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1.
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   

2.
Novel optically active aromatic poly(amide-imide)s (PAIs) were prepared from newly synthesized N,N′-(4,4′-diphthaloyl)-bis-l-isoleucine diacid (3) via polycondensation with various diamines. The diacid was synthesized by the condensation reaction of 3,3′,4,4′-biphenyltetracarboxylic dianhydride (1) with l-isoleucine (2) in a mixture of acetic acid and pyridine (3:2 v/v). All the polymers were obtained in quantitative yields with inherent viscosities of 0.20-0.43 dL g−1. All the polymers were highly organosoluble in solvents like N-methyl-2-pyrrolidinone (NMP), N,N-dimethylacetamide (DMAc), N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), tetrahydrofuran, γ-butyrolactone, cyclohexanone and chloroform at room temperature or upon heating. These poly(amide-imide)s had glass transition temperatures between 198 and 231 °C, and their 10% weight-loss temperatures were ranging from 368 to 398 °C and 353 to 375 °C under nitrogen and air, respectively. The polyimide films had tensile strengths in the range of 63-88 MPa and tensile moduli in the range of 0.8-1.4 GPa. These poly(amide-imide)s possessed chiral properties and the specific rotations were in the range of −3.10° to −72.92°.  相似文献   

3.
New polyesters having azomethine and phenylthiourea groups in the polymer backbone were synthesized by interfacial polycondensation method. The dihydroxy monomer N-(4-hydroxy-3-methoxybenzal) N′-(4′-hydroxyphenyl)thiourea was condensed with six diacid chlorides: terephthaloyl, isophthaloyl, azeloyl, suberoyl, pimeloyl and adipolyl chlorides. The resulting polyesters were characterized by viscosity, IR, NMR and TGA analysis. The wholly aromatic poly(azomethine ester) derived from terephthaloyl chloride when blended with polyaniline/NH4OH, polyaniline/HCl and pure polyaniline shows conductance in the range 3.2 × 10−3-0.91 × 10−1 S cm−1.  相似文献   

4.
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   

5.
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   

6.
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   

7.
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   

8.
Nitric oxide (NO) plays a very important role in human blood system. In this work, a novel approach has been developed for the quantitation of ultra-trace NO derivatized with 1,3,5,7-tetramethyl-8-(3′,4′-diaminophenyl)-difluoroboradiaza-s- indacene (DAMBO) using a polymer monolith microextraction (PMME) with a poly(methacrylic acid-ethylene glycol dimethacrylate) (MAA-EGDMA) monolith in conjunction with high-performance liquid chromatography (HPLC). Both derivatization and PMME conditions have been optimized in detail. The detection limit of derivatized NO was 2 × 10−12 mol L−1 (signal to noise = 3) and linear range was 9 × 10−11-4.5 × 10−8 mol L−1. The proposed DAMBO-based derivatization-PMME-HPLC-fluorescence detection method has been successfully applied for the determination of NO in 10 μL blood samples of healthy persons and patients suffering from ischemic cardio-cerebrovascular diseases with recoveries varying from 87.40 to 91.60%.  相似文献   

9.
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   

10.
N-2-(3-picolyl)-N′-phenylthiourea, 3PicTuPh, monoclinic, P21/n, a=7.617(2) b=7.197(5), c=22.889(5) Å, β=94.63(4)°, V=1250.7(1) Å3 and Z=4; N-2-(4-picolyl)-N′-phenylthiourea, 4PicTuPh, triclinic, P-1, a=7.3960(5), b=7.9660(12), c=21.600(3) Å, α=86.401(4), β=84.899(8), γ=77.769(8)°, V=1237.5(3) Å3 and Z=4; N-2-(5-picolyl)-N′-phenylthiourea, 5PicTuPh, monoclinic, P21/c, a=14.201(1), b=4.905(3), c=17.689(3) Å, β=91.38(1)°, V=1231.8(7) Å3 and Z=4; N-2-(6-picolyl)-N′-phenylthiourea, 6PicTuPh, monoclinic, C2/c2, a=14.713(1), b=9.367(1), c=18.227(1) Å, β=92.88(1)°, V=2515.5(1) Å3 and Z=8 and N-2-(4,6-lutidyl)-N′-phenylthiourea, 4,6LutTuPh, monoclinic, C2/c, a=11.107(2), b=11.793(2), c=20.084(4) Å, β=96.10(3)°, V=2616(1) Å3 and Z=8. Intramolecular hydrogen bonding between N′H and the pyridyl nitrogen and intermolecular hydrogen bonding involving the thione sulfur are affected by substitution of the pyridine ring, as is the planarity of the molecule. 1H NMR studies in CDCl3 show the NH′ hydrogen resonance considerably downfield from other resonances in the spectrum for each thiourea.  相似文献   

