Synthesis and Characterization of New Polyimide Containing Calix[4]arenes in the Polymer Backbone with Transport Ability

New polyimide containing calix [4] arene moieties on the polymer backbone was successfully synthesized in N- methy1 - 2 - pyrrolidone （NMP） by polycondensations of 3, 3＇, 4, 4＇- oxydiphthalic anhydride （ODPA） with the diaminocalix[4]arene monomer using 3,3＇- dimethy1- 4, 4＇- The polyimide prepared is soluble in common solvents, such as NMP, DMAc, DMF and chloroform. The polyimide films obtained have excellent thermal stability and mechanical property. At the same time, the liquid membrane transport of potassium ions by the new polyimide was investigated, which testified that compared to ODPA-DADPM polyimide, the polyimide containing culix[4] arenes has the transport ability to metal ions in regard to bulky, cone-like calix [-4] arene moieties.     

Transports of K^＋, Ca^2＋ Ions in Liquid Membrane with Calixarene Derivatives as Carriers

A few derivatives of calixarenes have been synthesized and characterized by IR, ^1H NNtR, thermal and elemental analysis. The transport of potassium or calcium ion through the liquid membrane, in which the derivatives act as carriers, has been studied. The electron-effect of the substituent on the upper rim of calixarene possesses important effect on the net transport of metal ions. The p- tert-butylcalix[4]arene is the best carrier of calcium ion, compared with p-tert-calix[4]arene（n = 4, 6, 8）. The ptert-butylcalix[4]arene acid is better than p-tert-butylcalix [4]arene. The calixr43crown is the best carrier of calcium ions of all the carriers. The pH gradient between the source and receiving phase, and the concentration of K^＋ , Ca^2＋ ions in the source phase affect mainly transport. After the transport, the pH value of the source phase is found to be decreased, once the calix [n ] arene derivatives act as carrier. But it is not the case for the calix[n] crowns. It might be interpreted as the result of their different mechanisms.     

A Novel Tetraphenylethylene-Based “Turn On” Fluorescent Sensor with Highly Sensitive Response to Mercury Ions

A novel 4-tert-butyl-N'-(4-(1, 2, 2-triphenylvinyl) benzylidene) benzohydrazide(TBB) was successfully synthesized in simple one-step process. It was characterized by FT-IR, 1 H NMR, 13 C NMR and HRMS. Its fluorescence sensing ability to 15 metal ions was investigated. Weak emission from TBB could be efficiently increased by trace Hg~(2+), through coordination reaction between TBB and Hg~(2+) with "turn on" character. The fluorescence intensity of TBB/Hg~(2+)([TBB] = 3.0×10~(–6) mol/L, [Hg~(2+)] = 1.3×10~(–4) mol/L) was 7.5 times higher than that of TBB. This TBB sensor exhibited high selectivity for Hg~(2+) and other metal ions did not interfere in this determination. The limit of detection was 0.566 μmol/L(S/N=3). The experimental results showed that this TBB sensor could sensitively respond to Hg~(2+) within concentration range(from 5×10~(–6) mol/L to 1.3×10~(–4) mol/L).     

A New Type of Dibenzoyl Tartaric Acid Selective Electrode Baded on Polymer Membrane Containing Calix[4] arene lonophore

A new type of dibenzoyl tartaric acid selective electrode has been developed. Three double-arm calix [4] arene derivatives were employed as the neutral ionophores. The poly(vinyl chloride) membrane electrode containing an amide derivative of calix [4] arene as the neutral carrier and a dibutyl phthalate as the plasticizer exhibited the highest sensitivity for dibenzoyl tartaric acid. The slope of linear portion was 27.8mV per concertration decade. The electrode has a fast response and a long lifetime.     

Assembly and Characterization of Coordination Polymer Nanostructural Materials at Interfaces

1 Results Molecular self-assembly of one-/two-dimensional (1D/2D) nanostructures has recently received great interest because the specific structures of crystals determine their unique physical and chemical properties. Coordination polymers contain two central components, connectors and linkers. Transition metal ions are often used as versatile connectors, with coordination numbers ranging from 2 to 7 dependant on the oxidation states of the metal ions. Multidentate ligands are often used as linkers, which can afford a wide variety of linking sites tuned binding strength and directionality. Thus, by using different connectors and linkers, one can design and prepare large amount of 1D, 2D and 3D coordination polymers with various structural frameworks.     

