Synthetic Design Research Articles

Synthesis and Crystallographic Characterization of Heteroleptic Ir(III) Complexes Containing the N-oxide Functional Group and Crystallographic Characterization of Ir(III) N-oxide Precursors

The N-oxide functional group has been exploited for synthetic strategies and drug design, and it has been utilized in imaging agents. Herein, we present rare examples of neutral heteroleptic cyclometallated Ir(III) compounds that contain an uncoordinated N-oxide functional group. These species, along with others described within, were verified by NMR, EA, HRMS, and single-crystal X-ray analysis. N-oxide-containing Ir(III) species were prepared selectively in high yields > 66% from chloro-bridged Ir(III) dimers with Acipimox, a picolinate-type ligand containing the N-oxide functional group. Non-N-oxide analogs were synthesized in a similar fashion (yields > 77%). Electrochemical comparison (cyclic voltammetry) indicates that the presence of an N-oxide functional group anodically shifts the reduction potential, suggesting that the N-oxide is acting as an electron-withdrawing group in these species. Crystallographic studies were pursued to examine the coordination behavior of these N-oxides compared to their non-oxidized congeners. The Ir(III) complexes with Acipimox indeed leave the N-oxide uncoordinated and exposed on the complexes. The uncoordinated N-oxide group is influential in directing the packing structures of these complexes directly through C-H···O and O···π interactions at the N-oxide. The crystallographic characterization of cationic Ir(III) compounds with uncoordinated nitrogen atoms is also presented. The C-H···N interactions between these complexes form a variety of dimers, finite chains, and continuous chains. Future work will focus on functionalizing the cationic Ir(III) species into their corresponding N-oxide derivatives and rigorously characterizing how the N-oxide functional group impacts the optical properties of transition metal compounds in both cationic and neutral complexes.

A complete methodology to assess hydraulic risk in small ungauged catchments based on HEC-RAS 2D Rain-On-Grid simulations

This paper explores the use of the rain-on-grid (or direct rainfall) method for flood risk assessment at a basin scale. The method is particularly useful for rural catchments with small vertical variations and complex interactions with man-made obstacles and structures, which may be oversimplified by traditional hydrologically based estimations. The use of a hydrodynamic model solving mass and momentum conservation equations allows the simulation of runoff over the watershed at a basin scale. As a drawback, more detailed and spatially distributed data are needed, and the computational time is extended. On the other hand, a smaller number of parameters is needed compared to a hydrological model. Roughness and rainfall loss coefficients need to be calibrated only. The direct rainfall methodology was here implemented within the two-dimensional HEC-RAS model for the low-land rural, and ungauged, watershed of the Terdoppio River, Northern Italy. The resulting hydrographs at the closing section of the watershed were compared to synthetic design hydrographs evaluated through pure hydrological modelling, showing agreement on the peak discharge values for the low-probability scenarios, but not on the total volumes. The results in terms of water depth and flow velocity maps were used to create flood hazard maps using the Australian Institute for Disaster Resilience methodology. The Index of Proportional Risk model was then adopted to generate a basin-scale flood risk map, by combining flood hazard maps, damage functions for different building-use classes, and the value of reconstruction and content per unit area.

Modular Synthesis of Improbable Rotaxanes with All-Benzene Scaffolds.

"Improbable" rotaxanes consisting of interlocked conjugated components represent non-trivial synthetic targets, not to mention those with all-benzene scaffolds. Herein, a modular synthetic strategy has been established using an isolable azo-linked pre-rotaxane as the core module, in which the azo group functions as a tracelessly removable template to direct mechanical bond formations. Through versatile connections of the pre-rotaxane and other customizable modules, [2]- and [3]rotaxanes derived from all-benzene scaffolds have been accomplished, demonstrating the utility and potential of the synthetic design for all-benzene interlocked supramolecules.

Solvent effects in anion recognition.

