- Electrochemical redox responsive polymeric micelles formed from amphiphilic supramolecular brushes
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The end-decorated homopolymer poly(ε-caprolactone)-ferrocene threaded onto a β-cyclodextrin-functionalized main-chain polymer can form a class of amphiphilic noncovalent graft copolymers based on the host-guest interactions of the terminal groups on the side chains. These new supramolecular polymer brushes can further self-assemble into micellar aggregates that exhibit reversible assembly and disassembly behavior under an electrochemical redox trigger, which opens up a new route to building dynamic block copolymer topologies. This journal is the Partner Organisations 2014.
- Feng, Anchao,Yan, Qiang,Zhang, Huijuan,Peng, Liao,Yuan, Jinying
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- Star polymers with both temperature sensitivity and inclusion functionalities
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We designed and synthesized novel star poly(N-isopropylacrylamide) (star-PNIPAm) and star-PNIPAm with cyclodextrin (CD) end groups (star-PNIPAm-CD) by atom transfer radical polymerization (ATRP). In the synthesis, β-CD-core with 21 initiation sites, heptakis[2,3,6-tri-O-(2- chloropropionyl)]-β-cyclodextrin (21Cl-β-CD), was first synthesized by the reaction of β-CD with 2-chloropropionyl chloride (CPC). Then, 21-arm star-PNIPAm (PDI = 1.03) was synthesized by ATRP of N-isopropylacrylamide (NIPAm) initiated via 21Cl-β-CD. Finally, a star-PNIPAm-CD (PDI = 1.02) was synthesized by ATRP of a monovinyl β-CD (GMA-EDA-β-CD) initiated via star-PNIPAm. The obtained star-PNIPAm and star-PNIPAm-CD were characterized by means of SEC/MALLS, NMR, IR, and DSC. By using 8-anilino-1-naphthalenesulfonic acid ammonium salt hydrate (ANS), 1-adamantanamine hydrochloride (ADA-NH 3Cl), and ibuprofen sodium salt (ibuprofen-Na) as guest molecules, thermal sensitivity and inclusion behaviors of the star polymers were investigated by fluorescence spectrophotometer and DLS. It is found that the star polymers can combine both thermal sensitivity of PNIPAm and inclusion behavior of β-CD. Interestingly, the star polymers can self-assembly to form nanosized aggregates in aqueous solution above their LCSTs. The self-assembly behavior shows molecular recognition capability. And formation and dissociation of the nanosized aggregation can change reversibly by changing temperature above and below the LCST.
- Liu, Yu-Yang,Zhong, Yao-Bing,Nan, Jiang-Kun,Tian, Wei
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- Thio[2-(benzoylamino)ethylamino]-β-CD fragment modified gold nanoparticles as recycling extractors for [60]fullerene
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Gold particles are modified with surface-attached bis(β-cyclodextrin)s bearing S-S bridges to give water-soluble cyclodextrin-modified gold nanoparticles, which are successfully used as recycling extractors for [60]fullerene. The Royal Society of Chemistry 2005.
- Liu, Yu,Yang, Ying-Wei,Chen, Yong
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- β-Cyclodextrin-modified hybrid magnetic nanoparticles for catalysis and adsorption
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β-Cyclodextrin-modified hybrid magnetic nanoparticles (Fe 3O4@SiO2-PGMACD) were synthesized via the combination of atom transfer radical polymerization on the surfaces of silica coated iron oxide particles (Fe3O4@SiO2) and ring-opening reaction of epoxy groups. The feasibility of using Fe 3O4@SiO2-PGMACD as separable immobilized catalyst and adsorbent was demonstrated. It was found: (1) the prepared Fe 3O4@SiO2-PGMACD could be used as catalyst in substrate-selective oxidation of alcohols system and the catalytic efficiency was close to pure β-Cyclodextrin of equal quantity; (2) the resulting particles appeared remarkably dominant adsorption capacity compared with poly(glycidyl methacrylate) grafted magnetic nanoparticles (Fe3O 4@SiO2-PGMA) in the removal of bisphenol A from aqueous solutions. The results suggest that the novel fabricated nanoparticles could serve as bifunctional materials in catalysis or adsorption and subsequently become potential multifunctional materials. The Royal Society of Chemistry 2011.
- Kang, Yan,Zhou, Lilin,Li, Xia,Yuan, Jinying
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- Synthesis of novel indolyl modified β-cyclodextrins and their molecular recognition behavior controlled by the solution's pH value
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In order to investigate the effects of substituent and tether length in molecular recognition, three novel indolyl-contained β-cyclodextrin derivatives were synthesized by the condensation of indol-3-ylbutyric acid with the corresponding oligo(aminoethylamino)-β-cyclodextrin in the presence of DCC. Their molecular recognition behavior with some representative dye guests, i.e. Acridine Red, Rhodamine B, Neutral Red, Brilliant Green and Methyl Orange, was studied by using absorption, fluorescence and circular dichroism spectrometry. From the results of induced circular dichroism spectra and two-dimensional NMR spectroscopy, it was found that the initial conformations of these compounds are dramatically different in aqueous buffers of pH 2.0 and 7.2, which intrinsically determine the molecular binding ability of the host. It was also revealed that both the guest structure and the host tether length were responsible for the inclusion complexation stability. Therefore, on the one hand the hydrophobicity and substituent effect of the guest simultaneously determine the stability of host-guest complex through hydrophobic, van der Waals, and electrostatic interactions. On the other hand, the size/shape-matching relationship and induced-fit concept working between host and guest also play crucial roles in the selective molecular binding process of cyclodextrin hosts.
- Liu, Yu,You, Chang-Cheng,He, Song,Chen, Guo-Song,Zhao, Yan-Li
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- Influence of supramolecular layer-crosslinked structure on stability of dual pH-Responsive polymer nanoparticles for doxorubicin delivery
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Undesired physiological instability remains a major limitation for nanoparticle-based drug delivery. To overcome this issue, a dual pH-responsive supramolecular layer-crosslinked nanoparticles (PCB-b-PCD/PBM-b-PDPA NPs, PDM NPs), which consisted of pH-responsive hydrophobic poly(diisopropylethyl methacrylate) (pKa ≈6.3) as the core, hydrophilic poly((methacrylic acid betaine) methyl methacrylate) as the shell and pH-responsive supramolecular crosslinked layer based on β-cyclodextrin and benzimidazole (pKa 6.0), was prepared. Effects of this supramolecular layer-crosslinked structure on dilution and stored stability, protein adsorption, and pH-responsibility were investigated. PDM NPs exhibited lower critical aggregation concentrations, good unimodal distribution and better dilution stability in comparison with non-crosslinked PCB-PDPA NPs. Moreover this pH-responsive supramolecular layer-crosslinked structure did not only influence the anti-protein adsorption ability, but also reduced the disintegrated pH (from 6.3 to below 6.0) of PDM NPs, which leads to the DOX was released from PDM NPs at the mildly acid condition effectively and sustainably in vitro. Therefore, this pH-responsive layer-crosslinked NPs held promising potentials as a smart nanocarriers for drug delivery.
- Feng, Hailiang,Sun, Yu,Zhang, Jianhua,Deng, Liandong,Dong, Anjie
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- In vitro dissolution study on inclusion complex of piperine with ethylenediamine-β-cyclodextrin
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The co-evaporation method was used to synthesize the EN-β-CD@Piperine inclusion complex with a molar ratio of 1:1. The properties and structures of the inclusion complex were characterized by various methods to investigate the inclusion mode and interactions between host and guest. The results of molecular modeling were theoretically analyzed to determine the inclusion mechanism of inclusion complexes. Finally, the vitro dissolution release studies showed that the water solubility of piperine was significantly enhanced when EN-β-CD was combined with piperine. Therefore, the EN-β-CD@Piperine inclusion complex provides a promising development for the clinical application of piperine in the future.
