship between protein sequence, structure, and function. A large variety of techniques have been developed and utilized to probe protein conformation and folding/unfolding transition. In this report, electrochemical monitoring of urea-induced unfolding of a large cofactor-free protein, bovine serum albumin (BSA), is described. Enhanced electrochemical oxidation of tyrosine and tryptophan in free amino acids and in BSA was achieved on an indium tin oxide electrode by using an electron mediator, Os(bpy)2dppz (bpy = 2,2'-bipyridine, dppz = dipyrido[3,2-a:2',3'-c]phenazine). The oxidation current was used as a signal reporter in the monitoring of urea-induced BSA denaturation. At high urea concentrations, the electrochemical signal increased by 3-fold relative to the native protein. The increase is attributed to the closer contact between the oxidizable residues in the unfolded BSA and Os(bpy)2dppz. The degree of unfolding assessed by electrochemistry correlates well with the established fluorescence technique in the range of 0-10 M urea. The method can be used to investigate the unfolding process of other cofactor-free proteins.     

高分子量聚苯硫醚的热分析

用ＤＳＣ和ＴＭＡ测定了高分子量聚苯硫醚树脂的玻璃化转变温度,结果温主、熔点等热转变参数,研究了热退火处理对这些转变参数的影响,结果表明,两种方法测定的ＰＰＳ的热转变温度是一致的。     

Thermal and IR studies on copper doped polyvinyl alcohol

5 mol% PVA: x mol% Cu²⁺ polymer films were prepared by casting process. Thermal transitions and thermal degradation of samples with respect to copper concentration were studied by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA), respectively. Increase in glass transition temperature as a function of copper concentration shows a strong branching and steric effects in copper doped PVA complexes. Thermal degradation of films to an extent of 4–5% was found with an increase in copper content. FTIR spectrum of PVA doped Cu²⁺ ions indicate the presence of O-H, C-H, C=C and C-O groups.     

Study of thermal dynamics of defatted bovine serum albumin in D2O solution by Fourier transform infrared spectra and evolving factor analysis

Fourier transform infrared (FT-IR) spectra have been measured for defatted bovine serum albumin (BSA) in D(2)O with a concentration of 2.0 wt % over a temperature range of 26-90 degrees C and the corresponding difference spectra have been calculated by subtracting the contribution of D(2)O at the same temperature. Evolving factor analysis (EFA) by selecting two factors and three factors has been employed to analyze the temperature-dependent difference IR spectra in the 1700-1600 cm(-1) spectral region of the defatted BSA in D(2)O solution. Three-factor EFA has been employed to determine the distinction of the three protein species involved in the process of temperature elevation: native, transitional, and denatured protein. The temperature profiles obtained from three-factor EFA indicate that heat-induced conformational change in the secondary structures of defatted BSA in D(2)O undergoes two two-state transitions, a drastic transition and a slight transition, which occur in the temperature ranges of 68-82 degrees C and 56-76 degrees C, respectively.