A novel enzyme-free electrochemical sensing strategy was proposed for sensitive monitoring of DNA and miRNA by smart combination of the cyclic cleavage reaction of Mg2+-dependent DNAzyme and the host–guest inclusion between ferrocene-labeled hairpin probe (H-1) and nitrogen-doped reduced graphene oxide/β-cyclodextrin polymer (NRGO/β-CDP) nanocomposites. The synthesized NRGO/β-CDP nanocomposites with high electrocatalytic activity and recognition capability were modified on the glassy carbon electrode to construct the sensing platform. Upon the hybridization reaction of subunit DNA in the loop region with target sequence, the active DNAzyme was liberated from the caged structure, which bound with H-1 to catalyze its cleavage in the presence of Mg2+ and triggered the target recycling amplification for the cleavage of a large number of H-1. Each cleaved H-1 was divided into two single-stranded oligonucleotides, leading to an obvious enhancement of peak current by the molecular recognition of β-CDP on the electrode. Thus, the constructed biosensor showed high sensitivity and selectivity for DNA and miRNA assays, with wide concentration ranges of 0.01–1000 and 0.05–500 pM and low detection limits of 3.2 and 18 fM, respectively. This developed sensing strategy may become a promising nucleic acid detection method in bioassays and clinical diagnosis.Keywords: biosensor; DNAzyme; electrochemical detection; nitrogen-doped reduced graphene oxide; β-cyclodextrin polymer;

Lithium–sulfur (Li–S) batteries have currently excited worldwide academic and industrial interest as a next-generation high-power energy storage system (EES) because of their high energy density and low cost of sulfur. However, the commercialization application is being hindered by capacity decay, mainly attributed to the polysulfide shuttle and poor conductivity of sulfur. Here, we have designed a novel dual core–shell nanostructure of S@C@MnO2 nanosphere hybrid as the sulfur host. The S@C@MnO2 nanosphere is successfully prepared using mesoporous carbon hollow spheres (MCHS) as the template and then in situ MnO2 growth on the surface of MCHS. In comparison with polar bare sulfur hosts materials, the as-prepared robust S@C@MnO2 composite cathode delivers significantly improved electrochemical performances in terms of high specific capacity (1345 mAh g–1 at 0.1 C), remarkable rate capability (465 mA h g–1 at 5.0 C) and excellent cycling stability (capacity decay rate of 0.052% per cycle after 1000 cycles at 3.0 C). Such a structure as cathode in Li–S batteries can not only store sulfur via inner mesoporous carbon layer and outer MnO2 shell, which physically/chemically confine the polysulfides shuttle effect, but also ensure overall good electrical conductivity. Therefore, these synergistic effects are achieved by unique structural characteristics of S@C@MnO2 nanospheres.Keywords: dual core−shell structure; in situ redox reaction; lithium−sulfur batteries; mesoporous carbon; MnO2 shell;

An innovative approach for efficient synthesis of petal-like molybdenum disulfide nanosheets inside hollow mesoporous carbon spheres (HMCSs), the yolk–shell structured MoS2@C, has been developed. HMCSs effectively control and confine in situ growth of MoS2 nanosheets and significantly improve the conductivity and structural stability of the hybrid material. The yolk–shell structured MoS2@C is proven to achieve high reversible capacity (993 mA h g–1 at 1 A g–1 after 200 cycles), superior rate capability (595 mA h g–1 at a current density of 10 A g–1), and excellent cycle performance (962 mA h g–1 at 1 A g–1 after 1000 cycles and 624 mA h g–1 at 5 A g–1 after 400 cycles) when evaluated as an anode material for lithium-ion batteries. This superior performance is attributed to the yolk–shell structure with conductive mesoporous carbon as the shell and the stack of two-dimensional MoS2 nanosheets as the yolk.Keywords: enhanced electrochemistry performance; hollow mesoporous carbon spheres; in situ confined growth; lithium-ion batteries; yolk−shell structured MoS2@C;

•Zero-dimensional (0D) polyaniline/polyoxometalates (PANI/PW12) nanospheres were first embedded into three-dimensional graphene framework to construct a novel 3D graphene/polyaniline/polyoxometalates hybrid (rGO@PANI/PW12).•The rGO@PANI/PW12 demonstrate extreme low capacity-decay rates of 0.028 % in half-cell and 0.035% in full-cell per cycle after 1000 cycles at 2 A g−1, representing the best performance for long-cycle POMs-based LIBs so far.•Complementary analytical methods strongly point to the electron-transfer (ET) mechanism from reduced PANI to POM as well as the “electron reservoir” model on PW12 molecule in LIBs.The energy crisis is currently a major concern worldwide due to the limited natural resources. Accordingly, lithium-ion batteries (LIBs) are in the focus of forefront energy storage investigations in our 21st century. Traditional lithium-insertion compounds for cathode materials, such as LiCoO2, LiMn2O4, LiNiO2 and LiFePO4, have been highly successful but they face serious limitations in energy storage density and production cost associated with their use. Therefore, the design of novel molecular cluster batteries (MCBs) as the next-generation energy storage device is an extremely important and hot topic of current research. Here, we first report preparation of zero-dimensional (OD) polyaniline/polyoxometalates [PW12O40]3− (PANI/PW12) nanospheres, and then have successfully embedded PANI/PW12 nanospheres into three-dimensional (3D) graphene sponge to construct a novel 3D graphene/polyaniline/polyoxometalates hybrid (rGO@PANI/PW12) as new cathode material in LIBs. The as-prepared rGO@PANI/PW12 hybrid in half-cell exhibits extraordinary electrochemical performances with high specific capacity (around 285 mAh g−1 at 50 mA g−1), excellent rate capability (140 mAh g−1 at 2 A g−1), and outstanding cycling stability (capacity fade rate of 0.028% per cycle even after 1000 cycles at 2 A g−1), representing the best performance for long-cycle POMs-based cathode in LIBs to date. Furthermore, a rGO@PANI/PW12-C lithium ion full-cell is first fabricated with an initial discharge specific capacity of 145 mAh g−1 at 2 A g−1, and then shows excellent cycling stability with a capacity decay rate of 0.035% per cycle over 1000 cycles at 2 A g−1. Importantly, the discharge and degradation mechanisms of rGO@PANI/PW12 cathode in LIBs are further deeply investigated. The electron-transfer (ET) from reduced PANI polymer to PW12 polyanion as well as the “electron reservoir” model on PW12 molecule both contribute to the high electroactivity. This study sheds thus new lights to the design of new generation electrode materials for lithium-ion batteries.Download high-res image (233KB)Download full-size imageThe self-assembled 3D rGO@PANI/PW12 nanocomposites, prepared through the hydrothermal reaction of 0D PANI@PW12 nanosphere with GO solution, can be rationally designed to exhibit outstanding electrochemical performances as new cathode material in lithium-ion batteries. The charge-discharge mechanism and structural stability of cathode materials in LIBs were also further deeply investigated with comprehensive analytical studies.

•Upconversion (UC) Er,Yb-CeO2 hollow spheres by carbonaceous spheres as template.•Both TiO2 and UC hollow spheres assembled to bilayer structure in DSSCs.•Cell efficiency improved 27% compared to the cell without scattering layer.•Improvement due to upconversion, scattering effect and higher dye-loading.Upconversion (UC) Er, Yb-CeO2 hollow spheres were successfully prepared using carbonaceous spheres as removable template via hydrothermal method for improving the efficiency of dye-sensitized solar cells (DSSCs). Light harvesting efficiency was enhanced 27% due to the upconversion effect, scattering effect and higher dye-loading capacities. It is expected that the work provides a new optimization approach for CeO2 application in DSSCs.

A new sandwiched polyoxometalate Na2Zn4H5[Zn3.2Bi0.8(B-α-ZnW9O34)2]·52H2O {Zn3.2Bi0.8} (1) was synthesized from one-pot transformations of the trilacunary Keggin-type [B-α-BiW9O33]9− precursor via Bi/Zn exchange, followed by self-assembly of the sandwich-type polyanions. The {Zn3.2Bi0.8} polyanion was further self-assembled into 2D architecture by adjusting Zn2+ and Na+ cations. The compound (1) was characterized with a wide range of analytical methods, including single crystal and powder X-ray diffraction, thermogravimetric analysis and various spectroscopic techniques (FT-IR, Raman, UV–Vis). Electrochemical behavior of the compound (1) was also studied by cyclic voltammetry (CV) in sodium acetate buffer solution. Moreover, compound (1) also can act as a catalyst in the oxidation of cyclohexanol with hydrogen peroxide.A novel 2D polyoxometalate framework is obtained from Zn2+-directed assembly of the new [Zn3.2Bi0.8(B-a-ZnW9O34)2]15− building block. Electrochemical behavior of the compound (1) is studied by cyclic voltammetry (CV) in sodium acetate buffer solution. Moreover, compound (1) also can act as a catalyst in the oxidation of cyclohexanol with hydrogen peroxide.Download high-res image (90KB)Download full-size image

•Fe3O4/C NFs with internal voids were synthesized without using any template.•The binder-free electrode membrane has good flexibility.•The internal voids can buffer the volume expansion of Fe3O4 during cycling.•Fe3O4/C NFs show high capacity and good cycling stability.Freestanding binder-free electrodes, as a new generation of electrode material, can effectively improve the energy density of lithium-ion batteries (LIBs). In this paper, novel structured Fe3O4/C composite nanofibers are successful synthesized by a simple electrospinning method followed by a thermal treatment process. The composite nanofibers have the unique internal voids between Fe3O4 nanoparticles and carbon matrix. The Fe3O4/C nanofibers film with good flexibility and excellent electrical conductivity can be directly used to fabricate half-cell without any current collector, binder and additional conductive agent. As anode material for LIBs, the Fe3O4/C composite nanofibers deliver high reversible capacity (762 mA h g−1 at 0.5 A g−1 after 300 cycles). The results show that the internal voids in flexible Fe3O4/C composite nanofibers effectively buffer volume expansion of Fe3O4 in lithium ion intercalation/deintercalation process and avoid the fracture of the nanofibers, which retain the structural integrity and improve the cycling stability of electrode. Therefore, the design and synthesis strategy of flexible nanofibers film are prospective for applications in next-generation flexible LIBs.Download high-res image (197KB)Download full-size image

Lysine-functionalized perylene was used to modify nanoparticles. Due to the benefits from a synergetic effect that originated between the perylene and silver nanoparticles, color-based metal sensor systems were established. At pH = 12.6, Cr6+ with a concentration of 100 nM could be detected by a color change from deep yellow to orange; after decreasing the pH to 12.0, the detection limit decreased to 2 μM. Interestingly, after further decreasing the pH to 11.0, another kind of metal ion (Cd2+) could be recognized with a detection concentration of 10 μM. At pH = 10.0, Pb2+ with a concentration of 2 μM could be detected.

