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Induced Proximity Approach Enables the Recombinant Production of Polyphosphorylated Silk Proteins with Improved Adhesiveness 诱导接近法使重组多磷酸化丝蛋白的生产具有更好的粘附性。
IF 5.4 2区 化学 Q1 BIOCHEMISTRY & MOLECULAR BIOLOGY Pub Date : 2025-12-08 DOI: 10.1021/acs.biomac.5c01431
Nea B. Möttönen , Ruxia Fan , Stefania Aspholm-Tsironi , Salla Keskitalo , Antti Tuhkala , Markku Varjosalo , A. Sesilja Aranko
Phosphorylation is considered to play a role in many of the functional properties of silk proteins, affecting their solubility, environmental adaptability, adhesion, and biocompatibility. However, investigating these effects has been hampered by the difficulty of isolating phosphorylated proteins from natural sources and the limitations of the current in vitro phosphorylation techniques. Here, we present a novel in vivo phosphorylation strategy for recombinant silk proteins in Escherichia coli, utilizing an engineered SpyCatcher/SpyTag system to induce proximity between the target protein and kinase. This scaffolding approach enhances kinase specificity and minimizes off-target effects, increasing the phosphorylation efficiency while preserving cell viability. We demonstrate the applicability of this system to both dragline and aggregate spider silks. Furthermore, we show that polyphosphorylation enhanced the adhesive properties of silk proteins. This modular and tunable strategy provides a powerful platform for producing polyphosphorylated fibrous proteins, offering broad implications for biomaterial design and functional protein engineering.
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磷酸化被认为在丝蛋白的许多功能特性中起作用,影响它们的溶解度、环境适应性、粘附性和生物相容性。然而,由于难以从天然来源分离磷酸化蛋白和目前体外磷酸化技术的局限性,研究这些影响受到阻碍。在这里,我们提出了一种新的在大肠杆菌中重组丝蛋白的体内磷酸化策略,利用一个工程的SpyCatcher/SpyTag系统诱导目标蛋白和激酶之间的接近。这种支架方法增强了激酶特异性,最大限度地减少了脱靶效应,在保持细胞活力的同时提高了磷酸化效率。我们演示了该系统对拖曳蛛丝和聚合蛛丝的适用性。此外,我们发现多磷酸化增强了丝蛋白的粘附性能。这种模块化和可调的策略为生产多磷酸化纤维蛋白提供了一个强大的平台,为生物材料设计和功能蛋白工程提供了广泛的意义。
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引用次数: 0
Self-Assembled Zwitterionic Lignin-Induced Joint Enhancement of Mechanics and Adhesion in High-Performance Hydrogels for Flexible Strain Sensors 自组装两性离子木质素诱导的柔性应变传感器高性能水凝胶的力学和粘附增强。
IF 5.4 2区 化学 Q1 BIOCHEMISTRY & MOLECULAR BIOLOGY Pub Date : 2025-12-08 DOI: 10.1021/acs.biomac.5c01574
Dawei Fang, Jiangping Bian, Yutong Xiang, Yu Wang, Tonglei Zhu, Ying Kang
The urgent demand for stable and accurate sensors emphasizes the importance of high mechanical and adhesion properties in conductive hydrogels. However, it remains challenging to concurrently enhance these two properties due to the inherent contradiction between internal cohesion and external adhesion. Here, lignin, an underutilized natural resource, is proposed to conquer the design difficulty described above by zwitterionization. Upon π–π aggregation, electronegative lignin readily self-assembles into zwitterionic lignin with a benzyltrimethylammonium cation. The zwitterionic lignin can simultaneously promote supramolecular interactions among lignin, polymer chains (poly­(acrylic acid) and gelatin), and adhesive substrates. Hence, the internal cross-linking and external adhesion are enhanced synchronously. Notably, the hydrogel demonstrates a remarkable true stress of 2.34 MPa at a strain of 1597.1%, and the peak adhesion strength of the hydrogel is achieved at 40.87 kPa. By valorizing waste lignin, this work opens up a new path to overcome the inherent design contradiction for high-performance hydrogels in the future.
