Soaking the Rare-Earth Carbonates for a Change: An Alternative Approach to Explore Carbonate Nonlinear Optical Crystals.

Alkali-metal rare-earth carbonates (ARECs) find great potential in nonlinear optical applications. As the most common method, the hydrothermal reaction is widely used in synthesizing ARECs. The black-box nature of the hydrothermal reaction makes it difficult for understanding the formation processes and therefore may slow down the pace of structural discovery. Here, by simply soaking the rare-earth carbonates in Na2CO3 solutions, we successfully obtain a series of noncentrosymmetric Na3RE(CO3)3·6H2O (RE = Tb 1, Sm 2, Eu 3, Gd 4, Dy 5, Ho 6, and Er 7) compounds without using the high-temperature hydrothermal method. The transformation process, investigated by powder X-ray diffraction and scanning electron microscopy, is governed by the concentration of the soaking solutions. Na3Tb(CO3)3·6H2O, as an example, is studied structurally, and its physical properties are characterized. It exhibits a second harmonic generation effect of 0.5 × KDP and a short UV cutoff edge of 222 nm (5.8 eV). Our study provides insights for exploring new AREC structures, which may further advance the development of carbonate nonlinear optical crystals.

Temperature-Dependent Separation of CO2 from Light Hydrocarbons in a Porous Self-Assembly of Vertexes Sharing Octahedra.

Design of flexible porous materials where the diffusion of guest molecules is regulated by the dynamics of contracted pore aperture is challenging. Here, a flexible porous self-assembly consisting of 1D channels with dynamic bottleneck gates is reported. The dynamic pendant naphthimidazolylmethyl moieties at the channel necks provide kinetic gate function, that enables unusual adsorption for light hydrocarbons. The adsorption for CO2 is mainly dominated by thermodynamics with the uptakes decreasing with increasing temperature, whereas the adsorptions for larger hydrocarbons are controlled by both thermodynamics and kinetics resulting in an uptake maximum at a temperature threshold. Such an unusual adsorption enables temperature-dependent separation of CO2 from the corresponding hydrocarbons.

Trapping an Ester Hydrate Intermediate in a π-Stacked Macrocycle with Multiple Hydrogen Bonds.

Ester hydrates, as the intermediates of the esterification between acid and alcohol, are very short-lived and challenging to be trapped. Therefore, the crystal structures of ester hydrates have rarely been characterized. Herein, we present that the mono-deprotonated ester hydrates [CH3OSO2(OH)2]-, serving as the template for the self-assembly of a π-stacked boat-shaped macrocycle (CH3OSO2(OH)2)0.67(CH3OSO3)1.33@{[ClLCoII]6}·Cl4·13CH3OH·9H2O (1) (L = tris(2-benzimidazolylmethyl) amine), can be trapped in the host by multiple NH···O hydrogen bonds. In the solution of CoCl2, L, and H2SO4 in MeOH, HSO4- reacts with MeOH, producing [CH3OSO3]- via the ester hydrate intermediate of [CH3OSO3(OH)2]-. Both the product and the intermediate serve as the template directing the self-assembly of the π-stacked macrocycle, in which the short-lived ester hydrate is firmly trapped and stabilized, as revealed by single-crystal analysis.

Metalation of a Hierarchical Self-Assembly Consisting of π-Stacked Cubes through Single-Crystal-to-Single-Crystal Transformation.

Single-crystal-to-single-crystal metalation of organic ligands represents a novel method to prepare metal-organic complexes, but remains challenging. Herein, a hierarchical self-assembly {(H12L8)·([N(C2H5)4]+)3·(ClO4-)15·(H2O)32} (1) (L = tris(2-benzimidazolylmethyl) amine) consisting of π-stacked cubes which are assembled from eight partially protonated L ligands is obtained. By soaking the crystals of compound 1 in the aqueous solution of Co(SCN)2, the ligands coordinate with Co2+ ions stoichiometrically and ClO4- exchange with SCN- via single-crystal-to-single-crystal transformation, leading to {([CoSCNL]+)8·([NC8H20]+)3·(SCN)11·(H2O)13} (2).

