Cerocene and Lanthanocene Chalcogenides: Synthesis, Structure, and Luminescence

A series of lanthanide chalcogenides {[η5–1,3-(Me3C)2C5H3]2Ln}2(μ-η2:η2-Te2) (Ln = Ce 1, La 2), {[η5–1,3-(Me3C)2C5H3]2Ln­(THF)}2(μ-Se) (Ln = Ce 3, La 4), and {[η5–1,3-(Me3C)2C5H3]2Ln­(THF)}2(μ-Te) (Ln = Ce 5, La 6) can be readily obtained by the reaction of the alkyl complexes [η5–1,3-(Me3C)2C5H3]2Ln­(CH2C6H4-o-NMe2) with elemental selenium or tellurium in the presence of 9-borabicyclo[3.3.1]­nonane (9-BBN). The reaction of the alkyl complexes [η5–1,3-(Me3C)2C5H3]2Ln­(CH2C6H4-o-NMe2) with 9-BBN in 1:2 molar ratio afforded the lanthanide (cyclooctane-1,5-diyl)­dihydroborate complexes [η5–1,3-(Me3C)2C5H3]2Ln­[(μ-H)2BC8H14] (Ln = Ce 7, La 8) concomitant with the (Me2N-o-C6H4CH2)­BC8H14 release, indicating that [η5–1,3-(Me3C)2C5H3]2LnH may be the reactive species for the synthesis of lanthanide chalcogenides. All the new compounds were characterized by various spectroscopic methods, and their solid-state structures were further confirmed by single-crystal X-ray diffraction analyses. Luminescence spectroscopy was also employed to characterize complexes 1–6. The Ce­(III) complexes 3 and 5 display distinct luminescence properties at room temperature, as compared to the corresponding La­(III) complexes 4 and 6. The complex {[η5–1,3-(Me3C)2C5H3]2Ce­(THF)}2(μ-Te) (5) exhibits unexpectedly red emission in solution which is found to depend strongly on the excitation wavelength

Flexible Conductive Fibers from Alginate, Cellulose Nanocrystals, and Polyaniline by Wet Spinning

Polyaniline (PANI) has indeed received significant attention and extensive research in both academic and electronic industrial fields. Its unique properties, such as conductivity and processability, make it a promising material for various applications. Researchers and industrialists have explored PANI for its potential use in electronic devices, such as sensors, batteries, capacitors, and actuators, as well as in other areas like corrosion protection, supercapacitors, and electromagnetic shielding. The poor compatibility, tendency to aggregate, and poor mechanical properties of nanostructured PANI have hindered its performance. Cellulose nanocrystals (CNCs) were used as a bio-template for covalent grafting PANI onto hydrophilic CNCs (CNC-g-PANI) through in situ oxidative polymerization. The resulting CNC-g-PANI suspension with the sodium alginate (SA) matrix was wet-spun into composite fibers, which were compared to composite fibers made by physical blending of pure PANI and hydrogen-bonded CNC/PANI. The parameters were characterized to investigate the performance of the composite fibers. The covalent grafted CNC-g-PANI suspension maintained stable dispersion throughout the wet spinning process, making it suitable for both fundamental research and industrial processing. Indeed, the development of CNC-g-PANI@SA composite fibers through the covalent grafting of PANI onto cellulose nanocrystals offers a simple and eco-friendly approach. These composite fibers exhibit improved properties, including enhanced tensile strength, electrical conductivity, flexibility, and fatigue resistance. These attributes make them highly suitable for applications in the antistatic textile and electronic industries

Flexible Conductive Fibers from Alginate, Cellulose Nanocrystals, and Polyaniline by Wet Spinning

