Mapping the Complete Photocycle that Powers a Large Stokes Shift Red Fluorescent Protein

Large Stokes shift (LSS) red fluorescent proteins (RFPs) are highly desirable for bioimaging advances. The RFP mKeima, with coexisting cis- and trans-isomers, holds significance as an archetypal system for LSS emission due to excited-state proton transfer (ESPT), yet the mechanisms remain elusive. We implemented femtosecond stimulated Raman spectroscopy (FSRS) and various time-resolved electronic spectroscopies, aided by quantum calculations, to dissect the cis- and trans-mKeima photocycle from ESPT, isomerization, to ground-state proton transfer in solution. This work manifests the power of FSRS with global analysis to resolve Raman fingerprints of intermediate states. Importantly, the deprotonated trans-isomer governs LSS emission at 620 nm, while the deprotonated cis-isomer's 520 nm emission is weak due to an ultrafast cis-to-trans isomerization. Complementary spectroscopic techniques as a table-top toolset are thus essential to study photochemistry in physiological environments.     

Ultrasound-Directed Symmetry Breaking and Spin Filtering of Supramolecular Assemblies from only Achiral Building Blocks

Herein we describe the self-assembly of an achiral molecule into macroscopic helicity as well as the emergent chiral-selective spin-filtering effect. It was found that a benzene-1,3,5-tricarboxamide (BTA) motif with an aminopyridine group in each arm could coordinate with Ag^I and self-assemble into nanospheres. Upon sonication, symmetry breaking occurred and the nanospheres transferred into helical nanofibers with strong CD signals. Although the sign of the CD signals appeared randomly, it could be controlled by using the as-made chiral assemblies as a seed. Furthermore, it was found that the charge transport of the helical nanofibers was highly selective with a spin-polarization transport of up to 45 %, although the chiral nanofibers are composed exclusively from achiral building blocks. This work demonstrates symmetry breaking under sonication and the chiral-selective spin-filtering effect.     

An In Situ Investigation of the Protein Corona Formation Kinetics of Single Nanomedicine Carriers by Self-Regulated Electrochemiluminescence Microscopy

Protein coronas are present extensively at the bio-nano interface due to the natural adsorption of proteins onto nanomaterials in biological fluids. Aside from the robust property of nanoparticles, the dynamics of the protein corona shell largely define their chemical identity by altering interface properties. However, the soft coronas are normally complex and rapidly changing. To real-time monitor the entire formation, we report here a self-regulated electrochemiluminescence (ECL) microscopy based on the interaction of the Ru(bpy)₃³⁺ with the nanoparticle surface. Thus, the heterogeneity of the protein corona is in situ observed in single nanoparticle “cores” before and after loading drugs in nanomedicine carriers. The label-free, optical stable and dynamic ECL microscopy minimize misinterpretations caused by the variation of nanoparticle size and polydispersity. Accordingly, the synergetic actions of proteins and nanoparticles properties are uncovered by chemically engineered protein corona. After comparing the protein corona formation kinetics in different complex systems and different nanomedicine carriers, the universality and accuracy of this technique were well demonstrated via the protein corona formation kinetics curves regulated by competitive adsorption of Ru(bpy)₃³⁺ and multiple proteins on surface of various carriers. The work is of great significance for studying bio-nano interface in drug delivery and targeted cancer treatment.     

Engineering Heterogeneous Catalysis with Strong Metal–Support Interactions: Characterization,Theory and Manipulation

Strong metal–support interactions (SMSI) represent a classic yet fast-growing area in catalysis research. The SMSI phenomenon results in the encapsulation and stabilization of metal nanoparticles (NPs) with the support material that significantly impacts the catalytic performance through regulation of the interfacial interactions. Engineering SMSI provides a promising approach to steer catalytic performance in various chemical processes, which serves as an effective tool to tackle energy and environmental challenges. Our Minireview covers characterization, theory, catalytic activity, dependence on the catalytic structure and inducing environment of SMSI phenomena. By providing an overview and outlook on the cutting-edge techniques in this multidisciplinary research field, we not only want to provide insights into the further exploitation of SMSI in catalysis, but we also hope to inspire rational designs and characterization in the broad field of material science and physical chemistry.     

Bio-Inspired Aerobic-Hydrophobic Janus Interface on Partially Carbonized Iron Heterostructure Promotes Bifunctional Nitrogen Fixation

Competition from hydrogen/oxygen evolution reactions and low solubility of N₂ in aqueous systems limited the selectivity and activity on nitrogen fixation reaction. Herein, we design an aerobic-hydrophobic Janus structure by introducing fluorinated modification on porous carbon nanofibers embedded with partially carbonized iron heterojunctions (Fe₃C/Fe@PCNF-F). The simulations prove that the Janus structure can keep the internal Fe₃C/Fe@PCNF-F away from water infiltration and endow a N₂ molecular-concentrating effect, suppressing the competing reactions and overcoming the mass-transfer limitations to build a robust “quasi-solid–gas” state micro-domain around the catalyst surface. In this proof-of-concept system, the Fe₃C/Fe@PCNF-F exhibits excellent electrocatalytic performance for nitrogen fixation (NH₃ yield rate up to 29.2 μg h⁻¹ mg⁻¹_cat. and Faraday efficiency (FE) up to 27.8 % in nitrogen reduction reaction; NO₃⁻ yield rate up to 15.7 μg h⁻¹ mg⁻¹_cat. and FE up to 3.4 % in nitrogen oxidation reaction).     

