Complexation of Surfactant/β‐Cyclodextrin to Inhibit Surfactant Adsorption onto Sand,Kaolin, and Shale for Applications in Enhanced Oil Recovery Processes. Part II: Dynamic Adsorption Analysis

Surfactant adsorption onto solid surfaces is problematic in some industrial processes, such as in surfactant flooding for enhanced oil recovery. In this work, it was hypothesized that the use of a surfactant delivery system could prevent surfactant adsorption onto solid surfaces. Therefore, the encapsulation of sodium dodecyl sulfate (SDS) into the hydrophobic core of β‐cyclodextrin (β‐CD) to generate a surfactant delivery system (SDS/β‐CD) was evaluated in this work. This complexation was characterized using optical and scanning electron microscopy (SEM), and Fourier transform infrared spectroscopy (FT‐IR). Dynamic adsorption evaluation was applied to determine the effectiveness of the complexation in inhibiting surfactant adsorption onto a variety of solid adsorbents including sand, and mixtures of sand–kaolin and sand–shale. Surfactant adsorption was also evaluated applying the quartz crystal microbalance technology (QCM‐D). The formation and morphology of the complexation was confirmed by optical microscopy, SEM, and FT‐IR. Dynamic adsorption tests demonstrated the effectiveness of the surfactant delivery approach in preventing the adsorption of surfactant (up to 74 % adsorption reduction). The QCM‐D technology confirmed these observations. Several mechanisms were proposed to explain the inhibition of surfactant adsorption including steric hindrance, self‐association of inclusion complexes, hydrophilicity increase, and disruption of hemimicelles formation.     

Complexation of Surfactant/β‐Cyclodextrin to Inhibit Surfactant Adsorption onto Sand,Kaolin, and Shale for Applications in Enhanced Oil Recovery Processes. Part III: Oil Displacement Evaluation

This proof of concept research evaluates the performance of a surfactant/β‐cyclodextrin (β‐CD) inclusion complex during chemical flooding for enhanced oil recovery. It was hypothesized that the encapsulated surfactant propagates well through the porous media. Sodium dodecyl sulfate (SDS) was used to study the surfactant/β‐CD complexations. Phase behavior analysis was carried out to prepare the most favorable chemical slug formulation. A series of core flooding tests were conducted to determine the efficiency of the SDS/β‐CD inclusion complex in displacing residual oil. Surfactant flooding was conducted as tertiary oil recovery mode (after mature water flooding) by injecting 0.3 pore volume (PV) of the optimum surfactant slug that was chased by 0.3 PV of a polymer slug; followed by continuous water flooding until oil production stopped. The experimental results indicate that the encapsulated surfactant propagates well through the sandpack system and consistently produces higher incremental oil recoveries that range from 40 to 82 % over the incremental oil recovery achieved by conventional surfactant flooding.     

Inclusion complex of cantharidin with β‐cyclodextrin: Preparation,characterization, in vitro and in vivo evaluation

Because of low aqueous solubility and slow dissolution rate, cantharidin has a low oral bioavailability. Our research aims to prepare the inclusion complex of cantharidin and β‐cyclodextrin (β‐CD) and accomplish characterization, in vitro and in vivo evaluation. CA‐β‐CD inclusion complex was prepared by saturated solution method. The CA was demonstrated by HPLC in vitro experiment and by GC‐MS in vivo experiment. CA‐β‐CD inclusion complex was characterized by differential scanning calorimetry (DSC), X‐ray diffractometry (XRD), and nuclear magnetic resonance (NMR). Through complexation with β‐CD, the solubility of CA in neutral aqueous solution was improved significantly. CA‐β‐CD inclusion complex also shows a significantly improved dissolution rate in comparison with free CA. Comparison of the pharmacokinetics between CA‐β‐CD inclusion complex and free CA was performed in rats. The in vivo results show that CA‐β‐CD inclusion complex has earlier t_max, higher C_max, and higher bioavailability than free CA after oral dosing. By comparing the AUC_0–t of CA and CA‐β‐CD inclusion complex, the relative bioavailability of CA‐β‐CD inclusion complex to free CA was 506.3%, which highlighted the evidence of significantly improved bioavailability of formulation of CA with β‐CD. Thus, this β‐CD‐based drug delivery system should be an effective oral dosage form to improve oral bioavailability of CA. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis and characterization of grafting β‐cyclodextrin with chitosan