Anion recognition is pertinent to a range of environmental, medicinal and industrial applications. Recent progress in the field has relied on advances in synthetic host design to afford a broad range of potent recognition motifs and novel supramolecular structures capable of effective binding both in solution and at derived molecular films. However, performance in aqueous media remains a critical challenge. Understanding the effects of bulk and local solvent on anion recognition by host scaffolds is imperative if effective and selective detection in real-world media is to be viable. This Review seeks to provide a framework within which these effects can be considered both experimentally and theoretically. We highlight proposed models for solvation effects on anion binding and discuss approaches to retain strong anion binding in highly competitive (polar) solvents. The synthetic design principles for exploiting the aforementioned solvent effects are explored.

High Quantum Yields from Perfluorinated Binolate Erbium Complexes and Their Circularly Polarized Luminescence.

High quantum yield and circularly polarized luminescence (CPL) brightness values are reported from Shibasaki-type erbium complexes supported by a perfluorinated Binol ligand (F12Binol). The total fluorination of the ligand circumvents nonradiative quenching from Csp2-H vibrations and leads to quantum yields of up to 11% and CPL brightness values of up to 317 M-1 cm-1 (a 19- and 6-fold increase, respectively, compared to (Binol)3ErNa3). These values are the highest values for any molecular erbium complex to date, making them comparable to Yb emitters. A series of fluorinated Shibasaki-type complexes are synthesized by varying the alkali metal (K, Na, Li) in the secondary coordination sphere, leading to unexpected structural differences. NMR (19F, 7Li) and chiroptical spectroscopy analyses provide insights into their structural geometry. With much improved quantum yields and CPL brightness values, we provide synthetic design principles toward other practical candidates for use in quantum communication technologies.

Progress in the Synthesis of Colloidal Machines.

For the past decade, the field of colloidal science has expanded the collection of colloidal particles to include an entire library of subunits that can be isotropic or anisotropic in terms of structural morphology or chemical composition. Using anisotropic subunits, the field has assembled a variety of static and dynamic structures. For this Account, we use the umbrella term "dynamic colloids" to describe subunits capable of movement, shape-shifting, or any other type of action in response to a stimulus and "static colloids" to describe those that are unresponsive to such stimuli. We view dynamic colloids as an access point to colloidal machines, a unique and emerging subfield of machines, and colloidal science. The assembly of dynamic subunits into colloidal machines differs from traditional self-assembly only in the final structures assembled, not the methods used. Dynamic assemblies have the capacity to interact with their environment in ways that traditional anisotropic self-assemblies do not. Here, we present the current state of the field of colloidal science toward the introduction of the next wave of colloidal machines. Machines are ubiquitous in nature and synthetic systems, governing every aspect of life. In mechanics, a machine is a device that transmits or modifies force or motion. In biology, nature's machines such as kinesin or ATP synthetase are essential to life. In the synthetic realm, molecular machines and nanomachines, recognized with the Nobel prize, include diverse systems, such as molecular rotors and elevators fabricated using bottom-up synthetic methods. On the microscale, microscopic motors based on microelectromechanical systems (MEMs) have been achieved via top-down methods such as micromachining. On the colloidal scale, machines are conspicuously absent due, in part, to the difficulty in navigating combinatory design spaces. We view colloidal machines (100 nm to 10 μm) as the next line of miniaturization in machines. Due to the bottom-up fabrication methods generally used in creating dynamic colloids, one can achieve complexity at a smaller scale than possible with top-down approaches. The introduction of colloidal scale machines would bridge the gap between the microscopic world with its macroscopic counterparts, the nanoworld with its molecular machines, and the biological world with nature's machinery. Reported colloidal machines to date are apparatuses that consist of multiple components of a single composition of dynamic subunits that come together to perform some work. The next step toward complex colloidal machines is systems containing multiple dynamic colloidal scale components that come together to act in tandem to perform some work on the surrounding environment. We envision repurposing a library of dynamic particles originally intended to be used as anisotropic subunits into dynamic components of a colloidal machine. Computationally, the idea of colloidal machines has been extensively explored; however, synthetically, there has been limited exploration. In order to implement this existing library into colloidal machines, the key next step is the development of synthetic combinatorial design spaces.

