Fabrication of thermo-responsive hydrogels from star-shaped copolymer with a biocompatible β-cyclodextrin core

A thermally reversible hydrogel composed of a three-arm star copolymer with a specific host β-cyclodextrin (β-CD) center has been developed. The synthesis of this star copolymer initiates with β-CD core, from which sequential polymerization of a temperature-responsive poly(N-isopropylacrylamide) (PNIPAM) block and a hydrophilic poly(N,N-dimethylacrylamide) (PDMA) block as asymmetric arms (named β-CD-g-(PNIPAM-b-PDMA)₃) is performed via RAFT protocol. Below the lower critical solution temperature (LCST) of PNIPAM segment, the polymer is of good water-solubility and exhibits a sol state. Upon thermal stimulus, free-standing hydrogels can be formed rapidly at sufficiently high concentrations. By comparing the sol–gel transition of the star polymer with that of its linear counterpart without this feature, we concluded that the special star-shape topology and the thermal-collapsed PNIPAM chains were responsible for this gelation behavior. The rheology measurements indicate the mechanical properties of the polymer hydrogels and the thermal reversibility of the sol–gel transition. Using Rhodamine B as a molecule to model a typical drug, we realize the favorable encapsulation and releasing process from the hydrogel, demonstrating that this star polymer has the potential to function as an injectable hydrogel for drug delivery and gene transport.     

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.     

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。     

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.     

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,characterization, and drug release properties of poly(2-hydroxyethyl methacrylate) hydrogels having β-cyclodextrin functionality

A new β-cyclodextrin urethane-methacrylate monomer was synthesized from the reaction of toluene-2,4-diisocyanate, 2-hydroxyethyl methacrylate (HEMA), and β-cyclodextrin (β-CD). Based on inclusion character of β-CD, a series of hydrogels were prepared by irradiating the mixtures of β-cyclodextrin urethane-methacrylate monomer (β-CD-UM), poly(ethylene glycol) diacrylate (PEG-DA), HEMA, and the photoinitator. Gel percentages and equilibrium swelling ratios (%) of hydrogels were investigated. It was observed that the equilibrium-swelling ratio increased with increasing β-CD-UM content in the hydrogel composition. SEM images demonstrated that β-CD-UM based hydrogel have porous fractured surface. In this study four different drug molecules, salicylic acid, sulfathiazole, rifampicin, and methyl orange as model drug, which are capable of forming inclusion complexes withβ-CD were chosen. For sulfathiazole and rifampicin, the drug loadings are very low (0.04 and 0.008 mmol/g dry gel), whereas methyl orange and salicylic acid drug uptakes are found as 0.15 and 0.18 mmol/g dry gel, respectively. The incorporation of β-CD-UM comonomer into the gel slightly reduces the methyl orange and salicylic acid releases. However, a significant enhancement was achieved in the case of sulfathiazole delivery. It can be concluded that the inclusion complex formation capability of β-CD moiety increases the drug release by improving the aqueous solubility of hydrophobic drugs. On the other hand, in the case of hydrophilic drugs, the drug release retards by forming strong drug-β-CD complex and reducing the drug diffusivity. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

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 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.     

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.     

Study on β-cyclodextrin grafting with chitosan and slow release of its inclusion complex with radioactive iodine

β-CD-2-CTS was synthesized by β-cyclodextrin reacting with p-toluenesulfonyl chloride, then grafting with chitosan. The infrared spectra analysis and ¹³C NMR confirmed that β-cyclodextrin reacted with p-toluenesulfonyl chloride at the 2-position carbon atom in the substituted glucose unit of β-cyclodextrin and formed β-CD-2-OTs. In the ¹³C NMR of β-CD-2-OTs, the characteristic peak of the 2-postion carbon atom in the substituted glucose unit of β-cyclodextrin appeared at 78.43 ppm. β-CD-2-CTS was characterized with infrared spectra analysis and X-ray diffraction. In the infrared spectra of β-CD-2-CTS, the characteristic peak of α-pyanyl vibration of β-CD was at 848.6 cm⁻¹. The characteristic peak of β-pyanyl vibration of CTS was at 894.9 cm⁻¹. The X-ray diffraction analysis showed that the peak at 2θ = 20° decreased greatly in β-CD-2-CTS. The polymer inclusion complex of β-CD-2-CTS with iodine was prepared and its inclusion ability was studied. The experimental results showed that a nice bit of iodine was included with β-CD-2-CTS and formed a stable inclusion complex. After the subcutaneous implantation of the polymer inclusion complex of β-CD-2-CTS with ¹³¹I₂ in rats, ¹³¹I₂ exhibited the property of slow release. ¹³¹I₂ in the blood of rats decreased slowly. ¹³¹I₂ in the blood of rats maintained approximately half of maximum for 70 days later, and maintained much higher radioactivity in the organs of rats compared to the inclusion complex of β-CD with ¹³¹ I₂, too. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2414–2421, 2001     

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.     

Synthesis of water dispersible reduced graphene oxide via supramolecular complexation with modified β-cyclodextrin

A noncovalent functionalization of the edges of reduced graphene oxide (RGO) with β-cyclodextrin-graft-hyperbranched polyglycerol (β-CD-g-HPG) was successfully performed via a host-guest interaction. The results showed that β-CD-g-HPG disperses the graphene sheets better than pure β-CD or HPG. The resulted supramolecular structure is stable in neutral water medium more than one week. However, in acidic medium the host-guest interaction is collapsed and graphene nanosheets precipitate.     

