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1.
A novel fluorescent probe‐based naphthalene Schiff, 1‐(C2‐glucosyl‐ylimino‐methyl)‐naphthalene‐2‐ol (L) was synthesized by coupling d ‐glucosamine hydrochloride with 2‐hydroxy‐1‐naphthaldehyde. It exhibited excellent selectivity and highly sensitivity for Al3+ in ethanol with a strong fluorescence response, while other common metal ions such as Pb2+, Mg2+, Cu2+, Co2+, Ni2+, Cd2+, Fe2+, Mn2+, Hg2+, Li+, Na+, K+, Fe3+, Cr3+, Zn2+, Ag+, Ba2+ and Ca2+ did not cause the same fluorescence response. The probe selectively bound Al3+ with a binding constant (Ka) of 5.748 × 103 M?1 and a lowest detection limit (LOD) of 4.08 nM. Moreover, the study found that the fluorescence of the L ? Al3+ complex could be quenched after addition of F? in the same medium, while other anions, including Cl?, Br?, I?, NO2?, NO3?, ClO4?, CO32?, HCO3?, SO42?, HSO4?, CH3COO?, PO43?, HPO42?, S2? and S2O32? had nearly no influence on probe behaviour. Binding of the [L ? Al3+] complex to a F? anion was established by different fluorescence titration studies, with a detection limit of 3.2 nM in ethanol. The fluorescent probe was also successfully applied in the imaging detection of Al3+ and F? in living cells.  相似文献   

2.
The behaviors of 15 kinds of metal ions in the thiol‐capped CdTe quantum dots (QDs)–H2O2 chemiluminescence (CL) reaction were investigated in detail. The results showed that Ag+, Cu2+ and Hg2+ could inhibit CdTe QDs and H2O2 CL reaction. A novel CL method for the selective determination of Ag+, Cu2+ and Hg2+ was developed, based on their inhibition of the reaction of CdTe QDs and H2O2. Under the optimal conditions, good linear relationships were realized between the CL intensity and the logarithm of concentrations of Ag+, Cu2+ and Hg2+. The linear ranges were from 2.0 × 10?6 to 5.0 × 10?8 mol L?1 for Ag+, from 5.0 × 10?6 to 7.0 × 10?8 mol L?1 for Cu2+ and from 2.0 × 10?5 to 1.0 × 10?7 mol L?1 for Hg2+, respectively. The limits of detection (S/N = 3) were 3.0 × 10?8, 4.0 × 10?8 and 6.7 × 10?8 mol L?1 for Ag+, Cu2+ and Hg2+, respectively. A possible mechanism for the inhibition of CdTe QDs and H2O2 CL reaction was also discussed. Copyright © 2009 John Wiley & Sons, Ltd.  相似文献   

3.
A Schiff base compound derived from naphthalene has been synthesized and characterized as an Al3+‐selective fluorescent probe. The chemosensor ( L ) exhibits high selectively for Al3+ in aqueous solution, even in the presence of biologically relevant cations such as Na+, K+, Ca2+, Mg2+, Pb2+ and several transition metal ions. There was no observed interference from anions like Br?, Cl?, HSO3?, SO32?, S2O32?, NO2?, CO32? and AC?. The lowest detection limit for the chemosensor L was found to be 1.89 × 10?8 M with a linear response towards Al3+ over a concentration range of 5 × 10?6 to 4 × 10?5 M. Furthermore, the proposed chemosensor has been used for imaging of Al3+ in two different types of cells with satisfying results, which further demonstrates its value for practical application in biological systems.  相似文献   

