Usefulness of cyclodextrin media for the determination of α-cypermethrin by photochemically induced fluorescence: analytical applications to natural waters

The photochemically induced fluorescence (PIF) spectral properties of α-cypermethrin in organic solvents (hexane, dichloromethane, acetonitrile, ethanol) and in cyclodextrin aqueous solutions (β-CD and 2-hydroxypropyl-β-CD, 2-HP-β-CD) were investigated. The photolysis kinetics of α-cypermethrin were evaluated in the various media. The PIF signal was found to be significantly enhanced in the CD media relative to the organic solvents. The stoichiometry and the formation constants of the α-cypermethrin inclusion complexes formed with the CDs were determined. The analytical performances of the PIF method were improved in the presence of HP-β-CD relative to the other media, and a CD-enhanced PIF analytical method was developed. The limits of detection and limits of quantification ranged, respectively, between 6 and 98 ng/mL and between 24 and 343 ng/mL, depending on the medium. Application to the analysis of tap water and Senegal natural water samples collected close to agricultural areas and spiked with α-cypermethrin yielded satisfactory recoveries going from about 77% to 98%. An interference study of foreign species, including pesticides and inorganic ions likely to be present in natural waters, was also carried out. Figure Photolysis reaction of α-cypermethrin in presence of HP-β-CD     

Pyrolysis mass spectrometry analysis of poly(vinyl acetate), poly(methyl methacrylate) and their blend coalesced from inclusion compounds formed with γ-cyclodextrin

Direct insertion probe pyrolysis mass spectrometry (DIP-MS) analyses of poly(methyl methacrylate) (PMMA), poly(vinyl acetate) (PVAc) and binary PMMA/PVAc guests, coalesced from their inclusion compounds (ICs) formed with host γ-cyclodextrin (γ-CD) through removal of the γ-CD host, have been performed. A slight increase in the thermal stabilities of the coalesced polymers were recorded both by TGA and DIP-MS compared to the corresponding as-received polymers. The DIP-MS observations pointed out that the thermal stability and degradation products of these polymers are affected once they are included inside the IC channels created by the stacked host γ-CDs. DIP-MS observations suggested that the degradation mechanisms for PMMA and PVAc chains in their coalesced blend were significantly altered from those observed in their as-received and solution blended samples. This was attributed to the presence of specific molecular interactions between the intimately mixed PMMA and PVAc chains in their coalesced blend.     

Strain gradient solution for a finite-domain Eshelby-type anti-plane strain inclusion problem

A solution for the finite-domain Eshelby-type inclusion problem of a finite elastic body containing an anti-plane strain inclusion of arbitrary cross-sectional shape prescribed with a uniform eigenstrain and a uniform eigenstrain gradient is derived in a general form using a simplified strain gradient elasticity theory (SSGET). The formulation is facilitated by an extended Betti’s reciprocal theorem and an extended Somigliana’s identity based on the SSGET and suitable for anti-plane strain problems. The disturbed displacement field is obtained in terms of the SSGET-based Green’s function for an infinite anti-plane strain elastic body. The solution reduces to that of the infinite-domain anti-plane strain inclusion problem when the boundary effect is not considered. The problem of a circular cylindrical inclusion embedded concentrically in a finite cylindrical elastic matrix undergoing anti-plane strain deformations is analytically solved by applying the general solution, with the Eshelby tensor and its average over the circular cross section of the inclusion obtained in closed forms. This Eshelby tensor, being dependent on the position, inclusion size, matrix size, and a material length scale parameter, captures the inclusion size and boundary effects, unlike existing ones. It reduces to the classical linear elasticity-based Eshelby tensor for the circular cylindrical inclusion in an infinite matrix if both the strain gradient and boundary effects are suppressed. Numerical results quantitatively show that the inclusion size effect can be quite large when the inclusion is small and that the boundary effect can dominate when the inclusion volume fraction is high. However, the inclusion size effect is diminishing with the increase of the inclusion size, and the boundary effect is vanishing as the inclusion volume fraction becomes sufficiently low.     

