The free radical homo- and copolymerisation behaviour of myrcene (3) and norbornadiene (1), was studied. Myrcene exhibited free radical polymerisation behaviour similar to the petroleum-based monomer isoprene, providing an alternative to non-renewable resources. Myrcene exhibited free radical polymerisation behaviour similar to that of the petroleum-based monomer isoprene, offering a potential alternative to non-renewable resources. Myrcene and the norbornadiene monoester were copolymerised to produce materials with a wide range of molecular weights and thermal properties. Notably, copolymerisation of monomer 1 and myrcene exhibited statistical copolymerisation behaviour with an almost ideal azeotropic trend, as confirmed by the reactivity ratios. This suggests that material properties could be customised based on specific application needs, ranging from films to elastomers.

Gold nanoparticles and calix[n]arenes are well-established platforms for creating multivalent carbohydrate ligands that enhance binding avidity and selectivity toward carbohydrate-recognizing receptors, such as bacterial lectins. In this study, we present a modular synthesis protocol for tailor-made and (multi)functional glycocalix[4]arene derivatives using solid-phase polymer synthesis. A calix[4]arene building block with a single carboxyl group on the lower rim and four nitro groups at the upper rim is introduced. This building block is attached to a solid support using standard solid phase peptide coupling conditions, followed by reduction of the upper rim nitro functionalities to yield four amine groups, that are further functionalized through solid-phase polymer synthesis. Using this modular approach, we access a series of glyco-calix[4]arene structures that are then further conjugated onto ultrasmall gold nanoparticles. Conjugation is promoted either via one or via four alkyne groups on the glycocalixarene structure, providing a handle to tune the overall valency of the final glyco[4]calixarene-gold nanoparticle conjugates. Finally, the glycocalix[4]arene derivatives and conjugates are evaluated for their inhibitory potential against bacterial adhesion showing the importance of multivalent carbohydrate presentation to effectively block Escherichia coli (E. coli) adhesion.

Imidazole-containing polymeric accelerators were synthesized through free-radical polymerization and applied in the curing of diglycidyl ether of bisphenol A resin with the hardener dicyandiamide. Reactivity and storage stability were followed via differential scanning calorimetry, and an increased pot life was observed after incorporation into polymers. Depending on the employed monomers and composition, the compatibility with epoxy resin was adjusted and the storage stability thereby improved, while a high reactivity is retained under curing conditions. Microscopy imaging showed the dissolution of the polymeric accelerators in epoxy resin above a critical temperature enabling a high reactivity. The best performing accelerator was then applied in an epoxy adhesive film formulation. The strength of the bonding of stainless-steel test bodies was examined in a lap shear test showing superior long-term stability while maintaining efficient acceleration of this type of polymeric accelerator for adhesive applications.

This study aims at quantifying the steric shielding effect of multivalent glycoconjugates targeting pathogens by blocking their carbohydrate binding sites. Specifically, PEGylated and non-PEGylated glycoconjugates are studied as inhibitors of lectins and bacterial adhesins evaluating the steric repulsion effect of the nonbinding PEG chains. We use the soft colloidal probe (SCP) adhesion assay to monitor the change in the adhesion energy of mannose (Man)-decorated hydrogel particles on a layer of concanavalin A (ConA) in the presence of sequence-defined multivalent glycoconjugate inhibitors over time. The results show that PEGylated glycoconjugates achieve a stronger adhesion inhibition when compared to non-PEGylated glycoconjugates although the dissociation constants (KD) of the PEGgylated compounds to ConA were larger. These results appear in line with Escherichia coli adhesion inhibition assays showing a small increase of bacteria detachment by PEGgylated glycoconjugates compared to non-PEGylated compounds. This suggests that an increase of sterical shielding via PEGylation may help reduce the invasiveness of pathogens even after they have adhered. Adhesion studies based on electrostatic interactions using amine-linked PEG of varying molecular weight confirm that such sterical shielding effect is not limited to carbohydrate-mediated adhesion.

We investigate the curing of low viscosity di-/tricyclic carbonates and amines for adjustable polyhydroxyurethanes and their application in a double chamber syringe.

Polymerizable merocyanine and cyanine dye monomers are synthesized and applied in a statistical copolymerization with methylmethacrylate, giving a series of highly fluorescent poly(methyl methacrylate) (PMMA) copolymers. Photophysical properties of yellow to red merocyanine- and of pink to dark purple cyanine-containing copolymers are studied by fluorescence spectroscopy in solid state as well as in different solvents. The highest quantum yield measured in the solid state is observed for copolymers with the lowest dye content: 16% for merocyanine-based and 13% for cyanine-based copolymers, respectively. Fluorescence properties in solution show positive solvatochromism for both merocyanine monomer and copolymer. Copolymer, in comparison to monomer, is hypsochromically shifted to lower wavelengths which point toward H-aggregation of the chromophores in the copolymer matrix.

