Thermal and oxidative stability of Atlantic salmon oil (Salmo salar L.) and complexation with β-cyclodextrin

• Daniel I. Hădărugă,
• Mustafa Ünlüsayin,
• Alexandra T. Gruia,
• Cristina Birău (Mitroi),
• Gerlinde Rusu and
• Nicoleta G. Hădărugă

Beilstein J. Org. Chem. 2016, 12, 179–191, doi:10.3762/bjoc.12.20

• -containing microcapsules [27][33] and spontaneous emulsification for obtaining nanoemulsions [20][31][32]. One nanoencapsulation method of fish oil components is the molecular encapsulation in cyclodextrins (CDs). The latter are natural or synthetically modified, cyclic oligosaccharides comprising 6, 7, and

Supramolecular structures based on regioisomers of cinnamyl-α-cyclodextrins – new media for capillary separation techniques

• Gabor Benkovics,
• Ondrej Hodek,
• Martina Havlikova,
• Zuzana Bosakova,
• Pavel Coufal,
• Milo Malanga,
• Eva Fenyvesi,
• Andras Darcsi,
• Szabolcs Beni and
• Jindrich Jindrich

Beilstein J. Org. Chem. 2016, 12, 97–109, doi:10.3762/bjoc.12.11

• This work focuses on the preparation and application of supramolecular structures based on mono-cinnamyl-α-cyclodextrins (Cin-α-CD). Pure regioisomers of Cin-α-CD having the cinnamyl moiety at the 2-O- or at the 3-O-position, respectively, were prepared, characterized and applied in capillary

Aggregation behavior of amphiphilic cyclodextrins in a nonpolar solvent: evidence of large-scale structures by atomistic molecular dynamics simulations and solution studies

• Giuseppina Raffaini,
• Fabio Ganazzoli and
• Antonino Mazzaglia

Beilstein J. Org. Chem. 2016, 12, 73–80, doi:10.3762/bjoc.12.8

• , Farmaceutiche ed Ambientali dell’Università di Messina, V. le F. Stagno d'Alcontres 31, 98166 Messina, Italy 10.3762/bjoc.12.8 Abstract Chemically modified cyclodextrins carrying both hydrophobic and hydrophilic substituents may form supramolecular aggregates or nanostructures of great interest. These systems

• with a hydrodynamic radius of the order of 80 nm and a relatively modest polydispersity, even though smaller nanometer-sized aggregates cannot be fully ruled out. Taken together, these simulation and experimental results indicate that amphiphilically modified cyclodextrins do also form large-scale

• nanoaggregates even in apolar solvents. Keywords: aggregation; amphiphilic cyclodextrins; molecular dynamics; nanoparticles; self-assembly; simulations; Introduction Amphiphilic cyclodextrins (aCD) are a class of molecules highly investigated for their self-assembly properties and inherent potential

Supramolecular polymer assembly in aqueous solution arising from cyclodextrin host–guest complexation

• Jie Wang,
• Zhiqiang Qiu,
• Yiming Wang,
• Li Li,
• Xuhong Guo,
• Duc-Truc Pham,
• Stephen F. Lincoln and
• Robert K. Prud’homme

Beilstein J. Org. Chem. 2016, 12, 50–72, doi:10.3762/bjoc.12.7

• ], chemical sensors [6] and drug delivery [7][8][9]. As discussed in a range of reviews [10][11][12][13][14] and books [15][16][17][18], cyclodextrins are naturally occurring cyclic oligosaccharides which are also produced industrially through the enzymatic metabolism of starch and related compounds. The

• enzymes used are cyclodextrin glucosyltransferases which are produced by several microorganisms including Bacillus macerans and Bacillus circulans. The most common cyclodextrins are α-, β- and γ-cyclodextrin (α-, β- and γ-CD) which consist of 6, 7 and 8 α-1,4-linked D-glucopyranose subunits, respectively

• . Stabilized by intramolecular hydrogen bonds, cyclodextrins form truncated toroidal structures with different internal annular diameters but the same depth of 7.9 Å (Figure 1, Table 1) [19]. The primary hydroxy groups are located on the C6 carbons of the D-glucopyranose subunits and delineate the narrower, or

