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The cathode interlayer is crucial for the development of organic solar cells (OSCs), but the research on simple and efficient interlayer materials is lagging behind. Here, a donor-acceptor (D-A) typed selenophene-fused perylene diimide (PDI) derivative (SePDI3) is developed as cathode interlayer material (CIM) for OSCs, and a non-fused PDI derivative (PDI3) is used as the control CIM for comparison. Compared to PDI3, SePDI3 shows a stronger self-doping effect and better crystallinity, resulting in better charge transport ability. Furthermore, the interaction between SePDI3 and L8-BO can form an efficient extraction channel, leading to superior charge extraction behavior. Finally, benefitting from significantly enhanced charge transport and extraction capacity, the SePDI3-based device displays a champion PCE of 19.04 % with an ultrahigh fill factor of 81.65 % for binary OSCs based on PM6 : L8-BO active layer, which is one of the top efficiencies reported to date in binary OSCs based novel CIMs. Our work prescribes a facile and effective fusion strategy to develop high-efficiency CIMs for OSCs.
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BACKGROUND: Myocardial metabolism is closely related to functional changes after myocardial infarction (MI). OBJECTIVE: This study aimed to present an integrative examination of human ischemic cardiomyopathy. METHODS: We used both GSE121893 single-cell suspension sequencing and GSE19303 transcription microarray data sets from the GEO database, along with a murine MI model for full-spectrum metabolite detection. Through a systematic investigation that involved differential metabolite identification and functional enrichment analysis, we shed light on the pivotal role of energy metabolism dysregulation in the progression of MI. RESULTS: Our findings revealed an association between the core regulatory genes CDKN1A, FOS, ITGB4, and MAP2K1 and the underlying pathophysiology of the disease. These genes are identified as critical elements in the complex landscape of myocardial ischemic disorder, highlighting novel insights into therapeutic targets and the intricate biological mechanisms involved. CONCLUSION: This analysis provides a framework for future research on the metabolic alterations associated with MI.
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Lysosome-targeted photodynamic therapy, which enhances reactive oxygen species (ROS)-responsive tumor cell death, has emerged as a promising strategy for cancer treatment. Herein, a uridine (dU)-modified Ru(II) complex (RdU) was synthesized by click chemistry. It was found that RdU exhibits impressive photo-induced inhibition against the growth of triple-negative breast cancer (TNBC) cells in normoxic and hypoxic microenvironments through ROS production. It was further revealed that RdU induces ferroptosis of MDA-MB-231 cells under light irradiation (650 nm, 300 mW/cm2). Additional experiments showed that RdU binds to lysosomal integral membrane protein 2 (LIMP-2), which was confirmed by the fact that RdU selectively localizes in the lysosomes of MDA-MB-231 cells and significantly augments the levels of LIMP-2. Molecular docking simulations and an isothermal titration calorimetry assay also showed that RdU has a high affinity to LIMP-2. Finally, in vivo studies in tumor-bearing (MDA-MB-231 cells) nude mice showed that RdU exerts promising photodynamic therapeutic effects on TNBC tumors. In summary, the uridine-modified Ru(II) complex has been developed as a potential LIMP-2 targeting agent for TNBC treatment through enhancing ROS production and promoting ferroptosis.
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All-polymer solar cells (all-PSCs) have been regarded as one of the most promising candidates for commercial applications owing to their outstanding advantages such as mechanical flexibility, light weight and stable film morphology. However, compared to large amount of new-emerging excellent polymer acceptors, the development of high-performance polymer donor lags behind. Herein, a new D-π-A type polymer donor, namely QQ1, was developed based on dithienoquinoxalineimide (DTQI) as the A unit, benzodithiophene with thiophene-conjugated side chains (BDTT) as the D unit, and alkyl-thiophene as the π-bridge, respectively. QQ1 not only possesses a strong dipole moment, but also shows a wide band gap of 1.80â eV and a deep HOMO energy level of -5.47â eV, even without halogen substituents that are commonly indispensable for high-performance polymer donors. When blended with a classic polymer acceptor PY-IT, the QQ1-based all-PSC delivers an outstanding PCE of 18.81 %. After the introduction of F-BTA3 as the third component, a record PCE of 19.20 % was obtained, the highest value reported so far for all-PSCs. The impressive photovoltaic performance originates from broad absorption range, reduced energy loss, and compact π-π stacking. These results provide new insight in the rational design of novel nonhalogenated polymer donors for further development of all-PSCs.