Lithium-sulfur batteries have currently attracted wide interest due to their high theoretical capacity, but the practical applications are being hampered by capacity decay, mainly attributed to the polysulfide shuttle. Here, we have designed a novel three-dimensional (3D) nanostructure of graphene hollow spheres (HGs) as the sulfur host. The 3D HGs were successfully prepared via a self-assembly method of wrapping graphene oxide (GO) on SiO2 spheres, and then followed by carbonization and etching of the SiO2. The impregnation of sulfur into the hollow graphene spheres lead to obtaining the HGs/S cathode, which reaches up a high sulfur loading of 90 wt% in the composite (72 wt % in the whole cathode). The HGs/S cathode material remains a high discharge capacity of 810 mAh g−1 after 200 cycles at 0.5C rate. Furthermore, it demonstrates a low capacity-decay rate of 0.083% per cycle after 600 cycles at 1C rate. Compared with pristine reduced graphene oxide/sulfur composites (RGO/S), the as-prepared 3D self-assembled graphene hollow spheres HGs/S exhibit significantly improved electrochemical performances in terms of high specific capacity, remarkable rate capability and excellent cycling stability. These synergistic effects are achieved by more effective 3D ion/electron transport pathways, and efficient confinement of polysulfide dissolution and shuttling.

•The electronic structures of Pillar[5]quinone (P5Q) accepting electrons and binding lithium atoms.•The microstructural evolution of P5Q as cathode active materials for LIBs during charging and discharging processes.•The relationship between structural stability and electrochemical performance of Pillar[n]quinones.Multi-carbonyl macrocyclic compounds have recently attracted much attention due to their high performance relative to some short chain carbonyl compounds as the cathode active constituents for lithium-ion batteries (LIBs). However, little is known about the evolution mechanism of their electrochemical properties during charging and discharging processes. In this paper, the application of density functional calculations at the M06-2X/6-31G(d,p) level of theory is presented to study systematically the electrochemical properties of pillar[5]quinone (P5Q) as a cathode active material for LIBs. The optimized structures of P5Q accepting different number of electrons and binding different number of lithium atoms are obtained, respectively. The geometry structure, thermodynamics property, electronic structural property, solvent effect and redox potential are discussed in detail. The uneven-distribution of extra electrons in several P5Qn− anions can minimize the repulsive interactions as far as possible. The macrocyclic skeletons in P5QLin structures are distorted to different extents by the binding interactions between Li atoms and P5Q. More than eight intercalated lithium atoms into per P5Q molecule are confirmed in this work, indicating a high utilization ratio of carbonyl groups of P5Q as a cathode material. Compared with pillar[4]quinone and pillar[6]quinone, P5Q is predicted to have better cycling performance due to its higher structural stability.Download high-res image (123KB)Download full-size image

•LTO NSs/CNTs composites are synthesized by a facile and scalable strategy.•The incorporation of CNTs into LTO NSs forms a delicate conductive network.•LTO NSs/CNTs composites display excellent rate and cycling performances.•LTO NSs/CNTs show low polarization and large diffusion coefficient of Li+.Li4Ti5O12 nanosheets (LTO NSs)/carbon nanotubes (CNTs) composites are synthesized using a facile, reproducible, and scalable strategy. In the hydrothermal process, the introduction of CNTs significantly improves the rate performance of LTO NSs. The incorporation of CNTs into the LTO NSs forms a delicate conductive network for rapid electron and lithium ions transport, resulting in excellent rate performance and superior cycling performance. LTO NSs/7.5%-CNTs composites show the highest reversible capacity and high-rate capability (a reversible capability of 157, 145, 132, 118, and 105 mA h g−1 at 1, 2, 3, 4, 5 A g−1, respectively) with good cycling performance (approximate 6.9% capacity loss after 1000 cycles at 2 A g−1 with a capacity retention of 135 mA h g−1), which is apparently larger than pristine LTO NSs. The significantly improved rate capability and cycling performance of the LTO NSs/CNTs composites are mainly attributed to their the lower polarization of potential difference, the larger diffusion coefficient of lithium ion and smaller charge-transfer resistance than pure LTO NSs.

•N-doped urchin-like Fe3O4@C are fabricated via a facile hydrothermal process.•Fe3O4@C-N has unique urchin-like structure and N-doped mesoporous carbon shell.•Fe3O4@C-N exhibits low initial capacity loss and high reversible capacity.•Property improvement is attributed to unique nanostructure and N-doped carbon shell.Nitrogen-doped urchin-like Fe3O4@C composites are successfully fabricated via a facile hydrothermal process and subsequent carbonization. Urchin-like hydroxyferric oxide (α-FeOOH) is used as a template and coated by polydopamine (PDA) to form α-FeOOH@PDA. Under high temperature and argon atmosphere, urchin-like Fe3O4 with N-doped carbon shell (Fe3O4@C-N) are finally formed. In the electrochemical test, N-doped carbon shell can form stable solid electrolyte interface (SEI) layer, reduce initial capacity loss and improve the reversibility of Fe3O4 for Li ion storage. Compared with naked Fe3O4 nanospheres, Fe3O4@C nanospheres and urchin-like Fe3O4@C composites, the urchin-like Fe3O4@C-N composites display excellent electrochemical performance. The as-prepared Fe3O4@C-N-20-600 shows a reversible specific capacity of 800 mA h g−1 after 100 cycles at 500 mA g−1. The significant electrochemical property improvements of urchin-like Fe3O4@C-N composites are attributed to the unique urchin-like structure and the N-doped mesoporous carbon shell. Such a simple and scalable route to construct N-doped carbon encapsulated core-shell structure may be further extended to other high capacity anode and cathode materials.

A new family of hexanuclear titanium(IV)-oxo-carboxylate cluster K7H[Ti6O9(ida)6]Cl2·13H2O {Ti6O9} has been synthesized via the H2O2-assisted reaction between TiCl4 and iminodiacetate ligands. This cluster was fully characterized by single-crystal X-ray diffraction and a wide range of analytical methods, including FT-IR, UV/vis spectroscopy as well as electrochemistry and thermogravimetric analysis. As a new type of carboxylate substituted Ti-oxo-cluster, the structural motif of the {Ti6O9} cluster consists of one symmetric {Ti6O6} hexagonal prism with two staggered triangular {Ti3O3} subunits linked by three μ2-O bridges. The {Ti6O9} polyanions are linked by K+ cations to form a novel 3D architecture. The structural information and stability of the {Ti6O9} polyanion in aqueous solution were thoroughly investigated by solid-state/solution NMR, ESI-MS spectroscopy. Moreover, this Ti-oxo cluster exhibits remarkable potential as a visible-light homogeneous photocatalyst for degradation of rhodamine B (RhB). Finally, a proposed peroxotitanium(IV)-mediated photocatalytic pathway involved is illustrated by spectroscopic data.

In this paper, ferroferric oxide (Fe3O4) nanoparticles/porous carbon nanofiber (Fe3O4/PCNFs) composites were successfully fabricated by electrospinning and subsequent calcination. The composites were characterized by X-ray diffraction, thermogravimetric analysis, scanning electron microscopy and transmission electron microscopy to analyze the structure, composition and morphology. The electrochemical performance was evaluated by coin-type cells vs. metallic lithium. The results indicated that Fe3O4/PCNFs composites exhibited high reversible capacity and good capacity retention. The discharge capacity was maintained at 717.2 mA h g−1 at 0.5 A g−1 after 100 cycles. The excellent performances of Fe3O4/PCNFs composites are attributed to good crystallinity and uniformly dispersive Fe3O4 nanoparticles, and a porous carbon shell with high conductivity. The carbon coating buffered the tremendous volumetric changes between Fe3O4 nanoparticles and Fe atoms in the charge/discharge processes and kept the structure integrity of Fe3O4 nanoparticles. Porous carbon nanofibers prepared by the unique calcination process improved the conductivity of composites and provided free space for migration of lithium ions. The preparation strategy is expected to be applicable to the preparation of other transition metal oxide materials as superior anode materials for lithium-ion batteries.

A novel and recyclable poly(polyethylene glycol diacrylate/maleamic acid) (p(PEGDA/MALA)) copolymer hydrogel beads were for the first time synthesized through a microfluidic method and used for the removal of heavy mental ions from water. The monodisperse and size-controlled pregel droplets were firstly prepared by a microfluidic device and then polymerized to the hydrogel beads under UV irradiation. The synthesized p(PEGDA/MALA) hydrogel beads were characterized using various techniques and showed good adsorption property for Pb2+. The influencing factors on the adsorption process of Pb2+ were investigated in detail. The experiment results indicated that Pb2+ adsorption process was pH dependent, and agreed with the Langmuir monolayer model and pseudo-second-order equation. The adsorbing mechanism of copolymer hydrogel beads for Pb2+ mainly resulted from the electrostatic interaction and chelation action. The competitive adsorption experiment indicated that the affinity order in multicomponent adsorption was Pb2+>Cu2+>Cd2+. The well-designed p(PEGDA/MALA) copolymer hydrogel beads had excellent adsorption capacity and high recyclability and showed a promising application prospect in the decontamination of heavy metal ions in water.