A Porous π-Stacked Self-Assembly of Cup-Shaped Palladium Complex for Iodine Capture.

Acquiring adsorbents capable of effective radioiodine capture is important for nuclear waste treatment; however, it remains a challenge to develop porous materials with high and reversible iodine capture. Herein, we report a porous self-assembly constructed by a cup-shaped PdII complex through intermolecular π···π interactions. This self-assembly features a cubic structure with channels along all three Cartesian coordinates, which enables it to efficiently capture iodine with an adsorption capacity of 0.60 g g-1 for dissolved iodine and 1.81 g g-1 for iodine vapor. Furthermore, the iodine adsorbed within the channels can be readily released upon immersing the bound solid in CH2Cl2, which allows the recycling of the adsorbent. This work develops a new porous molecular material promising for practical iodine adsorption.

Achieving stable photoluminescence by double thiacalix[4]arene-capping: the lanthanide-oxo cluster core matters.

Luminescence stability is a critical consideration for applying phosphors in practical devices. In this work, we report two categories of double p-tert-butylthiacalix[4]arene (H4TC4A) capped clusters that exhibit characteristic lanthanide luminescence. Specifically, {[Ln4(µ4-OH)(TC4A)2(DMF)6(CH3OH)3(HCOO)Cl2]}·xCH3OH (Ln = Eu (1), Tb (2); x = 0-1) with square-planar [Ln4(µ4-OH)] cluster cores and {[Ln9(µ5-OH)2(µ3-OH)8(OCH3) (TC4A)2 (H2O)24Cl9]}·xDMF (Ln = Gd (3), Tb (4), Dy (5); x = 2-6) with hourglass-like [Ln9(µ5-OH)2(µ3-OH)8] cluster cores are synthesized and characterized. By comparing 2 and 4, we find that several critical luminescence properties (such as quantum efficiency and luminescence stabilities) depend directly on the cluster core structure. With the square-planar [Ln4(µ4-OH)] cluster cores, 2 demonstrates high quantum yield (∼65%) and excellent luminescence stability against moisture, high temperature, and UV-radiation. A white light-emitting diode (LED) with ultrahigh color quality is successfully fabricated by mixing 2 with commercial phosphors. These results imply that high quality phosphors might be achieved by exploiting the double thiacalix[4]arene-capping strategy, with an emphasis on the cluster core structure.

From a Metal-Organic Square to a Robust and Regenerable Supramolecular Self-assembly for Methane Purification.

Porous supramolecular assemblies constructed by noncovalent interactions are promising for adsorptive purification of methane because of their easy regeneration. However, the poor stability arising from the weak noncovalent interactions has obstructed their practical applications. Here, we report a robust and easily regenerated polyhedron-based cationic framework assembled from a metal-organic square. This material exhibits a very low affinity for CH4 and N2 , but captures other competing gases (e.g. C2 H6 , C3 H8 , and CO2 ) with a moderate affinity. These results underpin highly selective separation of a range of gas mixtures that are relevant to natural gas and industrial off-gas. Dynamic breakthrough studies demonstrate its practical separation for C2 H6 /CH4 , C3 H8 /CH4 , CO2 /N2 , and CO2 /CH4 . Particularly, the separation time is ≈11 min g-1 for the C2 H6 /CH4 (15/85 v/v) mixture and ≈49 min g-1 for the C3 H8 /CH4 (15/85 v/v) mixture (under a flow of 2.0 mL min-1 ), respectively, enabling its capability for CH4 purification from light alkanes.

Effect of Fe(III) Modification on the Phosphorus Removal Behavior of Ce(III) Carbonate Adsorbents.

