HgCl2-头孢噻肟螯合阴离子与碱性三苯甲烷类染料相互作用的共振瑞利散射光谱及其分析应用

在pH为5.3～6.8的Britton-Robinson(BR) 缓冲溶液中, 头孢噻肟钠(CFTM)与HgCl2形成摩尔比为1∶1的螯合阴离子, 它能进一步与结晶紫、甲基紫、乙基紫、亮绿、碘绿、甲基绿和孔雀石绿等碱性三苯甲烷类染料反应形成三元离子缔合物, 导致共振瑞利散射(RRS)的显著增强. 最大RRS峰分别位于367, 367, 340, 367, 340, 340和340 nm附近, 在一定的CFFM质量浓度范围内散射强度与头孢噻肟钠的浓度均呈良好的线性关系. 用结晶紫、甲基紫、乙基紫、亮绿、碘绿、甲基绿和孔雀石绿体系测定头孢噻肟钠的线性范围和检出限(3σ) 分别为0.0090～3.5 μg/mL和2.7 ng/mL, 0.0092～3.5 μg/mL和2.8 ng/mL, 0.013～3.5 μg/mL和4.0 ng/mL, 0.010～3.5 μg/mL和3.1 ng/mL, 0.011～3.5 μg/mL和3.4 ng/mL, 0.012～4.0 μg/mL和3.5 ng/mL以及0.016～3.5 μg/mL和4.7 ng/mL, 其中以结晶紫体系灵敏度最高. 研究了适宜的反应条件和影响因素, 对离子缔合物的组成和离子缔合反应机理进行了探讨, 考察了共存物质的影响, 表明方法有良好的选择性, 据此发展了用HgCl2和碱性三苯甲烷类染料的灵敏、简便、快速测定痕量头孢噻肟钠的新方法.     

Study on the inclusion interaction of ethyl violet with cyclodextrins by MWNTs/Nafion modified glassy carbon electrode

The interactions of ethyl violet (EV) with cyclodextrins (CDs) were investigated by Multi-wall carbon nanotubes/Nafion composite film modified glassy carbon electrode (MWNTs/Nafion/GCE). It was found that the MWNTs/Nafion composite film can effectively catalyze the electrode reaction of EV. The variation of the electrochemical behavior of EV upon the addition of CDs indicated the formation of the inclusion complexes of EV with β-CD, heptakis (2,3,6-tri-O-methyl)-β-CD (TM-β-CD), heptakis (2,6-di-O-methyl)-β-CD (DM-β-CD), hydroxypropyl-β-CD (HP-β-CD), and carboxymethyl-β-CD (CM-β-CD). The stoichiometry ratios of EV and the above five CDs were found to be 1:1. The inclusion ability obeyed the order: CM-β-CD > HP-β-CD > TM-β-CD > DM-β-CD > β-CD. The results showed that the modified β-CDs exhibited stronger binding ability than native β-CD, especially the charged CM-β-CD, which implied that the inclusion capacity depends on not only size matching and hydrophobicity but also electrostatic interaction. ¹HNMR spectra and molecule mechanics calculations suggested that EV was included into the cavity of β-CD from the wider side.     

甲基绿的电化学行为及其与环糊精形成超分子体系研究

应用“电流法”研究了甲基绿—环糊精超分子体系 ,测定了甲基绿和 4种环糊精的包结常数 .其包结能力为HP_β_CD >β_CD >SBE_β_CD >CM_β_CD ,包结比为 1 :2 (甲基绿 :环糊精 )但甲基绿与α_CD和γ_CD不能形成超分子体系 .此外 ,本文还探讨了甲基绿的电极反应机理 ,初步表明 ,甲基绿在电极上还原的电子转移数为 4 ,有 2个质子参与反应     

十种以碱性染料制备的PVC膜ReO4-离子选择电极——碱性染料结构对ReO4-电极性能的影响

本文以不同碱性染料制备了十种PVC膜ReO₄^-离子选择电极,测试和比较了它们的性能,筛选出六种较优者,并根据其差别初步探讨了碱性染料结构对ReO₄^-电极性能的影响.     