In this work, we reported a facile approach to prepare a uniform copper ferrite nanoparticle-attached graphene nanosheet (CuFe2O4-GN). A one-step solvothermal method featuring the reduction of graphene oxide and formation of CuFe2O4 nanoparticles was efficient, scalable, green, and controllable. The composite nanosheet was fully characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS), which demonstrated that CuFe2O4 nanoparticles with a diameter of approximately 100 nm were densely and compactly deposited on GN. To investigate the formation mechanism of CuFe2O4-GN, we discussed in detail the effects of a series of experimental parameters, including the concentrations of the precursor, precipitation agent, stabilizer agent, and graphene oxide on the size and morphology of the resulting products. Furthermore, the electrochemical properties of the CuFe2O4-GN composite were studied by cyclic voltammetry and galvanostatic charge–discharge measurements. The composite showed high electrochemical capacitance (576.6 F·g–1 at 1 A·g–1), good rate performance, and cycling stability. These results demonstrated that the composite, as a kind of electrode materials, had a high specific capacitance and good retention. The versatile CuFe2O4-GN holds great promise for application in a wide range of electrochemical fields because of the remarkable synergistic effects between CuFe2O4 nanoparticles and graphene.Keywords: CuFe2O4; graphene; solvothermal procedure; supercapacitor

•β-Cyclodextrin polymer is used as a linker to prepare grapheme composites.•Amount and dispersity of AuNPs on rGO can be adjusted by changing the concentration of pATP.•Composites display high electrochemical response toward IDP and good catalytic property for ORR.•The method describes an effective process for fabrication rGO composites.Based on the self-assembly strategy, β-cyclodextrin polymer (β-CDP) was used as a linker to connect reduced graphene oxide (rGO) and p-aminothiophenol (pATP). Then, pre-prepared gold nanoparticles (AuNPs) can self-assemble onto the surface of pATP-β-CDP/rGO to obtain new ternary nanocomposites AuNPs/pATP-β-CDP/rGO. The amount or the density of AuNPs can be adjusted by changing the concentration of pATP. UV–vis and 1H NMR spectra confirmed the formation of inclusion complex between pATP and β-CDP. β-CDP might improve the dispersity of rGO in aqueous and the surface property of rGO. AuNPs/pATP-β-CDP/rGO modified electrode displayed high electrochemical response toward a pesticide-imidacloprid (IDP). The enrichment capability and molecular recognition of β-CDP and the catalytic property of AuNPs for IDP molecules synergistically promoted the electrochemical response of rGO modified electrode. Additionally, ternary nanocomposites exhibited the good electrocatalytic performance for oxygen reduction in O2-saturated 0.1 M H2SO4 solution. The proposed synthesis strategy provided a facile, feasible and effective method for development of electrochemical sensors and Au-based catalysts for fuel cells.

1D upconversion CeO2:Er, Yb nanofibers, which could absorb NIR light and upconvert it to visible light, to increase the photocurrent of DSSCs has been fabricated by an electrospinning method. The products were confirmed by transmission electron microscopy (TEM), high-resolution TEM (HRTEM) and X-ray diffraction (XRD), and fluorescence spectroscopy (PL) techniques. An enhancement of 14% in the light harvesting efficiency was observed due to the upconversion and scattering effect. It is anticipated that these nanostructures may provide a new direction for CeO2 application in DSSCs.

α-Fe2O3/reduced graphene oxide (RGO) nanocomposites were synthesized by a rapid and simple microwave method. Fe(OH)3 sol was used as the precursor of α-Fe2O3. Upon microwave heating, graphene oxide (GO) was reduced to RGO using hydrazine hydrate as a reductant and Fe(OH)3 sol transformed into α-Fe2O3 particles attached uniformly onto RGO surfaces at the same time. The structure, morphology and composition of α-Fe2O3/RGO nanocomposites were characterized by X-ray diffraction, transmission electron microscopy, scanning electron microscopy, thermogravimetric analysis and Raman spectroscopy. Electrochemical characteristics were evaluated by coin-type cells versus metallic lithium and cyclic voltammetry. The prepared α-Fe2O3/RGO nanocomposites exhibited a high reversible specific capacity of 650 mA h g−1 after 50 cycles at a current density of 1.0 A g−1, showing more superior rate capability than both α-Fe2O3 nanoparticles and RGO sheets. At the larger current density of 10.0 A g−1, the capacity of α-Fe2O3/RGO nanocomposites still remained 400 mA h g−1. The significant improvements in the electrochemical properties of α-Fe2O3/RGO nanocomposites could be attributed to the uniform α-Fe2O3 nanoparticles (30–50 nm) on the RGO substrate, which provided high electrical conductivity, confined the position and buffered the volume changes of α-Fe2O3 nanoparticles.

A stable aqueous inclusion complex of fullerene (C60) with macromolecules (C60 concentration as high as 3 × 10−4 mol L−1) was achieved by a one-step strategy using γ-cyclodextrin polymer (γ-CDP). The inclusion complex of C60 with γ-CDP (C60–γ-CDP) was characterized by ultraviolet-visible, Raman and 1H-NMR spectroscopies, powder X-ray diffraction analysis, and thermogravimetric analysis. The supramolecular interactions and the equilibrium constant for a 1:2 (C60:CD unit in γ-CDP) complex of C60 with γ-CDP were studied. Under ultraviolet A (UVA) irradiation C60–γ-CDP in water could generate singlet oxygen, which was detected by electron paramagnetic resonance spectroscopy. We also evaluated the cytotoxicities of C60–γ-CDP, and investigated the phototoxicity of C60–γ-CDP and pristine C60 toward B16-F10 melanoma cells. The cell viability test showed that C60–γ-CDP had a significantly higher photodynamic ability than that of the pristine C60 under UVA irradiation. This work demonstrated both a CDP-functionalized strategy for enhancing the water-solubility and phototoxicity of fullerenes for applications in cancer photodynamic therapy, as well as remediating the negative biological effects of pristine fullerenes.

Novel quantum-dot-tagged photonic crystal beads were fabricated for multiplex detection of tumor markers via self-assembly of quantum dot-embedded polystyrene nanospheres into photonic crystal beads through a microfluidic device.

The first amphiphilic pillar[6]arene was successfully synthesized. It can complex with adenosine triphosphate to form vesicles in water. Moreover, these vesicles are efficiently responsive to phosphatase.

In this work, a novel carbon-free core–shell α-iron oxide (α-Fe2O3)@ spinel lithium titanate (Li4Ti5O12, LTO) composite has been synthesized via a facile hydrothermal process. Element mapping confirmed the core–shell structure of α-Fe2O3@LTO. The effects of various experimental parameters, including thickness of TiO2 coating, reaction temperature, and time on the morphologies of the resulted products, were systematically investigated. The electrochemical measurements demonstrate that uniform α-Fe2O3 ellipsoids are coated with LTO to avoid forming a solid electrolyte interface (SEI) layer, to reduce initial capacity loss, and to improve the reversibility of α-Fe2O3 for Li ion storage. Compared with naked α-Fe2O3 ellipsoids, the α-Fe2O3@LTO composites exhibit lower initial capacity loss, higher reversible capacity, and better cycling performance for lithium storage. The electrochemical performance of α-Fe2O3@LTO composite heavily depends on the thickness and density of LTO coating shells. The carbon-free coating of LTO is highly effective in improving the electrochemical performance of α-Fe2O3, promising advanced batteries with high surface stability and excellent security.Keywords: carbon-free anode materials; core−shell structure; Li ion batteries; lithium titanate; α-Fe2O3;

A new amphiphilic pillar[5]arene (AP5-glycol) with five oligomeric glycol groups and five alkyl chains was prepared. AP5-glycol spontaneously formed bilayer vesicles in water, and these vesicles were still stable after several weeks. Additionally, when they were exposed to external physical stimuli, these vesicles also showed reversible thermal and dynamic properties. Interestingly, oleic-acid-stabilized magnetic iron oxide nanoparticles could be incorporated into the bilayer of the AP5-glycol vesicles to form hybrid magnetic-responsive supramolecular vesicles.Keywords: amphiphilie; host−guest interaction; magnetic-responsive; self-assembly; supramolecular chemistry

•PtNWs/pATP-β-CDP/rGO composites are fabricated by self-assembly strategy.•Amount and dispersity of PtNWs on rGO can be adjusted by changing the weight ratio of pATP-β-CDP/rGO.•The catalyst displays excellent catalytic performance for methanol oxidation reaction.•The proposed strategy provides a facile method for developing noble metals electrocatalysts.A noble Pt nanoworms (PtNWs)/p-aminothiophenol (pATP)-β-cyclodextrin polymer (β-CDP)/reduced graphene oxide (PtNWs/pATP-β-CDP/rGO) nanocomposite is synthesized using the self-assembly strategy. Inclusion complexes between β-CDP and pATP are modified onto the surface of rGO through non-covalent bond force. Then, pre-prepared PtNWs self-assemble onto the surface of pATP-β-CDP/rGO through thiol and amino groups of pATP to fabricate PtNWs/pATP-β-CDP/rGO hybrid materials. It is verified that the PtNWs may be uniformly scattered on rGO and the amount of PtNWs may be adjusted changing the weight ratio of pATP-β-CDP:rGO. Cyclic voltammograms show that the PtNWs/pATP-β-CDP/rGO catalysts have higher active surface area, more improved performance and better stability towards the electrocatalytic oxidation of methanol than commercial Pt/C catalysts. The proposed synthesis strategy provides a moderate, feasible and effective method for developing noble metals electrocatalysts for methanol oxidation reaction.

In this article, a new method was applied to synthesize magnetically responsive Fe3O4@polyaniline (PANI) @Au nanocomposites via a three-step process. Core–shell Fe3O4@PANI was prepared by the in situ surface polymerization method with the assistance of sodium dodecyl sulfonate (SDS). By means of electrostatic attraction, as-prepared Au nanoparticles were adsorbed on Fe3O4@PANI core–shell composites to fabricate Fe3O4@PANI@Au composites, which were characterized by transmission electron microscopy (TEM), X-ray powder diffraction (XRD), energy-dispersive X-ray (EDX), X-ray photoelectron spectroscopy (XPS), and vibrating sample magnetometer (VSM) measurements. The catalytic activity of the Fe3O4@PANI@Au composites was evaluated by monitoring the reduction reaction of Congo red. The Fe3O4@PANI@Au composite catalyst exhibited excellent catalytic performance at low or high concentration of dye solution. The influences of electrolytes and surfactants on the catalytic reduction rate were studied. Significantly, the Fe3O4@PANI@Au composite catalyst showed excellent catalytic performance, good stability and facile recovery by an external magnet.

