Search

A highly soluble, interlayer-expanded, and crystalline ionic graphdiyne was obtained through “framework charge-induced intercalation (FCII)” strategy.

Aerogels of cellulose nanocrystals with balanced thermal and mechanical performance can be fabricated via a 1 nm metal oxide cluster assisted unidirectional freeze-drying processing.

In the assemblies of subnanoscale polyhedral oligomeric silsesquioxane, topological interaction makes the dominant contribution to their viscoelasticity with broad tunability. The assembly molecules are designed with dumbbell, triangular, and tetrahedral shapes, and they demonstrate an intrinsic glassy feature with neither long-range ordering nor supramolecular assembly formation in their bulk. Their viscoelasticity can be broadly tuned through the tailoring of molecular topologies, while the trimer and tetramer assemblies afford elastic moduli comparable to those of rubbers (∼0.5 MPa) even 80 K above their glass transition temperatures. Molecular dynamics studies reveal the topological constraints resulting from the topology-disrupted cooperative dynamics among the cluster assemblies, and this finally leads to the typical caging dynamics of the structural units and the elasticity of the bulk materials. Further broadband dielectric spectroscopy studies uncover the unique hierarchical relaxation dynamics, inspiring the strategy for the decoupling of mechanical strengths and toughness for the design of impact resistant materials.

The fabrication of commercial cellulose nanofibrils (CNFs) into arrays with long-range ordering is of great significance for their extended applications, which, however, is severely hindered by their high disorder, aggregation, and hornified features. Herein, sub-nanoscale anionic metal oxide clusters (phosphotungstic acid, H

The urgent need for immediate personal protection against chemical warfare agents (CWAs) spurs the requirement on robust and highly efficient catalytic systems that can be conveniently integrated to wearable devices. Herein, as a new concept for CWA decontamination catalyst design, sub-nanoscale, catalytically active zirconium-oxo molecular clusters are covalently integrated in flexible polymer network as crosslinkers for the full exposure of catalytic sites as well as robust framework structures. The obtained membrane catalysts exhibit high swelling ratio with aqueous content as 84 wt% and therefore, demonstrate quasi-homogeneous catalytic activity toward the rapid hydrolysis of both CWA, soman (GD) (t1/2 = 5.0 min) and CWA simulant, methyl paraoxon (DMNP) (t1/2 = 8.9 min). Meanwhile, due to the covalent nature of cross-linkages and the high flexibility of polymer strands, the membranes possess promising mechanical strength and toughness that can stand the impact of high gas pressures and show high permeation for both CO2 and O2, enabling their extended applications in the field of collective/personal protective materials with body comfort.

To meet the challenges in resolving the complex morphologies of emergent nanoparticles, a program with a user-friendly graphical user interface has been developed for calculating small-angle scattering curves from custom shapes. The software allows STL-format 3D models, models defined by mathematical functions or combinations of the two as initial input. As a transitional stage, lattice models are generated and the orientation-averaged small-angle scattering data can be calculated using typical spherical harmonics expansion. The validity of the protocol is verified by demonstration models with Protein Data Bank structures and known scattering functions. The software is applied to successfully calculate the scattering curves of a porous spherical shell model where traditional mathematical derivation fails.

Angiosperms may be distinguished from their gymnosperm peers by their flowers, and thus a flower is a good proxy of fossil angiosperms. However, flowers and their parts are usually too frail to be preserved in the fossil record. This makes the origin of angiosperms and their flowers the foci of controversy in botany. Eliminating such botanical controversies can only be achieved by studying related plant fossils. Applying routine scanning electron microscopy, light microscopy and micro-computed tomography (micro-CT) technologies, we document a fossil flower bud, Florigerminis jurassica gen. et sp. nov., from the Jurassic of Inner Mongolia, China. This fossil includes not only a leafy branch but also physically connected fruit and flower bud. The developmentally interpolated existence of a blooming flower between the flower bud and mature fruit in Florigerminis suggests that angiosperm flowers were present in the Jurassic, in agreement with recent botanical progress. Florigerminis jurassica underscores the presence of angiosperms in the Jurassic and demands a rethinking of angiosperm evolution.

Coordination nanocages (CNCs) are under intense research in nanoscience and supramolecular chemistry for their enriched surface functionalities and micro-porosity; however, the understanding of their formation mechanism is still poor due to the difficulty in probing their solution structures. Herein, the CNC formation process from the coordination complexation of the macromolecular isophthalic acid (IPA) ligand and Cu2+ is studied via isothermal titration calorimetry, and its entropy-driven feature is revealed to be originated from the collapse of solvation layers of the assembly units. The CNC formation is thermodynamically less favored with smaller binding constants when the sizes of macromolecular IPA ligands are larger, which originated from the space crowding of macromolecules of the ligands on CNC surfaces and the resulting entropy loss of polymer chain conformations. Meanwhile, the chemical equilibrium of CNC formation can be tuned upon altering the Cu2+/IPA ratio, and the yield of CNCs, suggested from size exclusion chromatography studies, decreases when excessive Cu2+ is applied, providing guidelines for CNC design and synthesis.