Polyaniline (PANI) has indeed received significant attention and extensive research in both academic and electronic industrial fields. Its unique properties, such as conductivity and processability, make it a promising material for various applications. Researchers and industrialists have explored PANI for its potential use in electronic devices, such as sensors, batteries, capacitors, and actuators, as well as in other areas like corrosion protection, supercapacitors, and electromagnetic shielding. The poor compatibility, tendency to aggregate, and poor mechanical properties of nanostructured PANI have hindered its performance. Cellulose nanocrystals (CNCs) were used as a bio-template for covalent grafting PANI onto hydrophilic CNCs (CNC-g-PANI) through in situ oxidative polymerization. The resulting CNC-g-PANI suspension with the sodium alginate (SA) matrix was wet-spun into composite fibers, which were compared to composite fibers made by physical blending of pure PANI and hydrogen-bonded CNC/PANI. The parameters were characterized to investigate the performance of the composite fibers. The covalent grafted CNC-g-PANI suspension maintained stable dispersion throughout the wet spinning process, making it suitable for both fundamental research and industrial processing. Indeed, the development of CNC-g-PANI@SA composite fibers through the covalent grafting of PANI onto cellulose nanocrystals offers a simple and eco-friendly approach. These composite fibers exhibit improved properties, including enhanced tensile strength, electrical conductivity, flexibility, and fatigue resistance. These attributes make them highly suitable for applications in the antistatic textile and electronic industries

Synthesis of Heat-Resistant and Low-Sensitivity Energetic Materials Based on Hydrazine Bridge Linkage

In this work, a combination of vicinal amino–nitro groups and the hydrazine bridge was developed to synthesize two insensitive and heat-resistant energetic compounds 2,2′-hydrazo-bis(2-amino-3,5-dinitropyridine) (2) and 2,2′-hydrazo-bis(4-amino-3,5-dinitropyridine) (4) through a simple method. The structures of compound 2 and 4 were adequately characterized by NMR (1H and 13C), elemental analysis, differential scanning calorimetry, and infrared spectroscopy. Notably, compound 2 possesses thermal stability (Td = 350 °C) higher than that of 2-bis(2,4,6-trinitrophenyl) ethene (HNS) (Td = 318 °C) and comparable to that of 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) (Td = 350 °C). Moreover, compound 2 possess a higher energy level (2: D = 8759 m s–1, P: 34.1 GPa) than HNS (7612 m s–1, P: 24.3 GPa) and TATB (8114 m s–1, P: 31.4 GPa). These consequences indicate that compound 2 has potential applications as an insensitive and heat-resistant explosive

Supplementary document for Photomodulated cryogenic temperature sensing through photochromic reaction in Na0.5Bi2.5Ta2O9: Er/Yb multicolour upconversion - 6011629.pdf

Supplement

A Quantitative Metal-Encoded Conjugate Platform for Targeting Ligand Discovery

The indiscriminate biodistribution of therapeutics can be a key barrier to their safety and efficacy. Localization of compounds into non-diseased tissues often leads to both toxic and dose-limiting effects. To overcome this barrier, nanomedicine implements targeting agents to localize or selectively uptake drugs at disease sites. However, to date there are only a small number of targeting agents with limited scope for targeting tissues. Small-molecule ligands are particularly attractive as targeting agents due to their relatively low cost, tunability, and ease of conjugation. Currently, there are no systematic approaches to the discovery of new small-molecule targeting ligands. Here, we developed a quantitative metal-encoded conjugate platform to determine the biodistribution of multiple small molecules in vivo. By utilizing lanthanide metal complexes, this platform successfully distinguished known ligands with differential tissue targeting in vivo. This system will facilitate the discovery of small molecules as targeting ligands and can accelerate the identification of novel biological targets for tissue-targeted drug delivery

Efficacy of third-generation epidermal growth factor receptor-tyrosine kinase inhibitors in advanced NSCLC with different T790M statuses tested via digital droplet polymerase chain reaction ddPCR and next-generation sequencing