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对稳定和精确传感器的迫切需求强调了导电水凝胶中高机械和粘附性能的重要性。然而,由于内部粘接和外部粘接之间的内在矛盾,同时增强这两种性能仍然具有挑战性。在这里,木质素,一种未充分利用的自然资源,被提出克服上述设计困难的两性电离。通过π-π聚集,电负性木质素很容易自组装成带有苯三甲基铵阳离子的两性离子木质素。两性离子木质素可以同时促进木质素、聚合物链(聚丙烯酸和明胶)和粘附底物之间的超分子相互作用。因此,内部交联和外部粘附同步增强。值得注意的是,在1597.1%的应变下,水凝胶的真应力为2.34 MPa,水凝胶的最大粘附强度为40.87 kPa。通过对废木质素的活化,为克服未来高性能水凝胶固有的设计矛盾开辟了一条新的途径。
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引用次数: 0
Extracellular Matrix Microstructures Directly Regulate Glutathione Bioavailability in Human Hepatocytes 细胞外基质微结构直接调节人肝细胞中谷胱甘肽的生物利用度。
IF 5.4 2区 化学 Q1 BIOCHEMISTRY & MOLECULAR BIOLOGY Pub Date : 2025-12-08 DOI: 10.1021/acs.biomac.5c01269
John A. Terrell, Chengpeng Chen
Recent works in mechanobiology have investigated overarching changes in cell behavior in response to extracellular matrix (ECM) stiffness. Nonetheless, little is known about how key metabolic pathways and critical metabolites are regulated by the ECM microstructures. Glutathione, a tripeptide predominantly synthesized in the liver, is a critical molecule used for the metabolism of certain xenobiotics and the reduction of oxidative species. Here, we report that the ECM microstructures can directly regulate the glutathione bioavailability and synthesis. By preparing a fibrous scaffold to mimic healthy native liver ECM and a flat substrate mimicking severe fibrotic conditions with the same surface chemistry, we found that the fibrous ECM upregulated glutathione levels in hepatocytes with enhanced antioxidation capacity. Mechanistic studies involving reducing and increasing integrin β1 activation suggested that ECM microstructures, integrin β1, and intracellular hepatic glutathione synthesis were mechanistically linked. These results represented an unprecedented discovery in mechanobiology regarding ECM microstructures’ role in regulating the hepatic metabolome, i.e., glutathione bioavailability, which can provide new insights into understanding and treating fibrotic liver diseases.
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最近的机械生物学研究研究了细胞外基质(ECM)刚度对细胞行为的总体影响。然而,对于ECM微结构如何调节关键代谢途径和关键代谢物,我们知之甚少。谷胱甘肽是一种主要在肝脏中合成的三肽,是一种用于某些异种生物代谢和氧化物种减少的关键分子。在此,我们报道了ECM微结构可以直接调节谷胱甘肽的生物利用度和合成。通过制备一种纤维支架来模拟健康的天然肝脏ECM和一种平面底物,模拟具有相同表面化学成分的严重纤维化情况,我们发现纤维ECM上调肝细胞中的谷胱甘肽水平,增强抗氧化能力。机制研究涉及减少和增加整合素β1的激活,表明ECM微结构、整合素β1和细胞内肝谷胱甘肽合成存在机制联系。这些结果代表了机械生物学中ECM微结构在调节肝脏代谢组(即谷胱甘肽生物利用度)中的作用的前所未有的发现,可以为理解和治疗纤维化性肝病提供新的见解。
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引用次数: 0
Versatile Conductive Polydopamine via Tailoring Counterions 通过剪裁反离子的多用途导电聚多巴胺。
IF 5.4 2区 化学 Q1 BIOCHEMISTRY & MOLECULAR BIOLOGY Pub Date : 2025-12-08 DOI: 10.1021/acs.biomac.5c01689
Busra Ozlu , Bong Sup Shim
Polydopamine (PDA), a synthetic analogue of natural biopolymer melanin, possesses a conjugated backbone that theoretically offers conductive pathways. However, the synthesis of conductive PDA has proven to be challenging, with only a few studies successfully achieving structural control during polymerization. In this study, the electrochemical synthesis of conductive PDA using various counterions, including lithium perchlorate (LiClO4), potassium hexafluorophosphate (KPF6), sodium p-toluene sulfonate (Na+-pTS), iron p-toluene sulfonate (Fe3+-pTS), and sodium polystyrenesulfonate, was systematically investigated in terms of their effect on the surface morphology, chemical structure, and electrochemical properties of PDA. To our knowledge, this is the first study to explore the role of counterions during the electropolymerization of PDA, resulting in significant improvements in its structure, hence the electrochemical performance. These findings suggest that the incorporation of counterions can pave the way for developing conductive PDA, which can be tailored for a wide range of bioelectronic applications.
