Synthesis and Property Studies of Transparent Resins Containing Rare Earth Complex Eu(Ⅲ) (TTA)_2(MA)_2 Phen·H_2O

A new rare earth complex Eu(Ⅲ)(TTA)2(MA)2Phen·H2O was synthesized and characterized by element analysis, FTIR, UV, thermal analysis, and fluorescence spectra. The strong fluorescence and high thermal stability of Eu(Ⅲ)(TTA)2(MA)2Phen·H2O were used to modify resin. The copolymer containing europium was prepared by copolymerization of Eu(Ⅲ) and styrene/α-methylacrylic acid, and characterized by FTIR and fluorescence spectra. The fluorescence spectra showed that the copolymer was a sort of materials with good ...     

Facile and environment friendly synthesis of hierarchical BiOCl flowery microspheres with remarkable photocatalytic properties

A facile and environment friendly approach to synthesis of unique hierarchical BiOC1 flowery micro- spheres （FMs） using a biodegradable surfactant polyvinyl alcohol （PVA） was reported herein for the first time. Com- pared to the BiOC1 nanosheets synthesized in the absence of PVA, hierarchical BLOC1 FMs consist of large amounts of interwoven polycrystalline nanosheets that assemble into a porous flowery structure. The formation mechanism of the hierarchical BiOC1 FMs was also proposed, whereby PVA was believed to play a key role in the crystal growth and the formation of the final microstructures. Compared with TiO2- P25 and BiOC1 nanosheets, hierarchical BiOC1 FMs dis- played remarkably enhanced photocatalytic activity, and 20 mg of BiOC1 FMs could completely degrade 50 mL of methyl orange solution （20 rag/L） within 30 min under UV- light irradiation. According to the comprehensive analysis, it can be concluded that the larger specific surface area, porosity, suitable band gap, and the enhanced light absorp- tion capacity may contribute to the remarkably enhanced photocatalytic activity. This facile and green approach to fabricating hierarchical BiOC1 FMs would give vital clues to develop new route for synthesizing other hierarchical structured materials.     

Palladium(Ⅱ) and Platinum(Ⅱ) Compounds Derived From Potentially Terdentate Ligands

1Introduction Transition metalcomplexes derived from potentially terdentate ligands have attracted great interest in the late years. Among all the examples described so far, those containing palladium(Ⅱ) or platinum(Ⅱ) and ligands holding three heteroatoms with different donor abilities are particularly relevant. In compounds of this kind, the potential hemilability[1] of one of the terminal σ(M-donor atom) bonds, plays an important role in the view of their applications in homogeneous catalysis[2]. On the other hand, it is well-known that in dimetallic complexes the presence of two different metals in a close vicinity may influence their mutual cooperation in a wide variety of processes[3]. Besides that, some examples of the utility of chiral palladium( Ⅱ ) as well as platinum( Ⅱ ) complexes as precursors for organic and/or organometallic synthesis, as chiral recognitors or discriminators, or even in Bio-Medicine have also been reported[4- 6]. However, chiral heterodimetallic compounds holding ferrocenyl units and potentially terdentate ligands are scarce.     

Theoretic study of the reaction mechanism between (Me)_3CO· radical and trans-3-hexene

The reaction mechanism between(Me)3CO· radical and trans-3-hexene in benzene was studied for the first time at the B3LYP/6-311 G(d,p)//B3LYP/6-31G(d) ZPVE level.Two distinct elementary channels were identified as:(1) abstraction-addition;(2) addition-addition-elimination.Analysis of the potential energy surface demonstrates that for the title reaction,channels(1) and(2) have the major and minor contribution,respectively.Our calculated results can well explain the recently observed product distribution by Coseri et al.(J.Org.Chem.2005,70,4629).However,we found that the addition-abstraction channel proposed by Coseri et al.is kinetically infeasible.     

