Sequential Formation Research Articles

Core-shell structured tow-pregs enabled additive manufacturing of continuously reinforced thermoset composites

One of the major challenges in thermally curable polymer composite additive manufacturing is the slow curing time of thermally curable resins, coupled with a significant drop in thermoset viscosity upon heating, making the formation of complex shapes difficult. To tackle these issues, we have introduced a novel rapid composite preformation strategy called Tow-Preg Cladding (TPC). This technique involves the use of a thin and rapidly curable dual-cure resin, which combines a thermally curable resin (such as epoxy) with a fast photo-curable resin. The dual-cure resin is applied as a coating over a thermally curable resin tow-preg, enabling the formation of a rigid cladding that supports and shapes the tow-pregs into the desired geometries and patterns. The key advantage of this approach lies in the sequential formation of an interpenetrating polymer network (IPN) at the interlayer between laminates, resulting from the curing of the photocurable resin and the thermally curable resin sequentially. This IPN formation enhances interlaminar bonding in the composite, contributing to its overall strength and performance. The composites produced using this technique exhibited impressive mechanical properties, including longitudinal tensile strength of 1058.2 MPa, longitudinal tensile modulus of 74.2 GPa, flexural strength of 1080.4 MPa, and flexural modulus of 41.7 GPa. Overall, our Tow-Preg Cladding approach shows great promise in overcoming the challenges associated with thermally curable polymer composite additive manufacturing. It offers a viable solution to creating strong, shape-specific thermoset composites efficiently with enhanced mechanical properties.

Operando X-Ray Absorption Spectroscopy of Solid Electrolyte Interphase Formation on Silicon Anodes

Lithium-ion batteries (LIBs) are key to the transition from fossil fuels towards increased use of renewable energy sources. However, more widespread deployment requires improvements in energy density, cost and cycle-lifetime. Various cathode and anode materials are under consideration for next-generation LIBs, and the interfacial stability of these materials in contact with the electrolyte is a critical consideration. Interface-sensitive operando characterization techniques are thus urgently needed to reveal the reactions occurring in working batteries.1,2 The solid electrolyte interphase (SEI) that forms on Li-ion battery anodes is critical to their long-term performance, however observing SEI formation processes at the buried electrode-electrolyte interface is a significant challenge. Here we show that operando soft X-ray absorption spectroscopy in total electron yield mode can resolve the chemical evolution of the SEI during electrochemical formation in a Li-ion cell, with nm-scale interface sensitivity. O, F, and Si K-edge spectra, acquired as a function of potential, reveal when key reactions occur on high-capacity amorphous Si anodes cycled with and without fluoroethylene carbonate (FEC).3 Cross-referencing to cycling data, complementary bulk sensitive fluoresecent yield (FY) XAS measurements, and density functional theory (DFT) calculated spectra enables identification of the electrolyte and SEI species, and the dominant mechanisms of SEI formation. Without FEC present, LiF formation is detected at 0.6 V vs. Li/Li+ prior to significant lithiation of the a-Si, whilst at lower potentials the SEI grows in thickness with an increased contribution from organic components containing -C(=O)O- species. The observed sequential formation of inorganic and organic components is implicated in layering of the SEI. With FEC as an additive we see the onset of SEI formation at much higher potentials (1.0 V vs. Li/Li+), and attribute the improved cycle life seen with this additive to the rapid healing of SEI defects formed during delithiation. Operando TEY-XAS offers new insights into the formation mechanisms of electrode-electrolyte interphases and their stability for a wide variety of electrode materials and electrolyte formulations. References Wu et al. Phys. Chem. Chem. Phys. 2015, 17, 30229.Weatherup et al. Top. Catal. 2018, 61, 2085.Swallow et al. Nature Commun. 2022, 13, 6070.

