UV photopolymerized hydrogels with β-cyclodextrin moieties

Hydrophilic hydrogels based on poly(ethylene glycol)–poly(propylene glycol)–poly(ethylene glycol) block copolymers have potential applications in drug delivery, tissue engineering and other biomedical devices due to their excellent biocompatibility and environmental sensitivity. However, they also exhibit some shortcomings in terms of swelling and mechanical properties as well as affinity for water-insoluble or hydrophobic drug molecules. To address these limitations, new polymeric hydrogels with β-cyclodextrin moieties were prepared by UV photo-polymerization of maleic anhydride-substituted β-CD (MAH-CD) and the block copolymer macromer from Pluronic F68 and poly(ɛ-caprolactone). Their swelling and dynamic rheological properties were investigated with respect to the effects of feed compositions. It was found that the swelling ratio, storage modulus and loss modulus of the resulting hydrogel increased with the increase of MAH-CD amount. Incorporation of MAH-CD resulted in strong viscoelastic system with dominating elastic behavior.     

Fabrication of aerogels from cellulose nanofibril grafted with β-cyclodextrin for capture of water pollutants

Journal of Porous Materials - Interactions at the molecular and surface chemistry are some of the key factors that determine the adsorption capacity of pollutants and emerging contaminants in...     

Synthesis and drug-release properties of biodegradable hydrogels having β-cyclodextrin

A new β-cyclodextrin (β-CD) methacrylated monomer was synthesized from the reaction of β-CD, glycidyl methacrylate. Based on inclusion character of β-CD, a series of hydrogels were prepared by irradiating the mixtures of β-CD methacrylate monomer (β-CD-Met), poly(ethylene glycol) monoacrylate, poly(ethylene glycol)diacrylate, fumaric acid monoethyl ester-functionalized poly(lactic-co-glycolic) acid, 1-vinyl-2-pyrrolidone, N,N′-methylene bisacrylamide, and the photoinitiator. Gel percentages and equilibrium swelling ratios (%) of hydrogels were investigated. It was observed that equilibrium-swelling ratio increased with increasing β-CD-Met content in the hydrogel composition. SEM images demonstrated that β-CD-Met-based hydrogel have lots of voids on the fractured surface. In this study, ibuprofen (IBU) which is capable of forming inclusion complex with β-CD was chosen. For the hydrogel with maximum CD content, the IBU drug loading was found as 9 mg/g dry gel. It can be concluded that the inclusion complex-formation capability of β-CD moiety increases the drug release by improving the aqueous solubility of hydrophilic drugs.     

pH-Dependent release of blue dextran from carboxymethyl-β-cyclodextrin hydrogels

Carboxymethyl-β-cyclodextrin (CM-β-CD) hydrogel was prepared by cross-linking β-CD and substituting the hydroxyl groups with carboxymethyl group. Epichlorohydrin (EPI) was used as a cross-linker and the molar ratio of EPI to β-CD was 10:1. The number of carboxymethyl group per β-CD residue was determined by a back-titration method and the value was 0.86. The swelling ratio of CM-β-CD hydrogel increased as the pH of medium increased. The carboxyl group will be ionized with increasing pH and an electrostatic repulsion developed within the hydrogels would be responsible for a higher swelling ratio at a higher pH. The degree of release of blue dextran from the hydrogel also increased as the pH of medium increased. The pH-dependent swelling ratio could account for the pH-sensitive release.     

Electrochemical investigations into host-guest interactions of a natural antioxidant compound with β-cyclodextrin

The electrochemical behavior of mangiferin (MGN), a natural antioxidant compound, is examined using cyclic and differential pulse voltammetry in a protic medium on a glassy carbon electrode. The voltammograms exhibit a single irreversible pH-dependent anodic wave with current controlled by adsorption.Complexes of MGN with β-cyclodextrin (β-CD) were prepared and their formation was confirmed by UV-vis spectroscopy and electrochemical experiments, using a self-assembled monolayer of cyclodextrin on a gold electrode. The association constant of MGN:β-CD complexes was estimated by the Benesi-Hildebrand method, based on the spectrophotometric quantification of free β-CD and by the direct method using cyclic voltammetry and the Langmuir isotherm.PM IRRAS experiments corroborated the inclusion process based on the observation of the corresponding peaks in the spectra of the samples.MGN was quantified using a simple electrochemical method based on a β-CD incorporated carbon nanotube (CNT)-modified electrode (β-CDCNT). The presence of β-CD led to a 10-fold lower detection limit than that obtained with a CNT-modified electrode.     