Determination of formation constants and structural characterization of cyclodextrin inclusion complexes with two phenolic isomers: carvacrol and thymol

• Miriana Kfoury,
• David Landy,
• Steven Ruellan,
• Lizette Auezova,
• Hélène Greige-Gerges and
• Sophie Fourmentin

Beilstein J. Org. Chem. 2016, 12, 29–42, doi:10.3762/bjoc.12.5

• . However, they suffer from poor aqueous solubility and pronounced flavoring ability that limit their application in food systems. These drawbacks could be surpassed by encapsulation in cyclodextrins (CDs). Applications of their inclusion complexes with CDs were reported without investigating the inclusion

• : cyclodextrins; DOSY-NMR; formation constant; molecular modeling; solubility; Introduction Carvacrol (2-methyl-5-(1-methylethyl)phenol, 1) and thymol (5-methyl-2-(1-methylethyl)phenol, 2) are monoterpenic phenol isomers (Figure 1) produced by several aromatic plants (oregano, thyme, savory, marjoram, etc.) [1

• for loss during storage or heat treatement [16] and their relatively high flavor impact and low flavor threshold that lead to the deterioration of food organoleptic quality [4]. Encapsulation in cyclodextrins (CDs) could overcome these limitations. Indeed, CDs have the ability to increase the

Polydisperse methyl β-cyclodextrin–epichlorohydrin polymers: variable contact time ¹³C CP-MAS solid-state NMR characterization

• Isabelle Mallard,
• Davy Baudelet,
• Franca Castiglione,
• Monica Ferro,
• Walter Panzeri,
• Enzio Ragg and
• Andrea Mele

Beilstein J. Org. Chem. 2015, 11, 2785–2794, doi:10.3762/bjoc.11.299

• remove organic pollutants [6][11][12][13] and heavy metals [14] from water. The most efficient method for the synthesis of insoluble polymers is to use di- or polyfunctional linkers with monomers of cyclodextrins. Different effective crosslinkers have been reported in the literature such as

• epichlorohydrin [15][16], isocyanates [17][18], polycarboxylic acids [19][20] and anhydrides [21]. Following a slightly different approach, Trotta [18] and his group demonstrated that polymerization of cyclodextrins with a variety of synthetic equivalents of di- and tetracarboxylic acids provides an easy

Physical properties and biological activities of hesperetin and naringenin in complex with methylated β-cyclodextrin

• Waratchada Sangpheak,
• Jintawee Kicuntod,
• Roswitha Schuster,
• Thanyada Rungrotmongkol,
• Peter Wolschann,
• Nawee Kungwan,
• Helmut Viernstein,
• Monika Mueller and
• Piamsook Pongsawasdi

Beilstein J. Org. Chem. 2015, 11, 2763–2773, doi:10.3762/bjoc.11.297

• hesperetin with cyclodextrins (β-CD and DM-β-CD) were theoretically investigated by molecular dynamics simulation. The free energy values obtained suggested a more stable inclusion complex with DM-β-CD. The vdW force is the main guest–host interaction when hesperetin binds with CDs. The phase solubility

• three different cancer cell lines. The overall results suggested that solubilities and bioactivities of both flavanones were increased by complexation with methylated β-CDs. Keywords: binding energy; bioactivity; cyclodextrins; hesperetin; naringenin; Introduction Flavonoids are secondary metabolites

• physical properties and biological activities of hesperetin and naringenin through complexation with cyclodextrins. Computational tools (molecular dynamics simulation) were adopted to first predict the stability of flavanones/CDs inclusion complexes. Consequently, the experimental phase solubility and

Synthesis and photophysical characteristics of polyfluorene polyrotaxanes

• Aurica Farcas,
• Giulia Tregnago,
• Ana-Maria Resmerita,
• Pierre-Henri Aubert and
• Franco Cacialli

