DDR1 Drives Malignant Progression of Gastric Cancer by Suppressing HIF-1α Ubiquitination and Degradation.

The extracellular matrix (ECM) has been demonstrated to be dysregulated and crucial for malignant progression in gastric cancer (GC), but the mechanism is not well understood. Here, that discoidin domain receptor 1 (DDR1), a principal ECM receptor, is recognized as a key driver of GC progression is reported. Mechanistically, DDR1 directly interacts with the PAS domain of hypoxia-inducible factor-1α (HIF-1α), suppresses its ubiquitination and subsequently strengthens its transcriptional regulation of angiogenesis. Additionally, DDR1 upregulation in GC cells promotes actin cytoskeleton reorganization by activating HIF-1α/ Ras Homolog Family Member A (RhoA)/Rho-associated protein kinase 1 (ROCK1) signaling, which in turn enhances the metastatic capacity. Pharmacological inhibition of DDR1 suppresses GC progression and angiogenesis in patient-derived xenograft (PDX) and organoid models. Taken together, this work first indicates the effects of the DDR1-HIF-1α axis on GC progression and reveals the related mechanisms, providing experimental evidence for DDR1 as a therapeutic target for GC.

Stimuli-sensitive biomimetic nanoparticles for the inhibition of breast cancer recurrence and pulmonary metastasis.

Biomimetic nanoparticles represent a promising avenue for mitigating rapid clearance by the reticuloendothelial system (RES); however, current challenges include insufficient tumour targeting, suboptimal adhesion, and inadequate localized drug release within tumour regions. These shortcomings contribute to persistent contests, such as recurrence and pulmonary metastasis, even with advanced breast cancer therapies. Stimuli-sensitive drug release can furbish the membrane coated nanoparticles for their efficiency against the stated problems. To enhance the efficacy of biomimetic nanoparticles in addressing these issues, we proposed a versatile, stimuli-responsive drug delivery system by encapsulating doxorubicin (Dox) and perfluorohexane (PFH) within poly (lactic-co-glycolic acid) (PLGA) nanoparticles, subsequently coated with macrophage-derived cell membranes. Within this framework, PFH serves as the mediator for ultrasonic (US)-irradiation-triggered drug release specifically within tumour microenvironment, while the macrophage-derived cell membrane coating enhances cell adhesion, enables immune evasion, and natural tumour-homing ability. The characterization assays and in vitro evaluations yielded encouraging results, indicating enhanced targeting and release efficiencies. In vivo studies demonstrated marked inhibitory effects on both breast cancer recurrence and pulmonary metastasis. The resulting data indicate that these engineered nanoparticles have notable potential for targeted delivery and controlled release upon US irradiation, thereby offering significant therapeutic efficacy against primary breast cancer, pulmonary metastasis, and recurrent malignancies. Our findings lay the groundwork for a novel clinical approach, representing an intriguing direction for ongoing investigation by oncologists.

Fabrication and Optimization of Pickering Emulsion Stabilized by Lignin Nanoparticles for Curcumin Encapsulation.

To develop reversible pH-responsive emulsifiers of natural origin, alkali lignin (AL) was used to develop oil-in-water Pickering emulsions. AL was first modified to synthesize quaternized alkali lignin (QAL), which displayed pH-responsive properties and demonstrated solubility in both acidic and alkaline solutions. In contrast, QAL exhibited insolubility and formed particles in neutral solutions, thereby making it a suitable candidate for utilization as an emulsifier in doubly pH-responsive Pickering emulsions. At pH 5-9, the emulsions were stable. Above or below this pH range, the system demulsifies, resulting in a reversible Pickering emulsifier with two pH-controlled transitions. On the basis of this pH-dependent behavior, lignin-based Pickering emulsions (LPE) could be subjected to several cycles of emulsification-demulsification by alternating the pH of the aqueous phase between basic and acidic, while the droplet size and storage stability were maintained. Curcumin was used as a drug model to study the loading/release behavior of LPE, finding that 50.08% of curcumin could be encapsulated in LPE. The in vitro release of curcumin was pH-dependent. In addition, LPE exhibited an outstanding protective effect against the ultraviolet-induced degradation of curcumin.

Multifunctional Super-Hydrophilic MXene/Biomass Composite Aerogel Evaporator for Efficient Solar-Driven Desalination and Wastewater Treatment.

