Two ternary Zn(II) complexes, with 1,10-phenanthroline (phen) as the main ligand and a carboxylate-containing ligand [dipicolinate (dipico) or L-threoninate (L-Thr)] as the subsidiary ligand, were prepared and characterized by elemental analysis, Fourier transform IR, UV, and fluorescence spectroscopy, X-ray diffraction, molar conductivity, and electrospray ionization mass spectrometry. X-ray structure analysis shows that both [Zn(phen)(dipico)(H(2)O)]·H(2)O (1) and [Zn(phen)(L-Thr)(H(2)O)Cl]·2H(2)O (2) have octahedral geometry about the Zn(II) atom. Both complexes can inhibit topoisomerase I, and have better anticancer activity than cisplatin against nasopharyngeal cancer cell lines, HK1 and HONE-1, with concentrations causing 50 % inhibition of cell proliferation (IC(50)) in the low micromolar range. Complex 2 has the highest therapeutic index for HK1. Both Zn(II) complexes can induce cell death by apoptosis. Changing the subsidiary ligand in the Zn(II) complexes affects the UV-fluorescence spectral properties of the coordinated phen ligand, the binding affinity for some DNA sequences, nucleobase sequence-selective binding, the phase at which cell cycle progression was arrested for treated cancer cells, and their therapeutic index.
The aim of this study is to investigate the ability of zinc carnosine to protect the human lymphoblastoid (WIL2-NS) cell line from hydrogen peroxide-induced DNA damage. Cells were cultured with medium containing zinc carnosine at the concentrations of 0.4, 4, 16 and 32 μM for 9 days prior to treatment with 30 μM of hydrogen peroxide (30 min). Zinc carnosine at the concentration 16 μM was optimal in protecting cells from hydrogen peroxide-induced cytotoxicity and gave the lowest percentage of apoptotic and necrotic cells. Results showed that zinc carnosine was able to induce glutathione production and protect cells from hydrogen peroxide-induced oxidative stress at all concentration and the highest protection was observed at 32-μM zinc carnosine culture. Cytokinesis-block micronucleus cytome assay showed that cells cultured with 4-32 μM of zinc carnosine showed significant reduction in micronuclei formation, nucleoplasmic bridges and nuclear bud frequencies (p zinc carnosines possess antioxidant properties and are able to reduce hydrogen peroxide-induced DNA damage in vitro independent of poly(ADP-ribose) polymerase. Further studies are warranted to understand the mechanism of protection of zinc carnosine against hydrogen peroxide-induced damage.
Layered hydroxide nanoparticles are generally biocompatible, and less toxic than most inorganic nanoparticles, making them an acceptable alternative drug delivery system. Due to growing concern over animal welfare and the expense of in vivo experiments both the public and the government are interested to find alternatives to animal testing. The toxicity potential of zinc aluminum layered hydroxide (ZAL) nanocomposite containing anti-Parkinsonian agent may be determined using a PC 12 cell model. ZAL nanocomposite demonstrated a decreased cytotoxic effect when compared to levodopa on PC12 cells with more than 80% cell viability at 100 µg/mL compared to less than 20% cell viability in a direct levodopa exposure. Neither levodopa-loaded nanocomposite nor the un-intercalated nanocomposite disturbed the cytoskeletal structure of the neurogenic cells at their IC50 concentration. Levodopa metabolite (HVA) released from the nanocomposite demonstrated the slow sustained and controlled release character of layered hydroxide nanoparticles unlike the burst uptake and release system shown with pure levodopa treatment.
