Layered Silicates Exhibiting MOF-Like Gate-Opening Behaviors in Liquid-Phase Adsorptions: Experimental and Theoretical Investigations.

Layered silicates, including clay minerals, can be used as liquid-phase adsorbents in many important applications. However, because their two-dimensional interlayer space is narrow and not entirely opened due to the presence of interlayer species, guest species are forced to penetrate while expanding the interlayer space, which limits their adsorption performances compared with microporous materials such as MOFs and zeolites. Herein, as reported for the adsorption of gaseous species on flexible MOFs, we report a layered silicate that exhibits gate-opening adsorption in liquid phases. This layered silicate, synthesized via dilute acid treatment of the parent sodium-type, exhibits an abrupt increase in the basal spacing (layer thickness + interlayer space) to reach a plateau even at an earlier stage of benzoic acid adsorption from acetonitrile, whereas a typical layered silicate, magadiite, exhibits a gradual increase in the basal spacing as adsorption progress under identical conditions. The layered silicate shows an excellent adsorption capacity and rate for benzoic acid uptake from acetonitrile, which is considerably higher than that of magadiite. With comprehensive adsorption tests using different adsorbates and solvents, we propose that the layered silicate has zeolite-like but distorted, flexible open microchannels within each layer, and the intralayer microchannels can effectively and rapidly accommodate the solvent (acetonitrile) molecules, which are capable of expanding the framework to initiate the adsorption of aromatic compounds. The density function theory calculation revealed the adsorption mechanism, where the layered silicate accommodates acetonitrile in the intralayer microchannel followed by the interlayer space, and the former selectively plays a role as the adsorption site of aromatic compounds via exchange with acetonitrile.

Effect of Boron-Doping on Gate-Opening CO2 Adsorption in Zinc-Benzimidazolate Coordination Networks.

Flexible metal-organic frameworks (MOFs) have attracted much attention as selective gas adsorption and storage. This report describes boron doping in zeolitic imidazolate framework-7 (B-ZIF-7), which exhibits reversible phase transition during CO2 adsorption/desorption. We have successfully prepared B-ZIF-7 coordination networks using boron-bridged benzimidazolate (B(bim)4-) as organic ligands. Powder X-ray diffraction (PXRD) measurements and infrared spectroscopy revealed that B-ZIF-7 has a crystal structure similar to that of ZIF-7 while containing boron bridging in the coordination network. Since B-ZIF-7 forms a cationic coordination network, the guest anions are encapsulated within the pore. CO2 adsorption/desorption measurements at 300 K showed that B-ZIF-7(NO3), which contains nitrate ions (NO3-) as guest anions in its pores, exhibits a S-shaped CO2 adsorption/desorption isotherm, which is characteristic of gate-opening type MOFs. Compared with ZIF-7, B-ZIF-7(NO3) has superior CO2 adsorption capacity in the low-pressure and superior CO2 storage capacity. The CO2 adsorption and desorption behavior of B-ZIF-7(NO3) was analyzed by in situ temperature-controlled PXRD measurements and thermogravimetric analysis under a CO2 atmosphere, and a reversible phase transition was observed. We have also successfully prepared B-ZIF-7(Cl) and B-ZIF-7(OTf) (OTf = CF3SO3-) with different guest anions. The CO2 adsorption/desorption behaviors of B-ZIF-7(Cl) and B-ZIF-7(OTf) were significantly different from those of B-ZIF-7(NO3) and ZIF-7. B-ZIF-7(Cl) showed gate opening at a higher pressure than ZIF-7, and B-ZIF-7(OTf) did not show S-shaped CO2 adsorption isotherm and showed adsorption behavior in micropores. These results indicate that the CO2 adsorption behavior of B-ZIF-7 depends on the interaction between the guest anions and CO2 molecules or the cationic framework and the bulkiness of the guest anions. Boron doping in a coordination network with boron-bridged imidazolate ligands is a promising strategy to increase the gas adsorption capability of porous materials.

Effect of Polymorphism on the Sorption Properties of a Flexible Square-Lattice Topology Coordination Network.

