From Homogeneity to Turing Pattern: Kinetically Controlled Self-Organization of Transmembrane Protein.

Understanding the spatial organization of membrane proteins is crucial for unraveling key principles in cell biology. The reaction-diffusion model is commonly used to understand biochemical patterning; however, applying reaction-diffusion models to subcellular phenomena is challenging because of the difficulty in measuring protein diffusivity and interaction kinetics in the living cell. In this work, we investigated the self-organization of the plasmalemma vesicle-associated protein (PLVAP), which creates regular arrangements of fenestrated ultrastructures, using single-molecule tracking. We demonstrated that the spatial organization of the ultrastructures is associated with a decrease in the association rate by actin destabilization. We also constructed a reaction-diffusion model that accurately generates a hexagonal array with the same 130 nm spacing as the actual scale and informs the stoichiometry of the ultrastructure, which can be discerned only through electron microscopy. Through this study, we integrated single-molecule experiments and reaction-diffusion modeling to surpass the limitations of static imaging tools and proposed emergent properties of the PLVAP ultrastructure.

In Situ Infrared Spectroscopic Evidence of Enhanced Electrochemical CO2 Reduction and C-C Coupling on Oxide-Derived Copper.

The reaction mechanism of CO2 electroreduction on oxide-derived copper has not yet been unraveled even though high C2+ Faradaic efficiencies are commonly observed on these surfaces. In this study, we aim to explore the effects of copper anodization on the adsorption of various CO2RR intermediates using in situ surface-enhanced infrared absorption spectroscopy (SEIRAS) on metallic and mildly anodized copper thin films. The in situ SEIRAS results show that the preoxidation process can significantly improve the overall CO2 reduction activity by (1) enhancing CO2 activation, (2) increasing CO uptake, and (3) promoting C-C coupling. First, the strong *COO- redshift indicates that the preoxidation process significantly enhances the first elementary step of CO2 adsorption and activation. The rapid uptake of adsorbed *COatop also illustrates how a high *CO coverage can be achieved in oxide-derived copper electrocatalysts. Finally, for the first time, we observed the formation of the *COCHO dimer on the anodized copper thin film. Using DFT calculations, we show how the presence of subsurface oxygen within the Cu lattice can improve the thermodynamics of C2 product formation via the coupling of adsorbed *CO and *CHO intermediates. This study advances our understanding of the role of surface and subsurface conditions in improving the catalytic reaction kinetics and product selectivity of CO2 reduction.

The Role of Phase Mixing Degree in Promoting C-C Coupling in Electrochemical CO2 Reduction Reaction on Cu-based Catalysts.

Cu-based catalysts have been identified as the most promising candidates for generation of C2+ products in electrochemical CO2 reduction reaction. Defect engineering in catalysts is a widely employed strategy for promoting C-C coupling on Cu. However, comprehensive understanding of defect structure-to-activity relationship has not been obtained. In this study, controllable defects generation is achieved, which leads to a series of Cu-based catalysts with various phase mixing degrees. It is observed that the Faradaic efficiency toward C2+ products increases with the phase mixing degree, reaching 81 % at maximum. In situ infrared absorption spectroscopy reveals that the catalysts with higher phase mixing degree tend to form *CO more easily and possess higher retention of *CO under high overpotential window, thereby promoting C-C coupling. This work sheds new light on the relationship between defects and C-C coupling, and the rational developed of more advanced Cu-base catalysts.

A Sulfur-Doped Copper Catalyst with Efficient Electrocatalytic Formate Generation during the Electrochemical Carbon Dioxide Reduction Reaction.

Catalysts involving post-transition metals have shown almost invincible performance on generating formate in electrochemical CO2 reduction reaction (CO2 RR). Conversely, Cu without post-transition metals has struggled to achieve comparable activity. In this study, a sulfur (S)-doped-copper (Cu)-based catalyst is developed, exhibiting excellent performance in formate generation with a maximum Faradaic efficiency of 92 % and a partial current density of 321 mA cm-2 . Ex situ structural elucidations reveal the presence of abundant grain boundaries and high retention of S-S bonds from the covellite phase during CO2 RR. Furthermore, thermodynamic calculations demonstrate that S-S bonds can moderate the binding energies with various intermediates, further improving the activity of the formate pathway. This work is significant in modifying a low-cost catalyst (Cu) with a non-metallic element (S) to achieve comparable performance to mainstream catalysts for formate generation in industrial grade.

