Polymeric Precursor Research Articles

Influence of the Polymer Precursor Structure on the Porosity of Carbon Nanofibers: Application as Electrode in High-Temperature Proton Exchange Membrane Fuel Cells

Influence of the Polymer Precursor Structure on the Porosity of Carbon Nanofibers: Application as Electrode in High-Temperature Proton Exchange Membrane Fuel Cells

Recent Advances in Preceramic Polysilazane Precursors in Additive Manufacturing

Si3N4/SiCN ceramics have been extensively explored for applications in the aerospace, mechanical engineering, and biomedical fields. Recently, there has been significant focus on the additive manufacturing (AM) of polymer-derived ceramic (PDC) technology for fabricating Si3N4/SiCN ceramics. The chemical structure and composition of the preceramic polymer precursors have a crucial influence on the performance of ceramic products. In this paper, recent advances in the use of polysilazane and polycarbosilazane precursors in AM are reviewed and an outlook for future development is presented. The findings of this study could spark inspiration and reflection regarding AM applications and synthetic technology. It is believed that the development of PDCs in ceramic fabrication will become more versatile and application-oriented and provide more freedom in the design of high-performance ceramics.

The impact of polypyrrole:carboxymethyl cellulose composite nanostructure on conductivity and capacitance

Polypyrrole is a popular conjugated polymer that becomes highly conductive in its p-doped state. The intrinsically non-polar nature of the conjugated bond network limits the processing options of such polymers. Surfactants and polyanions help increase dispersity of conductive polymer in suitable solvents for processing. However, while such dispersions can be highly stable, they are formed by complex nanostructures that significantly impact the conducting polymer composite’s bulk properties. Similarly, complex nanostructures can be formed when surfactants or polyelectrolytes serve as templates during the polymerization of the conducting polymer precursor. Following the report of polypyrrole:carboxymethyl cellulose composites in battery electrodes as conductive binders, we are here investigating the role that nanostructure control can have in optimizing their performance. Using methyl orange as a structural template, we can control the composite’s nanoscopic shape between nanospheres and nanofibers. In the bulk material, the latter gives rise to significantly increased electronic conductivity and capacitance in battery use conditions, underlining the opportunities for improved performance of conducting polymer composites by controlling synthesis conditions.

Effects of Drug Conjugation on the Biological Activity of Single-Chain Nanoparticles.

The field of single-chain nanoparticles (SCNPs) continues to mature, and an increasing range of reports have emerged that explore the application of these small nanoparticles. A key application for SCNPs is in the field of drug delivery, and recent work suggests that SCNPs can be readily internalized by cells. However, limited attention has been directed to the delivery of small-molecule drugs using SCNPs. Moreover, studies on the physicochemical effects of drug loading on SCNP performance is so far missing, despite the accepted view that such small nanoparticles should be significantly affected by the drug loading content. To address this gap, we prepared a library of SCNPs bearing different amounts of a covalently conjugated therapeutic drug-sulfasalazine (SSZ). We evaluated the impact of the conjugated drug loading on both the synthesis and biological activity of SCNPs on pancreatic cancer cells (AsPC-1). Our results reveal that covalent drug conjugation to the side chains of the SCNP polymer precursor interferes with chain collapse and cross-linking, which demands optimization of reaction conditions to reach high degrees of cross-linking efficiencies. Small-angle neutron scattering and diffusion-ordered spectroscopy nuclear magnetic resonance (DOSY NMR) analyses reveal that SCNPs with a higher drug loading display larger sizes and looser structures, as well as increased hydrophobicity associated with a higher SSZ content. Increased SSZ loading led to reduced cellular uptake when assessed in vitro, whereby SCNP aggregation on the surface of AsPC-1 cells led to reduced toxicity. This work highlights the effects of drug loading on the drug delivery efficiency and biological behavior of SCNPs.

Sensitive Determination of 3-Hydroxy-2-Butanone with Double-Layer Mesoporous Tin (IV) Oxide Nanotubes Prepared by Single-Nozzle Electrospinning

Yolk-shell SnO2 mesoporous double-layer nanotubes were synthesized in one-step by single nozzle electrospinning. Compared with the traditional electrospinning using polyvinylpyrrolidone (PVP) as the precursor polymer to obtain the single nanotube material, two PVPs (PVPK88-96 and PVPK23-27) with different molecular weights in solution coupled with Sn2+ easily form the core-shell structure nanofiber through phase separation. The yolk-shell double-layer SnO2 nanotubes were obtained after calcination at 600 °C for 2 h. The yolk-shell SnO2 mesoporous double-layer nanotube is a promising sensing material toward 3-hydroxy-2-butanone as it shows high sensitivity, cycling stability, and selectivity. Moreover, the response and recovery times of the yolk-shell SnO2 mesoporous double-layer nanotubes toward 1 ppm 3-hydroxy-2-butanone were 122 s and 117 s.

