Photoinduced Iron‐Based Water‐Induced Phase Separable Catalysis (WPSC) ICAR ATRP of Poly(ethylene glycol) Methyl Ether Methacrylate

Iron‐mediated atom transfer radical polymerization (ATRP) has gained extensive attention because of the superiority of iron catalysts, such as low toxicity, abundant reserves, and good biocompatibility. Herein, a practical iron catalyst recycling system, photoinduced iron‐based water‐induced phase separable catalysis ATRP with initiators for continuous activator regeneration, at room temperature is developed for the first time. In this polymerization system, the polymerization is conducted in homogenous solvents consisting of p‐xylene and ethanol, using commercially available 5,10,15,20‐tetraphenyl‐21H,23H‐porphine iron(III) chloride as the iron catalyst, ethyl 2‐bromophenylacetate as the ATRP initiator, 2,4,6‐trimethylbenzoyl diphenylphosphine oxide as the photoinitiator, and poly(ethylene glycol) methyl ether methacrylate as the model hydrophilic monomer. After polymerization, a certain amount of water is added to induce the phase separation so that the catalyst can be separated and recycled in p‐xylene phase with very low residual metal complexes (<12 ppm) in the resultant polymers even after six times recycle experiments.

     

Effect of water on the retention on diol and amide columns in hydrophilic interaction liquid chromatography

The amount of water adsorbed on polar columns plays important role in hydrophilic interaction liquid chromatography. It may strongly differ for the individual types of polar columns used in this separation mode. We measured adsorption isotherms of water on an amide and three diol‐bonded stationary phases that differ in the chemistry of the bonded ligands and properties of the silica gel support. We studied the effects of the adsorbed water on the retention of aromatic carboxylic acids, flavonoids, benzoic acid derivatives, nucleic bases, and nucleosides in aqueous‐acetonitrile mobile phases over the full composition range. The graphs of the retention factors versus the volume fraction of water in mobile phase show “U‐profile” characteristic of a dual hydrophilic interaction–reversed phase retention mechanism. The minimum on the graph that marks the changing retention mechanism depends on the amount of adsorbed water. The linear solvation energy relationship model suggests that the retention in the hydrophilic interaction liquid chromatography mode is controlled mainly by proton–donor interactions in the stationary phase, depending on the column type. Finally, the accuracy of hydrophilic interaction liquid chromatography gradient prediction improves for columns that show a high water adsorption.     

Determination of triazine herbicides in juice samples by microwave‐assisted ionic liquid/ionic liquid dispersive liquid–liquid microextraction coupled with high‐performance liquid chromatography

A novel microextraction method, termed microwave‐assisted ionic liquid/ionic liquid dispersive liquid–liquid microextraction, has been developed for the rapid enrichment and analysis of triazine herbicides in fruit juice samples by high‐performance liquid chromatography. Instead of using hazardous organic solvents, two kinds of ionic liquids, a hydrophobic ionic liquid (1‐hexyl‐3‐methylimidazolium hexafluorophosphate) and a hydrophilic ionic liquid (1‐butyl‐3‐methylimidazolium tetrafluoroborate), were used as the extraction solvent and dispersion agent, respectively, in this method. The extraction procedure was induced by the formation of cloudy solution, which was composed of fine drops of 1‐hexyl‐3‐methylimidazolium hexafluorophosphate dispersed entirely into sample solution with the help of 1‐butyl‐3‐methylimidazolium tetrafluoroborate. In addition, an ion‐pairing agent (NH₄PF₆) was introduced to improve recoveries of the ionic liquid phase. Several experimental parameters that might affect the extraction efficiency were investigated. Under the optimum experimental conditions, the linearity for determining the analytes was in the range of 5.00–250.00 μg/L, with the correlation coefficients of 0.9982–0.9997. The practical application of this effective and green method is demonstrated by the successful analysis of triazine herbicides in four juice samples, with satisfactory recoveries (76.7–105.7%) and relative standard deviations (lower than 6.6%). In general, this method is fast, effective, and robust to determine triazine herbicides in juice samples.     

