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1.
Three cardo bisphenols containing decahydronaphthalene group viz., 4,4′-(octahydro-2(1H)-naphthylidene)bisphenol, 4,4′-(octahydro-2(1H)-naphthylidene)bis-3-methylphenol and 4,4′-(octahydro-2(1H)-naphthylidene)bis-3,5-dimethylphenol were synthesized starting from commercially available 2-naphthol and were utilized for synthesis of new aromatic polyesters by phase transfer-catalyzed interfacial polycondensation with isophthaloyl chloride, terephthaloyl chloride and a mixture of isophthaloyl chloride and terephthaloyl chloride (50:50 mol %). Inherent viscosities and number average molecular weights (Mn) of polyesters were in the range 0.35-0.84 dL/g and 13,300-48,500 (Gel Permeation Chromatography, polystyrene standard), respectively. Polyesters were readily soluble in organic solvents such as dichloromethane, chloroform, tetrahydrofuran, meta-cresol, pyridine, N,N-dimethylformamide, N,N-dimethylacetamide, and 1-methyl-2-pyrrolidinone at room temperature and could be cast into tough, transparent and flexible films from their chloroform solutions. Wide-angle X-ray diffraction measurements revealed the amorphous nature of polyesters. The glass transition temperature of polyesters was in the range 207-287 °C. The temperature at 10% weight loss (T10), determined from thermogravimetric analysis of polyesters, was in the range 425-460 °C indicating their good thermal stability.  相似文献   

2.
Three new chromophores and trans-4-(N-(ethyl 4″-nitrobenzoate)-N-ethyl amino)-4′-(dimethyl amino) stilbene (DMANHAS) have been synthesized and whose chemical structures have been characterized by 1H NMR, IR, and elemental analyses. Linear absorption, single-photon-induced fluorescence and two-photon-induced fluorescence are experimentally studied. Trans-4-(N-2-hydroxyethyl-N-ethyl amino)-4′-(dimethyl amino)stilbene (DMAHAS) and trans-4-(N-2-hydroxyethyl-N-ethyl amino)-4′-(diethyl amino)stilbene (DEAHAS) have effective two-photon absorption cross-sections of σ2=0.91×10−46 cm4 s/photon and σ2=1.19×10−46 cm4 s/photon at 532 nm by using an open aperture Z-scan technique, respectively. When pumped with 800 nm laser irradiation, DMAHAS and DEAHAS indicate strong two-photon-induced blue fluorescence of 436 and 440 nm, respectively, while trans-4-(N-(ethyl 4″-nitrobenzoate)-N-ethyl amino)-4′-(diethyl amino) stilbene (DEANHAS) and DMANHAS exhibit no fluorescence.  相似文献   

3.
Ion-selective membrane electrodes doped with the urea- or thiourea-functionalised calix[4]arenes, 5,11,17,23-tetra-tert-butyl-25,27-bis[[4-N′-(phenylureido)butyl]oxy]-26,28-dipropoxy calix[4]arene (I) and 5,11,17,23-tetra-tert-butyl-25,27-bis[[4-(N′-phenylthioureido)-butyl]oxy]-26,28-dipropoxy calix[4]arene (II), were evaluated for anion sensing. Potentiometric results show that these calixarene ionophore-based membrane electrodes exhibit a good sensitivity to aqueous solutions of the monohydrogen orthophosphate species HPO42− in the concentration range 5.0 × 10−5 to 1.0 × 10−1 M, with near-Nernstian response slopes of −33.0 and −28.0 mV dec−1 for ionophores I and II, respectively. Selectivity coefficient values for monohydrogen orthophosphate over a range of common anions were determined by the fixed interference and matched potential methods and indicated that these membrane electrodes exhibit a good selectivity for HPO42− with respect to the other anions, including sulfate and nitrate.  相似文献   