Organic polymer coating induced multiple heteroatom-doped carbon framework confined Co1-xS@NPSC core-shell hexapod for advanced sodium/potassium ion batteries

Synthesis of advanced structure and multiple heteroatom-doped carbon based heterostructure materials are the key to the preparation of high-performance energy storage electrode materials. Herein, the hexapod-shaped Co1-xS@NPSC has been triumphantly prepared using hexapod ZIF-67 as the sacrificial template to prepare Co1-xS inner core and N, P, and S tri-doped carbon (NPSC) as the shell through the carbonization of the organic polymer precursor. When applied as anode for Na+ batteries (SIBs) and K+ batteries (PIBs), Co1-xS@NPSC presents the high reversible specific capability of 747.4 mAh/g at 1.0 A/g after 235 cycles and 387.8 mAh/g at 5.0 A/g after 760 cycles for SIBs, as well as 326.7 mAh/g at 1.0 A/g after 180 cycles for PIBs. The excellent storage capacity and rate capability of Co1-xS@NPSC is ascribed to hexapod structure of ZIF-67 unlike the common dodecahedron, which is constructed with interior porous and exterior framework repository, donating supplemental active sites, and doping of multiple heteroatoms forming organic polymer coating inhibiting the volume expansion and restrains the agglomeration of Co1-xS nanoparticles. This approach has paved a bright avenue to exploit promising anode materials with novel structure and hetero-atom doping for high-performance energy storage devices.

Effect of BN interfacial layer on the mechanical behavior of SiC fiber reinforced SiC ceramic matrix composites

AbstractBoron nitride (BN) interfacial layer with controlled thickness and structure was prepared on the surface of near stoichiometric ratio SiC fiber preforms by a chemical vapor deposition process, and the SiC/SiC composites were obtained by polymer precursor infiltration and pyrolysis process. The microstructure of the BN interfacial layer and SiC/SiC composites was tested by scanning electron microscopy, and the mechanical behavior of SiC/SiC composites was characterized by a mechanical properties test. Results showed that BN interfacial layer was evenly distributed in the fiber preforms with excellent thickness consistency. As the thickness of the BN interfacial layer increased, the deflection path of the crack increased gradually, resulting in the flexural strength first increasing and then decreasing. The mechanical behavior mentioned above was mainly attributed to the dual effects of load transfer and crack propagation of the BN interfacial layer; that was, the crack propagation of ceramic matrix under external load lengthened the path of load transfer and formed a large number of fibers bridging and pulling out successively, which contributed to the energy dissipation mechanism.

A Visible Light Cross-Linked Underwater Hydrogel Adhesive with Biodegradation and Hemostatic Ability.

Hydrogel adhesives with integrated functionalities are still required to match their ever-expanding practical applications in the field of tissue repair and regeneration. A simple and effective safety strategy is reported, involving an in situ injectable polymer precursor and visible light-induced cross-linking. This strategy enables the preparation of a hydrogel adhesive in a physiological environment, offering wet adhesion to tissue surfaces, molecular flexibility, biodegradability, biocompatibility, efficient hemostatic performance, and the ability to facilitate liver injury repair. The proposed one-step preparation process of this polymer precursor involves the mixing of gelatin methacryloyl (GelMA), poly(thioctic acid) [P(TA)], poly(acrylic acid)/amorphous calcium phosphate (PAAc/ACP, PA) and FDA-approved photoinitiator solution, and a subsequent visible light irradiation after in situ injection into target tissues that resulted in a chemically-physically cross-linked hybrid hydrogel adhesive. Such a combined strategy shows promise for medical scenarios, such as uncontrollable post-traumatic bleeding.

Deciphering fast lithium storage kinetics via R-based self-derivation effects in siloxanes

Silicon oxycarbide (SiOC) is regarded as a promising anode material for lithium-ion batteries. However, the effect of SiOC's structural composition on lithium-ion storage behaviors, especially the controllable introduction of free carbon (Cfree) and its influence on electrochemical performance, remains a critical challenge that needs to be solved. In this study, based on our finding that the R-based functional group (composed exclusively of carbon and hydrogen atoms) in R-based triethoxysilane can be derived to carbon radicals through thermal decomposition, and then generates Cfree phases into SiOC, we propose a novel concept of R-based self-derivation effects in siloxanes to achieve controlled Cfree introduction for the SiOC anode material. SiOC spheres with tailored structural compositions and Cfree contents are subsequently prepared using a facile and scalable polymeric precursor method, and the effect of Cfree of SiOC spheres on lithium-ion storage performance is studied in combination with density functional theory calculations, revealing that higher Cfree content significantly enhances the lithium-ion storage kinetics of SiOC anode via constructing ion/electron migration “highways”. Notably, SiOC with a high Cfree content up to 37.5 wt% displays excellent lithium-ion storage capability, with a theoretical storage capacity of up to 1004 mAh g−1 and achieving a high reversible capacity of 453 mAh g−1 after 200 cycles at 0.5 A g−1.