Joining of Si3N4 ceramic using PdCo(Ni SiB)–V system brazingfi ller alloy and interfacial reactions

The wettability of V-active PdCo-based alloys on Si3N4ceramic was studied with the sessile drop method. And the alloy of Pd50.0–Co33.7–Ni4.0–Si2.0–B0.7–V9.6(wt%),was developed for Si3N4ceramic joining in the present investigation. The rapidly-solidified brazing foils were fabricated by the alloy Pd50.0–Co33.7–Ni4.0–Si2.0–B0.7–V9.6. The average room-temperature three-point bend strength of the Si3N4/Si3N4joints brazed at 1453 K for 10 min was 205.6 MPa,and the newly developed braze gives joint strengths of 210.9 MPa,206.6 MPa and 80.2 MPa at high temperatures of 973 K,1073 K and 1173 K respectively. The interfacial reaction products in the Si3N4/Si3N4joint brazed at 1453 K for10 min were identified to be VN and Pd2Si by XRD analysis. Based on the XEDS analysis result,the residual brazing alloy existing at the central part of the joint was verified as Co-rich phases,in which the concentration of element Pd was high up to 18.0–19.1 at%. The mechanism of the interfacial reactions was discussed. Pd should be a good choice as useful alloying element in newer high-temperature braze candidates for the joining of Si-based ceramics.     

Synthesis, characterization and properties of ruthenium-substituted polyoxometallic acid H_6Ru(H_2O)FeW_(11)O_(39)·18H_2O with Keggin structure

The ruthenium-substituted polyoxometallic acid H6 [Ru(H2O)FeW 11O39 ]·18H2O was synthesized by stepwise acidification and stepwise addition of solutions of the component elements, and an ion-exchange-cooling method. The product was characterized using inductively coupled plasma spectrometry (ICP), Infrared Spectroscopy (IR), Ultraviolet Spectroscopy (UV), and X-ray diffraction (XRD). The results show that this complex has the Keggin structure. The determination of the thermal stability and proton conductivi...     

Effect of chemical activation process on adsorption of As(Ⅴ) ion from aqueous solution by mechano-thermally synthesized zinc ferrite nanopowder

Nanostructured Zn Fe_2O_4 was synthesized by the heat treatment of a mechanically activated mixture of Zn O/α-Fe_2O_3. X-ray diffraction(XRD) and differential thermal analysis(DTA) results demonstrated that, after 5 h of the mechanical activation of the mixture, Zn Fe_2O_4 was formed by heat treatment at 750°C for 2 h. To improve the characteristics of Zn Fe_2O_4 for adsorption applications, the chemical activation process was performed. The 2 h chemical activation with 1 mol·L~(-1) HNO_3 and co-precipitation of 52%-57% dissolved Zn Fe_2O_4 led to an increase in the saturated magnetization from 2.0 to 7.5 emu·g~(-1) and in the specific surface area from 5 to 198 m~2·g~(-1). In addition, the observed particle size reduction of chemically activated Zn Fe_2O_4 in field emission scanning electron microscopy(FESEM) micrographs was in agreement with the specific surface area increase. These improvements in Zn Fe_2O_4 characteristics considerably affected the adsorption performance of this adsorbent. Adsorption results revealed that mechano-thermally synthesized Zn Fe_2O_4 had the maximum arsenic adsorption of 38% with the adsorption capacity of 0.995 mg·g~(-1) in a 130 mg·L~(-1) solution of As(V) after 30 min of agitation. However, chemically activated Zn Fe_2O_4 showed the maximum arsenic adsorption of approximately 99% with the adsorption capacity of 21.460 mg·g~(-1) under the same conditions.These results showed that the weak adsorption performance of mechano-thermally synthesized Zn Fe_2O_4 was improved by the chemical activation process.     

Theoretical characterization of electronic structures and properties of C-F···H-C pseudohydrogen bonds

The weak intermolecular interactions between 2-F-tetrahydrofuran and imidazole, pyrimidine, adenine, and guanine were studied theoretically using density functional B3LYP/6-311++G** and HF/6-311++G** methods. The results showed that both conven- tional N···H hydrogen bond and C-F···H-C pseudohydrogen bond (PHB) structures coexist in the four complexes. The weak intermolecular interaction energies indicate that the relative stabilities of the four complexes are in the order guanine···F > imidazole···F > adenine···F > pyrimidine···F. The characteristics of the four PHBs were determined using geometry optimizations, stretching vibrational frequencies, and natural bond orbital and electron density topological properties calculations. The most important result is that the F group of 2-F-tetrahydrofuran can activate the C-H to accept electrons from another molecule, and C-F···H-C PHB formation is relatively favorable.     

