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1.
5,11,17,23‐Tetra‐tert‐butyl‐25,26,27,28‐tetrakis(diphenylphosphinoylmethoxy)calix[4]arene ( 1 )has been used for the preparation of a graphite coated thorium ion‐selective electrode (Th4+‐ISE). The plasticized PVC membrane containing 30% PVC, 58% ortho‐nitrophenyloctylether (NPOE), 4% sodium tetraphenylborate (NaTPB) and 8% ionophore was directly coated on a graphite rod. This sensor gave good Nernstian responses with a slope of 15.5 ± 0.1 mV/decade over a concentration range of 1 × 10?5 ?1 × 10?3 M of thorium ions with a limit of detection of 7.9 × 10?6 M. The dynamic response time of the electrode to achieve a steady potential was found to be about 15 seconds. The potential of the prepared sensor was independent of the pH variation in the range 2.3–4.0. The selectivity relative to several mono‐, di‐ and tri‐valent metal ions, i.e. Li+, Na+, K+, Ag+, NH4+, Sr2+, Mn2+, Fe2+, Co2+, Ni2+, Cu2+, Zn2+, Cd2+, La3+, Sm3+, Dy3+, Er3+ and Y3+ was examined. This electrode can be used for 6 months without any considerable divergences in the potential response. The sensor was successfully used as an indicator electrode for the potentiometric titration of a thorium solution using a standard solution of EDTA.  相似文献   

2.
《Electroanalysis》2006,18(16):1620-1626
A polyvinylchloride membrane sensor based on N,N′‐bis(salecylidene)‐1,2‐phenylenediamine (salophen) as membrane carrier was prepared and investigated as a Al3+‐selective electrode. The sensor exhibits a Nernstian response toward Al(III) over a wide concentration range (8.0×10?7–3.0×10?2 M), with a detection limit of 6.0×10?7 M. The potentiometric response of the sensor is independent of the pH of the test solution in the pH range 3.2–4.5. The electrode possesses advantages of very fast response and high selectivity for Al3+ in comparison with alkali, alkaline earth and some heavy metal ions. The sensor was used as an indicator electrode, in the potentiometric titration of aluminum ion and in determination of Al3+ contents in drug, water and waste water samples.  相似文献   

3.
An optical chemical sensor based on 2-mercaptopyrimidine (2-MP) in plasticized poly(vinyl chloride) (PVC) membrane incorporating (N,N-diethyl-5-(octadecanoylimino)-5H benzo[a]phenoxazine-9-amine (ETH 5294) and sodium tetraphenyl borate (NaTPB) for batch and flow-through determination of mercury ion is described. The response of the sensor is based on selective complexation of Hg2+ with 2-MP in the membrane phase, resulting in an ion exchange process between H+ in the membrane and Hg2+ in the sample solution. The influences of several experimental parameters, such as membrane composition, pH, and type and concentration of the regenerating reagent, were investigated. The sensor has a response range of 2.0 × 10−9 to 2.0 × 10−5 mol L−1 Hg2+ with a detection limit of 4.0 × 10−10 mol L−1 and a response time of ≤45 s at optimum pH of 6.5 with high measurement repeatability and sensor-to-sensor reproducibility. It shows high selectivity for Hg2+ over several transition metal ions, including Ag+, Cd2+, Co2+, Cr3+, Cu2+, Fe3+, Mn2+, Ni2+, and common alkali and alkaline earth ions such as Na+, K+, Mg2+, Ca2+, and Pb2+. The sensor membrane can be easily regenerated with dilute acid solutions. The sensor has been used for the determination of mercury ion concentration in water samples.  相似文献   

4.
A coated‐wire type silver ion‐selective electrode has been constructed using a modified p‐tert‐butyl‐calix[4]arene by amide‐phosphoryl groups, named 5, 11, 17, 23‐tetra‐tert‐butyl‐25, 27‐bis(diethylcarbamoylmethoxy)‐26,28‐bis(diphenylphosphinoylmethoxy)calix[4]arene (Calix), as neutral carrier. A plasticized PVC membrane containing 30% PVC, 60% ortho‐nitrophenyloctylether (NPOE), 2% sodium tetraphenylborate (NaTPB) and 8% “Calix” was coated on a graphite rod. The prepared electrode exhibited a linear Nernstian response over the range 1 × 10?6 to 1 × 10?2 M with a slope 58.4 (±0.2) mV per decade change and a detection limit of 6.3 × 10?7 M. The working pH range of the sensor is 4‐6.7. It is found that the dynamic response time of the electrode to achieve a steady potential was very fast (~11 s). The selectivity of the sensor relative to NH4+, Li+, Na+, K+, Ca2+, Sr2+, Ba2+, Mn2+, Pb2+, Co2+, Ni2+, Cu2+, Zn2+, Cd2+, Fe3+, La3+, Sm3+ and Th4+ was examined. The prepared electrode exhibits adequate stability with good reproducibility (57.6 ± 0.5 mV per decade change for 10 weeks). It was successfully used as an indicator electrode in potentiometric titration of silver ions with standard solution of EDTA. The sensor was also used for silver ion measurements in various synthetic samples.  相似文献   