Spectral properties and supramolecular inclusion complex formation between 2-styrylbenzothiazolium dye and cyclodextrins

The effect of native and randomly methylated β-CDs on the absorption and steady-state fluorescence spectra of 2-(4-dimethylaminostyryl)-3-(2-hydroxyethyl)-benzothiazolium chloride (DHB) in aqueous buffer solutions with various pH values was studied. The inclusion with both CDs at pH 7.2 barely changed the UV spectra, whereas significant variations were produced in the emission spectra in all buffer solutions. In all cases the CDs increase guest fluorescence. The 1:1 stoichiometry of the inclusion complexes of the dye with both CDs was established according to the modified Benesi-Hildebrand method. Binding constant values were calculated using the iterative nonlinear least-squares regression approach. The pH of the solution and the type of the CD affected complex stability. The results indicate that native β-CD possesses better complexing ability towards DHB than randomly substituted β-CD and that the most stable inclusion complexes are formed in basic medium because of the structural changes in the guest molecule. In basic medium an attempt is made to interpret the proposed mechanism in terms of molecular rearrangement which take place as the dye penetrates the CD cavity.     

Complexation of 4‐dimethylaminoazobenzene with various kinds of cyclodextrins: Effects of cyclodextrins on the thermal cis‐to‐trans isomerization

On the basis of the change in electronic and induced circular dichroism spectra for complex formation, the complexation of 4‐dimethylaminoazobenzene (DAAB) with four kinds of cyclodextrins (α‐ and β‐cyclodextrin (CD), heptakis(2,6‐di‐O‐methyl)‐β‐cyclodextrin, and heptakis(2,3,6‐tri‐O‐methyl)‐β‐cyclodextrin) was studied in methanol–water and dimethyl sulfoxide–water mixtures. It was found that the trans and cis isomers of DAAB form two different types of complex (inclusion and lid type) with CDs, depending on the kinds of CDs and solvents. Further, we have examined the effect of CDs on the thermal cis‐to‐trans isomerization of DAAB. The accelerated or decelerated effect on the thermal isomerization was observed upon adding CDs. The effects of CDs on the thermal isomerization are discussed in connection with the complexation of the cis‐isomer of DAAB with CDs. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 34: 481–487, 2002     

Solvent‐dependent formation of inclusion complexes between methylated cyclodextrins and biodegradable polymers

The inclusion complexes (ICs) of unmodified natural and methylated α‐cyclodextrins (CDs) with biodegradable polymers, polyethylene glycol and poly(ε‐caprolactone), were prepared by two methods, that is, the one using water and the other using chloroform as the solvent for the respective CDs. The ICs obtained were characterized by IR, WAXD, DSC, and ¹³C CP/MAS NMR. It was found that the possibility and the phenomena of IC formation could be varied with the degree of methyl substitution of CD as well as the type of solvents used. Methylated α‐CDs showed the prominent characteristics of IC formation with polymers in the case where chloroform was used than in the case where water was used as the solvent for CDs, while vice versa in the case of native α‐CD. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 879–891, 2008     

Study of inclusion complex formation between a cationic surfactant, two cyclodextrins and a drug

In this study inclusion of hexadecyltrimethylammonium bromide (HTAB) with α-, and β-cyclodextrin (CD) in the presence and the absence of bromhexine (BH) was investigated using ion-selective electrode method. The association constants of HTAB with CDs were determined by potentiometry and were close to literature values. The obtained results indicated that α-CD formed 1:1 and 1:2 inclusion complexes, but β-CD formed only a 1:1 inclusion complex. In the presence of drug, the interaction between CDs and HTAB decreased, because both drug and HTAB could interact with CDs. The results showed that the interaction between drug and CDs are greater than HTAB and CDs. The stoichiometry of the inclusion complexes, the critical aggregation concentration (CAC), the monomer surfactant concentration of HTAB, [HTAB]_f, and also the effect of the inclusion complex on the micellization process of the HTAB were determined by conductivity measurements.     

