Small-molecule fluorescent sensors for investigating zinc metalloneurochemistry

The metalloneurochemistry of Zn(II) is of substantial current interest. Zinc is the second most abundant d-block metal ion in the human brain, and its distribution varies with relatively high concentrations found in the hippocampus. Brain zinc is generally divided into two types, protein-bound and loosely bound, the latter also being termed histochemically observable, chelatable, labile, or mobile zinc. The neurophysiological and neuropathological significance of mobile Zn(II) remains enigmatic. Studies of Zn(II) distribution, translocation, and function in vivo require tools for its detection. Because Zn(II) has a closed-shell d(10) configuration and no convenient spectroscopic signature, fluorescence is a well-suited method for monitoring Zn(II) in biological contexts. This Account summarizes work by our laboratory addressing the design, preparation, characterization, and use of small-molecule fluorescent sensors for imaging Zn(II) in living cells and samples of brain tissue. These sensors provide "turn-on" or ratiometric Zn(II) detection in aqueous solution at neutral pH. By making alterations to the Zn(II)-binding unit and fluorophore platform, we have devised sensors with varied photophysical and metal-binding properties. Several of these probes have been applied to image Zn(II) distribution, uptake, and mobilization in a variety of cell types, including neuronal cultures.     

Spectroscopic studies of copper, silver and gold-metallothioneins

Metallothionein is a ubiquitous protein with a wide range of proposed physiological roles, including the transport, storage and detoxification of essential and nonessential trace metals. The amino acid sequence of isoform 2a of rabbit liver metallothionein, the isoform used in our spectroscopic studies, includes 20 cysteinyl groups out of 62 amino acids. Metallothioneins in general represent an impressive chelating agent for a wide range of metals. Structural studies carried out by a number of research groups (using (1)H and (113)Cd NMR, X-ray crystallography, more recently EXAFS, as well as optical spectroscopy) have established that there are three structural motifs for metal binding to mammalian metallothioneins. These three structures are defined by metal to protein stoichiometric ratios, which we believe specifically determine the coordination geometry adopted by the metal in the metal binding site at that metal to protein molar ratio. Tetrahedral geometry is associated with the thiolate coordination of the metals in the M(7)-MT species, for M = Zn(II), Cd(II), and possibly also Hg(II), trigonal coordination is proposed in the M(11-12)-MT species, for M = Ag(I), Cu(I), and possibly also Hg(II), and digonal coordination is proposed for the metal in the M(17-18)-MT species for M = Hg(II), and Ag(I). The M(7)-MT species has been completely characterized for M = Cd(II) and Zn(II). (113)Cd NMR spectroscopic and x-ray crystallographic data show that mammalian Cd(7)-MT and Zn(7)-MT have a two domain structure, with metal-thiolate clusters of the form M(4)(S(cys))(11) (the alpha domain) and M(3)(S(cys))(9) (the beta domain). A similar two domain structure involving Cu(6)(S(cys))(11) (alpha) and Cu(6)(S(cys))(9) (beta) copper-thiolate clusters has been proposed for the Cu(12)-MT species. Copper-, silver- and gold-containing metallothioneins luminesce in the 500-600 nm region from excited triplet, metal-based states that are populated by absorption into the 260-300 nm region of the metal-thiolate charge transfer states. The luminescence spectrum provides a very sensitive probe of the metal-thiolate cluster structures that form when Ag(I), Au(I), and Cu(I) are added to metallothionein. CD spectroscopy has been used in our laboratory to probe the formation of species that exhibit well-defined three-dimensional structures. Saturation of the optical signals during titrations of MT with Cu(I) or Ag(I) clearly show formation of unique metal-thiolate structures at specific metal:protein ratios. However, we have proposed that these M=7, 12 and 18 structures form within a continuum of stoichiometries. Compounds prepared at these specific molar ratios have been examined by X-ray Absorption Spectroscopy (XAS) and bond lengths have been determined for the metal-thiolate clusters through the EXAFS technique. The stoichiometric ratio data from the optical experiments and the bond lengths from the XAS experiments are used to propose structures for the metal-thiolate binding site with reference to known inorganic metal-thiolate compounds.     

