Synergizing Steric Hindrance and Stacking Interactions to Facilitate the Controlled Assembly of Multiple 41 Metalla-Knots and Pseudo-Solomon Links.

In this work, a noncoplanar terphenyl served as building block to synthesize a novel 3,3'-substituted bipyridyl ligand (L1) which further reacted with binuclear half-sandwich units A/B, giving rise to two aesthetical 41 metalla-knots in high yields via coordination-driven self-assembly strategy. Furthermore, given the inherent compactness of the 41 metalla-knots, it creates favorable conditions for the emergence of steric repulsion. We focused on progressively introducing nitrogen atoms featuring lone pair electrons (LPEs) into ligand L1 to manipulate the balance of H···H/LPEs···LPEs steric repulsion during the assembly process, ultimately achieving controlled assembly from 41 metalla-knots to the pseudo-Solomon link and then to molecular tweezer-like assembly facilitated by stacking interactions. All the assemblies were well characterized by solution-state NMR techniques, ESI-TOF/MS, and single-crystal X-ray diffraction. The evolutionary process of topological architectures is equivalent to visualizing the synergistic effect of steric hindrance and stacking interactions on structural assembly, providing a new avenue for achieving the controlled synthesis of different topologies.

The Topological Transformation of Trefoil Knots to Solomon Links via Diels-Alder Click Reaction.

The quest for more efficient, user-friendly, and less wasteful topological transformations remains a significant challenge in the realm of postassembly modifications. In this article, high yields of two molecular trefoil knots (Rh-1, Ir-1) were obtained using ligand 3,6-bis(3-(pyridin-4-yl)phenyl)-1,2,4,5-tetrazine (L1) with reactive tetrazine units and binuclear half-sandwich organometallic units [Cp*2M2(µ-TPPHZ)(OTf)2](OTf)2 (Rh-B, M = RhIII; Ir-B, M = IrIII). 2,5-Norbornadiene was used as an inducer of the Diels-Alder click reaction to modulate rapidly and efficiently the transformation of Trefoil knots to Solomon links. However, the key to achieving this topological structural change is the subtle increase in site steric of the pyridazine fragments (L2), which allows the molecular structures to spread and bend in three-dimensional space, as confirmed by single-crystal X-ray diffraction, ESI-TOF/MS, elementary analysis and detailed solution-state NMR techniques.

A Novel Spectrum Contrast Mapping Method for Functional Magnetic Resonance Imaging Data Analysis.

Many studies reported that spontaneous fluctuation of the blood oxygen level-dependent signal exists in multiple frequency components and changes over time. By assuming a reliable energy contrast between low- and high-frequency bands for each voxel, we developed a novel spectrum contrast mapping (SCM) method to decode brain activity at the voxel-wise level and further validated it in designed experiments. SCM consists of the following steps: first, the time course of each given voxel is subjected to fast Fourier transformation; the corresponding spectrum is divided into low- and high-frequency bands by given reference frequency points; then, the spectral energy ratio of the low- to high-frequency bands is calculated for each given voxel. Finally, the activity decoding map is formed by the aforementioned energy contrast values of each voxel. Our experimental results demonstrate that the SCM (1) was able to characterize the energy contrast of task-related brain regions; (2) could decode brain activity at rest, as validated by the eyes-closed and eyes-open resting-state experiments; (3) was verified with test-retest validation, indicating excellent reliability with most coefficients > 0.9 across the test sessions; and (4) could locate the aberrant energy contrast regions which might reveal the brain pathology of brain diseases, such as Parkinson's disease. In summary, we demonstrated that the reliable energy contrast feature was a useful biomarker in characterizing brain states, and the corresponding SCM showed excellent brain activity-decoding performance at the individual and group levels, implying its potentially broad application in neuroscience, neuroimaging, and brain diseases.

Homochiral Dodecanuclear Lanthanide "Cage in Cage" for Enantioselective Separation.

It is extremely difficult to anticipate the structure and the stereochemistry of a complex, particularly when the ligand is flexible and the metal node adopts diverse coordination numbers. When trivalent lanthanides (LnIII) and enantiopure amino acid ligands are utilized as building blocks, self-assembly sometimes yields rare chiral polynuclear structures. In this study, an enantiopure carboxyl-functionalized amino acid-based ligand with C3 symmetry reacts with lanthanum cations to give a homochiral porous coordination cage, (Δ/Λ)12-PCC-57. The dodecanuclear lanthanide cage has an unprecedented octahedral "cage-in-cage" framework. During the self-assembly, the chirality is transferred from the enantiopure ligand and fixed by the binuclear lanthanide cluster to give 12 metal centers that have either Δ or Λ homochiral stereochemistry. The cage exhibits excellent enantioselective separation of racemic alcohols, 2,3-dihydroquinazolinones, and multiple commercially available drugs. This finding exhibits a rare example of a multinuclear lanthanide complex with a dual-walled topology and homochirality. The highly ordered self-assembly and self-sorting of flexible amino acids and lanthanides shed light on the chiral transformation between different complicated artificial systems that mimic natural enzymes.