Study on inclusion interaction of piroxicam with beta-cyclodextrin derivatives

The inclusion behavior of piroxicam (PX) with beta-cyclodextrin (beta-CD), hydroxypropyl-beta-cyclodextrin (HP-beta-CD), and carboxymethyl-beta-cyclodextrin (CM-beta-CD) was investigated by using steady-state fluorescence and nuclear magnetic resonance (NMR) technique. The various factors affecting the inclusion process were examined in detail. The remarkable fluorescence emission enhancement upon addition of CDs suggested that cyclodextrins (CDs) were most suitable for inclusion of the uncharged species of PX. The stoichiometry of the PX-CDs inclusion complexes was 1:1, except for beta-CD where a 1:2 inclusion complex was formed. The formation constants showed the strongest inclusion capacity of beta-CD. NMR showed the inclusion mode of PX with CDs.     

Adsorption of ethyl violet dye in aqueous solution by regenerated spent bleaching earth

The adsorption of basic dye (i.e., ethyl violet or basic violet 4) from aqueous solution onto the regenerated spent bleaching earth (RSBE) was carried out by varying the process parameters such as initial concentration, pH, and temperature. As analytical comparisons, activated bleaching earth (ABE) was also used as adsorbent for the adsorption of the basic dye at various initial concentrations. The experimental results showed that the adsorption process can be well described with the pseudo-second-order reaction model and less fitted by the intra-particle diffusion model. The kinetic parameters of both models obtained in the present work are in line with pore properties of the two adsorbents. According to the equilibrium adsorption capacity from the fitting of pseudo-second-order reaction model, it was further found that the both models of Langmuir and Freundlich appeared to fit well the isotherm data. In addition, the thermodynamic parameters were evaluated based on the pseudo-second-order rate constants, showing that the adsorption of ethyl violet onto the RSBE is endothermic in nature.     

〔I2Br〕- 与某些碱性三芳基甲烷染料的水相显色反应及其应用于碘的分光光度测定

研究〔I2Br〕-络阴离子与乙基紫、结晶紫、维多利亚蓝4R等碱性三芳基甲烷染料在聚乙烯醇存在下的离子缔合反应的条件、分光光度特征和分析化学性质。结果表明,在稀磷酸介质中,当形成上述离子缔合络合物时,溶液均发生明显的颜色变化。不同染料体系的摩尔吸光系数在2.6×104～6.2×104L*mol-1*cm-1之间,以乙基紫体系灵敏度最高。碘离子浓度在0～1.6mg/L（乙基紫体系）、0～1.4 mg/L（结晶紫体系）和0～0.8 mg/L(维多利亚蓝体系)符合比耳定律,可用于水相直接显色测定碘离子。方法也有良好的选择性,较大量的其他卤离子、一些无机酸根以及一定量的常见金属离子不干扰。用于海带、紫菜和黄豆中碘离子的测定,结果较为满意。     

β-环糊精及其衍生物对维生素分子的识别作用

以乙基紫(EV)为光谱探针,采用紫外-可见光谱法测定了两种维生素(V)与β-环糊精(β-CD)、羟丙基-β-环糊精(HP-β-CD)和磺丁醚-β-环糊精(SBE-β-CD)的包合特性.结果表明,多种弱相互作用力协同作用于环糊精的包合过程,主-客体间的尺寸匹配影响了包合物的稳定性.包合能力β-CDHP-β-CDSBE-β-CD.     

Resonance Rayleigh scattering method for the determination of trace amounts of cadmium with iodide-basic triphenylmethane dye systems

In dilute phosphoric acid solution, cadmium (II) reacts with a large excess of I- to form [CdI4]2- which reacts further with basic triphenylmethane dyes such as crystal violet (CV), ethyl violet (EV), methyl violet (MV), brilliant green (BG) or malachite green (MG) to form an ion-association complex. This results in a significant enhancement of resonance Rayleigh scattering (RRS) intensity and the appearance of new RRS spectra. The characteristics of RRS spectra of the ion-association complexes, the influencing factors and the optimum conditions of these reactions have been investigated. The intensity of RRS is directly proportional to the concentration of cadmium from 0 to 60 ng mL(-1) for EV and MV systems, 0 to 80 ng mL(-1) for CV system, and 0 to 100 ng mL(-1) for BG and MG systems. The methods exhibit high sensitivities and the detection limits for cadmium are between 0.35 and 2.00 ng mL(-1) depending on the different reaction systems. The new RRS method was applied to the direct determination of traces of cadmium in pure zinc and synthetic water samples.     

