Chemical Reviews

Investigating protein-protein interactions is crucial for understanding cellular biological processes because proteins often function within molecular complexes rather than in isolation. While experimental and computational methods have provided valuable insights into these interactions, they often overlook a critical factor: the crowded cellular environment. This environment significantly impacts protein behavior, including structural stability, diffusion, and ultimately the nature of binding. In this review, we discuss theoretical and computational approaches that allow the modeling of biological systems to guide and complement experiments and can thus significantly advance the investigation, and possibly the predictions, of protein-protein interactions in the crowded environment of cell cytoplasm...

All-perovskite tandem solar cells are attracting considerable interest in photovoltaics research, owing to their potential to surpass the theoretical efficiency limit of single-junction cells, in a cost-effective sustainable manner. Thanks to the bandgap-bowing effect, mixed tin-lead (Sn-Pb) perovskites possess a close to ideal narrow bandgap for constructing tandem cells, matched with wide-bandgap neat lead-based counterparts. The performance of all-perovskite tandems, however, has yet to reach its efficiency potential...

Polyesters carrying polar main-chain ester linkages exhibit distinct material properties for diverse applications and thus play an important role in today's plastics economy. It is anticipated that they will play an even greater role in tomorrow's circular plastics economy that focuses on sustainability, thanks to the abundant availability of their biosourced building blocks and the presence of the main-chain ester bonds that can be chemically or biologically cleaved on demand by multiple methods and thus bring about more desired end-of-life plastic waste management options...

Fluorescence imaging is one of the most promising approaches to achieve intraoperative assessment of the tumor/normal tissue margins during cancer surgery. This is critical to improve the patients' prognosis, and therefore various molecular fluorescence imaging probes have been developed for the identification of cancer lesions during surgery. Among them, "activatable" fluorescence probes that react with cancer-specific biomarker enzymes to generate fluorescence signals have great potential for high-contrast cancer imaging due to their low background fluorescence and high signal amplification by enzymatic turnover...

CO2 electrolyzers have progressed rapidly in energy efficiency and catalyst selectivity toward valuable chemical feedstocks and fuels, such as syngas, ethylene, ethanol, and methane. However, each component within these complex systems influences the overall performance, and the further advances needed to realize commercialization will require an approach that considers the whole process, with the electrochemical cell at the center. Beyond the cell boundaries, the electrolyzer must integrate with upstream CO2 feeds and downstream separation processes in a way that minimizes overall product energy intensity and presents viable use cases...

Electrocatalytic water splitting driven by renewable electricity has been recognized as a promising approach for green hydrogen production. Different from conventional strategies in developing electrocatalysts for the two half-reactions of water splitting (e.g., the hydrogen and oxygen evolution reactions, HER and OER) separately, there has been a growing interest in designing and developing bifunctional electrocatalysts, which are able to catalyze both the HER and OER. In addition, considering the high overpotentials required for OER while limited value of the produced oxygen, there is another rapidly growing interest in exploring alternative oxidation reactions to replace OER for hybrid water splitting toward energy-efficient hydrogen generation...

The breadth and importance of polymerized ionic liquids (PILs) are steadily expanding, and this review updates advances and trends in syntheses, properties, and applications over the past five to six years. We begin with an historical overview of the genesis and growth of the PIL field as a subset of materials science. The genesis of ionic liquids (ILs) over nano to meso length-scales exhibiting 0D, 1D, 2D, and 3D topologies defines colloidal ionic liquids, CILs, which compose a subclass of PILs and provide a synthetic bridge between IL monomers (ILMs) and micro to macro-scale PIL materials...

Hydrogen sulfide (H2 S) is not only a well-established toxic gas but also an important small molecule bioregulator in all kingdoms of life. In contemporary biology, H2 S is often classified as a "gasotransmitter," meaning that it is an endogenously produced membrane permeable gas that carries out essential cellular processes. Fluorescent probes for H2 S and related reactive sulfur species (RSS) detection provide an important cornerstone for investigating the multifaceted roles of these important small molecules in complex biological systems...

Zeolite catalysts and adsorbents have been an integral part of many commercial processes and are projected to play a significant role in emerging technologies to address the changing energy and environmental landscapes. The ability to rationally design zeolites with tailored properties relies on a fundamental understanding of crystallization pathways to strategically manipulate processes of nucleation and growth. The complexity of zeolite growth media engenders a diversity of crystallization mechanisms that can manifest at different synthesis stages...

In recent years, the issues of global warming and CO2 emission reduction have garnered increasing global attention. In the 21st Conference of the Parties (convened in Paris in 2015), 179 nations and the European Union signed a pivotal agreement to limit the global temperature increase of this century to well below 2 K above preindustrial levels. To fulfill this objective, extensive research has been conducted to use renewable energy sources as potential replacements for traditional fossil fuels. Among them, the production of hydrocarbon transportation fuels from CO2 -neutral and renewable biomass has proven to be a particularly promising solution due to its compatibility with existing infrastructure...

