3D Fe3S4 flower-like microspheres: high-yield synthesis via a biomolecule-assisted solution approach, their electrical, magnetic and electrochemical hydrogen storage properties

Well-defined 3D Fe3S4 flower-like microspheres were synthesized via a simple biomolecule-assisted hydrothermal process for the first time. On the basis of a series of contrast experiments, the probable growth mechanism and fabrication process of the products were proposed. The electrical conductivity property of the as-synthesized Fe3S4 sample exhibited a rectifying characteristic when a forward bias was applied for the bottom-contacted device. The magnetic properties of the products were studied as well and the results demonstrated that the products presented ferromagnetic properties related to the corresponding microstructure. In addition, we first verified that the Fe3S4 flower-like microspheres could store hydrogen electrochemically, and a discharge capacity of 214 mA h g(-1) was measured without any activation under normal atmospheric conditions at room temperature.

Synthesis and Characterization of Coil-Rod-Coil Triblock Copolymers Comprising Fluorene-Based Mesogenic Monodisperse Conjugated Rod and Poly(ethylene oxide) Coil

A series of coil-rod-coil triblock copolymers (i.e., F3T8EO8, F3T8EO17, F3T8EO45, and F3T8EO125) with a mesogenic monodisperse conjugated oligomer comprising 3 fluorene, 8 thiophene, and 2 phenyl units as the rod and poly(ethylene oxide) (PEO) as the coil were synthesized. A reference compound, that is F3T8ME2, with the identical rod but without PEO was also prepared for comparison. The volume fraction of PEO (f(PEO)) was 0, 0.16, 0.28, 0.50, and 0.73 for F3T8ME2, F3T8EO8, F3T8EO17, F3T8EO45, and F3T8EO125, respectively. It was found that the introduction of PEO into the triblock copolymers encouraged the formation of H-type aggregation and f(PEO)-dependent highly ordered mesophases while f(PEO) < 0.73. For F3T8ME2, only nematic mesophase was observed. In contrast, F3T8EO8 and F3T8EO17, with f(PEO) of 0.16 and 0.28, respectively, are smectic A (SA) mesomorphism.

Dispersions of carbon nanotubes in sulfonated poly[bis(benzimidazobenzisoquinolinones)] and their proton-conducting composite membranes

A sulfonated poly[bis(benzimidazobenzisoquinolinones)] (SPBIBI) possessing a conjugated pyridinone ring was shown to be effective for dispersing multiwalled carbon nanotubes (MWCNTs) in DMSO. The dispersions in which the SPBIBI to MWCNTs mass ratio was 4:1 demonstrated the highest MWCNTs concentrations, i.e., 1.5-2.0 mg mL(-1), and were found to be stable for more than six months at room temperature. Through casting of these dispersions, MWCNTs/SPBIBI composite membranes were successfully fabricated on substrates as proton exchange membranes for fuel cell applications and showed no signs of macroscopic aggregation. The properties of composite membranes were investigated, and it was found that the homogeneous dispersion of the MWCNTs in the SPBIBI matrix altered the morphology structures of the composite membranes, which lead to the formation of more regular and smaller cluster-like ion domains.

Structure stability and strengthening mechanism of die-cast Mg-Gd-Dy based alloy

Mg-8Gd-1Dy-0.3Zn (wt.%) alloy was prepared by high-pressure die-casting technique. The thermal stability, mechanical properties at temperature range from room temperature to 573 K and strengthening mechanism was investigated. The results showed that the die-cast state alloy was mainly composed of fine cellular equiaxed grain. The fine porosity-free skin region was related to the aggregation of rare earth elements. The long lamellar-shaped stacking compound containing Zn and polygon-shaped precipitate were observed along the grain boundaries. The die-cast sample exhibited high mechanical properties and good thermal stability until 523 K.

