Single Crystalline,Non-stoichiometric Cocrystals of Hydrogen-Bonded Organic Frameworks

Porous frameworks composed of non-stoichiometrically mixed multicomponent molecules attract much attention from a functional viewpoint. However, their designed preparation and precise structural characterization remain challenging. Herein, we demonstrate that cocrystallization of tetrakis(4-carboxyphenyl)hexahydropyrene and pyrene derivatives ( CP-Hp and CP-Py , respectively) yields non-stoichiometric mixed frameworks through networking via hydrogen bonding. The composition ratio of CP-Hp and CP-Py in the framework was determined by single crystalline X-ray crystallographic analysis, indicating that the mixed frameworks were formed over a wide range of composition ratios. Furthermore, microscopic Raman spectroscopy on the single crystal indicates that the components are not uniformly distributed such as ideal solid solution, but are done gradationally or inhomogeneously.     

An Unprecedented Interpenetrating Structure Built from Two Differently Bonded Frameworks: Synthesis,Characteristics, and Efficient Removal of Anionic Dyes from Aqueous Solutions

The first example of one single crystal (NTOU-5) containing two different organic-inorganic hybrid open-framework structures was obtained using a hydro(solvo)thermal method and structurally characterized by single-crystal X-ray diffraction. Remarkably, under the same synthetic conditions, the zinc ions are respectively coordinated by oxalic acid (OX) and 1,2,4,5-tetrakis(imidazol-1-ylmethyl)benzene (TIMB) linkers to form two significantly different frameworks: anionic [Zn₂(OX)₃]²⁻ and cationic [Zn(TIMB)]²⁺ networks that interweave with each other to give an unprecedented interpenetrating structure with two differently-bonded open-frameworks. From the inorganic chemistry perspective, it is extremely difficult to control to which metal center the oxygen-donor linkers or/and nitrogen-donor ligands bind. A mixed Co/Zn analogue was also obtained by a similar method. The single-crystal XRD and EDS analyses indicate that the octahedral Zn ions of the anionic framework are replaced by cobalt cations, whereas the Zn ions in the tetrahedral positions of the cationic networks remain intact. This leads to the formation of the interpenetrating analogue with a mixed metal composition. Furthermore, NTOU-5 shows structural stability and efficiently removes organic dyes from aqueous solutions at concentrations of 10 ppm.     

基于布谷鸟算法与BP神经网络的煤灰变形温度预测

以120种煤样为数据基础,采用布谷鸟算法(CS)优化BP(Back Propagation)神经网络,建立了CSBP模型对单煤、煤掺添加剂和配煤等3类样本的煤灰变形温度(DT)样本进行预测。模型以煤灰化学成分及其组合参数等13个变量作为输入量,以变形温度(DT)作为输出量。CSBP模型预测结果与BP神经网络模型预测结果进行对比发现,无论是单煤、煤掺添加剂还是配煤,CSBP模型较BP模型对煤灰变形温度(DT)的预测都更加精准,平均相对误差分别达到了3.11%、4.08%和4.22%。另外,对比3类样本预测结果发现,无论是CSBP模型还是BP模型,相比单煤预测而言,煤掺添加剂及配煤的预测误差都有明显的增加。     

Template–Framework Interactions in Tetraethylammonium‐Directed Zeolite Synthesis

Zeolites, having widespread applications in chemical industries, are often synthesized using organic templates. These can be cost‐prohibitive, motivating investigations into their role in promoting crystallization. Herein, the relationship between framework structure, chemical composition, synthesis conditions and the conformation of the occluded, economical template tetraethylammonium (TEA⁺) has been systematically examined by experimental and computational means. The results show two distinct regimes of occluded conformer tendencies: 1) In frameworks with a large stabilization energy difference, only a single conformer was found (BEA, LTA and MFI). 2) In the frameworks with small stabilization energy differences (AEI, AFI, CHA and MOR), less than the interconversion of TEA⁺ in solution, a heteroatom‐dependent (Al, B, Co, Mn, Ti, Zn) distribution of conformers was observed. These findings demonstrate that host–guest chemistry principles, including electrostatic interactions and coordination chemistry, are as important as ideal pore‐filling.     

