科研成果向教学实验的转化设计与实践成效*

围绕学校高水平应用型人才培养目标,依托省级重点实验室与省级化学化工大学生创新训练中心等科研教学平台,将“零排放型化学镀镍及其废液资源化为掺杂型LiFePO₄/C复合材料”的科研成果进行拆解和提炼,设计为分阶段、多层次的10个教学实验项目,并予以实践。结果表明,该科教融合模式营造出良好的科研氛围,有利于学生科研素养与创新意识的培养、实践能力与创新能力的提升。     

Coordinating Ability of Anions,Solvents, Amino Acids,and Gases towards Alkaline and Alkaline-Earth Elements,Transition Metals,and Lanthanides

After briefly reviewing the applications of the coordination ability indices proposed earlier for anions and solvents toward transition metals and lanthanides, a new analysis of crystal structures is applied now to a much larger number of coordinating species: anions (including those that are present in ionic solvents), solvents, amino acids, gases, and a sample of neutral ligands. The coordinating ability towards s-block elements is now also considered. The effect of several factors on the coordinating ability will be discussed: (a) the charge of an anion, (b) the chelating nature of anions and solvents, (c) the degree of protonation of oxo-anions, carboxylates and amino carboxylates, and (d) the substitution of hydrogen atoms by methyl groups in NH₃, ethylenediamine, benzene, ethylene, pyridine and aldehydes. Hit parades of solvents and anions most commonly used in the areas of transition metal, s-block and lanthanide chemistry are deduced from the statistics of their presence in crystal structures.     

Radiation exposure to operator and patients during cardiac electrophysiology study,radiofrequency catheter ablation and cardiac device implantation procedures

The purpose of this study was to measure the radiation exposure to operator and patient during cardiac electrophysiology study, radiofrequency catheter ablation and cardiac device implantation procedures and to calculate the allowable number of cases per year. We carried out 9 electrophysiology studies, 40 radiofrequency catheter ablation and 11 cardiac device implantation procedures. To measure occupational radiation dose and dose–area product (DAP), 13 photoluminescence glass dosimeters were placed at eyes (inside and outside lead glass), thyroids (inside and outside thyroid collar), chest (inside and outside lead apron), wrists, genital of the operator (inside lead apron), and 6 of photoluminescence glass dosimeters were placed at eyes, thyroids, chest and genital of the patient. Exposure time and DAP values were 11.7?±?11.8?min and 23.2?±?26.2?Gy?cm² for electrophysiology study; 36.5?±?42.1?min and 822.4?±?125.5?Gy?cm² for radiofrequency catheter ablation; 16.2?±?9.3?min and 27.8?±?16.5?Gy?cm² for cardiac device implantation procedure, prospectively. 4591 electrophysiology studies can be conducted within the occupational exposure limit for the eyes (150?mSv), and 658-electrophysiology studies with radiofrequency catheter ablation can be carried out within the occupational exposure limit for the hands (500?mSv). 1654 cardiac device implantation procedure can be conducted within the occupational exposure limit for the eyes (150?mSv). The amounts of the operator and patient's radiation exposure were comparatively small. So, electrophysiology study, radio frequency catheter ablation and cardiac device implantation procedures are safe when performed with modern equipment and optimized protective radiation protect equipment.     

How the Physicochemical Properties of the Bulk Material Affect the Ablation Crater Profile,Mass Balance,and Bubble Dynamics During Single-Pulse,Nanosecond Laser Ablation in Water

Understanding the key steps that drive the laser-based synthesis of colloids is a prerequisite for learning how to optimize the ablation process in terms of nanoparticle output and functional design of the nanomaterials. Even though many studies focus on cavitation bubble formation using single-pulse ablation conditions, the ablation efficiency and nanoparticle properties are typically investigated under prolonged ablation conditions with repetition rate lasers. Linking single-pulse and multiple-pulse ablation is difficult due to limitations induced by gas formation cross-effects, which occur on longer timescales and depend on the target materials’ oxidation-sensitivity. Therefore, this study investigates the ablation and cavitation bubble dynamics under nanosecond, single laser pulse conditions for six different bulk materials (Au, Ag, Cu, Fe, Ti, and Al). Also, the effective threshold fluences, ablation volumes, and penetration depths are quantified for these materials. The thermal and chemical properties of the corresponding bulk materials not only favor the formation of larger spot sizes but also lead to the highest molar ablation efficiencies for low melting materials such as aluminum. Furthermore, the concept of the cavitation bubble growth linked with the oxidation sensitivity of the ablated material is discussed. With this, evidence is provided that intensive chemical reactions occurring during the very early timescale of ablation are significantly enhanced by the bubble collapse.     

Investigation of different liquid media and ablation times on pulsed laser ablation synthesis of aluminum nanoparticles

Aluminum nanoparticles were synthesized by pulsed laser ablation of Al targets in ethanol, acetone, and ethylene glycol. Transmission Electron Microscope (TEM) and Scanning Electron Microscope (SEM) images, Particle size distribution diagram from Laser Particle Size Analyzer (LPSA), UV-visible absorption spectra, and weight changes of targets were used for the characterization and comparison of products. The experiments demonstrated that ablation efficiency in ethylene glycol is too low, in ethanol is higher, and in acetone is highest. Comparison between ethanol and acetone clarified that acetone medium leads to finer nanoparticles (mean diameter of 30 nm) with narrower size distribution (from 10 to 100 nm). However, thin carbon layer coats some of them, which was not observed in ethanol medium. It was also revealed that higher ablation time resulted in higher ablated mass, but lower ablation rate. Finer nanoparticles, moreover, were synthesized in higher ablation times.     

