Synthetic strategies for the fluorescent labeling of epichlorohydrin-branched cyclodextrin polymers

• Milo Malanga,
• Mihály Bálint,
• István Puskás,
• Kata Tuza,
• Tamás Sohajda,
• László Jicsinszky,
• Lajos Szente and
• Éva Fenyvesi

Beilstein J. Org. Chem. 2014, 10, 3007–3018, doi:10.3762/bjoc.10.319

• Cyclodextrins (CDs) are cyclic oligosaccharides consisting of 6, 7 or 8 glucopyranose units (α-, β- or γ-CD, respectively). The capability for complexation, as well as their ability to stabilize and solubilize guest compounds, makes these substances prime candidates for incorporation in delivery systems for

• that has contact with water, or when CD is to be used for the removal of specific component(s) of a water-based process. In addition, free CDs are more difficult to recover for commercial recycling. A solution to these challenges is encoded in polymeric cyclodextrin structures. The cyclodextrins fixed

• , the process of purification and the characterization for the epichlorohydrin branched water soluble polymers obtained from native cyclodextrins are well established processes [9][10]. The characteristics of the cyclodextrin polymers can be modulated by appending neutral or ionic functional groups

Modification of physical properties of poly(L-lactic acid) by addition of methyl-β-cyclodextrin

• Toshiyuki Suzuki,
• Ayaka Ei,
• Yoshihisa Takada,
• Hiroki Uehara,
• Takeshi Yamanobe and
• Keiko Takahashi

Beilstein J. Org. Chem. 2014, 10, 2997–3006, doi:10.3762/bjoc.10.318

• orientation [17][18][19][20][21][22][23][24][25][26][27]. However, the brittleness of PLLA prevents drawing. To improve this, it is necessary to control the interchain interactions and lower the glass transition temperature (Tg) of the amorphous phase. Cyclodextrins (CDs) are cyclic molecules composed of six

Synthesis of uniform cyclodextrin thioethers to transport hydrophobic drugs

• Lisa F. Becker,
• Dennis H. Schwarz and
• Gerhard Wenz

Beilstein J. Org. Chem. 2014, 10, 2920–2927, doi:10.3762/bjoc.10.310

• displacement reactions starting from the corresponding per-(6-deoxy-6-bromo)cyclodextrins. Further modification of all 2-OH positions by etherification with iodo terminated triethylene glycol monomethyl ether (and tetraethylene glycol monomethyl ether, respectively) furnished water-soluble hosts. Especially

• anaesthesia. Keywords: active pharmaceutical ingredient; binding constant; cyclodextrin; derivatization; gas chromatography; sevoflurane; substitution pattern; Introduction Cyclodextrins (CDs) are cyclic oligomers of α-1,4-linked glucose units. Those CDs consisting of 6, 7, and 8 glucose units are called α

Cyclodextrin–polysaccharide-based, in situ-gelled system for ocular antifungal delivery

• Anxo Fernández-Ferreiro,
• Noelia Fernández Bargiela,
• María Santiago Varela,
• Maria Gil Martínez,
• Maria Pardo,
• Antonio Piñeiro Ces,
• José Blanco Méndez,
• Miguel González Barcia,
• Maria Jesus Lamas and
• Francisco.J. Otero-Espinar

Beilstein J. Org. Chem. 2014, 10, 2903–2911, doi:10.3762/bjoc.10.308

• Pharmacy, University of Santiago de Compostela (USC), Praza Seminario de Estudos Galegos s/n, Santiago de Compostela, 15701, Spain 10.3762/bjoc.10.308 Abstract Fluconazole was studied with two different hydrophilic cyclodextrins (hydroxypropyl-β-cyclodextrin (HPBCD) and sulfobutyl ether-β-cyclodextrin

