Platinum-group-metal quaternary alloys with lattice defects for enhanced oxygen electrocatalysis.

We propose a facile coreduction method to synthesize a platinum-group-metal quaternary alloy anchored on nitrogen-doped hollow carbon spheres (PtPdRuIr/HCS) by using [MClx]y--1-butyl-3-methylimidazole (M = Pt, Pd, Ru, and Ir) ionic liquid. Owing to the steric hindrance of the imidazolium cations, Pt-group metal atoms of different sizes can be deposited at approximately the same pace for the growth of an alloy with lattice defects. The lattice-distorted PtPdRuIr/HCS exhibits enhanced activity toward oxygen electroreduction when benchmarked against Pt counterparts.

Functionalization of the Octahydro-Binaphthol Skeleton: A Universal Strategy for Directly Constructing D-A Type Axially Chiral Biphenyl Luminescent Molecules.

D-A type axially chiral biphenyl luminescent molecules are directly constructed through ingenious functionalization of the octahydro-binaphthol skeleton without optical resolution. The circularly polarized organic light-emitting diodes based on them display remarkable circularly polarized electroluminescence emission, a high luminance of >10 000 cd m-2, a maximum external quantum efficiency of 6.6%, and an extremely low-efficiency roll-off. This work provides a universal strategy for developing efficient and diverse axially chiral biphenyl emitters.

Rocking-chair proton battery based on a low-cost "water in salt" electrolyte.

A novel "water in salt" electrolyte is reported for the design of a rocking-chair proton battery. In 20 M ZnCl2 + 1 M HCl electrolyte, the electrochemical proton storage performance using MoO3 is significantly improved. When coupled with a Ni-PBA cathode, the device exhibits a good cycling stability of 76.1% after 400 cycles. This work opens a new avenue for designing low-cost "water in salt" electrolytes for aqueous proton electrochemistry.

Chemically grafting nanoscale UIO-66 onto polypyrrole nanotubes for long-life lithium-sulfur batteries.

A versatile strategy for a facile approach to chemical graft MOFs onto polypyrrole nanotubes (PPyNTs@MOFs) is designed and fabricated rationally by means of 1,4-dibromobutane linkage. Various MOFs arranged randomly close-packed on PPyNTs, including Co2+, Cu2+, Zn2+, Mn2+, Fe3+, Al3+, Ti4+, Cr4+, Zr4+ and V4+, have been synthesized successfully. The as-prepared PPyNT@UIO-66 hybrids, used as a cathode carrier, exhibit excellent cyclic stability in Li-S batteries via strong physical and chemical adsorption/affinity with polysulfides.

Development of ß-elemene and Cisplatin Co-Loaded Liposomes for Effective Lung Cancer Therapy and Evaluation in Patient-Derived Tumor Xenografts.

PURPOSE: ß-elemene and cisplatin combined chemotherapy currently is one of the most important settings available for lung cancer therapy in China. However, the clinical outcome is limited by their pharmacokinetic drawbacks. On the other hand, most of nanomedicines have failed in clinical development due to the huge differences between heterogeneous clinical tumor tissues and homogenous cell-derived xenografts. In this work, we fabricated a ß-elemene and cisplatin co-loaded liposomal system to effectively treat lung cancer. METHOD: In vitro cytotoxicity of co-loaded liposomes was studied by MTT, trypan and Hoechst/PI staining, and western blot in A549, A549/DDP, and LCC cells. In vivo antitumor efficacy was evaluated in cell-derived and clinically relevant patient-derived xenografts. RESULTS: Co-loaded liposomes were more cytotoxic to cancer cells, especially than the combination of single-loaded liposomes, benefiting from their simultaneous drug internalization and release. As a result, they exhibited desirable therapeutic outcome in both cell-derived and patient-derived xenografts. CONCLUSION: ß-elemene and cisplatin co-loaded liposomes are a clinically promising candidate for effective lung cancer therapy.

Surface Reconstruction for Preparation of Plasmonic Au/TiO2 Nanoparticle with Perfect Hetero Interface and Improved Photocatalytic Capacity.