Determination of phospholipids in milk samples by means of hydrophilic interaction liquid chromatography coupled to evaporative light scattering and mass spectrometry detection

The combined use of the state-of-the-art hybrid mass spectrometers together with high efficient liquid chromatography could surely be a useful tool for such a challenging task, as phospholipids (PLs) analysis. In this research, we used hydrophilic interaction liquid chromatography (150 mm×2.1 mm I.D., 2.7 μm d.p. partially porous column) to achieve the separation of major PLs classes in cow's and donkey's milk samples. Solid-phase extraction (SPE) was performed in order to pre-concentrate minor PLs from non polar lipids (triacylglycerols) and the recovery for the extraction method was assayed on a milk sample, fortified with 5 μg/mL of SM pure standard, and analyzed in triplicate. A value of 89.99% was calculated, with a coefficient of variation (CV%) of 1.93. A 70-min long stepwise gradient of water/acetonitrile afforded baseline separation of PLs classes, at 50 μL/min flow rate. Accurate detection by an ion trap-time of flight (IT-TOF) mass spectrometer (in both positive and negative ionization mode) allowed to fully characterize the distinctive phospholipid profile and fatty acid composition of cow's and donkey's milk, the latter being analyzed for the first time. Evaporative light scattering detection was further employed to attain the quantitative evaluation of major PLs classes identified, by the external calibration method using reference material solutions in the 5-200 μg/mL concentration range. Major difference between the two analyzed samples consisted in the total PLs amount, which in cow's milk was determined as over 20-fold higher than the donkey's.     

亲水作用色谱法测定组织中全基因组DNA甲基化水平

建立了亲水作用色谱(HILIC)测定组织中全基因组DNA甲基化水平的方法。采用苯酚-氯仿提取组织中的DNA,提取的DNA用88%甲酸在140 ℃下裂解,经N2吹干后,加乙腈-水(9:1, v/v)溶解,用Waters BEH HILIC柱进行分离,在277 nm波长下检测胞嘧啶(Cyt)及5-甲基胞嘧啶(5-mCyt)含量。结果表明,以乙腈-10 mmol/L甲酸铵溶液(94:6, v/v)为流动相,流速为0.5 mL/min, Cyt与5-mCyt分离较好,保留时间分别为2.6与3.1 min。胞嘧啶的线性范围为1～900 μmol/L,相关系数为0.9999; 5-甲基胞嘧啶的线性范围为1～64 μmol/L,相关系数为0.9998。胞嘧啶和5-甲基胞嘧啶的检出限为54 nmol/L(柱中为0.54 pmol),定量限为250 nmol/L(柱中为2.5 pmol);在5～900 μmol/L的添加水平下,胞嘧啶和5-甲基胞嘧啶的平均加标回收率为94.7%～100.5%,相对标准偏差小于1.48%。用该方法检测了结肠癌组织中DNA甲基化水平,结果显示该癌组织中全基因组的DNA甲基化均值为4.0%。该方法快速、简单,稳定性好,灵敏度较高,能满足全基因组DNA甲基化的检测要求。     

Simultaneous determination of estrogenic and androgenic hormones in water by isotope dilution gas chromatography-tandem mass spectrometry

