Structural Engineering of Co-Metal-Organic Frameworks via Ce Incorporation for Improved Oxygen Evolution.

The rational design of metal-organic framework (MOF)-based electrocatalysts plays a key role in achieving high-efficiency oxygen evolution reaction (OER). Herein, a synergetic morphology and electronic structure engineering strategy are proposed to design a Co-MOF nanoflower grown on carbon paper via rare-earth cerium doping (CoCe-MOF/CP). Compared with Co-MOF/CP, the developed CoCe-MOF/CP exhibited superior OER performance with a low overpotential of 267 mV at 10 mA cm-2 and outstanding long-term stability over 100 h. Theoretical calculations show that the unique 4f valence electron structure of Ce induced charge redistribution of the Co-MOF surface through the strong Co 3d-O 2p-Ce 4f orbital electronic coupling below the Fermi level. Ce-doped plays a key role in the engineering of the electronic states of the Co sites to endow them with the optimal free energy landscape for enhanced OER catalytic activity. This work provides new insights into comprehending the RE-enhanced mechanism of electrocatalysis and provides an effective strategy for the design of MOF-based electrocatalysts.

Highly Stable Europium(III) Tetrahedral (Eu4L4)(phen)4 Cage: Structure, Luminescence Properties, and Cellular Imaging.

Luminescent lanthanide cages have many potential applications in guest recognition, sensing, magnetic resonance imaging (MRI), and bioimaging. However, these polynuclear lanthanide assemblies' poor stability, dispersity, and luminescence properties have significantly constrained their practical applications. Furthermore, it is still a huge challenge to simultaneously synthesize and design lanthanide organic polyhedra with high stability and quantum yield. Herein, we demonstrate a simple and robust strategy to improve the rigidity, chemical stability, and luminescence of an Eu(III) tetrahedral cage by introducing the conjugated planar auxiliary phen ligand. The self-assembled tetrahedral cage, (Eu4L4)(phen)4 [L = (4,4',4″-tris(4,4,4-trifluoro-1,3-dioxobutyl)-triphenylamine), phen = 1,10-phenanthroline], exhibited characteristic luminescence of Eu3+ ions with high quantum yield (41%) and long lifetime (131 µs) in toluene (1.0 × 10-6 M). Moreover, the Eu(III) cage was stable in water and even in an aqueous solution with a pH range of 1-14. 3-(4,5-Dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay and cellular imaging revealed that the Pluronic F127-coated hybrid material, (Eu4L4)(phen)4@F127, exhibited low cytotoxicity, good biocompatibility, and cellular imaging ability, which may inspire more insights into the development of lanthanide organic polyhedra (LOPs) for potential biomedical applications.

Red Fluorescence of Eu3+-Doped ZnAl-LDH Response to Intercalation and Release of Ibuprofen.

A drug delivery system with identification function is attractive and important. For this reason, the red fluorescence of Eu3+-doped ZnAl-LDH response to intercalation and release of ibuprofen (IBU) has been studied. X-ray diffraction(XRD) results showed that the basal spacing of the Eu3+-doped ZnAl-LDH varied from 8.85 to 12.04 Å after the intercalation of IBU. The release of the IBU from the Eu3+-doped ZnAl-LDH was carried out in simulated intestinal medium (phosphate buffer solutions with pH 7.4 and 37 °C), and the releasing behavior of IBU exhibited an initial rapid release followed by a slow release. Moreover, the present delivery system has slower release of drug than those of other LDH-based delivery systems. Interestingly, the intercalation of IBU into the Eu3+-doped ZnAl-LDH obviously reduced the red fluorescence of the Eu3+-doped ZnAl-LDH, whereas the red fluorescence was recovered after the release of IBU. This fluorescent responsiveness may be a favorable signal for detecting the delivery and release of IBU. Therefore, the Eu3+-doped ZnAl-LDH with red fluorescence would be potential application as drug delivery system with identification function because of its cheapness, non-toxicity, good biocompatibility, and little damage to biological tissue.

Effect of strong electric field on the conformational integrity of insulin.

