Strong Host-guest Interactions Research Articles

Universal synthesis of single-atom electrocatalysts via in situ fluoride ion etching for hydrogen evolution.

Single-atom catalysts (SACs) have attracted considerable interest in the field of electrocatalysis due to their high efficiency of metal utilization and catalytic activity. However, traditional methods of SACs fabrication are often complex and time-consuming. Herein, F-Ru@TiO x N y was synthesized using a straightforward and universal approach via in situ surface etching and heteroatoms immobilization on a vacancies-rich hierarchical TiO x N y nanorods array. The fluorine ion-etched TiO x N y nanorods could produce abundant oxygen vacancies and F-Ti/F-C bonds, which could capture and stabilize Ru heteroatoms by strong host-guest electronic interactions. Due to the synergistic effect of oxygen vacancies anchoring and F-C bonds-assisted stabilization of single atoms, F-Ru@TiO x N y revealed excellent electrocatalytic hydrogen evolution performance, a low overpotential of 20.8 mV at 10 mA cm-2, a Tafel slope of 59.9 mV dec-1 and robust stability at 100 mA cm-2 over 48 h. Furthermore, this universal strategy could be applicable to various heterometals (Pd, Ir, Pt), which also exhibited high heteroatoms dispersity and high electrocatalytic HER activity/stability. This fabrication method is simple, easy-scalable and versatile, showcasing significant potential for electrocatalysts design and promising application prospects in electrocatalytic energy conversion.

Functionalization of Covalent Organic Frameworks with Cyclopentadienyl Cobalt for C2H2/CO2 Separation

AbstractEmerging covalent organic frameworks (COFs) have received great attention for their unique features, but the limited building blocks restrict their structural diversity and performance exploration. Reticular chemistry provides guidance for the structural expansion and performance regulation of COFs. Herein, we constructed two novel two‐dimensional (2D) COFs functionalized with cyclopentadienyl cobalt, denoted as UPC‐COF‐1 and UPC‐COF‐2, via [4+2] imine condensation with diamine building blocks of different length. Theoretical simulations combined with experimental results reveal that UPC‐COF‐1 with shorter building blocks, narrower pore sizes, and stronger host–guest interactions has better C2H2/CO2 separation performance. In addition, UPC‐COF‐1 can maintain separation stability in the presence of water vapor and methane impurities. This work provides a new evidence for the performance regulation of isoreticular COFs with modular and tunable building blocks.

Functionalization of Covalent Organic Frameworks with Cyclopentadienyl Cobalt for C2H2/CO2 Separation.

Emerging covalent organic frameworks (COFs) have received great attention for their unique features, but the limited building blocks restrict their structural diversity and performance exploration. Reticular chemistry provides guidance for the structural expansion and performance regulation of COFs. Herein, we constructed two novel two-dimensional (2D) COFs functionalized with cyclopentadienyl cobalt, denoted as UPC-COF-1 and UPC-COF-2, via [4+2] imine condensation with diamine building blocks of different length. Theoretical simulations combined with experimental results reveal that UPC-COF-1 with shorter building blocks, narrower pore sizes, and stronger host-guest interactions has better C2H2/CO2 separation performance. In addition, UPC-COF-1 can maintain separation stability in the presence of water vapor and methane impurities. This work provides a new evidence for the performance regulation of isoreticular COFs with modular and tunable building blocks.

Incorporation of Pd Single-Atom Sites in Perovskite with an Excellent Selectivity toward Photocatalytic Semihydrogenation of Alkynes.

Semihydrogenation is a crucial industrial process. Noble metals such as Pd have been extensively studied in semihydrogenation reactions, owing to their unique catalytic activity toward hydrogen activation. However, the overhydrogenation of alkenes to alkanes often happens due to the rather strong adsorption of alkenes on Pd active phases. Herein, we demonstrate that the incorporation of Pd active phases as single-atom sites in perovskite lattices such as SrTiO3 can greatly alternate the electronic structure and coordination environment of Pd active phases to facilitate the desorption of alkenes rather than further hydrogenation. Furthermore, the incorporated Pd sites can be well stabilized without sintering by a strong host-guest interaction with SrTiO3 during the activation of H species in hydrogenation reactions. As a result, the Pd incorporated SrTiO3 (Pd-SrTiO3) exhibits an excellent time-independent selectivity (>99.9 %) and robust durability for the photocatalytic semihydrogenation of phenylacetylene to styrene. This strategy based on incorporation of active phases in perovskite lattices will have broad implications in the development of high-performance photocatalysts for selective hydrogenation reactions.

