n‐Heptyl α‐D ‐mannoside (HM) has previously been identified as a nanomolar FimH antagonist able to prevent Escherichia coli adhesion. We have designed mono‐ and heptavalent glycoconjugates in which HM is tethered to β‐cyclodextrin (β‐CD) through short and long spacers. One‐pot click or co‐clicking procedures were developed to directly obtain the glycoconjugates from unprotected HM and β‐CD precursors. These FimH antagonists were examined biophysically and in vivo. Reverse titrations by isothermal calorimetry led to trapping of the short‐tethered heptavalent β‐CD in a complex with three FimH lectins. Combined dynamic light scattering and small‐angle X‐ray solution scattering data allowed the construction of a model of the FimH trimer. The heptavalent β‐CDs were shown to capture and aggregate living bacteria in solution and are therefore also able to aggregate FimH when attached to different bacteria pili. The first in vivo evaluation of multivalent FimH inhibitors has been performed. The heptavalent β‐CDs proved to be much more effective anti‐adhesive agents than monovalent references with doses of around 2 μg instilled in the mouse bladder leading to a significantly decreased E. coli load. Intravenously injected radiolabeled glycoconjugates can rapidly reach the mouse bladder and >2 μg concentrations can easily be retained over 24 h to prevent fluxing bacteria from rebinding. 相似文献
Owing to their broad spectrum of biological activities and low toxicity, β‐lactams are attractive lead structures for the design of novel molecular probes. However, the synthesis of positron emission tomography (PET)‐isotope‐labelled β‐lactams has not yet been reported. Herein, we describe the simple preparation of radiofluorinated β‐lactams by using the fast Kinugasa reaction between 18F‐labelled nitrone [18F]‐ 1 and alkynes of different reactivity. Additionally, 18F‐labelled fused β‐lactams were obtained through the reaction of a cyclic nitrone 7 with radiofluorinated alkynes [18F]‐ 6 a , b . Radiochemical yields of the Kinugasa reaction products could be significantly increased by the use of different CuI ligands, which additionally allowed a reduction in the amount of precursor and/or reaction time. Model radiofluorinated β‐lactam‐peptide and protein conjugates ([18F]‐ 10 and 18F‐labelled BSA conjugate) were efficiently obtained in high yield under mild conditions (aq. MeCN, ambient temperature) within a short reaction time, demonstrating the suitability of the developed method for radiolabelling of sensitive molecules such as biopolymers. 相似文献
Summary: We have successfully constructed a redox‐responsible hydrogel system by combination of β‐cyclodextrin (β‐CD), dodecyl‐modified poly(acrylic acid) [p(AA/C12)], and a redox‐responsive guest, ferrocenecarboxylic acid (FCA). In the reduced state of FCA, the ternary mixture exhibited a gel‐like behavior, whereas, in its oxidized state, the mixture exhibited a sol behavior.
Conceptual illustration for the redox‐responsive hydrogel system. 相似文献
Reactions of 5-(p-aminophenyl)-10,15,20-triphenyl porphyrin (1) with Ru3(CO)12 or M(OCOCH3)2 (M=Ni,Mn) afforded metalloporphyrins(4-6),respectively.6-Deoxy-6-io-do-β-cyclodextrin(2) and mono(6-O-trifluoromethanesulfonyl) permethylated β-cyclodextrin(3) reacted with complexes 4-6 to give β-cyclodextrin bonded metal porphyrins (7-9) and permethylated β-cyclodextrin bonded me-tal porphyrins (10-12) respectively.These new complexes were identified by MS,IR,UV-visible and ^1H NMR spectra,and elemental analysis. 相似文献
A convenient and environmentally benign procedure for the synthesis of glycals from glycosyl bromides with very low zinc dust loading (1.5 equiv.) is described. The process is activated by β‐cyclodextrin and ultrasound. Based on 19 samples, this method has been demonstrated to be highly effective for a broad range of glycosyl bromides, including acid‐ or base‐sensitive and disaccharide glycosyl bromides. A yield of 85%–96% of glycals was obtained. 相似文献
Novel 2‐(1‐substituted‐1H‐1,2,3‐triazol‐4‐yl)pyridine (pytl) ligands have been prepared by “click chemistry” and used in the preparation of heteroleptic complexes of Ru and Ir with bipyridine (bpy) and phenylpyridine (ppy) ligands, respectively, resulting in [Ru(bpy)2(pytl‐R)]Cl2 and [Ir(ppy)2(pytl‐R)]Cl (R=methyl, adamantane (ada), β‐cyclodextrin (βCD)). The two diastereoisomers of the Ir complex with the appended β‐cyclodextrin, [Ir(ppy)2(pytl‐βCD)]Cl, were separated. The [Ru(bpy)2(pytl‐R)]Cl2 (R=Me, ada or βCD) complexes have lower lifetimes and quantum yields than other polypyridine complexes. In contrast, the cyclometalated Ir complexes display rather long lifetimes and very high emission quantum yields. The emission quantum yield and lifetime (Φ=0.23, τ=1000 ns) of [Ir(ppy)2(pytl‐ada)]Cl are surprisingly enhanced in [Ir(ppy)2(pytl‐βCD)]Cl (Φ=0.54, τ=2800 ns). This behavior is unprecedented for a metal complex and is most likely due to its increased rigidity and protection from water molecules as well as from dioxygen quenching, because of the hydrophobic cavity of the βCD covalently attached to pytl. The emissive excited state is localized on these cyclometalating ligands, as underlined by the shift to the blue (450 nm) upon substitution with two electron‐withdrawing fluorine substituents on the phenyl unit. The significant differences between the quantum yields of the two separate diastereoisomers of [Ir(ppy)2(pytl‐βCD)]Cl (0.49 vs. 0.70) are attributed to different interactions of the chiral cyclodextrin substituent with the Δ and Λ isomers of the metal complex. 相似文献
Two novel monovinyl β‐cyclodextrin (β‐CD) monomers are synthesized. Their chemical compositions are characterized by means of element analysis, NMR and FT‐IR spectroscopy. The results show that the synthesis techniques used are convenient and efficient. Using N‐isopropylacrylamide as a comonomer, two novel linear copolymers can also be synthesized.
