Modification on Synthesis of Mixed Ligand Chelates by Using Di- and Trivalent Transition Metal Ions with Schiff Base as Primary Ligand

New mixed ligand chelates synthesized from di-and trivalent metal ions (Cr, Co, Ni, and Cu ions) and Schiff base (L1) resulted from the condensation of 4-dimethylaminobenzaldehyde with 2-aminophenol as primary ligand, whereas 2-nitroaniline (L2) represents the secondary ligand in a molar ratio of M:L1:L2 [1:1:1]. The synthesized Schiff base and chelates have been characterized by using several tools, such as, elemental analysis, molar conductivity, magnetic moment measurements, infrared and electronic spectra. The mass spectra of the ligands and Ni(II) chelate were used to justify the process of modification, as well as, the electron paramagnetic resonance spectrum which was carried out for Cu(II) chelate all in order to elucidate the chemical and geometrical structure of the chelates. On the basis of the obtained data, the geometry of the products was proposed for all the chelates.

Synthesis and Characterization of Some Transition Metal Chelates of 5-(1-Hydroxy-6-Naphthylazo-3-Sodium Sulphonate) Thiobarbituric (L_1) and Barbituric (L_2) Acids

Some transition metal chelates of two ligands L1 and L2 were prepared and characterized by elemental analysis. The IR and 1H NMR spectra of several chelates of two ligands L1 and L2 showed the involvement of the azo group in chelation with the transition metaI ions, in most of the studied chelates, and that the two ligands L1 and L2 showed the involvement of the azo group in chelation with the transition metal ions, in most of the studied chelates, and that the two ligands L1 and L2 were coordinated either in the enol or the keto form. IR spetra also showed that Fe(III)-, Ni(II)-, Mn(II)-, VO(II)-L1 and Cu(II)-L2 chelates behaved in a bidentate manner, in contrast with the two (1:1) M:L cobalt chelates with the two ligands are tridentate.TG analysis indicated the presence of three to twelve water molecules of hydration eliminated on heating up to 150℃ and one or two coordinated water molecules removed at 150~180℃.The octahedral structure is proposed fOr all the chelates, except Cu(II)-L2 and Ni(II)-L1 chelates which have square planar geometry, based on their electronic spectra

THE SYNTHESIS AND DIOXYGEN-AFFINITY OF SOME SCHIFF-BASE COBALT(Ⅱ)CHELATES COORDINATIVELY BOUND ON POLY(4-VINYLPYRIDINE-CO-STYRENE)

Some Schiff-base cobalt(Ⅱ)chelates like ethylenebis[(2-hydroxy-3- methoxy-5-methylphenyl)methylideneiminato]Cobalt(Ⅱ)were coordioatively anchored onto poly(4-vinylpyridine-co-styrene)in diglyme solution and the dioxygen-affinity of the resulting polymeric complexes were measured in situ.

Synthesis of Cobalt Chromite Nanoparticles by Thermolysis of Mixed Cr^(3+) and Co^(2+) Chelates of 2-Mercaptopyridin N-Oxide

Pure greenish-blue cobalt chromite(Co Cr/_2O_4) nanoparticles with narrow particle range of 4.1±1.9nm and surface area of 78.2 m2·g-1were synthesized through mixed chelates thermolysis of corresponding metals using 2-Mercaptopyridine N-oxide sodium salt as chelating agent. During the thermolysis procedure,high amount of gases were emitted that led to the formation of nanoparticles with high surface area. The product was characterized by TGA, DTG, XRD, TEM, SEM, LLS, BET and chemical analysis. Design of experiments was performed to fulfill the two levels L_4 Taguchi design. It was found that the temperature and time of thermolysis process have significant effect on the particle size reduction. The Oxidation of trichloroethylene was carried out over Co Cr_2O_4 nanocrystallite. Catalytic activity analysis revealed that the synthesis Co Cr_2O_4 possesses high catalytic activity for this process.

