Nanoparticles Covered Surfaces for Post-functionalization with Aromatic Groups to Obtain Parahydrophobic Surface with High Water Adhesion (Petal Effect)

Numerous exceptional properties can be observed in nature.Among these properties,parahydrophobic feature is of interest.This property describes material with high adhesion with water such as rose petals or gecko foot.Such kind of surface presents a real potential for applications in the field of water harvesting systems.In this work,we report a new synthetic strategy to mimic this property.Here,we combine three strategies in one.First,a monomer is electropolymerized in order to form the starting structured surface.Then,nanoparticles are grafted on the surface to increase the structuration and consequently to create the reactive surface.Finally,the grafted surface is post-functionalized (Huisgen reaction) with various aryl alkynes to control the surface chemistry and energy.This strategy allows to reach surfaces with both very high hydrophobic properties (θ=140°) and high water adhesion.This work also includes the surface wettability,roughness and morphology investigation in order to study the impact of the starting monomer structure and post-functionalization on the surface properties.     

A Composite Gel Polymer Electrolyte with High Performance Based on Poly(Vinylidene Fluoride) and Polyborate for Lithium Ion Batteries

A composite membrane based on electrospun poly(vinylidene fluoride) (PVDF) and lithium polyvinyl alcohol oxalate borate (LiPVAOB) exhibiting high safety (self‐extinguishing) and good mechanical property is prepared. The ionic conductivity of the as‐prepared gel polymer electrolyte from this composite membrane saturated with 1 mol L^?1 LiPF₆ electrolyte at ambient temperature can be up to 0.26 mS cm^?1, higher than that of the corresponding well‐used commercial separator (Celgard 2730), 0.21 mS cm^?1. Moreover, the lithium ion transference in the gel polymer electrolyte at room temperature is 0.58, twice as that in the commercial separator (0.27). Furthermore, the absorbed electrolyte solvent is difficult to evaporate at elevated temperature. Its electrochemical performance is evaluated by using LiFePO₄ cathode. The obtained results suggest that this gel‐type composite membrane shows great possibilities for use in large‐capacity lithium ion batteries that require high safety.     

Synthesis,characterization and luminescence of europium perchlorate with MABA‐Si complex and coating structure SiO2@Eu(MABA‐Si) luminescence nanoparticles

This article reports a novel category of coating structure SiO₂@Eu(MABA‐Si) luminescence nanoparticles (NPs) consisting of a unique organic shell, composed of perchlorate europium(III) complex, and an inorganic core, composed of silica. The binary complex Eu(MABA‐Si)₃·(ClO₄)₃·5H₂O was synthesized using HOOCC₆H₄N(CONH(CH₂)₃Si(OCH₂CH₃)₃)₂ (MABA‐Si) and was used as a ligand. Furthermore, the as‐prepared silica NPs were successfully coated with the ‐Si(OCH₂CH₃)₃ group of MABA‐Si to form Si–O–Si chemical bonds by means of the hydrolyzation of MABA‐Si. The binary complexes were characterized by elemental analysis, molar conductivity and coordination titration analysis. The results indicated that the composition of the binary complex was Eu(MABA‐Si)₃·(ClO₄)₃·5H₂O. Coating structure SiO₂@Eu(MABA‐Si) NPs were characterized using transmission electron microscopy (TEM), scanning electron microscopy (SEM) and infrared (IR) spectra. Based on the SEM and TEM measurements, the diameter of core‐SiO₂ particles was ~400 and 600 nm, and the thickness of the cladding layer Eu(MABA‐Si) was ~20 nm. In the binary complex Eu(MABA‐Si)₃·(ClO₄)₃·5H₂O, the fluorescence spectra illustrated that the energy of the ligand MABA‐Si transferred to the energy level for the excitation state of europium(III) ion. Coating structure SiO₂@Eu(MABA‐Si) NPs exhibited intense red luminescence compared with the binary complex. The fluorescence lifetime and fluorescence quantum efficiency of the binary complex and of the coating structure NPs were also calculated. The way in which the size of core‐SiO₂ spheres influences the luminescence was also studied. Moreover, the luminescent mechanisms of the complex were studied and explained.     

