Inclusion Complexation of Benzanilide and Fast Violet B with β-cyclodextrin-A Theoretical Approach

Organic Chemistry Plus ◽

10.37256/ocp.112020147 ◽

2020 ◽

pp. 23-28

Author(s):

A. Antony Muthu Prabhu

Keyword(s):

Gas Phase ◽

Aromatic Ring ◽

Inclusion Complexes ◽

Theoretical Investigation ◽

Theoretical Approach ◽

Inclusion Complexation ◽

The Other ◽

Guest Molecules ◽

Och3 Group ◽

Structural Assignment

The theoretical investigation of inclusion complexation of amide-imidol tautomer of two guest molecules benzanilide (BA) and fast violet B (FVB) with β-cyclodextrin (β-CD) using DFT B3LYP 3-21G method in the gas phase. Benzanilide has no substitution in the basic skeleton and the other selected compound substituted with three groups such as –NH2, -CH3 and –OCH3 group in the same aromatic ring. The tautomer of two selected compounds was formed the stable inclusion complexes with the β-CD supramolecule. The theoretically calculated complexation energy was observed the negative value for all the inclusion complexes. This method was applicable to determine the structural assignment of the inclusion complexes between BA, FVB and β-CD.

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Inclusion complexes of 2-methoxyestradiol with dimethylated and permethylated β-cyclodextrins: models for cyclodextrin–steroid interaction

Beilstein Journal of Organic Chemistry ◽

10.3762/bjoc.11.281 ◽

2015 ◽

Vol 11 ◽

pp. 2616-2630 ◽

Cited By ~ 13

Author(s):

Mino R Caira ◽

Susan A Bourne ◽

Halima Samsodien ◽

Vincent J Smith

Keyword(s):

Inclusion Complexes ◽

Anticancer Agent ◽

Inclusion Complexation ◽

Aqueous Solubility ◽

X Ray Diffraction ◽

Guest Molecules ◽

X Ray ◽

Rapid Dissolution ◽

First Time ◽

Secondary Side

The interaction between the potent anticancer agent 2-methoxyestradiol (2ME) and a series of cyclodextrins (CDs) was investigated in the solid state using thermal analysis and X-ray diffraction, while the possibility of enhancing its poor aqueous solubility with CDs was probed by means of equilibrium solubility and dissolution rate measurements. Single crystal X-ray diffraction studies of the inclusion complexes between 2ME and the derivatised cyclodextrins heptakis(2,6-di-O-methyl)-β-CD (DIMEB) and heptakis(2,3,6-tri-O-methyl)-β-CD (TRIMEB) revealed for the first time the nature of the encapsulation of a bioactive steroid by representative CD host molecules. Inclusion complexation invariably involves insertion of the D-ring of 2ME from the secondary side of each CD molecule, with the 17-OH group generally hydrogen bonding to a host glycosidic oxygen atom within the CD cavity, while the A-ring and part of the B-ring of 2ME protrude from the secondary side. In the case of the TRIMEB·2ME complex, there is evidence that complexation proceeds with mutual conformational adaptation of host and guest molecules. The aqueous solubility of 2ME was significantly enhanced by CDs, with DIMEB, TRIMEB, randomly methylated β-CD and hydroxypropyl-β-CD being the most effective hosts. The 2:1 host–guest β-CD inclusion complex, prepared by two methods, yielded very rapid dissolution in water at 37 °C relative to untreated 2ME, attaining complete dissolution within 15 minutes (co-precipitated complex) and 45 minutes (complex from kneading).

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Crystalline inclusion complexes as media of molecular recognitions and selective reactions

Pure and Applied Chemistry ◽

10.1351/pac200173071137 ◽

2001 ◽

Vol 73 (7) ◽

pp. 1137-1145 ◽

Cited By ~ 18

Author(s):

Fumio Toda

Keyword(s):

Inclusion Complexes ◽

Chemical Reaction ◽

Active Compound ◽

Inclusion Complexation ◽

Photochemical Reactions ◽

Optically Active ◽

Crystalline Inclusion ◽

Guest Molecules ◽

Water Suspension ◽

Enantioselective Reactions

Hexaol host compounds which include guest molecules maximum in 1:6 ratio were prepared. Aromatic hexaol host, hexahydroxytriphenylene, was found to form chiral inclusion crystal by complexation with achiral guest molecules. Some interesting and important optical resolutions of rac-guests by inclusion complexation with a chiral host were described. When chemical reaction and the inclusion complexation procedures in a water suspension medium are combined, new economical and ecological method of the preparation of optically active compound can be established. When photochemical reactions are carried out in an inclusion crystal with a chiral host, enantioselective reactions occur, and optically active product can be obtained. Several successful reactions are described.