4.
The main purpose of this study was to develop an inexpensive, simple, rapid and sensitive chemiluminescence (CL) method for the determination of glutamine (Gln) using a flow‐injection (FI) system. Gln was found to strongly inhibit the CL signal of the luminol–H2O2–CuSO4 system in Na2B4O7 solution. A new FI‐CL method was developed for the determination of Gln. Parameters affecting the reproducibility and CL detection were optimized systematically. Under the optimized conditions, the corresponding linear regression equation was established over the range of 5.0 × 10?7 to 2.5 × 10?6 mol/L with the detection limit of 1.8 × 10?8 mol/L. The relative standard deviation was found to be 1.8% for 11 replicate determinations of 1.5 × 10?6 mol/L Gln. The proposed method has been satisfactorily applied for the determination of Gln in real samples (Marzulene‐s granules) with recoveries in the range of 98.7–108.6%. The minimum sampling rate was about 100 samples/h. The possible mechanism of this inhibitory CL was studied by fluorescence spectrophotometer and UV–vis spectrophotometer. Copyright © 2009 John Wiley & Sons, Ltd.  相似文献   

5.
Two new twinborn benzimidazole derivates ( L and A ), which bonded pyridine via the ester space on the opposite and adjacent positions of the benzene ring of benzimidazole respectively, were designed and synthesized. Compound L displayed fluorescence quenching response only towards copper(II) ions (Cu2+) in acetonitrile solution with high selectivity and sensitivity. However, compound A presented ‘on–off’ fluorescence response towards a wide range of metal ions to different degrees and did not have selectivity. Furthermore, compound L formed a 1:1 complex with Cu2+ and the binding constant between sensor L and Cu2+ was high at 6.02 × 104 M?1. Job's plot, mass spectra, IR spectra, 1H‐NMR titration and density functional theory (DFT) calculations demonstrated the formation of a 1:1 complex between L and Cu2+. Chemosensor L displayed a low limit of detection (3.05 × 10?6 M) and fast response time (15 s) to Cu2+. The Stern–Volmer analysis illustrated that the fluorescence quenching agreed with the static quenching mode. In addition, the obvious difference of L within HepG2 cells in the presence and absence of Cu2+ indicated L had the recognition capability for Cu2+ in living cells.  相似文献   

6.
A new 2,5‐diphenyl‐1,3,4‐oxadiazole‐based derivative (L) was synthesized and applied as a highly selective and sensitive fluorescent sensor for relay recognition of Cu2+ and S2? in water (Tris–HCl 10 mM, pH = 7.0) solution. L exhibits an excellent selectivity to Cu2+ over other examined metal ions with a prominent fluorescence ‘turn‐off’ at 392 nm. L interacts with Cu2+ through a 1:2 binding stoichiometry with a detection limit of 4.8 × 10–7 M. The on‐site formed L–2Cu2+ complex exhibits excellent selectivity to S2? with a fluorescence ‘off–on’ response via a Cu2+ displacement approach. Copyright © 2016 John Wiley & Sons, Ltd.  相似文献   

7.
In this paper, a novel fluorescent sensor 1 for selective and sensitive detection of cysteine was developed based on a complex between bi‐8‐carboxamidoquinoline derivative ligand ( L ) and Cu2+. The interaction of Cu2+ with the ligand causes a dramatic fluorescence quenching most likely due to its high affinity towards Cu2+ and a ligand–metal charge transfer (LMCT) process. The in situ generated L–Cu 2 complex was utilized as a chemosensing ensemble for cysteine. In the presence of cysteine, the fluorophore, L , was released from L–Cu 2 complex because of the strong affinity of cysteine to Cu2+ via the Cu–S bond, leading to the fluorescence recovery of the ligand. The proposed displacement mechanism was confirmed by the results of mass spectrometry (MS) study. Under optimized conditions, the recovered fluorescence intensity is linear with cysteine concentrations in the range 1 × 10?6 mol/l to 8 × 10?6 mol/l. The detection limit for cysteine is 1.92 × 10?7 mol/l. Furthermore, the established method showed a highly sensitive and selective response to cysteine among the 20 fundamental α‐amino acids used as the building blocks of proteins, after Ni2+ was used as a masking agent to eliminate the interference of His. The proposed sensor is applicable in monitoring cysteine in practical samples with good recovery rate.  相似文献   