Recovery of zinc from pickling baths with amberlite LA-2. Influence of modifier on the extraction equilibrium

The extraction of zinc chloride by Amberlite LA-2, a long chain secondary alkylamine, dissolved in Shellsol K, a naphthenic solvent, has been studied at room temperature. Isodecanol was used as modifier. The aqueous phases were chloride solutions of Zn(II) and Fe(II) in the concentration range commonly encountered in pickling baths, viz. about 1 and 1.5 mol/l, respectively. The ionic strength was kept constant at 4 mol/l in all experiments. Measurement of the distribution equilibrium of zinc chloride was carried out over wide concentration ranges of amine, zinc chloride, free chloride and isodecanol. It was assumed that the zinc chloride was extracted according to the following reaction On the basis of this reaction, an easy to use model was developed to describe the extraction behaviour of Zn in typical pickling baths. Prediction and optimization of a solvent extraction plant performance under changing industrial feed conditions is then possible. This model takes account of the influence of isodecanol used as modifier.     

An aqua-adenine H-bonding interaction controlling the formation of the rare Zn(II)–N9(adenine) bond in crystal structure of diaqua(adenine)(iminodiacetato)zinc(II)

A novel mixed-ligand zinc(II) complex with iminodiacetato(2-) (IDA) and adenine (AdeH) ligands has been obtained. Its crystal consists of octahedral molecules [Zn(IDA)(AdeH)(H₂O)₂] where the selective Zn–N9(AdeH) bond, involving the most basic N(AdeH) donor atom, occupies the trans position versus the Zn–N(IDA) bond. The Zn(II)–N9(AdeH) binding mode seems to be rare enough in comparison to those previously reported for Zn(II) and AdeH or a variety of related ligands. The chelate-nucleobase recognition process is further accomplished by an O–H(aqua)⋯N3(adenine) inter-ligand H-bonding interaction, without any intra-molecular IDA–nucleobase interaction. This finding is attributed to the polarizing effect of Zn(II) on the aqua ligand and the possibilities of AdeH acting as N-donor for the metal(II) atom and H-acceptor for an intra-molecular inter-ligand H-bonding interaction. There are no aromatic π,π-stacking contributions in the 3D H-bonded network, where all polar N–H (IDA or AdeH) and O–H (aqua) bonds are involved as donors in H-bonding interactions, which include AdeH:AdeH and IDA:AdeH pairing by double inter-molecular bridges.     

Sorption of heavy metal ions from aqueous solutions in the presence of EDTA on monodisperse anion exchangers

Conventional precipitation methods of industrial sewage and wastewater purification are not very effective and are insufficient in many cases. This implies the necessity of searching new, effective methods exploiting cheap, accessible and ecologically safe ion exchangers and sorbents. The paper presents the studies on removal of heavy metal ions — Cu(II), Zn(II), Co(II), Ni(II) and Fe(III) — from aqueous solutions in the presence of EDTA carried out on commercially available, strongly basic monodisperse anion exchangers with the polystyrene skeleton gel, Lewatit MonoPlus M 500; and the macroporous, Lewatit MonoPlus MP 500, which are more widely applied in water purification processes. The research results indicate a high affinity of the Lewatit MonoPlus M 500 and Lewatit MonoPlus MP 500 anion exchangers in the chloride form for copper(II), nickel(II), cobalt(II) and zinc(II) complexes with EDTA. The affinity series for the heavy metal complexes in the 0.001 M M(II)/(III)–0.001 M EDTA and 0.001 M M(II)/(III)–0.001M EDTA–0.001 M–0.002 M NaOH systems were found for the Lewatit MonoPlus M 500 anion exchanger in the chloride form to be as follows: Cu(II) > Ni(II) > Co(II) > Zn(II) Fe(III). In the case of the Lewatit MonoPlus MP 500 anion exchanger in the chloride form there was found the following affinity series: Cu(II) > Co(II) > Ni(II) > Zn(II) Fe(III). These anion exchangers can be applied in the removal of copper(II) complexes from waters and wastewaters.     

