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The reduction of the boryl-substituted SnII bromide {(HCDippN)2 B}Sn(IPrMe)Br with 1.5â equivalents of potassium graphite leads to the generation of the cyclic tetratin tetraboryl system K2 [Sn4 {B(NDippCH)2 }4 ], a homo-metallic heavier analogue of the cyclobutadiene dianion. This system is non-aromatic as determined by Nucleus Independent Chemical Shift Calculations (NICS(0)=-0.28, NICS(1)=-3.17), with the primary contributing resonance structures shown by Natural Resonance Theory (NRT) to involve a Sn=Sn double bond and 1,2-localized negative charges. Abstraction of the K+ cations or oxidation leads to contraction or cleavage of the Sn4 unit, respectively, while protonation generates the neutral dihydride 1,2-Sn4 {B(NDippCH)2 }4 H2 (a heavier homologue of cyclobutene) in a manner consistent with the predicted charge distribution in the [Sn4 {B(NDippCH)2 }4 ]2- dianion.
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Boryltin compounds featuring the metal in the+1 or 0 oxidation states can be synthesized from the carbene-stabilized tin(II) bromide (boryl)Sn(NHC)Br (boryl={B(NDippCH)2 }; NHC=C{(Ni PrCMe)2 }) by the use of strong reducing agents. The formation of the mono-carbene stabilized distannyne and donor-free distannide systems (boryl)SnSn(IPrMe)(boryl) (2) and K2 [Sn2 (boryl)2 ] (3), using Mg(I) and K reducing agents mirrors related germanium chemistry. In contrast to their lighter congeners, however, systems of the type [Sn(boryl)]n are unstable with respect to disproportionation. Carbene abstraction from 2 using BPh3 , and two-electron oxidation of 3 both result in the formation of a 2 : 1 mixture of the Sn(II) compound Sn(boryl)2 , and the hexatin cluster, Sn6 (boryl)4 (4). A viable mechanism for this rearrangement is shown by quantum chemical studies to involve a vinylidene intermediate (analogous to the isolable germanium compound, (boryl)2 Ge=Ge), which undergoes facile atom transfer to generate Sn(boryl)2 and trinuclear [Sn3 (boryl)2 ]. The latter then dimerizes to give the observed hexametallic product 4, with independent studies showing that similar trigermanium species aggregate in analogous fashion.
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The synthesis of a novel mono-anionic phosphino-amide ligand based on a xanthene backbone is reported, togetherr with the corresponding GaI complex, (PON)Ga (PON = 4-(di(2,4,6-trimethylphenyl)phosphino)-5-(2,6-diisopropylanilido)-2,7-di-tert-butyl-9,9-dimethylxanthene). The solid-state structure of (PON)Ga (obtained from X-ray crystallography) reveals very weak Oâ â â Ga and Pâ â â Ga interactions, consistent with a R2 NGa fragment which closely resembles those found in one-coordinate amidogallium systems. Strong N-to-Ga π donation from the amido substituent is reflected in a very short N-Ga distance (1.961(2)â Å), while the Pâ â â Ga contact (3.076(1)â Å) is well outside the sum of the respective covalent radii. While the donor properties of the PON ligand towards GaI are highly unsymmetrical, oxidation to GaIII leads to much stronger coordination of the pendant phosphine as shown by P-Ga distances which are up to 20 % shorter. From a steric perspective, the PON ligand is shown to be significantly bulkier than related ß-diketiminate systems, a finding consistent with reactions of (PON)Ga towards O-atom sources that proceed without oligomerization. Despite this, the enhanced P-donor properties brought about by oxidation at gallium are not sufficient to quench the reactivity of the highly polar Ga-O unit. Instead, intramolecular benzylic C-H activation is observed across the Ga-O bond of a transient gallanone intermediate.
