Synthesis of gradient copolymers with simultaneously tailor‐made chain composition distribution and glass transition temperature by semibatch ATRP: From modeling to application

Recent studies have demonstrated that gradient copolymers exhibit unique thermal properties. Although these properties can be determined by copolymer composition, other factors such as chain and sequence lengths and their distributions can also influence them. Accordingly, the synthesis of gradient copolymers requires simultaneously tailor‐made chain structure and thermal properties. In this work, we carried out a systematic study on the preparation of poly(methyl methacrylate‐grad‐2‐hydroxyethyl methacrylate) [poly(MMA‐grad‐HEMA)] with synchronously tailor‐made chain composition distribution and glass transition temperature (T_g) through semibatch atom transfer radical polymerization. First, a comprehensive model for simultaneously predicting gradient copolymer microstructure and T_g was presented using the concept of pseudo‐kinetic rate coefficients and Johnston equation. The model was validated by comparing simulation results with the classical reference data. Furthermore, the model was used to guide the experimental synthesis of the poly(MMA‐grad‐HEMA) gradient copolymers potentially as excellent damping material. The thermal properties of these gradient copolymer samples were evaluated. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Mapping site‐specific protein N‐glycosylations through liquid chromatography/mass spectrometry and targeted tandem mass spectrometry

Glycosylation is one of the most common posttranslational modifications (PTMs) of proteins, the characterization of which is commonly achieved through proteomic protocol, involving trypsin digestion followed by liquid chromatography/tandem mass spectrometry (LC/MS/MS). However, it is often not possible to characterize all glycopeptides in a complex sample because of the high complexity of glycoproteomic samples, and the relative lower abundances of glycopeptides in comparison to the unmodified peptides. We present here a targeted MS/MS analysis approach, which utilizes a previously developed computational tool, GlyPID, to guide multiple experiments, thus permitting a complete characterization of all N‐glycosylation sites of glycoproteins present in a complex sample. We have tested our approach using model glycoproteins analyzed by high‐resolution LTQ‐FT MS. The results demonstrate a potential use of our method for a high‐throughput characterization of complex mixtures of glycosylated proteins. Copyright © 2010 John Wiley & Sons, Ltd.     

Diels–Alder dimerization of Morita–Baylis–Hillman acetates catalyzed by organocatalysts

DABCO-catalyzed dimerization of Morita–Baylis–Hillman acetates to synthesize a series of 3-alkyl-4-(E)-alkenyl-cyclohex-1-ene-1,4-dicarbonyl compounds in excellent yields with modest to excellent diastereoselectivity is reported. A plausible reaction mechanism is also proposed on the basis of previous literature and preliminary investigation the asymmetric version of the reaction.     

Existence of solutions for the p-Laplacian with critical Sobolev exponent and convection

In this article, we study the existence of solutions for the p-Laplacian involving critical Sobolev exponent and convection based on the theory of the Leray–Schauder degree for non-compact mappings.     

Aligned and molecularly oriented semihollow ultrafine polymer fiber yarns by a facile method

In this work, aligned and molecularly oriented bone‐like PLLA semihollow fiber yarns were manufactured continuously from an optimized homogeneous polymer‐solvent‐nonsolvent system [PLLA, CH₂Cl₂, and dimethyl formamide (DMF)] by a single capillary electrospinning via self‐bundling technique. Here, it should be emphasized that the self‐bundling electrospinning technique, a very facile electrospinning technique with a grounded needle (which is to induce the self‐bundling of polymer nanofibers at the beginning of electrospinning process), is used for the alignment and molecular orientation of the polymer fiber, and the take‐up speed of the rotating drum for the electrospun fiber yarn collection is very low (0.5 m/s). PLLA can be dissolved in DMF and CH₂Cl₂ mixed solvent with different ratios. By varying the ratios of mixed solvent system, PLLA electrospun semihollow fiber with the porous inner structure and compact shell wall could be formed, the thickness of the shell and the size of inner pores could be adjusted. The results of polarized FTIR and wide angle X‐ray diffraction investigations verified that as‐prepared PLLA semihollow fiber yarns were well‐aligned and molecularly oriented. Both the formation mechanism of semihollow fibers with core‐shell structure and the orientation mechanism of polymer chains within the polymer fibers were all discussed. The as‐prepared self‐bundling electrospun PLLA fiber yarns possessed enhanced mechanical performance compared with the corresponding conventional electrospun PLLA fibrous nonwoven membranes. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1118–1125, 2010     