The stimulus-responsive behavior of coordination networks (CNs), which switch between closed (nonporous) and open (porous) phases, is of interest because of its potential utility in gas storage and separation. Herein, we report two polymorphs of a new square-lattice (sql) topology CN, X-sql-1-Cu, of formula [Cu(Imibz)2]n (HImibz = {[4-(1H-imidazol-1-yl)phenylimino]methyl}benzoic acid), isolated from the as-synthesized CN X-sql-1-Cu-(MeOH)2·2MeOH, which subsequently transformed to a narrow pore solvate, X-sql-1-Cu-A·MeOH, upon mild activation (drying in air or heating at 333 K under nitrogen). X-sql-1-Cu-A·MeOH contains MeOH in cavities, which was removed through exposure to vacuum for 2 h, yielding the nonporous (closed) phase X-sql-1-Cu-A. In contrast, a more dense polymorph, X-sql-1-Cu-B, was obtained by exposing X-sql-1-Cu-(MeOH)2·2MeOH directly to vacuum for 2 h. Gas sorption studies conducted on X-sql-1-Cu-A and X-sql-1-Cu-B revealed different switching behaviors to two open phases (X-sql-1-Cu·CO2 and X-sql-1-Cu·C2H2), with different gate-opening threshold pressures for CO2 at 195 K and C2H2 at 278 K. Coincident CO2 sorption and in situ powder X-ray diffraction studies at 195 K revealed that X-sql-1-Cu-A transformed to X-sql-1-Cu-B after the first sorption cycle and that the CO2-induced switching transformation was thereafter reversible. The results presented herein provide insights into the relationship between two polymorphs of a CN and the effect of polymorphism upon gas sorption properties. To the best of our knowledge, whereas sql networks such as X-sql-1-Cu are widely studied in terms of their structural and sorption properties, this study represents only the second example of an in-depth study of the sorption properties of polymorphic sql networks.

Exploring the role of working memory gate opening process in creativity: An ERP study using the reference-back paradigm.

We investigated the relationship between the gate opening process of working memory and an individual's proficiency in divergent (DT) and convergent thinking (CT) using the reference-back paradigm. Event-related potentials and reaction times were measured across groups with varying DT (N = 40, 27.35 ± 5.05 years) and CT levels (N = 40, 27.88 ± 4.95 years). Based on the role of striatal dopamine in supporting cognitive flexibility, which facilitates DT, and considering the significance of phasic dopamine activity as the gate opening signal originating from the basal ganglia, we assumed that the gate opening process may contribute differently to DT and CT. Despite the absence of behavioural differences in gate opening costs, distinct neural patterns emerged. In the early time windows (P1, N1), gate opening effects were detected in both DT and CT groups, with a notable interaction influenced by the level of DT, resulting in significant effects within the lower DT group. The P2 component showed a gate opening effect only in the higher DT group. In the P3 time window, the process unfolded comparably in all groups. Our results suggest that groups with different levels of convergent thinking (based on Matrix reasoning) and those with lower DT (based on Creativity Index) tend to select and activate the prefrontal cortex representation containing the required task information at an earlier stage, compared to those with better DT. This could be beneficial especially in the early phase of idea generation, as more elements become available to create associations and original ideas.

Advanced Soft Porous Organic Crystal with Multiple Gas-Induced Single-Crystal-to-Single-Crystal Transformations for Highly Selective Separation of Propylene and Propane.

Soft porous organic crystals with stimuli-responsive single-crystal-to-single-crystal (SCSC) transformations are important tools for unraveling their structural transformations at the molecular level, which is of crucial importance for the rapid development of stimuli-responsive systems. Carefully balancing the crystallinity and flexibility of materials is the prerequisite to construct advanced organic crystals with SCSC, which remains challenging. Herein, a squaraine-based soft porous organic crystal (SPOC-SQ) with multiple gas-induced SCSC transformations and temperature-regulated gate-opening adsorption of various C1-C3 hydrocarbons is reported. SPOC-SQ is featured with both crystallinity and flexibility, which enable pertaining the single crystallinity of the purely organic framework during accommodating gas molecules and directly unveiling gas-framework interplays by SCXRD technique. Thanks to the excellent softness of SPOC-SQ crystals, multiple metastable single crystals are obtained after gas removals, which demonstrates a molecular-scale shape-memory effect. Benefiting from the single crystallinity, the molecule-level structural evolutions of the SPOC-SQ crystal framework during gas departure are uncovered. With the unique temperature-dependent gate-opening structural transformations, SPOC-SQ exhibits distinctly different absorption behaviors towards C3 H6 and C3 H8 , and highly efficient and selective separation of C3 H6 /C3 H8 (v/v, 50/50) is achieved at 273 K. Such advanced soft porous organic crystals are of both theoretical values and practical implications.