The photocatalytic activity of plasmonic Au/TiO2 nanoparticles (NPs) is dependent on distances between Au and TiO2. The preparation of plasmonic NPs is still a challenge because of an inherent lattice mismatch on heterogeneous interfaces. The combination between Au and TiO2 NPs often exhibits physical adsorption, which affect block the electron transferring process by photo-induction from TiO2 to Au NPs and weaken the photocatalytic activity. In this work an approach for preparing plasmonic Au/TiO2 NPs with perfect hetero-interface was proposed based on reconstruction of anatase TiO2 with (101) surface and in-situ reduction of Au NPs. Under UV-irradiation, anatase TiO2 NPs with a high percentage of (001) facets in formaldehyde solution undergo photochemical reactions to reconstruct the (101) surface of TiO2 and simultaneously allow polyformaldehyde to absorb on the same surface. Thus, Au(OH)-4 ions could be adsorbed on the (101) surfaces of TiO2 through electrostatic adsorption and reduced to form nano-Au in situ after recrystallization at 180 °C. The high-resolution transmission electron microscopy (HRTEM) images showed clear nanoscale lattice transition on heterogeneous interfaces of Au/TiO2 NPs. The surface structure of TiO2 NPs and the growth mechanism of Au/TiO2 NPs were evaluated with HRTEM, X-ray photoelectron spectra (XPS) and Fourier transform infrared spectroscopy (FTIR). It was demonstrated that the as-prepared plasmonic Au/TiO2 NPs had higher photocatalytic activity and corrosion resistance in comparison with primary TiO2 NPs by photo-electrochemical measurements. The reinforcing mechanism could be interpreted with Mott-Schottky analysis in terms of quantum mechanics. Our study implied that the reconstruction based synthesis may open up more opportunities to obtain lattice-mismatch nanomaterials for photocatalysis.

Silsesquioxane stabilized platinum-palladium alloy nanoparticles with morphology evolution and enhanced electrocatalytic oxidation of formic acid.

Bimetallic catalysts have attracted enormous attention with their enhanced electrocatalytic properties in fuel cells. Herein a series of silsesquioxane (POSS) stabilized platinum-palladium (PtPd) alloy nanoparticles (NPs) with morphology evolution were facilely synthesized with the co-chemical reduction using formaldehyde as the reductant. By varying the ratio of Pt to Pd, the PtPd alloy NPs evolved from truncated octahedrons to octahedrons, and triangular nanoplates. The mechanism of morphology evolution is that Pt and Pd could self-assemble on POSS to form PtxPd1-x intermediates with different Pt/Pd ratios. In addition, formaldehyde could selectively bind to the {1 1 1} facets of Pd to control the growth rates of different facets and help PtxPd1-x intermediates with different Pt/Pd ratio grow into different morphology of PtxPd1-x alloys. The morphology tuning endowed the PtPd alloy NPs superior performance for formic acid electrooxidation. Compared with Pt, Pd NPs, and commercial Pt/C catalyst, the PtPd alloy NPs displayed larger electrochemically active surface area, enhanced electrocatalytic activity and durability toward oxidation of formic acid, and increased CO tolerance. This work suggested that modification of catalytic activity through morphology tuning with composition adjustment might provide some new pathways for the design of promising catalysts with advanced performance.

In Situ Integration of Ultrathin PtCu Nanowires with Reduced Graphene Oxide Nanosheets for Efficient Electrocatalytic Oxygen Reduction.

Ultrathin Pt-based nanowires are considered as promising electrocatalysts owing to their high atomic utilization efficiency and structural robustness. Moreover, integration of Pt-based nanowires with graphene oxide (GO) could further increase the electrocatalytic performance, yet remains challenging to date. Herein, for the first time we demonstrate the in situ synthesis of ultrathin PtCu nanowires grown over reduced GO (PtCu-NWs/rGO) by a one-pot hydrothermal approach with the aid of amine-terminated poly(N-isopropyl acrylamide) (PNIPAM-NH2 ). The judicious selection of PNIPAM-NH2 facilitates the in situ nucleation and anisotropic growth of nanowires on the rGO surface and oriented attachment mechanism accounts for the formation of PtCu ultrathin nanowires. Owing to the synergy between PtCu NWs and rGO support, the PtCu-NWs/rGO outperforms the rGO supported PtCu nanoparticles (PtCu-NPs/rGO), PtCu-NWs, and commercial Pt/C toward the oxygen reduction reaction (ORR) with higher activity and better stability, making it a promising cathodic electrocatalyst for both fuel cells and metal-air cells. Moreover, the present synthetic strategy could inspire the future design of other metal alloy nanowires/carbon hybrid catalysts.

