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1.  Copper(II) Complexes of Amino Acids and Peptides Containing Chelating bis(imidazolyl) Residues 
Copper(II) complexes of amino acids and peptides containing the chelating bis(imidazolyl) residues have been reviewed. The results reveal that bis(imidazolyl) analogues of these biomolecules are very effective ligands for metal binding. The nitrogen donor atoms of the chelating agent are the major metal binding sites under acidic conditions. In the presence of terminal amino group the multidentate character of the ligands results in the formation of various polynuclear complexes including the ligand and the imidazole bridged dimeric species. The most intriguing feature of the coordination chemistry of these ligands is that the deprotonation of the coordinated imidazole-N(1)H groups results in the appearance of a new chelating site in the molecules. It leads to the formation of stable trinuclear complexes via negatively charged imidazolato bridges.
doi:10.1155/S1565363303000104
PMCID: PMC2267055  PMID: 18365048
2.  Gold(III) Compounds as New Family of Anticancer Drugs 
Gold(III) complexes are emerging as a new class of metal complexes with outstanding cytotoxic properties and are presently being evaluated as potential antitumor agents. This renewed interest is the result of recent studies in which various gold(III) complexes have been shown to be stable under physiological conditions and to manifest relevant antiproliferative properties against selected human tumor cell lines. The pharmacological investigation of some representative gold(III) complexes has been extended to consider their effects on the cell cycle and to reveal induction of apoptosis. Remarkably, preliminary studies suggest that the interactions in vitro of gold(Ill) complexes with calf thymus DNA are weak whereas significant binding to model proteins takes place. Our findings imply that the mechanism of action of cytotoxic gold(Ill) complexes might be substantially different from that of clinically established platinum compounds.
doi:10.1155/S1565363303000141
PMCID: PMC2267054  PMID: 18365052
3.  Sensory Perception: An Overlooked Target of Occupational Exposure to Metals 
The effect of exposure to industrial metals on sensory perception of workers has received only modest interest from the medical community to date. Nevertheless, some experimental and epidemiological data exist showing that industrial metals can affect vision, hearing and olfactory function, and a similar effect is also suggested for touch and taste. In this review the main industrial metals involved are discussed. An important limit in available knowledge is that, to date, the number of chemicals studied is relatively small. Another is that the large majority of the studies have evaluated the effect of a single chemical on a single sense. As an example, we know that mercury can impair hearing, smell, taste, touch and also vision, but we have scant idea if, in the same worker, a relation exists between impairments in different senses, or if impairments are independent. Moreover, workers are frequently exposed to different chemicals; a few available results suggest that a co-exposure may have no effect, or result in both an increase and a decrease of the effect, as observed for hearing loss, but this aspect certainly deserves much more study. As a conclusion, exposure to industrial metals can affect sensory perception, but knowledge of this effect is yet incomplete, and is largely inadequate especially for an estimation of “safe” thresholds of exposure. These data support the desirability of further good quality studies in this field.
doi:10.1155/S1565363303000165
PMCID: PMC2267053  PMID: 18365054
4.  Effect of Metal Ions on Melanin – Local Anaesthetic Drug Complexes 
The affinity of melanin biopolymers for metal ions, drugs and other organic compounds is an important factor in the etiology of toxic retinopathy, hiperpigmentation, otic lesions and irreversible extrapyramidal disorders. The aim of the presented work was to examine the interaction of local anaesthetic drugs used in ophthalmology with model DOPA-melanin in the presence of metal ions. It has been demonstrated that the analyzed drugs form complexes with melanin biopolymer. Based on the .values of association constants,, the following order of drugs affinity to melanin was found: tetracaine > procaine >> bupivacaine > lidocaine. It has also been shown that Cu2+ and Zn2+ ions administered to DOPA-melanin before complexing with drugs decrease the total amount of local anaesthetics bound to melanin. The blocking of some active centers in melanin molecules by metal ions, which potentially exist in living systems, may change the clinical therapeutic efficiency of the analyzed local anaesthetic drugs.
