ACS Central Science最新文献

Nanoconfinement provides a promising strategy to promote the electrochemical CO₂ reduction reaction (CO₂RR) owing to enhanced reactant enrichment and collision. However, the nanoconfinement influence on the CH₄ selectivity from the CO₂RR with related regulation mechanism is unclear. Herein, a series of mesoporous CeO₂ loaded Cu catalysts with controllable pore size (1.3–5.5 nm) are designed to modulate the CO₂RR selectivity to CH₄. It is found that decreasing the pore size can apparently enhance the CO₂RR performance while inhibiting the HER activity. Moreover, a volcano-type relationship between the CH₄ selectivity and the pore diameter is observed among these catalysts, while Cu-mCeO₂-3.0 (pore diameter of 3.0 nm) shows the highest CH₄ Faradaic efficiency (66.1 ± 2.9%). The in situ experiments and DFT calculations illustrate that a smaller pore size with stronger confinement over Cu-mCeO₂-x can promote the adsorption and transformation of reactants (*CO, *CHO, etc.) for CH₄ production, but too narrow confined space (1.3 nm) will contribute to much higher intermediate coverage and promote their collision for C–C coupling to C₂₊ products instead, thus reducing the CH₄ selectivity. This work provides designing insights into metal/oxide catalysts with controllable pore size to study the nanoconfinement effect on the CO₂RR-to-CH₄ activity, which can be extended to other oxide-based catalytic reactions.

This study establishes a correlation between the CO₂RR-to-CH₄ activity and the pore size of mesoporous Cu-CeO₂ catalysts, elucidating the underlying regulation mechanisms.

Sodium-ion batteries (SIBs) are considered potential alternatives to lithium-ion batteries (LIBs) due to the abundant resources and low sodium cost. The rational nanostructural design for anode materials plays a crucial role in SIBs. TiO₂, as a common electrode material, suffers from the drawbacks of low specific surface area and poor conductivity. To overcome these limitations, we propose a strategy combining solvent evaporation-induced self-assembly and chemical oxidative polymerization to construct an ultrathin polypyrrole (PPy)-coated mesoporous TiO₂ microsphere (meso-TiO₂@PPy) core–shell structure. The combination of the mesoporous structure and the conductive coating endows the micrometer-sized TiO₂ spheres with high specific surface area, excellent conductivity, and abundant sodium-ion diffusion pathways, leading to a dominant pseudocapacitance (94%) of total charge storage. Remarkably, such integration allows for a high reversible capacity of 160.6 mAh g^–1 at 1 A g^–1, good rate performance, and stable cycling performance (capacity retention of 80.8% after 2000 cycles). Our research provides a pathway for the design of compositive anode materials for high-performance SIBs.

A type of integrated mesoporous TiO₂−PPy composite is designed as an anode to guarantee high surface area, tap density, and conductivity for overall enhancement of pseudocapacitive Na⁺ storage.

The climate-resistant bean boasts a chemical profile similar to Arabica’s.

The stretchability (ability to be elongated) and toughness (capacity to absorb energy before breaking) of polymer network materials, such as elastomers and hydrogels, often determine their utility and lifetime. Direct correlations between the molecular behavior of polymer network components and the physical properties of the network inform the design of materials with enhanced performance, extended lifetime, and minimized waste stream. Here, we report the impact of the fused ring size in bicyclic cyclobutane mechanophores within the strands of polymer network gels. The mechanophores and their polymer strands share the same initial covalent contour length, whereas the capacity for reactive strand extension (RSE) is varied by changing the size of the ring fused to the cyclobutane from 5 to 12 carbon atoms. We observe the first evidence of covalent RSE effects in a single-network gel, and strands with greater RSE lead to gels with greater stretchability and toughness. The same qualitative correlation between molecular and macroscopic extension is also observed in DN hydrogels with mechanophores in the prestretched first network.

The strain at break of polymer network materials can be tuned by varying the molecular length hidden behind embedded cyclobutane mechanophores.

The lipid composition of cellular membranes is highly dynamic and undergoes continuous remodeling, affecting the biophysical properties critical to biological function. Here, we introduce an optical approach to manipulate membrane viscosity based on an exogenous synthetic fatty acid with an azobenzene photoswitch, termed FAAzo4. Cells rapidly incorporate FAAzo4 into phosphatidylcholine and phosphatidylethanolamine in a concentration- and cell type-dependent manner. This generates photoswitchable PC and PE analogs, which are predominantly located in the endoplasmic reticulum. Irradiation causes a rapid photoisomerization that decreases membrane viscosity with high spatiotemporal precision. We use the resulting “PhotoCells” to study the impact of membrane viscosity on ER-to-Golgi transport and demonstrate that this two-step process has distinct membrane viscosity requirements. Our approach provides an unprecedented way of manipulating membrane biophysical properties directly in living cells and opens novel avenues to probe the effects of viscosity in a wide variety of biological processes.

