Hold that shape: An achiral acetylene underwent helix‐sense‐selective polymerization in chiral micelles consisting of [{(nbd)RhCl}2] (nbd=2,5‐norbornadiene) and dodecylphenylalanine as a chiral emulsifier to produce optically active helical polymers and polymeric emulsions.

This article reports on the first catalytic microemulsion polymerizations of substituted acetylenes in aqueous medium, providing nanoscale particles exhibiting optical activities and consisting of helical polymers. Three types of substituted acetylenessone achiral N-propargylamide, two chiral N-propargylsulfamides, and chiral N-propaygylureaswere polymerized in the presence of hydrophobic Rh-based catalyst and with SDS as emulsifier and DMF as coemulsifier. Such microemulsion polymerizations led to nanoscale particles (70-110 nm in diameter) of polymers adopting helical conformations. The particles derived from the chiral monomers showed large specific rotations and intense circular dichroism (CD) signals. The obtained polymer dispersions demonstrated high stability. The thus-prepared polymers after removing the emulsifier and coemulsifier showed much stronger CD signals, and the helices were found to have higher thermal stability when compared with the corresponding polymers synthesized via catalytic polymerizations in organic solvents. The microemulsion polymerizations enable the polymers to form predominantly one-handed helical structures. The possible mechanisms were proposed for the formation of optically active polymer particles, for the formation of predominantly one-handed helices, and for the increased thermal stability of the helices formed in the polymers.

It can be larger: A facile self-assembly/solvothermal approach to synthesize monodispersed, large-pore (>12 nm) silica nanospheres (LPSNs) with ordered, accessible, and interconnected pore channels has been successfully developed by utilizing an amphiphilic block copolymer (polystyrene-b-poly (acrylic acid), PS-b-PAA) as pore template and cetyltrimethylammonium bromide (CTAB) as structure-stabilizing agent.

This article presents two novel artificial helical polymers, substituted polyacetylenes with urea groups in side chains. Poly(4) and poly(5) can be obtained in high yields (≥97%) and with moderate molecular weights (11,000–14,000). Poly(4) contains chiral centers in side chains, and poly(5) is an achiral polymer. Both of the two polymers adopted helical structures under certain conditions. More interestingly, poly(4) exhibited large specific optical rotations, resulting from the predominant one‐handed screw sense. The helical conformation in poly(5) was stable against heat, while poly(4) underwent conformational transition from helix to random coil upon increasing temperature from 0 to 55 °C. Solvents had considerable influence on the stability of the helical conformation in poly(4). The screw sense adopted by the helices was also largely affected by the nature of the solvent. Poly(4‐co‐5)s formed helical conformation and showed large optical rotations, following the Sergeants and Soldiers rule. By comparing the present two polymers (with one NH groups) with the three polymers previously reported (with two NH groups in side chains), the nature of the hydrogen bonds formed between the neighboring urea groups played big roles in the formation of stable helical conformation. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4112–4121, 2008

Achiral substituted acetylene monomers undergo aqueous catalytic emulsion asymmetric polymerizations in chiral micelles consisting of SDS and amino acid, providing optically active helical polymer emulsions. The asymmetric polymerizations lead to one-handed helical polymers, which are the origin of the optical activity of polymer emulsions.

Poly(N-methyl-4-piperidinyl methacrylate) (PMPMA) was synthesized and characterized. PMPMA formed complexes with poly(p-vinylphenol) (PVPh) in ethanol over the entire feed composition range. The yields of complexes were in the range 29-76%, which were lower than those of poly(4-vinylpyridine) (P4VPy)/PVPh complexes obtained in ethanol. Complexation did not occur in N,Ndimethylformamide (DMF), but the DMF-cast blends were miscible. Fourier-transform infrared spectroscopic studies showed that the hydroxyl groups of PVPh interact with the carbonyl groups of PMPMA, and the intermolecular hydrogen-bonding interactions are weaker than the self-association of PVPh. X-ray photoelectron spectroscopic studies showed that the nitrogen atoms in the piperidine groups are not involved in intermolecular interactions with PVPh, likely a result of steric effects asserted by the N-methyl groups. Because of the inaccessibility of the piperidine nitrogen atoms, PMPMA interacts less intensely with PVPh than P4VPy does.

A novel class of manganese-based dual-mode contrast agents (DMCAs) based on the core-shell structured manganese-loaded dual-mesoporous silica spheres (Mn-DMSSs) for simultaneous T1- and T2-weighted magnetic resonance imaging (MRI) has been successfully reported. The in vitro MR tests demonstrate that the Mn-based DMCAs display an excellent simultaneous T1-weighted and T2-weighted MR imaging effect with a noticeably high T1 relaxivity (r1) of 10.1 mM(-1) s(-1) and a moderately high T2 relaxivity (r2) of 169.7 mM(-1) s(-1). The Mn-based DMCAs exhibit negligible cytotoxicity with >80% cell viability at a concentration of up to 200 μg/mL in human liver carcinoma (HepG2) and mouse macrophage (RAW264.7) cells after 24 h. Confocal laser scanning microscopy (CLSM) results show that the Mn-DMSSs were internalized via endocytosis and located in the cytoplasm but not in the nucleus. The in vivo experiment shows that the signals of rat liver increased by 29% under T1-weighted imaging mode and decreased by 28% under T2-weighted imaging mode in 5 min postinjection of Mn-DMSSs, which reveal that the novel Mn-loaded DMSSs can be used as both positive (T1-weighted) and negative (T2-weighted) MR contrast agents in further biomedical applications.

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