- Liu, Kai,Liu, Huijun,Li, Zhendong,Li, Wei,Li, Liuxing
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- Synthesis and photodynamic therapy properties of a water-soluble hypocrellin modified by cyclodextrin
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For improving water solubility of hypocrellin B (HB), a cyclodextrin modified hypocrellin B (HBCD) was designed and synthesized. Electron spin resonance (ESR) measurement indicated that this HB derivative remained photodynamically active in terms of type I and type II mechanisms. HBCD is water-soluble and possesses stronger photosensitized damage ability to calf thymus DNA than hypocrellin B.
- Ou, Zhi-Ze,Chen, Jing-Rong,Wang, Xue-Song,Zhang, Bao-Wen,Cao, Yi
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- Alizarin yellow-modified β-cyclodextrin as a guest-responsive absorption change sensor
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Alizarin yellow-modified β-cyclodextrin (ACD), in which alizarin yellow is linked to β-cyclodextrin via an ethylenediamine spacer, was synthesized as a new absorption change indicator for molecules. Alizarin yellow is a pH indicator mat exhibits absorption peaks at 360 and 480 nm in the neutral region and in the alkaline region, respectively, with pKa = 10.98 for an equilibrium between two forms. ACD has two parts to be deprotonated: one is the phenolic hydroxyl group of alizarin yellow residue and the other is the secondary amine group of the spacer. ACD exhibits pH dependency very different from that of alizarin yellow. We obtained two pKa values, 4.88 (pKa1) and 8.89 (pKa2), for ACD by pH titration of its absorption intensity. The pKa1 and pKa2 values were suggested to be the pKa values of the phenolic hydroxyl group of alizarin yellow residue and the secondary amine group, respectively. Upon addition of guest species, the pKa1 and pKa2 values shifted to 5.11 and 7.56, respectively, indicating a larger shift in the pKa for the amine group than for the hydroxyl group. The guest-induced pKa shift in the alkaline region suggests that deprotonation of the amine group of ACD occurs when the alizarin yellow moiety is excluded from the cyclodextrin cavity associated with guest accommodation and exposed to an alkaline environment The sensitivities of this host to various guests were examined by absorption changes at 475 nm in pH 8.3 phosphate buffer, and the order of the sensitivities was found to be adamantane derivatives > borneol > bile acids. This order is not parallel with that of the binding constants, suggesting that the structural features of the host-guest complexes are important. All these results demonstrate that ACD can be used as an effective chemosensor for molecules.
- Aoyagi, Taiyo,Nakamura, Asao,Ikeda, Hiroshi,Ikeda, Tsukasa,Mihara, Hisakazu,Ueno, Akihiko
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- Interactions of some modified mono- and bis-β-cyclodextrins with bovine serum albumin
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Two mono-substituted β-cyclodextrins and two bridged bis-β-cyclodextrins, that is, mono(6-(2-aminoethylamino)-6-deoxy)-β- cyclodextrin (1), mono(6-(2-(2-aminoethylamino)ethylamino)-6-deoxy)-β- cyclodextrin (2), ethylene-1,2-diamino bis-6-(6-deoxy-β-cyclodextrin) (3), and iminodiethylene-2,2′-diamino bis-6-(6-deoxy-β-cyclodextrin) (4), were prepared from β-cyclodextrin. Their binding ability with bovine serum albumin as a model protein was investigated through proton magnetic resonance (1H NMR), ultraviolet visible spectroscopy (UV-vis), circular dichroism (CD), and fluorescence spectroscopy. In the 1H NMR spectra of the modified cyclodextrins, the resolution of proton signals decreases after the addition of BSA. From the UV and CD spectra, it is found that both the UV absorption and the α-helix content of BSA increase with the concentration of the modified cyclodextrins. The protein-ligand interactions cause a fluorescence quenching. The quenching constants are determined using the Stern-Volmer equation to provide an observation of the binding affinity between modified cyclodextrins and BSA. All these results indicate that the modified cyclodextrins can interact with BSA and the bridged bis(β-cyclodextrin)s (3 and 4) have much stronger interactions than the mono-substituted β-cyclodextrins (1 and 2). The strong binding stability of bis-cyclodextrins should be attributed to the cooperative effect of two adjacent cyclodextrin moieties. Job's plot shows that the complex stoichiometries of BSA to the modified cyclodextrins were 1:4 for 1 and 2, as well as 1:3 for 3 and 4, respectively.
- Gao, Hui,Wang, Yi-Nong,Fan, Yun-Ge,Ma, Jian-Biao
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- Evaluation of supramolecule conjugated magnetic nanoparticles as a simultaneous carrier for methotrexate and tamoxifen
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Supramolecular host–guest complexes have the ability to prolong the circulation time, and promote the efficiency of hydrophobic drugs. Therefore, in this project we immobilized cyclodextrin (CD), as a host molecule for tamoxifen (TMX), to mitoxantrone (MTX) conjugated magnetic nanoparticles for simultaneous delivery of anti-cancer drugs toward folate-positive cancer cells. FESEM photography of the magnetic multi-drugs carrier confirmed a hollow circular structure for self-assembled layers of cyclodextrin conjugated to MNPs with average size about 95 nm. Drugs release from supramolecular magnetic nanoparticles (with 86.08% of TMX encapsulation and 60.3% of MTX loading) revealed that protease enzymes can enhance the MTX liberation at pH 5, but don't have any noticeable effect on liberation of TMX at both pH conditions. Also, the simultaneous presence of two drugs onto MNPs induced cytotoxicity in two cancer cell lines, MCF-7 and A549, which is different from the impact of each one of drugs alone. Therefore, we believe that this simultaneous carrier could enhance the efficiency of TMX and MTX anti-cancer drugs and be useful for the intended applications, due to hydrophilicity of supramolecular host–guest complexes and its inherent ability to target folate receptors, simultaneously.
- Sargazi, Azam,Azhoogh, Mina,Allahdad, Sajedeh,Heidari Majd, Mostafa
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- Leading neuroblastoma cells to die by multiple premeditated attacks from a multifunctionalized nanoconstruct
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To conquer complex and devastating diseases such as cancer, more coordinated and combined attack strategies are needed. We suggest that these can be beautifully achieved by using nanoconstruct design. We present an example showing that neuroblastoma cells are selectively killed by a nanoconstruct that specifically targets neuroblastoma cells, pushes cells to the vulnerable phase of the cell cycle, and greatly enhances radiation-induced cell death. The success of this multipronged attack approach launched by cell-embedded nanoconstructs demonstrates the power and flexibility of nanotechnology in treating cancer, a difficult task for a small molecule.
- Jiao, Peifu,Zhou, Hongyu,Otto, Mario,Mu, Qingxin,Li, Liwen,Su, Gaoxing,Zhang, Yi,Butch, Elizabeth R.,Snyder, Scott E.,Jiang, Guibin,Yan, Bing
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- Molecular recognition thermodynamics and structural elucidation of interactions between steroids and bridged bis(β-cyclodextrin)s
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A series of bridged bis(β-cyclodextrin(CD))s (2-7) were synthesized, i.e., bridged bis(β-CD)s 2 and 3 bearing binaphthyl or biquinoline tethers and bridged bis(β-CD)s 4-7 possessing dithiobis(benzoyl) tether, and their complex stability constants (KS), enthalpy (ΔH°), and entropy changes (ΔS°) for the 1:2 inclusion complexation with representative steroids, deoxycholate, cholate, glycocholate, and taurocholate, have been determined in an aqueous phosphate buffer solution of pH 7.20 at 298.15 K by means of titration microcalorimetry. The original conformations of bridged bis(β-cyclodextrin)s were investigated by circular dichroism and 1H ROESY spectroscopy. Structures of the inclusion complexes between steroids and bridged bis(β-CD)s in solution were elucidated by 2D NMR experiments, indicating that anionic groups of two steroid molecules penetrate, respectively, into the two hydrophobic CD cavities in one 6,6′-bridged bis(β-CD) molecule from the secondary rim to give a 1:2 binding mode upon inclusion complexation. The results obtained from titration microcalorimetry and 2D NMR experiments jointly demonstrate that bridged bis(β-CD)s 2, 3 and 5-7 tethered by protonated amino group possessing different substituted groups can enhance not only the molecular binding ability toward steroids by electrostatic interaction but also molecular selectivity. Thermodynamically, the resulting 1:2 bis(β-CD)-steroid complexes are formed by an enthalpy-driven process, accompanied by smaller entropy loss. The increased complex stability mainly results from enthalpy gain, accompanied by large conformational change and extensive desolvation effects for the 1:2 inclusion complexation between bis(β-CD)s and steroids.