doi:10.1155/S1565363303000098
PMCID: PMC2267052  PMID: 18365047
5.  Impact of Potential Blockers on Ru(III) Complex Binding to Human Serum Albumin 
The effects of aspirin, vitamin B2 and warfarin as potential blockers of the ruthenium binding sites in HSA were investigated through UV/visible, circular dichroism (CD), fluorescence spectroscopy and the inductively coupled plasma-atomic emission spectroscopy ICP(AES). The studies on the interactions of several biologically relevant molecules with HSA have shown that drugs like aspirin or warfarin may strongly influence the interaction of serum protein with anticancer drugs. It can derive from the influence of the drug on protein conformation or binding close to binding site of anticancer drug. Aspirin, vitB2 and warfarin bind to IIA subdomain leading to partial blocking of the ruthenium binding site in HSA.
doi:10.1155/S1565363303000116
PMCID: PMC2267051  PMID: 18365049
6.  Synthetic and Spectroscopic Characterization of Organotin(IV) Complexes of Biologically Active Schiff Bases Derived from Sulpha Drugs 
A number of diorganotin(IV) complexes with Schiffbase have been synthesized and characterized by elemental analysis, conductance measurements, molecular weight determinations, infrared, electronic and multinuclear magnetic resonance (1H, 13C and 119Sn NMR) spectral data. The molar conductivity data shows non-electrolytic nature of complexes. The bidentate nature of the ligands is inferred from IR and NMR spectral studies. The antimicrobial activities of the ligands and their tin complexes have been screened in vitro against the organism Escherichia coli; Staphylococus aureus, Prouteus mirabilis, Bacillus thurengiensis, Penicillium co.,sogenum, Aspergillus niger and Fusarium oxysporum.
doi:10.1155/S1565363303000244
PMCID: PMC2267065  PMID: 18365062
7.  Environmental Lead Exposure in Polish Children: Blood Lead Levels, Major Sources and Principles of the Lead Poisoning Prevention 
In Poland, children are exposed to lead from the combustion of leaded gasoline and industrial processes. Since the early 1990s, emission levels have declined, and a ban on leaded petrol is anticipated in 2005. Major industrial sources are located in Silesia Province and the copper mining centre (Legnica region). Concerns about, lead exposure in children date back to the 1980s; mean blood lead levels (BILL)reported in children living near lead smelters in Silesia exceeded 20ug/dl. in the 1990s, mean BLLs were decreasing, both in urban children and those living near lead industry. Lower than the CDC action level of 101ug/dl, they were however higher than mean values in children from the other countries, where leaded gasoline had already been banned. Childhood lead poisoning prevention requires a comprehensive approach, involving different sectors. Medical prevention focuses on the early detection of exposed child by the blood lead testing and individual case management. An increasing body of evidence, indicating adverse effects even below the current “safe” level of 101ug/dl, argues for intensification of the primary prevention, which requires legal, economic and technical measures. Public health efforts should contribute to the reduction and elimination of sources of exposure in child’s environment and public education campaigns.
doi:10.1155/S1565363303000268
PMCID: PMC2267063  PMID: 18365064
8.  Complex Formation Between Ca(II), Mg(II), Al(III) Ions and Salicylglycine 
For modelling the interactions of proteins/peptides with hard metal ions the complex formation of salicylglycine (SalGly) with Ca(II), Mg(ll) and AI(III) ions was studied in aqueous solution using pHpotentiometric and UV-vis spectroscopic techniques. Al(lll) ion was found to form more stable complexes with SalGiy than Ca(ll) or Mg(ll) ions. While AI(III) ion forms various 1:1 complexes of different protonation states in the pH range 2-7, Ca(ll), Mg(ll) ions seem to interact with SalGly only in the basic pH range and form mixed hydroxo species MLH-1 at pH ~ 8. According to the UV-vis spectroscopic measurements in the species MLH-1 the carboxylate-O- atom and the phenolate-O- coordinate to the metal ions. SaIGiy is able to keep Al(lll) in solution through inner and outer sphere coordination to metastable amorphous AI(OH)3 particles. Deprotonation of the peptide amide Nil does not occur in these systems.