Two new adsorbents [β‐cyclodextrin–chitosan (β‐CD–CTS) and β‐cyclodextrin‐6–chitosan (β‐CD‐6‐CTS)] were synthesized by the reaction of β‐cyclodextrin (β‐CD) with epoxy‐activated chitosan (CTS) and the sulfonation of the C‐6 hydroxyl group of β‐cyclodextrin with CTS, respectively. Their structures were confirmed by IR spectral analysis and X‐ray diffraction analysis, and their apparent amount of grafting was determined by ultraviolet spectroscopy. The adsorption properties of β‐CD‐CTS and β‐CD‐6‐CTS for p‐dihydroxybenzene were studied. The experimental results showed that the two new adsorbents exerted adsorption on the carefully chosen target. The highest saturated capacity of p‐dihydroxybenzene of β‐CD‐CTS and β‐CD‐6‐CTS were 51.68 and 46.41 mg/g, respectively. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 860–864, 2004     

Preparation of bimodal porous copolymer containing β‐cyclodextrin and its inclusion adsorption behavior

A novel insoluble bimodal porous polymer containing β‐cyclodextrin (β‐CD) was prepared to adsorb aromatic amine compound. The process involved copolymerization of styrene and methyl methacrylate with a maleic acid derivative of β‐CD, subsequently, above formed copolymer was foamed by supercritical CO₂. The chemical properties and physical structure of obtained copolymer was analyzed using Fourier transform infrared spectra, Thermal gravimetric analysis, X‐ray diffraction, scanning electron microscope, and N₂ adsorption techniques. The inclusion adsorption of aromatic amine compounds on β‐CD copolymer was carried out in a batch system. The quantities of aromatic amine compounds adsorbed on β‐CD copolymer reached equilibrium within 60 min. The adsorption kinetic could be fitted to a pseudo‐second‐order kinetic equation, and the linear correlation coefficients varied from 0.9828 to 0.9935. With the influence of molecular structure and hydrophobicity of the aromatic amine compound, the sequence of quantity of aromatic amine compounds adsorbed on β‐CD copolymer is p‐toluidine > aniline > benzidine > o‐toluidine. The adsorption equilibrium data of aromatic amine compound adsorbed on β‐CD copolymer were fitted to Freundlich and Langmuir models, respectively. The linear correlation coefficients of Langmuir model varied from 0.9516 to 0.9940, and the linear correlation coefficients of Freundlich varied from 0.9752 to 0.9976. It is concluded that Freundlich model fits better than Langmuir model, because the adsorption of aromatic amine compound on β‐CD copolymer is a chemical process. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Viscometric Study of the Inclusion Complex Between β‐Cyclodextrin and HTAC in Aqueous Solution

The inclusion complex formed by β‐cyclodextrin (β‐CD) with the cationic surfactant hexadecyltrimethylammonium chloride (HTAC) was studied by viscometry using poly(ethylene oxide) (PEO)–HTAC aggregates as a viscosity indicator. The relative viscosity of β‐CD in aqueous PEO–HTAC solution profiles shows that the formation of the β‐CD/HTAC inclusion complex causes HTAC molecules to be stripped off the PEO chains, resulting in a decrease of aqueous solution viscosity as a result of the decrease in electrostatic repulsion between polymer‐bound HTAC micelles. The viscosity minimum at C_β‐CD/C_HTAC = 0.5 indicates that the molecular ratio of host molecule to guest molecule is 1:2 in the β‐CD/HTAC inclusion complex.     