Design and Model-Driven Analysis of Synthetic Circuits with the Staphylococcus aureus Dead-Cas9 (sadCas9) as a Programmable Transcriptional Regulator in Bacteria.

Synthetic circuit design is crucial for engineering microbes that process environmental cues and provide biologically relevant outputs. To reliably scale-up circuit complexity, the availability of parts toolkits is central. Streptococcus pyogenes (sp)-derived CRISPR interference/dead-Cas9 (CRISPRi/spdCas9) is widely adopted for implementing programmable regulations in synthetic circuits, and alternative CRISPRi systems will further expand our toolkits of orthogonal components. Here, we showcase the potential of CRISPRi using the engineered dCas9 from Staphylococcus aureus (sadCas9), not previously used in bacterial circuits, that is attractive for its low size and high specificity. We designed a collection of ∼20 increasingly complex circuits and variants in Escherichia coli, including circuits with static function like one-/two-input logic gates (NOT, NAND), circuits with dynamic behavior like incoherent feedforward loops (iFFLs), and applied sadCas9 to fix a T7 polymerase-based cascade. Data demonstrated specific and efficient target repression (100-fold) and qualitatively successful functioning for all circuits. Other advantageous features included low sadCas9-borne cell load and orthogonality with spdCas9. However, different circuit variants showed quantitatively unexpected and previously unreported steady-state responses: the dynamic range, switch point, and slope of NOT/NAND gates changed for different output promoters, and a multiphasic behavior was observed in iFFLs, differing from the expected bell-shaped or sigmoidal curves. Model analysis explained the observed curves by complex interplays among components, due to reporter gene-borne cell load and regulator competition. Overall, CRISPRi/sadCas9 successfully expanded the available toolkit for bacterial engineering. Analysis of our circuit collection depicted the impact of generally neglected effects modulating the shape of component dose-response curves, to avoid drawing wrong conclusions on circuit functioning.

Synthetic and Computational Design Insights toward Mimicking Protein Binding of Phosphate.

The unique and precise capabilities of proteins are renowned for their specificity and range of application. Effective mimicking of protein-binding offers enticing potential to direct their abilities toward useful applications, but it is nevertheless quite difficult to realize this characteristic of protein behavior in a synthetic material. Here, we design, synthesize, and evaluate experimentally and computationally a series of multicomponent phosphate-binding peptide amphiphile micelles to derive design insights into how protein binding behavior translates to synthetic materials. By inserting the Walker A P-loop binding motif into this peptide synthetic material, we successfully implemented the protein-binding design parameters of hydrogen-bonding and electrostatic interaction to bind phosphate completely and selectively in this highly tunable synthetic platform. Moreover, in this densely arrayed peptide environment, we use molecular dynamics simulations to identify an intriguing mechanistic shift of binding that is inaccessible in traditional proteins, introducing two corresponding new design elements─flexibility and minimization of the loss of entropy due to ion binding, in protein-analogous synthetic materials. We then translate these new design factors to de novo peptide sequences that bind phosphate independent of protein-extracted sequence or conformation. Overall, this work reveals that traditional complex conformational restrictions of binding by proteins can be replaced and repurposed in a multicomponent peptide amphiphile synthetic material, opening up opportunities for future enhanced protein-inspired design.

Exploring the topic structure and abuse trends of new psychoactive Substance since the 21st century from a bibliometric perspective