11.
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   

12.
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   

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.
A novel assay for the voltammetric detection of 18-bases DNA sequences relating to Chronic Myelogenous Leukemia (CML, Type b3a2) using methylene blue (MB) as the hybridization indicator was reported. DNA was covalently attached onto a glassy carbon electrode (GCE) through amines of the DNA bases using N-hydroxysulfosuccinimide (NHS) and N-(3-dimethylamion)propyl-N′-ethyl carbodiimidehydrochloride (EDC). The covalently immobilized single-stranded DNA (ssDNA) could selectively hybridize with its complementary DNA (cDNA) in solution to form double-stranded DNA (dsDNA) on the surface. A significant increase of the peak current for methylene blue upon the hybridization of immobilized ssDNA with cDNA in the solution was observed. This peak current change was used to monitor the recognition of CML DNA sequence. This electrochemical approach is sequence specific as indicated by the control experiments in which no peak current change was observed if a non-complementary DNA sequence was used. Factors, such as DNA target concentration and hybridization conditions determining the sensitivity of the electrochemical assay were investigated. Under optimal conditions, this sensor has a good calibration range between 1.25 × 10−7 and 6.75 × 10−7 M, with CML DNA sequence detection limit of 5.9 × 10−8 M.  相似文献   

15.
Ruhela R  Sharma JN  B S Tomar  Hubli RC  Suri AK 《Talanta》2011,85(2):1217-1220
A precise, sensitive and selective method for the spectrophotometric determination of palladium (II) using N,N,N′,N′-tetra(2-ethylhexyl) thiodiglycolamide T(2EH)TDGA as an extractant is described. Palladium (II) forms yellow colored complex with T(2EH)TDGA which exhibits an absorption maximum at ∼300 nm. The colored complex obeys Beer's law in the concentration range 1.0-15.0 μg ml−1 of palladium with a molar absorptivity of 1.29 × 105 M−1 cm−1. The effects of various experimental parameters have been studied to establish the optimum conditions for the extraction and determination of palladium. The precision of the method has been evaluated and the relative standard deviation has been found to be less than 0.5%. The method has been successfully applied to the determination of palladium in simulated high level liquid waste (SHLW) solution.  相似文献   

16.
A new PVC membrane electrode for Co2+ based on N,N′-bis(salicylidene)-3,4-diaminotoluene, an excellent neutral carrier, has been fabricated using sodium tetraphenylborate (NaTPB) as an anionic excluder and dioctylphthalte (DOP) as a solvent mediator. The electrode exhibits a linear potential response in the concentration range of 7.9 × 10−8 to 1.0 × 10−1 M with a slope of 30 ± 0.2 mV per decade. The detection limit of the proposed sensor is 5.0 × 10−8 M and it can be used over a period of 5 months. The proposed sensor revealed good selectivity over a wide variety of other cations including alkali, alkaline earth, heavy and transition metals and could be used in the pH range of 2.0-9.0. This electrode was successfully applied for the determination of Co2+in real samples and as an indicator electrode in potentiometric titration of cobalt ions.  相似文献   