A new inhibitive heavy metals determination method using trypsin has been developed. The enzyme was assayed using the casein-Coomassie-dye-binding method. In the absence of inhibitors, casein was hydrolysed to completion and the Coomassie-dye was unable to stain the protein and the solution became brown. In the presence of metals, the hydrolysis of casein was inhibited and the solution remained blue. The bioassay was able to detect zinc and mercury with IC50 (concentration causing 50% inhibition) values of 5.78 and 16.38 mg l(-1) respectively. The limits of detection (LOD), for zinc and mercury were 0.06 mg l(-1) (0.05-0.07, 95% confidence interval) and 1.06 mg l(-1) (1.017-1.102, 95% confidence interval), respectively. The limits of quantitation (LOQ) for zinc and mercury were 0.61 mg l(-1) (0.51-0.74 at a 95% confidence interval) and 1.35 mg l(-1) (1.29-1.40 at a 95% confidence interval), respectively. The IC50 value for zinc was much higher than the IC50 values for papain and Rainbow trout, but was within the range of Daphnia magna and Microtox. The IC50 value for zinc was only lower than those for immobilized urease. Other toxic heavy metals, such as lead, silver arsenic, copper and cadmium, did not inhibit the enzyme at 20 mg l(-1). Using this assay we managed to detect elevated zinc concentrations in several environmental samples. Pesticides, such as carbaryl, flucythrinate, metolachlor glyphosate, diuron, diazinon, endosulfan sulphate, atrazine, coumaphos, imidacloprid, dicamba and paraquat, showed no effect on the activity of trypsin relative to control (One-way ANOVA, F(12,26)= 0.3527, p> 0.05). Of the 17 xenobiotics tested, only (sodium dodecyl sulphate) SDS gave positive interference with 150% activity higher than that of the control at 0.25% (v/v).
A series of Zn(II)-Schiff bases I, II and III complexes were synthesized by reaction of o-phenylenediamine with 3-methylsalicylaldehyde, 4-methylsalicylaldehyde and 5-methylsalicylaldehyde. These complexes were characterized using FT-IR, UV-Vis, Diffuse reflectance UV-Vis, elemental analysis and conductivity. Complex III was characterized by XRD single crystal, which crystallizes in the triclinic system, space group P-1, with lattice parameters a=9.5444(2) Å, b=11.9407(2) Å, c=21.1732(3) Å, V=2390.24(7) Å(3), D ( c )=1.408 Mg m(-3), Z=4, F(000)=1050, GOF=0.981, R1=0.0502, wR2=0.1205. Luminescence property of these complexes was investigated in DMF solution and in the solid state. Computational study of the electronic properties of complex III showed good agreement with the experimental data.
The cobalt(II), copper(II) and zinc(II) complexes of 1,10-phenanthroline (phen) and maltol (mal) (complexes 1, 2, 3 respectively) were prepared from their respective metal(II) chlorides and were characterized by FT-IR, elemental analysis, UV spectroscopy, molar conductivity, p-nitrosodimethylaniline assay and mass spectrometry. The X-ray structure of a single crystal of the zinc(II) analogue reveals a square pyramidal structure with distinctly shorter apical chloride bond. All complexes were evaluated for their anticancer property on breast cancer cell lines MCF-7 and MDA-MB-231, and normal cell line MCF-10A, using (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide assay and morphological studies. Complex 2 was most potent for 24, 48 and 72 h treatment of cancer cells but it was not selective towards cancer over normal cells. The mechanistic studies of the cobalt(II) complex 1 involved apoptosis assay, cell cycle analysis, dichloro-dihydro-fluorescein diacetate assay, intracellular reactive oxygen species assay and proteasome inhibition assay. Complex 1 induced low apoptosis, generated low level of ROS and did not inhibit proteasome in normal cells. The study of the DNA binding and nucleolytic properties of complexes 1-3 in the absence or presence of H2O2 or sodium ascorbate revealed that only complex 1 was not nucleolytic.