Linear resistance limiting the current of intergranular barriers in varistor ceramics

Method for measuring the linear resistivity ρlin, which affects the volt-ampere characteristic (VAC) nonlinearity of varistor materials in a high current region is proposed. For ZnO based varistor ceramics the dependence of ρlin on amplitude density Jmax of current pulse is studied in the range 5 A cm-2 – 4600 A cm-2. At Jmax < 200 A cm-2 a sharp decrease of ρlin with increasing Jmax takes place. This behavior indicates a non-uniform distribution of high current over the cross section of ceramics sample. At Jmax > 1000 A cm-2 ρlin does not depend on Jmax and has a value of 0.49 – 0.50 Ohm cm corresponding to the volume resistivity ρg of ZnO grains. The decrease in nonlinearity of VAC at high currents is due to the formation of conductive paths of electric current between the electrodes of a sample. Along such paths, all intergranular double Schottky barriers are in a reversible electrical breakdown mode, probably due to impact ionization. The current in these paths is limited by small linear volume resistance of the grains. A spread of grain sizes is the reason for existence of current paths with different numbers of contacts between grains and therefore with different breakdown voltages. At voltage increases, the sequential formation of parallel-connected conductive paths occurs. This explains the inhomogeneous distribution of high current over the cross section of a sample at Jmax < 200 A cm-2. At Jmax > 1000 A cm-2 almost all current paths in a sample are switched on and the value of ρlin limiting the barriers current is close to the volume resistivity ρg of grains.

Defect-Induced Secondary Crystals Drive Two-Dimensional to Three-Dimensional Morphological Evolution in the Co-Self-Assembly of Polyferrocenylsilane Block Copolymer and Homopolymer.

Bottom-up fabrication protocols for uniform 3D hierarchical structures in solution are rare. We report two different approaches to fabricate uniform 3D spherulites and their precursors using mixtures of poly(ferrocenyldimethylsilane) (PFS) block copolymer (BCP) and PFS homopolymer (HP). Both protocols are designed to promote defects in 2D assemblies that serve as intermediate structures. In a multistep seeded growth protocol, we add the BCP/HP mixture to (1D) rod-like PFS micelles in a selective solvent as first-generation seeds. This leads to 2D platelet structures. If this step is conducted at a high supersaturation, secondary crystals form on the basal surface of these platelets. Co-crystallization and rapid crystallization of BCP/HP promote the formation of defects that act as nucleation sites for secondary crystals, resulting in multilayer platelets. This is the key step. The multilayer platelets serve as second-generation seeds upon subsequent addition of BCP/HP blends and, with increasing supersaturation, lead to the sequential formation of uniform (3D) hedrites, sheaves, and spherulites. Similar structures can also be obtained by a simple one-pot direct self-assembly (heating-cooling-aging) protocol of PFS BCP/HP blends. In this case, for a carefully chosen but narrow temperature range, PFS HPs nucleate formation of uniform structures, and the annealing temperature regulates the supersaturation level. In both protocols, the competitive crystallization kinetics of HP/BCP affects the morphology. Both protocols exhibit broad generality. We believe the morphological transformation from 2D to 3D structures, regulated by defect formation, co-crystallization, and supersaturation levels, could apply to various semicrystalline polymers. Moreover, the 3D structures are sufficiently robust to serve as recoverable carriers for nanoparticle catalysts, exhibiting valuable catalytic activity and opening new possibilities for applications requiring exquisite 3D structures.

Electrochemical silicification of Mo in molten CaCl2–CaSiO3 enhances high-temperature oxidation resistance

This work aims to demonstrate the feasibility and effectiveness of electrochemical silicification of Mo in molten CaCl2–CaSiO3. Through constant-current electrolysis at 1123 K, high-quality α-MoSi2 coatings are successfully deposited on Mo plates, following the sequential formation of Mo5Si3 and β-MoSi2 phases. Increased current density results in grain refinement and reduced surface roughness due to the increase in overpotential. The oxidation test indicates that the silicide-coated Mo plate can withstand exposure to air at 1573 K for more than 15 h with minimal damage, showcasing the excellent high-temperature oxidation resistance. These findings highlight the potential application of the electrochemical silicification process.

Multiplicative enhancement of stereoenrichment by a single catalyst for deracemization of alcohols.

Stereochemical enrichment of a racemic mixture by deracemization must overcome unfavorable entropic effects as well as the principle of microscopic reversibility; recently, photochemical reaction pathways unveiled by the energetic input of light have led to innovations toward this end, most often by ablation of a stereogenic C(sp3)-H bond. We report a photochemically driven deracemization protocol in which a single chiral catalyst effects two mechanistically different steps, C-C bond cleavage and C-C bond formation, to achieve multiplicative enhancement of stereoinduction, which leads to high levels of stereoselectivity. Ligand-to-metal charge transfer excitation of a titanium catalyst coordinated by a chiral phosphoric acid or bisoxazoline efficiently enriches racemic alcohols that feature adjacent and fully substituted stereogenic centers to enantiomeric ratios up to 99:1. Mechanistic investigations support a pathway of sequential radical-mediated bond scission and bond formation through a common prochiral intermediate and reveal that, although the overall stereoenrichment is high, the selectivity in each individual step is moderate.

