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

Torres, Fernando G.; Troncoso, Omar P.; Torres, Carlos; Cabrejos, Wilson

doi:10.1016/j.msec.2012.12.047

Cited by 9 publications

(13 citation statements)

References 47 publications

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“…No thermal transition was detected in either the cocoon raw fibers or the degummed fibers, indicating that the thermal stability of silk materials correlates with the ratio of crystalline to amorphous regions in the materials. Torres et al reported T g for degummed silk fibers was detected by DSC . They used the silk fibers after three-times degumming to extract the sericin, and hence the silk could contain more amorphous region to induce T g .…”

Section: Resultsmentioning

confidence: 99%

“…Torres et al reported T g for degummed silk fibers was detected by DSC. 42 They used the silk fibers after three-times degumming to extract the sericin, and hence the silk could contain more amorphous region to induce T g . Guan et al demonstrated that the occurrence of T g is dependent on the grade of the silk: the low grade of silk with damages showed the lower T g , while high grade of silk did not show such T g .…”

Section: ■ Results and Discussionmentioning

confidence: 99%

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Influence of Water Content on the β-Sheet Formation, Thermal Stability, Water Removal, and Mechanical Properties of Silk Materials

et al. 2016

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Silk, which has excellent mechanical toughness and is lightweight, is used as a structural material in nature, for example, in silkworm cocoons and spider draglines. However, the industrial use of silk as a structural material has garnered little attention. For silk to be used as a structural material, its thermal processability and associated properties must be well understood. Although water molecules influence the glass transition of silk, the effects of water content on the other thermal properties of silks are not well understood. In this study, we prepared Bombyx mori cocoon raw fibers, degummed fibers, and films with different water contents and then investigated the effects of water content on crystallization, degradation, and water removal during thermal processing. Thermal gravimetric analyses of the silk materials showed that water content did not affect the thermal degradation temperature but did influence the water removal behavior. By increasing the water content of silk, the water molecules were removed at lower temperatures, indicating that the amount of free water in silk materials increased; additionally, the glass transition temperature decreased with increasing water plasticization. Differential scanning calorimetry and wide-angle X-ray scattering of the silk films also suggested that the water molecules in the amorphous regions of the silk films acted as a plasticizer and induced β-sheet crystallization. The plasticizing effect of water was not detected in silk fibers, owing to their lower amorphous content and mobility. The structural and mechanical characterizations of the silk films demonstrated the silk film prepared at RH 97% realized both crystallinity and ductility simultaneously. Thus, the thermal stability, mechanical, and other properties of silk materials are regulated by their water content and crystallinity.

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Section: Resultsmentioning

confidence: 99%

Section: ■ Results and Discussionmentioning

confidence: 99%

Influence of Water Content on the β-Sheet Formation, Thermal Stability, Water Removal, and Mechanical Properties of Silk Materials

et al. 2016

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“…The thermal analysis reflects the thermal stability of material, which related to structural changes on polymers such as crystallization, and the higher the crystallinity, the higher the fastest thermal decomposition temperature [49]. As shown in Figure 7, two distinct regions of thermal weight loss were observed in the thermogravimetric curves of…”

Section: Thermal Performance Of Sf/ss Composite Filmsmentioning

confidence: 99%

Enhanced Silk Fibroin/Sericin Composite Film: Preparation, Mechanical Properties and Mineralization Activity

Tian

Zhang

et al. 2022

Polymers

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The periosteum plays an important role in bone formation and reconstruction. One of the reasons for the high failure rate of bone transplantation is the absence of the periosteum. Silk fibroin (SF) and silk sericin (SS) have excellent biocompatibility and physicochemical properties, which have amazing application prospects in bone tissue engineering, but lacked mechanical properties. We developed a series of SF/SS composite films with improved mechanical properties using boiling water degumming, which caused little damage to SF molecular chains to retain larger molecules. The Fourier transform infrared spectroscopy and X-ray diffraction results showed that there were more β-sheets in SF/SS films than in Na2CO3 degummed SF film, resulting in significantly improved breaking strength and toughness of the composite films, which were increased by approximately 1.3 and 1.7 times, respectively. The mineralization results showed that the hydroxyapatite (HAp) deposition rate on SF/SS composite films was faster than that on SF film. The SF/SS composite films effectively regulated the nucleation, growth and aggregation of HAp-like minerals, and the presence of SS accelerated the early mineralization of SF-based materials. These composite films may be promising biomaterials in the repair and regeneration of periosteum.

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“…Silks have been subjected to calorimetric tests for over 20 years but with the focus either on natural spun fibers (which are not directly relevant in the context of this work) or artificial silk feedstocks/films, where processing has altered the state of hydration so much that these artificial silks may no longer represent a native unspun silk protein/model aquamelt . However, in the early 2000s, Tanaka et al.…”

Section: Introductionmentioning

confidence: 99%

Differential Scanning Calorimetry of Native Silk Feedstock

Holland

Hawkins²,

Frydrych³

et al. 2018

Macromolecular Bioscience

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Native silk proteins, extracted directly from the silk gland prior to spinning, offer access to a naturally hydrated protein that has undergone little to no processing. Combined with differential scanning calorimetry (DSC), it is possible to probe the thermal stability and hydration status of silk and thus investigate its denaturation and solidification, echoing that of the natural spinning process. It is found that native silk is stable between −10 °C and 55 °C, and both the high‐temperature enthalpy of denaturation (measured via modulated temperature DSC) and a newly reported low‐temperature ice‐melting transition may serve as useful quality indicators in the future for artificial silks. Finally, compared to albumin, silk's denaturation enthalpy is much lower than expected, which is interpreted within a recently proposed entropic desolvation framework which can serve to unveil the low‐energy aquamelt processing pathway.

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

Cited by 9 publications

References 47 publications

Influence of Water Content on the β-Sheet Formation, Thermal Stability, Water Removal, and Mechanical Properties of Silk Materials

Influence of Water Content on the β-Sheet Formation, Thermal Stability, Water Removal, and Mechanical Properties of Silk Materials

Enhanced Silk Fibroin/Sericin Composite Film: Preparation, Mechanical Properties and Mineralization Activity

Differential Scanning Calorimetry of Native Silk Feedstock

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