A single 8-hydroxyquinoline-appended bile acid fluorescent probe obtained by click chemistry for solvent-dependent and distinguishable sensing of zinc(II) and cadmium(II)

Construction of fluorescent probes for zinc ion (Zn²⁺) and cadmium ion (Cd²⁺) is significant for the safety of humans. However, the discriminating recognition of Zn²⁺ and Cd²⁺ by a single probe remains challenging owing to their similar properties. Herein, a novel deoxycholic acid derivative containing 8-hydroxyquinoline fluorophore has been facilely synthesized through click chemistry to form a clamp-like probe. Using its perfect bonding cavity from 1,2,3-triazole and quinoline, this molecule showed favorable solvent-dependent fluorescent responses and distinguished Zn²⁺ and Cd²⁺ in different solvents. In ethanol aqueous solution, it displayed good selectivity and ratiometric fluorescence to Zn²⁺ with 30 nm spectroscopic red-shifts. In acetonitrile aqueous solution, it exhibited good selectivity and ratiometric fluorescence to Cd²⁺ with 18 nm spectroscopic red-shifts. Moreover, the unique microstructural features of the probe in assembly were used to reflect its recognition processes. Due to its merits of low detection limit and instant response time, the probe was utilized for sensing Zn²⁺ and Cd²⁺ in water, beer and urine with high accuracy. Meanwhile, this probe served as a handy tool and was employed to obtain inexpensive test strips for the prompt and semiqualitative analysis of Zn²⁺ and Cd²⁺ with the naked eye.     

Convenient and highly effective fluorescence sensing for Hg2+ in aqueous solution and thin film

A quinolinocyclodextrin, that is, MQAS-β-cyclodextrin (MQAS = N-(2-methyl-8-amino- quinolyl)-p-aminobenzene sulfonamide) was synthesized. Further experiments showed that it could form very stable stoichiometric 2:1 complex with Zn²⁺ in water. Significantly, the resultant quinolinocyclodextrin/Zn²⁺ complex showed the specific fluorescence response to Hg²⁺ over other metal ions, which could be readily distinguished in either aqueous solution or the PVA-based thin film. This finding would enable Zn·3₂ complex as a convenient and highly efficient fluorescence sensor for the detection of Hg²⁺.     

Role of Organic Acids in Sunflower Tolerance to Heavy Metals

Exposure of Helianthus annuus L. seedlings to Al³⁺, Cd²⁺ or Zn²⁺ resulted in a marked decrease of fresh and dry masses of the shoots and the roots. The increase of Al³⁺, Cd²⁺ or Zn²⁺ uptake was accompanied by a significant decrease of nitrate, phosphorus and K⁺ uptake. There was a significant increase of malic and citric acid contents in the shoots and roots of heavy metal-treated seedlings whereas the change in fumaric acid was insignificant. Al³⁺ and Zn²⁺ alone stimulated excretion of malic and citric acids to the rhizosphere. Addition of high concentrations of malic or citric acid alleviate to some extent the inhibitory effect of Al³⁺ and Zn²⁺ on plant growth. This revised version was published online in July 2006 with corrections to the Cover Date.     

Biosorption of Pb<Superscript>2+</Superscript> and Zn<Superscript>2+</Superscript> by Non-Living Biomass of <Emphasis Type="Italic">Spirulina</Emphasis> sp.

Removal of heavy metals (Pb²⁺, Zn²⁺) from aqueous solution by dried biomass of Spirulina sp. was investigated. Spirulina rapidly adsorbed appreciable amount of lead and zinc from the aqueous solutions within 15 min of initial contact with the metal solution and exhibited high sequestration of lead and zinc at low equilibrium concentrations. The specific adsorption of both Pb²⁺ and Zn²⁺ increased at low concentration and decreased when biomass concentration exceeded 0.1 g l⁻¹. The binding of lead followed Freundlich model of kinetics where as zinc supported Langmuir isotherm for adsorption with their r ² values of 0.9659 and 0.8723 respectively. The adsorption was strongly pH dependent as the maximum lead biosorption occurred at pH 4 and 10 whereas Zn²⁺ adsorption was at pH 8 and 10.     