One-Pot Approach to Synthesize Tough and Cell Adhesive Double-Network Hydrogels Consisting of Fully Synthetic Materials of Self-Assembling Peptide and Poly(ethylene glycol).

Hydrogels with a double network (DN) structure are compelling biomaterials, holding potential for use as artificial extracellular matrices. Generally, the DN approach imparts hydrogels with high mechanical strength and cell-adhesive properties. However, achieving this often demands a complex multistep process involving potentially hazardous free-radical polymerization, which can result in toxicity. This limits their broad biological applications. In this work, we introduce a straightforward yet biocompatible method to fabricate tough and cell-adhesive DN hydrogels using entirely synthetic materials: the self-assembling peptide (RADA16) and poly(ethylene glycol) (PEG). An in situ mixing of these components leads to the sequential formation of DN hydrogels─first through the self-assembly of the RADA16 peptide and then via chemical cross-linking between PEG molecules. Hydrogels produced this way exhibited up to a 10-fold increase in fracture energy, and cells seeded on their surfaces showcased good attachment. Our design underscores the efficacy of the DN approach and the promising applications of peptides in tissue engineering.

Electro-oxidative Synthesis of Unsymmetrical Alkyne-1,4-diones via Sequential Ring Formation and Cleavage.

Synthesis of unsymmetrical but-2-yne-1,4-diones is reported through oxidative alkyne translocation of readily accessible homopropargylic alcohols. The developed method consists of an unprecedented one-pot sequential electro-oxidative annulation-fragmentation-chemical selenoxide elimination process. Excellent functional group compatibility was observed, and an array of yne-1,4-diones were synthesized. Derivatization of the alkyne gave access to other valuable scaffolds. Detailed mechanistic studies through the isolation of key intermediates clarified the cascade transformation.

Regioselective Decarboxylative Transformations of Tetrahydro-β-carboline-1-carboxylic Acid: Reagent Controlled Selectivity toward Alkynylated or Enaminone Products.

A one-pot, regioselective decarboxylative alkynylation of tetrahydro-β-carboline-1-carboxylic acid under peroxide-free condition is reported. The reaction is highly selective for the 1-position over the 3-position of tetrahydro-β-carboline. The reaction can afford alkynylated or enaminone products depending on the reagent. The reaction proceeds through sequential decarboxylative iminium ion formation followed by an alkynylation and oxidative rearrangement cascade.

Essential role of CD38 in platelet aggregation through the PKC-mediated internalization and activation.

CD38 is a multifunctional enzyme with a potent Ca2+ mobilizing effect, cyclic ADP-ribose (cADPR), and nicotinic acid adenine dinucleotide phosphate (NAADP). Here, we aimed to demonstrate the role of CD38 in platelets via protein kinase C (PKC)-mediated internalization and activation. Mouse platelets were used in this study. Thrombin, an agonist of platelet function, provoked a prompt and long-lasting increase in intracellular Ca2+ concentration ([Ca2+]i), resulting from an interplay of multifold Ca2+ mobilizing messengers.The signaling pathway was delineated using different inhibitors and techniques such as platelet aggregation assay, intracellular calcium measurements, immunoprecipitation, immunoblotting, and flow cytometry. We observed a sequential formation of cADPR and NAADP through CD38 activation by PKC of non-muscle myosin heavy chain IIA (MHCIIA), resulting in phospholipase C (PLC) activation in the thrombin-stimulated platelets. These findings reveal that PKC is fundamental in activating CD38 and elicits a physiological response in the murine platelets. PKC is involved in many signaling pathways. Specifically, PKC is involved in the internalization of CD38 via MHCIIA in CD38+/+ wild-type (WT) and CD38-/- knockout mice (KO). CD38 generates calcium-mobilizing agents that act on specific receptors of the calcium stores. Calcium triggered platelet aggregation while serving as a secondary messenger.

