Conventional Study on Novel Dicationic Ionic Liquid Inclusion with β-Cyclodextrin

This study focuses on the synthesis and characterization of the inclusion complex of β-Cyclodextrin (β-CD) with dicationic ionic liquid, 3,3'-(1,4-Phenylenebis [methylene]) bis(1-methyl-1H-imidazol-3-ium) di(bromide) (PhenmimBr). The inclusion complex was prepared at room temperature utilizing conventional kneading technique. Proton ((1)H) NMR and 2D ((1)H-(1)H) COSY NMR were the primary characterization tools employed to verify the formation of the inclusion complex. COSY spectra showed strong correlations between protons of imidazolium and protons of β-CD which indicates that the imidazolium ring of PhenmimBr has entered the cavity of β-CD. UV absorption indicated that β-CD reacts with PhenmimBr to form a 2:1 β-CD-PhenmimBr complex with an apparent formation constant of 2.61 × 10(5) mol&(-2) L(2). Other characterization studies such as UV, FT-IR, XRD, TGA, DSC and SEM studies were also used to further support the formation of the β-CD-PhenmimBr inclusion complex.     

Synthesis and Characterization of the Inclusion Complex of β-cyclodextrin and Azomethine

A β-cyclodextrin (β-Cyd) inclusion complex containing azomethine as a guest was prepared by kneading method with aliquot addition of ethanol. The product was characterized by Fourier Transform Infrared (FTIR) spectrometer, ¹H Nuclear Magnetic Resonance (¹H NMR) and Thermogravimetric Analyzer (TGA), which proves the formation of the inclusion complex where the benzyl part of azomethine has been encapsulated by the hydrophobic cavity of β-Cyd. The interaction of β-Cyd and azomethine was also analyzed by means of spectrometry by UV-Vis spectrophotometer to determine the formation constant. The formation constant was calculated by using a modified Benesi-Hildebrand equation at 25 °C. The apparent formation constant obtained was 1.29 × 10⁴ L/mol. Besides that, the stoichiometry ratio was also determined to be 1:1 for the inclusion complex of β-Cyd with azomethine.     

Synthesis and Characterization of β-Cyclodextrin Functionalized Ionic Liquid Polymer as a Macroporous Material for the Removal of Phenols and As(V)

β-Cyclodextrin-ionic liquid polymer (CD-ILP) was first synthesized by functionalized β-cyclodextrin (CD) with 1-benzylimidazole (BIM) to form monofunctionalized CD (βCD-BIMOTs) and was further polymerized using a toluene diisocyanate (TDI) linker to form insoluble CD-ILP (βCD-BIMOTs-TDI). The βCD-BIMOTs-TDI polymer was characterized using various tools and the results obtained were compared with those derived from the native β-cyclodextrin polymer (βCD-TDI). The SEM result shows that the presence of ionic liquid (IL) increases the pore size, while the thermo gravimetric analysis (TGA) result shows that the presence of IL increases the stability of the polymer. Meanwhile, Brunauer-Emmett-Teller (BET) results show that βCD-BIMOTs-TDI polymer has 1.254 m²/g surface areas and the Barret-Joyner-Halenda (BJH) pore size distribution result reveals that the polymer exhibits macropores with a pore size of 77.66 nm. Preliminary sorption experiments were carried out and the βCD-BIMOTs-TDI polymer shows enhanced sorption capacity and high removal towards phenols and As(V).     

Inclusion Complex of Sea Buckthorn Fruit Oil with β-Cyclodextrin: Preparation Characterization and Antioxidant Activity

This study aims to produce an inclusion complex between β-cyclodextrin (β-CD) and sea buckthorn fruit oil (SBFO) by using the saturated aqueous solution method and then to compare the resultant solution with the crude mixtures. In this study, the SBFO is extracted by Soxhlet extraction, which is optimized through the single-factor test. The main constituent of the SBFO is identified by gas chromatography-mass spectrometry (GC-MS), which confirms eight fatty acids. Fourier transform infrared spectroscopy, thermogravimetric analysis-differential scanning calorimetry, optical microscopy, scanning electron microscopy, and the result-characterized synthesized compounds confirm the formation of stable inclusion compounds by the SBFO with β-CD. The yield values of the inclusion complex and the SBFO loading content are 64.87 ± 2.26% and 9.2 ± 1.58%, respectively. Comparing the crude fruit oil, β-CD–SBFO, and saponified fruit oil reveals differences in their 2,2-diphenyl-1-pycrylhydrazyl and 2,2′-azinobis-(3-ethylbenzthiazoline-6-sulfonate) antioxidant activities. These findings suggest that the SBFO inclusion complex after β-cyclodextrin is stabilized and is a good antioxidant. This solution improves the inadequacy of the water solution and the instability of the SBFO. This study also implies that β-CD is a cost-effective and straightforward carrier for extending the applications of SBFO as a food or medicinal additive. Practical applications: In this experiment, the SBFO is converted from oil to powder to increase its efficacy as an additive to health and food products.     

