Accounts of Chemical Research

ConspectusCircularly polarized luminescence (CPL) generated by chiral luminescent systems has sparked enormous attention in multidisciplinary field as it brings infinite potential for applications, such as 3D optical displays, biological probes, and chiroptical sensors. Satisfying both the conditions of chirality and luminescence (including fluorescence or phosphorescence) is a prerequisite for constructing CPL materials. In this regard, whether in organic, inorganic, or hybrid systems, chiral and luminescent components generally involve effective coupling through covalent or noncovalent bonds...

ConspectusMolecular docking, also termed ligand docking (LD), is a pivotal element of structure-based virtual screening (SBVS) used to predict the binding conformations and affinities of protein-ligand complexes. Traditional LD methodologies rely on a search and scoring framework, utilizing heuristic algorithms to explore binding conformations and scoring functions to evaluate binding strengths. However, to meet the efficiency demands of SBVS, these algorithms and functions are often simplified, prioritizing speed over accuracy...

ConspectusPolymer electrolytes constitute a promising type of material for solid-state batteries. However, one of the bottlenecks for their practical implementation lies in the transport properties, often including restricted Li+ self-diffusion and conductivity and low cationic transference numbers. This calls for a molecular understanding of ion transport in polymer electrolytes in which molecular dynamics (MD) simulation can provide both new physical insights and quantitative predictions. Although efforts have been made in this area and qualitative pictures have emerged, direct and quantitative comparisons between experiment and simulation remain challenging because of the lack of a unified theoretical framework to connect them...

ConspectusSupramolecular coordination complexes (SCCs) are predictable and size-tunable supramolecular self-assemblies constructed through directional coordination bonds between readily available organic ligands and metallic receptors. Based on planar and 3D structures, SCCs can be mainly divided into two categories: metallacycles (e.g., rhomboidal, triangular, rectangular, and hexagonal) and metallacages (e.g., tetrahedral, hexahedral, and dodecahedral). The directional coordination bonds enable the efficient formation of metallacycles and metallacages with well-defined architectures and geometries...

ConspectusSince their commercialization in the 1990s, lithium-ion batteries (LIBs) have been increasingly used in applications such as portable electronics, electric vehicles, and large-scale energy storage. The increasing use of LIBs in modern society has necessitated superior-performance LIB development, including electrochemical reversibility, interfacial stability, efficient kinetics, environmental adaptability, and intrinsic safety, which is difficult to simultaneously achieve in commercialized electrolytes...

ConspectusChemical reactions can be promoted at lower temperatures and pressures, thereby reducing the energy input, by introducing suitable catalysts. Despite its significance, the quest for efficient and stable catalysts remains a significant challenge. In this context, addressing the efficiency of catalysts stands out as a paramount concern. However, the challenges posed by the vague structure and limited tailorability of traditional catalysts would make it highly desirable to fabricate optimized catalysts based on the understanding of structure-activity relationships...

ConspectusTransition metal-catalyzed reductive cross-coupling of two carbon electrophiles, also known as cross-electrophile coupling (XEC), has transformed the landscape of C-C coupling chemistry. Nickel catalysts, in particular, have demonstrated exceptional performance in facilitating XEC reactions, allowing for diverse elegant transformations by employing various electrophiles to forge C-C bonds. Nevertheless, several crucial challenges remain to be addressed. First, the intrinsic chemoselectivity between two structurally similar electrophiles in Ni-catalyzed C(sp3 )-C(sp3 ) and C(sp2 )-C(sp2 ) cross-coupling has not been well understood; this necessitates an excess of one of the coupling partners to achieve synthetically useful outcomes...

ConspectusWe have learned over the past years how London dispersion forces can be effectively used to influence or even qualitatively tip the structure of aggregates and the conformation of single molecules. This happens despite the fact that single dispersion contacts are much weaker than competing polar forces. It is a classical case of strength by numbers, with the importance of London dispersion forces scaling with the system size. Knowledge about the tipping points, however difficult to attain, is necessary for a rational design of intermolecular forces...

ConspectusThe preparation of discrete and well-defined polymers is an emerging strategy for emulating the remarkable precision achieved by macromolecular synthesis in nature. Although modern controlled polymerization techniques have unlocked access to a cornucopia of materials spanning a broad range of monomers, molecular weights, and architectures, the word "controlled" is not to be confused with "perfect". Indeed, even the highest-fidelity polymerization techniques─yielding molar mass dispersities in the vicinity of Đ = 1...

ConspectusThe zinc-dependent histone deacetylases (HDACs 1-11) belong to the arginase-deacetylase superfamily of proteins, members of which share a common α/β fold and catalytic metal binding site. While several HDACs play a role in epigenetic regulation by catalyzing acetyllysine hydrolysis in histone proteins, the biological activities of HDACs extend far beyond histones. HDACs also deacetylate nonhistone proteins in the nucleus as well as the cytosol to regulate myriad cellular processes. The substrate pool is even more diverse in that certain HDACs can hydrolyze other covalent modifications...