Synthesis of a gold(I) complex with a (thio)phosphine-modified β-cyclodextrin

A gold(I) complex with the bidentate ligand 6^A-S-[2-(diphenylphosphino)-ethyl]thio-β-cyclodextrin has been prepared. The complex has been studied by mass spectrometry as well as IR and NMR spectroscopy. The influence of the ligand:metal ratio on the coordination mode has also been examined.     

Preparation and characterization of thermo-sensitive microspheres with β-cyclodextrin groups

采用沉淀聚合机理,由一步法和两步法制备聚（N-异丙基丙烯酰胺-甲基丙烯酸缩水甘油酯） [P(NIPAM-co-GMA)]温敏性微球。其中一步法是同时加入所有反应物反应成微球,而两步法是先加NIPAM成微球,再加入GMA,最终均生成P(NIPAM-co-GMA)微球;再将改性的乙二胺代环糊精（EDA-β-CD）通过化学反应引入到P(NIPAM-co-GMA)微球结构中,制备得到聚（N-异丙基丙烯酰胺-甲基丙烯酸-2-羟丙基乙二胺基环糊精） [P(NIPAM-co-GMA/β-CD)]共聚高分子微球。分别用扫描电镜、红外光谱、控温激光粒度仪及光学显微镜对产物的形貌、结构和温敏特性进行了表征。结果表明,两种方法制备的微球均具有良好的单分散性和球形度,均能成功地固载β-环糊精（β-CD）基团,并且都有温度响应特性;但是,同一步法制备的微球相比,两步法制得的微球粒径明显较大,且微球固载有更多的β-CD。     

Syntheses and self-assembly of novel polyurethane–itaconic acid copolymer hydrogels

Novel physically crosslinked polyurethane–itaconic acid (PU–I) copolymer hydrogels were synthesized by the macroiniferter-controlled radical polymerization method. The structures of the PU–I copolymer hydrogels were characterized by ¹H NMR, FTIR, GPC, and DSC. The water contact angles and self-assembly of the PU–I copolymer hydrogels have been investigated. The results revealed that PU–I copolymer hydrogels have good hydrophilicity, so the water contact angles of polyurethane could be easily adjusted by controlling the content of the hydrophilic vinyl monomers. The PU–I copolymer hydrogels were subjected to solvent-induced self-assembly in THF + water to construct a variety of morphologies. The morphology of the PU–I copolymer hydrogels’ self-assembly was observed by scanning electron microscopy (SEM) and transmission electron microscopy (TEM), and the mechanism of self-assembly was investigated.     

Thermosensitive supramolecular hydrogels from atom transfer radical polymerization of polypseudorotaxanes self-assembled by triblock copolymer and α-cyclodextrins

We report novel thermosensitive supramolecular hydrogels with tunable crosslinking networks by using polypseudo-rotaxanes (PPRs) as macroinitiators in atom transfer radical polymerization and polyethylene glycol diacrylate (PEGDA) as bridge units. The PPRs were prepared by supramolecular self-assembly of α-cyclodextrin or 2-bromoisobutyryl bromide modified α-cyclodextrin (α-CD-BIBB) and triblock copolymer of F127 with bromopropionyl bromide terminals. The supramolecular hydrogels possess the crystal structure of inclusion complexes (ICs) and thermo-sensitive properties. The addition of mono-functional 2-hydroxyethyl methacrylate (HEMA) can enhance gelation. The swelling ratio (SR) was mainly influenced by the concentration of α-CD or modified α-CD, HEMA and PEGDA. The introduction of α-CDs was found to decrease the SR of hydrogels, while the introduction of α-CD-BIBBs could improve the SR. Meanwhile, gelation was tuned by regulating the concentration of HEMA. The SR of hydrogels was increased with the increase of the concentration of PEGDA, but decreased with the increase of that of HEMA. In the temperature range from 20 to 50 °C, the temperature sensitivity of hydrogels was mainly controlled by the state of gels. The introduction of PHEMA chains decreased the temperature responsivity of networks. The hydrogels prepared with α-CD-BIBBs threading onto the F127 chains showed the high thermo-sensitivity. The thermosensitive mechanism of hydrogels is due to the aggregation of PPO blocks in the networks.     