DNA based gold nanoparticles colorimetric sensors for sensitive and selective detection of Ag(I) ions

In this work, we reported both unlabeled and labeled sensing strategies for Ag(I) ions detection by using the DNA based gold nanoparticles (AuNPs) colorimetric method. In the unlabeled strategy, C-base riched single strand DNA (C-ssDNA) enwinded onto AuNPs to form AuNPs/C-ssDNA complex. In the labeled method, sulfhydryl group modified C-ssDNA (HS-C-ssDNA) was covalently labeled on AuNPs to produce AuNPs-S-C-ssDNA complex. In both strategies, C-ss DNA or HS-C-ssDNA could enhance the AuNPs stability against the salt-induced aggregation. However, the presence of Ag(I) ions in the obtained AuNPs/C-ssDNA or AuNPs-S-C-ssDNA complex would decrease such stability to display purple even blue colors due to the formation of Ag(I) ions mediated C-Ag(I)-C base pairs. Through this phenomenon, Ag(I) ions could be detected qualitatively and quantitatively using both unlabeled and labeled sensing strategies.

Polyethyleneimine-Functionalized Platinum Nanoparticles with High Electrochemiluminescence Activity and Their Applications to Amplified Analysis of Biomolecules

Polyethyleneimine-functionalized platinum nanoparticles (PtNPs) with excellent electrochemiluminescence (ECL) properties were synthesized and applied to the amplified analysis of biomolecules. These particles were prepared at room temperature, with hyperbranched polyethyleneimine (HBPEI) as the stabilizer. The UV/Vis absorption spectra and transmission electron microscopy images clearly confirmed the formation of monodisperse PtNPs. Such particles proved to possess high stability against salt-induced aggregation, enabling them to be employed even under high-salt conditions. Owing to the existence of many tertiary amine groups, these particles exhibited excellent ECL behavior in the presence of tris(2.2'-bipyridyl)ruthenium(II). An HBPEI-coated particle possessed an ECL activity that was at least 60 times higher than that of a tripropylamine molecule. Furthermore, these particles could be immobilized on the 3-aminopropyltriethoxysilane-treated quartz substrates to amplify the binding sites for carboxyl groups. Through this approach, PtNPs were applied to the amplified analysis of the hemin/G-quadruplex DNAzyme by using the luminol/H2O2 chemiluminescence method.

Photoinduced DNA Cleavage by alpha-, beta-, and gamma-Cyclodextrin-Bicapped C-60 Supramolecular Complexes

Water-soluble supramolecular inclusion complexes of alpha-, beta-, and gamma-cyclodextrin-bicapped C-60 (CD/C-60) have been investigated for their photoinduced DNA cleavage activities, with the aim to assess the potential health risks of this class of compounds and to understand the effect of host cyclodextrins having different cavity dimensions. Factors such as incubation temperature, irradiation time, and concentration of NADH or CDs/C-60 supramolecular inclusion complexes have been examined. The results show that alpha-, beta-, and gamma-CDs/C-60 are all able to cleave double-stranded DNA under visible light irradiation in the presence of NADH. However, a difference in the photoinduced DNA cleavage efficiency is observed, where the cleavage efficiency increases in the order of alpha-, beta-, and gamma-CD/C-60. The difference is attributed to the different aggregation behavior of the inclusion complexes in aqueous solution, which is correlated to the cavity dimension of the host cyclodextrin molecules.

Microstructures, mechanical properties and corrosion behavior of high-pressure die-cast Mg-4Al-0.4Mn-xPr (x=1, 2, 4, 6) alloys

Mg-4Al-0.4Mn-xPr (x = 1, 2, 4 and 6 wt.%) magnesium alloys were prepared successfully by the high-pressure die-casting technique. The microstructures, mechanical properties, corrosion behavior as well as strengthening mechanism were investigated. The die-cast alloys were mainly composed of small equiaxed dendrites and the matrix. The fine rigid skin region was related to the high cooling rate and the aggregation of alloying elements, such as Pr. With the Pr content increasing, the alpha-Mg grain sizes were reduced gradually and the amounts of the Al2Pr phase and All, Pr-3 phase which mainly concentrated along the grain boundaries were increased and the relative volume ratio of above two phases was changed. Considering the performance-price ratio, the Pr content added around 4 wt.% was suitable to obtain the optimal mechanical properties which can keep well until 200 degrees C as well as good corrosion resistance. The outstanding mechanical properties were mainly attributed to the rigid casting surface layer, grain refinement, grain boundary strengthening obtained by an amount of precipitates as well as solid solution strengthening.