Beilstein J. Org. Chem. 2015, 11, 2677–2688, doi:10.3762/bjoc.11.288

• polyrotaxane compounds exhibit a granular morphology with lower dispersity and smaller roughness exponent of the film surfaces in comparison with those of the neat copolymer 3. Keywords: energy band gaps; fluorescence lifetimes; permethylated cyclodextrins; polyfluorene; polyrotaxanes; Introduction Over the

• wide variety of host molecules have the ability to encapsulate the π-conjugated backbones into their cavities based on intermolecular interactions, and thus leading to ICs. Cyclodextrins (CDs) are by far the most intensively investigated macrocyclic molecules in the synthesis of such supramolecular

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

• Mino R. Caira,
• Susan A. Bourne,
• Halima Samsodien and
• Vincent J. Smith

Beilstein J. Org. Chem. 2015, 11, 2616–2630, doi:10.3762/bjoc.11.281

• (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

• -methoxyestradiol; solubility; X-ray diffraction; Introduction This report focuses on the modes of inclusion of the anticancer agent 2-methoxyestradiol (2ME, Figure 1) in the host cyclodextrins (CDs) heptakis(2,6-di-O-methyl)-β-CD (DIMEB) and heptakis(2,3,6-tri-O-methyl)-β-CD (TRIMEB) in the solid state. The

Aggregation behaviour of amphiphilic cyclodextrins: the nucleation stage by atomistic molecular dynamics simulations

• Giuseppina Raffaini,
• Antonino Mazzaglia and
• Fabio Ganazzoli

Beilstein J. Org. Chem. 2015, 11, 2459–2473, doi:10.3762/bjoc.11.267

• Materiali Nanostrutturati, c/o Dipartimento di Scienze Chimiche, Biologiche, Farmaceutiche ed Ambientali dell’Università di Messina, Via F. Stagno d'Alcontres 31, 98166 Messina, Italy 10.3762/bjoc.11.267 Abstract Amphiphilically modified cyclodextrins may form various supramolecular aggregates. Here we

• report a theoretical study of the aggregation of a few amphiphilic cyclodextrins carrying hydrophobic thioalkyl groups and hydrophilic ethylene glycol moieties at opposite rims, focusing on the initial nucleation stage in an apolar solvent and in water. The study is based on atomistic molecular dynamics

• correlating their structures with the pharmaceutical properties. Keywords: aggregation; amphiphilic cyclodextrins; micelles; molecular dynamics simulations; nanoparticles; self-assembly; Introduction Inclusion complexes with supramolecular structures formed by native or modified cyclodextrins (CDs) are

Preparation of Pickering emulsions through interfacial adsorption by soft cyclodextrin nanogels

• Shintaro Kawano,
• Toshiyuki Kida,
• Mitsuru Akashi,
• Hirofumi Sato,
• Motohiro Shizuma and
• Daisuke Ono

Beilstein J. Org. Chem. 2015, 11, 2355–2364, doi:10.3762/bjoc.11.257

• to fabricate functional materials such as hollow permeable microcapsules. With regard to biomedical and pharmaceutical fields, emulsifiers derived from natural polymers such as saccharides are attractive compared to Pickering emulsifiers derived from synthetic polymers. Cyclodextrins (CDs) are cyclic

• . We have previously reported urethane-crosslinked CD polymers, which were prepared by reacting heptakis(2,6-di-O-methyl)-β-cyclodextrins (DM-β-CDs) with aromatic diisocyanates such as 4,4’-methylenebis(phenyl isocyanate) (MDI) and 1,4-phenylene diisocyanate (PDI) [18]. Although MDI- or PDI-crosslinked

Co-solvation effect on the binding mode of the α-mangostin/β-cyclodextrin inclusion complex

• Chompoonut Rungnim,
• Sarunya Phunpee,
• Manaschai Kunaseth,
• Supawadee Namuangruk,
• Kanin Rungsardthong,
• Thanyada Rungrotmongkol and
• Uracha Ruktanonchai

