Thermosensitive mucoadhesive gel formulation loaded with 5-Fu: cyclodextrin complex for HPV-induced cervical cancer

Human Papilloma Virus (HPV) infections are the major cause of cervical cancers. To achieve a better therapeutic efficacy and patient compliance in the treatment for HPV-induced cervical cancers, anticancer agent 5-fluorouracil has been formulated in a vaginal gel using the thermosensitive polymer Pluronic^® F127 together with alternative mucoadhesive polymers e.g., hyaluronic acid, Carbopol 934 and hydroxypropylmethylcellulose. To increase its aqueous solubility and to achieve the complete release of 5-FU from the gel, the drug was incorporated as its inclusion complex with 1:1 molar ratio with either β-cyclodextrin or hydroxypropyl-β-cyclodextrin. Following the characterization of drug:CD complexes, thermosensitive gel formulations containing different mucoadhesive polymers and the drug in free or complexed form were characterized in vitro by determining the gelation temperature and the rheological behavior of different formulations along with the in vitro release profiles of these formulations in pH 5.5 citrate buffer. It was observed that complexation with cyclodextrin accelerated the release of 5-FU with the exception of formulation containing Carbopol 934 as mucoadhesive polymer. As far as rheological properties are concerned, favorable thermosensitive in situ gelling properties were obtained with formulations containing HPMC as mucoadhesive polymer. Complete release of 5-FU from gels were obtained with both complexes of β-CD and HP-β-CD and cytotoxicity studies against HeLa human cervical carcinoma cells demonstrated that 1% 5-FU:CD complexes were equally effective as 1% free 5-FU indicating better therapeutic efficacy with lower dose.     

New biodegradable polymers for delivery of bioactive agents

Biodegradable, thermosensitive triblock copolymer, PLGA-PEG-PLGA, can be easily fabricated into drug-loaded microspheres or injectable in situ hydrogel system for protein or water-insoluble drugs without use of organic solvent. Aqueous-based microsphere exhibited continuous release of intact insulin in vitro for 3 weeks while the microspheres prepared using dichloromethane showed initial burst and incomplete release. Confocal miscoscopy images of microspheres corroborated the release pattern. Next study with an injectable in situ hydrogel (ReGel^TM) exhibited zero-order insulin release in vitro and sustained plasma insulin level for 2 weeks in vivo upon single subcutaneous injection in SD rats.     

Reactive methacrylate systems for dental bioadhesives

The procedure of restoring missing crown part of a human tooth with use of experimental materials, including new functional dimethacrylate monomers, is presented. The essential steps are precise evaluation of root canal cavities and providing a good adhesion of restorative materials to tooth structures. Magnetic resonance microscopy is considered to be a valuable supporting technique in restorative dentistry.     

Pyrrole/macrocycle/MOF supramolecular co-assembly for flexible solid state supercapacitors

Supramolecular assemblies constructed through the encapsulation of conductive polymers (CPs) by macrocyclic molecules have attracted increasing interest in the fields of supramolecular chemistry and electrochemistry. In this work, an effective strategy was reported to improve the stability and conductivity of CPs by electrochemically constructing different supramolecular assemblies composed of macrocycles and CPs. Typically, we uploaded zinc-based MOF (ZIF-8) onto carbon nanotube film (CNTF) and further electrically deposited macrocycles and CPs to gain the flexible conductive electrodes. Herein, five different supramolecular macrocycles, including α-cyclodextrin (α-CD), sulfato-β-cyclodextrin (SCD), sulfonatocalix[4]arene (SC[4]), cucurbit[6]uril (CB[6]) and cucurbit[7]uril (CB[7]) were utilized and the electrochemical performances of the assembly electrodes increased in an order of α-CD < SCD < SC[4] < CB[6] < CB[7], significantly improving the areal capacitance up to 1533 mF/cm². This strategy may provide a new way for the application of macrocyclic supramolecules in electrochemical systems.     

