Mn(Ⅲ)-四芳基卟啉与高碘酸四丁基铵催化羧酸的氧化脱羧:金属、取代基和轴向阴离子配体的影响

锰四芳基卟啉与高碘酸四丁基铵(n-Bu4NIO4)和咪唑(ImH)组合,为羧酸氧化脱羧提供了一个有效的催化剂体系.中位含有吸电子基团和/或大体积芳基的中位-四芳基卟啉使金属卟啉的活性降低.咪唑的存在和金属中心的选择对金属卟啉的催化性能起关键性作用,催化体系中的反离子也有重要影响.Mn(TPP)CN/n-Bu4NIO4/ImH体系的催化活性最好.二苯基乙酸的氧化脱羧可能涉及高价的含氧锰物种与反应物间的相互作用,提出了可能的反应机理.     

Visual detection of cancer cells by colorimetric aptasensor based on aggregation of gold nanoparticles induced by DNA hybridization

A simple but highly sensitive colorimetric method was developed to detect cancer cells based on aptamer–cell interaction. Cancer cells were able to capture nucleolin aptamers (AS 1411) through affinity interaction between AS 1411 and nucleolin receptors that are over expressed in cancer cells, The specific binding of AS 1411 to the target cells triggered the removal of aptamers from the solution. Therefore no aptamer remained in the solution to hybridize with complementary ssDNA-AuNP probes as a result the solution color is red. In the absence of target cells or the presence of normal cells, ssDNA-AuNP probes and aptamers were coexisted in solution and the aptamers assembled DNA-AuNPs, produced a purple solution. UV–vis spectrometry demonstrated that this hybridization-based method exhibited selective colorimetric responses to the presence or absence of target cells, which is detectable with naked eye. The linear response for MCF-7 cells in a concentration range from 10 to 10⁵ cells was obtained with a detection limit of 10 cells. The proposed method could be extended to detect other cells and showed potential applications in cancer cell detection and early cancer diagnosis.     

The Effect of Solution pH Value on the Morphology of Ceria–Yttria Co Stabilized Zirconia Particles Prepared Using the Polymerizable Complex Method

Ceria–yttria co stabilized zirconia (CYSZ) was synthesized from solutions through the polymerizable complex method. The only difference in the preparation of the CYSZ samples was the pH of the starting solution, which was set at 1, 7 and 12, respectively. Transmission electron microscopy and scanning electron microscopy analysis revealed that the sample with the pH value of 1 had good homogeneity, low agglomeration, and a quasi-spherical shape with the particle size of 41 nm, while by increasing the pH up to 7 and 12, the particles became more disordered and no more in the range of nano sized materials (≤100 nm). Fourier transform infrared spectroscopy was employed to evaluate the bonding characteristics of the obtained gels at different pH values. thermogravimetric analysis, together with differential thermal analysis, was used to study the differences in the properties of dried gels with temperature. Crystallographic structure of the final product was also studied using X-ray diffraction.     

Amidation and esterification of carboxylic acids with amines and phenols by N,N′-diisopropylcarbodiimide: A new approach for amide and ester bond formation in water

The present study reports the successful synthesis of two important and abundant functional groups "ester and amide" by N,N′-diisopropylcarbodiimide (DIC) in water as a green solvent. A wide range of substrates could be employed with high functional group tolerance. The products were obtained in high yields after short reaction times. This method provides an efficient, economic, simple and very mild protocol for ester and amide bond formation in aqueous media. In addition, this work not only may lead to environmentally benign systems but also will provide a new aspect of organic chemistry in water.     

Application of nanostructure ZnLI2 complex in construction of optical pH sensor

This is for the first time that application of complex nanostructure is reported as pH indicator in PVC matrix. This new optical pH sensor was constructed based on incorporation of ZnLI₂ complex nanostructure in PVC matrix. The synthesized nanostructure ZnLI₂ complex was characterized by SEM and XRD technique. The membrane solution was speared on the glass plate to provide thin film and the membrane surface morphology was investigated via field emission scanning microscope (FE‐SEM) technique. Central composite design (CCD) combined with desirability function (DF) was applied to find the best experimental composition of membrane providing the highest absorbance. These conditions were found in correspondence with 3 mg of pH indicator, 3 mg of ionic additive and 1.5 mg/mg of DBP/PVC weight ratio. Under optimum conditions, the proposed pH sensor has two linear working ranges of 4 ‐ 8 at 393 nm (R² = 0.9897) and 5 ‐ 8 (R² = 0.9982) at 570 nm with response time of 4 min. The pK_a of proposed pH optical sensor was calculated through three methods that found to be 5.63. The present optical sensor shows stability after 2 months without any significant divergence in response properties (less than 5% RSD). Furthermore, current pH optode was exhibited good repeatability (RSD = 1.14%) as well as reproducibility (RSD = 4.06%). No significant variation was observed on sensor response with increasing the ionic strength in the range of 0.0–0.5 M of sodium chloride. All above features indicated that the proposed sensor can be successfully used for detection of pH in solutions with different ionic strength.     

Synthesis of certain 1,2,4-triazole nucleoside derivatives

The syntheses of 3-amino-4-methyl-1-(β-D-ribofuranosyl)-1,2,4-triazolin-5-one ( 8a ) and its 2′-deoxy analog 8b as well as 5-amino-2-methyl-1-(β-D-ribofuranosyl)-1,2,4-triazolin-3-one ( 12 ) have been accomplished. Compounds 8a and 8b were synthesized via glycosylation of 3-bromo-5-nitro-1,2,4-triazole which was followed by replacement in three steps of the 3-bromo function to yield 3-nitro-1-(2,3,5-tri-O-acetyl-β-D-ribofuranosyl)-1,2,4-triazolin-5-one ( 4a ) and its 2′-deoxy analog 4b . Compounds 4a and 4b were methylated at N², hydrogenated and deblocked to give 3-amino-4-methyl-1-(β-D-ribofuranosyl)-1,2,4-triazolin-5-one ( 8a ) and the 2′-deoxy analog 8b . Compound 12 was synthesized by glycosylation of 3-amino-1-methyl-1,2,4-triazolin-5(2H)-one ( 10 ). The structures of 8b and 12 were confirmed by single crystal X-ray diffraction analysis.