CHARACTERIZATION OF SOME SCHIFF BASES OF HETEROCYCLIC COMPOUNDS AND THEIR TRANSITION METAL COMPLEXES

Some new Schiff bases were synthesized by the condensation of equimolar quantities of salicylaldehyde and 2-amino-5-phenylazo-pyridine or its derivatives in dry benzene(1):Metal complexes of the type ML_2and M'L_3 where M=Cu^(2+),Co^(2+),Ni^(2+),Mn^(2+)Pd^(2+),M'=Fe^(3+)and L=different newly synthesized monobasic Schiff bases were prepared in absolute ethanolic medium(2)and characterized by elementary analysis,conductance measurements,infrared spectra,electronic spectra,magnetic moments studies.

Electrocatalytic oxygen evolution activities of metal chalcogenides and phosphides:Fundamentals,origins,and future strategies

The development of inexpensive and efficient electrocatalysts is key to commercializing energy-related electrocatalytic techniques such as water electrolyzers and metal-air batteries.In particular,novel oxygen evolution reaction(OER)pre-catalysts,such as transition metal chalcogenides(TMCs)and phosphides(TMPs),have evolved in recent years from traditional stable OER electrocatalysts,which show superior OER electrocatalytic performance compared with transition metal oxides(TMOs)or(oxy)hydroxides(TMOHs).In this feature article,we summarize recent advances in the development of TMCand TMP-based OER electrocatalysts,as well as approaches to improve the OER performance in terms of morphology,structure,composition,surface engineering,lattice-strained and in-situ transformation in the electrolysis process.In particular,the electrochemical stability of TMCs and TMPs in alkaline electrolytes and the evolution of morphology,structure and composition under OER conditions are discussed.In the last section,we discuss the challenges that need to be addressed in this specific area of research and the implications for further research.

Test and application of 60 kg·m^(−1) bainite rails for heavy-haul railway

Purpose-In order to develop high-strength,high-toughness and high-wear-resistance rails suitable for the development and application of heavy-haul railways.Design/methodology/approach-Based on the trial production of 60 kg·m^(−1) bainite rails,the Zeiss inverted optical microscope,transmission electron microscope and static hydraulic universal tester were used to test the microstructure and property of rail base metal and welded joints.Meanwhile,a trial laying of rails,wing rails of frogs and switch rails for turnouts was performed to systematically analyze their strength,toughness and wear resistance.Findings-The results show that the base metal of 60 kg·m^(−1) bainite rail is of a uniform microstructure,with a carbide-free bainite matrix,a few of stable residual austenite and M/A islands,and it features high hardness,good wear resistance and good strength-toughness balance.The welded joint is of a uniform microstructure and has good properties.Originality/value-A bainite rail,laid in a curve section of heavy-haul railway is able to serve for 48 months with a gross traffic tonnage of nearly 600 million tons,whose service life is more than one time longer than that of pearlite rail;the service life of the wing rail of frog and the switch rail for turnout with 60 kg·m^(−1) bainite rails is 3-4 times longer than that with U75V rails,and no serious damage occurs.The bainite rails also have strong peeling and spalling resistance.

Geochemical Mobility Associated to Gold and Base Metal Occurrences of Mangodara Sector, in Southern Burkina Faso, Banfora Greenstone Belts (West African Craton)

In the Mangodara area within the Banfora greenstone belts (Baoulé-Mossi domain of the West African Craton), our study focused on geochemical assessment of the mobility of major and trace elements. Gold and base metal occurrences are hosted in highly metamorphic felsic (metarhyolite) and intermediate (metadacite and metaandesite) formations. Common mineral assemblages made up of staurolite - kyanite - pyrophyllite are interpreted to represent the metamorphosed equivalent of aluminous hydrothermal alteration. Associated felsic and intermediate volcanic rocks are enriched in Fe2O3, K2O (metaandesite, metarhyolite) and depleted in MgO, Al2O3, CaO, P2O5, Na2O (metarhyolite) and Fe2O3, MgO, CaO (metaandesite). Al2O3 depletion in mineralized kyanite-staurotide bearing metarhyolites suggests corroded minerals. Mineralized metarhyolites show enrichment in Au, Ag, Ba, Bi, Cr, Cu, Eu, La, Mo, Ni, Pb, S, Sc, V and depletion in As Sb Co, Sn, Zn while mineralized metaandesites show enrichment in Au, Ag, As, Mo, S, Sb and depletion in Co, Sn, Zn, Bi, Cr, Cu, Eu, Ni, Pb, Sc. Ba, La, V are immobile in metaandesites. Finally, Ag, As, Sn appear as geochemical vectors for gold exploration in the study area since gold mineralization is characterized by Au + Ba + Cu + Eu + La + Mo + Ni + S association in metarhyolites and Au + S + Sb + As + Ag + Bi in metaandesites.