- Liu, Yu,Yang, Ying-Wei,Yang, En-Cui,Guan, Xu-Dong
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- Synthesis of amphiphilic polyaspartamide derivatives and construction of reverse micelles
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A series of amphiphilic graft copolymers based on biodegradable and biocompatible poly(aspartic acid)s were synthesized by a successive aminolysis reaction of polysuccinimide using octadecylamine/dodecylamine, and ethylenediamine-β-cyclodextrin/ethanediamine. The chemical structures of the copolymers were confirmed by FT-IR and 1H NMR spectroscopy. Large compound reverse micelles consisting of numerous small reverse micelles with polar cores and hydrophobic shells were formed in octanol solution. The reverse micelles showed various particle sizes based on the different length of hydrophobic alkyl chains and molecular weight of polysuccinimide, as determined by dynamic light scattering. Interestingly, the particle size of micelles showed temperature dependence, the diameter decreased continuously with increasing temperature. Their morphology and assembly properties were characterized using scanning electron microscopy, transmission electron microscopy and fluorescence spectroscopy. The reverse micelles were extremely efficient in extracting Congo red from water into octanol, exhibiting a potential application as delivery vehicles in the pharmaceutical and cosmetic fields, and as nanocontainers for separation of inorganic molecules as well. the Partner Organisations 2014.
- Liu, De-E,Han, Hui,Lu, Hongguang,Wu, Guolin,Wang, Yinong,Ma, Jianbiao,Gao, Hui
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- Synthesis of copolymers with cyclodextrin as pendants and its end group effect as superplasticizer
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In this paper, the efficient approach for the synthesis of β-cyclodextrin (CD) based functional monomers was described. Based on the monovinyl β-CD monomer (GMA-EDA-CD), a new type poly(AA-co-GMA-EDA-CD) (PCDs) copolymer bearing pendent CD groups was synthesized and used as superplasticizer. Their chemical compositions were characterized by FT-IR, NMR, MALDI-TOF and GPC. The effects of PCDs on dispersion and adsorption in cement mortars were detailed discussed. The results indicated that PCD copolymers behaved excellent dispersion ability and strong retarding effect. PCD 2 with molar ratio (%) for monomer (AA:GMA-EDA-CD = 80:20) had the best dispersion and dispersion maintaining abilities, which were mainly attributed to the synergistic effects of steric hindrance and electrostatic repulsive force, and the retarding effect of PCD copolymers resulted from steric hindrance repulsion of CD pendants and the large number of hydroxyl groups, which affected the hydration reaction of cement.
- Li, Yinwen,Guo, Huilong,Zhang, Yunfei.,Zheng, Jian,Li, Zhaoxia,Yang, Chenghua,Lu, Mangeng
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- Supramolecular Fluorescent Nanoparticles Constructed via Multiple Non-Covalent Interactions for the Detection of Hydrogen Peroxide in Cancer Cells
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Overabundance of hydrogen peroxide originating from environmental stress and/or genetic mutation can lead to pathological conditions. Thus, the highly sensitive detection of H2O2 is important. Herein, supramolecular fluorescent nanoparticles self-assembled from fluorescein isothiocyanate modified β-cyclodextrin (FITC-β-CD)/rhodamine B modified ferrocene (Fc-RB) amphiphile were prepared through host-guest interaction between FITC-β-CD host and Fc-RB guest for H2O2 detection in cancer cells. The self-assembled nanoparticles based on a combination of multiple non-covalent interactions in aqueous medium showed high sensitivity to H2O2 while maintaining stability under physiological condition. Owing to the fluorescence resonance energy transfer (FRET) effect, addition of H2O2 led to obvious fluorescence change of nanoparticles from red (RB) to green (FITC) in fluorescent experiments. In vitro study showed the fluorescent nanoparticles could be efficiently internalized by cancer cells and then disrupted by endogenous H2O2, accompanying with FRET from "on" to "off". These supramolecular fluorescent nanoparticles constructed via multiple non-covalent interactions are expected to have potential applications in diagnosis and imaging of diseases caused by oxidative stresses.
- Wei, Xuan,Dong, Ruijiao,Wang, Dali,Zhao, Tianyu,Gao, Yongsheng,Duffy, Patrick,Zhu, Xinyuan,Wang, Wenxin
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- A water-soluble β-cyclodextrin derivative possessing a fullerene tether as an efficient photodriven DNA-cleavage reagent
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A simple synthetic route for a water-soluble cyclodextrin-fullerene conjugate based on the Diels-Alder reaction between anthryl-cyclodextrin and fullerene has been presented. Aided by the fascinating biochemical functions of fullerene, the resultant cyclodextrin-C60 conjugate displays a satisfactory DNA-cleavage ability under the visible-light irradiation.
- Liu, Yu,Zhao, Yan-Li,Chen, Yong,Liang, Peng,Li, Li
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- Pip-HoGu: An Artificial Assembly with Cooperative DNA Recognition Capable of Mimicking Transcription Factor Pairs
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Cooperation between pairs of transcription factors (TFs) has been widely demonstrated to play a pivotal role in the spatiotemporal regulation of gene expression, but blocking cooperative TF pair-DNA interactions synergistically has been challenging. To achieve this, we designed programmable DNA binder pyrrole-imidazole polyamides conjugated to host-guest assemblies (Pip-HoGu) to mimic the cooperation between natural TF pairs. By incorporating cyclodextrin (Cyd)-adamantane (Ada), we synthesized Ada1 (PIP1-Ada) and Cyd1 (PIP2-Cyd), which were evaluated using Tm, EMSA, competitive, and SPR assays and molecular dynamics studies. The results consistently demonstrated that Pip-HoGu system formed stable noncovalent cooperative complexes, thereby meeting key criteria for mimicking a TF pair. The system also had a longer recognition sequence (two-PIP binding length plus gap distance), favorable sequence selectivity, higher binding affinity, and in particular, a flexible gap distance (0-5 bp). For example, Ada1-Cyd1 showed thermal stability of 7.2 °C and a minimum free energy of interaction of -2.32 kcal·mol-1 with a targeting length of 14 bp. Furthermore, cell-based evaluation validated the capability of Pip-HoGu to exhibit potent cooperative inhibitory effects on gene expression under physiological conditions by disrupting TF pair-DNA function. In conclusion, the modular design of Pip-HoGu defines a general framework for mimicking naturally occurring cooperative TF pair-DNA interactions that offers a promising strategy for applications in the precise manipulation of cell fate.
- Yu, Zutao,Guo, Chuanxin,Wei, Yulei,Hashiya, Kaori,Bando, Toshikazu,Sugiyama, Hiroshi
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- Intranasal delivery of targeted polyfunctional gold–iron oxide nanoparticles loaded with therapeutic microRNAs for combined theranostic multimodality imaging and presensitization of glioblastoma to temozolomide
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The prognosis for glioblastoma (GBM) remains depressingly low. The biological barriers of the brain present a major challenge to achieving adequate drug concentrations for GBM therapy. To address this, we explore the potential of the nose-to-brain direct transport pathway to bypass the blood-brain barrier, and to enable targeted delivery of theranostic polyfunctional gold-iron oxide nanoparticles (polyGIONs) surface loaded with therapeutic miRNAs (miR-100 and antimiR-21) to GBMs in mice. These nanoformulations would thus allow presensitization of GBM cells to the systemically delivered chemotherapy drug temozolomide (TMZ), as well as in vivo multimodality molecular and anatomic imaging of nanoparticle delivery, trafficking, and treatment effects. First, we synthesized GIONs coated with β-cyclodextrin-chitosan (CD-CS) hybrid polymer, and co-loaded with miR-100 and antimiR-21. Then we decorated their surface with PEG-T7 peptide using CD-adamantane host-guest chemistry. The resultant polyGIONs showed efficient miRNA loading with enhanced serum stability. We characterized them for particle size, PDI, polymer functionalization, charge and release using dynamic light scattering analysis, TEM and qRT-PCR. For in vivo intranasal delivery, we used U87-MG GBM cell-derived orthotopic xenograft models in mice. Intranasal delivery resulted in efficient accumulation of Cy5-miRNAs in mice treated with T7-targeted polyGIONs, as demonstrated by in vivo optical fluorescence and MR imaging. We measured the therapeutic response of these FLUC-EGFP labelled U87-MG GBMs using bioluminescence imaging. Overall, there was a significant increase in survival of mice co-treated with T7-polyGIONs loaded with miR-100/antimiR-21 plus systemic TMZ, compared to the untreated control group, or the animals receiving non-targeted polyGIONs-miR-100/antimiR-21, or TMZ alone. Once translated clinically, this novel theranostic nanoformulation and its associated intranasal delivery strategy will have a strong potential to potentiate the effects of TMZ treatment in GBM patients.
