The synthesis and photophysical properties of water soluble tetrasulfonated, octacarboxylated and quaternised 2,(3)-tetra-(2 pyridiloxy) Ga phthalocyanines

The photophysical behaviour of chlorogallium 2,(3)-tetra-(2 pyridiloxy) phthalocyanine (ClGaT-2-PyPc) and its quaternised derivative were compared with that of the water soluble anionic tetrasulfonated gallium phthalocyanine ((OH)GaTSPc) and hydoxy gallium octacarboxy phthalocyanine ((OH)GaOCPc). Although both the quaternised compound and the tetrasulfonated gallium phthalocyanine aggregated in aq. solution at pH 11, resulting in low fluorescence and triplet yields, the presence of the surfactant Cremophore EL improved yields. Triplet quantum yields ranged from 0.52 to 0.70 and fluorescence quantum yields ranged from <0.01 to 0.21. The nature of substituent (sulfonate, carboxy and pyridiloxy) did not influence photophysical properties. Chlorogallium 2,(3)-tetra-(2 pyridiloxy) phthalocyanine and its quaternised derivative displayed longer triplet lifetime than both the tetrasulfonated gallium phthalocyanine ((OH)GaTSPc) and hydroxy gallium octacarboxy phthalocyanine in DMSO and in aq. media in both the presence and absence of surfactant.     

The synthesis,fluorescence behaviour and singlet oxygen studies of new water-soluble cationic gallium(III) phthalocyanines

The preparation of cationic water-soluble gallium phthalocyanine derivatives are described for the first time. Peripheral and non-peripheral 3-hydroxypyridine tetrasubstituted gallium(III)phthalocyanines (5a, 6a) and their quaternarized derivatives (5b and 6b) have been synthesized and characterized by elemental analysis, IR, ¹H NMR spectroscopy, electronic spectroscopy and mass spectra. The quaternarized compounds (5b and 6b) are soluble in water and not aggregated (in water and in organic solvents) within a wide concentration range. General trends are described for singlet oxygen quantum yields, fluorescence quantum yields and fluorescence lifetimes of these compounds. These complexes showed better singlet oxygen quantum yields in water than the related quarternarized porphyrazine complexes.     

Photochemistry and Cytotoxicity Evaluation of Heptamethinecyanine Near Infrared (NIR) Dyes

The present study investigates the photochemical properties of potential photosensitizers for photodynamic therapy, namely four commercial heptamethinecyanine dyes (IR125, IR780, IR813, IR820). Spectroscopic studies were made by means of laser induced fluorescence and laser flash photolysis in order to obtain fluorescence quantum yields and transient absorption spectra. Fluorescence lifetimes were also determined. The differences encountered were essentially related with the interaction of the sulfonate groups with the solvent, and also regarding the rigidification of the central bridge connecting the two nitrogen-containing heterocyclic groups. Transient absorption studies were performed both in aerated and oxygen free samples, to conclude about the formation of photoisomers and triplet state. For the four dyes under study, a cytotoxic evaluation in the dark and after irradiation was performed using HeLa cells as the model cell line, which revealed significant changes after irradiation mainly in IR125 and IR813 dyes. Confocal microscopy analysis showed that these dyes tend to enter to the intracellular space.     

Synthesis, absorption and fluorescence properties of N-triazinyl derivatives of 2-aminoanthracene

N-(4,6-dichloro-1,3,5-triazin-2-yl)-2-aminoanthracene was synthesized by substitution of one chlorine atom of 2,4,6-trichloro-1,3,5-triazine with 2-aminoanthracene. A new series of N-triazinyl-2-aminoanthracenes was prepared by nucleophilic substitution of one or both chlorine atoms on N-(4,6-dichloro-1,3,5-triazin-2-yl)-2-aminoanthracene with electron-donating methoxy or phenylamino groups. The UV/Vis absorption, fluorescence and excitation spectra as well as the fluorescence quantum yields of the prepared compounds were measured in 1,4-dioxane, ethyl acetate, dibutyl ether and acetonitrile; nanosecond kinetics of the fluorescence decay was measured in different solvents. The influence of the character of the substituent on triazinyl ring and of the solvent polarity upon the absorption and fluorescence spectra and fluorescence quantum yields are discussed.     