Determination of Dioxins in Blood Using Nano-baskets Doped in Emulsion Liquid Membranes

Extraction of dioxins from blood samples was carried out by inclusion-facilitated emulsion liquid membrane process. The novelty of this work is the application of nano-baskets of calixarene and emulsion liquid membranes in the selective and efficient preconcentration of dioxin. For this aim, four derivatives of p-tert-calix[4]arene bearing different sulfonamide moieties were synthesized and their inclusion-extraction parameters were optimized including the calixarene's scaffold and concentration(as the carrier/demulsifier), the diluent type in membrane, the phase and the treat ratio, mixing speed, and initial solute concentration. Determinations were followed by a gas chromatograph and the results reveal that under the optimized operating conditions, the preconcentration of dioxins was improved and the method achieved lower limit of detections(LODs). Under optimal conditions, the figures of merits were determined to be LOD 1.0 pg/L, dynamic range 0.6―112.0 pg/L, RSD 5.5%(n=5), and the maximum enrichment factor and recovery were determined to be 3.3 and 99%, respectively.     

包合作用与质子化程度对聚(N-丙烯酰-N′-丙基哌嗪)浊点的影响

聚（N-丙烯酰-N′-丙基哌嗪）(PAcrNPP) 是一种pH和温度双重响应的均聚物,通过调节PAcrNPP溶液的pH值可以改变其质子化程度,随着质子化程度的增加高分子溶液浊点逐渐升高。我们测试了不同尺寸的环糊精(CD)对PAcrNPP浊点的影响,在相同摩尔浓度时,α-CD对高分子溶液浊点影响最大,而α-CD对浊点几乎没有影响。分别在pH 9.0和pH 7.4时测量了含有不同浓度的α-CD的PAcrNPP水溶液的浊点,不同pH条件下,PAcrNPP水溶液的浊点随α-CD浓度的增大而升高。并根据溶液中不同存在形式的PAcrNPP对浊点的贡献,推导了一个方程,从化学平衡的角度说明了环糊精的包合与质子化程度对浊点的共同影响。     

Inclusion Compounds of the Host 9-(4-Methylphenyl)-9<Emphasis Type="Italic">H</Emphasis>-xanthen-9-ol with a Series of Organic Guests

Abstract  The host 9-(4-methylphenyl)-9H-xanthen-9-ol (H) forms inclusion compounds with the guests cyclohexane (H · ?CHEX), benzene (H · ?BENZ), 1,4-dioxane (H · ?DIOX), cyclohexanone (H · CYONE), N,N-dimethylformamide (H · DMF) and N,N-dimethylacetamide (H · DMA). For those guest molecules possessing electron acceptor atoms/functionalities hydrogen bonding with the host is the prominent mode of interaction and presents itself in the form of (Host)–OH···O(Guest) linkages. The cyclohexane and benzene guests however, occupy voids created by neighbouring host molecules which form hydrogen bonded dimers of the form (Host)–OH···O(Host). The structures of the inclusion compounds were investigated and their thermal stabilities determined. Selectivity experiments were also conducted. Graphical Abstract  The host 9-(4-methylphenyl)-9H-xanthen-9-ol (H) forms inclusion compounds with the guests cyclohexane (H · ?CHEX), benzene (H · ?BENZ), 1,4-dioxane (H · ?DIOX), cyclohexanone (H · CYONE), N,N-dimethylformamide (H · DMF) and N,N-dimethylacetamide (H · DMA). Crystal structures and thermal stabilities were determined. The host selectivity was also investigated.      