- Sukumar, Uday K.,Bose, Rajendran J.C.,Malhotra, Meenakshi,Babikir, Husam A.,Afjei, Rayhaneh,Robinson, Elise,Zeng, Yitian,Chang, Edwin,Habte, Frezghi,Sinclair, Robert,Gambhir, Sanjiv S.,Massoud, Tarik F.,Paulmurugan, Ramasamy
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- Pseudo-graft polymer based on adamantyl-terminated poly(oligo(ethylene glycol) methacrylate) and homopolymer with cyclodextrin as pendant: Its thermoresponsivity through polymeric self-assembly and host-guest inclusion complexation
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A series of well-defined adamantyl-terminated thermally responsive copolymers (Ad-POEGMAs) were synthesized by atom transfer radical polymerization (ATRP), in which 2-(2-methoxyethoxy) ethyl methacrylate (MEO2MA) and oligo(ethylene glycol) methacrylate (OEGMA) served as the thermosensitive building blocks. Moreover, cyclodextrins (CDs) as bulky pendant grafted polymers (PGCD) were synthesized by homopolymerization of aminoethyl methacrylate β-cyclodextrin (GCD). The thermal-responsive behaviors were investigated by a combination of 1H NMR, UV-vis spectroscopy, dynamic light scattering (DLS), and transmission electron microscopy (TEM). In comparison to other thermal-responsive copolymers based on POEGMAs, Ad-POEGMAs exhibited unusual thermally induced aggregation processes. The Ad group assembled and POEGMA chains associated to produce stable water-soluble nano-aggregates, followed by a rearrangement process at the second thermal transition. Moreover, it was found that a noncovalently connected supramolecular pseudo-graft polymer was formed via inclusion complexation in aqueous solution. This pseudo-graft polymer underwent a reversible temperature-induced transition from solution to micelle under suitable conditions. The cyclodextrin (CD) moiety attached to the main chain played two roles. As supramolecular host moieties, CDs formed inclusion complexes with guest-ended polymers, leading to graft-like polymers. As bulky hydrophilic moieties, CDs stabilized the micelles induced by the coil-to-globule transition of POEGMA segments. This journal is the Partner Organisations 2014.
- Li, Yinwen,Guo, Huilong,Zhang, Yunfei,Zheng, Jian,Gan, Jianqun,Guan, Xiaoxiao,Lu, Mangeng
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- Molecular encapsulation of berberine by a modified β-cyclodextrin and binding of host: guest complex to G-quadruplex DNA
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The capacity to control quadruplex formation, especially in cancer cells, is captivating and entails a reasonable comprehension of the ligand-G-quadruplex binding. Herein, we report an iminopyrenyl-β-cyclodextrin conjugate interacting with duplex and G-quadrulex DNAs. In addition, the host: guest association of the established G-quadruplex binder, berberine, with the β-cyclodextrin derivative is studied employing 2-D ROESY. NMR, UV-visible, and fluorescence spectroscopic techniques are utilized to explore the β-cyclodextrin conjugate's interaction with the quadruplexes. The Binding constants are accounted for the association of the ligands to each of the DNAs viz., calf thymus DNA (duplex), kit22, telo24, and myc22 (quadruplexes). The modulation of the iminopyrenyl-β-cyclodextrin binding to the DNAs are observed when berberine is loaded in the host molecule. A vivid distinction between the interactions of the ligands with duplex and quadruplex structures is inferred. Berberine-loaded iminopyrenyl-β-cyclodextrin shows a higher affinity for binding to kit22.
- Suganthi, Soundrapandian,Sivaraj, Ramasamy,Enoch, Israel V. M. V.
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- Fluorescent behaviour in host-guest interactions. Part 3. Fluorescent sensing for organic guests using three types of amino-β-cyclodextrins
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The pH- and temperature-dependent fluorescence behaviour in aqueous solution of three amino-β-cyclodextrins (amino-β-CDx), 1, 2 and 3, bearing an amide-linked naphthalene probe has been investigated. The emission intensity at λmax(em) of 1 decreased dramatically with increasing temperature. The pH-dependent fluorescence spectrum was also recorded. Operation of the in-out equilibrium of the naphthalene probe of 1 was mainly analyzed using 1H NMR and circular dichroism spectra. The application of 1 to organic-guest sensing is demonstrated by several examples. These findings suggest that the new host molecule, 1, will be an excellent CDx-based fluorescent sensor for temperature, pH and neutral organic guests.
- Takenaka, Yasushi,Higashi, Miwako,Yoshida, Noboru
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- Biomimetic mineralization of calcium carbonate mediated by a polypeptide-based copolymer
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A novel copolymer, β-cyclodextrin-b-poly(l-glutamic acid) (β-CD-b-PLGA), was synthesized by ring-opening polymerization and subsequent hydrolysis reaction. The β-CD-b-PLGA copolymer possesses an oligosaccharide β-CD segment and a polypeptide PLGA segment, with chemical structure resembling natural glycoprotein. The copolymers were applied in regulating the crystallization of calcium carbonate. The effects of the concentration of copolymers and calcium ions were systemically investigated. Various morphologies, including rhombohedra, rod, pseudo-dodecahedra and rosette-like structures, were obtained by adjusting the polymer and Ca 2+ concentrations of the initial solution. Investigation of the pseudo-dodecahedra growth mechanism indicates that the copolymers mediate amorphous calcium carbonate formation initially, and then regulate the meso-scale self-assembly of CaCO3 subunits. The morphology variation is influenced by the binding of β-CD-b-PLGA chains on specific crystal faces combined with the steric repulsive force of β-CD-b-PLGA chains. The Royal Society of Chemistry 2013.
- Zhu, Wenjie,Lin, Jiaping,Cai, Chunhua,Lu, Yingqing
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- Synthesis of bridged and metallobridged bis(β-cyclodextrin)s containing fluorescent oxamidobisbenzoyl linkers and their selective binding towards bile salts
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A series of β-cyclodextrin (β-CD) dimers containing fluorescent 2,2′-oxamidobisbenzoyl and 4,4′-oxamidobisbenzoyl linkers - that is, 6,6′-[2,2′-oxamidobis(benzoylamino)]ethyleneamino-6,6′-deoxy- bis(β-CD) (2), 6,6′-[2,2′-oxamidobis(benzoylamino)] diethylenediamino-6,6′-deoxy-bis(β-CD) (3), 6,6′-[4,4′- oxamidobis(benzoylamino)]ethyleneamino-6,6′-deoxy-bis(β-CD) (4), and 6,6′-[4,4′-oxamidobis(benzoylamino)]-diethylenediamino-6, 6′-deoxy- bis(β-CD) (5) - were synthesized from the corresponding oxamidobis(benzoic acid)s through treatment with mono[6-aminoethyleneamino-6- deoxy]-β-CD or mono[6-diethylenetriamino-6-deoxy]-β-CD. Further treatment of 2-5 with copper perchlorate gave their CuII complexes 6-9 in satisfactory yields. The conformation and binding behavior of 2-9 towards two bile salt guests - sodium cholate (CA) and sodium deoxycholate (DCA) - was comprehensively investigated by circular dichroism, 2D NMR spectroscopy, and fluorescence spectroscopy in TrisHCl buffer solution (pH 7.2) at 25 °C. Thanks to the cooperative host-linker-guestbinding mode, the stoichiometric 1:1 complexes formed by bis(β-CD)s 2-5 with bile salts gave high stability constants (KS values) of up to 103-104M-1. Significantly, benefiting from the intramolecular 1:2 or 2:4 binding stoichiometry, the resulting complexes of metallobis(β-CD)s 6-9 with bile salts gave much higher KS values of up to 106-107M -2. The enhanced binding abilities of bis(β-CD)s and metallobridged bis(β-CD)s are discussed from the viewpoints of induced-fit interactions and multiple recognition between host and guest.
