Synthesis and characterization of fluorine-containing cholesteric liquid crystalline polysiloxanes bearing trifluoromethyl-substituted mesogens

A series of side-chain liquid crystal (LC) polysiloxanes were synthesised with Poly(methylhydrogeno)siloxane, 4?-(undec-10-enoyloxy) biphenyl – 4 – yl 4- (trifluoromethyl) benzoate (M_th) and a chiral nematic (N*) LC monomer 1-allyl 10-(cholesteryl)-decanedioate (M_ch). The chemical structures and LC properties of the monomers and polymers were characterised by FTIR, ¹H-NMR, differential scanning calorimetry, thermogravimetric analysis, POM and X-ray diffractometer. M_ch is monotropic N* LC. The homopolymer derived from monomer M_ch is enantiotropic N* LC. Monomer M_th is a smectic A liquid crystal. The copolymers derived from M_ch and M_th are N* LCs. The temperatures at which 5% weight loss occurred are greater than 300°C for all the fluoro-containing polymers, and the residue weights of the samples at 600°C increased slightly as the content of trifluoromethyl mesogens increased in the polymers. The glass transition temperatures of the polymers increased as trifluoromethyl mesogens increased, too. The N*–I phase transition temperatures show a negative deviate from ideal or linear behaviour. The values of the enthalpy changes for the cholesteryl containing polymers are rather low and this is attributed to the biaxiality of cholesteryl moiety which tends to reduce the change in the orientational order at the N*–I transition. Compared to the monomers, the polymers show wider mesophase region.     

Mechanism studies of thermolysis process in copolyamide 66 containing triaryl phosphine oxide

Thermolysis behavior of flame-retardant copolyamide 66 (FR-PA66) in the presence of triaryl phosphine oxide (TPO) has been studied using different techniques such as differential scanning calorimetry, thermal gravimetric analysis, Fourier transform-infrared spectroscopy, and gas chromatography–mass spectrometry. The results indicate that TPO extends the thermolysis time of FR-PA66, and improves the thermolysis temperature. A three-stage mechanism for the decomposition of FR-PA66 has been proposed in this article. In the first stage, cleavage of P–C bond takes place in FR-PA66, while in the second stage, cleavage of polyamide chain occurs mainly. In the third stage, formation of cyclic compounds proceeds along with the formation of carbonized protective layer on the degraded polymer.     

Spectroscopic fingerprints of valence and spin states in manganese oxides and fluorides

We performed a systematic study of soft X-ray absorption spectroscopy in various manganese oxides and fluorides. Both Mn L-edges and ligand (O and F) K-edges are presented and compared with each other. Despite the distinct crystal structure and covalent/ionic nature in different systems, the Mn-L spectra fingerprint the Mn valence and spin states through spectral lineshape and energy position consistently and evidently. The clear O- and F-K pre-edge features in our high resolution spectra enable a quantitative definition of the molecular orbital diagram with different Mn valence. In addition, while the binding energy difference of the O-1s core electrons leads to a small shift of the O-K leading edges between trivalent and quadrivalent manganese oxides, a significant edge shift, with an order of magnitude larger in energy, was found between divalent and trivalent compounds, which is attributed to the spin exchange stabilization of half-filled 3d system. This shift is much enhanced in the ionic fluoride system. This work provides the spectroscopic foundation for further studies of complicated Mn compounds.     

Enhanced Sensitive Electrochemical Sensor for Simultaneous Catechol and Hydroquinone Detection by Using Ultrasmall Ternary Pt-based Nanomaterial

The simple and effective method for the novel synthesis of Pt-based nanoparticle was presented with high efficiency. The sensitive catalyst for the simultaneous detection of catechol and hydroquinone was prepared by depositing ternary metal complex on fluorine-doped tin-oxide (FTO). The composition and morphology of nanomaterials were characterized by TEM, HRTEM, XRD, XPS, and EDS (energy dispersive spectroscopy). The size of the Pt-based nanomaterial was about 5±1 nm. The electrochemical performance of the modified catalyst was studied by CV, DPV, and EIS. The modified PtNiCu@FTO catalyst possessed good electro-oxidation activity for hydroquinone and catechol and used for simultaneous detection of catechol and hydroquinone at scan rate of 20 mV s⁻¹ (vs. Ag/AgCl). Detection responses were found in the ranges of 5–2900 μM for hydroquinone and 5–3000 μM for catechol. The detection limits (LOD) for HQ and CC were observed as 0.35 and 0.29 μM, respectively. The sensitivity of HQ and CC were 1515.55 and 1485 μA mM⁻¹ cm⁻², respectively. The prepared nanomaterial were effectively applied for the determination of CC and HQ in real samples.     