吲哚美辛纳米胶体金分子印迹聚合物的制备及其在固相萃取中的应用

以吲哚美辛(IDM)为模板分子,丙烯酰胺(AA)为功能单体,乙二醇二甲基丙烯酸酯(EGDMA)为交联剂,本体聚合法制备过程中加入纳米胶体金,合成了吲哚美辛胶体金分子印迹聚合物(MIPs/Au),利用MIPs/Au表面胶体金对蛋白吸附作用,将抗吲哚美辛的多克隆抗体固定在MIPs/Au上,得到表面固定有抗体的新型聚合物(MIPs/Au-Ab)并对其进行了表征。制备了填充材料为MIPs/Au-Ab的固相萃取柱并对其上样、淋洗和洗脱条件进行了优化,并将所制备的新型萃取柱用于水样中IDM的分离富集。抗吲哚美辛抗体交联在聚合物表面,不仅增加了萃取柱的特异性吸附容量,而且有效地降低了MIP的非特异性吸附。     

Regioregular poly(thiophene-3-alkanoic acid)s: water soluble conducting polymers suitable for chromatic chemosensing in solution and solid state

Regioregular polythiophenes with pendant carboxylic acid functionality, poly(thiophene-3-propionic acid) (PTPA, 3) and poly(thiophene-3-octanoic acid) (PTOA, 4), were prepared as water soluble conducting polymers and their chemosensory response was studied. Treatment with aqueous base generated intensely colored water soluble conducting polymer salts, with the color varying both as a function of counter ion size and length of the carboxyalkyl substituent. PTPA showed a different colorimetric response to each of the alkali earth metals whereas the longer chain PTOA was only sensitive to ions larger than Et₄N⁺. Distinct color changes were also noted in studies of divalent cations known to selectively bind carboxylates, such as Zn²⁺, Mn²⁺, and Cd²⁺. Cast films of PTPA have been found to act as sensors to acid vapor (Δλ_max of up to 132 nm). IR shows that the polymer self-assembles upon HCl vapor exposure, and that the process is completely reversible, leading to a good solid-state sensor for acids. This work demonstrates that regioregular polythiophenes containing acid side-chains have tremendous potential in the development of new sensors.     

Ionic IPNs as novel candidates for highly conductive solid polymer electrolytes

Five ionic imidazolium based monomers, namely 1‐vinyl‐3‐ethylimidazolium bis(trifluoromethylsulfonyl)imide (ILM1), 1‐vinyl‐3‐(diethoxyphosphinyl)‐propylimidazolium bis(trifluoromethylsulfonyl)imide (ILM2), 1‐[2‐(2‐methyl‐acryloyloxy)‐propyl]‐3‐methylimidazolium bis(trifluoromethylsulfonyl)imide (ILM3), 1‐[2‐(2‐methyl‐acryloyloxy)‐undecyl]‐3‐methylimidazolium bis(trifluoromethylsulfonyl)imide (ILM4), 1‐vinyl‐3‐ethylimidazolium dicyanamide (ILM5) were prepared and used for the synthesis of linear polymeric ionic liquids (PILs), crosslinked networks with polyethyleneglycol dimethacrylate (PEGDM) and interpenetrating polymer networks (IPNs) based on polybutadiene (PB). The ionic conductivities of IPNs prepared using an in situ strategy were found to depend on the ILM nature, T_g and the ratio of the other components. Novel ionic IPNs are characterized by increased flexibility, small swelling ability in ionic liquids (ILs) along with high conductivity and preservation of mechanical stability even in a swollen state. The maximum conductivity for a pure IPN was equal to 3.6 × 10^?5 S/cm at 20 °C while for IPN swollen in [1‐Me‐3‐Etim] (CN)₂N σ reached 8.5 × 10^?3 S/cm at 20 °C or 1.4 × 10^?2 S/cm at 50 °C. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4245–4266, 2009     

Molecularly imprinted polymers for on-line preconcentration by solid phase extraction of pirimicarb in water samples

The synthesis and performance of a molecularly imprinted polymers (MIPs) as a selective solid phase extraction sorbent for the preconcentration of the carbamate pirimicarb from water samples is described. The MIP was prepared using pirimicarb as the template, methacrylic acid as the functional monomer and ethylene glycol dimethacrylate as the cross-linking monomer, and using chloroform as the solvent. The detection of pirimicarb was carried out by differential pulse voltammetry (DPV) at a hanging mercury drop electrode (HMDE) in 0.1 mol l⁻¹ HCl. Solvents of different polarities were checked for the polymer synthesis, and different experimental variables (sample pH, selection of the eluent used, eluent volume, analyte and eluent flow rates and sample volume) associated with the rebinding/extraction process were optimised. For a 25 ml sample, the process took about 13 min and resulted in a nominal enrichment factor of 50 (eluent MeOH:H₂O:HAc, 7:2:1; 0.5 ml) for pirimicarb. A limit of detection of 4.1 μg l⁻¹ was obtained, and a good reproducibility of the measurements using different MIP microcolumns was found. Furthermore, the MIP selectivity was evaluated by checking several substances with similar and different molecular structures to that of pirimicarb. As an application, pirimicarb was determined in water samples of diverse origin which were spiked at a concentration level of 71.5 μg l⁻¹.     

