The demand for petroleum dependent chemicals and materials has been increasing despite the dwindling of their fossil resources. As the dead-end of petroleum based industry has started to appear, today's modern society has to implement alternative energy and valuable chemical resources immediately. Owing to the importance of lignocellulosic biomass for being the most abundant and bio-renewable biomass on earth, this critical review provides insights into the potential of lignocellulosic biomass as an alternative platform to fossil resources. In this context, over 200 value-added compounds, which can be derived from lignocellulosic biomass by using various treatment methods, are presented with their references. Lignocellulosic biomass based polymers and their commercial importance are also reported mainly in the frame of these compounds. The review article aims to draw the map of lignocellulosic biomass derived chemicals and their synthetic polymers, and to reveal the scope of this map in today's modern chemical and polymer industry.

The overwhelming success of click chemistry encouraged researchers to develop alternative "spring-loaded" chemical reactions for use in different fields of chemistry. Initially, the copper(I)-catalyzed azide-alkyne cycloaddition was the only click reaction. In recent years, metal-free [3+2] cycloaddition reactions, Diels-Alder reactions, and thiol-alkene radical addition reactions have come to the fore as click reactions because of their simple synthetic procedures and high yields. Furthermore, these metal-free reactions have wide applicability and are physiologically compatible. These and other alternative click reactions expand the opportunities for synthesizing small organic compounds as well as tailor-made macromolecules and bioconjugates. This Minireview discusses the success and applicability of new, in particular metal-free, click reactions.

Smart materials with the ability to repair themselves have been the focus of different fields of science and engineering. This mini-review provides an insight into the rapidly expanding area of research into smart materials with self-healing properties and discusses both chemical (reversible and polymeric) and also non-chemical (irreversible and microvascular) systems, with emphasis focused on the recent reports in the field.

This work describes a study into thiol-ene based Michael addition reactions. Different catalysts, primary and tertiary amines and phosphines, were investigated for the reaction of a range of thiols with dimers and oligomers of some (meth)acrylates. Primary and tertiary amines are efficient catalysts for the thiol-ene reaction, although these catalysts require several hours to reach high conversion. Moreover, the phosphine catalysts, dimethylphenylphosphine (DMPP) and tris-(2carboxyethyl)phosphine (TCEP), were investigated in detail. DMPP is an efficacious catalyst yielding complete conversion in few minutes under optimized conditions. Importantly, the concentration of DMPP should be kept at catalytic levels to avoid the formation of by-products, originating from the addition of DMPP to the vinyl group. Furthermore, TCEP is an efficient catalyst for thiol-ene reactions in aqueous media when the pH of the medium is higher than 8.0 since at acidic pH the formation of by-products is observed.Scheme 1 Proposed mechanism for the nucleophile mediated hydrothiolation of an acrylic carbon-carbon bond under phosphine catalysis.

Glycopolymers are becoming more and more important in understanding biological interactions due to their unique recognition properties. Macromolecules with different chain lengths, compositions and architectures provide enormous diversity in the formation of primary and secondary structures that have a major effect on multivalent binding to lectins. It is crucial to control the precise structure of macromolecules to achieve specific and selective carbohydrate-lectin binding. The use of advanced synthesis techniques to prepare well-defined glycopolymers and selected advanced analytical techniques to study multivalent interactions are highlighted in this Feature Article.

Homopolymers of methacrylic acid (MAA), monoethyleneglycol methyl ether methacrylate (MEOMA), diethyleneglycol methyl ether methacrylate (MEO 2 MA), oligo(ethyleneglycol) methyl ether methacrylate (OEGMA 475 and OEGMA 1100) and oligo(ethyleneglycol) ethyl ether methacrylate (OEGEMA 246) were synthesized with various chain lengths via reversible addition fragmentation chain transfer (RAFT) polymerization. The homopolymers of MAA, MEOMA and OEGMA 1100 did not show any cloud point (CP) in the range of 0-100 C, whereas at a pH value of 7, the CPs were found to be 20.6, 93.7, and 20.0 C for p(MEO 2 MA), p(OEGMA 475) and p(OEGEMA 246), respectively, with an initial monomer to initiator ratio of 50. Furthermore, statistical copolymer libraries of MAA with OEGMA 475 and OEGMA 1100 were prepared. The cloud points of the random copolymers of MAA and OEGMA 475 were found to be in the range of 20-90 C; surprisingly, even though the homopolymers of MAA and OEGMA 1100 did not exhibit any LCST behavior, the copolymers of these monomers at certain molar ratios (up to 40% OEGMA 1100) revealed a double responsive behavior for both temperature and pH. Finally, the cloud points were found to be in the range of 22-98 C, measured at pH values of 2, 4, and 7, while no cloud point was detected at pH 10. V

The combination of controlled polymerization techniques and "click" reactions form an efficient platform for the preparation of polymers in various architectures. In this critical review, an update of our 2007 review in Chem. Soc. Rev., we focus on the "click" reactions that have been used widely in the last four years to create new polymer architectures. Not only block copolymers and star-shaped polymers but also cyclic and dendritic macromolecules could be synthesized using these robust "click" reactions (205 references).

Glycopolymers consisting of styrene (St) and pentafluorostyrene (PFS) were synthesized by a combination of nitroxide-mediated polymerization and "click" chemistry. A series of well-defined homopolymers as well as block and random copolymers of St and PFS were obtained with different ratios by using Bloc Builder as an alkoxyamine initiator. Some copolymers showed self-assembly behavior into regular nanospheres with diameters ranging from 70 to 720 nm by applying the nanoprecipitation technique. In addition, a thiol-glycoside (2,3,4,6-tetra-O-acetyl-1-thio-β-D-glucopyranose) was reacted under ambient conditions with PFS moieties on the polymeric backbone utilizing a thiol-para fluoro "click" reaction. This nucleophilic substitution reaction was performed with high yields, and the reaction kinetic was monitored online with 19 F NMR spectroscopy. Finally, the deacetylation of the protected glucose moieties was carried out to yield well-defined glycopolymers. The polymers were characterized in detail by 1 H, 13 C, and 19 F NMR spectroscopy, size exclusion chromatography, and MALDI TOF-MS.