CO2-Induced Gate-Opening Adsorption on a Chabazite/Phillipsite Composite Zeolite Transformed from a Faujasite Zeolite Using Organic Structure-Directing Agent-Free Steam-Assisted Conversion.

Organic structure-directing agent-free steam-assisted conversion and Cs+ ion exchange were used to transform the faujasite (FAU)-type zeolite to the Cs+-type chabazite/phillipsite (CHA/PHI) composite zeolite. Compared with the pure PHI-type zeolite, the Cs+-type CHA/PHI zeolite showed gate-opening CO2 adsorption behavior and good thermal stability. In situ powder X-ray diffraction (PXRD) of the CO2 adsorption was measured to elucidate the mechanism for the gate-opening adsorption on the CHA/PHI zeolite. The Na+-type CHA/PHI zeolite did not show such adsorption behavior, and the PXRD pattern of the Na+-type CHA/PHI zeolite did not change with increasing CO2 partial pressure, which suggests that this unique adsorption behavior was caused by the PHI framework transition or Cs+ ions moving in both the CHA and PHI frameworks. Furthermore, in situ Fourier-transform infrared spectra of CO2 adsorption and CO2 breakthrough measurement on the Cs+-type CHA/PHI zeolite suggest that the CHA and PHI frameworks in the CHA/PHI zeolite shared eight-membered-ring windows and that CO2 molecules could easily diffuse from a CHA cage to a PHI framework. The ideal adsorbed solution theory was used to calculate the CO2/N2 separation selectivity for the Cs+-type CHA/PHI zeolite. At 298 and 318 K, the Cs+-type CHA/PHI composite zeolite showed a high CO2/N2 separation coefficient of >10,000 compared with other zeolites with high CO2 adsorption capacity. Furthermore, the CO2 working capacity was calculated for the Cs+-type CHA/PHI zeolite in both the pressure- and temperature-swing processes, and the results showed that the CHA/PHI composite zeolite could selectively separate CO2 from the CO2/N2 gas mixtures released from power generation plants operating using these processes.

Flexible Luminescent Hydrogen-bonded Organic Framework for the Separation of Benzene and Cyclohexane.

A nonplanar phenothiazine derivative with three cyano moieties (PTTCN) is designed and synthesized to achieve functional crystals for absorptive separation of benzene and cyclohexane. PTTCN can crystallize into two kinds of crystals with different fluorescence colors in different solvent systems. The molecules in two crystals are in different stereo isomeric forms of nitrogen, quasi axial (ax), and quasi equatorial (eq). The crystals with blue fluorescence in ax form may selectively adsorb benzene by a single-crystal-to-single-crystal (SCSC) transformation, but separated benzene from a benzene/cyclohexane equimolar mixture with a low purity of 79.6%. Interestingly, PTTCN molecules with eq form and benzene co-assembled to construct a hydrogen-bonded framework (X-HOF-4) with S-type solvent channels and yellow-green fluorescence, and can release benzene to form nonporous guest-free crystal under heating. Such nonporous crystals strongly favor aromatic benzene over cyclohexane and may selectively reabsorb benzene from benzene/cyclohexane equimolar mixture to recover original framework, and the purity of benzene can reach ≈96.5% after release from framework. Moreover, reversible transformation between the nonporous crystals and the guest-containing crystals allows the material to be reused.

Discriminatory Gate-Opening Effect in a Flexible Metal-Organic Framework for Inverse CO2 /C2 H2 Separation.