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We report two BNB-type frustrated Lewis pairs which feature an acceptor-donor-acceptor functionalized cavity, and which differ in the nature of the B-bound fluoroaryl group (C6 F5 vs. C6 H3 (CF3 )2 -3,5, Arf ). These receptor systems are capable of capturing gaseous CO, and in the case of the -BArf 2 system this can be shown to occur in reversible fashion at/above room temperature. For both systems, the binding event is accompanied by migration of one of the aryl substituents to the electrophilic carbon of the CO guest. Experiments utilizing an additional equivalent of Pt Bu3 allow the initially formed (non-migrated) CO adduct to be identified and trapped (via demethylation), while also establishing the reversibility of the B-to-C migration process. When partnered with the slightly less Lewis acidic -BArf 2 substituent, this reversibility allows for release of the captured carbon monoxide in the temperature range 40-70 °C, and the possibility for CO sensing, making use of the associated colourless to orange/red colour change.
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Collagen, one of the most biocompatible materials in nature, is widely used in wound healing and organ repair. However, the limited mechanical strength and biological effectiveness of collagen restrain its application as a hemostasis and filling material in medicine. To overcome these limitations, ultraporous collagen/oxidized regenerated cellulose (Col/ORC) composites were prepared. The results showed that the Col-0.25%ORC composite had optimal wettability, porosity, and water absorption. An MTT assay proved that the Col and Col/ORC composites possessed no cytotoxicity in living cells. Evaluation of the hemostatic time in vivo and the amount of bleeding in two injury models revealed that the Col-0.25%ORC composite has the most outstanding biological effectiveness and could be biodegraded completely without any inflammatory reaction after 3 weeks. The SEM micrographs showed that the fasciculate ORC fibers were evenly dispersed into the reticulate structure of the Col sponge. The FT-IR spectra of the Col-ORC composites were completely different from that of neat ORC, but similar to Col spectra. Moreover, a possible hemostasis mechanism was discussed based on ELISA analysis, coagulation function, and physicochemical properties.
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With the development of technology, the humanoid robot is no longer a concept, but a practical partner with the potential to assist people in industry, healthcare and other daily scenarios. The basis for the success of humanoid robots is not only their appearance, but more importantly their anthropomorphic behaviors, which is crucial for the human-robot interaction. Conventionally, robots are designed to follow meticulously calculated and planned trajectories, which typically rely on predefined algorithms and models, resulting in the inadaptability to unknown environments. Especially when faced with the increasing demand for personalized and customized services, predefined motion planning cannot be adapted in time to adapt to personal behavior. To solve this problem, anthropomorphic motion planning has become the focus of recent research with advances in biomechanics, neurophysiology, and exercise physiology which deepened the understanding of the body for generating and controlling movement. However, there is still no consensus on the criteria by which anthropomorphic motion is accurately generated and how to generate anthropomorphic motion. Although there are articles that provide an overview of anthropomorphic motion planning such as sampling-based, optimization-based, mimicry-based, and other methods, these methods differ only in the nature of the planning algorithms and have not yet been systematically discussed in terms of the basis for extracting upper limb motion characteristics. To better address the problem of anthropomorphic motion planning, the key milestones and most recent literature have been collated and summarized, and three crucial topics are proposed to achieve anthropomorphic motion, which are motion redundancy, motion variation, and motion coordination. The three characteristics are interrelated and interdependent, posing the challenge for anthropomorphic motion planning system. To provide some insights for the research on anthropomorphic motion planning, and improve the anthropomorphic motion ability, this article proposes a new taxonomy based on physiology, and a more complete system of anthropomorphic motion planning by providing a detailed overview of the existing methods and their contributions.
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Owing to its crucial role in the human body, collagen has immense potential as a material for the biofabrication of tissues and organs. However, highly refined fabrication using collagen remains difficult, primarily because of its notably soft properties. A quantitative biofabrication platform to construct collagen-based peripheral nerve grafts, incorporating bionic structural and chemical guidance cues, is introduced. A viscoelastic model for collagen, which facilitates simulating material relaxation and fabricating collagen-based neural grafts, achieving a maximum channel density similar to that of the native nerve structure of longitudinal microchannel arrays, is established. For axonal regeneration over considerable distances, a gradient printing control model and quantitative method are developed to realize the high-precision gradient distribution of nerve growth factor required to obtain nerve grafts through one-step bioprinting. Experiments verify that the bioprinted graft effectively guides linear axonal growth in vitro and in vivo. This study should advance biofabrication methods for a variety of human tissue-engineering applications requiring tailored cues.