Incorporation of Pd Single‐Atom Sites in Perovskite with an Excellent Selectivity toward Photocatalytic Semihydrogenation of Alkynes

AbstractSemihydrogenation is a crucial industrial process. Noble metals such as Pd have been extensively studied in semihydrogenation reactions, owing to their unique catalytic activity toward hydrogen activation. However, the overhydrogenation of alkenes to alkanes often happens due to the rather strong adsorption of alkenes on Pd active phases. Herein, we demonstrate that the incorporation of Pd active phases as single‐atom sites in perovskite lattices such as SrTiO3 can greatly alternate the electronic structure and coordination environment of Pd active phases to facilitate the desorption of alkenes rather than further hydrogenation. Furthermore, the incorporated Pd sites can be well stabilized without sintering by a strong host–guest interaction with SrTiO3 during the activation of H species in hydrogenation reactions. As a result, the Pd incorporated SrTiO3 (Pd‐SrTiO3) exhibits an excellent time‐independent selectivity (>99.9 %) and robust durability for the photocatalytic semihydrogenation of phenylacetylene to styrene. This strategy based on incorporation of active phases in perovskite lattices will have broad implications in the development of high‐performance photocatalysts for selective hydrogenation reactions.

Vapor-Driven Crosslinked Hydroxypropyl-β-Cyclodextrin Electrospun Nanofibrous Membranes for Ultrafast Dye Removal

Traditional separation membranes used for dye removal often suffer from a trade-off between separation efficiency and water permeability. Herein, we propose a facile approach to prepare cyclodextrin-based high-flux nanofiber membranes by electrospinning and vapor-driven crosslinking processes. The application of glutaraldehyde vapor for crosslinking hydroxypropyl-β-cyclodextrin (HP-β-CD)/polyvinyl alcohol (PVA)/laponite electrospun membranes can build interconnected structures and lead to the formation of a porous hierarchical layer. In addition, the incorporation of inorganic salt, laponite, can alter the crosslinking process, resulting in membranes with improved hydrophilicity and highly maintained electrospun nanofibrous morphology, which contributes to an ultrafast water flux of 1.0 × 105 Lh−1m−2bar−1. Due to the synergetic effect of strong host–guest interaction and electrostatic interaction, the membranes exhibit suitable rejection toward anionic dyes with a high removal efficiency of >99% within a short time and achieve accurate separation for cationic against anionic dyes, accompanied by suitable recyclability with >97% separation efficiency after at least four separation–regenerations. The prepared membranes with remarkable separation efficiency and ultrafast permeation properties might be a promising candidate for high-performance membranes in water treatment.

Computational Screening of Hydrophobic Zeolites for the Removal of Emerging Organic Contaminants from Water.

The pollution of water resources by pharmaceuticals and agents of personal care products (PPCPs) poses an increasingly pressing issue that has received considerable attention from scientists and government agencies alike. Hydrophobic zeolites can serve as selective adsorbents to remove these contaminants from aqueous solution. So far, the adsorption of PPCPs in zeolites has often been investigated in case studies focusing on a small number of contaminants and one or a few zeolites. We present a computational screening approach to investigate the interaction of 53 PPCPs with 14 all-silica zeolites, aiming at a more comprehensive understanding of factors that are beneficial for a strong host-guest interaction and thus an efficient adsorption. The systems are modelled on the classical force field level of theory, allowing for the efficient computational treatment of a large number of PPCP-zeolite combinations and evaluated in terms of the interaction energy between PPCP and zeolite framework. For selected PPCP-zeolite combinations additional Free Energy Perturbation simulations are employed to compute Free Energies of Transfer between the aqueous phase and the adsorbed state. These results can serve as a starting point for experimental studies of relevant PPCP-zeolite combination or more in-depth theoretical investigations.

