Synthesis,structure and behavior of new polycaprolactam copolymers based on poly (ethylene oxide)–poly (propylene oxide)–poly (ethylene oxide) macroactivators derived from Pluronic block copolymers

Novel series of poly (CL–co–Pluronic) polymers were successfully synthesized in situ by ring-opening polymerization (ROP) of ε-caprolactam (ε-CL). The copolymerization was activated by new type macroactivators (MAs) based on hydroxyl-terminated poly (ethylene oxide)-poly (propylene oxide)-poly (ethylene oxide) [PEO-PPO-PEO] triblock copolymers, known under the trade name Pluronic^®. Toluene-2,4-diisocyanate (TDI) was used to obtain the isocyanate-terminated Pluronic prepolymers. The corresponding MAs were synthesized in situ with an N-carbamoyllactam structure. As an initiator of the copolymerization processes was used sodium lactamate (NaCL). To confirm the influence over the copolymerization process, microstructure, composition and molecular weight of the polymeric products two new types MAs based on Pluronic (P123 and F68) have been varied from 2 to 10 wt.% (vs. the monomer ε-CL). The structure of the both Pluronic based macroactivators (MAs) and accordingly obtained two series poly (CL-co-Pluronic) polymers were confirmed by ¹H NMR and FT-IR analyses. Additionally, the structure, molecular weight, physicomechanical behavior, thermal stability and morphology of the new synthesized poly (CL–co–Pluronic) polymers have been investigated by Differential Scanning Calorimetry (DSC), Wide-Angle X-ray Diffraction (WAXD), Thermogravimetric Analysis (TGA) and Scanning Electron Microscopy (SEM) analysis.     

Synthesis and photoluminescent properties of four novel trinuclear europium complexes based on two tris-β-diketones ligands

Four novel trinuclear europium complexes with two tris-β-diketones ligands have been synthesized, and the chemical structures of ligands and complexes were characterized by FT-IR, UV-vis, ¹H NMR, ¹³C NMR, XRD, ESI-MS, and element analysis. The potoluminescent properties of trinuclear complexes in solid and THF solution were investigated. All trinuclear complexes exhibited strong relative luminescent intensity and long luminescent lifetime. Meanwhile, the results of lifetime decay curves indicated that only one chemical environment existed around the europium ion. The intrinsic luminescent quantum yields (Φ_LN) and experimental intensity parameters of trinuclear complexes were obtained based on the emission spectra and luminescent lifetime of ⁵D₀ excited state for europium ion. All trinuclear europium complexes exhibited relative high intrinsic luminescent yield and intensity parameters. Especially, due to the contribution of addition two europium lumophors in trinuclear europium complexes, the trinuclear complexes containing TTA exhibited much longer lifetime and higher intrinsic quantum yield than mononuclear europium complex Eu(TTA)₃phen.     

Synthesis and characterization of polymers from β-propiolactone and poly(ethylene glycol)s

Uncatalysed polymerizations of β-propiolactone with low-molecular-weight poly(ethylene glycol)s were carried out in bulk, at temperatures in the range of 70 to 120°C. ¹H nuclear magnetic resonance (n.m.r.) and differential scanning calorimetry (d.s.c.) measurements on the resulting products indicated a block copolymer structure. Gel permeation chromatography (g.p.c.) and d.s.c. analyses showed that in some cases the copolymerization is accompanied by homopolymerization of β-propiolactone, probably due to the presence of residual water in the poly(ethylene glycol). N.m.r. and infra-red (i.r.) spectra of copolymers revealed the presence of hydroxyl and carboxyl end groups. The copolymerization reaction may be visualized as a two-step process, in which the ring opening of β-propiolactone takes place on both the hydroxyl groups of poly(ethylene glycol), followed by repetitive monomer addition forming an ester-ether-ester triblock copolymer.     

