Zhifei Wang

Chirality is an intrinsic structural feature of biological systems that governs precise molecular recognition and functional regulation. However, translating this stereochemical principle into artificial nanocatalytic systems to achieve controllable chiral catalytic reactivity and biological responses remains poorly understood. Here, a chirality-engineered cuprous sulfide (Cu2S) nanocatalytic platform was rationally developed through enantiomeric ligand-mediated synthesis strategy to enable stereochemistry-regulated ferroptosis induction for antitumor therapy. Benefiting from the strong thiol-Cu coordination interactions, D-/L-penicillamine (D/L-PEN) was employed as the chiral building block to direct the reductive self-assembly with Cu+ species to construct D/L-Cu2S nanoparticles (NPs), which were further functionalized with PEG-TPP to obtain final mitochondria-targeted D-Cu2S-TPP and L-Cu2S-TPP. Interestingly, we found that L-configured NPs exhibited superior catalytic capability for stereoselective H2O2-mediated hydroxyl radicals (•OH) generation compared with their D-configured counterparts. Density functional theory and molecular dynamics simulations validated that the L-configured NPs possessed enhanced Fenton-like catalytic activity toward H2O2 activation to induce higher levels of surface-confined •OH, which was attributed to the higher molecular collision efficiency, the more stable capture and orientation of H2O2 molecules, and the optimized reaction microenvironment associated with the L-configuration. This chirality-dependent catalytic amplification induced severe mitochondrial dysfunction, promoted lipid peroxidation accumulation, and activated ferroptosis by modulating key ferroptosis-associated pathways. Consequently, L-Cu2S-TPP exhibited markedly enhanced ferroptotic cytotoxicity in vitro and superior tumor growth inhibition in vivo. This work revealed the previously underexplored role of chirality in regulating nanocatalytic Fenton-like reactions and established a stereochemistry-guided strategy for modulating endogenous •OH generation.

The escalating heat flux in modern electronics has rendered efficient heat dissipation at standard operating temperatures (~80 °C) a critical bottleneck, severely constraining the performance scaling of next-generation devices. Here, we propose an active cooling strategy based on thermochemical energy storage, utilizing the reversible endothermic decomposition of ammonium carbamate (AC) (NH₂COONH₄(s) → 2NH3(g) + CO₂(g), ΔH = 159.32 kJ·mol⁻¹) for low-to-medium temperature applications (50–100 °C). Experimental results demonstrate that chemical cooling system achieves a gravimetric cooling capacity of 2010 kJ·kg⁻¹, surpassing that of paraffin (180 kJ·kg⁻¹) by an order of magnitude and exceeding typical hydrated salts (200–300 kJ·kg⁻¹) by more than sevenfold. Under a constant 100 W thermal load, a 140 g charge of AC maintained the system temperature below 100 °C for 92 minutes, validating its efficacy in high-performance heat removal. Importantly, experiments in a custom reactor revealed that the decomposition kinetics of AC are precisely tunable through temperature and pressure regulation, allowing for responsive, on-demand control of the cooling process. This combination of high energy density and precise controllability facilitates a shift from passive dissipation to active thermal regulation. Combined numerical and experimental investigations reveal that the persistent thermal protection arises from a synergistic mechanism: a spatially uniform reaction front guarantees maximum chemical enthalpy conversion, while advective transport of the gaseous by-products enables substantial sensible heat extraction. To ensure the practical viability of the AC-based cooling system, potential challenges associated with gaseous ammonia (NH₃) by-products were proactively addressed. A metal-salt-based sorption strategy was therefore implemented for effective NH₃ capture. Moreover, comprehensive corrosion assessments confirmed the excellent compatibility of the decomposition environment with aluminum reactor architectures. By rigorously validating by-product sequestration and material compatibility, this work establishes ammonium carbamate as a viable, high-enthalpy thermochemical heat sink that fundamentally transcends the energy density limits of traditional phase-change materials.