Kinetic Studies on Forming Iso-nuclear β-type Chelates of Rare Earths with p-Sulphoaminobromophosphonazo

The kinetic behavior of forming the iso-nuclear β-type chelates of rare earth ions (RE~3+) with p-sulphoaminobromophosphonazo (BPA-pSN) in ClCH2COOH-CH3COONa buffer solutions were studied by a spectrophotometric method.

pH-metric and thermodynamic studies of rare earth metal chelates

Proton ligand stability constants of hydroxybenzoic acid containing nitro group （2-Hydroxy-4-nitrobenzoic acid and 3-Hydroxy-4- nitrobenzoic acid） were determined through lrving-Rossoti pH titration technique. The stability constants of rare earth metal chelates containing 2-Hydroxy-4-nitrobenzoic acid and 3-Hydroxy-4-nitrobenzoic acid as ligands were studied in aqueous medium at different ionic strength （p=0.01, 0.05 and 0.1 mol/L） and temperatures （298, 308 and 318± 0.1 K）. The values of stability constant were evaluated through different computational methods like successive approximation, least square treatment, correction term method, and convergence method. The observed value of thermodynamic parameters （△G°, △H° and △S°） favors the complex formation between metal and ligands. The order of stabifity constant was found to be Pr（III）〈Nd（III）〈Sm（III）〈Tb（III）〈Ho（III）〈Er（III） as reported by Stagg and Powell.

PREPARATION AND CHARACTERIZATION OF BINUCLEAR μ-PHENOLATOCOPPER(II)CHELATES.

Two new water-soluble binuclear copper(II)chelates derived from the condensation of 2,6-diformyl-4-methylphenol with glycylglycine were characterized with spectral. magnetic and electrochemical techniques.

Mechanism of Hetero-nuclear β-type Chelates Formed by Rare Earths with p-sulphoaminobromophosphonazo

The reaction behavior of forming the hetero-nuclear β-type chelates of rare earth ions (RE 3+) with p-sulphoaminobromophosphonazo(BPA-pSN) in ClCH_2COOH-CH_3COONa buffer solutions were studied by a spectrophotometric method. The interaction of RE 3+ with BPA-pSN, which can forms hetero-nuclear β-type chelates having composition ratio of RE_1 (light rare earth):BPA-pSN:RE_2(heavy rare earth ion)=1∶3∶1, is a first-order reaction. Meanwhile, BPA-pSN can only forms homo-nuclear β-type chelates with heavy rare earth ions, having a composition ratio of RE∶BPA-pSN=1∶2 and being a second-order reaction. The rate constants of forming homo-and hetero-nuclear β-type chelates were obtained and the mechanism of forming hetero-nuclear β-type chelates was proposed.

Pre-Chelates, Post-Adducts and Implexes: A perspective proposal for the future of medicinal chemistry

The title of this little assay coins three new words: Pre-Chelates, Post-Adducts and Implexes. These, very daring new excursions into the scientific English language, come from the developments of Quelamycin and Sodium L-Thioproline, through our different group studies arriving to cancer reversal by a dual strategy. It is enough to read all our published materials, cites and related papers, dealing more or less with the chemistry and possible mechanism of action of these compounds, to gather somewhat what signified our monomeric-triferric-doxorubicine, as possibly one of the first Pre-Chelates and our Sodium L-Thioproline, probably as one of the first Post-Adducts. Both molecules come to the human patients with cancer blood from the exterior. After this indication, it will be proposed a seed concept of a new type of molecules, the “Implexes” in which the metals will be embraced instead of being linked.

Progress on Study of Luminescence of Rare Earth Organic Chelates

Based on the investigation of the luminescence of a series of rare earth organic chelates, some relationships between luminescence and the structure of the chelates were proposed: the intensity of sensitized luminescence of central lanthanide ions(Ln 3+ ) in a rare earth organic chelate depends on (1)the suitability of the energy gap between the excited triplet energy level of the ligands and the lowest excited energy level of Ln 3+ ions; (2)the rigidity and planarity of the structure of the chelate molecule; (3)the existence of a suitable secondary ligand which may increase rigidity and the stability of the chelate molecule; and (4) the existence of a suitable π conjugated system in the chelate molecule. According to the above relationships, 25 novel organic ligands were designed and synthesized, and their lanthanide chelates were prepared. Investigation of the photoluminescence for the new chelates shows that some of the chelates are strongly luminescent, and are applied to fluoroimmunoassay for determination of human immunoglobulin(IgG), to preparation of fluorescent plastics, and to determination of growth hormone for plants. Two novel spectroscopy probe techniques for structure of coordination compounds and biological molecules were proposed and developed based on vibronic spectroscopy of Tb 3+ complexes and fluorescence of Ce 3+ .