The oxidative coupling of 4-tert-butylphenol (1), 2,6-di-tert-butyl-p-cresol (11) and 4-cyanophenol (10) in the presence of iron salen catalysts (salen = N,N-bis(salicylidine)ethylenediamine) and the influence of amine additives on the conversion of 1 were investigated. Furthermore, the activity of the iron complexes was correlated with the substituents at the 5,5-positions of the salen ligands. Mechanistically conclusions based on dimer formation in the reaction between 10 and 11 are presented. In the second part of the study the obtained hydrophobic poly(4-tert-butylphenol) was modified with Jeffamine((R)) M-600, M-1000 or M-2070 to give amphiphilic copolymers (18a-c). The amphiphilic copolymers were characterized via size-exclusion chromatography and dynamic light scattering. The concentration dependence of the cloud point appearance in water of amphiphilic copolymer 18c was analysed via turbidity measurements. (c) 2016 Society of Chemical Industry

We describe the synthesis of bromo-tert-butyloxycarbonyl (Br-t-BOC)-amino-protected monomers 2-((1-bromo-2-methylpropan-2-yl)oxycarbonylamino)ethyl (meth)acrylate 3a,b. For this purpose, 2-isocyanatoethyl (meth)acrylate 1a,b was reacted with 1-bromo-2-methylpropan-2-ol (2a). The free radical polymerization of (Br-t-BOC)-aminoethyl (meth)acrylates 3a,b yielded poly((Br-t-BOC)-aminoethyl (meth)acrylate) 6a,b bearing protected amino side groups. The subsequent solvolysis of the Br-t-BOC function led to the new polymers poly(2-aminoethyl (meth)acrylate) 8a,b with protonated free amino groups. The monomers and the resulting polymers were thoroughly characterized by 1H NMR, IR, GPC and DSC methods. The kinetics of the deprotection step was followed by 1H NMR spectroscopy. The solvent polarity and neighboring group effects on the kinetics of deprotection are discussed.

A new series of crosslinkable dimethacrylates containing thioether and phosphonic acid were synthesized. The structures of the different synthesized crosslinkable agents based on oleic acid, cinnamic acid, acrylated glycerol 1,3-dimethacrylate and a chalcone derivative were established by electrospray ionization, DSC, NMR and Fourier transform infrared spectroscopy. In order to prove the accessability of the double bonds on network formation, the radical curing of these compounds with N,N-dimethylacrylamide as comonomer was examined. (C) 2015 Society of Chemical Industry

A crosslinking agent of thioether containing a phosphonic acid, (3‐((11‐((1,3‐bis(meth­acryloyl­oxy)propan‐2‐yl)oxy)‐11‐oxoundecyl)thio)‐propyl)phosphonic acid (6), is synthesized. The crosslinking agent is characterized by electrospray ionization (ESI), NMR, and Fourier transform infrared (FTIR) spectroscopy. After the copolymerization with N,N'‐dimethyl­acrylamide, the influence of the metal ions Ca2+, Fe3+, and La3+ on the swelling behavior of these disc‐shaped samples is examined. The rheological behavior of unswollen and swollen crosslinked copolymers is also investigated with respect to the added metal ions. image

Thiol-ene photopolymerizations gain a growing interest in academic research. Coatings and dental restoratives are interesting applications for thiol-ene photopolymerizations due to their unique features. In most studies the relative flexible and hydrophilic ester derivative, namely pentaerythritoltetra(3-mercaptopropionate) (PETMP), is investigated as the thiol component. Thus, in the present study we are encouraged to investigate the performance of more hydrophobic ester-free thiol-modified bis- and trisphenol derivatives in thiol-ene photopolymerizations. For this, six different thiol-modified bis- and trisphenol derivatives exhibiting four to six thiol groups are synthesized via the radical addition of thioacetic acid to suitable allyl-modified precursors and subsequent hydrolysis. Compared to PETMP better flexural strength and modulus of elasticity are achievable in thiol-ene photopolymerizations employing 1,3,5-triallyl-1,3,5-triazine-2,4,6-trione (TATATO) as the ene derivative. Especially, after storage in water, the flexural strength and modulus of elasticity is twice as high compared to the PETMP reference system.

