Role of precursors and coating polymers in sol–gel chemistry toward enhanced selectivity and efficiency in solid phase microextraction

To evaluate the selectivity and efficiency of solid phase microextraction (SPME) fiber coatings, synthesized by sol–gel technology, roles of precursors and coating polymers were extensively investigated. An on-line combination of capillary microextraction (CME) technique and high performance liquid chromatography (HPLC) was set up to perform the investigation. Ten different fiber coatings were synthesized in which five of them contained only the precursor and the rests were prepared using both the precursor and coating polymer. All the coatings were chemically bonded to the inner surface of copper tubes, intended to be used as the CME device and already functionalized by self-assembly monolayers of 3-(mercaptopropyl)trimethoxysilane (3MPTMOS). The selected precursors included tetramethoxysilane (TMOS), 3-(trimethoxysilyl)propylmethacrylate (TMSPMA), 3-(triethoxysilyl)-propylamine (TMSPA), 3MPTMOS, [3-(2,3-epoxypropoxy)-propyl]-trimethoxysilane (EPPTMOS) while poly(ethyleneglycol) (PEG) was chosen as the coating polymer. The effects of different precursors on the extraction efficiency and selectivity, was studied by selecting a list of compounds ranging from non-polar to polar ones, i.e. polycyclic aromatic hydrocarbon, herbicides, estrogens and triazines. The results from CME–HPLC analysis revealed that there is no significant difference between precursors, except TMOS, in which has the lowest extraction efficiency. Most of the selected precursors have rather similar interactions toward the selected analytes which include Van der Walls, dipole–dipole and hydrogen bond while TMOS has only dipole–dipole interaction and therefore the least efficiency. TMOS is silica but the other sorbents are organically modified silica (ORMOSIL). Our investigation revealed that it is rather impossible to prepare a selective coating using conventional sol–gel methodologies. The comparison study performed among the fiber coatings contained only a precursor and those synthesized by a precursor along with coating polymer proved that the extraction efficiency obtained for all coatings are the same. This is an indication that by selecting the appropriate precursor there is no need to use any coating polymer. In overall, a fiber coating in sol–gel process could be synthesize with no coating polymer which leads to faster, easier, cheaper and more controllable synthesis.     

Interactions between β-carboline alkaloids and bovine serum albumin: Investigation by spectroscopic approach

β-Carboline alkaloids are present in medicinal plants such as Peganum harmala L. that have been used as folk medicine in anticancer therapy. BSA¹ is the major soluble protein constituent of the circulatory system, and has many physiological functions including the transport of a variety of compounds. This study is the first attempt to investigate the binding of β-carboline alkaloids to BSA by using a constant protein concentration and varying drug concentrations at pH 7.2. FTIR² and UV–Vis³ spectroscopic methods were used to analyze the binding modes of β-carboline alkaloids, the binding constants and the effects of drug complexation on BSA stability and conformation. Spectroscopic evidence showed that β-carboline alkaloids bind BSA via hydrophobic interaction and van der Waals contacts along with H-bonding with the –NH groups, with overall binding constants of K_{harmine–BSA}=2.04×10⁴ M^?1, K_{tryptoline–BSA}=1.2×10⁴ M^?1, K_{harmaline–BSA}=5.04×10³ M^?1, K_{harmane–BSA}=1.41×10³ M^?1 and K_{harmalol–BSA}=1.01×10³ M^?1, assuming that there is one drug molecule per protein. The BSA secondary structure was altered with a major decrease of α-helix from 64% (free protein) to 59% (BSA–harmane), 56% (BSA–harmaline and BSA–harmine), 55% (BSA–tryptoline), 54% (BSA–harmalol) and β-sheet from 15% (free protein) to 6–8% upon β-carboline alkaloids complexation, inducing a partial protein destabilization.     

On the existence of 3-way k-homogeneous Latin trades

A $\mu$-way Latin trade of volume $s$ is a collection of $\mu$ partial Latin squares $T_1,T_2,\dots ,T_{\mu }$, containing exactly the same $s$ filled cells, such that, if cell $(i,j)$ is filled, it contains a different entry in each of the $\mu$ partial Latin squares, and such that row $i$ in each of the $\mu$ partial Latin squares contains, set-wise, the same symbols, and column $j$ likewise. It is called a $\mu$-way$k$-homogeneous Latin trade if, in each row and each column, $T_r$, for $1\le r\le \mu$, contains exactly $k$ elements, and each element appears in $T_r$ exactly $k$ times. It is also denoted as a $(\mu ,k,m)$ Latin trade, where $m$ is the size of the partial Latin squares.We introduce some general constructions for $\mu$-way $k$-homogeneous Latin trades, and specifically show that, for all $k\le m$, $6\le k\le 13$, and $k=15$, and for all $k\le m$, $k=4,5$ (except for four specific values), a $3$-way $k$-homogeneous Latin trade of volume $km$ exists. We also show that there is no $(3,4,6)$ Latin trade and there is no $(3,4,7)$ Latin trade. Finally, we present general results on the existence of $3$-way $k$-homogeneous Latin trades for some modulo classes of $m$.     