Considering the significant application of acetylene (C2 H2 ) in the manufacturing and petrochemical industries, the selective capture of impurity carbon dioxide (CO2 ) is a crucial task and an enduring challenge. Here, a flexible metal-organic framework (Zn-DPNA) accompanied by a conformation change of the Me2 NH2 + ions in the framework is reported. The solvate-free framework provides a stepped adsorption isotherm and large hysteresis for C2 H2 , but type-I adsorption for CO2 . Owing to their uptakes difference before gate-opening pressure, Zn-DPNA demonstrated favorable inverse CO2 /C2 H2 separation. According to molecular simulation, the higher adsorption enthalpy of CO2 (43.1 kJ mol-1 ) is due to strong electrostatic interactions with Me2 NH2 + ions, which lock the hydrogen-bond network and narrow pores. Furthermore, the density contours and electrostatic potential verifies the middle of the cage in the large pore favors C2 H2 and repels CO2 , leading to the expansion of the narrow pore and further diffusion of C2 H2 . These results provide a new strategy that optimizes the desired dynamic behavior for one-step purification of C2 H2 .

Metal Doping to Control Gate Opening and Increase Methane Working Capacity in Isostructural Flexible Diamondoid Networks.

Adsorbed natural gas (ANG) systems involve using porous materials to increase the working capacity and/or reduce the storage pressure compared to compressed natural gas (CNG). Flexible metal-organic materials (FMOMs) are particularly interesting in this context since their stepped isotherms can afford increased working capacity if the adsorption/desorption steps occur within the proper pressure range. We report herein that metal doping in a family of isostructural FMOMs, ML2 (M=Co, Ni or Nix Co1-x , L=4-(4-pyridyl)-biphenyl-4-carboxylic acid), enables control over the gate opening between non-porous (closed) and porous (open) phases at pressures relevant to methane storage. Specifically, methane-induced phase transformations can be fine-tuned by using different Ni/Co ratios to enhance methane working capacity. The optimal working capacity from 5 to 35 bar at 298 K (153 cm3  cm-3 ) was found for Ni0.89 Co0.11 L2 (X-dia-1-Ni0.89 Co0.11 ), which is greater than that of benchmark rigid MOFs.

Strengthening Intraframework Interaction within Flexible MOFs Demonstrates Simultaneous Sieving Acetylene from Ethylene and Carbon Dioxide.

Efficient separation of acetylene (C2 H2 )/ethylene (C2 H4 ) and acetylene/carbon dioxide (CO2 ) by adsorption is an industrially promising process, but adsorbents capable of simultaneously capturing trace acetylene from ethylene and carbon dioxide are scarce. Herein, a gate-opening effect on three isomorphous flexible metal-organic frameworks (MOFs) named Co(4-DPDS)2 MO4 (M = Cr, Mo, W; 4-DPDS = 4,4-dipyridyldisulfide) is modulated by anion pillars substitution. The shortest CrO4 2- strengthens intraframework hydrogen bonding and thus blocks structural transformation after activation, striking a good balance among working capacity, separation selectivity, and trace impurity removal of flexible MOFs out of nearly C2 H2 /C2 H4 and C2 H2 /CO2 molecular sieving. The exceptional separation performance of Co(4-DPDS)2 CrO4 is confirmed by dynamic breakthrough experiments. It reveals the specific threshold pressures control in anion-pillared flexible materials enabled elimination of the impurity leakage to realize high purity products through precise control of the intraframework interaction. The adsorption mechanism and multimode structural transformation property are revealed by both calculations and crystallography studies. This work demonstrates the feasibility of modulating flexibility for controlling gate-opening effect, especially for some cases of significant aperture shrinkage after activation.

Tuning the Structural Flexibility for Multi-Responsive Gas Sorption in Isonicotinate-Based Metal-Organic Frameworks.

