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1.
To meet the need for rapid and low-cost chemical sensing of explosive, new fluorescence chemosensors based on oligophenothiazines for probing vapor-phase nitro compounds have been developed. The phenothiazine-based trimer P3 and pentamer P5 have been synthesized via Heck and Wittig reactions by convergent approach. It was found that they can detect the vapors of nitro compounds, including p-nitrotoluene (p-NT), 2,4-dinitrotoluene (DNT), 2,4,6-trinitrotoluene (TNT) with good sensitivity and reversibility. And the sensor of P3 film gave a linear fluorescence quenching response to 7-800 ppb TNT with the detection limit of 4 ppb. For DNT vapor, a linear working range of the sensor was 2-24 ppm with the detection limit of 40 ppb. Meanwhile, the interferents, including common organic solvents, p-nitrophenol and 2,4-dinitrophenylhydrazine cannot lead to obvious fluorescence quenching, meaning that the film based on oligophenothiazines exhibited good specificity of fluorescence response to explosive. Based on the fluorescence lifetime and UV-vis absorption measurements, we suggested that the fluorescence quenching of oligophenothiazine-based films exposed to the vapors of nitro compounds was due to the formation of non-fluorescent charge-transfer complex between oligophenothiazine and nitro compounds.  相似文献   

2.
A porphyrin derivative (1), containing two 2-(oxymethyl)pyridine units has been designed and synthesized as chemosensor for recognition of metal ions. Unlike many common porphyrin derivatives that show response to different heavy metal ions, compound 1 exhibits unexpected ratiometric fluorescence response to Zn2+ with high selectivity. The response of the novel chemosensor to zinc was based on the porphyrin metallation with cooperating effect of 2-(oxymethyl)pyridine units. The change of fluorescence of 1 was attributed to the formation of an inclusion complex between porphyrin ring and Zn2+ by 1:1 complex ratio (K = 1.04 × 105), which has been utilized as the basis of the fabrication of the Zn2+-sensitive fluorescent chemosensor. The analytical performance characteristics of the proposed Zn2+-sensitive chemosensor were investigated. The sensor can be applied to the quantification of Zn2+ with a linear range covering from 3.2 × 10−7 to 1.8 × 10−4 M and a detection limit of 5.5 × 10−8 M. The experiment results show that the response behavior of 1 to Zn2+ is pH-independent in medium condition (pH 4.0-8.0) and show excellent selectivity for Zn2+ over transition metal cations.  相似文献   

3.
Comparative studies of neodymium (III)-selective PVC membrane sensors   总被引:1,自引:0,他引:1  
Sensors based on two neutral ionophores, N,N′-bis((1H-pyrrol-2-yl)methylene)cyclohexane-1,2-diamine (L1) and 3,3′-(cyclohexane-1,2-diylbis(azan-1-yl-1-ylidene)bis(methan-1-yl-1-ylidene)bis(5-hydroxymethyl)pyridine-2-ol) (L2) are described for quantification of neodymium (III). Effect of various plasticizers; 2-nitrophenyloctylether (o-NPOE), dibutyl butylphosphonate (DBBP), tri-n-butyl phosphates (TBP), dioctylpthalate (DOP) and chloronapthalen (CN) and anion excluder, sodiumtetraphenylborate (NaTPB) has been studied. The membrane composition of PVC:o-NPOE:ionophore (L1):NaTPB (w/w; mg) of 150:300:5:5 exhibited best performance. The sensor with ionophore (L1) exhibits significantly enhanced selectivity towards neodymium (III) in the concentration range 5.0 × 10−7 to 1.0 × 10−2 M with a detection limit of 1.0 × 10−7 M and a Nernstian compliance (19.8 ± 0.3 mV decade−1 of activity) within pH range 4.0-8.0. The response time of sensor was found as 10 s. The influence of the membrane composition and possible interfering ions has also been investigated on the response properties of the electrode. The fast and stable response, good reproducibility and long-term stability of the sensor are observed. The sensor has been found to work satisfactorily in partially non-aqueous media up to 20% (v/v) content of methanol, ethanol or acetonitrile and could be used for a period of 3 months. The selectivity coefficients determined by using fixed interference method (FIM) indicate high selectivity for neodymium. The proposed electrode shows fairly good discrimination of neodymium (III) from other cations. The application of prepared sensor has been demonstrated in the determination of neodymium (III) in spiked water samples.  相似文献   