Population dynamics of Pygoscelis penguins(1980–2012) and penguin dropping records(1916–2001) on Ardley Island of West Antarctica,in response to ENSO

El Nio-Southern Oscillation(ENSO)has affected penguins and their habitats in the western Antarctic Peninsula.We used both historical penguin population dynamics data(1980–2012)and sedimentary lipids in penguin droppings(1916–2001)on Ardley Island to examine the responses of the Antarctic ecosystem to ENSO(El Nin o/La Nin a)events.The results showed that during the last 30 years,climate,marine food chain changes,and human activity have significantly affected penguin population sizes on Ardley Island.The Chinstrap(Pygoscelis antarctica)and Ade′lie(P.adeliae)penguin populations showed a good correlation with ENSO events.The Chinstrap penguin population decreased significantly because it was more sensitive to increasing human disturbance(e.g.,scientific activity and tourism)than Ade′lie and Gentoo(P.papua),particularly during the breeding season.Compositional features of n-alkanes in penguin dropping sediments revealed that organic matter came from lower terrestrial plants,bacteria and algae.C23was the main nalkane heavy hydrocarbon indicating mosses and lichens in the penguin’s diet.Variation in the ratio of nC23/nC17was closely correlated with ENSO events.The bacteria intrusion index(ratio of(iC15:0?aC15:0)/nC15:0for fatty acids)reflected significant increases in microorganism activity during several periods in this area.Meanwhile,the CPIA value for fatty acids decreased because micro-organisms contributed light hydrocarbon fatty acids to penguin droppings.Our results showed that the fine structure and molecular indices of fatty acids and n-alkanes in penguin dropping sediments can be used to explain climate-driven microbial processes,and to reveal the important role that microbes and bacteria play in the relatively simple Antarctic ecosystem.     

Molecular cloning and polymorphism of major histocompatibility complex class I genes from grass carp (Ctenophayngodon idellus)

In order to clarify the molecular sequences,allelic polymorphism and the tertiary structure of grass carp (Ctenophayngodon idellus) MHC class I,and to further study their relationship with disease resistances,grass carp MHC class I gene (Ctid-MHC I) was cloned from a cDNA library and the allelic polymorphism in the population was investigated.The results showed that most of the variations exist in the peptide-binding domain (PBD) and high polymorphism was identified in the Ctid-MHC I allelic genes from 12 individuals.Based on the genetic distance,Ctid-MHC class I can be classified into 6 types (from Ctid-MHC I-UA to Ctid-MHC I-UF) which were subdivided into 9 lineages (from A to I).Comparison of the Ctid-MHC I among animals and humans showed that the key amino acids of the peptide binding sites are conserved.Analysis of the tertiary structure of the PBD between Grass carp and human crystallographic data of HLA-A2,the variation with insertion or deletion was found in eight regions (A～H).The phylogenetic tree of MHC class I indicates the evolution of MHC class I among grass carp,fish,amphibian,birds,higher vertebrates and humans.     

Hyperspectral retrieval model of phycocyanin in case II waters

Phycocyanin, a functional protein found in blue-green algae, with characteristic absorption peak around 620 nm, can be used to detect the quantity of blue-green algae in waters. Spectral characteristics of phycocyanin were studied by measuring hyperspectral water leaving radiance and absorption curve, and the results showed that the absorption peak of phycocyanin around 620 nm was evident in the curve of water leaving radiance. Bio-optical model of phycocyanin was set up with analytical methods and calibrated with error analysis. Linear relationship between phycocyanin concentration measured and that retrieved with calibrated bio-optical model (R = 0.755) was better than that retrieved with the band ratio of 709 nm/620 nm (R = 0.729), which proved that the calibration was neces-sary for improving the accuracy of phycocyanin concentration.     

Adsorption characteristics of Cd(II) and Ni(II) from aqueous solution using succinylated hay

An environmentally friendly organic biosorbent was fabricated using hay by succinylation. Metallic cation adsorption tests were performed using synthetic nickel(Ⅱ) and cadmium(Ⅱ) solutions to simulate heavy-metal recovery from aqueous solution. The adsorption efficiency was greater than 98% for both cadmium and nickel ions when the biosorbent concentration was 5.0 g/L and the initial metal concentrations were 50 mg/L. The surface of the biosorbent was characterized using Fourier transform infrared spectroscopy to investigate the changes in the surface functional groups. The functional groups changed according to the surface treatment, resulting in an effective biosorbent. The kinetics of the metals adsorption revealed that the reactions are pseudo-second order, and the adsorption isotherm well followed the Langmuir model. The maximum adsorption capacities predicted by the Langmuir model were 75.19 mg/g and 57.77 mg/g for cadmium and nickel, respectively. The fabricated biosorbent was regenerated using NaCl multiple times, with 2.1% for Cd and 4.0% for Ni in adsorption capacity after three regeneration cycles. The proposed biosorbent can be a good alternative to resin or other chemical adsorbents for heavy-metal recovery in metallurgical processing or municipal water treatment.     

