Thermal Stabilization of an Endoglucanase by Cyclization

An intein-driven protein splicing approach allowed for the covalent linkage between the N- and C-termini of a polypeptide chain to create circular variants of the endo-??-1,3-1,4-glucanase, LicA, from Bacillus licheniformis. Two circular variants, LicA-C1 and LicA-C2, which have connecting loops of 20 and 14 amino acids, respectively, showed catalytic activities that are approximately two and three times higher, respectively, compared to that of the linear LicA (LicA-L1). The thermal stability of the circular variants was significantly increased compared to the linear form. Whereas the linear glucanase lost half of its activity after 3?min at 65?°C, the two circular variants have 6-fold (LicA-C1) and 16-fold (LicA-C2) increased half-life time of inactivation. In agreement with this, fluorescence spectroscopy and differential scanning calorimetry studies revealed that circular enzymes undergo structural changes at higher temperatures compared to that of the linear form. The effect of calcium on the conformational stability and function of the circular LicAs was also investigated, and we observed that the presence of calcium ions results in increased thermal stability. The impact of the length of the designed loops on thermal stability of the circular proteins is discussed, and it is suggested that cyclization may be an efficient strategy for the increased stability of proteins.     

差示扫描量热法研究丙烯腈-衣康酸共聚物的热稳定化

应用差示扫描量热法(DSC)研究了衣康酸(IA)、气氛、升温速率对丙烯腈-衣康酸共聚物[P(AN-IA)]热稳定化的影响. IA能够显著降低放热峰起始温度、放热量和放热速率. P(AN-IA)共聚物的放热峰起始温度受气氛影响不大, 却随着IA含量的增加而明显降低, 表明在热稳定化过程中它可能首先以离子机理发生氰基环化反应, 再发生氧化反应. 提高升温速率会导致放热峰向高温偏移和放热速率加快. 采用Kissinger法计算了不同IA含量共聚物的热稳定化活化能, 结果表明IA可以有效降低活化能.     

Stabilization of PVC to Light and Heat

The actual status of the heat and light stabilization of PVC is reviewed with emphasis on the stabilizers and their mode of action.     

用热分析技术测定碳化硅粉体对聚乙二醇的吸附量

用热分析技术TG-DTA(thermal gravimetric and differential thermal analysis)测定浆料中碳化硅粉体对分散剂聚乙二醇PEG(polyethylene glycol)的吸附量. 结果显示PEG在Ar气氛中411.5 ℃时完全分解; 碳化硅表面分散剂PEG的吸附量随着pH的增大而下降, 在较高pH下大多数分散剂仍存在于溶液中; 分散剂PEG的吸附量通过公式(1)进行计算. 该方法简单方便, 可以应用于测量氧化物或非氧化物吸附紫外-可见分光光度法不能测定的一些有机聚合物分子.     

ICP-AES法快速分析聚氯乙烯中复合热稳定剂

聚氯乙烯（PVC）的热稳定性较差,在加工过程中必须通过添加2％～4％热稳定剂才能有效地阻止其热降解。工业上广泛应用铅、镉、钡、钙、锌的硬脂酸盐或油酸盐等的复合物作为PVC的复合热稳定剂,通常是二元或三元复合体系,如铅钡、镉钡、镉钡锌、钙锌体系等,由于体系内组分之间有协同热稳定性,不仅使PVC加工时期的色泽好,而且有非常好的长期稳定性。     

聚乳酸-聚乙二醇单甲醚共混体系的调制DSC分析

采用调制差示扫描量热法(MDSC)研究了聚乳酸(PLA)与聚乙二醇单甲醚(MPEG)共混体系的热性能。研究结果表明,MDSC可有效分辨PLA重结晶和熔融的重叠效应,在测试条件下,PLA的α’-α晶型转变与α晶体的熔融几乎同时进行。随着升温速率的加快和调制周期的延长,当增塑剂的质量分数为15%时,PLA-MPEG共混物分割在不可逆曲线的重结晶焓逐渐升高(最高约28J/g),熔融焓逐渐降低(最低约为3.3J/g);分割在可逆曲线的熔融峰逐渐由多重峰变为单峰,且焓变值逐渐升高(最高约66.1J/g),相应的可逆曲线熔融分割比例达到了95.2%。通过提高升温速率和延长调制周期,可使大部分熔融分割在可逆曲线上,但过快的升温速率和过长的调制周期会导致PLA相转变时的周期数过少,DSC调制功能的分辨率下降,设置测试条件时需综合考虑。     

Differential Thermal Analysis of Rapid High Pressure Decompositions

Abstract

A simple sample handling technique for recording differential thermograms of volatile and/or high pressure producing compounds is described. The calculation of activation energies for several hydrazines and explosives is reported.     