Probing the Structure and Function of the Cytosolic Domain of the Human Zinc Transporter ZnT8 with Nickel(II) Ions

The human zinc transporter ZnT8 provides the granules of pancreatic β-cells with zinc (II) ions for assembly of insulin hexamers for storage. Until recently, the structure and function of human ZnTs have been modelled on the basis of the 3D structures of bacterial zinc exporters, which form homodimers with each monomer having six transmembrane α-helices harbouring the zinc transport site and a cytosolic domain with an α,β structure and additional zinc-binding sites. However, there are important differences in function as the bacterial proteins export an excess of zinc ions from the bacterial cytoplasm, whereas ZnT8 exports zinc ions into subcellular vesicles when there is no apparent excess of cytosolic zinc ions. Indeed, recent structural investigations of human ZnT8 show differences in metal binding in the cytosolic domain when compared to the bacterial proteins. Two common variants, one with tryptophan (W) and the other with arginine (R) at position 325, have generated considerable interest as the R-variant is associated with a higher risk of developing type 2 diabetes. Since the mutation is at the apex of the cytosolic domain facing towards the cytosol, it is not clear how it can affect zinc transport through the transmembrane domain. We expressed the cytosolic domain of both variants of human ZnT8 and have begun structural and functional studies. We found that (i) the metal binding of the human protein is different from that of the bacterial proteins, (ii) the human protein has a C-terminal extension with three cysteine residues that bind a zinc(II) ion, and (iii) there are small differences in stability between the two variants. In this investigation, we employed nickel(II) ions as a probe for the spectroscopically silent Zn(II) ions and utilised colorimetric and fluorimetric indicators for Ni(II) ions to investigate metal binding. We established Ni(II) coordination to the C-terminal cysteines and found differences in metal affinity and coordination in the two ZnT8 variants. These structural differences are thought to be critical for the functional differences regarding the diabetes risk. Further insight into the assembly of the metal centres in the cytosolic domain was gained from potentiometric investigations of zinc binding to synthetic peptides corresponding to N-terminal and C-terminal sequences of ZnT8 bearing the metal-coordinating ligands. Our work suggests the involvement of the C-terminal cysteines, which are part of the cytosolic domain, in a metal chelation and/or acquisition mechanism and, as now supported by the high-resolution structural work, provides the first example of metal-thiolate coordination chemistry in zinc transporters.     

A [meso-tetrakis(4-sulfonatophenyl)porphyrinato]zinc(ii) complex as an oral therapeutic for the treatment of type 2 diabetic KKA(y) mice

We prepared and characterized [meso-tetrakis(4-sulfonatophenyl)porphyrinato]zinc(II) ([Zn(tpps)]), and investigated its in vitro insulin-mimetic activity and in vivo hypoglycemic effect in type 2 diabetic KKA(y) mice. The results were compared with those of previously proposed insulin-mimetic zinc(II) complexes and zinc sulfate (ZnSO(4)). The in vitro insulin-mimetic activity of [Zn(tpps)] was considerably better than that of bis(allixinato)zinc(II) ([Zn(alx)(2)]), bis(maltolato)zinc(II) ([Zn(mal)(2)]), bis(2-aminomethylpyridinato)zinc(II) ([Zn(2-ampy)(2)](2+)), and ZnSO(4). In particular, the order of in vitro insulin-mimetic activity of the complexes was determined to be: [Zn(tpps)]>[Zn(alx)(2)]>[Zn(mal)(2)]>[Zn(2-ampy)](2+)>ZnSO(4). [Zn(tpps)] normalized the hyperglycemia of KKA(y) mice within 21 days when administered orally at doses of 10-20 mg (0.15-0.31 mmol) Zn per kg body mass for 28 days. In addition, metabolic syndromes such as insulin resistance, the degree of renal disturbance, and the degree of liver disturbance were significantly improved in [Zn(tpps)]-treated KKA(y) mice relative to those administered with saline and ZnSO(4). The improvement in diabetes was validated by the results of oral glucose-tolerance tests and the decrease in the HbA(1c) level observed. In contrast, ZnSO(4) and the ligand H(2)tpps did not lower the elevated blood glucose level under the same experimental conditions. Based on these observations, [Zn(tpps)] is proposed to be the first orally active zinc(II)-porphyrin complex for the efficacious treatment of not only type 2 diabetes but also metabolic syndromes in animals.     