4.
New fluorescent peptide-based sensors (13) for monitoring heparin in serum sample were synthesized using short peptides (1∼3mer) as a receptor. The peptide-based sensors (2 and 3) showed a sensitive ratiometric response to heparin both in aqueous buffered solution (10 mM HEPES, pH 7.4) and in 2% human serum sample by increase of excimer emission of pyrene at 480 nm and concomitant decrease of monomer emission of pyrene at 376 nm, whereas the peptide-based sensor 1 showed a turn off response only by decrease of monomer emission at 376 nm. 2 and 3 exhibited excellent selectivity toward heparin among various anions and competitors of heparin including chondroitin 4-sulfate (ChS) and hyaluronic acid (HA). Peptide-based sensor 3 showed a more sensitive response to heparin than 2. The detection limit of 3 was determined as 36 pM (R2 = 0.998) for heparin in aqueous solution and 204 pM (R2 = 0.999) for heparin in aqueous solutions containing 2% human serum. The peptide-based sensors, 2 and 3 provided a practical and potential tool for the detection and quantification of heparin in real biological samples.  相似文献   

5.
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   

6.
Vinod K. Gupta  Manoj K. Pal 《Talanta》2010,82(4):1136-1142
A new terbium selective sensor based on N-(2-hydroxyphenyl)-3-(2-hydroxyphenylhydroxyphenylimino)-N-phenylbutanamidine (L1) and N,N′-bis((1H-indole-3-yl)methylene)butane-1,4 diamine (L2) as a ionophore is reported. Effect of various plasticizers; 2-nitrophenyloctylether (o-NPOE), dibutyl butylphosphonate (DBBP), chloronaphthelene (CN), dioctylphthalate (DOP) and tri-(2-ethylhexyl)phosphate (TEHP) with anion excluder, potassium tetrakis (p-chloropheny1)borate (KTpClPB) have been studied. The membrane with a composition of ionophore (L1):KTpClPB:PVC:o-NPOE (w/w, %) in ratio of 3.0:5.0:30.0:62.0 exhibited enhanced selectivity towards terbium ions (III) in the concentration range of 3.5 × 10−7 to 1.0 × 10−2 M with a detection limit of 1.2 × 10−7 M and a Nernstian slope (20.0 ± 0.5 mV dec−1 activity). The sensors showed the working pH range to be 3.5-7.5 with response time of 11 s. The sensor has been found to work satisfactorily in partially non-aqueous media up to 15% (v/v) content of methanol, ethanol or acetonitrile and could be used for a period of 3 months. The selectivity coefficients indicated high selectivity for terbium (III). The fast and stable response, good reproducibility and long-term stability of the sensors were observed. The application of the sensor has been demonstrated in determination of terbium (III) ions in spiked water samples.  相似文献   

7.
New pyrimidine derivatives (pyr) have been synthesized using palladium-catalyzed Suzuki coupling reaction. These compounds can undergo cyclometalation with iridium trichloride to form bis-cyclometalated iridium complexes, (pyr)2Ir(acac) (acac = acetylacetonate; pyr = cyclometalated pyr). The substituents at the both cyclometalated phenyl ring and pyrimidine ring were found to affect both electrochemical and photophysical properties of the complexes. Computation results on these complexes are consistent with the electrochemical and photophysical data. The complexes are green-emitting with good solution quantum yields at ∼0.30. Light-emitting devices using these complexes as dopants were fabricated, and the device performance at 100 mA/cm2 are moderate: 9 (17 481 cd/m2, 4.8%, 18 cd/A, 5.1 lm/W); 10 (18 704 cd/m2, 4.9%, 18.9 cd/A, 4.7 lm/W); 13 (20 942 cd/m2, 5.4%, 21.0 cd/A, 6.1 lm/W).  相似文献   