Fabrication and characterization of porous β-tricalcium phosphate scaffolds coated with alginate

All porous materials have a common limitation which is lack of strength due to the porosity. In this study, two different methods have been used to produce porous β-tricalcium phosphate (β-TCP) scaffolds: liquid-nitrogen freeze casting and a combination of the direct-foaming and sacrificial-template methods. Among these two methods, porous β-TCP scaffolds with acceptable pore size and compressive strength and defined pore-channel interconnectivity were successfully fabricated by the combined direct-foaming and sacrificial-template method. The average pore size of the scaffolds was in the range of 100–150 µm and the porosity was around 70%. Coating with 4 wt% alginate on porous β-TCP scaffolds led to higher compressive strength and low porosity. In order to make a chemical link between the β-TCP scaffolds and the alginate coating, silane coupling agent was used. Treated β-TCP scaffold showed improvements in compressive strength of up to 38% compared to the pure β-TCP scaffold and 11% compared to coated β-TCP scaffold.     

Synthesis and micellization of an amphiphilic biodegradable β-cyclodextrin/poly(γ-benzyl L-glutamate) copolymer

β-Cyclodextrin/poly(γ-benzyl L-glutamate) (β-CD-PBLG) copolymers were synthesized by ring-opening polymerization of N-carboxy-γ-benzyl L-glutamate anhydride (BLG-NCA) in N,N-dimethylformamide(DMF) initiated by mono-6-amino-β-cyclodextrin(H₂N-β-CD). The structures of the copolymers were determined by IR, ¹H NMR and GPC. The fluorescence technique was used to determine the critical micelle concentration (CMC) of copolymer micelle solution. The diameter and the distribution of micelles were characterized by dynamic light scattering(DLS) and its shape was observed by transmission electron microscopy(TEM). The results showed that BLG-NCA could be initiated by H₂N-β-CD to produce copolymer. These copolymers showed an amphiphilic nature and could self-assemble into nano-micelles in water. The CMC of copolymer solution and the size of micelle reduced with the increasing of the proportion of hydrophobic parts. TEM images demonstrated the micelles are all spherical. Such copolymers could be expected to find applications in drug delivery systems and other biomedical domains.     

Crosslinking of β-cyclodextrin and combining with ammonium polyphosphate for flame-retardant polypropylene

This work presents the synthesis of crosslinked hexamethylene diisocyanate β-cyclodextrins (HDI-CDs) by reacting β-cyclodextrin (β-CD) with HDI as a crosslinking agent at different feed ratios. As a novel char-forming agent, the HDI-CDs are combined with ammonium polyphosphate (APP) and applied in polypropylene (PP) to form intumescent flame-retardant composites. The structure of HDI-CDs is characterized by Fourier transform infrared spectra (FTIR), ¹³C nuclear magnetic resonance spectroscopy, and nitrogen adsorption–desorption test. The thermogravimetric analysis (TGA) results indicate that HDI-CDs have better char-forming performance than β-CD. FTIR spectra, X-ray diffraction, and Raman spectra characterization demonstrate that the reaction between HDI-CDs and APP contributes to the formation of a more stable char layer than β-CD and APP. According to the results of TGA, scanning electron microscopy, limiting oxygen index (LOI), UL-94, and X-ray photoelectron spectroscopy test, when the crosslinking degree of HDI-CDs is high enough (not less than β-CD:HDI = 1:3.6), the PP/APP/HDI-CDs composites can form a compact and dense char layer during combustion. Among all composites, PP/APP/HDI-CD(4) shows the best flame-retardant performance, which can pass the UL 94 V-0 rating with an LOI value of 32.8% when the loading of flame retardants is 28 wt %. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48320.     