5.
Highly selective all solid state electrochemical sensor based on a synthesized compound i.e. 2‐(1‐(2‐((3‐(2‐hydroxyphenyl)‐1H‐pyrozol‐1‐yl)methyl)benzyl)‐1H‐pyrazol‐3‐yl)phenol (I) as an ionophore has been prepared and investigated for the selective quantification of chromium(III) ions. The effect of various plasticizers, viz. dibutyl phosphonate (DBP), dibutyl(butyl) phosphonate (DBBP), nitrophenyl octyl ether (NPOE), tris‐(2‐ethylhexyl)phosphonate (TEP), tri‐butyl phosphonate (TBP), dioctyl phthalate (DOP), dioctyl sebacate (DOS), benzyl acetate (BA) and acetophenone (AP) along with anion excluders NaTPB (sodium tetraphenyl borate) and KClTPB (potassium(tetrakis‐4‐chlorophenyl)borate was also studied. The optimum composition of the best performing membrane contained (I):KClTPB:NPOE:PVC in the ratio 15 : 3 : 40 : 42 w/w. The sensor exhibited near Nernstian slope of 20.1±0.2 mV/decade of activity in the working concentration range of 1.2×10?7–1.0×10?1 M, and in a pH range of 3.8–4.5. The sensor exhibited a fast response time of 10 s and could be used for about 5 months without any considerable divergence in potentials. The proposed sensor showed very good selectivity over most of the common cations including Na+, Li+, K+, Cu2+, Sr2+, Ni2+, Co2+, Ba2+, Hg2+, Pb2+, Zn2+, Cs+, Mg2+, Cd2+, Al3+, Fe3+and La3+. The activity of Cr(III) ions was successfully determined in the industrial waste samples by using this sensor.  相似文献   

6.
A new ratiometric fluorescent sensor ( 1 ) for Cu2+ based on 4,4‐difluoro‐4‐bora‐3a,4a‐diaza‐s‐indacene (BODIPY) with di(2‐picolyl)amine (DPA) as ion recognition subunit has been synthesized and investigated in this work. The binding abilities of 1 towards different metal ions such as alkali and alkaline earth metal ions (Na+, K+, Mg2+, Ca2+) and other metal ions ( Ba2+, Zn2+, Cd2+, Fe2+, Fe3+, Pb2+, Ni2+, Co2+, Hg2+, Ag+) have been examined by UV‐vis and fluorescence spectroscopies. 1 displays high selectivity for Cu2+ among all test metal ions and a ~10‐fold fluorescence enhancement in I582/I558 upon excitation at visible excitation wavelength. The binding mode of 1 and Cu2+ is a 1:1 stoichiometry determined via studies of Job plot, the nonlinear fitting of the fluorometric titration and ESI mass.  相似文献   

7.
《中国化学》2017,35(8):1311-1316
Specific recognition of ultratrace levels of ions in semi‐water using super‐quicker methods is still a challenge for environmental monitoring. Herein we report a fluorescent and colormetric sensor ( ZH ) based on supramolecular self‐assembly, whose structure was destroyed by the addition of ultratrace of silver ions. The process promoted either naked eye visible color changes or fluorescence intensity quenched in conjunction with a wide pH range. Systematic studies revealed very high selectivity (0.07 µmol/L) for silver ions, and other common cations, e.g ., Hg2+, Cu2+, Cd2+, Pb2+ had nearly no influence on the sensing behavior. This sensor also served as a multiple use of component in sensing materials by addition of I into the mixture of ZH and Ag+ (about 5 times). What's more, ZH containing filter paper emerged distinct color and fluorescence changes upon exposure to silver (Ag+), which could be used as a portable method to undertake field testing for Ag + .  相似文献   