Phosphomolybdate-modified multi-walled carbon nanotubes as effective mediating systems for electrocatalytic reduction of bromate

Electrocatalytic properties (towards reduction of bromate in 0.5 mol dm⁻³ H₂SO₄) of multi-walled carbon nanotubes (CNTs) modified with phosphododecamolybdate (PMo₁₂) monolayers have been diagnosed using cyclic voltammetry and amperometry. The ability of negatively charged PMo₁₂-modified CNTs to attract electrostatically ultra-thin, positively charged conducting polymer (PEDOT or polypyrrole) structures is explored to grow in controlled manner hybrid organic-inorganic network electrocatalytic films. Due to the presence of three-dimensionally distributed CNTs, the films’ conductivity and porosity are improved. The hybrid systems utilizing polypyrrole, rather than PEDOT, have produced fairly higher bromate electroreduction catalytic currents. Comparison is also made to Nafion-stabilized dispersion of PMo₁₂-modified CNTs inks. The latter system is characterized by good stability and relatively the highest sensitivities with respect to bromate concentration.     

New terpyridine macroligands as potential synthons for supramolecular assemblies

A Williamson type etherification approach was applied for the reaction of 4′-chloro-2,2′:6′,2′′-terpyridine with a number of well-defined mono- and bis-hydroxy functionalized polymers, namely poly(tetrahydrofuran), poly(2-ethyl-2-oxazoline) and Pluronics®. The resulting terpyridine functionalized polymers were characterized by ¹H NMR spectroscopy and SEC, as well as MALDI-TOF-MS demonstrating the successful functionalization. This type of end-functionalized chelating macromolecules could be considered as key candidates for the preparation of metallo-supramolecular polymers via metallo-terpyridine complexation; the principle feasibility was demonstrated by UV-vis titration of iron(II) chloride to bis-terpyridine functionalized poly(tetrahydrofuran).     

Integral algorithm and density matrix integration scheme for ab initio band structure calculations on polymeric systems

A new program for band structure calculations of periodic one-dimensional systems has been constructed. It is distinguishable from other codes by the efficient two-electron integral evaluation and the integration schemes of the density matrix in the first Brillouin zone. The computation of polymeric two-electron integrals is based on the McMurchie Davidson algorithm and builds batches of the different cell indices included in the polymeric system. Consequently it presents efficient scaling with respect to the number of unit cells taken into account. Our algorithm takes into account fully the polymeric symmetry rather than the molecular symmetry. A semidirect procedure where only exchange integrals are computed at each SCF cycle is proposed in order to maintain balance between computation time and disk space. In addition, the integration of the density matrix over a large number of cell indices can be performed by different methods, such as Gauss-Legendre, Clenshaw-Curtis, Filon, and Alaylioglu-Evans-Hyslop. This last scheme is able to obtain an accuracy of 10(-13) a.u. on each individual density matrix element for all cell indices with only 48 k-points.     

New epoxy-siloxane hybrid binder for high performance coatings

The novel chemistry achieved by condensation reaction of an aliphatic epoxy with a polysiloxane results in an epoxy-siloxane hybrid binder whose unique physical characteristics allow its use as a durable binder for the protective coatings industry. The new epoxy-siloxane coating system enables the zinc primer to be protected by a single topcoat. This results in reductions in application time, less overspray and a much simplified maintenance for corrosion protection. Furthermore the reduced number of coats and overspray results in about 70% less solvent emission to the atmosphere.     

Design of New Reaction Fields for Spherical Polypyrrole Particle Synthesis

Summary: Polypyrrole conducting polymers have been investigated widely for various applications because of their thermal and environmental stability and good electrical conductivity. Using chemical oxidative polymerization for the synthesis of polypyrrole particles, the reaction rate is very fast. In this study, we designed two new reaction fields for the synthesis of spherical polypyrrole nanoparticles. In the first system, oxidative polymerization of monomer droplets infused in a water/oil (W/O) emulsion reaction field was investigated. The second system employed dispersed monomer in an aqueous solution with a low concentration of oxidant in which polymerization was augmented by ultrasonic irradiation. Effective control of the reaction rate was important for enabling the synthesis of fine spherical polypyrrole particles.     