Molecular orbital study on antiferromagnetic coupling mechanism in a silver (I) complex

Typically, magnetic interactions between paramagnetic centers through diamagnetic metal ions are negligibly small or weakly antiferromagnetic[1]. However, it has been proven that some metal complexes with organic radical ligands, in which the metal ions are diamagnetic, mediate substantial magnetic interactions. For example, metal complexes with semiquinones[2―4] show that a variety of magnetic interactions depend on metal ions and coordina-tion geometries, and the magnitude of the magnetic i…     

Simultaneous Fluorescence Detection of Mercury(Ⅱ) and Silver Ions Based on Rhodamine B Isothiocyanate and 5-Carboxyfluorescein-ss DNA Modified Probe

A new fluorescence sensor is developed for simultaneous detection of Hg~(2+) and Ag~+. During the detection process,Hg~(2+) forms complexes with the fluorescent dye rhodamine B isothiocyanate(RBITC) modified onto the surface of gold nanoparticles(Au NPs),resulting in RBITC's displacement from the surface of Au NPs and the recovery of fluorescence. Meanwhile,Ag~+ forms “C-Ag~+-C” complex with C-rich 5-carboxyfluorescein(FAM)-ss DNA modified onto the surface of Au NPs,which keeps the fluorescent dye FAM close to the Au NPs and results in quench of fluorescence. The experimental results show a wide linear range and a good sensitivity. The limit of detection is 1.06 nmol/L for Ag~+ and 0.48 nmol/L for Hg~(2+). This detection method is not only easy to operate but also efficient.     

Bridging of Calixarenes with N, N＇-Bis（Chloroacetyl） Propylenediamine

A new bridging reagent, N, N‘-bis (chloroacetyl) propylenediamine was used to explore the relativeactivity and bridging pattern of p-ten-bury lcalix [4] arene, p-tert-butylcalix [6] arene and butylcalix [8] arene. It wasfound that the bridging reaction is selectively, at least, preferably at 1, 3-position for p-tert-butylcalix [4] arene and p-tert-butylcalix [6] arene, 1,5-position for p-tert-butylcalix [8] arene. Taking the yield of bridged calixarene as a compar-sion standard, the activity decreases with the increasing of the number of phenolic units in calixarene.     

Macrocyclic compound as ionophores in lead(Ⅱ) ion-selective electrodes with excellent response characteristics

Macrocyclic compounds,such as crown ethers,azacrown ethers,thiacrown ethers,calixarenes and porphyrins,which act as ionophores in lead(Ⅱ) ion-selective electrodes,are systematically summarized based on the latest literatures.The molecular structure characteristics of the ionophores are general-ized.The modification regulations for the substituted ionophores are elaborated with the purpose of improving the response features of the lead(Ⅱ) ion-selective electrodes assembled by them.It is pointed out that the introduction of pendant moieties which contain soft base coordination centers like N,S and P atoms is in favor of adjusting the cavity size and conformation of the macrocyclic com-pounds.Furthermore,there is synergic effect between the cavity and the donor sites of the ligand and thus the selective complexation of lead ions is easily realized,resulting in significant avoidance of the interference from other metal ions.The macrocyclic ionophore having the best response characteris-tics thus far was found to be N,N'-dimethylcyanodiaza-18-crown-6 with the detection limit of 7.0×10-8(14.5 μg/L),which is one of the uncommon ionophores that can really eliminate the interference from silver and mercury ions.The selectivity coefficients of the ionophore for lead ions over other metal ions,such as alkali,alkaline earth and transition metal ions are in the order of 10-4 or smaller,where the se-lectivity coefficient of lead(Ⅱ) over mercury(Ⅱ) ions is much lower,down to 8.9×10-4.The structure de-sign idea for high-performance ionophore is proposed according to present results.The incorporation of nitrogen atom,especially cyano group or thiocyano group or amino/imino groups,rather than thio atom alone could result in new excellent lead ionophores.The aborative design for metacyclophanes containing aromatic nitrogen atoms with the aim of creating excellent ionophores would also become a potential research trend.The lead(Ⅱ) ion-selective electrodes have shown widely potential applications in the potentiometric titration,and flow injection potentiometry,and in the direct determination of lead in stack emissions of lead smelters,and assay of lead in rocks,particularly in the direct measurements of trace amount of lead(Ⅱ) in human hair,blood,edible oil,food,water,and air.     

