Surface characterization of TEMPO‐oxidized bacterial cellulose

In this study, we focused on the surface character of bacterial cellulose (BC) before and after oxidation mediated by 2,2,6,6‐tetramethylpiperidine‐1‐oxyl (TEMPO).Solid‐state ¹³C NMR, XPS, SEM, contact angle and surface free energy analyses were performed to investigate the effects of various parameters (reaction time and oxidant and catalyst concentrations) on the surface composition, morphology and polarity of the BC. The results provided by the combined use of these techniques showed that hydrogen bonds were disrupted on the BC surface after carboxylation occurred; therefore, the surface of oxidized BC was rougher than that of the original BC, and the surface free energy, especially the polar components, increased after oxidation. Copyright © 2013 John Wiley & Sons, Ltd.     

Conductivity as a Sensor for Monitoring Relative Magnesium Corrosion Rates in Real‐time,in Serum‐containing Media under Cell Culture Conditions

Because controlling the corrosion rate of magnesium metal will be crucial to the success of biomedical implants containing pure magnesium or magnesium alloys, many ways have been sought to improve in vitro tests to analyze corrosion rates, and also to identify new methods of preparing or post‐processing magnesium. In this work, for an in vitro assay, we explored the use of a commercially available conductivity sensor to study magnesium corrosion under cell culture conditions that duplicate many physiologically appropriate parameters. With this sensor, we studied the corrosion of two previously untested magnesium single crystal samples that differed in surface treatments that could alter corrosion rates. The results show that the relative conductivity changes in (mS/cm) over the total time of immersion were proportional to the corrosion rates in (mm/y) and also to the total magnesium released, as detected by inductively coupled plasma mass spectrometry (ICP‐MS).     

Attapulgite grafted with polystyrene via a simultaneous reverse and normal initiation atom transfer radical polymerization

The surface grafting of attapulgite (ATP) with polystyrene (PS) was established via a simultaneous reverse and normal initiation atom transfer radical polymerization (SR&NIATRP). 4‐(chloromethyl)phenyltrimethoxysilane (CMPTMS) chemical bounded on the surface of ATP (ATP‐Cl, Cl‐I) was prepared via one‐step self‐assembly. SR&NI ATRP of styrene was conducted using CuCl₂ complex tris(2‐(dimethylamino)ethyl)amine (Me₆‐TREN) as the catalytic system, initiated by 2,2‐azobis(isobutyronitrile) (AIBN) and ATP‐Cl. FT‐IR, XRD, XPS, TGA and TEM data were consistent with the grafting of benzyl chloride groups and PS chains on ATP surface. The controllability of polymerization was investigated by the kinetics behavior under different molar ratio of AIBN and CuCl₂. The obtained polymer possessed a uniform distribution of molecular weights with a lower polydispersity index of 1.2～1.4. The relationship between polymerization on the surface of ATP and in solution was discussed in detail based on TGA data of hybrid particles and GPC trace of free polymer in solution. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1508–1516     

Late-Stage Direct o-Alkenylation of Phenols by PdII-Catalyzed C−H Functionalization

o-Alkenylation of unprotected phenols has been developed by direct C−H functionalization catalyzed by Pd^II. This work features phenol group as a directing group and realizes highly site-selective C−H bond functionalization of phenols to achieve the corresponding products in moderate to excellent yields at 60 °C. The advantages of this reaction include unprecedented C−H functionalization using phenol as a directing group, high regioselectivity, good substrate scope, mild reaction conditions, and high efficiency. To the best of our knowledge, this is the first example of a regioselective C−H alkenylation of unprotected phenols utilizing phenolic hydroxyl group as a directing group. The alkenylation of unprotected tyrosine and intramolecular cyclization are also successfully carried out under this catalytic system in good yields. Furthermore, this novel method enables a late-stage modification of complex phenol-containing bioactive molecules toward a diversity-oriented drug discovery.     

