Chemical Reviews最新文献

When aiming at designing performant catalysts for existingor novel(sustainable) reactions, a wide variety of methodologies can be adopted,turning catalyst design into a science on its own. However, fundamentalknowledge and clear guidelines for the application of these methodologiesfor catalyst innovation are lacking, impeding truly efficient andadequate catalyst design, with serendipity still playing too importanta role. This review fills this gap by systematically categorizingand reviewing the most relevant methodologies and providing theirfundamentals. Despite the strong benefit from systematically collecteddata incoming from digital laboratories, the main common drawbackremains how to design catalysts truly “out of the box”?While various methodologies can serve more humble purposes (e.g.,fine-tuning catalyst compositions), truly innovative catalyst designcan only be achieved via a knowledge-driven approach, strongly supportedby kinetic models in combination with suitable catalysis informaticstools.

Artificialprosthetic manufacturing is moving toward patient-specificdesign and production, and zirconia-based three-dimensional printingis emerging as a promising approach because of its mechanical propertiesand biocompatibility. Yet the step from laboratory development toclinical use is still limited by the gap between laboratory-scaleprocess optimization and clinically relevant validation of performance,reproducibility, and long-term reliability. This review provides anapplication-oriented overview of zirconia-based photopolymerizationadditive manufacturing for dental, orthopedic, and scaffold applications,discussing relevant functional requirements alongside key processingparameters, postprocessing steps, and quality-critical variables.We outline major bottlenecks, such as optical scattering and slurryrheology during fabrication, as well as defects and dimensional deviationsintroduced during debinding and sintering, and we discuss recent performance-orientedstrategies, including triply periodic minimal surface (TPMS) architecturesand functionally graded additive manufacturing (FGAM) routes. Finally,we highlight the critical requirements for clinical translation, includingqualification-ready process control, lot-to-lot manufacturing consistency,and robust durability validation under clinically relevant conditions.Taken together, these aspects establish a process–defect–performancerelationship, where photopolymerization parameters govern defect evolutionduring debinding and sintering and, ultimately, determine the mechanicalreliability and clinical performance of zirconia-based prostheses.Addressing these challenges will be essential for bridging the gapbetween laboratory-scale demonstrations and the scalable productionof patient-specific zirconia prostheses.

Regarded as one of the most complex membrane proteinfolds, CLCsform a large family of membrane proteins that function as anion channelsand secondary active anion/proton transporters. Despite low sequencesimilarity, available structures are remarkably similar, maintainingthe same inverted topology and fold, with subunits assembled as dimersin wild-type structures. Because of these strong structural features,CLC-ec1, a prokaryotic homologue from E. coli, hasbecome a highly valuable model system for studying membrane proteinfolding and oligomerization assembly. Associating via a membrane-embeddeddimerization interface, the subunits participate in a dynamic equilibriumbetween monomers and dimers in lipid bilayers, enabling investigationof the physical driving forces underlying the formation of stablemembrane complexes. Like soluble protein assembly, studies indicatethat CLC-ec1 dimerization is driven by a solvophobic force arisingfrom the free energy gained by burying lipid bilayer defects. Dimerizationstability is influenced by lipid composition and pH, which, in turn,provide a mechanism for functional regulation through oligomerization.In this review, I provide an overview of how the exploration of CLCfolding and oligomerization advances our understanding of membraneprotein self-assembly in general and the role of oligomerization inregulating function.

Since its inception at the end of the last century, 2D-IRspectroscopyhas undergone continuous development into an established method forstudying the structure, dynamics and intermolecular interactions ofbiomolecules. Thanks to parallel advances in lasers and related technology,2D-IR data sets can now be acquired in minutes, using minimal samplequantities and under physiologically relevant conditions. This progresshas opened the door for 2D-IR spectroscopy to play a role as an analyticaltool, making measurements that characterize samples and inform decisionsin arenas ranging from drug design to biomedical diagnostics. Here,we briefly review the pioneering developments that have brought aboutthis scenario before discussing the current state of the art in analyticalapplications of 2D-IR spectroscopy. We consider the implementationof 2D-IR spectroscopy to measure label free protein structure, biomolecularinteractions and the use of 2D-IR to interrogate complex mixturesand biological tissues. We include strategies that have extended thereach of 2D-IR spectroscopy through advances in measurement sensitivityand data quality and highlight the potential impact that emergingmethods such as machine learning could have on the development of2D-IR. Finally, we look ahead to the challenges and opportunitiesfacing 2D-IR on its path toward a robust and widely used bioanalyticaltool.

Rational design of functional building blocks and precisecontrolover their hierarchical self-assembly form the cornerstones of supramolecularchemistry and materials science. Amphiphilic molecules, with theirinherent hydrophilic–hydrophobic duality, serve as criticalbuilding blocks across several disciplines. Integrating additionalfunctionalities such as π-conjugation and chirality significantlyexpands the design space and utility of common amphiphiles, givingrise to a new class of building blocks: chiral π-amphiphiles.Typically, a synthetic chiral π-amphiphile consists of two functionallydistinct segments, i.e., a hydrophobic π-extended chromophoreand a hydrophilic chiral unit, covalently linked via common chemicallinkers. The integration of chirality, functional π-systems,and amphiphilicity offers distinct advantages, such as chirality-guideddirectional π-stacking and superior chiroptical properties arisingfrom their hierarchical chiral architectures in both organic and aqueousphases. Emerging chiral functions of chiral π-amphiphiles includingcircularly polarized luminescence, chiral recognition and separation,chiral biomedicine, and spin electronics have witnessed groundbreakingprogress in recent years, which we believe will contribute to thedevelopment of novel chiral materials through molecular self-assemblyapproaches. This review systematically summarizes and discusses thedefinition, molecular design strategies, classification, nanostructures,applications, and future perspectives of chiral π-amphiphiles,aiming to help scientists evaluate the cutting-edge field of chiralityscience via diverse supramolecular technologies and systematic molecularengineering.

