Characteristic Transition Temperature Research Articles

Structural analysis of polyolefin-poly(methyl methacrylate) blends

Polyethylenes (PEs) of different type and crystallinity (LDPE, HDPE and UHMWPE) were used to prepare blends of 80/20 ratio with poly(methyl methacrylate) (PMMA) and to evaluate their mechanical and structural properties. Methyl methacrylate monomer was mixed with the polyethylenes and the mixture was irradiated to in situ form the PMMA polymer, the blend and by expectation some copolymer. By evaluating the glass transition temperatures, insight can be gained in the structural changes within the PE and PMMA polymers. DSC and DMA tests yielded results where the characteristic transition temperature of the matrix polyethylene has shifted. After carrying out the DMA test, the samples were retested via DSC to evaluate the effect of the mechanical stresses. TSD method was used here to analyze the molecular movements in PE-PMMA blends. The results of the measurements show the appearance of PMMA phase in the polyethylene matrix, which inhibits the relaxation of crosslinked polyethylene. It is an unexpected behavior, because according to the calculations, PMMA and the PE should form an immiscible blend. These results indicate that during cyclic loading, the structure of the composition changed significantly. Its importance is that similar cyclic deformations/loads affect the hip joint implants also. The wear resistance of the prepared PE/PMMA 80/20 w/w % samples was measured using tribological methods, which show some improvement in all cases.

Thermal characteristics and state diagram of extruded instant artificial rice

Instant artificial rice was developed by extrusion method using corn flour, glycerol monostearate (GSM), and glucomannan and guar gum. Moisture sorption isotherm and thermal characteristics of the artificial rice with glucomannan and guar gum were measured and modeled to develop different regions of a state diagram. The freezing point, glass transition, and solids-melting were measured and modeled by Chen’s model, modified Gordon–Taylor model, and Flory–Huggins model, respectively. The ultimate maximal-freeze-concentration conditions were found as (Tm′)u (i.e., annealed end glass transition temperature for the sample with moisture 0.40g/g sample) equal to −8.3°C and (Tg‴)u (i.e., annealed onset glass transition temperature for the sample with moisture 0.40g/g sample) equal to −8.4°C, and the characteristic solids content, Xs′ as 0.76g/g sample (i.e., un-freezable water, Xw′ equal to 0.24g/g sample). Similarly the characteristic glass transition temperature, Tgiv (i.e., intersection of vertical line passing through Tm′ and glass transition line above Xs′) was estimated as 29.8°C.

Nanogel formation from dilute solutions of clickable elastin-like recombinamers and its dependence on temperature: two fractal gelation modes.

Diluted, complementary, click-reactive elastin-like recombinamer (ELR) solutions have been prepared and mixed at two different temperatures, one below and one above the characteristic transition temperature (Tt) of these chemically modified ELRs. FTIR measurements, size, aspect ratio, zeta potential, and microrheological measurements have been carried out on the nanostructures formed under these dilute conditions as a way to better understand the relationship between the final macroscopic properties of ELR-based hydrogels and the molecular conditions governing the initial stages of the chemical cross-linking process that occurs, especially its dependence on the preparation temperature relative to Tt. As a result, two different fractal modes of gel formation have been found at the two temperatures studied (above and below Tt). Thus, when the reaction mixture is prepared below Tt, essentially one-dimensional linear nanogels with a high aspect ratio are obtained. In contrast, 3D nanogels are formed above Tt, with spherical shapes predominating. These different structures seem to reflect the two molecular organizations of the single components of the mixture under these conditions, namely extended chains below Tt and a spherical arrangement above Tt. In addition to the interest in these nanogels as models for understanding the formation of microscopic structures and differential macroscopic properties under more conventional hydrogel-formation conditions, these nanogels are of interest because of their thermoresponsiveness and biocompatibility, which provide them with potential uses for drug delivery and other biomedical applications in living systems.