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Computational Insights Into the Influence of Substitution Groups on the Inclusion Complexation of β-Cyclodextrin

Frontiers in Chemistry ◽

10.3389/fchem.2021.668400 ◽

2021 ◽

Vol 9 ◽

Author(s):

Xianghua Yan ◽

Yue Wang ◽

Tong Meng ◽

Hui Yan

Keyword(s):

Aromatic Hydrocarbons ◽

Inclusion Complexation ◽

Md Simulations ◽

Ring Structure ◽

Water Soluble ◽

The Other ◽

Guest Molecules ◽

Hydrophobic Cavity ◽

Polycyclic Aromatic ◽

The Stability

Cyclodextrins (CDs) and their derivatives have good prospects in soil remediation application due to their ability to enhance the stability and solubility of low water-soluble compounds by inclusion performance. To investigate the effect of different structural properties of cyclodextrin and its derivatives on the inclusion complexation, molecular dynamic (MD) simulations were performed on the inclusion complexes formed by three kinds of CDs with polycyclic aromatic hydrocarbons (PAHs). Based on neutral β-CD, the other two CDs were modified by introducing substitutional groups, including 2-hydroxypropyl and sulfonated butyl (SBE) functional groups in the ring structure, called HP-CD and SBE-CD. MD results show that PAH can merely enter into the cavity of SBE–β-CD from its wide rim. The substitutional groups significantly affect the structure of CDs, which may also cause the flipping of the glucose units. However, the substitutional groups can also enlarge the volume of the hydrophobic cavity, resulting in a tight combination with the guest molecules.

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Synthesis of Amylosic Supramolecular Materials by Glucan Phosphorylase-Catalyzed Enzymatic Polymerization According to the Vine-Twining Approach

Synlett ◽

10.1055/s-0039-1690804 ◽

2020 ◽

Vol 31 (07) ◽

pp. 648-656 ◽

Cited By ~ 1

Author(s):

Jun-ichi Kadokawa

Keyword(s):

Inclusion Complexes ◽

Inclusion Complexation ◽

Soft Materials ◽

Enzymatic Polymerization ◽

Hierarchical Architecture ◽

Supramolecular Network ◽

Guest Molecules ◽

Supramolecular Materials ◽

Glucan Phosphorylase ◽

Supramolecular Networks

This article overviews the synthesis of amylosic supramolecular materials through inclusion complexation in glucan phosphorylase (GP)-catalyzed enzymatic polymerization. Amylose is a polysaccharide that is known to form inclusion complexes with a number of hydrophobic small guest molecules. A pure amylose can be synthesized by the enzymatic polymerization of α-d-glucose 1-phosphate monomer with a maltooligosaccharide primer catalyzed by GP. The author has reported that the propagating amylosic chain in the enzymatic polymerization twines around hydrophobic polymers present in aqueous reaction media to form supramolecular inclusion complexes. As it is similar to the way that vines of a plant grow around a rod, this polymerization is termed ‘vine-twining polymerization’. Amylosic supramolecular network materials have been obtained through the vine-twining polymerization by using copolymers, where hydrophobic guest polymers are covalently grafted on hydrophilic main-chain polymers. The enzymatically produced amylosic chains form complexes with the guest polymers among graft copolymers, which act as cross-linking points to form supramolecular networks, resulting in the formation of soft materials, such as gels and films. Vine-twining polymerization using appropriately designed guest polymers has also been performed, which leads to supramolecular products that exhibit new functionality.1 Introduction2 Vine-Twining Polymerization to Form Supramolecular Inclusion Complexes3 Selective Complexation of Amylose toward Guest Polymers in Vine-Twining Polymerization4 Hierarchical Architecture of Amylosic Supramolecular Network Materials by Vine-Twining Polymerization Approach5 Hierarchical Fabrication of Amylosic Supramolecular Materials by Vine-Twining Polymerization Using Designed Guest Polymers6 Conclusions

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A polycentric growth model of gallium arsenide epitaxial layers from the gas phase with simultaneous diffusion, adsorption and chemical reaction

Collection of Czechoslovak Chemical Communications ◽

10.1135/cccc19882995 ◽

1988 ◽

Vol 53 (12) ◽

pp. 2995-3013

Author(s):

Emerich Erdös ◽

Jindřich Leitner ◽

Petr Voňka ◽

Josef Stejskal ◽

Přemysl Klíma

Keyword(s):

Growth Rate ◽

Gallium Arsenide ◽

Epitaxial Growth ◽

Gas Phase ◽

Surface Reaction ◽

Quantitative Description ◽

The Other ◽

Rate Equations ◽

Impact Interaction ◽

Partial Pressures

For a quantitative description of the epitaxial growth rate of gallium arsenide, two models are proposed including two rate controlling steps, namely the diffusion of components in the gas phase and the surface reaction. In the models considered, the surface reaction involves a reaction triple - or quadruple centre. In both models three mechanisms are considered which differ one from the other by different adsorption - and impact interaction of reacting particles. In every of the six cases, the pertinent rate equations were derived, and the models have been confronted with the experimentally found dependences of the growth rate on partial pressures of components in the feed. The results are discussed with regard to the plausibility of individual mechanisms and of both models, and also with respect to their applicability and the direction of further investigations.