A reversible calix[4]arene armed phenolphthalein based fluorescent probe for the detection of Zn2+ and an application in living cells

A reversible and easy assembled fluorescent sensor based on calix[4]arene and phenolphthalein (C4P) was developed for selective zinc ion (Zn²⁺) sensing in aqueous samples. The probe C4P demonstrated high selective and sensitive detection towards Zn²⁺ over other competitive metal ions. Interaction of Zn²⁺ with a solution of C4P resulted in a considerable increment in emission intensity at 440 nm (λ_ex = 365 nm) due to the suppression of photoinduced electron transfer (PET) process and the restriction of C=N isomerization . The binding constant (K_a) of C4P with Zn²⁺ was calculated to be 4.50 × 10¹¹ M^?2 and also the limit of detection of C4P for Zn²⁺ was as low as 0.108 μM (at 10^?7 M level). Moreover, the fluorescence imaging in the human colon cancer cells suggested that C4P had great potential to be used to examine Zn²⁺ in vivo.     

An inducible hydrolase from Mortierella isabellina (basidiomycetes). The deacylation of (+)-usnic acid

An inducible enzyme catalysing the hydrolysis of (+)-usnic acid to (+)-2-desacetylusnic acid and acetic acid has been purified 150-fold from the mycelium of Mortierella isabellina grown in the presence of (+)-usnic acid. Purification was achieved by treatment with protamine sulfate, (NH₄)₂SO₄ fractionation, negative adsorption on alumina Cγ gel and hydroxylapatite followed by chromatography on DEAE-cellulose and Sephadex G-200. The elution pattern from a Sephadex G-200 column indicated a MW of ca 7.6 × 10⁴ for the enzyme. The apparent K_m value for (+)-usnic acid at the pH optimum (pH 7) was 4.0 × 10^?5 M. The enzyme was specific for (+)-usnic acid and inactive towards (?)-usnic acid, (+)-isousnic acid or certain phloracetophenone derivatives. Its activity was enhanced in the presence of divalent metal ions such as Co²⁺, Ni²⁺, Mn²⁺, Mg²⁺ and Zn²⁺.     

Sorption of Copper and Zinc to the Plasma Membrane of Wheat Root

Sorption of Cu²⁺ and Zn²⁺ to the plasma membrane (PM) of wheat root (Triticum aestivum Lcv. Scout 66) vesicles was measured at different pH values and in the presence of organic acids and other metals. The results were analyzed using a Gouy-Chapman-Stem model for competitive sorption (binding and electrostatic attraction) to a negative binding site. The binding constants for the two investigated cations as evaluated from the sorption experiments were 5 M^–1 for Zn²⁺ and 400 M^–1 for Cu²⁺. Thus, the sorption affinity of Cu²⁺ to the PM is considerably larger than that of Ca²⁺, Mg²⁺ or Zn²⁺. The greater binding affinity of Cu²⁺ was confirmed by experiments in which competition with La³⁺ for sorption sites was followed. The amount of sorbed Cu²⁺ decreased with increasing K⁺, Ca²⁺, or La³⁺ concentrations, suggesting that all these cations competed with Cu²⁺ for sorption at the PM binding sites, albeit with considerable differences among these cations in effectiveness as competitors with Cu²⁺. The sorption of Cu²⁺ and Zn²⁺ to the PM decreased in the presence of citric acid or malic acid. Citric acid (as well as pH) affected the sorption of Cu²⁺ or Zn²⁺ to PM more strongly then did malic acid.     

Novel Zn2+-binding Sites in Human Transthyretin: IMPLICATIONS FOR AMYLOIDOGENESIS AND RETINOL-BINDING PROTEIN RECOGNITION*

