蓄能发光功能涂料研究及其应用

介绍了蓄能发光涂料中所用发光材料的种类与性能特点，阐述了目前稀土铝酸盐长余辉蓄能发光材料的研究成果及作为涂料添加剂的表面改性处理；列举了蓄能发光涂料在建筑装饰、消防安全等领域的应用，对其存在的问题和发展趋势进行了探讨；同时简述了相关的研究。     

稀土Eu掺杂的NaYF_4发光材料的制备及性能研究

稀土离子因其独特的电子结构,使稀土掺杂发光材料具有光化学稳定、荧光寿命长、发射光谱窄等优点。本文采用水热合成法制得六方相Na YF4:Eu3+发光材料;采用XRD、SEM、荧光光谱仪等测试技术手段对物相组成、颗粒尺寸、形貌、荧光强度进行了分析。     

聚合物发光材料发光波长及效率的组成和结构调控

介绍了聚合物电致发光材料的种类、结构及性能特点,阐述了聚合物电致发光材料的结构与其发光波长的关系,讨论了聚合物光电材料发光波长和效率的组成和结构调控。     

水热法制备稀土元素掺杂二氧化锡及其对乙醇气敏性能

利用水热法制备了SnO2粉末及掺杂不同稀土离子的SnO2粉末. 通过XRD和气敏测试仪对其结构和性能进行了表征和测试. 结果表明,所制备的SnO2粉末呈四方金红石结构,稀土离子的掺入并没有改变SnO2的晶体结构,也无新晶相的出现. 掺杂镧的SnO2样品(SnO2:La)对乙醇有较高的气敏性. 分析了气敏机理. SnO2:La的灵敏度随着乙醇浓度的增加而增加,随温度的升高呈现波动状,且当温度在250℃时,SnO2:La对1.00′10-4乙醇的灵敏度最大,可达到101.1. 在此条件下其响应时间和恢复时间约为5 s.     

Chemical bond characteristics and infrared reflectivity spectrum of a novel microwave dielectric ceramic CaIn2O4 with near-zero τf

Orthorhombic-structured CaIn₂O₄ ceramics with a space group Pca2₁ were synthesized via a solid-state reaction method. A high relative density (95.6 %) and excellent microwave dielectric properties (ε_r ～11.28, Qf = 74,200 GHz, τ_f ～ ?4.6 ppm/°C) were obtained when the ceramics were sintered at 1375 °C for 6 h. The dielectric properties were investigated on the basis of the Phillips–Van Vechten–Levine chemical bond theory. Results indicated that the dielectric properties were mainly determined by the InO bonds in the CaIn₂O₄ ceramics. These bonds contributed more (74.65 %) to the dielectric constant than the CaO bonds (25.35 %). Furthermore, the intrinsic dielectric properties of the CaIn₂O₄ ceramics were investigated via infrared reflectivity spectroscopy. The extrapolated microwave dielectric properties were ε_r ～10.12 and Qf = 112,200 GHz. Results indicated that ion polarization is the main contributor to the dielectric constant in microwave frequency ranges.     

Fast NMR Methods for Measuring in the Direct and/or Competition Mode the Dissociation Constants of Chemical Fragments Interacting with a Receptor

Ligand-based NMR screening represents a powerful method in fragment-based drug discovery for the identification of chemical matter interacting with the receptor of interest. The large dynamic range of these methods allows the detection of weakly binding ligands. However, the methodology has not been extensively used for quantifying the strength of these interactions. This knowledge is important for ranking fragments according to their binding strength and for prioritizing structure-based and medicinal chemistry activities. Rapid NMR methods for measuring the dissociation constant in direct and competition modes are presented here. The theory underpinning these methods are presented, along with their application to the measurement of the binding affinities of several ligands of the heat shock protein 90.     