Excessive phosphorus (P) in water is the main reason for eutrophication, which has been a global problem for many years. For the adsorption treatment of phosphorus-containing wastewater, adsorbents are key research topics. In this study, we develop the synthesis of a series of Ce/Fe adsorbents by modifying the commercial cerium carbonate with Fe2(SO4)3. By conducting comprehensive analysis with XRD, FTIR, and SEM, we find that the amorphous granular structure and large chunky structure created by the high and low Fe content, respectively, both had a negative effect on the adsorption capacity of phosphate. Among different adsorbents, Ce/Fe-15/3, with Ce loading of 28.33 wt % and Fe loading of 5.66 wt %, exhibits high P adsorption capacity of 58 mg P/g (in pH = 7, 30 mg P/L solution). It also demonstrates excellent selectivity toward phosphate adsorption in Cl-, SO4 2-, and NO3 - solution (up to 20 times of the phosphate molarity) and good adsorption stability in acidic environments (pH = 3-6). The adsorption behavior of Ce/Fe-15/3 can be modeled well by the Langmuir model and pseudo-second-order (PSO) model. By conducting the XPS analysis, we conclude that the adsorption mechanism is a combination effect of Ce/PO4 3- and Fe/PO4 3- chemical interactions.

Ultrastable Photoluminescence Enabled by 1D Rare-Earth Metal-Organic Frameworks Based on Double Thiacalix[4]arene-Capped Nodes.

Luminescent stability is a vital factor that dictates the application of lanthanide luminescent materials. Designing luminescent lanthanide cluster nodes that form an extended framework with predictable linking patterns may help enhance the structural stability of the lanthanide complexes and hence lead to improved luminescent stability. Herein, we report a series of one-dimensional (1D) rare-earth metal-organic framework compounds, {Ln4(µ4-OH)(TC4A)2(H2O)2(CH3O)(HCOO)2(HCOOH)}·xCH3OH (Ln = Sm (1), Eu (2), Tb (3), Dy (4); x = 1-5), based on double thiacalix[4]arene-capped Ln4(µ4-OH)(TC4A)2 nodes. The axially capped Ln4(µ4-OH)(TC4A)2 nodes are connected equatorially by formate bridges to form zigzag 1D-metal-organic framework (MOF) chains, which further assemble into a quasi-two-dimensional (2D) structure via hydrogen bonding. These unique features result in a stable structure and therefore superior luminescent stability. For example, the Tb-based 1D-MOF (3) exhibits intensive green photoluminescence with a quantum yield of 53% and an average decay time of 1.33 × 106 ns. It maintains its integrated emission intensity at 96.5, 94.5, and 89.4% of the original value after being exposed to moisture (soaking in water for 10 days), elevated temperature (150 °C), and UV (15 days of continuous radiation), respectively, demonstrating excellent luminescent stability. We adopt the Tb-based 1D-MOF (3) as the green phosphor and successfully fabricate a prototype white-light-emitting diode (LED) with stable emission under long-term operation. Our synthetic strategy allows control over the linking pattern of lanthanide nodes, providing a predictive route to obtain lanthanide MOFs with improved luminescent stability.

Enhancing the Phosphate Adsorption of a Polyallylamine Resin in Alkaline Environments by Lanthanum Oxalate Modification.

Sevelamer hydrochloride (SH), originally developed as an oral pharmaceutical for controlling blood phosphate levels, is a polyallylamine resin that could be used in water treatments. Although it binds phosphates effectively, its adsorption capacity suffers from a significant loss at high pH. Here, we modify SH with lanthanum oxalate to improve its phosphate adsorption in alkaline environments. With less than 6.00 wt% in La content, the composite adsorbent (SH-1C-1La) exhibits an adsorption capacity of 109.3 mg P g-1 at pH 8.0 and 100.2 mg P g-1 at pH 10.0, demonstrating significant enhancement from the original SH (86.3 mg P g-1 at pH 8.0 and 69.4 mg P g-1 at pH 10.0). Besides its high adsorption capacity and rapid adsorption kinetics, SH-1C-1La is capable of maintaining more than 78% of its capacity after four regeneration cycles, showing good durability in long-term applications. Zeta-potential measurements and XPS analysis reveal that the lanthanum oxalate species increase the surface potential to enhance the electrostatic adsorption while introducing chemical binding sites for phosphate ions. Both factors lead to the improved adsorption properties. The modification by lanthanum oxalate species might provide a new alternative for improving the phosphate adsorption properties of anion-exchange resins.