Formation of a Polymer-Coated Inclusion Complex of D-Limonene and β-Cyclodextrin by Spray Drying

The polymer-coated inclusion complex powder formation of D-limonene and β-cyclodextrin obtained by spray drying was investigated with respect to the effects of various types of polymer coating agents on the powder particle size and morphology. The addition of the polymer coating agent affected the average particle size, morphology, and internal structures of the spray-dried powders. The average particle diameter of the uncoated spray-dried powders was approximately 5 µm. The powder particle size increased upon the addition of a polymer coating reagent. With the addition of 9 wt% of the polymer coating agent, an average diameter of approximately 80 µm was obtained for the spray-dried powder particles. However, further addition showed a negligible effect on the particle size. Inclusion complex crystals were observed on the surface and inside of the powder particles.     

β-Cyclodextrin Inclusion Complex to Improve Physicochemical Properties of Pipemidic Acid: Characterization and Bioactivity Evaluation

The aptitude of cyclodextrins (CDs) to form host-guest complexes has prompted an increase in the development of new drug formulations. In this study, the inclusion complexes of pipemidic acid (HPPA), a therapeutic agent for urinary tract infections, with native β-CD were prepared in solid state by kneading method and confirmed by FT-IR and ¹H NMR. The inclusion complex formation was also characterized in aqueous solution at different pH via UV-Vis titration and phase solubility studies obtaining the stability constant. The 1:1 stoichiometry was established by a Job plot and the inclusion mechanism was clarified using docking experiments. Finally, the antibacterial activity of HPPA and its inclusion complex was tested on P. aeruginosa, E. coli and S. aureus to determine the respective EC_50s and EC_90s. The results showed that the antibacterial activity of HPPA:β-CD against E. coli and S. aureus is higher than that of HPPA. Furthermore, HPPA and HPPA:β-CD, tested on human hepatoblastoma HepG2 and MCF-7 cell lines by MTT assay, exhibited, for the first time, antitumor activities, and the complex revealed a higher activity than that of HPPA. The use of β-CD allows an increase in the aqueous solubility of the drug, its bioavailability and then its bioactivity.     

Simple Determination of Deoxycholic and Ursodeoxycholic Acids by Phenolphthalein-β-Cyclodextrin Inclusion Complex

An expeditious colorimetric methodology for the determination of the deoxycholic acid (DCA) and of the ursodeoxycholic acid (UDCA) in pharmaceutical formulations is reported. The method is based on their competitive complexation reaction with a color indicator to form β-cyclodextrin-inclusion complexes. Several pH color indicators were tested, but phenolphthalein (PHP) showed the best interaction with the β-cyclodextrin (β-CD) with an inclusion yield higher than 95%. The best concentrations of β-cyclodextrin to form inclusion complexes were 1.24 × 10⁻³ and 6.2 × 10⁻⁴ M at pH 9.5 and 10.5. Statistical analysis of the results showed that the pH had a significant effect on the DCA determination and that high β-CD-PHP inclusion complex concentrations had a significant negative effect on the UDCA determination (p < 0.05). The limit of detection and limit of quantification were 3.94 × 10⁻⁵ and 1.31 × 10⁻⁴ M for DCA (range: 6.1 × 10⁻⁶–3.13 × 10⁻³ M), 4.08 × 10⁻⁵  and 1.36 × 10⁻⁴ M for UDCA (range: 6.05 × 10⁻⁶–3.88 × 10⁻⁴ M). This simple and cheap method showed high stability and feasible instrumentation.     

Preparation and Characterization of Carboxymethyl Chitosan and β-Cyclodextrin Microspheres by Spray Drying

Three kinds of carboxymethyl chitosan/β-cyclodextrin microspheres loaded with theophylline were prepared by spray drying intended for pulmonary delivery. Mucociliotoxicity, permeation rate, and drug release characteristics of the product were investigated. The microspheres obtained by spray drying were found to be spherical with smooth or wrinkled surfaces. The mean particle size was between 3.39 and 6.06 µm. The microspheres demonstrated high product yield (43.7–50.2%), high drug loading (13.7–38.1%), and high encapsulation efficiency (86.9–92.8%). FT-IR indicated that there were interactions of theophylline with carboxymethyl chitosan matrix. Further studies on mucociliotoxicity and permeation confirmed that microspheres had better adaptability and high permeation rate. In vitro drug release from the microspheres was not related to the drug/polymer ratios.     