NMR Investigation of the Supramolecular Complex Formed by a Phenylboronic Acid-Ferrocene Electroactive Probe and Native or Derivatized β-Cyclodextrin

Specifically designed electrochemical sensors are standing out as alternatives to enzyme-based biosensors for the sensing of metabolites. In our previous works, we developed a new electrochemical assay based on cyclodextrin supramolecular complexes. A ferrocene moiety (Fc) was chemically modified by phenylboronic acid (4-Fc-PB) and combined with two different kinds of cyclodextrins (CDs): β-CD and β-CD modified by a dipicolylamine group (dpa-p-HB-β-CDs) for the sensing of fructose and adenosine-triphosphate (ATP), respectively. The aim of the present work is to better comprehend the features underlining the aforementioned complex formation. For the first time, a study about inclusion phenomena between the 4-Fc-PB electroactive probe with β-CD and with dpa-p-HB-β-CD was performed by using nuclear magnetic resonance (NMR) analysis. In particular, we focused on providing insights on the interaction involved and on the calculation of the binding constant of 4-Fc-PB/β-CD supramolecular complex, and elucidation about a drift in the time observed during the control experiments of the electrochemical measurements for the 4-Fc-PB/dpa-p-HB-β-CD supramolecular complex. In this sense, this paper represents a step further in the explanation of the electrochemical results obtained, pointing out the nature of the interactions present both in the formation of the inclusions and in the sensing with the analytes.     

Unraveling the Interaction between the LPS O‐Antigen of Burkholderia anthina and the 5D8 Monoclonal Antibody by Using a Multidisciplinary Chemical Approach,with Synthesis,NMR, and Molecular Modeling Methods

The interaction between the O‐chain from the lipopolysaccharide from Burkholderia anthina and a lipopolysaccharide‐specific monoclonal antibody (5D8) has been studied at high resolution by NMR spectroscopy. In particular, the 5D8‐bound epitope of the saccharide entity has been unraveled by a combination of saturation transfer difference (STD) and transferred NOESY (tr‐NOESY) experiments performed on the 5D8/polysaccharide complex. To dissect the fine details of the molecular recognition events, further experiments with simpler carbohydrate ligands were carried out. Thus, experiments were also performed with ad hoc synthesized trisaccharide and hexasaccharide O‐antigen repeating units. By using this multidisciplinary approach (chemical synthesis, NMR spectroscopy and molecular dynamics simulation), determination of the binding epitope and the contribution to the binding of the sugar units composing the O‐chain have been determined.     

Characterization of a coating layer on glass fibre used as reinforcing material in a polyepoxide matrix by means of FTIR spectroscopy and vapour phase interaction studies with monofunctional model compounds

Coatings on glass fibres, used to reinforce polyepoxide matrices, were examined by Fourier transform infra-red spectroscopy and by their reaction with styrene oxide, aniline, and also water in the vapour phase which was followed calorimetrically and gravimetrically. The coatings comprised an adhesive (of the DGEBA epoxy prepolymer type) applied on its own or together with a coupling agent (γ aminopropyltriethoxysilane). In all tests, these fibres were compared with untreated fibres of a similar type. The results of the studies indicate that the combination of the two coatings forms a reactive mixture within themselves which may inhibit uniform coating of the glass. It is also shown that the coating products on the glass control the process of water diffusion.     

Role of Conserved Residues and F322 in the Extracellular Vestibule of the Rat P2X7 Receptor in Its Expression,Function and Dye Uptake Ability

Activation of the P2X7 receptor results in the opening of a large pore that plays a role in immune responses, apoptosis, and many other physiological and pathological processes. Here, we investigated the role of conserved and unique residues in the extracellular vestibule connecting the agonist-binding domain with the transmembrane domain of rat P2X7 receptor. We found that all residues that are conserved among the P2X receptor subtypes respond to alanine mutagenesis with an inhibition (Y51, Q52, and G323) or a significant decrease (K49, G326, K327, and F328) of 2′,3′-O-(benzoyl-4-benzoyl)-ATP (BzATP)-induced current and permeability to ethidium bromide, while the nonconserved residue (F322), which is also present in P2X4 receptor, responds with a 10-fold higher sensitivity to BzATP, much slower deactivation kinetics, and a higher propensity to form the large dye-permeable pore. We examined the membrane expression of conserved mutants and found that Y51, Q52, G323, and F328 play a role in the trafficking of the receptor to the plasma membrane, while K49 controls receptor responsiveness to agonists. Finally, we studied the importance of the physicochemical properties of these residues and observed that the K49R, F322Y, F322W, and F322L mutants significantly reversed the receptor function, indicating that positively charged and large hydrophobic residues are important at positions 49 and 322, respectively. These results show that clusters of conserved residues above the transmembrane domain 1 (K49–Y51–Q52) and transmembrane domain 2 (G326–K327–F328) are important for receptor structure, membrane expression, and channel gating and that the nonconserved residue (F322) at the top of the extracellular vestibule is involved in hydrophobic inter-subunit interaction which stabilizes the closed state of the P2X7 receptor channel.     

