山杏仁蛋白源α-葡萄糖苷酶抑制肽的分离、纯化及鉴定

针对木本油料山杏的蛋白质高值化利用问题,利用蛋白酶Alcalase酶解山杏仁蛋白,以体外α-葡萄糖苷酶抑制能力作为评价指标,筛选高活性α-葡萄糖苷酶抑制肽。山杏仁蛋白酶解液通过超滤、G-25葡聚糖凝胶柱、分子筛以及反相高效液相色谱的分离纯化,最终筛选得到2种高活性的α-葡萄糖苷酶抑制肽,其抑制能力分别为6.6μg/mL和7.0μg/mL。利用质谱和氨基酸测序仪对两种α-葡萄糖苷酶抑制肽的分子质量以及序列结构进行了研究,确认2种山杏仁蛋白源α-葡萄糖苷酶抑制肽分别为色氨酸-丙氨酸(WA)和苏氨酸-色氨酸(TW),其α-葡萄糖苷酶抑制能力的IC_(50)值分别为23.97μmol/L和22.93μmol/L。     

生物基两性离子型表面活性剂在不同驱油体系中的乳化稳定动力学

为探索生物基两性离子型表面活性剂(CNBS)在矿化度高于5 g/L体系中的驱油性能,研究该表面活性剂在不同驱油体系中的界面活性和乳化稳定动力学。结果表明,当该表面活性剂质量浓度为1.29 g/L、矿化度为32 g/L、NaOH质量分数为2.5%时,形成稳定W/O型乳状液,油/水界面张力降低至9.60×10^-4mN/m。当体系中总含水体积分数在40%～80%范围时,表面活性剂的加入有利于形成W/O型乳状液,且表面活性剂浓度是影响模拟乳状液稳定动力学的关键因素;随其浓度增大,模拟乳状液的破裂速率常数降低、半衰期和油相含水率增大,模拟乳状液的稳定性增强;当表面活性剂质量浓度为1.50 g/L,模拟乳状液稳定性最好。该表面活性剂与NaOH和黏均相对分子质量为2.5×10⁷的部分水解聚丙烯酰胺(HPAM)具有良好的协同效应,当表面活性剂浓度较低时,三元体系形成稳定W/O型乳状液。分子动力学模拟结果表明,油/水中加入该表面活性剂可使油/水界面膜厚度增大、界面能降低,形成稳定的乳状液;体系中加入NaCl和NaOH,油/水界面膜厚度和界面能均降低,乳状液的稳...     

Molecular Design of Antifouling Polymer Brushes Using Sequence‐Specific Peptoids

Material systems that can be used to flexibly and precisely define the chemical nature and molecular arrangement of a surface would be invaluable for the control of complex biointerfacial interactions. For example, progress in antifouling polymer biointerfaces that prevents nonspecific protein adsorption and cell attachment, which can significantly improve the performance of an array of biomedical and industrial applications, is hampered by a lack of chemical models to identify the molecular features conferring their properties. Poly(N‐substituted glycine) “peptoids” are peptidomimetic polymers that can be conveniently synthesized with specific monomer sequences and chain lengths, and are presented as a versatile platform for investigating the molecular design of antifouling polymer brushes. Zwitterionic antifouling polymer brushes have captured significant recent attention, and a targeted library of zwitterionic peptoid brushes with different charge densities, hydration, separations between charged groups, chain lengths, and grafted chain densities, is quantitatively evaluated for their antifouling properties through a range of protein adsorption and cell attachment assays. Specific zwitterionic brush designs are found to give rise to distinct but subtle differences in properties. The results also point to the dominant roles of the grafted chain density and chain length in determining the performance of antifouling polymer brushes.     