Effect of Feeding a Combination of Zinc, Manganese and Copper Methionine Chelates of Early Lactation High Producing Dairy Cow

The objective of the study was to compare the effect of feeding mixed chelated minerals (Mn, Cu and Zn) methionine on dairy cow productive performance and milk yield and its components. The trial was conducted with dairy cows across various stage of lactation. The experimental treatments include chelated minerals (15 mg Zn as Zn Met, 20 mg Mn as Mn Met, 10 mg Cu as Cu Met). Inorganic mixture contains (15 mg Zn as ZnSO4, 20 mg Mn as MnSO4, 10 mg Cu as CuSO4) in sulphate forms. The experiment was commenced in the dry period of cows, 6 weeks before calving, and after calving the first three months of lactation was taken into consideration. Milk samples were collected from each cow evening and morning for estimation of milk yield production. The inorganic metals caused a significant decline (P < 0.05) in digestibility coefficients, nutritive value, nitrogen utilization, Cell wall constituents, total VFA’s, rumen volume, microbial and nitrogen synthesis compared to the organic metals. The treated group (chelated minerals) improved the milk yield, and the milk fat percentage of animals across various stages of lactation as compared to inorganic minerals treated group of animals, and no significant differences were observed among groups concerning the entire blood constituent.

PREPARATION AND CLEAVAGE MECHANISM OF CHELATES OF METAL IONS WITH EDTA LINKED TO OLIGODEOXYRIBONUCLEOTIDES

The chelates of metal ions with EDTA covalently linked to the 5′end of oligodeoxyribonuclotides(ODN),i.e,ODN5′EDTA·M(Ⅱ),are prepared,in which M(Ⅱ) is Fe(Ⅱ),Co(Ⅱ) or Cu(Ⅱ).The optimum pH value for forming these three chelates is calculated.For ODN5′EDTA Fe(Ⅱ) pH value is 5.8 to 8.6,pH 4.6～8.1 for ODN5′EDTA Co(Ⅱ),and pH 3.4～5.7 for ODN5′EDTA Cu(Ⅱ).Under such pH value conditions neither can Mg(Ⅱ) ion,necessary for cleavage reaction,be competitive with Fe(Ⅱ),Co(Ⅱ) or Cu(Ⅱ) to form EDTA chelate,nor can it be precipitated.The cleavage mechanism of ODN5′EDTA Fe(Ⅱ) for DNA duplex is discussed.Modified ODN binds with DNA duplex in the major groove via hydrogen bond to form triple helix.In the presense of oxygen and reducing agent dithiothreitol,hydroxyl radicals species are generated as intermediates by catalysis of metal ions,and then oxidize the ribo ring and cut the doublestranded DNA at the sites close to the EDTA· Fe(Ⅱ).

Synthesis and Fluorescent Properties of New Binuclear Europiumβ-Diketone Chelates Eu_mY_(1-m)(TTA)_3phen as Red Electroluminescent Materials

A new type of binuclear europlum β-diketone chelates Eum Y1-m(TTA)3 phen (0≤m≤1) and the influence of the proportion of Y on fluorescence intensity of the Eu-complexes were studied. It was found the proportion of Y3+ could affect the fluorescence properties and the film formation seriously. only m≥0.5.Y3+ could increase the luminescent intensity and improve the film formalion. As a resull. three new binuclear europium β-diketone chelales consisted of Eu, Y1-m (TTA)3phen (m=0.9. 0.7 and 0.5) were designed and synthesized. Their structures were elucidated by IR. UV. DSC and Elementary Analysis. Their PL properties were studied. The results showed that the three binuclear europium β-diketone chelates had better PL properties and film formation than Eu(TYA)3phen. They could emit sharply red light, and fluorescenl wavelength of them was all at 613nm (half bandwidth 10nm). They can be used as red organic electroluminescent materials (OELMs) in organic electrolminescent devices (OELDS).