Features of microstructure and fracture in the transient liquid phase bonded aluminium-based metal matrix composite joints

Transient liquid phase (TLP) bonded aluminium based metal matrix composite (MMC) joints can be classified into three distinct regions, i.e. the particulate segregation region, the denuded particulate region and the base material region. The microstructure of the particulate segregation region consists of alumina particulate and Al alloy matrix with the Al 2Cu and MgAl 2O 4. It contains more and smaller alumina particulates compared with the base material region. The TLP bonded joints have the tensile strength of 150 MPa ～200 MPa and the shear strength of 70 MPa ～100 MPa . With increasing tensile stress, cracks initiate in the particulate segregation region, especially in the particulate/particulate interface and the particulate/matrix interface, and propagate along particulate/matrix interface, througth thin matrix metal and by linking up the close cracks. The particulate segregation region is the weakest during tensile testing and shear testing due to obviously increased proportion of weak bonds (particulate particulate bond and particulate matrix bond).

Study on Property of Salicylaldehyde Schiff Base Metal Complexes for Catalytic Oxidation of Model Sulfides

Seven kinds of Schiff base metal complexes(C1-C7)were synthesized by the reaction of substituted salicylaldehyde Schiff base with cobalt nitrate,nickel nitrate,and copper nitrate,respectively.The oxygen carrying performance,and the catalytic property of complexes for the oxidation of model sulfides 1-hexanethiol,dibutyl sulfide,and 2-methylthiophene along with their influencing factors were explored,while the oxidized products of the model sulfides were also analyzed and characterized.The results show that the catalytic oxidation property of the complexes is determined by their oxygen carrying performance and solubility in n-octane.The oxygen carrying performance of the complexes is mainly affected by the central ion species,the electronic effects,and the spatial effects of the substituents as well as the degree of conjugation.More specifically,the oxygen carrying performance can be improved by enhancing the oxygenation capacity of the central metal ions,increasing the electron donating ability of the ligand substituent,and diminishing the steric hindrance as well as extending the conjugated chain.Complexes C7 were found to be with high oxygen carrying capacity and high solubility in n-octane,which shows the best catalytic oxidation property,and the oxidation conversion rates for 1-hexylthiol,dibutyl sulfide,and 2-methylthiophene are 74.2%,65.1%,and 22.7%,respectively.Upon using the oxidation catalyst of Schiff base metal complexes,three sulfides can be oxidized by oxygen to form sulfones and sulfoxides.1-Hexanethiol and dibutyl sulfide will continue to be oxidized to form sulfates and sulfites.

Use of centrifugal-gravity concentration for rejection of talc and recovery improvement in base-metal flotation

The possibility of using a centrifugal-gravity concentrator to reject Mg-bearing minerals and minimize metal losses in the flotation of base metals was evaluated. Sample characterization, batch scoping tests, pilot-scale tests, and regrind-flotation tests were conducted on a Ni flotation tailings stream. Batch tests revealed that the Mg grade decreased dramatically in the concentrate products. Pilot-scale testing of a continuous centrifugal concentrator（Knelson CVD6） on the flotation tailings revealed that a concentrate with a low mass yield, low Mg content, and high Ni upgrade ratio could be achieved. Under optimum conditions, a concentrate at 6.7% mass yield was obtained with 0.85% Ni grade at 12.9% Ni recovery and with a low Mg distribution（1.7%）. Size partition curves demonstrated that the CVD also operated as a size classifier, enhancing the rejection of talc fines. Overall, the CVD was capable of rejecting Mg-bearing minerals. Moreover, an opportunity exists for the novel use of centrifugal-gravity concentration for scavenging flotation tailings and/or after comminution to minimize amount of Mg-bearing minerals reporting to flotation.