8.
Two novel photoluminescent coordination polymers of the formula [Cd(Haip)2(H2O)2] · 2H2O (1) and [Zn(aip)(atz)] · 3H2O (2) (H2aip = 5-aminoisophthalic acid; atz = 3-amino-1,2,4-triazole) have been synthesized through the self-assembly of metal(II) ions with H2aip and N-containing ligands [2-amino-5-mercapto-1,3,4-thiadiazole for 1 and 3-amino-1,2,4-triazole for 2, respectively] in the presence of NaOH. These complexes were characterized by FT-IR spectroscopy, thermogravimetric analysis (TG), elemental analysis and X-ray analysis. X-ray crystallographic studies of the complexes reveal that 1 is a first example where only one carboxylate group of the H2aip ligand participates in coordination with the metal(II) ion and it exhibits a two-dimensional framework which further assembles into a three-dimensional supramolecular network via interlayer π–π stacking interactions and strong hydrogen bonds, while 2 exhibits a two-dimensional porous architecture. The extensively strong hydrogen bonds and interlayer π–π stacking interactions in 2 lead to the formation of a three-dimensional supramolecular network. Photoluminescence properties of the compounds 1 and 2 have been examined in the solid state at room temperature. These compounds have been found to exhibit blue photoluminescence and may be good candidates for photoactive materials.  相似文献   

9.
Four mercury(II) thiocyanate–organic polymeric complexes, [Hg(μ-4,4-bipy)(SCN)2]n (1), [Hg(μ-bpa)(SCN)2]n (2), [Hg(μ-bpe)(SCN)2]n (3), [Hg(μ-bpp)(SCN)2]n (4) {4,4-bipy = 4,4′-bipyridine, bpa = 1,2-bis(4-pyridyl)ethane, bpe = 1,2-bis(4-pyridyl)ethene and bpp = 1,3-di(4-pyridyl)propane} were prepared from reactions of mercury(II) thiocyanate with four rigid and flexible organic nitrogen donor-based ligands under thermal gradient conditions, brunched tube method. All these compounds were structurally determined by X-ray single-crystal diffraction. The thermal stabilities of compounds 14 were studied by thermal gravimetric (TG) and differential thermal analyses (DTA). Solid state luminescent spectra of compounds 1 and 3 indicate intense fluorescent emissions at 430 and 468 nm, respectively.  相似文献   

10.
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   

11.
Four platinum(II) complexes, [PtCl2L] (L = (4-fluorophenyl)pyridin-2-ylmethylene-amine, 1; (4-chlorophenyl)pyridin-2-ylmethyleneamine, 2; (4-bromophenyl)pyridin-2-ylmethyleneamine, 3 and (4-iodophenyl)pyridin-2-ylmethyleneamine, 4) have been synthesized and characterized by CHN analysis, IR and UV–Vis spectroscopy. The crystal structures of 1 and 2 were determined using single crystal X-ray diffraction. The coordination polyhedron about the platinum (II) center in the complexes is best described as distorted square planar. The complexes undergo stacking to form a zigzag Pt···Pt···Pt chain containing both short (3.57(7) Å in 1 and 3.62(8) Å in 2) and long (5.16(7) Å in 1 and 5.41(9) Å in 2) Pt···Pt separations through the crystal. The compounds absorb moderately in the visible region, owing to a charge-transfer-to-diimine electronic transition. The redox potentials are approximately insensitive to the substituents on the phenyl ring of the ligands.  相似文献   

12.
Two novel photoluminescent coordination compounds of the formula [Cd(atpt)phen(H2O)] · H2O (1) and [Zn2(atpt)2(bipy)2(H2O)2] (2) (H2atpt = 2-aminoterephthalic acid, bipy = 2,2′-bipyridine and phen = 1,10-phenanthroline) were synthesized through the self-assembly of H2atpt and N-containing ligands (bipy for 1 and phen for 2) with metal(II) ions in the presence of NaOH, and were characterized by FT-IR spectroscopy, thermogravimetric analysis (TG), X-ray analysis and photoluminescence spectra in the solid state. Compound 1 is the first structurally characterized Cd(II) complex with the atpt ligand. The coordination mode of the atpt ligand in 2 is novel and is first reported in this presentation. X-ray crystallographic studies reveal that compound 1 shows a 1D architecture. Compound 1 further assembles into a 3D supramolecular network via interchain hydrogen bonds and π–π stacking interactions. Compound 2 exhibits a binuclear structure with intramolecular π–π stacking interactions, which is further extended into a 3D supramolecular framework via intermolecular hydrogen bonds and C–H?π interactions. Compounds 1 and 2 exhibit green photoluminescence in the solid state at room temperature.  相似文献   

