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     

Synthesis of a new chitosan immobilized with β‐cyclodextrins and its adsorption properties for bilirubin

A new chitosan derivative of chitosan immobilized with β‐cyclodextrins (CTC) has been synthesized by the reaction of chitosan and allyl‐substituted β‐cyclodextrins (ASC). Its structure has been proved by Fourier transform infrared spectral analysis, X‐ray powder diffraction analysis, and chemical analysis. Its adsorption of bilirubin has been also studied. By the experiment, it has been found that this new product has good adsorption ability on bilirubin. At initial 2 h, the adsorption increased largely. The adsorption mechanism was also dealt with. It predicted that this new chitosan derivative could have application in removing the bilirubin. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1264–1268, 2006     

Preparation and characterization of β‐cyclodextrin‐linked chitosan microparticles

Hydrophobically modified chitosan containing β‐cyclodextrin (CD) units was synthesized by using tosylated β‐CD. The final product was characterized by Fourier transform infrared (FTIR) spectroscopy, elemental analysis and TGA, and rheometry. The polymer bearing β‐CD moieties was used to obtain crosslinked microparticles by spray‐drying which could then be used in a controlled release system for drugs. FTIR confirmed the formation of an amide linkage between cyclodextrin and chitosan. As fluorescence spectroscopy demonstrated, hydrophobic microenvironments were formed by chitosan bearing cyclodextrin in solution at lower concentrations than for chitosan. Rheometry and FTIR showed the crosslinking of the new polymer using genipin, a molecule of natural origin. Microspheres (MS) obtained by spray‐drying showed narrow size distribution when β‐CD was grafted onto chitosan and ξ‐potential of MS was slightly lower although it remained positive. In conclusion, β‐CD linked chitosan polymer can be considered as a very promising controlled drug delivery system for drugs. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

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     

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.     

Cationic copolymers of α,β‐poly‐(N‐2‐hydroxyethyl)‐DL‐aspartamide (PHEA) and α,β‐polyasparthylhydrazide (PAHy): synthesis and characterization

In the present study the derivatization of two water‐soluble synthetic polymers, α,β‐poly(N‐2‐hydroxyethyl)‐DL ‐aspartamide (PHEA) and α,β‐polyasparthylhydrazide (PAHy), with glycidyltrimethylammonium chloride (GTA) is described. This reaction permits the introduction of positive charges in the macromolecular chains of PHEA and PAHy in order to make easier the electrostatic interaction with DNA. Different parameters affect the reaction of derivatization, such as GTA concentration and reaction time. PHEA reacts partially and slowly with GTA; on the contrary the reaction of PAHy with GTA is more rapid and extensive. The derivatization of PHEA and PAHy with GTA is a convenient method to introduce positive groups in their chains and it permits the preparation of interpolyelectrolyte complexes with DNA. © 2000 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     

Synthesis and characterization of novel star polymer with β‐cyclodextrin core and its metal complexes

A novel star polymer with β‐cyclodextrin (β‐CD) core and polyacrylonitrile arms and its metal complexes (Cu²⁺, Zn²⁺, and Ag⁺) were synthesized and characterized by means of infrared spectra, ultraviolet, GPC, X‐ray photoelectron spectroscopy, differential scanning calorimetry, cyclic voltammetry, and electron spin resonance. The results indicate that the monomers of acrylonitrile were initiated by functionalized β‐CD. The thermal properties of star polymer were improved greatly after transitional metal ions were introduced into it. The novel star polymer metal complexes possess properties of metal ions, polymer, and β‐CD. Furthermore, it shows stable electrochemical activity. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Guided tissue regeneration with use of β‐TCP/chitosan composite membrane

Guided tissue regeneration (GTR) membranes with bioabsorbable characteristics have been employed, in recent years, for periodontal procedures to deflect the growth of gingival tissues away from root surface. They provide an isolated space over regions with defective tissues and allow the relatively slow growing periodontal ligament fibroblasts to be repopulated over the root surface. In this study, we have employed chitosan and tricalcium phosphate (β‐TCP) as viable membrane materials and evaluated their roles in GTR applications. Three types of β‐TCP/chitosan membranes, weight ratio of β‐TCP/chitosan 65 : 35, 33 : 67, and 10 : 90, were prepared for three categories: the mechanical strength to create an effective space; the rapid rate to reach hydrolytic equilibrium in phosphate buffer solution; and the ease of clinical manipulations. Consequently, standardized, transosseous, and critical‐sized (cavity of 8 mm) skull defects were made in adult rabbits, and the defective regions were covered with the specifically prepared chitosan membranes. After 4 weeks of recovering, varying degrees of bone healing were observed beneath the β‐TCP/chitosan membranes in comparison to the control group. The β‐TCP/chitosan membranes covered regions showed a clear boundary space between connective tissues and bony tissues. Over all, good cell‐occlusion and beneficial osteogensis effects by these bioabsorbable materials toward the wound recovery were indicated. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