Thiol‐ene photopolymerizations combine the unique features of step‐growth reactions and photoinitiated polymerizations, so that they experience a growing interest for applications such as coatings or dental restoratives. Most studies have making use of a relatively flexible ester and the hydrolytically labile derivative pentaerythritoltetra(3‐mercaptopropionate) (PETMP) as the thiol component in common. In this study, the performance of hydrolytically stable 1,3,5‐tris(3‐mercaptopropyl)‐1,3,5‐triazine‐2,4,6‐trione (4a), 1,3,5‐tris(2‐methyl‐3‐mercapto‐propyl)‐1,3,5‐triazine‐2,4,6‐trione (4b), and oligomers thereof in thiol‐ene photopolymerizations is investigated. The oligomers are prepared via thiol‐Michael or thiol‐isocyanate additions by using 4a and suitable diacrylates or diisocyanates containing a rigid core structure. Compared with PETMP, the thiol derivative 4a shows better flexural strength and modulus of elasticity in thiol‐ene photopolymerizations with 1,3,5‐triallyl‐1,3,5‐triazine‐2,4,6‐trione (TATATO) as the‐ene derivative. This phenomenon becomes especially evident after storage in water at 37 °C for 24 h. Furthermore, the performance regarding the flexural strength, the Young's modulus of elasticity, the polymerization shrinkage stress of 4a, and the polyadducts thereof in dental filling composites is evaluated and discussed. image

Free radical terpolymerization of (N,N)-dimethylacrylamide, ethylene-glycol-dimethacrylate and N-(p- or m-ethyl-phenyl)acrylamide leads to para- and meta-ethyl-phenyl-modified hydrophilic polymer networks. Polymeric networks of different molar ratios are prepared in special molds to give water swellable disc- shaped samples. The swelling behavior in water and aqueous cyclodextrin (CD) solution of the obtained samples is described while a distinctive differentiation between the para- and meta-ethyl-phenyl containing networks in CD solution can be found.

The microwave-assisted polycondensation of maleic anhydride and 1,6-hexanediol was carried out using p-toluenesulfonic acid as catalyst. The resulting unsaturated polyester was characterized using Fourier transform infrared (FTIR) and 1H NMR spectroscopy, and the molecular weight determined using gel permeation chromatography. 4,4′-Decanediyldioxydi(N-methyl-p-phenylenenitrone) was chosen as a model compound for the crosslinking of the unsaturated polyester. The crosslinking, which is known to proceed via 1,3-dipolaric cycloaddition, was followed using differential scanning calorimetry. Additionally, the kinetics of the cycloaddition was evaluated at 120 °C using FTIR spectroscopy. Copyright © 2012 Society of Chemical Industry

Polymerizable phenolphthalein derivatives with pH-sensitive properties were synthesized in the course of electrophilic aromatic substitution reactions. N-(2-hydroxy-5-(1-(4-hydroxyphenyl)-3-oxo-1,3-dihydroisobenzofuran-1-yl)benzyl)acrylamide (3) and N,N'-(((3-oxo-1,3-dihydroisobenzofuran-1,1-diyl)bis(2-hydroxy-5,1-phenylene))bis(methylene))diacrylamide (4) were obtained and characterized. Copolymerization of 3 and 4 with acrylic acid (5a), N-(isopropyl)acrylamide (5b), and N,N-dimethylacrylamide (5c) enabled the synthesis of color switchable materials. Thereby, water-soluble pH sensitive linear polymers 6 and 7 were prepared using monomer 3. Additionally, cross-linked polymers 8 were prepared successfully by copolymerization of 4 and 5c. These pH-sensitive polymers form hydrogels in aqueous solution. Linear viscoelastic behavior depending on the concentration of the cross-linker was observed.

We describe the synthesis of 5,11,17,23-tetra-tert-butyl-25,27-dioxypropylphosphonic acid-26,28-dimethacryloyloxy-calix [4]arene and 5,11,17,23-tetra-tert-butyl-25-oxypropylphosphonic acid-27-hydroxy-26,28-dimethacryloyloxy-calix[4]arene starting from para-tert-butyl-calix[4]arene. The complete reaction was proved by matrix-assisted laser desorption ionization time of flight mass spectrometry and nuclear magnetic resonance spectroscopy. The influence of these compounds on the kinetics of the radical polymerization of methyl methacrylate was shown by dilatometry. Furthermore, the adhesive properties of dental adhesives containing these calix[4]arene derivatives were investigated. Copyright (c) 2012 Society of Chemical Industry

The synthesis of 5,11,17,23-amino-25,26,27,28-propoxycalix[4]arene (calix[4]amine, 4) starting from 5,11,17,23-nitro-25,26,27,28-propoxy-calix[4]arene (3) via microwave-assisted transfer hydrogenation is reported. Furthermore, the calix[4]amine (4) is functionalized with an acrylamide moiety. The swelling behavior in water, the influence on the glass transition temperature, and the shear modulus of a crosslinked N,N-dimethylacrylamide (NDA) polymer with 5,11,17,23-acrylamido-25,26,27,28-propoxycalix[4]arene (5) and EGDMA, respectively, are investigated.