SYNTHESIS AND MESOMORPHIC PROPERTIES OF PALLADIUM CHELATES OF LIQUID CRYSTAL POLYSILOXANE WITH β-DIKETONE-BASED SIDE CHAINS

A new type of palladium chelate of β-diketone-based side chain liquid crystal polysiloxane (Pd-DKLCP) has been synthesized by chelation reaction of palladium dichloride with polymeric ligand, β-diketone polysiloxane (DKLCP), using THF as solvent at R.T.. The Pd-chelation results in greatly increasing the phase transition temperature T_K and the enthalpy change △H_K from crystal to liquid crystal state and making the temperature range of LC state △T(△T=T_(Cl)-T_K) widened. All these chelates Pd-DKLCP's do not show T_(Cl) until decomposition at 205℃. It is noteworthy that the Pd-chelation can exert more positive effect on the mesomorphic behaviour of the polymer ligand than the counterpart Cu-DKLCP does. It is probable due to the bigger size of disc-like mesogen formed from β-diketone and Pd^(+2) ion with 4d orbital.

Tetravalent Terbium Chelates: Stability Enhancement and Property Tuning

Coordination chemistry of rare-earth elements has been dominated by the+3 oxidation state.Complexes with higher-valence lanthanide ions are synthetically challenging but are of fundamental research interest and significance as advanced molecular materials.Herein,four tetravalent terbium complexes(2-5)of the common formula[Tb(OSiPh3)4L](L=ethylene glycol dimethyl ether(DME),2,2’-bipyridine(bpy),2,2’-bipyrimidine(bpym),and 1,10-phenanthroline(phen))are reported.Crystallographic analyses reveal in each of these complexes a hexacoordinate Tb(IV)ion situated in a distorted octahedral coordination environment formed by four triphenylsi-loxido ligands and a bidentate chelating ligand.The use of chelating ligands enhances the stability of the resulting complexes over their THF solvate precursor.More significantly,the aromatic N-chelating ligands have been found to tune effectively the electronic structures of the complexes,as evidenced by the sizable potential shifts observed for the quasi-reversible redox Tb(IV/III)process and by the changes in their absorption spectra.The experimental findings are augmented with quantum theoretical calculations in which the ligandπ-donation to the 5d orbitals of the Tb(IV)center is found to be primarily responsible for stability enhancement and the corresponding changes of physical properties observed.Magnetic measurements and results from electron paramagnetic resonance studies produced small absolute values of zero-field splittings of these complexes,ranging from 0.1071(22)to 1.1484(112)cm-1 and comparable to the values reported for analogous Tb(IV)complexes.

Calcium-chelating peptides from rabbit bone collagen:characterization,identification and mechanism elucidation

This study aimed to characterize and identify calcium-chelating peptides from rabbit bone collagen and explore the underlying chelating mechanism.Collagen peptides and calcium were extracted from rabbit bone by instant ejection steam explosion(ICSE)combined with enzymatic hydrolysis,followed by chelation reaction to prepare rabbit bone peptide-calcium chelate(RBCP-Ca).The chelating sites were further analyzed by liquid chromatography-tandem mass(LC-MS/MS)spectrometry while the chelating mechanism and binding modes were investigated.The structural characterization revealed that RBCP successfully chelated with calcium ions.Furthermore,LC-MS/MS analysis indicated that the binding sites included both acidic amino acids(Asp and Glu)and basic amino acids(Lys and Arg),Interestingly,three binding modes,namely Inter-Linking,Loop-Linking and Mono-Linking were for the first time found,while Inter-Linking mode accounted for the highest proportion(75.1%),suggesting that chelation of calcium ions frequently occurred between two peptides.Overall,this study provides a theoretical basis for the elucidation of chelation mechanism of calcium-chelating peptides.