The nanoconfinement of proton carrier molecules may contribute to the lowing of their proton dissociation energy. However, the free proton transportation does not occur as easily as in liquid due to the restricted molecular motion from surface attraction. To resolve the puzzle, herein, imidazole is confined in the channels of porous coordination polymers with tunable geometries, and their electric/structural relaxations are quantified. Imidazole confined in a square-shape channels exhibits dynamics heterogeneity of core-shell-cylinder model. The core and shell layer possess faster and slower structural dynamics, respectively, when compared to the bulk imidazole. The dimensions and geometry of the nanochannels play an important role in both the shielding of the blocking effect from attractive surfaces and the frustration filling of the internal proton carrier molecules, ultimately contributing to the fast dynamics and enhanced proton conductivity.

The formation of small 1 to 3 nm organic-ligand free metal-oxide nanocrystals (NCs) is essential to utilization of their attractive size-dependent properties in electronic devices and catalysis. We now report that hexaniobate cluster-anions, [Nb 6 O 19 ] 8- , can arrest the growth of metal-oxide NCs and stabilize them as water-soluble complexes. This is exemplified by formation of hexaniobate-complexed 2.4-nm monoclinic-phase CuO NCs ( 1 ), whose ca. 350 Cu-atom cores feature quantum-confinement effects that impart an unprecedented ability to catalyze visible-light water oxidation with no added photosensitizers or applied potentials, and at rates exceeding those of hematite NCs. The findings point to polyoxoniobate-ligand entrapment as a potentially general method for harnessing the size-dependent properties of small semiconductor NCs by utilizing them as the cores of versatile, entirely-inorganic complexes.

The hybridization of enzymes and inorganics in controlled manner is challenging, however, critical for the development of chemo-enzymatic cascade catalyst with high efficiency and selectivity. Here, proteins and metal oxide clusters can be facilely co-assembled on the surface of colloid of poly(4-vinylpyridine) (P4VP) via hydrogen bonding, due to their enriched surface hydrogen bonding donors. The co-assembly method can be generally applied for preparing chemo-enzymatic catalyst within the selected database of various proteins and metal oxide clusters while the assembly units retain their structures and activities. Typically, a 2.5 nm metal oxide cluster {Mo72Fe30}, with peroxidase-like activity, are complexed with glucose oxidase (GOX) on P4VP for the catalysis against the oxidization of o-dianisidine (ODA) with the existence of glucose. Due to the synergistic effects of chemical and enzymatic catalysis, the co-assemblies show even higher ODA oxidation activity compared to GOX/catalase bi-enzymatic system, confirming the effectiveness of the co-assembly protocol for cascade catalysis and enabling its applications in rapid glucose detection and biomass conversion.

With access to the solution structures of nanocomposites of coordination nanocages (CNCs) via scattering and chromatography techniques, their mysterious solution dynamics have been, for the first time, resolved, and interestingly, the surface macromolecules can be substituted by extra free macromolecules in solutions. Obvious exchange of macromolecules can be observed in the solution mixtures of CNC nanocomposites at high temperatures, revising the understanding of the dynamics of CNC nanocomposites. Being distinct from nanocomposites of a simple coordination complex, the quantified solution dynamics of CNC nanocomposites indicates a typical logarithmic time dependence with the dissociation of surface macromolecules as the thermodynamically limiting step, suggesting strongly coupled and hierarchically constrained dynamics among the surface macromolecules. Their dynamics can be activated only upon application of high temperature or selected solvents, and therefore, the rational design of polymer assemblies, for example, hybrid-arm star polymers with precisely controlled compositions and reprocessable, robust CNC-cross-linked supramolecular polymer networks, is facilitated.

Fractal structures with self-similarity are of fundamental importance in the fields of aesthetic, chemistry and mathematics. Here, by taking advantage of constructs the rational geometry-directed precursor design, we report the construction of two fascinating Platonic solids, the Sierpiński tetrahedron ST-T and the Sierpiński octahedron ST-O, in which each possesses a fractal Sierpiński triangle on their independent faces. These two discrete complexes are formed in near-quantitative yield from the multi-component self-assembly of truncated Sierpiński triangular kernel L