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聚多巴胺(PDA)是一种天然生物聚合物黑色素的合成类似物,具有理论上提供传导途径的共轭主链。然而,导电PDA的合成已被证明是具有挑战性的,只有少数研究成功地实现了聚合过程中的结构控制。本研究系统研究了高氯酸锂(LiClO4)、六氟磷酸钾(KPF6)、对甲苯磺酸钠(Na+-pTS)、对甲苯磺酸铁(Fe3+-pTS)和聚苯磺酸钠等不同反离子对导电PDA表面形貌、化学结构和电化学性能的影响。据我们所知,这是第一次探索反离子在PDA电聚合过程中的作用,从而显著改善了其结构,从而提高了电化学性能。这些发现表明,反离子的结合可以为开发导电PDA铺平道路,这种PDA可以用于广泛的生物电子应用。
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引用次数: 0
Triple-Dynamic-Bond-Engineered Self-Healing Conductive Hydrogels for Deformation-Immune Flexible Supercapacitors and Wearable Epidermal Sensors. 用于变形免疫柔性超级电容器和可穿戴表皮传感器的三动态键工程自修复导电水凝胶。
IF 5.4 2区 化学 Q1 BIOCHEMISTRY & MOLECULAR BIOLOGY Pub Date : 2025-12-08 DOI: 10.1021/acs.biomac.5c02106
Lixia Liao, Jiaqi Ding, Xiao Xiong, Fengjiao Quan, Xingxing Liu, Min Zhu, Zehui Chen, Sheng Li, Lian Zhu, Benmei Wei, Juntao Zhang, Haibo Wang

Conductive hydrogels are promising for flexible electronics, yet integrating high conductivity, mechanical robustness, biocompatibility, and environmental stability for flexible supercapacitors (FSCs) and wearable epidermal sensors remains challenging. Herein, a self-healing hydrogel with multiple energy dissipation pathways was constructed using synergistic dynamic borate ester bonds, Schiff base bonds, and hydrogen bonds. Incorporating polydopamine-coated MXene (MP) enhanced the mechanical strength, conductivity, and antibacterial/antioxidant properties. FSCs with the hydrogel electrolyte exhibited excellent electrochemical performance with a specific capacitance of 373.41 mF/cm2, an energy density of 74.67 μWh/cm2, a capacitance retention of 82.43% after 5000 cycles, and high deformation tolerance. As a strain sensor, it effectively detected both large and subtle human motions, including physiological microexpressions and pulse beats due to its high sensitivity (gauge factor = 1.73) and repeatability. Importantly, its notable degradability owing to the inherent degradability of the chitosan framework and the reversible dissociation of dynamic bonds addresses environmental concerns from traditional electronics.