doi:10.1155/S1565363303000256
PMCID: PMC2267059  PMID: 18365063
9.  Communication: Synthesis of a Novel Triphenyltin(IV) Derivative of 2- Mercaptonicotinic Acid with Potent Cytotoxicity in vitro  
A novel triphenyltin(IV) derivative of 2-mercaptonicotinic acid (H2mna) of formula {[(C6H5)3Sn]2(mna).[(CH3)2CO]} (1) has been synthesized and characterized by elemental analysis and 1H, 13C-NMR, and FT-IR spectroscopic techniques. The crystal structure of complex (1) has been determined by single crystal X-ray diffraction analysis at 173(1) K. Compound (1) contains two triphenyltin moieties linked by a doubly de-protonated 2,mercaptonicotinic acid (H>2mna). It is an example of a pentacoordinated Ph3SnXY system with an axial-equatorial arrangement of the phenyl groups at Sn(1). Compound (1), exhibits potent, in vitro, cytotoxicity against sarcoma cancer cells (mesenchymal tissue) from the Wistar rat, polycyclic aromatic hydrocarbons (PAH, benzo[a]pyrene) carcinogenesis.
doi:10.1155/S1565363303000189
PMCID: PMC2267064  PMID: 18365056
10.  Synthesis, Characterization and Antitumor Activity of cis-bis(acylthioureato) platinum(II) Complexes, cis-[PtL2] [HL1=N,N-Diphenyl-N'-Benzoylthiourea or HL2=N,N-diphenyl-N'-(p-nitrobenzoyl)thiourea] 
A low-molecular weight chromium-containing fraction of the material resulting from dichromate reduction by bovine liver homogenate was investigated by NMR and ES-MS. The ES-MS spectrum showed a readily detectable peak at m/z 786.1. The same molecular weight reasonably agreed with the relatively low diffusion coefficient measured by NMR-DOSY experiments on the main species observed in the 1H NMR spectrum. At least two downfield shifted and broad paramagnetic signals were apparent in the 1H NMR spectrum. Temperature dependence of chemical shift was exploited in order to estimate the diamagnetic shift of the signals in the diamagnetic region of the spectrum. 2D TOCSY, NOESY, COSY and 1H-13C HMQC spectra revealed the presence of aromatic protons (which were assigned as His residues), Gly and some other short chain amino-acids. Combinations of the molecular masses of such components together with acetate (which is present in the solution) and chromium atoms allowed a tentative proposal of a model for the compound.
doi:10.1155/S1565363303000219
PMCID: PMC2267062  PMID: 18365059
11.  Inferences on the Nature of a Cr(V) or Cr(IV) Species Formed by Reduction of Dichromate by a Bovine Liver Homogenate: NMR and Mass-Spectrometric Studies 
A low-molecular weight chromium-containing fraction of the material resulting from dichromate reduction by bovine liver homogenate was investigated by NMR and ES-MS. The ES-MS spectrum showed a readily detectable peak at m/z = 786.1. The same molecular weight reasonably agreed with the relatively low diffusion coefficient measured by NMR-DOSY experiments on the main species observed in the 1H NMR spectrum. At least two downfield shifted and broad paramagnetic signals were apparent in the 1H NMR spectrum. Temperature dependence of chemical shift was exploited in order to estimate the diamagnetic shift of the signals in the diamagnetic region of the spectrum. 2D TOCSY, NOESY, COSY and 1H-3C HMQC spectra revealed the presence of aromatic protons (which were assigned as His residues), Gly and some other short chain amino-acids. Combinations of the molecular masses of such components together with acetate (which is present in the solution) and chromium atoms allowed a tentative proposal of a model for the compound.