Synthesis of Enantiom eric Planar Square Ni^(2+) -and Cu^(2+) -Schiff Base Com plexes

Enantiomeric four chelated planar square schiff base Cu 2+ and Ni 2+ complexes were synthesized using ( 1R,trans ) and ( 1S,trans) N,N bis(2 hydroxyphenyl methylene) 1,2 diaminocyclohexane. The chirality could not be shown by usual UV Vis spectra. The intrinsic chiral difference of the enantiomeric complexes can be displayed by circular dichroism(CD) spectra. The Cotton effect of every polarlight sensitive absorption of one enantiomer will be the opposite of that of the other enantiomer. It was found that no tetrahedron form exists for Ni 2+ complexes, which was determined with UV Vis spectra and Electron Paramagnetic Resonance(EPR) measures.

Geochemical Characterization of Base Metals in Stream Water and Sediments in the Caddo Lake Watershed, Cass, Harrison and Marion Counties, Texas

The Caddo Lake watershed is located in northeastern Texas and encompasses much of Cass, Harrison, and Marion counties. The watershed is drained by major streams and tributaries flowing in an easterly direction over Eocene-aged rocks and sediments of the Wilcox and Claiborne groups, and empty into the western arm of Caddo Lake. Since 1995, Caddo Lake and some of its tributaries have been included on the State of Texas Clean Water Act 303(d) list by the Texas Commission on Environmental Quality (TCEQ) for impairment due to mercury content in edible tissue, depressed dissolved oxygen, base metal concentrations, and low pH values. The purpose of this multi-year study was to characterize base metal concentrations in stream water and sediments in the Caddo Lake watershed, and document the potential watershed transport and contribution to the impairment of Caddo Lake. Recent water (n = 58) and sediment (n = 116) sampling at 29 sites revealed copper, lead, and zinc concentrations within normal limits and below EPA actionable standards. Mercury concentrations were elevated at 21 of the 29 sampling sites, which could lead to methylation and bioavailability to organisms at all trophic level.

Optical Properties of Chiral Azo-Schiff Base Mn(II) and Zn(II) Complexes with Silver Nanoparticles

Herein we have originally designed chiral azo-salen Mn(II) and Zn(II) complexes for interacting silver nanoparticles (AgNPs) exhibiting localized surface plasmon resonance (LSPR). Understanding excited state and reaction intermediate during light irradiation to return to ground state may be important for such composite systems. Therefore, we investigated such optical properties for systems using time-resolved luminescence and transient absorption measurements. DMSO solutions of the four newly prepared and characterized complexes (MMn, MZn, CMn, and CZn) and ethanol solutions of the composite materials of each complex with AgNPs were served for optical measurements. The time-correlated single photon counting (TCSPC), the streak camera which is much shorter period of time than TCSPC and transient absorption measurement, was performed for the eight samples. The fluorescence lifetime of the sole complexes and the composite materials with AgNPs was derived from curve-fitting analysis of luminescence decay curves of TCSPC. Lifetime of the composite systems with AgNPs was longer than that of the corresponding sole metal complexes for three cases. It was revealed that composite systems may go through three reaction intermediates during relaxation from excited state to ground state.

STUDIES ON THE PROPERTIES OF SCHIFF BASE TYPE ARYLMERCURY COMPOUNDS Ⅲ TRANSMETALLATION REACTION OF SCHIFF BASE TYPE ARYLMERCURY COMPOUNDS WITH METALLIC TIN

The transmetallation reaction of 4 Schiff base type arylmercury compounds with metallic tin has been carried out in refluxing xylene.It was found that the reaction proceeds in the same manner as that of chloro[2-(phenylazo)phenyl]mercury(Ⅱ) to give dichlorobisaryltin(Ⅳ).The ~1H NMR spectra of the products provide evidence for the presence of N→Sn intramolecular coordination.The formation of dichlorobisaryltin(Ⅳ)as a unique product probably arises from the N→Sn intramolecular coordination which results in the increasing of the stability of the molecule.