Аntimicrobial and anticancer activity of new poly(propyleneamine) metallodendrimers

The synthesis, EPR characterisation and biological evaluation of two new metallodendrimers, i.e. a poly(propyleneamine) dendrimer functionalized at the external surface with 4-bromo-1,8-naphthalimide and conjugated with Cu(II) and Zn(II), was performed with the aim to evaluate their antimicrobial and anticancer activity. The antimicrobial activity was investigated in meat-peptone broth against bacteria B. subtilis and P. aeruginosa, and the yeast C. lipolytica. The results showed that the compounds inhibited effectively the tested pathogens even after their deposition on a textile fabric. Anticancer activity was investigated against three human permanent cell lines from non-small cell lung cancer (A549), triple negative breast cancer (MDA-MB-231) and carcinoma of the uterine cervix (HeLa) in the c?=?0.01–30 μM concentration range. The results suggest that these compounds are promising for application in biomedicine as anticancer drugs in the design of new effective preparations. The antimicrobial and anticancer activity may be related to the peculiar structural and dynamical properties revealed for the Cu(II) complexes, by a computer aided analysis of the electron paramagnetic resonance (EPR) spectra. This analysis indicated the formation, at the lowest Cu(II) concentrations, of a flexible rhombic Cu-N4 coordination with the internal amino groups of the dendrimer, which transformed into a Cu2-N4 coordination already at 0.25 equiv. of Cu(II).     

Enhanced Zn(II) uptake using zinc imprinted form of novel nanobiosorbent and its application as an antimicrobial agent

We investigated the use of zinc imprinted of novel nanobiosorbent prepared from Candida rugosa to remove Zn(II) from aqueous solution. The nanobiosorbent was characterized by SEM, FTIR and XRD. Effects of various parameters including pH of the solution, adsorbent dosage, initial Zn(II) ion concentration and contact time on Zn(II) removal by the nanobiosorbents were investigated through batch process. Equilibrium data for Zn(II) removal was fitted to Langmuir isotherm model with an enhanced adsorption capacity of 275.48mg/g for zinc imprinted C. rugosa nanobiosorbent, compared to nonimprinted nanobiosorbent of 172.41 mg/g. Pseudo-second-order kinetic model was best fitted to predict the sorption kinetics for both the nanobiosorbents. AFM study revealed monolayer adsorption with thin film diffusion for Zn(II) removal. The antimicrobial activity of zinc imprinted nanobiosorbent was investigated against pathogenic yeasts viz. Candida albicans and Cryptococcus neoformans using agar well diffusion method.     

The Effect of Number of Porphyrin Polymer Units on Bandgap for ππ* Conjugation and Charge Transfer System Based on Simulation

This paper discusses the effect of number of units on bandgap for conjugation versus charge transfer system by using a conjugated polymer ([Zn])_n and an unconjugated planar push–pull one (AQ–[Zn])_n built upon 2,3-anthraquinone and bis(ethynyl)zinc(II)porphyrin. They are supported by DFT and TDDFT calculations, along with some experimental data. The position of the Q-bands is highly adjustable due to the presence of the twisted conformations in ([Zn])_n chain.     

