In an ongoing effort to understand the thermodynamic properties of proteins, ovalbumin, lactoglobulin, lysozyme are studied
by adiabatic and differential scanning calorimetry over wide temperature ranges. The heat capacities of the samples in their
pure, solid states are linked to an approximate vibrational spectrum with the ATHAS analysis that makes use of known group
vibrations and a set of parameters, Θ1 and Θ3, of the Tarasov function for the skeletal vibrations. Good agreement is found between experiment and calculation with rms
errors mostly within ±3%. The analyses were also carried out with an empirical addition scheme using data from polypeptides
of naturally occurring amino acids. Due to space limitation, only selected results are reported.
A new, least-squares optimization method with interpolation is devised to fit skeletal vibrational heat capacities to the two parameters θ1 and θ3 in the Tarasov function used for heat capacity calculations of linear macromolecules. When heat capacities are available in the proper temperature range, θ1 and θ3 can be determined uniquely in a single computer run. Appended to our Advanced THermal Analysis System (ATHAS), this new method offers an improvement in analyzing heat capacity data and facilitates the systematic study of the physical significance of θ1 and θ3 values for all polymers and related molecules of the ATHAS data bank.
As a consequence
of their excellent barrier properties vinyl chloride/vinylidene chloride copolymers
have long been prominent in the flexible packaging market. While these polymers
possess a number of superior characteristics, they tend to undergo thermally-
induced degradative dehydrochlorination at process temperatures. This degradation
must be controlled to permit processing of the polymers. Three series of N-substituted
maleimides (N-alkyl-, N-aralkyl, and N-aryl) have been synthesized, characterized
spectroscopically, and evaluated as potential stabilizers for a standard vinyl
chloride/vinylidene chloride (85 mass%) copolymer. As surface blends with
the polymer, these compounds are ineffective as stabilizers. However, significant
stabilization may be achieved by pretreatment of the polymer with N-substituted
maleimides. The most effective stabilization of the polymer is afforded by
N-aralkyl- or N-arylmaleimides, most notably, N-benzylmaleimide and N-p-methoxyphenylmaleimide.
The organometallic precursor fac-[99mTc(CO)3(H2O)3]+ was reacted with N-ethoxy, N-ethyl dithiocarbamate (NOET) in phosphate buffered saline (pH 7.4) at room temperature for 30
minutes to produce the 99mTc(CO)3-NOET complex. The radiochemical purity (RCP) of the product was over 90% as measured by thin layer chromatography (TLC).
No decomposition of the complex at room temperature (RT) was observed over a period of 6 hours. Its partition coefficient
indicated that it was a lipophilic complex. The biodistribution comparison in mice of the 99mTc(CO)3-NOET complex and the 99mTcN-NOET complex showed that the former had a lower heart and brain uptake as compared to that of the latter, suggesting the
incorporation of the [99mTc(CO)3]+ core into the NOET ligand does not improve the biological features as a myocardial imaging agent.
Authors:B. Zhang, Y. Li, Q. Li, B. Ma, F. Gan, Z. Zhang, H. Cheng, and F. Yang
External-beam PIXE was used for the non-destructive analysis of early glasses unearthed from the tombs of Warring States (475–221BC) and Han Dynasty (BC 206–AD 220) in south China. It was found that these glasses were basically attributed to PbO—BaO—SiO2 system and K2O—SiO2 system. The results from the cluster analysis showed that some glasses had exactly the same recipe. The source of the K2O flux and the correlation between PbO and BaO are discussed. Some archeological information is revealed.
Authors:B. Hu, Y. Song, L. Wang, Q. Zhang, J. Li, K. Wei, Y. Chen, and L. Zhang
Electronic stopping power of 19F in Ni, Pd and Gd was measured and compared to Mstar and SRIM calculation as well as experimental results published in literature.
It turns out that the present electronic stopping power agrees reasonably well with them.