Rational synthesis of Ni nanoparticle-embedded porous graphitic carbon nanosheets with enhanced lithium storage properties.

Carbon-based materials have recently received increased attention as very promising anode materials for rechargeable lithium-ion batteries (LIBs) because of their non-toxicity, low cost, and excellent performances. Nanostructure engineering has been demonstrated as an effective approach to improve the electrochemical performance of electrode materials. Here, we present a facile and scalable synthesis of two-dimensional (2D) porous graphitic carbon nanosheets embedded by numerous homogeneously dispersed Ni nanoparticles. With both structural and compositional advantages, the as-synthesized nanohybrid manifests a very stable high reversible capacity of 740 mA h g(-1) after 100 cycles at a current density of 100 mA g(-1), and also excellent rate capability and cycling stability. We believe that the synthetic strategy outlined here can be extended to other rationally designed anode materials with high performances in LIBs.

In situ plasma sputtering synthesis of ZnO nanorods-Ag nanoparticles hybrids and their application in non-enzymatic hydrogen peroxide sensing.

In this paper, ZnO nanorods-Ag nanoparticles hybrids were first synthesized via a facile, rapid, and in situ plasma sputtering method without using any silver precursor. The obtained materials were then characterized by scanning electron microscopy, high-resolution transmission electron microscopy, energy-dispersive x-ray spectroscopy, and cyclic voltammetry. Based on the electrochemical catalytic properties of the obtained nanohybrids, a non-enzymatic hydrogen peroxide biosensor was constructed by immobilizing the obtained ZnO nanorods-Ag nanoparticles hybrids on the surface of a glassy carbon electrode. Under optimal conditions, the resulting biosensor displayed a good response for H2O2 with a linear range of 0.2 to 12.8 mM, and a detection limit of 7.8 µM at a signal-to-noise ratio of 3. In addition, it exhibited excellent anti-interference ability and fast response. The current work provides a feasible platform to fabricate a variety of non-enzymatic biosensors.

Interaction between Z-ligustilide from Radix Angelica sinensis and human serum albumin.

Z-ligustilide (LIG), an essential oil extract from Radix Angelica sinensis, has broad pharmaceutical applications in treating cardiovascular and cerebrovascular diseases. Interaction of LIG with the major transport protein of human blood circulation, human serum albumin (HSA) has been investigated by steady-state, UV-vis and circular dichroism (CD) spectroscopic methods, as well as the effect of metal ions (e.g. Zn(2+), Cu(2+), Fe(3+), Co(2+), Ni(2+)) on the LIG-HSA system. Fluorescence results revealed that a moderate binding affinity (1.59 × 10(4) M(-1) at 298 K) between LIG and HSA with a 1:1 stoichiometry. Thermodynamic analysis of the binding data (ΔS = +12.96 J mol(-1) K(-1) and ΔH =- 20.11 kJ mol(-1)) suggested the involvement of hydrophobic and van der Waals forces, as well as hydrogen bonding in the complex formation. The specific binding distance r (3.75 nm) between donor (Trp-214) and acceptor (LIG) was obtained according to fluorescence resonance energy transfer. CD results showed that slight conformational changes occurred in the protein upon complexation with LIG.

Binding of dihydromyricetin to human hemoglobin: fluorescence and circular dichroism studies.

The binding reaction between dihydromyricetin (DMY) and human hemoglobin (HHb) was investigated systematically with various spectroscopic methods including fluorescence quenching technique, ultraviolet (UV)-vis absorption, synchronous fluorescence, circular dichroism (CD) spectroscopy. The experimental results showed that DMY effectively quenched the intrinsic fluorescence of HHb via static quenching. DMY binds to HHb with a stoichiometry that varies from 0.972:1 to 0.906:1 as the temperature increases from 296 to 304 K. The DMY-HHb binding constants were determined to be K(296)=2.79 × 10(4) and K(304)=1.18 × 10(4) Lmol(-1). The reaction is characterized by negative enthalpy (ΔH=-80.46 kJ mol(-1)) and negative entropy (ΔS=-186.72 kJ mol(-1)), indicating that the predominant forces in the DMY-HHb complex are van der Waals and hydrogen bonding forces. Based on the Förster's theory of non-radiative energy transfer, the binding distance between DMY and the inner tryptophan residues of HHb was determined to be 3.15 nm. Furthermore, the CD spectroscopy indicated the secondary structure of HHb is not changed in the presence of DMY.