Human transthyretin (TTR) is a homotetrameric protein involved in several amyloidoses. Zn²⁺ enhances TTR aggregation in vitro, and is a component of ex vivo TTR amyloid fibrils. We report the first crystal structure of human TTR in complex with Zn²⁺ at pH 4.6–7.5. All four structures reveal three tetra-coordinated Zn²⁺-binding sites (ZBS 1–3) per monomer, plus a fourth site (ZBS 4) involving amino acid residues from a symmetry-related tetramer that is not visible in solution by NMR. Zn²⁺ binding perturbs loop E-α-helix-loop F, the region involved in holo-retinol-binding protein (holo-RBP) recognition, mainly at acidic pH; TTR affinity for holo-RBP decreases ∼5-fold in the presence of Zn²⁺. Interestingly, this same region is disrupted in the crystal structure of the amyloidogenic intermediate of TTR formed at acidic pH in the absence of Zn²⁺. HNCO and HNCA experiments performed in solution at pH 7.5 revealed that upon Zn²⁺ binding, although the α-helix persists, there are perturbations in the resonances of the residues that flank this region, suggesting an increase in structural flexibility. While stability of the monomer of TTR decreases in the presence of Zn²⁺, which is consistent with the tertiary structural perturbation provoked by Zn²⁺ binding, tetramer stability is only marginally affected by Zn²⁺. These data highlight structural and functional roles of Zn²⁺ in TTR-related amyloidoses, as well as in holo-RBP recognition and vitamin A homeostasis.     

Zinc and lead uptake by mycelium and regenerating protoplasts of Verticillium marquandii

The ability of the filamentous fungus Verticillium marquandii for Zn²⁺ and Pb²⁺ uptake from aqueous solution was studied. The 24-h-old living mycelium bound Zn²⁺ and Pb²⁺ (206.2 and 324.5 mg/g dry weight, respectively) effectively, in contrast to a very low Zn²⁺ uptake by autoclaved mycelium (20.2 mg/g). The most effective results were noted when the metals were introduced as acetates and incubated with mycelium for 24 h in case of Zn²⁺ while Pb²⁺ achieved the maximum level of metal binding after as early as 3 h. The cell wall was the main site of effective Zn²⁺ and Pb²⁺ binding by V. marquandii mycelium (91.0–93.6% of metals were located in cell wall after 24 h of exposure). The metabolic inhibitors: antimycin A and sodium azide had a strong limitation effect on Zn²⁺ uptake by a 24-h-old living mycelium, whereas Pb²⁺ binding did not decrease to a large extent. The freshly obtained protoplasts accumulated Zn²⁺ and Pb²⁺ on a low level in comparison with cells at different stages of cell wall regeneration. The use of regenerating protoplasts showed that resynthesis of cell wall was necessary for high binding of Zn²⁺, whereas Pb²⁺ uptake on the significant level took place during cell wall regeneration. This revised version was published online in August 2006 with corrections to the Cover Date.     

Fluorescent salicylaldehyde hydrazone as selective chemosensor for Zn2+ in aqueous ethanol: a ratiometric approach

4‐N,N‐diethylaminosalicylaldehyde hydrazone Schiff base ( 1 ) and its analogues ( 2 - 6 ) were synthesized and characterized by NMR, MS and elemental analysis. Compound 1 exhibited ratiometric fluorescent response to Zn²⁺ over other metal ions in aqueous ethanol solution with neutral buffer. The complexation ratio, site and constant and the effect of pH value and water fraction on its fluorescent response to Zn²⁺ were investigated. Copyright © 2009 John Wiley & Sons, Ltd.     

叶面喷施氨基酸和微量元素对金银花生长发育和质量的影响

以2年生金银花为试验材料,采用叶面喷施法,研究不同浓度的苯丙氨酸(Phe)、酪氨酸(Lyr)以及锌(Zn2+)、铜(Cu2+)对金银花生长发育和质量的影响。结果显示:(1)喷施不同浓度的Phe、Lyr以及Zn2+、Cu2+对叶面积无明显影响;不同处理的叶绿素含量随喷施次数的增加而出现不同程度的下降,喷施浓度适宜则有助于叶绿素的合成;喷施一定浓度的Phe、Lyr以及Zn2+、Cu2+可增加花蕾重量,如经1 000mg/g Phe处理后的花蕾鲜重与干重较对照增加了20.1%和51.4%。(2)不同浓度的Phe、Lyr可显著影响碳代谢,但对氮代谢影响不明显;Zn2+、Cu2+对碳氮代谢产物影响较明显,如喷施10mg/L的CuSO4及ZnSO4可提高可溶性糖及淀粉含量。(3)除Zn2+处理后的花蕾类黄酮含量显著低于对照外,其他处理较CK无显著差异;花蕾总黄酮含量均显著低于对照,但绿原酸含量均高于对照。(4)叶片中离子含量受喷施次数及浓度影响较明显,除30mg/L CuSO4处理外,其它处理的花蕾中Zn2+、Cu2+、Fe2+含量均显著低于对照。研究表明,在金银花的第一茬花抽枝初期喷施适宜浓度的Phe、Lyr(如1 000mg/g Phe、2 000mg/g Lyr)以及Zn2+、Cu2+(如50mg/L ZnSO4、10mg/L CuSO4)可改善金银花的生长发育,并提高产量和质量。     