NOTCH WEAR OF MACHINING NICKEL BASED ALLOYS WITH CERAMIC TOOLS

The performances of mixed ceramic and sialon ceramic tools in machining nickel based alloy are tested.The negative cutting edge inclination and small tool lead angle are recommended for reducing ceramic tool failure. So called“notching at depth of cut”is not actually at the depth of cutting line, but out of cutting area。 The real reason of notching is caused by shocking of “sawtooth”on sawtooth- shaped burr and fin- shaped edges of chip

Synthesis and crystal structure of Ni,Cu complexes of 5-methyl-10,10,15,15,20,20-hexaethylcalix[4]pyrrole mono-Schiff bases

The functionalized calix[4]pyrrole meso-substituted Schiff bases were conveniently prepared by four- step synthetic route. Furthermore, the nickel and copper complexes of calix[4]pyrrole meso-substituted Schiff base with 1：2 stoichiometry were obtained. The crystal structures of the calix[4]pyrroles and their metal complexes were determined by X-ray diffraction.

Synthesis,crystal structures and complexing ability of difunctionalized copillar[5]arene Schiff bases

An efficient method for the synthesis of some difunctionalized copillar[5]arene Schiff bases from condensation of salicylaldehyde and its 5-chloro,5-bromo,3,5-di（t-butyl） substituted derivatives with corresponding diamino-functionalized copillar[5]arene,which were prepared by Gabriel reaction according to the reported method.Single-crystals of six copillar[5]arenes were determined by X-ray diffraction.An ORTEP of compounds showed that the two chains units of Schiff base exist in the outside of the cavity of pillar[5]arene.Furthermore,the complexing ability of these Schiff bases to transition metal ions were investigated by UV and fluorescence spectroscopy.

Vacuum brazing TiAl intermetallic to K4169 alloy using amorphous filler metals Ti_(56.25–x)Zr_(x)Ni_(25)Cu1_(8.75)

A series of Ti_(56.25-x)Zr_(x)Ni_(25)Cu1_(8.75)(x=0–25,at.%) filler metals were designed based on a cluster-plus-glue-atom model to vacuum braze TiAl intermetallic to K4169 alloy. The impact of Zr content on the interfacial microstructure and shear strength of joints was examined. And the relationship between the interfacial lattice structure and the fracture behavior of the joint was investigated. The findings reveal a sectionalized characteristic with three reaction zones (Zone I, Zone II and Zone III) in the microstructure of the TiAl intermetallic to K4169 alloy joint. As the Zr content in filler metals increased, the diffusion of Ti transitioned from long-distance to short-distance in Zone I, changing the initial composition from TiNi_(3) /TiNi/NiNb/(Cr, Fe, Ni)SS to NiCrFe/(Cr, Fe, Ni)SS /TiNi. In Zone II, the initial composition altered from TiNi_(3) /TiNi to TiNi/Ti_(2) Ni/TiNi_(3) /TiCu/TiNi. The interface between Zones II and III altered from a non-coherent and semi-coherent interface of TiNi/TiAl/Ti_(3) Al with significant residual stress to a semi-coherent interface of TiNi/TiNi_(3) /TiAl_(2) /Ti_(3) Al with a gradient distribution. The shear strength of the joint initially decreased and then increased. When the Zr content of filler metal was 25 at.%, the shear strength of the joint reached 288 MPa. The crack initiation position changed from non-coherent TiNi/TiAl interface with high angle grain boundaries (HAGBs) and lattice mismatch of 65.86 at.% to a semi-coherent Ti3 Al/TiAl2 interface with a lattice mismatch of 20.07 at.% when the Zr content increased. The brittle fracture was present on the fracture surfaces of all brazed joints.