Thermal studies of DBSA-doped polyaniline/PVC blends by isothermal microcalorimetry

A series of blends of dodecylbenzenesulfonic acid (DBSA)-doped polyaniline (PANDR) and PVC were synthesized by solution blending technique and investigated by heatflow microcalorimetry (HFC) for thermal and oxidative stability and for PVC–PANDR compatibility. FTIR results provided evidence for strong dipole–dipole interactions between PANDR and PVC. The energy of the oxidation is independent of the composition. The interaction energy and thermal stability increased with the increase of PANDR content in the blend. The activation energies calculated by using Arrhenius relationship can be employed for accelerated ageing of the synthesized blends. It has been observed that the average degradation of PANDR component is higher than that of PVC.     

Secondary Processes of Thermal Degradation of PVC

A brief summary of secondary processes in PVC thermal degradation is given. This includes some details of crosslinking and gel formation, cyclization, chain scission and benzene formation, Diels-Alder reaction with additives, as well as oxidation of polyenes.     

Thermal degradation of silane crosslinked unplasticized PVC

The thermal decomposition behaviour of rigid PVC, crosslinked using bis(γ-trimethoxysilylpropyl)amine as crosslinking agent has been studied. Different thermal stabilizers (tin and lead based) have been used with different crosslinking agent concentrations, and the influence of these factors on the decomposition behaviour in inert atmosphere studied. Results obtained have shown that the main effect of aminosilane is an advance of the first stage of the PVC degradation (i.e. the dehydrochlorination process). Moreover, samples with different concentrations of silane, and at different stages of their processing (i.e. after milling, pressing, crosslinking) have also been used in order to elucidate the influence of these factors on their thermal behaviour. A quantitative kinetic model has been developed and the corresponding kinetic constants have been obtained by modelling the experimental thermogravimetric data. The kinetic parameters obtained have revealed a reduction in the apparent activation energy of the hydrogen chloride loss process, which has shown to be markedly dependent on the thermal stabilizer used.     

Study of Fusion Diagrams of Two-Component Systems n-Tricozane-Pentadecane and n-Tricosane-Hexadecane by Low-Temperature Differential Thermal Analysis

The two-component systems n-tricozane-pentadecane and n-tricozane-hexadecane were studied by low-temperature differential thermal analysis. The characteristics of the eutectic compositions were determined.     

Thermal stabilisation of PVC—An alternative approach

Although the Frye and Horst^1–3 theory of PVC stabilisation has been widely accepted, it has also been subject to some criticism. An alternative approach to the stabilisation of PVC, based on polar interactions within the PVC matrix, is postulated. Some of the results of research in this area which may be explained more convincingly on the basis of this approach are discussed in this paper.     

Kinetic Study of the Reaction Between Atactic Polypropylene and Dicumyl Peroxide by Differential Thermal Analysis

Abstract

The reaction kinetics of atactic polypropylene (APP) in bulk with dicumyl peroxide (DCP) as a radical generator have been studied by means of thermal differential analysis. Hydrogen abstraction from APP by cumyl radicals gives (polypropylen)yl radicals which undergo transfer to DCP, chain scission, disproportionation, and crosslinking, as well as reaction with cumyl radicals. Chain scission is shown to be the faster and crosslinking the slower of these two processes, even at temperatures of 473 K and above. Activation parameters are determined, and an analysis of the different processes is made on their basis.     

Thermal degradation of PVC cable insulation studied by simultaneous TG-FTIR and TG-EGA methods

Thermogravimetry (TG/DTG) coupled with evolved gas analysis (MS detection) of volatiles was used to characterize the thermal behavior of commercial PVC cable insulation material during heating in the range 20-800°C in air and nitrogen, respectively. In addition, simultaneous TG/FTIR was used to elucidate chemical processes that caused the thermal degradation of the sample. A good agreement between results of the methods was found. The thermal degradation of the sample took place in three temperature ranges, namely 200-340, 360-530 and 530-770°C. The degradation of PVC backbone started in the range 200-340°C accompanied by the release of HCl, H₂O, CO₂ and benzene. The non-isothermal kinetics of thermal degradation of the PVC cable insulation in the temperature range 200-340°C was determined from TG results measured at heating rates of 1.5, 5, 10, 15 and 20 K min^-1 in nitrogen and air, respectively. The activation energy values of the thermal degradation process in the range 200-340°C of the PVC cable insulation sample were determined from TG results by ASTM method. This revised version was published online in July 2006 with corrections to the Cover Date.     