Isothermal crystallization and melting behavior of polypropylene with lanthanum complex of cyclodextrin derivative as a β‐nucleating agent

A novel highly active β‐nucleating agent, β‐cyclodextrin complex with lanthanum (β‐CD‐MAH‐La), was introduced to isotactic polypropylene (iPP). Its influence on isothermal crystallization and melting behavior of iPP was investigated by differential scanning calorimeter (DSC), wide‐angle X‐ray diffraction (WAXD), and polarized light microscopy (PLM). WAXD results demonstrated that β‐CD‐MAH‐La was an effective β‐nucleating agent, with β‐crystal content of iPP being strongly influenced by the content of β‐CD‐MAH‐La and the isothermal crystallization temperature. The isothermal crystallization kinetics of pure iPP and iPP/β‐CD‐MAH‐La was described appropriately by Avrami equation, and results revealed that β‐CD‐MAH‐La promoted heterogeneous nucleation and accelerated the crystallization of iPP. In addition, the equilibrium melting temperature (T) of samples was determined using linear and nonlinear Hoffman‐Weeks procedure. Finally, the Lauritzen‐Hoffman secondary nucleation theory was applied to calculate the nucleation parameter (K_g) and the fold surface energy (σ_e), the value of which verify that the addition of β‐CD‐MAH‐La reduced the creation of new surface for β‐crystal and then led to faster crystallization rate. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Photocatalytic degradation of 2,2‐bis(4‐hydroxy‐3‐methylphenyl) propane (BPP) based on molecular recognition interaction

BACKGROUND: Endocrine disruptors in the aquatic environment and their potential adverse effects are currently issues of concern. One of these endocrine disruptors is 2,2‐bis(4‐hydroxy‐3‐methylphenyl)propane (BPP). In this work the molecular recognition interaction of BPP with β‐cyclodextrin (β‐CD) was studied using IR spectroscopy and steady state fluorescence spectroscopy, and the photocatalytic degradation behaviour of BPP based on molecular recognition interaction was investigated in a TiO₂/UV–visible (λ_max = 365 nm) system. This might provide a new method for the treatment of some organic pollutants in wastewater. RESULTS: β‐CD reacts with BPP to form a 1:1 inclusion complex, the formation constant of which is 4.94 × 10³ L mol^?1. The photodegradation rate constant of BPP after molecular recognition by β‐CD showed a 1.42‐fold increase in the TiO₂/UV–visible (λ_max = 365 nm) system. The photodegradation of BPP depended on the concentration of β‐CD, the pH value, the gaseous medium and the initial concentration of BPP. The photodegradation efficiency of BPP with molecular recognition was higher than that without molecular recognition. After 100 min of irradiation the mineralisation efficiency of BPP after molecular recognition by β‐CD reached 94.8%, whereas the mineralisation efficiency of BPP before molecular recognition by β‐CD was only 40.6%. CONCLUSION: The photocatalytic degradation of BPP after molecular recognition by β‐CD can be enhanced in the TiO₂/UV‐visible (λ_max = 365 nm) system. This enhancement is dependent on the enhancement of the adsorption of BPP, the moderate inclusion depth of BPP in the β‐CD cavity and the increase in the frontier electron density of BPP after molecular recognition. Copyright © 2008 Society of Chemical Industry     

Synthesis of a vinyl monomer containing β‐cyclodextrin and grafting onto cotton fiber

To chemically bond β‐cyclodextrin (β‐CD), which can form inclusion complexes, acrylamidomethyl CD (CD–NMA) obtained from the acid‐catalyzed reaction of N‐methylolacrylamide (NMA) and β‐CD was grafted onto cellulose fibers using CeIV as the initiator. The double‐bond content of CD–NMA increased with increase in the NMA/CD mol ratio, and a CD–NMA containing a maximum of three molecules of NMA bonded to a CD molecule could be obtained. Since the grafting condition is acidic, the hydrolytic stability of CD–NMA in aqueous nitric acid was studied. The temperature of hydrolysis proved to have a greater effect on the depletion of double bonds from CD–NMA compared with the concentration of the acid. Thus, CD–NMA was grafted onto cellulose fibers at a low temperature, and FTIR analysis of the CD–NMA‐grafted cotton fibers confirmed the chemical bonding of CD–NMA molecules to cellulose. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 438–446, 2001     

2‐Naphthol‐containing β‐cyclodextrin–epichlorohydrin copolymers: synthesis,characterization and fluorescence studies

