三维还原氧化石墨烯/β-环糊精复合物的合成及其电化学检测水中左氧氟沙星北大核心CSCD

成功构筑了β-环糊精修饰的三维还原氧化石墨烯复合材料(3D-rGO/β-CD),并对该复合材料进行扫描电子显微镜、傅里叶红外光谱、热重分析和拉曼光谱分析等一系列的表征,分析了其形貌和结构的特征。进一步将其修饰到玻碳电极(GCE)表面,构建了一种新型电化学传感器(3D-rGO/β-CD/GCE)。利用3D-rGO/β-CD/GCE电化学传感器,通过微分脉冲伏安法(DPV)对左氧氟沙星(LEV)进行了检测。其中,具有多孔结构的三维还原氧化石墨烯具有优异的导电性能、比表面积大、化学稳定性好等优良的性质,而修饰的β-环糊精能在其环形腔内与客体分子结合形成超分子包合物,进而可以对LEV进行有效识别。研究结果显示,在最优实验条件下,3D-rGO/β-CD/GCE对左氧氟沙星的检测具有较宽的线性范围(1~150μmol/L),且检测限可达0.33μmol/L,同时该修饰电极还表现出良好的选择性和稳定性。此外,成功将其应用于实际水样中LEV的检测,表明该传感器具有一定的应用潜力。     

Sensitive and selective detection of alcohols via fluorescence modulation

Reported herein is the selective detection of aliphatic alcohols using cyclodextrin-promoted, proximity-induced fluorescence modulation of a high-quantum yield fluorophore. This fluorescence modulation occurred when the analyte was held in close proximity to the fluorophore via non-covalent cyclodextrin–analyte–fluorophore interactions, and led to unique modulation responses for each analyte, fluorophore and cyclodextrin investigated. These changes in fluorescence were used for the generation of an array using linear discriminant analysis that successfully generated unique pattern identifiers for 99% of the investigated analytes, and could detect alcohols at micromolar concentrations. These results represent a fundamentally new detection approach for these challenging analytes, and have significant potential in the development of novel detection schemes.     

β‐Cyclodextrin as an Efficient and Recyclable Supramolecular Catalyst for the Synthesis of Heterocyclic Compounds

β‐Cyclodextrin (β‐CD ), a naturally occurring supramolecular structure, is an effective catalyst for the synthesis of heterocyclic compounds. Its ubiquity, high performance, nontoxicity, ease of separation, and reusability have drawn the attention of green chemists. Here we present the synthetic procedures of heterocyclic compounds catalyzed by β‐CD in water and compare them with those using organic solvents. In many cases, using water as the solvent shows better efficiency than conventional organic solvents with regard to catalytic activity and simplicity of recycling procedures. This review highlights the applications of β‐CD in catalysis covering the years 2004–2016.     

Chiral Separation of Esmolol and Terazosin by Cyclodextrinmodified Capillary Zone Electrophoresis

IntroductionTheincreasingnecessity0fpharmacologicalresearchforchiraldrugshasrenderedchiralseparationanactiveareaincaPillaryelectroph0resis(CE)today.Variousmodes0fCE,includingcaPillaryzoneelectroph0resis(CZE),micellarelectrokineticchromatography(MEKC),caPillarygelelectrophoresis(CGE)andcapillaryisotachophoresis(CITP),havebeenappliedforthispurp0se',amongwhichCZEisthemostpopularoneforitshighefficiency,lowexpenseandeaseofoperation.Forsuccessfulchiralseparati0ninCZE,theselectortypeisofcr…     

Determination of the Inclusion Constants for the Inclusion Complexes between meso-Tetrakis (4-sulfonatophenyl) Porphyrin and Cyclodextrins by Three Methods

In this paper, the interactions of meso-Tetrakis (4-sulfonatophenyl) porphyrin (TPPS 4 ) and six cyclodextrins have been studied, respectively, by fluorescence spectroscopy, polarography and thin-layer chromatography. The inclusion constants of different methods are determined and the comparison of inclusion capacity of various cyclodextrins indicates that for the ionic cyclodextrins the charge interaction plays an important role in the inclusion procedure. The thermodynamic parameters of interaction imply that the inclusion process shows the enthalpy-entropy compensation effect. Cyclodextrin, being regarded as an artificial analogue of proteinoid of heme, provides a protective sheath for porphyrin. However, the TPPS 4 , encapsulated within this saccharid-coated barrier, its solubility is enhanced prominently, which exhibits that this interaction may modify the biological properties of TPPS 4 that owned the similar properties as hematoporphyrin.     