• polysaccharides gellan gum and κ-carrageenan. This system showed good bioadhesive properties and effective control of fluconazole release. Keywords: cyclodextrins; eye drops; fluconazole; hydroxypropyl-β-cyclodextrin; sulfobutylether-β-cyclodextrin; Introduction Fungal keratitis is a serious disease that can

• solutions of both polysaccharides have characteristic properties related to their temperature dependence and cation-induced gelation [12]. A challenge in the design of bioadhesive ion-sensitive hydrogels is the incorporation of drugs with poor aqueous solubility. Cyclodextrins (CDs) are useful

Synthesis and characterization of a new photoinduced switchable β-cyclodextrin dimer

• Florian Hamon,
• Claire Blaszkiewicz,
• Marie Buchotte,
• Estelle Banaszak-Léonard,
• Hervé Bricout,
• Sébastien Tilloy,
• Eric Monflier,
• Christine Cézard,
• Laurent Bouteiller,
• Christophe Len and
• Florence Djedaini-Pilard

Beilstein J. Org. Chem. 2014, 10, 2874–2885, doi:10.3762/bjoc.10.304

• cavities of cis-AZO-CDim 1 are complexed simultaneously by two adamantyl units of the guest forming a 1:1 complex while trans-AZO-CDim 1 seems to lead to the formation of supramolecular polymers with an n:n stoichiometry. Keywords: azobenzene; cyclodextrins; inclusion complex; photoisomerization

• ; switchable binding behavior; Introduction α-, β- or γ-Cyclodextrins (CDs) are cyclic oligosaccharides composed of 6, 7 or 8 α-D-1,4 glucopyranose moieties, respectively. They are natural compounds produced from starch by the reaction of 4-α-glucanotransferases [1]. Their toroidal shape, with C6-primary

• -cyclodextrin (β-CD) is known to form supramolecular inclusion complexes with molecules, and such inclusion usually enhances the solubility of water-insoluble substances [1][2][3][4]. Pharmaceutical companies already use these cyclodextrins or their derivatives in their formulations [5][6]. In fact, they have a

Synthesis of modified cyclic and acyclic dextrins and comparison of their complexation ability

• Kata Tuza,
• László Jicsinszky,
• Tamás Sohajda,
• István Puskás and
• Éva Fenyvesi

Beilstein J. Org. Chem. 2014, 10, 2836–2843, doi:10.3762/bjoc.10.301

• compared the complex forming ability of α-, β- and γ-cyclodextrins (α-CD, β-CD and γ-CD) with their open ring analogs. In addition to the native cyclodextrins also modified cyclodextrins and the corresponding maltooligomers, functionalized with neutral 2-hydroxypropyl moieties, were synthesized. A new

• capillary electrophoresis (CE) using model guest compounds. In some cases cyclodextrins and their open-ring analogs (acyclodextrins) show similar complexation abilities, while with other guests considerably different behavior was observed depending on the molecular dimensions and chemical characteristics of

• from the three native α-, β-, and γ-cyclodextrins, respectively, are also suitable complexing agents. These maltooligomers are often considered as linear dextrins unable to form inclusion complexes [4]. Komiyama et al. found that there is complex formation but the complex forming ability of closed ring

Thermal and oxidative stability of the Ocimum basilicum L. essential oil/β-cyclodextrin supramolecular system

• Daniel I. Hădărugă,
• Nicoleta G. Hădărugă,
• Corina I. Costescu,
• Ioan David and
• Alexandra T. Gruia

Beilstein J. Org. Chem. 2014, 10, 2809–2820, doi:10.3762/bjoc.10.298

• compounds. One of the most frequently used matrices for molecular encapsulation, protection against oxidation or other degradation processes, as well as controlled release of relatively small bioactive compounds, are cyclodextrins (CDs) [30][31][32][33][34][35]. These are cyclic oligosaccharides consisting

Synthesis of an organic-soluble π-conjugated [3]rotaxane via rotation of glucopyranose units in permethylated β-cyclodextrin