ConspectusFor the delivery of drugs, different nanosized drug carriers (e.g., liposomes, lipid nanoparticles, and micelles) have been developed in order to treat diseases that afflict society. Frequently, these vehicles are formed by the self-assembly of small molecules to encapsulate the therapeutic cargo of interest. Over decades, nanoparticles have been optimized to make them more efficient and specific to fulfill tailor-made tasks, such as specific cell targeting or enhanced cellular uptake. In recent years, lipid-based nanoparticles in particular have taken center stage; however, off-targeting side effects and poor endosomal escape remain major challenges since therapies require high efficacy and acceptable toxicity...

ConspectusThe electrochemical reduction of carbon dioxide (CO2RR) is a promising strategy for mitigating global CO2 emissions while simultaneously yielding valuable chemicals and fuels, such as CO, HCOO- , and C2 H4 . This approach becomes especially appealing when integrated with surplus renewable electricity, as the ensuing production of fuels could facilitate the closure of the carbon cycle. Despite these advantages, the realization of industrial-scale electrolyzers fed with CO2 will be challenged by the substantial energy inputs required to isolate, pressurize, and purify CO2 prior to electrolysis...

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ConspectusThe advent of the twenty-first century marked a golden era in the realm of synthetic chemistry, exemplified by groundbreaking advancements in the field of C-H activation, which is a concept that quickly transitioned from mere academic fascination to an essential element within the synthetic chemist's toolkit. This methodological breakthrough has given rise to a wealth of opportunities spanning a wide range of chemical disciplines. It has facilitated the late-stage diversification of elaborate organic frameworks, encompassing the spectrum from simple methane to complex polymers, thus refining the lead optimization process and easing the production of diverse molecular analogues...

ConspectusThe heterogeneous coprecipitation of nanocrystals with metals on substrates plays a significant role in both natural and engineered systems. Due to the small dimensions and thereby the large specific surface area, nanocrystal coprecipitation with metals, which is ubiquitous in natural settings, exerts drastic effects on the biogeochemical cycling of metals on the earth's crust. Meanwhile, the controlled synthesis of nanocrystals with metal doping to achieve tunable size/composition enables their broad applications as adsorbents and catalysts in many engineered settings...

ConspectusSiderophores are secondary metabolites utilized by bacteria to acquire iron (Fe), an essential transition metal nutrient. Fe levels in the host environment are tightly regulated and can be further restricted to starve invading bacterial pathogens in a host-defense process known as nutritional immunity. To survive and colonize the Fe-limited host environment, bacteria produce siderophores and express cognate siderophore transport machinery. These active transport pathways present an opportunity for selective and efficient drug delivery into bacterial cells, motivating decades of research on synthetic siderophore-antibiotic conjugates (SACs) as a Trojan-horse strategy for the development of targeted antibiotics...

ConspectusBase excision repair (BER) enzymes are genomic superheroes that stealthily and accurately identify and remove chemically modified DNA bases. DNA base modifications erode the informational content of DNA and underlie many disease phenotypes, most conspicuously, cancer. The "OG" of oxidative base damage, 8-oxo-7,8-dihydroguanine (OG), is particularly insidious due to its miscoding ability that leads to the formation of rare, pro-mutagenic OG:A mismatches. Thwarting mutagenesis relies on the capture of OG:A mismatches prior to DNA replication and removal of the mis-inserted adenine by MutY glycosylases to initiate BER...

ConspectusSince the pioneering work of Curtius and Fischer, chemical peptide synthesis has witnessed a century's development and evolved into a routine technology. However, it is far from perfect. In particular, it is challenged by sustainable development because the state-of-the-art of peptide synthesis heavily relies on legacy reagents and technologies developed before the establishment of green chemistry. Over the past three decades, a broad range of efforts have been made for greening peptide synthesis, among which peptide synthesis using unprotected amino acid represents an ideal and promising strategy because it does not require protection and deprotection steps...

ConspectusAliphatic polyesters based on long-chain monomers were synthesized for the first time almost a century ago. In fact, Carothers' seminal observations that founded the entire field of synthetic polymer fibers were made on such a polyester sample. However, as materials, they have evolved only over the past decade. This is driven by the corresponding monomers becoming practically available from advanced catalytic conversions of plant oils, and future prospects comprise a possible generation from third-generation feedstocks, such as microalgae or waste...

ConspectusThe innovation of chiral ligands has been crucial for the asymmetric synthesis of functional molecules, as demonstrated by several types of widely applied "privileged" ligands. In this context, chiral pyridine-derived ligands, by far some of the oldest and most widely utilized ligands in catalysis, have attracted considerable research interest in the past half-century. However, the development of broadly applicable chiral pyridine units (CPUs) has been plagued by several intertwining challenges, thus delaying advancements in many asymmetric reactions...