The structure of catalysts determines the performance of catalytic processes. Intrinsically, the electronic and geometric structures influence the interaction between active species and the surface of the catalyst, which subsequently regulates the adsorption, reaction, and desorption behaviors. In recent decades, the development of catalysts with complex structures, including bulk, interfacial, encapsulated, and atomically dispersed structures, can potentially affect the electronic and geometric structures of catalysts and lead to further control of the transport and reaction of molecules...

Carbon dioxide (CO2 ) has long been recognized as an ideal C1 feedstock comonomer for producing sustainable materials because it is renewable, abundant, and cost-effective. However, activating CO2 presents a significant challenge because it is highly oxidized and stable. A CO2 /butadiene-derived δ-valerolactone (EVP), generated via palladium-catalyzed telomerization between CO2 and butadiene, has emerged as an attractive intermediate for producing sustainable copolymers from CO2 and butadiene. Owing to the presence of two active carbon-carbon double bonds and a lactone unit, EVP serves as a versatile intermediate for creating sustainable copolymers with a CO2 content of up to 29 wt % (33 mol %)...

The renewable energy industry demands rechargeable batteries that can be manufactured at low cost using abundant resources while offering high energy density, good safety, wide operating temperature windows, and long lifespans. Utilizing fluorine chemistry to redesign battery configurations/components is considered a critical strategy to fulfill these requirements due to the natural abundance, robust bond strength, and extraordinary electronegativity of fluorine and the high free energy of fluoride formation, which enables the fluorinated components with cost effectiveness, nonflammability, and intrinsic stability...

Fluorescent carbon nanomaterials have broadly useful chemical and photophysical attributes that are conducive to applications in biology. In this review, we focus on materials whose photophysics allow for the use of these materials in biomedical and environmental applications, with emphasis on imaging, biosensing, and cargo delivery. The review focuses primarily on graphitic carbon nanomaterials including graphene and its derivatives, carbon nanotubes, as well as carbon dots and carbon nanohoops. Recent advances in and future prospects of these fields are discussed at depth, and where appropriate, references to reviews pertaining to older literature are provided...

It is now generally accepted that macromolecules do not act in isolation but "live" in a crowded environment, that is, an environment populated by numerous different molecules. The field of molecular crowding has its origins in the far 80s but became accepted only by the end of the 90s. In the present issue, we discuss various aspects that are influenced by crowding and need to consider its effects. This Review is meant as an introduction to the theme and an analysis of the evolution of the crowding concept through time from colloidal and polymer physics to a more biological perspective...

Magnetic ionic liquids (MILs) stand out as a remarkable subclass of ionic liquids (ILs), combining the desirable features of traditional ILs with the unique ability to respond to external magnetic fields. The incorporation of paramagnetic species into their structures endows them with additional attractive features, including thermochromic behavior and luminescence. These exceptional properties position MILs as highly promising materials for diverse applications, such as gas capture, DNA extractions, and sensing technologies...

The human body continuously emits physiological and psychological information from head to toe. Wearable electronics capable of noninvasively and accurately digitizing this information without compromising user comfort or mobility have the potential to revolutionize telemedicine, mobile health, and both human-machine or human-metaverse interactions. However, state-of-the-art wearable electronics face limitations regarding wearability and functionality due to the mechanical incompatibility between conventional rigid, planar electronics and soft, curvy human skin surfaces...

Separation and reaction processes are key components employed in the modern chemical industry, and the former accounts for the majority of the energy consumption therein. In particular, hydrocarbon separation and purification processes, such as aromatics extraction, desulfurization, and denitrification, are challenging in petroleum refinement, an industrial cornerstone that provides raw materials for products used in human activities. The major technical shortcomings in solvent extraction are volatile solvent loss, product entrainment leading to secondary pollution, low separation efficiency, and high regeneration energy consumption due to the use of traditional organic solvents with high boiling points as extraction agents...

Proteins are highly labile molecules, thus requiring the presence of appropriate solvents and excipients in their liquid milieu to keep their stability and biological activity. In this field, ionic liquids (ILs) have gained momentum in the past years, with a relevant number of works reporting their successful use to dissolve, stabilize, extract, and purify proteins. Different approaches in protein-IL systems have been reported, namely, proteins dissolved in ( i ) neat ILs, ( ii ) ILs as co-solvents, ( iii ) ILs as adjuvants, ( iv ) ILs as surfactants, ( v ) ILs as phase-forming components of aqueous biphasic systems, and ( vi ) IL-polymer-protein/peptide conjugates...

The immune system's complexity and ongoing evolutionary struggle against deleterious pathogens underscore the value of vaccination technologies, which have been bolstering human immunity for over two centuries. Despite noteworthy advancements over these 200 years, three areas remain recalcitrant to improvement owing to the environmental instability of the biomolecules used in vaccines─the challenges of formulating them into controlled release systems, their need for constant refrigeration to avoid loss of efficacy, and the requirement that they be delivered via needle owing to gastrointestinal incompatibility...