NaBr-KCl和不同炭源对合成Ti(C,N)粉末的影响

采用质量分数76.9%的钛白粉分别和23.1%的炭黑、石墨或活性炭,或者40%的钛白粉和60%的淀粉为原料,10%NaBr-KCl为添加剂,试样经干法成型后,在埋炭条件下分别于1300℃、1400℃保温3h处理,利用XRD、SEM、EPMA分析了合成粉末的物相组成和微观形貌,研究了在埋炭条件下不同炭源及NaBr-KCl的存在与否对碳热还原法合成Ti(C,N)的影响。结果表明:分别以石墨、炭黑、活性炭或淀粉作为炭源均可合成Ti(C,N);外加剂NaBr-KCl的存在对以淀粉和炭黑为炭源的反应促进作用较大。在NaBr-KCl存在条件下,以炭黑为炭源经1300℃3h合成的Ti(C,N)晶粒大小为5~8μm;而分别以石墨、活性炭或淀粉作为炭源经1400℃3h合成的Ti(C,N)晶粒大小为1~3μm。     

The synthesis and mechanical properties of high pure Ti2Al(Sn)C solid solution

High pure Ti₂Al_(1?x)Sn_xC (x = 0‐1) powders were synthesized using Ti, Al, Sn, and TiC powders as raw materials by pressureless sintering method. The influence of sintering temperature and raw material ratio on the purity of Ti₂AlC and Ti₂Al_0.8Sn_0.2C powders were investigated. The results show that pure Ti₂AlC and Ti₂Al_0.8Sn_0.2C powders were obtained from the mixed raw materials ratio of Ti:1.1Al:0.9TiC and Ti:0.9Al:0.2Sn:0.9TiC at 1450°C, respectively. Subsequently, fully dense Ti₂AlC and Ti₂Al_0.8Sn_0.2C bulks were prepared using mechanically alloying and hot pressed sintering method. The Vickers hardness of Ti₂AlC and Ti₂Al_0.8Sn_0.2C approaches approximately about 6 GPa and 4 GPa, the flexural strength was measured to be 650 ± 36 MPa and 521 ± 33 MPa, respectively. Microstructural analysis reveals that grain delamination, kink bands, and crack deflection occurred around the indentation area and at the fracture surface.     

Investigation of the piezoelectric and anti-reduction properties of (Ba,Ca) (Ti,Sn, Hf) textured ceramics prepared under low oxygen partial pressure conditions at low sintering temperatures

Multilayer piezoelectric ceramics must be sintered in a reducing atmosphere, preventing oxidation of the inner base metal. Plate-like textured (Ba, Ca)(Ti, Sn, Hf)O₃ ceramics with a <001> preferred orientation were successfully developed at a low oxygen partial pressure (PO₂:10^?8 atm) using a BaTiO₃ (BT) template with sintering temperatures < 1300 °C, which is beneficial for multilayer applications using base metal co-firing with ceramics. When adding the 3 wt% BT template, the proposed samples had a Lottgering factor of 84 %, piezoelectric coefficients d₃₃ = 324 pC/N, -d₃₁ = 122 (pC/N), and Q_m = 452, and the strain values increased from 0.07 % for the randomly oriented ceramics to 0.115 % at 20 kV/cm for the textured ceramics, confirming that the texturing behavior assisted the grain growth and improved both the soft and hard behaviors and insulation resistance of the proposed lead-free ceramics. These findings make a significant contribution to the production of high-power piezoelectric components.     