• Jun Terao,
• Yohei Konoshima,
• Akitoshi Matono,
• Hiroshi Masai,
• Tetsuaki Fujihara and
• Yasushi Tsuji

Beilstein J. Org. Chem. 2014, 10, 2800–2808, doi:10.3762/bjoc.10.297

• . Partial ROESY NMR spectrum of 26 (400 MHz, CDCl3) showing the NOEs between aromatic protons of the axial hexa(para-phenylene) and inner protons of cyclodextrins. The synthetic route to the PMβ-CD based linked [3]rotaxane with a 5,15-di([1,1'-biphenyl]-4-yl)porphyrin backbone. Selective synthesis of fixed

Preparation and evaluation of cyclodextrin polypseudorotaxane with PEGylated liposome as a sustained release drug carrier

• Kayoko Hayashida,
• Taishi Higashi,
• Daichi Kono,
• Keiichi Motoyama,
• Koki Wada and
• Hidetoshi Arima

Beilstein J. Org. Chem. 2014, 10, 2756–2764, doi:10.3762/bjoc.10.292

• Graduate Schools “HIGO (Health life science: Interdisciplinary and Glocal Oriented) Program”, Kumamoto University, 5-1 Oe-honmachi, Chuo-ku, Kumamoto 862-0973, Japan 10.3762/bjoc.10.292 Abstract Cyclodextrins (CDs) can form polypseudorotaxanes (PPRXs) with drugs or drug carriers possessing linear polymers

• products. Keywords: cyclodextrins; doxorubicin; PEGylated liposome; polypseudorotaxane; sustained release; Introduction Cyclodextrins (CDs) are cyclic oligosaccharides comprising six (α-CD), seven (β-CD), and eight (γ-CD) glucopyranose units. They are characterized by a hydrophobic central cavity and a

Removal of volatile organic compounds using amphiphilic cyclodextrin-coated polypropylene

• Ludmilla Lumholdt,
• Sophie Fourmentin,
• Thorbjørn T. Nielsen and
• Kim L. Larsen

Beilstein J. Org. Chem. 2014, 10, 2743–2750, doi:10.3762/bjoc.10.290

• organic compounds are known to form stable inclusion complexes with cyclodextrins. Six different amphiphilic cyclodextrin derivatives were synthesised in order to elucidate whether or not the uptake abilities of the coating depend on the structure of the derivative. Headspace gas chromatography was used

• for quantification of the uptake exploiting the volatile nature of benzene and its derivatives. The capacity was shown to increase beyond the expected stoichiometries of guest–host complexes with ratios of up to 16:1. Keywords: amphiphilic cyclodextrins; polypropylene; static headspace chromatography

• , there is a great need to discover alternative methods to purify both industrial and private wastewater effectively in order to enable the EU member states to achieve the goals of the Water Framework Directive. Cyclodextrins (CDs) are cyclic, relatively small molecules consisting of units of glucose

A green approach to the synthesis of novel phytosphingolipidyl β-cyclodextrin designed to interact with membranes

• Yong Miao,
• Florence Djedaïni-Pilard and
• Véronique Bonnet

Beilstein J. Org. Chem. 2014, 10, 2654–2657, doi:10.3762/bjoc.10.278

• Yong Miao Florence Djedaini-Pilard Veronique Bonnet LG2A FRE-CNRS 3517 Institut de Chimie de Picardie FR CNRS 3085, SFR Condorcet, UPJV, 33 rue St Leu, 80039 Amiens, France 10.3762/bjoc.10.278 Abstract This work reports the synthesis of a new family of mono-substituted amphiphilic cyclodextrins

• using a green methodology. Reactions using greener and safer catalysts with more environmentally friendly purification solvents were performed. Four unreported mono-substituted cyclodextrins bearing a phytosphingolipidyl chain and a fatty acid chain (C10, C12, C14 and C18) were successfully obtained