4.
A series of macrobicyclic unsymmetrical binuclear copper(II) complexes of compartmental ligands were synthesized from the Schiff base condensation of 1,8[N,N′-bis{(3-formyl-2-hydroxy-5-methyl)benzyl}]-1,4,8,11- tetraaza-5,5,7,12,12,14-hexa methylcyclotetradecane with diamines like 1,2-diamino ethane, 1,3-diamino propane, 1,4-diaminobutane, 1,2-diaminobenzene and 1,8-diaminonaphthalene. The complexes were characterized by elemental and spectral analysis. Electrochemical studies of the copper(II) complexes show two irreversible one-electron reduction processes around E1pc = −0.70 to −1.10 V and E2pc = −0.98 to −1.36 V. ESR spectra of the binuclear copper(II) complexes show a broad signal at g = 2.10 and μeff values in the range 1.46–1.59 BM, which convey the presence of antiferromagnetic coupling. Cryomagnetic investigation of the binuclear complexes [Cu2L3(ClO4)](ClO4) and [Cu2L4(ClO4)](ClO4) show that the observed −2J values are 144 and 216 cm−1, respectively. The observed initial rate (Vin) for the catalytic hydrolysis of p-nitrophenyl phosphate by the binuclear copper(II) complexes were in the range 1.8 × 10−5 to 2.1 × 10−5 Ms−1. The initial rate (Vin) for the catalytic oxidation of catechol to o-quinone by the binuclear copper(II) complexes were in the range 2.7 × 10−5 to 3.5 × 10−5 Ms−1. The copper(II) complexes have been found to promote cleavage of plasmid pBR 322 DNA from the supercoiled form I to the open circular form II.  相似文献   

5.
A reagent tablet for determination of fluoride ion has been prepared using ethylenediamine-N,N,N′,N′-tetraacetate complex of zirconium (Zr-EDTA), 3-hydroxy-2′-flavone (FS) and an appropriate pH buffer. Dissolving of the tablet into water exhibits an intense blue fluorescence (λmax = 460 nm) upon excitation at 377 nm and the fluorescence intensity decreases with the presence of fluoride ion. Hence, a simple fluorescent detection procedure for fluoride ion in aqueous media was successfully constructed with this tablet. The principle of this detection system is the ligand exchange reaction of FS bound to Zr-EDTA with fluoride ion. The present system provides an easy, rapid and selective determination method of fluoride ion ranging from 5 × 10−6 to 1 × 10−3 mol dm−3. The measurement of real samples with this tablet showed the similar results as those by the common method with the Alfusone reagent.  相似文献   

6.
A new naphthalene-ring containing diamine, bis-[4-(5-amino-naphthalene-1-yloxy)-phenyl]-methanone was prepared from reaction of 5-amino-1-naphthol with 4,4′-dichlorobenzophenone in the presence of K2CO3. A series of novel polyamides were prepared by direct polycondensation of the diamine with various commercially available diacid chlorides including terephthaloyl chloride, isophthaloyl chloride, adipoyl chloride, and sebacoyl chloride. All the synthesized polyamides showed good solubility in amide type solvents such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, and N,N-dimethylformamide and they exhibited inherent viscosities in the range of 0.44-0.52 dL/g. According to the DMTA analysis, the glass transition temperatures of the polyamides were found to be 131-187 °C. Thermogravimetric analysis indicated that the polymers were stable up to 190 °C and the 10% weight loss temperatures were recorded in the range of 350-418 °C in air atmosphere.  相似文献   