doi:10.1155/S1565363303000220
PMCID: PMC2267061  PMID: 18365060
12.  Antitumor Effect of Some 3d-Metal Complexes of N-Isonicotinoyl-N'-o-Hydroxythiobenzhydrazide 
A new ligand, N-isonicotinoyl-N'-o-hydroxythiobenzhydrazide (H2Iotbh), forms complexes [Co(Iotbh)(H2O)2], [M(Iotbh)] [M Ni(II) Cu(II) and Zn(ll)] and [M(Iotbh-H)(H2O)2] [M Mn(III), Fe(III)], which were characterized by various physico-chemical techniques. DMSO solution of metal complexes was observed to inhibit the growth of tumor in vitro, whereas the ligand did not. In vivo administration of these complexes resulted in prolongation of survival of tumor-bearing mice. Tumor-bearing mice administered with the solution of metal complexes showed reversal of tumor growth associated induction of apoptosis in lymphocytes. The paper discusses the possible mechanisms and therapeutic implications of the H2lotbh and its metal complexes in tumor regression and tumor growth associated immunosuppression.
doi:10.1155/S1565363303000207
PMCID: PMC2267060  PMID: 18365058
13.  Fertility Inhibitors Macrocyclic Complexes of Bivalent Manganese: Synthetic, Spectroscopic and Medicinal Approach 
The modern physico-chemical, spectroscopic and biochemical methods have proved an important tool to elucidate the constitution of transition metal complexes. This paper presents a brief account of the synthesis, spectroscopic and medicinal aspects of tetraazamacrocyclic compounds of manganese(II). Sixteen to eighteen membered tetraamide macrocyclic ligands DTTD1 and DTTD2 have been synthesized by the condensation of 1,2-diaminoethane and 1,3-diaminopropane with phthalic acid in the presence of condensing reagents dicyclohexylcarbodiimide and 4-dimethylaminopyridine. On reduction these macrocyclic ligands give new tetraazamacrocycles TTD1 and TTD2 which form complexes with manganese (II) nitrate and manganese (II) acetate. Based on chemical analyses, molecular weight determinations, conductance measurements, magnetic moment, IR spectra, 1H NMR, 13C NMR spectra, electronic spectra, mass spectra and X-ray spectral analysis, an octahedral geometry has been assigned to the newly synthesized products. The formulation of the complexes of the type [Mn(TTDn)X2] [where, n or 2, X (NO3) or (CH3COO)] has been established on the basis of chemical composition. The possibilities of potential uses of these complexes as fungicides and bactericides, studied in vitro, are also discussed. The testicular sperm density, sperm morphology, sperm mortality, density of cauda epididymis, spermatozoa and fertility in mating trials and biochemical parameters of reproductive organs of rat have been examined and discussed.
doi:10.1155/S1565363303000190
PMCID: PMC2267058  PMID: 18365057
14.  Synthesis and Cytotoxicity of Silicon and Germanium Containing Pyridine Oxime O-Ethers 
Silicon and germanium containing pyridine aldoxime, ketoxime and amidoxime O-ethers have been prepared using phase transfer catalytic systems oxime alkyl halide solid KOH 18-crown-6 benzene and oxime alkyl halide solid K2CO3 or Cs2CO3 18-crown-6 toluene. Cytotoxic activity of silicon and germanium containing pyridine oxime O-ethers was tested in vitro on two monolayer tumor cell lines: MG- 22A (mouse hepatoma) and HT-1080 (human fibrosarcoma). O-[3-Yriethylsilylpropyl]- and O-[3-(1-methyl- 1-silacyclopentyl)propyl] oximes of pyridine aldehydes and ketones exhibit high cytotoxicity. Presence of methyl group in the pyridine ring considerably decreased activity of amidoxime O-ethers. Oxime ethers containing two elements are essentially inactive. For 2-acetylpyridine oxime ethers the activity increases in order of alkyl substituents: Et3GeCH2CH2SiMe2CH2 < Et3SiCH2CH2CH2 < (CH2)4SiCH2CH2CH2. Cytotoxicity of ketoxime O-ethers is considerably lower in comparison with aldoxime O-ethers.