A High‐Energy Density Asymmetric Supercapacitor Based on Fe2O3 Nanoneedle Arrays and NiCo2O4/Ni(OH)2 Hybrid Nanosheet Arrays Grown on SiC Nanowire Networks as Free‐Standing Advanced Electrodes

In this paper, a novel freestanding core‐branch negative and positive electrode material through integrating trim aligned Fe₂O₃ nanoneedle arrays (Fe₂O₃ NNAs) is first proposed with typical mesoporous structures and NiCo₂O₄/Ni(OH)₂ hybrid nanosheet arrays (NiCo₂O₄/Ni(OH)₂ HNAs) on SiC nanowire (SiC NW) skeletons with outstanding resistance to oxidation and corrosion, good conductivity, and large‐specific surface area. The original built SiC NWs@Fe₂O₃ NNAs is validated to be a highly capacitive negative electrode (721 F g^?1 at 2 A g^?1, i.e., 1 F cm^?2 at 2.8 mA cm^?2), matching well with the similarly constructed SiC NWs@NiCo₂O₄/Ni(OH)₂ HNAs positive electrode (2580 F g^?1 at 4 A g^?1, i.e., 3.12 F cm^?2 at 4.8 mA cm^?2). Contributed by the uniquely engineered electrodes, a high‐performance asymmetric supercapacitor (ASC) is developed, which can exhibit a maximum energy density of 103 W h kg^?1 at a power density of 3.5 kW kg^?1, even when charging the device within 6.5 s, the energy density can still maintain as high as 45 W h kg^?1 at 26.1 kW kg^?1, and the ASC manifests long cycling lifespan with 86.6% capacitance retention even after 5000 cycles. This pioneering work not only offers an attractive strategy for rational construction of high‐performance SiC NW‐based nanostructured electrodes materials, but also provides a fresh route for manufacturing next‐generation high‐energy storage and conversion systems.     

Terthieno[3,2‐b]Thiophene (6T) Based Low Bandgap Fused‐Ring Electron Acceptor for Highly Efficient Solar Cells with a High Short‐Circuit Current Density and Low Open‐Circuit Voltage Loss

A terthieno[3,2‐b]thiophene ( 6T ) based fused‐ring low bandgap electron acceptor, 6TIC , is designed and synthesized for highly efficient nonfullerene solar cells. The chemical, optical, and physical properties, device characteristics, and film morphology of 6TIC are intensively studied. 6TIC shows a narrow bandgap with band edge reaching 905 nm due to the electron‐rich π‐conjugated 6T core and reduced resonance stabilization energy. The rigid, π‐conjugated 6T also offers lower reorganization energy to facilitate very low V_OC loss in the 6TIC system. The analysis of film morphology shows that PTB7‐Th and 6TIC can form crystalline domains and a bicontinuous network. These domains are enlarged when thermal annealing is applied. Consequently, the device based on PTB7‐Th : 6TIC exhibits a high power conversion efficiency (PCE) of 11.07% with a high J_SC > 20 mA cm^?2 and a high V_OC of 0.83 V with a relatively low V_OC loss (≈0.55 V). Moreover, a semitransparent solar cell based on PTB7‐Th : 6TIC exhibits a relatively high PCE (7.62%). The device can have combined high PCE and high J_SC is quite rare for organic solar cells.     

Effects of rare earth ions (Tb,Ce, Eu,Dy) on the thermoluminescence characteristics of sol–gel derived and γ‐irradiated SiO2 nanoparticles

Highly pure SiO₂ and SiO₂:RE nanoparticles were synthesized by the sol–gel method. The morphological, structural and optical properties of the nanoparticles were characterized by X‐ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). XRD results indicate that all the samples studied were free from impurities. SEM/TEM results indicate that the samples were well dispersed. Surface characterization of the nanocrystals by Fourier transform infrared spectroscopy has been carried out and the structure of surface‐bound SiO₂ based on spectral analysis is proposed. Thermoluminescence (TL) characteristics were investigated to study the influence of rare earth dopants (Tb, Ce, Eu, Dy) on SiO₂ matrix subjected to 0.5 kG (1 h) γ‐irradiation. Among these rare earth elements, Eu³⁺ was found to be the most efficient dopant for SiO₂ showing maximum thermoluminescence intensity. SiO₂:Eu_0.5 seems to be a promising candidate for use as a TL dosimeter. Copyright © 2013 John Wiley & Sons, Ltd.     