The development oforganisms and the maintenance of tissue homeostasisdepend on complex intercellular signaling networks that govern basiccell functions. Because cells are typically exposed to many diverseligands simultaneously, distinct intracellular mechanisms of cellsignaling have evolved, allowing cells to accurately sense and respondto their environment. Here, we discuss the concept of ligand bias,which describes the ability of different ligands to preferentiallyactivate specific signaling pathways, and thus produce divergent responsesthrough the same receptor. Although bias can be challenging to identifyand quantify, protocols have been established to (i) determine whetherpreferences exist and (ii) quantify these preferences. We review theseprotocols and their utility in studies of signaling by RTKs, the largestfamily of single-pass membrane receptors. We summarize the literaturesuggesting that RTKs engage in biased signaling and discuss the utilityof signaling bias in therapeutics design. We discuss parallels withGPCR biased signaling, and lessons that have been learned after yearsof GPCR signaling research. Finally, we propose that RTK ligand biasappeared in evolution to diversify the morphogen signaling pathwaysthat direct the development of tissues and organs in the mammalianbody.

Rapid advances in photovoltaic technology have driven its exponential global deployment, establishing solar power as a central pillar of future electricity generation. Among next-generation photovoltaic concepts, perovskite/silicon tandem solar cells offer a compelling pathway to surpass the ∼29.4% efficiency limit of conventional crystalline-silicon devices at manufacturing scale. Laboratory demonstrations have already exceeded this threshold, enabled by innovations in perovskite composition engineering, additive incorporation, interfacial passivation, optimized charge-selective contacts, and improved silicon bottom-cell architectures. This Review provides an integrated overview of perovskite material fundamentals and device-engineering strategies that have propelled these rapid efficiency gains. Emphasis is placed on the interplay between performance, stability, and manufacturability of monolithic perovskite/silicon tandems, outlining key challenges and opportunities that will determine their progression from laboratory prototypes to commercially viable photovoltaic technologies.

Membrane proteins participate in most cellular processes from sensing the cellular environment to regulating gene expression. The fundamental unit in eukaryotic membrane proteins is the transmembrane (TM) helix, which in addition to anchoring the protein to the lipid bilayer, often plays a central functional role. We review here advances in our understanding of the factors underpinning the thermodynamic stability of TM helices in cellular membranes. Interestingly, a class of TM sequences exists that has the ability to, when isolated as a peptide, be stable both in solution and in the membrane. This Review covers such conditional TM peptides, including their discovery in the form of the pHLIP peptide, the factors that determine their membrane insertion, and the basis for their use in cancer theranostics. We also discuss how this knowledge has been the conceptual basis for the design of sequences that partition into lipid bilayers and target membrane proteins. These peptides act as both positive and negative allosteric regulators of their membrane targets. Such TM allosteric conditional peptides (TMACs) additionally constitute tools that can advance our understanding of the activity and regulation of membrane proteins.

Polysaccharide monooxygenases (PMOs) constitute a superfamily of enzymes that hydroxylate carbon atoms in glycosidic bonds, ultimately leading to the degradation of carbohydrate polymers. PMOs catalyze this challenging transformation at a mononuclear copper site and utilize either O₂ or H₂O₂ as a cosubstrate. In this review, the mechanisms of three types of catalytic chemistry are discussed: monooxygenase (O₂ as a cosubstrate), oxidase (O₂ reduction to H₂O₂), and peroxygenase (H₂O₂ as a cosubstrate). Key discoveries in the understanding of PMO mechanism and function are described. Several important questions remain unanswered about the utilization of O₂ and H₂O₂ as cosubstrates for polysaccharide hydroxylation. This review will summarize the progress toward understanding the mechanism of O₂ activation by this unique class of monooxygenases.

Printed metal halide perovskite photovoltaics combine high device performance with low-cost manufacturing, which have become one of the most promising candidates for next-generation photovoltaic technologies. With the rapid development of printing methods for scalable film deposition, printed perovskite solar cells have already achieved a power conversion efficiency (PCE) exceeding 26%. However, the PCE of commercial-size perovskite solar modules remains near 21%, indicating that the key bottleneck is no longer the intrinsic optoelectronic potential of the absorber but the translation of precursor inks into uniform, scalable, and durable films. During the printing process, ink design governs precursor solvent coordination, intermediate-phase evolution, colloidal stability, rheology, crystallization kinetics, wet-film stability, and ultimately large-area film quality. This Review summarizes perovskite precursor inks from a solution chemistry to manufacturing perspective and discusses the influences of chemical composition, solvent selection, mixed-solvent interactions, solvent–perovskite intermediates, crystallization control, solvent extraction methods, and rheological regulation on the film morphology during the scalable printing process. We further highlight industrially relevant metrics that increasingly determine viable ink systems, including shelf life, ambient air tolerance, coating-speed window, defect suppression, reproducibility, solvent toxicity, and compatibility with module integration and encapsulation. By linking ink formulation to film formation, scalable deposition, and module performance, this Review provides direction for printable ink design and identifies the critical challenges that should be addressed to realize reproducible, low-waste, high-throughput, and durable printed perovskite solar modules.