Non-chromatographic Purification of Recombinant Elastin-like Polypeptides and their Fusions with Peptides and Proteins from <em>Escherichia coli</em>

Elastin-like polypeptides are repetitive biopolymers that exhibit a lower critical solution temperature phase transition behavior, existing as soluble unimers below a characteristic transition temperature and aggregating into micron-scale coacervates above their transition temperature. The design of elastin-like polypeptides at the genetic level permits precise control of their sequence and length, which dictates their thermal properties. Elastin-like polypeptides are used in a variety of applications including biosensing, tissue engineering, and drug delivery, where the transition temperature and biopolymer architecture of the ELP can be tuned for the specific application of interest. Furthermore, the lower critical solution temperature phase transition behavior of elastin-like polypeptides allows their purification by their thermal response, such that their selective coacervation and resolubilization allows the removal of both soluble and insoluble contaminants following expression in Escherichia coli. This approach can be used for the purification of elastin-like polypeptides alone or as a purification tool for peptide or protein fusions where recombinant peptides or proteins genetically appended to elastin-like polypeptide tags can be purified without chromatography. This protocol describes the purification of elastin-like polypeptides and their peptide or protein fusions and discusses basic characterization techniques to assess the thermal behavior of pure elastin-like polypeptide products.

Non-chromatographic purification of recombinant elastin-like polypeptides and their fusions with peptides and proteins from Escherichia coli.

Elastin-like polypeptides are repetitive biopolymers that exhibit a lower critical solution temperature phase transition behavior, existing as soluble unimers below a characteristic transition temperature and aggregating into micron-scale coacervates above their transition temperature. The design of elastin-like polypeptides at the genetic level permits precise control of their sequence and length, which dictates their thermal properties. Elastin-like polypeptides are used in a variety of applications including biosensing, tissue engineering, and drug delivery, where the transition temperature and biopolymer architecture of the ELP can be tuned for the specific application of interest. Furthermore, the lower critical solution temperature phase transition behavior of elastin-like polypeptides allows their purification by their thermal response, such that their selective coacervation and resolubilization allows the removal of both soluble and insoluble contaminants following expression in Escherichia coli. This approach can be used for the purification of elastin-like polypeptides alone or as a purification tool for peptide or protein fusions where recombinant peptides or proteins genetically appended to elastin-like polypeptide tags can be purified without chromatography. This protocol describes the purification of elastin-like polypeptides and their peptide or protein fusions and discusses basic characterization techniques to assess the thermal behavior of pure elastin-like polypeptide products.

Design and Characterization of a Resistively Heated Shape Memory Polymer Micro-Release Device1

Design and Characterization of a Resistively Heated Shape Memory Polymer Micro-Release Device1

Thermal Spin Crossover Behaviour of Two-Dimensional Hofmann-Type Coordination Polymers Incorporating Photoactive Ligands

Two spin crossover (SCO)-active 2D Hofmann-type framework materials, [Fe(3-PAP)2Pd(CN)4] (A) and [Fe(4-PAP)2Pd(CN)4] (B) containing the photoactive azo-benzene-type ligands 3-phenylazo-pyridine (3-PAP) and 4-phenylazo-pyridine (4-PAP) were prepared. These materials form non-porous Hofmann-type structures whereby 2D [FeIIPd(CN)4] grids are separated by 3- or 4-PAP ligands. The iron(ii) sites of both materials (A and B) undergo abrupt and hysteretic spin transitions with characteristic transition temperatures T1/2↓,↑: 178, 190 K (ΔT: 12 K) and T1/2↓,↑: 233, 250 K (ΔT: 17 K), respectively. Photo-magnetic characterisations reveal light-induced excited spin state trapping (LIESST) activity in both A and B with characteristic T(LIESST) values of 45 and 40 K. Although both free ligands show trans- to-cis isomerisation in solution under UV-irradiation, as evidenced via absorption spectroscopy, such photo-activity was not observed in the ligands or complexes A and B in the solid state. Structural analysis of a further non-SCO active isomer to B, [Fe(4-PAP)2Pd(CN)4]·1/2(4-PAP) (B·(4-PAP)), which contains free ligand in the pore space is reported.

Optical, physical and structural studies of vanadium doped P2O5–BaO–Li2O glasses

Glasses in the compositions (Li2O)25–(BaO)25–(P2O5)50−x–(V2O5)x (with x=0.5,1.0,1.5,2.0,2.5, and 3.0mol%) have been prepared by the conventional melt quenching technique. X-ray powder diffractrogram show broad peaks which conforms glassy nature of the sample. Differential scanning calorimetry (DSC) thermograms show characteristic glass transition temperature (Tg) and it increases with increasing substitution of V2O5 for P2O5. The measured physical parameters like density, refractive index, ionic concentration and electronic polarizability are found to vary linearly with increasing x. Infrared spectra exhibits few bands, which are attributed to (P=O)AS, (P=O)S, (V=O), (P–O–P)AS,P–O–V, (P–O–P)AS and O–P–O vibrations. The optical absorption spectra of VO2+ ions in these glasses show three bands and are assigned to the 2B2→ 2E,2B2→ 2B1 and 2B2→ 2A1 transitions. Electron paramagnetic resonance spectra of all the glass samples exhibit resonance signals characteristic of VO2+ ions. The values of Spin-Hamiltonian parameters indicate that the VO2+ ions are present in octahedral sites with tetragonal compression and belong to C4V symmetry.