Flexible metal-organic frameworks (MOFs) are of high interest as smart programmable materials for gas sorption due to their unique structural changes triggered by external stimuli. Owing to this property, which leads to opportunities such as maximizing deliverable gas capacity, flexible MOFs sometimes offer more advantages in sorption applications compared to their more rigid counterparts. Herein, we elucidate the effect of transition metal identity of a series of isonicotinate-based flexible MOFs, M(4-PyC)2 [M═Mg, Mn, and Cu; 4-PyC = 4-pyridine carboxylic acid] on the structural dynamic response to different gases (C2H4, C2H6, Xe, Kr, and SO2). Isotherms at different temperatures show that C2H4, C2H6, and Xe can form sufficiently strong interactions with both Mg(4-PyC)2 and Mn(4-PyC)2 frameworks resulting in gate-opening behavior due to the rotation of the linker's pyridine ring, while Kr cannot induce this phenomenon for the two MOFs under the measured conditions. In contrast, the gate-opening behavior occurs for Cu(4-PyC)2 solely in the presence of C2H4, and no other measured gas, due to the open metal sites of Cu centers. In comparison, SO2, a strong polar molecule, triggers the gate-opening effect in all three MOFs. Interestingly, a shape memory effect is observed for Cu(4-PyC)2 during the second SO2 sorption cycle. When comparing the different gate-opening pressures of each gas, we observed that the structural flexibility of the three frameworks is highly sensitive to the chemical hardness of the Lewis acidic metal ions (Mg2+ > Mn2+ > Cu2+). As a result, the gate opening behavior is observed at lower pressures for the MOFs containing weaker M-N bonds (harder metal ions), with the exception of Cu(4-PyC)2 toward C2H4. These observations reveal that different transition metals can be used to finely control the structural flexibility of the frameworks.

Tuning Gate-Opening of a Flexible Metal-Organic Framework for Ternary Gas Sieving Separation.

In comparison with the fast development of binary mixture separations, ternary mixture separations are significantly more difficult and have rarely been realized by a single material. Herein, a new strategy of tuning the gate-opening pressure of flexible MOFs is developed to tackle such a challenge. As demonstrated by a flexible framework NTU-65, the gate-opening pressure of ethylene (C2 H4 ), acetylene (C2 H2 ), and carbon dioxide (CO2 ) can be regulated by temperature. Therefore, efficient sieving separation of this ternary mixture was realized. Under optimized temperature, NTU-65 adsorbed a large amount of C2 H2 and CO2 through gate-opening and only negligible amount of C2 H4 . Breakthrough experiments demonstrated that this material can simultaneously capture C2 H2 and CO2 , yielding polymer-grade (>99.99 %) C2 H4 from single breakthrough separation.

Separation of Xe from Kr with Record Selectivity and Productivity in Anion-Pillared Ultramicroporous Materials by Inverse Size-Sieving.

The separation of xenon/krypton (Xe/Kr) mixture is of great importance to industry, but the available porous materials allow the adsorption of both, Xe and Kr only with limited selectivity. Herein we report an anion-pillared ultramicroporous material NbOFFIVE-2-Cu-i (ZU-62) with finely tuned pore aperture size and structure flexibility, which for the first time enables an inverse size-sieving effect in separation along with record Xe/Kr selectivity and ultrahigh Xe capacity. Evidenced by single-crystal X-ray diffraction, the rotation of anions and pyridine rings upon contact of larger-size Xe atoms adapts cavities to the shape/size of Xe and allows strong host-Xe interaction, while the smaller-size Kr is excluded. Breakthrough experiments confirmed that ZU-62 has a real practical potential for producing high-purity Kr and Xe from air-separation byproducts, showing record Kr productivity (206 mL g-1 ) and Xe productivity (42 mL g-1 , in desorption) as well as good recyclability.

Tuning the Gate-Opening Pressure in a Switching pcu Coordination Network, X-pcu-5-Zn, by Pillar-Ligand Substitution.

Coordination networks that reversibly switch between closed and open phases are of topical interest since their stepped isotherms can offer higher working capacities for gas-storage applications than the related rigid porous coordination networks. To be of practical utility, the pressures at which switching occurs, the gate-opening and gate-closing pressures, must lie between the storage and delivery pressures. Here we study the effect of linker substitution to fine-tune gate-opening and gate-closing pressure. Specifically, three variants of a previously reported pcu-topology MOF, X-pcu-5-Zn, have been prepared: X-pcu-6-Zn, 6=1,2-bis(4-pyridyl)ethane (bpe), X-pcu-7-Zn, 7=1,2-bis(4-pyridyl)acetylene (bpa), and X-pcu-8-Zn, 8=4,4'-azopyridine (apy). Each exhibited switching isotherms but at different gate-opening pressures. The N2 , CO2 , C2 H2 , and C2 H4 adsorption isotherms consistently indicated that the most flexible dipyridyl organic linker, 6, afforded lower gate-opening and gate-closing pressures. This simple design principle enables a rational control of the switching behavior in adsorbent materials.

