Solvent replacement to thermo‐responsive nanoparticles from long‐subchain hyperbranched PSt grafted with PNIPAM for encapsulation

Long‐subchain hyperbranched polystyrene (lsc‐hp PSt) with uniform subchain length was obtained through copper‐catalyzed azide‐alkyne cycloaddition click chemistry from seesaw macromonomer of PSt having one alkynyl group anchored at the chain centre and two azido group attached to both chain ends [alkynyl‐(PSt‐N₃)₂]. After precipitation fraction, different portions of lsc‐hp PSt having narrow overall molecular weight distribution were obtained for further grafting with alkynyl‐capped poly(N‐isopropylacrylamide) (alkynyl‐PNIPAM), which was obtained via single‐electron transfer living radical polymerization of NIPAM with propargyl 2‐bromoisobutyrate as the initiator and grafted onto the peripheral azido groups of lsc‐hp PSt via click chemistry. Thus, amphiphilic lsc‐hp PSt grafted with PNIPAM chains (lsc‐hp PSt‐g‐PNIPAM) was obtained and would have star‐like conformation in tetrahydrofuran (THF). By replacing THF with water, lsc‐hp PSt‐g‐PNIPAM was dissolved at molecular level in aqueous solution due to the hydrophilicity of PNIPAM and exhibited thermal induced shrinkage of PNIPAM arms. The water‐insoluble lsc‐hp PSt would collapse densely and could be served as a reservoir to absorb hydrophobic chemicals in aqueous solution. The influence of overall molecular weight of lsc‐hp PSt on the absorption of pyrene was studied. © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Cerium (IV) ammonium nitrate (CAN)-mediated regioselective synthesis and anticancer activity of 6-substituted 5,8-dimethoxy-1,4-naphthoquinone

6-Substituted 5,8-O-dimethyl-1,4-naphthoquinones (6-DMNQ), the promising anticancer scaffolds, were selectively generated by oxidative demethylation of 2-substituted 1,4,5,8-tetramethoxynaphthalenes with CAN in EtOAc/H₂O in comparatively high yields. An interesting finding was that apart from the reported electron-withdrawing effects of substituents on position 2 of naphthalene ring, regioselective synthesis of 6-DMNQ was largely dependent on the steric effects in CAN-mediated oxidation. The selective cytotoxicities of 6-DMNQ from the in vitro cell-based assays were exhibited between the cancer cells and normal cells. Moreover, most of sulfur-containing 6-DMNQ derivatives displayed better anticancer activities than the corresponding oxygen-containing ones, which could provide an available strategy for the design of 6-DMNQ derivatives as potential anticancer agents.     

An improved exponential transformation for nearly singular boundary element integrals in elasticity problems

This paper presents an improved exponential transformation for nearly singular boundary element integrals in elasticity problems. The new transformation is less sensitive to the position of the projection point compared with the original transformation. In our work, the conventional distance function is modified into a new form in the polar coordinate system. Based on the refined distance function, an improved exponential transformation is proposed in the polar coordinate system. Moreover, to perform integrations on irregular elements, an adaptive integration scheme considering both the element shape and the projection point associated with the improved transformation is proposed. Furthermore, when the projection point is located outside the integration element, another nearest point is introduced to subdivide the integration elements into triangular or quadrilateral patches of fine shapes. Numerical examples are presented to verify the proposed method. Results demonstrate the accuracy and efficiency of our method.     

Cross‐Coupling of Organolithium with Ethers or Aryl Ammonium Salts by C−O or C−N Bond Cleavage

Various aryl‐, alkenyl‐, and/or alkyllithium species reacted smoothly with aryl and/or benzyl ethers with cleavage of the inert C?O bond to afford cross‐coupled products, catalyzed by commercially available [Ni(cod)₂] (cod=1,5‐cyclooctadiene) catalysts with N‐heterocyclic carbene (NHC) ligands. Furthermore, the coupling reaction between the aryllithium compounds and aryl ammonium salts proceeded under mild conditions with C?N bond cleavage in the presence of a [Pd(PPh₃)₂Cl₂] catalyst. These methods enable selective sequential functionalizations of arenes having both C?N and C?O bonds in one pot.     

Investigating the Photostability of Quantum Dots at the Single‐Molecule Level

Quantum dots (QDs) have shown great potential to provide spatial, temporal, and structural information for biological systems. However, blinking, photobleaching, and spectral blueshift are adverse effects on their practical applications in biomedical research. An investigation of the effects of six reducing agents including cysteine (Cys), 1,4‐dithiothreitol (DTT), ethyl gallate (EG), L ‐glutathione (GSH), mercaptoacetic acid (MAA), and thiourea (TU) on the photostability of single QDs was studied. Our experiments demonstrate that both DTT and EG effectively inhibit blinking, photobleaching, and spectral blueshift. GSH molecules block blinking and photobleaching of QDs. The other reagents, Cys, MAA, and TU, only have the ability to counteract blinking. Possible explanations are given on the basis of research evidence. The results suggest possibilities for significant improvements in QDs for biological applications by adjusting the environmental conditions.     

High dielectric constant nickel-doped titanium oxide films prepared by liquid-phase deposition

The electrical characteristics of nickel-doped titanium oxide films prepared by liquid-phase deposition on p-type (100) silicon substrate were investigated. The aqueous solutions of ammonium hexafluorotitanate and boric acid were used as precursors for the growth of titanium oxide films and the dielectric constant is 29. The dielectric constant can be improved to 94 by nickel doping at the thermal annealing at 700 °C in nitrous oxide.