Fluorescent 2‐naphthol (NOH)‐containing β‐cyclodextrin (β‐CD)–epichlorohydrin (EP) copolymers were synthesized. Polymerization was confirmed through viscosity and FT‐IR spectroscopic measurements. Under certain conditions, the copolymers were water‐soluble (molar ratio of EP/β‐CD <22:1), while under other conditions water‐insoluble gels were formed (EP/β‐CD ≥ 22:1). Increase of the EP content to EP/β‐CD ≤ 39:1 increased the fluorescence intensity of the copolymer and shifted the emission maximum from 422 nm toward 352 nm (measured at pH ≥ 12). Further increases in the EP content resulted in a slight decrease in the fluorescence intensity. The fluorescence properties of our system at EP/β‐CD < 22 were sensitive to pH variation, while at EP/β‐CD ≥ 22 no pH effect was observed. These variations can be explained in terms of the exposure of the fluorophore to solvent in soluble versus insoluble polymers, as well as changes in the mode of association (host–guest complexation, trapping within the polymer network, covalent bonding, etc) of NOH with the polymers. Crystallographic studies on a single crystal grown in the absence of EP, but under basic conditions, suggest that host–guest complexation is not an important mode for NOH incorporation. Copyright © 2005 Society of Chemical Industry     

Equilibrium of benzidine inclusion adsorption on cyclodextrin copolymer

Insoluble β‐cyclodextrin (β‐CD) copolymer was prepared by reacting β‐CD with hexamethylene diisocyanate, and its inclusion adsorption behavior was investigated. The physical and chemical properties of CD copolymer were characterized by SEM, FTIR, DSC, TGA, XRD, and BET N₂ adsorption. The effects that shaking time and temperature exerted on the inclusion adsorption of benzidine on CD copolymer have been studied at relative low initial benzidine concentration. The procedure of the inclusion adsorption could be described by the Freundlich equation, and the thermodynamic constants ΔH^θ, ΔS^θ and ΔG^θ were obtained simultaneously. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Negative effect of stretching on the development of β‐phase in β‐nucleated isotactic polypropylene

On the premise that shear in the slit die of an extruder was minimized as far as possible, β‐nucleated isotactic polypropylene (iPP) was extruded. Simultaneously, once the extrudate (in the melt state) left the die exit, it was stretched at various stretching rates (SRs). For iPP with a low content of β‐nucleating agent (β‐NA), the crystallinity of β‐phase (X_β) initially increases with increasing SR, and then decreases slightly with further increase in SR. However, for iPP containing a higher content of β‐NA, with increasing SR, X_β decreases monotonically, indicating a negative effect of SR on β‐phase formation. Small‐angle X‐ray scattering and polarized optical microscopy experiments reveal that, when SR is less than 30 cm min^?1, the increasing amount of row nuclei induced by increasing SR is mainly responsible for the increase of X_β. In contrast, when SR exceeds 30 cm min^?1, the overgrowth of shish structures unexpectedly restrains the development of β‐phase, and spatial confinement is considered as a better explanation for the suppression of β‐phase. Copyright © 2011 Society of Chemical Industry     

Adsorption of guanosine,cytidine, and uridine on a β‐cyclodextrin derivative grafted chitosan

A β‐cyclodextrin derivative grafted chitosan (CDD‐C) was synthesized with chitosan and carboxymethyl‐β‐cyclodextrin (β‐CD). Its structure was characterized by elemental, infrared spectra, and X‐ray diffraction analyses. The degree of substitution by the carboxymethyl‐β‐CD moiety achieved 0.27 with the addition of DMF to the reaction solution. The results are in agreement with the expectations. The static adsorption properties for guanosine, cytidine, and uridine were studied. Experimental results demonstrated that CDD‐C had higher adsorption capability for guanosine than cytidine and uridine, and the adsorption capacity for guanosine was 74.20 mg/g. The adsorption capacity was greatly influenced by pH, time, and temperature. The introduction of chitosan enhanced the adsorption ability and adsorption selectivity of β‐CD for guanosine. This novel derivative of chitosan is expected to have wide applications in separation, concentration, and analysis of guanosine, cytidine, and uridine in biological sample. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3050–3055, 2007     