Nowadays, NPS abuse are continuing to expand in terms of harm and scope, due to its cheap and easy to manufacture anywhere in the world. This study reviewed articles related to seven heavily abused NPS to analyze the structure and trends of NPS abuse. A total of 2476 articles were retrieved based on the search strategy for bibliometric analysis. A significant trend of research in recent years was the increasing number of research on synthetic opioids and designer benzodiazepines, but synthetic cannabinoid and synthetic cathinone still dominate, which were mainly concerned with the development of metabolic models and determining methods as well as their abuse characteristics and reasons. However, with the introduction of class-wide ban on synthetic cannabinoid in China and a series of enhancements in other countries, the abuse of it might decrease to some extent, but more than 20 kinds of synthetic cannabinoid beyond the scope of ban in China still reminded researchers of their potential threats. As for synthetic cathinone, an important phenomenon was some of the drugs first identified during certain period might be more widely distributed in the future. Besides, several problems such as the regulation and prevention mode of emerging NPS, development of testing technologies as well as the interpretation and identification of multiple NPS combinations were also worth paying attention to. This study could help entrants better understand the structure of NPS abuse and provided direction for future research in forensic toxicology.

Node-Aligned Graph-to-Graph: Elevating Template-free Deep Learning Approaches in Single-Step Retrosynthesis.

Single-step retrosynthesis in organic chemistry increasingly benefits from deep learning (DL) techniques in computer-aided synthesis design. While template-free DL models are flexible and promising for retrosynthesis prediction, they often ignore vital 2D molecular information and struggle with atom alignment for node generation, resulting in lower performance compared to the template-based and semi-template-based methods. To address these issues, we introduce node-aligned graph-to-graph (NAG2G), a transformer-based template-free DL model. NAG2G combines 2D molecular graphs and 3D conformations to retain comprehensive molecular details and incorporates product-reactant atom mapping through node alignment, which determines the order of the node-by-node graph outputs process in an autoregressive manner. Through rigorous benchmarking and detailed case studies, we have demonstrated that NAG2G stands out with its remarkable predictive accuracy on the expansive data sets of USPTO-50k and USPTO-FULL. Moreover, the model's practical utility is underscored by its successful prediction of synthesis pathways for multiple drug candidate molecules. This proves not only NAG2G's robustness but also its potential to revolutionize the prediction of complex chemical synthesis processes for future synthetic route design tasks.

Novel 2,5-Diketopiperazines with In Vitro Activities against Protozoan Parasites of Tropical Diseases.

Malaria, Chagas disease, and leishmaniasis are tropical diseases caused by protozoan parasites of the genera Plasmodium, Trypanosoma and Leishmania, respectively. These diseases constitute a major burden on public health in several regions worldwide, mainly affecting low-income populations in economically poor countries. Severe side effects of currently available drug treatments and the emergence of resistant parasites need to be addressed by the development of novel drug candidates. Natural 2,5-Diketopiperazines (2,5-DKPs) constitute N-heterocyclic secondary metabolites with a wide range of biological activities of medicinal interest. Its structural and physicochemical properties make the 2,5-DKP ring a versatile, peptide-like, and stable pharmacophore attractive for synthetic drug design. In the present work, twenty-three novel synthetic 2,5-DKPs, previously synthesized through the versatile Ugi multicomponent reaction, were assayed for their anti-protozoal activities against P. falciparum, T. cruzi, and L. infantum. Some of the 2,5-DKPs have shown promising activities against the target protozoans, with inhibitory concentrations (IC50) ranging from 5.4 to 9.5 µg/mL. The most active compounds also show low cytotoxicity (CC50), affording selectivity indices ≥ 15. Results allowed for observing a clear relationship between the substitution pattern at the aromatic rings of the 2,5-DKPs and their corresponding anti-Plasmodium activity. Finally, calculated drug-like properties of the compounds revealed points for further structure optimization of promising drug candidates.

Revolutionizing Synthetic Antibody Design: Harnessing Artificial Intelligence and Deep Sequencing Big Data for Unprecedented Advances.