Evaluation of the sinterability,densification behaviour and microhardness of spark plasma sintered multiwall carbon nanotubes reinforced Ti6Al4V nanocomposites

Structural and industrial demands for lightweight engineering materials with exclusive properties have been rising in recent decades for automobile and aerospace applications. This has encouraged various innovations in materials engineering communities to synthesis advanced engineering materials using improved fabrication technique such as spark plasma sintering (SPS). In this study, titanium-based nanocomposites were synthesized by reinforcing Ti6Al4V reinforced with (0.5, 1.0 and 1.5 wt%) multiwall carbon nanotubes (MWCNT) powders. The starting powders were blended by shift-speed ball milling. Thereafter, SPS technique was used to consolidate the admixed powders by employing the following sintering parameters; sintering rate, 100 °C/min, compressive pressure, 50 MPa, holding time, 10 min and sintering temperatures of 900–1100 °C. The influence of MWCNT additions on the sinterability, densification behaviours and microhardness of the sintered nanocomposites were investigated. The results revealed that the densification of the sintered nanocomposites was in the range of 97.51–99.61% which decreased with an increase in concentration of the MWCNT. Meanwhile, the densification and microhardness improved tremendously with an increase in sintering temperatures.     

碳热还原氮化制备Ti(C,N)技术的现状与发展

简单概述了Ti(C,N)的结构、性质、应用及其制备方法,并从热力学和动力学方面对碳热还原氮化制备Ti(C,N)技术进行了论述,分析了其制备过程中的工艺因素(如C/Ti摩尔比,原料种类及粒度大小,原料混合方式,气体流速,燃烧温度,添加剂等)的影响,同时还对碳热还原氮化制备Ti(C,N)技术的发展方向进行了展望。     

The role of Sb and Nb in rutile-type Sn/V/Nb/Sb mixed oxides, catalysts for propane ammoxidation to acrylonitrile

This paper describes the role of Sb and Nb, components of Sn/V/Nb/Sb mixed oxides catalysts for the gas-phase ammoxidation of propane to acrylonitrile. In samples without Nb and with atomic ratios Sn/V/Sb 1/0.2/x (x = 0 to 3), Sb in the form of amorphous oxide is necessary in order to obtain an active and selective catalyst. However, during reaction the dispersed Sb oxide segregates to α-Sb₂O₄, and the yield to acrylonitrile decreases considerably. The addition of Nb gives rise to the formation of Nb-containing SbO_x and non-stoichiometric rutile-type V/Nb/Sb mixed oxides. The presence of these compounds enhances the catalytic activity and the selectivity to acrylonitrile. Moreover, the catalyst shows a stable catalytic performance, with no segregation of α-Sb₂O₄.     

The behaviour of graphite, carbon black, and Li4Ti5O12 in LiBOB-based electrolytes

The film formation behaviour of lithium bis(oxalato)borate (LiBOB), a new electrolyte salt for lithium batteries, on graphite, carbon black and lithium titanate is reported. LiBOB is actively involved in the formation of the solid electrolyte interphase (SEI) at the anode. Part of this formation is an irreversible reductive reaction which takes place at potentials of around 1.75 V vs Li/Li⁺ and contributes to the irreversible capacity of anode materials in the first cycle. Carbon black interacts strongly with LiBOB-based electrolytes, which results in strong film formation and loss of electronic conductivity within the composite electrode. In LiBOB-based electrolytes the electrode kinetics increase in the order: carbon black << fine particulate graphite ~ metal powder, due to decreased film formation of the conductive additive. The influence of various solvents, surfactant additives, and potential impurities was also studied.     

The synthesis,characterisation and thermal behaviour of functionalised aryl cyanate ester monomers

The syntheses of several functionalised aryl cyanate esters bearing reactive allyl groups are presented. The monomers were purified (to c. 98%) using preparative HPLC and a range of techniques, including heteronuclear nuclear magnetic resonance (NMR) spectroscopy, was employed in their characterisation. A model functionalised aryl cyanate ester was doped with a variety of additives and the resulting thermal behaviour examined using dynamic differential scanning calorimetry (DSC). Furthermore, the postulated co-reaction of the model functionalised cyanate ester with bis-maleimides was investigated using heteronuclear NMR and dynamic mechanical techniques.     