- Liu, Yu,Yu, Hong-Mei,Chen, Yong,Zhao, Yan-Li
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- Synthesis and characterization of NADH model compound modified β-cyclodextrin and its role as an energy donor in FRET
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β-Cyclodextrin is chemically modified to selectively introduce an acridinedione moiety on the primary face. The synthesis involves the substitution of one of the primary hydroxyl groups of β-cyclodextrin by a tosyl group which facilitates the introduction of an ethylene diamine modification which is finally condensed to a tetraketone. The acridinedione modified β-cyclodextrin thus obtained was fully characterized by IR, NMR and Mass spectrometry. The photophysical properties of the compound were also analyzed. The potential of the modified β-cyclodextrin to act as an energy donor in FRET was investigated with a suitable acceptor.
- Krishnaveni,Ramamurthy,Padma Malar,Divya
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- Hyper-Cross-linked Porous MoS2-Cyclodextrin-Polymer Frameworks: Durable Removal of Aromatic Phenolic Micropollutant from Water
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A reasonable and efficient strategy for the construction of hyper-cross-linked porous MoS2-CD-polymer frameworks (MoS2CDPFs) was demonstrated. Here, MoS2 nanosheets (NSs) can be decorated with amino functionalized β-cyclodextrin, producing a nanoscale structural motif (MoS2@CD) for the synthesis of MoS2CDPFs. We demonstrated that CD polymer (CDP) as linker can be uniformly incorporated into the frameworks. Except for the pores created between MoS2 NSs, polymer doping generates extra interspace between MoS2 NSs and CD monomer. Interestingly, the resultant MoS2CDPFs can rapidly sequester aromatic phenolic micropollutant bisphenol A (0.1 mM) from water with 93.2% adsorption capacity, which is higher than that of MoS2, MoS2@CD, and CDP. The intercalation between MoS2 sheets with CDP imparts the frameworks durability in adsorption/desorption of aromatic phenolic micropollutants. Remarkably, the removal efficiency reduced only 3% after 10 regeneration-reuse cycles. These findings demonstrated that the porous MoS2-CD-polymer-based frameworks are promising adsorbents for rapid, flow-through water remediation.
- Liu, Jian,Yang, Yanmei,Bai, Jingwei,Wen, Huang,Chen, Fengjuan,Wang, Baodui
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- Solubility and bioavailability enhancement of ciprofloxacin by induced oval-shaped mono-6-deoxy-6-aminoethylamino-β-cyclodextrin
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Ciprofloxacin is a broad-spectrum fluoroquinolone antibiotic used to treat bacterial infections; however, its limited aqueous solubility inhibits its broader clinical uses. This study investigated the complexation effect of mono-6-deoxy-6-aminoethylamino-β-cyclodextrin on the aqueous solubility and bioavailability of ciprofloxacin. During complexation, the oval-shaped cavity induced by mono-aminoethylamine substitution on the primary rim of β-cyclodextrin, was considered to be a key factor according to NMR spectroscopy and molecular modeling studies. The ciprofloxacin with mono-6-deoxy-6-aminoethylamino-β-cyclodextrin complex was characterized using FE-SEM, DSC, FT-IR, T1 relaxation, 2D NOESY, and DOSY NMR spectroscopy and molecular modeling studies. The solubility property of ciprofloxacin complexed with mono-6-deoxy-6-aminoethylamino-β-cyclodextrin was enhanced by seven-fold compared to that of pure ciprofloxacin. Furthermore antibacterial activity of that complex against methicillin-resistant Staphylococcus aureus was enhanced and it clearly showed the growth inhibition. The mono-6-deoxy-6-aminoethylamino-β-cyclodextrin has the potential to be utilized for other oblong guest molecules besides ciprofloxacin based on the novel induced elliptical cavity.
- Choi, Jae Min,Park, Kyeonghui,Choi, Youngjin,Park, Seyeon,Yu, Jae-hyuk,Dindulkar, Someshwar D,Lee, Benel,Cho, Eunae,Jeong, Daham,Jung, Seunho
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- Surface immobilization of β-cyclodextrin on hybrid silica and its fast adsorption performance of p-nitrophenol from the aqueous phase
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Renewable β-cyclodextrin (β-CD) was immobilized onto the surface of hybrid silica using ethylenediamine as linking groups to construct an adsorbent in water treatment (CD@Si), and the obtained CD@Si was characterized through FT-IR, XPS, EDX, contact angle measurement, TGA, solid-state 13C NMR, SEM, and XRD analyses. The effect of initial pH, contact time on the adsorption performance of CD@Si for p-nitrophenol, and the adsorption kinetics, adsorption isotherms, adsorption thermodynamics, reusability and adsorption mechanism were investigated systematically, which indicate that the adsorption of p-nitrophenol onto CD@Si is a very fast process. The adsorption equilibrium can be reached in 15 s with an acceptable equilibrium adsorption capacity of 69.6 mg g-1 at pH 7.0, which is much faster than many reported adsorbents based on β-CD. The adsorption of p-nitrophenol onto CD@Si follows the pseudo-second-order model, obeys the Freundlich model, and is a feasible, spontaneous, and exothermic process which is more favorable at lower temperatures. And the formation of an inclusion complex and a hydrogen bond interaction are two origins of p-nitrophenol being adsorbed onto CD@Si. Additionally, CD@Si can be recycled and reused for at least five runs with an acceptable adsorption capacity, and is a very promising adsorbent for the fast adsorption of p-nitrophenol or its analogues from the aqueous phase. Additionally, this work also provides a strategy to increase the adsorption rate of adsorbents based on β-CD.
- Shen, Hai-Min,Zhu, Gong-Yuan,Yu, Wu-Bin,Wu, Hong-Ke,Ji, Hong-Bing,Shi, Hong-Xin,Zheng, Yi-Fan,She, Yuan-Bin
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- Smart GSH/pH dual-bioresponsive degradable nanosponges based on β-CD-appended hyper-cross-linked polymer for triggered intracellular anticancer drug delivery
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Efficient accumulation and on-demand intracellular drug release in the desired site are a crucial issue in developing ideal drug delivery systems (DDSs). Glutathione (GSH)/pH dual-bioresponsive degradable Nanosponges were developed based on β-CD-appended hyper-cross-linked polymer by one-pot polymerization of acryloyl-6- ethylenediamine-6-deoxy-β-Cyclodextrin (β-CD-NH-ACy), acrylic acid (AA) and N,N-bis(acryloyl)- cystamine (BACy) as cross-linker to deliver doxorubcin (DOX) and investigated for GSH/pH triggered DOX release, in which the massive carboxyl and amino groups, and disulfide bonds were used as pH and GSH bioresponsive fragments, respectively. In the proposed DDSs, DOX was readily incorporated into the three dimensional networks of the Nanosponges either as inclusion complexes or as non-inclusion complexes, with a high drug loading capacity of 22.6%. In vitro release studies suggested that the Nanosponges exhibited GSH/pH triggered disintegration and drug release performance, in which DOX release was significantly accelerated in acidic (pH5.0) and cytosolic reduction (10 mM GSH) conditions, with ~77.0% of DOX release. The morphology changes of DOX@Nanosponges in releasing media (pH5.0, 10 mM GSH) were further studied by TEM. Confocal microscopy observation demonstrated that DOX was delivered and released into cytoplasm and nucleus of A549 cells in 7 h incubation with DOX@Nanosponges. MTT assays manifested that the Nanosponges exhibited low cytotoxicity up to a concentration of 1000 μg/mL and DOX@Nanosponges had high anti-tumor activity. These findings demonstrated that the dual-bioresponsive Nanosponges may function as a promising platform for targeted delivery and intracellular drug controlled release in tumor therapy.