Synthetic antibodies (Abs) represent a category of engineered proteins meticulously crafted to replicate the functions of their natural counterparts. Such Abs are generated in vitro, enabling advanced molecular alterations associated with antigen recognition, paratope site engineering, and biochemical refinements. In a parallel realm, deep sequencing has brought about a paradigm shift in molecular biology. It facilitates the prompt and cost-effective high-throughput sequencing of DNA and RNA molecules, enabling the comprehensive big data analysis of Ab transcriptomes, including specific regions of interest. Significantly, the integration of artificial intelligence (AI), based on machine- and deep- learning approaches, has fundamentally transformed our capacity to discern patterns hidden within deep sequencing big data,including distinctive Ab features and protein folding free energy landscapes. Ultimately, current AI advances can generate approximations of the most stable Ab structural configurations, enabling the prediction of de novo synthetic Abs. As a result, this manuscript comprehensively examines the latest and relevant literature concerning the intersection of deep sequencing big data and AI methodologies for the design and development of synthetic Abs. Together, these advancements have accelerated the exploration of antibody repertoires, contributing to the refinement of synthetic Ab engineering and optimizations, and facilitating advancements in the lead identification process.

Hierarchical and Nanocrystallite-Assembled Ultraporous NiO/MnCo2O4 for All Solid-State Hybrid Supercapacitors with Robust Energy Efficiency and Extended Operational Durability.

To address the growing demand of highly Ragone efficient electrochemical energy storage devices, we have innovated a synthetic design strategy and employed a tartrate-mediated kinetic precipitation process to fabricate an ultraporous ribbon-like hierarchical microstructure of Ni-, Mn-, and Co-based ternary oxide, i.e., NiO/MnCo2O4, and employed it as a battery-type positive electrode material to assemble an ASSHSC (all-solid-state hybrid supercapacitor) device with nitrogen-doped reduced graphene oxide (N-rGO) as the positive electrode material. NiO/MnCo2O4 exhibits distinct crystallographic phase, near-perfect elemental stoichiometry, evident bulk porosity, and rich nanocrystallite assembly in the randomly arranged microstructure of near-uniform size and shape. Thorough electrochemical studies corroborate that the battery-type NiO/MnCo2O4 exhibits remarkable electrochemical reversibility during charge transfer, high efficiency in supercapacitive charge storage, low charge transfer, series and diffusion resistance. The NiO/MnCo2O4||N-rGO ASSHSC device assembled with the PVA-KOH film as the separator electrolyte offers rich charge storage physiognomies, which accentuates excellent electromicrostructural compatibility between the electrode materials in the device. The NiO/MnCo2O4||N-rGO ASSHSC device shows low charge transfer and diffusion resistance, and it also delivers high mass and areal specific capacitance/capacity, energy and power density, Ragone efficiency (∼131 Wh kg-1 at ∼2134 W kg-1 and ∼31 Wh kg-1 at ∼5005 W kg-1), and extended operational durability (98.2% specific capacitance retention after 12,000 successive GCD cycles) under high-rate working conditions. The present optimized approach to design highly efficient multiple transition-metal-based oxides as battery-type electrode materials and fabricate rich Ragone-efficient ASSHSC devices can be widely adopted in the future development of high-performance hybrid supercapacitors, which may be largely integrated in various pioneering technologies.

Porphyrin-Based Nanomaterials for the Photocatalytic Remediation of Wastewater: Recent Advances and Perspectives

Self-organized, well-defined porphyrin-based nanostructures with controllable sizes and morphologies are in high demand for the photodegradation of hazardous contaminants under sunlight. From this perspective, this review summarizes the development progress in the fabrication of porphyrin-based nanostructures by changing their synthetic strategies and designs. Porphyrin-based nanostructures can be fabricated using several methods, including ionic self-assembly, metal–ligand coordination, reprecipitation, and surfactant-assisted methods. The synthetic utility of porphyrins permits the organization of porphyrin building blocks into nanostructures, which can remarkably improve their light-harvesting properties and photostability. The tunable functionalization and distinctive structures of porphyrin nanomaterials trigger the junction of the charge-transfer mechanism and facilitate the photodegradation of pollutant dyes. Finally, porphyrin nanomaterials or porphyrin/metal nanohybrids are explored to amplify their photocatalytic efficiency.

A systems framework for investigating the roles of multiple transporters and their impact on drug resistance.