doi:10.1155/S1565363303000232
PMCID: PMC2267057  PMID: 18365061
15.  Synthesis and Characterisation of Some New Aluminium Derivatives of Schiff Bases Containing N, O and S Donor Atoms and the Anti Fertility Activity of the Derivative Al[SC6H4N:C(CH3)CH2COCH3]3  
Some new compounds of aluminium having the general formula AI[SC6H4N:C(R) CH2 C(O)R’]3 where R = CH3, R' = CH3 (1); R' = CH3, R' = C6H5 (2); R = CF3, R’ = -C = CH - CH = CHS (3); R = CF3, R’ = C6H5 (4) have been synthesised by the reactions of Al(OPri)3 and the corresponding ligands in 1:3 molar ratios in benzene. Elemental and spectroscopic (IR, 1H, 13C, and 27AI NMR) characterisation of these monomeric compounds reveals monofunctional bidentate behaviour of ligand moiety and the octahedral geometry around aluminium atom. Compound (1), AI[SC6H4N:C(CH3)CH2COCH3], has been tested for its antifertility activity in male albino rats. The oral administration of this compound at the dose level 6.5 rag/rat/day reduced the weights of testes and epididymides. Significant decrease in sperm motility as well as sperm density resulted in the reduction of male fertility by 100%. Production of primary spermatocytes (preleptotene and pachytene), secondary spermatocytes and step-19 spermatids declined by 56.10%, 44.42 %, 63.35 % and 64.57 % respectively. These results indicate that the administration of compound (1) in male rats brought about an interference with spermatogenesis which ultimately caused infertility.
doi:10.1155/S1565363303000177
PMCID: PMC2267056  PMID: 18365055
16.  Iron Supplementation During Pregnancy- A Necessary or Toxic Supplement? 
The effects of a single intramuscular iron dose, 10mg, to pregnant rats on Day of pregnancy, on the outcome of pregnancy, with respect to foetal weight and mother’s immune function has been investigated. Despite significantly elevated hepatic iron stores after iron supplementation in pregnant rats this had no significant effect upon blood haemoglobin or transferrin saturation levels. However the mean weight of the foetuses at Day 20-21 was significantly lower than that of the non-supplemented pregnant rats. Iron supplements significantly increased the activity of NADPH oxidase in the maternal alveolar macrophages, the primary event in the formation of the phagolysosome to combat invading organisms. However inducible nitric oxide synthase activity was significantly reduced in these macrophages as shown by decreases in LPSinduced and LPS+IFNγ-induced NOS activation. Iron supplementation to rats of normal iron status at the commencement of pregnancy did not show any beneficial effects to either the foetus or the mother.
doi:10.1155/S156536330300013X
PMCID: PMC2267050  PMID: 18365051
17.  Resistance to Arsenic- and Antimony-Based Drugs 
Organic arsenicals were the first antimicrobial agents specifically synthesized for the treatment of infectious diseases such as syphilis and sleeping sickness. For the treatment of diseases caused by trypanosomatid parasites, organic derivatives of arsenic and the related metalloid antimony are still the drugs of choice. Arsenic trioxide, As203, has been used for a long time in traditional Chinese medicines for treatment of various diseases, and it has recently been shown to be clinically active in acute promyelocytic leukemias. Resistance to metalloid salts is found in bacteria, fungi, parasites and animals. In some organisms, resistance involves overproduction of intracellular thiols. In many cases, resistance to arsenic salts is the result of removal of the metalloid from the cytosol usually by extrusion from the cell. In eukaryotes resistance to arsenic and antimony is conferred by membrane transport proteins of the MRP family. The human MRP1, a member of this family, is frequently amplified in cancer cells and it is well-documented that MRPl-overexpressing cells poorly accumulate arsenic and antimony because of enhanced cellular effiux which depends on the presence of GSH.