Preparation of superparamagnetic β-cyclodextrin-functionalized composite nanoparticles with core–shell structures

In this article, we report an original and feasible protocol for the preparation of superparamagnetic β-cyclodextrin-functionalized composite nanoparticles with core–shell structures via cross linking reaction on the surface of carboxymethyl β-cyclodextrin-modified magnetite (Fe₃O₄) nanoparticles by using epichlorohydrin as a crosslinking agent. The structure and morphology of the prepared composite nanoparticles were studied by Fourier transform infrared spectrometry, X-ray diffraction measurement, transmission electron microscopy and the thermogravimetric analysis. The results show that the prepared roughly spherical composite nanoparticles (diameter about 10–20 nm) with core–shell structures turned out to be magnetite nanoparticles surface-surrounded by a layer of cross-linked CM-β-cyclodextrin polymer. Results of vibrating sample magnetometry testing and inclusive behaviour studying confirmed the superparamagnetism with saturation magnetization value of 52.0 emu/g in an external applied magnetic field of 20000 Oe and inclusion functionality of the composite nanoparticles consisting of magnetite cores and β-cyclodextrin moiety, which implies very important applications in targeting drug delivery technology and separation for specific substances.     

Preparation and electrochemical behavior of water-soluble inclusion complex of ferrocene with β-cyclodextrin polymer

A new water-soluble inclusion complex of ferrocene (Fc) with β-cyclodextrin polymer (β-CDP) was prepared by a facile strategy and characterized by ¹H NMR spectroscopy, elemental analysis, powder X-ray diffractometry, thermogravimetry, UV–vis spectroscopy and cyclic voltammetry. Compared with Fc and the inclusion complex of Fc with β-cyclodextrin (Fc-β-CD), the solubility of ferrocene-β-cyclodextrin polymer (Fc-β-CDP) was greatly enhanced due to the water-soluble β-CDP host. The ratio of β-cyclodextrin (β-CD) unit in β-CDP to Fc was determined as 1:1. At 25 °C, the dissociated constant of Fc-β-CDP was measured as 3.65 mM by UV–vis spectroscopy and cyclic voltammetry. The electrochemical properties of Fc-β-CDP in water were studied. The diffusion coefficients of oxidation state and reduction state were calculated as 3.52 × 10⁻⁷ cm² s⁻¹ and 3.93 × 10⁻⁷ cm² s⁻¹. The resulting value of standard rate constant was measured as 1.95 × 10⁻³ cm s⁻¹. The diffusion activation energy was calculated as 21.8 kJ mol⁻¹.     

A novel bridged organocobaloxime/ β-cyclodextrin inclusion complex produced by a β-cyclodextrin induced reaction

A cobalt-to-oxime carbon bridged organocobaloxime/β-cyclodextrin inclusion complex has been formed in a β-cyclodextrin induced reaction, which was confirmed by X-ray structure analysis and FAB-MS.     

pH-responsive amphiphilic H-shaped supramolecular copolymer via the inclusion complexation between β-cyclodextrin and adamantane

pH-responsive amphiphilic H-shaped copolymer was prepared by the supramolecular self-assembly between β-cyclodextrin-graft-poly(2-(N,N-diethylamino)ethyl methacrylate) (β-CD-(PDEAEMA)₂) and bi-adamantyl terminated poly(ε-caprolactone) (Ad-PCL-Ad). β-CD-(PDEAEMA)₂ was synthesized by click reaction of alkynyl-modified β-CD with azide PDEAEMA (PDEAEMA-N₃). Ad-PCL-Ad was synthesized by the DCC reaction of bi-hydroxyl terminated PCL (HO-PCL-OH) with adamantaneacetic acid. The supramolecular copolymer can self-assemble into micelles in water at room temperature. The micellization and pH-responsivity of the amphiphilic copolymer solution were investigated by transmittance, dynamic light scattering spectrophotometer, and transmission electron microscopy in water. Investigation shows that the micelles’ sizes can be adjusted through the alteration of the pH values of solutions and the supramolecular copolymer will have the potential applications in biomedical field.     