13.
[(RR′-admpzp)2Ti(OPri)2] complexes (2a-c), synthesized from reaction of Ti(OPri)3Cl (0.5 equiv) with 1-dialkylamino-3-(3,5-dimethyl-pyrazol-1-yl)-propan-2-ol compounds in the presence of triethylamine (0.5 equiv), are pseudo-octahedral with each RR′-admpzp ligand κ2-O,N(pyrazolyl) coordinated to the titanium center. In solution, 2a-c adopt isomeric structures that are in dynamic equilibrium. At 23 °C, 2a-c/1000 MAO catalyst systems furnished high molecular weight polymers with narrow molecular weight distributions (Mw/Mn = 2.7-2.8). At 100 °C, 2a-c/MAO catalyst systems exhibited increased polymerization activity and 2c/1000 MAO system furnished high molecular weight polyethylene with a molecular weight distribution (Mw/Mn = 2.1) that is close to that found for single-site catalysts.  相似文献   

14.
New stable azido derivatives of divalent germanium and tin [N3-E14-OCH2CH2NMe2]2 (E14 = Ge (1), Sn (2)) have been synthesized by use of the β-dimethylaminoethoxy ligand that forms the intramolecular E14 ← N coordination bond. Their crystal structures have been determined by X-ray diffraction analysis. Compounds 1 and 2 are centrosymmetric dimers via two intermolecular dative E14 ← O interactions with essentially linear monodentate azide ligands. The dominant canonical form of the E14-azide moieties is E14-N-NN.  相似文献   

15.
Fifteen novel (3-chloro-5-(trifluoromethyl)pyridin-2-yloxy)phenyl containing Baylis-Hillman adduct derivatives were designed and synthesized. Evaluation of their biological activities showed that methyl 2-((3-(3-chloro-5-(trifluoromethyl)pyridin-2-yloxy)phenoxy)(phenyl)methyl)acrylate (2g) exhibited efficient broad-spectrum fungicidal activity, with 100% control of wheat powdery mildew and cucumber downy mildew and 98% control of cucumber anthracnose at 400 g ai/ha. Some of the other title compounds 2, 3 and two Baylis-Hillman bromide intermediates (11a, 11b) had moderate to good fungicidal activity.  相似文献   

16.
The two chromium chelates of Schiff bases, N-(acetoacetanilide)-1,2-diaminoethane (L1) and N,N′-bis(acetoacetanilide)-triethylenetetraammine (L2), have been synthesized and explored as neutral ionophores for preparing poly(vinylchloride) (PVC) based membrane sensors selective to Cr(III). The addition of lipophilic anion excluder (NaTPB) and various plasticizers viz. o-Nitrophenyloctyl ether (o-NPOE), dioctylpthalate (DOP), dibutylphthalate (DBP), tris(2-ethylhexyl)phosphate (TEHP), and benzyl acetate (BA) have found to improve the performance of the sensors. The best performance was obtained for the membrane sensor having a composition of L1:PVC:DBP:NaTPB in the ratio 5:150:250:3 (w/w). The sensor exhibits Nernstian response in the concentration range 8.9 × 10−8 to 1.0 × 10−1 M Cr3+ with limit of detection 5.6 × 10−8 M. The proposed sensor manifest advantages of relatively fast response (10 s) and good selectivity over some alkali, alkaline earth, transition and heavy metal ions. The selectivity behavior of the proposed electrode revealed a considerable improvement as compared to the best previously PVC-membrane electrode for chromium(III) ion. The potentiometric response of the proposed sensor was independent of pH of the test solution in the range of 2.0-7.0. The sensor has 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 3 months. The proposed electrode was used as an indicator electrode in potentiometric titration of chromium ion with EDTA and in direct determination in different water and food samples.  相似文献   