Solar-driven interfacial evaporation is recognized as a sustainable and effective strategy for desalination to mitigate the freshwater scarcity issue. Nevertheless, the challenges of oil contamination, salt accumulation, and poor long-term stability of the solar desalination process limit its applications. Herein, a 3D biomass-based multifunctional solar aerogel evaporator is developed for water production with fabricated chitosan/lignin (CSL) aerogel as the skeleton, encapsulated with carbonized lignin (CL) particles and Ti3C2TiX (MXene) nanosheets as light-absorbing materials. Benefitting from its super-hydrophilic wettability, interconnected macropore structure, and high broadband light absorption (ca. 95.50%), the prepared CSL-C@MXene-20 mg evaporator exhibited a high and stable water evaporation flux of 2.351 kg m-2 h-1 with an energy conversion efficiency of 88.22% under 1 Sun (1 kW m-2) illumination. The CSL-C@MXene-20 mg evaporator performed excellent salt tolerance and long-term solar vapor generation in a 3.5 wt.% NaCl solution. Also, its super-hydrophilicity and oleophobicity resulted in superior salt resistance and anti-fouling performance in high salinity brine (20 wt.% NaCl) and oily wastewater. This work offers new insight into the manufacture of porous and eco-friendly biomass-based photothermal aerogels for advanced solar-powered seawater desalination and wastewater purification.

Thiocyanogen-modulated N, S Co-doped lignin hierarchical porous carbons for high-performance aqueous supercapacitors.

Constructing heteroatom-doped porous carbons with distinct charge storage properties is significant for high-energy-density supercapacitors, yet it remains a formidable challenge. Herein, we employed a thiocyanogen-modulated alkali activation strategy to synthesize N and S co-doped lignin hierarchical porous carbon (NSLHPC). In this process, thiocyanogen serves as a surface modulation mediator to substitute oxygen with nitrogen and sulfur species, while the combination of KOH activation and MgO template generates numerous nanopores within the carbon structure. The three-dimensional interconnected nanosheet architecture facilitates rapid ion transfer and enhances accessibility to active sites. Density functional theory (DFT) calculations demonstrate that introducing N and S heteroatoms through oxygen substitution reduces the adsorption energy barrier of Zn2+. Consequently, the optimized NSLHPC exhibits a remarkable specific capacitance of 438F/g at 0.5 A/g in 6 M KOH, delivering an energy density of 10.4 Wh/kg in the symmetric supercapacitor and an impressive energy density of 104.9 Wh/kg in the zinc-ion hybrid capacitor. The NSLHPC cathode also shows an excellent lifespan with capacitance retention of 99.0 % and Columbic efficiency of 100 % over 10,000 cycles. This study presents innovative strategies for engineering high-performance porous carbon electrode materials by emphasizing pore structure modulation and N, S co-doping as crucial approaches.

Preparations of 25 wt% of Pyraclostrobin Nanosuspension Concentrate (SC) Using Lignosulfonate-Based Colloidal Spheres to Improve Its Thermal Storage Stability.

Improving the thermal storage stability of nanosuspension concentrate (SC) prepared from low-melting-point pesticide is a recognized problem. In this work, using pyraclostrobin as the raw material, 25 wt% of pyraclostrobin nano-SC was prepared through a water-based grinding method, and the optimal grinding conditions were obtained as follows: a grinding time of 23 h, D-3911 as dispersant and a dispersant dosage of 12 wt%. The pyraclostrobin nano-SC D90 size prepared based on this best formula was 216 nm. Adding glycerin could improve the stability of nano-SC at room temperature, but its thermal storage stability was still poor. For this problem, sodium lignosulfonate and cetyltrimethylammonium bromide (NaLS/CTAB) colloidal spheres were prepared through electrostatic and hydrophobic self-assembly and characterized. The delamination and precipitation of nano-SC can be significantly improved by adding an appropriate amount of colloidal spheres, and the nano-SC D90 size decreased from 2726 to 1023 nm after 7 days of thermal storage. Farmland experiments indicated the control efficiency of pyraclostrobin nano-SC against flowering cabbage downy mildew disease was about 30% higher than that of SC. Especially after adding the wetting agent, the effect of nano-SC could be comparable to that of commercial Kairun (currently the best pyraclostrobin formulation in the world).

Ultrasonic-assisted synthesis of lignin-based ultrasmall silver nanoparticles for photothermal-mediated sterilization.