A Carbene Relay Strategy for Cascade Insertion Reactions

AbstractInsertion reactions that involve stabilized electrophilic metallocarbenes are of great importance for installing α‐heteroatoms to carbonyl compounds. Nevertheless, the limited availability of carbene precursors restricts the introduction of only a single heteroatom. In this report, we describe a new approach based on an I(III)/S(VI) reagent that promotes the cascade insertion of heteroatoms. This is achieved by sequentially generating two α‐heteroatom‐substituted metal carbenes in one reaction. We found that this mixed I(III)/S(VI) ylide reacts efficiently with a transition metal catalyst and an X−H bond (where X=O, N). This transformation leads to the sequential formation of a sulfoxonium‐ and an X‐substituted Rh‐carbenes, enabling further reactions with another Y−H bond. Remarkably, a wide range of symmetrical and unsymmetrical α,α‐O,O‐, α,α‐O,N‐, and α,α‐N,N‐subsituted ketones can be prepared under mild ambient conditions. In addition, we successfully demonstrated other cascades, such as CN/CN double amidation, C−H/C−S double insertion, and C−S/Y−H double insertion (where Y=S, N, O, C). Notably, the latter two cascades enabled the simultaneous installation of three functional groups to the α‐carbon of carbonyl compounds in a single step. These reactions demonstrate the versatility of our approach, allowing for the synthesis of ketones and esters with multiple α‐heteroatoms using a common precursor.

A Carbene Relay Strategy for Cascade Insertion Reactions.

Insertion reactions that involve stabilized electrophilic metallocarbenes are of great importance for installing α-heteroatoms to carbonyl compounds. Nevertheless, the limited availability of carbene precursors restricts the introduction of only a single heteroatom. In this report, we describe a new approach based on an I(III) /S(VI) reagent that promotes the cascade insertion of heteroatoms. This is achieved by sequentially generating two α-heteroatom-substituted metal carbenes in one reaction. We found that this mixed I(III) /S(VI) ylide reacts efficiently with a transition metal catalyst and an X-H bond (where X=O, N). This transformation leads to the sequential formation of a sulfoxonium- and an X-substituted Rh-carbenes, enabling further reactions with another Y-H bond. Remarkably, a wide range of symmetrical and unsymmetrical α,α-O,O-, α,α-O,N-, and α,α-N,N-subsituted ketones can be prepared under mild ambient conditions. In addition, we successfully demonstrated other cascades, such as CN/CN double amidation, C-H/C-S double insertion, and C-S/Y-H double insertion (where Y=S, N, O, C). Notably, the latter two cascades enabled the simultaneous installation of three functional groups to the α-carbon of carbonyl compounds in a single step. These reactions demonstrate the versatility of our approach, allowing for the synthesis of ketones and esters with multiple α-heteroatoms using a common precursor.

NLRP3 Inhibition Leads to Impaired Mucosal Fibroblast Function in Patients with Inflammatory Bowel Diseases.

Inflammatory bowel diseases (IBD) are characterized by mucosal inflammation and sequential fibrosis formation, but the exact role of the hyperactive NLRP3 inflammasome in these processes is unclear. Thus, we studied the expression and function of the NLRP3 inflammasome in the context of inflammation and fibrosis in IBD. We analysed intestinal NLRP3 expression in mucosal immune cells and fibroblasts from IBD patients and NLRP3-associated gene expression via single-cell RNA sequencing and microarray analyses. Furthermore, cytokine secretion of NLRP3 inhibitor treated blood and mucosal cells, as well as proliferation, collagen production, and cell death of NLRP3 inhibitor treated intestinal fibroblasts from IBD patients were studied. We found increased NLRP3 expression in the inflamed mucosa of IBD patients and NLRP3 inhibition led to reduced IL-1β and IL-18 production in blood cells and diminished the bioactive form of mucosal IL-1β. Single cell analysis identified overlapping expression patterns of NLRP3 and IL-1β in classically activated intestinal macrophages and we also detected NLRP3 expression in CD163+ macrophages. In addition, NLRP3 expression was also found in intestinal fibroblasts from IBD patients. Inhibition of NLRP3 led to reduced proliferation of intestinal fibroblasts, which was associated with a marked decrease in production of collagen type I and type VI in IBD patients. Moreover, NLRP3 inhibition in intestinal fibroblasts induced autophagy, a cellular process involved in collagen degradation. In the presented study, we demonstrate that inhibiting NLRP3 might pave the way for novel therapeutic approaches in IBD, especially to prevent the severe complication of intestinal fibrosis formation.