Influence of Si substitution on the structure, magnetism, exchange bias and negative magnetoresistance in Ni48Mn39Sn13 Heusler alloys

The effect of partial Si substitution for Sn on the structure, magnetism, magnetic entropy change, exchange bias and negative magnetoresistance in Ni48Mn39Sn13−xSix(1 ⩽ x ⩽ 4) Heusler alloy systems is investigated. A small amount of Si in the Sn position influences the characteristic transition temperatures and the magnetocaloric effect. A maximum positive entropy change of 5.13 J kg−1 K−1 is observed for a field change of 9 T in the x = 1 alloy. An increase in Si content increases the exchange bias field. The exchange bias field and the coercive field strongly depend on the Si content. For the x = 4 alloy, an exchange bias field of 354 Oe is observed. In addition, a negative magnetoresistance is observed in this alloy system, which decreases with Si content. The increase in resistivity at the martensitic transition could be attributed to the formation of superzone boundary gaps that changes the density of states near the Fermi surface.

Predicting Transition Temperatures of Elastin-Like Polypeptide Fusion Proteins

Elastin-like polypeptides (ELPs) are thermally sensitive peptide polymers that undergo thermally triggered phase separation and this behavior is imparted to soluble proteins when they are fused to an ELP. The transition temperature of the ELP fusion protein is observed to be different than that of a free ELP, indicating that the surface properties of the fused protein modulate the thermal behavior of ELPs. Understanding this effect is important for the rational design of applications that exploit the phase transition behavior of ELP fusion proteins. We had previously developed a biophysical model that explained the effect of hydrophobic proteins on depressing the transition temperature of ELP fusion proteins relative to free ELP. Here, we extend the model to elucidate the effect of hydrophilic proteins on the thermal behavior of ELP fusion proteins. A linear correlation was found between overall residue composition of accessible protein surface weighted by a characteristic transition temperature for each residue and the difference in transition temperatures between the ELP protein fusion and the corresponding free ELP. In breaking down the contribution of residues to polar, nonpolar, and charged, the model revealed that charged residues are the most important parameter in altering the transition temperature of an ELP fusion relative to the free ELP.

Suppression of Metal-Insulator Transition in VO 2 by Electric Field–Induced Oxygen Vacancy Formation

Electrolyte gating with ionic liquids is a powerful tool for inducing novel conducting phases in correlated insulators. An archetypal correlated material is vanadium dioxide (VO(2)), which is insulating only at temperatures below a characteristic phase transition temperature. We show that electrolyte gating of epitaxial thin films of VO(2) suppresses the metal-to-insulator transition and stabilizes the metallic phase to temperatures below 5 kelvin, even after the ionic liquid is completely removed. We found that electrolyte gating of VO(2) leads not to electrostatically induced carriers but instead to the electric field-induced creation of oxygen vacancies, with consequent migration of oxygen from the oxide film into the ionic liquid. This mechanism should be taken into account in the interpretation of ionic liquid gating experiments.

Thermally Targeted Delivery of a c-Myc Inhibitory Polypeptide Inhibits Tumor Progression and Extends Survival in a Rat Glioma Model

Treatment of glioblastoma is complicated by the tumors’ high resistance to chemotherapy, poor penetration of drugs across the blood brain barrier, and damaging effects of chemotherapy and radiation to normal neural tissue. To overcome these limitations, a thermally responsive polypeptide was developed for targeted delivery of therapeutic peptides to brain tumors using focused hyperthermia. The peptide carrier is based on elastin-like polypeptide (ELP), which is a thermally responsive biopolymer that forms aggregates above a characteristic transition temperature. ELP was modified with cell penetrating peptides (CPPs) to enhance delivery to brain tumors and mediate uptake across the tumor cells’ plasma membranes and with a peptide inhibitor of c-Myc (H1). In rats with intracerebral gliomas, brain tumor targeting of ELP following systemic administration was enhanced up to 5-fold by the use of CPPs. When the lead CPP-ELP-fused c-Myc inhibitor was combined with focused hyperthermia of the tumors, an additional 3 fold increase in tumor polypeptide levels was observed, and 80% reduction in tumor volume, delayed onset of tumor-associated neurological deficits, and at least doubled median survival time including complete regression in 80% of animals was achieved. This work demonstrates that a c-Myc inhibitory peptide can be effectively delivered to brain tumors.