8.
A simple and nontoxic fluorescent chemosensor of di‐O‐methyl curcumin has been prepared from curcumin. The sensor exhibited selective and sensitive fluorescent responses toward Al3+ over a wide range of metal ions, such as Mn2+, Ce3+, Pt2+, Sn4+, Hg+, Sb3+, K+, Ca2+, Mg2+, Ba2+, Cu2+, Ni2+, Na+, NH4+, Ag+, Pb2+, Zn2+, Fe2+, Fe3+, Hg2+ and Cr3+ in ethanol/water. The free ligand showed quite weak fluorescence emission due to the isomerization of C?O double bond in the excited state, however, after addition of Al3+, fluorescence emission results in a prominent fluorescence enhancement.  相似文献   

9.
The alkaline hydrolysis reaction rates of 1,n‐bis(4‐cyanopyridinium)alkane derivatives Cnbis(CP)2+ with n = 3, 6, and 8 were studied and compared to the reaction rate of the N‐methyl‐4‐cyanopyridinium (MCP+). C6bis(CP)2+ and C8bis(CP)2+ obeyed the first‐order kinetic law. However for C3bis(CP)2+ data fitted to a consecutive two‐step model reaction, the observed rate constants (kobs) of C8bis(CP)2+ and C6bis(CP)2+ are approximately 50% and 100%, respectively, higher than those for MCP+, an effect mainly assigned to the higher charge density of these two derivatives. For C3bis(CP)2+, the kobs of the second (slow) step is almost twofold the value observed for C6bis(CP)2+, whereas the first (fast) step is approximately six times higher. As for MCP, the hydrolysis of Cnbis(CP)2+ generates pyridone (Po) and carbamidopyridinium (A+) units. For C3bis(CP)2+, however at pHs above 11.5, one additional product is formed. From the existence of the new product and the kinetic evidence, a “sandwiched‐type” complex with the OH? inserted between the rings is proposed. This structural effect in the C3bis(CP)2+ due to the conformational effect justifies the (i) two kinetic steps, (ii) high rate constants, (iii) high Po/A+ ratios, (iv) observed temperature and salt effects, and (v) the formation of the new product.  相似文献   

10.
The introduction of Lawesson′s reagent into a bis‐rhodamine spirolactam system afforded a new fluorescent sensor for Cu2+ ions, SRR , which contained a new tridentate sulfur ligand. SRR showed excellent specificity for Cu2+ ions over other cations (including Cu+, Hg2+, and Fe3+), very high sensitivity (10 nM ), and a rapid response time (3 min). The detection mechanism was investigated by 1H NMR, 13C NMR, 31P NMR, and ESR spectroscopy, MS, and Gaussian calculations. Coordination of a Cu2+ ion to the tridentate sulfur ligand, which promotes ring‐opening of the rhodamine groups, followed by a spontaneous reduction reaction (Cu2+ into Cu+), has been proposed as the sensing mechanism.  相似文献   

11.
Solvent extraction of a mixture of PbII, MnII, FeIII, CoII, NiII and CdII in aqueous perchlorate medium by a phosphorylated hexahomotrioxacalix[3]arene (calix‐3) in dichloromethane shows a significant selectivity towards lead ions. The ligand can also be incorporated into a membrane to provide a new lead ion‐selective electrode (PbII‐ISE). A plasticized PVC membrane containing 30% PVC, 53.5% ortho‐nitrophenyloctylether (NPOE), 4.5% sodium tetraphenylborate (NaTPB) and 12% ionophore was directly coated on a graphite rod. This sensor gave a good Nernstian response of 29.7 ± 0.7 mV decade?1 over a concentration range of 1 × 10?8 – 1 × 10?4 M of lead ions, independent of pH in the range 3‐7, with a detection limit of 0.4 × 10?8 M. The dynamic response time of the electrode to achieve a steady potential was very fast and found to be less than 7 s. The selectivity relative to Ag+, NH4+, Li+, Na+, K+, Ca2+, Sr2+, Ba2+, Mn2+, Fe2+, Co2+, Ni2+, Cu2+, Zn2+, Cd2+, Fe3+, La3+, Sm3+, Dy3+, Er3+, Y3+ and Th4+ was examined. The electrode exhibits adequate stability with good reproducibility (with a slope of 29.6 ± 1.5 mV for 8 weeks). The characteristics of the sensor are compared with those of a tetraphosphorylated calix[4]arene (calix‐4) based PbII‐ISE, reported recently. The electrode was successfully used as an indicator electrode for a potentiometric titration of a lead solution using a standard solution of EDTA. The applicability of the sensor for lead ion measurements in various synthetic samples was also investigated.  相似文献   