Stable Anticancer Gold(III)–Porphyrin Complexes: Effects of Porphyrin Structure

In the design of physiologically stable anticancer gold(III) complexes, we have employed strongly chelating porphyrinato ligands to stabilize a gold(III) ion [Chem. Commun. 2003 , 1718; Coord. Chem. Rev. 2009 , 253, 1682]. In this work, a family of gold(III) tetraarylporphyrins with porphyrinato ligands containing different peripheral substituents on the meso‐aryl rings were prepared, and these complexes were used to study the structure–bioactivity relationship. The cytotoxic IC₅₀ values of [Au(Por)]⁺ (Por=porphyrinato ligand), which range from 0.033 to >100 μM , correlate with their lipophilicity and cellular uptake. Some of them induce apoptosis and display preferential cytotoxicity toward cancer cells than to normal noncancerous cells. A new gold(III)–porphyrin with saccharide conjugation [Au(4‐glucosyl‐TPP)]Cl ( 2 a ; H₂(4‐glucosyl‐TPP)=meso‐tetrakis(4‐β‐D ‐glucosylphenyl)porphyrin) exhibits significant cytostatic activity to cancer cells (IC₅₀=1.2–9.0 μM ) without causing cell death and is much less toxic to lung fibroblast cells (IC₅₀>100 μM ). The gold(III)–porphyrin complexes induce S‐phase cell‐cycle arrest of cancer cells as indicated by flow cytometric analysis, suggesting that the anticancer activity may be, in part, due to termination of DNA replication. The gold(III)–porphyrin complexes can bind to DNA in vitro with binding constants in the range of 4.9×10⁵ to 4.1×10⁶ dm³ mol^?1 as determined by absorption titration. Complexes 2 a and [Au(TMPyP)]Cl₅ ( 4 a ; [H₂TMPyP]⁴⁺=meso‐tetrakis(N‐methylpyridinium‐4‐yl)porphyrin) interact with DNA in a manner similar to the DNA intercalator ethidium bromide as revealed by gel mobility shift assays and viscosity measurements. Both of them also inhibited the topoisomerase I induced relaxation of supercoiled DNA. Complex 4 a , a gold(III) derivative of the known G‐quadruplex‐interactive porphyrin [H₂TMPyP]⁴⁺, can similarly inhibit the amplification of a DNA substrate containing G‐quadruplex structures in a polymerase chain reaction stop assay. In contrast to these reported complexes, complex 2 a and the parental gold(III)–porphyrin 1 a do not display a significant inhibitory effect (<10 %) on telomerase. Based on the results of protein expression analysis and computational docking experiments, the anti‐apoptotic bcl‐2 protein is a potential target for those gold(III)–porphyrin complexes with apoptosis‐inducing properties. Complex 2 a also displays prominent anti‐angiogenic properties in vitro. Taken together, the enhanced stabilization of the gold(III) ion and the ease of structural modification render porphyrins an attractive ligand system in the development of physiologically stable gold(III) complexes with anticancer and anti‐angiogenic activities.     

Comments on “A bicriteria flowshop scheduling problem with setup times”

The aim of this paper is to point out that the integer programming model proposed by Eren and Güner [T. Eren, E. Güner, A bicriteria flowshop scheduling problem with setup times, Appl. Math. Comput. 183 (2006) 1292-1300] is incorrect. We propose a new integer programming model for the same scheduling problem based on their model.