Synthesis and characterization of a nano fluorescent starch.

A novel nano fluorescent starch, starch-bearing 3-epoxypropoxy fluorescein (ST-EF) was developed by a simple method. First, 3-epoxypropoxy fluorescein (EF) was prepared via a nucleophilic substitution reaction between fluorescein and epichlorohydrin. Then, ST-EF was synthesized via a ring-opening reaction to attach fluorescein to native cassava starch chains. The degree of substitution (DS) of ST-EF was determined by ultraviolet-visible spectrophotometry. The 1H nuclear magnetic resonance (NMR) spectroscopy, elemental analysis, fourier transformed infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), transmission electron microscope (TEM), dynamic laser scattering (DLS), X-ray diffraction (XRD) and differential scanning calorimetry (DSC) were used to characterize ST-EF. Fluorescent properties of ST-EF in water were studied. The results showed that the nano fluorescent starch shows strong fluorescence as fluorescein, and can be used as a fluorescent polymer in various applications, especially in biomedicine.

Potassium complexes supported by monoanionic tetradentate amino-phenolate ligands: synthesis, structure and catalysis in the ring-opening polymerization of rac-lactide.

A series of potassium complexes bearing monoanionic tetradentate amino-phenolate ligands, [LK]2 (L = {(2-R1)C6H4CH2N[(CH2)2R2]CH2(4-R4-6-R3)C6H2O-}, R1 = NMe2, R2 = NEt2, R3 = CPh3, R4 = Me (1); R1 = R2 = NEt2, R3 = CPh3, R4 = Me (2); R1 = NMe2, R2 = NEt2, R3 = R4 = cumyl (4); R1 = R2 = OMe, R3 = tBu, R4 = Me (6); L = (2-NMe2)C6H4CH2N[[CH2-(S)-1-butylpyrrolidinyl]CH2(4-Me-6-CPh3)C6H2O-] (3)), have been synthesized via reactions of KN(SiMe3)2 and 1 equiv. of the corresponding aminophenols. The solid-state structures of typical complexes 4 and 6 are determined via X-ray diffraction studies, which reveal the dinuclear nature of these complexes. By contrast, DOSY measurements of 1, 4 and 6 suggest that these complexes are monomeric in solution. It is noteworthy that the coordination chemistry of these potassium complexes is versatile, which is closely related to the nature of the ortho-substituent of the phenolate ring, as indicated by the results of the corresponding spectroscopic studies. In the presence of iPrOH, 1-4 and 6 could initiate the polymerization of 500 equiv. of rac-lactide to achieve high monomer conversions within several minutes but afford atactic PLAs with slightly isotactic-enriched microstructures (Pm = 0.58-0.60). Experimental results also demonstrated that a bulky trityl substituent at the ortho-position of the phenolate ring of the ligand framework is beneficial for the enhancement of the activities of these potassium complexes.

ß-Tricalcium phosphate/poly(glycerol sebacate) scaffolds with robust mechanical property for bone tissue engineering.

Despite good biocompatibility and osteoconductivity, porous ß-TCP scaffolds still lack the structural stability and mechanical robustness, which greatly limit their application in the field of bone regeneration. The hybridization of ß-TCP with conventional synthetic biodegradable PLA and PCL only produced a limited toughening effect due to the plasticity of the polymers in nature. In this study, a ß-TCP/poly(glycerol sebacate) scaffold (ß-TCP/PGS) with well interconnected porous structure and robust mechanical property was prepared. Porous ß-TCP scaffold was first prepared with polyurethane sponge as template and then impregnated into PGS pre-polymer solution with moderate viscosity, followed by in situ heat crosslinking and freezing-drying process. The results indicated that the freezing-drying under vacuum process could further facilitate crosslinking of PGS and formation of Ca(2+)-COO(-) ionic complexing and thus synergistically improved the mechanical strength of the ß-TCP/PGS with in situ heat crosslinking. Particularly, the ß-TCP/PGS with 15% PGS content after heat crosslinking at 130°C and freezing-drying at -50°C under vacuum exhibited an elongation at break of 375±25% and a compressive strength of 1.73MPa, 3.7-fold and 200-fold enhancement compared to the ß-TCP, respectively. After the abrupt drop of compressive load, the ß-TCP/PGS scaffolds exhibited a full recovery of their original shape. More importantly, the PGS polymer in the ß-TCP/PGS scaffolds could direct the biomineralization of Ca/P from particulate shape into a nanofiber-interweaved structure. Furthermore, the ß-TCP/PGS scaffolds allowed for cell penetration and proliferation, indicating a good cytobiocompatibility. It is believed that ß-TCP/PGS scaffolds have great potential application in rigid tissue regeneration.

Aluminum complexes with bidentate amido ligands: synthesis, structure and performance on ligand-initiated ring-opening polymerization of rac-lactide.