Lignin-based silver nanoparticles have been considered a promising antimicrobial material. However, it remains challenging to prepare ultra-small size silver nanoparticles sustainably with superior antibacterial performance. In this work, we modified ethanol-extracted lignin (EL) with carboxymethyl groups and further synthesized ultra-small particle size (3.8 ± 0.1 nm) nanosilver incorporated carboxymethyl lignin complexes (AgNPs@CEL) using ultrasonic technology. Due to the outstanding antibacterial properties of the ultra-small size nanosilver, AgNPs@CEL could cause 5.3 and 5.4 log10 CFU/mL reduction against E. coli and S. aureus in 5 min. Meanwhile, AgNPs@CEL exhibited remarkable photothermal antibacterial performance, which caused 6.2 and 6.1 log10 CFU/mL reduction of E. coli and S. aureus, with NIR irradiation for 5 min. Furthermore, the composite films prepared by doping only 0.5 wt% AgNPs@CEL into ethyl cellose could achieve a bactericidal rate more than 99.99 %. This study provides a new insight into design of controlled particle size lignin-based antibacterial nanosilver materials in a sustainable manner and holds promise for applications in antibacterial fields.

Aqueous amine enables sustainable monosaccharide, monophenol, and pyridine base coproduction in lignocellulosic biorefineries.

Thought-out utilization of entire lignocellulose is of great importance to achieving sustainable and cost-effective biorefineries. However, there is a trade-off between efficient carbohydrate utilization and lignin-to-chemical conversion yield. Here, we fractionate corn stover into a carbohydrate fraction with high enzymatic digestibility and reactive lignin with satisfactory catalytic depolymerization activity using a mild high-solid process with aqueous diethylamine (DEA). During the fractionation, in situ amination of lignin achieves extensive delignification, effective lignin stabilization, and dramatically reduced nonproductive adsorption of cellulase on the substrate. Furthermore, by designing a tandem fractionation-hydrogenolysis strategy, the dissolved lignin is depolymerized and aminated simultaneously to co-produce monophenolics and pyridine bases. The process represents the viable scheme of transforming real lignin into pyridine bases in high yield, resulting from the reactions between cleaved lignin side chains and amines. This work opens a promising approach to the efficient valorization of lignocellulose.

Enhancing Pollutant Mineralization through Organic-Inorganic Defect-Transit Dual S-scheme with a Robust Internal Electric Field.

Achieving superior photomineralization of pollutants relies on a rational design of a dual S-scheme with a robust internal electric field (IEF). In this study, to tackle the low mineralization rate in type-II In2 O3 /In2 S3 (IO/IS) systems, an organic-inorganic dual S-scheme In2 O3 /PDI/In2 S3 (IO/PDI/IS) nanostructured photocatalyst is synthesized via a method combining solvent-induced self-assembly and electrostatic forces. Due to the unique energy band position and strong IEF, the photoinduced defect-transit dual S-scheme IO/PDI/IS facilitates the degradation of lignin and antibiotics. Notably, a promising mineralization rate of 80.9% for sodium lignosulfonate (SL) is achieved. The charge transport pathway of IO/PDI/IS are further validated through the analysis of in situ X-ray photoelectron spectroscopy (in situ XPS), density functional theory calculations, and radical trapping experiments. In-depth, two possible pathways for the photocatalytic degradation of lignin are proposed based on the intermediates monitored by liquid chromatography-mass spectrometry (LC-MS). This study presents a new strategy for the design of organic-inorganic dual S-scheme photocatalysts with a robust IEF for pollutant degradation.

H3K27 acetylation activated-PDLIM7 promotes castration-resistant prostate cancer progression by inducing O-Glycosylation of YAP1 protein.

Castration-resistant prostate cancer (CRPC) is a fatal disease that evolves from prostate cancer due to drug resistance after long-term androgen deprivation therapy. In this study, we aimed to find novel molecular targets for treating CRPC. Through peptidome, we screened out polypeptides dysregulated in the serum of CRPC patients. According to RT-qPCR analysis and cell viability detection, we chose PDZ and LIM Domain 7 (PDLIM7) as the research object. As demonstrated by loss-of-function assays, silencing of PDLIM7 could suppress CRPC cell proliferation, migration, and angiogenesis. Moreover, PDLIM7 knockdown enhanced the sensitivity of CRPC cells to docetaxel treatment. Subsequently, we found that CBP/p300 increases the H3K27ac level in the PDLIM7 promoter to activate PDLIM7. Mechanism experiments such as IP and western blot revealed that PDLIM7 interacted with YAP1 to induce O-Glycosylation of YAP1 and thus stabilize YAP1 protein. Rescue assays demonstrated that PDLIM7 promoted the malignant processes of CRPC cells through YAP1. Finally, an animal study validated that PDLIM7 aggravated tumor growth. In conclusion, our findings highlighted the oncogenic role of PDLIM7 upregulated by CBP/p300-induced H3K27ac enhancement in CRPC by stabilizing YAP1.