Effect of Crystal Orientation and Conduction Band Grading of Absorber on Efficiency of Cu(In,Ga)Se2 Solar Cells Grown on Flexible Polyimide Foil at Low Temperature

Flexible Cu(In,Ga)Se₂ (CIGS) solar cells are developed on polyimide (PI) foil by using a three‐stage co‐evaporation method. To deposit CIGS on a PI substrate, low temperature deposition process (below 440 °C) is investigated. By optimizing the three‐stage process, power conversion efficiency (PCE) values of 12.1% and 13.6% are obtained at maximum process temperatures of 400 °C and 440 °C, respectively (without anti‐reflection coating). The CIGS absorber deposited at 400 °C is grown with (220)/(204) rather than (112) as its dominant growth orientation, accompanied by highly homogeneous crystal structure and phases. Admittance spectroscopy reveals that the defect levels were lower in the CIGS absorber with (220)/(204) dominant growth orientation, which could have contributed to the PCE of 12.1%. The CIGS solar cell deposited at a temperature of 440 °C exhibits worse defect characteristics compared to that fabricated at 400 °C. However, the CIGS solar cell fabricated below 440 °C exhibited marginal double‐grading of Ga/(Ga + In) in the absorber layer, which resulted in an improved PCE of 13.6%. This result implies that at a temperature below 440 °C, the double‐grading of Ga/(Ga + In) is the more dominant factor causing the PCE improvement above 13%.     

Potentiometric and spectroscopic studies on the solution molecular structures of copper(II)-[S]-2-[N-(2′-hydroxybenzyl)aminomethyl]pyrrolidine complexes, potential non-steroidal anti-inflammatory agents (NSAIDs)

The purpose of this study was to investigate the complexes formed by copper(II) with potential non-steroidal anti-inflammatory agents (NSAIDs) under physiological conditions. A former study suggested that 2-benzylaminomethylpyrrolidine ligands could be good candidates as potential OIL (OH-inactivating ligand) when complexed to copper(II). In order to assess the chemical behavior as OIL, [S]-2-[N-(2′-hydroxybenzyl)aminomethyl]pyrrolidine (OHbamp) was synthesized and bound to copper(II). Physico-chemical properties were determined at 37 °C in 0.15 M NaCl using glass electrode potentiometry, UV-Vis and circular dichroism spectroscopies, before and after copper(II) complexation. [Cu(OHbamp)(H₂O)₃]⁺ was the main complex found at both physiological and inflammatory pH values, showing appreciable stability at pathological pH compared to copper(II) complexes of histidine, the predominant low-molar-mass ligand of copper(II) in blood plasma. However, neutral species such as [Cu(OHbamp)₂(H₂O)₂] and [Cu(OHbamp)(OH)(H₂O)₃] are predominant only above pH 8, preventing a significant amount of drug from diffusing through membranes at inflammatory pH. In conclusion, copper(II)-OHbamp system does not meet all the requirements to be an OIL. Nevertheless, these results allow us to better identify the chemical features needed for a good OIL candidate.     

Immobilization of (1S,2R)-(+)-2-amino-1,2-diphenylethanol derivates on aminated silica gel with different linkages as chiral stationary phases and their enantioseparation evaluation by HPLC

A chiral selector was prepared through the reaction between (1S,2R)-(+)-2-amino-1,2-diphenylethanol and phenyl isocyanate. This selector was immobilized on aminated silica gel, respectively, with bifunctional group linkers of 1,4-phenylene diisocyanate, methylene-di-p-phenyl diisocyanate, and terephthaloyl chloride to produce corresponding three chiral stationary phases. The prepared compounds and chiral stationary phases were characterized by FT-IR, elemental analysis, (1)H NMR, and solid-state (1)H NMR. The enantioseparation ability of these chiral stationary phases was evaluated with structurally various chiral compounds. The chiral stationary phase prepared with 1,4-phenylene diisocyanate as linker showed excellent enantioseparation ability. The influence of different linkages on the enantioseparation was discussed.     

Lymphocyte subsets and T(h)1/T(h)2 immune responses in patients with adenocarcinoma of the oesophagus or oesophagogastric junction: relation to pTNM stage and clinical outcome