12.
《Electroanalysis》2006,18(10):1019-1027
A new PVC membrane potentiometric sensor for Ag(I) ion based on a recently synthesized calix[4]arene compound of 5,11,17,23‐tetra‐tert‐butyl‐25,27‐dihydroxy‐calix[4]arene‐thiacrown‐4 is developed. The electrode exhibits a Nernstian response for Ag(I) ions over a wide concentration range (1.0×10?2?1.0×10?6 M) with a slope of 53.8±1.6 mV per decade. It has a relatively fast response time (5–10 s) and can be used for at least 2 months without any considerable divergence in potentials. The proposed electrode shows high selectivity towards Ag+ ions over Pb2+, Cd2+, Co2+, Zn2+, Cu2+, Ni2+, Sr2+, Mg2+, Ca2+, Li+, K+, Na+, NH4+ ions and can be used in a pH range of 2–6. Only interference of Hg2+ is found. It is successfully used as an indicator electrode in potentiometric titration of a mixture of chloride, bromide and iodide ions.  相似文献   

13.
The well‐known rhodamine spiro‐lactam framework offers an ideal model for the development of fluorescence‐enhanced chemosensors through simple and convenient syntheses. Herein, we report a new tridentate PNO receptor, which was introduced into a rhodamine spiro‐lactam system to develop Pd2+‐chemosensor RPd4 , that displayed significantly improved sensing properties for palladium. Compound RPd4 shows a very fast response time (about 5 s), high sensitivity (5 nM ), and excellent specificity for Pd2+ ions over other PGE ions (Pt2+, Rh3+, and Ru3+). In addition, RPd4 displays quite different responses to different valence states of the Pd ions, that is, very fast response towards Pd2+ ions but slow response towards Pd0, which may provide us with a convenient method for the selective discrimination of Pd species in different valence states. According to proof‐of‐concept experiments, RPd4 has potential applications in Pd2+‐analysis in drug compounds, water, soil, and leaf samples. Owing to its good reversibility, RPd4 can also be used as a sensor material for the selective detection and visual recovery of trace Pd2+ ions in environmental samples.  相似文献   

14.
The construction, general performance characteristics and analytical application of a titanium dioxide–modified carbon paste electrode sensitive to hydrogen ions, based on incorporation of titanium dioxide in a carbon paste matrix, is described. The proposed electrochemical sensor exhibits a linear response in the pH range from 2 to 10, at 25 °C, with a sub‐Nernstian slope. The value of a slope is in a direct correlation with the electrode composition – the optimum content of a titanium dioxide in carbon paste is 30 %. Titanium dioxide‐modified carbon paste electrode shows fast response time and reproducibility, confirmed by different compounds determination in both, individual and complex material, namely, in synthetic and real samples. Besides, the electrode shows high selectivity in the presence of the alkali and the alkaline earth ions as Na+, K+, Ca2+ or Mg2+. The standard deviation of the investigated acids (acetic, oxalic, 5‐sulfosalicylic, p‐toluensulfonic acid, and amino acid‐glycine) and bases (N,N′‐diphenylguanidine and collidine) is less than 1.3 %. The obtained data are compared with those obtained by using a conventional glass pH‐electrode under the same experimental conditions and indicate a high correlation between them.  相似文献   

15.
The simple PVC‐based membrane containing N,N′,N″,N′′′‐tetrakis(2‐pyridylmethyl)‐1,4,8,11‐tetraazacyclotetradecane (tpmc) as an ionophore and dibutyl phthalate as a plasticizer, directly coated on a glassy carbon electrode was examined as a new sensor for Cu2+ ions. The potential response was linear within the concentration range of 1.0×10?1–1.0×10?6 M with a Nernstian slope of 28.8 mV/decade and detection limit of 7.0×10?7 M. The electrode was used in aqueous solutions over a wide pH range (1.3–6). The sensor exhibited excellent selectivity for Cu2+ ion over a number of cations and was successfully used in its determination in real samples.  相似文献   

16.
刘勉  叶蕴华 《中国化学》2002,20(11):1347-1353
IntroductionCyclicpeptides ,whichareconstrainedconforma tionallyandmoreresistanttoproteasedigestionsthantheirlinearprecursors ,havebeenofgreatinterestassynthetictargetsbothaspotentialdrugleadsandasmodelsforcon formationalanalysis .1 4 Currentmethodsforsynt…  相似文献   