导电性水凝胶在柔性电子产品方面很有前景,但将高导电性、机械稳健性、生物相容性和环境稳定性集成到柔性超级电容器(fsc)和可穿戴表皮传感器中仍然具有挑战性。本文利用协同动态硼酸酯键、希夫碱键和氢键构建了具有多种能量耗散途径的自愈水凝胶。加入聚多巴胺包被的MXene (MP)增强了机械强度、电导率和抗菌/抗氧化性能。采用水凝胶电解质制备的FSCs具有优异的电化学性能,比电容为373.41 mF/cm2,能量密度为74.67 μWh/cm2,循环5000次后电容保持率为82.43%,且具有较高的抗变形能力。作为一种应变传感器,它具有很高的灵敏度(测量因子= 1.73)和可重复性,可以有效地检测人体的大的和细微的运动,包括生理微表情和脉搏跳动。重要的是,由于壳聚糖框架固有的可降解性和动态键的可逆解离,其显著的可降解性解决了传统电子产品的环境问题。
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引用次数: 0
Fault-Tolerant Adhesive Intelligent Hydrogels Accelerate Diabetic Wound Healing through On-Demand Release of Photothermal/Nitric Oxide and Real-Time Monitoring 容错胶粘剂智能水凝胶通过按需释放光热/一氧化氮和实时监测加速糖尿病伤口愈合。
IF 5.4 2区 化学 Q1 BIOCHEMISTRY & MOLECULAR BIOLOGY Pub Date : 2025-12-08 DOI: 10.1021/acs.biomac.5c01549
Suqing Shi , Qingyan Kang , Chang Yang , Xudong Liu , Yumeng Zhang , Mengya Sun , Linghan Xiao , Wei Zhu , Yujing Liu
Diabetic wounds suffer from delayed healing due to impaired angiogenesis, bacterial infection, and mechanical damage from dressing changes. This study developed an AP-G-OSA-GB-ICG hydrogel via Schiff base and borate ester bonds. The temperature-responsive conductive system integrates photothermal therapy (PTT) and nitric oxide (NO) release for synergistic antibacterial effects. Graphene oxide-BNN6 (GB) and indocyanine green (ICG) eliminate bacteria via near-infrared (NIR) photothermal effects, while light-triggered NO from BNN6 promotes angiogenesis. Gelatin-based thermal responsiveness enables body temperature-triggered adhesion switching to reduce neotissue damage. Graphene oxide (GO) endows electrical conductivity for potential physiological signal monitoring. In type 1 diabetic SD rats, the hydrogel with NIR irradiation and NO release achieved 100% wound closure at day 14. Masson trichrome staining showed orderly collagen fiber deposition, CD31 and α-SMA immunostaining confirmed a significant increase in vessel density. Hematoxylin and eosin (H&E) staining further revealed the absence of significant inflammatory cell infiltration. This multifunctional system integrates antibacterial activity, angiogenesis promotion, intelligent adhesion, and physiological monitoring, offering a mechanistically innovative and clinically translatable strategy for diabetic wound precision treatment.
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糖尿病伤口由于血管生成受损、细菌感染和换药造成的机械损伤而延迟愈合。本研究通过希夫碱和硼酸酯键制备了ap - g - sa - gb - icg水凝胶。该温度响应传导系统集成了光热疗法(PTT)和一氧化氮(NO)释放,具有协同抗菌作用。氧化石墨烯-BNN6 (GB)和吲哚菁绿(ICG)通过近红外(NIR)光热效应消除细菌,而BNN6的光触发NO促进血管生成。基于明胶的热响应性使体温触发的粘附切换能够减少新组织损伤。氧化石墨烯(GO)具有良好的导电性,可用于监测潜在的生理信号。在1型糖尿病SD大鼠中,近红外照射和NO释放的水凝胶在第14天达到100%的伤口愈合。马松三色染色显示胶原纤维有序沉积,CD31和α-SMA免疫染色证实血管密度明显增加。苏木精和伊红(H&E)染色进一步显示没有明显的炎症细胞浸润。该多功能系统集抗菌活性、促进血管生成、智能粘附和生理监测于一体,为糖尿病伤口精准治疗提供了一种机制创新和临床可翻译的策略。
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引用次数: 0
Facial Preparation of Multifunctional Silk Fibroin Nanofiber Hydrogel Microspheres as a Biomedical Platform 作为生物医学平台的多功能丝素纳米纤维水凝胶微球的面部制备。
IF 5.4 2区 化学 Q1 BIOCHEMISTRY & MOLECULAR BIOLOGY Pub Date : 2025-12-08 DOI: 10.1021/acs.biomac.5c01004