• with a promising yield. Keywords: fatty ester; green chemistry; lipase; mono-substituted amphiphilic cyclodextrins; peptide Coupling; solvent-free medium; transesterification; Introduction Cyclodextrins (CDs) are sustainable compounds which are particularly interesting in the frame of pharmaceutical

Cyclodextrin-grafted polymers functionalized with phosphanes: a new tool for aqueous organometallic catalysis

• Jonathan Potier,
• Stéphane Menuel,
• David Mathiron,
• Véronique Bonnet,
• Frédéric Hapiot and
• Eric Monflier

Beilstein J. Org. Chem. 2014, 10, 2642–2648, doi:10.3762/bjoc.10.276

• Frères (Lestrem, France) is gratefully acknowledged for generous gifts of cyclodextrins. We thank Pr. Patrice Woisel and Dr. Aurélie Malfait for GPC analysis and Dr. Nicolas Kania for technical assistance.

Improving ITC studies of cyclodextrin inclusion compounds by global analysis of conventional and non-conventional experiments

• Eléonore Bertaut and
• David Landy

Beilstein J. Org. Chem. 2014, 10, 2630–2641, doi:10.3762/bjoc.10.275

• stability, enthalpy, or solubility. Keywords: cyclodextrins; global analysis; inclusion compounds; isothermal titration calorimetry; non-conventional experiments; Introduction The stability and thermodynamics of cyclodextrin inclusion compounds in solutions may be investigated with various analytical

• be designed to study the complexation phenomenon. Concerning the host, guest, and host–guest solutions to be prepared, some theoretical and experimental facts have to be considered. Firstly, as cyclodextrins are often used to solubilize hydrophobic guests, titration experiments generally employ the

• as the release protocol; it has been introduced by Heerklotz [14] for vesicles and then applied to cyclodextrins [30][31]. Protocol D (called “dilution”) corresponds to the reverse of protocol C: buffer injections within the host–guest mixture induce weak dilutions, thus dissociating a weak part of

Synthesis of a resin monomer-soluble polyrotaxane crosslinker containing cleavable end groups

• Ji-Hun Seo,
• Shino Nakagawa,
• Koichiro Hirata and
• Nobuhiko Yui

Beilstein J. Org. Chem. 2014, 10, 2623–2629, doi:10.3762/bjoc.10.274

• (PRX) crosslinker with cleavable end groups was synthesized to develop degradable photosetting composite resins. The PRX containing 50 α-cyclodextrins (α-CDs) with disulfide end groups was initially modified with n-butylamine to obtain a resin monomer-soluble PRX. The PRX containing 13 n-butyl groups

Encapsulation of biocides by cyclodextrins: toward synergistic effects against pathogens

• Véronique Nardello-Rataj and
• Loïc Leclercq

Beilstein J. Org. Chem. 2014, 10, 2603–2622, doi:10.3762/bjoc.10.273

• hosts are probably the cyclodextrins (CDs). CDs can form water-soluble complexes with numerous hydrophobic compounds. They have been widespread used in medicine, drug delivery and are of interest for the biocides encapsulation. Indeed, this enables the development of more or less complex systems that

• : cyclodextrin; biocide; encapsulation; host–guest chemistry; pathogen; textile; Introduction Since the first reference to cyclodextrins (CDs) in 1891 by Villiers, CD has been of great interest to researchers [1]. Cyclodextrins are composed of several α-D-glucopyranose units linked 1→4 and arranged in a conical

Synthesis and characterization of a hyper-branched water-soluble β-cyclodextrin polymer

• Francesco Trotta,
• Fabrizio Caldera,
• Roberta Cavalli,
• Andrea Mele,
• Carlo Punta,
• Lucio Melone,
• Franca Castiglione,
• Barbara Rossi,
• Monica Ferro,
• Vincenza Crupi,
• Domenico Majolino,
• Valentina Venuti and
• Dominique Scalarone