Here we report the formation of giant {Mo

Coordination nanocage (CNC) incorporated gels have attracted enormous attention for the effective integration of micro-porosity, mechanical flexibility and processability; however, the understanding of their microscopic structure-property relationships remains unclear. Herein, CNCs with 24 surface grafted cholesterol groups are constructed precisely and their gelation can be manipulated upon the tunning of solvent polarities. Optically homogeneous organogels can be formed by introducing a certain amount of bad solvents into the solutions of hairy CNCs and the gelation can be reversed through temperature variation. Suggested from scattering and molecular dynamics studies, the solvophobic interaction-driven aggregation of cholesterol units contributes to the physical crosslinking of CNCs and finally the gelation of CNC solutions. The mechanical strength of the obtained gels is observed to be highly dependent on the flexibility of the organic linkers that bond the cholesterol units on the CNC surface. The effective interaction and dense packing of the cholesterol units in their aggregates highly rely on the degree of freedom of the cholesterol, which is controlled by the flexibility of the organic linkers that bond them on the CNC surface. The observed viscoelastic performance accompanied by the well-controlled mechanical strength of the organogels unambiguously demonstrates the potential for exploiting the synergistic physical correlations to fabricate novel functional materials from CNCs.

The therapeutic application of vanadium compounds is plagued by their poor bioavailability and potential adverse effects. Herein, 1 nm polyoxovanadate (POV) clusters are functionalized with alkyl chains of various lengths and studied for the effect of surface engineering on their preclinical pharmacokinetics and typical insulin-sensitizing activity. The concentrations of surface engineered POVs in plasma, urine, and feces are monitored after a single administration to rats. The POVs exhibit a two-compartment profile of in vivo kinetics, and the surface engineering effect plays an important role in renal clearance of the POVs comparable to small molecules. POVs functionalized with long alkyl chains show much shorter elimination half time tsub1/2β/suband higher elimination fractions (50%) within 48 h than pristine POVs, suggesting favorable elimination kinetics to mitigate the possible side effects of vanadium. Meanwhile, long alkyl chain modification leads to a 76% increment of oral bioavailability in contrast to unmodified POVs. As suggested by glucose tolerance tests and sub-chronic toxicity tests, the above two factors contribute to the enhanced therapeutic efficacy of POVs while mitigating their adverse effects. The surface engineering protocol provides a feasible approach to the optimization of the bioavailability and pharmacokinetic properties of POVs for promoted insulin-sensitizing activities.

Hybrid nanocomposites of uranyl peroxide nanocages are assembled from the ionic interaction between anionic uranyl peroxide nanocage clusters (Li44K16[UO2(O2)(OH)]60, U60) and cationic surfactants....

Films that can maintain their flexibilities and conductivities under low humidity and broad temperature range represent the next generation of solid-state proton conductors, which would extend the ...

Developing proton-conducting membranes with three-dimensional conductivity and expedited interfacial contact is requested in the field of fuel cells. Here, we present a design strategy by combining solution processing and material flexibility into amorphous and porous polymers. We design a nanoporous polymer whose skeleton contains dihydrophenazine as a proton-accepting site, and subsequently protonate these sites to produce abundant charges on the polymer skeletons, which enables ionic polymers to be well dispersed in organic solvents and guarantees that they can be fabricated into uniform and amorphous membranes in a solution-processed manner. Importantly, after protonation, the dihydrophenazines change to proton-donating sites, which exhibit dynamic local motions that assist proton exchange on the polymer skeletons and thus construct three-dimensional and unimpeded proton-conduction pathways, with a striking proton conductivity of 0.30 S cm−1 (298 K and 90% relative humidity), a low resistance of 3.02 Ω, and a H+ transport number of 0.98 that was very close to the upper limitation of 1.0.

Structural transitions of polyamide 46 (PA46) films during the tensile stretch at temperatures from 37 to 249 °C were studied using in situ synchrotron radiation wide-angle X-ray diffraction (SR-WAXD) and Fourier transform infrared (FTIR) techniques. The structural evolution during the stretch at different temperatures can be roughly divided into three regions. In region I (37 ≤ T < 180 °C), stretch enlarges the d-spacing gap between the (100) and (010/110) planes of α phase (triclinic), which is opposite to that during heating. In region II (180 ≤ T < 230 °C), stretch induces a reverse Brill transition, which is characterized by the single diffraction of γ phase (pseudohexagonal) splitting into two diffractions of α phase, while further increasing the strain drives the two split diffractions to transform to a single broad diffraction. As in situ FTIR measurements reveal the continuously increasing content of trans conformation, we speculate that stretch may induce a new form, which is an intermediate structure close to both α and γ phases (named α′ phase) at large strain. In region III (230 ≤ T ≤ 249 °C), the γ phase may skip the α phase and directly transform into the α′ phase. The nonequilibrium crystal phase diagrams of PA46 were constructed in the strain–temperature space and true stress–temperature space. Current results demonstrate that stretch plays a countereffect of heating on the Brill transition of PA46.

Materials under space confinement can alter their physical and chemical properties, paving the way for new science and novel applications. Nanoparticles can enforce spatial constraints on the polym...