Two bidentate NS ligands were synthesized by the condensation reaction of S-2-methylbenzyldithiocarbazate (S2MBDTC) with 2-methoxybenzaldehyde (2MB) and 3-methoxybenzaldehyde (3MB). The ligands were reacted separately with acetates of Cu(II), Ni(II) and Zn(II) yielding 1:2 (metal:ligand) complexes. The metal complexes formed were expected to have a general formula of [M(NS)2] where M = Cu2+, Ni2+, and Zn2+. These compounds were characterized by elemental analysis, molar conductivity, magnetic susceptibility and various spectroscopic techniques. The magnetic susceptibility measurements and spectral results supported the predicted coordination geometry in which the Schiff bases behaved as bidentate NS donor ligands coordinating via the azomethine nitrogen and thiolate sulfur. The molecular structures of the isomeric S2M2MBH (1) and S2M3MBH (2) were established by X-ray crystallography to have very similar l-shaped structures. The Schiff bases and their metal complexes were evaluated for their biological activities against estrogen receptor-positive (MCF-7) and estrogen receptor-negative (MDA-MB-231) breast cancer cell lines. Only the Cu(II) complexes showed marked cytotoxicity against the cancer cell lines. Both Schiff bases and other metal complexes were found to be inactive. In concordance with the cytotoxicity studies, the DNA binding studies indicated that Cu(II) complexes have a strong DNA binding affinity.
Fatty acid methyl ester was produced from used vegetable cooking oil using Mg(1-)(x) Zn(1+)(x)O(2) solid catalyst and the performance monitored in terms of ester content obtained. Used vegetable cooking oil was employed to reduce operation cost of biodiesel. The significant operating parameters which affect the overall yield of the process were studied. The highest ester content, 80%, was achieved with the catalyst during 4h 15 min reaction at 188°C with methanol to oil ratio of 9:1 and catalyst loading of 2.55 wt% oil. Also, transesterification of virgin oil gave higher yield with the heterogeneous catalyst and showed high selectivity towards ester production. The used vegetable cooking oil did not require any rigorous pretreatment. Catalyst stability was examined and there was no leaching of the active components, and its performance was as good at the fourth as at the first cycle.
The synthesis of fatty acid methyl esters (FAME) as a substitute to petroleum diesel was investigated in this study from crude jatropha oil (CJO), a non-edible, low-cost alternative feedstock, using aluminium modified heterogeneous basic oxide (Mg-Zn) catalyst. The transesterification reaction with methanol to methyl esters yielded 94% in 6h with methanol-oil ratio of 11:1, catalyst loading of 8.68 wt.% at 182°C and the properties of CJO fuel produced were determine and found to be comparable to the standards according to ASTM. In the range of experimental parameters investigated, it showed that the catalyst is selective to production of methyl esters from oil with high free fatty acid (FFA) and water content of 7.23% and 3.28%, respectively in a single stage process. Thus, jatropha oil is a promising feedstock for methyl ester production and large scale cultivation will help to reduce the product cost.
Layered organic-inorganic hybrid nanocomposite material was synthesised using 4-chlorophenoxyacetate (4CPA) as guest anion intercalated into the Zn-Al layered double hydroxide inorganic host by direct co-precipitation method at pH = 7.5 and Zn to Al molar ratio of 4. Both PXRD and FTIR results confirmed that the 4CPA was successfully intercalated into the Zn-AI-LDH interlayer. As a result, a well-ordered nanolayered organic-inorganic hybrid nanocomposite, with the expansion of the basal spacing from 8.9 angstroms in the layered double hydroxide to 20.1 angstroms in the resulting nanocomposite was observed. The FTIR spectrum of the nanocomposite (ZAC) showed that it composed spectral features of Zn-AI-LDH (ZAL) and 4CPA. The nanocomposites synthesized in this work are of mesoporous-type containing 39.8% (w/w) of 4CPA with mole fraction of Al3+ in the inorganic brucite-like layers (xAI) of 0.224. The release studies showed a rapid release of the 4CPA for the first 600 min, and more sustained thereafter. The total amount of 4CPA released from the nanocomposite interlayer into the aqueous solution were 21%, 66%, and 72% in 0.0001, 0.00025, and 0.0005 M sodium carbonate, respectively. In distilled water, about 75, 35, and 57% of 4CPA could be released in 1000 min, when the pH of the release media was set at 3, 6.25, and 12, respectively. In comparison with a structurally similar organic moiety with one more chlorine atom at the 2-position of the aromatic ring, namely 2,4-dichlorophenoxyacetate (24D), the 4CPA showed a slower release rate. The slightly bulkier organic moiety of 24D together with the presence of chlorine atom at the 2-position presumably had contributed to its higher release rate, and it seems that these factors may be exploited for tuning the release rate of intercalated guest anions with similar properties. This study suggests that layered double hydroxide can be used as a carrier for an active agent and the chemical structure of the intercalated moiety can be used to tune the desired release kinetics of the beneficial agent.