- Dai, Yutong,Li, Qingman,Zhang, Shurong,Shi, Shan,Li, Yang,Zhao, Xudong,Zhou, Liping,Wang, Xin,Zhu, Yijian,Li, Wei
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- Functional carrier based on alkylamino cyclodextrin in entrapment of ferulic acid
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The invention discloses application of a functional carrier based on alkylamino cyclodextrin in entrapment of ferulic acid. On the one hand, alkylamino-modified beta-cyclodextrin is designed as a mainbody to prepare a ferulic acid clathrate compound; and on the other hand, an alkylamino cyclodextrin high-molecular polymer connected with linear polymer molecules is designed to load ferulic acid. Compared with the ferulic acid monomer, the ferulic acid entrapped by the carrier has advantages that the water solubility is obviously improved and the thermal stability is also enhanced; and a certain theoretical reference is provided for developing a novel water-soluble ferulic acid material and expanding the application of ferulic acid in the field of food and medicine.
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Paragraph 0039; 0050-0052
(2020/04/02)
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- NITRIC OXIDE-RELEASING CYCLODEXTRINS AS BIODEGRADABLE ANTIBACTERIAL SCAFFOLDS AND METHODS PERTAINING THERETO
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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.
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Page/Page column 97-99; 100
(2019/10/01)
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- Nitric Oxide-Releasing Cyclodextrins
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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.
- Jin, Haibao,Yang, Lei,Ahonen, Mona Jasmine R.,Schoenfisch, Mark H.
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supporting information
p. 14178 - 14184
(2018/10/24)
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- Picolinamide modified β-cyclodextrin/Pd (II) complex: Asupramolecular catalyst for Suzuki-Miyaura coupling of aryl, benzyl and allyl halides with arylboronic acids in water
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Novel supramolecular catalysts for Suzuki-Miyaura coupling were prepared and characterized by NMR, FT-IR, TEM, XRD, TGA, and XPS. The resulting picolinamide-modified β-cyclodextrin/Pd(II) complex (Pd(II)@PCA-β-CD) showed very efficient catalytic activity for Suzuki-Miyaura coupling of aryl, benzyl, and allyl halides with arylboronic acids in an environmentally benign aqueous solution. Various organic halides including chlorides can produce good to excellent yields with phenyl-boronic acid and a catalytic amount of Pd(II)@PCA-β-CD. This hydro-soluble catalyst was capable of being reused for at least eight runs with only a slight loss of catalytic activity. A putative mechanism of the Pd(II)/Pd(IV) catalytic cycle was also explored and calculated by ab initio QM/MM methods.
- Luo, Kaixiu,Zhang, Lu,Yang, Rui,Jin, Yi,Lin, Jun
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p. 200 - 210
(2018/08/09)
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- Preparation of magnetic nano-drug carrier and method for using magnetic nano-drug carrier to load doxorubicin hydrochloride
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The invention relates to the preparation of a magnetic nano-drug carrier and a method for using the magnetic nano-drug carrier to load doxorubicin hydrochloride, belonging to the technical field of magnetic nano-material drug transport. The invention mainly aims at solving the technical problems of high toxicity and poor treatment effect of the prior art. According to a technical scheme, a preparation method of the magnetic nano-drug carrier comprises the following steps: (1) preparing a cyclodextrin-hyaluronic acid supermolecule polymer; (2) preparing magnetic graphene oxide; (3) preparing the cyclodextrin-hyaluronic acid polymer-functionalized magnetic magnetic nano-drug carrier. Compared with the prior art, the magnetic nano-drug carrier is high in biocompatibility and low in toxicity,and has the characteristics of cancer cell targeted localization and drug controlled release, thus having an important application value in the aspect of biological drug carriers.
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Paragraph 0044
(2018/04/01)
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- An oxaliplatin(iv) prodrug-based supramolecular self-delivery nanocarrier for targeted colorectal cancer treatment
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A redox-responsive supramolecular nanocarrier was constructed from the self-assembly of spermine modified cyclodextrin and oxaliplatin prodrug. The nanocarrier could preferentially accumulate in polyamine transporter over-expressing HCT116 cells, releasing drugs under a reducing intracellular environment to maximize anticancer treatment.
- Lim, Wei Qi,Phua, Soo Zeng Fiona,Chen, Hongzhong,Zhao, Yanli
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supporting information
p. 12762 - 12765
(2018/12/12)
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- A oleanolic acid with amine cyclodextrin clathrate
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The invention discloses a clathrate compound of pentacyclic triterpene oleanolic acid and amine cyclodextrin, the amine cyclodextrin is amino-substituted beta-cyclodextrin, The clathrate compound is prepared by employing a solvent method or an ultrasonic method; after oleanolic acid and amine cyclodextrin form the clathrate, the solubility of clathrate in water can be greatly increased, stability is increased, and bioavailability is increased. The antitumor in-vitro experiment shows that the clathrate has good antitumor in-vitro activity; the preparation method has the advantages of simple process, easy operation and mild reaction condition, and can be used for development of new oleanolic acid preparation.
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Paragraph 0031
(2017/12/02)
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- Host-guest inclusion system of glycyrrhetic acid with polyamine-β-cyclodextrin: Preparation, characterization, and anticancer activity
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The inclusion complexation behaviors of glycyrrhetic acid (CTA) with four polyamine-modified β-cyclodextrins (CDs) have been investigated by 1H and 2D NMR, thermal gravimetric analysis, X-ray power diffraction and scanning electron microscopy. The results showed that Glycyrrhetic acid was encapsulated into the cavity of cyclodextrin to form the complexes with 1:1 stoichiometry. The water solubility of GTA was significantly enhanced by inclusion complexation with polyamine-modified β-cyclodextrins. The calculated IC50 values indicated that the antitumor activities of inclusion complexes were better than that of GTA. Satisfactory aqueous solubility, along with high thermal stability of inclusion complexes will be potentially useful for their application on the formulation design of natural medicine.
- Shen, Zhi,Qin, Qi,Liao, Xiali,Yang, Bo
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p. 155 - 161
(2017/08/04)
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- Triterpenoid-Based Self-Healing Supramolecular Polymer Hydrogels Formed by Host–Guest Interactions
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Pentacyclic triterpenoids, a class of naturally bioactive products having multiple functional groups, unique chiral centers, rigid skeletons, and good biocompatibility, are ideal building blocks for fabricating versatile supramolecular structures. In this research, the natural pentacyclic triterpenoid glycyrrhetinic acid (GA) was used as a guest molecule for β-cyclodextrin (β-CD) to form a GA/β-CD (1:1) inclusion complex. By means of GA and β-CD pendant groups in N,N′-dimethylacrylamide copolymers, a supramolecular polymer hydrogel can be physically cross-linked by host–guest interactions between GA and β-CD moieties. Moreover, self-healing of this hydrogel was observed and confirmed by step-strain rheological measurements, whereby the maximum storage modulus occurred at a [GA]/[β-CD] molar ratio of 1:1. Additionally, these polymers displayed outstanding biocompatibility. The introduction of a natural pentacyclic triterpenoid into a hydrogel system not only provides a biocompatible guest–host complementary GA/β-CD pair, but also makes this hydrogel an attractive candidate for tissue engineering.