The polymerization behavior and thermal properties of benzoxazine based on o-allylphenol and 4,4′-diaminodiphenyl methane

Three bifunctional benzoxazines (oAP-ddm, oC-ddm, and P-ddm) were synthesized from 4,4′-diaminodiphenyl methane, formaldehyde, and three phenols, namely o-allylphenol, o-cresol, and phenol. The polymerization temperatures and activation energies of oAP-ddm and oC-ddm are very similar and higher than those of P-ddm; however, their reaction enthalpies exhibit inverse behavior. The storage moduli of the corresponding polybenzoxazines, PoAP-ddm, PoC-ddm, and PP-ddm, are approximately 2.1, 3.2, and 2.9 GPa at 25 °C, respectively, and their glass transition temperatures are 139, 166, and 198 °C, respectively. The thermal stabilities of PoAP-ddm and PoC-ddm are similar and lower than that of PP-ddm. The results indicate that polybenzoxazines based on ortho-substituted phenols provide higher flexibility than their counterparts prepared from unsubstituted phenol.     

A new 3D metal–organic framework based on a hexanuclear cobalt(II): Synthesis,structure, and magnetic property

A new 3D framework 1 based on {Co₆} cluster as node was successfully synthesized and fully characterized, which showed an 8-connected bcu topology with the Schläfli symbol of {4²⁴,6⁴}. Furthermore, the thermal stability and magnetic property reveal that 1 displays high thermal stability and antiferromagnetic interaction among the Co^II spin carries.     

Synthesis,structure, and catalytic activity of a new chiral NHC–iridium(III) complex

The new chiral NHC–iridium complex 3 has been prepared in CH₃CN from the reaction between [Ir(COD)Cl]₂, NaOAc, KI, and dibenzimidazolium salt 2 which is derived from (S)-2,2′-diamino-6,6′-dimethyl-1,1′-biphenyl. Complex 3 has been characterized by various spectroscopic techniques, elemental analyses, and X-ray diffraction analysis. It has a distorted-octahedral IrC₂N₂IH core structure, and shows good catalytic activity for the asymmetric hydrosilylation of arylmethyl ketones, leading to 1-arylethanol with moderate ee values.     

Synthesis,characterization and As(III) adsorption behavior of β-cyclodextrin modified hydrous ferric oxide

This study investigates the adsorption of As(III) on β-cyclodextrin modified hydrous ferric oxide (HCC). This is characterized by XRD, FESEM, AFM, XPS, BET, surface site concentration and FTIR. The modification of hydrous ferric oxide (HFO) surface by β-cyclodextrin provides ample OH groups which in turn increase As(III) adsorption on HCC compared to HFO. The adsorption remains almost constant in pH range 3–8 which decreases at higher pH (>8) and followed monolayer and pseudo first order kinetics. It is spontaneous at 303 K with increasing entropy and decreasing enthalpy. Thus HCC is found to be more efficient adsorbent than HFO.     

Synthesis of amphiphilic polycyclooctene-graft–poly(ethylene glycol) copolymers by ring-opening metathesis polymerization

In this paper, a novel monomer of 4-methyl-3-(carbamate)–carbanilic acid-4-cyclooctene ester (MCCCE) was synthesized and characterized by FTIR, NMR and ESI-MS. Polycyclooctene-graft-blocked isocyanate copolymers were prepared by the copolymerization of MCCCE and cyclooctene via ring-opening metathesis polymerization (ROMP). Amphiphilic polycyclooctene-graft–PEG copolymers were prepared by melt mixing the polycyclooctene-graft-blocked isocyanate copolymers with poly(ethylene glycol) (PEG) at 200 °C. The blocked isocyanate group on MCCCE can be dissociated to produce free isocyanate group, which will react with the end hydroxyl groups on PEG molecules. The effects of monomer-to-catalyst, monomer-to-chain transfer agent ratios on molecular weight of the copolymer were detailedly studied. The water contact angle of polycyclooctene-graft–PEG copolymer is much smaller than that of polycyclooctene.     

