One-Pot Synthesis of Lignin Thermosets Exhibiting Widely Tunable Mechanical Properties and Shape Memory Behavior

A series of kraft lignin based thermosets were successfully synthesized by a one-pot heat curing method composed of lignin, PEG400, and citric acid through esterification reactions with water as the only produced byproduct. The polyester thermosets were prepared by varying the ratio of lignin and PEG400 in combination with citric acid as the cross-linker. Lignin and PEG400 were chosen as the rigid and soft segments, respectively, to tailor the thermal mechanical properties of the thermosets. An increase of lignin content from 20 to 40 wt % facilitated an increase in the cross-linking density and aromatic content. This was reflected in the storage modulus at 25 °C, which increased from 5.7 to 2000 MPa, and the glass transition temperature, which increased from −0.3 to 102 °C. At the same time, the tensile strength changed from 1.2 to 34.3 MPa. The mechanical properties were, thus, tunable from flexible to rigid, demonstrating a significantly high storage modulus and tensile strength for a biobased thermoset. Furthermore, a superb thermally stimulated shape memory property was illustrated. This is promising for the use of commercial kraft lignin as a building block for versatile applications

Isosorbide as Core Component for Tailoring Biobased Unsaturated Polyester Thermosets for a Wide Structure–Property Window

Biobased unsaturated polyester thermosets as potential replacements for petroleum-based thermosets were designed. The target of incorporating rigid units, to yield thermosets with high thermal and mechanical performance, both in the biobased unsaturated polyester (UP) and reactive diluent (RD) while retaining miscibility was successfully achieved. The biobased unsaturated polyester thermosets were prepared by varying the content of isosorbide, 1,4-butanediol, maleic anhydride, and succinic anhydride in combination with the reactive diluent isosorbide-methacrylate (IM). Isosorbide was chosen as the main component in both the UP and the RD to enhance the rigidity of the formed thermosets, to overcome solubility issues commonly associated with biobased UPs and RDs and volatility and toxicity associated with styrene as RD. All UPs had good solubility in the RD and the viscosity of the mixtures was primarily tuned by the feed ratio of isosorbide but also by the amount of maleic anhydride. The flexural modulus and storage modulus were tailorable by altering the monomer composition The fabricated thermosets had superior thermal and mechanical properties compared to most biobased UP thermosets with thermal stability up to about 250 °C and a storage modulus at 25 °C varying between 0.5 and 3.0 GPa. These values are close to commercial petroleum-based UP thermosets. The designed tailorable biobased thermosets are, thus, promising candidates to replace their petroleum analogs

Rapid Crystallization of Poly(lactic acid) by Using Tailor-Made Oxalamide Derivatives as Novel Soluble-Type Nucleating Agents

The crystallization rate and crystallinity of poly­(lactic acid) (PLA) was significantly increased by the incorporation of 0.25–1.0 wt % of tailor-made oxalamide derivatives (NAs). The nucleation effect and nucleation mechanisms of the NAs were studied via diferential scanning calorimetry (DSC), polarized optical microscopy (POM), and wide-angle X-ray diffraction (WAXD) techniques. The experimental results convincingly revealed that the NA molecules are soluble in a PLA melt and are capable of self-organizing into fibrils upon cooling. The fibrils as efficient nucleation sites induced rapid growth of α-form PLA crystal along the fibrils, forming shish-kebab-like structures. In isothermal crystallization, very fine PLA sperrulites with high density were obtained in the presence of NAs. The high nucleation efficiency and the simple synthetic routes of the NAs make them promising to be a new generation of nucleating agents for (bio)­polymers, e.g., PLA

Additional file 2 of Machine learning-derived identification of tumor-infiltrating immune cell-related signature for improving prognosis and immunotherapy responses in patients with skin cutaneous melanoma

Additional file 2: Table S2. The sequence of primers was used in this study

Additional file 3 of Machine learning-derived identification of tumor-infiltrating immune cell-related signature for improving prognosis and immunotherapy responses in patients with skin cutaneous melanoma

Additional file 3: Table S3. List of 132 module genes used in this study

Additional file 1 of Machine learning-derived identification of tumor-infiltrating immune cell-related signature for improving prognosis and immunotherapy responses in patients with skin cutaneous melanoma

Additional file 1: Table S1. Clinical characteristics of the 30 SKCM patients used in this study

Additional file 6 of Machine learning-derived identification of tumor-infiltrating immune cell-related signature for improving prognosis and immunotherapy responses in patients with skin cutaneous melanoma

Additional file 6: Figure S2. Differentially expressed module genes between tumor and normal tissue in TCGA-SKCM dataset

Additional file 4 of Machine learning-derived identification of tumor-infiltrating immune cell-related signature for improving prognosis and immunotherapy responses in patients with skin cutaneous melanoma

Additional file 4: Table S4. Differentially expressed genes between 2 clusters in the meta-cohort

Additional file 5 of Machine learning-derived identification of tumor-infiltrating immune cell-related signature for improving prognosis and immunotherapy responses in patients with skin cutaneous melanoma

Additional file 5: Figure S1. WGCNA analysis. (A and B) The heatmap revealed the eigengene adjacency of modules

Reprocessable, Highly Transparent Ionic Conductive Elastomers Based on β‑Amino Ester Chemistry for Sensing Devices

Ionic conductive elastomers (ICEs) exhibit a compelling combination of ionic conductivity and elastic properties, rendering them excellent candidates for stretchable electronics, particularly in applications like sensing devices. Despite their appeal, a significant challenge lies in the reprocessing of ICEs without compromising their performance. To address this issue, we propose a strategy that leverages covalent adaptable networks (CANs) for the preparation of ICEs. Specifically, β-amino ester bonds as dynamic motifs are incorporated into a poly(ethylene oxide) network containing lithium bis(trifluoromethane) sulfonimide (LiTFSI) salt. LiTFSI-containing β-amino ester networks (LBAEs) exhibit superb transparency (94%), thermal stability (>280 °C), and modest conductivity (0.00576 mS·cm–1 at 20 °C), and some LBAEs maintain operational capability across a wide temperature range (−20 to 100 °C). By regulating the lithium salt content, the mechanical properties, conductivities, and viscoelastic behaviors can be tailored. Benefiting from these features, LBAEs have been successfully applied in sensing devices for monitoring human motion (e.g., finger bending, swallowing, and clenching). Notably, even after four reprocessing cycles, LBAEs demonstrate structural integrity and maintain their operational capability. This novel approach represents a promising solution to the reprocessing challenges associated with flexible conductive devices, demonstrating the successful integration of CANs and ICEs