Zinc(II) coordination complexes as membrane-active fluorescent probes and antibiotics

Molecular probes with zinc(II)-(2,2'-dipicolylamine) coordination complexes associate with oxyanions in aqueous solution and target biomembranes that contain anionic phospholipids. This study examines a new series of coordination complexes with 2,6-bis(zinc(II)-dipicolylamine)phenoxide as the molecular recognition unit. Two lipophilic analogues are observed to partition into the membranes of zwitterionic and anionic vesicles and induce the transport of phospholipids and hydrophilic anions (carboxyfluorescein). These lipophilic zinc complexes are moderately toxic to mammalian cells. A more hydrophilic analogue does not exhibit mammalian cell toxicity (LD(50) >50 microg mL(-1)), but it is highly active against the Gram-positive bacteria Staphylococcus aureus (MIC of 1 microg mL(-1)). Furthermore, it is active against clinically important S. aureus strains that are resistant to various antibiotics, including vancomycin and oxacillin. The antibiotic action is attributed to its ability to depolarize the bacterial cell membrane. The intense bacterial staining that was exhibited by a fluorescent conjugate suggests that this family of zinc coordination complexes can be used as molecular probes for the detection and imaging of bacteria.     

Metal binding properties of poly[N,N,N′,N′-tetrakis(2-hydroxypropyl)ethylenediamine methacrylate]

Summary When incorporated into a polymer hydrogel, the metal chelator, N,N,N,N-tetrakis(2-hydroxypropyl)ethylenediamine (THPED), retains its metal binding properties. The resultant poly(THPED methacrylate) homopolymer is a polybase with displacement binding constants for copper (II) and zinc(II) of-3.11 and-6.55, respectively, as compared to values for THPED of-3.83 and-7.44. The chelating capacity of the polymer for various divalent metal ions at pH 5.5 follows the order Cu>Cd>Co>Zn>Mn, while calcium and magnesium do not bind. Metal ion release curves indicate that after 30 hours, Cd(II), Co(II), Zn(II), and Mn(II) are released at a slow, steady rate, while Cu(II) is not released under experimental conditions.     

Synergistic Solvent Extraction and Transport of Zn(II) and Cu(II) across Polymer Inclusion Membranes with a Mixture of TOPO and Aliquat 336

Separation of zinc(II) and copper(II) ions from aqueous solutions by synergistic extraction and transport through polymer inclusion membranes (PIMs) has been investigated. A mixture of trioctylphosphine oxide (TOPO) and trioctymethylammonium chloride (Aliquat 336) was used as a selective extractant as well as an ion carrier in polymer membranes. The effects of hydrochloric acid concentration in the aqueous phase and extractants concentration in the organic phase on the separation process of zinc(II) and copper(II) ions have been studied. Zn(II) ions were successfully separated from Cu(II) ions in solvent extraction process using 0.025 M TOPO and 0.06 M Aliquat 336 in kerosene. Polymer inclusion membranes (PIMs) containing a mixture of TOPO and Aliquat 336 as the ion carrier have been prepared and the facilitated transport of Zn(II) and Cu(II) ions has been studied. The influence of membrane composition on the transport kinetic of Zn(II) and Cu(II) has been evaluated. Zn(II) ions were preferably transported from the aqueous solutions containing Cu(II) and above 87% of Zn(II) ions were effectively recovered from the 0.5 M HCl solution as the source phase through PIM into 0.5 M H₂SO₄ as the stripping phase.     

Hollow mesoporous silica capsules loaded with copper,silver, and zinc oxide nanoclusters for sustained antibacterial efficacy