A drug-inorganic nanostructured material involving pharmaceutically active compound lawsone intercalated Zn-Al layered double hydroxides (Law-LDHs) with Zn/AI = 4 has been assembled by co-precipitation and ion exchange methods. Powder X-ray diffraction (XRD) and Fourier transform infrared spectra (FTIR) analysis indicate a successful intercalation of lawsone between the layers of layered double hydroxides. It suggests that layered double hydroxides may have application as the basis of a drug delivery system.
We report significant enhancements in Er(3+) luminescence as well as in Raman intensity in silver nanoparticles embedded zinc-tellurite glass. Surface enhanced Raman scattering effect is highlighted for the first time in tellurite glass containing silver NPs resulting in an enhanced Raman signal (~10 times). SAED manifest the growth of Ag(0) nanoparticles along the (111) and (200) crystallographic planes having average diameter in the range 14-36 nm. Surface plasmon resonance bands are observed in the range 484-551 nm. Furthermore, four prominent photoluminescence bands undergo significant enhancements up to 3 times. The enhancement is majorly attributed to the local field effect of silver NPs.
In our previous paper, we reported that a dimeric Zn(2+) complex with a 2,2'-bipyridyl linker (Zn2L(1)), cyanuric acid (CA), and a Cu(2+) ion automatically assemble in aqueous solution to form 4:4:4 complex 3, which selectively catalyzes the hydrolysis of mono(4-nitrophenyl)phosphate (MNP) at neutral pH. Herein, we report that the use of barbital (Bar) instead of CA for the self-assembly with Zn2L(1) and Cu(2+) induces 2:2:2 complexation of these components, and not the 4:4:4 complex, to form supramolecular complex 6 a, the structure and equilibrium characteristics of which were studied by analytical and physical measurements. The finding show that 6 a also accelerates the hydrolysis of MNP, similarly to 3. Moreover, inspired by the crystal structure of 6 a, we prepared barbital units that contain functional groups on their side chains in an attempt to produce supramolecular phosphatases that possess functional groups near the Cu2(μ-OH)2 catalytic core so as to mimic the catalytic center of alkaline phosphatase (AP).
Klebsiella pneumoniae is a Gram-negative, cylindrical rod shaped opportunistic pathogen that is found in the environment as well as existing as a normal flora in mammalian mucosal surfaces such as the mouth, skin, and intestines. Clinically it is the most important member of the family of Enterobacteriaceae that causes neonatal sepsis and nosocomial infections. In this work, a combination of protein sequence analysis, structural modeling and molecular docking simulation approaches were employed to provide an understanding of the possible functions and characteristics of a hypothetical protein (KPN_02809) from K. pneumoniae MGH 78578. The computational analyses showed that this protein was a metalloprotease with zinc binding motif, HEXXH. To verify this result, a ypfJ gene which encodes for this hypothetical protein was cloned from K. pneumoniae MGH 78578 and the protein was overexpressed in Escherichia coli BL21 (DE3). The purified protein was about 32 kDa and showed maximum protease activity at 30 °C and pH 8.0. The enzyme activity was inhibited by metalloprotease inhibitors such as EDTA, 1,10-phenanthroline and reducing agent, 1,4-dithiothreitol (DTT). Each molecule of KPN_02809 protein was also shown to bind one zinc ion. Hence, for the first time, we experimentally confirmed that KPN_02809 is an active enzyme with zinc metalloprotease activity.