PhotoCells enable the dynamic control of protein viscosity in living cells. A decrease of membrane viscosity increases the amount of protein recruited at ERES but slows down the transport to Golgi.

The development of artificial catalysts with efficiency that can rival those of Nature’s enzymes represents one of the foremost yet challenging goals in homogeneous metal catalysis. Inspired by the exceptional performance of metalloenzymes, the design and development of highly efficient bi/multinuclear catalysts via judicious ligand design, by taking advantage of the cooperative action of the proximal catalytic sites, has attracted great attention. Herein, we report the self-assembly of a chiral hexadentate BINOL-dipyox ligand with zinc acetate into a well-defined trinuclear zinc complex, which demonstrated ultrahigh catalytic productivity in the enantioselective hydroboration of ketones with an unprecedented turnover number (TON) of 19,400 at an extremely low catalyst loading (0.005 mol %). Mechanistic investigations reveal that a cooperative Lewis acid activation mode is operating in the catalytic process, hence, underscoring the unique advantages of the trinuclear architecture.

This work reports the rational design and self-assembly of an artificial chiral trinuclear zinc catalyst, which exhibits exceptional efficiency in enantioselective ketone hydroboration.

Natural products continue to play important roles in biomedical, agricultural and ecological science. Yet despite ongoing advances in “omics” technologies, including genomics, transcriptomics, phenomics and metabolomics, there is still no clear consensus on the scope and scale of chemical diversity in the natural world. The evolution and maturation of chemical databases for natural products offer opportunities to explore this question from a range of different perspectives. This Outlook will use data from the Natural Products Atlas to examine rates of similarity and variation among biosynthetic classes of molecules, to explore how structure can be related to function, and to examine the scope and scale of new scaffold discovery in the current era of natural products science. It presents an examination of known chemical diversity, investigates what this diversity can tell us about potential translational applications, and explores how current knowledge informs what we might expect to discover in future studies.

Open-source databases inform our understanding of the known landscape of natural products. These analyses can identify themes among known compound classes and highlight new avenues for investigation.

Mas Subramanian’s hunt to create red that’s vivid, durable, and safe.

Chimeric antigen receptor (CAR) T cell therapy has revolutionized the treatment of hematologic malignancies; however, durable remissions remain limited due to antigen-negative cancer relapse, where tumor cells downregulate or lose the targeted antigen to evade immune recognition. To address this challenge, we developed cysteine-engineered CAR (CysCAR) T cells that redirect T cells to target cancer cells based on extracellular redox imbalances and the altered thiol/disulfide ratios, a marker we identified on B cell lymphomas. Here, we show that CysCAR-T cells, engineered with different cysteine-modified antibody fragments, exhibit a potent and specific cytotoxicity in vitro across various B cell lymphoma (BCL) subtypes, even in antigen escape models. Moreover, by integrating cysteine engineering with clinically used anti-CD19 CAR-T cells, we enabled simultaneous targeting of CD19 and altered redox states on BCL, potentially reducing the risk of antigen escape. In a pilot in vivo study, these bifunctional CD19-CysCAR-T cells suppressed tumor growth and prolonged survival of BCL-bearing mice without inducing systemic toxicity. Given that aberrant exofacial redox states are a hallmark of multiple cancers, our findings suggest a promising strategy to enhance the efficacy of anti-CD19 CAR-T cell therapy, overcome antigen escape, and reduce tumor relapse in BCL, with potential applicability to other malignancies.

Thiol-mediated engineering of CAR-T cells overcomes antigen escape in BCL with potential applicability to other malignancies.

Nature combines different materials in a single structure to achieve functions that no single material could accomplish alone, an approach that inspires efforts to build synthetic systems with precisely tailored properties. Vat photopolymerization (VPP) enables fast, high-resolution 3D printing, but most printed parts still use only one material. This Outlook highlights emerging strategies for single-vat multimaterial VPP, where light selectively activates different chemical reactions to build complex structures with multiple materials. Key advances will depend on expanding resin chemistry beyond standard acrylates, improving reaction selectivity, and using grayscale and multiwavelength light control to define where and how materials form. Standardized mechanical, thermal, and interface testing methods are essential for ensuring reliable results. With advances in chemistry, optics, and data-driven design, multimaterial VPP could unlock transformative applications in medicine, manufacturing, and aerospace.

Stimuli-selective resins offer key opportunities for fast, high-resolution multimaterial 3D printing. This Outlook highlights advances needed in chemistry, processing, and characterization.