硬脂酸稀土对PVC热稳定效能的递变

研究了钪、钷外其他稀土金属硬脂酸皂对PVC热稳定作用. 结果表明 它们均属长期型热稳定剂, 与少量硬脂酸锌并用可有效改善其抑制PVC初期着色的效能;不同硬脂酸稀土与硬脂酸锌并用稳定的PVC具有相似的初期色相, 但中、长期热稳定性不同, 其中镧系金属皂的中、长期热稳定性随原子序数呈现明显的奇偶效应递变规律性;硬脂酸稀土具有类似于碱土金属皂的热稳定作用机制.     

Differential Thermal Analysis as an Acidity Probe in Zeolite Catalysts

Abstract

Differential thermal analysis is used as an acidity strength probe for a series of mordenite (zeolite) catalysts via determining the temperature at which presorbed pyridine completely desorbs from the catalyst. The findings obtained for metal(s) containing mordenite catalysts have been correlated with the Pearson's assumption concerning Lewis acids and bases and the Pauling's electronegativity of the metals contained and found compatible.

The investigated catalysts can be arranged in their observed order of acidity strength as follows: HTI > Th-HM > Re-HM > Pt-HM > Pt-Th-HM > Pt-Re-HM.     

Improvement of Structural and Thermal Stabilities of PVC and Wood/PVC Composite by Zn and Pb Stearates,and Zeolite

Three different chemical stabilizers were introduced into neat PVC and a wood/PVC composite (containing 50 phr wood flour) to improve their thermal and structural stabilities. The changes in CIE yellowness index, polyene index, %wt loss, and decomposition temperature (T_d) were monitored. The effects of type and content of thermal stabilizers, thermal ageing time, and the presence of wood flour were our main interests. The experimental results suggested that the additions of Zn and Pb stearates into PVC and wood/PVC composite could improve the thermal stability of the PVC. At the test temperature of 177°C, the additions of Zn and Pb stearates could improve the thermal stabilities of PVC by retarding the upzipped reaction and by reducing the conjugated double bonds in PVC, Pb stearate being the most suitable for thermally stabilizing the PVC. Around the T_d range (～264°C), the addition of Zn stearate reduced the T_d value of PVC whereas that of Pb stearate had no effect on the change in T_d value. Zeolite loading could shift the T_d value of the PVC from 264 to 280°C. The addition of wood particles increased the polyene content and decreased the decomposition temperature of the PVC. The effect of wood flour on the thermal and structural changes of PVC overruled that of thermal stabilizer loading.     

Thermal Degradation of Blends of PVC with Other Polymers

The thermal degradation behavior of blends of polyvinyl chloride) with polyacrylonitrile, poly(n-butyl methacrylate), poly-acrylamide, poly(N-butyl methacrylamide) and poly(methyl acrylate) is discussed, and the results for these blends and five other binary polyblends containing PVC previously studied are compared. The various types of interactions which can occur in these heterogeneous systems are considered, and the mechanisms of degradation are compared with those of each polymer when degraded alone. The most important interactive effects result when a small reactive species produced in the degradation of one of the two polymers in the blend diffuses into the domains of the other polymer in the two-phase system and reacts with that polymer.     

Thermal Denaturation of Bacterial Cells Examined by Differential Scanning Calorimetry

Thermal stability of vegetative cells of Listeria monocytogenes, Escherichia coli and Lactobacillus plantarum was studied by counting viable fractions and determining DSC curves of their suspensions. DSC curves in the 5–99°C range showed a series of endothermic transitions between 50 and 60°C, where the heat destruction of cells occurred. Heat denaturation of DNA required a higher temperature than cell killing. Thermal death was strongly influenced by the pH, composition and NaCl content of the suspending buffer. A mathematical model developed by us enabled comparison of DSC peak temperatures and temperatures required for loss of viability.This revised version was published online in November 2005 with corrections to the Cover Date.     

电感耦合等离子体原子发射光谱法测定聚氯乙烯热稳定剂中的金属元素

应用电感耦合等离子体原子发射光谱法同时测定了聚氯乙烯热稳定剂中铅、镉、钡、钙、锌、镁、锡、锑、镧、铈、镨及钕等元素.对分析线选择、消解方法的选择、介质的影响等进行了试验.与碳化一混合酸消解法相比较,高压罐消解法处理样品所得结果的精密度更好.选择波长为220.353,214.438,233.527,393.366,213.856,279.553, 242.949,206.833,408.672,418.660,417.939及401.225 nm等12条谱线依次作为测定铅、镉、钡、钙、锌、镁、镧、铈、镨和钕的分析线,测得12种元素的检出限(3s)均低于0.02 mg·L-1.应用此法测定了聚氯乙烯热稳定剂中12种金属元素的含量,回收率在95.0%～112.0%之间.