Submicrometre scale single-crystalline gold plates of nanometre thickness: synthesis through a nucleobase process and growth mechanism

Synthesis of submicrometre scale single-crystalline gold plates of nanometre thickness in the presence of nucleobase guanine through chemical reduction of HAuCl4 was investigated. The elemental composition of the as-prepared gold nanoplates was estimated using energy-dispersive x-ray spectroscopy. The as-prepared gold plates were composed of essentially (111) lattice planes, as revealed by both x-ray diffraction (XRD) and transmission electron microscopy (TEM) results. It was found that the molar ratio of HAuCl4 to guanine played a very important role in the formation of gold nanoplates. Gold nanoplates could be produced at a molar ratio of [HAuCl4]/[guanine] = 50: 1 while only smaller gold spherical nanoparticles were obtained at molar ratios of [HAuCl4]/[guanine] <= 20:1. A possible growth mechanism of the as-prepared gold nanoplates is proposed and discussed. The results and conclusion presented in this work may be valuable for our further understanding of the roles of precursor ligands in the control of nanoparticles aggregation states and the preparation of shape-controlled nanoparticles.

Spontaneous formation of two-dimensional gold networks at the air-water interface and their application in surface-enhanced Raman scattering (SERS)

Two-dimensional (2-D) gold networks were spontaneously formed at the air-water interface after HAuCl4 reacted with fructose at 90 degrees C in a sealed vessel, in a reaction in which fructose acted as both a reducing and a protecting agent. Through fine-tuning of the molar ratio of HAuCl4 to fructose, the thus-formed 2-D gold networks can be changed from a coalesced pattern to an interconnected pattern. In the coalesced pattern, some well-defined single-crystalline gold plates at the micrometer-scale could be seen, while in the interconnected pattern, many sub-micrometer particles and some irregular gold plates instead of well-defined gold plates appeared. It is also found that the 2-D gold networks in the form of an interconnected pattern can be used as substrates for surface-enhanced Raman scattering (SERS) because of the strong localized electromagnetic field produced by the gaps between the neighboring particles in the 2-D gold networks.

Tight intermolecular packing through supramolecular interactions in crystals of cyano substituted oligo(para-phenylene vinylene): a key factor for aggregation-induced emission

Strong supramolecular interactions, which induced tight packing and rigid molecules in crystals of cyano substituent oligo(para-phenylene vinylene) (CN-DPDSB), are the key factor for the high luminescence efficiency of its crystals; opposite to its isolated molecules in solution which have very low luminescence efficiency.

Study of controllable aggregation morphology of ABA amphiphilic triblock copolymer in dilute solution by changing the solvent property

We have studied, both experimentally and theoretically, the aggregation morphology of the ABA amphiphilic triblock copolymer in dilute solution by changing the solvent property. Experimental results showed that the micellar morphology changed from spheres to rods and then to vesicles by changing the common solvent from N-N-dimethylformamide (DMF) to dioxane and then to tetrahydrofuran (THF). These controllable aggregates were also obtained by Monte Carlo simulation. The simulative results showed that the solvent property is a key factor that determines the copolymer aggregation morphology. The morphology changed from spheres to rods and then to vesicles by increasing the solvent solubility, corresponding to the change of stretched of the copolymer chains in the micellar cores. This result is in good agreement with the experimental one. Moreover, the simulative results revealed that the end-to-end distant of the ABA triblock copolymer in the vesicle was larger than that in the spheres and rods, indicating that the copolymer chains were more stretched in vesicles than in the spheres and rods. Furthermore, we gave the distribution of the fraction of the chain number with the end-to-end distance. The results indicated that the amount of folded chains is almost the same as that of stretched chains in the vesicle. Although most chains were folded, stretched chains could be found in the rod and sphere micelles.

