Chemical Reviews最新文献

Functionally graded surfaces and materials, featuring spatial variations in terms of composition, structure, and other properties across distance, have emerged as powerful platforms for mimicking native tissue architectures and enabling a wide range of biomedical applications. This review aims to provide a comprehensive overview of their fabrication methods and biomedical applications. We begin by introducing the concept of gradients and their inherent biological relevance in nature. With a distinct focus on either surfaces or materials, we then discuss the fabrication methods and characterization techniques capable of controlling the graded profiles. Importantly, representative examples are provided to highlight how engineered gradients regulate specific cellular responses and functionalities in biomedical contexts. Despite significant progress, challenges remain in translating laboratory-scale fabrication to clinical use, such as ensuring good reproducibility and scalability. At the end, we discuss how computational modeling and artificial intelligence offer new opportunities to address these challenges. We hope this review provides a framework for advancing the development of next-generation functionally graded surfaces and materials toward diverse biomedical applications.

Microbubbles (MBs) have served as ultrasound (US) contrast agents for over 30 years in cardiac imaging and liver tumor characterization. Moreover, in recent years, molecularly targeted MBs are currently under clinical evaluation for oncological and inflammatory diseases. Beyond diagnostics, MBs are gaining attention as therapeutic tools, leveraging their strong acoustic properties for US-mediated drug delivery, sonopermeation of biological barriers (i.e., the blood–brain barrier), and targeted thrombolysis. Loading MB shells with magnetic or optical functionalities allows therapy monitoring using magnetic resonance or photoacoustic imaging, aligning with recent multimodal advances in (pre)clinical device developments. Therefore, this review summarizes and critically assesses advances in the use of multifunctional MBs for biomedical applications. A comprehensive overview of existing MB formulations is provided, analyzing the primary types of functional agents incorporated, including small molecules, nanomaterials, and targeting ligands, as well as the conjugation and functionalization strategies involved in constructing next-generation MBs. Current trends in multifunctional MBs for imaging and therapy are critically evaluated, along with the challenges in their clinical translation. Overall, this review highlights the potential of multifunctional MBs to address unmet biomedical needs that plain additives cannot fulfill, and it showcases promising future directions for the diagnostic and therapeutic use of next-generation MB formulations.

Agriculture is under pressure to provide food for a growing population and the feedstock required to drive the bioeconomy. Methods to breed and genetically modify plants are inadequate to keep pace. When engineering crops, traits are painstakingly introduced into plants one-at-a-time, combine unpredictably, and are continuously expressed. Synthetic biology is changing these paradigms with new genome construction tools, computer aided design (CAD), and artificial intelligence (AI). “Smart plants” contain circuits that respond to environmental change, alter morphology, or respond to threats. Further, the plant and associated microbes (fungi, bacteria, archaea) are now being viewed by genetic engineers as a holistic system. Historically, plant health has been enhanced by many natural and laboratory-evolved soil microbes marketed to enhance growth or provide nutrients, or pest/stress resistance. Synthetic biology has expanded the number of species that can be engineered, increased the complexity of engineered functions, controlled environmental release, and can assemble stable consortia. New CAD tools will manage genetic engineering projects spanning multiple plant genomes (nucleus, chloroplast, mitochondrion) and the thousands of genomes of associated bacteria/fungi. This review covers advanced genetic engineering techniques to drive the next agricultural revolution, as well as push plant engineering into new realms for manufacturing, infrastructure, sensing, and remediation.

The pursuit of high-energy-density batteries that tolerate extreme conditions and use earth-abundant elements is fundamentally constrained by the slow pace of materials innovation. By enabling broad compositional tuning and property optimization, the high-entropy strategy defines a new design paradigm for battery materials chemistry. High-entropy concepts were applied to various battery components, ranging from solids to liquids. However, this field is still in its infancy, requiring substantial groundwork to address the ambiguous definitions, unclear or even contradictory performance-enhancement mechanisms, and a lack of rational design principles. Therefore, a comprehensive review summarizing current issues and future developments across the entire battery system is urgently needed. It begins with the fundamental principles of high-entropy materials chemistry (HEMC) and their applications in batteries, followed by a systematic discussion of entropy-driven mechanisms in both solid and liquid phases. An integrated perspective on the challenges and opportunities across the full battery system is presented. Furthermore, we highlight recent advances in synthesis and characterization techniques, multiscale computation, and the integration of artificial intelligence in accelerating the development of HEMC in batteries.