Beilstein J. Org. Chem. 2015, 11, 2306–2317, doi:10.3762/bjoc.11.251

• 10330, Thailand 10.3762/bjoc.11.251 Abstract Cyclodextrins (CDs) have been extensively utilized as host molecules to enhance the solubility, stability and bioavailability of hydrophobic drug molecules through the formation of inclusion complexes. It was previously reported that the use of co-solvents

• addition [2][3][4][5][6][7][8] and surfactant addition [9]. Complexation is one of the most utilized methods for enhancing the solubility of poorly soluble drugs. Cyclodextrins (CDs) are well-known macrocyclic oligosaccharides that are produced by enzymatic degradation of starch. CDs consist of 6, 7 and 8

• . [23] reviewed the hydrophobic effect of supramolecular complexes from MD simulation studies and emphasized that the non-covalent driving force of high-energy water in the cavity of cyclodextrins, cyclophanes and cucurbiturils was an essential factor for complexation with the guest molecule. MD

Self-assemblies of γ-CDs with pentablock copolymers PMA-PPO-PEO-PPO-PMA and endcapping via atom transfer radical polymerization of 2-methacryloyloxyethyl phosphorylcholine

• Jing Lin,
• Tao Kong,
• Lin Ye,
• Ai-ying Zhang and
• Zeng-guo Feng

Beilstein J. Org. Chem. 2015, 11, 2267–2277, doi:10.3762/bjoc.11.247

• -chain-stranded; pentablock copolymer; poly(pseudorotaxane); polyrotaxane; single-chain-stranded; Introduction Cyclodextrins (CDs) are a series of macrocyclic molecules composed of 6, 7, or 8 (α-, β-, and γ-CD, respectively) glucopyranose units. Their hydrophilic surface and hydrophobic inner cavity

Synthesis, structure, and mechanical properties of silica nanocomposite polyrotaxane gels

• Kazuaki Kato,
• Daisuke Matsui,
• Koichi Mayumi and
• Kohzo Ito

Beilstein J. Org. Chem. 2015, 11, 2194–2201, doi:10.3762/bjoc.11.238

• . These toughness and softness properties are attributable to both the characteristic sliding of polymer chains through the immobilized cyclodextrins on the silica nanoparticle and the entropic contribution of the cyclic components to the elasticity of the gels. Keywords: cyclodextrin; gel; mechanical

• . Polyrotaxane comprising an end-capped backbone polymer and threaded cyclic molecules such as cyclodextrins (CDs) can form a network structure by intermolecular binding of the cyclic components [10]. Since the polymer chains are topologically connected to each other without chemical bonds, the chains can slide

Cholesterol lowering effects of mono-lactose-appended β-cyclodextrin in Niemann–Pick type C disease-like HepG2 cells

• Keiichi Motoyama,
• Yumi Hirai,
• Rena Nishiyama,
• Yuki Maeda,
• Taishi Higashi,
• Yoichi Ishitsuka,
• Yuki Kondo,
• Tetsumi Irie,
• Takumi Era and
• Hidetoshi Arima

Beilstein J. Org. Chem. 2015, 11, 2079–2086, doi:10.3762/bjoc.11.224

• cholesterol sequestration is found to be a crucial factor in developing NPC disease. Cyclodextrins (CyDs) are non-reducing cyclic glucose oligosaccharides obtained by enzymatic means from starch-containing raw materials and have been used for the enhancement of drugs solubility, stability and bioavailability

Star-shaped tetrathiafulvalene oligomers towards the construction of conducting supramolecular assembly

• Masahiko Iyoda and
• Masashi Hasegawa

Beilstein J. Org. Chem. 2015, 11, 1596–1613, doi:10.3762/bjoc.11.175

• examples [30][31][32][33]. Other functional units such as fullerenes [34][35], cyclodextrins [36], porphyrin [37], and phthalocyanine [38][39][40] can also be introduced into the core of radial oligo-TTFs. As shown in Figure 1, TTF-annelated porphyrin 1 was synthesized by Becher and co-workers in 2001 [37

Qualitative evaluation of regioselectivity in the formation of di- and tri-6-O-tritylates of α-cyclodextrin