8.
Heavy metal ions (Pb2+, Cd2+, Mn2+, Cu2+, and Cr2O7 2?) were biosorbed by brown seaweeds (Hizikia fusiformis, Laminaria japonica, and Undaria pinnatifida) collected from the southern coast of South Korea. The biosorption of heavy metal ions was pH-dependent showing a minimum absorption at pH 2 and a maximum biosorption at pH 4 (Pb2+, Cd2+, Mn2+, and Cr2O7 2?) or pH 6 (Cu2+). Biosorption increased most noticeably for pH changes from 2 to 3. In the latter pH range, biosorption increased, because a higher pH decreased the electrostatic repulsion between metal ions and functional groups on the seaweed. In the pH range of 2 ~ 4, biosorption of negatively-charged chromium species (Cr2O7 ?2) followed the pattern of positively-charged metal ions (Pb2+, Cd2+, Mn2+, and Cu2+). This suggests that the most prevalent chromium species were positively-charged Cr3+, reduced from Cr6+ in Cr2O7 ?2. Whereas positively-charged heavy metal ions (Pb2+, Cd2+, Mn2+, and Cu2+) reached a plateau after the maximum level, biosorption of chromium ions decreased noticeably between pH 5 and 8. Kinetic data showed that biosorption by brown seaweed occurred rapidly during the first 10 min, and most of the heavy metals were bound to the seaweed within 30 min. Equilibrium adsorption data for a lead ion could fit well in the Langmuir and Freundlich isotherm models with regression coefficients (R 2) between 0.93 and 0.98.  相似文献   

9.
The natural dihydroflavonol (+) taxifolin was investigated for its protective effect on Fenton reagent-treated bone marrow-derived mesenchymal stem cells (bmMSCs). Various antioxidant assays were used to determine the possible mechanism. These included ?OH-scavenging, 2-phenyl-4, 4, 5, 5-tetramethylimidazoline-1-oxyl-3-oxide radical-scavenging (PTIO?-scavenging), 1, 1-diphenyl-2-picryl-hydrazl radical-scavenging (DPPH?-scavenging), 2, 2′-azino-bis (3-ethylbenzo-thiazoline-6-sulfonic acid) radical-scavenging (ABTS+?-scavenging), Fe3+-reducing, and Cu2+-reducing assays. The Fe2+-binding reaction was also investigated using UV-Vis spectra. The results revealed that cell viability was fully restored, even increasing to 142.9?±?9.3% after treatment with (+) taxifolin. In the antioxidant assays, (+) taxifolin was observed to efficiently scavenge ?OH, DPPH? and ABTS+? radicals, and to increase the relative Cu2+- and Fe3+-reducing levels. In the PTIO?-scavenging assay, its IC50 values varied with pH. In the Fe2+-binding reaction, (+) taxifolin was found to yield a green solution with two UV-Vis absorbance peaks: λmax =?433 nm (ε =5.2?×?102 L mol?1 cm ?1) and λmax =?721 nm (ε?=?5.1?×?102 L mol?1 cm ?1). These results indicate that (+) taxifolin can act as an effective ?OH-scavenger, protecting bmMSCs from ?OH-induced damage. Its ?OH-scavenging action consists of direct and indirect antioxidant effects. Direct antioxidation occurs via multiple pathways, including ET, PCET or HAT. Indirect antioxidation involves binding to Fe2+.  相似文献   

10.
A copper‐oxide‐based catalyst enriched with paramelaconite (Cu4O3) is presented and investigated as an electrocatalyst for facilitating electroreduction of CO2 to ethylene and other hydrocarbons. Cu4O3 is a member of the copper‐oxide family and possesses an intriguing mixed‐valance nature, incorporating an equal number of Cu+ and Cu2+ ions in its crystal structure. The material is synthesized using a solvothermal synthesis route and its structure is confirmed via powder X‐ray diffraction, transmission electron microscope based selected area electron diffraction, and X‐ray photoelectron spectroscopy. A flow reactor equipped with a gas diffusion electrode is utilized to test a copper‐based catalyst enriched with the Cu4O3 phase under CO2 reduction conditions. The Cu4O3‐rich catalyst (PrC) shows a Faradaic efficiency for ethylene over 40% at 400 mA cm?2. At ?0.64 versus reversible hydrogen electrode, the highest C2+/C1 product ratio of 4.8 is achieved, with C2+ Faradaic efficiency over 61%. Additionally, the catalyst exhibits a stable performance for 24 h at a constant current density of 200 mA cm?2.  相似文献   