Post-transcriptional inhibition of ornithine decarboxylase induction by zinc in a difluoromethylornithine resistant cell line

Addition of Zn^2+_ to cell medium inhibited the induction of ornithine decarboxylase (ODC) activity in ODC overproducing L1210-DFMO^r cells. A significant effect was observed at a concentration as low as 0.01 mM, however a more marked inhibition was caused by the addition of 0.1 mM Zn²⁺. The inhibition of the induction of ODC activity was accompanied by a proportional decrease in the content of immunoreactive ODC protein, whereas the level of ODC mRNA, detemined by a solution hybridization RNase protection assay, was not affected signigicantly. Instead, some acceleration of ODC turnover was observed. the addition of 0.1 mM Co²⁺ or Mn²⁺, but not of other divalent metal ions, also inhibited ODC induction; differently from Zn²⁺ however, these metals affected cell viability and/or cell growth. Removal of endogenous Zn²⁺ by a chelator also provoked a strong decrease of ODC induction, which was reversed by Zn²⁺. However, addition of Zn²⁺ in excess of the chelator proved to be markedly inhibitory. These results indicate that both a restricted Zn²⁺ availability and an enhanced presence of the metal can inhibit the induction of ODC in L1210-DFMO^r cells.     

Effect of manganese on ninhydrin color development by amino acids

Addition of microgram quantities (5–10 μg per 2 ml) of Mn²⁺, Fe²⁺, and Mo²⁺ increases the intensity of color developed by amino acids two- to three-fold when reacting with ninhydrin. The lowest limit detected by the increased sensitivity of the reaction is 3 nmol of an amino acid. Cd²⁺, Zn²⁺, and Al³⁺ depress the color formation due to reaction between amino acids and ninhydrin. When chromatograms of amino acids are first sprayed with aqueous manganese chloride and later with ninhydrin or with ninhydrin solution containing manganese, not only is the sensitivity increased, but the stained spots retain their color for longer periods.     

Raman spectroscopic studies on the interaction between divalent counterion and polyion

The nature of the interaction between polyacrylalc ion and several divalent cations, such as Cu²⁺, Mn²⁺, Zn²⁺, Ba²⁺ and Mg²⁺, was investigated using Raman spectroscopy. A specific Raman band characteristic of a carboxyl group is shifted upon addition of Cu²⁺. Zn²⁺ and Mn²⁺ to partially neutralized poly(acrylic acid). On the other hand. no frequency shift of the specific Raman band is observed on addition of Mg²⁺ and Ba²⁺*, though the intensity of the specific Raman band decreases with concentration of MgCl₂. It is concluded from these Raman data that the interaction between polyacrylatc ion and Cu²⁺. Zn²⁺ or Mn²⁺ includes a specific interaction with bond formation, whereas in the case of Mg²⁺ and Ba²⁺, the electrostatic interaction is dominant.     

Effect of calcium on synthesis of dipicolinic acid inPenicillium citreoviride and its feedback resistant mutant

Dipicolinic acid synthesis inPenicillium citreoviride strain 3114 was inhibited by Ca²⁺ ions, but not by Ba²⁺, Cu²⁺or Fe²⁺. Among the metals tested, only Zn²⁺ inhibited the synthesis of dipicolinic acid and promoted sporulation. None of these metals reversed the inhibition by Ca²⁺ or Zn²⁺. A mutant 27133-dpa-ca selected for resistance to feedback inhibition by dipicolinic acid: Ca²⁺ complex showed cross-resistance to inhibition by dipicolinic acid: Zn²⁺. Both 3114 and271 33-dpa-ca excreted a number of aliphatic and amino acids during secondary metabolism of dipicolinic acid. In the presence of 1000 ppm of Ca²⁺, accumulation of citric acid and α-aminoadipic acid was completely inhibited under conditions of inhibition of dipicolinic acid in parent strain 3114 but not in the mutant. Citric acid with or without Ca²⁺ did not inhibit thede novo synthesis of dipicolinic acid in the strain 3114. In fact, citric acid in the presence of Ca²⁺ improved significantly rate of dipicolinic acid synthesis. Apart from resistance to feed back inhibition by dipicolinic acid: Ca²⁺ complex, mutant differed from the parent in three other aspectsviz. (i) dipicolinic acid synthesis was not subject to catabolite repression by glucose, (ii) sporulation as well as dipicolinic acid synthesis was dependent on the presence of Ca²⁺ ions in the medium and (iii) Mg²⁺ requirement for the mutant increased three fold. Higher requirement of the Mg²⁺ could be partially relieved by Ca²⁺ during secondary metabolism. The results support the inference thatde novo synthesis of dipicolinic acid is regulated through feedback inhibition by dipicolinic acid: Ca²⁺complex.     