A series of mononuclear aluminum dimethyl complexes bearing bidentate N-[2-(1-piperidinyl)benzyl]anilino or N-(2-morpholinobenzyl)anilino ligands were synthesized via reactions of the corresponding proligands with trimethylaluminum upon heating, while at ambient temperature two trimethylaluminum adducts with neutral N-[2-(1-piperidinyl)benzyl]aniline proligands were obtained. These complexes were well characterized by NMR spectroscopy, elemental analysis and occasionally by EI-HRMS. The molecular structures of the typical trimethylaluminum adduct 2b and aluminum dimethyl complex 3b were further confirmed by X-ray diffraction studies. All the aluminum dimethyl complexes could effectively initiate the ring-opening polymerization (ROP) of rac-lactide in a well-controlled manner to afford PLAs with narrow molecular weight distributions (PDI = 1.06-1.18). The polymer samples obtained are systematically end-capped with the bidentate ancillary ligands as characterized by (1)H NMR and ESI-TOF mass spectroscopy. Moreover, the introduction of substituent(s) at the ortho-position(s) of the anilino moiety in the ligand results in an obvious decrease in the catalytic activity of the corresponding aluminum complex, and complexes with meta-chloro substituted anilino units show higher activities likely due to the enhanced electrophilicity of the metal centers induced by the anilino groups.

Exploitation of dinuclear salan aluminum complexes for versatile copolymerization of ε-caprolactone and L-lactide.

By combining the influence of excess alcohol, temperature and monomer-to-initiator ratios in the feed, dinuclear salan aluminum complexes L(R)Al(2)Me(4) exhibited a high degree of control towards the copolymerization of L-LA and ε-CL, producing blocky, gradient, tapered and random copolymers.

Mode of action of membrane-disruptive lytic compounds from the marine dinoflagellate Alexandrium tamarense.

Certain allelochemicals of the marine dinoflagellate Alexandrium tamarense cause lysis of a broad spectrum of target protist cells but the lytic mechanism is poorly defined. We first hypothesized that membrane sterols serve as molecular targets of these lytic compounds, and that differences in sterol composition among donor and target cells may cause insensitivity of Alexandrium and sensitivity of targets to lytic compounds. We investigated Ca(2+) influx after application of lytic fractions to a model cell line PC12 derived from a pheochromocytoma of the rat adrenal medulla to establish how the lytic compounds affect ion flux associated with lysis of target membranes. The lytic compounds increased permeability of the cell membrane for Ca(2+) ions even during blockade of Ca(2+) channels with cadmium. Results of a liposome assay suggested that the lytic compounds did not lyse such target membranes non-specifically by means of detergent-like activity. Analysis of sterol composition of isolates of A. tamarense and of five target protistan species showed that both lytic and non-lytic A. tamarense strains contain cholesterol and dinosterol as major sterols, whereas none of the other tested species contain dinosterol. Adding sterols and phosphatidylcholine to a lysis bioassay with the cryptophyte Rhodomonas salina for evaluation of competitive binding indicated that the lytic compounds possessed apparent high affinity for free sterols and phosphatidylcholine. Lysis of protistan target cells was dose-dependently reduced by adding various sterols or phosphatidylcholine. For three tested sterols, the lytic compounds showed highest affinity towards cholesterol followed by ergosterol and brassicasterol. Cholesterol comprised a higher percentage of total sterols in plasma membrane fractions of A. tamarense than in corresponding whole cell fractions. We conclude therefore that although the molecular targets of the lytic compounds are likely to involve sterol components of membranes, A. tamarense must have a complex self-protective mechanism that still needs to be addressed.

Zinc complexes supported by multidentate aminophenolate ligands: synthesis, structure and catalysis in ring-opening polymerization of rac-lactide.

Monomeric zinc silylamido and ethyl complexes bearing tetradentate aminophenolato ligands [(DNNO)ZnR] (D = NMe(2), OMe; R = N(SiMe(3))(2) (1-5, 8), Et (6, 7, 9, 10)), were isolated from the reaction of Zn[N(SiMe(3))(2)](2) or ZnEt(2) and one equivalent of aminophenols {aryl-CH(2)N[(CH(2))(2)NMe(2)]CH(2)-phenol} in moderate to high yields. The monomeric nature of these complexes was further confirmed by X-ray diffraction studies of silylamido complexes 1, 3 and ethyl complexes 7, 9, 10. The methoxy or N,N-dimethylamino group of the aryl unit does not coordinate with the metal center in the solid state, only the remaining three donors of the ligand and silylamido or ethyl group interact with zinc center constructing a distorted tetrahedral coordination geometry at the metal center. All these zinc complexes efficiently initiated the ring-opening polymerization of rac-lactide, and the polymerization runs were better controlled in the presence of isopropanol, giving atactic PLAs end-capped with isopropyl ester and hydroxyl groups. The structure of the ancillary ligands showed some influence on the catalytic activity and selectivity of the corresponding zinc complexes. The introduction of bulky ortho-substituents on the phenoxy unit resulted in a decrease of the polymerization rate, whereas the isotactic dyad selectivity in the ROP of rac-lactide was enhanced.

Amidinate aluminium complexes: synthesis, characterization and ring-opening polymerization of rac-lactide.