The design and synthesis of a novel 1,8-naphthalimide PAMAM light-harvesting dendron with fluorescence “off-on” switching core

A novel polyamidoamine dendron core, peripherally functionalized with 1,8-naphthalimide fluorophores, was configured as a light harvesting antenna in which the system surface was labelled with blue emitting 4-allyloxy-1,8-naphthalimide “donor” dyes capable of both absorbing light and efficiently (96%) transferring the energy to a single, yellow-green emitting 4-N-methylpiperazinyl-1,8-naphthalimide “acceptor” dye. The 1,8-naphthalimide core was designed on the “fluorophore-spacer-receptor” format and was able to function as a fluorescence photoinduced electron transfer sensor. Two different photoinduced electron transfer effects were observed in the new antenna namely that from the receptor to the core fluorophore and that from the polyamidoamine backbone to the peripheral 1,8-naphthalimides. Althogh the core emission intensity of the system was enhanced > four times by reducing the pH from 10 to 2, the fluorescence enhancement of the system in acidic medium, excited within the periphery (λ_ex = 360 nm), was approximately twice that of the core fluorescence enhancement after direct excitation of the focal 1,8-naphthalimide (λ_ex = 420 nm), because of more efficient energy transfer. The observed “off-on” switching of the core fluorescence over a wid pH scale indicates that the novel light harvesting antenna would be able to act as a highly efficient fluorescent sensor.     

The synthesis, crystal structures and photophysical properties of a series of novel 4,6-diphenyl-1,9-anthrazolines

The synthesis and properties of a series of nine new 4,6-diphenyl-1,9-anthrazolines molecules 1a-1i are reported. Compounds 1a-1i were synthesized by Friedländer condensation of 4,6-dibenzoyl-1,3-phenylenediamines and acetyl-functionalized compounds in the presence of polyphosphoric acid as catalyst, in yields ranging from 60% to 94%. The 4,6-diphenyl-1,9-anthrazolines are thermally robust with high decomposition temperatures (>371.0 °C) and high melt transitions (215.1-322.8 °C). Compounds 1a and 1f crystallized in the triclinic system with the space groups P-1. All of them show the lowest energy absorption bands (λ_max^Abs: 397-454 nm), revealing low optical band gaps (2.55-3.00 eV). The compounds emit blue fluorescence with λ_max^Em ranging from 432 to 493 nm in dilute toluene solution. 4,6-Diphenyl-1,9-anthrazolines 1a-1i have a formal reduction potential in the range −1.02 to −1.19 V (versus SCE) and estimated electron affinities (LUMO levels) of 3.21-3.38 eV. These results demonstrate that the new 4,6-diphenyl-1,9-anthrazolines are promising thermally stable n-type semiconductors for organic electronics.     

The role of composition, morphology and crystalline structure in the electrochemical behaviour of TiNx thin films for dry electrode sensor materials

A morphological, structural and electrochemical study of titanium nitride (TiN_x) thin films, obtained by DC reactive sputtering on titanium substrates, was carried out for a wide range of compositions (0 < x < 1.34) aiming a selection of the best coatings for dry biomedical electrodes. The films displayed a columnar-type structure, with morphologies strongly dependent on the composition: a compact and smooth surface was found for the Ti-rich films, (x < 1), whereas the N-rich films, (x ≥ 1) displayed a rough and porous structure. The electrochemical study of the TiN_x films was performed in synthetic sweat, aiming at simulating the contact with the skin. The voltammetric analysis showed anodic currents higher for TiN_x films than for titanium for low and medium polarization potentials, whereas for potentials beyond 2 V the blocking behaviour of the TiN_x films allowed them to display lower current values. The passive dissolution currents in the sub-μA/cm² range and the charge transfer resistances of the order of the MΩ proved the excellent stability of all films in sweat conditions. Finally, the electrochemical noise analysis showed that the near-stoichiometric and N-rich films display the lowest noise, being therefore the most suitable for electrode applications, where signals in the microvolt range, such as the electroencephalographic (EEG) signals, are to be monitored.     