A series of molecular dynamics (MD) simulations up to 1 µs for bovine insulin monomer in different external electric fields were carried out to study the effect of external electric field on conformational integrity of insulin. Our results show that the secondary structure of insulin is kept intact under the external electric field strength below 0.15 V/nm, but disruption of secondary structure is observed at 0.25 V/nm or higher electric field strength. Although the starting time of secondary structure disruption of insulin is not clearly correlated with the strength of the external electric field ranging between 0.15 and 0.60 V/nm, long time MD simulations demonstrate that the cumulative effect of exposure time under the electric field is a major cause for the damage of insulin's secondary structure. In addition, the strength of the external electric field has a significant impact on the lifetime of hydrogen bonds when it is higher than 0.60 V/nm. The fast evolution of some hydrogen bonds of bovine insulin in the presence of the 1.0 V/nm electric field shows that different microwaves could either speed up protein folding or destroy the secondary structure of globular proteins deponding on the intensity of the external electric field.

Mechanically Robust, Durable, and Multifunctional Hyper-Crosslinked Elastomer Based on Metal-Organic-Cluster Crosslinker: The Role of Topological Structure.

Polymer materials formed by conventional metal-ligand bonds have very low branch functionality, the crosslinker of such polymer usually consists of 2-4 polymer chains and a single metal ion. Thus, these materials are weak, soft, humidity-sensitive, and unable to withstand their shape under long-term service. In this work, a new hyperbranched metal-organic cluster (MOC) crosslinker containing up to 16 vinyl groups is prepared by a straightforward coordination reaction. Compared with the current typical synthesis of metal-organic cages (MOCs) or metal-organic-polyhedra (MOP) crosslinkers with complex operations and low yield, the preparation of the MOC is simple and gram-scale. Thus, MOC can serve as a high-connectivity crosslinker to construct hyper-crosslinked polymer networks. The as-prepared elastomer exhibits mechanical robustness, creep-resistance, and humidity-stability. Besides, the elastomer possesses self-healing and recyclability at mild condition as well as fluorescence stability. These impressive comprehensive properties are proven to originate from the hyper-crosslinked topological structure and microphase-separated morphology. The MOC-driven hyper-crosslinked elastomers provide a new solution for the construction of mechanically robust, durable, and multifunctional polymers.

Synthesis of Hierarchical Layered Quasi-Triangular Ce(OH)CO3 and Its Thermal Conversion to Ceria with High Polishing Performance.

Layered quasi-triangular Ce(OH)CO3 assembled from primary nanoparticles was synthesized via a solvothermal method and converted into CeO2 abrasive particles by calcination at 800-1000 °C. With the increase of calcination temperature, the primary particle size increased and the microstructure, mechanical hardness, and chemical activity of the CeO2 particles changed, thus affecting the polishing performance. The calcined products obtained at 800, 850, and 900 °C maintained the layered edge structure of the Ce(OH)CO3 precursor and had a relatively high specific surface area and surface Ce3+ concentration. The samples calcined at 950 and 1000 °C lost the layered structure due to the large-scale melting of the primary particles, and their surface chemical activity decreased. The polishing experiments on K9 glass showed that, with the calcination temperature rising from 800 to 1000 °C, the material removal rate (MRR) first increased and then decreased sharply. The initial increase of MRR was attributed to the increase of mechanical hardness of the layered quasi-triangular CeO2, and the subsequent decrease of MRR was related to the decrease in surface chemical activity and disappearance of the layered edge structure. The product calcined at 900 °C had the highest MRR and best surface quality after polishing due to the layered edge structure and optimal match of chemical activity and mechanical hardness.

A new type of silica-coated Gd2(CO3)3:Tb nanoparticle as a bifunctional agent for magnetic resonance imaging and fluorescent imaging.

We report a new type of dual modal nanoprobe to combine optical and magnetic resonance bioimaging. A simple reverse microemulsion method and coating process was introduced to synthesize silica-coated Gd(2)(CO(3))(3):Tb nanoparticles, and the particles, with an average diameter of 16 nm, can be dispersed in water. As in vitro cell imaging of the nanoprobe shows, the nanoprobe accomplishes delivery to gastric SGC7901 cancer cells successfully in a short time, as well as NCI-H460 lung cancer cells. Furthermore, it presents no evidence of cell toxicity or adverse affect on kidney cell growth under high dose, which makes the nanoprobe's optical bioimaging modality available. The possibility of using the nanoprobe for magnetic resonance imaging is also demonstrated, and the nanoprobe displays a clear T(1)-weighted effect and could potentially serve as a bimodal T(1)-positive contrast agent. Therefore, the new nanoprobe formed from carbonate nanoprobe doped with rare earth ions provides the dual modality of optical and magnetic resonance imaging.