Star‐shaped polymers having side chain poss groups for solid polymer electrolytes; synthesis,thermal behavior,dimensional stability,and ionic conductivity

A series of organic/inorganic hybrid star‐shaped polymers were synthesized by atom transfer radical polymerization using 3‐(3,5,7,9,11,13,15‐heptacyclohexyl‐pentacyclo[9.5.1.1^3,9.1^5,15.1^7,13]‐octasiloxane‐1‐yl)propyl methacrylate (MA‐POSS) and poly(ethylene glycol) methyl ether methacrylate (PEGMA) as monomers and octakis(2‐bromo‐2‐methylpropionoxypropyldimethylsiloxy)octasilsesquioxane as an initiator. Star‐shaped polymers with methyl methacrylate (MMA) and PEGMA moieties were also prepared for comparison purposes. Dimensionally stable freestanding film could be obtained from the hybrid star‐shaped polymer containing 26 wt % of MA‐POSS moieties although its glass transition temperature is very low, ?60.9 °C. As a result, the hybrid star‐shaped polymer electrolyte containing lithium bis(trifluoromethanesulfonyl)imide showed ionic conductivities (1.75 × 10^?5 S/cm at 30 °C), which were two orders of magnitude higher than those of the star‐shaped polymer electrolyte with MMA moieties. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

New imidazole‐functionalized polyfluorene derivatives: convenient postfunctional syntheses,sensitive probes for metal ions and cyanide,and adjustable output signals with diversified fluorescence color

Based on our previous work on the sensitive and selective conjugated fluorescent polymeric sensors toward cyanide, 2,1,3‐benzothiadiazole and 4,7‐bis(thiophen‐2‐yl)‐2,1,3‐benzothiadiazole were incorporated into the polyfluorene backbone to yield three new polymers bearing imidazole moieties in the side chains, with different fluorescence color. The fluorescence could be turned off by Cu²⁺ ions and then recovered on addition of cyanide, making them good cyanide sensors with the detection limit down to 1.9 μM. Moreover, by fully understanding this “turn off–turn on” strategy and using the cooperation of two polymers with different fluorescence color, the emission color of the mixture system of one of the imidazole‐containing polymers and one from the corresponding polymers without imidazole ones, could be adjusted by the concentrations of the added copper and cyanide ions, leading to the output fluorescent signals diversity. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

New reaction for the preparation of liquid rubber

The article reports on the noncatalytic transformation of a polybutadiene (number‐average molecular weight = 128,000) into a functionalized liquid rubber via the carboxidation of the polymer C?C bonds by nitrous oxide. The reaction was conducted in a benzene solution at 160–230 °C and a pressure of 3–6 MPa. The carboxidation mechanism was determined. The main route (95%) of the reaction proceeded without cleavage of C?C bonds and led to the formation of ketone groups in the polymer backbone. A minor route (5%) of the reaction proceeded with the cleavage of C?C bonds, yielding two smaller fragments containing aldehyde and vinyl end groups. The availability of the cleavage route could lead to a dramatic decrease in the molecular weight, which, depending on the carboxidation degree, could be 1–2 orders of magnitude less than that of the initial material. Thus, the carboxidation of more than 15% of the polybutadiene C?C bonds transformed it into a C?O‐functionalized liquid rubber with a narrow molecular weight distribution. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2510–2520, 2006     

Thermotropic laterally attached liquid crystalline polymers: I. New stationary phases for high-performance liquid chromatography

Up to now thermotropic liquid crystalline side chain polymers have been seldom used as stationary phases in high-performance liquid chromatography (HPLC). The preparation of a new class of surface modified silica gels is reported. They are obtained by coating on the silica support liquid crystalline polysiloxanes with mesogenic side groups laterally attached to the polymer backbone through a flexible spacer. Their chromatographic behavior in reversed-phase HPLC is described for the separation of polycyclic aromatic hydrocarbons. The results show excellent planarity and rod shape recognition capabilities. Comparisons with low-molecular-mass liquid crystalline-bonded silica and longitudinally attached liquid crystalline polymer-coated stationary phase are also reported. Finally, comparisons to commercially available C₁₈ phases are described for the separation of complex mixtures.