An amphiphilic amino resorcinarene (T) was modified onto the surface of graphene oxide (GO) through covalent bond forces and non-covalent bond forces to prepare GO–T. The water-soluble graphene–T (GN–T) composite was prepared by the reduction of GO–T. Then, pre-prepared platinum nanoparticles (PtNPs) and different sized gold nanoparticles (AuNPs) could self-assemble onto the surface of GN–T through the plentiful amido groups of T to obtain GN–T–AuNPs and GN–T–PtNPs hybrid materials. It was verified that the AuNPs and PtNPs could be uniformly scattered on GN and the amount of AuNPs and PtNPs modified on GN could be adjusted by changing the weight ratio of T/GO. GN-T-PtNPs and GN-T-AuNPs composites showed the characteristics of being dispersible, stable and recyclable in water. Electrochemical results obviously revealed that GN–T–AuNPs and GN–T–PtNPs composites exhibited outstanding electrocatalytic properties.

In this article, a study was presented on the catalytic activity of silver nanoparticles immobilized on magnetic Fe3O4@C (MFC) core–shell nanocomposites (Ag/MFC) that were used as carriers. MFC composites consist of a magnetic core of an Fe3O4 microsphere onto which a thin layer of carbon was coated by in situ carbonization of glucose under hydrothermal conditions. The catalytic activity of the as-prepared Ag/MFC is investigated by photometrically monitoring the reduction of 4-nitrophenol and methylene blue by an excess of NaBH4. The kinetic data of both reduction reactions could be explained by the assumption of a pseudo-first-order reaction with regard to 4-nitrophenol or methylene blue. Significantly, the Ag/MFC catalysts can be easily separated from the reaction media by applying an external magnet, and can be reused for several cycles.

In this work, CuFe2O4 nanospheres with hierarchically porous structure have been synthesized via a facile solvothermal procedure. The superstructures consist of the textured aggregations of nanocrystals with high specific surface area, pore volume, and uniform pore size distribution.To figure out the formation mechanism, we discussed in detail the effects of a series of experimental parameters, including the concentrations of the precipitation agent, stabilizer agent, and reaction temperature and time on the size and morphology of the resulting products. Furthermore, the electrochemical properties of CuFe2O4 nanospheres were evaluated by cyclic voltammetry and galvanostatic charge-dischrge studies. The results demonstrate that the as-prepared CuFe2O4 nanospheres are excellent electrode material in supercapacitor with high specific capacitance and good retention. The hierarchically CuFe2O4 nanospheres show the highest capacitance of 334F/g, and 88% of which can still be maintained after 600 charge–discharge cycles.Keywords: CuFe2O4; hierarchically porous; solvothermal procedure; supercapacitor;

An amphiphilic pillar[5]arene (AP5) was modified onto the surface of reduced graphene oxide (RGO) to form the water-dispersive RGO-AP5 nanocomposite. And then, as-prepared gold nanoparticles (AuNPs) self-assembled onto the surface of RGO-AP5 through amido groups of AP5 to achieve RGO-AP5-AuNPs nanocomposites. It was verified that a large amount of AP5 molecules had been effectively loaded onto the surface of RGO and lots of AuNPs could be uniformly dispersed on RGO-AP5. Electrochemical results showed that the RGO-AP5 could exhibit selective supramolecular recognition and enrichment capability toward guest molecules. More significantly, in electrochemical sensing the guest molecules, ternary nanocomposites RGO-AP5-AuNPs performed the synergetic action of multifunctional properties, which were excellent performances of RGO, selective supramolecular recognition, and enrichment capability of AP5 and catalytic property of AuNPs for guest molecules. Therefore, RGO-AP5-AuNPs showed an outstanding analyzing performance for DA with broad linear range (1.5 × 10–8 to 1.9×10–5 M) and low detection limit (1.2 × 10–8 M) at a signal-to-noise ratio of 3.Keywords: gold nanoparticles; host−guest recognition; pillar[5]arene; reduced graphene oxide; synergetic action;

Reduced graphene oxide (rGO) modified with three kinds of water-soluble p-sulfonated calix[4,6,8]arene sodium (SCn: SC4, SC6, SC8) were successfully prepared by using a simple wet chemical strategy. Three obtained SCn-rGO nanocomposites were characterized by Fourier transform infrared spectroscopy, Ultraviolet–visible spectroscopy, static contact angle measurement, thermogravimetric analysis, scanning electron microscope and electrochemical impedance spectroscopy, which confirmed that different amount of SCn molecules had been effectively loaded onto the surface of rGO, and the water-dispersity and stability of SCn-rGO increased with the increase of the value of n in SCn (n = 4, 6, 8). More significantly, cyclic voltammetry measurement showed that the SCn-rGO could exhibit high supramolecular recognition and enrichment capability and consequently displayed excellent electrochemical response toward four probe molecules (biological and organic dye molecules). Especially, SC8-rGO exhibited an excellent electrochemical performance for dopamine with high current densities of 73.04 mA mM–1 L cm–2, broad linear range (1 × 10–8 to 2.1 × 10–5 M) and very low detection limit (8 × 10–9 M) at a signal-to-noise ratio of 3.Keywords: calix[4,6,8]arenesulfonates; electrochemical detection; graphene nanocomposites; host−guest recognition; reduced graphene oxide; supramolecular self-assembly;

Functionalization of carbon nanomaterials (including fullerenes, single-walled carbon nanotubes, multi-walled carbon nanotubes (MWCNTs), and graphene sheets) dispersed in water with macromolecules was achieved by a one-step strategy using β-cyclodextrin polymer (CDP). CDP-carbon nanomaterials were characterized by ultraviolet–visible, Raman, and Fourier transform infrared spectroscopies, transmission and scanning electron microscopies, and thermogravimetric analysis. These nanomaterials showed high solubility and stability in water because of the noncovalent interaction between carbon nanomaterials and CDP. The supramolecular recognition abilities of CDP-carbon nanomaterials were studied by cyclic voltammetry (CV). CDP-MWCNTs were also decorated by p-aminothiophenol (PATP) which formed inclusion complexes with the CDP. The conjugates (PATP-CDP-MWCNTs) were ideal templates for the highly efficient assembly of noble metal nanoparticles (Au and Pt) with dramatically different properties. Methanol oxidation of Pt-decorated PATP-CDP-MWCNTs in CV analyses indicated its potential application in direct methanol fuel cells, facilitating the feasibility of metal-decorated CDP-carbon nanomaterials in real technological applications. This universal method of producing carbon nanomaterials functionalized with macromolecules is beneficial for investigating the structure–performance relationship of carbon nanomaterials for designing compounds with specialized functions.

Reduced graphene oxide (RGO) modified glassy carbon electrode (GCE), RGO/GCE, was used to investigate electrocatalytic reduction of m-nitrophenol. This reduction behavior was explored by cyclic voltammetry and linear sweep voltammetry. The reduction potential of m-nitrophenol on the RGO/GCE shifts toward the positive potential relative to the GCE or GO/GCE. The reduction peak current on the RGO/GCE was much greater than that on the GCE or GO/GCE. The reduction peak current on RGO/GCE is 12 times of that on bare GCE, and 8 times of that on GO/GCE. The results show much better catalytic ability than ever reported works. The influence of pH and m-nitrophenol concentration on the electrocatalytic ability of the RGO/GCE was also studied. The optimal pH is found to be 5.50. The reduction mechanism of m-nitrophenol on the RGO/GCE is presented.

•β-CDP/rGO nanocomposites were prepared by a facile strategy.•β-CDP/rGO nanocomposites displayed the excellent water-dispersity and stability.•β-CDP/rGO exhibited high supramolecular recognition and enrichment capability.•β-CDP/rGO electrode showed excellent electrochemical performance for IDP.Reduced-graphene oxide (rGO) modified with water-soluble β-cyclodextrin polymer (β-CDP) were successfully prepared by using a simple wet chemical strategy. The obtained β-CDP/rGO nanocomposites were characterized by Fourier transform infrared spectroscopy (FTIR), static contact angle measurement, thermogravimetric analysis (TGA), scanning electron microscope (SEM) and electrochemical impedance spectroscopy (EIS), which confirmed that β-CDP molecules had been effectively loaded onto the surface of rGO. β-CDP/rGO nanocomposites displayed the excellent water-dispersity and stability. More significantly, cyclic voltammetry and differential pulse voltammetry measurement showed that the β-CDP/rGO could exhibit high supramolecular recognition and enrichment capability, and consequently display excellent electrochemical response toward a pesticide-imidacloprid (IDP). As compared with various modified electrodes, β-CDP/rGO modified glassy carbon electrode exhibited an excellent electrochemical performance for IDP. Based on the cyclic voltammograms (CV) of different concentration of IDP at pH 6.8, the detection line range of IDP is 1 × 10−6 to 1.5 × 10−4 mol L−1 IDP and the detection limit is 1 × 10−7 mol L−1. Differential pulse voltammetry (DPV) measurement at β-CDP/rGO/GCE modified electrode revealed that the reduction peak current increased linearly with the concentration of IDP in linear range of 5 × 10−8 to 1.5 × 10−5 mol L−1 and 2 × 10−5 to 1.5 × 10−4 mol L−1 with detection limit of 2 × 10−8 mol L−1 at a signal-to-noise ratio of 3.

Hollow carbon nanonets (HCN), which are attractive materials for catalyst support, were fabricated using the pre-synthesized hematite nanoparticles as the hard template. And then the HCN supported Pd nanoparticles (Pd/HCN) were prepared by precipitation-reduction method. The catalytic performance of Pd/HCN was investigated using Suzuki and Heck coupling reactions as model reactions. The results demonstrated that the as-prepared Pd/HCN nanocomposites exhibit high catalytic activity for the two types of coupling reactions under ligand free conditions. Especially, the Suzuki reactions between various aryl halides and phenylboronic acid gave excellent yields in water. Moreover, the as-prepared Pd/HCN catalysts can be easily recovered from the reaction medium by centrifugation for recycling, and the catalytic efficiency shows no obvious loss even after 6 repeated cycles.