Modifying LnHPDO3A Chelates for Improved T1 and CEST MRI Applications

The new ligand HPDO3MA [(R,R,R,R)-10-(2-hydroxypropyl)-α,α′,α′′-trimethyl-1,4,7,10-tetraazacyclododecane-1,4,7-triacetic acid] was designed to combine and optimize the chemical properties of the macrocyclic ligands HPDO3A and DOTMA. The presence of the methyl groups on the acetic pendant arms of HPDO3A is expected to rigidify the structure of the ligand and favor an increase of the kinetic inertness of the Ln complexes. ¹H NMR spectra of Eu(HPDO3MA) displayed the presence of two pairs of diastereoisomers: SAP (square antiprismatic) and TSAP (twisted square antiprismatic) isomers (56 and 44 %, respectively). In addition, ¹H and ¹⁷O relaxometric NMR studies of Gd(HPDO3MA) showed approximately a 10 % increase in relaxivity and a faster water exchange rate with respect to Gd(HPDO3A). Moreover, a detailed chemical exchange saturation transfer (CEST) characterization of Yb(HPDO3MA) displayed a sensitivity about two times larger than that of Yb(HPDO3A) both in phantom and in cell labeling experiments. Finally, the kinetic inertness of Yb(HPDO3MA) was measured to be twice as high as that of Yb(HPDO3A), with a dissociation half-life at physiological pH of about 2500 years.     

Effect of gemini surfactant additives on pour point depressant of crude oil

Efficiencies of cationic gemini surfactant additives in improving the pour point depressant of crude oil were investigated. The length of alkyl chain is a major factor affecting the improvement of the pour point depression. The adsorption behavior of these gemini surfactants at air/solution and oil/solution interfaces were investigated by measuring the surface tension and interfacial tension as functions of concentration. It is found that there is a good relation between surface properties especially interfacial tension of the gemini surfactants and their efficiency in depressing the pour point. Also, the surface parameters and free energies of micellization and adsorption confirm the decreasing and improving of pour point depression. Crystallization study in crude oil revealed the relationship between the structure and activity of gemini surfactant additives. It is found that the x-ray diffraction patterns of waxes with additives are remarkably different from those without additives. The mechanism of the depressants action has been suggested according the adsorption of each additive. Adsorption of the additive on the surface of the wax particles inhibits their growth and alters the crystal habits through micelle core. Pretreatment of the crude oil with pour point depressants has received the greatest acceptance due to its simplicity and economy.     

Importance of verifying queue model assumptions before planning with simulation software

This case study uses empirical data gathered at an Australian refinery to verify the assumptions for queue distributions before using special-purpose software to plan the off-road-truck hauling of titanium dioxide to a refinery (n = 773). Easy-to-use spreadsheet software is utilized to verify assumptions for queue models. Managers are able to make decisions based on economic implications of queue models to avoid making costly planning mistakes. Analysts can use nonparametric hypothesis-testing techniques to verify distribution assumptions for optimization without having to write hard-to-maintain and complex algebraic linear equations or nonlinear search routines.     

含酮基团对煤焦异相还原NO的影响

基于量子化学密度泛函理论和过渡态理论研究了含酮基团对煤焦异相还原NO的影响及其产物发生氧脱附的微观反应机理。计算结果表明，NO更易于吸附在含酮基团煤焦表面。椅形含酮基团强化了煤焦异相还原NO；锯齿形含酮煤焦表面与NO异相反应决速步能垒值（495.45 kJ/mol）大于锯齿形纯碳基煤焦表面与NO决速步能垒值（331.32 kJ/mol），基于锯齿形含酮煤焦模型中的氧浓度不在利于NO还原的范围内而不易于NO的还原。中间产物P1在无CO存在情况下，较纯碳基煤焦表面更易于发生氧脱附而产生表面缺陷；在CO存在条件下，含酮煤焦表面为氧脱附过程提供自由活性位点，降低了过程能垒消耗。