Solid-state batteries promise higher energy density and safety, but simply replacing liquid electrolytes with solid ones does not guarantee improvement over lithium-ion batteries. Achieving higher energy density requires high active material (AM) content and high AM loading, which is hindered by solid-state electrolyte’s (SSE’s) low ionic conductivity, poor AM–SSE interfaces, sluggish Li⁺ transport, and processing challenges. In this review paper, the fundamental mechanisms of ion transport in SSEs and composite electrodes are comprehensively reviewed and discussed. It is found that reducing the internal ionic resistance and the diffusion impedance of AM are effective ways to boost the effective current density of the composite electrode and decrease the overpotential of SSBs to enhance the delivered energy. The mechanisms and advanced techniques for measuring both ionic and electronic conductivities, as well as directly observing the ionic conductivity and diffusion of the composite electrodes are summarized. Furthermore, the strategies for improving ion diffusion within the AM, and enhancing ion transfer across the high AM content composite electrode are discussed. In addition, the challenges associated with industrialization of composite electrodes and potential solutions are discussed. This review paper summarizes the key aspects of ion transport in the solid-state composite electrode, aiming to support the design of ultrahigh energy density SSBs.

Thermoset polymers have desirable properties, such as excellent thermal and mechanical stability, but their covalent cross-links typically prevent repair or recycling. By enabling and controlling dynamic exchange reactions within polymer networks, their covalent bonds rearrange and allow the polymer to be reshaped. These viscoelastic polymer networks, now known as covalent adaptable networks (CANs), are an important frontier for improving plastic circularity, as well as for designing valuable stimuli-responsive materials. This Review describes the history of CANs, dating back to the early days of polymer science, and the evolution of their classification and nomenclature. A comprehensive survey of dynamic reactions and linkage chemistries is provided, as well as methods to characterize and reprocess CANs. Beyond straightforward reprocessing, many advanced applications of CANs and their composites are now emerging. Finally, we provide perspective on how the development of new chemistries, strategies to control stimuli-responsive bond exchange and mechanical properties, and a deep understanding of exchange reactions will advance this field toward scalable, sustainable, and high-value materials.

Bionic structured milli-fluidics, as an emerging interdisciplinary subject of fluidics and biomimetics, is fast developing due to its diverse applications in various fields such as biomedical detection, material synthesis, water collection, etc. Researchers have mimicked natural surfaces with unique milli-structures like Araucaria leaves and cactus to achieve droplet manipulation for milli-fluidics. Furthermore, wetting gradient surfaces and external stimuli, including light, thermal, electricity, magnetism, and acoustics, have been utilized to create energy gradients and enhance bionic structured milli-fluidic performance. We comprehensively review the passive methods (bioinspired structures) and active strategies (external fields) for milli-fluidics. Moreover, the relationships between Laplace pressure, wettability gradients, and milli-fluidics are discussed first. Then, the advantages and disadvantages of different external stimuli are examined, and future directions for the field are suggested as well. Finally, a brief overview of key issues, current obstacles, and emerging trends of bionic structured milli-fluidics is presented, aiming to provide guidance for future research endeavors.

The (bio)chemical reaction dynamics of polymers and supramolecular systems are intimately related to the conformational dynamics of these systems. A relatively new approach to studying the structure and structural dynamics of large (bio)molecular systems in aqueous solution is the measurement of the dynamics of the solvating water molecules. A suitable technique to measure the reorientation dynamics of solvating water molecules is polarization-resolved femtosecond mid-infrared pump–probe spectroscopy (PR-fs-IR). PR-fs-IR measures the full orientation correlation function of the water molecules in solution and is capable of distinguishing water molecules that are bulk-like and that are in direct (solvation) contact with hydrophobic, hydrophilic, and ionic groups of the solute. In this review, we show how the measurement of the reorientation of the solvating water can provide information on the structures of micelles, water–oil emulsions, and large polymers. We also discuss how the measurement of the water reorientation provides information on the origin of the temperature sensitivity of hydrogels and the folding of proteins. We compare the results obtained with PR-fs-IR with the results obtained with other experimental techniques, such as nuclear magnetic resonance (NMR), terahertz Fourier-transform infrared (THz-FTIR), Raman-multivariate curve resolution (Raman-MCR), dielectric relaxation (DR), and time-resolved optical Kerr effect (OKE) spectroscopy.

All-inorganic perovskites have gained significant attention in recent years due to their superior thermal and environmental stability compared to their organic–inorganic hybrid counterparts. These materials, typically represented by CsPbX₃, exhibit excellent optoelectronic properties such as high absorption coefficients, suitable bandgaps, and long carrier diffusion lengths, making them promising candidates for next-generation photovoltaic applications. This review provides a comprehensive overview of the structural characteristics, phase behavior, and optoelectronic properties of inorganic perovskites. Various fabrication techniques, including solution processing, vacuum deposition, and hybrid approaches, are discussed with respect to their influence on film quality and device performance. Key issues, including phase instability and defect formation, are discussed, together with recent advances in composition engineering, additive optimization, and interfacial modification. In addition, the environmental and health concerns associated with lead usage have driven the development of lead-free alternatives, such as bismuth-, tin-, or antimony-based perovskites. This review also summarizes progress in the fabrication of large-area and flexible IPSCs and explores their potential applications under extreme environmental conditions. Finally, the remaining challenges and future opportunities for advancing high-performance all-inorganic perovskite photovoltaics are highlighted.