53784-83-1Relevant articles and documents
Synthesis of glycopolymer nanosponges with enhanced adsorption performances for boron removal and water treatment
Liao, Xueping,Wang, Bingyu,Zhang, Qiang
, p. 21193 - 21206 (2018)
The high-affinity interactions between cis-diols and boric/boronic acid have been widely employed as a tool for carbohydrate analysis, protein separation and boron removal. Herein we report the design and synthesis of cyclodextrin-scaffolded glycopolymers as bifunctional nanosponges for boron removal and water treatment for the first time. Different glycopolymer nanosponges (GNs) have been successfully synthesized from monosaccharides and β-cyclodextrin via a combination of a cross-linking reaction, Fischer glycosylation and a click reaction. Such functional GNs are mesoporous polymer frameworks with cis-diol-containing saccharides immobilized on the surface, which have exhibited selective adsorption behaviour towards boric acid depending on the structure of the GNs and the loaded saccharides. The GNs have also shown remarkable adsorption rates and capacities for an organic dye as a model pollutant in this work. Secondary bonding, such as hydrogen bonding and van der Waals forces between the immobilized saccharides and the adsorbates is believed to be responsible for the significantly enhanced adsorption rates and capacities. Such bifunctional materials may exhibit potential applications in seawater desalination and water treatment.
A host-guest supramolecular complex with photoregulated delivery of nitric oxide and fluorescence imaging capacity in cancer cells
Kandoth, Noufal,Malanga, Milo,Fraix, Aurore,Jicsinszky, Laszlo,Fenyvesi, Eva,Parisi, Tiziana,Colao, Ivana,Sciortino, Maria Teresa,Sortino, Salvatore
, p. 2888 - 2894 (2012)
Herein we report the design, preparation, and properties of a supramolecular system based on a tailored nitric oxide (NO) photodonor and a rhodamine-labeled β-cyclodextrin conjugate. The combination of spectroscopic and photochemical experiments shows the absence of significant interchromophoric interactions between the host and the guest in the excited states. As a result, the complex is able to release NO under the exclusive control of visible light, as unambiguously demonstrated by direct detection of this transient species through an amperometric technique, and exhibits the typical red fluorescence of the rhodamine appendage. The supramolecular complex effectively internalizes in HeLa cancer cells as proven by fluorescence microscopy, shows a satisfactory biocompatibility in the dark, and induces about 50 % of cell mortality upon irradiation with visible light. The convergence of all these properties in one single complex makes the present host-guest ensemble an appealing candidate for further delevopment of photoactivatable nanoscaled systems addressed to photostimulated NO-based therapy. NO delivery today: A supramolecular host-guest complex, based on a rhodamine-labeled β-cyclodextrin conjugate and a tailored NO photodonor, effectively internalizes in cancer cells, can be easily mapped intracellularly due to its satisfactory red fluorescence emission, and induces about 50 % of cellular death under the exclusive control of visible light stimuli. Copyright
A versatile δ -aminolevulinic acid (ALA)-cyclodextrin bimodal conjugate-prodrug for PDT applications with the help of intracellular chemistry
Aggelidou, Chrysie,Theodossiou, Theodossis A.,Gonalves, Antonio Ricardo,Lampropoulou, Mariza,Yannakopoulou, Konstantina
, p. 2414 - 2420 (2014)
Grafting of aδ-aminolevulinic acid (1) moieties on the narrow periphery of a β-cyclodextrin (β-CD) derivative through hydrolysable bonds was implemented, in order to generate a water-soluble, molecular/drug carrier with the capacity to undergo intracellular transformation into protoporphyrin IX (PpIX), an endogenous powerful photosensitizer for photodynamic therapy (PDT). The water-soluble derivative 2 was prepared by esterifying aδ-azidolevulinic acid with heptakis(6-hydroxyethylamino-6-deoxy)-β- cyclodextrin, with an average degree of substitution, DS = 3. Delivery of water-soluble, colorless 2 to cells resulted in intense red fluorescence registered by confocal microscopy, evidently due to the engagement of the intracellular machinery towards formation of PpIX. Conjugate 2 was further complexed with a fluorescein-labeled model guest molecule which was successfully transported into the cells, thereby demonstrating the bimodal action of the derivative. The present work shows the versatility of CDs in smart applications and constitutes advancement to our previously shown PpIX-β-CD conjugation both in terms of water solubility and lack of aggregation. lack of aggregation.