Syntheses,Crystal Structures and Photoluminescence Properties of Two Cadmium(Ⅱ) Coordination Polymers

The solvothermal reaction of CdCl_2·2.5 H_2O with terephthalic acid yields two new three-dimensional(3 D) cadmium(II) coordination polymers(CPs), namely {[Cd(C_8H_4O_4)Cl]·C_2H_8N}_n and [Cd(C_8H_4O_4)]_n, we use the abbreviations CP1 and CP2 to refer to them, respectively. The compounds are characterized in detail by single-crystal X-ray diffraction, powder X-ray diffraction, IR spectroscopy, elemental analysis and thermogravimetric analysis(TGA). The results indicate that compounds CP1 and CP2 are 3 D frameworks, and both the compounds feature a uninodal 4-connected framework with a dia net. The empty spaces of such 3 D framework are filed by the other two identical frameworks, leading to a 3-fold interpenetrated network. In addition, the photochemical properties of the frameworks are also investigated. The two frameworks show strong solid-state fluorescence emission at 463 and 503 nm, respectively, which are obvious red-shift compared to the emission of ligand.     

A specific fluorescent chemosensor for copper(Ⅱ) cation recognition

The fluorescent spectra of 2, 6-bis(benzimidazol-2-yl) pyridine (compound 2) and its N-substituted compound (1) are studied. The fluorescent characteristics of these compounds and the complexes formed from these compounds with different metal ions have also been investigated. The results show that compound 1 possesses a specific ability to form complex with Cu2+ ions, but compound 2 has not such a property. It is proposed that the specific recognition ability of compound 1 to Cu2+ may attribute to the cyclic configuration of this compound in polar solvent.     

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.     

Synthesis of Novel Nanocomposites of Silica and Guar Gum:Efficient Zinc Ion Binder

1 Results Adsorption using commercial activated carbon (CAC)[1] can remove heavy metals from wastewater[2-4].However,CAC remains an expensive material for heavy metal removal.Ion exchange techniques are also used but it generates volumetric sludge and increases the cost[5].Using naturally occurring seed polysaccharides can solve these problems but their solubility in water limits its application as an adsorbent.Guar gum is a commercially available,industrially important[6-7] polysaccharide material having backbone of β-D (1→4) mannopyranosyl units with α-D-galactopyranosyl units as side chains.However being water soluble it cannot be used and recycled as metal ion binder under aqueous conditions.Present study describes synthesis of novel nanostructured composite materials out of guar gum[8] and silica which have been evaluated as efficient Zn2 metal binder.Zinc ions could be easily stripped off from the used material by washing with acid and used again for two cycles without any significant change in adsorption capacities.It's composite with silica offer materials with efficient metal ion binding properties due to porosity,water insolubility and outstanding thermal property of silica[9-10].     

Storage Characteristics of LiNi_(0.8)Co_(0.1 X)Mn_(0.1-X)O_2 (X=0,0.03,0.06) Cathode Materials for Lithium Batteries

1 Results LiNi0.8Co0.1 xMn0.1-xO2 cathodes with x=0,0.03 and 0.06 were prepared by firing a mixture of stoichiometric amounts of LiOH·H2O and coprecipitated Ni0.8Co0.1 xMn0.1-x(OH)2 at 800 ℃ for 15 h.Using these powders,their storage characteristics upon exposure to air and electrolytes at 90 ℃ were compared before charging and after charging to 4.3 V with a variation of the storage time.As the Co content (x) increased in the cathode,both the Ni2 content in the lithium 3a sites,and the contents of the LiOH and Li2CO3 impurity phases decreased.In particular,changes in the oxidation state of the Ni and Mn ions after 4.3 V charging upon storage at 90 ℃ were monitored using X-ray absorption near edge spectra (XANES),and Ni4 was found to reduce to Ni3 while the oxidation state of the predominant Mn4 did not change.However,residual Mn3 ions in the cathodes dissolved into the electrolytes.Moreover,the cathodes stored at 90 ℃ for 7 days were transformed into a spinel phase (Fd3m),regardless of the Co content.In an effort to resolve this dissolution problem,Al2O3 and Co3(PO4)2 nanoparticles were coated onto the cathode (LiNi0.8Co0.1Mn0.1O2) with the highest amounts of metal dissolution at 90 ℃.The results showed that the Co3(PO4)2-coated cathode exhibited greatly decreased metal dissolution and decreased its irreversible capacity by 5%,compared with a bare and Al2O3-coated cathodes.     