Hysteresis effects in the inverse magnetocaloric effect in martensitic Ni-Mn-In and Ni-Mn-Sn

The presence of a large inverse magnetocaloric effect around the martensitic transformation in Ni-Mn-Sn and Ni-Mn-In alloys is expected to lead to substantial cooling on applying a magnetic field. However, the occurrence of hysteresis around the transition causes limitations on adiabatic temperature-changes. We study the adiabatic temperature-change in both systems in relation to the hysteresis effects. Ni-Mn-In, having a relatively narrower hysteresis and a greater shift of the characteristic transition temperatures with applied field with respect to Ni-Mn-Sn, shows reversibility in the adiabatic-temperature change related to the inverse magnetocaloric effect when the state of the system is cycled within a minor transitional hysteresis loop. Ni-Mn-Sn does not show reversibility in the inverse magnetocaloric effect under cycling-fields up to 5 T. The reversibility in the adiabatic temperature-change is directly related to the reversibility in the relative amount of austenite and martensite in the sample when the field is cycled.

Preparation and characterization of elastin-like polypeptide scaffolds for local delivery of antibiotics and proteins

Tissue engineering applications could benefit from simultaneous release of growth factors, signaling molecules, and antibiotics to obtain optimal healing of tissues. Elastin-like polypeptides (ELPs) are genetically engineered polymers that possess good biocompatibility, are biodegradable, and exhibit mechanical properties similar to natural elastin. In addition, ELPs exhibit a characteristic inverse phase transition temperature (T(t)). This T(t) behavior is widely exploited in hyperthermia mediated drug delivery. The objectives of this research were to prepare ELP hydrogel scaffolds using a novel ultrasonication method and to investigate the release of a model protein (bovine serum albumin, BSA) and a commonly used antibiotic in periodontal therapy (doxycycline) from the scaffolds at two different temperatures (25 °C <T(t) vs. 37 °C >T(t)). Both BSA and doxycycline showed a gradual time dependent release and showed a trend of higher release fractions with higher loading doses. Based on the comparison between the release profiles at the two selected temperatures, the release was higher at 37 °C compared to that at 25 °C for both the loading concentrations of doxycycline (0.05 and 0.1 % v/v) and only one of the loading concentrations of BSA (0.5 % v/v) studied, while the release was higher at 25 °C compared to that at 37 °C only for the other loading concentration of BSA (1 % v/v) studied. These results suggested that the drug molecular weight and loading concentration were significant factors that affected the release kinetics. The experiments in this study demonstrated that the ELP hydrogel scaffolds can successfully release proteins and antibiotics critical to tissue engineering.

Calorimetric study and thermal analysis of Al–Sn system

The results of calorimetric study and thermal analysis of binary Al–Sn system are presented in this paper. The Oelsen calorimetry was used in thermodynamic analysis. Following thermodynamic properties were determined at 727 °C: activities, activity coefficients, partial/integral molar Gibbs excess, and mixing energies. The energetics of mixing in liquid Al–Sn alloys has been analyzed through the study of concentration fluctuation in the long-wavelength limit. Thermal analysis of selected alloys in Al–Sn system was done using differential thermal analysis. Defined characteristic phase transition temperatures were used for comparison with calculated phase diagram of investigated system. Good agreement with available literature data was obtained. Structural analysis of selected alloys was done using optic microscopy.

Effect of chirality on domain wall dynamics in molecular ferrimagnet [MnII(HL-pn)(H2O)][MnIII(CN)6]·2H2O

In this paper we distinguish the contributions of switching, slide, creep and Debye relaxation modes of the domain wall dynamics to the low-frequency magnetic properties of chiral and racemic [MnII(HL-pn)(H2O)][MnIII(CN)6]·2H2O molecular ferrimagnets. We demonstrate that crystal and spin chirality affects the characteristic transition temperatures between different modes. In chiral crystals, transitions to the creep and Debye relaxation modes were observed at T = 7 K and 5 K, whereas in racemic crystals the same transitions occurred at higher temperatures T = 13 K and 9 K, respectively. Difference of the Peierls relief in chiral and racemic crystals is a possible reason of the chirality effect on the domain walls dynamics.

FeCr2O4 and CoCr2O4 spinels: Multiferroicity in the collinear magnetic state?