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     

Ruthenium(II)‐Catalyzed Protocol for Preparation of Diverse α,β‐ and β,β‐Dihaloenones from Diazodicarbonyls

Efficient one‐step syntheses of α,β‐ and β,β‐dihaloenones were achieved by ruthenium(II)‐catalyzed reactions between cyclic or acyclic diazodicarbonyl compounds and oxalyl chloride or oxalyl bromide in moderate to good yields. This methodology offers several significant advantages, which include ease of handling, mild reaction conditions, one‐step reaction, and the use of an effective and non‐toxic catalyst. The synthesized compounds were further transformed into highly functionalized novel molecules bearing aromatic rings on the enone moiety using the Suzuki reaction.

     

Michael Reaction of Nitroalkanes with β‐Nitroacrylates under a Solid Promoter: Advanced Regio‐ and Diastereoselective Synthesis of Nitro‐Functionalized α,β‐Unsaturated Esters and 1,3‐Butadiene‐2‐carboxylates

A new class of nitro‐functionalized α,β‐unsaturated esters has been prepared by a regio‐ and diastereoselective Michael addition of nitroalkanes to β‐nitroacrylates, performed at room temperature, under carbonate on polymer as promoter, and in the presence of ethyl acetate as eco‐friendly solvent. Moreover, by the modular choice of the reaction conditions the method allows the synthesis of 1,3‐butadiene‐2‐carboxylates.     

Synthesis and characterization of polyimide‐γ‐Fe2O3 nanocomposites

Novel polyimide‐γ‐Fe₂O₃ hybrid nanocomposite films (PI/γ‐Fe₂O₃) has been developed from the poly(amic acid) salt of oxydianiline with different weight percentages (5, 10, 15 wt %) of γ‐Fe₂O₃ using tetrahydrofuran (THF) and N,N‐dimethylacetamide (DMAc) as aprotic solvents. The prepared polyimide‐γ‐Fe₂O₃ nanocomposite films were characterized for their structure, morphology, and thermal behavior employing Fourier transform infrared spectroscopy (FTIR), scanning electron micrograph (SEM), transmission electron micrograph (TEM), X‐ray diffraction (XRD), ¹³C‐NMR, and thermal analysis (TGA/DSC) techniques. These studies showed the homogenous dispersion of γ‐Fe₂O₃ in the polyimide matrix with an increase in the thermal stability of the composite films on γ‐Fe₂O₃ loadings. Magnetization measurements (magnetic hysteresis traces) have shown very high values of coercive force indicating their possible use in memory devices and in other related applications. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 834–840, 2007     

Preparation and characterization of chitosan/α‐zirconium phosphate nanocomposite films

Nano‐fillers play an important role in the final structure and properties of nanocomposites. The objective of the work presented here was to prepare nanocomposite films of chitosan/α‐zirconium phosphate using a casting process, with α‐zirconium phosphate (α‐ZrP) as nano‐filler and chitosan as matrix. The effects of α‐ZrP on the structure and properties of the nanocomposites were investigated. X‐ray diffraction patterns showed that α‐ZrP crystals were intercalated by n‐butylamine. The results from scanning electron microscopy and transmission electron microscopy indicated that α‐ZrP could be uniformly dispersed in the chitosan matrix when α‐ZrP loading in the composites was less than 2 wt%. A strong interaction between α‐ZrP and chitosan formed during the film‐forming process. Tensile testing showed that the tensile strength and elongation at break of nanocomposite films achieved maximum values of 61.6 MPa and 58.1%, respectively, when α‐ZrP loading was 2 wt%. The parameter B calculated from tensile yield stress according to the Pukanszky model was used to estimate the interfacial interaction between the chitosan matrix and α‐ZrP. Films with a loading of 2 wt% α‐ZrP had the highest B value (3.2), indicating the strongest interfacial interaction. The moisture uptake of the nanocomposites was reduced with addition of α‐ZrP. It can be concluded that α‐ZrP as nano‐filler in a chitosan matrix can enhance the mechanical properties of nanocomposites due to the strong interactions between α‐ZrP and chitosan. Copyright © 2010 Society of Chemical Industry     

Synthesis and characterization of polyurethane elastomers based on chitosan and poly(ε‐caprolactone)