Synthesis and coordination behaviors of 14-membered tetraaza macrocyclic copper(II) complexes bearing two N-propionic acid or N-propionic methyl ester groups

A di-N-functionalized 14-membered tetraaza macrocycle, [H₄L³](ClO₄)₂ (L³ = 1,8-bis(2-carboxyethyl)-3,5,7,7,10,12,14,14-octamethyl-1,4,8,11-tetraazacyclotetradecane), has been synthesized by acid hydrolysis of 1,8-bis(2-cyanoethyl)-3,5,7,7,10,12,14,14-octamethyl-1,4,8,11-tetraazacyclotetradecane (L²). The copper(II) complexes [CuL²](ClO₄)₂ and [Cu(H₂L³)](ClO₄)₂ were prepared and characterized. The complex [Cu(H₂L³)]²⁺ readily reacts with methanol to yield [CuL⁴]²⁺ (L⁴ = 1,8-bis(2-carbomethoxyethyl)-3,5,7,7,10,12,14,14-octamethyl-1,4,8,11-tetraazacyclotetradecane). The N-CH₂CH₂COOH groups of [Cu(H₂L³)](ClO₄)₂ are not coordinated to the metal ion in the solid state but are involved in coordination in various non-aqueous solvents or in aqueous solutions of pH ? 1.0. Interestingly, [CuL⁴](ClO₄)₂ exists as two stable structural isomers, 1 (the pendant ester groups are not involved in coordination) and 2 (one of the two ester groups is coordinated to the metal ion), in the solid state; the two isomers can be prepared selectively by controlling ionic strength of a methanol solution of the complex. Crystal structures and coordination behaviors of the two isomers are described. The di-N-cyanoethylated macrocyclic complex [CuL²](ClO₄)₂ is rapidly decomposed in 0.1 M NaOH solution even at room temperature. On the other hand, [Cu(H₂L³)](ClO₄)₂ and [CuL⁴](ClO₄)₂ are quite inert against decomposition under similar basic conditions. In acidic or basic aqueous solutions, [CuL⁴]²⁺ is hydrolyzed to [Cu(H₂L³)]²⁺ or [CuL³].     

Inhibition of nitrogen fixation in alfalfa by arsenate, heavy metals, fluoride, and simulated Acid rain

The acute effects of aqueous solutions of As, Cd, Cu, Pb, F, and Zn ions at concentrations from 0.01 to 100 micrograms per milliliter and solutions adjusted to pH 2 to 6 with nitric or sulfuric acid were studied with respect to acetylene reduction, net photosynthesis, respiration rate, and chlorophyll content in Vernal alfalfa (Medicago sativa L. cv. Vernal). The effects of the various treatments on acetylene reduction varied from no demonstrable effect by any concentration of F⁻ and 42% inhibition by 100 micrograms Pb²⁺ per milliliter, to 100% inhibition by 10 micrograms Cd²⁺ per milliliter and 100 micrograms per milliliter As, Cu²⁺, and Zn²⁺ ions. Zn²⁺ showed statistically significant inhibition of activity at 0.1 micrograms per milliliter. Acid treatments were not inhibitory above pH 2, at which pH nitric acid inhibited acetylene reduction activity more than did sulfuric acid. The inhibition of acetylene reduction by these ions was Zn²⁺ > Cd²⁺ > Cu²⁺ > AsO₃⁻ > Pb²⁺ > F⁻. The sensitivity of acetylene reduction to the ions was roughly equal to the sensitivity of photosynthesis, respiration, and chlorophyll content when Pb²⁺ was applied, but was 1,000 times more sensitive to Zn²⁺. The relationship of the data to field conditions and industrial pollution is discussed.     