Recent Advances in Zeolite-like Cluster Organic Frameworks

During the past decade, research on the design and synthesis of zeolite-like metal–organic frameworks (ZMOFs) has developed greatly. As an important subclass of ZMOFs, zeolite-like cluster organic frameworks (ZCOFs) built from 4-connected metal-cluster secondary building units (SBUs) and appropriate linear organic ligand bridges have attracted sustained interest, because such materials not only integrate the merits of inorganic zeolites, ZMOFs, and metal clusters, including interesting topologies, high surface areas, extra-large cavities and channels, structural tunability, and unique physicochemical properties from various metal clusters, but also open up a new avenue to design and fabricate hybrid zeolite-like materials that have many potential applications in material sciences. In this review, recent developments in ZCOFs are summarized by classifying the ZCOFs into four categories according to the composition of the SBUs: 1) ZCOFs based on metal–halide cluster SBUs, 2) ZCOFs based on metal–oxygen cluster SBUs, 3) ZCOFs based on metal–chalcogen cluster SBUs, and 4) ZCOFs based on mixed types of metal-cluster SBUs. Besides, challenges associated with the design and synthesis of ZCOFs and the vast potential of this area are also discussed.     

From Metal–Organic Frameworks to Single‐Atom Fe Implanted N‐doped Porous Carbons: Efficient Oxygen Reduction in Both Alkaline and Acidic Media

It remains highly desired but a great challenge to achieve atomically dispersed metals in high loadings for efficient catalysis. Now porphyrinic metal–organic frameworks (MOFs) have been synthesized based on a novel mixed‐ligand strategy to afford high‐content (1.76 wt %) single‐atom (SA) iron‐implanted N‐doped porous carbon (Fe_SA‐N‐C) via pyrolysis. Thanks to the single‐atom Fe sites, hierarchical pores, oriented mesochannels and high conductivity, the optimized Fe_SA‐N‐C exhibits excellent oxygen reduction activity and stability, surpassing almost all non‐noble‐metal catalysts and state‐of‐the‐art Pt/C, in both alkaline and more challenging acidic media. More far‐reaching, this MOF‐based mixed‐ligand strategy opens a novel avenue to the precise fabrication of efficient single‐atom catalysts.     

Solvothermal synthesis of two polymorphs of an indium germanate incorporating an organic amine ligand: β- and γ-In2Ge6O15(NH2CH2CH2NH2)2

Two new polymorphs, β- and γ-In(2)Ge(6)O(15)(NH(2)CH(2)CH(2)NH(2))(2), have been synthesized under solvothermal conditions using 2-methylpentamethylenediamine as a solvent and structurally characterized by single-crystal X-ray diffraction. Both structures contain single layers with the composition [Ge(6)O(15)] that are connected by In(2)O(6)N(4) octahedral dimers to form 3D frameworks. The germanate layers contain four-, six-, and eight-membered rings and six-membered rings in the β and γ polymorphs, respectively. Compounds with related structures are discussed for comparison.     

A mixed ligand route for the construction of tetrahedrally coordinated porous lithium frameworks

Reported here are two 4-connected 3D frameworks based on monomeric lithium nodes, which are synthesized through a mixed ligand route. By combining a negatively charged imidazole ligand and a neutral bis(imidazolyl)methane ligand (or one of its derivatives), neutral frameworks adopting chiral quartz-dual and diamond topologies have been obtained. These materials have low framework density and can reversibly adsorb hydrogen gas.     