The simultaneous improvement of catalytic activity and recyclability of metal oxides is exciting, however challenging, due to the paradox for particle size requirements. Herein, we report the design of polymer nanocomposites (PNCs) by covalently integrating a sub-nanoscaled metal oxide cluster (∼0.7 nm) into a polymer network with superelasticity. Due to the ultrasmall sizes of loaded clusters and the high swelling ratios (SRs) of PNCs, the swelled organogels from PNCs claim similar catalytic efficiencies to homogeneous catalysts, while their recyclability can be simply achieved after the catalytic reactions. Thanks to their robust mechanical properties, the PNCs can be processed into microgel particles for column reactors, enabling large-scale and continuous-flow catalysis.

Despite numerous studies have been conducted to explore the crystalline structures of various metal-organic polyhedra (MOPs), the direct probing of solvated and deformed structures of MOPs is still...

The precise construction of the high-order mechanically interlocked molecules (MIMs) with well-defined topological arrangements of multiple mechanically interlocked units has been a great challenge. Herein, we present the first successful preparation of a new family of daisy chain dendrimers, in which the individual [c2]daisy chain rotaxane units serve as the branches of dendrimer skeleton. In particular, the third-generation daisy chain dendrimer with 21 [c2]daisy chain rotaxane moieties was realized, which might be among the most complicated discrete high-order MIMs comprised of multiple [c2]daisy chain rotaxane units. Interestingly, such unique topological arrangements of multiple stimuli-responsive [c2]daisy chain rotaxanes endowed the resultant daisy chain dendrimers controllable and reversible nanoscale dimension modulation through the collective and amplified extension/contraction of each [c2]daisy chain rotaxane branch upon the addition of acetate anions or DMSO molecules as external stimulus. Furthermore, on the basis of such an intriguing size switching feature of daisy chain dendrimers, dynamic composite polymer films were constructed through the incorporation of daisy chain dendrimers into polymer films, which could undergo fast, reversible, and controllable shape transformations when DMSO molecules were employed as stimulus. The successful merging of [c2]daisy chain rotaxanes and dendrimers described herein provides not only a brand-new type of high-order mechanically interlocked systems with well-defined topological arrangements of [c2]daisy chain rotaxanes, but also a successful and practical approach toward the construction of supramolecular dynamic materials.

Water in different physical states has been attracting great interest for decades for its strong association with the origin of life, the biophysical behaviors of biomacromolecules, and the transpo...

Among molecular building blocks, metal oxide cluster anions and their countercations provide multiple options for the self-assembly of functional materials. Currently, however, rational design concepts are limited to electrostatic interactions with metal or organic countercations or to the attachment and subsequent reactions of functionalized organic ligands. We now demonstrate that bridging μ-oxo linkages can be used to string together a bifunctional Keggin anion building block, [PNb2Mo10O40]5– (1), the diniobium(V) analogue of [PV2Mo10O40]5– (2). Induction of μ-oxo ligation between the NbV=O moieties of 1 in acetonitrile via step-growth polymerization gives linear polymers with entirely inorganic backbones, some comprising over 140 000 repeating units, each with a 3– charge, exceeding that of previously reported organic or inorganic polyelectrolytes. As the chain grows, its flexible μ-oxo-linked backbone, with associated countercations, coils into a compact 270 nm diameter spherical secondary structure as a result of electrostatic interactions not unlike those within ionic lattices. More generally, the findings point to new options for the rational design of multidimensional structures based on μ-oxo linkages between NbV=O-functionalized building blocks.

The critical size limit for general structural material design is challenged in the dimers of sub-nm molecular clusters that possess small sizes (

Understanding the dynamics of soft colloids, such as star polymers, dendrimers, and microgels, is of scientific and practical importance. It is known that the excluded volume effect plays a key role in colloidal dynamics. Here, we propose a condition of compressibility equivalence that provides a simple method to experimentally evaluate the excluded volume of soft colloids from a thermodynamic view. We apply this condition to survey the dynamics of a series of star polymer dispersions. It is found that as the concentration increases, the slowing of the long-time self-diffusivity of the star polymer, normalized by the short-time self-diffusivity, can be mapped onto the hard-sphere behavior. This phenomenon reveals the dynamic equivalence between soft colloids and hard spheres, despite the apparent complexity of the interparticle interaction of the soft colloids. The methods for measuring the osmotic compressibility and the self-diffusivities of soft colloidal dispersions are also presented., 18 pages, 4 figures

Hospital-acquired infections are a serious threat to the recovery of patients. To prevent such infections, an antibacterial coating is an effective method to eliminate bacterial colonization on healthcare-related surfaces. Herein, we report an antibacterial hydrogel composed of silver-containing polyoxometalate (AgP