Surface Design in Solid‐State Dye Sensitized Solar Cells: Effects of Zwitterionic Co‐adsorbents on Photovoltaic Performance

In solid‐state dye sensitized solar cells (SSDSCs) charge recombination at the dye‐hole transporting material interface plays a critical role in the cell efficiency. For the first time we report on the influence of dipolar co‐adsorbents on the photovoltaic performance of sensitized hetero‐junction solar cells. In the present study, we investigated the effect of two zwitterionic butyric acid derivatives differing only in the polar moiety attached to their common 4 carbon‐chain acid, i.e., 4‐guanidinobutyric acid (GBA) and 4‐aminobutyric acid (ABA). These two molecules were implemented as co‐adsorbents in conjunction with Z907Na dye on the SSDSC. It was found that a Z907Na/GBA dye/co‐adsorbent combination increases both the open circuit voltage (V_oc) and short‐circuit current density (J_sc) as compared to using Z907Na dye alone. The Z907Na/ABA dye/co‐adsorbent combination increases the J_sc. Impedance and transient photovoltage investigations elucidate the cause of these remarkable observations.     

Multitriggered Tumor‐Responsive Drug Delivery Vehicles Based on Protein and Polypeptide Coassembly for Enhanced Photodynamic Tumor Ablation

Tumor‐responsive nanocarriers are highly valuable and demanded for smart drug delivery particularly in the field of photodynamic therapy (PDT), where a quick release of photosensitizers in tumors is preferred. Herein, it is demonstrated that protein‐based nanospheres, prepared by the electrostatic assembly of proteins and polypeptides with intermolecular disulfide cross‐linking and surface polyethylene glycol coupling, can be used as versatile tumor‐responsive drug delivery vehicles for effective PDT. These nanospheres are capable of encapsulation of various photosensitizers including Chlorin e6 (Ce6), protoporphyrin IX, and verteporfin. The Chlorin e6‐encapsulated nanospheres (Ce6‐Ns) are responsive to changes in pH, redox potential, and proteinase concentration, resulting in multitriggered rapid release of Ce6 in an environment mimicking tumor tissues. In vivo fluorescence imaging results indicate that Ce6‐Ns selectively accumulate near tumors and the quick release of Ce6 from Ce6‐Ns can be triggered by tumors. In tumors the fluorescence of released Ce6 from Ce6‐Ns is observed at 0.5 h postinjection, while in normal tissues the fluorescence appeared at 12 h postinjection. Tumor ablation is demonstrated by in vivo PDT using Ce6‐Ns and the biocompatibility of Ce6‐Ns is evident from the histopathology imaging, confirming the enhanced in vivo PDT efficacy and the biocompatibility of the assembled drug delivery vehicles.     

Locking and Unlocking the Molecular Spin Crossover Transition

The Fe(II) spin crossover complex [Fe{H₂B(pz)₂}₂(bipy)] (pz = pyrazol‐1‐yl, bipy = 2,2′‐bipyridine) can be locked in a largely low‐spin‐state configuration over a temperature range that includes temperatures well above the thermal spin crossover temperature of 160 K. This locking of the spin state is achieved for nanometer thin films of this complex in two distinct ways: through substrate interactions with dielectric substrates such as SiO₂ and Al₂O₃, or in powder samples by mixing with the strongly dipolar zwitterionic p ‐benzoquinonemonoimine C₆H₂(—? NH₂)₂(—? O)₂. Remarkably, it is found in both cases that incident X‐ray fluences then restore the [Fe{H₂B(pz)₂}₂(bipy)] moiety to an electronic state characteristic of the high spin state at temperatures of 200 K to above room temperature; that is, well above the spin crossover transition temperature for the pristine powder, and well above the temperatures characteristic of light‐ or X‐ray‐induced excited‐spin‐state trapping. Heating slightly above room temperature allows the initial locked state to be restored. These findings, supported by theory, show how the spin crossover transition can be manipulated reversibly around room temperature by appropriate design of the electrostatic and chemical environment.     