doi:10.1155/S1565363303000153
PMCID: PMC2267049  PMID: 18365053
18.  Objectives and Methods of Iron Chelation Therapy 
Recent developments in the understanding of the molecular control of iron homeostasis provided novel insights into the mechanisms responsible for normal iron balance. However in chronic anemias associated with iron overload, such mechanisms are no longer sufficient to offer protection from iron toxicity, and iron chelating therapy is the only method available for preventing early death caused mainly by myocardial and hepatic damage. Today, long-term deferoxamine (DFO) therapy is an integral part of the management of thalassemia and other transfusion-dependent anemias, with a major impact on well-being and survival. However, the high cost and rigorous requirements of DFO therapy, and the significant toxicity of deferiprone underline the need for the continued development of new and improved orally effective iron chelators. Within recent years more than one thousand candidate compounds have been screened in animal models. The most outstanding of these compounds include deferiprone (L1); pyridoxal isonicotinoyl hydrazone (PIH) and; bishydroxy- phenyl thiazole. Deferiprone has been used extensively as a substitute for DFO in clinical trials involving hundreds of patients. However, L1 treatment alone fails to achieve a negative iron balance in a substantial proportion of subjects. Deferiprone is less effective than DFO and its potential hepatotoxicity is an issue of current controversy. A new orally effective iron chelator should not necessarily be regarded as one displacing the presently accepted and highly effective parenteral drug DFO. Rather, it could be employed to extend the scope of iron chelating strategies in a manner analogous with the combined use of medications in the management of other conditions such as hypertension or diabetes. Coadministration or alternating use of DFO and a suitable oral chelator may allow a decrease in dosage of both drugs and improve compliance by decreasing the demand on tedious parenteral drug administration. Combined use of DFO and L1 has already been shown to result in successful depletion of iron stores in patients previously failing to respond to single drug therapy, and to lead to improved compliance with treatment. It may also result in a “shuttle effect” between weak intracellular chelators and powerful extracellular chelators or exploit the entero-hepatic cycle to promote fecal iron excretion. All of these innovative ways of chelator usage are now awaiting evaluation in experimental models and in the clinical setting.
doi:10.1155/S1565363303000128
PMCID: PMC2267048  PMID: 18365050
19.  Interaction of Cu(II)with His-Val-Gly-Asp and of Zn(II) with His-Val-His, Two Peptides at the Active Site of Cu,Zn-Superoxide Dismutase 
His-Val-His and His-Val-Gly-Asp are two naturally occurring peptide sequences, present at the active site of Cu,Zn-superoxide dismutase (Cu,Zn-SOD). We have already studied the interaction of His-Val-His=A (copper binding site) with Cu(II) and of His-Val-Gly-Asp=B (zinc binding site) with Zn(II). As a continuation of this work and for comparison purposes we have also studied the interaction of Zn(II) with His-Val-His and Cu(II) with His-Val-Gly-Asp using both potentiometric and spectroscopic methods (visible, EPR, NMR). The stoichiometry, stability constants and solution structure of the complexes formed have been determined. Histamine type of coordination is observed for/ZnAH/2+, /ZnA/+, /ZnA2H/+ and/ZnA2/ in acidic pH while deprotonation of coordinated water molecules is observed at higher pH. /CUB/ species is characterized by the formation of a macrochelate and histamine type coordination. Its stability results in the suppression of amide deprotonation which occurs at high pH resulting in the formation of the highly distorted from square planar geometry 4N complex/CuBH-3/3.
doi:10.1155/S1565363303000086
PMCID: PMC2267047  PMID: 18365046
20.  Synthesis, Spectral and Antibacterial Studies of Binuclear Titanium(IV) / Zirconium(IV) Complexes of Piperazine Dithiosemicarbazones 
The reactions of mono(cyclopentadienyl)titanium(IV) trichloride and bis(cyclopentadienyl)titanium(IV)/ zirconium(IV) dichloride with a new class of dithiosemicarbazone, derived by condensing piperazine dithiosemicarbazide with benzaldehyde (L1H2), 2-chlorobenzaldehyde (L2H2), 4-nitrobenzaldehyde (L3H2) or salicylaldehyde (L4H4) have been studied and different types of binuclear products, viz. [{CpTiCl2}2L], [{Cp2MCl}2L], ((L=L1, L2 or L3), [{CpTiCI}2L4] and [{Cp2M}2L4] (M=Yi or Zr), have been isolated. Tentative structures are proposed for these complexes based upon elemental analyses, electrical conductance, magnetic moment and spectral (electronic, IR, 1H and 13C NMR) data. Attempts have been made to establish a correlation between antibacterial activity and the structures of the products.