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The A2 -A1 -D-A1 -A2 -type molecules consist of one electron-donating (D) core flanked by two electron-accepting units (A1 and A2 ) and have emerged as an essential branch of nonfullerene acceptors (NFAs). These molecules generally possess higher molecular energy levels and wider optical bandgaps compared with those of the classic A-D-A- and A-DA'D-A-type NFAs, owing to the attenuated intramolecular charge transfer effect. These characteristics make them compelling choices for the fabrication of high-voltage organic photovoltaics (OPVs), ternary OPVs, and indoor OPVs. Herein, the recent progress in the A2 -A1 -D-A1 -A2 -type NFAs are reviewed, including the molecular engineering, structure-property relationships, voltage loss (Vloss ), device stability, and photovoltaic performance of binary, ternary, and indoor OPVs. Finally, the challenges and provided prospects are discussed for the further development of this type of NFAs.
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A third component featuring a planar backbone structure similar to the binary host molecule has been the preferred ingredient for improving the photovoltaic performance of ternary organic solar cells (OSCs). In this work, we explored a new avenue that introduces 3D-structured molecules as guest acceptors. Spirobifluorene (SF) is chosen as the core to combine with three different terminal-modified (rhodanine, thiazolidinedione, and dicyano-substituted rhodanine) benzotriazole (BTA) units, affording three four-arm molecules, SF-BTA1, SF-BTA2, and SF-BTA3, respectively. After adding these three materials to the classical system PM6 : Y6, the resulting ternary devices obtained ultra-high power-conversion efficiencies (PCEs) of 19.1 %, 18.7 %, and 18.8 %, respectively, compared with the binary OSCs (PCE=17.4 %). SF-BTA1-3 can work as energy donors to increase charge generation via energy transfer. In addition, the charge transfer between PM6 and SF-BTA1-3 also acts to enhance charge generation. Introducing SF-BTA1-3 could form acceptor alloys to modify the molecular energy level and inhibit the self-aggregation of Y6, thereby reducing energy loss and balancing charge transport. Our success in 3D multi-arm materials as the third component shows good universality and brings a new perspective. The further functional development of multi-arm materials could make OSCs more stable and efficient.
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Dithieno[3',2':3,4;2",3":5,6]benzo[1,2-c][1,2,5]thiadiazole (DTBT) is a newly emerging building block to construct effective photovoltaic polymers. Organic solar cells (OSCs) based on DTBT-based polymers have realized power conversion efficiency (PCEs) over 18%, despite their relatively low open-circuit voltage (VOC ) of 0.8-0.95 V. To extend the application of DTBT-based polymers in high-voltage OSCs, herein, D18-Cl and PE55 are used to combine with a wide-bandgap non-fullerene acceptor (NFA), BTA3, and achieve ultrahigh VOC of 1.30 and 1.28 V, respectively. Compared with D18-Cl based on tricyclic benzodithiophene (BDT) segment, PE55 containing the pentacyclic dithienobenzodithiophene (DTBDT) unit possesses better hole mobility, higher charge-transfer efficiency, and more desirable phase separation. Hence, PE55:BTA3 blend exhibits a higher efficiency of 9.36% than that of D18-Cl: BTA3 combination (6.30%), which is one of the highest values for OSCs at ≈1.3 V VOC . This work attests that DTBT-based p-type polymers are ideal for the application in high-voltage OSCs.