Tunable synthesis, growth mechanism, and magnetic properties of La0.5Ba0.5MnO3

La0.5Ba0.5MnO3 products with novel flowerlike, microcube, and nanocube structures were successfully synthesized by a simple hydrothermal route by controlling the alkalinity of the reaction solutions. The synthesized products were systematically studied by X-ray powder diffraction, field-emission scanning electron microscopy, transmission electron microscopy, and energy dispersive X-ray spectroscopy. The results showed that the formation of the flowerlike structures with a layer assembly experienced a nucleation-aggregation-crystallization growth process, while the cubic structures experienced a nucleation-crystallization growth process due to the effect of different alkalinity in the reaction solutions. The higher alkalinity also led to a decrease in the size in the cubic structures. Suitable temperature and pressure were demonstrated to be crucial to the formation of the flowerlike structures by carrying out further control experiments. The measurement of the magnetic properties of three samples obtained at different alkaline conditions indicated that the size of the La0.5Ba0.5MnO3 products had an obvious influence on their properties; however, the dependence of the properties upon the morphology of the La0.5Ba0.5MnO3 products was minor.

Self-assembly of polypeptide-containing ABC-type triblock copolymers in aqueous solution and its pH dependence

Self-assembling of novel biodegradable ABC-type triblock copolymer poly(ethylene glycol)-poly(L-lactide)-poly(L-glutamic acid) (PEG-PLLA-PLGA) is studied. In aqueous media, it self-assembles into a spherical micelle with the hydrophobic PLLA segment in the core and the two hydrophilic segments PEG and PLGA in the shell. With the lengths of PEG and PLLA blocks fixed, the diameter of the micelles depends on the length of the PLGA block and on the volume ratio of H2O/dimethylformamide (DMF) in the media. When the PLGA block is long enough, morphology of the self-assembly is pH-dependent. It assembles into the spherical micelle in aqueous media at pH 4.5 and into the connected rod at or below pH 3.2. The critical micelle concentration (cmc) of the copolymer changes accordingly with decreasing solution pH. Both aggregation states can convert to each other at the proper pH value. This reversibility is ascribed to the dissociation and neutralization of the COOH groups in the LGA residues. When the PLGA block is short compared to the PEG or PLLA block, it assembles only into the spherical micelle at various pH values.

Preparation and antibacterial effects of PVA-PVP hydrogels containing silver nanoparticles

The poly(vinyl alcohol)/ poly(N-vinyl pyrrolidone) (PVA-PVP) hydrogels containing silver nanoparticles were prepared by repeated freezing-thawing treatment. The silver content in the solid composition was in the range of 0.1-1.0 wt %, the silver particle size was from 20 to 100 nm, and the weight ratio of PVA to PVP was 70 : 30. The influence of silver nanoparticles on the properties of PVA-PVP matrix was investigated by differential scanning calorimeter, infrared spectroscopy and UV-vis spectroscopy, using PVA-PVP films containing silver particles as a model. The morphology of freeze-dried PVA-PVP hydrogel matrix and dispersion of the silver nanoparticles in the matrix was examined by scanning electron microscopy. It was found that a three-dimensional structure was formed during the process of freezing-thawing treatment and no serious aggregation of the silver nanoparticles occurred. Water absorption properties, release of silver ions from the hydrogels and the antibacterial effects of the hydrogels against Escherichia coli and Staphylococcus aureus were examined too. It was proved that the nanosilver-containing hydrogels had an excellent antibacterial ability.