Intensive and overuse of antibiotics during the last years has triggered a distinct rise in antibiotic resistance worldwide. In addition to the newly developed antimicrobials, there is a high demand for alternative treatment options against persistent bacterial infections. The biocidal impact of metal ions like copper (Cu²⁺), silver (Ag⁺), and zinc (Zn²⁺), also known as the oligodynamic effect has been used for ages to kill or inhibit the growth of microorganisms and to employ long-term prevention strategies against their biological antagonists. Herein, we report on the synthesis of Cu, Ag, and Zn metal and corresponding oxide nanoparticles immobilized on hollow mesoporous silica capsules (HMSCs) obtained by a hard-template assisted sol-gel synthesis followed by reduction of appropriate metal salts in the presence of HMSCs. Compartmentalization of nanosized metal and oxide clusters in Ag@HMSCs, Cu@HMSCs, and ZnO@HMSCs particles prevented their agglomeration and offered high release kinetics of metal ions between 2.0 and 3.7 mM during 24 h, as monitored by UV-vis analyses. The distribution and morphology of pristine and metal functionalized HMSCs were evaluated by transmission electron microscopy analysis revealing the successful synthesis of Ag, Cu, and ZnO nanoparticles supported on HMSCs. X-ray photoelectron spectroscopy revealed that mainly Cu(II), Ag(0), and Zn(II) species were present in the modified HMSCs. In addition to the surface attachment of preformed metal (Ag and Cu) and metal oxide (ZnO) cluster, nucleation of metal nanoparticles inside the void of HMSCs provided an internal reservoir which allowed for a time-dependent release of metal ions through slower dissolution rates leading to a long-term and sustained bacterial inhibition over several hours. The high antimicrobial efficiency of Ag@HMSCs, Cu@HMSCs, and ZnO@HMSCs particles was investigated toward both Gram-positive (Bacillus subtilis) and Gram-negative (Escherichia coli) bacteria by INT assays showing a complete growth inhibition for both bacteria types after 24 h. While Ag@HMSCs and Cu@HMSCs showed a higher susceptibility against Gram-negative bacteria, ZnO@HMSCs showed a higher susceptibility against Gram-positive bacteria. This demonstrates the promise of metal-loaded capsules as antibacterial delivery vehicles with dual-mode time-release profiles being potential alternatives for antibiotic drugs.     

Hydrothermal Syntheses,Crystal Structure and Luminescent Properties of Two New Zn(II) Coordination Polymers

Two new zinc(II) coordination polymers; namely, [Zn(BDC)(L)_0.5]_n (1) and {[Zn(BDC)(L)]·3H₂O}(2), were successfully synthesized by the assembly of Zn(II) ion, 1.2-benzene-dicarboxylate acid (H₂BDC) and 1,4-bis(2-methylimidazole-3-ium-1-yl) biphenyl (L). A change in the pH values resulted in complexes with different compositions and dimensionalities. Formed at the lower pH, 1 exhibits a three-dimensional structure with mab topology. At a higher pH, 2 shows a two-dimensional structure, which contains one-dimensional helical chains. The luminescent properties for 1 and 2 were investigated in the solid state at room temperature.     

Synthesis of the Bacteriostatic Poly(l-Lactide) by Using Zinc (II)[(acac)(L)H2O] (L = Aminoacid-Based Chelate Ligands) as an Effective ROP Initiator

The paper presents a synthesis of poly(l-lactide) with bacteriostatic properties. This polymer was obtained by ring-opening polymerization of the lactide initiated by selected low-toxic zinc complexes, Zn[(acac)(L)H₂O], where L represents N-(pyridin-4-ylmethylene) tryptophan or N-(2-pyridin-4-ylethylidene) phenylalanine. These complexes were obtained by reaction of Zn[(acac)₂ H₂O] and Schiff bases, the products of the condensation of amino acids and 4-pyridinecarboxaldehyde. The composition, structure, and geometry of the synthesized complexes were determined by NMR and FTIR spectroscopy, elemental analysis, and molecular modeling. Both complexes showed the geometry of a distorted trigonal bipyramid. The antibacterial and antifungal activities of both complexes were found to be much stronger than those of the primary Schiff bases. The present study showed a higher efficiency of polymerization when initiated by the obtained zinc complexes than when initiated by the zinc(II) acetylacetonate complex. The synthesized polylactide showed antibacterial properties, especially the product obtained by polymerization initiated by a zinc(II) complex with a ligand based on l-phenylalanine. The polylactide showed a particularly strong antimicrobial effect against Pseudomonas aeruginosa, Staphylococcus aureus, and Aspergillus brasiliensis. At the same time, this polymer does not exhibit fibroblast cytotoxicity.     