Luyao Zhong , Jiaxin Wang , Renchuan You, Ying Huang, Shuqin Yan, Qiang Zhang
Nanofiber microspheres are widely used in biomedical devices and tissue engineering for their unique structure and nanoscale effects but suffer from complex fabrication and limited biocompatibility. This study prepared hydrogel microspheres (specific surface area: 153.69 m2/g) via electrostatic spraying, using silk nanofibers (SNF) and sodium alginate (SA). These microspheres showed excellent biocompatibility (over 90% viability of human umbilical vein endothelial cells after 7 days of culture). As drug carriers, doxorubicin hydrochloride-loaded ones achieved 60% drug release within 72 h and reduced cancer cell viability to below 40%. Fluorescent peptide-grafted SNF/SA microspheres enhanced protease detection sensitivity (detection limit: 9.75 pM), outperforming conventional probes. Moreover, SNF/SA/hydroxyapatite (HAp) hybrid microspheres (with a hierarchically porous structure) promoted deep cellular migration in 7 days, increased osteoblast differentiation by over 50%, and accelerated proliferation by 30%, offering dual osteogenic activity and biocompatibility. This study provides an innovative strategy for silk fibroin-based biomedical devices and materials.
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纳米纤维微球以其独特的结构和纳米效应在生物医学器件和组织工程中得到了广泛的应用,但其制备工艺复杂,生物相容性有限。本研究以丝纳米纤维(SNF)和海藻酸钠(SA)为原料,采用静电喷涂法制备了比表面积为153.69 m2/g的水凝胶微球。这些微球具有良好的生物相容性(培养7天后,人脐静脉内皮细胞的存活率超过90%)。作为药物载体,装载盐酸阿霉素的药物在72 h内达到60%的药物释放,并将癌细胞存活率降低到40%以下。荧光肽接枝的SNF/SA微球提高了蛋白酶检测灵敏度(检测限:9.75 pM),优于传统探针。此外,SNF/SA/羟基磷灰石(HAp)杂交微球(具有分层多孔结构)在7天内促进深层细胞迁移,使成骨细胞分化率提高50%以上,增殖速度加快30%,具有双重成骨活性和生物相容性。本研究为基于丝素蛋白的生物医学器件和材料提供了一种创新策略。
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引用次数: 0
Bio-Modified UFBC Interlocking Structure for Enhanced Interfacial Design of PLA Films with Improved Plasticity and Compatibility 生物改性UFBC联锁结构增强PLA膜的界面设计,提高PLA膜的可塑性和相容性。
IF 5.4 2区 化学 Q1 BIOCHEMISTRY & MOLECULAR BIOLOGY Pub Date : 2025-12-08 DOI: 10.1021/acs.biomac.5c01633
Haifeng Chen , Zijian Deng , Wenzhu Li , Weimiao Lu , Jingda Huang , Wenbiao Zhang
Polylactic acid (PLA) films are limited in their further applications due to their high brittleness. To enhance the toughness of PLA-based films, UFBC modified with biocohesive agents (TA-ESO) was used, in this study, to improve compatibility and interlocking adhesion with PLA. Benefiting from the effects of TA-ESO in plasticization and interface improvement, TA-ESO-modified UFBC can make PLA more pliable while establishing a stronger mechanical interlocking structure, thus raising the mechanical properties of the system. Compared to pure PLA films, the tensile elongation of TA-ESO-modified UFBC/PLA composite films increased by 189.11%, and the tensile strength remained at a high level of 23.95 MPa, along with an increase in crystallinity (X c) from 1.09 to 2.05%. Given their excellent strength and toughness, TA-ESO-modified UFBC/PLA composite films are expected to offer various potential applications in the packaging, medical, and agricultural fields.