Support effects on the dissociation of hydrogen over gold clusters on ZnO(101) surface: Theoretical insights.

We perform density functional studies of the support effects on the gold-catalyzed dissociation of H(2) using the model clusters (Au(10) and Au(13)) on ZnO(101) surface and find that H(2) prefers to adsorb on the bottom layer of Au clusters on the ZnO surface. The interaction energies of H(2) are exponentially correlated with the H-H and H-Au bond parameters. The dissociation of H(2) easily occurs on the bottom layer with the energy barriers no more than 0.44 eV. The support effects on the dissociation barriers are greatly dependent on the H-H bond distance in the transition state (TS), i.e., the early TSs with small barriers have larger support effects than the late TSs with large barriers. We find that the charge transfer from the gold clusters to the oxide support creates the localized charging states of the interface gold with the high feasibility for H(2) activation and dissociation.

Changing the calcination temperature to tune the microstructure and polishing properties of ceria octahedrons.

Ceria octahedrons with different microstructure and surface characteristics were prepared by calcining an octahedral CeO2 precursor self-assembled from spherical primary nanocrystals of about 5 nm at 500-900 °C. Structural characterization revealed that with the calcination temperature increasing from 500 to 700 °C, the products maintained a hierarchical structure and primary nanocrystals changed from spherical to octahedral particles. Significant fusion occurred between the primary nanocrystals and the surface of the octahedrons became smooth at the calcination temperature of 800 °C. Single crystal CeO2 octahedrons were formed when the calcination temperature reached 900 °C. The change in microstructure induced by elevated calcination temperature led to increased mechanical hardness and decreased surface chemical activity (specific surface area and surface Ce3+ concentration) of the octahedrons, which had an impact on their polishing performance. The polishing experiments on K9 glass showed that the polishing rate first increased and then decreased with the increment of calcination temperature, indicating that in addition to the mechanical hardness, the surface chemical activity of the octahedrons is also important for material removal. Owing to the best matching of chemical activity and mechanical hardness, CeO2 octahedrons calcinated at 700 °C exhibited the highest polishing rate and the best surface quality for K9 glass.

One-dimensional Europium-coordination polymer as luminescent sensor for highly selective and sensitive detection of 2,4,6-trinitrophenol.

Three isostructural lanthanide coordination polymers (LnCPs), [Ln(L)6(DMF)]n {HL = 2-(2-formylphenoxy) acetic acid, Ln = Sm (1); Eu (2); Tb (3)} have been synthesized by solvothermal reaction and characterized. Single crystal analyses revealed that the architectures of these LnCPs own one dimensional chain which can be further packed into two-dimensional architectures by hydrogen bonds. Moreover, these LnCPs can offer strategically placed uncoordinated formyl groups, which may act as hydrogen-bond acceptor in the sensing of nitro explosives. Luminescence measurements reveal that LnCPs 2 and 3 exhibit strong luminescence in solid states. LnCP 2 shows quick, highly selective and sensitive detection of 2,4,6-trinitrophenol (TNP) with the high quenching constant (2.6 × 104 M-1) and low detection limit (3.39 µM), which indicates that LnCP 2 is more efficient than most of Eu-based coordination polymers for the sensing of TNP. Furthermore, LnCP 2 represents the first example of one-dimensional Eu-based sensors with formyl group as hydrogen-bonding site in the detection of TNP.

Recent Advances in Stimuli-Sensitive Amphiphilic Polymer-Paclitaxel Prodrugs.