17.
N-(3-ferrocenyl-2-naphthoyl) dipeptide esters (5-7) and N-(6-ferrocenyl-2-naphthoyl) dipeptide esters (8-10) were prepared by coupling either 3-ferrocenylnaphthalene-2-carboxylic acid 2 or 6-ferrocenylnaphthalene-2-carboxylic acid 4 to the dipeptide ethyl esters GlyAla(OEt) (5, 8), AlaGly(OEt) (6, 9), and AlaAla(OEt) (7, 10) using the standard N-(3-dimethylaminopropyl)-N′-ethylcarbodiimide hydrochloride (EDC), 1-hydroxybenzotriazole (HOBt) protocol. All the compounds were fully characterized using a combination of 1H NMR, 13C NMR, DEPT-135 and 1H-13C COSY (HMQC) spectroscopy, electrospray ionization mass spectrometry (ESI-MS) and cyclic voltammetry (CV). In vitro, the cytotoxic effects of compounds 5-10 show improvements over the corresponding N-(ferrocenyl)benzoyl derivatives, with IC50 values against the H1299 lung cancer cells ranging from 1.2 μM to 8.0 μM. N-(6-ferrocenyl-2-naphthoyl)-glycine-l-alanine ethyl ester 8 was found to be the most active derivative of the naphthoyl series so far, displaying an IC50 value of 1.3 ± 0.1 μM. This value is slightly lower than that found for the clinically employed anti-cancer drug cisplatin (IC50 = 1.5 ± 0.1 μM against H1299).  相似文献   

18.
A new unsymmetrical aromatic diamine, viz., 4-pentadecylbenzene-1,3-diamine was synthesized through a series of reaction steps starting from 3-pentadecylphenol. 4-Pentadecylbenzene-1,3-diamine was employed to synthesize a series of new polyimides by one-step polycondensation in m-cresol with four commercially available aromatic dianhydrides, viz., 3,3′,4,4′-biphenyltetracarboxylic dianhydride (BPDA), 3,3′,4,4′-benzophenonetetracarboxylic dianhydride (BTDA), 4,4′-oxydiphthalic anhydride (ODPA) and 4,4′-(hexafluoroisopropylidene)diphthalic anhydride (6-FDA). Inherent viscosities of resulting polyimides were in the range 0.33-0.67 dL/g and number average molecular weights were in the range 14,700-52,200 (GPC, polystyrene standard). Polyimides containing pendent pentadecyl chains were soluble in organic solvents such as chloroform, m-cresol, N,N-dimethylacetamide (DMAc), 1-methyl-2-pyrrolidinone (NMP), pyridine and nitrobenzene. Strong and flexible films of polyimides could be cast from their chloroform solutions. Polyimides exhibited glass transition temperature in the range 158-206 °C. The temperature at 10% wt. loss (T10), determined by TGA in nitrogen atmosphere, of polyimides was in the range 470-480 °C indicating good thermal stability.  相似文献   

19.
Molecularly imprinted polymer gel film on the gold substrate of a chip was prepared with minute amount of cross-linker for the fabrication of a surface plasmon resonance (SPR) sensor sensitive to 3,3′-dichlorobenzidine. The molecularly imprinted gel film was anchored on a gold chip by a surface-bound photo-radical initiator. The sensing of 3,3′-dichlorobenzidine is based on responsive shrinkage of the imprinted polymer gel film that is triggered by target binding. This change can improve the responsiveness of the imprinted SPR sensor to 3,3′-dichlorobenzidine. The molecularly imprinted polymer gel film was characterized with contact angle measurements, electrochemical impedance spectroscopy, cyclic voltammogram, swelling measurements and atomic force microscopy. The changes of SPR spectroscopy wavenumber shifts revealed that the imprinted gel sensing film can ‘memorize’ the binding of 3,3′-dichlorobenzidine compared to non-imprinted one. The imprinted gel-SPR sensor showed a linear response in the range of 9.0 × 10−12 to 5.0 × 10−10 mol L−1 (R2 = 0.9998) for the detection of 3,3′-dichlorobenzidine, and it also exhibited high selectivity to 3,3′-dichlorobenzidine compared to its structurally related analogues. We calculated the detection limits to be 0.471 ng L−1 for tap water and 0.772 ng kg−1 for soil based on a signal to noise ratio of 3. The method showed good recoveries and precision for the samples spiked with 3,3′-dichlorobenzidine. This suggest that the imprinted gel-SPR sensing method can be used as a promising alternative for the detection of 3,3′-dichlorobenzidine.  相似文献   

20.
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   

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