Structural Basis of CO2 Adsorption in a Flexible Metal-Organic Framework Material.

This paper reports on the structural basis of CO2 adsorption in a representative model of flexible metal-organic framework (MOF) material, Ni(1,2-bis(4-pyridyl)ethylene)[Ni(CN)4] (NiBpene or PICNIC-60). NiBpene exhibits a CO2 sorption isotherm with characteristic hysteresis and features on the desorption branch that can be associated with discrete structural changes. Various gas adsorption effects on the structure are demonstrated for CO2 with respect to N2, CH4 and H2 under static and flowing gas pressure conditions. For this complex material, a combination of crystal structure determination and density functional theory (DFT) is needed to make any real progress in explaining the observed structural transitions during adsorption/desorption. Possible enhancements of CO2 gas adsorption under supercritical pressure conditions are considered, together with the implications for future exploitation. In situ operando small-angle neutron and X-ray scattering, neutron diffraction and X-ray diffraction under relevant gas pressure and flow conditions are discussed with respect to previous studies, including ex situ, a priori single-crystal X-ray diffraction structure determination. The results show how this flexible MOF material responds structurally during CO2 adsorption; single or dual gas flow results for structural change remain similar to the static (Sieverts) adsorption case, and supercritical CO2 adsorption results in enhanced gas uptake. Insights are drawn for this representative flexible MOF with implications for future flexible MOF sorbent design.

Rotational Dynamics of Linkers in Metal⁻Organic Frameworks.

Among the numerous fascinating properties of metal⁻organic frameworks (MOFs), their rotational dynamics is perhaps one of the most intriguing, with clear consequences for adsorption and separation of molecules, as well as for optical and mechanical properties. A closer look at the rotational mobility in MOF linkers reveals that it is not only a considerably widespread phenomenon, but also a fairly diverse one. Still, the impact of these dynamics is often understated. In this review, we address the various mechanisms of linker rotation reported in the growing collection of literature, followed by a highlight of the methods currently used in their study, and we conclude with the impacts that such dynamics have on existing and future applications.

In Situ Tracking of Dynamic NO Capture through a Crystal-to-Crystal Transformation from a Gate-Open-Type Chain Porous Coordination Polymer to a NO-Adducted Discrete Isomer.

Optimal control of gas adsorption properties in metal-organic frameworks (MOFs) or porous coordination polymers (PCPs) remains a great challenge in the field of materials science. An efficient strategy to capture electron-acceptor-type gas molecules such as nitrogen monooxide (NO) is to use host-guest interactions by utilizing electron-donor-type MOFs/PCPs as host frameworks. Herein, we focus on a highly electron-donating chain compound by using the paddlewheel-type [Ru2 II,II ] complex [Ru2 (2,4,5-Me3 PhCO2 )4 ] (2,4,5-Me3 PhCO2 - =2,4,5-trimethylbenzoate) with the phenazine (phz) linker: [Ru2 (2,4,5-Me3 PhCO2 )4 (phz)] (1). Compound 1 exhibited a specific gated adsorption for NO under gas pressures greater than 60 kPa at 121 K, which finally resulted in approximately seven molar equivalents being taken up at 100 kPa followed by four molar equivalents remaining under vacuum at 121 K; its Rh isomorph (2) with weaker donation ability was inactive for NO. When the sample of 1⊃4 NO was heated to room temperature, the compound underwent a crystal-to-crystal phase transition to give [Ru2 (2,4,5-Me3 PhCO2 )4 (NO)2 ](phz) (1-NO), involving a post-synthetic nitrosylation on the [Ru2 ] unit, accompanied by an eventful site-exchange with phz. This drastic event, which is dependent on the NO pressure, temperature, and time, was coherently monitored by using several different in situ techniques, revealing that the stabilization of NO molecules in nanosized pores dynamically and stepwisely occurred with the support of strong electronic/magnetic host-guest interactions.

Microporous Organically Pillared Layered Silicates (MOPS): A Versatile Class of Functional Porous Materials.