Haptotropic Migration of Metal Templates on Arene Surfaces

1 Results The chromium-templated benzannulation of arylcarbenes by alkynes provides a direct regio- and diastereoselective access to densely functionalized chromium arenes[1]. The chromium fragment undergoes a haptotropic migration along the π-face of the fused arenes which can be controlled by thermodynamics,by the substitution pattern of the arene and by the metal coligand sphere(See Scheme 1).The controlled regioselective labeling of benzene rings can be exploited in diastereoselective C-C bond formation as demonstrated for [4 2] cycloaddition reactions[2].     

In fl uence of the extraction parameters on the cytotoxicity test results of Mg materials

Recently more and more researchers query the predictability of cytotoxicity results of biomedical Mg alloys obtained according to ISO 10993 due to significant difference between in vitro and in vivo corrosion. This study aimed to observe the influence of different extraction parameters(time, volume/surface ratio and medium composition) on cytotoxicity results and illustrate whether more predictable results could be obtained by adjusting the extraction parameters. The results showed that longer extraction time and smaller extraction volume/surface ratio improve the sensitivity of screening Mg materials by making inferior Mg materials release relatively more ions to the extract; and more predictable results could not be obtained by the way of simply adding bovine serum albumin(BSA) into the extraction medium to the same level in vivo or simply using fetal bovine serum(FBS) directly as extraction medium, since BSA and FBS accelerated the corrosion of Mg materials during extraction and they affected the cells’ health states during the test. In order to get more predictable results, in our opinions, it is necessary to establish a database of primary cells’ hazards(metal ions, p H and H2gas) tolerance and a set of in vitro corrosion test with high similarity in vivo, which is very difficult to realize now however.     

Synthesis and Photophysical Properties of Novel Rod-shaped and Star Shaped Fluorescent Phosphane Derivatives

1 Results Over the past few years significant research has been directed toward the development of organic materials for potential application in molecular photonic devices[1] and the development of sensors[2].Interest in these materials is primarily due to the infinite numbers of possible molecular structures with the desired properties,by virtue of the tremendous capabilities of organic synthesis.For the development of a new fluorescent molecular sensor consisting of a recognition moiety linked to a fluorescent moiety,the choice of the fluorophore is of major importance[3] in order to ensure better sensitivity.This presentation will focus on the design,the synthesis and the photophysical investigation on new fluorophores based on phosphane oxide[4] and phosphane sulfide[5] derivatives (See Fig.1).     

Study the effects of metallic ions on the combination of DNA and histones with molecular combing technique

The effects of monovalent (Na^ , K^ ) and divalent (Mg^2 , Ca^2 , Mn^2 ) ions on the interaction between DNA and histone are studied using the molecular combing technique. λ-DNA molecules and DNA-histone complexes incubated with metal cations (Na^ , K^ , Mg^2 , Ca^2 , Mn^2 ) are stretched on hydrophobic surfaces, and directly observed by fluorescence microscopy. The results indicate that when these cations are added into the DNA solution, the fluorescence intensities of the stained DNA are reduced differently. The monovalent cations (Na^ , K^ ) inhibit binding of histone to DNA. The divalent cations (Mg^2 , Ca^2 , Mn^2 ) enhance significantly the binding of histone to DNA and the binding of the DNA-histone complex to the hydrophobic surface. Mn^2 also induces condensation and aggregation of the DNA- histone complex.     

Cu(II) effect on the conformation of regenerated silk fibroin in dilute aqueous solution

In nature, metal ions play a vital role in the function of protein and nucleic acid. It has been demonstrated that there are many kinds of metal ions in the gland of Bombyx mori (B. mori) silkworm, and their contents are different in different parts of silk gland[1]. These ions may promote the transition of gel to sol in the gland of silkworm when the silk fibroin (SF) goes forward to the spinneret. Many investigations have shown that K(I) and Ca(II) can induce the conformational transitio…     

Synthesis of Novel Low-band-Gap Thiophene-based Oligomers and Copolymers

1 Results In this contribution,the synthesis and characterization of low-band-gap oligothiophenes and copolymers based on fluorene and thiophene units are reported.First,5,5′-dibromo derivative of 1 was synthesised and used as a building block for synthesis of quinquethiophene and septithiophene analogues of 1 and the synthesis of a novel low band-gap polymer - soluble alternating copolymer 3,which was prepared by the Suzuki coupling of 5,5′-dibromo derivative of 1 with bis(propane-1,3-diyl) 9,9-bis(2-ethylhexyl)fluorene-2,7-bisboronate.Further,two soluble random copolymers 4 of 3-(3-methylbutyl)thiophene with 3-[2-(pyren-1-yl)vinyl]thiophene were prepared by Grignard metathesis copolymerization of corresponding dibromo monomers.See Fig.1.