Combining renewable gum rosin and lignin: Towards hydrophobic polymer composites by controlled polymerization

Rosin polymer–grafted lignin composites were prepared via “grafting from” atom transfer radical polymerization (ATRP) with the aid of 2‐bromoisobutyryl ester‐modified lignin as macroinitiators. Three different monomers derived from dehydroabietic acid (DA) were used for execution of grafting from ATRP, while DA was separately attached onto lignin by a simple esterification reaction. Kinetic studies indicated controlled and “living” characteristics of all monomer polymerizations. Thermal studies indicated that rosin polymer–grafted lignin composites exhibited glass transition temperatures in a broad temperature range from ～20 to 100°C. The grafting of both DA and rosin polymers significantly enhanced hydrophobicity of lignin. Static contact angle measurement of water droplets showed ～90° for all these rosin modified lignin composites. X‐ray photoelectron spectroscopy demonstrated that the surface of rosin–lignin composites was dominated with chemical compositions originating from the hydrocarbon rich rosin moiety. The impartation of hydrophobicity of rosin into lignin provided excellent water resistance of this class of renewable polymers, as all rosin‐modified lignin composites showed water uptake below 1.0 wt %. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Novel perfluorocyclobutyl aryl ether‐based well‐defined amphiphilic block copolymer

A series of fluorine‐containing amphiphilic diblock copolymers comprising hydrophobic poly(p‐(2‐(p‐tolyloxy)perfluorocyclobutoxy)phenyl methacrylate) (PTPFCBPMA) and hydrophilic poly(2‐(diethylamino)ethyl methacrylate) (PDEAEMA) segments were synthesized via successive reversible addition fragmentation chain transfer (RAFT) polymerizations. RAFT homopolymerization of p‐(2‐(p‐tolyloxy)perfluorocyclobutoxy)phenyl methacrylate was first initiated by 2,2′‐azobisisobutyronitrile using cumyl dithiobenzoate as chain transfer agent, and the results show that the procedure was conducted in a controlled way as confirmed by the fact that the number‐average molecular weights increased linearly with the conversions of the monomer while the polydispersity indices kept below 1.30. Dithiobenzoate‐capped PTPFCHPMA homopolymer was then used as macro‐RAFT agent to mediate RAFT polymerization of 2‐(diethylamino)ethyl methacrylate, which afforded PTPFCBPMA‐b‐PDEAEMA amphiphilic diblock copolymers with different block lengths and narrow molecular weight distributions (M_w/M_n ≤ 1.28). The critical micelle concentrations of the obtained amphiphilic diblock copolymers were determined by fluorescence spectroscopy technique using N‐phenyl‐1‐naphthylamine as probe. The morphology and size of the formed micelles were investigated by transmission electron microscopy and dynamic light scattering, respectively. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Palladium(II)-catalyzed oxidative Heck coupling of thiazole-4-carboxylates

Oxidative Heck coupling of thiazole-4-carboxylates via palladium(II)-catalyzed C-H bond activation has been achieved in moderate to good yields. No ligand, and no acidic additive were used in the reaction. The results showed that this protocol tolerated a series of substitutions on the thiazole ring. A preliminary attempt of direct arylation with p-xylene via Pd(II)-catalyzed C-H bond activation has also been done.     

Peptide dendrimer-crosslinked inorganic-organic hybrid supramolecular hydrogel for efficient anti-biofouling

A novel kind of inorganic-organic hybrid supramolecular hydrogel with excellent anti-biofouling capability was developed. The hydrogel was formed via ionic interaction between the negative-charged sodium polyacrylate (SPA) entwined clay nanosheets (CNS) and positive-charged polyhedral oligomeric silsesquioxane (POSS) core-based generation one (L-Arginine) dendrimer (POSS-R).     

Finite-time lag synchronization of coupled reaction–diffusion systems with time-varying delay via periodically intermittent control

In this paper, the issue of finite-time lag synchronization of coupled reaction–diffusion systems with time-varying delay (CRDSTD) is considered. A periodically intermittent controller is designed such that drive system and corresponding response system can achieve finite-time lag synchronization. By using graph theory and Lyapunov method, two sufficient criteria are presented to guarantee the finite-time lag synchronization of CRDSTD. Moreover, the time of achieving lag synchronization of CRDSTD is estimated. Finally, a numerical example is given to show the effectiveness of the proposed results.     

A 4-Methylumbelliferone-based Fluorescent Probe for Sodium New Houttuyfonate

A new fluorogenic probe for sodium new houttuyfonate (SNH) was proposed. 4‐Methylumbelliferyl‐2,4‐dinitrobenzenesulfonate (4‐MUDNBS) was a nonfluorescent compound and was synthesized via the one‐step reaction of 4‐methylumbelliferone (4‐MU) with 2,4‐dinitrobenzenesulfonyl chloride. In basic media, SNH was decomposed to produce sodium sulfite, which then reacted with 4‐MUDNBS to yield highly fluorescent 4‐MU, hence leading to the fluorescence increase of the reaction solution. A linear correlation existed between the emission intensity and the concentration of SNH within the range from 0.5 to 15 μg·mL⁻¹ with a detection limit of 0.15 μg· mL⁻¹ (3δ). The effect of substituents on the benzenesulfonyl moiety of the probe is discussed, and the presence of electronegative groups is favorable for the proposed cleavage reaction.     

Electrogenerated chemiluminescence of poly[(2,2′-bipyridyl)(4-(2-pyrrol-1-ylethyl)-4′-methyl-2,2′-bipyridyl)2]ruthenium (II) film

Elelctrogenerated chemiluminescence (ECL) of electropolymerized films based on [(2,2′-bipyridyl)(4-(2-pyrrol-1-ylethyl)-4′-methyl-2,2′-bipyridyl)₂]ruthenium (II) was firstly investigated in both organic and aqueous solution. The ECL behaviors have been explained by two typical mechanisms, namely, redox-cycling type and oxidative-reduction type. For the former, no co-reactant was required and for the latter, tripropylamine (TPA) and (NH₄)₂C₂O₄ were selected as co-reactants in the organic and aqueous system, respectively.     

Photopromoted carbonylation of 1-bromo-6-chlorohexane under ambient conditions

Photopromoted carbonylation of 1-bromo-6-chlorohexane with CO catalyzed by CuBr2 and CdI2 has been carried out under ambient conditions. The results indicate that the carbonylation proceeds with the major product of chloroester ClCH2（CH2）5COOCH3 under catalysis of CuBr2. Furthermore, the activity of the carbonylation can be improved by addition of basic additives （NaOAc, Na3PO4 or （n-C4H9）3N）. Among these additives, （n-C4H9）3N is the most efficient in terms of the yield of ClCH2（CH2）5COOCH3. However, the methoxycarbonyl substituting chlorine product of BrCH2（CH2）5COOCH3 is not obtained in the presence of CdI2. This is quite different from the carbonylation of monochloroalkane.