Paclitaxel (PTX) is a broad-spectrum chemotherapy drug employed in the treatment of a variety of tumors. However, the clinical applications of PTX are limited by its poor water solubility. Adjuvants are widely used to overcome this issue. However, these adjuvants often have side effects and poor biodistribution. The smart drug delivery system is a promising strategy for the improvement of solubility, permeability, and stability of drugs, and can promote sustained controlled release, increasing therapeutic efficacy and reducing side effects. Polymeric prodrugs show great advantages for drug delivery due to their high drug loading and stability. There has been some groundbreaking work in the development of PTX-based stimulus-sensitive polymeric prodrug micelles, which is summarized in this study. We consider these in terms of the four main types of stimulus (pH, reduction, enzyme, and reactive oxygen species (ROS)). The design, synthesis, and biomedical applications of stimulus-responsive polymeric prodrugs of PTX are reviewed, and the current research results and future directions of the field are summarized.

Rational design of MoSe2 nanosheet-coated MOF-derived N-doped porous carbon polyhedron for potassium storage.

For potassium-ion battery (PIB), it remains a huge challenge to develop an appropriate anode material to compensate the large radius of K+. MoSe2 shows great potential for efficient K+ insertion/extraction due to its unique lamellar structures with an interlayer spacing of 6.46 Å. However, pure MoSe2 has low electronic conductivity and agglomerates during long-term cycling. In the present work, MoSe2 nanosheets were fabricated on the N-doped porous carbon polyhedron (NPCP). The obtained product was designated as NPCP@MoSe2 and functioned as anode materials for PIBs. NPCP@MoSe2 displayed a promising reversible capacity (325 mAh/g at 100 mA/g after 80 cycles), long-term cycling performance (128 mAh/g at 500 mA/g after 800 cycles), and superior rate property at 5000 mA/g. The enhanced electrochemical performance of NPCP@MoSe2 could be attributed to the rational design of hybrid structures. Notably, the hollow NPCP provide a large contact area for the interactions among the electrolytes and electro-active materials as well as partly buffer the volume expansion. The synergistic effects between MoSe2 and NPCP could mitigate the agglomeration of MoSe2 nanosheets. Besides, the uniformly doping N elements enhanced the conductivity of the carbon matrix, and the N-group also provided potential binding active sites for K-ion accommodation. This work paves the ideas for the design of novel anode materials with high specific capacity, good cycling stability and outstanding rate capability for PIBs.

A Co-delivery System Based on a Dimeric Prodrug and Star-Shaped Polymeric Prodrug Micelles for Drug Delivery.

Chemotherapy is one of the commonly used therapies for the treatment of malignant tumors. Insufficient drug-loading capacity is the major challenge for polymeric micelle-based drug delivery systems of chemotherapy. Here, the redox-responsive star-shaped polymeric prodrug (PSSP) and the dimeric prodrug of paclitaxel (PTX) were prepared. Then the dimeric prodrug of PTX (diPTX, diP) was loaded into the core of the star-shaped polymeric prodrug micelles of PSSP by hydrophobic interaction forming the redox-responsive prodrug micelles of diPTX@PSSP for intracellular drug release in tumor cells. The hydrodynamic diameter of diPTX@PSSP nanoparticles was 114.3 nm ± 2.1 (PDI = 0.219 ± 0.016), and the micelles had long-term colloidal stability and the drug-loading content (DLC) of diPTX and PTX is 16.7 and 46.9%, respectively. The prepared micelles could broke under the reductive microenvironment within tumor cells, as a result, the dimeric prodrug of diP and polymeric prodrug micelles of PSSP were rapidly disassembled, leading to the rapid release of intracellular drugs. In vitro release studies showed that under the condition of reduced glutathione (GSH) (10 mM), the release of PTX was significantly accelerated with approximately 86.6% released within 21 h, and the released PTX in cytoplasm could promote the disintegration of microtubules and induce cell apoptosis. These results indicated that the new type of this reduction-sensitive nanodrug delivery system based on dimeric prodrug@polymeric prodrug micelles would be a promising technology in chemotherapy.

Methyl 2-hydr-oxy-3-nitro-benzoate.

The title compound, C(8)H(7)NO(5), assumes an approximately planar mol-ecular structure with an intra-molecular O-H⋯O hydrogen bond between the hydr-oxy and carboxyl-ate groups. Weak inter-molecular C-H⋯O hydrogen bonding is present in the crystal structure.

Fabrication and biological imaging of hydrazine hydrate cross-linked AIE-active fluorescent polymeric nanoparticles.

