Expanding Linker Dimensionality in Metal-organic Frameworks for sub-Ångstrom Pore Control for Separation Applications

Metal-organic frameworks (MOFs) are a class of porous materials with high surface areas, which are acquiring rapid attention on an exponential basis. A significant characteristic of MOFs is their ability to act as adsorbents to selectively separate component mixtures of similar size, thereby addressing the technological need for an alternative approach to conventional distillation methods. Recently, MOFs comprising a 3-Dimensional (3D) linker have shown outstanding capabilities for difficult separations compared to the parent 2-Dimensional (2D) analogue. 3D-linkers with a polycyclic core are underrepresented in the MOF database due to the widespread preferred use of 2D-linkers and the misconceived high-cost of 3D linkers. We summarize the recent research of 3D-linker MOFs and highlight their beneficial employment for selective gas and hydrocarbon adsorption and separation. Furthermore, we outline forecasts in this area to create a platform for widespread adoption of 3D-linkers in MOF synthesis.     

Electrochemical rectification by redox-labeled bioconjugates: molecular building blocks for the construction of biodiodes

In the present work, we describe the properties of a bifunctional redox-labeled bioconjugate at electrode surfaces mediating the electron transfer across the electrode-electrolyte interface. We show that the assembly of ferrocene-labeled streptavidin on biotinylated electrodes results in a reproducible unidirectional current flow in the presence of electron donors in solution. Such rectifying films were built up by spontaneous binding of tetrameric streptavidin molecules to biotin centers immobilized on the electrode surface. Due to the high affinity of biotin to streptavidin, such bifunctional films completely bind any biotinylated compounds. The charge transport between donors in solution and the Au electrode is mediated by the ferrocene moieties, allowing us to develop a molecular rectifier. Our experimental results suggest that such redox-labeled proteins with a high binding capacity constitute a promising alternative to organic compounds used in molecular electronics.     

Facile large-scale fabrication of proton conducting channels

A new approach to the facile large-scale fabrication of robust silicon membranes with artificial proton conducting channels is presented. Ordered two-dimensional macroporous silicon was rendered proton conducting by growing a thick uniform polyelectrolyte brush using surface-initiated atom transfer radical polymerization throughout the porous matrix. The fabricated silicon-poly(sulfopropyl methacrylate) hybrid membranes were evaluated for their proton conductivity, ion exchange capacity, and water uptake. With proton conductivities in the range of 10(-2) S/cm, these proof-of-concept experiments highlight a promising alternative for producing tailorable proton conducting membranes. This approach constitutes a benchmark for the preparation and study of model systems and, in addition, for the large-scale fabrication of membranes suitable for a wide range of technological applications.     

Heteroleptic copper(I) complexes coupled with methano[60]fullerene: synthesis, electrochemistry, and photophysics

Heteroleptic copper(I) complexes CuPOP-F and CuFc-F have been prepared from a fullerene-substituted phenanthroline ligand and bis[2-(diphenylphosphino)phenyl] ether (POP) and 1,1'-bis(diphenylphosphino)ferrocene (dppFc), respectively. Electrochemical studies indicate that some ground-state electronic interaction between the fullerene subunit and the metal-complexed moiety are present in both CuPOP-F and CuFc-F. Their photophysical properties have been investigated by steady state and time-resolved UV-vis-NIR luminescence spectroscopy and nanosecond laser flash photolysis in a CH2Cl2 solution and compared to those of the corresponding model copper(I) complexes CuPOP and CuFc and of the fullerene model compound F. Selective excitation of the methanofullerene moiety in CuPOP-F results in regular deactivation of the lowest singlet and triplet states, indicating no intercomponent interactions. Conversely, excitation of the copper(I)-complexed unit (405 nm, 40% selectivity) shows that the strongly luminescent triplet metal-to-ligand charge-transfer ((3)MLCT) excited state located at 2.40 eV is quenched by the carbon sphere with a rate constant of 1.6 x 10(8) s(-1). Details on the mechanism of photodynamic processes in CuPOP-F via transient absorption are hampered by the rather unfavorable partition of light excitation between the two chromophores. By determination of the yield of formation of the lowest fullerene triplet level through sensitized singlet oxygen luminescence in the NIR region, it is shown that the final sink of photoinduced processes is always the fullerene triplet. This can be populated via a two-step charge-separation charge-recombination process and a less favored (3)MLCT --> (3)C60 triplet-triplet energy-transfer pathway. In CuFc-F, both of the photoexcited copper(I)-complexed and fullerene moieties are quenched by the presence of the ferrocene unit, most likely via ultrafast energy transfer.     