Der Chemische Transport von Mischkristallen im System CoO/NiO

Chemical Vapor Transport of Solid Solutions. 1 Chemical Transport of CoO/NiO‐Mixed Crystals CVT‐methods are a suitable pathway to prepare single crystals of ionic mixed‐crystals with variable composition. This is shown in the case of CoO/NiO‐mixed crystals. The composition of the product is mainly determined by the composition of the starting material. Homogeneous single crystals of a well defined composition can be prepared in a foreseeable manner. The experiments can be understood by thermochemical calculations.     

Stoichiometry of clathrates

Two aspects of clathrate stoichiometry are discussed: structural stoichiometry and variation in composition due to variable occupation of host cavities in the framework by guest molecules. The solid solutions that are due to the variable occupation of cavities (iskhoric solutions) are classified into two types according to the stability of the hollow clathrate framework of the host. The first type involves compounds with stable hollow frameworks (the occupancies change from zero), and the second type are compounds with metastable hollow frameworks (the occupancies change from certain positive values). Special attention is paid to a wide class of clathrate compounds of constant composition (currently all clathrates are regarded as nonstoichiometric compounds). Clathrates of constant composition are formed when the hollow framework of the host is absolutely unstable. Reasons for instability of the frameworks are discussed, and theoretical models designed on the basis of the available data are considered. Examples of alloxenic (with one guest replaced by another) and allokiric (with replacements in the host subsystem) solid clathrate solutions are given. Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences. Translated fromZhurnal Struktumoi Khimii, Vol. 36, No. 6, pp. 1088–1141, November–December, 1995. Translated by L. Smolina     

Curie-point pyrolysis–gas chromatography–mass spectroscopic analysis of theabrownins from fermented Zijuan tea

Zijuan tea theabrownins (ZTTBs) was extracted from a type of fermented Zijuan tea and separated into fractions according to molecular weight. The extract was found to contain predominantly two fractions: <3.5 kDa and >100 kDa. These two fractions were analyzed for chemical composition, structural characteristics by Curie-point pyrolysis–gas chromatography–mass spectroscopy (CP-Py–GC/MS). The affects of pyrolysis temperature on pyrolytic products were also investigated. The fraction >100 kDa produced 50 GC/MS peaks during pyrolysis at 280 °C, 70 peaks at 386 °C, and 134 peaks at 485 °C. Fourteen of the products formed at 280 °C, 12 of those formed at 386 °C, and 21 of those formed at 485 °C were identified with match qualities of greater than 80%. The fraction <3.5 kDa gave 51 peaks during pyrolysis at 280 °C, 99 peaks at 386 °C, and 257 peaks at 485 °C. Six products formed at 280 °C, four products formed at 386 °C, and 61 products formed at 485 °C were identified with match qualities of greater than 80%. Pyrolysis temperatures of 485 °C and 386 °C were found suitable for the two fractions respectively. CP-Py–GC/MS revealed that, the fraction >100 kDa mainly consisted of phenolic pigments, esters, proteins, and polysaccharides, while the fraction <3.5 kDa contained no polysaccharide. CP-Py–GC/MS is an effective tool for the composition difference and structural characteristics of ZTTBs as well as other complex macromolecular plant pigments.     

Pore Surface Engineering with Controlled Loadings of Functional Groups via Click Chemistry in Highly Stable Metal-Organic Frameworks

Reactions of ZrCl(4) and single or mixed linear dicarboxylic acids bearing methyl or azide groups lead to highly stable isoreticular metal-organic frameworks (MOFs) with content-tunable, accessible, reactive azide groups inside the large pores. These Zr-based MOFs offer an ideal platform for pore surface engineering by anchoring various functional groups with controlled loadings onto the pore walls via the click reaction, endowing the MOFs with tailor-made interfaces. Significantly, the framework and crystallinity of the functionalized MOFs are well-retained, and the engineered pore surfaces have been demonstrated to be readily accessible, thus providing more opportunities for powerful and broad applications of MOFs.     