Amphiphilic copolymers play a paramount role in the fabrication of fluorescent polymeric nanoparticles (FPNs) through the self-assembly procedure. In this work, novel hydrazine hydrate cross-linked amphiphilic poly(PEG­co­FHMA) copolymers were constructed via reversible addition-fragmentation chain transfer (RAFT) polymerization, containing an aggregation-induced emission (AIE) active hydrophobic moiety and a hydrophilic poly(ethylene glycol) (PEG) group. Different characterization techniques have been employed to confirm their successful synthesis. Due to their amphiphilic property, the resulting poly(PEG­co­FHMA) copolymers can self-assemble into FPNs in aqueous solution and form poly(PEG­co­FHMA) FPNs with size ranging from 100 to 200 nm. The investigation of photophysical properties demonstrated poly(PEG­co­FHMA) FPNs possess strong fluorescence, large Stokes shift, excellent AIE characteristic, low critical micelle concentration and remarkable photostability. Biological assay results suggested that these cross-linked AIE-active FPNs are of low toxicity and excellent cell dyeing performances. All of these features make them promising candidates for biomedical applications. As compared with typical AIE-active FPNs based on the synthetic AIE-active compounds, the novel cross-linked AIE-active FPNs based on the Schiff base is rather simple, good designable and universal. More importantly, this strategy could also be adopted for preparation of a large number of AIE-active FPNs because of the well designability of copolymers and salicylaldehyde derivatives. Thus this work will provide a novel route for preparation of multifunctional AIE-active FPNs in a rather facile manner.

Facile preparation of magnetic composites based on carbon nanotubes: Utilization for removal of environmental pollutants.

The preparation of multifunctional composites that combine magnetic nanoparticles and supported nanomaterials has attracted great attention for various applications. In this work, a facile method was developed for the preparation of carbon nanotube (CNT)-based magnetic composites through a one-pot oxidation method using K2FeO4 as the oxidant, which was subsequently used as the reagent to generate the Fe3O4 nanoparticles and fabricate the magnetic CNT composites. This strategy could be performed at room temperature, so it is very mild and straightforward. The properties and structure of the as-fabricated CNT-Fe3O4 composites were characterized by Fourier transform infrared spectroscopy, thermogravimetric analysis, transmission electron microscopy, X-ray photoelectron spectroscopy, X-ray diffraction, and vibrating sample magnetometry. The results suggested that this approach not only generated Fe3O4 magnetic nanoparticles on the surface of the CNTs but also produced a series of functional groups. In addition, the dried CNT-Fe3O4 composites were highly dispersible in water or organic solutions, and they also had a magnetic response that could satisfy the demand for magnetic separation. Finally, we adsorbed copper ions (Cu2+) and methylene blue (MB) using the CNT-Fe3O4 composites as adsorbents. The results indicated that the obtained composites could adsorb both Cu2+ and MB effectively. Taken together, we report a novel strategy for the fabrication of magnetic carbon nanotube composites through a facile oxidation and subsequent deposition procedure. These magnetic composites show great potential for the removal of environmental pollutants.

Preparation, Structure, Photoluminescent and Semiconductive Properties, and Theoretical Calculation of a Mononuclear Nickel Complex with 3-Hydroxy-2- Methylquinoline-4-Carboxylato Ligand.

A novel nickel complex with mixed ligands [Ni(L)2(EtOH)2(MeOH)2] (HL = 3-hydroxy-2-methylquinoline-4-carboxylic acid) has been synthesized through solvothermal reaction and its crystal structure was determined by single-crystal X-ray diffraction technique. Single-crystal X-ray diffraction analyses reveals that the title compound crystallizes in the triclinic system of the P-1 space group, and exists as isolated mononuclear complex. The intermolecular hydrogen bonds lead to the formation of chains, and the layered supramolecular structure is formed by the strong ααααα stacking interactions. Solid-state photoluminescent characterization reveals that the title compound has an emission in the green region. Time-dependent density functional theory (TDDFT) calculation shows that the nature of the photoluminescence of the title compound originates from the ligand-to-ligand charge transfer (LLCT; from the HOMO of the p-orbital of ligand HMCA to the LUMO of the oxygen atoms). A wide optical band gap of 2.25 eV is found by the solid-state UV/vis diffuse reflectance spectrum.