17.
A terpyridine derivative DPTP [di-(4-methylphenyl)-2,2':6',2"-terpyridine] was conveniently synthesized from 2-bromopyridine via halogen-dance reaction, Kharash coupling and Stille coupling reaction. Then its corresponding ruthenium complex Ru-DPTP [N,N,N-4,4''-di-(4-methy,phenyl)-2,2':6',2"-terpyridine-N,N,N-tris(is,-thi,cyanat,)- ruthenium(H) ammonium] was obtained and fully characterized by IR, UV-Vis, ESI MS and elemental analysis. The MLCT absorption band of Ru-DPTP was blue-shifted from 570 to 500 nm upon addition of Hg^2+. Among a series of surveyed metal ions, the complex showed a unique recognition to Hg^2+, indicating that it can be used as a selective colorimetric sensor for Hg^2+.  相似文献   

18.
A hydrophobic organic monomer GRBE with a polymerizable methacrylester moiety had been synthesized by reaction of rhodamine B‐ethanediamine with glycidyl methacrylate. A water‐soluble polymeric chemosensor poly(VP‐GRBE) had been prepared via copolymerization with a hydrophilic comonomer (vinylpyrrolidone) and GRBE, which was able to sense environmentally poisonous cations in completely aqueous media. The chemosensor was a derivative of rhodamine B, which behaved as a fluorescent and chromogenic sensor toward various heavy cations, particularly Cr3+, Fe3+, and Hg2+. Titration curves of Cr3+, Fe3+, and Hg2+ were constructed using rapid, cheap, and widely available technique of fluorescence spectroscopies. The detection limits for Cr3+, Fe3+, or Hg2+ ions were found to be 2.20 × 10?12, 2.39 × 10?12, and 1.11 × 10?12 mol/l in the same medium, respectively. Moreover, a colorimetric response from the polymeric chemosensor permitted the detection of Cr3+, Hg2+, or Fe3+ by “naked eye” because of the development of a pink or brown yellow color when Cr3+, Hg2+, or Fe3+ cations interacted with the copolymer in aqueous media. Copyright © 2015 John Wiley & Sons, Ltd.  相似文献   

19.
Three chiral polymers P‐1 , P‐2 , and P‐3 could be obtained by the polymerization of (R)‐6,6′‐dibutyl‐3,3′‐diiodo‐2, 2′‐binaphthol (R‐M‐1) , (R)‐6,6′‐dibutyl‐3,3′‐diiodo‐2,2′‐bisoctoxy‐1,1′‐binaphthyl ( R‐M‐2 ), and (R)‐6,6′‐dibutyl‐3,3′‐diiodo‐2,2′‐bis (diethylaminoethoxy)‐1,1′‐binaphthyl ( R‐M‐3 ) with 4,7‐diethynyl‐benzo[2,1,3]‐thiadiazole ( M‐1) via Pd‐catalyzed Sonogashira reaction, respectively. P‐1 , P‐2 , and P‐3 can show pale red, blue–green, and orange fluorescence. The responsive optical properties of these polymers on various metal ions were investigated by fluorescence spectra. Compared with other cations, such as Co2+, Ni2+, Ag+, Cd2+, Cu2+, and Zn2+, Hg2+ can exhibit the most pronounced fluorescence response of these polymers. P‐1 and P‐2 show obvious fluorescence quenching effect upon addition of Hg2+, on the contrary, P‐3 shows fluorescence enhancement. Three polymer‐based fluorescent sensors also show excellent fluorescence response for Hg2+ detection without interference from other metal ions. The results indicate that these kinds of tunable chiral polybinaphthyls can be used as fluorescence sensors for Hg2+ detection. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 997–1006, 2010  相似文献   

20.
A K+‐sensitive capacitive electrolyte‐membrane‐insulator‐semiconductor (EMIS) based on a novel dibromoaza[7]helicene ionophore has been developed. An ion‐sensitive membrane based on polyvinylchloride (PVC) doped with the ionophore was deposited on the Si3N4/SiO2/Si‐p/Cu‐Al transducer. The properties of the K+‐EMIS chemical sensor were investigated by electrochemical impedance spectroscopy (EIS). All the developed devices upon being tested have shown good sensitivity and linearity responses within the range 10?6 M to 10?1 M of potassium activity, with good selectivity over a wide variety of other cations (Na+, Li+, Cu2+, Ca2+, and Mg2+). To our knowledge, this is the first time that a capacitive field‐effect sensor has been fabricated using helicene as a carrier for K+‐detection, combined with the structure: Si3N4/SiO2/Si‐p/Cu‐Al as a transducer.  相似文献   

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