Ionic Liquids Containing Silsesquioxane and Cyclic Siloxane Frameworks

This paper describes the author's recent work on the preparation and properties of thermally stable ionic liquids (ILs) containing siloxane frameworks. Quaternary ammonium and imidazolium salt-type ILs containing random oligosilsesquioxane frameworks were successfully prepared via the hydrolytic condensation of the corresponding organotrialkoxysilanes by using an aqueous superacid bis(trifluoromethanesulfonyl)imide (HNTf₂) solution as a catalyst and solvent. Imidazolium salt-type ILs containing polyhedral oligomeric silsesquioxane (POSS) frameworks were also prepared through a reaction similar to that described above by using a water/methanol mixed solution of HNTf₂. In addition, amorphous POSSs with two types of ionic groups randomly distributed in the side chain were prepared. These POSSs were ILs exhibiting fluidity at relatively low temperatures. Furthermore, imidazolium and ammonium salt-type ILs containing cyclic oligosiloxane frameworks were prepared through a reaction similar to that of the corresponding organodialkoxysilanes. The thermal decomposition temperatures of the above ILs containing siloxane frameworks were higher than those of general ILs.     

(3,4)-connected zincophosphites as structural analogues of zinc hydrogen phosphate

The synthesis and crystal structures of three new open-framework zincophosphites with helical channels are reported here in the context of the synthetic design of an open architecture from three- and four-connected polyhedral centers. These zincophosphites were prepared under hydrothermal conditions from HF-containing media in mixed water-ethylene glycol solvents. Their three-dimensional frameworks consist of alternating ZnO4(6-) tetrahedra and HPO3(2-) trigonal pyramids with an overall framework composition of [Zn3(HPO3)4]2-. The topology was analyzed by converting these zincophosphites from their (3,4)-connected network into a four-connected framework. The symmetry and charge density of three different structure-directing agents dictate the symmetry and framework density of resulting inorganic frameworks. These zincophosphites are structural analogues of a known hydrogen phosphate, suggesting that the bonding difference between -P-H and -P-OH plays an insignificant role in the formation of phosphite and hydrogen phosphate open frameworks.     

Mixed Linker Metal Organic Framework as an Efficient and Reusable Catalyst for Suzuki Miyaura Coupling Reaction

Series of metal organic frameworks from nitrogen based ligand were synthesized as efficient and reusable catalyst via mixed linker methods. The thermogravimetric study of the mixed linker metal organic framework (MIXMOF) reveals that the complexes are potential thermally stable materials. The palladium supported catalysts exhibits high catalytic activity toward the Suzuki-Miyaura cross coupling reaction and can be reused several times without any visible loss of activity even after five consecutive times.     

Porous Frameworks Based on Supramolecular Ball Joints: Bringing Flexibility to Ordered 3D Lattices

XOFs-type materials (X=M, C, S, that is, metal–organic frameworks, covalent organic frameworks and supramolecular organic frameworks, respectively) share a common unifying feature: mutual spatial orientation of constituting components is strictly directional and unchanging by design. Herein, we illustrate an alternate design for porous architectures, as rigid joints constituted by coordinative (MOFs), covalent (COFs), or hydrogen-donor/acceptor (SOFs) bonds, are replaced by supramolecular ball joints, which confer unprecedented flexibility, especially angular, to porous networks. The obtained frameworks remain highly organized but are also permutable: lacking a forced convergence towards an immutable minimum energy structure, these systems remain able to adjust depending on external conditions. Results of POF (permutable organized framework) synthesis is a family of structures rather than a single pre-determined three-dimensional arrangement, as we demonstrate with an illustrative set of 5 XRD structures.     