[Preparation and photoluminescence study of Er3+ : Y2O3 transparent ceramics].

Y2O3 acted as the matrix material, which was doped with different concentrations of Er3+, Er3+ : Y2O3 nanocrystalline powder was prepared by co-precipitation method, and Er3+ : Y2O3 transparent ceramics was fabricated by vacuum sintering at 1700 degrees C, 1 x 10(-3) Pa for 8 h. By using the X-ray diffraction (D/MAX-RB), transmission electron microscopy(Philips EM420), automatic logging spectrophotometer(DMR-22), fluorescence analyzer (F-4500) and 980 nm diode laser, the structural, morphological and luminescence properties of the sample were investigated. The results show that Er3+ dissolved completely in the Y2O3 cubic phase, the precursor was amorphous, weak diffraction peaks appeared after calcination at 400 degrees C, and if calcined at 700 degrees C, the precursor turned to pure cubic phase. With increasing the calcining temperature, the diffraction peaks became sharp quickly, and when the calcining temperature reached 1100 degrees C, the diffraction peaks became very sharp, indicating that the grains were very large. The particles of Er+ : Y2O3 is homogeneous and nearly spherical, the average diameter of the particles is in the range of 40-60 nm after being calcined at 1000 degrees C for 2 h. The relative density of Er3+ : Y2O3 transparent ceramics is 99.8%, the transmittance of the Er2+ : Y2O3 transparent ceramics is markedly lower than the single crystal at the short wavelength, but the transmittance is improved noticeably with increasing the wavelength, and the transmittance exceeds 60% at the wavelength of 1200 nm. Excited under the 980 nm diode laser, there are two main up-conversion emission bands, green emission centers at 562 nm and red emission centers at 660 nm, which correspond to (4)S(3/2) / (2)H(11/2) - (4)I(15/2) and (4)F(9/2) - (4)I(15/2) radiative transitions respectively. By changing the doping concentrations of Er3+, the color of up-conversion luminescence can be tuned from green to red gradually. The luminescence intensity is not reinforce with the increase in the concentration, so the doping concentration of Er3+ should not exceed 2%. If the doping concentration of Er3+ exceeds the range, the concentration has very small effect on the improvement of luminescence intensity.

2-[(2H-Tetra-zol-2-yl)meth-yl]benzonitrile.

The title compound, C(9)H(7)N(5), is non-planar with a dihedral angle between the substituted benzene and tetra-zole rings of 71.13 (9)°. Molecules are connected in centrosymmetric dimers by weak C-H⋯N inter-actions [C⋯N is 3.548 (5) Å]; these are the only interactions of significance in the crystal structure.

A facile strategy for fabrication of aggregation-induced emission (AIE) active fluorescent polymeric nanoparticles (FPNs) via post modification of synthetic polymers and their cell imaging.

Aggregation-induced emission (AIE) active fluorescent polymeric nanoparticles (FPNs) have recently emerged as the promising nanoprobes for biological imaging for their intensive fluorescence, good photostability, desirable biocompatibility and well designability of structure and optical properties. Herein, we proposed a novel strategy for fabrication of AIE-active FPNs through the post modification of synthetic copolymers to form Schiff base. The size, morphology, optical properties and biocompatibility as well as cell uptake behavior were evaluated in detailed. To fabricate these AIE-active FPNs, poly(PEG-co-VA) copolymers were first obtained via addition-fragmentation chain transfer polymerization using poly(ethylene glycol) methyl ether methacrylate (PEGMA) and 3-vinylaniline (VA) as the monomers. Then the AIE-active SA-poly(PEG-co-VA) FPNs were formed through the reaction between salicylaldehyde (SA) and VA. Results demonstrated that SA-poly(PEG-co-VA) FPNs possess bright fluorescence, superior photo-bleaching resistance, excellent biocompatibility and efficient cell uptake behavior. To the best of our knowledge, this is the first report for fabrication AIE-active FPNs through post modification of synthetic copolymers. The facile fabrication procedure and the remarkable features suggested that these AIE-active FPNs promising candidates for biomedical applications.