Synthesis, Characterization and Properties of Novel Star-Shaped π-Conjugated Oligomers with Triphenylamine Core

Four new star‐shaped π‐conjugated oligomers ( TPA‐CZ3 , TPA‐TPA3 , TPA‐PTZ3 and TPA‐BT3 ) with triphenylamine as a core and different electron‐donating ability groups, carbazole, triphenylamine, phenothiazine and bithiophene, as peripheral units have been designed and synthesized via the Heck reaction. These oligomers show good solubility in common organic solvents. Their photophysical, electrochemical, electronic structure and charge transfer properties between these star‐shaped π‐conjugated oligomers and N,N′‐bis(1‐ethylpropyl)‐3,4:9,10‐perylene bis(tetracarboxyl diimide) (EP‐PDI) have been investigated by UV‐vis absorption spectra, photoluminescence (PL) spectra, cyclic voltammetry (CV) measurement, theoretical calculations and fluorescence quenching. The results show that the absorptions and fluorescences of TPA‐CZ3 , TPA‐TPA3 and TPA‐PTZ3 are red shifted with the electron‐donating ability of the peripheral unit increasing from carbazole to triphenylamine and phenothiazine. In addition, although the bithiophene group has a weaker electron‐donating ability than carbazole, triphenylamine and phenothiazine, the absorption and fluorescence of TPA‐BT3 have a red shift than those of TPA‐CZ3 , TPA‐TPA3 and TPA‐PTZ3 because TPA‐BT3 has a longer conjugation length than TPA‐CZ3 , TPA‐TPA3 and TPA‐PTZ3 . The triphenylamine core and the peripheral units can constitute a large conjugated structure. The fluorescence quenching properties indicate that efficient charge transfer can happen between the star‐shaped oligomers and EP‐PDI.     

Low Band Gap Donor‐Acceptor Conjugated Polymer Nanoparticles and their NIR‐mediated Thermal Ablation of Cancer Cells

Low band gap D‐A conjugated PNs consisting of 2‐ethylhexyl cyclopentadithiophene co‐polymerized with 2,1,3‐benzothiadiazole (for nano‐PCPDTBT) or 2,1,3‐benzoselenadiazole (for nano‐PCPDTBSe) have been developed. The PNs are stable in aqueous media and showed no significant toxicity up to 1 mg · mL^?1. Upon exposure to 808 nm light, the PNs generated temperatures above 50 °C. Photothermal ablation studies of the PNs with RKO and HCT116 colorectal cancer cells were performed. At concentrations above 100 µg · mL^?1 for nano‐PCPDTBSe, cell viability was less than 20%, while at concentrations above 62 µg · mL^?1 for nano‐PCPDTBT, cell viability was less than 10%. The results of this work demonstrate that low band gap D‐A conjugated polymers 1) can be formed into nanoparticles that are stable in aqueous media; 2) are non‐toxic until stimulated by IR light and 3) have a high photothermal efficiency.

     

Molecularly imprinted polymers on the surface of silica microspheres via sol‐gel method for the selective extraction of streptomycin in aqueous samples

Streptomycin‐imprinted silica microspheres were prepared by combining a surface molecular‐imprinting technique with the sol‐gel method. A mixture of tetrahydrofuran, ethanol, and water (6:1:1, v/v/v) was selected as dispersing solvent while 3‐aminopropyltriethoxysilane and triethoxyphenylsilane acted as functional monomers, and tetraethyl orthosilicate as a cross‐linker. Characterization of the molecularly imprinted polymers was conducted using scanning electron microscope and dynamic binding experiments. As compared to the nonimprinted polymers, the imprinted polymers exhibited a higher degree of saturated adsorption volume up to 26.3 mg/g, and better selectivity even in an aqueous solution with interfering compounds, including dihydrostreptomycin, neomycin, and tetracycline. The adsorption ability and selectivity were observed to be influenced by the mole ratio of 3‐aminopropyltriethoxysilane and triethoxyphenylsilane. Feasibility of the polymers to be used for actual application was also evaluated with spiked samples, indicating great potential for large‐scale applications. Moreover, the streptomycin‐imprinted polymers can be repeatedly used for 12 cycles without losing original performance, which is beneficial for commercial use.     

Microstructural evolution during oxidative ablation in air for polyacrylonitrile based carbon fibers with different graphite degrees

Polyacrylonitrile‐based carbon fibers with different graphite degrees were oxidative ablated at 500 and 600 °C in air. By Thermal gravimetric (TG), Raman spectroscopy, X‐ray diffraction, and SEM, the mass loss, microstructure, and surface morphology of carbon fibers were investigated. The mass loss of carbon fiber increases linearly with increasing oxidative ablated time under 500 and 600 °C. The carbon fiber with higher graphite degree shows higher oxidative resistance, and the surface roughness increases gradually because of chemical ablation during the whole oxidation. A gloss morphology appears on the surface primarily because of physical denudation for carbon fibers with lower graphite degree and then burn off according to carbon and oxygen reaction. The crystallite size (La) decreases significantly, while interlayer spacing(d₀₀₂) remains nearly unchanged. SEM observation suggests the two kinds of ablation mechanisms for carbon fibers with different graphite degrees indicating that CC band in sp³ hybridization prefers to be attacked by oxygen molecule more than that in sp² hybridization during oxidation ablation in air. Copyright © 2012 John Wiley & Sons, Ltd.