Modelling a Linker Mix‐and‐Match Approach for Controlling the Optical Excitation Gaps and Band Alignment of Zeolitic Imidazolate Frameworks

Tuning the electronic structure of metal–organic frameworks is the key to extending their functionality to the photocatalytic conversion of absorbed gases. Herein we discuss how the band edge positions in zeolitic imidazolate frameworks (ZIFs) can be tuned by mixing different imidazole‐based linkers within the same structure. We present the band alignment for a number of known and hypothetical Zn‐based ZIFs with respect to the vacuum level. Structures with a single type of linker exhibit relatively wide band gaps; however, by mixing linkers of a low‐lying conduction edge with linkers of a high‐lying valence edge, we can predict materials with ideal band positions for visible‐light water splitting and CO₂ reduction photocatalysis. By introducing copper in the tetrahedral position of the mixed‐linker ZIFs, it would be possible to increase both photo‐absorption and the electron–hole recombination times.     

Self-assembly combining two bioactive peptide-amphiphile molecules into nanofibers by electrostatic attraction

We describe a new approach to peptide-amphiphile (PA) nanofiber preparation that allows PAs with different bioactive amino acid sequences to be combined into a single fiber. Oppositely charged PAs are synthesized separately and then mixed to produce gels of nanofiber networks at physiological pH. Transmission electron microscopy reveals the formation of fibers approximately 7 nm in diameter and several micrometers long in these dimeric systems. On the basis of NMR and microscopy, we suggest that these nanofibers are cylindrical micelles of mixed composition, formed due to electrostatic attraction between the oppositely charged PAs. This strategy for self-assembly may be useful in cell therapies that can be implemented without invasive surgery or in in vitro tissue engineering.     

Effect of Micelle Composition on Acidic Drugs Separation Behavior by Micellar Electrokinetic Capillary Chromatography

Micellar electrokinetic capillary chromatography (MECC) is a branch of capillary electrophoretic techniques, in which surfactant micelles are added to the electrolyte solution as pseudostationary phase. Separation in MECC is based on electrophoretic mobilities of the analytes when partitioned into micelles1. In this work, four acidic drugs similar in structure with aryl carboxylic acid were separated by MECC. The effects of type of surfactant, such as anionic surfactant SDS, nonionic …     

Thermodynamics, adsorption kinetics and rheology of mixed protein-surfactant interfacial layers

Depending on the bulk composition, adsorption layers formed from mixed protein/surfactant solutions contain different amounts of protein. Clearly, increasing amounts of surfactant should decrease the amount of adsorbed proteins successively. However, due to the much larger adsorption energy, proteins are rather strongly bound to the interface and via competitive adsorption surfactants cannot easily displace proteins. A thermodynamic theory was developed recently which describes the composition of mixed protein/surfactant adsorption layers. This theory is based on models for the single compounds and allows a prognosis of the resulting mixed layers by using the characteristic parameters of the involved components. This thermodynamic theory serves also as the respective boundary condition for the dynamics of adsorption layers formed from mixed solutions and their dilational rheological behaviour. Based on experimental studies with milk proteins (β-casein and β-lactoglobulin) mixed with non-ionic (decyl and dodecyl dimethyl phosphine oxide) and ionic (sodium dodecyl sulphate and dodecyl trimethyl ammonium bromide) surfactants at the water/air and water/hexane interfaces, the potential of the theoretical tools is demonstrated.The displacement of pre-adsorbed proteins by subsequently added surfactant can be successfully studied by a special experimental technique based on a drop volume exchange. In this way the drop profile analysis can provide tensiometry and dilational rheology data (via drop oscillation experiments) for two adsorption routes — sequential adsorption of the single compounds in addition to the traditional simultaneous adsorption from a mixed solution. Complementary measurements of the surface shear rheology and the adsorption layer thickness via ellipsometry are added in order to support the proposed mechanisms drawn from tensiometry and dilational rheology, i.e. to show that the formation of mixed adsorption layer is based on a modification of the protein molecules via electrostatic (ionic) and/or hydrophobic interactions by the surfactant molecules and a competitive adsorption of the resulting complexes with the free, unbound surfactant. Under certain conditions, the properties of the sequentially formed layers differ from those formed simultaneously, which can be explained by the different locations of complex formation.