Microarchitected Compliant Scaffolds of Pyrolytic Carbon for 3D Muscle Cell Growth.

The integration of additive manufacturing technologies with the pyrolysis of polymeric precursors enables the design-controlled fabrication of architected 3D pyrolytic carbon (PyC) structures with complex architectural details. Despite great promise, their use in cellular interaction remains unexplored. This study pioneers the utilization of microarchitected 3D PyC structures as biocompatible scaffolds for the colonization of muscle cells in a 3D environment. PyC scaffolds are fabricated using micro-stereolithography, followed by pyrolysis. Furthermore, an innovative design strategy using revolute joints is employed to obtain novel, compliant structures of architected PyC. The pyrolysis process results in a pyrolysis temperature- and design-geometry-dependent shrinkage of up to 73%, enabling the geometrical features of microarchitected compatible with skeletal muscle cells. The stiffness of architected PyC varies with the pyrolysis temperature, with the highest value of 29.57±0.78GPa for 900°C. The PyC scaffolds exhibit excellent biocompatibility and yield 3D cell colonization while culturing skeletal muscle C2C12 cells. They further induce good actin fiber alignment along the compliant PyC construction. However, no conclusive myogenic differentiation is observed here. Nevertheless, these results are highly promising for architected PyC scaffolds as multifunctional tissue implants and encourage more investigations in employing compliant architected PyC structures for high-performance tissue engineeringapplications.

Consecutive one-pot alkyne semihydrogenation/alkene dioxygenation reactions by Pt(II)/Cu(II) single-chain nanoparticles in green solvent.

Heterobimetallic Pt(II)/Cu(II) single-chain polymer nanoparticles (SCNPs) were sequentially synthesized from a polymeric precursor featuring both α-diazo-β-ketoester and naked β-ketoester functional groups. Photoactivated carbene generation at λexc = 365 nm from α-diazo-β-ketoester moieities was triggered for bonding Pt(II) ions from dichloro(1,5-cyclooctadiene)Pt(II) to the polymeric precursor, whereas Cu(II) ions were subsequently incorporated via Cu(II)-(β-ketoester)2 complex formation using Cu(II) acetate. Both intrachain Pt(II) bonding and Cu(II) complexation were found to contribute to the folding of the polymeric precursor generating Pt(II)/Cu(II)-SCNPs as evidenced by infrared spectroscopy, size exclusion chromatography and dynamic light scattering. These heterobimetallic SCNPs proved highly efficient as soft nanocatalysts for the consecutive one-pot alkyne semihydrogenation/alkene dioxygenation reactions at room temperature in N-butylpyrrolidone, as a non-toxic alternative solvent to N,N-dimethylformamide.

Preparation of poly(vinyl alcohol) with enhanced stereoselectivity via hydrolysis of poly(vinyl acetate) produced by radical polymerization using 7-membered ring controlling agents

Controlling tacticity is crucial in polymer chemistry since it impacts the characteristics of synthetic polymers. Poly(vinyl alcohol) (PVA), generally obtained by hydrolysis of poly(vinyl acetate) (PVAc), is a prevalent polymer whose properties are susceptible to even a small change in the main chain stereostructure. Thus, new polymerization methods that improve the tacticity of PVA or its precursor polymer are highly desirable. Herein, 7-membered ring compounds (tropolone (Tro-H), 2-tosyloxytropone (Tro-OTs), potassium tropolonate (Tro-K), methanesulfonic acid, 1,1,1-trifluoro-,7-oxo-1,3,5-cycloheptatrien-1-yl ester (Tro-OTf), potassium 4-((7-oxocyclohepta-1,3,5-trien-1-yl)oxy)butane-1-sulfonate (Tro-SO3K) are explored for the first time as controlling agents for the radical polymerization of VAc with azobisisobutyronitrile (AIBN) as initiator. The obtained PVAc was hydrolyzed to obtain PVA. Process parameters such as monomer concentration, amount of controlling agent and initiators were optimized. The results revealed that the hydrolysis of PVAc produced in the presence of controlling agents gave PVA with improved stereoselectivity. Higher stereoselectivity, that is, isotactic triad (mm) = 24.24% of PVA, was obtained by the hydrolysis of PVAc produced with Tro-SO3K compared to VAc polymerization with other controlling agents. Moreover, hydrolysis of PVAc produced with Tro-SO3K under a wavelength radiation source (λmax, 365 nm) gave PVA with increased mm to 24.59% under similar conditions. In addition, flow chemistry, an emerging technology, was also used for VAc polymerization under optimized reaction conditions to obtain PVA with a mm of 24.62%. This work therefore provides an effective strategy to produce PVA with improved stereoselectivity via both batch and continuous flow techniques, enabling technical advantages for potential large-scale uses.