Evaluation on the optical properties of Ga2O3−x thin films co-doped with Tb and transition metals (Mn,Cr) prepared by a photochemical route

Gallium β-diketonate complexes were studied as precursors for the photochemical deposition of amorphous thin films of gallium oxide doped with terbium and co-doped with chromium or manganese. Solutions of the inorganic complexes were spin coated on Si(100) and quartz substrates and photolyzed at room temperature using 254 nm UV light. The photolysis of these films induces the fragmentation of the complexes and the partial reduction of the metal ion together with the release of volatile organic compounds as sub-products. When the metallic complexes are irradiated under air, the products of the reactions are metal oxide thin films. The photochemical reactivity of these films was monitored by UV–vis spectroscopy, followed by a post-annealing treatment. The obtained films were characterized by X-ray photoelectron spectroscopy and X-ray diffraction. The optical properties of the films showed that these are highly transparent in the visible spectrum but decrease significantly in doped and co-doped films. Under UV light excitation (254 nm) the doped films (Ga₂O_3−x/Tb) show the characteristic emissions at 486, 530, 542 and 610 nm associated to ⁵D₄→⁷F_J (J=6,5,4,3) transitions of Tb⁺³ ion. However, these emissions decrease and deteriorate in the co-doped films (Ga₂O_3−x/Tb/M, where M=Mn or Cr). A possible emission mechanism and energy transfer have been proposed.     

Characterization of polymeric film of a new manganese phthalocyanine complex octa-substituted with 2-diethylaminoethanethiol, and its use for the electrochemical detection of bentazon

Manganese acetate octakis-(2-diethyaminoethanethiol) phthalocyanine (AcMnODEAETPc) was newly synthesized and characterized by spectroscopic and electrochemical methods. Solution electrochemistry of the complex showed three redox processes assigned to Mn^IIIPc⁻¹/Mn^IIIPc⁻², Mn^IIIPc⁻²/Mn^IIPc⁻² and Mn^IIPc⁻²/Mn^IIPc⁻³ species. The new molecule was polymerized onto a glassy carbon electrode (GCE) to form thin films of different thickness, giving poly-10-AcMnODEAETPc-GCE, poly-20-AcMnODEAETPc-GCE and poly-30-AcMnODEAETPc-GCE, where 10, 20 and 30 represent the number of voltammetry scans during polymerization. Three distinct redox processes were observed on the modified electrode in 0.1 M phosphate buffer solution, pH 5, which confirmed the formation of the polymer. The current signal due to the herbicide, bentazon, was dependent on film thickness; the best signal was obtained on poly-20-AcMnODEAETPc-GCE while poly-10-AcMnODEAETPc-GCE gave the least signal. However, the signals due to the herbicide were better on the different films compared to the bare electrode. Electrochemical impedance spectroscopy (EIS) technique revealed that differences in film thickness offered different charge transfer resistances, R_ct, hence difference in current signals for bentazon oxidation were observed on these films. A Tafel slope of 77 mV/decade, obtained for the herbicide on poly-20-AcMnODEAETPc-GCE, denotes a fast one electron transfer followed by a slow chemical step in the electro-oxidation of bentazon. The voltammetry signals of the herbicide on the films indicated the likely involvement of ring-based redox processes in the detection of the herbicide. A plot of background corrected current response, on this film, versus the concentration of bentazon was linear within the range 50–750 μM with a detection limit of 2.48 × 10⁻⁷ M.     

