Chemical Reviews最新文献

The chemistry and physics of soft matter interfaces, especially aqueous-organic interfaces, are centrally important to many areas of science and technology. Often, the thermodynamics, kinetics, and selectivity of reactions are modified at interfaces. Here, we review the electrostatics and hydration at charged monolayers on water and their influence on interfacial chemical equilibria. First, we provide an understanding of interfaces as a conceptual continuation of the solvation shell of small molecules, along with recent relevant experimental work. Then, we provide a summary of models for describing the electrostatics of aqueous interfaces. While we will discuss a range of new developments, our focus will be on systems where the electrostatics of the surface is controllable by the choice of relatively simple insoluble surfactants. New insights into the molecular structure of the double layer, with particular attention on the knowledge gained from spectroscopy will be reviewed. Our approach is to familiarize the reader with simple models, followed by discussion of models with further complexity for explaining interfacial phenomena. Experiments that test the limits of such models will also be discussed. Finally, we will provide an outlook on engineering the interfacial environment for tailored reactivity, along with the anticipated experimental advancements and potentials impacts.

Genetic code expansion (GCE) in mammalian cells has emerged as a powerful technology for investigating and engineering protein function. This method allows for the precise incorporation of a rapidly growing toolbox of noncanonical amino acids (ncAAs) into predefined sites of target proteins expressed in living cells. Due to the minimal size of these genetically encoded ncAAs, the wide range of functionalities they provide, and the ability to introduce them freely at virtually any site of any protein by simple mutagenesis, this technology holds immense potential for probing the complex biology of mammalian cells and engineering next-generation biotherapeutics. In this review, we provide an overview of the underlying machinery that enables ncAA mutagenesis in mammalian cells and how these are developed. We have also compiled an updated list of ncAAs that have been successfully incorporated into proteins in mammalian cells. Finally, we provide our perspectives on the current challenges that need to be addressed to fully harness the potential of this technology.

Cell-surface receptors are vital for controlling numerous cellular processes with their dysregulation being linked to disease states. Therefore, it is necessary to develop tools to study receptors and the signaling pathways they control. This Review broadly describes molecular approaches that enable 1) the visualization of receptors to determine their localization and distribution; 2) sensing receptor activation with permanent readouts as well as readouts in real time; and 3) perturbing receptor activity and mimicking receptor-controlled processes to learn more about these processes. Together, these tools have provided valuable insight into fundamental receptor biology and helped to characterize therapeutics that target receptors.

Electric fields generated by protein scaffolds are crucial in enzymatic catalysis. This review surveys theoretical approaches for detecting, analyzing, and comparing electric fields, electrostatic potentials, and their effects on the charge density within enzyme active sites. Pioneering methods like the empirical valence bond approach rely on evaluating ionic and covalent resonance forms influenced by the field. Strategies employing polarizable force fields also facilitate field detection. The vibrational Stark effect connects computational simulations to experimental Stark spectroscopy, enabling direct comparisons. We highlight how protein dynamics induce fluctuations in local fields, influencing enzyme activity. Recent techniques assess electric fields throughout the active site volume rather than only at specific bonds, and machine learning helps relate these global fields to reactivity. Quantum theory of atoms in molecules captures the entire electron density landscape, providing a chemically intuitive perspective on field-driven catalysis. Overall, these methodologies show protein-generated fields are highly dynamic and heterogeneous, and understanding both aspects is critical for elucidating enzyme mechanisms. This holistic view empowers rational enzyme engineering by tuning electric fields, promising new avenues in drug design, biocatalysis, and industrial applications. Future directions include incorporating electric fields as explicit design targets to enhance catalytic performance and biochemical functionalities.

Neuromorphic electronics are inspired by the human brain’s compact, energy-efficient nature and its parallel-processing capabilities. Beyond the brain, the entire human nervous system, with its hierarchical structure, efficiently preprocesses complex sensory information to support high-level neural functions such as perception and memory. Emulating these biological processes, artificial nerve electronics have been developed to replicate the energy-efficient preprocessing observed in human nerves. These systems integrate sensors, artificial neurons, artificial synapses, and actuators to mimic sensory and motor functions, surpassing conventional circuits in sensor-integrated electronics. Organic synaptic transistors (OSTs) are key components in constructing artificial nerves, offering tunable synaptic plasticity for complex sensory processing and the mechanical flexibility required for applications in soft robotics and bioelectronics. Compared to traditional sensor-integrated electronics, early implementations of organic artificial nerves (OANs) incorporating OSTs have demonstrated a higher signal-to-noise ratio, lower power consumption, and simpler circuit designs along with on-device processing capabilities and precise control of actuators and biological limbs, driving progress in neuromorphic robotics and bioelectronics. This paper reviews the materials, device engineering, and system integration of the OAN design, highlights recent advancements in neuromorphic robotics and bioelectronics utilizing the OANs, and discusses current challenges and future research directions.

The cation−π interaction is an important noncovalent binding force that impacts all areas of chemistry and biology. Extensive computational and gas phase experimental studies have established the potential strength and the essential nature of the interaction. Previous reviews have emphasized studies of model systems and a variety of biological examples. This work includes discussion of those areas but emphasizes other areas that are perhaps less well appreciated. These include the novel cation−π binding ability of alkali metals in water; the application of the cation−π interaction to organic synthesis and chemical biology; cooperative behaviors of multiple cation−π interactions, including adhesive proteins from mussels and similar organisms and the formation and modulation of biomolecular condensates (phase separation); and cation−π interactions involved in recognizing DNA/RNA.