Hydrophobic CHA-ZIFs with a junctional trap between cha and d6r cages for adsorption of 2,3-butanediol in aqueous solution

Hydrophobic CHA-ZIFs with a junctional trap between cha and d6r cages for adsorption of 2,3-butanediol in aqueous solution

Recognition site modifiable tetrapodal receptor and the effect of alkane chains on monosaccharide recognition

Traditional molecular recognition studies usually focus on obtaining strong host–guest interactions, which may lead to the neglect of important tendencies caused by other factors. Moreover, most receptors typically fix their recognition sites in the backbone of the receptor, resulting in great synthetic challenges for varying recognition functional groups. In this contribution, we developed a new class of tetrapodal receptors. The terminal functional groups of the receptor can be varied by simple chemistry. Through 1H NMR titration experiments and binding constant analysis, the influence of the size and shape of alkane chains on monosaccharide recognition was investigated. The introduction of ester functional groups allows the access of moderate binding affinity to unveil otherwise masked contribution of dispersion force in saccharide recognition. These results also imply that stronger forces may not always be beneficial for host–guest binding while functional groups with a particular shape may favor the discrimination of isomers through steric hindrance effect. Thereby, these tetrapodal receptors and their analogues provide an ideal platform for comparing the effects of various functional groups on molecular recognition.

X-Ray-Triggered CO-Release from Gold Nanocluster: All-in-One Nanoplatforms for Cancer Targeted Gas and Radio Synergistic Therapy.

Glycolysis-dominant metabolic pathway in cancer cells can promote their therapeutic resistance against radiotherapy (RT). Carbon monoxide (CO) as a glycolysis inhibitor can enhance the efficiency of RT. Herein, an X-ray responsive CO-releasing nanocomposite (HA@AuNC@CO) based on strong host-guest interactions between the radiosensitizer and CO donor for enhanced RT is developed. The encapsulated gold nanoclusters (CD-AuNCs) can effectively generate cytotoxic reactive oxygen species (ROS) under X-ray radiation, which not only directly inactivate cancer cells but also induce in situ CO gas generation from adamantane modified metal carbonyl (Ada-CO) for glycolysis inhibition. Both in vitro and in vivo results demonstrate that HA@AuNC@CO exhibits active targeting toward CD44 overexpressed cancer cells, along with excellent inhibition of glycolysis and efficient RT against cancer. This study offers a new strategy for the combination of gas therapy and RT in tumor treatment.

Rational Design and Precise Synthesis of Single-Atom Alloy Catalysts for the Selective Hydrogenation of Nitroarenes.

Single-atom alloys (SAAs) have gained increasing prominence in the field of selective hydrogenation reactions due to their uniform distribution of active sites and the unique host-guest metal interactions. Herein, 15 SAAs are constructed to comprehensively elucidate the relationship between host-guest metal interaction and catalytic performance in the selective hydrogenation of 4-nitrostyrene (4-NS) by density functional theory (DFT) calculations. The results demonstrate that the SAAs with strong host-guest metal interactions exhibit a preference for N─O bond cleavage, and the reaction energy barrier of the hydrogenation process is primarily influenced by the host metal. Among them, Ir1Ni SAA stands out as the prime catalyst candidate, showcasing exceptional activity and selectivity. Furthermore, the Ir1Ni SAA is subsequently prepared through precise synthesis techniques and evaluated in the selective hydrogenation of 4-NS to 4-aminostyrene (4-AS). As anticipated, the Ir1Ni SAA demonstrates extraordinary catalytic performance (yield>96%). In situ FT-IR experiments and DFT calculations further confirmed that the unique host-guest metal interaction at the Ir-Ni interface site of Ir1Ni SAA endows it with excellent 4-NS selective hydrogenation ability. This work provides valuable insights into enhancing the performance of SAAs catalysts in selective hydrogenation reactions by modulating the host-guest metal interactions.

Selective wetting and transport of systemic pesticides on bionic stomatal surface regulated by host–guest interaction

Pesticide residues in the environment pose serious threats to ecosystem and human health, and how to achieve the selective transport and enrichment of specific pesticide residues through hydrophobic surface are still an important challenge. Herein, inspired by the “stomatal gating effect” of plant leaves, amino pillar[5]arene-based host–guest gating systems are introduced into artificial porous surfaces with hydrophobicity to fabricate bionic stomatal surfaces (AP5A porous surface), which is expected to modulate the interaction between pesticide and bionic surface through host–guest interaction to selective promote the wetting and transport of specific pesticide on the surface. Experimental and simulation results indicated the AP5A porous surface would selectively capture and adsorb the triclopyr pesticide by strong host–guest interaction to enhance pesticide wettability, and realized the host–guest interaction induced fast transport and enrichment of triclopyr (246.4 μM cm−2h−1) on the bionic stomatal surface. This work provides a new perspective that host–guest interaction between pesticides and solid surface as a gating switch to selective induce the systemic pesticides wetting and transport on bionic porous surface, which is believed to be useful in applications such as the enrichment and removal of pesticide residues from environment in the future.

