Mixed d/f Complexes Zn(H2L)Ln(NO3)3(Ln=Sm,Tb and Dy)：Crystal Structure,Fluorescence and Thermal Stability

A series of isostructural d/f molecular compounds Zn（H2L）Ln（NO3）3·CH3OH（Ln = Dy（1）, Tb（2） and Sm（3）） were synthesized by the introduction of a designed multifunctional ligand N,N？,N？？,N？？？-tetra（2-hydroxy-3-methoxy-5-methylbenzyl）-1,4,7,10-tetraazacyclododecan（H4L = C（44）H（60）N4O8）. In the isostructural molecules, each crystallographically independent Zn2＋ and Ln3＋ centers are connected by two phenolic oxygen atoms. For the six-coordinate Zn-（2＋） ion, the coordination geometry can be viewed as a regular bicapped square pyramid. While for the ten-coordinate Ln-（3＋） ion, if each O,O？-chelated nitrate ligand is seen as a single coordination site, the coordination geometry can be viewed as a distorted pentagonal bipyramid. The fluorescent spectra show that compounds 2 and 3 exhibited characteristic sharp emissions of Tb-（3＋） and Sm-（3＋）, respectively, while compound 1 was found to be a single-component white-light-emitting complex in the solid state. Thermal stabilities of the three compounds were investigated by using thermal gravimetric analysis. In addition, the thermal decomposition of compound 1 was confirmed by temperature-dependent powder X-ray diffraction technique.

Crystal Structure, Spectroscopic Characterization, and Electrochemical and Thermal Stability Properties of a Dinuclear Nickel(Ⅱ) Complex

A new nickel（Ⅱ） complex Ni2（L）2（2,2＇-bipy）2·5.5H2O with methy-bicycle[2.2.1]hept-5-ene-2,3-dicarboxylic acid（H2L） and 2,2？-bipyridine（2,2＇-bipy） as ligands has been synthesized in the mixed solvent DMF and water（v：v = 5：2）. It crystallizes in the triclinic space group P1 with a = 10.414（2）, b = 12.884（3）, c = 16.176（4） A, α = 70.715（5）, β = 80.599（5）, γ = 77.383（6）°, V = 1989.4（8） A^3, Dc = 1.531 g/cm^3, Z = 2, F（000） = 958, GOOF = 1.028, the final R = 0.0808 and w R = 0.2036. The crystal structure shows that the whole molecule consists of two independent dinuclear units, in which two nickel ions are bridged by two μ2-η1：η0 3-carboxylate groups of L2- anions. The coordination environment of Ni（Ⅱ） ion is Ni N2O3, giving a distorted square pyramidal geometry. The thermal stability and electrochemical properties of the complex were investigated.

Stability on the ^(109)Cd,^(65)Zn Complex with Humus Acids

The radioactive isotope tracer and ion exchange balanced method was used to study the stability of 109Cd, 65 Zn complexes with humus acids. In the 109Cd and 65 Zn single existing system with humic acids, the stability constants of the humic-109Cd(65Zn) complex compound was higher than the fulvic-109 Cd(65Zn) complex compound. The stability constant of the humic (fulvic) -65Zn was higher than that of the humic (ful-vic)-109Cd. In the 109Cd and 65 Zn coexisting system, the stability constant and the co-ordination number of the humic (fulvic)-65Zn complex obviously increased, but the stability constant and the co-ordination number of the humic (fulvic)-109Cd complex obviously decreased as compared with its respectively single existing system . The result showed that the humus matter with higher molecular weight could more effectively reduce plant availability of heavy metals than that with lower molecular weight in polluted soil by heavy metals. The humus matter could more effectively reduce plant availability of Zn than that of Cd. Application of humus-acid increased the harm of Cd and decreased the harm of Zn to plants in Cd-Zn coexisting system.

Syntheses, Structure and Properties of a Strontium(Ⅱ) Complex with 5-Sulfoisophthalic Acid Monosodium

A new Sr（Ⅱ） complex, [Sr（Hsip）（H2O）] （1, NaH2sip = 5-sulfoisophthalic acid monosodium）, has been synthesized by solvothermal reaction of SrCO3 and NaH2sip at 120 ℃, and characterized by single-crystal X-ray diffraction studies, elemental analysis and FT-IR. Single- crystal X-ray diffraction reveals that compound 1 has a 3D architecture, and there is only one crystallographically independent Sr（Ⅱ） ion in 1. The coordination geometry of Sr（Ⅱ） is a distorted tetragonai anti-prism. The whole Hsip2- ligand performs aμ6-coordination model. In the solid state, complex 1 shows luminescence with the maximum emission intensity at 417 nm upon excitation at 320 nm. Thermal stability of complex 1 was also investigated.

