Preparation,Characterization and Drug Release Behavior of 5-Fluorouracil Loaded Carboxylic Poly(ε-caprolactone) Nanoparticles

In this paper, 5-Fluorouracil (5-FU) loaded carboxylic poly(ε-caprolactone) nanoparticles have been prepared by emulsification/solvent evaporation o/w method, and the drug release behaviors of 5-FU were investigated. The novel carboxylic poly (ε-caprolactone) (P(CL-OPD)-mal) was synthesized via conjugation of maleic anhydride to sodium borohydride (NaBH₄) reduced poly(ε-caprolactone-co -4- carbonyl -ε-caprolactone) (P(CL-OPD)), while P(CL-OPD) was synthesized in bulk by ring-opening polymerization of ε-caprolactone and 4-carbonyl-ε-caprolactone (OPD) with stannous octoate as a catalyst. Their structures were confirmed by ¹HNMR, FT-IR and GPC. Dynamic light scattering (DLS), transmission electron microscopy (TEM), zeta potential measurements were used for nanoparticle characterization. TEM and DLS showed the nanoparticles were with spherical shape and uniform size distribution (mean diameter 70～100 nm), respectively. Zeta potential analysis revealed that the nanoparticles had an increased negative surface with the increase of carboxyl group concentration. UV spectroscopy was adopted to study the entrapment and release behaviour. The maximum 5-FU loading efficiency was 14.39% with the entrapment efficiency be 42%. In vitro release studies were performed in PBS at 37°C. Results of the study showed that the release behavior can be well-controlled, and the balanced release was up to 96 h. P(CL-OPD)-mal nanoparticles would provide increased benefit in biomedical and pharmaceutical applications.     

Synthesis and Properties of Poly(Aryl Ether Ketone) Copolymers with Trifluoromethyl‐Substituted Benzene in the Side Chain

The new monomer (4‐(4′‐trifluoromethyl)phenoxyphenyl)hydroquinone (TFPOPH) was synthesized in a three‐step synthesis. A series of poly(aryl ether ketone) copolymers were prepared by the reaction of (4‐(4′‐Trifluoromethyl)phenoxyphenyl)hydroquinone and hydroquinone (HQ) with 4,4′‐difluorobenzophenone (DFB) in the presence of potassium carbonate in tretramethylene sulfone (TMS). Thermal analyses of the fluorinated copolymers showed that the glass transition temperature and 5.0% weight loss temperature are similar with that of PEEK, and the crystallinity decreased with increasing of TFPOPH. For the copolymer synthesized with the molar fraction of TFPOPH in the diphenol monomers (TFPOPH, HQ) being over 0.2, no cold crystallization temperature and melting temperature were detected, indicating that these copolymers are almost amorphous. The crystal structure of the copolymers with the molar fraction of TFPOPH being not higher than 0.2 is rhombic. The solubility in polar aprotic solvents of poly(aryl ether ketone)s copolymers increases and dielectric constant decreases step by step.     

The side chain effects on TPD-based copolymers: the linear chain leads to a higher jsc

Abstract

Alkyl substituents appended to polymers play the determining role on self-assembly and film-forming properties, and on device performance. In this work, we highlight the effects of the linear and branched flexible chains appended to the acceptor moiety (A) in D-A type copolymers. Two thieno[3,4-c]-pyrrole-4,6-dione (TPD) based copolymers PT1 and PT2 with different alkyl chains, were designed and synthesized. By comparison their UV-vis absorptions, HOMO/LUMO energy levels, as well as the characters in polymer solar cells, the influences of alkyl chains were investigated. Both copolymers showed molecular weights of 21?kDa and similar optical properties with a medium band gap of 1.93?eV, while PT2 with the branched chain exhibited a lower HOMO than that of PT1 (?5.43 vs???5.37?eV). In bulk heterojunction (BHJ) solar cells, PT1 with a linear chain presented a short circuit current (J_sc) of 6.76?mA cm^?2, open circuit voltage (V_oc) of 0.89?V and power conversion efficiency (PCE) of 2.92%. To the contrary, PT2 showed a J_sc of 3.53?mA cm^?2, V_oc of 0.99?V, delivering a relatively lower PCE of 2.05%. The result indicates that appending a linear alkyl chain to the TPD unit could sufficient enhance the J_sc value of the related polymer.     

Fabrication of Gold Nano‐Structures with Azopolymer Templates

Fabrication of gold nano‐patterns has been demonstrated employing surface relief structures created on films of an azobenzene‐functionalized polymer as templates. The surface relief templates were photoinscribed on the azopolymer films in one‐step with two laser beams. Thin layers of gold were over‐coated on the polymer templates by thermal evaporation. Gold lines of a few hundred nanometer width were successfully fabricated by pyrolyzing the azobenzene polymer. Sub‐micron gold dots were also created. The resulting gold structures exhibited the same periodicity as the polymer templates.     

Multi-responsive cyclodextrin vesicles assembled by ‘supramolecular bola-amphiphiles’

Multi-responsive cyclodextrin vesicles (CDVs) self-assembled by ‘supramolecular bola-amphiphiles’, consisting of a guest (N,N′-bis(ferrocenylmethylene)-diaminohexane, 1) and a host (γ-hydroxybutyric-β-cyclodextrin, γ-HB-β-CD), were prepared and investigated for the first time. The morphologies and sizes of these novel vesicles in water were observed by transmission electron microscopy (TEM), scanning electron microscopy and dynamic light scattering. The effects of the host–guest ratio, the concentration and the solvent composition are also discussed. The host–guest interactions, complex stoichiometry and structures of 1·γ-HB-β-CD in water were investigated by cyclic voltammetry, UV and NMR spectroscopy. According to the complex stoichiometry, TEM observations and Chem3D estimation, the ‘supramolecular bola-amphiphiles’, made from 1·γ-HB-β-CD and assumed for the first time, formed the membranes of the CDVs. The CDV system was responsive to an oxidising agent, which is the first report on redox-responsive systems in this field. The CDVs are also responsive to pH and the presence of metal ions, such that they disassemble upon addition of acetic acid or Cu²⁺ ions, providing possible routes to drug delivery systems.     