Thermodynamics of complexes between nucleobase-modified β-cyclodextrins and bile salts

The binding of three nucleobase-modified β-CDs, (i.e., mono(6-ade-6-deoxy)-β-CD 2, mono(6-thy-6-deoxy)-β-CD 3, and mono(6-ura-6-deoxy)-β-CD 4) with four bile salts (deoxycholate, DCA; cholate, CA; glycocholate, GCA; and taurocholate, TCA) were investigated by means of circular dichroism, 2D NMR spectroscopy and calorimetric titration. The results show the binding of host 2 with bile salts is weaker and different from hosts 3 and 4. Enthalpy changes between hosts 2–4 and bile salts are much more favorable than those of native β-CD 1, whereas the entropy changes are unfavorable.     

New SPE loading material for affinity‐based separation of cyclodextrins from drug:CD complexes in order to overcome Beer's law deviations

Molecular inclusion of guest molecules within CDs is known to alter guest molecule spectrophotometric absorptivity, making their determination, based on spectrophotometric data, inaccurate. Therefore specific analytical methods capable of quantifying the drugs as free molecules must be developed and validated. SPE was selected to simplify sample and avoid more time‐consuming alternatives. A new solid phase was synthesized and characterized by infrared spectrometry, differential scanning calorimetry and elemental analysis. The competitive complexation of adamantane groups immobilized on the silica substrate facilitates drug:CD complex dissociation and elimination of CD from samples. The drug molecules, now free from CD, can be easily analysed by an already available HPLC method. This new SPE loading material was employed in the determination of ketoprofen in its CD complex as a representative example of the utility of this novel material. The calculated analytical errors were reduced from a maximum of 20.79% (without SPE) to a minimum of 3.99%.     

TritonX-100 selective chemosensor based on β-cyclodextrin modified by anthracene derivative

β-Cyclodextrin (CD) modified by 2-(9-anthracenecarboxamido)phenyl group (Ant-CD) was synthesized and their complexation behavior was investigated by UV and fluorescence spectroscopy. Fluorescence intensity of Ant-CD was dramatically enhanced ca. 10-fold by the addition of TritonX-100 (TX-100) in water below the critical micelle concentration. Ant-CD also showed ca. 4-fold fluorescence increasing in the addition of analogous materials, n-octylbenzenesulfonate in water. These results indicate that Ant-CD can act as a highly sensitive and selective chemosensor for TX-100. Ant-CD and TX-100 formed a pseudorotaxane supramolecular complex. This result was supported by ¹H-¹H NOESY NMR measurement.     

Water-soluble γ-cyclodextrin polymers with high molecular weight and their complex forming properties

Polymeric cyclodextrins (CDs) derivatives combine the complex forming properties of CDs and properties of polymers such as high molecular weight and high solubility, justifying the increasing interest for its use in biomedical science. In this paper, a series of water-soluble epichlorohydrin/γ-CD polymers were synthesized and the influences of the epichlorohydrin/γ-CD ratio, NaOH concentration and reaction time were studied in order to get high molecular weight polymers. The M_w distribution and CD content of the polymers were determined by size exclusion chromatography and ¹H NMR, respectively. The complexing properties of the polymers were studied by isothermal titration calorimetry using Methyl Orange (MO) and Sodium Fusidate (Fus) as guests for the γ-cyclodextrin host. The complex formation with MO is exclusively enthalpy driven whereas the one with Fus is totally entropy driven.