Materials Chemistry Frontiers最新文献

Persistent organic radicals are attractive building blocks for constructing functional metal-organic frameworks owing to their unique electronic, magnetic, and optical properties. However, tuning the ratio of open- and closed-shell organic linkers within a single metal-organic radical framework (MORF) has remained unexplored. Herein, we report the synthesis of multivariate MORFs incorporating perchlorotriphenylmethyl tricarboxylate (PTMTC) linkers in both their radical (PTMTC^R) and non-radical (PTMTC^NR) forms within the same crystalline structure. By simply varying the ratio of the starting PTMTC^R and PTMTC^NR ligands, we obtained three different multivariate MORFs (MORF-40, MORF-60, and MORF-80) with radical contents of ca. 40, 60, and 80%, respectively, while preserving the same framework architecture. Single-crystal X-ray diffraction directly reveals the statistical co-occupancy of PTMTC^R and PTMTC^NR linkers at the same crystallographic site in MORF-40, providing a rare example of a crystalline framework containing both open- and closed-shell organic building blocks. Complementary Raman spectroscopy, electron paramagnetic resonance, fluorescence microscopy, and Kelvin probe force microscopy confirm the systematic variation in radical content across the series. This ability to tune the radical content without altering the underlying framework architecture provides a versatile strategy for modulating the electronic, optical, and magnetic properties of multivariate metal-organic radical frameworks.

[This corrects the article DOI: 10.1039/D4QM00632A.].

The Materials Chemistry Frontiers Emerging Investigators Series highlights the best research being conducted by scientists in the early stages of their independent careers. This profile features the emerging investigators contributing to this series in 2025. Each contributor was recommended as carrying out work with the potential to influence future directions in materials chemistry. Congratulations to all the researchers, we hope you enjoy reading their work.

The ongoing water crisis requires the development of functional materials that can tap into the atmospheric water reservoir. Sorption-based atmospheric water harvesting using porous materials presents a promising solution. Many porous, crystalline networks have been investigated thus far, however, simple, hydrophilic polymers may prove a promising branch of sorbents for versatile water capture. Here, poly-PETMP is produced via thiol self-condensation in a bulk synthesis at room temperature in the absence of organic solvents. The resulting poly-PETMP is then loaded with calcium chloride to yield a sorbent with an impressive water sorption capacity of 1.34 g g^-1 at 90% relative humidity (RH) and 0.29 g g^-1 at 30% RH, while retaining a consistent performance over repeated sorption/desorption cycles.

The catalytic upgrading of biomass-derived compounds in zeolites such as ZSM-5 remains poorly understood at a molecular level, particularly with respect to adsorption and confinement of trapped species. Guaiacol, a key product of catalytic fast pyrolysis of lignocellulosic biomass, exhibits complex behaviour in ZSM-5, yet direct experimental evidence of zeolite-guaiacol host-guest interactions has been lacking. Here, we directly identify distinct in-pore and ex-pore guaiacol species in adsorbed ZSM-5 and trapped unreacted species following catalytic upgrading. These species are distinguished using ¹H and ¹³C magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy differentiating through characteristic differences in chemical shifts, linewidths and relaxation data observables, and are complemented by thermogravimetric analysis coupled with mass spectrometry (TGA-MS) to reveal differences in their desorption profiles. Furthermore, ¹⁷O isotopic enrichment of the ZSM-5 framework enables two-dimensional ¹H-¹⁷O dipolar heteronuclear multiple-quantum coherence (D-HMQC) NMR experiments, providing molecular-level insight into the through-space interactions between guaiacol and framework oxygen atoms. Together, these results suggest the location, confinement and reactivity of guaiacol within ZSM-5 pores, offering atomic-scale observations for the rational design of future zeolite catalysts for sustainable fuel production.

Correction for ‘From lab to tap: 2D material innovations in detection and elimination of waterborne pathogens’ by Soumyanti Panda et al., Mater. Chem. Front., 2026, https://doi.org/10.1039/d5qm00758e.