A Noncovalent π-Stacked Porous Organic Molecular Framework for Selective Separation of Aromatics and Cyclic Aliphatics.

Selective separation using porous adsorbents is an energy-efficient alternative to traditional separation techniques. Stacked porous organic molecular frameworks (POMFs) capable of noncovalent π⋅⋅⋅π interactions are emerging as a new kind of adsorbents that facilitate green separation. Here we report a robust porous molecular crystal (TAPM-1), which is stabilized by multiple intermolecular π⋅⋅⋅π interactions. With its long-range π-stacking, TAPM-1 has excellent hydrophobicity, thermostability, recyclability, and high selectivity for aromatics over the corresponding cyclic aliphatics. This enables TAPM-1 to serve as the stationary phase in the high-resolution gas chromatographic separation of benzene and cyclohexane or toluene and methylcyclohexane.

Constructing π-Stacked Supramolecular Cage Based Hierarchical Self-Assemblies via π···π Stacking and Hydrogen Bonding.

Constructing supramolecular cages with multiple subunits via weak intermolecular interactions is a long-standing challenge in chemistry. So far, π-stacked supramolecular cages still remain unexplored. Here, we report a series of π-stacked cage based hierarchical self-assemblies. The π-stacked cage (π-MX-cage) is assembled from 16 [MXL]+ ions (M = Mn2+, Co2+; X = Br-, SCN-, Cl-; and L = tris(2-benzimidazolylmethyl)amine) via 18 intermolecular π-stacking interactions. The tetrahedral cage, consisting of four [MXL]+ ions as the vertexes and six pairs of [MXL]+ ions as the edges, features 48 exterior N-H hydrogen bond donors for hydrogen bond formation with guest molecules. By variation of the M2+/X- pair, the π-MX-cage demonstrates unique versatility for incorporating a wide variety of species via different hydrogen-bonding modes during the assembly of hierarchical superstructures. In specific, the π-MnBr-cages encapsulate acetonitrile (CH3CN) or cis-1,3,5-cyclohexanetricarbonitrile (cis-HTN) molecules in the central voids, while a core-shell tetrahedral inorganic cluster [Mn(H2O)6]@([Mn(H2O)4]4[Br42-]6) (Mn@Mn4-cage) is captured within the interstitial regions between cages. The π-CoSCN-cages are capable of stabilizing reactive sulfur-containing species, such as S2O42-, S2O62-, and HSO3- ions, in the hierarchical superstructure. Finally, H2PO4- ions are incorporated between π-CoCl-cages, resulting in an inorganic mesoporous framework. These results provide insights into further exploring the chemistry and hierarchical assembly of supramolecular cages based on π-π stacking intermolecular interactions.

Anisotropic Thermal Expansion in an Anionic Framework Showing Guest-Dependent Phases.

Crystalline materials generally show small positive thermal expansion along all three crystallographic axes because of increasing anharmonic vibrational amplitudes between bonded atoms or ions pairs on heating. In very rare cases, structural peculiarities may give rise to negative, anomalously large or zero thermal expansion behaviors, which remain poorly understood. Host-guest composites may exhibit such anomalous behavior if guest motions controllable. Here we report an anionic framework of helical nanotubes comprising three parallel helical chains. The anisotropic interaction between the guest and the framework, results in anisotropic thermal expansion in this framework. A series of detailed structural determination at 50 K intervals enable process visualization at the molecular level and the observed guest-dependent phases of the framework strongly support our proposed mechanism.