11.
Superoxide radical anion (O2˙?) as an important member of reactive oxygen species (ROS) plays a vital role both in physiology and pathology. Herein we designed and synthesized a novel phosphinate‐based bioluminescence probe for O2˙? detection in living cells, which exhibited good sensitivity for capturing O2˙? at the nanomole level and high selectivity against other ROS. The probe was further found to be of low toxicity for living cells and was then successfully employed for sensing endogenous O2˙? by using phorbol‐12‐myristate‐13‐acetate (PMA) as a traditional O2˙? stimulator in Huh7 cells. Moreover, the increasing production and use of nanoparticles, has given rise to many concerns and debates among the public and scientific authorities regarding their safety and final fate in biological systems. Herein it was found that mondisperse polystyrene particles could stimulate O2˙? generation in Huh7 cells. Overall, the probe was demonstrated to have a great potential as a novel bioluminescent sensor for detecting O2˙? in living cells. To our knowledge, this is the first small‐molecule phosphinate‐based bioluminescence probe that will open up great opportunities for unlocking the mystery of O2˙? in human health and disease.  相似文献   

12.
P1B-type ATPases transport a variety of metals (Cd2+, Zn2+, Pb2+, Co2+, Cu2+, Ag+, Cu+) across biomembranes. Characteristic sequences CP[C/H/S] in transmembrane fragment H6 were observed in the putative transporting metal site of the founding members of this subfamily (initially named CPx-ATPases). In spite of their importance for metal homeostasis and biotolerance, their mechanisms of ion selectivity are not understood. Studies of better-characterized PII-type ATPases (Ca-ATPase and Na,K-ATPase) have identified three transmembrane segments that participate in ion binding and transport. Testing the hypothesis that metal specificity is determined by conserved amino acids located in the equivalent transmembrane segments of P1B-type ATPases (H6, H7, and H8), 234 P1B-ATPase protein sequences were analyzed. This showed that although H6 contains characteristic CPX or XPC sequences, conserved amino acids in H7 and H8 provide signature sequences that predict the metal selectivity in each of five P1B-ATPase subgroups identified. These invariant amino acids contain diverse side chains (thiol, hydroxyl, carbonyl, amide, imidazolium) that can participate in transient metal coordination during transport and consequently determine the particular metal selectivity of each enzyme. Each subgroup shares additional structural characteristics such as the presence (or absence) of particular amino-terminal metal-binding domains and the number of putative transmembrane segments. These differences suggest unique functional characteristics for each subgroup in addition to their particular metal specificity.  相似文献   

13.
An electrochemiluminescence (ECL) sensor based on reduced graphene oxide–CdTe quantum dots (RGO–CdTe QDs) composites for detecting copper ion (Cu2+) was proposed. The ECL behaviours of the RGO–CdTe QD modified electrode were investigated with H2O2 as the co‐reactant. Quantitative detection of Cu2+ was realized as Cu2+ could effectively quench the ECL signal of the RGO–CdTe QDs. A wide linear range of 1.00 × 10?14 to 1.00 × 10?4 M (R = 0.9953) was obtained under optimized conditions, and a detection limit (S/N = 3) was achieved of as low as 3.33 × 10?15 M. The proposed sensor also exhibited good stability and selectivity for the detection of copper ions. Finally, the analytical application of the proposed sensor was also evaluated using river water.  相似文献   