Nitric Oxide-Releasing Cyclodextrins
Jin, Haibao,Yang, Lei,Ahonen, Mona Jasmine R.,Schoenfisch, Mark H.
, p. 14178 - 14184 (2018)
A series of secondary amine-modified cyclodextrin (CD) derivatives was synthesized with diverse exterior terminal groups (i.e., hydroxyl, methyl, methoxyl, and primary amine). Subsequent reaction with nitric oxide (NO) gas under alkaline conditions yieldedN-diazeniumdiolate-modified CD derivatives. Adjustable NO payloads (0.6-2.4 μmol/mg) and release half-lives (0.7-4.2 h) were achieved by regulating both the amount of secondary amine precursors and the functional groups around the NO donors. The bactericidal action of these NO-releasing cyclodextrin derivatives was evaluated againstPseudomonas aeruginosa, a Gram-negative pathogen, with antibacterial activity proving dependent on both the NO payload and exterior modification. Materials containing a high density of NO donors or primary amines exhibited the greatest ability to eradicateP. aeruginosa. Of the materials prepared, only the primary amine-terminated heptasubstituted CD derivatives exhibited toxicity against mammalian L929 mouse fibroblast cells. The NO donor-modified CD was also capable of delivering promethazine, a hydrophobic drug, thus demonstrating potential as a dual-drug-releasing therapeutic.
Mechanistic Understanding of a Robust and Scalable Synthesis of Per(6-deoxy-6-halo)cyclodextrins, Versatile Intermediates for Cyclodextrin Modification
Zultanski, Susan L.,Kuhl, Nadine,Zhong, Wendy,Cohen, Ryan D.,Reibarkh, Mikhail,Jurica, Jon,Kim, Jungchul,Weisel, Lauren,Ekkati, Anil R.,Klapars, Artis,Gauthier, Donald R.,McCabe Dunn, Jamie M.
supporting information, p. 597 - 607 (2020/10/12)
Cyclodextrin (CD) perfunctionalization reactions are challenging to study because they proceed through a number of regioisomeric intermediates, thus warranting creative approaches to understanding the reaction mechanism. Particularly useful perfunctionalization targets are per(6-deoxy-6-halo)cyclodextrins. Their standard synthesis entails selective SN2 halogenation at their primary alcohols using a Vilsmeier reagent, but this requires a strongly basic quench to unmask the Vilsmeier-capped secondary alcohols. Herein we present an alternative and simple acidic hydrolytic quench that utilizes existing HX in the end-of-reaction solution and requires only the addition of water. We performed a detailed mechanistic investigation of the new quench, and a central feature was the use of proton sponge to develop an 1H NMR titration method for HX in organic solvent. This method was used to both quantify and remove HX in the prequenched reaction solution. The HX-free prequenched solution enabled us to (1) identify sensitive intermediates during the quench, (2) quantify all of the reaction byproducts, and (3) determine that HX is critical for hydrolysis. We then studied the halogenation reaction, wherein the new acidic quench facilitated high-throughput experimentation, using mass spectrometry as well as Design of Experiments with automated reaction profiling. Through this, we were able to establish robustness and understand the complex effects of Vilsmeier equivalents and temperature on the reaction outcome.
NITRIC OXIDE-RELEASING CYCLODEXTRINS AS BIODEGRADABLE ANTIBACTERIAL SCAFFOLDS AND METHODS PERTAINING THERETO
-
Page/Page column 97; 101, (2019/10/01)
Disclosed herein are cyclodextrin molecules covalently modified to store and release nitric oxide, as well as methods of making and uses thereof. The covalently modified cyclodextrin molecules may be tailored, in several embodiments, to release nitric oxide in a controlled manner and are useful for reduction and/or eradication of bacteria and for the treatment of disease.