A new water-soluble inclusion complex of ilexgenin A (IGA) with β-cyclodextrin polymer (CDP) was prepared by a facile strategy and characterized by 1H NMR , FT-IR, and UV-vis spectroscopy. Compared with IGA and the inclusion complex of IGA with β-cyclodextrin (IGA–CD), the solubility of IGA–β-cyclodextrin polymer (IGA–CDP) was greatly enhanced due to the water-soluble CDP host. The ratio of β-cyclodextrin (β-CD) units in CDP to IGA was determined as 2:1. KD of the inclusion complex was evaluated as 2.6 × 10−3 mol L−1. The effects of IGA–CDP on a hyperlipidemia mouse model were studied by intragastric administration. After 4 weeks, the IGA–CDP treatment resulted in decreased serum levels of total cholesterol and low-density lipoprotein-cholesterol. The effects of IGA–CDP on serum apolipoprotein levels were similar to its effects on lipid levels. By comparing liver area, the effects of IGA–CDP on pre-existing lesions were assessed. Furthermore, the efficacy and potency of water-soluble inclusion complex of IGA–CDP was 2–3 times higher than that of IGA. Taken together, it was possible to develop it to a novel drug candidate to regulate lipid abnormality.

•The water solubility of HY was improved by complexation with CDP.•The mole ratio of β-CD unit to HY was determined as 2:1.•It provided an approach for a more rational pharmaceutical application of HY.A water-soluble inclusion complex of hypericin (HY) with β-cyclodextrin polymer (CDP) was achieved by supramolecular interactions between HY and CDP. The inclusion complex (HY-CDP) was characterized by 1H NMR, FTIR, and UV–vis spectroscopies. Compared with HY, the water-solubility of HY-CDP was greatly enhanced because of the water-soluble CDP host. The mole ratio of β-cyclodextrin (β-CD) unit in CDP to HY was determined as 2:1. At 25 °C, the dissociated constant of HY-CDP was measured as 1.47 × 10−7 mol L−1 by UV–vis spectroscopy. In the formation of inclusion complexes, CDP could overcome the β-CD drawbacks – such as the poor water-solubility and the restriction of single cavity size, indicating it was able to use as a universal solubilizer for pharmaceutical application.

A new water-solution inclusion complex of imidacloprid (IDP) with β-cyclodextrin polymer (β-CDP) was prepared by a facile strategy and characterized by FTIR, powder X-ray diffractometry, thermogravimetry, 1H NMR spectroscopy and UV–vis spectroscopy. The ratio of β-cyclodextrin (β-CD) unit in β-CDP to IDP is determined as 2:1. At 25 °C, the dissociated constant of IDP-β-CDP is measured as 1.79 ± 0.17 × 10−5 M2 by UV–vis spectroscopy. The well behaved electrochemical properties of IDP-β-CDP in water are observed. The diffusion coefficient of reduced state and the diffusion activation energy are calculated as 4.0 ± 0.5 × 10−7 cm2 s−1 and 9.8 ± 0.3 kJ mol−1, respectively. Compared with IDP, the solubility of IDP-β-cyclodextrin polymer (IDP-β-CDP) is greatly enhanced due to the water-soluble β-CDP host.Highlights► Water-solution inclusion complex of IDP-β-CDP was prepared by a facile strategy. ► IDP-β-CDP exhibited good electrochemical behavior. ► Diffusion coefficient and diffusion activation energy of IDP-β-CDP were calculated. ► The high solubility of IDP-β-CDP might increase the insecticidal efficacy.

In this work, adsorption and desorption of azo dye-Congo red on a supramolecular sorbent (SiO2-CD) were studied. Static adsorption study showed that the adsorption of Congo red onto SiO2-CD obeyed Langmuir’s model. The sorbent may be easily regenerated by using β-cyclodextrin (β-CD) and hydroxypropyl-β-cyclodextrin (HP-β-CD) as a desorption agent. The desorption efficiency of Congo red was strongly dependent on the concentration of the desorption agent and the temperature. The electrochemical degradation of dye solutions revealed that the average current efficiency (ACE) was sharply increased with dye concentration. The combination of above three techniques dramatically increased the concentration of the dye by a factor of 30, improved the removal (approaching 80% color removal), and enhanced ACE by over 50%. These findings suggest that an organic combination of adsorption, condensation, and electrochemical degradation techniques can achieve a satisfactory outcome for the degradation of low-concentration dye effluents with large volume.

Crystalline silver nanowires, with diameters of 50–500 nm and lengths up to tens of micrometers, have been successfully synthesized by a simple wet chemical route by using cuprous oxide nanospheres as a reductant and directional agent. The products are characterized by powder X-ray diffraction, scanning electron microscopy, transmission electron microscopy, high-resolution transmission electron microscopy, X-ray photoelectron spectroscopy, and UV–vis absorption spectroscopy. The two-dimensional netlike nanostructure is composed of several silver nanowires. The possible mechanism for the formation of silver nanowires is discussed. It is found that the architecture of silver crystals is drastically influenced by the concentration of the precursors and the reaction temperature. The experimental results reveal that the Cu2O nanospheres might play the two roles during the growth process of silver nanowires. Except for a reducing agent, Cu2O nanospheres act as a growth substrate to induce the formation of silver nanowires and a two-dimensional netlike nanostructure. Furthermore, the obtained two-dimensional netlike silver nanostructure can be used as surface-enhanced Raman scattering (SERS) substrates with high SERS activity and stability for detecting Rhodamine 6G (R6G) molecules. The analytical enhancement factor on the two-dimensional netlike silver nanostructure substrate is about 8 × 1010. Compared with other morphologies of silver substrates, it is found that the two-dimensional netlike silver nanowires exhibit the highest SERS sensitivity. Hence, SERS substrates of the two-dimensional netlike silver nanowires described in this work have potential applications in chemical and biological analysis as well as medical detection.

Polyacrylonitrile (PAN) nanofiber membranes functionalized with calix[8]arenes (C[8]) were successfully prepared by electrospinning of PAN solutions with addition of various calixarenes. Uniform electrospun C[8]/PAN nanofibers were obtained by incorporating three types of calix[8]arenes into the PAN matrix and characterized by scanning electron microscopy (SEM), attenuated total reflection Fourier transform infrared (ATR-FTIR), thermal gravimetric analysis (TGA), and X-ray powder diffraction (XRD). The SEM results showed that the addition of calix[8]arenes resulted in a decrease in the diameter of PAN nanofibers. Static adsorption behavior was studied by using C[8]/PAN nanofibers as an adsorbent and Congo red and Neutral red as model dye molecules. The adsorption of Congo red onto Amide-Cal[8]-15/PAN nanofibers fitted the second-order kinetic model, and the apparent adsorption rate constant was 1.1 × 10–3 g·mg–1·min–1 at 25 °C. Then, by virtue of electrostatic attraction, as-prepared Au nanoparticles were immobilized on Amide-Cal[8]/PAN nanofibers to form Au/Amide-Cal[8]/PAN composite nanofibers. The catalytic activity of the as-prepared Au/Amide-Cal[8]/PAN composite nanofibers was investigated by monitoring the reduction of Congo red in the presence of NaBH4. The reduction kinetics was explained by the assumption of a pseudo-first-order reaction with regard to Congo red. Au/Amide-Cal[8]/PAN composite nanofibers exhibited high catalytic activity, excellent stability, and convenient recycling.

A mesoporous silica nanoshpere (MSN) was proposed to modify glassy carbon electrode (GCE) for the immobilization of protein. Using glucose oxidase (GOD) as a model, direct electrochemistry of protein and biosensing at the MSN modified GCE was studied for the first time. The MNS had large surface area and offered a favorable microenvironment for facilitating the direct electron transfer between enzyme and electrode surface. Scanning electron microscopy, transmission electron microscopy, UV–vis spectroscopy and cyclic voltammetry were used to examine the interaction between GOD and the MSN matrix. The results demonstrated that the immobilized enzyme on the MSN retained its native structure and bioactivity. In addition, the electrochemical reaction showed a surface controlled, reversible two-proton and two-electron transfer process with the apparent electron transfer rate constant of 3.96 s−1. The MNS-based glucose biosensor exhibited the two linear ranges of 0.04–2.0 mM and 2.0–4.8 mM, a high sensitivity of 14.5 mA M−1 cm−2 and a low detection limit of 0.02 mM at signal-to-noise of 3. The proposed biosensor showed excellent selectivity, good reproducibility, acceptable stability and could be successfully applied in the reagentless detection of glucose in real samples at −0.45 V. The work displayed that mesoporous silica nanosphere provided a promising approach for immobilizing proteins and fabrication of excellent biosensors.Highlights► A novel mesoporous silica nanosphere matrix was proposed for immobilizing protein. ► Direct electrochemistry of GOD and biosensing on this matrix was studied. ► The constructed electrochemical glucose biosensor showed remarkable performances. ► This matrix provided a new and efficient approach for electrochemical biosensing.

Copper oxide (CuO) nanorods were synthesized via a facile hydrothermal process, which exhibit excellent catalytic oxidation of cyclohexene to 2-cyclohexene-1-one by tert-butyl hydrogen peroxide (TBHP) in acetonitrile. This would provide a novel method for directly synthesizing α,β-unsaturated ketones from olefins.

In this paper, the formation of hydroxypropyl-β-cyclodextrin (HPCD) nanofibers in electrospinning and the adsorption of organic molecules on the HPCD nanofiber were studied. The properties of a polymer-like solution from the highly concentrated HPCD/N,N-dimethylformamide (DMF) solution revealed HPCD supramolecular aggregates formation. The entanglements of HPCD self-organized aggregates were one of the most important factors that significantly influenced fiber formation during cyclodextrin electrospinning. The HPCD self-organized aggregates entanglement concentration (Ce) was investigated. Analyzing the dependence of specific viscosity (ηsp) on concentration enabled the determination of the aggregates unentangled and entangled regimes for HPCD polymer-like solutions. The dynamic light scattering (DLS) measurements and the 1H NMR spectra of the HPCD solutions confirmed the presence of considerable HPCD self-organized aggregates in high concentrated HPCD/DMF solutions due to the intermolecular hydrogen bonding. The scanning electron microscopy (SEM) showed the electrospinning morphology transitioned from regular beads to uniform fibers with increasing the HPCD concentration. The dependence of the fiber diameter on the zero shear rate viscosity (η0) was determined. The static adsorption behavior of the HPCD fibers was studied. Neutral red (NR) was used as a model organic molecule. The adsorption of NR onto HPCD fibers fitted the pseudo-second-order kinetic model. The equilibrium adsorption amount of NR was 18.41 mg g−1, and the apparent adsorption rate constant was 9.83 × 10−4 g mg−1 min−1 at 25 °C.