Dynamic mechanical relaxation and thermal creep of high-entropy La30Ce30Ni10Al20Co10 bulk metallic glass

Spatial frequency shift(SFS) microscopy with evanescent wave illumination shows intriguing advantages, including large field of view(FOV), high speed, and good modularity. However, a missing band in the spatial frequency domain hampers the SFS superresolution microscopy from achieving resolution better than 3 folds of the Abbe diffraction limit. Here, we propose a novel tunable large-SFS microscopy, making the resolution improvement of a linear system no longer restricted by the detection numerical aperture(NA). The complete wide-range detection in the spatial frequency domain is realized by tuning the illumination spatial frequency actively and broadly through an angle modulation between the azimuthal propagating directions of two evanescent waves. The vertical spatial frequency is tuned via a sectional saturation effect, and the reconstructed depth information can be added to the lateral superresolution mask for 3D imaging. A lateral resolution of λ/9, and a vertical localization precision of ~λ/200(detection objective NA = 0.9) are realized with a gallium phosphide(GaP) waveguide. Its unlimited resolution enhancing capability is demonstrated by introducing a designed metamaterial chip with an unusual large refractive index. Besides the great resolution enhancement, this method shows better anti-noise capability than classical structured illumination microscopy without SFS tunability. This method is chip-compatible and can potentially provide a massproducible illumination chip module achieving the fast, large-FOV, and deep-subwavelength 3D nanoscopy.     

Polypyrrole Shell@3D‐Ni Metal Core Structured Electrodes for High‐Performance Supercapacitors

Three‐dimensional (3D) nanometal films serving as current collectors have attracted much interest recently owing to their promising application in high‐performance supercapacitors. In the process of the electrochemical reaction, the 3D structure can provide a short diffusion path for fast ion transport, and the highly conductive nanometal may serve as a backbone for facile electron transfer. In this work, a novel polypyrrole (PPy) shell@3D‐Ni‐core composite is developed to enhance the electrochemical performance of conventional PPy. With the introduction of a Ni metal core, the as‐prepared material exhibits a high specific capacitance (726 F g^?1 at a charge/discharge rate of 1 A g^?1), good rate capability (a decay of 33 % in C_sp with charge/discharge rates increasing from 1 to 20 A g^?1), and high cycle stability (only a small decrease of 4.2 % in C_sp after 1000 cycles at a scan rate of 100 mV s^?1). Furthermore, an aqueous symmetric supercapacitor device is fabricated by using the as‐prepared composite as electrodes; the device demonstrates a high energy density (≈21.2 Wh kg^?1) and superior long‐term cycle ability (only 4.4 % and 18.6 % loss in C_sp after 2000 and 5000 cycles, respectively).     

Thermal stability of soil organic matter was affected by 23-yr maize and soybean continuous cultivation in northeast of China

Long-term continuous cropping affects the biochemical quality of soil organic matter (SOM), but whether the effects are relevant with their thermal stability is less clear. In northeast China, long-term continuous cropping occurred frequently owing to higher yield and economic interest requirement. To verify the thermal stability properties of SOM affected by the long-term continuous cropping, the study focused on 23-yr continuous cultivated maize and soybean plots, where the effect of cropping is likely to be detected. Bulk soils sampled in 1991 and 2014 were studied by thermogravimetry and differential scanning calorimetry (DSC). The results showed typical bimodal peaks in DSC curve in bulk Mollisols. A labile fraction peak was observed at 354–366 °C low-temperature zone and recalcitrant fraction one at high temperature of 430–438 °C. Energy density (J mg^?1 OM) was greater in soybean plots compared to maize plots; in contrast, long-term continuous maize cultivation also increased energy density, in reverse in soybean plots after 23-yr cultivation. The DSC-T₅₀, temperature at which half of energy release occurred, typically showed larger responses to long-term cultivation than crop species. Results obtained support the hypothesis of a potential link between long-term continuous cropping and the thermal stability of SOM, and a correlation with crop species.     

Generally applicable and efficient esterification of aldehydes with alcohols catalyzed by cyclopalladated ferrocenylimine

The palladacycle‐catalyzed esterification of a variety of aldehydes with alcohols was developed. This reaction allows formation of esters in moderate to excellent yields not only for various aldehydes but also alcohols. In addition, the esterification could proceed well under mild conditions with a low catalyst loading of 0.0625 mol%. Copyright © 2013 John Wiley & Sons, Ltd.