Transcriptome analysis of genes and metabolic pathways associated with nicotine degradation in Aspergillus oryzae 112822.

BACKGROUND: Nicotine-degrading microorganisms (NDMs) have recently received much attention since they can consume nicotine as carbon and nitrogen source for growth. In our previous work, we isolated an efficient nicotine-degrading fungus Aspergillus oryzae 112822 and first proposed a novel demethylation pathway of nicotine degradation in fungi. However, the underlying mechanisms of the demethylation pathway remain unresolved. In the present study, we performed a comparative transcriptome analysis to elucidate the molecular mechanisms of nicotine tolerance and degradation in A. oryzae 112822. RESULTS: We acquired a global view of the transcriptional regulation of A. oryzae 112822 exposed to nicotine and identified 4381 differentially expressed genes (DEGs) by nicotine treatment. Candidate genes encoding cytochrome P450 monooxygenases (CYPs), FAD-containing amine oxidase, molybdenum cofactor (Moco)-containing hydroxylase, and NADH-dependent and FAD-containing hydroxylase were proposed to participate in the demethylation pathway of nicotine degradation. Analysis of these data also revealed that increased energy was invested to drive nicotine detoxification. Nicotine treatment led to overproduction of reactive oxygen species (ROS), which formed intracellular oxidative stress that could induce the expression of several antioxidant enzymes, such as superoxide dismutase (SOD), catalase (CAT), and peroxiredoxin (Prx). Thioredoxin system was induced to restore the intracellular redox homeostasis. Several glutathione S-transferases (GSTs) were induced, most likely to participate in phase II detoxification of nicotine by catalyzing the conjugation of glutathione (GSH) to active metabolites. The toxin efflux pumps, such as the ATP-Binding Cassette (ABC) transporters and the major facilitator superfamily (MFS) transporters, were overexpressed to overcome the intracellular toxin accumulation. By contrast, the metabolic pathways related to cellular growth and reproduction, such as ribosome biogenesis and DNA replication, were inhibited by nicotine treatment. CONCLUSION: These results revealed that complex regulation networks, involving detoxification, transport, and oxidative stress response accompanied by increased energy investment, were developed for nicotine tolerance and degradation in A. oryzae 112822. This work provided the first insight into the metabolic regulation of nicotine degradation and laid the foundation for further revealing the molecular mechanisms of the nicotine demethylation pathway in filamentous fungi.

Selective CO2 Capture and High Proton Conductivity of a Functional Star-of-David Catenane Metal-Organic Framework.

Network structures based on Star-of-David catenanes with multiple superior functionalities have been so far elusive, although numerous topologically interesting networks are synthesized. Here, a metal-organic framework featuring fused Star-of-David catenanes is reported. Two triangular metallacycles with opposite handedness are triply intertwined forming a Star-of-David catenane. Each catenane fuses with its six neighbors to generate a porous twofold intercatenated gyroid framework. The compound possesses exceptional stability and exhibits multiple functionalities including highly selective CO2 capture, high proton conductivity, and coexistence of slow magnetic relaxation and long-range ordering.

Anisotropic Change in the Magnetic Susceptibility of a Dynamic Single Crystal of a Cobalt(II) Complex.

Atypically anisotropic and large changes in magnetic susceptibility, along with a change in crystalline shape, were observed in a CoII complex at near room temperature. This was achieved by combining oxalate molecules, acting as rotor, and a CoII ion with unquenched orbital angular momentum. A thermally controlled 90° rotation of the oxalate counter anion triggered a symmetry-breaking ferroelastic phase transition, accompanied by contraction-expansion behavior (ca. 4.5 %) along the long axis of a rod-like single crystal. The molecular rotation induced a minute variation in the coordination geometry around the CoII ion, resulting in an abrupt decrease and a remarkable increase in magnetic susceptibility along the direction perpendicular and parallel to the long axis of the crystal, respectively. Theoretical calculations suggested that such an unusual anisotropic change in magnetic susceptibility was due to a substantial reorientation of magnetic anisotropy induced by slight disruption in the ideal D3 coordination environment of the complex cation.