14.
Quenching effects of bergenin, based on the electrochemiluminescence (ECL) of the tris(2,2′‐bipyridyl)‐ruthenium(II) (Ru(bpy)32+)/tri‐n‐propylamine (TPrA) system in aqueous solution, is been described. The quenching behavior can be observed with a 100‐fold excess of bergenin over Ru(bpy)32+. In the presence of 0.1 m TPrA, the Stern–Volmer constant (KSV) of the ECL quenching is as high as 1.16 × 104 M?1 for bergenin. The logarithmic plot of the inhibited ECL versus logarithmic plot of the concentration of bergenin was linear over the range 3.0 × 10?6–1.0 × 10?4 mol/L. The corresponding limit of detection was 6.0 × 10?7 mol/L for bergenin (S/N = 3). In the mechanism of quenching it is believed that the competition of the active free radicals between Ru(bpy)32+/TPrA and bergenin was the key factor for the ECL inhibition of the system. Photoluminescence, cyclic voltammetry, coupled with bulk electrolysis, supports the supposition mechanism of the Ru(bpy)32+/TPrA–bergenin system. Copyright © 2015 John Wiley & Sons, Ltd.  相似文献   

15.
Fluorescence study of the complexation between uranyl salophen (L) and some common anions in acetonitrile–water (90:10, v/v) solution showed a tendency of L toward acetate ion (AcO?). The fluorescence enhancement of L is attributed to a 1:1 complex formation between L and acetate ion which was utilized as the basis for the selective detection of AcO?. The association constant of the 1:1 complex formation of L–AcO? was calculated as 6.60 × 106. The linear response range of the fluorescent chemosensor covers a AcO? concentration range of 1.6 × 10?7 to 2.5 × 10?5 mol/L, with a detection limit of 2.5 × 10?8 mol/L. L showed a selective and sensitive fluorescence enhancement response toward acetate ion over I3?, NO3?, CN?, CO32?, Br?, Cl?, F?, H2PO4? and SO42?, which was attributed to the higher stability of inorganic complex between acetate and L. Copyright © 2012 John Wiley & Sons, Ltd.  相似文献   

16.
Erythritol, a well-known natural sweetener, is mainly produced by microbial fermentation. Various metal ions (Al3+, Cu2+, Mn2+, and Ni2+) were added to the culture medium of Trichosporonoides oedocephalis ATCC 16958 at 30?mg/L in shake flask cultures. Compared with controls, Cu2+ increased the erythritol content by 86% and decreased the glycerol by-product by 31%. After 48 hr of shake flask culture, sodium dodecyl sulfate polyacrylamide gel electrophoresis showed that expression levels of erythrose reductase (ER) in the presence of 30?mg/L CuSO4?·?5H2O were higher than those obtained after treatment with other examined metal ions. Furthermore, after 108 hr of batch culture in a 5-L bioreactor, supplementation with 30?mg/L of CuSO4?·?5H2O increased the specific erythritol content by 27%. Further studies demonstrated that ER activity under 30?mg/L CuSO4?·?5H2O supplementation in a fermentor was overtly increased compared with the control after 60 hr, while glycerol-3-phosphate dehydrogenase activity was clearly reduced in most of the fermentation process. Furthermore, the NADPH/NADP ratio was slightly lower in T. oedocephalis cells treated with Cu2+ compared with control cells. These results provide further insights into Cu2+ effects on erythritol biosynthesis in T. oedocephalis and should improve the industrial production of erythritol by biological processes.  相似文献   

17.
A novel colorimetric probe RP1 was synthesized using rhodamine derivatives and heterocyclic compounds for the purpose of detecting Cu2+. RP1 showed good selectivity, high sensitivity and affinity toward Cu2+ over other competing ions in CH3OH–H2O (1/1, v/v) solution. Absorbance intensity showed a good linear fit between probe R1 and Cu2+ over the concentration range 1–8 μM and the association constant was also calculated to be 1.145 × 105 M?1. The sensing mechanism was deduced using Job's plot, Fourier transform infrared spectroscopy, and density functional theory studies. In addition, the colorimetric experiment indicated that probe RP1 could be made into test paper to detect Cu2+ with a colour change from colourless to pink.  相似文献   