Inclusion of Paracetamol into β-cyclodextrin nanocavities in solution and in the solid state

We report on steady-state UV-visible absorption and emission characteristics of Paracetamol, drug used as antipyretic agent, in water and within cyclodextrins (CDs): β-CD, 2-hydroxypropyl-β-CD (HP-β-CD) and 2,6-dimethyl-β-CD (Me-β-CD). The results reveal that Paracetamol forms a 1:1 inclusion complex with CD. Upon encapsulation, the emission intensity enhances, indicating a confinement effect of the nanocages on the photophysical behavior of the drug. Due to its methyl groups, the Me-β-CD shows the largest effect for the drug. The observed binding constant showing the following trend: Me-β-CD>HP-β-CD>β-CD. The less complexing effectiveness of HP-β-CD is due to the steric effect of the hydroxypropyl-substituents, which can hamper the inclusion of the guest molecules. The solid state inclusion complex was prepared by co-precipitation method and its characterization was investigated by Fourier transform infrared spectroscopy, 1H NMR and X-ray diffractometry. These approaches indicated that Paracetamol was able to form an inclusion complex with CDs, and the inclusion compounds exhibited different spectroscopic features and properties from Paracetamol.     

A liquid chromatography-electrospray ionization-mass spectrometry method for quantification of cyclotides in plants avoiding sorption during sample preparation

Cyclotides are plant-produced, bioactive, cyclic mini-proteins with interesting pharmaceutical and agricultural applications. A reverse phase liquid chromatography electrospray ionization mass spectrometry (RP-LC-ESI-MS) method for analysis of cyclotides in plant materials with a minimum of sample pre-treatment is presented. Three exemplary cyclotides (kalata B1, kalata B2 and cycloviolacin O2) were used as reference substances for the method development. Linearity (r(2)>0.99) was achieved in the concentration range 0.05-10 mg/L and the limit of detection was 1.7-4.0 μg/L. The present study is the first to demonstrate that cyclotides dissolved in water sorb to glass vials, but the addition of 15% of acetonitrile or 40 mg/L of bovine serum albumin is sufficient to keep the cyclotides in solution. Cyclotides were extracted from candied violets, violet tea, and the plants Oldenlandia affinis and Viola odorata using 70% methanol containing 0.1% formic acid (v/v). The plant content was determined to be 23.5-14,200 μg/g (dry weight). The highest content of cyclotide was found in wild Danish V. odorata, and it is the highest content of cyclotide in a plant reported hitherto. Candied violets contained 0.00-8.66 μg/g (dry weight), while no cyclotides were detected in commercial violet tea.     

Carbon Dots as a Promising Green Photocatalyst for Free Radical and ATRP‐Based Radical Photopolymerization with Blue LEDs

Carbon dots (CDs) have been used for the first time as a sensitizer to initiate and activate free radical and controlled radical polymerization, respectively, based on an ATRP protocol with blue LEDs. Consideration of diverse heteroatom‐doped CDs indicated that N‐doped CDs could serve as an effective photocatalyst and photosensitizer in combination with LEDs emitting either at 405 nm or 470 nm. Free radical polymerization was initiated by combining the CDs with an iodonium or sulfonium salt in tri(propylene glycol) diacrylate. Polymerization of methyl methacrylate (MMA) by photo‐induced ATRP was achieved with CDs and ethyl α‐bromophenylacetate using Cu^II as catalyst in the ppm range. The polymers obtained showed temporal control, narrower dispersity ?1.5, and chain‐end fidelity. The first‐order kinetics and ON/OFF experiments additionally gave evidence of the constant concentration of polymer radicals. No remarkable cytotoxic activity was observed for the CDs, underlining their biocompatibility.     