Dielectric permittivity (ɛ′) and electrical polarization (P) have been measured as a function of temperature for two polycrystalline ACr2O4 spinels (A = Fe and Co). Anomalies on the ɛ′(T) curves are detected at the characteristic magnetic transition temperatures (TC, TS, and Tlock-in) for FeCr2O4 and CoCr2O4 and also at the Jahn-Teller (JT) transition for FeCr2O4. The P(T) curves of both spinels exhibit transitions at TC showing that polar and ferrimagnetic states coexist in these oxides. The link between the distortion of the spinel structure due to the Jahn-Teller Fe2+ and the larger polarization value at 8 K, P = 35 μC/m2, against P = 3.5 μC/m2 for CoCr2O4, is also discussed.

Stability of Anthocyanins in Frozen and Freeze‐Dried Raspberries during Long‐Term Storage: In Relation to Glass Transition

Anthocyanins, natural plant pigments in the flavonoid group, are responsible for the red color and some of the nutraceutical benefits of raspberries. This study explores anthocyanin degradation in frozen and freeze-dried raspberries during storage in relation to glass transition temperatures. Frozen raspberries were stored at -80, -35, and -20 °C, while freeze-dried raspberries were stored at selected water activity (a(w)) values ranging from 0.05 to 0.75 at room temperature (23 °C) for more than a year. The characteristic glass transition temperatures (T'(g)) of raspberries with high water content and glass transition temperature (T(g)) of raspberries with small water content were determined using a differential scanning calorimeter. The pH differential method was used to determine the quantity of anthocyanins in frozen and freeze-dried raspberries at selected time intervals. The total anthocyanins in raspberries fluctuated during 378 d of storage at -20 and -35, and -80 °C. Anthocyanin degradation in freeze-dried raspberries ranged from 27% to 32% and 78% to 89% at a(w) values of 0.05 to 0.07 and 0.11 to 0.43, respectively, after 1 y. Anthocyanins were not detectable in freeze-dried raspberries stored at a(w) values of 0.53 to 0.75 after 270 d. First order and Weibull equations were used to fit the anthocyanin degradation in freeze-dried raspberries. The 1(st)-order rate constant (k) of anthocyanin degradation ranged from 0.003 to 0.023 days⁻¹ at the selected water activities. Significant anthocyanin degradation occurred in both the glassy and rubbery states of freeze-dried raspberries during long-term storage. However, the rate of anthocyanin degradation in freeze-dried raspberries stored in the glassy state was significantly smaller than the rate of anthocyanin degradation in the rubbery state.

Assessment and Formation Mechanism of Laser-Induced Periodic Surface Structures on Polymer Spin-Coated Films in Real and Reciprocal Space

In this work we evaluate the potential of grazing incidence X-ray scattering techniques in the investigation of laser-induced periodic surface structures (LIPSSs) in a series of strongly absorbing model spin-coated polymer films which are amorphous, such as poly(ethylene terephthalate), poly(trimethylene terephthalate), and poly(carbonate bisphenol A), and in a weaker absorbing polymer, such as semicrystalline poly(vinylidene fluoride), over a narrow range of fluences. Irradiation was performed with pulses of 6 ns at 266 nm, and LIPSSs with period lengths similar to the laser wavelength and parallel to the laser polarization direction are formed by devitrification of the film surface at temperatures above the characteristic glass transition temperature of the polymers. No crystallization of the surface is induced by laser irradiation, and crystallinity of the material prevents LIPSS formation. The structural information obtained by both atomic force microscopy and grazing incidence small-angle X-ray scattering (GISAXS) correlates satisfactorily. Comparison of experimental and simulated GISAXS patterns suggests that LIPSSs can be well described considering a quasi-one-dimensional paracrystalline lattice and that irradiation parameters have an influence on the order of such a lattice.

In‐Situ Incorporation of Amoxicillin in PVA/PVAc‐co‐PMMA Particles during Suspension Polymerizations

AbstractEmbolization is a radiological technique that consists in occluding a blood vessel intentionally with an embolic agent (particle). A suspension polymerization process was developed to allow for production of embolic particles with core‐shell morphology. This technology was modified to allow for the in‐situ incorporation of antibiotics (amoxicillin) in PVA/PVAc‐co‐PMMA core‐shell particles. The incorporation of amoxicillin led to modification of some of the final polymer properties, including the particle morphology, the molecular weight distribution and the characteristic transition temperatures of the polymer material. The final polymer properties depended on the antibiotic concentration and on how the drug was added into the polymerization medium.