Covalent organic frameworks (COFs) possess infinitely extended large π-conjugated structures, which provide tremendous potential for enhancing the nonlinear optical (NLO) properties of materials. Herein, we have successfully constructed a series of benzotrithiophene-based covalent organic framework powders (BT-COFs) via Schiff-base condensation reaction. Furthermore, high-quality BT-COF thin films were fabricated by the in-situ growth method for the investigation of third-order NLO properties. The nonlinear optical performance parameters of BT-COF thin films were obtained through Z-scan measurements. Among them, BT-PT exhibits the highest nonlinear response, with a maximum nonlinear absorption coefficient (β) of −3.44 × 10⁻⁶ m W⁻¹, a maximum nonlinear refractive index (n₂) of 3.59 × 10⁻¹³ m² W⁻¹, and a maximum third-order nonlinear susceptibility (|χ⁽³⁾|) of 10.11 × 10⁻⁷ esu. This study regulates the electronic structure and conjugation degree of COFs by introducing heteroatoms, reveals the effective role of heteroatom doping in enhancing the third-order NLO properties of COFs, and provides a new idea for designing high-performance COFs NLO materials.

The coupled acoustic-thermal loads in high-temperature power systems pose significant risks to both personnel and equipment, demanding protective materials with combined broadband sound absorption and thermal insulation. Inspired by the hierarchical layered structure of silkworm cocoons for protecting the pupa, gradient mullite nanofibrous aerogels were fabricated through humidity-controlled electrospinning, in which a programmed decrease in ambient humidity enabled the gradual evolution of the fibrous pore structure. As the humidity decreased, the bulk density decreased from 19.2 to 6.4 mg cm⁻³, while the mean pore diameter increased from 2.89 to 7.24 µm. Benefiting from this gradient pore architecture, the material exhibited an α value greater than 0.8 within the 0.8 to 6 kHz frequency range, with an average α and NRC reaching 0.86 and 0.61, respectively. At room temperature, its thermal conductivity was measured to be as low as 0.024 W m⁻¹ K⁻¹, and it exhibited excellent stability under both high-temperature and cryogenic conditions. These results demonstrate that humidity-controlled electrospinning provides an effective and scalable route for constructing gradient ceramic fibrous materials for high-temperature acoustic-thermal protection.

Poly(lactic acid) (PLA) is one of the most widely used biodegradable polymers for tissue engineering due to its biocompatibility, processability, and favorable mechanical strength. However, its intrinsic brittleness, hydrophobicity, and limited control over degradation and biological signaling require extensive modification. This review summarizes recent advances in polymer-based modification strategies that tailor PLA for tissue engineering applications. We systematically discuss physical blending, chemical copolymerization, and bulk and surface grafting, emphasizing how each approach regulates mechanical behaviour, degradation kinetics, surface bioactivity, and process compatibility across films, fibres, and three-dimensional scaffolds. Particularly, we discuss emerging liquid crystalline modification strategies that introduce intrinsic molecular order beyond conventional isotropic composites. By comparing structure–property–function relationships of molecularly programmed, multifunctional PLA platforms across various modification routes and fabrication methods, this review highlights current limitations and outlines future opportunities capable of meeting the complex demands of tissue engineering applications.

The tumor microenvironment (TME) is a dynamic biochemical environment that controls how tumors grow, spread, and respond to treatment. Endogenous TME characteristics, including acidity, redox imbalance, enzyme dysregulation, hypoxia, and abnormal nucleic acid expression, constitute a multidimensional signaling network that encodes disease-specific information. Using these signals to selectively activate therapies has become a major idea in precision nanomedicine. Inorganic nanomaterials provide a versatile platform for decoding signals and transforming them into programmable therapeutic responses due to their structural robustness, adjustable physicochemical properties, and inherent catalytic and imaging capabilities. Nonetheless, the majority of contemporary systems are constrained by single-signal dependence, insufficient specificity, and inadequate adaptability to tumor heterogeneity. In this review, we characterize TME-responsive nanomedicines as signal-processing systems that include signal encoding, transduction, and functional output. We summarize the molecular origins of key endogenous signals and corresponding material design strategies, such as bond cleavage, physicochemical transformation, catalytic activation, and structural reconfiguration. We also describe how single-stimulus designs have changed into multi-stimuli logic-gated nanoplatforms that can make programmable therapeutic decisions. Lastly, we discuss the main problems and future paths for inorganic nanomedicines that can adapt, are based on logic, and can be used in clinical settings.