Nanoagents Based on Poly(ethylene glycol)‐b‐Poly(l‐thyroxine) Block Copolypeptide for Enhanced Dual‐Modality Imaging and Targeted Tumor Radiotherapy

Future healthcare requires development of novel theranostic agents that are capable of not only enhancing diagnosis and monitoring therapeutic responses but also augmenting therapeutic outcomes. Here, a versatile and stable nanoagent is reported based on poly(ethylene glycol)‐b‐poly(l ‐thyroxine) (PEG‐PThy) block copolypeptide for enhanced single photon emission computed tomography/computed tomography (SPECT/CT) dual‐modality imaging and targeted tumor radiotherapy in vivo. PEG‐PThy acquired by polymerization of l ‐thyroxine‐N‐carboxyanhydride (Thy‐NCA) displays a controlled M_n, high iodine content of ≈49.2 wt%, and can spontaneously form 65 nm‐sized nanoparticles (PThyN). In contrast to clinically used contrast agents like iohexol and iodixanol, PThyN reveals iso‐osmolality, low viscosity, and long circulation time. While PThyN exhibits comparable in vitro CT attenuation efficacy to iohexol, it greatly enhances in vivo CT imaging of vascular systems and soft tissues. PThyN allows for surface decoration with the cRGD peptide achieving enhanced CT imaging of subcutaneous B16F10 melanoma and orthotopic A549 lung tumor. Taking advantages of a facile iodine exchange reaction, ¹²⁵I‐labeled PThyN enables SPECT/CT imaging of tumors and monitoring of PThyN biodistribution in vivo. Besides, ¹³¹I‐labeled and cRGD‐functionalized PThyN displays remarkable growth inhibition of the B16F10 tumor in mice (tumor inhibition rate > 89%). These poly(l ‐thyroxine) nanoparticles provide a unique and versatile theranostic platform for varying diseases.     

Zwitterionic Electrochemiluminescence Biointerface Contributes to Label-Free Monitoring of Exosomes Dynamics in a Fluidic Microreaction Device

The competence to construct sensing platforms capable of selective manipulation in complex biological fluids undoubtedly underpins critical future advances in healthcare. Despite the fact that electrochemiluminescence (ECL) has long been an influential technology for clinical diagnosis worldwide, ECL interface that optimizes fouling resistance has been mimicked less often, especially in an integrated platform. Herein, ECL transducer is prepared by the integration of protonated g-C₃N₄ and Ti₃C₂T_x MXene nanosheets, displaying enhanced charge injection/transfer, and inherent catalytic capacities for coreactant ECL. Mussel-bioinspired polydopamine was exploited as a thin, surface-adherent substrate to coat the solid-state transducer and further initiate secondary reactions via Michael Addition for tailing recognition element and zwitterionic segment. This architecture guarantees not only the least suppression of ECL performance but also desired antifouling properties, ensuring < 7.45% of ECL loss after 96 h of exposure to complex biological fluids. Creatively, a highly integrated platform is equipped with the established biointerface, gas diffusion electrode, and fluidic ECL microreactor, affording high-performance exosome checking and dynamics tracking in a non-label manner. Our study provides a general design strategy to obtain a robust antifouling ECL sensing interface based on zwitterionic chemistries and provides a fresh perspective in developing point-of-care and implantable ECL devices.     

Molecular simulations on the hydration and underwater oleophobicity of zwitterionic self-assembled monolayers

Zwitterionic materials have attracted increasing attentions in the underwater super-oleophobic applications for its strong hydration via electrostatic interactions. Herein, molecular dynamics simulations were used to investigate the hydration and underwater oleophobicity of sulfobetaine-terminated self-assembled monolayers (SB-SAMs) with different carbon spacer lengths (CSL) between oppositely charged groups of SB molecules. Simulation results show that the hydration of SB-SAMs is positively dependent on CSL; the underwater oleophobicity is strengthened and then weakened with the increase of CSL, reaching optimal performance when CSL = 3; adhesion force of oil droplet on SB-SAMs is inversely correlated with their contact angles, reaching the minimum value when CSL = 3. Moreover, the addition of NaCl can weaken the self-association of SB molecules resulted from interactions between cationic and anionic groups, which promotes hydration and enhances underwater oleophobicity of SB-SAMs. These results will benefit for the design of novel zwitterion-based materials for anti-fouling and oil–water separation applications.