A novel twin-grasper assisted mucosal inverted closure technique for closing large artificial gastric mucosal defects.

BACKGROUND: Large artificial gastric mucosal defects are always left unclosed for natural healing due to technique difficulties in closure. This study aims to evaluate the feasibility and safety of a new Twin-grasper Assisted Mucosal Inverted Closure (TAMIC) technique in closing large artificial gastric mucosal defects. METHODS: Endoscopic submucosal dissection (ESD) was performed in fifteen pigs to create large gastric mucosal defects. The mucosal defects were then either left unclosed or closed with metallic clips using TAMIC technique. Successful closure rate and the wound outcomes were assessed. RESULTS: Two mucosal defects with size of about 4.0 cm were left unclosed and healed two months after surgery. Thirteen large gastric mucosal defects were created by ESD with a medium size of 5.9 cm and were successfully closed with the TAMIC technique (100%), even in a mucosal defect with a width up to 8.5 cm. The mean closure time was 59.0 min. Wounds in eight stomachs remained completely closed 1 week after surgery (61.5%), while closure in the other five stomachs had partial wound dehiscence (38.5%). Four weeks later, all the closed defects healed well and 61.5% of the wounds still remained completely closed during healing. There was no delayed perforation or bleeding after surgery. In addition, there was less granulation in the submucosal layer of the closed wound sites than those under natural healing. CONCLUSIONS: The present study suggests that TAMIC is feasible and safe in closing large artificial gastric mucosal defects and could improve mucosal recovery compared to natural healing process.

The Role of Vasodilator-stimulated Phosphoproteins in the Development of Malignant Tumors.

Vasodilator-stimulated phosphoprotein (VASP) is an actin-binding protein that includes three structural domains: Enabled/VASP homolog1 (EVH1), EVH2, and proline-rich (PRR). VASP plays an important role in various cellular behaviors related to cytoskeletal regulation. More importantly, VASP plays a key role in the progression of several malignant tumors and is associated with malignant cell proliferation, invasion, and metastasis. Here, we have summarized current studies on the impact of VASP on the development of several malignant tumors and their mechanisms. This study provides a new theoretical basis for clinical molecular diagnosis and molecular targeted therapy.

Full biomass-based multifunctional flocculant from lignin and cationic starch.

Flocculation is a common process for wastewater treatment. However, the most commonly used organic synthetic flocculants such as polyacrylamide are petroleum-based. In this work, biomass lignin was grafted with cationic starch to synthesize low-cost, green and fully biomass-based multifunctional flocculants. The cationic polyacrylamide was replaced by cheap industrial cationic starch. Hyperbranched multifunctional lignin-grafted cationic starch flocculant (CS-L) was successfully prepared via ring-opening reaction with epichlorohydrin. The mass content of lignin in the grafted product was between 16.6 % and 70.1 %. With the dosage of CS-L between 4.0 and 7.5 mg/l, the turbidity removal rate for 500 mg/l kaolin suspension reached more than 97 %. When the dosage of CS-L was 24 mg/l, the removal rate of 50 mg/l Cu2+ reached 85.7 %. Importantly, when the mixed solution of kaolin particles and Cu2+ was treated, the synchronous removal rates of kaolin and Cu2+ reached 90 % and 72 % respectively in the range of 8.0-12.0 mg/l flocculant addition. The synthesized lignin-grafted cationic starch flocculant showed an excellent multifunctional flocculation function.

Preparation, characterization, and adsorption performance of porous polyamine lignin microsphere.

In this study, a porous polyamine lignin microsphere (PPALM) was prepared through the inverse suspension polymerization combined with freeze-drying, during which sodium lignosulfonate and polyetheramine (PEA) were crosslinked with epichlorohydrin (ECH) as the cross-linker. By adjusting the amount of ECH and PEA, the optimized PPALM exhibited suitable crosslinking degree, ensuring a balance of framework flexibility and rigidity, thereby facilitating the formation of abundant and fine pores. PPALM demonstrated good mechanical properties comparable to commercial sulfonated polystyrene cationic resin, with a porosity of 61.12 % and an average pore size of 283.51 nm. The saturation adsorption capacity of PPALM for Pb2+ was measured to be 156.82 mg/g, and it remained above 120 mg/g after five cycles of regeneration. Particularly, the concentration of 50 mg/L Pb2+ solution could be reduced to 0.98 mg/L after flowing through the PPALM packed bed, indicating the great potential of PPALM for application in wastewater treatment.