- Li, Ying,Li, Jianzuo,Zhao, Xia,Yan, Qiang,Gao, Yuxia,Hao, Jie,Hu, Jun,Ju, Yong
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supporting information
p. 18435 - 18441
(2016/12/16)
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- Biomimetic asymmetric Michael addition reactions in water catalyzed by amino-containing β-cyclodextrin derivatives
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Nine β-cyclodextrin derivatives containing an amino group were synthesized via nucleophilic substitution from mono(6-O-p-tolylsulfonyl)-β-cyclodextrin and used in asymmetric biomimetic Michael addition reactions in water at room temperature. The mechanism responsible for the moderate activity and enantioselectivity of the β-cyclodextrin derivatives was explored using nuclear magnetic resonance spectroscopy, namely 2D 1H rotating-frame overhauser effect spectroscopy (ROESY), ultraviolet absorption spectroscopy, and quantum chemical calculations, which provide a useful technique for investigating the formation of inclusion complexes. The effects of the pH of the reaction medium, the β-cyclodextrin derivative dosage, the structure of the modifying amino group, and various substrates on the yield and enantioselectivity were investigated. The results indicated that these factors had an important effect on the enantiomeric excess (ee) in the reaction system. Experiments using a competitor for inclusion complex formation showed that a hydrophobic cavity is necessary for enantioselective Michael addition. A comparison of the reactions using 4-nitro-β-nitrostyrene and 2-nitro-β-nitrostyrene showed that steric hindrance improved the enantioselectivity. This was verified by the optimized geometries obtained from quantum chemical calculations. An ee of 71% was obtained in the asymmetric Michael addition of cyclohexanone and 2-nitro-β-nitrostyrene, using (S)-2-aminomethylpyrrolidine-modified β-CD as the catalyst, in an aqueous buffer solution, i.e., CH3COONa-HCl (pH 7.5).
- Zhu, Qingying,Shen, Haimin,Yang, Zhujin,Ji, Hongbing
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p. 1227 - 1234
(2016/09/07)
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- Merging supramolecular catalysis and aminocatalysis: Amino-appended β-cyclodextrins (ACDs) as efficient and recyclable supramolecular catalysts for the synthesis of tetraketones
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Well-designed amino-appended β-cyclodextrins (ACDs) with an amino side chain of different lengths at the primary face of β-CD were synthesized and employed in the catalytic synthesis of a series of tetraketones as supramolecular catalysts in water for the first time. Yields of 58-97% were obtained with up to 30 examples of substrate. The catalyst could be recycled easily, while a 92% yield and 84% rate of catalyst recovery could be achieved after 8 cycles of catalyst recycling. Moreover, a catalytic mechanism merging supramolecular catalysis and aminocatalysis could be proposed through detailed 1D and 2D NMR, ESI-MS and Job plot analyses. This protocol retained the promising characteristics of ambient temperature, green medium, simple operation, broad substrate scope, excellent yields, superb catalyst recycling performance and unique catalytic mechanism.
- Ren, Yufeng,Yang, Bo,Liao, Xiali
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p. 22034 - 22042
(2016/03/08)
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- Fabrication of AIE-active amphiphilic fluorescent polymeric nanoparticles through host-guest interaction
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Fluorescent polymeric nanoparticles (FPNs) have obtained more and more attention in recent years due to their excellent performance in the fields of bioimaging, biosensing, theranostics and many other biomedical applications. In this work, we reported a novel method to fabricate amphiphilic fluorescent copolymers through host-guest interactions based on an aggregation-induced emission (AIE) active dye (named as Ad-PhNH2) and β cyclodextrin (β-CD) contained polymers, which were synthesized by free radical polymerization and subsequent ring-opening reaction. These AIE active copolymers can self assemble into FPNs (named as PEGMA-IA-β-CD/Ad-PhNH2) due to their amphiphilic properties. The hydrophobic dye was aggregated in the core and therefore can emit strong fluorescent intensity due to its AIE feature. However, the hydrophilic polymers that covered the hydrophobic core can endow good dispersibility in pure aqueous solution. Biological evaluation results demonstrated that PEGMA-IA-β-CD/Ad-PhNH2 FPNs can be effectively internalized into cells and they have shown low cytotoxicity. More importantly, the molar ratio of β-CD to Ad-PhNH2 can be facilely adjusted and the surplus β-CD can be used for carrying chemical anticancer agents. Furthermore, a large number of carboxyl groups were generated during the ring opening reaction. These negative carboxyl groups can be potentially used for further conjugation reactions and for biological delivery. The above described features of PEGMA-IA-β-CD/Ad-PhNH2 FPNs make them a prospect in biological imaging and delivery applications.
- Chen, Junyu,Luo, Songsong,Xu, Dazhuang,Xue, Yun,Huang, Hongye,Wan, Qing,Liu, Meiying,Zhang, Xiaoyong,Wei, Yen
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p. 54812 - 54819
(2016/07/06)
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- Supramolecular nanoparticle carriers self-assembled from cyclodextrin- and adamantane-functionalized polyacrylates for tumor-targeted drug delivery
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The advancement of nanobiotechnology has led to the development of various techniques for addressing target-specific drug delivery issues. In this article, we successfully developed a supramolecular self-assembly approach for the fabrication of polyacrylate-based nanoparticles with simultaneous loading of the anticancer drug doxorubicin (DOX) for targeted delivery towards cancer treatment in vitro and in vivo. Two types of polyacrylates functionalized with adamantane and β-cyclodextrin respectively could self-assemble to form supramolecular nanoparticles through strong host-guest complexation between adamantane and β-cyclodextrin. Folic acid was incorporated within the supramolecular nanoparticles in order to impart the targeting specificity towards selected cancerous cell lines, namely MDA-MB231 and B16-F10. The as-synthesized supramolecular nanoparticles were fully characterized by several techniques, revealing an average nanoparticle size of 35 nm in diameter, which is small enough for excellent blood circulation. The cytotoxicity studies indicate that the supramolecular nanoparticles without drug loading were non-cytotoxic under the concentrations measured, while DOX-loaded supramolecular nanoparticles showed significant cytotoxicity. In order to investigate the targeting specificity of DOX-loaded supramolecular nanoparticles towards the cancerous cells, a healthy cell line model HEK293 was employed for carrying out the comparison studies. Due to the presence of the targeting ligand, experimental results demonstrate that the supramolecular nanoparticles were highly specific for targeting the cancerous cells, but not for HEK293 cells. After the in vitro investigations, the in vivo drug delivery study using DOX-loaded supramolecular nanoparticles was performed. Tumor-bearing nude mice were treated with DOX-loaded supramolecular nanoparticles, and the analysis results indicate that DOX-loaded supramolecular nanoparticles have the capability to enhance the therapeutic effects of DOX for effectively inhibiting the tumor growth. Thus, the self-assembled polymeric nanoparticles exhibit a highly promising potential to serve as drug carriers for targeted drug delivery towards improved cancer treatment.
- Ang, Chung Yen,Tan, Si Yu,Wang, Xiaoling,Zhang, Quan,Khan, Majad,Bai, Linyi,Tamil Selvan, Subramanian,Ma, Xing,Zhu, Liangliang,Nguyen, Kim Truc,Tan, Nguan Soon,Zhao, Yanli
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p. 1879 - 1890
(2014/04/03)
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- Synthesis, characterization, and in vitro evaluation of artesunate-β-cyclodextrin conjugates as novel anti-cancer prodrugs
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A novel series of artesunate-β-cyclodextrin (ATS-β-CD) conjugates, in which artesunate (ATS) was coupled covalently to one of the primary hydroxyl groups of β-cyclodextrin (β-CD) through amino bond formation, were synthesized and characterized by 1H NMR, HRMS, 2D NMR (ROESY), X-ray diffraction (XRD), and thermogravimetric analysis (TGA). The results showed that the aqueous solubility of ATS-β-CD conjugates was 26-45 times better than that of free ATS. The cytotoxicity of the ATS-β-CD conjugates was evaluated on human colon cancer cell lines HCT116, LOVO, SW480, and HT-29, and the results indicated that ATS-2NβCD exhibited a very high cytotoxicity against HCT116, LOVO, and HT-29 with IC50 values of 0.58, 1.62, and 5.18 μmol/L, respectively. In addition, the supposition of better cytotoxicity was further supported by the control experiment of fluorescent cyclodextrin.