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Polímeros , TiadiazóisRESUMO
BACKGROUND: The crosstalk of purine biosynthesis and metabolism exists to balance the cell energy production, proliferation, survival and cytoplasmic environment stability, but disorganized mechanics of with respect to developing heart failure (HF) is currently unknown. METHODS: We conducted a multi-omics wide analysis, including microarray-based transcriptomes, and full spectrum metabolomics with respect to chronic HF. Based on expression profiling by array, we applied a bioinformatics platform of quantifiable metabolic pathway changes based on gene set enrichment analysis (GSEA), gene set variation analysis (GSVA), Shapley Additive Explanations (SHAP), and Xtreme Gradient Boosting (XGBoost) algorithms to comprehensively analyze the dynamic changes of metabolic pathways and circular network in the HF development. Additionally, left ventricular tissue from patients undergoing myocardial biopsy and transplantation were collected to perform the protein and full spectrum metabolic mass spectrometry. RESULTS: Systematic bioinformatics analysis showed the purine metabolism reprogramming was significantly detected in dilated cardiomyopathy. In addition, this result was also demonstrated in metabolomic mass spectrometry. And the differentially expressed metabolites analysis showing the guanine, urea, and xanthine were significantly detected. Hub markers, includes IMPDH1, ENTPD2, AK7, AK2, and CANT1, also significantly identified based on XGBoost, SHAP model and PPI network. CONCLUSION: The crosstalk in the reactions involved in purine metabolism may involving in DCM metabolism reprogramming, and as coregulators of development of HF, which may identify as potential therapeutic targets. And the markers of IMPDH1, ENTPD2, AK7, AK2, and CANT1, and metabolites involved in purine metabolism shown an important role.
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Cardiomiopatia Dilatada , Insuficiência Cardíaca , Humanos , Cardiomiopatia Dilatada/genética , Redes e Vias Metabólicas , Metabolômica/métodos , Insuficiência Cardíaca/genética , Biomarcadores , PurinasRESUMO
The molecular design of a wide-bandgap polymer donor is critical to achieve high-performance organic photovoltaic devices. Herein, a new dibenzo-fused quinoxalineimide (BPQI) is successfully synthesized as an electron-deficient building block to construct donor-acceptor (D-A)-type polymers, namely P(BPQI-BDT) and P(BPQI-BDTT), using benzodithiophene and its derivative, which bears different side chains, as the copolymerization units. These two polymers are used as a donor, and the narrow bandgap (2,20-((2Z,20Z)-((12,13-bis(2-ethylhexyl)-3,9-diundecyl-12,13-dihydro-[1,2,5]thiadiazolo [3,4-e]thieno[2,â³30':4',50]thieno[20,30:4,5]pyrrolo[3,2g]thieno[20,30:4,5]thieno[3,2-b]indole-2,10 diyl)bis(methanylylidene))bis(5,6-difluoro-3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalononitrile) Y6 is used as an acceptor to fabricate bulk heterojunction polymer solar cell devices. Y6, as a non-fullerene receptor (NFA), has excellent electrochemical and optical properties, as well as a high efficiency of over 18%. The device, based on P(BPQI-BDTT):Y6, showed power conversion efficiencies (PCEs) of 6.31% with a JSC of 17.09 mA cm-2, an open-circuit voltage (VOC) of 0.82 V, and an FF of 44.78%. This study demonstrates that dibenzo-fused quinoxalineimide is a promising building block for developing wide-bandgap polymer donors.
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Owing to the advantages of adjustable bandgap, low-cost fabrication and superior photovoltaic performance, wide-bandgap (WBG) perovskite solar cells (PSCs) are considered as the promising top-cell for multi-junction solar cells. At the same time, WBG PSCs have also shown great potential for indoor photovoltaic applications. To further improve the performance of WBG PSCs, in this work, we fabricated efficient WBG PSCs via introducing cesium formate (CsFa) as the Cs precursor. Due to the HCOO·Pb+ and HCOOH·Cs+ complex formation and HCOOH volatilization accompanying the crystallization process, the crystallization of the perovskite using the CsFa precursor (CsFa-perovskite) is promoted. Compared to the perovskite prepared using the CsBr precursor (CsBr-perovskite), the WBG CsFa-perovskite shows better perovskite crystallization, reduced trap-state density, and better phase stability under light illumination. Finally, the 1.63 eV WBG PSCs based on the CsFa-perovskite achieve a significant PCE of 20.01% under one sun illumination (AM 1.5G, 100 mW cm-2), which is higher than that of PSCs based on the CsBr-perovskite (18.27%). Moreover, the PCE of CsFa-perovskite PSCs also under indoor warm-white 2700 K LED light illumination (1000 lux) is as high as 38.52%. Our results demonstrate that CsFa as the Cs precursor is a promising candidate to promote the device performance of WBG PSCs.