We hypothesize that digital droplet polymerase chain reaction (ddPCR) would optimize the treatment strategies in epidermal growth factor receptor (EGFR)-tyrosine kinase inhibitors (TKIs) relapsed patients. In this study, we compared the efficacy of third-generation TKIs with various T790M statuses via ddPCR and next-generation sequencing (NGS). NGS was performed on blood samples of patients progressed from previous EGFR-TKIs for resistance mechanism. T790M-negative patients received further liquid biopsy using ddPCR for T790M detection. A cohort of 40 patients were enrolled, with 30.0% (12/40) T790M-positive via NGS (Group A). In another 28 T790M-negative patients by NGS, 11 (39.3%) were T790M-positive (Group B) and 17 (60.7%) were T790M-negative (Group C) via ddPCR. A relatively longer progression-free survival (PFS) was observed in group A (NR) and group B (10.0 months, 95% CI 7.040–12.889) than in group C (7.0 months, 95% CI 0.000–15.219), with no significant difference across all three groups (p = 0.196), or between group B and C (p = 0.412). EGFR-sensitive mutation correlated with inferior PFS (p = 0.041) and ORR (p = 0.326), and a significantly lower DCR (p = 0.033) in T790M-negative patients via NGS (n = 28). This study indicates that ddPCR may contribute as a supplement to NGS in liquid biopsies for T790M detection in EGFR-TKIs relapsed patients and help to optimize the treatment strategies, especially for those without coexistence of EGFR-sensitive mutation. www.clinicaltrials.gov identifier is NCT05458726.</p

Tough and Biocompatible Hydrogel Tissue Adhesives Entirely Based on Naturally Derived Ingredients

Hydrogel tissue adhesives have tremendous potential applications in biological engineering. Existing hydrogel tissue adhesives generally do not have adequate mechanical robustness and acceptable biocompatibility at the same time. Herein, we report a one-step method to synthesize tough and biocompatible hydrogel tissue adhesives entirely made of naturally derived ingredients. We select two natural polymers, chitosan and gelatin, to construct the backbone and a bioderived compound, genipin, as the cross-linker. We show that, upon gelation, genipins cross-link chitosan and gelatin to form two interpenetrated networks and interlink them to tissue surfaces. Meanwhile, hydrogen bonds form in the matrix to strengthen the networks and at the interface to strengthen the adhesion between the hydrogel and tissue. Furthermore, we elaborately use high initial polymer contents to induce topological entanglements in the polymer networks to toughen the hydrogel. The resulting chitosan–gelatin hydrogel provides a tough matrix, and the robust covalent interlinks and hydrogen bonds provide a strong interface, achieving a tensile strength of ∼190 kPa, a fracture toughness of 205.7 J/m2, a mode I adhesion energy of 197.6 J/m2, and a mode II adhesion energy of 51.2 J/m2. We demonstrate that the hydrogel tissue adhesive is injectable, degradable, and noncytotoxic and can be used for the controlled release of the anticancer drug cisplatin. All-natural ingredient-based tough and biocompatible hydrogels are promising as tissue adhesives for biomedical and related applications

Stretchable Heterogeneous Polymer Networks of High Adhesion and Low Hysteresis

Adhesives are ubiquitous, but the mutual exclusion between hyperelasticity and adhesiveness impedes their uses in emerging techniques such as flexible/stretchable electronics. Herein, we propose a strategy to synthesize hyperelastic adhesives (HEAs), by designating hyperelasticity and adhesiveness to the bulk and the surface of a polymer network, respectively. The bulk is hyperelastic but nonadhesive, and the surface is viscoelastic but adhesive, while the HEA is hyperelastic and adhesive. We exemplify the principle by synthesizing poly­(butyl acrylate) as the bulk and poly­(butyl acrylate-co-isobornyl acrylate) as the surface. The resulting HEA exhibits a low hysteresis of 4% at 100% strain and an adhesion energy of 270 J m–2. Moreover, the HEA is optically transparent, thermally stable, spontaneously adhesive to various materials, and mechanically stable against cyclic load, relaxation, and creep. We demonstrate two applications enabled by the unique combination of hyperelasticity and adhesiveness. The proposed strategy is generic, paving new avenues for stretchable yet resilient adhesives for diverse applications

Additional file 2 of Efficacy of first-line treatments in the elderly and non-elderly patients with advanced epidermal growth factor receptor mutated, non-small cell lung cancer: a network meta-analysis

Additional file 2