- Jiang, Rui-Jian,Zhao, Yu-Lin,Chen, Yun-Jian,Xiao, Dan,Wang, Fen,Han, Bin,Yang, Jian,Liao, Xia-Li,Yang, Li-Juan,Gao, Chuan-Zhu,Yang, Bo
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- Scutellarin-cyclodextrin conjugates: Synthesis, characterization and anticancer activity
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A series of scutellarin-cyclodextrin conjugates (SCU-CD conjugates), in which scutellarin was covalently bound to one of the primary hydroxyl groups of β-CD, were prepared, and their structures were determined using NMR and MS. These conjugates were further characterized by XRD and TG. The results showed that the aqueous solubility of the conjugates was much higher than that of scutellarin, and the conjugates could hardly be hydrolyzed to scutellarin in aqueous solutions. The cytotoxicity of SCU-CD conjugates on human colon cancer cell lines HT-29, SW480, Lovo and HTC116 indicated that the antitumor activities of the conjugates were better than that of scutellarin. This high antitumor activity, along with the satisfactory aqueous solubility and high stability of the conjugates, will be potentially useful for their application on human colon cancer chemotherapies.
- Yang, Bo,Zhao, Yu-Lin,Yang, Xia,Liao, Xia-Li,Yang, Jian,Zhang, Ji-Hong,Gao, Chuan-Zhu
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p. 1308 - 1314
(2013/08/24)
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- Microwave-assisted synthesis of 6-amino-β-cyclodextrins
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A general microwave-assisted procedure for the synthesis of 6-amino-β-cyclodextrins is reported. Mono-tosyl-β-cyclodextrin was used as the starting material in a one-pot route employing a solvent-free microwave-assisted reaction with a liquid amine. Shorter reaction times were observed for the formation of 6-amino-β-cyclodextrins using this novel microwave approach compared to the thermal procedure.
- Puglisi, Antonino,Spencer, John,Clarke, James,Milton, John
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scheme or table
p. 475 - 478
(2012/08/28)
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- Carboxy and diphosphate ester hydrolysis promoted by di- or tri-nuclear zinc(II) complexes based on β-cyclodextrin
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A new ligand (L), 6-mono-(2-(2-hydroxy-3-(hydroxymethyl)-5-methyl benzylamino)-ethylamino)-β-cyclodextrin, based on β-cyclodextrin derivatives with dinucleating units was synthesized and used to prepare a trimetallic bis-ligands zinc complex (Zn3(L2-) 2). The esterase activity of the complex was investigated by the hydrolysis of two carboxylic acid esters, bis(4-nitrophenyl)carbonate (BNPC) and 4-nitrophenyl acetate (NA), and a DNA model bis(4-nitrophenyl)phosphate (BNPP) as a phosphate ester. The catalytic rate for BNPC was very high, which was found to be a 5.63 × 103-fold rate enhancement over uncatalyzed hydrolysis and 1.62 × 102-fold rate enhancement over uncatalyzed hydrolysis for NA hydrolysis at pH = 7.0. For the catalytic hydrolysis of BNPP, the initial first-order rate constant of 0.1 mM catalyst was 5.85 × 10-8 s-1 at pH = 8.50 and 35 °C, which is a 731-fold acceleration over uncatalyzed hydrolysis. The second rate constant (kBNPP) was found to be 1.22 × 10-3 M-1 s-1 at pH = 10.0. According to the potentiometric titration study, the zinc complex exists in a dinuclear single ligand coordinated mode and a trinuclear bis-ligands system at pH ≥ 7.0. The ester hydrolysis activity was attributed to the cooperative interaction of the two metal centers and the hydrophobic cavity of β-cyclodextrin with substrates.
- Tang, Si-Ping,Hu, Ping,Chen, Huo-Yan,Chen, Sha,Mao, Zong-Wan,Ji, Liang-Nian
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experimental part
p. 222 - 227
(2011/04/12)
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- Cyclodextrin-Containing Polymers and Uses Thereof
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The invention provides a cyclodextrin-containing polymer comprising one or more cyclodextrin residues. The polymer is selected from a peptide, a polypeptide, an oligonucleotide or a polynucleotide or a mixture thereof. The peptide or polypeptide has at least one amino acid residue containing a functional side group and at least one of the cyclodextrin residues is covalently linked to the functional side group of the amino acid residue of said peptide or polypeptide or to the sugar moiety of a nucleotide residue of the oligonucleotide or polynucleotide.
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Page/Page column 11
(2008/12/08)
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- Spectrophotometric study of selective binding behaviors of dye molecules by pyridine-and bipyridine-modified ?2-cyclodextrin derivatives with a functional tether in aqueous solution
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Four ?2-cyclodextrin (?2-CD) derivatives bearing pyridine or bipyridine linkers, i.e., mono[6-(3-pyridinecarboxamide)ethyleneamino-6-deoxy]-?2-CD(2), mono[6-(4-pyridinecarboxamide)ethyleneamino-6-deoxy]-?2-CD (3), N,Na?2-bis(2-aminoethyl)-2,2a?2-bipyridine-4, 4a?2-dicarboxamide-bridged bis(6-amino-6-deoxy-?2-CD) (4), N,Na?2-bis(2-aminoethyl)-2,2a?2-bipyridine-3, 3a?2-dicarboxamide-bridged bis(6-amino-6-deoxy-?2-CD) (5), and their copper-(II) complexes (6 and 7) were selected as molecular receptors to explore the conformation-function relationship of oligo(?2-CD)s. The original conformations of hosts 4-7 and their inclusion complexation behaviors with some guest molecules, i.e., ammonium 8-anilino-1-naphthalenesulfonate (ANS), sodium 6-(p-toludino)-2-naphthalenesulfonate (TNS), and rhodamine B (RhB), were comprehensively investigated by means of UV-vis, 2D NMR, and fluorescence spectroscopy. The results indicated that these oligo(?2-CD)s, especially bis(?2-CD) 5 and its copper(II) complex 7, exhibited the significantly enhanced binding abilities toward guest molecules as compared with native ?2-CD. Typically, hosts 5 and 7 efficiently enhanced the original binding ability of native ?2-CD toward ANS by a factor of 38-42 times. These increased binding abilities of oligomeric hosts were discussed from the viewpoint of the size/shape-fit and multipoint recognition between host and guest.
- Liu, Yu,Li, Xue-Qing,Chen, Yong,Guan, Xu-Dong
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p. 19541 - 19549
(2008/04/18)
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- Synthesis of novel cyclomaltoheptaose (β-cyclodextrin) derivatives containing the Ebselen key moiety of benzoisoselenazolone
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A series of five novel cyclomaltoheptaose (β-cyclodextrin) derivatives containing benzoisoselenazolone groups have been synthesized as glutathione peroxidase mimics.
- Yang, Xiangliang,Wang, Qin,Xu, Huibi
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p. 1309 - 1312
(2007/10/03)
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- Synthesis of a water-soluble cyclodextrin modified hypocrellin and ESR study of its photodynamic therapy properties
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A water-soluble cyclodextrin modified hypocrellin B (HBCD) was designed and synthesized. HBCD retained the phototherapeutic properties and exhibited much stronger photoinduced damage to calf thymus DNA (CT DNA) than hypocrellin B and mercaptoacetic acid substituted hypocrellin B (MAHB). The mechanism of electron transfer from CT DNA to the triplet state of HBCD was confirmed by steady-state electron spin resonance (ESR) and a time-resolved ESR study.
- Ou, Zhi-Ze,Chen, Jing-Rong,Wang, Xue-Song,Zhang, Bao-Wen,Cao, Yi
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p. 1130 - 1136
(2007/10/03)
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- Cyclodextrin-based class I aldolase enzyme mimics to catalyze crossed aldol condensations
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A variety of mono- and unsymmetrical bifunctional β-cyclodextrins have been developed as efficient mimics of class I aldolases, some of which show a large rate acceleration and substrate selectivity.
- Yuan, De-Qi,Dong, Steven D.,Breslow, Ronald
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p. 7673 - 7676
(2007/10/03)
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