The reaction of [W(CN)8]3− with Ln3+ and pyrazine in acetonitrile yielded a series of isostructural compounds formulated as Ln(H2O)4(pyrazine)0.5W(CN)8 (Ln = La(1), Ce(2), Pr(3), Nd(4), Sm(5), Eu(6), Gd(7)). The Ln(III) and W(V) centers in the structure are linked through cyanide groups to form two-dimensional (2D) layers, which are further pillared by pyrazine, generating 3D frameworks. The magnetic behavior for compounds 1–7 were driven by the lanthanide ions involved. The Ln(III) and W(V) ions in compounds 2 and 5 are ferromagnetically coupled with magnetic ordering occurring at 2.8 K, comparable with magnetic ordering with the critical temperature of 1.9 K for compound 4. In addition, the antiferromagnetic interactions were observed in compounds 3 and 7, while no significant magnetic couplings were found in compounds 1 and 6.

Two temperature-dependent structures of 2D and 3D Zn(II)-organic frameworks (ZOFs) with a new 5-substituted benzene-1, 3-dicarboxylic ligand, 5-iodoisophthalic acid (H2IIP), and an auxiliary flexible ligand, 1,4-bis(1,2,4-triazol-1-yl)butane (btb), with different motifs, have been investigated. Results show that when the reaction was carried out at room temperature, a undulating 2D (4,4)-network, {[Zn(IIP)(btb)]·4H2O}n (1), which further extends into a novel “soft” 3D supramolecular microporous framework with two kinds of 1D nanochannels supported by face to face π⋯π stacking interactions and C–I⋯I halogen bonds, was generated. Under hydrothermal condition at 170 °C, however, a two-fold interpenetrated 3D framework with α-Po network topology, [Zn(IIP)(btb)]n (2), would be obtained. Interestingly, both the right- and left-handed 21 helical water chains lie in one kind of the nanochannels in 1. When the auxiliary ligand was replaced by a less flexible one with a shorter spacer length, 1,3-bis(1,2,4-triazol-1-yl)propane (btp), a novel temperature-independent single-walled discrete coordination tube, {[Zn(IIP)(btp)]·2H2O}n (3), was obtained at the same two temperatures. Inside the tube is found the 21 helical water chain. Interestingly, the reversible desorption/adsorption behavior to water is significantly observed in the frameworks 1 and 3. The framework 1 falls within the category of “recoverable collapsing” and “guest-induced re-formation” frameworks. The result shows their potential application as late-model water absorbents in the field of adsorption materials. Remarkably, the first discrete single-walled Zn(II) coordination tube 3 shows high framework stability and exhibits reversible desorption/adsorption to some small guest organic molecules (methanol, ethanol and isopropanol). Furthermore, these compounds exhibit blue fluorescence in the solid state.

A simple hydrothermal process for fabrication of hematite (α-Fe2O3) nanostructures with narrow size distribution was developed by using PVP as surfactant and NaAc as precipitation agent. The influence of experimental parameters including the concentration of the precursor, precipitation agent, stabilizing agent, and reaction time was systematically investigated to study the possible formation mechanism of α-Fe2O3. Finally, the electrochemical properties of the obtained hematite particles were studied using cyclic voltammetry and galvanostatic charge–discharge measurement by a three-electrode system. The results reveal that their specific capacitances are related to their sizes. By virtue of large surface area, the as-prepared hematite nanoparticles can present the highest capacitance (340.5 F·g–1) and an excellent long cycle life within the operated voltage window (−0.1 to 0.44 V), demonstrating that the as-prepared hematite nanoparticles can serve as one of the most excellent electrode materials for supercapacitors.

This review focuses on the synthesis and application of nanostructured composites containing magnetic nanostructures and carbon-based materials. Great progress in fabrication of magnetic carbon nanocomposites has been made by developing methods including filling process, template-based synthesis, chemical vapor deposition, hydrothermal/solvothermal method, pyrolysis procedure, sol–gel process, detonation induced reaction, self-assembly method, etc. The applications of magnetic carbon nanocomposites expanded to a wide range of fields such as environmental treatment, microwave absorption, magnetic recording media, electrochemical sensor, catalysis, separation/recognization of biomolecules and drug delivery are discussed. Finally, some future trends and perspectives in this research area are outlined.

Calixarenes and their derivatives may be a promising material for enzyme immobilization owing to their particular configuration, unique molecule recognition function and aggregation properties. In this paper, p-tert-butylthiacalix[4]arene tetra-amine (TC4TA) was first used as enzyme immobilization material. This attractive material was exploited for the mild immobilization of glucose oxidase (GOD) to develop glucose amperometric biosensor. GOD was strongly adsorbed on the TC4TA modified electrode to form TC4TA/GOD composite membrane. The adsorption mechanism was driven from the covalent bond between amino-group of TC4TA and carboxyl group of GOD and molecule recognition function of TC4TA. Amperometric detection of glucose was evaluated by holding the modified electrode at 0.60 V (versus SCE) to oxidize the hydrogen peroxide generated by the enzymatic reaction. The sensor (TC4TA/GOD) showed a relative fast response (response time was about 5 s), low detection limit (20 μM, S/N = 3), and high sensitivity (ca. 10.2 mA M−1 cm−2) with a linear range of 0.08–10 mM of glucose, as well as a good operational and storage stability. In addition, optimization of the biosensor construction, the effects of the applied potential as well as common interfering compounds on the amperometric response of the sensor were investigated and discussed herein.

Palladium nanoparticles modified glassy carbon electrodes (Pd/GC) were prepared via the electrodeposition of palladium on a glassy carbon (GC) electrode using cyclic voltammetry in different sweeping potential ranges. The scanning electron microscope images of palladium particles on the GC electrodes indicate that palladium particles with diameters of 20–50 nm were homogeneously dispersed on the GC electrode at the optimal deposition conditions, which can effectively catalyze the reduction of m-nitrophenol in aqueous solutions, but their catalytic activities are strongly related to the deposition conditions of Pd. The X-ray photoelectron spectroscopy spectra of the Pd/GC electrode confirmed that 37.1% Pd was contained in the surface composition of the Pd/GC electrode. The cyclic voltammograms of the Pd/GC electrode in the solution of m-nitrophenol show that the reduction peak of m-nitrophenol shifts towards the more positive potentials, accompanied with an increase in the peak current compared to the bare GC electrode. The electrocatalytic activity of the Pd/GC electrode is affected by pH values of the solution. In addition, the electrolysis of m-nitrophenol under a constant potential indicates that the reduction current of m-nitrophenol on the Pd/GC electrode is approximately 20 times larger than that on the bare GC electrode.Highlights► The deposition of palladium on a GC electrode was performed by cyclic voltammetry. ► SEM images showed palladium nanoparticles deposited on a glassy carbon (GC) electrode. ► The Pd/GC electrode can effectively catalyze m-nitrophenol in aqueous media. ► The reduction of m-nitrophenol on the Pd/GC electrode depended on potential and pH. ► XPS spectra of the Pd/GC electrodes demonstrated the presence of palladium.

A new water-soluble inclusion complex of ferrocene (Fc) with β-cyclodextrin polymer (β-CDP) was prepared by a facile strategy and characterized by 1H NMR spectroscopy, elemental analysis, powder X-ray diffractometry, thermogravimetry, UV–vis spectroscopy and cyclic voltammetry. Compared with Fc and the inclusion complex of Fc with β-cyclodextrin (Fc-β-CD), the solubility of ferrocene-β-cyclodextrin polymer (Fc-β-CDP) was greatly enhanced due to the water-soluble β-CDP host. The ratio of β-cyclodextrin (β-CD) unit in β-CDP to Fc was determined as 1:1. At 25 °C, the dissociated constant of Fc-β-CDP was measured as 3.65 mM by UV–vis spectroscopy and cyclic voltammetry. The electrochemical properties of Fc-β-CDP in water were studied. The diffusion coefficients of oxidation state and reduction state were calculated as 3.52 × 10−7 cm2 s−1 and 3.93 × 10−7 cm2 s−1. The resulting value of standard rate constant was measured as 1.95 × 10−3 cm s−1. The diffusion activation energy was calculated as 21.8 kJ mol−1.Highlights► Water-soluble Fc-β-CD polymer inclusion complex is prepared with a supermolecular method. ► Fc-β-CDP shows better aqueous solubility remarkably than Fc and Fc-β-CD. ► It also reserves the electrochemical properties of Fc-β-CDP in aqueous solution. ► It is determined the electrochemical constants and dissociated constant. ► The method opens up aqueous applications of insoluble organic compounds in electrochemistry.

A novel β-cyclodextrin/poly(vinyl alcohol) nanofibrous membrane (β-CD/PVAnfm) with the function of molecular capture was successfully prepared by electrospinning homogeneous aqueous solutions of β-CD and PVA. β-CD/PVAnfm was characterized by scanning electronic microscopy and Fourier transform infrared spectroscopy. The viscosity of β-CD/PVA solution was increased with the concentration of β-CD and high viscosity of β-CD/PVA solution was beneficial to form more uniform nanofibers. The interaction between β-CD and PVA in the solution was studied by rheological measure and 1H NMR spectra. The rheological change of electrospinning solutions was attributed to the intermolecular hydrogen bonding between β-CD and PVA in the solution, which was confirmed by 1H NMR spectra. The electrochemical measurement showed that β-CD/PVAnfm could recognize small hydrophobic molecules such as ferrocene (Fc) by forming inclusion complexes. The molecular capturing ability of β-CD/PVAnfm was increased with the amount of β-CD in composite nanofibrous membrane. The results suggested that the composite nanofibrous membrane was potentially applied to purification/separation processes, electrochemical sensor, drug delivery, and so on.Highlights• In this work, we produce β-CD/PVA nanofibrous membrane by electrospinning. The morphology of nanofibers is strongly correlated with the viscosity of β-CD/PVA solution. • We confirm the molecular capturing ability of β-CD functional nanofibrous membrane. • The novel nanofibrous membrane will be exploited purification/separation processes.