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PTB7-Th is considered one of the most classic donor polymers for organic photovoltaic (OPV) cells. However, the power conversion efficiency (PCE) of PTB7-Th-based OPV is lagging behind that of other promising polymers mainly because of the relatively low open-circuit voltage (VOC). To increase the VOC and PCE of PTB7-Th-based OPV, the development of nonfullerene acceptors (NFAs) and studies of structure-property-performance relationship are vital. Here, three A2-A1-D-A1-A2-type acceptors, namely BTA45, F-BTA45, and F-BTA5, were developed by fluorination on the benzotriazole (BTA) unit and regulating alkoxy or alkyl phenyl side chains. Compared with BTA45, light absorption and π-π packing can be simultaneously improved for the two fluorinated BTA acceptors, resulting in an increased JSC and FF. Moreover, the F-BTA5-based blend film exhibits better phase separation morphology and electron transport than those of BTA45 and F-BTA45, which contribute to a device efficiency of 10.36% with a VOC of 1.03 V. In addition, the ΔE2 values of the three blends are less than 0.15 eV, together with their moderate ΔE3, efficiently decreasing their energy loss. These results highlight the importance of fluorination and side chain engineering for NFAs to boost the VOC and PCE for low-band gap photovoltaic polymers.
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We evaluated an independently developed novel percutaneous implantable left ventricular assist device for resuscitation in a pig model of ventricular fibrillation cardiac arrest. The model was established in 10 domestic pigs by blocking the anterior descending coronary artery with a balloon after anesthesia. With ventilator-assisted ventilation, the independently developed percutaneous implantable left ventricular assist device was inserted via the femoral artery to assist circulation. According to whether effective circulatory support was achieved, the pigs were randomly divided into an experimental group and a control group. The experimental group was subjected to insertion of the assist device and received continuous circulatory support. The control group underwent insertion of the assist device; however, it did not start it within 15 minutes. For all animals, if successful rescue was achieved (sinus rhythm restoration within 15 minutes and maintenance for over 5 minutes), circulatory support was stopped, and the arterial blockage was removed. If sinus rhythm was not restored within 15 minutes, electric defibrillation, adrenaline injection, and removal of the arterial blockage were performed, and circulatory support was provided until sinus rhythm recovered. A determination of failed rescue was made when sinus rhythm was not restored after 1 hour. All successfully rescued animals were fed for 1 week. There were no significant differences in baseline data between the groups. All animals underwent successful novel left ventricular assist device implantation through the femoral artery. The rescue rate was significantly higher in the experimental group than in the control group (80% vs. 0%, [Formula: see text]). All successfully rescued animals survived after 1 week of feeding, and no eating or movement abnormalities were observed. We conclude that this independently developed percutaneous implantable left ventricular assist device can be conveniently and rapidly implanted through the femoral artery and can maintain basic circulatory perfusion during resuscitation in an animal model of cardiac arrest.
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Parada Cardíaca , Coração Auxiliar , Animais , Modelos Animais de Doenças , Parada Cardíaca/terapia , Ressuscitação , Suínos , Fibrilação Ventricular/terapiaRESUMO
Currently, effective drugs for triple-negative breast cancer (TNBC) are lacking in clinics. c-myc is one of the core members during TNBC tumorigenesis, and G-rich sequences in the promoter region can form a G-quadruplex conformation, indicating that the c-myc inhibitor is a possible strategy to fight cancer. Herein, a series of chiral ruthenium(II) complexes ([Ru(bpy)2(DPPZ-R)](ClO4)2, Λ/Δ-1: R = -H, Λ/Δ-2: R = -Br, Λ/Δ-3: R = -C≡C(C6H4)NH2) were researched based on their interaction with c-myc G-quadruplex DNA. Λ-3 and Δ-3 show high affinity and stability to decrease their replication. Additional studies showed that Λ-3 and Δ-3 exhibit higher inhibition against different tumor cells than other molecules. Δ-3 decreases the viability of MDA-MB-231 cells with an IC50 of 25.51 µM, which is comparable with that of cisplatin, with an IC50 of 25.9 µM. Moreover, Δ-3 exhibits acceptable cytotoxic activity against MDA-MB-231 cells in a zebrafish xenograft breast cancer model. Further studies suggested that Δ-3 decreases the viability of MDA-MB-231 cells predominantly through DNA-damage-mediated apoptosis, which may be because Δ-3 can induce DNA damage. In summary, the results indicate that Ru(II) complexes containing alkinyl groups can be developed as c-myc G-quadruplex DNA binders to block TNBC progression.