18.
The oxidation reaction of H2O2 with KIO4 can produce chemiluminescence (CL) in the presence of the surfactant Tween40 and the CL intensity of the CL system KIO4–H2O2–Tween40 can be strikingly enhanced after injection of tannic acid. On this basis, a flow injection method with CL detection was established for the determination of tannic acid. The method is simple, rapid and effective to determine tannic acid in the range of 7.0 × 10?9 to 1.0 × 10?5 mol/L with a determination limit of 2.3 × 10?9 mol/L. The relative standard deviation is 2.6% for the determination of 5.0 × 10?6 mol/L tannic acid (n = 11). The method has been applied to determine the content of tannic acid in industrial wastewater with satisfactory results. It is believed that the CL reaction formed singlet oxygen 1O2* and the emission was from an excited oxygen molecular pair O2(1Δg)O2(1?g) in the KIO4–H2O2–Tween40 reaction. Tween40 played an important role in enhancing stabilization of the excited oxygen molecular pair O2(1Δg)O2(1?g) and in increasing CL intensity. Copyright © 2010 John Wiley & Sons, Ltd.  相似文献   

19.
Peroxidases were isolated from Sapindus mukorossi (Reetha) and partially purified using acetone precipitation, ion-exchange chromatography with a 14-fold purification, 22% recovery and a specific activity of 266?×?103 units/mg protein. Sapindus peroxidases (SPases) showed six bands after acetone precipitation and one distinct band after ion exchange chromatography on Native-PAGE after zymography. Enzymes purified by ion exchange chromatography were loaded on Sepahdex G-50 superfine column and their molecular weight was reported to be 25?kDa. They showed temperature optima at 50°C and pH optima at 5.0.?km for SPases was reported to be 1.05?mM and 0.186?mM for guaiacol and H2O2 respectively. The Vmax/Km value for o-dianisidine was 449 while for H2O2 it was 5?×?105. Protocatechuic acid acts as a potent inhibitor for SPases (6.0% relative activity at 4.5???M) but ferulic acid inhibits its activity at a much lower concentration (0.02???M). Enzymes were stimulated by metal cations like Cu2+, Ca2+ (145, 168; percentage relative activity respectively) and showed mild inhibition (up to 20%) with Mn2+ and Mg2+. Alanine stimulated the enzyme activity (up to 33%; at 0?C100???M) while other amino acids like cysteine, methionine, tryptophan and tyrosine inhibited the SPases (13?C57% at 0?C100???M).  相似文献   

20.
A novel multifunctional fluorescent peptide sensor based on pentapeptide dansyl‐Gly‐His‐Gly‐Gly‐Trp‐COOH (D‐P5) was designed and synthesized efficiently using Fmoc solid‐phase peptide synthesis (SPPS). This fluorescent peptide sensor shows selective and sensitive responses to Hg2+ and Cu2+ among 17 metal ions and six anions studied in N‐2‐hydroxyethylpiperazine‐N‐2‐ethane sulfonic acid (HEPES) buffer solution. The peptide probe differentiates Hg2+ and Cu2+ ions by a ‘turn‐on’ response to Hg2+ and a ‘turn‐off’ response to Cu2+. Upon addition of Hg2+ or Cu2+ ions, the sensor displayed an apparent color change that was visible under an ultraviolet lamp to the naked eye. The limits of detection (LOD) of DP‐5 were 25.0 nM for Hg2+ and 85.0 nM for Cu2+; the detection limits for Cu2+ were much lower than the drinking water maximum contaminant levels set out by the United States Environmental Protection Agency (USEPA). It is noteworthy that both D‐P5‐Hg and D‐P5‐Cu systems were also used to detect S2? successfully based on the formation of ternary complexes. The LODs of D‐P5‐Hg and D‐P5‐Cu systems for S2? were 217.0 nM and 380.0 nM, respectively. Furthermore, the binding stoichiometry, binding affinity and pH sensitivity of the probe for Hg2+ and Cu2+ were investigated. This study gives new possibilities for using a short fluorescent peptide sensor for multifunctional detection, especially for anions.  相似文献   

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