Chitin-glucan improves important pathophysiological features of irritable bowel syndrome

BACKGROUND Irritable bowel syndrome(IBS)is one of the most frequent and debilitating conditions leading to gastroenterological referrals.However,recommended treatments remain limited,yielding only limited therapeutic gains.Chitin-glucan(CG)is a novel dietary prebiotic classically used in humans at a dosage of 1.5-3.0 g/d and is considered a safe food ingredient by the European Food Safety Authority.To provide an alternative approach to managing patients with IBS,we performed preclinical molecular,cellular,and animal studies to evaluate the role of chitin-glucan in the main pathophysiological mechanisms involved in IBS.AIM To evaluate the roles of CG in visceral analgesia,intestinal inflammation,barrier function,and to develop computational molecular models.METHODS Visceral pain was recorded through colorectal distension(CRD)in a model of long-lasting colon hypersensitivity induced by an intra-rectal administration of TNBS[15 milligrams(mg)/kilogram(kg)]in 33 Sprague-Dawley rats.Intracolonic pressure was regularly assessed during the 9 wk-experiment(weeks 0,3,5,and 7)in animals receiving CG(n=14)at a human equivalent dose(HED)of 1.5 g/d or 3.0 g/d and compared to negative control(tap water,n=11)and positive control(phloroglucinol at 1.5 g/d HED,n=8)groups.The anti-inflammatory effect of CG was evaluated using clinical and histological scores in 30 C57bl6 male mice with colitis induced by dextran sodium sulfate(DSS)administered in their drinking water during 14 d.HT-29 cells under basal conditions and after stimulation with lipopolysaccharide(LPS)were treated with CG to evaluate changes in pathways related to analgesia μ-opioid receptor(MOR),cannabinoid receptor 2(CB2),peroxisome proliferator-activated receptor alpha,inflammation[interleukin(IL)-10,IL-1b,and IL-8]and barrier function[mucin 2-5AC,claudin-2,zonula occludens(ZO)-1,ZO-2]using the real-time PCR method.Molecular modelling of CG,LPS,lipoteichoic acid(LTA),and phospholipomannan(PLM)was developed,and the ability of CG to chelate microbial pathogenic lipids was evaluated by docking and molecular dynamics simulations.Data were expressed as the mean±SEM.RESULTS Daily CG orally-administered to rats or mice was well tolerated without including diarrhea,visceral hypersensitivity,or inflammation,as evaluated at histological and molecular levels.In a model of CRD,CG at a dosage of 3 g/d HED significantly decreased visceral pain perception by 14%after 2 wk of administration(P<0.01)and reduced inflammation intensity by 50%,resulting in complete regeneration of the colonic mucosa in mice with DSS-induced colitis.To better reproduce the characteristics of visceral pain in patients with IBS,we then measured the therapeutic impact of CG in rats with TNBS-induced inflammation to long-lasting visceral hypersensitivity.CG at a dosage of 1.5 g/d HED decreased visceral pain perception by 20%five weeks after colitis induction(P<0.01).When the CG dosage was increased to 3.0 g/d HED,this analgesic effect surpassed that of the spasmolytic agent phloroglucinol,manifesting more rapidly within 3 wk and leading to a 50%inhibition of pain perception(P<0.0001).The underlying molecular mechanisms contributing to these analgesic and anti-inflammatory effects of CG involved,at least in part,a significant induction of MOR,CB2 receptor,and IL-10,as well as a significant decrease in pro-inflammatory cytokines IL-1b and IL-8.CG also significantly upregulated barrier-related genes including muc5AC,claudin-2,and ZO-2.Molecular modelling of CG revealed a new property of the molecule as a chelator of microbial pathogenic lipids,sequestering gram-negative LPS and gram-positive LTA bacterial toxins,as well as PLM in fungi at the lowesr energy conformations.CONCLUSION CG decreased visceral perception and intestinal inflammation through master gene regulation and direct binding of microbial products,suggesting that CG may constitute a new therapeutic strategy for patients with IBS or IBSlike symptoms.