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Antineoplásicos , Complexos de Coordenação , Quadruplex G , Rutênio , Neoplasias de Mama Triplo Negativas , Animais , Humanos , Neoplasias de Mama Triplo Negativas/tratamento farmacológico , Neoplasias de Mama Triplo Negativas/genética , Peixe-Zebra , Antineoplásicos/farmacologia , Dano ao DNA , DNA , Rutênio/farmacologia , Complexos de Coordenação/farmacologiaRESUMO
Polymerizations of perfluorinated vinyl ethers (PFVEs) provide an important category of fluoropolymers that have received considerable interests in applications. In this work, we report the development of an organocatalyzed controlled radical alternating terpolymerization of PFVEs and vinyl ethers (VEs) under visible-light irradiation. This method not only enables the synthesis of a broad scope of fluorinated terpolymers of low dispersities and high chain-end fidelity, facilitating tuning the chemical compositions by rationally choosing the type and/or ratio of comonomers, but also allows temporal control of chain-growth, as well as the preparation of a variety of novel fluorinated block copolymers. To showcase the versatility of this method, fluorinated alternating terpolymers have been synthesized and customized to simultaneously display a variety of desirable properties for solid polymer electrolyte design, creating new opportunities in high-performance energy storage devices.
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Thin solid polymer electrolytes (SPEs) with good processability, improved room-temperature ionic conductivity, and better interfacial compatibility are urgently needed to develop solid-state batteries without safety and leakage issues. In-built electrolyte polymerization has emerged as a novel and effective platform to obtain such electrolytes. However, existing in-built methods usually involve heat, UV, γ irradiation, and so forth to initiate the polymerization and often require the addition of solvents to avoid the concentrated active propagating species, which inevitably afford solvent residues that persist in the electrolyte matrix, leading to complex SPE preparation processes, safety hazards, and side reactions with the electrodes. Herein, a simple solvent-free preparation of the poly(mPEGAA)-based electrolyte film was achieved via the photo-controlled radical polymerization under visible light irradiation via an in-built manner, which resulted in 99% monomer conversion within 5 min to obtain the polymer electrolytes with a controlled molecular weight distribution. Thanks to the mild and green conditions, a thin, solvent-free, and cross-linked SPE electrolyte film was obtained efficiently yet in a well-regulated manner, which gave rise to good interfacial compatibility and an improved room-temperature ionic conductivity of 1.5 × 10-4 S cm-1 at 25 °C. As-prepared solid-state LiFePO4|Li batteries based on the in-built thin SPE exhibited a high discharge areal capacity of 1.7 mA h cm-2 (164.6 mA h g-1) at an ambient temperature. Furthermore, the system displayed lithium dendrite suppression behavior and good long-term charge-discharge cycling in the Li symmetric battery for over 270 h, representing enhanced stability and capacities compared with ex-built systems.
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In this study, a bio-based soy protein adhesive derived from environmentally friendly and renewable enzymatic hydrolysis lignin (EHL), epoxidized soybean oil (ESO), and soy protein isolate (SPI), was successfully prepared. A novel biopolymer (EHL-ESO), as a multifunctional crosslinker, was firstly synthesized from modified EHL and ESO, and then crosslinked with soy protein isolate to obtain a bio-based soy protein adhesive. The structure, thermal properties, and adhesion performance of the obtained soy protein adhesives were determined by Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), scanning electron microscopy (SEM) and wet shear strength. The maximum degradation temperature of SPI/EHL-ESO adhesives (332-343 °C) was higher than that of the pristine SPI adhesive (302 °C). Moreover, plywood bonded by the modified adhesive reached a maximum wet shear strength value of 1.07 MPa, a significant increase of 101.8% from the plywood bonded by pristine SPI adhesive. The enhancements in the thermal stability and wet shear strength were attributed to the formation of a dense crosslinking network structure. This work not only highlights the potential to replace petroleum-based polymers, but also presents a green approach to fabricate fully bio-based soy protein adhesive for preparing all-biomass wood composite materials.