Introduction Recent studies have indicated that the cytokines produced by CD4⁺ T helper type 1 (T_h1) and type 2 (T_h2) cells are critically important in antitumour immunity and perhaps clinical outcome. From this perspective, we investigated the immunocompetence of patients with previously untreated cancer of the oesophagus or oesophagogastric junction (OGJ) in relation to stage of disease and postoperative survival.Methods Blood samples were taken prior to surgery from 32 patients with adenocarcinoma of the oesophagus or OGJ. Ten healthy volunteers served as normal controls. T-cell and monocyte subpopulations were determined using flow cytometry. Monocyte as well as T_h1- and T_h2-lymphocyte cytokine levels were assessed in stimulated whole blood cultures.Results Absolute T-cell and monocyte (subset) counts as well as monocyte cytokine levels were similar among patients and controls. Production of T_h1-type cytokines was higher in patients than in controls (IFN-, p=0.01; IL-2, p=0.05), whereas T_h2-type cytokine levels were comparable (IL-4, p=0.5; IL-13, p=0.3). T-cell CD4⁺/CD8⁺ ratios decreased as pTNM stage worsened (stage I/II vs stage III/IV, p=0.009). Of all measured immunological parameters, only IL-2 production significantly affected both overall survival (p=0.015) and disease-free survival (p=0.0062). High IL-2 levels corresponded with a favourable prognosis.Conclusions Patients awaiting surgery for adenocarcinoma of the oesophagus or oesophagogastric junction demonstrated a shift in the T_h1/T_h2 balance—in favour of T_h1—compared with healthy volunteers. The ability of T cells to produce IL-2 was related to survival indicating a crucial role of T_h1-type cells in antitumour immunosurveillance.     

Ablating both Fabp1 and Scp2/Scpx (TKO) induces hepatic phospholipid and cholesterol accumulation in high fat-fed mice

Although singly ablating Fabp1 or Scp2/Scpx genes may exacerbate the impact of high fat diet (HFD) on whole body phenotype and non-alcoholic fatty liver disease (NAFLD), concomitant upregulation of the non-ablated gene, preference for ad libitum fed HFD, and sex differences complicate interpretation. Therefore, these issues were addressed in male and female mice ablated in both genes (Fabp1/Scp2/Scpx null or TKO) and pair-fed HFD. Wild-type (WT) males gained more body weight as fat tissue mass (FTM) and exhibited higher hepatic lipid accumulation than WT females. The greater hepatic lipid accumulation in WT males was associated with higher hepatic expression of enzymes in glyceride synthesis, higher hepatic bile acids, and upregulation of transporters involved in hepatic reuptake of serum bile acids. While TKO had little effect on whole body phenotype and hepatic bile acid accumulation in either sex, TKO increased hepatic accumulation of lipids in both, specifically phospholipid and cholesteryl esters in males and females and free cholesterol in females. TKO-induced increases in glycerides were attributed not only to complete loss of FABP1, SCP2 and SCPx, but also in part to sex-dependent upregulation of hepatic lipogenic enzymes. These data with WT and TKO mice pair-fed HFD indicate that: i) Sex significantly impacted the ability of HFD to increase body weight, induce hepatic lipid accumulation and increase hepatic bile acids; and ii) TKO exacerbated the HFD ability to induce hepatic lipid accumulation, regardless of sex, but did not significantly alter whole body phenotype in either sex.     

Synthesis and chemiluminescence of copolymers of 5-amino-8-vinyl-phthalazine-1, 4(2H,3H)-dione with methyl methacrylate or styrene,and of α, ω-bis[5-amino-phthalazine-1,4 (2H,3H)-dion-]8-yl alkanes [=α, ω-bis(6-luminyl) alkanes]: Investigations on an intramolecular ‘distance effect’

Oligomers of 5-amino-8-vinyl-phthalazine-1,4(2H,3H)-dione exhibit about 0.05% of the chemiluminescence quantum yield of the corresponding ‘monomer unit’, i.e. 5-amino-8-ethyl-phthalazine-1,4(2H,3H)-dione which has a similar quantum yield to luminol. The quantum yields of copolymers of 5-amino-8-vinyl-phthalazine-1,4(2H,3H)-dione (1a) with methyl methacrylate or with styrene increase up to 1000-fold, relative to the quantum yield of oligomers of (1a). Thus the monomer units of methyl methacrylate or styrene appear to act as ‘spacers’ between the lumigenic groups. α,ω-Bis[(5-amino-phthalazine-1,4(2H,3H)-dion-)8-yl] alkanes show an analogue ‘distance’ effect: the chemiluminescence quantum yield increases with increasing alkane chain length. As the fluorescence of the corresponding amino phthalates (which are intermediates in the synthesis of the phthalazine diones) is only slightly influenced by the distance between the lumigenic groups it is suggested that a mainly chemical ‘distance effect’ is working here: the smaller the intramolecular distance between the hydrazide groups the more inhibition exists in respect of the oxidative reaction producing the luminol-type chemiluminescence.