Beilstein J. Org. Chem. 2014, 10, 2586–2593, doi:10.3762/bjoc.10.271

• ; polyelectrolytes; soluble β-cyclodextrin polymers; Introduction Cyclodextrins (CDs) are biomolecules consisting of glucopyranoside units linked 1,4 to form cyclic oligossacharides. CDs composed of 6, 7 or 8 sugar units, which are known as α-, β- and γ-cyclodextrins respectively, are characterized by a toroidal

Synthesis of graft polyrotaxane by simultaneous capping of backbone and grafting from rings of pseudo-polyrotaxane

• Kazuaki Kato,
• Katsunari Inoue,
• Masabumi Kudo and
• Kohzo Ito

Beilstein J. Org. Chem. 2014, 10, 2573–2579, doi:10.3762/bjoc.10.269

• and cyclic molecules, are characterized by intramolecular mobility, namely rotation and sliding of the rings along the chains. Cyclodextrins (CDs) are often used as the cyclic components owing to their versatile and efficient inclusion abilities toward polymer guests [1][2]. The advantage of CD usage

Loose-fit polypseudorotaxanes constructed from γ-CDs and PHEMA-PPG-PEG-PPG-PHEMA

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

Beilstein J. Org. Chem. 2014, 10, 2461–2469, doi:10.3762/bjoc.10.257

• -hydroxyethyl methacrylate); polypseudorotaxane; Introduction Cyclodextrins (CDs) are a family of cyclic oligosaccharides composed of 6, 7 or 8 glucose units linked via α-1,4-glycosidic bonds. Due to the presence of a hydrophobic inner cavity with different geometric dimensions, CDs can act as host molecules

Towards the sequence-specific multivalent molecular recognition of cyclodextrin oligomers

• Michael Kurlemann and
• Bart Jan Ravoo

Beilstein J. Org. Chem. 2014, 10, 2428–2440, doi:10.3762/bjoc.10.253

• , with non-complementary strands aggregates of higher stoichiometry are generated. Keywords: cooperativity; cyclodextrins; molecular recognition; multivalency; sequence specificity; Introduction Multivalency is the interaction of a receptor and a ligand with at least two recognition motifs on each

• short peptides made of natural amino acids with aromatic side chains by different host moieties like coordination cages [37] and cucurbiturils [38][39] has been demonstrated. For cyclodextrins (CD) a similar approach is reported, but by using CD strands and different model peptides of natural and

• the uncomplexed cyclodextrins more easily than the 2:1 adduct of 5 and 14, resulting in a higher intrinsic binding constant (Figure 9D). These results demonstrate, that the homotrivalent guest strand 14 shows sequence-specificity in its molecular recognition. With the complementary CD strand a closed

A versatile δ-aminolevulinic acid (ΑLA)-cyclodextrin bimodal conjugate-prodrug for PDT applications with the help of intracellular chemistry

• Chrysie Aggelidou,
• Theodossis A. Theodossiou,
• Antonio Ricardo Gonçalves,
• Mariza Lampropoulou and
• Konstantina Yannakopoulou

Beilstein J. Org. Chem. 2014, 10, 2414–2420, doi:10.3762/bjoc.10.251

• in terms of water solubility and lack of aggregation. Keywords: cyclodextrins; PDT; protoporphyrin IX; prodrug; δ-aminolevulinic acid; Introduction Porphyrins have long been used as agents for tumor photodiagnosis (PDD) and photodynamic therapy (PDT) because of their preferential accumulation in

• hydrophobic cavity [7]. The cyclodextrins (CDs) are a notable family of semi-natural carbohydrate molecules approved as pharmaceutical excipients that improve the solubility and bioavailability of drugs through molecular encapsulation. We demonstrated [6] the conjugate’s (PpIX-CD) bimodal action of

Phosphinocyclodextrins as confining units for catalytic metal centres. Applications to carbon–carbon bond forming reactions