7.
A novel biomimetic sensor for rutin determination based on a dinuclear complex [MnIIIMnII(Ldtb)(μ-OAc)2]BPh4 containing an unsymmetrical dinucleating ligand, 2-[N,N-bis(2-pyridylmethyl)-aminomethyl]-6-[N-(3,5-di-tert-butyl-2-oxidoben-zyl)-N-(2-pyridylamino)aminomethyl]-4-methylphenol (H2Ldtb), as a manganese peroxidase mimetic was developed. Several parameters were investigated to evaluate the performance of the biomimetic sensor obtained after the incorporation of the dinuclear complex in a carbon paste. The best performance was obtained in 75:15:10% (w/w/w) of the graphite powder:Nujol:MnIIIMnII complex, 0.1 mol L−1 phosphate buffer solution (pH 6.0) and 4.0 × 10−5 mol L−1 hydrogen peroxide. The response of the sensor towards rutin concentration was linear using square wave voltammetry in the range of 9.99 × 10−7 to 6.54 × 10−5 mol L−1 (r = 0.9998) with a detection limit of 1.75 × 10−7 mol L−1. The recovery study performed with pharmaceuticals ranged from 96.6% to 103.2% and the relative standard deviation was 1.85% for a solution containing 1.0 × 10−3 mol L−1 rutin (n = 6). The lifetime of this biomimetic sensor was 200 days (at least 750 determinations). The results obtained for rutin in pharmaceuticals using the biomimetic sensor and those obtained with the official method are in agreement at the 95% confidence level.  相似文献   

8.
Mononuclear copper(II) complexes, [Cu L1] (ClO4)2 (1), [Cu L2] (ClO4)2 (2) and [Cu L3] (ClO4)2 (3) with quadridentate Schiff base ligands L1 (N,N′-bis-pyridin-2-ylmethyl-butane-1,4-diimine), L2 (N,N′-bis-pyridin-2-ylmethyl-pentane-1,5-diimine) and L3 (N,N′-bis-pyridin-2-ylmethyl-hexane-1,6-diimine) have been synthesized and characterized. The crystal structure data of 1 reveals the existence of the complex in two different geometries, namely a square pyramid and a distorted octahedron, which eventually leads to the packing of the molecule into helical and anti-parallel structures respectively. Absorption titration studies with calf thymus DNA for all three complexes are suggestive of groove binding with binding constant values for 1, 2 and 3 being 2.6 ± 0.2 × 104 M−1, 11.5 ± 0.2 × 104 M−1 and 1.83 ± 0.2 × 104 M−1 respectively. Control cleavage experiments using pBR 322 plasmid DNA and distamycin suggest minor groove binding for these complexes. In the presence of ascorbic acid, the complexes show efficient DNA cleavage, the order of efficiency being 1 > 2 ≅ 3.  相似文献   

9.
The construction and performance characteristics of polymeric membrane electrodes based on two neutral ionophores, N,N′-[bis(pyridin-2-yl)formylidene]butane-1,4-diamine (S1) and N-(2-pyridinylmethylene)-1,2-benzenediamine (S2) for quantification of cadmium ions, are described. The influences of membrane compositions on the potentiometric response of the electrodes have been found to substantially improve the performance characteristics. The best performance was obtained with the electrode having a membrane composition (w/w) of (S1) (2.15%):PVC (32.2%):o-NPOE (64.5%):KTpClPB (1.07%). The proposed electrode exhibits Nernstian response in the concentration range of 7.9 × 10−8 to 1.0 × 10−1 M Cd2+ with limit of detection 5.0 × 10−8 M, performs satisfactorily over wide pH range (2.0-8.0) with a fast response time (10 s). The sensor has been found to work satisfactorily in partially non-aqueous media up to 30% (v/v) content of methanol, ethanol and acetonitrile and could be used for a period of 2 months. The analytical usefulness of the proposed electrode has been evaluated by its application in the determination of cadmium in real samples. The practical utility of the membrane electrode has also been observed in the presence of surfactants.  相似文献   

10.
Fakhari AR  Khorrami AR  Naeimi H 《Talanta》2005,66(4):813-817
A novel sensitive chromogenic reagent, N,N′-bis(3-methylsalicylidene)-ortho-phenylene diamine (MSOPD), has been synthesized and used in the spectrophotometric determination of nickel. At pH 8, MSOPD can react with nickel ion at room temperature to form a 1:1 complex. The apparent molar absorptivity is 9.5 × 104 l mol−1 cm−1 at 430 nm. Beer's low is obeyed over the range 0-1.0 × 10−5 M of nickel with a detection limit of 1.36 × 10−8 M. The relative standard deviation for measurement of 3.41 × 10−6 M nickel is 1.3% (n = 10). The method has successfully been applied to determination of trace amounts of nickel in some natural food samples.  相似文献   