doi:10.1155/S1565363303000037
PMCID: PMC2267046  PMID: 18365041
21.  One and Two Dimensional Pulsed Electron Paramagnetic Resonance Studies of in vivo Vanadyl Coordination in Rat Kidney 
The biological fate of a chelated vanadium source is investigated by/n vivo spectroscopic methods to elucidate the chemical form in which the metal ion is accumulated. A pulsed electron paramagnetic resonance study of vanadyl ions in kidney tissue, taken from rats previously treated with bis(ethylmaltolato)oxovanadium(IV) (BEOV) in drinking water, is presented. A combined approach using stimulated echo (3-pulse) electron spin echo envelope modulation (ESEEM) and the two dimensional 4-pulse hyperfine sublevel correlation (HYSCORE) spectroscopies has shown that at least some of the VO2+ ions are involved in the coordination with nitrogen-containing ligands. From the experimental spectra, a 4N hyperfine coupling constant of 4.9 MHz and a quadrupole coupling constant of 0.6 + 0.04 MHz were determined, consistent with amine coordination of the vanadyl ions. Study of VO-histidine model complexes allowed for a determination of the percentage of nitrogen-coordinated VO2+ ions in the tissue sample that is found nitrogen-coordinated. By taking into account the bidentate nature of histidine coordination to VO2+ ions, a more accurate determination of this value is reported. The biological fate of chelated versus free (i.e. salts) vanadyl ion sources has been deduced by comparison to earlier reports. In contrast to its superior pharmacological efficacy over VOSO4, BEOV shares a remarkably similar biological fate after uptake into kidney tissue.
doi:10.1155/S1565363303000062
PMCID: PMC2267045  PMID: 18365044
22.  The Effect of Fused 12-Membered Nickel Metallacrowns on DNA and their Antibacterial Activity 
The synthesis, characterization and the biological study of a series of Ni(ll)2(carboxylato)2 [12- MCNi(II)N(shi)2(pko)2-4][12-MCNi(ii)N(sh03(pko)-4] (CH3OH)3(H3O) fused 12-membered metallacrowns with 10 metal ions and commercial available herbicides or anti-inflammatory drugs as carboxylato ligands are reported. All the compounds have a mixed ligand composition with salicylhydroxamic acid and di-2-pyridylketonoxime as chelate agents. The compounds construct metallacrown cores {[12-MCNi(n)N(sj02(pko)2-4][12-MCNi(ll)N(shO3(pko)-4]}2+ following the pattern [-Ni-O-N-]4. The neutral decanuclear [Ni(II)(A)]2[12-MCNi(II)N(shi)2(pko)2-4][12-MCNi(II)N(pko)3(pko)-4] fused metallacrown, consists of two [12-MCM(ox)N(ligand)-4] units the {Ni(ll)(A)[12-MCNi(II)N(shi)2(pko)2-4]} and {Ni(II)(A)[12-MCNi(II)N(shi)3(pko)-4]} with 1+ and 1- charge, respectively. Each metallacrown unit has four ring Ni(II) ions and one additional encapsulated Ni(II) ion in planar arrangement. The anionic unit is bonded with cationic one creating binuclear moieties. The herbicide or antiiflammatory carboxylato ligands are bridging the central octahedral nickel atom with a ring metal ion in a bindetate fashion. The effect on DNA and their antibacterial activity was examined. The changes in the mobility can be attributed to the altered structures of the pDNA treated with Ni(II) complexes. Evaluating the data of the antibacterial activity of the compounds tested, we can conclude that nickel complexes present strong antibacterial activity.