Contact analysis in the presence of an ellipsoidal inhomogeneity within a half space

Many materials contain inhomogeneities or inclusions that may greatly affect their mechanical properties. Such inhomogeneities are for example encountered in the case of composite materials or materials containing precipitates. This paper presents an analysis of contact pressure and subsurface stress field for contact problems in the presence of anisotropic elastic inhomogeneities of ellipsoidal shape. Accounting for any orientation and material properties of the inhomogeneities are the major novelties of this work. The semi-analytical method proposed to solve the contact problem is based on Eshelby’s formalism and uses 2D and 3D Fast Fourier Transforms to speed up the computation. The time and memory necessary are greatly reduced in comparison with the classical finite element method. The model can be seen as an enrichment technique where the enrichment fields from the heterogeneous solution are superimposed to the homogeneous problem. The definition of complex geometries made by combination of inclusions can easily be achieved. A parametric analysis on the effect of elastic properties and geometrical features of the inhomogeneity (size, depth and orientation) is proposed. The model allows to obtain the contact pressure distribution – disturbed by the presence of inhomogeneities – as well as subsurface and matrix/inhomogeneity interface stresses. It is shown that the presence of an inclusion below the contact surface affects significantly the contact pressure and subsurfaces stress distributions when located at a depth lower than 0.7 times the contact radius. The anisotropy directions and material data are also key elements that strongly affect the elastic contact solution. In the case of normal contact between a spherical indenter and an elastic half space containing a single inhomogeneity whose center is located straight below the contact center, the normal stress at the inhomogeneity/matrix interface is mostly compressive. Finally when the axes of the ellipsoidal inclusion do not coincide with the contact problem axes, the pressure distribution is not symmetrical.     

β-Cyclodextrin as a mimetic of the natural GFP-chromophore environment

The green fluorescent protein (GFP) chromophore has been anchored to β-cyclodextrin (βCD) via a copper(I)-catalyzed azide-alkyne cycloaddition. The photophysical properties of this new GFP-CD derivative have been evaluated, showing the formation of a self-inclusion complex and enhancement of fluorescence of the GFP-chromophore covalently bound to the βCD. This enhancement of fluorescence by encapsulation and hence fixation of the chromophore in a binding pocket mimics the effect exerted by the natural protein environment.     

七、八元瓜环对盐酸雷尼替丁的包合作用及缓释性能

研究了七元瓜环(Q[7])和八元瓜环(Q[8])与盐酸雷尼替丁(RH)的包合作用及包合物的体外药物缓释性能.采用紫外-可见光谱法测定了体系的包合比、包合稳定常数和药物累积释放度;用1H NMR技术考察了体系主-客体的包合作用.结果表明,Q[7]和Q[8]与RH在酸性及中性条件下均能发生1∶1包合作用,包合稳定常数分别为1.21×104和2.06×104 L/mol;在碱性条件下则不发生包合作用.原药RH,Q[7]-RH及Q[8]-RH包合物在人工胃液(pH=1.2)中的60 min累积释放度分别为89.1%,56.6%和38.4%;而在人工肠液(pH=6.8)中三者的60 min累积释放度分别为90.2%,58.7%和38.0%.实验结果表明,Q[7]及Q[8]包合对RH有明显的体外缓释作用.     

基于区间数度量的区间值模糊集合的归一化距离、相似度、模糊度和包含度的关系研究

区间值模糊集合的距离、相似度、模糊度和包含度及其关系研究是区间值模糊集合的一个研究热点.考虑到区间值模糊集合所表示信息的丰富性,本文使用区间数而非实数来刻画区间值模糊集合的距离,首先给出基于区间数度量的区间值模糊集合的归一化距离的公理化定义,然后通过五个定理详细研究了基于公理化定义的区间值模糊集合的归一化距离、相似度、模糊度和包含度之间的相互转换关系,最后,给出了若干公式来计算基于区间数度量的区间值模糊集合的相似度、模糊度和包含度.这些结论,一方面丰富了区间值模糊集合的信息测度(距离、相似度、模糊度和包含度)的内容,另一方面也为区间值模糊集合的近似推理、决策分析、模式识别等领域的应用提供了新方法和新理论.