A highly selective and sensitive boronic acid-based sensor for detecting Pd2+ ion under mild conditions

Herein, a boronic acid-based sensor was reported selectively to recognize Pd²⁺ ion. The fluorescence intensity increased 36-fold after sensor binding with 2.47 × 10⁻⁵ M of Pd²⁺ ion. It was carried out in the 99% aqueous solution for binding tests, indicating sensor having good water solubility. In addition, it is discernible that Pd²⁺ ion turned on the blue fluorescence of sensor under a UV–lamp (365 nm), while other ions (Ag⁺, Al³⁺, Ba²⁺, Ca²⁺, Cr²⁺, Cd²⁺, Co²⁺, Cs²⁺, Cu²⁺, Fe²⁺, Fe³⁺, K⁺, Li⁺, Mg²⁺, Mn²⁺, Na⁺, Ni²⁺ and Zn²⁺) did not show the similar change. Furthermore, sensor has a low limit of detection (38 nM) and high selectivity, which exhibits the potential for the development of Pd²⁺ recognition in practical environments.     

Removal of Cd2+, Pb2+, and Zn2+ from contaminated water using dolomite powder

Dolomite collected from Surat Thani Province in Thailand was investigated for use as a sorbent for the removal of divalent heavy metal cations from an aqueous solution. The sorbent had a surface area of 2.46 m²/g and a pH of zero point charge (pHzpc) of 9.2. Batch sorption was used to examine the effect of the pH (pH 3–7) on the sorption capacity of Cd²⁺, Pb²⁺ and Zn²⁺, alone or together as an equimolar mixture at various concentrations. Alone, each heavy metal cation was adsorbed faster at a higher pH, where the sorption of Cd²⁺ and Pb²⁺ fitted a Langmuir isotherm, but Zn²⁺ sorption best fitted a Freundlich isotherm. Under equimolar competitive sorption, the sorption capacity of each cation was decreased by 75.8% (0.29–0.07 mM/g), 82.8% (0.53–0.09 mM/g), and 95.7% (0.84–0.04 mM/g) for Cd²⁺, Pb²⁺ and Zn²⁺, respectively, compared to that with the respective single cation. Desorption of these heavy metal cations from dolomite was low, with an average desorption level of 0.06–17.4%. Furthermore, since dolomite is readily available and rather cheap, it is potentially suitable for use as an efficient sorbent to sorb Cd²⁺ and Pb²⁺, and perhaps Zn²⁺, from contaminated water.     

Proton‐dependent zinc release from intracellular ligands

In cultured cortical and hippocampal neurons when intracellular pH drops from 6.6 to 6.1, yet unclear intracellular stores release micromolar amounts of Zn²⁺ into the cytosol. Mitochondria, acidic organelles, and/or intracellular ligands could release this Zn²⁺. Although exposure to the protonophore FCCP precludes reloading of the mitochondria and acidic organelles with Zn²⁺, FCCP failed to compromise the ability of the intracellular stores to repeatedly release Zn²⁺. Therefore, Zn²⁺‐releasing stores were not mitochondria or acidic organelles but rather intracellular Zn²⁺ ligands. To test which ligands might be involved, the rate of acid‐induced Zn²⁺ release from complexes with cysteine, glutathione, histidine, aspartate, glutamate, glycine, and carnosine was investigated; [Zn²⁺] was monitored in vitro using the ratiometric Zn²⁺‐sensitive fluorescent probe FuraZin‐1. Carnosine failed to chelate Zn²⁺ but did chelate Cu²⁺; the remaining ligands chelated Zn²⁺ and upon acidification were releasing it into the medium. However, when pH was decreasing from 6.6 to 6.1, only zinc–cysteine complexes rapidly accelerated the rate of Zn²⁺ release. The zinc–cysteine complexes also released Zn²⁺ when a histidine‐modifying agent, diethylpyrocarbonate, was applied at pH 7.2. Since the cytosolic zinc–cysteine complexes can contain micromolar amounts of Zn²⁺, these complexes may represent the stores responsible for an acid‐induced intracellular Zn²⁺ release.