Fingerprinting the degradation product patterns of different polyester‐ether networks by electrospray ionization mass spectrometry

Fingerprinting of the degradation product patterns by electrospray ionization mass spectrometry (ESI‐MS) was evaluated as a tool to monitor the degree of degradation in polyester‐ether networks. Four different crosslinked caprolactone (CL) and/or 1,5‐dioxepan‐2‐one (DXO) networks were subjected to hydrolytic degradation in aqueous solution at 37 °C for up to 147 days. After predetermined time periods, the water‐soluble degradation products were analyzed by ESI‐MS and tandem ESI‐MS. In addition, changes in pH, mass loss, and copolymer composition were determined. In the case of more slowly hydrolyzed CL‐rich (co)polymers, CL and/or DXO oligomers terminated by hydroxyl and carboxyl end groups were predominantly formed as degradation products. However, on prolonged hydrolysis oligomers with attached crosslinking agent dominated the degradation product patterns of more easily hydrolyzed DXO‐rich (co)polymers. It was shown that in the recorded mass spectra the variation of intensities in the series of ions corresponding to DXO and CL/DXO oligomers with or without attached crosslinking agent could be utilized to monitor the extent of hydrolytic degradation in the polyester matrix and the disruption of the network structure. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4617–4629, 2008     

Oxidation of elemental gold in alcohol solutions

Gold is designated as the noblest metal because of its chemical inertness. It is known to dissolve in cyanide solutions in the presence of air or H2O2 or in halogen-containing solutions, aqua regia being the most famous example. Herein, we report a unique thiol, especially 4-pyridinethiol (4-PS), assisted dissolution of Au in alcohol solutions. Although dissolution was found to be very selective for pyridinethiols, such a phenomenon is astonishing since thiols are commonly used as etch resists for Au and even 4-PS is extensively used as a surface modifier for Au. To gain further understanding of the dissolution process, the influence of the reaction conditions was extensively studied. On the basis of the obtained results, a mechanism for the dissolution reaction is proposed. Fascinatingly, by tuning of the reaction conditions, this phenomenon can be applied in selective preparation of self-supporting nanometer-thick Au foils.     

Grafting of hydroxymethylacrylamide and acrylic acid copolymer onto polyvinylidene fluoride membrane by supercritical carbon dioxide and its application in dye separation

We report a thermally induced graft copolymerization of acrylic acid and N‐hydroxymethylacrylamide onto polyvinylidene fluoride microporous membrane by using supercritical carbon dioxide as a solvent and carrier agent. The effects of monomer mole ratio, pressure, reaction temperature, time, and initiator concentration on the degree of grafting were investigated. The morphology of the grafted membrane was studied via scanning electron microscopy. Attenuated total reflectance infrared spectroscopy spectroscopy and X‐ray diffraction proved the existence of grafting monomers. The results of contact angle measurement and water filtration at different pH levels indicated pronounced pH‐sensitive behavior and increased hydrophilicity of the polyvinylidene fluoride grafted membrane. In particular, the grafted membrane was applied to the removal of methylene blue with a relative rejection of 98.1% compared with 30.5% of rejection observed from the pristine polyvinylidene fluoride membrane. Copyright © 2014 John Wiley & Sons, Ltd.     

Facile synthesis of polyoxometalate-thionine composite via direct precipitation method and its photocatalytic activity for degradation of rhodamine B under visible light

(TH)(3)PW(12) (TH=thionine, PW(12)=PW(12)O(40)(3-)) composite was prepared by direct precipitation of TH and PW(12). The (TH)(3)PW(12) was characterized via UV-vis spectrum, FT-IR, SEM, and BET surface area. PW(12) was intact during the precipitation process. The composite has a bar-like shape and relatively large surface area (Langmuir surface of (TH)(3)PW(12) was 31.59 m(2)g(-1), BET surface was 20.26 m(2)g(-1)). Using the material as the photocatalyst, rhodamine B (RhB) was efficiently bleached and mineralized under visible light irradiation (λ>420 nm). The kinetics of the photodecomposition follow the first-order reaction. The (TH)(3)PW(12) catalyst can be easily separated from the reaction system and has good stability for reuse.     