Carbolong Chemistry: Planar CCCCX-Type (X = N, O, S) Pentadentate Chelates by Formal [3+1] Cycloadditions of Metalla-Azirines with Terminal Alkynes

Three-membered unsaturated rings have been widely utilized in organic synthesis due to their inherent highly strained structures.Although much research has been applied to ring-expansion reactions of such strained ring systems,pathways other than[3+2]cycloadditions have rarely been observed in their reactions with alkynes,and to date,no[3+1]cycloadditions of isolated three-membered unsaturated rings with alkynes have been reported.Here we demonstrate an unprecedented[3+1]cycloaddition in which a fused metalla-azirine is used as a template to generate a series of planar CCCCX-type(X=N,O,S)pentadentate carbolong complexes 3–6.A series of substituted alkynes was tested for further exploration of the scope and mechanism for the[3+1]cycloaddition reactions.Complexes 3–6 represent rare examples of planar pentadentate complexes that assemble fourπ-conjugated fused rings by one bridgehead atom.These novel complexes are thermally stable in air and absorb ultraviolet,visible,and near-infrared light,and thus are potentially applicable in photoelectric devices and pharmaceuticals.

Therapeutic Effect of Rhodopseudomonas palustris-Bioconverted Extract of Lycium barbarum on Rats with Lead Exposure

Lead is a ubiquitous pollutant and Pb pollution is a global public health problem.Lead has been reported to induce multiple adverse effects,including reproductive toxicity,neurotoxicity,carcinogenicity,nephrotoxicity,immunotoxicity,and hypertension[1].The traditional medical treatment available for Pb poisoning is chelation,which can save lives in individuals with very high blood Pb levels.The commonly used chelating agents include CaNa2EDTA and meso-2,3-dimercaptosuccinic acid.However,chelation therapy has strong short-term effects on the overall long-term management of Pb exposure.

The chemical characteristics of different sodium iron ethylenediaminetetraacetate sources and their relative bioavailabilities for broilers fed with a conventional corn‑soybean meal diet

Background Our previous studies demonstrated that divalent organic iron(Fe)proteinate sources with higher complexation or chelation strengths as expressed by the greater quotient of formation(Qf)values displayed higher Fe bioavailabilities for broilers.Sodium iron ethylenediaminetetraacetate(NaFeEDTA)is a trivalent organic Fe source with the strongest chelating ligand EDTA.However,the bioavailability of Fe when administered as NaFeEDTA in broilers and other agricultural animals remains untested.Herein,the chemical characteristics of 12 NaFeEDTA products were determined.Of these,one feed grade NaFeEDTA(Qf=2.07×10^(8)),one food grade NaFeEDTA(Qf=3.31×10^(8)),and one Fe proteinate with an extremely strong chelation strength(Fe-Prot ES,Qf value=8,590)were selected.Their bioavailabilities relative to Fe sulfate(FeSO_(4)·7H_(2)O)for broilers fed with a conventional corn-soybean meal diet were evaluated during d 1 to 21 by investigating the effects of the above Fe sources and added Fe levels on the growth performance,hematological indices,Fe contents,activities and gene expressions of Fe-containing enzymes in various tissues of broilers.Results NaFeEDTA sources varied greatly in their chemical characteristics.Plasma Fe concentration(PI),transferrin saturation(TS),liver Fe content,succinate dehydrogenase(SDH)activities in liver,heart,and kidney,catalase(CAT)activity in liver,and SDH mRNA expressions in liver and kidney increased linearly(P<0.05)with increasing levels of Fe supplementation.However,differences among Fe sources were detected(P<0.05)only for PI,liver Fe content,CAT activity in liver,SDH activities in heart and kidney,and SDH mRNA expressions in liver and kidney.Based on slope ratios from multiple linear regressions of the above indices on daily dietary analyzed Fe intake,the average bioavailabilities of Fe-Prot ES,feed grade NaFeEDTA,and food grade NaFeEDTA relative to the inorganic FeSO_(4)·7H_(2)O(100%)for broilers were 139%,155%,and 166%,respectively.Conclusions The bioavailabilities of organic Fe sources relative to FeSO_(4)·7H_(2)O were closely related to their Qf values,and NaFeEDTA sources with higher Qf values showed higher Fe bioavailabilities for broilers fed with a conventional corn-soybean meal diet.