Biodegradable polyurethane (PU) elastomers with potential for biomedical and industrial applications were synthesized by the reaction of poly(ε‐caprolactone) (PCL) and isophorone diisocyanate (IPDI), extended with different mass ratio of chitosan and 1,4‐butane diol (BDO). Their chemical structures were characterized using FTIR, ¹HNMR, and ¹³CNMR, and thermal properties were determined by TGA and DMTA. Incorporation of chitosan contents into the polyurethane backbone caused improvement in thermal stability and thermal degradation rate. Optimum thermal properties and degradation profile were obtained from elastomer extended with chitosan. The crystallinity and hydrophilicity of the prepared polymers were also examined by X‐ray and contact angle measurements. The results showed that hydrophilicity decreased and crystallinity increased with increasing of chitosan content in polyurethane backbone. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and properties of hydrogels of poly(acrylic‐co‐acroloyl β‐cyclodextrin)

Novel acrylic monomers (β‐CD‐A and β‐CD‐6‐EA) containing β‐cyclodextrin (β‐CD) with different extent of substitution were prepared by using dicyclohexylcarbodiimide (DCC) as a condensation agent at room temperature. Two kinds of functional hydrogels were also synthesized by copolymerization of β‐CD‐A and β‐CD‐6‐EA with acrylic acid (AAc) using a redox initiator system in aqueous solution. The nuclear magnetic resonance (¹H NMR), infrared spectroscopy (IR), thermogravimetric analysis (TGA) were employed to character the molecular structures of β‐CD modified monomers and their copolymers. The swelling experiments indicate that the hydrogels with different equilibrium swelling ratio (ESR) possess obvious pH‐sensitivity and distinct dynamic swelling behavior. Using an anti‐cancer drug, chlorambucil (CHL), able to form complexes with β‐CD in water, as a model compound, the controlled drug release behaviors of these hydrogels were investigated. The release behavior of CHL from two kinds of hydrogels synthesized reveals that the release rate of CHL can be effectively controlled by pH values, cross‐linking density, and β‐CD content. In addition, it is found that the β‐CD with the proper frame and concentration can increase release efficiency of CHL from the hydrogels. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

The Synthesis of trans‐Perhydroindolic Acids and their Application in Asymmetric Domino Reactions of Aldehyde Esters with β,γ‐Unsaturated α‐Keto Esters

(2S,3aR,7aS)‐Perhydroindolic acid, the key intermediate in the synthesis of trandolapril, and its trans‐isomers, were readily prepared. These proline‐like molecules are unique in that they contain a rigid bicyclic structure, with two hydrogen atoms trans to each other at the bridgehead carbon atoms. These molecules were used successfully as chiral organocatalysts in asymmetric domino Michael addition/cyclization reactions of aldehyde esters with β,γ‐unsaturated α‐keto esters. They proved to have excellent catalytic behavior, allowing for the synthesis of multi‐substituted, enantiomerically enriched hemiacetal esters. Under optimal conditions (using 10 mol% catalyst loading), a series of β,γ‐unsaturated α‐keto esters was examined with up to 99% de, ee and yield, respectively. Additionally, the enantiomerically enriched hemiacetal esters could be readily transformed into their corresponding bioactive pyrano[2,3‐b]pyrans (possessing a multi‐substituted bicyclic backbone).     

Highly Enantioselective Phase‐Transfer Catalytic α‐Alkylation of α‐tert‐Butoxycarbonyllactams: Construction of β‐Quaternary Chiral Pyrrolidine and Piperidine Systems

A new enantioselective α‐alkylation of α‐tert‐butoxycarbonyllactams for the construction of β‐quaternary chiral pyrrolidine and piperidine core systems is reported. α‐Alkylations of N‐methyl‐α‐tert‐butoxycarbonylbutyrolactam and N‐diphenylmethyl‐α‐tert‐butoxycarbonylvalerolactam under phase‐transfer catalytic conditions (solid potassium hydroxide, toluene, −40 °C) in the presence of (S,S)‐3,4,5‐trifluorophenyl‐3,3′,5,5′‐tetrahydro‐2,6‐bis(3,4,5‐trifluorophenyl)‐4,4′‐spirobi[4H‐dinaphth[2,1‐c:1′,2′‐e]azepinium] bromide [(S,S)‐NAS Br] (5 mol%) afforded the corresponding α‐alkyl‐α‐tert‐butoxycarbonyllactams in very high chemical (up to 99%) and optical yields (up to 98% ee). Our new catalytic systems provide attractive synthetic methods for pyrrolidine‐ and piperidine‐based alkaloids and chiral intermediates with β‐quaternary carbon centers.