Effect of chemical activation process on adsorption of As(V) ion from aqueous solution by mechano-thermally synthesized zinc ferrite nanopowder

Nanostructured ZnFe₂O₄ was synthesized by the heat treatment of a mechanically activated mixture of ZnO/α-Fe₂O₃. X-ray diffraction (XRD) and differential thermal analysis (DTA) results demonstrated that, after 5 h of the mechanical activation of the mixture, ZnFe₂O₄ was formed by heat treatment at 750°C for 2 h. To improve the characteristics of ZnFe₂O₄ for adsorption applications, the chemical activation process was performed. The 2 h chemical activation with 1 mol·L?1 HNO₃ and co-precipitation of 52%?57% dissolved ZnFe₂O₄ led to an increase in the saturated magnetization from 2.0 to 7.5 emu·g?1 and in the specific surface area from 5 to 198 m2·g?1. In addition, the observed particle size reduction of chemically activated ZnFe₂O₄ in field emission scanning electron microscopy (FESEM) micrographs was in agreement with the specific surface area increase. These improvements in ZnFe₂O₄ characteristics considerably affected the adsorption performance of this adsorbent. Adsorption results revealed that mechano-thermally synthesized ZnFe₂O₄ had the maximum arsenic adsorption of 38% with the adsorption capacity of 0.995 mg·g?1 in a 130 mg·L?1 solution of As(V) after 30 min of agitation. However, chemically activated ZnFe₂O₄ showed the maximum arsenic adsorption of approximately 99% with the adsorption capacity of 21.460 mg·g?1 under the same conditions. These results showed that the weak adsorption performance of mechano-thermally synthesized ZnFe₂O₄ was improved by the chemical activation process.     

Preparation and performance of LiNi_(0.8)Co_(0.2)O_2 cathode material based on Co-substituted α–Ni(OH)_2 precursor

Co-substituted α-Ni(OH)2 was synthesized by a novel microwave homogeneous precipitation method in the presence of urea. LiNi0.8Co0.2O2 cathode material was synthesized by calcining Co-substituted α-Ni(OH)2 precursor and LiOH·H2O at 900℃ for 10 h in flowing oxygen. XRD, FTIR, FESEM and electro- chemical tests were used to study the physical and the electrochemical performances of the materials. The results show that the prepared LiNi0.8Co0.2O2 compound has a good layered hexagonal structure. Moreover, the LiNi0.8Co0.2O2 cathode material demonstrates stable cyclability with a high initial specific discharge capacity of 183.9 mAh/g. The good electrochemical performance could be attributed to the uniform distribution of Ni2 and Co2 ions in the crystal structure and a minimal cation mixing in LiNi0.8Co0.2O2 host structure.     

A new biselector chiral stationary phase derived from tartaric acid and its enantioseparation evaluation

Two chiral selectors were synthesized from tartaric acid. The selectors were simultaneously immobilized on 3-aminopropyl silica gel to obtain a new biselector chiral stationary phase (CSP) in order to determine the influence of selector structure of biselector CSPs on the chiral recognition capability. For comparison, the single-selector CSP was also prepared. The biselector CSP shows an improved overall chiral recognition capability in comparison with the single-selector CSP. During the enantioseparation, temporary diastereoisomers are likely formed by complexation between a chiral analyte and the two selectors on the biselector CSP. The functional groups in the two selectors are complementary in electronic effect and/or in steric hindrance for the chiral recognition.     

Co-oxidation of arsenic(Ⅲ) and iron(Ⅱ) ions by pressurized oxygen in acidic solutions

The co-oxidation of As(Ⅲ) and Fe(Ⅱ) in acidic solutions by pressured oxygen was studied under an oxygen pressure between 0.5 and2.0 MPa at a temperature of 150℃. It was confirmed that without Fe(Ⅱ) ions, As(Ⅲ) ions in the solutions are virtually non-oxidizable by pressured oxygen even at a temperature as high as 200℃ and an oxygen pressure up to 2.0 MPa. Fe(Ⅱ) ions in the solutions did have a catalysis effect on the oxidation of As(Ⅲ), possibly attributable to the production of such strong oxidants as hydroxyl free radicals(OH·) and Fe(IV) in the oxidation process of Fe(Ⅱ). The effects of such factors as the initial molar ratio of Fe(Ⅱ)/As(Ⅲ), initial pH value of the solution, oxygen pressure, and the addition of radical scavengers on the oxidation efficiencies of As(Ⅲ) and Fe(Ⅱ) were studied. It was found that the oxidation of As(Ⅲ) was limited in the co-oxidation process due to the accumulation of the As(Ⅲ) oxidation product, As(V), in the solutions.     