• Keisuke Yoshikiyo,
• Yoshihisa Matsui and
• Tatsuyuki Yamamoto

Beilstein J. Org. Chem. 2015, 11, 1530–1540, doi:10.3762/bjoc.11.168

• ,6C-di-O-trityl-α-CD’s. Keywords: 1H and 13C NMR spectroscopy; quantitative analysis; regioselectivity; tritylation; ultra-fast liquid chromatography (UFLC); Introduction Regioselective modification and deprotection on the primary hydroxy side of cyclodextrins (CDs) are of great importance in

Synthesis of tripodal catecholates and their immobilization on zinc oxide nanoparticles

• Franziska Klitsche,
• Julian Ramcke,
• Julia Migenda,
• Andreas Hensel,
• Tobias Vossmeyer,
• Horst Weller,
• Silvia Gross and
• Wolfgang Maison

Beilstein J. Org. Chem. 2015, 11, 678–686, doi:10.3762/bjoc.11.77

• an effector was prepared. This triscatecholate might be useful for the construction of diamandoid hydrophobic coatings [44] or for the reversible attachment of cyclodextrins to NPs by the formation of cyclodextrin/adamantane inclusion complexes [45]. Alternatively, acrylamide 4 and bromide 12 [42

Superstructures with cyclodextrins: Chemistry and applications II

• Gerhard Wenz

Beilstein J. Org. Chem. 2015, 11, 271–272, doi:10.3762/bjoc.11.30

• Gerhard Wenz Saarland University, Organic Macromolecular Chemistry, Campus C4 2, 66123 Saarbrücken, Germany 10.3762/bjoc.11.30 Keywords: cyclodextrins; Cyclodextrins (CDs) are cyclic α(1→4)-linked oligomeres of anhydroglucose. Since the 6-, 7- and 8-membered rings, called α-, β- and γ-CD

• polyrotaxanes [5][6][7]. The solubility and stability of CD complexes are controllable through the derivatization of CDs. Remarkable progress has been achieved over the past 10 years regarding the regioselective derivatization of cyclodextrins. Synthetic procedures for CD key derivatives such as mono-6-O-tosyl

Properties of cationic monosubstituted tetraalkylammonium cyclodextrin derivatives – their stability, complexation ability in solution or when deposited on solid anionic surface

• Martin Popr,
• Sergey K. Filippov,
• Nikolai Matushkin,
• Juraj Dian and
• Jindřich Jindřich

Beilstein J. Org. Chem. 2015, 11, 192–199, doi:10.3762/bjoc.11.20

• , yet robust and a straightforward process as well. Keywords: cyclodextrins; inclusion properties; solid surface; tetraalkylammonium derivatives; thermal stability; Introduction Cyclodextrins (CDs) are a very interesting group of natural macrocyclic carbohydrates, which were first described by

Formation of nanoparticles by cooperative inclusion between (S)-camptothecin-modified dextrans and β-cyclodextrin polymers

• Thorbjørn Terndrup Nielsen,
• Catherine Amiel,
• Laurent Duroux,
• Kim Lambertsen Larsen,
• Lars Wagner Städe,
• Reinhard Wimmer and
• Véronique Wintgens

Beilstein J. Org. Chem. 2015, 11, 147–154, doi:10.3762/bjoc.11.14

• -cyclodextrin polymers. In aqueous solution nanoparticles were formed from association between the (S)-camptothecin–dextran polymers and the β-cyclodextrin polymers. Keywords: (S)-camptothecin; cyclodextrins; fluorescence; nanoparticles; ITC; Introduction Cancer remains to be the major cause of mortality in

• size. Interaction with suitable correspondent polymers with pendent cyclodextrins may form nanoparticles with the target properties. In recent years cyclodextrin (CD) polymer-based drug-delivery systems have attracted much attention in this field [7][8]. CDs are cyclic sugar molecules constituted of

Effects of RAMEA-complexed polyunsaturated fatty acids on the response of human dendritic cells to inflammatory signals