Targeting the S100A2-p53 Interaction with a Series of 3,5-Bis(trifluoromethyl)benzene Sulfonamides: Synthesis and Cytotoxicity

In silico approaches identified 1 , N-(6-((4-bromo- benzyl)amino)hexyl)-3,5-bis(trifluoromethyl)benzene sulfonamide, as a potential inhibitor of the S100A2-p53 protein-protein interaction, a validated pancreatic cancer drug target. Subsequent cytotoxicity screening revealed it to be a 2.97 μM cell growth inhibitor of the MiaPaCa-2 pancreatic cell line. This is in keeping with our hypothesis that inhibiting this interaction would have an anti-pancreatic cancer effect with S100A2, the validated PC drug target. A combination of focused library synthesis (three libraries, 24 compounds total) and cytotoxicity screening identified a propyl alkyl diamine spacer as optimal; the nature of the terminal phenyl substituent had limited impact on observed cytotoxicity, whereas N-methylation was detrimental to activity. In total 15 human cancer cell lines were examined, with most analogues showing broad-spectrum activity. Near uniform activity was observed against a panel of six pancreatic cancer cell lines: MiaPaCa-2, BxPC-3, AsPC-1, Capan-2, HPAC and PANC-1. In all cases there was good to excellent correlation between the predicted docking pose in the S100A2-p53 binding groove and the observed cytotoxicity, especially in the pancreatic cancer cell line with high endogenous S100A2 expression. This supports S100A2 as a pancreatic cancer drug target.     

Synthesis of a soluble functionalized-silica by the hydrolysis and condensation of organotrialkoxysilanes bearing (β-hydroxy) tertiary amine groups with tetraethoxysilane

The hydrolytic condensation of organotrialkoxysilanes containing (β-hydroxy) tertiary amine groups generates a significant fraction of intramolecular cycles and leads to the formation of closed structures. The aim of this study was to investigate if their co-condensation with a tetraalkoxy silane would take place by predominant intramolecular cyclization steps, eventually leading to functionalized silicas that can be dissolved in appropriate solvents. Co-condensation of tetraethoxysilane (TEOS) with the organotrialkoxysilane derived from the reaction of N-(β-aminoethyl)-γ-aminopropyl trimethoxysilane with phenyl glycidyl ether, was performed in the presence of HCOOH using a thermal cycle attaining 150 °C. For TEOS molar fractions lower than 0.7, soluble functionalized-silicas containing up to about 25 wt% of inorganic silica chemically bonded to bulky organic groups, could be synthesized. The glass transition temperature of the organic part was close to 25 °C; it was inferred that the inorganic part was vitrified at the maximum temperature of the selected thermal cycle (150 °C). Most of the Si atoms supplied by the trialkoxysilane were present in fully condensed structures (T³), while those supplied by TEOS were present mostly as Q³ and Q⁴ structures. These soluble functionalized-silicas may be used to introduce silica as a reinforcement of a polymer network. An example is shown, using an epoxy-diamine formulation. The equivalent of 10 wt% silica could be incorporated to the final network at the expense of a reduction of 26 °C in its glass transition temperature.     

Enzymatic Interesterification of Extra Virgin Olive Oil with a Fully Hydrogenated Fat: Characterization of the Reaction and Its Products

The lipase-catalyzed interesterification of extra virgin olive oil (EVOO) and fully hydrogenated palm oil (FHPO) was studied in a batch reactor operating at 75 °C. The compositions of the semi-solid fat products depend on the reaction conditions and the initial ratio of EVOO to FHPO. The dependence of the quasi-equilibrium product TAG profile on the reaction time was determined for initial weight ratios of EVOO to FHPO from 80:20 to 20:80. Lipozyme TL IM, Lipozyme RM IM and Novozym 435 were employed as biocatalysts. The interesterification reaction was optimized with respect to the type and loading of biocatalyst. Equilibrium was approached in the shortest time with Novozym 435 (80% conversion in 4 h). The chemical, physical, and functional properties of the products were characterized. Appropriate choices of the reaction conditions and the initial ratio of EVOO to FHPO lead to TAG with melting profiles and solid fat contents similar to those of commercial products. Differences were observed in the solid fat contents, melting profiles, and oxidative stabilities of the various interesterified products and also between the indicated properties of each category of product and the corresponding physical blend of the precursor reagents.     