Experimental and theoretical studies of the interactions of alanine onto surfaces of olivine and montmorillonite: relevance in astrobiology

Abstract Amino acids have been detected in some meteorites and are readily synthesized in prebiotic experiments. These molecules may have been precursors of oligomers and polymers in the early Earth. These reactions were likely to happen in the protected confined spaces on the porous surface of olivine and in the interlayer nanospace of montmorillonite. This study describes experimental and theoretical research on the sorption of l-alanine onto surfaces of silicate minerals, olivine and montmorillonite. Kinetics of the sorption of this amino acid at different pH media was performed. This sorption has been also studied at atomic scale by means of quantum mechanical calculations finding that this sorption is energetically favourable. These results strongly support the premise that minerals could have actively participated in prebiotic reactions.

The role of cattle manure-driven polysaccharide precursors in humus formation during composting of spent mushroom substrate.

The study examined the impact of adding cattle manure to the composting process of Agaricus bisporus mushroom substrate on compost humification. A control group CK comprised entirely of Agaricus bisporus mushroom substrate, while the experimental group CD (70 percent Agaricus bisporus mushroom substrate and 30 percent cattle manure) comprised the two composting treatments that were established. The study determined that the addition of cow dung has promoted the formation of humus components. Particularly, humic substance (HS-C) and humic acid (HA) increased by 41.3 and 74.7%, respectively, and the ratio of humic acid to fulvic acid (HA/FA) also increased by 2.78. It showed that the addition of cow dung accelerated the synthesis and decomposition of precursors, such as polysaccharides, polyphenols, and reducing sugars. Thereby promoting the formation of humic acid. Network analysis revealed that adding cow dung promoted microbial interactions increased the complexity and stability of the bacterial and fungal symbiotic network, enhanced cooperation and reciprocity among microbes, and assisted in transforming fulvic acid (FA) components. Structural equation modeling (SEM) is a multivariate data analysis method for analyzing complex relationships among constructs and core indicators. SEM illustrated that introducing cattle manure into the composting process resulted in alterations to the correlation between physicochemical parameters and the microbial community, in addition to humus formation. Polysaccharides are the primary precursors for polymerization to form HA, which is an essential prerequisite for the conversion of fulvic acid to humic acid. Additionally, microbes affected the formation of humus, with bacteria substantially more influential than fungi. These findings provide new ideas for regulating the degree of humification in the composting process and have important practical implications for optimizing mushroom cultivation and composting techniques today.

A high-spin s-triazine linked fluorenyl radical polymer.

The syntheses of high-spin organic polymers have been a daunting task due to the highly reactive nature of organic radicals, especially when they are ferromagnetically coupled. In this paper, we report our approach to obtain high-spin organic polymers, in which a reasonably stable fluorenyl radical was employed as the primary radical unit, and s-triazine serves as the connector that facilitates ferromagnetic coupling between them. Initially, the diamagnetic polymer precursor was synthesized by cyclotrimerization of a cyano-monomer. Subsequently, the high-spin polymers were obtained by oxidizing corresponding anionic polymers using O2 (6) or I2 (7). The temperature-dependent magnetic moments, and field-dependent magnetization data obtained from SQUID measurements revealed ferromagnetic couplings between primary radical units, with coupling J = 7.5 cm-1 and 38.6 cm-1. The percentages of primary unit in the radical form are 29%, and 47% for 6 and 7, respectively. Notably, this marks the first reported instance of a high-spin fluorenyl radical polymer exhibiting ferromagnetic coupling.

Effects of polymer precursor conjugation length on the optoelectronic properties of fluorinated benzothiadiazole-based D–A systems

Due to their high electronegativity and small atomic radius without undesirable steric hindrance, the incorporation of fluorine atoms onto a conjugated backbone has been proven to be a very effective way to tune the energy levels of organic semiconductors.