Properties and the inclusion behavior of 6-O-alpha-D-galactosyl- and 6-O-alpha-D-mannosyl-cyclodextrins

The novel heterogeneous branched cyclodextrins (CDs), 6-O-alpha-D- galactosyl-alpha, -beta, and -gamma CDs (Gal-alpha, -beta, and -gamma CDs) and 6-O-alpha-D-mannosyl-alpha, -beta, and -gamma CDs (Man-alpha, -beta, and -gamma CDs) dissolved sufficiently in water and in 10-50% (v/v) methanol aqueous solutions, as did the homogeneous branched CDs, 6-O-alpha-D-glucosyl-alpha, -beta, and -gamma CDs (Glc-alpha, -beta, and -gamma CDs). The solubilities of heterogeneous branched CDs were higher than those of each parent non-branched CDs. The hemolytic activities of heterogeneous and homogeneous branched CDs were lower than those of each parent non-branched CDs and the hemolytic activity became weaker in the order of non-branched CD > Man-CD > Glc-CD > Gal-CD in each series of alpha, beta, and gamma CD. AL type solubility-phase diagrams were displayed in the formation of inclusion complexes of the guest compounds of small size (methyl benzoate, estriol, and dexamethasone) with Gal-, Man-, and Glc-CDs, and marked differences among the three kinds of branched CDs could not be detected. However, solubility-phase diagrams between these branched CDs and the insoluble guest compounds of large cyclic structure (cyclosporin A, tacrolimus, and amphotericin B) showed AP type, and the improvement of water solubilities of these guest compounds with three kinds of branched CDs was enhanced in the order of Man-CDs > Glc-CDs > Gal-CDs.     

Preparation and characterization of inclusion complexes of pefloxacin mesylate with three kinds of cyclodextrins

The ability of alpha-cyclodextrin, beta-cyclodextrin and hydroxypropyl-beta-cyclodextrin (alpha-CD, beta-CD and HP-beta-CD) to break pefloxacin mesylate (PM) aggregates by forming inclusion complexes has been studied using 1H NMR (nuclear magnetic resonance spectroscopy), 13C NMR and fluorescence spectra. The inclusion constants are determined to compare the corresponding inclusion capacity. Solid-inclusion complexes of PM with CDs are synthesized by coprecipitation method, and all the inclusion ratios are found to be 1:1. Additionally, spatial characterization of complexes has been proposed based on two-dimensional nuclear magnetic resonance technique (2D NMR) and spatial conformation is also investigated to propose two possible models between PM and CDs.     

1H NMR study of the inclusion of Costa-type organocobalt(III) complexes in cyclodextrins

The inclusion behavior between Costa-type complexes and cyclodextrins (CDs) was studied by 1H NMR in aqueous solution. The results indicated that 1:1 inclusion complex was formed, in which the alkyl group of the guest was included in the cavity of CDs. The stability constants of the inclusion complexes were determined by the quantitative 1H NMR method. The effects on stability constants were discussed when various host and guest compounds were used.     

Dynamic analyses on induced-fit gaseous guest binding to organic crystals with a quartz-crystal microbalance

The inclusion behavior of gaseous guest molecules in a solid apohost, an orthogonal anthracene-bis(resorcinol)tetraol (1), was investigated with a quartz-crystal microbalance (QCM). Compound 1 forms crystals composed of molecular sheets bound together by an extensive hydrogen-bonded network. An apohost of 1 was cast onto a QCM and the binding of gaseous guest molecules was followed as a function of time by observing the decrease in the oscillation frequency, which is directly related to the increase in mass. Ethyl acetate and methyl ethyl ketone were significantly included into the apohost, whereas benzene and cyclohexane were simply adsorbed onto the surface of the solid; all these guests have similar vapor pressures at 25 degrees C. On the other hand, a host analogue 2, a tetramethoxy derivative of 1, barely included these guest molecules. The inclusion amount and the rate of inclusion of ethyl acetate or methyl ethyl ketone showed a drastic increase above a threshold concentration of guests in the gas phase. Thus, the structure of the apohost changed cooperatively in order to bind guest molecules above the threshold guest concentration. This cooperativity of the binding behavior was kinetically analyzed.