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Bioimpressão , Alicerces Teciduais , Humanos , Alicerces Teciduais/química , Engenharia Tecidual/métodos , Colágeno/química , Nervos Periféricos , Bioimpressão/métodos , Impressão TridimensionalRESUMO
Three-dimensional (3D) printing has emerged as a transformative technology for tissue engineering, enabling the production of structures that closely emulate the intricate architecture and mechanical properties of native biological tissues. However, the fabrication of complex microstructures with high accuracy using biocompatible, degradable thermoplastic elastomers poses significant technical obstacles. This is primarily due to the inherent soft-matter nature of such materials, which complicates real-time control of micro-squeezing, resulting in low fidelity or even failure. In this study, we employ Poly (L-lactide-co-ϵ-caprolactone) (PLCL) as a model material and introduce a novel framework for high-precision 3D printing based on the material plasticization process. This approach significantly enhances the dynamic responsiveness of the start-stop transition during printing, thereby reducing harmful errors by up to 93%. Leveraging this enhanced material, we have efficiently fabricated arrays of multi-branched vascular scaffolds that exhibit exceptional morphological fidelity and possess elastic moduli that faithfully approximate the physiological modulus spectrum of native blood vessels, ranging from 2.5 to 45 MPa. The methodology we propose for the compatibilization and modification of elastomeric materials addresses the challenge of real-time precision control, representing a significant advancement in the domain of melt polymer 3D printing. This innovation holds considerable promise for the creation of detailed multi-branch vascular scaffolds and other sophisticated organotypic structures critical to advancing tissue engineering and regenerative medicine.
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Materiais Biocompatíveis , Elastômeros , Poliésteres , Impressão Tridimensional , Engenharia Tecidual , Alicerces Teciduais , Elastômeros/química , Alicerces Teciduais/química , Engenharia Tecidual/métodos , Poliésteres/química , Materiais Biocompatíveis/química , Módulo de Elasticidade , Teste de Materiais , Humanos , Estresse Mecânico , Vasos Sanguíneos , Prótese VascularRESUMO
Over the past two decades, 3D bioprinting has become a popular research topic worldwide, as it is the most promising approach for manufacturing vascularized organs in vitro. However, transitioning from bioprinting of simple tissue models to real biomedical applications is still a challenge due to incomplete interdisciplinary theoretical knowledge and imperfect multi-technology integration. This review examines the goals of vasculature manufacturing and proposes new strategic objectives in three stages. We then outline a bidirectional manufacturing strategy consisting of top-down reconstruction (bioprinting) and bottom-up regeneration (cellular behaviour). We also provide an in-depth analysis of the four aspects of design, ink, printing and culture. Furthermore, we present the 'construction-comprehension cycle' research paradigm and the 'math-model-based batch insights generator' research paradigm for the future, which may have the potential to revolutionize the biomedical field.
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Bioimpressão , Engenharia Tecidual , Impressão TridimensionalRESUMO
A tetraboryl digermene synthesized by the reaction between a dianionic digermanide nucleophile and a boron halide electrophile is dimeric both in the solid state and in hydrocarbon solution. It features both a planar 'alkene-like' geometry for the Ge2B4 core, and an exceptionally short GeîGe double bond. These structural features are consistent with the known electronic properties of the boryl group, and with lowest energy (in silico) fragmentation into two triplet bis(boryl)germylene fragments.
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Fabricating connective tissue with printing fidelity, structural stability, biocompatibility, and cellular orientation remains a challenge for bioink. Collagen, as inherent fibers to provide strengthin vivo, should be the ideal material for tissue printing. However, current collagen-bioink exhibits poor printability and mechanical properties. Here, the light-crosslinkable norbornene-collagen (NorCol) is developed to solve this dilemma. NorCol with complete collagen structure exhibits outstanding shear-thinning properties and light-crosslinking strength, realizing the construction of complicated constructs with excellent printing fidelity and structural stability. Neutral-dissolved NorCol with different concentrations is directly integrated to print pure collagen structure with composite modulus, providing top-class biocompatibility that mimics the heterogeneous microarchitecture of the extracellular matrix (ECM). This composite structure also permits extensive infiltration of host tissue and capillaries during subcutaneous transplants. By the designed tight interface of printed filaments, a geometric-guided and modulus-independent anisotropic mechanical environment is constructed, realizing cellular orientation. Furthermore, the cellular orientation is in the same direction as the printed high-concentration NorCol, which is the same case of cells and collagen fibersin vivo. This capability of NorCol breaks new ground for printing pure ECM protein-based, implantable and functional constructs, applicable in connective tissue engineering for human applications.