The drug release from a coated planar matrix with a sub-saturation loading in the core

A model was proposed for the drug release from a coated matrix system.To validate thismodel,5-Fu/EVAL matrices coated with various polymeric materials with different diffusivities wereprepared and characterized.These coated systems were experimentally investigated and graphically andquantitatively compared with theoretical values.The results show a good correlation between theoryand experiment.     

Synthesis and characterization of curdlan/β-cyclodextrin composite hydrogels for sustained-release

Curdlan/β-cyclodextrin (β-CD) composite hydrogels were prepared by using epichlorohydrin (ECH) and ethylene glycol diglycidyl ether (EGDGE) as cross-linkers respectively. The results showed that a macromolecular network structure was formed. This composite hydrogels showed certain temperature sensitivity, regular swelling ratio and unique mechanical property. The addition of β-CD improved the swelling property of hydrogels in neutral aqueous solution, showing completely opposite results to the cellulose/β-CD hydrogels. This composite hydrogel had certain temperature sensitivity and could sustained-release sodium salicylate for more than 8?hours. The curdlan/β-CD hydrogels, which were cross-linked by natural polymers, had a unique application prospect in the medicine.     

Synthesis of star poly(N-isopropylacrylamide) by β-cyclodextrin core initiator via ATRP approach in water

Star poly(N-isopropylacrylamide) (PNIPAAm) based on a β-cyclodextrin (β-CD) core macroinitiator was synthesized by means of atomic transfer radical polymerization (ATRP) in water using copper(I)/2,2bipyridyl complex as a catalytic system at temperature above the lower critical solution temperature (LCST) of the PNIPAAm. The macroinitiator was prepared by the transesterification reaction of the (β-CD) with 2-bromopropionyl bromide. The LCST of the samples upshifts slightly when the absolute molecular mass of the star PNIPAAm increases. Over the phase transition, the solutions became bluish opalescent due to formation of a heterogeneous phase system consisting of collapsed polymer particles in water. Atomic force microscopy and dynamic light scattering analyses indicated two populations of self-assembled polymer structure: a larger population and a smaller population. The smaller size suggests to self-assembly of polymer micelles and the large one corresponds to aggregates of polymer micelles or star polymers coupled. Polydispersity of the star PNIPAAm ranged from 1.60 to 4.04 within 15 h of reaction, which was attributed to the collapse of the PNIPAAm chains at temperature above the LCST that causes a decrease of the polymer reactivity. This was also attributed to the star–star coupling that generates twice the value of the polydispersity for any time before 15 h of polymerization.     

Compatibilization of polystyrene/poly(dimethyl siloxane) solutions with star polymers containing a γ-cyclodextrin core and polystyrene arms

Solutions of polystyrene and poly(dimethyl siloxane) in chloroform are compatibilized by the addition of a small amount of a star polymer consisting of a γ-cyclodextrin core and polystyrene arms. Compatibilization is visually observed when turbid PDMS/PS emulsions become clear upon addition of the CD-star molecule. The mechanism of compatibilization involves threading of the CD-core by PDMS and solubilization of the resulting “slip-ring graft copolymer” via the PS star arms. This process breaks up the undissolved PDMS domains into smaller, more stable micelles. Evidence for threading of the CD-core by PDMS is found using ROESY 2D-NMR. Intrinsic viscosity measurements for the compatibilized solutions show behavior similar to conventional graft copolymers which form micelles in a selective solvent. Dynamic light scattering measurements suggest that the micelle size is approximately 20 nm. The effects of varying the PDMS molecular weight, PDMS concentration and CD-star concentration are studied.