Color vision deficiency (CVD), particularly red‐green color blindness, significantly impairs color discrimination in daily life. Conventional colored lenses and filters often suffer from dye leakage and poor biocompatibility, limiting their clinical use. In this article, colorblind‐correcting contact lenses are developed by chemically grafting a Rhodamine B derivative onto 2‐hydroxyethyl methacrylate‐based polymer networks. This covalent immobilization prevents dye leaching and confers selective light absorption within the 540–570 nm spectral range, thereby specifically targeting red‐green CVD. Compared with physical doping, the chemically grafted lenses exhibit over 95% dye retention, maintained mechanical and optical integrity, and demonstrated excellent biocompatibility with >95% cell viability in L929 and human corneal epithelial cells assays. Simulated clinical tests using the Ishihara plates revealed up to an 85% improvement in recognition accuracy. This approach presents a safe, stable, and effective pathway toward wearable visual correction technologies.

This study aims to enhance the signal-to-noise ratio (SNR) in chemiluminescence immunoassays (CLIA) by increasing the protein immobilization capacity on magnetic bead surfaces. Proteins are macromolecules with three-dimensional conformations where merely increasing the density of surface functional groups on magnetic beads is insufficient to substantially enhance protein immobilization. To address this limitation, we grafted polyamidoamine (PAMAM) dendrimers with three-dimensional architectures onto magnetic beads, simultaneously augmenting the functional group density and expanding the spatial distribution to improve protein loading capacity. PAMAMs were synthesized via iterative Michael addition and amidation cycles between ethylenediamine and methyl acrylate, with its grafting density and behavior on magnetic beads characterized by nuclear magnetic resonance (NMR) spectroscopy. Dynamic light scattering (DLS) analysis revealed an increased hydrodynamic radius of the PAMAM-grafted beads, confirming the successful expansion of protein-binding spatial domains. We investigated the impact of PAMAM grafting on the immobilization efficiency of bovine serum albumin (BSA) and mouse immunoglobulin G (IgG). Experimental results demonstrated that PAMAM grafting enhanced the protein immobilization capacity from 11.5 to 33.5 mg/g for BSA and from 8.3 to 19.2 mg/g for IgG, representing 2.9-fold and 2.3-fold improvements, respectively. The SNR improvement was evaluated by using a CLIA-based detection system for the creatine kinase-MB (CK-MB) biomarker. PAMAM grafting achieved 7.21-fold and 4.79-fold improvements in low-to-background and high-to-background ratios and reduced the limits of detection (LOD) from 52.58 to 7.73 pg/mL, respectively, and the optimized LOD fully meets the clinical sensitivity requirements for detecting CK-MB. This work demonstrates that grafting three-dimensional PAMAM dendrimer effectively enhances protein immobilization on magnetic beads, significantly improving CLIA SNR, thereby providing a novel strategy for optimizing immunoassay performance.

Magnetic polymer microspheres have attracted significant attention due to their wide applications in bioanalysis. However, achieving stable and controllable magnetic functionalization remains a critical challenge. Here, covalent layer-by-layer (LBL) self-assembly technique was first applied to the magnetic functionalization of polymer microspheres, preparing P(GMA-co-tBMA)@(Fe₃O₄@APTES/Fe₃O₄@GPTMS)_n (PG@(FeA/FeG)_n) microspheres with controllable magnetic content, suppressed detachment of magnetic particles, and surface functionalization. The alternating loading of Fe₃O₄@APTES nanoparticles and Fe₃O₄@GPTMS nanoparticles onto the porous P(GMA-co-tBMA) microsphere templates was achieved through covalent bonds formed between amino groups and epoxy groups. The results indicated that the loading capacity of magnetic particles in a single-layer assembly on the porous microspheres reached its upper limit when the mass ratio ω (MFe₃O₄@APTES/M_{P(GMA-co-tBMA)}) was 0.05:1, at which point the saturation magnetization value of PG@(FeA/FeG)₁ microspheres was 3.00 emu/g. PG@(FeA/FeG)_n microspheres were prepared under this condition, and their saturation magnetization value were proportionally with the count of layers, reaching 13.90 emu/g at n = 7. Compared to electrostatic self-assembly, the covalent self-assembly strategy reduced magnetic leakage by approximately 83.4%. PGMA was coated onto magnetic PG@(FeA/FeG)₃ microspheres utilizing the amino groups on their surface, and subsequent surface carboxylation was developed. Finally, the carboxylated magnetic microspheres were employed as carriers for chemiluminescence immunoassay to detect creatine kinase-MB (CKMB), a biomarker for acute myocardial infarction (AMI), and exhibited higher chemiluminescence intensity compared to commercially available magnetic beads from JSR Corporation. This method provides a novel approach for achieving stable, controllable, and facile loading of other metals and their compounds, organic compounds, and biomolecules onto polymer substrate.