11.
A new interesting class of linear unsaturated polyesters based on dibenzylidenecycloalkanones have been synthesized by interfacial polycondensation of 4,4-azodibenzoyl chloride or 3,3-azodibenzoyl chloride with: 2,5-bis(p-hydroxybenzylidene)cyclopentanone I, 2,6-bis(p-hydroxybenzylidene)cyclohexanone II, 2,6-divanillylidenecyclohexanone III, or 2,7-bis(p-hydroxybenzylidene)cycloheptanone IV at ambient temperature. The copolyesters are also synthesized from the monomers I, II, III or IV with the diacid chlorides. The resulting polyesters and their copolyesters were characterized by elemental analyses, IR spectroscopy and solubility. Additionally, inherent viscosity of the polyesters in the range 0.32-0.86 dL g−1 and the inherent viscosity of the copolyesters in the range 0.28-0.65 dL g−1 were determined. The UV-visible spectra of certain polymers were measured in m-cresol solution and showed a characteristic absorption band at 435-473 nm due to n-π* transition. The thermal properties of the polymers were evaluated by thermo gravimetric analysis and differential scanning calorimetry measurements and correlated with their structural units. The crystallinity of some polyesters and copolyesters were tested. In addition, the electrical properties of all polyesters and copolyesters were measured.  相似文献   

12.
Palladium sensors based on two neutral ionophores, N,N′-bis(acetylacetone) cyclohexanediamine (L1) and N,N′-bis(o-hydroxyacetophenone)-1,2-cyclohexanediamine (L2) for quantification of palladium ions are described. Effect of various plasticizers (o-NPOE, DBP, DEP, DOP, TBP, and CN) and anion excluder, sodium tetra phenyl borate (NaTPB) has been studied. The best performance is obtained with a membrane composition of PVC:o-NPOE:ionophore (L1):NaTPB of 150:300:5:5 (%, w/w). The sensor exhibits significantly enhanced selectivity towards palladium ion over the concentration range 1.0 × 10−8 to 1.0 × 10−1 M with a lower detection limit of 4.0 × 10−9 M and a Nernstian compliance (29.1 ± 0.3 mV decade−1 of activity) within pH range 2.0-6.0 and fast response time of 10 s. Influence of the membrane composition and possible interfering ions has also been investigated on the response properties of the electrode. Fast and stable response, good reproducibility and long-term stability of the sensor are demonstrated. The sensor has been found to work satisfactorily in partially non-aqueous media up to 20% (v/v) content of methanol, ethanol and acetonitrile and could be used for a period of 4 months. Selectivity coefficients determined with fixed interference method (FIM) indicate high selectivity for palladium. The proposed electrode shows fairly good discrimination of palladium from other cations. The application of prepared sensor has been demonstrated in determination of palladium ions in spiked water sample.  相似文献   

13.
Kim DW  Park KW  Yang MH  Kim TH  Mahajan RK  Kim JS 《Talanta》2007,74(2):223-228
The new ion-selective electrodes (ISEs) based on salphenH2 derivatives such as N,N′-(propylenedioxy)benzenebis(salicylideneimine) L1 and N,N′-4,5-(propylenedioxy)benzenebis(3,5-di-tert-butylsalicylideneimine) L2 as cation carriers are developed for a uranyl ion. The combination of these new ionophores with tris(2-ethylhexyl)phosphate (TEHP) as a plasticizer particularly shows near Nernstian slope in the wide concentration range (1.0 × 10−6 to 1.0 × 10−2 M) of UO22+ and is observed well in the pH range from 1.0 to 5.0 with a response time less than 20 s. Since the employed ionophores were confirmed to form well-defined stable 1:1 complexes with UO22+, the observed high selectivity for a uranyl ion over the other cations was attributed to the selective complexation as well as the lipophilic behavior of these ligands especially for L2. The proposed electrodes offered practically low detection limit of 6.5 × 10−7 M and reasonably good end-points within experimental error were obtained when the sensor was used as an indicator electrode for the potentiometric titration.  相似文献   