17.
Praseodymium ion selective polyvinyl chloride (PVC) membrane sensors, based on two new Schiff's bases 1,3-diphenylpropane-1,3-diylidenebis(azan-1-ylidene)diphenol (M1) and N,N′-bis(pyridoxylideneiminato) ethylene (M2) have been developed and studied. The sensor having membrane composition of PVC: o-NPOE: ionophore (M1): NaTPB (w/w; mg) of 150: 300: 8: 5 showed best performances in comparison to M2 based membranes. The sensor based on (M1) exhibits the working concentration range 1.0 × 10−8 to 1.0 × 10−2 M with a detection limit of 5.0 × 10−9 M and a Nernstian slope 20.0 ± 0.3 mV decade−1 of activity. It exhibited a quick response time as <8 s and its potential responses were pH independent across the range of 3.5-8.5.The influence of the membrane composition and possible interfering ions have also been investigated on the response properties of the electrode. The sensor has been found to work satisfactorily in partially non-aqueous media up to 15% (v/v) content of methanol, ethanol or acetonitrile and could be used for a period of 3 months. The selectivity coefficients determined by using fixed interference method (FIM) indicate high selectivity for praseodymium(III) ions over wide variety of other cations. To asses its analytical applicability the prepared sensor was successfully applied for determination of praseodymium(III) in spiked water samples.  相似文献   

18.
Four transition–lanthanide metal–organic coordination polymers, namely [Ag2Ln(nic)4(H2O)4 · (ClO4) · H2O] [Ln = Eu (1), Gd (2)] and [AgLn(nic)2(ox)0.5(H2O)2 · (ClO4) · H2O] [Ln = Tb (3), Yb (4)] (nic = nicotinate; ox = oxalate) have been synthesized by the hydrothermal reactions of 4d and 4f metal salts with N-/O-donor ligands. The isostructural complexes 1 and 2 exhibit novel 2D wave-like heterometallic layers constructed by the assembly of 1D chains of lanthanide–carboxylate with Ag(nic)2 subunits. Complexes 3 and 4 show another unusual 3D heterometallic coordination framework constructed from 2D lanthanide–oxalate layers and pillar-like Ag(nic)2 subunits. Furthermore, the luminescent properties of complexes 1 and 3 were studied.  相似文献   

19.
Butylamide-terminated poly(amidoamine) dendrons with either a Boc group (C-n (n = 1, 2, 3)) or a carboxyl group (E-n (n = 1, 2)) at the focal point, as a new kind of dendritic gelators, were synthesized and their gelation properties were studied by TEM, WAXD, SAXS, NMR,and FTIR spectroscopy. It was found that the structure of focal groups impacted greatly on their gelation ability and the dendrons with higher generations facilitated the gel phase assembly. Hydrogen-bonding and hydrophobic interactions were proved to be the main driving forces responsible for the fibrous assembly with the diameter in the range of 30-100 nm. The molecular packing pattern of the xerogels of C-2, C-3, E-1, and E-2 all showed a lamellar structure, which was revealed by WAXD and SAXS.  相似文献   

20.
A series of new HgI2 organic polymeric complexes, [Hg2(L1)I4]n (1), [Hg(L2)I2]n (2), [Hg(L3)I2]n (3), [Hg2(L4)I4]n (4), [Hg(L5)I2]n (5), [Hg(L6)I3](HL6) (6) {L1 = 1,4-bis(2-pyridyl)-2,3-diaza-1,3-butadiene, L2 = 1,4-bis(3-pyridyl)-2,3-diaza-1,3-butadiene, L3 = 1,4-bis(4-pyridyl)-2,3-diaza-1,3-butadiene, L4 = 2,5-bis(2-pyridyl)-3,4-diaza-2,4-hexadiene, L5 = 2,5-bis(3-pyridyl)-3,4-diaza-2,4-hexadiene and L6 = 2,5-bis(4-pyridyl)-3,4-diaza-2,4-hexadiene} was prepared from reactions of mercury(II) iodide with six organic nitrogen donor-based ligands under thermal gradient conditions using the branched tube method. All these compounds were structurally characterized by single-crystal X-ray diffraction. The HgI2 coordination polymers obtained with the ligands L2, L3 and L5 show one-dimensional zig-zag motifs and in these compounds the HgI2 units are connected to each other by the ligands L2, L3 and L5 through the pyridyl nitrogen atoms. The L1 and L4 ligands in the compounds 1 and 4 act as both a chelating and bridging group. In the compound 6 the ligand L6 acts as a monodentate ligand, resulting form a discrete compound. The thermal stabilities of compounds 16 were studied by thermal gravimetric (TG) and differential thermal analyses (DTA).  相似文献   

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