表面合金Cu(001)c(2×2)-Pd原子结构的第一原理计算研究

在层晶模型近似下,采用薄膜全电子线性缀加平面波(LAPW)方法研究了表面合金Cu(001)c(2×2)-Pd的原子结构.能量计算表明Pd原子的皱折小于0.01 nm,该结果与低能电子衍射(LEED)和扫描隧道显微镜(STM)实验结果一致.     

A new synthetic route to MgO–MgAl_2O_4–ZrO_2 highly dispersed composite material through formation of Mg_5Al_(2.4)Zr_(1.7)O_(12) metastable phase:synthesis and physical properties

Mg_5Al_(2.4)Zr_(1.7)O_(12) metastable phase was successfully synthesized from analytical-grade Mg O,α-Al_2O_3,MgAl_2O_4,and ZrO_2 under an N_2 atmosphere.The sintering temperature was varied from 1650 to 1780°C,and the highest amount of Mg_5Al_(2.4)Zr_(1.7)O_(12) appeared in the composite material when the sintering temperature was 1760°C.According to our research of the formation mechanism of Mg_5Al_(2.4)Zr_(1.7)O_(12),the formation and growth of MgAl_2O_4 dominated when the temperature was not higher than 1650°C.When the temperature was higher than 1650°C,MgO and ZrO_2 tended to diffuse into MgAl_2O_4 and the Mg_5Al_(2.4)Zr_(1.7)O_(12) solid solution was formed.When the temperature reached 1760°C,the formation of Mg_5Al_(2.4)Zr_(1.7)O_(12) was completed.The effect of Mg Al_2O_4 spinel crystals was also studied,and their introduction into the composite material promoted the formation and growth of Mg_5Al_(2.4)Zr_(1.7)O_(12).A highly dispersed MgO–Mg Al_2O_4–ZrO_2 composite material was prepared through the decomposition of the Mg_5Al_(2.4)Zr_(1.7)O_(12) metastable phase.The as-prepared composite material showed improved overall physical properties because of the good dispersion of MgO,MgAl_2O_4,and ZrO_2 phases.     

Preparation of MCM-41-supported chiral Salen Mn （Ⅲ） catalysts and their catalytic properties in the asymmetric epoxidation of olefins

A secondary amino-modified mesoporous molecular sieve MCM-41 was obtained by reaction of bis(3-(triethoxysilyl)propyl)amine with MCM-41. The chiral Salen-Mn (III) complex was anchored onto the modified MCM-41 by a multi-step grafting method and two heterogenized catalysts with different Mn contents were obtained. The catalysts were characterized by XRD, N2 adsorption, ICP, FT-IR and DR UV-Vis. Their catalysis on asymmetric epoxidation of several olefins was studied with NaClO and m-CPBA as oxidants respectively. It was found that both the activity and enantioselectivity of the cata- lysts decreased after the homogeneous catalyst was heterogenized. The reasons resulting in the de- crease of catalytic performance were discussed.     

The comparison of Cu(II) adsorption capability of baker’s yeast, nano-titania and their composite adsorbent

The anatase nano-TiO2 powder, with crystal size between 40 and 80 nm, was prepared by the liquid phase hydrolysis of TiCl4. At the same time, the nano-TiO2 was utilized with the baker’s yeast biomass as a composite adsorbent to adsorb the Cu ions in the artificial aqueous solution. The investigation showed that the composite adsorbent had a fine adsorption efficiency. The TiO2 in the composite ad- sorbent could cooperate well with baker’s yeast to improve the adsorbing capability of Cu2 under the following experimental conditions as well: a quantity of composite adsorbent of 5 g·L?1, pH≥4.0, an adsorption time of 40 min and an initial concentration of Cu ions of 10 mg·L?1. In addition, the results of measurements, obtained with a scanning electron microscope, an infrared spectrophotometer and a Zeta potential analyzer, revealed that the baker’s yeast and nano-TiO2 produced the composite ad- sorbent through coordination and hydrogen bonds in particular, etc. The stability of the composite adsorbent and the amount of titania loaded were largely dependent on the concentration of hydrogen ion in the solution.