Extraction and separation of Nd(Ⅲ), Sm(Ⅲ), Dy(Ⅲ), Fe(Ⅲ), Ni(Ⅱ), and Cs(Ⅰ) from concentrated chloride solutions with N,N,N',N'-tetra(2-ethylhexyl) diglycolamide as new extractant

The feasibility of using N,N,N＇,N＇-tetra（2-ethylhexyl）diglycolamide （TEHDGA） in 75 vol.% n-dodecane-25 vol.% n-octanol as agents for the extraction and separation ofNd（III）, Sm（III）, Dy（llI）, Fe（III）, Ni（II）, and Cs（I） from concentrated chlo- ride solution was investigated. Different extraction behaviors were obtained towards rare earth elements （REE） studied and Fe（IIl）, Ni（II） and Cs（I）. Efficient separation of Nd（III）, Sm（III） and Dy（III） from Fe（III）, Ni（II）, and Cs（I） was achieved by TEHDGA, depending on the HCI, HNO3 or H2SO4 concentration. A systematic investigation was carried out on the detailed extraction prop- erties of Nd（III）, Sm（III）, and Dy（III） with TEHDGA from chloride media. The IR spectra of the extracted species were investi- gated.

Effect of annealing treatment on the anti-pulverization and anti-corrosion properties of La_(0.67)Mg_(0.33)Ni_(2.5)Co_(0.5) hydrogen storage alloy

The Lao.67Mg0.33Ni2.5Co0.5 hydrogen storage alloy was prepared by the vacuum intermediate frequency induction furnace followed by annealing treatment. The pulverization degree of both the as-cast and annealed alloy powders after gaseous hydriding and dehydriding cycle was investigated and the discovery was that annealing treatment could hardly ameliorate their anti-pulverization ability. The element content of La, Mg, Ni and Co existing in electrolyte before and after the electrochemical cycles by using ICP-AES technology was also analyzed and it showed that a large amount of La and Mg were dissolved in the electrolyte, but the amount of dissolution for La and Mg significantly declined when the alloy was annealed. The XRD analysis revealed that all the al- loys consisted of two main phases AB3 and AB2 and a residual phase AB5 while annealing treatment made the AB2 phase decrease slightly. Furthermore, the anti-corrosion abilities of various elements in different phases of the as-cast and annealed alloy samples were studied by analyzing the element （La, Mg, Ni, Co） change with the corrosion time in phases AB3 and AB2 by means of EDS. It turned out that the element of La was mainly corroded out from the phase AB2 while not easily from the phase AB3. However, the element of Mg was both easily corroded out from the phases AB2 and AB3, but the corrosion was more obvious in the phase AB3. Therefore, annealing improved the anti-corrosion performances of La and Mg in the phase AB2.

Photothermal ablation therapy for cancer based on metal nanostructures

Besides conventional surgery, radiation therapy, and chemotherapy, which all tend to have side-effects and damage normal tissues, new medical strategies, such as photothermal sensitization and photo-thermal ablation therapy (PTA) with near-IR laser light, have been explored for treating cancer. Much of the current excitement surrounding nanoscience is directly connected to the promise of new nanotechnology for cancer diagnosis and therapy. The basic principle behind PTA is that heat generated from light can be used to destroy cancer cells. Strong optical absorption and high efficiency of photothermal conversion at the cancer sites are critical to the success of PTA. Because of their unique optical properties, e.g., strong surface plasmon resonance (SPR) absorption, noble metal nanomaterials, such as gold and silver, have been found to significantly enhance photothermal conversion for PTA applications. Substantial effort has been made to develop metal nanostructures with optimal structural and photothermal properties. Ideal metal nanostructures should have strong and tunable SPR, be easy to deliver, have low toxicity, and be convenient for bioconjugation for actively targeting specific cancer cells. This review would highlight some gold nanostructures with various shapes and properties, including nanoparticles (NPs), nanorods (NRs), nanoshells, nanocages, and hollow nanospheres, which have been studied for PTA applications. Among these structures, hollow gold nanospheres (HGNs) exhibit arguably the best combined properties because of their small size (30―50 nm), spherical shape, and strong, narrow, and tunable SPR absorption.

Plasmonic sensor with variable claddings based on metallic slit arrays

We propose a plasmonic sensor with variable refractive index （RI）, which exhibits high sensitivity and extraordinary optical transmission （EOT）. Its variable RI is attributed to its dielectric layers and metallic slit arrays. According to simulation results, the third resonant wavelength has a wavelength sensitivity of 800 nm/RIU and an ultra-high transmittance of 0.8 by adjusting the RIs of the upper and lower dielectrics, incident light angle, and structural geometric parameters. With its unique features, the proposed structure holds considerable potential for extensive application to metal–dielectric grating sensors operating at visible and near-infrared frequencies.