Effect of γ-Cyclodextrin Inclusion Complex on the Absorption of R-α-Lipoic Acid in Rats

R-α-lipoic acid (RLA) is an endogenous organic acid, and works as a cofactor for mitochondrial enzymes and as a kind of antioxidant. Inclusion complexes of RLA with α-, β- or γ-cyclodextrins (CD) were prepared and orally administered as a suspension to rats. Among them, RLA/γ-CD showed the highest plasma exposure, and its area under the plasma concentration-time curve (AUC) of RLA was 2.2 times higher than that after oral administration of non-inclusion RLA. On the other hand, the AUC after oral administration of non-inclusion RLA and RLA/γ-CD to pylorus-ligated rats did not differ. However, the AUC after intraduodenal administration of RLA/γ-CD was 5.1 times higher than that of non-inclusion RLA, and was almost comparable to the AUC after intraduodenal administration of RLA-Na solution. Furthermore, the AUC after intraduodenal administration of RLA/γ-CD was not affected by biliary ligation or co-administration of an amylase inhibitor. These findings demonstrated that RLA was absorbed from the small intestine effectively when orally administered as a γ-CD inclusion complex, which could be easily dissolved in the lumen of the intestine. In conclusion, γ-CD inclusion complex is an appropriate formulation for supplying RLA as a drug or nutritional supplement with respect to absorption.     

Synthesis and Characterization of Silica–Polymer Nanocomposites Functionalized with Piperazine for the Synthesis of β-Nitro Alcohols

Abstract  

In order to compare the activity and selectivity for the synthesis of β-nitro alcohols, piperazine was functionalized directly and after surface modification into the ordered mesoporous SBA-15 framework. The materials were characterized by powder X-ray diffraction, N₂-adsorption–desorption isotherm, FT-IR, SS-NMR and scanning electron microscopy. The catalyst synthesized via surface modification under solvent free conditions showed very high activity and selectivity of β-nitro alcohols compared to the one synthesized by direct functionalization of SBA-15. Finally the possible reaction pathways were explained mechanistically.     

Synthesis and Self-Assembly of β-Cyclodextrin Terminated DMA/NIPAM Diblock Copolymers

A series of β-cyclodextrin (β-CD) terminated diblock copolymers has been prepared via click reaction. The Huisgen cycloaddition between alkyne decorated copolymer and azide functionalized β-CD was performed in organic solvent in the presence of a Cu(I) catalyst, resulting in the formation of β-CD terminated diblock copolymers, which contain thermally responsive poly(N-isopropylacrylamide) (PNIPAM) block and hydrophilic poly(N,N-dimethylacrylamide) (PDMA) block. Using dynamic light scattering and fluorescence spectroscopy measurements, it is demonstrated that these β-CD functionalized block copolymers are capable of reversibly forming micelles in response to changes in solution temperature and that the critical micelle concentration, micellar size, and transition temperature are dependent on both the NIPAM block length and the polymer functionalization.     

Synthesis of a Novel Strong Brønsted Acidic Ionic Liquid and its Catalytic Activities for the Oxathioacetalization

The novel efficient procedure has been developed for the oxathioacetalization of carbonyl compounds and 2-mercaptoethanol at room temperature under solvent-free condition. The results showed that the novel multi-SO₃H functionalized ionic liquid was very efficient for the reactions with the good to excellent yields in short time. Operational simplicity, without need of any solvent, room temperature, low cost of the catalyst used, high yields, applicability to large-scale reactions, reusability and chemoselectivity are the key features of this methodology.     

Preparation of Silica-Based Ionic Liquid an Efficient and Recyclable Catalyst for One-Pot Synthesis of α-Aminonitriles

Abstract  

Preparation of N-(3-silicapropyl) imidazolium hydrogen sulfate ([Sipim]HSO₄) as a heterogeneous acidic ionic liquid is described. This heterogeneous ionic liquid was used as catalyst for the synthesis of α-aminonitriles by a one-pot condensation of aldehydes, amines, and trimethylsilyl cyanide at room temperature. Catalyst could be recycled for several times without any additional treatment.     