The design of microporous hybrid materials, tailored for diverse applications, is a key to address our modern society's imperative of sustainable technologies. Prerequisites are flexible customization of host-guest interactions by incorporating various types of functionality and by adjusting the pore structure. On that score, metal-organic frameworks (MOFs) have been the reference in the past decades. More recently, a new class of microporous hybrid materials emerged, microporous organically pillared layered silicates (MOPS). MOPS are synthesized by simple ion exchange of organic or metal complex cations in synthetic layered silicates. MOFs and MOPSs share the features of "component modularity" and "functional porosity". While both, MOFs and MOPS maintain the intrinsic characteristics of their building blocks, new distinctive properties arise from their assemblage. MOPS are unique since allowing for simultaneous and continuous tuning of micropores in the sub-Ångström range. Consequently, with MOPS the adsorbent recognition may be optimized without the need to explore different framework topologies. Similar to the third generation of MOFs (also termed soft porous crystals), MOPS are structurally ordered, permanently microporous solids that may also show a reversible structural flexibility above a distinct threshold pressure of certain adsorbents. This structural dynamism of MOPS can be utilized by meticulously adjusting the charge density of the silicate layers to the polarizability of the adsorbent leading to different gate opening mechanisms. The potential of MOPS is far from being fully explored. This Concept article highlights the main features of MOPS and illustrates promising directions for further research.

Liquid Intrusion into Zeolitic Imidazolate Framework-7 Nanocrystals: Exposing the Roles of Phase Transition and Gate Opening to Enable Energy Absorption Applications.

Liquid intrusion into zeolitic imidazolate framework 7 (ZIF-7) has been observed for the first time. Among the three typical phases of ZIF-7, we discover that only the guest-free ZIF-7-II structure can be intruded by mechanical pressure, and intriguingly, this pressurized liquid intrusion behavior is detected only in nanocrystals, indicating the crystal size effect. Because of its unique combination of non-outflow property and high intrusion pressure, water intrusion into ZIF-7-II generates a marked energy dissipation capacity of ∼2 J/g despite its limited pore volume. We present several strategies that can be easily implemented to tune its intrusion pressure and energy dissipation and accomplish material reusability. Remarkably, we found that the pore cavities of ZIF-7-II can accommodate water molecules without experiencing any phase transition, which is entirely different from other solvents whose incorporation will trigger a spontaneous conversion into ZIF-7-I. Our pressure-vs-volume data further reveal that the process of water infiltration and retainment is controlled by the gate-opening/closing mechanism, which has enabled us to probe the viscoelasticity of ZIF-7 via cyclic liquid intrusion experiments. This study has deepened our understanding of the time-dependent mechanical properties of ZIFs and shed new light on the structural flexibility central to the novel applications of metal-organic framework materials.

Measurement of the Multiple Activities of 26S Proteasomes.

Because proteasomes catalyze most of the protein degradation in mammalian cells, and their functioning is essential for cellular homeostasis, proteasome structure, biochemical mechanisms, and regulation in normal and disease states are now widely studied and are of major importance. In addition, inhibitors of the proteasome's peptidase activity have proven to be very valuable as research tools and in the treatment of hematologic malignancies, and a number of newer pharmacological agents that alter proteasome function are being developed. The rapid degradation of ubiquitinated proteins by the 26S proteasome involves multiple enzymatic and non-enzymatic steps, including the binding of ubiquitinated substrates to the 19S particle (Subheading 3.2), opening the gated substrate entry channel into the 20S particle (Subheading 3.3), disassembly of the Ub chain (Subheading 3.4), ATP hydrolysis (Subheading 3.5), substrate unfolding and translocation, and proteolysis within the 20S particle (Subheadings 3.3 and 3.7). Assaying each of these processes is important if we are to fully understand the physiological regulation of proteasome function and the effects of disease or drugs. Here, we describe several methods that we have found useful to measure many of these individual activities using purified proteasomes. Studies using these approaches have already provided valuable new insights into the effects of post-synthetic modifications to 26S subunits, the physiological regulation of the ubiquitin-proteasome system, and the impairment of proteasome activity in neurodegenerative disease. These advances would not have been possible if only the standard assays of peptidase activity were used.