Porous magnetite (Fe3O4) nanospheres composed of primary nanocrystals have been successfully synthesized by solvothermal method with FeCl3·6H2O serving as the single iron resource, polyvinylpyrrolidone (PVP) as the capping agent, and sodium acetate as the precipitation agent. To understand the formation mechanism of the porous Fe3O4 nanospheres, the reaction conditions such as the concentration of the precursor, capping agent, precipitation agent, the reaction temperature, and reaction time were investigated. The characterization of the as-prepared product was identified with transmission electronic microscopy (TEM), field emission scanning electronic microscopy (FE-SEM), X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), vibrating sample magnetometer (VSM), N2 adsorption–desorption technique, and Fourier transform infrared spectroscopy (FTIR). The results indicate that the porous Fe3O4 nanospheres display excellent magnetic properties at room temperature, which allows them to be easily separated from the reaction system with the help of external magnet when they serve as catalysts. Catalytic activity studies show that the as-prepared porous Fe3O4 nanospheres are highly effective catalysts for the degradation of xylenol orange (XO) in aqueous solution with H2O2 as oxidant. The degradation reaction is first-order, its rate constant at room temperature being 0.056 min–1. Furthermore, the catalytic activity of Fe3O4 nanospheres decreases very slightly after seven cycles of the catalysis experiment. Therefore, porous Fe3O4 nanospheres can serve as effective recyclable catalysts for the degradation of XO.

An efficient magnetic carbon nanocomposite supported Pd nanoparticle catalyst has been prepared by a three-step process in this report. The morphology, inner structure, and magnetic properties of all products were studied with transmission electron microscopy, X-ray powder diffraction, Fourier translation infrared spectroscopy, X-ray photoelectron spectroscopy, and vibrating sample magnetometer. The Suzuki and Heck coupling reactions were used to demonstrate the catalytic efficiency of the as-prepared Pd/Fe3O4@C (Pd/MFC) nanocomposite catalyst. The results showed that the catalyst is completely recoverable with the simple application of an external magnetic field and the catalytic efficiency shows no obvious loss for Suzuki and Heck coupling reactions even after five repeated cycles.

A novel dopamine sensor was fabricated by forming the inclusion complex between mono-6-thio-β-cyclodextrin (CD-SH) and ferrocene (Fc) functionalized gold nanoparticles (GNPs) films on a platinum electrode. The properties of the GNPs/CDSH-Fc nanocomposite were characterized by Fourier transform infrared spectra, UV–visible absorption spectroscopy, transmission electron microscopy and cyclic voltammetry. The electrochemistry of dopamine (DA) was investigated by cyclic voltammetry (CV) and differential pulse voltammograms (DPV). The electrooxidation of dopamine could be catalyzed by Fc/Fc+ couple as a mediator and had a higher electrochemical response due to the unique performance of GNPs/CDSH-Fc. The anodic peaks of DA and ascorbic acid (AA) in their mixture can be well separated by the prepared electrode. Under optimum conditions linear calibration graphs were obtained over the DA concentration range 2.0 × 10− 6 to 5.0 × 10− 5 M with a correlation coefficient of 0.998 and a detection limit of 9.0 × 10− 8 M (S/N = 3). The modified electrode had been effectively applied for the assay of DA in dopamine hydrochloride injections. This work provides a simple and easy approach to selectively detect DA in the presence of AA.Research highlights► The sensor of DA was constructed by using GNPs/CDSH-Fc as the building block. ► Inclusion complex on the surface of GNPs decreased the leakage of mediator. ► The electro-oxidation of DA could be catalyzed by Fc/Fc+ couple as a mediator. ► This work provides a simple approach to selectively detect DA in the presence of AA.

The reaction of neutral two-dimensional (2D) layer Tb(H2O)5W(CN)8 with pyrazine in the acetonitrile solution has led to a 3D bimetallic complex, Tb(H2O)4(pyrazine)0.5W(CN)8 (1). In the structure of 1, the eight-coordinated W center adopts a slightly distorted dodecahedron, while the Tb center exhibits a nine-coordinated slightly distorted tricapped trigonal prism. The Tb3+ atoms and the [W(CN)8]3- units are linked in alternating fashion in the ab crystallographic plane, resulting in an infinite 2D corrugated layers. The linear bis-monodentate pyrazine ligands acting as pillars link adjacent layers along the c axis to form an extended 3D open framework. The possible formation mechanism is proposed, and the temperature has played a crucial role for the formation of 1. Magnetic measurements revealed the presence of ferromagnetic interaction between TbIII and WV centers. 1 marks the first structural pattern using the neutral 2D layer as building block and the first 3D complex with LnIII-[WV(CN)]8 found in octacyanometallate-based system. Such a novel and effective building-block methodology will provide a new attractive path forward in developing functionalities of 3D 4f−5d system and may provide an opportunity to obtain 3D magnet in 4f−5d assembly.

New-style adsorbents of p-tert-butyl-calix[4,6,8]arene-bonded silica gel—CnABS (C4ABS, C6ABS, C8ABS)—were prepared by bonding p-tert-butyl-calix[4,6,8]arene to the silica gel surface through the coupling reagent, 3-glycidoxypropyltrimethoxysilane. The products were characterized by FTIR, thermogravimetry, elemental analysis, and scanning electron microscopy. The adsorption of methylene blue from aqueous solution by CnABS was studied. Kinetic studies showed that the adsorption of the dye onto CnABS fit a first-order kinetic model. The equilibrium adsorption data were interpreted using the Langmuir and Freundlich models. The adsorption of methylene blue onto CnABS was better represented by the Langmuir equation. The saturation adsorption quantity monotonically increased with the number of phenolic units in the calixarene ring. The thermodynamic parameters for the adsorption reaction were calculated through a van’t Hoff analysis. The whole adsorption process was endothermic, which resulted in an increase of the adsorption quantity with a temperature increase. The new-style adsorbent of CnABS was regarded as a potential adsorbent to deal with dyes or organics in wastewaters.

A novel amperometric glucose sensor based on inclusion complex of mono-6-thio-β-cyclodextrin/ferrocene capped on gold nanoparticles (GNPs/CD–Fc) and glucose oxidase (GOD) was described. The inclusion complex of mono-6-thio-β-cyclodextrin/ferrocene capped on gold nanoparticles played an effective role of an electron shuttle and allowed the detection of glucose at 0.25 V (versus SCE), with dramatically reduced interference from easily oxidizable constituents. The sensor (GNPs/CD–Fc/GOD) showed a relatively fast response time (5 s), low detection limit (15 μM, S/N = 3), and high sensitivity (ca. 18.2 mA M−1 cm−2) with a linear range of 0.08–11.5 mM of glucose. The excellent sensitivity was possibly attributed to the presence of the GNPs/CD–Fc film that can provide a convenient electron tunneling between the protein and the electrode. In addition, the biosensor demonstrated high anti-interference ability, stability and natural life. The good stability and natural life can be attributed to the following two aspects: on the one hand, the fabrication process was mild and no damage was made on the enzyme molecule, on the other hand, the GNPs possessed good biocompatibility that could retain the bioactivity of the enzyme molecules immobilized on the electrode.

The water-soluble p-sulfonated sodium salt of calix[8]arene (III) was synthesized. The product was characterized by FT-IR, NMR and UV–Vis spectra.Then the electrochemical behaviors of p-sulfonated sodium salt of calix[8]arene in NaAc+HAc (pH = 4) buffer solution was studied. In aqueous solution, p-sulfonated calix[8]arene can be oxidized when the potential is more than 0.7 V vs SCE. It was confirmed that the reaction was a two-electron irreversible electrochemical reaction. The transfer coefficient, α, was measured as 0.7. At 25°, the diffusion coefficient of p-sulfonated calix[8]arene was determined as 8.6  ×  10−7 cm2 s−1. The diffusion activation energy of p-sulfonated calix[8]arene was 18.9  kJ mol−1 at pH = 4.

•Fe3O4@C-N yolk−shell nanocapsules were synthesized without sacrificial template.•Yolk−shell structure allows Fe3O4 to expand freely without breaking carbon shell.•The volume expansion of Fe3O4 results in the in-depth nanocrystallization.•In-depth nanocrystallization of Fe3O4 enhances the capability.•Fe3O4@C-N-700 delivers a high capacity and excellent cycling stability.In this paper nitrogen-doped carbon-encapsulation Fe3O4 yolk−shell magnetic nanocapsules (Fe3O4@C-N nanocapsules) have been successfully constructed though a facile hydrothermal method and subsequent annealing process. Fe3O4 nanoparticles are completely enclosed in nitrogen-doped carbon shells with void space between the nanoparticle and the shell. The yolk−shell structure allows Fe3O4 nanoparticles to expand freely without breaking the outer carbon shell during the lithiation/delithiation processes. The volume expansion of Fe3O4 results in the in-depth nanocrystallization. Fortunately, the new generated small nanoparticles can increase the capability with the cycle increase due to the unique confinement effect and excellent electronic conductivity of the nitrogen-doped carbon shells. Hence, after 150 cycles, the discharge capacity of Fe3O4@C-N-700 nanocapsules still remained 832 mA h g−1 at 500 mA g−1, which corresponds to 116.7% of the lowest capacity (713 mA h g−1) at the 16th cycle. We believe that the yolk−shell structure is conducive to enhance the capacity of easy pulverization metal oxidation during the charge/discharge processes.

In this paper, the formation of hydroxypropyl-β-cyclodextrin (HPCD) nanofibers in electrospinning and the adsorption of organic molecules on the HPCD nanofiber were studied. The properties of a polymer-like solution from the highly concentrated HPCD/N,N-dimethylformamide (DMF) solution revealed HPCD supramolecular aggregates formation. The entanglements of HPCD self-organized aggregates were one of the most important factors that significantly influenced fiber formation during cyclodextrin electrospinning. The HPCD self-organized aggregates entanglement concentration (Ce) was investigated. Analyzing the dependence of specific viscosity (ηsp) on concentration enabled the determination of the aggregates unentangled and entangled regimes for HPCD polymer-like solutions. The dynamic light scattering (DLS) measurements and the 1H NMR spectra of the HPCD solutions confirmed the presence of considerable HPCD self-organized aggregates in high concentrated HPCD/DMF solutions due to the intermolecular hydrogen bonding. The scanning electron microscopy (SEM) showed the electrospinning morphology transitioned from regular beads to uniform fibers with increasing the HPCD concentration. The dependence of the fiber diameter on the zero shear rate viscosity (η0) was determined. The static adsorption behavior of the HPCD fibers was studied. Neutral red (NR) was used as a model organic molecule. The adsorption of NR onto HPCD fibers fitted the pseudo-second-order kinetic model. The equilibrium adsorption amount of NR was 18.41 mg g−1, and the apparent adsorption rate constant was 9.83 × 10−4 g mg−1 min−1 at 25 °C.

