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.

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.

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.

Role of copper chelating agents: between old applications and new perspectives in neuroscience

The role of copper element has been an increasingly relevant topic in recent years in the fields of human and animal health, for both the study of new drugs and innovative food and feed supplements. This metal plays an important role in the central nervous system, where it is associated with glutamatergic signaling, and it is widely involved in inflammatory processes. Thus, diseases involving copper(Ⅱ) dyshomeostasis often have neurological symptoms, as exemplified by Alzheimer's and other diseases(such as Parkinson's and Wilson's diseases). Moreover, imbalanced copper ion concentrations have also been associated with diabetes and certain types of cancer, including glioma. In this paper, we propose a comprehensive overview of recent results that show the importance of these metal ions in several pathologies, mainly Alzheimer's disease, through the lens of the development and use of copper chelators as research compounds and potential therapeutics if included in multi-target hybrid drugs. Seeing how copper homeostasis is important for the well-being of animals as well as humans, we shortly describe the state of the art regarding the effects of copper and its chelators in agriculture, livestock rearing, and aquaculture, as ingredients for the formulation of feed supplements as well as to prevent the effects of pollution on animal productions.

Polarizable Additive with Intermediate Chelation Strength for Stable Aqueous Zinc‑Ion Batteries

Aqueous zinc-ion batteries are promising due to inherent safety,low cost,low toxicity,and high volumetric capacity.However,issues of dendrites and side reactions between zinc metal anode and the electrolyte need to be solved for extended storage and cycle life.Here,we proposed that an electrolyte additive with an intermediate chelation strength of zinc ion—strong enough to exclude water molecules from the zinc metal-electrolyte interface and not too strong to cause a significant energy barrier for zinc ion dissociation—can benefit the electrochemical stability by suppressing hydrogen evolution reaction,overpotential growth,and den-drite formation.Penta-sodium diethylene-triaminepentaacetic acid salt was selected for such a purpose.It has a suitable chelating ability in aqueous solutions to adjust solvation sheath and can be readily polarized under electrical loading conditions to further improve the passivation.Zn||Zn symmetric cells can be stably operated over 3500 h at 1 mA cm^(-2).Zn||NH4V4O10 full cells with the additive show great cycling stability with 84.6%capacity retention after 500 cycles at 1 A g^(-1).Since the additive not only reduces H2 evolution and corrosion but also modifies Zn2+diffusion and deposition,highlyreversible Zn electrodes can be achieved as verified by the experimental results.Our work offers a practical approach to the logical design of reliable electrolytes for high-performance aqueous batteries.

Achieving structurally stable O3-type layered oxide cathodes through site-specific cation-anion co-substitution for sodium-ion batteries

O3-type layered oxides have garnered great attention as cathode materials for sodium-ion batteries because of their abundant reserves and high theoretical capacity.However,challenges persist in the form of uncontrollable phase transitions and intricate Na^(+)diffusion pathways during cycling,resulting in compromised structural stability and reduced capacity over cycles.This study introduces a special approach employing site-specific Ca/F co-substitution within the layered structure of O_(3)-NaNi_(0.5)Mn_(0.5)O_(2) to effectively address these issues.Herein,the strategically site-specific doping of Ca into Na sites and F into O sites not only expands the Na^(+)diffusion pathways but also orchestrates a mild phase transition by suppressing the Na^(+)/vacancy ordering and providing strong metal-oxygen bonding strength,respectively.The as-synthesized Na_(0.95)Ca_(0.05)Ni_(0.5)Mn_(0.5)O_(1.95)F_(0.05)(NNMO-CaF)exhibits a mild O3→O3+O'3→P3 phase transition with minimized interlayer distance variation,leading to enhanced structural integrity and stability over extended cycles.As a result,NNMO-CaF delivers a high specific capacity of 119.5 mA h g^(-1)at a current density of 120 mA g^(-1)with a capacity retention of 87.1%after 100 cycles.This study presents a promising strategy to mitigate the challenges posed by multiple phase transitions and augment Na^(+)diffusion kinetics,thus paving the way for high-performance layered cathode materials in sodium-ion batteries.

Designing ultrastable P2/O3-type layered oxides for sodium ion batteries by regulating Na distribution and oxygen redox chemistry

P2/O3-type Ni/Mn-based layered oxides are promising cathode materials for sodium-ion batteries(SIBs)owing to their high energy density.However,exploring effective ways to enhance the synergy between the P2 and 03 phases remains a necessity.Herein,we design a P2/O3-type Na_(0.76)Ni_(0.31)Zn_(0.07)Mn_(0.50)Ti_(0.12)0_(2)(NNZMT)with high chemical/electrochemical stability by enhancing the coupling between the two phases.For the first time,a unique Na*extraction is observed from a Na-rich O3 phase by a Na-poor P2 phase and systematically investigated.This process is facilitated by Zn^(2+)/Ti^(4+)dual doping and calcination condition regulation,allowing a higher Na*content in the P2 phase with larger Na^(+)transport channels and enhancing Na transport kinetics.Because of reduced Na^(+)in the O3 phase,which increases the difficulty of H^(+)/Na^(+) exchange,the hydrostability of the O3 phase in NNZMT is considerably improved.Furthermore,Zn^(2+)/Ti^(4+)presence in NNZMT synergistically regulates oxygen redox chemistry,which effectively suppresses O_(2)/CO_(2) gas release and electrolyte decomposition,and completely inhibits phase transitions above 4.0 V.As a result,NNZMT achieves a high discharge capacity of 144.8 mA h g^(-1) with a median voltage of 3.42 V at 20 mA g^(-1) and exhibits excellent cycling performance with a capacity retention of 77.3% for 1000 cycles at 2000 mA g^(-1).This study provides an effective strategy and new insights into the design of high-performance layered-oxide cathode materials with enhanced structure/interface stability forSIBs.

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+ .

SYNTHESES AND ADSORPTION PROPERTIES OF PHENOL-FORMALDEHYDE-TYPE CHELATING RESINS BEARING THE FUNCTIONAL GROUP OFTAR TARIC ACID

Several kinds of novel chelating resins bearing the functional group of tartaric acid (TTA-FQ-12, TTA-FQ-23, and TTA-FQ-34) were synthesized by reacting epoxy maleic anhydride, which was prepared through the oxidization reaction of maleic anhydride by hydrogen peroxide, with phenol-formaldehyde resin containing polyamine (FQ resins series). The effects of such factors as reaction time, reaction temperature and pH value on the loading capacity of TTA in resins were investigated. The results showed that the optimum reaction conditions are as follows: time 9-12 h; temperature 90-105'C; pH value 6-10. The loading capacities of TTA can reach 0.15, 0.14, and 0.11 mmol/g-1 when the functional group of FQ resin was - OCH2CH2NHC2H4NH2, - O(CH2CH2NH)2C2H4NH2 and - O(CH2CH2NH)3C2H4NH2), respectively. The structures of resins were characterized by FTIR spectra. The primary study on the adsorption properties of the resins for metal ions showed that there are two kinds of adsorption mechanisms i.e. ion exchange and chelate in the adsorption process. TTA-FQ resins have much higher adsorption selectivity for Pb2+and Zn2+ than for Cu2+ and Ni2+. These resins can probably be used for separating Pb2+ or Zn2+ in the mixture of metal ions or for treating wastewater containing heavy metal ions.

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.

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.

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

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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.

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.

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.

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.

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.

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 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