Ortho-Alkoxy-benzamide Directed Formation of a Single Crystalline Hydrogen-bonded Crosslinked Organic Framework and Its Boron Trifluoride Uptake and Catalysis

Boron trifluoride (BF₃) is a highly corrosive gas widely used in industry. Confining BF₃ in porous materials ensures safe and convenient handling and prevents its degradation. Hence, it is highly desired to develop porous materials with high adsorption capacity, high stability, and resistance to BF₃ corrosion. Herein, we designed and synthesized a Lewis basic single-crystalline hydrogen-bond crosslinked organic framework (H_COF-50) for BF₃ storage and its application in catalysis. Specifically, we introduced self-complementary ortho-alkoxy-benzamide hydrogen-bonding moieties to direct the formation of highly organized hydrogen-bonded networks, which were subsequently photo-crosslinked to generate H_COFs. The H_COF-50 features Lewis basic thioether linkages and electron-rich pore surfaces for BF₃ uptake. As a result, H_COF-50 shows a record-high 14.2 mmol/g BF₃ uptake capacity. The BF₃ uptake in H_COF-50 is reversible, leading to the slow release of BF₃. We leveraged this property to reduce the undesirable chain transfer and termination in the cationic polymerization of vinyl ethers. Polymers with higher molecular weights and lower polydispersity were generated compared to those synthesized using BF₃ ⋅ Et₂O. The elucidation of the structure–property relationship, as provided by the single-crystal X-ray structures, combined with the high BF₃ uptake capacity and controlled sorption, highlights the molecular understanding of framework-guest interactions in addressing contemporary challenges.     

Anion Directed Self‐Assembly of One‐Dimensional and Two‐Dimensional Coordination Polymers Containing Bridging Diphosphine Ligands

The reactions of 1,2‐bis(diphenylphosphanyl)ethane (dppe) with different silver(I) salts facilitated the formation of 1D and 2D coordination polymers, [Ag(dppe)(OAc)]_n · nH₂O ( 1 ) and [Ag₂(dppe)_1.5(NO₃)₂]_n ( 2 ), respectively. The complexes were characterized by elemental analysis, ATR‐IR spectroscopy, ¹H NMR, ¹³C NMR, and ³¹P NMR spectroscopy, and single‐crystal X‐ray diffraction. Structural analysis revealed that complex 1 exhibits a 1D infinite wavy structure, in which each silver(I) ion is bridged by dppe ligands. Structure 2 has a 2D topologically promising architecture that displays a 6.6.6 graphitic net, which corresponds to hnd topology. The nitrate ions and dppe ligands are in a μ₂ bridging mode and support the formation of this net. Moreover, significant π–π interactions between the phenyl rings in the apertures of (6,3) grid stabilized complex 2 .     

Estimates for the real and imaginary parts of the eigenvalues of matrices and applications

This paper is a continuation of our recent work on the localization of the eigenvalues of matrices. We give new bounds for the real and imaginary parts of the eigenvalues of matrices. Applications to the localization of the zeros of polynomials are also given.     

Characterization and properties of low-linear-density polyethylene/Typha latifolia composites

The characterization of the effects of different sizes and loadings of Typha latifolia on the tensile, thermal, and morphological properties of linear-low-density polyethylene (LLDPE)/T. latifolia composites were evaluated using tensile test, Fourier transform infrared spectroscopy, thermogravimetric analysis, and scanning electron microscopy analyses. Results indicated the tensile strength and elongation at break decreased as T. latifolia loading increased. However, T. latifolia fine size (fs) exhibited better tensile properties than coarse size at the same loading in the composite. T. latifolia (15%, fs) recorded higher thermal stability than LLDPE control and other T. latifolia loadings and sizes due to the strong interaction of T. latifolia (15%, fs) in LLDPE matrix as shown in morphology.