Biphasic inflammatory response induced by intra-plantar injection of L-cysteine: Role of CBS-derived H2S and S1P/NO signaling

This study investigates the inflammatory response to intra-plantar injection of L-cysteine in a murine model. L-cysteine induces a two-phase response: an early phase lasting 6 h and a late phase peaking at 24 h and declining by 192 h. The early phase shows increased neutrophil accumulation at 2 h up to 24 h, followed by a reduction at 48 h. On the other hand, the late phase exhibits increased macrophage infiltration peaking at 96 h. Inhibition of cystathionine β-synthase (CBS), the first enzyme in the transsulfuration pathway, significantly reduces L-cysteine-induced edema, suggesting its dependence on CBS-derived hydrogen sulfide (H2S). Sequential formation of sphingosine-1-phosphate (S1P) preceding nitric oxide (NO) generation suggests the involvement of a CBS/S1P/NO axis in the inflammatory response. Inhibition of de novo sphingolipid biosynthesis, S1P1 receptor, and endothelial NO synthase (eNOS) attenuates L-cysteine-induced paw edema. These findings indicate a critical role of the CBS/H2S/S1P/NO signaling pathway in the development and maintenance of L-cysteine-induced inflammation. The co-presence of H2S and NO is necessary for inducing and sustaining the inflammatory response, as NaHS or L-arginine alone do not replicate the marked and prolonged inflammatory effect observed with L-cysteine. This study enhances our understanding of the complex molecular mechanisms of the interplay between NO and H2S pathways in inflammation and identifies potential therapeutic targets for inflammatory disorders.

Nanoscale Wear Triggered by Stress-Driven Electron Transfer.

Wear of sliding contacts causes device failure and energy costs; however, the microscopic principle in activating wear of the interfaces under stress is still open. Here, the typical nanoscale wear, in the case of silicon against silicon dioxide, is investigated by single-asperity wear experiments and density functional theory calculations. The tests demonstrate that the wear rate of silicon in ambient air increases exponentially with stress and does not obey classical Archard's law. Series calculations of atomistic wear reactions generally reveal that the mechanical stress linearly drives the electron transfer to activate the sequential formation and rupture of interfacial bonds in the atomistic wear process. The atomistic wear model is thus resolved by combining the present stress-driven electron transfer model with Maxwell-Boltzmann statistics. This work may advance electronic insights into the law of nanoscale wear for understanding and controlling wear and manufacturing of material surfaces.

Decoding the age–chemical structure of the Milky Way disc: an application of copulas and elicitable maps

ABSTRACT In the Milky Way, the distribution of stars in the [α/Fe] versus [Fe/H] and [Fe/H] versus age planes holds essential information about the history of star formation, accretion, and dynamical evolution of the Galactic disc. We investigate these planes by applying novel statistical methods called copulas and elicitable maps to the ages and abundances of red giants in the Apache Point Observatory Galactic Evolution Experiment survey. We find that the high- and low-α disc stars have a clean separation in copula space and use this to provide an automated separation of the α sequences using a purely statistical approach. This separation reveals that the high-α disc ends at the same [α/Fe] and age at high [Fe/H] as the low-[Fe/H] start of the low-α disc, thus supporting a sequential formation scenario for the high- and low-α discs. We then combine copulas with elicitable maps to precisely obtain the correlation between stellar age τ and metallicity [Fe/H] conditional on Galactocentric radius R and height z in the range 0 < R < 20 kpc and |z| < 2 kpc. The resulting trends in the age–metallicity correlation with radius, height, and [α/Fe] demonstrate a ≈0 correlation wherever kinematically cold orbits dominate, while the naively expected negative correlation is present where kinematically hot orbits dominate. This is consistent with the effects of spiral-driven radial migration, which must be strong enough to completely flatten the age–metallicity structure of the low-α disc.

Pre-mandibular pharyngeal pouches in early non-teleost fish embryos.