Mixed-phase PdRu bimetallic structures with high activity and stability for formic acid electrooxidation

Aiming at investigating the effect of structure on electrocatalytic properties, Pd(50)Ru(50) nanoparticles (NPs) with three different structures were carefully designed in a one-pot polyol process for application in formic acid electrooxidation. The three structures are: (1) single-phase PdRu nanodendrites (denoted as PR-1), (2) a mixed-phase mixture of PdRu nanodendrites and monometallic Ru NPs (denoted as PR-2), and (3) a mixed-phase mixture of monometallic Pd and Ru NPs (denoted as PR-3). From PR-1 to PR-3, the structure was varied from single-phase to mixed-phase. The relative position of Ru was altered from completely Pd-connected (PR-1), to a mixture of Pd-connected and monometallic (PR-2), and completely monometallic (PR-3). All PdRu NPs outperform the commercial Pd/C. PR-2 exhibits the highest peak current density, but its stability is slightly lower than that of PR-3. When both the current density and the durability are taken into consideration, PR-2 is the best choice of catalyst for formic acid oxidation. It indicates that both the Pd-connected Ru NPs and monometallic Ru NPs in the mixed-phase PR-2 are essential to improve the electrocatalytic properties. Our study also illustrates that the electrochemical active surface area (ECSA) and hydrogen storage capacity of the as-prepared PdRu NPs are greatly enhanced after several hundred scans in formic acid, indicating the possibility for highly restorable catalysts in direct formic acid fuel cells.     

Young children's recognition of quantitative relations in mathematically unspecified settings

Children have been found to be able to reason about quantitative relations, such as non-symbolic proportions, already by the age of 5 years. However, these studies utilize settings in which children were explicitly guided to notice the mathematical nature of the tasks. This study investigates children's spontaneous recognition of quantitative relations on mathematically unspecified settings. Participants were 86 Finnish-speaking children, ages 5–8. Two video-recorded tasks, in which participants were not guided to notice the mathematical aspects, were used. The tasks could be completed in a number of ways, including by matching quantitative relations, numerosity, or other aspects. Participants’ matching strategies were analyzed with regard to the most mathematically advanced level utilized. There were substantial differences in participants’ use of quantitative relations, numerosity and other aspects in their matching strategies. The results of this novel experimental setting show that investigating children's spontaneous recognition of quantitative relations provides novel insight into children's mathematical thinking and furthers the understanding of how children recognize and utilize mathematical aspects when not explicitly guided to do so.     

A Supramolecular Hydrogen‐Bonded Network as a Diffusion Barrier for Metal Adatoms

Confined in a molecular corral : A supramolecular network changes the mechanism by which underpotential deposition (UPD) of copper proceeds on a gold electrode modified by a self‐assembled monolayer (SAM). Lateral diffusion of Cu adatoms is suppressed between adjacent cells of a network/SAM hybrid structure. Instead, UPD occurs by direct deposition into the SAM filled pores of the network, where the Cu adatoms are confined.

     

Negative gastrointestinal contrast enhancement and image distortion induced by superparamagnetic particles at 0.02 Tesla

Gastrointestinal contrast enhancement and image distortion induced by superparamagnetic particles were evaluated in vitro and in rabbits at 0.02 Tesla. Test tubes containing 0.01–1.0 mg particles/ml were imaged in an oil or water bath in order to demonstrate the concentration-dependent signal void and image distortion in vitro at several pulse sequences. The lowest concentration of particles tested clearly decreased the signal intensity. Image distortion was observed when the concentration exceeded 0.07 mg/ml and was more pronounced on the T₂-weighted images. The in vitro T₂ relaxation time decreased from 122 ms to 56 ms with an increase in the particle concentration from 0.01 to 0.06 mg/ml. A loss of the GI-tract signal was observed in rabbits after the administration of 1 mg particles/kg, given as a 0.03 mg/ml suspension. At a dose of 20 mg/kg (0.6 mg/ml suspension) significant image distortion was observed.     

疏水载流子传输层上制备高效钙钛矿太阳电池的锚固策略

几种常用的导电聚合物(如PTAA(聚三芳基胺))具有优良的光电特性,因此适合用作钙钛矿太阳电池中的空穴传输材料来提升器件性能.然而,这些材料的疏水特性导致难以形成致密且高质量的钙钛矿薄膜.此外,即使通过一些方法实现载流子传输层与钙钛矿膜之间的接触,但界面处也会存在严重的载流子复合.同时,这样制备出的粗糙钙钛矿薄膜会导致后续沉积在钙钛矿薄膜上的电子传输层的非均匀覆盖.因此,在疏水载流子传输层上实现良好钙钛矿薄膜沉积以获得优良器件性能仍然具有很大挑战性.在本研究中,利用PbI2进行锚固工程被证明是一种简便、绿色且有效的方法,可有效解决疏水载流子传输层浸润性问题.通过本方法,钙钛矿薄膜质量和器件性能得到了显著提高,并获得了效率高达19.53;的器件.同时,本方法也普遍适用于其他疏水的载流子传输层,进而制备优异的钙钛矿薄膜,这为高性能钙钛矿太阳电池的发展提供了一种可行策略.