Effect of Co-catalyst CdS on the Photocatalytic Performance of ZnMoO4 for Hydrogen Production

Zinc molybdate (ZnMoO₄), a layer perovskite material, has the advantages of high stability, excellent optical and charge properties. However, its high band gap and high electron–hole recombination efficiency limit its application in the photocatalytic reduction field like hydrogen production. In this study, we used CdS as a co-catalyst and successfully prepared CdS/ZnMoO₄ composite photocatalysts with different loadings. The hydrogen evolution rate of CdS/ZnMoO₄ reached 530.2 µmol h^?1 g^?1, which was approximately 11 and 100 times more than rates of pure CdS and ZnMoO₄ under the same conditions, respectively. It is the presence of CdS that contributed to this improved performance, which acted as an electron acceptor to separate electrons and holes. Besides, a reasonable mechanism was provided based on photoelectrochemical characterizations. CdS loading greatly improved the hydrogen evolution performance of ZnMoO₄ under visible light, providing a direction to improving the performance of perovskite based photocatalysts.

     

气驱油油气混相过程的界面传质特性及其分子机制

油气混相过程的界面传质特性对气驱提高原油采收率技术非常重要。本文针对吉林某油田的实际油组分,采用分子动力学模拟研究了气驱油过程,分析了不同气体和驱替压力下油气两相的状态变化以及界面特性,获得不同驱替气体的最小混相压力(MMP)。结果表明,随着驱替气体压力的升高,气相的密度逐渐增大,油相膨胀密度降低,气相与油相的混合程度增强,油气两相界面厚度增加,界面张力随之减小。同时发现,驱替相中二氧化碳浓度越高,在同等气体压力下,油气界面更厚,油气混合程度更高。纯CO₂驱油得到的MMP远远小于纯N₂驱油,当这两种气体摩尔比为1 : 1混合时MMP介于两种纯气体之间,说明要达到同样的驱油效果二氧化碳需要的压力更小。最后,本文从分子微观作用力角度解释了驱替气体不同时影响油气混相程度的机制,通过分子平均作用势曲线发现油相分子对CO₂的吸引力要大于N₂分子,因此CO₂分子更容易与油相混合,驱替效果更明显。     

Tendon-bone junction healing by injectable bioactive thermo-sensitive hydrogel based on inspiration of tendon-derived stem cells

The rotator cuff repaired construct must establish a contiguous and functioning tendon-bone junction to provide adequate stability. However, fibrocartilage deficiency and bone loss were hardly reversed after physical suture, especially in chronic rotator cuff tears. In this study, we synthesized an injectable methylcellulose/polyvinyl alcohol/polyvinylpyrrolidone-based thermo-sensitive hydrogel, which delivered kartogenin-loaded mesoporous bioactive glass nanoparticles. Physicochemical studies the revealed phase transition temperatures of 35 °C and its ability to induce chondrogenesis and osteogenesis differentiation of tendon-derived stem cells. Furthermore, experiments in rabbit chronic rotator cuff tears model confirmed the fibrocartilage and bone layer regenerative capability of the injected bioactive hydrogel, which could, in turn, support the ultimate tensile stress of the repaired rotator cuff. The bioactive agents-loaded hydrogel reported in this study is a valuable addition to the arsenal of biomaterials in applications to chronic tendon-bone junction injuries.     

Nonenzymatic Electrochemical Sensor for Wearable Interstitial Fluid Glucose Monitoring

We report on a nonenzymatic electrochemical sensor for wearable glucose monitoring in interstitial fluid. The sensor exhibited acceptable selectivity and reliability for continuous glucose detection for up to 30 days. The sensor tip is coated with polyurethane, and the biocompatibility of the tip is investigated by tissue staining. A fully integrated wearable glucose monitoring system is developed with a wireless connection with a smartphone. The test results are in agreement with reference methods. So, we believe the sensor is promising for the development of a continuous glucose monitoring system and diabetes management.     

Photoelectrochemical Cytosensors

Photoelectrochemical (PEC) cytosensors, a combination of the PEC process and the living-cell assay, have emerged as a powerful tool in the analytical and biological science. This mini review provides a brief introduction of this arena and summaries the key steps about the development of PEC cytosensors with representative examples, followed by future prospects based on our own opinions.