The vertebrate pharynx is a key embryonic structure with crucial importance for the metameric organization of the head and face. The pharynx is primarily built upon progressive formation of paired pharyngeal pouches that typically develop in post-oral (mandibular, hyoid and branchial) domains. However, in the early embryos of non-teleost fishes, we have previously identified pharyngeal pouch-like outpocketings also in the pre-oral domain of the cranial endoderm. This pre-oral gut (POG) forms by early pouching of the primitive gut cavity, followed by the sequential formation of typical (post-oral) pharyngeal pouches. Here, we tested the pharyngeal nature of the POG by analysing expression patterns of selected core pharyngeal regulatory network genes in bichir and sturgeon embryos. Our comparison revealed generally shared expression patterns, including Shh, Pax9, Tbx1, Eya1, Six1, Ripply3 or Fgf8, between early POG and post-oral pharyngeal pouches. POG thus shares pharyngeal pouch-like morphogenesis and a gene expression profile with pharyngeal pouches and can be regarded as a pre-mandibular pharyngeal pouch. We further suggest that pre-mandibular pharyngeal pouches represent a plesiomorphic vertebrate trait inherited from our ancestor's pharyngeal metameric organization, which is incorporated in the early formation of the pre-chordal plate of vertebrate embryos.

Kinetic resolution of substituted amido[2.2]paracyclophanes via asymmetric electrophilic amination

Planar chiral [2.2]paracyclophane derivatives are a type of structurally intriguing and practically useful chiral molecules, which have found a range of important applications in the field of asymmetric catalysis and material science. However, access to enantioenriched [2.2]paracyclophanes represents a longstanding challenge in organic synthesis due to their unique structures, which are still highly dependent on the chiral chromatography separation technique and classical chemical resolution strategy to date. In this work, we report on an efficient and versatile kinetic resolution protocol for various substituted amido[2.2]paracyclophanes, including those with pseudo-geminal, pseudo-ortho, pseudo-meta and pseudo-para disubstitutions, using chiral phosphoric acid (CPA)-catalyzed asymmetric amination reaction, which was also applicable to the enantioselective desymmetrization of an achiral diamido[2.2]paracyclophane. Detailed experimental studies shed light on a new reaction mechanism for the electrophilic aromatic C-H amination, which proceeded through sequential triazane formation and N[1,5]-rearrangement. The facile large-scale kinetic resolution reaction and diverse derivatizations of both the recovered chiral starting materials and the C-H amination products showcased the potential of this method.

Heterogeneity in sequential network formation games

In the benchmark model of network formation by Bala and Goyal (2000), the equilibrium network is known as the Center-Sponsored Star (CSS), wherein one player establishes a link with every other player. However, laboratory experiments have shown that CSS do not emerge due to coordination failure and fairness concerns. The difficulty arises from the fact that participants are homogeneous and make simultaneous decisions, making it highly challenging for them to converge on an asymmetric network. In this study, we addressed this coordination issue by introducing a sequential linking decision process. Furthermore, we introduced heterogeneity among the participants and examined whether the presence of a special individual (such as one with a higher monetary value or a different status) affected the network structure. The results revealed that the sequential decision-making process enables the coordination on fair and efficient networks, but not CSS. The impact of heterogeneity varies depending on the type of heterogeneity: the participants with higher values attract more links, leading to increased network asymmetry, whereas non-monetary heterogeneity does not influence linking decisions.

Controlled, supramolecular polymer formulation to engineer hydrogels with tunable mechanical and dynamic properties

AbstractNature uses combined covalent (chemical bonds) and non‐covalent (physical bonds) synthesis in a highly, controlled multi‐step fashion to create functional materials with different mechanical and dynamic properties out of similar building blocks. Surprisingly, this control in fully synthetic systems remains elusive, even though the effects of formulation pathways on the assembly processes have been emphasized—highlighting the importance of and relationship between energy landscapes and function in synthetic systems. Here, we control multiple, coherent supramolecular assembly processes (fiber formation and crosslinking) to formulate hydrogels with tunable mechanical and dynamic properties. Hydrogels are prepared via two different formulation methods using similar building blocks (monofunctional and bifunctional supramolecular monomers), including (1) the mixing of the supramolecular monomers under basic conditions (Fbasic) and (2) the mixing of the supramolecular monomers under neutral conditions (Fneutral). In Fbasic, network formation is induced via simultaneous fiber formation and crosslinking, yielding homogeneously mixed networks which are dense, stiff (~10 kPa) and robust. In Fneutral, network formation is induced through sequential fiber formation and crosslinking, yielding heterogenous, soft (~2 kPa) and dynamic networks. With these results, we advance towards the controlled, multistep, non‐covalent synthesis to create larger hierarchical, functional structures, similar to nature.