Carbon dioxide detection by boron nitride nanotubes

The effect of gas molecule adsorption is investigated on the density of states of (9,0) zigzag boron nitride nanotube within a random tight-binding Hamiltonian model. The Green function approach and coherent potential approximation have been implemented. The results show that the adsorption of carbon dioxide gas molecules by boron atoms only leads to a donor type semiconductor while the adsorption by nitrogen atoms only leads to an acceptor. Since the gas molecules are adsorbed by both boron and nitrogen atoms, a reduction of the band gap is found. In all cases, increasing the gas concentration causes an increase in the height of the peaks in the band gap. This is due to an increasing charge carrier concentration induced by adsorbed gas molecules.     

Multiple moving cracks in a functionally graded strip

This paper considers several finite moving cracks in a functionally graded material subjected to anti-plane deformation. The distributed dislocation technique is used to carry out stress analysis in a functionally graded strip containing moving cracks under anti-plane loading. The Galilean transformation is employed to express the wave equations in terms of coordinates that are attached to the moving crack. By utilizing the Fourier sine transformation technique the stress fields are obtained for a functionally graded strip containing a screw dislocation. The stress components reveal the familiar Cauchy singularity at the location of dislocation. The solution is employed to derive integral equations for a strip weakened by several moving cracks. Numerical examples are provided to show the effects of material properties, the crack length and the speed of the crack propagating upon the stress intensity factor.     

碱金属封装到氧化锌纳米笼的第一原理研究

利用密度泛函理论研究了碱金属(Li、Na、K、Ru)封装到Zn₁₂O₁₂纳米笼的过程. 在298 K和100 kPa,Li和Na原子的封装在热力学上是有利的, 吉布斯自由能为负值, 分别为约-130.12和-68.43 kJ/mol. 随着封装原子大小的增加,封装过程变得不那么有利,封装K和Rb过程的吉布斯自由是正值. 结果表明,LUMO、费米能级、尤其是HOMO向更高的能量转移,以至于HOMO-LUMO能隙明显变窄. 封装后的碱金属簇的功函数由于费米能级转移到     

B12N12 Nano-cage as Potential Sensor for NO2 Detection

The NO₂ molecule adsorption on B₁₂N₁₂ nano-cage was investigated using density func-tional theory calculations in terms of adsorption energy, HOMO/LUMO energy gap (Eg) changes, charge transfer, structural deformation, etc. Furthermore, some aspects of stability and properties of B₁₂N₁₂ including calculation of binding electronic and Gibbs free energies, density of states, and molecular electrostatic potential surfaces are investigated. Three pos-sible configurations for NO₂ adsorption on the B₁₂N₁₂ nano-cage are energetically found. Interestingly, the results reveals that the Eg of B₁₂N₁₂ cluster is very sensitive to the pres-ence of NO₂ molecules as its value reduces from 6.84 eV in free cluster to 3.23 eV in the most stable configuration of NO₂/cluster complex. This phenomenon dramatically increases the electrical conductivity of the cluster, suggesting that the B₁₂N₁₂ nano-cluster may be potential sensor for NO₂ gaseous molecule detection.     

Analytical solution of multiple moving cracks in functionally graded piezoelectric strip

The dynamic behaviors of several moving cracks in a functionally graded piezoelectric (FGP) strip subjected to anti-plane mechanical loading and in-plane electrical loading are investigated. For the first time, the distributed dislocation technique is used to construct the integral equations for FGP materials, in which the unknown variables are the dislocation densities. With the dislocation densities, the field intensity factors are determined. Moreover, the effects of the speed of the crack propagation on the field intensity factors are studied. Several examples are solved, and the numerical results for the stress intensity factor and the electric displacement intensity factor are presented graphically finally.     

Design and Application of a Non‐enzymatic Sensor Based on Metal‐organic Frameworks for the Simultaneous Determination of Carbofuran and Carbaryl in Fruits and Vegetables

A novel, stable and sensitive non‐enzymatic sensor was developed with metal‐organic frameworks (MOFs) that have attracted great attention in electrochemical sensors applications in recent years. The pore structures of MIL (Fe)‐101 and MIL (Fe)‐53 are the families of MOFs that were constructed via a simple solvothermal procedure. The 35MIL‐101(Fe)‐reduced graphene oxide nanocomposite has been used for modification of glassy carbon electrode for the determination of carbofuran (CBF) and carbaryl (CBR). The porosity of the composites increased the voltammetric responses significantly for CBF and CBR in a mixed solution that makes the simultaneous determination of both carbamate pesticides possible. Characterization of MIL (Fe)‐101 and MIL (Fe)‐53 were performed with FT‐IR, XRD, BET and SEM. Finally, the introduced sensor under the optimal conditions showed low detection limits of 1.2 and 0.5 nM within the linear ranges of 5.0–200.0 nM and 1.0–300.0 nM for CBF and CBR, respectively. The non‐enzymatic sensor was successfully used to monitoring of carbamates residue in vegetable and fruit samples.