Flattening of a Bent Sulfonated MOF Linker: Impact on Structures, Flexibility, Gas Adsorption, CO2/N2 Selectivity, and Proton Conduction.

Rational design of organic building blocks provides opportunities to control and tune various physicochemical properties of metal-organic frameworks (MOFs), including gas handling, proton conduction, and structural flexibility, the latter of which is responsible for new adsorption phenomena and often superior properties compared to rigid porous materials. In this work, we report synthesis, crystal structures, gas adsorption, and proton conduction for a flexible two-dimensional cadmium-based MOF (JUK-13-SO3H-SO2) containing a new sulfonated 4,4'-oxybis(benzoate) linker with a blocking SO2 bridge. This two-dimensional (2D) MOF is compared in detail with a previously reported three-dimensional Cd-MOF (JUK-13-SO3H), based on analogous, but nonflat, SO2-free sulfonated dicarboxylate. The comprehensive structure-property relationships and the detailed comparisons with insights into the networks flexibility are supported by five guest-dependent structures determined by single-crystal X-ray diffraction (XRD), and corroborated by spectroscopy (IR, 1H NMR), powder XRD, and elemental/thermogravimetric analyses, as well as by volumetric adsorption measurements (for N2, CO2, H2O), ideal adsorbed solution theory (IAST), density-functional theory (DFT+D) quantum chemical and grand-canonical Monte Carlo (GCMC) calculations, and electrochemical impedance spectroscopy (EIS) studies. Whereas both dynamic MOFs show moderate proton conductivity values, they exhibit excellent CO2/N2 selectivity related to the capture of CO2 from flue gases (IAST coefficients for 15:85 mixtures are equal to ca. 250 at 1 bar and 298 K). The presence of terminal sulfonate groups in both MOFs, introduced using a unique prechlorosulfonation strategy, is responsible for their hydrophilicity and water-assisted proton transport ability. The dynamic nature of the MOFs results in the appearance of breathing-type adsorption isotherms that exhibit large hysteresis loops (for CO2 and H2O) attributed to strong host-guest interactions. Theoretical modeling provides information about the adsorption mechanism and supports interpretation of experimental CO2 adsorption isotherms.

Photoinduced Electron Transfer in Inclusion Complexes of Carbon Nanohoops.

ConspectusPhotoinduced electron transfer (PET) in carbon materials is a process of great importance in light energy conversion. Carbon materials, such as fullerenes, graphene flakes, carbon nanotubes, and cycloparaphenylenes (CPPs), have unusual electronic properties that make them interesting objects for PET research. These materials can be used as electron-hole transport layers, electrode materials, or passivation additives in photovoltaic devices. Moreover, their appropriate combination opens up new possibilities for constructing photoactive supramolecular systems with efficient charge transfer between the donor and acceptor parts. CPPs build a class of molecules consisting of para-linked phenylene rings. CPPs and their numerous derivatives are appealing building blocks in supramolecular chemistry, acting as suitable concave receptors with strong host-guest interactions for the convex surfaces of fullerenes. Efficient PET in donor-acceptor systems can be observed when charge separation occurs faster than charge recombination. This Account focuses on selected inclusion complexes of carbon nanohoops studied by our group. We modeled charge separation and charge recombination in both previously synthesized and computationally designed complexes to identify how various modifications of host and guest molecules affect the PET efficiency in these systems. A consistent computational protocol we used includes a time-dependent density-functional theory (TD-DFT) formalism with the Tamm-Dancoff approximation (TDA) and CAM-B3LYP functional to carry out excited state calculations and the nonadiabatic electron transfer theory to estimate electron-transfer rates. We show how the photophysical properties of carbon nanohoops can be modified by incorporating additional π-conjugated fragments and antiaromatic units, multiple fluorine substitutions, and extending the overall π-electron system. Incorporating π-conjugated groups or linkers is accompanied by the appearance of new charge transfer states. Perfluorination of the nanohoops radically changes their role in charge separation from an electron donor to an electron acceptor. Vacancy defects in π-extended nanohoops are shown to hinder PET between host and guest molecules, while large fully conjugated π-systems improve the electron-donor properties of nanohoops. We also highlight the role of antiaromatic structural units in tuning the electronic properties of nanohoops. Depending on the aromaticity degree of monomeric units in nanohoops, the direction of electron transfer in their complexes with C60 fullerene can be altered. Nanohoops with aromatic units usually act as electron donors, while those with antiaromatic monomers serve as electron acceptors. Finally, we discuss why charged fullerenes are better electron acceptors than neutral C60 and how the charge location allows for the design of more efficient donor-acceptor systems with an unusual hypsochromic shift of the charge transfer band in polar solvents.