Thermally Induced Intra-Carboxyl Proton Shuttle in a Molecular Rack-and-Pinion Cascade Achieving Macroscopic Crystal Deformation.

Proton transport via dynamic molecules is ubiquitous in chemistry and biology. However, its use as a switching mechanism for properties in functional molecular assemblies is far less common. In this study, we demonstrate how an intra-carboxyl proton shuttle can be generated in a molecular assembly akin to a rack-and-pinion cascade via a thermally induced single-crystal-to-single-crystal phase transition. In a triply interpenetrated supramolecular organic framework (SOF), a 4,4'-azopyridine (azpy) molecule connects to two biphenyl-3,3',5,5'-tetracarboxylic acid (H4 BPTC) molecules to form a functional molecular system with switchable mechanical properties. A temperature change reversibly triggers a molecular movement akin to a rack-and-pinion cascade, which mainly involves 1) an intra-carboxyl proton shuttle coupled with tilting of the azo molecules and azo pedal motion and 2) H4 BPTC translation. Moreover, both the molecular motions are collective, and being propagated across the entire framework, leading to a macroscopic crystal expansion and contraction.

Influence of Intermolecular Interactions on Valence Tautomeric Behaviors in Two Polymorphic Dinuclear Cobalt Complexes.

Two polymorphic structures have been well determined in a valence tautomeric (VT) dinuclear cobalt complex. These polymorphs showed distinct thermal- and photomagnetic behavior, and are thus ideal for studying the "pure" intermolecular factors to VT transitions. In polymorph 1A, the VT cations are arranged head-to-waist with their neighbors and exhibit weak π⋅⋅⋅π interactions, resulting in a gradual and incomplete thermal VT transition. In contrast, the cations in polymorph 1B are arranged head-to-tail and exhibit relatively strong π⋅⋅⋅π interactions, leading to an abrupt and complete thermal VT transition with adjustable hysteresis loop at around room temperature. The VT process for both polymorphs can be induced by light, but the light-excited state of 1B⋅2H2 O has a higher thermal relaxation temperature than that of 1A⋅3H2 O.

Superior thermoelasticity and shape-memory nanopores in a porous supramolecular organic framework.

Flexible porous materials generally switch their structures in response to guest removal or incorporation. However, the design of porous materials with empty shape-switchable pores remains a formidable challenge. Here, we demonstrate that the structural transition between an empty orthorhombic phase and an empty tetragonal phase in a flexible porous dodecatuple intercatenated supramolecular organic framework can be controlled cooperatively through guest incorporation and thermal treatment, thus inducing empty shape-memory nanopores. Moreover, the empty orthorhombic phase was observed to exhibit superior thermoelasticity, and the molecular-scale structural mobility could be transmitted to a macroscopic crystal shape change. The driving force of the shape-memory behaviour was elucidated in terms of potential energy. These two interconvertible empty phases with different pore shapes, that is, the orthorhombic phase with rectangular pores and the tetragonal phase with square pores, completely reject or weakly adsorb N2 at 77 K, respectively.

Visualizing the Dynamics of Temperature- and Solvent-Responsive Soft Crystals.

We demonstrate that three flexible MOFs termed FJI-H11-R (FJI-H=Hong's group in Fujian Institute of Research on the Structure of Matter, R=Me, Et, (i) Pr) can reversibly respond to temperature and solvents via structural transformations, which can be visualized by in situ single-crystal X-ray snapshot analyses. FJI-H11-R exhibit colossal anisotropic thermal expansion, with a record-high uniaxial positive thermal-expansion coefficient of 653.2×10(-6)  K(-1) observed in FJI-H11-Me. Additionally, large c-axial shrinkage of 32.4 % is also observed during desolvation. The stimuli-responsive mechanism reveals the structural evolutions are related to the rotations and deformations of the organic linkers.