A series of aluminium alkyl complexes {PhC(NR')(NR'')}AlR(2) (4a-n, R' = 2,6-(i)Pr(2)C(6)H(3), 2,6-Me(2)C(6)H(3); R'' = aryl groups with various ortho-, para- or meta-substituents, tert-butyl; R = methyl, ethyl) bearing non-symmetrically N-substituted benzamidinate ligands were synthesized via the reaction of trialkylaluminium and the corresponding benzamidine proligands. Complex 5 bearing symmetric amidinate ligand was also obtained for comparison purposes. The X-ray diffraction studies of complexes 4b, 4c and 5 show in each case a distorted tetrahedral geometry around the aluminium center. All the amidinate aluminium complexes were found to catalyze the ring-opening polymerization (ROP) of rac-lactide with moderate activities. The steric and electronic characteristics of the ancillary ligands have a significant influence on the polymerization performance of the corresponding aluminium complexes. The introduction of electron-withdrawing substituents at the ortho-positions of N-phenyl ring of the ligands resulted in an obvious increase in catalytic activity. Complex 4b showed the highest activity among the investigated aluminium complexes due to the high electrophilicity of the metal center induced by the ortho-chloro substituents on the phenyl ring. The existence of ortho-substituents of small steric bulkiness is also beneficial for the increase of activity of these catalysts. However, further increase of steric hindrance of the ligands by introducing bulky ortho-substituents onto the phenyl moieties resulted in a decrease of activity and an increase in the isotactic bias of the obtained polylactides. The broad molecular weight distributions (PDI = 1.13-2.02) of the polymer samples indicated that the ROP of rac-lactide initiated by these complexes was not well-controlled.

beta-Diketiminate aluminium complexes: synthesis, characterization and ring-opening polymerization of cyclic esters.

A series of aluminium alkyl complexes (BDI)AlEt(2) (3a-m) bearing symmetrical or unsymmetrical beta-diketiminate ligand (BDI) frameworks were obtained from the reaction of triethyl aluminium and the corresponding beta-diketimine. The monomeric structure of the aluminium complex 3k was confirmed by an X-ray diffraction study, which shows that the aluminium center is coordinated by both of the nitrogen donors of the chelating diketiminate ligand and the two ethyl groups in a distorted tetrahedral geometry. Attempt to synthesize beta-diketiminate aluminium alkoxide complexes by the reactions of monochloride complex "(BDI-2a)AlMeCl" (4) with alkali salts of 2-propanol gave unexpectedly an aluminoxane [(BDI-2a)AlMe](2)(micro-O) (7) as characterized by X-ray diffraction methods. Complexes 3a-m and [(2,6-(i)Pr(2)C(6)H(3)NCMe)(2)HC]AlEt(2) (8) were found to catalyze the ring-opening polymerization (ROP) of epsilon-caprolactone with moderate activities. The steric and electronic characteristics of the ancillary ligands have a significant influence on the polymerization performance of the corresponding aluminium complexes. The introduction of electron-donating substituents at the para-positions of the aryl rings in the ligand resulted in an apparent decrease in catalytic activity. Complex 3h showed the highest activity among the investigated aluminium complexes due to the high electrophilicity of the metal center induced by the meta-trifluoromethyl substituents on the aryl rings. The increase of steric hindrance of the ligand by introducing ortho-substituents onto the phenyl moieties also resulted in a decrease in the catalytic activity. Although the viscosity average molecular weights (M(eta)) of the obtained poly(caprolactone)s increased with the enhancement of monomer conversion, the ROPs of epsilon-caprolactone initiated by complexes 3a-m and 8 were not well-controlled, as judged from the broad molecular weight distributions (PDI = 1.66-3.74, M(w)/M(n)) of the obtained polymers and the nonlinear relationship of molecular weight versus monomer conversion.

Aluminium alkyl complexes supported by [OSSO] type bisphenolato ligands: synthesis, characterization and living polymerization of rac-lactide.

Aluminium alkyl complexes [(OSSO)AlR](1-3: R = Me, Et) were isolated in good yields from the protonolysis reaction of AlR3 with the corresponding tetradentate 1,omega-dithiaalkanediyl-bridged bisphenols (1,4-dithiabutanediyl-bis(6-tert-butyl-4-methylphenol), etbmpH2; ortho-xylylenedithio-bis(6-tert-butyl-4-methylphenol), xytbmpH2). The monomeric structures of all three complexes were confirmed by X-ray diffraction studies. Complexes 1 and 2 have an isotypic packing arrangement. The aluminium center is coordinated by the etbmp ligand and one alkyl group with distorted trigonal bipyramidal geometry. Complex 3 shows Cs symmetry with square pyramidal geometry around the metal center. Substitution reaction of complex 1 with trityl alcohol gave the monomeric alkoxide complex [(etbmp)Al(OCPh3)] 4, which has a similar trigonal bipyramidal geometry around the aluminium atom as complex 1. In the presence of isopropanol, complexes 1-3 initiated the living ring-opening polymerization of rac-lactide (PDI = 1.03-1.06, Mw/Mn). The ligand structure influenced the tacticity of the obtained polymer, with complex 3 giving heterotactic-enriched polylactides.