• Éva Rajnavölgyi,
• Renáta Laczik,
• Viktor Kun,
• Lajos Szente and
• Éva Fenyvesi

Beilstein J. Org. Chem. 2014, 10, 3152–3160, doi:10.3762/bjoc.10.332

• Solubilization of n−3 PUFAs Cyclodextrins (CDs) are efficient solubilizers of lipids [42]. The water-insoluble n−3 PUFAs were solubilized in aqueous solutions of randomly methylated α- and β-CD (RAMEA and RAMEB, respectively), but the similar γ-CD derivative, RAMEG was ineffective to modulate the solubility

• solubilized by RAMEA provide with a new tool for optimizing the anti-inflammatory effects exerted on human moDC and mediated via the GPR120 receptor without interfering with the cell membrane structure. Experimental Fatty acids, cyclodextrins The fatty acids were purchased from Sigma-Aldrich. The randomly

Inclusion of trans-resveratrol in methylated cyclodextrins: synthesis and solid-state structures

• Lee Trollope,
• Dyanne L. Cruickshank,
• Terence Noonan,
• Susan A. Bourne,
• Milena Sorrenti,
• Laura Catenacci and
• Mino R. Caira

Beilstein J. Org. Chem. 2014, 10, 3136–3151, doi:10.3762/bjoc.10.331

• , poor aqueous solubility) limit such applications and its inclusion in cyclodextrins (CDs) has potential for addressing these shortcomings. Here, various methods of the attempted synthesis of inclusion complexes between trans-resveratrol and three methylated cyclodextrins (permethylated α-CD

• shortcoming [5], among them inclusion complexation with cyclodextrins (CDs), which are well-known solubilisers of lipophilic molecules [6]. In addition to enhancing the solubility of guest molecules, CDs can confer chemical stability on bioactive molecules through inclusion of sensitive guest moieties within

• preparation of binary mixtures was a generous gift from Denk Feinchemie GmbH (München, Germany). For co-precipitation experiments, the RSV used was supplied by Sigma-Aldrich (South Africa). Cyclodextrins were purchased from Wacker Chemie Italia Srl (Milan, Italy) and Cyclolab (Budapest, Hungary). All other

Release of β-galactosidase from poloxamine/α-cyclodextrin hydrogels

• César A. Estévez,
• José Ramón Isasi,
• Eneko Larrañeta and
• Itziar Vélaz

Beilstein J. Org. Chem. 2014, 10, 3127–3135, doi:10.3762/bjoc.10.330

• : controlled release; cyclodextrins; lactase; polypseudorotaxane; supramolecular gel; Introduction In the Western diet, carbohydrates contribute about 50% of calories, distributed in the following ratio: starch (50%), sucrose (30%), lactose (6%), maltose (1–2%), and others (12%: trehalose, glucose, fructose

• nanocarriers, they have the ability to hold/release drugs as a function of pH [9]. Cyclodextrins (CD) are macrocyclic compounds consisting of several glucose units linked by α-D-1,4-glycosidic bonds. Despite their high solubility in water, the internal cavity of cyclodextrins is non-polar and these compounds

• are able to form host–guest complexes by the inclusion of hydrophobic molecules. Cyclodextrins also act as hosts in the formation of inclusion compounds with polymer chains through non-covalent interactions [10]. For instance, incorporation of 5% α-CD transforms dilute Tetronic solutions into gels

Conjugates of methylated cyclodextrin derivatives and hydroxyethyl starch (HES): Synthesis, cytotoxicity and inclusion of anaesthetic actives

• Lisa Markenstein,
• Antje Appelt-Menzel,
• Marco Metzger and
• Gerhard Wenz

Beilstein J. Org. Chem. 2014, 10, 3087–3096, doi:10.3762/bjoc.10.325

• ; occupancy; polymer; sevoflurane; solubility; starch; Introduction Cyclodextrins (CDs), α(1→4) linked cyclic oligomers of anhydroglucose, are produced nowadays in industrial scale [1]. CDs are able to complex hydrophobic or amphiphilic guest molecules in aqueous phase [2]. β-CD, the seven membered ring