Modification of σ‐Donor Properties of Terminal Carbide Ligands Investigated Through Carbide–Iodine Adduct Formation

The terminal carbide ligands in [(Cy₃P)₂X₂Ru≡C] complexes (X=halide or pseudohalide) coordinate molecular iodine, affording charge‐transfer complexes rather than oxidation products. Crystallographic and vibrational spectroscopic data show the perturbations of iodine to vary with the auxiliary ligand sphere on ruthenium, demonstrating the σ‐donor properties of carbide complexes to be tunable.     

Synthesis of Depo‐Medrol–chitosan hydrogel as new drug slow‐release appliance and investigation of release kinetics by high‐performance liquid chromatography

The present study deals with preparation and optimization of a novel chitosan hydrogel‐based matrix by suspension cross‐linking method for controlled release of Depo‐Medrol. The controlled release of Depo‐Medrol for effective Rheumatoid arthritis disease has become an imperative field in the drug delivery system. In this context, it was intended to optimize loading circumstances by experimental design and also study the release kinetics of Depo‐Medrol entrapped in the chitosan matrix in order to obtain maximal efficiency for drug loading. The optimum concentrations of chitosan (2.5 g), glutaraldehyde (3.05 μL) and Depo‐Medrol (0.1 mg) were set up to achieve the highest value of drug loaded and the most sustained release from the chitosan matrix. In vitro monitoring of drug release kinetic using high‐performance liquid chromatography showed that 73% of the Depo‐Medrol was released within 120 min, whereas remained drug was released during the next 67 h. High correlation between first‐order and Higuchi's kinetic models indicates a controlled diffusion of Depo‐Medrol through the surrounding media. Moreover, recovery capacity >82% and entrapment efficiency of 58–88% were achieved under optimal conditions. Therefore, the new synthesized Depo Medrol–chitosan is an applicable appliance for arthritis therapy by slow release mechanism. Copyright © 2016 John Wiley & Sons, Ltd.     

Circular DNA by “Bis‐Click” Ligation: Template‐Independent Intramolecular Circularization of Oligonucleotides with Terminal Alkynyl Groups Utilizing Bifunctional Azides

A highly effective and convenient “bis‐click” strategy was developed for the template‐independent circularization of single‐stranded oligonucleotides by employing copper(I)‐assisted azide–alkyne cycloaddition. Terminal triple bonds were incorporated at both ends of linear oligonucleotides. Alkynylated 7‐deaza‐2′‐deoxyadenosine and 2′‐deoxyuridine residues with different side chains were used in solid‐phase synthesis with phosphoramidite chemistry. The bis‐click ligation of linear 9‐ to 36‐mer oligonucleotides with 1,4‐bis(azidomethyl)benzene afforded circular DNA in a simple and selective way; azido modification of the oligonucleotide was not necessary. Short ethynyl side chains were compatible with the circularization of longer oligonucleotides, whereas octadiynyl residues were used for short 9‐mers. Compared with linear duplexes, circular bis‐click constructs exhibit a significantly increased duplex stability over their linear counterparts. The intramolecular bis‐click ligation protocol is not limited to DNA, but may also be suitable for the construction of other macrocycles, such as circular RNAs, peptides, or polysaccharides.     

Optimization of the process parameters of synthesis of vinblastine imprinted polymer

Molecularly imprinted polymers (MIPs) are tailor-made polymers with high selectivity for the template molecule. This selectivity arises from the synthetic procedure followed to prepare the MIP. In this work, the influence of process parameters on the preparation of vinblastine (VLB) imprinted polymers was presented. In the procedure of polymerization, VLB (0.1 mmol) was used as the template molecule and a commonly used initiator, azobisisobutyronitrile (AIBN), was employed to initiate the reaction at 60 °C. The influence of the following parameters was investigated: the moles of functional monomer (MAA, 0.3-1.0 mmol), the moles of cross-linker (EDMA, 1.5-5.0 mmol) and the porogenic solvent (toluene or acetonitrile). A mathematical method of uniform design was applied to optimize these selected parameters in order to increase the selectivity of MIP for template molecule. The experimental data were analyzed to obtain the regression model and the optimal conditions were achieved by optimization with uniform design software. The MIP was synthesized under the optimal conditions that 1.0 mmol of MAA and 5.0 mmol of EDMA copolymerized in toluene in the presence of 0.1 mmol of VLB. After removal of the template molecule, the obtained MIP was then employed as the sorbents of solid-phase extraction (SPE) to separate VLB from Catharanthus roseus extract. The results showed that the polymer exhibited high affinity to the template molecule and could separate and enrich VLB from C. roseus extract effectively. The recovery of VLB on the optimal MIP was 89.00%, which agreed closely with the predicted recovery. Therefore it is possible to further improve the nature of the polymer by optimizing the polymerization parameters with the method of uniform design.     