Correction: Effects of polymer precursor conjugation length on the optoelectronic properties of fluorinated benzothiadiazole-based D–A systems

Correction for ‘Effects of polymer precursor conjugation length on the optoelectronic properties of fluorinated benzothiadiazole-based D–A systems’ by Daize Mo et al., New J. Chem., 2024, https://doi.org/10.1039/d4nj00131a.

Injectable, shear-thinning, photocrosslinkable, and tissue-adhesive hydrogels composed of diazirine-modified hyaluronan and dendritic polyethyleneimine.

In the present study, we report the first synthesis of diazirine-modified hyaluronic acid (HA-DAZ). In addition, we also produced a precursor polymer solution composed of HA-DAZ and dendritic polyethyleneimine (DPI) that showed strong shear-thinning properties. Furthermore, its viscosity was strongly reduced (i.e., from 5 × 105 mPa s at 10-3 s-1 to 6 × 101 mPa s at 103 s-1), substantially, which enhanced solution injectability using a 21 G needle. After ultraviolet irradiation at 365 nm and 6 mW cm-2, the HA-DAZ/DPI solution achieved rapid gelation, as measured using the stirring method, and its gelation time decreased from 200 s to 9 s as the total concentrations of HA-DAZ and DPI increased. Following UV irradiation, the storage modulus increased from 40 to 200 Pa. In addition, reversible sol-gel transition and self-healing properties were observed even after UV irradiation. This suggests that the HA-DAZ/DPI hydrogel was crosslinked in multiple ways, i.e., via covalent bonding between the diazirine and amine groups and via intermolecular interactions, including hydrogen bonding, electrostatic interactions, and hydrophobic interactions. A lap shear test showed that the HA-DAZ/DPI hydrogel exhibited strong adhesiveness as a fibrin glue following UV irradiation. Finally, the HA-DAZ/DPI hydrogel showed higher tissue reinforcement than fibrin glue in an ex vivo burst pressure test of the porcine esophageal mucosa.

Turning Complexity into Simplicity: In Situ Synthesis of High-Performance Si@C Anode in Battery Manufacturing Process by Partially Carbonizing the Slurry of Si Nanoparticles and Dual Polymers.

For Si/C anodes, achieving excellent performance with a simple fabrication process is still an ongoing challenge. Herein, we report a green, facile and scalable approach for the in situ synthesis of Si@C anodes during the electrode manufacturing process by partially carbonizing Si nanoparticles (Si NPs) and dual polymers at a relatively low temperature. Due to the proper mass ratio of the two polymer precursors and proper carbonization temperature, the resultant Si-based anode demonstrates a typical Si@C core-shell structure and has strong mechanical properties with the aid of dual-interfacial bonding between the Si NPs core and carbon shell layer, as well as between the C matrix and the underlying Cu foil. Consequently, the resultant Si@C anode shows a high specific capacity (3458.1 mAh g-1 at 0.2 A g-1), good rate capability (1039 mAh g-1 at 4 A g-1) and excellent cyclability (77.94% of capacity retention at a high current density of 1 A g-1 after 200 cycles). More importantly, the synthesis of the Si@C anode is integrated in situ into the electrode manufacturing process and, thus, significantly decreases the cost of the lithium-ion battery but without sacrificing the electrochemical performance of the Si@C anode. Our results provide a new strategy for designing next-generation, high-capacity and cost-effective batteries.

Cost-Effective Ultrabright Silicon Quantum Dots and Highly Efficient LEDs from Low-Carbon Hydrogen Silsesquioxane Polymers.

Cost-effective methods of synthesizing bright colloidal silicon quantum dots (SiQDs) for use as heavy-metal-free QDs, which have applications as light sources in biomedicine and displays, are required. We report simple protocols for synthesizing ultrabright colloidal SiQDs and fabricating SiQD LEDs based on hydrogen silsesquioxane (HSQ) polymer synthesis. Red photoluminescence with a quantum yield (PLQY) of 60-80% and LEDs with an external quantum efficiency (EQE) of >10% were obtained at 1/3600th of the cost of existing methods. This was achieved by using HSiCl3 and a low-polarity solvent to prepare the HSQ polymer and by optimizing the LED hole-injection layer thickness. A stochastic analysis of 31 SiQD syntheses revealed that SiQDs with the highest PLQYs were obtained from a hard, low-carbon HSQ polymer precursor containing many Si-H groups and cage structures. Notably, simple FTIR measurements predicted whether a HSQ polymer would yield high-PLQY SiQDs and high-EQE LEDs. These straightforward, cost-effective protocols should lead to advances in SiQD synthesis and LED fabrication methods.