14.
We report the synthesis of a novel bistriazene, 4,4′-bis(3-(4-phenylthiazol-2-yl)triazenyl)biphenyl (BPTTBP), and its highly sensitive color reaction with Hg2+. The new reagent was synthesized in good yield by coupling 2-amino-4-phenylthiazole with 4,4′-biphenyldiamine bisdiazonium salt. Using a blend of surfactants N-cetylpyridinium chloride (CPC) and polyethylene glycol n-octanoic phenyl ether (OP) as a micelle sensitizer, the red colored reagent assembles with Hg2+ in pH 9.8 borate buffer according to a 1:1 stoichiometry, forming a blue oligomeric/polymeric chelating complex with a high apparent stability constant (1.1 × 108 M−1). Whereas the maximum absorption of reagent occurs at 510 nm with an extinct coefficient of 1.35 × 104 M−1 cm−1, the complex absorbs at 611 nm, with an apparent extinct coefficient of 1.04 × 105 M−1 cm−1. Beer's law is obeyed in the range of 0-15 μg/25 mL Hg2+, and Sandell's sensitivity is 1.92 × 10−3 μg/cm2. In the presence of thiourea and Na4P2O7 as masking agents, the method was found free from interferences of foreign ions commonly occurring with mercury. The optimized protocol has been successfully applied to spectrophotometric determination of mercury in waste water samples. The features of the new reagent associated with its special structure were discussed, and an unprecedented “domino effect” was proposed to account for its unique chelating stoichiometry with Hg2+.  相似文献   

15.
Songnan Qu 《Tetrahedron》2008,64(48):10890-10895
A linear-shaped bi-1,3,4-oxadiazole derivative, oxalyl acid N′,N′-di(4-(2-ethylhexyloxy)benzoyl)-hydrazide (FH-Z8) was designed and synthesized. Quadruple hydrogen bonds between bi-dihydrazide units and π-π interactions cooperatively participated in forming supramolecules in chloroform at higher concentrations of FH-Z8. The association constants (K) in chloroform were 2.2×103 and 1.8×103 M−1 based on NH1 and NH2 in FH-Z8, respectively. FH-Z8 could gel dichloroethane efficiently with the critical gelation concentration (CGC) of 0.14 wt %, while spontaneously crystallized from the gel during storage.  相似文献   

16.
We have synthesized a bis(terthiophene)-appended uranyl-salophen complex, comprising N,N′-bis[4-(5,2′:5′,2″-terthiophen-3′-yl)salicylidene]-1,2-ethanediamine-uranyl complexes (TUS), and used it as a monomer for the electrochemical polymerizations (poly-TUS) on glassy carbon surfaces to prepare functionalized conducting polymer (CP) films. The poly-TUS films prepared from propylene carbonate/0.1 M tetrabutyl ammonium perchlorate (TBAP) on a glassy carbon electrode have both the functionality of ion-to-electron transducers (solid contact) and Lewis-acidic binding sites for a monohydrogen phosphate (MHP) ion-selective electrode (ISE). The CP/poly-TUS sensor showed a linear range between 1.0 × 10−1 and 1.0 × 10−4.5 M with a near-Nernstian behavior (−30.4 mV decade−1) at a pH of 8.2. The detection limit of the electrode was 10−5.0 M and the response time was improved (<10 s) compared to that of conventional ISEs (<20 s). For comparison, a conventional ISE (with an internal aqueous solution) based on a TUS monomer/o-nitrophenyl octylether (o-NPOE)/polyvinyl chloride (PVC) liquid membrane with or without tridodecylmethylammonium chloride (TDMACl) as an additive was also constructed and its performance as an MHP-ISE were studied. The superior selectivity and sensitivity of the CP/poly-TUS sensor enabled the direct measurement of MHP in a wide variety of applications.  相似文献   