Synthesis,structure and magnetic property of a Gd–Mn coordination polymer based on 2,3,5-pyrazinetricarboxylate

A new three-dimensional lanthanide–manganese metal–organic framework [Gd₂Mn₃(PZTC)₄(H₂O)₁₂]·5H₂O (PZTC = 2,3,5-Pyrazinetricarboxylate) has been synthesized under hydrothermal conditions and characterized by IR, elemental analyses, and X-ray diffraction. Single-crystal X-ray diffraction shows that Gd^3 + and Mn^2 + ions are linked together to form a porous 3D Gd–Mn MOF by the alternative arrangement of two kinds of PZTC^3 − ligands. Taking the Gd, Mn and PZTC as node, the Schläfli symbol of the topology can be expressed as {4;8²}₂{4²;6}₂{4²;8⁴}₂{4³;6;8⁴;10²}₂{8}. Magnetic study indicates the magnetic coupling between two Mn^2 + ions through double monatomic carboxylate–oxo bridges is weak antiferromagnetic, while that between Gd^3 + and Mn^2 + ions through the carboxylate group in syn–anti-bridging mode is negligible.     

The synthesis,structure and photoluminescent properties of solid-state green to yellow emitters based on β-carboline

A series of solid-state green to yellow emitters based on β-carboline core were synthesized and characterized. The crystal structures of four of them were determined by single crystal X-ray diffraction analysis. The photoluminescent properties of β-carbolines were examined in solution and in the solid state. It was found that these fluorophores were luminescent, having solid-state emission at wavelengths ranging from 505 to 582 nm, depending on structure. Significantly, two naphthalene-carboline hybrids exhibit strong green fluorescence emission both in solution and in crystalline state. However, two methoxyl-phenyl substituted β-carboline derivative show intense green/yellow emission peaked at 540–582 nm, and display red-shifted by 40–82 nm with respect to the solution behavior. The experimental results demonstrated that the solid-state emission ranging from green to yellow can be readily tuned by simply varying molecular structure. The solid-state luminescent properties are highly dependent on the nature and position of the substituents and also on the molecular arrangements and the intermolecular interactions.     

Influences of molecular structure on the isothermal crystallization behavior and mechanical properties of β-nucleated isotactic polypropylene

ABSTRACT

To investigate the influence of molecular structure of isotactic polypropylene (iPP) on the crystallization behavior and mechanical properties of its β-nucleated product, in this study, four iPP samples were selected. Results of molecular structure characterizations revealed that the molecular weight of the iPP resins are close, while the average isotacticities and the isotacticity distributions of the samples are quite different from each other. Isothermal crystallization kinetics study suggested that due to their different average isotacticities and isotacticity distributions, the crystallinity difference of the four samples is as high as 5.3%, and the crystallinity of β-crystal difference is as high as 7.2%. Generally, the higher the average isotacticity of the iPP and the wider its distribution are, the stronger the β-crystallization ability of the sample is. Moreover, the mechanical measurement revealed that high average isotacticity and the wide isotacticity distribution of the iPP resulted in the strong the β-crystallization ability and thus better the toughness.     

Syntheses,structures and photoluminescence of Ln(III)–Cu(I) coordination polymers based on benzimidazole-5-carboxylate and oxalate ligands

Three novel Ln(III)–Cu(I) coordination polymers, namely [LnCu(Hbic)₃(ox)_0.5] [Ln = Sm (1), Dy (2), Hbic = benzimidazole-5-carboxylate, ox = oxalate] and [EuCu(Hbic)₂(ox)H₂O]·2H₂O (3) have been hydrothermally synthesized and stucturally characterized. Both complexes 1 and 2 display the same unusual 2D layer heterometallic coordination frameworks that are built up by dimeric [Ln₂(Hbic)₆] cores and oxalate ligands by sharing Cu(I) ions. Complex 3 represents 1D polymeric chain architecture constructed from Eu₂Cu₂ ring units and oxalate ligands. Furthermore, the luminescent property of complex 3 has also been investigated.     