Efflux transporters are a fundamental component of both prokaryotic and eukaryotic cells, play a crucial role in maintaining cellular homeostasis, and represent a key bridge between single cell and population levels. From a biomedical perspective, they play a crucial role in drug resistance (and especially multi-drug resistance, MDR) in a range of systems spanning bacteria and human cancer cells. Typically, multiple efflux transporters are present in these cells, and the efflux transporters transport a range of substrates (with partially overlapping substrates between transporters). Furthermore, in the context of drug resistance, the levels of transporters may be elevated either due to extra or intracellular factors (feedforward regulation) or due to the drug itself (feedback regulation). As a consequence, there is a real need for a transparent systems-level understanding of the collective functioning of a set of transporters and their response to one or more drugs. We develop a systems framework for this purpose and examine the functioning of sets of transporters, their interplay with one or more drugs and their regulation (both feedforward and feedback). Using computational and analytical work, we obtain transparent insights into the systems level functioning of a set of transporters arising from the interplay between the multiplicity of drugs and transporters, different drug-transporter interaction parameters, sequestration and feedback and feedforward regulation. These insights transparently arising from the most basic consideration of a multiplicity of transporters have broad relevance in natural biology, biomedical engineering and synthetic biology. Insight, Innovation, Integration: Innovation: creating a structured systems framework for evaluating the impact of multiple transporters on drug efflux and drug resistance. Systematic analysis allows us to evaluate the effect of multiple transporters on one/more drugs, and dissect associated resistance mechanisms. Integration allows for elucidation of key cause-and-effect relationships and a transparent systems-level understanding of the collective functioning of transporters and their impact on resistance, revealing the interplay of key underlying factors. Systems-level insights include the essentially different behaviour of transporters as part of a group; unintuitive effects of influx; effects of elevated transporter-levels by feedforward and drug-induced mechanisms. Relevance: a systems understanding of efflux, their role in MDR, providing a framework/platform for use in designing treatment, and in synthetic biology design.

Co/NM/Pt]n-based seedless synthetic anti-ferromagnetic layer design for preventing MgO crystallinity degradation from Pt diffusion

Co/NM/Pt]n-based seedless synthetic anti-ferromagnetic layer design for preventing MgO crystallinity degradation from Pt diffusion

Thermoresponsive Injectable Hydrogel To Mimic the Heat- and Strain-Stiffening Behavior of Biopolymers toward Muscle Cell Proliferation.

Injectable hydrogels with nonlinear mechanical attributes to emulate natural biopolymers hold paramount significance in tissue engineering, offering the potential to create scaffolds that seamlessly mimic the biomechanical intricacies of living tissues. Herein, we unveil a synthetic design strategy employing Schiff base chemistry to furnish a peptide-polymer hierarchical contractile injectable hydrogel network. This innovative design demonstrates cross-linking of supramolecular peptide nanostructures such as nanofibers, 1NF, and twisted bundles, 1TB, with a thermosensitive aldehyde-functionalized polymer, PCHO. These networks exhibit interesting nonlinear mechanical stiffening responses to temperature and external stress. Furthermore, the hydrogels transform into a gel state at physiological temperature to exhibit injectable behavior and demonstrate compression load-bearing capabilities. Finally, the hydrogel network exhibits excellent biocompatibility and cell proliferation toward fibroblast, L929, and myoblast, C2C12, to validate their use as potential extracellular matrix mimetic injectable scaffolds.

Synthesis of Amphiphilic Block Copolymer and Its Application in Pigment-Based Ink.