Preparation and characterisation of a novel copper‐imprinted polymer based on β‐cyclodextrin copolymers for selective determination of Cu2+ ions

A novel ion‐imprinted polymer (IIP) using (6‐O‐butene diacid ester)‐β‐cyclodextrin (β‐CD‐MAH) as the functional monomer and copper ions as the template was developed for Cu²⁺ sensing. First, reactive β‐cyclodextrin (β‐CD) monomers with vinyl carboxylic acid functional groups were synthesised and were co‐polymerised with styrene via radical polymerisation. Then, the β‐CD copolymers were complexed with Cu²⁺ in order to obtain the IIP. The imprinting effect was realised by removing the template ions from the imprinted polymer. The structure, composition and morphology of the IIP were characterised by Fourier transform IR spectroscopy, energy‐dispersive spectroscopy and field‐emission SEM. The adsorption capacity was investigated by UV–visible spectroscopy in batch operation mode. The maximum adsorption capacity for the Cu²⁺ template ions was 28.91 mg g^?1, and the adsorption selectivity was clearly illustrated from the increased sorption affinity towards Cu²⁺ ions over other competing ions. The adsorption was affected by the pH of the aqueous medium, and enhanced adsorption capacity was observed at pH 5. The prepared IIP could be used 10 times after its regeneration without significant loss of the adsorption capacity. © 2018 Society of Chemical Industry     

Equilibrium studies on enantioselective extraction of oxybutynin enantiomers by hydrophilic β‐cyclodextrin derivatives

The enantioselective extraction of hydrophobic oxybutynin (OBN) enantiomers by hydrophilic β‐cyclodextrin (β‐CD) derivatives was studied. The efficiency of extraction depends strongly on a number of process variables such as types of organic solvents and β‐CD derivatives, concentration of selector, pH, and temperature. The experimental data were described by a reactive extraction model with a homogeneous aqueous phase reaction of R,S‐OBN with β‐CD. Important parameters of this model were determined experimentally. The physical distribution coefficients for molecular and ionic OBN were 4.96 × 10^?3 and 9.52, respectively. The equilibrium constants of the complexation reactions were 1770 and 1340 L/mol for S‐ and R‐OBN, respectively. By modeling and experiment, an optimal extraction condition with pH of 5 and HP‐β‐CD concentration of 0.1 mol/L was obtained with enantioselectivity (α) of 1.26, which was close to the theoretical maximum of 1.32 and performance factor (pf_i) of 0.036. The model was verified experimentally with excellent results. © 2011 American Institute of Chemical Engineers AIChE J, 2011     

Synthesis and characterization of novel biocidal cyclodextrin inclusion complexes grafted onto polyamide‐6 fabric by a redox method

The synthesis of immobilized β‐cyclodextrin derivatives onto polyamide‐6 fabric is presented. These novel fabrics were prepared by graft‐copolymerization of glycidyl methacrylate (GMA) onto polyamide 6 fabric, using a chemical redox system K₂S₂O₈/CuSO₄·5H₂O, followed by reaction of β‐cyclodextrins (CD) or monochlorotriazinyl (MCT β‐CD) with the GMA epoxy group. Some biocidal guests were complexed into CD cavity including p‐hydroxy benzoic acid, AgNO₃–ethanolamine mixture, iodine, N,N‐diethyltoluamide (DETA), citronella, jasmine, and sweet basil. Characterization of the novel fabrics was done by Fourier transform infrared spectroscopy (IR), electron scanning microscopy (SEM), and thermo gravimetric analysis (TGA). The biocidal activity of the grafted fabrics was tested against five strains of microorganisms. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 2586–2593, 2006     

Preparation and evaluation of chitosan/β‐cyclodextrin magnetic nanoparticles as a photodegradable and hydrophobic drug delivery carrier

In this study, novel tumor targeting nanocarriers comprised of chitosan (CS)/β‐cyclodextrin (β‐CD) magnetic nanoparticles were prepared to improve the photodegradable stability and bioavailability of hydrophobic drug. Resveratrol (Res) with photodegradable and hydrophobic properties was selected as a model drug. The photodegradation rate of Res in Fe₃O₄ nanoparticles solution was 7.8 times lower than that in the ethanol solution_. In addition, the value of the saturation magnetization of CS/β‐CD nanoparticles was found to be 19.56 emu/g with characteristic of superparamagnetism. Approximately 90% Res was entrapped into the CS/β‐CD magnetic nanoparticles with the size distribution ranging from 200 to 359 nm, and the nanoparticles were spherical in shape with high zeta potentials. Furthermore, the formation of CS/β‐CD nanoparticles showed a sustained release in vitro. These results indicated that the obtained CS/β‐CD magnetic nanoparticles were a promising magnetic targeting carrier for photodegradable and hydrophobic drugs. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45076.     