We report the synthesis of a hydrophilic copolymer with one polyethylene glycol (PEG) block and one β‐cyclodextrin (β‐CD) containing block by a “click” reaction between azido‐substituted β‐CD and propargyl flanking copolymer. 1H NMR study suggested a highly efficient conjugation of β‐CD units by this approach. The obtained copolymer was used as a host macromolecule to construct assemblies in the presence of hydrophobic guests. For assemblies containing a hydrophobic polymer, their size can be simply adjusted by simply changing the content of hydrophobic component. By serving as a guest molecule, hydrophobic drugs can also be loaded accompanying the formation of nanoparticles, and the drug payload is releasable. Therefore, the copolymer synthesized herein can be employed as a carrier for drug delivery. 相似文献
Summary: Polypyrrole (PPy) microtubes with an actinomorphic morphology are synthesized by a chemical method in the presence of an inclusion complex (IC) of mono [6‐deoxy‐6‐(2‐butenedinitrile‐2,3‐dimercapto sodium salt)]‐β‐cyclodextrin (6‐mnt‐β‐CD) with methyl orange (MO) as a dopant in aqueous solution. The morphologies of the obtained PPy were studied using transmission electron microscopy (TEM). It was found that the IC of 6‐mnt‐β‐CD with MO significantly affects the morphology of the resulting PPy.
The morphology of polypyrrole synthesized in the presence of 6‐mnt‐β‐CD/MO, determined by TEM. 相似文献
We report a novel, green hydrothermal‐synthesis route to well‐dispersed anatase TiO2 nanoparticles with particle sizes of 9–16 nm in the presence of β‐CD (β‐cyclodextrin). During the synthesis process, the CD‐containing synthesis mixture assembled in both longitudinal and latitudinal directions. Driven by the interaction between molecules, the β‐CDs assembled in the longitudinal direction to form long‐chain compounds, whereas in the latitudinal direction, they tended to form regular aggregates through coordination with the Ti species from the hydrolysis of tetrabutyl titanate. In view of the effect of the coordination and the steric hindrance of β‐CDs as a supramolecular shell, homogeneous nuclei and slow growth of TiO2 crystals during the synthesis process was observed, which was responsible for the formation of uniform TiO2 nanoparticles. The low β‐CD dosage and the high product yield (>90 %) demonstrated well the potential of this synthesis route in the large‐scale industrial production of anatase nanoparticles. 相似文献
Molecular imaging holds considerable promise for elucidating biological processes in normal physiology as well as disease states, but requires noninvasive methods for identifying analytes at sub‐micromolar concentrations. Particularly useful are genetically encoded, single‐protein reporters that harness the power of molecular biology to visualize specific molecular processes, but such reporters have been conspicuously lacking for in vivo magnetic resonance imaging (MRI). Herein, we report TEM‐1 β‐lactamase (bla) as a single‐protein reporter for hyperpolarized (HP) 129Xe NMR, with significant saturation contrast at 0.1 μm . Xenon chemical exchange saturation transfer (CEST) interactions with the primary allosteric site in bla give rise to a unique saturation peak at 255 ppm, well removed (≈60 ppm downfield) from the 129Xe‐H2O peak. Useful saturation contrast was also observed for bla expressed in bacterial cells and mammalian cells. 相似文献
Summary: A water‐soluble gold nanoparticle aggregate 2 was prepared by chloroauric acid and a polypseudorotaxane 1 of mono‐6‐thio‐β‐cyclodextrin with poly(propylene glycol) bis(2‐aminopropyl ether) ( ≈ 2 000) in the presence of sodium borohydride in N,N‐dimethylformamide (DMF) solution. The investigative results indicated that the gold nanoparticle aggregate 2 might act as an efficient DNA‐cleavage reagent.
A typical TEM image of gold nanoparticle aggregate 2 . 相似文献
The supramolecular interaction of gemfibrozil with β-cyclodextrin (β-CD) was studied by spectrofluorimetry. The mechanism of the inclusion was discussed by spectrofluoremetry, infrared spectrum and ^1H NMR spectrum. The results showed that a 1 : 1 (β-CD : gemfibrozil) complex was formed with an apparent association constant of 3.844 × 10^3 L·mol^-1. Based on the enhancement of the fluorescent intensity of gemfibrozil, a spectrofluorimetric method for the determination of gemfibrozil in bulk aqueous solution in the presence of β-CD was developed. The linear range was 3.30 ng·mL^- 1 -6.00 ug·mL^-1 with the detection limit of 0.980 ng·mL^-1. There was no interference from the excipients normally used in tablet composition and the serum main compositions. The proposed method was then successfully applied to the determination of gemfibrozil in capsules and serum. 相似文献