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Bioimpressão , Alicerces Teciduais , Humanos , Alicerces Teciduais/química , Impressão Tridimensional , Colágeno/química , Tecido ConjuntivoRESUMO
Engineered implantable functional thick tissues require hierarchical vasculatures within cell-laden hydrogel that can mechanically withstand the shear stress from perfusion and facilitate angiogenesis for nutrient transfer. Yet current extrusion-based 3D printing strategies are unable to recapitulate hierarchical networks, highlighting the need for bioinks with tunable properties. Here, we introduce an approach whereby crosslinkable microgels enhance mechanical stability and induce spontaneous microvascular networks comprised of human umbilical cord vein endothelial cells (HUVECs) in a soft gelatin methacryoyl (GelMA)-based bioink. Furthermore, we successfully implanted the 3D printed multi-branched tissue, being connected from the rat carotid artery to the jugular vein direct surgical anastomosis. The work represents a significant step toward in the field of large vascularized tissue fabrication and may have implications for the treatment of organ failure in the future.
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Bioimpressão , Microgéis , Ratos , Humanos , Animais , Engenharia Tecidual , Alicerces Teciduais , Células Endoteliais da Veia Umbilical HumanaRESUMO
Biodegradable polycaprolactone/ß-tricalcium phosphate (PT) composites are desirable candidates for bone tissue engineering applications. A higher ß-tricalcium phosphate (TCP) ceramic content improves the mechanical, hydrophilic and osteogenic properties of PT scaffolds in vitro. Using a dynamic degradation reactor, we established a steady in vitro degradation model to investigate the changes in the physio-chemical and biological properties of PT scaffolds during degradation.PT46 and PT37 scaffolds underwent degradation more rapidly than PT scaffolds with lower TCP contents. In vivo studies revealed the rapid degradation of PT (PT46 and PT37) scaffolds disturbed macrophage responses and lead to bone healing failure. Macrophage co-culture assays and a subcutaneous implantation model indicated that the scaffold degradation process dynamically affected macrophage responses, especially polarization. RNA-Seq analysis indicated phagocytosis of the degradation products of PT37 scaffolds induces oxidative stress and inflammatory M1 polarization in macrophages. Overall, this study reveals that the dynamic patterns of biodegradation of degradable bone scaffolds highly orchestrate immune responses and thus determine the success of bone regeneration. Therefore, through evaluation of the biological effects of biomaterials during the entire process of degradation on immune responses and bone regeneration are necessary in order to develop more promising biomaterials for bone regeneration.
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Nerve guidance conduits (NGCs) are an essential solution for peripheral nerve repair and regeneration in tissue engineering and medicine. However, the ability of current NGCs is limited to repairing longer nerve gap (i.e., >20 mm) because it cannot meet the following two conditions simultaneously: (1) directional guidance of the axial high-density channels and (2) regenerative stimulation of the extracellular matrix secreted by Schwann cells (SCs). Therefore, we propose a multi-material 3D bioprinting process to fabricate multi-channel nerve guide conduits (MNGCs) containing SCs. In the article, cell-laden methacrylate gelatin (GelMA) was used as the bulk material of MNGCs. To improve the printing accuracy of the axial channels and the survival rate of SCs, we systematically optimized the printing temperature parameter based on hydrogel printability analysis. The multi-material bioprinting technology was used to realize the alternate printing of supporting gelatin and cell-laden GelMA. Then, the high-accuracy channels were fabricated through the UV cross-linking of GelMA and the dissolving technique of gelatin. The SCs distributed around the channels with a high survival rate, and the cell survival rate maintained above 90%. In general, the study on multi-material 3D printing was carried out from the fabricating technology and material analysis, which will provide a potential solution for the fabrication of MNGCs containing SCs.