Authors:B. Lin, L. Yang, H. Dai, Q. Hou, and L. Zhang
Soybean oil based polyols (5-OH polyol, 10-OH polyol and 15-OH polyol) were synthetised from epoxidized soybean oil. The melting
peak of polyols and the relationship between melting peak and the number-average functionality of hydroxyl in polyols were
investigated by differential scanning calorimetry (DSC). The thermal decomposition of polyols and some of their thermal properties
by thermogravimetry (TG) and derivative thermogravimetry (DTG) were also studied. The thermal stability of polyols in a nitrogen
atmosphere was very close hence they had a same baseplate of triglyceride for polyols. The extrapolated onset temperature
of polyols in their thermal mass loss, first step had a decreasing order: 5-OH polyol>10-OH polyol>15-OH polyol due to the
difficulty in forming multiple elements ring of them had the same order.
The thermal behavior of polyols under non-isothermal conditions using Friedman’s differential isoconversional method with
different heating rates indicated that the 5-OH polyol had the lowest activation energy in thermal decomposition amongst these
polyols according to the same fractional mass loss because of the weakest intramolecular oligomerization. The 15-OH polyol
was prior to reach the mass loss region because the six-member ring is more stable than the three-member ring from 10-OH polyol
and more easily formed.
The low-temperature heat capacity Cp,m of erythritol (C4H10O4, CAS 149-32-6) was precisely measured in the temperature range from 80 to 410 K by means of a small sample automated adiabatic
calorimeter. A solid-liquid phase transition was found at T=390.254 K from the experimental Cp-T curve. The molar enthalpy and entropy of this transition were determined to be 37.92±0.19 kJ mol−1 and 97.17±0.49 J K−1 mol−1, respectively. The thermodynamic functions [HT-H298.15] and [ST-S298.15], were derived from the heat capacity data in the temperature range of 80 to 410 K with an interval of 5 K. The standard
molar enthalpy of combustion and the standard molar enthalpy of formation of the compound have been determined: ΔcHm0(C4H10O4, cr)= −2102.90±1.56 kJ mol−1 and ΔfHm0(C4H10O4, cr)= − 900.29±0.84 kJ mol−1, by means of a precision oxygen-bomb combustion calorimeter at T=298.15 K. DSC and TG measurements were performed to study the thermostability of the compound. The results were in agreement
with those obtained from heat capacity measurements.
A fully automated adiabatic calorimeter controlled on line by a computer used for heat capacity measurements in the temperature
range from 80 to 400 K was constructed. The hardware of the calorimetric system consisted of a Data Acquisition/Switch Unit,
34970A Agilent, a 7 1/2 Digit Nano Volt /Micro Ohm Meter, 34420A Agilent, and a P4 computer. The software was developed according
to modern controlling theory. The adiabatic calorimeter consisted mainly of a sample cell equipped with a miniature platinum
resistance thermometer and an electric heater, two (inner and outer) adiabatic shields, two sets of six junction differential
thermocouple piles and a high vacuum can. A Lake Shore 340 Temperature Controller and the two sets of differential thermocouples
were used to control the adiabatic conditions between the cell and its surroundings. The reliability of the calorimeter was
verified by measuring the heat capacities of synthetic sapphire (α-Al2O3), Standard Reference Material 720. The deviation of the data obtained by this calorimeter from those published by NIST was
within ±0.1% in the temperature range from 80 to 400 K.
Authors:A. Boller, I. Okazaki, K. Ishikiriyama, G. Zhang, and B. Wunderlich
The quality of measurement of heat capacity by differential scanning calorimetry (DSC) is based on the symmetry of the twin
calorimeters. This symmetry is of particular importance for the temperature-modulated DSC (TMDSC) since positive and negative
deviations from symmetry cannot be distinguished in the most popular analysis methods. Three different DSC instruments capable
of modulation have been calibrated for asymmetry using standard non-modulated measurements and a simple method is described
that avoids potentially large errors when using the reversing heat capacity as the measured quantity. It consists of overcompensating
the temperature-dependent asymmetry by increasing the mass of the sample pan.