Organometallic ruthenium complexes with thiosemicarbazone ligands: Synthesis,structure and cytotoxicity of [(η6-p-cymene)Ru(NS)Cl]+ (NS = 9-anthraldehyde thiosemicarbazones)

A series of half-sandwich arene ruthenium complexes containing bidentate thiosemicarbazone ligands have been synthesized and their biological activity investigated. The compounds have the general formula [(6-p-cymene)Ru(R-ATSC)Cl]X (ATSC = 9-anthraldehyde thiosemicarbazone and R = H, CH₃ and C₆H₅). The crystal structure of [(6-p-cymene) Ru(MeATSC)Cl]Cl have been determined and represents the first structurally characterized arene–ruthenium half-sandwich complex with a thiosemicarbazone ligand. The complexes show good cytotoxic profiles against MCF-7 and MDA-MB-231 (breast adenocarcinoma) as well as HCT 116 and HT-29 (colorectal carcinoma) cell lines.     

Synthesis,structures, luminescent and magnetic properties of four coordination polymers based on biphenyl-2,4′,5-tricarboxylic acid and different N-donor ligands

Four new coordination polymers [Zn(HL)(bibp)]_n (1: H₃L = biphenyl-2,4′,5-tricarboxylic acid, bibp = 4,4′-bis(imidazolyl)biphenyl), [Co(HL)(bibp)]_n (2), [Co(HL)(bib)]_n·4nH₂O (3: bib = 1,4-bis(1-imidazoly)-benzene), [Co_1.5(L)(bib)_1.5(H₂O)]_n·3nH₂O (4), have been synthesized under solvo/hydrothermal conditions, and have been fully characterized by single-crystal X-ray diffraction, powder X-ray diffraction (PXRD), IR spectra, elemental analysis and thermogravimetric analysis (TGA). Structural analyses reveal that both 1 and 2 display a 4-fold interpenetrated framework. Complex 3 possesses a 2D (4,4) network. Complex 4 exhibits a 3D framework with the point symbol of {3²·4·6⁷}₂{3²·6¹⁰·7²·8}. Moreover, photoluminescence properties of 1 and magnetic properties of 2–4 have also been studied in detail.     

Effects of electron beam irradiation on the structure–property behavior of blends based on low density polyethylene and styrene-ethylene-butylene-styrene-block copolymers

Low density polyethylene (LDPE) blends with different additives were exposed to various doses of electron beam irradiation. The additives used were styrene-ethylene-butylene-styrene-block copolymers (SEBS), styrene-ethylene-butylene-styrene-block copolymer grafted with maleic anhydride (SEBS-g-MA) and mineral compounds. The structure–property behavior of electron beam irradiated blends was characterized in terms of mechanical, thermal, and electrical resistivity properties. The results indicated that the unirradiated LDPE blends with the different compositions showed improved mechanical properties, thermal and volume resistivity properties than pure LDPE. However, the improvement in properties of unirradiated blends by using SEBS-g-MA was higher than using SEBS copolymer. Further improvement in the mechanical, thermal and electrical properties of the LDPE blends was achieved after electron beam irradiation. The limited oxygen index (LOI) data revealed that the LDPE/SEBS-g-MA/ATH blend was changed from combustible to self-extinguishing material after electron beam irradiation to a dose of 100 kGy. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis,characterization, crystal structure and in vitro anticancer potentials of mono and bimetallic palladium(II)–N–heterocyclic carbene complexes

N–heterocyclic carbene (NHC) complexes of palladium(II) are generally active as catalysts toward various coupling reactions, while their pharmacological efficiencies are seldom explored. A new series of palladium(II) complexes of both, functionalized and non–functionalized NHCs that were active against the human colon cancer (HCT116) cells are reported. Complexes were prepared by the technique of transmetallation using palladium source and in situ prepared silver(I)–NHC complexes in acetonitrile, and all complexes are characterized using spectroscopic and analytical tools. Additionally, the structure of palladium complex 9 was elucidated using single crystal X–ray diffraction method. In vitro anticancer studies revealed that the palladium complexes, 9 and 10, having xylyl–spacers significantly inhibited the HCT116 cell growth, exhibiting IC₅₀ values in low micromolar range in MTT assay.