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Charge extraction layers with excellent charge extraction capability are essential for achieving high photovoltaic performance in cells. In this work, a hole extraction layer (HEL) is developed by doping conductive polymer TFB into CuSCN (CuSCN:TFB(X)), which exhibits good light transparency and high affinity for the light absorber. Compared to the reference cell, the CuSCN:TFB(X) HEL-based cells show impressive enhancement owing to the increased exciton dissociation and charge extraction processes and weak recombination losses. Furthermore, matched work function, better interface contact, and appropriate domain size also contribute to the enhanced power conversion efficiency. As a consequence, the highest conversion efficiency of 15.28% is observed in a cell based on the PM6:Y6 blend film and CuSCN:TFB(1.0%) HEL, which is >16% higher than the efficiency of 13.13% in a cell with CuSCN HEL.
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A nanoporous all-solid-state MOF-laden polymer electrolyte that is simply mediated by an electronic effect shows remarkably high lithium electrodeposition stability of hundreds of charge-discharge cycles and over 1500 operating hours, while maintaining a very small voltage polarization. This result is a significant improvement relative to conventional PEO and, when used in an all-solid-state battery (ASSB), this electrolyte enabled enhanced cycle life. This new all-solid-state electrolyte shows a promising rational design for the emerging microporous polymeric materials as novel SPEs in ASSBs.
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Per- and polyfluorinated alkyl substances (PFASs) are broadly used as surfactants and water/oil repellents for many decades. However, they are toxic, environmental persistence, and widely detected in water sources. In this work, we developed a fluorous-core nanoparticle-embedded hydrogel (FCH) synthesized by the metal-free tandem photocontrolled radical polymerization under visible-light irradiation. With the FCH material, the scope of absorbable PFASs has been expanded to neutral, anionic, cationic and zwitterionic PFASs with the same adsorbent for the first time. The fluorous nanoparticles exhibited strong and selective affinity toward PFASs without being dramatically influenced by pH levels and background ions, enabling efficient removing of PFASs at high to environmentally relevant concentrations (10 mg/L to 1 µg/L). Furthermore, the FCH network has shown good mechanical performance, facilitating the separation, regeneration, and recycling of adsorbent for multiple runs. These results demonstrate the promise of the FCH material for PFASs separation and adsorbent recycling toward sustainable environment.
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A simple and useful approach by using non-toxic and water-soluble raw material to improve the bonding properties of soy protein adhesive has attracted much attention recently. The objective of this research was to provide a simple and environmentally friendly approach for preparing a high adhesion performance soy protein adhesive in aqueous solution by using waterborne-epoxy resin, soy protein and water-soluble polyacrylamide (PAM). The chemical structure and curing characteristics, as well as the initial viscosity and adhesion performance of the resulted soy protein adhesive were characterized by 1H nuclear magnetic resonance (1H-NMR), differential scanning calorimetry (DSC), a rotary viscosity meter and a plywood panel test. The 1H-NMR analysis results confirmed that epoxy resin was successfully crosslinked with the -NH2 groups of the soy protein molecule to form a water-resistance network structure, and the resulting adhesive contains active epoxy groups. It was found that the addition of PAM can decrease the apparent viscosity, lower curing temperature, and enhancing the wet shear strength of soy protein adhesives effectively, which were capable of facilitating their application as wood adhesives. The resulting soy protein adhesive containing 4% epoxy resin and 0.05% PAM dosage had a reasonable viscosity and lower cure temperature, and showed good water resistance and wet shear strength, which met the requirement for interior use plywood of the Chinese Industrial Standard. These results suggested that waterborne-epoxy resin can be used to prepare high-performance environmentally friendly soy protein adhesives, which might provide a feasible methodology to prepare bio-adhesive adhesives for plywood industrial applications.