A COMPARISON OF THE DETERMINATION OF STABILITY CONSTANTS OF COMPLEXES OF Cd(Ⅱ)WITH AMINO ACIDS AND SIMPLE PEPTIDES USING MICRO—pH—METRIC TITRATIONS AND CYCLIC VOLTAMMETRY

This paper reports the determination of stability constants for complexes of Cd(Ⅱ)with Gly, Ala,Val,Asp,Gly—Asp,Asp Gly,Gly—Gly and Gly—Gly—Gly using both micro—pH—metric titra- tions and the application of convolution—deconvolution cyclic voltammetry at 25℃ and I=0.10 mol· dm^(-3)(KNO_3).Stability constants were calculated from pH—metric data using the SUPERQUAD com- puter program and cyclic voltammograms were collected,stored and manipulated using the EG and G CONDECON 300 software.A considerably larger ligand:metal ratio(e,g.50:1)was possible using voltammetry.Evaluation of results from the two techniques suggests that stability constants for the species[CdL_2]and[CdL_3]are reliable when calculated fromvoltammetry while those for[CdL]are more reliable when determined by pH-metric titration.

DETERM INATION OF THE STABILITY CONSTANTS OF COMPLEXES OF HISTIDINE,SOME DIPEPTIDES AND TRIGLYCINE WITH Zn(Ⅱ)AND Cd(Ⅱ)USING SMALL-SCALE PH-METRIC TITRATIONS

A potentiometric study on the complexes of His,Gly-His,ALa-His,Gly-Gly and Gly—Gly—Gly with Zn(Ⅱ)and Cd(Ⅱ)has been reported.Small-scale potentiometric titrations were car- ried out to determine stabil ity constants of complexes at 25℃ with I=0.10 mol dm^(-3)(KNO_3).The com- puter programs SUPERQUAD were applied for data treatment with satisfactory results.

SUSPENSION-SWELLING GRAFT COPOLYMERIZATION——SYNTHESIS OF ACS RESINS

Acrylonitrile (AN)-chlorinated polyethylene (CPE)-styrene (St) (ACS) terpolymer was synthesized by suspension-swelling graft copolymerization method, in which two key factors such as dispersing system and time were studied. Highly effective comples dispersing system was chosen and determined, and two-layer protection model was put forward to clarify the stable effect mechanism Varying the swelling time of CPE in AN and St monomer mixture, some results such as grafting effect, particle characteristics, rubber particle morphology and its size distribution, and properties of ACS resins were investigated , thus the optimum swelling time was proposed.

Synthesis of barium mercaptides and application of antimony/barium mercaptides

Mercaptoacetic acid, isooctyl thioglycolate and barium hydroxide used as start materials, barium bis (2 ethylhexyl thioglycolate) (Ba(2EHTG) 2), barium thioglycolate (Ba(TG)) and barium bisthioglycolate (Ba(TG) 2) were synthesized. Their optimum synthetic techniques were discussed, and some physicochemical data were reported. Infrared spectroscopy and elemental analysis methods were used to identify the structures. They were put into PVC plastic products together with antimony tris (2 ethylhexyl thioglycolate) (Sb(2EHTG) 3) under the suitable compounding, and their heat stability to PVC was studied. It is shown that these barium mercaptides have remarkable synergisms with antimony mercaptides and the long term stabilizing effect of organoantimony stabilizer can be effectively improved, reducing the amount of antimony compounds so as to avoid the decrease of its stabilizing effect.

Novel hybrids of Cu^(2+) ternary complexes of salicylidene-amino acid Schiff base with phenanthroline(or bipyridine) intercalated in Mg/Al-NO_3-layered double hydroxide

Four Cu2＋ complexes of salicylidene-amino acid Schiff base with 1,10-phenanthroline （Phen） or 2,2＇- bipyridine （Bipy） were successfully intercalated in interlayer galleries of Mg/AI-NO3-1ayered double hydroxide （LDH） by the swelling-restored method. The hybrids were characterized by elemental analysis, X-ray diffraction, FT-IR spectra, UV-vis DRS, TG-DTA and SEM observation. Good protection of the complexes by LDH in neutral and weak acidic solutions was revealed by UV spectra, cyclic voltammograms and luminescence spectra.

Linear Complexity Problem of Binary Jacobi Sequence

This paper contributes to the stability of linear complexity of a binary periodic Jacobi sequence.By employing a pair of reference sequences,we prove that the linear complexity of a binary Jacobi sequence is unstable,namely,by changing its few bits in one-period length,the linear complexity of the modified sequences will become far less than the required value.