• Matthieu Jouffroy,
• Rafael Gramage-Doria,
• David Sémeril,
• Dominique Armspach,
• Dominique Matt,
• Werner Oberhauser and
• Loïc Toupet

Beilstein J. Org. Chem. 2014, 10, 2388–2405, doi:10.3762/bjoc.10.249

• HUGPHOS-2 [39], see Figure 1), which consists of methylated cyclodextrins (CD) equipped with an embedded phosphorus atom. In contrast to previously reported monophosphines [40][41][42][43] based on methylated CDs [41][42][43][44], our ligands have confining properties because of the presence of an inward

Oligomerization of optically active N-(4-hydroxyphenyl)mandelamide in the presence of β-cyclodextrin and the minor role of chirality

• Helmut Ritter,
• Antonia Stöhr and
• Philippe Favresse

Beilstein J. Org. Chem. 2014, 10, 2361–2366, doi:10.3762/bjoc.10.246

• spectroscopy. The magnetic interaction of the monomer with the cavity of RAMEB-CD is obvious in the 2D ROESY NMR spectra as shown in Figure 1 (marked areas). Principally, cyclodextrins and their derivatives are able to discriminate enantiomeric compounds [9][10]. Such chirality recognition is provable with 1H

Effect of cyclodextrin complexation on phenylpropanoids’ solubility and antioxidant activity

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

Beilstein J. Org. Chem. 2014, 10, 2322–2331, doi:10.3762/bjoc.10.241

• , France ULCO, UCEIV, F-59140 Dunkerque, France 10.3762/bjoc.10.241 Abstract The complexation abilities of five cyclodextrins (CDs) with seven phenylpropanoids (PPs) were evaluated by UV–visible spectroscopy, phase solubility studies and molecular modeling. Formation constants (Kf), complexation

• efficiency; cyclodextrins; formation constant; phenylpropanoids; solubility; Introduction Phenylpropanoids (PPs), produced through the shikimic acid pathway, are one of the major groups of natural compounds. They could be found in a wide variety of plants (clove, anise, basil, tarragon, fennel, parsley

• limited water solubility, stability and poor bioavailability [8][9]. Thus, their encapsulation may enhance their apparent solubility without losing their structural integrity and bioactivity. During the past years, cyclodextrins (CDs) have been widely used as encapsulating agents to enhance the solubility

End group functionalization of poly(ethylene glycol) with phenolphthalein: towards star-shaped polymers based on supramolecular interactions

• Carolin Fleischmann,
• Hendrik Wöhlk and
• Helmut Ritter

Beilstein J. Org. Chem. 2014, 10, 2263–2269, doi:10.3762/bjoc.10.235

• combination of CRP with supramolecular complex formation, e.g., by the use of cyclodextrins (CDs) [6][7][34]. The most important representatives of these cyclic oligosaccharides with respect to industrial applications consist of six (α-CD), seven (β-CD) and eight (γ-CD) glucopyranose units and have a cone

• moieties serving as the dipolarophil in a subsequent treatment with β-cyclodextrin azide. Thereby, a dipentaerythritol derivative carrying six cyclodextrins (DPE-CD) that are covalently attached through triazole rings was obtained. Mixing of mPEG-PP and DPE-CD resulted in the formation of stable complexes

Synthesis and optical properties of pyrrolidinyl peptide nucleic acid carrying a clicked Nile red label

• Nattawut Yotapan,
• Chayan Charoenpakdee,
• Pawinee Wathanathavorn,
• Boonsong Ditmangklo,
• Hans-Achim Wagenknecht and
• Tirayut Vilaivan

Beilstein J. Org. Chem. 2014, 10, 2166–2174, doi:10.3762/bjoc.10.224

• confirmed that the Nile red label is buried well within the hydrophobic pocket of the bulged duplexes and therefore not available to form an inclusion complex with the cyclodextrins [17]. Less pronounced shifts were observed with complementary and mismatched duplexes (2 and 4 nm, respectively) upon the