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ß-Cyclodextrin Inclusion Complexes with Catechol-Containing Antioxidants Protocatechuic Aldehyde and Protocatechuic Acid—An Atomistic Perspective on Structural and Thermodynamic Stabilities

Molecules ◽

10.3390/molecules26123574 ◽

2021 ◽

Vol 26 (12) ◽

pp. 3574

Author(s):

Thammarat Aree

Keyword(s):

Inclusion Complexes ◽

Protocatechuic Acid ◽

Inclusion Complexation ◽

Geometry Optimization ◽

Therapeutic Effects ◽

Full Geometry Optimization ◽

Oh Groups ◽

X Ray ◽

Protocatechuic Aldehyde ◽

Crystal Contacts

Protocatechuic aldehyde (PCAL) and protocatechuic acid (PCAC) are catechol derivatives and have broad therapeutic effects associated with their antiradical activity. Their pharmacological and physicochemical properties have been improved via the cyclodextrin (CD) encapsulation. Because the characteristics of b-CD inclusion complexes with PCAL (1) and PCAC (2) are still equivocal, we get to the bottom of the inclusion complexation by an integrated study of single-crystal X-ray diffraction and DFT full-geometry optimization. X-ray analysis unveiled that PCAL and PCAC are nearly totally shielded in the b-CD wall. Their aromatic rings are vertically aligned in the b-CD cavity such that the functional groups on the opposite side of the ring (3,4-di(OH) and 1-CHO/1-COOH groups) are placed nearby the O6–H and O2–H/O3–H rims, respectively. The preferred inclusion modes in 1 and 2 help to establish crystal contacts of OH×××O H-bonds with the adjacent b-CD OH groups and water molecules. By contrast, the DFT-optimized structures of both complexes in the gas phase are thermodynamically stable via the four newly formed host–guest OH⋯O H-bonds. The intermolecular OH×××O H-bonds between PCAL/PCAC 3,4-di(OH) and b-CD O6–H groups, and the shielding of OH groups in the b-CD wall help to stabilize these antioxidants in the b-CD cavity, as observed in our earlier studies. Moreover, PCAL and PCAC in distinct lattice environments are compared for insights into their structural flexibility.

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Methylene. III. Gas phase reactions with 1-chloropropane

Proceedings of the Royal Society of London Series A - Mathematical and Physical Sciences ◽

10.1098/rspa.1969.0146 ◽

1969 ◽

Vol 312 (1509) ◽

pp. 141-161 ◽

Cited By ~ 2

Keyword(s):

Gas Phase ◽

Rate Constants ◽

Hydrogen Abstraction ◽

The Other ◽

Gas Phase Reactions ◽

Other Hand ◽

Chlorine Substituent ◽

High Degree ◽

Singlet Methylene

The work described in this and the following paper is a continuation of that in parts I and II, devoted to elucidation of the mechanism of the reactions of methylene with chloroalkanes, with particular reference to the reactivities of singlet and triplet methylene in abstraction and insertion processes. The products of the reaction between methylene, prepared by the photolysis of ketene, and 1-chloropropane have been identified and estimated and their dependence on reactant pressures, photolysing wavelength and presence of foreign gases (oxygen and carbon monoxide) has been investigated. Both insertion and abstraction mechanisms contribute significantly to the over-all reaction, insertion being relatively much more important than with chloroethane. This type of process appears to be confined to singlet methylene. If, as seems likely, there is no insertion into C—Cl bonds under our conditions (see part IV), insertion into C2—H and C3—H bonds occurs in statistical ratio, approximately. On the other hand, the chlorine substituent reduces the probability of insertion into C—H bonds in its vicinity. As in the chloroethane system, both species of methylene show a high degree of selectivity in their abstraction reactions. We find that k S Cl / k S H >7.7, k T Cl / k T H < 0.14, where the k ’s are rate constants for abstraction, and the super- and subscripts indicate the species of methylene and the type of atom abstracted, respectively. Triplet methylene is discriminating in hydrogen abstraction from 1-C 3 H 7 Cl, the overall rates for atoms attached to C1, C2, C3 being in the ratios 2.63:1:0.

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