Drug-polymer inclusion complex as a new pharmaceutical solid form

The solid forms of drugs play a central role in controlling their physicochemical properties and consequently the bioavailability. Multiple types of drug solid forms have been developed to achieve the desirable pharmaceutical profiles, but new solid forms will provide more options for the solid-state property optimization and hence are highly desirable. This review focuses on a new pharmaceutical solid form, drug-polymer inclusion complexes （ICs）, and summarizes their structural features, structure- property relationships, as well as potential pharmaceutical applications

Crystalline inclusion complexes formed between the drug diflunisal and block copolymers

The solid form of drugs plays a central role in optimizing the physicochemical properties of drugs,and new solid forms will provide more options to achieve the desirable pharmaceutical profiles of drugs.Recently,certain drugs have been found to form crystalline inclusion complexes（ICs） with multiple types of linear polymers,representing a new subcategory of pharmaceutical solids.In this study,we used diflunisal（DIF） as the model drug host and extended the guest of drug/polymer ICs from homopolymers to block copolymers of poly（ethylene glycol）（PEG） and poly（s-caprolactone）（PCL）.The block length in the guest copolymers showed a significant influence on the formation,thermal stability and dissolution behavior of the DIF ICs.Though the PEG block could hardly be included alone,it could indeed be included in the DIF ICs when the PCL block was long enough.The increase of the PCL block length produced IC crystals with improved thermal stability.The dissolution profiles of DIF/block copolymer ICs exhibited gradually decreased aqueous solubility and dissolution rate with the increasing PCL block length.These results demonstrate the possibility of using drug/polymer ICs to modulate the desired pharmaceutical profiles of drugs in a predictable and controllable manner.

Highly Active Pd-PEPPSI Complexes for Suzuki-Miyaura Cross-coupling of Aryl Chlorides:an Investigation on the Effect of Electronic Properties

Three new Pd-pyridine enlianced precatalyst preparation stabilization and initiation(PEPPSI)complexes with halogen groups on the N-heterocyclic carbene and pyridine were prepared.Tlieir structures have been clearly characterized by nuclear magnetic resonance spectroscopy and X-ray single-crystal di fraction.The e fleets of the electronic properties of halogen groups on the catalytic activity in the Suzuki-Miyaura cross-coupling of aryl chlo-rides were investigated.These Pd-PEPPSI complexes could catalyze the cross-coupling reaction efficiently with a low catalyst loading(0.05%,molar ratio)at room temperature and the products were obtained in high yields.

A comparison of the determination of stability constants of complexes of Pb(II) with amino acids using micro-pH-metric titrations and cyclic voltammetry

This paper reports the determination of stability constants for complexes of Pb(Ⅱ) with Gly, Ala, Asp and Gly-Gly using both micro-pH-metric titrations and the application of convolution-de- convolution cyclic voltammetry at 25℃ and I = 0.10 mol.dm^(-3)(KNO_3). Stability constants were calculated from pH-metric data using the SUPERQUAD computer program and cyclic voltammograms were collected, stored and manipulated using the E G and G CONDECON 300 software. A consider- ably larger ligand: metal ratio (e.g. 50:1) was possible using voltammetry. Under these conditions, hydroxy complex formation was minimised and the formation of bis-complexes optimised. Computer based calculations were carried out on PC-compatible microcomputers fitted with mathematics co- processors. Evaluation of results from the two techniques suggests that stability constants for the species [PbL_2] are reliable when calculated from voltammetry while those for [PbL] are mote reliable when determined by pH-metric titration.

Determination of the acid dissociation constants of N-carboxymethyl-N-(p-hydroxy phenyl carbamoylmethyl)-2,3-dihydroxy- 5-carbomethoxy benzylamine and the stability constants of its metal complexes

The acid dissociation constants of N-carboxymethyl-N-(p-hydroxy phenyl carbamoyl- methyl)-2,3-dihydroxy-5-carbomethoxy benzylamine(CHDCB) and the stability constants of its 1:1 complexes with alkaline earth, Cd(Ⅱ), Co(Ⅱ), Ni(Ⅱ), Cu(Ⅱ), Zn(Ⅱ), Fe(Ⅲ),Th(Ⅳ)and U(Ⅵ)ions have been determined at 25.0±0.1℃ and at an ionic strength of 0.1(KNO_3)by pH titration method. The probable coordination sites have also been discussed.

Effect of molecular weight of dissolved organic matter on toxicity and bioavailability of copper to lettuce

To clarify the effects of molecular weight of dissolved organic matter （DOM） on the toxicity and bioavailability of copper （Cu） to plants, DOM extracted from chicken manure was ultra-filtered into four fractions according to their molecular weights by means of sequential-stage ultrafiltration technique. Lettuce seeds were germinated by being exposed to the solutions containing Cu^2＋ with or without different fractions of DOM. The concentration of copper in roots, leaves, sprouts and the length of roots were investigated. The results showed that not all fractions of DOM could improve copper availability or toxicity. The fraction of DOM with larger molecular weight more than 1 kDa had higher complexation stability with Cu^2＋ and caused lower concentration of free Cu^2＋ ion in the solution of copper plus the fraction, resulting in lower availability and toxicity of copper to lettuce, but the fraction with molecular weight less than 1 kDa had the opposite function. Therefore, the molecular weight of 1 kDa may be the division point to determine DOM to increase or decrease copper availability and toxicity.