doi:10.1155/S1565363303000074
PMCID: PMC2267044  PMID: 18365045
23.  Unusual Non-Occupational Exposure to Metals 
Exposure to metals at workplaces is well known and in many cases occupational studies led to an adoption of limit values. For airborne concentrations of substances as metals refer to the “Maximaleo Arbeitsplatz-Konzentration” (MAK) in Germany or the “Threshold Limit Value” (TLV) in USA. Biological monitoring consists of an assessment of overall exposure to chemicals at the workplace and in the environment. The “Biologischer Arbeitsstoff Toleranzwert” (BAT) in Germany and the “Biological Exposure Index” in the USA serve as reference values. Besides these occupational limit values, reference values exist in Germany for the background exposure of the non occupationally exposed general population. In some cases the reference values are exceeded without any occupational exposure. Several cases of unusual environmental exposure to cobalt, mercury and manganese are reported. In such cases, it is often difficult to evaluate the measured concentration. In Germany, therefore, the “Human-Biomonitoring-Werte” (HBMValues) have been adopted in order to evaluate such high background exposures. The HBM-concept is presented. Environmental exposure to metals is usual within some limits. Reference values are helpful for an assessment. Unusual exposure occurs and the physician should be alert to symptoms of poisoning.
doi:10.1155/S1565363303000049
PMCID: PMC2267043  PMID: 18365042
24.  Comparison of Crystal Field Dependent and Independent Methods to Analyse Lanthanide Induced NMR Shifts in Axially Symmetric Complexes. Part II: Systems with a C4 Symmetry Axis 
Analysis of the LIS data for several series of Ln3+ complexes of C4 symmetry in terms of structural changes, crystal-field effects and/or variation of hyperfine constants along the lanthanide series was undertaken using a combination of the two-nuclei and three-nuclei techniques together with the classical onenucleus technique. Isostructurality of whole series of complexes, with changes of the Fi, and B02 parameters, was clearly defined for the complexes of L by the combination of the two first methods. Small changes, involving the three Fi, Gi and B02 parameters, are observed for the series of complexes of L-L4, using the three data plotting methods. Some of the plots according to the two- and three-nuclei methods are accidentally linear, without necessarily implying isostructurality of the complexes, as they involve parameters, which may be insensitive to any small structural changes occurring in these systems. These parameter variations could result from a magnification, by the present graphical analysis, of the breaks expected from the gradual structural changes along the series due to the lanthanide contraction. The α and β parameters of the three-nuclei method are not diagnostic of the type of structures the complexes have in solution, due to their very indirect dependence on the geometric factors.
doi:10.1155/S1565363303000013
PMCID: PMC2267042  PMID: 18365039
25.  Degradation of Single Stranded Nucleic Acids by the Chemical Nuclease Activity of the Metal Complex [Cu(phen)(nal)]+  
The chemical design of metal complexes of the type [Cu(phen)(antib)]+ (where antib is a quinolone or a fluoroquinolone) has been carried out in an approach to better understand how the coordination of their components affect the activity of quinolones. The ability of [Cu(phen)(nal)]+ to interact with DNA in vivo and its capacity to promote the degradation of plasmid and chromosomal DNA, under reductive conditions has been previously reported. However whether this compound utilizes other intracellular targets to promote bacterial killing was a question that deserved to be answered. In this paper, the studies of the chemical nuclease properties encoded by the metal complex [Cu(phen)(nal)]+ were extended by using different types of single chain nucleic acids, i.e, ribosomal and tumor mosaic virus RNAs as well as poly-dA-dT. Our results showed that degradation of the nucleic acids occurred only under reductive conditions. Although MPA and [3-mercaptoethanol were the chemical reducers that best assisted the nuclease reaction, other biological compounds such as citric and succinic acid also were shown to act like reducers in that reaction. All.hough the nuclease activity of [Cu(phen)(nal)]+ was comparable to that exhibited by bis copper phenanthroline [Cu(phen)z]2+our results showed that none of the individual components of [Cu(phen)(nal)]+ was able to promote the degradation of either the RNAs or poly(dA-dT). These results strongly support the hypothesis that the metal complex [Cu(phen)(nal)] uses not only DNA but also RNA as targets to promote bacterial killing.
doi:10.1155/S1565363303000025
PMCID: PMC2267041  PMID: 18365040

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