Measurement of the Interaction Between Recombinant I-domain from Integrin alpha 2 beta 1 and a Triple Helical Collagen Peptide with the GFOGER Binding Motif Using Molecular Force Spectroscopy

The role of the collagen-platelet interaction is of crucial importance to the haemostatic response during both injury and pathogenesis of the blood vessel wall. Of particular interest is the high affinity interaction of the platelet transmembrane receptor, alpha 2 beta 1, responsible for firm attachment of platelets to collagen at and around injury sites. We employ single molecule force spectroscopy (SMFS) using the atomic force microscope (AFM) to study the interaction of the I-domain from integrin alpha 2 beta 1 with a synthetic collagen related triple-helical peptide containing the high-affinity integrin-binding GFOGER motif, and a control peptide lacking this sequence, referred to as GPP. By utilising synthetic peptides in this manner we are able to study at the molecular level subtleties that would otherwise be lost when considering cell-to-collagen matrix interactions using ensemble techniques. We demonstrate for the first time the complexity of this interaction as illustrated by the complex multi-peaked force spectra and confirm specificity using control blocking experiments. In addition we observe specific interaction of the GPP peptide sequence with the I-domain. We propose a model to explain these observations.     

Permeability and corrosion resistance of the porous alumina doped by Y2O3 with monodispersed PMMA as pore former

Porous alumina, with monodispersed PMMA as pore former and Y₂O₃ as sintering additive, was prepared via a gel casting route with Isobam as a gelling agent. The effects of PMMA addition on its properties, including apparent porosity, bulk density, strength, permeability, and corrosion resistance to acid/alkali, were investigated. With PMMA addition increased, the apparent porosity and permeability were increased obviously, while strength and corrosion resistance to acid/alkali were deteriorated due to increased porosity. Higher firing temperature resulted in lower porosity, higher strength, lower permeability, and better corrosion resistance to acid/alkali. Coarser raw powders resulted in lower strength and higher permeability due to the coarser structure and larger pores of the fabricated samples. Because Y₂O₃ was used as a sintering additive, and no silica was introduced, the resulting samples possess better corrosion resistance to acid and alkali, especially much better corrosion resistance to alkali, than those reported with silica introduced.     

Kinetics of the Interactions between Copper and Amyloid‐β with FAD Mutations and Phosphorylation at the N terminus

Mutations and post‐translational modifications of amyloid‐β (Aβ) peptide in its N terminus have been shown to increase fibril formation, yet the molecular mechanism is not clear. Here we investigated the kinetics of the interactions of copper with two Aβ peptides containing Familial Alzheimer's disease (FAD) mutations (English (H6R) and Tottori (D7N)), as well as with Aβ peptide phosphorylated at serine 8 (pS8). All three peptides bind to copper with a similar rate as the wild‐type (wt). The dissociation rates follow the order pS8>H6R>wt>D7N; the interconversion between the two coordinating species occurs 50 % faster for H6R and pS8, whereas D7N had only a negligible effect. Interestingly, the rate of ternary complex (copper‐bridged heterodimer) formation for the modified peptides was significantly faster than that for wt, thus leading us to propose that FAD and sporadic AD might share a kinetic origin for the enhanced oligomerisation of Aβ.     

Electrochemical behavior of Ge and GeX2 (X = O, S) glasses: Improved reversibility of the reaction of Li with Ge in a sulfide medium

Sulfide glasses have been considered as new anode materials for lithium-ion batteries because their high ionic conductivity (approximately ≥10⁻⁴ S/cm) (more than one order of magnitude higher than oxide glasses (approximately ≤10⁻⁶ S/cm)) was expected to accelerate Li⁺ ion insertion into and extraction from anode materials during charge and discharge reactions. This intrinsic property can yield the reversible lithium-alloying reaction by minimizing the aggregation of lithium-alloy phases leading to the improvement of cycling behavior. To examine sulfide glasses as new anode materials, GeS₂ glass was chosen for study in this work due to its stability in air-atmospheres. The electrochemical properties of the GeS₂ glass were compared with those of the Ge metal and GeO₂ glass. The initial insertion of lithium into the GeX₂ (X = O, S) glasses leads to the formation of Li₂X (X = O, S) phases associated with the irreversible capacity on the first cycle. The improved reversibility of the reaction of lithium with Ge was observed in the Li₂S medium rather than Li₂O one, which leads to the improvement of cycle performance in the GeS₂ glass anode.