Synthesis and Characterization of Nanoscale Mullite Powder

Nanoscale mullite powder were synthesized via solgel-SCFD and middle temperature treatment by using AIP (aluminum-isopropoxde)and TEOS(tetraethyl orthosilicate) as starting materials.Both of the binary aerogel of alumina-silica and calcined nanoscale materials were investigated by using TG-DSC(thermogravimetry-differential scanning calorimeter),TEM(transmission electron microscope),XRD(X-Ray diffractometer)and specific surface area and porosimetry.TG-DSC indicated the removal of most of the volatiles,i.e.15.98% up to about 700℃,and in the DSC curve,existence of two exothermic peak at about 445℃ and 1015℃ may be due to the crystallization of Si-O-Al-O in diphasic gels and mullitization and a small endothermic peak at about 805℃ indicated the decomposition of structural water molecules.On the colligation of the results of TG-DSC,XRD and TEM,the beginning temperature of mullitization in Al2O3-SiO2 aerogel system can be confirmed at about 1015℃.XRD results also showed the formation of mullite at the range 1100-1200℃.TEM and surface area and porosimetry results showed that the nanosized mullite were calcinated at 1100 and 1200℃ exhibited size 30nm and 50nm,specific surface area 138.91m^2/g and 95.81m^2/g.     

Advance in the Polymerization Strategy for the Synthesis of β-Peptides and β-Peptoids

Peptide mimics, possessing excellent biocompatibility and protease stability, have attracted broad attention and research in the biomedical field. β-Peptides and β-peptoids, as two types of vital peptide mimics, have demonstrated great potential in the field of foldamers, antimicrobials and protein binding, etc. Currently, the main synthetic strategies for β-peptides and β-peptoids include solid-phase synthesis and polymerization. Among them, polymerization in one-pot can minimize the repeated separation and purification used in solid-phase synthesis, and has the advantages of high efficiency and low cost, and can synthesize β-peptides and β-peptoids with high molecular weight. This review summarizes the polymerization methods for β-peptides and β-peptoids. Moreover, future developments of the polymerization method for the synthesis of β-peptides and β-peptoids will be discussed.     

Ionic liquid effects on the reaction of β-enaminones and tert-butylhydrazine and applications for the synthesis of pyrazoles

In order to evaluate the effect of a series of 10 different ionic liquids ([BMIM][BF₄], [BMIM][Br], [OMIM][BF₄], [BMIM][PF₆], [DBMIM][Br], [DBMIM][BF₄], [BMIM][OH], [BMIM][SCN], [HMIM][HSO₄] and [HMIM][CF₃CO₂]) the cyclocondensation reaction between 4-dimethylamino-1-phenyl-3-alken-2-ones (RC(O)CHCHNMe₂, where R = Ph, 4-Me-Ph, 4-F-Ph, 4-Cl-Ph, 4-Br-Ph, 4-NO₂-Ph, thien-2-yl, fur-2-yl, pyrrol-2-yl, pyrid-2-yl, hexyl, dimethoxymethyl) and tert-butylhydrazine was performed. The effects of each ionic liquid are discussed and the best yields for the cyclocondensation reaction studied were obtained using [BMIM][BF₄].     

Complex formation of Ibuprofen and β-Cyclodextrin by controlled particle deposition (CPD) using SC-CO2

Modern therapeutically used drugs are often lipophilic compounds. To reach the target structures, the drugs must be dissolved in physiological fluids and absorbed through entrance ports. In modern medicine, due to costs, convenience and compliance, oral application of solid forms is the preferential way. Since the bioavailability of orally applied drugs depends on the velocity of dissolution and absorption, methods to increase the dissolution of the lipophilic substances are often necessary to obtain significant blood levels. A well suitable way is the reduction of particle size to increase the dissolution velocity. However submicron particles are very difficult to be included in solid dosage forms. To overcome this, the controlled particle deposition (CPD) process was developed. The key idea behind CPD is to dissolve the drug of interest in supercritical CO₂, followed by permeation of the supercritical solution into the pores of the carrier and precipitation of the drug inside the pores. Thus, the attractive feature of CPD is the possibility to produce solvent-free, drug loaded carrier particles in a single processing step. In order to ensure that both, the drug and the carrier, exist as a solid under the conditions of study, the phase behaviour of RS(±)-Ibuprofen and of β-Cyclodextrin in the presence of CO₂ was investigated prior to the inclusion experiments. The results of the present investigations show, that an almost complete inclusion of RS(±)-Ibuprofen in β-Cyclodextrin at the solid state could be achieved. In addition, the dissolution rate of the complex formed by CPD was found to be significantly higher than that of untreated RS(±)-Ibuprofen and its physical mixture with β-Cyclodextrin.     

Enhancement of Lipase-catalyzed Synthesis of Caffeic Acid Phenethyl Ester in Ionic Liquid with DMSO Co-solvent☆

Caffeic acid phenethyl ester (CAPE) is a natural and rare ingredient with several biological activities, but its indus-trial production using lipase-catalyzed esterification of caffeic acid (CA) and 2-...