Engineering a homochiral metal-organic framework based on an amino acid for enantioselective separation.

A chiral metal-organic framework possessing an open amphiphilic channel is constructed from a dicarboxylate ligand derived from an amino acid and is shown to be an efficient and recyclable chiral solid adsorbent, which is capable of separating racemic secondary alcohols, epoxides, and ibuprofen with very high enantioselectivity.

Optimization of ultrasound-assisted extraction of poly-phenols from Ajuga ciliata Bunge and evaluation of antioxidant activities in vitro.

Effective extraction of natural antioxidants from cheap plant sources is still a problem. In this paper, an excellent method of ultrasound-assisted extraction of phenolic compounds from Ajuga ciliata Bunge was studied. The effects of four factors including ethanol volume fraction, ultrasonic time, ultrasonic temperature and material liquid ratio were discussed. After single factor experiments had been investigated, a 4-factor, 3-level Box-Behnken design experiment was used to obtain the model optimum conditions, which are shown as follows: ethanol volume fraction of 41%, liquid-solid ratio of 35:1 mL/g, ultrasonic temperature of 60 °C and ultrasonic time of 50 min. Under these conditions, the experimental productivity is 3.552 mg/g. The spectra of Fourier infrared and energy dispersive X-ray suggest that phenolic compounds exist in the extracts. Besides, free radical scavenging potentials of superoxide anion, hydroxyl and DPPH were measured to evaluate their antioxidant properties. This study proves that the ultrasonic-assisted extraction technique can extract phenolic compounds with antioxidant capacity from Ajuga ciliata Bunge.

Bottom-Up Assembly of a Highly Efficient Metal-Organic Framework for Cooperative Catalysis.

In this study, we demonstrate a bottom-up assembly of a monomeric copper complex and a two-dimensional (2-D) heterometallic metal-organic framework (MOF) from a carboxylate-functionalized tridentate Schiff base ligand and metal ions. The obtained 2-D MOF features a unique bimetallic copper center which is different from its monometallic precursor and acts as an efficient heterogeneous catalyst for the Friedel-Crafts reaction and Henry reaction. The MOF catalyst shows a remarkably superior activity compared to its homogeneous counterparts in a wide range of substrates. It is presumably ascribed to the dual activation of the substrates by the active bimetallic copper center confined in the MOF network, which is supported by the significant changes in catalytic activity at low catalyst/substrates ratios when using the 2-D MOF and its precursor as catalysts, respectively. Moreover, the MOF catalyst also shows an excellent stability and recyclability. Our work, therefore, provides a stepwise strategy to design a heterogeneous cooperative catalyst, by taking advantage of the modulated structure of MOF and tunable functionality of the tridentate Schiff base, with high performance in a variety of organic synthesis.

Facile synthesis of hierarchical CNF/SnO2/Ni nanostructures via self-assembly process as anode materials for lithium ion batteries.

Hierarchical carbon nanofibre (CNF)/SnO2/Ni nanostructures of graphitized carbon nanofibres and SnO2 nanocrystallines and Ni nanocrystallines have been prepared via divalent tin-alginate assembly on polyacrylonitrile (PAN) fibres, controlled pyrolysis and ball milling. Fabrication is implemented in three steps: (1) formation of a tin-alginate layer on PAN fibres by coating sodium alginate on PAN in a water medium followed by polycondensation in SnCl2 solution; (2) heat treatment at 450°C in a nitrogen atmosphere; (3) ball milling the mixture of CNF/SnO2 fibres and Ni powder. The CNF/SnO2/Ni nanocomposite exhibits good lithium ion storage capacity and cyclability, providing a facile and low-cost approach for the large-scale preparation of anode materials for lithium ion batteries.

Self-Assembly of Antisite Defectless nano-LiFePO4 @C/Reduced Graphene Oxide Microspheres for High-Performance Lithium-Ion Batteries.

LiFePO4 @C/reduced graphene oxide (rGO) hierarchical microspheres with superior electrochemical activity and a high tap density were first synthesized by using a Fe3+ -based single inorganic precursor (LiFePO4 OH@RF/GO; RF=resorcinol-formaldehyde, GO=graphene oxide) obtained from a template-free self-assembly synthesis followed by direct calcination. The synthetic process requires no physical mixing step. The phase transformation pathway from tavorite LiFePO4 OH to olivine LiFePO4 upon calcination was determined by means of the in situ high-temperature XRD technique. Benefitting from the unique structure of the material, these microspheres can be densely packed together, giving a high tap density of 1.3 g cm-3 , and simultaneously, defectless LiFePO4 primary nanocrystals modified with a highly conductive surface carbon layer and ultrathin rGO provide good electronic and ionic kinetics for fast electron/Li+ ion transport.