"Rigid-Flexible" Anisotropic Biomass-Derived Aerogels with Superior Mechanical Properties for Oil Recovery and Thermal Insulation.

Aerogels with low density, high mechanical strength, and excellent elasticity have a wide potential for applications in wastewater treatment, thermal management, and sensors. However, the fabrication of such aerogels from biomass materials required complex preparation processes. Herein, a sustainable and facile strategy was reported to construct lignin/cellulose aerogels (LCMA) with three-dimensional interconnected structures by introducing homologous lignin with a polyphenyl propane structure as a structural enhancer through a top-down directional freezing approach, prompting a 2036% enhancement in compressive modulus and an 8-12-fold increase in oil absorption capacity. In addition, the hydrophobic aerogels with superelasticity were achieved by combining the aligned polygon-like structure and flexible silane chains, which exhibited remarkable compressional fatigue resistance and superhydrophobicity (WCA = 168°). Attributed to its unique pore design and surface morphology control, the prepared aerogel exhibited excellent performance in immiscible oil-water separation and water-in-oil emulsion separation. Due to the ultra-low density (8.3 mg·cm-3) as well as high porosity (98.87%), the obtained aerogel showed a low thermal conductivity (0.02565 ± 0.0024 W·m-1·K-1), demonstrating a potential in insulation applications. The synthetic strategy and sustainability concept presented in this work could provide guidance for the preparation of advanced biomass-based aerogels with unique properties for a wide range of applications.

Unveiling the role of long-range and short-range forces in the non-productive adsorption between lignin and cellulases at different temperatures.

Quantitatively understanding of interaction mechanism between lignin and cellulases is essential for the efficient improvement of lignocellulose enzymatic hydrolysis. However, the individual contribution of multiple forces between lignin and cellulases to the non-productive adsorption of enzymes still remains deeply ambiguous, especially in situations of near enzymatic hydrolysis temperatures. Herein, atomic force microscopy (AFM) and computational simulations were utilized to quantitatively analyze the intermolecular forces between lignin and enzyme at 25 °C and 40 °C. Our results unveiled that an increase in temperature obviously improved adsorption capacity and total intermolecular forces between lignin and cellulases. This positive relationship mainly comes from the increase in the decay length of hydrophobic forces for lignin-cellulases when temperature increases. Different from the hydrophobic interaction which provides long-range part of attractions, van der Waals forces dominate the intermolecular force only at approaches < 2 nm. On the other hand, electrostatic forces exhibited repulsive effects, and its intensity and distance were limited due to the low surface potential of cellulases. Short-range forces including hydrogen bonding (main) and π-π stacking (minor) stabilize the non-specific binding of enzymes to lignin, but increasing temperature reduces hydrogen bond number. Therefore, the relative contribution of long-range forces increased markedly at higher temperatures, which benefits protein capture and brings lignin and cellulase close together. Finally, the structure-activity relationships between lignin physicochemical properties and its inhibitory effect to enzymes indicated that hydrophobic interactions, hydrogen bonding, and steric effects drive the final adsorption capacity and glucose yields. This work provides quantitative and basic insights into the mechanism of lignin-cellulase interfacial interactions and guides design of saccharification enhancement approaches.

Preparation of a new gel-type lignin-based cationic adsorption resin for efficient removal of Ca2+ from aqueous solutions.

Presently, most studies on modified lignin focused on the adsorption to heavy metal cations, but rarely to Ca2+ in hard water. Therefore, this work prepared a new gel-type lignin-based cationic adsorption resin (E-LSAF) through the crosslinking and curing of alkali lignin grafted by sodium sulfite sulfonated acetone to remove Ca2+ in water. Under the determined optimum synthesis conditions, E-LSAF with a highest sulfonic group content of 1.99 mmol/g was obtained. Structural and physicochemical measuring results showed E-LSAF was a gel-type resin, owning strong hydrophilicity, high mechanical strength, excellent thermal stability and acid-alkaline resistance. Adsorption results indicated the adsorption of E-LSAF to Ca2+ was well-fitted by Langmuir model, and the maximum adsorption capacity reached 45.8 mg/g. Pseudo-second-order model can describe this adsorption process well, suggesting it a chemisorption process. Dynamic column adsorption results showed E-LSAF could transform hard water into soft or even very soft water. The regeneration efficiency still maintained 80 % after 5 cycles. The adsorption mechanism was attributed to electrostatic attraction, ion exchange and complexation. This work provided a high-performance lignin-based cationic adsorption material with high adsorption capacity to Ca2+ and excellent acid-alkaline resistance, which filled the research gap of using modified sulfonated lignin to remove Ca2+ from water.