Homogeneous liquid-liquid extraction of trace amounts of mononitrotoluenes from waste water samples

Homogeneous liquid-liquid extraction method was studied based on a phase separation phenomenon in a ternary solvent system. According to this procedure, mononitrotoloenes were extracted by single-phase extraction in a water/methanol/chloroform, homogeneous ternary solvent system. Methanol and chloroform were used as consolute and extraction solvents, respectively. The homogeneous solution was broken by the addition of salt and a cloudy solution was formed. After centrifugation, the fine droplets of the extraction solvent were sedimented in the bottom of the conical test tube. Analysis of the extracts was carried out by gas chromatography. The optimization procedure was performed using Box-Behnken design. The variables involved were: sample and extraction solvent volumes, consolute solvent volume and phase separator reagent concentration. Optimum results were obtained under the following conditions: sample volume of 5 mL, extraction solvent volume of 55 μL, consolute solvent volume of 1 mL and phase separator reagent concentration; 5% (w/v). Under these conditions, the enrichment factors of 354, 311 and 300, dynamic linear ranges of 0.5-500, 1-500 and 1-500 μg L⁻¹, and limit of detections (LODs) of 0.09, 0.09 and 0.1 μg L⁻¹ were obtained for o-nitrotoluene, m-nitrotoluene and p-nitrotoluene, respectively. Finally, the method was successfully applied to the extraction and determination of MNTs in the waste water samples in the range of micrograms per liter with R.S.Ds. < 13.2%.     

Optimization of the process variables for the synthesis of cardanol-based novolac-type phenolic resin using response surface methodology

Models capable of predicting the maximum extent of conversion (p) of cardanol-based novolac-type phenolic resin, have been developed using response surface methodology to determine the optimum reaction conditions. Three-dimensional response surface and their contour plot were drawn. The maximum extent of conversion (98.93%) was predicted when the cardanol was condensed with formaldehyde (molar ratio 1:0.652) at 119.84 °C for a time period of 3 h with the catalyst (e.g., citric acid) concentration of 1.988% of total volume of cardanol and formaldehyde. The pH of the reaction mixture was maintained at 3.0. These predicted values for optimum process conditions were in good agreement with experimental data.     

A new multiresponse optimization approach in combination with a D-Optimal experimental design for the determination of biogenic amines in fish by HPLC-FLD

A new strategy to approach multiresponse optimization in conjunction to a D-optimal design for simultaneously optimizing a large number of experimental factors is proposed. The procedure is applied to the determination of biogenic amines (histamine, putrescine, cadaverine, tyramine, tryptamine, 2-phenylethylamine, spermine and spermidine) in swordfish by HPLC-FLD after extraction with an acid and subsequent derivatization with dansyl chloride. Firstly, the extraction from a solid matrix and the derivatization of the extract are optimized. Ten experimental factors involved in both stages are studied, seven of them at two levels and the remaining at three levels; the use of a D-optimal design leads to optimize the ten experimental variables, significantly reducing by a factor of 67 the experimental effort needed but guaranteeing the quality of the estimates. A model with 19 coefficients, which includes those corresponding to the main effects and two possible interactions, is fitted to the peak area of each amine. Then, the validated models are used to predict the response (peak area) of the 3456 experiments of the complete factorial design. The variability among peak areas ranges from 13.5 for 2-phenylethylamine to 122.5 for spermine, which shows, to a certain extent, the high and different effect of the pretreatment on the responses. Then the percentiles are calculated from the peak areas of each amine. As the experimental conditions are in conflict, the optimal solution for the multiresponse optimization is chosen from among those which have all the responses greater than a certain percentile for all the amines. The developed procedure reaches decision limits down to 2.5 μg L⁻¹ for cadaverine or 497 μg L⁻¹ for histamine in solvent and 0.07 mg kg⁻¹ and 14.81 mg kg⁻¹ in fish (probability of false positive equal to 0.05), respectively.     

可观察到氢气燃烧呈淡蓝色火焰的实验设计

现行高中化学教科书中钠与水的反应实验未提供验证反应所产生气体的实验装置。为使学生通过观察实验现象,直观地认识和理解钠与水反应产生的气体是氢气,在已设计"钠与水反应的实验装置"的基础上,从普通玻璃尖嘴导管焰色反应的干扰、煤油蒸气的干扰2个维度进行分析,最终设计出可以观察到氢气燃烧呈淡蓝色火焰的实验。     

有机波谱分析课程绪论部分的教学设计

针对有机波谱分析课程的特点,对绪论部分进行教学设计,使学生认识到有机波谱分析课程的重要性,了解课程讲授的主要内容,掌握学习方法,培养科学素养,为学生以后的学习和提高上课效果奠定基础。     

一体化教学模式在涂料配方设计课程中的应用

介绍了高职背景下涂料配方设计课程的开展过程。采用一体化教学模式,从高职学生的特点入手剖析课程,使用课堂讨论、引发、对比等多种教学方法,使涂料配方设计课程的讲授取得了更好的教学效果。