A stable aqueous inclusion complex of fullerene (C60) with macromolecules (C60 concentration as high as 3 × 10−4 mol L−1) was achieved by a one-step strategy using γ-cyclodextrin polymer (γ-CDP). The inclusion complex of C60 with γ-CDP (C60–γ-CDP) was characterized by ultraviolet-visible, Raman and 1H-NMR spectroscopies, powder X-ray diffraction analysis, and thermogravimetric analysis. The supramolecular interactions and the equilibrium constant for a 1:2 (C60:CD unit in γ-CDP) complex of C60 with γ-CDP were studied. Under ultraviolet A (UVA) irradiation C60–γ-CDP in water could generate singlet oxygen, which was detected by electron paramagnetic resonance spectroscopy. We also evaluated the cytotoxicities of C60–γ-CDP, and investigated the phototoxicity of C60–γ-CDP and pristine C60 toward B16-F10 melanoma cells. The cell viability test showed that C60–γ-CDP had a significantly higher photodynamic ability than that of the pristine C60 under UVA irradiation. This work demonstrated both a CDP-functionalized strategy for enhancing the water-solubility and phototoxicity of fullerenes for applications in cancer photodynamic therapy, as well as remediating the negative biological effects of pristine fullerenes.

An amphiphilic amino resorcinarene (T) was modified onto the surface of graphene oxide (GO) through covalent bond forces and non-covalent bond forces to prepare GO–T. The water-soluble graphene–T (GN–T) composite was prepared by the reduction of GO–T. Then, pre-prepared platinum nanoparticles (PtNPs) and different sized gold nanoparticles (AuNPs) could self-assemble onto the surface of GN–T through the plentiful amido groups of T to obtain GN–T–AuNPs and GN–T–PtNPs hybrid materials. It was verified that the AuNPs and PtNPs could be uniformly scattered on GN and the amount of AuNPs and PtNPs modified on GN could be adjusted by changing the weight ratio of T/GO. GN-T-PtNPs and GN-T-AuNPs composites showed the characteristics of being dispersible, stable and recyclable in water. Electrochemical results obviously revealed that GN–T–AuNPs and GN–T–PtNPs composites exhibited outstanding electrocatalytic properties.

In this article, a study was presented on the catalytic activity of silver nanoparticles immobilized on magnetic Fe3O4@C (MFC) core–shell nanocomposites (Ag/MFC) that were used as carriers. MFC composites consist of a magnetic core of an Fe3O4 microsphere onto which a thin layer of carbon was coated by in situ carbonization of glucose under hydrothermal conditions. The catalytic activity of the as-prepared Ag/MFC is investigated by photometrically monitoring the reduction of 4-nitrophenol and methylene blue by an excess of NaBH4. The kinetic data of both reduction reactions could be explained by the assumption of a pseudo-first-order reaction with regard to 4-nitrophenol or methylene blue. Significantly, the Ag/MFC catalysts can be easily separated from the reaction media by applying an external magnet, and can be reused for several cycles.

A new family of hexanuclear titanium(IV)-oxo-carboxylate cluster K7H[Ti6O9(ida)6]Cl2·13H2O {Ti6O9} has been synthesized via the H2O2-assisted reaction between TiCl4 and iminodiacetate ligands. This cluster was fully characterized by single-crystal X-ray diffraction and a wide range of analytical methods, including FT-IR, UV/vis spectroscopy as well as electrochemistry and thermogravimetric analysis. As a new type of carboxylate substituted Ti-oxo-cluster, the structural motif of the {Ti6O9} cluster consists of one symmetric {Ti6O6} hexagonal prism with two staggered triangular {Ti3O3} subunits linked by three μ2-O bridges. The {Ti6O9} polyanions are linked by K+ cations to form a novel 3D architecture. The structural information and stability of the {Ti6O9} polyanion in aqueous solution were thoroughly investigated by solid-state/solution NMR, ESI-MS spectroscopy. Moreover, this Ti-oxo cluster exhibits remarkable potential as a visible-light homogeneous photocatalyst for degradation of rhodamine B (RhB). Finally, a proposed peroxotitanium(IV)-mediated photocatalytic pathway involved is illustrated by spectroscopic data.

Novel quantum-dot-tagged photonic crystal beads were fabricated for multiplex detection of tumor markers via self-assembly of quantum dot-embedded polystyrene nanospheres into photonic crystal beads through a microfluidic device.

Hollow carbon nanonets (HCN), which are attractive materials for catalyst support, were fabricated using the pre-synthesized hematite nanoparticles as the hard template. And then the HCN supported Pd nanoparticles (Pd/HCN) were prepared by precipitation-reduction method. The catalytic performance of Pd/HCN was investigated using Suzuki and Heck coupling reactions as model reactions. The results demonstrated that the as-prepared Pd/HCN nanocomposites exhibit high catalytic activity for the two types of coupling reactions under ligand free conditions. Especially, the Suzuki reactions between various aryl halides and phenylboronic acid gave excellent yields in water. Moreover, the as-prepared Pd/HCN catalysts can be easily recovered from the reaction medium by centrifugation for recycling, and the catalytic efficiency shows no obvious loss even after 6 repeated cycles.

Transition metal complexes with substituted high affinity mixed ligands as potential anticancer agents can overcome the drawbacks of platinum-based drugs that are currently being marketed. Here, a new water-soluble asymmetric binuclear iminodiacetato-zinc(II) complex [Zn2(ida)(phen)3(NO3)]·NO3·5H2O (1) with a phenanthroline ligand has been synthesized and fully characterized with a wide range of analytical techniques including single crystal X-ray diffraction as well as spectroscopic techniques, such as FT-IR, UV/Vis, photoluminescence spectroscopy, and furthermore by elemental and thermogravimetric analyses. Moreover, unprecedented (H2O)10 water clusters consisting of a quasi-planar tetramer and six dangling water molecules were observed in the void space of 3D supramolecular assemblies. The conversion behavior of (1) into two monomeric species [Zn(ida)(phen)(H2O)] (2) and [Zn(phen)2(H2O)2]2+ (3) in aqueous solution was first studied by solid-state/solution NMR, ESI-MS, and solution UV/vis spectra. Next, these zinc(II) complexes (1–3), a mixture of (2) and (3) (mole ratio 1/1), ligands (phen and ida) and zinc ions (ZnCl2 and ZnSO4) were further evaluated for the in vitro cytotoxic profile in human hepatoma cell lines (HepG2 and SMMC-7721). We found that complex (1) effectively inhibited the proliferation of hepatocellular carcinoma cells, which is similar to a mixture of (2) and (3) in a 1:1 molar ratio, and IC50 values of (1) were almost about 20–50% of (2) or (3). Therefore, this binuclear complex (1) mainly acts as a cooperative inhibitor with complexes (2) and (3) toward tumor growth in solution. We further extended the preliminary research of complex (1) and found that (1) could induce cell cycle arrest at the G0/G1 phase. Additionally, overdosing on (1) exhibited low toxicity of mice (LD50 of (1) in ICR mice = 736 mg kg−1, with 95% confidence interval 635–842 mg kg−1). In conclusion, complex (1) with a high antitumor activity and low toxicity provides a new strategy for the treatment of liver cancer.

Copper oxide (CuO) nanorods were synthesized via a facile hydrothermal process, which exhibit excellent catalytic oxidation of cyclohexene to 2-cyclohexene-1-one by tert-butyl hydrogen peroxide (TBHP) in acetonitrile. This would provide a novel method for directly synthesizing α,β-unsaturated ketones from olefins.

The first amphiphilic pillar[6]arene was successfully synthesized. It can complex with adenosine triphosphate to form vesicles in water. Moreover, these vesicles are efficiently responsive to phosphatase.

A new water-soluble inclusion complex of ilexgenin A (IGA) with β-cyclodextrin polymer (CDP) was prepared by a facile strategy and characterized by 1H NMR , FT-IR, and UV-vis spectroscopy. Compared with IGA and the inclusion complex of IGA with β-cyclodextrin (IGA–CD), the solubility of IGA–β-cyclodextrin polymer (IGA–CDP) was greatly enhanced due to the water-soluble CDP host. The ratio of β-cyclodextrin (β-CD) units in CDP to IGA was determined as 2:1. KD of the inclusion complex was evaluated as 2.6 × 10−3 mol L−1. The effects of IGA–CDP on a hyperlipidemia mouse model were studied by intragastric administration. After 4 weeks, the IGA–CDP treatment resulted in decreased serum levels of total cholesterol and low-density lipoprotein-cholesterol. The effects of IGA–CDP on serum apolipoprotein levels were similar to its effects on lipid levels. By comparing liver area, the effects of IGA–CDP on pre-existing lesions were assessed. Furthermore, the efficacy and potency of water-soluble inclusion complex of IGA–CDP was 2–3 times higher than that of IGA. Taken together, it was possible to develop it to a novel drug candidate to regulate lipid abnormality.

The reaction of [W(CN)8]3− with Ln3+ and pyrazine in acetonitrile yielded a series of isostructural compounds formulated as Ln(H2O)4(pyrazine)0.5W(CN)8 (Ln = La(1), Ce(2), Pr(3), Nd(4), Sm(5), Eu(6), Gd(7)). The Ln(III) and W(V) centers in the structure are linked through cyanide groups to form two-dimensional (2D) layers, which are further pillared by pyrazine, generating 3D frameworks. The magnetic behavior for compounds 1–7 were driven by the lanthanide ions involved. The Ln(III) and W(V) ions in compounds 2 and 5 are ferromagnetically coupled with magnetic ordering occurring at 2.8 K, comparable with magnetic ordering with the critical temperature of 1.9 K for compound 4. In addition, the antiferromagnetic interactions were observed in compounds 3 and 7, while no significant magnetic couplings were found in compounds 1 and 6.