Hierarchically porous amino-functionalized nanoMOF network anchored phosphomolybdic acid for oxidative desulfurization and shaping application

The applications of hierarchically porous metal–organic frameworks (HP-MOFs) against traditional microporous counterparts for oxidative desulfurization (ODS) have triggered wide research interests due to their highly exposed accessible active sites and fast mass transfer of substrate molecules, particularly for the large-sized refractory sulfur compounds. Herein, a series of hierarchically porous amino-functionalized Zr-MOFs (HP-UiO-66-NH2-X) network with controllable mesopore sizes (3.5–9.2 nm) were firstly prepared through a template-free method, which were further utilized as anchoring support to bind the active phosphomolybdic acid (PMA) via the strong host–guest interaction to catalyze the ODS reaction. Benefitting from the hierarchically porous structure, accessible active sites and the strong host–guest interaction, the resultant PMA/HP-UiO-66-NH2-X exhibited excellent ODS performance, of which, the PMA/HP-UiO-66-NH2-9 with an appropriate mesopore size (4.0 nm) showed the highest catalytic activity, achieving a 99.9% removal of dibenzothiophene (DBT) within 60 min at 50 °C, far exceeding the microporous sample and PMA/HP-UiO-66. Furthermore, the scavenger experiments confirmed that •OH radical was the main reactive species and the density functional theory (DFT) calculations revealed that electron transfer (from amino group to PMA) made PMA react more easily with oxidant, thereby generating more •OH radical to promote the ODS reaction. Finally, from the industrial point of view, the powdered MOF nanoparticles (NPs) were in situ grown on the carboxymethyl cellulose (CMC) substrates and shaped into monolithic MOF-based catalysts, which still exhibited satisfying ODS performance in the case of model real fuel with good reusability, indicating its potential industrial application prospect.

Heat Transport in Clathrate Hydrates Controlled by Guest Frequency and Host-Guest Interaction.

The underlying mechanism of common limited lattice thermal conductivity (κ) in energy-related host-guest crystalline compounds has been an ongoing topic in recent decades. Here, the guest-triggered intrinsic ultralow κ of the representative xenon clathrate hydrate was investigated using the time domain thermoreflectance technique and theoretical calculations. The localized guest modes were observed to hybridize with acoustic branches and severely limit the acoustic κ contribution. Besides, the strong mode coupling enables the reshaping of the overall lattice dynamics, especially for optical branches. More importantly, we identified that guest fillers prompt great phonon scattering in wide frequencies, which originates from both the guest-frequency-controlled enhancement of phase space and the host-guest-interaction-governed lattice anharmonicity. The extremely low guest frequency and strong host-guest interaction and coupling were thereby underlined to play vital but distinct roles in κ minimization. Our results unveil the dominant factors of guest reduction effects and facilitate the design of efficient thermoelectric or other thermal-related materials.