Coordination polymers, 1. Magnetic,spectral, and thermal properties of coordination polymers derived from terephthalaldehyde bis(S-benzyldithiocarbazate)

New Mn(II), Fe(II), Co(II), Ni(II), Cu(II), and Zn(II) coordination polymers of Schiff base ligand derived from terephthalaldehyde and S-benzyldithiocarbazate have been synthesized in DMF media. The coordination polymers have been characterized by their elemental analysis, magnetic susceptibility, and by electronic and infrared spectral measurements. The thermal stability of each polymer was found out by thermogravimetric analysis. The thermal stability of coordination polymers obtained from thermograms has the following order: $ {\rm Zn} \simeq {\rm Fe} > {\rm Co} > {\rm Ni} > {\rm Min} \simeq {\rm Cu}$ Mn(II), Fe(II), Co(II), and Ni(II) coordination polymers are of a six-coordinated octahedral structure while Cu(II) and Zn(II) coordination polymers are found to be four-coordinated square planar and tetrahedral structure, respectively. The ligand-field and nephelauxetic parameters have been determined from the spectra, using ligand-field theory of spin-allowed transitions which are found consistent with six-coordinate structure for Mn(II), Fe(II), Co(II), and Ni(II) coordination polymers. Elemental analyses indicates a ligand: metal ratio of 1 : 1 in all the coordination polymers and the association of water molecules with central metal atom in case of Mn(II), Fe(II), Co(II), and Ni(II) coordination polymers.     

The influence of sorbitol on zinc film deposition, zinc dissolution process and morphology of deposits obtained from alkaline bath

A novel cyanide-free zinc deposition bath was developed in which sorbitol was added at various concentrations. Voltammetric studies indicated that the reduction process is influenced thermodynamically and kinetically by the sorbitol concentration. Also, two cathodic processes were observed, one (wave) associated with the hydrogen evolution reaction (HER) on 1010 steel, the other (peak) with zinc bulk reduction, simultaneous to the HER. Furthermore, the plating-process kinetics was controlled by mass transport. The presence of sorbitol in the bath led to formation of light-grey zinc films, even during the HER, without cracks and dendrites. Plating current efficiency decreased from ∼ ∼62% to 43% on increasing the sorbitol concentration in the plating bath. In the presence of 0.1 M and/or sorbitol concentrations higher than 0.2 M, Zn electrode dissolution was inhibited. However, a small dissolution of zinc electrode was observed with 0.05 M sorbitol in alkaline solution without zincate. SEM micrographs showed that the 1010 steel substrate was fully covered by Zn film and that the sorbitol affected the morphology of zinc films, acting as a grain refiner.     

Metal ion imprinted microsphere prepared by surface molecular imprinting technique using water-in-oil-in-water emulsions

A novel metal ion imprinted polymer was prepared by the surface molecular imprinting technique. Trimethylolpropane trimethacrylate (TRIM), zinc ions, and 1,12-dodecanediol-O,O′-diphenyl phosphonic acid (DDDPA) were used as the matrix-forming monomer, imprint molecule, and functional monomer, respectively. We have prepared Zn(II)-imprinted microspheres utilizing water-in-oil-in-water emulsions, which are spherically well defined and uniform. TRIM comprises of three polymerizable groups that serve to align the recognition sites produced on the polymer surface with better template effect. We conducted diagnostic zinc adsorption tests by using the Zn(II)-imprinted and unimprinted polymers in order to make an assessment on the effectiveness of TRIM-based and divinylbenzene-based imprinted polymers. The template effect of the TRIM-based polymer was enhanced by the high rigidity of the polymer matrix compared to that of the imprinted polymer whose matrix is divinylbenzene. In addition, the adsorption equilibrium constant was evaluated on the basis of the Langmuir analysis for the adsorption data. The method to prepare metal-imprinted microspheres on the surface of polymers crosslinked by TRIM is easy, and the adsorbent produced can be readily used without subsequent grinding or sieving. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 1223–1230, 1999