Cu2ZnSnS4 (CZTS) ink was synthesized from metal chloride precursors, sulfur, and oleylamine (OLA), as a ligand by a simple and low-cost hot-injection method. Thin films of CZTS were then prepared by spin coating, followed by thermal annealing. The effects of the fabrication parameters, such as ink concentration, spinning rate, and thermal treatment temperatures on the morphology and structural, optical, and electrical properties of the films were investigated. As expected, very thin films, for which the level of transmittance and band-gap values increase, can be obtained either by reducing the concentration of the inks or by increasing the rate of spinning. Moreover, the thermal treatment affects the phase formation and crystallinity of the film, as well as the electrical conductivity, which decreases at a higher temperature.
Hydrotalcite-like inorganic layers of Zn-Al, a host containing an organic moiety, 2,4-dichlorophenoxy-acetate, as a guest, was prepared by the spontaneous self-assembly method from an aqueous solution for the formation of a new layered organic-inorganic hybrid nanocomposite material. In this synthesis, the host- and guest-forming species were simultaneously included in the mother liquor, aged, and separated. Various Zn/Al ratios (R = 2, 3, and 4), concentrations of 2,4-dichlorophenoxyacetic acid (0.03-0.1 M), and pH (7 and 10) were studied to optimize the formation of the layered nancomposite. It was found that the optimum conditions for the formation of the nanocomposite were R = 4, pH 7, and concentration of 2,4-dichlorophenoxyacetic acid = 0.08 M. X-ray diffraction shows that this sample affords a nanolayered structure with a basal spacing of 24.6 A.
MCR (mobile colistin resistance) enzymes catalyse phosphoethanolamine (PEA) addition to bacterial lipid A, threatening the "last-resort" antibiotic colistin. Molecular dynamics and density functional theory simulations indicate that monozinc MCR supports PEA transfer to the Thr285 acceptor, positioning MCR as a mono- rather than multinuclear member of the alkaline phosphatase superfamily.
Zeolites P in sodium (NaP) and potassium (KP) forms were used as adsorbents for the removal of calcium (Ca2+) and zinc (Zn2+) cations from aqueous solutions. Zeolite KP was prepared by ion exchange of K+ with Na+ which neutralizes the negative charge of the zeolite P framework structure. The ion exchange capacity of K+ on zeolite NaP was determined through the Freundlich isotherm equilibrium study. Characterization of zeolite KP was determined using infrared spectroscopy and X-ray diffraction (XRD) techniques. From the characterization, the structure of zeolite KP was found to remain stable after the ion exchange process. Zeolites KP and NaP were used for the removal of Ca and Zn from solution. The amount of Ca2+ and Zn2+ in aqueous solution before and after the adsorption by zeolites was analysed using the flame atomic absorption spectroscopy method. The removal of Ca2+ and Zn2+ followed the Freundlich isotherm rather than the Langmuir isotherm model. This result also revealed that zeolite KP adsorbs Ca2+ and Zn2+ more than zeolite NaP and proved that modification of zeolite NaP with potassium leads to an increase in the adsorption efficiency of the zeolite. Therefore, the zeolites NaP and KP can be used for water softening (Ca removal) and reducing water pollution/toxicity (Zn removal).
Adhesive bond strength studies for the tray adhesive of an addition vinyl polysiloxane (President) impression material were conducted with an acrylic resin, chromium-plated brass, and plastic trays. Tensile and shear stress studies were performed on the Instron Universal testing machine. Acrylic resin specimens roughened with 80-grit silicon carbide paper exhibited appreciably higher bond strengths compared with different types of tray material and methods of surface preparation.