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聚乳酸(PLA)薄膜的高脆性限制了其进一步的应用。为了提高PLA基薄膜的韧性,在本研究中,使用生物内聚剂(TA-ESO)修饰的UFBC来改善与PLA的相容性和联锁附着力。得益于TA-ESO的塑化和界面改善作用,TA-ESO改性UFBC可以使PLA更加柔韧,同时建立更强的机械联锁结构,从而提高体系的力学性能。与纯PLA膜相比,ta - eso改性UFBC/PLA复合膜的拉伸伸长率提高了189.11%,拉伸强度保持在23.95 MPa的较高水平,结晶度(Xc)从1.09提高到2.05%。由于其优异的强度和韧性,ta - eso改性UFBC/PLA复合薄膜有望在包装、医疗和农业领域提供各种潜在的应用。
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引用次数: 0
Correction to "Arabinoxylan in Water through SANS: Single Chain Conformation, Chain Overlap, and Clustering". 更正“通过SANS在水中的阿拉伯木聚糖:单链构象、链重叠和聚类”。
IF 5.4 2区 化学 Q1 BIOCHEMISTRY & MOLECULAR BIOLOGY Pub Date : 2025-12-08 DOI: 10.1021/acs.biomac.5c02360
Maike Petermann, Lucie Dianteill, Amal Zeidi, Roméo Vaha Ouloassekpa, Paul Budisavljevic, Claude Le Men, Cédric Montanier, Pierre Roblin, Bernard Cabane, Ralf Schweins, Claire Dumon, Antoine Bouchoux
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引用次数: 0
Tuning Protein–Nanoparticle Interfacial Interactions via Zwitterionic Surface Functionalization: A Molecular Dynamics Study of HSA Adsorption on Dendrimer-Coated Carbon Quantum Dots 通过两性离子表面功能化调节蛋白质-纳米颗粒界面相互作用:树状聚合物包覆碳量子点吸附HSA的分子动力学研究。
IF 5.4 2区 化学 Q1 BIOCHEMISTRY & MOLECULAR BIOLOGY Pub Date : 2025-12-08 DOI: 10.1021/acs.biomac.5c01178
Pawel Wolski , Chris Oostenbrink , Tomasz Panczyk
Understanding nanoparticle–protein interactions is crucial for designing biocompatible nanocarriers. Here, we performed atomistic molecular dynamics simulations to investigate the binding of human serum albumin (HSA) with carbon quantum dot (CQD)–based nanoparticles functionalized with poly­(amidoamine) (PAMAM) dendrimers modified by zwitterionic carboxybetaine acrylamide (CBAA). Three systems with 0% (M0), 50% (M50), and 90% (M90) CBAA modifications were constructed to assess the effect of surface zwitterion density on protein adsorption, hydration, and structural stability. The fully modified M90 nanoparticles exhibited the weakest HSA binding due to reduced electrostatic attraction and steric shielding as well as the formation of a stable, dense hydration layer that hindered protein attachment. Across all systems, HSA retained its secondary structure, confirming its structural compatibility. These findings provide molecular insights into the antifouling mechanisms of CBAA-modified CQD–PAMAM nanocarriers and guide their rational design for enhanced biocompatibility.
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了解纳米粒子与蛋白质的相互作用对于设计生物相容性纳米载体至关重要。在这里,我们通过原子分子动力学模拟研究了人血清白蛋白(HSA)与碳量子点(CQD)纳米粒子的结合,这些纳米粒子被两性离子羧基甜菜碱丙烯酰胺(CBAA)修饰的聚氨基胺(PAMAM)树状大分子功能化。构建了0% (M0)、50% (M50)和90% (M90) CBAA修饰的三种体系,以评估表面两性离子密度对蛋白质吸附、水合作用和结构稳定性的影响。完全修饰的M90纳米颗粒由于静电吸引力和空间屏蔽减少,以及形成稳定、致密的水合层,阻碍了蛋白质的附着,从而表现出最弱的HSA结合。在所有体系中,HSA保持了二级结构,证实了其结构相容性。这些发现为cbaa修饰的CQD-PAMAM纳米载体的防污机制提供了分子视角,并指导其合理设计以增强生物相容性。
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引用次数: 0
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