As one of the key diagnostic methods for detecting biomarkers and antigen-antibody interactions, the luminescent oxygen channel immunoassay (LOCI) has been widely applied in bioanalysis and other fields. In the context of LOCI, the performance of the prepared donor polystyrene (PS) microspheres significantly impacts the detection signal values. In this study, an attempt was made to synthesize PS microspheres via one-step polymerization of styrene with an amphiphilic monomer (PEOOH), followed by swelling the silicon phthalocyanine photosensitizer into the PS microspheres, resulting in the functionalization of the PS microspheres with polyethylene glycol segments. The chemical stability and water solubility of polyethylene glycol (PEG) make it a versatile surface modification material while also inhibiting nonspecific protein adsorption. Results indicated that with increasing PEOOH content, the nonspecific protein adsorption of the resulting PS microspheres reduced, with the adsorption ability for BSA decreasing from 26.8 to 1.3 mg/g, approximately decreasing by 95.2%. Furthermore, the results demonstrated that PS microspheres prepared with 6% PEOOH exhibited a maximum signal-to-noise ratio (S/N) (approximately 28.7), nearly 14 times higher than PS microspheres without PEOOH (approximately 2.1). The analytical performance of the system for detecting staphylococcal enterotoxin B (SEB) revealed a detection limit of 0.1 ng/mL and a linear concentration range of 0.1 to 50 ng/mL for the donor PS microspheres (6% PEOOH). The synthesized donor PS microspheres exhibit a uniform particle size and stable signals, making them effective LOCI microcarriers. These properties facilitate a deeper understanding of molecular interactions and signal transduction mechanisms within biological systems.

This study aims to improve the signal-to-noise ratio (SNR) of chemiluminescence immunoassay (CLIA) by increasing the amount of protein immobilized on the surface of the magnetic bead (MB). Proteins are macromolecules with three-dimensional structures, and merely increasing the density of functional groups on the two-dimensional surface of the MB cannot significantly enhance protein immobilization. Therefore, we grafted spatially extended functional polymer to not only increase the density of functional groups on the MB surface but also expand their distribution in three-dimensional space, ultimately increasing protein immobilization. We synthesized poly(sodium methacrylate) (P-COONa) using atom transfer radical polymerization (ATRP) and examined its grafting density and behavior on the MB surface via nuclear magnetic resonance (NMR). Dynamic light scattering (DLS) results showed that grafting P-COONa increased the hydrodynamic radius of MBs, indicating its spatial extension. Next, we investigated the effect of P-COONa grafting on the immobilization of bovine serum albumin (BSA). Experimental results demonstrated that P-COONa grafting increased BSA immobilization from 19.9 to 42.92 mg/g. Finally, we evaluated the impact of P-COONa grafting on the SNR by detecting the D-dimer biomarker using CLIA. The results indicated that P-COONa grafting increased the low-value-to-background and high-value-to-background ratios by 4.21× and 17.17×, respectively. This study demonstrates that grafting spatially extended P-COONa increases protein immobilization on the MB surface, significantly improving the SNR of CLIA.