17.
3,4-Di-(2′-hydroxyethoxy)-4′-nitrobenzylidene II was prepared by condensation reaction of 3,4-dihydroxy-4′-nitrobenzylidene I with 1-chloro-2-ethanol. Monomer II was reacted with p-phenylene diisocyanate to yield polyurethane containing the non-linear optical chromophore 3,4-di-(2′-hydroxyethoxy)-4′-nitrobenzylidene. Polymer III shows thermal stability up to 300 °C in TGA thermogram. Tg value of the polymer obtained from DSC thermogram was 110 °C. The resulting polyurethane III was soluble in common organic solvents such as acetone, DMF and DMSO. The values of electro optic coefficient d33 and d31 of the poled polymer film were 3.15 × 10 −7 and 1.5 × 10 −7 esu, respectively.  相似文献   

18.
The two nickel chelates of Schiff bases, 3-hydroxy-N-{2-[(3-hydroxy-N-phenylbutyrimidoyl)-amino]-phenyl}-N′-phenylbutyramidine (M1) and bis-4-(ethyliminomethyl)naphthalene-1-ol (M2), have been synthesized and explored as ionophores for preparing PVC-based membrane sensors selective to nickel ion. The influences of membrane compositions on the potentiometric response of the electrodes have been found to substantially improve the performance characteristics. The best performance was obtained with the electrode having a membrane composition (w/w; mg) of (M1): PVC:NaTPB:CN in the ratio 5:150:5:150. The sensor shows a linear potential response for Ni2+ over a wide concentration range 1.6 × 10−7 to 1.0 × 10−2 M with Nernstian compliance (30.0 ± 0.2 mV/decade of activity) within pH range 2.5-9.5 and a fast response time of 10 s. The sensor has been found to work satisfactorily in partially non-aqueous media up to 20% (v/v) content of methanol, ethanol, and acetonitrile and could be used for a period of 4 months. The analytical usefulness of the proposed electrode has been evaluated by its application in the determination of nickel in real samples. The practical utility of the membrane electrode has also been observed in the presence of surfactants.  相似文献   

19.
N,N′,N″,N′′′-1,5,8,12-tetraazadodecane-bis(salicylaldiminato)(H2L) has been used as ionophore for preparing Mn2+ selective sensor. Membranes of different composition with regard to ratio of H2L:PVC:NPOE:NaTPB have been prepared and investigated. The best performance was obtained with the membrane of composition 10:150:150:10 (H2L:PVC:NPOE:NaTPB) (w/w; mg). This membrane generated linear potential response in the concentration range of 5.0 × 10−6 to 1.0 × 10−1 M with a Nernstian slope of 30.0 mV/decade of activity and fast response time (10 s). Hydrogen ion does not effect to the performance of sensor in the pH range 3.0-6.5. The sensor was found to be sufficient selective for Mn2+ over a number of alkali, alkaline and heavy metal ions and could therefore be used for the determination of manganese in various samples by direct potentiometry.  相似文献   

20.
A polyvinyl chloride (PVC) based membrane sensor for cerium ions was prepared by employing N,N′-bis[2-(salicylideneamino)ethyl]ethane-1,2-diamine as an ionophore, oleic acid (OA) as anion excluder and o-nitrophenyloctyl ether (o-NPOE) as plasticizer. The plasticized membrane sensor exhibits a Nernstian response for Ce(III) ions over a wide concentration range (1.41 × 10−7 to 1.0 × 10−2 M) with a limit of detection as low as 8.91 × 10−8 M. It has a fast response time (<10 s) and can be used for 4 months. The sensor revealed a very good selectivity with respect to common alkali, alkaline earth and heavy metal ions. The response of the proposed sensor is independent of pH between 3.0 and 8.0. It was used as an indicator electrode in potentiometric titration of fluoride, carbonate and oxalate anions and determination of cerium in simulated mixtures.  相似文献   

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