Cathodic stripping synthesis and cytotoxity studies of glutathione-capped CdTe quantum dots.

A cathodic stripping of Te precursor in the presence of Cd2+ and biocompatible glutathione (GSH) was reported for facile synthesis of lowly cytotoxic and highly luminescent CdTe quantum dots (QDs) in aqueous solution. The photoluminescence, electrogenerated chemiluminescence (ECL), toxicity, and cyto-osmosis of the QDs were evaluated to reveal their potential bio-applications. The morphology and composition of as-prepared QDs were investigated by HRTEM and powder XRD spectroscopy, which indicated that the QDs consisted of a CdTe core coated with a CdS shell. The obtained CdTe/CdS core/shell QDs possessed good crystallinity, narrow monodispersity and long-term stability. These QDs showed high fluorescence quantum yields of 49% to 63% over a broad spectral range of 540-650 nm. Efficient and stable ECL of QDs was observed on the anodic potential region upon the electrode potential cycled between 1.5 and -2.0 V versus Ag/AgCl. Furthermore, human liver cancer HepG2 cells were chosen as model cells for toxicity assay of QDs. Effects of the concentration, size, and incubation time of CdTe QDs capped with GSH or mercaptoacetic acid (MAA) on the cell metabolic viability and cyto-osmosis were evaluated. GSH-capped CdTe QDs could infiltrate cytomembrane and karyothecas, and were less cytotoxic than MAA-capped ones under the same experimental conditions. The reported CdTe QDs could be good candidates of fluorescent and ECL probes for biosensing and cell imaging.

Preparation and characterization of highly luminescent water-soluble CdTe quantum dots as optical temperature probes.

Highly luminescent water-soluble CdTe quantum dots were synthesized with an electrogenerated precursor. The size, morphology, optical properties as well as fluorescence stability were characterized by transmission electron microscope, high-resolution transmission electron microscope, powder X-ray diffraction, UV-vis-NIR spectrophotometer, and fluorescence spectrophotometer. The results show that the CdTe QDs with diameter ranging from 2.0 nm to 3.5 nm have good crystallizability, high quantum yield and favorable fluorescence stability. Moreover, the CdTe QDs demonstrate temperature-dependent reversible PL intensity variations at moderate temperatures above room temperature. It is also found that the QDs with different sizes possess different sensitivity to the temperature. All the studies indicate that the CdTe QDs are expected to be promising candidates for a variety of biological and biomedical applications.

[The photological function of MPA coated CdTe QDs and their biocompatibility].

AIM: To investigate the CdTe quantum dots coated with MPA and explore its biocompatibility with living cells. METHODS: CdTe quantum dots coated with MPA were prepared in aqueous phase and MPA CdTe QDs were Characterized with TEM, fluorospectrophotometer and ultraviolet spectrophotometer. QDs were Modified with with avidin, purified and prepared as fluorescent probe. LSCM was used to observe the expression of MHCII antigen on PMphi cells, which was labeled by QDs. Cell culture and MTT assays were used to determine the biocompatibility of MPA coated CdTe quantum dots with the B-16 cells as target cells. RESULTS: The particle diameter of CdTe quantum dots prepared in aqueous phase was well distributed. They had good photological performance and greater stability after coated with MPA. MHCII antigen on PMphi was labeled with the QDs-Avidin fluorescent probe showed great fluorescence intensity, which was easy to be detected by fluorescence microscope and LSCM. MPA CdTe QDs showed cytotoxicity when its density was very high, but they showed little cytotoxicity during the normal use of influence label density limit. CONCLUSION: MPA CdTe QDs can be used as new fluorescent label as they are of even size, not easy to bleach or quench, have good photological performance and stability and good biocompatibility.

Facile synthesis and application of highly luminescent CdTe quantum dots with an electrogenerated precursor.