A rapid gas chromatography-tandem mass spectrometry (GC-MS/MS) analytical method was developed for the simultaneous analysis of 7 estrogenic hormones (17α-estradiol, 17β-estradiol, estrone, mestranol, 17α-ethynylestradiol, levonorgestrel, estriol) and 5 androgenic hormones (testosterone, androsterone, etiocholanolone, dihydrotestosterone, androstenedione) in aqueous matrices. This method is unique in its inclusion of all 12 of these estrogens and androgens and is of particular value due to its very short chromatographic run time of 15 min. The use of isotope dilution for all analytes ensures the accurate quantification, accounting for analytical variabilities that may be introduced during sample processing and instrumental analysis. Direct isotopically labelled analogues were used for 8 of the 12 hormones and satisfactory isotope standards were identified for the remaining 4 hormones. Method detection levels (MDLs) were determined to describe analyte concentrations sufficient to provide a signal with 99% certainty of detection. The established MDLs for most analytes were 1-5 ngL(-1) in a variety of aqueous matrices. However, slightly higher MDLs were observed for etiocholanolone, androstenedione, testosterone, levonorgestrel and dihydrotestosterone in some aqueous matrices. Sample matrices were observed to have only a minor impact on MDLs and the method validation confirmed satisfactory method stability over intra-day and inter-day analyses of surface water and tertiary treated effluent samples.     

Synthesis and characterization of aromatic polyesters with dicyanovinyl substituents

The synthesis, characterization, and structure—property relations of aromatic polyesters with dicyanovinyl substituents is presented. Two comparable series of polyesters based on 3,4-dihydroxybenzylidenemalononitrile and 3,4-dihydroxy-5-methoxybenzylidenemalononitrile were prepared. As aromatic diacid components, terephthalic acid, phenylterephthalic acid, isophthalic acid, and 2-phenylisophthalic acid were used. The polyesters were prepared by solution polycondensation. GPC investigations revealed the existence of substantial amounts of defined cyclic products. These cycles could be isolated by preparative GPC. The polyesters are soluble in common low boiling organic solvents, particularly the phenyl-substituted ones. The polyesters are amorphous and have glass transition temperatures between 140 and 170°C. The absorption maxima are in the 306–322 nm range. The cut-off wavelength is between 400 and 428 nm. The polyesters with methoxy substitutent have generally the absorptions at longer wavelength. The refractive index of thin films of these polyesters were between 1.61 and 1.63 at 632.8 nm. © 1993 John Wiley & Sons, Inc.     

Synthesis,structural analysis,and self-assembly of phenylene ethynylene oligomers and their ?F, ?CF3, and ?CH3 substituted derivatives

Oligomers consisting of aromatic building blocks separated by alkynyl units were synthesized by Sonogashira cross-coupling of aryl halides with terminal acetylenes. Strong electron acceptors such as  F and  CF₃ and weak electron donors like  CH₃ were placed as substituents on one of the benzene rings. Acetyl-protected sulfhydryl groups were attached to one end of these molecules to promote their self-organization on gold surfaces. The electron-transport properties of such self-assembled monolayers (SAMs) are highly sensitive to the local order of the molecules in the solid state. Single crystals were analyzed by X-ray diffraction experiments that revealed structural details that could lead to a better understanding of the electron-transport properties. The unsymmetrical substitution of the aromatic rings by electron-active groups in the ortho-, meta-, or para positions resulted in changes of such molecular parameters as bonding and torsion angles and planarity. These parameters, in turn, can affect the angle of the molecular attachment to a gold substrate and the density of the resulting SAMs. Patterned SAMs of some of these molecules and comparison alkane thiols were obtained on gold by microcontact printing or flooding. The SAM thickness was determined by spectroscopic ellipsometry. Surface potential differences between adjacent SAMs or between SAMs and the gold substrate were measured by scanning surface potential microscopy under ambient conditions. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 541–550, 2004     

Effect of substituent distribution on water solubility of O-methylcellulose

The effect of substituent distribution on the water solubility of O-methylcellulose (MC) was re-examined to elucidate the lower limit of the degree of substitution (DS) in water-soluble MC. To this end, a series of 2,3-MCs which are regioselectively substituted at the C-2 and C-3 hydroxyl groups were prepared by homogeneous methylation. It was found that the lower limit for the DS value of water-soluble 2,3-MC was almost the same as that for MCs having even distributions of substituents along the cellulose chain as well as in the anhydroglucose units. This revised version was published online in August 2006 with corrections to the Cover Date.