Effect of β‐cyclodextrin on the solid‐state synthesized polyaniline doped with hydrochloric acid

Polyaniline (PANI) salts doped with hydrochloric acid were prepared by using solid‐state polymerization in the presence of β‐cyclodextrin (β‐CD) at room temperature. The fourier transform infrared (FTIR) spectra, ultraviolet‐visible absorption spectra, X‐ray diffraction patterns were used to characterize the molecular structures of these polymers. Cyclic voltammetry study and conductivity measurements were done to investigate their electrochemical behaviors. The morphology of polymers was studied by the scanning electron microscopy and transmission electron microscopy. The results showed that PANI salts prepared in the presence of β‐CD had different physicochemical characteristics compared with PANI salt prepared in the absence of β‐CD. When the molar ratio of aniline to β‐CD was 80/20, the obtained PANI salt displayed higher crystallinity, conductivity and electrochemical properties. However, these properties were opposite on condition that the molar ratio of aniline to β‐CD was 50/50. The results also revealed that the morphology of PANI salt was affected by β‐CD, especially at aniline/β‐CD molar ratio in the feed of 50/50, in which PANI salt displayed rodlike structure morphology with a diameter of near 80–100 nm. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

A facile and practical approach to randomly methylated β‐cyclodextrin

BACKGROUND: Because of its high demand for use in pharmaceutical products, cosmetics, soil remediation technologies, etc., randomly methylated β‐cyclodextrin (RM‐β‐CD) is one of the most important cyclodextrin (CD) derivatives. The aim of this present work is to use a green and commercially available approach to obtain RM‐β‐CD. Compared with other methylated CDs, RM‐β‐CD with an asymmetric molecular structure has higher water solubility. When the degree of substitution (DS) is about 1.8, the solubility tends to increase with increasing temperature and is suitable for pharmaceutical applications. RESULTS: RM‐β‐CD was synthesized using a green approach with ideal DS equal to 1.79. The one step process of β‐cyclodextrin methylation by CH₃Cl instead of (CH₃)₂SO₄ at mild temperature (80 °C) and pressure (1.60 MPa) with a good yield (78%), is convenient and environmentally friendly. The mixture of RM‐β‐CD obtained contained five compounds with various DS, from which the main compound with a DS equal to 1.8 was separated by column chromatography. The compounds were carefully characterized by infra‐red, NMR and mass spectrometry. CONCLUSIONS: The one‐step process to RM‐β‐CDs with CH₃Cl is more economical, more efficient and less noxious than the usual method using (CH₃)₂SO₄. Moreover, this approach avoids some poisonous residual materials and meets the demand for protecting the environment. Copyright © 2009 Society of Chemical Industry     

Synthesis of a novel linear water‐soluble β‐cyclodextrin polymer

A novel linear water‐soluble β‐cyclodextrin polymer has been prepared by grafting β‐cyclodextrin on poly[(methyl vinyl ether)‐alt‐(maleic anhydride)]. First, lithium hydride was used to obtain the mono‐alkoxide β‐CD. Grafting of β‐CD derivatives to the polymer backbone was then carried out by an esterification method. Using this method, polymers containing various amounts of β‐CD were synthesized. The resulting grafted polymers were characterized by two complementary methods, ¹H NMR and IR spectroscopy. The first was used to calculate the degree of substitution for the low amounts of β‐CD. The second method was very useful to evaluate the degree of substitution and the molar ratio of CD especially for high amounts of grafting. Our results indicate good agreement between both methods for intermediate rates. Copyright © 2004 Society of Chemical Industry