A novel host–guest recognition electrochemiluminescence system for phenylalanine detection based on Ir@ZnO nanocomposites and cucurbit[8]uril

Iridium complexes have been considered as potential promising electrochemiluminescent (ECL) reagents in recent years. However, the instability of ECL signal and easy leaching from the electrode severely limit their applications. In this work, iridium complex doped zinc oxide (ZnO) nanocomposites (Ir@ZnO) were synthesized, which could not only increase the loading amount of iridium complex, but also improve the stability of ECL signal. A sensitive ECL sensor for the detection of phenylalanie (Phe) was proposed via the host–guest recognition of cucurbit[8]uril (Q[8]) and Phe with Ir@ZnO nanocomposites as a signal probe. Q[8] was combined with Ir@ZnO nanocomposites via coordinate bond between carbonyl group of Q[8] and Ir and Zn atoms, which could quench the ECL intensity due to the accommodating ability of Q[8] for dissolved oxygen. In the presence of Phe, Q[8] could be released from the electrode surface through the strong host–guest interaction, and the ECL intensity was restored. The ECL system performed high sensitivity and low detection limit, indicating that the proposed ECL strategy was suitable for the detection of amino acids. Moreover, this work provided a new avenue for the application of water insoluble Ir complexes in ECL sensing field.

Highly Selective Transport and Enrichment of Lithium Ions through Bionic Ion Pair Receptor Nanochannels.

Inspired by ion pair cotransport channels in biological systems, a bionic nanochannel modified with lithium ion pair receptors is constructed for selective transport and enrichment of lithium ions (Li+). NH2-pillar[5]arene (NP5) is chosen as ion pair receptors, and the theoretical simulation and NMR titration experiments illustrate that NP5 has good affinity for the ion pair of LiCl through a strong host-guest interaction at the molecular level. Due to the confinement effect and ion pair cooperation recognition, an NP5-based receptor was introduced into an artificial PET nanochannel. An I-V test indicated that the NP5 channel realized the highly selective recognition for Li+. Meanwhile, transmembrane transport and COMSOL simulation experiments proved that the NP5 channel achieved the transport and enrichment of Li+ through the cooperative interaction between NP5 and LiCl. Moreover, the receptor solution of transmembrane transport LiCl in the NP5 channel was used to cultivate wheat seedlings, which obviously promoted their growth. This nanochannel based on the ion pair recognition will be much useful for practical applications like metal ion extraction, enrichment, and recycle.

Supramolecular nanoparticles constructed by orthogonal assembly of pillar[5]arene-cyclodextrin dimacrocycle for chemo-photodynamic combination therapy

Chemotherapy combined with photodynamic therapy has emerged as a promising strategy for cancer treatment. However, simultaneously delivering chemotherapeutic drugs and photosensitizers and precisely adjusting the ratio of the two components as needed remains a challengeable task. Herein, novel supramolecular nanoparticles (donated as BODIPY-CPT-NPs) for chemo-photodynamic combination cancer therapy are constructed from a glutathione-responsive camptothecin-based prodrug, BODIPY photosensitizer, and dimacrocyclic host molecule through orthogonal host-guest recognitions and co-assembly. With this strategy, the ratio of prodrugs and photosensitizers in nanoparticles can be easily and precisely controlled as needed. Benefiting from the strong host-guest interactions and stable self-assembly, the nanoparticles exhibit excellent stability and photobleaching resistance. Furthermore, camptothecin can be released from nanoparticles for chemotherapy in the presence of reduction agent and single oxygen can be efficiently generated for PDT with light irradiation. The combined effects of the BODIPY-CPT-NPs have been verified in CT26 and HeLa cancer cells.

Benzimidazole-based covalent organic framework embedding single-atom Pt sites for visible-light-driven photocatalytic hydrogen evolution

Visible-light-driven photocatalytic hydrogen evolution reaction (HER) over a semiconductor provides an effective avenue to produce renewable clean energy and alleviate energy and environmental crises. However, the HER efficiency is still limited by the sluggish electron transfer process. Herein, a highly active covalent organic framework (COF) was constructed from the unusual benzimidazole monomer in a microwave-assisted solvothermal pathway. With single-atom Pt sites as cocatalyst, the catalyst exhibited an HER rate up to 115 mmol g–1 h–1 and a high turnover frequency of 4475.1 h–1 under visible-light irradiation. The above performance relied on the combination of benzimidazole moieties and COF framework, which, on the one hand, stabilized photogenerated electrons to prolong the electron lifetime, and on the other hand provided a strong host-guest interaction that resulted in the creation of single-atom Pt sites and the acceleration of the electron-transfer to the active sites for proton reduction. This work demonstrates the perspective of electron stabilization and interfacial charge transfer avenue construction in the HER process, which can be reached by a molecular-level design of COF-based organic semiconductors by using structural and functional diverse asymmetric building blocks.