Fe-N-C Boosts the Stability of Supported Platinum Nanoparticles for Fuel Cells.

The poor durability of Pt-based nanoparticles dispersed on carbon black is the challenge for the application of long-life polymer electrolyte fuel cells. Recent work suggests that Fe- and N-codoped carbon (Fe-N-C) might be a better support than conventional high-surface-area carbon. In this work, we find that the electrochemical surface area retention of Pt/Fe-N-C is much better than that of commercial Pt/C during potential cycling in both acidic and basic media. In situ inductively coupled plasma mass spectrometry studies indicate that the Pt dissolution rate of Pt/Fe-N-C is 3 times smaller than that of Pt/C during cycling. Density functional theory calculations further illustrate that the Fe-N-C substrate can provide strong and stable support to the Pt nanoparticles and alleviate the oxide formation by adjusting the electronic structure. The strong metal-substrate interaction, together with a lower metal dissolution rate and highly stable support, may be the reason for the significantly enhanced stability of Pt/Fe-N-C. This finding highlights the importance of carbon support selection to achieve a more durable Pt-based electrocatalyst for fuel cells.

Single-Molecule Imaging of Membrane Proteins on Vascular Endothelial Cells.

Transporting substances such as gases, nutrients, waste, and cells is the primary function of blood vessels. Vascular cells use membrane proteins to perform crucial endothelial functions, including molecular transport, immune cell infiltration, and angiogenesis. A thorough understanding of these membrane receptors from a clinical perspective is warranted to gain insights into the pathogenesis of vascular diseases and to develop effective methods for drug delivery through the vascular endothelium. This review summarizes state-of-the-art single-molecule imaging techniques, such as super-resolution microscopy, single-molecule tracking, and protein-protein interaction analysis, for observing and studying membrane proteins. Furthermore, recent single-molecule studies of membrane proteins such as cadherins, integrins, caveolins, transferrin receptors, vesicle-associated protein-1, and vascular endothelial growth factor receptor are discussed.

Mid-old cells are a potential target for anti-aging interventions in the elderly.

The biological process of aging is thought to result in part from accumulation of senescent cells in organs. However, the present study identified a subset of fibroblasts and smooth muscle cells which are the major constituents of organ stroma neither proliferative nor senescent in tissues of the elderly, which we termed "mid-old status" cells. Upregulation of pro-inflammatory genes (IL1B and SAA1) and downregulation of anti-inflammatory genes (SLIT2 and CXCL12) were detected in mid-old cells. In the stroma, SAA1 promotes development of the inflammatory microenvironment via upregulation of MMP9, which decreases the stability of epithelial cells present on the basement membrane, decreasing epithelial cell function. Remarkably, the microenvironmental change and the functional decline of mid-old cells could be reversed by a young cell-originated protein, SLIT2. Our data identify functional reversion of mid-old cells as a potential method to prevent or ameliorate aspects of aging-related tissue dysfunction.

Fracture of the L-4 vertebral body after use of a stand-alone interbody fusion device in degenerative spondylolisthesis for anterior L3-4 fixation.

Many studies attest to the excellent results achieved using anterior lumbar interbody fusion (ALIF) for degenerative spondylolisthesis. The purpose of this report is to document a rare instance of L-4 vertebral body fracture following use of a stand-alone interbody fusion device for L3-4 ALIF. The patient, a 55-year-old man, had suffered intractable pain of the back, right buttock, and left leg for several weeks. Initial radiographs showed Grade I degenerative spondylolisthesis, with instability in the sagittal plane (upon 15° rotation) and stenosis of central and both lateral recesses at the L3-4 level. Anterior lumbar interbody fusion of the affected vertebrae was subsequently conducted using a stand-alone cage/plate system. Postoperatively, the severity of spondylolisthesis diminished, with resolution of symptoms. However, the patient returned 2 months later with both leg weakness and back pain. Plain radiographs and CT indicated device failure due to anterior fracture of the L-4 vertebral body, and the spondylolisthesis had recurred. At this point, bilateral facetectomies were performed, with reduction/fixation of L3-4 by pedicle screws. Again, degenerative spondylolisthesis improved postsurgically and symptoms eased, with eventual healing of the vertebral body fracture. This report documents a rare instance of L-4 vertebral body fracture following use of a stand-alone device for ALIF at L3-4, likely as a consequence of angular instability in degenerative spondylolisthesis. Under such conditions, additional pedicle screw fixation is advised.