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It is well known that welding dissimilar metals can play the advantages and characteristics of those different metals, but it is easy to encounter some problems. In this paper, the thermomechanical behavior of the weldolet-branch dissimilar steel joints in different welding cases is analyzed by establishing a three-dimensional finite element model, and the predicted thermal cycling and residual stresses are verified using experimental tools. The results show that the high temperature area and the heat affected zone on the side of the branch pipe are larger, and there is a large stress gradient at the fusion line on both sides of the weld. Too high or too low temperature between welding layers will cause large residual stress, thus, 200 °C is more suitable for the welding of weldolet-branch joints. The residual stresses of path-1, path-2 and path-3 have similar distributions at 0° and 180° sections, and the circumferential and axial residual stresses on the inner surface are larger than those on the outer surface. The residual stress on the inner and outer surfaces of path-3 is smaller than that of path-1 and path-2 at the 90° and 270° sections as a whole, and the residual stress at the 90° section reaches the minimum.
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Traditional tissue engineering skin are composed of living cells and natural or synthetic scaffold. Besize the time delay and the risk of contamination involved with cell culture, the lack of autologous cell source and the persistence of allogeneic cells in heterologous grafts have limited its application. This study shows a novel tissue engineering functional skin by carrying minimal functional unit of skin (MFUS) in 3D-printed polylactide-co-caprolactone (PLCL) scaffold and collagen gel (PLCL + Col + MFUS). MFUS is full-layer micro skin harvested from rat autologous tail skin. 3D-printed PLCL elastic scaffold has the similar mechanical properties with rat skin which provides a suitable environment for MFUS growing and enhances the skin wound healing. Four large full-thickness skin defects with 30 mm diameter of each wound are created in rat dorsal skin, and treated either with tissue engineering functional skin (PLCL + Col + MFUS), or with 3D-printed PLCL scaffold and collagen gel (PLCL + Col), or with micro skin islands only (Micro skin), or without treatment (Normal healing). The wound treated with PLCL + Col + MFUS heales much faster than the other three groups as evidenced by the fibroblasts migration from fascia to the gap between the MFUS dermis layer, and functional skin with hair follicles and sebaceous gland has been regenerated. The PLCL + Col treated wound heals faster than normal healing wound, but no skin appendages formed in PLCL + Col-treated wound. The wound treated with micro skin islands heals slower than the wounds treated either with tissue engineering skin (PLCL + Col + MFUS) or with PLCL + Col gel. Our results provide a new strategy to use autologous MFUS instead "seed cells" as the bio-resource of engineering skin for large full-thickness skin wound healing.
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A novel peptide-based polymer is developed by lysine-diisocyanate (LDI), glycerol (Gly), and fully reduced HMGB1 (frHMGB1). This frHMGB1-LDI-Gly polymer either forms sponge-like foam (scaffold) or a hydrogel or a film under different reaction conditions. It degrades into nontoxic lysine, glycerol, and frHMGB1. The hydrogel glues tissues together and the glued tissues have strong mechanical properties. The film and scaffold provide the suitable environment for enhancing cell proliferation by releasing frHMGB1. The scaffold carries 1 mm diameter of full-thickness rat skin-island as a minimal functional unit of skin (MFUS) to treat large full thickness skin wounds, and the hydrogel glues the MFUS and scaffold with skin edges together (MFUS+Scaffold group). The scaffold treated wounds (Scaffold group) heal much faster than the wounds either treated with MFUS (MFUS group) or without treatment (Wound group). The MFUS+Scaffold treated wound regenerates more functional full-thickness skin with more hair follicles and sweat glands, higher CD146 and α-smooth muscle actin levels, more blood vessels and collagen productions, and less scar tissues when compared to the other three groups. The results demonstrate that the combination of frHMGB1-LDI-Gly polymer with MFUS provides a new tissue engineering approach for large full-thickness skin wound healing.