Three coordination polymers of 5-aminoisophthalic acid with similar benzimidazole derivative ligands: synthesis,structure and DNA-binding studies

Three novel coordination polymers, [Co(NH₂-Aip)(H₂Bibim)] _n (1), [Co(NH₂-Aip)(HBibimop)] _n  √ nH₂O (2) and [Mn(NH₂-Aip) √ H₂O] _n  √ 2nH₂O (3) with NH₂-Aip and similar benzimidazole derivative ligands (NH₂-Aip = 5-aminoisophthalic acid, H₂Bibim = 2,2′-bibenzimidazole and HBibimop = 1,3-bis(benzimidazol-2-yl)-2-oxapropane), have been synthesised under hydrothermal conditions and structurally characterised by single-crystal X-ray diffraction analysis, elemental analysis and IR spectroscopy. 5-Aminoisophthalic acid ligand adopts μ₂-, μ₃- and μ₄-bridge coordination fashion and benzimidazole derivatives exist as terminal- and bridge-mode in complexes 1–3. The intricate hydrogen bonds and π–π stacking interactions in supramolecular framework are discussed. Using the combination of ultraviolet–visible absorption titration and fluorescence spectra, the experimental results show that complexes 1 and 2 bind to DNA in an intercalative mode and their DNA-binding constants (K _b ) are also found.     

Profiling primaquine metabolites in primary human hepatocytes using UHPLC‐QTOF‐MS with 13C stable isotope labeling

Therapeutic efficiency and hemolytic toxicity of primaquine (PQ), the only drug available for radical cure of relapsing vivax malaria are believed to be mediated by its metabolites. However, identification of these metabolites has remained a major challenge apparently due to low quantities and their reactive nature. Drug candidates labeled with stable isotopes afford convenient tools for tracking drug‐derived metabolites in complex matrices by liquid chromatography‐tandem mass spectrometry (LC‐MS‐MS) and filtering for masses with twin peaks attributable to the label. This study was undertaken to identify metabolites of PQ from an in vitro incubation of a 1:1 w/w mixture of ¹³C₆‐PQ/PQ with primary human hepatocytes. Acquity ultra‐performance LC (UHPLC) was integrated with QTOF‐MS to combine the efficiency of separation with high sensitivity, selectivity of detection and accurate mass determination. UHPLC retention time, twin mass peaks with difference of 6 (originating from ¹³C₆‐PQ/PQ), and MS‐MS fragmentation pattern were used for phenotyping. Besides carboxy‐PQ (cPQ), formed by oxidative deamination of PQ to an aldehyde and subsequent oxidation, several other metabolites were identified: including PQ alcohol, predictably generated by oxidative deamination of PQ to an aldehyde and subsequent reduction, its acetate and the alcohol's glucuronide conjugate. Trace amounts of quinone‐imine metabolites of PQ and cPQ were also detected which may be generated by hydroxylation of the PQ/cPQ quinoline ring at the 5‐position and subsequent oxidation. These findings shed additional light on the human hepatic metabolism of PQ, and the method can be applied for identification of reactive PQ metabolites generated in vivo in preclinical and clinical studies. Copyright © 2013 John Wiley & Sons, Ltd.     

Hydrothermal synthesis, crystal structure, and photoluminescence of a new 2D cadmium(II) complex: {Cd(C8H5O3Cl2)2(C10H8N2)} n

One new cadmium coordination polymer, [Cd(2,4-Dcp)₂(4,4-Bipy)] _n (I) (2,4-HDcp = 2,4-dichlorophenoxyacetic acid, 4,4′-Bipy = 4,4′-bipyridine) with 2D layer structure, has been prepared by the hydrothermal synthesis and characterized by elemental analysis, IR, TGA and single-crystal X-ray diffraction. Complex I crystallizes belong to monoclinic system and has C2/c space group. Each Cd²⁺ ion is six-coordinated and located at an octahedral geometry. The Cd²⁺ ions are linked by bidentate 2,4-Dcp groups into a linear chain in which the benzene rings of 2,4-Dcp ligands point alternately up and down. These chains are further connected into a sandwich-like layer though 4,4′-Bipy ligands. Furthermore, the photoluminescence and life-time of I in the solid state have been studied.     

Thermogravimetry study of the pyrolytic characteristics and kinetics of macro-algae Macrocystis pyrifera residue

Macrocystis pyrifera is one important marine macro-algae, while its residues produced by industrial alginate extraction is a hot potato. To figure out whether its residue is suitable for pyrolysis for biofuel, the pyrolytic characteristics and kinetics of macro-algae M. pyrifera residue was investigated using thermogravimetric method from 50 to 800 °C in an inert argon atmosphere at different heating rates of 5, 10, 20, and 30 °C min^?1. The activation energy and pre-exponential factor was calculated by Flynn–Wall–Ozawa, Kissinger–Akahira–Sunose, and Popescu methods, and the kinetic mechanism was deduced by Popescu method. The results showed that the primary devolatilization stage of M. pyrifera residue can be described by Jander function $ \left(\left[ {1 - \left( {1 - \alpha } \right)^{1/3} } \right]^{2}\right) $ . The average activation energy of M. pyrifera residue was 222.4 kJ mol^?1. The results suggested that the experimental results and kinetic parameters provided useful information for the design of pyrolytic processing system using M. pyrifera residue as feedstock.