确定低渗透油藏启动压力梯度的新方法及应用

通过对江汉油田低渗透油藏20块不同渗透率岩心室内驱替实验,从流体在低渗透多孔介质渗流机理出发,对所得实验数据进行了处理,研究了一种求解启动压力梯度的新方法。通过对实验数据进行回归分析,得到低渗透油藏启动压力梯度与地层流度的关系式,并绘制了求解低渗透油田启动压力梯度的图版。利用实验所得到的回归关系式和求解启动压力梯度的图版,结合低渗透油田实际,进行应用,得到不同生产压差下确定极限注采井距的方法。     

Mono (V, Nb) or bimetallic (V–Ti, Nb–Ti) ions modified MCM-41 catalysts: synthesis, characterization and catalysis in oxidation of hydrocarbons (aromatics and alcohols)

Mesoporous MCM-41 molecular sieves modified by single (V and Nb) or bimetal (Nb–Ti and V–Ti) ions with highly ordered hexagonal arrangement of their cylindrical channels were prepared by direct synthesis with two different silica sources (sodium silicate and TEOS) and characterized (as-synthesized samples and those used after reaction) by XRD, N₂ adsorption–desorption, TEM, SEM and FTIR techniques. Niobium and titanium were stabilized in the autoclavized gel by complexation with a ligand (acetylacetone and oxalic acid, respectively). V modified MCM-41 catalysts gave a very high activity in hydroxylation reaction of benzene and toluene and a low conversion in oxidation of styrene while Nb-modified MCM-41 samples showed very high conversion in oxidation of styrene but low oxidation conversion of benzene and toluene. Further introduction of titanium in V- and Nb-modified MCM-41 materials conducted to the less well-ordered hexagonal arrangement and gave very different effect on activity in oxidation of aromatics. Introduction of Ti into V-MCM-41 solids led to an increase in activity in oxidation of styrene and benzene but a decrease in conversion in oxidation of toluene. While the addition of Ti in Nb-MCM-41 resulted in a slight increase in conversion of styrene oxidation but a significant decrease in activity of benzene and toluene oxidation. It reveals that the introduction mode of oxidant in the reactors can also influence the activity and selectivity of reaction. An increase in reaction rate of oxidation, in the first 20 h, was obtained by introduction of H₂O₂ step by step during the reaction. The present paper evidenced that the side chain oxidation is main reaction of styrene oxidation while the hydroxylation is main reaction of benzene and toluene. That is why these two reactions need different catalytic centers as revealed by this paper. The oxidation of alcohols using V-modified MCM-41 as catalysts has also been explored and these catalysts showed a very low catalytic activity which increases in the order: hexanol相似文献   

The synthesis, spectroscopic and electrochemical properties, and application of new dyeing photoinitiator systems for acrylate monomers polymerization

New symmetrical bicationic polymethine dyes were synthesized and their spectroscopic and electrochemical properties were described. The bichromophoric dyes (benzothiazole, benzoxazole, indolinium derivatives) were investigated as sensitizers in the free radical photopolymerization initiated by their borate salts. The obtained kinetic results shown that bicationic polymethine dyes as the organoborate salts are much efficient photoinitiating systems of acrylate monomers polymerization than monocationic parent dyes. The rate of polymerization depends on ΔG_ET of electron transfer from borate anion to the excited singlet state of bicationic polymethine dye. The relationship between the rate of polymerization and the free energy of electron transfer process shows the dependence predicted by the classical theory of electron transfer.