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Proteína HMGB1 , Poliuretanos , Alicerces Teciduais , Cicatrização , Animais , Proteína HMGB1/farmacologia , Peptídeos/farmacologia , Poliuretanos/farmacologia , Ratos , Pele/metabolismo , Cicatrização/fisiologiaRESUMO
How to generate anthropomorphic reaching movement remains a challenging problem in service robots and human motor function repair/reconstruction equipment. However, there is no universally accepted computational model in the literature for reproducing the motion of the human upper limb. In response to the problem, this article presents a computational framework for generating reaching movement endowed with human motion characteristics that imitated the mechanism in the control and realization of human upper limb motions. This article first establishes the experimental paradigm of human upper limb functional movements and proposes the characterization of human upper limb movement characteristics and feature movement clustering methods in the joint space. Then, according to the specific task requirements of the upper limb, combined with the human sensorimotor model, the estimation method of the human upper limb natural postures was established. Next, a continuous task parametric model matching the characteristic motion class is established by using the Gaussian mixture regression method. The anthropomorphic motion generation method with the characteristics of the smooth trajectory and the ability of natural obstacle avoidance is proposed. Finally, the anthropomorphic motion generation method proposed in this article is verified by a human-like robot. The measurement index of the human-likeness degree of the trajectory is given. The experimental results show that for all four tested tasks, the human-likeness degrees were greater than 90.8%, and the trajectories' jerk generated by this method is very similar to the trajectories' jerk of humans, which validates the proposed method.
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Robótica , Humanos , Robótica/métodos , Extremidade Superior/fisiologia , Movimento/fisiologia , PosturaRESUMO
In this paper, based on Simufact Welding finite element analysis software, a numerical simulation of the temperature and residual stress distribution of the weldolet-header multi-layer multi-pass welding process is carried out, and the simulation results are verified through experiments. The experimental results are in good agreement with the numerical simulation results, which proves the validity of the numerical simulation results. Through the results of the numerical simulation, the influence of the welding sequence and interlayer temperature on the temperature and residual stress distribution at different locations of the saddle-shaped weld was studied. The results show that the temperature and residual stress distribution on the header and weldolet are asymmetric, and the high-stress area of the saddle-shaped welded joint always appears at the saddle shoulder or saddle belly position. When the interlayer temperature is 300 °C, the peak residual stress reaches a minimum of 428.35 MPa. Adjusting the welding sequence can change the distribution trend of residual stress. There is no high-stress area on the first welding side of the two-stage welding path-2. The peak values of residual stresses for continuous welding path-1 and two-stage welding path-2 are 428.35 MPa and 434.01 MPa, respectively, which are very close to each other.
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As the essential foundation of bioprinting technology, cell-laden bio-ink is confronted with the inevitable contradiction between printability and bioactivity. For example, type I collagen has been widely applied for its excellent biocompatibility; however, its relatively low self-assembly speed restricts the performance in high-precision bioprinting of cell-laden structures. In this study, we synthesize norbornene-functionalized neutral soluble collagen (NorCol) by the reaction of acid-soluble collagen (Col) and carbic anhydride in the aqueous phase. NorCol retains collagen triple-helical conformation and can be quickly orthogonally cross-linked to build a cell-laden hydrogel via a cell-friendly thiol-ene photoclick reaction. Moreover, the additional carboxyl groups produced in the reaction of carbic anhydride and collagen obviously improve the solubility of NorCol in neutral buffer and miscibility of NorCol with other polymers such as alginate and gelatin. It enables hybrid bio-ink to respond to multiple stimuli, resulting in continuous cross-linked NorCol networks in hybrid hydrogels. For the first time, the collagen with a triple helix structure and gelatin can be mixed and printed, keeping the integrity of the printed construct after gelatin's dissolution. The molecular interaction among giant collagen molecules allows NorCol hydrogel formation at a low concentration, which leads to excellent cell spreading, migration, and proliferation. These properties give NorCol flexible formability and excellent biocompatibility in temperature-, ion-, and photo-based bioprinting. We speculate that NorCol is a promising bio-ink for emerging demands in tissue engineering, regenerative medicine, and personalized therapeutics.