Graphene–polymer hydrogels with stimulus-sensitive volume changes

The reversible stimulus-responsive volume change in graphene materials has never been realized, due to the irreversible restacking or agglomeration of graphene sheets. In this study, the graphene–polymer hydrogel with reversible volume changes has been prepared by a hydrothermal method. It has good electrical conductivity, high mechanical strength and a tunable electrical conductivity. The hydrogel exhibits reversible volume changes in response to an electric current, which makes it a potential candidate for artificial muscle devices.     

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...     

Structure-retention correlation of isomeric bile acids in inclusion high-performance liquid chromatography with methyl β-cyclodextrin

The structure-retention correlation of various C₂₄ bile acid isomers was studied by the addition of methyl β-cyclodextrin (Me-β-CD) to mobile phases in reversed-phase high-performance liquid chromatography (HPLC). The compounds examined include a series of monosubstituted bile acids related to cholanoic acids differing from one another in the position and configuration of an oxygen-containing function (hydroxyl or oxo group) at the position C-3, C-6, C-7, or C-12 and the stereochemistry of the A/B-ring fusion (trans 5α-H and cis 5β-H) in the steroid nucleus. The inclusion HPLC with Me-β-CD was also applied to biologically important 4β- and 6-hydroxylated bile acids substituted by three to four hydroxyl groups in the 5β-steroid nucleus. These bile acid samples were converted into their fluorescence prelabeled 24-pyrenacyl ester derivatives and chromatographed on a Capcell Pak C₁₈ column eluted with methanol-water mixtures in the presence or absence of 5 mM Me-β-CD. The effects of Me-β-CD on the retentions of each compound were correlated quantitatively to the decreasing rate of capacity factors and the relative strength of host-guest inter-actions. On the basis of the retention data, specific and nonspecific hydrogen-bonding interactions between the bile acids and the Me-β-CD were discussed.     

Synthesis,characterization of β-CD based novel hydrogels with dual objectives of drug release and dye removal

Iranian Polymer Journal - In our recent work, we have reported on hydrogels devoid of cross-linkers. After observing the successful swelling and water retention properties, we have introduced...     

Suprarmolecular hydrogels driven by the dual host–guest interactions between α-cyclodextrin and ferrocene-modified poly(ethylene glycol) with low-molecular-weight

In general, α-cyclodextrin (α-CD) and low-molecular weight poly(ethylene glycol) (low-MW PEG) (M_w = 400–10,000) cannot construct supramolecular hydrogels but easily form crystalline precipitates. In this study, low-MW PEG (M_n = 2000, PEG-2000) was functionalized by ferrocene as mono-end-group. The obtained ferrocene-modified PEG-2000 (FcPEG-2000) further self-assembled into supramolecular hydrogel with α-CD even at low concentration (C_FcPEG-2000 = 17 mg/ml), driven by dual host–guest interaction between α-CD and FcPEG-2000. Interestingly, the hydrogel was still observed even when hydrophobic Fc group was oxidized to hydrophilic ferrocenium (Fc⁺) or included into the cavity of β-CD. In the former case, the existence of Fc⁺ end groups is considered to decrease the probability of PEG de-penetration from α-CD cavity, so that α-CDs have more location and opportunities to aggregate into more channel-type crystalline domains as physical cross-linking points. While in the later case, the synergistic effect of host–guest interaction between β-CD and ferrocenyl groups and host–guest interaction between α-CD and PEG chains are considered to be the main reason. The resultant FcPEG-2000 based hydrogels showed the property of shear-thinning.     

Inclusion complexes of eucalyptus essential oil with β-cyclodextrin: preparation,characterization and controlled release

In this study, eucalyptus essential oil (EEO) was encapsulated into β-cyclodextrin (β-CD) by saturated aqueous solution method. The success of EEO encapsulation was confirmed by laser light scatting, scanning electron microscopy, Fourier transform infrared spectroscopy, differential scanning calorimeter and thermogravimetric analysis. Releasing characteristics experiments were carried out at various temperatures, relative humidity (RH), storage time and high temperature stability test. Release kinetics of EEO from the inclusion complexes was investigated by zero-order kinetics, first-order kinetics and Avrami’s equation. The result showed that the release model of EEO from inclusion complexes fitted better for Avrami’s equation. Kinetics analysis based on the Avrami’s equation revealed that the release of EEO was accelerated with the increases of RH and temperature. For storage time treatment, the volatilization of EEO was significantly inhibited after encapsulation. High temperature stability test further revealed that EEO was protected after having been encapsulated into β-CD. For all treatments, the release parameter n was between 0.5 and 1.0, which presenting a diffusion-limited and first-order mode. These results indicated that encapsulation enhanced the stability and prolonged the acting time of EEO, and the release rate of EEO can also be passively controlled by the ambient temperature, humidity and storage time.     

Ligandless Suzuki–Miyaura reaction in neat water with or without native β-cyclodextrin as additive

Efficient green ligand-free Suzuki cross coupling in neat water was developed by using low loading of catalyst (0.5 mol%) in neat water in the presence or not of β-cyclodextrin (0.5 mol%) as additive at 25 °C and 100 °C respectively.     

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.