An electrogenerated precursor has been developed for green synthesis of highly luminescent aqueous CdTe quantum dots (QDs) with unique quantum yield and strong electrogenerated luminescence, which can access cellular targets via specific binding and have potential application as biolabels in highly sensitive biosensing and cell imaging.

Glutaraldehyde-modified electrode for nonlabeling voltammetric detection of p16 INK4A gene.

A nonlabeling electrochemical detection method for analyzing the polymerase-chain-reaction-amplified sequence-specific p16 ( INK4A ) gene, in which the basis for the covalent immobilization of deoxyribonucleic acid (DNA) probe is described, has been developed. The self-assembly process was based on the covalent coupling of glutaraldehyde (GA) as an arm molecule onto an amino-functional surface. The p16 ( INK4A ) gene was used as the model target for the methylation detection of early cancer diagnosis. An amino-modified DNA probe was successfully assembled on the GA-coupling surface through the formation of Schiff base under potential control. The hybridization of amino-modified DNA probes with the target was investigated by means of electrochemical measurements, including cyclic voltammetry and square wave voltammetry. Furthermore, the functions of GA coupling for sequence-specific detection were compared with those obtained based on mercaptopropionic acid. Hybridization experiments indicated that the covalent coupling of GA was suitable for the immobilization of DNA probe and was sensitive to the electrochemical detection of single-base mismatches of label-free DNA targets in hybridization. Moreover, reported probe-modified surfaces exhibited excellent stability, and the hybridization reactions were found to be completely reversible and highly specific for recognition in subsequent hybridization processes. The strategy provided the potential for taking full advantage of existing modified electrode technologies and was verified in microarray technology, which could be applied as a useful and powerful tool in electrochemical biosensor and microarray technology.

Detection of methylation of human p16(Ink4a) gene 5'-CpG islands by electrochemical method coupled with linker-PCR.

Aberrant DNA methylation of the CpG site is among the earliest and most frequent alterations in cancer. Detection of promoter hypermethylation of cancer-related genes may be useful for cancer diagnosis or the detection of recurrence. p16, an inhibitor of the cyclin D-dependent protein kinases, is a classical tumor suppressor gene, and its inactivation is closely associated with carcinogenesis. p16 hypermethylation could be detected in each stage, which is consistent with the finding that aberrant methylation of p16 is a very early event in carcinogenesis. We have developed an electrochemical procedure for detecting DNA methylation of the human p16(Ink4a) gene. The procedure is based on the coupling of DNA electrochemical sensors with linker-PCR- amplified DNA from human gastric tumor tissue and whole blood cells of healthy human. The synthesized oligonucleotide was immobilized on the modified gold electrode to fabricate a DNA biosensor. The hybridization reaction on the electrode surface was monitored by cyclic voltammogram (CV) and square wave voltammogram (SWV), using [Co(phen)(3)](ClO(4))(3) as a redox indicator. Methylation status of human p16(Ink4a) gene was detected and the results were validated by bisulfite DNA sequencing. A good reproducibility was observed in several parallel experiments. The coupling of DNA electrochemical sensors with PCR allowed quick detection and have the potential of the quantitative evaluation of the methylation status of the human p16(Ink4a) gene.

Electric potential control of DNA immobilization on gold electrode.

The assembly of synthetic, controllable molecules is one of the goals in nanotechnology. The primary objective of this contribution is to selectively immobilize DNA on gold via electric potential control. The self-assembly monolayer (SAM) was prepared with 2-aminoethanethiol (AET) on the gold electrode. A new approach based on electric potential was firstly used to control DNA immobilization covalently onto the SAM with the activation of 1-ethyl-3(3-dimethyl-aminopropyl)-carbodiimide (EDC) and N-hydroxysulfosuccinimide (NHS) in low ionic strength solution. The influence of electric potential on DNA immobilization was investigated by means of cyclic voltammogram, A.C. impedance, auger electron spectrometer as well as atomic force microscope (AFM) on template-stripped gold surface. The result proves that controlled potential can affect the course of DNA immobilization. More negative potential can restrain the DNA immobilization, while the more positive potential can accelerate the DNA immobilization. It is of great significance for the control of DNA self-assembly and will find wide application in the fields of DNA-based devices.