Amphiphilic block copolymers-based aqueous color inks show great potential in the field of visual communication design. However, the conventional step-by-step chemistry employed to synthesize the amphiphilic block copolymers is intricate, with low yield and high economic and environmental costs. In this work, we present a novel method for preparing an amphiphilic AB di-block copolymer of PCL-b-PAA by employing a combined polymerization strategy that involves both cationic ring-opening polymerization (ROP) of the ε-caprolactone monomer and the reversible addition-fragmentation chain-transfer (RAFT) polymerization on the acrylic acid monomer simultaneously. The corresponding polycaprolactone (PCL) and polyacrylic acid (PAA) serve as the hydrophobic and hydrophilic units, respectively. The effectiveness of the amphiphilic AB di-block copolymer as the polymeric pigment dispersant for water-based color inks is evaluated. The amphiphilic AB di-block copolymer of PCL-b-PAA exhibits a molecular weight of 1400 g mol-1, which is consistent with the theoretical value and suitable for polymeric dispersant application. The high surface excess (Γmax) of the PCL-b-PAA in water indicates a densely packed molecular morphology at the water/air interface. Additionally, micelles can be stably formed in the aqueous PCL-b-PAA solution at very low concentrations by demonstrating a low CMC value of 10-4 wt% and a micelle dimension of approximately 30 nm. The model ink dispersion is prepared using organic dyes (Disperse Yellow 232) and the amphiphilic block copolymer of PCL-b-PAA. The dispersion demonstrates near-Newtonian behavior, which is highly favorable for the application as inkjet ink. Furthermore, the ink dispersion displays a low viscosity, making it particularly suitable for visual communication design and printing purposes. Moreover, the ink dispersion demonstrates an unimodal distribution of the particle size, with an average diameter of approximately 500 nm. It retains exceptional stability of dispersion and even conducts a thermal aging treatment at 60 °C for 5 days. This work presents a facile and efficient synthetic strategy and molecular design of AB di-block copolymer-based dispersants for dye dispersions.

Exploiting the Mechanical Bond Effect for Enhanced Molecular Recognition and Sensing.

The ubiquity of charged species in biological and industrial processes has resulted in ever-increasing interest in their selective recognition, detection, and environmental remediation. Building on the established coordination chemistry principles of the chelate and macrocyclic effects, and host preorganization, supramolecular chemists seek to construct specific 3D binding cavities reminiscent of biotic systems to enhance host-guest binding affinity and selectivity. Mechanically interlocked molecules (MIMs) present a wholly unique platform for synthetic host design, wherein topologies afforded by the mechanical bond enable the decoration of 3D cavities for non-covalent interactions with a range of target guest geometries. Notably, MIM host systems exhibit mechanical bond effect augmented affinities and selectivities for a variety of charged guest species, compared to non-interlocked acyclic and macrocycle host analogs. Furthermore, the modular nature of MIM synthesis facilitates incorporation of optical and electrochemical reporter groups, enabling fabrication of highly sensitive and specific molecular sensors. This review discusses the development of recognition and sensing MIMs, from the first reports in the late 20th century through to the present day, delineating how their topologically preorganized and dynamic host cavities enhance charged guest recognition and sensing, demonstrating the mechanical bond effect as a potent tool in future chemosensing materials.

Revealing proton-coupled exchange mechanism in aqueous ion-exchange synthesis of nickel-rich layered cathodes for lithium-ion batteries

Ion exchange is a promising synthetic method for alleviating severe cation mixing in traditional layered oxide materials for lithium-ion batteries, leading to enhanced structural stability. However, the underlying mechanisms of ion exchange are still not fully understood. Such a fundamental study of the ion-exchange mechanism is needed for achieving the controllable synthesis of layered oxides with a stable structure. Herein, we thoroughly unearth the underlying mechanism that triggers the ion exchange of Ni-rich materials in aqueous solutions by examining time-resolved structural evolution combined with theoretical calculations. Our results reveal that the reaction pathway of ion exchange can be divided into two steps: protonation and lithiation. The proton is the key to achieving charge balance in the ion exchange process, as revealed by X-ray adsorption spectroscopy and inductive coupled plasma analysis. In addition, the intermediate product shows high lattice distortion during ion exchange, but it ends up with a most stable product with high lattice energy. Such apparent discrepancies in lattice energy between materials before and after ion exchange emphasize the importance of synthetic design in structural stability. This work provides new insights into the ion-exchange synthesis of Ni-rich oxide materials, which advances the development of cathode materials for high-performance lithium-ion batteries.