Boosting capacitive performance of N, S co-doped hierarchical porous lignin-derived carbon via self-assembly assisted template-coupled activation.

Heteroatom-doped porous carbon materials show promise for use as supercapacitor electrodes, but the tradeoff between surface area and the heteroatom dopant levels limits the supercapacitive performance. Here, we modulated the pore structure and surface dopants of N, S co-doped hierarchical porous lignin-derived carbon (NS-HPLC-K) via self-assembly assisted template-coupled activation. The ingenious assembly of lignin micelles and sulfomethylated melamine into a magnesium carbonate basic template greatly promoted the KOH activation process, which endowed the NS-HPLC-K with uniform distributions of activated N/S dopants and highly accessible nanosized pores. The optimized NS-HPLC-K exhibited a three-dimensional hierarchically porous architecture composed of wrinkled nanosheets and a high specific surface area of 2538.3 ± 9.5 m2/g with a rational N content of 3.19 ± 0.01 at.%, which boosted the electrical double-layer capacitance and pseudocapacitance. Consequently, the NS-HPLC-K supercapacitor electrode delivered a superior gravimetric capacitance of 393 F/g at 0.5 A/g. Furthermore, the assembled coin-type supercapacitor showed good energy-power characteristics and cycling stability. This work provides a novel idea for designing eco-friendly porous carbons for use in advanced supercapacitors.

Functionalized Regulation of Metal Defects in ln2S3 of p-n Homojunctions.

The introduction of metal vacancies into n-type semiconductors could efficiently construct intimate contact interface p-n homojunctions to accelerate the separation of photogenerated carriers. In this work, a cationic surfactant occupancy method was developed to synthesize an indium-vacancy (VIn)-enriched p-n amorphous/crystal homojunction of indium sulfide (A/C-IS) for sodium lignosulfonate (SL) degradation. The amount of VIn in the A/C-IS could be regulated by varying the content of added cetyltrimethylammonium bromide (CTAB). Meanwhile, the steric hindrance of CTAB produced mesopores and macropores, providing transfer channels for SL. The degradation rates of A/C-IS to SL were 8.3 and 20.9 times higher than those of crystalline In2S3 and commercial photocatalyst (P25), respectively. The presence of unsaturated dangling bonds formed by VIn reduced the formation energy of superoxide radicals (•O2-). In addition, the inner electric field between the intimate contact interface p-n A/C-IS promoted the migration of electron-hole pairs. A reasonable degradation pathway of SL by A/C-IS was proposed based on the above mechanism. Moreover, the proposed method could also be applicable for the preparation of p-n homojunctions with metal vacancies from other sulfides.

Construction of Macroporous ß-Glucosidase@MOFs by a Metal Competitive Coordination and Oxidation Strategy for Efficient Cellulose Conversion at 120 °C.

Metal-organic frameworks (MOFs) have become promising accommodation for enzyme immobilization in recent years. However, the microporous nature of MOFs affects the accessibility of large molecules, resulting in a significant decline in biocatalysis efficiency. Herein, a novel strategy is reported to construct macroporous MOFs by metal competitive coordination and oxidation with induced defect structure using a transition metal (Fe2+) as a functional site. The feasibility of in situ encapsulating ß-glucosidase (ß-G) within the developed macroporous MOFs endows an enzyme complex (ß-G@MOF-Fe) with remarkably enhanced synergistic catalysis ability. The 24 h hydrolysis rate of ß-G@MOF-Fe (with respect to cellobiose) is as high as approximately 99.8%, almost 32.2 times that of free ß-G (3.1%). Especially, the macromolecular cellulose conversion rate of ß-G@MOF-Fe reached 90% at 64 h, while that of ß-G@MOFs (most micropores) was only 50%. This improvement resulting from the expansion of pores (significantly increased at 50-100 nm) can provide enough space for the hosted biomacromolecules and accelerate the diffusion rate of reactants. Furthermore, unexpectedly, the constructed ß-G@MOF-Fe showed a superior heat resistance of up to 120 °C, attributing to the new strong coordination bond (Fe2+-N) formation through the metal competitive coordination. Therefore, this study offers new insights to solve the problem of the high-temperature macromolecular substrate encountered in the actual reaction.